Passive air sampling theory for semivolatile organic compounds

The mathematical modelling underlying passive air sampling theory can be based on mass transfer coefficients or rate constants. Generally, these models have not been inter-related. Starting with basic models, the exchange of chemicals between the gaseous phase and the sampler is developed using mass transfer coefficients and rate constants. Importantly, the inter-relationships between the approaches are demonstrated by relating uptake rate constants and loss rate constants to mass transfer coefficients when either sampler-side or air-side resistance is dominating chemical exchange. The influence of sampler area and sampler volume on chemical exchange is discussed in general terms and as they relate to frequently used parameters such as sampling rates and time to equilibrium. Where air-side or sampler-side resistance dominates, an increase in the surface area of the sampler will increase sampling rates. Sampling rates are not related to the sampler/air partition coefficient (K(SV)) when air-side resistance dominates and increase with K(SV) when sampler-side resistance dominates.     

Distribution and partitioning of phosphorus in solid waste and sediments from drainage canals in the industrial belt of Delhi, India

Phosphorus is an essential and often limiting nutrient in both marine and freshwater ecosystems. However, its oversupply is of great concern in many environments due to its role in eutrophication. The concentration and distribution of sediment bound phosphorus species not only record its input into the environment, but also suggest their possible sources. It is recognized that the features of phosphorus behaviour have not been extensively studied in urban environments. In this study, phosphorus in solid waste and sediments from drainage canals within the industrial belt of Delhi were fractionated into five operationally defined forms, i.e., exchangeable or loosely sorbed phosphorus (Exch-P), Fe-bound phosphorus (Fe-P), authigenic apatite, CaCO3-bound phosphorus and biogenic apatite (Acet-P), detrital apatite (Det-P) and organic-bound phosphorus (Org-P), in order to assess the potential bioavailability status in these systems.     

Limited microbial degradation of pyrene metabolites from the estuarine polychaete Nereis diversicolor

We compared microbial mineralization of [4,5,9,10-14C]pyrene and its eukaryotic [4,5,9,10-14C]pyrene metabolites in estuarine sediments. Metabolites were obtained by exposing the estuarine deposit-feeding polychaete Nereis diversicolor to sediment-associated 14C-pyrene, followed by homogenization of the worms and extraction of the pyrene-metabolites. In sediment from a pristine Danish Fjord only 2.6% of the added metabolite-label and 1.7% of the pyrene-label were mineralized to 14CO2 during 175 days incubation. Pre-exposure of the pristine sediment to unlabelled pyrene for 60 days increased the mineralization potential for 14C-pyrene substantially, as 81.2% was mineralized to 14CO2 during 95 days incubation, whereas 14C-pyrene metabolite label was unaffected by pre-exposure to pyrene. In comparison, naturally aged bunker-oil contaminated sediment did not show elevated potentials for mineralization of neither 14C-pyrene nor 14C-metabolites. Six bacterial strains of known pyrene degraders were tested for growth on crystalline 1-hydroxypyrene. 1-Hydroxypyrene is the only intermediate eucaryotic metabolite of pyrene. The results indicate that 1-hydroxypyrene was not utilized as a sole source of carbon and energy by any of them. In addition, respiration was depressed in all six strains when exposed to crystalline 1-Hydroxypyrene, demonstrating an acute toxic effect of 1-hydroxypyrene. The results presented here suggest that microbial degradation of pyrene is not enhanced by release of aqueous and polar metabolites by marine invertebrates.     

Dissolved oxygen and dietary phosphorus modulate utilization and effluent partitioning of phosphorus in rainbow trout (Oncorhynchus mykiss) aquaculture

Phosphorus (P) is the limiting nutrient in freshwater primary production, and excessive levels cause premature eutrophication. P levels in aquaculture effluents are now tightly regulated. Increasing our understanding of waste P partitioning into soluble, particulate, and settleable fractions is important in the management of effluent P. When water supply is limited, dissolved oxygen concentration (DO) decreases below the optimum levels. Therefore, we studied effects of DO (6 and 10mg/L) and dietary P (0.7 and 1.0% P) on rainbow trout growth, P utilization, and effluent P partitioning. Biomass increased by 40% after 3 weeks. DO at 10mg/L significantly increased fish growth and feed efficiency, and increased the amount of P in the soluble fraction of the effluent. Soluble effluent P was greater in fish fed 1.0% P. DO increases fish growth and modulates P partitioning in aquaculture effluent.     

Long-term increases in surface water dissolved organic carbon: observations, possible causes and environmental impacts

Dissolved organic carbon (DOC) concentrations in 22 UK upland waters have increased by an average of 91% during the last 15 years. Increases have also occurred elsewhere in the UK, northern Europe and North America. A range of potential drivers of these trends are considered, including temperature, rainfall, acid deposition, land-use, nitrogen and CO2 enrichment. From examination of recent environmental changes, spatial patterns in observed trends, and analysis of time series, it is suggested that DOC may be increasing in response to a combination of declining acid deposition and rising temperatures; however it is difficult to isolate mechanisms based on monitoring data alone. Long-term DOC increases may have wide-ranging impacts on freshwater biota, drinking water quality, coastal marine ecosystems and upland carbon balances. Full understanding of the significance of these increases requires further knowledge of the extent of natural long-term variability, and of the natural "reference" state of these systems.     

Temporal variation of trace metal geochemistry in floodplain lake sediment subject to dynamic hydrological conditions

Climate change and land use may significantly influence metal cycling in dynamic river systems. We studied temporal variation of sediment characteristics in a floodplain lake, including concentrations of dissolved organic carbon, acid volatile sulfide and trace metals. The sampling period included a severe winter inundation and a dramatic water level drop during summer. Temporal changes were interpreted using multivariate analysis and chemical equilibrium calculations. Metal concentrations in sediment increased with depth, indicating a gradual improvement of sediment quality. In contrast, dissolved metal concentrations were highest in top layers due to mobilization from oxyhydroxides and precipitation with sulfides in deeper layers. Inundation had a mobilizing effect as it stimulated resuspension and oxygenation of sediment top layers. Water table lowering combined with organic matter decomposition led to immobilization due to sulfide formation. The chemistry of the sediments was consistent with model calculations, especially for macro-elements. The results illustrate the importance of seasonality for metal risk assessment.     

Influence of hydroxypropyl-beta-cyclodextrin (HPCD) on the bioavailability and biodegradation of pyrene

It is well known that the limited aqueous solubilities of polycyclic aromatic hydrocarbons (PAH) often reduce their bioavailability to bacterial populations. The objective of this study was to test the impact of a solubility-enhancement reagent, hydroxypropyl-beta-cyclodextrin (HPCD), on the bioavailability and biodegradation of pyrene. No measurable loss of pyrene occurred for the control vials throughout the first 22 weeks of the experiment, indicating the absence of mass loss via abiotic transformation and volatilization. The vials containing pyrene and the degrader isolate (Burkholderia CRE 7), but no HPCD, also exhibited no measurable loss of pyrene throughout the experiment. Conversely, biodegradation of pyrene appears to have been initiated after approximately 15 weeks for the vials containing 10(4) mg l(-1) HPCD. By the end of the experiment, approximately 14% (w/w) of the pyrene was biodegraded in the presence of HPCD. These results indicate that HPCD may be useful for enhancing the bioavailability and biodegradation of pyrene and other PAHs.     

Modeling mercury fluxes and concentrations in a Georgia watershed receiving atmospheric deposition load from direct and indirect sources

This paper presents a modeling analysis of airborne mercury (Hg) deposited on the Ochlockonee River watershed located in Georgia. Atmospheric deposition monitoring and source attribution data were used along with simulation models to calculate Hg buildup in the subwatershed soils, its subsequent runoff loading and delivery through the tributaries, and its ultimate fate in the mainstem river. The terrestrial model calculated annual watershed yields for total Hg ranging from 0.7 to 1.1 microg/m2. Results suggest that approximately two-thirds of the atmospherically deposited Hg to the watershed is returned to the atmosphere, 10% is delivered to the river, and the rest is retained in the watershed. A check of the aquatic model results against survey data showed a reasonable agreement. Comparing observed and simulated total and methylmercury concentrations gave root mean square error values of 0.26 and 0.10 ng/L, respectively, in the water column, and 5.9 and 1 ng/g, respectively, in the upper sediment layer. Sensitivity analysis results imply that mercury in the Ochlockonee River is dominated by watershed runoff inputs and not by direct atmospheric deposition, and that methylmercury concentrations in the river are determined mainly by net methylation rates in the watershed, presumably in wetted soils and in the wetlands feeding the river.     

Organochlorine residues in odontocete species from the southeast coast of India

Blubber from bottle-nose dolphins, spinner dolphins, humpback dolphin (Tursiops truncatus, Stenella longirostris and Sousa chinensis) were collected from the Bay of Bengal (southeast coast of India) and analyzed for the organochlorine pesticides hexachlorocyclohexane (HCHs), p,p'-dichlorodiphenyl trichloroethane (DDTs), and polychlorinated biphenyls (PCBs). All nine specimens analyzed contained considerable levels of all the three chemical classes where DDT was in the range of 3330-23330 ng/g; HCHs in the range of 95-765 ng/g; and PCBs in the range of 210-1220 ng/g (wet weight basis). The reasons for this and the variations in the isomer pattern of HCHs and DDT and its metabolites in marine mammal tissues are discussed.     

Halogenated compounds in a dated sediment core of the Teltow Canal, Berlin: time related sediment contamination

To study the recent contamination history of DDT (1,1,1-trichloro-2,2-bis(chlorophenyl)ethane) and its metabolites, as well as methoxychlor (1,1,1-trichloro-2,2-bis(p-methoxyphenyl)ethane), chlorfenson (4-chlorophenyl-p-chlorobenzenesulfonate), and further halogenated aromatics, a sediment core was collected from the Teltow Canal in Berlin (Germany). The sampling site is located nearby a former industrial point source, where recently analyses on pre-samples have indicated high concentrations of halogenated organic compounds. The deposition time of the investigated sediments was determined by gamma-spectrometrical dating. Pollution trends of selected contaminants were attributed to a time period between 5 and 10 years. Concentration profiles reflect not only the recent pollution history of these compounds, but also the time-depending effects of the ban, restriction and termination of DDT-production in the German Democratic Republic (GDR). DDT and other chlorinated aromatic compounds were produced onsite until the late 1980s. Maximum values of 133 mg kg(-1) (dry weight) for p,p'-DDD (1,1-dichloro-2,2-bis(chlorophenyl)ethane) and approximately 100 mg kg(-1) (dry weight) for p,p'-DDMS (1-chloro-2,2-bis(chlorophenyl)ethane), main metabolites of the anaerobic degradation of DDT, were determined. The occurrence of all selected contaminants, most of which have been banned more than 10 years ago, demonstrate recent contamination pathways, and the necessity of a continuous long-term monitoring of the affected environment.