Spatial gradients of OCPs in European butter--integrating environmental and exposure information.

The Stockholm Convention and the Global Monitoring Plan encourage the production of monitoring data to effectively evaluate the presence of the persistent organic pollutants (POPs) in all regions, in order to identify changes in levels over time, as well as to provide information on their regional and global environmental transport. Here, we report the first step of two to investigate whether butter is a feasible matrix to screen with the purpose to reflect regional ambient atmospheric air levels of POPs. The first step described here is to generate monitoring data; the second is to investigate the relationship between the two matrixes, i.e., POP concentrations in air and butter, which will be reported in another article published in this journal. Here, the 27 organochlorine pesticides listed under the Stockholm Convention have been analyzed in 75 butter samples from Europe. The general conclusions were as follows: Total organochlorine pesticide concentration is lower in butter from northern and central Europe. The spatial gradient of 1,1,1-trichloro-2,2-di(4-chlorophenyl)ethane and hexachlorocyclohexane is increasing in the eastern region of Europe (Romania, Bulgaria, and Ukraine), dieldrin towards France, and endosulfan levels were elevated on the Azores Island in the Atlantic Ocean. One butter sample from Romania exceeded the European Maximum Residue Limit value for lindane, but the other butter pesticide levels were all below the limit values. The dataset reported here can be used for the calibration of the air-grass-dairy products model, which would support the feasibility to use butter as biomonitor for measuring POP levels in ambient air.

Seasonality of PCDD/Fs in the ambient air of Malopolska region, southern Poland.

BACKGROUND, AIM, AND SCOPE: The aim of the study was to identify the impact of polychlorinated dibenzo-p-dioxin and furan (PCDD/F) emission sources on ambient air concentrations in the Malopolska Region, southern Poland. Three sites were selected: the city center of Krakow (Aleje), an industrial area (Nova Huta), and a rural site (Zakopane). In order to investigate the annual variations of PCDD/F sources, summer and winter time samples were taken. MATERIALS AND METHODS: Ambient air particulate matter (PM10) was collected using an Anderson High-Volume sampler during June and December 2002 in the three mentioned sites. Analysis of PCDD/Fs was based on isotope dilution using high-resolution gas chromatography-high-resolution mass spectrometry for quantification. RESULTS AND DISCUSSION: Total concentrations of 2,3,7,8-PCDD/Fs in air particulate phase from Malopolska region ranged from 0.6 to 37 pg m(-3) (0.04-3.2 pg WHO(98)-TEQ per cubic meter, 0.037-2.9 pg I-TEQ per cubic meter). Higher PCDD/F concentrations were measured at all three sites during winter. A linear correlation among PCDD/F concentrations, benzo(a)pyrene (B(a)P) and PM10 concentrations, was found in Aleje and Zakopane, which suggested that all compounds were originating from the same source, solid fuel domestic heating. Instead, PCDD/F levels in Nova Huta did not correlate with the seasonality of B(a)P or PM10 levels and 2,3,7,8-PCDD/F congener patterns for this site were significantly different from the other sites. CONCLUSIONS: Domestic solid fuel combustion is likely the main PCDD/F source in winter in this part of Poland for urban and rural sites. PCDD/F fingerprints in the industrial site remained almost identical during summer and winter, confirming the yearly prevalence of the emissions from the nearby metal industry. RECOMMENDATIONS AND PERSPECTIVES: PCDD/F concentrations found in Malopolska Region are in the upper range of ambient air concentrations of PCDD/Fs reported worldwide. However, further research is needed in order to study the impact of the deposition of these PCDD/F emissions on the region. A more extended study is being conducted in the area to analyze soil samples, such as sink of atmospheric deposition, and spruce needles, as indicator of PCDD/F availability.

Levels of PCDD/Fs and trace elements in superficial soils of Pavia Province (Italy).

Trace elements and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were analyzed in soils from rural and light-industrialized sites (n = 168) of Province of Pavia (Northern Italy). Most of the trace element values fit in typical ranges of concentrations in soils and are similar to the ones reported for rural sites in Italy or sites with no direct anthropogenic impact. Total concentrations of 2,3,7,8 chlorine substituted PCDD/Fs in superficial soils ranged between 24.4 and 1287 pg g(-1) dw (0.5-28.9 pg WHO98-TEQ g(-1) dw). The North Eastern part of the Province presented significantly higher levels (p < 0.001) than the rest of the Province for As, Cd, Hg, Pb, Zn and PCDD/Fs. While the existence of a defined heavy metal polluting source for this specific site has been suggested, in the case of PCDD/Fs, profiles were not linked to any specific emission source fingerprint. In the whole extension of Pavia Province, OCDD/F dominated the 2,3,7,8 chlorine substituted congener soil pattern, followed by the 1,2,3,4,6,7,8 hepta-CDD/F congener. Principal Component Analysis (PCA) showed that this profile could not be associated to any described PCDD/F emission source fingerprint and was relatively similar to the baseline deposition of sites with no direct impact of PCDD/F emission sources independently of land use.

Organochlorine residue levels in livers of birds of prey from Spain: inter-species comparison in relation with diet and migratory patterns.

Livers from 130 specimens corresponding to 18 species of raptors from Spain were analysed for persistent organochlorine (OC) residues. In all species, p,p'-DDE was the most abundant individual OC compound detected, with geometric means ranging from 61 to 40,086 ng/g ww. The geometric mean for summation operator PCB ranged from 225 to 9184 ng/g ww. Migration to Africa, south of Sahara, where p,p'-DDT is still in use, was not associated with higher liver concentrations of its metabolite, p,p'-DDE. The presence of birds in the diet of the species was an important species-specific factor determining the mean liver concentrations of p,p'-DDE and summation operator PCB. The effect of the diet on OC concentrations in liver is explained by the lower metabolising capacity of OC compounds in birds, especially for p,p'-DDE.

Occurrence of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in Lake Maggiore (Italy and Switzerland).

Samples of air (gas and particulate phases), bulk deposition, aquatic settling material and sediments were collected in Lake Maggiore (LM) in order to determine their content of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Air (gas and particulate phases) concentrations were 0.5 pg m(-3), 80 pg m(-3), 13 pg m(-3) and 106 pg m(-3) for SigmaPCDD/Fs, SigmaPCBs, Sigma dioxin-like PCBs (DL-PCBs) and SigmaPBDEs, respectively. Deposition fluxes ranged from 0.7 ng m(-2) d(-1) for SigmaPCDD/Fs to 32 ng m(-2) d(-1) for SigmaPCBs. Aquatic settling material presented concentrations of 0.4 ng g(-1) dry weight (dw) for SigmaPCDD/Fs, 13 ng g(-1) dw for SigmaPCB, 3.4 ng g(-1) dw for SigmaDL-PCBs and 5.7 ng g(-1) dw for SigmaPBDEs. Mean sediment concentrations were 0.4 ng g(-1) dw for SigmaPCDD/Fs, 11 ng g(-1) dw for SigmaPCB, 3 ng g(-1) dw for SigmaDL-PCBs and 5.1 ng g(-1) dw for SigmaPBDEs. Similar PCDD/F and DL-PCB congener patterns in all the environmental compartments of LM point to an important, if not dominant, contribution of atmospheric deposition as source of these pollutants into LM. In contrast, PBDE congener distribution was not similar in the different environmental compartments. BDE 47 dominated air and settling material, while BDE 209 was the predominant congener in the bulk atmospheric deposition. Moreover, sediments showed two distinct PBDE congener profiles. Lower PBDE concentrated sediments were dominated by congeners 47 and 99, while BDE 209 dominated in higher PBDE concentrated samples. This suggests the influence of local sources as well as atmospheric input of PBDEs into LM.

Estrogenic activity associated with organochlorine compounds in fish extracts from European mountain lakes.

Fish muscle extracts from ten European mountain lakes were analyzed for organochlorine compounds (OCs) and estrogenic activity, the latter by a recombinant yeast assay based on the human estrogen receptor. Seventy percent of the samples showed estrogenic activity above detection limits and a subset of five samples showed estrogenic activities, equivalent to more than 10,000 pg/g of estradiol. These highly estrogenic samples occurred in two lakes, Velké Hinçovo in the Tatra Mountains and Redon in the Pyrenees. Principal component analysis correlated estrogenic activity of muscle extracts to fish age and concentrations of the more chlorinated polychlorobiphenyls (PCBs). This is consistent with previously observed correlations of these PCBs with fish age. In addition, most fish with high estrogenic activity were found in lakes containing high OC levels in the sediments, which gives further ground to atmospheric deposition of anthropogenic pollutants as main process leading to the observed endocrine disruption effects.

Distribution of polycyclic aromatic hydrocarbons in the food web of a high mountain lake, Pyrenees, Catalonia, Spain.

We investigated the contents of polycyclic aromatic hydrocarbons (PAHs) in the food web organisms included in the diet of brown trout from a remote mountain lake. The preferential habitat and trophic level of the component species have been assessed from the signature of stable isotopes (delta13C and delta15N). Subsequently, the patterns of accumulation and transformation of these hydrocarbons in the food chain have been elucidated. Most of the food web organisms exhibit PAH distributions largely dominated by phenanthrene, which agrees with its predominance in atmospheric deposition, water, and suspended particles. Total PAH levels are higher in the organisms from the littoral habitat than from the deep sediments or the pelagic water column. However, organisms from deep sediments exhibit higher proportions of higher molecular weight PAH than those in other lake areas. Distinct organisms exhibit specific features in their relative PAH composition that point to different capacities for uptake and metabolic degradation. Brown trout show an elevated capacity for metabolic degradation because they have lower PAH concentrations than food and they are enriched strongly in lower molecular weight compounds. The PAH levels in trout highly depend on organisms living in the littoral areas. Fish exposure to PAH, therefore, may vary from lake to lake according to the relative contribution of littoral organisms to their diet.

The roles of food and water in the bioaccumulation of organochlorine compounds in high mountain lake fish.

An integrated study encompassing the distribution of organochlorine compounds (OC) in water, food web (chironomids, terrestrial insects, cladocerans, mollusks, and cyanobacteria), and fish (brown trout) from a high mountain lake (Redon, Pyrenees) is reported. OC distributions in these compartments have been determined to assess theirtransport routes into fish. Food diets have been estimated by analysis of fish stomach content and food web stable isotopes (delta13C and delta15N). OCs with octanol--water partition coefficient (Kow) higher than 10(6) showed lower concentrations in food than expected from theoretical octanol--water partition, indicating thatthe distribution of these compounds does not reach equilibrium within the life span of the food web organisms (ca. 1 year). On the other hand, the degree of biomagnification in fish increased with Kow, except in the case of the largest compound analyzed (seven chlorine substituents, PCB #180). OC exchange at fish gill and gut has been evaluated using a fugacity model based on the water, food, and fish concentrations. All compounds exhibited a net gill loss and a net gut uptake. A pseudostationary state was only achieved for compounds with log(Kow) < 6. Calculation of fish average residence times for the compounds in apparent steady state gave values of days to a few weeks for HCHs, 1 year for HCB and 4,4'-DDE, and 2-3 years for 4,4'-DDT and PCB#28 and PCB#52. Residence times longer than one decade were found for the more chlorinated PCB.

Polybromodiphenyl ether flame retardants in fish from lakes in European high mountains and Greenland.

Individual polybromodiphenyl ethers (PBDEs) were investigated in liver and muscle tissue of trout from 11 high mountain lakes in Europe and one in Greenland. Trouts in these lakes [brown trout (Salmo trutta), brook trout (Salvelinus fontinalis) and arctic char (Salvelinus alpinus)] are important sentinel species because they are located in the top of the food chain and pollution can only reach these ecosystems by atmospheric transport. The major PBDE congeners were BDE 47 and BDE 99, followed by BDE 100, BDE 153, BDE 154, and BDE 28. These compounds were found in all the samples examined. Their average concentrations [110-1300 and 69-730 pg g(-1) wet weight (ww) in liver and muscle or 2400-40000 and 2900-41000 pg g(-1) lipid weight (lw), respectively] were in the lower range when compared with those of fish from other less remote locations. The highest levels of PBDEs in liver and muscle are found in Lochnagar, Scotland: 11000 and 1200 pg g(-1) ww, respectively (366 000 and 177000 pg g(-1) lw, respectively). Male specimens exhibited higher PBDE concentrations in liver than female. The concentrations of most PBDEs in liver were correlated with fish age (p < 0.01) and, inversely, with condition factor (p < 0.01). Muscle PBDE concentrations did not correlate with age, and only some congeners showed significant positive correlations with condition factor (p < 0.05). The main differences between species were found in the accumulation of the more abundant PBDEs, brook trout showing the highest concentrations in muscle and the lowest in liver. No correlation between the occurrence of these compounds in high mountain fish and altitude, latitude, or temperature was observed. This fact and the lack of correlation between muscle concentrations and age suggest that the fluxes of PBDEs arriving at high mountain lakes are still not constant. In view of the present use of these compounds, they are probably increasing.

Influence of altitude and age in the accumulation of organochlorine compounds in fish from high mountain lakes.

The analysis of hexachlorobenzene, hexachlorocyclohexanes, polychlorobiphenyls, and DDTs in muscle of fish from high mountain lakes shows that a proportion of their concentration variance depends on fish age and lake altitude. Interestingly, the magnitude of this share corresponds linearly with the log-transformed vapor pressure (Vp) of the organochlorine compounds (OC). Thus, the distributions of OC with Vp < 10(-2.5) Pa are mostly determined by these two variables. Altitude gradients mainly respond to temperature differences, involving concentration increases of 25-150 times between 8.7 and -2.3 degrees C. The age effect encompasses concentration increments of 2.4-7.8 for average lake differences between 2 and 13 yr. However, both effects are independent since no correlation between fish age and lake altitude is observed. Fish liver concentrations exhibit the same pattern, but the correlations are only significantfor age, suggesting thatthe temperature trend is more related to long-term accumulation than episodic intake. The temperature effect is independent from compound origin. In addition, the sites situated at highest altitude, those most distant from possible ground pollution sources, are the most polluted. The results can be explained by condensation effects such as those described for the latitudinal trends that support the global distillation theory. However, in the high altitude lakes a temperature-dependent amplification mechanism, probably related to low metabolism and respiration at lowtemperatures, enhances OC accumulation in fish beyond the increases predicted from theoretical condensation and solubilization enthalpies. The observed temperature dependence suggests that a general remobilization of OC accumulated in high mountain areas could take place as a consequence of the general warming of these areas anticipated in the climatic change studies.

Method for integrated analysis of polycyclic aromatic hydrocarbons and organochlorine compounds in fish liver.

An analytical method for integrated analysis of organochlorine compounds and polycyclic aromatic hydrocarbons (PAH) in large numbers of fish liver samples has been developed using one single clean-up step. Tissues are homogenized with anhydrous sodium sulphate and Soxhlet extracted with n-hexane-dichloromethane (4:1, v/v) for 24 h. The extracts are cleaned-up and fractionated with an alumina chromatographic column allowing the separation of the extracts in two fractions. One containing most organochlorine compounds, including hexachlorobenzene, DDTs and polychlorobiphenyls, and the other the hexachlorocyclohexane isomers and PAH. These two fractions are subsequently analysed by GC-MS. Tests of repeatability result in relative standard deviations mainly under 20%. Evaluation by the standard addition method shows good linearities and recoveries.