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MICROBIAL METHYLATION and VOLATILIZATION of ARSENIC By MICROBIAL METHYLATION AND VOLATILIZATION OF ARSENIC by CORINNE RITA LEHR B. Sc., University of Calgary, 1994 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE STUDIES (Department of Chemistry) We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA March 2003 © Corinne Lehr, 2003 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of C.()e<P^'f("y The University of British Columbia Vancouver, Canada Date OJ/W h 1 JOC'J ABSTRACT The basis of the "Toxic Gas Hypothesis" of Sudden Infant Death Syndrome (SIDS) is that the microorganisms present on infants bedding materials volatilize sufficient arsenic, antimony or phosphorus from these materials to be acutely toxic to an infant. The volatilization of arsenic by aerobic microorganisms isolated from new sheepskin bedding materials, as well as from materials used by a healthy infant and by an infant who perished of SIDS was examined. Three arsenic-methylating fungi were isolated from a piece of sheepskin bedding material on which an infant perished of SIDS. These fungi form trimethylarsenic(V) species, precursors to volatile trimethylarsine. Their ribosomal RNA PCR products were used to identify the fungi as Scopulariopsis koningii, Fomitopsis pinicola and Penicillium gladioli. S. koningii, as well as two other sheepskin isolates, Mycobacterium neoaurum and Acinetobacter junii are human pathogens which should also be of concern in connection with SIDS. Few microogransism have been shown to methylate antimony. S. koningii methylated the antimony(III) compounds, potassium antimonyl tartrate and antimony trioxide yielding trimethylantimony. P. gladioli and S. koningii volatilized arsenic as trimethylarsine, but only under conditions such that the production of sufficient trimethylarsine to be acutely toxic to an infant is urilikely. These fungi did not volatilize antimony. ii Very little is known about the demethylation of methylarsenicals. One of the sheepskin isolates, Mycobacterium neoaurum, demethylated methylarsenic compounds to mixtures of As(III) and As(V). There was some evidence that MMA(V) is reductively demethylated to As(III) which is then oxidized to As(V). Iodide decreased the demethylation of MMA(V) by M. neoaurum and increased the methylation of MMA(V) by both P. gladioli and S. koningii. The techniques developed for studying the volatilization of arsenic by the lTiicroorganisrns on sheepskin bedding materials were applied to two other environments - garden waste compost and Meager creek hot springs. Composting of garden waste yielded iodomethane. Aerobic incubation of microbial mats and sediment from Meager creek hot springs yielded trimethylarsine and trimethylstibine. iii TABLE OF CONTENTS ABSTRACT ii TABLE OF CONTENTS iv LIST OF TABLES ix LIST OF FIGURES xi LIST OF ABBREVIATIONS xiii ACKNOWLEDGEMENTS xiv Chapter 1 INTRODUCTION 1 1.1 Chemistry of Arsenic 1 1.2 Biological Transformations of Arsenic by Microorganisms 3 1.2.1 Volatilization 3 1.2.2 Mechanism of Arsenic Methylation 4 1.3 Toxicity 7 1.4 Sudden Infant Death Syndrome 9 1.5 Scope of Thesis 12 iv Chapter 2 ANALYTICAL METHODS 14 2.1 Introduction 14 2.2 Materials 16 2.2.1 Reagents 16 2.3 HG-GC-AAS Analysis 17 2.3.1 Introduction 17 2.3.2 Experimental 21 2.3.2.1 Materials 21 2.3.2.2 General HG-GC-AAS Procedure 22 2.3.2.3 Instrumental 23 2.3.2.4 Arsenic Analysis 25 2.3.2.5 As(III)/As(V) Speciation 25 2.3.2.6 Sample Preparation for Antimony Analysis by Solid Phase Extraction....26 2.3.2.7 Antimony Analysis 26 2.3.3 Results and Discussion 27 2.3.3.1 Arsenic Analysis 27 2.3.3.2 As(III)/As(V) Speciation 30 2.3.3.3 Antimony Analysis 30 2.4 Purge and Trap-GC-AAS 33 2.4.1 Experimental 33 2.4.1.1 General Purge and Trap-GC-AAS Procedure 33 2.4.1.2 Purge-and-Trap Flasks 33 2.4.1.3 Preparation of a Trimethylarsine Standard 34 2.4.1.4 Quantification of Trimethylarsine Standard ' 35 2.4.1.5 Quantification of Trhnethylarsine in Sample 35 2.4.2 Results and Discussion 36 2.5 FIA-ICP-MS 37 2.6 GC-ICP-MS 40 2.6.1 Experimental 40 2.6.1.1 Gas Trapping 40 2.6.1.2 GC-ICP-MS General Procedure 40 2.6.1.3 Semi-quantification 44 2.7 Summary 46 Chapter 3 ISOLATION AND IDENTIFICATION OF ARSENIC METHYLATING MICROORGANISMS 47 3.1 Introduction 47 3.2 Experimental 49 3.2.1 Materials 49 3.2.2 Characterization of Sheepskin Bedding Materials 49 3.2.2.1 Analysis of Sheepskin Bedding Materials for Total Arsenic Content 50 3.2.3 Isolation of Aerobic Microorganisms Extant on Sheepskin Bedding Materials 50 3.2.4 Screening of the Isolated Microorganisms for their Ability to Methylate Arsenic 52 3.2.5 Identification of Selected Microorganisms 53 3.2.5.1 Materials Used in the Identification of Microorganisms 53 3.2.5.2 Extraction of Genomic DNA from Selected Isolates 53 3.2.5.3 Polymerase Chain Reaction 54 3.2.5.4 Purification of rDNA PCR Products 55 3.2.5.5 Sequencing Reactions and Isolate Identification 56 3.3 Results and Discussion 58 3.3.1 Arsenic and Antimony Concentration in the Wool and the Skin of Sheepskin Bedding Materials 58 3.3.2 Aerobic Microorganisms Isolated from Sheepskin Bedding Materials 59 3.3.3 Arsenic Methylation by Isolates 65 3.3.4 Identification of Bacteria and Fungi Isolated from Sheepskin Bedding Materials 69 3.3.5 Photographs of Arsenic Methylatmg and Demethylating Microorganisms..72 3.4 Summary 75 vi Chapter 4 METHYLATION AND DEMETHYLATION: INVOLATILE ARSENIC AND ANTIMONY METABOLITES 77 4.1 Introduction 77 4.2 Experimental 79 4.2.1 Time Study of Arsenic Methylation and Demethylation 79 4.2.2 Incubation of S. koningii, F. pinicola and P. gladioli, M. neoaurum with Inorganic and with Methylated Arsenic Species 80 4.2.2.1 Extraction of Inorganic and Methylated Arsenic Species from Biota 81 4.2.3 Incubation of S. koningii, F. pinicola and P. gladioli with Inorganic Antimony Species 82 4.2.4 Incubation of a Mixed Culture of S. koningii, F. pinicola and P. gladioli with As(III) and with MMA(V) 82 4.2.5 Incubation of S. koningii, P. gladioli and M. neoaurum withMMA(V) and Iodide 83 4.3 Results and Discussion 84 4.3.1 Growth Curves of S. koningii and M. neoaurum 84 4.3.2 Time Study of MMA(V) Methylation by S. koningii 88 4.3.3 Arsenic Methylation by S. koningii, P. gladioli and F. pinicola 90 4.3.3.1 F. pinicola 91 4.3.3.2 S. koningii 91 4.3.3.3 P. gladioli 92 4.3.4 Methylation of As(III) and MMA(V) by a Mixed Culture of S. koningii, F. pinicola and P. gladioli 93 4.3.5 Incubation of S. koningii, F. pinicola and P. gladioli with Inorganic Antimony Species 94 4.3.6 Demethylation of Methylarsenic species by M. neoaurum 97 4.3.7 Time Study of MMA(V) Demethylation by M. neoaurum 98 4.3.8 Incubation of M. neoaurum with Inorganic As 102 4.3.9 Incubation of S. koningii, P. gladioli and M. neoaurum with MMA(V) and Iodide 102 4.4 Summary 106 vii Chapter 5 VOLATILIZATION OF ARSENIC 108 5.1 Introduction 108 5.2 Experimental 110 5.2.1 Arsenic and Antimony Volatilization by Fungi Isolated from Sheepskin Bedding Materials 110 5.2.2 Incubation of S. brevicaulis with Sheepskin Bedding Material 112 5.2.2.1 Preparation of Seed Culture of S. brevicaulis 112 5.2.2.2 Preparation of Incubation Flasks 113 5.2.3 Arsenic Volatilization by Composting 114 5.2.3.1 Sampling of Compost Gases 115 5.2.3.2 Analysis of Compost for Arsenic Content 116 5.2.3.3 Compo st Incubation 117 5.2.4 Arsenic Uptake and Volatilization by Biota from Hot Springs of South• western British Columbia 118 5.2.4.1 Meager Creek Hot Springs 118 5.2.4.2 Incubation of Microbial Mats and Sediment 121 5.2.4.3 Aerobic/Anaerobic Incubation of Microbial Mats 123 5.2.5 Clear Creek Hot Spring 125 5.3 Results and Discussion 127 5.3.1 Volatilization of Arsenic by Fungi Isolated from Sheepskin Bedding Materials 127 5.3.2 Volatilization of Arsenic from Sheepskin Bedding Materials by S. brevicaulis 128 5.3.3 Compost 133 5.3.3.1 Analysis of Compost Gases 133 5.3.3.2 Analysis of Compost Incubation Gases 135 5.3.4 Hot Springs of South-western British Columbia 136 5.3.4.1 Volatile Species at Meager Creek Hot Springs 136 5.3.4.2 Microbial Mat and Sediment Incubations 137 5.3.4.3 Aerobic/Anaerobic Incubation of Microbial Mats 139 5.3.5 Clear Creek Hot Spring 141 5.4 Summary 144 Chapter 6 SUMMARY .147 viii LIST OF TABLES Chapter 1 Table 1.1 Some arsenic compounds Chapter 2 Table 2.1 Boiling points of arsenic and antimony hydrides Table 2.2 Operating parameters ICP-MS Table 2.3 Analyte masses (ICP-MS) and dieir relative natural abundance Chapter 3 Table 3.1 Arsenic content (ppb) of sheepskin bedding materials, determined by nitric acid digestion of the materials, HG-GC-AAS analysis of the digests, (SD) Table 3.2 Isolates from New 1 Table 3.3 Isolates from New2 Table 3.4 Isolates from Usedl Table 3.5 Isolates from SIDS 1 Table 3.6 Identification of isolates from sheepskin bedding materials Chapter 4 Table 4.1 Dry biomass of fungi after 28 days of growth with arsenicals (mg) Table 4.2 Percent conversion of starting substrates to methylated products by S.
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