Methylmercury and total mercury in estuarine organisms from Rio de Janeiro, Brazil

Guanabara Bay (GB), located in the Rio de Janeiro State, is still a productive estuary on the south-eastern Brazilian coast. It is an ecosystem heavily impacted by organic matter, oil and a number of other toxic compounds, including Hg. The present study aimed to comparatively evaluate the aquatic total mercury (THg) and MeHg contamination, and the ratios of MeHg to THg (% MeHg), in 3 species of marine organisms, Micropogonias furnieri-carnivorous fish (N = 81), Mugil spp.--detritivorous fish (N = 20) and Perna perna--filter-feeding bivalves (N = 190), which are widely consumed by the population. A total of 291 specimens were collected at the bay in different periods between 1988 and 1998. THg concentrations were determined by cold vapour AAS with stannous chloride as a reducing agent. MeHg was extracted by dithizone-benzene and measured by GC-ECD. Analytical quality was checked through certified standards. All organisms presented both low THg and MeHg concentrations and they were below the maximum limit of 1,000 micrograms Hg.kg-1 wet wt. as established for human intake of predatory fish by the new Brazilian legislation. Carnivorous fish showed higher THg and MeHg concentrations, and also % MeHg in muscle tissues, than organisms with other feeding habits and lower trophic levels. The average of THg concentrations in carnivorous fish was 108.9 +/- 58.6 micrograms.kg-1 wet wt. (N = 61) in 1990 and 199.5 +/- 116.2 micrograms.kg-1 wet wt. (N = 20) in 1998, but they presented different total length and body weights. The average THg content in detritivorous fish was 15.4 +/- 5.8 micrograms.kg-1 wet wt., whereas THg concentrations ranged from 4.1 to 53.5 micrograms.kg-1 wet wt. for the molluscs. The THg and MeHg contents of mussel varied according to the sampling point and water quality. MeHg concentration in detritivorous fish was similar to MeHg concentration in molluscs, but there was a significant difference in the MeHg/THg ratio: the carnivorous fish presented higher MeHg percentages (98%) than the detritivorous fish (54%) and the molluscs (33%). Weight-normalised average concentration of THg in carnivorous fish collected in 1990 (0.18 +/- 0.08 microgram.g-1/0.7 kg wet wt.) and in 1998 (0.16 +/- 0.09 microgram.g-1/0.7 kg wet wt.) presented no significant difference (t = 1.34; P < 0.5). In conclusion, the low THg and MeHg concentrations in the organisms from the GB ecosystem, are related to its eutrophic conditions and elevated amounts of suspended matter. In this situation, Hg could be strongly complexed or adsorbed by the particulate, which would dilute the Hg inputs and reduce its residence time in the water column, with a consequent decrease in its availability to organisms.     

Methods for the analysis of PCBs in human food, faeces and serum.

A method was developed to determine trace concentrations of a range of individual PCB congeners in biological samples (serum, food and faeces) using GC-MS, to prepare a mass balance of PCBs in humans. A simple method for the analysis of PCBs in human serum, which excluded an extraction step, was first employed. Results indicated that the recoveries of 13C12 PCB spikes were variable. A soxhlet extraction step was added and was found to be efficient and reproducible. A quality control routine and method validation results are presented. In batch tests of the methods presented it was found that the serum analysis method gave within batch mean 13C12 spike recoveries of 98-120% and standard deviations between 6 and 20%. The food/faeces analysis method gave within-batch mean 13C12 spike recoveries of 88-100%, and within batch standard deviations between 4 and 12%. The batch to batch mean recovery for serum analysis was 100%, with an RSD of 9% for high spikes and 10% for low spikes. For food/faeces analysis the batch to batch average recovery was 110%, with an RSD of 5% for high spikes and 9% for low spikes.     

A laboratory study of the mineralization and binding of 14C-labeled herbicide rimsulfuron in a rendzina soil.

The fate of pyrimidine-2-14C-rimsulfuron in a rendzina soil was investigated using a laboratory microcosm approach. Measurement of CO2 evolution suggested that rimsulfuron applied at 5 times the recommended dose did not affect soil respiration. Under abiotic conditions, no mineralization of 14C-rimsulfuron into 14C-CO2 occurred and under biotic ones it was very low reaching 0.75% of the applied 14C-rimsulfuron after 246 days of incubation. The analysis of data showed that a three-half order model provided the best fit for the mineralization curve. Extractable 14C-residues decreased over time to 70-80% of the applied 14C-rimsulfuron at the end of the incubation. After 246 days of incubation, non extractable residues (NER) accounted for up to 24.7% of the applied 14C-rimsulfuron and were distributed according to organic carbon in soil size fractions, suggesting a progressive incorporation process of NER to soil humus.     

Metallothionein induction and cadmium uptake in Bufo arenarum embryos following an acclimation protocol

Bufo arenarum embryos at the end of their embryonic development were acclimated to cadmium (Cd) by means of a 10-day treatment protocol. Embryos were processed for metallothionein (Mt) isolation and Cd and zinc (Zn) contents were measured. The results showed that: (1) the uptake of Cd in the experimental embryos was 7 microg/g embryo (wet weight) representing a bioaccumulation of Cd 255 times higher than in the maintaining medium; (2) a major Mt-like fraction was Cd-induced 7.8 times that in control embryos; two other protein fractions also bound Cd and Zn but were induced by Cd only about 2 and 1.4 times; (3) the Zn concentration was about 44 microg Zn/g embryo (wet weight) and did not change significantly (p>0.01) in the experimental embryos with respect to controls, but in acclimated embryos the essential metal was released from the Mts. The enhanced Mt synthesis and release of Zn from the native Mts are discussed in relation to the acclimation phenomenon.     

Air pollution and forest decline in Central Europe

The term 'Waldsterben' was introduced in the early 1980s to describe the progressive death of forests that was believed to be occurring in Central Europe as a result of air pollution. Subsequent surveys and investigations have failed to confirm that forests are dying or are even declining over large areas of Central Europe, defined here as consisting of Germany, Switzerland, southeastern France (Alsace), the Czech Republic, northern Italy and Austria. Foliar injury by air pollutants, together with mortality, has occurred, but is generally restricted to specific locations in the Czech Republic and in eastern Germany, such as the Fichtelgebirge. Where foliar damage has been recorded, it can often be attributed to high concentrations of sulphur dioxide, often acting in combination with other stresses (e.g. frost or insects). Outside areas affected by local sources of pollution, there is little, if any, evidence that the crown condition of trees has been adversely affected by pollution over large areas. Instead, climate appears to have a major effect on the crown condition and growth of trees. Measurements and surveys have revealed a very different picture to that forecasted in the mid-1980s. Growth rates of trees and stands in Central Europe are currently higher than have been recorded at any time in the past; the reasons for this are uncertain, although increases in forest area have not substantially contributed to the observed trends. Although declines in individual species in specific areas have been recorded, past records indicate that these do not represent a new phenomenon. Consequently, the terms 'Waldsterben' (forest deaths) and 'neuartige Waldsch?den' (novel type of forest damages) should not be used in the context of the phenomenon reported in Central Europe in the 1980s. Instead, different problems should be described separately and the term forest decline used only when there is clear evidence of a general deterioration in the condition of all tree species within a forest.     

Chemical composition and ecophysiological responses of Empetrum nigrum to aboveground element application

Empetrum nigrum L. (crowberry) is one of the plants surviving near the Cu-Ni smelters in Finland and Russia. According to field observations, the fine roots of E. nigrum are situated below 40 cm depth and the root biomass is reduced in the polluted sites. This could cause a reduced root uptake of macronutrients and trace elements in the field and, therefore, the possible element uptake by aboveground parts of E. nigrum was studied in a greenhouse. Six different treatment solutions containing various heavy metal and macronutrient concentrations were applied to the stems and leaves of E. nigrum and the chemical composition and ecophysiological parameters were measured. Heavy metal concentrations in the leaves and stem bark, and Cu concentrations in the stems, increased with increasing metal concentrations in the spraying solutions. The bark and leaves had higher heavy metal concentrations than the stems of comparable age classes. The macronutrient and Mn concentrations in E. nigrum did not change significantly with increasing element concentrations in the spraying solution. Neither the stem water potential nor the leaf chlorophyll concentrations showed any clear response to element applications. Therefore, the element uptake by aboveground parts of E. nigrum was not confirmed by this study. However, there was a tendency to a decrease in CO2 exchange rate and increase in foliar abscisic acid content in plants treated with the highest element concentrations.     

Geochemical characterization of acid mine drainage from a waste rock pile, Mine Doyon, Québec, Canada

Water quality in the unsaturated and saturated zones of a waste rock pile containing sulphides was investigated. The main objectives of the project were (1) the evaluation of geochemical trends including the acid mine drainage (AMD)-buffering mechanism and the role of secondary minerals, and (2) the investigation of the use of stable isotopes for the interpretation of physical and geochemical processes in waste rock. Pore water in unsaturated zone was sampled from suction lysimeters and with piezometers in underlying saturated rocks. The investigation revealed strong temporal (dry period vs. recharge period), and spatial (slope vs. central region of pile) variability in the formation of acid mine drainage. The main secondary minerals observed were gypsum and jarosite. There was a higher concentration of gypsum in solid phase at Site TBT than at Site 6, suggesting that part of the gypsum formed at Site 6 in the early stage of AMD has been already dissolved. Formation of secondary minerals contributed to the formation of AMD by opening of foliation planes in waste rock, thus increasing the access of oxidants like O2 and Fe3+ to previously encapsulated pyrite. The behavior of several dissolved species such as Mg, Al, and Fe2+ can be considered as conservative in the leachate. Stable isotopes, deuterium and 18O, indicated internal evaporation within the pile, and were used to trace recharge pulses from snowmelt. Isotope trends for 34S and 18O(SO4) indicated a lack of sulfate reduction and zones of active oxidation of pyrite, respectively. Results of numerical modeling of pyrite oxidation and gas and water transport were consistent with geochemical and isotopic trends and confirmed zones of high evaporation rate within the rock pile close to the slope. The results indicate that physical and chemical processes within the pile are strongly coupled and cannot be considered separately when oxidation rates are high and influence gas transport as a result of heat generation.     

Effects of heavy metals on growth and arsenic accumulation in the arsenic hyperaccumulator Pteris vittata L

The effects of Cd, Ni, Pb, and Zn on arsenic accumulation by the arsenic hyperaccumulator Pteris vittata were investigated in a greenhouse study. P. vittata was grown for 8 weeks in an arsenic-contaminated soil (131 mg As kg(-1)), which was spiked with 50 or 200 mg kg(-1) Cd, Ni, Pb, or Zn (as nitrates). P. vittata was effective in taking up arsenic (up to 4100 mg kg(-1)) and transporting it to the fronds, but little of the metals. Arsenic bioconcentration factors ranged from 14 to 36 and transfer factors ranged from 16 to 56 in the presence of the metals, both of which were reduced with increasing metal concentration. Fern biomass increased as much as 12 times compared to the original dry weight after 8 weeks of growth (up to 19 g per plant). Greater concentrations of Cd, Ni, and Pb resulted in greater catalase activity in the plant. Most of the arsenic in the plant was present as arsenite, the reduced form, indicating little impact of the metals on plant arsenic reduction. This research demonstrates the capability of P. vittata in hyperaccumulating arsenic from soils in the presence of heavy metals.