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USGS2021

Stability of inorganic and methylated arsenic species in laboratory standards, surface water and groundwater under three different preservation regimes

Geogenic arsenic (As) adversely affects drinking water quality in geologically diverse aquifers across the globe. Although the species of As significantly affects its fate, transport, toxicity, and As treatment technology efficacy, reported effectiveness of As species preservation methods varies widely with preservation methods and natural water geochemistry. Our study 1) evaluates the shelf life of As(III), As(V), dimethylarsinate (DMA), and monomethylarsonate (MMA) in standards prepared with ultrapure water; 2) establishes a hold time for these As species in low-iron (Fe) groundwater and surface water samples preserved with a concentration of EDTA that exceeded the sum of the molar concentrations of Al, Fe, Mn, Ca, Mg, and Sr (molar excess of EDTA); and 3) evaluates As(III) species stability in groundwater samples with detectable SO 4 and up to 6.5 mg/L Fe concentrations preserved in 3 ways: less than molar excess EDTA, molar excess EDTA, and Vacuette® tubes with an unknown (proprietary) amount of EDTA. Arsenic species standards prepared with 2.5 mM EDTA in ultrapure water and stored at 4 °C had a shelf life of at least 180 days. As(III) was stable for at least 15 days and DMA and MMA were stable for at least 90 days in environmental samples with Fe less than 1 mg/L that were preserved with a molar excess of EDTA and stored in opaque containers at 4 °C. As(III) species were not stable for any holding time in samples with Fe greater than 1 mg/L and detectable SO 4 when preserved with a molar excess of EDTA and stored in white high density polyethylene bottles at room temperature, or when preserved by storage in EDTA containing Vacuette® tubes at 4 °C. For geochemical or water quality studies where the distribution of As(III) and As(V) is a critical factor, an understanding of the sample chemistry, rapid As speciation analysis after sample collection, and collecting a field spike with the sample can be helpful for collecting accurate inorganic As species data.

Applied Geochemistry↗

USGS2015

Arsenic and antimony geochemistry of mine wastes, associated waters and sediments at the Giant Mine, Yellowknife, Northwest Territories, Canada

Elevated levels of arsenic (As) and antimony (Sb) in water and sediments are legacy residues found downstream from gold-mining activities at the Giant Mine in Yellowknife, Northwest Territories (NWT), Canada. To track the transport and fate of As and Sb, samples of mine-waste from the mill, and surface water, sediment, pore-water, and vegetation downstream of the mine were collected. Mine waste, pore-water, and sediment samples were analyzed for bulk chemistry, and aqueous and solid-state speciation. Sediment and vegetation chemistry were evaluated using scanning electron microscope imaging, synchrotron-based element mapping and electron microprobe analysis. The distributions of As and Sb in sediments were similar, yet their distributions in the corresponding pore-waters were mostly dissimilar, and the mobility of As was greater than that of Sb. Competition for sorption sites is the most likely cause of elevated Sb concentrations in relatively oxidized pore-water and surface water. The aqueous and solid-state speciation of As and Sb also differed. In pore-water, As(V) dominated in oxidizing environments and As(III) in reducing environments. In contrast, the Sb(V) species dominated in all but one pore-water sample, even under reducing conditions. Antimony(III) appears to preferentially precipitate or adsorb onto sulfides as evidenced by the prevalence of an Sb(III)-S secondary solid-phase and the lack of Sb(III)(aq) in the deeper zones. The As(V)–O solid phase became depleted with depth below the sediment–water interface, and the Sb(V)–O phase persisted under relatively reducing conditions. In the surficial zone at a site populated by Equisetum fluviatile (common horsetail), As and Sb were associated with organic material and appeared mobile in the root zone. In the zone below active plant growth, As and Sb were associated primarily with inorganic phases suggesting a release and reprecipitation of these elements upon plant death. The co-existence of reduced and oxidized As and Sb species, instability of some phases under changing redox conditions, and plant uptake and release pose challenges for remediation efforts at the mine.

Northwest Territories↗

USGS2009

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV Acid-sulfate waters

Many waters sampled in Yellowstone National Park, both high-temperature (30-94 ??C) and low-temperature (0-30 ??C), are acid-sulfate type with pH values of 1-5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H2S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH < 2.7. Field pH measurements were predominantly used because the charge imbalance was <??10%. When the charge imbalance was generally >??10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H2S or S2O3 oxidation, CO2 degassing, and the temperature-dependence of pK2 for H2SO4. Charge imbalances are shown to be dependent on a speciation model for pH values <3. The highest SO4 concentrations, in the thousands of mg/L, result from evaporative concentration at elevated temperatures as shown by the consistently high ??18O values (-10??? to -3???) and a ??D vs. ??18O slope of 3, reflecting kinetic fractionation. Low SO4 concentrations (<100 mg/L) for thermal waters (>350 mg/L Cl) decrease as the Cl- concentration increases from boiling which appears inconsistent with the hypothesis of H2S oxidation as a source of hydrothermal SO4. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid-sulfate water analyses are occasionally high in As, Hg, and NH3 concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO4, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone's acid waters but have not been observed in acid rock drainage of the same pH.

Applied Geochemistry↗

USGS2022

Occurrence and sources of lead in private wells, Sturbridge, Massachusetts

Lead (Pb) occurrence and sources and aqueous geochemistry were assessed in private wellhead and tap water at a targeted area of concern for possible exceedances and at a control area in the same geologic formation, and in wells at a nearby landfill in south-central Massachusetts (MA). Total Pb concentrations were below the U.S. Environmental Protection Agency (USEPA) Action Level of 15 μg/L in all samples, and about 6% of unfiltered samples contained Pb concentrations that exceeded 1.0 μg/L. Pb concentrations were higher under conditions that are acidic and oxic (pH ≤ 6.5 and dissolved oxygen [DO] ≥ 2 mg/L), in which minerals that could sequester lead or manganese typically are undersaturated, and adsorption by hydrous ferric oxide is limited. Under more neutral to alkaline conditions, the precipitation of Pb in solid solution series minerals such as (Ca,Pb)CO 3 and (Ba,Pb)SO 4 −2 , and adsorption by amorphous ferric hydroxides, could limit Pb solubility in the bedrock aquifer or in the plumbing. The low Pb concentrations and the absence of distinctive Pb and strontium (Sr) isotope ratio patterns in samples indicate that a nearby landfill is not likely a significant Pb source. Dissolved concentrations of Pb, copper (Cu), and zinc (Zn) in tap samples were significantly greater than those in wellhead samples, indicating that some Pb is derived from plumbing. Wellhead or tap samples with the highest Pb concentrations also had the greatest corrosivity potential based on the calcite saturation index and the PPGC (Potential to Promote Galvanic Corrosion) and supports the premise that Pb concentrations in tap samples were derived partly from corrosion of plumbing. Concentrations of other constituents, including arsenic (As), uranium (U), Sr, boron (B), and lithium (Li) were not statistically different between the tap and wellhead samples but, apart from Sr, all were statistically higher in the control area than in the target area. This variation in constituent concentrations suggests geochemical variation within the host Paxton Formation, possibly related to faulting and contact with the Ayer granite east of the control area.

Massachusetts↗

USGS2009

A regional-scale study of chromium and nickel in soils of northern California, USA

A soil geochemical survey was conducted in a 27,000-km 2 study area of northern California that includes the Sierra Nevada Mountains, the Sacramento Valley, and the northern Coast Range. The results show that soil geochemistry in the Sacramento Valley is controlled primarily by the transport and weathering of parent material from the Coast Range to the west and the Sierra Nevada to the east. Chemically and mineralogically distinctive ultramafic (UM) rocks (e.g. serpentinite) outcrop extensively in the Coast Range and Sierra Nevada. These rocks and the soils derived from them have elevated concentrations of Cr and Ni. Surface soil samples derived from UM rocks of the Sierra Nevada and Coast Range contain 1700-10,000 mg/kg Cr and 1300-3900 mg/kg Ni. Valley soils west of the Sacramento River contain 80-1420 mg/kg Cr and 65-224 mg/kg Ni, reflecting significant contributions from UM sources in the Coast Range. Valley soils on the east side contain 30-370 mg/kg Cr and 16-110 mg/kg Ni. Lower Cr and Ni concentrations on the east side of the valley are the result of greater dilution by granitic sources of the Sierra Nevada. Chromium occurs naturally in the Cr(III) and Cr(VI) oxidation states. Trivalent Cr is a non-toxic micronutrient, but Cr(VI) is a highly soluble toxin and carcinogen. X-ray diffraction and scanning electron microscopy of soils with an UM parent show Cr primarily occurs within chromite and other mixed-composition spinels (Al, Mg, Fe, Cr). Chromite contains Cr(III) and is highly refractory with respect to weathering. Comparison of a 4-acid digestion (HNO 3 , HCl, HF, HClO 4 ), which only partially dissolves chromite, and total digestion by lithium metaborate (LiBO 3 ) fusion, indicates a lower proportion of chromite-bound Cr in valley soils relative to UM source soils. Groundwater on the west side of the Sacramento Valley has particularly high concentrations of dissolved Cr ranging up to 50 ??g L -1 and averaging 16.4 ??g L -1 . This suggests redistribution of Cr during weathering and oxidation of Cr(III)-bearing minerals. It is concluded that regional-scale transport and weathering of ultramafic-derived constituents have resulted in enrichment of Cr and Ni in the Sacramento Valley and a partial change in the residence of Cr.

Applied Geochemistry↗

USGS1990

Hydrogeochemistry and stable isotopes of ground and surface waters from two adjacent closed basins, Atacama Desert, northern Chile

The geochemistry and stable isotopes of groundwaters, surface waters, and precipitation indicate different sources of some dissolved constituents, but a common source of recharge and other constituents in two adjacent closed basins in the Atacama Desert region of northern Chile (24°15′–24°45′S). Waters from artesian wells, trenches, and ephemeral streams in the Punta Negra Basin are characterized by concentrations of Na>Ca>Mg and Cl≥SO 4 ,with TDS<10 g/l. Values of δD and δ 18 O for Punta Negra Basin waters follow an evaporitic trend typical of closed basin waters in northern Chile and elsewhere. In contrast, ground waters in the Hamburgo Basin, located about 25 km NW of the Punta Negra Basin, have concentrations of Na > Mg≥Ca and SO 4 >Cl, with TDS also <10 g/l. Aqueous speciation calculations indicate that Hamburgo Basin groundwaters are close to saturation with respect to gypsum. The relatively high SO 4 and low Ca in Hamburgo Basin waters result from SO 4 influx and subsequent gypsum precipitation related to weathering at La Escondida, a large porphyry copper deposit located near to the center of the basin. Deep mine waters from 130 m below the water table at La Escondida also have Na>Mg≥Ca and SO 4 >Cl, but with TDS up to 40 g/l. The deep mine waters have pH between 3.2 and 3.9, and are high in dissolved CO 2 (δ 13 C= −4.8%PDB), indicating probable interaction with oxidizing sulfides. The deep mine waters have δ 18 O values of ≈−1.8%.compared with values < −3.5‰ for other Hamburgo Basin waters; thus the mine waters may represent a mixture of meteoric waters with deeper “metamorphic” waters, which had interacted with rocks and exchanged oxygen isotopes at elevated temperatures. Alternatively, the deep mine waters may represent fossil meteoric waters which evolved isotopically along an evaporative trend starting from values quite depleted in δ 18 O and °Dd relative to either precipitation or shallow groundwaters. High I/Br ratios in the Hamburgo Basin waters and La Escondida mine waters are consistent with regionally high I in surficial deposits in the Atacama Desert region and may represent dissolution of a wind-blown evaporite component.

Atacama Desert↗

USGS2013

U–Pb, Rb–Sr, and U-series isotope geochemistry of rocks and fracture minerals from the Chalk River Laboratories site, Grenville Province, Ontario, Canada

As part of the Geologic Waste Management Facility feasibility study, Atomic Energy of Canada Ltd. (AECL) is evaluating the suitability of the Chalk River Laboratories (CRL) site in Ontario, situated in crystalline rock of the southwestern Grenville Province, for the possible development of an underground repository for low- and intermediate-level nuclear waste. This paper presents petrographic and trace element analyses, U–Pb zircon dating results, and Rb–Sr, U–Pb and U-series isotopic analyses of gneissic drill core samples from the deep CRG-series characterization boreholes at the CRL site. The main rock types intersected in the boreholes include hornblende–biotite (±pyroxene) gneisses of granitic to granodioritic composition, leucocratic granitic gneisses with sparse mafic minerals, and garnet-bearing gneisses with variable amounts of biotite and/or hornblende. The trace element data for whole-rock samples plot in the fields of within-plate, syn-collision, and volcanic arc-type granites in discrimination diagrams used for the tectonic interpretation of granitic rocks. Zircons separated from biotite gneiss and metagranite samples yielded SHRIMP-RG U–Pb ages of 1472 ± 14 (2 σ ) and 1045 ± 6 Ma, respectively, in very good agreement with widespread Early Mesoproterozoic plutonic ages and Ottawan orogeny ages in the Central Gneiss Belt. The Rb–Sr, U–Pb, and Pb–Pb whole-rock errorchron apparent ages of most of the CRL gneiss samples are consistent with zircon U–Pb age and do not indicate substantial large-scale preferential element mobility during superimposed metamorphic and water/rock interaction processes. This may confirm the integrity of the rock mass, which is a positive attribute for a potential nuclear waste repository. Most 234 U/ 238 U activity ratios (AR) in whole rock samples are within errors of the secular equilibrium value of one, indicating that the rocks have not experienced any appreciable U loss or gain within the past 1 Ma. However, 234 U/ 238 U AR in fracture mineral samples collected down to borehole lengths of about 740 m deviate from the secular equilibrium value and 234 U/ 238 U model ages calculated for fracture mineral samples showing excess 234 U range from 593 to 1415 ka, thus providing evidence of fracture flow in the associated bedrock during the past 1.5 Ma. Rare earth element patterns are variable in fracture-filling calcites and Fe oxides/hydroxides but are similar to those observed in associated whole-rock samples. The observed Ce anomalies are very small ( Ce N / Ce N ∗ ≈ 1 "> CeN/CeN∗≈1 ), do not vary with depth, and, therefore, do not contain evidence that the studied fracture minerals precipitated from oxidizing waters at the conceptual depth of a repository.

Ontario↗

USGS2011

Chromium(VI) generation in vadose zone soils and alluvial sediments of the southwestern Sacramento Valley, California: a potential source of geogenic Cr(VI) to groundwater

Concentrations of geogenic Cr(VI) in groundwater that exceed the World Health Organization’s maximum contaminant level for drinking water (50 μg L −1 ) occur in several locations globally. The major mechanism for mobilization of this Cr(VI) at these sites is the weathering of Cr(III) from ultramafic rocks and its subsequent oxidation on Mn oxides. This process may be occurring in the southern Sacramento Valley of California where Cr(VI) concentrations in groundwater can approach or exceed 50 μg L −1 . To characterize Cr geochemistry in the area, samples from several soil auger cores (approximately 4 m deep) and drill cores (approximately 25 m deep) were analyzed for total concentrations of 44 major, minor and trace elements, Cr associated with labile Mn and Fe oxides, and Cr(VI). Total concentrations of Cr in these samples ranged from 140 to 2220 mg per kg soil. Between 9 and 70 mg per kg soil was released by selective extractions that target Fe oxides, but essentially no Cr was associated with the abundant reactive Mn oxides (up to ~1000 mg hydroxylamine-reducible Mn per kg soil was present). Both borehole magnetic susceptibility surveys performed at some of the drill core sites and relative differences between Cr released in a 4-acid digestion versus total Cr (lithium metaborate fusion digestion) suggest that the majority of total Cr in the samples is present in refractory chromite minerals transported from ultramafic exposures in the Coast Range Mountains. Chromium(VI) in the samples studied ranged from 0 to 42 μg kg −1 , representing a minute fraction of total Cr. Chromium(VI) content was typically below detection in surface soils (top 10 cm) where soil organic matter was high, and increased with increasing depth in the soil auger cores as organic matter decreased. Maximum concentrations of Cr(VI) were up to 3 times greater in the deeper drill core samples than the shallow auger cores. Although Cr(VI) in these vadose zone soils and sediments was only a very small fraction of the total solid phase Cr, they are a potentially important source for Cr(VI) to groundwater. Enhanced groundwater recharge through the vadose zone due to irrigation could carry Cr(VI) from the vadose zone to the groundwater and may be the mechanism responsible for the correlation observed between elevated Cr(VI) and NO 3 - source concentrations in previously published data for valley groundwaters. Incubation of a valley subsoil showed a Cr(VI) production rate of 24 μg kg −1 a −1 suggesting that field Cr(VI) concentrations could be regenerated annually. Increased Cr(VI) production rates in H + -amended soil incubations indicate that soil acidification processes such as nitrification of ammonium in fertilizers could potentially increase the occurrence of geogenic Cr(VI) in groundwater. Thus, despite the natural origin of the Cr, Cr(VI) generation in the Sacramento Valley soils and sediments has the potential to be influenced by human activities.

California↗

USGS2013

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development, north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH 4 gas content and its C isotopes (δ 13 C CH4 ), and select isotope tracers (δ 11 B, 87 Sr/ 86 Sr, δ 2 H, δ 18 O, δ 13 C DIC ) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH 4 was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH 4 /L. The δ 13 C CH4 of dissolved CH 4 ranged from −42.3&permil; to −74.7&permil;, with the most negative values characteristic of a biogenic source also associated with the highest observed CH 4 concentrations, with a possible minor contribution of trace amounts of thermogenic CH 4 . The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ 13 C CH4 = −35.4&permil; to −41.9&permil;). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO 3 dominated, (3) TDS > 100 mg/L and Na–HCO 3 dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr ( 87 Sr/ 86 Sr = 0.7097–0.7166), C (δ 13 C DIC = −21.3&permil; to −4.7&permil;), and B (δ 11 B = 3.9–32.9&permil;) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO 3 , and higher-mineralized Na–HCO 3 composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS &sim;10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH 4 and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.

Applied Geochemistry↗

USGS2008

Thermal history of the unsaturated zone at Yucca Mountain, Nevada, USA

Secondary calcite, silica and minor amounts of fluorite deposited in fractures and cavities record the chemistry, temperatures, and timing of past fluid movement in the unsaturated zone at Yucca Mountain, Nevada, the proposed site of a high-level radioactive waste repository. The distribution and geochemistry of these deposits are consistent with low-temperature precipitation from meteoric waters that infiltrated at the surface and percolated down through the unsaturated zone. However, the discovery of fluid inclusions in calcite with homogenization temperatures (Th) up to ???80 ??C was construed by some scientists as strong evidence for hydrothermal deposition. This paper reports the results of investigations to test the hypothesis of hydrothermal deposition and to determine the temperature and timing of secondary mineral deposition. Mineral precipitation temperatures in the unsaturated zone are estimated from calcite- and fluorite-hosted fluid inclusions and calcite ??18O values, and depositional timing is constrained by the 207Pb/235U ages of chalcedony or opal in the deposits. Fluid inclusion Th from 50 samples of calcite and four samples of fluorite range from ???35 to ???90 ??C. Calcite ??18O values range from ???0 to ???22??? (SMOW) but most fall between 12 and 20???. The highest Th and the lowest ??18O values are found in the older calcite. Calcite Th and ??18O values indicate that most calcite precipitated from water with ??18O values between -13 and -7???, similar to modern meteoric waters. Twenty-two 207Pb/235U ages of chalcedony or opal that generally postdate elevated depositional temperatures range from ???9.5 to 1.9 Ma. New and published 207Pb/235U and 230Th/Uages coupled with the Th values and estimates of temperature from calcite ??18O values indicate that maximum unsaturated zone temperatures probably predate ???10 Ma and that the unsaturated zone had cooled to near-present-day temperatures (24-26 ??C at a depth of 250 m) by 2-4 Ma. The evidence of elevated temperatures persisting in ash flow tuffs adjacent to parent calderas for as much as ???8 Ma is a new finding, but consistent with thermal modeling. Simulations using the HEAT code demonstrate that prolonged cooling of the unsaturated zone is consistent with magmatic heat inputs and deep-seated (sub-water table) hydrothermal activity generated by the large magma body ???8 km to the north that produced the 15-11 Ma ash flows and ash falls that make up Yucca Mountain. The evidence discussed in this and preceding papers strongly supports unsaturated zone deposition of the secondary minerals from descending meteoric waters. Although depositional temperatures reflect conductive (and possibly vapor-phase convective) heating of the unsaturated zone related to regional magmatic sources until perhaps 6 Ma, depositional conditions similar to the present-day unsaturated zone have prevailed for at least the past 2-4 Ma.

Applied Geochemistry↗

USGS2020

Geochemistry and age of groundwater in the Williston Basin, USA: Assessing potential effects of shale-oil production on groundwater quality

Thirty water wells were sampled in 2018 to understand the geochemistry and age of groundwater in the Williston Basin and assess potential effects of shale-oil production from the Three Forks-Bakken petroleum system (TBPS) on groundwater quality. Two geochemical groups are identified using hierarchical cluster analysis. Group 1 represents the younger (median 4 He = 21.49 × 10 −8 cm 3 STP/g), less chemically evolved water. Group 2 represents the older (median 4 He = 1389 × 10 −8 cm 3 STP/g), more chemically evolved water. At least two samples from each group contain elevated Cl concentrations (>70 mg/L). Br/Cl, B/Cl, and Li/Cl ratios indicate multiple sources account for the elevated Cl concentrations: septic-system leachate/road deicing salt, lignite beds in the aquifers, Pierre Shale beneath the aquifers, and water associated with the TBPS (one sample). 3 H and 14 C data indicate that 10.8, 21.6, and 67.6% of the samples are modern (post-1952), mixed age, and premodern (pre-1953), respectively. Lumped-parameter modeling of 3 H, SF 6 , 3 He, and 14 C concentrations indicates mean ages of the modern and premodern fractions range from ~1 to 30 years and 1300 to >30,000 years, respectively. Group 2 contains the highest CH 4 concentrations (0.0018–32 mg/L). δ 13 C–CH 4 and C 1 /C 2 +C 3 data in groundwater (−91.7 to −70.0‰ and 1280 to 13,600) indicate groundwater CH 4 is biogenic in origin and not from thermogenic shale gas. Four volatile organic compounds (VOCs) were detected in two samples. One mixed-age sample contains chloroform (0.25 μg/L) and dichloromethane (0.05 μg/L), which are probably associated with septic leachate. One premodern sample contains butane (0.082 μg/L) and n-pentane (0.032 μg/L), which are probably associated with thermogenic gas from a nearby oil well. The data indicate hydrocarbon production activities do not currently (2018) widely affect Cl, CH 4 , and VOC concentrations in groundwater. The predominance of premodern recharge in the aquifers indicates the groundwater moves relatively slowly, which could inhibit widespread chemical movement in groundwater overlying the TBPS. Comparison of groundwater-age data from five major unconventional hydrocarbon-production areas indicates aquifer zones used for water supply in the TBPS area have a lower risk of widespread chemical movement in groundwater than similar aquifer zones in the Fayetteville (Arkansas) and Marcellus (Pennsylvania) Shale production areas, but have a higher risk than similar aquifer zones in the Eagle Ford (Texas) and Haynesville (Texas, Louisiana) Shale production areas.

Montana, North Dakota, South Dakota↗

USGS2015

Temporal geochemical variations in above- and below-drainage coal mine discharge

Water quality data collected in 2012 for 10 above- and 14 below-drainage coal mine discharges (CMDs), classified by mining or excavation method, in the anthracite region of Pennsylvania, USA, are compared with data for 1975, 1991, and 1999 to evaluate long-term (37 year) changes in pH, SO 4 2− , and Fe concentrations related to geochemistry, hydrology, and natural attenuation processes. We hypothesized that CMD quality will improve over time because of diminishing quantities of unweathered pyrite, decreased access of O 2 to the subsurface after mine closure, decreased rates of acid production, and relatively constant influx of alkalinity from groundwater. Discharges from shafts, slopes, and boreholes, which are vertical or steeply sloping excavations, are classified as below-drainage; these receive groundwater inputs with low dissolved O 2 , resulting in limited pyrite oxidation, dilution, and gradual improvement of CMD water quality. In contrast, discharges from drifts and tunnels, which are nearly horizontal excavations into hillsides, are classified as above-drainage; these would exhibit less improvement in water quality over time because the rock surfaces continue to be exposed to air, which facilitates sustained pyrite oxidation, acid production, and alkalinity consumption. Nonparametric Wilcoxon matched-pair signed rank tests between 1975 and 2012 samples indicate decreases in Fe and SO 4 2− concentrations were highly significant ( p < 0.05) and increases in pH were marginally significant ( p < 0.1) for below-drainage discharges. For above-drainage discharges, changes in Fe and SO 4 2− concentrations were not significant, and increases in pH were highly significant between 1975 and 2012. Although a greater proportion of above-drainage discharges were net acidic in 2012 compared to below-drainage discharges, the increase in pH between 1975 and 2012 was greater for above- (median pH increase from 4.4 to 6.0) compared to below- (median pH increase from 5.6 to 6.1) drainage discharges. For cases where O 2 is limited, transformation of aqueous Fe II species to Fe III may be kinetically limited. In contrast, where O 2 is abundant, aqueous Fe concentrations may be limited by Fe III mineral precipitation; thus, trends in Fe may not follow those for SO 4 2− . In either case, when the supply of alkalinity is sufficient to buffer decreased acidity, the pH could increase by a step trend from strongly acidic (3–3.5) to near neutral (6–6.5) values. Modeled equilibrium with respect to Fe III precipitates varies with pH and Fe and SO 4 2− reconcentrations: increasing pH promotes the formation of ferrihydrite, while decreasing concentrations of Fe limit the formation of ferrihydrite, and decreasing Fe and SO 4 2− concentrations limit the precipitation of schwertmannite and favor formation of Fe III hydroxyl complexes and uncomplexed Fe 2+ and Fe 3+ . The analysis of the long-term geochemical changes in CMDs in the anthracite field and the effect of the hydrologic setting on water quality presented in this paper can help prioritize CMD remediation and facilitate selection and design of the most appropriate treatment systems.

Pennsylvania↗

USGS2010

Aquifer geochemistry at potential aquifer storage and recovery sites in coastal plain aquifers in the New York city area, USA

The effects of injecting oxic water from the New York city (NYC) drinking-water supply and distribution system into a nearby anoxic coastal plain aquifer for later recovery during periods of water shortage (aquifer storage and recovery, or ASR) were simulated by a 3-dimensional, reactive-solute transport model. The Cretaceous aquifer system in the NYC area of New York and New Jersey, USA contains pyrite, goethite, locally occurring siderite, lignite, and locally varying amounts of dissolved Fe and salinity. Sediment from cores drilled on Staten Island and western Long Island had high extractable concentrations of Fe, Mn, and acid volatile sulfides (AVS) plus chromium-reducible sulfides (CRS) and low concentrations of As, Pb, Cd, Cr, Cu and U. Similarly, water samples from the Lloyd aquifer (Cretaceous) in western Long Island generally contained high concentrations of Fe and Mn and low concentrations of other trace elements such as As, Pb, Cd, Cr, Cu and U, all of which were below US Environmental Protection Agency (USEPA) and NY maximum contaminant levels (MCLs). In such aquifer settings, ASR operations can be complicated by the oxidative dissolution of pyrite, low pH, and high concentrations of dissolved Fe in extracted water.The simulated injection of buffered, oxic city water into a hypothetical ASR well increased the hydraulic head at the well, displaced the ambient groundwater, and formed a spheroid of injected water with lower concentrations of Fe, Mn and major ions in water surrounding the ASR well, than in ambient water. Both the dissolved O2 concentrations and the pH of water near the well generally increased in magnitude during the simulated 5-a injection phase. The resultant oxidation of Fe2+ and attendant precipitation of goethite during injection provided a substrate for sorption of dissolved Fe during the 8-a extraction phase. The baseline scenario with a low (0.001M) concentration of pyrite in aquifer sediments, indicated that nearly 190% more water with acceptably low concentrations of dissolved Fe could be extracted than was injected. Scenarios with larger amounts of pyrite in aquifer sediments generally resulted in less goethite precipitation, increased acidity, and increased concentrations of dissolved Fe in extracted water. In these pyritic scenarios, the lower amounts of goethite precipitated and the lower pH during the extraction phase resulted in decreased sorption of Fe2+ and a decreased amount of extractable water with acceptably low concentrations of dissolved Fe (5.4??10-6M). A linear decrease in recovery efficiency with respect to dissolved Fe concentrations is caused by pyrite dissolution and the associated depletion of dissolved O2 (DO) and increase in acidity. Simulations with more than 0.0037M of pyrite, which is the maximum amount dissolved in the baseline scenario, had just over a 50% recovery efficiency. The precipitation of ferric hydroxide minerals (goethite) at the well screen, and a possible associated decrease in specific capacity of the ASR well, was not apparent during the extraction phase of ASR simulations, but the model does not incorporate the microbial effects and biofouling associated with ferric hydroxide precipitation.The host groundwater chemistry in calcite-poor Cretaceous aquifers of the NYC area consists of low alkalinity and moderate to low pH. The dissolution of goethite in scenarios with unbuffered injectate indicates that corrosion of the well could occur if the injectate is not buffered. Simulations with buffered injectate resulted in greater precipitation of goethite, and lower concentrations of dissolved Fe, in the extracted water. Dissolved Fe concentrations in extracted water were highest in simulations of aquifers (1) in which pyrite and siderite in the aquifer were in equilibrium, and (2) in coastal areas affected by saltwater intrusion, where high dissolved-cation concentrations provide a greater exchange of Fe2+ (FeX2). Results indicate that ASR in pyrite-beari

Applied Geochemistry↗

USGS2007

New isotopic evidence for the origin of groundwater from the Nubian Sandstone Aquifer in the Negev, Israel

The geochemistry and isotopic composition (H, O, S, O sulfate , C, Sr) of groundwater from the Nubian Sandstone (Kurnub Group) aquifer in the Negev, Israel, were investigated in an attempt to reconstruct the origin of the water and solutes, evaluate modes of water–rock interactions, and determine mean residence times of the water. The results indicate multiple recharge events into the Nubian sandstone aquifer characterized by distinctive isotope signatures and deuterium excess values. In the northeastern Negev, groundwater was identified with deuterium excess values of ∼16‰, which suggests local recharge via unconfined areas of the aquifer in the Negev anticline systems. The δ 18 O H2O and δ 2 H values (−6.5‰ and −35.4‰) of this groundwater are higher than those of groundwater in the Sinai Peninsula and southern Arava valley (−7.5‰ and −48.3‰) that likewise have lower deuterium excess values of ∼10‰. Based on the geochemical differences between groundwater in the unconfined and confined zones of the aquifer, a conceptual geochemical model for the evolution of the groundwater in the Nubian sandstone aquifer has been reconstructed. The isotopic composition of shallow groundwater from the unconfined zone indicates that during recharge oxidation of pyrite to SO 4 ( δ 34 S SO4 ∼−13‰; δ 18 O SO4 ∼+7.7‰) and dissolution of CaCO 3 ( 87 Sr/ 86 Sr ∼0.70787; δ 13 C DIC = −3.7‰) occur. In the confined zone of the aquifer, bacterial SO 4 reduction removes a significant part of dissolved SO 4 2 - "> SO42- , thereby modifying its isotopic composition ( δ 34 S SO4 ∼−2‰; δ 18 O SO4 ∼+8.5‰) and liberating dissolved inorganic C that contains little or no radiocarbon ( 14 C-free) with low δ 13 C DIC values (<−12‰). In addition to local recharge, the Sr and S isotopic data revealed contribution of external groundwater sources to the Nubian Sandstone aquifer, resulting in further modifications of the groundwater chemical and isotopic signatures. In the northeastern Negev, it is shown that SO 4 -rich groundwater from the underlying Jurassic aquifer contributes significantly to the salt budget of the Nubian Sandstone aquifer. The unique chemical and isotopic composition of the Jurassic groundwater ( δ 34 S SO4 ∼ +14‰; δ 18 O SO4 ∼ 14‰; 87 Sr/ 86 Sr ∼0.70764) is interpreted as reflecting dissolution of Late Triassic marine gypsum deposits. In the southern Arava Valley the authors postulate that SO 4 -rich groundwater with distinctively high Br/Cl (3 × 10 −3 ) low 87 Sr/ 86 Sr (0.70734), and high δ 34 S SO4 values (+15‰) is derived from mixing with underlying brines from the Paleozoic units. The radiocarbon measurements reveal low 14 C activities (0.2–5.8 pmc) in both the northeastern Negev and southern Arava Valley. Taking into account dissolution of carbonate rocks and bacterial SO 4 reduction in the unconfined area, estimated mean residence times of groundwater in the confined zone in the northeastern Negev are on the order of 21–38 ka, which suggests recharge predominantly during the last glacial period. The 14 C signal in groundwater from the southern Arava Valley is equally low but due to evidence for mixing with external water sources the residence time estimates are questionable.

Applied Geochemistry↗

USGS2009

Relative spatial soil geochemical variability along two transects across the United States and Canada

To support the development of protocols for the proposed North American Soil Geochemical Landscapes project, whose objective is to establish baselines for the geochemistry of North American soils, two continental-scale transects across the United States and Canada were sampled in 2004. The sampling employed a spatially stratified random sampling design in order to estimate the variability between 40-km linear sampling units, within them, at sample sites, and due to sample preparation and analytical chemical procedures. The 40-km scale was chosen to be consistent with the density proposed for the continental-scale project. The two transects, north–south (N–S) from northern Manitoba to the USA–Mexico border near El Paso, Texas, and east–west (E–W) from the Virginia shore north of Washington, DC, to north of San Francisco, California, closely following the 38th parallel, have been studied individually. The purpose of this study was to determine if statistically significant systematic spatial variation occurred along the transects. Data for 38 major, minor and trace elements in A- and C-horizon soils where less than 5% of the data were below the detection limit were investigated by Analysis of Variance (ANOVA). A total of 15 elements (K, Na, As, Ba, Be, Ce, La, Mn, Nb, P, Rb, Sb, Th, Tl and W) demonstrated statistically significant ( p <0.05) variability at the between-40-km scale for both horizons along both transects. Only Cu failed to demonstrate significant variability at the between-40-km scale for both soil horizons along both transects. The patterns of relative variability differ by transect and horizon. The N–S transect A-horizon soils show significant between-40-km scale variability for 29 elements, with only 4 elements (Ca, Mg, Pb and Sr) showing in excess of 50% of their variability at the within-40-km and ‘at-site’ scales. In contrast, the C-horizon data demonstrate significant between-40-km scale variability for 26 elements, with 21 having in excess of 50% of their variability at the within-40-km and ‘at-site’ scales. In 36 instances, the ‘at-site’ variability is statistically significant in terms of the sample preparation and analysis variability. It is postulated that this contrast between the A- and C- horizons along the N–S transect, that is dominated by agricultural land uses, is due to the local homogenization of Ap-horizon soils by tillage reducing the ‘at-site’ variability. The spatial variability is distributed similarly between scales for the A- and C-horizon soils of the E–W transect. For all elements, there is significant variability at the within-40-km scale. Notwithstanding this, there is significant between-40-km variability for 28 and 20 of the elements in the A- and C-horizon data, respectively. The differences between the two transects are attributed to (1) geology, the N–S transect runs generally parallel to regional strikes, whereas the E–W transect runs across regional structures and lithologies; and (2) land use, with agricultural tillage dominating along the N–S transect. The spatial analysis of the transect data indicates that continental-scale maps demonstrating statistically significant patterns of geochemical variability may be prepared for many elements from data on soil samples collected on a 40 x 40 km grid or similar sampling designs resulting in a sample density of 1 site per 1600 km 2 .

Applied Geochemistry↗

USGS2012

Mineralogy and environmental geochemistry of historical iron slag, Hopewell Furnace National Historic Site, Pennsylvania, USA

The Hopewell Furnace National Historic Site in southeastern Pennsylvania, which features an Fe smelter that was operational in the 18th and 19th centuries, is dominated by three slag piles. Pile 1 slag, from the Hopewell Furnace, and pile 2 slag, likely from the nearby Cornwall Furnace, were both produced in cold-blast charcoal-fired smelters. In contrast, pile 3 slag was produced in an anthracite furnace. Ore samples from the nearby Jones and Hopewell mines that fed the smelter are mainly magnetite-rich with some sulfides (pyrite, chalcopyrite, sphalerite) and accessory silicates (quartz, garnet, feldspar, and clay minerals). Slag piles 1 and 2 are similar mineralogically containing predominantly skeletal and dendritic aluminian diopside and augite, skeletal forsteritic olivine, glass, rounded blebs of metallic Fe, and exotic quartz. Olivine is a major phase in all samples from pile 2, whereas it occurs in only a few samples from pile 1. Samples of the <2 mm-size fraction of surface composite slag material or crushed slag from at depth in piles 1 and 2 are mineralogically similar to the large surface slag fragments from those piles with the addition of phases such as feldspars, Fe oxides, and clay minerals that are either secondary weathering products or entrained from the underlying bedrock. Pile 3 slag contains mostly skeletal forsteritic olivine and Ti-bearing aluminian diopside, dendritic or fine-grained subhedral melilite, glass, euhedral spinel, metallic Fe, alabandite–oldhamite solid solution, as well as a sparse Ti carbonitride phase. The bulk chemistry of the slag is dominated by Al 2 O 3 (8.5–16.2 wt.%), CaO (8.2–26.2 wt.%), MgO (4.2–24.7 wt.%), and SiO 2 (36.4–59.8 wt.%), constituting between 81% and 97% of the mass of the samples. Piles 1 and 2 are chemically similar; pile 1 slag overall contains the highest Fe 2 O 3 , K 2 O and MnO, and the lowest MgO concentrations. Pile 3 slag is high in Al 2 O 3 , CaO and S, and low in Fe 2 O 3 , K 2 O and SiO 2 compared to the other piles. In general, piles 1 and 2 are chemically similar to each other, whereas pile 3 is distinct – a conclusion that reflects their mineralogy. The similarities and differences among piles in terms of mineralogy and major element chemistry result from the different smelting conditions under which the slag formed and include the fuel source, the composition of the ore and flux, the type of blast (cold versus hot), which affects the furnace temperature, and other beneficiation methods. The three distinct slag piles at Hopewell are enriched in numerous trace elements, such as As (up to 12 mg/kg), Cd (up to 0.4 mg/kg), Co (up to 31.8 mg/kg), Cu (up to 647 mg/kg), Mn (up to 0.69 wt.%), Pb (up to 172 mg/kg) and Zn (up to 393 mg/kg), together with Fe (13.9 wt.%), when compared to the average for the continental crust, with the <2 mm-size fraction commonly containing the highest concentrations. Enrichments in various elements (e.g., Cd, Co, Cu, Pb, Zn) were also found in the ore samples. Despite these enrichments, comparison of bulk chemistry trace-element concentrations to the environmental guidelines suggests most elements are likely not problematic with the exception of As, Co, Fe and Mn. Leachate tests that simulate weathering indicate Fe (up to 973 μg/L) and Mn (up to 133 μg/L) are readily released in potentially harmful concentrations compared to secondary drinking water and some aquatic ecosystem toxicity criteria. Aluminum and Cu, although not high in the solid compared to environmental guidelines, also exceed relevant criteria in leachate extracts with maximum concentrations of 2700 μg/L and 17.7 μg/L, respectively. In contrast, As and Co, which are significant in the solids, are not leached in concentrations that exceed guidelines (i.e., 3 μg/L or less for both elements). The weathering rates of the Fe metal and Fe oxides, which host Cu and some Fe, are likely higher than the silicate glass, which hosts the majority of Al, Mn and some Fe, and the crystalline silicates and spinels affecting which elements and how much are released into the environment and surrounding aquatic ecosystem. The mineral assemblages and their chemical composition, the bulk sample chemistry, and leachability of trace elements are all important components in understanding the potential environmental impacts of the slag piles.

Pennsylvania↗

USGS1986

Geochemical evaluation of the geothermal resources in the San Marcos region, Guatemala

The chemical and isotopic compositions of hot springs in the San Marcos region of Guatemala are internally consistent with a hydrologic model in which a deep 240°C reservoir and one or more shallow 195–200°C reservoirs are present. Variations in hot-spring water compositions results from a combination of boiling, mixing with cold, dilute water, and chemical re-equilibration with decreasing temperature. The recharge water for the deep 240°C reservoir is isotopically heavier than the local meteoric water and probably comes from many kilometers to the west or southwest. The water in the shallow reservoir is a mixture of the 240°C water with about 20 ± 5% of cold, locally derived meteoric water. After mixing, the water in the shallow reservoir re-equilibrates with reservoir rock at 195–200°C. In some places additional mixing with cold water occurs after water leaves the shallow reservoir.

San Marcos region↗

USGS1986

Organic geochemical analysis of sedimentary organic matter associated with uranium

Samples of sedimentary organic matter from several geologic environments and ages which are enriched in uranium (56 ppm to 12%) have been characterized. The three analytical techniqyes used to study the samples were Rock-Eval pyrolysis, pyrolysis-gas chromatography-mass spectrometry, and solid-state C-13 nuclear magnetic resonance (NMR) spectroscopy. In samples with low uranium content, the pyrolysis-gas chromatography products contain oxygenated functional groups (as hydroxyl) and molecules with both aliphatic and aromatic carbon atoms. These samples with low uranium content give measurable Rock-Eval hydrocarbon and organic-CO 2 yields, and C-13 NMR values of > 30% aliphatic carbon. In contrast, uranium-rich samples have few hydrocarbon pyrolysis products, increased Rock-Eval organic-CO 2 contents and > 70% aromatic carbon contents from C-13 NMR. The increase in aromaticity and decrease in hydrocarbon pyrolysis yield are related to the amount of uranium and the age of the uranium minerals, which correspond to the degree of radiation damage. The three analytical techniques give complementary results. Increase in Rock-Eval organic-CO 2 yield correlates with uranium content for samples from the Grants uranium region. Calculations show that the amount of organic-CO 2 corresponds to the quantity of uranium chemically reduced by the organic matter for the Grants uranium region samples.

Applied Geochemistry↗