BACKGROUND: There has been an increasing concern about the treatment and disposal of contaminated sediment from dredged river, harbor or estuary due to the accumulated toxic organics such as dioxins and inorganics particularly heavy metals like Cr, Pb, Zn, Cu, Hg and Cd. However, considering the huge amount of materials and financial costs involved, any candidate technology must ultimately result to reusable residual by-products. This can only be made possible if the toxic pollutants are removed or stabilized in the raw sediment and then fed back into the materials cycle. Currently, we are developing a pyrolysis process for the commercial-scale cleanup of dioxins and heavy metal-contaminated river sediment to yield reusable char for various economical applications. In this connection, this paper describes our preliminary investigation into the extent of dioxins and heavy metal volatilization from actual contaminated sediment. The stabilization of certain metallic species particularly Cr ions was studied.METHODS: Laboratory scale pyrolysis experiments were conducted using a special horizontal lab-scale pyrolyzer. Sediment samples from Shanghai Suzhou Creek and Tagonoura Harbor were pyrolyzed in the reactor under nitrogen gas at 800°C and different retention times of 30, 60 and 90 min. A constant heating rate of 10°C min-1 was employed. The pyrolysis gas was first allowed to pass through a cold trap to condense the tar. Uncondensed gases were then channeled through a column containing an adsorbent (XAD-2 Resin) for dioxins. Heavy metal concentrations in the initial and final sediment residues were analyzed by ICP (Nippon Jarrel-Ash) following their acid and alkali (for Cr6+) digestion. Dioxins content of the pyrolysis char, tar, and exhaust gases in the dioxin adsorbent were also determined. For comparative purpose, thermal treatment under air flow was conducted.RESULTS: The data for the removal of heavy metals from Suzhou Creek sediment showed very significant reductions in Pb, Zn and Cr6+ content of the sediment at this condition. Percentage removals were 42.4%, 60.8% and 42.2%, respectively. The disappearance of Cr6+ was due to reduction reactions rather than volatilization since the total Cr content remained almost unchanged. Other heavy metals such as Cu, Fe and Ni showed very minimal reductions. Nonetheless, Toxicity Characteristics Leaching Procedure (TCLP) tests confirmed that these residual heavy metals were rather stable in the pyrolysis char. Reduction of toxic Cr6+ at 42.2% has also been achieved by pyrolysis (with N2) as opposed to the more than 580 % increase in Cr6+ observed during thermal oxidation (with air).DISCUSSION: Pyrolysis also remove toxic organics particularly dioxins from the sediment. For the total dioxins, removal percentage of 99.9999% was achieved even at the lowest retention time of 30 min. Almost all polychlorinated dibenzo-p-dioxine (PCDDs) and polychlorinated dibenzo-furans (PCDFs) were removed at any retention time. The TEQs detected from the solid residues were mainly contributed by dioxin-like PCBs, yet these were present in relatively trace quantities. At the shortest retention time of 30 min, only 0.000085 pg-TEQ g-1 of polychlorinated biphenyls (PCBs) was detected in the pyrolysis char. Furthermore, the residual PCBs have very low toxicity ratings and none of the highly toxic PCBs, which were initially present in the sediment such as 3,3',4,4',5-PeCB and 3,3',4,4'5,5'-HxCB, were detected in the char. Results further confirmed that most of the dioxins that were removed were transferred to the gas phase so that volatilization may be considered as the main mechanism for their removal.CONCLUSION: Some heavy metals particularly Pb and Zn can be volatilized under N2 pyrolysis at 800oC. Pyrolysis also prevented the formation of more toxic Cr6+ ions and at the same time resulted to its reduction by around 42.2% contrast to the 580% increase during thermal oxidation. PCDDs and PCDFs have been removed and were not formed in the solid products over the retention time range of 30-90 min at 800°C. Dioxin-like PCBs mostly remained and a retention time of 30 min was found sufficient for its maximum removal. RECOMMENDATIONS AND PERSPECTIVE: . With the above results, a temperature of 800oC at a retention time of 30 min is sufficient for the removal of total dioxins and some heavy metals by volatilization. It is however necessary to destroy the dioxins as well as recover heavy metals in the gas phase. Stability of remaining heavy metals in the char also needs to be confirmed by leaching tests. These are the major concerns, which we are currently evaluating to establish the feasibility of our proposed large scale pyrolysis system for sediment treatment.

GOALS, SCOPE AND BACKGROUND: Anaerobic digestion of organic household waste can lead to an increase in dioxin-like content, as determined by dioxin-specific bioassays. This may be a result of bioactivation of Ah receptor (AhR) agonists into more potent congeners. Work towards identifying the contributing compound groups is important in order to understand the mechanisms and to assess the relevance behind this increase in dioxin-like toxicity, since the residue can be used as a soil fertilising agent. The aim with the present work was to identify compound groups with AhR agonistic properties that caused the previously reported increase in dioxin-like activity after anaerobic biodegradation METHODS: Firstly, chemical fractionation combined with dioxin bioassay testing was used to find bioactive classes of compounds. Secondly, batch digestion experiments with an externally added polychlorinated biphenyl (PCB) mixture (Clophen A50) and with decabrominated diphenyl ether (decaBDE), respectively, were studied as a possible process for transformation of precursors into more potent, dioxin-like compounds. Mesophilic (37ºC) and thermophilic (55ºC) anaerobic digestion were studied. Two different dioxin-specific bioassays were used to analyse AhR agonists in the biodegraded material, the CELCAD and the DR-CALUX. RESULTS AND DISCUSSION: AhR agonist activity was detected in both di- and polyaromatic fractions of digestate extracts, which indicated that a diverse mixture of compounds contributed to the bioassay responses. No quantifiable activities were induced by the monoaromatic fractions. Further fractionation based on planarity revealed higher concentrations of AhR agonists than what was detected after the first fractionation, probably due to non-additive biological interactions of compounds in the extract that were removed in the second fractionation. These results showed significant activity in the non-planar diaromatic fractions and in the co-planar fractions of both diaromates and polyaromates. In the batch experiment with externally added PCB, an increase in dioxin-like activity was seen after 21 days of digestion at mesophilic conditions. After completed digestion, the content of AhR agonists was equal to the start concentration. PCB analysis with GC-MS indicated that dehalogenation of PCBs occurred in the digestors. The batch experiment with decaBDE showed no significant changes in TEQ-concentrations over time. CONCLUSIONS: The results show that the previously reported increase of AhR agonists during mesophilic anaerobic digestion is probably due to an accumulation of several different groups of AhR agonists, both diaromatic and polyaromatic, and both co-planar and non-planar. Batch experiments with externally added PCBs and decaBDE, respectively, did not result in any accumulation of AhR agonist activity after completed digestion, even though chemical analysis indicate a dechlorination of PCBs. Complex, unfractionated extracts were difficult to test using the bioassay approach. Removal of AhR antagonists or otherwise interacting compounds during fractionation may yield bio-TEQ values that are much higher than in the original extract. RECOMMENDATIONS AND PERSPECTIVE: Our results indicate that the environmental risk that AhR agonists may pose concerning large-scale anaerobic digestion of organic household waste probably depends on the efficiency of the digester and the sludge residence time. In order to obtain reliable results with the bioassays, an extensive cleanup and fractionation procedure is necessary. Without clean up and fractionation, there is a risk for false negatives and misleading conclusions. DR-CALUX and CELCAD were both suitable for these kinds of studies, provided that suitable fractionation methods are used.

BACKGROUND, AIM AND SCOPE: Current scientific studies and evaluations clearly show that an increase of urban dust loads, alone or combined with other pollutants und certain meteorological conditions lead to different significant health effects. Premature death, increased hospital admissions and increased respiratory symptoms and diseases as well as decreased lung function can be observed in combination with high pollutant levels. Sensitive groups like elderly people or children and persons with cardiopulmonary diseases such as asthma are more strongly affected. Because of the direct contact between fine particles and lung tissue more information concerning the surface structure (mapping of toxic elements) is required. Materials and Methods:The NanoSims50 ion microprobe images the element composition at the surface of sub-micrometer air dust particles and documents hot spots of toxic elements as a possible threat for human health.Results:The atmospheric fine dust consists of a complex mixture of organic and inorganic compounds. Heavy metals are fixed on airborn particles in the form of hot spots in a nanometer scale. From a sanitary point of view, the hot spots consisting of toxic elements are particularly relevant as they react directly with the lung tissues. Discussion:To what extent particles can penetrate the various areas of the lungs and be deposited there depends on the one hand on their physical characteristics and on the other on breathing patterns and the anatomy of the lung, which is subject to change as the result of growth, ageing or illness. Once inhaled, some particles can reach the pulmonary alveoli and thus directly expose the lung tissues to toxic elements.Conclusions:Especially the mapping of toxic arsenic or heavy metals like copper on the dust particles shows local hot spots of pollution in the dimension of only 50 nanometers.Recommendations and Perspectives:Imaging of elements in atmospheric particles with NanoSIMS will help to identify the material sources.

GOAL, SCOPE AND BACKGROUND: The aim of this work is to show the ability of several fungal species, isolated from arsenic polluted soils, to biosorb and volatilize arsenic from a liquid medium under laboratory conditions. Mechanisms of biosorption and biovolatilization play an important role in the biogeochemical cycle of arsenic in the environment. The quantification of production of volatile arsenicals is discussed in this article. METHODS: Heat-resistant filamentous fungi Neosartorya fischeri, Talaromyces wortmannii, T. flavus, Eupenicillium cinnamopurpureum, originally isolated from sediments highly contaminated with arsenic (more than 1403 mg.l-1 of arsenic), and the non-heat-resistant fungus Aspergillus niger were cultivated in 40 mL liquid Sabouraud medium (SAB) enriched by 0.05, 0.25, 1.0 or 2.5 mg of inorganic arsenic (H3AsO4). After 30-day and 90-day cultivation under laboratory conditions, the total arsenic content was determined in mycelium and SAB medium using the HG AAS analytical method. Production of volatile arsenic derivates by the Neosartorya fischeri strain was also determined directly by hourly sorption using the sorbent Anasorb CSC (USA). RESULTS: Filamentous fungi volatilized 0.025–0.321 mg of arsenic from the cultivation system, on average, depending on arsenic concentrations and fungal species. The loss of arsenic was calculated indirectly by determining the sum of arsenic content in the mycelium and culture medium. The amount of arsenic captured on sorption material was 35.7 ng of arsenic (22nd day of cultivation) and 56.4 ng of arsenic (29th day of cultivation) after one hour's sorption. Biosorption of arsenic by two types of fungal biomass was also discussed, and the biosorption capacity for arsenic of pelletized and compact biomass of Neosartorya fischeri was on average 0.388 mg and 0.783 mg of arsenic, respectively. DISCUSSION: The biosorption and amount of volatilized arsenic for each fungal species was evaluated and the effect of initial pH on the biovolatilization of arsenic was discussed. CONCLUSIONS: The most effective biovolatilization of arsenic was observed in the heat-resistant Neosartorya fischeri strain, while biotransformation of arsenic into volatile derivates was approximately two times lower for the non-heat-resistant Aspergillus niger strain. Biovolatilization of arsenic by Talaromyces wortmannii, T. flavus, Eupenicillium cinnamopurpureum was negligible. Results from biosorption experiments indicate that nearly all of an uptaken arsenic by Neosartorya fischeri was transformed into volatile derivates. RECOMMENDATIONS AND PERSPECTIVE: Biovolatilization and biosorption have a great potential for bioremediation of contaminated localities. However, results showed that not all fungal species are effective in the removal of arsenic. Thus, more work in this research area is needed.

GOAL, SCOPE AND BACKGROUND: One of the burning problems of our industrial society is the high consumption of water and the high demand for clean drinking water. Numerous approaches have been taken to reduce water consumption, but in the long run it seems only possible to recycle waste water into high quality water. It seems timely to discuss alternative water remediation technologies that are fit for industrial as well as less developed countries to ensure a high quality of drinking water throughout Europe. MAIN FEATURES: The present paper discusses a range of phytoremediation technologies to be applied in a modular approach to integrate and improve the performance of existing wastewater treatment, especially towards the emerging micro pollutants, i.e. organic chemicals and pharmaceuticals. This topic is of global relevance for the EU. RESULTS: Existing technologies for waste water treatment do not sufficiently address increasing pollution situation, especially with the growing use of organic pollutants in the private household and health sector. Although some crude chemical approaches exist, such as advanced oxidation steps, most waste water treatment plants will not be able to adopt them. The same is true for membrane technologies. DISCUSSION: Incredible progress has been made during recent years, thus providing us with membranes of longevity and stability and, at the same time, high filtration capacity. However, these systems are expensive and delicate in operation, so that the majority of communities will not be able to afford them. Combinations of different phytoremediation technologies seem to be most promising to solve this burning problem. CONCLUSIONS: To quantify the occurrence and the distribution of micropollutants, to evaluate their effects, and to prevent them from passing through wastewater collection and treatment systems into rivers, lakes and ground water bodies represents an urgent task for applied environmental sciences in the coming years. RECOMMENDATIONS: Public acceptance of green technologies is generally higher than that of industrial processes. The EU should stimulate research to upgrade existing waste water treatment by implementing phytoremediation modules and demonstrating their reliability to the public.

BACKGROUND, AIM AND SCOPE: Electrocoagulation (EC) may be a potential answer to environmental problems dealing with water reuse and rational waste management. The aim of this research was to assess the feasibility of EC-process for industrial contaminated effluents from copper production, taking into consideration technical and economical factors. EC-technology claims to offer efficient removal rates for most types of wastewater impurities at low power consumption and without adding any precipitating agents. MATERIALS AND METHODS: Real wastewater from Saraka stream with high concentrations of heavy metals was provided by RTB-BOR, a Serbian copper mining and smelting complex. Runs were performed on a 10 1 EC-reactor using aluminum plates as sacrificial electrodes and powered by a 40 A supply unit. Results concerning key factors like pH, conductivity and power consumption were measured in real time. Analysis of dissolved metal concentrations before and after treatment were carried out via ICP-OES and confirmed by an independent test via AAS. RESULTS: Several aspects were taken into account, including current density, conductivity, interfacial resistivity and reactor settings throughout the runs, in order to analyze all possible factors playing a role in neutralization and metal removal in real industrial wastewater. DISCUSSION: Electrode configurations and their effects on energy demand were discussed and exemplified based on fundamentals of colloidal and physical chemistry. CONCLUSIONS: Based on experimental data and since no precipitating agents were applied, the EC-process proved to be not only feasible and environmentally-friendly, but also a cost-effective technology. RECOMMENDATIONS AND PERSPECTIVES: The EC-technology provides strategic guidelines for further research and development of sustainable water management processes. However, additional test series concerning continuous operation must be still performed in order to get this concept ready for future large-scale applications.

BACKGROUND, AIMS AND SCOPE: The global problem concerning contamination of the environment as a consequence of human activities is increasing. Most of the environmental contaminants are chemical by-products and heavy metals such as lead (Pb). Lead released into the environment makes its way into the air, soil and water. Lead contributes to a variety of health effects such as decline in mental, cognitive and physical health of the individual. An alternative way of reducing Pb concentration from the soil is through phytoremediation. Phytoremediation is an alternative method that uses plants to clean up a contaminated area. The objectives of this study were: (1) to determine the survival rate and vegetative characteristics of three grass species such as vetivergrass, cogongrass and carabaograss grown in soils with different Pb levels; and (2) to determine and compare the ability of the three grass species as potential phytoremediators in terms of Pb accumulation by plants. METHODS: The three test plants: vetivergrass (Vetiveria zizanioides L.); cogongrass (Imperata cylindrica L.); and carabaograss (Paspalum conjugatum L.) were grown in individual plastic bags containing soils with 75 mg kg⁻¹ (37.5 kg ha⁻¹) and 150 mg kg⁻¹ (75 kg ha⁻¹) of Pb, respectively. The Pb contents of the test plants and the soil were analyzed before and after experimental treatments using an atomic absorption spectrophotometer. This study was laid out following a 3 × 2 factorial experiment in a completely randomized design. RESULTS: On the vegetative characteristics of the test plants, vetivergrass registered the highest whole plant dry matter weight (33.85–39.39 Mg ha⁻¹). Carabaograss had the lowest herbage mass production of 4.12 Mg ha⁻¹ and 5.72 Mg ha⁻¹ from soils added with 75 and 150 mg Pb kg⁻¹, respectively. Vetivergrass also had the highest percent plant survival which meant it best tolerated the Pb contamination in soils. Vetivergrass registered the highest rate of Pb absorption (10.16 ± 2.81 mg kg⁻¹). This was followed by cogongrass (2.34 ± 0.52 mg kg⁻¹) and carabaograss with a mean Pb level of 0.49 ± 0.56 mg kg⁻¹. Levels of Pb among the three grasses (shoots + roots) did not vary significantly with the amount of Pb added (75 and 150 mg kg⁻¹) to the soil. DISCUSSION: Vetivergrass yielded the highest biomass; it also has the greatest amount of Pb absorbed (roots + shoots). This can be attributed to the highly extensive root system of vetivergrass with the presence of an enormous amount of root hairs. Extensive root system denotes more contact to nutrients in soils, therefore more likelihood of nutrient absorption and Pb uptake. The efficiency of plants as phytoremediators could be correlated with the plants’ total biomass. This implies that the higher the biomass, the greater the Pb uptake. Plants characteristically exhibit remarkable capacity to absorb what they need and exclude what they do not need. Some plants utilize exclusion mechanisms, where there is a reduced uptake by the roots or a restricted transport of the metals from root to shoots. Combination of high metal accumulation and high biomass production results in the most metal removal from the soil. CONCLUSIONS: The present study indicated that vetivergrass possessed many beneficial characteristics to uptake Pb from contaminated soil. It was the most tolerant and could grow in soil contaminated with high Pb concentration. Cogongrass and carabaograss are also potential phytoremediators since they can absorb small amount of Pb in soils, although cogongrass is more tolerant to Pb-contaminated soil compared with carabaograss. The important implication of our findings is that vetivergrass can be used for phytoextraction on sites contaminated with high levels of heavy metals; particularly Pb. RECOMMENDATIONS AND PERSPECTIVES: High levels of Pb in localized areas are still a concern especially in urban areas with high levels of traffic, near Pb smelters, battery plants, or industrial facilities that burn fuel ending up in water and soils. The grasses used in the study, and particularly vetivergrass, can be used to phytoremediate urban soil with various contaminations by planting these grasses in lawns and public parks.

GOAL, SCOPE AND BACKGROUND: This paper is a part of the research work on ‘Integrated treatment of industrial wastes towards prevention of regional water resources contamination — INTREAT’ the project. It addresses the environmental pollution problems associated with solid and liquid waste/effluents produced by sulfide ore mining and metallurgical activities in the Copper Mining and Smelting Complex Bor (RTB-BOR), Serbia. However, since the minimum solubility for the different metals usually found in the polluted water occurs at different pH values and the hydroxide precipitates are amphoteric in nature, selective removal of mixed metals could be achieved as the multiple stage precipitation. For this reason, acid mine water had to be treated in multiple stages in a continuous precipitation system-cascade line reactor. MATERIALS AND METHODS: All experiments were performed using synthetic metal-bearing effluent with chemical a composition similar to the effluent from open pit, Copper Mining and Smelting Complex Bor (RTB-BOR). That effluent is characterized by low pH (1.78) due to the content of sulfuric acid and heavy metals, such as Cu, Fe, Ni, Mn, Zn with concentrations of 76.680, 26.130, 0.113, 11.490, 1.020 mg/dm³, respectively. The cascade line reactor is equipped with the following components: for feeding of effluents, for injection of the precipitation agent, for pH measurements and control, and for removal of the process gases. The precipitation agent was 1M NaOH. In each of the three reactors, a changing of pH and temperature was observed. In order to verify efficiency of heavy metals removal, chemical analyses of samples taken at different pH was done using AES-ICP. RESULTS: Consumption of NaOH in reactors was 370 cm³, 40 cm³ and 80 cm³, respectively. Total time of the experiment was 4 h including feeding of the first reactor. The time necessary to achieve the defined pH value was 25 min for the first reactor and 13 min for both second and third reactors. Taking into account the complete process in the cascade line reactor, the difference between maximum and minimum temperature was as low as 6°C. The quantity of solid residue in reactors respectively was 0.62 g, 2.05 g and 3.91 g. In the case of copper, minimum achieved concentration was 0.62 mg/dm³ at pH = 10.4. At pH = 4.50 content of iron has rapidly decreased to < 0.1 mg/dm³ and maintained constant at all higher pH values. That means that precipitation has already ended at pH=4.5 and maximum efficiency of iron removal was 99.53%. The concentration of manganese was minimum at pH value of 11.0. Minimum obtained concentration of Zn was 2.18 mg/dm³ at a pH value of 11. If pH value is higher than 11, Zn can be re-dissolved. The maximum efficiency of Ni removal reached 76.30% at a pH value of 10.4. DISCUSSION: Obtained results show that efficiency of copper, iron and manganese removal is very satisfactory (higher than 90%). The obtained efficiency of Zn and Ni removal is lower (72.30% and 76.31%, respectively). The treated effluent met discharge water standard according to The Council Directive 76/464/EEC on pollution caused by certain dangerous substances into the aquatic environment of the Community. Maximum changing of temperature during the whole process was 6°C. CONCLUSION: This technology, which was based on inducing chemical precipitation of heavy metals is viable for selective removal of heavy metals from metal-bearing effluents in three reactor systems in a cascade line. RECOMMENDATIONS AND PERSPECTIVES: The worldwide increasing concern for the environment and guidelines regarding effluent discharge make their treatment necessary for safe discharge in water receivers. In the case where the effluents contain valuable metals, there is also an additional economic interest to recover these metals and to recycle them as secondary raw materials in different production routes.

BACKGROUND, AIM AND SCOPE: Air quality is an field of major concern in large cities. This problem has led administrations to introduce plans and regulations to reduce pollutant emissions. The analysis of variations in the concentration of pollutants is useful when evaluating the effectiveness of these plans. However, such an analysis cannot be undertaken using standard statistical techniques, due to the fact that concentrations of atmospheric pollutants often exhibit a lack of normality and are autocorrelated. On the other hand, if long-term trends of any pollutant's emissions are to be detected, meteorological effects must be removed from the time series analysed, due to their strong masking effects. MATERIALS AND METHODS: The application of statistical methods to analyse temporal variations is illustrated using monthly carbon monoxide (CO) concentrations observed at an urban site. The sampling site is located at a street intersection in central Valencia (Spain) with a high traffic density. Valencia is the third largest city in Spain. It is a typical Mediterranean city in terms of its urban structure and climatology. The sampling site started operation in January 1994 and monitored CO ground level concentrations until February 2002. Its geographic coordinates are W0º22'52\ N39º28'05\ and its altitude is 11 m. Two nonparametric trend tests are applied. One of these is robust against serial correlation with regards to the false rejection rate, when observations have a strong persistence or when the sample size per month is small. A nonparametric analysis of the homogeneity of trends between seasons is also discussed. A multiple linear regression model is used with the transformed data, including the effect of meteorological variables. The method of generalized least squares is applied to estimate the model parameters to take into account the serial dependence of the residuals of this model. This study also assesses temporal changes using the Kolmogorov-Zurbenko (KZ) filter. The KZ filter has been shown to be an effective way to remove the influence of meteorological conditions on O3 and PM to examine underlying trends. RESULTS: The nonparametric tests indicate a decreasing, significant trend in the sampled site. The application of the linear model yields a significant decrease every twelve months of 15.8% for the average monthly CO concentration. The 95% confidence interval for the trend ranges from 13.9% to 17.7%. The seasonal cycle also provides significant results. There are no differences in trends throughout the months. The percentage of CO variance explained by the linear model is 90.3%. The KZ filter separates out long, short-term and seasonal variations in the CO series. The estimated, significant, long-term trend every year results in 10.3% with this method. The 95% confidence interval ranges from 8.8% to 11.9%. This approach explains 89.9% of the CO temporal variations. DISCUSSION: The differences between the linear model and KZ filter trend estimations are due to the fact that the KZ filter performs the analysis on the smoothed data rather than the original data. In the KZ filter trend estimation, the effect of meteorological conditions has been removed. The CO short-term component is attributable to weather and short-term fluctuations in emissions. There is a significant seasonal cycle. This component is a result of changes in the traffic, the yearly meteorological cycle and the interactions between these two factors. There are peaks during the autumn and winter months, which have more traffic density in the sampled site. There is a minimum during the month of August, reflecting the very low level of vehicle emissions which is a direct consequence of the holiday period. CONCLUSIONS: The significant, decreasing trend implies to a certain extent that the urban environment in the area is improving. This trend results from changes in overall emissions, pollutant transport, climate, policy and economics. It is also due to the effect of introducing reformulated gasoline. The additives enable vehicles to burn fuel with a higher air/fuel ratio, thereby lowering the emission of CO. The KZ filter has been the most effective method to separate the CO series components and to obtain an estimate of the long-term trend due to changes in emissions, removing the effect of meteorological conditions. RECOMMENDATIONS AND PERSPECTIVE: Air quality managers and policy-makers must understand the link between climate and pollutants to select optimal pollutant reduction strategies and avoid exceeding emission directives. This paper analyses eight years of ambient CO data at a site with a high traffic density, and provides results that are useful for decision-making. The assessment of long-term changes in air pollutants to evaluate reduction strategies has to be done while taking into account meteorological variability.

Background, Aim and Scope Numerous herbicides and xenobiotic organic pollutants are detoxified in plants to glutathione conjugates. Following this enzyme catalyzed reaction, xenobiotic GS-conjugates are thought to be compartmentalized in the vacuole of plant cells. In the present study, evidence is presented for long range transport of these conjugates in plants, rather than storage in the vacuole. To our knowledge this is the first report about the unidirectional long range transport of xenobiotic conjugates in plants and the exudation of a glutathione conjugate from the root tips. This could mean that plants possess an excretion system for unwanted compounds which give them similar advantages as animals. Materials and Methods: Barley plants (Hordeum vulgare L. cv. Cherie) were grown in Petri dishes soaked with tap water in the greenhouse. - Fluorescence Microscopy. Monobromo- and Monochlorobimane, two model xenobiotics that are conjugated rapidly in plant cells with glutathione, hereby forming fluorescent metabolites, were used as markers for our experiments. Their transport in the root could be followed sensitively with very good temporal and spatial resolution. Roots of barley seedlings were cut under water and the end at which xenobiotics were applied was fixed in an aperture with a thin latex foil and transferred into a drop of water on a cover slide. The cover slide was fixed in a measuring chamber on the stage of an inverse fluorescence microscope (Zeiss Axiovert 100). - Spectrometric enzyme assay. Glutathione S-transferase (GST) activity was determined in the protein extracts following established methods. Aliquots of the enzyme extract were incubated with 1-chloro-2,4-dinitrobenzene (CDNB), or monochlorobimane. Controls lacking enzyme or GSH were measured. - Pitman chamber experiments. Ten days old barley plants or detached roots were inserted into special incubation chambers, either complete with tips or decapitated, as well as 10 days old barley plants without root tips. Compartment A was filled with a transport medium and GSH conjugate or L-cysteine conjugate. Compartments B and C contained sugar free media. Samples were taken from the root tip containing compartment C and the amount of conjugate transported was determined spectro-photometrically. Results: The transport in roots is unidirectional towards the root tips and leads to exsudation of the conjugates at rates between 20 and 200 nmol min-1. The microscopic studies have been complemented by transport studies in small root chambers and spectroscopic quantification of dinitrobenzene-conjugates. The latter experiments confirm the microscopic studies. Furthermore it was shown that glutathione conjugates are transported at higher rates than cysteine conjugates, despite of their higher molecular weights. This observation points to the existence of glutathione specific carriers and a specific role of glutathione in the root. Discussion: It can be assumed that long distance transport of glutathione conjugates within the plant proceeds like GSH or amino acid transport in both, phloem and xylem. The high velocity of this translocation of the GS-X is indicative of an active transport. For free glutathione, a rapid transport-system is essential because an accumulation of GSH in the root tip inhibits further uptake of sulfur. Taking into account that all described MRP transporters and also the GSH plasmalemma ATPases have side activities for glutathione derivatives and conjugates, co-transport of these xenobiotic metabolites seems credible. - On the other hand, when GS-B was applied to the root tips from the outside, no significant uptake was observed. Thus it can be concluded that only those conjugates can be transported in the xylem which are formed inside the root apex. Having left the root once, there seems to be no return into the root vessels, probably because of a lack of inward directed transporters. Conclusions: Plants seem to possess the capability to store glutathione conjugates in the vacuole, but under certain conditions, these metabolites might also undergo long range transport, predominantly into the plant root. The transport seems dependent on specific carriers and is unidirectional, this means that xenobiotic conjugates from the rhizosphere are not taken up again. The exudation of xenobiotic metabolites offers an opportunity to avoid the accumulation of such compounds in the plant. Recommendations and Perspectives: The role of glutathione and glutathione related metabolites in the rhizosphere has not been studied in any detail, and only scattered data are available on interactions between the plant root and rhizosphere bacteria that encounter such conjugates. The final fate of these compounds in the root zone has also not been addressed so far. It will be interesting to study effects of the exuded metabolites on the biology of rhizosphere bacteria and fungi.