Concentrations of organochlorine pesticides and 2,4,6-trichloroanisole in cork bark

Organochlorine pesticides are persistent lipophilic organic pollutants and tend to accumulate in growing plants. During growth, cork is in contact with the open air for long periods (9-12 years). Owing to the previous widespread use of organochlorine pesticides and their high persistence in the environment, there is a risk that residues of such pesticides may be present in cork.In this study, the concentrations of 14 organochlorine pesticides—all of which are indicators of environmental pollution—were analyzed in cork bark samples from three regions in Spain and one in Portugal. In addition, the concentrations of 2,4,6-trichlorophenol (TCP) and 2,4,6-trichloroanisole (TCA) were also analyzed.Our results show only very low concentrations of lindane, γ-HCH (<2.6 ng g⁻¹) and its byproducts α-HCH (<3.5 ng g⁻¹) and β-HCH (<0.6 ng g⁻¹).Among the DDT and its metabolites, only two were found: p,p′-DDT was found in a cork sample from Extremadura (0.1 ng g⁻¹) and p,p′-DDE was present at a maximum concentration of 2.9 ng g⁻¹ in a cork sample from Castile-La Mancha. However, all concentrations were well below the legal limit established by Regulation (EC) No. 396/2005 (10 ng g⁻¹ in foodstuffs). We can conclude, therefore, that the cork samples we studied complied with food safety standards.     

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.     

Baseline soil levels of PCDD/Fs established prior to the construction of municipal solid waste incinerators in China

In order to determine the baseline contamination by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in different areas in China, prior to the construction of municipal solid waste incinerators (MSWIs), a total of 32 representative soil samples was collected near 16 incinerators and analyzed for their PCDD/F concentrations. The PCDD/F baseline concentrations in the soil samples ranged from 0.32 to 11.4 ng I-TEQ kg⁻¹ (dry matter), with average and median value of 2.73 and 2.24 ng I-TEQ kg⁻¹ (dry matter), respectively, and a span between maximum and minimum recorded value of 36. The PCDD homologues predominated in 26 out of 32 soil samples, with the ratio (PCDDs)/(PCDFs) ranging from 1.1 to 164; however in the other 6 samples, PCDF homologues were larger, with the same ratio varying from 0.04 to 0.8. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were used to examine PCDD/F amount and profile in these soil samples, and their possible associations with known emission sources: in this process 6 really distinct isomer fingerprints were identified. Background PCDD/F levels and profiles were comparable to those found in soils from China and other countries and indicate a rather low baseline PCDD/F contamination of soils. The present data provide the tools for future assessment of a possible impact of these MSWIs.     

Lindane removal by pure and mixed cultures of immobilized actinobacteria

Stereoselective dissipation of epoxiconazole had been studied in grape and soil during plant growing under field conditions in this paper. A sensitive and rapid chiral method was developed and validated for the determination of epoxiconazole stereoisomers in grape and soil based on liquid chromatography coupled with triple quadrupole mass spectrometry (LC-MS/MS). Phenomenex Lux Cellulose-1 column was used for enantioseparation with a mixture of acetonitrile/water (90/10, v/v) as mobile phase at flow rate of 0.3 mL min⁻¹. Fortified recoveries in grape and soil samples ranged from 76.0% to 91.9% and relative standard deviations were less than 11.4% with fortified levels of 0.025-1.0 mg kg⁻¹. The limits of detection and quantification were 0.005 mg kg⁻¹ and 0.025 mg kg⁻¹, respectively, with linear calibration curves extending up to 5.0 mg kg⁻¹. The field experimental results showed that dissipations of epoxiconazole stereoisomers in grape followed first-order kinetics (R² > 0.92) and stereoselectivity occurred in 2 h after spraying. The (−)-stereoisomer with half-life of 9.3 d degraded faster than (+)-stereoisomer with that of 13.2 d, and resulted in relative enrichment of (+)-stereoisomer. However, the stereoisomeric dissipations in soil were triphasic (“increase-decrease-steady”) with lower dissipation rates, and also occurred with preferential degradation of (−)-stereoisomer under field condition. The results for stereoselective dissipations can be applied for food and environmental assessments of chiral pesticides.     

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in breast milk of first-time Irish mothers: impact of the 2008 dioxin incident in Ireland

The 2008 dioxin incident in Ireland resulted in elevated concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in Irish pork and pork products, due to the consumption of contaminated animal feed by pigs. In order to investigate any resulting impact on the Irish population, these contaminants were measured in pooled breast milk samples from 109 first-time mothers, collected in 2010. A comparison of the results with similar data from 2002 revealed generally lower concentrations of PCDD/Fs and dioxin-like PCBs in the 2010 samples, confirming the declining trend reported by many authors. Contaminant concentration levels for both 2002 and 2010 were generally slightly lower than those reported internationally, with a mean combined PCDD/F and PCB WHO-TEQ of 9.66 pg g⁻¹ fat, for an overall pooled sample of milk from 2010. An apparent slight increase in PCDFs was observed between 2002 and 2010 (from 2.73 pg WHO-TEQ g⁻¹ fat to 3.21 pg WHO-TEQ g⁻¹ fat), with the main contributory congener being 2,3,4,7,8-PentaCDF. While it cannot be totally discounted that the slight increase in 2,3,4,7,8-PentaCDF and in the overall PCDF WHO-TEQ in breast milk could be attributable to consumption of Irish pork during the 2008 incident, we consider that it is more likely that this was due to other factors, including the predominantly urban/industrial sampling locations for the 2010 samples, compared to 2002.     

Formation of PCDD/Fs from oxidation of 2-monochlorophenol over an Fe2O3/silica surface

The role of iron in surface-mediated formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from 2-chlorophenol (2-MCP) was investigated over the temperature range of 200-550 °C under oxidative conditions. In order to compare and contrast with previous work on copper and ferric oxide-mediated pyrolysis of 2-MCP, identical reaction conditions were maintained (50 ppm 2-MCP, model fly-ash particles containing 5% Fe₂O₃ on silica). Observed products included dibenzo-p-dioxin (DD), 1-monochlorodibenzo-p-dioxin (1-MCDD), dibenzofuran (DF), 4,6-dichlorodibenzofuran (4,6-DCDF), 2,4- and 2,6-dichlorophenol, 2,4,6-trichlorophenol, quinone, catechol, chloro-o-quinone, chlorocatechol and polychlorinated benzenes. Yields of DD and 1-MCDD were 2 and 5 times higher than under pyolysis conditions, respectively. Although 4,6-DCDF was the major PCDD/F product formed with a yield that was 2.5× greater than under pyrolysis, the yield of non-chlorinated DF, which was the dominant PCDD/F product under pyrolysis, decreased by a factor of 3. Furthermore, the ∼2× higher yield of PCDDs under oxidative conditions resulted in a PCDD to PCDF ratio of 0.75 compared to a relatively low ratio of 0.39 previously observed under pyrolytic conditions.     

Subcellular distribution and toxicity of cadmium in Potamogeton crispus L

The submerged macrophyte Potamogeton crispus L. was subjected to varying doses of cadmium (0, 20, 40, 60 and 80 μM) for 7 d, and the plants were analyzed for subcellular distribution of Cd, accumulation of mineral nutrients, photosynthesis, oxidative stress, protein content, and ultrastructural distribution of calcium (Ca). Leaf fractionation by differential centrifugation indicated that 48-69% of Cd was accumulated in the cell wall. At all doses of Cd, the levels of Ca and B rose and the level of Mn fell; the levels of Fe, Mg, Zn, Cu, Mo, and P rose initially only to decline later. Exposure to Cd caused oxidative stress as evident by increased content of malondialdehyde and decreased contents of chlorophyll and protein. Photosynthetic efficiency, as indicated by the quenching of chlorophyll a fluorescence (Fv/Fm, Fo and Fm), decreased significantly, the extent of decrease being directly proportional to the concentration of Cd. Increased amounts of precipitates of calcium were noticed in the treated plants, located either outside the cell membrane or in chloroplasts, mitochondria, the nucleus, and the cytoplasm whereas control plants showed small deposits of the precipitates around surface of the vacuole membrane and in the intercellular space but rarely in the cytoplasm. Photosynthetic efficiency and oxidative stress could be used as indicators of physiological end-points in determining the extent of Cd phytotoxicity.     

Emission characterization of unintentionally produced persistent organic pollutants from iron ore sintering process in China

Emission of unintentionally produced persistent organic pollutants (Unintentional POPs), including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychorinated biphenyls (PCBs), hexachlorobenzene (HxCBz) and pentachlorobenzene (PeCBz), were investigated in four typical iron ore sintering plants in China. The emission factors and annual mass releases of the Unintentional POPs were calculated. The results indicated that PCDFs contributed more than 60% to the overall toxic equivalent quantity (TEQ) values, while the contribution of the dl-PCBs is relatively low, and only in the range of 8-9%. The dominant congeners of PCDD/Fs and dl-PCBs contributing most to the total TEQ were 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and PCB-126. With regard to the TEQ contributions, the most abundant homologues were PeCDFs and HxCDD/Fs, followed by PeCDDs and non-ortho dl-PCB, whereas HpCDD/Fs, OCDD/Fs and mono-ortho dl-PCBs almost made no contributions. Due to the massive use of recycled waste in the feeding materials, the average emission factor of PCDD/Fs and dl-PCBs of the four plants was 3.95 μg WHO-TEQ ton⁻¹. Based on the results, the annual release of PCDD/Fs and dl-PCBs in 2007-2009 were estimated to be 2070 g, 2212 g, and 2307 g WHO-TEQ, respectively.     

Altered toxicity of organic pollutants in water originated from simultaneous exposure to UV photolysis and CdSe/ZnS quantum dots

The paper reports unforeseen results of increased toxicity of water, subsequent to interactions between CdSe/ZnS quantum dots (QDs), phenol and toluene under UV irradiation. The consistent pattern of changes in measured toxicity (TU) was observed and correlated with degradation of phenol and/or toluene. Spearman rank coefficients (SRCs) for data pairs sum-parameters vs. TU were calculated. The highest correlation between toxicity and degradation by-products was observed for hydroquinone (0.86) and catechol (0.89). The presence of QDs in tested concentration range in the absence of UV has shown low toxicity and no interactions with phenol and/or toluene. The leak of constituent core and shell metal ions was observed. The minor differences in physical characteristics of tested QDs of the same chemical composition led to rather different degradation patterns of phenol and toluene, and the amount of leak of the metal ions as well.