Contaminant mass flux and forensic assessment of polycyclic aromatic hydrocarbons: Tools to inform remediation decision making at a contaminated site in Canada

Polycyclic aromatic hydrocarbons (PAHs) and metal(loid) mass flux estimates and forensic assessment using PAH diagnostic ratios were used to inform remediation decision making at the Sydney Tar Ponds (STPs) and Coke Ovens cleanup project in eastern Canada. Environmental effects monitoring of surface marine sediments in Sydney Harbor indicated significantly higher PAH concentrations during the first year of remediation monitoring compared to baseline. This was equivalent to PAH loadings of ～2,000 kg over a 15‐month period. Increases in sediment PAH concentrations raised serious concerns for regulators, who requested cessation of remediation activities early in the $400 M (CAD) project. Historically, the STPs were reported as the primary source of PAH contamination in Sydney Harbor with estimated discharges of 300 to 800 kg/year between 1989 and 2001. Mass flux estimates of PAHs and metal(loid)s and PAH diagnostic ratios were used to evaluate if increases in PAH concentrations in marine sediments were the result of the STPs remediation activities. PAH mass flux estimates approximated that 17 to 97 kg/year were discharged from the STPs during three years of remediation and were corroborated by an independent PAH flux estimate of 119 kg in year 1. PAH fluxes to the Sydney Harbor were mostly surface water derived, with groundwater contributing negligible quantities (0.002–0.005 kg/year). Fluxes of metal(loid)s to harbor sediments were stable or declining across all years and were mirrored in sediment metal(loid) concentrations, which lacked temporal variation, unlike total PAH concentrations. Flux results were also corroborated using PAH diagnostic ratios, which found a common source of PAHs. Coal combustion was likely the principal source of PAHs and not migration from the STPs during remediation. Although short‐term residual sediment PAH increases during onset of remediation raised concerns for regulators, calls for premature cessation of remediation early in the project were unwarranted based on only one year of monitoring data. Mass flux estimates and forensic assessments using PAH diagnostic ratios proved useful tools to inform remediation decision making that helped environmental protection and reduced costs associated with lost cleanup time.     

Climate change,future Arctic Sea ice,and the competitiveness of European Arctic offshore oil and gas production on world markets

A significant share of the world’s undiscovered oil and natural gas resources are assumed to lie under the seabed of the Arctic Ocean. Up until now, the exploitation of the resources especially under the European Arctic has largely been prevented by the challenges posed by sea ice coverage, harsh weather conditions, darkness, remoteness of the fields, and lack of infrastructure. Gradual warming has, however, improved the accessibility of the Arctic Ocean. We show for the most resource-abundant European Arctic Seas whether and how a climate induced reduction in sea ice might impact future accessibility of offshore natural gas and crude oil resources. Based on this analysis we show for a number of illustrative but representative locations which technology options exist based on a cost-minimization assessment. We find that under current hydrocarbon prices, oil and gas from the European offshore Arctic is not competitive on world markets.     

Increased bioavailability of metals in two contrasting agricultural soils treated with waste wood-derived biochar and ash

Recycled waste wood is being increasingly used for energy production; however, organic and metal contaminants in by-products produced from the combustion/pyrolysis residue may pose a significant environmental risk if they are disposed of to land. Here we conducted a study to evaluate if highly polluted biochar (from pyrolysis) and ash (from incineration) derived from Cu-based preservative-treated wood led to different metal (e.g., Cu, As, Ni, Cd, Pb, and Zn) bioavailability and accumulation in sunflower (Helianthus annuus L.). In a pot experiment, biochar at a common rate of 2 % w/w, corresponding to ～50 t ha^?1, and an equivalent pre-combustion dose of wood ash (0.2 % w/w) were added to a Eutric Cambisol (pH 6.02) and a Haplic Podzol (pH 4.95), respectively. Both amendments initially raised soil pH, although this effect was relatively short-term, with pH returning close to the unamended control within about 7 weeks. The addition of both amendments resulted in an exceedance of soil Cu statutory limit, together with a significant increase of Cu and plant nutrient (e.g., K) bioavailability. The metal-sorbing capacity of the biochar, and the temporary increase in soil pH caused by adding the ash and biochar were insufficient to offset the amount of free metal released into solution. Sunflower plants were negatively affected by the addition of metal-treated wood-derived biochar and led to elevated concentration of metals in plant tissue, and reduced above- and below-ground biomass, while sunflower did not grow at all in the Haplic Podzol. Biochar and ash derived from wood treated with Cu-based preservatives can lead to extremely high Cu concentrations in soil and negatively affect plant growth. Identifying sources of contaminated wood in waste stream feedstocks is crucial before large-scale application of biochar or wood ash to soil is considered.     

Potential use of Caulerpa fastigiata biomass for removal of lead: kinetics, isotherms, thermodynamic, and characterization studies

The present study attempts to analyze the biosorption trend of biosorbent Caulerpa fastigiata (macroalgae) biomass for removal of toxic heavy metal ion Pb (II) from solution as a function of initial metal ion concentration, pH, temperature, sorbent dosage, and biomass particle size. The sorption data fitted with various isotherm models and Freundlich model was the best one with correlation coefficient of 0.999. Kinetic study results revealed that the sorption data on Pb (II) with correlation coefficient of 0.999 can best be represented by pseudo-second-order. The biosorption capacity (q _e ) of Pb (II) is 16.11?±?0.32 mg g^?1 on C. fastigiata biomass. Thermodynamic studies showed that the process is exothermic (ΔH° negative). Free energy change (ΔG°) with negative sign reflected the feasibility and spontaneous nature of the process. The SEM studies showed Pb (II) biosorption on selective grains of the biosorbent. The FTIR spectra indicated bands corresponding to –OH, COO^?, –CH, C?=?C, C?=?S, and –C–C– groups were involved in the biosorption process. The XRD pattern of the C. fastigiata was found to be mostly amorphous in nature.     

Comparative statistical study of hourly precipitation determined by radar-based Stage IV and ground-based methods in the North Central United States

Detailed hourly precipitation data are required for long-range modeling of dispersion and wet deposition of particulate matter and water-soluble pollutants using the CALPUFF model. In sparsely populated areas such as the north central United States, ground-based precipitation measurement stations may be too widely spaced to offer a complete and accurate spatial representation of hourly precipitation within a modeling domain. The availability of remotely sensed precipitation data by satellite and the National Weather Service array of next-generation radars (NEXRAD) deployed nationally provide an opportunity to improve on the paucity of data for these areas. Before adopting a new method of precipitation estimation in a modeling protocol, it should be compared with the ground-based precipitation measurements, which are currently relied upon for modeling purposes. This paper presents a statistical comparison between hourly precipitation measurements for the years 2006 through 2008 at 25 ground-based stations in the north central United States and radar-based precipitation measurements available from the National Center for Environmental Predictions (NCEP) as Stage IV data at the nearest grid cell to each selected precipitation station. It was found that the statistical agreement between the two methods depends strongly on whether the ground-based hourly precipitation is measured to within 0.1 in/hr or to within 0.01 in/hr. The results of the statistical comparison indicate that it would be more accurate to use gridded Stage IV precipitation data in a gridded dispersion model for a long-range simulation, than to rely on precipitation data interpolated between widely scattered rain gauges.

Implications:

The current reliance on ground-based rain gauges for precipitation events and hourly data for modeling of dispersion and wet deposition of particulate matter and water-soluble pollutants results in potentially large discontinuity in data coverage and the need to extrapolate data between monitoring stations. The use of radar-based precipitation data, which is available for the entire continental United States and nearby areas, would resolve these data gaps and provide a complete and accurate spatial representation of hourly precipitation within a large modeling domain.     

Radiation modeling of a photo-reactor using a backward ray-tracing method: an insight into indoor photocatalytic oxidation

This article aims to understand the radiation behavior within a photo-reactor, following the ISO 22197-1:2007 standard. The RADIANCE lighting simulation tool, based on the backward ray-tracing modeling method, is employed for a numerical computation of the radiation field. The reflection of the glass cover in the photo-reactor and the test sample influence the amount of irradiance received by the test-sample surface in the photo-reactor setup. The reflection of a white sample limits the irradiance reduction by the glass cover to 1.4 %, but darker samples can lead to an overestimation up to 9.8 % when used in the same setup. This overestimation could introduce considerable error into the interpretation of experiments. Furthermore, this method demonstrates that the kinetics for indoor photocatalytic pollutant degradation can be refined through radiation modeling of the reactor setup. In addition, RADIANCE may aid in future modeling of the more complex indoor environment where radiation affects significantly photocatalytic activity.     

Mechanistic insights into the specificity of human cytosolic sulfotransferase 2A1 (hSULT2A1) for hydroxylated polychlorinated biphenyls through the use of fluoro-tagged probes

Determining the relationships between the structures of substrates and inhibitors and their interactions with drug-metabolizing enzymes is of prime importance in predicting the toxic potential of new and legacy xenobiotics. Traditionally, quantitative structure activity relationship (QSAR) studies are performed with many distinct compounds. Based on the chemical properties of the tested compounds, complex relationships can be established so that models can be developed to predict toxicity of novel compounds. In this study, the use of fluorinated analogues as supplemental QSAR compounds was investigated. Substituting fluorine induces changes in electronic and steric properties of the substrate without substantially changing the chemical backbone of the substrate. In vitro assays were performed using purified human cytosolic sulfotransferase hSULT2A1 as a model enzyme. A mono-hydroxylated polychlorinated biphenyl (4-OH PCB 14) and its four possible mono-fluoro analogues were used as test compounds. Remarkable similarities were found between this approach and previously published QSAR studies for hSULT2A1. Both studies implicate the importance of dipole moment and dihedral angle as being important to PCB structure in respect to being substrates for hSULT2A1. We conclude that mono-fluorinated analogues of a target substrate can be a useful tool to study the structure activity relationships for enzyme specificity.     

Foliar nutrient and metal levels of crops in the Mount Cameroon area—reference values for plant nutrition and environmental monitoring

The growing population number and traffic loads, increasing environmental pressures, agricultural intensification, and the establishment of Mount Cameroon National Park demand farsighted environmental management in the region and the definition of a favorable ecological status. Since plants grow in the interface between soils and the atmosphere they can be used as passive biomonitors for the environmental quality. At the same time, the accumulation of nutrients and pollutants in crops is linked to human health, so that foliar elemental levels can be used as an integrative measure for environmental pollution and impact assessment. In the present study, we collected leaf samples of plantain, cassava, cocoyam, and maize on 28 sites at the southern flanks of Mt. Cameroon and determined 20 chemical elements. Air pollution in the study area comes from biomass and waste burning mainly, but emissions from traffic and a large refinery were believed to also play a significant role. However, spatial patterns in foliar elemental concentrations reflected the geochemistry rather than specific sources of pollution. Significant differences in foliar metal and nutrient levels were observed between the four species, indicating a different demand and uptake of specific elements. The results were compared to published data on nutrient concentrations in the tested species and the so-called reference plant. The data can be used as a baseline for future studies in plant nutrition and the environmental monitoring in inner tropical regions where these crops are grown.     

Projecting current and potential future distribution of the Fire-bellied toad Bombina bombina under climate change in north-eastern Germany

Environmental change is likely to have a strong impact on biodiversity, and many species may shift their distribution in response. In this study, we aimed at projecting the availability of suitable habitat for an endangered amphibian species, the Fire-bellied toad Bombina bombina, in Brandenburg (north-eastern Germany). We modelled a potential habitat distribution map based on (1) a database with 10,581 presence records for Bombina from the years 1990 to 2009, (2) current estimates for ecogeographical variables (EGVs) and (3) the future projection of these EGVs according to the statistical regional model, respectively, the soil and water integrated model, applying the maximum entropy approach (Maxent). By comparing current and potential future distributions, we evaluated the projected change in distribution of suitable habitats and identified the environmental variables most associated with habitat suitability that turned out to be climatic variables related to the hydrological cycle. Under the applied scenario, our results indicate increasing habitat suitability in many areas and an extended range of suitable habitats. However, even if the environmental conditions in Brandenburg may change as predicted, it is questionable whether the Fire-bellied toad will truly benefit, as dispersal abilities of amphibian species are limited and strongly influenced by anthropogenic disturbances, that is, intensive agriculture, habitat destruction and fragmentation. Furthermore, agronomic pressure is likely to increase on productive areas with fertile soils and high water retention capacities, indeed those areas suitable for B. bombina. All these changes may affect temporary pond hydrology as well as the reproductive success and breeding phenology of toads.     

Diatoms in bottom sediments as indicators of pollution of urban aquatic ecosystems

Analysis of the concentrations of chemical elements and the composition of diatoms in the surface layer of bottom sediments has been performed in a small reservoir at the mouth of dammed river to evaluate the levels of pollution and the impact of toxicants on diatom communities of the river ecosystem. Data on interrelations between the concentrations of chemical elements and the relationship between inorganic pollution and accumulation of diatoms in bottom sediments as an indicator of development of the diatom assemblage have been obtained using linear correlation analysis and graphical plotting.