Serum levels of PCDDs, PCDFs and dl-PCBs in general population residing far and near from an urban waste treatment plant under construction in Gipuzkoa, Basque Country (Spain).

This research focused on investigating the basal serum concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in the general population residing in two urban-industrial zones near and far from an energy recovery plant under construction in Gipuzkoa, Basque Country (Spain). The study used a cross-sectional design and included 227 participants who were randomly selected from municipal censuses in both areas. The participants were stratified based on age (ranging from 18 to 70 years) and sex. Serum samples were collected from the participants and analysed following the established protocol to measure the concentrations of PCDD/Fs and dl-PCBs. The study used multiple linear regression models to assess the impact of various sociodemographic variables, lifestyle factors, reproductive history, and diet on the variability of the measured compounds in the participants' serum. The median total toxicity equivalent (TEQ) in serum, was 10.58 pg WHO-TEQ2005 g-1 lipid. Serum PCDD levels were lower in the population residing in the "far" zone than the "near" zone. Age was positively associated with both PCDD/F and dl-PCB levels, indicating that older participants had higher concentrations of these compounds in their serum. This finding might be attributed to cumulative exposure over time. In terms of sex differences, women exhibited lower levels of dl-PCBs compared to men. Among lifestyle factors, smokers showed lower levels of dl-PCBs compared to non-smokers. Furthermore, daily alcohol consumption was significantly associated with higher serum levels of these compounds, with daily drinkers showing higher levels than non-drinkers. Consumption of local poultry was associated with significantly higher serum levels and oil consumption with low levels of PCDD/Fs.

Dioxin-like POPs in national samples from global monitoring plan projects (2017-2019).

The global monitoring plan (GMP) established under the Stockholm Convention on Persistent Organic Pollutants (POPs) had defined ambient air, human milk or blood, and water as core matrices to be analyzed and assessed for spatial and temporal distribution. Within projects coordinated by the United Nations Environment Programme (UNEP), developing countries were offered to have other matrices analyzed for dioxin-like POPs (dl-POPs) in experienced laboratories. Subsequently, 185 samples from 27 countries located in Africa, Asia, and Latin America were collected during 2018-2019 and analyzed for polychlorinated dibenzodioxins (PCDD), dibenzofurans (PCDF), and biphenyls (PCB). Using the WHO2005 toxic equivalency approach (TEQ), the amounts of dl-POPs found were low (<1 pg TEQ/g); however, singular samples had higher values; e.g., egg from Morocco, fish from Argentina or Tunisia; soil and sediment samples. Results showed that the matrix, abiotic or biota, had more impact on the TEQ pattern than the geographic location. Independent of the location and across all samples, dl-PCB in (shell)fish and beef samples had a contribution of 75% to the total TEQ; milk (63%), chicken (52%), and butter (50.2%) more than 50%. Sediment (57% and 32%) and soil (40% and 36%)) samples were dominated by PCDD and PCDF, respectively; therein, dl-PCB had shares of 11% and 24%. Egg samples (N = 27) did not follow the general biota pattern and had 21% of the TEQ from the PCDD, 45% from PCDF, and 34% from dl-PCB; thus, indicating that abiotic matrices such as soil or other material may have an impact.

Levels of regulated POPs in fish samples from the Sava River Basin. Comparison to legislated quality standard values.

Fish samples of different species (i.e. rainbow trout (Onchorhynchus mykiss), barbel (Barbus barbus) and European chub (Squalius cephalus)) were collected from the Sava River Basin for a preliminary investigation of the levels of PCDD/Fs, PCBs, PBDEs and PFAS as a whole. Concentrations of PCDD/Fs, in terms of pg WHO-TEQ/g ww, were below the maximum limit established at the Commission Regulation (EU) No 1259/2011. On the contrary, when DL-PCBs were also included, levels increase up to 11.7 pg WHO-TEQPCDD/Fs+DL-PCBs/g ww in a particular case, with two samples out of a total of ten exceeding the maximum set at this EU Regulation and the EQS established at the European Directive regarding priority substances in the field of water policy (0.0065 ng WHO-TEQPCDD/Fs+DL-PCBs/g ww). A similar trend was also observed for NDL-PCBs, whit the same two samples, from the lower stretch of the river basin, exceeding the maximum limit allowed at the EU Regulation (125 ng/g ww). For PBDEs, levels found in all the samples exceeded the EQS (0.0085 ng/g ww) up to more than a thousand times and 40% of the samples presented PFOS values above the EQS. Data from this study were compared to values reported at the literature for fish from other geographical areas.

Changes in serum dioxin and PCB levels in residents around a municipal waste incinerator in Bilbao, Spain.

There is a great concern in the Basque Country regarding emissions from waste incineration, in particular that of organochlorines (OCs), including dioxins, furans and polychlorinated biphenyls (PCBs), and their potential effect on human health. In 2005, a municipal solid waste plant (MSWP) started to operate in Bilbao, representing an opportunity to assess the exposure to the aforementioned pollutants among people living at various distances from the plant. In 2006 and 2008, we carried out two cross-sectional studies to quantify and assess changes in levels of these pollutants. The objective of this study was to describe the levels of OCs in the blood serum in 2013 of 127 adults of this prospective cohort, in four centres of population, near to and further away from the MSWP, and to study trends over time since it started to operate. This study shows the levels of OCs have decreased significantly, from 37.2% to 80.1%. Further, levels of OCs in areas near to the MSWP were not found to be higher than those in areas further afield.

Dioxins and dl-PCBs in gull eggs from Spanish Natural Parks (2010-2013).

The aim of this study was to evaluate the presence and distribution of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and biphenyls (PCBs), concretely those so-called as dioxin-like PCBs, in yellow-legged gull eggs (Larus michahellis) collected from five Natural Parks (some of them National Parks) in Spain during the period 2010-2013. PCDD/Fs and dl-PCBs were detected in all the samples. Due to the proximity to important urban and industrial areas higher concentrations were determined in colonies located in the Northern Mediterranean coast than those found in the Southern Mediterranean or Atlantic colonies where a softer anthropogenic impact occurs. Mean ∑PCDD/F concentrations ranged from 49 to 223pg/g lipid weight (lw) and ∑dl-PCB concentrations varied from 146 to 911ng/g lw. In the Natural Park of the Ebro Delta (Northern Mediterranean coast) two gull species share habitat: yellow-legged and Audouin gull (Larus audouinii). Eggs from both species were collected and PCDD/F and dl-PCB levels compared. The species that feeds exclusively on pelagic fish (L. audouinii) had significantly higher PCDD/F and dl-PCB levels than the scavenger L. michahellis, pointing out the diet-dependent differences in the accumulation of persistent organic pollutants between similar cohabitant breeding species. Finally, mean TEQ values were in general below those considered as critical for toxicological effects in birds.

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.

Levels of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in placentas from the Spanish INMA birth cohort study.

Because fetuses are considered significantly more sensitive to various environment toxicants, there is a need for continuous biomonitoring of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls PCBs (DL-PCBs) to assess their impact on this susceptible population. The aim of this study was to assess the concentration of PCDD/Fs and DL-PCBs in placenta samples from women participating in the Spanish Environment and Childhood (INMA) birth cohort study and to evaluate whether maternal and child characteristics predict placenta concentrations of these pollutants. The presence of PCDD/Fs and DL-PCBs was investigated in 50 placenta samples selected at random in the recruitment period 2000-2008. Multivariable regression models were constructed. Mothers had a mean age at delivery of 30.7 years (18.0-38.0 years), pre-pregnancy BMI of 23.3 kg/m² (18.0-40.2 kg/m²), and 31% were smokers. Median total concentrations of PCDD/Fs and DL-PCBs were 6.9 pg WHO-TEQ/g lipid and 2.1 pg WHO-TEQ/g lipid, respectively. In comparison to the few previous studies in placenta, total TEQ levels were among the lowest recorded in comparable general populations. The congener distribution pattern and the frequencies and concentrations of PCDD/F and DL-PCB congeners were similar to previous reports in placenta. PCDD/F and DL-PCB exposure was related to the age of the mother and the year of the delivery. Although placental concentrations cannot be considered wholly appropriate predictors for evaluating fetal exposure to these contaminants, they can provide a good indication of both maternal and infant prenatal and postnatal exposure and can be used as a proxy for fetal exposure.

Persistent Organic Pollutants in gull eggs of two species (Larus michahellis and Larus audouinii) from the Ebro delta Natural Park.

The aim of this study was to determine the impact of priority and emerging Persistent Organic Pollutants (POPs) in gull eggs from two species, the scavenger Larus michahellis and the protected species, Larus audouinii. These two species share habitat in the Natural Park of the Ebro delta (Catalonia, Spain). Compounds studied are included or under consideration in the Stockholm Convention and comprise polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorinated compounds (OCs), perfluorinated compounds (PFCs) and short chain chlorinated paraffins (SCCPs). Four methods based in selective extraction and gas or liquid chromatography coupled to mass spectrometry were used and quality parameters are provided. OC pesticides and marker PCBs were the most abundant chemical families detected in eggs from the two species, followed by PFCs, PBDEs (especially BDE 209) and SCCPs. Dioxin-like PCBs and PCDD/Fs were also detected in all samples. The overall widespread presence of POPs is discussed in terms of feeding habits, bird ecology and anthropogenic pressures in the protected Ebro delta breeding area.

Decontamination trends in the aquacultured fish gilthead seabream (Sparus aurata) after feeding long-term a PCDD/F spiked feed.

Aquacultured fish gilthead seabream (Sparusaurata), previously exposed to low levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) trough the diet for a 13 months period, were fed on a clean feed for another 22 months. Gilthead seabream is a protandrous hermaphrodite species and this "decontamination" period coincided with the stages of sex differentiation, maturity and reproduction of the fish. PCDD/F levels in the fish tissues (i.e. muscle, liver, perivisceral fat and gonads), expressed in pg WHO-TEQg⁻¹ fresh weight, showed a general decreasing trend during the "decontamination" period. However, this general trend varied among tissues and was also dependent on sex and lipid contents. Toxicological effects affecting fish behaviour and hepatic marker responses were also evaluated. The results pointed out that exposure to PCDD/Fs did not have an impact on fish development and reproduction, since the proportion of sexes found after the sex reversal process was within the normal range described for this species. In addition, long-term exposure to low PCDD/F levels did not significantly affect the response of most of the biochemical markers considered. On the contrary, some of them (e.g. EROD activity) showed variations in their responses during the sex differentiation process and onwards. Finally, the hepatic AhR mRNA levels increased during dioxin exposure but they returned to values typical for non-exposed fish after the "decontamination" period.

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.