Assessment of five bioaccessibility assays for predicting the efficacy of petroleum hydrocarbon biodegradation in aged contaminated soils

In this study, the bioaccessibility of petroleum hydrocarbons in aged contaminated soils (1.6-67gkg(-1)) was assessed using four non-exhaustive extraction techniques (100% 1-butanol, 100% 1-propanol, 50% 1-propanol in water and hydroxypropyl-β-cyclodextrin) and the persulfate oxidation method. Using linear regression analysis, residual hydrocarbon concentrations following bioaccessibility assessment were compared to residual hydrocarbon concentrations following biodegradation in laboratory-scale microcosms in order to determine whether bioaccessibility assays can predict the endpoint of hydrocarbon biodegradation. The relationship between residual hydrocarbon concentrations following microcosm biodegradation and bioaccessibility assessment was linear (r(2)=0.71-0.97) indicating that bioaccessibility assays have the potential to predict the extent of hydrocarbon biodegradation. However, the slope of best fit varied depending on the hydrocarbon fractional range assessed. For the C(10)-C(14) hydrocarbon fraction, the slope of best fit ranged from 0.12 to 0.27 indicating that the non-exhaustive or persulfate oxidation methods removed 3.5-8 times more hydrocarbons than biodegradation. Conversely, for the higher molecular weight hydrocarbon fractions (C(29)-C(36) and C(37)-C(40)), biodegradation removed up to 3.3 times more hydrocarbons compared to bioaccessibility assays with the resulting slope of best fit ranging from 1.0-1.9 to 2.0-3.3 respectively. For mid-range hydrocarbons (C(15)-C(28)), a slope of approximately one was obtained indicating that C(15)-C(28) hydrocarbon removal by these bioaccessibility assays may approximate the extent of biodegradation. While this study demonstrates the potential of predicting biodegradation endpoints using bioaccessibility assays, limitations of the study include a small data set and that all soils were collected from a single site, presumably resulting from a single contamination source. Further evaluation and validation is required using soils from a range of hydrocarbon contamination sources in order to develop robust assays for predicting bioremediation endpoints in the field.     

Differing effects of inorganic and organic arsenic on uptake and distribution of multi-elements in Rice grain

Environmental Science and Pollution Research - Arsenic (As) pollution can lead to an element imbalance in rice. A hydroponic study was carried out to examine the influence of inorganic (arsenate)...     

Clay mineral adsorbents for heavy metal removal from wastewater: a review

Environmental Chemistry Letters - Heavy metal pollution such as water contamination by Pb, Hg, Cu, Cd and Cr ions is induced by rapid urbanization and industrialization and is a major threat to...     

Diffusive gradients in thin films: devices,materials and applications

Environmental Chemistry Letters - A large number of ex situ sampling techniques have been used traditionally to investigate the impact and fate of pollutants in soil, sediment and waters. However,...     

Assessment and monitoring tools for aerobic bioremediation of vinyl chloride in groundwater

Direct aerobic biodegradation of vinyl chloride (VC) offers a remedial solution for persistent vinyl chloride plumes that are not amenable to the anaerobic process of reductive dechlorination because of either prevailing geochemical conditions or the absence of active Dehalococcoides ethenogenes. However, tools are needed to evaluate and optimize aerobic VC bioremediation. This article describes the development and testing of two techniques—a microbiological tool and a molecular tool—for this purpose. Both methods are based on detection of bacteria that can use vinyl chloride and ethene as growth substrates in the presence of oxygen. The microbiological tool is an activity assay that indicates whether bacteria capable of degrading ethene under aerobic conditions are present in a groundwater sample. This activity assay gave positive results in the area of active VC degradation of an aerobic VC bioremediation test site. A rapid semiquantitative genetic assay was also developed. This molecular tool, based on polymerase chain reaction (PCR) detection of a gene involved in the metabolism of both ethene and VC, revealed the presence of potential VC degraders in an enrichment culture and site groundwater. These tools could provide a basis for judging the potential of aerobic VC degradation by ethenotrophs at other sites in addition to offering a mechanism for treatment monitoring and system optimization. © 2009 Wiley Periodicals, Inc.     

Future land use and land cover influences on regional biogenic emissions and air quality in the United States

A regional modeling system was applied with inputs from global climate and chemistry models to quantify the effects of global change on future biogenic emissions and their impacts on ozone and biogenic secondary organic aerosols (BSOA) in the US. Biogenic emissions in the future are influenced by projected changes in global and regional climates and by variations in future land use and land cover (LULC). The modeling system was applied for five summer months for the present-day case (1990–1999, Case 1) and three future cases covering 2045–2054. Individual future cases were: present-day LULC (Case 2); projected-future LULC (Case 3); and future LULC with designated regions of tree planting for carbon sequestration (Case 4). Results showed changing future meteorology with present-day LULC (Case 2) increased average isoprene and monoterpene emission rates by 26% and 20% due to higher temperature and solar insolation. However when LULC was changed together with climate (Case 3), predicted isoprene and monoterpene emissions decreased by 52% and 31%, respectively, due primarily to projected cropland expansion. The reduction was less, at 31% and 14% respectively, when future LULC changes were accompanied by regions of tree planting (Case 4). Despite the large decrease in biogenic emission, future average daily maximum 8-h (DM8H) ozone was found to increase between +8 ppbv and +10 ppbv due to high future anthropogenic emissions and global chemistry conditions. Among the future cases, changing LULC resulted in spatially varying future ozone differences of ?5 ppbv to +5 ppbv when compared with present-day case. Future BSOA changed directly with the estimated monoterpene emissions. BSOA increased by 8% with current LULC (Case 2) but decreased by 45%–28% due to future LULC changes. Overall, the results demonstrated that on a regional basis, changes in LULC can offset temperature driven increases in biogenic emissions, and, thus, LULC projection is an important factor to consider in the study of future regional air quality.     

Effects of intense agricultural practices on heterotrophic processes in streams

In developed countries, changes in agriculture practices have greatly accelerated the degradation of the landscape and the functioning of adjacent aquatic ecosystems. Such alteration can in turn impair the services provided by aquatic ecosystems, namely the decomposition of organic matter, a key process in most small streams. To study this alteration, we recorded three measures of heterotrophic activity corresponding to microbial hydrolasic activity (FDA hydrolysis) and leaf litter breakdown rates with (k_c) and without invertebrates (k_f) along a gradient of contrasted agricultural pressures. Hydrolasic activity and k_f reflect local/microhabitat conditions (i.e. nutrient concentrations and organic matter content of the sediment) but not land use while k_c reflects land-use conditions. k_c, which is positively correlated with the biomass of Gammaridae, significantly decreased with increasing agricultural pressure, contrary to the taxonomic richness and biomass of Trichoptera and Plecoptera. Gammaridae may thus be considered a key species for organic matter recycling in agriculture-impacted streams.     

Evaluation of PCDD/F oxidation catalysts: confronting studies on model molecules with tests on PCDD/F-containing gas stream

Titania supported vanadium oxide is a renowned catalyst for the abatement of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from gas effluents. To develop more active formulations, researchers mainly rely on lab-scale experiments on “PCDD/Fs-mimicking substances”, like (chloro)-benzene. Using such model compounds is convenient whereas handling PCDD/Fs in the laboratory is potentially hazardous and complicated. Recent studies, however, challenged some foremost conclusions of model compound based studies, starting from the observation that different model compounds gave contrasted results. Thus the present work aims at confronting some of these dubious conclusions with direct experimental tests on PCDD/Fs. One reference V₂O₅/TiO₂ catalyst and three modified formulations (V₂O₅/TiO₂-SO₄, V₂O₅-MoO₃/TiO₂, and V₂O₅-WO₃/TiO₂) have been evaluated. A dedicated apparatus was used which allows safe and reliable tests on a mixture of PCDD/Fs congeners. Some of the previously proposed catalyst improvement strategies actually prove to be disadvantageous in the removal of PCDD/Fs. In particular, MoO₃- and WO₃-modified catalysts were significantly less active than the reference catalyst. These observations show that conclusions from model compound based studies must be drawn with care and should ideally be confronted with tests on the actual target pollutants.     

Halogenated persistent organic pollutants in deep water fish from waters to the west of Scotland

Halogenated persistent organic pollutants [polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)] along with total lipid, were measured in the liver and muscle of three species of deep water fish (black scabbard, black dogfish (liver only) and roundnose grenadier) collected from the Rockall fishing area, to the west of Scotland, between 2006 and 2008. Both contaminant groups were detected in the muscle and liver, with concentrations of PCBs being higher than PBDEs. There were no significant differences in the PCB or PBDE concentrations between the three species, or different sampling locations in the Rockall fishing area. PCB concentrations (ΣICES (International Council for the Exploration of the Sea)7 PCBs) greater than 500 μg kg⁻¹ lipid weight were found in 26 of the 106 liver samples. PCB concentrations were compared to OSPAR assessment criteria, concentrations were above background but below Environmental Assessment Criteria. Estimated Toxic Equivalent (TEQ) concentrations, calculated using published models, in the fish muscle and liver indicated that consumption of deep water fish is unlikely to represent a risk to human health. The high squalene content in some of the black dogfish liver necessitated an additional clean-up step, involving gel permeation chromatography, when analyzing for PBDEs. Concentrations of PBDEs were low with many congeners being below detection limits, particularly in the muscle. There are currently no assessment criteria available for PBDEs. Furthermore, there is only very limited data on PBDEs in deep water fish. However, the concentrations observed in this study were similar to the concentrations recently reported in Mediterranean deep water fish.     

Microbial physiology-based model of ethanol metabolism in subsurface sediments

Dense non-aqueous phase liquids (DNAPLs) present in the subsurface may contain surface active compounds that impact DNAPL migration and distribution. While a number of studies have revealed the role surface active compounds play in altering the wettability of quartz sand, few have considered the implications for other minerals common to contaminated sites. This study extends understanding of DNAPL/surfactant wettability to iron oxide surfaces. Specifically, quartz and iron oxide-coated sands in a tetrachloroethene (PCE)/water system containing the organic base (an organic molecule that acts as a base) dodecylamine (DDA) were compared at a variety of scales. Wettability of the minerals' surfaces, and the impact of wettability on capillary resistance to DNAPL entry, were assessed as a function of pH through: (i) advancing and receding contact angles, (ii) primary drainage capillary pressure-saturation experiments, and (iii) small, two-dimensional, flow cell experiments. The work revealed that, at neutral pH and under identical boundary capillary pressures, DNAPL invaded quartz sand but not iron oxide-coated sand; however, at low pH, DNAPL invaded both sands equally. These differences were demonstrated to be due to wettability alterations associated with the strength of attractive forces between DDA and the mineral surface, dictated by the isolectric point of the minerals and system pH. Observed differences in DNAPL invasion behavior were consistent with measured intrinsic contact angles and P(c)-S relationships, the latter requiring scaling by the operative contact angle inside the porous medium for a meaningful comparison. This study suggests that the distribution of minerals (and, more specifically, their isoelectric points), as well as the aqueous phase pH at a given site, may have a significant impact on the DNAPL source zone architecture.