In‐well sediment incubators to evaluate microbial community stability and dynamics following bioimmobilization of uranium

An in‐well sediment incubator (ISI) was developed to investigate the stability and dynamics of sediment‐associated microbial communities to prevailing subsurface oxidizing or reducing conditions. Herein we describe the use of these devices at the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site. During a seven‐month period in which oxidized Rifle Aquifer background sediment (RABS) were deployed in previously biostimulated wells under iron‐reducing conditions, cell densities of known iron‐reducing bacteria, including Geobacteraceae, increased significantly, showing the microbial community response to local subsurface conditions. Phospholipid fatty acid (PLFA) profiles of RABS following in situ deployment were strikingly similar to those of adjacent sediment cores, suggesting ISI results could be extrapolated to the native material of the test plots. Results for ISI deployment with laboratory‐reduced sediments showed only slight changes in community composition and pointed toward the ability of the ISI to monitor microbial community stability and response to subsurface conditions. © 2009 Wiley Periodicals, Inc.     

Using Fallout Lead-210 Measurements to Estimate Soil Erosion in Three Small Catchments in Southern Italy

Soil erosion and associated off-site environmental impacts have attracted increasing attention in recent decades, and there is a growing need for reliable information on rates of soil loss. The potential for using ¹³⁷Cs fallout to quantify rates and patterns of soil redistribution over medium-term timescales (ca. 45 years) has been successfully demonstrated in a wide range of environments around the world. The similar behaviour of fallout ²¹⁰Pb in soils offers potential for its use as an alternative to ¹³⁷Cs, in areas where ¹³⁷Cs inventories are low or are complicated by additional fallout from the Chernobyl accident. There have, however, to date been few attempts to validate the use of fallout ²¹⁰Pb measurements for assessing erosion rates. This paper reports an attempt to explore the use of fallout ²¹⁰Pb to estimate rates of water-induced soil erosion on uncultivated land. It focuses on three small forest/rangeland catchments located in Calabria, southern Italy, for which measurements of sediment output are available. Comparison of the estimates of net soil loss from the catchments derived from ²¹⁰Pb measurements with the measured sediment output, confirmed the validity of the ²¹⁰Pb approach. The soil redistribution rates estimated using ²¹⁰Pb measurements were also consistent with equivalent estimates obtained for the same study catchments using ¹³⁷Cs measurements.     

Spatial Distribution of Geobacteraceae and Sulfate‐Reducing Bacteria During In Situ Bioremediation of Uranium‐Contaminated Groundwater

Analysis of the physiological status of subsurface microbial communities generally relies on the study of unattached microorganisms in the groundwater. These approaches have been employed in studies on bioremediation of uranium‐contaminated groundwater at a study site in Rifle, Colorado, in which Geobacter species typically account for over 90 percent of the microbial community in the groundwater during active uranium reduction. However, to develop efficient in situ bioremediation strategies it is necessary to know the status of sediment‐associated microorganisms as well. In order to evaluate the distribution of the natural community of Geobacter during bioremediation of uranium, subsurface sediments were packed into either passive flux meters (PFMs) or sediment columns deployed in groundwater monitoring wells prior to acetate injection during in situ biostimulation field trials. The trials were performed at the Department of Energy's (DOE's) Rifle Integrated Field Research Challenge site. Sediment samples were removed either during the peak of Fe(III) reduction or the peak of sulfate reduction over the course of two separate field experiments and preserved for microscopy. Direct cell counts using fluorescence in situ hybridization (FISH) probes targeting Geobacter species indicated that the majority of Geobacter cells were unattached during Fe(III) reduction, which typically tracks with elevated rates of uranium reduction. Similar measurements conducted during the sulfate‐reducing phase revealed the majority of Geobacter to be attached following exhaustion of more readily bioavailable forms of iron minerals. Laboratory sediment column studies confirmed observations made with sediment samples collected during field trials and indicated that during Fe(III) reduction, Geobacter species are primarily unattached (90 percent), whereas the majority of sulfate‐reducing bacteria and Geobacter species are attached to sediment surfaces when sulfate reduction is the predominant form of metabolism (75 percent and 77 percent, respectively). In addition, artificial sediment experiments showed that pure cultures of Geobacter uraniireducens, isolated from the Rifle site, were primarily unattached once Fe(III) became scarce. These results demonstrate that, although Geobacter species must directly contact Fe(III) oxides in order to reduce them, cells do not firmly attach to the sediments, which is likely an adaptive response to sparsely and heterogeneously dispersed Fe(III) minerals in the subsurface. © 2013 Wiley Periodicals, Inc.     

Phosphorus Storage in Fine Channel Bed Sediments

Deposition and storage of fine sediment on channel beds represents an important component of a catchment’s sediment budget and can have important implications for sediment-associated P fluxes, due to storage and remobilisation, and for P concentrations through water–sediment interactions. Spatial and temporal variations in P content and storage in fine bed sediment have been studied in two UK lowland catchments, the Rivers Frome and Piddle in Dorset. Fine bed sediment was sampled in representative reaches on a bi-monthly basis using a re-suspension cylinder, and the resulting samples were analysed for total P, a range of P fractions and particle size. The results demonstrate significant spatial and temporal variability in PP concentrations and storage, with maximum and minimum P concentrations and storage occurring in late summer and winter, respectively. Temporal variations in concentrations reflect residence times of the sediment and ambient P concentrations, while variations in storage are mainly due to hydrological regimes. Spatial variations reflect catchment characteristics, the location of inputs and local variations in hydrological and channel bed conditions.     

Evaluation of the physical stability,groundwater seepage control,and faunal changes associated with an AquaBlok® sediment cap

Active sediment caps are being considered for addressing contaminated sediment areas in surface‐water bodies. A demonstration of an active cap designed to reduce advective transport of contaminants using AquaBlok® (active cap material) was initiated in a small study area of the Anacostia River in Washington, D.C. The cap remained physically stable, demonstrated the ability to divert groundwater flow, and was recolonized with native organisms after 30 months of monitoring following cap placement. However, the long‐term performance of active caps associated with harsh environmental conditions, hydrogeological settings, and subsurface gas production needs to be further evaluated. © 2008 Wiley Periodicals, Inc.     

Potential and Limitations of Microbial Reductive Dechlorination for Bioremediation Applications

Current knowledge and recent advances in the area of microbial reductive dechlorination of polychlorinated organic compounds are summarized. Factors which may limit the efficacy of the dechlorination process for the in situ bioremediation of contaminated soil and sediment systems are identified. Results of recent studies on the anaerobic biotransformation of soil-sorbed chlorinated ethenes and sediment-sorbed chlorinated benzenes are provided to illustrate how low contaminant bioavailability may control the rate and extent of dechlorination in subsurface systems, especially those with long-term contamination. Use of nonionic, polysorbate surfactants as the sole electron donors of a mixed, methanogenic culture supported the microbial sequential reductive dechlorination of either free or sediment-bound hexachlorobenzene (HCB) to primarily 1,3-dichlorobenzene, but did not enhance the bioavailability of sediment-bound HCB as compared to microcosms, which used glucose. Because current knowledge on the interactions of dechlorinating populations with other microbial populations in the presence of alternative terminal electron acceptors (e.g., nitrate, Fe³⁺ , Mn⁴⁺) is limited, such interactions and their effect on the dechlorination process in subsurface systems need to be further explored to improve our understanding of the reductive dechlorination process in complex environmental systems and lead to the development of more efficient in situ bioremediation technologies and strategies.     

Changes in Sediment Sources following Wildfire in Mountainous Terrain: A Paired–Catchment Approach,British Columbia,Canada

This paper describes a study examining the potential of mineral magnetic, geochemical and organic properties to determine if a 2003 wildfire in a catchment in British Columbia, Canada, caused a change in the sources of the suspended sediment transported in the channel relative to a nearby unburnt (reference) catchment. The results show that some of the properties offer the potential to determine sediment sources in the unburnt catchment. However, the 2003 wildfire modified the concentrations of some properties and this can either compromise or enhance their ability as tracers in the burnt catchment. At present, the source tracing results are inconclusive. This has implications for the use of certain properties as fingerprints and raises important issues about approaches to sediment source identification.     

Using an integrated approach for quantifying VOC source areas for site remediation

Locating and quantifying free-phase volatile organic compounds (VOCs) in the subsurface represent one of the more difficult challenges facing hazardous waste site remediation programs. Successful remediation programs require reliable data on the size and extent of potential VOC contamination sources. Improving subsurface quantification of VOCs requires a large number of reliable low-cost samples. Satisfying this objective relies on improved sampling techniques, field analysis of samples, and a modified quality assurance program. This paper describes an integrated approach using conventional split-spoon samplers, microcore sampling, hexane extractions, and a field gas chromatograph with an autosampler as part of a technical demonstration for innovative remediation technologies. Using this approach, it was possible to delineate a subsurface source of free-phase VOCs at a cost of $15 per sample. The distribution of dense nonaqueous phase liquid determined by this sampling approach agreed with the conceptual model for the site.     

Application of passive soil gas technology to determine the source and extent of a PCE groundwater plume in an urban environment

In situations where groundwater supplies have been impacted by volatile organic compounds (VOCs), such as tetrachloroethene (PCE), and the source has not been identified, the costs to identify the source and plume migration patterns may be extremely high. The costs for an investigation increase with the number and depth of borings and the number of samples that are collected and analyzed. An environmental investigator and the Arizona Department of Environmental Quality (ADEQ) have successfully utilized passive soil gas (PSG) surveys in Arizona to cost‐effectively investigate VOC impacts to groundwater and identify potential sources of impact. PSG surveys are minimally intrusive, and more samples can be collected for the same cost when compared to active soil gas surveys and conventional soil and groundwater sampling programs. The result is a surficial representation of the contaminant plume and the location of “hot spots,'' which are the potential sources. This provides a better understanding of the nature and extent of the impact and allows for a focused subsurface investigation, which subsequently reduces drilling and sampling costs. © 2008 Wiley Periodicals, Inc.     

Non-Uniform Regulations of Underground Storage Tanks in the United States: Calls for a National-Scale Revision

Leaking underground storage tanks (USTs) are one of the major sources of ground water contamination. United States federal regulations for USTs were established in September of 1988. Since that time little or no amendments have been made to these regulations. In order to protect sensitive areas such as aquifer recharge zones for public water supply wells and wetlands, different states have been obligated to apply more stringent standards than the federal UST regulations. This practice however, has led to a non-uniform application of regulations for USTs throughout the country. In this article, United States regulations for USTs are reviewed and its deficits are highlighted. Based on these regulations and the experience of northeastern states of United States, a sequence of leak and spill preventive measures for USTs is proposed. Application of the proposed measures could substantially reduce the possibility of UST failure and would be more protective of the subsurface environment.     

The effect of biodiesel on the rate of removal and weathering characteristics of crude oil within artificial sand columns

The physical and chemical properties of crude oils differ greatly, and these properties change significantly once oil is spilled into the marine environment as a result of a number of weathering processes. Quantitative information on the weathering of spilled crude is a fundamental requirement for a fuller understanding of the fate and behaviour of oil in the environment. Additionally, such data are also essential for estimating windows-of-opportunities, where specific response methods, technologies, equipment or products are most effective in clean-up operations. In this study, the effects of a relatively low toxicity compound, biodiesel (rape seed oil methyl ester) on the rate of removal and weathering characteristics of crude oil within artificial sand columns are thoroughly investigated using GC/MS techniques. In the absence of the biodiesel, the crude oil exhibits low mobility and a slow rate of microbial degradation within the sediment and as a result, a high degree of persistance. Brent crude oil was subject to a progressive loss of the low molecular weight n-alkanes with respect to time through evaporation and a preferential migration of these fractions through the sediment to depth. The addition of the biodiesel led to greater recovery of oil from the sediment if applied to relatively unweathered crude oil. This was as the result of the crude oil dissolving within the more mobile biodiesel. The negligible concentration of the n-C₁₀ to n-C₂₁ fraction in surface sediment samples suggests a greater solubility of these fractions within the biodiesel and that their subsequent adsorption onto subsurface sediment particles was responsible for their absence from water flushed through the sands. These results suggest that biodiesel may have an active role in the beach clean-up of spilt crude oil.     

Estimating PAH sources in harbor sediments using diagnostic ratios

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the global environment and are subsequently transported into aquatic sediments. As PAHs are formed by various processes, source identification using diagnostic ratios can provide insight to PAH emission sources to distinguish between pyrogenic and petrogenic PAH sources. PAH diagnostic ratios were applied as a forensic source apportionment technique to assess aggregate historical sediment data from 31 small craft harbors (SCHs) across Nova Scotia, Canada. Multiple diagnostic ratios suggest that PAHs present in Nova Scotia SCH sediments are pyrogenic (combustion) in origin, while consistently suggesting that coal‐related PAH sources are potential dominant specific sources. National Institute of Standards and Technology Standard Reference Materials (SRMs) were used as reference for coal tar, urban dust, and diesel exhaust particulates in ratio applications. The SRM for coal tar was most similar to Nova Scotia SCH sediments in multiple ratio applications. Diagnostic ratio results were corroborated by comparing the PAH profile of sediments to source profiles from the literature. Results indicate that Nova Scotia SCH sediments follow global trends by exhibiting a dominant pyrogenic PAH signature, and the specific coal‐related PAH signature of Nova Scotia SCH sediments may be influenced by contamination inputs related to historical industrial coal mining and combustion activities in the province.     

Simulation of flow and mercury transport in Upper East Fork Poplar Creek,Oak Ridge,Tennessee

As a result of nuclear processing activities started back in the 1950s, the environment in the vicinity of the Y‐12 National Security Complex (Y‐12 NSC) in Oak Ridge, Tennessee, and surrounding watersheds has been contaminated by nearly 1,000 tons of elementary mercury. To comply with the state and federal surface water quality standards, a significant reduction in mercury concentration to parts‐per‐trillion levels has been proposed. In order to analyze the mercury cycle in the environment and provide forecasting capabilities for the flow and transport of mercury within the Upper East Fork Poplar Creek (UEFPC) watershed, an integrated surface and subsurface flow and transport model has been developed using the hydrodynamic and transport numerical package, MIKE, developed by the Danish Hydraulic Institute. The model has been constructed and calibrated using an extensive collection of historical records (i.e., hydrological data, and mercury concentration measurements in groundwater, soil, and sediment) obtained from the Oak Ridge Environmental Information System database. Daily fluctuations in stream flow, as a result of scattered rainfall, flooding, and flow augmentation, resuspend the contaminated streambed sediments and/or erode the polluted streambank soil and provide a secondary source of mercury to the creek. In order to investigate the significance of sediment‐mercury interactions on the fate and transport of mercury within the UEFPC study domain, simulations were performed for two different cases (i.e., with and without consideration of sediment‐mercury interactions). Computed total suspended solids and mercury concentrations at the integration point of the creek are compared with the corresponding historical records in both cases. As confirmed by the numerical simulations, a substantial portion of the mercury detected in the river is likely in the form of sediment particle–bound mercury (i.e., mercury particulates). © 2012 Wiley Periodicals, Inc.     

Groundwater Impacts on Surface Water and Sediment—Gowanus Canal,Brooklyn, New York

The Gowanus Canal Superfund Site in Brooklyn, New York, is an approximately 1.5‐mile (1.61‐km) long estuary that was historically converted into a canal for industrial and commercial purposes. Three manufactured gas plants (MGPs) were formerly located on the Gowanus Canal and discharged waste into it. Surface sediments remain highly contaminated with polycyclic aromatic hydrocarbons (PAHs) long after the MGPs were razed. A hydrogeologic assessment indicates that groundwater passes through the deeper coal tar–contaminated sediment prior to discharging to the canal. This study was undertaken to investigate if groundwater passing through coal tar–contaminated sediment could be responsible for the ongoing contamination of both surface sediments and surface water in the canal. PAH compound distributions in surface water samples collected from the tidal canal at low tide were compared with PAH compounds found in adjacent groundwater‐monitoring wells, point sources (combined sewer overflows [CSOs]), and surface sediments. The results indicate a strong correlation between PAH contaminant distributions in groundwater, sediment, and surface water, indicating that contaminated groundwater passing through the deeper coal tar–contaminated sediments is the primary mechanism contributing to the contamination of both surface sediment and surface water in the canal. Therefore, any sediment remediation efforts in the Gowanus Canal that fail to evaluate and control the upward transport processes have a high chance of failure due to recontamination from below.  ©2016 Wiley Periodicals, Inc.     

Overview of state approaches to vapor intrusion

A large number of states have issued guidance addressing the vapor intrusion pathway making it difficult to keep up with various policies and requirements. We have compiled and reviewed guidance from 35 states, half of which have issued documents within the last three years. A comparison of policies among states shows reasonable consistency in some areas—for example, 20 of 23 states that provide an exclusion distance for subsurface sources of chlorinated volatile organic compounds (VOCs) use a distance of 100 feet. However, more commonly, the policy decisions vary widely. Among states, indoor air screening concentrations for the same VOC vary by more than 2,000 times and subsurface screening concentrations vary by more than 2,000,000 times. These wide discrepancies suggest a need for communication and consensus building in order to increase consistency in the management of the vapor intrusion pathway. © 2012 Wiley Periodicals, Inc.     

Spectral Analysis of Chemical Time Series from Long-Term Catchment Monitoring Studies: Hydrochemical Insights and Data Requirements

Hydrological and hydrochemical data from long-term monitoring stations are vital for inferring travel times and flowpaths of water, and transport of contaminants through catchments. Spectral analysis is particularly powerful for studying the hydrological and chemical dynamics of catchments across a wide range of time scales. Here, recent work is reviewed that illustrates how spectral analyses of long-term monitoring data can be used to infer the travel-time distribution of water through catchments, and to measure the chemical retardation of reactive solutes at the catchment scale. For spectral analysis, it is desirable to have data sets with high sampling frequency and long periods of coverage. Using two data sets, a 3-yr daily data series and a 17-yr weekly data series from the Hafren catchment at Plynlimon, Wales, we demonstrate that high-frequency sampling (e.g., daily or more frequent) is particularly useful for revealing the short-term chemical dynamics that most clearly reflect the interplay of subsurface chemical and hydrological processes. However, data sets that combine high-frequency sampling during storm events with low-frequency sampling between storms can cause spectral artifacts and must be treated with special care.     

Nitrate Leaching from Moorland Soils: Can Soil C:N Ratios Indicate N Saturation?

Links between forest floor carbon:nitrogen (C:N) ratios, atmospheric N deposition and nitrate leaching into surface waters have been reported for forest ecosystems, but similar studies have not been reported previously for the equivalent compartments of moorland ecosystems in Great Britain, despite the importance of nitrate in contributing to the acidification of moorland streams and lakes in British uplands. In this paper, the relationships between the C:N ratio of moorland soil surface organic matter, N deposition, and nitrate leaching are explored for 13 soils in four moorland catchments. Although there is spatial variability in the C:N ratio of soils, major differences are apparent between soils and especially between catchments. The C:N ratio appears to be inversely related to modelled inorganic N deposition and, to a lesser degree, measured nitrate leaching, for three of the four catchments studied (Allt a'Mharcaidh, Afon Gwy, and Scoat Tarn). Nitrification may make an important contribution to nitrate leaching at the two higher deposition sites. At the fourth site, the heavily acidified River Etherow catchment, extremely high rates of nitrate leaching are not accompanied by low C:N ratios or high nitrification potentials in the upper soil horizons. Hence the C:N ratio of surface soil organic matter may have potential as an indicator of nitrogen saturation and leaching in some systems, but it is not universally applicable.     

Total Lead and Stable Lead Isotopes in Stockholm Sediments

Lead (Pb) in the environment is derived from both naturaland anthropogenic sources. The aim of this study is to estimate the isotopic signature of anthropogenic Pb in sediments from a highly contaminated area (Stockholm), to discuss the influence of different sources on this signature, and to suggest natural Pb background concentrations. Also distribution patterns and differences between different water areas in Stockholm have been studied, both by total Pb and stable Pb isotopes. In 1993, sediment samples were collected at 24 stations in the Stockholm area and analysed for total Pb, zirconium (Zr), scandium (Sc) and stable Pb isotopes (^{204, 206-208}Pb). Total Pb data show that the Stockholm sediments are severely contaminated by Pb. The contamination seems to be rather local since the small lakes surrounding the central parts of Stockholm are much less effected than the central parts. Stockholm is clearly influenced by anthropogenic and natural sources, but in some of the small lakes also by Pb in zircons from the geological basement. The anthropogenic Pb in Stockholm has typical ²⁰⁷Pb/²⁰⁶Pb ratios of 0.85–0.89 and ²⁰⁸Pb/²⁰⁴Pb ratios of 36–38, which are distinct from natural sources. Pb/Sc ratios suggest that the natural background Pb concentration is 10–20 mg kg^-1 d.w.     

Ambient levels of PFOS and PFOA in multiple environmental media

Making remediation and risk management decisions for widely‐distributed chemicals is a challenging aspect of contaminated site management. The objective of this study is to present an initial evaluation of the ubiquitous, ambient environmental distribution of poly‐ and perfluoroalkyl substances (PFAS) within the context of environmental decision‐making at contaminated sites. PFAS are anthropogenic contaminants of emerging concern with a wide variety of consumer and industrial sources and uses that result in multiple exposure routes for humans. The combination of widespread prevalence and low screening levels introduces considerable uncertainty and potential costs in the environmental management of PFAS. PFAS are not naturally‐occurring, but are frequently detected in environmental media independent of site‐specific (i.e., point source) contamination. Information was collected on background and ambient levels of two predominant PFAS, perfluorooctane sulfonate and perfluorooctanoate, in North America in both abiotic media (soil, sediment, surface water, and public drinking water supplies) and selected biotic media (human tissues, fish, and shellfish). The background or ambient information was compiled from multiple published sources, organized by medium and concentration ranges, and evaluated for geographical trends and, when available, also compared to health‐based screening levels. Data coverage and quality varied from wide‐ranging and well‐documented for soil, surface water, and serum data to more localized and less well‐documented for sediment and fish and shellfish tissues and some uncertainties in the data were noted. Widespread ambient soil and sediment concentrations were noted but were well below human health‐protective thresholds for direct contact exposures. Surface water, drinking water supply waters (representing a combination of groundwater and surface water), fish and shellfish tissue, and human serum levels ranged from less than to greater than available health‐based threshold values. This evaluation highlights the need for incorporating literature‐based or site‐specific background into PFAS site evaluation and decision‐making, so that source identification, risk management, and remediation goals are properly focused and to also inform general policy development for PFAS management.     

Pollutant source identification and allocation: Advances in hydrocarbon fingerprinting

Often liability for environmental damage and cleanup of contaminated sites is made difficult, especially with chemically complex environments containing different pollutants, by the inability to differentiate potential sources (or “owners”) of pollutants from each other. As a result, unnecessary costs may be associated with having to assume financial responsibility for alleged contamination of a site. This article reviews the advances in chemical fingerprinting as a tool in identifying and differentiating sources of hydrocarbon pollutants in chemically complex environments. Appropriate hydrocarbon target analytes and required analytical methods for hydrocarbon fingerprinting are discussed, and new interpretative tools are presented that may be applied to contaminated soil, sediment, and groundwater environmental situations. With these analytical and interpretative techniques, an appropriate allocation of chemical contamination and costs at a site can be made.