ABSTRACT The tropical and subtropical nearshore marine environments of Queensland, Australia sustain diverse and unique marine wildlife. Continuous population growth and land-use changes along the Queensland coastline are known to exert numerous anthropogenic pressures on these marine ecosystems, including the delivery of high sediment loads. Sediments also provide a transport pathway for persistent organic pollutants (POPs) from rural and urban catchments into the marine environment. While such pollutants are known to be elevated in marine sediment and biota from nearshore areas in Queensland, their input and distribution pathways, as well as exposure and associated risks to wildlife populations are only partially understood. Mounting evidence suggests that POPs may contribute to population declines in marine wildlife species; however, limited information is available regarding the accumulation and effects of these contaminants in endangered or threatened marine turtles. This study aimed to redress some of these information gaps using a case study approach in marine turtle habitats of Moreton Bay, and other embayments in Queensland. Among persistent organic pollutants (POPs), dioxins (polychlorinated dibenzo-p-dioxins; PCDDs) and to some extent also dioxin-like PCBs (polychlorinated biphenyls; PCBs) were found to be widespread and often present at elevated (ppb) levels in surface sediments from Moreton Bay. However, while PCDD/F toxic equivalencies (TEQs) are above international (Canadian) sediment quality guidelines at numerous sites in Moreton Bay, in general TEQs across the Bay are relatively low compared to those from contaminated locations near dense industrial activities. POP contamination in surface sediments across Moreton Bay was investigated by a combination of GIS spatial mapping, geostatistical and traditional statistical modalities. High spatial variability and complex spatial distribution patterns were revealed. High resolution GIS kriging model outputs from the mid to southern Bay facilitated identification of distinct sediment contamination zones, with highest PCB and PCDD/F levels present in nearshore locations, associated with nearby river systems. While primarily governed by organic carbon, a multitude of physical, chemical and hydrological factors were identified to influence the spatial variance of PCDD/F concentrations. The main parameters governing PCDD/F spatial distribution were identified as sediment geochemistry, water depth and anthropogenic alterations of the physical environment and, together, all quantifiable explanatory variables (including hydrodynamic flushing) explained ≈75% of spatial PCDD/F variance. Together, the interaction of these parameters results in complex distribution patterns and highly variable concentrations even among neighbouring sites of 1-3 km resolution. These results suggest that prediction models of POP distributions in the nearshore marine environment may require high-resolution validation, and highlights that the design of low resolution monitoring strategies can have profound impacts on the reliability of contaminant information or any subsequent extrapolations. This knowledge and methodology can be utilised to optimise on-going and future near-shore sediment monitoring programs both locally and in other regions around the world. Using the spatial distributions of dioxin-like contaminants within sediments, this study provided an opportunity to assess field-based relationships between habitat contamination and local marine biota contamination. Detectable levels of PCDD/Fs and dioxin-like PCBs were measured in all green, hawksbill, loggerhead and flatback marine turtle tissues. POP concentrations in sediments were found to significantly correlate with those in the herbivorous green turtle from different sediment contamination zones. These findings demonstrate that sediments represent an important secondary contaminant source and lead to redistribution of POPs to the marine food chain. POP concentrations and TEQs clearly increased from sediment to turtles as well as with increasing trophic levels in marine turtle species. The results from this study demonstrate that the extent of sediment contamination within foraging habitats governs marine turtle exposure, while, trophic status and to some extent age influence contaminant exposure within a particular contamination zone. Despite the relatively low TEQ in sediments from Moreton Bay, TEQ levels in green turtle sub-populations foraging from near-shore locations and higher trophic loggerhead and flatback turtles are similar or elevated compared to those reported for other marine wildlife from Moreton Bay and elsewhere, even compared to higher trophic species from locations impacted by dense industrial activities. High bioaccumulation potential of 2,3,7,8-PCDD/F and dioxin-like PCBs compounds were estimated for green turtles using biota to sediment accumulation factors. Selective accumulation of toxicologically more potent (i.e. lower chlorinated) PCDD/Fs was observed for higher trophic marine turtles, resulting in increasing TEQs for the carnivorous species. Biomagnification was also observed for some non-2,3,7,8-substituted dioxin congeners which typically do not accumulate in most biota. These results are proposed to be due to relatively high accumulation efficiency and/or low metabolic capacity for these POP compounds in marine turtles. These findings are also hypothesised to reflect temperature dependant, greater bioavailability of hydrophobic chemicals in sub-tropical and shallow marine systems. An additional pilot study revealed that in contrast to PCDD/Fs and PCBs, levels of persistent flame retardants (polybrominated diphenyl ethers; PBDEs) were relatively low in marine turtles and other marine species (dugong, fish and shellfish) from Moreton Bay. This suggests relatively low level input of these more recent industrial products into the marine environment. However, as elevated levels of PBDEs have been reported in blood from the general population of Australia, ongoing transport from the terrestrial to the marine system and redistribution of these contaminants, similar to PCDD/F and PCBs, would be expected to occur into the future. Limited information is available regarding the sensitivity of reptiles to and effects of POPs, however, studies have shown that reptiles are sensitive to POPs albeit with uncharacterised relative potency. In the absence of robust toxicological information for reptiles or marine turtles, the potential risks associated with PCDD/F and PCB exposure of Queensland turtle populations was evaluated using toxicity for sensitive biological endpoints observed in mammals and birds. Using probabilistic methodology for marine turtles from Queensland, the body burden of up to 31% and 55% of green and loggerhead turtles, respectively, are above the threshold levels where the most sensitive physiological effects are observed in mammals and birds. While this evaluation illustrates that the contaminants investigated have the potential to impact on the health of marine turtle populations, it must be highlighted that it is compromised by the lack of species-specific (and in this case, class-specific) information, the uncertainty of which is often considered to represent a factor of at least 10. The findings of the present study indicate that exposure to POPs has the potential to adversely affect the health of Queensland’s marine turtle populations, and highlight the need for robust information on reptile specific sensitivity to these compounds.

Polychlorinated-p-dibenzo dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) (collectively termed ‘dioxins’) and polychlorinated biphenyls (PCBs) are three groups of persistent organic pollutants (POPs) ubiquitous in the environment due to their emission from numerous sources, high persistency and a propensity to be transported long distances. These compounds bioaccumulate in animal tissue, biomagnify through the food web and are toxic to humans and wildlife at relatively low concentrations. Humans may be exposed to POPs via ingestion, inhalation and dermal absorption, however, for the general population, approximately 90% of the total exposure occurs through intake of contaminated food particularly from lipid rich products, including seafood. An Australian national study highlighted that, similar to many other countries, seafood contributes a major proportion to dioxin and PCB exposure of Australians. As typical for national studies, the exposure assessment utilised contaminant concentrations in retail (sea)food and consumption information based on national dietary surveys. The risk assessment showed that the Australian population on the whole has a very low risk of exposure to dioxins through food. However, more than 80% of the Australian population lives within 50 km of the coast, where recreational, cultural and/or subsistence fishing of local seafood is prominent, potentially from areas with elevated PCDD/F and PCB concentrations. Through analysis of local seafood contamination and community seafood consumption patterns, this study assessed PCDD/F and PCB exposure for a coastal subpopulation in Moreton Bay, Queensland who consume locally caught seafood from an area with elevated PCDD/F and PCB concentrations but relatively low (background) toxic equivalency (TEQDP) in sediments, which is typical for Australian nearshore marine systems. Despite low sediment TEQDP levels, due to the dominance of octachlorodibenzo-p-dioxin (which is considered less potent compared to the most toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin), elevated TEQDP concentrations were present in local seafood. In particular higher trophic fish species and some traditional seafood were found to contain TEQDP above current EU action and maximum limits. This highlights the efficiency of species specific contaminant uptake, bioaccumulation and biomagnification processes, which can result in accumulation of higher toxic dioxin and PCB congeners in biota. In contrast, concentrations of most organochlorine pesticides and flame retardants (polybrominated diphenylehters (PBDEs)) were relatively low in seafood from Moreton Bay. For fish, uptake of highly lipophilic contaminants, such as PCDD/Fs and PCBs occurs predominantly via food (biomagnification) and respiratory processes (bioconcentration) followed by selective accumulation of the more toxic, lower chlorinated 2,3,7,8 PCDD/F congeners. This study discovered that physical contact with sediment and dermal absorption of lipophilic contaminants also represents an important exposure pathway for sediment dwelling fish, resulting in higher lipid normalised PCDD/F, PCB and TEQ levels (up to 8, 5 and 3 fold) in skin compared to muscle tissue. PCDD/F and PCB congener profiles differed between muscle and skin suggesting biomagnification and skin absorption as the respective predominant uptake pathways for these tissues. Dermal uptake was estimated to contribute up to 46% to the total TEQDP load on a lipid basis in sediment dwelling fish species, thus representing an important exposure pathway, and extending the bioavailability of sediment-sorbed pollutants to the food web. Accurate determinations of lipid content and lipid TEQDP contamination within seafood samples are critical to human exposure assessments. To ensure quality assurance, different seafood extraction methods were tested to evaluate their impact on lipid yields and contaminant concentration. While levels of PCDD/Fs and PCBs on a lipid basis did not vary across the different methods employed in this study, sample preparation is a significant determinant of lipid yield from fattier fish species. If samples were freeze dried prior to extraction, 30% higher TEQDP values (on a wet weight basis) were obtained as compared to extraction using fresh sample material. Such variance in lipid results will have a significant impact on exposure assessments and should be taken into consideration during seafood contaminant analysis. The median TEQDP concentration from local seafood was approximately 25 fold higher compared to the retail seafood analysed for the national Australian risk assessment. The seafood consumption survey results from this study further indicate that coastal subpopulations consume considerably more seafood than the general population (2 to 6 times more in the present case study). This proved to be an important driver for contaminant exposure in this subpopulation. The average monthly dioxin intake for the coastal community ranged between 34 (best case) to 107 (worst case) pg TEQ kg bw-1 month1, (95th percentile: 114 - 362 pg TEQ kg bw-1 month1), an order of magnitude higher than that estimated for the general population. The contaminant exposure via the local seafood consumption pathway alone exceeded WHO tolerable daily intake levels in 11-44% of the population. These results have important implications with respect to adequate contaminant exposure assessments of Australian and other coastal subpopulations. The study outcomes highlight the importance of considering local conditions and information on contaminant fate processes for human exposure evaluations. Local seafood consumption in coastal communities can result in high exposure to PCDD/F and PCBs, even in background contamination areas. This information would be important to consider for developing future sediment quality guidelines and with respect to exposure and associated risks for coastal communities in general.

Due to environmental concerns, most of persistent organic pollutants (POPs) have been eliminated or reduced in production and use; however, due to their great persistency, POPs are expected still to be found in the environment long after their use has ceased. Although, in recent years, POPs have rarely been detected in river water in the United Kingdom (UK), their concentrations in fish (biota) and sediment are expected to be notable due to their lipophilicity and bioaccumulation; however, there is a lack of information and data to understand the current contamination of POPs in catchments and evaluate their potential risk to the environment and ecosystem. This thesis describes the application of mathematical modelling approaches to (i) predict the current distribution and concentration of POPs in catchments, (ii) evaluate the influence of climate change and extreme weather conditions on the fate of POPs, and (iii) provide guidelines to inform decision-making on managing the potential risks of POPs in river basins. The modelling studies have mainly focused on polychlorinated biphenyls (PCBs). The River Thames catchment was chosen as the study area. The Fugacity level III model was initially used to describe the general distribution of PCBs between different compartments; it was predicted that the greatest mass of PCBs remain in the soil, but the fish and sediments represent compartments with the highest PCB concentrations. The contamination of PCBs in Thames fish was estimated to exceed the unrestricted consumption thresholds of 5.9 μg/kg for ∑PCBs set by the U.S. Environmental Protection Agency (EPA); no current EU Environmental Quality Standards (EQS) are available for PCBs in fish. It was indicated that the PCBs in fish could be linked to PCB contamination in sediment, which was predicted to be about three times higher than the fish concentrations, but insufficient observed data of PCBs in Thames fish and sediment are available to validate the results. In order to address this limitation in observed data, fish and sediment sampling and chemical analysis were carried out for the presence of POPs. In addition to PCBs, the measured results for hexachlorobenzene (HCB) and polybrominated diphenyl ethers (PBDEs) in Thames fish and sediment were assessed. Although the observed fish- and sediment concentrations of the chemicals appear quite variable, when normalised to organic carbon the levels in sediment, they were comparable to the fish lipid normalised concentrations. Using the temperature and rainfall data forecasts in the UK Climate Projections 2009 (UKCP09), climate change scenarios were established and assessed in the fugacity modelling. The modelling results suggested a modest influence of climate change on PCB fate over the next 80 years. The most significant result was a tendency, in the Thames catchment, for climate change to enhance the evaporation of PCBs from soil to air. While the fugacity model successfully simulated the distribution and fate of PCBs, we used greatly simplified representations of climate, hydrology and biogeochemical processes of the catchment: to have a deeper understanding, a newly developed dynamic hydrobiogeochemical transport model - the Integrated Catchment Contaminants model (INCAContaminants) was applied. Using additional information about weather, river flows and water chemistry, the INCA-Contaminants model provided new insights into the behaviour of contaminants in the catchment; this led to a better representation of PCB contamination in sediment. In addition, INCA demonstrated the important impact of short-term weather variation on PCB movement through the environment. It was shown that PCBs contamination in Thames sediment was greatly disturbed by the severe flooding that occurred in early 2014. This thesis presents the application of the INCA model to assess - in addition to POPs - the behaviour of metaldehyde in the River Thames catchment. Metaldehyde is a type of pesticide used mainly to kill snails and slugs. Its application in agricultural areas within the catchment area has in recent years caused severe problems with drinking water supply. The INCA model has proved to be an effective tool for simulating the transport of metaldehyde in the catchment, predicting observed metaldehyde concentrations at multiple locations in the River Thames; this is the first time that a dynamic modelling approach has been used to predict the behaviour of metaldehyde in river basins. Modelling results showed that high concentrations of metaldehyde in the river system are a direct consequence of excessive application rates. In this thesis, a simple decision-support tool was derived from modelling results, based on variable application rates and application areas. This decision-support tool is now being used by Thames Water to help control peak concentrations of metaldehyde at key water supply locations.

Seafood represents the most important source of long-chain polyunsaturated fatty acids (LC-PUFAs) in the human diet. However, consuming fish can present risks from persistent organic pollutants (POPs) that bioaccumulate in edible tissues following dietary exposure. In farmed fish, POPs accumulate as a result of feeding diets based on fish oil (FO). Fish oil substitution can reduce POP accumulation, but also results in loss of beneficial LC-PUFAs. Fish oil-based finishing diets at the end of production can restore LC-PUFAs, but this strategy also increases POPs. The present study assessed the use of saturated fatty acid (SFA)-rich lipids to replace fish oil in grow-out feeds in conjunction with a fish oil-rich finishing diet to determine if this strategy could produce hybrid striped bass with equal production performance, equivalent LC-PUFA levels, and reduced POP concentrations. Triplicate tanks of hybrid striped bass were raised on diets containing fish oil (100% FO), fish oil spiked with additional POPs (100% FO Spike), or blends (50/50 or 25/75) of FO and coconut (CO) or palm (PO) oils (50% CO, 50% PO, 75% CO, 75% PO) with and without an eight week finishing period with the 100% FO diet prior to harvest. Production performance, fillet LC-PUFA, and POP content were assessed. Production performance was not adversely affected by any of the feeding regimens. However, fatty acid profile was altered, with fillets of fish consuming less fish oil having lower LC-PUFA and POP levels. Finishing yielded a modest increase in fillet LC-PUFAs and POPs, but POPs accumulated more readily than LC-PUFAs during finishing. However, harvest fillet POP and LC-PUFA levels in the experimental groups were lower relative to levels in the 100% FO group. Replacing fish oil in aquafeeds can produce fish with reduced LC-PUFAs, and also reduced POPs. Feeding fish oil results in more rapid accumulation of POPs than LC-PUFA. Overall, the 75% fish oil replacement feeds yielded fish with the highest ratio of LC-PUFAs to POPs. Despite lower LC-PUFA content, fillets of fish fed the 75% fish oil replacement feeds could be incorporated into a weekly meal plan with other dietary sources of LC-PUFAs to meet dietary recommendations for these essential nutrients.

Persistent organic pollutants such as polychlorinated biphenyls (PCBs), DDT and polybrominated diphenyl ethers (PBDEs) tend to accumulate in biota and are transferred through the aquatic food web, which result in a high accumulation in marine mammals. In recent years various novel flame retardants (nBFRs), which have replaced the banned PBDEs, have also started to occur in the environment. These nBFRs have similar properties as PBDEs, such as long-range transport and accumulation in biota. The purpose with this study was to evaluate a method by using pre-packed silica columns for quantification of PCBs, DDT, PBDEs and nBFRs in seal blubber, in order to facilitate the pre-treatment and decrease the time. To elute the different POPs from the pre-packed silica column; hexane, toluene and dichloromethane were used in different stages. By using this method levels of PCB and DDT were determined. For DDT the concentration was 8.28 ng/g lipid and 8.94 ng/g lipid for the two samples that was analysed, and the analysis of the PCBs showed a higher trend for the higher chlorinated PCBs. As the pre-packed silica columns are a relative new method. Further studies are therefore needed on these columns to further improve the sample clean-up and fractionation of the different POPs in environmental samples.

Permafrost thaw slumping along lakeshores in lakes of the Mackenzie Delta Uplands, NT is known to alter water chemistry significantly. Its impact on benthic communities and persistent organic pollutant (POP) behaviour in lakes is not known. Benthic invertebrate communities responded to slumps through changes to community composition and size spectra. Larger taxa tended to dominate in lakes with slumps. Variability in biomass size spectra was related to total dissolved nitrogen concentration and slump size. Concentrations of POPs in Gammarus were negatively correlated with total phosphorus and positively correlated with the percentage of the catchment slumped. Lakes with slumps generally had higher mean concentrations of POPs in Gammarus (ex. ΣPCBsDisturbed = 27.54 ng/g lipid, ΣPCBsUndisturbed = 16.97 ng/g lipid; ΣDDT Disturbed =18.47 ng/g lipid and ΣDDTUndisturbed =10.86 ng/g lipid). Benthic invertebrate biomass was also negatively correlated with concentrations of contaminants in Gammarus, supporting the biomass dilution hypothesis. Thaw slumps have large enough impacts on the physico-chemical characteristics of lakes that they alter benthic invertebrate community composition and size-structure, and contaminant concentrations in Gammarus.

Reactive Black 5 and Procion Red MX 5B, an azo and anthraquinone dye repectively were decoulorized by mean of microorganisms growing on wood chips. The process consisted of three reactors, two anaerobic reactors and one aerobic reactor. The anaerobic process was used in order to make it possible to break the nitrogen bond of the azo group, (-N=N-) and the aerobic one to increase the possibility for the degradation of possible intermediates. After pumping wastewater through the system it was shown that mixtures or Reactive Black 5 and Procion Red MX 5B were efficiently decolourised at 50 mg/l as well as 200 mg/l of each of the dyes.

Apesar de os defensivos agrícolas atualmente classificados como Poluentes Orgânicos Persistentes (POPs) terem sua produção e uso banidos na maior parte do mundo desde a década de 1980, o gerenciamento de estoques remanescentes permanece um desafio até a atualidade. Com estimativas que variam entre 500 mil (FAO, 2015) e 2 milhões de toneladas (VIJGEN et al., 2011), poucas informações sobre seu efetivo gerenciamento e destruição são encontradas nas principais bases de dados acadêmicas sobre o tema e nos documentos oficiais da Convenção de Estocolmo sobre Poluentes Orgânicos Persistentes. O Brasil integra a lista de signatários da Convenção, mas a fabricação, o armazenamento e o uso dos agrotóxicos POPs foram proibidos em 1985, por meio da Portaria do Ministério da Agricultura nº 329. Este abrupto banimento do armazenamento colocou o agricultor brasileiro imediatamente fora da lei, uma vez que não foram planejadas medidas e procedimentos legais para dar destino adequado aos produtos que ainda estivessem em estoque nas propriedades rurais. De forma independente da Convenção de Estocolmo e das ações nacionais relacionadas a este tratado, dois estados brasileiros elaboraram programas para o levantamento de estoque dos defensivos agrícolas banidos e planejamento de sua destinação. Finalizado em 2013, o Paraná incinerou cerca de 1.200 toneladas que estavam estocadas em mais de 2.000 propriedades rurais do estado. São Paulo finalizou o inventário em 2012, resultando em 420 toneladas estocadas em aproximadamente 330 propriedades rurais. O grupo de trabalho paulista planejou as etapas seguintes e em abril de 2016, o projeto se encontrava em fase de alocação de recursos para execução das fases finais de acondicionamento, transporte e destinação. A proposta deste projeto de pesquisa é apresentar como Paraná e São Paulo gerenciaram os estoques remanescentes de agrotóxicos banidos há décadas, avaliando como os grupos de trabalho foram formados, as normativas de apoio utilizadas, como foram realizadas as etapas de levantamento de inventário e de que forma foram planejadas, financiadas, comunicadas e executadas as etapas de coleta, acondicionamento, transporte e destinação. Dessa forma, busca-se contribuir para um aumento de conhecimento prático sobre o tema e para a construção de uma política pública para gerenciamento de agrotóxicos banidos em outros estados brasileiros. / Although the pesticides currently classified as Persistent Organic Pollutants (POPs) have had their production and use banned in most of the world since the 1980s, the management of remaining stocks remains a challenge to the present. With estimates ranging from 500,000 (FAO, 2015) and 2 million tons (Vijgen et al., 2011), little information about its effective management and destruction are found in major academic databases on the subject and official documents of the Stockholm Convention on Persistent Organic Pollutants. Brazil is one of the signatories but the manufacture, storage and use of pesticides POPs were banned in 1985 by the Ministry of Agriculture Decree No. 329. However, this abrupt ban put the Brazilian farmers immediately outside the law since the government did not plan measures and legal procedures to give proper destination to the products that were still in stock on farms. Independently of the Stockholm Convention and the National Plans related to this treaty, two Brazilian states have developed programs to inventory banned pesticides and plan their destination. Finished in 2013, Paraná State incinerated about 1,200 tons that had been stored in more than 2,000 rural properties. Sao Paulo finished its inventory in 2012 resulting in 420 tons stored in about 330 rural properties. The São Paulo working group has planned the next steps and, in April 2016, the project was waiting for resource in order to implement the final stages of packaging, transport and disposal. The purpose of this research is to present as Parana and Sao Paulo managed the remaining stocks of banned pesticides evaluating how the working groups were formed, the support normative used, how the inventory has been planned and carried out and how the projects have financed, communicated and executed the steps of collection, packaging, transportation and disposal. Thus, it is expected to contribute to increase the practical knowledge on the topic and to construct a public policy for pesticide management banned in other Brazilian states.

Bulk atmospheric deposition samples were taken every two months for a year in 2009-2010 at two sites in northern Sweden and analyzed for a suite of legacy and emerging persistent organic chemicals including legacy organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs)  and novel flame retardants (NFRs).  To further investigate the urban occurrence and contribution to remote contamination of flame retardants, indoor air, ventilation system air, and dust were sampled in several microenvironments in Stockholm during the winter of 2012 for analysis of PBDEs, isomer-specific hexabromocyclododecane (HBCDD), and NFRs.  Outdoor air and soil samples were also sampled around the same time period for analysis of the same compounds.  Five emerging pollutants were detected in atmospheric deposition: the current-use pesticides trifluralin and chlorothalonil; and the NFRs 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), 1,2-bis(tribromophenoxy)ethane (BTBPE), and Dechlorane Plus (DP).  A decrease in the fraction of the anti isomer of DP was observed at the more remote site, indicating isomer-selective degradation or isomerization during long range atmospheric transport.  The more remote site also received more total deposition of organic pollutants despite its receiving less precipitation.  Although PBDEs and emerging organic pollutants were detected, the bulk of the deposition consisted of PCBs and hexachlorocyclohexanes (HCHs) at both sites.   Several NFRs were identified in indoor and ventilation air samples including TBECH, pentabromotoluene (PBT), hexabromobenzene (HBB), 1,2-bis(pentabromodiphenyl)ethane (DBDPE), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB), and bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (TBPH).  There was no significant difference between concentrations of contaminants in ventilation system air and indoor air indicating that the flame retardants included in this study reach the outdoor environment via ventilation systems.  Dust and outdoor air samples have only been analyzed for HBCDDs so far.  HBCDD concentrations in apartments, offices, and schools were lower than reported concentrations for other countries in similar microenvironments.   However, an enrichment of α-HBCDD compared to γ-HBCDD was observed in dust taken from near treated products in stores when compared to dust taken directly from those products.  Very low concentrations of HBCDDs were detected in outdoor air.

Polychlorinated biphenyls (PCBs) are toxic and persistent chemicals that have been largely dispersed into the environment. The biological and abiotic transformations of PCBs often generate hydroxylated derivatives, which have been detected in a variety of environmental samples, including animal tissues and feces, water, and sediments. Because of their toxicity and widespread dispersion in the environment, hydroxylated PCBs (OH-PCBs) are today increasingly considered as a new class of environmental contaminants. Although PCBs are known to be susceptible to microbial degradation under both aerobic and anaerobic conditions, bacterial degradation of OH-PCBs has received little attention. The overall objective of this study is therefore to evaluate the transformation of mono-hydroxylated PCBs by the well characterized aerobic PCB-degrading bacterium, Burkholderia xenovorans LB400. In order to achieve our overall objective, a series of model mono-hydroxylated PCBs have been selected and they are used to determine the toxicity of hydroxylated congeners toward the bacterium B. xenovorans LB400. The biodegradation kinetics and metabolic pathways of the selected OH-PCBs by B. xenovorans LB400 are then characterized using GC/MS. To understand further the molecular basis of the metabolism of OH-PCBs by B. xenovorans LB400, gene expression analyses are conducted using reverse-transcription real-time (quantitative) polymerase chain reaction (RT-qPCR) and microarray technology. More formally, the specific aims of the proposed research are stated as follows: (1) To evaluate the toxicity of selected mono-hydroxylated derivatives of lesser-chlorinated PCBs toward the bacterium B. xenovorans LB400. (2) To assess the degradation of the selected OH-PCBs by B. xenovorans LB400. (3) To gain further understanding of the molecular bases of the metabolism of the selected OH-PCBs by B. xenovorans LB400. Three hydroxylated derivatives of 4-chlorobiphenyl and 2,5-dichlorobiphenyl, including 2'-hydroxy-, 3'-hydroxy-, and 4'-hydroxy- congeners, were significantly transformed by Burkholderia xenovorans LB400 when the bacterium was growing on biphenyl (biphenyl pathway-inducing conditions). On the contrary, only 2'-OH-4-chlorobiphenyl and 2'-OH-2,5-dichlorobiphenyl were transformed by the bacterium growing on succinate (conditions non-inductive of the biphenyl pathway). Gene expression analyses showed that only exposure to 2'-OH-4-chlorobiphenyl and 2'-OH-2,5-dichlorobiphneyl resulted in induction of key genes of the biphenyl pathway, when cells grown on succinate. These observations suggest that 2'OH-PCBs were capable of inducing the genes of biphenyl pathway. These results provide the first evidence that bacteria are able to cometabolize PCB derivatives hydroxylated on the non-chlorinated ring. Genome-wide transcriptional analyses using microarrays showed that 134 genes were differentially expressed in cells exposed to biphenyl, 2,5-dichlorobiphenyl, and 2'-OH-2,5-dichlorobiphneyl as compared to non-exposed cells. A significant proportion of differentially expressed genes were simultaneously expressed or down regulated by exposure to the three target compounds i.e., biphenyl, 2,5-DCB, and 2'-OH-2,5-DCB, which suggests that these structurally similar compounds induce similar transcriptional response of B.xenovorans LB400. Results of this study may have important implications for the natural attenuation of PCBs and fate of OH-PCBs in the environment. The recalcitrance to biodegradation and the high toxicity of some OH-PCBs may provide a partial explanation for the persistence of PCBs in the environment. / Civil Engineering