Sources and historical record of tin and butyl-tin species in a Mediterranean bay (Toulon Bay,France)

Concentrations of inorganic tin (Sn_inorg), tributyltin (TBT) and its degradation products dibutyltin (DBT) and monobutyltin (MBT) were measured in surface sediments and in two cores from the Toulon Bay, hosting the major French military harbour. Anticipating planned dredging, the aim of the present work is to map and evaluate for the first time the recent and historic contamination of these sediments by inorganic and organic Sn species derived from antifouling paints used for various naval domains including military, trade, tourism and leisure. Tin and butyl-Sn concentrations in the bay varied strongly (4 orders of magnitude), depending on the site, showing maximum values near the shipyards. The concentrations of total Sn (1.3–112 μg g^?1), TBT (<0.5–2,700 ng g^?1), DBT (<0.5–1,800 ng g^?1) and MBT (0.5–1,000 ng g^?1) generally decreased towards the open sea, i.e. as a function of both distance from the presumed main source and bottom currents. Progressive degradation state of the butyl-Sn species according to the same spatial scheme and the enrichment factors support the scenario of a strongly polluted bay with exportation of polluted sediment to the open Mediterranean. Low degradation and the historical records of butyl-Sn species in two ²¹⁰Pb-dated sediment cores, representative of the Northern Bay, are consistent with the relatively recent use of TBT by military shipyards and confirm maximum pollution during the 1970s, which will persist in the anoxic sediments for several centuries. The results show that (a) degradation kinetics of butyl-Sn species depend on environmental conditions, (b) the final degradation product Sn_inorgBT is by far the dominant species after 10–12 half-life periods and (c) using recent data to reliably assess former TBT contamination requires the use of a modified butyl-Sn degradation index BDI_mod. Resuspension of extremely contaminated subsurface sediments by the scheduled dredging will probably result in mobilization of important amounts of butyl-Sn species.     

PAH-sequestration capacity of granular and powder activated carbon amendments in soil, and their effects on earthworms and plants

A field lysimeter study was carried out to investigate whether the amendment of 2% powder and granular activated carbon (PAC and GAC) to a soil with moderate PAH contamination had an impact on the PAH bioaccumulation of earthworms and plants, since AC is known to be a strong sorbent for organic pollutants. Furthermore, secondary effects of AC on plants and earthworms were studied through growth and nutrient uptake, and survival and weight gain. Additionally, the effect of AC amendments on soil characteristics like pH, water holding capacity, and the water retention curve of the soil were investigated. Results show that the amendment of 2% PAC had a negative effect on plant growth while the GAC increased the growth rate of plants. PAC was toxic to earthworms, demonstrated by a significant weight loss, while the results for GAC were less clear due to ambiguous results of a field and a parallel laboratory study. Both kinds of AC significantly reduced biota to soil accumulation factors (BSAFs) of PAHs in earthworms and plants. The GAC reduced the BSAFs of earthworms by an average of 47 ± 44% and the PAC amendment reduced them by 72 ± 19%. For the investigated plants the BSAFs were reduced by 46 ± 36% and 53 ± 22% by the GAC and PAC, respectively.     

Toxicokinetics,toxicity and lethal body residues of two chlorophenols in the oligochaete worm,Lumbriculus variegatus,in different sediments

Bioavailability, toxicokinetics and toxicity (LC(50)) of water- and sediment-associated 2,4,5-trichlorophenol (2,4,5-TCP) and pentachlorophenol (PCP) were measured in Lumbriculus variegatus Müller in a set of experiments. The critical body residue approach was applied by measuring also the lethal body residues (LBR(50)). Freshwater and three different sediments with various sediment organic carbon (SOC) concentrations were used as exposure media. SOC decreased the bioavailability of both chlorophenols, and the uptake rates decreased by 81% and 91% for 2,4,5-TCP and PCP, respectively, in the sediment with a SOC of 6.9% compared to those in sediment with a SOC of 0.5%. SOC appeared to be an important factor controlling the bioavailability as after the carbon normalisation the difference between the sediments was much smaller. The 96-h LC(50) values for instance for PCP were 145.3 microg/l in freshwater, and 6.8 and 8.1 microg/g dry weight in sediments with SOC concentrations of 0.5% and 2.4%, respectively. The LBR(50) values, were practically the same in freshwater and sediments: between 1.0 and 1.6 and from 0.4 to 0.9 micromol/g wet weight for 2,4,5-TCP and PCP, respectively, demonstrating the usefulness of this method for accurate, and more comparable, measurement of toxicity of chemicals with the same mode of toxic action in varying conditions. L. variegatus expressed a dose-response sediment avoidance behaviour but the PCP tissue concentrations were not affected by this behaviour.     

Resilience and vulnerability of northern regions to social and environmental change

The arctic tundra and boreal forest were once considered the last frontiers on earth because of their vast expanses remote from agricultural land-use change and industrial development. These regions are now, however, experiencing environmental and social changes that are as rapid as those occurring anywhere on earth. This paper summarizes the role of northern regions in the global system and provides a blueprint for assessing the factors that govern their sensitivity to social and environmental change.     

Removal of chromate ions from leachate-contaminated groundwater samples of Khan Chandpur,India, using chitin modified iron-enriched hydroxyapatite nanocomposite

Environmental Science and Pollution Research - Chromite ore processing residues (COPR) are real environmental threats, leading to CrO42-, i.e., Cr (VI) leaching into groundwater. It is of serious...     

A computationally feasible quantum chemical model for 13C NMR chemical shifts of PCB-derived carboxylic acids

Two quantum chemical models have been derived for the prediction of 13C NMR chemical shifts of novel PCB acids obtained from PCBs by catalytic carbonylation. 13C isotropic shielding constants were calculated employing the GIAO (gauge-independent atomic orbital) method with density functional theory (DFT). The best results were obtained by cluster calculations, which took the solvent effects into account properly. In this approach, a solvent molecule (acetone) was attached by a hydrogen bond to every hydrogen atom present in a PCB acid, and the geometry of the molecular cluster was optimized employing the AM1 method. For 158 chemical shifts, the cross-validated standard error was 2.8 ppm and the cross-validated correlation coefficient was 0.94.     

Recent trends of biocides in pikes of the Lake Päijänne

Pikes were sampled in May 1980 from three areas of the Lake Päijänne, Finland and analyzed for their contents of total mercury, methyl mercury, hexachlorobenzene (HCB), DDE, PCB and chlorophenolic residues. An improved method for methyl mercury determination was applied and 82–84 % methylation of mercury in pikes regardless of area or biological variation was observed. Statistical analysis with previous results from the same areas gave a very significant decreasing trend of mercury levels at all three areas from 1970 to 1980. Future levels of mercury in fish to be consumed as food could be estimated from the trend regression. The very low levels of DDE and PCB showed some increasing trend when the influence of fat contents was eliminated by covariance analysis. General appearance of HCB at sub-ppb level was observed. Also pentachlorophenol occured at 10–70 ppb (fresh weight) levels at all areas, but the other chlorophenols were abundant only at Tiirinselkä which is most contaminated by pulp bleaching effluents.     

From critical levels to critical loads for ozone: a discussion of a new experimental and modelling approach for establishing flux-response relationships for agricultural crops and native plant species

Present critical levels for ozone (O3) for protecting vegetation against adverse effects are based on exposure-response relationships mainly derived from open-top chamber experiments and are expressed as an Accumulated exposure Over a Threshold of 40 ppb (AOT40). In that context with a revision of the UN (United Nations)-ECE (Economic Commission for Europe) Gothenburg protocol, AOT40 values should be replaced by flux-oriented quantities, i.e. in the end by critical loads. At present, the database for the derivation of critical loads for O3 is extremely inadequate. Furthermore, the currently available flux-response relationships are also derived from open-top chamber experiments. The use of a relationship for spring wheat in a risk assessment for an agricultural site in Hesse, Germany, demonstrates in principle, the applicability of the critical load concept for O3. Comparisons of diurnal variation of stomatal uptake and AOT40 showed that a major part of toxicologically effective stomatal uptake occurred before noon whereas the AOT40 values were dominated by the O3 concentrations during afternoon. In other words, the AOT40 exposure index do not adequately address the O3 burden during hours when plants are sensitive to O3 uptake. However, due to the differences in radiation, air temperature and humidity between the chamber and the ambient microclimates, a derivation of flux-response relationships from chamber experiments is likely to be questionable, especially for species rich ecosystems: Here, without any changes in the pollution climate, significant modifications of species composition as well as an earlier beginning of the growing season has been previously observed. To overcome the problems associated with chamber-derived flux-response relationships, a new experimental and modelling concept, was developed. The approach, briefly described in this paper, combines methods in air pollution toxicology and micrometeorology. As an analogy to the free-air fumigation concept, O3 is released into the air by an injection system above the plant canopy. The assessment of dispersion and surface deposition of O3 released is based on Lagrangian trajectory modelling. Depending on wind direction and velocity, atmospheric stratification and surface roughness, without any disturbance of the microclimate and micrometeorology, several sub-areas can be identified around the source position with differing deposition rates above the ambient level. Taking into account the actual O3 background deposition, deposition rates and vegetation responses observed in these sub-areas can easily be used to derive flux-effect relationships under ambient conditions and more realistic limiting values to protect our environment.     

A simple procedure for correcting loading effects of aethalometer data

A simple method for correcting for the loading effects of aethalometer data is presented. The formula BC(CORRECTED) = (1 + k x ATN) x BC(NONCORRECTED), where ATN is the attenuation and BC is black carbon, was used for correcting aethalometer data obtained from measurements at three different sites: a subway station in Helsinki, an urban background measurement station in Helsinki, and a rural station in Hyyti?l? in central Finland. The BC data were compared with simultaneously measured aerosol volume concentrations (V). After the correction algorithm, the BC-to-V ratio remained relatively stable between consequent filter spots, which can be regarded as indirect evidence that the correction algorithm works. The k value calculated from the outdoor sites had a clear seasonal cycle that could be explained by darker aerosol in winter than in summer. When the contribution of BC to the total aerosol volume was high, the k factor was high and vice versa. In winter, the k values at all wavelengths were very close to that obtained from the subway station data. In summer, the k value was wavelength dependent and often negative. When the k value is negative, the noncorrected BC concentrations overestimated the true concentrations.     

Phytotoxicity of low-weight carboxylic acids

Presence of low-weight carboxylic acids (LWCAs) can be the reason for phytotoxicity of green manures, treated bio-waste or digestates from biogas production applied to soils. As the phytotoxic concentrations of LWCA are poorly known, this work presents data on six acids (C(1)C(6): formic, acetic, propionic, butyric, valeric, and caproic). Phytotoxicity was measured in acute (72 or 120 h) and subchronic (21 d) assays for seed germination, seedling elongation, and plant growth for garden cress Lepidium sativum and ryegrass Lolium multiflorum. The dose-response relationship was modeled using Weibull model. Results showed a trend that toxicity of LWCA increases with the length of the carbon chain, formic acid (C(1)) being the least and caproic acid (C(6)) the most toxic. EC50 values in the acute seed germination of cress ranged between 1.9 and 4.2mM and for ryegrass between 1.8 and 6.4mM. In subchronic assays EC50 values for germination were in a range from 11 to 46mMkg(-1)dm for cress, and from 18 to 127 mM kg(-1) dm for ryegrass. EC50 values for early seedling growth of cress based on acute assays ranged from 0.7 to 2.3mM and that of ryegrass from 1.2 to 1.8mM. Range of EC50 values for shoot biomass of cress was between 8 and 40 mM kg(-1) dm and of ryegrass between 12 and 93 mM kg(-1) dm.