Geology topics

Charles A. Cravotta

Publications and source records attributed to Charles A. Cravotta.

At least 37 records · Page 2Linked to original sources

USGS2021

Interactive PHREEQ-N-AMDTreat water-quality modeling tools to evaluate performance and design of treatment systems for acid mine drainage

The PHREEQ-N-AMDTreat aqueous geochemical modeling tools described herein simulate changes in pH and solute concentrations resulting from passive and active treatment of acidic or alkaline mine drainage (AMD). The “user-friendly” interactive tools, which are publicly available software, utilize PHREEQC equilibrium aqueous and surface speciation models and kinetics models for O 2 ingassing and CO 2 outgassing, iron and manganese oxidation and precipitation, limestone dissolution, and organic carbon oxidation combined with reduction of nitrate, sulfate, and ferric iron. Reactions with synthetic caustic chemicals (CaO, Ca(OH) 2 , NaOH, Na 2 CO 3 ) or oxidizing agents (H 2 O 2 ) also may be simulated separately or combined with sequential kinetic steps. A user interface facilitates input of water chemistry data for one or two (mixed) influent AMD solutions and adjustment of kinetic variables. Graphical and tabular output indicates the changes in pH, metals and other solute concentrations, total dissolved solids, and specific conductance of treated effluent plus the cumulative quantity of precipitated solids as a function of retention time or the amount of caustic agent added. By adjusting kinetic variables or chemical dosing, the effects of independent or sequential treatment steps that have different retention time (volume/flow rate), aeration rate, quantities of reactive solids, and temperature can be simulated for the specified influent quality. The size (land area) of a treatment system can then be estimated using reaction time estimates (volume for a corresponding treatment step is the product of reaction time and flow rate; area is volume divided by depth). Given the estimated system size, the AMDTreat cost-analysis model may be used to compute approximate costs for installation (capital) and annual operations and maintenance. Thus, various passive and/or active treatment strategies can be identified that could potentially achieve the desired effluent quality, but require different land area, equipment, and costs for construction and operation.

Applied Geochemistry↗

USGS2021

Lithium in groundwater used for drinking-water supply in the United States

Lithium concentrations in untreated groundwater from 1464 public-supply wells and 1676 domestic-supply wells distributed across 33 principal aquifers in the United States were evaluated for spatial variations and possible explanatory factors. Concentrations nationwide ranged from <1 to 396 μg/L (median of 8.1) for public supply wells and <1 to 1700 μg/L (median of 6 μg/L) for domestic supply wells. For context, lithium concentrations were compared to a Health Based Screening Level (HBSL, 10 μg/L) and a drinking-water only threshold (60 μg/L). These thresholds were exceeded in 45% and 9% of samples from public-supply wells and in 37% and 6% from domestic-supply wells, respectively. However, exceedances and median concentrations ranged broadly across geographic regions and principal aquifers. Concentrations were highest in arid regions and older groundwater, particularly in unconsolidated clastic aquifers and sandstones, and lowest in carbonate-rock aquifers, consistent with differences in lithium abundance among major lithologies and rock weathering extent. The median concentration for public-supply wells in the unconsolidated clastic High Plains aquifer (central United States) was 24.6 μg/L; 24% of the wells exceeded the drinking-water only threshold and 86% exceeded the HBSL. Other unconsolidated clastic aquifers in the arid West had exceedance rates comparable to the High Plains aquifer, whereas no public supply wells in the Biscayne aquifer (southern Florida) exceeded either threshold, and the highest concentration in that aquifer was 2.6 μg/L. Multiple lines of evidence indicate natural sources for the lithium concentrations; however, anthropogenic sources may be important in the future because of the rapid increase of lithium battery use and subsequent disposal. Geochemical models demonstrate that extensive evaporation, mineral dissolution, cation exchange, and mixing with geothermal waters or brines may account for the observed lithium and associated constituent concentrations, with the latter two processes as major contributing factors.

Science of the Total Environment↗

USGS2020

Groundwater quality in relation to drinking water health standards and hydrogeologic and geochemical characteristics for 47 domestic wells in Potter County, Pennsylvania, 2017

As part of a regional effort to characterize groundwater in rural areas of Pennsylvania, water samples from 47 domestic wells in Potter County were collected from May through September 2017. The sampled wells had depths ranging from 33 to 600 feet in sandstone, shale, or siltstone aquifers. Groundwater samples were analyzed for physicochemical properties that could be evaluated in relation to drinking-water health standards, geology, land use, and other environmental factors. Laboratory analyses included concentrations of major ions, nutrients, bacteria, trace elements, volatile organic compounds (VOCs), ethylene and propylene glycol, alcohols, gross-alpha/beta-particle activity, uranium, radon-222, and dissolved gases. A subset of samples was analyzed for radium isotopes (radium-226 and -228) and for the isotopic composition of methane. Results of this 2017 study show that groundwater quality generally met most drinking-water standards that apply to public water supplies. However, a percentage of samples exceeded maximum contaminant levels (MCLs) for total coliform bacteria (69.6 percent), Escherichia coli (30.4 percent), arsenic, and barium; and secondary maximum contaminant levels (SMCLs) for field pH, manganese, sodium, iron, total dissolved solids, aluminum, and chloride. All of the analyzed VOCs were below limits of detection and associated drinking water criteria. Radon-222 activities exceeded the proposed drinking-water standard of 300 picocuries per liter in 80.9 percent of the samples. The field pH of the groundwater ranged from 4.6 to 9.0. Generally, the lower pH samples had greater potential for elevated concentrations of dissolved metals, including beryllium, copper, lead, nickel, and zinc, whereas the higher pH samples had greater potential for elevated concentrations of total dissolved solids, sodium, fluoride, boron, and uranium. Near-neutral samples (pH 6.5 to 7.5) had greater hardness and alkalinity concentrations than other samples with pH values outside this range. Calcium/bicarbonate waters were the predominant hydrochemical type for the sampled aquifers, with mixed water types for many samples, including variable contributions from calcium, magnesium, and sodium combined with bicarbonate, sulfate, chloride, and nitrate. Water from 45 wells had concentrations of methane greater than the 0.0002 milligrams per liter (mg/L) detection limit. One sample had the maximum value of 11 mg/L, which exceeds the Pennsylvania action level of 7 mg/L. Additionally, three other samples had concentrations of methane greater than 4 mg/L. Outgassing of such levels of methane from the water to air within a confined space can result in a potential hazard. The elevated concentrations of methane generally were associated with suboxic groundwater (dissolved oxygen less than 0.5 mg/L) that had near-neutral to alkaline pH with relatively elevated concentrations of iron, manganese, ammonia, lithium, fluoride, and boron. Other constituents, including barium, sodium, chloride, and bromide, commonly were elevated, but not limited to, those well-water samples with elevated methane. Low levels of ethane (as much as 1.2 mg/L) were present in eight samples with the highest methane concentrations. Five samples were analyzed for methane isotopes. The isotopic and hydrocarbon compositions in these five samples suggest the methane may be of microbial origin or a mixture of thermogenic and microbial gas, but differed from the compositions reported for mud-gas logging samples collected during drilling of gas wells. The concentrations of sodium (median 8.2 mg/L), chloride (median 7.64 mg/L), and bromide (median 0.02 mg/L) for the 47 groundwater samples collected for this study ranged widely and were positively correlated with one another and with specific conductance and associated measures of ionic strength. Sixty percent of the Potter County well-water samples had chloride concentrations less than 10 mg/L. Samples with higher chloride concentrations had variable bromide concentrations and corresponding chloride/bromide ratios that are consistent with sources such as road-deicing salt and septic effluent (low bromide) or brine (high bromide). Brines are naturally present in deeper parts of the regional groundwater system and, in some cases, may be mobilized by gas drilling. It is also possible that valley wells were drilled close to or into the brine-freshwater interface, so brine signatures do not necessarily indicate contamination due to drilling. The chloride, bromide, and other constituents in road-deicing salt or brine solutions tend to be diluted by mixing with fresh groundwater in shallow aquifers used for water supply. Although 1 of 8 groundwater samples with the highest methane concentrations (greater than 0.2 mg/L) had concentrations of chloride and bromide with corresponding chloride/bromide ratios that indicated mixing with road-deicing salt, the other 7 of 8 samples with elevated methane had concentrations of chloride and bromide with corresponding chloride/bromide ratios that indicated mixing with a small amount of brine (0.02 percent or less) similar in composition to those reported for gas and oil well brines in Pennsylvania. In several eastern Pennsylvania counties where gas drilling is absent, groundwater with comparable chloride/bromide ratios and chloride concentrations have been reported. Approximately 50 percent of Potter County well-water samples, including two samples with the fourth (72.9 mg/L) and fifth (47.0 mg/L) highest chloride concentrations, have chloride/bromide ratios that indicate predominantly anthropogenic sources of chloride, such as road-deicing salt or septic effluent.

Pennsylvania↗

USGS2020

Occurrence and geochemistry of lead-210 and polonium-210 radionuclides in public-drinking-water supplies from principal aquifers of the United States

On the basis of lifetime cancer risks, lead-210 ( 210 Pb) and polonium-210 ( 210 Po) ≥ 1.0 and 0.7 pCi/L (picocuries per liter), respectively, in drinking-water supplies may pose human-health concerns. 210 Pb and 210 Po were detected at concentrations greater than these thresholds at 3.7 and 1.5%, respectively, of filtered untreated groundwater samples from 1263 public-supply wells in 19 principal aquifers across the United States. Nationally, 72% of samples with radon-222 ( 222 Rn) concentrations > 4000 pCi/L had 210 Pb ≥ 1.0 pCi/L. 210 Pb is mobilized by alpha recoil associated with the decay of 222 Rn and short-lived progeny. 210 Pb concentrations ≥ 1.0 pCi/L occurred most frequently where acidic groundwaters inhibited 210 Pb readsorption (felsic-crystalline rocks) and where reducing alkaline conditions favored dissolution of iron–manganese- (Fe–Mn-) oxyhydroxides (which adsorb 210 Pb) and formation of lead–carbonate complexes (enhancing lead (Pb) mobility). 210 Po concentrations ≥ 0.7 pCi/L occurred almost exclusively in confined Coastal Plain aquifers where old (low percent-modern carbon-14) groundwaters were reducing, with high pH (>7.5) and high sodium/chloride (Na/Cl) ratios resulting from cation exchange. In high-pH environments, aqueous polonium (Po) is poorly sorbed, occurring as dihydrogen polonate (H 2 PoO 3 (aq)) or, under strongly reducing conditions, as a hydrogen-polonide anion (HPo – ). Fe–Mn- and sulfate-reduction and cation-exchange processes may mobilize polonium from mineral surfaces. Po 2+ occurrence in low-to-neutral-pH waters is attenuated by adsorption.

Environmental Science Technology↗

USGS2020

Groundwater quality in relation to drinking water health standards and geochemical characteristics for 54 domestic wells in Clinton County, Pennsylvania, 2017

Despite the reliance on groundwater by approximately 2.4 million rural Pennsylvania residents, publicly available data to characterize the quality of private well water are limited. As part of a regional effort to characterize groundwater in rural areas of Pennsylvania, samples from 54 domestic wells in Clinton County were collected and analyzed in 2017. The samples were evaluated for a wide range of constituents and compared to drinking-water health standards and geochemical characteristics. The sampled wells were completed to depths ranging from 46 to 500 feet in bedrock that was of predominantly sandstone, shale, or carbonate lithology. Results of this study show that the sampled groundwater quality in Clinton County generally met most drinking-water standards that apply to public water supplies. However, a percentage of samples exceeded drinking-water maximum contaminant levels (MCLs) for total coliform bacteria (57.4 percent), Escherichia coli ( E. coli ) (25.9 percent), nitrate (1.9 percent), and arsenic (1.9 percent); and secondary maximum contaminant levels (SMCLs) for pH (31.5 percent), manganese (29.6 percent), iron (13 percent), total dissolved solids (7.4 percent), aluminum (1.9 percent), and chloride (1.9 percent). Sodium concentrations exceeded the U.S. Environmental Protection Agency drinking-water advisory recommendation in 16.7 percent of the samples. Radon-222 activities exceeded the proposed drinking-water standard of 300 picocuries per liter (pCi/L) in 59.3 percent of the samples. The only volatile organic compounds (VOCs) detected were acetone and methyl ethyl ketone in two separate samples; neither constituent exceeded drinking-water standards. Higher median nitrate concentrations were found in the carbonate (3.26 milligrams per liter [mg/L]) versus shale (less than 0.04 mg/L) and sandstone (0.27 mg/L) aquifer subsets. Most of the elevated nitrate concentrations were associated with E. coli detections in the carbonate aquifers, where transmissive bedrock can facilitate groundwater contamination by human activities at the land surface. The median pH of groundwater from the sandstone aquifers (6.53) was less than those for the shale aquifers (7.31) and carbonate aquifers (7.43). Generally, the lower pH samples had greater potential for elevated concentrations of dissolved metals, including beryllium, copper, lead, nickel, and zinc, whereas the higher pH samples had greater potential for elevated concentrations of total dissolved solids, sodium, fluoride, boron, and uranium. Near-neutral samples (pH 6.5 to 7.5) had greater hardness and alkalinity concentrations than other samples with pH outside this range. Many samples from the shale or sandstone aquifers, particularly those with pH less than 6.5, were identified as having serious potential corrosivity based on the combination of the calcite saturation index and the chloride to sulfate mass ratio; however, none of the samples from the carbonate aquifers was identified as seriously corrosive. Groundwater from 3.7 percent of the wells had concentrations of methane greater than the Pennsylvania action level of 7 mg/L, and 48 of the 54 wells (88.9 percent) had detectable concentrations of methane greater than the 0.0002 mg/L detection limit. Greater methane concentrations were found more frequently in groundwater sampled from the shale aquifers than the carbonate or sandstone aquifers in the study area. Most of the samples containing elevated methane (greater than 0.2 mg/L) were located outside the area of the Appalachian Plateaus. The elevated concentrations of methane generally were associated with suboxic groundwater (dissolved oxygen less than 0.5 mg/L) that had near-neutral to alkaline pH and were correlated with concentrations of iron, manganese, ammonia, sodium, lithium, barium, fluoride, and boron. The stable carbon and hydrogen isotopic compositions of methane in two of four samples analyzed for isotopes were consistent with compositions reported for mud-gas logging samples from gas-bearing geologic units (thermogenic gas) in the Appalachian Plateaus region, whereas two others were consistent with methane of microbial origin or a mixture of microbial and thermogenic gas. Forty-two percent of samples had chloride concentrations greater than 20 mg/L with variable bromide concentrations. Corresponding chloride/bromide ratios are consistent with low-bromide sources such as road-deicing salt and septic effluent or animal waste, or, in a few cases, high-bromide brine. Brines characterized by relatively high bromide are naturally present in deeper parts of the regional groundwater system and, in some cases, may be mobilized by gas drilling. The chloride, bromide, and other constituents in road-deicing salt or brine solutions tend to be diluted by mixing with fresh groundwater in shallow aquifers used for water supply. One of the four groundwater samples with methane concentrations greater than 4 mg/L had chloride and bromide concentrations and a chloride/bromide ratio that indicates mixing with a salinity source such as road-deicing salt, whereas the chloride and bromide concentrations and ratios for the other three high-methane samples indicate mixing with a small amount of brine (0.03 percent or less). In two other eastern Pennsylvania county studies where gas drilling is absent, groundwater with comparable chloride/bromide ratios, bromide, and chloride concentrations plus other element associations have been reported. Additional sampling and analysis, such as isotopic analysis of the dissolved gas, fracture analysis, and more detailed evaluation of surrounding land uses, may be warranted to better understand the origin of the methane and brine constituents in groundwater at specific locations.

Pennsylvania↗

USGS2020

Batch extraction method to estimate total dissolved solids (TDS) release from coal refuse and overburden

A rapid batch extraction method was evaluated to estimate potential for total dissolved solids (TDS) release by 65 samples of rock from coal and gas-bearing strata of the Appalachian Basin in eastern USA. Three different extractant solutions were considered: deionized water (DI), DI equilibrated with 10% CO 2 atmosphere (DI + CO 2 ), or 30% H 2 O 2 under 10% CO 2 (H 2 O 2 +CO 2 ). In all extractions, 10 g of pulverized rock (<0.5-mm) were mixed with 20 mL of extractant solution and shaken for 4 h at 50 rpm and 20–22 °C. The 65 rock samples were classified as coal (n=3), overburden (n = 17), coal refuse that had weathered in the field (n = 14), unleached coal refuse that had oxidized during indoor storage (n = 20), gas-bearing shale (n = 10), and pyrite (n = 1). Extracts were analyzed for specific conductance (SC), TDS, pH, and major and trace elements, and subsequently speciated to determine ionic contributions to SC. The pH of extractant blanks decreased in the order DI (6.0), DI + CO 2 (5.1), and H 2 O 2 +CO 2 (2.6). The DI extractant was effective for mobilizing soluble SO 4 and Cl salts. The DI + CO 2 extractant increased weathering of carbonates and resulted in equivalent or greater TDS than the DI leach of the same material. The H 2 O 2 +CO 2 extractant increased weathering of sulfides (and carbonates) and resulted in the greatest TDS production and lowest pH values. Of the 65 samples, 19 had leachate chemistry data from previous column experiments and 35 were paired to 10 field sites with leachate chemistry data. When accounting for the water-to-rock ratio, TDS from DI and DI + CO 2 extractions were correlated to TDS from column experiments while TDS from H 2 O 2 +CO 2 extractions was not. In contrast to column experiments, field SC was better correlated to SC measured from H 2 O 2 +CO 2 extractions than DI extractions. The field SC and SC from H 2 O 2 +CO 2 extractions were statistically indistinguishable for 7 of 9 paired data sets while SC from DI extractions underestimated field SC in 5 of 9 cases. Upscaling comparisons suggest that (1) weathering reactions in the field are more aggressive than DI water or synthetic rainwater extractants used in batch or column tests, and (2) a batch extraction method utilizing 30% H 2 O 2 (which is mildly acidic without CO 2 enrichment) could be effective for identifying rocks that will release high amounts of TDS.

Applied Geochemistry↗

USGS2019

Kinetic study on clogging of a geothermal pumping well triggered by mixing-induced biogeochemical reactions

The sustainability of ground-source geothermal systems can be severely impacted by microbially mediated clogging processes. Biofouling of water wells by hydrous ferric oxide is a widespread problem. Although the mechanisms and critical environmental factors associated with clogging development are widely recognized, effects of mixing processes within the wells and time scales for clogging processes are not well characterized. Here we report insights from a joint hydrological, geochemical, and metagenomics characterization of a geothermal doublet in which hydrous ferric oxide and hydrous manganese oxide deposits had formed as a consequence of mixing shallow groundwater containing dissolved oxygen and nitrate with deeper, anoxic groundwater containing dissolved iron (Fe II ) and manganese (Mn II ). Metagenomics identify distinct bacteria consortia in the pumping well oxic and anoxic zones, including autotrophic iron-oxidizing bacteria. Batch mixing experiments and geochemical kinetics modeling of the associated reactions indicate that Fe II and Mn II oxidation are slow compared to the residence time of water in the pumping well; however, adsorption of Fe II and Mn II by accumulated hydrous ferric oxide and hydrous manganese oxide in the well bore and pump riser provides “infinite” time for surface-catalyzed oxidation and a convenient source of energy for iron-oxidizing bacteria, which colonize the surfaces and also catalyze oxidation. Thus, rapid clogging is caused by mixing-induced redox reactions and is exacerbated by microbial activity on accumulated hydrous oxide surfaces.

Orleans↗

USGS2019

Drinking water health standards comparison and chemical analysis of groundwater for 72 domestic wells in Bradford County, Pennsylvania, 2016

Pennsylvania has the second highest number of residential wells of any state in the Nation with approximately 2.4 million residents that depend on groundwater for their domestic water supply. Despite the widespread reliance on groundwater in rural areas of the state, publicly available data to characterize the quality of private well water are limited. In Bradford County, more than half of the residents use groundwater from private domestic-supply wells as their primary drinking source. The quality of private well water is influenced by the regional and local setting, including the surrounding soil, geology, land use, household plumbing, and well construction. The groundwater used for domestic water supply in Bradford County is obtained primarily from shallow bedrock and from unconsolidated (glacial) deposits that overlie the bedrock. Historical land use has been predominately forested, agricultural, and residential, but more recently unconventional oil/gas development has been distributed throughout the landscape. Pennsylvania is one of only two states in the Nation without statewide water-well construction standards. To better assess the quality of groundwater used for drinking water supply in Bradford County, data for 72 domestic wells were collected and analyzed for a wide range of constituents that could be evaluated in relation to drinking water health standards, geology, land use, and other environmental factors. Groundwater samples were collected from May through August 2016 and analyzed for physical and chemical properties, including major ions, nutrients, trace elements, volatile organic compounds, ethylene and propylene glycol, alcohols, gross-alpha/beta-particle activity, uranium, radon-222, and dissolved gases. A subset of samples was analyzed for radium isotopes (radium-226 and -228) and for the isotopic composition of methane. This study was conducted by the U.S. Geological Survey in cooperation with the Northern Tier Regional Planning and Development Commission and is part of a regional effort to characterize groundwater in rural areas of Pennsylvania. Results of the 2016 study show that groundwater quality generally met most drinking-water standards. However, a percentage of samples failed to meet maximum contaminant levels (MCLs) for total coliform bacteria (49.3 percent), Escherichia coli (8.5 percent), barium (2.8 percent), and arsenic (2.8 percent); and secondary maximum contaminant levels (SMCL) for sodium (48.6 percent), manganese (30.6 percent), gross alpha and beta activity (16.7 percent), iron (11.1 percent), pH (8.3 percent), total dissolved solids (5.6 percent), chloride (1.4 percent), and aluminum (1.4 percent). Radon-222 activities exceeded the proposed drinking-water standard of 300 picocuries per liter (pCi/L) in 70.4 percent of the samples. There were no exceedances of drinking water health standards for any volatile organic compounds, and the only detections were for three trihalomethanes in one sample. The pH of the groundwater had a large influence on chemical characteristics and ranged from 6.18 to 9.31. Generally, the higher pH samples had higher potential for elevated concentrations of several constituents, including total dissolved solids, sodium, lithium, chloride, fluoride, boron, arsenic, and methane. For the Bradford County well-water samples, calcium/bicarbonate type waters were most abundant, with others classified as sodium/bicarbonate or mixed water types including calcium-sodium/bicarbonate, calcium-sodium/bicarbonate-chloride, sodium/bicarbonate-chloride, sodium/bicarbonate-sulfate, or sodium/chloride types. Six principal components (pH, redox, hardness, chloride-bromide, strontium-barium, and molybdenum-arsenic) explained nearly 78.3 percent of the variance in the groundwater dataset. Groundwater from 12.5 percent of the wells had concentrations of methane greater than the Pennsylvania action level of 7 milligrams per liter (mg/L); detectable methane concentrations ranged from 0.01 to 77 mg/L. In addition, low levels of ethane (as much as 0.13 mg/L) were present in seven samples with the highest methane concentrations. The isotopic composition of methane in five of these groundwater samples was consistent with the isotopic compositions reported for mud-gas logging samples from these geologic units and a thermogenic source. Isotopic composition from a sixth sample suggested the methane in that sample may be of microbial origin. Well-water samples with the higher methane concentrations also had higher pH values and elevated concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide. Relatively elevated concentrations of some other constituents, such as barium and chloride, commonly were present in, but not limited to, those well-water samples with elevated methane. Four of the six groundwater samples with the highest methane concentrations had chloride/bromide ratios that indicate mixing with a small amount of brine (0.02 percent or less) similar in composition to those reported for gas and oil well brines in Pennsylvania. In several other eastern Pennsylvania counties where gas drilling is absent, groundwater with comparable chloride/bromide ratios and chloride concentrations have been reported, implying a potential natural source of brine. Most of Bradford County well-water samples have chloride concentrations less than 20 mg/L, and those with higher chloride concentrations have chloride/bromide ratios that indicate anthropogenic sources (such as road-deicing salt and septic effluent) or brine. Brines that are naturally present may originate from deeper parts of the aquifer system, whereas anthropogenic sources are more likely to affect shallow groundwater because they occur on or near the land surface. The available data for this study indicate that no one physical factor, such as the topographic setting, well depth, or altitude at the bottom of the well, was particularly useful for predicting those well locations with an elevated dissolved concentration of methane. The 2016 assessment of groundwater quality in Bradford County shows groundwater is generally of good quality, but methane and some constituents that occur in high concentration in naturally occurring brine and also in produced waters may be present at low to moderate concentrations in groundwater in various parts of the aquifer.

Pennsylvania↗

USGS2019

Factors affecting the occurrence of lead and manganese in untreated drinking water from Atlantic and Gulf Coastal Plain aquifers, eastern United States—Dissolved oxygen and pH framework for evaluating risk of elevated concentrations

Groundwater samples collected during 2012 and 2013 from public-supply wells screened in the Atlantic and Gulf Coastal Plain aquifers of the eastern and southeastern U.S. rarely contained lead or manganese concentrations that exceeded drinking-water limits, despite having corrosive characteristics. Data indicate that the occurrence of dissolved lead and manganese in sampled groundwater, prior to its distribution or treatment, was related to several explanatory factors including the presence of source minerals, hydrologic position along the flow path, water-rock interactions, and associated geochemical conditions such as pH and dissolved oxygen (DO) concentrations. Elevated concentrations of lead compared to health-based benchmarks were associated with groundwater that is acidic (pH ≤ 6.5), oxygenated (DO ≥ 2 mg/L), and closer to recharge zones (relatively young water). Elevated concentrations of manganese were associated with groundwater that is acidic to neutral (pH ≤ 7.5), has low DO (<2 mg/L), and further from recharge zones (relatively old). Under these geochemical conditions, minerals that could sequester lead or manganese tended to be undersaturated, and adsorption by hydrous ferric oxide was limited. Under neutral to alkaline pH conditions, precipitation of impure calcium carbonate or phosphate compounds containing traces of lead or manganese (solid solutions) could maintain low concentrations of the trace elements. Additionally, adsorption of lead or manganese cations by hydrous ferric oxides (HFO) could be another attenuating factor where conditions are oxidizing and dissolved inorganic carbon concentrations are relatively low. A DO/pH framework was developed as a screening tool for evaluating risk of elevated lead or manganese, based on the occurrence of elevated lead and manganese concentrations and the corresponding distributions of DO and pH in the Atlantic and Gulf Coastal Plain aquifers. Validation of the DO/pH framework was accomplished using an independent national dataset that showed consistent results for elevated lead (pH ≤ 6.5; DO ≥ 2 mg/L) and manganese (pH ≤ 7.5; DO < 2 mg/L).

Atlantic and Gulf Coastal Plain aquifers↗

USGS2019

Radium accumulation in carbonate river sediments at oil and gas produced water discharges: Implications for beneficial use as disposal management

In the western U.S., produced water from oil and gas wells discharged to surface water augments downstream supplies used for irrigation and livestock watering. Here we investigate six permitted discharges on three neighboring tributary systems in Wyoming. During 2013-16, we evaluated radium activities of the permitted discharges and the potential for radium accumulation in associated stream sediments. Radium activities of the sediments at the points of discharge ranged from approximately 200-3600 Bq/kg with elevated activities above the background of 74 Bq/kg over 30 km downstream of one permitted discharge. Sediment as deep as 30 cm near the point of discharge had radium activities elevated above background. X-ray diffraction and targeted sequential extraction of radium in sediments indicate that radium is likely coprecipitated with carbonate, and to a lesser extent sulfate minerals. PHREEQC modeling predicts radium coprecipitation with aragonite and barite, but over-estimates the latter compared to observations of downstream sediment, where carbonate predominates. Mass-balance calculations indicate over 3 billion Bq of radium activity (226Ra+228Ra) is discharged each year from five of the discharges, combined, with only 5 percent of the annual load retained in stream sediments within 100m of the effluent discharges; the remaining 95 percent of the radium is transported farther downstream as sediment-associated and aqueous species

Environmental Science↗

USGS2018

Hydrologic characteristics and water quality of headwater streams and wetlands at the Allegheny Portage Railroad National Historic Site, Summit area, Blair and Cambria Counties, Pennsylvania, 2014–16

The Allegheny Portage Railroad National Historic Site (ALPO) in Blair and Cambria Counties, Pennsylvania, protects historic features of the first railroad portage over the Allegheny Front and the first railroad tunnel in the United States. This report, which was completed by the U.S. Geological Survey in cooperation with the National Park Service, summarizes water resources in the headwaters of the Blair Gap Run and Bradley Run watersheds at the ALPO Summit area during 2014–16. These new baseline data fill an existing gap in knowledge and may be helpful to evaluate potential changes in the hydrologic characteristics of streams and associated wetlands at the Summit area. Results of synoptic water-quality surveys and continuous stage records at two streamgages near the headwaters of Blair Gap Run and Bradley Run indicate that the headwater streams of the ALPO Summit area are perennial but have different water-quality characteristics. The water sampled in the headwaters of Blair Gap Run had pH that ranged from acidic to near neutral, combined with elevated concentrations of dissolved solids, mainly sulfate, chloride, and sodium. These characteristics can be attributed to drainage from legacy coal mines and runoff from nearby roads treated with deicing salt. More than once during the study, the chloride and associated contaminant concentrations in tributaries of Blair Gap Run exceeded chronic thresholds for protection of freshwater aquatic organisms. In contrast, the water quality at tributaries of Bradley Run in the Summit area was characterized by near-neutral pH and relatively low concentrations of dissolved constituents, which met criteria for protection of freshwater aquatic life. By comparison, the deep groundwater discharged as abandoned mine drainage to Sugar Run from the Argyle Stone Bridge Mine, which underlies the Summit area, had acidic pH and elevated concentrations of sulfate and metals, which exceeded chronic and acute thresholds for aquatic life. Data on shallow groundwater levels in piezometers at two wetlands in the Summit area, which were monitored during spring through fall of 2016, indicate downward hydraulic gradients (higher water level in shallow piezometer than in deeper piezometer) and potential for local groundwater recharge during rainfall events, particularly in the summer and fall seasons. The wetlands in the upland area (wetland 3, at altitude 2,370 feet NAVD 88) near the divide between Blair Gap Run and Bradley Run between the Lemon House and Picnic Area, exhibited a consistent downward gradient from spring through fall of 2016. The associated surface seepage at wetland 3 dried up in the summer of 2016. In contrast, the wetlands in the adjoining valley (wetland 6, at altitude 2,198 feet NAVD 88) in the northwestern Summit area exhibited upward hydraulic gradients in the spring and produced continuous seepage. Despite downward gradients during summer and fall, the seepage associated with wetland 6 sustained perennial conditions in the Bradley Run drainage through the summer of 2016. Differences in groundwater altitudes and associated water quality among the surface water, shallow groundwater, and deep groundwater in the Summit area imply that the surface water and shallow groundwater in the Summit area could recharge the groundwater of the underlying coal mines. Seasonally upward and downward vertical gradients in the near-surface soil and bedrock at wetland 6, and unimpaired water quality in the Bradley Run headwaters, are consistent with a perched water table and local hydrology that is influenced by local recharge. Persistent downward gradients and impaired water quality at wetland 3 and the adjacent headwaters seeps and tributaries of Blair Gap Run could be attributed to subsidence and drainage from shallow coalbeds (Upper Freeport, seam E) and associated mine workings in that area; however, the underlying deep coal mine pool (Lower Kittanning, seam B), which is hundreds of feet below the surface, does not appear to affect the hydrologic characteristics of the headwater streams and wetlands in the Summit area.

Pennsylvania↗

USGS2018

Radium attenuation and mobilization in stream sediments following oil and gas wastewater disposal in western Pennsylvania

Centralized waste treatment facilities (CWTs) in Pennsylvania discharged wastewater from conventional and unconventional oil and gas (O&G) wells into surface waters until 2011, when a voluntary request from the Pennsylvania Department of Environmental Protection (PA DEP) encouraged recycling rather than treating and discharging unconventional O&G wastewater. To determine the effect of this request on the occurrence of radium in streams, we sampled sediments at five CWTs that processed conventional O&G wastewater from 2011 to 2017 and compared results to published data. Despite the policy change in 2011 that reduced disposal of unconventional wastes (i.e., Marcellus) to surface water in Pennsylvania, the continued disposal of conventional O&G wastewater led to elevated radium activities in sediments at the point of discharge that were often hundreds of times higher than background. While these elevated activities were also present in downstream sediments (1.5× higher than background), the elimination of unconventional O&G wastewater disposal through the CWTs since 2011 decreased radium loading to the stream by approximately 95%. Sequential extractions and geochemical modeling using PHREEQC indicate that radium likely co-precipitates with barite or barite-celestite solid solutions and accumulates in the sediment as treated O&G effluent enters the stream. Adsorption of “exchangeable” radium, barium , and strontium on hydrous iron and manganese oxide coatings on fine-grained stream sediments is an important radium sequestration mechanism further downstream that can decrease the cation concentrations and potential for radio-barite co-precipitation. Radium downstream of CWTs was more abundant and more available for dissolution and desorption than radium in upstream sediments.

Pennsylvania↗

USGS2017

Baseline assessment of groundwater quality in Pike County, Pennsylvania, 2015

The Devonian-age Marcellus Shale and the Ordovician-age Utica Shale, which have the potential for natural gas development, underlie Pike County and neighboring counties in northeastern Pennsylvania. In 2015, the U.S. Geological Survey, in cooperation with the Pike County Conservation District, conducted a study that expanded on a previous more limited 2012 study to assess baseline shallow groundwater quality in bedrock aquifers in Pike County prior to possible extensive shale-gas development. Seventy-nine water wells ranging in depths from 80 to 610 feet were sampled during June through September 2015 to provide data on the presence of methane and other aspects of existing groundwater quality in the various bedrock geologic units throughout the county, including concentrations of inorganic constituents commonly present at low values in shallow, fresh groundwater but elevated in brines associated with fluids extracted from geologic formations during shale-gas development. All groundwater samples collected in 2015 were analyzed for bacteria, dissolved and total major ions, nutrients, selected dissolved and total inorganic trace constituents (including metals and other elements), radon-222, gross alpha- and gross beta-particle activity, dissolved gases (methane, ethane, and propane), and, if sufficient methane was present, the isotopic composition of methane. Additionally, samples from 20 wells distributed throughout the county were analyzed for selected man-made volatile organic compounds, and samples from 13 wells where waters had detectable gross alpha activity were analyzed for radium-226 on the basis of relatively elevated gross alpha-particle activity. Results of the 2015 study show that groundwater quality generally met most drinking-water standards for constituents and properties included in analyses, but groundwater samples from some wells had one or more constituents or properties, including arsenic, iron, manganese, pH, bacteria, sodium, chloride, sulfate, total dissolved solids, and radon-222, that did not meet (commonly termed failed or exceeded) primary or secondary maximum contaminant levels (MCLs) or Health Advisories (HA) for drinking water. Except for iron, dissolved and total concentrations of major ions and most trace constituents generally were similar. Only 1 of 79 well-water samples had any constituent that exceeded a MCL, with an arsenic concentration of about 30 micrograms per liter (µg/L) that was higher than the MCL of 10 µg/L. However, total arsenic concentrations were higher than the HA of 2 µg/L in samples from another 12 of 79 wells (about 15 percent). Secondary maximum contaminant levels (SMCLs) were exceeded most frequently by pH and concentrations of iron and manganese. The pH was outside of the SMCL range of 6.5–8.5 in samples from 24 of 79 wells (30 percent), ranging from 5.5 to 9.2; more samples had pH values less than 6.5 than had pH values greater than 8.5. Total iron concentrations typically were much greater than dissolved iron concentrations, indicating substantial presence of iron in particulate phase, and exceeded the SMCL of 300 µg/L more often [35 of 79 samples (44 percent)] than dissolved iron concentrations [samples from 8 of 79 wells (10 percent)]. Total manganese concentrations exceeded the SMCL of 50 µg/L in samples from 31 of 79 wells (39 percent) and the HA of 300 µg/L in samples from 13 of 79 wells (about 16 percent). A few (1–2) samples had concentrations of sodium, chloride, sulfate, or TDS higher than the SMCLs of 60, 250, 250, and 500 mg/L, respectively. However, dissolved sodium concentrations were higher than the HA of 20 mg/L in samples from 15 of 79 wells (nearly 20 percent). Total coliform bacteria were detected in samples from 25 of 79 wells (32 percent) but Escherichia coli were not detected in any sample. Radon-222 activities ranged from 11 to 5,100 picocuries per liter (pCi/L), with a median of 1,440 pCi/L, and exceeded the proposed and the alternate proposed drinking-water standards of 300 and 4,000 pCi/L, respectively, in samples from 60 of 79 wells (75 percent) and in samples from 2 of 79 wells (3 percent), respectively. Groundwater samples from all wells were analyzed for dissolved methane by one contract laboratory that determined water from 19 of the 79 wells (24 percent) had concentrations of methane greater than the reporting level of 0.010 milligrams per liter (mg/L) with a maximum methane concentration of 2.5 mg/L. Methane concentrations in 18 replicate samples submitted to a second laboratory for dissolved gas and isotopic analysis generally were higher by as much as a factor of 2.7 from those determined by the first laboratory, indicating potential bias related to combined sampling and analytical methods, and therefore, caution needs to be used when comparing methane results determined by different methods. The isotopic composition of methane in 9 of 10 samples with sufficient dissolved methane (about 0.3 mg/L) for isotopic analysis is consistent with values reported for methane of microbial origin produced through carbon dioxide reduction; an isotopic shift in 1 or 2 samples may indicate subsequent methane oxidation. The low concentrations of ethane relative to methane in these samples further indicate that the methane may be of microbial origin. Groundwater samples with relatively elevated methane concentrations (near or greater than 0.3 mg/L) also had chemical compositions that differed in some respects from groundwater with relatively low methane concentrations (less than 0.3 mg/L) by having higher pH (greater than 8) and higher concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide and chloride/bromide ratios indicative of mixing with a small amount of brine of probable natural occurrence. The spatial distribution of groundwater compositions differs by topographic setting and lithology and generally shows that (1) relatively dilute, slightly acidic, oxygenated, calcium-carbonate type waters tend to occur in the uplands underlain by the undivided Poplar Gap and Packerton members of the Catskill Formation in southwestern Pike County; (2) waters of near neutral pH with the highest amounts of hardness (calcium and magnesium) generally occur in areas of intermediate altitudes underlain by other members of the Catskill Formation; and (3) waters with pH values greater than 8, low oxygen concentrations, and the highest arsenic, sodium, lithium, bromide, and methane concentrations can be present in deep wells in uplands but most frequently occur in stream valleys, especially at low altitudes (less than about 1,200 feet above North American Vertical Datum of 1988) where groundwater may be discharging regionally, such as to the Delaware River in northern and eastern Pike County. Thus, the baseline assessment of groundwater quality in Pike County prior to gas-well development shows that shallow (less than about 1,000 feet deep) groundwater generally meets primary drinking-water standards for inorganic constituents but varies spatially, with methane and some constituents present in high concentrations in brine (and connate waters from gas and oil reservoirs) present at low to moderate concentrations in some parts of Pike County.

Pennsylvania↗

USGS2017

Groundwater quality for 75 domestic wells in Lycoming County, Pennsylvania, 2014

Groundwater is a major source of drinking water in Lycoming County and adjacent counties in north-central and northeastern Pennsylvania, which are largely forested and rural and are currently undergoing development for hydrocarbon gases. Water-quality data are needed for assessing the natural characteristics of the groundwater resource and the potential effects from energy and mineral extraction, timber harvesting, agriculture, sewage and septic systems, and other human influences. This report, prepared in cooperation with Lycoming County, presents analytical data for groundwater samples from 75 domestic wells sampled throughout Lycoming County in June, July, and August 2014. The samples were collected using existing pumps and plumbing prior to any treatment and analyzed for physical and chemical characteristics, including nutrients, major ions, metals and trace elements, volatile organic compounds, gross-alpha particle and gross beta-particle activity, uranium, and dissolved gases, including methane and radon-222. Results indicate groundwater quality generally met most drinking-water standards, but that some samples exceeded primary or secondary maximum contaminant levels (MCLs) for arsenic, iron, manganese, total dissolved solids (TDS), chloride, pH, bacteria, or radon-222. Arsenic concentrations were higher than the MCL of 10 micrograms per liter (µg/L) in 9 of the 75 (12 percent) well-water samples, with concentrations as high as 23.6 μg/L; arsenic concentrations were higher than the health advisory level (HAL) of 2 μg/L in 23 samples (31 percent). Total iron concentrations exceeded the secondary maximum contaminant level (SMCL) of 300 μg/L in 20 of the 75 samples. Total manganese concentrations exceeded the SMCL of 50 μg/L in 20 samples and the HAL of 300 μg/L in 2 of those samples. Three samples had chloride concentrations that exceeded the SMCL of 250 milligrams per liter (mg/L); two of those samples exceeded the SMCL of 500 mg/L for TDS. The pH ranged from 5.3 to 9.15 and did not meet the SMCL range of 6.5 to 8.5 in 22 samples, with 17 samples having a pH less than 6.5 and 8 samples having pH greater than 8.5. Generally, the samples that had elevated TDS, chloride, or arsenic concentrations had high pH. Total coliform bacteria were detected in 39 of 75 samples (52 percent), with Escherichia coli detected in 10 of those 39 samples. Radon-222 activities ranged from non-detect to 7,420 picocuries per liter (pCi/L), with a median of 863 pCi/L, and exceeded the proposed drinking-water standard of 300 pCi/L in 50 (67 percent) of the 75 samples; radon-222 activities were higher than the alternative proposed standard of 4,000 pCi/L in 3 samples. Water from 15 of 75 (20 percent) wells had concentrations of methane greater than the reporting level of 0.01 mg/L; detectable methane concentrations ranged from 0.04 to 16.8 mg/L. Two samples had methane concentrations (13.1 and 16.8 mg/L) exceeding the action level of 7 mg/L. Low levels of ethane (up to 0.12 mg/L) were present in the five samples with the highest methane concentrations (near or above 1 mg/L) that were analyzed for hydrocarbon compounds and isotopic composition. The isotopic composition of methane in four of these groundwater samples, from the Catskill and Lock Haven Formations and the Hamilton Group, have sample carbon isotopic ratio delta values (carbon-13/carbon-12) ranging from –42.36 to –36.08 parts per thousand (‰) and hydrogen isotopic ratio delta values (deuterium/protium) ranging from –212.0 to –188.4 ‰, which are consistent with the isotopic compositions reported for mud-gas logging samples from these geologic units and a thermogenic source of the methane. However, the isotopic composition and ratios of methane to ethane in a fifth sample indicate the methane in that sample may be of microbial origin that subsequently underwent oxidation. The fifth sample had the highest concentration of methane, 16.8 mg/L, with an carbon isotopic ratio delta values of -50.59 ‰ and a hydrogen isotopic ratio delta values of -209.7 ‰. The six well-water samples with the highest methane concentrations also had among the highest pH values (8.25 to 9.15) and elevated concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide. Relatively elevated concentrations of some other constituents, such as barium, strontium, and chloride, commonly were present in, but not limited to, those well-water samples with elevated methane. Three of the six groundwater samples with the highest methane concentrations had chloride/bromide ratios that indicate mixing with a small amount of brine (0.02 percent or less) similar in composition to those reported at undetermined depth below the freshwater aquifer and for gas and oil well brines in Pennsylvania. The sample with the highest methane concentration and most other samples with low methane concentrations (less than about 1 mg/L) have chloride/bromide ratios that indicate predominantly anthropogenic sources of chloride, such as road-deicing salt, septic systems, and (or) animal waste. Brines that are naturally present may originate from deeper parts of the aquifer system, while anthropogenic sources are more likely to affect shallow groundwater because they occur on or near the land-surface. The spatial distribution of groundwater compositions generally indicate that (1) uplands along the western border of Lycoming County usually have dilute, slightly acidic oxygenated, calcium-bicarbonate type waters; (2) intermediate altitudes or areas of carbonate bedrock usually have water of near neutral pH, with highest amounts of hardness (calcium and magnesium); (3) stream valleys, low elevations where groundwater may be discharging, and deep wells in uplands usually have water with pH values greater than 8 and highest arsenic, sodium, lithium, bromide concentrations. Geochemical modeling indicated that for samples with elevated pH, sodium, lithium, bromide, and alkalinity, the water chemistry could have resulted by dissolution of calcite (calcium carbonate) combined with cation-exchange and mixing with a small amount of brine. Through cation-exchange reactions between water and bedrock, which are equivalent to processes in a water softener, calcium ions released by calcite dissolution are exchanged for sodium ions on clay minerals. Thus, the assessment of groundwater quality in Lycoming County indicates groundwater is generally of good quality, but various parts of Lycoming County can have groundwater with low to moderate concentrations of methane and other constituents that appear in naturally present brine and produced waters from gas and oil wells at high concentrations."

Pennsylvania↗

USGS2017

Enhanced Al and Zn removal from coal-mine drainage during rapid oxidation and precipitation of Fe oxides at near-neutral pH

Net-alkaline, anoxic coal-mine drainage containing ∼20 mg/L Fe II and ∼0.05 mg/L Al and Zn was subjected to parallel batch experiments: control, aeration (Aer 1 12.6 mL/s; Aer 2 16.8 mL/s; Aer 3 25.0 mL/s), and hydrogen peroxide (H 2 O 2 ) to test the hypothesis that aeration increases pH, Fe II oxidation, hydrous Fe III oxide (HFO) formation, and trace-metal removal through adsorption and coprecipitation with HFO. During 5.5-hr field experiments, pH increased from 6.4 to 6.7, 7.1, 7.6, and 8.1 for the control, Aer 1, Aer 2, and Aer 3, respectively, but decreased to 6.3 for the H 2 O 2 treatment. Aeration accelerated removal of dissolved CO 2 , Fe, Al, and Zn. In Aer 3, dissolved Al was completely removed within 1 h, but increased to ∼20% of the initial concentration after 2.5 h when pH exceeded 7.5. H 2 O 2 promoted rapid removal of all dissolved Fe and Al, and 13% of dissolved Zn. Kinetic modeling with PHREEQC simulated effects of aeration on pH, CO 2 , Fe, Zn, and Al. Aeration enhanced Zn adsorption by increasing pH and HFO formation while decreasing aqueous CO 2 available to form ZnCO 3 0 and Zn(CO 3 ) 2 2− at high pH. Al concentrations were inconsistent with solubility control by Al minerals or Al-containing HFO, but could be simulated by adsorption on HFO at pH < 7.5 and desorption at higher pH where Al(OH) 4 − was predominant. Thus, aeration or chemical oxidation with pH adjustment to ∼7.5 could be effective for treating high-Fe and moderate-Zn concentrations, whereas chemical oxidation without pH adjustment may be effective for treating high-Fe and moderate-Al concentrations.

Pennsylvania↗

USGS2017

Hydrological and geophysical investigation of streamflow losses and restoration strategies in an abandoned mine lands setting

Longitudinal discharge and water-quality campaigns (seepage runs) were combined with surface-geophysical surveys, hyporheic-temperature profiling, and watershed-scale hydrological monitoring to evaluate the locations, magnitude, and impact of streamwater losses from the West Creek subbasin of the West West Branch Schuylkill River into the underground Oak Hill Mine complex that extends beneath the watershed divide. Abandoned mine drainage (AMD), containing iron and other contaminants, from the Oak Hill Boreholes to the West Branch Schuylkill River was sustained during low-flow conditions and correlated to streamflow lost through the West Creek streambed. During high-flow conditions, streamflow was transmitted throughout West Creek; however, during low-flow conditions, all streamflow from the perennial headwaters was lost within the 300-to-600-m "upper reach" where an 1889 mine map indicated steeply dipping coalbeds underlie the channel. During low-flow conditions, the channel within the "intermediate reach" 700-to-1650-m downstream gained groundwater seepage with higher pH and specific conductance than upstream; however, all streamflow 1650-to-2050-m downstream was lost to underlying mines. Electrical resistivity and electromagnetic conductivity surveys indicated conductive zones beneath the upper reach, where flow loss occurred, and through the intermediate reach, where gains and losses occurred. Temperature probes at 0.06-to-0.10-m depth within the hyporheic zone of the intermediate reach indicated potential downward fluxes as high as 2.1x10-5 m/s. Cumulative streamflow lost from West Creek during seepage runs averaged 53.4 L/s, which equates to 19.3 percent of the daily average discharge of AMD from the Oak Hill Boreholes and a downward flux of 1.70x10-5 m/s across the 2.1-km-by-1.5-m West Creek stream-channel area.

Pennsylvania↗

USGS2016

Dissolution of fluorapatite by Pseudomonas fluorescens P35 resulting in fluorine release

Chemical weathering of fluorine-bearing minerals is widely accepted as the main mechanism for the release of fluorine (F) to groundwater. Here, we propose a potential mechanism of F release via microbial dissolution of fluorapatite (Ca 5 (PO 4 ) 3 F), which has been neglected previously. Batch culture experiments were conducted at 30°C with a phosphate-solubilizing bacteria strain, Pseudomonas fluorescens P35, and rock phosphates as the sole source of phosphate for microbial growth in parallel with abiotic controls. Rock phosphates consisted of 55–91% of fluorapatite and 5–10% of dolomite before microbial dissolution as indicated by X-ray diffraction (XRD). Mineral composition and morphology changed after microbial dissolution characterized by the disappearance of dolomite and the development of etched cavities on rock phosphate surfaces. The pH of media used was approximately 7.4 at the beginning and increased gradually to 7.7 in abiotic controls; with the inoculum, the pH decreased to acidic values of 3.7–3.8 after 27 h. Phosphate, calcium, and fluoride were released from the rock phosphate to the acidified medium. At 42 h, the concentration of F reached 8.1–10.3 mg L −1 . The elevated F concentration was two times higher than the F levels in groundwater in regions diagnosed with fluorosis, and was toxic to the bacteria, as demonstrated by a precipitous decrease in live cells. Geochemical modeling demonstrated that the oxidation of glucose (the carbon source for microbial growth in the medium) to gluconic acid could decrease the pH to 3.7–3.8 and result in the dissolution of fluorapatite and dolomite. Dolomite and fluorapatite remained unsaturated, while concentrations of dissolved phosphorus (P), calcium (Ca), and F increased throughout the time course Fluorite reached saturation [saturation index (SI) 0.22–0.42] after 42 h in rock phosphate–amended biotic systems. However, fluorite was not detected in XRD patterns of the final residue from microcosms. Given that phosphate-solubilizing bacteria are ubiquitous in soil and groundwater ecosystems, they could play an important role in fluorapatite dissolution and the release of F to groundwater.

Geomicrobiology Journal↗

USGS2016

Acid mine drainage

Acid mine drainage (AMD) consists of metal-laden solutions produced by the oxidative dissolution of iron sulfide minerals exposed to air, moisture, and acidophilic microbes during the mining of coal and metal deposits. The pH of AMD is usually in the range of 2–6, but mine-impacted waters at circumneutral pH (5–8) are also common. Mine drainage usually contains elevated concentrations of sulfate, iron, aluminum, and other potentially toxic metals leached from rock that hydrolyze and coprecipitate to form rust-colored encrustations or sediments. When AMD is discharged into surface waters or groundwaters, degradation of water quality, injury to aquatic life, and corrosion or encrustation of engineered structures can occur for substantial distances. Prevention and remediation strategies should consider the biogeochemical complexity of the system, the longevity of AMD pollution, the predictive power of geochemical modeling, and the full range of available field technologies for problem mitigation.

Book chapter↗