Partitioning of perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) between water and sediment

Laboratory partitioning experiments were conducted to elucidate the sorption behaviour and partitioning of perfluoroalkyl compounds (PFCs). Three different sediment types were used and separately spiked with perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) at low environmentally realistic concentrations. PFOA, PFOS and PFOSA were mainly distributed in the dissolved phase at low suspended solid concentrations, indicating their long-range transport potential in the marine environment. In all cases, the equilibrium isotherms were linear and the organic carbon normalised partition coefficients (K_OC) decreased in the following order: PFOSA (log K_OC = 4.1 ± 0.35 cm³ g⁻¹) > PFOS (3.7 ± 0.56 cm³ g⁻¹) > PFOA (2.4 ± 0.12 cm³ g⁻¹). The level of organic content had a significant influence on the partitioning. For the sediment with negligible organic content the density of the sediment became the most important factor influencing the partitioning. Ultimately, data on the partitioning of PFCs between aqueous media and suspended solids are essential for modelling their transport and environmental fate.     

Transport of Escherichia coli in 25 m quartz sand columns

To help improve the prediction of bacteria travel distances in aquifers laboratory experiments were conducted to measure the distant dependent sticking efficiencies of two low attaching Escherichia coli strains (UCFL-94 and UCFL-131). The experimental set up consisted of a 25 m long helical column with a diameter of 3.2 cm packed with 99.1% pure-quartz sand saturated with a solution of magnesium sulfate and calcium chloride. Bacteria mass breakthrough at sampling distances ranging from 6 to 25.65 m were observed to quantify bacteria attachment over total transport distances (α(L)) and sticking efficiencies at large intra-column segments (α(i)) (>5m). Fractions of cells retained (F(i)) in a column segment as a function of α(i) were fitted with a power-law distribution from which the minimum sticking efficiency defined as the sticking efficiency of 0.001% bacteria fraction of the total input mass retained that results in a 5 log removal were extrapolated. Low values of α(L) in the order 10(-4) and 10(-3) were obtained for UCFL-94 and UCFL-131 respectively, while α(i)-values ranged between 10(-6) to 10(-3) for UCFL-94 and 10(-5) to 10(-4) for UCFL-131. In addition, both α(L) and α(i) reduced with increasing transport distance, and high coefficients of determination (0.99) were obtained for power-law distributions ofα(i) for the two strains. Minimum sticking efficiencies extrapolated were 10(-7) and 10(-8) for UCFL-94 and UCFL-131, respectively. Fractions of cells exiting the column were 0.19 and 0.87 for UCFL-94 and UCL-131, respectively. We concluded that environmentally realistic sticking efficiency values in the order of 10(-4) and 10(-3) and much lower sticking efficiencies in the order 10(-5) are measurable in the laboratory, Also power-law distributions in sticking efficiencies commonly observed for limited intra-column distances (<2m) are applicable at large transport distances(>6m) in columns packed with quartz grains. High fractions of bacteria populations may possess the so-called minimum sticking efficiency, thus expressing their ability to be transported over distances longer than what might be predicted using measured sticking efficiencies from experiments with both short (<1m) and long columns (>25 m). Also variable values of sticking efficiencies within and among the strains show heterogeneities possibly due to variations in cell surface characteristics of the strains. The low sticking efficiency values measured express the importance of the long columns used in the experiments and the lower values of extrapolated minimum sticking efficiencies makes the method a valuable tool in delineating protection areas in real-world scenarios.     

Fate of nitrogen for subsurface drip dispersal of effluent from small wastewater systems

Subsurface drip irrigation systems apply effluent from onsite wastewater systems in a more uniform manner at a lower rate than has been possible with other effluent dispersal methods. The effluent is dispersed in a biologically active part of the soil profile for optimal treatment and where the water and nutrients can be utilized by landscape plants. Container tests were performed to determine the fate of water and nitrogen compounds applied to packed loamy sand, sandy loam, and silt loam soils. Nitrogen removal rates measured in the container tests ranged from 63 to 95% despite relatively low levels of available carbon. A Hydrus 2D vadose zone model with nitrification and denitrification rate coefficients calculated as a function of soil moisture content fit the container test results reasonably well. Model results were sensitive to the denitrification rate moisture content function. Two-phase transport parameters were needed to model the preferential flow conditions in the finer soils. Applying the model to generic soil types, the greatest nitrogen losses (30 to 70%) were predicted for medium to fine texture soils and soils with restrictive layers or capillary breaks. The slow transport with subsurface drip irrigation enhanced total nitrogen losses and plant nitrogen uptake opportunity.     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.     

Effects of C60 nanoparticle exposure on earthworms (Lumbricus rubellus) and implications for population dynamics

Effects of C₆₀ nanoparticles (nominal concentrations 0, 15.4 and 154 mg/kg soil) on mortality, growth and reproduction of Lumbricus rubellus earthworms were assessed. C₆₀ exposure had a significant effect on cocoon production, juvenile growth rate and mortality. These endpoints were used to model effects on the population level. This demonstrated reduced population growth rate with increasing C₆₀ concentrations. Furthermore, a shift in stage structure was shown for C₆₀ exposed populations, i.e. a larger proportion of juveniles. This result implies that the lower juvenile growth rate due to exposure to C₆₀ resulted in a larger proportion of juveniles, despite increased mortality among juveniles. Overall, this study indicates that C₆₀ exposure may seriously affect earthworm populations. Furthermore, it was demonstrated that juveniles were more sensitive to C₆₀ exposure than adults.     

Plant communities in relation to flooding and soil contamination in a lowland Rhine River floodplain

Using canonical correspondence analysis (CCA), relationships were investigated between plant species composition and flooding characteristics, heavy metal contamination and soil properties in a lowland floodplain of the Rhine River. Floodplain elevation and yearly average flooding duration turned out to be more important for explaining variation in plant species composition than soil heavy metal contamination. Nevertheless, plant species richness and diversity showed a significant decrease with the level of contamination. As single heavy metal concentrations seemed mostly too low for causing phytotoxic effects in plants, this trend is possibly explained by additive effects of multiple contaminants or by the concomitant influences of contamination and non-chemical stressors like flooding. These results suggest that impacts of soil contamination on plants in floodplains could be larger than expected from mere soil concentrations. In general, these findings emphasize the relevance of analyzing effects of toxic substances in concert with the effects of other relevant stressors.     

Integrated analysis of the effects of agricultural management on nitrogen fluxes at landscape scale

The integrated modelling system INITIATOR was applied to a landscape in the northern part of the Netherlands to assess current nitrogen fluxes to air and water and the impact of various agricultural measures on these fluxes, using spatially explicit input data on animal numbers, land use, agricultural management, meteorology and soil. Average model results on NH₃ deposition and N concentrations in surface water appear to be comparable to observations, but the deviation can be large at local scale, despite the use of high resolution data. Evaluated measures include: air scrubbers reducing NH₃ emissions from poultry and pig housing systems, low protein feeding, reduced fertilizer amounts and low-emission stables for cattle. Low protein feeding and restrictive fertilizer application had the largest effect on both N inputs and N losses, resulting in N deposition reductions on Natura 2000 sites of 10% and 12%, respectively.     

A mathematical model for the interactive behavior of sulfate-reducing bacteria and methanogens during anaerobic digestion

Anaerobic degradation of waste involves different classes of microorganisms, and there are different types of interactions among them for substrates, terminal electron acceptors, and so on. A mathematical model is developed based on the mass balance of different substrates, products, and microbes present in the system to study the interaction between methanogens and sulfate-reducing bacteria (SRB). The performance of major microbial consortia present in the system, such as propionate-utilizing acetogens, butyrate-utilizing acetogens, acetoclastic methanogens, hydrogen-utilizing methanogens, and SRB were considered and analyzed in the model. Different substrates consumed and products formed during the process also were considered in the model. The experimental observations and model predictions showed very good prediction capabilities of the model. Model prediction was validated statistically. It was observed that the model-predicted values matched the experimental data very closely, with an average error of 3.9%.     

Comparing universal kriging and land-use regression for predicting concentrations of gaseous oxides of nitrogen (NOx) for the Multi-Ethnic Study of Atherosclerosis and Air Pollution (MESA Air)

BACKGROUND: Epidemiological studies that assess the health effects of long-term exposure to ambient air pollution are used to inform public policy. These studies rely on exposure models that use data collected from pollution monitoring sites to predict exposures at subject locations. Land use regression (LUR) and universal kriging (UK) have been suggested as potential prediction methods. We evaluate these approaches on a dataset including measurements from three seasons in Los Angeles, CA. METHODS: The measurements of gaseous oxides of nitrogen (NOx) used in this study are from a "snapshot" sampling campaign that is part of the Multi-Ethnic Study of Atherosclerosis and Air Pollution (MESA Air). The measurements in Los Angeles were collected during three two-week periods in the summer, autumn, and winter, each with about 150 sites. The design included clusters of monitors on either side of busy roads to capture near-field gradients of traffic-related pollution. LUR and UK prediction models were created using geographic information system (GIS)-based covariates. Selection of covariates was based on 10-fold cross-validated (CV) R(2) and root mean square error (RMSE). Since UK requires specialized software, a computationally simpler two-step procedure was also employed to approximate fitting the UK model using readily available regression and GIS software. RESULTS: UK models consistently performed as well as or better than the analogous LUR models. The best CV R(2) values for season-specific UK models predicting log(NOx) were 0.75, 0.72, and 0.74 (CV RMSE 0.20, 0.17, and 0.15) for summer, autumn, and winter, respectively. The best CV R(2) values for season-specific LUR models predicting log(NOx) were 0.74, 0.60, and 0.67 (CV RMSE 0.20, 0.20, and 0.17). The two-stage approximation to UK also performed better than LUR and nearly as well as the full UK model with CV R(2) values 0.75, 0.70, and 0.70 (CV RMSE 0.20, 0.17, and 0.17) for summer, autumn, and winter, respectively. CONCLUSION: High quality LUR and UK prediction models for NOx in Los Angeles were developed for the three seasons based on data collected for MESA Air. In our study, UK consistently outperformed LUR. Similarly, the 2-step approach was more effective than the LUR models, with performance equal to or slightly worse than UK.     

Total fuel-cycle analysis of heavy-duty vehicles using biofuels and natural gas-based alternative fuels

Heavy-duty vehicles (HDVs) present a growing energy and environmental concern worldwide. These vehicles rely almost entirely on diesel fuel for propulsion and create problems associated with local pollution, climate change, and energy security. Given these problems and the expected global expansion of HDVs in transportation sectors, industry and governments are pursuing biofuels and natural gas as potential alternative fuels for HDVs. Using recent lifecycle datasets, this paper evaluates the energy and emissions impacts of these fuels in the HDV sector by conducting a total fuel-cycle (TFC) analysis for Class 8 HDVs for six fuel pathways: (1) petroleum to ultra low sulfur diesel; (2) petroleum and soyoil to biodiesel (methyl soy ester); (3) petroleum, ethanol, and oxygenate to e-diesel; (4) petroleum and natural gas to Fischer-Tropsch diesel; (5) natural gas to compressed natural gas; and (6) natural gas to liquefied natural gas. TFC emissions are evaluated for three greenhouse gases (GHGs) (carbon dioxide, nitrous oxide, and methane) and five other pollutants (volatile organic compounds, carbon monoxide, nitrogen oxides, particulate matter, and sulfur oxides), along with estimates of total energy and petroleum consumption associated with each of the six fuel pathways. Results show definite advantages with biodiesel and compressed natural gas for most pollutants, negligible benefits for e-diesel, and increased GHG emissions for liquefied natural gas and Fischer-Tropsch diesel (from natural gas).