Assessing exposure to polybrominated diphenyl ethers (PBDEs) for workers in the vicinity of a large recycling facility

Increased levels of polybrominated diphenyl ethers (PBDEs) can occur particularly in dust and soil surrounding facilities that recycle products containing PBDEs. This may be the source of increased exposure for nearby workers and residents. To investigate, we measured PBDE levels in soil, office dust and blood of workers at the closest workplace (i.e. within 100m) to a large automotive shredding and metal recycling facility in Brisbane, Australia. The workplace investigated in this study was independent of the automotive shredding facility and was one of approximately 50 businesses of varying types within a relatively large commercial/industrial area surrounding the recycling facility. Concentrations of PBDEs in soils were at least an order of magnitude greater than background levels in the area. Congener profiles were dominated by larger molecular weight congeners; in particular BDE-209. This reflected the profile in outdoor air samples previously collected at this site. Biomonitoring data from blood serum indicated no differential exposure for workers near the recycling facility compared to a reference group of office workers, also in Brisbane. Unlike air, indoor dust and soil sample profiles, serum samples from both worker groups were dominated by congeners BDE-47, BDE-153, BDE-99, BDE-100 and BDE-183 and was similar to the profile previously reported in the general Australian population. Estimated exposures for workers near the industrial point source suggested indoor workers had significantly higher exposure than outdoor workers due to their exposure to indoor dust rather than soil. However, no relationship was observed between blood PBDE levels and different roles and activity patterns of workers on-site. These comparisons of PBDE levels in serum provide additional insight into the inter-individual variability within Australia. Results also indicate congener patterns in the workplace environment did not match blood profiles of workers. This was attributed to the relatively high background exposures for the general Australian population via dietary intake and the home environment.

Short term variability in urinary bisphenol A in Australian children

Used frequently in food contact materials, bisphenol A (BPA) has been studied extensively in recent years, and ubiquitous exposure in the general population has been demonstrated worldwide. Characterising within- and between-individual variability of BPA concentrations is important for characterising exposure in biomonitoring studies, and this has been investigated previously in adults, but not in children. The aim of this study was to characterise the short-term variability of BPA in spot urine samples in young children. Children aged ≥2-<4 years (n = 25) were recruited from an existing cohort in Queensland Australia, and donated four spot urine samples each over a two day period. Samples were analysed for total BPA using isotope dilution online solid phase extraction-liquid chromatography-tandem mass spectrometry, and concentrations ranged from 0.53–74.5 ng/ml, with geometric mean and standard deviation of 2.70 ng/ml and 2.94 ng/ml, respectively. Sex and time of sample collection were not significant predictors of BPA concentration. The between-individual variability was approximately equal to the within-individual variability (ICC = 0.51), and this ICC is somewhat higher than previously reported literature values. This may be the result of physiological or behavioural differences between children and adults or of the relatively short exposure window assessed. Using a bootstrapping methodology, a single sample resulted in correct tertile classification approximately 70% of the time. This study suggests that single spot samples obtained from young children provide a reliable characterization of absolute and relative exposure over the short time window studied, but this may not hold true over longer timeframes.

Why are there Different Age Related Trends for Different Chemicals?

Persistent organic pollutants (POPs) such as dioxins, PCBs, persistent organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) as well as perfluorinated compounds (PFCs) and triclosan are ubiquitous in the human population. In Australia, we have pooled and subsequently analysed over 10 000 human serum samples for the determination of these chemicals by age group (0–0.5; 0.6–1; 1.1–1.5; 1.6–2; 2.1–2.5; 2.6–3; 3.1–3.5; 3.6–4; 4.1–6; 6.1–9; 9.1–12; 12.1–15; 16–30; 31–45; 46–60 and >60 years) and gender. The results of this analysis were then used to assess the trends of these different chemicals as a function of age, gender and to a lesser extent region. Our data demonstrate clear chemical specific age trends. In particular we demonstrate that for the traditional POPs there is an increase in body burden with age whereas the opposite is true for chemicals such as PBDEs. For PFCs we find chemical specific age trends that vary from compound to compound. For triclosan we show that no apparent age trend is observable. The results of the study and its implications to the collection and archiving of samples for retrospective analysis are discussed.

Human exposure to brominated flame retardants

Human polybrominated diphenyl ether (PBDE) exposure occurs through a range of pathways including: ingestion of dust including hand-to-mouth contact; inhalation (air/particulate matter); and ingestion via food including the unique nutrition sources of human milk and placental transfer. While inhalation has been deemed a minor source of exposure, ingestion of food and dust make greater contributions to overall PBDE body burden with intake via dust reported to be much higher in infants than in adults. PBDEs have been detected in samples of human milk, blood serum, cord blood, and adipose tissue worldwide. Concentrations have been found to be highest in populations from North America, followed by Australia, Europe, and Asia. While factors such as gender and parity may not affect concentrations, occupational exposure and age (infants and children) are associated with higher PBDE concentrations. In contrast to “traditional” persistent organic pollutants, there is an inverse relationship between PBDE body burden and age. Predicted body burden calculated using available information on intake and elimination rates of BFRs appears to underestimate measured human body burden data obtained through analysis of BFRs in blood or human milk. This may be due to unknown exposure or inaccurate elimination data. Further exposure studies should focus on younger age groups and an investigation of human PBDE half-lives.

Assessment of polybrominated diphenyl ethers (PBDEs) in samples collected from indoor environments in South East Queensland, Australia

Polybrominated diphenyl ethers (PBDEs) are compounds that are used as flame retardants. Human exposure is suggested to be via food, dust and air. An assessment of PBDE exposure via indoor environments using samples of air, dust and surface wipes from eight sites in South East Queensland, Australia was conducted. For indoor air, ΣPBDEs ranged from 0.5 -179 pg/m3 for homes and 15 - 487 pg/m3 for offices. In dust, ΣPBDEs ranged from 87 - 733 ng/g dust and 583 - 3070 ng/g dust in homes and offices, respectively. PBDEs were detected on 9 out of 10 surfaces sampled and ranged from non-detectable to 5985 pg/cm2. Overall, the congener profiles for air and dust were dominated by BDE-209. This study demonstrated that PBDEs are ubiquitous in the indoor environments of selected buildings in South East Queensland and suggest the need for detailed assessment of PBDE concentrations using more sites to further investigate the factors influencing PBDE exposure in Australia.

Use of simple pharmacokinetic modeling to characterize exposure of Australians to perfluorooctanoic acid and perfluorooctane sulfonic acid

Perflurooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) have been used for a variety of applications including fluoropolymer processing, fire-fighting foams and surface treatments since the 1950s. Both PFOS and PFOA are polyfluoroalkyl chemicals (PFCs), man-made compounds that are persistent in the environment and humans; some PFCs have shown adverse effects in laboratory animals. Here we describe the application of a simple one compartment pharmacokinetic model to estimate total intakes of PFOA and PFOS for the general population of urban areas on the east coast of Australia. Key parameters for this model include the elimination rate constants and the volume of distribution within the body. A volume of distribution was calibrated for PFOA to a value of 170ml/kgbw using data from two communities in the United States where the residents' serum concentrations could be assumed to result primarily from a known and characterized source, drinking water contaminated with PFOA by a single fluoropolymer manufacturing facility. For PFOS, a value of 230ml/kgbw was used, based on adjustment of the PFOA value. Applying measured Australian serum data to the model gave mean+/-standard deviation intake estimates of PFOA of 1.6+/-0.3ng/kgbw/day for males and females >12years of age combined based on samples collected in 2002-2003 and 1.3+/-0.2ng/kg bw/day based on samples collected in 2006-2007. Mean intakes of PFOS were 2.7+/-0.5ng/kgbw/day for males and females >12years of age combined based on samples collected in 2002-2003, and 2.4+/-0.5ng/kgbw/day for the 2006-2007 samples. ANOVA analysis was run for PFOA intake and demonstrated significant differences by age group (p=0.03), sex (p=0.001) and date of collection (p<0.001). Estimated intake rates were highest in those aged >60years, higher in males compared to females, and higher in 2002-2003 compared to 2006-2007. The same results were seen for PFOS intake with significant differences by age group (p<0.001), sex (p=0.001) and date of collection (p=0.016).

Controlled automated discovery of collections of business process models

Automated process discovery techniques aim at extracting process models from information system logs. Existing techniques in this space are effective when applied to relatively small or regular logs, but generate spaghetti-like and sometimes inaccurate models when confronted to logs with high variability. In previous work, trace clustering has been applied in an attempt to reduce the size and complexity of automatically discovered process models. The idea is to split the log into clusters and to discover one model per cluster. This leads to a collection of process models – each one representing a variant of the business process – as opposed to an all-encompassing model. Still, models produced in this way may exhibit unacceptably high complexity and low fitness. In this setting, this paper presents a two-way divide-and-conquer process discovery technique, wherein the discovered process models are split on the one hand by variants and on the other hand hierarchically using subprocess extraction. Splitting is performed in a controlled manner in order to achieve user-defined complexity or fitness thresholds. Experiments on real-life logs show that the technique produces collections of models substantially smaller than those extracted by applying existing trace clustering techniques, while allowing the user to control the fitness of the resulting models.

Perturbing event logs to identify cost reduction opportunities: a genetic algorithm-based approach

Organisations are constantly seeking new ways to improve operational efficiencies. This research study investigates a novel way to identify potential efficiency gains in business operations by observing how they are carried out in the past and then exploring better ways of executing them by taking into account trade-offs between time, cost and resource utilisation. This paper demonstrates how they can be incorporated in the assessment of alternative process execution scenarios by making use of a cost environment. A genetic algorithm-based approach is proposed to explore and assess alternative process execution scenarios, where the objective function is represented by a comprehensive cost structure that captures different process dimensions. Experiments conducted with different variants of the genetic algorithm evaluate the approach's feasibility. The findings demonstrate that a genetic algorithm-based approach is able to make use of cost reduction as a way to identify improved execution scenarios in terms of reduced case durations and increased resource utilisation. The ultimate aim is to utilise cost-related insights gained from such improved scenarios to put forward recommendations for reducing process-related cost within organisations.

Combining passive sampling and toxicity testing for evaluation of mixtures of polar organic chemicals in sewage treatment plant effluent

Effluent from sewage treatment plants has been associated with a range of pollutant effects. Depending on the influent composition and treatment processes the effluent may contain a myriad of different chemicals which makes monitoring very complex. In this study we aimed to monitor relatively polar organic pollutant mixtures using a combination of passive sampling techniques and a set of biochemistry based assays covering acute bacterial toxicity (Microtox™), phytotoxicity (Max-I-PAM assay) and genotoxicity (umuC assay). The study showed that all of the assays were able to detect effects in the samples and allowed a comparison of the two plants as well as a comparison between the two sampling periods. Distinct improvements in water quality were observed in one of the plants as result of an upgrade to a UV disinfection system, which improved from 24× sample enrichment required to induce a 50% response in the Microtox™ assay to 84×, from 30× sample enrichment to induce a 50% reduction in photosynthetic yield to 125×, and the genotoxicity observed in the first sampling period was eliminated. Thus we propose that biochemical assay techniques in combination with time integrated passive sampling can substantially contribute to the monitoring of polar organic toxicants in STP effluents.

Population variation in biomonitoring data for persistent organic pollutants (POPs) : an examination of multiple population-based datasets for application to Australian pooled biomonitoring data

Background Australian national biomonitoring for persistent organic pollutants (POPs) relies upon age-specific pooled serum samples to characterize central tendencies of concentrations but does not provide estimates of upper bound concentrations. This analysis compares population variation from biomonitoring datasets from the US, Canada, Germany, Spain, and Belgium to identify and test patterns potentially useful for estimating population upper bound reference values for the Australian population. Methods Arithmetic means and the ratio of the 95th percentile to the arithmetic mean (P95:mean) were assessed by survey for defined age subgroups for three polychlorinated biphenyls (PCBs 138, 153, and 180), hexachlorobenzene (HCB), p,p-dichlorodiphenyldichloroethylene (DDE), 2,2′,4,4′ tetrabrominated diphenylether (PBDE 47), perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Results Arithmetic mean concentrations of each analyte varied widely across surveys and age groups. However, P95:mean ratios differed to a limited extent, with no systematic variation across ages. The average P95:mean ratios were 2.2 for the three PCBs and HCB; 3.0 for DDE; 2.0 and 2.3 for PFOA and PFOS, respectively. The P95:mean ratio for PBDE 47 was more variable among age groups, ranging from 2.7 to 4.8. The average P95:mean ratios accurately estimated age group-specific P95s in the Flemish Environmental Health Survey II and were used to estimate the P95s for the Australian population by age group from the pooled biomonitoring data. Conclusions Similar population variation patterns for POPs were observed across multiple surveys, even when absolute concentrations differed widely. These patterns can be used to estimate population upper bounds when only pooled sampling data are available.

Decline in perfluorooctane sulfonate and perfluorooctanoate serum concentrations in an Australian population from 2002 to 2011

Some perfluoroalkyl and polyfluoroalkyl substances (PFASs) have become widespread pollutants detected in human and wildlife samples worldwide. The main objective of this study was to assess temporal trends of PFAS concentrations in human blood in Australia over the last decade (2002–2011), taking into consideration age and sex trends. Pooled human sera from 2002/03 (n=26); 2008/09 (n=24) and 2010/11 (n=24) from South East Queensland, Australia were obtained from de-identified surplus pathology samples and compared with samples collected previously from 2006/07 (n=84). A total of 9775 samples in 158 pools were available for assessment of PFASs. Stratification criteria included sex and age: <16 years (2002/03 only); 0–4 (2006/07, 2008/09, 2010/11); 5–15 (2006/07, 2008/09, 2010/11); 16–30; 31–45; 46–60; and >60 years (all collection periods). Sera were analyzed using on-line solid-phase extraction coupled to high-performance liquid chromatography-isotope dilution-tandem mass spectrometry. Perfluorooctane sulfonate (PFOS) was detected in the highest concentrations ranging from 5.3–19.2 ng/ml (2008/09) to 4.4–17.4 ng/ml (2010/11). Perfluorooctanoate (PFOA) was detected in the next highest concentration ranging from 2.8–7.3 ng/ml (2008/09) to 3.1–6.5 ng/ml (2010/11). All other measured PFASs were detected at concentrations <1 ng/ml with the exception of perfluorohexane sulfonate which ranged from 1.2–5.7 ng/ml (08/09) and 1.4–5.4 ng/ml (10/11). The mean concentrations of both PFOS and PFOA in the 2010/11 period compared to 2002/03 were lower for all adult age groups by 56%. For 5-15 year olds, the decrease was 66% (PFOS) and 63% (PFOA) from 2002/03 to 2010/11. For 0-4 year olds the decrease from 2006/07 (when data were first available for this age group) was 50% (PFOS) and 22% (PFOA). This study provides strong evidence for decreasing serum PFOS and PFOA concentrations in an Australian population from 2002 through 2011. Age trends were variable and concentrations were higher in males than females. Global use has been in decline since around 2002 and hence primary exposure levels are expected to be decreasing. Further biomonitoring will allow assessment of PFAS exposures to confirm trends in exposure as primary and eventually secondary sources are depleted.

Historical intake and elimination of polychlorinated biphenyls and organochlorine pesticides by the Australian population reconstructed from biomonitoring data

Quantifying the competing rates of intake and elimination of persistent organic pollutants (POPs) in the human body is necessary to understand the levels and trends of POPs at a population level. In this paper we reconstruct the historical intake and elimination of ten polychlorinated biphenyls (PCBs) and five organochlorine pesticides (OCPs) from Australian biomonitoring data by fitting a population-level pharmacokinetic (PK) model. Our analysis exploits two sets of cross-sectional biomonitoring data for PCBs and OCPs in pooled blood serum samples from the Australian population that were collected in 2003 and 2009. The modeled adult reference intakes in 1975 for PCB congeners ranged from 0.89 to 24.5 ng/kg bw/day, lower than the daily intakes of OCPs ranging from 73 to 970 ng/kg bw/day. Modeled intake rates are declining with half-times from 1.1 to 1.3 years for PCB congeners and 0.83 to 0.97 years for OCPs. The shortest modeled intrinsic human elimination half-life among the compounds studied here is 6.4 years for hexachlorobenzene, and the longest is 30 years for PCB-74. Our results indicate that it is feasible to reconstruct intakes and to estimate intrinsic human elimination half-lives using the population-level PK model and biomonitoring data only. Our modeled intrinsic human elimination half-lives are in good agreement with values from a similar study carried out for the population of the United Kingdom, and are generally longer than reported values from other industrialized countries in the Northern Hemisphere.

Polybrominated diphenyl ether (PBDE) human half lives estimated from North Americans moving to Australia

Human half-lives of PentaBDE congeners have been estimated from the decline in serum concentrations measured over a 6-12 month period for a population of exchange students moving from North America to Australia. Australian serum PBDE concentrations are typically between 5 -10 times lower than in North America and we can therefore hypothesize that if the biological half-life is sufficiently short we would observe a decline in serum concentration with length of residence in Australia. Thirty students were recruited over a period of 3 years from whom serum were archived every 2 months during their stay in Australia. Australian residents (n=22) were also sampled longitudinally to estimate general population background levels. All serum samples were analyzed by gas chromatography high resolution mass spectrometry. Key findings confirmed that BDE-47 concentrations in the Australians (median 2.3;

Polybrominated diphenyl ethers and age: analysis of pooled human blood serum from birth to over 60 years

Polybrominated diphenyl ethers (PBDEs) are considered to be a cost effective and efficient way to reduce flammability therefore reducing harm caused by fires. PBDEs are incorporated into a variety of manufactured products and are found worldwide in biological and environmental samples (e.g. Hites et al. 2004). Unlike other persistent organic pollutants there is limited data on PBDE concentrations by age and/or other population specific factors. Some studies have shown no variation in adult serum PBDE concentrations with age (e.g. Mazdai et al., 2003, Meironyte Guvenius et al., 2003) while Petreas et al. (2003) and Schecter et al. (2005) found results to be suggestive of an age trend in adult data but no statistically significant correlation was found. In addition to the data on adult concentrations there is limited data which investigates the levels of PBDEs in infants and young children. Fangström et al. (2005) showed that in seven year olds there was no difference in PBDE concentration when compared to adult concentrations. While Thomsen et al. (2002, 2005) found the concentration of PBDEs in pooled samples of blood serum from a 0-4 years age group to be higher than other age groups (4 to > 60 years). In addition, a family of four was studied in the U.S. and the concentrations were found to be greatest in the 18-month-old infant followed by the 5 year old child, then the mother and father (Fischer et al., 2006). The objectives of this study were to assess age, gender and regional trends of PBDE concentrations in a representative sample of the Australian population.