Residue Reviews: Residues of Pesticides and Other Contaminants in the Total Environment

155 Pages·1975·4.4 MB·English

by  Francis A. Gunther (eds.), M. H. B. Hayes, M. E. Pick, B. A. Toms (auth.)

RESIDUE REVIEWS
VOLUME 57
RESIDUE REVIEWS
Residues of Pesticides and Other
Contaminants in the Total Environment
Editor
FRANCIS A. GUNTHER
Assistant Editor
JANE DAVIES GUNTHER
Riverside, California
ADVISORY BOARD
F. BAR, Berlin, Germany· F. BRO-RASMUSSEN, S~borg, Denmark
D. G. CROSBY, Davis, California· S. DORMAL-VAN DEN BRUEL, Bruxelles, Belgium
C. L. DUNN, Wilmington, Delaware· H. EGAN, London, England
H. FREHSE, Leverkusen-Bayerwerk, Germany· K. FUKUNAGA, Saitama, Japan
H. GEISSBUHLER, Basel, Switzerland· G. K. KOHN, Richmond, California
H. F. LINSKENS, Nijmegen, The Netherlands· N. N. MELNIKOV, Moscow, U.S.S.R.
R. MESTRES, Montpellier, France· P. DE PIETRI-TONELLI, Milano, Italy
I. S. TAYWR, Melbourne, Australia· R. TRUHAUT, Paris, France
I. ZIEGLER, Miinchen, Germany
VOLUME 57
SPRINGER-VERLAG
NEW YORK HEIDELBERG BERLIN
1975
Coordinating Board of Editors
FRANCIS A. GUNTHER, Editor
Residue Reviews
Department of Entomology
University of California
Riverside, California 92502
JOHN W. HYLIN, Editor
Bulletin of Environmental Contamination and Toxicology
Department of Agricultural Biochemistry
University of Hawaii
Honolulu, Hawaii 96822
WILLIAM E. WESTI.AKE, Editor
Archives of Environmental Contamination and Toxicology
P.O. Box 1225
Twain Harte, California 95383
All rights reserved. No part of this book may be translated or reproduced in
any form without written pemiission from Springer-Verlag.
© 1975 by Springer-Verlag New York Inc.
Softcover reprint of the hardcover 1s t edition 1975
Library of Congress Catalog Card Number 62-18595.
The use of general descriptive names, trade names, trade marks, etc. in this
publication, even if the former are not especially identified, is not to be taken
as a sign that such names, as understood by the Trade Marks and Merchandise
Marks Act, may accordingly be used freely by anyone.
New York: 175 Fifth Avenue, New York, N.Y. 10010
Heidelberg: 6900 Heidelberg I, Postfach 1780, West Germany
ISBN-13: 978-1-4613-9393-1 e-ISBN-13: 978-1-4613-9391-7
DOl: 10.1007/978-1-4613-9391-7
Preface
That residues of pesticide and other contaminants in the total environ-
ment are of concern to everyone everywhere is attested by the reception
accorded previous volumes of "Residue Reviews" and by the gratifying
enthusiasm, sincerity, and efforts shown by all the individuals from whom
manuscripts have been solicited. Despite much propaganda to the con-
trary, there can never be any serious question that pest-control chemicals
and food-additive chemicals are essential to adequate food production,
manufacture, marketing, and storage, yet without continuing surveillance
and intelligent control some of those that persist in our foodstuffs could
at times conceivably endanger the public health. Ensuring safety-in-use
of these many chemicals is a dynamic challenge, for established ones are
continually being displaced by newly developed ones more acceptable to
food technologists, pharmacologists, tOxicologists, and changing pest-
control requirements in progressive food-producing economies.
These matters arc of genuine concern to increasing numbers of gov-
ernmental agencies and legislative bodies around the world, for some of
these chemicals have resulted in a few mishaps from improper use. Ade-
quate safety-in-use evaluations of any of these chemicals persisting into
our foodstuffs are not simple matters, and they incorporate the considered
judgments of many individuals highly trained in a variety of complex
biological, chemical, food technological, medical, pharmacological, and
toxicological disciplines.
It is hoped that "Residue Reviews" will continue to serve as an
integrating factor both in focusing attention upon those many residue
matters requiring further attention and in collating for variously trained
readers present knowledge in specific important areas of residue and
related endeavors involved with other chemical contaminants in the total
environment. The contents of this and previous volumes of "Residue
Reviews" illustrate these objectives. Since manuscripts are published in
the order in which they are received in final form, it may seem that some
important aspects of residue analytical chemistry, biochemistry, human
and animal medicine, legislation, pharmacology, physiology, regulation,
and toxicology are being neglected; to the contrary, these apparent omis-
sions are recognized, and some pertinent manuscripts are in preparation.
However, the field is so large and the interests in it are so varied that the
editors and the Advisory Board earnestly solicit suggestions of topics and
authors to help make this international book-series even more useful and
informative.
vi Preface
"Residue Reviews" attempts to provide concise, critical reviews of
timely advances, philosophy, and significant areas of accomplished or
needed endeavor in the total field of residues of these and other foreign
chemicals in any segment of the environment. These reviews are either
general or specific, but properly they may lie in the domains of analytical
chemistry and its methodology, biochemistry, human and animal medicine,
legislation, pharmacology, physiology, regulation, and toxicology; certain
affairs in the realm of food technology concerned specifically with pesti-
cide and other food-additive problems are also appropriate subject matter.
The justification for the preparation of any review for this book-series is
that it deals with some aspect of the many real problems arising from
the presence of any "foreign" chemicals in our surroundings. Thus, manu-
scripts may encompass those matters, in any country, which are involved
in allowing pesticide and other plant-protecting chemicals to be used
safely in producing, storing, and shipping crops. Added plant or animal
pest-control chemicals or their metabolites that may persist into meat and
other edible animal products (milk and milk products, eggs, etc.) are also
residues and are within this scope. The so-called food additives (sub-
stances deliberately added to foods for flavor, odor, appearance, etc., as
well as those inadvertently added during manufacture, packaging, dis-
tribution, storage, etc.) are also considered suitable review material. In
addition, contaminant chemicals added in any manner to air, water, soil or
plant or animal life are within this purview and these objectives.
Manuscripts are normally contributed by invitation but suggested
topics are welcome. Preliminary communication with the editors is neces-
sary before volunteered reviews are submitted in manuscript form.
Department of Entomology F.A.G.
University of California J.D.G.
Riverside, California
September 8, 1975
Table of Contents
Interactions between clay minerals and bipyridylium herbicides
By M. H. B. HAYES, M. E. PICK, and B. A. TOMS . 1
Pesticide residues in the Great Lakes Region of Canada
By C. R. HARRIS and J. R. W. MILES . . . . . 27
Secondary effects of pesticides on aquatic ecosystems
By STUART H. HURLBERT 81
Subject Index . . . . . . . . . . . . . . 149
Interactions between clay minerals
and bipyridylium herbicides
By
M. H. B. HAYES,o M. E. PICK,oo and B. A. TOMSo
Contents
I. Introduction ____________________________________________________ 1
II. Clay minerals ___________________________________________________ 2
a) Structures of clays ___________________________________________ 2
b) Some properties of clay minerals ______________________________ 3
III. Bipyridylium herbicides ______________________________ ~___________ 5
a) Structure and properties ______________________________________ 5
b) Biological availability in the soil environment _____________________ 6
IV. Adsorption of bipyridylium herbicides by clays ____________________ 7
a) Influence of time and temperature on adsorption ________________ 7
b) Influence of resident inorganic cation on adsorption ______________ 8
c) Adsorption of paraquat versus diquat __________________________ 8
d) Applications of microcalorimetry in the study of
bipyridylium-clay interactions __________________________________ 9
e) X-ray and spectroscopic studies on bipyridylium-clay complexes ____ 13
f) Comparison of the adsorption characteristics of paraquat and
diquat by Na+-montmorillonite and Na+-vermiculite clays _________ 15
V. Adsorption of bipyridylium cations with structures related to
paraquat and diquat _____________________________________________ 16
VI. Mechanisms of adsorption of bipyridylium herbicides by clays _______ 18
VII. Desorption of bipyridylium herbicides from clays __________________ 21
VIII. Conclusions _____________________________________________________ 22
Summary _____________________________________________________________ 23
References ____________________________________________________________ 23
I. Introduction
Adsorption of bipyridylium cations by clay minerals is a major
mechanism for the biological inactivation of the herbicides diquat (1,
° Department of Chemistry, University of Birmingham, P.O. Box 363, Birming-
ham B15 2TT, England.
00 C.E.G.B., Berkeley Nuclear Laboratories, Berkeley, Glocs., England.
© 1975 by Springer-Verlag New York Inc.
2 M. H. B. HAYES, M. E. PICK, AND B. A. TOMS
1'-ethylene-2, 2'bipyridylium dibromide) and paraquat (1, 1'-dimethyl-4,
4'-bipyridylium dichloride) in the soil environment (COATS et al. 1966,
KNIGHT and TOMLINSON 1967). Although humic substances also adsorb
bipyridyls (I. G. BURNS and HAYES 1974, KHAN 1974), it has been shown
(R. G. BURNS and AUDUS 1970) that paraquat bound by soil organic
matter is susceptible to microbial attack. \Vhen clay was added to this
medium the paraquat was transferred to the clay and then became un-
available to plants and to microorganisms. That the type of clay mineral
present in soil is important is implicit in the work of WEED and WEBER
( 1969) which indicates that bipyridylium herbicides can remain to an
extent in biologically available form when applied to soils where kaolinite
and vermiculite are the predominant clay minerals.
TOMLINSON et al. (1968) have shown that little paraquat was des orbed
from montmorillonite clay by even 6M solutions of ammonium acetate.
Displacement from illite or from kaolinite required a large excess of
ammonium ion. They concluded that all herbicidal bipyridylium cations
were likely to be sufficiently strongly adsorbed by clay minerals in order
to make displacement unlikely under field conditions in view of the large
excess of "strong adsorption sites" in soils. Microcalorimetry results by
HAYES et al. (1972 a) indicate that the bipyridylium cation is readily and
strongly bound by kaolinite, montmorillonite, and illite to an extent which
approaches the cation exchange capacity (CEC) of these clays. On
vermiculite, however, the extent and the mechanism of binding are influ-
enced by the nature of the charge-neutralizing inorganic cation on the
clay.
This review will consider in some detail the adsorption of paraquat
and of diquat by commonly occurring clay minerals and it will give some
consideration to the adsorption of compounds chemically related to these
herbicides. It is not proposed to review bipyridylium-soil and -plant
interactions.
II. Clay minerals
a) Structures of clays
In soil science the clay fraction is generally defined as the crystalline
inorganic material with an equivalent Stokes diameter of < 2 p.m. This
fraction can contain nonclay materials including some oxides and hy-
droxides and minerals such as quartz which have particle sizes below this
dimension. Clays can be formed directly by crystallization from solution
of silicates and aluminates (genesis), or by alteration (diagenesis) of
rocks and minerals by direct changes in the solid phase, or via the solu-
tion phase.
Several different clay minerals have been characterized, and many
detailed structures are described in standard texts (e.g., VAN OLPHEN
1963, MARSHALL 1964, GRIM 1968). Features which are necessary to un-
Clays and bipyridylium herbicides 3
derstand the general structures of clays and their properties (in relation
to their adsorption of organic chemicals) have been well described by
BAILEY and WmTE (1970). Thus only a very brief description of the
more common and readily characterizable minerals will be given here.
It should be remembered that soil clays are often complex interstratified
structures.
The fundamental structural units of clay minerals are two-dimensional
arrays of silicon-oxygen tetrahedra and two-dimensional arrays of alu-
minium-hydroxyl octahedra. Silicon atoms in the tetrahedral arrays are
coordinated with four oxygen atoms of which the three basal oxygen
atoms lie in the same plane, and each is shared by three neighbouring
tetrahedra. Thus these oxygen atoms have a hexagonal arrangement with
a "hole" in the middle. Aluminium atoms lie in the centre of the octa-
hedrallayer and are coordinated with six hydroxyl groups. Neighbouring
octahedra share edges and corners, and hence the hydroxyl groups form
a hexagonal close-packing arrangement in two parallel planes. The tetra-
hedral and octahedral sheets have similar dimensions in the plane of the
sheets (a, b axis) and are held together by sharing the. oxygen atoms at
the apices ("tip" oxygens) of the tetrahedral sheets, and these "tip"
oxygens replace two-thirds of the hydroxyls in one plane of the octahedral
layer. Thus, in a 1: 1 layer lattice (e.g., kaolinite) the "tip" oxygens are
coordinated with two aluminium atoms in the octahedral sheet. The
remaining ligands of the aluminium are coordinated with three basal
hydroxyls and with one hydroxyl which lies in the same plane as the
"tip" oxygens. This hydroxyl is coordinated with two aluminium atoms,
and it lies directly below the perforation of the hexagonal net of oxygens
in the tetrahedral sheet. A 2: 1 clay lattice is formed by combination of
an octahedral sheet with two tetrahedral sheets (one above and one
below) in the manner described. Such combinations produce .distortions
in the sheets, as shown by detailed crystallographic measurements by
NEWNHAM (1961) and RADOSLOVICH (1963).
Model clays, as described, are electroneutral and non expanding (with
layer thicknesses of ca. 0.72 nm for the 1:1 and ca. 0.96 nm for the 2:1
species). Isomorphous substitutions in the tetrahedral and octahedral
layers give rise to different clay structures. Al3+, and less frequently
Fe3+, can replace Si4 + in the tetrahedral sheet. Mg2+, Fe2+, Fe3 +, and
occasionally ions such as Zn2+ and Cr2+ replace AP+ in the octahedral
sheet. Replacement of the resident atom by one of lower valence gives
rise to negative charge in the lattice.
b) Some properties of clay minerals
Full classifications and properties of clay minerals are described in
standard texts and only a brief review of the properties relevant to the
adsorption of organocations will be given here.
In addition to the charge arising from isomorphous substitution
4 M. H. B. HAYES, M. E. PICK, AND B. A. TOMS
charges can also arise at the broken edges of the clay lattices. There
primary bonds are broken and the valencies of the exposed lattice atoms
are not completely compensated. As a result, depending on the pH of the
bulk solution of the medium, the surface will be positively or negatively
charged: it will be more positive as the pH is decreased.
Generally metallic cations from the medium balance the negative
lattice charges. However, the measured CEC can be distinctly different
from that based on the amounts of neutralizing cations present. For in-
stance, where potassium is the adsorbed balancing cation, it is of the
right size to enter the hexagonal holes and "cement" adjacent layers in
some 2:1 lattice structures. This behaviour is prevalent where isomor-
phous substitution predominates in the tetrahedral layers and is responsi-
ble for the nonexpanding lattice behaviour in illite, in mica, and in
K+-saturated vermiculite. Under such circumstances cation-exchange is
normally limited to the outside surfaces only. Hence, although the charge
per unit cell can be high, the CEC can be relatively low.
Other charge-neutralizing cations, such as Ca2 +, Mg2+, and Na +,
become hydrated in the interlamellar spaces and force the lattices apart.
Thus Na+- and Li+-montmorillonites (where isomorPhous substitution
is predominantly in the octahedral layer) disperse in water, but inter-
lamellar expansion in Ca2 +- and Mg2+-montmorillonites is limited to
ca. 0.9 nm, or the equivalent of three layers of water between the layers.
Vermiculite (with the exception of the Li+-clay) expands by only ca.
0.5 nm (or the equivalent of two layer thicknesses of water) for most
charge neutralizing cations. The K+- and NH,+-vermiculites do not dis-
play interlamellar expansion, for the reasons described earlier for the
K+-clay.
Table I shows that wide variations in cation-exchange capacities and
Table I. Selected properties of four clay minerals.
Clay Lattice Swelling CEC Surface area
mineral structure properties (meq g-l) (sq m g_l)
Montmorillonite 2:1 Expanding 80-120 75~00
Vermiculite 2:1 Limited expanding 100-150 500-700
Illite 2:1 Nonexpanding 10-40 50-125
Kaolinite 1:1 Nonexpanding 3-10 10-50
in surface-area measurements can exist between different clay minerals,
and to a lesser extent within different members of the same species. The
surface areas depend, of course, on whether or not interlamellar expan-
sion can take place. CEC data can be combined with surface area meas-
urements to give values for surface density of charge. Such values are
important when determining the adsorption characteristics and the orien-
tation of adsorbed organocations at clay surfaces. Charges on clays are
often visualized as point charges. A more realistic model, however, should