Geology topics

Madeline E. Schreiber

Publications and source records attributed to Madeline E. Schreiber.

7 recordsLinked to original sources

USGS2021

Arsenic in petroleum-contaminated groundwater near Bemidji, Minnesota is predicted to persist for centuries

We used a reactive transport model to investigate the cycling of geogenic arsenic (As) in a petroleum-contaminated aquifer. We simulated As mobilization and sequestration using surface complexation reactions with Fe(OH) 3 during petroleum biodegradation coupled with Fe-reduction. Model results predict that dissolved As in the plume will exceed the U.S. and EU 10 µg/L drinking water standard for ~400 years. Non-volatile dissolved organic carbon (NVDOC) in the model promotes As mobilization by exerting oxygen demand, which maintains anoxic conditions in the aquifer. After NVDOC degrades, As re-associates with Fe(OH) 3 as oxygenated conditions are re-established. Over the 400-year simulation, As transport resembles a “roll front” in which: (1) arsenic sorbed to Fe(OH) 3 is released during Fe-reduction coupled to petroleum biodegradation; (2) dissolved As resorbs to Fe(OH) 3 at the plume’s leading edge; and (3) over time, the plume expands, and resorbed As is re-released into groundwater. This “roll front” behavior underscores the transience of sorption as an As attenuation mechanism. Over the plume’s lifespan, simulations suggest that As will contaminate more groundwater than benzene from the oil spill. At its maximum, the model simulates that ~5.7× more groundwater will be contaminated by As than benzene, suggesting that As could pose a greater long-term water quality threat than benzene in this petroleum-contaminated aquifer.

Minnesota↗

USGS2017

A mass balance approach to investigate arsenic cycling in a petroleum plume

Natural attenuation of organic contaminants in groundwater can give rise to a series of complex biogeochemical reactions that release secondary contaminants to groundwater. In a crude oil contaminated aquifer, biodegradation of petroleum hydrocarbons is coupled with the reduction of ferric iron (Fe(III)) hydroxides in aquifer sediments. As a result, naturally occurring arsenic (As) adsorbed to Fe(III) hydroxides in the aquifer sediment is mobilized from sediment into groundwater. However, Fe(III) in sediment of other zones of the aquifer has the capacity to attenuate dissolved As via resorption. In order to better evaluate how long-term biodegradation coupled with Fe-reduction and As mobilization can redistribute As mass in contaminated aquifer, we quantified mass partitioning of Fe and As in the aquifer based on field observation data. Results show that Fe and As are spatially correlated in both groundwater and aquifer sediments. Mass partitioning calculations demonstrate that 99.9% of Fe and 99.5% of As are associated with aquifer sediment. The sediments act as both sources and sinks for As, depending on the redox conditions in the aquifer. Calculations reveal that at least 78% of the original As in sediment near the oil has been mobilized into groundwater over the 35-year lifespan of the plume. However, the calculations also show that only a small percentage of As (∼0.5%) remains in groundwater, due to resorption onto sediment. At the leading edge of the plume, where groundwater is suboxic, sediments sequester Fe and As, causing As to accumulate to concentrations 5.6 times greater than background concentrations. Current As sinks can serve as future sources of As as the plume evolves over time. The mass balance approach used in this study can be applied to As cycling in other aquifers where groundwater As results from biodegradation of an organic carbon point source coupled with Fe reduction.

Environmental Pollution↗

USGS2017

The role of alluvial aquifer sediments in attenuating a dissolved arsenic plume

In a crude-oil-contaminated sandy aquifer at the Bemidji site in northern Minnesota, biodegradation of petroleum hydrocarbons has resulted in release of naturally occurring As to groundwater under Fe-reducing conditions. This study used chemical extractions of aquifer sediments collected in 1993 and 2011–2014 to evaluate the relationship between Fe and As in different redox zones (oxic, methanogenic, Fe-reducing, anoxic-suboxic transition) of the contaminated aquifer over a twenty-year period. Results show that 1) the aquifer has the capacity to naturally attenuate the plume of dissolved As, primarily through sorption; 2) Fe and As are linearly correlated in sediment across all redox zones, and a regression analysis between Fe and As reasonably predicted As concentrations in sediment from 1993 using only Fe concentrations; 3) an As-rich “iron curtain,” associated with the anoxic-suboxic transition zone, migrated 30 m downgradient between 1993 and 2013 as a result of the hydrocarbon plume evolution; and 4) silt lenses in the aquifer preferentially sequester dissolved As, though As is remobilized into groundwater from sediment after reducing conditions are established. Using results of this study coupled with historical data, we develop a conceptual model which summarizes the natural attenuation of As and Fe over time and space that can be applied to other sites that experience As mobilization due to an influx of bioavailable organic matter.

Journal of Contaminant Hydrology↗

USGS2016

Analysis of hydrologic and geochemical time-series data at James Cave, Virginia: Implications for epikarst influence on recharge in Appalachian karst aquifers

The epikarst, which consists of highly weathered rock in the upper vadose zone of exposed karst systems, plays a critical role in determining the hydrologic and geochemical characteristics of recharge to an underlying karst aquifer. This study utilized time series (2007–2014) of hydrologic and geochemical data of drip water collected within James Cave, Virginia, to examine the influence of epikarst on the quantity and quality of recharge in a mature, doline-dominated karst terrain. Results show a strong seasonality of both hydrology and geochemistry of recharge, which has implications for management of karst aquifers in temperate climatic zones. First, recharge (discharge from the epikarst to the underlying aquifer) reaches a maximum between late winter and early spring, with the onset of the recharge season ranging from as early as December to as late as March during the study period. The timing and duration of the recharge season were found to be a function of precipitation in excess of evapotranspiration on a seasonal time scale. Secondly, seasonally variable residence times for water in the epikarst influence rock-water interaction and, hence, the geochemical characteristics of recharge. Overall, results highlight the strong and complex influence that the epikarst has on karst recharge, which requires long-term and high-resolution data sets to accurately understand and quantify.

Virginia↗

USGS2015

Instrumenting caves to collect hydrologic and geochemical data: case study from James Cave, Virginia

Karst aquifers are productive groundwater systems, supplying approximately 25 % of the world’s drinking water. Sustainable use of this critical water supply requires information about rates of recharge to karst aquifers. The overall goal of this project is to collect long-term, high-resolution hydrologic and geochemical datasets at James Cave, Virginia, to evaluate the quantity and quality of recharge to the karst system. To achieve this goal, the cave has been instrumented for continuous (10-min interval) measurement of the (1) temperature and rate of precipitation; (2) temperature, specific conductance, and rate of epikarst dripwater; (3) temperature of the cave air; and (4) temperature, conductivity, and discharge of the cave stream. Instrumentation has also been installed to collect both composite and grab samples of precipitation, soil water, the cave stream, and dripwater for geochemical analysis. This chapter provides detailed information about the instrumentation, data processing, and data management; shows examples of collected datasets; and discusses recommendations for other researchers interested in hydrologic and geochemical monitoring of cave systems. Results from the research, briefly described here and discussed in more detail in other publications, document a strong seasonality of the start of the recharge season, the extent of the recharge season, and the geochemistry of recharge.

Virginia↗

USGS2015

Arsenic cycling in hydrocarbon plumes: secondary effects of natural attenuation

Monitored natural attenuation is widely applied as a remediation strategy at hydrocarbon spill sites. Natural attenuation relies on biodegradation of hydrocarbons coupled with reduction of electron acceptors, including solid phase ferric iron (Fe(III)). Because arsenic (As) adsorbs to Fe-hydroxides, a potential secondary effect of natural attenuation of hydrocarbons coupled with Fe(III) reduction is a release of naturally occurring As to groundwater. At a crude-oil-contaminated aquifer near Bemidji, Minnesota, anaerobic biodegradation of hydrocarbons coupled to Fe(III) reduction has been well documented. We collected groundwater samples at the site annually from 2009 to 2013 to examine if As is released to groundwater and, if so, to document relationships between As and Fe inside and outside of the dissolved hydrocarbon plume. Arsenic concentrations in groundwater in the plume reached 230 µg/L, whereas groundwater outside the plume contained less than 5 µg/L As. Combined with previous data from the Bemidji site, our results suggest that (1) naturally occurring As is associated with Fe-hydroxides present in the glacially derived aquifer sediments; (2) introduction of hydrocarbons results in reduction of Fe-hydroxides, releasing As and Fe to groundwater; (3) at the leading edge of the plume, As and Fe are removed from groundwater and retained on sediments; and (4) downgradient from the plume, patterns of As and Fe in groundwater are similar to background. We develop a conceptual model of secondary As release due to natural attenuation of hydrocarbons that can be applied to other sites where an influx of biodegradable organic carbon promotes Fe(III) reduction.

Minnesota↗

USGS2015

Statistical analysis of soil geochemical data to identify pathfinders associated with mineral deposits: An example from the Coles Hill uranium deposit, Virginia, USA

Soil geochemical anomalies can be used to identify pathfinders in exploration for ore deposits. In this study, compositional data analysis is used with multivariate statistical methods to analyse soil geochemical data collected from the Coles Hill uranium deposit, Virginia, USA, to identify pathfinders associated with this deposit. Elemental compositions and relationships were compared between the collected Coles Hill soil and reference soil samples extracted from a regional subset of a national-scale geochemical survey. Results show that pathfinders for the Coles Hill deposit include light rare earth elements (La and Ce), which, when normalised by their Al content, are correlated with U/Al, and elevated Th/Al values, which are not correlated with U/Al, supporting decoupling of U from Th during soil generation. These results can be used in genetic and weathering models of the Coles Hill deposit, and can also be applied to future prospecting for similar U deposits in the eastern United States, and in regions with similar geological/climatic conditions.

Virginia↗