Guidelines for routine mercury speciation analysis in seafood by gas chromatography coupled to a home-modified AFS detector. Application to the Andalusian coast (south Spain)

A home-modified atomic fluorescence detector (mAFS) has been employed for mercury and methylmercury determination in bivalves from the Andalusian coast (south Spain). This modification consists on the inclusion of a quartz flow cell into the detector, which increases the concentration of mercury atoms in the detector and therefore enhances sensitivity about two fold. Two analytical approaches for mercury speciation based on the coupling of gas chromatography on-line pyrolysis and mAFS (GC-Pyro-mAFS) have been tested. The first approach (Method 1) is based on aqueous ethylation followed by extraction into an organic solvent, and the second one (Method 2) in the extraction of monoalkylated mercury as chloride. Method 1 is a rapid procedure but not sensitive enough for the analysis of methylmercury in non-polluted sites (detection limit: 20 ng g(-1) as mercury, wet basis). The second one is quite more sensitive (detection limit: 0.2 ng g(-1), wet weight), but sample treatment is cumbersome and time-consuming. The optimum range for mercury determination for both methods are complementary and exhibit an overlapping measurable concentration range (OMCR) in which methylmercury can be indistinctly determined (75-100 ng g(-1) as mercury, wet basis). The suitability of both methods has been assayed with spiking experiences at levels within the OMCR with good recoveries. Both approaches have been validated with two certified reference materials (BCR-463, mercury and methylmercury in tuna fish; and NIST-2977, organic contaminants and trace metals in mussel tissue). Both procedures have been used for the analysis of three species of bivalve molluscs collected along the Andalusian coast (south Spain), all of them employed for human consumption (Chamelea gallina, Donax trunculus and Scrobicularia plana), and their potential use in routine analysis has been established.     

Degradation of some biorecalcitrant pesticides by homogeneous and heterogeneous photocatalytic ozonation

Photo-Fenton/ozone (PhFO) and TiO2-photocatalysis/ozone (PhCO) coupled systems are used as advanced oxidation processes for the degradation of the following biorecalcitrant pesticides: alachlor, atrazine, chlorfenvinfos, diuron, isoproturon and pentachlorophenol. These organic compounds are considered Priority Hazardous Substances by the Water Framework Directive of the European Commission. The degradation process of the different pesticides, that occurs through oxidation of the organic molecules by means of their reaction with generated OH radical, follows a first and zero-order kinetics, when PhFO and PhCO are applied, respectively. These two Advanced Oxidation Processes, together with the traditional ozone+UV, have been used to investigate TOC reduction of the different pesticide aqueous solutions. The best results of pesticide mineralization are obtained when PhFO is applied; with the use of this advanced oxidation process the aqueous pesticide solutions become detoxyfied except in the case of atrazine and alachlor aqueous solutions for which no detoxification is achieved at the experimental conditions used in the work, at least after 2 and 3 h of treatment, respectively.     

Hexazinone and simazine dissipation in forestry field nurseries

Hexazinone and simazine field dissipation was studied in two different soils from Spain (Toledo and Burgos), devoted to forest nurseries for Pinus nigra. Laboratory experiments (adsorption-desorption isotherms, leaching experiment and degradation study) were carried out to determine possible mechanisms of dissipation. Higher adsorption was observed for hexazinone in Toledo (KfT = 0.69) compare to in Burgos soil (KfB = 0.20) probably due to the higher organic matter (OM) content of Toledo soil. No differences in adsorption were obtained for simazine in both soils (KfT = 1.27; KfB = 1.34). In every case, adsorption was higher for simazine than for hexazinone, in both soils. The total recovery of hexazinone in the leachates from handpacked soil columns was higher in Burgos (100%) than in Toledo (80%), because of the larger adsorption of hexazinone in this last soil. No differences in simazine leaching between both soils were found, although the total amount of pesticide recovered in leachates (40% in the two soils) was lower for simazine than for hexazinone. Finally, lower degradation was found in Burgos (t1/2 = 91 d) vs Toledo (t1/2 = 47 d), directly related with the high OM content of Toledo. No half-life was calculated for simazine in Toledo because no changes in herbicide soil content were observed during the period of time studied. In the case of Burgos, the half-life for simazine was 50 days. The field residues study showed larger persistence of simazine than hexazinone mainly due to the higher adsorption and lower mobility of simazine in the two soils. The lower persistence of hexazinone in Toledo soil than in Burgos soil is related to the larger rainfall occurred in this soil besides the higher degradation of this herbicide observed in Toledo soil. The much lower temperature in Burgos than in Toledo soil during winter contribute to the higher persistence of the two herbicides in Burgos soil.     

Comparison of toxicological impacts of integrated and chemical pest management in Mediterranean greenhouses

The goal of this paper is to assess the relative impacts of pest-control methods in greenhouses, based on current LCA tools. As a case study, the relative impacts of two tomato production methods, chemical pest management (CPM) and integrated pest management (IPM), are assessed. The amount of the active ingredients applied, the fate of the ingredients in the various greenhouse and environmental compartments, the human exposure routes via the various compartments and the inherent toxicity of the ingredients were taken into account in the relative impact calculations. To assess the importance of model selection in the assessment, pesticide-specific fate and exposure factors for humans and aquatic and terrestrial ecosystems, used to aggregate pesticide emissions, were calculated with two different models: (1) the USES-LCA model, adapted in order to calculate the pesticide transfer from greenhouse air and soil to fruits, and (2) the empirical model critical surface time (CST). Impact scores have in general shown a higher level of potential contamination in greenhouses treated with CPM compared to IPM (a factor of 1.4 to 2.3). Relative impacts have been shown highly dependent on the selection of specific pesticides and crop stage development at the moment of pesticide application. This means that both CPM and IPM could be improved by a careful selection of pesticides. In order to improve the relative impact calculations, future research in pesticide transfer to food will be necessary.     

Speciation as a screening tool for the determination of heavy metal surface water pollution in the Guadiamar river basin

The Guadiamar river basin has traditionally received pollutants from two main sources: in its northern section of mining origin, and in its southern section (next to Do?ana National Park) from urban-industrial and agricultural sources. In April 1998, the spill of 6 million m3 of mining wastes (acidic waters and sludge) severely polluted the Guadiamar river basin with heavy metals, which caused serious damage to the local ecosystem. There is a direct association between the physicochemical speciation of an element and its toxicity, biological activity, bioavailability, solubility, etc. This work describes a distribution study of the metals Zn, Cd, Pb and Cu by speciation analysis of surface waters in eleven sampling points of the Guadiamar river basin. Four metal fractions were determined using anodic stripping voltammetry: labile metal forms, H+ exchangeable metal forms, strongly inert forms (associated with organic and inorganic matter in solution), and forms associated with suspended matter. Total concentrations in surface waters followed the trend Zn > Cu > Pb > Cd. The speciation study showed that Zn and Cd were present to a large extent in available forms (labile and H+ exchangeable), while Pb and Cu were found mostly in the less available forms (strongly inert). Moreover, the available forms were found in the northern section (mining pollution) and the strongly inert forms in the southern section (urban, industrial and agricultural pollution). These results can illustrate the potential value of speciation to discern between different sources of pollution.     

Effect of temperature on the disappearance of four triazine herbicides in environmental waters

The influence of temperature on the disappearance of four s-triazine herbicides, terbuthylazine, simazine, atrazine and prometryn was studied in sea, river and groundwaters spiked with approx. 5 mg l(-1) of each during long-term laboratory incubation. Residues were analyzed by GC-NPD and confirmed by GC-MSD. No clean-up was necessary and a micro on-line method for the determination of herbicide residues was used. The results showed that temperature had little effect on the behaviour of the four herbicides in river and seawaters but strongly affected their behaviour in groundwater. Simazine was the most readily affected compound in sea, river and groundwaters, while terbuthylazine and atrazine were the most persistent in all cases, especially in riverwater. Half-lives ranged from 41 days (constant rate = 0.017 days(-1)) to 196 days (constant rate = 0.003 days(-1)) for simazine (40 degrees C) and terbuthylazine (20 degrees C), respectively, in riverwater. Only for terbuthylazine in riverwater was the remaining percentage at the end of the experiment higher than 50% (58%, 3.21 mg l(-1)). In the other cases, the remaining percentage varied from 4% (0.20 mg l(-1), 40 degrees C) to 43% (2.25 mg l(-1), 20 degrees C) for simazine and terbuthylazine, respectively, in groundwater.     

Evaluating the heavy metal contamination in sediments from the guadalquivir estuary after the Aznalcóllar mining spill (SW Spain): a multivariate analysis approach

The Doñana National Park is one of the most importantNatural Reserves in west Europe. The park and theGuadalquivir estuary were impacted by the release of 5million cubic meters of acid waste from the processing ofpyrite ore. Here are presented a multivariate analysisapproach to evaluate the extension and the magnitude of theaccidental spill on the estuarine sediments. Sediments wereused to analyze 6 different metals (Fe, Mn, Zn, Cd, Pb, Cu).Also the concentration of the metals in the differentgeochemical sediment fractions were determined as a means ofassessing the potential impact of the acid water from themine. The analysis of the results obtained permits toestablish that the impact of the accident was acute on theecosystem due to the set up of a treatment plan in June 1998and to the high hydrodynamic of the estuary that absorb theearly impact. Chronic contamination by Cu was also detectedduring the monitoring of the impact of the accident in theestuary but this did not appear to be related to theaccidental spill. Because the likelihood of long term adverseeffects from the heavy metal contamination of estuarinesediments, further ecotoxicological evaluations should becarried out for the estuary and the park using an integrated approach.     

Air quality monitoring for multiple pollutants: Optimization of a network around a hypothetical potash plant and two thermal power stations in open countryside

A method is presented for the design of multi-pollutant air quality monitoring networks (AQMN). This technique leads to an optimal network, i.e. a network providing a maximum of information with a minimum of measurement devices. The spatial correlation analysis technique is used to compare the information given by the potential sites that may form the network. The concept of potential of violation is defined to take into account the number of times that the maximum emission values tolerated by law are exceeded. Both objectives are weighted automatically through an adjustable parameter, b, for which an estimation procedure has been developed in this study, depending on the purpose of the network. Several methods are described, allowing simultaneous consideration of different pollutants. As an illustration of these methods, a number of air quality monitoring networks is designed to perform an analysis of the environmental impact due to a hypothetical potash processing plant and two thermal power stations.     

Collaborative evaluation of the analytical state-of-the-art of platinum, palladium and rhodium determinations in road dust

In order to control the quality of platinum, palladium and rhodium determinations in road dust, the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission has started a project, the final aim of which is to certify a road dust reference material for its contents of platinum group elements. The first part of this project consisted of an interlaboratory study, which aimed to test the feasibility of the preparation of a candidate road dust reference material and to detect and remove most of the pitfalls observed in platinum, palladium and rhodium determinations. This paper presents the main results of this interlaboratory study carried out prior to the certification campaign. The concordance of the data obtained by the participating laboratories for the three elements was considered to reflect the state-of-the-art and was encouraging enough to decide on the organization of a certification campaign to be conducted during the year 2000. The progress made with respect to the analytical state-of-the-art for these elements will be of great benefit to the quality of measurements carried out in environmental monitoring in this particular field.     

Detection of phenol-induced subcellular alteration by electron microscopy in the liver and panceres of carp

A sublethal dose (5 mg L^-1) of phenol was applied in the experiment. Liver and pancreas samples were taken at 24, 48, 72, and 96 hr for electron microscopy. The following alterations were manifested during the experiment: amitosis, irregular nuclear forms, decrease of chromatin, nucleolar segregation and numerous phagosomes and autophagic vacuoles in the cytoplasm. After 72 hr, large empty vacuoles also developed in the cells. The rEr was often dilated, and the accumulation of paraprotein crystals in their lumen was also common. All these alterations prove the serious cytopathological effects of phenol on the metabolism of parenchymal cells.