Nuclear Magnetic Resonance Spectroscopy in Environmental Chemistry

341 Pages·1997·16.98 MB·English

by  Mark A. Nanny, Roger A. Minear, Jerry A. Leenheer

NUCLEAR MAGNETIC
RESONANCE SPECTROSCOPY IN
ENVIRONMENTAL CHEMISTRY
TOPICS IN ENVIRONMENTAL CHEMISTRY
A Series of Advanced Textbooks and Monographs
Series Editor
John W. Birks, University of Colorado
Associate Editors
Michael R. Hoffmann, California Institute of Technology
Richard D. Noble, University of Colorado
William M. Lewis, University of Colorado
John H. Seinfeld, California Institute of Technology
Garrison Sposito, University of California, Berkeley
William Davison, Lancaster University
Environmental Chemistry of Soils
M. McBride
Atmospheric Chemistry and Global Change
G. Brasseur, editor
NMR Spectroscopy in Environmental Chemistry
M. Nanny, R. Minear, and J. Leenheer, editors
NUCLEAR MAGNETIC
RESONANCE SPECTROSCOPY IN
ENVIRONMENTAL CHEMISTRY
Edited by
MARK A. NANNY
ROGER A. MINEAR
JERRY A. LEENHEER
New York Oxford
Oxford Unversity Press
1997
Oxford University Press
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Copyright © 1997 by Oxford University Pres, Inc.
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Library of Congress Cataloging-in-Publication Data
Nanny, Mark A.
Nuclear magnetic resonance spectroscopy in environmental
chemistry
edited by Mark A. Nanny, Roger A. Minear, Jerry A. Leenheer.
p. cm.
Includes bibliographical references and index.
ISBN 0-19-509751-3
1. Environmental chemistry. 2. Nuclear magnetic resonance
spectroscopy. I. Minear, R. A. II. Leenheer, J. A. III. Title.
TD193-N36 1997
628-dc20 95-47215
1 3 5 7 9 8 6 4 2
Printed in the United States of America
on acid-free paper
Preface
Nuclear magnetic resonance (NMR) spectroscopy has been an important
analytical and qualitative tool in chemistry, material science, and organic
geochemistry for quite some time, and now is becoming recognized as a
valuable tool in environmental science and technology. Because it is a non-
destructive and element-specific probe, it is useful for examining a myriad of
environmental reactions occurring in a variety of complex and heterogeneous
matrices. The intent of this book is to show how NMR is becoming such a
useful tool, and how it is being applied to a wide variety of environmental
science and technology topics. Research involving numerous NMR-active
L 2 13 15 19 23 27 31 133
nuclei ( H, H, C, N, F, Na, A1, P, and Cs) in highly hetero-
geneous and complex samples of environmental significance is presented.
Also included is a wealth of information pertaining to sample preparation,
instrumental techniques, and data interpretation.
A major reason why NMR has not been considered useful for environ-
mental research is that NMR spectroscopy is not sensitive enough for most of
the chemical concentrations that occur in many environmental reactions. In
addition, environmental reactions usually occur in heterogeneous matrices
which often hinder and reduce the resolution and sensitivity of NMR spectro-
scopy. Likewise, many isolation and concentration methods used to over-
come low concentrations are not feasible or introduce unacceptable sample
alterations. Despite the fact that these problems still exist and in many
instances are difficult to overcome, the introduction of stronger magnets,
the development of new and better software and hardware, new sample pro-
cessing and experimental methods, and most importantly, increased accessi-
bility to NMR instrumentation have permitted environmental NMR studies
to gain a foothold and grow. The research presented in this book illustrates
how these problems have been addressed and how the advances listed above
VI PREFACE
have furthered environmental studies. This book provides a survey of the
current application of NMR to research problems in environmental science
and technology, and also demonstrates the diversity and breadth of environ-
mental research problems that NMR spectroscopy can address.
The book is divided into three parts, of which the first, on Contaminant
Interactions, presents NMR research examining interactions of various mole-
cules, such as pollutants with humic materials. The second part, Solution and
Condensed Phase Characterization, presents studies examining the chemistry
of various environmentally important species in a variety of phases: solution,
colloidal, and condensed phase. Nutrient and Natural Organic Matter
Cycling in the Environment, the final part, includes research exploring phos-
phorus and nitrogen cycling in the environment, in addition to new research
involving the characterization of natural organic carbon material, especially
with difficult samples, i.e., low-carbon sediments.
To complement each part, an overview chapter is included, providing a
discussion as to why and how NMR spectroscopy has advanced research in
the areas concerned. In addition, an introductory chapter is included that
reviews the basic principles of solution and solid-state NMR spectroscopy
for those unfamiliar with NMR. Finally, the future needs and directions of
NMR research in environmental science and technology are presented in the
closing chapter, which results from a panel discussion involving several of the
chapter authors. In this chapter, they recommend areas in which environ-
mental NMR spectroscopy can be the most advantageous technique and, in
addition, discuss the difficulties an environmental scientist faces in imple-
menting NMR in a research project.
With its focus on NMR studies in environmental research, it is hoped
that this book will be of use to NMR spectroscopists interested in analyzing
environmental samples, and requiring a basic body of knowledge regarding
spectroscopy of environmental samples. Likewise, it is hoped that environ-
mental scientists will use this book as a guide to incorporating NMR into
their research. Hopefully, it will serve as a benchmark for current environ-
mental NMR research, as well as a stepping-stone to spur future work in the
same area.
M.A.N
R.A.M
J.A.L
Contents
Introduction
Nuclear Magnetic Resonance Spectroscopy: Basic Theory and Background
H. KNICKER & M. A. NANY 3
Contaminant Interactions
1.
Sorption Processes in the Environment: Nuclear Magnetic Resonance
Spectroscopy as a New Analytical Method
M. A. NANY 19
2.
13 13
The Development of C Labeling and C NMR Spectroscopy Techniques
to Study the Interaction of Pollutants with Humic Substances
J. M. BORTIATYNSKI, P. G. HATCHER, & R. D. MINARD 26
3.
19
Proton and F NMR Spectroscopy of Pesticide Intermolecular
Interactions
S.J.ANDERSON 51
4.
19 2
A F and H NMR Spectroscopic Investigation of the Interaction Between
Nonionic Organic Contaminants and Dissolved Humic Material
B. E. HERBERT & P. M. BERTSCH 73
Viii CONTENTS
5.
13
Adsorption Isotherms and C Solid-state NMR Study of Hazardous
Organic Compounds Sorbed on Coal Fly Ash
D. A. NETZEL, F. P. MIKNIS, D. C. LANE, J. F. ROVANI, J. D. COX,
& J . A. CLARK 91
Solution and Condensed Phase Characterization
6.
Solution and Condensed Phase Characterization
R. A. MINEAR & M. A. NANNY 123
7.
NMR Studies of the Reaction of Amino Acids with Aqueous Chlorine
F. E. SCULLY, JR., B. CONYERS, E. FORRER, & E. P. LOCKE 130
8.
27
Comparative Results of A1 NMR Spectrometric and Perron Colorimetric
Analyses of Hydroxyaluminum Hydrolysis Products in Aged, Mildly
Acidic, Aqueous Systems
D. V. VIVIT, K. A. THORN, & J. D. HEM 140
9.
27
A1 NMR Study of the Hydrolysis and Condensation of Organically
Complexed Aluminum
F. THOMAS, A. MASION, J. Y. BOTTERO, & P. TEKELY 161
10.
Cation and Water Interactions in the Interlamellae of a Smectite Clay
A. LABOURIAU, C. T. JOHNSTON, & W. L. EARL 181
11.
2
H NMR and Gel Formation of the Ultrafine Solids Fraction Associated
with the Athabasca Oil Sands Fine Tails
J. A. RIPMEESTER, L. S. KOTLYAR, B. D. SPARKS, & R. SCHUTTE 198
Nutrient and Natural Organic Matter Cycling in the Environment
12.
Characterization of Natural Organic Matter by Nuclear Magnetic
Resonance Spectroscopy
J. A. LENHER 213
13.
31
P FT-NMR of Concentrated Lake Water Samples
M. A. NANNY & R. A. MINEAR 221
CONTENTS ix
14.
31
Use of P NMR in the Study of Soils and the Environment
L. M. CONDRON, E. FROSSARD, R. H. NEWMAN, P. TEKELY, & J.-L. MOREL 247
15.
Characterization of Nitrogen in Plant Composts and Native Humic
15
Material by Natural-Abundance N CPMAS and Solution NMR Spectra
H. KNICKER, R. FRUND, & H.-D. LUDEMANN 272
16.
J
Acquisition and Interpretation of Liquid-state H NMR Spectra of Humic
and Fulvic Acids
J. A. LEENHEER, T. I. NOYES, & R. L. WERSHAW 295
17.
Preparation of Low-Carbon Sediments from the Mississippi River and
13
Certain Tributaries for Solid-state CPMAS C NMR Analysis
J. A. LEENHEER, G. E. MACIEL, & T. I. NOYES 304
18.
Research Needs for Environmental NMR
M. A. NANNY, R. A. MINEAR, & J. A. LEENHEER 313
Index 317