<p>The dietary intake of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) have been estimated for Swedish children. A dietary survey performed in 2003, including 4, 8-9 and 11-12 year olds, and concentrations in individual food items were combined. The food included in the study was mainly of animal origin, consisting of fish and shellfish, dairy products, meat products, eggs, animal and vegetable fats and fats from miscellaneous food products. The medium-bound intake of PBDEs (9 congeners) were estimated to 23.0 ng/day, 30.9 ng/day and 27.7 ng/day for 4, 8-9 and 11-12 years olds respectively. The corresponding estimations for HBCD were 7.94 ng/day 10.7 ng/day and 9.46 ng/day for 4, 8-9 and 11-12 years olds respectively. These results show a higher daily intake for 8-9 year olds compared with the other age groups. However, when estimating the daily intake per kg bw, the intake decreases with age. BDE-47 contributed the most to the total intake of PBDEs, with approximately 40%. The food group contributing the most to the intake of PBDEs and HBCD was fish and shellfish, of which non-Baltic fatty fish was the largest contributor. There were no considerable differences between boys and girls in any of the aspects examined. The result from this study show a lower intake of PBDEs and HBCD in Swedish children compared with children in other studies made in Europe and the United States.</p> / <p>Bromerade flamskyddsmedel används för att skydda brännbara material från att fatta eld, till exempel skyddas textilier och plaster i bland annat elektronik, fordon och möbler. Två typer av bromerade flamskyddsmedel är polybromerade difenyletrar (PBDE) och hexabromocyklododekan (HBCD). Dessa är additiva flamskyddsmedel och blandas i materialet som ska skyddas men binder inte in i produkten och kan därför lätt läcka ut i miljön, vilket också har skett. Halter har påträffats i miljön och i biota långt från plaster där ämnena produceras eller används.</p><p>PBDE och HBCD har visats ha hormonstörande och neurotoxiska effekter i studier på råtta och mus. Thyroxinnivåerna sjunker vid exponering av PBDE och HBCD, vilket skulle kunna leda till sköldkörtelproblem och störd utveckling av bland annat hjärnan om exponering sker perinatalt. De neurotoxiska effekterna inkluderar inlärnings- och minnessvårigheter och ett förändrat beteende med hyper- och hypoaktivitet som följd.</p><p>Human exponering för PBDE och HBCD sker främst via födan och speciellt via animaliska produkter då dessa ämnen är lipofila, bioackumulerande och ofta biomagnifierande vilket gör att de påträffas i högre koncentrationer högre upp i trofinivåerna. Studier från bland annat Sverige och Finland visar att fisk och skaldjur är den största källan till intag av PBDE.</p><p>De flesta intagsberäkningar av PBDE och HBCD baseras på livsmedelskonsumtionen hos vuxna och visar följaktligen endast hur intaget ser ut för den delen av populationen. För barn, som är en av de känsligaste grupperna i populationen, finns inte många studier att tillgå, varken från Sverige eller andra delar av världen. I den här studien har därför intaget av PBDE (summan av 9 kongener) och HBCD beräknats för barn i Sverige.</p><p>I en rikstäckande kostundersökning utförd 2003 deltog barn i åldrarna 4, 8-9 och 11-12 år. De fick i en matdagbok ange sin konsumtion under fyra på varandra följande dagar. Data från denna undersökning kombinerades sedan med haltdata från olika livsmedel för att räkna ut intaget av PBDE och HBCD på individbasis. Undersökningen innefattade främst animaliska livsmedel och innehöll därför fisk och skaldjur, mejeriprodukter, köttprodukter, ägg, animaliskt och vegetabiliskt fett och fett från övriga livsmedel.</p><p>Resultaten visar att födointaget av PBDE var 23,0 ng/dag, 30,9 ng/dag och 27,7 ng/dag för 4, 8-9 respektive 11-12 åringar. Intaget av HBCD beräknades till 7,94 ng/dag, 10,7 ng/dag och 9,46 ng/dag för 4, 8-9 respektive 11-12 åringar. Detta visar att 8-9 åringar har det högsta dagliga intaget av PBDE och HBCD. När intaget beräknas på kroppsvikt däremot, har de yngsta barnen det högsta intaget som sedan sjunker med åldern. Fisk och skaldjur var den största källan till intaget av PBDE och HBCD, trots att konsumtionen av dessa livsmedel var relativt lågt. Det fanns ingen större skillnad mellan pojkar och flickor, varken i intag av PBDE eller av HBCD. Jämfört med de få studier som gjorts i andra länder, är det tydligt att svenska barn har ett lägre intag av PBDE och HBCD.</p><p>Undersökningen tyder också på att intaget av PBDE och HBCD hos svenska barn, utifrån de kunskaper vi har idag, inte utgör någon risk med avseende på de effekter av PBDE och HBCD som påträffats i toxikologiska studier. Däremot är barn i ett känsligt skede i livet och upprepad exponering samt exponering för flera miljögifter samtidigt skulle kunna påverka deras utveckling negativt.</p>

[pt] PCBs, PBDEs e OCPs foram determinados em amostras de pequenos cetáceos, lulas e peixes oriundos da Costa Centro-Norte do Estado do Rio de Janeiro. Esta faixa litorânea apresenta extrema importância para a economia do país e compreende duas regiões distintas, que são o Norte Fluminense e a Região dos Lagos. Os níveis de todos os POPs determinados foram superiores nos pequenos cetáceos, seguidos de peixes e lulas. Os níveis de PCBs variaram entre 12,54 e 5202,95 ng g-1 (ww), onde os principais congêneres encontrados foram PCB 138, 153 e 180. Os PCBs predominantes em cetáceos foram os hexaclorados e nas demais espécies os pentaclorados. PBDEs foram encontrados apenas em amostras de pequenos cetáceos, com exceção dos músculos de P. blainvillei. Foram determinadas concentrações de PBDEs entre 7,82 e 184,02 ng g-1. O perfil da contaminação por PCBs e PBDEs sugere a utilização das misturas Aroclor 1254, 1260 e Penta-BDE. O principal pesticida organoclorado encontrado em todas as amostras foi o p,p -DDE, o qual apresentou valores entre 4,47 e 373,97 ng g-1. Foram estabelecidas correlações significativas entre os níveis de POPs e as variáveis morfométricas dos indivíduos de todas as espécies. Por fim, a análise dos isótopos estáveis de carbono e nitrogênio foi realizada a fim de determinar relações tróficas, preferências alimentares e diferenças no habitat destas espécies. Estes resultados contribuem para aumentar os dados disponíveis acerca da contaminação orgânica em organismos costeiros do Brasil e Hemisfério Sul. / [en] PCBs, PBDEs and OCPs were determined in samples of small cetacean, squid and fish from the Central-northern coast of Rio de Janeiro. This region has great importance for the Brazilian economy and comprises two distinct regions, which are Norte Fluminense and Região dos Lagos. The levels of all POPs were higher in small cetaceans, followed by fish and squid. PCB levels ranged from 12.54 to 5202.95 ng g-1 (wet wt). The main congeners found were PCB 138, 153 and 180. Hexachlorinated PCBs were the predominant congeners in cetaceans and pentachlorinanted PCBs were predominant in fish and squid. PBDEs were found only in cetaceans, except in muscles of P. blainvillei. PBDE concentrations ranged from 7.82 to 184.02 ng g-1. Contamination patterns suggest the previous use of Aroclor 1254, 1260 and Penta-BDE mixtures in Brazil. The main organochlorine pesticide found in this study was p,p-DDE, which presented levels in the range of 4.47 to 373.97 ng g-1. Significant correlations were found between the levels of POPs and morphometric variables of all the individuals. Finally, the analysis carbon and nitrogen stable isotopes was performed in order to assess trophic relationships, feeding preferences and differences on their habitat. These results contribute to extend the database on organic contamination in the Brazilian southeastern coast and in the Southern Hemisphere.

In the assessment of the environment pollution level, bio indicators of vegetable or animal origin are often used. Bio indicators include also needles and moss. The samples of moss and needles taken in different locations in the Czech Republic were examined to find out the presence of xenobiotics of polychlorine biphenyls and polybromide diphenylethers types. Selected analytes have been extracted from the matrix by hexan. Extracts have been refined using column chromatography on mixed florisil/silicagel sorbent. To analysis of selected compounds, GC/ECD method has been chosen. Based on our results a comparison of the contamination level in individual locations was enabled.

In recent years considerable attention is paid to problems of brominated flame retardants (BFR's – Brominated Flame retardants), which are a diverse group of organic compounds. Even in the recent past have been the most often represented group particularly polybrominated diphenyl ethers (PBDEs), which have found wide use in many industrial sectors. The reason of aplication of these substances is the ability to slow down the combustion process and reduce the risk of ignition by the excessive heating of material. On the other hand, serious concerns about the use of PBDEs was added. The most serious trouble is particular their possible to release from consumer products during their normal use, toxicity and high persistence in parts of environment. Some of these contaminants are more characterized by a high degree of accumulation in biological systems. In this work by several sub-studies the issue of assessment the level of pollution of the aquatic ecosystem of selected localities of the Czech Republic just PBDEs was addressed. One of objectives was monitored the situation of breeding ponds near the village Záhlinice in Central Moravia. Here was assessed level of contamination in fish and birds as two consecutive segments of food chain. The obtained results largely confirmed the assumption that with increasing trophic level of organisms leads to bioaccumulation and thus also higher findings. For comparison, the capture of fish and birds in other localities of the CR was also implemented. In Bartošovice and Hustopeče nad Becvou levels at the buzzard and heron were detected as comparable. The cormorants of the order higher levels of PBDEs were found. Further were also evaluated levels of PBDEs detected in individuals of bioindicator kind of chub caught in two locations on the river Svratka in spring and autumn. Findings of PBDE in muscle, skin and intestines were compared. The obtained results show that between tissues and sites wasn’t significant variability respectively and the findings of controlled substances are practically comparable. With aim to determine the dependence of the concentration of PBDEs in organisms on the length of the river was conducted monitoring of Vír and Brno water reservoirs. In both locations was main monitored kind of bream, which was completed by the other species. The results of the analysis indicate a higher total concentration at the lower part of river Svratka. Differences were also the distribution of individual congeners in both sampling locations. For monitoring of terrestrial system contamination levels of PBDEs has been selected several types of plant bioindicators. These are mainly pine needles (Scots pine, Eastern white pine, Silver fir, Blue spruce) collected from different localities of the Czech Republic. Other matrices were chosen roughages (Common wheat, Naked barley, Alfalfa wheat, Red clover) and oilseeds (Rapeseed) from the Novy Jicin, where Agriculture plant school of the University of Veterinary and Pharmaceutical Sciences Brno. Detected values of PBDE concentrations were very low, generally ranged at the detection limits of the analytical method.

Reclaimed water has increased in popularity as a means to recycle water and thus decrease the amount of wasteful water use. This process is widely used in Tampa Bay for watering of lawns. This increase in popularity and use has raised questions as to what contaminants are in the reclaimed water. The purpose of this study was to analyze reclaimed water for contaminants believed to be detrimental to health and conduct interviews to ascertain perceptions of risk in the local population. As water reuse grows in popularity further research will need to be conducted to address potential human health concerns. This research shows that there are potential health concerns related to reclaimed water when we use dioxin as a surrogate compound. Additionally, the research shows that local governments aren't doing enough to communicate information to local communities. Any policy that moves forward in regards to supplementing drinking water with reclaimed water must incorporate local communities in the decision making process. Decisions made in the absence of information can be misguiding and the first feedback of these decisions is felt by local communities. With their input in the beginning, throughout the decision making process, and during the evaluation period, new information will be generated. The incorporation of the community in the decision making process will make the reclaimed for drinking water initiative, more successful.

[pt] O atual trabalho teve como objetivo o desenvolvimento de um método multiresíduo e aplicação em testemunhos sedimentares para uma análise geocronológica da contaminação da Baía de Sepetiba por quatro classes de contaminantes orgânicos: (i) hidrocarbonetos policíclicos aromáticos (HPAs), (ii) bifenilos policlorados (PCBs); (iii) éteres difenílicos polibromados (PBDEs) e (iv) pesticidas organoclorados (OCPs). Além dos analitos contemplados no método desenvolvido, foram analisados outros parâmetros (HPAs alquilados, Biomarcadores de petróleo, Hidrocarbonetos Alifáticos, Carbono Orgânico Total e Nitrogênio Total) para que fosse possível uma análise mais aprofundada das fontes e da origem da MO e de compostos associados ao petróleo. Os testemunhos sedimentares foram coletados entre julho e outubro de 2016 e foram datados pela análise da atividade do decaimento de 210Pb e validado usando perfis de Zn e Cd. O método desenvolvido é baseado na extração ultrassônica com uma mistura de diclorometano:metanol (9:1 v/v) e cromatografia gasosa acoplada com análise de espectrometria de massa em tandem (GC-MS/MS) no modo de monitoramento de reações múltiplas (MRM). Um total de 89 compostos, dentre HPAs, PCBs, OCPs e PBDEs, foram identificados usando dois padrões de íon produto/precursor para cada analito. O limite de detecção do método (MDL; 0,001 – 0,055 ng g-1) e limite de quantificação do método (MQL; 0,002 – 0,184 ng g-1) estão abaixo dos níveis de poluição aceitáveis adotados pelas diretrizes internacionais de qualidade de sedimentos. O método, que foi publicado na revista Analytical and Bioanalytical Chemstry em maio de 2022, mostrou-se seletivo, sensível, preciso e linear, com a vantagem de reduzir o tempo de manuseio da amostra e a quantidade utilizada de materiais como solvente e adsorventes. A fim de analisar de forma mais aprofundada as fontes e origens dos HPAs nos testemunhos analisados, foi aplicado uma análise de dados baseada na Lógica Fuzzy, mais especificamente pelo algoritmo Fuzzy C-Means (FCM). Para que tivéssemos um melhor embasamento teórico da aplicação dessa ferramenta, um artigo foi publicado na revista Ocean and Coastal Research em fevereiro de 2022, com base na reavaliação estatística dos dados de dois trabalhos sobre contaminação do sedimento de baías costeiras por HPAs. Resultados obtido por meio de ferramentas de avaliação tradicionais foram comparadas com aqueles obtidos por FCM, que apresentaram maior detalhamento qualitativo. Embora a Lógica Fuzzy não produza interpretações quantitativas, sua aplicação gera dados adequados para que se evite uma inferência enviesada de fontes de contaminação de HPAs. A aplicação do método na análise dos testemunhos sedimentares foi bem-sucedida e a maioria das camadas apresentou valores de OCPs e PBDEs abaixo do MQL. Os valores de PCBs variaram de <MQL a 1,47 ng g-1 (média de 0,24 ± 0,38 ng g-1) em T18 e de 0,35 a 6,24 ng g-1 (média de 1,82 ± 1,37 ng g-1) em T26. Os HPAs variaram de 67,97 a 404,61 ng g-1 (média de 192,38 ± 98,48 ng g-1) em T18 e de 154,59 a 685,47 ng g-1 (média de 382,55 ± 168,45 ng g-1) em T26. / [en] The present work aimed at developing a multiresidue method and application in sedimentary testimonies for a geochronological analysis of the contamination of Sepetiba Bay by four classes of organic contaminants: (i) polycyclic aromatic hydrocarbons (PAHs), (ii) polychlorinated biphenyls (PCBs); (iii) polybrominated diphenyl ethers (PBDEs) and (iv) organochlorinated pesticides (OCPs). In addition to the analytes contemplated in the method developed, other parameters were analyzed (alkylated PAHs, petroleum biomarkers, aliphatic hydrocarbons, total organic carbon and total nitrogen) to allow a more in-depth analysis of the sources and origin of organic matter and compounds associated with petroleum. Sediment cores were collected between July and October 2016 by Gonçalvez et al. (2020) and were dated by analysis of 210Pb decay activity and validated using Zn and Cd profiles. The developed method is based on ultrasonic extraction with a mixture of dichloromethane:methanol (9:1 v/v) and gas chromatography coupled with tandem mass spectrometry analysis (GC-MS/MS) in multiple reaction monitoring (MRM) mode. A total of 89 compounds, among PAHs, PCBs, OCPs, and PBDEs, were identified using two product/precursor ion standards for each analyte. The method detection limit (MDL; 0.001 - 0.055 ng g-1) and method quantification limit (MQL; 0.002 - 0.184 ng g-1) are below acceptable pollution levels adopted by international sediment quality guidelines. The method, which was published in the journal Analytical and Bioanalytical Chemstry in May 2022, was shown to be selective, sensitive, accurate, and linear, with the advantage of reducing sample handling time and the amount used of materials such as solvent and adsorbents.In order to further analyze the sources and origins of PAHs in the analyzed core samples, we applied a data analysis based on Fuzzy Logic, more specifically the Fuzzy C-Means (FCM) algorithm. In order to have a better theoretical basis for the application of this tool, an article was published in the journal Ocean and Coastal Research in February 2022, based on the statistical re-evaluation of data from two studies on sediment contamination of coastal bays by PAHs. Results obtained through traditional assessment tools were compared with those obtained by FCM, which showed greater qualitative detail. Although Fuzzy Logic does not produce quantitative interpretations, its application generates adequate data to avoid biased inference of PAH contamination sources. The application of the method in the analysis of the sediment cores was successful and most layers showed OCPs and PBDEs values below the MQL. PCBs values ranged from <MQL to 1.47 ng g-1 (mean 0.24 ± 0.38 ng g-1) in T18 and from 0.35 to 6.24 ng g-1 (mean 1.82 ± 1.37 ng g-1) in T26. PAHs ranged from 67.97 to 404.61 ng g-1 (mean 192.38 ± 98.48 ng g-1) at T18 and from 154.59 to 685.47 ng g-1 (mean 382.55 ± 168.45 ng g-1) at T26.

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are naturally produced in aquatic ecosystems e.g. by algae. Many OH-PBDEs have been observed to be highly bioactive and to cause adverse effects through several pathways, e.g. via disrupting oxidative phosphorylation (OXPHOS). The levels of some OH-PBDEs have increased in Baltic biota over the past decades. This may be associated with the nutrient enrichment of the Baltic Sea, which has favored growth of some of the OH-PBDE producers. Ceramium tenuicorne has been suggested to be a producer of OH-PBDEs in the Baltic Sea, which is supported by the results presented in this thesis. The levels of OH-PBDEs were observed to fluctuate greatly in C. tenuicorne over the summer season, and to correlate with the levels of pigments in the algae. However, the observed congener pattern in C. tenuicorne questioned theories regarding the mechanism of their biosynthesis. The results indicate a much more selective pathway for biosynthesis than previously suggested for the production of OH-PBDEs. One of the most abundant OH-PBDEs in C. tenuicorne, 6-OH-BDE137, has previously been observed to be toxic to bacteria, fungi, and crustaceans. Furthermore, Baltic gammarids seemed to change their feeding preferences towards less grazing on C. tenuicorne during the production peek of OH-PBDEs in the alga. This suggests that OH-PBDEs may serve as allelochemical defense agents for C. tenuicorne. The transport and fate of OH-PBDEs through a Baltic food chain was also studied, including C. tenuicorne, Gammarus spp., three-spined stickleback (Gasterosteus aculeatus), and perch (Perca fluviatilis). A small portion of the OH-PBDEs were observed to be methylated in the alga, or by associated bacteria. The methylated OH-PBDEs biomagnified in the food chain up to perch, in which they were converted back to the OH-PBDEs via demethylation. The OH-PBDEs and their methylated counterparts were also partially debrominated in the food chain, which resulted in high concentration of 6-OH-BDE47 in the perch. This congener is the most toxic OH-PBDE with regards to OXPHOS disruption. Another biotransformation of OH-PBDEs was identified in Baltic Sea blue mussels (Mytilus edulis). High concentrations of OH-PBDEs were conjugated with lipophilic moieties, e.g. fatty acids. This increases the residence time of the OH-PBDEs in the mussels. Mussels have been suggested to conjugate steroids with fatty acids as a means to regulate hormone levels. The conjugation of OH-PBDEs to fatty acids may occur due to intrusion into this pathway. Methods were developed to include quantification of conjugated OH-PBDEs in the analysis of mussels. OH-PBDEs were also quantified in blood from Baltic Sea grey seals (Halichoerus grypus). Seals originating from the Baltic proper were observed to be more highly exposed to 6-OH-BDE47 than seals from the Gulf of Bothnia. However, the levels of OH-PBDEs were generally low. A major effort was invested into securing these results, including development of a new analytical method. Blood obtained from dead seals is a difficult matrix for quantification of OH-PBDEs, and previous attempts using an established method yielded unsatisfactory results. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.</p>

En la present tesi doctoral s’han estudiat diversos mètodes per a l’eliminació de contaminants orgànics persistents en olis de peix amb finalitat alimentària. S’han posat al punt les metodologies d’anàlisi necessàries per a la correcta determinació d’aquests compostos en la matriu d’estudi. S’han avaluat amb detall les etapes de purificació de la mostra, fraccionament dels analits i anàlisi instrumental. El mètode ha estat validat amb resultats satisfactoris, i s’ha comprovat el seu bon funcionament a través de la participació en diversos exercicis d’intercalibtage, així com la realització de diversos estudis amb mostres reals d’oli de peix. S’ha estudiat l’eliminació dels contaminants orgànics persistents a través d’adsorbents sòlids amb base silícica i carbonàcia. Les condicions experimentals han estat estudiades més a fons mitjançant dissenys d’experiències, per acabar optimitzant el mètode d’adsorció amb un disseny d’evolució. Els millors resultats s’han obtingut amb el carbó actiu, que mostra una elevada eficàcia en l’eliminació de PCDD/Fs, d-l PCBs i HCB. S’ha estudiat l’eliminació dels contaminants orgànics persistents mitjançant tècniques de degradació fotoquímiques. Inicialment s’ha fotodegradat cada família de contaminants per separat, per poder estudiar més a fons les condicions necessàries per la seva eliminació, així com els seus mecanismes i productes de degradació. Posteriorment s’ha estudiat la fotodegradació simultània dels analits d’interès en oli de peix. Aquesta tècnica s’ha mostrat efectiva en l’eliminació de DDT, PBDEs, HCB i PCBs similars a dioxines. Paral•lelament als estudis d’eliminació mitjançant adsorbents sòlids i tècniques fotoquímiques, s’ha comprovat la qualitat dels olis de peix abans i després del tractament. El procés d’adsorció en sòlids no afecta significativament a la qualitat de l’oli, mentre que les tècniques fotoquímiques degraden una part dels àcids grassos insaturats. S’ha estudiat l’eliminació de contaminants orgànics persistents en oli de peix mitjançant la combinació de les dues tècniques estudiades anteriorment, amb una primera etapa de degradació fotoquímica i una segona etapa d’adsorció. S’han comparat els resultats finals d’eliminació que s’obtenen amb cada un dels mètodes desenvolupats (adsorció, fotodegradació i combinat). L’adsorció en carbó actiu és el procés més adequat per l’eliminació de COPs en oli de peix. S’ha realitzat un estudi dels nivells diastereomèrics i enantiomèrics d’un contaminant emergent -l’hexabromociclododecà (HBCD)- en oli de peix. S’ha avaluat la seva eliminació de la matriu d’estudi mitjançant adsorbents amb base carbonàcia i degradació fotoquímica, sent principalment eliminat per aquesta segona via. / En la presente tesis doctoral se han estudiado diversos métodos para la eliminación de contaminantes orgánicos persistentes en aceites de pescado con finalidad alimentaria. Se han desarrollado los métodos de análisis necesarios para la correcta determinación de estos compuestos en la matriz de estudio. Se han evaluado con detalle las etapas de purificación de la muestra, fraccionamiento de los analitos y análisis instrumental. El método ha sido validado con resultados satisfactorios, y se ha comprobado su buen funcionamiento mediante ejercicios de intercalibraje, así como la realización de diversos estudios con muestras reales de aceite de pescado. Se ha estudiado la eliminación de los contaminantes persistentes mediante adsorbentes sólidos con base silícica y carbonacea. Las condiciones experimentales han estado estudiadas en profundidad mediante diseños de experiencias y de evolución. Los mejores resultados se han obtenido con carbón activo, que demuestra una elevada eficacia en la eliminación de PCDD/Fs, dl-PCBs y HCB. Se ha estudiado la eliminación de los contaminantes orgánicos persistentes mediante técnicas de degradación fotoquímica. Inicialmente se ha fotodegradado cada familia de contaminantes por separado, para poder estudiar más a fondo las condiciones necesarias para su eliminación. Posteriormente se ha estudiado la degradación simultánea de los analitos de interés en aceite de pescado. Esta técnica se ha mostrado efectiva en la eliminación de DDT, PBDEs, HCB y PCBs similares a dioxinas. Paralelamente a los estudios de eliminación mediante adsorbentes sólidos y técnicas fotoquímicas, se ha comprobado la calidad de los aceites de pescado antes y después del tratamiento. El proceso de adsorción en sólidos no afecta significativamente a la calidad del aceite, mientras que las técnicas fotoquímicas degradan una parte de los ácidos grasos insaturados. Se ha estudiado la eliminación de contaminantes orgánicos persistentes en aceites de pescado mediante la combinación de las dos técnicas estudiadas anteriormente, con una primera etapa de degradación fotoquímica y una segunda etapa de adsorción. Se han comparado los resultados finales de eliminación que se obtienen con cada uno de los métodos desarrollados. La adsorción en carbón activo es el proceso más adecuado para la eliminación de COPs en aceite de pescado. Se ha realizado un estudio de los niveles diastereoisoméricos y enantioméricos de un contaminante emergente –HBCD- en aceite de pescado. Se ha evaluado su capacidad de eliminación de la matriz de estudio mediante adsorbentes con base carbonacia y degradación fotoquímica, siendo principalmente eliminado por la segunda vía. / During the present doctoral thesis several methods for the elimination of persistent organic pollutants from fish oil have been studied. Analytical methodologies for the determination of these compounds in fish oil have been developed. Sample purification, fractionation of the analytes and instrumental determination steps have been deeply studied. The method has been validated with satisfactory results, and its performance has been verified through its participation in several intercalibration exercises and studies with real fish oil samples. Elimination of persistent organic pollutants with silicon and carbon-based adsorbents has been studied. The experimental conditions have been studied in depth with an experimental design, to finally optimize the adsorption method using an evolutionary design. Best results have been obtained with the active carbon, showing high efficiency of the removal of PCDD/Fs, dioxin-like PCBs and HCB. Elimination of persistent organic pollutants with photochemical degradation techniques has been studied. Initially, each family of pollutants has been photodegraded separately, to determine its degradation conditions, as well as degradation mechanisms and by-products. Later, simultaneous photodegradation of the analytes has been studied in fish oil. This technique has shown high efficiency on the degradation of DDT, PBDEs, HCB and dioxin-like PCBs. The quality of the oils before and after the treatments with solid adsorbents and photochemical degradation has also been studied. The adsorption process does not significantly affect the quality of the oils, while photochemical techniques can degrade the unsaturated fatty acids. Elimination of persistent organic pollutants in fish oil combining adsorption in solids and photochemical degradation has been studied. Results obtained with each of the developed methodologies (adsorption, photodegradation and combined method) were compared. Adsorption in active carbon is the most suitable process for COPs elimination in fish oil. Finally, diastereoisomeric and enantiomeric levels of an emerging pollutant –hexabromocyclododecane (HBCD)- in fish oil have been studied. Its elimination has been evaluated with carbon-based adsorbents and photochemical degradation, being mainly eliminated with the photodegradation techniques.

The dietary intake of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) have been estimated for Swedish children. A dietary survey performed in 2003, including 4, 8-9 and 11-12 year olds, and concentrations in individual food items were combined. The food included in the study was mainly of animal origin, consisting of fish and shellfish, dairy products, meat products, eggs, animal and vegetable fats and fats from miscellaneous food products. The medium-bound intake of PBDEs (9 congeners) were estimated to 23.0 ng/day, 30.9 ng/day and 27.7 ng/day for 4, 8-9 and 11-12 years olds respectively. The corresponding estimations for HBCD were 7.94 ng/day 10.7 ng/day and 9.46 ng/day for 4, 8-9 and 11-12 years olds respectively. These results show a higher daily intake for 8-9 year olds compared with the other age groups. However, when estimating the daily intake per kg bw, the intake decreases with age. BDE-47 contributed the most to the total intake of PBDEs, with approximately 40%. The food group contributing the most to the intake of PBDEs and HBCD was fish and shellfish, of which non-Baltic fatty fish was the largest contributor. There were no considerable differences between boys and girls in any of the aspects examined. The result from this study show a lower intake of PBDEs and HBCD in Swedish children compared with children in other studies made in Europe and the United States. / Bromerade flamskyddsmedel används för att skydda brännbara material från att fatta eld, till exempel skyddas textilier och plaster i bland annat elektronik, fordon och möbler. Två typer av bromerade flamskyddsmedel är polybromerade difenyletrar (PBDE) och hexabromocyklododekan (HBCD). Dessa är additiva flamskyddsmedel och blandas i materialet som ska skyddas men binder inte in i produkten och kan därför lätt läcka ut i miljön, vilket också har skett. Halter har påträffats i miljön och i biota långt från plaster där ämnena produceras eller används. PBDE och HBCD har visats ha hormonstörande och neurotoxiska effekter i studier på råtta och mus. Thyroxinnivåerna sjunker vid exponering av PBDE och HBCD, vilket skulle kunna leda till sköldkörtelproblem och störd utveckling av bland annat hjärnan om exponering sker perinatalt. De neurotoxiska effekterna inkluderar inlärnings- och minnessvårigheter och ett förändrat beteende med hyper- och hypoaktivitet som följd. Human exponering för PBDE och HBCD sker främst via födan och speciellt via animaliska produkter då dessa ämnen är lipofila, bioackumulerande och ofta biomagnifierande vilket gör att de påträffas i högre koncentrationer högre upp i trofinivåerna. Studier från bland annat Sverige och Finland visar att fisk och skaldjur är den största källan till intag av PBDE. De flesta intagsberäkningar av PBDE och HBCD baseras på livsmedelskonsumtionen hos vuxna och visar följaktligen endast hur intaget ser ut för den delen av populationen. För barn, som är en av de känsligaste grupperna i populationen, finns inte många studier att tillgå, varken från Sverige eller andra delar av världen. I den här studien har därför intaget av PBDE (summan av 9 kongener) och HBCD beräknats för barn i Sverige. I en rikstäckande kostundersökning utförd 2003 deltog barn i åldrarna 4, 8-9 och 11-12 år. De fick i en matdagbok ange sin konsumtion under fyra på varandra följande dagar. Data från denna undersökning kombinerades sedan med haltdata från olika livsmedel för att räkna ut intaget av PBDE och HBCD på individbasis. Undersökningen innefattade främst animaliska livsmedel och innehöll därför fisk och skaldjur, mejeriprodukter, köttprodukter, ägg, animaliskt och vegetabiliskt fett och fett från övriga livsmedel. Resultaten visar att födointaget av PBDE var 23,0 ng/dag, 30,9 ng/dag och 27,7 ng/dag för 4, 8-9 respektive 11-12 åringar. Intaget av HBCD beräknades till 7,94 ng/dag, 10,7 ng/dag och 9,46 ng/dag för 4, 8-9 respektive 11-12 åringar. Detta visar att 8-9 åringar har det högsta dagliga intaget av PBDE och HBCD. När intaget beräknas på kroppsvikt däremot, har de yngsta barnen det högsta intaget som sedan sjunker med åldern. Fisk och skaldjur var den största källan till intaget av PBDE och HBCD, trots att konsumtionen av dessa livsmedel var relativt lågt. Det fanns ingen större skillnad mellan pojkar och flickor, varken i intag av PBDE eller av HBCD. Jämfört med de få studier som gjorts i andra länder, är det tydligt att svenska barn har ett lägre intag av PBDE och HBCD. Undersökningen tyder också på att intaget av PBDE och HBCD hos svenska barn, utifrån de kunskaper vi har idag, inte utgör någon risk med avseende på de effekter av PBDE och HBCD som påträffats i toxikologiska studier. Däremot är barn i ett känsligt skede i livet och upprepad exponering samt exponering för flera miljögifter samtidigt skulle kunna påverka deras utveckling negativt.

The recent developments and improvements of instrumental methods for the analyses of the environmental contaminants, especially the persistent organic pollutants (POPs), have made it possible to detect and quantify these at very low concentrations in environmental and biotic matrices. The main objective of this thesis is to demonstrate the capability of the atmospheric pressure chemical ionization technique (APCI), using gas chromatography coupled to tandem mass spectrometry for the determination of a wide range of environmental contaminants, including the POPs regulated by Stockholm Convention, such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), but also the derivates of PBDEs and novel brominated flame retardants (NBFRs). The APCI was operated in charge transfer condition, preferably producing molecular ions. Multiple reaction monitoring (MRM) experiments were optimized by adjusting cone voltage, collision energy and dwell time. Optimization of source parameters, such as gas flows and temperatures was also performed. Low concentration standards were analyzed, achieving a visible chromatographic peak for 2 fg 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) demonstrating the excellent sensitivity of the system. Adequate linearity and repeatability were observed for all the studied compounds. The performance of APCI methods was validated against the conventional methods using gas chromatography coupled to high resolution mass spectrometry for chlorinated compounds in a wide range of matrices including environmental, air, human and food matrices. The GC-APCI-MS/MS method was successfully applied to a set of 75 human serum samples to study the circulating levels of POPs in epidemiologic studies. Moreover the method was utilized to establish temporal trends of POPs in osprey eggs samples collected during the past five decades.