M RIBS) REPORT
Guidance Document for
Testing and Permitting
Sewage Sludge Incinerators
Revised Draft Final Report
For U.S. Environmental Protection Agency
Prime Contractor
Pynamac Corporation
Subcontract No. S-011 -1188
EPA Contract No. 68-03-3533
Task No. 216
MRI Project No. 9549-16
September 21,1990
MIDWEST RESEARCH INSTITUTE 425 Volker Boulevard, Kansas City, MO 64110-2299 • (816) 753-7600
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MRIBB REPORT
Guidance Document for Testing and
Permitting Sewage Sludge Incinerators
Revised Draft Final Report
For U.S. Environmental Protection Agency
Wastewater Solids Criteria Branch (WH-585)
Criteria and Standards Division
Office of Water Regulations and Standards
401 M Street, SW
Washington, D.C. 20460
Prime Contractor
Dynamac Corporation
11140RockvillePike
Rockville, Maryland 20832
Subcontract No. S-011 -1188
EPA Contract No. 68-03-3533
Task No. 216
MRI Project No. 9549-16
September 21,1990
MIDWEST RESEARCH INSTITUTE 425 Volker Boulevard, Kansas City, MO 64110-2299 • (816) 753-7600
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PREFACE
This draft document was prepared by Midwest Research Institute (MRI)
for the U.S. Environmental Protection Agency (EPA) under subcontract to
Dynamac Corporation on EPA Contract No. 68-03-3533. The document was devel-
oped by Bruce Boomer and Thomas Dux with assistance from Steven Schliesser and
Phil Englehart. The contents of this draft have not been reviewed or approved
by EPA.
Approved for:
I
MIDWEST RESEARCH INSTITUTE
:har!les F. Holt, Ph.D., Director
Engineering and Environmental
Technology Department
September 21, 1990
ii
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CONTENTS
; Page
I. ; Introduction 1
II. | Testing and Monitoring Activities 3
! A. Sampling and analysis of sludge inputs !i 3
i B. Monitoring of key operating parameters -. lo
I C. Stack gas sampling 24
I D. Dispersion modeling 29
III.| Reviewing and Interpreting Test Results.. 31
A. Sewage sludge sampling and analysis results '.'.'. 33
j B. Process monitoring results 33
; C. Results of stack sampling and analysis 36
IV. | Approach to Establishing Permit Limits 36
A. Sludge feed rate „ " 33
i B. Temperature, oxygen, and total hydrocarbons (THC) 40
I C. Air pollution control limits 40
' D. Deviations from limits 41
i E. Calibration and maintenance of monitoring
I instrumentation 41
i F. Record keeping !!!!! 42
V. Continuing Enforcement Objectives 43
VI. i References .... 44
Appepdix A: Draft multiple metals sampling train test procedures A-l
Appendix B: Measurement of total hydrocarbons in stack gases B-l
Appendix C: Draft method for determination of hexavalent chromium
i emissions from stationary sources „ C-l
Appendix D: Example calculation for determining the allowable
I sludge feed rate.... .- D_l
iii
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I. ! INTRODUCTION
This document provides practical guidance for the testing and
permitting of sewage sludge incinerators under regulations being proposed
under the Clean Water Act. Designed for use by the organizations that own and
operjate sludge incinerators and control agency permit writers (EPA and state),
the [document provides guidance for testing, monitoring, and evaluating the
performance of sewage sludge incinerators in conjunction with proposed rules
published in the Federal Register on February 6, 1989.
I
! The rules (proposed as 40 CFR 503) will establish numerical require-
ment^ for sewage sludge incinerators. A previous ruling, incorporated into
40 CFR 501, established the framework for a permitting program for sewage
sludge incinerators. Although specific details in the proposed rules are
subject to revision prior to final promulgation, the general approach is not
expected to change. Since the Clean Water Act requires compliance within
12 mpnths of the date the rule is promulgated (or within 24 months if the
regulation requires construction of new pollution control facilities),
owner/operators of sludge incineration facilities are encouraged to evaluate
the jimpact of the proposed rules upon their facilities as soon as possible.
This; document provides a basis for evaluating sludge incinerators in response
to the proposed rules.
I
I This document addresses only the requirements proposed and
promulgated under the Clean Water Act; these requirements may be administered
through other EPA or state control Agency programs and permits. However, it
is important to note that sewage sludge incinerators must comply as applicable
with regulations of the Clean Air Act (CAA) and the Resource Conservation and
Recovery Act (RCRA); this document does not address the requirements of these
two programs.
i
i
Based upon the rules proposed on February 6, 1989, and subsequent
developments, the permitting program for sewage sludge incinerators is
expected to include the following major components:
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A
li
series
of equations are provided in the proposed rule for determining input
imits for metals.
collect
compl
control
of
ow
to
A risk-based limitation of inputs of beryllium, mercury, lead,
arsenic, cadmium, chromium, and nickel to the incinerators.
A technology-based limitation of total hydrocarbons (THC) in
incinerator emissions.
Limitations on maximum combustion temperature, maximum oxygen
content of exit gas, and selected air pollution control system
parameters.
Continuing monitoring and record keeping requirements for sludge
feed and specific key operating parameters.
This document describes how an incinerator owner/operator can
the appropriate data and establish an appropriate monitoring system to
y with the proposed regulations. The document also provides guidance to
Agency permit writers for reviewing test plans, reviewing the results
testing and monitoring, and establishing permit conditions. Both
owner/operators and permit writers are encouraged to read this entire document
become familiar with the testing/monitoring methods available and the
objectives of the permitting program. The remaining sections of the document
are organized as follows:
Chapter II—Testing and Monitoring '
Chapter III—Reviewing and Interpreting Test Results
Chapter IV—Establishing Permit Conditions
Chapter V—Continuing Enforcement Objectives
In an attempt to make this document as concise and functional as
possible, the remaining sections are highly referenced, providing background
descriptions of standard methods as appropriate and referring to readily
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available EPA documents for the details associated with established proce-
dures. For further information on the proposed rules, specific limitations,
equations, and general background on sewage sludge incinerators, the reader is
referred to the proposed rule and preamble (Federal Register, February 6, 1989)
and ,the technical support document for sewage sludge incineration (EPA, 1989a,
whidh is available from EPA).
II. | TESTING AND MONITORING ACTIVITIES
j
The permitting program for sewage sludge incinerators is based upon
limiting the toxic metal loading to the incinerator and continuously moni-
toring key indicators of adequate combustion and air pollution control. This
requires (1) a continuing sludge characterization program to assess the input
of metals and (2) instruments for continuously monitoring the operating
parameters. Facilities must also measure stack emissions to develop site-
speciific control efficiency factors and conduct dispersion modeling to
calculate a site-specific dispersion factor. These are used to calculate
sitei-specific operating limits. This chapter describes the testing,
monitoring, and modeling options available to satisfy the needs of the sludge
incinerator permitting program.
j
iA. SAMPLING AND ANALYSIS OF SLUDGE INPUTS
: Sludge inputs to incinerators must be characterized at a minimum in
terms of the concentrations of toxic metals. The metals concentrations are
used; in a calculation to compute the allowable concentration of each metal in
the jfeed sludge and the allowable maximum feed rate of sludge to the
incinerator. These calculations are based upon the risk factors associated
withjeach of the toxic metals. (The equations and basis for these calcu-
lations are provided in the preamble and proposed rules in the February 6,
1989^ Federal Register).
I
i
i The best sludge characterization data will result from a long-term
sampling and analysis program that is designed to minimize the effect of
random variation in sludge quality. Suggested methods for developing such a
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program are provided in the POTW Sludge Sampling and Analysis Guidance Document
(EPA| 1989c). This document notes the importance of addressing anticipated
cycljc variation in pollution loading and treatment plant characteristics in
characterizing the sludge characteristics. Additional guidance on sampling
plan design can be found in Chapter 9 of SW-846 (EPA, 1986). This chapter
provides guidance on designing a sampling plan to demonstrate that a
particular waste (sludge) is beneath a particular regulatory limit (calculated
maximum sludge concentration for metal of interest).
i
; 1. Frequency of Sampling;
I Ideally, sludge characterization data used for determining permit
limiis for sludge feed rates will result from a long-term sampling and
analysis program or at least from a shorter term program specifically designed
to collect samples that are representative of the expected range of vari-
ation. An exception will be the sampling programs designed to determine
control efficiencies of toxic metals in an incineration facility. Such tests
(described in Section C of this chapter) will be based upon only the charac-
teristics of the sludge fed to the incinerator at the time of the test.
i
j Continuing sludge characterization is required during the life of
each| operating permit. Required minimum frequencies (e.g., monthly,
quarterly, or annually) for sampling and analysis of input sludge are based
upon|the design capacity of the treatment works, as described in Subpart I of
the proposed rules.
| 2. Access to Sludge Inputs and Sampling Methods:
|
j Suggested sampling points and sampling methods are described in EPA
(1989c). Each facility is required to provide access to the sewage sludge
feedi so that representative samples of the sewage sludge can be collected.
Major considerations for sampling include the following:
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Each grab sample should be collected in a manner to be as
representative per guidelines (EPA, 1989c) as possible of the total
flow stream. Particular attention should be paid to obtaining
samples which are representative of both liquids and solids
fractions of the sludge. Metal concentrations for some sludges are
higher in the solids fraction.
Efforts must be made to minimize the possibility of contamination or
any other potential chemical change to the sample during sampling
and subsequent handling/storage prior to analysis,,
!
! 3. Analytical Methods For Metals:
; Measurements of the sludge for metals concentration are required.
The JFollowing discussion concerning these analyses are based upon guidance in
the Hazardous Waste Incineration Measurement Guidance Manual (EPA, 1989b), POTW
Sludge Sampling and Analysis Guidance Document (EPA, 1989c), and Proposed Methods
for Measurements of CO, O2, THC, HCl, and Metals at Hazardous Waste Incinerators
(EPA; 1989e).
The physical properties of the waste and the calculated regulatory
threshold limits (equations 1, 29 3, and 4 of the proposed rule) should guide
the fhoice of sample preparation and analysis methods. The method of sample
preparation should be sufficiently rigorous to provide for complete digestion
of |:he sludge, and the analytical technique must provide sufficient
sensitivity to generate reliable data at the concentration levels of
regulatory concern. For example, if the regulatory limit is low,
determination of arsenic by inductively coupled plasma would not provide an
adequate detection limit of sufficient sensitivity, and the more sensitive
technique of graphite furnace atomic absorption would be appropriate.
The last two guidance documents in the previous paragraph give
general background information on metals analysis. Table II-l summarizes the
specific methods given in the guidance manuals. The methods come from SW-846
(EPA 1 1986) with the following specific recommendations:
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TABLE. II-l
METHODS OF PREPARATION AND ANALYSIS OF
SLUDGE SAMPLES FOR METAL ANALYTES*"
Analyte
As
Be
Cd
Cr
Pb
Hg
Ni
Preparation Method Analysis Method
3050
3050
7061
3050
3050
3050
3050
3050
3050
3050
3050
3050
3050
3050
3050
7471
3050
3050
6010
7060
7061
7090
6010
7091
7130
6010
7131
7190
6010
7191
7420
6010
7421
7471
7520
6010
Analyses
Typeb
ICP
AAS-6F
Hydride
AAS-DA
ICP
AAS-6F
AAS-DA
ICP
AAS-6F
AAS-DA
ICP
AAS-6F
AAS-DA
ICP
AAS-6F
AAS-CV
AAS-DA
ICP
All methods come from the Test Methods for Evaluating
. Solid Waste (SW-846 Third Edition, November 1986).
AAS-DA: Atomic absorption spectrometry by direct
aspiration method.
AAS-6F: Atomic absorption spectrometry by graphite
furnace method.
AAS-CV: Atomic absorption spectrometry by cold vapor
method.
ICP: Inductively coupled plasma atomic emission
spectroscopy.
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Method 3050 for digestion. In Table II-l the preferred method
is 3050 which is applicable to sludges, sediments, and soil
samples. However, if the sample is more aqueous in nature,
Methods 3010 or 3020 are suggested in EPA (1989b).
Analysis by direct aspiration atomic
Method 6010 for inductively coupled plasma.
spectrometry or
Low concentration analysis by graphite furnace atomic
spectrometry.
Method 7471 for mercury cold vapor atomic absorption (CVAA).
4. Quality Assurance and Quality Control (QA/QC) Procedures;
I General quality assurance and control procedures are discussed in
SW-846 and are covered in detail in EPA (1989c; 1990). The "POTW Sludge
Sampling and Analysis Guidance Document" (EPA, 1989c) states that "sludge
sampling and analysis programs for determining compliance with permit
conditions should include a written QA Plan." A QA plan gives the data
quality objectives of a sampling and analysis effort and details the sampling,
analysis, quality control, and quality assurance procedures which will be
employed to ensure that data quality is sufficient to support the regulatory
decisions based upon the data. A general discussion on QA plan development
can jbe found in EPA (1980). EPA (1990) contains specific information on
development of QA plans for sampling and analysis of hazardous waste
incinerators. Some general applicable topics concerning QA/QC are discussed
in this section.
i
i
; a. Sampling QA/QC; One primary objective in sampling for
thisj rule is to obtain representative comparable sludge samples over a
relatively long compliance period. The POTW sampling document (EPA, 1989c)
andiChapters 1, 2, 3, and 9 of SW-846 are useful in designing a sampling
strajtegy. From a QA/QC perspective, the sampling design should be formalized
into a standard operating procedure (SOP). This SOP should justify the sta-
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tist-jcal design of the sampling strategy, specify the sampling frequency, give
a derailed description of the sampling procedures, and delineate required
sample documentation. Each time a sample is taken, the documentation of the
sampling event needs to be sufficient to demonstrate compliance to the SOP.
! *>. Sample custody, handling, and holding: times; General
guidance on sample preservation, sample custody, sample storage containers,
and holding times can be found in Section 2.5 of the POTW sampling document
and Chapter 2 of SW-846. For sample custody considerations, all samples must
be gjiven unique identifiers which are readily traceable from the field sam-
i
pi ing; records, through the analysis records to the final reportable data.
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j Holding times, sample preservation methods, and sample
containers must be specified for each analysis type and must follow the
established guidance. Holding times are dependent upon the properties of the
sample matrix and the analytes of interest. Holding times can vary from
28 days for mercury to 6 months for chromium. These preservation procedures
should be delineated in the sampling SOP. There must be sufficient field and
laboratory documentation to ensure that sample handling and holding time
procedures were followed. All sample results should be reported with the
dates of sample collection, sample preparation, and sample analysis. If the
established procedures are not followed, the acceptance of analytical data
mustjbe justified in terms of the end use of the information.
i
j As an additional check on sample handling, field blanks should
be ccjllected on a regular basis. Field blanks should consist of a water rinse
(free, of metal analytes) of sampling equipment before the sample has been
collected. This check will assure that the observed sample concentration was
higher than any possible contamination from sample handling.
i c. Analysis QA/QC: The methods of analysis of the sludge for
metals should be designated during the planning stage arid should also be
writtjen as an SOP to be a companion document to the ssimpling SOP. The
analyjsis SOP should indicate the following:
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The sampling SOP reference.
The estimated analyte concentration of regulatory concern.
The analytical methodology.
The QC procedures for documenting the accuracy and
precision of the analytical result.
The reportable data and required records for complete
documentation.
! Each determination for metals analysis should be reported along
with! QA/QC information giving the precision and accuracy of the data.
However, the specific analysis method and QC procedures for documenting the
precision and accuracy of the determination can vary depending upon the
laboratory conducting the analysis. For example, precision can be measured by
analysis of the sludge sample and a sample split, while accuracy is measured
by splitting the sample and fortifying the split sample. Some laboratories
use ^ different method employing a control sample of known constant concentra-
tion, and multiple analyses of the control sample to provide the determination
of bpth accuracy and precision. Control samples of metals in a sludge matrix
can be commercially obtained.
} All the analytical methods have QC procedures concerning
calibration, accuracy, and precision. These should be supplemented with some
additional QC. To establish the precision and accuracy of metals analyses,
analysis of duplicate and analyte-fortified sludge samples is recommended. In
the jbeginning of the monitoring program, a small study is recommended to
demonstrate acceptable precision and accuracy for the analysis of the sludge
samples. Three sludge samples are each split into three portions. Two
portions are prepared and analyzed to provide precision data as percent
range. The third portion is fortified with the analyte of interest at two
times the level of regulatory concern and then prepared and analyzed like the
othe^ two split samples. Accuracy is measured as the recovery of the
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f
fortjified analyte compared to the average analyte level found in the two
sampjles for precision analysis. This precision and accuracy determination
shoujld be done with a single sample for every 20 field samples or once per
year;, whichever is greater. The accuracy and precision should meet the
statistical criteria of the sampling and analysis design presented in the QA
plant
i
[
I B. MONITORING OF KEY OPERATING PARAMETERS
j Key operating parameters for sludge incinerators are monitored
continuously to indicate that adequate combustion conditions are being
maintained in the incinerator and to minimize toxic metals emissions. Key
parameters specifically identified in the proposed rules to be monitored
continuously include:
i
; • Sludge feed rate.
i
i • Temperature.
Oxygen.
I • Total hydrocarbons.
j
I • Selected air pollution control device parameters.
i
!
| Maximum or minimum values will be established for each of these
monitored parameters. Limits are established for maximum sludge feed rate
based upon formulas provided in the proposed rule. Sludge feed rate
1 imitations are based upon the risk associated with the total sewage sludge
feed [rates for all. sewage sludge incinerators located at each treatment
facility.
I Limits for maximum combustion temperature in a sewage sludge
incinerator and maximum oxygen content for exit gas from incinerators will be
based upon the results of performance testing. Limitations for selected
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parameters for the air pollution control system will also be specified in a
permjit to indicate appropriate performance of the emission control devices.
Thesp limits will be based upon monitored information collected during
performance tests.
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| The following pages briefly discuss the monitoring of each of the
identified parameters.
i
i 1. Sludge Feed Rate;
i
i
i Although the sludge feed rate to a sewage sludge incinerator can be
monitored by a variety of flow devices, conveyor weighing systems and
volumetric methods appear to be the most common methods used.
Conveyor weighing systems include belt weighers and weigh
belts/augers. All conveyor weighing systems are fairly similar in operation,
mainly differing because of placement locations of the weighing device. In
general, the accuracy of these systems is around ±2%. Sludges can be moni-
tored with the systems, provided that wet material does not drain off the
conveyor belt. Screw augers, however, may be used in such cases to replace
the Conventional conveyor belt. A summary of details on weight belt/auger
systems is provided in Table I1-2.
I Volumetric methods include calibrated augers emd pumps, rotary
feeders, and belt conveyors. These systems are not generally available
preca'librated but must be calibrated by the user for each particular feed
material. The accuracy of the method depends upon steady operation at a given
speed and assumes appropriate feeders are used to ensure the cavities are
always filled to capacity. Most of these methods can provide some kind of
tachometer signal to indicate speed, which must be related to feed rate by
performing calibration tests. A summary of details about calibrated screw
feeders used in sewage sludge applications is provided in Table II-2.
i Each selected feed rate device must have an accuracy of at least ±5%
over :its operating range. The device must be designed and installed to
facilitate periodic recalibration of the device over its operating range
(i.e.-, a zero adjustment and an adjustment near the maximum flow rate).
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i TABLE 1 1-2
! SUMMARY DETAILS ON TWO COMMON SLUDGE FEED RATE MEASUREMENT DEVICES
: Weigh Belts or Augers
t • "~~"" ' "•• "*
Operation/implementation; This is a combination belt scale and conveyor
system. A prefeeding unit (typically an auger screw) feeds material onto a
conveyor belt, which is mounted on a weight sensor (i.e., load cells). As the
weight of material is sensed, adjustments to the screw speed are made by a
microprocessor /controller, enabling a constant mass feed rate to be
achieved. Similar systems are available which use an auger conveying system.
Usage: All types of solids, granules, and powders.
sludge and shredded metal.
Uses include sewage
Operating range: Capacity typically is 60 Ib/hr to 48,000 Ib/hr (based upon
average density of 40 Ib/fts on a dry material basis).
Output; Typically mass flow rate and totalization.
Measurement frequency; Continuous, with signal averaged at 1-min intervals.
Weigh system is counterbalanced and includes electronic
Calibration:
adjustments for any on-site dampening necessary. Load cells; may be calibrated
by vendor.
Accuracy: ±1% based upon 1-min sampling cycles.
Limitations; Due to effects of momentum, shifting weights, etc., feeds of
widely varying density will affect accuracy somewhat, perhaps to ±3%. Over-
load of weigh belt may cause poorer performance as well. May not give direct
indication of weight charged to incinerator. (The material may "roll" along
the cjonveyor, so that its velocity lags behind that of the conveyor.)
Notes: Similar operations can be installed with feed systems other than
conveying belts. For example, a screw auger can be mounted upon the weight
sensors, thereby making a weigh auger system.
(continued)
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TABLE I1-2 (CONCLUDED)
j Calibrated Screw Feeders
i
Operation/Implementation; A vibrating (to maintain constant flow) hopper
filled with process material empties into a screw auger which has been cali-
bratjed by the vendor or user to give a volumetric feed rate. Auger speed can
be varied, allowing for a broad range of volumetric feed rates, dependent upon
the -size of the auger screw.
Usage: Used for dry materials of fairly consistent density including powders
and jgranules, solvent-laden filter cakes at an industrial facility, sewage
sludge, and contaminated soil.
Operating ranges; 0.04 ft3/hr maximum up to 600 ft3/hr maximum depending upon
size! of the auger screw and rotational speed. For a dry material basis of
40 Ib/fta, this amounts to 1.5 Ib/hr maximum up to 24,000 llb/hr maximum.
Output: Tachometer reading indicates rpm which correlates with volumetric
feed rate.
Measurement frequency: Continuous.
i
Calibration; Tachometer of screw calibrated by rpm, which is correlated to
volup of materials tested.
Accuracy: ±2% of set rate.
i
Limitations; Due to volumetric calibration of feed system, use with materials
of varying density may not provide suitable mass feed rate.
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i 2. Temperature;
i
i
Temperatures within a sewage sludge incinerator are typically
monijtored by thermocouples located at various points within the system.
Minitaum required locations for thermocouples are specified in the proposed
rules for multiple hearth, fluidized bed, electric, and rotary kiln incin-
eratjors. Maximum temperatures in the combustion zone (or outlet duct) are
monitored to minimize the emission of toxic metals from the incinerator.
i
j The thermocouples are always enclosed in a thermowell to protect the
small thermocouple wires and the critical thermocouple "hot" junction from
direjct exposure to the combustion gases and entrained dust particles. Thermo-
coupjles are usually located near the exit of the combustion chamber to provide
a representative temperature reading away from the flame zone, which can
otherwise cause erratic temperature readings as well as damage to the thermo-
coupjle. Thermowells may extend several inches past the inner wall of the
refractory into the gas stream, or may extend only to the depth of the
refractory. Thermowells that extend past the refractory provide a more
accurate measure of the gas temperature and respond more quickly to tempera-
ture; changes; however, this type also may be subject to dust and slag buildup,
which can slow response to temperature changes. Thermocouples may also be
locajted upstream of the air pollution control system to provide a warning or
control mechanism for high temperature excursions that could damage control
equipment.
Thermocouples are available in a variety of types, with each type
constructed of specific metals or alloys. The temperature ranges and reported
accuracy vary by type. The environment the thermocouple is suited for also
varites.
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A summary of thermocouple types and limitations is given below.
Upper Thermocouple
Temp. Accuracy
Type Materials (°F) (+%)
J
E
K
S
R
B
Iron/constantan
Chrome! /constantan
Chrome! /alumel
Pt 10% rhodium/pure Pt
Pt 13% rhodium/pure Pt
Pt 30% rhodium/pure Pt
6% rhodium
•
Note: Accuracies do not consider
1400
1650
2300
2650
2650
3100
environmental
0.
0.
0.
0.
0.
0.
75
50
75
25
25
50
effects or
Environment
Reducing, vacuum, or
i nert
Oxidizing or inert
Oxidizing or inert
Oxidizing or inert
(no metal tubes)
Oxidizing or inert
(no metal tubes)
Oxidizing or inert
(no metal tubes)
location.
Source: Complete Temperature Measurement Handbook and Encvn/nnerffn . dmpna
; Engineering Inc., 1986.
i
i Replacement thermocouples must always be the same type as the
original because the receiver to which a thermocouple is connected is designed
to rj-eceive the signal from a specific type of thermocouple. Thermocouples
genejrate a small millivolt signal that increases with increasing temperature,
but ithe amount of voltage for a given temperature is different for each type
of thermocouple. It is important to realize that thermocouples operate on the
basijs of a junction between two different metals that generates only a small
millivolt signal. Consequently, any wiring connections from the thermocouple
to tfie receiver or any interfering electrical signals can affect the resulting
temperature reading. This sensitivity necessitates the special shielding of
the Wire in electrical conduit.
j Although thermocouples typically are very reliable, they can fail or
give; erroneous readings. For example, a thermocouple junction or wire may
brea|< after long exposure to high temperatures or repetitive cycling.
However, a thermocouple can give erroneous readings for reasons that are not
[
as obvious as a broken junction or wire. For example, if mechanical vibration
abrades the insulation and one of the thermocouple wires comes into contact
with; the metal wall of the thermowell or other grounded metal surface, an
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erroneous temperature reading will likely result. As noted earlier, faulty
thermocouple readings may also be the result of external conditions; for
example, excessive dust buildups around a thermowell can insulate it from the
gas jstream and result in erroneously low temperature readings. To have the
abiljity to compare readings to identify a faulty thermocouple, dual
thermocouples are often used at nearby locations in the incinerator chamber.
Also* the second thermocouple enables continued monitoring of temperatures
while the faulty thermocouple is being checked or replaced.
j
Periodic replacement of thermocouples, and checking the physical
integrity of the thermowell and any outer dust buildup, is; probably the best
maintenance procedure. Because it is not practical to perform a high tempera-
ture |calibration of the thermocouple, only periodic replacement ensures that a
properly operating thermocouple is in place. The receiver should be checked
periodically using calibrated equipment that produces a known millivolt signal
equivalent to a specific temperature reading for a particular type of thermo-
couple. The generated signal can be applied to the thermocouple leads to
check that the receiver's output produces the correct "temperature" reading.
j
| 3. Oxygen:
i
j Oxygen in the exit gas is monitored continuously in a sewage sludge
incinerator as an indirect indicator of gas velocity in the incinerator.
j Oxygen monitors may be of two types: in situ or extractive. In
situ(merely means that the analyzer's sensor is mounted in direct contact with
the :gas stream. In an extractive system, the gas sample is continuously
withdrawn (extracted) from the gas stream and directed to the analyzer which
may lj>e located several feet or several hundred feet away.
j Extractive analyzers include a conditioning system to remove dust
and moisture from the gas sample; thus, the oxygen concentration measurement
is on a dry basis. In situ analyzers, on the other hand,, do not include a
conditioning system, and the oxygen concentration measurement in on a "wet
t
basis." For the same gas stream, the oxygen measurement obtained with an in
situ | analyzer will be slightly lower than that obtained with an extractive
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analyzer. For example, a typical combustion gas stream that contains 10%
water vapor will yield a reading of 8% oxygen using an in situ analyzer and a
reading of 10% oxygen using an extractive analyzer. The oxygen values for
sewage sludge incinerators must be reported on a dry basis.
j Oxygen analyzers are capable of good accuracy (±1% of full scale) as
long as the actual gas to be sampled reaches the analyzer (no pluggage or
in-l^akage of air), the conditioning system (if one is present) is operating
properly, and the instrument is calibrated. Electrocatalytic in situ monitors
havej rapid response time (i.e., seconds). The response times for polaro-
I
graphic and paramagnetic extractive analyzers are slower (several seconds to a
minujte). Extractive systems inherently involve longer response times, usually
on the order or 1 to 2 min, depending on the sampling rate and the volume of
the sampling line and conditioning system.
i
j Problems with oxygen analyzer systems may be difficult to discern
since they commonly are associated with slowly developing pluggage in the
system, or small air in-leaks, etc. The extractive systems should be checked
daily by the operators, and maintained and calibrated on a weekly basis by the
incinerator instrument personnel.
i
| a. In situ oxygen analyzers; In situ analyzers provide rapid
respbnse to changes in the oxygen content of the gas because the sensor is in
direqt contact with the gas stream. In most cases, the sensing element is
enclosed in a sintered stainless steel tube, which allows the gas to permeate
through the tube but prevents particles in the gas stream from entering. Most
in s|itu oxygen analyzers are equipped with connections so that zero gas
(nitfogen) or calibration gas (air) can be flushed through the permeable tube
in contact with the sensing element. Flushing provides a means of zeroing and
spanning the analyzer, and also creates reverse flow of gas through the
permeable tube that helps to remove dust particles that eventually will clog
the tube and slow the detector's response time. Even so, the tube periodi-
cally must be removed for cleaning or replaced if warranted.
! Most in situ oxygen analyzers are of the electrocatalytic type,
sometimes referred to as fuel-cell analyzers. Operation of these analyzers is
17
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base|d upon an electron flow created by reaction of oxygen with a solid
zirconium oxide electrolyte. Consequently, manufacturers recommend that the
sensling element be replaced after several months of service.
b. Extractive oxygen analyzers; Extractive analyzers always
involve a "conditioning system" for removal of water, dust, and sometimes
other constituents that would interfere with operation of the analyzer. An
example extractive system is illustrated in Figure II-l. The moisture
knockout for removal of water vapor and the normal connections for zeroing and
calibrating the analyzer are shown.
j The integrity of the sample line and the conditioning system is
crucjial to obtaining a representative sample and accurate results. Any
in-leakage of air can drastically distort the reading. The extractive system
requjires a pump to draw the sample gas continuously through the sample line,
conditioning system, and analyzer. Most systems include a small rotameter
(fToy/meter) which shows that sample gas is flowing through the system. This
flowmeter is always one of the first items that should be checked if any
problem is suspected because loss of flow will occur if' the pump fails or the
system is plugged. However, even if the flow rate is correct, the measured
gas Concentration will not be correct if there is any problem with the leakage
of air into the gas sample.
i
j Two types of extractive oxygen analyzers, paramagnetic and polaro-
graphic analyzers, are available in addition to the electrocatalytic type
described previously for in situ analyzers. Paramagnetic analyzers measure
the joxygen concentration as the strength of a magnetic field in which oxygen
molecules are present. Oxygen molecules are somewhat unique in displaying a
permanent magnetic moment (paramagnetism), allowing oxygen concentration to be
differentiated from the stack gas sample. Calibration is performed by moni-
toring an inert gas such as nitrogen (zero) and a gas of known oxygen
concentration (span). A potential problem with this type of analyzer is its
susceptibility to paramagnetic molecules other than oxygen. Nitrogen oxide
and initrogen dioxide in particular display a high degree of paramagnetism
(about one-half that of oxygen), but their concentration is usually low
compared to that of oxygen.
18
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Back Plus
Purge Air
-Solenoid
Valve
Reheat
Nitrogen
!
Air Cooled
Condenser
Drain
Zero
Span
Dryer
Low Mid
Level Level
Calibration Calibration
^T
t
Sample
Line
Analyzer
Vent
uf
! I
iJ
I
Strip
Chart
Microprocessor
j Data Logger
Figure II-l. Schematic of an extractive monitoring system.
19
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Polarographic analyzers monitor oxygen concentration by allowing
oxygen to pass through a selective, semipermeable membrane and react at an
electrode in an oxidation-reduction reaction. Measuring the current
produced by the reaction indicates the oxygen concentration. Improper
conditioning of the sample gas is a potential problem with these analyzers,
since moisture and particles will hinder performance of the semipermeable
membrane. Calibration is performed by zeroing with an oxygen-free gas
(nitjrogen) and spanning with a gas of known oxygen concentration (e.g.,
air)|. Furthermore, these monitors contain a liquid electrolyte that has a
i
limited life span and must be replaced at regular intervals.
i
I Additional background information on oxygen monitors is available in
EPA i(1979); additional guidance on the operation and calibration of oxygen
mom'itors is provided in EPA (1989e).
{ 4. Total Hydrocarbon;
t
i
THC is continuously monitored in a sewage sludge incinerator as an
indirect indicator of combustion efficiency for organic material in the
sludge. The method measures the total hydrocarbons as a surrogate for the
total gaseous organic concentration of the combustion gas stream. The concen-
tration is expressed in terms of propane. A gas sample is extracted from the
source through a heated sample line, if necessary, and a fiber filter to a
flame ionization detector (FID). A standard method, Method 25A (40 CFR 60,
Appendix A), is provided as Appendix B of this document. Another variation is
presented in MRI (1989e) and is currently undergoing review at EPA.
The monitors equipped with FIDs essentially respond to unoxidized
carbon. Monitoring efficiency remains relatively constant over a wide range
of concentrations. However, water vapor may have an effect on response.
|
I A wide variety of FID systems are comrnercially available for THC
monitoring. A sample is usually extracted using a diaphragm pump. Prior to
entering the FID, moisture may be removed by use of a condenser, and particu-
late| may be removed by use of one or more filters. Calibration gas may be
injected into the monitor immediately after the sample probe (i.e., before
20
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filters and condensers) or immediately before the FID analyzer (i.e., after
filtjars and condensers). A recent survey of manufacturers and facilities that
use iTHC monitors indicated that the THC monitoring systems were operated
contiinuously on hazardous waste incinerators with reliability (MRI, 1989). .
j
5. Air Pollution Control System:
i
f '
i Permits for sewage sludge incinerators will include permit limits
and continuous monitoring requirements for selected parameters that indicate
adequate performance of air pollution control (ARC) devices. Such
requirements will be developed on a case-by-case basis, depending on the ARC
devijce used and facility-specific issues.
j Selected APC parameters are monitored continuously to indicate that
the APC system is operated and maintained to meet all applicable requirements
and !to minimize toxic metal emissions. A list of performance indicator param-
eters for various APC technologies is presented in Table II-3 along with the
common measuring devices for the respective parameters.
The performance indicator parameters include (a) APC technology-
spedific parameters and (b) universal APC parameters. Examples of APC
technology-specific parameters include pressure drop and liquid flow for wet
scrubbers, and secondary voltage and secondary current for wet electrostatic
precipitators (ESPs). Because the performance of all APC devices is
influenced by gas flow rate and gas temperature, these two parameters are
i
considered to be universal APC parameters and are included for each APC
technology.
I
i 6. Other Parameters;
j
I Other indicator parameters may be appropriate for continuous moni-
toring or permit limits for special cases or for facilities using technologies
different from the types addressed in the proposed rules. Such requirements
woul^d be developed on a case-by-case basis.
21
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ARC Device
Venturi scrubber
Impingement scrubber
TABLE I1-3
PERFORMANCE INDICATOR PARAMETERS FOR
AIR POLLUTION CONTROL DEVICES
Mist eliminator (types
include a wet cyclone, vane
demister, chevron demister,
mesh pad, etc.)
Dry scrubber
(spray dryer absorber)
Parameter
Pressure drop
Liquid flow rate
Gas temperature
(inlet and/or
outlet)
Gas flow rate
Pressure drop
Liquid flow rate
Gas temperature
(inlet and/or
outlet)
Gas flow rate
Pressure drop
Liquid flow
Liquid/reagent
flow rate to
atomizer
pH of liquid/
reagent to
atomizer
For rotary
atomizer:
Atomizer motor
power
(continued)
22
Example Measuring Devices
Differential pressure (AP)
gauge/transmi tter
Orifice plate with AP
gauge/transmitter
Thermocouple/transmitter
Annubar or induced fan (ID)
parameters
AP gauge/transmitter
Orifice plate with AP gauge/
transmitter
Thermocouple/transmitter
Annubar or ID fan parameters
Differential pressure gauge/
transmitter
Orifice plate with AP gauge/
transmitter
Magnetic flowmeter
pH meter/transmitter
Wattmeter
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-------
TABLE II-3 (CONCLUDED)
Fabriic filter
Wet electrostatic precip-
itator (ESP)
For dual fluid
flow:
Compressed air
pressure
Compressed
airflow rate
Gas temperature
(inlet and/or
outlet)
Pressure drop (for
each compartment)
Broken bags
Opacity
Gas temperature
(inlet and/or
outlet)
Gas flow rate
Secondary voltage
(for each trans-
former/rectifier)
Secondary currents
(for each trans-
former /rect i f i er)
Liquid flow(s)
(for separate
liquid feeds)
Gas temperature
(inlet and/or
outlet)
Gas flow rate
Pressure gauge
Orifice plate with
AP gauge/transmitter
Thermocouple/transmitter
AP gauges/transmitters
Proprietary monitors
Transmissometer
Thermocouple(s)
Annubar or ID fan
parameters
Kilovolt meters/transmitter
Mi 11i ammeters/transmitter
Orifice plate(s) with AP
gauge/transmi tter
Thermocouple(s)
Annubar or ID fan parameters
23
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;C. STACK GAS SAMPLING
| This section describes testing activities used in determining
facility-specific control efficiency values for toxic metals emissions. These
efficiency values are used to calculate the maximum allowable concentration of
toxic metals in the sludge feed and the maximum allowable sludge feed rate
to tljie incinerator based upon the equations provided in the proposed rule.
The {test data will also be used to determine facility-specific limits for
temperature, oxygen, and air pollution control conditions.
f
i
| 1. Test Design;
i
I The stack test must be designed to gather all needed information in
an acceptable manner. Major elements of the testing are:
i
i
| • Sampling and analysis of sludge feed for metcils»
1
j
I • Sampling and analysis of stack emissions for metals.
I
I • Monitoring and documentation of operating conditions during the
i test (including temperature(s), oxygen, total hydrocarbon,
! sludge feed rate, and air pollution control devices).
i
A feW general guidelines are appropriate:
| • The test should be conducted at worst case conditions (i.e.,
i with the highest expected feed rate of sludge, at the highest
j temperature, etc.) for metals emissions in order to obtain the
i most flexible permit conditions. However, the system must be
! operated within its design specifications to demonstrate
! adequate performance in controlling metals emissions.
24
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All testing and monitoring must be conducted concurrently (or
phased to account for material lag time). Sludge feed samples
must be collected and analyzed to calculate an input loading
rate for each investigated toxic metal for comparison with
outlet emission rates.
Three replicate test runs are requested for each specific set
of operating conditions. This provides added assurance that
the incinerator is operating in a consistent manner. Operating
conditions should be maintained as consistently as possible for
the three test runs.
Measurements of temperature, oxygen, THC, sludge feed rate, and
air pollution control indicators should be recorded continu-
ously, or, at a minimum, every 60 sec.
All monitoring instruments should be recalibrated immediately
prior to and after the test. Documentation of calibrations
should be included in the test report.
Sludge feed samples should be collected at least every 15 min
during each stack sampling test period. Individual samples can
be composited into one sample analyzed per test run.
Sampling should not begin until the incinerator has reached a
steady state on sludge feed. A minimum of 60 min (or 120 min
for a multiple hearth) of operation feeding sludge is recom-
mended prior to sampling.
Minimum stack sampling time for each run (actual sampling time
not including time for port changes, etc.) should be 1 hr.
Custody procedures should be used for handling all samples.
Full chain-of-custody procedures are typically much more labor-
intensive but may be used at the applicant's option.
25
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Results should be reported In a format which includes all
information and data necessary to calculate final results and
verify quality assurance objectives. Results should be
presented in as clear and succinct a format as possible.
2. Methods for Measuring Metals Emissions;
Specific EPA methods for sampling and analysis of metal emissions
are Method 12 for lead, Method 101A for mercury, Methods 103 and 104 for
beryllium, and Method 108 for arsenic. These methods may be applicable to
sewage sludge incinerators in cases where only one metal is being
invejstigated. However, for the past 3 years a method has been under
development for sampling and analysis of multiple metal analytes, "Methodology
for the Determination of Trace Metal Emissions in Exhaust Gases From
Stationary Source Combustion Processes." A copy of this method is provided in
Appendix A. Currently the draft method can be applied to 16 analytes. This
makejs the "Multiple Metals Method" highly appropriate for the sampling and
analysis of the regulated metals emitted in the exit gas from a sewage sludge
incinerator.
|
•j The Multiple Metals Method is a variation of U.S. EPA Method 5
(40 CFR 60, Appendix A) which was originally used to sample particulate matter
emitted from power plants. In Method 5, samples are taken at several desig-
nated sampling points in the stack, which represent equal areas. At each sam-
pling point, the velocity, temperature, and static pressure of the
parth'cu late-laden gas stream are measured. The sampling probe is placed at
the .first sampling point, and the sampling apparatus (commonly referred to as
the sampling train) adjusted to take a sample at the conditions measured at
thisj point. The sampling probe is then moved to the next point, and the pro-
cessj is repeated continuously until a sample has been taken from each desig-
natejd sampling point. To achieve valid results in a particulate source test,
the jsample must be withdrawn at the same velocity as the flow of gas in the
stack. This is commonly referred to as isokinetic sampling. Measurement of
26
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stack conditions allows adjustment of the sampling rate to meet this
requirement.
! As the gas stream proceeds through a Method 5 sampling train, the
partjiculate matter is trapped on a filter, the moisture Is removed, and the
volume of the sample is measured. Upon completion of sampling, the collected
material is recovered and sent to a laboratory for analysis.
Since the metals emitted from a sewage sludge incinerator may be in
a solid form within the particulate or in a volatile form within the gas
stream, a modification of the Method 5 train is necessary to collect appro-
priajte samples for analysis of all of the regulated toxic metals simultane-
ously. Appendix A of this document contains the draft metals protocol
Methodology fop the Determination of Trace Metal Emissions in Exhaust Gases From
\
Stationary Source Combustion Processes, This method describes the only system
that! has been proposed to collect both the volatile and nonvolatile fraction
of the stack gases. This draft protocol will be incorporated into a methods
document under preparation by EPA's Office of Solid Waste as background for
proppsed amendments to the RCRA incinerator regulations, and is also appro-
priate for sampling sewage sludge incinerators.
j The metals train contains special solutions in the impingers to
collect volatile metals. A glass probe tip is used. Full instructions on the
sampjling apparatus, sampling procedure, recovery of the samples, analysis, and
quality assurance/quality control associated with the metals train is provided
in Appendix A.
i
j As a special note, sampling specifically for hexavalent chromium (as
opposed to trivalent or total chromium) presents several problems. These
problems are the stability of the sample and recovery efficiencies when
separating . low level samples. Both oxidizing and reducing materials may
affect the stability of the samples and produce errors in the determination.
At this time, EPA has a first draft of a procedure for collecting and
analyzing chromium(VI) stack samples. This is included in Appendix C.
27
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3. QA/QC for Metals Determinations in Stack Samples:
I As noted previously, the "POTW Sludge Sampling
Guidance" (EPA, 1989c) recommends a QA plan for sludge
analysis.
and Analysis
sampling and
The EPA also recommends a QA plan for demonstration tests at
hazardous waste incinerators (EPA, 1990). Any demonstration test involving
stack sampling is a complex and expensive experiment; a QA plan is recommended
to ensure that the field sampling and laboratory analysis will provide data of
'sufficient quality for regulatory decision making. Guidance on preparing a QA
planlfor a demonstration test can be found in EPA (1990).
i
i
i a. Method design: One of the biggest difficulties in metals
determinations in stack samples is lack of. a clear target concentration. The
draft method requires specific adaptations of the procedures in order to
I
obtain various detection limits. Using the equations in the proposed rule,
the critical removal efficiency can be calculated given the known sludge metal
input. This critical removal efficiency and the sludge metal input can then
be used to calculate the stack gas concentration and resulting sample concen-
tration for analysis. To assure reliable quantisation of the analyte in the
stack gas, the sample concentration at the critical level should be at least
five) to ten times higher than the detection limit specified for the method.
i i
! b. Determination of precision and accuracy: The analysis for
metals in stack gas should be accompanied by determination of the precision
and accuracy of the measurement system. Various procedures are discussed in
EPA (1990). Precision and accuracy are determined using the QA/QC procedures
in the associated methods, plus additional analysis of two sets of metal sam-
pling train components fortified at the critical concentration level and pre-
pared and analyzed along with the stack gas sampling train components.
Accuracy is measured as percent recovery of fortified analyte, and precision
is measured as the percent range of the found analyte in each of the two sets
of sampling train components.
i c. Data reporting: Data reported for stack gas samples
should be calculated according to the methods. In addition, data reported for
the removal efficiency should be uncorrected for any background levels found
28
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in blanks. If significant levels are found in blanks, stack gas data should
be corrected only if sufficient statistical justification is given. Any
removal efficiency reported from blank-corrected data should also be reported
uncofrected for comparison.
i
;D. DISPERSION MODELING
i
i
! In broad terms, an atmospheric dispersion model provides a
relatively inexpensive means of predicting the impact that mass emissions from
a gijven source have on ambient air concentrations experienced at locations
surrpunding the source. Dispersion models have a long history of application
to criteria .pollutant [e.g., particulate, sulfur oxides (S02)] air quality
problems. For criteria pollutant analyses, the U.S. EPA has developed a set
of approved models and has a well established set of procedures to address
issues such as:
selection of an appropriate model given site location relative to
surrounding topography and land use;
meteorological data requirements; and
source data requirements
I Although there are no directly comparable procedures that are
specific to modeling metals emissions from sewage sludge incinerators, a set
of modeling recommendations has been prepared for a similar source—hazardous
waste incinerators. These recommendations borrow extensively from the
I
criteria pollutant modeling procedures.
I
i
! As an initial step in performing a dispersion analysis for a sewage
sludge incinerator, it is recommended that the applicant become familiar with
the information contained in the documents given below.
29
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j • Guideline on Air Quality Models (Revised), 1986, EPA-450/2-78-027R
• from the U.S. EPA Office of Air Quality Planning and Standards.
I This document is available from the National Technical Information
j Service (NTIS) as PB86-245248 and is the criteria pollutant modeling
guidance cited above.
j
i • Workbook of Atmospheric Dispersion Estimates, 1970, by
| D. B. Turner. This document is available from NTIS as PB191482.
i This document provides a very readable introduction to the
i
; fundamentals of Gaussian dispersion models.
i The actual dispersion model programs (i.e., the computer source code
or ^executable versions) can be obtained from at least two sources. For
example, one can purchase a specific model from a commercial software
vendor. There are many model vendors and one can obtain names and telephone
numbers for several vendors by looking at the advertisements given in the
Professional Services Directory of any recent issue of the Journal of the Air
and i Waste Management Association. Alternatively, one aan obtain the most
recent version of a model by accessing the U.S. EPA's computerized bulletin
board system (BBS) maintained by the Support Center for Regulatory Air Models
(SCIJIAM). For information regarding the SCRAM BBS one should write to the
following address:
i
; Support Center for Regulatory Air Models
i SRAB (MD 14)
j U.S. Environmental Protection Agency
I Research Triangle Park, NC 27711
! In many instances the Industrial Source Complex Long Term model
(ISCLT) will be the appropriate model for estimating the impact of emissions
from sewage sludge incinerators. This model is used very extensively in
regulatory applications. It is generally considered to be applicable unless
the; topography in the area immediately surrounding the facility (0.5 km)
consists of locations where the elevation exceeds the physical height of the
incjinerator stack. In this case it probably would be necessary to use what
30
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are [commonly referred to as complex terrain models. These models include
COMPLEXI and LON6Z. Note that atmospheric dispersion in complex terrain is an
ongoing research area and that there are still many questions involved in
applying and interpreting the results obtained by use of the COMPLEXI and
LONGZ models.
III.I REVIEWING AND INTERPRETING TEST RESULTS
i ' i
i
| This chapter serves two primary purposes. Frirst, it provides
descriptive advice to control agency permit writers who are reviewing and
interpreting test results from sewage sludge sampling and analysis, data from
process monitoring instrumentation, and the results from stack sampling and
analysis of emissions from sewage sludge incinerators. Secondly, this chapter
summarizes typical reporting requirements for the testing of sewage sludge
incinerators and, thus, provides guidance to owner/operators in providing a
complete test report to the control agency.
i
In general, the owner/operator must provide in a report to the
control agency adequate information (see Table III-l) to develop a permit in
resppnse to the requirements of the proposed rules for sewage sludge
incinerators. Minimum information includes a description of the incinerator
facility, operating conditions, and monitoring instrumentation; the results of
slud|ge sampling and analysis; full stack test results including documentation
of sludge sampling and analysis; data from the monitoring of key process
instruments; and complete documentation of stack sampling and analysis
resujlts/activities. A modeling report will be submitted to document the
dispjersion factor to be used for each site.
i
| The findings of the stack testing should be presented in a concise
and 'complete summary format, at the beginning of the test report. Test
results, QC results, and analysis system performance should be thoroughly
disc|ussed and documented in.the subsequent pages of the report. Sufficient
detajil is needed in the report to allow an agency reviewer to trace the calcu-
lations for all results from the summary presentation back to the raw data.
Resullts also are compared to the original test methods to verify that all
31
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TABLE III-l
SUMMARY OF MINIMUM DATA REQUIREMENTS FOR A SEWAGE SLUDGE
INCINERATOR PERMIT APPLICATION
Type of incinerator
Type of air pollution control
Sludge characteristics
* Concentration of Be, Hg, Pb, As, Cd, Cr, and Ni
Details of adequate continuous process monitoring instrumentation
(including appropriate calibration and maintenance programs) for the
following:
* Sludge feed rate
* Temperature(s) (in specified locations)
* Oxygen in exit gas
* Total hydrocarbon in exit gas
* Air pollution control device indicator(s)
Results of stack testing program (see Table III-4)
Values for:
* Sludge feed rate (annual average, dry basis, daily rate)
* Stack parameters such as stack height exit diameter, exit
temperature, exit velocity, etc.
* Dispersion factor including the EPA approval of dispersion modeling
report
Details of program to meet requirements for record keeping, reporting,
and sludge monitoring
32
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phas|es of the sampling, monitoring, and analysis activities were carried out
in accordance with the methods. Requirements are discussed in more detail in
the jfoilowing sections.
I A. SEWAGE SLUDGE SAMPLING AND ANALYSIS RESULTS
I A report of the results of the sewage sludge sampling and analysis
is essentially a summary of the test results and documentation of the various
sampling and analysis activities and requirements as discussed in Chapter II
and iin the references (EPA, 1989c; 1986). A summary of critical issues for
sewage sludge sampling and analysis is listed in Table III-2; the failure to
document an adequate response to any of the issues on the list may justify
issuance of deficiency comments or potentially the rejection of the results by
theicontrol agency as incomplete.
1
I Minimum required sludge data will be based ideally on long-term test
data. In addition, data must be provided for the sludge samples collected
during the stack tests; these data will be correlated with stack emissions
data to calculate facility-specific control efficiency values for regulated
toxic metals.
I Minimum required test results for sewage sludge characterization
will include data for beryllium, mercury, lead, arsenic, cadmium, chromium,
and nickel.
1 B. PROCESS MONITORING RESULTS
j The control agency permit writer will evaluate the adequacy of
process monitoring instrumentation based upon specific requirements in the
proposed rules and the various design capabilities and practical limitations
of each instrument, as discussed in Chapter II. Table III-3 summarizes the
critical issues for the monitoring of the key operating parameters.
I
I As noted in Table III-l, monitored data for sludge feed rate must be
submitted in a permit application to provide the minimum data requirements for
determining permit conditions. In addition, the stack test report must
33
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I TABLE III-2
i
! CRITICAL ISSUES FOR SEWAGE SLUDGE SAMPLING AND ANALYSIS
i -
( • ,
justification for sampling and analysis strategy
Sampling frequency/number of samples
Sampling method and location
i
JGollection of equal volumes for each subsample making up composite
Duration and timing of sampling (timing is especially important during a
(stack sampling effort)
(Preparation of containers and equipment
i
jField compositing methods
i
Sample storage, preservation, holding time, and shipping
j
(Sample custody
i
Sample preparation methods
Analysis parameters and methods
I
(Preparation and analysis of standards
i
Analytical instrument operation/calibration curves
i
(Blanks (sampling/analysis)
i
(Determination of accuracy and precision
[Detection limits
Calculation of results
'Discussion of the fulfillment and attainment of quality assurance and
'quality control objectives
(Discussion of any sampling and analysis difficulties
34
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TABLE II1-3
CRITICAL ISSUES FOR MONITORED INDICATORS OF SEWAGE SLUDGE
INCINERATOR PERFORMANCE
: Monitoring of appropriate parameters
i Location and number of sensors
j Methods of monitoring
i
i
i Instrument calibration
! * Method
I * Frequency
; * Documentation
; * Calibration prior to stack sampling
Frequency of data readouts/records
! Correction of data (e.g., dry basis, oxygen correction) as required
! Other maintenance issues (availability of spare parts, etc.)
i Discussion of the fulfillment and attainment of quality assurance and
! quality control objectives
35
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include documentation of the monitored parameters during each stack sampling
run. Data to be reported and documented in the test report should include:
A summary table of each parameter indicating average, minimum,
and maximum values for each test run.
Printouts from a data logger or strip chart of the raw data
collected.
Documentation of instrument calibrations made prior to the
first test (or prior to each test run if applicable).
Documentation of calculations and factors used to adjust raw
data to final data (i.e., dry basis, oxygen correction for THC,
etc.).
C. RESULTS OF STACK SAMPLING AND ANALYSIS
The results of stack sampling and analysis are reported in a summary
tabl(e; detailed in a descriptive report of findings, methods/activities, and
problems; and fully documented via field sheets, raw data, etc., to allow a
i
thorough review of the requirements of the sampling and analysis methods. A
summary list of critical issues for testing metals emissions from sewage
sludge incinerators is provided in Table III-4; the failure to document an
adequate response to any of the issues on the list may justify the issuance of
Table III-3 deficiency comments or potentially the rejection of the results by
the jcontrol agency as incomplete.
IV. | APPROACH TO ESTABLISHING PERMIT LIMITS
i
This chapter describes how a permit writer will develop specific
penfiit limits for a sewage sludge incinerator based on the required informa-
tioi) submitted by the applicant. This decision process can also be used by a
permit applicant to preview possible permit conditions.
36
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TABLE II1-4
CRITICAL ISSUES FOR TESTING METALS EMISSIONS FROM
SEWAGE SLUDGE INCINERATORS
! Identification of sampling objectives and methods
|Location of sampling ports
Traverse points
;Absence of cyclonic flow verified
i
jEquipment calibration
•Stack gas velocity/flow rate calculation
;Gas analysis/calculation
I Field data sheets
'Isokinetic calculations
iProper temperatures maintained
Sampling rate/volume/time
|Mandatory leak checks performed with acceptable results
;Number of replicate runs per test condition
Cample recovery documentation
I Hand!ing/distribution of samples for analysis
Filter weight/moisture determination
I Sample storage, preservation, shipping, and holding time
iSample custody
jSample preparation methods
I Analysis methods
i
iPreparation and analysis of standards
•Analytical instrument operation/calibration curves
!Blanks (sampling/analysis)
[Determination of accuracy and precision
{Calculation of results (based upon input sludge characteristics)
Discussion of the fulfillment and attainment of quality assurance and
;quality control objectives
37
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-------
Many of the numerical permit limits are calculated using formulas
provided in the proposed rules (Federal Register, February 6, 1989). The
specjific formulas and factors are not repeated here since they are subject to
revision prior to promulgation. However, the following pages discuss how a
permit writer will use the calculations and submitted information to develop
specific permit conditions. Individual parameters are addressed in the
following sections. The use of assumed factors will allow an applicant to
estimate possible permit limitations.
jA. SLUDGE FEED RATE
j
j A major objective of the sewage sludge incinerator permitting pro-
gram is a risk-based limitation of inputs of beryllium, mercury, lead,
arsefiic, cadmium, chromium, and nickel to each incinerator. Limitations of
metajl inputs result in limitations of potential metal emissions to the atmo-
sphere.
The specific limits for each metal are based upon formulas contained
in tjie proposed rule that involve such factors as control efficiency and dis-
persion. Two major variables in each formula are the concentration of the
reguHated metal in the sewage sludge and the input rate of sludge to the
incinerator.
i
i
I Sludge feed rate will serve as the continuously monitored parameter;
a maximum value specified in the permit will serve as a limit to the input of
the most critical metal, i.e., the metal that requires the lowest sludge feed
rate! in the risk-based calculations described in the proposed rule. In
determining permit conditions, the concentration of each metal will be assumed
to bk a constant, based upon the average of accumulated sludge analysis data
for that metal. (Ideally, long-term information will be available for these
evalRations.) Allowable sludge feed rates are calculated for each metal using
the 'formulas; the lowest value is selected as an operating limit. A
continuing sludge analysis effort, required by the regulations, serves as a
long-term check of the validity of the average concentration values used to
determine maximum sludge feed rate.
38
-------
-------
; The individual steps of determining the maximum allowable sludge
feed! rate are as follows:
I
i
j 1. Gather the input information needed to use the formulas pro-
; vided in the proposed rules. Inputs include:
j - Average concentration of each regulcited metal in the
: sewage sludge (based upon long-term data collection)
( - Site-specific factors for dispersion and control effi-
: ciency obtained from site-specific studies/emission tests
Note that the calculations involve the combined feed of all
incinerators within the property line of the treatment works.
2. Solve the formulas for sewage sludge feed rate for each regu-
lated metal.
3. Select the lowest calculated sewage sludge feed rate (i.e. for
the metal that requires the lowest feed rate in the formulas),
convert this value from dry basis to wet basis (based on
historic moisture data) and compare with the design (or
manufacturers recommended) maximum sludge feed rate of each
incinerator.
4. Select the smaller value (i.e. the lowest calculated rate or
design maximum) as the permitted maximum feed rate. The rate
should be expressed on a wet basis in the permit if monitored
by the facility on a wet basis. If the facility has more than
one incinerator, allocate allowable feed rates to individual
units so that the total feed rate (to all of the incinerators)
does not exceed the sludge feed limit for the entire site.
A limited example set of calculations involving two metals is
provided in Appendix D of this document.
39
-------
-------
! The permit will correlate the maximum allowable sewage sludge feed
rate! with average concentration values for each regulated toxic metal. Each
faciility is required to conduct a continuing characterization of sewage sludge
in the proposed rules; if the results of this characterization indicate a
trend in averaged sludge data requiring a 10% or greater decrease in the
maximum allowable sludge feed rate, the permit limit must be modified.
Likewise, a facility can request a permit modification if data trends indicate
a bajsis for increasing the allowable sludge rate by 10% or greater.
i
| An incinerator owner/operator, as a result of completing the above
exerjcise with preliminary or estimated information, may identify a need to
modify or replace air pollution control equipment in order to maximize the
allowable sludge feed rate limit.
I B. TEMPERATURE, OXYGEN, AND TOTAL HYDROCARBONS (THC)
j
|
! Limits for maximum temperature and maximum oxygen are based on the
conditions documented during the tests. The maximum temperature limit should
be njo more than 100°F higher than the average temperature demonstrated during
the tests. Likewise, the oxygen limit should be no more than 1% 02 higher
than; the average demonstrated during the test. Oxygen limits are expressed on
!
a dry basis. A technology-based limit for THC will be included in the
promulgated regulation.
! c.
AIR POLLUTION CONTROL LIMITS
j The selection and monitoring of selected indicators of air pollution
control was addressed in Chapter II. Permit limits for the indicators
i
selected by the permit writer should reflect design operating conditions
(i.ej., within design minimum/maximum ranges recommended by the manufacturer of
the ! control device) and the operating conditions documented during stack
testing. Permit limits for the indicator parameters should not be more than
;
20% jabove/below the average value demonstrated during the tests (e.g., a
minimum scrubber pressure drop of 16 in if the test avenige was 20 in or a
maximum flow rate of 120 gpm if the test average was 100 gpm.)
40
-------
-------
! D. DEVIATIONS FROM LIMITS
; Permit writers should identify general requirements related to
deviations from limits in each sewage sludge incinerator permit. Brief
excursions above/below the maximum/minimum limits for continuously limited
parameters are allowed if they do not cause the limit to be exceeded for more
than 60 min. A report must be submitted to the control agency whenever permit
limirts are exceeded more than 60 min.
i
; E. CALIBRATION AND MAINTENANCE OF MONITORING INSTRUMENTATION
; The permit should include requirements for the calibration and
maintenance of instrumentation used to continuously monitor permit-limited
parameters. Required calibration methods and the minimum frequency of
calibration should be clearly identified in each permit. The method should be
as specific as possible. Recommended minimum frequencies of calibration are
daily for oxygen monitors, daily or weekly for THC monitors, and every
6 months for sludge feed rate and air pollution control indicators.
' Permits should also identify the key steps of a preventative
maintenance program for the THC and oxygen monitors. The preventive
maintenance program typically is based on manufacturers' recommendations and
includes such items as:
1. Checking the integrity of probe and sample line and backflush-
ing as necessary.
2. Checking and maintaining the sample conditioning system, e.g.,
cleaning or replacing filters.
3. Cleaning optical lens (in situ monitors).
4. Checking operation of recorders and data loggers (e.g., replac-
ing pens, ink, charts, etc.).
41
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-------
i The preventive maintenance program should be established by the
facility and should identify daily, weekly, monthly, and annual maintenance
activities. The permit should require a maintenance log to document adherence
to the maintenance program.
|F. RECORD KEEPING
f
; Sewage sludge incineration facilities are required to maintain
detailed records to document compliance with regulations and permit condi-
tions. These records are important for compliance inspections conducted by
EPA land state agency staff. The required records can be reviewed by
inspectors to demonstrate recent and past operations at the facility. Permit
i
writers should be very specific in each permit in defining the following:
I
i
| • Which records must be maintained?
t
: • What is the content and format of the records?
; • What is the frequency of inputs to each type of records (con-
' tinuous, weekly, etc.)?
1 ' ' .
| • How are the records stored for ease of access?
In general, documentation to be maintained by the facility includes:
j
I • Records associated with continuously monitored operating param-
eters (e.g., strip charts, computerized logs,, operator logs).
| • Records associated with sludge characterization and the calcu-
| lation of allowable sludge feed rates.
i • Calibration and maintenance logs.
\ ;
i The content and format of each record should be defined in the
I
permit in sufficient detail to ensure that all needed information will be
42
-------
-------
available to inspectors. Records of calibrations should document date, cali-
bratjion method, initial reading, and final reading. The permit should clearly
identify the minimum frequency of inputs to records (i.e. continuous strip
charits or data logging every 60 seconds). Specific requirements for strip
charjts may include minimum chart speed and minimum labeling of date and time
(e.g1., daily manual labeling by the operator).
i
i
I All records should be stored for ease of access for inspections
(i.e., in one central location).
V. CONTINUING ENFORCEMENT OBJECTIVES
| After a permit is issued for a sewage sludge incinerator, the
control agency will evaluate the facility's continuing compliance with the
applicable regulations and permit conditions by reviewing submitted reports
i
and iconducting inspections.
r
| The basis for enforcement includes:
i
t • Records of sewage sludge characterization.
i
i
! • Records/observations of continuously monitored operating
conditions.
• Records/observation of monitoring instrumentation function.
The control agency will review submitted reports and on-site records
of continuing sewage sludge sampling and analysis to evaluate any variations
in metals concentrations that would impact the risk-based calculation of the
maximum allowable sludge feed rate.
i
i
Inspectors will observe instrument readouts and review records of
monitored parameters to determine compliance with operating permit limits and
reporting requirements. Observations of the function of monitoring instru-
ments and the review of calibration and maintenance records serve as a check
43
-------
-------
of the completeness and validity of readings and response to specific permit
requirements.
vi. ^REFERENCES
!A. PRIMARY REFERENCES
The following references were used to develop this; document:
U.S.!Environmental Protection Agency. 1979. Continuous air pollution source
imonitoring systems handbook. EPA 625/6-79-005. June 1979.
U.S.jEnvironmental Protection Agency. 1980. Interim guidelines and specifi-
jcations for quality assurance project plans, EPA/QAM-005/80, Office of
'Research and Development.
U.S. j Environmental Protection Agency. 1986. Test methods for evaluating
|sol id wastes. SW-846, Office of Solid Waste and Emergency Response,
Washington, DC. 3rd Edition. September 1986.
U.S.! Environmental Protection Agency. 1989a. Technical support document -
!incineration of sewage sludge. EPA Office of Water Regulations and
|Standards, Washington, DC, February 1989.
U.S. Environmental Protection Agency. 1989b. Hazardous waste incineration
measurement guidance manual. Prepared for the U.S. Environmental
|Protection Agency, Office of Solid Wastes, Washington, DC.
•EPA 625/6-89-021. June 1989.
U.S. Environmental Protection Agency. 1989c. POTW sludge sampling and
!analysis guidance document. Environmental Protection Agency, Washington,
i
iDC, Office of Water Programs. August 1989.
44
-------
-------
U.S. Environmental Protection Agency. 1989d. Operation and maintenance of
hospital medical waste incinerators. Prepared for the U.S. Environmental
Protection Agency, Research Triangle Park, NC. EPA-450/3-89-002. March
1989.
U.S. Environmental Protection Agency. 1989e. Proposed methods for
measurements of CO, 02, THC, HC1, and metals. Prepared for the U.S.
Environmental Protection Agency, Office of Solid Wastes, Washington,
DC. Environmental Protection Agencys Office of Solid Waste. November
1989.
U.S.! Environmental Protection Agency. 1990. Handbook on quality
I assurance/quality control procedures for hazardous waste incineration.
! Prepared for the U.S. Environmental Protection Agency, Cincinnati, OH.
i EPA-625/6-89/023, January 1990.
j
FedeV-al Register. 1989. Standards for the disposal of sewage sludge,
| proposed rule. U.S. Environmental Protection Agency, Washington, DC.
! February 6, 1989.
I
Midwjest Research Institute. 1986. Methods for continuous rate monitoring of
j nonliquid hazardous wastes to incinerations. Prepared for the U.S. Envi-
I ronmental Protection Agency, Region IV, Atlanta, GA. EPA Contract
! No. 68-01-7038, Work Assignment R04-01-73. October 1986.
i
Midwest Research Institute. 1989. THC monitor survey. Prepared for the U.S.
j Environmental Protection Agency, Office of Solid Wastes, Washington,
1 DC. Draft Final Report. June 1989.
i B. SECONDARY REFERENCES
, The following references may provide additional detailed information
on air pollution control devices and incineration:
45
-------
-------
Air Pollution Control Devices
U.S. 1Environmental Protection Agency. 1981. Inspection manual for evaluation
|of electrostatic precipitator performance. EPA-340/1-79-007. March
11981.
U.S. j Environmental Protection Agency. 1983. Wet scrubber inspection and
(evaluation manual. EPA-340/1-83-022. September 1983.
!
i
U.S. j Environmental Protection Agency. 1984. Fabric filter inspection and
ievaluation manual. EPA-340/1-84-002. February 1984.
U.S.iEnvironmental Protection Agency. 1985. Operation and maintenance manual
jfor electrostatic precipitators. EPA/625/1-85-017. September 1985.
i
t
U.S. Environmental Protection Agency. 1985. Flue gas desulfurization
iinspection and performance evaluation. EPA/625/1-85-019. October 1985.
U.S.) Environmental Protection Agency. 1987. Municipal waste combustion
!study - flue gas cleaning technology. EPA/530-SW-87-021d. June 1987.
i
I
U.S. Environmental Protection Agency. 1989. Hospital waste incinerator field
!inspection and source evaluation manual. EPA-340/1-89-001. February
11989.
Incineration
U.S.1 Environmental Protection Agency. 1989. Guidance on setting permit
I conditions and reporting trial burn results. EPA/625/6-89/019. January
11989.
Water Pollution Control Federation.
jOM-11. Alexandria, VA.
1988. Incineration manual of practice
46
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-------
APPENDIX A
DRAFT MULTIPLE METALS SAMPLING TRAIN PROCEDURE0
aThis method is a preliminary draft that has not been formally released by
EPA.
A-l
-------
-------
e.P*
i!-.--W re; at tn;* st^e oe
: Agena> pc'icy. It .» oemg
-or co— ment on its •"••-nic?'
anc n lirv
DRAFT 8/28/89
METHODOLOGY FOR THE DETERMINATION OF METALS EMISSIONS IN EXHAUST GASES
i FROM HAZARDOUS WASTE INCINERATION AND SIMILAR COMBUSTION PROCESSES
1. Applicability and Principle
1.1 Applicability. This method is applicable for the determination of
total;chromium (Cr), cadmium (Cd), arsenic (As), nickel (Ni), manganese (Mn),
beryllium (Be), copper (Cu), zinc (Zn), lead (Pb), selenium (S',e), phosphorus
(P), thallium (Tl), silver (Ag), antimony (Sb), barium (Ba), sind mercury (Kg)
emissions from hazardous waste incinerators and similar combusi'tion processes.
|
This method may also be used for the determination of particulate emissions
following the additional procedures described. Modifications to the sample'
recovery and analysis procedures described in this protocol for the purpose of
determining particulate emissions may potentially impact the front half mercury
determination.*
E • —
1.2 Principle. The stack sample is withdrawn isokinetically from the
source, with, particulate emissions collected in the probe and on a heated
filter and gaseous emissions collected in a series of chilled impingers
.containing a solution of dilute nitric acid in hydrogen peroxide in two
impingers, and acidic potassium permanganate solution in two (or one)
impingers. Sampling train components are recovered and digested in separate
frontiand back half fractions. Materials collected in the sampling train are
digested with acid solutions to dissolve inorganics and to remove organic
constituents that may create analytical interferences. Acid digestion is
performed using conventional Parr" Bomb or microwave digestion techniques. The
nitric acid and hydrogen peroxide impinger solution, the acidic potassium
permanganate impinger solution, and the probe rinse and digested filter
solutions are analyzed for mercury by cold vapor atomic absorption spectroscopy
(CVAAS). Except for the permanganate solution, the remainder of the sampling
*Field tests to date have shown that of the total amount of mercury measured
by the method, only 0 to <2% was measured in the front half. Therefore, it is
tentatively concluded, based on the above data, that particulate emissions may
be measured by this train, without significantly altering the; mercury results."'
*>c:urtr«nt * a .preliminary drift
H\n°f b*en fc"1""* refeasad by EPA
«e» should not at thlc staS«i D, construe
» rrnt Agenay policy, it I* b»mg
tor comment on its tec
) ana p-jJcy Jmpllaition*.
c-
-------
-------
train catches are analyzed for Cr, Cd, Ni, Mn, Be, Cu, Zn, Pb, Se, P, Tl, Ag,
Sb, Ba, and As by inductively coupled argon plasma emission spectroscopy (ICAP)
or atomic absorption spectroscopy (AAS). Graphite furnace atomic absorption
spectijoscopy (GFAAS) is used for analysis of antimony, arsenic, cadmium, lead,
selenium, and thallium, if these elements require greater analytical
sensitivity than can be obtained by ICAP. Additionally, if desired, the tester
may us!e AAS for analyses of all metals if the resulting in-stack method
detection limits meet the goal of the testing program. For convenience,
i
aliqupts of each digested sample fraction can be combined proportionally for a
single analytical determination. The efficiency of the analytical procedure is
quantified by the analysis of spiked quality control samples containing each of
the target metals including actual sample matrix effects checks.
2. Range, Sensitivity, Precision, and Interferences
2il Range. For the analyses described in this methodology and for similar
analyses, the ICAP response is linear over several orders of magnitude. Sam-
ples containing metal concentrations in the nanograms per,milliliter (ng/ml) to
micrograms per milliliter (ug/ml) range in the analytical finish solution can
be analyzed using this technique. Samples containing greater than
approximately 50 ug/ml of chromium, lead, or arsenic should be diluted to that
level or lower for final analysis. Samples containing greater- than
approximately 20 ug/ml of cadmium should be diluted to that level before
analysis.
2i.2 Analytical Sensitivity. ICAP analytical detection limits for the
samplje solutions (based on SW-846. Method 6010) are approximately as follows:
Sb (3|2 ng/ml), As (53 ng/ml). Ba (2 ng/ml), Be (0.3 ng/ml). Get (4 ng/ml), Cr (7
ng/ml|), Cu (6 ng/ml), Pb (42 ng/ml). Mn (2 ng/ml), Ni (15 ng/ml), P (75 ng/ml).
Se (75 ng/ml), Ag (7 ng/ml), Ti (40 ng/ml), and Zn (2 ng/ml). The actual
method detection limits are sample dependent and may vary as 1;he sample matrix
may affect the limits. The analytical detection limits for analysis by direct
aspirjation AAS (based on SW-846, Method 7000) are approximately as follows: Sb
(200ing/ml), As (2 ng/ml), Ba (100 ng/ml). Be (5 ng/ml), Cd (5 ng/ml), Cr (50
ng/mi). Cu (20 ng/ml), Pb (100 ng/ml). Mn (10 ng/ml), Ni (40 ng/ml), Se (2
ng/ml), Ag (10 ng/ml), Tl (100 ng/ml), and Zn (5 ng/ml). The detection limit
for mercury by CVAAS is approximately 0.2 ng/ml. The use of GFAAS can give
added sensitivity compared to the use of direct aspiration AAS for the
'•;c fhuLld not
'• '••'•f=**':'. Agenoy- policy."
•«•-»•- 'or «.o,v,m«m o-,
cCv..-acv anu
,--;, ,..•«
-------
-------
following metals: Sb (3 ng/ml). As (1 ng/ml), Be (0.2 ng/ml), Cd (0.1 ng/ml).
Cr (1 |ng/ml), Pb (1 ng/ml), Se (2 ng/ml), and Tl (1 ng/ml).
Using (1) the procedures described in this method, (2) the analytical
detection limits described in the previous paragraph, (3) a volume of 300 ml
for the front half and 150 ml for the back half samples, and (4) a stack gas
sample volume of 1.25 m3 , the corresponding in-stack method detection limits
are presented in Table A-l and calculated as shown:
where: A = analytical detection limit, ug/ml.
B = volume of sample prior to aliquot for analysis, ml.
C = stack sample volume, dscm (dsm3).
D = in-stack detection limit, ug/m3.
Values in Table A-l are calculated for the front and back half and/or the total
train.
To ensure optimum sensitivity in obtaining the measurements, the
concentrations of target metals in the solutions are suggested to be at least
ten times the analytical detection limits. Under certain conditions, and with
greater care in the analytical procedure, this concentration can be as low as
approximately three times the analytical detection limit. In all cases,
repetitive analyses, method of standard additions (MSA), serial dilution, or
matrix spike addition should be used to establish the quality of the data.
Actual in-stack method detection limits will be determined based on actual
source sampling parameters and analytical results as described, above. If
required, the method in-stack detection limits can be made more sensitive than
those
following options:
shown in Table A-l for a specific test by using one or more of the
A normal 1-hour sampling run collects a stack gas sampling volume of
about 1.25 m3. If the sampling time is increased and 5 ffl3 are
collected, the in-stack method detection limits would be one fourth of
the values shown in Table A-l (this means that with this change, the
method is four times more sensitive than normal).
The in-stack detection limits assume that all of the sample is digested
(with exception of the aliquot for mercury) and the final liquid
volumes for analysis are 300 ml for the front half and 150 ml for the
ntr «•»:«;„...,. 13 (.
tas ry-t o*,.-, fa.-7
*™ th-^ nor at t
te a pr*2Imiftary draft
not been formally released by EPA
should not at this stage M construe
nt Aganaf policy, ft i» being
lor comment on Jts tacnnica*
and
represent
.s::y reused by
, ' cn-
-------
-------
TABLE A-l. IN-STACK METHOD DETECTION LIMITS (ug/m3)
FOR TRAIN FRACTIONS USING ICAP AND AAS
Metal
Front Half Back Halfj
Fraction 1 Fraction 2
Probe and Filter Impingers 1-3
Back Half2
Fraction 3
Impingers 4-5
Total Train
Antimbny
Arsenic
Barium
Beryllium
Cadmium
Chromium
Coppefr
Lead |
Manganese
Mercury
Nickel
Phosphorus
Selenium
Silveir
Thallium
Zinc i
7-7
12.7
0.5
0.07 (0.05V
(0.7)*
(0.3)*
1.0
1.7
1.4
10.1
0.5
(0.02}*
(0.2)*
(0.2)*
(0.2)*
»*
0.05
3.6
18
18 (0.5)*
1.7
9.6 (0.2)*
0.5
3.8 (0.4)*
6.4 (0.1)*
3
04 (0.03)*
5 (0.01)*
8 (0.1)*
7-
0 (0.1)*
2 (0.1)*
03**
8
0
0
0
0
0
5
0
0
1
9
9 (0.3)*
0.9
4.8 (0.1)*
0.3
11.5 (l.D*
19.1 (0.4)*
0.8
0.11 (0.08)*
1.5 (0.03)*
2.5 (0.3)*
0.03
2.
15.
0,
*»
(0.3)*
(0.3)*
0.11**
5.4
27
27 (0.8)*
2.6
14.4 (0.3)*
0.8
( )* Detection limit when analyzed by GFAAS.
** Detection limit when analyzed by CVAAS.
Actual-.-method in-stack detection limits will be determined based
pn actual source sampling parameters and analytical resul,ts as
described earlier in this section.
i back half sample. If the front half volume is reduced from 300 ml to
| 30 ml, the front half in-stack detection limits would be one tenth of
• the values shown above (ten times more sensitive). If the back half
i volume is reduced from 150 ml to 25 ml, the in-stack detection limits
j would be one sixth of the above values. Matrix effects checks are
| necessary on analyses of samples and typically are of greater signifi-
cance for samples that have been concentrated to less than the normal
; sample volume. A volume less than 25 ml may not allow resolubiliza-
j tion of the residue and may increase interference by other compounds.
o| When both of the above two improvements are used on one sample at the
I same time, the resultant improvements are multiplicative. For example,
| where stack gas volume is increased by a factor of five and the total
! liquid sample digested volume of both the front and back halves is
I reduced by factor of six, the in-stack method detection limit is
j reduced by a factor of thirty (the method is thirty times more
i sensitive).
! ^ •*» *xusn.nl t* • preliminary flr»n
n« noi b««n formally released by €fr-
j «na should net at this staga o« construes
i » reor«s»nt Agenoy policy/ It is being
: * »l«o tor comnmnt on its recnmc**
' accuracy «no ir-Hcy Implication*.
-------
-------
o! Conversely, reducing stack gas sample volume and increasing sample
j liquid volume will .increase limits. The front half arid back halfi
i samples (Fractions 1 and 2) can be combined prior to analysis. The
| resultant liquid volume (excluding Fraction 3. which must be analyzed
j separately) is recorded. Combining the sample as described does not
i allow determination (whether front or back half) of where in the train
: the sample was captured. The in-stack method detection limit then
i
becomes a single value for all metals except mercury, for which the
j contribution of Fraction 3 must be considered.
o1 The above discussion assumes no blank correction. Blank corrections
! are discussed later in this method.
2|.3 Precision. The precisions (relative standard deviation) for each
metali detected in a method development test at a sewage sludge incinerator, are
as follows: Sb (12.1%}, As (13-5?), Ba (20.6%), Cd (11.5%). Cr (11.2%), Cu
(11.5;%). Pb (11.6%), P (14.6%). Se (15.3%). Tl (12.3%), and Zn (11.8%). The
precijsion for nickel was 7-7% for another test conducted at a source simulator.
Beryllium, manganese and silver were not detected in the tests; however, based
on the analytical sensitivity of the ICAP for these metals, it is assumed that
their| precisions should be similar, to those for the other me tills, when detected
[ f
at similar levels.
I
2.4 Interferences. Iron can be a spectral interference during the
analysis of arsenic, chromium, and cadmium by ICAP. Aluminum can be a spectral
interference during the analysis of arsenic and lead by ICAP. Generally, these
interferences can be reduced by diluting the sample, but this increases the
method detection limit. Refer to EPA Method 6010 (SW-846) for details on
potential interferences for this method. For all GFAAS analyr.es, matrix
modifiers should be used to limit interferences, and standards! should be matrix
matched.
3. Apparatus
3.1 Sampling Train. A schematic of the sampling train isi shown in Figure
A-l. ; It is similar to the Method 5 train. The sampling train consists of the
following components.
3.1.1 Probe Nozzle (Probe Tip) and Borosilicate or Quarts: Glass Probe
Liner;. Same as Method 5. Sections 2.1.1 and 2.1.2. Glass nosizles are required
unless an alternate probe tip prevents the possibility of contamination or
docuriTent t* a pranrmrwry «r*r.
* Mas nor oeen formally released by EP*
s.id EhoLid net at thi* stage. t>e construe*
-o weseot Agen^r policy. It I* oesng
v-cuietea tor comment on «s t«cnnic»»
secufHCv «na tr-liey
-------
-------
~N» aicujr.'eni Is a prenmmary artr.
• nas not oeen formally released oy £P*
«:io should not at this staja oe ccnstr.jer
w represent Agen^r policy, ft is being
circulaiied tor comment on its technical
accuracy and ff-Jlcy ImpIicaUen*.
S
05
10
•8
"5
_o
.9-
o
.53
"53
I
I
.!>
u.
I
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-------
interference of the sample with its materials of construction. If a probe tip
other than glass is used, no correction of the stack sample test results can be
made because of the effect on the results by the probe tip.
3;. 1.2 Pitot Tube and Differential Pressure Gauge. Same as Method 2,
Sections 2.1 and 2.2. respectively.
3.1.3 Filter Holder. Glass, same as Method 5, Section 2.1.5, except that
a Teflon filter support must be used to replace the glass frit.
3.1.4 Filter Heating System. Same as Method 5, Section 2.1.6.
3-1.5 Condenser. The following system shall be used for the condensation
! -
and collection of gaseous metals and for determining the moisture content of
the stack gas. The condensing system should consist of four to six impingers
connected in series with leak-free ground glass fittings or other leak- free,
non-qontaminating fittings. The first impinger is optional and is recommended
as a iwater knockout trap for use during test conditions which require such a
trap.; The impingers to be used in the metals train are now described. When
the fjirst impinger is used as a water knockout, it shall be appropriately-sized
l
for an expected large moisture catch and constructed generally as described for
I
the first impinger in Method 5. Paragraph 2.1.7. The second impinger {or the
first HNOj/HjO-j impinger) shall also be as described for the first impinger in
Method 5. The third impinger (or the impinger used as the second -HNC^/HjOj
impiijiger) shall be the same as the Greenburg Smith impinger with the standard
tip described as the second impinger in Method 5t Paragraph 2.1.7. All other
impingers used in the metals train are the same as the second impinger (the
first HNOj/HjOj impinger) previously described in this paragraph. In summary,
the first impinger should be empty, the second and third shall contain known
quantities of a nitric acid/hydrogen peroxide solution (Section 4.2.1), the
fourth (and fifth, if required) shall contain a known quantity of acidic
potassium permanganate solution (Section 4.2.2), and the last impinger shall
contain a known quantity of silica gel or equivalent desiccant. A thermometer
capable of measuring to within 1°C (2°F) shall be placed at the outlet of the
last '} impinger. When the water knockout impinger is not needed, it is removed
from j the train and the other impingers remain the same. If mercury analysis is
not needed, the potassium permanganate impingers are removed.
3-1.6 Metering System, Barometer, and Gas Density Determination
Equipment. Same as Method 5, Sections 2.1.8 through 2.1.10, respectively.
* h*s net been formally released Sy EP*
*rw should not at till* SU3» oe construec
« represent Agenoy policy. It i* oemg
circulated tor conynent on
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I
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311.7 Teflon Tape. For capping openings and sealing connections on the
sampling train.
! i
3^2 Sample Recovery. Same as Method 5, Sections 2.2.1 through 2.2.8
(Nonmetallic Probe-Liner and Probe-Nozzle Brushes, Wash Bottles, Sample
Storage Containers, Petri Dishes, Glass Graduated Cylinder, Plastic Storage
Containers, Funnel and Rubber Policeman, and Glass Funnel), respectively, with
the fallowing exceptions and additions:
3,2.1 Nonmetallic Probe-Liner and Probe-Nozzle Brushes. For quantitative
recovery of materials collected in the front half of the sampling train.
I
Description of acceptable all-Teflon component brushes to be included in EPA's
Emission Measurement Technical Information Center (EMTIC) files.
3:2.2 Sample Storage Containers. Glass bottles with Teflon-lined caps,
1000-'and 500-ml, shall be used for KMn04-containing samples eind blanks.
Polyethylene bottles may be used for other sample types.
3;.2.3 Graduated Cylinder. Glass or equivalent.
31.2.4 Funnel. Glass or equivalent.
3J.2.5 Labels. For identification of samples.
3J.2.6 Polypropylene Tweezers and/or Plastic Gloves. For recovery of the
filter from .the sampling train filter holder.
i
3!.3 Sample Preparation and Analysis. For the analysis, the following
equipment is needed:
i
3'.3-l Volumetric Flasks, 100 ml, 250 ml, and 1000 ml. For preparation of
standards and sample dilution.
!
3;.3-2 Graduated Cylinders. For preparation of reagents.
3'.3-3 Parr" Bombs or Microwave Pressure Relief Vessels with Capping
Station (CEM Corporation model or equivalent).
3J.3.4 Beakers and Watchglasses. 250 ml beakers for sample digestion with
watchglasses to cover the tops.
3|.3.5 Ring Stands and Clamps. For securing equipment such as filtration
apparatus.
3.3.6 Filter Funnels. For holding filter paper.
i
3.3.7 Whatman 5^1 Filter Paper (or equivalent). For filtration of
digested samples.
3.3.8 Disposable Pasteur Pipets and Bulbs.
$.3.9 Volumetric Pipets.
3.3.10 Analytical Balance. Accurate to within 0.1 mg.
! » oocum«ru « • .preliminary arift
1 • nas not keen formally released by EP*
j O j;w should not at thUi stag* ee construe
j TO represent Agenay policy, ft Is belnf
i orcuiated tor comment on its technlc*
i accuracy arc p-Wlcy Implication*.
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3. 3 -11 Microwave or Conventional Oven. For heating samples at fixed
power? levels or temperatures.
3J.3.12 Hot Plates.
3|.3-13 Atomic Absorption Spectrometer (AAS) . Equipped with a background
corrector.
i •
3.3.13.1 Graphite Furnace Attachment. With antimony, arsenic, cadmium,
lead.' selenium, thallium, and hollow cathode lamps (HCLs) or electrodeless
discharge lamps (EDLs) . Same as EPA Methods 7041 (antimony), 7060 (arsenic),
7131 I (cadmium), 7421 (lead), 7740 (selenium), and 7841 (thallium).
3.3.13.2 Cold Vapor Mercury Attachment. With -a mercury HCL or EDL. The
equipment needed for the cold vapor mercury attachment includes an air
1
recirjculation pump, a quartz cell, an aerator apparatus, and a heat lamp or
desiccator tube. The heat lamp should be capable of raising the ambient
tempejrature at the quartz cell by 10° C such that no condensation forms on the
wall ;of the quartz cell. Same as EPA Method 7*170.
3.3.14 Inductively Coupled Argon Plasma Spectrometer. With either a
direct or sequential reader and an alumina torch. Same as EPA Method 6010.
!
4 . Reagents
Unless .otherwise indicated, it is intended that all reagents conform to
the specifications established by the Committee on Analytical Reagents of the
American Chemical Society, where such specifications are available; otherwise,
use tihe best available grade.
4.1 Sampling. The reagents used in sampling are as follows:
4J.1.1 Filters. The filters shall contain less than 1.3 ug/in.2 of each of
the petals to be measured. Analytical results provided by filter manufacturers
are acceptable. However, if no such results are available, filter blanks must
be analyzed for each target metal prior to emission testing. Quartz fiber or
1
glasst fiber filters without organic binders shall be used. The filters should
exhibit at least 99-95 percent efficiency (<0.05 percent penetration) on 0.3
micron dioctyl phthalate smoke particles. The filter efficiency test shall be
conducted in accordance with ASTM Standard Method D2986-71 (incorporated by
reference) . For particulate determination in sources containing SO or SO
the fjilter material must be of a type that is unreactive to S02 or SO, , as
described in EPA Method 5- Quartz fiber filters meeting these requirements are
recomlmended.
c»c.«ir.r»t
l^K00! bee" *"TMHy released b/ Eft
«* shook, ,», .t thl« was, & construe.
» reores^t Ag.nsy policy, ft K being
TO, comment on fe tecrtnfc*
.no
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4.1.2 Water. To conform to ASTM Specification D1193-77, Type II
(incorporated by reference). Analyze the water for all target metals prior to
field use. All target metals should be less than 1 ng/ml.
4.1.3 Nitric Acid. Concentrated. Baker Ins tra- analyzed or equivalent.
4.1.4 Hydrochloric Acid. Concentrated. Baker Ins tra- analyzed or
h!re nof
*" formally reused ey
inn should not at thl* sia*» n»
* reo-esem Ajansj- policy? tTt8
«rcu»ted for conynent on its
accuracy ana
4.1.5 Hydrogen Peroxide, 30 Percent (V/V) .
I
4.1.6 Potassium Permanganate.
4 1 7 Stilfurie Acid Concentrated-
H..1.7 bull uric Acid, concentrated.
4.1.8 Silica Gel and Crushed Ice. Same as Method 5, Sections 3.1.2 and
3.1.4, respectively.
4.2 Pretest Preparation for Sampling Reagents.
i
4.2.1 Nitric Acid (HN03 } /Hydrogen Peroxide (HjC^) Absorbing Solution,
5 Percent HN03/10 Percent H.,02. Add 50 ml of concentrated HNQ3 and 333 ml of
30 percent HjOj to a 1000-ml volumetric flask or graduated cylinder containing
approximately 500 ml of water. Dilute to volume with water. The reagent shall
contain less than 2 ng/ml of each target metal.
4.2.2 Acidic Potassium Permanganate (KMn04 ) Absorbing Solution, 4 Percent
KMnO^ (W/V).. Prepare fresh daily. Dissolve 40 g of KMn04 in sufficient 10
percent HgSC^ to make 1 liter. Prepare and store in glass bottles to prevent
degradation. The reagent shall contain less than 2 ng/ml of Hg.
Precaution: To prevent autocatalytic decomposition of the permanganate
solution, filter the solution through Whatman 54l filter paper. Also, due to
reaction of the potassium permanganate with the acid, there may be pressure
buildup in the sample storage bottle; these bottles should not be fully filled
and should be vented both to relieve excess pressure and prev<»nt explosion due
to pressure buildup. Venting is highly recommended, but should not allow
contamination of the sample; a No. 70-72 hole drilled in the container cap and
Teflon liner has been used.
4.2.3 Nitric Acid, 0.1 N. Add 6.3 ml of concentrated HNO, (70 percent) to
E . -3
a graduated cylinder containing approximately 900 ml of water,. Dilute to 1000
ml with water. Mix well. The reagent shall contain less than 2 ng/ml of each
target metal.
jf.2.4 Hydrochloric Acid (HC1), 8 N. Add 690 ml of concentrated HC1 to a
j
graduated cylinder containing 250 ml of water. Dilute to 1000 ml with water.
Mix well. The reagent shall contain less than 2 ng/ml of Hg.
10
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4.J3 Glassware Cleaning Reagents.
4.3-1 Nitric Acid, Concentrated. Fisher ACS grade or equivalent.
4.3.2 Water. To conform to ASTM Specifications D1193-77, Type II.
i
4.J3.3 Nitric Acid, 10 Percent (V/V). Add 500 ml of concentrated HN03 to a
graduated cylinder containing approximately 4000 ml of water. Dilute to 5000
ml with water.
4.i4 Sample Digestion and Analysis Reagents.
4J4.1 Hydrochloric Acid, Concentrated.
4.J4.2 Hydrofluoric Acid, Concentrated.
' 4.4.3 Nitric Acid, Concentrated. Baker Instra-analyzed or equivalent.
4.|4.4 Nitric Acid, 10 Percent (V/V). Add 1QO ml of concentrated HN03 to
800 ml) of water. Dilute to 1000 ml with water. Mix well. Reagent shall
contain less than 2 ng/ml of each target metal.
4.J4.5 Nitric Acid, 5 Percent (V/V). Add 50 ml of concentrated HN03 to
800 ml| of water. Dilute to 1000 ml with water. Reagent shall contain less
than 2 ng/ml of each target metal.
4.J4.6 Water. To conform to ASTM Specifications D1193-77, Type II.
4.j4.7 Hydroxylamine Hydrochloride and Sodium Chloride Solution. See EPA
Method 7^70 for preparation.
4J4.8 Stannous Chloride.
4.14.9 Potassium Permanganate, 5 Percent (W/V).
4.J4.10 Sulfuric Acid, Concentrated.
4.J4.11 Nitric Acid, 50 Percent (V/V).
4.4.12 Potassium Persulfate, 5 Percent (W/V).
4.J4.13 Nickel Nitrate, Ni(N03)2- 6^0.
4 J4.14 Lanthanum Oxide, Laj 03.
4.-.4.15 AAS Grade Hg Standard, 1000 ug/ml.
4.14.16 AAS Grade Pb Standard, 1000 ug/ml.
4.J4.17 AAS Grade As Standard, 1000 ug/ml.
4.J4.18 AAS Grade Cd Standard, 1000 ug/ml.
4.J4.19 AAS Grade Cr Standard, 1000 ug/ml.
4.(4.20 AAS Grade Sb Standard, 1000 ug/ml.
4.J4.21 AAS Grade Ba Standard, 1000 ug/ml.
4.14.22 AAS Grade Be Standard, 1000 ug/ml.
4J4.23 AAS Grade Cu Standard, 1000 ug/ml.
4.J4.24 AAS Grade Mn Standard, 1000 ug/ml.
3 ».prenmtMry efraf*.
* nas not t*en faf.T.s'.ly released by EPA
i:irt Should net S\ thlf
•o "-i!-es=^j: A
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ena
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11
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feeurfAnt ft «.prallmfntiy
has not been formally r.iwi
i* *hoUJd not at thi, a,j. *
a ren/esant Agensy policy. ft I* oeirw
•9-cuiwen tor comment on its. t«=
-
414.25 AAS Grade Ni Standard, 1000 ug/ml.
4i4.26 AAS Grade P Standard, 1000 ug/ml.
4J4.27 AAS Grade Se Standard, 1000 ug/ml.
414.28 'AAS Grade Ag Standard, 1000 ug/ml.
4(4.29 AAS Grade Tl Standard, 1000 ug/ml.
4[4.30 AAS Grade Zn Standard, 1000 ug/ml.
4t4.31 AAS Grade Al Standard, 1000 ug/ml.
414.32 AAS Grade Fe Standard, 1000 ug/ml.
414.33 The metals standards may also be made from solid chemicals as
described in EPA Method 200.7. EPA Method 7470 or Standard Methods for the
Analysis of Water and Wastewater. 15th Edition, Method 303F should be referred
to for additional information on mercury standards.
4i4.34 Mercury Standards and Quality Control Samples. Prepare fresh
weekly a 10 ug/ml intermediate mercury standard by adding 5 ml of 1000 ug/ml
mercury stock solution to a 500 ml volumetric flask; dilute to 500 ml by first
adding 20 ml of 15 percent HN03 and then adding water. Prepare a working
mercury standard solution fresh daily: add 5 ml of the 10 ug/ml intermediate
standard to .a 250 ml volumetric flask and dilute to 250 ml with 5 ml of
4 percent KMn04, 5 ml of 15 percent HN03, and then water. At least six '
separate aliquots of the working mercury standard solution should be used to
prepare the standard curve. These aliquots should contain 0.0, 1.0, 2.0, 3.0,
4.0, and 5-0 ml of the working standard solution. Quality control samples
shoulik be prepared by making'"a separate 10 ug/ml standard and diluting until in
the r^nge of the calibration.
4|4.35 ICAP Standards and Quality Control Samples. Calibration standards
for ICAP analysis can be combined into four different mixed standard solutions
as shown below.
! MIXED STANDARD SOLUTIONS FOR ICAP ANALYSIS
Solution
Elements
I
II
III
IV
As, Be, Cd, Mn, Pb, Se, Zn
Ba, Cu, Fe
Al, Cr, Ni
Ag, P, Sb, Tl
Prepare these standards by combining and diluting the appropriate volumes of
the 1000 ug/ml solutions with 5 percent nitric acid. A minimum of one stan-
dard and a blank can be used to form each calibration curve. However, a
12
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separate quality control sample spiked with known amounts of the target metals
in quantities in the nidrange of the calibration curve should be prepared.
Suggested standard levels are 50 ug/ml for Al, 25 ug/ml for Cr and Pb, 15 ug/ml
for Fe, and 10 ug/ml for the remaining elements. Standards containing less
than jl ug/ml of metal should be prepared daily. Standards containing greater
than jl ug/ml of metal should be stable for a minimum of 1 to 2 weeks.
4J.4.36 Graphite Furnace AAS Standards for Antimony, Arsenic, Cadmium,
Lead, Selenium, and Thallium. Prepare a 10 ug/ml standard by adding 1 ml of
1000 ug/ml standard to a 100 ml volumetric flask. Dilute to 100 ml with 10
percent nitric acid. For graphite furnace AAS, the standards must be matrix
matched; e.g., if the samples contain 6 percent nitric acid and 4 percent
hydrofluoric acid, the standards should also be made up with 6 percent nitric
acid and 4 percent hydrofluoric acid. Prepare a 100 ng/ml-standard by adding
1 ml bf the 10 ug/ml standard to a 100 ml volumetric flask and dilute to 100 ml
with jthe appropriate matrix solution. Other standards should be prepared by
dilution of the 100 ng/ml standards. At least five standards should be used to
make up the standard curve. Suggested levels are 0, 10, 50, 75, and 100 ng/ml.
Quality control samples should be prepared by making a separate 10 ug/ml
standard and diluting until it is in the range of the samples, Standards
containing less than 1 ug/ml of metal should be prepared dailyi Standards •
containing greater than 1 ug/ml of metal should be stable for a minimum of 1 to
2 weeks.
4.4.37 Matrix Modifiers.
4|.4.37.1 Nickel Nitrate, 1 Percent (V/V). Dissolve 4.956 g of
NiCNO^j-SHjO in approximately 50 ml of water in a 100 ml volumetric flask.
Dilutie to 100 ml with water.
4J.4.37.2 Nickel Nitrate, One-tenth Percent (V/V). Dilutes 10 ml of 1 per-
cent nickel nitrate solution to 100 ml with water. Inject an equal amount of
sample and this modifier into the graphite furnace during AAS analysis for As.
/H4.37.3 Lanthanum. Dissolve 0.5864 g of La.,03 in 10 ml of concentrated
HNO,
and dilute to 100 ml with water. Inject an equal amount of sample and
this modifier into the graphite furnace during AAS analysis for Pb.
i
5. Procedure
5|1 Sampling. The complexity of this method is such that, to obtain reli-
able results, testers should be trained and experienced with the test procedures,
13
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5 .'1.1 Pretest Preparation. Follow the same general procedure given in
Method! 5, Section 4.1.1, except that, unless particulate emissions are to be
determined, the filter need not be desiccated or weighed. All sampling train
!
glassware should first be rinsed with hot tap water and then washed in hot
soapy water. Next, glassware should be rinsed three times with tap water,
followed by three additional rinses with water. All glassware should then be
soaked in a 10 percent (V/V) nitric acid solution for a minimum of 4 hours,
rinsed three times with water, rinsed a final time with acetone, and allowed
to ait; dry. All glassware openings where contamination can occur should be
covered until the sampling train is assembled, prior to sampling.
5.;1. 2 Preliminary Determinations. Same as Method 5» Section 4.1.2.
5 .'1-3 Preparation of Sampling Train. Follow the same general, procedures
given Jin Method -5, Section 4.1.3t except place 100 ml of the nitric
acid/Hydrogen peroxide solution (Section 4.2.1) in the two HNC3 /H^ impingers
(normally the second and third impingers), place 100 ml of the acidic potassium
permanganate solution (Section 4.2.2) in the fourth and fifth impinger, and
transfer approximately 200 to 300 g of preweighed silica gel from its container
I
to the last impinger. Alternatively, the silica gel may be weighed directly in
the impinger just prior to train assembly.
Several -options are available to the tester based on the siampling
conditions. The use of an empty first impinger can be eliminated if the
moistikre to be collected in the impingers is calculated or determined to be
less £han 150 ml. The tester shall include two impingers containing the
acidic potassium permanganate solution for the first test run, unless past
} '
testing experience at the same or similar sources has shown that only one is
necessary. The last permanganate impinger may be discarded if both
permanganate impingers have retained their original deep purple permanganate
color I A maximum of 200 ml in each permanganate impinger (and; a maximum of
I
three j permanganate impingers ) may be used, if necessary, to maintain the
desired color in the last permanganate impinger.
Retain for reagent blanks, 100 ml of the nitric acid/hydrcigen peroxide
solution and 100 ml of the acidic potassium permanganate solution. These
solutions should be labeled and treated as described in Secticin 7, Set up the
sampling train as shown in Figure A-l. If necessary to ensure leak- free
i
sampling train connections, Teflon tape should be used instead' of silicone
grease to prevent contamination. ^ ^^ ^ , ^^^ ^
* has not Men formally released by
t:w should nor at thl« sti>s» «« csnstruea
-o represent Agenojr policy, ft Is befng
.sirttuistea tor comment oit ttt tech»wc*
accuracy »ne p-l\cy implication*
-------
-------
Precaution; Extreme care should be taken to prevent contamination within
the train. Prevent the mercury collection reagent (acidic potassium
permanganate) from contacting any glassware of the train which is washed and
i
analyzed for Mn. Prevent hydrogen peroxide from mixing with the acidic
potassium permanganate.
5.1.4 Leak-Check Procedures. Follow the leak-check procedures given in
Method: 5, Section 4.1.4.1 (Pretest Leak-Check), Section 4.1.4.2 (Leak-Checks
During; the Sample Run), and Section 4.1.4.3 (Post-Test Leak-Checks).
5.1.5 Sampling Train Operation. Follow the procedures given in Method 5,
Section 4.1.5. For each run, record the data required on a'data sheet such as
the on^ shown in Figure 5~2 of Method 5.
5.1.6 Calculation of Percent Isokinetic. Same as Method ;>, Section 4.1.6.
i
5.2 Sample Recovery. Begin cleanup procedures as soon as the probe is
removed from the stack at the end of a sampling period.
The probe should be allowed to cool prior to sample recovery. When it can
be safely handled, wipe off all external particulate matter near the tip of
the prbbe nozzle and place a rinsed, non-contaminating cap over the probe
nozzle, to prevent losing or gaining particulate matter. Do not cap the probe
tip tightly'-while the sampling train is cooling. This normally causes a vacuum
to form in the filter holder, thus causing the undesired result of drawing
liquid! from the impingers into the filter.
Before moving the sampling train to the cleanup site, remove the probe from
the sampling 'train and cap the open outlet. Be careful not to lose any
condensate that might be present. Cap the filter inlet where the probe was
fastened. Remove the umbilical cord from the last impinger and cap the '
impinger. Cap off the filter holder outlet and impinger inlet„ Use non- .
contaminating caps, whether ground-glass stoppers, plastic cap«, serum caps,
or Teflon tape to close these openings.
Alternatively, the train can be disassembled before the probe and filter
holder;/oven are completely cooled, if this procedure is followed: Initially
disconnect the filter holder outlet/impinger inlet and loosely cap the open
ends. | Then disconnect the probe from the filter holder or cyclone inlet and
loosely cap the open ends. Cap the probe tip and remove the umbilical cord as
previously described.
Triansfer the probe and filter-impinger assembly to a cleanup area that is
clean iand protected from the wind and other potential causes of contamination
I
; 15 T?*
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or loss of sample. Inspect the train before and during disassembly and note
any abnormal conditions. The sample is recovered and treated as follows (see
schematic in Figure A-2) . Assure that all items necessary for recovery of the
sample1 do not contaminate it.
5.;2.1 Container No. 1 (Filter). Carefully remove the filter from the
i
filter holder and place it in its identified petri dish container. Acid-
washed polypropylene or Teflon coated tweezers or clean, disposable surgical
gloves rinsed with water should be used to handle the filters. If it is
necessary to fold the filter, make certain the particulate cake is inside the
fold. I Carefully transfer the filter and any particulate matter or filter
fibers; that adhere to the filter holder gasket to the petri dish by using a dry
(acid-j cleaned) nylon bristle brush. Do not use any metal-containing materials
when recovering this train. Seal the labeled petri dish.
5.J2.2 Container No. 2 (Acetone Rinse). Taking care to see that dust on
the outside of the probe or other exterior surfaces does not .get into the
sample;, quantitatively recover particulate matter and any condensate from the
probe pozzle, probe fitting, probe liner, and front half of the filter holder
by wasjhing these components' with 100 ml of acetone and placing the wash in a
glass (container. Note; The use of exactly 100 ml is necessary for the
subsequent blank correction procedures. Distilled water may be used instead of
acetone when approved by the Administrator and shall be used when specified by
the Administrator; in these cases, save a water blank and follow the
Administrator's directions on analysis. Perform the acetone rinses as follows:
Carefully remove the probe nozzle and clean the inside surface by rinsing with
aceton.e from a wash bottle and brushing with a nonmetallic brush. Brush until
the acetone rinse shows no visible particles, after which make a final rinse of
the iriside surface with acetone.
Brush and rinse the inside parts of the Swagelok fitting with acetone in a
similar way until no visible particles remain.
Rinse the probe liner with acetone by tilting and rotating the probe while
squirtjing acetone into its upper end so that all inside surfaces will be wetted
with acetone. Allow the acetone to drain from the lower end into the sample
container. A funnel may be used to aid in transferring liquid washings to the
container. Follow the acetone rinse with a nonmetallic probe brush. Hold the
probe 'in an inclined position, squirt acetone into the upper end as .the probe
brush |is being pushed with a twisting action through the probe; hold a sample
i 16 rh» oocun-.*™ t,
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container underneath the lower end of the probe, and catch any acetone and
partibulate matter which is brushed through the probe three times or more until
no visible particulate matter is carried out with the acetone or until none
remains in the probe liner on visual inspection. Rinse the brush with acetone,
and quantitatively collect these washings in the sample container. After the
brushing, make a final acetone rinse of the probe as described above.
lit is recommended that two people clean the probe to minimize sample
losseis. Between sampling runs, keep brushes clean and protected from
contamination.
CJlean the inside of the front half of the filter holder by rubbing the
surf apes with a nonmetallic nylon bristle brush and rinsing with acetone.
Rinsej each surface three times or more if needed to remove visible particulate.
Make & final rinse of the brush and filter holder. After all acetone washings
and particulate matter have been collected in the sample container, tighten the
lid oji the sample container so that acetone will not leak out when it is
shipped to the laboratory. Mark the height of the fluid level to determine
whether or not leakage occurred during transport. Label the container clearly
to identify its contents.
5J.2.3 .Container No. 3 (Probe Rinse). Rinse the probe liner, probe nozzle,
and fi-ont half of the filter holder thoroughly with 100 ml of 0.1 N nitric acid
and place the wash into a sample storage container. Note; The use of exactly
100 mf is necessary for the subsequent blank correction procedures. Perform
the rinses as described in Method 12, Section 5.2.2. Record the volume of the
combined rinse. Mark the height of the fluid level on the outside of the
storage container and use this mark to determine if leakage occurs during
transport. Seal the container and clearly label the contents. Finally, rinse
the nozzle, probe liner, and front half of the filter holder with water
followed by acetone and discard these rinses.
5:2.4 Container No. 4 (Impingers 1 through 3, Contents and Rinses). Due
to th^ large quantity of liquid involved, the tester may place the impinger
solutions in more than one container. Measure the liquid in the first three
impingers volumetrically to within 0.5 ml using a graduated cylinder. Record
the volume of liquid present. This information is required to calculate the
moisture content of the sampled flue gas. Clean each of the first three
impingers, the filter support, the back half of the filter housing, and
connecting glassware by thoroughly rinsing with 100 ml of 0.1 N nitric acid as
18
not been formally
at
an«
« '»
on
-------
-------
described in Method 12, Section 5-2.4. Note; The use of exactly 100 ml of 0.1
N nitjric acid rinse is necessary for the subsequent blank correction
procedures. Combine the rinses and impinger solutions, measure and record the
volume. Calculate the 0.1 N nitric acid rinse volume by difference. Mark the
heighjt of the fluid level on the outside of the container to determine if
leaka'ge occurs during transport. Seal the container and clearly label the
contents .
5;.2.5 Container No. 5 {Acidified Potassium Permanganate Solution and
Rinses, Impingers No. 4 & 5). Pour all the liquid from the permanganate
impingers (fourth and fifth, if two permanganate impingers ar« used) into a
graduated cylinder and measure the volume to within 0.5 ml. This information
is required to calculate the moisture content of the sampled flue gas. Using
100 ml total of the acidified potassium permanganate solution,, rinse the
permanganate impinger(s) and connecting glass pieces a minimum of three times.
j
Combine the rinses with the permanganate impinger solution. Finally, rinse the
permainganate impinger(s) and connecting glassware with 50 ml of 8 N HCT to
remove any residue. Note: The use of exactly 100 ml and 50 ml for the two
I
rinse|s is necessary for the subsequent blank correction procedures. Place the
combined rinses and impinger contents in a labeled glass storage bottle. Mark
the Weight of the fluid level on the outside of the bottle to determine if
leakajge occurs during transport. See the following note and the Precaution in
Paragraph 4.2.2 and properly seal the bottle and clearly label the contents.
Njote: Due to the potential reaction of the potassium permanganate with the
acid,,; there may be pressure buildup in the sample storage bottles. These
bottles should not be filled full and should be vented to relieve excess
pressure. Venting is highly recommended. A No. 70-?2 hole drilled in the
container cap and Teflon liner has been found to allow adequate venting without
loss of sample.
i
5J.2.6 Container No. 6 (Silica Gel). Note the color of the indicating
silicja gel to determine whether it has been completely spent and make a
notation of its condition. Transfer the silica gel from its impinger to its
original container and seal. The tester may use a funnel to pour the silica
gel and a rubber policeman to remove the silica gel from the impinger. The
small! amount of particles that may adhere to the impinger wall need not be
removed. Do not use water or other liquids to transfer the silica gel since
weighjt gained in the silica gel impinger is used for moisture calculations.
' 19 °
formally
*
po"cy-
tor
«n« p-Wlcy imprtaatton.
-------
-------
Alternatively, if a balance is available in the field, record the weight of
the s|pent silica gel (or silica gel plus impinger) to the nearest 0.5 g.
5;.2.7 Container No. 7 (Acetone Blank). Once during each field test, place
100 ml of the acetone used in the sample recovery process into a labeled
i
container for use in the front half field reagent blank. Seal the container.
5J.2.8 Container No. 8 (0.1 N Nitric Acid Blank). Once during each field
test,| place 200 inl of the 0.1 N nitric acid solution used in the sample
recovery process into a labeled container for use in the front half and back
half 'field reagent blanks. Seal the container.
5|.2.9 Container No. 9 (5% Nitric Acid/10% Hydrogen Peroxide Blank). Once
durinjg each field test, place 200 ml of the 5% nitric acid/lOtf hydrogen
peroxide solution used as the nitric acid impinger reagent into a labeled
container for use in the back half field reagent blank. Seal the container.
5|.2.10 Container No. 10 (Acidified Potassium Permanganate Blank). Once
durinjg each field test, place 300 ml of the acidified potassixua permanganate
solution used as the impinger solution and in the sample recovery process into
a labeled container for use in the back half field reagent blank for mercury
analysis. Seal the container.
N&te: This container should be vented, as described in Section 5.2.4, to
relieve excess pressure.
5;.2.11 Container No. 11 (8 N HC1 Blank). Once during each field test,
place| 50 ml of the 8 N hydrochloric acid used to rinse the acidified potassium
permanganate impingers into "a labeled container for use in the back half
reagent blank for mercury.
5J.2.12 Container No. 12 (Filter Blank). Once during each field test,
place! an unused filter from the same lot as the sampling filters in a labeled
petrij dish. Seal the petri dish. This will be used in the front half field
reagent blank.
5j.3 Sample Preparation. Note the level of the liquid in each of the
containers and determine if any sample was lost during shipment. If a
noticeable amount of leakage has occurred, either void the sample or use
methods, subject to the approval of the Administrator, to correct the final
results. A diagram illustrating sample preparation and analysis procedures for
each of the sample train components is shown in Figure A-3.
5J3-1 Container No. 1 (Filter). If particulatre emissions are "being
determined, then desiccate the filter and filter catch without heat and weigh to
20
-------
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a constant weight as described in Section 4.3 of Method 5. For analysis of
metals, divide the filter with its filter catch into portions containing
approximately 0.5 g each and place into the analyst's choice of either
individual microwave pressure relief vessels or Parr11 Bombs. Add 6 ml of
concentrated nitric acid and 4 ml of concentrated hydrofluoric acid to each
vessel. For microwave heating, microwave the sample vessels for approximately
12-15 minutes in intervals of 1 to 2 minutes at 600 Watts. For conventional
heating, heat the Parr Bombs at l40°C (285°F) for 6 hours. Then cool the
samples to room temperature and combine with the acid digested probe jinse as
required in Section 5-3-3, below.
Notes: 1. Suggested microwave heating times are approximate land are dependent
upon the number of samples being digested. Twelve to 15 minute
heating times have been found to be acceptable for simultaneous
digestion of up to 12 individual samples. Sufficient heating is
evidenced by sorbent reflux within the vessel.
2. If the sampling train uses an optional cyclone, the cyclone catch
should be prepared and digested using the same procedures described
for the filters and combined with the digested filter samples.
5.3.2 .-Container No. 2 (Acetone Rinse). Note the level of liquid in the
container and confirm on the analysis sheet whether or not leakage occurred
durinjg transport. If a noticeable amount of leakage has occurred, either void
the s|ample or use methods, subject to the approval of the Administrator, to
correct the final results. Measure the liquid in this container either
volumjetrically to +1 ml or gravimetrically to +0.5 g. Transfer the contents to
an aqid-cleaned tared 250-ml beaker and evaporate to dryness at ambient
temperature and pressure. If particulate emissions are being determined,
desiqcate for 24 hours without heat, weigh to a constant weight according to
the procedures described in Section 4.3 of Method 5, and report the results to
the riearest 0.1 mg. Resolubilize the residue with concentrated nitric acid and
combine the resultant sample including all liquid and any particulate matter
with 'Container No. 3 prior to beginning the following Section 5.3.3.
5.3-3 Container No. 3 (Probe Rinse). The pH of this sample shall be 2 or
lower!. If the pH is higher, the sample should be acidified with concentrated
nitric acid to pH 2. The sample should be rinsed into a beaker with water and
the beaker should be covered with a ribbed watchglass. The'sample volume should
I
be reduced to approximately 50 ml by heating on a hot plate at a temperature
i 22
m (• • preliminary «r»ft.
hw not b«en formally released by EPA
*nc ahould not ai this istas» Be construed
•ft r»pi*s«m Agensjr policy, ft Is oelng
•.u...,i»i*d tor comment on «s tacnn/c*
«cu.->cy *no p-llcy taruiticatloa*.
-------
-------
just below boiling. Inspect the sample for visible particulate matter, and
depending on the results of the inspection, perform one of the following. If no
partipulate matter is observed, combine the sample directly with the acid
digested portions of the filter prepared previously in Section 5.3.1. If
particulate matter is observed, digest the sample in microwave vessels or Parr*
Bombs|following the procedures described in Section 5-3.1; then combine the
resultant sample directly with the acid digested portions of the filter prepared
previously in Section 5-3.1. The resultant combined sample is referred to as
Fraction 1. Filter the combined solution of the acid digested filter and probe
rinse!samples using Whatman 54l filter paper. Dilute to 300 ml (or the
appropriate volume for the expected metals concentration) with water. Measure
and record the combined volume of the Fraction 1 solution to within 0.1 ml.
Quantitatively remove a 50 ml aliquot and label as Fraction IB,. Label the
remaining 250 ml portion as Fraction 1A. Fraction 1A is used for ICAP or AAS
analysis. Fraction IB is used for the determination of front half mercury.
5p4 Container No. 4 (Impingers 1-3). Measure and record the total vol-
ume of this sample (Fraction 2) to within 0.5 ml. Remove a 50 ml aliquot for
mercury analysis and label as Fraction 2B. Label the remaining portion of
Container No. 4 as Fraction.2A, The Fraction 2B aliquot should be prepared and
analysed as described in Section 5-4.3. Fraction 2A shall be ;pH 2 or lower.
If necessary, use concentrated nitric acid to lower Fraction 2A to pH 2. The
sample; should be rinsed into a beaker with water and the beaker should be
covered with a ribbed watchglass. The sample volume should be reduced to
approximately 20 ml by heating on a hot plate at a temperature just below
boiling. Then follow either of the digestion procedures described in Sections
5.3.4.1 and 5.3.4.2, below.
5.J3.4.1 Conventional Digestion Procedure. Add 30 ml of 50 percent nitric
acid and heat for 30 minutes on a hot plate to just below boiling. Add 10 ml of
3 percent hydrogen peroxide and heat for 10 more minutes. Add 50 ml of hot
water land heat the sample for an additional 20 minutes. Cool, filter the
sample,, and dilute to 150 ml (or the appropriate volume for the expected metals
concentrations) with water.
5-3-4.2 Microwave Digestion Procedure. Add 10 ml of 50 percent nitric
acid and heat for 6 minutes in intervals of 1 to 2 minutes at 600 Watts. Allow
the sample to cool. Add 10 ml of 3 percent hydrogen peroxide and-heat for 2
more minutes. Add 50 ml of hot water and heat for an. additional 5 minutes.
Ul™ *"" fo*m» '"''SHy
tnci *houu not at tW« 8«s. M C9n«tro*
•» represent Agenay policy, tt I* being
ra tor comment o:n its technical
ane j»WIcy fmplioatlaoa.
-------
-------
filter the sample, and dilute to 150 ml (or the appropriate volume for the
Cool,
expected metals concentrations) with water.
Note: All microwave heating times given are approximate and are dependent
upon the number of samples being digested at a time. Heating times as given
above have been found acceptable for simultaneous digestion of up to .12
individual samples. Sufficient heating is evidenced by solvent reflux within
the vessel. •
5.3.5 Container No. 5 (Impingers 4 & 5). Measure and record the total
volume of this sample to within 0.5 ml. This sample is referred to as Fraction
3. Follow the analysis procedures described in Section 5.4.3.
5-3-6 Container No. 6 (Silica Gel). Weigh the spent silica gel (or silica
gel plus impinger) to the nearest 0.5 g using a balance. (This step
may b|e conducted in the field.)
5(.4 Sample Analysis. For each sampling train, five individual samples are
generated for analysis. A schematic identifying each sample and the prescribed
sampie preparation and analysis scheme is shown in Figure A-3; The first two
samplies, labeled Fractions 1A and IB, consist of the digested samples from the
front! half of the train. Fraction 1A is for ICAP or AAS analysis as described
in Sections. 5.4.1 and/or 5.4.2. Fraction IB is for determination of front half
meroiry as described in Section 5.4.3.
The back half of the train was used to prepare the third through fifth
samples. The third and fourth samples, labeled Fractions 2A and 2B, contain
the digested samples from the H.,0 and HNO^Oj Impingers 1 through 3. Fraction
2A is for ICAP or AAS analysis. Fraction 2B will be analyzed for mercury.
The fifth sample, labeled Fraction 3, consists of the impinger contents and
rinsejs from the permanganate Impingers 4 and 5. This sample is analyzed for
merculry as described in Section 5-4.3. The total back half mercury catch is
determined from the sum of Fraction 2B and Fraction 3.
5;. 4.1 ICAP Analysis. Fraction 1A and Fraction 2A are ansilyzed by ICAP
using; EPA Method 200.7 (40 CFR 136, Appendix C). Calibrate the ICAP, and set up
an anjalysis program as described in Method 200.?. The quality control proce-
dures! described in Section 7.3.1 of this method shall be followed. Recommended
wavelengths for use in the analysis are listed below.
-K
fecutftint to a .ipranmimiy .
* fan not b*«n formally released fr/ CM
ana should not at this *taj». M eon«ru«e
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-------
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Element
Wavelength (run)
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Iron
Lead
Manganese
Nickel
Selenium
Silver
Thallium
Zinc
308.215
206.833
193.696
455.403
313.042
226.502
267.716
324.754
259-940
220.353
257.610
231.604
196.026
328.068
190.864
213.856
docu-TTent la * preliminary draft
» h« not' been formally released
*nd should not at thU *t*se De construw
•c represent Agency policy, rt i* being
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*ccur<,cv ,1100 t> -)i«
The wajvelengths listed are recommended because of their sensitivity and overall
acceptance. Other wavelengths may be substituted if they can provide the
needed] sensitivity and are treated with the same corrective techniques for
spectrjal interference.
Initially, analyze all samples for the target metals plus iron and
aluminpn. If iron and aluminum are present in the sample, the sample may have
to be (diluted so that each of these elements is at a concentration of less than
50 ppm: to reduce their spectral interferences on arsenic and lead.
Nojte: When analyzing samples in a hydrofluoric acid matrix, an alumina
torch jshould be used; since all front half samples will contain hydrofluoric
acid, iise an alumina torch. .
i
5.4.2 AAS by Direct Aspiration and/or Graphite Furnace. If analysis of
metalsj in Fraction 1A and Fraction 2A using graphite furnace or1 direct
aspiration AAS is desired, Table A-2 should be used to determine which
1
techniques and methods should be applied for each target uetal. Table A-2
should! also be consulted to determine possible interferences and techniques to
be followed for their minimization. Calibrate the instrument according to
Sectiop 6.3 and follow the quality control procedures specified in Section
7.3.2.|
5.4.3 Cold Vapor AAS Mercury Analysis. Fraction IB, Fraction 2B, and
Fraction 3 should be analyzed for mercury using cold vapor atomic absorption
spectroscopy following the method outlined in EPA Method 7470 or in Standard
Methods for Water and Wastewater Analysis. 15th Edition, Method 303P. Set up
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en
rn
CO
r>j
cr.
Rr
< h , C b
•H -H -rt fci i-(
a a. a 3 a
co co tn tu 03
< < <
o
03
g
1
3
ffl
03
-U
-------
-------
the calibration curve as described in Section 7-3 of Method 303F. Add
approximately 5 ml of each sample to BOD bottles. Record the amount of sample
added. The amount used is dependent upon the expected levels of mercury.
Dilute to approximately 120 ml with mercury- free water. Add approximately 15
ml of 5 percent potassium permanganate solution to the Fraction 2B and Fraction
3 samples. Add 5 percent potassium permanganate solution to the Fraction IB
sample as needed to produce a purple solution lasting at least 15 minutes. A
minimum of 25 ml is suggested. Add 5 ml of 50 percent nitric acid, 5 ml of
concentrated sulfuric acid, and 9 ml of 5 percent potassium persulfate to each
sample and each standard. Digest the solution in the capped BOD bottle at 95°C
(205°jF) in a convection oven or water bath for 2 hours. Cool, Add 5 al of
hydroxylamine hydrochloride solution and mix the sample. Then add 7 ml of
stannous chloride to each sample and analyze immediately.
i
6. Calibration • ^
i
Maintain a laboratory log of all calibrations.
6,.l Sampling Train Calibration. Calibrate the sampling train components
according to the indicated sections of Method 5: Probe Nozzl« (Section 5.1);
Pitot| Tube (Section 5-2); Metering System (Section 5.3); Prob« Heater (Section
5.4);| Temperature Gauges (Section 5.5); Leak-Check of the Metesring System
(Section 5-6); and Barometer (Section 5.7).
6:. 2 Inductively Coupled Argon Plasma Spectrometer Calibration. Prepare
standards as outlined in Section 4.4. Profile and calibrate the instrument
according to the instrument manufacturer's recommended procedures using the
above: standards. The instrument calibration should be checked once per hour.
If thje instrument does not reproduce the concentrations of the standard within
10 percent, the complete calibration procedures should be performed.
6j. 3 Atomic Absorption Spectrometer - Direct Aspiration, Graphite Furnace
and' Cold Vapor Mercury Analyses. Prepare the standards as outlined in Section
4.4. : Calibrate the spectrometer using these prepared standards. Calibration
procedures are also outlined in the EPA methods referred to in, Table A-2 and in
Standard Methods for Water and Wastewater. 15th Edition, Method 303F (for
mercury) . Each standard curve should be run in duplicate and the mean values
used jto calculate the calibration line. The instrument should be recalibrated
approximately once every 10 to 12 samples.
*
20
has not been formally released t>y
i *h°UW not 8t 0>U 8taS* »• con
» represent Agenaj- policy. tt to bejng
circulated for comroitnt on Jts
ana p^Jcy ImpllcaUeaa
-------
-------
7. Quality Control
7j.l Sampling. Field Reagent Blanks. The blank samples in Container
Numbers 7 through 12 produced previously in Sections 5.2.7 through 5.2.11,
respectively, shall be processed, digested, and analyzed as follows. Digest
and pjrocess Container No. 12 contents per Section 5-3-1. Container No. 7 per
Section 5.3.2. and half of Container No. 8 per Section 5.3.3. This produces
Fraction Blank 1A and Fraction Blank IB from Fraction Blank 1. Combine the
remaining half of Container No. 8 with the contents of Container No. 9 and
digesjt and process the resultant volume per Section 5.3.4. This produces
Fraction Blank 2A and Fraction Blank 2B from Fraction Blank 2. Container No. 10
and Container No. 11 contents are Fraction Blank 3- Analyze Fraction Blank 1A
and Fraction Blank 2A per Section 5.4.1 and/or 5.4.2. Analyze Fraction Blank
IB, Fraction Blank 2B, and Fraction Blank 3 per Section 5.4'.3- The analysis of
Fraction Blank 1A produces the front half reagent blank correction values for
the metals except mercury; the analysis of Fraction Blank IB produces the front
half Reagent blank correct value for mercury. The analysis of Fraction Blank 2A
produpes the back half reagent blank correction values.for the metals except
mercury, while separate analysis of Fraction Blanks 2B and 3 produce the back
half j^eageot blank correction value for mercury.
7^2 An .attempt may be made to determine if the laboratory reagents used in
Section 5-3 caused contamination. They should be analyzed by the procedures in
Section 5.4. The Administrator will determine whether or not the laboratory
blank! reagent values can be used in the calculation of the stationary source
test results.
7j3 Quality Control Samples. The following quality control samples should
be analyzed.
7,3.1 ICAP Analysis. Follow the quality control shown in. Section 8 of
Methock 6010. For the purposes of a three run test series, these requirements
have Ipen modified to include the following: two instrument check standard
runs,jtwo calibration blank runs, one interference check sample at the
beginning of the analysis (must be within 25* or analyze by standard addition),
one quality control sample to check the accuracy of the calibration standards '
(must[be within 25* of calibration), and one duplicate analysis (must be within
5% of |average or repeat all analysis).
7.j3.2 Direct Aspiration and/or Graphite Furnace AAS Analysis for Antimony,
Arsenic, Barium, Beryllium, Cadmium, Copper, Chromium, Lead, Nickel,' Manganese,
I L*? "°.'*an *r™$}™™££
****** *>»<*. »t I, being
4»rcul»t«6 for convneni: *n its tocftnic*
accuracy »n« p-Rcy taipl!c«U*as,
-------
-------
Mercery, Phosphorus, Selenium, Silver, Thallium, and Zinc. All samples should
be analyzed in duplicate. Perform a matrix spike on one front half sample and
one b|ack half sample or one combined sample. If recoveries of less than 75
percent or greater than 125 percent are obtained for the matrix spike, analyze
eachjsample by the method of additions. A quality control sample should be
analyzed to check the accuracy of the calibration standards. The results must
be wijthin 10% or the calibration repeated.
7.3.3 Cold Vapor AAS Analysis for Mercury. All samples should be analyzed
in duplicate. A quality control sample should be analyzed to check the accuracy
of the calibration standards (within 10* or repeat calibration). Perform a
matrix spike on one sample from the nitric impinger portion (must be within 25*
or samples must be analyzed by the method of standard additions). Additional
information on quality control can be obtained from EPA Method 7470 or in
Standard Methods for Water and Wastewater. 15th Edition, Method 303F.
8. Calculations
8,1 Dry Gas Volume. Using the data from this test, calculate VB , the
dry g^s sample volume at standard conditions as outlined in Section 6.3 of
Methoii 5. .-",
8|.2 Volume of Water Vapor and Moisture Content. Using the data obtained
from pis test, calculate the volume of water vapor Vw(.ta) arid the moisture
content Bw. of the stack gas. Use Equations 5-2 and 5-3 of Method 5.
8^3 Stack Gas Velocity, Using the data from this test and Equation 2-9 of
Method 2, calculate the average stack gas velocity.
8^4 Metals (Except Mercury) in Source Sample.
8;4.1 Fraction 1A, Front Half, Metals (except Hg). Calculate the amount
of eaih metal collected in Fraction 1 of the sampling train using the following
equation:
r,*
«»«
M
T h
C. F_ V
»oln.i
Eq.
•If Fractions 1A and 2A are combined, proportional aliquots must be used
Appropriate changes must be made in Equations 1-3 to reflect this approach.
30
-------
-------
where:
M
fh
» o 1 n , 1
total mass of each metal (except Hg) collected in the
front half of the sampling train (Fraction 1), ug.
concentration of metal in sample Fraction 1A as read from the
standard curve (ug/ml).
dilution factor (Fd = the inverse of the fractional portion of the
concentrated sample in the solution actually used in the instrument to
produce the reading Ca. For example, when the dilution of Fraction 1A
is from 2 to 10 ml, Fd = 5).
total volume of digested sample solution (Fraction 1), ml.
8.ft.2 Fraction 2A, Back Half, Metals (except Hg). Calculate the amount of
each mjstal collected in Fraction 2 of the sampling train using the following
equatibn.
Eq. 2*
where:!
M^ = total mass of each metal (except Hg) collected in the back half
| of the sampling train (Fraction 2), ug.
C^ = concentration of metal in sample Fraction 2A, as read from the
i standard curve (ug/ml).
F. = aliquot factor, volume of Fraction 2 divided by volume of aliquot
Fraction 2A.
V^ * volume of digested sample analyzed (concentrated Fraction 2A), ml.
i
8.^.3 Total Train, Metals (except Hg). Calculate the toteO. amount of each
of the; quantified metals collected in the sampling train as follows:
Mt «
(M,, -
Eq. 3*
where::
M
Mt! * total mass of each metal (separately stated for each metal) collected
i in the sampling train, ug.
I = blank correction value for mass of metal detected in front half
field reagent blank, ug.
h'b! = blank correction value for mass of metal detected in back half
; field reagent blank, ug.
fhb
*If Friactions 1A and 2A are combined, proportional aliquots must be used.
Appropriate changes must be made in Equations 1-3 to reflect this approach.
b a .prenrain.fy
h*s not faesn formally
nm ,t
«na
comm.m en
-------
-------
Note; i If the measured blank value for the front half (mrhb) is in the range 0.0
to A ug [where A ug equals the value determined by multiplying 1.4 ug per square
inch {1.4 ug/in.2) times the actual area in square inches (in.2) of the filter
used in the emission sample], nfhb may be used to correct the emission sample
value (nfh); if nfhb exceeds A ug, the greater of the two following values
(either I. or II.) may be used:
I.j A ug, or
II. the lesser of (a) nfhb, or (b) 5 percent of mf h .
If the measured blank value for the back half (n^,^) is in the range 0.0 to 1
ug, Jnbhb may be used to correct the emission sample value (m^); if m,,,,,, exceeds,
1 ug, the greater of the two following values may be used: 1 ug or 5 percent of
8. 1 5 Mercury in Source Sample.
8.'5-l Fraction IB, Front Half, Hg. Calculate the amount of mercury
collected in the front half. Fraction 1, of .the sampling train using the
following equation:
.om.l
Eq. 4
where:
Hgfh - total mass of mercury collected in the front half of the sampling
| train (Fraction 1), ug.
(j^jj * quantity of mercury in analyzed sample, ug.
v«oitl.i ~ total volume of digested sample solution (Fraction 1), ml.
fs
= volume of Fraction IB analyzed, ml. See the following Note.
Note: JVF1B is the actual amount of Fraction IB analyzed. For example, if 1 ml
of Fraction IB were diluted to 100 ml to bring it into the proper analytical
rangei and 1 ml of the 100 ml dilution was analyzed, VflB would be 0.01.
8i5.2 Fraction 2B and Fraction 3, Back Half, Hg. Calculate the amount of
mercury collected in Fractions 2 and 3 using Equations 5 and 6, respectively.
Calculate the total amount of mercury collected in the back half of the sampling
train jus ing Equation 1.
Hg,
bh2
f IB
x V
• oln , 2
Eq. 5
ascument fa • .preliminary draft
* n« net been formally released fey
32
-------
-------
wherie:
Qbh2
vr2B
•oin.2
total mass °f mercury collected in Fraction 2,
quantity of mercury in analyzed sample, ug.
volume of Fraction 2B analyzed, ml (see Note in
Section 8.5-1).
total volume of Fraction 2, ml.
ug.
Hg,
*bh3
't2Z
x V
• o 1 n . 3
Eq. 6
where:
&bh3
V3
Vf3
'ioln. 3
total mass of mercury collected in Fraction 3, ug.
quantity of mercury in analyzed sample, ug.
volume of Fraction 3 analyzed, ml (see Note in
Section 8.5.1).
total volume of Fraction 3, ml.
*bh
Hg,
bh3
Eq. 7
where:
total mass of mercury collected in the back half of the sampling
train, ug.
i
8.5.3 Total Train Mercury Catch. Calculate the total amount of mercury
collected in the sampling train using Equation 8.
Mt "
- Hgfhb) + (Hgbh - Hgbhb)
Eq. 8
where:
Mt = total mass of mercury collected in the sampling train, ug.
= blank correction value for mass of mercury detected in front half
field reagent blank, ug.
- blank correction value for mass of mercury detected in back
, half field reagent blank, ug.
Note:; If the total of the measured blank values (Hgfhb + Hgbllb) is in the range
of 0 ;to 3 ug, then the total may be used to correct the emission sample value
(Hgfh; + Hgbh); if it exceeds 3 ug, the greater of the following two values may
be u^ed: 3 ug or 5 percent of the emission sample value (Hgfh + Hg ').
33 Hifr oocuritent (• • pi^jrminary a«*ft
ran not t*«n formally released fr/ £f*
i *ntf »houla net at thU staje t» oonstrueo
i » rtpfesem As«n«y pulley, tt !» being
circulated tor con\m«jt on Jts tacfw/c*
end (Mtay taiplleaUwot #.
-------
-------
8.16 Metal Concentration of Stack Gas. Calculate the cadmium, total
chromium, arsenic, nickel, manganese, beryllium, copper, lead, phosphorus,
thallium, silver, barium, zinc, selenium, antimony, and mercury concentrations
in the stack gas (dry basis, adjusted to standard conditions) as follows:
where:
t
s td)
8.
(Mt/VB(itd))
Eq.9
= concentration of each metal in the stack gas, mg/dscm.
= 10*3 mg/ug.
= total mass of each metal collected in the sampling train, ug.
= volume of gas sample as measured by the dry gas meter, corrected
to dry standard conditions, dscm.
• 7 Isokinetic Variation and Acceptable Results. Same as Method 5,
Sections 6.11 and 6.12, respectively.
9. Bibliography :
9-1 Method 303F in Standard Methods for the Examination of Water
Wastewater. 15th Edition, 1980. Available from the American Public Health
Association, 1015 18th Street N.W., Washington, D.C. 20036.
9.2 EPA Methods 6010, 7000. 704l, 7060, 7131, 7421, 7470, 7740, and, 7841,
Test Methods Tor Evaluating Solid Waste; Physical/Chemical Methods. SW-846,
Third lotion. September 1988. Office of Solid Waste and Emergency Response,
U. S. Environmental Protection Agency, Washington, D.C. 20460.
9-3 EPA Method 200.7, Code of Federal Regulations. Title 40. Part 136,
Appendix C. July 1, 1987.
9.4 EPA Methods 1 through 5, Code of Federal Regulations. Title 40, Part
60, Appendix A, July 1, 1987.
«*ocutff»nt \» » preliminary «r»it
* ha* net been formally ml««t«d by
ina should not at thfc «taj!» M comtruw*
* represent Agenojr policy. Jt I*
circulated tor comrnent on its
accuracy ano p^lcy Implication*
-------
-------
APPENDIX B
MEASUREMENT OF TOTAL HYDROCARBONS IN STACK GASES
B-l
-------
-------
Pt. 60, App. A, Meih. 25A
40 CFR Ch. I (7-1-39 Edition)
METHOD 25A—DETERMINATION OF TOTAL GAS-
EOUS ORGANIC CONCENTRATION USING A
FLAME IONIZATION ANALYZER
1. Applicability and Principle
1.1 Applicability. This method applies to
the measurement of total gaseous organic
concentration of vapors consisting primarily
of alkanes, alkenes, and/or arenes (aromatic
hydrocarbons). The concentration is ex-
pressed in terms of propane (or other appro-
priate organic calibration gas) or in terms of
carbon.
1.2 Principle. A gas sample is extracted
from the source through a heated sample
line, if necessary, and glass fiber filter to a
flame ionization analyzer (FIA). Results are
reported as volume concentration equiva-
lents of the calibration gas or as carbon
equivalents.
2. Definitions
2.1 Measurement System. The total
equipment required for the determination
of the gas concentration. The system con-
sists of the following major subsystems:
2.1.1 Sample Interface. That portion of
the system that is used for one or more of
the following: sample acquisition, sample
transportation, sample conditioning, or pro-
tection of the analyzer from the effects of
the stack effluent.
2.1.2 Organic Analyzer. That portion of
the system that senses organic concentra-
tion and generates an output proportional
to the gas concentration.
2.2 Span Value. The upper limit of a gas
concentration measurement range that is
specified for affected source categories in
the applicable part of the regulations. The
span value is established in the applicable
regulation and is usually 1.5 to 2.5 times the
applicable emission limit. If no span value is
provided, use a span value equivalent to 1.5
to 2.5 times the expected concentration. For
convenience, the span value should corre-
spond to 100 percent of the recorder scale.
2.3 Calibration Gas. A known concentra-
tion of a gas in an appropriate diluent gas.
2.4 Zero Drift. The difference in the
measurement system response to a zero
level calibration gas before and after a
stated period of operation during which no
unscheduled maintenance, repair, or adjust-
ment took place.
2.5 Calibration Drift. The difference in
the measurement system response to a mid-
level calibration gas before and after a
stated period of operation during which no
unscheduled maintenance, repair or adjust-
ment took place.
2.6 Response Time. The time interval
from a step change in pollutant concentra-
tion at the inlet to the emission measure-
ment system to the time at which 95 per-
cent of the corresponding final value is
reached as displayed on the recorder.
2.7 Calibration Error. The difference be-
tween the gas concentration indicated by
the measurement system and the known
concentration of the calibration gas.
3. Apparatus
A schematic of an acceptable measure-
ment system, is shown in Figurei 25A-1. The
essential components of the measurement
system are described below:
raoae
CALIBRATION
VALVE
*1A«C
I. Otipiiic ConcwtlNitiun MaaMitiaiium Sydtan.
942
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Environmental Protection Agency
3.1 Organic Concentration Analyzer. A
flame ionization analyzer (FIA) capable of
meeting or exceeding the specifications in
this method.
3.2 Sample Probe. Stainless steel, or
equivalent, three-hole rake type. Sample
holes shall be 4 mm in diameter or smaller
and located at 16;7, 50, and 83.3 percent of
the equivalent stack diameter. Alternative-
ly, a single opening probe may be used so
that a gas sample is collected from the cen-
trally located 10 percent area of the stack
cross-section.
3.3 Sample Line. Stainless steel or
Teflon* tubing to transport the sample gas
to the analyzer. The sample line should be
heated, if necessary, to prevent condensa-
tion in the line.
3.4 Calibration Valve Assembly. A three-
way valve assembly to direct the zero and
calibration gases to the analyzers is recom-
mended. Other methods, such as quick-con-
nect lines, to route calibration gas to the
analyzers are applicable.
3.5 Particulate Filter. An in-stack or an
out-of-stack glass fiber filter is recommend-
ed if exhaust gas particulate loading is sig-
nificant. An out-of-stack filter should be
heated to prevent any condensation.
3.6 Recorder. A strip-chart recorder,
analog computer, or digital recorder for re-
cording measurement data. The minimum
data recording requirement is one measure-
ment value per minute. Note: This method
is often applied in highly explosive areas.
Caution and care should be exercised in
choice of equipment and installation.
4. Calibration and Other Gases
Gases used for calibrations, fuel, and com-
bustion air (if required) are contained in
compressed gas cylinders. Preparation of
calibration gases shall be done according to
the procedure in Protocol No. 1, listed in
Reference 9.2. Additionally, the manufac-
turer of the cylinder should provide a rec-
ommended shelf life for each calibration gas
cylinder over which the concentration does
not change more than ±2 percent from the
certified value. For calibration gas values
°ot generally available (i.e., organics be-
tween 1 and 10 percent by volume), alterna-
tive methods for preparing calibration gas
fixtures, such as dilution systems, may be
used with prior approval of the Administra-
tor.
Calibration gases usually consist of pro-
pane in air or nitrogen and are determined
>n terms of the span value. Organic com-
pounds other than propane can be used fol-
lowing the above guidelines and making the
appropriate corrections for response factor.
„ "Mention of trade names or specific prod-
ucts does not constitute endorsement by the
-ental Protection Agency.
Pt. 60, App. A, Meth. 25A
4.1 Fuel. A 40 percent H,/60 percent He
or 40 percent H,/60 percent N, gas mixture
is recommended to avoid an oxygen syner-
gism effect that reportedly occurs when
oxygen concentration varies significantly
from a mean value.
4.2 Zero Gas. High purity ail- with less
than 0.1 parts- per million by volume (ppmv)
of organic material (propane or carbon
equivalent) or less than 0.1 percent of the
span value, whichever is greater.
4.3 Low-level Calibration Gas. ,An organic
calibration gas with a concentration equiva-
lent to 25 to 35 percent of the applicable
span value.
4.4 Mid-level Calibration Gas. ,An organic
calibration gas with a concentration equiva-
lent to 45 to 55 percent of the applicable
span value.
4.5 High-level Calibration Gas. An organ-
ic calibration gas with a concentration
equivalent to 80 to 90 percent of the appli-
cable span value.
5. Measurement System. Performance Speci-
fications
5.1 Zero Drift. Less than ±3 percent of
the span value.
5.2 Calibration Drift. Less than ±3 per-
cent of span value.
5.3 Calibration Error. Less than ±5 per-
cent of the calibration gas value.
6. Pretest Preparations
6.1 Selection of Sampling Site. The loca-
tion of the sampling site is generally speci-
fied by the applicable regulation or purpose
of the test: i.e., exhaust stack, inlet line, etc.
The sample port shall be located at least 1.5
meters or 2 equivalent diameters upstream
of the gas discharge to the atmosphere.
6.2 Location of Sample Probe. Install the
sample probe so that the probe is centrally
located in the stack, pipe, or duct and is
sealed tightly at the stack port connection.
6.3 Measurement System Preparation.
Prior to the emission test, assemble the
measurement system following the manu-
facturer's written instructions in preparing
the sample interface and the organic analyz-
er. Make the system operable.
FIA equipment can be calibrated for
almost any range of total organics concen-
trations. For high concentrations of organ-
ics (>1.0 percent by volume as propane)
modifications to most commonly available
analyzers are necessary. One accepted
method of equipment modification is to de-
crease the size of the sample to the analyzer
through the use of a smaller diameter
sample capillary. Direct and continuous
measurement of organic concentration is a
necessary consideration when determining
any modification design.
6.4 Calibration Error Test. Immediately
prior to the test series, (within 2 hours of
the start of the test) introduce zero gas and
943
-------
-------
Pt. 60, App. A, Meth. 25B
high-level calibration gas at the calibration
valve assembly. Adjust the analyzer output
to the appropriate levels, if necessary. Cal-
culate the predicted response for .the low-
level and mid-level gases based on a linear
response line between the zero and high-
level responses. Then introduce low-level
and mid-level calibration gases successively
to the measurement system. Record the an-
alyzer responses for low-level and mid-level
calibration gases and determine the differ-
ences between the measurement system re-
sponses and the predicted responses. These
differences must be less than 5 percent of
the respective calibration gas value. If not.
the measurement system is not acceptable
and must be replaced or repaired prior to
testing. No adjustments to the measurement
system shall be conducted after the calibra-
tion and before the drift check (Section 7.3).
If adjustments are necessary before the
completion of the test series, perform the
drift checks prior to the required adjust-
ments and repeat the calibration following
the adjustments. If multiple electronic
ranges are to be used, each additional range
must be checked with a mid-level calibration
gas to verify the multiplication factor.
6.5 Response Time Test. Introduce zero
gas into the measurement system at the
calibration valve assembly. When the
system output has stabilized, switch quickly
to the high-level calibration gas. Record the
time from the concentration change to the
measurement system response equivalent to
95 percent of the step change. Repeat the
test three times and average the results.
7. Emission Measurement Test Procedure
7.1 Organic Measurement. Begin sam-
pling at the start of the test period, record-
ing time and any required process informa-
tion as appropriate. In particular, note on
the recording chart periods of process inter-
ruption or cyclic operation.
7.2 Drift Determination. Immediately
following the completion of the test period
and hourly during the test period, reintro-
duce the zero and mid-level calibration
gases, one at a time, to the measurement
system at the calibration valve assembly.
(Make no adjustments to the measurement
system until after both the zero and calibra-
tion drift checks are made.) Record the ana-
lyzer response. If the drift values exceed the
specified limits, invalidate the test results
preceding the check and repeat the test fol-
lowing corrections to the measurement
system. Alternatively, recalibrate the test
measurement system as in Section 8.4 and
report the results using both sets, of calibra-
tion data (i.e., data determined prior to the
test period and data determined following
the test period).
8. Organic Concentration Calculations
Determine the average organic concentra-
tion in terms of ppmv as propane or other
40 CFR Ch. I (7-1-89 Edition)
calibration gas. The average shall be deter-
mined by the integration of the output re-
cording over the period specified in the ap-
plicable regulation.
If results are required in terms of ppmv as
carbon, adjust measured concentrations
using Equation 25A-1.
CC=K Cnm Eq. 25A-1
Where:
Ce=Organic concentration as csirbon, ppmv.
Cnai=Organic concentration as measured,
ppmv.
K=Carbon equivalent correction factor,
»K=2 for ethane.
K=3 for propane.
K=4 for butane.
K=Appropriate response factor for other
organic calibration gases.
9. Bibliography
9.1 Measurement of Volatile Organic
Compounds—Guideline Series. U.S. Envi-
ronmental Protection Agency. Research Tri-
angle Park, NC. Publication No. EPA-450/2-
78-041. June 1978. p. 46-54.
9.2 Traceability Protocol for Establishing
True Concentrations of Gases Used for Cali-
bration and Audits of Continuous Source
Emission Monitors (Protocol No. 1). U.S.
Environmental Protection Agency, Environ-
mental Monitoring and Support Laboratory.
Research Triangle Park, NC. June 1978.
9.3 Gasoline Vapor Emission Laboratory
Evaluation—Part 2. U.S. Enirironmental
Protection Agency, Office of Air Quality
Planning and Standards. Research Triangle
Park, NC. EMB Report No. 75-GAS-S.
August 1975.
METHOD 25B—DETERMINATION op TOTAL GAS-
EOUS ORGANIC CONCENTRATION USING A
NONDISPERSIVE INFRARED ANA1.Z2ES
1. Applicability and Principle
1.1 Applicability. This method applies to
the measurement of total, gaseous organic
concentration of vapors consisting primarily
of alkanes. (Other organic materials may be
measured using the general procedure in
this method, the appropriate calibration
gas. and an analyzer set to the appropriate
absorption band.) The concentration is ex-
pressed in terms of propane (or other appro-
priate organic calibration gas) or in terms of
carbon.
1.2 Principle. A gas sample is extracted
from the source through a heated sample
line, if necessary, and glass fiber filter to a
nondispersive infrared analyzer (NDIR)- Re-
suits are reported as volume concentration
equivalents of the calibration gas or as
carbon equivalents.
2. Definitions
944
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Environmental Protection Agency
The terms and definitions are the same as
for Method 25A.
3. Apparatus
The apparatus is the same as for Method
25A with the exception of the following:
3.1 Organic Concentration Analyzer. A
nondispersive infrared analyzer designed to
measure alkane organics and capable of
meeting or exceeding the specifications in
this method.
4. Calibration Gases
• The calibration gases are the same as re-
quired for Method 25A, Section 4. No fuel
gas is required for an NDIR.
5. Measurement System Performance Speci-
fications
5.1 Zero Drift. Less than ±3 percent of
the span value.
5.2 Calibration Drift. Less than ±3 per-
cent of the span value.
5.3 Calibration Error. Less than ±5 per-
cent of the calibration gas value.
6. Pretest Preparations
6.1 Selection of Sampling Site. Same as
in Method 25A, Section 6.1.
6.2 Location of Sample Probe. Same as in
Method 25A. Section 6.2.
6.3 Measurement System Preparation.
Prior to the emission test, assemble the
measurement system following the manu-
facturer's written instructions in preparing
the sample interface and the organic analyz-
er. Make the system operable.
6.4 Calibration Error Test. Same as in
Method 25A, Section 6.4.
6.5 Response Time Test Procedure. Same
as in Method 25A. Section 6.5.
7. Emission Measurement Test Procedure
Proceed with the emission measurement
immediately upon satisfactory completion
of the calibration.
7.1 Organic Measurement. Same as in
Method 25A, Section 7.1.
7.2 Drift Determination. Same as in
Method 25A, Section 7.2.
8- Organic Concentration Calculations
ifc£!«3ffi£5£ir the same •• ta
9. Bibliography
The bibliography is the same as in
Method 25A. Section 9.
27— DETEBJUNATIOlf OP VAPOR
TIGHTNESS OP GASOLINE DELIVERY TASK
USING PRESSURE- VACUUM TEST
!- -Applicability and Principle
ble fn^EPl!fabaity- This "ethod is applica-
«« lor the determination of vapor tightness
eouin,, 5as°lme delivery tank which is
<"iuipped with vapor collection equipment.
anDliort™011316- ^essure and vacuum are
spued alternately to the compartments of
Pt. 60, App. A, Meth. 27
a gasoline delivery tank and the change in
pressure or vacuum is recorded after a speci-
fied period of time.
2. Definitions and Nomenclature
2.1 Gasoline. Any petroleum distillate or
petroleum distillate/alcohol blend having a
Reid vapor pressure of 27.6 kilopascals or
greater which is used as a fuel, for internal
combustion engines.
2.2 Delivery Tank. Any container includ-
ing associated pipes and fittings, that is at-
tached to or forms a part of any truck, trail-
er, or railcar used for the transport of gaso-
line.
2.3 Compartment. A liquid-tight division
of a delivery tank.
2.4 Delivery Tank Vapor Collection
Equipment. Any piping, hoses, and devices
on the delivery tank used to collect and
route gasoline vapors either from the tank
to a bulk terminal vapor control system or
from a bulk plant or service station into the
tank.
2.5 Time Period of the Pressure or
Vacuum Test (t). The time period of the
test, as specified in the appropriate regula-
tipn, during which the change in pressure or
vacuum is monitored, in minutej!.
2.6 Initial Pressure (P,). The pressure ap-
plied to the delivery tank at the beginning
of the static pressure test, as specified in
the appropriate regulation, in mm H»O.
2.7 Initial Vacuum (7,). The vacuum ap-
plied to the delivery tank at the beginning
of the static vacuum test, as specified in the
appropriate regulation, in mm HaO. '
2.8 Allowable Pressure Change (Ap). The
allowable amount of decrease in pressure
during the static pressure test, within the
time period t, as specified in the appropriate
regulation, in mm H,O.
2.9 Allowable Vacuum Change (Ai7). The
allowable amount of decrease in vacuum
during the static vacuum test, within the
time period t, as specified in the appropriate
regulation, in mn^ H,O.
3. Apparatus
3.1 Pressure Source. Pump or compressed
gas cylinder of air or inert,gas sufficient to
pressurize the delivery tank to 500 mm H»O
above atmospheric pressure.
3.2 Regulator. Low pressure regulator for
controlling pressurization of the delivery
tank.
3.3 Vacuum Source. Vacuum pump capa-
ble of evacuating the delivery tank to 250
mm HjO below atmospheric pressure.
3.4 Pressure-Vacuum Supply Hose.
3.5 Manometer. Liquid manometer, or
equivalent instrument, capable of measur-
ing up to 500 mm H,O gauge pressure with
±2.5 mm H,O precision.
3.6 Pressure-Vacuum Relief Valves. The
test apparatus shall be equipped with an in-
line pressure-vacuum relief valve set to acti-
945
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APPENDIX C
DRAFT METHOD FOR DETERMINATION OF HEXAVALENT CHROMIUM
EMISSIONS FROM STATIONARY SOURCESa
aThis method is a preliminary draft that has not been formally released by
EPAi
C-l
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DRAFT - 08/13/90
METHOD Cr*6 - DETERMINATION OF HEXAVALENT CHROMIUM EMISSIONS
FROM STATIONARY SOURCES
1. Applicability and Principle
,1 Applicability, This method applies to the determination, of hexavalent
chromium1 (Cr*&) emissions from hazardous waste incinerators, municipal waste
combustdrs, and • sewage sludge incinerators. With the approval of the
Administrator, this method may also be used to measure total chromium. The
sampling! train, constructed of Teflon components, has only been evaluated at
temperatures less than 300°?. Trains constructed of other materials, for
testing Jat higher temperatures, are currently being evaluated.
1.2 'Principle. Per incinerators and combustors, the Cr** emissions are
collected isokinetically from the source. To eliminate the possibility of Cr*6
reduction between the nozzle and impinges-, the emission samples* are collected
with a ' recirculatory train where the impinger reagent i« continuously
recirculated to the nozzle. Recovery procedures include a post-sampling purge
and filirsttion. The iapinger train samples are analysed for Cr*° by an ion
chroma to'graph equipped with a post-column reactor and a visible wavelength
detector. The IC/PCR separates the Cr*6 as chromate (CrOt") from other
components in the sample matrices Chat may interfere with the Cr*6-specific
diphenylcarbazide reaction that occurs in the post-column reactor. To increase
sensitivity for trace levels of chromium, a preconcentration system is also
used in icon junction with, the IC/PCR.
2. Range. Sensitivity, Precision, and Interference
2.1 i Range. Employing a preconcentration procedure, the lower limit of the
detection range can bo extended to 16 nanograms per dry standard cubic meter
(ng/dscm) with a 3 dscm gas sample (0.1 ppb in solution). With sample
dilution, there is no upper limit.
i • .
2.2 i Sensitivity. A minimum detection limit of 8 ng/dscm with a 3 dson gas
sample £an be achieved by preconcentration {0.05 PPb in solution) .
i
2.3 (Precision. The precision of the IC/PCR with sample preconcentration is
5 to 10- percent. The overall precision for sewage sludge incinerators emitting
120 ng/idscm of CV6 and 3.5 ug/dscm of total chromium is 25* and 3% for Cr*6
and total chromium, respectively.
1
2.4 ! Interference. Components in the sample matrix may cause Cr*6 to
convert to tH.valent chromium (Cr*3) or cause Cr'3 to convert to Cr*6. A post-
sampling ni trcjgen purge and sample filtration .are included to eliminate many of
these iinterf crences. The chromatographic separation of Cr*& using ion
chroraatbgraphy reduces the potential for other metals to ..interfere, with the
- post-co|lumn reaction. For the IC/PCR analysis, only compounds that coelute
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with Cr'i^ and affect the diphenylcarbazide reaction will causa interference.
Periodic! analysis of deionized (DI) water blanks is used to demonstrate that
the anally tical system is essentially- free from contamination. Sample cross-
contaminjation that can occur when high-level and low- level samples or standards
are anal'yzad alternately is eliminated by thorough purging of the sample loop.
Purging j can easily be obtained by increasing the injection volume of the
samples 'to ten times the sias of the sample loop.
3. Apparatus
i
3.1 jSampling Train. Schematics of the recirculatory sampling trains
employed in this method are shown in Figures Cr*6-l and Cr**-2. The
rccircuiatory train is readily assembled from comnercia.lly available
components. All portions of the train in contact with the sample are either
glass, iquartz, Tygon, or Teflon, and are to be cleaned as per subsection
5.1.1. !
The ietering system is identical to that specified by Method 5 (see section
3.8.1); j the sampling train consists of the following components :,
{
3.1.1 Probe Nozzle. Glass or Teflon with a sharp, tapered leading edge.
The angjle of taper shall be <_3P° and the taper shall be. on the outside to
preserve a constant internal "diameter. The probe nozzle shall be of the
button-ljujok or elbow design, unless otherwise- specified by the Administrator.
A range of nozzle sizes suitable for isokinetic sampling should be
available, e.g., 0-32 to 1.2? cm (1/8 to 1/2 in.) -- or larger if higher volume
sample trains are used -- inside diameter (ID) nozzles in increments of 0.16 cm
( 1/16 "in.). Each nozzle shall be calibrated according to the procedures
outlined in Section 6.
3.1.2 Teflon Aspirator or Pump/Sprayer Assembly/ Teflon aspirator capable
of recilrculating absorbing reagent at 50 ml/min while operating at 0.75 cfm.
Alternatively, a pump/sprayer assembly may be used instead of the Teflon
aspiratbr. A Teflon union-T is connected behind the nozzle to provide the
absorbing reagent/sample gas mix; a peristaltic pump is used to recirculate the
absorbing reagent at a flow rate of at least 50 tnl/min. Teflon fittings.
Teflon iferrules, and Teflon nuts are used to connect a glass or Teflon nozzle,
recircukation line, and sample line to the Teflon aspirator or union-T. Tygon,
Of lex*- or other suitable inert tubing for use with peristaltic , pump.
3.1. i3 Teflon Sample Line. Teflon, 3/3" outside diameter (OD) and
inside ! diameter (ID), or 1/2" OD x 3/8" ID, of suitable length to connect
aspiratjor (or T-union) to first Teflon impinger.
3.1.14 Teflon Recirculation Line. Teflon, 1/4" O.D. and 1/8" I.D. , of
suitable length to connect first impinger to aspirator (or T-union) .
*NOTE:j Mention of trade names or specific product does not constitute
endors4nrent by the Enviornmental Protection Agency.
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.a
2
in
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e
i
o
£
it
to
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3-1.5 Teflon Impingers. Four Teflcn impingers; Teflon tubes and fittings,
such as i mads by Savillex" , can be used to construct impingers 2" diameter by
12" loiig, with vacuum-tight 3/8" O.D. Teflon compression fittings.
Altarnatlively, standard glass imping«rs that have been Teflon-lined, with
Teflon atsms and U-tubes, may be used. Inlet Fittings on impdlnger top to be
bored through to accept 3/8" O.D. tubing as impinger stem. The second and
third 3J8" OD Teflon szem has a 1/4" OD Teflon' tube, 2" long, inserted at its
end to duplicate the effects of the Greenburg-Smith impinger stem.. The first
impinger stem, should extend to 2" from impinger bottom, high enough in the
impinger reagent to prevent air from entering recirculating line;, the second'
and third impinger stecs should extend to.1/2" from impinger bottom. The first
impinge'r should" include a 1/4" O.D, Teflon compression fitting for
recircuiatian line. The fourth impinger serves as a knockout impinger.
i
3.1.6 Glass Impinger. Silica gel impinger. Vacuum-tight impingers,
capable; of containing ^00 g. of silica gel, with compatible fittings. The
silica gel -fmpinger will have a modified stem (1/2" ID at tip of stem).
j
3.1.7 Thersometer, (identical to that specified by Method 5)' at the outlet
of the Silica gel impinger, to monitor the exit temperature of 'the gas.
i
3.1.8 Metering System, Barometer, and Gas Density Determinations
Equipment. Same as Me-hod 5, Section 2.1.8 through 2.1.10, respectively.
3.2 i Sampla Recovery. Clean all items for sample handling or storage with
W% nitjric acid solution by soaking, where possible, and rinse- thoroughly with
DI water before use.
'3.2.1 Nitrogen Purg-o Line. Inert tubing and fittings capable of delivering
0 to 1 !scf/min (continuously adjustable) of nitrogen'gas to thsj i mpinger train
from aj standard gas cylinder (See Figure Cr'6-3). Standard 3/8-inch Teflon
tubing !and compression fittings in conjunction with an adjustable pressure
regulator and needle, valve may be used.
3.2.J2 Wash Bottles.
rinse solution.
Two polyethylene wash bottles, for Dl water and nitric
3.2.3 Sa:r.ple Storage Containers. Polyethylene, with leak- free screw cap,
5QQ-ml lor IQOQ-ml.
l
3.2.'! 10Cn-ml Graduated Cylinder and Balance.
3.2.i5 Plastic Storage Containers.
gel. i
Air tight containers ,to store silica
3. 2. -6 Funnel and Rubber Policeman. To aid in transfer of silica gel from
impinger to storage container; not necessary if silica gel is weighed directly
in the ! impinger.
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I
2
tt
a
to
8.
"5
<0
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3-3 !Sample Prepara-ion for Analysis. Sample preparation prior to analysis
includes purging the sample train, immediately following the sample run, and
filtering the recovered sample to remove particulate matter immediately
following recovery.
3.3.1 Beakers, Funnels, Volumetric Flasks, Volumetric Pipets, and
Graduated Cylinders. Assorted sizes, Teflon or glass, for preparation of
samples| sample dilution, and preparation of calibration standards. Prepare
initially following procedure described in Section 5'»1«3 and rinse between use
with O.i N HN03 and DI water.
3.3.2 Filtration Apparatus. Teflon, or equivalent, for filtering samples,
and Teflon filter holder. Teflon impinger components have been found to be
satisfactory as a sample reservoir for pressure filtration using nitrogen,
3.4 ^Analysis.
3-4.1 IC/PCR System. High performance liquid chromatograph pump, sample
injection valve, post-column reagent delivery and mixing system, and a visible
detector, capable of operating at 520 nm, all with a non-metallic (or inert)
flow path. An electronic recording integrator operating in thss peak area-mode
is recommended, but other recording devices and integration .techniques are
acceptable provided the repeatab.ility criteria and the linearity criteria for
the calli.brati.ori. curve described in Section 5«5 can be satisfied. A sample
loading!system will be required if preconcentration is employed.
3.4.$ Analytical Column. A high performance ion chromatograph (HPIC) non-
meta.11 l
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4.1 ;Sampling.
4.1.JL Wacar. 'Deionized water. It is recommended that water blanks be
checked; prior to preparing sampling reagents to ensure that the Cr*6 content
is less; than the analytical detection limit.
I
4.1.2 Potassium Hydroxide, 0.1 N. Add 5-6 gm of KOH{a) t;o approximately
900 "ml 'of DI water and let dissolve. Dilute to 1000 ml with Dl water.
4.1.J3 Silica Gel and Crushed Ice. Same as Method 5, Sections 3.1.2 and
3.1.4, respectively.
4.2 jSample Recovery. The reagents used in sample recovery are as follows:
i
4.2.2. Water. Same as subsection 4.1.1.
i
4.2.J2 Nitric Acid, 0.1 N. Add 6.3 ml of concentrated HNQ3 (70 percent) to
a graduated cylinder containing approximately 900 ml of DI water, Dilute to
1000 ml] with DI water, and mix well.
4.3 ! Sample Preparation
4.3-il Water. Same as subsection 4.1.1.
4.3.|2 Nitric Acid, 0.1 N. Same as subsection 4.2.2.
4.3.3 Filters. Acetate -membrane, or -equivalent, filters with 0.45
micromeltar or smaller pore size to remove insoluble material.
4.4 | Analysis.
4.4.jl Chromatographic Eluent. The eluent used in the analytical system is
ammoniuin sulfate based. It is prepared by adding 6,5 ml of 25% ammonium
hydroxijde (NH;|QH) and 33 grams of ammonium sulfate ttNH/,) 3^04 3 to 500 ml of DI
water. • The mixture should then be diluted to 1 liter with DI water and mixed
well. jOther combinations of eluants and/or columns may be employed provided
peak resolution, as described in Section 5.4, repeatability and linearity, as
described in Section 6.2, and analytical sensitivity are acceptable.
4,4.|2 Post-column Reagent. An effective post-column reagent for use with
the chromatographic eluent described in Section 4.4.1 is a diphenylcarbazide
(DPC) based system. Dissolve 0.5 g of 1,5-diphenylcarbazide (DPC) in 100 ml of
ACS grade methanol. Add to 500 ml of degassed containing 50 ml of 96%
spcctrcjpho tome trie grade sulfuric acid. Dilute to 1 liter with degassed DI
water. !
4.4.:4 Cr*5 Calibration Standard. Prepare Cr*6 standards from potassium
dichroniate (K-Cr2Oy, FW 294.19). To prepare a 1000 ug/ml Cr*6 stock solution,
dissolve 2.829 g of dry K2Cr,07 in 1 liter of DI water. To prepare working
standards, dilute the stock solution to'the chosen standard concentrations for
.instrument calibration with 0.05 N KOH to achieve a. matrix similar to the
'"actual |field samples.
: 8
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4.4.5, Performance Audit Sample. A performance audit sample shall be
obtained from the Quality Assurance Division of EPA and analyzed with the field
samplesJ The mailing address to request audit 'samples is:
j U. S. Environmental Protection Agency
j Atmospheric Research And Exposure Assessment Laboratory
I Qualify Assurance Division
j Source Branch, Mail Drop 77-A
i Research Triangle Park, North Carolina 27711
i
The audit sample should be prepared in a suitable sample matrix at a
concentration similar zo the actual field samples,
5, Procedure
5.1 i Sampling. The complexity of this method is such that to obtain
reliabije results, tasters should be trained and experienced with test
procedures.
5.1.1 Pretest Preparation. All components shall be maintained and
calibrated according to the procedures described in APTD-0576, unless otherwise
specified herein.
Rinse all sample train components from the glass noaale up to the silica
gal impinger and sample containers with hot tap water followed by washing with
hot soapy water. Next, rinse the train components and sample containers three
times with tap water followed by three rinses with Dl water. All the
namponehts and containers should then be soaked overnight, or a minimum of 4
hours, |in a 10 % (v/v) nitric acid solution, then rinsed three times with DI
water. } Allow the components to air dry prior to covering all openings with
Parafiljn, or equivalent. -
5.1.2 Preliminary Determinations. Same as Method 5, Section. 4.1.2.
5.1.J3 Preparation of Sampling Train. Measure 300 ml of 0,1 N KOH into a
graduated cylinder (or tare-wenghed predeaned polyethylene container). Place
approximately 150 ml of the 0.1 N KOH reagent in the first Teflon impinger.
Split cine rest of the 0.1 N KOH between the second and third Teflon impingers.
The next Teflon impinger is left dry. Place a preweighed 200-to 400-g portion
of indicating silica gel in the final glass impinger. (For sampling periods in
excess jof two hours, or for high moisture sites, 40Q-g of silica gel is
recommended.)
Reta'in reagent blanks of the 0.1 N KOH equal to the volumes used with the
field sjamples.
5.1.!4 Leak-Check Procedures. Follow the leak-check procedures given in
Method J5, Section 4.1.4.1 (Pretest Leak-Check), Section 4.1.4.2 (Leak-Checks
During jthe Sample Run), and Section 4.1.4.3 (Post-Test Leak-Checks).
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5.1.ip Sampling Train Operation. Follow the procedures given, in Mechod 5,
Section; 4.1.?. The sampling train should be iced down with water and ice to
insure heat transfer with the Teflon impingers.
.For leach run, record the data required on a data sheet auch as the one
shown in Figure 5'2 of Method 5.
5.1.6 Calculation of Percent Isokinetie. Same as Method 5, Section k.1.6.
5.2 | Post-test Nitrogen Purge. The nitrogen purge is used as a safeguard
against; the conversion of hexavalent chromium to the trivalent oxidation stata.
The purge is effective in the removal of S02 from the impin§er contents.
Attach the nitrogen purge line to the input of the impinger train. Check to
insure ;the output of the impinger train is open, and that the recirculating
line isj capped off. Open the nitrogen gas flow slowly and adjust the delivery
rate to| 10 L/min. Check the recalculating line to insure that: the pressure is
not forcing the impinger reagent out through this line. Continue the purga
under these conditions for one-half hour periodically checking the flow rate.
5,3 '; Sample Recovery. Begin cleanup procedures as soon as the train
assembliy has been purged at the end of the sampling run. The probe assembly
does majy be disconnected from the sample train prior to sample purging.
The iprobe assembly should be allowed to cool prior to sample recovery.
Disconnect the umbilical cord from the sample train. When the probe assembly
can be [safely handled, wipe off all external particulate matter near the tip of
the nozzle, and cap the nozzle prior to transporting the sample train to a
clean vlp area that is clean and protected from the wind and other potential
causes iof con lamination or loss of sample. -Inspect the train before and- during
disassembly and note any abnormal conditions.
5.3.|1. Container No. 1 (Inipingers 1 through 3). Disconnect the first
impingelr from the ssccnd impinger and disconnect the recirculation line from
the aspirator or peristaltic pump. Drain the Teflon impingers into a
preclea'ned graduated cylinder or • tare-weighed precleaned polyethylene sample
container and measure the volume of the liquid to within 1 ml or 1 gm. Record
the volume of liquid present as this information is required to calculate the
moisture content of the flue gas sample. If necessary, transfer the sample
from the graduated cylinder to a precleaned polyethylene ssuaple container.
With dl water, rinse four times the insides of the glass nozzle, the
aspirator, the sample and recirculation lines, the impingers, and the
connecting tubing-, and combine the rinses with the impinger solution in the
sample [container.
j
5.3..2 Container No. 2 (UNO, rinse optional for total chromium). With 0.1 N
HN03, rinse three times the entire train assembly, from th« nozzle to the
fourth |impingcr_ and combine the rinses into a separate precleaned polyethylene
sample , container for possible total chromium analysis. Repeat the rinse
procedure a final time with DI water, and discard the water rinses. Mark the
height!of the fluid level on the container or, alternatively if a balance is
available, weigh the container and record the weight to permit determination of
any leakage during transport. Label the container clearly to identify its
contents.
10
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5-3-3 Container No. 3 (Silica Gel). Nota the color of the indicating
silica jgel to determine if it has been completely spent. Quantitatively
transfer- the silica gel from its impinger to the original container, and seal
the container. A funnel and a rubber- policeman may be used to aid in the
transfer. The small ancunt of particulate that may adhere to the Impinger wall
need not be-removed. Do not use water or other liquids to transfer" the silica
gel, Alternatively, if a balance is available in the field, record the weight
of the spent silica gel (or the silica gel plus impinger} to th« nearest 0.5 g.
5-3.^ Container No. 4 (0.1 N KQH Blank), Once during each, field teat,
place a i volume of reagent equal to the volume placed in the sample train into a
precleaned polyethylene sample container, and seal the container. Mark the
height pf the fluid level on the container or, alternatively if a balance Is
available, weigh the container and record the weight to permit determination of
any leakage during transport. Label the container clearly to identify its
content^,
5-3-ip Container No. 5 (DI water Blank), Once during esich field test,
place ei volume of Di water equal to the volume employed to rinse the sample
train into a precleaned polyethylene sample container, and seal the container.
Mark the height of the fluid level on the container or, alternatively if a
balance; is available, weigh the container and record the weight to permit
determination of any leakage during transport.- Label the container clearly to
identify its contents.
5.3.6 Container No. 6 (0.1 N HNO, Blank). Once during each field test if
total chromium is to be determined, place 'a volume of 0.1 N HNO, reagent equal
to the volume employed to rinse the • sample train into a precleaned
polyethylene sample container, and seal the container. Mark the height of the
fluid Ijsvel on the container or, alternatively if a balance is available, weigh
the container and record the weight to permit determination of any leakage
during transport. Label the container clearly to identify its contents.
i
5.4 I Sample Preparation. For determination of Cr'$, the sample should be
filtere|i immediately . following recovery to remove any insoluble matter.
Nitrogen gas may be used as a pressure assist to the filtration process (see
Figure pr*°-4). • •
Filtjer the entire impinger sample through a 0.45 micrometer Teflon filter
(or equivalent), and collect the filtrate in a 1000-ml' graduated cylinder.
Rinse the sample container with DI water three separate times and pass these
rinses [through the filter, and add the rinses to the sample filtrate. Rinse
the Tefjlon reservoir with DI water three separate times and pass these rinses
through: the filter, and add the rinses to the sample. Determine the final
volume iof the filtrate and rinses and return them to the rinsied polyethylene
sample container. Label the container clearly to identify its contents. Rinse
the Teflon reservoir once with 0.1 N HNO, and once with DI waiter and discard
these riinses.
Tf 4otal chromium is to be determined, quantitatively recover the filter
and residue and place them in a vial. (The acetate filter may lie digested with
5 ml of ?Q# nitric acid; this digestion solution may then be diluted with DI
water fpr total chromium analysis.)
11
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n
VALVE
-a-
REGULATOR
TEFLON
RESERVOIR
NaTANK
TEFLON FILTER HOLDER
WITH .45 MICRON FILTER
1000ml
GRADUATED CYLINDER
Figure Cr+e -4. Schematic of sample filter system,
12
4196 2/90
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5,ii,l Container 2 (HN03 rinse, optional for total chromium). This sample
shall be analyzed in accordance with the selected procedure for total chromium
analysis, At a minimum, the sample should be subjected to a digestion
procedure sufficient to solubilize all chromium present.
j
5.U.2 Container 3 (Silica Gel), Weigh the spent silica gel to the nearest
0-5 s using a balance. (This step may be conducted in the field..)
3.5 iSample Analysis, The Cr*6 content of the sample filtrate is
determined by ion chroaatography coupled with a post column reactor (IC/PCR) .
To increase aansitiv-J ty for- trace levels of chromium a preconcentration system
is also j used in conjunction with the IC/PCR.
Prior to preconcer.tration and/or analysis, all field samples will be
filtered through a 0.^5 urn filter. This filtration should be conducted just
prior to sample injection/analysis.
The preconcfintraticr. is accomplished by selectively retaining the analyte on;
a solid! absorbent (as described in 3-^-3), followed by removal of the analyta
from the absorbent. The sample is injected into a sample loop of the desired
size (rjspeatad loadings or larger siae loop for greater sensitivity) and the
Cr*6 is I collected on the resin bed of the column. When the injection valve is
switched, the eluent displaces the concentrated Cr*6 sample "moving it off the
preconcentration column and onto the 1C anion separation column. • After
separation from other sample components, Cr*6 forms a specific complex in the
post-column reactor with a diphenylcarbazide reaction solution, and the complex
is then> detected by visible absorbance at a wavelength of 520 nm. The amount
of absorfaance measured is proportional to the concentration of the Cr*6 complex
formed., The 1C retention time and absorbance of the Cr*° complex is compared
with knpwn Cr*fj standards analyzed under identical conditions to provide-both
qualitative ar.d quanticative analyses.
Prior to sanple analysis establish a stable baseline with the detector set
at the required attenuation by setting1 the eluent flowrate at approximately 1
ml/min (and post column reagent flow rate at approximately 0.5 ml/min. (Note:
As long as the ratio of eluent flowrate to PCR flowrate remains constant, the
standarji curve should remain linear.) Inject a sample of DI water to insure
that no! Cr*6 appears in the water blank.
First, inject the calibration standards prepared, as described in Section
4.^.4, !to cover the appropriate concentration range, starting with the lowest
standard first. Next, inject, in duplicate, the performance audit sample,
followejd by the 0.1 N KOH field blank and the field samples. Finally, repeat
the infection of the calibration standards to allow for compensation of
instrument drift. Measure areas or heights of the Cr*6/DPC complex
chromatjagram peak. The response for replicate, consecutive! injections of
samples' must be within 3 percent of the average response, or the injection
should [be repeated until the 5 percent criteria can be met. Use the average
responses (peak areas or heights) from the duplicate injections of calibration
standards to generate a linear calibration curve. From the calibration curve,.,
determine the concentration of the field samples employing the average response
from the duplicate injections.
The 'results for the analysis of the performance audit sample must be within
10 percent of the reference value for the field sample analysis to be valid.
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6. Calibration. Maintain a written log of all calibration activities.
6.1 Sample Train Calibration. Calibrate the sample train components
according to the indicated sections of Method 5: Probe Nozzle (Section 5.1);
Pitot Tuipe (Section 5-2); Metering System (Section 5-3) i Temperature Gauges
(Section 15.5): Leak-Cheek of the Metering System (Section 5.6); and Barometer
(SectionJ5.7).
6.2 ' Calibration Curve for the 1C./PGR. Prepare working standards from the
stock solution described in Section 4.4.4. by dilution with a Dl water
solution; to approximate the field sample matrix. Prepare at least four
standards to cover one order of magnitude that bracket the field sample
concentrations. Run the standards with the field samples ass described in
Section 5.5-. "or each standard, determine the peak areas (recommended) or the
peak he-fights, calculate the average response from the duplicate injections,
and plot; the average response against the Cr*6 concentration in ug/1. The
individual responses for each calibration standard determined before and after
field sample analysis must be within 5 percent of the average response for the
analysis} to be valid. If the 5 percent criteria is exceeded, wxcessive drift
and/or ihstrumenc degradation may have occxirred, and must be corrected before
further knalyses are performed. .
Employing linear regression, calculate a predicted value for each
calibration standard with the average response for the duplicate injections.
Each predicted value must be within 7 percent of the actual value for the
calibration curve to be considered acceptable. Remake andi/or rerun the
calibration standards. If the calibration curve is still unacceptable, reduce
Che range of the curve.
7. Calculations - '
7-1
dry gas
Method :
7-2
test,
content
5.
7.3
Method .
7-4
Where
Dry Gas Volume. Using the data from the test, calculate Vm(atd , the
sample volume at standard conditions as outlined in Section 0.3 of
Volume of Water Vapor and Moisture Content. Using the> data from the
calculate Vw, afed) and BW3, the volume of water vapor and the moisture
of the stack gas, respectively, using Equations 5-2 and 5-3 of Method
Stack Gas Velocity. Using the data from the test and Equation 2-9 of
!, calculate the average stack gas velocity.
Total us? Cr*6 Per Sample. Calculate as described below:
a = (S-3) x Vls x d
m = Mass of Or*6 in the sample, ug,
S = Analysis of sample, ug Cr'Vml,
B a Analysis of blank, ug Cr*6/ml,
via = Volum« of sample after filtration, ml, and,
d = Dilution, factor (1 if not diluted).
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APPENDIX D
EXAMPLE CALCULATION FOR DETERMINING THE ALLOWABLE SLUDGE FEED RATE
D-l
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1
The following calculations demonstrate the determination of the
maximum sludge feed rate allowed within the proposed rules for the disposal of
sewage sludge published in the Federal Register on February 6, 1989. The
formulas used are provided in the proposed rule.
j These example calculations show the steps involved in calculating
the maximum allowable sludge feed rate based upon:
i « the average concentration of each toxic metal in sludge feed
i (obtained via long term monitoring);
j • the control efficiency of the incineration system for each
i toxic metal (obtained from stack sampling); and
j
i « the dispersion factor (obtained from dispersion modeling).
i The calculation is demonstrated in this case for two metals.
Facility "X" collected the following information involving two of the
regulated metals.
; « Chromium~50 mg/kg of sludge
I :
I • Lead—ISO mg/kg of sludge
i « 96% control of chromium by the incinerator and air pollution
| 'control device
| « 85% control of lead by the incinerator and air pollution
i control device
i
« • A calculated dispersion factor of 7.52 vg/mVg/sec
i • An average sludge feed rate of 7 metric tons/hr (dry weight
I basis)
CALCULATION FOR CHROMIUM
i
! From the proposed rule, the formula is
I
RSC x 86,400
C =
OF x (1-CE) x SF
Wherle: .
C=Maximum allowable concentration of arsenic, cadmium, chromium, or nickel in
sewage sludge, in milligrams per kilogram (dry weight basis).
CE=Sewage sludge incinerator control efficiency.
DF=Oispersion factor, in micrograms per cubic meter, per gram, per second.
RSC=Risk specific concentration, in micrograms per cubic meter.
86,400=Number of seconds in a day.
SF=Sewage sludge feed rate, in .metric tons per day (dry weight basis).
D-2
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Solve
for SF and make substitutions:
RSC x 86,400
OF x (1-CE) x
= 0.085
._ 0.085 x 86,400
>F = 7.52 X (1-.96) x 50
i SF = 488 metric tons/day (dry basis)
| = 20 metric tons/hr (dry basis)
Conclusion: The allowable feed rate of sludge based on chromium content is
higher than the average sludge feed rate of 7 metric tons per hour (dry
basis).
CALCULATION FOR LEAD
- .25 (NAAQS) x 86,400
DF.x (1-CE) x 5h
1Jl*py»a •
OMaximuni allowable concentration of lead 1n sewage sludge, 1n milligrams per
NM^Son^bient MMuallty Standard for lead (15 n,1crogra,s per, cubic
i meter maximum arithematic mean averaged over a calendar quarter).
86.400=Number of seconds in a day.
DF^Olspersion factor, in micrograms per cubic meter, per gram, per second.
CE=s|ewage sludge incinerator control efficiency.
SF=S|ewage sludge feed rate, in metric tons per day (dry weight basis).
Solve for SF and make substitutions:
SF
_ .25 (NAAQSt x 86,400
~ DF x (1-CE) x C
.25 g.5H86,400)
" 7.52 (1-.85) x 180
= 160 metric tons/day (dry basis)
=6.6 metric tons/hr (dry basis)
D-3
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Conclusion: Based upon the lead content of the sludge feed, the maximum
allowable feedi rate is less the average feed rate of 7 metric tons per hour
(drylasis) .This facility would need to operate at less than the .average
feed rate unless improvements can be demonstrated in the control efficiency of
lead Emissions.
D-4
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