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UNIVERSITY OF STOCKHOLM INSTITUTE OF PHYSICS NEW METALS — A study on the use of and exposure to certain metals and their compounds from a toxicological viewpoint U. BERGQVIST USIP Report 83 - 11 December 1983 NEW METALS A study on the use of and exposure to certain metals and their compounds from a toxicological viewpoint Ulf Bergqvist, with contributions from Foad Vojdani Ghamsari Theoretical Physics, University of Stockholm Vanadisvägen 9, S—113 46 Stockholm, Sweden I'm still confused - but on a higher level USIP Report 83--1 December 1983 - I - LIST OF CONTENTS (IN BRIEF) Page: List of contents (in brief) I List of contents (in details) III Acknowledgements X Disposition of this report XI Introduction 1 Section 1: Exposure to metals and metal compounds Preamble 3-6 Criteria based on total world consumption 7-13 Criteria based on probable increases in world metal consumption 1 4-22 Criteria based on exposure to metal emissions from sources other than metal consumption 23-29 Reconfirmation of metals found interesting in this section 30-33 Summary of section 1 34-38 Section 2: ' 1 e extent of toxicological knowledge and * search on metals and their compounds Preamb c 39-42 The re.://ch activity on toxic effects of metals ,nd metal compounds 43-49 Differe t organisms responses to metal compounds 50-r54 Introciu :• ,ion of new metal compounds in industrial consumption and its toxicological impli- cation 55-60 An es . mate of the quantity of toxicological infor- mation on metal and metal compounds in reviews 61-65 An evaluation of the relevance of available toxico- logical information to present and future industrial consumption of certain metals 66-72 Summar. of section 2 73-80 Section 3- A description of some metals found interesting in this sTudy Preamble 81 Barium 82-88 Cerium 89-93 Cesium 94-97 Gallium 98-110 Lanthanum 111-11 4 Manganese 115-118 Niobium . 119-120 Praseodymium - Lutetium 121-124 - ii - Titanium Yttrium Appendices Appendix 1: The world consumption of metal com- pounds (parameters cons and prog) IV- Appendix 2: The world metal industrial consump- tion related to the total body burden (parameter dose) 13'-- Appendix 3: The world metal industrial consump- tion weighted by the threshold limit values (parameter toxic) 1^G- Appendix 4: The appearance of articles in jour- nals on technical applications of metals (parameter jour) 1 ^'-- Appendic 5: The status of research on catalytic properties of metals (parameter catai) V-.•'.'- (By Foad Vojdani Ghamsari) Appendix 6: Metal content in oil and coal (para- meters oilchem, oilenv, coalcherr. and coalenv) Y-J.J- Appendix 7: Metals connected with acid precipi- tation 1 f •", _ ' Appendix 8: Research activities on toxic effects of metals and metal compounds (parameter res) 1*3 2- Appendix 9: Variations in metal effects on diffe- rent biological systems (parameter spe) "<6"-' Appendix 10: The quantity of review information available on toxic effects of metal com- pounds (parameter rev) •?"- Appendix 11: English names anc chemical symbols of metals 1 91 -•' i;ei e r en c e s - III - LIST OF CONTENTS (IN DETAILS) List of contents (in brief) 1 Li.;t of contents (in details) III Acknowledgements X Disposition of this report XI Introduction 1 Section 1: Exposure to metals and metal compounds 3 Preamble 3 Purpose of this section 3 Prerequisits of criteria definitions 3 Metals considered in this section 4 Exposure interest criteria used 6 Criteria based on total world consumption 7 General purpose 7 Data used 7 Parameters used 7 Fallacies of each parameter definition 9 Results 1U Comments 13 Criteria based on probable increases in world metal consumption 14 General purpose 1 u Prognosis - methods and results 'i k Examples; prognoses for aluminium and beryllium 17 Technical journals - methods and results 19 Research activity of metals as catalysts 20 Comments 21 Criteria based on exposure to metal emissions from sources other than metal consumption 23 General purpose 23 Problems in defining criteria related to these sources of exposure 2 4 Metals as contaminants in oil and coal - methods and problems 2M Metals as contaminants in oil and coal - results and discussion 26 Metals released by acidifying processes - methods and results 28 Comments 29 Reconfirmation of metals found interesting in "this section 30 General purpose 3G Metals interesting due to a high present consurnption 3C - IV - Page: Metals interesting due to a fast (expected) in- crease in world industrial consumption 32 Summary 33 .Summary of section J 3A Fulfilment of purpose 34 Criteria evaluation 34 Results - general description 34 Discussion of results 36 Section 2: Tne extent of toxicological knowledge and research on metals and their compounds 39 Preamble 39 Purpose of this section 39 Criteria for 'interesting' metals in this section 39 Evaluation procedures - step 1 40 Evaluation procedures - step 2 42 Final evaluation 42 The research activity on toxic effects of metals and metal compounds 43 Purpose of this study 43 Methods 43 Results 44 Evaluation of interesting metals 47 Comments 47 Summary 49 Different orRanisms responses to metal compounds 50 General purpose 50 Concept of biological reactivity 50 Detection of biological reactivity 51 Methods 51 Results 52 Evaluation of interesting metals 52 Comments 5 4 Summary 5 4 Introduction of new metal compounds in industrial consumption and its toxicological impli- cation 55 Purpose of this study 55 Criteria for identifying new compounds 55 Fallacies of these criteria 57 Results 58 As: Arsenic compounds used in micro-electronic industry 58 Fe: Certain organic iron compounds 59 Ru: Certain organic ruthenium compounds 59 - v - W: Metallic tungsten and tungsten carbide Zn and Mn: Manganese-ethylenebis (dithiocarba- mate)(maneb) and zinc-ethylenebis (di- thiocarbamate)(zineb) 60 An estimate of the quantity of toxicological infor- mation on metal and metal compounds in reviews 61 General purpose 61 Motivation for this investigation 61 Type of information retrieved 61 Data collection and computation 61 Results 62 Comments 62 An evaluation of the relevance of available toxico- logical linformation to present and future industrial consumption of certain metals 66 Purpose of this investigation 66 Methods 66 Results 70 Summary 70 Summary of section 2 7 3 Fulfilment of purpose 73 Discussion of criteria used 73 Results - general discussion 75 Final evaluation 76 Comments 76 Some general comments on certain research needs (authors view) 78 Section 3: A description of some metals found inte- resting in this study 81 Preamble 81 Purpose of this study 81 Barium 82 The industrial use of barium compounds 82 Toxic effects of insoluble barium compounds (BaS0H, barite) 82 Toxic effects of soluble barium salts 83 Suggestions for further study 84 Some barium references 85 Cerium 89 Industrial use of cerium metal, alloys and com- pounds 89 Toxic effects of cerium metal and alloys (including 'mischmetal') 89 Toxic effects of cerium oxides 89 - VI - Toxic effects of other cerium compounds ( e g halogens) 90 Suggestions for further study 91 Some cerium references 91 Cesium 94 The industrial use of cesium metal and compounds 94 Toxic effects of caustic cesium compounds (CsOH) 94 Toxic effects of noncaustic cesium compounds 95 Suggestions for further study 95 Some cesium references 96 Gallium 98 Gallium chemistry 98 The industrial use of gallium 99 Gallium compounds of major industrial and medi- cal use 100 Gallium exposure in certain industries (authors evaluation) 100 Gallium distribution in the body after industrial exposure (authors evaluation) 101 Toxic effects of gallium in man and other orga- nisms 102 The regulation of gallium in the work environment 103 Author's evaluation of possible toxic effects of gallium in work environments 104 Present research activity on gallium toxicology 104 Summary of some research need 105 Some gallium references 105 Lanthanum 11 1 Industrial use of lanthanum metal, alloys and compounds 11 1 Toxic effects of lanthanum metal and alloys 111 Toxic effects of lanthanum oxide 111 Toxic effects of lanthanum halogens and other compounds 111 Suggestions for further study 112 Some lanthanum references 112 Manganese 115 The industrial use of manganese metal, alloys and compounds 115 Toxic effects of manganese metal or inorganic compounds 115 Toxic effects of organic manganese compounds 116 Suggestions for further study 116 Some references manganese 117 - VII - Niobium 11 9 Industrial use of niobium metal, alloys and compounds 11 9 Toxic effects of niobium metal or alloys 119 Toxic effects of niobium compounds 119 Suggestions for further study 120 Some references niobium 120 Praseodymium - Lutetium 121 The industrial use of lanthanoids other than lanthanum and cerium 121 Toxic effects of Pr and Nd metal and alloys 121 Toxic effects of Pr and Nd oxides 121 Toxic effects of Pr and Nd halogens and other salts 122 Some suggestions for further study 122 Some references praseodymium - lutetium 122 Ti tanium 125 The industrial use of titanium metal, alloys and compounds 125 Toxic effects of titanium metal and inorganic noncaustic compounds 125 The toxic effects of titanium tetrachloride, oxychloride etc 126 Toxic effects of organic titanium compounds 126 Some suggestions for further study 127 Some references titanium 127 Yttrium 129 The industrial use of yttrium metal, alloys and compounds 129 Toxic effects of yttrium metal and alloys 129 Toxic effects of yttrium oxides and other compounds 129 Some suggestions for further study 129 Some references yttrium 130 Appendices