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This study aimed to develop and chromatographic method for the determination of bisphenol A in four different food simulants using high performance liquid chromatography and diode array detector (PDA) to support in enasios migration. The simulating used were A (purified water), B (solution aquosade 3% acetic acid), C (aqueous 10% ethanol) and D (aqueous 95% ethanol). Preliminary assessment of the analytical conditions was conducted in order to establish those that confer the best results, which were the system of mobile phase acetonitrile-water in the ratio 70:30 by volume, 40 ° C oven and length of the column wavelength of 201 nm. The retention time of the bisphenol A was found to be 3.25 minutes. For simulating the method of treatment consists of evaporation of sample 1 ml of sample at 60 ° C with duration of 1 hour and 45 minutes (A and C), 2 hours (B) and 1 hour (D). In sequence, the method was evaluated with respect to the parameters of analytical validation, including linearity, limit of detection and quantification, repeatability, intermediate precision between different analysts and between different days, recovery, selectivity and robustness. The method for simulating the coefficient for determining (r ²) or greater than 0.9988 in the range tested (50 to 2000 ppb); detection limit and quantitation, respectively, 14.7 ppb and 48.9 ppb; coefficient variation in repeatability of 2.07% for the inter-day precision of 1.05% and the accuracy of inter-Analyst 1.76%, recovery of 97.9% (CV = 1.3%) (50 ppb ), 99.2% (CV = 0.7%) (1000 ppb) and 103.6% (CV = 0.4%). The results for the simulant B includes coefficient of determination (r ²) 0.9972 or higher; limit of detection and quantification, respectively, 7.8 ppb and 26.0 ppb; coefficients of variation for repeatability of 3.74%, inter day precision, accuracy and 0.14% cross-Analyst 0.2%, 94.8% recovery (CV = 4.8%) (50 ppb) and 99.8% (CV = 0.2% ) (1000 ppb) and 92.3% (CV = 1.2%) (2000 ppb). For the simulant C results include a coefficient of determination (r ²) 0.9988 or higher; limit of detection and quantification, respectively, 4.8 ppb and 16.1 ppb, coefficient of variation for repeatability of 2.84%, accuracy inter-day precision of 1.37% and inter-analysts of 0.14%; de104 recovery, 6% (CV = 2.5%) (50 ppb), 99.8% (CV = 1.3%) ( 1000 ppb) to 102.5% (CV = 2.9%) (2000 ppb). The results for simulating D was 0.9984 r ² or more, detection limit and quantitation, respectively, 13.7 ppb and 45.6 ppb; coefficient of variation of 2.0% to repeatability, accuracy of an inter-day 9% and accurate inter-de1 analysts, 2%; recuperção 92.6% (CV = 1.76%) (50 ppb) and 99.9% (CV = 0.9%) (1000 ppb) and 104 8% (CV = 2.7%) (2000 ppb). There were no significant interferences to the method tested and proved to be robust. Este trabalho teve como objetivo o desenvolvimento e metodologia cromatográfica para a determinação de bisfenol A em quatro diferentes simulantes de alimentos utilizando cromatografia líquida de alta eficiência e detector de arranjo de diodo (PDA) para suporte em enasios de migração. Os simulantes utilizados foram A (água purificada), B (solução aquosade ácido acético a 3%), C (solução aquosa de etanol a 10%) e D (solução aquosa de etanol a 95%). A avaliação preliminar das condições de análise foi conduzida com a finalidade de estabelecer aquelas que conferem os melhores resultados, os quais foram o sistema de fase móvel acetonitrila-água na proporção volumétrica 70:30, temperatura de 40°C do forno da coluna e comprimento de onda em 201 nm. O tempo de retenção do bisfenol A encontrado foi de 3,25 minutos. Para os simulantes, o método de tratamento consistiu da evaporação de 1 ml de amostra amostra a 60°C com duração de 1 hora e 45 minutos (A e C), 2 horas (B) e 1 hora (D). Em sequência, o método foi avaliado com relação aos parâmetros de validação analítica, incluindo linearidade, limite de detecção e de quantificação, repetibilidade, precisão intermediária entre analistas diferentes e entre dias diferentes, recuperação,seletividade e robustez. O método desenvolvido para o simulante A apresentou coeficiente de determinação (r²) 0,9988 ou superior no intervalo testado (50 a 2000 ppb); limite de detecção e de quantificação , respectivamente, 14,7 ppb e 48,9 ppb; coeficiente de variação para repetibilidade de 2,07%, para a precisão inter-dias de 1,05% e para a precisão inter-analistas de 1,76%; recuperação de 97,9% (CV= 1,3%) (50 ppb), 99,2% (CV= 0,7%) (1000 ppb) e 103,6% (CV= 0,4%). Os resultados obtidos para o simulante B incluem coeficiente de determinação (r²) 0,9972 ou superior; limite de detecção e de quantificação, respectivamente, 7,8 ppb e 26,0 ppb; coeficientes de variação para repetibilidade de 3,74%, precisão inter-dias de 0,14% e precisão inter-analistas de 0,2%; recuperação de 94,8% (CV= 4,8%) (50 ppb), 99,8% (CV= 0,2%) (1000 ppb) e 92,3% (CV= 1,2%) (2000 ppb). Para o simulante C os resultados incluem coeficiente de determinação (r²) 0,9988 ou superior; limite de detecção e de quantificação, respectivamente, 4,8 ppb e 16,1 ppb; coeficiente de variação para repetibilidade de 2,84%, precisão inter-dias de 1,37%e precisão inter-analistas de 0,14%; recuperação de104,6% (CV= 2,5%) (50 ppb), 99,8% (CV= 1,3%) (1000 ppb) e 102,5% (CV= 2,9%) (2000 ppb). Os resultados para o simulante D foram r² 0,9984 ou superior; limite de detecção e de quantificação,respectivamente, 13,7 ppb e 45,6 ppb; coeficiente de variação para repetibilidade de 2,0%, precisão inter-dias de 1,9% e precisão inter-analistas de1,2%; recuperção de 92,6% (CV= 1,76%) (50 ppb), 99,9% (CV= 0,9%) (1000 ppb) e 104,8% (CV= 2,7%) (2000 ppb). Não foram observados interferentes importantes para o método testado, mostrando-se robusto.

Today a lot of attention is focused on compounds called endocrine disrupters (EDs) among substances released to environment by humans. They are a group of substances which can disturb function of hormonal system of organisms including humans. Their poor removal at wastewater treatment plants (WwTP) were shown at various studies, thus they can reach the environment in water. A prospective way for the degradation of EDs at WwTP can be their removal by ligninolytic fungi. They are able to degrade lots of lignin-like aromatic substances because of their highly nonspecific enzymes. In this work growth and enzyme production capability of four ligninolytic fungal strains were monitored on three solid substrates (straw pellets, poplar sawdust mixed with straw pellets, oak sawdust with straw pellets), which may be suitable substrates for fungal growth in bioreactors for wastewater treatment. Ability of these enzymes to degrade EDs were tested in in-vitro degradation experiment. Trametes versicolor was found as best degrading strain with 20 μg/ml of bisphenol A, 17 α- ethynylestradiol and nonylphenol degraded below a quantification limit within 24 hours. Fungal strains degraded EDs well on all of the three substrates but wood sawdust seemed to be a better substrate for fungal growth because straw pellets...

Hormonaly active compounds in wastewaters represent nowdays a serious problem. Proceses currently used in watewater treatment plants (WWTP) are unefficient in removing these compounds from contaminated wastewaters. The compounds are supposed to sorb onto solid sludge elements and sediments. In this work seven endocrine disruptors were detected in the sludge samples from WWTPs. A new sensitive method for detection of seven selected endocrine disruptors (4-nonylphenol, bisphenol A, estriol, 17β-estradiol, estrone, 17α- ethynylestradiol, irgasan) was developed. The method is based on accelerated solvent extraction (ASE), gel permeation chromatography (GPC) and solid phased extraction. For final extract analysis, gas chromatography coupled with mass spectrometry (GC/MS) was used. The efficiency of this method was tested using artificially contaminated sludge and the method was used to analyse real samples from several WWTPs in Czech Republic. The effect of sludge age on detection of individual analytes was assessed as well. The concentrations of endocrine disruptors measured in the samples reached up to 1 µg/g. The results are comparable or higher then those reported in other works and they show the necessity of further research on endocrine disruptors in the environment.

Totalförbjud Bisfenol A helt, enligt miljöbalkens lag omförsiktighetsprincipen, säger Ulrika Dahl på Naturskyddsföreningen. På andra sidan står Europeiska myndigheten för livsmedelssäkerhet, EFSA, och pekar på tester som visar att Bisfenol A inte är skadligt förmänniskan i de mängder vi får i oss. Tester som inte är gjorda för kemikalier som Bisfenol A. Så vad ska vi tro på?

Los contaminantes ambientales, como los disruptores endocrinos,podrían provocar profundos cambios en los seres vivos. Aqui se analizan las alteraciones neuroendocrinas y reproductivas en mamíferos, incluyendo las descriptas en humanos, causadas por una molécula de origen industrial, el Bisfenol A. Exposure to endocrine disruptors may produce profound alterations in several species. As an example, the neuroendocrine and reproductive alterations due to Bisphenol A in mammals are summarized here. Os contaminantes ambientais, como os disruptores endócrinos, poderiam provocar profundas alterações nos seres vivos. Aqui são analisadas as alterações neuroendócrinas e reprodutivas em mamíferos, incluindo as descritas em humanos, causadas por uma molécula de origem industrial,o Bisfenol A Fil: Bourguignon, Nadia. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Biología y Medicina Experimental (i); Argentina Fil: Fernández, Marina . Universidad de Buenos Aires. Facultad de Medicina; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Biología y Medicina Experimental (i); Argentina Fil: Lux, Victoria Adela R.. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Biología y Medicina Experimental (i); Argentina Fil: Libertun, Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Biología y Medicina Experimental (i); Argentina. Universidad de Buenos Aires. Facultad de Medicina; Argentina

Bu çalışmanın amacı Afyonkarahisar ilinde yaşayan 100 anneye ait süt örneklerinde Nonilfenol (NF) ve Bisfenol A (BFA) konsantrasyonlarını belirlemek ve annelerin demografik özellikleri, beslenme alışkanlıkları, obstetrik öyküleri ve temizlik ve kozmetik ürün kullanma faktörleri ile değişimlerini incelemektir. Süt örneklerindeki BFA ve NF konsantrasyonları HPLC tekniği ile asetonitril ve katı faz ekstraksiyon kullanılarak hesaplanmıştır. BFA düzeyi 0,36–16,34 ng/ml arasında değişen değerlerde tespit edilmiştir. Ortalama BFA konsantrasyonu 1,82±0,22 (Ort ± SH) olarak değişmektedir. NF yüksek oranlarda ortalama 10,10±0,98 ng/ml olarak (0,04– 47,5 ng/ml) değişmektedir. Bu çalışmada, BFA veya NF konsantrasyonları ile annelerin yaş, mesleki durum, eğitim durumu ve gebelik sayısı ile herhangi bir farklılık görülmemiştir. Balık tüketim sıklığı ile sütlerdeki NF düzeyi arasında pozitif bir ilişki bulunmuştur. Ayrıca sıklıkla temizlik ürünü kullanan kadınlarda önemli bir şekilde yüksek oranlarda NF düzeyi görülmüştür. Süt ve süt ürünleri, yiyecekler ve kışlık malzemeler için plastik kap kullanan annelerde besin saklama kaplarında plastik kullanılması ile BFA düzeyleri arasında anlamlı bir ilişki bulunmuştur. The aims of this study were to determine the concentrations of Nonylphenol (NP) and Bisphenol A (BPA) in 100 human milk samples in Afyonkarahisar, and to examine related factors including mothers’ demographics, eating habits, obstetric histories, usage of cleaning and cosmetic products. The BPA and NP concentrations of milk samples were estimated by HPLC after the acetonitrile extraction and solid phase extraction column purification. BPA was detected in the concentration range of 0.36–16.34 ng/ml. The mean concentration of BPA was 1.82±0.22 (mean ± SE) ng/ml. NP has been found at the highest levels with mean concentrations of 10.10±0.98 ng/ml in the concentration range of 0.04–47.5 ng/ml. In this study, there was no significant correlation between the concentrations of BPA or NP in milk samples and the mother’s age, occupation, education, number of pregnancy. A positive correlation among fish consumption and levels of NP in the milk was observed. Women who used cleaning products had significantly higher NP concentrations than those who used less. A significant correlation was found between the levels of BPA and usage of plastic container in milk and dairy products, food and winter food storage containers.

Tez (Yüksek Lisans) -- İstanbul Teknik Üniversitesi, Fen Bilimleri Enstitüsü, 2011, Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2011, Bu çalışmada, Bisfenol A (BPA) ve 4-Nitrofenol (4-NP) fenolik bileşiklerinin, üretilen ve daha sonraki aşamada saflaştırılan çok duvarlı karbon nanotüpler (ÇDKNT) ile sistematik olarak gerçekleştirilen adsorpsiyonunu kapsamaktadır. Bu çalışmanın temel hedefi, seçilen fenolik bileşiklerin karbon nanotüpler ile adsorpsiyon davranımını incelemek ve laboratuar ortamında hazırlanan çok duvarlı karbon nanotüplerin adsorpsiyon verimliliğini ortaya koymaktır. ÇDKNT üretimi, kimyasal buhar birikimi yöntemi ile akışkan yatak sisteminde karbon kaynağı olarak asetilen gazı, katalizör malzemesi olarak demir nitrat ve magnezyum oksit kullanılarak gerçekleştirilmiştir. Üretilen ÇDKNT yapıları, sıvı faz oksidasyon yöntemi ile saflaştırılmıştır. Fenolik bileşiklerin adsorpsiyon davranımını gözlemlemek için süre, pH, sıcaklık ve adsorban miktarının etkisi incelenmiştir. Adsorpsiyon sürecinin, incelenen bazı parametrelere bağımlı olduğu, ÇDKNT yapısının içerdiği metalik katalizörün bu süreci engellediği tespit edilmiştir. Saflaştırılmış ÇDKNT numunesi ile yapılan çalışmalarda, adsorpsiyon kapasitesinin önemli ölçüde arttırıldığı gözlenmiştir. Denge durumundaki deneysel verilerin değerlendirilmesi için Freundlich, Langmuir ve Temkin izotermleri uygulanmıştır. Her iki bileşiğin deneysel verilerinin Freundlich modeli ile uyum sağladığı tespit edilmiştir., In this study, adsorption of phenolic compounds Bisphenol A (BPA) and 4-Nitrophenol (4-NP) by pristine and purified MWCNTs has been studied systematically. The ultimate goal of this study was to reveal the adsorption behaviour of BPA and 4-NP compound on MWCNTs and determine adsorption efficiency of the MWCNTs prepared in our laboratories. MWCNTs are prepared by using chemical vapour deposition (CVD) of acetylene in argon flow on a magnesium oxide powder impregnated with an iron nitrate solution. Pristine MWCNTs were purified by liquid phase oxidation method. Adsorption behaviors of phenolic compounds were studied by varying parameters such as agitation time, pH, temperature, and mass of MWCNTs. It was observed that adsorption was dependent some parameters examined and impurities that MWCNTs contain interfere the adsorption mechanism. Purification of MWCNTs enhanced the adsorption capacity dramatically. The Freundlich, Langmuir and Temkin models were applied to define adsorption equilibrium and it was found that the experimental data fitted very well to Freundlich model for both phenolic compounds., Yüksek Lisans, M.Sc.

BPA je tvar koja se proizvodi u velikim količinama. Godišnja svjetska proizvodnja procjenjuje se na 3-4 milijuna tona. BPA je također prisutan u nekim materijalima koji dolaze u dodir s hranom, jer se koristi u proizvodnji polikarbonata i epoksi-fenolne smole. Polikarbonat (PC) je polimer koji se naširoko koristi u proizvodima poput bočica za hranjenje dojenčadi, priboru za jelo (tanjuri, vrčevi), posudama za mikrovalnu pećnicu, povratnim bocama za vodu i mlijeko te galonima za vodu. PC se također koristi u proizvodnji vodovodnih cijevi. Epoksi-fenolne smole koriste se kao unutarnje zaštitne obloge za izradu limenki te kao premaz metalnih poklopaca za boce i staklenke u kojima se čuva hrana i napitci. Epoksi-fenolne smole se koriste kao površinski premaz za velike spremnike za pitku vodu i vino. BPA se također koristi u proizvodnji poli(vinil- klorida) (PVC). Poznato je da se monomeri mogu izlučiti (migrirati) iz polimera i prijeći u hranu te se naći u ljudskom organizmu i našem okolišu. Mali dio ukupne proizvodnje (ali još uvijek prilično velik iznos od 1500 tona godišnje) koristi se za proizvodnju termopapira. Kako se svi ovi proizvodi mogu reciklirati BPA se vrlo lako može naći u recikliranom papiru u svim oblicima. Osim toga u Europi oko 7000 tona ove sirovine završi i kod malih potrošača, te se sudbina ovog dijela proizvodnje BPA u okolišu ne može predvidjeti. Utjecaj BPA na rizik po ljudsko zdravlje i okoliš sa znanstvenog stanovišta vrlo su različiti. U posljednjih deset godina, intenzivno se raspravlja o ovoj temi. Iako se mnoge regulatorne agencije oslanjaju na rezultate istraživanja provedene u skladu s postojećim regulatornim smjernicama, dio znanstvene zajednice je mišljenja da se smjernice proizišle iz neistraživanih studija, a koje pokazuju učinak pri nižim dozama ili koncentracijama, nebi smjele odbaciti pri procjeni rizika. U skladu s time postoje i različita mišljenja među poznatim i priznatim regulatorinim agencijama u Svijetu.

Prov från svensk yttre miljö har analyserats på en eller flera av ämnesgrupperna fenolära ämnen, ftalater, kvartära ammoniumföreningar och tennorganiska föreningar. Proven omfattar främst vatten och slam från kommunala reningsverk, ytvatten och sediment. Sediment har även analyserats på diuron, irgarol 1051, DCOIT (Sea nine 211) och capsaicin Prov från svensk yttre miljö har analyserats på en eller flera av ämnesgrupperna fenolära ämnen, ftalater, kvartära ammoniumföreningar och tennorganiska föreningar. Proven omfattar främst vatten och slam från kommunala reningsverk, ytvatten och sediment. Sediment har även analyserats på diuron, irgarol 1051, DCOIT (Sea nine 211) och capsaicin

Tesis Univ. Granada. Departamento de Química Inorgánica. Leída el 18 de junio de 2010

Proizvodnja petrokemikalija je dio organske kemijske industrije, koja je specifična po komparativnim mogućnostima proizvodnje pa se iz različitih sirovina može proizvesti isti proizvod ili pak iz iste sirovine nastaju različiti proizvodi, naravno ovisno o uvjetima provedbe procesa (temperatura, tlak, katalizatori). Te su mogućnosti otvorene i u proizvodnji monomera, s posebnim naglaskom na izbor primijenjenoga katalizatora. Broj raspoloživih monomera iz kojih se danas proizvodi veliki broj polimernih materijala mnogo je manji, ali ipak dovoljno obiman za cjelokupno prikazivanje njihove proizvodnje. Stoga će u ovom radu biti prikazani samo katalizatori (i možebitne novosti na tom polju) za sintezu monomera koji su ishodne komponente za proizvodnju široko primjenjivih plastomera (PE, PVC, PP, PS i PET) i još nekih polimera koji se u svijetu najviše proizvode, bilo lančanom ili postupnom polimerizacijom.

Los efectos adversos de los disruptores endocrinos (DE) sobre la salud, crean la necesidad de generar sistemas de detección de xenoestrógenos (DE). En este proyecto desarrollamos un sistema para la detección de uno de estos xenoestrógenos, el Bisfenol A (BPA), a través de la construcción de un biosensor basado en medidas de espectroscopia de impedancia para mejorar la sensibilidad. El biosensor consta de un soporte (electrodo) y una doble capa lipídica a la que le incorporamos una proteína receptor de estrógenos. Esta idea fue inicialmente concebida por V. Granek y J. Rishpon (Detecting Endocrine-Disrupting Compounds by Fast Impedance Measurements, Environ. Sci. Technol. 36 (2002) 1574-1578). Realizamos una evaluación de la bioactividad de BPA con la membrana, a través del análisis de cambios en la impedancia en función de la concentración de BPA. Los resultados encontrados indicaron que el BPA cambia la configuración de la membrana, pero en concentraciones no fisiológicas (>1ppm). Posteriormente, con la incorporación del receptor de estrógeno sobre la membrana lipídica, desarrollamos un biosensor de mayor sensibilidad haciendo posible la detección de BPA en ppb. The adverse effects of endocrine disrup tors on human health have created a need for screening systems to detect xenoestrogens. In this project, we develop a system to detect one of these xenestrogens, Bisphenol A (BPA), through the development of a biosensor based on impedance measurements. The biosensor consists of a supported lipid bilayer that incorporates a protein receptor sensitive to the presence of BPA. This setup was originally proposed by V. Granek and J. Rishpon [19]; we now present an alternative method of analysis to increase sensibility. As a preliminary evaluation of bioactivity of BPA we measured the direct interaction of this xenoestrogen with the membrane by analyzing changes in the membrane impedance as a function of BPA concentration. The results indicate that BPA inserts and disrupts the membrane, but only at very high unphysiological BPA concentrations (> 1 ppm). We then developed a high sensitivity biosensor, based on the detection of the electric signal by means of impedance spectroscopy, resulting from the interaction between BPA and an estrogen receptor reconstituted in a lipid membrane. The results show that the presence of the receptor increases by several orders of magnitude the sensitivity of the system, making it possible to detect BPA at ppb.

Prov från svensk yttre miljö har analyserats på en eller flera av ämnesgrupperna fenolära ämnen,ftalater, kvartära ammoniumföreningar och tennorganiska föreningar. Proven omfattar främst vattenoch slam från kommunala reningsverk, ytvatten och sediment. Sediment har även analyserats på diuron,irgarol 1051, DCOIT (Sea nine 211) och capsaicin.

O bisfenolu A je posljednjih godinu dana napisano toliko napisa u medijima u Hrvatskoj i svijetu, da se čini da o njemu svi sve znaju. No pitanje je koliko je od tih napisa znanstveno utemeljeno, a koliko ih je poslužilo samo za nepotrebno sijanje panike i širenje negativnog imidža plastike u javnosti: Nije ovo niti prvi niti posljednji napad na plastiku, a takvi napisi i krive interpretacije periodički se ponavljaju. Bili smo svjedoci napada na PVC, PET boce, kao i na polietilenske vrećice, pa je tako došao red i na polikarbonatne bočice za hranjenje, osobito dojenčadi.

Oktaklorstyren samt penta- och hexaklorbensen har analyserats i strömming från 17 lokaler längs Norrlands- och Svealandskusten. Oktaklorstyren kunde påvisas i samtliga prov. - Flyktiga metylsiloxaner samt 4-nonylfenol, 4-t-oktylfenol, triclosan och bisfenol A har analyserats i in- och utgående vatten samt slam från Borlänge reningsverk. Transporterade mängder har beräknats. - Flyktiga metylsiloxaner har analyserats i förpackade livsmedel. Låga halter av cykliska siloxaner kunde påvisas i ett av tio prover. - Endosulfan har analyserats i luft- och depositionsprov från bakgrundsstationerna Råö och Pallas. Medelkoncentrationen i luft var högst under sommarhalvåret: 22 pg/m3 i Råö och 11 pg/m3 i Pallas. Deponerade mängder var också högst under sommarhalvåret: 1,0 ng/m2/dygn i Råö och 0,26 ng/m2/dygn i Pallas. - En översikt har gjorts över tidigare analyserade endosulfanhalter i svenska livsmedel. Antalet varor som innehöll halter av endosulfan över detektionsgränsen (0,01-0,04 mg/kg) har minskat under perioden 1995-2005 vilket speglar den minskade användningen i Europa. Efter år 2000 finns inga rapporter om endosulfan i svenskodlade grönsaker. Några gånger per år hittas importerad frukt och grönsaker med endosulfanhalter som vid stor konsumtion bedöms kunna ge barn akuta hälsoeffekter. Beräkningar av kroniskt intag visar att intaget i Sverige ligger på ca 1 % av 'acceptabelt dagligt intag' dvs under risknivån för kroniska hälsoeffekter - Oktaklorstyren samt penta- och hexaklorbensen har analyserats i strömming från 17 lokaler längs Norrlands- och Svealandskusten. Oktaklorstyren kunde påvisas i samtliga prov. - Flyktiga metylsiloxaner samt 4-nonylfenol, 4-t-oktylfenol, triclosan och bisfenol A har analyserats i in- och utgående vatten samt slam från Borlänge reningsverk. Transporterade mängder har beräknats. - Flyktiga metylsiloxaner har analyserats i förpackade livsmedel. Låga halter av cykliska siloxaner kunde påvisas i ett av tio prover. - Endosulfan har analyserats i luft- och depositionsprov från bakgrundsstationerna Råö och Pallas. Medelkoncentrationen i luft var högst under sommarhalvåret: 22 pg/m3 i Råö och 11 pg/m3 i Pallas. Deponerade mängder var också högst under sommarhalvåret: 1,0 ng/m2/dygn i Råö och 0,26 ng/m2/dygn i Pallas. - En översikt har gjorts över tidigare analyserade endosulfanhalter i svenska livsmedel. Antalet varor som innehöll halter av endosulfan över detektionsgränsen (0,01-0,04 mg/kg) har minskat under perioden 1995-2005 vilket speglar den minskade användningen i Europa. Efter år 2000 finns inga rapporter om endosulfan i svenskodlade grönsaker. Några gånger per år hittas importerad frukt och grönsaker med endosulfanhalter som vid stor konsumtion bedöms kunna ge barn akuta hälsoeffekter. Beräkningar av kroniskt intag visar att intaget i Sverige ligger på ca 1 % av 'acceptabelt dagligt intag' dvs under risknivån för kroniska hälsoeffekter

Bisphenol A (BPA) is a high volume chemical with potential to interact with hormone systems in humans and wildlife. Previous studies in both Sweden and elsewhere have demonstrated the presence of BPA in freshwaters as well as in the marine environment, mostly in surface waters and sediments. In order to strengthen the knowledge on the environmental occurrence of BPA in Sweden, a study was undertaken where BPA was analysed in fish from background lakes, urban lakes, coastal sites and the marine environment. In total 23 samples were analysed. Bisphenol A was detected in most samples in the range of

ÖZDOKTORA TEZİBİSFENOL A'nın BİYOLOJİK PARÇALANMASI,BİYOKONSANTRASYON FAKTÖRLERİ ve ÖSTROJENİK AKTİVİTEDÜZEYLERİNİN BELİRLENMESİOsman GÜLNAZÇUKUROVA ÜNİVERSİTESİFEN BİLİMLERİ ENSTİTÜSÜBİYOLOJİ ANABİLİM DALIDanışman: Prof. Dr. Sadık DİNÇERİkinci Danışman: Prof. Dr. E. Sultan GİRAYYıl: 2006 Sayfa:117Jüri: Prof. Dr. Sadık DİNÇERProf. Dr. Mustafa CANLIProf. Dr. E. Sultan GİRAYDoç. Dr. Gökhan CORALYrd. Doç. Dr. Güray KILINÇÇEKERBisfenol A, endokrin yıkıcı bir kimyasaldır. Bu çalışmada Bisfenol A'nın mikrobiyal fizyoloji üzerineetkisi, Chlorella vulgaris ve Aeromonas hydrophyla ile biyodegredasyonu, biyodegredasyondan sonra endokrinyıkıcı özelliğinde meydana gelen değişimler araştırılmıştır.Topraktan izole edilen Gram negatif, çomak BPAd30 suşu API 20NE test kiti ile %86.4 benzerlikleAeromonas hydrophila olarak tanımlanmıştır. Bisfenol A biyodegradasyon çalışmalarında tek karbon kaynağıolarak 60 ve120mgL-1 kullanılmış, Bisfenol A'nın yüzde azalışı 24-120. saatler arasında 60 mgL-1 için %18, 52,61, 89 ve 93 olarak, 120 mgL-1 için %15, 36, 60, 85 ve 91 olarak belirlenmiştir. Maksimum hücre gelişimi 72.saatte gerçekleşmiştir. Son gün protein içeriği kontrol, 60 ve 120 mgL-1 Bisfenol A konsantrasyonunda sırasıyla103, 203 ve 228 mgg-1, karbonhidrat içeriği 65, 121 ve 124 mgg-1 ve lipid içeriği sırasıyla 455, 454 ve 443 mgg-1yaş ağırlık olarak belirlenmiştir. Bakteriyel biyodegradasyon sırasında ortam pH'sı 6.6-6.8 arasındabelirlenmiştir. Bisfenol A'nın algal hücre fizyolojisi, hücre gelişimi, pigment içeriği, protein, karbohidrat ve lipidüzerine etkisi 0.5-80 mgL-1 konsantrasyonlar arasında belirlenmiştir. Bisfenol A'nın 20 mgL-1 üzerindekikonsantrasyonlarında hücre gelişimi baskılanmış ve bu nedenle biyodegradasyon çalışmaları 20 mgL-1konsantrasyonda gerçekleştirilmiştir. Çalışma sırasında maksimum hücre gelişimi 120. saatte belirlenmiştir.Zamana bağlı Bisfenol A azalışı 24-144.saatler arasında %9, 12, 23, 47, 70, 83 ve 99 olarak belirlenmiştir. Songün protein içeriği kontrol ve 20 mgL-1 Bisfenol A konsantrasyonunda sırasıyla 11.7 ve 9.7 mgg-1, karbonhidratiçeriği 11 ve 17 mgg-1 ve lipid içeriği 46 ve 61 mgg-1 yaş ağırlık olarak belirlenmiştir. Biyodegradasyonçalışmalarında ortam pH'sının zamana bağlı olarak 7.5'den 9.2'ye kadar yükseldiği belirlenmiştir. Bisfenol A'nınalgal ve bakteriyel parçalanması first order kinetik modele uygunluk göstermiş ve Bisfenol A'nın yarılanmasüresi, bakteriyel olarak 60 ve 120 mgL-1 konsantrasyonda 27 ve 46, algal olarak 20 mgL-1 konsantrasyonda 57saat olarak belirlenmiştir.Bisfenol A'nın östrojenik aktivite değişimi diklorometan ekstraktı, C18 ve PPL katı faz elüentlerindebelirlenmiştir. Hormonal aktivite 72. ve 120. saatten sonra algal ve bakteriyel çalışmada düşüş göstermiştir. 168.saatte alınan örneklerde hormonal aktivite belirlenmemiştir. C18 katı faz ekstraksiyonunda 60, 20 ve 120 mgL-1konsantrasyonlarda östrojenik aktivite sırasıyla 48, 72 ve 120. saatten sonra düştüğü belirlenmiştir. PPL katı fazekstraksiyonunda 3-72. saatler arasında zayıf hormonal aktivite (1.2-1.5) belirlenmiştir. Çalışmada Bisfenol Aabiyotik olarak parçalanmadığından dolayı hormonal aktivitesinde değişme olmadığı belirlenmiştir. Sonuç olarakBisfenol A'nın östrojenik aktivitesi, Aeromonas hydrophyla ve Chlorella vulgaris ile biyolojik muamelesonucunda azalmaktadır. Bu organizmalar atıksu ve yüzey sularında bol bulunan organizmalardır.Anahtar Kelimeler: Bisfenol A, Östrojenik Aktivite, Biyodegradasyon, Aeromonas hydrophila,Chlorella vulgaris.I ABSTRACTPhD THESISDETERMINATION of BIODEGREDATION, BIOCONCENTRATIONFACTORS and OESTROGENIC ACTIVITY LEVELS of BISPHENOL AOsman GÜLNAZDEPARTMENT OF BIOLOGYINSTITUTE OF NATURAL APPLIED SCIENCESUNIVERSITY OF CUKUROVASupervisor: Prof Dr. Sadık DİNÇERCo Supervisor: Prof. Dr. E. Sultan GİRAYYear: 2006 Page: 117Jury: Prof. Dr. Sadık DİNÇERProf. Dr. Mustafa CANLIProf. Dr. E. Sultan GİRAYAssoc. Prof. Dr. Gökhan CORALAssist. Prof. Dr. Güray KILINÇÇEKERBisphenol A is an endocrine disrupter chemical. In this study effect of Bisphenol A on microbialphysiology, biodegradation of Bisphenol A by Chlorella vulgaris and Aeromonas hydrophyla and changing ofendocrine disrupter properties after biodegradation process were investigated.Soil isolates Gram negative, rod shaped BPAd30 strains were identified with API 20NE as anAeromonas hydrophila (%86.4). Bisphenol A are used sole carbon sources for biodegredation as 60 and 120mgL-1concentrations and percentage decreasing of Bisphenol A in 24-120th hours were determined as 18, 52, 61, 89and 93 for 60 mgL-1, 15, 36, 60, 85 and 91 for 120 mgL-1. Maximum cell growth was determined in 72th hour.At the end of the study, 103, 203 and 228 mgg-1 cellular protein, 65, 121 and 124 mgg-1 cellular carbohydrate and455, 454 and 443 mgg-1 cellular lipid were determined as a wet weight for control, 60 and 120 mgL-1 Bisphenol Aconcentrations, respectively. pH of the medium were determined at about 6.6-6.8 whole biodegradationprocesses. The effect of Bisphenol A onto algal cell physiology such as cell growth, pigment, proteins,carbohydrate and lipid content were determined at various Bisphenol A concentrations (0.5- 80 mgL-1). BisphenolA is suppressed of cell growth at above 20 mgL-1 concentrations for this reason algal biodegradation study wasconducted at 20 mgL-1 Bisphenol A concentrations. Maximum cell growth was determined in 120th hour at 20mgL-1, percentage decreasing of Bisphenol A in 24-144th hours were determined as 9, 12, 23, 47, 70, 83 and 99.At the end of the study, 11.7 and 9.7 mgg-1 cellular protein, 11 and 17 mgg-1 cellular carbohydrate and 46 and 61mgg-1 cellular lipid were determined as a wet weight for control and 20 mgL-1 Bisphenol A concentrations,respectively. pH of the medium was increased from 7.5 to 9.2 in biodegradation processes. Algal and bacterialbiodegradation kinetics are obeyed first order kinetics model and half life of Bisphenol A were determined as a27 ve 46 hours for 60 and 120 mgL-1 at bacterial biodegradation studies and 57 hour for algal study at 20 mgL-1Aconcentration.The chancing of estrogenic activities was determined with dichloromethane extracts, C18 and PPL solidphase cartridge eluents. The estrogenic activity were decreased after 72 and 120th hours for algal and bacterialbiodegradation study at dichloromethane extracts. No estrogenic activity was determined after 168th hours. ForC18 solid phase cartridge eluents, estrogenic activity were decreased after 48, 72 and 120th hours for 60, 20 and120 mgL-1 concentrations. The PPL solid phase cartridge eluents showed the weak estrogenic activity (1.2-1.5) in3-72th hours. This weak estrogenic activity had decreased after 72th hours. Estrogenic activity was not determinedin control samples due to the Bisphenol A is not abiotically degrade. Finally, estrogenic activity of Bisphenol Adoes decreases by Aeromonas hydrophila and Chlorella vulgaris biologic treatment. They are most abundantmicroorganisms of wastewater and surface water.Key Words: Bisphenol A, Estrogenic Activity, Biodegradation, Aeromonas hydrophila, ChlorellavulgarisII 130

Número de solicitud: 200002432, Se describe un método para la síntesis y purificación de los derivados monoclorado, diclorado y triclorado de Bisfenol A. El método consiste en la cloración del Bisfenol A y posterior separación de los compuestos mediante cromatografía. Los patrones se identifican de forma unívoca presentando una pureza superior al 99,99 %. La disponibilidad de estos compuestos es de gran interés para los laboratorios de control y análisis químico, fisioquímico y toxicológico con objeto de poder determinar estos compuestos en muestras de interés ambiental, alimentario, cliínico industrial y legal.

Evidências acumuladas indicam que a saúde dos seres humanos, animais e espécies selvagens pode sofrer conseqüências adversas da exposição a produtos químicos presentes no meio ambiente e que interagem com o sistema endócrino, tais como bifenilas policloradas, dioxinas, estrogênios de ocorrência natural e sintéticos. Por outro lado, permanecem incertezas científicas com respeito aos dados relatados e, também, quanto à hipótese de haver níveis suficientemente elevados de exposição a estes agentes, a ponto de exercer efeito estrogênico generalizado sobre a população. Este trabalho revisa os principais tópicos relacionados a um dos xenoestrogênios que vem sendo mais recentemente estudado: o Bisfenol A (BFA), um monômero de plástico poli-carbonato, com pouca homologia estrutural com o estradiol (E2) mas semelhante ao dietilestilbestrol (DES), hexestriol e componente bisfenólico do tamoxifeno. O presente trabalho comenta e analisa criticamente os efeitos do BFA sobre o trato reprodutivo e função lactotrófica em animais de experimentação, à luz das informações disponíveis e experiência do grupo nesta área, e recomenda algumas necessidades de pesquisa. Some evidences indicate that humans and domestic and wildlife species might suffer adverse consequences from exposure to environmental chemicals that interact with the endocrine system, including polychlorinated biphenyls, dioxins, synthetic and naturally occurring plant estrogens. However, considerable scientific uncertainty remains regarding the causes of these reported effects and whether sufficiently high levels of endocrine-disrupting chemicals exist in the ambient environment to exert adverse effects on the general population. This review summarizes the principal issues related to bisphenol A, an environmental endocrine disrupting chemical with estrogen activity. Bisphenol A is a monomer of plastics and has little structural homology with estradiol, sharing similarity with synthetic estrogens such as diethylstilbestrol and with the bisphenolic component of tamoxifen. In the light of available information and our laboratory experience in this field of research, this work comments and critically analyses the effects of BPA on the reproductive tract and lactotroph function in several rat strains, and also offers some recommendations for additional research.

The present paper aimed to evaluate the impact of microaeration on both the removal performance of some emerging micropollutants (pharmaceuticals, hormones, and bisphenol A) and the microbial community structure of an anaerobic reactor treating synthetic wastewater. Under anaerobic conditions, the removal efficiencies of the micropollutants were very low (< 10%). However, the microaeration (1.0 mL air·min-1 at 27 °C and 1 atm, equivalent to a QAIR/QINF ratio of 0.1) expressively improved the removal efficiencies of all compounds (> 50%). Therefore, supplementing anaerobic reactors with low amounts of oxygen seems to be an interesting strategy to enhance the removal of the micropollutants tested. However, further studies should be carried out with other compounds in order to evaluate the wide applicability of microaeration to different classes of micropollutants in lab- and full-scale treatment systems. Concerning the microbiota structure, both bacterial and archaeal communities were not compromised by the different operational conditions and preserved their functional organization with high richness during the whole experiment. RESUMO O presente trabalho teve como objetivo avaliar o impacto da microaeração tanto no desempenho de remoção de alguns micropoluentes emergentes (fármacos, hormônios e bisfenol A) quanto na estrutura da comunidade microbiana de um reator anaeróbio tratando uma água residuária sintética. Sob condições anaeróbias, as eficiências de remoção dos micropoluentes foram muito baixas (< 10%). Entretanto, a microaeração (1,0 mL de ar·min-1 a 27 °C e 1 atm, equivalente a uma relação QAR/QAF de 0,1) melhorou expressivamente as eficiências de remoção de todos os compostos (> 50%). Portanto, a suplementação de reatores anaeróbios com baixas quantidades de oxigênio parece ser uma estratégia interessante para melhorar a remoção dos micropoluentes testados. Entretanto, mais estudos devem ser realizados com outros compostos para avaliar a ampla aplicabilidade da microaeração a diferentes classes de micropoluentes em sistemas de tratamento em escala laboratorial e real. Com relação à estrutura da microbiota, tanto as comunidades de bactérias quanto as de arqueias não foram comprometidas pelas diferentes condições operacionais e preservaram sua organização funcional com elevada riqueza durante todo o experimento.