Residue Reviews / Ruckstands-Berichte: Residues of Pesticides and Other Foreign Chemicals in Foods and Feeds / Ruckstande von Pesdciden und anderen Fremdstoffen in Nahrungs- und Futtermitteln

155 Pages·1968·7.61 MB·English

by  N. A. Smart (auth.)

RESIDUE REVIEWS
VOLUME 23
RESIDUE REVIEWS
Residues of Pesticides and Other
Foreign Chemicals in Foods and Feeds
RUCKSTA NDS. . BERICHTE
Riickstande von Pesdciden und anderen
Fremdstoffen in Nahrungs- und Futtermitteln
Edited by
FRANCIS A. GUNTHER
Riverside, California
ADVISORY BOARD
F. BAR, Berlin, Germany • F. BRD-RAsMUSSEN, Copenhagen, Denmark
J. W. COOK, Washington, D.C. • D. G. CROSBY, Davis, California
S. DORMAL-VAN DEN BRUEL, Bruxelles, Belgium
C. 1. DUNN, Wilmington, Delaware • H. FREHSE, Leverkusen-Bayerwerk, Germany
J. C. GAGE, Macclesfield, England· H. GEISSBUHLER, Basel, Switzerland
S. A. HALL, Beltsville, Maryland • T. H. HARRIS, Bethesda, Maryland
L. W. HAzLETON, Falls Church, Virginia • H. HURTIG, Ottawa, Canada
o. R. KLIMMER, Bonn, Germany • G. K. KOHN, Richmond, California
H. F. LINSKENS, Nijmegen, The Netherlands • H. MAIER.BoDE, Bonn, Germany
N. N. MELNIKOV, Moscow, U.S.S.R. • R. MESTRES, Montpellier, France
P. DE PIETRI·ToNELLI, Milano, Italy • R. TRUHAUT, Paris, France
VOLUME 23
SPRINGER-VERLAG
BERLIN • HEIDELBERG • NEW YORK
1968
ISBN-13: 978-1-4615-8439-1 e-ISBN-13: 978-1-4615-8437-7
DOl: 10.1007/978-1-4615-8437-7
All rights, especially that of translation into foreign languages, reserved. It is also
forbidden to reproduce this book, either whole or in part, by photomechanical means
(photostat, microfilm and/or microcard) or by other procedure without written
permission from the Publishers.
© 1968 by Springer-Verlag New York Inc.
Softcover reprint of the hardcover 1st edition 1968
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.
Title No. 6625
Preface
That residues of pesticide and other "foreign" chemicals in foodstuffs
are of concern to everyone everywhere is amply attested by the reception
accorded previous volumes of "Residue Reviews" and by the gratifying en-
thusiasm, sincerity, and efforts shown by all the individuals from whom
manuscripts have been solicited. Despite much propaganda to the contrary,
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, pharma-
cologists, toxicologists, and changing pest-control requirements in progressive
food-producing economies.
These matters are also of genuine concern to increasing numbers of
governmental agencies and legislative bodies around the world, for some of
these chemicals have resulted in a few mishaps from improper use. Adequate
safety-in-use evaluations of any of these chemicals persisting into our food-
stuffs are not simple matters, and they incorporate the considered judgments
of many individuals highly trained in a variety of complex biological, chemi-
cal, food technological, medical, pharmacological, and toxicological dis-
ciplines.
It is hoped that "Residue Reviews" will continue to serve as an integrat-
ing 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 en-
deavors; no other single publication attempts to serve these broad purposes.
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 omissions are recognized, and some pertinent
manuscripts are in preparation. However, the field is so large and the in-
terests in it are so varied that the editor and the Advisory Board earnestly
solicit suggestions of topics and authors to help make this international
book-series even more useful and informative.
"Residue Reviews" attempts to provide concise, critical reviews of timely
advances, philosophy, and significant areas of accomplished or needed en-
deavor in the total field of residues of these chemicals in foods, in feeds, and
in transformed food products. These reviews are either general or specific, but
properly they may lie in the domains of analytical chemistry and its method-
ology, biochemistry, human and animal medicine, legislation, pharmacology,
physiology, regulation, and toxicology; certain affairs in the realm of food
technology concerned specifically with pesticide and other food-additive
problems are also appropriate subject matter. The justification for the prepara-
tion of any review for this book-series is that it deals with some aspect of
the many real problems arising from the presence of residues of "foreign"
chemicals in foodstuffs. Thus, manuscripts 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 (substances deliberately added to foods for flavor, odo!', ap-
pearance, etc., as well as those inadvertently added during manufacture,
packaging, distribution, storage, etc.) are also considered suitable review
material.
Manuscripts are normally contributed by invitation, and may be in
English, French, or German. Preliminary communication with the editor
is necessary before volunteered reviews are submitted in manuscript form.
Department of Entomology F.A.G
University of California
Riverside, California
May 3, 1968
Table of Contents
Use and residues of mercury compounds in agriculture
By N. A. SMART . 1
Pesticide residues in Canada
By A. B. SWACKHAMER 37
Ueber den Abbau von Dazomet im Boden
By N. DRESCHER and S. Orro . 49
Examinations of Danish milk and butter for contaminating organo-
chlorine insecticides
By F. BRO-RASMUSSEN, Sv. DALGAARD-MIKKELSEN, Th. JAKOB-
SEN, Sv. O. KOCH, F. RODIN, E. UHL, and K. VOLDUM-CLAUSEN. 55
The fundamental kinetics of cholinesterase reaction with substrates
and inhibitors in an automated, continuous flow system
By G. Voss. 71
The dipyridylium herbicides, paraquat and diquat
By A. A. AKHAVEIN and D. 1. LINSCOTT 97
Subject Index . 147
Manuscripts in Press 152
Use and residues of mercury
compounds in agriculture
By
N. A. SMART*
Contents
I. Introduction . 2
II. Mercury compounds used 3
III. Diseases controlled and rate of use of mercury compounds 4
IV. Formulation and extent of use 9
(a) Formulation 9
(b) Extent of use 9
V. Methods of residue analysis 10
(a ) Wet oxidation-thiocarbazone methods 10
(b) Schoniger flask combustion methods 14
(c) Neutron·activation analysis 15
(d) General 15
VI. Residues in edible crops and tissues 15
(a) Apples . 16
(b) Pears 19
(c) Tomatoes 19
( d) Potatoes 20
(e) Grain 21
(f) Animal material, including eggs 22
(g) Water . 25
(h) Soil. 26
(i) Other crops and materials 26
VII. Movement of mercury in plants and trees 27
VIII. Regulatory 29
Summary 30
Resume. 31
Zusammenfassung 32
References . 32
.. Ministry of Agriculture, Fisheries & Food, Plant Pathology Laboratory, Hatching
Green, Harpenden, Hertfordshire, England.
2 N. A. SMART
I. Introduction
Mercury compounds were first used in Germany as seed dressings to con-
trol seed-borne diseases of cereals about 1914. 'Uspulun', described as a
'chlorophenolmercury' compound was placed on the market in 1915 by
Bayer A.G. as a liquid dressing and was soon widely used. Dusts, such as
'Ceresan', at first having phenylmercury acetate as the active ingredient and,
subsequently, a methoxyethylmercury compound, and 'Agrosan', a tolylmercury
acetate formulation, became more widely used ten years later. Liquid treat-
ments, using alkylmercury active ingredients, were reintroduced about the
time of World War II because of the reduced hazards and inconvenience to
operators dressing the grain in specially designed machines, although alkyl-
mercury compounds are more toxic than arylmercurials. In Sweden it has
recently been found that the extensive use of alkylmercury compounds can
lead to harmful contamination of the environment and there they have been
replaced by other organomercury compounds. In most countries both liquid
and dust treatments are commonly used. Formulations containing organo-
mercurials have been found to give a better control of fungal diseases of
grain than non-mercurial formulations.
Mercury compounds are now also used as foliar sprays, as aerosols in
glasshouses, in the wood pulp and paper industries, and in a variety of other
ways. The monetary value of mercury compounds used in world agriculture
is at least five million pounds sterling per annum.
The possible hazardous nature of mercury residues in foodstuffs was
emphasized in the 1950's at Minamata, Kyushu, Japan. An efHuent system
from a chemical factory had been opened for passing waste containing,
among other products, amounts of mercury into Minamata Bay. The bay
was regularly used as a source of seafood for many of the families inhabit-
ing the eleven small villages along its shores. In 1953 severe neurological
disorders among people living in the area were recorded, most ending fatally
or with severe disability. All the persons affected had eaten fish or shell-
fish, which contained high levels of mercury, caught on the bay. Cats and
fish-eating birds were also affected. A methylmercury compound in the fish
was considered to be the main toxic agent.
In January, 1966, the Swedish Royal Commission on Natural Resources
held an international symposium in Stockholm on a number of facets of the
mercury residue problem; the extent to which grain is dressed, mercury
levels in the Swedish aquatic environment, modern methods of determining
mercury residues such as neutron-activation analysis, the chemical nature of
mercury residues, and other related topics were covered. Attention was
drawn to the importance of distinguishing between alkyl, aryl, and inor-
ganic mercury in order to evaluate the potential hazards of mercury residues
Residues of mercury compounds 3
and chromatographic procedures for achieving these separations were pre-
sented. Although proceedings of this interesting symposium have not yet
been published, some of the work presented there is discussed in this pres-
ent review.
Information on the diseases controlled, mode of application and residues
of mercury compounds in crops and foodstuffs, and methodology of residue
analysis are widely dispersed in numerous publications; this review brings
together essential data for those concerned with crop protection and its
problems.
II. Mercury compounds used
Organomercury compounds are widely used in world agricultute con-
trasted with lesser amounts of inorganic mercury compounds. The former
may be divided, chemically, into three groups: alkylmercury, alkyloxyalkyl-
mercury, and arylmercury compounds. Many of the organomercury com-
pounds may be regarded as salts of the moderately strong bases methyl-
mercury, ethylmercury, and alkyloxyalkylmercury hydroxides, or the weaker
base phenylmercury hydroxide, with acids such as hydrochloric, hydrobromic,
hydriodic, nitric, acetic, propionic, lactic, salicylic, benzoic, and silicic. Com-
pounds known to be used in world agricultute at the present time are:
Alkylmel'cul'Y compounds
Methylmercury sulphate, acetate, nitrile, propionate, 8-hydroxyquinolate,
2,3-dihydroxypropyl mercaptlide, pentachlorophenolate, p-chlorobenzoate,
benzoate, dicyandiamide
N -Methylmercury I,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6, 7, 7 -hexachloro-
phthalimide
Ethylmercury silicate, chloride, bromide, phosphate, acetone, urea, oleate,
stearate, pentachlorophenolate, hydroxide, thiouronium chloride, p-
toluene sulphonamide, 8-hydroxyquinolate
N -Ethylmercury 1,2,3 ,6-tetrahydro-3 ,6-endomethano-3 ,4,5 ,6, 7,7 -hexachloroph-
thalimide
Ethyl phenethynylmercury
Mercury pentanedione
Alkyloxyalkylmel'cury compounds
Methoxyethylmercury ohloriide, silicate, dicyandiamide, benzoate, lactate,
acetate
Ethoxyethylmercury ohloride, silicate, hydroxide
I-Carboxy-3-ethoxyethylmercury propandicarboxylate
Chloromethoxypropy lmercury acetate
p- (t-Oetyl) phenoxyethoxyethyl dimethylmercury benzyl ammonium chloride
Al'ylmel'cury compounds
Phenylmercury acetate, dimethyl dithiocal1bamate, chloride, dinaphthyl methane
sulphonate, urea, nitrate, iodide, benzoate, pyrocatechinate, triethanol
ammonium lactate, 8-hydroxyqUlinolate, hydroxide, lactate, oleate, pro-
pionate, salicylate, salicylanilide, formamide, naphthenate
4 N. A. SMART
N -Tolylmercury-p-toluene sulphanilide, tolylmercury chloride
Hydroxymercurichlorophenol, ihydroxymerourinitrophenol
Cresolmercury naphthenate
Diphenylmercury dodecenyl succinate
o-(Hydroxymercury) benzoic acid
Inorganic mercury compounds
Mercurous chloride
Mercutlic chloride
Mercuric oxide
III. Diseases controlled and rate of use of mercury compounds
Many fungus diseases of seeds, bulbs, plants, fruits, and vegetation are
controlled by mercury compounds, as shown in Table 1. Mercury compounds
are used for control of soil-borne fungi as well as of seed-borne diseases in
the United States whereas in most European countries they are predomi-
nantly used to control the latter.
Phenylmercury acetate is widely used in the wood-pulp and paper-making
industry: about 90 percent of ground wood pulp exported from Norway,
Sweden, Canada, and the United States contains up to 20 p.p.m. of mer-
curial and the compound is also widely used in slime control. A minor use
of organomercury compounds in forestry is in helping to preserve cut timber.
Table I also gives the range of rate of use of mercurials in world agri-
culture as far as can be ascertained. The ranges are large in some cases re-
flecting the different practices of countries.