Organohalogen contaminants in wildlife from the Yangtze River Delta : Development of methods and assessments of legacy and emerging persistent organic pollutants

Rapid economic development has occurred during the past few decades in China with the Yangtze River Delta (YRD) area as one of the most progressive areas. The urbanization, industrialization, agricultural and aquaculture activities result in extensive production and application of chemicals. Organohalogen contaminants (OHCs) have been widely used as i.e. pesticides, flame retardants and plasticizers. They are persistent, bioaccumulative and pose a potential threat to ecosystem and human health. However, limited research has been conducted in the YRD with respect to chemicals environmental exposure. The main objective of this thesis is to investigate the contamination level, distribution pattern and sources of OHCs in the YRD. Wildlife from different habitats are used to indicate the environmental pollution situation, and evaluate selected matrices for use in long term biomonitoring to determine the environmental stress the contamination may cause. In addition, a method is developed for dicofol analysis. Moreover, a specific effort is made to introduce statistic power analysis to assist in optimal sampling design. The thesis results show extensive contamination of OHCs in wildlife in the YRD. The occurrences of high concentrations of chlorinated paraffins (CPs) are reported in wildlife, in particular in terrestrial species, (i.e. short-tailed mamushi snake and peregrine falcon). Impurities and byproducts of pentachlorophenol products, i.e. polychlorinated diphenyl ethers (PCDEs) and hydroxylated polychlorinated diphenyl ethers (OH-PCDEs) are identified and reported for the first time in eggs from black-crowned night heron and whiskered tern. High concentrations of octachlorodibenzo-p-dioxin (OCDD) are determined in these samples. The toxic equivalents (TEQs) of polychlorinated dibenzo-p-dioxin (PCDDs) and polychlorinated dibenzofurans (PCDFs) are at mean levels of 300 and 520 pg TEQ g-1lw (WHO2005 TEQ) in eggs from the two bird species, respectively. This is two orders of magnitude higher than European Union (EU) regulation limit in chicken eggs. Also, a novel pattern of polychlorinated biphenyls (PCBs) with octa- to decaCBs, contributing to as much as 20% of total PCBs therein, are reported in birds. The legacy POPs shows a common characteristic with relatively high level of organochlorine pesticides (i.e. DDT, hexacyclohexanes (HCHs) and Mirex), indicating historic applications. In contrast, rather low concentrations are shown of industrial chemicals such as PCBs and polybrominated diphenyl ethers (PBDEs). A refined and improved analytical method is developed to separate dicofol from its major decomposition compound, 4,4’-dichlorobenzophenone. Hence dicofol is possible to assess as such. Statistic power analysis demonstrates that sampling of sedentary species should be consistently spread over a larger area to monitor temporal trends of contaminants in a robust manner. The results presented in this thesis show high CPs and OCDD concentrations in wildlife. The levels and patterns of OHCs in YRD differ from other well studied areas of the world. This is likely due to the extensive production and use of chemicals in the YRD. The results strongly signal the need of research biomonitoring programs that meet the current situation of the YRD. Such programs will contribute to the management of chemicals and environment in YRD, with the potential to grow into the human health sector, and to expand to China as a whole.

Transnational environmental policy:reconstructing ozone

Transnational Environmental Policy analyses a surprising success story in the field of international environmental policy making: the threat to the ozone layer posed by industrial chemicals, and how it has been averted. The book also raises the more general question about the problem-solving capacities of industrialised countries and the world society as a whole. Reiner Grundmann investigates the regulations which have been put in place at an international level, and how the process evolved over twenty years in the US and Germany.

BPA occupational exposure assessment in Europe: a scientific gap

Bisphenol A (BPA), 2,2-bis(4-hydroxyphenyl) propane one is of the greatest volume industrial chemicals utilized in the world with increased production every year. Environmental exposure to this xenoestrogen is considered a generalized phenomenon with a Tolerable Daily Intake (TDI) of4 µg/kg body weight/day established by the European Food Safety Authority. Several studies have focused in estimate human daily intake and potential associated health effects of environmental exposures, however despite of the massive BPA production and consumption in European countries, with policarbonate and epoxy resins as the major applications, occupational exposure to BPA have been overlooked and considered safe by the European authorities.

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

Potentially toxic and hazardous substances in the industrial organic chemicals and organic dyes and pigments industries /

Mode of access: Internet.

Demilitarization procedures for FSC 4230, decontaminating and impregnating equipment; FSC 4410, industrial boilers; FSC 6810, chemicals; FSC 6850, miscellaneous.

"September 1976."

Avaliação das melhores técnicas disponíveis relativas à refrigeração industrial e às emissões resultantes da armazenagem

Esta dissertação foi realizada em colaboração com o grupo empresarial Monteiro, Ribas e teve como principais objetivos efetuar uma avaliação das melhores técnicas disponíveis relativas à refrigeração industrial e às emissões resultantes da armazenagem. O primeiro objetivo teve como alvo todas as instalações da Monteiro, Ribas enquanto que o segundo objetivo se debruçou sobre Monteiro, Ribas, Embalagens Flexíveis, S.A.. Para cumprir estes objetivos, inicialmente efetuou-se um levantamento das melhores técnicas disponíveis apresentadas nos respetivos documentos de referência. Em seguida selecionaram-se as técnicas que se adequavam às condições e às instalações em estudo e procedeu-se a uma avaliação de forma a verificar o grau de implementação das medidas sugeridas no BREF (Best Available Techniques Reference Document). Relativamente aos sistemas de refrigeração industrial verificou-se que estão implementadas quase todas as medidas referenciadas no respetivo documento de referência. Isto prende-se com o facto dos sistemas de refrigeração existentes no complexo industrial Monteiro, Ribas serem relativamente recentes. Foram implementados no ano de 2012, e são caracterizados por apresentarem uma conceção moderna com elevada eficiência. No que diz respeito à armazenagem de produtos químicos perigosos, a instalação em estudo, apresenta algumas inconformidades, uma vez que a maioria das técnicas mencionadas no BREF não se encontram implementadas, pelo que foi necessário efetuar uma avaliação de riscos ambientais, com recurso à metodologia proposta pela Norma Espanhola UNE 150008:2008 – Análise e Avaliação do Risco Ambiental. Para isso procedeu-se então à formulação de vários cenários de riscos e à quantificação de riscos para à Monteiro, Ribas Embalagens Flexíveis S.A., tendo-se apurado que os riscos estavam avaliados como moderados a altos. Por fim foram sugeridas algumas medidas de prevenção e de minimização do risco que a instalação deve aplicar, como por exemplo, o parque de resíduos perigosos deve ser equipado com kits de contenção de derrames (material absorvente), procedimentos a realizar em caso de emergência, fichas de dados de segurança e o extintor deve ser colocado num local de fácil visualização. No transporte de resíduos perigosos, para o respetivo parque, é aconselhável utilizar bacias de contenção de derrames portáteis e kits de contenção de derrames. Relativamente ao armazém de produtos químicos perigosos é recomendado que se proceda a sua reformulação tendo em conta as MTD apresentadas no subcapítulo 5.2.3 desta dissertação.

Plasma Elaidic Acid Level as Biomarker of Industrial Trans Fatty Acids and Risk of Weight Change: Report from the EPIC Study.

BACKGROUND Few epidemiological studies have examined the association between dietary trans fatty acids and weight gain, and the evidence remains inconsistent. The main objective of the study was to investigate the prospective association between biomarker of industrial trans fatty acids and change in weight within the large study European Prospective Investigation into Cancer and Nutrition (EPIC) cohort. METHODS Baseline plasma fatty acid concentrations were determined in a representative EPIC sample from the 23 participating EPIC centers. A total of 1,945 individuals were followed for a median of 4.9 years to monitor weight change. The association between elaidic acid level and percent change of weight was investigated using a multinomial logistic regression model, adjusted by length of follow-up, age, energy, alcohol, smoking status, physical activity, and region. RESULTS In women, doubling elaidic acid was associated with a decreased risk of weight loss (odds ratio (OR) = 0.69, 95% confidence interval (CI) = 0.55-0.88, p = 0.002) and a trend was observed with an increased risk of weight gain during the 5-year follow-up (OR = 1.23, 95% CI = 0.97-1.56, p = 0.082) (p-trend<.0001). In men, a trend was observed for doubling elaidic acid level and risk of weight loss (OR = 0.82, 95% CI = 0.66-1.01, p = 0.062) while no significant association was found with risk of weight gain during the 5-year follow-up (OR = 1.08, 95% CI = 0.88-1.33, p = 0.454). No association was found for saturated and cis-monounsaturated fatty acids. CONCLUSIONS These data suggest that a high intake of industrial trans fatty acids may decrease the risk of weight loss, particularly in women. Prevention of obesity should consider limiting the consumption of highly processed foods, the main source of industrially-produced trans fatty acids.

A database to aid the identification of chemicals potentially posing a health risk through percutaneous exposure

In the context of recent attempts to redefine the 'skin notation' concept, a position paper summarizing an international workshop on the topic stated that the skin notation should be a hazard indicator related to the degree of toxicity and the potential for transdermal exposure of a chemical. Within the framework of developing a web-based tool integrating this concept, we constructed a database of 7101 agents for which a percutaneous permeation constant can be estimated (using molecular weight and octanol-water partition constant), and for which at least one of the following toxicity indices could be retrieved: Inhalation occupational exposure limit (n=644), Oral lethal dose 50 (LD50, n=6708), cutaneous LD50 (n=1801), Oral no observed adverse effect level (NOAEL, n=1600), and cutaneous NOAEL (n=187). Data sources included the Registry of toxic effects of chemical substances (RTECS, MDL information systems, Inc.), PHYSPROP (Syracuse Research Corp.) and safety cards from the International Programme on Chemical Safety (IPCS). A hazard index, which corresponds to the product of exposure duration and skin surface exposed that would yield an internal dose equal to a toxic reference dose was calculated. This presentation provides a descriptive summary of the database, correlations between toxicity indices, and an example of how the web tool will help industrial hygienist decide on the possibility of a dermal risk using the hazard index.

Óleo da castanha de caju: oportunidades e desafios no contexto do desenvolvimento e sustentabilidade industrial

The new millennium is marked by a growing search for renewable fuels and alternative raw materials from biomass in the petrochemicals industry. However, there are many challenges to overcome regarding technological and human resources aspects. In this scenario, cashew nut oil, which is rich in natural phenols, is considered to be very promising for the development of synthetic and functional products and as a feedstock for production of fine chemicals and a wide variety of new materials.

Do engenho à biorrefinaria: a usina de açúcar como empreendimento industrial para a geração de produtos bioquímicos e biocombustíveis

A sugar cane mill is at the present moment a modest biorefinery producing few products such as sugar, ethanol and polyhydroxybutyrate (PHB). In the near future, this mill can expand its production using several renewable feedstock's to produce biofuels and high value biobased chemicals. However, the choice of appropriate products for addition to the portfolio is challenged by a lack of broad-based conversion technology coupled with a plethora of potential targets. The intent of this revision was to catalyze research efforts to expand the list of products and to present an updated evaluation of potential target structures for chemical production.

Inovação & propriedade industrial & indústria química

ABSTRACT The main aim of this paper was to contribute to reflections in Brazil on the need to transfer knowledge held at universities and R&D institutions over to companies, i.e. to transfer scientific knowledge of chemistry to technology. It discusses how the competitiveness of countries is increasingly dependent on their technological capacity. The chemicals industry is a fundamental driver of social, environmental, economic and industrial indicators of sustainable development. In Brazil, the chemicals industry's deficit has grown over the last three decades. Patents are important sources of information because patent documents contain 75% of all technological information available. The National Institute of Industrial Property in Brazil has created a Technology Observatory with the purpose of identifying and analyzing technological information contained in patent documents within the ambit of partnerships with government entities or business associations, in order to support their technology-related decision-making processes. The paper gives examples of ethanol and biotechnology patent documents, including pharmaceuticals, of which there are very few in Brazil. However, a few of the patent applications identified are filed in Brazil, giving the country the opportunity to transform this scientific knowledge into technology by means of partnership agreements with companies. Finally, the paper presents information on the patent applications filed by the world's leading chemicals companies as measured by their revenues, and the respective numbers of patent applications in the last five years in organic chemistry and polymers, sectors in which Brazil is currently dependent on imports for over 50% of its needs. The patent assignees in these sectors in Brazil are also identified, and the paper concludes that Brazil needs to invest in the development of professionals, providing clearly-defined career paths in technology innovation teams at R&D institutions, and to foster more initiatives such as the creation of a new research and innovation entity, EMBRAPII, since investing in science and technology is a prerequisite for knowledge production, industrial property, economic development and, consequently, the competitiveness of the country.

Electrocoagulation in the treatment of industrial waters and wastewaters

Chemical coagulation is commonly used in raw water and wastewater treatment plants for the destabilisation of pollutants so that they can be removed in the subsequent separation processes. The most commonly used coagulation chemicals are aluminium and iron metal salts. Electrocoagulation technology has also been proposed for the treatment of raw waters and wastewaters. With this technology, metal cations are produced on the electrodes via electrolysis and these cations form various hydroxides in the water depending on the water pH. In addition to this main reaction, several side reactions, such as hydrogen bubble formation and the reduction of metals on cathodes, also take place in the cell. In this research, the applications of electrocoagulation were investigated in raw water treatment and wastewater applications. The surface water used in this research contained high concentrations of natural organic matter (NOM). The effect of the main parameters – current density, initial pH, electric charge per volume, temperature and electrolysis cell construction – on NOM removal were investigated. In the wastewater treatment studies, the removal of malodorous sulphides and toxic compounds from the wastewaters and debarking effluents were studied. Also, the main parameters of the treatment, such as initial pH and current density, were investigated. Aluminium electrodes were selected for the raw water treatment, whereas wastewaters and debarking effluent were treated with iron electrodes. According to results of this study, aluminium is more suitable electrode material for electrocoagulation applications because it produces Al(III) species. Metal ions and hydroxides produced by iron electrodes are less effective in the destabilisation of pollutants because iron electrodes produce more soluble and less charged Fe(II) species. However, Fe(II) can be effective in some special applications, such as sulphide removal. The resulting metal concentration is the main parameter affecting destabilisation of pollutants. Current density, treatment time, temperature and electrolysis cell construction affect the dissolution of electrodes and hence also the removal of pollutants. However, it seems that these parameters have minimal significance in the destabilization of the pollutants besides this effect (in the studied range of parameters). Initial pH and final pH have an effect on the dissolution of electrodes, but they also define what aluminium or iron species are formed in the solution and have an effect on the ζ-potential of all charged species in the solution. According to the results of this study, destabilisation mechanisms of pollutants by electrocoagulation and chemical coagulation are similar. Optimum DOC removal and low residual aluminium can be obtained simultaneously with electrocoagulation, which may be a significant benefit of electrocoagulation in surface water treatment compared to chemical coagulation. Surface water treatment with electrocoagulation can produce high quality water, which could be used as potable water or fresh water for industrial applications. In wastewater treatment applications, electrocoagulation can be used to precipitate malodorous sulphides to prevent their release into air. Technology seems to be able to remove some toxic pollutants from wastewater and could be used as pretreatment prior to treatment at a biological wastewater treatment plant. However, a thorough economic and ecological comparison of chemical coagulation and electrocoagulation is recommended, because these methods seem to be similar in pollutant destabilisation mechanisms, metal consumption and removal efficiency in most applications.

Novel technology for preparation of optically active chemicals

Asymmetric synthesis using modified heterogeneous catalysts has gained lots of interest in the production of optically pure chemicals, such as pharmaceuticals, nutraceuticals, fragrances and agrochemicals. Heterogeneous modified catalysts capable of inducing high enantioselectivities are preferred in industrial scale due to their superior separation and handling properties. The topic has been intensively investigated both in industry and academia. The enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst in a laboratory-scale semi-batch reactor was studied as a function of modifier concentration, reaction temperature, stirring rate and catalyst particle size. The main product was always (R)-ethyl mandelate while small amounts of (S)-ethyl mandelate were obtained as by product. The kinetic results showed higher enantioselectivity and lower initial rates approaching asymptotically to a constant value as the amount of modifier was increased. Additionally, catalyst deactivation due to presence of impurities in the feed was prominent in some cases; therefore activated carbon was used as a cleaning agent of the raw material to remove impurities prior to catalyst addition. Detailed characterizations methods (SEM, EDX, TPR, BET, chemisorption, particle size distribution) of the catalysts were carried out. Solvent effects were also studied in the semi-batch reactor. Solvents with dielectric constant (e) between 2 and 25 were applied. The enantiomeric excess (ee) increased with an increase of the dielectric coefficient up to a maximum followed by a nonlinear decrease. A kinetic model was proposed for the enantioselectivity dependence on the dielectric constant based on the Kirkwood treatment. The non-linear dependence of ee on (e) successfully described the variation of ee in different solvents. Systematic kinetic experiments were carried out in the semi-batch reactor. Toluene was used as a solvent. Based on these results, a kinetic model based on the assumption of different number of sites was developed. Density functional theory calculations were applied to study the energetics of the EBF adsorption on pure Pt(1 1 1). The hydrogenation rate constants were determined along with the adsorption parameters by non-linear regression analysis. A comparison between the model and the experimental data revealed a very good correspondence. Transient experiments in a fixed-bed reactor were also carried out in this work. The results demonstrated that continuous enantioselective hydrogenation of EBF in hexane/2-propanol 90/10 (v/v) is possible and that continuous feeding of (-)-cinchonidine is needed to maintain a high steady-state enantioselectivity. The catalyst showed a good stability and high enantioselectivity was achieved in the fixed-bed reactor. Chromatographic separation of (R)- and (S)-ethyl mandelate originating from the continuous reactor was investigated. A commercial column filled with a chiral resin was chosen as a perspective preparative-scale adsorbent. Since the adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post-reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug flow model with a linear driving force approximation. The focus of this research project was the development of a new integrated production concept of optically active chemicals by combining heterogeneous catalysis and chromatographic separation technology. The proposed work is fundamental research in advanced process technology aiming to improve efficiency and enable clean and environmentally benign production of enantiomeric pure chemicals.