Humic Substances in the Aquatic and Terrestrial Environment: Proceedings of an International Symposium Linkoping, Sweden, August 21–23, 1989

493 Pages·1991·6.05 MB·English

by  Bert Allard

Lecture Notes ni
Earth Sciences
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Springer-Verlag
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Editors
Prof. Bert Allard
Dr. Hans Bor6n
Prof. Anders Grimvall
Department of Water and Environmental Studies
Link6ping University
S-581 83 Link6ping, Sweden
ISBN 3-540-53?02-3 Springer-Verlag Berlin Heidelberg NewYork
ISBN 0-387-53702-3 Springer-Verlag New York Berlin Heidelberg
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Preface
In 1986 a Nordic conference on humic substances was arranged in Oslo, Norway.
The conference was very successful, and it was suggested that there should be
continued regular meetings for Scandinavian scientists working within this area.
Linkrping University accepted the responsibility of hosting the second meeting in this
series.
At an early stage it was decided that the meeting should also be open to non-
Nordic participants. Thus, the International Symposium on Humic Substances in the
Aquatic and Terrestrial Environment, August 21-23, 1989, in Linktiping, Sweden,
attracted about 120 participants from 19 nations. A total of 71 contributions were
presented, orally or as posters. Papers from both the oral and poster sessions have
been collected in this proceedings volume, in which the chapters have the same titles
as the oral sessions of the symposium. Each chapter (with the exception of Chap. 2)
starts with a paper based on the plenary lecture of the session.
The program and final selection of papers were made by the Scientific
Committee (Prof Bert Allard, Linkrping University; Dr GOran Bengtsson, University
of Lund, Sweden; Dr Hans Borrn, Linkrping University; Dr James Ephraim,
Linkrping University; Dr Egil Gjessing, National Institute of Public Health, Norway;
Prof Anders Grimvall, Linkrping University; Prof Bjarne Holmbom, University of
/~bo Academy, Finland; Dr Ronald Malcolm, US Geological Survey, USA; and Prof
Robert Petersen, University of Lund, Sweden). The assistance of Ms Irina Arsenie,
Ms Gunilla Asplund, Ms Maria Nordrn and Ms Catharina Pettersson, and also of the
members of the Scientific Committee, in editing and preparing the conference
proceedings is gratefully acknowledged, as well as the excellent help with word
processing and lay-out by Ms Susanne Eriksson, Ms Lisbeth Thombury and Ms Pia
Sandholm.
Financial contribution was obtained from the Swedish National Environmental
Protection Board.
Bert Allard, Hans Borrn and Anders Grimvall
Table of Contents
Introduction
The Different Roles of Hurnic Substances in the Environment
Bert Allard, Hans Bor6n and Anders Grimvall ................................................................
Session :1 Isolation, Fractionation, and Characterization
Factors to be Considered in the Isolation and Characterization of Aquatic Humic
Substances
R.L. Malcolm ...........................................................................................................................
Comparison of Aquatic Humic Substances of Different Origin
F.H. Frimmel and G. Abbt-Braun ....................................................................................... 37
Structural Features of Aquatic Fulvic Acids by Analytical and Preparative HPLC
Followed by Spectroscopic Characterization
F.Y. Saleh, W.A. Ong, L Kim, and Q. Haj-Mahmoud ..................................................... 47
Fluorescence Spectroscopy as a Means of Distinguishing Fulvic and Humic Acids
from Dissolved and Sedimentary Aquatic Sources and Terrestrial Sources
N. Senesi, T.M. Miano, and M.R. Provenzano ................................................................. 63
Dielectric Spectroscopy of Aqueous Solutions of Fulvic Acids
F.J. Gonzfilez.Vila, U. Kaatze, H. Lentz, F. Martin and R. Pottel ................................ 75
Cobaltihexamine as an Index Cation for Measuring the Cation Exchange Capacity
of Humic Acids
A. Maes, F. Van Elewijck, J. Vancluysen, J. Tits and A. Cremers ............................. 85
Investigation of Humic Acid Samples from Different Sources by Photon
Correlation Spectroscopy
M.S. Caceci and V. Moulin ................................................................................................. 97
The Behaviour of Diborane-Reduced Fulvic Acids in Flash Pyrolysis
F. Martin and F.J. Gonz~tles-Vila ....................................................................................... 105
Some Aspects of the Characterization of Humic Substances in Lake Waters
K. Pihlaja, J. Peuravuori, P. Vainiotalo and B. Nord4n ................................................ 113
Isolation and Fractionation of Humic Substances in Lake Waters
J. Peuravuori and K. Pihlaja .............................................................................................. 123
Dating of Groundwaters by 14C-analysis of Dissolved Humic Substances
C. Pettersson and B. Allard ................................................................................................. 135
Characterization of Organic Materials by Means of Electrofocusing
M. Govi, C. Ciavatta, L. Vittori Antisari and P. Sequi ................................................. 143
IV
Nature of Humic Substances of Mollisol and Luvisol in the Canadian Prairies
A. Singer and P.M. Huang .................................................................................................. 151
Session 2: Biological and Chemical Transformation and
Degradation
Influence of Vegetation Changes on Soil Organic Matter
P. Nornberg ............................................................................................................................ 165
Humification Parameters of Organic Materials Applied to Soil
C. Ciavatta, L. Vittori Antisari and P. Sequi .................................................................. 177
Solid State C31 CP MAS NMR Characterization of the Chemical Structure of
Terrestrial Organic Matter from Areas with Differing Vegetational Backgrounds
M. Krosshavn, J.O. Bjfrgum, T.E. Southon and E. Steinnes ....................................... 187
Carbon-13 Nuclear Magnetic Resonance Analysis, Lignin Content and
Carbohydrate Composition of Humic Substances from Salt Marsh Estuaries
J.J. Alberts, P.G. Hatcher, M.T. Price and Z. Filip ....................................................... 195
The Effect of Composting on the Organic Colloidal Fraction from Domestic
Sewage Sludge
G. Almendros, J.A. Leal, F. Martin and F.J. Gonzalez-Vila ......................................... 205
Some Effects of Ozonation of Humic Substances in Drinking Water
D. Hongve, V. Lurid, G..~kesson and G. Becher ............................................................ 217
Upgrading the Removal of Humic Substances and Mutagen Precursors in Water
Treatment
A. J/irvinen, M. Pelkonen and T. Vartiainen ................................................................... 225
Effects of Gamma Irradiation on an Aquatic Fulvic Acid
I. Arsenie, H. Bor4n and B. Anard .................................................................................... 233
Coloured Substances in Swedish Lakes and Rivers - Temporal Variation and
Regulating Factors
T. Anderson, A. Nilsson and M. Jansson .......................................................................... 243
Large-Scale Pattern of Mor Layer Degradability in Sweden Measured as
Standardized Respiration
E. Bringmark and L. Bringmark ........................................................................................ 255
Session 3: Complex Formation and Interactions with
Solids
Ion Binding by Humic Substances: Considerations Based on the Solution
Chemistry and Heterogeneity of Humic Substances
J.H. Ephraim, M.M. Reddy and J.A. Marinsky .............................................................. 263
IIV
The Incorporation of Natural Organic Matter - Cation Interaction into the
Speciation Code PHREEQE
W.E. Falek ............................................................................................................................. 277
Calcium Binding to an Aquatic Fulvic Acid
N. Paxtus and M. Wedborg ............................................................................................... 287
Interaction of Strontium and Europium with an Aquatic Fulvic Acid Studied by
Ultrafiltration and Ion Exchange Techniques
M. Nord4n, J. Ephraim and B. Allard .............................................................................. 297
Complexation Behaviour of Humic Substances from Granitic Groundwater
Towards Am(HI)
V. Moulin, M. Caeeei and M. Theyssier ........................................................................... 305
Natural Organic Acids in Acidic Surface Water. Acid-Base Properties, Complex
Formation with Aluminium, and their Contribution to Acidification
Y. H. Lee ................................................................................................................................ 315
Investigations of the Interaction of Transuranic Radionuclides with Humic and
Fulvic Acids Chemically Immobilized on Silica Gel
R.A. Bulman and G. Szabo ................................................................................................. 329
Complexing Properties of Humic Substances Isolated from Sea Water; the
Contribution of these Substances to Complexing Capacities of Water from the
Baltic Sea and Geochemical Implications of this Penomenon
J. Pempkowiak ...................................................................................................................... 339
An Evaluation of Chemically Immobilized Humic Acid: A New Stationary Phase
for RP-HPLC Prediction of Uptake of Organic Pollutants by Soils and Sediments
G.Y. Szabo, S. L. Prosser and R.A. Bulman .................................................................... 349
The Influence of Aquatic Humic Substances on the Octanol/Water Partition
Coefficient (Kow) of Pesticides and Trace Elements at Different pH Values
G. Riise and B. Salbu ........................................................................................................... 357
Session 4: Biological Activity
The Contradictory Biological Behavior of Humic Substances in the Aquatic
Environment
R.C. Petersen JR ................................................................................................................... 369
Effects of Humic Substances from Different Sources on Growth and Nutrient
Content of Cucumber Plants
M. Abad, F. Fornes, D. Garcla, J. Cegarra and A. Roig .............................................. 391
Phytotoxic Substances in Runoff from Forested Catchment Areas
A. Grimvall, M.-B. Bengtsson, H. Bortn and D. Wahlstrtm ........................................ 397
Interaction of Humic Acids and Humic-Acid-Like Polymers with Herpes gimplex
Virus Type 1
R. KI6cking and B. Helbig ................................................................................................ 407
IIIV
Effects of pH and Natural Humic Substances on the Accumulation of Organic
Pollutants in two Freshwater Invertebrates
J. Kukkonen ........................................................................................................................... 413
Influence of Natural Humic Acids and Synthetic Phenolic Polymers on
Fibrinolysis
H.-P. Klrcking ....................................................................................................................... 423
Differential Inhibitory Effects of Humic Acids on Coagulation Systems of Human
Blood
H. Kiibler ............................................................................................................................... 429
Session 5: Halogenation of Humic Substances
Mutagenic Compounds from Chlorination of Humic Substances
B. Holmbom ........................................................................................................................... 439
Mutagenic Activity in Disinfected Waters and Recovery of the Potent Bacterial
Mutagen "MX" from Water by XAD Resin Adsorption
P. Baeklund, E. Wondergem and L. Kronberg ................................................................ 449
Formation of 3-Chloro-4-(Dichloromethyl)-5-Hydroxy-2(5H)-Furanone (MX) and
Mutangenic Activity by Chlorination of Phenolic Compounds
V.-A. LCtngvik, O. Hormi, L. Kronberg, L. Tikkanen and B. Holmbom .................... 459
Iodinated Hurnic Acids
J.V. Christiansen and L. Carlsen ....................................................................................... 467
Soil Peroxidase-Mediated Chlorination of Fulvic Acid
G. Asplund, H. Borrn, U. Carlsson and A. Grimvan ..................................................... 475
Natural Organochlorine in Humic Soils. GC and GC-MS Studies of Soil
Pyrolysates
H.J.P. de Lijser, C. Erkelens, A. Knoll, W. Pool and E.W.B. de Leer ....................... 485
Organic Halogens in Danish Groundwaters
............................................................................................................C. .......G.rc.n .............. 495
xidneppA
List of Participants 509
Introduction

The Different Roles of Humic Substances
in the Environment
Bert Allard, Hans Borrn and Anders Grimvall
Department of Water and Environmental Studies, Linkrping University,
S-581 83 Linktiping, Sweden
Humic substances, comprise a class of biogenic, coloured, organic substances that
are ubiquitous in soil, sediment and water. Originally, the occurrence and nature of
humic substances were regarded as issues of primarily academic interest. This
situation is now rapidly changing, and studies of humics have gained recognition as
important contributions to environmental science. In particular it has been shown that
humic substances, in several different ways can interact with biologically active
substances, thereby modifying their environmental impact (see Table 1).
Whereas the history of soil humus studies goes back to the 19th century, the
awareness of aquatic humus is more recent. The brownish colour that, in many
surface waters, shows the presence of substantial amounts of humic substances, was
long considered to be a harmless phenomenon that did not call for detailed
investigations. Hnmic waters had few known toxic effects, and the refractory
character of hnmic substances indicated the they played a peripheral role in most
biochemical processes. In fact, it was not until the mid 70's that aquatic humus was
brought into focus in environmental science. The event trigging this was the
discovery of the interaction between humic substances and chlorine used for
disinfection of drinking water. Toxic substances, such as chloroform, were detected in
all chlorinated waters, and humic substances were identified as the main precursors.
The role of humics in the mobilization and subsequent transport of trace elements
in the environment was recognized for the first time in the early 80's. This role was
considered to be of particular importance in connection with geologic storage of
high-level radioactive waste. In water with "normal" concentration levels of humic
compounds, the speciation of e.g. the trivalent actinides, would be entirely dominated
by the complexation with these agents.
Table 1 Some different roles of humic substances in the environment.
Complexing agent Complexing agent Precursor of Precursor of
or adsorbent or adsorbent toxic substances toxic substances
for man-made for naturally ni technical ni natural
pollutants gnirrucco processes processes
substances