_ANNUAL REPORT No 4

The IGCP 429 Annual Report No.3, 2000

ORGANICS IN MAJOR ENVIRONMENTAL ISSUES

DURATION AND STATUS: 1998 - 2002 - ONGOING

PROJECT LEADERS: JAN PASAVA & JAN JENIK, (IGCP) (MAB)

Czech Geological Survey (address on guiding pages) & Faculty of Botany, Klarov 3 Charles University, CS-118 00 Praha 1 Benatska 2, Czech Republic CS-128 01 Praha 2

phone: (+420)-2-5817390 & phone:(+420)-2-21953119; fax: (+420)-2-5818748& fax: (+420)-2-21953125, e-mail: pasava@cgu.cz & jenik@prfdec.natur.cuni.cz

PROJECT SECRETARY: ANDREW P. GIZE, Department of Geology, The University of Manchester, Manchester, M13 9PL, UK

phone: (+44)-61-275-3832; fax: (+44)-61-275-3947; e-mail: andy_gize@email.msn.com

INTRODUCTION

IGCP Project 429 "Organics in Major Environmental Issues" (1998-2002) was approved by UNESCO in February 1998. In the period from October 15, 1998 to October 15, 2000 around 80 scientists from 31 countries participated in the Project activities and new links have been established in African and other development countries (Botswana and Burkina Faso, for example).

The present configuration of the Project is as follows:

National Working Group Suggested Representative

Albania	E. Xhemo
Argentina	M. Brodtkorb
Australia	B. Lottermoser
Austria	H. Lobitzer
Botswana	M. Segola
Brazil	Laecio C. de Souza
Bulgaria	T. Todorov
Burkina Faso	U. Wenmenga
Canada	J.F. Barker
China	Fan Delian
Czech Republic	B. Kribek
Estonia	E. Puura
Finland	K. Loukola-Ruskeeniemi
France	M. Leblanc
Germany	K. Bosecker
Hungary	M. Polgari
Israel	Y. Chen
Italy	P. Lattanzi
Japan	S. Nakashima
Jordan	T.M. El-Hasan
Korea	H.T. Chon
Macedonia	T. Serafimovski
Mongolia	B. Tumenbayar
Nigeria	S. Akande
Philippines	E.C. Santiago
Poland	W. Mayer
Romania	C. Dinulescu
Russia	A. Kontorovich
Slovakia	I. Rojkovic
Slovenia	T. Dimkovski
South Africa	K. Walemba
Spain	I. Suarez-Ruiz
Switzerland	J. Spangenberg
United Kingdom	J. Parnell
United States	T. Giordano

1. SUMMARY OF MAJOR PAST ACHIEVEMENTS OF THE PROJECT

1999 was the second year of the IGCP 429, characterized by a significant progress within all eight topical working groups covering major issues of the Project. Besides 31 countries involved in the Project, new links have been established in Albania and Jordan. Two major international events and a number of meetings on national level were arranged within IGCP 429 activities. The very well attended Annual International Meeting was held in London, U.K. in August. Another very important aspect of the IGCP 429 activities was a “training component”, which was represented by an active Project involvement in the preparation and organization of the GEOCHIM 99 - a Postgraduate Certificated Training Course on the Geochemical Prospecting Methods and their Environmental Applications. The course was held in the Czech Republic in September and 12 scientists from developing countries took part in this event.

The results of the IGCP 429 have been summarized in more than 80 scientific papers.

2. ACHIEVEMENTS OF THE PROJECT THIS YEAR

2.1. GENERAL SCIENTIFIC ACHIEVEMENTS

From October 15, 1999 to October 15, 2000, the activities of the Project successfully continued.

Two major international events and several meetings on national level were arranged within IGCP 429.

The 2000 Annual International Meeting on the "Organics in Major Environmental Issues (C7 Special Symposium)", took place in Rio de Janeiro, Brazil, between August 6-17, within the 31^st International Geological Congress. Eight scientific talks (each 30 min. plus 5 min. discussion) were presented by scientists from 8 countries at a very well attended half day session of the IGCP 429 (30-60 people). Altogether 9 peer reviewed extended (4 page) abstracts were published in the Congress Abstract Volume on CD-ROM and selected papers are planned to be published in the Geochemical Transactions (a new electronic journal published by the Royal Society of Chemistry, in collaboration with the Division of Geochemistry of the American Chemical Society).

Another very important aspect of the IGCP 429 activities - a “training component”, was an active involvement in the preparation and organization of a training course for people from developing countries. IGCP 429 was together with the Czech Geological Survey in Prague, Czech Commission for UNESCO and UNESCO/Paris one of the organizers and scientific guarantees of the GEOCHIM 2000 Postgraduate Certificated Training Course. The course was held in Prague and Dolni Rozinka (Czech Republic) from September 4 through September 18, 2000 and 13 geoscientists representing 9 developing countries were trained both theoretically and practically in the geochemical exploration methods and their environmental applications. Soil geochemistry, biogeochemistry and hydrogeochemistry including their environmental applications as well as up to date results on the role of organic matter in major environmental issues were lectured by J. Pasava, M. Duris, B. Kribek, M. Novak and J. Vesely (IGCP 429 members from the Czech Geological Survey).

Call for abstracts was made for the IGCP #429 symposium "The role of organic matter in the formation of mineral deposits and related environmental issues" which will take place in Cracow, Poland in 2001 within the framework of a joint SGA-SEG Meeting.

Project activities planned for 2001, including a schedule and a scope of the next annual international meetings, work plan and a call for final publication (2002) have been discussed during the IGCP 429 meeting in Rio de Janeiro.

Newsletter summarizing 2000 activities and plans for 2001 was distributed to the participants.

The scientific results reached within individual eight topical workin groups can be briefly summarized as follows:

One of major highlights of the IGCP 429 activities came out of Swiss-U.S.-Slovenian collaborative study. The carbon isotope ratios of the individual lipids from different vegetable oils were analyzed by gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS). This approach provides further insight into the purity and geographic origin of the oils. The d¹³C of the fatty acids appear to be preserved where lipids distribution have been altered by degradation or burial. The results indicate that GC/C/IRMS of plants lipids may be a potential tracer of the global changes recorded in the terrestrial carbon cycle.

working hypothesis on a possible geochemical mechanism for the origin of life: coupled dehydration - polymerization - crystallization in the hydrous silica - iron hydroxides - amino and nucleonic acids systems.

WG1: Organic Matter - Metals Interaction

(A.P. Gize, UK - e-mail: <andy_gize@email.msn.com>

Numerous important studies on organic-metal interaction were carried out within the IGCP 429 activities.

Highlights of the study of complexation of Pd by natural organic ligands were presented by U.S. scientists. It was proved that all the organic ligands (acetate, oxalate, salicylate, phthalate and fulvic acids) increase the solubility of Pd in aqueous solutions and that this effect is indeed due to the formation of stable Pd(II)-organic ligand complexes. It is very likely that O-, N--, and S-groups on natural fulvic acids are capable of solubilizing and transporting significant amounts of Pd in natural waters, particularly soil solutions and sediment porewaters.

Very important scientific results have been reached by Russian scientists on the experimental modeling of platinum sorption on organic matter. The interactions of Pt-bearing aqueous solutions with fractionated organic matter was studied at 200-400°C and 1 kbar total pressure. It was concluded that Pt sorption on activated carbonized organic matter may be an affective mechanism of Pt accumulation in newly discovered low grade Pt deposits bound to low-rank brown coals and black shales.

The reversibility of metal-bacteria interactions through comparing estimated extents of desorption based on surface complexation modeling, to those observed in the experimental adsorption/desorption system was studied by U.S. scientists. The results have shown that the adsorption of Cd and Ca on Bacillus subtilis is rapid, fully reversible, and an equilibrium process. This is why the use of surface complexation modeling of aqueous metal adsorption onto bacterial surfaces yields accurate estimates of the distribution of metals in bacteria-bearing solutions.

The review of the investigations that quantify metal-bacteria, organic-bacteria, and bacteria-mineral adsorption reactions has shown that the surface complexation approach can successfully account for metal-bacteria, organic acid-bacteria, and bacteria-mineral adsorption reactions. This offers a powerful means for estimating the effects of bacteria on solute adsorption over a wide range of subsurface conditions.

Chinese scientists have concluded that the effects of humic substances on sorption of Yb³⁺, UO₂²⁺, Zn²⁺, I^- and SeO₃^2- onto Al₂O₃, Fe₂O₃, and SiO₂ depends not only on pH, but also on the nature of oxide, the nature of humic substance, fractionation of the humic substance by sorption, the relative strength of complexes of both soluble and sorbed humic substances, the extent of surface coverage by humic substance, the initial concentration of humic substance and the inorganic electrolyte composition.

A joint U.S.-Canadian experimental study has resulted in bringing new data on the impact of the Fe(III)-reducing bacteria Shewanella alga on the solid phase partitioning of dissolved Sr²⁺. The results have shown that non-viable S. alga cells and cell envelopes can sorb significantly greater quantities of Sr²⁺ compared to hydrous ferric oxide alone, and that siderite precipitation in live S. alga cultures enhances the solid partitioning of Sr²⁺.

Evaluation of the ability of hyperthermophilic microorganisms to transfer electrons to humic substances and other extracellular quinones has been carried out by U.S. scientists. They evidenced that the ability to reduce extracellular quinones is a characteristic of all of the hyperthermophiles studied which are in fact the organisms most closely related to the last common ancestor of extant organisms. This suggests that electron transfer to extracellular quinones and Fe(III) were initial steps in the eventual evolution of intracellular eletcron transport chains that employ quinones and iron-containing proteins.

Summary on organic-metal interactions pointing at a close association between migrated organic matter (bitumen) and metalliferous minerals in several Andean regions (western Argentina, Chile, Peru and Colombia) was presented by British scientists.

WG 2: Microbial Leaching in Environmental Clean Up

(K. Bosecker, Germany - e-mail: <k.bosecker@bgr.de> )

Bacteria play an important role in the concentration, crystallization, transportation and accumulation of almost all elements in the Earth´s environment. It is no secret that bacterial biomineralization plays a key role in the remediation of toxic heavy metals in polluted soils and water systems at abandoned mining sites.

Considerable progress in the field of remediation of heavy metals polluted soils was achieved by Belgium and U.S. scientists who reported on the use of heavy metal resistant bacteria in a bioreactor concept to remove bioavailable heavy metals in polluted soils. Contaminated soil is treated in a special tank reactor at the presence of Ralstonia metallidurans CH34, which allows the contaminating metals to be transferred from the soil particles to the bacterial cell walls. Special properties of the bacteria make settling process very slow allowing the separation between the soil and the metal loaded bacteria. These achievements are very important as heavy metals in soils are still a challenging problem all over the world and because of very restricted use of other remediation technologies as e.g. bioconversion.

Japanese scientists have been successful in biodegradation of hazardeous organochlorine compounds in groundwater using indigenous microbe. For example, methanotrophic bacteria cultivated from the polluted field is able to degrade trichlorethylene. This process is based on maintaining aerobic conditions in aquifer with adding nutrients and methane from a carbon source. Oxygen, methane and nutrients are liquified and diffused into aquifer through injection wells. Trichlorethylen is then detoxified by biodegradation during pumping up groundwater.

Interesting results have been reported by scientist from India and Trinidad who evaluated biosorption properties of nonedible woodrotting macro fungi (mushrooms) from India, which occur abundantly in tropical forests worldwide. Among the nine mushrooms screened for copper (II) uptake, Ganoderma lucidum exhibited the highest binding potential. Simple gravity settling could be used for separating the sorbent from the aqueous stream and it was suggested that Ganoderma. lucidum could bind many other metallic cations. These results are very important as biosorption, in which viable or nonviable biomass, is directed to accumulate toxic heavy metals from aqueous stream is attracting wide attention as an alternate wastewater treatment technology.

The study of factors controlling the bioaccumulation of mercury and methylmercury into benthic invertebrates and fish, carried out by U.S. scientists, has brought important scientific data. It was documented that the extent to which inorganic mercury and methylmercury are released from the solid phase (sediment or food) during digestion appears to be the process limiting the extent of bioaccumulation. These results are of high importance because the bioaccumulation of methylmercury into aquatic food chains is an important environmental health concern as levels of methylmercury in top predator fish are locally elevated enough to pose a threat to humans, and fish-eating mammals and birds.

German scientists have continued the study of microbial activity in various old mining dumps with new sampling in Zimbabwe, Namibia, Bolivia and Kazakhstan. Depending on the mineral composition of mine tailings and waste rocks and on the environmental conditions (temperature, humidity, oxygen availability) the microbial activity may cause major environmental problems. Microbial investigations will help to predict the evolution of acid mine drainage in mine wastes by looking for the presence of metal solubilizing bacteria (Thiobacillus ferrooxidans, Thiobacillus thioooxidans, Leptospirillum ferrooxidans) and heterotrophic acidophilic bacteria, by calculating the amount of various types of leaching bacteria and by measuring the biological activity under different environmental conditions. The results of this study have a great potential to provide guidance how to reduce or to inhibit the bacterial activity for mitigating acid mine drainage.

Bioaccumulation of Ag, As, Cd, Cu, Hg, Fe, Mn, Pb and Zn in some plants (Agrostis tenuis, Salix fragilis, Alnus glutinosa) and microscopic fungi living on/in highly polluted alluvial soils of the Stiavnicky potok brook area, a classical old mining district (Slovakia) was studied by Slovak scientists.

WG 3: Weathering of Organic Matter

(B. Kribek, Czech Republic- e-mail: <kribek@cgu.cz>)

Another for society very useful applied scientific results have been reached by Czech scientist on the weathering of organic matter in waste dumps of coal mines of various age (1 - 112 years) from the Pilsen Basin (West Bohemia, Czech Republic). This study has shown that significant amount of oxidation products (humic substances) is produced during weathering. From the agrochemical point of view, the weathering of organic matter affects namely the sorption capacity of rocks dumped on the tips. Both the long-term weathering and the experimental oxidation (low-temperature oxidation at T=140°C) of the organic matter manifest themselves namely by the decrease of the hydrogen content in their structure. This is evidenced by the decrease of the vibration intensity of aliphatic C-H bonds and by the increase in the vibration intensity of carbonyl and carboxyl groups. In contrast to the oxidation of aliphatic (algae-type) organic matter, the oxidation of coal-type organic matter is more complex. Very quick consumption of O₂ dominates the initial stage of oxidation and is followed by a temporary period when dehydrataion- and decarboxylation-reactions predominate. In the final stage of the oxidation, the O₂-consumption and reaction product formation are in equilibrium. These results should be taken into consideration at the remediation of various dumpsites after coal mining worldwide.

Studies of organic matter in lignites and waste material deposited around the open pit coal mines at Suvodol (Bitola), Brik (Berovo) and Oslomej (Kicevo) have successfully continued in Macedonia and also in Romania.

The U.S. scientists studied weathering profiles developed on organic carbon-rich black shales to examine the loss and degradation of organic matter during weathering and its role in the geochemical carbon cycle. They suggested a two component model for kerogen weathering: largely non-selective oxidation and hydration, followed by cleavage/dissolution of oxidized kerogen fragments. It was concluded that the extent of weathering in a given outcrop is likely limited by a combination of the rate of physical erosion and exposure of the rock to oxidizing surface waters, with organic matter type/composition playing a lesser role.

Interesting results have been obtained from the study of the inhibiting effect of fertilization and soil compaction on CH₄ oxidation by measuring gas fluxes and soil mineral N dynamics in the field, and CH₄ oxidation rates in laboratory-incubated soil samples by Norwegian scientists. They found that the substrate affinity of the CH₄-oxidizing microflora was about the same in both the fertilized and the unfertilized soils and that soil compaction resulted in a persistent reduction of CH₄ influx, also confirmed in laboratory incubations with sieved (4-mm mesh) soil samples. These results may indicate that soil compaction has affected the biological potential for CH₄ oxidation in the soil.

Notable scientific results were reached by British scientists who studied impact of inorganic N on microbial biomass C and N and extractable dissolved organic carbon in raised bog peat beneath Sphagnum capillifolium and S. recurvum in north-east Scotland. They found that microbial biomass C and N from raised bog peats showed similar seasonal patterns for most depths and that the effects of added N on microbial biomass C and N changed with time. The addition of inorganic N had greatest effect during October when water table had risen to the surface and microbial C and N in the untreated cores had decreased.

Studying contemporary carbon stocks of mineral forest soils in the Swiss Alps, Swiss scientists have estimated that the 0-20 cm layers of mineral forest soils in Switzerland store about half of the C sequestered by forest trees (136 Tg C) and more than five times more than organic horizons (13.2 Tg C).

WG 4: Acid Mine Drainage

(E. Puura, Estonia - e-mail: <epuura@math.ut.ee> or <erx@ket.kth.se>)

Organic fossil fuels contain often pyrite, as the sedimentation under anaerobic conditions leads to the reduction of both Fe(III) and sulfate, with pyrite becoming oversaturated. During mining activities, pyritic material is brought into the connection with atmosphere. The result is active oxidation of pyrite and formation of acid leachate, commonly known as acid mine drainage (AMD) or acid rock drainage (ARD). The leachate often contains high concentrations of heavy metals, that were originally in the sulfidic form, or were adsorbed to the other solid phases of the source rock (or bound to organic matter). The deterioration of the surrounding environment depends mainly on the buffering capacity of the rocks and sediments the leachate is flowing through. If the buffering capacity is low, it becomes depleted and the leachate needs to be treated not to cause major regional scale problems.

Important progress was made by Brazilian scientists on the treatment of AMD. They investigated the removal of heavy metals of acid effluents from coal mines using a Brazilian peat with high decomposition grade, emphasizing the mechanisms of adsorption of the metallic ions in the peat/solution interface. They evidenced that the peat catches the divalent cations lead and zinc by two different mechanisms. The lead adsorbs specifically in the active sites of the peat surface, by coordination reactions with the polar functional groups; while zinc undergoes non-specific adsorption as counter-ion in the peat interface. The selectivity sequence determined in the peat adsorption essays, accomplished with the effluents of coal mining, was Pb2+ > Cu2+ > Cd2+ > Fe2+ > Zn2+ > Mn2+.

Further progress was reported by Estonian scientists on the study of minimizing of acid mine drainage problems associated with exploitation of the Estonian alum shale. They evaluated alumosilicate neutralization potential in Maardu waste-rock dumps through incongruent dissolution of illite with the respective formation of smectite. It was suggested that this complex reaction leads to the buffering of 8% of the acidity by K⁺, and temporary precipitation of 25% of the acidity as K-jarosite. The fact that K-jarosite, but not alunite, is the detected precipitate, is an indicator that the process goes on at low pH until all pyrite in the shale particle is oxidized. The next stage in weathering profile development is the incongruent dissolution of K-jarosite with the release of disposed acidity and the formation of ferric oxyhydroxide. Thus, illite, although having a large surface area, buffers only a certain proportion of the acidity, depending on the partial equilibrium with respect to the dominating secondary phase. These results are very important for development of the proper buffering model at the site.

Microbial populations associated with the generation and treatment of AMD were studied by Canadian scientists at the Nickel Rim mine tailings impoundment (Ontariao). They found that elevated populations of iron-oxidizing bacteria and sulfur-oxidizing bacteria are restricted to hydrologically defined zones of recharge and discharge. Sulfur oxidizers are highest in the tailings where sulfide minerals are exposed to O₂ and O₂-rich recharge water. Iron-oxidizing bacteria were highest where tailings-derived effluent, rich in Fe(II), discharges to the aerobic surface water environment. Sulfur-reducing bacteria is elevated in the tailings and in portions of the down-gradient aquifer where organic carbon concentrations are high. It is important that at locations with high sulfur reducers, elevated populations of sulfur oxidants were also found, suggesting that the latter oxidants are metabolizing the reduced sulfur species produced by the sulfur-reducing bacteria in adjacent, but disparate, redox microenvironments.

To minimize the discharge of mine leachate-contaminated groundwater to surface water at the Nickel Rim mine site at Ontario, a reactive barrier composed of leaf and municipal compost and wood chips was designed. A joint Swedish Canadian study has revealed that sulfur is accumulating in the organic material as primarily acid volatile sulfides, at concentrations up to 195 mmol S g^-1 d.w. (0.63 wt.%) in a zone of preferential flow while pyrite and/or S⁰ account for only a small fraction of the total reduced inorganic sulfur. The precipitation of poorly crystalline Fe-monosulfides (mackinawite) was recognized as a primary sink for Fe and S in the barrier. Siderite formation was proposed as an additional Fe sink in areas of high Fe flux. Minor accumulations of organically-bound sulfur in the reactive barrier occur in zones of low aqueous Fe concentrations. These results should be considered at the development of techniques leading to the next minimization of AMD at similar sites worldwide.

WG 5: Environmental Models of Black Shale Hosted Mineral Deposits

(W. Mayer, Poland - e-mail: <wmayer@geol.agh.edu.pl>)

Sulfidic black shale can cause serious environmental harm by (1) generation of acids; (2) release of toxic metals contained in sulfides and other ore minerals and (3) leaching of metals from other minerals such as silicates, due to the acid.

Significant progress in the study of sulfidic - environmentally hazardous facies of the Upper Proterozoic black shales in the Bohemian Massif was achieved by Czech scientists. Numerous natural outcrops, anthropogenic waste damps and pit lakes often turning acid remained in many locations of the Upper Proterozoic Formation of the Teplá-Barrandian Unit where in the past pyritic metal-rich black shales have been exploited and processed for the production of the Bohemian sulfuric acid. The generation of acid mine drainage (AMD) which results from the oxidation of pyrite together with leaching of toxic heavy metals (Zn, Cu, Ni, Cd, Pb etc.) seems to be the most serious problem in this region. Considering that carbonate lithology with buffering potential is developed at the locations of metal-rich black shales only rarely if any, such objects represent a potential danger for human living especially when located in the vicinity of populated areas. For example about 766 000 t of ore were mined between 1833 and 1872 at Hromnice, the best known locality where an open pit (~190x130x50m) with a 15 m deep acid water lake remains. Acidification of local wells, strong corrosion of municipal water pipe line and killings of local biota in surface waters through leaking of acid mine waters from the former open pit mine located in the immediate vicinity of the Hromnice village have been recently reported. Similar problems can be expected at many other places of the Upper Proterozoic Formation of the Teplá-Barrandian Unit. Similarly oriented studies have been progressing in Austria, China, Georgia, Finland, Kazakhstan, Korea, Macedonia, Poland, Ukraine, U.S., Uzbekistan and other countries.

Effects of black shale weathering on the mobility of rhenium and platinum group elements were studied by U.S. scientists. They documented, on the example of comparison of PGE values in both fresh and weathered late Ordovician Utica Shale magnafacies (Québec) that 25-64% of the initial Re budget, 45-90% of the Os budget, 14-65 % of the Ir budget, 60-77% of the Pt budget, 69-86% of the Pd budget, and 44-96% of the Corg. budget are lost during weathering, Although black shales make up < 1% of the continental crust, mass balance calculations indicate that such facies contribute significantly to the labile Os inventory of the continental crust.

Another study on the effects of metal release from black shale weathering on the development of at-risk watersheds was performed by another group of U.S. scientists in two black shale dominated watersheds (Mohawk New York and Belt-Purcell Montana, USA). Their experimental data showed that, using a reaction medium of pH=5, up to 30% of the total metals were leached from the shale after two weeks of weathering. It was also confirmed that the trace metals, particularly Cu, Cr, and As are free metal species and are not complexed and removed from solution within the groundwater.

WG 6: Organic Atmospheric Particulates

(K. Hall, U.K. - e-mail: <Keith_Hall_GC2@compuserve.com>)

Atmospheric pollution from fossil fuel combustion has increased dramatically during this century. Beside the principal gaseous pollutants (CO₂, CO, SO₂ and a number of N-oxides), fossil fuel burning also delivers a variety of particulate matter, such as smoke particles and fly ashes, to the atmosphere. A range of experiments led to the result that atmospheric particles were classified into two categories according to their features. Organic atmospheric particulates are usually of spherical shape with the size of 0.1 mm and produced by the combustion of fossil fuel and petrochemical products. Understanding of the chemical and physical behavior of atmospheric particles is very much in its infancy.

Important scientific results in this field were achieved by Italian scientists who studied lead isotope composition of tree rings as biogeochemical tracers of heavy metal pollution in Firenze (Italy). They documented that Pb-isotope composition of tree rings from 1950 and 1995 was within the range of European aerosols and can be well correlated with the temporal evolution of Pb-isotopes measured in air particulates from Firenze. They concluded that tree rings are potentially powerful bio-geochemical tracer for monitoring air pollution history due to human activities.

Another group of Italian and Swiss scientists focused on the evaluation of pine needles as bioindicators of environmental trace metal contamination in the urban area of Palermo. They evidenced the presence of Pb, Sb, and Br in excess with respect to soil composition which resulted from anthropogenic emissions. Lead isotope data confirmed the anthropogenic origin of Pb. Morphological alterations attributable to phenol accumulation, such as modifications in the length of mesophyll cells and the appearance of lacunae in the distal portions, were observed in needles. The accumulation of phenols, linked to the presence of lead, gives rise to a specific pattern of metabolites providing mechanisms of detoxification and protection, so that the accumulation degree may be proposed as a marker of environmental pollution.

Chinese-Korean collaborative project on the evaluation of multiple sources of heavy metal contamination from Hunchun basin (NE China) also brought important findings. It was documented that the distribution of heavy metals in the alluvial soils of the basin has been influenced by several interacting factors of which one of the most important was coal combustion in power stations and households. The study of behavior of atmospheric particulates is needed to face successfully environmental problems related to these emissions because of expected future growing coal consumption especially in developing countries.

Considerable scientific results have been also achieved within a joint Chinese-U.S. study on geochemical analyses of a Himalayan snowpit profile from the Qinghai-Tibetan Plateau at an altitude of 7000m a.s.l. Surprisingly, organic compounds, indicative of petroleum residues such as automobile and diesel exhaust were identified. This indicates that the remote mountainous region, and to some extent, the middle-upper troposphere are polluted by human activities.

WG 7: Organic Matter in Nuclear Waste Issues

(D. Mossman, Canada - e-mail: <dmossman@mailserv.mta.ca>)

Safe disposal of radioactive wastes is one of the most urgent political and scientific problems facing society today. Over the long term, geologic properties of specific sites together with various engineered barriers to contain nuclear waste, are the chief determinants of the total system.

According to the IAEA the most critical aspect of a natural analogue study is the manner in which it tests repository effects. For various reasons the Oklo natural reactors in Gabon provide ideal subjects for study by workers concerned with the safe disposal of nuclear waste. For example, these reactors are analogues to modern pressurized water reactors in several significant respects: a) their cores consist of UO₂, similar to spent fuel, b) bitumen of Oklo reactors resembles the alpha-waste matrices proposed to confine wastes, c) hydrothermal clays surround them, similar to the clay backfill proposed for repositories, and d) fractured rocks surround the reactors as at many proposed repositories.

A joint Canadian-French-Australian research project has focused on the geochemistry of solid bitumen associated with uranium ore at Oklo and Bangombé. Earlier studies employing reflected light microscopy, pyrolysis-gas chromatography-mass spectrometry and microfocused laser Raman spectroscopy showed the solid bitumen to consist of a mixture of polycyclic aromatic hydrocarbons and cryptocrystalline graphite enclosing uraninite and entrapped fission-generated isotopes. Thermal ionization mass spectrometry, X-ray fluorescence, neutron activation analysis and laser ablation-inductively coupled plasma-mass spectrometry (LAM-ICP-MS) helped to confirm that at Oklo, the immobilization of uraninite in solidified graphitic bitumen enhanced containment of ²³⁵U and various fission products. Similar engineered barriers therefore should be incorporated into nuclear waste depository designs. In this year, LAM-ICP-MS has proven most effective by providing in situ trace element and isotopic analyses of Oklo bitumen. Preliminary studies are in progress to test the Oklo analogue at the Bangombé reactor (the so-called "last natural nuclear fission reactor on Earth"), which lies buried in a deeply weathered tropical soil only 12 meters below the surface of the earth. The Bangombé reactor probably represents the best known natural analogue to the worst case scenario of a nuclear waste spill; specifically LAM-ICP-MS is being employed to evaluate the role played by its constituent solid bitumens as barriers to radionuclide migration.

A new "conservative roof" model on trace metal-humate interactions was applied to situation generally to be expected in deep groundwater and selected cases of interest for planned Swiss repositories of radioactive waste by Swiss scientists. This approach estimates the maximum negative influence of the process on a property of the system, such as the safety of a waste disposal site. The major effects influencing radionuclide-humic interactins are: metal concentration, pH effect, ternary complexes, organic coating, ion strength, competing anions, competing cations and sorption. At the Wellenberg site characterized by the presence of NaHCO₃ water, generally a strong effect for lanthanides and 3-valent actinides is expected if humic substance concentration exceeds the ppb (10^-6 g/l) range. The effects on transition metals (Ni, Co) and hexavalent actinides become important at 2 to 3 orders of magnitude higher concentrations of humic substance (i.e. in the ppm range - 10^-3 g/l). Alkaline earth metals (Ca, Sr) and pentavalent actinides are influenced by humic substance only if its concentration exceeds 0.1 g/l. These results are extremely important for safe development of HLWRS in similar geological and hydrogeological situations worldwide.

Interesting scientific results came out of a joint Ukrainian-U.S. study on the evaluation of decontamination of heavy metals and radionuclides by some agricultural plant species. They have examined the efficiency of some ‘classic’ phytoremediation technologies based on already existing high accumulation ability of some plant species. It was suggested that inoculation of the experimental plants with mycorrhizal fungi seems to be most effective and accessible treatment for the increasing of phytoextraction efficiency. They also concluded that soils stabilization with woody plants may be effectively used for the prevention of vertical and horizontal migration of pollutants at soil complex especially in some selected critical landscapes. These results are useful for future projects focused on the nvironmental clean up of heavily polluted areas.

WG 8: Organics in Aquifers and Water Systems

(L. de Souza - <<laecio@geologia.ufrn.br>and R. Melo, Brazil, J. Spangenberg, Switzerland - <Jorge.Spangenberg@imp.unil.ch>)

One of highlights of this WG is a pioneering study of organic compositions of geothermal waters in the Panonian Basin (Hungary), carried out by Hungarian scientists. They were able to determine various organic compounds and relate them to various stages of the basinal evolution. Humic acids occurred in very early stage and were a part of the thermal water precursors. During diagenesis - microbially produced gases and during early catagenesis -thermogenic hydrocarbon gases were generated. The origin of aromatic hydrocarbons is related to early catagenesis. The appearance of phenols and later that of fatty acids was also governed by maturation and resulted from advanced stage of catagenesis. Division of thermal waters into maturity groups was suggested based on their organic composition. More data from other geothermal waters worldwide are needed to evaluate suggested classification scheme.

On the example of the hydrogeochemical study and the study of the transport of organic contaminants in an urban watershed of Chesapeake Bay (Washington D.C.). U.S. scientists have found higher amounts of polychlorinated biphenyls, polycyclic aromatic hydrocarbons and organochlorine pesticides in the tidal Anacostia River during high flow events. Polycyclic aromatic hydrocarbons in the particulate phase within fluvial transport consisted primarily of pyrogenic homologues characteristic of weathered or combusted petroleum products. It was suggested that aromatic hydrocarbons in runoff from urban regions may serve as an important source of polycyclic aromatic hydrocarbon fluxes to the tidal waters of Chesapeake Bay. These results of applied characted are very important for the evaluation of the provenance of various organic pollutants in aquifers.

Important findings on the distribution and sources of humic substances in various German groundwater aquifers were reported by German scientists. They demonstrated that in-situ generation of dissolved organic carbon is associated with the microbiologically mediated mineralization of sedimentary organic carbon. This leads to the reduction of SO₄ and to the release of P into groundwater. It was also documented that where SO₄ is depleted, the mineralization of sedimentary organic carbon occurs via fermentation, resulting in CH₄ generation.

Interesting results have come up from the Czech-U.S. collaboration on the study of sulfur isotope dynamics in two Central European watersheds affected by high atmospheric deposition of SO₂. It was suggested that the extremely negative watershed S input/output budget (output ->>-input) was caused by delayed removal of S accumulated over the decades-long period of heavy pollution. The anthropogenic S was stored largely in an organic form in the humus layer. Approximately 30% of total sulfate S in the discharge were organically recycled.

Very useful study of the quality of underground waters of the Metropolitan Natal (Rio Grande do Norte State, Brazil), carried out within the Brazil-Swiss cooperative project, have continued.

2.2. LIST OF MEETINGS WITH APPROXIMATE ATTENDANCE AND NUMBER OF COUNTRIES

1. Annual International Meeting C- Global Changes and Future Environment Symposia, C7 Symposium “Organics in Major Environmental Issues”; co-convenors: J. Pašava (Czech Republic) and Laecio Cunha de Souza (Brazil); organized within the 31^st IGC, Rio de Janeiro, Brazil (August 6-17, 2000); the meeting passed on August 11^th , 2000; 30-60 scientists from 18 countries

2. GEOCHIM 2000 - A Training Course in Geochemical Exploration Methods and Their Environmental Applications; co-organized with the Czech Geological Survey and UNESCO (Paris); Prague and Dolní Rožínka, September 4-18, 2000; 13 participants mostly from developing countries (Albania, Botswana, Burkina Faso, Jordan, Malaysia, Nepal, Romania, Russia and Zambia); the course hosted the Czech IGCP 429 WG Meeting on September 9^th, 2000

2.3. NUMBER OF PUBLICATIONS (INCLUDING MAPS) - LIST OF MAJOR OR MOST IMPORTANT PUBLICATIONS

More than 80 scientific papers resulted from the Project 429 activities and were published in the form of monographs, articles in various scientific journals and abstracts to the IGCP 429 meetings. Selected major publications are as follows:

Alaimo, M.G., Dongarra, G., Melati, M.R., Monna, F. and Varrica, D., 2000, Recognition of environmental trace metal contamination using pine needles as bioindicators. The urban are of Palermo (Italy). Environmental Geology, 39, 914-924, Springer Verlag.

Andersson, E., Simoneit, B.R.T. and Holm, N.G., 2000, Amino acid abundances and stereochemistry in hydrtothermally altered sediments from the Juan de Fuca Ridge, northeastern Pacific Ocean. Applied Geochemistry 15, 1169-1190. Pergamon.

Andreevski, B., and Stefanova, V., 1999:The geology and abundance of grey slates in the eastern parts of the Pelagonian Tertiary basin. Geologica Macedonica, Vol.13, p.41-46, Stip.

Benner, S.G., Gould, W.D. and Blowes, D.W., 2000, Microbial populations associated with the generation and treatment of acid mine drainage. Chemical Geology, 169, 435-448, Elsevier.

Buckau, G., Artinger, R., Geyer, S., Wolf, M., Fritz, P. and Kim, J.I., 2000, Groundwater in-situ generation of aquatic humic and fulvic acids and the mineralization of sedimentary organic carbon. Applied Geochemistry 15, 819-832. Pergamon.

Carman, R., Ellund, G. And Damberg, Ch., 2000, Distribution of organic and inorganic phosphorus compounds in marine and lacustrine sediments: a 31P NMR study. Chemical Geology 163, 101-114, Elsevier.

Chon, H.T., Kim, J.Y. and Choi, S.Y., 1999, Hydrogeochemical characteristics of acid mine drainage around the abandoned Youngdong coal mine in Korea. Resource Geology, 49, 113-120.

Costa dos Santos, M.D. and de Salles Leal Filho, L., 2000, The adsorption of metals lead and zinc from acid waters by Brazilian peat. In: 11th Annual International Conference on Heavy Metals in the Environment (J. Nriagu, Editor), University of Michigan, School of Public Health, Ann Arbor, MI (CD-ROM).

Dumurdzanov, N., and Krstic, N., 1999: The Skopje Neogene basin in the Republic of Macedonia. Geologica Macedonica, 13, 47-56, Stip.

Fein, J.B., 2000, Quantifying the effects of bacteria on adsorption reactions in water-rock systems. Chemical Geology 169, 265-280, Elsevier.

Forgac, J., Stresko, V., Somsak, L. and Simonovicova, A., 2000, Bioaccumulation of some metals on highly polluted alluvial soils of the Stiavnicky potok brook area (Slovak Republic). Mineralia Slovaca, 32, 103-108, Bratislava.

Foster, G.D., Roberts, E.C. Jr., Gruessner, B. and Velinsky, J., 2000, Hydrogeochemistry and transport of organic contaminants in an urban watershed of Chesapeake Bay (USA). Applied Geochemistry 15, 901-915. Pergamon.

Fowle, D.A., and Fein, J.B., 2000, Experimental measurements of the reversibility of metal-bacteria adsorption reactions. Chemical Geology, 168, 27-36, Elsevier.

Haggan, T. and Parnell, J. 2000. Hydrocarbon-metal associations in the Western Cordillera, Central Peru. Journal of Geochemical Exploration, 69-70, 229-234.

Hailian Dong, Frederickson, J.K., Kennedy, D.W., Zachara, J.M., Kukkadapu, R.K. and Onstott, T.C., 2000, Mineral transformation associated with the microbial reduction of magnetite. Chemical Geology 169, 299-318.

Hailin Deng, Liang Qi, Shirong Liu, 1999, Platinum Group Elements and Environment of Ancient Oceans: Preliminary Results from Lower Cambrian Black Shales in Southern China, Fourth International Conference on Asian Marine Geology in Qingdao on October 14 to 18, 1999.

Hannigan, R. and Latkoczy, C., 2000, Effects of metal release from black shale weathering on the development of at-risk watersheds. Proceedings of the 31st IGC, Rio de Janeiro, C7 Symposium, August 6-17, 2000, CD-ROM.

Herbert, R.B., Benner, S.G., Blowes, D.W., 2000, Solid phase iron-sulfur geochemistry of a reactive barrier for treatment of mine drainage. Applied Geochemistry 15, 1331-1343, Pergamon.

Hidaka, H. and Gauthier-Lafaye, 2000, Redistribution of fissiogenic and non-fissiogenic REE, Th and U in and around natural fission reactors at Oklo and Bangome, Gabon. Geochimica et Cosmochimica Acta 64, 2093-2108, Pergamon.

Hummel, W., Glaus, M.A. and Van Loon, 2000, Trace metal-humate interactions. II. The “conservative roof” model and its application. Applied Geochemistry 15, 975-1001, Pergamon.

Hu, W., Zhou, H, Gu, L., Zhang, W., Lu, X., Fu, Q., Pan, J. and Zhang, H., 2000, New evidence of microbe origin for ferromanganese nodules from the East Pacific deep sea floor. Science in China (Series D), 43, 187-192, Beijing.

Jia Rongfen and Liu Dehan, 2000, The relationship between dolomitization and organic matter occurrence in Lower Paleozoic carbonate in the Ordos Basin. Chinese science bulletin, 45, 41-46, Beijing.

Kribek, B., Pasava, J., and Lobitzer, H., 1999, The Behavior of Selected Trace Elements in Alpine Soils Developed on Black Shales in the upper part of the ”Hauptdolomit” in the Seefeld Area, Tyrol, Austria. Abhandlungen der Geologischen Bundesanstalt, 56/2, Wien.

Kribek, B., 2000, Weathering of organic matter in tips of coal mines, Plzen Basin, Czech Republic. Proceedings of the 31st IGC, Rio de Janeiro, C7 Symposium, August 6-17, 2000, CD-ROM

Kribek, B. and Landais, P., 2000, Organic matter in ore deposits: from the genesis to the environmental issues. Scientific bridges for 2000 and beyond, a virtual colloquium by the Elf “Professeurs de l´Academie des Sciences, Academie des Sciences, 121-130, ISBN 2-7430-0365-0, Londres-Paris-New York.

Kumar, A. and Patterson, R.T., 2000, Arcellaceans (thecamoebians): new tools for monitoring long- and short-term changes in lake bottom acidity. Environmental Geology, 39, 689-695, Springer Verlag.

Li Shengrong and Gao Zhenmin, 2000, Origin trace for noble metal group elements in the lower Cambrian black rock series of south China. Science in China (Series D), 30,169-174. Beijing.

Liu Dehan, Xiao Xianming, Jia Rongfen and Shen Jiagui, 2000, Observation of hydrocarbon generation and migration of highly- matured carbonates by means of laser-induced fluorescence microscopy, Chinese science bulletin, 45 Supp., 16-20. Beijing.

Lovley, D.R., Kashefi, K., Vargas, M., Tor, J.M. and Blunt-Harris, E.L., 2000, Reduction of humic substances and Fe(III) by hyperthermophilic microorganisms. Chemical Geology 169, 289-298, Elsevier.

Lu Jia-lan, Zhuang Han-ping, Fu Jia-mo and Liu Jinzhong, 2000, Sedimentation, diagenesis, hydrothermal process and mineralization of germanium in the Lincang superlarge germanium deposit in Yunan Province. China,Geochimica, 29, 36-42. Beijing.

Mason, R.P., McAloon,K.C., Leaner, J.J., Laporte, J.M.and Andres, S., 2000, Factors controlling the bioaccumulation of mercury and methylmercury into benthic invertebrates and fish. In: 11th Annual International Conference on Heavy Metals in the Environment (J. Nriagu, Editor),University of Michigan, School of Public Health, Ann Arbor, MI (CD-ROM).

Middleton, D. et al., 2000, Reconstruction of fluid migration history in Northwest Ireland using fluid inclusion studies. Journal of Geochemical Exploration, 69-70, 673-677.

Moon, J.W., Moon, H.S., Woo, N.C., Hahn, J.S., Won, J.S., Song, Y., Lin, X. and Zhao, Y, 2000, Evaluation of heavy metal contamination and implication of multiple sources from Hunchun basin, northeastern China. Environmental Geology 39, 1039-1052, Springer Verlag.

Mossman, D.J.,Jackson, S.E. and Gauthier-Lafaye, F., 2000, Nuclear waste disposal - the Oklo analogue. Proceedings of the 31st IGC, Rio de Janeiro, C7 Symposium, August 6-17, 2000, CD-ROM.

Muraleedharan, T.M., Iyengar, L.,Philip, L. and Venkobachar, C., 2000, Biosorption of heavy metals by microfungi Ganoderma lucidum. In: 11th Annual International Conference on Heavy Metals in the Environment (J. Nriagu, Editor),University of Michigan, School of Public Health, Ann Arbor, MI (CD-ROM).

Novak, M., Kirchner, J.W., Groscheova, H., Havel, M., Cerny, J., Krejci, R. and Buzek, F., 2000, Sulfur isotope dynamics in two Central European watersheds affected by high atmospheric deposition of SOX. Geochimica and Cosmochimica Acta 64, 367-383. Pergamon.

O’Reilly, C. and Parnell, J., 1999, Fluid flow and thermal histories for Cambrian-Ordovician platform deposits, New York: Evidence from fluid inclusion studies. Geological Society of America Bulletin, 111, 1884-1896.

Parmar, N., Warren, L.A., Roden, E.E. and Ferris, F.G., 2000, Solid phase capture of stroncium by the iron reducing bacteria Shewanella alga strain BrY. Chemical Geology 169, 281-288, Elsevier.

Parnell, J. and Haggan, T., 2000, Metal-organic interactions and Andean deformation. Proceedings of the 31st IGC, Rio de Janeiro, C7 Symposium, August 6-17, 2000, CD-ROM.

Parnell, J. and McCready, A., 2000, Paragenesis of gold- and hydrocarbon-bearing fluids in gold deposits. In: M. Glikson and M. Mastalerz (eds), Organic Matter and Mineralization. Kluwer, Dordrecht, 38-52.

Pasava, J., 1999, Geochim 99 - Postgraduate certificated training course in geochemical exploration methods and their environmental applications. Episodes, 22, 4, 311-312.

Pasava, J. and Pouba, Z., 1999, Geology and geochemistry of toxic sulfidic black shales from the Tepla-Barrandian Unit on the example of two model sites. In: V. Lysenko, ed., Reviews of geological research, Ministry of the Environment, Czech Republic, Division of Geology, 30, Prague, ISBN 80-7212-117-0 (in Czech with English abstract).

Pasava, J. and Schonlaub, H.P., 1999, Stratigraphy, geochemistry and origin of Silurian black graptolitic shales of the Carnic Alps (Austria). Abh.Geol.B.A., 56/1, 317-324, Wien.

Peng Xianzhi, Jia Rongfen, Li Rongson, Gai Shungying and Liu Tungsheng, 2000, Paleo-environmental study on the growth of magnetotactic bacteria and precipitation of magnetosomes in Chinese loess-paleosol sequences,Chinese science bulletin, 45 Supp. 21-25. Beijing.

Perruchoud, D., Walthert, L., Zimmermann, S. and Luscher, P., 2000, Contemporary carbon stocks of mineral forest soils in the Swiss Alps. Biogeochemistry, 50, 111-136, Kluwer Academic Publisher.

Petsch, S.T., Berner, R.A. and Eglinton, T.I., 2000, A field study of the chemical weathering of ancient sedimentary organic matter. Organic Geochemistry 31, 475-487, Pergamon.

Peucker-Ehrenbrink, B. and Hannigan, R.E., 2000, Effects of black shale weathering on the mobility of rhenium and platinum group elements. Geology, 5, 475-478.

Phoenix, V.R., Adams, D.G. and Konhauser, K.O., 2000, Cyanobacterial viability during hydrothermal biomineralisation. Chemical Geology 169, 329-338, Elsevier.

Plyusnina, L.P., Kyzmina, T.V., Likhoidov, G.G. and Narnov, G.A., 2000, Experimental modeling of platinum sorption on organic matter. Applied Geochemistry 15, 777-784, Pergamon..

Puura, E., Neretnieks, I. and Kirsimae, K., 1999, Atmospheric oxidation of pyritic waste rock in Maardu, Estonia, 1: field study and modelling. Environmental Geology, 38, Springer Verlag.

Puura, E. and Neretnieks, I., 2000, Atmospheric oxidation of the pyritic waste rock in Maardu, Estonia, 2: an assessment of alumosilicate buffering potential. Environmental Geology, 39, 560-566, Springer Verlag.

Qi Liang, Hu Jing and Deng Hailin. Determination of disperse elements in black shale by inductively coupled plasma mass spectrometry, Chinese Science Bulletin, 1999, 44 Supp, September, 173-174. Beijing.

Sajgo, C., Karpati, Z. and Veto, I, 2000, Organic compositions of geothermal waters. Proceedings of the 31st IGC, Rio de Janeiro, C7 Symposium, August 6-17, 2000, CD-ROM.

Schucheng, X., Tandong, Y, Shichang, K., Baiqing, X., Keqin, D. and Thompson, L.G., 2000, Geochemical analyses of a Himalayan snowpit profile: implications for atmospheric pollution and climate. Organic Geochemistry 31, 15-23. Pergamon.

Serafimovski, T., 2000: Pb-Zn mineral deposits associated with black shales in the Sasa-Toranica ore district, Republic of Macedonia (Southeastern Europe). Proceedings of the 31st IGC, Rio de Janeiro, 11-3 Symposium, August 6-17, 2000, CD-ROM.

Shepherd, T.J. et al., 2000, Chemical analysis of palaeogroundwaters: a new frontier for fluid inclusion research. Journal of Geochemical Exploration, 69-70, 415-418.

Simoneit, B.R.T., Aboul-Kassim, T.A.T. and Tiercelin, J.J., 2000, Hydrothermal petroleum from lacustrine sedimentary organic matter in the East African Rift. Applied Geochemistry 15, 335-368, Pergamon.

Sitaula, B.K., Hansen, S., Sitaula, J.I.B. and Bakken, L.R., 2000, Methane oxidation potentials and fluxes in agricultural soil: Effects of fertilisation and soil compaction. Biogeochemistry 48, 323-339, Kluwer Academic Publisher.

Sorochinsky,B., Grodzinsky, D. and Dushenkov, S., 2000, Using of some agricultural plant species for the decontamination of heavy metals and radionuclides in the environment. In: 11th Annual International Conference on Heavy Metals in the Environment (J. Nriagu, Editor),University of Michigan, School of Public Health, Ann Arbor, MI (CD-ROM).

Spangenberg, J.E., Macko, S.A. and Ogrinc, N., 2000, Carbon isotope analysis of vegetable lipids as tracer of environmental changes ? Proceedings of the 31st IGC, Rio de Janeiro, C7 Symposium, August 6-17, 2000, CD-ROM.

Tao Zuyi, Chu Taiwei, Du Jinzhou, Dai XiongXin and Gu Yingije, 2000, Effects of fulvic acids on sorption of U (VI), Zn, Yb, I and Se(IV) onto oxides of aluminum, iron and silicon. Applied Geochemistry 15, 133-139. Pergamon.

Thuy, H.T.T., Tobschall, H.J. and An, P.V., 2000, Distribution of heavy metals in urban soils - a case study of Danang-Hoian area (Vietnam). Environmental Geology, 39, 603-610, Springer Verlag.

Tommasini, S., Davies, G.R. and Elliot, T., 2000, Lead isotope composition of tree rings as bio-geochemical tracers of heavy metal pollution: a reconaissance study from Firenze, Italy. Applied Geochemistry 15, 891-900, Pergamon.

van der Lelie, D., Corbisier, P., Taghavi, S., Mergeay, M.,De Smet, M., Hooyberghs, L., Kinnaer, L., Diels, L., Spelmans, N., Vangronsveld, J., Brox, G., 2000, Use of heavy metal resistant bacteria in a bioreactor concept (bacteria metal sludge reactor) to remove bioavailable heavy metals from polluted soils. In: 11th Annual International Conference on Heavy Metals in the Environment (J. Nriagu, Editor), University of Michigan, School of Public Health, Ann Arbor, MI (CD-ROM).

Wood, S.C., 2000, Complexation of Pd by natural organic ligands. Proceedings of the 31st IGC, Rio de Janeiro, C7 Symposium, August 6-17, 2000, CD-ROM.

Williams, B.L., Silcock, D.J., 2000, Impact of NH4NO3 on microbial biomass C and N and extractable DOM in raised bog peat beneath Sphagnum capillifolium and S. recurvum. Biogeochemistry, 49, 259-276, Kluwer Academic Publisher.

Zachara, J.M., Smith, S.C. and Frederickson, J.K., 2000, The effect of biogenic Fe(II) on the stability and sorption of Co(II)EDTA2- to goethite and subsurface sediment. Geochemica et Cosmochimica Acta, 64, 1345-1362, Pergamon.

Zanin,Yu.N., Gavshin V.M., Pisareva G.M., 2000, Trace elements in hypergene karst phosphorites of southern Siberia; experience of ecological geochemistry. Geologia i Geophysika (Geology and Geophysics), 41, 722-732 [in Russian].

Zanin, Yu.N., Zamirailova, A.G. and Pisareva, G.M., 2000, Cadmium, vanadium and zinc of phosphorites in catagenic processes. Doklady of the Russian Academy of Sciences, 374, 228-231[in Russian].

2.4. LIST OF COUNTRIES INVOLVED IN PROJECT

(* COUNTRIES ACTIVE THIS YEAR

*Albania, Argentina, *Australia, *Austria *Bulgaria, Botswana, *Brazil, Burkina Faso, *Canada, *China, *Czech Republic, *Estonia, *Finland, *France, *Germany, *Hungary, *Israel, *Italy, *Japan, *Jordan, *Korea, *Macedonia, Mongolia, Nigeria, Philippines, *Poland, Republic of South Africa, *Romania, *Russia, *Slovakia, *Slovenia, *Spain, *Switzerland, *UK, *USA.

2.5. ACTIVITIES INVOLVING OTHER IGCP PROJECT, IUGS OR MAJOR PARTICIPATION OF SCIENTISTS FROM DEVELOPING COUNTRIES.

A very successful Postgraduate Training Course on the Geochemical Exploration Methods and their Environmental Applications was organized by IGCP 429 in collaboration with the Czech Geological Survey in Prague, Czech Commission for UNESCO and UNESCO/Paris. Thirteen participants mostly from developing countries (Albania, Botswana, Burkina Faso, Jordan, Malaysia, Nepal, Romania, Russia and Zambia) took part in this course which was held in Prague and Dolni Rozinka, Czech Republic between September 4-18, 2000.

Many participants very highly appreciated both organization and scientific level of the course through their personal letters mailed either directly to the organizers or to Mr. F. Repetto from the Division of Earth Sciences, UNESCO, Paris. Involvement of more people especially from developing through “training course” has became a very important aspect of IGCP 429 activities.

3. PROPOSED ACTIVITIES OF THE PROJECT FOR THE YEAR AHEAD

3.1. GENERAL GOALS

Based on the approved IGCP 429 work plan the following activities were proposed for 2001:

v Continuation of ongoing transdisciplinary research projects covering the eight major topics of the Project with possible involvement of MAB specialists on both national and international levels

v Active participation in the GEOCHIM 2001 - a postgraduate certificated training course on the geochemical exploration methods and their environmental applications

v Presentation of scientific results on both national and international levels

v Publication of new results in local and internationally recognized periodics

v Editing Newsletters

3.2. SPECIFIC MEETINGS AND FIELD TRIPS (*INDICATION OF PARTICIPATION BY DEVELOPING COUNTRIES

1. The role of organic matter in the formation of mineral deposits and related environmental issues

Session S1 in the joint SGA-SEG Meeting; convenors: Jan Pasava (Czech Republic), H. Kucha (Poland) and A.P. Gize (UK); August 26-29, 2001, Cracow, Poland; more info at http://galaxy.uci.agh.edu.pl/sga

2. GEOCHIM 2001; A Training Course in Geochemical Exploration Methods and Their Environmental Applications; co-organized with the Czech Geological Survey and UNESCO, Prague and Dolni Rozinka, September 3-17, 2001; expected 15 participants mostly from developing countries

3.3 PROPOSED MAJOR PUBLICATIONS

N/A

4. PROJECTED FUNDING REQUEST

In 2000, the IGCP 429 appreciated high funding (USD 4,000 from UNESCO budget and USD 5,000 from IUGS budget). This budget, coupled with contributions from the Czech Geological Survey, Czech Commission for UNESCO and Czech IGCP National Committee contributed to the participation of:

6 scientists from 6 countries in the Annual International Meeting of the IGCP 429 held in Rio de Janeiro, Brazil and,
12 scientists from 9 countries in the GEOCHIM 2000 postgraduate training course.

The complete financial statement was mailed together with a brief report shortly after the last meeting to the Secretary General of IUGS for approval.

In 2001, IGCP 429 will hold two major events - Annual International Meeting in Cracow, Poland with at least half day oral session and associated poster presentation, and GEOCHIM 2000 - a postgraduate training course on geochemical exploration methods and their environmental applications (Prague and Dolni Rozina, Czech Republic) where similarly as in 1999 and 2000 about 15 people from developing countries are expected to attend. Frankly, both places mean quite high travel and local expenditures, especially for African, Asian, Australian and North American people traveling to Cracow (Poland) or African, Asian and South American people traveling to the Czech Republic for GEOCHIM 2001.

We hope that based on the progress highlighted in this report, the Members of the IGCP Scientific Board will be able to recommend high funding for IGCP 429 for the year of 2001.

5. REQUEST FOR EXTENSION

N/A

6. SUMMARY

2000 was the third year of the IGCP 429, characterized by continuing progress within all eight topical working groups covering major issues of the Project. Besides 33 countries involved in the Project, new links have been established in Burkina Faso and Botswana. Two major international events and several meetings on national level were arranged within IGCP 429 activities. The very well attended Annual International Meeting was held in Rio de Janeiro, Brazil within the 31^st IGC. Another very important aspect of the IGCP 429 activities was a “training component”, which was represented by an active Project involvement in the preparation and organization of the GEOCHIM 2000 - a Postgraduate Certificated Training Course on the Geochemical Prospecting Methods and their Environmental Applications. The course was held in the Czech Republic in September and 13 scientists from developing countries took part in this event.

One of major highlights of the IGCP 429 activities came out of Swiss-U.S.-Slovenian collaborative study. The d¹³C of the fatty acids from different vegetable oils appear to be preserved where lipids distribution have been altered by degradation or burial. The results indicate that GC/C/IRMS of plants lipids may be a potential tracer of the global changes recorded in the terrestrial carbon cycle.

In the field of organic matter - metals interactions (WG 1), important scientific results have been reached on the study of sorption of PGE and various other metals especially by U.S. and Russian scientists. It was suggested that the use of surface complexation modeling of aqueous metal adsorption onto bacterial surfaces yields accurate estimates of the distribution of metals in bacteria-bearing solutions. Experiments on Pt sorption on activated carbonized organic matter have proven to be an affective mechanism of Pt accumulation in newly discovered low grade Pt deposits bound to low-rank brown coals and black shales.

In the field of microbial leaching in environmental clean up (WG 2), considerable progress was achieved by Belgium and U.S. scientists who reported on the use of heavy metal resistant bacteria in a bioreactor concept to remove bioavailable heavy metals in polluted soils. Japanese scientists have been successful in biodegradation of hazardous organochlorine compounds in groundwater using indigenous microbe. Scientists from India and Trinidad highlighted significant biosorption properties of Ganoderma lucidum (macro fungi), widely occurring in tropical rainforests worldwide, as an alternate wastewater treatment technology.

In the field of weathering of organic matter (WG 3), further for society very useful applied scientific results have been reported by Czech scientists on the weathering of organic matter in waster dumps of coal mines of various age from the Pilsen Basin (West Bohemia, Czech Republic). This study has shown that significant amount of oxidation products (humic substances) is produced during weathering. From the agrochemical point of view, the weathering of organic matter affects namely the sorption capacity of rocks dumped on the heaps. These results should be taken into consideration at the remediation of various dumpsites after coal mining worldwide. Norwegian scientists have demonstrated that soil compaction has affected the biological potential for CH₄ oxidation in the soil.

In the field of acid mine drainage (WG 4), considerable scientific results have been obtained by Brazilian scientists who suggested that Brazilian peat is suitable for the removal of heavy metals of acid effluents from coal mines. Similar studies, based on organic barriers, were successfully applied by Canadian scientists in Quebec. Estonian scientists demonstrated that alumosilicate (smectite) is able to buffer only a certain proportion of the acidity at the Maardu site, depending on the partial equilibrium with respect to the dominating secondary phase. All these results are very important for the treatment of acid mine drainage at various sites of the world.

In the field of environmental models of black shale hosted mineral deposits (WG 5), very useful results came out of the study of sulfidic - environmentally hazardous facies of the Upper Proterozoic black shales in the Bohemian Massif which cause local acidification of wells, strong corrosion of municipal water pipe line and killings of local biota in surface waters through leaking of acid mine waters from the abandoned mining sites. Similarly oriented studies have been progressing in Austria, China, Georgia, Finland, Kazakhstan, Korea, Macedonia, Poland, Ukraine, U.S., Uzbekistan and other countries.

In the field of organic atmospheric particulates (WG 6), Chinese-Korean collaborative project identified coal combustion in power stations and households as major factor influencing heavy metal contamination in the Hunchun basin (NE China). It was concluded that the study of behavior of atmospheric particulates is needed to face successfully environmental problems related to these emissions because of expected future growing coal consumption especially in developing countries.

In the field of organic matter in nuclear waste issues (WG 7), research activities using the most advanced analytical methods and carried out by Canadian, French and Australian scientists helped to confirm that at Oklo (Gabon), the immobilization of uraninite in solidified graphitic bitumen enhanced containment of ²³⁵U and various fission products. A new model on trace metal-humate interactions was applied to situation generally to be expected in deep groundwater at selected repositories of radioactive waste by Swiss scientists. These results should be considered in development of safe nuclear waste depository sites.

In the field of organics in aquifers and water systems (WG 8), a new classification of geothermal waters of the Panonian Basin (Hungary) was suggested by Hungarian scientist based on the study of organic composition. They were able to determine various organic compounds and link them to individual stages of the basinal evolution. More data from other geothermal waters worldwide are needed to verify suggested classification scheme. Important results in this field have been also reported by Brazilian, U.S. and German scientists.

The results of the IGCP 429 have been summarized in more than 80 scientific papers. Two major events are planned for 2001 - the Annual International Meeting in Poland and GEOCHIM - a Postgraduate Certificated Training Course for people from developing countries in the Czech Republic.

Newsletter summarizing 2000 results and plans for 2001 was distributed to the participants.

7. OTHER RELEVANT INFORMATION

N/A

8. ACKNOWLEDGEMENTS

The Project leadership wishes to acknowledge the Czech Geological Survey in Prague, Czech Commission for UNESCO and the North Bohemian Coal Mines Inc. for their co-sponsorship of the GEOCHIM 2000 Postgraduate Training Course.