Correlates of mercury in fish from lakes near Clyde Forks, Ontario, Canada

Subsurface soils near Clyde Forks, Ontario, Canada, can have naturally high concentrations of mercury (Hg) from local geological sources. To investigate Hg in local aquatic food webs, Hg was measured in fish dorsal muscle (mainly yellow perch [YP] and pumpkinseed sunfish [PS]) and surface sediments from 10 regional lakes. Water chemistry, along with fork length, weight, and stable isotopes (delta15N, delta13C, delta34S) in fish were also measured. No lake sediments had elevated (>0.3microg/g dw) Hg, and average Hg concentrations in fish were not sufficiently high (<1microg/g dw) to be of concern for fish-eating wildlife. Variance in fish Hg was best explained by dietary carbon source (delta13C), and certain lake variables (e.g., pH for YP). PS with more pelagic feeding habits had higher delta34S and Hg than those with more littoral feeding habits. Potential biological linkages between fish Hg and delta34S, a parameter that may be related to the lake sulphate-reducing bacteria activity, requires further investigation.     

Neurotoxic effect and metabolic responses induced by a mixture of six pesticides on the earthworm Aporrectodea caliginosa nocturna

The effects of a mixture of insecticides and/or fungicides at different environmental concentrations were investigated on a Aporrectodea caliginosa nocturna population. This laboratory experiment was carried out in order to reproduce Gaillac (France) vineyard conditions. Neurotoxicity (cholinesterase), metabolisation (glutathione-S-transferase) and oxidative stress (catalase) enzymes were studied as biomarkers in earthworms after short-term exposure in terraria. The aim was to observe the global effects of pesticide exposure, as in a vineyard, rather than focus on each isolated biomarker variation, or on each compound's impact. ChE activity was inhibited after a few days of insecticide and/or fungicide exposure, indicative of a neurotoxic effect in earthworms. The significant increase in GST and CAT activities revealed the metabolisation of these products resulting in the production of reactive oxygen species. After a long period of exposure or high concentrations, earthworms were physiologically damaged: they could not cope with the high toxicity (cellular dysfunction, protein catabolism...). Chemical analysis showed that pesticide bioaccumulation in earthworm tissues, even in those exposed to the highest concentrations and for the longest periods, was very low (under LOD) or absent. However, the study of pesticide residues in terraria after 34 days in a climate chamber suggested that earthworms participate in soil pesticide breakdown.     

Humic substances

GOAL, SCOPE AND BACKGROUND: Freshwater bodies which chemistry is dominated by dissolved humic substances (HS) seem to be the major type on Earth, due to huge non-calcareous geological formations in the Northern Hemisphere and in the tropics. Based on the paradigm of the inertness of being organic, direct interactions of dissolved HS with freshwater organisms are mostly neglected. However, dissolved organic carbon, the majority of which being HS, are natural environmental chemicals and should therefore directly interact with organisms. Major results that widened our perspective on humic substance ecology come from experiments with the compost nematode, Caenorhabditis elegans, which behaved contradictorily to textbook knowledge and provoked an in-depth re-consideration of some paradigms. APPROACH: To overcome old paradigms on HS and their potential interactions with organisms, we reviewed recent international literature, as well as 'grey' literature. We also include results from own ongoing studies. RESULTS: This review focuses on direct interactions of dissolved HS with freshwater organisms and disregards indirect effects, such as under-water light quenching. Instead we show with some macrophyte and algal species that HS adversely interfere with photosynthesis and growth, whereby closely related algal species show different response patterns. In addition to this, HS suppress cyanobacteria more than eukaryotic algae. Quinones in the HS appear to be the effective structure. Furthermore, HS can modulate the offspring numbers in the nematode C. elegans and cause feminization of fish and amphibians--they possess hormone-like properties. The ecological consequences of this potential remain obscure at present. HS also have the potential to act as chemical attractants as shown with C. elegans and exert a mild chemical stress upon aquatic organisms in many ways: induction of molecular chaperons (stress proteins), induction and modulation of biotransformation and anti-oxidant enzymes. Furthermore, they produce an oxidative stress with lipidperoxidation as one clear symptom or even stress defense strategy. Stronger chemical stresses by HS may even lead to teratogenic effects as shown with fish embryos; all physiological responses to HS-mediated stress require energy, which were compensated on the expense of yolk as shown with zebra fish embryos. One Finnish field survey supports the view of a strong chemical stress, as the weight yield in fish species decreases with increasing HS content in the lakes. DISCUSSION: HS exert a variety of stress symptoms in aquatic and compost organisms. According to current paradigms of ecotoxicology, these symptoms have to be considered adverse, because their compensation consumes energy which is deducted from the main metabolism. However, the nematode C. elegans looks actively for such stressful environments, and this behavior is only understandable in the light of new paradigms of aging mechanisms, particularly the Green Theory of Aging. In this respect, we discuss the mild HS-mediated stress to aquatic and compost organisms. New empirical findings with HS themselves and HS building blocks appear to be consistent with this emerging paradigm and show that the individual lifespan may be expanded. At present the ecological consequences of these findings remain obscure. However, a multiple-stress resistance may be acquired which improves the individual fitness in a fluctuating environment. CONCLUSIONS: It appears that dissolved HS have to be considered abiotic ecological driving forces, somewhat less obvious than temperature, nutrients, or light. PERSPECTIVES: The understanding of the ecological control by dissolved humic substances is still fragmentary and needs to be studied in more details.     

An enzyme-linked immunosorbent assay for the determination of dioxins in contaminated sediment and soil samples

A 96-microwell enzyme-linked immunosorbent assay (ELISA) method was evaluated to determine PCDDs/PCDFs in sediment and soil samples from an EPA Superfund site. Samples were prepared and analyzed by both the ELISA and a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. Comparable method precision, accuracy, and detection level (8 ng kg(-1)) were achieved by the ELISA method with respect to GC/HRMS. However, the extraction and cleanup method developed for the ELISA requires refinement for the soil type that yielded a waxy residue after sample processing. Four types of statistical analyses (Pearson correlation coefficient, paired t-test, nonparametric tests, and McNemar's test of association) were performed to determine whether the two methods produced statistically different results. The log-transformed ELISA-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin values and log-transformed GC/HRMS-derived TEQ values were significantly correlated (r=0.79) at the 0.05 level. The median difference in values between ELISA and GC/HRMS was not significant at the 0.05 level. Low false negative and false positive rates (<10%) were observed for the ELISA when compared to the GC/HRMS at 1,000 ng TEQ kg(-1). The findings suggest that immunochemical technology could be a complementary monitoring tool for determining concentrations at the 1,000 ng TEQ kg(-1) action level for contaminated sediment and soil. The ELISA could also be used in an analytical triage approach to screen and rank samples prior to instrumental analysis.     

Changes in sewage sludge carbon forms along a treatment stream

The behaviour and fate of macronutrients and pollutants in sewage sludge applied to the land are affected by the chemical composition of the sludge organic matter, which in turn is influenced by both sewage source and by sewage treatment processes. In this study, (13)C nuclear magnetic resonance (NMR) spectroscopy was used to characterise the organic matter of sludges collected at three different points along the treatment stream of a municipal sewage works with a domestic catchment. Sludge at the first point, an undigested liquid (UL) sludge, had a substantially different composition to the anaerobically digested (AD) and dewatered sludge cake (DC) materials, which were similar to each other. In particular, the UL sludge contained more alkyl C than the AD or DC sludges. All three sludges were found to contain mobile alkyl C that is poorly observed using the cross polarisation (CP) technique, necessitating the use of the less sensitive, but more quantitatively reliable direct polarisation (DP) technique to obtain accurate distributions of C types.     

Empirical and simulated critical loads for nitrogen deposition in California mixed conifer forests

Empirical critical loads (CL) for N deposition were determined from changes in epiphytic lichen communities, elevated NO(3)(-) leaching in streamwater, and reduced fine root biomass in ponderosa pine (Pinus ponderosa Dougl. ex Laws.) at sites with varying N deposition. The CL for lichen community impacts of 3.1kg ha(-1) year(-1) is expected to protect all components of the forest ecosystem from the adverse effects of N deposition. Much of the western Sierra Nevada is above the lichen-based CL, showing significant changes in lichen indicator groups. The empirical N deposition threshold and that simulated by the DayCent model for enhanced NO(3)(-)leaching were 17kg N ha(-1) year(-1). DayCent estimated that elevated NO(3)(-) leaching in the San Bernardino Mountains began in the late 1950s. Critical values for litter C:N (34.1), ponderosa pine foliar N (1.1%), and N concentrations (1.0%) in the lichen Letharia vulpina ((L.) Hue) are indicative of CL exceedance.     

Influence of Na2S on the degradation kinetics of CCl4 in the presence of very pure iron

This paper presents the results of kinetic studies to investigate the effect of FeS film formation on the degradation rate of CCl(4) by 99.99% pure metallic iron. The film was formed by submersing metallic iron grains in an oxygen free HCO(3)(-)/CO(3)(2-) electrolyte solution. When the grains had reached a quasi steady-state value of the corrosion potential, Na(2)S((aq)) was injected. Upon injection, a microm thick poorly crystalline FeS film formed immediately on the iron surface. Over time, the iron became strongly corroded and both the FeS film and the metallic iron grains began to crack leading to exposure of bare metallic iron to the solution. The effect of the surface film on the degradation rate of CCl(4) was investigated following four periods of aging, 1, 10, 30, and 60 days. Relative to the controls, the 1-day sulfide-aged iron showed a substantial decrease in rate of degradation of CCl(4.) However, over time, the rate of degradation increased and surpassed the degradation rate obtained in the controls. It has been proposed that CCl(4) is reduced to HCCl(3) by metallic iron by electron transfer. The FeS film is substantially less conducting than the bulk iron metal or non-stoichiometric magnetite and from the results of this study, greatly decreases the rate of CCl(4) degradation relative to iron that has not been exposed to Na(2)S. However, continued aging of the FeS film results in breakdown and stress-induced cracking of the film, followed by dissolution and cracking of the iron itself. The cracking of the bulk iron is believed to be a consequence of hydrogen embrittlement, which is promoted by sulfide. The increase in CCl(4) degradation rate, as the FeS films age, suggests that the process of hydrogen cracking increases the surface area available for charge transfer.     

The effect of nitroaromatics' composition on their toxicity in vivo: novel, efficient non-additive 1D QSAR analysis

Novel 1D QSAR approach that allows analysis of non-additive effects of molecular fragments on toxicity has been proposed. Twenty-eight nitroaromatic compounds including some well-known explosives have been chosen for this study. The 50% lethal dose concentration for rats (LD50) was used as the estimation of toxicity in vivo to develop 1D QSAR models on the framework of Simplex representation of molecular structure. The results of 1D QSAR analysis show that even the information about the composition of molecules provides the main trends of toxicity changes. The necessity of consideration of substituents' mutual impacts for the development of adequate QSAR models of nitroaromatics' toxicity was demonstrated. Statistic characteristics for all the developed partial least squares QSAR models, except the additive ones are quite satisfactory (R2=0.81-0.92; Q2=0.64-0.83; R2 test=0.84-0.87). A successful performance of such models is due to their non-additivity i.e. possibility of taking into account the mutual influence of substituents in benzene ring which plays the governing role for toxicity change and could be mediated through the different C-H fragments of the ring. The correspondence between observed and predicted by these models toxicity values is good. This allowing combine advantages of such approaches and develop adequate consensus model that can be used as a toxicity virtual screening tool.     

The changing sediment load of the Mekong River

The sediment loads of many of the world's major rivers have changed significantly in recent years due to land-use change, reservoir construction, and other human impacts on their drainage basins. For many rivers, the loads have decreased, whereas for others, they have increased. Such changes can have important implications for both the natural functioning of the system as well as for human exploitation of the river system. This paper considers the evidence for recent changes in the sediment load of the Mekong River. The available data have a number of limitations in terms of both sampling frequency and the period of coverage, but they have been processed to provide a basis for considering the changes in the sediment load of the river over the period extending from the early 1960s to 2002. Although there is evidence of increasing loads at some measuring stations, the overall trends show little evidence of major changes, and the system provides evidence of buffering through storage. As of 2002, the construction of major dams on the headwaters in China appears to have had little impact on the sediment load, although as further larger dams are commissioned, the sediment load of the Mekong can be expected to decrease.     

Assessment of chemical, biochemical and ecotoxicological aspects in a mine soil amended with sludge of either urban or industrial origin

A greenhouse pot experiment was conducted to evaluate the effect of sewage sludge (SS), of sugar beet sludge (SBS), or of a combination of both, in the remediation of a highly acidic (pH 3.6) metal-contaminated soil, affected by mining activities. The SS was applied at 100 and 200 Mg ha(-1) (dry weight basis), and the SBS at 7 Mg ha(-1). All pots were sown with Italian ryegrass (Lolium multiflorum Lam.). After 60 d of growth, shoot biomass was quantified and analysed for Cu, Pb and Zn. The pseudo-total and bioavailable contents of Cu, Pb and Zn and the enzymatic activities of beta-glucosidase, acid phosphatase, cellulase, protease and urease were determined in the soil mixtures. Two indirect acute bioassays with leachates from the soil (luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) were also used. The SS, in particular when in combination with SBS, corrected soil acidity, while increasing the total organic matter content and the cation exchange capacity. The application of SS led to a decrease in the level of effective bioavailable metals (extracted by 0.01 M CaCl(2), pH 5.7, without buffer), but caused an increase in their potential bioavailability (extracted by a solution of 0.5M NH(4)CH(3)COO, 0.5 M CH(3)COOH and 0.01 M EDTA, pH 4.7). Plant biomass increased more than 10 times in the presence of 100 Mg SS ha(-1), and more than five times with the combined use of 100 Mg SS ha(-1) and SBS, but a considerable phytotoxic effect was observed for the application rate of 200 Mg SS ha(-1). Copper, Pb and Zn concentrations in the shoots of L. multiflorum decreased significantly when using 100 Mg SS ha(-1) or SBS. The activities of beta-glucosidase, urease and protease increased with increasing SS applications rates, but cellulase had a reduced activity when using 200 Mg ha(-1)SS. Both amendments were able to suppress soil toxicity to levels that did not affect D. magna, but increased the soil leachate toxicity towards V. fischeri, especially with the application of 200 Mg SS ha(-1). This study showed that for this type of mine soils, and when using SS of similar composition, the maximum SS application rate should be 100 Mg ha(-1), and that liming the SS amended soil with SBS did not contribute to a further improvement in soil quality.