Biological evidence for a 1:1 Ca2+:glyphosate association in deposit residuals on the leaf surface of barley

It has long been known that calcium ion antagonizes glyphosate, but it was not clear whether the stoichiometry of their interaction is 1:1 or 1:2. Two independent methods were used to determine which stoichiometry was the most probable. First, dose–response curves of barley ( Hordeum vulgare L.) plants treated with glyphosate were determined in the presence of 0, 1.25, 2.5, 5 and 10 mM CaCl₂. The doses of 'free' glyphosate (=not inactivated by calcium ion) were computed using the assumptions of 1:1 and 1:2 stoechiometries. The response curves were redrawn as a function of 'free' glyphosate. Analysis showed that the 1:2 hypothesis could be rejected, whereas the 1:1 hypothesis was highly probable. Second, kinetics of glyphosate penetration into barley leaves were determined in the presence of 0, 2.5 and 10 mM CaCl₂. The concentrations of 'free' glyphosate were computed as above. The kinetics of glyphosate penetration at these concentrations were established and were compared to the kinetics of glyphosate penetration in the presence of CaCl₂. Again, the 1:2 hypothesis was rejected, whereas the 1:1 hypothesis was more probable. These results strongly suggest that the stoichiometry of the Ca²⁺:glyphosate association is 1:1 in deposit residuals on the leaf surface.     

Geochemistry of mercury in pristine and flooded ferralitic soils of a tropical rain forest in French Guiana,South America

In ferralitic soils of the dense Guianese forest, mercury (Hg) concentrations of the surface horizons varied from 122 to 318 ng/g d.w. The behaviour and accumulation of Hg is not related to the accumulation of organic matter but to the penetration of humic substances and the progressive adsorption onto iron (Fe) oxy-hydroxydes in the mineral horizons. The flooding of such soils with the creation of a small reservoir has lead to a release of 20% of the Hg initially present. This observation is related to the reduction of the Fe oxy-hydroxydes and to the migration of the organo-metallic complexes to the water column. Although physico-chemical conditions are appropriate for bacterial methylation, methyl Hg (MeHg) levels of these soils are very low. The process regulating MeHg production and its possible loss from the soil are unknown.     

Mercury Concentrations in Lake Sediments – Revisiting the Predictive Power of Catchment Morphometry and Organic Matter Composition

Lake sediments are a potential source of mercury (Hg) for aquatic biota. Here, we investigated the predictive power of (a) key parameters for lake catchment morphometry and (b) organic matter composition of sediments in an effort to account for observed variations of total (THg) and methyl (MeHg) mercury concentrations in lake sediments. Using regression models we demonstrate that the morphometric parameters lake depth as well as inclination of catchment soils and lake bottoms can significantly predict variations of THg concentrations, but not MeHg, at profundal lake sediments. Although THg and MeHg concentrations in sediments could not be predicted by specific organic matter sources, as elucidated by atomic C/N ratios, our data suggest that wetland-derived total organic carbon (TOC) contained less THg concentrations than TOC derived from mostly forested watersheds. However, TOC concentrations could significantly predict MeHg concentrations and the proportion of methylated Hg at all sediment stations. Finally, from an ecotoxicological point of view, we propose that concentrations of TOC at surface lake sediments, rather than parameters of catchment morphometry, may predict dietary sources of MeHg for benthic consumers and consequently perhaps for organisms at higher trophic levels.     

Methylmercury in a benthic food web of two hydroelectric reservoirs and a natural lake of Northern Québec (Canada)

Total mercury (Hg) concentrations in benthic insects from a 14 years old hydroelectric reservoir (La Grande 2) were 2 to 3 times higher than those from a reference lake and, in some groups, up to 7 times. The difference was even more pronounced for methylmercury (MeHg) concentrations, with a mean of 4 fold and a maximum of 12 fold between systems. The enrichment factors (dw) of insects, relative to the substrate in which they reside was around 3 for total Hg and 6 to 22 for MeHg. On the basis of their diet, we have classified the insects into four different trophic levels: detritivores, grazers, grazers-predators and predators. In insects collected in the reservoirs, the McHg:Hg ratio was 20–25% in dipterans-ephemeropterans (detritivores) and 30–40% in trichopterans (grazers), but 60–85% in heteropterans-coleopterans (grazers-predators) and 95% in odonates (predators). The pattern was similar in the lake with slightly lower values. In both systems, the proportion of MeHg increases in direct relation to our defined trophic levels. Given that insects are an important food source for many fish, our results suggest that they are a strong vector of McHg to these fish in hydroelectric reservoirs. The bioavailability of MeHg to insect larvae appears to depend on the nature and composition of the substrate in which they reside.     

Effects of Recent Human Colonization on the Presence of Mercury in Amazonian Ecosystems

Three Hg sources were characterised and mass balance calculations were used to determine their relative contributions to the contamination of the Amazonian environment. About an order of magnitude more Hg is emitted to the atmosphere by goldmining activity than by the burning of forest biomass. However, anthropogenic atmospheric Hg cannot account for the high Hg burdens found in terrestrial ecosystems: deposition of Hg from goldmining sources is estimated to account for less than 3% of the Hg present in the surface horizons of soils. We propose that erosion of deforested soils following human colonization constitutes a major disturbance of the natural Hg cycle. Deforestation thus increases soil Hg mobilisation by runoff, which may explain the increase of Hg burdens in Amazonian aquatic ecosystems in newly colonized watersheds.     

Trophic Structure and Bioaccumulation of Mercury in Fish of Three Natural Lakes of the Brazilian Amazon

The bioaccumulation of mercury by fish was studied in three natural lakes lining the Tapajós River, Brazilian Amazon. The Hg content variations are also reported between the rainy and the rising water seasons. Position of fish in the food chain and the source of carbon at the base of the food chain were determined using nitrogen and carbon stable isotopes ratios respectively. During the two seasons, the effect of the Hg biomagnification between the non-piscivorous and piscivorous fish of the three lakes is observed. The correlation between the mercury concentrations and the nitrogen isotopic ratios suggests that the fish mercury content variability is connected with the trophic position and size. Aside from classic observations on mercury biomagnification by certain species of fish (i.e. contents increase with size or trophic status), novel results were revealed as well, such as some species decrease of mercury contents with size of fish. Aquatic organisms in the Amazon are adapted to the complexity of trophic webs coupled with changes in environmental variables, depending on the location and/or the season, which results in a wide range of mercurial contamination among the Tapajós ichthyofauna.     

Different factors related to mercury concentration in sediments and zooplankton of 73 Canadian Lakes

Surficial sediments were sampled with a light-weight gravity corer at 175 sites in 73 Ontario and Québec lakes and Zooplankton was collected with a 225 μm mesh size net in 24 lakes. Hg concentrations in surficial sediments (0–2 cm) ranged from 3 to 267 ng g^?1 dry weight with a mean of 80 ng g^?1 dry weight for all sites. A regression model including organic content of sediments and the ratio of the catchment area/lake surface explained 60% of the variation in sediments Hg concentrations. Hg in Zooplankton ranged from about 25 to 377 ng g^?1 dw with a mean of 108 ng g^?1 dw and was weakly correlated with catchment area, primary productivity and TOC. Our data indicate that an important fraction of Hg originates from the catchments, but do not show a clear west-east regional gradient for Hg concentrations in surficial sediments or in zooplankton.     

Anthropogenic mercury enrichment in remote lakes of northern Québec (Canada)

In a sub-Arctic region of the province of Québec, at sites situated 200 to 1400 km away from the closest industrial centers, we find the ubiquitous presence of anthropogenic Hg, reflected by steadily increasing concentrations of this metal in lake sediments, since about 1940, to rates averaging 2.3 times the preindustrial levels. Mercury concentrations in lake sediments were found to be proportional to the amounts of terrestrial organic carbon from the catchment area. It would, therefore, be misleading to derive continental-scale gradients of this pollutant based on Hg concentrations in oligotrophic lake sediments, unless they are normalized to their organic carbon content. Our normalized data for sediments of remote lakes along a 1200 km transect (45 to 55°N) clearly indicate that the distribution pattern of long-range Hg contamination is independent of the latitude over the boreal forest domain. This uniform contamination contrasts with that of Pb, which decreases towards the north over the same latitudinal span, away from the industrial centers of the St Lawrence Valley and the U.S. Mid-West.     

Fish Diet and Mercury Exposure in a Riparian Amazonian Population

The incorporation of mercury into the food chain and its assimilation by humans is a universally recognized potential health hazard. Studies carried out in the Amazon Basin have shown that mercury (Hg) is present in fish and in humans, however, the relation between fish diet and human exposure has received limited attention in this region. The present study focused on a small village, Brasília Legal (3°59′00″S, 55°30′00″W), situated on the banks of the Rio Tapajós. A total of 181 fish (40 species) were captured in March, 1995 and analysed for Hg concentration. Of these, 132 fish were among species consumed by the population during the rainy season (mid-November to mid-May) and the dry season (mid-May to mid-November). Wide intra- and inter-species variations in Hg concentrations were observed. Thirty four fish (25.8% of the consumed species) had levels above 0.5 μg/g Hg fresh weight; all were among the piscivorous and omnivorous species. Hair Hg concentrations (HHg), showed that villagers with a high fish diet (n=31; median HHg=16.1 μg/g) and mixed fish diet (n=36; median HHg=14.8 μg/g) had significantly higher HHg concentrations compared to the low fish diet group (n=29; mean HHg=7.8 μg/g). Time series function of HHg measurements, made for 26 persons with over 24 cm of hair, revealed sinusoidal variations, with peaks during the rainy season and troughs during the low water period, paralleling the seasonal shift in dietary habits. Piscivorous and omnivorous fish species, with higher mercury levels, are the main component of the fish diet during the rainy season, while herbivorous fish species predominate during the dry season. Preventive actions should take into account the risk to human health, particularly for fetal and neonatal development, the importance of fish in the riparian diet, the wide intra- and inter-species variations in mercury content and seasonal fluctuations in diet.