Melinda L. Erickson

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.

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.

Crude Oil Metabolites in Groundwater at Two Spill Sites

Two groundwater plumes in north central Minnesota with residual crude oil sources have 20 to 50 mg/L of nonvolatile dissolved organic carbon (NVDOC). These values are over 10 times higher than benzene and two to three times higher than Diesel Range Organics in the same wells. On the basis of previous work, most of the NVDOC consists of partial transformation products from the crude oil. Monitoring data from 1988 to 2015 at one of the sites located near Bemidji, MN show that the plume of metabolites is expanding toward a lakeshore located 335 m from the source zone. Other mass balance studies of the site have demonstrated that the plume expansion is driven by the combined effect of continued presence of the residual crude oil source and depletion of the electron accepting capacity of solid phase iron oxide and hydroxides on the aquifer sediments. These plumes of metabolites are not covered by regulatory monitoring and reporting requirements in Minnesota and other states. Yet, a review of toxicology studies indicates that polar metabolites of crude oil may pose a risk to aquatic and mammalian species. Together the results suggest that at sites where residual sources are present, monitoring of NVDOC may be warranted to evaluate the fates of plumes of hydrocarbon transformation products.

Detecting sulfamethoxazole and carbamazepine in groundwater: Is ELISA a reliable screening tool? ☆

In recent years, numerous studies have reported the prevalence of organic micropollutants in natural waters. There is an increasing interest in assessing the occurrence and transport of these contaminants in groundwater because a large number of people in the United States rely on groundwater for their drinking water. However, commonly used mass-spectrometry-based analytical methods are expensive and time-consuming. The enzyme-linked immunosorbent assay (ELISA) method offers an inexpensive analytical alternative that provides semi-quantitative results in a relatively quick timeframe. We investigated the use of ELISA for two commonly detected micropollutants, sulfamethoxazole (SMX) and carbamazepine (CBZ), in groundwater collected as part of two different studies, one in Minnesota and the other in Iowa. The ELISA results were compared with two mass-spectrometry-based methods: (1) direct aqueous injection-high performance liquid chromatography/tandem mass spectrometry (HPLC) and (2) online solid-phase extraction with liquid chromatography/electrospray ionization-mass spectrometry (SPE LC). Differences in SMX and CBZ observations between ELISA and both HPLC and SPE LC were analyzed using the Paired Prentice-Wilcoxon test. Estimates of bias and limits of agreement between paired observations also were calculated. The SMX determinations by ELISA yielded results that were 30 and 14% greater than HPLC and SPE LC, respectively. The CBZ determinations by ELISA yielded results that were 25 and 9% greater than HPLC and SPE LC, respectively. The ELISA determinations were in presence-absence agreement with HPLC for 83% of samples for SMX and CBZ; and with SPE LC for 76 and 80% of samples for SMX and CBZ, respectively. Results indicate that ELISA for SMX and CBZ is a reliable and cost effective screening-tool alternative to more commonly used mass spectrometry-based analytical methods.

How or When Samples Are Collected Affects Measured Arsenic Concentration in New Drinking Water Wells: M. L. Erickson et al. Groundwater xx, no. y: x-xx

Abstract Naturally occurring arsenic can adversely affect water quality in geologically diverse aquifers throughout the world. Chronic exposure to arsenic via drinking water is a human health concern due to risks for certain cancers, skin abnormalities, peripheral neuropathy, and other negative health effects. Statewide in Minnesota, USA, 11% of samples from new drinking water wells have arsenic concentrations exceeding 10 μg/L; in certain counties more than 35% of tested samples exceed 10 μg/L arsenic. Since 2008, Minnesota well code has required testing water from new wells for arsenic. Sample collection protocols are not specified in the well code, so among 180 well drillers there is variability in sampling methods, including sample collection point and sample collection timing. This study examines the effect of arsenic sample collection protocols on the variability of measured arsenic concentrations in water from new domestic water supply wells. Study wells were drilled between 2014 and 2016 in three regions of Minnesota that commonly have elevated arsenic concentrations in groundwater. Variability in measured arsenic concentration at a well was reduced when samples were (1) filtered, (2) collected from household plumbing instead of from the drill rig pump, or (3) collected several months after well construction (instead of within 4 weeks of well installation). Particulates and fine aquifer sediments entrained in groundwater samples, or other artifacts of drilling disturbance, can cause undesirable variability in measurements. Establishing regulatory protocols requiring sample filtration and/or collection from household plumbing could improve the reliability of information provided to well owners and to secondary data users.