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Widespread use of pesticides in intensive agriculture indicates the need for permanent monitoring of their residues in soil. For this purpose, a total of 22 evenly distributed sampling points of arable land were chosen in the sampling area in Serbia. Soils were divided into groups according to the previous crop (pepper, vegetables, maize, wheat and soybean). Soil properties and residues of 68 pesticides, of which 22 herbicides, 25 insecticides and 21 fungicides, were analysed in the collected soil samples. The obtained data confirm the heterogeneity of soil samples regarding their organic matter content (1.41-3.39%) and pH value (pH 4.27-8.08). The average number of active ingredients detected per type of previous crop was 1-2 herbicides, 14-16 insecticides, and 3-4 fungicides, while the residues of 3 herbicides, 20 insecticides and 9 fungicides were found in total. Insecticides with mainly organochlorine compounds represented the majority of the detected active ingredients. Although rapid degradability of sulfonylurea herbicides is a well-known fact, the residues of nicosulfuron, ranging from 0.15 to 1.99 mu g/kg, were found in three soil samples where maize was grown as a previous crop. Furthermore, triazoles prothioconazole (0.08 +/- 0.11 mu g/kg), tebuconazole (0.10 +/- 0.24 mu g/kg) and epoxyconazole (0.13 +/- 0.42 mu g/kg) were detected in 36%, 18% and 14% soil samples, respectively, while difenoconazole and flusilazole were detected in only one sample. Soil pH value mostly correlated with pesticides. The levels of pesticides detected in agricultural soils should be monitored further, especially in terms of environmental risks posed by their transfer to groundwater and surface waters.

In the present thesis, analytical methods based on gas chromatography coupled with mass spectrometry, both single (GC-MS) or tandem (GC-MS/MS), have been developed and optimized for the detection and quantification of persistent organic pollutants (POPs) such as organochlorinated pesticides (OCPs) and polychlorinated byphenils (PCBs) and emerging pollutants such as organophosphate esters (OPEs), which are currently used as flame retardants, additives and plasticizers. Another family of flame retardants, also classified as POPs, polybrominated diphenil ethers (PBDEs), was also studied and quantified using already optimized and validated methods. The presence of target POPs in environmentally protected areas of the Iberian Peninsula has been evaluated using seagull eggs as bioindicators. Two species, namely yellow-legged gull (Larus michahellis) and Audouin´s gull (Larus Audouinii), have been selected for this purpose. The former is an abundant and widely distributed species with scavenging and opportunistic behavior, while the later is more vulnerable, even though the population is growing during recent years and new colonies are emerging, and showed a strict fish-based diet. Pollution levels detected in gull eggs were dominated by PCBs, followed by various OCPs. Among OCPs, high levels of dichlorodiphenyldichloroethylene (DDE) were found, which is a metabolic and degradation product of dichlorodiphenyltrichloroethane (DDT), a pesticide widely used during the last decades of the 20th century, which showed high toxicity for birds, being able to reduce the reproduction success because it may affect the eggshell thickness and prevent hatching when present at high enough levels. PBDEs were also widespread in the marine environments of the Iberian Peninsula but at lower levels. Audouin´s gull eggs showed higher pollution levels than yellow-legged gulls from the same colonies, suggesting differences in their feeding habits and their bioaccumulation capacity of POPs. In gen, En la presente tesis doctoral se ha estudiado la presencia y distribución de pesticidas organoclorados y retardantes de llama en áreas ambientalmente protegidas de España y China y en una zona afectada por residuos electrónicos en China. Para ello se han desarrollado y aplicado métodos multiresiduo basados en cromatografía de gases acoplada a espectrometría de masas, tanto simple como en tándem, para la detección y cuantificación de, por un lado, contaminantes cuyo uso ha sido restringido y prohibido bajo las directrices del Convenio de Estocolmo y conocidos por sus características fisicoquímicas como compuestos orgánicos persistentes (COPs), los cuales incluyen pesticidas organoclorados (OCPs por sus siglas en inglés), bifenilos policlorados (PCBs) y polibromodifenil éteres (PBDEs) y, por otro lado, una familia de contaminantes emergentes utilizados como plastificantes, aditivos y retardantes de llama como son los ésteres organofosforados (OPEs). En España, el estudio de COPs se ha llevado a cabo mediante el uso de huevos de gaviota como bioindicadores de la contaminación ambiental y se han evaluado los niveles de estos compuestos antropogénicos en las mayores colonias de gaviotas de la península Ibérica, constituidas en zonas con diferentes grados de protección ambiental. Los compuestos detectados a mayor nivel fueron los OCPs, y más en concreto el dicloro difenil tricloroetano (DDT) y sus productos de degradación, seguidos por los PCBs y a menores niveles los PBDEs. En China, se ha detectado la presencia tanto de COPs como de OPEs en suelos y sedimentos de zonas protegidas como parques nacionales y/o reservas naturales que, en principio, deberían ser prístinas. Los contaminantes detectados a mayores niveles fueron los OPEs, probablemente debido a su uso actual. Sin embargo, el isómero alfa del hexaclorociclohexano, así como el PBDE 209 demostraron ser ubicuos en el medio ambiente, lo cual concuerda con los grandes volúmenes de producción y consumo de los mismos e

In the present thesis, analytical methods based on gas chromatography coupled with mass spectrometry, both single (GC-MS) or tandem (GC-MS/MS), have been developed and optimized for the detection and quantification of persistent organic pollutants (POPs) such as organochlorinated pesticides (OCPs) and polychlorinated byphenils (PCBs) and emerging pollutants such as organophosphate esters (OPEs), which are currently used as flame retardants, additives and plasticizers. Another family of flame retardants, also classified as POPs, polybrominated diphenil ethers (PBDEs), was also studied and quantified using already optimized and validated methods. The presence of target POPs in environmentally protected areas of the Iberian Peninsula has been evaluated using seagull eggs as bioindicators. Two species, namely yellow-legged gull (Larus michahellis) and Audouin´s gull (Larus Audouinii), have been selected for this purpose. The former is an abundant and widely distributed species with scavenging and opportunistic behavior, while the later is more vulnerable, even though the population is growing during recent years and new colonies are emerging, and showed a strict fish-based diet. Pollution levels detected in gull eggs were dominated by PCBs, followed by various OCPs. Among OCPs, high levels of dichlorodiphenyldichloroethylene (DDE) were found, which is a metabolic and degradation product of dichlorodiphenyltrichloroethane (DDT), a pesticide widely used during the last decades of the 20th century, which showed high toxicity for birds, being able to reduce the reproduction success because it may affect the eggshell thickness and prevent hatching when present at high enough levels. PBDEs were also widespread in the marine environments of the Iberian Peninsula but at lower levels. Audouin´s gull eggs showed higher pollution levels than yellow-legged gulls from the same colonies, suggesting differences in their feeding habits and their bioaccumulation capacity of POPs. In gen, En la presente tesis doctoral se ha estudiado la presencia y distribución de pesticidas organoclorados y retardantes de llama en áreas ambientalmente protegidas de España y China y en una zona afectada por residuos electrónicos en China. Para ello se han desarrollado y aplicado métodos multiresiduo basados en cromatografía de gases acoplada a espectrometría de masas, tanto simple como en tándem, para la detección y cuantificación de, por un lado, contaminantes cuyo uso ha sido restringido y prohibido bajo las directrices del Convenio de Estocolmo y conocidos por sus características fisicoquímicas como compuestos orgánicos persistentes (COPs), los cuales incluyen pesticidas organoclorados (OCPs por sus siglas en inglés), bifenilos policlorados (PCBs) y polibromodifenil éteres (PBDEs) y, por otro lado, una familia de contaminantes emergentes utilizados como plastificantes, aditivos y retardantes de llama como son los ésteres organofosforados (OPEs). En España, el estudio de COPs se ha llevado a cabo mediante el uso de huevos de gaviota como bioindicadores de la contaminación ambiental y se han evaluado los niveles de estos compuestos antropogénicos en las mayores colonias de gaviotas de la península Ibérica, constituidas en zonas con diferentes grados de protección ambiental. Los compuestos detectados a mayor nivel fueron los OCPs, y más en concreto el dicloro difenil tricloroetano (DDT) y sus productos de degradación, seguidos por los PCBs y a menores niveles los PBDEs. En China, se ha detectado la presencia tanto de COPs como de OPEs en suelos y sedimentos de zonas protegidas como parques nacionales y/o reservas naturales que, en principio, deberían ser prístinas. Los contaminantes detectados a mayores niveles fueron los OPEs, probablemente debido a su uso actual. Sin embargo, el isómero alfa del hexaclorociclohexano, así como el PBDE 209 demostraron ser ubicuos en el medio ambiente, lo cual concuerda con los grandes volúmenes de producción y consumo de los mismos e

Background: Breastfed children absorb persistent and toxic chemicals such as organohalogen compounds (OHCs) during the entire lactation period. Nursing is a main contributor to the burden of these pollutants in the first years of life, hence further assessments on the OHC load processes are needed. Objectives: To identify the determinants of OHC increase in children at four years of age, considering concentration gains, maternal venous concentrations and breastfeeding time. Methods: Concentrations of 19 organochlorine compounds (OCs) and 14 polybrominated diphenyl ethers (PBDEs) were analyzed in maternal venous (n = 466), cord blood (n = 326) and children venous serum at four years of age (n = 272) in the Asturias INMA cohort representing the Spanish general population. Data were evaluated considering the socio-demographic and individual information collected at recruitment and follow up surveys, as well as the OHC physical-chemical constants. Results: The four years-old children concentration gains of the most abundant OHCs showed strong correlations (R2 = 0.65–0.93) with the maternal concentrations during pregnancy and lactation period. The child gain/maternal transfer rates of most correlated pollutants were similar. Discussion: Between 65 and 93% of the variance of OCs in four years-old children was explained by the maternal concentrations during pregnancy and the lactation period. The compounds with log(Kow) > 3.7 (hydrophobic) showed analogous child gain/maternal transfer rates indicating similar processes of membrane lipid dissolution and passive diffusion from the epithelial cells into the milk. Molecular weight of these pollutants did not influence on these rates. Compounds with low log(Koa) such as hexachlorobenzene are more volatile and less retained, involving lower child gain/maternal transfer rates. These results may be useful to anticipate the increase of the concentrations of OCs in children using the maternal concentration of these compounds during

The significance of the offshore vertical convection currents in the transport and sinking of water-soluble organic pollutants into marine deep basins has been evaluated. For this purpose, sediment cores were collected in the Gulf of Lion (GoL) at sites between 26 and 2330 m water depth. The top core layers were analyzed for aromatic and aliphatic hydrocarbons and organochlorine compounds. Organic compounds with logK (air water partition coefficient) between −2 and −4, e.g. lindane, PCB 28, PCB 52, phenanthrene, methylphenanthrenes, dimethylphenanthrenes, C–C n-alkanes, are found in higher concentrations or exhibit relative concentration increases in the sediments deposited in the continental rise as consequence of the open-sea convection processes associated with the formation of Western Mediterranean Deep Water (WMDW). In contrast, the organic pollutants with intermediate air-water distribution coefficients, logK between −2 and 0, and high octanol water distribution coefficients (logKow > 6), e.g. highly chlorinated PCBs, DDTs, DDEs, DDDs, C–C n-alkanes, and polycyclic aromatic hydrocarbons with molecular weight higher than 200, occur in association to sediment particles, which are mainly transported by the Northern current along the continental shelf forming the mud belt. The Rhône prodelta is therefore the area of the GoL showing the highest concentrations of this group of organic compounds, which are preferentially associated with water particles. Overall, the results show that vertical open-sea convection processes related with offshore formation of WMDW may have an important role in the transport and accumulation of water soluble pollutants to deep marine environments of the GoL (>2000 m water depth)

La major part de les activitats industrials ocasionen danys mediambientals, provocats per una mala gestió dels residus i un mal aïllament a l'hora d'eliminar algunes d'aquestes matèries. Això provoca que les substàncies contaminants acabin penetrant en el subsòl, i, el que és pitjor, a les aigües subterrànies, provocant una ràpida i forta expansió del focus de contaminació. En aquest treball es desenvoluparà d'una interfase gràfica per l'anàlisi de riscos associats a problemes de contaminació per organoclorats.

Total syntheses of natural products is one of the most important subjects for chemical science. It is very useful for structural elucidation. Moreover, it could be used for the discovery of new methodology and applications of natural products to chemical biology and drug discovery. Polychlorinated compounds are unique and abundant natural products, which displayed potent antibiotic or cytotoxic activities. The big challenge for syntheses of these natural products is how to diastereoselective construct the vicinal dichlorinated functionalized groups. This thesis research deals with a convenient dichlorination method by in situ generation of various active dichlorinating agents from an environmentally friendly oxone and various cheap chloride sources, which may be exploited in synthesis of other chlorinated organic compounds. This thesis also deals with the total synthesis of natural products with 6,8-dioxabicyclo-[3.2.1]octane (6,8-DOBCO) framework by Achmatowicz rearrangement/bicycloketalization (AR/BCK) sequence. As one important kind of fused bicyclic acetals, 6,8-DOBCO is a very common structural motif in many biologically active natural products. Not surprisingly, natural products containing 6,8-DOBCO framework have attracted much interest in the synthetic communities due to their potent and broad biological activities and unique complex structures. In chapter 1, the relevant methodologies of dichlorination and their applications in the total syntheses of polychlorosulfolipids were overviewed. Next a convenient method was developed for in situ generation of various active dichlorinating agents (c.f. Cl2, NCl3, Et4NCl3, ArICl2) from an environmentally friendly oxone and various cheap chloride sources. The counter ion of the chloride has a tremendous effect on generation of different dichlorinating species using oxone as the oxidant. The synthetic utility of this protocol was demonstrated by diastereoselective

Total syntheses of natural products is one of the most important subjects for chemical science. It is very useful for structural elucidation. Moreover, it could be used for the discovery of new methodology and applications of natural products to chemical biology and drug discovery. Polychlorinated compounds are unique and abundant natural products, which displayed potent antibiotic or cytotoxic activities. The big challenge for syntheses of these natural products is how to diastereoselective construct the vicinal dichlorinated functionalized groups. This thesis research deals with a convenient dichlorination method by in situ generation of various active dichlorinating agents from an environmentally friendly oxone and various cheap chloride sources, which may be exploited in synthesis of other chlorinated organic compounds. This thesis also deals with the total synthesis of natural products with 6,8-dioxabicyclo-[3.2.1]octane (6,8-DOBCO) framework by Achmatowicz rearrangement/bicycloketalization (AR/BCK) sequence. As one important kind of fused bicyclic acetals, 6,8-DOBCO is a very common structural motif in many biologically active natural products. Not surprisingly, natural products containing 6,8-DOBCO framework have attracted much interest in the synthetic communities due to their potent and broad biological activities and unique complex structures. In chapter 1, the relevant methodologies of dichlorination and their applications in the total syntheses of polychlorosulfolipids were overviewed. Next a convenient method was developed for in situ generation of various active dichlorinating agents (c.f. Cl2, NCl3, Et4NCl3, ArICl2) from an environmentally friendly oxone and various cheap chloride sources. The counter ion of the chloride has a tremendous effect on generation of different dichlorinating species using oxone as the oxidant. The synthetic utility of this protocol was demonstrated by diastereoselective

Total syntheses of natural products is one of the most important subjects for chemical science. It is very useful for structural elucidation. Moreover, it could be used for the discovery of new methodology and applications of natural products to chemical biology and drug discovery. Polychlorinated compounds are unique and abundant natural products, which displayed potent antibiotic or cytotoxic activities. The big challenge for syntheses of these natural products is how to diastereoselective construct the vicinal dichlorinated functionalized groups. This thesis research deals with a convenient dichlorination method by in situ generation of various active dichlorinating agents from an environmentally friendly oxone and various cheap chloride sources, which may be exploited in synthesis of other chlorinated organic compounds. This thesis also deals with the total synthesis of natural products with 6,8-dioxabicyclo-[3.2.1]octane (6,8-DOBCO) framework by Achmatowicz rearrangement/bicycloketalization (AR/BCK) sequence. As one important kind of fused bicyclic acetals, 6,8-DOBCO is a very common structural motif in many biologically active natural products. Not surprisingly, natural products containing 6,8-DOBCO framework have attracted much interest in the synthetic communities due to their potent and broad biological activities and unique complex structures. In chapter 1, the relevant methodologies of dichlorination and their applications in the total syntheses of polychlorosulfolipids were overviewed. Next a convenient method was developed for in situ generation of various active dichlorinating agents (c.f. Cl2, NCl3, Et4NCl3, ArICl2) from an environmentally friendly oxone and various cheap chloride sources. The counter ion of the chloride has a tremendous effect on generation of different dichlorinating species using oxone as the oxidant. The synthetic utility of this protocol was demonstrated by diastereoselective

The exposure to persistent pollutants such as organochlorine compounds (OCs) or metals has been associated with declines in top predator populations, which can accumulate high amounts of these pollutants from their prey. However, understanding how variation in OC and metal accumulation in wild species affects their biochemical and physiological responses is a big challenge, especially for endangered predators like the Bonelli's eagle (Aquila fasciata). This bird of prey is an interesting study model because the differences in diet composition among populations and territories can account for important pollutant uptake variations. We compared OC and metal accumulation in blood of Bonelli's eagle nestlings from three populations across Spain as a function of origin, age class (nestlings vs. adults), sex and number of siblings per nest, and related accumulation patterns to responses indicative of body condition, biochemistry and antioxidant status. Nestlings from Catalonia, the most industrialized area, showed the highest concentrations of PCBs and arsenic, and the lowest concentrations of zinc. The two former substances, together with DDTs, exerted an overall influence on nestling's physiology. PCBs and arsenic were associated with reduced retinol levels, pointing to oxidative damage in exposed individuals, which was also consistent with the low zinc levels in individuals from the polluted region. Increased plasma DDT levels were related to reduced body condition and lower levels of triglycerides. Mercury accumulation in Castile and Leon was higher in nestlings that were alone in the nest than in nestlings that shared it with a sibling; this suggests an increased mercury uptake from secondary prey in territories where preferred prey (i.e. rabbits) are scarce, which are also the territories where productivity is reduced. Overall, the results reveal a spatial variation in pollutant accumulation patterns and associated physiological effects, and suggest the major role th

Environmental exposures need to be assessed for the understanding of the health risks of general population. Organochlorine compounds (OCs) from chlor-alkali plants (CAPs) are significant for the exposomes of individuals living in locations receiving their emissions and have to be determined. The aims of the study are to identify the area of influence of past and present OC emissions from CAPs and to set quantitative body burden estimates. A CAP situated in a rural area was selected for study. The geographic distribution of the atmospheric emissions was monitored using olive tree leaves. Human biomonitoring was assessed by serum analysis from general population (n= 1340). OC concentrations followed exponential decay functions with maxima in the immediate vicinity of the factory. The individuals living within 1. km exhibited hexachlorobenzene (HCB), polychlorobiphenyls (PCBs) and DDT-DDE (dichlorodiphenyltrichloroethane-dichlorodiphenyldichloroethylene) concentrations that were 12, 1.3-1.9 and 3.9 times higher than in sites not influenced by the emissions from this factory. Individuals from municipalities situated 15-25. km away from the CAP showed 1.5, 1.2-1.4 and 1.3 times higher serum HCB, PCB and DDT concentrations than in distant sites. The high serum concentrations of DDT and PCBs were observed even 23-31. years and 9-17. years after manufacture completion of these compounds, respectively. Our methodology provides a way for assessment of the influence of past and present atmospheric OCs emissions from CAPs into the exposome of individuals living in nearby areas.

In this report historical data are used to give insight into the trends in levels of organochlorine compounds in compound feeds and feeding materials for animals in the Netherlands. The main focus is on pesticides, but non-dioxin-like PCBs have been studied as well. The latter will be included in the trend analysis reports about dioxins and dioxin-like PCBs in the future. This analysis was performed on request of the NVWA (Netherlands Food and Consumer Product Safety Authority). The results of these analyses will enable the NVWA to develop a risk-directed sampling strategy for the National Feed Monitoring program. More than 5000 feed samples were analysed for organochlorine compounds in the period 2001-2011. The materials in these samples originate from all over the world, but were sampled in the Netherlands. Samples were taken by the NVWA for the Netherlands National Feed Monitoring program and by the feed industry.

Aquest estudi resumeix els avenços en el coneixement dels trastorns de salut associats a l’exposició fetal a compostos organoclorats en una cohort de nens de Menorca. S’ha observat una incidència major de diversos efectes perjudicials per la salut als 4 anys d’edat, per exemple, hexaclorobenzè (HCB) i comportament social pobre i trastorn per dèficit d’atenció amb hiperactivitat, 4,4’- DDE i asma, xiulets pulmonars, infeccions de les vies respiratòries baixes i alteració de coproporfirines urinàries, HCB, ß-hexaclorociclohexà i 4,4’-DDE i alteració de les hormones tiroïdals, HCB, 4,4’-DDE i policlorobifenils (PCBs) i sobrepès, 4,4’-DDT i PCBs i menor desenvolupament neurològic. També s’ha documentat un efecte protector de la lactància materna contra la disminució de les habilitats cognitives dels nens a causa de l’exposició a 4,4’-DDT. Aquest efecte protector mostra que altres factors, a més de l’exposició a contaminants i genètica personal, influeixen en els efectes de salut dels contaminants ambientals en les poblacions humanes. Aquests resultats són importants per comprendre les implicacions per la salut dels estudis d’exposomes., The present study summarizes the advances on the knowledge of the health disturbances associated to fetal exposure to organochlorine compounds in a cohort of children from Menorca. Higher incidence of diverse deleterious health effects at 4 years of age have been observed, e.g. hexachlorobenzene (HCB) and poor social behavior and attention-deficit hyperactivity disorder, 4,4’-DDE and asthma, wheeze, lower respiratory tract infections and alteration of urinary coproporphyrins, HCB, ß-hexachlorocyclohexane and 4,4’-DDE and alteration of thyroid hormones, HCB, 4,4’-DDE and polychlorobiphenyls (PCBs) and overweight, 4,4’-DDT and PCBs and lower neurodevelopment. A protective effect of breastfeeding against decreases of cognitive skills in children due to 4,4’-DDT exposure has also been documented. This protective effect shows that other factors besides pollutant exposure and genetic variability influence on the health effects of environmental pollutants into human populations. These results are important for the understanding of the health implications of exposome studies.

Environmental exposures need to be assessed for the understanding of the health risks of general population. Organochlorine compounds (OCs) from chlor-alkali plants (CAPs) are significant for the exposomes of individuals living in locations receiving their emissions and have to be determined. The aims of the study are to identify the area of influence of past and present OC emissions from CAPs and to set quantitative body burden estimates. A CAP situated in a rural area was selected for study. The geographic distribution of the atmospheric emissions was monitored using olive tree leaves. Human biomonitoring was assessed by serum analysis from general population (n = 1340). DC concentrations followed exponential decay functions with maxima in the immediate vicinity of the factory. The individuals living within 1 km exhibited hexachlorobenzene (HCB), polychlorobiphenyls (PCBs) and DDT-DDE (dichlorodiphenyltrichloroethane-dichlorodiphenyldichloroethylene) concentrations that were 12, 1.3-1.9 and 3.9 times higher than in sites not influenced by the emissions from this factory. Individuals from municipalities situated 15-25 km away from the CAP showed 1.5, 12-1.4 and 1.3 times higher serum HCB. PCB and DDT concentrations than in distant sites. The high serum concentrations of DDT and PCBs were observed even 23-31 years and 9-17 years after manufacture completion of these compounds, respectively. Our methodology provides a way for assessment of the influence of past and present atmospheric OCs emissions from CAPs into the exposome of individuals living in nearby areas., AuthorCount:4

PCB and DDT levels were evaluated in populations of endemic Iberian barbel (. Barbus bocagei) in the Jarama River in Spain via a pollution gradient from well-preserved areas upstream to contaminated downstream areas. Age structure, abundance, recruitment and levels of morphological abnormalities and ectoparasites were assessed. Upstream to downstream PCB concentrations ranged from 3.4 to 101.4. ng/g (ww) and from 0.9 to 19.6. ng/g ww for DDTs. The PCB pattern was dominated by the PCB 153, 138 and 180 congeners, and the less chlorinated ones had a relatively high contribution upstream.Barbels exposed to low PCB and DDT levels had a well-balanced population with a predominant cohort of young fish, indicating good recruitment. The most contaminated sites displayed a disrupted age distribution, where the proportion of young fish was clearly under-represented. Recruitment and total density of barbel populations decreased downstream where the highest PCB and DDT levels were found. In addition, a higher incidence of abnormalities and ectoparasites was observed at these sites. High concentrations of PCBs and DDTs most likely contribute to the reduction of Iberian barbel reproductive performance in the most contaminated sites, as shown by the disrupted age-distribution found in our study. © 2014 Elsevier B.V.

Thousands of potentially toxic chemical substances are introduced into the oceans every day. Even following decades of research and monitoring there is still a limited understanding of their effects on marine organisms and ecosystems. A complicating factor is the general lack of a direct relationship between elevated concentrations of contaminants in the tissues of marine organisms and effects. In addition, some biological responses have been shown to occur even at very low contaminant concentrations. A development and deployment of biological effects measurements (biomarkers and bioassays) along with analytical chemistry has increasingly been used as early warning signals of adverse environmental change in marine ecosystems. Contaminant-related biomarker responses include physiological or biochemical responses in organisms exposed to certain class of contaminants. Biomarker responses in fish from natural populations appear to be more sensitive than other methods, as they provide integrated information about contaminant exposure and effects as well as indicate acute pollution incidences. In vivo and in vitro bioassays contribute to our understanding of how pollutants affect living organisms but can also aid in deducing general mechanisms of action, to aid in categorization and overall assessment of effects. Fish is the most diverse class of vertebrates and can bridge human and ecological health in ecotoxicology studies. Benthic fish are suitable organisms for marine chemical pollution studies and the assessment of its health is it is not only an issue of conservation ecology but has clear links to utilisation of marine resources and human health. The main aims of this thesis were to clarify sublethal effects of environmental chemical contaminants on biological responses in three benthic fish species (Lepidorhombus boscii, Callionymus lyra and Mullus barbatus) from Spanish marine areas as well as to develop the use of contaminant-related biological responses in fish

En aquest projecte s’ha desenvolupat i validat un programa de MatLab per determinar l’eliminació de compostos volàtils en l’aire mitjançant carbó actiu. El programa (Active Carbon SATuration, Acsat) s’ha aplicat a aire provinent de tractaments d’aigua subterrània, com són air sparging, bombeig i tractament d’air stripping i extracció de vapors del sòl., mitjançant carbó actiu. A mesura que s’ha anat creant el programa s’ha validat amb un model lineal de transports de contaminants i un model binari que considera la cinètica. Els models s’han validat per mitjà d’exemple en articles i comparant aquest entre ells incloent una sèrie d’hipòtesis. S’han modelitzat diversos paràmetres d’un flux d’aire amb diverses concentracions de mescles binàries dels contaminants volàtils per estudiar la seva evolució un cop travessat el llit de carbó actiu i establir la sensibilitat dels temps de ruptura i la concentració màxima. El programa elaborat ha permès determinar la corba de ruptura de diversos volàtils quan es produeix la saturació del carbó actiu en una columna i el senyal de sortida d’ un detector PID del corrent efluent respecte el percentatge de senyal PID del corrent influent per conèixer el moment aproximat de regenerar el carbó actiu. El projecte forma una part d’un projecte emmarcat dins del projecte europeu anomenat SmartStripping. En el present projecte s’ha elaborat un manual del programa. Paral·lelament, també s’ha realitzat l’estudi experimental d’equilibri de vapors saturats d’alguns compostos volàtils (tetracloroetilè, percloroetilè, 1-2-dicloroetà i 1,1,2- tricloroetà) amb carbó actiu per determinar l’adsorció màxima. El projecte conté una part experimental per estudiar l’equilibri de vapors saturats procedents de 4 compostos volàtils utilitzant la tècnica de termogravimetria (TGA) i la determinació certs paràmetres del carbó actiu, com són la determinació de la densitat de bulk, densitat de partícula i la porositat del carbó actiu.

Organochlorine pesticides (OCPs) are persistent in the environments and have the ability to bioaccumulate in the food chain and are capable of causing various health hazards. The sample preparation techniques used for monitoring of OCPs in food are usually complicated, time consuming, use large volume of solvents and expensive. An ideal multi-residue method with high recoveries should be rapid, easy to perform, accurate, low cost and safer to the analyst due to less exposure to organic solvent and waste. The Quick Easy Cheap Effective Rugged and Safe (QuEChERS) is one of such methods. The objectives of this study are to evaluate the effectiveness of dispersive solid phase extraction (DSPE) sorbents in removing matrix interferences in Pacific white shrimp, to validate the most effective sorbent using the QuEChERS method and compare to the modified AOAC Official method 983.21. Thus, the QuEChERS sample preparation method DSPE and gas chromatography mass spectrometry (GC-MS) with selected ion monitoring mode (SIM) has been improved and applied for the analysis of common OCPs (α-HCH, β-HCH, γ-HCH, δ-HCH, trans-chlordane, cis-chlordane, p,p’-DDE, p,p’-DDD and p,p’-DDT) in Pacific white shrimp (Litopenaeus vannamei). The combination of primary and secondary amine (PSA), octadecyl (C18) and/or graphitized carbon black (GCB) have been evaluated as clean-up sorbents to samples collected from the state of Kedah, Selangor and Terengganu. Sampling was conducted twice a year between February - June and July - November 2011 at two selected farms from each state. The results have shown the mean recoveries for PSA:C18, PSA:GCB and PSA:C18:GCB ranged between 93–100%, 98-105% and 98-105%, respectively. The relative standard deviations (RSD) of <14%, <15% and <10% were obtained for PSA:C18, PSA:GCB and PSA:C18: GCB, respectively. The PSA:C18 was not able to remove matrix interference, such as cholesterol. The sorbent efficiency to minimize matrix interferences was PSA:C18:GCB > PSA:GC

Introduction. Contamination due to organochlorine pesticides on food is considered as a serious threat for human health, given their high toxicity, bioaccumulation and persistence. Cow milk is used as an indicator of the persistence of these pesticides in the environment, because of the milk Ls importance and, in general, of the role of dairy products, especially for children. This has been a reason to study pasteurized milk from Colombia and compare the results with previous research works in other countries. Objective. To determine the remains of organochlorine pesticides contained in liquid pasteurized milk sold by stores located near to pasteurization plants in Cartagena. Materials and methods. 24 bags of milk, from randomly chosen commercial brands and daily provided, were analyzed. The analytic technique of gas chromatography with detector of micro electrons capture was used to determine the content of organochlorine insecticides. Results. For this research work the remains of ¿-chlordane (0,90 mg/kg), À-chlordane (0,12 mg/kg), endosulfan I (0,04 mg/kg), endosulfan II (0,001 mg/kg), endosulfansulphate (0,002 mg/kg), p,pf-DDT (not detected) p,pf-DDE (0,01 mg/kg), p,pf-DDD (0,01 mg/kg), endrin (0,027 mg/kg), endrinketone (0,042 mg/kg) and endrin aldehyde (0,009 mg/kg) were determined. Conclusion. The research work concluded that some concentrations of the pesticides analyzed were high when their values were compared to those recommended by FAO/WHO in their maximum residual levels (MRL)., Introducao. A contaminacao por residuos de pesticidas organoclorados nos alimentos se considera uma seria ameaca para a saude humana pela alta toxicidade, bio-acumulacao e persistencia. O leite de vaca se utiliza como um indicador da persistencia dos pesticidas organoclorados no meio-ambiente, devido a importancia da mesma e, em general, dos produtos lacteos na nutricao humana, especialmente nos meninos. O anterior motivou a realizar um estudo no leite pasteurizada de Colombia e comparar seus resultados com investigacoes anteriores, em outros paises. Objetivo. Determinar os residuos de pesticidas organoclorados em leite de vaca, liquida pasteurizada, vendida em lojas proximas a pasteurizadores da cidade de Cartagena. Materiais e metodos. Analisaram-se 24 bolsas de leite, com fornecimento diario de duas marcas comerciais tomadas a esmo. Foi utilizada a tecnica analitica de cromatografia de gases com detector de captura de micro electrones, para determinar o conteudo de inseticidas organoclorados. Resultados. Nesta investigacao foram determinados os residuos de ¿-clordano (0,90 mg/kg), À-clordano (0,12 mg/kg), endosulfan I (0,04 mg/kg), endosulfan II (0,001 mg/kg), endosulfan sulfato (0,002 mg/kg), p,pf-DDT (nao detectado), p,pf-DDE (0,01 mg/kg), p f-DDD (0,01 mg/ kg), endrin (0,027 mg/kg), endrin cetona (0,042 mg/kg) e endrin aldehido (0,009 mg/kg). Conclusao. O estudo concluiu que algumas concentracoes dos pesticidas analisados foram elevadas ao contrastar-se seus valores com os limites maximos residuais (LMR) recomendados pela Organizacao das Nacoes Unidas para a Agricultura e a Alimentacao/Organizacao Mundial da Saude (FAO/OMS)., Introducción. La contaminación por residuos de plaguicidas organoclorados en los alimentos se considera una seria amenaza para la salud humana por la alta toxicidad, bioacumulación y persistencia. La leche de vaca se utiliza como un indicador de la persistencia de los plaguicidas organoclorados en el medio ambiente, debido a la importancia de la misma y, en general, de los productos lácteos en la nutrición humana, especialmente en los niños. Lo anterior ha motivado a realizar un estudio en la leche pasteurizada de Colombia y comparar sus resultados con investigaciones anteriores, en otros países. Objetivo. Determinar los residuos de plaguicidas organoclorados en leche de vaca, liquida pasteurizada, vendida en tiendas cercanas a pasteurizadoras de la ciudad de Cartagena. Materiales y metodos. Se analizaron 24 bolsas de leche, con suministro diario de dos marcas comerciales tomadas al azar. Fue utilizada la tecnica analitica de cromatografia de gases con detector de captura de microelectrones, para determinar el contenido de insecticidas organoclorados. Resultados. En esta investigacion fueron determinados los residuos de ¿-clordano (0,90 mg/kg), À-clordano (0,12 mg/kg), endosulfan I (0,04 mg/kg), endosulfan II (0,001 mg/kg), endosulfan sulfato (0,002 mg/kg), p,pf-DDT (no detectado), p,pf-DDE (0,01 mg/kg), p,pf-DDD (0,01 mg/kg), endrin (0,027 mg/kg), endrin cetona (0,042 mg/kg) y endrin aldehido (0,009 mg/kg). Conclusion. El estudio concluyo que algunas concentraciones de los plaguicidas analizados fueron elevadas al contrastarse sus valores con los limites maximos residuales (LMR) recomendados por la Organizacion de las Naciones Unidas para la Agricultura y la Alimentacion/Organizacion Mundial de la Salud (FAO/OMS).

Introduction. Contamination due to organochlorine pesticides on food is considered as a serious threat for human health, given their high toxicity, bioaccumulation and persistence. Cow milk is used as an indicator of the persistence of these pesticides in the environment, because of the milk Ls importance and, in general, of the role of dairy products, especially for children. This has been a reason to study pasteurized milk from Colombia and compare the results with previous research works in other countries. Objective. To determine the remains of organochlorine pesticides contained in liquid pasteurized milk sold by stores located near to pasteurization plants in Cartagena. Materials and methods. 24 bags of milk, from randomly chosen commercial brands and daily provided, were analyzed. The analytic technique of gas chromatography with detector of micro electrons capture was used to determine the content of organochlorine insecticides. Results. For this research work the remains of ¿-chlordane (0,90 mg/kg), À-chlordane (0,12 mg/kg), endosulfan I (0,04 mg/kg), endosulfan II (0,001 mg/kg), endosulfansulphate (0,002 mg/kg), p,pf-DDT (not detected) p,pf-DDE (0,01 mg/kg), p,pf-DDD (0,01 mg/kg), endrin (0,027 mg/kg), endrinketone (0,042 mg/kg) and endrin aldehyde (0,009 mg/kg) were determined. Conclusion. The research work concluded that some concentrations of the pesticides analyzed were high when their values were compared to those recommended by FAO/WHO in their maximum residual levels (MRL)., Introducao. A contaminacao por residuos de pesticidas organoclorados nos alimentos se considera uma seria ameaca para a saude humana pela alta toxicidade, bio-acumulacao e persistencia. O leite de vaca se utiliza como um indicador da persistencia dos pesticidas organoclorados no meio-ambiente, devido a importancia da mesma e, em general, dos produtos lacteos na nutricao humana, especialmente nos meninos. O anterior motivou a realizar um estudo no leite pasteurizada de Colombia e comparar seus resultados com investigacoes anteriores, em outros paises. Objetivo. Determinar os residuos de pesticidas organoclorados em leite de vaca, liquida pasteurizada, vendida em lojas proximas a pasteurizadores da cidade de Cartagena. Materiais e metodos. Analisaram-se 24 bolsas de leite, com fornecimento diario de duas marcas comerciais tomadas a esmo. Foi utilizada a tecnica analitica de cromatografia de gases com detector de captura de micro electrones, para determinar o conteudo de inseticidas organoclorados. Resultados. Nesta investigacao foram determinados os residuos de ¿-clordano (0,90 mg/kg), À-clordano (0,12 mg/kg), endosulfan I (0,04 mg/kg), endosulfan II (0,001 mg/kg), endosulfan sulfato (0,002 mg/kg), p,pf-DDT (nao detectado), p,pf-DDE (0,01 mg/kg), p f-DDD (0,01 mg/ kg), endrin (0,027 mg/kg), endrin cetona (0,042 mg/kg) e endrin aldehido (0,009 mg/kg). Conclusao. O estudo concluiu que algumas concentracoes dos pesticidas analisados foram elevadas ao contrastar-se seus valores com os limites maximos residuais (LMR) recomendados pela Organizacao das Nacoes Unidas para a Agricultura e a Alimentacao/Organizacao Mundial da Saude (FAO/OMS)., Introducción. La contaminación por residuos de plaguicidas organoclorados en los alimentos se considera una seria amenaza para la salud humana por la alta toxicidad, bioacumulación y persistencia. La leche de vaca se utiliza como un indicador de la persistencia de los plaguicidas organoclorados en el medio ambiente, debido a la importancia de la misma y, en general, de los productos lácteos en la nutrición humana, especialmente en los niños. Lo anterior ha motivado a realizar un estudio en la leche pasteurizada de Colombia y comparar sus resultados con investigaciones anteriores, en otros países. Objetivo. Determinar los residuos de plaguicidas organoclorados en leche de vaca, liquida pasteurizada, vendida en tiendas cercanas a pasteurizadoras de la ciudad de Cartagena. Materiales y metodos. Se analizaron 24 bolsas de leche, con suministro diario de dos marcas comerciales tomadas al azar. Fue utilizada la tecnica analitica de cromatografia de gases con detector de captura de microelectrones, para determinar el contenido de insecticidas organoclorados. Resultados. En esta investigacion fueron determinados los residuos de ¿-clordano (0,90 mg/kg), À-clordano (0,12 mg/kg), endosulfan I (0,04 mg/kg), endosulfan II (0,001 mg/kg), endosulfan sulfato (0,002 mg/kg), p,pf-DDT (no detectado), p,pf-DDE (0,01 mg/kg), p,pf-DDD (0,01 mg/kg), endrin (0,027 mg/kg), endrin cetona (0,042 mg/kg) y endrin aldehido (0,009 mg/kg). Conclusion. El estudio concluyo que algunas concentraciones de los plaguicidas analizados fueron elevadas al contrastarse sus valores con los limites maximos residuales (LMR) recomendados por la Organizacion de las Naciones Unidas para la Agricultura y la Alimentacion/Organizacion Mundial de la Salud (FAO/OMS).

In 2003 is ten behoeve van het ministerie van Landbouw, Natuur en Voedselkwaliteit (LNV) programma 378, “Bewaking van de kwaliteit en veiligheid van land-, tuinbouw- en visserijproducten” (momenteel programma 438, gecoördineerd door het RIKILT Instituut voor Voedselveiligheid), opgestart waarbij als onderdeel van dit programma jaarlijks gehalten van organische microverontreinigingen in kabeljauw- en heeklever worden gemeten. Dit deelonderzoek is uitgevoerd naar polychloorbifenylen (PCBs), organochloor pesticiden (OCPs) en toxafeen.

The biomarker of xenobiotic exposure cytochrome p450A1 (Cyp1A) was used to analyze the biological response to chemical pollution in Salmo trutta (brown trout) from nine high mountain European lakes in Norway, Tatras, Tyrol, and central Pyrenees. Hepatic Cyp1A mRNA levels correlated both with the reciprocal of absolute annual average air temperatures of the sampled lakes and with muscle concentrations of several hydrophobic organohalogen compounds (OC), including chlorinated polychlorobiphenyls (PCB), DDE, and DDT. The correlation between Cyp1A expression and OC content was observed across the whole temperature range (between 0.7 C and þ6.2 C), but also in the absence of any thermal gradient. We concluded that airborne pollutants accumulate in high mountain lake fish at concentrations high enough to increase Cyp1A expression, among other possible effects. As geographical distribution of semi-volatile OC is strongly influenced by air temperatures, future climate modifications will potentially enhance their physiological effects in lake ecosystems.

A method for the calculation of the limits of detection (LD) and quantification (LQ) for the analysis of organochlorine compounds in serum is described. The method is based on the analysis of proficiency testing materials, an external quality assessment for selected pollutants, and the study of the signal/noise ratio of chromatograms obtained from GC-ECD injection. This method provides representative results for matrix effects, instrumental variability and extraction recoveries in the analysis of serum samples.

Blood biomarkers and levels of major pollutants in eggs and feathers were used to determine pollution effects in nestlings of the Purple Heron Ardea purpurea and the Little Egret Egretta garzetta, sampled on three Ebro River (NE Spain) areas: a reference site, a site affected by the effluents of a chlor-alkali industry and the river Delta. The two impacted heron populations showed mutually different pollutant and response patterns, suggesting different sources of contamination. In the population nesting near the chlor-alkali plant, elevated levels of hexachlorobenzene (HCB) and polychlorobiphenyls (PCBs) in eggs, and mercury in feathers in A. purpurea chicks were related with reduced blood antioxidant defenses and increased levels of micronuclei. In Ebro Delta, high levels of plasmatic lactate dehydrogenase in A. purpurea chicks and high frequency of micronuclei in blood of both species were tentatively associated with intensive agricultural activities taking place in the area. These results provide the first evidence of a biological response in heron chicks to the release of pollutants at a chlor-alkali plant. High levels of organochlorine and mercury levels in eggs and feathers were related with altered blood biomarkers of heron nesting chicks

El término calentamiento global identifi ca el aumento generalizado de la temperatura en la superfi cie de la tierra desde la época de la Revolución Industrial y que se acentuó a partir de 1950, debido a la presencia de gran cantidad de gases con efecto invernadero en la atmósfera, la mayoría, producidos por el hombre. Una de las más graves consecuencias de este fenómeno es el aumento en el nivel del mar debido al deshielo de los glaciares y al descongelamiento en los polos, situación que afecta principalmente las poblaciones costeras. Para disminuir este calentamiento, 169 países fi rmaron el Protocolo de Kyoto, un compromiso para reducir un promedio de 5.2% en las emisiones de gases con efecto invernadero que resultan de las actividades antropogénicas, tomando como base los niveles existentes en 1990, Los científi cos no se han puesto de acuerdo acerca de la causa específi ca del calentamiento global. De cualquier forma, sea cual sea la fuente del calentamiento, es necesario que tengamos muy en cuenta que el efecto invernadero contribuye al calentamiento de la superfi cie de la tierra en un gran porcentaje. Desde ese punto de vista, el hombre debe reducir las emisiones de los gases responsables del efecto invernadero, actividad que, si no detiene el calentamiento, por lo menos lo mitiga. Cada uno de nosotros podemos contribuir a esa causa, aunque sea modestamente. Recuerde que 6.000 millones de personas vivimos en este planeta., The global warming term defi nes the general increase in the average temperature of the Earth surface which began with the Industrial Revolution period and got stronger since 1950, because of the green house gasses concentration in the atmosphere, most of them produced by human activities. One of the most severe consequences of this phenomenon is a signifi cant increase in the level sea due to the defrosting of glaciers and ice in North and South Poles, which affect cities located on shore. In order to reduce the Earth warming, the Protocol of Kyoto was signed by 169 countries with the commitment to reduce the emission of green house gasses produced by anthropogenic activities, in an average of 5.2% in comparing the fi gure with the existing levels in 1990. We must take in account that the green house effect contributes to the warming of Earth surface in a high percentage, no matter the source of heating.From this point of view, the man must be aware about the importance of reducing the emissions of gasses responsible for green house effect .This activity will not stop the global warming, but at least it will mitigate it. We can modestly contribute to achieve this goal. Remember that 6.000 millions of people are living in this planet.

El término calentamiento global identifi ca el aumento generalizado de la temperatura en la superfi cie de la tierra desde la época de la Revolución Industrial y que se acentuó a partir de 1950, debido a la presencia de gran cantidad de gases con efecto invernadero en la atmósfera, la mayoría, producidos por el hombre. Una de las más graves consecuencias de este fenómeno es el aumento en el nivel del mar debido al deshielo de los glaciares y al descongelamiento en los polos, situación que afecta principalmente las poblaciones costeras. Para disminuir este calentamiento, 169 países fi rmaron el Protocolo de Kyoto, un compromiso para reducir un promedio de 5.2% en las emisiones de gases con efecto invernadero que resultan de las actividades antropogénicas, tomando como base los niveles existentes en 1990, Los científi cos no se han puesto de acuerdo acerca de la causa específi ca del calentamiento global. De cualquier forma, sea cual sea la fuente del calentamiento, es necesario que tengamos muy en cuenta que el efecto invernadero contribuye al calentamiento de la superfi cie de la tierra en un gran porcentaje. Desde ese punto de vista, el hombre debe reducir las emisiones de los gases responsables del efecto invernadero, actividad que, si no detiene el calentamiento, por lo menos lo mitiga. Cada uno de nosotros podemos contribuir a esa causa, aunque sea modestamente. Recuerde que 6.000 millones de personas vivimos en este planeta., The global warming term defi nes the general increase in the average temperature of the Earth surface which began with the Industrial Revolution period and got stronger since 1950, because of the green house gasses concentration in the atmosphere, most of them produced by human activities. One of the most severe consequences of this phenomenon is a signifi cant increase in the level sea due to the defrosting of glaciers and ice in North and South Poles, which affect cities located on shore. In order to reduce the Earth warming, the Protocol of Kyoto was signed by 169 countries with the commitment to reduce the emission of green house gasses produced by anthropogenic activities, in an average of 5.2% in comparing the fi gure with the existing levels in 1990. We must take in account that the green house effect contributes to the warming of Earth surface in a high percentage, no matter the source of heating.From this point of view, the man must be aware about the importance of reducing the emissions of gasses responsible for green house effect .This activity will not stop the global warming, but at least it will mitigate it. We can modestly contribute to achieve this goal. Remember that 6.000 millions of people are living in this planet.

Prirodna organska materija zemljišta/sedimenata predstavlja glavnu oblast za sorpciju hidrofobnih organskih jedinjenja, a njene osobine utiču na stepen retencije i konsekventnu (bio)dostupnost organskih jedinjenja. Da bi se procenio ekotoksikološki rizik zagađenih zemljišta/sedimenata po okolinu, dizajnirala odgovarajuća strategija remedijacije ili predvidela sudbina i transport organskih polutanata u zagađenim zonama, neophodno je razumevanje mehanizma sorpcije i desorpcije na nivou mehanizma uspostavljenih veza. U radu je izvršeno ispitivanje sorpcije i desorpcije odabranih hidrofobnih organskih polutanata, pentahlorbenzena i lindana, na sekvencijalno ekstrahovanim huminskim kiselinama i huminima iz jednog uzorka sedimenta u cilju pronalaženja veze između strukturnih karakteristika izolovanih huminskih kiselina i humina i sorpcionih i desorpcionih parametara. Afinitet za sorpciju, nelinearnost izotermi i prividna sorpciono-desorpciona histereza korelirani su sa osobinama sorbenata dobijenim iz elementarne i FTIR spektroskopske analize. Predloženo je da je mehanizam sorpcije na huminskim kiselinama rezultat odigravanja raspodele i specifične adsorpcije, pri čemu se pri nižim koncentracijama pentahlorbenzena i lindana prvo popune sorpciona mesta u kondenzovanoj aromatičnoj oblasti, a tek potom pri višim koncentracijama sorpciona mesta u amorfnim alifatičnim oblastima. Sveukupno viši koeficijenti nelinearnosti dobijeni za sorpciju pentahlorbenzena na huminskim kiselinama u odnosu na nelinearnost sorpcionih izotermi lindana, ukazuju na to da u ukupnoj sorpciji pentahlorbenzena veći značaj ima mehanizam raspodele i smeštanje molekula pentahlorbenzena u hidrofobne šupljine huminskih kiselina, u odnosu na specifičnu adsorpciju. Ovi zaključci su potvrđeni rezultatima spektroskopskih istraživanja interakcija odabranih organskih jedinjenja i N-metilformamida. Predloženi mehanizam sorpcije ne može objasniti sorpciju pentahlorbenzena i lindana na uzorcima humina, većje pret, Natural organic matter of soil/sediment make the main region for sorption of hydrophobic organic compounds, ant its properties influence the degree of retention and, consequently, (bio)availability of organic compounds. In order to assess the ecotoxicological risks of contaminated soils/sediments to the environment and design the appropriate remediation strategy or predict the fate and transport of organic pollutants in contaminated zones, it is necessary to understand the mechanisms of sorption/desorption at the level of the mechanism of established bonds. Study of the sorption and desorption of selected hydrophobic organic pollutants, pentachlorobenzene and lindane, on sequentially extracted humic acids and humins from a single sediment sample with the aim of finding the relationship between the structural characteristics of the isolated humic acids and humin and sorption and desorption parameters. Sorption affinity, nonlinearity of isotherms, and apparent sorption-desorption hysteresis were correlated to the sorbent characteristics obtained from elemental analysis and FTIR spectroscopic data. The proposed sorption mechanism on humic acids assumes that at low concentrations of pentachlorobenzene and lindane the sorption sites in the condensed aromatic region are occupied first, and then, at their higher concentrations, the sorption sites in the amorphous and aliphatic regions. Generally higher nonlinearity coefficient obtained for the sorption of pentachlorobenzene on umic acids compared with the nonlinearity of sorption isotherms for lindane, indicate that in the overall sorption of pentachlorobenzene of higher significance is the echanism of distribution and insertion of pentachlorobenzene molecule into hydrophobic dips of humic acids, compared to specific adsorption. These conclusions were confirmed with the results of spectroscopic investigation of intermolecular interaction of chosen organic compounds and N-methylformamide.Since suggested sorption mechanis

In het jaar 2006 zijn op 14 locaties in watersystemen van de Nederlandse rijkswateren monsters rode aal verzameld. In de filets zijn analyses uitgevoerd van kwik, PCB’s en een aantal andere prioritaire organochloorverbindingen . Voor de betreffende locaties is een trendanalyse voor de diverse microcontaminanten uitgevoerd en een risicoanalyse gedaan voor doorvergiftiging van visetende hogere organismen

A study of intake of organochlorine compounds (OCs) in children both in utero and at the age of four years has been performed in two cohorts. One encompasses children born in Menorca Island between 1997 and 1998, and the other those born between 1997–1999 in Ribera d’Ebre, an in-land industrial–agricultural area of Catalonia. Comparison of the OC concentrations in serum samples from both populations, including those obtained from cord blood and blood collected at four years, provides information on the influence of local pollution sources in the accumulation of these compounds. Statistically significant differences (p < 0.01) have been found for hexachlorobenzene, indicating that chronic airborne contamination to this compound in Ribera d’Ebre involved higher in utero exposure, which increased in the first four years of growth. Similarly, in the cohort of Menorca, higher in utero exposure to PCBs was observed and this increased subsequently in the first four years of growth. Other compounds encompassing temporal contamination episodes such as g-HCH involved higher in utero exposure but strongly diminished in the first four years of growth. Overall, it can be concluded that local chronic pollution by OCs has a direct effect in children living in the surrounding areas. This influence is reflected in higher exposure, both in utero and in the first years of growth, that significantly stands out over the background contamination due to the ubiquity of these compounds.

Fish from Dutch markets were analysed for concentrations of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) and compared with the new European maximum residue levels (MRLs), set in 2006. In a first study on 11 different fish and shellfish from various locations, concentrations of PCDD/Fs were nearly all below the MRL for PCDD/Fs [4 pg toxic equivalents (TEQ) per gram wet weight (ww)] and nearly all below 8 pg total TEQ/g ww, the new MRL for the sum of PCDD/Fs and DL-PCBs. Some samples exceeded the total TEQ MRL, such as anchovy, tuna and sea bass. Furthermore, 20 (out of 39) wild eel samples exceeded the specific MRL for eel (12 pg total TEQ/g ww), as the study revealed PCDD/F TEQ levels of 0.2-7.9 pg TEQ/g ww and total TEQ values of 0.9 to 52 pg/g ww. TEQ levels in farmed and imported eel were lower and complied with the MRLs. Smoking eel, a popular tradition in the Netherlands, only had marginal effects on PCDD/F and DL-PCB concentrations. Owing to volatilization, concentrations of lower-chlorinated PCBs were reduced to below the limit of quantification after smoking. DL-PCBs contributed 61-97% to the total TEQ in all eel samples. This also holds for other fish and shellfish (except shrimps): DL-PCB contributed (on average) from 53 (herring) to 83% (tuna) to the total TEQ. Principal-component analysis revealed distinctive congener profiles for PCDD/Fs and non-ortho PCBs for mussels, pikeperch, herring and various Mediterranean fish. The application of new TCDD toxic equivalency factors (TEFs) set by the World Health Organization in 2006 (to replace the 1997 TEFs) resulted in lower TEQ values, mainly owing to a decreased mono-ortho PCB contribution. This decrease is most pronounced for eel, owing to the relative high mono-ortho PCB concentrations in eel. Consequently, a larger number of samples would comply with the MRLs when the new TEFs are applied. The DR CALUX (R) assay may be used for screening tota

A study of intake of organochlorine compounds (OCs) in children both in utero and at the age of four years has been performed in two cohorts. One encompasses children born in Menorca Island between 1997 and 1998, and the other those born between 1997–1999 in Ribera d’Ebre, an in-land industrial–agricultural area of Catalonia. Comparison of the OC concentrations in serum samples from both populations, including those obtained from cord blood and blood collected at four years, provides information on the influence of local pollution sources in the accumulation of these compounds. Statistically significant differences (p < 0.01) have been found for hexachlorobenzene, indicating that chronic airborne contamination to this compound in Ribera d’Ebre involved higher in utero exposure, which increased in the first four years of growth. Similarly, in the cohort of Menorca, higher in utero exposure to PCBs was observed and this increased subsequently in the first four years of growth. Other compounds encompassing temporal contamination episodes such as g-HCH involved higher in utero exposure but strongly diminished in the first four years of growth. Overall, it can be concluded that local chronic pollution by OCs has a direct effect in children living in the surrounding areas. This influence is reflected in higher exposure, both in utero and in the first years of growth, that significantly stands out over the background contamination due to the ubiquity of these compounds.

Fish muscle extracts from ten European mountain lakes were analyzed for organochlorine compounds (OCs) and estrogenic activity, the latter by a recombinant yeast assay based on the human estrogen receptor. Seventy percent of the samples showed estrogenic activity above detection limits and a subset of five samples showed estrogenic activities, equivalent to more than 10,000 pg/g of estradiol. These highly estrogenic samples occurred in two lakes, Velké Hinçovo in the Tatra Mountains and Redon in the Pyrenees. Principal component analysis correlated estrogenic activity of muscle extracts to fish age and concentrations of the more chlorinated polychlorobiphenyls (PCBs). This is consistent with previously observed correlations of these PCBs with fish age. In addition, most fish with high estrogenic activity were found in lakes containing high OC levels in the sediments, which gives further ground to atmospheric deposition of anthropogenic pollutants as main process leading to the observed endocrine disruption effects., Estrogen receptor agonists in lake fish are correlated with organochlorine compound content.

The frequency of micronuclei (MN) in peripheral erythrocytes was tested for 59 heron nestlings (Ardea purpurea, Egretta garzetta and Bubulcus ibis) sampled at two areas (polluted and reference) on the River Ebro (NE Spain) and at its Delta during Spring 2006. Flow-cytometry analysis revealed higher (three- to six-fold) MN counts in samples from the most polluted site relative to samples from the reference area. Samples from the Delta showed intermediate values. Age, morphometric parameters (weight, tarsus size and bill-head length) and maturation status showed no significant differences among the different populations for each species; nor were they correlated with MN levels. The data suggest that elevated levels of MN in chicks in impacted areas reflected the chemical pollution of their nesting sites. The use of nestlings for this assay appears to be a convenient, non-destructive method to assess the impact of pollution in natural bird populations., Frequency of micronucleated erythrocytes in peripheral blood of waterbird nestlings correlates with chemical pollution loads in their nesting sites.

In het jaar 2005 zijn op 14 locaties in watersystemen van de Nederlandse rijkswateren monsters rode aal verzameld. Analyses zijn uitgevoerd voor kwik, PCB’s en een aantal andere prioritaire organochloorverbindingen. Beschreven wordt wat opvalt in vergelijking met de voorgaande jaren vanaf 2001.

A multivariate statistical data analysis, using principal component analysis, of historical data from 1996 to 2003 concerning the concentration of different polycyclic aromatic hydrocarbons and organochlorine compounds in sediment samples from different sampling sites of the Ebro River Basin was performed under the UE funded project AQUATERRA. Three major contamination sources were identified and their composition and distribution profiles were resolved. The first contamination profile was mostly loaded by polycyclic aromatic hydrocarbons, the second contamination profile was loaded by some organochlorine compounds and the third contamination profile was more specifically loaded by naphthalene. Samples from the different geographical regions of the Ebro River Basin were grouped according to the contamination described by these three major profiles.

Volatile organochlorine compounds emitted from natural sources can participate in environmentally relevant processes affecting life on Earth, such as stratospheric ozone destruction and warming of the troposphere. The aim of this study was to investigate if forest bogs contribute to the environmental input of naturally produced volatile organochlorine compounds. The concentrations of four different volatile organochlorine compounds were determined in ambient air, rainwater, surface water, and sub-surface water. For chloroform, up to 10-times higher concentrations were detected in the surface water compared to the sub-surface water taken at 40 cm depth. As the concentrations of chloroform in rainwater where almost in the same range as the concentrations in the sub-surface water, a formation of chloroform is suggested in the surface water. The results of this study indicate forest bogs as a possible new natural source for the input of volatile organochlorine into the environment.

Persistent organic pollutants (POPs), including organochlorine compounds (OCs) and polycyclic aromatic hydrocarbons (PAHs) were measured in two European remote mountain lakes situated in the Pyrenees (Lake Redon) and the Tatra Mountains (Ladove). Both dissolved and particulate water phases were analyzed at different water column depths., OCs already banned in most European countries showed similar concentrations in the two lakes, e.g. 6.7–8.5 pg L−1 for HCB, 8.0–12 pg L−1 for DDTs, and 60–64 pg L−1 for PCBs (sum of seven individual congeners), being in general lower than those reported in other remote aquatic systems. On the contrary, compounds of present use or currently emitted to the atmosphere exhibited significant concentration differences between sites. Thus, the higher levels of HCHs (1000–2630 pg L−1) and endosulfans (780–1610 pg L−1) in Lake Redon than in Ladove are in agreement with an impact of agricultural activities in the former. In contrast, the higher PAH concentrations in Ladove, 12 ± 1 ng L−1 (mean ± standard deviation), than in Lake Redon, 0.77–1.6 ng L−1 evidence higher deposition of combustion residues in the Tatras., POP concentration decreases with depth were observed for the compounds present in the dissolved phase such as endosulfan, HCB, and the low molecular weight PCBs and PAH. The vertical differences were higher in Lake Redon, probably due to its deeper basin. These gradients are consistent with the incorporation of these compounds into the lakes by air-water exchange through the gas-dissolved phase. In contrast, PCBs or PAH associated to the suspended particulate material (those of higher molecular weight) showed uniform concentrations throughout the water column, which may reflect high efficiency in the vertical transport of the compounds associated to this phase.

Exposure to organochlorine compounds (OCs) occurs both in utero and through breastfeeding. Levels of hexachlorobenzene (HCB) in the cord serum of newborns from a population located in the vicinity of an electrochemical factory in Spain are among the highest ever reported. We aimed to assess the degree of breast milk contamination in this population and the subsequent exposure of children to these chemicals through breastfeeding. A birth cohort including 92 mother–infant pairs (84% of all births in the study area) was recruited between 1997 and 1999 in five neighboring villages. OCs were measured in cord serum, colostrum, breast milk, and children's serum at 13 months of age. Concentrations of OCs were detected and quantified in all colostrum and milk samples. The concentrations in mature milk were lower than those encountered in colostrum. At 13 months of age the highest concentration of OC was found for dichlorodiphenyl dichloroethane (p,p′-DDE), in contrast to what these children presented at birth, where HCB was the highest compound. Those infants who were breastfed had higher concentrations at the age of 1 than those who were formula fed (2.13 ng/mL of HCB among formula feeders vs 4.26 among breast feeders, and 1.95 of p,p′-DDE vs 6.00 (P<0.05)). Long-term breastfeeding leads to a dose–response increase of the concentrations in children's serum during the first year of life.

Polychlorobiphenyls (PCBs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB) and DDT were examined in the muscle of brown trout (Salmo trutta) from a high mountain lake located in the Pyrenees (Catalonia, Spain) that was used as a model of these lacustrine environments. Results indicate that fish age is the main factor of variability among specimens in this population that is subjected to atmospheric inputs of the organochlorine compounds (OC). Increases of 2- and 20-fold between fish aged 1 year and 15 years old are found. The observed pattern cannot be explained in terms of fish size, condition factor, or muscle lipid content. Higher molecular weight compounds (higher lipophilicity) are better correlated with fish age than low molecular weight compounds. A transformation from 4,4′-DDT to 4,4′-DDE occurs in fish after ingestion; this results in amplified age-dependent signals, especially in male specimens. In contrast, PCB congener #180 has lower age dependence than the general OC group, which could be due to its high hydrophobicity (log Kow > 7). In any case, selective accumulation of hydrophobic compounds is already observed among younger fish (age, 1 year). Due to this effect, the relative OC composition does not reflect the main OC pollutants in the lake waters., Trout in high mountain lakes display age-dependent accumulation of certain organochlorine pollutants.

Volatile organochlorine compounds emitted from natural sources can participate in environmentally relevant processes affecting life on Earth, such as stratospheric ozone destruction and warming of the troposphere. The aim of this study was to investigate if forest bogs contribute to the environmental input of naturally produced volatile organochlorine compounds. The concentrations of four different volatile organochlorine compounds were determined in ambient air, rainwater, surface water, and sub-surface water. For chloroform, up to 10-times higher concentrations were detected in the surface water compared to the sub-surface water taken at 40 cm depth. As the concentrations of chloroform in rainwater where almost in the same range as the concentrations in the sub-surface water, a formation of chloroform is suggested in the surface water. The results of this study indicate forest bogs as a possible new natural source for the input of volatile organochlorine into the environment.

The composition of persistent organochlorine compounds (OC) in soils and sediments from two high altitude European mountain lakes, Redon in the Pyrenees and Ladove in the Tatra mountains, has been studied. Sediment cores from two additional lakes in the Tatra mountains, Starolesnianske Pleso and Dlugi Staw, have also been examined. DDTs (1.7–13 ng g−1) were the most abundant OC in soils followed by total polychlorobiphenyls (PCBs; 0.41–1.5 ng g−1) and hexachlorobenzene (HCB; 0.15–0.91 ng g−1). In sediments, the dominant OC were also DDTs (3.3–28 ng g−1) and PCBs (2.3–15 ng g−1). These concentrations are low, involving absence of major pollution sources in these high mountain regions., The downcore OC profiles in soils and sediments were similar but higher concentrations and steeper vertical gradients were observed in the latter. Radiometric determinations showed absence of significant OC transport from catchment to lake. The sediment–soil difference points therefore to a better retention of the OC load in sediments than soils which may be related to the low temperatures that are currently encountered at the bottom of the lake water column and the depletion of sediment bioturbation in these cold environments., Significant qualitative changes in the soil PCB distributions are observed downcore. These involve a dominance of the high molecular weight congeners in the top core sections and those of lower weight (i.e. less chlorinated) in the bottom. Anaerobic dechlorination of higher molecular weight congeners occurring in microsites, e.g. as observed in flooded or poorly drained soils, could be responsible for these changes. This process could be concurrent to bioturbation.

Organochlorine compounds (OC), namely pentachlorobenzene, hexachlorobenzene, hexachlorocyclohexanes, polychlorobiphenyls (PCBs), and DDTs, have been studied in mosses distributed over three altitude gradients of the Andean mountains in Chile at 18°S (3200−4500 m above sea level), 37°S (345−1330 m), and 45°S (10−700 m). The observed concentrations range among the lowest values ever reported in remote sites, but they are still higher than those found in previously studied Antarctic areas. The log transformed OC concentrations show a significant linear dependence from reciprocal of temperature independently of the origin of the compounds, e.g. industrial, agricultural, or mixed. In the case of the more volatile OC these correlations involve variance percentages higher than 50%. This good agreement gives further ground to temperature as the driving factor for the retention of long-range transported OC in remote ecosystems, including those in the southern hemisphere such as the Andean mountains. In the context of the samples selected for study, the temperature dependences in the areas of similar latitude are related to altitude. Thus, all OC in the highest altitude gradient (18°S) and most compounds in the other two profiles (37°S and 45°S) exhibit higher concentrations with decreasing annual average temperature and thus increase with elevation above sea level. However, theoretical examination of the exponential equation relating OC concentrations to reciprocal of absolute temperatures shows that besides the temperature differences between highest and lowest elevation, the most relevant factor determining the OC concentration gradients is the lowest temperature value of each altitudinal series. That is, the point at highest elevation.

The analysis of hexachlorobenzene, hexachlorocyclohexanes, polychlorobiphenyls, and DDTs in muscle of fish from high mountain lakes shows that a proportion of their concentration variance depends on fish age and lake altitude. Interestingly, the magnitude of this share corresponds linearly with the log-transformed vapor pressure (Vp) of the organochlorine compounds (OC). Thus, the distributions of OC with Vp < 10-2.5 Pa are mostly determined by these two variables. Altitude gradients mainly respond to temperature differences, involving concentration increases of 25−150 times between 8.7 and −2.3 °C. The age effect encompasses concentration increments of 2.4−7.8 for average lake differences between 2 and 13 yr. However, both effects are independent since no correlation between fish age and lake altitude is observed. Fish liver concentrations exhibit the same pattern, but the correlations are only significant for age, suggesting that the temperature trend is more related to long-term accumulation than episodic intake. The temperature effect is independent from compound origin. In addition, the sites situated at highest altitude, those most distant from possible ground pollution sources, are the most polluted. The results can be explained by condensation effects such as those described for the latitudinal trends that support the global distillation theory. However, in the high altitude lakes a temperature-dependent amplification mechanism, probably related to low metabolism and respiration at low temperatures, enhances OC accumulation in fish beyond the increases predicted from theoretical condensation and solubilization enthalpies. The observed temperature dependence suggests that a general remobilization of OC accumulated in high mountain areas could take place as a consequence of the general warming of these areas anticipated in the climatic change studies.

Air samples were taken onboard the RRS Bransfield on an Atlantic cruise from the United Kingdom to Halley, Antarctica, from October to December 1998, with the aim of establishing PCB oceanic background air concentrations and assessing their latitudinal distribution. Great care was taken to minimize pre- and post-collection contamination of the samples, which was validated through stringent QA/QC procedures. However, there is evidence that onboard contamination of the air samples occurred, following insidious, diffusive emissions on the ship. Other data (for PCBs and other persistent organic pollutants (POPs)) and examples of shipboard contamination are presented. The implications of these findings for past and future studies of global POPs distribution are discussed. Recommendations are made to help critically appraise and minimize the problems of insidious/diffusive shipboard contamination.

The use of organochlorine pesticides in rice growing in Laos is widespread. Potential contamination of pesticides to the aquatic organisms and sediments is a major concern. This study investigates the organochlorine pesticide contamination in fish, mollusks, and sediment from five main fishing areas of Vientiane, the capital of Laos. The fishing areas are located within the rice fields around Vientiane. Fifteen species of freshwater fish and one species of mollusks were homogenized, extracted, fractionated and subsequently analysed with Gas Chromatography Mass Spectrometry (GC-MS). Sediment samples were extracted and fractionated and analysed similarly as those of fish and mollusks. The target compounds of interest were lindane, chlordane, dieldrin, DDT and its derivatives. The result of this study shows that DDT, lindane, HCH, chlordane and dieldrin were present in 14 of 15 species of fish and mollusks. DDT, chlordane and dieldrin were present in the samples of sediment. This study also shows that lindane and chlordane has the highest concentrations both in fish and mollusk while DDT and its metabolites reveals next highest concentrations. Results show that highest concentrations of DDT, dieldrin and chlordane were observed in sediments. Results from this study indicate that organochlorine contamination occurs in fish and mollusks. Laotian depends on fish and mollusks for their dietary needs of protein and this is a cause of major concern for potential human health impacts. Furthermore, sedimentary environments where the study were being conducted shows appearance of DDT, dieldrin and chlordane and this would increase the bio-availability of those compounds to the aquatic organisms including fish and mollusks. Although, this study indicate that the levels of pesticides in fish, mollusk and sediment are below the World Health Organization (WHO) standards, the authority should try their best to reduce pesticide contamination in Vientiane, Laos. This study is the firs

The use of organochlorine pesticides in rice growing in Laos is widespread. Potential contamination of pesticides to the aquatic organisms and sediments is a major concern. This study investigates the organochlorine pesticide contamination in fish, mollusks, and sediment from five main fishing areas of Vientiane, the capital of Laos. The fishing areas are located within the rice fields around Vientiane. Fifteen species of freshwater fish and one species of mollusks were homogenized, extracted, fractionated and subsequently analysed with Gas Chromatography Mass Spectrometry (GC-MS). Sediment samples were extracted and fractionated and analysed similarly as those of fish and mollusks. The target compounds of interest were lindane, chlordane, dieldrin, DDT and its derivatives. The result of this study shows that DDT, lindane, HCH, chlordane and dieldrin were present in 14 of 15 species of fish and mollusks. DDT, chlordane and dieldrin were present in the samples of sediment. This study also shows that lindane and chlordane has the highest concentrations both in fish and mollusk while DDT and its metabolites reveals next highest concentrations. Results show that highest concentrations of DDT, dieldrin and chlordane were observed in sediments. Results from this study indicate that organochlorine contamination occurs in fish and mollusks. Laotian depends on fish and mollusks for their dietary needs of protein and this is a cause of major concern for potential human health impacts. Furthermore, sedimentary environments where the study were being conducted shows appearance of DDT, dieldrin and chlordane and this would increase the bio-availability of those compounds to the aquatic organisms including fish and mollusks. Although, this study indicate that the levels of pesticides in fish, mollusk and sediment are below the World Health Organization (WHO) standards, the authority should try their best to reduce pesticide contamination in Vientiane, Laos. This study is the firs

The enrichment of semi-volatile compounds from water using solid-phase microextraction (SPME) and stir bar sorptive extraction (SBSE) was compared. The investigations (analysis of PAHs and organochlorine compounds) were performed to compare SPME-GC/MS and SBSE-thermodesorption-GC/MS. Additionally, SPME fibres and stir bars were desorbed in a small volume of solvent and analysed by HPLC with fluorescence detection. This method was applied to PAHs. SBSE is more robust and under the given conditions (extraction from a 10 mL sample, 1 h exposure time of fibres and stir bars) enables higher recoveries (20.1–97.2%) for the compounds investigated than SPME (recoveries of 6.3–51.6%). Detection limits between 0.1 and 4.5 ng/L were calculated for the SPME-GC/MS combination, whereas the SBSE-GC/MS combination enabled detection limits between 0.05 and 1.0 ng/L. Coupled to HPLC, the detection limits of the PAHs investigated were found to range between 1.0 and 10.0 ng/L (SPME) or between 0.3 and 2.0 ng/L (SBSE). The advantage of SPME is that the procedure can be completely automated, which is not possible when combining SBSE with GC or LC.