Table Of ContentG. Matthess F. Frimmel P. Hirsch
H.D. Schulz H.-E. Usdowski (Eds.)
Progress in
Hydrogeochemistry
Organics - Carbonate Systems - Silicate Systems -
Microbiology - Models
Foreword by D. Maronde
With 285 Figures
and 108 Tables
Springer-Verlag
Berlin Heidelberg New York
London Paris Tokyo
Hong Kong Barcelona
Budapest
Professor Dr. G. Matthess Professor Dr. H.D. Schulz
Geologisch-PaHiontologisches Institut FB 5 - Geowissenschaften
Universitat Kiel Universitat Bremen
OlshausenstraBe 40-60 Klageniurter StraBe
W-2300 Kiel1, FRG W-2800 Bremen 33, FRG
Professor Dr. F. Frimmel Professor Dr. H.-E. Usdowski
Engler-Bunte-Institut Sedimentopetrographisches
Technische Universitat Karlsruhe Institut
Richard-Willstatter-Allee 5 Universitat G6ttingen
W-7500 Karlsruhe, FRG GoldschmidtstraBe 1
W-3400 G6ttingen, FRG
Professor Dr. P. Hirsch
Institut flir Allgemeine Mikrobiologie
Universitat Kiel Biozentrum
Am Botanischen Garten 19
W-2300 Kiel, FRG
ISBN-13 :978-3-642-76631-2 e-ISBN-13 :978-3-642-76629-9
DOl: 10.1007/978-3-642-76629-9
Library of Congress Cataloging-in-Publication Data
Progress in hydrogeochemistry: organics, carbonate systems, silicate systems, microbiology,
models/G. Matthess ... ret al.l, (eds.) p. cm. "This volume summarizes the main results of a
priority programme of the Deutsche Forschungsgemeinschaft (DFG), Bonn-Bad Godesberg"
- Pref. Includes bibliographical references and index
ISBN-13:978-3-642-76631-2 (U.S.)
1. Hydrogeology - Congresses. 2. Water chemistry - Congresses. I. Matthess, Georg. II.
Deutsche Forschungsgemeinschaft. GB1001.2.P77 1991551.48-dc20 91-22482 CIP
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1 Foreword
Earth scientists, who have worked together for 6 years in the priority pro
gram "Hydrogeochemical Processes in the Hydrological Cycle Within the
Unsaturated and Saturated Zones", have summarized the results of their
research in this volume. This is the occasion to take stock and then look
ahead. The priority program was set up by the Senate of The Deutsche
Forschungsgemeinschaft in October 1981. This was preceded by lengthy
and careful preparation by a Program Committee, and was finally recom
mended by the Senate Commission for Joint Research in Earth Sciences.
The main aim was the interdisciplinary research of geochemical processes
in natural systems in the total underground water cycle, whereby water
pollution was not to be considered.
Officially started on 1 September 1982, the program has received a
grant of DM 10.9 Mio. from the DFG, and this has enabled it to support a
total of 50 projects. Although at the beginning, practice-oriented projects,
which were funded elsewhere, were not to be included, many of the results
are applicable. The four categories presented were investigated with vary
ing intensity. An early concentration on certain representative fields of
measurement and research areas proved to be the right approach - this
avoided a waste of effort in other fields. During the period of the priority
program, new and topical questions arose, e.g. in context with the research
on the influence of microbacteria, the interaction of humic substances, as
well as with the development and application of hydrogeochemical and
geochemical-hydraulic models. This was one of the main reasons why the
program could be extended into the 6th year.
Cooperation in the priority program was strengthened by annual
workshops, in which all the scientists involved in the program participate.
In addition, there were also working group meetings, where results and
future plans could be discussed, as well as many meetings in the field. It is
but natural that at the end of the program, not all the questions originally
raised can be answered. Many new problems arose and have to be worked
on in the future. For example, a number of working groups from this
priority program have been involved for quite a while in another priority
program "Pollutants in Ground Water" and several scientists working in the
priority program are keen on participating in other interdisciplinary
projects in the future.
The major part of the grant - a DFG average of 75% - was utilised for
the financing of personnel. In contrast, there was a marked decrease in
VI Foreword
expenses for equipment, working material and travel. This enabled many
young scientists to complete their doctorates within the projects and some
were later even able to work there in a postdoctorate capacity.
The published results speak for the success ofthe program. While many
lectures given at congresses and workshops, as well as various publications
informed in detail about progress made in the projects, this volume sum
marizes most of the research undertaken by the participants and includes
some special contributions. It is due to the intensive efforts and active
support from the group of expert reviewers and the editing committee, to
whom we owe our heartfelt thanks. Special thanks go to the coordinator,
Prof. Georg Matthe~ and his helpers, without whose untiring efforts the
program could not have been successfully completed. It is to be hoped that
even in the future, cooperation will be a basis for further interdisciplinary
projects between earth scientists and scientists from related fields like
chemistry, hydrology, microbiology, physics and soil science.
Bonn-Bad Godesberg Dietrich Maronde
Preface
This volume summarizes the main results of a priority programme of the
Deutsche Forschungsgemeinschaft (DFG), Bonn-Bad Godesberg, on
Hydrogeochemical Processes in The Hydrological Cycle Within the Un
saturated and Saturated Zones, in which interdisciplinary projects of sci
entific institutions and single scientists were involved and financially
supported. Between 1982 and 1989, annual workshops were held at Bonn
Bad Godesberg or NeustadtlWeinstraBe which offered opportunities for
intensive discussions of preliminary results and for exchange of method
ological experiences.
During the last workshop in February 23/24,1989, at Kiel, the results
were publicly presented in lectures and posters to an international scien
tific forum. Invited speakers contributed overviews of the state of the art as
bases for critical discussion of the new achievements. The participants of
the programme have to thank Professor M. Schnitzer (Land Resources
Center, Agriculture Canada, Ottawa), Professor P. Deines (Dept. of Geo
chemistry, Pennsylvania State University, State College, Pa.), Dr. W.M.
Edmunds (Institute of Hydrology, Wallingford, UK), Professor D.L.
Balkwill (Dept. of Biological Sciences, Florida State University, Talla
hassee, Fla.), Professor W. Kinzelbach (Technical Hydraulics and Engi
neering Hydrology, Department of Civil Engineering, Gesamthochschule
University Kassel), and Dr. Tomas Paces (Geological Survey of Czecho
slovakia, Prague) for their valuable contributions to this event.
It is quite normal that a research programme which lasts for up to 10
years should lead to a number of results which have to be published
immediately. Therefore this volume is a mixture of review-type chapters
with references to already published experimental data and research pub
lications on work which has been done recently.
The contributions presented here were reviewed by international ex
perts for the respective chapters. We would like to express our very sincere
thanks to Professor P. Fritz, Professor P. Deines, Dr. W.M. Edmunds,
Professor W.e. Ghiorse (Cornell University, Ithaca, N.Y.), Dr. T: Paces, and
Professor E.M. Perdue (Georgia Institute of Technology, Atlanta, Ga.) for
their help in the preparation and improvement of chapters of this book.
The participants ofthe priority programme thank the DFG (Deutsche
Forschungsgemeinschaft), Bonn-Bad Godesberg, for the generous funding
of our programme, which enabled the interdisciplinary approach. Stimu
lating scientific discussion and team work became possible by the DFG
VIII Preface
providing adequate platforms, such as specific working groups, or the
annual workshops mentioned above. We especially thanks Drs. D. Maronde
and W. Eder, who have accompanied our efforts by helpful advice and
active help.
Our work could not have succeeded without the willing help of the
board of scientific programme reviewers Professors E. Althaus
(Karlsruhe), G. Einsele (Tiibingen), E. Jackwerth (Bochum), H. Kobus
(Stuttgart), B. Meier (Gottingen), K.O. Miinnich (Heidelberg), E. Thofem
(Bonn), and G. TOlg (Bochum). This board supported the programme by
criticism and many helpful suggestions.
A highlight during the 6 years' programme was the team work and
friendships which became established between different scientific institu
tions and single researchers. As an obvious effect of this, cross references
and information on help from co-participants can be found in different
sections of this volume. All these authors are particularly grateful for the
various help provided by the respective laboratories and scientists.
At July 1, 1990 Professor Reinhard Schweisfurth passed away unex
pectedly after a heart attack. We all feel sorrow for the loss of an honest,
creative and enthusiastic partner of scientific research in the subsurface
ecosystems. We have to thank him for all his engagement to this work.
On behalf of the participants
of the priority programme
G. Matthess, coordinator
Contents
1 Scope
G. Matthess . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2 Polar Organic Substances a~d Their Role
in the Wate .... Saturated and -Unsaturated Zones
2.0 Introduction
RH. Frimmel ....... 7
2.1 Isolation Procedures and Characterization Methods . .9
2.1.1 Isolation and General Characterization of Organic Acids
from Pore Water
RH. Frimmel . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.2 Isolation and Characterization of Soil Humic Matter
W. Finger, B. Post and H. Klamberg ..... . . . . . . . . . . . 13
2.1.3 Isolation and Characterization of Organic Substances
in Ground Water and Sediments
R Selenka and A. Hack ................. . . 19
2.1.4 Chromatographic Characterization of the Acid-Soluble Part
of Humic Substances
RH. Frimmel . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.1.5 Spectroscopic Characterization of Humic Substances
in the Ultraviolet and Visible Region
and by Infrared Spectroscopy
G. Abbt-Braun ............................ 29
2.1.6 Temperature-ProgrammedfTime-Resolved Pyrolysis Field
Ionization Mass Spectrometry - a New Method
for the Characterization of Humic Substances
H.-R. Schulten ............................ 36
X Contents
2.1.7 Interpretation of the Pyrolysis Products of Isolated Humic
and Fulvic Acids
G. Abbt-Braun ........................... 46
2.1.8 Characterization of Isolated Humic Material
by BC Nuclear Magnetic Resonance Spectroscopy
1. Buddrus and P. Burba . . . . . . . . . . . . .. ....... 52
2.1.9 Characterization of Humic Substances Extracted
by Organic Solvents
B. Post and H. Klamberg . . . . . . . . . . . . . . . . . . . . .. 56
2.2 Interaction of Inorganics with Humic Substances
2.2.1 Investigation of Metal Complexation by Polarography
and Fluorescence Spectroscopy
F.H. Frimmel. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 61
2.2.2 Determination of Complexation Equilibria
by the Ion-Exchange Method
W. Finger and H. Klamberg .................... 65
2.2.3 Sorption of Metals on Humic Material
R. Becker and H. Klamberg . . . . . . . . . . . . . . .. 71
2.2.4 Interactions of Humic Substances with Iodine
K.G. Heumann and C. Reifenhiiuser ..... . . . . . .. 77
2.2.5 Experiments on the Influence of Organic Ligands
upon Kinetics of Feldspar Weathering
A. Petersen, G. Matthess and D. Schenk. . . . . . . . . . . . .. 86
2.3 Characterization of Some Organic Acids
in the Subsurface of the Sandhausen Ecosystem
T. Cordt and H. Kussmaul . . . . . . . . . . . . . . . . . . . .. 93
2.3.4 Organic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . .. 94
2.3.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 94
Contents XI
3 Carbonate Systems
3.0 Introduction
E. Usdowski ............................ 101
3.1 Dissolution Kinetics iu the Generation
of Carbonate Ground Waters . . . . . . . . ..... 103
3.1.1 Theoretical and Experimental Results of the Kinetics
of Calcite Dissolution and Precipitation
W. Dreybrodt . . . . . . . . . . . . . . . . . . . . . . . ... 1O~
3.1.2 Field Measurements and Laboratory Experiments
on Calcite Dissolution Kinetics of Natural Porous Media
J. Baumann and H.D. Schulz . . . . . . . . . . . . . . . . . . . 112
3.2 Field Studies on Subsurface Water of Selected Sites
B. Merkel and J. Grossmann ........ . 129
3.2.1 Pore Water Sampling in Carbonate Terrains .... 129
3.2.2 Variation of Inorganic Carbon in the Unsaturated Zone
of a Carbonate Gravel System
L. Eichinger and B. Merkel ................ . . 139
3.2.3 Isotope Geochemistry of the Subsurface Carbonate System
in Sandhausen and Bocholt
H. Dorr, W. Leuchs, P. Obermann, W. Regenberg
and C. Sonntag . . . . . . . . . . . . . . . . . . . . .. 149
3.2.4 Application of Stable Carbon and Sulfur Isotope Models
to the Development of Ground Water
in a Limestone-Dolomite-Anhydrite-Gypsum Area
K. W. Schaefer and E. Usdowski . . . . . . . . . . . . . . 157
3.2.5 A dissolution Front at the Contact of Sands
to Marly Limestone Aquifers
H.R. Langguth and R. Schulz . . . . . . .......... 163
3.2.6 Carbonate Rock Dissolution
Under Intermediate System Conditions
J. Michaelis . ............................ 167
