Bioavailability of contaminants estimated from uptake rates into soil invertebrates

It is often argued that the concentration of a pollutant inside an organism is a good indicator of its bioavailability, however, we show that the rate of uptake, not the concentration itself, is the superior predictor. In a study on zinc accumulation and toxicity to isopods (Porcellio scaber) the dietary EC(50) for the effect on body growth was rather constant and reproducible, while the internal EC(50) varied depending on the accumulation history of the animals. From the data a critical value for zinc accumulation in P. scaber was estimated as 53 microg/g/wk. We review toxicokinetic models applicable to time-series measurements of concentrations in invertebrates. The initial slope of the uptake curve is proposed as an indicator of bioavailability. To apply the dynamic concept of bioavailability in risk assessment, a set of representative organisms should be chosen and standardized protocols developed for exposure assays by which suspect soils can be evaluated.     

Atmospheric trace metal pollution in the Naples urban area based on results from moss and lichen bags

The results of trace element content analysed in Sphagnum capillifolium and Pseudevernia furfuracea exposed in bags in 1999 are reconsidered to evaluate the reliability of moss and lichen transplants to detect urban trace element atmospheric pollution, using Naples as a case example. After 4 months' exposure, trace element concentrations were at least twice as high as the pre-exposure values and in general higher in Sphagnum than in Pseudevernia. Moss samples were enriched in the following order: As=Cu>Mo>Pb>V>Co>Cr>Zn; lichen samples in the order: Mo>Cu>As=Co=Ni>V>Pb. Based on the calculation of a cumulative load factor, all sites located along the coast had higher trace element loads compared to sites in the hilly inland area. Complementary SEM, TEM and EDS observations showed, despite significant damage to tissue and cell integrity, the recurrent presence of particulate matter in moss and lichen, indicating the considerable presence of dust in the urban atmosphere which, according to chemical composition, may be due both to anthropogenic and natural sources such as volcanic rock and soil and sea salts.     

Enhancing bioremediation of diesel oil and gasoline in soil amended with an agroindustry sludge

This paper presents a study of the bioremediation of diesel oil and gasoline by a series of controlled laboratory tests. Sludge from an agroindustry was used to enhance bioremediation of both gasoline and diesel oil mixed with a soil mass to compare its efficiency with that of a mineral fertilizer. Effects of soil microbiology and soil mixtures were investigated by means of evolution of CO2, microorganism populations at 90 days, pH at 65 and 95 days, mineral nitrogen, and gas chromatographic analysis of the benzene, toluene, methyl tertiary butyl ether, C8, and C9+total aromatics at the end of the experiments. Treatments containing sludge showed better soil conditions after 170 days of treatment (inorganic nitrogen and microbiota activity) compared with gasoline and diesel oil without amendments. Samples had no detectable traces of the measured hydrocarbons at 170 days of treatment.     

Monitoring and toxicity of sulfonated derivatives of benzene and naphthalene in municipal sewage treatment plants

Monitoring benzenesulfonates (BS) and naphthalenesulfonates (NS) took place in five municipal sewage treatment plants (STP). A previously optimized method based on solid phase extraction with polymeric cartridges followed by ion-pair liquid chromatography-electrospray-mass spectrometry (SPE-IPC-ESI-MS) was used. This work confirmed the little or no effect of primary settlement on total organic carbon (TOC) and monosulfonated compounds removal, whereas the main reduction is obtained at the biological stage. However, the most polar compounds, such as naphthalenedisulfonates (NDS), were not effectively removed using the biological treatment. An aromatic sulfonated compound is suggested to be used as a tracer of the origin of industrial pollutants discharged into STPs. A bioluminescence inhibition test, Microtox assay, allowed toxicity determination of the most relevant aromatic sulfonated compounds detected and toxicity comparison between primary and secondary effluents.     

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.     

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.     

Photo-Fenton-assisted ozonation of p-Coumaric acid in aqueous solution

The degradation of p-Coumaric acid present in olive oil mill wastewater was investigated as a pretreatment stage to obtain more easily biodegradable molecules, with lower toxicity that facilitates subsequent anaerobic digestion. Thus, photo-Fenton-assisted ozonation has been studied and compared with ozonation at alkaline pH and conventional single ultraviolet (UV) and acid ozonation treatments. In the combined process, the overall kinetic rate constant was split into various components: direct oxidation by UV light, direct oxidation by ozone and oxidation by hydroxyl radicals. Molecular and/or radical ozone reaction was studied by conducting the reaction in the presence and absence of tert-butylalcohol at pHs 2, 7 and 9. Ozone oxidation rate increases with pH or by the addition of Fenton reagent and/or UV radiation due to generation of hydroxyl radicals, *OH. Hydrogen peroxide and ferrous ion play a double role during oxidation since at low concentrations they act as initiators of hydroxyl radicals but at high concentrations they act as radical scavengers. Finally, the additional levels of degradation by formation of hydroxyl radicals have been quantified in comparison to the conventional single processes and an equation is proposed for the reaction rate as a function of studied operating variables.     

The impact of pumped water from a de-watered Magnesian limestone quarry on an adjacent wetland: Thrislington, County Durham, UK

Although quarrying is often cited as a potential threat to wetland systems, there is a lack of relevant, quantitative case studies in the literature. The impact of pumped groundwater discharged from a quarry into a wetland area was assessed relative to reference conditions in an adjacent fen wetland that receives only natural runoff. Analysis of vegetation patterns at the quarry wetland site, using Detrended Correspondence Analysis and the species indicator values of Ellenberg, revealed a clear disparity between community transitions in the quarry wetland and the reference site. Limited establishment of moisture-sensitive taxa, the preferential proliferation of robust wetland species and an overall shift towards lower species diversity in the quarry wetland were explicable primarily by the physico-chemical environment created by quarry dewatering. This encompassed high pH (up to 12.8), sediment-rich effluent creating a nutrient-poor substrate with poor moisture retention in the quarry wetland, and large fluctuations in water levels.