Cover Page i Preconcentration Techniques for Natural and Treated Waters Page ii This page intentionally left blank. Page iii Preconcentration Techniques for Natural and Treated Waters High Sensitivity Determination of Organic and Organometallic Compounds, Cations and Anions T.R.Crompton LONDON AND NEW YORK Page iv First published 2003 by Spon Press 11 New Fetter Lane, London EC4P 4EE Simultaneously published in the USA and Canada by Spon Press 29 West 35th Street, New York, NY 10001 Spon Press is an imprint of the Taylor & Francis Group This edition published in the Taylor & Francis eLibrary, 2004. To purchase your own copy of this or any of Taylor & Francis or Routledge’s collection of thousands of eBooks please go to www.eBookstore.tandf.co.uk. © 2003 T.R.Crompton Publisher’s note: This book was prepared from cameraready copy supplied by the author. The author has made considerable effort to trace and contact copyright holders and secure replies prior to publication. 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ISBN 0203303385 Master ebook ISBN ISBN 0203356314 (OEB Format) ISBN 0415268117 (Print Edition) Page v Contents Preface xxix 1 Introduction 1 1.1 Purity of reagents and detection limits 1 1.2 Prepurification of reagents 6 1.3 Effect of pH 7 1.4 Effect of chelating agentmetal ratio 9 1.5 Matrix interference effects 9 1.6 Adsorption efficiency of solid adsorbents 13 1.7 Ion exchange resin theory 14 1.8 Coprecipitation techniques 20 1.9 Preconcentration of organics by direct solvent extraction 21 1.9.1 Theory of mutual solubility effects 22 1.9.2 Theory of partition coefficient effects 26 1.10 Preconcentration of organics by static headspace analysis 30 1.11 Preconcentration of organics by purge and trap analysis 31 References 34 2 Organics: Chelationsolvent extraction techniques 35 Organic compounds 35 2.1 Non saline waters 35 2.1.1 Amines 35 Organometallic compounds 35 2.2 Non saline waters 35 2.2.1 Organolead compounds 35 2.2.2 Organomercury compounds 36 2.3 Seawater 36 2.3.1 Organotin compounds 36 2.3.2 Organomercury compounds 36 References 37 Page vi 3 Organics: Macroreticular nonpolar resins 38 Organic compounds 38 3.1 XAD1 resins 38 3.1.1 Sewage effluents 39 3.1.1.1 Chlorophyll, coprostanol 39 3.2 XAD2 and XAD4 resins 39 3.2.1 Non saline waters 39 3.2.1.1 General discussion 39 Applications of XAD resins 52 3.2.1.2 Polyaromatic hydrocarbons 52 3.2.1.3 Coprostanol 58 3.2.1.4 Non ionic surfactants 59 3.2.1.5 Organophosphorus insecticides 62 3.2.1.6 Organochlorine pesticides PCBs, organophosphorus pesticides, triazine herbicides, chlorophenoxyacetic acid herbicides and phthalate 67 esters 3.2.1.7 Carbamate insecticides 69 3.2.1.8 Sulphur containing insecticides 70 3.2.1.9 Polychlorinated biphenyls 70 3.2.1.10 Polychlorodibenzopdioxins and furans 70 3.2.1.11 Hydrocarbons 70 3.2.1.12 Chlorinated aliphatic hydrocarbons 71 3.2.1.13 Haloforms 71 3.2.1.14 Chlorophenols and chloroamines 71 3.2.1.15 Carboxylic acids 71 3.2.1.16 Carbanilides 71 3.2.1.17 Cytokinins 72 3.2.2 Seawater 72 3.2.2.1 General discussion 72 3.2.2.2 Polychlorinated biphenyls and chlorinated insecticides 72 3.2.2.3 Organophosphorus insecticides 74 3.2.2.4 Chlorinated aliphatic compounds 74 3.2.2.5 Azarenes 74 3.2.2.6 Humic and fulvic acids 75 3.2.2.7 Sterols 75 3.2.2.8 Organosulphur compounds 75 3.2.3 Waste waters 76 3.2.3.1 Polyaromatic hydrocarbons 76 3.2.4 Potable waters 76 3.2.4.1 Haloforms and aliphatic chlorocompounds 76 Page vii 3.2.5 Miscellaneous waters/miscellaneous organocompounds 76 3.3 Tenax GC 83 Organic compounds 84 3.3.1 Non saline waters 84 3.3.1.1 Semivolatile organic compounds 84 3.3.1.2 Miscellaneous organic compounds 84 3.3.2 Seawater 84 3.3.2.1 Poly chlorinated biphenyls and organochlorine and organophosphorus insecticides 84 3.3.3 Potable water 86 3.3.3.1 Triazine herbicides 86 3.3.4 Waste waters 86 3.3.4.1 Polyaromatic hydrocarbons 86 Organometallic compounds 90 3.4 Tenax GC 90 3.4.1 Seawater 90 3.4.1.1 Organotin compounds 90 References 91 4 Organics: Cation exchange resins 97 Organic compounds 99 4.1 Non saline and other waters 99 4.1.1 Amino acids 99 4.1.2 Miscellaneous organic compounds 99 4.2 Seawater 102 4.2.1 Amino acids 102 4.3 Waste waters 102 4.3.1 Phenolic compounds 102 4.3.2 Chlorolignosulphonic acids 103 4.3.3 Alkyl ethoxylated sulphates 103 Organometallic compounds 103 4.4 Non saline waters 103 4.4.1 Organotin compounds 103 4.5 Seawater 103 4.5.1 Organoarsenic compounds 103 References 104 5 Organics: Anion exchange resins 106 Organic compounds 107 5.1 Non saline waters 107 5.1.1 Carboxylic acids 107 5.1.2 Nitriloacetic acid 107 Page viii 5.1.3 Humic and fulvic acids 107 5.1.4 Aldicarb insecticide 109 5.1.5 Organophosphorus insecticides 109 5.1.6 α, α dichloropropionate, 2,3,6 trichloro benzoate, 2methoxy 3,6dichlorobenzoate and 2,4D 109 5.2 Seawater 109 5.2.1 Organophosphorus insecticides 109 5.3 Surface waters 110 5.3.1 Nitriloacetic acid 110 5.4 Potable water 110 5.4.1 Paraquat and Diaquat 110 Organometallic compounds 110 5.5 Non saline waters 110 5.5.1 Organomercury compounds 110 References 110 6 Organics: Organic and inorganic solid adsorbents and chelators 112 6.1 Sulphydryl cotton fibre 112 6.1.1 Non saline waters 112 6.1.1.1 Organomercury compounds 112 6.2 Cellulose acetate 113 6.2.1 Non saline waters 113 6.2.1.1 Chlorinated insecticides and PCBs 113 6.2.1.2 Miscellaneous organics 113 6.3 Cellulose 113 6.3.1 Non saline waters 113 6.3.1.1 Urea herbicides 113 6.4 Chromosorb W 113 6.4.1 Non saline waters 113 6.4.1.1 Polychlorobiphenyls 113 6.5 Chromosorb 105 113 6.5.1 Non saline waters 113 6.5.1.1 Phenols 113 6.6 Lipidex 5000 114 6.6.1 Non saline waters 114 6.6.1.1 Polychlorophenols 114 6.7 Support bonded silicones 114 6.7.1 Non saline waters 114 6.7.1.1 Organochlorine insecticides 114 6.8 Polytetrafluoroethylene (Chromosorb T) 114 6.8.1 Non saline waters 114 6.8.1.1 Linear alkyl benzene sulphonates 114 Page ix 6.9 Polyethylene and polypropylene 115 6.9.1 Non saline waters 115 6.9.1.1 Chlorinated insecticides 115 6.9.1.2 Miscellaneous organics 115 6.10 Polysorb1 115 6.10.1 Mineral waters 115 6.10.1.1 Miscellaneous organics 115 6.11 Poropak 116 6.11.1 Trade effluents 116 6.11.1.1 Nitro compounds 116 6.12 Carbopak B 116 6.12.1 Non saline waters 116 6.12.1.1 Volatile organics 116 6.13 Separalyte 116 6.13.1 Non saline waters 116 6.13.1.1 2, 3, 7, 8 tetrachlorodibenzopdioxin 116 6.14 CN bonded SPE 117 6.14.1 Non saline waters 117 6.14.1.1 Chlorinated insecticides 117 6.15 Dowex in [Co(SCN)4]2− form 117 6.15.1 Non saline waters 117 6.15.1.1 Tween K100 and Tween 20 117 6.16 Glass beads 117 6.16.1 Non saline waters 117 6.16.1.1 Pentachloronitrobenzene and trichloroacetic acid 117 6.17 Graphite fluoride 117 6.17.1 Non saline waters 117 6.17.1.1 Miscellaneous organics 117 6.18 Cyclohexyl bonded phase resin 117 6.18.1 Groundwater 117 6.18.1.1 Creosote and pentachlorophenol 117 6.19 Apiezon L 118 6.19.1 Non saline waters 118 6.19.1.1 Dimethylbenzene 118 6.20 Silicic acid 118 6.20.1 Non saline waters 118 6.20.1.1 Phenols 118 6.20.2 Surface and coastal waters 118 6.20.2.1 Chlorinated insecticides 118 6.21 Potassium aluminium silicate 118 6.21.1 Non saline waters 118 6.21.1.1 Phenyl urea herbicides 118 6.21.1.2 Mineral, animal and vegetable oils 119