Perfluorinated chemicals in selected residents of the American continent

Perfluorinated chemicals (PFCs) are used in multiple consumer products. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), the most widely studied PFCs, may be potential developmental, reproductive, and systemic toxicants. Although PFCs seem to be ubiquitous contaminants found both in humans and animals, geographic differences may exist in human exposure patterns to PFCs. We measured 11 PFCs in 23 pooled serum samples collected in the United States from 1990 through 2002, and in serum samples collected in 2003 from 44 residents from Trujillo, Peru. PFOS and PFOA were detected in all the pooled samples; perfluorohexane sulfonic acid (PFHxS) was detected in 21. Median concentrations were 31.1 micrograms per liter (mug/l, PFOS), 11.6 microg/l (PFOA), and 2 microg/l (PFHxS). The 90th percentile concentrations of PFCs in the 44 Peruvian residents were 0.7 microg/l (PFOS), 0.1 microg/l (PFOA), and <0.3 microg/l (PFHxS). The frequencies of detection were 20% (PFOS), 25% (PFOA), and 9% (PFHxS). The frequent detection of selected PFCs in the pooled samples from the United States and the lack of clear concentration trends based on a year of collection suggest a sustained widespread exposure to these compounds among US residents, at least since the 1990s. By contrast, the much lower frequency of detection and concentration ranges of PFCs in Peru suggest a lower exposure of Peruvians to PFCs compared with North Americans. Genetic variability, diet, lifestyle, or a combination of all these may contribute to the different patterns of human exposure to PFCs in the United States and Peru.     

Human exposure to dioxins through the diet in Catalonia,Spain: carcinogenic and non-carcinogenic risk

The main objectives of this study were to estimate the dietary intake of dioxins by the population of Catalonia, Spain, to determine which food groups showed the greatest contribution to this intake, and to assess the health risks potentially associated with the dietary dioxin intake. From June to August 2000, food samples were randomly acquired in seven cities of Catalonia. Dioxin concentrations were determined in 108 samples belonging to the following groups: vegetables, fruits, pulses, cereals, fish and shellfish, meats and meat products, eggs, milk and dairy products, and oils and fats. Estimates of average daily food consumption were obtained from recent studies. Total dietary intake of dioxins for the general population of Catalonia was estimated to be 95.4 pg WHO-TEQ/day (78.4 pg I-TEQ/day), with fish and shellfish (31%), diary products (25%), cereals (14%) and meat (13%) showing the greatest percentages of contribution to dioxin intake. The contribution of all the rest of food groups to the total dietary intake was under 20%. The non-carcinogenic risk index of dioxin intake through the diet was in the range 0.34-1.36, while the carcinogenic risk level was 1,360 excess cancer over a lifetime of 70 years. Our results corroborate the decreasing tendency in dietary intake of dioxins found in recent studies (2000-2001) from various countries.     

Effects of elevated soil copper on phenology,growth and reproduction of five ruderal plant species

The repeated use of copper (Cu) fungicides to control vine downy mildew, caused by Plasmopara viticola, has been responsible for the heavy increase of Cu concentration in the upper layers of vineyard soils. To determine the effects of elevated soil Cu on plant development, we created an artificial soil gradient with Cu enrichments ranging from 0 to 400 mg kg-1. On this gradient, and for five ruderal plant species commonly found in vineyards in southern France (Poa annua L., Dactylis glomerata L., Senecio vulgaris L., Hypochoeris radicata L., and Andryala integriflolia L.), we quantified survival, growth, and reproduction throughout one flowering season. High concentrations of Cu in the soil resulted in low survival, low total plant biomass, delay in flowering and fruiting, and low seed set. However, the effects differed among species. Furthermore, high soil Cu concentrations had contrasting effects on patterns of resource allocation depending on the plant species.     

Changes of copper speciation in maize rhizosphere soil

Chemical forms of copper in the rhizosphere and bulk soil of maize were investigated using rhizobox cultivation and sequential extraction techniques. The copper accumulations were also determined. The results demonstrated that there were continuous changes in copper fractionation within the maize rhizosphere. Initially, the amount of exchangeable copper increased before dropping below the initial level after 40 days or so. Carbonate associated copper followed a similar trend of change, but with a slower pace than the exchangeable copper. The increase in carbonate associated copper only become evident after 30 days, with the net loss occurring after 60 days. There were also initial increases in oxide bound copper as well as decreases in the organic matter associated copper, both followed by a turnover after 40-50 days. The accumulation of copper in the maize plant was found to be biomass dependent. The amount of accumulated copper absorbed in the plant material exceeded the initial quantity of the exchangeable copper in the soil, revealing a transformation from less bioavailable to more bioavailable fractions. During cultivation, decreases in redox potential and increases in pH, dissolved organic carbon (DOC), and microbial activity in the maize rhizosphere were observed. The change in copper speciation may result from root-induced changes in DOC, redox potential, and microbial activity in the rhizosphere.     

Trace metal behaviour in the Conwy estuary,North Wales

The distribution of trace metals Zn, Ni, Mn, Fe, Cu, Pb, Cd and Cr between suspended particulate matter (SPM) and water in the Conwy estuary, North Wales, has been studied in three surveys in 1998. Dissolved Cu and Mn showed some monthly variations. Most of the dissolved trace metals displayed a negative association with salinity, indicating rivers as a major source of inputs for them. Particulate Zn, Mn and Fe showed a decreasing concentration seaward, whilst the levels of Ni, Cu, Cr and Pb increased with salinity. SPM concentration was the most important variable significantly related to trace metal concentrations in SPM, with an inverse relationship between the two parameters. This was explained by the relative enrichment of trace metals in fine particles at low SPM concentrations and relative depletion of trace metals in coarse particles at high SPM concentrations. Particulate Zn, Mn and Pb were dominated by the fraction available to acetic acid (non-detrital), whilst particulate Ni, Fe and Cr were dominated by the fraction available to nitric acid (detrital). The partition coefficient of trace metals between SPM and water declined with increasing SPM concentration, consistent with the so-called "particle concentration effect". Such a phenomenon may be explained by the presence of fine particles (including colloids) enriched with trace metals at low SPM concentrations, and the salinity-induced desorption.     

Electrochemical degradation of chlorophenoxy and chlorobenzoic herbicides in acidic aqueous medium by the peroxi-coagulation method

The degradation of 4-chlorophenoxyacetic acid (4-CPA), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) as chlorophenoxy herbicides, as well as of 3,6-dichloro-2-methoxybenzoic acid (dicamba) as chlorobenzoic herbicide, has been studied by peroxi-coagulation. This electrochemical method yields a very effective depollution of all compounds in acidic aqueous medium of pH 3.0 working under pH regulation, since they are oxidized with hydroxyl radicals produced from Fenton's reaction between Fe(2+) and H(2)O(2) generated by the corresponding Fe anode and O(2)-diffusion cathode. Their products can then be removed by mineralization or coagulation with the Fe(OH)(3) precipitate formed. Both degradative paths compete at low currents, but coagulation predominates at high currents. The peroxi-coagulation process of dicamba at I>or=300 mA leads to more than 90% of coagulation, being much more efficient than its comparative electro-Fenton treatment with a Pt anode and 1 mM Fe(2+), where only mineralization takes place. For the chlorophenoxy compounds, electro-Fenton gives a slightly lower depollution than peroxi-coagulation, because more easily oxidable products are produced. Oxidation of chlorinated products during peroxi-coagulation is accompanied by the release of chloride ion to the solution. The efficiency of this method decreases with increasing electrolysis time and current. The decay of all herbicides follows a pseudo-first-order reaction, with a similar constant rate for 4-CPA, MCPA, 2,4-D and 2,4,5-T, and a higher value for dicamba.     

Understanding the effectiveness of precursor reductions in lowering 8-hr ozone concentrations

Analyses of ambient measured ozone data were used in conjunction with the application of photochemical modeling to determine the technical feasibility of attaining the federal 8-hr ozone standard in central California. Various combinations of volatile organic compound (VOC) and oxides of nitrogen (NOx) emission reductions were effective in lowering modeled peak 1-hr ozone concentrations. However, VOC emissions reductions were found to have only a modest impact on modeled peak 8-hr ozone concentrations. NOx emission reductions generally lowered 8-hr ozone concentrations, but their effectiveness was partially or, in some cases, wholly offset by the increase in the number of NO cycles and, hence, in the ozone produced per NO. As a result, substantial NOx emission reductions--70 to 90%--were required to reduce peak 8-hr ozone concentrations to the level of the standard throughout the modeling domain. These modeling results provide a possible physical explanation for recent analyses that have reported more prominent trends in peak 1-hr ozone levels than in peak 8-hr ozone concentrations or in occurrences of mid-level (60-90 parts per billion by volume) ozone concentrations. The findings also have serious implications for the feasibility of attaining the 8-hr ozone standard in central California. Further efforts are needed to clarify the applicability of the modeling results to the full set of days with ozone levels exceeding the 8-hr ozone standard, as well as their applicability to other geographical areas.     

Congener-specific accumulation of polychlorinated biphenyls in ovarian follicular wall follows repeated exposure to PCB 126 and PCB 153. Comparison of tissue levels of PCB and biological changes

OBJECTIVE: Small (SF), medium (MF) and large (LF) preovulatory porcine follicles were isolated and incubated in an Erlenmeyer flask containing 5 ml of medium with addition of PCB 126 or PCB 153 to test differences in their accumulation in the follicular wall. METHODS; The follicles were incubated in M199 medium at 37 degrees C with constant shaking at 70 rpm, for 6 days. The media were changed every day and repeated dose 25 pg/ml of PCB 126 or 25 ng/ml of PCB 153 was added each day till 6 days of culture. Media were collected every day and frozen for steroid analysis by RIA. 24 h after the last treatment follicles were frozen for further polychlorinated biphenyls (PCB) content analysis. PCB concentrations in the follicular wall were analysed by mass spectrometry. RESULTS: 3.3%; 3.6% and 5.6% of total PCB 126 dose, and 71%; 71.4% and 30.4% of total PCB 153 dose accumulated in SF, MF and LF follicles, respectively. The accumulative effect of PCB was manifested by the disruption of estradiol (E2) secretion. In SF antiestrogenic action of PCB 126 was observed during the whole time of exposure while PCB 153 decreased E2 till 4 days of culture and then estrogenic action was observed. In MF, both these congeners decreased E2 till 5 days of exposure and then estrogenic actions were noted with the highest magnification in the case of PCB 126. In LF both PCB studied increased E2 till 3 days of exposure with the highest magnification of PCB 126, then antiestrogenic action was noted. Testosterone secretion was generally affected in a pattern oposite to that of E2 suggesting action on P450arom activity. CONCLUSION: The results of these studies demonstrated that disruption of aromatization process in the follicles following repeated exposure to both congeners is not directly correlated with the bioaccumulation or amount of PCB within the follicular wall.     

Fate and assessment of persistent organic pollutants in water and sediment from Minjiang River Estuary,Southeast China

Persistent organochlorine compounds were analyzed in surface water, porewater and surficial sediment samples from Minjiang River Estuary, which is the first large river in Fujian Province, Southeast of China. The total concentrations of 18 organochlorine pesticides were 214.4-1819, 4541-13,699 ng/l, 28.79-52.07 ng/g in surface water, porewater and sediments (dry weight) respectively, and those of 21 polychlorinated biphenyls (PCBs) in the three phases were: 203.9-2473, 3192-10,855 ng/l, 15.14-57.93 ng/g respectively. The results showed that the concentrations of these selected organochlorine pesticides and PCBs in porewater were higher than those in surface water. It may be due to the fact that these organic hydrophobic pollutants tend to stay in the sediments, and then re-suspend from the sedimentary phase to the upper water. We have analyzed the distribution characteristics of individual organochlorine pesticide components and PCBs, and found that alpha-HCH, DDE, Heptachlor, Endosulfan II, Methoxychlor were the most common organochlorine pesticides contaminants. Considering the groups of HCHs (HCHs=alpha-HCH+beta-HCH+gamma-HCH+delta-HCH) and DDTs (DDTs=DDT+DDD+DDE), the predominance of beta-HCH, DDE in all water, porewater and sediment samples was clearly observed. This observation suggested that beta-HCH was resistant to biodegradation and the DDTs had been transformed to its metabolites, DDE and DDD, of which DDE that was more un-degradable. The PCB congeners containing 3-6 chlorines had the great preponderance in the three phase. These results were compared with those present in other estuaries and harbors. A risk assessment was evaluated for the persistent organic pollutants in the Minjiang River Estuary.     

Removal of biocide pentachlorophenol in water system by the spent mushroom compost of Pleurotus pulmonarius

Pentachlorophenol (PCP) has been widely used as a wood preservative since 1980s. Although it has been banned worldwide, residues of PCP are still commonly found. The spent compost of oyster mushroom Pleurotus pulmonarius (SMC) which was a degraded paddy straw-based substrate, contained 25% chitin. Five percentage of the SMC could remove 89.0 +/- 0.4% of 100 mg PCPl(-1) within 2 days at room temperature predominantly by biodegradation. The maximum removal capacity was 15.5 +/- 1.0 mg g(-1) SMC. The sorption kinetics of PCP by SMC can be described by the Freundlich monolayer model with a theoretical sorption capacity similar to that found for chitin. A PCP-degradative bacterium was isolated from the SMC. Yet, biodegradation was predominantly contributed by the immobilized ligninolytic enzymes secreted by the mushroom to the SMC. Degradation of PCP involves dechlorination, methylation, carboxylation and ring cleavage as verified by GC-MSD and ion chromatography. Thus, the SMC has a potential for treating PCP-contaminated water.