Non-Radioactive Air Emissions at LANL

Overview

LANL Non-Radioactive Air Emissions

This portion of the air emissions monitoring program is limited, since under the Clean Air Act the Laboratory is classified as a small quantity generator for air emissions or is exempt due to the age of our facilities.

We perform engineering calculations to estimate emissions for a number of specific air pollutants (New Mexico 2.73 Emissions Inventory) and publish annual reports. Data may be updated more recently, as shown on each data page. The Laboratory has the potential to emit 100 tons per year of suspended particulate matter, nitrogen oxides, carbon monoxide, and volatile organic compounds (VOCs).

For 1997, combustion products from the industrial sources contributed the greatest amount of regulated air emissions from the Laboratory. Research and development activities contributed the greatest amount of VOCs. Emissions of beryllium and aluminum were reported for activities permitted under 20 NMAC 2.72, Construction Permits.

We also do a limited amount of actual stack emissions monitoring for non-radioactive species. An initial description of our stack monitoring program at our permitted beryllium facility will be included here in the near future.

Monitoring

Non-Radioactive Air Constituents in Los Alamos County

During the spring of 2000, the Cerro Grande Fire reached LANL and ignited both above-ground vegetation and disposed material in landfills. There was concern at the time about the potential human health impacts from chemicals emitted by the fire; therefore, short-term intensive air monitoring studies were performed. LANL did not have an adequate database of airborne non-radiological constituents under baseline conditions with which to compare data collected during the fire. For this reason, LANL developed a non-radiological air quality monitoring program.

In September 2001, we initiated a multi-year study, named NonRadNet, to monitor the composition of particulate matter and volatile organic compounds in the ambient atmosphere at three locations in Los Alamos County. This has been undertaken to provide better background data for these types of constituents for use in the event of another emergency such as the Cerro Grande Fire of May 2000.

Program Objectives
The primary objectives for this monitoring program are as follows:

• Develop the capability to collect non-radiological air monitoring data in case of any future forest fires or other emergency releases.
• Conduct monitoring to develop a database of typical background levels of selected non-radiological constituents in the communities near the Laboratory.
• Measure LANL's contribution to non-radiological air pollution in the surrounding communities.

Program Design
LANL's air quality subject matter experts wish to establish a baseline for certain non-radiological species and contaminants in the air surrounding LANL. The NonRadNeT program is designed to sample environmental levels of non-radiological air constituents at LANL and in communities near the Laboratory. Species or parameters to be monitored include total suspended particulate (TSP), particles with diameters of 10 micrometers or less (PM-10), particles with diameters of 2.5 micrometers or less (PM-2.5), 160 volatile organic compounds (VOCs), and 20 metals (Ag, As, Ba, Be, Cd, Ce, Cr, Co, Cu, Fe, Mn, Nd, Ni, Pb, Sb, Se, Sr, Tl, V, and Zn). Simultaneous monitoring takes place at three different locations - two in Los Alamos and one in White Rock, New Mexico.

Sampling commenced on September 22, 2001, at three sites and is being conducted on a continuous and on-going basis. The air samplers are operated throughout the year; consequently, there will be complete sampling of temporal variations. Air samplers are located in areas open to the public. These locations were chosen to obtain samples representative of the concentrations of natrually present organic and inorganic constitutents in the ambient atmosphere.

Station number	Station Name	Location
81	Intersection of Diamond Dr. and East Jemez Road	On the southeast corner of intersection
61	Los Alamos Hospital	On the east side of the Hospital east parking lot
15	White Rock Fire Station	On north side of White Rock Fire Station on Rover Blvd

No specific regulatory requirements exist for this program, so normally no actions will be taken. However, when a level is exceeded, an investigation will be made to attempt to determine and understand the result and possible source.

The project has chosen action levels ("investigation levels") to be 1/1000th of the Occupational Safety and Health Administration occupational exposure levels (OSHA 29 CFR 1910.1000, Table Z-1, "Limits for Air Contaminants"). The project has chosen regulatory criteria in Environmental Protection Agency (EPA) Compendium Method TO-15 for VOC analyses and criteria in EPA Compendium Methods IO-3.4 and IO-3.5 for metals analyses.

The specific constituents collected and measured were identified as being the species of greatest concern based upon a review of literature pertaining to air emissions from fires and a review of data collected by LANL during the Cerro Grande Fire. The selected analytical methods provide information on other compounds as well.

The following parameters will be measured at each location:

• TSP concentration through periodic monitoring
• selected metals concentration through periodic monitoring
• concentration of 160 VOCs through periodic monitoring
• PM-10 and PM-2.5 through continuous monitoring
• sample collection time and date
• air flow rate through filter media for TSP
• hours of operation for PM-10 and PM-2.5
• beginning and ending cannister pressures for VOC

Summary statistics for each sampler will be calculated periodically. The elements of the summary record consist of:

• daily and annual mean constituent concentrations at each station
• percent sampling completeness
• range of measured concentrations
• percent analytical completeness
• standard deviation of air concentrations at each station for each analyte

Analysis

Sampling and Chemical Analysis

Size-fractionated Particulate Material
Continuous particles with diameters of 10 micrometers or less (PM-10) particles with diameters of 2.5 micrometers or less (PM-2.5) data are collected using a Rupprecht & Patashnick TEOM (tapered element oscillating microbalance) Series 1400a ambient particulate monitor fitted with a PM-10 or PM-2.5 sample inlet. Data collected from the TEOM units are recorded electronically by the internal microprocessor computer electronics and periodically transferred to the air quality databases.

PM-10 and PM-2.5 concentrations are measured continuously and averaged over 30-minute and 24-hour time periods. VOC and total suspended particulate (TSP)/metals samples are collected every 12th day to coincide with the Enviromental Protection Agency's (EPA) national ambient air monitoring schedule and each sampling period lasts 24 hours.

Total Suspended Particulate Material and Inorganic Elemental Measurements
Samples for 24-hour time-integrated TSP are collected on filters using Tisch Environmental TE-5170V volumetric flow controlled units. Filters are placed in the sampler within one working day of the start of a sampling run. Filters are placed and collected, data pertaining to the sampling are recorded on pre-printed field forms or recorded electronically. Several types of filter material were evaluated before choosing Whatman 41 cellulose. This filter material was selected based upon the guidance obtained from EPA/625/R-96/010a, Table 2, page 3.1-17, overall handling characteristics, and the filter blank inorganic elemental concentrations.

The filters are weighed according to procedure MAQ-224 (following moisture equilibration) before and after sampling using a calibrated microbalance to determine the net weight gain. The total volume of air that is sampled is determined from the measured sampler flow rate and the sampling envelopes are sent to an analytical laboratory to be analyzed for selected metals by inductively coupled plasma emissions spectrometry following EPA SW-846 Method 6010 and by inductively coupled plasma - mass spectrometry following EPA SW-846 Method 6020.

Volatile Organic Compounds
A ThermoAnderson AVOCS (ambient volatile organic collection system) is used to collect samples of ambient air in a 15-liter SUMMA canister. When the canisters are placed and collected by field personnel, data are reported electronically. Canisters are then sent to an analytical laboratory for chromatography with a mass selective detector to determine VOC concentrations.

Concentrations

Ambient Air Concentrations

Explanation of Reported Concentrations
Data tables below summarize the ambient air concentrations calculated from field and analytical data, inorganic elements, and volatile organic compounds. For many of these elements and compounds, these are the first measurements reported in an annual Environmental Surveillance Report since this series began in 1971. The summaries include the number of measurements (samples), number of measurements that were determined to be less than their analytical detection limits, the minimum and maximum values (range) where two or more measurements had positive results, the mean value of the positive results, and the 1s (standard deviation) of the mean where three or more positive values were available.

Total Suspended Particulate Matter
Local total suspended particulate (TSP) data have been reported in several previous Environmental Surveillance Reports (1971 and 1986 through 1989). These show annual geometric means for both Los Alamos and White Rock to be in the 20 to 30 ug/m3 range, with the maximum value observed to be 242 ug/m3 during those time periods.

In our 2001 TSP data, both negative values and concentrations up to three times the previously reported maximum were observed for individual samples. The overall station means were also a factor of ten above historical measurements. These considerations led us to believe that the 2001 data are largely invalid and they were rejected as not being representative of actual atmospheric conditions due to their failure to meet our established quality goals. A different filter material, Whatman cellulose paper, has been selected for use during 2002, partially in an effort to improve our overall TSP measurement procedure.

Inorganic Elements
The summaries of these measurements for 15 elements at three stations located in Los Alamos and White Rock are shown in Table 1 (pdf) and Table 2 (pdf), respectively. There are relatively little air concentration data in previous Environmental Surveillance Reports for inorganic species, and most of what is available was determined using analytical procedures that have much higher detection limits than those used this year.

Volatile Organic Compounds
Summary data for 160 compounds measured in Los Alamos and White Rock during 2001 are presented in the linked Tables below. The first three of these tables contain summaries for 124 compounds where at least one positive detection was achieved at one site. The final table presents a summary for 36 compounds that have only detection limit data at all sites for all measurements.

• Table 3: VOCs at the Los Alamos Hospital site (pdf)
• Table 4: VOCs at the Intersection of Diamond Drive and Jemez Road in Los Alamos (pdf)
• Table 5: VOCs at the White Rock Fire Station site (pdf)
• Table 6: VOCs not detected at any site (pdf)

Background levels of these compounds are not nearly so easily determined as they can be for inorganics. Organic compounds have a variety of natural and anthropogenic sources, and many of these compounds are well mixed in the troposphere. As our program matures we hope to be able to group this large number of compounds into major source groups (e.g., fuel hydrocarbons, refrigerants, paint solvents, natural vegetation emissions, etc.) to help provide a simpler basis for evaluating seasonal variations and potential impacts from Laboratory operations.

References

References and Guidance Documents

• EPA QA/R-5, "EPA Requirements for Quality Assurance Project Plans for Environmental Data Operations," Interim Final, January 1994
• EPA Compendium Method IO-3.1, "Selection, Preparation, And Extraction of Filter Material," Compendium of Methods for the Determination of Inorganic Compounds in Ambient Air, Second Edition, EPA/625/R-96/010b
• EPA Compendium Method IO-3.4, "Determination Of Metals In Ambient Particulate Matter Using Inductively Coupled Plasma (ICP) Spectroscopy", Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air, Second Edition, EPA/625/R-96/010b
• EPA Compendium Method IO-3.5, "Determination Of Metals In Ambient Particulate Matter Using Inductively Coupled Plasma/ Mass Spectrometry Compounds in Ambient Air, Second Edition, EPA/625/R-96/010b
• EPA Compendium Method TO-15, "Determination Of Volatile Organic Compounds (VOCs) In Air Collected In Specially-Prepared Canisters And Analyzed by Gas Chromatography/ Mass Spectrometry (GC/MS)", Compendium of Methods Edition, EPA/625/R-96/010b
• EPA SW-846 Methods 6010 and 6020, "Test Methods of Evaluating Solid Waste," 3rd ed., 2nd update; US EPA. Office of Solid Waste and Emergency Response, Sept. 1994; Vol. 1A.
• Title 29 Code of Federal Regulations Part 1910.1000, Table Z-1, OSHA, "Limits for Air Contaminants"
• Title 40 Code of Federal Regulations Part 58, "Ambient Air Quality Surveillance," Appendix E
• Title 40 Code of Federal Regulations Part 136, Appendix B, "Definition and Procedure For The Determination Of The Method Detection Limit-Revision 1.11"