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Modeling and management of pit lake water chemistry 2: Case studies

Pit lakes, a common product of open pit mining techniques, may become long-term, post-mining environmental risks or long-term, post-mining water resources depending upon management decisions. This study reviews two published pit lake modeling studies and one pit lake monitoring program in order to increase the transparency of approaches used in pit lake prediction and management. The first model is a two-year limnological simulation of the existing Dexter pit lake, Nevada, USA that accurately modeled temperature profiles, salinity profiles, and turnover events observed between 1999 and 2000. The second model is a 55-year prediction of a future pit lake in the Martha Mine, New Zealand that identified the need for additional mitigation and evaluated potential effects of cost-effective mitigation options. The final study reviews eight years of monitoring data collected from the Berkeley pit lake, Montana, USA, from 2004 to 2012. This study identifies changes in the physical limnology and water quality of the pit lake that resulted from metal recovery operations, and highlights the value of monitoring programs in general. Whereas these pit lakes are different in many ways, the management tools discussed herein maximized the value and understanding of the post-mining resources.

Applied Geochemistry↗

Fate of injected CO2 in the Wilcox Group, Louisiana, Gulf Coast Basin: Chemical and isotopic tracers of microbial–brine–rock–CO2 interactions

The “2800’ sandstone” of the Olla oil field is an oil and gas-producing reservoir in a coal-bearing interval of the Paleocene–Eocene Wilcox Group in north-central Louisiana, USA. In the 1980s, this producing unit was flooded with CO 2 in an enhanced oil recovery (EOR) project, leaving ∼30% of the injected CO 2 in the 2800’ sandstone post-injection. This study utilizes isotopic and geochemical tracers from co-produced natural gas, oil and brine to determine the fate of the injected CO 2 , including the possibility of enhanced microbial conversion of CO 2 to CH 4 via methanogenesis. Stable carbon isotopes of CO 2 , CH 4 and DIC, together with mol% CO 2 show that 4 out of 17 wells sampled in the 2800’ sandstone are still producing injected CO 2 . The dominant fate of the injected CO 2 appears to be dissolution in formation fluids and gas-phase trapping. There is some isotopic and geochemical evidence for enhanced microbial methanogenesis in 2 samples; however, the CO 2 spread unevenly throughout the reservoir, and thus cannot explain the elevated indicators for methanogenesis observed across the entire field. Vertical migration out of the target 2800’ sandstone reservoir is also apparent in 3 samples located stratigraphically above the target sand. Reservoirs comparable to the 2800’ sandstone, located along a 90-km transect, were also sampled to investigate regional trends in gas composition, brine chemistry and microbial activity. Microbial methane, likely sourced from biodegradation of organic substrates within the formation, was found in all oil fields sampled, while indicators of methanogenesis (e.g. high alkalinity, δ 13 C-CO 2 and δ 13 C-DIC values) and oxidation of propane were greatest in the Olla Field, likely due to its more ideal environmental conditions (i.e. suitable range of pH, temperature, salinity, sulfate and iron concentrations).

Louisiana↗

Alpha-emitting isotopes and chromium in a coastal California aquifer

The unadjusted 72-h gross alpha activities in water from two wells completed in marine and alluvial deposits in a coastal southern California aquifer 40 km north of San Diego were 15 and 25 picoCuries per liter (pCi/L). Although activities were below the Maximum Contaminant Level (MCL) of 15 pCi/L, when adjusted for uranium activity; there is concern that new wells in the area may exceed MCLs, or that future regulations may limit water use from the wells. Coupled well-bore flow and depth-dependent water-quality data collected from the wells in 2011 (with analyses for isotopes within the uranium, actinium, and thorium decay-chains) show gross alpha activity in marine deposits is associated with decay of naturally-occurring 238 U and its daughter 234 U. Radon activities in marine deposits were as high as 2230 pCi/L. In contrast, gross alpha activities in overlying alluvium within the Piedra de Lumbre watershed, eroded from the nearby San Onofre Hills, were associated with decay of 232 Th, including its daughter 224 Ra. Radon activities in alluvium from Piedra de Lumbre of 450 pCi/L were lower than in marine deposits. Chromium VI concentrations in marine deposits were less than the California MCL of 10 μg/L (effective July 1, 2014) but δ 53 Cr compositions were near zero and within reported ranges for anthropogenic chromium. Alluvial deposits from the nearby Las Flores watershed, which drains a larger area having diverse geology, has low alpha activities and chromium as a result of geologic and geochemical conditions and may be more promising for future water-supply development.

California↗

Using lead isotopes and trace element records from two contrasting Lake Tanganyika sediment cores to assess watershed – Lake exchange

Lead isotopic and trace element records of two contrasting sediment cores were examined to reconstruct historic, industrial contaminant inputs to Lake Tanganyika, Africa. Observed fluxes of Co, Cu, Mn, Ni, Pb, and Zn in age-dated sediments collected from the lake varied both spatially and temporally over the past two to four centuries. The fluxes of trace elements were lower (up to 10-fold) at a mid-lake site (MC1) than at a nearshore site (LT-98-58), which is directly downstream from the Kahama and Nyasanga River watersheds and adjacent to the relatively pristine Gombe Stream National Park. Trace element fluxes at that nearshore site did not measurably change over the last two centuries (1815&ndash;1998), while the distal, mid-lake site exhibited substantial changes in the fluxes of trace elements &ndash; likely caused by changes in land use &ndash; over that period. For example, the flux of Pb increased by &sim;300% from 1871 to 1991. That apparent accelerated weathering and detrital mobilization of lithogenic trace elements was further evidenced by (i) positive correlations (r = 0.77&ndash;0.99, p < 0.05) between the fluxes of Co, Cu, Mn, Ni, Pb, and Zn and those of iron (Fe) at both sites, (ii) positive correlations (r = 0.82&ndash;0.98, p < 0.01, n = 9) between the fluxes of elements (Al, Co, Cu, Fe, Mn, Ni, Pb, and Zn) and the mass accumulation rates at the offshore site, (iii) the low enrichment factors (EF < 5) of those trace elements, and (iv) the temporal consistencies of the isotopic composition of Pb in the sediment. These measurements indicate that accelerated weathering, rather than industrialization, accounts for most of the increases in trace element fluxes to Lake Tanganyika in spite of the development of mining and smelting operations within the lake&rsquo;s watershed over the past century. The data also indicate that the mid-lake site is a much more sensitive and useful recorder of environmental changes than the nearshore site. Furthermore, the lead isotopic compositions of sediment at the sites differed spatially, indicating that the Pb (and other trace elements by association) originated from different natural sources at the two locations.

Lake Tanganyika↗

A modified procedure for mixture-model clustering of regional geochemical data

A modified procedure is proposed for mixture-model clustering of regional-scale geochemical data. The key modification is the robust principal component transformation of the isometric log-ratio transforms of the element concentrations. This principal component transformation and the associated dimension reduction are applied before the data are clustered. The principal advantage of this modification is that it significantly improves the stability of the clustering. The principal disadvantage is that it requires subjective selection of the number of clusters and the number of principal components. To evaluate the efficacy of this modified procedure, it is applied to soil geochemical data that comprise 959 samples from the state of Colorado (USA) for which the concentrations of 44 elements are measured. The distributions of element concentrations that are derived from the mixture model and from the field samples are similar, indicating that the mixture model is a suitable representation of the transformed geochemical data. Each cluster and the associated distributions of the element concentrations are related to specific geologic and anthropogenic features. In this way, mixture model clustering facilitates interpretation of the regional geochemical data.

Colorado↗

BET surface area distributions in polar stream sediments: Implications for silicate weathering in a cold-arid environment

BET surface area values are critical for quantifying the amount of potentially reactive sediments available for chemical weathering and ultimately, prediction of silicate weathering fluxes. BET surface area values of fine-grained (<62.5 &mu;m) sediment from the hyporheic zone of polar glacial streams in the McMurdo Dry Valleys, Antarctica (Wright and Taylor Valleys) exhibit a wide range (2.5&ndash;70.6 m 2 /g) of surface area values. Samples from one (Delta Stream, Taylor Valley) of the four sampled stream transects exhibit high values (up to 70.6 m 2 /g), which greatly exceed surface area values from three temperate proglacial streams (0.3&ndash;12.1 m 2 /g). Only Clark stream in Wright Valley exhibits a robust trend with distance, wherein surface area systematically decreases (and particle size increases) in the mud fraction downstream, interpreted to reflect rapid dissolution processes in the weathering environment. The remaining transects exhibit a range in variability in surface area distributions along the length of the channel, likely related to variations in eolian input to exposed channel beds, adjacent snow drifts, and to glacier surfaces, where dust is trapped and subsequently liberated during summer melting. Additionally, variations in stream discharge rate, which mobilizes sediment in pulses and influences water:rock ratios, the origin and nature of the underlying drift material, and the contribution of organic acids may play significant roles in the production and mobilization of high-surface area sediment. This study highlights the presence of sediments with high surface area in cold-based glacier systems, which influences models of chemical denudation rates and the impact of glacial systems on the global carbon cycle.

Applied Geochemistry↗

Evaluation of selected static methods used to estimate element mobility, acid-generating and acid-neutralizing potentials associated with geologically diverse mining wastes

A comparison study of selected static leaching and acid&ndash;base accounting (ABA) methods using a mineralogically diverse set of 12 modern-style, metal mine waste samples was undertaken to understand the relative performance of the various tests. To complement this study, in-depth mineralogical studies were conducted in order to elucidate the relationships between sample mineralogy, weathering features, and leachate and ABA characteristics. In part one of the study, splits of the samples were leached using six commonly used leaching tests including paste pH, the U.S. Geological Survey (USGS) Field Leach Test (FLT) (both 5-min and 18-h agitation), the U.S. Environmental Protection Agency (USEPA) Method 1312 SPLP (both leachate pH 4.2 and leachate pH 5.0), and the USEPA Method 1311 TCLP (leachate pH 4.9). Leachate geochemical trends were compared in order to assess differences, if any, produced by the various leaching procedures. Results showed that the FLT (5-min agitation) was just as effective as the 18-h leaching tests in revealing the leachate geochemical characteristics of the samples. Leaching results also showed that the TCLP leaching test produces inconsistent results when compared to results produced from the other leaching tests. In part two of the study, the ABA was determined on splits of the samples using both well-established traditional static testing methods and a relatively quick, simplified net acid&ndash;base accounting (NABA) procedure. Results showed that the traditional methods, while time consuming, provide the most in-depth data on both the acid generating, and acid neutralizing tendencies of the samples. However, the simplified NABA method provided a relatively fast, effective estimation of the net acid&ndash;base account of the samples. Overall, this study showed that while most of the well-established methods are useful and effective, the use of a simplified leaching test and the NABA acid&ndash;base accounting method provide investigators fast, quantitative tools that can be used to provide rapid, reliable information about the leachability of metals and other constituents of concern, and the acid-generating potential of metal mining waste.

Applied Geochemistry↗

Baseline and premining geochemical characterization of mined sites

A rational goal for environmental restoration of new, active, or inactive mine sites would be ‘natural background’ or the environmental conditions that existed before any mining activities or other related anthropogenic activities. In a strictly technical sense, there is no such thing as natural background (or entirely non-anthropogenic) existing today because there is no part of the planet earth that has not had at least some chemical disturbance from anthropogenic activities. Hence, the terms ‘baseline’ and ‘pre-mining’ are preferred to describe these conditions. Baseline conditions are those that existed at the time of the characterization which could be pre-mining, during mining, or post-mining. Protocols for geochemically characterizing pre-mining conditions are not well-documented for sites already mined but there are two approaches that seem most direct and least ambiguous. One is characterization of analog sites along with judicious application of geochemical modeling. The other is reactive-transport modeling (based on careful synoptic sampling with tracer-injection) and subtracting inputs from known mining and mineral processing. Several examples of acidic drainage are described from around the world documenting the range of water compositions produced from pyrite oxidation in the absence of mining. These analog sites provide insight to the processes forming mineralized waters in areas untouched by mining. Natural analog water-chemistry data is compared with the higher metal concentrations, metal fluxes, and weathering rates found in mined areas in the few places where comparisons are possible. The differences are generally 1–3 orders of magnitude higher for acid mine drainage.

Applied Geochemistry↗

Comparing activated alumina with indigenous laterite and bauxite as potential sorbents for removing fluoride from drinking water in Ghana

Fluoride is considered beneficial to teeth and bones when consumed in low concentrations, but at elevated concentrations it can cause dental and skeletal fluorosis. Most fluoride-related health problems occur in poor, rural communities of the developing world where groundwater fluoride concentrations are high and the primary sources of drinking water are from community hand-pump borehole drilled wells. One solution to drinking high fluoride water is to attach a simple de-fluoridation filter to the hand-pump; and indigenous materials have been recommended as low-cost sorbents for use in these filters. In an effort to develop an effective, inexpensive, and low-maintenance de-fluoridation filter for a high fluoride region in rural northern Ghana, this study conducted batch fluoride adsorption experiments and potentiometric titrations to investigate the effectiveness of indigenous laterite and bauxite as sorbents for fluoride removal. It also determined the physical and chemical properties of each sorbent. Their properties and the experimental results, including fluoride adsorption capacity, were then compared to those of activated alumina, which has been identified as a good sorbent for removing fluoride from drinking water. The results indicate that, of the three sorbents, bauxite has the highest fluoride adsorption capacity per unit area, but is limited by a low specific surface area. When considering fluoride adsorption per unit weight, activated alumina has the highest fluoride adsorption capacity because of its high specific surface area. Activated alumina also adsorbs fluoride well in a wider pH range than bauxite, and particularly laterite. The differences in adsorption capacity are largely due to surface area, pore size, and mineralogy of the sorbent.

Applied Geochemistry↗

Hydrogeochemistry and microbiology of mine drainage: An update

The extraction of mineral resources requires access through underground workings, or open pit operations, or through drillholes for solution mining. Additionally, mineral processing can generate large quantities of waste, including mill tailings, waste rock and refinery wastes, heap leach pads, and slag. Thus, through mining and mineral processing activities, large surface areas of sulfide minerals can be exposed to oxygen, water, and microbes, resulting in accelerated oxidation of sulfide and other minerals and the potential for the generation of low-quality drainage. The oxidation of sulfide minerals in mine wastes is accelerated by microbial catalysis of the oxidation of aqueous ferrous iron and sulfide. These reactions, particularly when combined with evaporation, can lead to extremely acidic drainage and very high concentrations of dissolved constituents. Although acid mine drainage is the most prevalent and damaging environmental concern associated with mining activities, generation of saline, basic and neutral drainage containing elevated concentrations of dissolved metals, non-metals, and metalloids has recently been recognized as a potential environmental concern. Acid neutralization reactions through the dissolution of carbonate, hydroxide, and silicate minerals and formation of secondary aluminum and ferric hydroxide phases can moderate the effects of acid generation and enhance the formation of secondary hydrated iron and aluminum minerals which may lessen the concentration of dissolved metals. Numerical models provide powerful tools for assessing impacts of these reactions on water quality.

Applied Geochemistry↗

Monitoring, field experiments, and geochemical modeling of Fe(II) oxidation kinetics in a stream dominated by net-alkaline coal-mine drainage, Pennsylvania, USA

Watershed-scale monitoring, field aeration experiments, and geochemical equilibrium and kinetic modeling were conducted to evaluate interdependent changes in pH, dissolved CO 2 , O 2 , and Fe(II) concentrations that typically take place downstream of net-alkaline, circumneutral coal-mine drainage (CMD) outfalls and during aerobic treatment of such CMD. The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO 2 outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law &minus;d[Fe(II)]/d t = k 1 &middot;[O 2 ]&middot;[H + ] &minus; 2 &middot;[Fe(II)] that indicates an increase in pH by 1 unit at pH 5&ndash;8 and at constant dissolved O 2 (DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant ( k 1 &prime;) of 0.5&ndash;1.7 times the reference value of k 1 = 3 &times; 10 &minus;12 mol/L/min (for pH 5&ndash;8 and 20 &deg;C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO 2 outgassing and O 2 ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the model results for Fe(II) or pH. In contrast, the model results for pH and Fe(II) were sensitive to the CO 2 mass transfer rate constant ( k L , CO2 a). The value of k L , CO2 a estimated for the stream (0.010 min &minus;1 ) was within the range for the batch aeration experiments (0&ndash;0.033 min &minus;1 ). These results indicate that the abiotic homogeneous Fe(II) oxidation rate law, with adjustments for variations in temperature and CO 2 outgassing rate, may be applied to predict changes in aqueous iron and pH for net-alkaline, ferruginous waters within a stream (natural conditions) or a CMD treatment system (engineered conditions).

Pennsylvania↗

Priority pollutants and associated constituents in untreated and treated discharges from coal mining or processing facilities in Pennsylvania, USA

Clean sampling and analysis procedures were used to quantify more than 70 inorganic constituents, including 35 potentially toxic or hazardous constituents, organic carbon, and other characteristics of untreated (influent) and treated (effluent) coal-mine discharges (CMD) at 38 permitted coal-mining or coal-processing facilities in the bituminous coalfield and 4 facilities in the anthracite coalfield of Pennsylvania. Of the 42 facilities sampled during 2011, 26 were surface mines, 11 were underground mines, and 5 were coal refuse disposal operations. Treatment of CMD with caustic soda (NaOH), lime (CaO or Ca(OH) 2 ), flocculent, or limestone was ongoing at 21%, 40%, 6%, and 4% of the facilities, respectively; no chemicals were added at the remaining facilities. All facilities with CMD treatment incorporated structures for active or passive aeration and settling of metal-rich precipitate. The untreated influent samples had wide ranges of pH (2.8&ndash;7.6), hot acidity (&minus;600 to 8000 mg/L as CaCO 3 ), specific conductance (SC; 253&ndash;13,000 &mu;S/cm), total dissolved solids (TDS; 168&ndash;18,100 mg/L), and associated dissolved (<0.45-&mu;m pore-size filter) constituents, including SO 4 (14.7&ndash;10,700 mg/L), Fe (<0.01 to 4100 mg/L), Mn (0.02&ndash;136 mg/L), Al (<0.01 to 128 mg/L), and Zn (<0.003 to 18.8 mg/L). Concentrations of Ag (<1 &mu;g/L), Hg (<1 &mu;g/L), Sn (<0.5 &mu;g/L), and CN (<0.01 mg/L) were below detection limits. Only one influent sample met permitted mine effluent (PME) limits plus dissolved-constituent criteria maximum concentration (CMC) thresholds for the protection of freshwater aquatic organisms. The pH of the treated effluent samples ranged from 5.5 to 11.9 and was greater than or equal to the pH of the corresponding influent at all sites. All the effluent samples met CMC levels for dissolved concentrations of Ag, As, Ba, Cd, Cl, Cr, Pb, Ni, Sb, Se, Tl, V, NH 3 , NO 2 , NO 3 , and CN; however, nine violated one or more of the PME limits for pH (<6, n = 1), net acidity (>0, n = 3), Fe (>7 mg/L, n = 1), or Mn (>5 mg/L, n = 8), plus one or more exceeded CMC levels for Al (>0.75 mg/L, n = 2), Co (>95 &mu;g/L, n = 5), Zn (>307 &mu;g/L, n = 1), Cu (>7.4 &mu;g/L, n = 1), or Se (>12.8 &mu;g/L, n = 3). Although CMC exceedances for Co and Zn were attributed to samples also violating the PME limit for pH or Mn, the samples that exceeded the CMC for Al, Cu, or Se met applicable PME limits for pH, Fe, and Mn. Furthermore, many of the pH-compliant effluents did not meet reference criteria for SO 4 and related measures of ionic strength, including TDS, SC, and osmotic pressure. The Wilcoxon matched-pair signed-ranks statistic was used to test if the overall difference between the effluent and influent pairs was equal to zero. Constituents that statistically were the same for effluent and influent ( p > 0.05) included flow rate, SC, osmotic pressure, hardness, alkalinity, total organic carbon (TOC), K, Cl, NO 3 , PO 4 , Sb, Sr, Br, Se, Mo, and V. Although temperature, dissolved oxygen, pH, Ca, and Na were greater in the effluent than the influent, most constituents decreased as a result of treatment, including TDS, acidity, SO 4 , Al, Fe, Mn, Mg, As, Ba, Be, Cd, Cr, Co, Cu, F, Pb, Ni, NH 3 , Tl, Ti, U, Zn, Zr, total phenols, total inorganic carbon (TIC), biological oxygen demand (BOD), and chemical oxygen demand (COD). Nevertheless, some constituents that decreased, such as SO 4 , still did not meet reference criteria. Findings from this study suggest that typical chemical or aerobic treatment of CMD to pH > 6 with removal of Fe to <7 mg/L and Mn to <5 mg/L may provide a reasonable measure of protection for aquatic life from priority pollutant metals and other toxic or hazardous constituents in effluent but may not be effective for achieving permissible or background levels for TDS, SC, osmotic pressure, or concentrations of SO 4 and some other pollutants, including Se, Br, and Cl, if present.

Pennsylvania↗

Hydrogeochemical effects of a bulkhead in the Dinero mine tunnel, Sugar Loaf mining district, near Leadville, Colorado

The Dinero mine drainage tunnel is an abandoned, draining mine adit near Leadville, Colorado, that has an adverse effect on downstream water quality and aquatic life. In 2009, a bulkhead was constructed (creating a mine pool and increasing water-table elevations behind the tunnel) to limit drainage from the tunnel and improve downstream water quality. The goal of this study was to document changes to hydrology and water quality resulting from bulkhead emplacement, and to understand post-bulkhead changes in source water and geochemical processes that control mine-tunnel discharge and water quality. Comparison of pre-and post-bulkhead hydrology and water quality indicated that tunnel discharge and zinc and manganese loads decreased by up to 97 percent at the portal of Dinero tunnel and at two downstream sites (LF-537 and LF-580). However, some water-quality problems persisted at LF-537 and LF-580 during high-flow events and years, indicating the effects of the remaining mine waste in the area. In contrast, post-bulkhead water quality degraded at three upstream stream sites and a draining mine tunnel (Nelson tunnel). Water-quality degradation in the streams likely occurred from increased contributions of mine-pool groundwater to the streams. In contrast, water-quality degradation in the Nelson tunnel was likely from flow of mine-pool water along a vein that connects the Nelson tunnel to mine workings behind the Dinero tunnel bulkhead. Principal components analysis, mixing analysis, and inverse geochemical modeling using PHREEQC indicated that mixing and geochemical reactions (carbonate dissolution during acid weathering, precipitation of goethite and birnessite, and sorption of zinc) between three end-member water types generally explain the pre-and post-bulkhead water composition at the Dinero and Nelson tunnels. The three end members were (1) a relatively dilute groundwater having low sulfate and trace element concentrations; (2) mine pool water, and (3) water that flowed from a structure in front of the bulkhead after bulkhead emplacement. Both (2) and (3) had high sulfate and trace element concentrations. These results indicate how analysis of monitoring information can be used to understand hydrogeochemical changes resulting from bulkhead emplacement. This understanding, in turn, can help inform future decisions on the disposition of the remaining mine waste and water-quality problems in the area.

Colorado↗

Stable-isotope and solute-chemistry approaches to flow characterization in a forested tropical watershed, Luquillo Mountains, Puerto Rico

The prospect of changing climate has led to uncertainty about the resilience of forested mountain watersheds in the tropics. In watersheds where frequent, high rainfall provides ample runoff, we often lack understanding of how the system will respond under conditions of decreased rainfall or drought. Factors that govern water supply, such as recharge rates and groundwater storage capacity, may be poorly quantified. This paper describes 8-year data sets of water stable isotope composition ( δ 2 H and δ 18 O) of precipitation (4 sites) and a stream (1 site), and four contemporaneous stream sample sets of solute chemistry and isotopes, used to investigate watershed response to precipitation inputs in the 1780-ha Río Mameyes basin in the Luquillo Mountains of northeastern Puerto Rico. Extreme δ 2 H and δ 18 O values from low-pressure storm systems and the deuterium excess ( d -excess) were useful tracers of watershed response in this tropical system. A hydrograph separation experiment performed in June 2011 yielded different but complementary information from stable isotope and solute chemistry data. The hydrograph separation results indicated that 36% of the storm rain that reached the soil surface left the watershed in a very short time as runoff. Weathering-derived solutes indicated near-stream groundwater was displaced into the stream at the beginning of the event, followed by significant dilution. The more biologically active solutes exhibited a net flushing behavior. The d- excess analysis suggested that streamflow typically has a recent rainfall component (∼25%) with transit time less than the sampling resolution of 7 days, and a more well-mixed groundwater component (∼75%). The contemporaneous stream sample sets showed an overall increase in dissolved solute concentrations with decreasing elevation that may be related to groundwater inputs, different geology, and slope position. A considerable amount of water from rain events runs off as quickflow and bypasses subsurface watershed flowpaths, and better understanding of shallow hillslope and deeper groundwater processes in the watershed will require sub-weekly data and detailed transit time modeling. A combined isotopic and solute chemistry approach can guide further studies to a more comprehensive model of the hydrology, and inform decisions for managing water supply with future changes in climate and land use.

Applied Geochemistry↗

High-frequency, long-duration water sampling in acid mine drainage studies: a short review of current methods and recent advances in automated water samplers

Hand-collected grab samples are the most common water sampling method but using grab sampling to monitor temporally variable aquatic processes such as diel metal cycling or episodic events is rarely feasible or cost-effective. Currently available automated samplers are a proven, widely used technology and typically collect up to 24 samples during a deployment. However, these automated samplers are not well suited for long-term sampling in remote areas or in freezing conditions. There is a critical need for low-cost, long-duration, high-frequency water sampling technology to improve our understanding of the geochemical response to temporally variable processes. This review article will examine recent developments in automated water sampler technology and utilize selected field data from acid mine drainage studies to illustrate the utility of high-frequency, long-duration water sampling.

Applied Geochemistry↗

Organic and inorganic composition and microbiology of produced waters from Pennsylvania shale gas wells

Hydraulically fractured shales are becoming an increasingly important source of natural gas production in the United States. This process has been known to create up to 420 gallons of produced water (PW) per day, but the volume varies depending on the formation, and the characteristics of individual hydraulic fracture. PW from hydraulic fracturing of shales are comprised of injected fracturing fluids and natural formation waters in proportions that change over time. Across the state of Pennsylvania, shale gas production is booming; therefore, it is important to assess the variability in PW chemistry and microbiology across this geographical span. We quantified the inorganic and organic chemical composition and microbial communities in PW samples from 13 shale gas wells in north central Pennsylvania. Microbial abundance was generally low (66&ndash;9400 cells/mL). Non-volatile dissolved organic carbon (NVDOC) was high (7&ndash;31 mg/L) relative to typical shallow groundwater, and the presence of organic acid anions (e.g., acetate, formate, and pyruvate) indicated microbial activity. Volatile organic compounds (VOCs) were detected in four samples (&sim;1 to 11.7 &mu;g/L): benzene and toluene in the Burket sample, toluene in two Marcellus samples, and tetrachloroethylene (PCE) in one Marcellus sample. VOCs can be either naturally occurring or from industrial activity, making the source of VOCs unclear. Despite the addition of biocides during hydraulic fracturing, H 2 S-producing, fermenting, and methanogenic bacteria were cultured from PW samples. The presence of culturable bacteria was not associated with salinity or location; although organic compound concentrations and time in production were correlated with microbial activity. Interestingly, we found that unlike the inorganic chemistry, PW organic chemistry and microbial viability were highly variable across the 13 wells sampled, which can have important implications for the reuse and handling of these fluids

Pennsylvania↗

Insights into controls on hexavalent chromium in groundwater provided by environmental tracers, Sacramento Valley, California, USA

Environmental tracers are useful for determining groundwater age and recharge source, yet their application in studies of geogenic Cr(VI) in groundwater has been limited. Environmental tracer data from 166 wells located in the Sacramento Valley, northern California, were interpreted and compared to Cr concentrations to determine the origin and age of groundwater with elevated Cr(VI), and better understand where Cr(VI) becomes mobilized and how it evolves along flowpaths. In addition to major ion and trace element concentrations, the dataset includes &delta; 18 O, &delta; 2 H, 3 H concentration, 14 C activity (of dissolved inorganic C), &delta; 13 C, 3 He/ 4 He ratio, and noble gas concentrations (He, Ne, Ar, Kr, Xe). Noble gas recharge temperatures (NGTs) were computed, and age-related tracers were interpreted in combination to constrain the age distribution in samples and sort them into six different age categories spanning from <60 yr old to >10,000 yr old. Nearly all measured Cr is in the form of Cr(IV). Concentrations range from <1 to 46 &mu;g L &minus;1 , with 10% exceeding the state of California&rsquo;s Cr(VI) maximum contaminant level of 10 &mu;g L &minus;1 . Two groups with elevated Cr(VI) (⩾5 &mu;g L &minus;1 ) were identified. Group 1 samples are from the southern part of the valley and contain modern (<60 yr old) water, have elevated NO 3 &minus; concentrations (>3 mg L &minus;1 ), and commonly have &delta; 18 O values enriched relative to local precipitation. These samples likely contain irrigation water and are elevated due to accelerated mobilization of Cr(VI) in the unsaturated zone (UZ) in irrigated areas. Group 2 samples are from throughout the valley and typically contain water 1000&ndash;10,000 yr old, have &delta; 18 O values consistent with local precipitation, and have unexpectedly warm NGTs. Chromium(VI) concentrations in Group 2 samples may be elevated for multiple reasons, but the hypothesis most consistent with all available data (notably, the warm NGTs) is a relatively long UZ residence time due to recharge through a deep UZ near the margin of the basin. A possible explanation for why Cr(VI) may be primarily mobilized in the UZ rather than farther along flowpaths in the oxic portion of the saturated zone is more dynamic cycling of Mn in the UZ due to transient moisture and redox conditions.

California↗

Weathering and transport of chromium and nickel from serpentinite in the Coast Range ophiolite to the Sacramento Valley, California, USA

A soil geochemical study in northern California was done to investigate the role that weathering and transport play in the regional distribution and mobility of geogenic Cr and Ni, which are both potentially toxic and carcinogenic. These elements are enriched in ultramafic rocks (primarily serpentinite) and the soils derived from them (1700&ndash;10,000 mg Cr per kg soil and 1300&ndash;3900 mg Ni per kg soil) in the Coast Range ophiolite. Chromium and Ni have been transported eastward from the Coast Range into the western Sacramento Valley and as a result, valley soil is enriched in Cr (80&ndash;1420 mg kg &minus;1 ) and Ni (65&ndash;224 mg kg &minus;1 ) compared to median values of U.S. soils of 50 and 15 mg kg &minus;1 , respectively. Nickel in ultramafic source rocks and soils is present in serpentine minerals (lizardite, antigorite, and chrysotile) and is more easily weathered compared to Cr, which primarily resides in highly refractory chromite ([Mg,Fe 2+ ][Cr 3+ ,Al,Fe 3+ ] 2 O 4 ). Although the majority of Cr and Ni in soils are in refractory chromite and serpentine minerals, the etching and dissolution of these minerals, presence of Cr- and Ni-enriched clay minerals and development of nanocrystalline Fe (hydr)oxides is evidence that a significant fractions of these elements have been transferred to potentially more labile phases.

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