Trace Element Speciation for Environment, Food and Health

by Ebdon, Les; Crews, Helen; Cornelis, Rita; Pitts, Les; Donard, O. F. X.; Quevauviller, Philippe

• ISBN13: 9780854044597
• ISBN10: 0854044590
• Format: Hardcover
• Copyright: 2002-02-01
• Publisher: Royal Society of Chemistry

Summary

The ongoing progress of science has shown that it is important for analytical scientists to determine not only the presence of particular elements, but also their species. There are many fields where this is applicable, and where there are a number of topics to be addressed. Developing separation and measurement systems for the many element species has tested the resourcefulness of analytical chemists over recent decades. A product of the EU sponsored Speciation 21 Network, this book presents a detailed review of the state-of-the-art of speciation issues in the occupational health, food and environment sectors, along with the main conclusions arising from discussions held during expert meetings. Topics covered include mercury and organotin compounds in the environment; factors affecting the health of workers; the importance of speciation of trace elements for health, and subsequent metabolism in the body; analytical methodologies; risk assessment; and legislation. Trace Element Speciation for Environment, Food and Health provides an insight into applied research in the speciation field and how it has become so important in all the fields represented. With its comprehensive coverage, it will be of particular interest to researchers in industry and academia, as well as government agencies and legislative bodies.

Table of Contents

Foreword	v
Philippe Quevauviller
IUPAC Definitions for Terms Related to Chemical Speciation and Fractionation of Elements	ix
Rita Cornelis
List of Abbreviations	xxiii
Contributors	xxv
General Aspects
Accuracy and Traceability in Speciation Analysis	3	(14)
Philippe Quevauviller
Introduction	3	(1)
Accuracy	4	(1)
The Traceability Concept as Applied to Speciation	5	(10)
Stated References for Speciation Analysis	6	(1)
Generalities	6	(1)
CRMs as Stated References	6	(1)
Reference to Well-defined Species	7	(1)
Reference Methods	8	(1)
Significance of the Unbroken Chain of Comparisons for Speciation	9	(1)
Traceability Links	9	(1)
Extraction Recoveries	9	(1)
A Particular Case- Distillation	9	(1)
Derivatisation Yields	10	(1)
Separation	11	(1)
Detection	12	(1)
Calibration	13	(1)
Measurement Uncertainties	13	(1)
Conclusions	14	(1)
References	15	(2)
Quality Control in Speciation Analysis	17	(34)
Erwin Rosenberg
Freek Ariese
Introduction	17	(3)
General Aspects of Quality Control in Speciation Analysis	20	(1)
Sampling Conservation and Storage	20	(2)
Subsampling	22	(1)
Extraction/Digestion	23	(3)
Derivatisation	26	(6)
Separation	32	(2)
Detection	34	(1)
Calibration	35	(4)
Calculation of Results and Reporting	39	(2)
Achieving Quality in Speciation Analysis on a Daily Basis	41	(5)
Conclusions	46	(1)
References	46	(5)
Sample Treatment and Storage in Speciation Analysis	51	(30)
J.L. Gomez-Ariza
E. Morales
I. Giraldez
D. Sanchez-Rodas
Introduction	51	(2)
Sample Treatment	53	(16)
Species Pre-treatment and Extraction	53	(1)
Solvent Extraction Procedures	54	(1)
Organotin Species	54	(1)
Organolead Species	55	(1)
Organomercury Species	55	(1)
Organoarsenic and Organoantimony Species	56	(1)
Organoselenium Species	56	(1)
Basic and Enzymatic Hydrolysis	57	(1)
Supercritical Fluid Extraction (SFE)	58	(1)
Accelerated Solvent Extraction (ASE)	58	(1)
Solid Phase Extraction (SPE) for Species Separation and Pre-concentration	59	(1)
Chelating Sorbents	59	(1)
Columns and Cartridges	60	(1)
Derivatization	61	(1)
Hydride Generation	61	(2)
Alkylation Reactions	63	(1)
Aqueous Alkylation	64	(1)
Fast Extraction Methods	65	(1)
Microwave-assisted Sample Preparation	65	(1)
Solid Phase Micro-extraction (SPME)	66	(1)
Fully Automated Systems for Speciation	67	(1)
Other Fast Methods	67	(1)
Speciation of Volatile Species	68	(1)
Sample Preservation and Storage	69	(3)
Mercury Species	69	(1)
Arsenic Species	70	(2)
Selenium Species	72	(1)
Acknowledgement	72	(1)
References	72	(9)
Aspects of the Threshold Limit Concept	81	(12)
Bernd Neidhart
Introduction	81	(2)
Analytical aspects	83	(2)
Importance of Speciation	83	(1)
Sampling	83	(1)
Time-dependent Inhomogeneous Populations	84	(1)
Spatially Inhomogeneous Populations	84	(1)
Analytical Quality Criteria	85	(1)
Legal Aspects	85	(4)
General View	86	(1)
Legal Reasoning for TLVs	86	(1)
Legal Reasoning and Analytical Reality	87	(1)
Legal Certainty	87	(1)
More Rapid Judgement	88	(1)
Public Acceptance	88	(1)
Suggestions for Dealing with TLVs	89	(2)
Conclusion	91	(1)
References	92	(1)
Considerations of the Legislative Aspects of the Data Quality Requirements in Trace Element Analysis	93	(22)
Roger Wood
Helen Crews
Introduction	93	(1)
Legislative Requirements	93	(4)
The European Union	94	(1)
The Council Directive on the Official Control of Foodstuffs	94	(1)
Directive on Additional Measures Concerning the Control of Foodstuffs	94	(1)
Codex Alimentarius Commission	95	(1)
Guidelines for the Assessment of the Competence of Testing Laboratories Involved in the Import and Export Control of Foods	95	(1)
CAC Criteria for Laboratories Involved in the Import and Export Control of Foods	96	(1)
An Example of National Requirements for Food Chemical Surveillance	97	(1)
UK Food Standards Agency Surveillance Requirements	97	(1)
Consequence of the Legislative Requirements	97	(1)
IUPAC/ISO/AOAC Internal Quality Control (IQC) Guidelines	98	(1)
Quantitative Chemical Analysis	98	(1)
Harmonised Guidelines for the Use of Recovery Information in Analytical Measurement	99	(1)
In-House Method Validation	99	(2)
Existing In-House Method Validation Protocols and Measurement Uncertainty Standards/Guides	100	(1)
Criteria Approach For Evaluating Acceptable Methods of Analysis for Codex Purposes	101	(2)
Method Criteria	102	(1)
Conclusions	103	(1)
References	103	(12)
Appendix: Example of Application of Criteria	105	(10)
Environment
Metal Speciation for Improved Environmental Management	115	(12)
O. F. X. Donard
The Occurrence and Importance of Metal Species in the Environment	115	(2)
Analytical Responses and Legislative Implications	117	(3)
Existing Analytical Responses and Current Needs	120	(4)
Current Status and Future Needs	124	(2)
References	126	(1)
Mercury - Do We Know Enough?	127	(15)
Milena Horvat
Introduction	127	(1)
Chronology of Mercury Investigation	127	(2)
The Role of Analytical Chemistry	129	(2)
Mercury as a Global Pollutant	131	(1)
The Mercury Cycle	132	(2)
Mercury Toxicity	134	(4)
What is Safe'?	138	(1)
Conclusions	139	(1)
References	139	(3)
Organotin Compounds in the Environment: Still a Critical Issue	142	(34)
O. F. X. Donard
G. Lespes
D. Amouroux
R. Morabito
General Background	142	(2)
Organotins in Industrial and Domestic Products	144	(2)
Occurrence of Organotins in the Environment	146	(12)
Environmental Behaviour of Organotin Compounds	146	(1)
Marine Environments	146	(3)
Freshwater and Terrestrial Environments	149	(1)
Organotin Compounds in Marine Environments and Related Questions	150	(5)
Organotins in Freshwater and Terrestrial Ecosystems	155	(3)
Increasing Awareness of Biological Effects of Organotin Compounds	158	(2)
Critical Considerations with Respect to Determination and Environmental Monitoring Strategies	160	(7)
Sample Preparation	160	(1)
Sample Treatment	160	(1)
Extraction	161	(1)
Derivatisation	162	(1)
Sample Collection	163	(1)
Sampling	163	(1)
Choice of Samples	164	(1)
Number of Samples	165	(1)
Sample Collection	165	(1)
Spatial Variability	165	(1)
Temporal Variability	166	(1)
Sample Storage	166	(1)
Environmental Policies and Regulations	167	(1)
Policy Evolution	167	(1)
Industrial Responses	167	(1)
Conclusions	168	(2)
Acknowledgement	170	(1)
References	170	(6)
An Environmental Case History of the Platinum Group Metals	176	(12)
Sebastien Rauch
Gregory M. Morrison
Introduction	176	(1)
Natural Occurrence	176	(1)
Uses of Platinum Group Metals	177	(1)
Platinum Group Metal Research	178	(1)
The Analytical Challenge	179	(1)
Speciation of Platinum Emission	180	(1)
Platinum Speciation in the Environment	181	(2)
Platinum Group Metals in Man	183	(2)
Future Research	185	(1)
References	185	(3)
Speciation in the Frame of Environmental Bio-monitoring-Challenges for Analytical and Environmental Sciences	188	(8)
Hendrik Emons
Environmental Bio-monitoring	188	(1)
Bio-indicator Matrices	189	(1)
Total Procedures for Speciation	190	(3)
Future Needs	193	(2)
Acknowledgement	194	(1)
References	195	(1)
Arsenic Speciation in the Environment	196	(15)
Peter Fodor
General	196	(1)
Arsenic Sources	196	(2)
Arsenic in Soils and Sediment	198	(1)
Soils	198	(1)
Sediments	199	(1)
Microbial Activity	199	(2)
Arsenic in the Atmosphere	201	(1)
Arsenic in Natural Waters	202	(2)
Terrestrial Organisms	204	(2)
Plants	204	(1)
Animals Humans	205	(1)
Marine Environment	206	(1)
Seawater	206	(1)
Marine Sediment	206	(1)
Marine Algae	207	(1)
Marine Animals	207	(1)
References	207	(4)
Rapid Tests- A Convenient Tool for Sample Screening with regard to Element speciation	211	(12)
Martina Unger-Heumann
Introduction	211	(1)
Definition of Rapid Test	211	(3)
Reasons for the Use of Rapid Tests	214	(1)
Rapid Tests for Element Speciation	215	(2)
Nitrogen	215	(1)
Phosphorus	215	(1)
Sulfur	216	(1)
Chlorine	216	(1)
Chromium	217	(1)
Iron	217	(1)
Fields of Application	217	(2)
Environmental Analysis	217	(2)
Food Analysis	219	(1)
Conclusion	219	(1)
References	219	(4)
Food
The Importance of Trace Element Speciation in Food Issues	223	(5)
Helen M. Crews
Introduction	223	(1)
Bioavailability	223	(3)
Iron	224	(1)
Selenium	224	(1)
Arsenic	225	(1)
Tin	225	(1)
Tributyltin from Industrial Activity in the Food Chain	225	(1)
Requirements for Better Risk Assessment of Dietary Trace Elements	226	(1)
Analytical Requirements	227	(1)
Conclusions	227	(1)
References	227	(1)
Trace Metal Speciation - A View from Inside the Food Industry	228	(4)
Simon Branch
Introduction	228	(1)
Reasons for Speciation in Industry	229	(1)
Legislation Based on Speciation	229	(1)
Dietary Supplementation and Fortification of Foods	229	(1)
Existing Speciation Measurements	230	(1)
Conclusion	230	(1)
References	231	(1)
Trace Element Speciation in Food: A Tool to Assure Food Safety and Nutritional Quality	232	(9)
Peter Van Dael
Introduction	232	(1)
Speciation and Food Safety	233	(2)
Arsenic	233	(1)
Chromium	234	(1)
Mercury	235	(1)
Speciation and Nutritional Food Quality	235	(2)
Selenium	236	(1)
Conclusion	237	(1)
References	238	(3)
Arsenic Intake in the Basque Country (Spain): A Real Need for Speciation	241	(10)
I. Urieta
M. Jalon
M. L. Macho
Introduction	241	(3)
Dietary Intake of Total Arsenic	244	(1)
Inorganic Arsenic Intake of Average Consumers	245	(1)
Theoretical Intake of Inorganic Arsenic of Extreme Fish Consumers	246	(1)
Dietary Intake of Total and Inorganic Arsenic: 1996-1998	247	(2)
Conclusions	249	(1)
References	249	(2)
Trace Element Speciation and International Food Legislation - A Codex Alimentarius Position Paper on Arsenic as a Contaminant	251	(10)
Erik H. Larsen
Torsten Berg
Introduction - What is a Codex Position Paper'?	251	(1)
Position Paper on Arsenic	252	(6)
Occurrence of Arsenic in Food	252	(1)
Toxicological Evaluations	253	(1)
Analytical Data	254	(1)
Intake Data	255	(1)
Potential Health Risks	256	(1)
Fair Trade Considerations	257	(1)
Conclusions and Recommendations	257	(1)
References	258	(3)
The Need for Speciation to Realise the Potential of Selenium in Disease Prevention	261	(26)
Suen Moesgaard
Richard Morrill
Introduction	261	(1)
Historical Background of Selenium	262	(2)
Recognition as an Essential Trace Element	262	(1)
Anti-carcinogenic Agent	263	(1)
Animal Studies	263	(1)
Human Studies	264	(1)
Clinical Intervention Trials	264	(4)
Linxian Study	264	(1)
Clark Study	264	(2)
Bonelli Study	266	(2)
Summary	268	(1)
The Precise Trial	268	(1)
Species of Selenium in Foodstuffs and Dietary Supplements	268	(3)
Selenium in Foodstuffs	268	(1)
Selenium in Dietary Supplements	269	(1)
Selenium in Body Fluids and Tissues	270	(1)
Selenium Metabolism in Humans and Animals	271	(1)
Adsorption	271	(1)
Transport	271	(1)
Storage	272	(1)
Elimination	272	(1)
Selenium Intake Levels	272	(1)
Safe and Adequate Levels	273	(1)
Recommended Levels	273	(1)
Upper Safety Levels	273	(1)
Uptake Variability of Selenium Species	273	(4)
Speciation of Selenium	277	(2)
Selenium in Foodstuffs	277	(1)
Selenium in Dietary Supplements	277	(1)
Selenium in Body Fluids And Tissues	278	(1)
Methods of Speciation	278	(1)
Pharmaceutical Quality Control	279	(1)
Public Health Implications of a Positive Population Study	279	(2)
Fortification of Foodstuffs and Feed stuffs	280	(1)
Enrichment of Fertilizers	280	(1)
Selenium Tablets (Dietary Supplement or Drug)	281	(1)
Need for Research and Legislation/Regulation	281	(1)
Conclusion	282	(1)
References	282	(5)
Health
The Importance of Speciation of Trace Elements in Health Issues	287	(10)
Rita Cornelis
Introduction	287	(1)
Biological Monitoring of Trace Element Species by Measuring Biomarkers of Exposure	288	(1)
The Study of Trace Element Kinetics in the Body Due to Industrial Exposure and the Dependency on the Chemical Form of Exposure	289	(3)
Identification of the Chemical Form of the Species That Will Become the Basis of Toxicity Studies	292	(4)
Conclusions	296	(1)
References	296	(1)
Occupational Health and Speciation Using Nickel and Nickel Compounds as an Example	297	(11)
Sally Pugh Williams
Introduction	297	(1)
Sources of Exposure to Nickel	298	(2)
Is it all Nickel `NICKEL'?	300	(1)
Nickel and Health	301	(1)
Nickel and Respiratory Cancer	302	(1)
Occupational Exposure Limits for Nickel	303	(1)
Air Monitoring and Biological Monitoring for Nickel	304	(2)
Conclusion	306	(1)
References	306	(2)
Surface Structure and Speciation of Metal Aerosols: A Key to the Understanding of Their Biological Effects	308	(7)
Markku Huvinen
Introduction	308	(1)
Ferrochromium Production	308	(1)
Production Process	309	(1)
Exposure	309	(1)
Production of Stainless Steel	309	(3)
Production Process	310	(1)
Exposure	311	(1)
Health Effects	312	(1)
Chromium	312	(1)
Stainless Steel	313	(1)
Health Effects in the Production Chain of Ferrochromium and Stainless Steel	313	(1)
Conclusions and Research Needs	313	(1)
References	314	(1)
The Importance of Chromium in Occupational Health	315	(16)
Grant Darrie
Introduction	315	(1)
Occurrence Production and Use	315	(2)
The Redox Chemistry of Chromium	316	(1)
Chromium Metallurgy	316	(1)
Chromium in Refractories	317	(1)
Chromium Chemicals	317	(5)
Hexavalent Chromium	318	(1)
Chromates	318	(1)
Dichromates	318	(1)
Chromic Acid	319	(1)
Tetravalent Chromium	320	(1)
Trivalent Chromium	320	(1)
Chromic Sulfate	320	(1)
Chromic Oxide	321	(1)
Complexes	321	(1)
Toxicity	322	(6)
Occupational	322	(1)
Hexavalent Chromium	322	(2)
Carcinogenicity	324	(3)
Genotoxcity	327	(1)
Trivalent Chromium	327	(1)
Behaviour of Chromium in the Body	328	(1)
Conclusion	328	(1)
References	328	(3)
Speciation Related to Human Health	331	(23)
Riansares Munoz-Olivas
Carmen Camara
Introduction	331	(2)
Usefulness of Samples	333	(1)
Blood	333	(1)
Urine	333	(1)
Hair	333	(1)
Human Milk	334	(1)
Main Analytes and Species	334	(12)
Essential Trace Elements	334	(1)
Copper	334	(1)
Selenium	335	(2)
Zinc	337	(1)
Iron	338	(1)
Probably Essential Trace Elements	338	(1)
Nickel	338	(1)
Vanadium	339	(1)
Cobalt	339	(1)
Potentially Toxic Trace Elements	339	(1)
Aluminium	339	(2)
Arsenic	341	(1)
Cadmium	342	(1)
Lead	342	(1)
Mercury	343	(1)
Platinum	344	(1)
Tin	345	(1)
Antimony	345	(1)
Conclusion: Needs for Elemental Speciation in Human Studies	346	(3)
Sample Collection	346	(1)
Storage and Stability of the Species	347	(1)
Pre-treatment of the Sample	347	(1)
Clean-up Processes	348	(1)
Analysis	348	(1)
Methods Validation	348	(1)
Regulations	349	(1)
References	349	(5)
Risk Assessment and Trace Element Speciation	354	(21)
John H. Duffus
Introduction	354	(2)
Trace Elements as Hazards	356	(2)
Risk Assessment of Trace Elements - General Considerations	358	(1)
Cationic Metal Uptake Mechanisms and Their Relation to Chemical Speciation	359	(5)
Bioavailability of Metals in Sediments	363	(1)
Uptake of Anions and Non-metals	364	(3)
Selection by Charge and Size; the Hydration of Anions and Binding to Proteins	365	(1)
Selection of Anions by Differences in Binding Affinity for Different Cationic Centres	365	(1)
Kinetic Binding Traps for Anions with or without Accompanying Redox Reactions	366	(1)
Competition and the Uptake and Toxicity of Non-nutrient Elements	367	(2)
Conclusions	369	(1)
References	370	(5)
Overview
An Overview	375	(10)
Les Ebdon
Les Pitts
Introduction	375	(1)
Analytical Needs and Instrumentation	375	(2)
Sample Preparation	377	(1)
Certified Reference Materials	378	(1)
Spiking	379	(1)
Speciation at the Cellular Level	379	(1)
Communication	380	(2)
Legislation	382	(2)
Conclusion	384	(1)
Subject Index	385