Table Of ContentACS SYMPOSIUM SERIES 393
Biogenic Sulfur
in the Environment
Eric S. Saltzman, EDITOR
University of Miami
Willia
Florida International University
Developed from a symposium sponsored
by the Division of Environmental Chemistry
at the 194th Meeting
of the American Chemical Society,
New Orleans, Louisiana
August 30-September 4, 1987
American Chemical Society, Washington, DC 1989
In Biogenic Sulfur in the Environment; Saltzman, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
Library of Congress Cataloging-in-Publication Data
Biogenic sulfur in the environment.
Eric S. Saltzman, editor. William J. Cooper, editor
Developed from a symposium sponsored by the Division
of Environmental Chemistry at the 194th Meeting of the
American Chemical Society, New Orleans, Louisiana,
August 30-September 4, 1987.
p. cm.—(ACS Symposium Series, 0097-6156; 393).
Includes index.
ISBN 0-8412-1612-6
1. Sulfur—Environmental aspects—Congresses
2. Sulfur cycle—Congresses.
I. Saltzman, Eric S. 1955- . II. Cooper, William J.
III. American Chemical Society. Division of
Environmental Chemistry. IV. American Chemical
Society. Meeting (194th: 1987: New Orleans, La.).
V. Series
TD196.S95B56 1989
574.5'.222—dc19 89-6566
CIP
Copyright © 1989
American Chemical Society
All Rights Reserved The appearance of the code at the bottom of the first page of each
chapter in this volume indicates the copyright owner's consent that reprographic copies
of the chapter may be made for personal or internal use or for the personal or internal
use of specific clients. This consent is given on the condition, however, that the copier
pay the stated per-copy fee through the Copyright Clearance Center, Inc., 27 Congress
Street, Salem, MA 01970, for copying beyond that permitted by Sections 107 or 108 of the
U.S. Copyright Law. This consent does not extend to copying or transmission by any
means—graphic or electronic—for any other purpose, such as for general distribution, for
advertising or promotional purposes, for creating a new collective work, for resale, or for
information storage and retrieval systems. The copying fee for each chapter is indicated in
the code at the bottom of the first page of the chapter.
The citation of trade names and/or names of manufacturers in this publication is not to
be construed as an endorsement or as approval by ACS of the commercial products or
services referenced herein; nor should the mere reference herein to any drawing,
specification, chemical process, or other data be regarded as a license or as a conveyance
of any right or permission to the holder, reader, or any other person or corporation, to
manufacture, reproduce, use, or sell any patented invention or copyrighted work that may
in any way be related thereto. Registered names, trademarks, etc., used in this publication,
even without specific indication thereof, are not to be considered unprotected by law.
PRINTED IN THE UNITED STATES OF AMERICA
In Biogenic Sulfur in the Environment; Saltzman, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
ACS Symposium Series
M. Joan Comstock, Series Editor
1989 ACS Books Advisory Board
Paul S. Anderson Mary A. Kaiser
Merck Sharp & Dohm
Laboratories
Michael R. Ladisch
Alexis T. Bell
Purdue University
University of California—Berkeley
John L. Massingill
Harvey W. Blanch
Dow Chemical Company
University of California—Berkeley
Daniel M. Quinn
Malcolm H. Chisholm
University of Iowa
Indiana University
James C. Randall
Alan Elzerman Exxon Chemical Company
Clemson University
Elsa Reichmanis
John W. Finley AT&T Bell Laboratories
Nabisco Brands, Inc.
C. M. Roland
U.S. Naval Research Laboratory
Natalie Foster
Lehigh University
Stephen A. Szabo
Conoco Inc.
Marye Anne Fox
The University of Texas—Austin Wendy A. Warr
Imperial Chemical Industries
G. Wayne Ivie
U.S. Department of Agriculture, Robert A. Weiss
Agricultural Research Service University of Connecticut
In Biogenic Sulfur in the Environment; Saltzman, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
Foreword
The ACS SYMPOSIUM SERIES was founded in 1974 to provide a
medium for publishing symposia quickly in book form. The
format of the Series parallels that of the continuing ADVANCES
IN CHEMISTRY SERIES except that, in order to save time, the
papers are not typeset but are reproduced as they are submitted
by the authors in camera-ready form. Papers are reviewed under
the supervision of the Editors with the assistance of the Series
Advisory Board and are selected to maintain the integrity of the
symposia; however
lished papers are no accepted report
research are acceptable, because symposia may embrace both
types of presentation.
In Biogenic Sulfur in the Environment; Saltzman, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
Preface
E CHEMISTRY OF SULFUR COMPOUNDS in the environment has taken
on a new significance in recent years due to its involvement in the
formation of atmospheric aerosols and its impact on acid precipitation,
human health, and the radiation balance of the atmosphere. A major
focus of research on the sulfur problem is the natural cycling of
biologically produced sulfur compounds through the environment. An
understanding of the processe
assess the background level
emissions are superimposed and to develop mechanistic models for the
chemical conversions that biogenic and anthropogenic sulfur undergo
after release into the environment.
The content of the symposium on which this book is based was
unusual in that it involved an extremely wide range of disciplines, from
gas kinetics to biochemistry. The purpose behind this was to help
broaden the perspective of investigators beyond that of their own
disciplines; to encourage interaction and collaboration on multi-
disciplinary aspects of the sulfur cycle; and to promote the transfer of
new analytical techniques across disciplinary boundaries. Normally, the
research papers reported at the symposium would be published in a
diverse array of specialized scientific journals. We felt that publishing
the papers in one volume would give scientists who are interested in
sulfur cycling ready access to current ideas in fields that are outside their
specialties.
Biogenic Sulfur in the Environment is divided into eight sections. The
first two sections, which deal with terrestrial and freshwater systems,
address the emission of volatile reduced sulfur gases into the atmosphere
by soils, plants, and wetlands. This subject has received a lot of attention
recently because of the possibility that, at least locally, the emissions of
natural sulfur compounds may be substantial even compared to
anthropogenic sources of sulfur dioxide. Efforts to quantify fluxes
accurately and to inventory these sources on a regional scale have
required advances in both analytical techniques and the design of flux
experiments. Developing predictive or mechanistic models of such
processes is currently in an early stage because it requires an
ix
In Biogenic Sulfur in the Environment; Saltzman, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
understanding of the diverse factors controlling the natural variability of
complex environments. Two chapters address the question of emissions
of sulfur gases from higher plants, a source about which little is currently
known.
Sulfur cycling in fresh water is also important to understanding the
impact of acid precipitation in these environments. The presence of
hydrogen sulfide results not only from dissimilatoiy sulfate reduction, as
commonly assumed, but also from putrefaction. Chapter 8 addresses an
entirely different question: the potential reactivity of sulfur species
toward nucleophilic reactions with halogenated organic compounds of
anthropogenic origin. These reactions may be an interesting link
between natural sulfur cycling and pollutant transport in subsurface
environments.
The third, fourth, and fifth sections investigate the distribution and
biological and chemical
the oceans. The third sectio
which is the predominant form of volatile sulfur in the ocean. Research
in the past has concentrated on documenting the distribution of DMS in
various oceanic environments. The factors controlling this distribution
are not well understood. These chapters examine laboratory and field
investigations relating DMS production to productivity and speciation.
The fourth section focuses on marine sediments, stressing the
biological transformations of DMS and other organosulfur compounds.
The fate of sulfur in sediments is interesting because of its role as a
microbial matabolite and because of its ultimate fate as an impurity in
fossil fuels.
Hydrogen sulfide formation through dissimilatory sulfur reduction
has for years been known as a source of environmental sulfur. This
compound has invited recent study because of its possible effect on the
redox chemistry of sea water. Both the lifetime and the oceanic
concentrations of this reactive and highly toxic compound are the focus
of the fifth section.
The sixth, seventh, and eighth sections of this volume deal with the
atmospheric cycling of biogenic sulfur compounds. This aspect of the
sulfur cycle has received a great deal of attention in recent years because
of its obvious relationship to the acid rain problem and the discovery
that natural marine sources constitute a major portion of the total global
atmospheric sulfur burden. The chapters in these sections focus on
three aspects of this cycle: field measurements and techniques used to
establish the distributions and fluxes, experimental studies of reaction
mechanisms and rates, and numerical simulations of the atmospheric
sulfur cycle. Two chapters address the chemical processes involving cloud
x
In Biogenic Sulfur in the Environment; Saltzman, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
droplets and aerosols. Such multiphase processes are an important
aspect of the atmospheric sulfur cycle, although one which is particularly
difficult to study experimentally.
Acknowledgments
Support for the symposium that served as the catalyst for this volume
was obtained from the Office of Naval Research and the Division of
Environmental Chemistry of the American Chemical Society. This
support provided many speakers with travel allowances to present papers
at the symposium. The participation of authors, many of whom would
not normally attend an ACS meeting, resulted in lively discussions, a
more comprehensive coverage of the subject, and new collaborative
research efforts after the symposium.
The session chairmen
Edward J. Green, Joh
considerable time during the symposium.
All of the chapters in this volume were reviewed by at least one
reviewer. We thank them for their efforts and the timeliness of the
reviews.
We appreciate the helpful assistance of the acquisitions editors of the
ACS Books Department. Our initial efforts were guided by Susan
Robinson, whose good-natured persistence was invaluable. The finishing
touches were skillfully handled by Robin Giroux.
We wish to thank Maria Fernandez-Reynardus for her energetic
administrative assistance throughout the review process. All of the final
word processing of the chapters was accomplished under the watchful
guidance of Marva Loi. Without her, the production of this book would
not have been possible. She was assisted by Sonia Ling, who provided
invaluable support in word processing. We would also like to thank
Joseph Prospero, chairman of the Division of Marine and Atmospheric
Chemistry at the University of Miami, for generously allowing us the use
of divisional facilities to produce Biogenic Sulfur in the Environment.
ERIC S. SALTZMAN
University of Miami
Miami, FL 33149
WILLIAM J. COOPER
Florida International University
Miami, FL 33199
December 13, 1988
xi
In Biogenic Sulfur in the Environment; Saltzman, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
Chapter 1
Biogenic Sulfur Emissions
A Review
Viney P. Aneja1 and William J. Cooper2
1Department of Marine, Earth, and Atmospheric Sciences,
North Carolina State University, Raleigh, NC 27695
2Drinkin
Florida Internationa
Biogenic sulfur emission rates are reviewed for important
components of the sulfur cycle. A summary of emission estimates
is provided for vegetation, coastal and wetland ecosystems, inland
soils, and oceanic environments. One area which is briefly
reviewed, emissions from plants, may play a significant role in
global sulfur cycling and very little work has been reported
covering this subject. An important trend is that estimates of
biogenic emissions are being lowered for terrestrial and wetlands
areas. This, coupled with decreased wetland acreage, may
significantly decrease local estimates of biogenic sulfur to acid
precipitation.
Sulfur in the atmosphere originates either from natural processes or
anthropogenic activity. The natural biogenic sources are thought to constitute a
large fraction (estimates as high as 50 % have been reported) of the
atmospheric sulfur burden (1-8). As such, these natural sources may have a
substantial impact on global sulfur cycling.
Biogenic sulfur, that is sulfur compounds which result from biological
processes, are only one component of the natural sulfur cycle. The first
measurements of biogenic sulfur fluxes were those of Aneja and co-workers
(9.10). Numerous studies have been published in the last decade which add to
our understanding of the natural sulfur emissions (11-29). This research has
provided experimental data, which is helpful in refining the biogenic emission
estimates necessary to refine the global sulfur cycle. This data base, although
sparse for detailed quantitative estimates, is helpful for estimating emissions
from both terrestrial and oceanic environments.
In the initial attempts at developing global sulfur budgets, biogenic
emissions were usually obtained from the amount of sulfur necessary to balance
the cycle. This resulted in considerable scatter in the biogenic estimates, from
34 Tg S yr1 (4) to 267 Tg S yr1 (2), where Tg = 1012 g. It is possible with the
existing data to begin to make estimates of biogenic emissions based on direct
measurements. However, additional data are necessary to assess biogenic sulfur
emissions independent of other portions of the global sulfur cycle.
0097-6156/89/0393-0002$06.00/0
* 1989 American Chemical Society
In Biogenic Sulfur in the Environment; Saltzman, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
1. ANEJA AND COOPER Biogenic Sulfur Emissions 3
The objectives of this overview chapter are:
1. To review the extant data base of biogenic sulfur emissions for terrestrial
and oceanic environments and to summarize direct estimates of emissions
where possible.
2. To integrate the other chapters of this section into the discussion.
Biogenic Sulfur Emissions from Vegetation
It has been recognized for some time that sulfur is essential for plant growth. It
is used in amino acids, and many other biochemicals. The biological
transformation of sulfur compounds in natural ecosystems is closely coupled to
the formation of living biomass and to the subsequent decomposition and
remineralization of the biomass. Plants contain an average sulfur content of
0.25 % (dry weight basis) (2Q). Hence sulfur may be released directly from
vegetation or during the process(es) of decomposition of the organic matter.
Data on sulfur released by
are not known in any detail
and a more detailed discussion follows in the next chapter (21).
Sulfur compounds are known to be volatilized from living plant leaves (22),
and from decaying leaves (22). It has been estimated that sulfur emission rates
from decaying leaves are about 10 to 100 times higher than those from living
leaves of the same species (22). Many fungi and bacteria release sulfur
compounds (24) during plant decomposition. Some plants are known to emit
H2S (11.29.31.35.36). Emission rates of HoS from several lawns and from a pine
forest on aerobic soils, in France, ranged from 0.006 to 0.25 g S nr2 yr1 (25).
However, in the Ivory Coast, West Africa, emission rates of H2S from humid
forests ranged between 0.24 and 2.4 g S nr2 yr1 (26).
Some plants are also known to emit dimethyl sulfide, DMS, (13.37).
carbonyl sulfide, COS, (22), and carbon disulfide, CS2, (13.37-41). and possibly
ethyl mercaptan (40.41). A study conducted in a tropical rain forest which
focused on Stryphnodendron excelsum is trteated in more detail in a following
chapter (41). It is quite possible that additional studies as described in Chapter
5 (41) will lead to the discovery of other terrestrial Mhot spots" which may be
important in biogenic sulfur cycling.
Emission rates of sulfur from crops including corn, soybeans, oats, alfalfa,
and miscellaneous vegetables have been measured (27-29). The flux from crops
range from 0.008 to 0.3 g S nr2 yr1. H2S and DMS are the two primary sulfur
species being emitted by crops. Emission rates of sulfur from a variety of plants
are summarized in Table I.
It is also possible that plants emit volatile sulfur containing compounds
which are not easily analyzed by current gas chromatographic methods. Thus,
the use of other analytical methods may reveal compounds as yet unidentified
which serve as a source of volatile biogenic sulfur compounds.
Biogenic Sulfur Emissions from Wetlands
The tidal flats of marine environments are areas of extreme complexity and
biological activity. They serve as both sources and sinks of a wide variety of
compounds and materials. They are in a constant state of mass, energy and
momentum flux with the surrounding environment. In these areas sulfur plays a
major role in biological processes, principally because of the relatively high
concentration of sulfate ion in marine waters.
Sulfate ion is the major electron acceptor for respiration in anoxic marine
sediments and may account for 25 % of the total sediment respiration in near
shore sediments, 0.3 to 3 g C nr2 day1. In salt marsh sediments, where total
In Biogenic Sulfur in the Environment; Saltzman, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
BIOGENIC SULFUR IN THE ENVIRONMENT
Table I. Biogenic Emissions of Sulfur From Vegetation
Plant Mean Sample Primary Sulfur Emission Rate Ref.
Temperature Species
(°C) g S nr2 yr1
Spartina
alterniflora, N.C. 30 DMS 0.66
S. alterniflora, N.C. 25 CS 0.20
2
Stryphnodendron
excelsum, Costa Rica NR* (41)
4 meters from tree trunk 1.5
0.022
16 meters from tree trun
Lawn, France 22 H S 0.24
Pine Forest, France 10 Hz2S 0.023
Humid Forest,
Ivory Coast 25 H S 0.88 (26)
2
Crops
Oats (with soil), IA 35.4 DMS, H S 0.016 (22)
Cora, IA, OH 28.9 DMS, H2S 0.032 (22)
Soybeans, IA 32.8 DMS, H2S 0.066 (22)
Alfalfa, WA 22.4 DMS, H2S 0.056 (22
2
Trees
Deciduous, IA, OH, NC 29.5 DMS, H S,
COS 2 0.007
Coniferous, NC 29.2 COS 0.005
Crops
Soybeans, IA 25 5 0.0018 (22)
Carrots, OH 22 0.113 (27.)
Onions, OH 22 0.104 (27.)
Grass, IA 25.5 0.018 (27.)
Crops
Soybeans, 30 DMS 0.037 (28)
Oats, 30 DMS 0.023 22
Orchard Grass, 30 DMS 0.008 (28.)
Purple Clover, 30 DMS 0.007 (28.)
Corn, 30 DMS 0273 (28)
NR = not reported
In Biogenic Sulfur in the Environment; Saltzman, E., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
