Migration and Fate of Pollutants in Soils and Subsoils PDF
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Migration and Fate of Pollutants in Soils and Subsoils NATO ASI Series Advanced Science Institutes Series A series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical and Kluwer Academic Publishers Physical Sciences Dordrecht, Boston and London D Behavioural and Social Sciences E Applied Sciences F Computer and Springer-Verlag Systems Sciences Berlin Heidelberg New York G Ecological Sciences London Paris Tokyo Hong Kong H Cell Biology Barcelona Budapest I Global Environmental Change NATO-PCO DATABASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 30000 contributions from international scientists published in all sections of the NATO ASI Series. a Access to the NATO-PC DATABASE compiled by the NATO Publication Coordination Office is possible in two ways: -via online FILE 128 (NATO-PCO DATABASE) hosted by ESRIN, Via Galileo Galilei, 1-00044 Frascati, Italy. -via CD-ROM "NATO-PCO DATABASE" with user-friendly retrieval software in English, French and German (© WTV GmbH and DATAWARE Technologies Inc. 1989). The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium. Series G: Ecological Sciences, Vol. 32 Migration and Fate of Pollutants in Soils and Subsoils Edited by Domenico Petruzzelli Istituto Ricerca Acque National Research Council 5, Via de Blasio 1-70123 Bari, Italy Friedrich G. Helfferich The Pennsylvania State University Department Chemical Engineering University Park, PA 16802-4400, USA Springer-Verlag Berlin Heidelberg New York London Paris Tokyo Hong Kong Barcelona Budapest Published in cooperation with NATO Scientific Affairs Division Proceedings of the NATO Advanced Study Institute on Migration and Fate of Pollutants in Soils and Subsoils held at Maratea, Italy, from May 24 to June 5, 1992 ISBN-13: 978-3-642-77864-3 e-ISBN-13: 978-3-642-77862-9 001: 10.1007/978-3-642-77862-9 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of thiS publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in ItS current verSion, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution under the German Copyright Law © Springer-Verlag Berlin Heidelberg 1993 Softcover reprint of the hardcover 1s t edition 1993 Typesetting: Camera ready by authors 31/3145 -5 4 3 210 -Printed on acid-free paper Preface Mass transport phenomena in natural permeable media are of practical importance in a variety of fields. Examples from civil, hydraulic and environment engineering are groundwater pollution and seepage from landfills or other disposal operations, an example from petroleum engineering is enhanced oil recovery. Other disciplines having major impact include chemistry, biology, hydrology, geochemistry, ecology. By their very nature, permeable media and thus the transport phenomena taking place in them are highly complex. Often, finding solutions to practical problems calls for close cooperation between experts from different fields. In recent years, highly complex theories and methods, based on novel concept of non-linear wave propagation have been developed, verified and successfully applied in chemical, petroleum and environmental engineering. Yet, a truly comprehensive understanding of migration and fate of chemicals in soils and subsoils and an ability to make reliable predictions have not been fully obtained. The authors (from European and American countries) are experts in soil and environmental sciences as well as in theory of wave propagation and numerical modeling methods. The focus was essentially posed on the analysis of contributing phenomena and their interactions, modeling, and practical use of such knowledge and models for guidance in disposal operations, preventive measures to minimize ecological damage, prediction of consequences of seepage, and design of remedial actions. No specialty thrives in isolation. It was from this background that the idea arose to convene qualified experts from different areas to work together in an international study meeting for the benefit of those attending as well as for mutual enrichment. This gave the meeting the spice of contribution, formal and informal, from experts of many diverse backgrounds and nationalities, and helped to secure the broad-based support from NATO, Consiglio Nazionale delle Ricerche of Italy (National Research Council), Ente Autonomo Acquedotto Pugliese (Apulian Water Authority) and industrial companies that made the Summer School possible in the first place. VI It is not for the organizers and lecturers to say that the meeting was a success. This has to come from future perspectives by those who derived benefit from attending the School or from reading the contributions presented here. n is a pleasure, however, to express our deep appreciation for the untiring work of the other members of the Scientific Board of the meeting: Prof. W.I. Weber, Prof. R.Passino, Prof. L. Liberti , Prof. A.I. Valocchi, Dr G. Tiravanti, Prof. T.Asano, Prof. V.S.Soldatov, and for the support of all who helped to provide a stimulating climate, both technical and social, for a true meeting of minds amid beatiful surroundings, at Acquafredda di Maratea. D.Petruzzelli F.G .Helfferich NATO ADVANCED STUDY INSTITUTE MIGRATION AND FATE OF POLLUTANTS IN SOILS AND SUBSOILS Acquafredda di Maratea, Italy, May 24 - June 5, 1992 Director: D. PETRUZZELLI, Istituto Ricerca Acque, C.N.R., Bari, Italy. Co-Director: F.G. HELFFERICH, The Pennsylvania State University, University Park, U.S.A. Lecturers: ASANO T., University of California, Davis, CA, USA. CORAPCIOGLU M.Y ., Texas A&M University, College Station, TX, USA. FORSTNER U., Technical University Hamburg-Harburg, Germany. GAMBOLATI G., Universita di Padova, Padua, Italy. GANOULIS J., Aristotle University, Thessaloniki, Greece. HARWELL J.H., The University of Oklahoma, Norman, OK, USA. HELFFERICH F.G., Penn State University, University Park, PA, USA. LOPEZ A., Istituto Ricerca Acque C.N.R., Bari, Italy. MANSOUR M., Institut Okologische Chemie, Freising, Germany. NERETNIEKS I., Kungl Tekniska Ogskolan, Stockholm, Sweden. NOVAK C.F., Sandia National Laboratories, Albuquerque, NM, USA. PETRUZZELLI D., Istituto Ricerca Acque C.N.R., Bari, Italy. ROY W.R., Illinois State Geological Survey, Champaign, IL, USA. SCHWEICH D., Lab.Sci. Genie Chimique, CNRS-ENSIC, Nancy, France. SENESI N., Universita di Bari, Bari, Italy. SOLDATOV V.S., Bielorussia Academy of Science, Minsk, Bielorussia. SPARKS D.L., University of Delaware, Newark, DE, USA. VALOCCm A.J., University of Illinois, Urbana, USA. VAN DER ZEE S.E., Agricultural University, Wageningen, The Netherlands. WEBER W.J. Jr., The University of Michigan, Ann Arbor, MI, USA. TABLE OF CONTENTS Preface. .................................................... V PART I. LOCAL PHENOMENA. Walter J. Weber Jr. TRANSPORT AND FATE OF POLLUTANTS IN SUBSURFACE SYSTEMS: CONTAMINANTS SORPTION AND RETARDATION ...........3 -Subsurface Sorption Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 3 -Sorption Models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 4 - Mechanistic Equilibrium Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 -Ion Exchange and Surface Complexation. . . . . . . . . . . . . . . . . . . . . . . ... 5 - Hydrophobic Sorption ..................................... 6 -Phenomenological Equilibrium Models. . . . . . . . . . . . . . . . . . . . . . . . . . .. 7 - Classical models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 - The Distributed Reactivity Model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8 - Rate Models ............................................. 9 -Mass Transfer Models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 - Type I Domains and Models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 - Application Considerations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 - Contaminant Fate and Transport. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .16 - The ADR Equation ........................................ 16 - Common Assumptions and Approximations. . . . . . . . . . . . . . . . . . . . . . " 17 - Analyses of Field Scale Sensitivity. .............................. 19 - Closure. ................................................2 5 - References ...............................................2 6 x Sjoerd E. Van Der Zee THEORETICAL AND PRACTICAL ASPECTS OF SOIL CHEMICAL BEHAVIOUR OF CONTAMINANTS IN SOILS ..................... 27 - General Background of Metal Ion Binding. . . . . . . . . . . . . . . . ......... 28 - Chemical Heterogeneity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....... 29 - Electrostatic Effects .......................................3 2 - Competition ............................................3 3 - Specific Binding to Oxides ....................................3 5 - Specific Binding to Organic Matter. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 - Sorption by Soil. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 37 - References ..............................................4 4 Nicola Senesi ORGANIC POLLUTANT MIGRATION IN SOILS AS AFFECTED BY SOIL ORGANIC MATTER. MOLECULAR AND MECHANISTIC ASPECTS ..... 47 - Soil Humic Substances. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 - Organic Pollutants in Soil. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 51 - Adsorption Mechanisms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53 -Ionic Bonding (cation exchange) ............................... 54 - Hydrogen Bonding ........................................ 55 - Charge-Transfer (electron donor-acceptor) ........................ 55 - Covalent Binding .........................................5 8 - Ligand Exchange (cation bridge) ...............................6 0 - Dipole-Dipole and Van Der Waals Forces .........................6 0 -Hydrophobic Adsorption and Partition ........................... 60 - Solubilization Effects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 - Hydrolysis Catalysis ........................................6 4 - Photosensitization ......................................... 66 - Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......... 70 - References .............................................. 71 XI Domenico Petruzzelli, Antonio Lopez SOLID-PHASE CHARACTERISTICS AND ION EXCHANGE PHENOMENA IN NATURAL PERMEABLE MEDIA ..................7 5 - Physico Chemical Properties at Mineral-Water Interface .................7 5 - Soil Constituents and Origin of Charges. . . . . . . . . . . . . . . . . . . . . . . . . . .76 - Inorganic Constituents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76 - The Organic and Organo-Mineral Fraction of Soils ................... 82 - pH Dependence of Charges. . . . . . . . . . . . . . . . . . . .'. . . . . . . . . . . . . .. 83 - Cation Exchange. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 83 - Anion Exchange. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 84 - Cation Exchange Capacity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 86 - Thermodynamics of Ion Exchange in Natural Permeable Media. . . . . . . . . . . . 86 - The Electric Double Layer Model, General Considerations ...............8 6 - Highly Selective Retention of Cations in Porous Media. . . . . . . . . . . . . . .... 88 - Specific Retention of Cations in Clay Lattices. . . . . . . . . . . . . . . . . . . . ... 89 -Selective Ion Exchange Reactions in Zeolites ........................9 0 - Conclusions ..............................................9 0 - References ...............................................9 1 Antonio Lopez, Domenico Petruzzelli INTERACTIONS OF roXIC ORGANICS WITH SUBSOILS COMPONENTS ........................................... 93 - Physico-Chemical Properties of Organic Contaminants (Solute) .............9 4 - Relevant Physico-chemical Properties of Mineral Constituents of Subsoils (Sorbent) ........................................ 98 - Clays ................................................. 98 - Metal Oxides and Hydroxides ................................ 100 - Main Physico-Chemical Properties of liquid-phase (Solvent) .............. 102 - Conclusions ............................................. 107 - References .............................................. 108
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