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.     

Levels of PCBs, PCDDs and PCDFs in commercial butter samples in Spain

Feasibility of three different extraction methods for the simultaneous determination of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in butter is discussed. The method based on liquid-liquid extraction with water of the non fatty solids from butter dissolved in hexane was found to be the most efficient for the determination of the lipid content and the levels of the investigated pollutants. This method was used to evaluate the background levels of PCBs, PCDDs and PCDFs in butters commercially available in Spain. Broad ranges of PCB, specifically, PCDD and PCDF concentrations were found in the different brands analysed. Levels, profiles and patterns of these pollutants in butter were compared with those previously reported for different Spanish dairy products. The toxic tetra-equivalents of 2,3,7,8-TCDD (1-TEQ) averages for PCDDs and PCDFs in the 21 butter samples analysed were 0.41 and 0.70 pg/g fat basis, respectively. These values were similar or lower than those cited in the literature for other countries.     

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 Unpublished, 19 p] has been carried out during 2001-2003 in sludge samples from Catalonia (NE Spain).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.     

A comparison of TEQ contributions from PCDDs,PCDFs and dioxin-like PCBs in sewage sludges from Catalonia,Spain

Eight sewage sludges from rural, urban and industrial wastewater treatment plants (WWTPs) in Catalonia (Spain) were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) to determine the present levels of contamination. A method based on an automated cleanup system followed by an isotope-dilution high-resolution mass spectrometric analysis was employed. Total toxicity equivalent (WHO-TEQ) values were calculated using the toxicity equivalent factors (WHO-TEFs) proposed by WHO for dioxin-like PCBs, PCDDs and PCDFs. The WHO-TEQ(PCDD/F) values for these samples ranged from 4.9 to 20.8 pg/g dry weight (d.w.), with a mean value of 9.3 pg/g d.w., whereas WHO-TEQ(PCB) levels ranged between 1.9 and 6.6 pg/g d.w., with a mean value of 4.2 pg/g d.w. The WHO-TEQ(PCB) contribution varied from 13% to 50%, suggesting that PCB contribution on the toxicity of the samples must be taken into account. Moreover, these contemporary PCDD, PCDF and PCB concentrations were compared with previous data obtained from sewage sludge samples collected during the 80s. Our findings show that contemporary PCDD, PCDF and PCB levels have declined since the 80s.     

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.     

Atmospheric deposition of PCDD/Fs near an old municipal solid waste incinerator: levels in soil and vegetation

The levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were determined in soil and vegetation samples taken from 24 sites in the vicinity of an old municipal solid waste incinerator (San Adrià del Besòs, Barcelona, Spain). Duplicate samples were collected within a radius of 3 km from the stack. PCDD/F concentrations in soils ranged from 1.22 to 34.28 ng I-TEQ/kg (d.m.) with median and mean values of 9.06 and 12.24 ng I-TEQ/kg, respectively. In turn, the levels of PCDD/Fs in vegetation samples ranged from 0.33 to 1.98 ng I-TEQ/kg (d.m.), with median and mean values of 0.58 and 0.70 ng I-TEQ/kg, respectively. Although the present PCDD/F concentrations in soil samples were higher than those recently found in soils taken near other incinerators from Catalonia, they are of the same order of magnitude than the levels of these pollutants found in incinerators from other countries. By contrast, the concentrations of PCDD/Fs in herbage samples were comparable to those found in recent surveys carried out in Catalonia.     

Organic pollutants in the Odra river ecosystem

The paper presents the results of the analysis of water and bottom sediment samples from different locations along the Odra river, collected during eight campaigns in the years 1997-2000. All the basic organic pollutants were determined. Pollution of water with PCBs was negligible while with PAHs was not critical. Concentrations of volatile organochlorine compounds in water were the highest in Brzeg Dolny and its surroundings. Concentrations of tetrachloroethene were exceptionally high in the Szczecin Lagoon. The Odra sediments were non-polluted or only slightly polluted with PCBs, pesticides and different classes of volatile organic pollutants. However, PAHs were present in rather large concentrations, especially in the upper course of the Odra river. The data obtained contributed to the evaluation of pollutants discharges to the Baltic sea via Szczecin Lagoon as well as to the characterization of pollution sources (point sources and area sources) in the Odra catchment area.     

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.     

Selective organic compounds degradation under controlling composting conditions

Organic matter stabilization resulted from the decrease of cellulose, xylan, arabinan, acetyl groups, glucuronic acids, galacturonic acids (easily biodegradable fractions) and the increase of lignin (resistant compound) and humic substances coming from the initial wastes have been studied. A central composite experimental design was used to investigate the influence of environmental composting parameters (moisture, aeration and particle size) on organic matter evolution. The organic matter evolution was clearly influenced by the studied composting parameters. All results were concordant, with an increase of humic substances and lignin and a decrease of the rest of the cellulose and hemicellulose compounds. Lower cellulose, xylan, acetyl groups and glucuronic acids contents (higher degradation) have been observed under low particle size (1 cm) and higher moisture content (70%). However lower lignin and higher humic substances under medium (3 cm) to low particle size and low moisture content (40%) have been found.     

Study on PCDDs/PCDFs and co-PCBs content in food samples from Catalonia (Spain)

The results of a surveillance programme on polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (co-PCBs) determination in 70 foodstuffs samples produced all over the four provinces of Catalonia is presented. The study included the analyses of raw milk, pure virgin olive oil, butter, chicken, pork and mussel samples collected between November 1999 and January 2000. Milk, virgin oil, pork or butter presented a variable dioxin and co-PCBs content, even though the limits proposed in the draft of the EC Regulation for its commercialization in the European countries were not reached. The levels of PCDDs/PCDFs and co-PCBs determined in chicken samples varied between 0.36–3.59 pg I-TEQ/g fat chicken (0.4–3.8 WHO-TEQ/g fat). Just one case presented remarkable content of dioxins (about 30 pg I-TEQ/g fat) with a complex congener-specific profile which indicates the presence of an external contamination. On the other hand, a congener-specific profile dominated by 2,3,7,8-TCDF and OCDD was observed in mussel samples from Catalonia. This fact was also observed in mussel samples from other sites in Spain.