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Barbara A. Bekins

Publications and source records attributed to Barbara A. Bekins.

At least 19 recordsLinked to original sources

Comparative properties of saponitic fault gouge and serpentinite muds cored from mud volcanoes of the Mariana subduction zone

We obtained 12 core samples for physical and chemical characterization from three serpentinite mud volcanoes (Yinazao, Asùt Tesoru, and Fantangisña) located on the forearc of the Mariana subduction system, that were drilled during International Ocean Discovery Program Expedition 366. Two samples from the Fantangisña mud volcano are interpreted to be clay-rich fault gouges derived from the subduction channel. Their bulk compositions are intermediate between the serpentinites and oceanic basalts. The oceanic crustal materials in the gouges have been thoroughly metasomatized and the serpentinites extensively altered to the trioctahedral, Mg-rich smectite clays saponite and corrensite. The only relict phases in clasts of crustal rock are accessory Ti- and P-bearing minerals. The two fault gouge samples have lower frictional strengths ( μ < 0.2) than the serpentinites ( μ = 0.2–0.4), and their measured permeabilities are also somewhat lower. Their physical and compositional properties correspond to saponitic gouges from other faults that juxtapose serpentinite against crustal rocks, in particular gouges from the two creeping traces of the San Andreas Fault recovered in the core from the San Andreas Fault Observatory at Depth. The décollement beneath Fantangisña mud volcano is thus expected to be very weak and likely characterized by stable slip.

Geophysics, Geochemistry, Geosystems↗

Distribution of ancient carbon in groundwater and soil gas from degradation of petroleum near the Red Hill Bulk Fuel Storage Facility, O‘ahu, Hawai‘i

The groundwater below the Red Hill Bulk Fuel Storage Facility (the facility) in Oʻahu, Hawaiʻi, contains fuel compounds from past spills. This study used carbon-14 analyses to distinguish fuel-derived carbon from background carbon, along with other biodegradation indicators, to address two goals: (1) determine the extent and migration direction of groundwater affected by residual fuel below the facility and (2) determine if residual fuel locations in the subsurface could be identified by analyzing soil gas at the surface above the facility. Groundwater from 19 wells was sampled between September 2022 and April 2023. Nonvolatile dissolved organic carbon (NVDOC) from a well presumed to be unaffected by past spills contained 38 percent ancient carbon indicating a natural source of ancient carbon in the subsurface. The NVDOC concentrations and ancient carbon percentages indicate fuel biodegradation products are likely present on the north and south of Red Hill with the greatest effects at well RHMW02 near the 2014 spill site. The NVDOC concentrations are almost three times higher than diesel range organic (DRO) concentrations in groundwater from the same sites. Major ion data indicate that iron reduction is an important biodegradation process. Soil probe samples and soil carbon traps were used to determine the carbon-14 content of soil carbon dioxide. Ancient carbon from fuel biodegradation was not detected at any soil probe or carbon trap site in contrast to a 2017 study which reported ancient carbon detections. A reanalysis of the 2017 results using a range of local values for background carbon-14 indicates that ancient carbon from fuel biodegradation was probably only detected in lower tunnel exhaust system samples and not in any soil carbon trap samples. Measurements of carbon dioxide efflux with a dynamic closed chamber were highly variable. The soil gas results indicate that soil gas measurements at land surface were not useful for detecting residual fuel at the facility.

Hawaii↗

Photochemical mobilization of dissolved hydrocarbon oxidation products from petroleum contaminated soil into a shallow aquifer activate human nuclear receptors

Elevated non-volatile dissolved organic carbon (NVDOC) concentrations in groundwater monitoring wells under oil-contaminated hydrophobic soils originating from a pipeline rupture at the National Crude Oil Spill & Natural Attenuation Research Site near Bemidji, MN are documented.. We hypothesized the elevated NVDOC is comprised of water-soluble photooxidation products transported from the surface to the aquifer. We use field and laboratory samples in combination with complementary analytical methods to test this hypothesis and determine the biological response to these products. Observations from optical spectroscopy and ultrahigh-resolution mass spectrometry reveal a significant correlation between the chemical composition of NVDOC leached from photochemically weathered soils and groundwater monitoring wells with high NVDOC concentrations measured in the aquifer beneath the contaminated soil. Conversely, the chemical composition from the uncontaminated soil photoleachate, matches the NVDOC observed in the uncontaminated wells. Contaminated groundwater and photodissolution leachates from contaminated soil activated biological targets indicative of xenobiotic metabolism and exhibited potential for adverse effects. Newly formed hydrocarbon oxidation products (HOPs) from fresh oil could be distinguished from those downgradient. This study illustrates another pathway for dissolved HOPs to infiltrate groundwater and potentially affect human health and the environment.

Minnesota↗

Methanogens and their syntrophic partners dominate zones of enhanced magnetic susceptibility at a petroleum contaminated site

Geophysical investigations documenting enhanced magnetic susceptibility (MS) within the water table fluctuation zone at hydrocarbon contaminated sites suggest that MS can be used as a proxy for investigating microbial mediated iron reduction during intrinsic bioremediation. Here, we investigated the microbial community composition over a 5-year period at a hydrocarbon-contaminated site that exhibited transient elevated MS responses. Our objective was to determine the key microbial populations in zones of elevated MS. We retrieved sediment cores from the petroleum-contaminated site near Bemidji, MN, United States, and performed MS measurements on these cores. We also characterized the microbial community composition by high-throughput 16S rRNA gene amplicon sequencing from samples collected along the complete core length. Our spatial and temporal analysis revealed that the microbial community composition was generally stable throughout the period of investigation. In addition, we observed distinct vertical redox zonations extending from the upper vadose zone into the saturated zone. These distinct redox zonations were concomitant with the dominant microbial metabolic processes as follows: (1) the upper vadose zone was dominated by aerobic microbial populations; (2) the lower vadose zone was dominated by methanotrophic populations, iron reducers and iron oxidizers; (3) the smear zone was dominated by iron reducers; and (4) the free product zone was dominated by syntrophic and methanogenic populations. Although the common notion is that high MS values are caused by high magnetite concentrations that can be biotically formed through the activities of iron-reducing bacteria, here we show that the highest magnetic susceptibilities were measured in the free-phase petroleum zone, where a methanogenic community was predominant. This field study may contribute to the emerging knowledge that methanogens can switch their metabolism from methanogenesis to iron reduction with associated magnetite precipitation in hydrocarbon contaminated sediments. Thus, geophysical methods such as MS may help to identify zones where iron cycling/reduction by methanogens is occurring.

Frontiers in Earth Science↗

Hydrocarbons to carboxyl-rich alicyclic molecules: A continuum model to describe biodegradation of petroleum-derived dissolved organic matter in contaminated groundwater plumes

Relationships between dissolved organic matter (DOM) reactivity and chemical composition in a groundwater plume containing petroleum-derived DOM (DOM HC ) were examined by quantitative and qualitative measurements to determine the source and chemical composition of the compounds that persist downgradient. Samples were collected from a transect down the core of the plume in the direction of groundwater flow. An exponential decrease in dissolved organic carbon concentration resulting from biodegradation along the transect correlated with a continuous shift in fluorescent DOM HC from shorter to longer wavelengths. Moreover, ultrahigh resolution mass spectrometry showed a shift from low molecular weight (MW) aliphatic, reduced compounds to high MW, unsaturated (alicyclic/aromatic), high oxygen compounds that are consistent with carboxyl-rich alicyclic molecules. The degree of condensed aromaticity increased downgradient, indicating that compounds with larger, conjugated aromatic core structures were less susceptible to biodegradation. Nuclear magnetic resonance spectroscopy showed a decrease in alkyl (particularly methyl) and an increase in aromatic/olefinic structural motifs. Collectively, data obtained from the combination of these complementary analytical techniques indicated that changes in the DOM HC composition of a groundwater plume are gradual, as relatively low molecular weight (MW), reduced, aliphatic compounds from the oil source were selectively degraded and high MW, alicyclic/aromatic, oxidized compounds persisted.

Minnesota↗

Biological effects of hydrocarbon degradation intermediates: Is the total petroleum hydrocarbon analytical method adequate for risk assessment?

In crude oil contaminant plumes, the dissolved organic carbon (DOC) is mainly hydrocarbon degradation intermediates only partly quantified by the diesel range total petroleum hydrocarbon (TPHd) method. To understand potential biological effects of degradation intermediates, we tested three fractions of DOC: (1) solid-phase extract (HLB); (2) dichloromethane (DCM-total) extract used in TPHd; and (3) DCM extract with hydrocarbons isolated by silica gel cleanup (DCM-SGC). Bioactivity of extracts from five wells spanning a range of DOC was tested using an in vitro multiplex reporter system that evaluates modulation of the activity of 46 transcription factors; extracts were evaluated at concentrations equivalent to the well water samples. The aryl hydrocarbon receptor (AhR) and pregnane X receptor (PXR) transcription factors showed the greatest upregulation, with HLB exceeding DCM-total, and no upregulation in the hydrocarbon fraction (DCM-SGC). The HLB extracts were further studied with HepG2 chemically activated luciferase expression (CALUX) in vitro assays at nine concentrations ranging from 40 to 0.01 times the well water concentrations. Responses decreased with distance from the source but were still present at two wells without detectable hydrocarbons. Thus, our in vitro assay results indicate that risks associated with degradation intermediates of hydrocarbons in groundwater will be underestimated when protocols that remove these chemicals are employed.

Minnesota↗

Mariana serpentinite mud volcanism exhumes subducted seamount materials: Implications for the origin of life

The subduction of seamounts and ridge features at convergent plate boundaries plays an important role in the deformation of the overriding plate and influences geochemical cycling and associated biological processes. Active serpentinization of forearc mantle and serpentinite mud volcanism on the Mariana forearc (between the trench and active volcanic arc) provides windows on subduction processes. Here, we present (1) the first observation of an extensive exposure of an undeformed Cretaceous seamount currently being subducted at the Mariana Trench inner slope; (2) vertical deformation of the forearc region related to subduction of Pacific Plate seamounts and thickened crust; (3) recovered Ocean Drilling Program and International Ocean Discovery Program cores of serpentinite mudflows that confirm exhumation of various Pacific Plate lithologies, including subducted reef limestone; (4) petrologic, geochemical and paleontological data from the cores that show that Pacific Plate seamount exhumation covers greater spatial and temporal extents; (5) the inference that microbial communities associated with serpentinite mud volcanism may also be exhumed from the subducted plate seafloor and/or seamounts; and (6) the implications for effects of these processes with regard to evolution of life.

Philosophical Transactions of the Royal Society A:↗

Examining the extraction efficiency of petroleum-derived dissolved organic matter in contaminated groundwater plumes

The extraction efficiency of petroleum-derived dissolved organic matter (DOM) was examined for groundwater samples from an aquifer contaminated with crude oil. Four different types of extraction were used to determine which method is best suited for the analysis of potentially toxic petroleum-derived DOM. The four types were a liquid-liquid extraction (LLE) with dichloromethane (EPA method 3510C), and three solid-phase extraction (SPE) stationary phases that are routinely used for extraction of polar analytes from water. For the LLE, that is selective for non-polar compounds, the extraction efficiency of petroleum-derived DOM decreased downgradient as the petroleum-derived DOM becomes increasingly polar due to biodegradation. In contrast, the average extraction efficiency by the SPE methods was greater than 65 % across the gradient. The results showed that SPE is more efficient for extracting petroleum-derived DOM at hydrocarbon-contaminated sites. The use of a method with greater extraction efficiency for partially-oxidized hydrocarbons may prove useful in determining relationships between their composition and structure and potential for risks to human health or the environment.

Ground Water Monitoring and Remediation↗

Data Report: Permeability, porosity, and frictional strength of core samples from IODP Expedition 366 in the Mariana forearc

Core samples from the International Ocean Discovery Program (IODP) Expedition 366 were tested in the laboratory to determine permeability, porosity, density, and frictional strength and their relation to mineralogy as part of an effort to understand hydro-mechanical processes at convergent plate margins. Seven samples were tested from a depth range of 19.6 to 197.9 m below the sea floor. The samples were derived from three serpentinite mud volcanoes in the Mariana forearc region, formed where slab-derived fluids and materials ascend along faults. The physical characteristics mirror compositional differences between predominantly serpentine-rich and saponite-rich samples. Permeability values ranged from 10-17 to 10-19 m2, low enough to facilitate the formation of high fluid pressures, which have been observed in the Mariana and other subduction megathrust environments. Porosities ranged from 0.37 to 0.51 and densities from 1.66 to 2.01 gm/cc. Serpentine-rich samples have coefficients of friction of 0.2 to 0.4, consistent with crustal serpentinite from a variety of fault zones, whereas saponite-rich samples have friction values below 0.2, consistent with saponite fault gouge from the San Andreas Fault Zone at Depth (SAFOD) drillhole in California.

Book chapter↗

Case studies in groundwater contaminant fate and transport

A case study of groundwater contamination is a detailed study of a single site contaminated with a chemical or mixture that is known to be a problem at many sites. The goal of case studies is to provide insights into the physical, chemical, and biological processes controlling migration, natural attenuation, or remediation of common groundwater contaminants. Ideally, processes occurring at a case study site are representative of other sites so that knowledge gained from these intensive studies can be applied at thousands of sites where fewer data are available. Several characteristics of case studies contribute to their value. First, they may have tens to hundreds of monitoring wells, compared to fewer than ten wells at some contaminated sites. Second, some case studies continue for many years or even decades, providing insights into temporal progression of slow processes. Third, analytical methods prohibitively expensive for routine use or under development may be tested at case study sites. Finally, the ongoing characterization typical of case study sites builds a foundation of knowledge that facilitates sophisticated experimental design and testing of new methods. This article is divided into sections based on the contaminant type because the chemical and biological processes required for remediation vary for each contaminant. Most importantly, some contaminants can be biodegraded whereas metals and radionuclides cannot be destroyed but can be immobilized or rendered less toxic. The emphasis is on case studies of natural processes that control the fate and transport of contaminants in groundwater rather than on active remediation methods. The principles learned from these studies may form the basis for design of remedial strategies. The organic contaminants are divided into: petroleum hydrocarbons, fuel oxygenates, coal tar and wastes from manufactured gas plants, and chlorinated solvents. The inorganic contaminants covered are metals and radionuclides, arsenic, and nitrate. Case studies of mixed waste plumes from landfills are also described. Experimental sites where contaminants have been introduced into an aquifer as an emplaced source or a controlled release may not meet the above definition of case studies, but some are included because the overall goal is to impart lessons learned from detailed field studies. It is impossible to cover all case studies in this short format. Conversely, focusing on one or two does not convey the breadth of research results in entire range of case studies. Instead, the strategy is to describe the evolution of knowledge for each contaminant class while providing citations of relevant case studies. Much of the progress in understanding of the fate of contaminants in groundwater is based on laboratory studies; thus whenever possible, papers that included both field and laboratory results have been included among the citations. Two topics of growing importance have not been covered. These are the fate of pharmaceuticals in groundwater and discharge of contaminant plumes to surface water. These topics merit coverage in the future as knowledge grows and case studies increase in number.

Environmental Science↗

Geophysical mapping of plume discharge to surface water at a crude oil spill site: Inversion versus machine learning

The interpretation of geophysical survey results to answer hydrologic, engineering, and geologic questions is critical to diverse problems for management of water, energy, and mineral resources. Although geophysical images provide valuable qualitative insight into subsurface architecture and conditions, translating geophysical images into quantitative information (e.g., saturation, concentration, and hydraulic properties) often involves substantial nonuniqueness and uncertainty owing to the limited resolution of geophysical imaging and uncertainty in petrophysical relations. We have developed a machine-learning approach to address these challenges in the context of a field-based investigation to map zones where a hydrocarbon plume was discharging to surface water at the National Crude Oil Spill Fate and Natural Attenuation Research Site in Bemidji, Minnesota, USA. The two-step approach combines multiple types of geophysical and direct information and effectively bypasses inversion and its associated assumptions. Integrating multifrequency electromagnetic induction, ground-penetrating radar, and fluid-sampling data, we first identify discharge zones and second estimate specific conductance versus depth. Compared with conventional inversion results, the machine-learning results (1) directly address the study objectives (delineating the discharge zones); (2) better extract depth-dependent information from the data, for which sensitivity diminishes rapidly with depth; and (3) quantify the uncertainty of the predictions (i.e., discharge versus nondischarge zones), rather than the uncertainty of the geophysical estimates (i.e., the standard error of estimation for the logarithm of electrical conductivity).

Minnesota↗

Natural Attenuation in Source Zone and Groundwater Plume - Bemidji Crude Oil Spill

A long-term study of a 40-year-old crude oil spill provides insights about petroleum hydrocarbon natural attenuation processes and rates. In the source zone, fermentation coupled to methanogenesis is the dominant natural source zone depletion (NSZD) process, and most of the carbon mass exits the surface as CO2 efflux. Monitored natural attenuation (MNA) of the groundwater plume shows that benzene degradation is coupled to iron reduction and that the benzene plume is stable. A plume of hydrocarbon oxidation products measured as nonvolatile dissolved organic carbon (NVDOC) expanded ~20 m in 20 years. Most of the NVDOC is biodegraded by 200 m from the source, but optical data suggest there are components that persists for 300 m. Biological effects screening indicates decreasing biological effects with distance from the source.

Minnesota↗

Toxicity assessment of groundwater contaminated by petroleum hydrocarbons at a well-characterized, aged, crude oil release site

Management of petroleum-impacted waters by monitored natural attenuation requires an understanding of the toxicology of both the original compounds released and the transformation products formed during natural breakdown. Here, we report data from a groundwater plume consisting of a mixture of crude oil compounds and transformation products in an effort to bridge the gap between groundwater quality information and potential biological effects of human exposures. Groundwater samples were characterized for redox processes, concentrations of nonvolatile dissolved organic carbon (NVDOC) and total petroleum hydrocarbons in the diesel range, as well as for activation of human nuclear receptors (hNR) and toxicologically relevant transcriptional pathways. Results show upregulation of several biological pathways, including peroxisome proliferator-activated receptor gamma and alpha, estrogen receptor alpha, and pregnane X receptor (PXR) with higher levels of hNR activity observed in more contaminated samples. Our study of affected groundwater contaminated by a crude-oil release 39 years ago shows these types of waters may have the potential to cause adverse impacts on development, endocrine, and liver functioning in exposed populations. Additionally, positive trends in activation of some of the molecular targets (e.g., PXR) with increasing NVDOC concentrations (including polar transformation products) demonstrate the importance of improving our understanding of the toxicity associated with the unknown transformation products present in hydrocarbon-impacted waters. Our results begin to provide insight into the potential toxicity of petroleum-impacted waters, which is particularly timely given the ubiquitous nature of waters impacted by petroleum contamination not only recently but also in the past and the need to protect drinking-water quality.

Environmental Science & Technology↗

A direct-push freezing core barrel for sampling unconsolidated subsurface sediments and adjacent pore fluids

Contaminants passing through the unsaturated zone can undergo changes in narrow reaction zones upon reaching saturated sediments. Understanding these reactions requires sampling of sediment together with adjacent water and microbes in a manner that preserves in situ redox conditions. Use of a basket-type core catcher for saturated, noncohesive sediments results in redistribution or loss of fluids during sample retrieval. Previously developed sample-freezing drive shoes for hollow-stem auger drilling rigs lessened fluid redistribution and retained all material that entered the core barrel in noncohesive sediment cores by freezing the base of the core with liquid CO 2 . This technology has not previously been compatible with direct-push rigs that are commonly used for contaminated site assessments. Here, we describe a freezing core barrel designed for direct-push rigs that is compatible with commercially available tool strings. The device can be used interchangeably with unsaturated-zone direct-push tool strings, enabling core collection for studies of contaminant transport and transformation spanning unsaturated to saturated profiles. In all 10 attempts during testing near Bemidji, MN, the device froze a 10- to 15-cm (4–6-in) plug that retained fluids and sediments in a 1.2-m (4-ft)-long, 5.0-cm (2.0-in)-diameter polyvinyl chloride (PVC) sleeve. Cores were collected from variably saturated sediments spanning the capillary fringe through the upper 2 m of the saturated zone in sandy glacial outwash sediments. The median recovery was 81% of the drive length, similar to a sample-freezing drive shoe developed for a wire-line piston core sampler operated with a hollow-stem auger drill rig.

Vadose Zone Journal↗

Examining natural attenuation and acute toxicity of petroleum-derived dissolved organic matter with optical spectroscopy

Groundwater samples containing petroleum-derived dissolved organic matter (DOM HC ) originating from the north oil body within the National Crude Oil Spill Fate and Natural Attenuation Research Site near Bemidji, MN, USA were analyzed by optical spectroscopic techniques (i.e., absorbance and fluorescence) to assess relationships that can be used to examine natural attenuation and toxicity of DOM HC in contaminated groundwater. A strong correlation between the concentration of dissolved organic carbon (DOC) and absorbance at 254 nm ( a 254 ) along a transect of the DOM HC plume indicates that a 254 can be used to quantitatively assess natural attenuation of DOM HC . Fluorescence components, identified by parallel factor (PARAFAC) analysis, show that the composition of the DOM HC beneath and adjacent to the oil body is dominated by aliphatic, low O/C compounds (“protein-like” fluorescence) and that the composition gradually evolves to aromatic, high O/C compounds (“humic-/fulvic-like” fluorescence) as a function of distance downgradient from the oil body. Finally, a direct, positive correlation between optical properties and Microtox acute toxicity assays demonstrates the utility of these combined techniques in assessing the spatial and temporal natural attenuation and toxicity of the DOM HC in petroleum-impacted groundwater systems.

Environmental Science & Technology↗

Relative contributions of microbial and infrastructure heat at a crude oil-contaminated site

Biodegradation of contaminants can increase the temperature in the subsurface due to heat generated from exothermic reactions, making temperature observations a potentially low-cost approach for determining microbial activity. For this technique to gain more widespread acceptance, it is necessary to better understand all the factors affecting the measured temperatures. Biodegradation has been occurring at a crude oil-contaminated site near Bemidji, Minnesota for 39 years, creating a quasi-steady-state plume of contaminants and degradation products. A model of subsurface heat generation and transport helps elucidate the contribution of microbial and infrastructure heating to observed temperature increases at this site. We created a steady-state, two-dimensional, heat transport model using previous-published parameter values for physical, chemical and biodegradation properties. Simulated temperature distributions closely match the observed average annual temperatures measured in the contaminated area at the site within less than 0.2 °C in the unsaturated zone and 0.4 °C in the saturated zone. The model results confirm that the observed subsurface heat from microbial activity is due primarily to methane oxidation in the unsaturated zone resulting in a 3.6 °C increase in average annual temperature. Another important source of subsurface heat is from the active, crude-oil pipelines crossing the site. The pipelines impact temperatures for a distance of 200 m and contribute half the heat. Model results show that not accounting for the heat from the pipelines leads to overestimating the degradation rates by a factor of 1.7, demonstrating the importance of identifying and quantifying all heat sources. The model results also highlighted a zone where previously unknown microbial activity is occurring at the site.

Minnesota↗

Weathering of oil in a surficial aquifer

The composition of crude oil in a surficial aquifer was determined in two locations at the Bemidji, MN, spill site. The abundances of 71 individual hydrocarbons varied within 16 locations sampled. Little depletion of these hydrocarbons (relative to the pipeline oil) occurred in the first 10 years after the spill, whereas losses of 25% to 85% of the total measured hydrocarbons occurred after 30 years. The C 6‐30 n ‐alkanes, toluene, and o ‐xylene were the most depleted hydrocarbons. Some hydrocarbons, such as the n‐ C 10–24 cyclohexanes, tri‐ and tetra‐ methylbenzenes, acyclic isoprenoids, and naphthalenes were the least depleted. Benzene was detected at every sampling location 30 years after the spill. Degradation of the oil led to increases in the percent organic carbon and in the δ 13 C of the oil. Another method of determining hydrocarbon loss was by normalizing the total measured hydrocarbon concentrations to that of the most conservative analytes. This method indicated that the total measured hydrocarbons were depleted by 47% to 77% and loss of the oil mass over 30 years was 18% to 31%. Differences in hydrocarbon depletion were related to the depth of the oil in the aquifer, local topography, amount of recharge reaching the oil, availability of electron acceptors, and the presence of less permeable soils above the oil. The results from this study indicate that once crude oil has been in the subsurface for a number of years there is no longer a “starting oil concentration” that can be used to understand processes that affect its fate and the transport of hydrocarbons in groundwater.

Minnesota↗

Evidence of coupled carbon and iron cycling at a hydrocarbon-contaminated site from time lapse magnetic susceptibility

Conventional characterization and monitoring of hydrocarbon (HC) pollution is often expensive and time-consuming. Magnetic susceptibility (MS) has been proposed as an inexpensive, long-term monitoring proxy of the degradation of HC. We acquired repeated down hole MS logging data in boreholes at a HC-contaminated field research site in Bemidji, MN, USA. The MS data were analyzed in conjunction with redox conditions and iron availability within the source zone to better assess whether MS can serve as a proxy for monitoring HC contamination in unconsolidated sediments. The MS response at the site diminished during the sampling period, which was found to coincide with depletion of solid phase iron in the source zone. Previous geochemical observations and modeling at the site suggest that the most likely cause of the decrease in MS is the transformation of magnetite to siderite, coupled with the exhaustion of ferrihydrite. Although the temporal MS response at this site gives valuable field-scale evidence for changing conditions of iron cycling and stability of iron minerals it does not provide a simple proxy for long-term monitoring of biodegradation of hydrocarbons in the smear zone.

Minnesota↗