Spatial, temporal, and inter-compartmental environmental monitoring of lipophilic pollutants by virtual organisms.

Sampling points belonging to the Harz National Park river system, Germany, were selected between the period of 2014 and 2017 for monitoring polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in water, air, and sediment. Triolein-containing Virtual Organisms (VO) were employed to assess the levels of chemicals in water, air and triolein as surrogate for natural fat. To avoid overestimation of the concentrations 20 performance reference compounds (PRCs)-16 PRCs-PAHs and 4 PRCs-PCBs were covering the range of properties of native compounds. Results manifested the highest concentration of individual PAH as follows: 31 ng fluoranthene/L water, 3600 ng pyrene/g fat, 62 ng phenanthrene/m3 air and 2800 ng fluoranthene/g dw sediment. All PCBs and OCPs values were below above mentioned PAH concentrations and far below EU-limit levels. Environmental partition of chemicals was investigated by calculating fugacity, suggesting a mass transport from water to air. Only quite volatile compounds such as hexachlorobutadiene showed higher fugacity in air. Ratios of sediment/water concentrations and log Kow within individual sampling periods at Holtemme River exhibited strong linear relationships. Interestingly, during summer months of the years water and fat contents well correlate to the flow rates of Holtemme River. Our results show that VO can be successfully used as a tool for ongoing exposure assessment studies and predictions of worst case levels in food and nutrition.

Comparative exposomics of persistent organic pollutants (PCBs, OCPs, MCCPs and SCCPs) and polycyclic aromatic hydrocarbons (PAHs) in Lake Victoria (Africa) and Three Gorges Reservoir (China).

Exposomics is assessment of organism exposure to high priority environmental pollutants in an ecosystem using OMIC technologies. A virtual organism (VO) is an artificial property-tool (OMIC) reflecting exposomic process in compartments of real organisms. The exposomics of aquatic organisms inhabiting Lake Victoria (L.V.) and Three Gorges Reservoir (TGR) were compared using VOs. The two reservoirs are heavily depended on for food and water both in Africa and China. The target priority pollutants in the reservoirs were polyclic aromatic hydrocarbons (PAHs) and persistent organic pollutants such as polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), medium chain chlorinated paraffins (MCCPs) and short chain chlorinated paraffins (SCCPs). The VOs showed that in a period of 28 days, aquatic organisms in TGR were exposed to total (∑) PAHs of 8.71 × 10-6 mg/L, PCBs of 2.81 × 10-6 mg/L, OCPs of 2.80 × 10-6 mg/L, MCCPs of 8.9 × 10-10 mg/L and SCCPs of 1.13 × 10-7 mg/L. While in a period of 48 days, organisms in L. V. were exposed to total (∑) PAHs of 7.45 × 10-6 mg/L, PCBs of 4.70 × 10-6 mg/L, OCPs of 3.39 × 10-8 mg/L, MCCPs of 4.6 × 10-10 mg/L and SCCPs of 3.6 × 10-9 mg/L. The exposomic levels in TGR after 28 days were higher than those in Lake Victoria after 48 days. In both reservoirs, bioaccumulation levels are above set standards for aquatic organisms. The sources of the pollutants into the reservoirs were diagnostically determined to originate from anthropogenic processes such as petrogenic, diesel emissions, biomass burning, coal combustion, electronic wastes, traffic emissions and historic uses.

Comparative study of dioxin contamination from forest soil samples (BZE II) by mass spectrometry and EROD bioassay.

Dioxins and dioxin-like compounds can be analyzed by bioanalytical screening methods to evaluate their biotoxicity. In vitro bioassays, based on 7-ethoxyresorufin-O-deethylase (EROD) and the activity of cytochrome P450 1A1 and the aryl hydrogen receptor (AhR) pathway, are employed for the evaluation of bioanalytical equivalents (BEQ) of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) from a wide variety of sample matrices. Here, we present the evaluation of 11 humic soil samples derived from forest stands across Germany and a comparison of the BEQ values against toxic equivalents (TEQ, PCDD/Fs+PCBs) derived by chemical analysis. BEQ values ranged from 8.8 to 34.1 while TEQ values from 13.9 to 60.5 pg/g dry weight. Additional two subsequent mineral layers were analyzed to identify the BEQ/TEQ gradient vertically, showing a TEQ decrease of 85.1 and 93.8 % from the humic to the first and second mineral layers, respectively. For BEQ values, a decrease as well as an increase was detected. BEQ measurements were performed with and without sample clean-up. Omitting clean-up revealed about 20 times increased BEQ values presumably due to non-persistent bioactive compounds not detected by chemical analysis. The results we present suggest that the EROD assay can be used for the screening of large sample quantities for the identification of samples showing dioxin and dioxin-like contaminations even at low levels, which can then be further analyzed by chemical analysis to identify the congener composition. The study also shows that EROD results give a qualitative image of the contamination. EROD seems to be interfered with cross-contaminants specifically for soils with high biological activity as forest layers.

Results of the second national forest soil inventory in Germany - Interpretation of level and stock profiles for PCDD/F and PCB in terms of vegetation and humus type.

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were detected in 86 humic topsoil layers and in a subset of 11 randomly selected top mineral forest soils at the depths of 0-5cm and 5-10cm collected from different federal states of Germany. The distribution of these persistent organic pollutants (POPs) in humic topsoils with respect to vegetation cover (coniferous vs. deciduous vs. mixed), total organic carbon (TOC), altitude and latitude data was investigated. There is cross correlation between the contents and TOC while the correlation with latitude indicates higher abundances of POPs in central Germany where there is high population density accompanied with industrial activities. The calculated stocks suggest that humus type (mor, mull, or moder) in conjunction with forest type can explain the relative POPs abundances in different soil layers. Generally, humic topsoils show highest contents of POPs compare to the two mineral soils with a ratio of 100:10:1. However, the stock humic layers of coniferous stands contribute about 50% to the total stock, whereas at deciduous stands the stock is mainly located in the upper mineral soil layer (0-5cm). The soil-water distribution coefficients (Kd) were calculated to estimate the potential translocation in the different soil types. The Kd values vary among the PCBs and PCDD/Fs congeners and are most variable for humic topsoils. There is pronounced chemical abundance in the top mineral soils with increasing Kd and this points to non-water bound transport processes for superlipophilic compounds.

Persistent organic pollutants in shallow percolated water of the Alps Karst system (Zugspitze summit, Germany).

In the German Calcareous Alps at the Zugspitze, percolated water close to a permafrost bedrock in a tunnel system was monitored long-term for polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), polychlorinated biphenyls (PCB), polycyclic aromatic hydrocarbons (PAH), and 28 organochlorine pesticides (OCP). Semi-permeable membrane devices (SPMD) were deployed in a temporary surface water system at the Zugspitze plateau and analysed for PCB, PAH, and OCP. The high-volume water sampling was successfully implemented and all compounds were identified in the water percolated through the Karst system. However, the percentage distribution of contaminants in the percolated water differed significantly from that found in surface waters. The highest chlorinated PCDD homologues were the predominant compounds of the PCDD/F family, whereas percentages of PCB #52 increased in percolated water. Toxic equivalent values (TEQ) of samples ranged from 2.0 to 4.2pgTEQ/m3 and from 0.017 to 0.069pgTEQ/m3 for PCDD/F and PCB, respectively. Low and intermediate molecular weight PAH were the prevailing compounds in the samples. Endosulfan sulfate, endrin, and cis-heptachlor epoxide were enhanced after water percolation through the Karst system in comparison with the surface waters (wet deposition). The relative enrichment on these pesticides was related to the environmental bedrock conditions and glacier melting sources. In summary, the Karst system highly influenced the fate of organic persistent pollutants generating different chemical patterns in their percolated waters than those found at the surface systems.

The fingerprints of dioxin-like bromocarbazoles and chlorocarbazoles in selected forest soils in Germany.

The occurrence of bromocarbazoles and chlorocarbazoles was studied in 86 forest soil samples from different regions in Germany. Carbazole, 3-chlorocarbazole, 3-bromocarbazole and 3,6-dibromocarbazole were qualitatively detected in the humic layer of 59 soil samples with bromocarbazoles reported here for the first time in soil. Furthermore, the halogenated carbazoles, PCDD/Fs and PCBs were detected in the humic and mineral soil horizons (0-5 cm and 5-10 cm) of a subset of 11 soil samples subjected to quantitative analysis. Concentrations ranged from 0.6 to 267.6 ng/g (carbazole); 0.2-7.2 ng/g (3-bromocarbazole); 0.0-9.1 ng/g (3-chlorocarbazole); 0.2-19.8 ng/g (3,6-dibromocarbazole); 0.4-67.6 ng/g (3,6-dichlorocarbazole); 0.0-0.7 ng/g (PCDDs); 0.0-0.3 ng/g (PCDFs) and 0.0-33.7 ng/g (PCBs). Concentrations decreased with depth and correlated positively to total organic carbon (TOC). When it was based on TOC%, an increase in concentration with depth was observed in most soil samples. With respect to dioxin-like toxicity, 3-bromocarbazole, 3-chlorocarbazole, 3,6-dibromocarbazole and 3,6-dichlorocarbazoles caused induction of CYP1A1-dependent EROD activity in HII4E rat hepatoma cell line. Their relative effect potency after 72 h exposure ranged from 0.00005 to 0.00013 and was directly related to the degree of halogenation with 2,3,7,8-tetrachlorodibenzo-p-dioxin as reference. Furthermore, their contribution to overall soil dioxin-like toxicity was not significant in comparison to PCDD/Fs and PCBs though the sum toxic equivalency was limited to three halogenated carbazole congeners. Bromocarbazoles and chlorocarbazoles are emerging dioxin-like toxic environmental contaminants with potential for wide distribution occurring simultaneously with PCDD/Fs and PCBs.

Persistent endosulfan sulfate is found with highest abundance among endosulfan I, II, and sulfate in German forest soils.

Endosulfan - an agricultural insecticide and banned by Stockholm Convention - is produced as a 2:1 to 7:3 mixture of isomers endosulfan I (ESI) and endosulfan II (ESII). Endosulfan is transformed under aerobic conditions into endosulfan sulfate (ESS). The study shows for 76 sampling locations in German forests that endosulfan is abundant in all samples with an opposite ratio between the ESI and ESII than the technical product, where the main metabolite ESS is found with even higher abundance. The ratio between ESI/ESII and ESS show clear dependence on the type of stands (coniferous vs. deciduous) and humus type and increases from deciduous via mixed to coniferous forest stands. The study argues for a systematic monitoring of ESI, ESII, and ESS and underlines the need for further research, specifically on the fate of endosulfan including biomagnifications and bioaccumulation in soil.

Coexposure to phytoestrogens and bisphenol a mimics estrogenic effects in an additive manner.

Endocrine-disrupting chemicals (EDC) are abundant in our environment. A number of EDCs, including bisphenol A (BPA) can bind to the estrogen receptors (ER), ERα and ERß, and may contribute to estrogen-linked diseases such as breast cancer. Early exposure is of particular concern; many EDCs cross the placenta and infants have measurable levels of, eg, BPA. In addition, infants are frequently fed soy-based formula (SF) that contains phytoestrogens. Effects of combined exposure to xeno- and phytoestrogens are poorly studied. Here, we extensively compared to what extent BPA, genistein, and an extract of infant SF mimic estrogen-induced gene transcription and cell proliferation. We investigated ligand-specific effects on ER activation in HeLa-ERα and ERß reporter cells; on proliferation, genome-wide gene regulation and non-ER-mediated effects in MCF7 breast cancer cells; and how coexposure influenced these effects. The biological relevance was explored using enrichment analyses of differentially regulated genes and clustering with clinical breast cancer profiles. We demonstrate that coexposure to BPA and genistein, or SF, results in increased functional and transcriptional estrogenic effects. Using statistical modeling, we determine that BPA and phytoestrogens act in an additive manner. The proliferative and transcriptional effects of the tested compounds mimic those of 17ß-estradiol, and are abolished by cotreatment with an ER antagonist. Gene expression profiles induced by each compound clustered with poor prognosis breast cancer, indicating that exposure may adversely affect breast cancer prognosis. This study accentuates that coexposure to BPA and soy-based phytoestrogens results in additive estrogenic effects, and may contribute to estrogen-linked diseases, including breast cancer.

Genistein and dicarboximide fungicides in infant formulae from the EU market.

A method based on ultrasonic extraction and purification by solid phase extraction followed by LC-MS/MS and GC-MS analysis was developed for the determination of genistein, genistin, iprodione, vinclozolin and procymidone in infant powdered formulas. The method was tested for different formulations: milk, soy and hypoallergenic, and was applied to European pooled samples. Spike recoveries ranged from 53.1% to 91.5% and the relative standard deviation values for repeatability ranged from 9.6% to 17.7%, except for iprodione in milk formula (22.3%). None of the fungicides were found in the European pooled formulae, while genistein was found at 9.7µg/g in soy formula and the concentration of genistin, its ß-glycosylated form, was respectively 31.4ng/g and 476ng/g in milk and soy formula.

Human and environmental biomonitoring of polychlorinated biphenyls and hexachlorobenzene in Saxony, Germany based on the German Environmental Specimen Bank.

The objective of the present study was to investigate the principle relationships between concentrations in human and environmental matrices of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) in short distance comparable areas within Saxony, Germany by employing the data of the German Environmental Specimen Banking (ESB). Examples supporting this idea were presented by selecting data on blood plasma collected from students in University of Halle and pine shoots, egg matter of city pigeons, earthworm, and roe deer liver. Similar pattern for PCB 138 and PCB 180 was found for the human plasma and pine shoots samples during investigated years and the human data followed the corresponding environmental levels with some delay of approximately two years. However, PCB 153 that was the prevailing congener did not manifest this relationship. In addition, the correlation of the ratios of concentrations (human/environmental concentration) to some physicochemical constants such as molecular weight (MW), octanol-water partition coefficient (logK(ow)), Henry's law constant (K(H)), and sorption partition coefficient (logK(oc)) of HCB, PCB 138, PCB 153, and PCB 180 were studied. The resulted negative slopes with all constants in case of blood plasma/city pigeons egg matter pairs suggested that the accumulation of lipophilic compounds is more pronounced in pigeon eggs than in human blood.

Laboratory studies on formation and minimisation of polychlorinated dibenzodioxins and -furans (PCDD/F) in secondary aluminium process.

The objectives of this work were to study the formation mechanisms of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) in thermal aluminium recycling processes by use of laboratory experiments. The pattern of isomers of PCDD/F indicates that de novo synthesis is important in aluminium smeltery. The mechanisms of PCDD/F formation in aluminium smelting are similar to that of various incineration processes of waste material. The results of bioanalysis (EROD-test) confirms the existence of de novo synthesis of PCDD/F, but points out to the existence to some additional, toxic compounds of unknown structure. To reduce the amount of PCDD/F the input of carbon at the metal should be reduced; in addition the metal smeltery plants should be cleaned from fly ash particles. It is suggested to use good primary methods in the technical plants like constant feeding of the metal into the oven will minimise PCDD/F concentration. The biological EROD-bioassay is a good tool to estimate PCDD/F-TEQ values also for this technical process simulated in the laboratory.

Assessment of energy intake of infants exclusively fed with infant formulae available on the European market.

The aim of the present study was to assess the total daily energy intake of infants (aged 0-4 months) exclusively fed with infant formulae available on the European Union market. All of the products were identified from the European market share data of the year 2007 covering 22 countries. The calculated daily energy intake based on the instructions labelled on these products was compared with the energy requirements based on World Health Organization recommendations, considering the standard body weight established by the Food and Agriculture Organization. In addition, the daily energy intake was also calculated based on direct measurements of the amount of formulae contained in the spoon provided by the supplier. It was found that the kcal/day intakes provided by the supplier were higher than the values recommended by international organizations. The energy intake values calculated based on the direct spoon measurements were even higher.

Correlation of PCDD/F and PCB at combustion experiments using wood and hospital waste. Influence of (NH(4))(2)SO(4) as additive on PCDD/F and PCB emissions.

The objectives of this work were to study the emissions of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyl (PCB) during the combustion of wood, wood and hospital waste as well as wood, hospital waste and (NH(4))(2)SO(4) in a pilot plant and to determine the relation of the toxic emissions to the fuel properties. The presence of PVC (experiments b and c) increases PCDD/F and PCB formation compared to burning only eco-farm wood (a). However, analysis and quantification of PCDD/F and PCB showed that the amount of 5% of (NH(4))(2)SO(4) in the fuel mixture significantly impacted the dioxins emissions and suppressed it by approximately 50%. In addition, longer duration of the combustion experiment by using (NH(4))SO(4) resulted in a stronger inhibition of the toxic emissions. Overall, the lowest values were observed during the combustion of the fuel blends containing wood only. Relationships of PCDD/F (WHO-TEQ) and individual congeners of WHO-PCDD/F, WHO-PCB and six PCB indicator congeners were also found. As a result, all single PCB congeners were identified as PCDD/F (WHO-TEQ) surrogates in the flue gas. Furthermore, the correlation between PCDD/F and PCB congeners was examined by statistical methods such as cluster analysis (CA). Closely neighboured pairs on the dendrogram were additionally confirmed by a high linear coefficient of determination (R(2)). (NH(4))(2)SO(4)-containing samples did not affect the correlations between PCDD/F and PCB at the concentrations given.

Primary measures for reduction of PCDD/F in Co-combustion of lignite coal and waste: effect of various inhibitors.

Co-combustion of coal and waste in power plants poses both environmental and economic challenges, especially because of the high polychlorinated dibenzo-p-dioxin and furan (PCDD/F) emissions from solid waste. In this study, we performed a series of experiments focusing on the prevention of PCDD/F formation by the use of various inhibitors added to the fuel before combustion. A mixture of lignite coal, solid waste, and poly(vinyl chloride) (PVC) was thermally treated in a laboratory-scale furnace at 400 degrees C. Twenty different additives were investigated at a level of 10 wt% of the total fuel during the experiments. We have divided them into four general groups according to their chemical nature: metal oxides, N-containing compounds, S-containing compounds, and N- and S-containing compounds. The resulting values showed a significant reduction of PCDD/F levels when N- and S-containing compounds were used as additives to the fuel. Principle component analysis (PCA) was used to illustrate the effect of the 20 different inhibitors on the congener patterns emitted. As a result, the most effective inhibitors for PCDD/F formation in flue gases were determined to be (NH4)2SO4 and (NH4)2S2O3; they are inexpensive and nontoxic materials. Both compounds can suppress the formation of toxic compounds such as PCDD/Fs by more than 98-99%, and the most toxic PCDD/F congeners were not detectable in most of the samples. Thus, these compounds were also studied as a lower percentage of the fuel. (NH4)2SO4 resulted in a greater than 90% reduction of PCDD/F even when composing only 3% of the fuel combusted. However, less than 5% (NH4)2S2O3 resulted in far weaker inhibition. The PCDD/F homologue distribution ratio for samples with varying percentages of (NH4)2SO4 and (NH4)2S2O3 was also investigated. Higher percentages of the inhibitors produced a lower percentage of lower chlorinated PCDDs. The opposite effect was found for PCDFs.