Radiocarbon content of synthetic and natural semi-volatile halogenated organic compounds

Some halogenated organic compounds, such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polybrominated diphenyl ethers (PBDEs), have been suggested to have natural sources but separating these compounds from their commercially synthesized counterparts is difficult. Molecular-level 14C analysis may be beneficial since most synthetic compounds are manufactured from petrochemicals (14C-free) and natural compounds should have "modern" or "contemporary" 14C levels. As a baseline study, we measured, for the first time, the 14C abundance in commercial PCB and PBDE mixtures, a number of organochlorine pesticides, as well as one natural product 2-(3',5'-dibromo-2'-methoxyphenoxy)-3,5-dibromoanisole. The latter compound was isolated from a marine sponge and is similar in structure to a PBDE. All of the synthetic compounds were 14C-free except for the pesticide toxaphene. which had a modern 14C abundance, as did the brominated natural compound. The result for toxaphene was not surprising since it was commercially synthesized by the chlorination of camphene derived from pine trees. These results suggest that measuring the 14C content of halogenated organic compounds may be quite useful in establishing whether organic compounds encountered in the environment have natural or synthetic origins (or both) provided that any synthetic counterparts derive from petrochemical feedstock.     

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.     

Genetic engineering in the improvement of plants for phytoremediation of metal polluted soils

Metal concentrations in soils are locally quite high, and are still increasing due to many human activities, leading to elevated risk for health and the environment. Phytoremediation may offer a viable solution to this problem, and the approach is gaining increasing interest. Improvement of plants by genetic engineering, i.e. by modifying characteristics like metal uptake, transport and accumulation as well as metal tolerance, opens up new possibilities for phytoremediation. So far, only a few cases have been reported where one or more of these characteristics have been successfully altered; e.g. mercuric ion reduction causing improved resistance and phytoextraction, and metallothionein causing enhanced cadmium tolerance. These, together with other approaches and potentially promising genes for transformation of target plants are discussed.     

Pesticides in rainfall in Europe

Papers and published reports investigating the presence of pesticides in rainfall in Europe were reviewed. Approximately half of the compounds that were analysed for were detected. For those detected, most concentrations were below about 100 ng/l, but larger concentrations, up to a few thousand nanograms per litre, were detected occasionally at most monitoring sites. The most frequently detected compounds were lindane (gamma-HCH) and its isomer (alpha-HCH), which were detected on 90-100% of sampling occasions at most of the sites where they were monitored. For compounds developed more recently, detection was usually limited to the spraying season. A classification of pesticides according to their deposition pattern is proposed.     

Solar photocatalytic mineralization of commercial pesticides: methamidophos

Aqueous solutions of methamidophos (O,S-dimethyl phosphoramidothioato) are mineralised in sunlight in the presence of dispersed particles of TiO2 in a pre-industrial pilot plant. A commercial pesticide (Tamaron 50, 50% Methamidophos) is used as a model to demonstrate the application of the treatment. Total Organic Carbon (TOC) and PO4(3-) are analysed to confirm the mineralization of the contaminants. The concentration of organics in water was set at TOC approximately 100 mg/L, but with only illuminated TiO2, mineralization was slow. Oxidation of the organics present in the formulation is enhanced 18 times by use of an appropriate electron scavenger (peroxydisulphate) compared to TiO2 alone.     

Assessing the effect of climate oscillations and land-use changes on streamflow in the central Spanish Pyrenees

Plans to increase the amount of irrigated land in Mediterranean countries should consider how changes in climate and land-use affect water resources. In this study, both precipitation and temperature were used to analyze regional trends in discharge in the basins of the Central Spanish Pyrenees since the mid-20th century. Annual variations in the relationship between precipitation and discharge suggested that discharge was relatively lower in the second half of the study period, coinciding with major changes in land use. On a monthly scale, precipitation increased significantly in October, April, and July, and decreased in March, and temperature increased in January and February and decreased in April. Nevertheless, discharge has decreased significantly in most months in the past 50 years. Land-use and plant-cover changes are the only nonclimatic factor that can explain the loss of around 30% of the average annual discharge.     

Air quality management in Portugal: example of needs and available tools

The Framework Directive (FWD) and the proposed Daughter Directives are the newest legislative instruments concerning a new political strategy and air quality management approach for Europe. Additionally, the member countries of the United Nations Economic Commission for Europe have included the concepts of critical load and level for planning air pollution abatement strategies and as a base of international agreements concerning limitation of the emissions of air pollutants. These concepts imply an accurate knowledge about pollutants deposition fluxes. The paper describes the main needs and the tools available to define a strategy of air quality management in Portugal. Two study cases are presented: (1) extensive monitoring plan to assess the impact of an urban incinerator plant; and (2) contribution to a methodology to estimate critical levels for a coastal region in Portugal. These different approaches allowed illustrating the complexity of the implementation of an air pollution management strategy.     

Toxicological assessment of chlorinated diphenyl ethers in the rat

Chlorinated diphenyl ethers are environmental contaminants that have been found in Great Lakes fish and birds. Because of their presence in the food chain, and potential for human exposure, the present short-term study was conducted to assess their toxicity. Groups of 10 male and 10 female rats were each given by gavage 2,2',4,4'6-pentachlorodiphenyl ether (CDE1), 2,2',4,4',5,6-hexachlorodiphenyl ether (CDE2) or 2,2',3,3',4,6'-hexachlorodiphenyl ether (CDE3) at dose levels of 0.04, 0.4, 4.0 or 40 mg/kg b.w./day for a period of 28 days. The control group received an equivalent volume of corn oil only (0.5 ml/100 g b.w.). Treatment with the three CDE congeners did not result in suppression of growth rate or food consumption. Increased liver weights were seen in the animals of both sexes fed 40 mg/kg CDE2, in males treated with 40 mg/kg CDE1, and in females with 40 mg/kg CDE3. Hepatic microsomal aminopyrine demethylase activity was significantly higher in the male rats administered 40 mg/kg CDE2, and aniline hydroxylase activity was elevated in the females following the same treatment. Serum glucose, calcium, protein and urea nitrogen of CDE1-treated males were higher than the control. Levels of uric acid, potassium and LDH of CDE3-treated females were also elevated. No hematological changes were observed. Histological examination revealed that the liver and thyroid were the target organs affected by CDE treatment but the morphological changes were mild even at the highest dose level. Changes in the liver consisted of nuclear vesiculation and increased cytoplasmic volume. Alterations in the thyroid were characterized by increased epithelial height and follicular collapse. Based on the data presented above, the 3 CDE congeners can only be considered moderately toxic in the rat.     

Effects of composting on phytotoxicity of spent pig-manure sawdust litter

The phytotoxicity of spent pig-manure sawdust litter (spent litter) was evaluated during further composting. Aqueous extracts of the spent litter were prepared by shaking the sample with water (1:10 w/v), and the toxicity of these extracts was determined on relative seed germination, relative root elongation and germination index (GI, a factor of relative seed germination and relative root elongation). The sensitivity of six plant species, namely Brassica parachinensis (Chinese cabbage), Brassica albogalera (Chinese kale), Allium sativum (onion), Cucumis sativus (cucumber), Amaranthus espinosus (Chinese spinach), and Lycopersicon esculentum (tomato) were compared. The effect of different moisture levels during composting on the phytotoxicity of the spent litter was also examined. Phytotoxicity of the spent litter was only evident during the earlier stage of composting (first 14 days) and, that seed germination and root elongation reached 100% (same as the control) towards the end of the composting. The concentrations of the major inhibitors, water-extractable Cu and Zn, and NH4(+)-N of the spent litter, declined during composting, indicating that these inhibitors were gradually eliminated as composting proceeded. Multiple regression analysis showed that the NH4(+)-N content of the spent litter was the most important chemical factor affecting phytotoxicity of the plant species selected for this study. Relative root elongation and GI were more sensitive indicators of phytotoxicity than seed germination. In the present study, the GI's of all plant species were >80% at day 60, indicating that the spent litter had reached its maturation by day 60. The responses of different plant species to the water-extracts of the spent litter were different. Among the six species, Chinese cabbage and Chinese spinach were the most sensitive species, and tomato and cucumber were the least sensitive species to indicate phytotoxicity of the spent litter. Moisture adjustment during the composting process did not affect the results of the phytotoxicity test.