Geology topics

Zoltan Szabo

Publications and source records attributed to Zoltan Szabo.

At least 19 recordsLinked to original sources

USGS2024

Predictive understanding of stream salinization in a developed watershed using machine learning

Stream salinization is a global issue, yet few models can provide reliable salinity estimates for unmonitored locations at the time scales required for ecological exposure assessments. Machine learning approaches are presented that use spatially limited high-frequency monitoring and spatially distributed discrete samples to estimate the daily stream-specific conductance across a watershed. We compare the predictive performance of space- and time-unaware Random Forest models and space- and time-aware Recurrent Graph Convolution Neural Network models (KGE: 0.67 and 0.64, respectively) and use explainable artificial intelligence methods to interpret model predictions and understand salinization drivers. These models are applied to the Delaware River Basin, a developed watershed with diverse land uses that experiences anthropogenic salinization from winter deicer applications. These models capture seasonality for the winter first flush of deicers, and the streams with elevated predictions correspond well with indicators of deicer application. This result suggests that these models can be used to identify potential salinity-impaired streams for winter best management practices. Daily salinity predictions are driven primarily by land cover (urbanization) trends that may represent anthropogenic salinization processes and weather at time scales up to three months. Such modeling approaches are likely transferable to other watersheds and can be applied to further understand salinization risks and drivers.

Environmental Science and Technology↗

USGS2023

Gross alpha-particle activity and high 226Ra concentrations do not correspond with high 210Po in the Atlantic and Gulf Coastal Plain aquifers of the United States

210 Po, which is of human-health concern based on lifetime ingestion cancer risk, is indirectly regulated in drinking water through the U.S. Environmental Protection Agency’s gross alpha-particle activity (GAPA) maximum contaminant level of 15 pCi/L (picocuries per liter). This regulation requires independent measurement of 226 Ra for samples exceeding the GAPA screening level of 5 pCi/L. There is no such requirement for 210 Po. Co-occurrence of 226 Ra and 210 Po, alpha-emitting 238 U-decay-series progeny, might be helpful in locating high- 210 Po waters but is unverified. Relations among 210 Po, 226 Ra, and GAPA evaluated for samples from 257 public-supply wells from Coastal Plain aquifers showed that concentrations of 226 Ra correlated with GAPA but neither correlated with 210 Po concentrations. The highest concentrations of 226 Ra and 210 Po were found under differing geochemical conditions. The highest 226 Ra occurred in low-pH oxidizing waters and in neutral-pH reducing waters, where geochemical conditions render Fe–Mn-hydroxide sorbents inefficient. 210 Po was highest (10.1 pCi/L) in reducing waters with high pH (>7.5, which results from progressive cation exchange), where 226 Ra was lowest─exchanged to clay minerals. Because 226 Ra and 210 Po did not co-occur, the GAPA screening might not be protective for 210 Po. Independent 210 Po analysis is prudent, especially where groundwater is reducing with high pH and low 226 Ra concentrations.

Environmental Science & Technology Water↗

USGS2021

Relation between road-salt application and increasing radium concentrations in a low-pH aquifer, southern New Jersey

The Kirkwood–Cohansey aquifer in southern New Jersey is an important source of drinking-water supplies, but the availability of the resource is limited in some areas by high concentrations of radium, a potential carcinogen at elevated concentrations. Radium ( 226 Ra plus 228 Ra) concentrations from a network of 25 drinking-water wells showed a statistically significant increase over a decadal time scale ( p < 0.05), with a median increase of 0.35 picocuries per liter. Increases in Ra are correlated with road-salt application rates, and we hypothesize that the correlation is causal. Geochemical processes associated with road-salt applications that can mobilize Ra into solution include competition by excess sodium for sorption sites and formation of chloride complexes (RaCl + and RaCl 2 ). The largest increases in Ra were in groundwater with low pH (≤5), which is an indirect surrogate for low cation-sorption capacity. Correlations with other potential anthropogenic causes for the increase in Ra were not observed, further suggesting a road-salt effect. Given the significant increase in Ra concentrations in this drinking-water source, the known carcinogenic risks from Ra, the direct link to road-salt application, and the likelihood for continued increases, additional monitoring is necessary in areas with similar hydrogeologic and geochemical settings.

New Jersey↗

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

The relation of geogenic contaminants to groundwater age, aquifer hydrologic position, water type, and redox conditions in Atlantic and Gulf Coastal Plain aquifers, eastern and south-central USA

Groundwater age distributions developed from carbon-14 (14C), tritium (3H), and helium-4 (4He) concentrations, along with aquifer hydrologic position, water type, and redox conditions, were compared to geogenic contaminants of concern (GCOC) from 252 public-supply wells in six Atlantic and Gulf Coastal Plain unconsolidated-sediment aquifers. Concentrations of one or more GCOCs in 168 (67%) wells exceeded MCLs (maximum contaminant levels), SMCLs (secondary MCLs), or HBSLs (health-based screening levels). Human-health benchmark thresholds (MCLs or HBSLs) were exceeded in 31 (12%) wells, and included 0.8% for fluoride (F), 2.4% for arsenic (As), 4% for lead-210 (210Pb), and 4.8% for polonium-210 (210Po). Values of pH increase with age and were outside the SMCL in 31% of wells (23% < 6.5 and 7.5% > 8.5, SMCL). Among GCOCs with concentrations that increased significantly with groundwater age, the frequency of sentry threshold exceedances (i.e., one-half of MCL, SMCL, or HBSL) included 40% for dissolved solids (DS), 12% for chloride (Cl), 3.6% for F, 4.4% for As, and 9.1% for 210Po. Iron (Fe) concentrations did not correlate with groundwater age but exceeded sentry thresholds in 29% of wells. Groundwater age, water types, redox, pH, and GCOCs varied because of unique hydrogeologic features of the aquifers (recharge locations and geometry). As expected, primarily confined aquifers had young, oxic, low to near-neutral pH water near the outcrop (recharge area), and older, reduced, high pH water deeper and farther along flow paths. However, unique aquifer hydrogeologic conditions, such as multiple-recharge zones produced anomalous patterns of young and old groundwater at varying depths and locations along flow paths. Evidence for this variability is seen in disequilibrium patterns in the progression of the chemical evolution of groundwater with hydrologic position. When hydrogeologic differences are considered, groundwater age combined with hydrologic-position data, can provide a strong basis for inferring potential occurrence of GCOCs.

Gulf Coastal Plain aquifers↗

USGS2018

Radium mobility and the age of groundwater in public-drinking-water supplies from the Cambrian-Ordovician aquifer system, north-central USA

High radium (Ra) concentrations in potable portions of the Cambrian-Ordovician (C-O) aquifer system were investigated using water-quality data and environmental tracers ( 3 H, 3 He trit , SF 6 , 14 C and 4 He rad ) of groundwater age from 80 public-supply wells (PSWs). Groundwater ages were estimated by calibration of tracers to lumped parameter models and ranged from modern (<50 yr) in upgradient, regionally unconfined areas to ancient (>1 Myr) in the most downgradient, confined portions of the potable system. More than 80 and 40 percent of mean groundwater ages were older than 1000 and 50,000 yr, respectively. Anoxic, Fe-reducing conditions and increased mineralization develop with time in the aquifer system and mobilize Ra into solution resulting in the frequent occurrence of combined Ra (Ra c = 226 Ra + 228 Ra) at concentrations exceeding the USEPA MCL of 185 mBq/L (5 pCi/L). The distribution of the three Ra isotopes comprising total Ra (Ra t = 224 Ra + 226 Ra + 228 Ra) differed across the aquifer system. The concentrations of 224 Ra and 228 Ra were strongly correlated and comprised a larger proportion of the Ra t concentration in samples from the regionally unconfined area, where arkosic sandstones provide an enhanced source for progeny from the 232 Th decay series. 226 Ra comprised a larger proportion of the Ra t concentration in samples from downgradient confined regions. Concentrations of Ra t were significantly greater in samples from the regionally confined area of the aquifer system because of the increase in 226 Ra concentrations there as compared to the regionally unconfined area. 226 Ra distribution coefficients decreased substantially with anoxic conditions and increasing ionic strength of groundwater (mineralization), indicating that Ra is mobilized to solution from solid phases of the aquifer as adsorption capacity is diminished. The amount of 226 Ra released from solid phases by alpha-recoil mechanisms and retained in solution increases relative to the amount of Ra sequestered by adsorption processes or co-precipitation with barite as adsorption capacity and the concentration of Ba decreases. Although 226 Ra occurred at concentrations greater than 224 Ra or 228 Ra, the ingestion exposure risk was greater for 228 Ra owing to its greater toxicity. In addition, 224 Ra added substantial alpha-particle radioactivity to potable samples from the C-O aquifer system. Thus, monitoring for Ra isotopes and gross-alpha-activity (GAA) is important in upgradient, regionally unconfined areas as downgradient, and GAA measurements made within 72 h of sample collection would best capture alpha-particle radiation from the short-lived 224 Ra.

Applied Geochemistry↗

USGS2016

Urban development and stream ecosystem health—Science capabilities of the U.S. Geological Survey

Urban development creates multiple stressors that can degrade stream ecosystems by changing stream hydrology, water quality, and physical habitat. Contaminants, habitat destruction, and increasing streamflow variability resulting from urban development have been associated with the disruption of biological communities, particularly the loss of sensitive aquatic biota. Understanding how algal, invertebrate, and fish communities respond to these physical and chemical stressors can provide important clues as to how streams should be managed to protect stream ecosystems as a watershed becomes increasingly urbanized. The U.S. Geological Survey continues to lead monitoring efforts and scientific studies on the effects of urban development on stream ecosystems in metropolitan areas across the United States.

Fact Sheet↗

USGS2016

Arsenic and radionuclide occurrence and relation to geochemistry in groundwater of the Gulf Coast Aquifer System in Houston, Texas, 2007–11

The U.S. Geological Survey (USGS), in cooperation with the City of Houston, began a study in 2007 to determine concentrations, spatial extent, and associated geochemical conditions that might be conducive for mobility and transport of selected naturally occurring trace elements and radionuclides in the Gulf Coast aquifer system in Houston, Texas. Water samples were collected from 91 municipal supply wells completed in the Evangeline and Chicot aquifers of the Gulf Coast aquifer system in northeastern, northwestern, and southwestern Houston; hereinafter referred to as northeast, northwest and southwest Houston areas. Wells were sampled in three phases: (1) 28 municipal supply wells were sampled during 2007–8, (2) 60 municipal supply wells during 2010, and (3) 3 municipal supply wells during December 2011. During each phase of sampling, samples were analyzed for major ions, selected trace elements, and radionuclides. At a subset of wells, concentrations of arsenic species and other radionuclides (carbon-14, radium-226, radium-228, radon-222, and tritium) also were analyzed. Selected physicochemical properties were measured in the field at the time each sample was collected, and oxidation-reduction potential and unfiltered sulfides also were measured at selected wells. The source-water (the raw, ambient water withdrawn from municipal supply wells prior to water treatment) samples were collected for assessment of aquifer conditions in order to provide community water-system operators information that could be important when they make decisions about which treatment processes to apply before distributing finished drinking water. Geochemical conditions of groundwater of the Gulf Coast aquifer system are suitable in some instances for release of arsenic and radionuclides from aquifer materials. Recent changes to the U.S. Environmental Protection Agency (EPA) primary drinking-water regulations for arsenic and a selected number of natural radionuclides have highlighted the necessity for municipal supply system managers to be aware of the occurrence and distribution of these constituents in their source water. Concentrations of arsenic ranged from 0.58 to 23.5 micrograms per liter (μg/L), with relatively low median and 75th percentile concentrations (2.7 and 3.6 μg/L, respectively). The gross alpha-particle activity completed within 72 hours after sample collection ranged from R-1.1 (nondetect where the result was below the sample specific critical level) to 39.7 picocuries per liter (pCi/L), with a median of 10.3 pCi/L. After 30 days, the gross alpha-particle activities in the 91 samples ranged from R-0.94 to 25.5 pCi/L, with a median of 5.60 pCi/L. Concentrations of uranium ranged from less than 0.02 to 42.7 μg/L, with a median value of 1.69 μg/L and a 75th-percentile value of 6.48 μg/L. The maximum concentrations of radium-226 and combined radium (sum of radium-226 plus radium-228) were 4.34 pCi/L and 3.23 pCi/L, respectively. Aquifer major-ion geochemistry was characterized and shown to contain three chemical types of water as grouped by a simplified predominant cation and anion classification system: (1) calcium- bicarbonate type, (2) sodium-bicarbonate type, and (3) sodium-chloride type. Aquifer geochemistry also was characterized into four reduction-oxidation (redox) categories: (1) oxic, (2) suboxic, (3) mixed, and (4) anoxic. Within the anoxic category, groundwater was further characterized into four presumed predominant reduction processes: (1) iron or sulfate or both [Fe(III)/SO 4 ] reducing, (2) iron [Fe(III)] reducing, (3) iron and sulfate [Fe(III)-SO 4 ] reducing, or (4) methanogenic, as defined by composition of redox species. The oxic category was associated with calcium-bicarbonate-type water, and the methanogenic-anoxic process was associated exclusively with the sodium-bicarbonate-type water. The species of arsenic and the dominant radionuclide present were associated with specific redox categories. Arsenate was associated primarily with oxic water and did not exceed 3.5 µg/L, whereas arsenite was associated with iron-reducing, anoxic water samples and, at the highest concentrations, occurred in sulfate-reducing, anoxic; methanogenic-anoxic; or both water samples. Uranium was associated exclusively with the oxic water, whereas the highest concentrations of combined radium were associated with the iron-reducing, anoxic water. The gross alpha-particle activity was greatest in the oxic waters where the source of the radioactivity was the uranium. Associated geochemical conditions conducive for mobility of arsenic and radionuclides and their spatial and vertical extent in the Gulf Coast aquifer system in Houston are important aspects to the areal management of the municipal groundwater supplies in Houston. Ongoing research is seeking to define chemical or geological factors that are the optimal indicators for elevated concentrations of these naturally occurring constituents.

Texas↗

USGS2016

Sediment chemistry and toxicity in Barnegat Bay, New Jersey: Pre- and post-Hurricane Sandy, 2012–13

Hurricane Sandy made landfall in Barnegat Bay, October, 29, 2012, damaging shorelines and infrastructure. Estuarine sediment chemistry and toxicity were investigated before and after to evaluate potential environmental health impacts and to establish post-event baseline sediment-quality conditions. Trace element concentrations increased throughout Barnegat Bay up to two orders of magnitude, especially north of Barnegat Inlet, consistent with northward redistribution of silt. Loss of organic compounds, clay, and organic carbon is consistent with sediment winnowing and transport through the inlets and sediment transportmodeling results. The number of sites exceeding sediment quality guidance levels for trace elements tripled post-Sandy. Sediment toxicity post-Sandy was mostly unaffected relative to pre-Sandy conditions, but at the site with the greatest relative increase for trace elements, survival rate of the test amphipod decreased (indicating degradation). This study would not have been possible without comprehensive baseline data enabling the evaluation of storm-derived changes in sediment quality.

New Jersey↗

USGS2016

An assessment of mercury in estuarine sediment and tissue in Southern New Jersey using public domain data

Mercury (Hg) is considered a contaminant of global concern for coastal environments due to its toxicity, widespread occurrence in sediment, and bioaccumulation in tissue. Coastal New Jersey, USA, is characterized by shallow bays and wetlands that provide critical habitat for wildlife but share space with expanding urban landscapes. This study was designed as an assessment of the magnitude and distribution of Hg in coastal New Jersey sediments and critical species using publicly available data to highlight potential data gaps. Mercury concentrations in estuary sediments can exceed 2 μg/g and correlate with concentrations of other metals. Based on existing data, the concentrations of Hg in mussels in southern New Jersey are comparable to those observed in other urbanized Atlantic Coast estuaries. Lack of methylmercury data for sediments, other media, and tissues are data gaps needing to be filled for a clearer understanding of the impacts of Hg inputs to the ecosystem.

New Jersey↗

USGS2015

The quality of our Nation's waters: Water quality in the Northern Atlantic Coastal Plain surficial aquifer system, Delaware, Maryland, New Jersey, New York, North Carolina, and Virginia, 1988-2009

The surficial aquifer system of the Northern Atlantic Coastal Plain is made up of unconfined aquifers that underlie most of the area. This aquifer system is a critical renewable source of drinking water and is the source of most flow to streams and of recharge to underlying confined aquifers. Millions of people rely on the surficial aquifer system for public and domestic water supply, in particular in the densely populated areas of Long Island, New York, and in southern New Jersey, but also in more rural areas. Because the aquifer sediments are permeable and the water table is shallow, the surficial aquifer system is vulnerable to contamination from chemicals that are applied to the land surface and carried into groundwater with infiltrating rainfall and snowfall. Major Findings The quality of most groundwater produced for public and domestic water supply is suitable for drinking, although contaminants at concentrations greater than human-health benchmarks have been detected in some places Nitrate is one of the most widespread contaminants in groundwater Radium occurs commonly in groundwater as a result of the degradation of uranium and thorium minerals naturally present in aquifer sediments Chemicals in groundwater move slowly and can be detected in the environment for several decades after they enter the surficial aquifer system

Delaware, Maryland, New Jersey, New York, North Ca↗

USGS2015

The quality of our nation's waters: Water quality in the Principal Aquifers of the Piedmont, Blue Ridge, and Valley and Ridge regions, eastern United States, 1993-2009

The aquifers of the Piedmont, Blue Ridge, and Valley and Ridge regions underlie an area with a population of more than 40 million people in 10 states. The suburban and rural population is large, growing rapidly, and increasingly dependent on groundwater as a source of supply, with more than 550 million gallons per day withdrawn from domestic wells for household use. Water from some of these aquifers does not meet human-health benchmarks for drinking water for contaminants with geologic or human sources. Water from samples in crystalline- and siliciclastic-rock aquifers frequently exceeded standards for contaminants with geologic sources, and samples in carbonate-rock aquifers frequently exceeded standards for contaminants with human sources, most often nitrate and bacteria. Major Findings Many contaminants in groundwater have geologic sources, but geochemical conditions control whether or not those contaminants dissolve and move through groundwater Concentrations of nitrate and bacteria—the main drinking-water contaminants with human sources—were high in carbonate-rock aquifers and frequently exceeded human-health benchmarks Large contributions of nitrate and phosphorus from groundwater to streams have a negative effect on ecological health of estuaries, such as the Chesapeake Bay and Albemarle-Pamlico Sound

Piedmont, Blue Ridge, Valley and Ridge regions↗

USGS2013

Variable contributions of mercury from groundwater to a first-order urban coastal plain stream in New Jersey, USA

Filtered total mercury (FTHg) concentrations in a rapidly urbanizing area ranged from 50 to 250 ng/L in surface waters of the Squankum Branch, a tributary to a major river (Great Egg Harbor River (GEHR)) traversing both urban and forested/wetland areas in the Coastal Plain of New Jersey. An unsewered residential area with Hg-contaminated well water (one of many in the region) is adjacent to the stream’s left bank. Although the region’s groundwater contains total Hg (THg) at background levels of <10 ng/L, water from about 700 domestic wells in urbanized areas completed in the acidic, quartzose unconfined aquifer typically at depths 20 to 30 m below land surface has been found to exceed 2,000 ng/L (the USEPA maximum contaminant level). Within urbanized areas, THg concentrations in shallow groundwater (<20 m below land surface at or near the water table) and the potential for Hg transport were not well known, representing a considerable knowledge gap. Sampling of streamwater in, and groundwater discharge to, the Squankum Branch watershed revealed that concentrations of THg generally were in the range of 1 to 10 ng/L, but narrow plumes (“plumelets”) of shallow groundwater discharging to the stream from the opposing banks contained FTHg at a concentration > 5,000 ng/L (left bank) and nearly 2,000 ng/L (right bank). The Hg content of bankside soils and sediments was high (up to 12 mg/kg) and mostly acid leachable where groundwater with high Hg concentrations discharged, indicating contributions of Hg by both runoff and shallow groundwater. Elevated concentrations of nutrients and chloride in some groundwater plumelets likely indicated inputs from septic-system effluent and (or) fertilizer applications. The Hg probably derives mainly from mercurial pesticide applications to the former agricultural land being urbanized. The study results show that soil disturbance and introduction of anthropogenic substances can mobilize Hg from soils to shallow groundwater and the Hg contamination travels in narrow plumelets to discharge points such as stream tributaries. In the entire GEHR watershed, THg concentrations in groundwater discharging to streams in urban areas tended to be higher than concentrations in water discharging to streams of forested areas, consistent with the results from this small watershed. Other areas with similar quartzose coastal aquifers, land-use history, and hydrogeology may be similarly vulnerable to Hg contamination of shallow groundwater and associated surface water.

New Jersey↗

USGS2013

Electrical signatures of ethanol-liquid mixtures: implications for monitoring biofuels migration in the subsurface

Ethanol (EtOH), an emerging contaminant with potential direct and indirect environmental effects, poses threats to water supplies when spilled in large volumes. A series of experiments was directed at understanding the electrical geophysical signatures arising from groundwater contamination by ethanol. Conductivity measurements were performed at the laboratory scale on EtOH–water mixtures (0 to 0.97 v/v EtOH) and EtOH–salt solution mixtures (0 to 0.99 v/v EtOH) with and without a sand matrix using a conductivity probe and a four-electrode electrical measurement over the low frequency range (1–1000 Hz). A Lichtenecker–Rother (L–R) type mixing model was used to simulate electrical conductivity as a function of EtOH concentration in the mixture. For all three experimental treatments increasing EtOH concentration resulted in a decrease in measured conductivity magnitude (|σ|). The applied L–R model fitted the experimental data at concentration ≤ 0.4 v/v EtOH, presumably due to predominant and symmetric intermolecular (EtOH–water) interaction in the mixture. The deviation of the experimental |σ| data from the model prediction at higher EtOH concentrations may be associated with hydrophobic effects of EtOH–EtOH interactions in the mixture. The |σ| data presumably reflected changes in relative strength of the three types of interactions (water–water, EtOH–water, and EtOH–EtOH) occurring simultaneously in EtOH–water mixtures as the ratio of EtOH to water changed. No evidence of measurable polarization effects at the EtOH–water and EtOH–water–mineral interfaces over the investigated frequency range was found. Our results indicate the potential for using electrical measurements to characterize and monitor EtOH spills in the subsurface.

Journal of Contaminant Hydrology↗

USGS2013

Complex resistivity signatures of ethanol in sand-clay mixtures

We performed complex resistivity (CR) measurements on laboratory columns to investigate changes in electrical properties as a result of varying ethanol (EtOH) concentration (0% to 30% v/v) in a sand–clay (bentonite) matrix. We applied Debye decomposition, a phenomenological model commonly used to fit CR data, to determine model parameters (time constant: τ, chargeability: m, and normalized chargeability: m n ). The CR data showed a significant (P ≤ 0.001) time-dependent variation in the clay driven polarization response (~ 12 mrad) for 0% EtOH concentration. This temporal variation probably results from the clay–water reaction kinetics trending towards equilibrium in the sand–clay–water system. The clay polarization is significantly suppressed (P ≤ 0.001) for both measured phase (ϕ) and imaginary conductivity (σ″) with increasing EtOH concentration. Normalized chargeability consistently decreases (by up to a factor of ~ 2) as EtOH concentration increases from 0% to 10% and 10 to 20%, respectively. We propose that such suppression effects are associated with alterations in the electrical double layer (EDL) at the clay–fluid interface due to (a) strong EtOH adsorption on clay, and (b) complex intermolecular EtOH–water interactions and subsequent changes in ionic mobility on the surface in the EDL. Changes in the CR data following a change of the saturating fluid from EtOH 20% to plain water indicate strong hysteresis effects in the electrical response, which we attribute to persistent EtOH adsorption on clay. Our results demonstrate high sensitivity of CR measurements to clay–EtOH interactions in porous media, indicating the potential application of this technique for characterization and monitoring of ethanol contamination in sediments containing clays.

Journal of Contaminant Hydrology↗

USGS2013

Complex resistivity signatures of ethanol biodegradation in porous media

Numerous adverse effects are associated with the accidental release of ethanol (EtOH) and its persistence in the subsurface. Geophysical techniques may permit non-invasive, real time monitoring of microbial degradation of hydrocarbon. We performed complex resistivity (CR) measurements in conjunction with geochemical data analysis on three microbial-stimulated and two control columns to investigate changes in electrical properties during EtOH biodegradation processes in porous media. A Debye Decomposition approach was applied to determine the chargeability ( m ), normalized chargeability ( m n ) and time constant ( τ ) of the polarization magnitude and relaxation length scale as a function of time. The CR responses showed a clear distinction between the bioaugmented and control columns in terms of real ( σ′ ) and imaginary ( σ″ ) conductivity, phase ( ϕ ) and apparent formation factor ( F app ). Unlike the control columns, a substantial decrease in σ′ and increase in F app occurred at an early time (within 4 days) of the experiment for all three bioaugmented columns. The observed decrease in σ′ is opposite to previous studies on hydrocarbon biodegradation. These columns also exhibited increases in ϕ (up to ~ 9 mrad) and σ″ (up to two order of magnitude higher) 5 weeks after microbial inoculation. Variations in m and m n were consistent with temporal changes in ϕ and σ″ responses, respectively. Temporal geochemical changes and high resolution scanning electron microscopy imaging corroborated the CR findings, thus indicating the sensitivity of CR measurements to EtOH biodegradation processes. Our results offer insight into the potential application of CR measurements for long-term monitoring of biogeochemical and mineralogical changes during intrinsic and induced EtOH biodegradation in the subsurface.

Journal of Contaminant Hydrology↗

USGS2013

Water resources and shale gas/oil production in the Appalachian Basin: critical issues and evolving developments

Unconventional natural gas and oil resources in the United States are important components of a national energy program. While the Nation seeks greater energy independence and greener sources of energy, Federal agencies with environmental responsibilities, state and local regulators and water-resource agencies, and citizens throughout areas of unconventional shale gas development have concerns about the environmental effects of high volume hydraulic fracturing (HVHF), including those in the Appalachian Basin in the northeastern United States (fig. 1). Environmental concerns posing critical challenges include the availability and use of surface water and groundwater for hydraulic fracturing; the migration of stray gas and potential effects on overlying aquifers; the potential for flowback, formation fluids, and other wastes to contaminate surface water and groundwater; and the effects from drill pads, roads, and pipeline infrastructure on land disturbance in small watersheds and headwater streams (U.S. Government Printing Office, 2012). Federal, state, regional and local agencies, along with the gas industry, are striving to use the best science and technology to develop these unconventional resources in an environmentally safe manner. Some of these concerns were addressed in U.S. Geological Survey (USGS) Fact Sheet 2009–3032 (Soeder and Kappel, 2009) about potential critical effects on water resources associated with the development of gas extraction from the Marcellus Shale of the Hamilton Group (Ver Straeten and others, 1994). Since that time, (1) the extraction process has evolved, (2) environmental awareness related to high-volume hydraulic fracturing process has increased, (3) state regulations concerning gas well drilling have been modified, and (4) the practices used by industry to obtain, transport, recover, treat, recycle, and ultimately dispose of the spent fluids and solid waste materials have evolved. This report updates and expands on Fact Sheet 2009–3032 and presents new information regarding selected aspects of unconventional shale gas development in the Appalachian Basin (primarily Virginia, West Virginia, Maryland, Pennsylvania, Ohio, and New York). This document was prepared by the USGS, in cooperation with the U.S. Department of Energy, and reviews the evolving technical advances and scientific studies made in the Appalachian Basin between 2009 and the present (2013), addressing past and current issues for oil and gas development in the region.

Maryl;New York;Ohio;Pennsylvania;Virginia;West Vir↗

USGS2013

Naturally occurring contaminants in the Piedmont and Blue Ridge crystalline-rock aquifers and Piedmont Early Mesozoic basin siliciclastic-rock aquifers, eastern United States, 1994–2008

Groundwater quality and aquifer lithologies in the Piedmont and Blue Ridge Physiographic Provinces in the eastern United States vary widely as a result of complex geologic history. Bedrock composition (mineralogy) and geochemical conditions in the aquifer directly affect the occurrence (presence in rock and groundwater) and distribution (concentration and mobility) of potential naturally occurring contaminants, such as arsenic and radionuclides, in drinking water. To evaluate potential relations between aquifer lithology and the spatial distribution of naturally occurring contaminants, the crystalline-rock aquifers of the Piedmont and Blue Ridge Physiographic Provinces and the siliciclastic-rock aquifers of the Early Mesozoic basin of the Piedmont Physiographic Province were divided into 14 lithologic groups, each having from 1 to 16 lithochemical subgroups, based on primary rock type, mineralogy, and weathering potential. Groundwater-quality data collected by the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) Program from 1994 through 2008 from 346 wells and springs in various hydrogeologic and land-use settings from Georgia through New Jersey were compiled and analyzed for this study. Analyses for most constituents were for filtered samples, and, thus, the compiled data consist largely of dissolved concentrations. Concentrations were compared to criteria for protection of human health, such as U.S. Environmental Protection Agency (USEPA) drinking water maximum contaminant levels and secondary maximum contaminant levels or health-based screening levels developed by the USGS NAWQA Program in cooperation with the USEPA, the New Jersey Department of Environmental Protection, and Oregon Health & Science University. Correlations among constituent concentrations, pH, and oxidation-reduction (redox) conditions were used to infer geochemical controls on constituent mobility within the aquifers. Of the 23 trace-element constituents evaluated, arsenic, manganese, and zinc were detected in one or more water samples at concentrations greater than established human health-based criteria. Arsenic concentrations typically were less than 1 microgram per liter (µg/L) in most groundwater samples; however, concentrations of arsenic greater than 1 µg/L frequently were detected in groundwater from clastic lacustrine sedimentary rocks of the Early Mesozoic basin aquifers and from metamorphosed clastic sedimentary rocks of the Piedmont and Blue Ridge crystalline rock aquifers. Groundwater from these rock units had elevated pH compared to other rock units evaluated in this study. Of the nine samples for which arsenic concentration was greater than 10 µg/L, six were classified as oxic and three as anoxic, and seven had pH of 7.2 or greater. Manganese concentrations typically were less than 10 µg/L in most samples; however, 8.3 percent of samples from the Piedmont and Blue Ridge crystalline-rock aquifers and 3.0 percent of samples from the Early Mesozoic basin siliciclastic rock aquifers had manganese concentrations greater than the 300-µg/L health-based screening level. The positive correlation of manganese with iron and ammonia and the negative correlation of manganese with dissolved oxygen and nitrate are consistent with the reductive dissolution of manganese oxides in the aquifer. Zinc concentrations typically were less than 10 µg/L in the groundwater samples considered in the study, but 0.4 percent and 5.5 percent of the samples had concentrations greater than the health-based screening level of 2,000 µg/L and one-tenth of the health-based screening level, respectively. The mean rank concentration of zinc in groundwater from the quartz-rich sedimentary rock lithologic group was greater than that for other lithologic groups even after eliminating samples collected from wells constructed with galvanized casing. Approximately 90 percent of 275 groundwater samples had radon-222 concentrations that were greater than the proposed alternative maximum contaminant level of 300 picocuries per liter. In contrast, only 2.0 percent of 98 samples had combined radium (radium-226 plus radium-228) concentrations greater than the maximum contaminant level of 5.0 picocuries per liter, and 0.6 percent of 310 samples had uranium concentrations greater than the maximum contaminant level of 30 µg/L. Radon concentrations were highest in the Piedmont and Blue Ridge crystalline-rock aquifers, especially in granite, and elevated median concentrations were noted in the Piedmont Early Mesozoic basin aquifers, but without the extreme maximum concentrations found in the crystalline rocks (granites). Although the siliciclastic lithologies had a greater frequency of elevated uranium concentrations, radon and radium were commonly detected in water from both siliciclastic and crystalline lithologies. Uranium concentrations in groundwater from clastic sedimentary and clastic lacustrine/evaporite sedimentary lithologic groups within the Early Mesozoic basin aquifers, which had median concentrations of 3.6 and 3.1 µg/L, respectively, generally were higher than concentrations for other siliciclastic lithologic groups, which had median concentrations less than 1 µg/L. Although 89 percent of the 260 samples from crystalline-rock aquifers had uranium concentrations less than 1 µg/L, 0.8 percent had uranium concentrations greater than the 30-µg/L maximum contaminant level, and 6.5 percent had concentrations greater than 3 µg/L.

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