Analysis of dioxins and furans in environmental samples by GC-ion-trap MS/MS

The work aims to characterise PCDDs/Fs in environmental matrices by high resolution gas chromatography coupled to low resolution quadrupole ion-trap mass spectrometry (GC-QITMS/MS). In particular, the study was mainly focused in different environmental samples such as sewage sludge, soils, and sediments and in combustion residues as fly ashes. Previous experiences have already detected and quantified PCDDs/PCDFs in all matrices studied. Moreover, isomer-specific analysis of 2,3,7,8-PCDDs/Fs compounds corroborated good correlation between GC-QITMS/MS and a well-established technique such as high resolution mass spectrometry (HRMS). Finally, QC measures included the participation in intercalibration exercises. Successful results were achieved using GC-QITMS/MS in the analysis of fly ashes, soils and sediment materials. In general, GC-QITMS/MS constitutes an interesting alternative for routine analysis of dioxins in such as matrices.     

Study of the degradation of dyes by MnP of Phanerochaete chrysosporium produced in a fixed-bed bioreactor

The production of ligninolytic enzymes by the fungus Phanerochaete chrysosporium in a fixed-bed tubular bioreactor, filled with cubes of nylon sponge, operating in semi-solid-state conditions, was studied. Maximum individual manganese-dependent peroxidase (MnP) and lignin peroxidase (LiP) activities of 1293 and 225 U/l were detected.The in vitro decolourisation of two structurally different dyes (Poly R-478, crystal violet) by the extracellular liquid obtained in the above-mentioned bioreactor was monitored in order to determine its degrading capability. The concentration of some compounds (sodium malonate, manganese sulphate) from the reaction mixture was optimised in order to maximise the decolourisation levels. A percentage of Poly R-478 decolourisation of 24% after 15 min of dye incubation was achieved.On the other hand, a methodology for a long treatment of these dyes based on the continuous addition of MnP enzyme and H(2)O(2) was developed. Moreover, this enzymatic treatment was compared with a photochemical decolourisation process. The former allowed to maintain the degradation rate almost constant for a long time, resulting in a decolourisation percentage of 70% and 30% for crystal violet and Poly R-478, respectively, after 2 h of treatment. As for the latter, it was not able to degrade Poly R-478, whereas crystal violet reached a degradation of 40% in 2 h.     

Evaluation of sequentially-coupled POP fluxes estimated from simultaneous measurements in multiple compartments of an air-water-sediment system

Bulk atmospheric deposition fluxes, air-water exchange fluxes, particle settling fluxes out of the upper water column, sediment trap fluxes in deep waters, and sediment burial fluxes of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in the Koster Fjord, eastern Skagerak, on the Swedish west coast. The aim of the study was to compare the magnitude and direction of the compound fluxes in the system in order to diagnose key fate processes. The PCB and PAH fluxes via net atmospheric deposition, settling particles out of the surface and through deep waters, as well as into the accreting underlying sediments were shown to be remarkably similar, agreeing within a factor of a few for any given target compound. Fluxes of all PCB and PAH target compounds remained fairly constant with water column depth. Thus there was no evidence for net desorption from sinking particles. The net unidirectional and near balancing of vertical fluxes suggests a net transport of PCBs and PAHs from the atmosphere to the continental shelf sediments in the Koster Fjord, which is consistent with the hypothesis that the shelf sediments are important sinks for these compounds.     

Kinetics of thermophilic anaerobes in fixed-bed reactors

The main objective of this study is to estimate growth kinetic constants and the concentration of "active" attached biomass in two anaerobic thermophilic reactors which contain different initial sizes of immobilized anaerobic mixed cultures and decompose distillery wastewater. This paper studies the substrate decomposition in two lab-scale fixed-bed reactors operating at batch conditions with corrugated tubes as support media. It can be demonstrated that high micro-organisms-substrate ratios favor the degradation activity of the different anaerobic cultures, allowing the stable operation without lag-phases and giving better quality in effluent. The kinetic parameters obtained--maximum specific growth rates (mu(max)), non-biodegradable substrate (S(NB)) and "active or viable biomass" concentrations (X(V0))--were obtained by applying the Romero kinetic model [L.I. Romero, 1991. Desarrollo de un modelo matemático general para los procesos fermentativos, Cinética de la degradación anaerobia, Ph.D. Thesis, University of Cádiz (Spain), Serv. Pub. Univ. Cádiz], with COD as substrate and methane (CH4) as the main product of the anaerobic process. This method is suitable to calculate and to differentiate the main kinetic parameters of both the total anaerobic mixed culture and the methanogenic population. Comparison of experimental measured concentration of volatile attached solids (VS(att)) in both reactors with the estimated "active" biomass concentrations obtained by applying Romero kinetic model [L.I. Romero, 1991. Desarrollo de un modelo matemático general para los procesos fermentativos, Cinética de la degradación anaerobia, Ph.D. Thesis, University of Cádiz (Spain), Serv. Pub. Univ. Cádiz] shows that a large amount of inert matter is present in the fixed-bed reactor.     

Mercury burdens in Chinese mitten crabs (Eriocheir sinensis) in three tributaries of southern San Francisco Bay, California, USA

Chinese mitten crabs (Eriocheir sinensis), endemic to Asia, were first reported in the San Francisco Bay in 1992. They are now established in nearly all San Francisco Bay tributaries. These crabs accumulate more metals, such as mercury, than crustaceans living in the water column. Because their predators include fish, birds, mammals and humans, their mercury burdens have an exceptional potential to impact the ecosystem and public health. We sought to elucidate the potential threat of mitten crab mercury burdens in three adjacent streams in southern San Francisco Bay, one of which is known to be contaminated with mercury. Mitten crabs had hepatopancreas concentrations of total mercury and methylmercury that did not differ among streams. The maximum burden we measured was below the action level of 1 ppm recommended by the USEPA. Hepatopancreas concentrations of methylmercury declined with increasing crab size, suggesting a mechanism for mercury excretion and that predators might reduce mercury exposure if they select larger crabs. Because mercury may be heterogeneously distributed among tissues, estimation of the impacts of crab mercury burdens on the environment requires more data on the feeding preferences of predators.     

Sorption, degradation and mobility of ptaquiloside, a carcinogenic Bracken (Pteridium sp.) constituent, in the soil environment

Ptaquiloside (PTA) is a carcinogenic norsesquiterpene glucoside produced by Bracken in amounts up to at least 500 mg m(-2). The toxin is transferred from Bracken to the underlying soil from where it may leach to surface and groundwater's impairing the quality of drinking water. The objectives of the present study were to characterize the solubility, degradation and retention of PTA in soils in order to evaluate the risk for groundwater contamination. PTA was isolated from Bracken. The logarithmic octanol-water and ethyl acetate-water partitioning coefficients for PTA were -0.63 and -0.88, respectively, in agreement with the high water solubility of the compound. PTA hydrolysed rapidly in aqueous solution at pH 4 or lower, but was stable above pH 4. Incubation of PTA with 10 different soils at 25 degrees C showed three different first order degradation patterns: (i) rapid degradation observed for acid sandy soils with half life's ranging between 8 and 30 h decreasing with the soil content of organic matter, (ii) slow degradation in less acid sandy soils with half-lives of several days, and (iii) fast initial degradation with a concurrent solid phase-water partitioning reaction observed for non-acid, mostly clayey soils. The presence of clay silicates appears to retard the degradation of PTA, possibly through sorption. Degradation at 4 degrees C was generally of type (iii) and degradation rates were up to 800 times lower than at 25 degrees C. Sorption isotherms for the same set of soils were almost linear and generally showed very low sorption affinity with distribution coefficients in the range 0.01-0.22 l kg(-1) at a solution concentration of 1 mg l(-1) except for the most acid soil; Freundlich affinity coefficients increased linearly with clay and organic matter contents. Negligible sorption was also observed in column studies where PTA and a non-sorbing tracer showed almost coincident break-through. Leaching of PTA to the aqueous environment will be most extensive on sandy soils, having pH >4 and poor in organic matter which are exposed to high precipitation rates during cold seasons.     

Leaching of glyphosate and AMPA under two soil management practices in Burgundy vineyards (Vosne-Romanée, 21-France)

Some drinking water reservoirs under the vineyards of Burgundy are contaminated with herbicides. Thus the effectiveness of alternative soil management practices, such as grass cover, for reducing the leaching of glyphosate and its metabolite, AMPA, through soils was studied. The leaching of both molecules was studied in structured soil columns under outdoor conditions for 1 year. The soil was managed under two vineyard soil practices: a chemically treated bare calcosol, and a vegetated calcosol. After 680 mm of rainfall, the vegetated calcosol leachates contained lower amounts of glyphosate and AMPA (0.02% and 0.03%, respectively) than the bare calcosol leachates (0.06% and 0.15%, respectively). No glyphosate and only low amounts of AMPA (<0.01%) were extracted from the soil. Glyphosate, and to a greater extent, AMPA, leach through the soils; thus, both molecules may be potential contaminants of groundwater. However, the alternative soil management practice of grass cover could reduce groundwater contamination by the pesticide.     

Determination of polybrominated diphenyl ethers in soil and sediment from an electronic waste recycling facility

In this study samples of ten species of fish were analyzed for concentrations of organochlorine pesticides, PCBs and heavy metals (Pb, Cd, and Cu). Fish were captured using electric fishing on ten sites along the Dr?me river (Rh?ne-Alpes region). Quantitative determination of the organochlorine and PCBs compounds was performed by gas chromatography-electron-capture detection (GC-ECD). The concentrations of heavy metals were determined by atomic absorption spectrophotometry. Samples contained detectable concentrations of lindane, PCBs, and heavy metals but at concentrations below the maximum residue limit (MRL). Non-parametric statistical analysis was performed to distinguish groups of sites with different levels of contamination. PCBs concentrations increased along the river with four groups of sites significantly different from each other. Cadmium concentrations were below the MRL. Lead contamination showed two groups significantly different and a repartition similar to PCBs. Copper contamination was correlated with the localization of vineyards. We assessed the potential effects of contamination the otter (Lutra lutra). The concentrations of all pollutants analyzed in fish sampled in this study are lower than the threshold values described in literature. The Dr?me river is relatively unpolluted river, and the establishment of otter populations should not be affected by pollution.     

Organic mercury levels among the Yanomama of the Brazilian Amazon Basin

The Catrimani River basin in northern Brazil is the home of the Yanomama and has been the site of renegade gold mining since 1980. Gold-mining operations release inorganic mercury (Hg) into the environment where it is organified and biomagnified in aquatic ecosystems. Ingestion of mercury-contaminated fish poses a potential hazard to fish-eating populations such as the Yanomama. We surveyed Hg levels in Yanomama villagers living near mined and unmined rivers in 1994 and 1995, and analyzed Hg levels in piranha caught by villagers. In 1994, 90 Yanomama Indians from 5 villages and in 1995, 62 Yanomama Indians from 3 villages participated in the studies. Four villages surveyed in 1994 were located directly on the Catrimani River, approximately 140-160 km downstream from past gold-mining activities. The other village surveyed in 1994 was situated on the unmined Ajaraní River. In 1995, 2 of the Catrimani River villages were revisited, and a third Yanomama village, on the unmined Pacu River, was surveyed. Blood organic mercury levels among all villagers surveyed ranged from 0 to 62.6 microg L(-1) (mean levels in each village between 21.2 microg L(-1) and 43.1 microg L(-1)). Mercury levels in piranha from the mined Catrimani River ranged from 235 to 1084 parts per billion (ppb). Nine of 13 piranhas, measuring 30 cm or longer had total mercury levels which exceeded mercury consumption limits (500 ppb) set by both the World Health Organization and the Brazilian Ministry of Health. Unexpectedly, high mercury levels were also observed in fish and villagers along the unmined Ajaraní and Pacu Rivers suggesting that indirect sources may contribute to environmental mercury contamination in the Amazon basin.     

Toxicity evaluation of reactive dyestuffs, auxiliaries and selected effluents in textile finishing industry to luminescent bacteria Vibrio fischeri

The toxicity of 17 selected process effluents, 11 reactive dyestuffs and 8 auxiliaries from a textile dyeing and finishing mill in Ayazaga, Istanbul, Turkey was evaluated by bioluminescence test using bacteria Vibrio fischeri in LUMIStox 300. The EC20 and EC50 for auxiliaries, the EC20 for dyestuffs were determined. For selected process effluents GL-values, the dilution level at which a wastewater sample causes less than 20% inhibition, were examined. Our results demonstrate that the toxicity assessment with luminescent bacteria is effective and of practical use for chemicals applied in textile finishing industry with the limitation of the deep dark-colored dye bath samples and for the related effluents. Inhibition effects of numerous dyestuffs as well as auxiliaries to luminescent bacteria differed considerably with a range 5-600 mg l(-1) for EC20 and 9-6930 mg l(-1) for EC50, respectively. Among 17 effluents, I sample exhibited high toxicity (GL = 100), 7 showed moderate toxicity (GL = 12-32), and 9 had a GL-value <10 indicating a low or no toxicity.