The Scheldt estuary is historically a highly polluted river system. While several studies have focused on contamination with metals, pesticides, Polycyclic Aromatic Hydrocarbons (PAHs) and marker ...PolyChlorinated Biphenyls (PCBs), no data are available concerning past contamination by dioxin-like compounds.
The objective of this study is to determine spatial and time trends of PolyChlorinated Dibenzo-p-Dioxins and DibenzoFurans (PCDD/Fs) and dioxin-like PCBs (dl-PCBs) in sediment samples and Suspended Particulate Matter (SPM) from the Scheldt River basin and the North Sea Coast.
Dioxin-like compounds (PCDD/F and dl-PCB fractions) were measured with the CALUX-bioassay. Bioanalytical EQuivalent concentrations (BEQs) and Total Organic Carbon (TOC) content of historical (1982–1984) and recent (2011–2015) sediment and SPM samples from different locations in the coastal area and the estuary, were evaluated.
A decrease in dioxin-like compound concentrations was found at all stations over time, especially for the PCDD/Fs. Dl-PCBs were relatively low in all samples. The Scheldt mouth and the Antwerp harbor yielded the highest BEQs and levels were higher in SPM than in sediment due to the higher organic carbon content in this fraction.
Current PCDD/F and dl-PCB levels in the Belgian Coastal Zone and Scheldt estuary are much lower than their levels 30 years ago and pose a relatively low risk to the aquatic system. This is the result of a strong decrease in emissions, however, large local variabilities in sediment concentration levels can still exist because of local variability in sedimentation, erosion rates and in organic carbon content.
•Recent and adequately stored historical sediment and SPM samples were analyzed.•PCDD/F levels in sediments are much lower than 30 years ago.•dl-PCB levels are low in recent and historical samples.•PCDD/F results are in good agreement with their atmospheric emission decrease.
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Sodium nitrite (NaNO
) is an inorganic compound that is commonly used as a preservative (E250) in the fish and meat industry. When ingested, sodium nitrite will lead to methemoglobinemia, ...hypotension, and arrhythmias. An increasing trend in the use of sodium nitrite as a suicide agent has been reported. In Belgium however it remains a rare phenomenon. The ingestion of sodium nitrite is not always apparent from the death scene investigation, especially in cases of covert administration or accidental ingestion. Hence, the forensic pathologist must be aware of this trend and the postmortem changes related to the ingestion of sodium nitrite to effectively identify these cases and determine the cause and manner of death. We describe a case of fatal self-poisoning following the oral ingestion of sodium nitrite with suicidal intent. Postmortem investigations showed signs of methemoglobinemia, such as a gray-brown discoloration of lividity and a chocolate brown discoloration of the blood. Postmortem toxicological investigation revealed methemoglobinemia (35%) in cardiac blood, hypernatremia (159.6 mmol/L) in vitreous humor, and the presence of nitrite in gastric contents (1.15 g/L) and, for the first time in a forensic case, in serum (38 µg/mL). A review of the existing literature regarding cases of sodium nitrite intoxications was performed to correlate these findings.
Paperboard used as packaging, a non-inert material, can transfer chemicals into food. Over the years, endocrine disrupting compounds (EDCs), such as NonylPhenols (NPs), BisPhenol A (BPA) and ...phthalates have been shown to migrate from packaging materials into food. Due to chronic exposure and mixture effects of these EDCs, they could cause health effects even at very low doses. Many EDCs are still unknown and many more are still unregulated. The ERE-CALUX bioassay was used as a bioanalytical tool to investigate estrogenic activities of paperboard food packaging and its characteristics, including recycling rate and printing ink. A “worst case” scenario with full extraction is compared to a dry food migration experiment. By measuring an overall estrogenic activity, known and unknown estrogenic chemicals and mixture effects are taken into account and the data are compared to molecule specific analysis. Estrogenic activities ranged from 682 ± 66 pg E2 eq./dm2 to 3250 ± 400 pg E2 eq./dm2 for “worst case” extraction and from 347 ± 30 pg E2 eq./dm2 to 1350 ± 70 pg E2 eq./dm2 for migration experiments. A two-factor ANOVA revealed a relationship between estrogenic activity and the recycling rate of the paperboard, but no significant difference with printing ink was observed for these paperboard samples. Bis(2-ethylhexyl)phthalate (DEHP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP) and 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH) were determined in all extraction and migrations experiment samples. A Spearman rank correlation analysis showed a relationship between the estrogenic activity and the total phthalates as well as with each compound individually.
•Estrogenic activities of paperboard in “worst case” extractions and in migrations.•Activities have relative standard deviations below 18% with a median value of 9.7%.•Recycling rate of paperboard food packaging highly related to estrogenic activity.•Estrogenic activities are compared to molecule specific analysis of plasticizers.•A relationship was shown between the estrogenic activity and the phthalates.
► POP levels were measured in the human milk samples of 84 mothers. ► The concentrations were compared to the Belgian WHO human milk study (2006). ► For most pollutants lower or comparable ...concentrations were found. ► While for ΣDDT and metabolites, trans-nonachlor and HBCD higher levels were observed. ► Associations were found between POP levels and personal characteristics/dietary habits.
To collect information on the concentrations of persistent organic pollutants (POPs) in the rural areas in Flanders (Belgium), 84 breastfeeding mothers were recruited in rural communities in East and West Flanders and Flemish Brabant in 2009–2010. Polychlorinated biphenyl (PCB) congeners, organochlorine pesticides, brominated flame retardants, perfluorinated compounds, polychlorinated dibenzodioxines and dibenzofurans, and dioxin-like PCBs were measured in individual milk samples and in a pooled milk sample, while some additional pollutants were only measured in the pooled sample. For most pollutants, the concentrations in this study were lower or comparable to the concentrations measured in the pooled Belgian sample of the WHO human milk study of 2006, except for the pesticides dichlorodiphenyltrichloroethane DDT (+25% for ΣDDT and metabolites) and trans-nonachlor (+94%), and for the brominated flame retardant hexachlorocyclododecane HBCD (+153%). Perfluorinated compounds were for the first time determined in human milk samples from Belgium and the concentrations were comparable to those from other European countries. Also, interesting associations were found between the concentrations of POPs measured in human milk and personal characteristics as well as dietary habits of the study population. PFOS en PFOA concentrations were significantly higher in milk of primiparous participants compared to mothers who gave birth to their second child. Lower brominated PBDE congeners increased with increasing BMI of the mothers (p=0.01 for BDE 47, p=0.02 for BDE 99 and p=0.02 for BDE 100). Participants consuming milk or dairy products daily had significant higher concentrations of ΣDDTs (p=0.03) and oxychlordane (p=0.047) in their human milk samples.
The Zenne River, crossing the Brussels region (Belgium) is an extremely urbanized river impacted by both domestic and industrial effluents. The objective of this study was to monitor the occurrence ...and activity of Endocrine Active Substances (EAS) in river water and sediments in the framework of the Environmental Quality Standards Directive (2008/105/EC and 2013/39/EU). Activities were determined using Estrogen and Dioxin Responsive Elements (ERE and DRE) Chemical Activated Luciferase Gene Expression (CALUX) bioassays.
A potential contamination source of estrogen active compounds was identified in the river at an industrial area downstream from Brussels with a peak value of 938 pg E2 eq./L water (above the EQS of 0.4 ng/L) and 195 pg E2 eq./g sediment. Estrogens are more abundantly present in the sediments than in the dissolved phase. Principal Component Analysis (PCA) showed high correlations between Suspended Particulate Matter (SPM), Particulate (POC) and Dissolved Organic Carbon (DOC) and estrogenic EAS.
The dioxin fractions comply with previous data and all were above the United States Environmental Protection Agency (US EPA) low-level risk, with one (42 pg TCDD eq./g sediment) exceeding the high-level risk value for mammals.
The self-purifying ability of the Zenne River regarding estrogens was examined with an in vitro biodegradation experiment using the bacterial community naturally present in the river. Hill coefficient and EC50 values (Effective Concentration at 50%) revealed a process of biodegradation in particulate and dissolved phase. The estrogenic activity was decreased by 80%, demonstrating the ability of self-purification of estrogenic compounds in the Zenne River.
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•ERE-CALUX implementation on an urban river with domestic and industrial effluents.•Sediment profiles differ significantly for dioxin- and estrogen-like compounds.•Estrogenic compounds were found more abundantly in sediments.•High correlations between SPM, POC, DOC and estrogenic EAS in water.•Dose-response curves of EE2 change drastically during biodegradation.
Cu pumping in TSVs: Effect of pre-CMP thermal budget De Wolf, I.; Croes, K.; Varela Pedreira, O. ...
Microelectronics and reliability,
09/2011, Letnik:
51, Številka:
9-11
Journal Article, Conference Proceeding
Recenzirano
When Cu ‘Through-Silicon-Vias’ (TSVs) are exposed to high temperatures as typically encountered during the back-end of line (BEOL) processing, the higher coefficient of thermal expansion (CTE) of Cu ...forces it to expand more than Si. This causes compressive stress in the confined Cu inside the TSV. This stress can partly be released near the top of the TSV, by out-of-plane expansion of the Cu, the so-called ‘Cu pumping’. It can severely damage the BEOL layers. In this paper the effect of a pre-CMP thermal budget (temperature and time) on Cu pumping is studied for various Cu chemistries and TSV aspect ratios. It is shown that to suppress Cu pumping a pre-CMP anneal is required that is either very long or at a temperature very close to the maximum temperature used in the BEOL processing.
Since the CALUX (Chemically Activated LUciferase gene eXpression) bioassay is a fast and inexpensive tool for the determination of dioxin-like compounds in a large number of samples and requires only ...small sample volumes, the use of this technique in human biomonitoring programs provides a good alternative to GC-HRMS. In this study, a new CALUX method for the separate analysis of PCDD/Fs and dioxin-like PCBs (dl-PCBs) in small amounts of human milk samples with the new sensitive H1L7.5c1 cell line was used to analyze 84 human milk samples, collected from mothers residing in the Flemish rural communities. The geometric mean CALUX-Bioanalytical Equivalent (CALUX-BEQ) values, reported for the 84 mothers from the study area were 10.4 (95% CI: 9.4–11.4) pg CALUX-BEQ per gram lipid or 0.41 (95% CI: 0.37–0.45) pg CALUX-BEQ per gram milk for the PCDD/Fs and 1.73 (1.57–1.91) pg CALUX-BEQ per gram lipid or 0.07 (95% CI: 0.06–0.08) pg CALUX-BEQ per gram milk for the dioxin-like PCBs. Multiple regression analysis showed significant associations between PCDD/Fs and weight change after pregnancy, smoking and consumption of local eggs. One pooled human milk sample was analyzed with both CALUX and GC-HRMS. The ratio of CALUX and GC-HRMS results for this sample were respectively 1.60, 0.58 and 1.23 for the PCDD/Fs, the dl-PCBs and the sum of both fractions, when using the 2005-TEF values. Additionally, also low levels of certain brominated dioxins and furans were detected in the pooled sample with GC-HRMS.
•PCDD/Fs and dl-PCBS were measured in the human milk samples of 84 mothers.•PCDD/Fs are still quite high compared to other (European) countries.•Low levels of brominated dioxins and furans were detected.•CALUX/GC-HRMS ratios were 1.60 (PCDD/Fs), 0.58 (dl-PCBs) and 1.23 (sum of both).•Associations between PCDD/Fs and weight change, smoking and local eggs were found.
•We characterised the ERE-CALUX bioassay and used the 4 parameter Hill equation.•We collected dust in 12 different kindergartens classes in Flanders and Brussels.•The interior score and the BEQ, or ...estrogenic activity, showed a good relationship.•Increasing amounts of phthalates lead to an increase in BEQ.
Estrogen-like endocrine disrupting chemicals (EEDCs) can be found abundantly in the environment. Due to their low-dose effects and the large amount of unknown EEDCs, it is difficult to assess and manage possible human health risks. For young children, who are particularly vulnerable to endocrine disruption due to their development rate, indoor dust is one of the main routes of exposure. In this study, an estrogen responsive elements chemically activated luciferase gene expression (ERE-CALUX) bioassay was characterized and implemented for the analysis of 12 dust samples from kindergartens in Flanders and Brussels (Belgium). The human ovarian carcinoma BG 1CALUX cell line showed reproducible results and a low limit of detection (LOD). The effective concentration at 50% of the maximum response (EC50) yielded 497fg/well, while the LOD was 16fg/well.
For all dust samples, full dose–response curves and their corresponding EC50 values could be calculated. All samples yielded bio-analytical equivalent concentrations (BEQs) that were significantly higher than the procedural blank level and ranged from 426 to 8710pg E2 equivalents/g dust. A clear relationship was observed between a semi-quantitative interior score and the ERE-CALUX response of the samples. In addition, the concentration of phthalates, a major group of EEDCs used as plasticizers in plastics, was determined in the samples by GC–MS. Diisoheptyl phthalate (DiHP) and di(2-ethylhexyl) phthalate (DEHP) were present in every dust sample. A good correlation was found between ERE-CALUX activities and phthalate concentrations, when all phthalates except diisononyl phthalate (DiNP) and diisodecyl phthalate (DiDP), which do not bind to the estrogen receptor, were taken into account.
This shows that the ERE-CALUX can provide relevant results concerning exposure to EEDCs from indoor dust.
This article is part of a Special Issue entitled ‘Endocrine disruptors & steroids’.
Within the Flemish Environment and Health studies (FLEHS I, 2002–2006, and FLEHS II, 2007–2012), pesticide exposure, hormone levels and degree of sexual maturation were measured in 14–15-year-old ...adolescents residing in Flanders (Belgium). In FLEHS II, geometric mean concentrations (with 95 % confidence interval (CI)) of 307 (277–341) and 36.5 ng L
−1
(34.0–39.2) were found for
p,p
′-dichlorophenyldichloroethylene (
p,p
′-DDE) and hexachlorobenzene (HCB). These values were respectively 26 and 60 % lower than levels in FLEHS I, 5 years earlier. Metabolites of organophosphorus pesticides (OPPs) and of
para
-dichlorobenzene were measured for the first time in FLEHS II, yielding concentrations of 11.4, 3.27 and 1.57 μg L
−1
for the sum of dimethyl- and diethyl phosphate metabolites and 2,5-dichlorophenol (2,5-DCP), respectively. Data on internal exposure of HCB showed a positive correlation with sexual maturation, testosterone and the aromatase index for boys and with free thyroxine (fT4) and thyroid stimulating hormone (TSH) (both boys and girls). For both
p,p
′-DDE and HCB, a negative association with sexual development in girls was found. The OPP metabolites were negatively associated with sex hormone levels in the blood of boys and with sexual maturation (both boys and girls). The pesticide metabolite 2,5-DCP was negatively correlated with free T4, while a positive association with TSH was reported (boys and girls). These results show that even exposure to relatively low concentrations of pesticides can have significant influences on hormone levels and the degree of sexual maturation in 14–15-year-old adolescents.
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