PBDE and PCB contamination of eels from the Gironde estuary: from glass eels to silver eels

Since the 1980s, the eel population has been decreasing dangerously. Persistent Organic Pollutants (POPs) such as Polychlorinated Biphenyls (PCBs) are one of the suspected causes of this decline. A preliminary study of PCB contamination carried out on different fish from the Gironde estuary (southwest of France, Europe) has shown a relatively high level of contamination of eel muscles. In order to characterize the contamination level of PCBs and PBDEs (PolyBrominated Diphenyl-Ethers) in eels from this estuary more than 240 eels were collected during the years 2004-2005 in the Gironde estuarine system, from glass eels to silver eels. Individual European eels were grouped according to length and localization sites. The results have shown a low contamination level of glass eels: respectively 28 ± 11 ng g⁻¹ dw for PCBs and 5 ± 3 ng g⁻¹ dw for PBDEs. The contamination level in eels (expressed in ng g⁻¹ dw) increases from glass eels to silver eels up to 3399 ng g⁻¹ dw of PCBs for the most contaminated silver eel. Such levels of PCBs similar to those observed in Northern Europe, could raise sanitary problems connected with the World Health Organization (WHO) recommendations. These results are worrying for the local people who regularly eat eels caught in the Gironde estuary.     

Occurrence of PCDD/F, PCB, PBDE, PFAS, and organotin compounds in fish meal, fish oil and fish feed

We analysed polychlorinated dibenzo-p-dioxins and furans (PCDD/F, dioxins), and polychlorinated biphenyls (PCB) in 13 fish meal, five fish oil, and seven fish feed samples. Polybrominated diphenyl ethers (PBDE), organotin compounds (OTC), and perfluoroalkylated substances (PFAS) were analysed in ten fish meal, two fish oil, and two fish feed samples. All measured TEQ concentrations of PCDD/F and PCB were below the maximum levels set by Directive 2002/32/EC. There was no correlation between concentrations of WHOPCDD/F-TEQ and indicator PCB in our samples. The most common congeners among PBDEs were BDE-47 and BDE-100. BDE-209 was present in five fish meals of the ten analysed. Tributyltin (TBT) was the predominant congener in all samples except in three fish meals, where monobutyltin (MBT) was the major congener. Perfluorooctane sulphonate (PFOS) was the predominant congener in six fish meals of the ten analysed. There was large variation in concentrations and congener distributions of the studied compounds between our samples. Our results underline a need to pay special attention to the origin and purity of feed raw material of marine origin.     

PCDD/F, PCB, PBDE, HBCD and chlorinated pesticides in a Swedish market basket from 2005--levels and dietary intake estimations

Based on consumption data statistics, food items from four regions in Sweden were sampled in a so-called market basket study. Food items from five food groups, i.e. fish, meat, dairy products, eggs and fat/oils, were analyzed for persistent organic pollutants (POPs) followed by per capita intake calculations. The highest levels of PCDD/F, PCB, PBDE, HBCD and chlorinated pesticides were found in the fish/fish products. The estimated market basket per capita intake of PCDD/F and dl-PCB was 0.7 pg WHO-TEQ kg bw⁻¹ d⁻¹ (TEFs from 1998). The intake of ∑PCB was estimated to 4.9 ng kg bw⁻¹ d⁻¹ and fish was found to be the major contributor with 64%. The intake of ∑PBDE was found to be 0.7 ng kg bw⁻¹ d⁻¹. Fish (38%) and dairy products (31%) were the largest contributors to the total PBDE intake. The intake of HBCD was estimated to 0.14 ng kg bw⁻¹ d⁻¹. HBCD mainly came from fish (65%), but also dairy products (24%) and meat (10%) contributed. Also regarding the chlorinated pesticides, fish was found to be the major contributor, with 51% of the ∑DDT coming from fish. The intake of ∑DDT, ∑HCH and HCB was 4.0, 1.0 and 1.1 ng kg bw⁻¹ d⁻¹, respectively. Most of the ∑HCH and HCB originate from dairy products (43% and 55%, respectively). This study shows that the levels, and intake, of different POPs from food of animal origin in the market basket of 2005 seem to have decreased since the market basket study in 1999.     

PCDD, PCDF, PCB and PBDE concentrations in breast milk of mothers residing in selected areas of Slovakia

The concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and polybrominated diphenylethers (PBDEs) in 33 breast milk samples collected in 2006-2007 from primipara mothers close to four industrial areas of Slovak Republic were determined. The total PCDDs/PCDFs and dl-PCBs expressed as TEQ based on WHO TEFs 1998 in breast milk samples varied from 5.0 to 51.8 pg g⁻¹ fat (median: 13.1 pg g⁻¹ fat; mean: 18.0 pg g⁻¹ fat). The measurements of seven PBDE congeners (IUPAC No. 28, 47, 99, 100, 153, 154, and 183) were performed for the first time in human milk from Slovakia. PBDE levels ranged between 0.22 and 1.62 ng g⁻¹ fat, with median and mean value of 0.43 ng g⁻¹ fat and 0.57 ng g⁻¹ fat respectively. No statistically significant differences were observed between studied areas in total PBDE concentrations.Furthermore, this study presents first results concerning the daily intake (DI) of PCDDs/PCDFs and dioxin-like compounds for the most vulnerable breast-fed infant population in Slovakia. The total PCDD/PCDF and dl-PCB DI for an infant during the first 2 months of life was estimated in a range from 14.4 to 230 pg TEQ kg⁻¹ b.w., with a median value of 58.9 pg TEQ kg⁻¹ b.w.. The DI values substantially exceeded the tolerable daily intake (TDI) 1-4 pg TEQ kg⁻¹ b.w. recommended by WHO. The dietary infant intake concerning PBDEs was estimated to be between 0.69 and 7.1 ng kg⁻¹ b.w. d⁻¹, with median value of 1.7 ng kg⁻¹ b.w. d⁻¹.     

Antimicrobial potential of commercial silver nanoparticles and the characterization of their physical properties toward probiotic bacteria isolated from fermented milk products

The application of nanotechnology in the agriculture and food sector is relatively recent compared to its usage in drug delivery or pharmaceuticals. Therefore, this paper presents a study of the effect of silver nanoparticles on probiotic bacteria based on the example of Lactobacillus acidophilus LA-5, Bifidobacterium animalis subsp. lactis BB-12 and Streptococcus thermophilus ST-Y31 isolated from fermented milk products. Probiotic bacteria are one of the most crucial groups of bacteria for the food industry, because of their claimed health-promoting properties. Studies have shown that the type and concentration of silver nanoparticle solutions have a significant impact on the tested probiotic bacteria which are profitable for the digestive system. In the presence of all tested silver nanoparticles, St. thermophilus ST-Y31 growth was inhibited significantly by the dilution method as opposed to the disk-diffusion method. Both the disk-diffusion and the dilution methods showed no significant differences between L. acidophilus LA-5 and B. animalis subsp. lactis BB-12. The concentrations 2 μg mL^?1 and 0.25 μg mL^?1 had the highest antibacterial activity and statistically significant impacts on the tested probiotic strains. To our knowledge, this is the first report on potential antimicrobial effect of nanosilver against the health-promoting probiotic bacteria L. acidophilus LA-5, B. animalis subsp. lactis BB-12 and St. thermophilus ST-Y31 isolated from fermented milk products.     

PCDD/PCDF, dl-PCB and PBDE serum levels of Slovak general population

Blood serum specimens from 81 non-occupationally exposed adults residing in four areas close to municipal and waste incinerators as well as metallurgical industry plant and 44 adult subjects coming from control area of Slovakia were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and polybrominated diphenylethers (PBDEs). The concentration of total WHO(98)TEQ PCDD/F/dl-PCBs in whole group of donors from areas where known sources causing dioxin contamination are present was significantly higher than in control group of donors (p<0.001). Correlation between the age of donors and PCDD/F and dl-PCB levels was confirmed (Spearman's r(PCDD/Fs)=0.543, r(dl-PCBs)=0.521, p<0.001). Furthermore, this study presents first results concerning the PBDE congeners in human serum of Slovak general population. The total concentration (congeners 28, 47, 99, 100, 153, 154, 183) in control group was approximately 1.5-times higher in comparison to that of residents coming from areas with supposed environmental pollution. The most abundant congeners in all samples were BDE-47 and BDE-153 with median values of 0.24 ng g(-1) lipid and 0.23ngg(-1) lipid, respectively. The positive association between PBDE values and age of donors was not found.     

MAP热分解产物的氨氮吸附性能研究

以TG-DTA、XRD、SEM等手段研究了MAP的热分解行为,并对热分解产物的氨氮吸附性能进行了研究。结果表明,热分解MAP可将水和氨释放出来,热分解产物粒径变小,结晶度降低,其XRD图谱主要出现MgHPO₄·3H₂O的特征衍射峰,但在吸附氨氮后,则主要出现MgNH₄PO₄·6H₂O的特征衍射峰;控制MAP在100℃条件下热分解3 h再用于氨氮的处理药剂是合适的,氨氮吸附反应体系的pH值以10较为适宜,在此条件下反应40 min对氨氮的去除率即达90%。     

PCDD/F and PCB in spruce forests of the Alps

PCDD/F and PCB concentrations in remote mountainous spruce stands of the Central European Alps show strong geographic variation. Independent of the matrix (0.5 year old needles, humus or mineral soil), the highest pollutant levels were always found at the lateral zones of the mountain range. High levels coincided with strong precipitation, particularly along the northern margin of the study region. The most volatile PCB congener propagated farther into the colder, drier central Alps than the heavier species. Matrices with different accumulation history (needles and humus) repeatedly reflected different spatial immission patterns. Consistent with its much longer exposure, pollutant levels in humus exceeded those of needles by up to two orders of magnitude. Needle contamination varied with altitude but the vertical trends were highly variable between transsects and changed between years, too.     

Photolysis of flumequine: identification of the major phototransformation products and toxicity measures

Direct photolysis of flumequine (FLU, 20 mg L⁻¹) in different types of water (demineralised water (DW) and synthetic seawater (SW)), was conducted in a Suntest CPS + solar simulator to evaluate its persistence and toxicity, and to identify the major phototransformation products (PTPs) generated during photolysis in DW. It was observed that FLU is susceptible to transformation when subjected to direct solar radiation. The composition of the water affects the FLU degradation kinetics, which is slower in SW. Photolytic transformation products generated during direct photolysis were identified by liquid chromatography-time of flight-mass spectrometry (LC-TOF-MS). Fourteen PTPs generated in DW were identified. The transformation of FLU begins with the opening of the heterocyclic ring by oxidation of the double bond. Loss of the fluorine atom and the hydroxylation of the aromatic ring also appear as the majority, especially in the early stages. Comparative acute toxicity evaluation by Vibrio fischeri and Daphnia magna bioassays was performed for the first and last irradiated solutions in both matrices studied. These bioassays demonstrated that in the SW matrix, the most persistent PTPs are highly toxic to D. magna but less so to V. fischeri.     

A summary of the 209 PCB congener nomenclature

Primary publications of congener numbering shorthand systems for PCB congener identification were reviewed, including the original Ballschmiter-Zell (BZ) system; recommended changes by Schulte and Malisch, and Guitart et al.; and listings by the Chemical Abstracts Service. Comparisons of the various congener numbering shorthands and chlorine substitution numberings in the structural name listings are presented. Several changes, to adhere more closely to IUPAC rules, have been incorporated into the BZ structural nomenclature, and these resulted in renumbering congeners. These corrected listings have been erroneously identified as "IUPAC" numbers, a misnomer, because IUPAC has not published a shorthand system. Guitart pointed out additional inconsistencies with IUPAC rules for nine congeners which would result in further order changes, but did not recommend renumbering, to avoid further confusion. We noted an additional error in the structural name for congener 97, named 2,2',3',4,5 using Ballschmiter and Zell nomenclature and 2,2',3,4',5' using strict IUPAC nomenclature. This renaming would cause the renumbering of the IUPAC number system reported by Guitart for isomers 91 through 98. No further changes are recommended, however. Tables summarizing each publication, and the discrepancies between them are provided in hopes of clarifying the current state of the nomenclature.     

Studies on the coupling product between oxidation products derived from pentachlorophenol and cyclodextrins

The coupling products (CPs), which were formed via the peroxosulfate catalyzed oxidation of pentachlorophenol (PCP) with iron(III)-tetrakis(sulfonatophenyl)porphyrin (Fe(III)-TPPS) in the presence of hydroxypropyl-beta -cyclodextrin (HP-beta -CD) or HP-gamma -CD, were separated by ultrafiltration from the reaction mixture. When the percentages of chlorine species in the reaction mixture were calculated from the concentrations of organic chlorine in the reaction mixture and CPs, 10-25% of chlorine species in the reaction mixture was organic chlorine that was incorporated into CDs. Analyses of the CPs by pyrolysis-GC/MS (Py-GC/MS) and 13C NMR showed that the PCP-derived products were covalently incorporated into the CDs. To evaluate the acute toxicity of the CPs, a Microtox test was examined. Toxicities of the CPs were reduced slightly, compared to the controls (PCP alone and PCP + reaction blanks). In the reaction blanks, mesaconic acid (MA) moieties were detected as a result of the oxidation of CDs in the absence of PCP. Thus, factors in the toxicities, detected in the CPs, can be attributed to the oxidation products derived from CDs, such as MA, as well as the PCP-derived products incorporated into the CDs.     

Improvements to the UK PCDD/F and PCB atmospheric emission inventory following an emissions measurement programme

PCDD/F data are presented from 75 samples of primary emissions sampled between 1995-97 as part of the compliance monitoring survey undertaken by the UK Environment Agency. Municipal solid waste (MSW), chemical waste and clinical waste incinerators, cement kilns, sinter plants and sewage sludge incinerators were the source categories monitored and reported here. Based on this monitoring programme, the previous national UK emission estimates by Eduljee and Dyke (1) of 560-1100 g I-TEQ a(-1) for 1993 have been revised downwards to 220-660 g I-TEQ a(-1). Despite source reduction measures, MSW incinerators remain a significant source of PCDD/Fs to the atmosphere, contributing between 30-50% of the EPCDD/F I-TEQ emission, rather than the approximately 80% they were estimated to contribute in 1993. 2,3,7,8-substituted PCDD/F congener profile data are presented for some of the source categories and generally support the view that differences in the mixtures ('fingerprints') of PCDD/Fs emitted from different sources are observed. New data on the dioxin-like PCB emissions are presented for cement kilns and sinter plants. These show that TEQ-rated PCBs can make an important contribution to the I-TEQ emitted from certain combustion sources. High concentrations of a full range of PCB congeners/homologues have been measured in the atmosphere close to sintering strands, although the precise source of PCBs from this process remains unclear.     

A contemporary assessment of polybrominated diphenyl ethers (PBDE) in the ambient air and soil of Azerbaijan

PBDEs were measured in air and soil across Azerbaijan to establish contemporary concentrations at 13 urban and rural sites. Polyurethane foam passive air samplers (PUF-PAS) were deployed for a period of a month with surface soil samples collected at the same sites. Unlike organochlorine pesticides previously surveyed by our group, PBDE concentrations in both contemporary air and soil were low in comparison to recent European and Asian studies. For example, mean ∑₉PBDE concentrations in air and soil were 7.13 ± 1.66 pg m^?3 and 168 ± 57 pg g^?1, respectively. The fully brominated BDE-209 was the most abundant congener observed in soil (174.8 ± 58.5 pg g^?1), comprising ~ 96% of ∑₁₀PBDE. However, the PAS-derived air concentrations for highly brominated congeners must be viewed with caution as there is uncertainty over the uptake rates of particle-bound chemicals using these devices. Some of the highest concentrations in air were observed at sites with the highest wind speeds and at several remote locations in the north of the country and this requires further research. Levels of BDE-47 and 99 (the two most abundant congeners in the widely used penta-formulation) were lower than levels reported elsewhere suggesting limited use/import of the penta-BDE formulation in Azerbaijan.     

Changes to the TEF schemes can have significant impacts on regulation and management of PCDD/F and PCB

The changes recommended by the World Health Organisation (WHO) to the toxic equivalency factors (TEFs) for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) and the recommendation to extend both the TEF scheme and the tolerable daily intake (TDI) to include "dioxin-like" PCB congeners have significant implications for regulators who have relied heavily on the International TEF (I-TEF) scheme in setting and monitoring limits and exposure to these compounds. This paper examines example data sets of sources, environmental concentrations, food and exposure to indicate likely changes in calculated toxic equivalent (TEQ) due to the recommended changes to TEFs. Many published data sets available do not provide congener specific data for PCDD/F which limits the ability to recalculate TEQs. There are even fewer congener specific data published to enable calculation of TEQs for the dioxin-like PCBs. In general TEQs calculated using the WHO scheme for emissions to air were found to show small increases (in the order of 1-10%) in comparison to the I-TEQ (for PCDD/F), some sludge samples showed substantial decreases (up to 70%). Levels in food and calculations of exposure showed that the change to TEFs for PCDD/F increased calculated exposure by 10-20% while the change to PCB TEFs decreased calculated TEQ attributable to PCB by 0-10%. The effects of including PCB in the overall TEQ and the changes to TEFs for PCDD/F substantially increase calculated TEQ exposure. Congener specific data should be presented to allow calculation of desired TEQ and the impact of the changes on emission limits, regulations on sludge use and environmental quality standards should all be carefully considered. The absence of data on emissions of dioxin-like PCB means that it is not possible to estimate with any certainty the impact on overall TEQ emissions of including the nominated PCB. Given the potential for confusion with the proliferation of TEFs and the extension to include both PCDD/F and PCB in the calculation of TEQs it is important that great care is taken to clearly express which compounds are included and which TEF scheme has been applied in each case.     

A study of the influence of sewage sludge fertilization on the concentrations of PCDD/F and PCB in soil and milk

The influence of the agricultural use of sewage sludge on the concentrations of PCBs and PCDD/Fs in soil, feed and milk was investigated on four dairy farms. Evidence of contaminant accumulation in the soil was found on both farms that fertilized with sewage sludge. The concentrations in feed and milk from one of these farms were similar to the concentrations in the matched control, while the concentrations in the samples from the second sludge user were elevated. The study demonstrates that the agricultural use of sewage sludge does under some conditions lead to higher levels of PCBs and PCDD/Fs in food products.     

Assessment of dietary exposure to PCDD/F and dioxin-like PCB in infant formulae available on the EU market

In infant period, human milk and infant formulae are the major sources of exposure to dioxins (polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (PCB). Since in many parts of Europe the mothers are increasingly reluctant to breastfeed their babies, the main objective of the present study is to assess the level of exposure of non-breast-fed infants during their early development. Consequently, the concentration levels of PCDD/F and dioxin-like PCB were determined in industrial infant formulae including "starting" (aged 0-4months) and "follow-on" (after 4months) products of milk formula, soy formula and hypoallergenic infant formula, available on the EU market. Furthermore, dietary exposure to dioxin of exclusively formula-fed infants was assessed at each month from 0 to 9months. The results suggest that dietary exposure to dioxins via formulae is higher when consuming "starting" than "follow-on" infant formulae on a body-weight basis. Estimated dietary exposure after 4months of age was always below the lowest range of the Tolerable Daily Intake (TDI) of 1pg WHO-TEQkg(-1)bwd(-1) and Provisional Tolerable Monthly Intake (PTMI) of 70pg WHO-TEQkg(-1)bwmonth(-1). The highest estimated cumulative dietary exposure to PCDD/F and dioxin-like PCB was obtained considering infants of 0-1months fed with the "starting" hypoallergenic infant formula (2.8pg WHO-TEQkg(-1)bwd(-1) and 84pg WHO-TQkg(-1)bwmonth(-1)). However, these elevated levels are much lower than those observed in some studies in breast-fed infants. The study can be used for further risk assessments in regard to infant exposure.     

Fate of PCDF/PCB congeners and change of clinical symptoms in patients with Yusho PCB poisoning for 30 years

Two mass-food poisonings called Yusho and Yucheng occurred in Japan and Taiwan in 1968 and 1979, respectively. Blood samples from five Yusho patients and three Yucheng patients were collected several times from 1982 to 1998 and from 1980 to 1995, respectively, and analyzed for polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB) congeners. Fat base concentrations of 2,3,4,7,8-penta-CDF in the Yusho patients, which were responsible for about 70% of the dioxin toxicity, are estimated to be decreased from 60 ppb in 1969 to 800 ppt in 1997 with the median half-life of 2.9 years in the first 15 years after onset and 7.7 years in the next stage of 15 years. Typical Yusho symptoms of acneiform eruption, dermal pigmentation and increased eye discharge were very gradually recovered with lapse of several years. However, enzyme and/or hormone-mediated signs of high serum triglyceride, high serum thyroxin, immunoglobulin disorder and others are persistently maintained for 30 years.     

涂料废渣水热减量及其产物特性

采用水热技术处理涂料废渣,考察了水热温度、反应时间、含水率和投碱量对涂料废渣减量及其产物特性的影响,并用SEM、元素分析对涂料废渣进行表征。实验结果表明：随着水热温度的升高及时间的延长,涂料废渣减量效果及水热液中COD、TN浓度不断增加,固体产物的热值也随之增加,而含水率对涂料废渣减量的影响不大;随着碱投加量的增加,涂料废渣减量效果和水热液中COD、TN浓度逐渐提高,固体产物的热值呈不规则变化。水热温度220 ℃、水热时间4 h、含水率77.5%、投碱量0.17 g（NaOH,投加量以每克干物质（DS）计）为涂料废渣减量的最佳反应条件。在最优条件下,总减量率和干重减量率分别为79.1%和52.1%,含水率为47.2%。水热固体产物热值较高,可以作燃料为其他工艺提供热能。     

Congener-specific accumulation of polychlorinated biphenyls in ovarian follicular wall follows repeated exposure to PCB 126 and PCB 153. Comparison of tissue levels of PCB and biological changes

OBJECTIVE: Small (SF), medium (MF) and large (LF) preovulatory porcine follicles were isolated and incubated in an Erlenmeyer flask containing 5 ml of medium with addition of PCB 126 or PCB 153 to test differences in their accumulation in the follicular wall. METHODS; The follicles were incubated in M199 medium at 37 degrees C with constant shaking at 70 rpm, for 6 days. The media were changed every day and repeated dose 25 pg/ml of PCB 126 or 25 ng/ml of PCB 153 was added each day till 6 days of culture. Media were collected every day and frozen for steroid analysis by RIA. 24 h after the last treatment follicles were frozen for further polychlorinated biphenyls (PCB) content analysis. PCB concentrations in the follicular wall were analysed by mass spectrometry. RESULTS: 3.3%; 3.6% and 5.6% of total PCB 126 dose, and 71%; 71.4% and 30.4% of total PCB 153 dose accumulated in SF, MF and LF follicles, respectively. The accumulative effect of PCB was manifested by the disruption of estradiol (E2) secretion. In SF antiestrogenic action of PCB 126 was observed during the whole time of exposure while PCB 153 decreased E2 till 4 days of culture and then estrogenic action was observed. In MF, both these congeners decreased E2 till 5 days of exposure and then estrogenic actions were noted with the highest magnification in the case of PCB 126. In LF both PCB studied increased E2 till 3 days of exposure with the highest magnification of PCB 126, then antiestrogenic action was noted. Testosterone secretion was generally affected in a pattern oposite to that of E2 suggesting action on P450arom activity. CONCLUSION: The results of these studies demonstrated that disruption of aromatization process in the follicles following repeated exposure to both congeners is not directly correlated with the bioaccumulation or amount of PCB within the follicular wall.