Partial List of Abstracts, 1998

The 1500 km Upper Mississippi River (UMR) consists of 29 navigation pools and can be divided into the upper reach (pools 1-4), the middle reach (pools 5-13), and the lower reach (pools 14-26). Comparison of composite bed sediment samples collected from the downstream third of 24 pools before and after the 1993 UMR flood provides field-scale data on the effect of the flood on sediment organic compound distributions. The sediments were analyzed for organic carbon, coprostanol, polynuclear aromatic hydrocarbons including pyrene, linear alkylbenzenesulfonates, polychlorinated biphenyls (PCBs), and organochlorine pesticides. Most of the target compounds were detected in all of the sediment samples, although concentrations were generally <1 mg/kg. The highest concentrations typically occurred in the upper reach, an urbanized area on a relatively small river. Pool 4 (Lake Pepin) is an efficient sediment trap, and concentrations of the compounds below pool 4 were substantially lower than those in pools 2-4. Differences in concentrations before and after the 1993 flood also were greatest in the upper reach. In pools 1-4, concentrations of pyrene and PCBs decreased after the flood whereas coprostanol increased. These results suggest that bed sediments stored in the pools were diluted or buried by sediments with different organic compound compositions washed in from urban and agricultural portions of the watershed.

A three-dimensional inverse groundwater flow and transport model that fits hydraulic-head and concentration data simultaneously using nonlinear regression is presented and applied to a layered sand and silt groundwater system beneath the Grindsted Landfill in Denmark. The aquifer is composed of rather homogeneous hydrogeologic layers. Two issues common to groundwater flow and transport modelling are investigated: 1) The accuracy of simulated concentrations in the case of calibration with head data alone; and 2) The advantages and disadvantages of using a two-dimensional cross-sectional model instead of a three-dimensional model to simulate contaminant transport when the source is at the land surface. Results show that using only hydraulic heads in the nonlinear regression produces a simulated plume that is profoundly different from what is obtained in a calibration using both hydraulic-head and concentration data. The present study provides a well-documented example of the differences that can occur. Representing the system as a two-dimensional cross-section obviously omits some of the system dynamics. It was, however, possible to obtain a simulated plume cross-section that matched the actual plume cross-section well. The two-dimensional model execution times were about a seventh of those for the three-dimensional model, but some difficulties were encountered in representing the spatially variable source concentrations and less precise simulated concentrations were calculated by the two-dimensional model compared to the three-dimensional model. Summed up, the present study indicates that three-dimensional modelling using both hydraulic heads and concentrations in the calibration should be preferred in the considered type of transport studies.

A p finite element scheme and parallel iterative solver are introduced for a modified form of the shallow water equations. The governing equations are the three-dimensional shallow water equations. After a harmonic decomposition in time and rearrangement, the resulting equations are a complex Helmholz problem for surface elevation, and a complex momentum equation for the horizontal velocity. Both equations are nonlinear and the resulting system is solved using the Picard iteration combined with a preconditioned biconjugate gradient (PBCG) method for the linearized subproblems. A subdomain-based parallel preconditioner is developed which uses incomplete LU factorization with thresholding (ILUT) methods within subdomains, overlapping ILUT factorizations for subdomain boundaries and under-relaxed iteration for the resulting block system. The method builds on techniques successfully applied to linear elements by introducing ordering and condensation techniques to handle uniform p refinement. The combined methods show good performance for a range of p (element order), h (element size), and N (number of processors). Performance and scalability results are presented for a field scale problem where up to 512 processors are used.

Large-scale mining activities have generated a plume of acidic ground water more than 15 km long in the regional aquifer of the Pinal Creek Basin. A one-dimensional reactive-transport model was developed using PHREEQC to aid in the analysis of transport and chemical processes in the plume and to determine the uses and limitations of this type of modeling approach. In 1984, the acidic part of the plume had a pH as low as 3.4 and contained milligram-per-liter concentrations of iron, copper, aluminum and other metals. From 1984 to 1994, concentrations of contaminants in the alluvial aquifer in Pinal Creek Basin, Arizona, decreased as a result of mixing, recharge, remedial pumping and chemical reactions. For reactions involving gypsum and rhodochrosite, the equilibrium modeling assumption of a local geochemical equilibrium was generally valid. From 1984 to 1990, water along the simulated flow path was at equilibrium or slightly supersaturated with gypsum, and gypsum equilibria controlled dissolved concentrations of calcium and sulfate. Beginning in 1991, water in the acidic part of the plume became increasingly undersaturated with respect to gypsum, indicating that the gypsum available for dissolution in the aquifer may have been completely consumed by about 1991.

Calculation of chemical flux rates for streams requires integration of continuous measurements of discharge with discrete measurements of solute concentrations. We compared two commonly used methods for interpolating chemistry data (time-averaging and flow-weighting) to determine whether discrepancies between the two methods were large relative to other sources of error in estimating flux rates. Flux rates of dissolved Si and SO₄^2- were calculated from 10 years of data (1981-1990) for the NW inlet and outlet of Mirror Lake and for a 40-day period (March 22 to April 30. 1993) during which we augmented our routine (weekly) chemical monitoring with collection of daily samples. The time-averaging method yielded higher estimates of solute flux during high-flow periods if no chemistry samples were collected corresponding to peak discharge. Concentration-discharge relationships should be used to interpolate stream chemistry during changing flow conditions if chemical changes are large. Caution should be used in choosing the appropriate time-scale over which data are pooled to derive the concentration-discharge regressions because the model parameters (slope and intercept) were found to be sensitive to seasonal and inter-annual variation. Both methods approximated solute flux to within 2-10% for a range of solutes that were monitored during the intensive sampling period. Our results suggest that errors arising from interpolation of stream chemistry data are small compared with other sources of error in developing watershed mass balances.

Field investigations of the hydrodynamics and the resuspension and transport of particulate matter in a bottom boundary layer were carried out in South San Francisco Bay, California during March- April 1995. The GEOPROBE, an instrumented bottom tripod, and broad-band acoustic Doppler current profilers were used in this investigation. The instrument assemblage provided detailed measurements of 1) turbulent mean velocity distribution within 1.5 m of sediment-water interface; 2) characteristics of 3-D tidal current in the water column; 3) friction velocity u* or bottom shear stress and bottom roughness length Z_o; 4) hydrodynamic conditions conducive for sediment resuspension; and 5) circulation patterns which are responsible for transporting suspended particulate matter in South San Francisco Bay. An unusual flow event was recorded by these instruments during March 8-11, 1995. A 3-D numerical model was implemented which reproduced, qualitatively, the unusual observations and supported the hypothesis that the unusual flow event was caused by a combination of wind driven circulation and weak neap tides.

Pinal Creek, Arizona receives an inflow of ground water with high dissolved inorganic carbon (57-75 mg/l) and low pH (5.8-6.3). There is an observed increase of in-stream pH from approximately 6.0-7.8 over the 3 km downstream of the point of groundwater inflow. We hypothesized that CO₂ gas-exchange was the most important factor causing the pH increase in this stream-aquifer system. An existing transport model, for coupled ground water-surface water systems (OTIS), was modified to include carbonate equilibria and CO₂ degassing, used to simulate alkalinity, total dissolved inorganic carbon C_t, and pH in Pinal Creek. Because of the non-linear relation between pH and C_t, the modified transport model used the numerical iteration method to solve the non-linearity. The transport model parameters were determined by the injection of two tracers, bromide and propane. The resulting simulations of alkalinity, C_t) and pH reproduced, without fitting, the overall trends in downstream concentrations. A multi-parametric sensitivity analysis (MPSA) was used to identify the relative sensitivities of the predictions to six of the physical and chemical parameters used in the transport model. MPSA results implied that C_t and pH in stream water were controlled by the mixing of ground water with stream water and CO₂ degassing. The relative importance of these two processes varied spatially depending on the hydrologic conditions, such as stream flow velocity and whether a reach gained or lost stream water caused by the interaction with the ground water. The coupled transport model with CO₂ degassing and generalized sensitivity analysis presented in this study can be applied to evaluate carbon transport and pH in other coupled stream-ground water systems.

A new method for collecting pore-water samples in sand and gravel streambeds is presented. We developed a mini drivepoint solution sampling (MINIPOINT) technique to collect pore-water samples at 2.5-cm vertical resolution. The sampler consisted of six small-diameter stainless steel drivepoints arranged in a 10-cm-diameter circular array. In a simple procedure, the sampler was installed in the streambed to preset drivepoint depths of 2.5, 5.0, 7.5, 10.0, 12.5, and 15.0 cm. Sampler performance was evaluated in the Shingobee River, Minnesota, and Pinal Creek, Arizona, by measuring the vertical gradient of chloride concentration in pore water beneath the streambed that was established by the uninterrupted injection to the stream. Pore-water samples were withdrawn from all drivepoints simultaneously. In the first evaluation, the vertical chloride gradient was unchanged at withdrawal rates between 0.3 and 4.0 ml/min but was disturbed at higher rates. In the second evaluation, up to 70 ml of pore water was withdrawn from each drivepoint at a withdrawal rate of 2.5 ml/min without disturbing the vertical chloride gradient. Background concentrations of other solutes were also determined with MINIPOINT sampling. Steep vertical gradients were present for biologically reactive solutes such as DO, NH₄⁺, NO₃^-, and dissolved organic C in the top 20 cm of the streambed. These detailed solute profiles in the hyporheic zone could not have been determined without a method for close interval vertical sampling that does not disturb natural hydrologic mixing between stream water and groundwater.

Sediment transport through the Brazilian sector of the Amazon River valley, a distance of 2010 km, involves exchanges between the channel and the flood plain that in each direction exceed the annual flux of sediment out of the river at Obidos ( approximately 1200 Mt yr^-1). The exchanges occur through bank erosion, bar deposition, settling from diffuse overbank flow, and sedimentation in flood-plain channels. We estimated the magnitude of these exchanges for each of 10 reaches of the valley, and combined them with calculations of sediment transport into and out of the reaches based on sediment sampling and flow records to define a sediment budget for each reach. Residuals in the sediment budget of a reach include errors of estimation and erosion or deposition within the channel. The annual supply of sediment entering the channel from bank erosion was estimated to average 1570 Mt yr^-1) (1.3 X the Obidos flux) and the amount transferred from channel transport to the bars (380 Mt yr^-1) and the flood plain (460 Mt yr^-1 in channelized flow; 1230 Mt yr^-1) in diffuse overbank flow) totaled 2070 Mt yr^-1 (1.7 X the Obidos flux). Thus, deposition on the bars and flood plain exceeded bank erosion by 500 Mt yr^-1 over a 10-16 yr period. Sampling and calculation of sediment loads in the channel indicate a net accumulation in the valley floor of approximately 200 Mt yr^-1 over 16 yr, crudely validating the process-based calculations of the sediment budget, which in turn illuminate the physical controls on each exchange process. Another 300-400 Mt yr^-1 are deposited in a delta plain downstream of Obidos. The components of the sediment budget reflect hydrologic characteristics of the valley floor and geomorphic characteristics of the channel and flood plain, which in turn are influenced by tectonic features of the Amazon structural trough.

The response of rivers and riparian forests to upstream dams shows a regional pattern related to physiographic and climatic factors that influence channel geometry. We carried out a spatial analysis of the response of channel geometry to 35 dams in the Great Plains and Central Lowlands, USA. The principal response of a braided channel to an upstream dam is channel-narrowing, and the principal response of a meandering channel is a reduction in channel migration rate. Prior to water management, braided channels were most common in the southwestern Plains where sand is abundant, whereas meandering channels were most common in the northern and eastern Plains. The dominant response to upstream dams has been channel-narrowing in the southwestern Plains (e.g., six of nine cases in the High Plains) and reduction in migration rate in the north and east (e.g., all of twelve cases in the Missouri Plateau and Western Lake Regions). Channel-narrowing is associated with a burst of establishment of native and exotic woody riparian pioneer species on the former channel bed. In contrast, reduction in channel migration rate is associated with a decrease in reproduction of woody riparian pioneers. Thus, riparian pioneer forests along large rivers in the southwestern Plains have temporarily increased following dam construction while such forests in the north and east have decreased. These patterns explain apparent contradictions in conclusions of studies that focused on single rivers or small regions and provide a framework for predicting effects of dams on large rivers in the Great Plains and elsewhere. These conclusions are valid only for large rivers. A spatial analysis of channel width along 286 streams ranging in mean annual discharge from 0.004 to 1370 cubic meters per second did not produce the same clear regional pattern, in part because the channel geometries of small and large streams are affected differently by a sandy watershed.

Agricultural irrigation has a substantial impact on water quantity and quality in the lower Arkansas River valley of southeastern Colorado. A two-dimensional flow and solute transport model was used to evaluate the potential effects of changes in irrigation on the quantity and quality of water in the alluvial aquifer and in the Arkansas River along an 17.7 km reach of the river. The model was calibrated to aquifer water level and dissolved solids concentration data collected throughout the 24 year study period (1971-95). Two categories of irrigation management were simulated with the calibrated model: (1) a decrease in ground water withdrawals for irrigation; and (2) cessation of all irrigation from ground water and surface water sources. In the modeled category of decreased irrigation from ground water pumping, there was a resulting 6.9% decrease in the average monthly ground water salinity, a 0.6% decrease in average monthly river salinity, and an 11.1% increase in ground water return flows to the river. In the modeled category of the cessation of all irrigation, average monthly ground water salinity decreased by 25%; average monthly river salinity decreased by 4.4%; and ground water return flows to the river decreased by an average of 64%. In all scenarios, simulated ground water salinity decreased relative to historical conditions for about 12 years before reaching a new dynamic equilibrium condition. Aquifer water levels were not sensitive to any of the modeled scenarios. These potential changes in salinity could result in improved water quality for irrigation purposes downstream from the affected area.

Bacterial oxidation of ¹⁴CH₂Br₂ and ¹⁴CH₃Br was measured in freshwater, estuarine, seawater, and hypersaline-alkaline samples. In general, bacteria from the various sites oxidized similar amounts of ¹⁴CH₂Br₂ and comparatively less ¹⁴CH₃Br. Bacterial oxidation of ¹⁴CH₃)Br was rapid in freshwater samples compared to bacterial oxidation of ¹⁴CH₃Br in more saline waters. Freshwater was also the only site in which methyl fluoride-sensitive bacteria (e.g., methanotrophs or nitrifiers) governed brominated methane oxidation. Half-life calculations indicated that bacterial oxidation of CH₂Br₂ was potentially significant in all of the waters tested. In contrast, only in freshwater was bacterial oxidation of CH₃Br as fast as chemical removal. The values calculated for more saline sites suggested that bacterial oxidation of CH₃Br was relatively slow compared to chemical and physical loss mechanisms. However, enrichment cultures demonstrated that bacteria in seawater can rapidly oxidize brominated methanes. Two distinct cultures of nonmethanotrophic methylotrophs were recovered; one of these cultures was able to utilize CH₂Br₂ as a sole carbon source, and the other was able to utilize CH₃Br as a sole carbon source.

In this study a stochastic approach to calibration of an orographic precipitation model was applied in the Gunnison River Basin of south-western Colorado. The stochastic approach to model calibration was used to determine: (1) the model parameter uncertainty and sensitivity; (2) the grid-cell resolution to run the model (10 or 5 km grids); (3) the model grid rotation increment; and (4) the basin subdivision by elevation band for parameter definition. Results from the stochastic calibration are location and data dependent. Uncertainty, sensitivity and range in the final parameter sets were found to vary by grid-cell resolution and elevation. Ten km grids were found to be a more robust model configuration than 5 km grids. Grid rotation increment, tested using only 10 km grids, indicated increments of less than 10 degrees to be superior. Basin subdivision into two elevation bands was found to produce 'optimal' results for both 10 and 5 km grids.

Observed April 1 snowpack accumulations within and near the Gunnison River basin in southwestern Colorado are compared with simulations from the Rhea-orographic-precipitation model to determine if the model simulates reliable magnitudes and temporal and spatial variability in winter precipitation for the basin. Twenty simulations of the Rhea model were performed using 'optimal' parameter sets determined for 10-kilometer (km) grids (10-km by 10-km grid cells) through stochastic calibration. Comparisons of Rhea-model simulations of winter precipitation with April 1 snowpack accumulations at 32 snowcourse stations were performed for the years 1972-1990. For most stations and most years the Rhea model reliably simulates the temporal and spatial variability in April 1 snowpack accumulations. However, in general, the Rhea-model underestimates April 1 snowpack accumulations in the Gennison River basin area, and the underestimation is greatest for locations that receive the largest amount of snow. A significant portion of the error in Rhea-model simulations is due to the calibration of the Rhea model using gauge-catch precipitation measurements which can be as much as 50 percent below actual snowfall accumulations. Additional error in the Rhea-model simulations is a result of the comparison of gridded precipitation values to observed values measured at points.

We extend the finite-volume Eulerian-Lagrangian localized adjoint method (FVELLAM) for solution of the advection-dispersion equation to two dimensions. The method can conserve mass globally and is not limited by restrictions on the size of the grid Peclet or Courant number. Therefore, it is well suited for solution of advection-dominated ground-water solute transport problems. In test problem comparisons with standard finite differences, FVELLAM is able to attain accurate solutions on much coarser space and time grids. On fine grids, the accuracy of the two methods is comparable. A critical aspect of FVELLAM (and all other ELLAMs) is evaluation of the mass storage integral from the preceding time level. In FVELLAM this may be accomplished with either a forward or backtracking approach. The forward tracking approach conserves mass globally and is the preferred approach. The backtracking approach is less computationally intensive, but not globally mass conservative. Boundary terms are systematically represented as integrals in space and time which are evaluated by a common integration scheme in conjunction with forward tracking through time. Unlike the one-dimensional case, local mass conservation cannot be guaranteed, so slight oscillations in concentration can develop, particularly in the vicinity of inflow or outflow boundaries.

Reliable estimates of sediment-budget errors are important for interpreting sediment-budget results. Sediment-budget errors are commonly considered equal to sediment-budget imbalances, which may underestimate actual sediment-budget errors if they include compensating positive and negative errors. We modified the sediment 'fingerprinting' approach to qualitatively evaluate compensating errors in an annual (1991) fine (<63 mm) sediment budget for the North Halawa Valley, a mountainous, forested drainage basin on the island of Oahu, Hawaii, during construction of a major highway. We measured concentrations of aeolian quartz and ¹³⁷Cs in sediment sources and fluvial sediments, and combined concentrations of these aerosols with the sediment budget to construct aerosol budgets. Aerosol concentrations were independent of the sediment budget, hence aerosol budgets were less likely than sediment budgets to include compensating errors. Differences between sediment-budget and aerosol-budget imbalances therefore provide a measure of compensating errors in the sediment budget. The sediment-budget imbalance equalled 25 per cent of the fluvial fine-sediment load. Aerosol-budget imbalances were equal to 19 per cent of the fluvial ¹³⁷Cs load and 34 per cent of the fluvial quartz load. The reasonably close agreement between sediment- and aerosol-budget imbalances indicates that compensating errors in the sediment budget were not large and that the sediment-budget imbalance is a reliable measure of sediment-budget error. We attribute at least one-third of the 1991 fluvial fine-sediment load to highway construction. Continued monitoring indicated that highway construction produced 90 per cent of the fluvial fine-sediment load during 1992. Erosion of channel margins and attrition of coarse particles provided most of the fine sediment produced by natural processes. Hillslope processes contributed relatively minor amounts of sediment.

Nonlinear regression was introduced to ground water modeling in the 1970s, but has been used very little to calibrate numerical models of complicated ground water systems. Apparently, nonlinear regression is thought by many to be incapable of addressing such complex problems. With what we believe to be the most complicated synthetic test case used for such a study, this work investigates using nonlinear regression in ground water model calibration. Results of the study fall into two categories. First, the study demonstrates how systematic use of a well designed nonlinear regression method can indicate the importance of different types of data and can lead to successive improvement of models and their parameterizations. Our method differs from previous methods presented in the ground water literature in that (1) weighting is more closely related to expected data errors than is usually the case; (2) defined diagnostic statistics allow for more effective evaluation of the available data, the model, and their interaction; and (3) prior information is used more cautiously. Second, our results challenge some commonly held beliefs about model calibration. For the test case considered, we show that (1) field measured values of hydraulic conductivity are not as directly applicable to models as their use in some geostatistical methods imply; (2) a unique model does not necessarily need to be identified to obtain accurate predictions; and (3) in the absence of obvious model bias, model error was normally distributed. The complexity of the test case involved implies that the methods used and conclusions drawn are likely to be powerful in practice.

A comparison of the new hydrogen isotope-ratio technique of Vaughn and others [Vaughn, B.H., and others, 1998. An automated system for hydrogen isotope analysis of water: Chemical Geology, v. 152, p. 309-319] for the analysis of water samples utilizing automated on-line reduction by elemental uranium showed that 94% of 165 samples of Antarctic snow, ice, and stream water agreed with the d²H values determined by platinum equilibration, exhibiting a bias of +0.5 per mil and a 2-sigma variation of 1.9 per mil. The isotopic results of 10 reduction technique samples, however, gave d²H values that differed by 3.5 per mil or more, and were too negative by as much as 5.4 per mil and too positive by as much as 4.9 per mil with respect to those determined using the platinum equilibration technique.

The forms and partitioning of aqueous mercury species in the canals and marshes of the Northern Florida Everglades exhibit strong spatial and temporal variability. In canals feeding Water Conservation Area (WCA) 2A, unfiltered total Hg (HgT_U) is less than 3 ng L^-1 and relatively constant. In contrast, methyl mercury (MeHg) exhibited a strong seasonal pattern, with highest levels entering WCA-2A marshes during July. Stagnation and reduced flows also lead to particle enrichment of MeHg. In the marshes of WCA-2A, 2B and 3A, HgT_U is usually <5 ng L^-1 with no consistent north-south patterns. However, for individual dates, aqueous unfiltered MeHg (MeHg_U) levels increase from north to south with generally lowest levels in the eutrophied regions of northern WCA-2A. A strong relationship between filtered Hg species and dissolved organic carbon (DOC), evident for rivers draining wetlands in Wisconsin, was not apparent in the Everglades, suggesting either differences in the binding sites of DOC between the two regions, or non-organic Hg complexation in the Everglades.

The impact on ground water quality from increasing fertilizer application rates over the past 40 years is evaluated within a glacial aquifer system beneath a thick unsaturated zone. Ground water ages within the aquifer could not be accurately determined from the measured distribution of ³H and as a result, chlorofluorocarbon (CFC) and ³H/³He dating techniques were applied. Beneath a 25 m thick unsaturated zone, ground water ages based on CFC-11 concentrations were greater than ³H/³He ground water ages by 6 to 10 years, due to the time lag associated with the diffusion of CFCs through the unsaturated zone. Using the corrected CFC-11 and ³H/³He ground water ages and the estimated travel time of ³H within the unsaturated zone, the approximate position of ground water recharged since the mid-1960s was determined. Nitrate concentrations within post mid-1960s recharge were generally elevated and near or above the drinking water limit of 10 mg-N/L. In comparison, pre mid-1960s recharge had nitrate concentrations <2.5 mg-N/L. The elevated NO₃^- concentrations in post mid-1960s recharge are attributed mainly to increasing fertilizer application rates between 1970 and the mid- to late 1980s. Anaerobic conditions suitable for denitrification are present within pre mid-1960s recharge indicating that removal of DO is a slow process taking tens of years. Over the next 10 to 20 years, nitrate concentrations at municipal well fields that are currently capturing aerobic ground water recharged near the mid-1960s are expected to increase because of the higher fertilizer application rates beginning in the 1970s and 1980s.

The Little River, an ephemeral stream that drains a watershed of approximately 88 km² in northern Florida, disappears into a series of sinkholes along the Cody Scarp and flows directly into the carbonate Upper Floridan aquifer, the source of water supply in northern Florida. The changes in the geochemistry of ground water caused by a major recharge pulse from the sinking stream were investigated using chemical and isotopic tracers and mass-balance modeling techniques. Nine monitoring wells were installed open to the uppermost part of the aquifer in areas near the sinks where numerous subterranean karst solution features were identified using ground penetrating radar. During high-flow conditions in the Little River, the chemistry of water in some of the monitoring wells changed, reflecting the mixing of river water with ground water. Rapid recharge of river water into some parts of the aquifer during high-flow conditions was indicated by enriched values of d¹⁸O and delta deuterium (-1.67 to -3.17 per mil and -9.2 to -15.6 per mil, respectively), elevated concentrations of tannic acid, higher (more radiogenic) ⁸⁷Sr/⁸⁶Sr ratios, and lower concentrations of ²²²Rn, silica, and alkalinity compared to low-flow conditions. The proportion of river water that mixed with ground water ranged from 0.10 to 0.67 based on binary mixing models using the tracers ¹⁸O, deuterium, tannic acid, silica, ²²²Rn, and ⁸⁷Sr/⁸⁶Sr. On the basis of mass-balance modeling during steady-state flow conditions, the dominant processes controlling carbon cycling in ground water are the dissolution of calcite and dolomite in aquifer material, and aerobic degradation of organic matter.

Optical properties are presented for 66 samples of mica covering the range from annite-->biotite-->zinnwaldite-->ferroan lepidolite and ferroan muscovite from occurrences of granitic pegmatite (NYF type) throughout the Pikes Peak batholith (PPB) in Colorado. Chemical composition was determined for 34 of these samples. The optical data are correlated with composition, mode of occurrence, and relation to pegmatite paragenesis. Optical properties of the trioctahedral micas show a consistent trend of decreasing beta index of refraction, from an average of 1.693 in annite of the host granite to 1.577 in zinnwaldite and ferroan lepidolite of the miarolitic cavities, which correlates with a progressively decreasing content of Fe. A comparison of optical and compositional data for micas from localities throughout the PPB indicates a variation in geochemical evolution among pegmatites of different districts, and between the Pikes Peak Granite and its late satellite plutons. Analyses of mica samples taken from cross-sections through individual pegmatites reveal a decrease in index of refraction and total iron that unambiguously document a progressive geochemical evolution within a given pegmatite. Such data, in addition to field evidence, indicate that micas enclosed within massive quartz are paragenetically older than those within miarolitic cavities; minerals within miarolitic cavities represent the final stages of primary crystallization. A general model of pegmatite paragenesis is proposed that hypothesizes formation of miarolitic cavities as a consequence of pegmatite configuration and inclination, as well as early crystallization of massive quartz that confines the silicate melt and volatile phase, resulting in closed-system crystallization with a concomitant increase in pressure, consequent episodic cavity-rupture events, and corresponding changes in mica composition.

Two natural-gradient tracer tests were conducted to determine the transport and biodegradation behavior of linear alkylbenzenesulfonate (LAS) surfactant under in situ conditions in a sewage-contaminated aquifer. The tests were conducted in two biogeochemically distinct zones of the aquifer: (1) an aerobic uncontaminated zone (oxic zone) and (2) a moderately aerobic, sewage-contaminated zone (transition zone). Chromatographic separation of the surfactant mixture was observed in both zones and attributed to the retardation of the longer alkyl chain homologues during transport. No significant loss of LAS mass was observed for the oxic zone while 20% of the LAS mass injected into the transition zone was removed due to biodegradation. Biodegradation preferentially removed the longer alkyl chain homologues and the external isomers (i.e., 2- and 3-phenyl). The removal of LAS mass coincided with a decrease in dissolved oxygen concentrations, the appearance of LAS metabolites, and an increase in the number of free-living bacteria with a concomitant change in bacteria morphology. The formation of LAS metabolites accounted for 86% of the LAS mass removed in the transition zone. Over the duration of the test, sorption and biodegradation enriched the LAS mixture in the more water-soluble and biologically resistant components.

Transport and biodegradation of linear alkylbenzenesulfonate (LAS) in sewage-contaminated groundwater were investigated for a range of dissolved oxygen concentrations. Both laboratory column and an 80-day continuous injection tracer test field experiments were conducted. The rates of LAS biodegradation increased with increasing dissolved oxygen concentrations and indicated the preferential biodegradation of the longer alkyl chain LAS homologues (i.e., C₁₂ and C₁₃) and external isomers (i.e., 2-and 3-phenyl). However, for similar dissolved oxygen concentrations, mass removal rates for LAS generally were 2-3 times greater in laboratory column experiments than in the field tracer test. Under low oxygen conditions (<1 mg/L) only a fraction of the LAS mixture biodegraded in both laboratory and field experiments. Biodegradation rate constants for the continuous injection field test (0.002-0.08/day) were comparable to those estimated for a 3-h injection (pulsed) tracer test conducted under similar biogeochemical conditions, indicating that increasing the exposure time of aquifer sediments to LAS did not increase biodegradation rates.

Wetlands in the prairie known as potholes or sloughs represent an ever-changing mosaic of surface waters interacting with the atmosphere, groundwater, and each other in a variety of ways. Studies of groups of adjacent wetlands in different parts of the glaciated North American prairie have enabled some connections to be made between hydrologic processes, biological communities, and use of these wetlands by wetland-dependent wildlife. Understanding controls on variability in water levels, water volume, and salinity in these wetlands sets the stage for understanding controls on biological communities utilizing these wetlands. The role that natural variability in water and salinity plays in making these wetlands an important resource for waterfowl will provide an important context for those who are responsible for artificially altering the variability of water and salinity in prairie wetlands.

Ice rafting is the dominant mechanism responsible for the transport of fine-grained sediments from coastal zones to the deep Arctic Basin. Therefore, the drift of ice-rafted debris (IRD) could be a significant transport mechanism from the shelf to the deep basin for radionuclides originating from nuclear fuel cycle activities and released to coastal Arctic regions of the former Soviet Union. In this study, 28 samples of IRD collected from the Arctic ice pack during expeditions in 1989-95 were analyzed for ¹³⁷Cs by gamma spectrometry and for ²³⁹Pu and ²⁴⁰Pu by thermal ionization mass spectrometry. The two samples with the highest ¹³⁷Cs concentrations were collected in the vicinity of Franz Josef Land, and their backward trajectories suggest origins in the Kara Sea. Among the lowest ¹³⁷Cs values are seven measured on sediments entrained on the North American shelf in 1989 and 1995, and sampled on the shelf less than six months later. The two highest concentrations of ^239,240Pu came from samples collected in the central Canada Basin and near Spitsbergen; calculated backward trajectories suggest at least 14 years of circulation in the Canada Basin in the former case, and an origin near Severnaya Zemlya (at the Kara Sea/Laptev Sea boundary) in the latter case. While most of the IRD samples showed ²⁴⁰Pu/²³⁹Pu ratios near the mean global fallout value of 0.185, five of the samples had lower ratios, in the 0.119 to 0.166 range, indicative of mixtures of Pu from fallout and from the reprocessing of weapons-grade Pu. The backward trajectories of these five samples suggest origins in the Kara Sea or near Severnaya Zemlya.

The bioavailability to clams (Potamocorbula amurensis and Macoma balthica) of Cd, Cr, and Zn from suspended particulate material (SPM) collected during a phytoplankton bloom was compared to bioavailability from SPM dominated by resuspended sediments. Bioavailability was also compared among mudflat sediments amended with different levels of living benthic microalgae. Bioavailability was defined by absorption efficiencies determined using pulse chase protocols, modified for studying natural particle assemblages. The partitioning of Cd and Zn to particles (K_d) increased as the microalgae biomass (Chl a) increased in the particle assemblages; partitioning of Cr was less affected by the algal biomass. The clams fed particle assemblages enriched with microalgae absorbed Cd and Zn with significantly greater efficiency than did the clams fed algae-poor particles. This was partially explained by the greater occurrence of Cd and Zn in the cytosolic fraction of the particle assemblages that were microalgae enriched, as well as by the efficient absorption of cytosolic material by the clams. Among metals, Zn was most efficiently absorbed by both clams, and Cr the least. M. balthica absorbed Zn more efficiently from all types of food particles (39-82%) than did P. amurensis (13-50%). P. amurensis absorbed Cd with greater efficiency from the bloom SPM (44-48%) than did M. balthica (13-21%), but the two clams absorbed Cd similarly from benthic microalgae (26-51%). The addition of microalgae to complex natural particle assemblages clearly affected the bioavailability of associated metals, so studies using sediments (or suspended particulate material) that do not include a realistic living food component could underestimate metal bioavailability from particle ingestion.

Seasonal and annual variation in biomass and structure of algal assemblages of hyposaline Devils Lake were examined in relation to turbidity, ambient concentrations of major ions, trace elements and nutrients, and the standing crop of herbivores. Lake level declined during the early years of study, but rose markedly in subsequent years as historically large volumes of water flowed into this hydrologically-closed basin. Winter algal assemblages were dominated (in biomass) most years by small, non-motile chlorophytes (Choricystis minor, Kirchneriella lunaris or Dunaliella sp.), or Euglena sp. in the most saline sub-basin. Spring assemblages were dominated by diatoms (Stephanodiscus cf. minutulus, Surirella peisonis, Cyclotella meneghiniana and Entomoneis paludosa were especially prominent) or chlorophytes (C. minor) until the lake level rose. C. minor abundances then declined in spring assemblages and diatoms (Stephanodiscus cf. agassizensis and S. niagarae; E. paludosa in the more saline sub-basins) dominated. The potential for nitrogen-deficient conditions for phytoplankton growth was evidenced most summers and early autumns by consistently high concentrations of reactive-P relative to inorganic-N and blooms of the N-fixing cyanophyte Aphanizomenon flos-aquae; Microcystis aeruginosa typically was a co-dominant (>30% of biomass) in these assemblages. Pulses of diatoms (S. cf. agassizensis and C. meneghiniana) occurred in summers following unusually prolonged periods of calm weather or large water inflows. Physical (irradiance, turbulence) and chemical (major nutrients) variables were the primary factors associated with phytoplankton growth. Transparency and major nutrient concentrations accounted for more of the annual variation in phytoplankton structure than did salinity. Seasonal abundance patterns of the dominant zooplankton (the copepod Diaptomus sicilis; the cladocerans Ceriodaphnia quadrangula, Chydorus sphaericus, Daphnia pulex and Diaphanosoma birgei; and the rotifers Brachionus spp., Filinia longiseta, Keratella cochlearis and K. quadrata) also indicated variation in algal populations related to grazing.

The invertebrate fauna of nontidal portions of the lower San Joaquin River and its major tributaries is described in relation to water quality and habitat using canonical correspondence analysis, autecological metrics, and indicator species analysis. A large-scale (basin-wide) pattern in community response to salinity (sulfate-bicarbonate type) was detected when standardized, stable substratum was sampled. Community structure, taxa richness and EPT (ephemeropterans, plecopterans, and trichopterans) richness varied with dissolved-solids concentration (55 to 1700 mg total dissolved solids L^-1), and distributions of many taxa indicated salinity optima. Distinct assemblages associated with either high or low salinity were evident over this range. Large-scale patterns in community structure were unrelated to pesticide distributions. Structure and taxa richness of invertebrate assemblages in sand substratum varied both with salinity and with microhabitat heterogeneity. The benthic fauna generally was dominated by a taxa-poor assemblage of specialized psammophilous species, contributing to a weaker relationship between community structure and water quality than was observed using standardized substratum. Habitat types and associated dominant species were characterized using indicator species analysis. Species assemblages did not vary substantially with irrigation regime or river discharge, indicating that structure of invertebrate communities was a conservative measure of water quality.

The chemical composition of the Cu-mining-related acidic ground water (pH approximately 3.5 to near neutral) in Pinal Creek Basin, Arizona has been monitored since 1980. In-situ experiments are planned using alluvial sediments placed in the ground-water flow path to measure changes in mineral and chemical composition and changes in dissolution rates of subsurface alluvial sediments. The test results should help refine developed models of predicted chemical changes in ground-water composition and models of streamflow. For the preliminary test, sediment from the depth of the well screen of a newly drilled well was installed in three wells, the source well (pH 4.96) and two up-gradient wells (pHs 4.27 and 4.00). The sediment was placed in woven macrofilters, fastened in series to polyvinyl chloride (PVC) pipes, and hung at the screened level of each well. After interacting with the slowly moving ground water for 48 days, the test sediments were removed for analysis. There was no evidence that any of the materials used were biologically or chemically degraded or that the porosity of the filters was diminished by ferric hydroxide precipitation. These materials included 21-mm-pore (21PEMF) and 67-mm-pore polyester and the 174-mm-pore fluorocarbon Spectra/mesh macrofilters containing the in-situ sediment, the polypropylene (PP) macrofilter support structures, and the Nylon (NY) monofilament line used to attach the samples to the PVC pipe. Based on chemical and mineral composition and on particle-size distribution of the sediment before and after ground-water exposure, the 21PEMF macrofilter was chosen as the most suitable macrofilter for the long-term in-situ experiment. Tests also showed that the PP support structures and the NY monofilament line were sufficiently durable for this experiment.

Lovley, D.R., Fraga, J.L., Blunt-Harris, E.L., Hayes, L.A., Phillips, E.J.P., Coates, J.D., 1998, Humic substances as a mediator for microbially catalyzed metal reduction: Acta Hydrochimica et Hydrobiologica, v. 26, no. 3, p. 152-157.

The potential for humic substances to serve as terminal electron acceptors and to function as electron shuttles between iron(III)-reducing micro-organisms and insoluble iron(III) oxides was investigated. Geobacter metallireducens, an iron(III)-reducing micro-organism conserved energy to support growth from electron transport to humics. Growth with poorly crystalline iron(III) oxide, an electron acceptor, was significantly stimulated in G. metallireducens by 100 mM of the humics analog, anthraquinone-2,6-disulphonate (AQDS). Studies with other quinones which included; lawsone, menadione and anthraquinone-2-sulphonate all stimulated iron(III) reduction by G. metallireducens. Screening a diversity of micro-organisms indicated that organisms which had the capability to reduce iron(III) also had the ability to reduce AQDS. However, micro-organisms that did not reduce iron(III) oxides showed little or no AQDS reducing capacity. Humics stimulated the reduction of iron(III) in clay and crystalline iron(III) forms, geothite and hematite.

In this paper we use numerical models of coupled biological-hydrodynamic processes to search for general principles of bloom regulation in estuarine waters. We address three questions: What are the dynamics of stratification in coastal systems as influenced by variable freshwater input and tidal stirring? How does phytoplankton growth respond to these dynamics? Can the classical Sverdrup Critical Depth Model (SCDM) be used to predict the timing of bloom events in shallow coastal domains such as estuaries? We present results of simulation experiments which assume that vertical transport and net phytoplankton growth rates are horizontally homogeneous. In the present approach the temporally and spatially varying turbulent diffusivities for various stratification scenarios are calculated using a hydrodynamic code that includes the Mellor-Yamada 2.5 turbulence closure model. These diffusivities are then used in a time- and depth-dependent advection-diffusion equation, incorporating sources and sinks, for the phytoplankton biomass. Our modeling results show that, whereas persistent stratification greatly increases the probability of a bloom, semidiurnal periodic stratification does not increase the likelihood of a phytoplankton bloom over that of a constantly unstratified water column.

Marine ecosystems include a subset in which at least some interrelated geochemical, biochemical, physiological, population and community characteristics are changed by pollutants. Moderate contamination is relatively widespread in coastal and estuarine ecosystems, so the subset of ecosystems with at least some processes affected could be relatively large. Pollutant influences have changed and will probably continue to change on time scales of decades. Biological exposures and dose in such ecosystems are species-specific and determined by how the species is exposed to different environmental media and the geochemistry of individual pollutants within those media. Bioaccumulation models offer significant promise for interpreting such exposures. Biological responses to pollutants need to be more directly linked to exposure and dose. At the level of the individual this might be improved by better understanding relationships between tissue concentrations of pollutants and responses to pollutants. Multi-discipline field and laboratory studies combined with advanced understanding of some basic processes have reduced the ambiguities in interpreting a few physiological/organismic responses' to pollutants in nature. Recognition of pollutant-induced patterns in population responses could lead to similar advances. A rational framework for ecotoxicology is developing, but its further advance is dependent upon better integration of ecotoxicology with basic marine ecology and biology.

The 1994 spring phytoplankton bloom in South San Francisco Bay caused substantial reductions in concentrations of dissolved Cd, Ni, and Zn, but not Cu. We estimate that the equivalent of similar to 60% of the total annual input of Cd, Ni, and Zn from local waste-water treatment plants is cycled through the phytoplankton in South Bay. The results suggest that processes that affect phytoplankton bloom frequency or intensity in estuaries (e.g. nutrient enrichment) may also affect metal trapping. The bloom was characterized by hydrographic surveys conducted at weekly intervals for 9 weeks. Metal samples were collected from the water column on three occasions, timed to bracket the period when the bloom was predicted. Factors that might confound observations of biological influences, such as freshwater inputs, were relatively constant during the study. Before the bloom, concentrations of dissolved Cd were 0.81 plus or minus 0.02 nmol kg^-1, Zn concentrations were 19.8 ± 1.5 nmol kg^-1, Ni were 42 ± 1.4 nmol kg^-1, and Cu were 37 ± 1.4 nmol kg^-1. These values are elevated relative to riverine and coastal end-members, reflecting inputs from wastewater and (or) sediments. At the height of the bloom, dissolved Zn, Cd, and Ni were reduced to 19, 50, and 75% of their prebloom concentrations, respectively. Dissolved Cu concentrations increased 20%. The mass of Cd taken up by phytoplankton was similar to the mass of Cd removed from solution if particle settling was considered, and Cd concentrations estimated in phytoplankton were higher than concentrations in suspended particulate material (SPM). Particulate concentrations of Zn and Ni during the bloom appeared to be dominated by the influence of changes in resuspension of Zn-and Ni-rich sediments.

Factors controlling the spatial distribution of benthic sulfate reduction (SR) were investigated at 3 stations [upper (UB), mid (MB) and lower bay (LB)] along the Chesapeake Bay (eastern USA) central channel from early spring through late fall, 1989 to 1994. Annual rates of 0 to 12 cm depth-integrated SR were 0.96, 9.62 and 6.33 mol S m^-2 yr^-1 for UB, MB and LB, respectively, as calculated from ³⁵SO₄^2- incubations. SR was carbon limited at UB, LB, and at the sediment surface at MB, and SO₄^2- limited at depth at MB. Temperature explained 33 to 68% of the variability in annual rates, with an apparent influence on SR which increased in the seaward direction in surface sediments. We speculate that the enhanced response of SR to temperature in LB surface sediments was linked to seasonal variations in macrofaunal activity associated with temperature. Estimates of reduced-S burial indicated that only 4 to 8% of sulfur reduced annually was buried as Fe-S minerals at MB and LB, with the remainder presumably being reoxidized. In contrast, >50% of the sulfur reduced annually was buried at UB, due to comparatively low SR rates and the high concentration of reactive iron in the oligohaline region. SR mineralized 18 to 32% of the annual primary production. Our results indicate that organic quality may be more important than the absolute quantity of organic loading in dictating the magnitude of benthic SR rates along an estuarine gradient. Spatial trends in SR reflected the combined influence of deposited organic matter quality and quantity, SO₄^2- availability, the presence or absence of benthic macrofauna, overlying water dissolved O₂ conditions, reduced-S reoxidation dynamics, and iron-sulfide mineral formation.

Methylmercury (MeHg) degradation was investigated along an eutrophication gradient in the Florida Everglades by quantifying ¹⁴CH₄ and ¹⁴CO₂ production after incubation of anaerobic sediments with ¹⁴C-MeHg. Degradation rate constants (k) were consistently less than or equal to 0.1 d^-1, and decreased with sediment depth. Higher k values were observed when shorter incubation times and lower MeHg amendment levels were used, and k increased two-fold as in-situ MeHg concentrations were approached. The average floc layer k was 0.046 ± 0.023 d^-1 (n=17) for 1-2 day incubations. In-situ degradation rates were estimated to be 0.02 to 0.5 ng MeHg (g dry sed)^-1 d^-1, increasing from eutrophied to pristine areas. Nitrate-respiring bacteria did not demethylate MeHg, and NO₃^- addition partially inhibited degradation in some cases. MeHg degradation rates were not affected by PO₄^-3 addition. ¹⁴CO₂ production in all samples indicated that oxidative demethylation (OD) was an important degradation mechanism. OD occurred over five orders of magnitude of applied MeHg concentration, with lowest limits [1-18 ng MeHg (g dry sediment)^-1] in the range of in-situ MeHg levels. Sulfate reducers and methanogens were the primary agents of anaerobic OD, although it is suggested that methanogens dominate degradation at in-situ MeHg concentrations. Specific pathways of OD by these two microbial groups are proposed.

This report describes the hydrologic system of the Bonneville Salt Flats with emphasis on the mechanisms of solute transport. Variable-density, three-dimensional computer simulations of the near-surface part of the ground-water system were done to quantify both the transport of salt dissolved in subsurface brine that leaves the salt-crust area and the salt dissolved and precipitated on the land surface. The study was designed to define the hydrology of the brine ground-water system and the natural and anthropogenic processes causing salt loss, and where feasible, to quantify these processes. Specific areas of study include the transport of salt in solution by ground-water flow and the transport of salt in solution by wind-driven ponds and the subsequent salt precipitation on the surface of the playa upon evaporation or seepage into the subsurface. In addition, hydraulic and chemical changes in the hydrologic system since previous studies were documented.

Samples of soil, saprolite, bedrock, and porewater from a lower montane wet forest, the Luquillo Experimental Forest (LEF) in Puerto Rico, were studied to investigate the rates and mechanisms of biotite weathering. The soil profile, at the top of a ridge in the Rio Icacos watershed, consists of a 50-100-cm thick layer of unstructured soil above a 600-800 cm thick saprolite developed on quartz diorite. The only minerals present in significant concentration within the soil and saprolite are biotite, quartz, kaolinite, and iron oxides. Biotite is the only primary silicate releasing significant K and Mg to porewaters. Although biotite in samples of the quartz diorite bedrock is extensively chloritized, chlorite is almost entirely absent in the saprolite phyllosilicates. Phyllosilicate grains are present as 200-1000 mm wide books below about 50 cm depth. X-ray diffraction (XRD) and electron microprobe analyses indicate that the phyllosilicate grains contain a core of biotite surrounded by variable amounts of kaolinite. Lattice fringe images under transmission electron microscope (TEM) show single layers of biotite altering to two layers of kaolinite, suggesting dissolution of biotite and precipitation of kaolinite at discrete boundaries. Some single 14-Å layers are also observed in the biotite under TEM. The degree of kaolinitization of individual phyllosilicate grains as observed by TEM decreases with depth in the saprolite. This TEM work is the first such microstructural evidence of epitaxial growth of kaolinite onto biotite during alteration in low-temperature environments.

The rate of release of Mg in the profile, calculated as a flux through the soil normalized per watershed land area, is approximately 500 mol hectare^-1 yr ^-1 (1.6 x 10^-9 mol_Mg m_soil^-2s ^-1). This rate is similar to the flux estimated from Mg discharge out the Rio Icacos (1000 mol hectare ^-1 yr^-1, or 3.5 x 10^-9 mol_Mg m_soil^-2s ^-1), indicating that scaling up from the soil to the watershed is possible for Mg release. The rate of Mg release from biotite, normalized to Brunauer-Emmett-Teller (BET) surface area, is calculated using a mass balance equation which includes the density and volume of phyllosilicate grains, porewater chemistry and flux, and soil porosity. The mean rates of biotite weathering calculated from K and Mg release rates are approximately 6 and 11 x 10^-16 mol _(biotite) m_(biotite)^-2 s^-1 respectively, significantly slower than laboratory rates (10^-12 to 10^-11 mol _(biotite) m_(biotite)^-2 s^-1). The discrepancy in scaling down from the soil to the laboratory is probably explained by (1) differences in weathering mechanism between the two environments, (2) higher solute concentrations in soil porewaters, (3) loss of reactive surface area of biotite in the saprolite due to kaolinite and iron oxide coatings, and/or (4) unaccounted-for heterogeneities in flow path through the soil.

A fluvial island is a landform, elevated above and surrounded by stream-channel branches or waterways, that persists sufficiently long to establish permanent vegetation. Natural fluvial islands occur in any part of a drainage network but most commonly in montane, piedmont-valley, and coastal flood-plain environments. Processes, often interactive, by which islands form include avulsion (the sudden separation of land by a flood or by an abrupt change in the course of a stream), rapid and gradual channel incision, channel migration, dissection of both rapidly and slowly deposited bed sediment, and deposition of bed sediment on a vegetated surface or behind a channel obstruction. Products of high-energy conditions, fluvial islands typically lack stability over decades to millennia. Fluvial islands in Plum Creek, Colorado, USA, results of sorting processes following a recent high-magnitude flood, and in the Snake River, Idaho, USA, partly results of the Pleistocene Bonneville Flood, illustrate how islands form, develop, and disappear. The examples consider differing conditions of island shape, size, height, sediment, and vegetation.

Evaporation from Wetland P1 in the Cottonwood Lake area of North Dakota, USA was determined by the energy-budget method for 1982-85 and 1987. Evaporation rates were as high as 0.672 cm day^-1. Incoming solar radiation, incoming atmospheric radiation, and long-wave radiation emitted from the water body are the largest energy fluxes to and from the wetland. Because of the small heat storage of the water body, evaporation rates closely track solar radiation on short time scales. The effect of advected energy related to precipitation is small because the water quickly heats up by solar radiation following precipitation. Advected energy related to ground water is minimal because ground-water fluxes are small and groundwater temperature is only about 7 degree C. Energy flux related to sediment heating and thermal storage in the sediments, which might be expected to be large because the water is clear and shallow, affects evaporation rates by less than 5 percent.

Tritium/helium-3 (³H/³He) and chlorofluorocarbon (CFCs, CFC-11, CFC-12, CFC-113) data are used to date the young fraction in groundwater mixtures from a karstic limestone aquifer near Valdosta, Georgia, where regional paleowater in the Upper Floridan aquifer receives recharge from two young sources - the flow of Withlacoochee River water through sinkholes in the river bed, and leakage of infiltration water through post-Eocene semi-confining beds above the Upper Floridan aquifer. In dating the young fraction of mixtures using CFCs, it is necessary to reconstruct the CFC concentration that was in the young fraction prior to mixing. The ³H/³He age is independent of the extent of dilution with older (³H-free and ³He_trit-free) water. The groundwater mixtures are designated as Type-1 for mixtures of regional paleowater and regional infiltration water and Type-2 for mixtures containing more than approximately 4% of river water. The fractions of regional paleowater, regional infiltration water, and Withlacoochee River water in the groundwater mixtures were determined from Cl^- and d¹⁸O data for water from the Upper Floridan aquifer at Valdosta, Georgia.

The chlorofluorocarbons CFC-11 and CFC-113 are removed by microbial degradation and/or sorption processes in most anaerobic (Type-2) groundwater at Valdosta, but are present in some aerobic Type-1 water. CFC-12 persists in both SO₄-reducing and methanogenic water. The very low detection limits for CFCs (approximately 0.3 pg kg^-1) permitted CFC-11 and CFC-12 dating of the fraction of regional infiltration water in Type-1 mixtures, and CFC-12 dating of the river-water fraction in Type-2 mixtures. Overall, approximately 50% of the 85 water samples obtained from the Upper Floridan aquifer have CFC-12-based ages of the young fraction that are consistent with the ³H concentration of the groundwater. Because of uncertainties associated with very low ³H and ³He content in dilute mixtures, ³H/³He dating is limited to the river-water fraction in Type-2 mixtures containing more than about 10% river water. Of the 41 water samples measured for 3H/3He dating, dilution of ³H and low ³He concentration limited ³H/³He dating to 16 mixtures in which ³H/³He ages are defined with errors ranging from ±2 to ±7.5 a (1s). After correction for dilution with (assumed) CFC-free regional infiltration water and regional paleowater in the Upper Floridan aquifer, adjusted CFC-12 ages agree with ³H/³He ages within 5 a or less in 7 of the 9 co-dated Type-2 mixtures.

Tritium data and dating based on both CFC-11 and CFC-12 in Type-1 mixtures indicate that travel times of infiltration water through the overlying Post-Eocene semi-confining beds exceed 35 a. The CFC and ³H/³He dating indicate that the river fraction in most groundwater entered the groundwater reservoir in the past 20 to 30 a. Few domestic and municipal supply wells sampled intercept water younger than 5 a. Calculated velocities of river water in the Upper Floridan aquifer downgradient of the sinkhole area range from 0.4 to 8.2 m/d. Radiocarbon data indicate that ages of the regional paleowater are on the 10000-a time scale. An average lag time of approximately 10 to 25 a is determined for discharge of groundwater from the surficial and intermediate aquifers above the Upper Floridan aquifer to the Withlacoochee River.

The quality of water in the Upper Floridan aquifer near Valdosta, Georgia is affected locally by discharge of Withlacoochee River water through sinkholes in the river bed. Data on transient tracers and other dissolved substances, including Cl^-, ³H, tritiogenic helium-3 (³He), chlorofluorocarbons (CFC-11, CFC-12, CFC-113), organic C (DOC), O₂ (DO), H₂S, CH₄, d¹⁸O, dD and ¹⁴C were investigated as tracers of Withlacoochee River water in the Upper Floridan aquifer. The concentrations of all tracers were affected by dilution and mixing. Dissolved Cl^-, d¹⁸O, dD, CFC-12, and the quantity (³H+³He) are stable in water from the Upper Floridan aquifer, whereas DOC, DO, H2S, CH4, ¹⁴C, CFC-11, and CFC-113 are affected by microbial degradation and other geochemical processes occurring within the aquifer. Groundwater mixing fractions were determined by using dissolved Cl^- and d¹⁸O data, recognizing 3 end-member water types in the groundwater mixtures: (1) Withlacoochee River water (d¹⁸O = -2.5 ± 0.3^0/00, Cl^- = 12.2 ± 2 mg/l), (2) regional infiltration water (d¹⁸O = -4.2 ± 0.1^0/00, Cl^- = 2.3 ± 0.1 mg/l), and (3) regional paleowater resident in the Upper Floridan aquifer (d¹⁸O = -3.4 ± 0.1^0/00, Cl^- = 2.6 ± 0.1 mg/l) (uncertainties are ±1s). Error simulation procedures were used to define uncertainties in mixing fractions. Fractions of river water in groundwater range from 0 to 72% and average 10%. The influence of river-water discharge on the quality of water in the Upper Floridan aquifer was traced from the sinkhole area on the Withlacoochee River 25 km SE in the direction of regional groundwater flow. Infiltration of water is most significant to the N and NW of Valdosta, but becomes negligible to the S and SE in the direction of general thickening of post-Eocene confining beds overlying the Upper Floridan aquifer.

Historical and geologic records may be used to enhance magnitude estimates for extreme floods along mountain channels, as demonstrated in this study from the San Juan Mountains of Colorado. Historical photographs and local newspaper accounts from the October 1911 flood indicate the likely extent of flooding and damage. A checklist designed to organize and numerically score evidence of flooding was used in 15 field reconnaissance surveys in the upper Animas River valley of southwestern Colorado. Step-backwater flow modeling estimated the discharges necessary to create longitudinal flood bars observed at 6 additional field sites. According to these analyses, maximum unit discharge peaks at approximately 1.3 m³s^-1km^-2 around 2200 m elevation, with decreased unit discharges at both higher and lower elevations. These results (1) are consistent with Jarrett's (1987, 1990, 1993) maximum 2300-m elevation limit for flash-flooding in the Colorado Rocky Mountains, and (2) suggest that current Probable Maximum Flood (PMF) estimates based on a 24-h rainfall of 30 cm at elevations above 2700 m are unrealistically large. The methodology used for this study should be readily applicable to other mountain regions where systematic streamflow records are of short duration or nonexistent.

Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release (up to 35 mM total dissolved mercury) from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca²⁺. Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in DI water (pH = 6.0) had no detectable (<2.5 nm) dissolved mercury. the presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, edta, or cysteine) did not enhance the dissolution of mercury from the mineral. aromatic carbon content in the isolates (determined by ¹³C NMR) correlated positively with enhanced cinnabar dissolution.

The chemical evolution of the Kurnub Group paleowater was studied starting from rainwater in recharge areas of the Sinai and along groundwater flowpaths leading to the natural outlets of this regional aquifer. This was achieved by investigating the chemical composition of groundwater, ionic ratios, degrees of saturation with common mineral species, normative analysis of dissolved salts and by modeling of rock/water interaction and mixing processes occurring along groundwater flow paths. The initial groundwater composition used is from the Nakhel well in Sinai. It evolves from desert rainwater percolating through typical Kurnub Group lithology in Sinai. This rainwater dissolves mainly gypsum, halite and dolomite together with smaller amounts of marine aerosol and K-feldspar. At the same time it precipitates calcite, SiO₂, smectite and degasses CO₂. Between the area of Nakhel and the northern Negev the chemistry of Kurnub Group waters is influenced by dissolution of halite and lesser amounts of gypsum of surficial origin in recharge areas, small amounts of feldspars and of dolomite cement in sandstones eroded from the Arabo-Nubian igneous massif of Sinai and organic degradation-derived CO₂. Concomitantly, there is precipitation of calcite, smectite, SiO₂ and probably analcime characteristic of sediments in continental closed basins. North of the Negev, the Kurnub Group fluids are diluted and altered by mixing with Judea Group aquifer groundwaters. On the east there is mixing with residual brines from the water body ancestral to the Dead Sea, prior to discharge into the Arava valley. Rock/water interaction indicated by NETPATH and PHREEQC modeling is in agreement with lithology and facies changes previously observed in the Kurnub Group sequence.

An on-board technique was developed that combined discharge-weighted pumping to a high-speed continuous-flow centrifuge for isolation of the particulate-sized material with ultrafiltration for isolation of colloid-sized material. In order to address whether these processes changed the particle sizes during isolation, samples of particles in suspension were collected at various steps in the isolation process to evaluate changes in particle size. Particle sizes were determined using laser light-scattering photon correlation spectroscopy and indicated no change in size during the colloid isolation process. Mississippi River colloid particle sizes from twelve sites from Minneapolis to below New Orleans were compared with sizes from four tributaries and three seasons, and from predominantly autochthonous sources upstream to more allochthonous sources downstream.

Before Glen Canyon Dam was completed upstream from Grand Canyon, floods scoured sand from the channel bed and deposited sand on bars within recirculating eddies. After completion of Glen Canyon Dam in 1963, peak discharge of the mean annual floods dropped from about 2600 to 900 m³/s, and 85% of the sediment supply was eliminated. Under the postdam flow regime, sand bars in eddies have degraded. In an experiment to study, in part, the effects of floods in rebuilding these bars, a controlled flood was released from Glen Canyon Dam in late March and early April 1996. Although fluvial sequences characteristically fine upward, the deposits of the experimental flood systematically coarsen upward. Measurements of suspended-sediment concentration and grain size and of bed-material grain size suggest that the upward coarsening results from the channel becoming relatively depleted of fine-grained sediment during the seven days of the high-flow experiment. Predam flood beds of the Colorado River also coarsen upward, indicating that supply-limitation and grain-size evolution are natural processes that do not require the presence of a dam.

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In this article, we examine the appropriate role of science in determining whether or not to restore or rehabilitate the Colorado River in the Grand Canyon by summarizing studies carried out by numerous agencies, universities, and consulting firms since 1983. This reach of the Colorado extends 425 km between Glen Canyon Dam and Lake Mead reservoir. Efforts to manipulate ecosystem processes and components in the Grand Canyon have received widespread public attention, such as the 1996 controlled flood released from Glen Canyon Dam and the proposal to drain Lake Powell reservoir.

Isotope tracer methods were used to determine flow paths, recharge areas and relative age for groundwater in the Kilauea volcano area of the Island of Hawaii. A network of up to 66 precipitation collectors was emplaced in the study area and sampled twice yearly for a three-year period. Stable isotopes in rainfall show three distinct isotopic gradients with elevation, which are correlated with trade wind, rain shadow and high-elevation climatological patterns. Temporal variations in precipitation isotopes are controlled more by the frequency of storms than by seasonal temperature fluctuations. Results from this study suggest that (1) sampling network design must take into account areal variations in rainfall patterns on islands and in continental coastal areas and (2) isotope/elevation gradients on other tropical islands may be predictable on the basis of similar climatology. Groundwater was sampled yearly in coastal springs, wells and a few high-elevation springs. Areal contrasts in groundwater stable isotopes and tritium indicate that the volcanic rift zones compartmentalize the regional groundwater system, isolating the groundwater south of Kilauea's summit and rift zones. Part of the Southwest Rift Zone appears to act as a conduit for water from higher elevation, but there is no evidence for downrift flow in the springs and shallow wells sampled in the lower East Rift Zone.

Slug tests in fractured rock usually are interpreted with models that assume homogeneous formation properties, even though hydraulic properties of fractures can vary by many orders of magnitude over the length of boreholes. To investigate the impact of heterogeneity on the interpretation of slug tests in fractured rock, slug tests were conducted over large intervals of boreholes in crystalline rock in central New Hampshire, and interpreted using a homogeneous model. The results of the slug tests were then compared with estimates of transmissivity from fluid-injection tests conducted over shorter intervals in the same boreholes. The fluid-injection tests showed transmissivity to vary more than six orders of magnitude over the length of the boreholes; however, the sum of the transmissivities from the fluid-injection tests were within an order of magnitude of the transmissivity estimated from the slug tests. Although the two estimates of transmissivity were within an order of magnitude of each other, the water level responses during the slug tests did not exactly match the responses predicted by the homogeneous model. To investigate the effect of heterogeneity on water level responses during slug tests, a Laplace-transform solution was developed for slug tests conducted in boreholes containing multiple fractures with hydraulic properties that vary over the length of the borehole. A comparison of this solution with the homogeneous model shows no difference between the shape of water level responses in a homogeneous formation and a (layered) heterogeneous formation. Furthermore, the transmissivity estimated using a homogeneous model is within an order of magnitude of the prescribed transmissivity in the heterogeneous model. Thus, differences between responses predicted from a homogeneous model and measured water levels during slug tests can be attributed to phenomena such as nonradial flow in the vicinity of the borehole, and not heterogeneous hydraulic properties over the length of the borehole. The experimental results of this investigation show that even when conditions such as nonradial flow are present in the vicinity of the borehole, interpretations of slug tests using a homogeneous model provided order-of-magnitude estimates of transmissivity in the crystalline rock terrane under consideration.

A mathematical model is developed to interpret the early-time recovering water level following the termination of pumping in wells subject to turbulent head losses. The model assumes that turbulent head losses dissipate immediately when pumping ends. In wells subject to both borehole storage and turbulent head losses, the early-time recovery exhibits a slope equal to 1/2 on log-log plots of the recovery versus time. This half-slope response should not be confused with the half-slope response associated with a linear flow regime during aquifer tests. The presence of a borehole skin due to formation damage or stimulation around the pumped well alters the early-time recovery in wells subject to turbulent head losses and gives the appearance of borehole storage, where the recovery exhibits a unit slope on log-log plots of recovery versus time. Type curves can be used to estimate the formation storativity from the early-time recovery data. In wells that are suspected of having formation damage or stimulation, the type curves can be used to estimate the 'effective' radius of the pumped well, if an estimate of the formation storativity is available from observation wells or other information. Type curves for a homogeneous and isotropic dual-porosity aquifer are developed and applied to estimate formation properties and the effect of formation stimulation from a single-well test conducted in the Madison limestone near Rapid City, South Dakota.

Sediment samples were collected from the lower Calcasieu River and estuary, Louisiana, in a study of the release of metals from sediments to the overlying water column. Whole samples were characterized by analyses that included: (1) determination of total sediment ammonium concentrations; (2) determination of total sediment Cr, Mn and Fe concentrations; (3) extraction of sediment with hydrogen peroxide followed by dilute hydrochloric acid to obtain recoverable metals, including oxides; and (4) extraction of sediment with hydrogen peroxide plus pyrophosphate at a pH of 7-8 to recover organically-bound Cr but not metal oxides. Concentrations of Cr, Mn and Fe in sediment interstitial water were determined. The concentrations of Cr in interstitial water could not be predicted from total sediment concentrations of Cr. Degradation of organic matter appeared to be the mechanism that caused elevated Cr concentrations in the interstitial water. Concentrations of Cr in interstitial water were positively correlated with total concentrations of ammonium in sediment. Concentrations of Cr in interstitial water that exceeded water-column concentrations of Cr were found when the total concentrations of ammonium in sediment exceeded 1 mu mol per gram wet weight. Concentrations of metals in interstitial water that are larger than metal concentrations in the water column create a potential for diffusive flux and metal enrichment of the overlying water column.

Annual emissions of (CH₄ + CO₂) to the atmosphere were proportional to net hydrologic inputs of C, mostly by groundwater, at two lakes in the Shingobee River watershed in north-central Minnesota. Williams Lake (WL), a closed basin lake near the top of the watershed, had a hydraulic residence time of 2-4 yr and groundwater exchange of about +2 mol dissolved inorganic carbon (DIC) and -0.1 mol dissolved organic carbon (DOC) m^-2 lake area yr^-1. The Shingobee River flows through Shingobee Lake (SL) that had a hydraulic residence of 0.3-0.4 yr and received net groundwater plus surface-water inputs of +5.3 to +7.3 mol DIC and fewer than +1.3 mol (DOC + particulate organic carbon) m^-2 yr^-1). Approximately 60-80% of net annual C input to SL was from groundwater. Lake storage of CH₄ and CO₂ was greatest in late winter, with maximum emissions to the atmosphere immediately following ice melt. The lakes emitted CH₄ continuously during open water, having annual losses of -1.6 mol CH₄ m^-2 yr^-1 at WL and -1.9 mol CH₄ m^-2 yr^-1 at SL. Although the WL epilimnion was CO₂ depleted throughout summer, net annual CO₂ exchange with the atmosphere was near zero because springtime emission offset summertime uptake. CO₂ supersaturation resulted in emission of -8.0 mol CO₂ m^-2 yr^-1 at SL.

Ecological responses to climatic variability in the Southwest include regionally synchronized fires, insect outbreaks, and pulses in tree demography (births and deaths). Multicentury, tree-ring reconstructions of drought, disturbance history, and tree demography reveal climatic effects across scales, from annual to decadal, and from local (<10² km²) to mesoscale (10⁴ -10⁶ km²). Climate–disturbance relations are more variable and complex than previously assumed. During the past three centuries, mesoscale outbreaks of the western spruce budworm (Choristoneura occidentalis) were associated with wet, not dry episodes, contrary to conventional wisdom. Regional fires occur during extreme droughts but, in some ecosystems, antecedent wet conditions play a secondary role by regulating accumulation of fuels. Interdecadal changes in fire-climate associations parallel other evidence for shifts in the frequency or amplitude of the Southern Oscillation (SO) during the past three centuries. High interannual, fire-climate correlations (r = 0.7 to 0.9) during specific decades (i.e., circa 1740-80 and 1830-60) reflect periods of high amplitude in the SO and rapid switching from extreme wet to dry years in the Southwest, thereby entraining fire occurrence across the region. Weak correlations from 1780 to 1830 correspond with a decrease in SO frequency or amplitude inferred from independent tree-ring width, ice core, and coral isotope reconstructions.

Episodic dry and wet episodes have altered age structures and species composition of woodland and conifer forests. The scarcity of old, living conifers established before circa 1600 suggests that the extreme drought of 1575-95 had pervasive effects on tree populations. The most extreme drought of the past 400 years occurred in the mid–twentieth century (1942-57). This drought resulted in broadscale plant dieoffs in shrublands, woodlands, and forests and accelerated shrub invasion of grasslands. Drought conditions were broken by the post-1976 shift to the negative SO phase and wetter cool seasons in the Southwest. The post-1976 period shows up as an unprecedented surge in tree-ring growth within millennia-length chronologies. This unusual episode may have produced a pulse in tree recruitment and improved rangeland conditions (e.g., higher grass production), though additional study is needed to disentangle the interacting roles of land use and climate. The 1950s drought and the post-1976 wet period and their aftermaths offer natural experiments to study long-term ecosystem response to interdecadal climate variability.

As the result of a pipeline burst, a body of light aliphatic crude oil floats atop the groundwater in a shallow sand and gravel aquifer in a remote area outside Bemidji, Minnesota. Biodegradation has resulted in the formation of a plume of DOC downgradient from the oil body. Groundwater has also been contaminated in an area known as the spray zone, from vertical infiltration of DOC resulting from biodegradation of crude oil in the overlying unsaturated zone. The majority of DOC in the contaminated groundwater is in the form of nonvolatile organic acids (NVOA's) which represent the partial oxidation products of the crude oil constituents. The NVOA's have been classified into three fractions according to their isolation on XAD resins: hydrophobic neutrals (HPO-N), hydrophobic acids (HPO-A) and hydrophilic acids (HPI-A). These fractions of NVOA's were isolated from a well downgradient from the oil body (well 530; DOC=21 mg C/l), from a well in the spray zone (well 603; DOC=15 mg C/l) and from an uncontaminated well upgradient of the oil body where the naturally occurring DOC is 2.9 mg C/l (well 310). The three sets of NVOA's were characterized by elemental analyses, molecular weight determinations, ¹⁴C ages and liquid phase ¹H and ¹³C NMR. The crude oil and the saturate, aromatic, resin and asphaltene fractions of the crude oil were similarly analyzed by elemental analysis and NMR. The NVOA's from the contaminated wells were clearly distinguishable from the naturally occurring groundwater DOC. Based upon molecular weights, sulfur contents, aromaticities and the presence of methyl groups bonded to aromatic rings, the characterization data suggests that the NVOA's originate from the C₁₈ or greater alkylaromatic, naphthenoaromatic and sulfur-containing constituents of the crude oil, including possibly the resins and asphaltenes.

Analysis of sediment cores from Elephant Butte Reservoir, New Mexico, provides a method for investigating historical trends in water quality in the upper Rio Grande. Dating using ¹³⁷Cs abundance is combined with core lithology and reservoir history to interpret the sedimentary record. Sediments at the coring site date only from about 1957, due to removal by erosion of sediment deposited from 1916, when the reservoir was built, to the drought in the 1950s. Polychlorinated biphenyls (PCBs) and total DDT (= p,p'-DDT+p,p'-DDE+p,p'-DDD) are present at low concentrations in the sediment core. Concentrations peak at 5.0 and 11.3 ug/kg, respectively, in sediment deposited in about 1970-72, then decrease in sediments deposited after that date. This decrease correlates closely with National bans on the uses of these chemicals. The chemical signature of the reservoir sediments supports the hypothesis that sediment from the Rio Grande is diluted by sediment from the Rio Puerco. The sediment signature of the Rio Puerco also is reflected in uranium-thorium activity ratios greater than unity in recent reservoir sediments, indicating the release of drainage waters into the Rio Puerco from uranium mines.

Although it is well-known that concentrations of anthropogenic radionuclides and organochlorine compounds in aquatic systems have decreased since their widespread release has stopped in the United States, the magnitude and variability of rates of decrease are not well-known. Paleolimnological studies of reservoirs provide a tool for evaluating these long-term trends in riverine systems. Rates of decrease from the 1960s to the 1990s of ¹³⁷Cs, PCBs, and total DDT in dated sediment cores from 11 reservoirs in the eastern and central United States were modeled using first-order rate models. Mean half-times of 10.0 ± 2.5, 9.5 ± 2.2, and 13 ± 5.8 yr for decay-corrected ¹³⁷Cs, PCBs, and total DDT, respectively, are surprisingly similar. Similar rates of decrease in a few reservoirs are also demonstrated for chlordane and lead. Conceptual and simple mathematical models relating two soil distributions of ¹³⁷Cs to trends in the cores provide insight into differences in trends between watersheds with different land uses and suggest that trends are controlled by erosion, transport, mixing, and deposition of sediments. These results, supported by similar trends reported for other settings and environmental media, could provide an estimate of the decadal response time of riverine systems to changes in the regulation of other persistent hydrophobic or particle-reactive contaminants.

In 1983, current data were collected by the National Oceanic and Atmospheric Administration using mechanical current meters. During 1992 through 1996, acoustic Doppler current profilers as well as mechanical current meters and tide gauges were used. These measurements not only document tides and tidal currents in San Diego Bay, but also provide independent data sets for model calibration and verification. A high resolution (100-m grid), depth-averaged, numerical hydrodynamic model has been implemented for San Diego Bay to describe essential tidal hydrodynamic processes in the bay. The model is calibrated using the 1983 data set and verified using the more recent 1992-1996 data. Discrepancies between model predictions and field data in both model calibration and verification are on the order of the magnitude of uncertainties in the field data. The calibrated and verified numerical model has been used to quantify residence time and dilution and flushing of contaminant effluent into San Diego Bay. Furthermore, the numerical model has become an important research tool in ongoing hydrodynamic and water quality studies and in guiding future field data collection programs.

A comparison of the stable-isotope signatures of spring waters, snow, snowmelt, summer (July thru September) rain, and cool season (October thru June) rain indicates that the high-intensity, short-duration summer convective storms, which contribute approximately a third of the annual precipitation to the Spring Mountains, provide only a small fraction (perhaps 10%) of the recharge to this major upland in southern Nevada, USA. Late spring snowmelt is the principal means of recharging the fractured Paleozoic-age carbonate rocks comprising the central and highest portion of the Spring Mountains. Daily discharge measurements at Peak Spring Canyon Creek during the period 1978-94 show that snowpacks were greatly enhanced during El Niño events.

From 1988 to 1992 the north-central plains of North America had a drought that was followed by a wet period that continues to the present (1997). Data on the hydrology of the Cottonwood Lake area (CWLA) collected for nearly 10 years before, and during, the recent dry and wet periods indicate that some prairie pothole wetlands served only a recharge function under all climate conditions. Transpiration from groundwater around the perimeter of groundwater discharge wetlands drew water from the wetlands by the end of summer, even during very wet years. Long-term records of a climate index (Palmer Drought Severity Index), stream discharge (Pembina River), and lake level (Devils Lake) were used to put the 17-year CWLA record into a longer term perspective. In addition, proxy records of climate determined from fossils in the sediments of Devils Lake were also used. These data indicate that the drought of 1988-92 may have been the second worst of the 20th century, but that droughts of that magnitude, and worse, were common during the past 500 years. In contrast, the present wet period may be the wettest it has been during the past 130 years, or possibly the past 500 years.

Xu, Y., Schoonen, M. A. A., Nordstrom, D. K., Cunningham, K. M., and Ball, J. W., 1998, Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: Park: I. The origin of thiosulfate in hot spring waters: Geochem. Cosmochem. Acta 62, p. 3729-3743.

Thiosulfate (S2O32-), polythionate (SxO62-), dissolved sulfide (H2S), and sulfate (SO42-) concentrations in thirty-nine alkaline and acidic springs in Yellowstone National Park (YNP) were determined. The analyses were conducted on site, using ion chromatography for thiosulfate, polythionate, and sulfate, and using colorimetry for dissolved sulfide. Thiosulfate was detected at concentrations typically less than 2 µmol/L in neutral and alkaline chloride springs with low sulfate concentrations (Cl-/SO42- > 25). The thiosulfate concentration levels are about one to two orders of magnitude lower than the concentration of dissolved sulfide in these springs. In most acid sulfate and acid sulfate-chloride springs (Cl-/SO42- < 10), thiosulfate concentrations were also typically lower than 2 µmol/L. However, in some chloride springs enriched with sulfate (Cl-/SO42- between 10 to 25), thiosulfate was found at concentrations ranging from 9 to 95 µmol/L, higher than the concentrations of dissolved sulfide in these waters. Polythionate was detected only in Cinder Pool, Norris Geyser basin, at concentrations up to 8 µmol/L, with an average S-chain-length from 4.1 to 4.9 sulfur atoms.

The results indicate that no thiosulfate occurs in the deeper parts of the hydrothermal system. Thiosulfate may form, however, from (1) hydrolysis of native sulfur by hydrothermal solutions in the shallower parts (<50 m) of the system, (2) oxidation of dissolved sulfide upon mixing of a deep hydrothermal water with aerated shallow groundwater, and (3) the oxidation of dissolved sulfide by dissolved oxygen upon discharge of the hot spring. Upon discharge of a sulfide-containing hydrothermal water, oxidation proceeds rapidly as atmospheric oxygen enters the water. The transfer of oxygen is particularly effective if the hydrothermal discharge is turbulent and has a large surface area.