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Background: In 1996, the Committee on the Assessment of Wartime Exposure to Herbicides in Vietnam of the National Academy of Sciences’ Institute of Medicine (IOM) issued a report on an exposure model for use in epidemiological studies of Vietnam veterans. This exposure model would consider troop locations based on military records; aerial spray mission data; estimated ground spraying activity; estimated exposure opportunity factors; military indications for herbicide use; and considerations of the composition and environmental fate of herbicides, including changes in the TCDD content of the herbicides over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of the herbicides into the ground. When the final report of the IOM Committee was released in October 2003, several components of the exposure model envisioned by the Committee were not addressed. These components included the environmental fate of the herbicides, including changes in the TCDD content over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of herbicides into the ground. This paper is intended to help investigators understand better the fate and transport of herbicides and TCDD from spray missions, particularly in performing epidemiological studies. Methods: This paper reviews the published scientific literature related to the environmental fate of Agent Orange and the contaminant, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), and discusses how this affected the potential exposure to TCDD of ground troops in Vietnam. Specifically, the mechanisms of dissipation and degradation as they relate to environmental distribution and bioavailability are addressed. Results: The evaluation of the spray systems used to disseminate herbicides in Vietnam showed that they were capable of highly precise applications both in terms of concentrations sprayed and area treated. Research on tropical forest canopies with leaf area indices (a measure of foliage density) from 2 to 5 indicated that the amount of herbicide and associated TCDD reaching the forest floor would have been between 1 and 6% of the total aerial spray. Studies of the properties of plant surface waxes of the cuticle layer suggested that Agent Orange, including the TCDD, would have dried (i.e., be absorbed into the wax layer of the plant cuticle) upon spraying within minutes and could not be physically dislodged. Studies of Agent Orange and the associated TCDD on both leaf and soil surface have demonstrated that photolysis by sunlight would have rapidly decreased the concentration of TCDD, and this process continued in shade. Studies of ‘dislodgeable foliar residues’ (DFR, the fraction of a substance that is available for cutaneous uptake from the plant leaves) showed that only 8% of the DFR was present 1 hr after application. This dropped to 1% of the total 24 hrs after application. Studies with human volunteers confirmed that after 2 hrs of saturated contact with bare skin, only 0.15–0.46% of 2,4,5-T, one of the phenoxy acetic acid compounds that was an active ingredient of Agent Orange, entered the body and was eliminated in the urine. Conclusions: The prospect of exposure to TCDD from Agent Orange in ground troops in Vietnam seems unlikely in light of the environmental dissipation of TCDD, little bioavailability, and the properties of the herbicides and circumstances of application that occurred. Photochemical degradation of TCDD and limited bioavailability of any residual TCDD present in soil or on vegetation suggest that dioxin concentrations in ground troops who served in Vietnam would have been small and indistinguishable from background levels even if they had been in recently treated areas. Laboratory and field data reported in the literature provide compelling evidence on the fate and dislodge-ability of herbicide and TCDD in the environment. This evidence of the environmental fate and poor bioavailability of TCDD from Agent Orange is consistent with the observation of little or no exposure in the veterans who served in Vietnam. Appreciable accumulation of TCDD in veterans would have required repeated long-term direct skin contact of the type experienced by United States (US) Air Force RANCH HAND and US Army Chemical Corps personnel who handled or otherwise had direct contact with liquid herbicide, not from incidental exposure under field conditions where Agent Orange had been sprayed.

Goal and Scope and Background: The application of a promising method, termed sorptive flotation, for the removal of chromium(VI) and zinc ions was the aim of the present paper. A special case of sorptive flotation is adsorbing colloid flotation. Suitable sorbent preparation techniques have been developed in the laboratory. Methods: Sorptive flotation, consisting of the sorption and flotation processes combined in series, has proved to give fast and satisfactory treatment of the industrial streams and effluents bearing dilute aqueous solutions of zinc and chromium(VI). Results and Discussion: Goethite has proved to be effective for the removal of chromium(VI) and zinc ions. Also, adsorbing colloid flotation with ferric hydroxide (as the co-precipitant) could be an alternative method to the above-mentioned separation of metal ions. In both cases, chromium(VI) (pH=4) and zinc (pH=7) removal was about 100%. Conclusion: The reasons for selecting the iron-based bonding materials, like goethite and/or in-situ produced ferric hydroxide, are that they are cheap, easily synthesized, suitable both for cation and anion sorption, and, furthermore, that they present low risks for adding a further pollutant to the system. Promising results were obtained. Recommendation and Outlook: The application of goethite and in-situ produced ferric hydroxide has demonstrated their effectiveness in the removal of heavy metal ions, such as chromium anions and zinc cations. A proposed continuation of current work is the utilization of similar iron oxides, for instance synthesized akaganeite. The comparison between the results reported in this paper with the results reported in the literature, also deserves attention.

Mercury (Hg) emission from combustion flue gas is a significant environmental concern due to its toxicity and high volatility. A number of the research efforts have been carried out in the past decade exploiting mercury emission, monitoring and control from combustion flue gases. Most recently, increasing activities are focused on evaluating the behavior of mercury in coal combustion systems and developing novel Hg control technologies. This is partly due to the new regulatory requirement on mercury emissions from coalfired combustors to be enacted under the U.S. Title III of the 1990 Clean Air Act Amendments. The aim of this review work is to better understand the state-of-the-art technologies of flue gas mercury control and identify the gaps of knowledge hence areas for further opportunities in research and development. Main Features. This paper examines mercury behaviors in combustion systems through a comprehensive review of the available literature. About 70 published papers and reports were cited and studied. This paper summarizes the mechanisms of formation of mercury containing compounds during combustion, its speciation and reaction in flue gas, as well as subsequent mobilization in the environment. It also provides a review of the current techniques designed for real-time, continuous emission monitoring (CEM) for mercury. Most importantly, current flue gas mercury control technologies are reviewed while activated carbon adsorption, a technology that offers the greatest potential for the control of gas-phase mercury emissions, is highlighted. Although much progress has been achieved in the last decade, techniques developed for the monitoring and control of mercury from combustion flue gases are not yet mature and gaps in knowledge exist for further advancement. More R&D efforts are required for the effective control of Hg emissions and the main focuses are identified.

Abstract: Rare-earth elements (REEs) have been used in fertilizers in the agriculture of China for about 20 years. They have been shown to be beneficial elements for plants. For example, they have improved the yield and quality for several kinds of crops. This paper reviews the current literature on studies of REEs being used as fertilizers. Some studies have focused on the effects of REEs on metabolic nutrients, photosynthesis and stress resistance of plants. Other studies have shown that the environmental behaviors of REEs in soil are dominated by their low solubility. Fluorides, carbonates, phosphates and hydroxides may form neutral complexes containing REEs with a low solubility. The amount of extraneous REEs demonstrate the following relationship: residual» bound to organic matter> bound to Fe-Mn oxides> bound to carbonate»exchangeable and water soluble forms. The adsorption capacity of REEs depends on the clay type and the content of amorphous and manganese oxides, whereas the desorption of REEs is usually very low. At the end of the paper, authors discuss the needs for future environmental research on REEs, which would shed new light on the effects of REEs on agriculture, environment and human health.

Caged common lake mussels (Anodonta piscinalis) have been used in the monitoring of organochlorine compounds in pulp and paper mill recipient watercourses of Finland annually from 1984 to 1998. Statistically significant decreasing trends of chlorophenols and chloroguaiacols originating from chlorobleaching were observed in all recipients in parallel with the decreasing discharges from the mills. Metabolites of chlorophenols, chloroanisoles and chloroveratroles had no or slightly increasing trends. Elevated PCB concentrations were measured in four watercourses. In two areas, PCBs were found to be significantly increasing, in two other cases they showed no trend. A mill producing recycled paper was apparently responsible for an increase of PCBs and DDE in recipient watercourses. Overall decreases were observed for other chlorohydrocarbons except for DDT. Material flows of chlorohydrocarbons were positively correlated with waterflows (Q) in some cases.

This paper outlines the state-of-the-art in discussing tests with functional endpoints for the soil compartment for regulatory purposes. In spite of the fact that organic matter decomposition is one of the most important functions in the soil ecosystem, this process has not been the subject of a test requirement for risk assessment of plant protection products until very recently. Since EU Directive 91/414/EEC concerning the placing of plant protection products on the market requires in its Annex III, point 10.6.2 (entitled “Effects on other soil, non-target macro-organisms”), the evaluation of effects on organic matter breakdown, there is an urgent need to fulfil this requirement. The use of functional endpoints in terrestrial model ecosystems is also under discussion in the framework of the notification process for chemicals. Four potential methods (bait-lamina-test, litterbag test, minicontainer test, cotton-strip assay) taken from ecological literature are briefly reviewed and evaluated in this paper using several defined criteria regarding their usefulness for registration purposes. In this context, areas for further research are identified. The insecticide Dimilin (a.i. diflubenzuron) is used as an example to show how such a test improves risk assessment. Therefore, it is strongly recommended that a guidance paper describing the main principles of at least one test method on organic matter decomposition should be written in order to realise the EU requirement.

Background, Aims and Scope: Current dredged material disposal alternatives have several limitations. Options for dealing with dredged materials include leaving them alone, capping them with clean sediments, placing them in confined facilities, disposing of them at upland sites, treating them chemically, or using them for wetlands creation or other beneficial uses The ability to reuse lake-dredge materials (LDM) for agricultural purposes is important because it reduces the need for offshore disposal and provides an alternative to disposal of the materials in landfills. Often these materials can be obtained at little or no cost to the farmers or landowners. Thus, forage production offers an alternative to waste management since nutrients in the LDM are recycled into crops that are not directly consumed by humans. The objective of this study (Part 2) were to: (1) assess dredge materials from Lake Panasoffkee, Florida as a soil amendment to establish bahiagrass (BG) in a subtropical beef cattle pasture in Sumter County, Florida; and (2) determine the effect of LDM application on the crude protein (CP) and nutrient uptake of BG. This series of two papers aims at providing assessment of the efficacy of lake-dredged materials especially its implication to environment (soil quality, Part 1) and agriculture (forage quality and pasture establishment. Part 2). Methods: The experimental treatments that were evaluated consisted of different ratios of natural soil (NS) to LDM: LDMO (100% NS:0% LDM); LDM25 (75% NS:25% LDM); LDM50 (50% NS:50% LDM); LDM75 (25% NS:75% LDM); and LDM100 (0% NS:100% LDM). Bahiagrass plots at its early establishment were cut to a 5-cm stubble height on Julian days 112 and harvested to the same stubble height on Julian days 238 and on Julian days 546 following the double-ring method. Field layout was based on the principle of a completely randomized block design with four replications. Plant samples harvested at 546 Julian days were ground to pass through a 1-mm mesh screen in a Wiley mill. Ground forage was analyzed for crude protein. Ground forage samples were also analyzed for tissue P, K, Ca, Mg, Mn, Cu, Fe, Al, and Mo concentrations using an ICP spectroscopy. The effects of dredged materials addition on forage yield and on crude protein and nutrient uptake that were taken at 546 Julian days were analyzed statistically following the PROC ANOVA procedures. Results and Discussion: Part 1 of this study demonstrated that the heavy and trace metal contents of LDM were below the probable effect levels and threshold effect levels. As such, the agricultural or livestock industry could utilize these LDM to produce forages. Results showed consistently and significantly (p ≤ 0.001) higher BG biomass production and CP from plots amended with LDM than those of BG planted on plots with 0% LDM. Forage yield of BG during its establishment increased linearly (Forage Yield = 1724.3 + 25.64*LDM; R2= 0.83; p ≤ 0.0001) with increasing rates of LDM application. The CP of BG also varied significantly with varying levels of LDM applications. The tissues of BG with 100% LDM had the greatest CP content while the lowest CP content was from the control plots (LDMO). The CP of BG increased linearly with increasing rates of LDM application. The crude protein response to BG application can be described by a linear equation: Crude Protein = 10.38 + 0.052*LDM; R2= 0.85 p ≤ 0.0001. Addition of LDM had increased the levels of Ca by about 1811 % when compared with the level of soil Ca among plots with no LDM application. Liming the field could have some direct and indirect effects on the chemical status of the soils. The physiological functions performed by Ca in plants are not clearly defined, but it has been suggested that Ca favors the formation of and increases the protein content of mitochondria. Conclusions: Beneficial uses of dredged materials from LP, Florida are both economical and environmental. Often these materials can be obtained at little or no cost to the farmers or landowners. Results showed that dredged materials can be used as soil amendments (lime and fertilizer) for early establishment of BG in beef cattle pastures. Environmentally, dredging of sediments that are rich in CaCO3should restore the 19.4-sq km LP by removing natural sediments from the lake bottom to improve the fishery, water quality, and navigation of the lake. The nutritional uptake of BG grown in unfertile sandy soils of Sumter County was enhanced significantly (p≤0.001) by LDM addition. Uptake of TKN, TP, K, Ca, and Mg were remarkably increased as a result of LDM. Recommendation and Outlook: Land application of LDM from LP may not only provide substantial benefits that will enhance the environment, community, and society in south Florida, but also in other parts of the world especially those areas with forage-based beef cattle pastures and similar climatic conditions. The heavy and trace metal contents of these materials were below the PEL and TEL (see Part 1). As such, the agricultural or livestock industry could utilize these LDM to produce forages. LDM should be regarded as a beneficial resource, as a part of the ecological system. Although our results have demonstrated the favorable and beneficial effects of added LDM on the early establishment of BG in pasture fields., further studies are still needed not only in pastures of south Florida, but also in other areas with subtropical or tropical climatic conditions to determine whether the environmental and ecological implications of LDM application are satisfied over the longer term.

Background: Potential exposure of ground troops in Vietnam to Agent Orange and 2,3,7,8-tetrachIorodibenzo-p-dioxin (TCDD) remains controversial despite the passage of 30 years since the Vietnam War. Because of uncertainty over the serum dioxin levels in ground troops at the end of their service in Vietnam, attempts have been made to develop a methodology for characterizing exposure of ground troops in Vietnam to Agent Orange and other herbicides based upon historical reconstruction from military records. Historical information is often useful in evaluating and modeling exposure, but such information should be reasonably accurate, complete, and reliable. Methods: This paper reviews the procedures and supporting historical information related to the spraying of herbicides in Vietnam. The historical information is classified into two categories: procedural information and operational information. Procedural information covered the process and procedures followed in spraying herbicides from US Air Force fixed wing aircraft (Operation RANCH HAND) in Vietnam, and included approval procedures for spray missions, the criteria required to conduct a mission, the control exercised by the Forward Air Controller and the Tactical Air Control Center and the characteristics of the equipment used to apply the herbicides. Operational information includes data from the RANCH HAND Daily Air Activities Reports, which included geographic locations of specific spray missions, the amount of herbicide sprayed by a specific mission, reports of battle damage to spray aircraft, reports of fighter aircraft support for aerial spray missions, and any comments, such as reasons for canceling a mission. Results: Historical information demonstrates that herbicide spray missions were carefully planned and that spraying only occurred when friendly forces were not located in the target area. RANCH HAND spray missions were either not approved or cancelled if approved when there were friendly forces in the area designated for spraying. Stringent criteria had to be met before spray missions could be approved. The operational information shows that spray missions for both defoliation and crop destruction were conducted in an extremely hostile environment. Heavy ‘fighter suppression’ with antipersonnel ordnance was used to minimize the impact of hostile ground fire on RANCH HAND aircraft. Procedures were in place that prohibited movement of troops into sprayed areas immediately after a mission due to the possible presence of unexploded ordnance delivered by fighter aircraft supporting RANCH HAND missions. The optimal nature of the spray equipment and application procedures minimized the possibility of significant spray drift. Conclusions: Few friendly troops were sprayed by fixed wing aircraft during Operation RANCH HAND, which delivered 95% of all defoliants used in Vietnam. Similarly, few troops were sprayed during helicopter or surface-based spray operations, which constituted the remaining 5 % of defoliants. Detailed policies and procedures for approval and execution of spray missions ensured that friendly forces were not located in the areas targeted for spraying. Fighter aircraft assigned to accompany each spray mission frequently suppressed much of the hostile fire with bombs and other ordnance. Confirmed clearance of the target area was necessary to avoid friendly casualties. Historical records establish that these policies and procedures were strictly followed. Exposure of troops whether from direct spraying or movement through areas recently sprayed was very unlikely. Outlook: The distribution and levels of serum dioxin in RANCH HAND veterans and the US Army Chemical Corps Vietnam veterans (the unit responsible for helicopter and ground-based spray operations) are distinguishable from typical levels in the population decades after the Vietnam conflict. An exposure model similar to that proposed in the 2003 report of the Institute of Medicine’s Committee on ‘Characterizing Exposure of Veterans to Agent Orange and Other Herbicides Used in Vietnam’ was tested in 1988 by the Centers for Disease Control and Prevention and found to be a poor predictor of absorbed dose of TCDD. Military records during the Vietnam War lack the precision to determine that troops were directly sprayed with herbicides during Operation RANCH HAND, especially given the procedures in place to ensure clearance of friendly forces from the target area and the lack of elevated serum levels of TCDD in ground troops judged to have operated in heavily sprayed areas.

Abstract: Background: Plant cell cultures may serve as biosensors for the detection of heavy metals and other toxic substances. Standard culture media and protocols are frequently utilised, but in these media no care is usually taken to control the influence of hormones and nutrients on the reaction of the enzymes or metabolites under consideration as parts of the sensor. The present paper investigates the influence of media composition on the reaction of spruce cells towards heavy metals. Methods: Spruce cell cultures were grown in a standard medium, either i) alone, ii) containing 0.3% sucrose or iii) containing 3% sucrose and the hormones BAP and NAA. The cell cultures were then incubated in medium with fungal elicitor, H2O2, CdSO4 (50 to 500 µM), or, alternatively, with a standard heavy metal mixture containing 80 µM Na2HAsO4, 150 µM CdSO4 and 200 µM PbCl2. Results: Depending on the nutrient status and hormone availability, large differences in glutathione contents and the GSH/ GSSG ratio were observed. However, the cellular redox state seemed to remain more or less constant. Glutathione S-trans-ferase activity was determined with four substrates, and high induction rates for the conjugation of three substrates were observed when hormones were omitted from the media. 1,2-epoxy-nitrophenoxy-propane conjugation was highest in starving cells in the presence of hormones, showing a transient GST induction, with highest rates occurring after 16 hrs following incubation; the induction effect was lost after 24 hrs. Conclusion: A medium containing 3 % sucrose and both hormones (BAP and NAA) appears to be most favourable for cellular growth as well as the expression of a basis level of detoxification enzymes and antioxidants. With this combination, early responses towards heavy metals at low concentration can be monitored. Recommendations and Perspective: Plant cell cultures are valuable tools for the bioindication of heavy metals and toxic xenobiotics. If standard media and protocols are utilised, the influence of hormones and nutrients on the reaction of the biosensor have to be evaluated thoroughly.

Background, Aim and Scope: Problems of long-term existence of the environmental contaminant 2,4,6-trinitrotoluene (TNT) and necessities for the use of trees (‘dendroremediation’) in sustainable phytoremediation strategies for TNT are described in the first part of this paper. Aims of the second part are estimation of [14C]-TNT uptake, localisation of TNT-derived radioactivity in mature tree tissues, and the determination of the degree of TNT-degradation during dendroremediation processes. Methods. Four-year-old trees of hybrid willow(Salix spec, clone EW-20) and of Norway spruce(Picea abies)were cultivated in sand or ammunition plant soil (AP-soil) in wick supplied growth vessels. Trees were exposed to a single pulse application with water solved [U-14C]-TNT reaching a calculated initial concentration of 5.2 mg TNT per kg dry soil. Two months after application overall radioactivity and extractability of14C were determined in sand/soil, roots, stem-wood, stem-bark, branches, leaves, needles, andPiceaMay sprouts. Root extracts were analysed by radio TLC. Results: 60 days after [14C]-TNT application, recovered14C is accumulated in roots (70% for sand variants, 34% for AP-soil variant). 15-28% of14C remained in sand and 61% in AP-soil. 3.3 to 14.4% of14C were located in aboveground tree portions. Above-ground distribution of14C differed considerably between the angiospermSalixand the gymnospermPicea.InSalix, nearly half of above-ground-14C was detected in bark-free wood, whereas inPiceaolder needles contained most of the above-ground-14(54-69%). Discussion: Pulse application of [14C]-TNT provided evidence for the first time that after TNT-exposure, in tree root extracts, no TNT and none of the known metabolites, mono-amino-dinitro-toluenes (ADNT), diaminonitrotoluenes (DANT), trinitrobenzene (TNB) and no dinitrotoluenes (DNTs) were present. Extractable portions of14C were small and contained at least three unknown metabolites (or groups) forSalix.InPicea, four extractable metabolites (or groups) were detected, where only one metabolite (or group) seemed to be identical forSalixandPicea.All unknown extractables were of a very polar nature. Conclusions: Results of complete TNT-transformation in trees explain some of our previous findings with ‘cold analytics’, where no TNT and no ADNT-metabolites could be found in tissues of TNT-exposedSalixandPopulusclones. It is concluded that ‘cold’ tissue analysis of tree organs is not suited for quantitative success control of phytoremediationin situ. Recommendations and Outlook: Both short rotationSalicaceaetrees and conifer forests possess a dendroremediation potential for TNT polluted soils. The degradation capacity and the large biomass of adult forest trees with their woody compartments of roots and stems may be utilized for detoxification of soil xenobiotics.

Background, Aims and Scope: Dredged materials because of its variable but unique physical and chemical properties are often viewed by society and regulators as pollutants, but many have used these materials in coastal nourishment, land or wetland creation, construction materials, and for soil improvement as a soil amendment. Environmental impact assessment is an important pre-requisite to many dredging initiatives. The ability to reuse lake-dredge materials (LDM) for agricultural purposes is important because it reduces the need for offshore disposal and provides an alternative to disposal of the materials in landfills. Additional research on disposal options of dredged materials are much needed to supply information on criteria testing and evaluation of the physical and chemical impacts of dredged materials at a disposal site, as well as information on many other aspects of dredging and dredged material disposal. While preliminary efforts are underway to provide information to establish criteria for land disposal, testing procedures for possible land disposal of contaminated sediments are still in their developing stage. The objective of this study (Part 1) was to quantify the effect of applied LDM from Lake Panasoffkee (LP), Florida on soil physico-chemical properties (soil quality) at the disposal site. This series of two papers aims at providing assessment of the efficacy of lake-dredged materials from LP especially its implication to environment (soil quality, Pan 1) and agriculture (forage quality and pasture establishment, Part 2). Methods: The experimental treatments that were evaluated consisted of different ratios of natural soil (NS) to LDM: LDMO (100% NS:0% LDM); LDM25 (75% NS:25% LDM); LDM50 (50% NS:50% LDM); LDM75 (25% NS:75% LDM); and LDM100 (0% NS:100% LDM). Field layout was based on the principle of a completely randomized block design with four replications. The Mehlich 1 method (0.05NHCl in 0.025NH2SO4) was used for chemical extraction of soil. Soil P and other exchangeable cations (Ca, Mg, K, Al, and Fe) were analyzed using an Inductively Coupled Plasma (ICP) Spectroscopy. The effects of dredged materials addition on soil quality and compaction were analyzed statistically following the PROC ANOVA procedures. Results and Discussion: Sediments that were dredged from LP have high CaCO3content (82%) and when these materials were incorporated into existing topsoil they would have the same favorable effects as liming the field. Thus, sediments with high CaCO3may improve the physical and chemical conditions of subtropical sandy pastures. The heavy and trace metal contents of LDM were below the probable effect levels (PEL) and threshold effect levels (TEL). Average values for Pb, Zn, As, Cu, Hg, Se, Cd, and Ni of 5.2 ± 1.3, 7.0 ± 0.6,4.4 ± 0.1, 8.7 s= 1.2, 0.01 ± 0.02,0.02 ± 0.02,2.5 s 0.1, and 14.6 = 6.4 mg kg-1, respectively, were below the TEL and the PEL. TEL represents the concentrations of sediment-associated contaminants that are considered to cause significant hazards to aquatic organisms, while, PEL represents the lower limit of the range of the contaminant concentrations that are usually or always associated with adverse biological effects. As such, the agricultural or livestock industry could utilize these LDM to produce forages. LDM should be regarded as a bénéficiai resource, as a part of the ecological system. Addition of LDM had significant (p ≤ 0.001) effects on soil physico-chemical properties and soil quality. Compared with the control plots, the soils in plots amended with LDM exhibited: (1) lower degree of soil compaction; (2) an increase in soil pH, Ca, and Mg; (3) decrease in the levels of soil Mn, Cu, Fe, Zn, and Si; and (4) no significant change in the level of Na in the soil. Results have shown the favorable influence that LDM had on soil compaction. The treatment x year interaction effect was not significant, but the average soil compaction varied widely (p ≤ 0.001) with LDM application. In 2002 and 2003, soil compaction of plots was lowered significantly as a result of LDM additions. The least compacted soils in 2002 and 2003 were observed from plots with LDM75 with mean soil compaction of 300 × 103and 350 × 103Pa, respectively. Conclusion: Beneficial uses of dredged materials from LP, Florida are both economical and environmental. Often these materials can be obtained at little or no cost to the farmers or landowners in south Florida. Environmentally, dredging of sediments that are rich in CaCO3should restore the 19.4-sq km LP by removing natural sediments from the lake bottom to improve the fishery, water quality, and navigation of the lake. The bottom sediment materials from lakes, river, and navigational channels usually are composed of upland soil enriched with nutrients and organic matter. These materials should be regarded as a beneficial resource to be used productively and not to be discarded as spoil materials. Recommendation and Outlook: Land application of LDM from LP may not only provide substantial benefits that will enhance the environment, community, and society in south Florida, but also in other parts of the world especially those areas having tropical and subtropical climate with forage-based beef cattle pastures. The heavy and trace metal contents of LDM from LP were below the PEL and TEL. As such, the agricultural or livestock industry could utilize these LDM to produce forages (Part 2 of this study). LDM should be regarded as a beneficial resource, as a part of the ecological system. Further studies are still needed to determine whether the environmental and ecological implications of LDM application are satisfied over the longer term.

Goal, Scope and Background: This paper uses two case studies of U.S. Department of Energy nuclear weapons complex installations to illustrate the integration of expedited site characterization (ESC) and multimedia modeling in the remedial action decision making process. Conceptual Site Models, Multimedia Models, and Expedited Site Characterization: Conceptual site models outline assumptions about contaminates and the spatial/temporal distribution of potential receptors. Multimedia models simulate contaminant transport and fate through multiple environmental media, estimate potential human exposure via specific exposure pathways, and estimate the risk of cancer and non-cancer health outcomes. ESC relies on using monitoring data to quantify the key components of an initial conceptual site model that is modified iteratively using the multimedia model. Case Studies: Two case studies are presented that used the ESC approach: Los Alamos National Laboratory (LANL) and Pantex. LANL released radionuclides, metals, and organic compounds, into canyons surrounding the facility. The Pantex Plant has past waste management operations which included burning chemical wastes in unlined pits, burying wastes in unlined landfills, and discharging plant wastewaters into on-site surface waters. Conclusions: The case studies indicate that using multimedia models with the ESC approach can inform assessors about what, where, and how much site characterization data needs to be collected to reduce the uncertainty associated with risk assessment. Lowering the degree of uncertainty reduces the time and cost associated with assessing potential risk and increases the confidence that decision makers have in the assessments performed.

Background: Organotins have been used world-wide as antifoulants in ship paints. Repeatedly, severe effects on aquatic species have resulted. The use of organotins for this purpose was ruled out, and dumping of contaminated harbor sludge into the sea was prohibited. Land-based dumping is seen as an alternative. Objective: This study investigates sorption, uptake and translocation of tributyltin (TBT) to willow trees in order to evaluate1 phytoremediation as treatment option. The study considers the influence of pH on the plant uptake of organotins. Experimental set-up: Chemicals investigated were the weak base tributyltin chloride (TBTCl) and the neutral tributyltin hydride (TBTH). Organotins were extracted from solution and plant material with toluene, and analyzed as tin by AAS with graphite oven. The pH in solution varied from pH 4 to pH 7. The sorption to living and dead roots, stems and leaves was measured in shaking experiments. The uptake into intact trees was measured at nominal levels of 1 and 10 mg TBT/1 for TBTH and TBTCl at low and high pH. Results: The sorption to roots and leaves dropped for dead tissue, but did not vary much with pH. The sorption to stems increased for dead stems and with pH. The solubility of TBTCl in water was below 10 mg/1 and lowest at pH 4. Concentrations of TBTCl and TBTH in solutions with trees dropped rapidly to low values. Highest TBT contents in trees were found in roots and lower stems. The concentrations followed the concentrations in solution. The pH had only a small effect on the plant uptake of TBTCl, and no effect on the uptake of TBTH. No effective translocation to higher stems or leaves was found. Discussion: An ion trap mechanism that accumulates the weak base TBTCl in the xylem sap of plants and leads to upward translocation could not be detected. Neither TBTCl at low or high pH, nor the neutral lipophilic chemical TBTH, were translocated effectively to leaves. The TBT* cation sorbed strongly to plant tissue. The exact mechanism for the strong sorption of the cation is unknown, but similar effects have been observed for algae, liposomes and isolated biomembranes. Conclusions: Both the uptake of the neutral TBTH and the uptake of the neutral molecule form of TBTCl into willows was as is to be expected from theory. The cation TBT* showed an unexpected behavior which has been observed before. No ion trap occurs, and the phytoextraction of TBT is not feasible. Outlook: Planting trees, or other appropriate vegetation, could have a beneficial remediation effect by aeration of the TBT-con-taminated soil or sludge. In a follow-up paper, the toxicity of TBT to willow trees will be described.

Intention, Goal, Scope, Background: Following the introduction of automobile catalytic converters the platinum group metals (PGM) platinum (Pt), palladium (Pd) and rhodium (Rh) gain on increasing interest in environmental research as these metals are emitted with exhaust fumes into the environment. Consequently, elevated PGM levels were found in different environmental matrices uch as road dusts, soils along heavily frequented roads, sediments of urban rivers etc. Accordingly, the effects of increasing PGM emissions on the biosphere are controversially discussed. Objective: This paper summarizes the present knowledge on the biological availability of PGM to plants and animals. As biological availability is one of the most decisive factors determining the toxicologi-cal potential of xenobiotics, this information is very important to evaluate the possible threat of the noble metals to ecosystems. Results and Discussion: The availability of soluble as well as particle bound PGM to terrestrial plants was demonstrated in several studies. Experimental investigations revealed uptake of Pt, Pd and Rh also by aquatic plants. Additionally, the biological availability of the noble metals for animals has been verified in experimental studies using soluble metal salts, catalytic converter model substances, sediments of urban rivers, road dust or tunnel dust as metal sources. These studies refer mainly to aquatic animals. Beside of free living organisms, in particular worms parasitizing fish demonstrated a high potential to accumulate PGM. This could be of great interest in respect of biomonitoring purposes. Generally, for plants as well as for animals Pd turns out to be the best available metal among the PGM. Compared to other heavy metals, the biological availability of PGM from road dust to zebra mussels(Dreissena polymorpha)ranged between that of Cd and Pb. Conclusion: Especially chronic effects of PGM on the biosphere can not be excluded due to (1) their cumulative increase in the environment, (2) their unexpected high biological availability and bioaccumulation and (3) their unknown toxicological and ecotoxicological potential. However, it appears that acute effects on ecosystems due to anthropogenic PGM emission are not likely. Recommendation and Outlook: Research on environmental PGM contamination of the biosphere, especially the fauna, and on long-term toxiciry of low PGM concentrations is highly appreciated. These studies require very sensitive analytical techniques to determine PGM even in low sample amounts. Research has to be done in particular on reliable determination of (ultra) trace levels of Pd and Rh as the lack of data on these two metals is mainly due to analytical problems.

This paper shows the geographic distribution in Germany of iron (Fe), nickel (Ni) and lead (Pb) analyzed in mosses in 1995/96 and compares it with the results of the 1990/91 pilot study within a European moss-monitoring programme. Other elements (As, Cd, Cr, Cu, Ti, V, Zn) are compared on basis of the overall element medians for Germany of the 1990/91 and 1995/96 survey.

Background: Chlorophenols (CPs) constitute a group of organic pollutants that are introduced into the environment as a result of several man-made activities, such as uncontrolled use of pesticides and herbicides, and as byproducts in the paper pulp bleaching. Promising removal technologies of chlorinated aromatics consist in the application of advanced oxidation processes (AOPs) that can provide an almost total degradation of a variety of contaminants. Among these, wide application find Fenton systems based on generation of reactive species having a high oxidizing power, such as hydroxyl radical HO•. Our objective was that of determining the overall degradation efficiency of the model compound 2,4-dichlorophenol (DCP) by thermal Fenton-type oxidation systems with a view toward defining in more details relevant process parameters, the effect of reaction temperature and of co-catalyst Cu2+. Methods: Reaction conditions were similar to those generally adopted as optimal in many practical applications, i.e. pollutant /Fe2+(as FeSO4) ratio ca. 20, Fe2+/Cu2+(co-catalyst) 2:1, pH adjusted and controlled at pH 3, and H2O2in excess (up to four-fold over the stoichiometric amount required for complete mineralization). Results and Discussion: The results demonstrate that it is advantageous to carry out the reaction at a temperature markedly higher (70°C) than ambient. The stepwise addition of H2O2in aliquots yields an efficient transformation, while allowing a convenient control of the reaction exothermicity. Under these conditions, the essentially complete removal of the initial DCP is accomplished using just one equiv of H2O2during 15 min; excess H2O2(5 equivalents) yields extensive substrate mineralization. Also relevant, at 70°C dechlorination of the initial DCP (and of derived reaction intermediates) is remarkably extensive (3-5% residual TOX), already with the addition of 1 equiv of H2O2. At the end of the reaction, IC and IC-MS analyses of the solution reveal that only low-molecular weight carboxylic acid (acetic, formic, oxalic, malonic, tartaric, etc.) contribute to the residual TOC. Conclusions: The whole of the results herein point to the advantage of performing the process at temperatures substantially higher than ambient (70°C). Under the conditions adopted, almost complete degradation of the initial toxic compound can be achieved using hydrogen peroxide in fair excess (e.g., 3.5 equiv H2O2). Recommendations and Outlook: In applying practical Fenton-type degradation systems to heavily polluted wastes, either for the pre-treatment of waters with a high COD value prior to biodegradation or for complete mineralization of pollutants, the set up of appropriate reaction conditions appears to be a key factor. Also, it is desirable to keep the concentration of iron salts within the lower limits in order to minimize the production and disposal of iron oxide sludges.

In this paper we review an interesting method of PET recycling, i.e. chemical recycling; it is based on the concept of depolymerizing the condensation polymer through solvolytic chain cleavage into low molecular products which can be purified and reused as raw materials for the production of high-quality chemical products. In this work our attention is confined to the hydrolysis (neutral, acid and alkaline) and glycolysis processes of PET chemical recycling; operating conditions and mechanism of each method are reported and described. The neutral hydrolysis has an auto accelerating character; two kinetic models have been proposed: an half-order and a second order kinetic model. The acid hydrolysis could be explained by a modified shrinking core model under chemical reaction control and the alkaline hydrolysis by a first-order model with respect to hydroxide ion concentration. To describe glycolysis, two different kinetic models have been proposed where EG can act or not as internal catalyst. Further experimental and theoretical investigations are required to shed light on the promising processes of PET chemical recycling reviewed in this work.

The possibility of exploiting self-propagating reactions for environmental protection is discussed in this paper. In particular, results obtained at the laboratory scale and related to the fixation and consolidation of high level radioactive wastes, the recycling of silicon sludge and aluminum dross produced by semiconductor industries and aluminum foundries, the treating and recycling of a highly toxic solid waste from electrolytic zinc plants, and the degradation of chlorinated aromatics, are examined with particular emphasis on the latter case. Specifically, the self-propagating destruction of hexachlorobenzene and 2-(2-4-dichlorophenoxy)-propanoic acid with calcium hydride as reductive substrate is demonstrated. In fact, the heat liberated by the reactions involved is large enough to guarantee the self-sustaining character of the process within a wide range of reactants compositions. Moreover, no residual chlorinated organic compounds were found in the final solid product. Some reactor engineering aspects, as well as other significant future scientific and technological issues, are also addressed in view of large-scale applicability of processes based on self-propagating reactions. To date, the batch reactor technology seems to be more easily applicable, although the use of continuous reactors is not excluded in the next future.

Goal, Scope and Background: Over the last decade Greece has become a leading country in the EU as concerns the cage farming of seabream and seabass. A strong debate has risen, however, about the environmental impacts of aquacultures in the coastal areas. The present paper deals with this problem and it is based on measurements of physico-chemical parameters in the water column, particulate matter and sediments in the area of Astakos Gulf, a coastal embayment in western Greece where three big fish farms are currently operating. Methods: Water samples were collected by using Hydro-Bios sampling bottles, whereas a prototype sediment trap was installed under a fish cage for the collection of particulate matter. Temperature, dissolved oxygen, pH and salinity were measured in situ using portable equipment. Nutrients were determined by standard spectrophoto-metric methods. Trace metals were determined by Atomic Absorption Spectrometry. Dissolved organic carbon was determined by a Shimadzu 5000A carbon analyzer, whereas organic carbon in seiments was determined titrimetrically. Results and Discussion: No clear eutrophication incidents have been identified, although the water column near the fish farms was enriched in nutrients and organic carbon. A sludge ‘blanket’ covers considerable parts of the seabed and is enriched in colloidal organic carbon and trace metals (Cd, Cu, Fe and Zn) that come from unused fish food. The biodegradation of this sludge leads to the development of anoxic conditions followed by the formation of undesirable gases, precipitation or remobilization of metals and the extinction of benthic fauna. Conclusion: The operation of fish farms at the coastal area of Astakos Gulf, and probably in similar Mediterranean gulfs, affects the marine environment, particularly in the vicinity of the cages. The most significant influence concerns the near-bottom water layer. The environmental impacts depend on the amount of food given to fishes, the mode of feeding, the fish density in cages, the annual production and the years of unit operation. The hydrology and the geomorphology of the area are also critical factors for its environmental quality. Recommendation and Outlook: The success of the fish-farming sector in the Mediterranean is accompanied by environmental and, in some extents, by social and marketing problems. These problems, derived from the rapid development of fish farming, can be solved only through an integrated management, using methods such as environmental impact assessment, risk assessment, economic evaluation, vulnerability assessments, resource accounting, cost-benefit analysis and outcome-based monitoring.

According to directive 93/67/EEC of the European Commission, this paper deals with the generic exposition evaluation of the environmental concentration of cooling lubricant chemicals from the metal working industry into the hydrosphere. After considering the relevant life-cycle steps and the selection of a representative point source for the ’reasonable worst case’, the emission per day Elocalwateris determined. It leads to the predicted environmental concentration (PEClocalwater) for the local stage in the compartment water. In order to gain the PEClocalwaterfor an example - a corrosion inhibitor as additive in a cooling lubricant -, the relevant emission paths and the corresponding representative point source are described for the reasonable worst case. For non-water-miscible cooling lubricants, none of the operations in the life cycle leads to a release into the compartment water. To evaluate the hazard potential for cooling lubricant chemicals, the complete risk assessment has to be done. Also, the assessment has to be done for all high production volume chemicals, new substances and existing hazard chemicals. This means that even industrial categories like chemicals used in the textile industry or biocides and others have to be evaluated.

Background, Aims and Scope: In the first part of this paper the main principles which control the dehalogenation of polychlorinated aromatic compounds on municipal waste incineration fly ash (MWI-FA) have been discussed and the model fly ash of similar dehalogenation activity has been proposed. Even if both systems show comparable dehalogenation properties, the main question concerning the postulated identical reaction mechanism in both cases is left unanswered. The other very important point is to what extent is this dechlorination mechanism thermodynamically controlled. The same problem is often discussed in the literature also for the de novosynthetic reactions. From the data it is clear that metallic copper plays a decisive role in the mechanism of the dehalogenation reaction. Although the results reported in the first part strongly support the idea that copper acts in this dechlorination as the reaction component, in contrast to its generally accepted catalytic behaviour, we believed that additional support for this conclusion can be obtained with the help of a thermodynamic interpretation of the mechanism of the reaction. Results and Discussion: The pathways of hexachlorobenzene dechlorination on MWI-FA and model fly ash were studied in a closed system at 260-300°C under nitrogen atmosphere. These pathways were the same for both systems, with the following prevailing sequences: hexachlorobenzene → pentachlorobenzene → 1,2,3,5-tetrachlorobenzene → 1,3,5-trichlorobenzene → 1,3-dichlorobenzene. Thermodynamic calculations were carried out by using the method of minimization total Gibbs energy of the whole system. In the calculations, the following reaction components were taken into account: all gaseous chlorinated benzenes, benzene, hydrogen chloride, a gaseous trimer Cu3Cl3, and also Cu2O and CuCl2as solid components. The effect of the reaction temperature and the amount of copper and water vapour were considered as well. The effect of reaction temperature was determined from the data calculated for the 500 to 750 K temperature region. The effect of the initial composition was determined for the molar amounts of copper = 0.01-3 moles and water vapour = 0.2 to 3 moles per mole of chlorobenzene isomer. Conclusions: The results of hexachlorobenzene dechlorination by MWI-FA and model fly ash under comparable reaction conditions allow us to conclude that both dechlorinations proceed via the same dechlorination pathways, which can be taken as an evidence of the identical dehalogenation mechanism for both systems. The relative percentual distribution of the dehalogenated products depends on the temperature, but not on the initial amount of water vapour or copper metal. On the other hand, the initial amount of copper substantially affects the conversion of the dehalogenation as well as the molar ratio of Cu3Cl3to HCl in the equilibrium mixture. Comparison of the experimental with thermodynamic results supports the idea that dehalogenation reactions are thermodynamically controlled. Recommendations and Outlook: Thermodynamic analysis of the dehalogenation reactions may prove useful for a wide range of pollutants. The calculations concerning polychlorinated biphenyls and phenols are under study.

The present paper summarises the results of the project: ‘Survey of Anthropogenic Sources of Dioxins and Furans in the Baltic Region’. As a part of the project, inventories have been carried out in Estonia, Latvia, Lithuania and Poland by applying the toolkit for quantification of dioxin and furan releases developed by UNEP Chemicals. The main route of direct releases to the environment is emission to air. Total emission to air from Poland was estimated at 490 (88–1,300) g I-TEQ/year, whereas the emissions from Estonia, Latvia and Lithuania were estimated as being 14 (2.4-54), 23 (2.6-63) and 17 (2.6-38) g I-TEQ, respectively. In general, the uncertainty on the estimates is very high, and recommendations regarding further development of the inventories have been made, and measures for reducing the releases have been provided.

Background, Aims and Scope: It is well known that the fly ash from filters of municipal waste incinerators (MWI-FA) shows dehalogenation properties after heating it to 240-450°C. However, this property is not general, and fly ash samples do not possess dehalogenation ability at all in many cases. Fly ash has a very variable composition, and the state of the fly ash matter therefore plays the decisive role. In the present paper, the function of important components responsible for the dehalogenation activity of MWI-FA is analysed and compared with the model fly ash. Methods: With the aim of accounting for the dehalogenation activity of MWI-FA, the following studies of hexachlorobenzene (HCB) dechlorination were performed: The role of copper in dehalogenation experiments was evaluated for five types of metallic copper. The gasification of carbon in MWI-FA was studied in the 250-350°C temperature range. Five different kinds of carbon were used, combined with conventional Cu° and activated nanosize copper powder. The dechlorination experiments were also carried out with Cu(II) compounds such as CuO, Cu(OH)2, CuCl2and CuSO4. The results were discussed from the standpoint of thermodynamics of potential reactions. Based on these results, the model of fly ash was proposed, containing silica gel, metallic copper and carbon. The dechlorination ability of MWI-FA and the model fly ash are compared under oxygen-deficient atmosphere. Conclusions: The results show that, under given experimental conditions, copper acts in the dechlorination as a stoichiometric agent rather than as a catalyst. The increased surface activity of copper enhances its dechlorination activity. It was found further that the presence of copper leads to a decrease in the temperature of carbon gasification. The cyclic valence change from Cu° to Cu+ or Cu2+is a prerequisite for the dehalogenation to take place. Recommendation and Outlook: Thermodynamic analysis of the dechlorination effect, as well as the comparison of dechlorination pathways on MWI-FA and model fly ash, can provide a deeper understanding of the studied reaction.

This paper assesses the feasibility of using atmospheric measurement of fluorinated greenhouse gases (HFCs, PFCs and SF6) for the review and verification of greenhouse gas inventories provided by national governments. For this purpose, available data were compiled. It was found that atmospheric measurements of these gases are available and provide an indication of global annual emissions with sufficient certainty to reach the following conclusions: Within the uncertainty of the method, it was found that emissions of HFC-23, a by-product of HCFC-22 production, as obtained from atmospheric measurements did not decrease as fast, as the countries have reported. In contrast, SF6concentrations in the atmosphere suggest higher emissions than reported by countries. Regional emission estimates from atmospheric measurements are still in a more pioneering state and cannot be compared to national estimates. Intensified efforts to measure HFCs, PFCs and SF6in the atmosphere are recommended.

Soil pollution data is also strongly scattering at small scale. Sampling of composite samples, therefore, is recommended for pollution assessment. Different statistical methods are available to provide information about the accuracy of the sampling process. Autocorrelation and variogram analysis can be applied to investigate spatial relationships. Analysis of variance is a useful method for homogeneity testing. The main source of the total measurement uncertainty is the uncertainty arising from sampling. The sample mass required for analysis can also be estimated using an analysis of variance. The number of increments to be taken for a composite sample can be estimated by means of simple statistical formulae. Analytical results of composite samples obtained from different fusion procedures of increments can be compared by means of multiple mean comparison. The applicability of statistical methods and their advantages are demonstrated for a case study investigating metals in soil at a very small spatial scale. The paper describes important statistical tools for the quantitative assessment of the sampling process. Detailed results clearly depend on the purpose of sampling, the spatial scale of the object under investigation and the specific case study, and have to be determined for each particular case.

The Baltic Sea Region has a large number of landfills that need remediation after care routines and control, in order to avoid future emissions to the environment and to fulfil the demands in the EU Waste Council Directive on the landfill of waste. Based on the Måsalycke test screening, an excavation of whole or of parts of the landfill can be seen as a potential measure for some of the old landfills. The material excavated in the test was screened into the fractions: < 18 mm, 182-50 mm and > 50 mm. The coarsest fraction (> 50 mm) contained 50% wood and paper. The medium-sized fraction (18–50 mm) contained stones and indefinable soil-like material, while the fine fraction contained peat-like material with some other small waste components. The spectral analysis of heavy metals indicated only high concentrations of zinc and there was no significant difference between the fine and the medium-sized fractions. The medium sized and the unsorted fraction was moisturized and refilled into the pit. The methane content in the landfill gas from the pit was 50–57% in the sorted material with a flow of 8–17 l/min and 38–57% in the unsorted fraction with a flow of 2–13 l/min during the first 1.5 year. The Måsalycke landfill is in the methanogenic phase and leachate concentrations are normal. Landfill mining can be used to prolong the landfill lifetime and/or used as a tool for remedial actions in contaminated sites.

In this paper, we present applied methanol recycling technology utilising Chromatographic applications, which has been designed for an academic-size institution. The procedure is combined out of proper recovery technique and the biodegradation method intended for postprocessing residues. Additionally, analytical methods controlling the quality of the process are described in detail in order to enable full transfer of the proposed methodology to the analogous institution. The recovered solvent is of relatively high purity (> 99.92%), containing traces of water and volatile compounds. The spectral purity is sufficient to employ recycled methanol in HPLC applications where low wayelength detection is necessary. Biodegradation of distillation first-cuts and still bottoms is implemented using isolated strains ofMethylobacterium organophilum. During the biodegradation process, a series of carotenoids are biosynthesized, which are of a high commercial value. The proposed application, therefore, offers not only a sustainable, waste-free solution in handling methanol waste, but can also serve as a potential source of value.

Environmental monitoring faces the challenge of measuring an increasing number of analytes at ever decreasing concentrations. Since not all species of a given analyte have the same detrimental impact on the environment, new analytical devices and techniques are required to distinguish between the different species of a pollutant or different groups of pollutants. This paper describes analytical techniques based on biomaterials that are toxically sensitive to pollutants. This approach permits the biomonitoring of certain compounds by looking at their toxic properties. Although these techniques are based on a sound analytical strategy, their applications are limited because most of the interactions between the biological material and the analyte are irreversible. Additionally, the immobilised biological material has a limited stability. Several biomonitoring strategies based on electrochemical biosensing are discussed here and how to recover the bioactivity of biosensing system, both in discrete and automated procedures, is also reviewed.

The conclusion in December 2000 of the negotiations for the ‘Stockholm Convention’ can clearly be labeled as a success. The Convention text was negotiated in merely five sessions of the Intergovernmental Negotiating Committee (INC) and accomplished after its fifth session despite the fact that numerous controversial issues, such as the inclusion of new substances under the ambit of the Convention, the acknowledgement of the precautionary principle or — clearly most controversial the financing mechanisms, remained to be resolved. This paper attempts to provide a somewhat impressionistic account of the negotiations leading to the conclusion of the ‘Stockholm Convention’ as experienced by the members of the Swiss delegation participating in the negotiations of the INC. Besides a brief overview on the ‘history’ of the negotiations, it will focus on some issues of special interest — and controversy — to the negotiators, and finally attempt to provide an outlook on the future of the work performed by the INC and the implementation of the Convention. Issues of special interest are environmental policy issues, capacity building and financing, trade-related issues, precautionary principles, and technical and scientific issues.

Marine macroalgae species from the polar regions were investigated for their importance as natural sources of volatile halogenated compounds released into the biosphere. Several different halogenated C1to C4hydrocarbons were identified and their release rates determined. The compounds contained mainly bromine and iodine, and form was the dominant compound released. Although an annual atmospheric input of approximately 108−1010g bromine and 107−108g iodine was calculated from the release rates, marine macroalgae are apparently not the major source on a global scale, as the release is up to four orders of magnitude lower than a presumed annual flow from the oceans. Despite this, macroalgae may be more important on a local scale due to their occurrence at a high biomass in the coastal regions. The present paper gives an overview about studies done on the release of volatile halocarbons by macroalgae from polar regions. Furthermore, the function of these compounds in the macroalgal metabolism is discussed.

During the operation “Allied Force” in the spring of 1999, the burning or damaging of industrial and military targets in the Former Republic of Yugoslavia resulted in the release of a large number of chemicals into the atmosphere. The releases contained not only conventional air pollutants, but also Semi-Volatile Organic compounds (SVOs) which are known to be hazardous to health. Under suitable meteorological conditions, these chemicals can be transported across borders over large distances. In this paper, an analysis of measurements and dispersion calculations is presented which provides evidence of pollutant transport from the conflict area to Greece. The measuring program was carried out in Xanthi, Greece and included aerosol sampling and subsequent analysis for the determination of the concentration of SVOs including dioxins, furans, PCBs (PolyChlorinated Biphenyls), PAHs (Polycyclic Aromatic Hydrocarbons) and organic phthalates.

This paper contains a literature review of the occupational injuries and ill-health in agriculture world-wide and a survey of the attempts that have been made to estimate the resulting economic and social costs.

Microbial decontamination of hydrocarbon-polluted soil was paralleled with soil respiration measurements. About 1,500 tons of a loamy top soil were found to be contaminated with approximately 2000 mg/kg of aliphatic hydrocarbons, mainly oleic (C18:1) and linoleic acid (C18:2) found in the vicinity of a linoleum manufacturing and then a car dewaxing plant. The contaminated soil was analysed for dry matter, pH, dehydrogenase activity, electrical conductivity and nutrient content viz. nitrate, phosphorus and potassium, as well as a number of indigenous microbes. The soil was low in salt and nutrients. This paper describes the procedure and measures to decontaminate this bulk soil on site from approx. 2,000 to 500 mg of aliphatic hydrocarbons/kg dry matter by use of a nutrient emulsion, indigenous micro-organisms and aeration over 13 months. This 75% reduction in aliphatic hydrocarbons resulted in a concomitant carbon efflux, measured as soil respiration, and was used to calculate carbon fluxes.

In general, contamination levels tend to be highest close to sources of a chemical and decline with increasing distance as a result of dilution, dispersion and degradation. However, contrary to this, circumstances have been described when contamination levels are higher further away from sources than at the sources themselves. Examples are elevated levels of persistent, hydrophobic, organic chemicals in the Arctic, in mountain regions and in forest soils. In order to address the questions of why and when such an inversion of environmental levels is occurring, this paper seeks to identify, name and categorise principles of general validity leading to such behaviour. By compiling and analysing various causes of elevated contamination levels in the environment, three main categories became apparent, 1. equilibrium partitioning effects, 2. effects resulting from changes in phase composition, volume or temperature, and 3. dynamic or kinetic effects. These principles are illustrated with several examples. The case can be made that understanding, quantifying and predicting these causes could provide a general conceptual framework for studying the fate of chemicals in the environment.

The paper consists of two main parts. The first part is concerned with different aspects of mathematical modeling of material flow systems for the linear static case. The problems considered are the description of the model class, data reconciliation, identification of subsystems and the analysis of system properties relevant e.g. for simulation. In the second part an application of the modeling tools proposed in the first part to a study on the metabolism of phosphorus in an Austrian region is given.

This is the second of a two-part series describing the sorption kinetics of hydrophobic organic chemicals. Part I “The Use of First-Order Kinetic Multi-Compartment Models” is published in issue 1 of this journal, pp. 21–28. Sorption kinetics of chlorinated benzenes from a natural lake sediment have been investigated in gas-purge desorption experiments. Biphasic desorption curves, with an initial “fast” part and a subsequent “slow” part, were found for all tested chlorobenzenes. From these results first-order sorption uptake and desorption rate constants were calculated with a two-sediment compartment model, which is presented in the first paper.

According to present understanding, persistent superlipophilic chemicals — such as octachlorodibenzo-p-dioxin, octachlorodibenzofuran, Mirex etc — with log Kow> 6 and cross sections > 9.5 Å, bioconcentrate in aquatic organisms only little from ambient water. The most convincing argument against it is that in bioconcentration experiments with superlipophilic chemicals amounts applied exceeded water solubility by several orders of magnitude. This paper describes various methods for determining bioconcentration factors (BCF) of superlipophilic compounds. As exemplified with octachlorodibenzo-p-dioxin, BCF values evaluated by these methods match well with those calculated by QSARs for fish and mussels based on log Kowand water solubility. As expected, these BCF values exceed previous values by several orders of magnitude. For BCF evaluation of superlipophilic chemicals in aquatic organisms we recommend:flow-through systems, kinetic method (OECD guideline No. 305 E)ambient concentrations < water solubilityduring the uptake and especially during the elimination phase no toxic effects of the test organisms should occur.

This is the first of a two-part series describing the Sorption kinetics of hydrophobic organic chemicals. This paper discusses the use of first-order kinetic compartment models in environmental studies, of subjects such as bioaccumulation and sorption. A comprehensive mathematical description and model calculations are presented. Differences between these models and the pharmacokinetic compartment models will be indicated, emphasis being given to the use of the former in sorption studies.

This paper summarizes recent research on the adsorption of organic vapors on surfaces. Since the low gas phase concentration range is typical for environmental situations, this review is restricted to these adsorption coefficients.

Material Flow Analysis (MFA) has become an important instrument in environmental science and pollution research. In this paper, we look at the MFA problem as a particularly structured system identification problem. Special emphasis is given to the linear, static case, where we describe a procedure for reconciliating the flow measurements and for estimating the unmeasured flows and the transfer coefficients by taking into account a priori restrictions such as balance equations.

A review has been made recently studying global total ozone changes (including stratospheric and troposphere components), as well as biologically active surface solar ultraviolet (UV-B) radiation variations on the basis of satellite and conventional surface observations (Kondratyev and Varotsos, Part I). In the aforementioned review, relevant impacts on terrestrial and aquatic ecosystems, as well as on biochemical cycles and man, have been discussed. Special attention has been paid to the analysis of observed and potential impacts of enhanced UV-B radiation on biogeochemical cycles and the chemical composition of the atmosphere. In this context, possibilities remote sensing techniques applications aimed at obtaining more complete information on atmospheric concentrations of various trace gases determining the ozone content have been considered in the present paper.