Ostracoda and foraminifera as short-term tracers of environmental changes in very polluted areas: the Odiel Estuary (SW Spain)

The analysis of 17 cores collected in the Odiel Estuary (SW Spain) permits delimiting the recent evolution of this zone during the past decades and the influence of natural and anthropogenic factors on the distribution of Ostracoda and Foraminifera. In the upper estuary, the coincidence of acid waters, prolonged subaerial exposure, and coarse sediments may explain the absence or the disappearance of these microorganisms during the industrial period (1966-1985) in the major part of this area. In the lower estuary, sedimentary evolution and industrial wastes are the main factors influencing both the distribution and trends of the populations of these two groups. Finally, the main changes observed in the marine estuary are due to the sedimentary effects of the construction of two banks and the dredging of the main estuarine channel.     

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.     

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.     

Assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans in sludges according to the European environmental policy

The amount of sewage sludge generated in Europe is expected to surpass the 10 million tons/year in 2006 as a result of the waste water treatment process according to the Water Policy in European Union. Sewage sludge is what is left behind after water is cleaned in waste treatment plants and is characterized for this high content in nitrogen and phosphorous that could be of great importance in agriculture as fertilizer or soil conditioner. On the other hand, pollutants like metals and organic contaminants are usually removed from water and are accumulated in the sewage sludge, reaching the food chain if their concentrations are not below the safe limits established by the European legislation. The latter issue is of great concern nowadays and in this sense, different works alert against the use of the sewage sludge in agriculture arguing that serious illnesses, even resulting in death as well as adverse environmental impacts are associated to the application of sewage sludge. This work is a continuation of a former comprehensive survey on of priority organic pollutant in sludges for agricultural purposes carried out by our group in Catalonia and this time is focused on the polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), one of the most toxic group of organic compounds listed in the Work Document on Sludge which is the reference tool in this field in Europe and is also included in the Stockholm Convention. Eighty eight samples were collected from the end of 2003 to April 2006 and the concentrations detected were lower than the 100 ng/kg I-TEQ limit recommended by the European legislation (EC, 2000). Thus, sewage sludges generated in Catalonia do not represent a threat to human health if they are used as fertilizers in agriculture.     

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

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

Priority organic pollutant assessment of sludges for agricultural purposes

A comprehensive characterization of five of the seven priority organic pollutants listed in the draft of the "Working document on sludge" [EU, 2000. Working Document on Sludge 3rd Draft. Unpublished, 19 p] has been carried out during 2001-2003 in sludge samples from Catalonia (NE Spain). One hundred and thirty-nine samples belonging to 20 Waste Water Treatment Plants (WWTPs), seven sludge treatment (thermal drying) and three composting sludge plants were taken in order to determine the concentration of polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs), di-2-(ethyl-hexyl)-phthalate (DEHP), nonylphenol and nonylphenol ethoxylates with one or two ethoxy groups (NPE), polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). PCDD/F concentrations were in general lower than the 100 ng I-TEQ/kg limit suggested in the above-mentioned document. In the same way, 98.5% for PCBs, 97% for PAH and 92.8% for DEHP of the samples presented concentrations lower than 0.8 mg/kg dm, 6 mg/kg dm and 100 mg/kg dm, respectively. In contrast, the vast majority of samples contained NPE concentrations much higher than 50mg/kg dm limit. The values ranged from 14.3 to 3150 mg/kg dm (median value=286.6 mg/kg) being composted sludge samples the less contaminated ones (17.9-363.4 mg/kg dm; median value=89.3 mg/kg). Special attention should be paid to the Catalan sludge NPE contamination owing to the high levels detected.     

Evaluation of the susceptibility of the cultured shrimp Litopenaeus vannamei to vibriosis when orally exposed to the insecticide methyl parathion

The causes of disease in cultured shrimp are difficult to ascertain but there is evidence that disease is correlated with environmental factors. Crustaceans are particularly sensitive to insecticides due to their close phylogenetic relationship with insects. The objective of this study was to investigate whether there was an increased susceptibility of the shrimp Litopenaeus vannamei to Vibrio parahaemolyticus, when exposed to methyl parathion. The outline of the study was the following: An LC50 96 h was determined to methyl parathion orally offered to juvenile shrimp. Further experiments were carried out in order to determine a concentration that affected the shrimp (verified by measuring the acethylcholinesterase activity) while producing minimal mortalities. This sublethal concentration was used in a susceptibility experiment where methyl parathion was offered to shrimp which were later injected with V. parahaemolyticus in a dose expected to kill less than 15%. Probit analysis estimated a 96 h median lethal concentration (LC50) of 1.56 microg g(-1). Mortality and AChE activity showed a concentration-response relationship in the exposure treatments. The median inhibitory concentration (IC50) determined was 0.029 microg g(-1). These results suggested that a concentration of 0.1 microg g(-1) was appropriate for the bacteria-pesticide interaction test as it was able to elicit 11.1% mortality after 10 days of exposure, while producing an AChE inhibition of 57.12%. Cumulative mortalities were significantly increased (P<0.01) in the treatment that combined exposure to methyl parathion and V. parahaemolyticus (35.19%) in comparison with methyl parathion or V. parahaemolyticus alone (9.26% and 7.41%, respectively).     

Study on PCBs,PCDD/Fs,organochlorine pesticides,heavy metals and arsenic content in freshwater fish species from the River Turia (Spain)

In this study samples of common trout, European eel and barbel have been analysed for the levels of heavy metals such as lead (Pb), cadmium (Cd), zinc (Zn), copper (Cu), and the metalloid arsenic (As). Polychlorinated biphenyls (PCBs), including three non-ortho substituted PCBs, 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and DDT and its two main metabolites were also analysed in some selected samples, in order to evaluate the extent of contamination of the River Turia basin. All samples presented detectable levels of the elements analysed, presenting zinc the highest concentrations. European eel was the species found to highly accumulate these contaminants. Regarding organochlorinated compounds, seven samples exhibited detectable levels of the most toxic PCDD/Fs congener, the 2,3,7,8-TCDD. Non-ortho PCBs were not detected or not quantified in almost all samples and the sum of the individual PCB congeners determined were low compared to other aquatic ecosystems with similar fish species.