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USGS2006

Geochemical patterns of arsenic-enriched ground water in fractured, crystalline bedrock, Northport, Maine, USA

High mean As concentrations of up to 26.6 ??mol/L (1990 ??g/L) occur in ground water collected from a fractured-bedrock system composed of sulfidic schist with granitic to dioritic intrusions. Sulfides in the bedrock are the primary source of the As in the ground water, but the presence of arsenopyrite in rock core retrieved from a borehole with As concentrations in the ground water barely above the detection limit of 2.0 ??mol/L, shows that there are complicating factors. Chemical analyses of water from 35 bedrock wells throughout a small watershed reveal spatial clustering of wells with high As concentrations. Stiff diagrams and box plots distinguish three distinct types; calcium-bicarbonate-dominated water with low As concentrations (CaHCO 3 type), sodium-bicarbonate-dominated water with moderately high As concentrations (NaHCO3 type), and calcium-bicarbonate-dominated water with very high As concentrations (High-As type). It is proposed that differences in recharge area and ground-water evolution, and possible bedrock composition difference are responsible for the chemical distinctions within the watershed. Lack of correlation of As concentrations with pH indicates that desorption of As is an insignificant control on As concentration. Correlations of As concentrations with Fe and redox parameters indicates that reductive dissolution of Fe(III) oxyhydroxides may play a role in the occurrence of high As concentrations in the NaHCO3 and High-As type water. The oxidation of sulfide minerals occurs within the ground-water system and is ultimately responsible for the existence of As in the ground water, but there is no correlation between As and SO4 concentrations, probably due to precipitation of Fe(III) oxyhydroxides and adsorption of As under oxidizing conditions. Crown Copyright ?? 2006 Published by Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2006

Modeling spatial and temporal variations in temperature and salinity during stratification and overturn in Dexter Pit Lake, Tuscarora, Nevada, USA

This paper examines the seasonal cycling of temperature and salinity in Dexter pit lake in arid northern Nevada, and describes an approach for modeling the physical processes that operate in such systems. The pit lake contains about 596,200 m 3 of dilute, near neutral (pHs 6.7–9) water. Profiles of temperature, conductivity, and selected element concentrations were measured almost monthly during 1999 and 2000. In winter (January–March), the pit lake was covered with ice and bottom water was warmer (5.3 °C) with higher total dissolved solids (0.298 g/L) than overlying water (3.96 °C and 0.241 g/L), suggesting inflow of warm (11.7 °C) groundwater with a higher conductivity than the lake (657 versus 126–383 μS/cm). Seasonal surface inflow due to spring snowmelt resulted in lower conductivity in the surface water (232–247 μS/cm) relative to deeper water (315–318 μS/cm). The pit lake was thermally stratified from late spring through early fall, and the water column turned over in late November (2000) or early December (1999). The pit lake is a mixture of inflowing surface water and groundwater that has subsequently been evapoconcentrated in the arid environment. Linear relationships between conductivity and major and some minor (B, Li, Sr, and U) ions indicate conservative mixing for these elements.

Nevada↗

USGS2006

Geochemical evolution of solutions derived from experimental weathering of sulfide-bearing rocks

The chemical composition of natural waters is affected by the weathering of geologic materials at or near the surface of the Earth. Laboratory weathering experiments of whole-rock sulfide rocks from the Shoe-Basin Mine (SBM) and the Pennsylvania Mine (PM) from the Peru Creek Basin, Summit County, Colorado, indicate that the mineral composition of the sulfide rocks, changes in pH, the duration of the experiment, and the formation of sorbents such as Fe and Al oxyhydroxides affect the chemical composition of the resulting solution. Carbonate minerals in the rock from SBM provide buffering capacity to the solution, contribute to increases in the pH and enhance the formation of Fe and Al oxyhydroxides, which sorb cations from solution. The final solution pH obtained in the experiments was similar to those measured in the field (i.e., 2.8 for PM and 5.0 for SBM). At PM, acidic, metal-rich mine effluent is discharged into Peru Creek where it mixes with stream water. As a result, the pH of the effluent increases causing Fe and Al oxyhydroxide and schwertmannite to precipitate. The resulting solids sorb metal cations from the water thereby improving the quality of the water in Peru Creek. ?? 2006.

Applied Geochemistry↗

USGS2006

The influence of geology and land use on arsenic in stream sediments and ground waters in New England, USA

Population statistics for As concentrations in rocks, sediments and ground water differ by geology and land use features in the New England region, USA. Significant sources of As in the surficial environment include both natural weathering of rocks and anthropogenic sources such as arsenical pesticides that were commonly applied to apple, blueberry and potato crops during the first half of the 20th century in the region. The variation of As in bedrock ground water wells has a strong positive correlation with geologic features at the geologic province, lithology group, and bedrock map unit levels. The variation of As in bedrock ground water wells also has a positive correlation with elevated stream sediment and rock As chemistry. Elevated As concentrations in bedrock wells do not correlate with past agricultural areas that used arsenical pesticides on crops. Stream sediments, which integrate both natural and anthropogenic sources, have a strong positive correlation of As concentrations with rock chemistry, geologic provinces and ground water chemistry, and a weaker positive correlation with past agricultural land use. Although correlation is not sufficient to demonstrate cause-and-effect, the statistics favor rock-based As as the dominant regional source of the element in stream sediments and ground water in New England. The distribution of bedrock geology features at the geologic province, lithology group and map unit level closely correlate with areas of elevated As in ground water, stream sediments, and rocks. ?? 2006 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2006

Mercury in coal and the impact of coal quality on mercury emissions from combustion systems

The proportion of Hg in coal feedstock that is emitted by stack gases of utility power stations is a complex function of coal chemistry and properties, combustion conditions, and the positioning and type of air pollution control devices employed. Mercury in bituminous coal is found primarily within Fe-sulfides, whereas lower rank coal tends to have a greater proportion of organic-bound Hg. Preparation of bituminous coal to reduce S generally reduces input Hg relative to in-ground concentrations, but the amount of this reduction varies according to the fraction of Hg in sulfides and the efficiency of sulfide removal. The mode of occurrence of Hg in coal does not directly affect the speciation of Hg in the combustion flue gas. However, other constituents in the coal, notably Cl and S, and the combustion characteristics of the coal, influence the species of Hg that are formed in the flue gas and enter air pollution control devices. The formation of gaseous oxidized Hg or particulate-bound Hg occurs post-combustion; these forms of Hg can be in part captured in the air pollution control devices that exist on coal-fired boilers, without modification. For a given coal type, the capture efficiency of Hg by pollution control systems varies according to type of device and the conditions of its deployment. For bituminous coal, on average, more than 60% of Hg in flue gas is captured by fabric filter (FF) and flue-gas desulfurization (FGD) systems. Key variables affecting performance for Hg control include Cl and S content of the coal, the positioning (hot side vs. cold side) of the system, and the amount of unburned C in coal ash. Knowledge of coal quality parameters and their effect on the performance of air pollution control devices allows optimization of Hg capture co-benefit.

Applied Geochemistry↗

USGS2006

Mercury in water and biomass of microbial communities in hot springs of Yellowstone National Park, USA

Ultra-clean sampling methods and approaches typically used in pristine environments were applied to quantify concentrations of Hg species in water and microbial biomass from hot springs of Yellowstone National Park, features that are geologically enriched with Hg. Microbial populations of chemically-diverse hot springs were also characterized using modern methods in molecular biology as the initial step toward ongoing work linking Hg speciation with microbial processes. Molecular methods (amplification of environmental DNA using 16S rDNA primers, cloning, denatured gradient gel electrophoresis (DGGE) screening of clone libraries, and sequencing of representative clones) were used to examine the dominant members of microbial communities in hot springs. Total Hg (THg), monomethylated Hg (MeHg), pH, temperature, and other parameters influential to Hg speciation and microbial ecology are reported for hot springs water and associated microbial mats.

Applied Geochemistry↗

USGS2006

A review of isotopic composition as an indicator of the natural and anthropogenic behavior of mercury

There are seven stable isotopes of Hg that can be fractionated as a result of inorganic and organic interactions. Important inorganic reactions involve speciation changes resulting from variations in environmental redox conditions, and phase changes resulting from variations in temperature and/or atmospheric pressure. Important organic reactions include methylation and demethylation, reactions that are bacterially mediated, and complexing with organic anions in soils. The measurement of Hg isotopes by multi-collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) is now sufficiently precise and sensitive that it is potentially possible to develop the systematics of Hg isotopic fractionation. This provides an opportunity to evaluate the utility of Hg isotopes in identifying source processes, transport mechanisms, and sinks. New values are provided for, 201Hg/198Hg, 200Hg/198Hg, 199Hg/198Hg for three standard materials (IRMM-AE639, SRM 1641c, SRM 3133) that can be used to make inter-laboratory data comparisons, and these values are tabulated with published isotopic information. Overall, the isotopic data for these standards agree to approximately 0.2???. The paper reviews Hg isotope studies that deal with hydrothermal ore deposits, sediments, coal and organic complexing. ?? 2006 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2006

Mercury methylation influenced by areas of past mercury mining in the Terlingua district, Southwest Texas, USA

Speciation and microbial transformation of Hg was studied in mine waste from abandoned Hg mines in SW Texas to evaluate the potential for methyl-Hg production and degradation in mine wastes. In mine waste samples, total Hg, ionic Hg2+, Hg0, methyl-Hg, organic C, and total S concentrations were measured, various Hg compounds were identified using thermal desorption pyrolysis, and potential rates of Hg methylation and methyl-Hg demethylation were determined using isotopic-tracer methods. These data are the first reported for Hg mines in this region. Total Hg and methyl-Hg concentrations were also determined in stream sediment collected downstream from two of the mines to evaluate transport of Hg and methylation in surrounding ecosystems. Mine waste contains total Hg and methyl-Hg concentrations as high as 19,000 ??g/g and 1500 ng/g, respectively, which are among the highest concentrations reported at Hg mines worldwide. Pyrolysis analyses show that mine waste contains variable amounts of cinnabar, metacinnabar, Hg0, and Hg sorbed onto particles. Methyl-Hg concentrations in mine waste correlate positively with ionic Hg2+, organic C, and total S, which are geochemical parameters that influence processes of Hg cycling and methylation. Net methylation rates were as high as 11,000 ng/g/day, indicating significant microbial Hg methylation at some sites, especially in samples collected inside retorts. Microbially-mediated methyl-Hg demethylation was also observed in many samples, but where both methylation and demethylation were found, the potential rate of methylation was faster. Total Hg concentrations in stream sediment samples were generally below the probable effect concentration of 1.06 ??g/g, the Hg concentration above which harmful effects are likely to be observed in sediment dwelling organisms; whereas total Hg concentrations in mine waste samples were found to exceed this concentration, although this is a sediment quality guideline and is not directly applicable to mine waste. Although total Hg and methyl-Hg concentrations are locally high in some mine waste samples, little Hg appears to be exported from these Hg mines in stream sediment primarily due to the arid climate and lack of precipitation and mine runoff in this region. ?? 2006 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2007

Effects of surface-water irrigation on sources, fluxes, and residence times of water, nitrate, and uranium in an alluvial aquifer

Effects of surface-water irrigation on an alluvial aquifer were evaluated using chemical and isotopic data including δ 2 H, δ 18 O, 3 H, δ 3 He, Ar, Ne, N 2 , δ 15 N, and 234 U/ 238 U activity ratios in a transect of nested wells in the North Platte River valley in western Nebraska, USA. The data were used to evaluate sources and fluxes of H 2 O, NO 3 - "> NO3- and U, all of which were strongly affected by irrigated agriculture. Combined results indicate that the alluvial aquifer was dominated by irrigation water that had distinctive chemical and isotopic features that were inherited from the North Platte River or acquired from agricultural soils or recharge processes. Values of δ 2 H, δ 18 O, Ar and Ne indicate that most of the ground water in the alluvial aquifer was irrigation water that was derived from the North Platte River and distributed during the growing season. The irrigation water was identified by an evaporated isotopic signature that was acquired by the river in major upstream reservoirs in Wyoming, and by relatively warm gas-equilibration temperatures related to warm-season recharge. Apparent 3 H– 3 He ages indicate that the ground water in the alluvium was stratified and mostly <30 a old, with apparent recharge rates varying widely from about 0.2 to >3.0 m/a. Age gradients and NO 3 - "> NO3- concentrations indicate that recharge occurred by a combination of focused leakage from irrigation canals (rapid local recharge, low NO 3 - "> NO3- ) and distributed infiltration beneath the irrigated agricultural fields (lower recharge, high NO 3 - "> NO3- ). Large amounts of U with relatively low 234 U/ 238 U activity ratios were present in the alluvial aquifer as a result of irrigation with U-bearing river water, and minor amounts of U with higher 234 U/ 238 U activity ratios were added locally from basal and underlying volcanic-rich sediments. Distributions of NO 3 - "> NO3- , δ 15 N [ NO 3 - ] "> δ15N[NO3-] , dissolved gases, and ground-water ages indicate that NO 3 - "> NO3- concentrations increased and δ 15 N [ NO 3 - ] "> δ15N[NO3-] values decreased in distributed recharge in the last few decades, possibly in relation to a documented increase in the agricultural use of artificial fertilizers. Canal leakage caused substantial dilution of NO 3 - "> NO3- within the alluvial aquifer, whereas denitrification occurred mainly near the bottom of the alluvium. The average residence time of the irrigation water within the aquifer was relatively short (about 9 a) and reactions such as respiration, denitrification and U exchange in the saturated zone had relatively little effect on the overall composition of the alluvial ground water in comparison to what they might have had in the absence of irrigation recharge.

Nebraska↗

USGS2007

A review of land–sea coupling by groundwater discharge of nitrogen to New England estuaries: Mechanisms and effects

Hydrologists have long been concerned with the interface of groundwater flow into estuaries, but not until the end of the last century did other disciplines realize the major role played by groundwater transport of nutrients to estuaries. Mass balance and stable isotopic data suggest that land-derived NO 3 , NH 4 , and dissolved organic N do enter estuaries in amounts likely to affect the function of the receiving ecosystem. Because of increasing human occupancy of the coastal zone, the nutrient loads borne by groundwater have increased in recent decades, in spite of substantial interception of nutrients within the land and aquifer components of watersheds. Groundwater-borne nutrient loads have increased the N content of receiving estuaries, increased phytoplankton and macroalgal production and biomass, decreased the area of seagrasses, and created a cascade of associated ecological changes. This linkage between land use and eutrophication of estuaries occurs in spite of mechanisms, including uptake of land-derived N by riparian vegetation and fringing wetlands, “unloading” by rapid water removal, and direct N inputs to estuaries, that tend to uncouple the effects of land use on receiving estuaries. It can be expected that as human activity on coastal watersheds continues to increase, the role of groundwater-borne nutrients to the receiving estuary will also increase.

New England↗

USGS2007

Progressive oxidation of pyrite in five bituminous coal samples: An As XANES and 57 Fe Mössbauer spectroscopic study

Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period of 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32–1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26–0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O 2 atmosphere; (3) room atmosphere (relative humidity &sim;20–60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and 57 Fe Mössbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. 57 Fe Mössbauer spectroscopy also shows a much greater proportion of Fe 3+ forms (jarosite, Fe 3+ sulfate, FeOOH) for samples stored under wet conditions, but much less difference among samples stored under dry conditions in different atmospheres. The air-wet experiments show evidence of pyrite re-precipitation from soluble ferric sulfates, with As retention in the jarosite phase. Extents of As and Fe oxidation were similar for samples having differing As substitution in pyrite, suggesting that environmental conditions outweigh the composition and amount of pyrite as factors influencing the oxidation rate of Fe sulfides in coal.

Applied Geochemistry↗

USGS2007

Assessing the concentration, speciation, and toxicity of dissolved metals during mixing of acid-mine drainage and ambient river water downstream of the Elizabeth Copper Mine, Vermont, USA

The authors determine the composition of a river that is impacted by acid-mine drainage, evaluate dominant physical and geochemical processes controlling the composition, and assess dissolved metal speciation and toxicity using a combination of laboratory, field and modeling studies. Values of pH increase from 3.3 to 7.6 and the sum of dissolved base metal (Cd + Co + Cu + Ni + Pb + Zn) concentrations decreases from 6270 to 100 μg/L in the dynamic mixing and reaction zone that is downstream of the river’s confluence with acid-mine drainage. Mixing diagrams and PHREEQC calculations indicate that mixing and dilution affect the concentrations of all dissolved elements in the reach, and are the dominant processes controlling dissolved Ca, K, Li, Mn and SO 4 concentrations. Additionally, dissolved Al and Fe concentrations decrease due to mineral precipitation (gibbsite, schwertmannite and ferrihydrite), whereas dissolved concentrations of Cd, Co, Cu, Ni, Pb and Zn decrease due to adsorption onto newly formed Fe precipitates.

Vermont↗

USGS2007

Formation of mixed Al-Fe colloidal sorbent and dissolved-colloidal partitioning of Cu and Zn in the Cement Creek - Animas River Confluence, Silverton, Colorado

Transport and chemical transformations of dissolved and colloidal Al, Fe, Cu and Zn were studied by detailed sampling in the mixing zone downstream from the confluence of Cement Creek (pH 4.1) with the Animas River (pH 7.6). Complete mixing resulted in circumneutral pH in the downstream reach of the 1300 m study area. All four metals were transported through this mixing zone without significant losses to the streambed, and they exhibited transformations from dissolved to colloidal forms to varying degrees during the mixing process. Nearly all of the Al formed colloidal hydrous Al oxides (HAO) as pH increased (4.8–6.5), whereas colloidal hydrous Fe oxides (HFO) were supplied by Cement Creek as well as formed in the mixing zone primarily at higher pH (>6.5). The short travel time through the mixing zone (approx. 40 min) and pH limited the formation of HFO from dissolved Fe 2+ supplied by Cement Creek. Although the proportions of HAO and HFO varied as the streams mixed, the colloidal sorbent typically was enriched in HAO relative to HFO by a factor of 1.5–2.1 (by mole) in the pH range where dissolved-to-colloidal partitioning of Cu and Zn was observed. Model simulations of sorption by HFO (alone) greatly underestimated the dissolved-to-colloidal partitioning of Zn. Previous studies have shown that HAO–HFO mixtures can sorb greater amounts of Zn than HFO alone, but the high Zn-to-sorbent ratio in this mixing zone could also account for greater partitioning. In contrast to Zn, comparisons with model simulations did not show that Cu sorption was greater than that for HFO alone, and also indicated that sorption was possibly less than what would be expected for a non-interactive mixture of these two sorbents. These field results for Cu, however, might be influenced by (organic) complexation or other factors in this natural system. Laboratory mixing experiments using natural source waters (upstream of the confluence) showed that the presence of HFO in the mixed sorbent resulted in greater Cu partitioning than for HAO alone, and that the effect was greater with increasing (mole fraction) HFO. This was consistent with field results that showed greater Cu sorption when additional HFO was formed in the downstream reach of the mixing zone. Further research is needed to identify the significance of surface-related mechanisms specific to HAO–HFO mixtures that could affect the partitioning of Cu in natural systems.

Colorado↗

USGS2007

A critical review of three methods used for the measurement of mercury (Hg2+)-dissolved organic matter stability constants

Three experimental techniques - ion exchange, liquid-liquid extraction with competitive ligand exchange, and solid-phase extraction with competitive ligand exchange (CLE-SPE) - were evaluated as methods for determining conditional stability constants (K) for the binding of mercury (Hg2+) to dissolved organic matter (DOM). To determine the utility of a given method to measure stability constants at environmentally relevant experimental conditions, experimental results should meet three criteria: (1) the data must be experimentally valid, in that they were acquired under conditions that meet all the requirements of the experimental method, (2) the Hg:DOM ratio should be determined and it should fall within levels that are consistent with environmental conditions, and (3) the stability constants must fall within the detection window of the method. The ion exchange method was found to be limited by its detection window, which constrains the method to stability constants with log K values less than about 14. The liquid-liquid extraction method was found to be complicated by the ability of Hg-DOM complexes to partition into the organic phase. The CLE-SPE method was found to be the most suitable of these methods for the measurement of Hg-DOM stability constants. Stability constants for DOM isolates measured using the CLE-SPE method at environmentally relevant Hg:DOM ratios were log K = 25-30 (M-1). These values are consistent with the strong Hg2+ binding expected for reduced S-containing binding sites.

Applied Geochemistry↗

USGS2007

A simulation-based approach for estimating premining water quality: Red Mountain Creek, Colorado

Regulatory agencies are often charged with the task of setting site-specific numeric water quality standards for impaired streams. This task is particularly difficult for streams draining highly mineralized watersheds with past mining activity. Baseline water quality data obtained prior to mining are often non-existent and application of generic water quality standards developed for unmineralized watersheds is suspect given the geology of most watersheds affected by mining. Various approaches have been used to estimate premining conditions, but none of the existing approaches rigorously consider the physical and geochemical processes that ultimately determine instream water quality. An approach based on simulation modeling is therefore proposed herein. The approach utilizes synoptic data that provide spatially-detailed profiles of concentration, streamflow, and constituent load along the study reach. This field data set is used to calibrate a reactive stream transport model that considers the suite of physical and geochemical processes that affect constituent concentrations during instream transport. A key input to the model is the quality and quantity of waters entering the study reach. This input is based on chemical analyses available from synoptic sampling and observed increases in streamflow along the study reach. Given the calibrated model, additional simulations are conducted to estimate premining conditions. In these simulations, the chemistry of mining-affected sources is replaced with the chemistry of waters that are thought to be unaffected by mining (proximal, premining analogues). The resultant simulations provide estimates of premining water quality that reflect both the reduced loads that were present prior to mining and the processes that affect these loads as they are transported downstream. This simulation-based approach is demonstrated using data from Red Mountain Creek, Colorado, a small stream draining a heavily-mined watershed. Model application to the premining problem for Red Mountain Creek is based on limited field reconnaissance and chemical analyses; additional field work and analyses may be needed to develop definitive, quantitative estimates of premining water quality.

Colorado↗

USGS2007

Fate and identification of oil-brine contamination in different hydrogeologic settings

Past disposal of oil-field brine at the surface has caused substantial contamination of water resources in Kansas. Natural saline water occurs in and discharges from Permian bedrock in parts of the state, and other anthropogenic sources of saline water exist, requiring clear identification of different sources. Time-series analysis of Cl- concentration and streamflow relative to pre-contamination contents, and end-member mixing plots, especially for Br- and Cl-, are practical methods for source differentiation and quantification. Although regulations preventing escape of saltwater from oil wells were first passed in Kansas in 1935, much oil and gas brine was disposed on the surface through the 1940s. Hydrogeologic characteristics of the areas with past surface disposal of oil brine differ appreciably and result in large differences in the ratio of saltwater transported in streams or ground water. Much of the brine disposed during the 1910s to 1940s in an area of silty clay soils overlying shale and limestone bedrock in south-central Kansas soon ran off or was flushed from the surface by rain into streams. Chloride concentration in the rivers draining this area often exceeded 1000 mg/L after the start of oil production up to the 1950s. Chloride content in the rivers then generally declined to about 100 mg/L or less in recent low flows. Oil brine was also disposed in surface ponds overlying the unconsolidated High Plains aquifer in south-central Kansas from the latter 1920s into the 1940s. Most of the surface-disposed brine infiltrated to the underlying aquifer. Where the High Plains aquifer is thin, saltwater has migrated along the top of clay layers or the underlying shaly bedrock and either discharged into small streams or flowed into thicker parts of the aquifer. Where the aquifer is thick, surface-disposed oil brine moved downward until reaching clay lenses, migrated latterly to the edge of the clay, and again moved downward if still dense enough. Water-level declines from pumping have increased the lateral migration rate of the saltwater contamination in the aquifer towards water-supply wells. The period of flushing most of the surface-disposed saltwater from the area of shale and limestone bedrock is on the order of many decades but is at least many centuries for the deeper parts of the High Plains aquifer. ?? 2007 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2007

Hydrology and subsurface transport of oil-field brine at the U.S. Geological Survey OSPER site "A", Osage County, Oklahoma

Spillage and improper disposal of saline produced water from oil wells has caused environmental damage at thousands of sites in the United States. In order to improve understanding of the fate and transport of contaminants at these sites, the U.S. Geological Survey carried out multidisciplinary investigations at two oil production sites near Skiatook Lake, Oklahoma. As a part of this effort, the hydrology and subsurface transport of brine at OSPER site “A”, a tank battery and pit complex that was abandoned in 1973, was investigated. Based on data from 41 new boreholes that were cored and completed with monitoring wells, a large (∼200 m × 200 m × 20 m) plume of saline ground water was mapped. The main dissolved species are Na and Cl, with TDS in the plume ranging as high as 30,000 mg/L. Analysis of the high barometric efficiency of the wells indicated a confined aquifer response. Well-slug tests indicated the hydraulic conductivity is low (0.3–7.0 cm/day). Simplified flow and transport modeling supports the following conceptual model: (1) prior to the produced water releases, recharge was generally low (∼1 cm/a); (2) in ∼60 a of oil production enough saline produced water in pits leaked into the subsurface to create the plume; (3) following abandonment of the site in 1973 and filling of Skiatook Reservoir in the mid-1980s, recharge and lateral flow of water through the plume returned to low values; (4) as a result, spreading of the brine plume caused by mixing with fresh ground water recharge, as well as natural attenuation, are very slow.

Oklahoma↗

USGS2007

Fate and groundwater impacts of produced water releases at OSPER "B" site, Osage County, Oklahoma

For the last 5 a, the authors have been investigating the transport, fate, natural attenuation and ecosystem impacts of inorganic and organic compounds in releases of produced water and associated hydrocarbons at the Osage-Skiatook Petroleum Environmental Research (OSPER) “A” and “B” sites, located in NE Oklahoma. Approximately 1.0 ha of land at OSPER “B”, located within the active Branstetter lease, is visibly affected by salt scarring, tree kills, soil salinization, and brine and petroleum contamination. Site “B” includes an active production tank battery and adjacent large brine pit, two injection well sites, one with an adjacent small pit, and an abandoned brine pit and tank battery site. Oil production in this lease started in 1938, and currently there are 10 wells that produce 0.2–0.5 m 3 /d (1–3 bbl/d) oil, and 8–16 m 3 /d (50–100 bbl/d) brine. Geochemical data from nearby oil wells show that the produced water source is a Na–Ca–Cl brine (∼150,000 mg/L TDS), with high Mg, but low SO 4 and dissolved organic concentrations. Groundwater impacts are being investigated by detailed chemical analyses of water from repeated sampling of 41 boreholes, 1–71 m deep. The most important results at OSPER “B” are: (1) significant amounts of produced water from the two active brine pits percolate into the surficial rocks and flow towards the adjacent Skiatook reservoir, but only minor amounts of liquid petroleum leave the brine pits; (2) produced-water brine and minor dissolved organics have penetrated the thick (3–7 m) shale and siltstone units resulting in the formation of three interconnected plumes of high-salinity water (5000–30,000 mg/L TDS) that extend towards the Skiatook reservoir from the two active and one abandoned brine pits; and (3) groundwater from the deep section of only one well, BR-01 located 330 m upslope and west of the site, appear not to be impacted by petroleum operations.

Oklahoma↗