Natural production of organohalogen compounds handbook of environmental chemistry

Editor-in-Chief Prof em Dr Otto Hutzinger University of Bayreuth c/o Bad Ischl Office Grenzweg 22 5351 Aigen-Vogelhub, Austria E-mail: hutzinger-univ-bayreuth@aon.at Advisory Board Dr T.A.T Aboul-Kassim Prof Dr D Mackay Department of Civil Construction and Environmental Engineering, College of Engineering, Oregan State University, 202 Apperson Hall, Corvallis, OR 97331, USA Department of Chemical Engineering and Applied Chemistry University of Toronto Toronto, Ontario, Canada M5S 1A4 Dr D Barcelo Environment Chemistry IIQAB-CSIC Jordi Girona, 18 08034 Barcelona, Spain Prof Dr P Fabian Chair of Bioclimatology and Air Pollution Research Technical University Munich Hohenbacherstraße 22 85354 Freising-Weihenstephan, Germany Prof Dr A.H Neilson Swedish Environmental Research Institute P.O.Box 21060 10031 Stockholm, Sweden E-mail: ahsdair@ivl.se Prof Dr J Paasivirta Department of Chemistry University of Jyväskylä Survontie P.O.Box 35 40351 Jyväskylä, Finland Dr H Fiedler Prof Dr Dr H Parlar Scientific Affairs Office UNEP Chemicals 11–13, chemin des Anémones 1219 Châteleine (GE), Switzerland E-mail: hfiedler@unep.ch Institute of Food Technology and Analytical Chemistry Technical University Munich 85350 Freising-Weihenstephan, Germany Prof Dr H Frank Chair of Environmental Chemistry and Ecotoxicology University of Bayreuth Postfach 10 12 51 95440 Bayreuth, Germany Department of Veterinary Physiology and Pharmacology College of Veterinary Medicine Texas A & M University College Station, TX 77843-4466, USA E-mail: ssafe@cvm.tamu.edu Prof Dr M A K Khalil Prof P.J Wangersky Department of Physics Portland State University Science Building II, Room 410 P.O Box 751 Portland, Oregon 97207-0751, USA E-mail: aslam@global.phy.pdx.edu University of Victoria Centre for Earth and Ocean Research P.O.Box 1700 Victoria, BC, V8W 3P6, Canada E-mail: wangers@attglobal.net Prof Dr S.H Safe Preface Environmental Chemistry is a relatively young science Interest in this subject, however, is growing very rapidly and, although no agreement has been reached as yet about the exact content and limits of this interdisciplinary discipline, there appears to be increasing interest in seeing environmental topics which are based on chemistry embodied in this subject One of the first objectives of Environmental Chemistry must be the study of the environment and of natural chemical processes which occur in the environment A major purpose of this series on Environmental Chemistry, therefore, is to present a reasonably uniform view of various aspects of the chemistry of the environment and chemical reactions occurring in the environment The industrial activities of man have given a new dimension to Environmental Chemistry We have now synthesized and described over five million chemical compounds and chemical industry produces about hundred and fifty million tons of synthetic chemicals annually We ship billions of tons of oil per year and through mining operations and other geophysical modifications, large quantities of inorganic and organic materials are released from their natural deposits Cities and metropolitan areas of up to 15 million inhabitants produce large quantities of waste in relatively small and confined areas Much of the chemical products and waste products of modern society are released into the environment either during production, storage, transport, use or ultimate disposal These released materials participate in natural cycles and reactions and frequently lead to interference and disturbance of natural systems Environmental Chemistry is concerned with reactions in the environment It is about distribution and equilibria between environmental compartments It is about reactions, pathways, thermodynamics and kinetics An important purpose of this Handbook, is to aid understanding of the basic distribution and chemical reaction processes which occur in the environment Laws regulating toxic substances in various countries are designed to assess and control risk of chemicals to man and his environment Science can contribute in two areas to this assessment; firstly in the area of toxicology and secondly in the area of chemical exposure The available concentration (“environmental exposure concentration”) depends on the fate of chemical compounds in the environment and thus their distribution and reaction behaviour in the environment One very important contribution of Environmental Chemistry to the above mentioned toxic substances laws is to develop laboratory test methods, or mathematical correlations and models that predict the environ- VIII Preface mental fate of new chemical compounds The third purpose of this Handbook is to help in the basic understanding and development of such test methods and models The last explicit purpose of the Handbook is to present, in concise form, the most important properties relating to environmental chemistry and hazard assessment for the most important series of chemical compounds At the moment three volumes of the Handbook are planned Volume deals with the natural environment and the biogeochemical cycles therein, including some background information such as energetics and ecology Volume is concerned with reactions and processes in the environment and deals with physical factors such as transport and adsorption, and chemical, photochemical and biochemical reactions in the environment, as well as some aspects of pharmacokinetics and metabolism within organisms.Volume deals with anthropogenic compounds, their chemical backgrounds, production methods and information about their use, their environmental behaviour, analytical methodology and some important aspects of their toxic effects The material for volume 1, and was each more than could easily be fitted into a single volume, and for this reason, as well as for the purpose of rapid publication of available manuscripts, all three volumes were divided in the parts A and B Part A of all three volumes is now being published and the second part of each of these volumes should appear about six months thereafter Publisher and editor hope to keep materials of the volumes one to three up to date and to extend coverage in the subject areas by publishing further parts in the future Plans also exist for volumes dealing with different subject matter such as analysis, chemical technology and toxicology, and readers are encouraged to offer suggestions and advice as to future editions of “The Handbook of Environmental Chemistry” Most chapters in the Handbook are written to a fairly advanced level and should be of interest to the graduate student and practising scientist I also hope that the subject matter treated will be of interest to people outside chemistry and to scientists in industry as well as government and regulatory bodies It would be very satisfying for me to see the books used as a basis for developing graduate courses in Environmental Chemistry Due to the breadth of the subject matter, it was not easy to edit this Handbook Specialists had to be found in quite different areas of science who were willing to contribute a chapter within the prescribed schedule It is with great satisfaction that I thank all 52 authors from countries for their understanding and for devoting their time to this effort Special thanks are due to Dr F Boschke of Springer for his advice and discussions throughout all stages of preparation of the Handbook Mrs A Heinrich of Springer has significantly contributed to the technical development of the book through her conscientious and efficient work Finally I like to thank my family, students and colleagues for being so patient with me during several critical phases of preparation for the Handbook, and to some colleagues and the secretaries for technical help I consider it a privilege to see my chosen subject grow My interest in Environmental Chemistry dates back to my early college days in Vienna I received significant impulses during my postdoctoral period at the University of California and my interest slowly developed during my time with the National Research Preface IX Council of Canada, before I could devote my full time of Environmental Chemistry, here in Amsterdam I hope this Handbook may help deepen the interest of other scientists in this subject Amsterdam, May 1980 O Hutzinger Twentyone years have now passed since the appearance of the first volumes of the Handbook Although the basic concept has remained the same changes and adjustments were necessary Some years ago publishers and editors agreed to expand the Handbook by two new open-end volume series: Air Pollution and Water Pollution These broad topics could not be fitted easily into the headings of the first three volumes All five volume series are integrated through the choice of topics and by a system of cross referencing The outline of the Handbook is thus as follows: The Natural Environment and the Biogeochemical Cycles, Reaction and Processes, Anthropogenic Compounds, Air Pollution, Water Pollution Rapid developments in Environmental Chemistry and the increasing breadth of the subject matter covered made it necessary to establish volume-editors Each subject is now supervised by specialists in their respective fields A recent development is the accessibility of all new volumes of the Handbook from 1990 onwards, available via the Springer Homepage http://www.springer de or http://Link.springer.de/series/hec/ or http://Link.springerny.com/ series/hec/ During the last to 10 years there was a growing tendency to include subject matters of societal relevance into a broad view of Environmental Chemistry Topics include LCA (Life Cycle Analysis), Environmental Management, Sustainable Development and others.Whilst these topics are of great importance for the development and acceptance of Environmental Chemistry Publishers and Editors have decided to keep the Handbook essentially a source of information on “hard sciences” With books in press and in preparation we have now well over 40 volumes available.Authors, volume-editors and editor-in-chief are rewarded by the broad acceptance of the “Handbook” in the scientific community Bayreuth, July 2001 Otto Hutzinger Contents Foreword Dušan Gruden XIII Introduction Dušan Gruden Power Units for Transportation Dušan Gruden, Klaus Borgmann, Oswald Hiemesch 15 Means of Transportation and Their Effect on the Environment Hans Peter Lenz, Stefan Prüller, Dušan Gruden 107 Legislation for the Reduction of Exhaust Gas Emissions Wolfgang Berg 175 Fuels Dušan Gruden 255 Subject Index 289 Foreword Over centuries mankind has pursued technical progress for the benefit of improved prosperity without simultaneously taking appropriate steps to ensure the environmental friendliness of the involved processes However, in the middle of the 20th century environmental episodes drew attention to the negative impacts on the environment caused by this progress As a matter of fact, concern about the influence of human activities on the environment is neither a new phenomenon nor a new attribute of modern people but has accompanied human society throughout its existence What is new, however, is the increasing intensity of man’s efforts to protect his environment as reflected in a multitude of national and international environmental laws enacted all around the globe Life as a whole, and human existence in particular, are characterized by constant movement and changes This means that living beings need to be mobile to survive By developing suitable technical means man has enormously increased his mobility – expressed in terms of speed and distance – when compared with other living beings on our planet The automobile is one of the inventions that has made a decisive contribution to this mobility and it has become an inseparable part of modern human society In the second half of the 20th century, the automobile developed from a luxury article and prestige object for a few into a basic commodity for millions of people It is through this widespread use that negative impacts on the environment have become clearly visible Therefore, since the late 1960s and early 1970s, automotive development has been accompanied by an ever increasing number of strict legal standards, e.g., about the reduction of exhaust gas pollutants, noise emissions, hazardous substances and waste, as well as about improved recyclability of materials and other aspects Achievements in improving the ecological characteristics of the automobile are highly impressive: A modern car emits only fractions of the amounts of noise and exhaust gas pollutants produced by its predecessors 30 years ago Today, 100 modern passenger cars in total emit less of the legally limited exhaust gas constituents than one single car of 1970 The same trend can be found with all the other ecologically relevant automotive features so that the absolute impact of the automobile on our environment is considerably lower today than it was in the past The development of the automobile is increasingly linked to deliberations about sustainable development.While this term in the recent past was only related to the aspect of ecological consequences for the environment, it comprises XIV Foreword today at least two further essential pillars, namely economic consequences and social responsibility When discussing sustainability in the context of automotive development, it must be borne in mind that essential technical elements of the automobile – such as safety, power output, torque, fuel consumption, durability, maintenance intervals, and comfort should not be compromised The modern automobile has achieved outstanding performance and superiority compared to its predecessors in all theses elements and will continue to proceed along this evolutionary development path This book focuses on ecological aspects related to the development and use of automobiles, leaving many environment-related initiatives towards improvements of the automotive production process out of consideration It shall, however, be mentioned in this context that also the production of modern cars is not possible without the observance of a wide range of stringent environmental laws Thus, in order to be allowed to enter the market, a car must not only perform environmental-friendly during its operation but must have been produced to ecological standards as well Company audits carried out routinely according to EMAS (Eco Management Auditing Scheme) and ISO 14001 show that automotive manufacturers are constantly improving the ecological compatibility of their production processes The contributions to this book were written by experts, most of whom have been actively involved in the development of modern automobiles and their combustion engines for more than 30 years They have participated in all phases of the ecological development of the automobile – from the basic attempts to respond to the first exhaust gas emission control requirements in the USA (1966) and Europe (1970) to the cost-intensive efforts towards meeting the comprehensive and highly demanding emission legislations currently existing and further anticipated worldwide As the 20th century ends and the 21st century begins, these experts have summarized their experience and know-how in this book which bears witness to the successful implementation of ecological considerations into automotive development work In my capacity as coordinator of the preparatory work for this book I would like to thank my colleagues – Prof Dr sc techn Hans Peter Lenz and his collaborator, Mr Stefan Prüller (Dipl.-Ing.) of Technical University of Vienna, Dr Klaus Borgmann and Mr Otto Hiemesch (Dipl.-Ing.) of BMW AG and Dr Wolfgang Berg, Consultant and long-standing collaborator of DaimlerChrysler AG – for their cooperation and valuable contributions I would like to express particular gratitude to Dr Ing h.c F Porsche AG for permission to carry out this project Weissach, June 2003 D Gruden The Handbook of Environmental Chemistry Vol 3, Part P (2003): 1–15 DOI 10.1007/b 10445 The Diversity of Naturally Produced Organohalogens Gordon W Gribble Department of Chemistry, Dartmouth College, Hanover, NH 03755, USA E-mail: ggribble@dartmouth.edu More than 3700 organohalogen compounds, mainly containing chlorine or bromine but a few with iodine and fluorine, are produced by living organisms or are formed during natural abiogenic processes, such as volcanoes, forest fires, and other geothermal processes The oceans are the single largest source of biogenic organohalogens, which are biosynthesized by a myriad of seaweeds, sponges, corals, tunicates, bacteria, and other marine life Terrestrial plants, fungi, lichen, bacteria, insects, some higher animals, and even humans also account for a diverse collection of organohalogens Keywords Organohalogen, Organochlorine, Organobromine, Natural halogen Introduction 2 Sources and Compounds 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 Marine Plants Marine Sponges Other Marine Animals Marine Bacteria and Fungi Terrestrial Plants Fungi and Lichen Bacteria Insects Higher Animals and Humans Abiogenic Sources Concluding Remarks 13 References 13 10 11 12 © Springer-Verlag Berlin Heidelberg 2003 G W Gribble Introduction Thirty years ago some 200 natural organohalogen compounds had been documented (150 organochlorines and 50 organobromines) [1] Nevertheless, the scientific community generally considered these compounds to be isolation artifacts or rare abnormalities of nature For example,“present information suggests that organic compounds containing covalently bound halogens are found only infrequently in living organisms” [2] Unfortunately, even today this myth persists and has entered modern textbooks: “unlike metals, most of these compounds [halogenated hydrocarbons] are man-made and not occur naturally …” [3] The striking increase in the number of known natural organohalogens to more than 3700 is partly a consequence of the general revitalization of interest in natural products as a potential source of new medicinal drugs Furthermore, the relatively recent exploration of the oceans has yielded large numbers of novel organohalogens from marine plants, animals, and bacteria Much of the success of these explorations is attributed to improved collection methods (SCUBA and remote submersibles for the collection of previously inaccessible marine organisms), selective bioassays for identifying biologically active compounds, powerful multidimensional nuclear magnetic resonance spectroscopy techniques for characterizing sub-milligram quantities of compounds, and new separation and purification techniques (liquid-liquid extraction, high-pressure liquid chromatography) Furthermore, an awareness and appreciation of folk medicine and ethobotany have guided natural product chemists to new medicinal leads Although most of the biogenic organohalogens discovered over the past thirty years are marine-derived, many other halogenated compounds are found in terrestrial plants, fungi, lichen, bacteria, insects, some higher animals, and humans [4–9] As of June 2002, the breakdown of natural organohalogens was approximately: organochlorines, 2200; organobromines, 1900; organoiodines, 100; organofluorines, 30 [10].A few hundred of these compounds contain both chlorine and bromine Sources and Compounds 2.1 Marine Plants Seaweeds produce an array of both simple and complex organohalogens, presumably for chemical defense Some simple haloalkanes found in marine algae are shown in Fig Laboratory cultures of marine phytoplankton produce chloromethane, bromomethane, and iodomethane [11] The favorite edible seaweed of native Hawaiians is “limu kohu” (Asparagopsis taxiformis), and this delicacy contains more than 100 organohalogens, most of which were previously unknown compounds [12, 13] Bromoform is the major organohalogen in this seaweed.A selection of others is depicted in Fig 2.Another red alga, Bonnemaisonia hamifera, contains several brominated heptanones that might be precursors to bromoform formed via a classical “haloform reaction” 206 J P Hendersen and J W Heinecke Results from mass spectrometric analysis of head space gas derived from the myeloperoxidase-H2O2-chloride system are consistent with this interpretation The system produced a gas with the expected mass-to-charge ratio and isotope pattern of Cl2 [33] Taken together, these observations suggest that the myeloperoxidase system of human neutrophils generates Cl2 , a potent halogenating agent that would be expected to more readily permeate lipid membranes than HOCl Eosinophil peroxidase and, to a variable degree, myeloperoxidase can generate brominating oxidants [26 – 28, 30, 34] When compared with HOCl, peroxidase-derived brominating agents have a greater propensity for halogenating aromatic compounds under physiologically plausible conditions Accordingly, mammalian peroxidases generate significant yields of 3-bromotyrosine at physiological concentrations of chloride and bromide (Fig 2) [34, 70] Mass spectrometric studies have detected a rise in 3-bromotyrosine levels in mice during acute infection and inflammation and in asthmatic humans after exposure to allergens [45, 70] 3-Bromotyrosine production is impaired in mice deficient in either myeloperoxidase or eosinophil peroxidase, indicating that both pathways might generate brominating intermediates in vivo [70, 72] Nucleic Acid Halogenation in Humans In addition to oxidizing amino acids, phagocyte products can also oxidize nucleic acids This ability might help explain why chronic inflammation caused by bacteria, parasites, viruses, foreign bodies, environmental exposures, anatomical malformations, or unknown agents has been linked to human cancer [9, 73–75] Infections associated with specific cancers include schistosomiasis (bladder cancer), liver fluke infection (bile duct carcinoma), chronic viral hepatitis (liver cancer), and Helicobacter pylori infection (gastric cancer) Non-infectious inflammatory diseases with cancer associations include ulcerative colitis (colon cancer), reflux esophagitis (esophageal adenocarcinoma), and pulmonary asbestosis (mesothelioma) Moreover, the ability of cigarette smoke to provoke an inflammatory response in the lungs might contribute to the increased risk of lung cancer among smokers The great variety of inflammatory conditions that predispose humans to cancer has intensified interest in identifying features of the inflammatory response that contribute to mutagenesis and cancer development Recent genetic epidemiological studies have found a relationship between polymorphisms in the promoter of the myeloperoxidase gene and the risk for promyelocytic leukemia, lung, and laryngeal cancers [35–40] This observation, along with the strong association between specific cancers and infection by parasites such as Schistosoma haematobium, Chlonorchis sinensis, and Opisthorchis viverrini, also raise the question of whether eosinophil peroxidase exerts similarly mutagenic effects during inflammation To determine whether the halogenating agents produced by mammalian myeloperoxidase and eosinophil peroxidase might be mutagenic and potentially carcinogenic, we determined whether these agents react with deoxyribonucleosides We found that phagocyte peroxidase systems modify deoxycytidine to form the aromatic electrophilic substitution products 5-chlorodeoxycytidine and Myeloperoxidase and Eosinophil Peroxidase: Phagocyte Enzymes for Halogenation in Humans 207 Fig Halogenation of pyrimidines by myeloperoxidase (MPO) and eosinophil peroxidase (EPO) 5-bromodeoxycytidine (Fig 3) [29 – 32] Both activated neutrophils and the myeloperoxidase system generated 5-chlorodeoxycytidine.Activated eosinophils, activated neutrophils, the eosinophil peroxidase system, and the myeloperoxidase system generated 5-bromodeoxycytidine in the presence of physiologically plausible bromide concentrations Thus, halogenation of nucleobases might be one potential mechanism for cytotoxicity and mutagenesis during inflammation Unlike oxidized bases such as 8-hydroxydeoxyguanosine, halogenated pyrimidines are base analog mutagens that can be taken up from the extracellular space and erroneously used for DNA synthesis [76, 77] The best-known base analog mutagen is 5-bromodeoxyuridine (BrdU), a thymidine analog 5-Chloro, 5bromo-, and 5-iododeoxyuridine are thymidine analogs because the halogen group mimics the 5-methyl group of the thymine ring 5-Fluorouracil is an analog of the RNA base uracil because of fluorine’s smaller atomic radius Thymine normally forms a base pair with adenine in double-stranded DNA However, the electron-withdrawing effect of 5-halopyrimidines increases the likelihood that a tautomer and/or anion will form [78, 79].As a result, thymidine analogs can base pair with guanine, and incorporation of these analogs leads to transition mutations (T to C, C to T, G to A, A to G) Dividing fibroblasts exposed to the product of deoxycytidine oxidation by eosinophil peroxidase incorporated BrdU into their nuclear DNA [31] This observation is consistent with the mutagenic scheme offered in Fig The model suggests that mammalian peroxidases convert deoxycytidine to 5-halogenated deoxycytidine The latter is transported into cells, where it is deaminated and phosphorylated The resulting nucleotide can then be incorporated into DNA 208 J P Hendersen and J W Heinecke Fig A model for mutagenesis involving incorporation of halogenated nucleotides during DNA synthesis Most studies of mutagenesis have focused on direct oxidative damage to DNA, but mutations could also arise if nucleobase analogs were incorporated into DNA in place of normal nucleobases, as occurs when proliferating cells are incubated with 5-chlorouracil, 5bromouracil, or 5-bromodeoxyuridine We propose that reactive species produced by peroxidases halogenate nucleotides and nucleotide precursors that can be subsequently incorporated into DNA Our observations suggest a novel mechanism for nucleotide precursor mutagenesis This process might alter genes, enabling pyrimidine halogenation by myeloperoxidase (MPO) or eosinophil peroxidase (EPO) to produce carcinogenic changes in inflamed tissue This model is unique for two reasons First, it implicates endogenous halogenating agents in mutagenesis Second, it places the critical oxidative event in the cytoplasm or outside the cell rather than directly in chromosomal DNA Indeed, bacteria exposed to the myeloperoxidase chlorinating system accumulate 5-chlorodeoxycytidine in their RNA but not their DNA [29] The surprising conclusion is that that RNA – rather than DNA – is the major target for oxidative damage by halogenating intermediates in bacteria and perhaps mammalian cells Its susceptibility to damage might result from its single-stranded structure or location in the cell Because cells can halogenate and deaminate cytosine and incorporate the resulting halogenated uracil into DNA, uracil itself might serve as a substrate for peroxidase-induced mutagenesis (Fig 4) In vitro experiments have shown that phagocyte peroxidases can halogenate both deoxyuridine and uracil, the latter in near-quantitative yield [32] These enzymes might therefore act as mutagenic alternatives to thymidylate synthase, converting the RNA base uracil to an analog of a DNA base by adding a bulky group (in this case chlorine or bromine) to the position of the pyrimidine ring Interestingly, halogenated deoxyuridines can act as irreversible, mechanism-based inhibitors of thymidylate synthase, depleting cells of thymidine and facilitating their own incorporation as thymidine analogs into DNA [77] Myeloperoxidase and Eosinophil Peroxidase: Phagocyte Enzymes for Halogenation in Humans 209 We recently used mass spectrometry to demonstrate that free 5-chlorouracil and 5-bromouracil are detectable in human tissue obtained from sites of inflammation These molecules represent initial products of endogenous halogenation by myeloperoxidase and eosinophil peroxidase (Fig 4) and can also be derived by deaminating halogenated cytosine We identified them by molecular mass, chromatographic retention time, and the unique isotope patterns characteristic of chlorinated and brominated compounds We used isotope-labeled uracil to verify that the products could not be attributed to artifactual halogenation during the analytical workup Plasma and urine from healthy volunteers used as controls contained no detectable 5-chlorouracil or 5-bromouracil These observations provide compelling evidence that the inflammatory response in humans involves pyrimidine chlorination and bromination Collectively, our results demonstrate that halogenation of pyrimidines is a physiological process and not a reaction confined to the chemist’s bench Phagocyte Peroxidases as a Source of Interhalogen Compounds Although oxidation of chloride by myeloperoxidase is well documented, both human neutrophils and eosinophils preferentially brominate uracil and deoxycytidine in the presence of physiological chloride and bromide concentrations [30] We resolved this seemingly contradictory observation by showing that reagent HOCl and bromide generate brominating intermediates at plasma concentrations of halide ion Taurine, a potent HOCl scavenger, inhibited this pathway but did not affect bromination by HOBr It also inhibited bromination of nucleobases and nucleosides by both the myeloperoxidase system and activated neutrophils These experiments suggest that oxidation of bromide by myeloperoxidase-derived HOCl might be a significant mechanism for generating brominating agents in vivo Bromide and HOCl might react to form interhalogen compounds, which are combinations of different halogens (XXn¢) Both binary (BrCl, IBr, and ICl) and ternary (ICl3) interhalogens have been characterized One pathway for their formation requires hypohalous acid (HOX) and halide ion (X¢ –) HOX + H+ + X¢ – a XX¢ + H2O (5) HOCl then reacts with bromide to form the interhalogen gas BrCl, itself a potent brominating agent [80] HOCl + Br– + H+ Ỉ BrCl a HOBr + Cl– + H+ (6) The redox potentials of chloride and bromide make this reaction essentially irreversible.Anions of interhalogens and polyhalides are also known; they include Cl3–, Br–3, Br2Cl–, and BrCl2– [81] Interhalogens are extremely corrosive species that attack a wide range of compounds To determine whether BrCl might play a role in bromination by myeloperoxidase, we sparged a reaction mixture containing the HOCl-Br– or the 210 J P Hendersen and J W Heinecke Fig A – C Mass spectrometric detection of 1-bromo-2-chlorocyclohexane (A) produced by HOCl-bromide (B) and the myeloperoxidase-H2O2-chloride-bromide system (C) (Figure reproduced with permission from the Journal of Biological Chemistry [30]) myeloperoxidase-H2O2-Cl–-Br– system with nitrogen gas that was subsequently passed through cyclohexene [30] Mass spectrometric analysis of the resulting solution detected an ion with the expected mass-to-charge ratio, GC retention time, and isotopic abundance of 1-bromo-2-chlorocyclohexane (Fig 5) Because cyclohexene is an aprotic, non-polar solvent that should not contain halide ions under these conditions, its bromination cannot involve a backsided nucleophilic attack of a bromonium ion intermediate by free Cl– Instead, bromination is likely to involve attack on the double bond by [Br+ – Cl–] derived from molecular BrCl Detecting 1-bromo-2-chlorocyclohexane therefore provides strong evidence that HOCl and myeloperoxidase generate the interhalogen gas BrCl Although interhalogen compounds have not previously been invoked in living organisms, our observations strongly suggest that myeloperoxidase and, by extension, human neutrophils generate the interhalogen gas bromine chloride Thus, production of molecular halides and interhalogen compounds by phagocyte peroxidases might be a physiologically relevant pathway for generating oxidants (Fig 6) To determine if myeloperoxidase helps generate brominating agents in vivo, we determined levels of 3-bromotyrosine (an established marker of amino acid bromination by eosinophil peroxidase) in inflammatory fluid from normal mice and mice lacking functional myeloperoxidase by mass spectrometry [70] The myeloperoxidase-deficient mice produced 60 % less 3-bromotyrosine than the normal mice, suggesting that myeloperoxidase provides one pathway for bromination during inflammation Myeloperoxidase and Eosinophil Peroxidase: Phagocyte Enzymes for Halogenation in Humans 211 Fig Generation of molecular halides and interhalogen compounds by HOCl and HOBr Ul- traviolet absorption spectrum of solutions following addition of 100 µM HOCl to 0.1 N HCl, 100 µM NaBr; 0.1 N HCl, 10 mM NaBr; or 0.1 N HBr, upper panel The observed absorption maxima at 232, 245, 269 nm are consistent with formation of the interhalogen species BrCl2–, Br2Cl–, and Br3– respectively These results support the conclusion that eosinophil peroxidase (EPO) and myeloperoxidase (MPO) generate interhalogens at physiological halide concentrations, lower panel Chemical Mechanisms of Bromination by Phagocytes Eosinophil peroxidase uses the peroxidase catalytic cycle to oxidize bromide to HOBr [26–28] HOCl also reacts with bromide to generate brominating intermediates that are in equilibrium with HOBr and BrCl [30] Under physiologically plausible conditions, HOBr and other brominating agents halogenate aromatic compounds more effectively than HOCl Indeed, eosinophil peroxidase readily halogenates L-tyrosine and pyrimidines in quantitative yields [31, 32, 34] HOBr, the initial brominating oxidant released by eosinophil peroxidase, also rapidly reacts with primary amines to form bromamines Rather than being inert products, bromamines are equally or more reactive than HOBr toward biomolecules This suggests that microenvironments high in primary amines might concentrate reactive bromine in vivo 212 J P Hendersen and J W Heinecke Although HOBr has a lower oxidation potential than HOCl, it may be more reactive in some instances because it can produce higher order molecular halogens (Fig 6) [81] HOBr + nX– + H+ a BrXn (7) Intermediates such as Br2 and BrCl are much more effective at brominating aromatic compounds than is HOBr itself [82] Moreover, Br2 and BrCl are in equilibrium with HOBr by reactions that require bromide and chloride [80] HOBr + Br– + H+ Ỉ Br2 + H2O (8) HOBr + Cl– + H+ Ỉ BrCl + H2O (9) It is thus possible that stronger oxidants such as Br2 or BrCl derived from HOBr (or HOCl) in the presence of physiological concentrations of chloride and bromide are involved in brominating tyrosine and pyrimidines Conclusions The demonstration of links between phagocytes and oxidative damage to amino acids and nucleic acids implicates myeloperoxidase and eosinophil peroxidase in host defense mechanisms and tissue injury The detection of the 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267, 269 Acetylene 21 Acid rain Additives 23, 46, 87, 270, 271, 274, 282 Agriculture 131, 134 Air pollution 9, 30, 110, 176, 182–184, 186, 203 Air pollution control act 183, 186 Air quality 73, 110, 116, 130, 177, 179, 183, 185, 186, 191, 192, 195, 203 Air-fuel mixture 22, 26–28, 30, 35, 39, 51, 74, 257 Air-Fuel Ratio (A/F) 20, 25, 27, 39, 44, 209, 263 Air-Toxic Components 266 Alcoholes 21, 105, 179, 279, 281, 282 Aldehydes 21, 179 Alkaline 45 Alternative fuels 11, 105, 276, 277, 284, 285 Alternative propulsion systems 19, 25, 91, 101, 283, 287 Aluminium (Al) 166, 167, 170 AMA (Automobile Manufacturer Association) 222 Ammonia (NH3) 46, 83 Anthropogenic greenhouse effect 118, 120 Anthropogenic sources 114, 120, 124, 129, 131, 134, 227 Aromatics 21, 23, 211, 261–264, 267, 269, 270, 274 Arrhenius 19 Automobile 6, 7, 9, 10, 284 Auto-Oil Programm 262, 266 B Baiersbronner Programm 203 Barium oxide (BaO) 45 Benzene 113, 266, 267, 269, 270 Bio-fuels 280–283 Biomass 105, 124, 277, 279, 280–282 Boiling curve 257, 258 Butane 277–279 C C/H ratio 23, 270, 279, 287 Cadmium (Cd) 165, 170 CAFE (Corporate Average Fuel Economy) 231, 232 California Air Resources Board (CARB) 95, 177, 178, 185, 193, 224, 236, 283 California test 209 Carbon (C) 22, 73, 281 Carbon canister 223 Carbon dioxide (CO2) 9, 13, 20, 38, 40, 41, 71, 81, 105, 113, 115, 116, 118, 121, 146, 151, 220, 227, 229, 233–235, 250, 258, 262, 266, 267, 271, 272, 275, 277, 279, 281–285 Carbon monoxide (CO) 9, 13, 20, 28, 30, 31, 35, 38, 41, 44, 73, 79, 81, 88, 113, 116, 126–128, 140, 141, 146, 147, 179, 184, 186, 187, 192, 193, 195, 196, 198–202, 205, 209, 214, 216, 219, 224, 239, 245, 263, 267, 274, 278, 282 Carburetor 27, 221–223, 268, 269 Catalyst 36, 37, 38, 88, 144, 184, 191, 203–205, 218, 236, 245, 273, 282 Cerium (Ce) 87 Cetan index 260 Cetane number 50, 258, 260, 264, 266, 269, 274, 282, 284, 287 Chamber Diesel engine 52 Charge turbulence 20, 34 Chlorofluorocarbons (CFCs) 124 Chromium VI (CrVI) 165, 170 Clean air act 113, 183, 184, 185, 195–197, 262 Clean fuels 179, 185, 270, 275, 287 Climate change 9, 233, 266 Closed crankcase ventilation 202 CO2 equivalent 119 290 Combustion 18, 20, 22, 27, 33, 50, 51, 74, 75, 91, 93, 94, 260, 275, 282 Combustion chamber 20, 22, 25, 30, 32–34, 37, 43, 50, 52, 54, 74, 75, 89, 93, 94, 260, 270 Combustion engine 22, 30, 268 Combustion products 20, 261, 277, 281 Commercial vehicle 110, 121, 137, 138, 147, 151, 152, 159, 160, 164 Common Rail 57, 59, 63, 65, 77, 80, 87, 88 Compression ratio (CR) 33, 34, 53, 69, 74, 258, 259 Compression stroke 25, 27, 34 Conformity of production (COP) 177, 178, 180 Continuously regenerating trap (CRT) 87, 88 CRC (Coordinating Research Council) 222 CVS (constant volume sampler) 211, 214, 219 Cylinder 20, 21, 30, 31, 33, 36, 51, 52, 79 D DeNOX catalyst 44–46, 82, 272 Deposition 115 Deposits 33, 115, 270, 271 Design parameters 33 Diesel engines 19, 21–23, 26, 27, 30, 48, 54, 103, 137, 140, 145, 180, 184, 185, 192, 195–197, 199, 200, 205, 211, 214, 229, 233, 236, 238, 239, 241, 249, 256–258, 260, 261, 266, 271, 273, 274, 277, 282, 284 Diesel fuel 19, 241, 244, 256, 258, 260, 266, 269, 271, 275, 276, 283, 284 Diffusion flame 23 Dimethyl Ether (DME) 279, 280 Dinitrogen monoxide (N2O) 118, 125 Direct injection 43, 50, 63, 75, 269, 270, 272 Direct injection Diesel 52–54, 63, 65, 71, 200, 239, 244, 266, 272 Distributor pump 57, 65 DOE (Department of Energy) 232, 283 DOT (Department of Transportation) 232 Driving cycle 209, 211, 214, 217, 218, 230 Dual-bed catalyst 38 Dumping 164, 165, 167, 171 E ECE – Regulation 202–204, 219, 245, 250 ECE test 35, 37, 73, 219 EEC – Commission 188, 201–205, 245, 269 Electric batteries 91, 95, 180 Electric energy 95, 101 Electric motor 95, 97, 101 Electric vehicle 95, 180, 182, 234 Emission 9, 74, 115, 138, 176, 183, 188 Subject Index Emission regulations 35, 88, 89, 184, 185, 187, 188, 190, 191 Emission standards 35, 38, 141, 191, 195, 198, 201–204, 209, 211, 218, 224, 238, 239, 245 Emission testing 183, 192, 209, 214, 216, 217 End of life vehicles (ELV) 163, 165, 166 Energy 3, 4, 9, 48, 50, 95, 115, 164, 167–169, 257, 274–276, 280, 281, 283, 284 Engine 3, 9, 160, 179, 185, 284, 285 Engine control 27, 62, 80, 271 Engine external measures 35, 36 Engine internal measures 30, 35, 41, 74, 88, 239 Environment 3, 8, 138 Environmental audits 171 Environmental friendly vehicle 284 Environmental management and auditing system (EMAS) 171 Environmental protection 9, 185 Environmental protection agency (EPA) 178, 184, 185, 192, 222, 230, 239, 268, 274 Ethane 277, 278 Ethanol 103, 277, 281–283, 285 EU3 – Emission Standard 73, 82, 88, 144, 151, 199, 219, 236, 245, 246, 267 EU4 – Emission Standard 73, 77, 146, 152, 178, 183, 199, 206, 245, 246, 267, 272 European stationary cycle (ESC) 245, 246 European transient cycle (ETC) 245 EUROPIA (European Petroleum Industry) 262 Evaporative emission 52, 117, 177, 179, 184, 220–222, 224, 227, 237, 238, 250, 258, 264, 270 Exhaust after-treatment 9, 36–38, 43–46, 74, 81, 83, 88, 89, 191, 197, 239, 263, 268, 271, 274, 284 Exhaust gas 8, 9, 20–23, 31–33, 116, 175, 179, 204, 217, 250, 264, 270 Exhaust gas emission 30, 33, 34, 50, 51, 67, 68, 73, 74, 93, 94, 211, 214, 227, 230, 238, 261, 262, 273 Exhaust pipe 37, 160 Exhaust port 36 Exhaust-gas recirculation (EGR) 36, 38, 55, 63, 77, 79, 88, 89, 236, 239, 245, 270 F Federal standards 192, 195, 222, 223, 239 Federal test procedures 209, 224 Ferocene 87 FID (flame ionization detection) 211, 214 Flame 20, 22 291 Subject Index Flexible fuel vehicle 185, 282 Fluff 166–168 Fly-wheel accumulators 91, 96 Forest decay Formaledehyde (HCHO) 179, 197, 224, 266, 267, 279 Fossil fuels 266, 276, 277, 280 Four stroke 54, 68, 91, 94, 97 Fuel 19, 20, 22, 23, 25, 74, 177, 179, 185, 186, 204, 250, 256–258, 261, 266–268, 274, 275, 284, 285 Fuel cells 91, 97, 101–103, 234, 283, 287 Fuel consumption 9, 11, 12, 27, 28, 30, 32, 34–36, 40, 41, 43, 51, 55, 65, 67, 68, 71, 93, 141, 220, 227, 229, 230, 234, 239, 241, 258, 259, 266, 267, 271, 275, 277, 284 Fuel injection 48, 57, 59 Fuel vapors 22, 25 G Gas guzzler 232 Gas to liquid (GTL) 279 Gas turbine 91, 93 Gasoline 19, 25, 103, 185, 203, 256–258, 269, 273, 275, 276, 279, 282–284, 287 Gasoline/air mixture 25 Gasoline direct injection (GDI) engines 43 Gasoline engine 19, 21, 22, 25, 27, 34, 40, 41, 103, 141, 145, 185, 195, 198, 199, 204, 205, 214, 217–219, 236, 256, 257, 261, 266, 270, 279 Global warming effect 227, 229, 234 Glow plugs 54 Greenhouse effect 9, 113, 115, 116, 118, 120, 152, 266 Greenhouse gases 11, 118, 120, 145, 146, 152, 227, 233, 282 GRPA (Group de Rapporteurs sur la Pollution de l’Air) 202, 204 H Halogenated hydrocarbons 115, 118, 124 Heavy duty vehicles (HDV) 238, 239, 241, 244–246, 249 Heavy methals 165 Helium (He) 93 Heterogenous air fuel mixtures 43, 51, 73, 81, 257 Highway cycle 230 Homogenous air/fuel mixtures 43 Homogenous diesel combustion 80 Hybrid drive 71, 97, 234 Hydrocarbons (HC) 9, 13, 19–21, 23, 28, 35, 36, 73, 79, 81, 88, 97, 113, 116, 117, 140, 141, 147, 152, 177, 184, 186, 187, 192, 193, 196, 198–200, 205, 209, 211, 214, 219, 223, 224, 239, 245, 261, 263, 264, 267, 271, 274, 278 Hydrogen (H2) 93, 99, 101, 102, 234, 277, 281, 283, 285, 287 I Ignition 32 Ignition delay 22, 260 Ignition timing 27, 32, 33, 39, 198 Immission 114, 115, 128, 130, 132, 137, 158 Injector nozzle 59, 62, 74, 75, 271, 274 Injection pressure 52 Injection system 75, 76, 80, 89 Inlet manifold 55 Inline pump 57 Inspection and maintenance (I/M) 178 Intake manifold 27, 33, 34, 39, 43, 65 Intake ports 53, 65 Intake stroke 25, 34 Internal combusiton engine 18, 91, 256, 268, 278, 280, 282–284, 287 In-use testing 178 Iron (Fe) 163, 166, 167, 170 ISO 14001 171 K Ketones 21, 179 Knock limit 39 Knocking combustion 34, 258, 259, 270 Kyoto 11, 227, 229, 234 L LA4-cycle 191, 211, 217 Lambda 27, 28, 30, 80, 82, 130 Lambda probe 39 LDT (light duty trucks) 232 LDV (light duty vehicles) 232 Lead (Pb) 38, 113, 165, 166, 170, 186, 204, 218, 273 Lead-acid batteries 95 Lean burn 34, 36, 41, 43–46, 73, 81, 82, 84, 272 Lean limit 32, 34, 36, 41 Lean mixture 20, 31, 32, 34, 35, 38, 40, 41, 43, 46, 205 Leer engine 94 Life cycle assessment (LCA) 171, 274, 275 Limites exhaust gas components 113 Liquid petroleum gas (LPG) 277, 279, 285 Low emisison vehicle (LEV) 179, 180, 193, 194, 224, 244 Lubricating oil 22, 23, 54 292 M Marine diesels 67, 68, 89, 91 Mean effective pressure (pme) 27 Mercury (Hg) 165, 170 Methane (CH4) 115, 118, 121, 146, 179, 192, 277, 278 Methanol (CH3OH) 102, 179, 185, 277, 279, 283, 285, 287 Methyl bromide (CH3Br) 124 Methyl chloride (CH3Cl) 124 Methyl esters 105 Mineral oil 19, 102, 256, 257, 276, 283 Misfiring of combustion 32 Mixture control 22, 39 Mobility 5, 6, 9, 110 Motor vehicle emissions group (MVEG) 249 Multi Point Injection (MPI) 269 N National ambient air quality standards (NAAQS) 178 Natural gas (LNG, CNG) 102, 277–279, 283, 285 Natural sources 114, 120, 121, 125, 134, 227 Naturaly aspirated engines 29 Nature 1, 3–5 NDIR (Non dispersiv infra red) 209, 211, 214 NEDC (New European Driving cycle) 217, 219, 220 Nicolaus Augustus Otto 25 Nitrates 45 Nitrogen (N2) 20–22, 38, 46, 114 Nitrogen dioxide (NO2) 22, 38, 116, 117, 130, 131 Nitrogen monoxide (NO) 22, 38, 73, 116, 117, 130, 131 Nitrogen oxides (NOX) 9, 13, 20, 21, 28, 30, 31, 35, 36, 44, 68, 73, 75, 76, 88, 113, 117, 125, 130–132, 140, 141, 146, 147, 152, 177, 179, 180, 184, 187, 192, 193, 196–200, 205, 211, 214, 224, 229, 233, 239, 244, 245, 261, 263, 264, 267, 274, 283 Nitrous oxide (N2O) 22, 44, 115, 125, 126, 146 Noble metal catalyst 38, 41, 44, 45, 271 Noise 8, 9, 50, 55, 63, 67, 68, 74, 158–160 Non methane hydrocarbons (NMHC) 129, 130, 146, 239 Non methane organic gases (NMOG) 118, 179, 180, 194, 197, 224 Non-ferrous metals 166, 167 Non-selective catalyst reaction (NSCR) 83 NOX storage catalyst 45, 46, 83, 84, 272 Subject Index O Octane number (ON) 258, 259, 269, 274, 282, 283, 287 Octane requirement 32, 259, 284 Off-road vehicles 127 Olefins 21, 23, 211, 261, 270 On board diagnostic (OBD) 88, 178, 184, 220, 224, 236–238, 246, 249, 250, 273 Operating parameters 30, 74 Organic fuels 22 Organis compounds 177, 179 Otto cycle 26, 92 Otto engine 19, 25, 27, 30, 34, 41, 141, 218, 257, 258, 264, 272, 277, 284 Oxidation catalyst 38, 41, 44, 63, 81, 82, 87, 88, 245, 272 Oxigen (O2) sensor 39, 45, 81, 196, 236, 262, 271, 273, 279 Oxygen (O2) 2, 20–22, 31, 99, 101, 261, 273, 282 Ozone (O3) 117, 118, 144, 151, 177, 179 Ozone formation potential (OFP) 117, 118, 144, 151, 152, 179, 266 Ozone hole Ozone layer 115, 116 Ozone smog Ozone-precursor 118, 179 P Palladium (Pd) 38, 39 Paraffins 21, 23, 211, 261, 283 Partial zero emission vehicles (PZEV) 180, 182 Particle filter 81, 84, 87, 89, 197, 214, 241, 245, 272 Particulate matter (PM) 13, 22–24, 73, 76, 79, 88, 117, 134, 147, 180, 184, 186, 192–194, 196, 199, 200, 205, 214, 224, 233, 239, 241, 244, 250, 264, 267, 271, 273, 274, 282 Passenger cars 6, 9, 25, 48, 88, 110, 113, 121, 137, 138, 140, 144, 145, 158, 164, 230, 233, 236, 239 Petrol engine 48, 63 Phosphorus (P) 38 Photooxidants 113, 195 Photosynthesis 105, 116, 281 Piston 18, 21, 50, 51, 53, 54, 91, 92 Plastic 164, 166–168, 170 Platinum (Pt) 38, 101, 103 Pollutants 9, 116, 261, 266, 268, 274, 277, 284 Polyciclic aromatic hydrocarbons (PAH) 266, 267, 269, 270 Portliners 36, 37 Subject Index Power output 27, 29, 32, 34, 36, 39, 43, 62, 65, 67–69, 74, 259, 278 Power units 15, 25, 53, 91 Pre-catalyst 77 Pre-chamber engines 63, 75, 200, 266 Precious metals 83 Pre-injection 65, 76, 77, 80 Propane 277–279 Propulsion system 25, 91 R Rapseed methyl ester (RME) 282 Reciprocting piston engine 25, 91, 93, 94, 97 Recycling rate 165, 169 Recycling 125, 163, 164, 166–171, 281 Reduction catalyst 38, 241 Reformer 103, 283 Reformulated gasoline 262, 282 Regulated emissions 184, 204, 262, 270, 271 Renewable energy 234, 280–282 Residual gases 20, 36 Rhodium (Rh) 38 Rich mixture 31, 38 Road traffic 7, 8, 10, 12, 110, 112, 113, 121, 127, 128, 134, 137, 158, 284 Road transport 48 Rotary-piston engine 92, 93 Rudolf Diesel 48 Running losses 224 S Saturated hydrocarbons 261, 267, 270, 283 Scrap 163, 166, 167 Secondary air injection 36–38 Seiliger Process 48 Selective catalyst reaction (SCR) 83, 84, 88, 89, 241 Self ignition 22, 48, 50, 51 257, 264 Seven (7)-mode cycle 192, 211, 216 SHED (Sealed Housing for Evaporative Emission Determination) 222–224 Shredding 166–168 SiNOX 83, 84 Smog 176, 177, 211 Smoke 22, 80, 176, 186, 200, 214, 241, 271 Society of automotive engineers (SAE) 230 Solvents 129 Soot 22, 23, 73, 81, 137, 186, 246, 271, 279 Spark ignited engine 53, 63, 69, 71, 74, 82, 257 Specific fuel consumpiton 27 Specific work (we) 27, 259 Squish 34 293 Steam engine 18, 48, 91, 93, 94 Stirling engine 91, 93 Stoichiometric mixtures 20, 26, 30, 31, 39, 41, 43–45 Stratified charge engine 43 Sulfates 23, 73, 82, 273 Sulfur 21, 23, 38, 46, 73, 84, 113, 239, 241, 244, 267, 269, 272, 274, 282–284, 287 Sulfur hexafluoride 118 Summer smog 112 Super ultra low emission vehicle (SULEV) 180, 194, 224, 227 Sustainable development 171 Swirl 34, 53, 63, 65, 74, 79, 88 Swirl chamber 75 T 10-mode test 200 Technical guideline for air quality 129, 134, 137 Telematic 12 Test procedure 199–201 Thermal efficiency 94 Thermal reactor 36, 37 Three-way catalyst 38, 39, 41, 43–45, 82, 103, 114, 126, 141, 184, 196, 199, 217, 262, 263, 273, 279 Torque 30, 32, 34, 41, 43, 69 Toxicity 116 Trace gases 113, 115, 118 Trace substances 115, 116 Traffic 6–9, 11, 12, 115, 160, 217, 268, 275 Traffic management 11 Transport 5, 7, 115, 227, 233, 283 Transportation 5, 11, 12, 15, 18, 19, 48, 284, 285 Trucks 6, 67 Tumble 34 Turbocharged engines 30, 55, 56, 63, 69, 77, 88 Two-stroke 54, 68, 91, 92, 130 U Ultra low emission vehicle (ULEV) 179, 180, 193, 194 UBA (Umweltbundesamt, German Environment Agency) 203 Unburnt hydrocarbons (HC) 20, 21, 23, 30, 31, 41, 83, 113, 282 Underfloor catalyst 77 UNECE 130, 131 Unit injector 57 Unregulated exhaust gas components 113, 250, 266, 270 Urea 46, 83 294 UTAC (Union Techniques de l’Automobile du Motorcycle et du Cycle) 218 Utility vehicle 67, 87, 89 V Valve timing 33 Vapor pressure 264 VDA ( Association of German Automobil Makers) 146, 201, 202, 217, 218, 229 VDI (Association of German Engineers) 201, 218 Vegetable oil 277, 280–282 Volatile organic gases 118, 130 W Wankel engine 91–93 Waste 164, 167, 168, 171 Subject Index Water steam (H2O) 20, 281 Water vapor (H2O) 44, 81, 99, 101, 102, 105, 114, 115, 120, 281, 283 Well to wheel analysis 274 WHO (World Health Organisation) 129, 134 Working cylce 25, 41, 51 Working medium 94 World Wide Fuel Charter (WWFC) 269–271, 284 Z Zeolites 45, 46, 83 Zero-emission vehicle (ZEV) 95, 179, 180, 182, 185, 193, 194, 206, 224, 227, 250 ... objectives of Environmental Chemistry must be the study of the environment and of natural chemical processes which occur in the environment A major purpose of this series on Environmental Chemistry, ... D Gruden The Handbook of Environmental Chemistry Vol 3, Part P (2003): 1–15 DOI 10.1007/b 10445 The Diversity of Naturally Produced Organohalogens Gordon W Gribble Department of Chemistry, Dartmouth... encouraged to offer suggestions and advice as to future editions of “The Handbook of Environmental Chemistry Most chapters in the Handbook are written to a fairly advanced level and should be of interest