Biological monitoring of PCDD/Fs and PCBs in the City of Mataró. A population-based cohort study (1995-2012).

There is great concern about the exposure to PCDD/Fs in areas near solid waste incineration (SWI) plants as, in the past, thermal waste treatment was a major source of PCDD/Fs, affecting negatively the environment and the population living nearby the area of influence. The aim of the present study was to monitor PCDD/Fs and PCBs levels in blood samples in general population living nearby a modern SWI. Up to 7 different campaigns were performed between 1995 and 2012. Overall, 104 exposed subjects (living <1000 m from the incinerator plant) and 97 non-exposed subjects (living >3000 m from the incinerator plant) were randomly selected from the municipal census of the City of Mataró in 1995. In addition, workers of the SWI plant were included in the study. Moreover, in 1999, 100 non-exposed subjects living in the nearby City of Arenys de Mar were added to the project. Overall, this study represents the longest consecutive human biomonitoring study of dioxins, furans and PCBs ever conducted in Spain. Concentrations of PCDD/Fs and PCBs were determined according to age, sex and distance to the SWI exposure in whole blood sample pools. No relevant differences in PCDD/Fs and PCBs levels were observed between SWI exposure groups. It could be noted that since 1999 all groups experienced a slight decrease in the levels of PCDD/Fs and marker PCBs. Moreover, concentrations of PCDD/Fs and marker PCBs were higher in women than in men, and in older age group in comparison to the younger ones.

PCDD/F and DL-PCB levels in meat from broilers and rabbits fed with fish-oil enriched feeds.

The aim of this study was to assess the effect on the final levels of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in meat when fats, in particular fish oils, are included as ingredients in feeds. Two types of animals (broilers and rabbits) were fed with three different experimental feeds containing varying amounts of two selected fish oils. PCDD/Fs and DL-PCBs were determined in the fish oils, the feeds and in the animals' meat. For broilers, PCDD/F and DL-PCB profiles in meat samples were similar to those found in the corresponding feeds, even though bioaccumulation of the highest chlorinated PCDD/F congeners seemed to decrease. Depending on the treatment, PCDD/F and the sum of PCDD/F and DL-PCB levels were 1.11-4.60 and 6.03-16.71 pg WHO-TEQ/g fat, respectively. For most of the cases, these values exceeded the maximum established by the Commission Regulation (EC) No. 1881/2006. In contrast, the levels of these contaminants in the corresponding feeds ranged from 0.11 to 0.54 pg WHO-TEQ/g, in the case of PCDD/Fs, and from 0.59 to 1.75 pg WHO-TEQ/g, when DL-PCBs were also included. These levels were, in general, below the maximum allowed by the Commission Directive 2006/13/EC. The results of the experiments with rabbits were not as conclusive as those for broilers although bioaccumulation appeared to be slower.

Assessment of the emission of PCDD/Fs and dioxin-like PCBs from an industrial area over a nearby town using a selective wind direction sampling device.

The development of new sampling devices or strategies to assess the concentration of persistent organic pollutants (POPs) in the environment has increased in the last two decades. In this study, a selective sampling device was used to evaluate the impact of potential local sources of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) and dioxin-like polychlorinated biphenyl (dl-PCBs) emissions on the ambient air levels of such compounds in a town near an important industrial estate. Average concentrations of target compounds of up to 2.5 times for PCDD/Fs and 2 times for dl-PCBs were found to come from the industrial state confirming this area as the main responsible for the majority of such compounds reaching the town. This finding was supported by a PCDD/F and dl-PCB sample profile analysis and a principal component analysis (PCA), which established a direct link between the dioxin-like compounds found in the samples collected in the town and their source.

Dioxins in beef samples from Mexico using a low resolution GC/MS screening method.

Dioxins in beef were quantified by high resolution gas chromatography coupled to low-resolution mass spectrometry (GC/LRMS). The analyses were performed according to the minimum requirements described in the USEPA 1613 method with some minor modifications. Levels found in the samples were in the range 1.02-8.04 pg WHO-TEQ PCDDs/PCDFs g(-1) fat. For comparison purposes, the maximum level allowed by the European Union is 3 pg WHO-TEQ PCDDs/PCDFs g(-1) fat, and some of these samples surpassed the above-mentioned limit and can be considered as contaminated food. The results confirm that a preliminary screening of dioxins in beef can be performed by GC/LRMS. As far as we know, this is the first report of dioxins in beef in Mexico. After the appropriated tests, the applied methodology could be considered as an alternative screening method for the analysis of PCDD/Fs in other food products.

Analysis of nitrosamines in water by automated SPE and isotope dilution GC/HRMS Occurrence in the different steps of a drinking water treatment plant, and in chlorinated samples from a reservoir and a sewage treatment plant effluent.

A method based on automated solid-phase extraction (SPE) and isotope dilution gas chromatography/high resolution mass spectrometry (GC/HRMS) has been developed for the analysis of nine nitrosamines in water samples. The combination of automated SPE and GC/HRMS for the analysis of nitrosamines has not been reported previously. The method shows as advantages the selectivity and sensitivity of GC/HRMS analysis and the high efficiency of automated SPE with coconut charcoal EPA 521 cartridges. Low method detection limits (MDLs) were achieved, along with a greater facility of the procedure and less dependence on the operator with regard to the methods based on manual SPE. Quality requirements for isotope dilution-based methods were accomplished for most analysed nitrosamines, regarding to trueness (80-120%), method precision (<15%) and MDLs (0.08-1.7 ng/L). Nineteen water samples (16 samples from a drinking water treatment plant {DWTP}, 2 chlorinated samples from a sewage treatment plant {STP} effluent, and 1 chlorinated sample from a reservoir) were analysed. Concentrations of nitrosamines in the STP effluent were 309.4 and 730.2 ng/L, being higher when higher doses of chlorine were applied. N-Nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA) were the main compounds identified in the STP effluent, and NDEA was detected above 200 ng/L, regulatory level for NDMA in effluents stated in Ontario (Canada). Lower concentrations of nitrosamines were found in the reservoir (20.3 ng/L) and in the DWTP samples (n.d. -28.6 ng/L). NDMA and NDEA were respectively found in the reservoir and in treated and highly chlorinated DWTP samples at concentrations above 10 ng/L (guide value established in different countries). The highest concentrations of nitrosamines were found after chlorination and ozonation processes (ozonated, treated and highly chlorinated water) in DWTP samples.

Effects on growth and biochemical responses in juvenile gilthead seabream 'Sparus aurata' after long-term dietary exposure to low levels of dioxins.

The farmed fish gilthead seabream (Sparus aurata) were fed with a dry feed spiked with a low level (23 ng WHO-TEQ/kg of feed) polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) mixture in order to assess bioaccumulation of these contaminants in the muscle and liver tissues after long-term exposure (approximately 390 days). Furthermore, effects on fish growth, feeding and on the response of some biochemical markers (induction of the CYP1A dependent EROD activity, the conjugating enzyme GST, the antioxidant enzymes CAT, t-GPX and DTD, lipid peroxidation and the AhR gene expression) were also evaluated. After feeding with the spiked dry feed for 3 months the PCDD/F concentrations in the exposed fish were 5.50 pg WHO-TEQ/g fresh weight (f.w.) in flesh and 8.45 pg WHO-TEQ/g f.w in liver tissue, which are approximately 24-fold and 14-fold higher than background levels, respectively. However, a progressive increase in PCDD/F levels was not found during the rest of the exposure period. Differences in fish growth were not observed between dioxin-exposed and non-exposed animals and, in addition, no mortalities were recorded attributable to the dioxin intake. Significant increases in the EROD activity, as well as in AhR gene expression were observed in liver after approximately 300 days of exposure. However, no effect on the antioxidant enzymes CAT and t-GPX was found.

Unexpected high PCB and total DDT levels in the breeding population of red kite (Milvus milvus) from Doñana National Park, south-western Spain.

This study provides information on the current status of contamination by organochlorines (DDTs, PCBs, PCDDs and PCDFs) in the declining red kite (Milvus milvus L.) population breeding in the Doñana National Park (DNP), south-western Spain. Analyses were performed in addled eggs collected between 1999 and 2001. DDE concentrations ranged from 0.1 to 33.5 microg/g ww, representing more than 86% of the total DDTs. Of the samples studied, 50% showed DDE levels above those associated with reproductive impairment in other raptor species. Concentrations of ortho PCBs (average 36.8 microg/g ww+/-37.7) in 50% of the eggs were much higher than levels reported to cause reduced hatching success, embryo mortality, and deformities in birds (>20 microg/g ww). It is remarkable that average ortho PCB and DDE concentrations showed an increase of one order of magnitude compared to previous data for the species during the 80s. Total PCDD/Fs showed levels in the low pg/g range (7.2-42 pg/g ww), having PCDDs and PCDFs similar contributions in most samples. Total mean TEQs were 238 pg/g (ww), being the range 7.02-667 pg/g (ww). Spatial variation within DNP was observed for PCBs, DDTs, as well as for TEQs. Since some eggs exceeded the NOEL (67%) and LOEL (33%) reported for other raptor species, we would expect the red kite to experience detrimental effects to dioxin-like toxicity. Our results suggest that organochlorine contaminants should be regarded as an element of concern in the population under study, in addition to other conservation problems already reported. Further investigations should be undertaken to identify potential sources of these chemicals in DNP, and to find out if organochlorine contamination is present in other predator species in the area, as well as their potential health effects on individuals and/or populations.

Evaluation of the Spanish hot dip galvanising sector as a source of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans.

A survey to estimate the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) emissions of Spanish hot dip galvanising sector was carried out during 2002. This investigation is the first presenting Spanish experimental data related to this industrial sector. Three different matrices: flue gas, ash and filter dust were tested to quantify the PCDD/Fs generated during the galvanising process. The organic source of PCDD/F formation could be from the insufficient degreasing o from inhibitors or additives used in the pickling steps such as quinoline, isoquinoline, 8-methylquinoline or polyether phosphoric acid. Low levels PCDD/Fs were achieved in air emissions when air control devices are used. On the contrary, filter dusts are highly contaminated; indicating that the absence of air control devices would increase the risk of fugitive emissions. Homologue profiles and Principal Component Analysis demonstrate there are differences in the formation mechanisms in the bath zone (ashes) compared to the stack location (filter dusts and air emissions), related to the de novo synthesis and reaction time. The annual PCDD/F emission to the atmosphere for this sector during 2002 has been estimated in 0.023g I-TEQ. The emission factor of plants with air control devices has been calculated at 0.030microg I-TEQ/ton of galvanised steel.

Ion-trap tandem mass spectrometry for the analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in food.

This paper reports on the applicability of gas chromatography coupled to ion-trap tandem mass spectrometry (GC/ITMS/MS) for the analysis of polychlorinated dibenzo- p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) in food. MS/MS parameters were selected to achieve the high sensitivity and selectivity required for food analysis. Good precision (RSD=5-18% for PCDD/Fs and 6-14% for dl-PCBs) and low limits of detection for PCDD/Fs (0.1-0.93 pg/g of fat) and dl-PCBs (0.1-0.89 pg/g of fat) were obtained. A comparative study of the congener-specific determination using both GC/ITMS/MS and GC-high resolution mass spectrometry (GC/HRMS) was performed by analyzing several matrices such as milk, fish oil, chicken, pork, fish, eggs, and a chicken compound feed, at low pg/g levels. The results using GC/ITMS/MS were in good agreement with those obtained by GC/HRMS. Consequently, GC/ITMS/MS is proposed for the analysis of PCDD/Fs and dl-PCBs in food and feed samples.

Ten years measuring PCDDs/PCDFs in ambient air in Catalonia (Spain).

This work summarizes the results of a ten year surveillance programme on PCDD/F in ambient air carried out in Catalonia (Spain). The study has been conducted by the Dioxin Laboratory of Spanish Council for Scientific Research (CSIC) in collaboration with the Environment Department of the Catalonian Government. 175 samples have been collected throughout Catalonia from 1994 to 2004. Different sampling locations classified as industrial, traffic, urban, suburban and rural sites have been monitored in order to find the most contaminated zones as well as the ones with expected background concentrations. The highest concentrations found in this study were determined at the industrial locations. Concentrations ranging from 5 to 1196 fg I-TEQ/m3, with a mean value of 140 fg I-TEQ/m3 and from 10 to 357 fg I-TEQ/m3, with a mean value of 72 fg I-TEQ/m3 were determined in industrial and traffic sampling points, respectively. In contrast, the lowest concentrations were found in rural stations, ranging from 5 to 45 fg I-TEQ/m3, with a mean value of 28 fg I-TEQ/m3. The PCDD/F concentration trend in Catalonian ambient air shown a clear drop of the median values occurred during the study sampling period. A decline of about 70% was observed from 1997-1998 to 2003-2004.

Evaluation of Organochlorine Compounds (PCDDs, PCDFs, PCBs and DDTs) in Two Raptor Species Inhabiting a Mediterranean Island in Spain (8 pp).

UNLABELLED: -: DOI: http://dx.doi.org/10.1065/espr2006.01.015 BACKGROUND: Species that are at high levels of the food web have often been used as bioindicators to evaluate the presence of persistent contaminants in ecosystems. Most of these species are long-lived, so pollutant burdens may be integrated in some complex way over time. This makes them particularly sensitive to deleterious effects of Persistent Organic Pollutants (POPs). Birds have been suggested as useful organisms for monitoring pollutant levels. Traditionally such studies have been carried out with raptors such as osprey (Pandion haliaetus), peregrine falcon (Falco peregrinus), bald eagle (Haliaetus leucocephalus), etc. In this paper we present the results of a monitoring study conducted on two raptor species, osprey (Pandion haliaetus) and red kite (Milvus milvus), inhabiting a Mediterranean island (Menorca, Spain). These two species have different feeding habits; ospreys prey on fish and red kites feed on terrestrial species. This study constitutes a good opportunity to investigate if differences in feeding habits (aquatic vs. terrestrial) influences the contaminants pattern in two species inhabiting the same area. METHODS: The study was conducted in a non-destructive way, using only failed eggs, to avoid the damage of the population stability. Eggs were collected during the period 1994-2000. The contaminants examined were dichlorodiphenyltrichloroethanes (DDTs, including DDT and its main metabolite, DDE), polychlorinated biphenyls (PCBs), including ortho PCBs (PCBs with at least one Chlorine atom in the ortho position): #28, 52, 95, 101, 123+149, 118, 114, 153, 132+105, 138, 167, 156, 157, 180, 170, 189, 194; and non ortho PCBs (PCBs with no Chlorine atom in the ortho position): #77, 126, 169 and all the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) with Chlorine atoms at the 2,3,7 and 8 position (2,3,7,8-substituted PCDDs and PCDFs). The analysis of organochlorine compounds was performed using a sample treatment based on a Solid Phase Matrix Dispersion procedure. Ortho PCBs and DDTs were determined by HRGC-µECD; non ortho PCBs and PCDD/Fs were determined by HRGC-HRMS. RESULTS AND DISCUSSION: The sum of the ortho PCB congeners analysed ranged from 0.94 to 15.03 µg/g wet weight (ww) for ospreys and from 1.0 to 11.2 µg/g ww for red kites. In both species, PCB congeners #153, #138 and #180 accounted about 75% to total ortho PCB concentrations. Regarding non ortho PCBs, for ospreys, concentrations ranged from 0.16 to 1.39 ng/g wet weight (ww) and for red kites from 0.12 to 0.51 ng/g ww, being congener #126 the most abundant. Concerning DDTs, concentration for ospreys ranged from 0.07 to 1.03 µg/g ww; and for red kites ranged from 0.90 to 2.10 µg/g ww, representing DDE more than 95% of the total DDTs, which proves a past use of DDT in the study area. Differences in contaminant levels between species are probably associated to feeding habits. The fish-eating species presents the highest PCB levels, whereas the terrestrial species exhibits the highest DDT levels. PCDD/Fs in ospreys were in the range 2.6-14.2 pg/g ww, while in red kites the range was slightly wider (22.2-43.2 pg/g ww), being PCDDs the major contributors in black kites. Ospreys had PCDDs similar to PCDF concentrations. PCDD/F profiles were mostly influenced by OCDD in both species. Non ortho PCBs were the major contributors to calculated Toxic Equivalent Quantity (TEQs) in both species. CONCLUSION: In both species studied, ortho-PCBs could represent a problem of concern since 57% of the eggs exhibited levels higher than 4 µg/g ww, reported as the level that could cause reduced hatchability, embryo mortality, and deformities in birds. RECOMMENDATIONS AND OUTLOOK: Results found in this study suggest that a more detailed study to clear up possible deleterious effects of PCBs on the bird populations studied here should be done.

Analysis of pesticides and metabolites in Spanish surface waters by isotope dilution gas chromatography/mass spectrometry with previous automated solid-phase extraction Estimation of the uncertainty of the analytical results.

A method based on isotope dilution gas chromatography/mass spectrometry (GC/MS) with automated solid-phase extraction (SPE) is described for the analysis of 32 pesticides and metabolites in surface waters. This approach consist in the use of nine isotopically labelled representative pesticides as internal standards, which allows high accuracy (trueness and precision) and sensitivity for most analysed compounds, as it is required for isotope dilution-based methods. Uncertainties associated with pesticide determination in real samples were estimated using quality assurance/quality control (QA/QC) data. For most pesticides expanded uncertainty was below 40%, according to the commonly established requirements for analytical results. Ninety three Spanish surface waters collected in June-July and September-November 2004 were analysed. Concentration and occurrence of pesticides were evaluated. These parameters were higher in the summer than in the autumn period. In summer four pesticides were found in more than 50% of the analysed samples and four compounds were detected above the concentration level of 1 microg/l (atrazine, terbutylazine, 3,4-dichloroaniline and fenitrothion), while in autumn percentage of detection was below 50% for all pesticides and only one compound (terbutylazine) exceeded 1 microg/l.

Analysis of alkyl and 2-6-ringed polycyclic aromatic hydrocarbons by isotope dilution gas chromatography/mass spectrometry. Quality assurance and determination in Spanish river sediments.

An accurate, precise and sensitive method is described for the analysis of 29 polycyclic aromatic hydrocarbons (PAHs), including 19 2-6-ringed PAHs and 10 alkyl-PAHs. The method is based on an isotope dilution technique using gas chromatography/mass spectrometry (GC/MS) and available labeled PAHs as internal standards. Quality parameters were calculated with satisfactory results and 36 Spanish river sediments were analysed. Results were evaluated regarding to the sediment quality guidelines (SQGs) based on the effects range-low (ERL) and the effects range-median (ERM) values. Most analysed sediments showed a good quality, since only 7 of them exceeded ERL values, including one sample surpassing ERM values. PAH profiles were studied in order to identify PAH sources as mainly petrogenic or pyrogenic. Most samples showed petrogenic-type fingerprints, although 6 of the 11 sediments with the highest PAH concentrations (> 1000 ng/g) were classified as pyrogenic, including 4 of the 7 samples exceeding ERL values. Quality assurance was carried out by the triplicate analysis of one preanalysed river sediment without PAHs subsequently spiked at a medium (500 ng/g) and a low concentration level (10 ng/g) of each analyte. Main quality requirements for methods based on isotope dilution were accomplished. Method accuracy was 80-120% for most PAHs, method precision was <15% for all the analysed compounds and method detection limits (MDLs) were 1-3 ng/g.

Surveillance programme on dioxin levels in soils in the Campo de Gibraltar (southwest Spain).

The results of an epidemiologic study undertaken by the Spanish Council for Scientific Research (CSIC) after commission by the Spanish Parliament indicated that Huelva and Cádiz were the zones in Andalusia with elevated risk of cancer. A 6% (women) and 10% (men) cancer mortality excess was observed with respect to the other six Andalusian provinces. Huelva and Cádiz are located in the south-western region of Spain, and are characterized by a strong industrial activity concentrated in several industrial sites. This situation led to two environmental surveys in these areas, in which the presence of dioxins was studied among other parameters. A PCDD/F assessment in soils of the Campo de Gibraltar (Cádiz) was carried out from June 2003 to June 2004. A total of 20 samples were collected in this study divided in two sampling campaigns. The first 10 samples were taken in locations affected by high industrial activity zones as well as in landfills (hotspots). The rest of the samples were collected in areas that were not expected to be contaminated, such as agricultural zones and forests. I-TEQ values of the samples ranged from 0.26 to 15.08 ng/kg dm. In all, 85% of the samples were below the limit of 5 ng I-TEQ/kg I-TEQ concentrations of three samples only surpassed this limit. These zones corresponded to a landfill, a quarry used for dumping chemical product containers and a sample from the sewage system of the industrial site. These sites were used neither for agricultural nor for public purposes.

Evaluation of organochlorine compounds in peregrine falcon (Falco peregrinus) and their main prey (Columba livia) inhabiting central Spain.

The population of peregrine falcon (Falco peregrinus sbs. brookei) inhabiting the Regional Park of southeastern Madrid (RPSM), Spain, has experienced an increase of unsuccessful pairs (from 15% among a total of 20 pairs in 1995 to 55% among a total of 18 pairs in 2001). Traditionally, this area has been known to be contaminated with organochlorine compounds and toxic metals, which are known to be deleterious to the reproductive system of birds. During the breeding seasons of 2000 and 2001, contaminant residues were measured in unhatched eggs of peregrine falcons and liver of their main prey, to determine if they could be affecting the survival of the population. The most abundant contaminants were ortho-polychlorinated biphenyls (ortho-PCBs), ranging from 202.56 to 3,335.16 ng/g (wet wt) in falcon eggs and from 10.25 to 53.51 ng/g (wet wt) in pigeon livers. In all samples, the 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were detected, although these levels never exceeded 20 pg/g (wet wt). The major contributor to total toxic equivalent quantities (TEQs) were non-ortho-PCBs. Organochlorine levels found in this study may contribute to the entire suite of stressors that are negatively affecting the peregrine population.

EROD induction and PCDD/F levels in fish liver from the Biobio River in Chile.

The Biobio River basin, located in central Chile, is one of the most important freshwater resources for a population of 1 million inhabitants. The river receives discharges of pulp mills, sewage treatment plants and there is a diffuse input of materials coming from the drainage basin. Previous studies reported high levels of etoxyresorufin-O-deethylase (EROD) induction in fish from the lower stretch of the river, mainly due to polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) exposure. The present study investigates polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) levels as well as EROD induction in fish livers from Central Chile's Biobio River. Dioxin and furan levels in fish livers are reported for the first time in three areas of the Basin. In all samples the highest concentrations were found for the octachlorodibenzo-p-dioxin (OCDD) and PCDD/F TEQ concentrations ranged from 2.83 to 6.33 ppt (wet weight). The results indicate a clear induction of EROD activity in different fish species as the river mouth is approached, although this induction is not clearly related with dioxin and furan levels found in the fish livers. Our results clearly show that other pollutants might be acting as EROD inductors in the Biobio Basin.

Optimization of intracellular microcystin extraction for their subsequent analysis by high-performance liquid chromatography.

Microcystins are a family of heptapeptide hepatotoxins produced by some genera of cyanobacteria. These toxins have been responsible for the illness and death of both animals and humans. Due to their hazard to human health, extraction of all intracellular microcystin variants is required to characterize and quantify all microcystins present in a sample. To date, there is little work reported comparing results obtained with different extraction methods. Findings reported to date indicate that selection of solvent will vary depending on sample and its microcystin contents. In the present work, a wide range of extraction volumes and solvents were evaluated over a range of pH and extraction times in order to optimize a suitable method for the extraction of a wide range of microcystins. The number of extractions required was also studied. This study was carried out using mainly two laboratory cultures which contain microcystin variants with quite different hydrophobicities. This is the first time that the most commonly used solvents for intracellular microcystin extraction have been studied in detail.

Results and evaluation of the first study of organochlorine contaminants (PCDDs, PCDFs, PCBs and DDTs), heavy metals and metalloids in birds from Baja California, México.

Organochlorine compounds (OCs) including polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p-p'-DDE), heavy metals (Pb, Cd, Zn, Cu), and arsenic were measured in house sparrows (Passer domesticus) and common ground doves (Columbina passerina) from Baja California Sur, México. Concentrations of PCDD/Fs were low, with 21 pg/g for house sparrows, and 7.7 pg/g for common ground doves. Non-ortho-PCB concentrations in house sparrow and common ground doves were 58 and 254 pg/g, respectively, and are within the highest concentrations reported in species that are in the low levels of food webs. The major differences in organochlorine levels between species were found for ortho-PCBs and DDTs. ortho-PCB levels were higher in the seedeater species, whereas DDT levels were higher in the omnivorous species. Heavy metal levels were far below those associated with negative effects.

Determination of microcystin variants and related peptides present in a water bloom of Planktothrix (Oscillatoria) rubescens in a Spanish drinking water reservoir by LC/ESI-MS.

A water bloom of Planktothrix (Oscillatoria) rubescens was observed in a drinking water reservoir in central Spain in 2003. Microcystins where analysed by LC/ESI-MS in 21 samples collected from this reservoir in five different days between March and May. A demethylated variant of microcystin-RR was identified as the major microcystin in most samples. Trace levels of microcystin-LR, -RR and -YR were detected in some samples. Four less common microcystins, with [M+H]+ ions at m/z 960, 981, 1045 and 1053, were also found. Total extracellular microcystin concentration varied from 0.010 to 19.126 microg l(-1). Furthermore, anabaenopeptins B and F as well as Oscillamide Y were also identified in these samples.

Polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran releases into the atmosphere from the use of secondary fuels in cement kilns during clinker formation.

The aim of this study was to evaluate the influence of using waste materials, such as tires or meat meal, as a secondary fuel during clinker production on the polychlorinated dibenzo-p-dioxin (PCDD)/polychlorinated dibenzofuran (PCDF) emission levels to the atmosphere. For this purpose, three different cement plants in Spain were chosen to conduct the project in different sampling episodes. Different materials were separately evaluated in each plant: the first plant included the addition of meat meal in the kiln, the second plant used rejected tires, and the third plant used a mixture of both. In all cases, PCDD/F emission values remained below the limit established by the European Union Directive of 0.1 ng I-TEQ/Nm3, with values ranging from 0.001 to 0.042 ng I-TEQ/Nm3. The major contribution to total TEQ in the majority of cases came from 2,3,7,8-tetrachlorodibenzofuran owing to its relatively higher levels and 2,3,4,7,8-pentachlorodibenzofuran because of its TEF of 0.5. The remaining 15 toxic congeners collectively provided only a minor contribution to TEQ. Furthermore, no marked differences were found compared with reported data obtained from Spanish cement kiln plants using conventional fuel. This fact indicates that the addition of used tires or meat meals had no effect on PCDD/PCDF emission levels.