The Life Cycle of Chlorine, Part II: Conversion Processes and Use in the European Chemical Industry

The major purpose of this article is to construct a plausible emissions profile for the European chemical industry from process data and mass balance considerations.' In it we describe this industry and its major conversion processes and emissions. Four major process chains, beginning with methane, ethylene, propylene, and benzene are analyzed, along with five important stand-alone processes. A self-consistent version of the industry is constructed for 1992, based on data from a variety of sources.
In 1992 Europe consumed 9,297 metric kilotons as measured by weight of chlorine (kMT[CI]) of salt and 2 I I kMT(CI) of recycled hydrochloric acid (HCI) to produce 86 I0 kMT of virgin elemental chlorine, plus 278 kMT(CI) of virgin by-product HCI. Total chlorine input to the industry was 8,689 kMT including I2 kMT(CI) of recycled chlorinated hydrocarbons (CHCs) and (net) 79 kMT(CI) of HCI. Shipments of chlorine and HCI to other sectors was 1,367 kMT(CI), while 7,322 kMT(CI) was embodied in products or lost within the sector: Of this subtotal, 350 kMT(CI) was used to manufacture identified inorganic chemicals, 5,694 kMT(CI) for identified organic chemicals, and 1,278 kMT(CI) for "other unspecified" chemicals.
We estimate that products account for 41.6% of inputs (measured at the "fence"), while wastes account for 24.7%     

The Life Cycle of Chlorine, Part III

In the two previous articles in this series we reviewed the major processes of chlorine production (Part I) and its intermediate uses and waste products in the production of other chemicals (Part 11). In this article I consider some of the final applications of chlorine (e.g., for water treatment and pulp bleaching) and the uses of the most important chlorinated compounds such as solvents, chlorofluorocarbons, and the plastic polyvinyl chloride in the industrial economy. I summarize known evidence regarding their environmental fates. The special case of persistent long-lived toxic compounds (e.g., pesticides) will be discussed in a subsequent article.     

The Life-Cycle of Chlorine, Part IV

Some cyclic organo-chlorines share key characteristics to a significant degree, notably volatility, solubility in lipids, environmental persistence, a tendency to bioaccumulation, and toxicity to animals. A subset of this group has been designated "persistent organic pollutants" (POPs). Because of their volatility, persistence, and tendency to bioaccumulate, POPs are found in remote locations, such as the Arctic, far from the locations where they were initially used or produced.
Except PCDDs (dioxins) and PCDFs (furans), all are, or were, originally produced for use as such , mainly as pesticides or herbicides. PCDDs and PCDFs have never been produced for their own sake; they are unwanted contaminants of chemical intermediates that were passed on and incorporated in final products, notably herbicides; they are also generated spontaneously in most combustion processes and chlorine bleaching of paper. Most POPs have been sharply restricted or banned outright in most of the industrialized countries, but not in less developed countries.
The qualities of persistence and bioaccumulation give special urgency to monitoring not only point source emissions and local concentrations, but also the mobile environmental reservoirs and exposure routes of these chemicals. To conduct adequate risk analyses, far more detailed data is needed on quantities produced and used, quantities and location of storage, mode of use, location of use, and period of use. Such data are not collected consistently by government or international agencies.     

Routes to Potential Bioproducts from Lignocellulosic Biomass Lignin and Hemicelluloses

An essential feature of proposed fermentation-based lignocellulose to biofuel conversion processes will be the co-production of higher value chemicals from lignin and hemicellulose components. Over the years, many routes for chemical conversion of lignin and hemicelluloses have been developed by the pulp and paper industry and we propose that some of these can be applied for bioproducts manufacturing. For lignin products, thermochemical, chemical pulping, and bleaching methods for production of polymeric and monomeric chemicals are reviewed. We conclude that peroxyacid chemistry for phenol and ring-opened products looks most interesting. For hemicellulose products, preextraction of hemicelluloses from woody biomass is important and influences the mixture of solubilized material obtained. Furfural, xylitol, acetic acid, and lactic acid are possible targets for commercialization, and the latter can be further converted to acrylic acid. Pre-extraction of hemicelluloses can be integrated into most biomass-to-biofuel conversion processes.     

The use of enzymes in the chemical industry in Europe

Many European chemical industries are in a phase of reorganization resulting in a general opening towards life sciences. Traditional chemical markets are served increasingly with products derived from bioprocesses or hybrid chemical/biocatalytic processes. Biocatalytic steps are already being used to produce a wide range of products, including agricultural chemicals, organics, drugs and plastic materials, to name but a few. Apart from the rapidly growing number of commercialized bioprocesses, a partial survey of exploratory activities points to future applications of enzymes in the European chemical industry, which will bring new products and technologies and, in some cases, replace traditional syntheses.     

Chlorine in the Netherlands, Part II: Risk Management in Uncertainty for Chlorine

The debate over chlorine in industrialized economies has become extremely polarized in the last decade. Environmental pressure groups are striving for a virtual phaseout of chlorine and chlorinated hydrocarbons (CHCs), because they are convinced that the risks cannot be managed. Industry argues this is not necessary because environmental risks can be controlled, nor is it feasible, because at least 60% of all firms use CHCs, produds made with CHCs, or elemental chlorine. In an attempt to give this discussion a more factual basis, the Dutch minister of environment launched a strategic study on chlorine (see Kleijn et al. I997;Tukker et al. 1995). Using all available knowledge about emissions and contemporary evaluation methods, the study found only a limited number of environmental issues outstanding related to the chlorine chain: however, it also found important uncertainties. This article describes the outstanding uncertainties in more detail. It defines which uncertainties have to be regarded as chlorine-specific and the extent to which additional research can resolve them. For the remaining uncertainties the potential benefts of uncertainty reduction strategies are evaluted, relying mainly on the precautionary principle     

Application of whole cell rhodococcal biocatalysts in acrylic polymer manufacture

Rhodococci are ubiquitous in nature and their ability to metabolise a wide range of chemicals, many of which are toxic, has given rise to an increasing number of studies into their diverse use as biocatalysts. Indeed rhodococci have been shown to be especially good at degrading aromatic and aliphatic nitriles and amides and thus they are very useful for waste clean up where these toxic chemicals are present.The use of biocatalysts in the chemical industry has in the main been for the manufacture of high-value fine chemicals, such as pharmaceutical intermediates, though investigations into the use of nitrile hydratase, amidase and nitrilase to convert acrylonitrile into the higher value products acrylamide and acrylic acid have been carried out for a number of years. Acrylamide and acrylic acid are manufactured by chemical processes in vast tonnages annually and they are used to produce polymers for applications such as superabsorbents, dispersants and flocculants. Rhodococci are chosen for use as biocatalysts on an industrial scale for the production of acrylamide and acrylic acid due to their ease of growth to high biomass yields, high specific enzyme activities obtainable, their EFB class 1 status and robustness of the whole cells within chemical reaction systems.Several isolates belonging to the genus Rhodococcus have been shown in our studies to be among the best candidates for acrylic acid preparation from acrylonitrile due to their stability and tolerance to high concentrations of this reactive and disruptive substrate. A critical part of the selection procedure for the best candidates during the screening programme was high purity product with very low residual substrate concentrations, even in the presence of high product concentrations. Additionally the nitrile and amide substrate scavenging ability which enables rhodococci to survive very successfully in the environment leads to the formation of biocatalysts which are suitable for the removal of low concentrations of acrylonitrile and acrylamide in waste streams and for the removal of impurities in manufacturing processes.     

Flows of Chemical Risk Information in the Consumer Paint Product Chain

In this study the flows of chemical risk information for paint as a consumer product were investigated from a product chain perspective. The main method of research involved semi‐structured interviews with Swedish manufacturers of paint and chemicals. In addition, retailers and consumers were interviewed. The flows of chemical risk information between actors within (e.g., manufacturers, retailers, and consumers) and outside (e.g., industry associations and regulators) the paint product chain are described. Because the European chemical legislation REACH (Registration, Evaluation, Authorization and restriction of CHemicals) plays a large role in the management of chemical risk information at companies, some consequences of REACH on actors in the paint product chain are described. Examples of such consequences are that importing of chemicals from non–European Union (EU) countries may be discouraged and that some low‐volume chemicals may no longer be produced. However, manufacturers do not yet see these consequences as impediments to innovation. The results of this work show that chemical risk information is most comprehensive during the manufacturing steps of the product chain. This is due not only to tradition and industry initiatives, but also to REACH and other legislation. The results also illustrate the need for evaluation of how chemical risk information is used in different contexts and the importance of directing the right information at the right target group. Following legislative development, more specialized information is required in the safety data sheet (SDS), and because of this many manufacturers find it necessary to create simplified safety sheets that make the most pertinent safety and hazard information easily accessible to individuals that handle the chemicals in their factories. The study found that in creating the simplified safety sheets, the content and use of chemical risk information is evaluated and adjusted for presentation to this particular target group. It is evident that the Swedish Paint and Printing Ink Makers Association plays an important role in the interpretation of legal requirements and even in agreements for providing information that exceeds legal requirements.     

Microbial utilization of crude glycerol for the production of value-added products

Energy fuels for transportation and electricity generation are mainly derived from finite and declining reserves of fossil hydrocarbons. Fossil hydrocarbons are also used to produce a wide range of organic carbon-based chemical products. The current global dependency on fossil hydrocarbons will not be environmentally or economically sustainable in the long term. Given the future pessimistic prospects regarding the complete dependency on fossil fuels, political and economic incentives to develop carbon neutral and sustainable alternatives to fossil fuels have been increasing throughout the world. For example, interest in biodiesel has undergone a revival in recent times. However, the disposal of crude glycerol contaminated with methanol, salts, and free fatty acids as a by-product of biodiesel production presents an environmental and economic challenge. Although pure glycerol can be utilized in the cosmetics, tobacco, pharmaceutical, and food industries (among others), the industrial purification of crude glycerol is not economically viable. However, crude glycerol could be used as an organic carbon substrate for the production of high-value chemicals such as 1,3-propanediol, organic acids, or polyols. Microorganisms have been employed to produce such high-value chemicals and the objective of this article is to provide an overview of studies on the utilization of crude glycerol by microorganisms for the production of economically valuable products. Glycerol as a by-product of biodiesel production could be used a feedstock for the manufacture of many products that are currently produced by the petroleum-based chemical industry.     

The toxic origins of disease

Researchers say that endocrine-disrupting chemicals can permanently damage the developing organism and may even promote obesity. But the chemical industry doesn't want you to believe them.     

Effect of Algicidal Quaternaries on the Germicidal Activity of Chlorine on Swimming Pool Water

The Swimming Pool Water Disinfectant Test Method of the Association of Official Analytical Chemists was used to determine the effect of the accepted level of 2 ppm of some commercial quaternary ammonium algicides on the germicidal activity of chlorine. Accurate determinations on the amounts of residual available chlorine in chlorine-quaternary mixtures could not be made by the usual chemical methods. This made it necessary to base all comparisons on the starting concentrations of available chlorine rather than the final concentration as specified in the method employed. No evidence was obtained to support the use of lower concentrations of residual available chlorine for disinfection in the presence of algicidal quaternaries than those commonly recognized as effective by the American Public Health Association. The rate of kill against the gram-positive test organism Streptococcus faecalis was faster in quaternary-chlorine mixtures than in the sodium hypochlorite control solutions. The practical significance of this result in the bench method identified cannot be ascertained in the absence of more sensitive and precise chemical procedures for determining concentrations of residual available chlorine in the presence of quaternaries or in actual swimming pool tests.     

Methanol,a potential feedstock for biotechnological processes

A wide variety of bacteria and yeasts is able to grow in inexpensive synthetic media with methanol as the sole or major source of carbon and energy. This is due to the presence of a few unique enzymes which enable these organisms to generate metabolic energy and synthesize cell constituents from this one-carbon substrate. In the chemical industry there is currently much interest in the production of fuels and chemicals from methanol. As a feedstock for industrial fermentations methanol is also attractive because of its low cost, ease of handling and abundant availability. In many countries methanol-utilizing microbes are being studied and their potential utility in biotechnological processes is explored. These studies are aimed at making use of their characteristic properties, exploiting known organisms and new strains for improving existing processes and developing novel products.     

Factors in the Testing and Application of Algicides

A review is presented of some of the factors affecting the laboratory testing and practical applications of chemicals toxic to algae. The basic factor demonstrated is that the amount of chemical required to inhibit the growth of algae is dependent on the amount of algae present and not on the volume of water in which the algae are dispersed. It is shown how a chemical can be tested for algistatic or algicidal properties, thus enabling one to decide how best to apply a particular chemical. The selectivity of chemicals and the development of resistance in algae towards certain chemicals is demonstrated. Also, it is shown how certain algae can appear to be resistant to chemical treatments because of their growth habit or their production of extracellular products which affect the toxicity of added chemicals. With a better understanding of how various factors can influence the effectiveness of toxic chemicals, it is hoped that the selection of a chemical and method of application to a particular problem will be more successful.     

Quality Control and Assurance: crucial for the sustainability of the applied phycology industry

The chemical and nutritional properties of microalgae are well known, which has led to an ever expanding industry for foods and dietary supplements both in terms of quantity and products. Little has been done to regulate or control quality and assurance in the applied phycology industry and it is known that it varies considerably. Nutritional aspects of produced biomass and consumption as dietary supplements have become issues of concern, especially since the industry is lucrative and fast growing. Various claims are made regarding dietary and food supplements that include health, nutrition, structure and functioning, many often unsubstantiated. Although quality is a subjective term many organisations are involved in testing, controlling and determining criteria. Today quality is more than just standards where it is an "integrated quality management approach" involving amongst others "hazard analyses and critical control points" (HACCP) practices. Microalgae are not recognised as a food or food supplement and they are also not categorised under herbals or botanicals, but as "other supplements". Produced microalgal biomass is subject to contamination from the entire range of contaminants and pathogens. Contamination of products by algal toxins in mixed culture populations also occurs. The industry has largely regulated itself, but there is considerable scope for improvement. There is a need for support and dissemination of information in the industry.     

Bioactivities,bioactive compounds and chemical constituents of mangrove plants

This review article presents the traditional and medicinal uses, and examines recent investigations on the biological activities of extracts, and chemicals identified from mangroves and mangal associates. Metabolites identified from mangrove plants are classified according to ‘chemical classes’, and some of their structures are illustrated. The article also presents some of the functions of the chemicals present and attempt to emphasize and create an awareness of the great of potential mangroves and mangal associates possess as a source of novel agrochemicals, compounds of medicinal value, and a new source of many already known biologically active compounds. This revised version was published online in July 2006 with corrections to the Cover Date.     

平台化学品短链支链脂肪酸和短链支链醇的微生物代谢工程

短链支链脂肪酸和短链支链醇均为重要的平台化学品,是合成多种高附加值产品的前体物质,市场需求巨大。目前两者的生产主要是利用基于石化原料的化学合成法。化学合成法存在着严重依赖化石燃料、反应效率低以及极易造成环境污染等缺点。微生物代谢工程的快速发展为这些平台化学品的生产提供了一条极具潜力的生物合成路线。利用微生物代谢工程技术构建生产这些平台化学品的微生物细胞工厂具有绿色清洁、可持续发展和经济效益好等独特优势。本文系统综述了近年来微生物代谢工程技术在短链支链脂肪酸和短链支链醇合成方面的研究进展,包括所涉及的宿主菌株、关键酶、代谢途径及其改造等,并探讨了未来的发展前景。     

The natural chlorine cycle – fitting the scattered pieces

Chlorine is one of the most abundant elements on the surface of the earth. Until recently, it was widely believed that all chlorinated organic compounds were xenobiotic, that chlorine does not participate in biological processes and that it is present in the environment only as chloride. However, over the years, research has revealed that chlorine takes part in a complex biogeochemical cycle, that it is one of the major elements of soil organic matter and that the amount of naturally formed organic chlorine present in the environment can be counted in tons per km(2). Interestingly enough, some of the pieces of the chlorine puzzle have actually been known for decades, but the information has been scattered among a number of different disciplines with little or no exchange of information. The lack of communication appears to be due to the fact that the points of departure in the various fields have not corresponded; a number of paradoxes are actually revealed when the known pieces of the chlorine puzzle are fit together. It appears as if a number of generally agreed statements or tacit understandings have guided perceptions, and that these have obstructed the understanding of the chlorine-cycle as a whole. The present review enlightens four paradoxes that spring up when some persistent tacit understandings are viewed in the light of recent work as well as earlier findings in other areas. The paradoxes illuminated in this paper are that it is generally agreed that: (1) chlorinated organic compounds are xenobiotic even though more than 1,000 naturally produced chlorinated compounds have been identified; (2) only a few, rather specialised, organisms are able to convert chloride to organic chlorine even though it appears as if the ability among organisms to transform chloride to organic chlorine is more the rule than the exception; (3) all chlorinated organic compounds are persistent and toxic even though the vast majority of naturally produced organic chlorine is neither persistent nor toxic; (4) chlorine is mainly found in its ionic form in the environment even though organic chlorine is as abundant or even more abundant than chloride in soil. Furthermore, the contours of the terrestrial chlorine cycle are outlined and put in a concrete form by constructing a rough chlorine budget over a small forested catchment. Finally, possible ecological roles of the turnover of chlorine are discussed.     

Chlorine in the Netherlands, Part I, An Overview

Over the last decade debate among environmental pressure groups, industry, and the authorities overthe threat posed by chlorine has become extremely polarized. In response, the Dutch minister of the environment commissioned a strategic study on chlorine. The first phase of the study described in this article, was designed as a substance flow analysis, encompassing some 99% of the flows of chlorinated hydrocarbons (CHC) in the Netherlands. The study provided an overview of flows of CHC through the Dutch anthroposphere and to inventory the leaks to the environment. Emissions, wastestreams, exports, imports, and flows through the anthroposphere were inventoried, drawing on all possible sources including the Dutch emission registration database, life-cycle assessment (LCA) databases, and industrial data. Emissions were evaluated using the characterization step from LCA methodology. Emissions with toxicological effects were also evaluated on the basis of actual risk assessments of the National Institute of Public Health and Environmental Protection (RIVM).This resulted in the establishment of six groups of priority segments in the Dutch chlorine chain, for which additional measures will be prepared. The study showed that the environmental groups' pronouncements about the structural dangers associated with the chlorine chain are not supported by current knowledge. The study however; also indicates that important areas of uncertainty require attention, especially relating to the possible emissions of persistent bioaccumulating toxic micropollutants.     

Combining bio- and chemo-catalysis: from enzymes to cells, from petroleum to biomass

In the future, biomass will continue to emerge as a viable source of chemicals. The development of new industries that utilize bio-renewables provides opportunities for innovation. For example, bio- and chemo-catalysts can be combined in 'one pot' to prepare chemicals of commercial value. This has been demonstrated using isolated enzymes and whole cells for a variety of chemical transformations. The one-pot approach has been successfully adopted to convert chemicals derived from biomass, and, in our opinion, it has an important role to play in the design of a more sustainable chemical industry. To implement new one-pot bio- and chemo-catalytic processes, issues of incompatibility must be overcome; the strategies for which are discussed in this opinion article.