To Örebro University

Objectives: Exposure to high-molecular-weight polycyclic aromatic hydrocarbons (PAHs) may cause cancer in chimney sweeps and creosote-exposed workers, however, knowledge about exposure to low-molecular-weight PAHs in relation to cancer risk is limited. In this study, we aimed to investigate occupational exposure to the low-molecular-weight PAHs phenanthrene and fluorene in relation to different cancer biomarkers.

Methods: We recruited 151 chimney sweeps, 19 creosote-exposed workers and 152 unexposed workers (controls), all men. We measured monohydroxylated metabolites of phenanthrene and fluorene in urine using liquid chromatography coupled to tandem mass spectrometry. We measured, in peripheral blood, the cancer biomarkers telomere length and mitochondrial DNA copy number using quantitative PCR; and DNA methylation ofF2RL3andAHRRusing pyrosequencing.

Results: Median PAH metabolite concentrations were higher among chimney sweeps (up to 3 times) and creosote-exposed workers (up to 353 times), compared with controls (p<0.001; adjusted for age and smoking). n-ary sumation OH-fluorene (sum of 2-hydroxyfluorene and 3-hydroxyfluorene) showed inverse associations with percentage DNA methylation ofF2RL3andAHRRin chimney sweeps (B (95% CI)=-2.7 (-3.9 to -1.5) forF2RL3_cg03636183, and -7.1 (-9.6 to -4.7) forAHRR_cg05575921: adjusted for age and smoking), but not in creosote-exposed workers. In addition, n-ary sumation OH-fluorene showed a 42% mediation effect on the inverse association between being a chimney sweep and DNA methylation ofAHRRCpG2.

Conclusions: Chimney sweeps and creosote-exposed workers were occupationally exposed to low-molecular-weight PAHs. Increasing fluorene exposure, among chimney sweeps, was associated with lower DNA methylation ofF2RL3andAHRR, markers for increased lung cancer risk. These findings warrant further investigation of fluorene exposure and toxicity.

Some polycyclic aromatic hydrocarbons (PAH) are known carcinogens and workplace PAH exposure may increase the risk of cancer. Monitoring early cancer-related changes can indicate whether the exposure is carcinogenic. Here, we enrolled 151 chimney sweeps, 152 controls, and 19 creosote-exposed male workers from Sweden. We measured urinary PAH metabolites using LC/MS/MS, the cancer-related markers telomere length (TL) and mitochondrial DNA copy number (mtDNAcn) using qPCR, and DNA methylation of lung cancer-related genes F2RL3 and AHRR using pyrosequencing. The median 1-hydroxypyrene (PAH metabolite) concentrations were highest in creosote-exposed workers (8.0 μg/g creatinine) followed by chimney sweeps (0.34 μg/g creatinine) and controls (0.05 μg/g creatinine). TL and mtDNAcn did not differ between study groups. Chimney sweeps and creosote-exposed workers had significantly lower methylation of AHRR CpG site cg05575921 (88.1% and 84.9%, respectively) than controls (90%). Creosote-exposed workers (73.3%), but not chimney sweeps (76.6%) had lower methylation of F2RL3 cg03636183 than controls (76.7%). Linear regression analyses showed that chimney sweeps had lower AHRR cg05575921 methylation (B=-2.04; P<0.057, adjusted for smoking and age) and lower average AHRR methylation (B=-2.05; P<0.035), and non-smoking chimney sweeps had lower average F2RL3 methylation (B=-0.81; P<0.042, adjusted for age) compared with controls. These cancer-related markers were not associated with urinary concentrations of PAH metabolites. In conclusion, although we found no associations with PAH metabolites in urine (short-term exposure), our results suggest dose-response relationship between PAH exposure and DNA hypomethylation of lung cancer-related loci. These findings indicate that further protective measures should be taken to reduce PAH exposure.

Blubber from Faroese pilot whales (Globicephala melas) was analysed for brominated dioxins PBDD/Fs, with a subset also analysed for chlorinated dioxins, PCDD/Fs. The studied individuals were restricted to juvenile male whales sampled in the Faroe Islands during the period 1997–2013. Among the PBDD/Fs, the furans were predominant, although the relative abundance of various congeners differed between samples. Furans accounted for, on average, 79% of the ∑PBDD/Fs in the samples, with 1,2,3,4,6,7,8-HpBDF the most abundant congener, found in half of the analysed pilot whales. The concentration range for ∑PBDD/Fs among the samples was 0.080–71 pg/g l.w. (lipid weight), and the sum of toxic equivalents ranged from 0.0039 to 4.7 pg TEQ/g l.w. No relationship was found between PBDD/Fs and PCDD/Fs. In addition, 20 pilot whale samples from the period 2010–2013 were analysed for PBDEs. Several PBDE congeners were found in all of the sampled pilot whales, and at noticeably higher levels than PBDD/Fs and PCDD/Fs. The ∑PBDEs ranged from 140 to 1900 ng/g l.w., with BDE #47 the most abundant congener detected in the samples. Results from the present study were then compared with data from previous studies on pilot wales to investigate temporal trends between 1986 and 2013. The comparison indicated that PBDE concentrations in juvenile males have decreased from 1996 to the latest observations in 2013. No relationship between the concentration levels of PBDD/Fs and PBDEs in the sampled pilot whales could be identified, which indicates possible differences in the metabolism of, or exposure to, PBDEs and PBDD/Fs.

The use of different firefighting methods influences how fast a fire is extinguished and how fast the temperature drops in the area affected by the fire. These differences may also influence the formation of harmful pollutants during firefighting of an accidental fire. The aim was to study occurrence of brominated dibenzo-p-dioxins and furans (PBDD/Fs) in gas and soot during five fire scenarios resembling a small apartment fire and where different firefighting methods were used. Samples of gas and soot were taken both during the buildup of the fire and during the subsequent extinguishing of the fire while using different firefighting methods (nozzle, compressed air foam system, cutting extinguisher) and an extinguishing additive. New containers equipped with identical sets of combustible material were used for the five tests. The use of different firefighting methods and extinguishing additive induced variations in concentration and congener profiles of detected PBDD/Fs. The concentration range of Sigma PBDD/Fs in gas was 4020-18,700 pg/m(3), and in soot 76-4092 pg/m(2). PBDFs were the predominant congeners and 1,2,3,4,6,7,8-HpBDF was the most abundant congener. Chlorinated dibenzo-p-dioxins and furans (PCDD/Fs) were also monitored. The PBDD/Fs contributed with in average 97% to the total (PCDD/Fs plus PBDD/Fs) toxic equivalents, in soot and gas. During extinguishing, the shorter time the temperature was around 300 degrees C, the lower occurrence of PBDD/Fs. In the study the firefighting methods showed a difference in how effectively they induced a temperature decrease below 300 degrees C in the fire zone during quenching, where cutting extinguishing using additive and the compressed air foam system showed the fastest drop in temperature.

Temporal trends in exposure to persistent organic pollutants (POPs) were assessed in 22 pooled samples gathered from 69 individuals of Baltic ringed seal (Pusa hispida botnica) from 1974 to 2015. Samples were analysed for polybrominated dibenzo-p-dioxins and furans (PBDD/Fs), polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). No previous study has reported on the occurrence of PBDD/Fs in marine mammals in the Baltic Sea. Concentrations of pollutants in Baltic ringed seal, a marine mammal and top predator, can be used as an indicator of pollutants concentrations in the Baltic region.

Visual inspection of data did not show any temporal trends for PBDD/Fs, while the PCDD/Fs and PCBs showed decreasing concentrations between 1974 and 2015. PBDEs increased until the end of the 1990s and then decreased until the end of the period. ∑ PBDD/Fs ranged from 0.5–52.3 pg/g lipid weight (l.w.) (0.08–4.8 pg TEQ/g l.w.), with 1,2,3,4,6,7,8-HpBDF contributing on average 61% to ∑ PBDD/Fs. ∑ PCDD/Fs ranged from 103 to 1480 pg/g l.w. (39–784 pg TEQ/g l.w.), with 1,2,3,6,7,8-HxCDD, 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF showing the highest average concentrations. PBDD/F toxic equivalents (TEQ) contributed on average 1.1% to the total (PBDD/F + PCDD/F) TEQ. The ∑ PBDEs concentration range was 18.7–503 ng/g l.w., with BDE #47 the predominant congener. The concentration range for ∑ PCBs was 2.8–40.1 μg/g l.w., with #138 and #153 the most abundant congeners. Visual inspection of the data showed decreasing concentrations for all compound groups except PBDD/Fs. A slight increase in the PBDD/Fs concentrations was observed from 2004 onwards. This observation needs to be investigated further.

This article provides an overview of concentrations of persistent organic pollutants (POPs) in ambient air on a global scale, including recent measurements and an extensive compilation of literature data. In this study, passive air samplers (PASs) were successfully employed to assess concentrations of POPs in ambient air from Africa, Latin America, the Caribbean, and the Pacific Islands. The project aimed to extend the knowledge on environmental contamination by POPs in these regions, where the currently available data are still limited to a few monitoring studies.

The ambient air concentrations of PCB in Africa were relatively high when compared to other regions. Waste, in particular electronic waste, exported to Africa from industrialized countries may be a possible source of PCB in Africa, where PCB have never been extensively used or produced. For DDTs, the wide range of concentrations and particularly high levels in some countries of Africa and the Pacific Islands reflect the use of DDT for malaria control in these regions. For PCDD/PCDF, concentrations in Africa and Latin America are similar to or even higher than in Europe, probably due to unfavorable combustion practices of chlorine-containing materials.

The data support the needs for further monitoring in developing countries and countries with economies in transition, and action to reduce environmental contamination by, and human exposure to, hazardous chemicals.

A capillary zone electrophoretic method for the analysis of low molecular weight carboxylic acids in water was developed. The application uses the chromophore trimellitic acid that allows for indirect photometric detection at 254 nm. Selectivity control by the addition of Ca2+ to the carrier electrolyte made possible a baseline resolved separation of 14 carboxylic acids. Good linearity and repeatability were obtained for both electrokinetic and hydrostatic injection modes. The usefulness of the method is demonstrated by the analysis of a snow sample.

The use of UV/Vis spectroscopy in combination with partial least squares (PLS) regression for the simultaneous prediction of nitrate and non-purgeable organic carbon (NPOC) in groundwaters was evaluated. A model of high quality was obtained using first order derivative spectra in the range 200–300 nm. Inclusion of non-UV-absorbing constituents in the modeling procedure, i.e., chloride, sulfate, fluoride, total carbon (TC), inorganic carbon (IC), alkalinity, pH and conductivity was also evaluated. This model seemed to be useful for prediction of chloride, TC, IC, alkalinity and conductivity, while its ability to predict sulfate, fluoride and pH was poor. In conclusion, application of PLS regression, which requires neither filtration of samples nor addition of chemicals, is a promising alternative for fast interpretation of geochemical patterns of groundwater quality.

The tailings at Kristineberg, northern Sweden, have a very low content of organic carbon, a feature common with many sulfidic tailing impoundments. Three different experiments were set-up to assess the role of carbon dioxide in a depth profile. Firstly, pore gas was collected in vials from ground water pipes at various points in the profile of a dry covered tailings impoundment and analyzed in the laboratory for CO2, O-2, N-2, H-2, and CH4 contents. Secondly, pore water was extracted from tension lysimeters at various depths. This water was analyzed for numbers of bacteria (iron-oxidizing and sulfur-oxidizing, both by MPN), and low molecular weight organic acids. Thirdly, Acidithiobacillus ferrooxidans (Strain DSMZ No 1927) was grown on a mixture of irradiated tailings and sterile water. The amount of organic acids produced was monitored. The largest bacterial count of iron-oxidizing bacteria, 4.7 x 10(5)/g tailings, was at the oxidation front, while the heterotrophic sulfur-oxidizing bacteria were mainly found in the unsaturated, oxidized zone, 2.65 x 10(4)/g tailings. The oxidation front was also the location where the largest amount of organic acids was found in the field study (formate 0.83 mg/l and acetate 0.51 mg/l). The acetic acid found coincides with the highest count of iron-oxidizing bacteria. The intrusion of O-2 and CO2 at the studied location is enough for microbiological activity, although the overall effect on AMD production is not addressed. The results from laboratory incubations indicate that the microbial community produces organic carbon with CO2 as the sole carbon source, up to 1.35 mg/l after 16 weeks measured as TOC. To conclude, we suggest that knowledge of the intrusion of both CO2 and O-2 is vital for a full understanding of the microbial ecology, and thus the weathering processes, in a dry covered tailings impoundment. Hence, the CO, produced in the till cover and entering the tailings ecosystem is crucial to the function of the ecosystem. (c) 2006 Elsevier B.V. All rights reserved.

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) were analyzed in both human adipose tissue and plasma from nine individuals, from the Swedish general population, using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). In addition, several other persistent organic pollutants (POPs) were determined in the same samples, including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and perfluorinated chemicals (PFCs). Polybrominated dibenzofurans were detected in all of the human adipose tissue samples confirming their presence in the Swedish population. The highest concentration was found for 2,3,7,8-TeBDF, ranging from 0.27 to 2.4 pg g(-1) lipid. followed by 1,2,3,7,8-PeBDF, 0.23-0.89 pg g(-1) lipid, 2,3,4,7,8-PeBDF, 0.44-0.54 pg g(-1) lipid, and 2,7/2,8-DiBDF, 0.19-0.30 pg g(-1) lipid. No PBDDs could be detected above the limit of detection (<0.02-<0.21 pg g(-1) lipid) in any of the samples. The levels of PCDD/Fs were in the range 1.79-31.5 pg toxic equivalents (TEQ) g(-1) lipid, and PBDEs were found in the 1.16-7.46 ng g(-1) lipid range. The measured chlorinated dioxins indicate decreasing human concentrations in Sweden. The toxicity equivalents (TEQ) for PBDD/Fs (0.2-0.8 pg TEQ g(-1) lipid) were found to contribute 1-15% of the total dioxin TEQ of the chlorinated dioxins and furans (5-18 pg TEQ g(-1) lipid) depending on the individual. Also PBDEs concentrations are decreasing compared to 1997-2000, but most noteworthy a shift in BDE pattern where BDE#47 is surpassed by BDE#153. The levels of PFCs are in the same range as the highest levels of the traditional POPs (sum of 60 PCBs) based on volume. These findings illustrate the importance of continuous monitoring of brominated compounds in both human and the environment. (C) 2009 Elsevier Ltd. All rights reserved.

A method using a novel atmospheric pressure chemical ionization source for coupling gas chromatography (GC/APCI) to triple quadrupole mass spectrometry (MS/MS) for the determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) regulated by the Stockholm Convention is presented. One microliter injection of a six-point calibration curve of native PCBs and OCPs, ranging from 0.04 to 300 pg/μL, was performed. The relative standard deviation (RSD) of the relative response factors (RRFs) was less than 15% with a coefficient of determination (r2) &gt;0.995. Meanwhile, two calibration solutions (CS), CS 2 (0.4 pg/μL) and CS 3 (4 pg/μL) were analyzed to study the repeatability calculated for both area and RRFs. The RSD for RRF ranged from 3.1 to 16% and 3.6 to 5.5% for CS 2 and CS 3, respectively. The limits of detection (LOD) determined by peak-to-peak signal-to-noise ratio (S/N) of 3 were compared between the GC/APCI/MS/MS and a GC coupled to high resolution mass spectrometry (GC/HRMS) system. GC/APCI/MS/MS resulted in lower LOD for most of the compounds, except for PCB#74, cis-chlordane and trans-chlordane. GC/APCI/MS/MS and GC/HRMS were also compared by performing analysis on 75 human serum samples together with eight QA/QC serum samples. The comparison between GC/APCI/MS/MS system and GC/HRMS system for 16 of the targeted compounds was carried out. No statistically significant difference was discovered. Due to increased sensitivity and user friendly operation under atmospheric pressure, GC/APCI/MS/MS is a powerful alternative technique that can easily meet the specification of GC/HRMS.

This article reviews the available literature on the analysis of brominated dibenzo-p dioxins and furans(PBDD/Fs) by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS).Sample extraction and clean up, injection techniques, chromatographic separation, labelled standardsand QA/QC works are discussed. Furthermore, full separation of PBDD/Fs from polybrominated diphenylethers (PBDEs) during clean up and control of possible chromatographic interference of PBDEs duringinstrumental analysis as well as possible actions to further enhance the quality of published data arediscussed in detail.

Capillary zone electrophoretic (CZE) methods were developed to identify and quantify low molecular weight (LMW) organic acids in environmental samples. Sensitivity and selectivity were optimised by adapting the background electrolyte to the characteristics of analytes, and by using different modes of detection and injection. Electrokinetic injection mode in combination with an isotachophoretic state increased the sensitivity remarkably for LMW organic acids using UV detection. Calcium ions were added to the background electrolyte, inducing an on-column complexation between acids and calcium ions, which gave good separation of the acids. Mass spectrometric detection (compared to UV detection) increased the sensitivity when using hydrodynamic injection mode during analysis, and selectivity was improved by mass identification. A CZE method for determination of the dissociation constants of LMW organic acids in the pKa range of 3.54.5 was also developed.

The developed procedures were applied to different areas where LMW organic acids play an important environmental role:

Low molecular weight organic acids were analysed in rainwater and soil water in the low μg/l range, within ten minutes after sampling. Rapid analysis and high sensitivity are essential when studying samples with rapid turnover due to microbial activity and photodegradation.

The use of CZE-ESI-MS proved to be a robust analytical tool for determining LMW organic acids in samples rich in interfering ions. Organic acids excreted by soil fungi as response to metal exposure was easily and rapidly quantified with CZE-ESI-MS compared to HPLC and CZE-UV analysis.

Dissociation constants for isosaccharinic acid (ISA) and gluconic acid were determined by CZE to 3.87 and 3.64, respectively. The ability to make the determinations in the presence of impurities as well as not having to know the exact concentration of analyte were identified as the major benefits of CZE.

Isosaccharinic acid was identified as the main degradation product from alkaline degradation of cellulose by CZE analysis. Long-term predictions on both cellulose degradation and ISA production were made based on three years of sampling data. A control sampling after seven years indicated that the degradation of cellulose and the production of ISA were lower than predicted.

The applicability of a recently developed capillary zone electrophoretic (CZE) method for the determination of low molecular weight (LMW) organic acids in water was tested on five types of environmental samples (rainwater, water extract from peat, and soil water from two polluted sites). A full baseline resolved separation of fourteen commonly found LMW carboxylic acids in natural waters (malonic, oxalic, fumaric, maleic, formic, succinic, tartaric, glutaric, adipic, acetic, propionic, butyric, valeric and citric acids), was achieved within eight minutes. The limits of detection (2 x noise) were in the ranges 90-200 mug/l and 0.5 - 5 mug/l for hydrodynamic and electrokinetic injection, respectively. Two different CZE systems, a Waters Quanta 4000 and a Hewlett Packard HP (CE)-C-3D system, were used and their performance compared.

A capillary zone electrophoretic (CZE) method has been developed to determine dissociation constants (pK(a)) for anionic, non-UV absorbing species in the range 3.3-4.3. The procedure was evaluated by determining the ply, for two well-characterised low molecular weight organic acids: formic and lactic acids. The results correspond well with literature values (in parentheses): formic acid 3.71 (3.75) and lactic acid 3.84 (3.85). The pK(a) of two polyhydroxycarboxylic acids were also determined, namely 3.64 for gluconic acid and 3.87 for isosaccharinic acid (only poorly described in the literature).

A substantial formation of PBDF congeners was observed during photolytic decomposition of decaBDE in toluene. The decaBDE degradation was monitored by chemical and toxicological analysis and in all, twenty-seven mono- to hexasubstituted polybrominated dibenzofurans (PBDFs) were detected in toluene solutions of decabromodiphenyl ether (decaBDE) after irradiation with UV-A, UV-AB and UV-ABC. The concentration levels of PBDFs formed after 16 h of UV exposure increased with wider spectra and were determined to be 3.5, 4.2 and 14 microg/ml after UV-A, UV-AB and UV-ABC irradiation, respectively. In accordance, bioassay derived TEQs (bio-TEQs), determined with the DR-CALUX assay, increased with a similar pattern. The PBDFs formed after the three UV exposures accounted for 0.31%, 0.35% and 1.2% of the initial amount of decaBDE (molar basis). The PBDF congener patterns were consistent in all three UV experiments which imply that no alterations were induced in the PBDF formation or degradation processes due to differences in UV irradiation. However, these processes tended to increase with wider spectra and increasing radiation energy most likely due to the strong absorbance of for example decaBDE at shorter wavelengths. After total decaBDE decomposition the PBDF formation increased significantly in the UV-ABC experiment. The tetra to hexasubstituted BDFs constituted the majority of detected compounds in all experiments. In all samples, the estimated chemical TEQ indicate that the bio-TEQs observed are largely explained by the presence of non-2,3,7,8-substituted PBDFs with relatively low toxicological potencies.

Background: Since we spend most of our time indoors the indoor environment can lead to exposure to substances like metals. Small children are often more exposed than adults, for instance due to their hand-to-mouth behaviour. Since some metals can have adverse health effects in children the aim of this study was to investigate indoor exposure to metals on children’s hands in preschools.

Method: In the study, 60 children at 8 preschools in two cities in Sweden participated. Metals on the hands were sampled at two different periods (winter and spring) giving a total of 109 samples. During sampling, both hands were wiped using hand-wipes soaked in 1 % HNO3, and sampling was done after two hours of indoor activities. The following metals were analyzed using ICP-MS; beryllium, magnesium, aluminium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, molybdenum, silver, cadmium, antimony, barium, thallium and lead. Results All samples were above limit of quantification (LOQ) except for beryllium and molybdenum (4 %<LOQ) and silver (100 %<LOQ, LOQ=0.001 µg/sample). The lowest mean level was seen for beryllium (0.0034 µg/sample) and highest for magnesium (140 µg/sample). For cadmium, arsenic and lead the mean levels were 0.023, 0.049 and 0.51 µg/sample, respectively. For about half of the metals statistically significantly higher levels (p<0.05) were seen during spring and in one of the cities.

Conclusion: Metals linked to severe health effects like cadmium, arsenic and lead as well as a range of other metals could be detected on children’s hands. These findings indicate an exposure to metals for children both via dermal uptake and oral intake due to hand-to-mouth transfer, but potential contributions to the body burden are unknown. Higher levels were seen during spring and in one of the cities, possible explanations to these observations needs to be looked into more closely.

Uptake of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was studied in earthworms collected from a sawmill site in Sweden with severe PCDD/Fs contamination (the hot spot concentration was 690,000 ng TEQ_WHO2005/kg d.w.) in order to investigate the transfer of PCDD/Fs from the site to the biota. PCDD/Fs concentrations in the collected earthworms were compared to PCDD/Fs concentrations in laboratory exposed earthworms (Eisenia fetida), which were exposed to contaminated soils from the sawmill site for 34 days. All analyses were performed by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). PCDD/Fs concentrations in the earthworms ranged from 290 to 520,000 pg/g (f.w.). The main congeners found in both soils and earthworms were OCDF, 1234678-HpCDF, OCDD and 1234678-HpCDD. The study showed that the PCDD/Fs in the soil were biovailable to the earthworms and the PCDD/Fs concentrations in the soils correlated with the concentrations in the earthworms. Earthworm samples from soil with lower concentration had higher bioaccumulation factors than samples from soils with high concentration of contamination. Thus, a less contaminated soil could yield higher concentrations in earthworms compared to a higher contaminated soil. Assuming that when assessing risks with PCDD/F contaminated soil, a combination of chemical analysis of soil PCDD/Fs concentrations and bioavailability should be employed for a more comprehensive risk assessment.

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo-p-furans (PCDD/Fs) were analysed in soil from a Swedish sawmill site where chlorophenols (CPs) had been used more than 40 years ago. The most contaminated area at the site was the preservation subarea where the PCDD/F WHO2005-TEQ level was 3450 times higher than the current Swedish guideline value of 200 ng TEQ/kg soil for land for industrial use. It was also shown that a fire which destroyed the sawmill might have affected the congener distribution at the concerned areas. To get a broader picture of the contamination both GIS (spatial interpolation analysis) and multivariate data analysis (PCA) were applied to visualize and compare PCDD/F levels as well as congener distributions at different areas at the site. It is shown that GIS and PCA are powerful tools in decisions on future investigations, risk assessments and remediation of contaminated sites.

Background: To decrease contamination of needleless catheter hubs, caps or port protectors impregnated with isopropanol (IPA) have been developed and shown to be superior to other disinfection methods. The safety of the caps has been questioned, as they can be associated with alcohol leakage across the hub membrane.

Objectives: We evaluated the use of IPA caps and the scrub-the-hub method from the safety standpoint of possible alcohol leakage across the hub membrane.

Methods: Circuits imitating an intravenous line were constructed. Circuits with an IPA cap were flushed with sodium chloride after the hub had been exposed to the cap for 1 hour, 24 hours, and 7 days. At the end of each period the fluid was collected and amounts of IPA in it were measured, using gas chromatography. Scrub circuits without IPA caps were also tested and ethanol from these was measured using the same method.

Results: In this in vitro study, IPA was detected in all samples from cap circuits, and ethanol was detected from all scrub circuits. Leakage increased over time in IPA circuits. After 24 hours and 7 days of exposure, the first injection resulted in higher amounts of IPA; thereafter, the levels decreased. The amounts of ethanol measured from the scrub circuits were low.

Conclusions: IPA caps can cause leakage of alcohol across the hub membrane. Leakage increased over time, and a 30 sec drying time was not sufficient to solve the problem. Scrub-the-hub seems safe to use with regard to alcohol leakage.

BACKGROUND: Hexavalent chromium (Cr(Ⅵ)) is classified as a group 1 human carcinogen and increases the risk of lung cancer. Non-coding RNAs (ncRNAs) have key regulatory roles in lung cancer, but less is known about their relation to Cr(Ⅵ) exposure.

OBJECTIVES: We aimed to 1) measure the expression of lung cancer-related circulating ncRNAs in exposed workers and controls; 2) assess associations between ncRNAs expression and Cr concentrations in red blood cells (RBC) and urine; and 3) evaluate correlations between the ncRNAs.

METHODS: The study included 111 Cr(VI) exposed workers and 72 controls recruited from the SafeChrom project. Cr concentrations were measured in RBC (biomarker of long-term exposure) and urine (biomarker of short-term exposure) samples. Long ncRNA (lncRNA) and microRNA (miRNA) were extracted from plasma followed by deoxyribonuclease treatment, complementary DNA synthesis, and quantitative real-time polymerase chain reaction using target-specific assays for three lncRNAs (H19, MALAT1, NORAD), and four miRNAs (miR-142-3p, miR-15b-5p, miR-3940-5p, miR-451a).

RESULTS: Expression levels of lncRNAs MALAT1 and NORAD, and all four miRNAs, were significantly lower in Cr(VI) exposed workers compared with controls, and correlated significantly with RBC-Cr concentrations (rS = -0.16 to -0.38). H19 was non-significantly increased in exposed workers but significantly correlated with miR-142-3p (rS = -0.33) and miR-15b-5p (rS = -0.30), and NORAD was significantly positively correlated with all four miRNAs (rS = 0.17 to 0.46). In multivariate regression models adjusting for confounders, expressions of lncRNAs MALAT1 and NORAD and all miRNAs were still significantly lower in the exposed group compared with controls, and the expression decreased with increasing RBC-Cr concentrations.

CONCLUSIONS: Cr(VI) exposure was inversely and in a dose-response manner associated with the expression of circulating non-coding RNA, which suggests ncRNAs as potential biomarkers for Cr(VI)-induced toxicity. Correlations between miRNAs and lncRNAs suggest that they participate in the same lncRNA-miRNA-messenger RNA regulatory axes, which may play important roles in Cr(VI) carcinogenesis.

Objectives: Hexavalent chromium (Cr(VI)) is classified as a human carcinogen. Occupational Cr(VI) exposure can occur during different work processes, but the current exposure to Cr(VI) at Swedish workplaces is unknown.

Methods: This cross-sectional study (SafeChrom) recruited non-smoking men and women from 14 companies with potential Cr(VI) exposure (n = 113) and controls from 6 companies without Cr(VI) exposure (n = 72). Inhalable Cr(VI) was measured by personal air sampling (outside of respiratory protection) in exposed workers. Total Cr was measured in urine (pre-and post-shift, density-adjusted) and red blood cells (RBC) (reflecting Cr(VI)) in exposed workers and controls. The Bayesian tool Expostats was used to assess risk and evaluate occupational exposure limit (OEL) compliance.

Results: The exposed workers performed processing of metal products, steel production, welding, plating, and various chemical processes. The geometric mean concentration of inhalable Cr(VI) in exposed workers was 0.15 mu g/m3 (95% confidence interval: 0.11-0.21). Eight of the 113 exposed workers (7%) exceeded the Swedish OEL of 5 mu g/m3, and the Bayesian analysis estimated the share of OEL exceedances up to 19.6% for stainless steel welders. Median post-shift urinary (0.60 mu g/L, 5th-95th percentile 0.10-3.20) and RBC concentrations (0.73 mu g/ L, 0.51-2.33) of Cr were significantly higher in the exposed group compared with the controls (urinary 0.10 mu g/ L, 0.06-0.56 and RBC 0.53 mu g/L, 0.42-0.72). Inhalable Cr(VI) correlated with urinary Cr (rS = 0.64) and RBC-Cr (rS = 0.53). Workers within steel production showed the highest concentrations of inhalable, urinary and RBC Cr. Workers with inferred non-acceptable local exhaustion ventilation showed significantly higher inhalable Cr(VI), urinary and RBC Cr concentrations compared with those with inferred acceptable ventilation. Furthermore, workers with inferred correct use of respiratory protection were exposed to significantly higher concentrations of Cr(VI) in air and had higher levels of Cr in urine and RBC than those assessed with incorrect or no use. Based on the Swedish job-exposure-matrix, approximately 17 900 workers were estimated to be occupationally exposed to Cr(VI) today.

Conclusions: Our study demonstrates that some workers in Sweden are exposed to high levels of the non-threshold carcinogen Cr(VI). Employers and workers seem aware of Cr(VI) exposure, but more efficient exposure control strategies are required. National strategies aligned with the European strategies are needed in order to eliminate this cause of occupational cancer.

A selective and fast method for the quantitative determination of 2,4,6-trichloroanisole (TCA) and 2,4,6-tribromoanisole (TBA) in wine was developed. Microextraction in packed syringe (MEPS) was optimized for the extraction and preconcentration of the analytes using extremely small volume samples (0.1-1 mL). For GC-EI-MS, the limit of detection (LOD) for red and white wine was in the range 0.17-0.49 mu g L-1 for TCA and TBA. In addition to GC-EI-MS both GC-NCI-MS and GC-HRMS were used to further improve both selectivity and sensitivity. The lowest LODs were achieved using GC-HRMS in the El mode. In red and white wine samples the LODs were between 0.22-0.75 ng L-1 for TCA and TBA. The reproducibility and linearity for the GC-HRMS method was good, with RSD-values of 4-10% for spiked red wine samples at 1 ng L-1 and linearity with R-2 > 0.962 over a concentration range of 1 to 100 ng L-1.

This study is a consequence of a distinct fish decline in the Danube river since the beginning of the 1990s. In contrast to the decline of fish population, former studies have repeatedly documented that the water quality along the Danube river is improving. However, the conclusion of a pilot study in 2002 was that a high hazard potential is associated with local sediments. The present study documents that sediment samples from the Danube river showed comparatively high aryl hydrocarbon receptor mediated activity in biotests, using the cell lines GPC.2D.Luc, H4IIE (DR-CALUX®) and RTL-W1. The combination of chemical analysis, fractionation techniques and different in vitro tests revealed that priority pollutants could not explain the main induction, even though the concentrations of priority polycyclic aromatic hydrocarbons (PAHs) were very high (maximum in the tributary Schwarzach, sum of 16 EPA PAHs 26 μg/g). In conclusion, this investigation shows that nonpriority pollutants mainly mediate the high induction rates. Nevertheless, owing to the effects of PAHs towards fish and the connection between dioxin-like activity and carcinogenicity, the link between contamination and the fish population decline cannot be ruled out.

This study is a consequence of a distinct fishdecline in the Danube river since the beginning of the 1990s. In contrast to the decline of fish population, former studies have repeatedly documented that the water quality along the Danube river is improving. However, the conclusion of a pilot study in 2002 was that a high hazard potentialis associated with local sediments. The present study documents that sediment samples from the Danube river showed comparatively high aryl hydrocarbon receptor mediated activity in biotests, using the cell lines GPC.2D.Luc, H4IIE(DR-CALUX®) and RTL-W1. The combination of chemical analysis, fractionation techniques and different in vitro tests revealed that priority pollutants could not explain the main induction, even though the concentrations of prioritypolycyclic aromatic hydrocarbons (PAHs) were very high (maximum in the tributary Schwarzach, sum of 16 EPAPAHs 26 μg/g). In conclusion, this investigation shows that nonpriority pollutants mainly mediate the high inductionrates. Nevertheless, owing to the effects of PAHs towards fish and the connection between dioxin-like activity andcarcinogenicity, the link between contamination and the fish population decline cannot be ruled out.

The H4IIE-luc transactivation bioassay for aryl hydrocarbon receptor (AhR) agonists was used to investigate the relative potency factors (REPs) of 22 individual polycyclic aromatic hydrocarbons (PAHs) and their oxygenated-, methylated-, and N-containing derivatives (azaarenes), which are often present in PAH-contaminated soils. Naphthacene and dibenz[ah]acridine exhibited greater AhR-mediated potency, whereas lesser molecular-weight azaarenes were less potent AhR agonists. Six oxygenated PAHs had calculable REPs, but their potencies were less than their parent PAHs. Unlike the parent, unsubstituted PAHs, oxidation of methylated PAHs seemed to increase the AhR-mediated potency of the compounds, with 2-methylanthracene-9,10-dione being almost 2 times more potent than 2-methylanthracene. Both bioassay and gas chromatography-mass spectrometry analysis were used to examine the exposure time-dependent effects on the REPs at 24 h, 48 h, and 72 h of exposure in the H4IIE-luc transactivation bioassay. Changes in concentrations of 5 compounds including the model reference 2,3,7,8-tetrachlorodibenzo-p-dioxin in the cell culture wells were measured, and the amounts in the cell medium, in the cells, and adsorbed to the wells was determined and the influence on the REPs was studied. Declining REP values with increased duration of exposure were shown for all compounds, which we concluded were a consequence of the metabolism of PAHs and PAH derivatives in H4IIe-luc cells. The present study provides new knowledge regarding the degradation and distribution of compounds in the wells during exposure. Environ Toxicol Chem 2014;33:943-953. (c) 2014 SETAC

The H4IIE-luc transactivation bioassay for aryl hydrocarbon receptor (AhR) agonists was used to investigate relative potency factors (REPs) of 22 individual polycyclic aromatic hydrocarbons (PAHs) and their oxygenated-, methylated- and N-containing derivatives (azaarenes), which are often present in PAH-contaminated soils. Naphthacene and dibenz[ah]acridine exhibited greater AhRmediated potency, whereas lesser-molecular azaarenes were less potent AhR agonists. Six oxy-PAHs had calculable Relative potencies (REPs), but their potencies were less than their parent PAHs. Unlike the parent, unsubstituted PAHs, oxidation of methylated PAHs seemed to increase the AhR-mediated potency of the compounds, with methylanthracene-9,10-dione being almost two times more potent than methylanthracene. Both bioassay and gas chromatography–mass spectrometry (GC/MS) analysis were used to examine the exposure time dependent effects on the REPs at 24, 48 and 72 h of exposure in the H4IIE-luc transactivation bioassay. Changes in concentrations of five compounds including the model reference 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in the cell culture wells were measured, and the amounts in the cell medium, the cells and adsorbed to the wells determined and the influence on the REPs was studied. Declining REP values with increased duration of exposure were shown for all compounds and proved to be a consequence of the metabolism of PAHs and PAH derivatives in H4IIe-luc cells. The present study provides new knowledge regarding the degradation and distribution of compounds in the wells during exposure.

Abstract Polycyclic aromatic hydrocarbons (PAHs) are common contaminants in soil at former industrial areas; and in Sweden, some of the most contaminated sites are being remediated. Generic guideline values for soil use after so-called successful remediation actions of PAHcontaminated soil are based on the 16 EPA priority pollutants, which only constitute a small part of the complex cocktail of toxicants in many contaminated soils. The aim of the study was to elucidate if the actual toxicological risks of soil samples from successful remediation projects could be reflected by chemical determination of these PAHs. We compared chemical analysis (GC-MS) and bioassay analysis (H4IIE-luc) of a number of remediated PAH-contaminated soils. The H4IIE-luc bioassay is an aryl hydrocarbon (Ah) receptor-based assay that detects compounds that activate the Ah receptor, one important mechanism for PAH toxicity. Comparison of the results showed that the bioassay-determined toxicity in the remediated soil samples could only be explained to a minor extent by the concentrations of the 16 priority PAHs. The current risk assessment method for PAH-contaminated soil in use in Sweden along with other countries, based on chemical analysis of selected PAHs, is missing toxicologically relevant PAHs and other similar substances. It is therefore reasonable to include bioassays in risk assessment and in the classification of remediated PAH-contaminated soils. This could minimise environmental and human health risks and enable greater safety in subsequent reuse of remediated soils. 

Polycyclic aromatic hydrocarbons (PAHs) are common contaminants in soil at former industrial areas; and in Sweden, some of the most contaminated sites are being remediated. Generic guideline values for soil use after so-called successful remediation actions of PAH-contaminated soil are based on the 16 EPA priority pollutants, which only constitute a small part of the complex cocktail of toxicants in many contaminated soils. The aim of the study was to elucidate if the actual toxicological risks of soil samples from successful remediation projects could be reflected by chemical determination of these PAHs. We compared chemical analysis (GC-MS) and bioassay analysis (H4IIE-luc) of a number of remediated PAH-contaminated soils. The H4IIE-luc bioassay is an aryl hydrocarbon (Ah) receptor-based assay that detects compounds that activate the Ah receptor, one important mechanism for PAH toxicity. Comparison of the results showed that the bioassay-determined toxicity in the remediated soil samples could only be explained to a minor extent by the concentrations of the 16 priority PAHs. The current risk assessment method for PAH-contaminated soil in use in Sweden along with other countries, based on chemical analysis of selected PAHs, is missing toxicologically relevant PAHs and other similar substances. It is therefore reasonable to include bioassays in risk assessment and in the classification of remediated PAH-contaminated soils. This could minimise environmental and human health risks and enable greater safety in subsequent reuse of remediated soils.

GOAL, SCOPE AND BACKGROUND: The use of polybrominated diphenyl ethers (PBDEs) as flame retardants increases the risk for emissions of other brominated compounds, such as polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). The large homology in structure of PBDD/Fs and mechanism of toxic action, i.e. the capacity to activate the Ah receptor (AhR) pathway, compared to their well-studied chlorinated analogues, justifies a raised concern to study the environmental levels and fate of these compounds. Decabromodiphenyl ether (decaBDE) is the most widely used PBDE today. Studies on photolytic debromination of decaBDE in organic solvents have shown debromination of decaBDE, as well as formation of PBDFs. However, little is known about the transformation mechanisms and there are only scarce data on photoproducts and PBDE transformation in environmentally relevant matrices. In this study, mechanism-specific dioxin bioassays were used to study photolytic formation of AhR agonists in toluene solutions of decaBDE. In addition, the influence of irradiation time and UV-light wavelength on the formation was studied. PBDE congener patterns and presence of PBDD/Fs were analysed. Further, AhR agonists were analysed in agricultural soils contaminated with PBDEs. Soils were also exposed to UV-light to study changes in AhR agonist levels. METHODS: Toluene solutions of decaBDE were irradiated using three different spectra of UV-light, simulating UV-A (320-400 nm), UV-AB (280-400 nm), and UV-ABC (250-400 nm). Additionally, decaBDE solutions were exposed to narrow wavelength intervals (10 nm bandwidth) with the central wavelengths 280, 290, 300, 310, 320, 330, 340, 350, 360 nm. AhR agonists in decaBDE solutions were analysed with two different bioassays, the chick embryo liver-cell assay for dioxins (Celcad) and the dioxin responsive, chemically activated luciferase expression assay (DR-Calux). Also, the decaBDE solutions were analysed with LRGC-LRMS to obtain PBDE congener patterns for breakdown of decaBDE, and with HRGC-HRMS, for presence of PBDD/Fs. Four soils were exposed to UV-AB light, under both dry and moist conditions. Levels of AhR agonists in soil extract fractions, before and after UV-exposure, were analysed with the DR-Calux. RESULTS AND DISCUSSION: Significant levels of photoproducts able to activate the AhR pathway, up to 31 ng bio-TEQ/ml, were formed in UV-exposed decaBDE solutions. The transformation yield of decaBDE into AhR agonists was estimated to be at the 0.1%-level, on a molar basis. The net formation was highly dependent on wavelength, with the sample irradiated at 330 nm showing the highest level of dioxin-like activity. No activity was detected in controls. PBDE analysis confirmed decaBDE degradation and a clear time-dependent pattern for debromination of PBDE congeners. AhR agonist effect in the recalcitrant fractions of the soils corresponded to the levels of chemically derived TEQs, based only on chlorinated dioxin-like compounds in an earlier study. It was concluded that no significant levels of other AhR agonists, e.g. PBDFs, were accumulated in the soil. UV-light caused changes in AhR-mediated activity in the more polar and less persistent fractions of the soils, but it is not known which compounds are responsible for this. RECOMMENDATIONS AND PERSPECTIVES: The laboratory experiments in this study show that high levels of AhR agonists can be formed as photoproducts of decaBDE and it is important to elucidate if and under which conditions this might occur in nature. However, soil analysis indicates that photoproducts of PBDE do not contribute to the accumulated levels of persistent dioxin-like compounds in agricultural soil. Still, more data is needed to fully estimate the environmental importance of PBDE photolysis and occurrence of its photoproducts in other environmental compartments. Analysis with dioxin bioassays enabled us to gather information about photoproducts formed from decaBDE even though the exact identities of these compounds were not known. CONCLUSION: Bioassays are valuable for studying environmental transformation processes like this, where chemical analysis and subsequent toxicological evaluation requires available standard compounds and information on toxicological potency. The use of bioassays allows a rapid evaluation of toxicological relevance.

Cellulose powder and softwood sawdust were subjected to alkaline degradation under conditions representative of a cementitious environment for periods of 7 and 3 years, respectively. During the first 3 years, sampling was frequent, and data on the degradation of cellulose and production of isosaccharinic acid was used for establishing long-term prediction models. Samples after an additional period of 4 years were compared to the predicted values. The total rate of degradation was measured as the increase in total organic carbon (TOC) in corresponding solutions. A previously published theoretical model of degradation kinetics gave a good approximation of the present experimental data. Peeling-off, stopping, and alkaline hydrolysis reaction rate constants were obtained as model parameters, and the results suggested that the transformation of the glucose end group is the rate-limiting step in the cellulose peeling-off reaction and also determines the pH dependence of that reaction. After 3 years, isosaccharinic (ISA) acid represented 70-85% of all degradation products as quantified by capillary zone electrophoresis. The long-term prediction model indicated that all of the cellulose would be degraded after only 150-550 years. The control sampling after 7 years points toward a lower degradation of cellulose and production of ISA than predicted by the model, reflecting either a degradation of ISA that was faster than the production or a termination of the ISA production.

The use of an airtight frame in low-energy buildings could increase the risk of health-related problems, such as allergies and sick building syndromes (SBS), associated with chemical emissions from building materials, especially if the ventilation system is not functioning properly. In this study, the indoor air quality (IAQ) was investigated in newly built low-energy and conventional preschools by monitoring the indoor air temperature, relative humidity, particle-size distribution and levels of carbon dioxide (CO2), nitrogen dioxide (NO2), formaldehyde and total volatile organic compounds (TVOC). The thermal comfort was satisfactory in all preschools, with average indoor air temperature and a relative humidity at 21.4C and 36%, respectively. The highest levels of TVOC (range: 130–1650 mg/m3 toluene equivalents) and formaldehyde (range: 1.9–28.8 mg/m3) occurred during the first sampling period associated with strong emissions from building materials. However, those preschools constructed with environmental friendly building materials (such as Swan Eco-label) had lower initial TVOC levels compared to those preschools constructed with conventional building materials. The IAQ and indoor chemical emissions were also strongly dependent on the functioning of the ventilation system. Preliminary risk assessment indicated that exposure to acrolein and crotonaldehyde might lead to respiratory-tract irritation among occupants.