Geology topics

Nathaniel R. Warner

Publications and source records attributed to Nathaniel R. Warner.

7 recordsLinked to original sources

USGS2024

Evaluation of coal mine drainage and associated precipitates for radium and rare earth element concentrations

Coal mine drainage (CMD) and associated metal-rich precipitates have recently been proposed as unconventional sources of rare earth elements (REEs). However, the potential occurrence of radium (Ra), a known carcinogen, with the REE-bearing phases has not been investigated. We hypothesized that Ra may occur in solids that are precipitated from CMD as a “radiobarite” solid solution ((Ba,Sr,Ra)SO 4 ) and/or adsorbed with hydrous metal oxides. REEs have been documented to sorb or co-precipitate with iron (Fe), manganese (Mn), and aluminum (Al) oxyhydroxide in CMD solids. Likewise, Ra has been documented to sorb to hydrous Fe and Mn oxides especially where sulfate (SO 4 ) and/or barium (Ba) concentrations are insufficient to precipitate radiobarite. Thus, we conducted the first-ever survey of Ra concentrations in corresponding CMD water and solid samples in the United States. Samples were analyzed from 4 untreated and 9 treated CMD sites in both the bituminous and anthracite coal regions of Pennsylvania across a range of pH and SO 4 concentrations. The dissolved Ra in CMD was relatively low (<0.5 Bq/L), consistent with radiobarite solubility; however, CMD solids were largely composed of amorphous Fe, Al, and Mn oxyhydroxide and silicate minerals. Ra was associated with Mn-enriched CMD solids, upwards of 875 Bq/kg. Total REE + yttrium (Y) content in the CMD solids was enriched upwards of 3600 mg/kg and was significantly correlated with Al content. These preliminary results suggest that REE extraction may target Al-rich solids to avoid Ra in Mn-rich solids.

Pennsylvania↗

USGS2024

Utica/Point Pleasant brine isotopic compositions (δ7Li, δ11B, δ138Ba) elucidate mechanisms of lithium enrichment in the Appalachian Basin

Global Li production will require a ~500 % increase to meet 2050 projected energy storage demands. One potential source is oil and gas wastewater (i.e., produced water or brine), which naturally has high total dissolved solids (TDS) concentrations, that can also be enriched in Li (>100 mg/L). Understanding the sources and mechanisms responsible for high naturally-occurring Li concentrations can aid in efficient targeting of these brines. The isotopic composition (δ 7 Li, δ 11 B, δ 138 Ba) of produced water and core samples from the Utica Shale and Point Pleasant Formation (UPP) in the Appalachian Basin, USA indicates that depth-dependent thermal maturity and water-rock interaction, including diagenetic clay mineral transformations, likely control Li concentrations. A survey of Li content in produced waters throughout the USA indicates that Appalachian Basin brines from the Marcellus Shale to the UPP have the potential for economic resource recovery.

Maryland, Ohio, Pennsylvania, West Virginia↗

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↗

USGS2019

Accuracy of methods for reporting inorganic element concentrations and radioactivity in oil and gas wastewaters from the Appalachian Basin, U.S. based on an inter-laboratory comparison.

Accurate and precise analyses of oil and gas (O&G) wastewaters and solids ( e.g. , sediments and sludge) are important for the regulatory monitoring of O&G development and tracing potential O&G contamination in the environment. In this study, 15 laboratories participated in an inter-laboratory comparison on the chemical characterization of three O&G wastewaters from the Appalachian Basin and four solids impacted by O&G development, with the goal of evaluating the quality of data and the accuracy of measurements for various analytes of concern. Using a variety of different methods, analytes in the wastewaters with high concentrations ( i.e. , >5 mg L −1 ) were easily detectable with relatively high accuracy, often within ±10% of the most probable value (MPV). In contrast, often less than 7 of the 15 labs were able to report detectable trace metal(loid) concentrations ( i.e. , Cr, Ni, Cu, Zn, As, and Pb) with accuracies of approximately ±40%. Despite most labs using inductively coupled plasma mass spectrometry (ICP-MS) with low instrument detection capabilities for trace metal analyses, large dilution factors during sample preparation and low trace metal concentrations in the wastewaters limited the number of quantifiable determinations and likely influenced analytical accuracy. In contrast, all the labs measuring Ra in the wastewaters were able to report detectable concentrations using a variety of methods including gamma spectroscopy and wet chemical approaches following Environmental Protection Agency (EPA) standard methods. However, the reported radium activities were often greater than ±30% different to the MPV possibly due to calibration inconsistencies among labs, radon leakage, or failing to correct for self-attenuation. Reported radium activities in solid materials had less variability (±20% from MPV) but accuracy could likely be improved by using certified radium standards and accounting for self-attenuation that results from matrix interferences or a density difference between the calibration standard and the unknown sample. This inter-laboratory comparison illustrates that numerous methods can be used to measure major cation, minor cation, and anion concentrations in O&G wastewaters with relatively high accuracy while trace metal(loid) and radioactivity analyses in liquids may often be over ±20% different from the MPV.

Appalachian Basin↗

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↗

USGS2013

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

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

Applied Geochemistry↗

USGS2012

Shallow groundwater quality and geochemistry in the Fayetteville Shale gas-production area, north-central Arkansas, 2011

The Mississippian Fayetteville Shale serves as an unconventional gas reservoir across north-central Arkansas, ranging in thickness from approximately 50 to 550 feet and varying in depth from approximately 1,500 to 6,500 feet below the ground surface. Primary permeability in the Fayetteville Shale is severely limited, and successful extraction of the gas reservoir is the result of advances in horizontal drilling techniques and hydraulic fracturing to enhance and develop secondary fracture porosity and permeability. Drilling and production of gas wells began in 2004, with a steady increase in production thereafter. As of April 2012, approximately 4,000 producing wells had been completed in the Fayetteville Shale. In Van Buren and Faulkner Counties, 127 domestic water wells were sampled and analyzed for major ions and trace metals, with a subset of the samples analyzed for methane and carbon isotopes to describe general water quality and geochemistry and to investigate the potential effects of gas-production activities on shallow groundwater in the study area. Water-quality analyses from this study were compared to historical (pregas development) shallow groundwater quality collected in the gas-production area. An additional comparison was made using analyses from this study of groundwater quality in similar geologic and topographic areas for well sites less than and greater than 2 miles from active gas-production wells. Chloride concentrations for the 127 groundwater samples collected for this study ranged from approximately 1.0 milligram per liter (mg/L) to 70 mg/L, with a median concentration of 3.7 mg/L, as compared to maximum and median concentrations for the historical data of 378 mg/L and 20 mg/L, respectively. Statistical analysis of the data sets revealed statistically larger chloride concentrations (p-value <0.001) in the historical data compared to data collected for this study. Chloride serves as an important indicator parameter based on its conservative transport characteristics and relatively elevated concentrations in production waters associated with gas extraction activities. Major ions and trace metals additionally had lower concentrations in data gathered for this study than in the historical analyses. Additionally, no statistical difference existed between chloride concentrations from water-quality data collected for this study from 94 wells located less than 2 miles from a gas-production well and 33 wells located 2 miles or more from a gas-production well; a Wilcoxon rank-sum test showed a p-value of 0.71. Major ion chemistry was investigated to understand the effects of geochemical and reduction-oxidation (redox) processes on the shallow groundwater in the study area along a continuum of increased rock-water interaction represented by increases in dissolved solids concentration. Groundwater in sandstone formations is represented by a low dissolved solids concentration (less than 30 mg/L) and slightly acidic water type. Shallow shale aquifers were represented by dissolved solids concentrations ranging upward to 686 mg/L, and water types evolving from a dominantly mixed-bicarbonate and calcium-bicarbonate to a strongly sodium-bicarbonate water type. Methane concentration and carbon isotopic composition were analyzed in 51 of the 127 samples collected for this study. Methane occurred above a detection limit of 0.0002 mg/L in 32 of the 51 samples, with concentrations ranging upward to 28.5 mg/L. Seven samples had methane concentrations greater than or equal to 0.5 mg/L. The carbon isotopic composition of these higher concentration samples, including the highest concentration of 28.5 mg/L, shows the methane was likely biogenic in origin with carbon isotope ratio values ranging from -57.6 to -74.7 per mil. Methane concentrations increased with increases in dissolved solids concentrations, indicating more strongly reducing conditions with increasing rock-water interaction in the aquifer. As such, groundwater-quality data collected for this study indicate that groundwater chemistry in the shallow aquifer system in the study area is a result of natural processes, beginning with recharge of dilute atmospheric precipitation and evolution of observed groundwater chemistry through rock-water interaction and redox processes.

Arkansas↗