The concentration and storage of organic chlorine and chloride were determined in soil, to a depth of 40 cm, in a coniferous forest in the Stubbetorp catchment area in south-east Sweden. Also, the spatial distribution of the two forms of chlorine was determined. Soil samples were collected at 49 of the nodes in a grid with approximately 105 m between the nodes. The analysis of spatial variability suggested that no spatial autocorrelation was present either within the variable organic chlorine or chloride. This means that no sample was more influenced by another nearby sample, as compared to other samples further away. Instead, linear interpolation was used to construct contour maps of the concentrations. The contour maps indicated that the two forms of chlorine have similar spatial patterns and the highest concentrations could be found in the main valley area, with moss soil and forest dominated by pine (Pinus sylvestris (L.)). The two variables showed a significant positive correlation. This could be due to the fact that chloride is the limiting factor for formation in Swedish soil or that the two forms of chlorine are only indirectly related through variables as soil moisture or organic matter. The storage of organic chlorine when a depth of 40 cm was taken into account was seven times the storage compared to an earlier study where only the top-soil was sampled. The storage of organic chlorine in the area is of such size that changes in this storage are likely to have an impact on the transport of chloride. The fact that no spatial autocorrelation could be found in either of the variables suggests that the scale chosen is not suitable for describing spatial autocorrelation on a smaller level, due to processes e.g. microbially induced formation. At the same time the chosen scale is probably too small for detecting spatial autocorrelation on the larger scale due to e.g. deposition and precipitation.

Made available in DSpace on 2014-10-09T12:43:41Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:56Z (GMT). No. of bitstreams: 1 06654.pdf: 9860874 bytes, checksum: a9212efd0462f2603abb2f237d62a703 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Chlorine is an element commonly found in the environment of our planet, in the atmosphere, the earth crust and the oceans. Chlorine occurs in two forms, inorganic chloride (Clin) and organically bound chlorine (Clorg), also called organochlorine. For a long time, the organic halogens (among them the organic chlorine) had been considered as produced only by human activities. However, the research of the recent decades suggests a considerably amount of naturally produced organic chlorine in soil and water. Through the research, a hypothesis have emerged, suggesting that there occur a formation of organic chlorine in the top soil layer where chloride is consuming, while the organic chlorine is degrading on deeper soil levels, causing a release of chloride. The study in this thesis attempts to explore the transportation of organic chlorine through soil. 49 soil water samples were collected at three transects, S04, S12 and S22, nearby a stream in northern Sweden and analysed for Clorg, using an AOX-analyser. The results suggest a decrease in concentrations of Clorg by soil depth for transects S04 and S12. The study also indicates that concentrations of Clorg are decreasing with increasing distance from the stream, where the highest mean concentration was found in the organic matter-rich riparian transect S04. Further conclusions are that the spring flood and changes in groundwater level may influence the concentrations of Clorg. / Ämnet klor är vanligt förekommande på vår planet och finns både i atmosfären, jordskorpan och världens oceaner. Klor uppträder i två olika former: oorganisk klorid (Clin) och organiskt bundet klor (Clorg). De organiska halogenerna (bland vilka organiskt klor ingår) har under lång tid ansetts härstamma från enbart antropogena källor. De senaste decenniernas forskning har dock tytt på en naturlig produktion av organiskt klor i mark och vatten. Genom denna forskning har en hypotes tagit form som föreslår en bildning av organiskt klor i de övre marklagren, där klorid binds, medan det i djupare marklager sker en nedbrytning av det organiska kloret vilket medför ett frigörande av klorid. Denna studie syftar till att studera transporten av organiskt klor genom mark. 49 stycken markvattenprover insamlades vid tre provpunkter (S04, S12 och S22) på ett avrinningsområde i norra Sverige och analyserades med hjälp av ett AOX-instrument. Resultaten tyder på en minskning av Clorg med ökande markdjup för provpunkterna S04 och S12. Studien visar även en minskning i koncentration av organiskt klor med ökande avstånd till vattendraget, där den högsta medelkoncentrationen återfanns i provpunkten S04 som ligger nära bäcken och är rik på organiskt material. Vidare slutsater är att vattenflödena under vårflod samt variasionen i grundvattennivå har en påverkan på koncentrationerna av Clorg.

De senaste decenniernas forskning har påvisat att en omfattande bildning och nedbrytning av klororganiska föreningar sker i mark. Bildning av sådana föreningar sker genom att klorid binds in i organiskt material. Denna naturliga bildning har rönt uppmärksamhet dels för att många klorerade ämnen är giftiga och dels för man tidigare trott att alla klororganiska ämnen uteslutande kommer från mänsklig verksamhet. Huvudmålet för föreliggande avhandling var att (i) uppskatta transporten av klorerade föreningar i nederbörd och avrinningsvatten, (ii) diskutera de klorerade föreningarnas ursprung med utgångspunkt från hur deras förekomst varierar i avrinningsvatten, (iii) undersöka hur transporten av klorid (salt) påverkas av olika faktorer och (iv) studera hur frisättningen av flyktiga klorerade föreningar från mark påverkas av kväve. Avhandlingen bygger på en klorbudget som konstruerats utifrån fältstudier som genomförts i ett litet skogsbeklätt avrinningsområde i sydöstra Sverige. Dessutom har laboratoriestudier genomförts med jord som inhämtats från samma område. Resultaten visar att lagret av klor i marken är betydligt större än flödena och att det främst består av organiska ämnen medan flödet domineras av klorid (salt). Detta tyder på att en stor del av kloriden deltar i en biogeokemisk cykel vilket strider mot gängse uppfattning att klorid rör sig opåverkat genom mark. Hypotesen är att de översta marklagren fungerar som en sänka för klorid genom att omvandlas till organiskt bundet klor. De djupare jordlagren fungerar däremot som en kloridkälla genom att det klorerade organiska materialet transporterats med regnvatten från de ytligare till de djupare liggande lagren för att så småningom brytas ner, varvid klorid frisätts. Ovan beskrivna hypotes stöds av laboratoriestudierna där man kunnat notera att det sker såväl en fastläggning som en frisättning av klorid i mark. Resultaten från avhandlingen tillsammans med resultat från tidigare studier tyder på att en stor del av den klorid som finns i avrinningsvatten kommer från förmultnande organiskt material och att klorid med andra ord inte följer regnvattnets väg genom marken, vilket man tidigare trott. Studierna tyder alltså på att klorid till viss del ”gör en omväg” med en tidsfördröjning på troligen åtskilliga upp till hundratals år. Vidare tyder studierna på att flyktiga klorerade föreningar som kloroform och tetraklormetan bildas i mark och att tillsats av kväve orsakar en minskning av kloroform och en ökning av tetraklormetan. Avhandlingen visar tydligt att det är nödvändigt att rikta uppmärksamhet mot klors biogeokemi i mark och då inte minst mot de processer som påverkar transporten av klor från de övre marklagren till grundvatten och ytvatten om vi ska öka förståelsen av hur klorerade ämnen som tillförts naturen genom mänskliga aktiviteter beter sig. / It is generally known that chlorine compounds are ubiquitous in the environment. In recent years, researchers have concluded that chlorine is part of a biogeochemical cycle in soil involving an interaction between chloride (Clin) and organic-matter-bound chlorine (Clorg). Even though there is indisputable evidence that Clorg is formed naturally, there are actually few simultaneous field measurements of Clorg and Clin. Previously stipulated conclusions with respect to underlying processes and transport estimates have thus been deduced from rather few concentration measurements. It is well known that the chemical composition in soil and runoff water varies widely over time and in space. The main objective of the thesis is to investigate the on-site variation of Clin, Clorg and VOCls in runoff water in order to (i) construct a chlorine budget on a catchment scale to visualize the relative contribution of Clin, Clorg, and VOCls; (ii) more reliably estimate how and why the concentrations of Clin, Clorg, and VOCls in runoff water vary; and (iii) analyze the influence of various environmental variables on the transport. The present thesis highlights the on-site variation and fluxes of Clin, Clorg, and VOCls in a small forested catchment in southeast Sweden. Field flux data collected during a twoyear period and a constructed overall chlorine budget were evaluated. The results show that the storage is dominated by Clorg whereas the transport is dominated by Clin and that the storage is far much larger than the transport. Still, input and output is nearly in balance for all investigated chlorine species. It is interesting to note that these observations resemble observations made for carbon, nitrogen and sulphur; i.e. a large storage, small transport, complex biogeochemical cycling processes at hand but still close to steady state conditions with respect to output-input balances. It appears as if topsoil acts as a sink for Clin, while deeper soil acts as a source of Clin. In addition, the results of the thesis suggest that on-site variation depend on seasonal variations. These variations are to some extent caused by water discharge, but also by water residence time, internal chlorination/dechlorination of organic matter, and different soil water origins. Furthermore, both a net retention and a net release of Clin were observed in laboratory studies. The study indicates that simultaneous retention and release of Clin takes place in soil, which probably has an impact on the Clin import and export fluxes. Finally, the results show for the first time that tetrachloromethane can be emitted from laboratory incubated soil, and that soil nitrogen concentrations has quite different effects on the emission rates of chloroform and tetrachloromethane. The results of the thesis, considered together with results of previous research, suggest that the turnover of chlorine in soils is extensive and potentially important for chlorine cycling in general, which must be taken into account if one wishes to increase the understanding of the cycling of anthropogenic chlorine compounds in the environment. / <p>On the day of the public defence the status of article IV was: Accepted.</p>

Made available in DSpace on 2014-06-11T19:26:10Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-06-09Bitstream added on 2014-06-13T19:54:11Z : No. of bitstreams: 1 sorianojunior_r_me_rcla.pdf: 1949675 bytes, checksum: a6d5cc4f07790ee2fa65e002e7a11372 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A contaminação de solos e água subterrânea por hidrocarbonetos derivados de petróleo tende a liberar vapores que migram da subsuperfície para o ar, expondo, principalmente o ser humano à inalação de compostos que podem oferecer risco a sua saúde. Porém a volatilização destes compostos pode indicar as possíveis fontes de contaminação em subsuperfície. As agências de proteção ambiental, como a EPA (Environmental Protection Agency), nos Estados Unidos, e os órgãos ambientais no Brasil, como a CETESB - Companhia de Tecnologia de Saneamento Ambiental, tem recomendado a avaliação dos Compostos Orgânicos Voláteis – VOC, por meio da técnica denominada Soil Gas Survey. Esta técnica vem sendo largamente utilizada por empresas de consultoria ambiental. Consiste na verificação de concentrações anômalas de VOC no solo in-situ, por meio de analisadores portáteis como FID, PID e Oxidação Catalítica, balizando os trabalhos de investigação e direcionando a quantidade de sondagens e poços de monitoramento para coletas de amostras de solo e água subterrânea para análises químicas. Desta forma o presente trabalho avaliou a presença de possíveis vapores em uma antiga área industrial abandonada contaminada por BTEX e Organoclorados. Esta avaliação foi feita por meio da técnica Soil Gas Survey com a utilização do analisador portátil de Oxidação Catalítica e simulou a volatilização dos contaminantes presentes na água subterrânea por meio do modelo matemático RBCA – Risk- Based Corrective Action Tool Kit Version 2. Os baixos resultados da modelagem da volatilização dos compostos confirmaram os resultados nulos na campanha de avaliação dos VOC no solo pela técnica Soil Gas Survey. Estes resultados sugerem à não capacidade destes compostos chegarem até a superfície. / The contamination of soils and underground water by hydrocarbonates of petroleum derivatives tend to release vapors that migrate from the subsurface to the air, exposing, mainly the human being to the inhalation of compounds that can offer risk to their health. However this volatilization of this compounds can indicate possible sources of contamination in the subsurface. The agencies of environmental protection, like the EPA (Environmental Protection Agency), in the United States, and the environmental organizations in Brazil, like CETESB – Company of Technology of Environmental Sanitation, has recommended the evaluation of Volatile Organic Compounds – VOC, through the technique called Soil Gas Survey. This technique has been largely used by companies of environmental consulting. It consists on the verification of VOC anomalous concentration in the soil in-situ, by portable analyzers like FID, PID and Catalytic Oxidation, beaconing the investigation work directing the quantity of polls and monitoring wells to the collection of samples of soil and underground water to chemical analyses. This way the present work evaluated the presence of possible vapors in an old abandoned industrial area contaminated by BTEX and organochlorines. This evaluation was made through the Soil Gas Survey technique with the use of the portable analyzer of Catalytic Oxidation and simulated the volatilization of the contaminants presented in the underground water through the mathematical model RBCA – Risk- Based Corrective Action Tool Kit Version 2. The low results of the simulation of the compounds volatilization confirmed the null results in the evaluation campaign of the VOC in the soil through the technique Soil Gas Survey. This results suggest the non capacity of this compound reaching the surface

Orientador: José Eduardo Zaine / Banca: Scandar Gasperazzo Ignatius / Banca: Fábio Augusto Gomes Vieira Reis / Resumo: A contaminação de solos e água subterrânea por hidrocarbonetos derivados de petróleo tende a liberar vapores que migram da subsuperfície para o ar, expondo, principalmente o ser humano à inalação de compostos que podem oferecer risco a sua saúde. Porém a volatilização destes compostos pode indicar as possíveis fontes de contaminação em subsuperfície. As agências de proteção ambiental, como a EPA (Environmental Protection Agency), nos Estados Unidos, e os órgãos ambientais no Brasil, como a CETESB - Companhia de Tecnologia de Saneamento Ambiental, tem recomendado a avaliação dos Compostos Orgânicos Voláteis - VOC, por meio da técnica denominada Soil Gas Survey. Esta técnica vem sendo largamente utilizada por empresas de consultoria ambiental. Consiste na verificação de concentrações anômalas de VOC no solo in-situ, por meio de analisadores portáteis como FID, PID e Oxidação Catalítica, balizando os trabalhos de investigação e direcionando a quantidade de sondagens e poços de monitoramento para coletas de amostras de solo e água subterrânea para análises químicas. Desta forma o presente trabalho avaliou a presença de possíveis vapores em uma antiga área industrial abandonada contaminada por BTEX e Organoclorados. Esta avaliação foi feita por meio da técnica Soil Gas Survey com a utilização do analisador portátil de Oxidação Catalítica e simulou a volatilização dos contaminantes presentes na água subterrânea por meio do modelo matemático RBCA - Risk- Based Corrective Action Tool Kit Version 2. Os baixos resultados da modelagem da volatilização dos compostos confirmaram os resultados nulos na campanha de avaliação dos VOC no solo pela técnica Soil Gas Survey. Estes resultados sugerem à não capacidade destes compostos chegarem até a superfície. / Abstract: The contamination of soils and underground water by hydrocarbonates of petroleum derivatives tend to release vapors that migrate from the subsurface to the air, exposing, mainly the human being to the inhalation of compounds that can offer risk to their health. However this volatilization of this compounds can indicate possible sources of contamination in the subsurface. The agencies of environmental protection, like the EPA (Environmental Protection Agency), in the United States, and the environmental organizations in Brazil, like CETESB - Company of Technology of Environmental Sanitation, has recommended the evaluation of Volatile Organic Compounds - VOC, through the technique called Soil Gas Survey. This technique has been largely used by companies of environmental consulting. It consists on the verification of VOC anomalous concentration in the soil in-situ, by portable analyzers like FID, PID and Catalytic Oxidation, beaconing the investigation work directing the quantity of polls and monitoring wells to the collection of samples of soil and underground water to chemical analyses. This way the present work evaluated the presence of possible vapors in an old abandoned industrial area contaminated by BTEX and organochlorines. This evaluation was made through the Soil Gas Survey technique with the use of the portable analyzer of Catalytic Oxidation and simulated the volatilization of the contaminants presented in the underground water through the mathematical model RBCA - Risk- Based Corrective Action Tool Kit Version 2. The low results of the simulation of the compounds volatilization confirmed the null results in the evaluation campaign of the VOC in the soil through the technique Soil Gas Survey. This results suggest the non capacity of this compound reaching the surface / Mestre

Submitted by Aline Batista (alinehb.ufpel@gmail.com) on 2018-05-16T14:30:50Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertacao_Fernanda_Demoliner.pdf: 883689 bytes, checksum: 17b2361f24d2dcbcf6fa64f2b8eb26cc (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2018-05-16T20:23:53Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertacao_Fernanda_Demoliner.pdf: 883689 bytes, checksum: 17b2361f24d2dcbcf6fa64f2b8eb26cc (MD5) / Approved for entry into archive by Aline Batista (alinehb.ufpel@gmail.com) on 2018-05-16T20:24:07Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertacao_Fernanda_Demoliner.pdf: 883689 bytes, checksum: 17b2361f24d2dcbcf6fa64f2b8eb26cc (MD5) / Made available in DSpace on 2018-05-16T20:24:07Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertacao_Fernanda_Demoliner.pdf: 883689 bytes, checksum: 17b2361f24d2dcbcf6fa64f2b8eb26cc (MD5) Previous issue date: 2015-03-20 / Sem bolsa / A adesão e formação de biofilmes de micro-organismos a superfícies de equipamentos e utensílios no processamento de alimentos resulta em grave problema para a indústria, pois atua como fonte de contaminação do alimento, por serem mais resistentes a ação de sanitizantes e antimicrobianos. O objetivo deste trabalho foi avaliar a capacidade de Pseudomonas spp. e Listeria spp., provenientes de cortes de carnes de frango e de búfalo de frigoríficos e do comércio varejista da região sul do Rio Grande do Sul, de formar biofilmes em superfície de placas de poliestireno e aço inoxidável, bem como verificar a resistência destes a sanificantes e a antimicrobianos. Foram utilizados 69 isolados bacterianos provenientes de cortes de carnes de frango e de búfalo, sendo 19 de espécies de Listeria e 50 de Pseudomonas spp. Os isolados foram avaliados quanto à formação de biofilme em microplacas de poliestireno e em corpos de prova de aço inoxidável. Os isolados formadores de biofilme em aço inoxidável foram testados quanto à ação de sanitizantes: cloro orgânico e quaternário de amônio (200 ppm) e submetidos ao teste de resistência antimicrobiana. A formação biofilme em microplacas de poliestireno foi de 73,7 % para isolados de Listeria spp. e de 32 % para isolados de Pseudomonas spp. Todos os isolados de Listeria spp. e 72% dos isolados de Pseudomonas spp. formaram biofilmes em corpos de prova de aço inoxidável. O quaternário de amônio foi mais eficaz que o cloro orgânico na redução de biofilme de Listeria spp. e Pseudomonas spp. Os isolados pertencentes ao gênero Listeria apresentaram maior resistência à penicilina (94,7 %), à clindamicina (84,2 %), à oxacilina (73,7 %) e à cefepime (57,9 %), sendo que 94,7 % foram resistentes a dois ou mais antimicrobianos. Meropenem foi o antimicrobano menos efetivo para Pseudomonas spp. Também foram encontrados 84% dos isolados de Pseudomonas spp. multirresistentes a antimicrobianos. Conclui-se que os isolados provenientes de cortes de carnes de frango e de bubalino foram formadores de biofilme em poliestireno e aço inoxidável e apresentaram resistência a antimicrobianos, o que confere riscos a saúde do consumidor. / The adhesion and microorganisms biofilm formation on surfaces of equipment and utensilsin food processingresults inserious problem for the industry because it actsas a source of contamination are less resistant to sanitizers and antimicrobial action. The objective of this study was to evaluate the ability of Pseudomonas spp. and Listeria spp. present in chicken and buffalo meat, to form biofilms on the surface of polystyrene plates and stainless steel as well as verify their resistance to sanitizers and antimicrobials. Sixty nine bacterial isolates were used, 19 species of Listeria and 50 species of Pseudomonas spp. The isolates were evaluated to their biofilm formation capacity in polystyrene microplates and stainless steel. Isolated stainless steel biofilm formers were tested for sanitizing action of organic chlorine and quaternary ammonium (200 ppm) and submitted antimicrobial resistance testing. The ability to form biofilmon polystyrene microplates was 73,7 % in isolates of Listeria spp. and 32 % for Pseudomonas spp. All isolates of Listeria spp. and 72 % of Pseudomonas spp. showed the ability to form biofilm on stainless steel specimens. The sanitizing organic chlorine and quaternary ammonium were effective to reduce Listeria spp. and Pseudomonas spp. biofilm formation in stainless steel. Quaternary ammonium was more effective than organic chlorine to reduce Listeria spp. biofilm formation from buffalo meat. Isolates belonging to the Listeria generous showed greater resistance to penicillin (94.7 %), clindamycin (84.2 %), oxacillin (73.7 %) and cefepime (57.9 %), and 94.7 % were resistant to two or more antimicrobial. Meropenem was the less effective antimicroban of or Pseudomonas spp. It was also found that 84 % of isolates of Pseudomonas spp. were multirresistentes to antimicrobianos. The isolates from chicken meat cuts and buffalo were biofilm-forming polystyrene and stainless steel and were resistant to antimicrobials, which gives risk to consumer health.

No / Novel 1- and 1,4-substituted chloroethylaminoanthraquinones with DNA binding and alkylating properties along with their respective hydroxyethylaminoanthraquinone intermediates were synthesized. Selected chloroethylaminoanthraquinones were shown to cross-link DNA and alkylate guanines (at low nM concentration) with a preference for reaction sites containing 5'-PyG. A compound (Alchemix) with the bis-chloroethyl functionality confined to one side chain alkylated but did not cross-link DNA. All the 1,4-disubstituted chloroethylaminoanthraquinones were potently cytotoxic (nM IC50s) against cisplatin-resistant ovarian cancer cell lines.