J. Diaz-Ferrero

Congener profile, occurrence and estimated dietary intake of dioxins and dioxin-like PCBs in foods marketed in the Region of Valencia (Spain).

During 2006-2008, a monitoring program was conducted on 29 target compounds, including PCDD/Fs and dl-PCBs, comprising 150 randomly collected individual food samples marketed in the Region of Valencia, Spain, grouped into 8 categories (vegetables, cereals, fats and oils, eggs, milk and dairy products, fish products, meat and meat products and fish oil). For PCDD/Fs, the highest frequency of detection corresponds to 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF; and PCBs 118, 105 and 156 were the more frequent dl-PCBs. The food groups presenting higher contamination, expressed as toxic equivalents (WHO-TEQs), were fish oil (6.38 pg WHO-TEQ g(-1)fat), fish (1.21 pg WHO-TEQ g(-1)w.w.) and milk and dairy products (0.90 pg WHO-TEQ g(-1)fat). Of all analysed samples, only two fish oils presented levels higher than the EU limits for total WHO-TEQ. The average PCDD/Fs and dl-PCBs intakes were estimated as 2.86 pg WHO-TEQ kg(-1)b.w.d(-1) and 4.58 pg WHO-TEQ kg(-1)b.w.d(-1), for adults and children, respectively, using the deterministic method for chronic exposure. The main contributors to total intake for adults were fish (59%), milk and dairy products (19%), and fat and oils (9%). The average daily intake for adults (2.86 pg WHO-TEQ kg(-1)b.w.d(-1)) is within range of TDI recommended by the WHO (1-4 pg WHO-TEQ kg(-1)b.w.d(-1)), and slightly above the TWI and PTMI adopted by SCF and JECFA respectively.

Persistent organic pollutants (PCDD/Fs, dioxin-like PCBs, marker PCBs, and PBDEs) in health supplements on the Spanish market.

During the last years, consumption of health supplements has increased in our society. They are recommended as an additional source of minerals, vitamins, omega-3 and omega-6 fatty acids, in the diet. A lot of these supplements contain oils among their components (fish oils or vegetable oils), especially those recommended for their omega-3 content. Due to their persistence and lipophilic characteristics, polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs), marker PCBs, and polybrominated diphenyl ethers (PBDEs) bioaccumulate in fat tissues, especially in those animals, as fish, which show low metabolic capability. Therefore, the consumption of nutritional supplements with oil components can increase the intake of persistent organic pollutants (POPs) through the diet. The aim of this study was to analyse 15 of these supplements commercialized in Spain to determinate their POPs concentrations and their intake for their consumers. Concentrations of POPs in the dietary supplements studied (PCDD/Fs: 0.04-2.4 pg TEQ g(-1); dl-PCBs: 0.01-12.1 pg TEQ g(-1); marker PCBs: 0.17-116 ng g(-1); and PBDEs: 0.07-18.2 ng g(-1)) were in the low-medium range of those reported in literature for other countries. Vegetable oil and mineral-based supplements showed concentrations of POPs clearly lower than those based on fish oil. Among these, those based on cod liver oil presented the highest concentrations detected in the study, exceeding the maximum levels established in European regulations for marine oils for human consumption. In general, the intake of POPs via the consumption of these supplements would be lower than the intake derived from fish consumption.

Separation of non-ortho polychlorinated biphenyl congeners on pre-packed carbon tubes. Application to analysis in sewage sludge and soil samples

The analysis of planar (non-ortho) polychlorinated biphenyls (PCB) by HRGC-ECD or HRGC-HRMS requires a fractionation step to avoid the interferences of the bulk of PCB, usually in much higher concentration than the planar ones. In this paper, a new method, based on the fractionation of PCB on SPE commercial tubes pre-packed with Carbopack B, has been developed. After the extract has been applied on the stationary phase, the bulk of PCD are eluted with 15 ml of hexane (fraction I), mono-ortho PCB with 20 ml of hexane/toluene 99:1 (fraction II) and planar PCB with 20 ml of toluene (fraction III) in a station under vacuum. The method has been validated: accuracy (expressed as recovery in %) is >70% and precision (expressed as % RSD) is <20% considering changes of day, analyst and batch of tubes. The method is linear in the range studied. Other advantages are that the method is simple, rapid and it can be easily automated. The application of this separation to the determination of planar PCB in fly-ash extracts from an intercalibration exercise and to sewage sludge, sediment and soil samples has been successful. In addition, this method removes hydrocarbons from the planar PCB fraction and allows its concentration to very small volumes.

Baseline levels of PCDD/Fs in soil and herbage samples collected in the vicinity of a new hazardous waste incinerator in Catalonia, Spain

The construction in Constanti (Catalonia, Spain) of a new hazardous waste incinerator (HWI), which is the first one in Spain, finished in 1999. In order to determine the temporal variation (1996-1998) in the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the vicinity of the new HWI, 40 soil and 40 herbage samples were collected (1998) at the same sampling points in which samples had been taken two years before (1996). Each sample was analyzed for PCDDs and PCDFs by high resolution gas chromatography/high resolution mass spectrometry. In the 1996 survey, PCDD/F concentrations in soils ranged from 0.13 to 24.20 ngl-TEQ/kg (d.m.), with median and mean values of 0.67 and 1.68 ngl-TEQ/kg (d.m.), respectively. In the present study, PCDD/F concentrations ranged from 0.12 to 17.20 ng I-TEQ/kg (d.m.), with a median value of 0.75 ng I-TEQ/kg (d.m.) and a mean value of 1.59 ng I-TEQ/kg (d.m.). In turn, in the present study PCDD/F concentrations in vegetation ranged from 0.14 to 2.01 ng I-TEQ/kg(d.m.) (median and mean values: 0.23 and 0.31 ng I-TEQ/kg, respectively), while in the 1996 survey PCDD/F concentrations ranged from 0.24 to 1.22 ngl-TEQ/kg (d.m.) (median and mean values: 0.53 and 0.61 ng I-TEQ/kg. respectively). According to the present (1998) and the previous (1996) levels of PCDD/Fs found in soils and vegetation, the area under potential influence of the new facility shows a rather low contamination by these compounds. The current results should be useful to establish the environmental impact of the HWI.

Human exposure to PCDD/Fs and PCBs through consumption of fish and seafood in Catalonia (Spain): Temporal trend

The concentrations of PCDD/Fs and 18 PCBs (DL- and NDL-) were analyzed in 16 fish and seafood species widely consumed in Catalonia (Spain). The exposure of these pollutants was subsequently estimated according to various groups of population. The concentrations of PCDD/Fs and PCBs showed an important decrease in relation to the baseline study (2000) and our last survey (2008). Sardine and red mullet were the species showing the highest pollutant concentrations, while canned tuna and cuttlefish presented the lowest levels. Sardine was the main contributor to the exposure of PCDD/Fs and PCBs. In contrast, swordfish was the species with the lowest contribution to the exposure of PCDD/Fs, DL-PCBs, and PCDD/Fs+DL-PCBs, while clam was the minor contributor for NDL-PCBs and total PCBs. For all groups of population, the current intakes of PCDD/Fs and PCBs were lower than the TDI (1-4 pg WHO-TEQ/kg body weight/day), being children the group with the highest exposure. However, this exposure should not mean a health risk for this group of population. The current intake of PCDD/Fs and PCBs through fish and seafood consumption was similar or even lower than most values reported in recent studies all over the world.

Elimination of persistent organic pollutants from fish oil with solid adsorbents.

Fish oils are one of the main sources of ω-3 fatty acids in animal and human diet. However, they can contain high concentrations of persistent organic pollutants due to their lipophilic properties. The aim of this study is the reduction of persistent organic pollutants in fish oil using silicon-based and carbon-based solid adsorbents. A wide screening study with different commercially available adsorbents was carried out, in order to determine their capacity of pollutant removal from fish oil. Moreover, adsorption conditions were evaluated and optimized with using an experimental design and adjustment of the experimental results to response surfaces, obtaining removals rates of more than 99% of PCDD/Fs, 81% of dioxin-like PCBs, 70% of HCB, 41% of DDTs, 16% of marker PCBs and 10% of PBDEs. Finally, fish oil fatty acids were analyzed before and after the treatment with solid adsorbents, confirming that it did not affect its nutritive properties.

Environmental impact of a new hazardous waste incinerator in Catalonia, Spain: PCDD/PCDF levels in herbage samples.

In April 1996 and 1998, the concentrations of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were determined in 40 herbage samples collected in the neighborhood of a hazardous waste incinerator (HWI) under construction in Constanti (Catalonia, Spain). In April 2000, 20 months after the HWI began operating, herbage samples were again collected at the same sampling points in which samples had been taken in the previous surveys. PCDD/F concentrations ranged between 0.13 and 0.65 ng I-TEQ/kg (dry matter), with a median and mean values of 0.29 and 0.32 ng I-TEQ/kg (dry matter), respectively. The results were compared with those obtained in the 1996 (median, 0.53 ng I-TEQ/kg; mean, 0.61 ng I-TEQ/kg) and the 1998 (median, 0.23 ng I-TEQ/kg; mean, 0.31 ng I-TEQ/kg) surveys. While in the period 1996-1998 a significant decrease (49%, P < 0.001) in the mean PCDD/F levels was noted, in the period 1998-2000 an increase of 3% (P > 0.05) was found in the concentrations of PCDD/Fs. The analysis of the results suggests two potential hypotheses: either the emissions of PCDD/Fs from the HWI are not negligible, or the current PCDD/F emissions from other sources near the HWI remained at similar levels to those reached in 1998. Anyhow, an exhaustive evaluation of the present data shows an absence of notable PCDD/F contamination by the HWI in the area under its direct influence. It seems also probable that the decline in the atmospheric levels of PCDD/Fs due other emission sources of PCDD/Fs in this area is currently stopped.

Human exposure to environmental pollutants after a tire landfill fire in Spain: Health risks.

In May 2016, a fire occurred in one of the largest landfills in Europe (Seseña, Toledo, Spain), where 70,000-90,000tons of tires had been illegally accumulated for >15years. Because of the proximity of population nuclei and the duration of the episode (>20days), we conducted a preliminary human health risk assessment study just after the tire fire. Samples of air and soil were collected in 3 areas surrounding the landfill (El Quiñón, at only 500m, and Seseña Nuevo and Seseña Viejo, both at 4km), as well as in background sites. In addition, samples of crops (barley, wheat, cabbage and lettuce) were also obtained from local farmers. The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and a number of trace elements (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Sn, Tl, and V) were analyzed in all the samples. The concentrations of all the target pollutants, excepting PAHs, were relatively similar at the different sampling zones, irrespective of the distance to the landfill. In turn, a significant increase of PAHs was noted near the tire landfill, with air levels up to 6-times higher than those found at 4km (134 vs. 19.5-22.7ng/m3). Similarly, PAH concentrations in lettuce were relatively higher than those typically found in monitoring programs of food safety. Because of the increase of airborne PAHs, cancer risks due to exposure to environmental pollutants for the population living at El Quiñón, near the landfill, were between 3- and 5-times higher than those estimated for the inhabitants of Seseña. After this preliminary study, further investigations, focused only on PAHs, but more extensive in terms of number of samples, should be conducted to assure that PAHs have been progressively degraded through time.

Development and validation of a method for analyzing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sewage sludge samples

SummaryA method has been developed for the analysis of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in sewage sludge samples. It was found that PCDD/F are best Soxhlet extracted from the matrix with toluene for 24h, after having tested other solvents (dichloromethane and hexane/acetone 41/59) and other extraction times. Several clean up steps (sulfuric acid, multilayer silica and Florisl columns) and concentration are required prior to analysis of the extract by high resolution gas chromatography-high resolution mass spectrometry (HRGC-HRMS). The complete procedure has been validated and the accuracy and precision data (repeatability and reproducibility) are given. The method is linear in the range studied and the limit of detection ranges between 0.2 and 2.2 pg g−1 of dry matter for the 2,3,7,8-substituted congeners. Moreover, the suitability of the method has been checked in an international interlaboratory comparison. The successful application of this method to several samples from Catalan and Dutch urban wastewater treatment plants was demonstrated.