Brominated flame retardants in the Australian population : 1993-2009

Brominated flame retardants, including hexabromocyclododecane (HBCD) and polybrominated diphenyl ethers (PBDEs) are used to reduce the flammability of a multitude of electrical and electronic products, textiles and foams. The use of selected PBDEs has ceased, however, use of decaBDE and HBCD continues. While elevated concentrations of PBDEs in humans have been observed in Australia, no data is available on other BFRs such as HBCD. This study aimed to provide background HBCD concentrations from a representative sample of the Australian population and to assess temporal trends of HBCD and compare with PBDE concentrations over a 16 year period. Samples of human milk collected in Australia from 1993 to 2009, primarily from primiparae mothers were combined into 12 pools from 1993 (2 pools); 2001; 2002/2003 (4 pools); 2003/2004; 2006; 2007/2008 (2 pools); and 2009. Concentrations of ∑HBCD ranged from not quantified (nq) to 19 ng g−1 lipid while α-HBCD and γ-HBCD ranged from nq to 10 ng g−1 lipid and nq to 9.2 ng g−1 lipid. β-HBCD was detected in only one sample at 3.6 ng g−1 lipid while ∑4PBDE ranged from 2.5 to 15.8 ng g−1 lipid. No temporal trend was apparent in HBCD concentrations in human milk collected in Australia from 1993 to 2009. In comparison, PBDE concentrations in human milk show a peak around 2002/03 (mean ∑4PBDEs = 9.6 ng g−1 lipid) and 2003/04 (12.4 ng g−1 lipid) followed by a decrease in 2007/08 (2.7 ng g−1 lipid) and 2009 (2.6 ng g−1 lipid). In human blood serum samples collected from the Australian population, PBDE concentrations did not vary greatly (p = 0.441) from 2002/03 to 2008/09. Continued monitoring including both human milk and serum for HBCD and PBDEs is required to observe trends in human body burden of HBCD and PBDEs body burden following changes to usage.

Partitioning of persistent organic pollutants (POPs) between human serum and breast milk : a literature review

The literature was reviewed to assess the relationship between the lipid adjusted concentration in human serum and breast milk (expressed as the serum/milk ratio) of a broad range of POPs in paired samples. Thirteen studies were identified, including seven studies that reported serum/milk ratios for polychlorinated dibenzo-dioxins and -furans (PCDD/Fs), ten for polychlorinated biphenyls (PCBs), five for polybrominated diphenyl ethers (PBDEs), and five for organochlorine pesticides (OCPs). Mean serum/milk ratios ranged between 0.7 and 25 depending on the compound and congener. For PCDD/Fs, PCBs and PBDEs, a clear trend of increasing mean serum/milk ratio by increasing molar volume, hydrophobicity and number of halogen substitutes was observed. The mean serum/milk ratios reported by the 13 studies summarized here will aid comparison between human POPs exposure studies using either serum or milk samples. More studies are needed to allow a valid comparison between data obtained from analysis of breast milk and serum samples for a broader range of POPs. Furthermore such studies may shed light on compound specific factors as well as other determinants that may affect the partitioning and partition kinetics of POPs between serum and breast milk.

Spatial mapping of city-wide PBDE levels using an exponential decay model

Passive air samplers (PAS) consisting of polyurethane foam (PUF) disks were deployed at 6 outdoor air monitoring stations in different land use categories (commercial, industrial, residential and semi-rural) to assess the spatial distribution of polybrominated diphenyl ethers (PBDEs) in the Brisbane airshed. Air monitoring sites covered an area of 1143 km2 and PAS were allowed to accumulate PBDEs in the city's airshed over three consecutive seasons commencing in the winter of 2008. The average sum of five (∑5) PBDEs (BDEs 28, 47, 99, 100 and 209) levels were highest at the commercial and industrial sites (12.7 ± 5.2 ng PUF−1), which were relatively close to the city center and were a factor of 8 times higher than residential and semi-rural sites located in outer Brisbane. To estimate the magnitude of the urban ‘plume’ an empirical exponential decay model was used to fit PAS data vs. distance from the CBD, with the best correlation observed when the particulate bound BDE-209 was not included (∑5-209) (r2 = 0.99), rather than ∑5 (r2 = 0.84). At 95% confidence intervals the model predicts that regardless of site characterization, ∑5-209 concentrations in a PAS sample taken between 4–10 km from the city centre would be half that from a sample taken from the city centre and reach a baseline or plateau (0.6 to 1.3 ng PUF−1), approximately 30 km from the CBD. The observed exponential decay in ∑5-209 levels over distance corresponded with Brisbane's decreasing population density (persons/km2) from the city center. The residual error associated with the model increased significantly when including BDE-209 levels, primarily due to the highest level (11.4 ± 1.8 ng PUF−1) being consistently detected at the industrial site, indicating a potential primary source at this site. Active air samples collected alongside the PAS at the industrial air monitoring site (B) indicated BDE-209 dominated congener composition and was entirely associated with the particulate phase. This study demonstrates that PAS are effective tools for monitoring citywide regional differences however, interpretation of spatial trends for POPs which are predominantly associated with the particulate phase such as BDE-209, may be restricted to identifying ‘hotspots’ rather than broad spatial trends.

Triclosan and benzophenone-3 in Australian pooled infant urine

The period of developmental vulnerability begins at conception and extends through gestation, parturition, infanthood and adolescence. The World Health Organisation (WHO) acknowledges that children experience quantitatively and qualitatively different exposures to chemicals than adults, and that children may be more or less sensitive to a chemical than adults [1, 2]. For instance, because of mouthing behaviours, children have higher exposure to chemicals through non-dietary ingestion than adults [3, 4], and the possibility exists for different metabolism and/or toxicity between different groups due to the immaturity of defense mechanisms that are fully developed in adults [1]. Traditional toxicological studies are inappropriate for assessing the results of exposure at very low levels during critical periods of development. Biomonitoring data can be used to identify where policies should be directed in order to reduce exposure.

Temporal trend of organochlorine pesticides in Australia

Persistent, lipophilic organochlorine pesticides (OCPs) such as dichlorodiphenyltrichloroethane (DDT), hexachlorocyclohexanes (HCHs), dieldrin, chlordanes, hexachlorobenzene (HCB) and mirex are known to accumulate in human samples [1, 2]. Persistent OCPs are among the chemicals that are covered under the Stockholm Convention on persistent organic pollutants [3]. Exceptions to this include relatively less lipophillic compounds like HCH (KOW<10^5). In Australia, OCPs such as DDT and HCHs were introduced in the 1940s. This followed a period of widespread use until the 1970s when recognition of risks related to OCPs resulted in reduced use and their ultimate ban in the 1980s. Mirex, however, remained in very restricted use in Northern Australia for treatment of one species of termites (the Giant Termite (Mastotermes darwinensis)) but this use was phased out in 2007.

Estimation of reference values for dioxin, furan, and PCB congener concentrations for the Australian population

Population-representative data for dioxin and PCB congener concentrations are available for the Australian population based on measurements in age- and gender-specific serum pools.1 Such data provide a basis for characterizing the mean concentrations of these compounds in the population, but do not provide information on the inter-individual variation in serum concentrations that may exist in the population within an age- and gender-specific group. Such variation may occur due to inter-individual differences in long-term exposure levels or elimination rates. Reference values are estimates of upper percentiles (often the 95th percentile) of measured values in a defined population that can be used to evaluate data from individuals in the population in order to identify concentrations that are elevated, for example, from occupational exposures.2 The objective of this analysis is to estimate reference values corresponding to the 95th percentile (RV95s) for Australia on an age-specific basis for individual dioxin-like congeners based on measurements in serum pools from Toms and Mueller (2010).

Using a pharmacokinetic model to interpret biomonitoring data of PBDEs in the Australian population

From human biomonitoring data that are increasingly collected in the United States, Australia, and in other countries from large-scale field studies, we obtain snap-shots of concentration levels of various persistent organic pollutants (POPs) within a cross section of the population at different times. Not only can we observe the trends within this population with time, but we can also gain information going beyond the obvious time trends. By combining the biomonitoring data with pharmacokinetic modeling, we can re-construct the time-variant exposure to individual POPs, determine their intrinsic elimination half-lives in the human body, and predict future levels of POPs in the population. Different approaches have been employed to extract information from human biomonitoring data. Pharmacokinetic (PK) models were combined with longitudinal data1, with single2 or multiple3 average concentrations of a cross-sectional data (CSD), or finally with multiple CSD with or without empirical exposure data4. In the latter study, for the first time, the authors based their modeling outputs on two sets of CSD and empirical exposure data, which made it possible that their model outputs were further constrained due to the extensive body of empirical measurements. Here we use a PK model to analyze recent levels of PBDE concentrations measured in the Australian population. In this study, we are able to base our model results on four sets5-7 of CSD; we focus on two PBDE congeners that have been shown3,5,8-9 to differ in intake rates and half-lives with BDE-47 being associated with high intake rates and a short half-life and BDE-153 with lower intake rates and a longer half-life. By fitting the model to PBDE levels measured in different age groups in different years, we determine the level of intake of BDE-47 and BDE-153, as well as the half-lives of these two chemicals in the Australian population.

Age-related trends in urinary excretion of bisphenol A in Australian children and adults : evidence from a pooled sample study using samples of convenience

Bisphenol A (BPA or 4,4’-(propane-2,2-diyl)diphenol) is a chemical intermediate in the production of polycarbonate and epoxy resins, and used in a wide range of applications. BPA has attracted significant attention in the past decade due to its frequency of detection in human populations worldwide, demonstrated animal toxicity and potential impact on human health, particularly during critical periods of development. The aim of this study was to perform a preliminary assessment of age-related trends in urinary concentration and to estimate daily excretion of BPA in Australian children (aged (>0 – <5 years) and adults (≥15 – <75 years). This was achieved using 79 samples pooled by age and gender, created from 868 individual samples of convenience collected as part of routine, community-based pathology testing. Total BPA was analyzed using online-SPE-LC-MS/MS and detected in all samples with a range of 0.65 – 265 ng/ml. No significant differences were observed between males and females. A urine flow model was constructed from published values and used to provide an estimate of daily excretion per unit bodyweight for each pooled sample. The daily excretion estimates ranged from 26.2 – 18200 ng/kg-d for children; and 20.1 – 165 ng/kg-d for adults. Urinary concentrations and estimated excretion rates were inversely associated with age, and estimated daily excretion rates in infants and young children were significantly higher than in adults (geometric mean: 107 and 47.0 ng/kg-d, respectively). Higher excretion of BPA in children may be explained by their higher food consumption relative to body weight compared to adults and adolescents, and may also reflect alternative exposure pathways and sources. Keywords: bisphenol A, biomonitoring, children, urine flow, Australia

Pooled biological specimens for human biomonitoring of environmental chemicals : opportunities and limitations

Biomonitoring has become the ‘gold standard’ in assessing chemical exposures, and plays an important role in risk assessment. The pooling of biological specimens – combining multiple individual specimens into a single sample – can be used in biomonitoring studies to monitor levels of exposure and identify exposure trends, or to identify susceptible populations in a cost-effective manner. Pooled samples provide an estimate of central tendency, and may also reveal information about variation within the population. The development of a pooling strategy requires careful consideration of the type and number of samples collected, the number of pools required, and the number of specimens to combine per pool in order to maximize the type and robustness of the data. Creative pooling strategies can be used to explore exposure-outcome associations, and extrapolation from other larger studies can be useful in identifying elevated exposures in specific individuals. The use of pooled specimens is advantageous as it saves significantly on analytical costs, may reduce the time and resources required for recruitment, and in certain circumstances, allows quantification of samples approaching the limit of detection. In addition, use of pooled samples can provide population estimates while avoiding ethical difficulties that may be associated with reporting individual results.

Assessing exposures to emerging environmental contaminants in children

The period of developmental vulnerability to toxicants begins at conception and extends through gestation, parturition, infanthood and childhood to adolescence. The concern is that children: (1) may experience quantitatively and qualitatively different exposures, and (2) may have different sensitivity to chemical pollutants. Traditional toxicological studies are inappropriate for assessing the results of chronic exposure at very low levels during critical periods of development. This paper will discuss (1) the health effects associated with exposure to selected emerging organic pollutants, including brominated flame retardants, perfluorinated compounds, organophosphate pesticides and bisphenol A; (2) difficulties in monitoring these substances in children, and (3) suggest techniques and strategies for overcoming these difficulties. Such biomonitoring data can be used to identify where policies should be directed in order to reduce exposure, and to document policies that have successfully reduced exposure.

A preliminary study on assessing body burden of persistent organic pollutants (POPs) in infants through analysis of faeces

Most persistent organic pollutants (POPs) like polychlorinated biphenyls (PCBs), a range of polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs) are readily absorbed (via the ingestion and inhalation) and accumulate in fatty tissue, including adipose tissue and human milk [1]. Health effects related to exposure to these chemicals may include neurological effects, altered functioning of the nervous system and/or endocrine disruption [2-4]. The burden of environmental disease is recognized as much higher for children than adults, especially in young children under 5 years of age worldwide [5]. There is increased concern regarding the environmental impact on the health of children who have been disproportionately affected by environmental problems. For example they may be subjected to relatively higher exposure, have greater physiological susceptibility and/or suffer more extreme consequences due to growth [6-9]. It is therefore worthwhile to assess the correlation between burden of disease and exposure to xenobiotic chemical pollutants like POPs. Such assessment may provide guidance for legislative changes regarding chemical bans and give reliable advice to parents including lactating mothers.

Knowledge, attitudes and practices to reduce exposure among residents living near Danang dioxin hot spot : 2.5 years after a preventative intervention

Da Nang Airbase in Viet Nam served as a bulk storage and supply facility for Agent Orange and other herbicides during Operation Ranch Hand 1961-1971[1]. Studies have shown that environmental and biological samples taken around the airbase site have elevated levels of dioxin [1-3]. Residents living in the vicinity of the airbase are at risk of exposure to dioxin in soil, water and mud and particularly through the consumption of local contaminated food. In 2009, a pre-intervention cross sectional survey was undertaken. This survey examined the knowledge, attitudes and practices (KAP) of householders living near Da Nang Airbase, relevent to reducing dioxin exposure through contaminated food. The results showed that despite living near a severe dioxin hot spot, the residents had very limited knowledge of both exposure risk and measures to reduce exposure to dioxin[4]. In response, the Vietnam Public Health Association (VPHA) and Da Nang Public Health Association implemented a risk reduction program at four residential wards in the vicinities of the Da Nang Airbase in 2010. A post intervention KAP survey was under taken in 2011, and the results showed that knowledge of the existence of dioxin in food, dioxin exposure pathways, potential high risk foods, and preventive measures was significantly enhanced. This new study monitored KAP 2.5 years after the intervention through a 2013 survey of food handlers from 400 households that were randomly selected from the four intervention wards. The results show that most of the positive outcomes remained stable or had increased; some KAP indicators decreased compared to those in the post-intervention survey, but were still significantly higher than the pre-intervention levels. In 2014, these findings will be incorporated with qualitative assessments and the results of laboratory analysis of dioxin concentrations in foods in Da Nang and Bien Hoa dioxin hot spots to comprehensively assess the sustained effects of the intervention.

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.

The effectiveness of an intervention in reducing risk of dioxin exposure in Da Nang : changes in community knowledge, attitudes and prevention practices after 2.5 years

Introduction Environmental and biological samples taken around Da Nang Air Base have shown elevated levels of dioxin over many years [1-3]. A pre-intervention knowledge, attitudes and practices (KAP) survey (2009), a risk reduction program (2010) and a post intervention KAP survey (2011) were undertaken in four wards surrounding Danang Airbase. A follow-up evaluation was undertaken in 2013. Methods A KAP survey was implemented among 400 randomly selected food handlers. Eleven indepth interviews and four focus group discussions were also undertaken. Results The knowledge of respondents remained positive and/or improved at 2.5 years follow-up. There were no significant differences in attitudes toward preventing dioxin exposure across surveys; most respondents were positive in all three surveys. An increase in households (69.5%) undertaking measures to prevent exposure was observed, which was higher than in the pre-intervention survey (39.6%) and post- intervention survey (60.4%) (χ2 = 95.6; p < 0.001). The proportion of respondents practicing appropriate preventive measures was also significantly improved. Conclusions Despite most of the intervention program’s activities ceasing in 2010, the risk reduction program has resulted in positive outcomes over the longer-term, with many knowledge and attitude measures remaining stable or imporving. Some KAP indicators decreased, but these KAP indicators were still significantly higher than the pre-intervention levels.