Life Cycle Assessment as Part of Sustainability Assessment for Chemicals (5 pp)

Background LCA is the only internationally standardized environmental assessment tool (ISO 14040-43) for product systems, including services and processes. The analysis is done ‘from cradle-to-grave’, i.e. over the whole life cycle. LCA is essentially a comparative method: different systems fulfilling the same function (serving the same purpose) are compared on the basis of a ‘functional unit’ - a quantitative measure of this function or purpose. It is often believed that LCA can be used for judging the (relative) sustainability of product systems. This is only partly true, however, since LCA is restricted to the environmental part of the triad ‘environment/ecology - economy - social aspects (including intergenerational fairness)’ which constitutes sustainability. Standardized assessment tools for the second and the third part are still lacking, but Life Cycle Costing (LCC) seems to be a promising candidate for the economic part. Social Life Cycle Assessment still has to be developed on the basis of known social indicators.Method and Limitations LCA is most frequently used for the comparative assessment or optimization analysis of final products. Materials and chemicals are difficult to analyse from cradle-to-grave, since they are used in many, often innumerable product systems, which all would have to be studied in detail to give a complete LCA of a particular material or substance! This complete analysis of a material or chemical is evidently only possible in such cases where one main application exists. But even if one main application does exist, e.g. in the case of surfactants (chemicals) and detergents (final products), the latter may exist in a great abundance of compositions. Therefore, chemicals and materials are better analysed ‘from cradle-to-factory gate’, leaving the analysis of the final product(s), the use phase and the ‘end-of-life’ phases to specific, full LCAs.Conclusion A comparative assessment of production processes is possible, if the chemicals (the same is true for materials) produced by different methods have exactly the same properties. In this case, the downstream phases may be considered as a ‘black box’ and left out of the assessment. Such truncated LCAs can be used for environmental comparisons, but less so for the (environmental) optimization analysis of a specific chemical: the phases considered as ‘black box’ and left out may actually be the dominant ones. A sustainability assessment should be performed at the product level and contain the results of LCC and social assessments. Equal and consistent system boundaries will have to be used for these life cycle tools which only together can fulfil the aim of assessing the sustainability of product systems.     

Green Chemistry - Views and Strategies * (5 pp)

Background and Goal The object of Green Chemistry is the reduction of chemical pollutants flowing to the environment. The Chemistry and the Environment Division of EuCheMS has assumed Green Chemistry as one of its areas of interest, but one question to solve is where Green Chemistry should be placed within the context of Chemistry and the Environment. The concept of Green Chemistry, as primarily conceived by Paul Anastas and John Warner, is commonly presented through the Twelve Principles of Green Chemistry. However, these Twelve Principles, though fruit of a great intuition and common sense, do not provide a clear connection between aims, concepts, and related research areas of Green Chemistry. These two unsolved questions are the object of the present article.Discussion Green Chemistry is here placed as a part of Chemistry for the Environment, concerning the still non-existent pollutants. Indeed, the object of Green Chemistry is the reduction of pollution and risks by chemicals by avoiding their generation or their introduction into the biosphere. The distinction between pollutant chemicals and dangerous chemicals, along with the consideration of the exhaustion of fossil resources and the acknowledgement of the harmful effects of the chemicals employed in a great variety of activities, leads to the recognition of four general objectives for Green Chemistry. In order to accomplish these general objectives, a number of strategies, or secondary objectives and some fundamental concepts, namely, atomic economy, selectivity, potential harm or historical harm can be visualized. A connection is finally established between the strategies and current and future research areas of Green Chemistry.Conclusion The ultimate aim of green chemistry is to entirely cut down the stream of chemicals pouring into the environment. This aim seems unattainable at present, but progress in the green chemical research areas and their application through successive approaches will certainly provide safer specialty chemicals and much more satisfactory processes for the chemical industry.- * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on ‘Chemistry and Environment’, 29 August to 1 September 2004, Bordeaux, France.     

城市污水处理厂反硝化聚磷菌的聚磷持久性

以桂林市第四污水处理厂氧化沟活性污泥为对象,研究在具有厌氧-缺氧-好氧环境的污水处理构筑物中富集存在的反硝化聚磷菌聚磷能力的持久性问题。结果表明,在此环境中富集的反硝化聚磷菌在经过3个周期的厌氧-缺氧条件下运行,最大释磷率由0.90 mg P/（g VSS.h）下降为0.07 mg P/（g VSS.h）,反硝化聚磷率由0.17 mg P/（g VSS.h）下降为0.04 mg P/（g VSS.h）。比较而言,在厌氧-缺氧-好氧环境下最大释磷率及聚磷率降幅较小,释磷率由0.59 mg P/（gVSS.h）下降为0.37 mg P/（g VSS.h）,反硝化聚磷率由0.17 mg P/（g VSS.h）下降为0.10 mg P/（g VSS.h）,厌氧-缺氧-好氧运行条件比单纯的厌氧-缺氧运行条件更有利于维持反硝化聚磷菌的聚磷性能。     

Biomass Burning in the Amazon-Fertilizer for the Mountaineous Rain Forest in Ecuador (7 pp)

Background Biomass burning is a source of carbon, sulfur and nitrogen compounds which, along with their photochemically generated reaction products, can be transported over very long distances, even traversing oceans. Chemical analyses of rain and fogwater samples collected in the mountaineous rain forest of south Ecuador show frequent episodes of high sulfate and nitrate concentration, from which annual deposition rates are derived comparable to those found in polluted central Europe. As significant anthropogenic sources are lacking at the research site it is suspected that biomass burning upwind in the Amazon basin is the major source of the enhanced sulfate and nitrate imput. Methods Regular rain and fogwater sampling along an altitude profile between 1800 and 3185 m has been carried out in the Podocarpus National Park close to the Rio SanFrancisco (3°58'S, 79°5'W) in southern Ecuador. pH values, electrical conductivity and chemical ion composition were measured at the TUM-WZW using standard methods. Results and Discussion Results reported cover over one year from March 2002 until May 2003. Annual deposition rates of sulfate were calculated ranging between 4 and 13 kg S/ha year, almost as high as in polluted central Europe. Nitrogen deposition via ammonia (1.5–4.4 kg N/ha year) and nitrate (0.5–0.8 kg N/ha year) was found to be lower but still much higher than to be expected in such pristine natural forest environment. By means of back trajectory analyses it can be shown that most of the enhanced sulfur and nitrogen deposition is most likely due to forest fires far upwind of the Ecuadorian sampling site, showing a seasonal variation, with sources predominantly found in the East/NorthEast during January–March (Colombia, Venezuela, Northern Brazil) and East/SouthEast during July–September (Peru, Brazil). Conclusion Our results show that biomass burning in the Amazon basin is the predominant source of sulfur and nitrogen compounds that fertilize the mountaineous rain forest in south Ecuador. Recommendation and Outlook The mountaineous rain forest in south Ecuador has developed on poor and acid soils, with low nutrient availability. The additional fertilization resulting from anthropogenic biomass burning constitutes a significant disturbance of this ecosystem, its functioning and biodiversity. Thus it is planned to employ isotope analyses for quantifying the pathways of nitrate and sulfate deposition in these natural forests.     

基于能值分析的农村污水处理工艺可持续性评价

随着我国城镇化和农村污水治理工作的不断推进,开展农村污水治理可持续性发展研究具有重要的现实意义。从工艺、地域等角度入手选取5个典型案例,分析农村污水处理工艺的可持续性。采用能值分析法探讨同种工艺在不同地区及不同工艺在同一地区的可持续性特点,并结合污水处理系统独特的复杂性对传统能值分析法进行改进,以更好地考察各系统对生态环境的影响及其可持续性。结果表明,对比分析分处常州、北京、广州的1#、2#和3#人工湿地系统,常州的1#系统的可持续性最强,北京的2#系统的可持续性最弱;对比地域相同的4#MBR、5#SBR、1#人工湿地系统发现,3个系统的可持续性依次增强。     

Successful Treatment of Low PAH-Contaminated Sewage Sludge in Aerobic Bioreactors (7 pp) *

Background, Aims and Scope Polycyclic Aromatic Hydrocarbons (PAHs) are known for their adverse and cumulative effects at low concentration. In particular, the PAHs accumulate in sewage sludge during wastewater treatment, and may thereafter contaminate agricultural soils by spreading sludge on land. Therefore, sludge treatment processes constitute the unique opportunity of PAH removal before their release in the environment. In this study, the ability of aerobic microorganisms to degrade light and heavy PAHs was investigated in continuous bioreactors treating trace-level PAH-contaminated sludge. Methods Several aerobic reactors were operated under continuous and perfectly mixed conditions to simulate actual aerobic sludge digesters. Three sterile control reactors were performed at 35°C, 45°C or 55°C to assess PAH abiotic losses under mesophilic and thermophilic conditions. Three biological reactors were also operated at 35°C, 45°C or 55°C. Furthermore, 250 mM methanol were added in an additional mesophilic reactor (35°C). All reactors were fed with long-term PAH-contaminated sewage sludge, and PAH removal was assessed by inlet/outlet mass balance. In this study, PAH compounds ranged from 2 to 5-unsubstituted aromatic rings, i.e. respectively from Fluorene to Indeno(123cd)pyrene. Results and Discussion Significant abiotic losses were observed for the lightest PAHs (fluorene, phenanthrene and anthracene), while biodegradation occurred for all PAHs. More than 80% of the lightest PAHs were removed. Biodegradation rates inversely correlated with the increasing molecular weight, and seemed limited by the low bioavailability of the heaviest PAHs (only 50% of removal). The enhancement of PAH bioavailability by increasing the process temperature or adding methanol was tested. A temperature increase from 35°C to 45°C and then to 55°C significantly enhanced the biodegradation of the heaviest PAHs from 50% to 80%. However, high abiotic losses were observed for all PAHs at 55°C, which was attributed to volatilization. Optimal conditions were found at 45°C considering the low abiotic losses and the high PAH biodegradation rates. Similar performances were achieved by addition of methanol in the sludge. It was concluded that increasing temperatures or addition of methanol favored PAH diffusion from solids to an aqueous compartment, and enhanced their bioavailability to PAH-degrading microorganisms. Conclusion In this study, the use of long-term acclimated aerobic ecosystems showed the high potential of aerobic microorganisms to degrade a wide range of PAHs at trace levels. However, PAH biodegradation was likely controlled by their low bioavailability. Two aerobic processes have been finally proposed to achieve efficient decontamination of sewage sludge, at 45°C or in the presence of methanol. The PAH concentrations in reactor outlet were lower than the French requirements, and allow the treated sludge to be spread on agricultural land. Recommendations and Outlook The two proposed aerobic processes used physical or chemical diffusing agents. The global ecological impact of using the latter agents for treating trace level contamination must be considered. Since methanol was completely removed during the process, no additional harm is expected after treatment. However, an increase of temperature to 45°C could drastically increase the energy demand in full-scale plants, and therefore the ecological impact of the process. Moreover, since bioavailability controls PAH biodegradation, efficiency of the processes could also be influenced by the hydraulic parameters, such as mixing and aeration rates. Further experimentations in a pilot scale are therefore recommended, as well as a final assessment of the global environmental benefit of using such aerobic processes in the bioremediation of trace level compounds. - Abbreviations (PAHs): Ant – anthracene; B(a)A – benzo(a)anthracene ; B(b)F – benzo(b)fluoranthene; B(k)F – benzo(k)fluoranthene; B(ghi)P – benzo(g,h,i)perylene; B(a)P – benzo(a)pyrene; Chrys – chrysene; DB – dibenzo(a,h)anthracene; Fluor – fluoranthene; Fluo - fluorene; Ind – indeno(1,2,3-c,d)pyrene; Phe - phenanthrene; Pyr – pyrene - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

Phytoplankton Community and Chlorophyll a as Trophic State Indices of Lake Skadar (Montenegro,Balkan) (7 pp)

Background, Aims and Scope Phytoplankton, as a first step in trophic cascades of lakes, can be a good indicator of trophic states, considering that every environmental change affects this community and many species of this community are sensitive to changes, and that they response very quickly. In this study, we tried to assess and predict the trophic state of Lake Skadar according to phytoplankton data.Methods Water samples were collected using Ruttner sampling bottle. Temperature, dissolved oxygen, ph, conductivity and transparence were measured in situ using portable equipment. Nutrients and chlorophyll a were measured using standard spectrophotometric methods. A determination of phytoplankton species was performed using relevant keys and the counting of cells was performed using sedimentation methods.Results and Discussion The species composition of Lake Skadar revealed 95 taxa, with Chlorophyceae and Bacillariophyceae being represented best. According to an average chlorophyll a concentration of 5.9 µg/l, Lake Skadar belongs to the mesotrophic level of the trophic scale. Developed prediction equation for chlorophyll a revealed a good prediction (R2=0.71) and the parameter Secchi depth was primarily correlated with chlorophyll a concentration. Trophic state indices derived from chlorophyll a and transparency, were close together, but both were below the phosphorous index. Values of trophic state indices rank the Lake Skadar as being mesotrophic. This study also showed that indices of diversity based on phytoplankton are weak indicators of trophic status and that they can well characterize only differences between assemblages and associations. According to calculated saprobic indices (ranging from 1.5 to 2.15), Lake Skadar is on betamesosaprobic level of saprobity, which means that it is moderately polluted with organic compounds. Conclusions Total phosphorus is not the main limiting factor for the phytoplankton community in Lake Skadar. Disagreements between chlorophyll and the transparency index, on the one hand, and the total phosphorus index, on the other, suggest that the phytoplankton in Lake Skadar is probably limited by other factors than phosphorus, such as nitrogen, toxic substances or intense zooplankton grazing. According to the majority of investigated parameters and indices derived from phytoplankton data, Lake Skadar is mesotrophic, with tendencies toward eutrophic levels during the summer period. Recommendations and Outlook Long-term monitoring is required for a better estimation of state and the conditions of Lake Skadar. Further studies on factors influencing the phytoplankton community, especially zooplankton grazing and toxic substances, which were not included in this study, should be continued in the future to improve the efficiency of phytoplankton usage in estimating the ecological and trophic conditions of Lake Skadar.     

An Estimate of Biogenic Emissions of Volatile Organic Compounds during Summertime in China (7 pp)

Background and Aim An accurate estimation of biogenic emissions of VOC (volatile organic compounds) is necessary for better understanding a series of current environmental problems such as summertime smong and global climate change. However, very limited studies have been reported on such emissions in China. The aim of this paper is to present an estimate of biogenic VOC emissions during summertime in China, and discuss its uncertainties and potential areas for further investigations. Materials and Methods This study was mainly based on field data and related research available so far in China and abroad, including distributions of land use and vegetations, biomass densities and emission potentials. VOC were grouped into isoprene, monoterpenes and other VOC (OVOC). Emission potentials of forests were determined for 22 genera or species, and then assigned to 33 forest ecosystems. The NCEP/NCAR reanalysis database was used as standard environmental conditions. A typical summertime of July 1999 was chosen for detailed calculations. Results and Discussion The biogenic VOC emissions in China in July were estimated to be 2.3×10¹²gC, with 42% as isoprene, 19% as monoterpenes and 39% as OVOC. About 77.3% of the emissions are generated-from forests and woodlands. The averaged emission intensity was 4.11 mgC m⁻² hr⁻¹ for forests and 1.12 mgC m⁻² hr⁻¹ for all types of vegetations in China during the summertime. The uncertainty in the results arose from both the data and the assumptions used in the extrapolations. Generally, uncertainty in the field measurements is relatively small. A large part of the uncertainty mainly comes from the taxonomic method to assign emission potentials to unmeasured species, while the ARGR method serves to estimate leaf biomass and the emission algorithms to describe light and temperature dependence. Conclusions This study describes a picture of the biogenic VOC emissions during summertime in China. Due to the uneven spatial and temporal distributions, biogenic VOC emissions may play an important role in the tropospheric chemistry during summertime. Recommendations and Perspectives Further investigations are needed to reduce uncertainties involved in the related factors such as emission potentials, leaf biomass, species distribution as well as the mechanisms of the emission activities. Besides ground measurements, attention should also be placed on other techniques such as remotesensing and dynamic modeling. These new approaches, combined with ground measurements as basic database for calibration and evaluation, can hopefully provide more comprehensive information in the research of this field. Submission Editor: Prof. Dr. Gerhard Lammel (lammel@recetox.muni.cz)     

Changes in Chlorinated Organic Pollutants and Heavy Metal Content of Sediments during Pyrolysis (7 pp)

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.     

Levels of Lead in Urban Soils from Selected Cities in a Central Region of the Philippines (7 pp)

Background Aims, and Scope. Lead (Pb) is a naturally occurring element that poses environmental hazards when present at elevated concentration. It is being released into the environment because of industrial uses and from the combustion of fossil fuels. Hence, Pb is ubiquitous throughout global ecosystems. The existence of potentially harmful concentrations of Pb in the environment must be given full attention. Emissions from vehicles are major source of environmental contamination by Pb. Thus, it becomes imperative that concentrations of Pb and other hazardous materials in the environment not only in the Philippines, but elsewhere in the world be adequately examined in order that development of regulations and standards to minimize risk associated with these materials in urban areas is continued. The objectives of this study were: (1) to determine the levels of Pb in soil from selected urbanized cities in central region of the Philippines; (2) to identify areas with soil Pb concentration values that exceed estimated natural concentrations and allowable limits; and (3) to determine the possible sources that contribute to elevated soil Pb concentration (if any) in the study area. Methods This study was limited to the determination of Pb levels in soils of selected urbanized cities located in central region in the Philippines, namely: Site 1 – Tarlac City in Tarlac; Site 2 – Cabanatuan City in Nueva Ecija; Site 3 – Malolos City in Bulacan; Site 4 – San Fernando City in Pampanga; Site 5 – Balanga City in Bataan; and Site 6 – Olongapo City in Zambales. Soil samples were collected from areas along major thoroughfares regularly traversed by tricycles, passenger jeepneys, cars, vans, trucks, buses, and other motor vehicles. Soil samples were collected from five sampling sites in each of the study areas. Samples from the selected sampling sites were obtained approximately 2 to 3 meters from the road. Analysis of the soil samples for Pb content was conducted using an atomic absorption spectrophotometer. This study was conducted from 2003 to 2004. Since this study assumed that vehicular emission is the major source of Pb contamination in urban soil, other information which the researchers deemed to have bearing on the study were obtained such as relative quantity of each gasoline type disposed of in each city within a given period and volume of traffic in each sampling site. A survey questionnaire for gasoline station managers was prepared to determine the relative quantity of each fuel type (diesel, regular gasoline, premium gasoline, and unleaded gasoline) disposed of or sold within a given period in each study area. Results and Discussion Analysis of soil samples for Pb content showed the presence of Pb in all the soil samples collected from the 30 sampling sites in the six cities at varying concentrations ranging from 1.5 to 251 mg kg–1. Elevated levels of Pb in soil (i.e. greater than 25 mg kg–1 Pb) were detected in five out of the six cities investigated. Site 4 recorded the highest Pb concentration (73.9 ± 94.4 mg kg–1), followed by Site 6 (56.3 ± 17.1 mg kg–1), Site 3 (52.0 ± 33.1 mg kg–1), Site 5 (39.3 ± 19.0 mg kg–1), and Site 2 (38.4 ± 33.2 mg kg–1). Soil Pb concentration in Site 1 (16.8 ± 12.2 mg kg–1) was found to be within the estimated natural concentration range of 5 to 25 mg kg–1. Site 1 registered the least Pb concentration. Nonetheless, the average Pb concentration in the soil samples from the six cities studied were all found to be below the maximum tolerable limit according to World Health Organization (WHO) standards. The high Pb concentration in Site 4 may be attributed mainly to vehicular emission. Although Site 4 only ranked 3rd in total volume of vehicles, it has the greatest number of Type B and Type C vehicles combined. Included in these categories are diesel trucks, buses, and jeepneys which are considered the largest contributors of TSP (total suspended particles) and PM10 (particulate matter less than 10 microns) emissions. Conclusion Only one (San Juan in Site 4) of the thirty sampling sites recorded a Pb concentration beyond the WHO permissible limit of 100 mg kg–1. San Juan in Site 4 had a Pb concentration of >250 mg kg–1. On the average, elevated Pb concentration was evident in the soil samples from San Fernando, Olongapo, Malolos, Balanga, and Cabanatuan. The average soil Pb concentrations in these cities exceeded the maximum estimated natural soil Pb concentration of 25 mg kg–1. Average soil Pb concentration in Site 1 (16.8 mg kg–1) was well within the estimated natural concentration range of 5 to 25 mg kg–1. Data gathered from the study areas showed that elevated levels of Pb in soil were due primarily to vehicular emissions and partly to igneous activity. Recommendation and Outlook The findings of this study presented a preliminary survey on the extent of Pb contamination of soils in urban cities in central region of Philippines Island. With this kind of information on hand, government should develop a comprehensive environmental management strategy to address vehicular air pollution in urban areas, which shows as one of the most pressing environmental problems in the country. Basic to this is the continuous monitoring of Pb levels and other pollutants in air, soil, and water. Further studies should be conducted to monitor soil Pb levels in the six cities studied particularly in areas with elevated Pb concentration. The potential for harm from Pb exposure cannot be understated. Of particular concern are children who are more predisposed to Pb toxicity than adults. Phytoremediation of Pb-contaminated sites is strongly recommended to reduce Pb concentration in soil. Several studies have confirmed that plants are capable of absorbing extra Pb from soil and that some plants, grass species in particular, and can naturally absorb far more Pb than others.     

PAH Metabolites in Bile Fluids of Dab (Limanda limanda) and Flounder (Platichthys flesus): Spatial Distribution and Seasonal Changes (7 pp)

Background, Aim and Scope Polycyclic aromatic hydrocarbons (PAH) are important environmental contaminants which may lead to increased levels of neoplastic aberrations or tumours in fish liver. Therefore, monitoring of PAH and their effects are part of several international environmental programmes. The aim of the present field study was to investigate the concentrations of the PAH metabolites in fish bile, to elucidate spatial, seasonal and species differences as well as to discuss different strategies of normalisation with regard to environmental monitoring. Materials and Methods: PAH metabolites were determined in the bile fluid of dab (Limanda limanda) and flounder (Platichthys flesus) caught in the North Sea and Baltic Sea between 1997 and 2004. After enzymatic deconjugation, two metabolites were determined by means of HPLC. The limit of detection and the limit of quantification were calculated. The accuracy of the method was tested with a standard reference material. Results were referred to bile volume as well as to biliverdin. Results: The main metabolite, 1-hydroxypyrene, was determined in concentrations from <0.7 to 838 ng/ml in bile of dab (Limanda limanda) and flounder (Platichthys flesus) caught between 1997 and 2004. The values for 1-hydroxyphenanthrene in fish bile were considerably lower (<0.4 – 87 ng/ml). Significant differences in the 1-hydroxypyrene levels were found between summer and winter surveys as well as between the sampling sites in the data set from 2004 (383 dabs and 62 flounders): Highest levels of PAH contamination were found in dab from the German Bight and in flounder from the Baltic Sea. Discussion: Spatial differences in 1-hydroxypyrene concentrations between North Sea and Baltic Sea were discussed, as well as differences in relation to season, sex and species. Three parameters of normalisation (biliary protein, biliverdin and bile pigments) were discussed. Biliverdin was identified as a suitable parameter for the normalisation of PAH metabolites in field samples. Conclusions: Spatial differences in 1-hydroxypyrene concentrations of dab demonstrate the usefulness of PAH metabolites in fish bile as a monitoring parameter in marine regions. Significant differences in 1-hydroxypyrene concentrations were found between summer and winter sampling campaigns. This may be linked to an annual cycle of 1-hydroxyprene in dab. It is also possible that bile synthesis/release in dab differs between the seasons. There is no indication for a time trend from 1997 to 2004. Recommendations and Perspectives: It is recommended to relate PAH metabolites in fish bile to biliverdin concentrations. Although the concentrations are low in offshore regions and bile volumes are small, the method presented here allows one to measure PAH metabolites on an individual level which is a crucial prerequisite for meaningful monitoring studies.     

Influence of Lead on Atrazine Uptake by Rice (Oryza sativa L.) Seedlings from Nutrient Solution (7 pp)

Background Atrazine is a widely used herbicide, and its persistence in soil and water causes environmental concerns. In the past, plat uptake processes are mainly investigated for single contaminants. However, in many cases, contaminants co-exist in environmental matrix, such as soil, and plant uptake of one contaminant may be influenced by its co-existing ones.Methods The uptake of atrazine by rice seedlings (Oryza sativa L.) from nutrient solution through the roots was investigated in a solution culture, over an exposure period of 4 weeks. Atrazine accumulation in plant tissues was determined by gas chromatography, and lead was determined using atomic absorption spectrometry.Results and Discussion With different ratios of atrazine and Pb2+ concentrations in solution, the observed atrazine concentrations in shoots and roots varied significantly. In atrazine-Pb2+ mixture systems, the added Pb2+ either increased or decreased the concentrations or BCFs of atrazine in seedlings (relative to those without Pb2+), depending on the atrazine-Pb2+ ratio in nutrient solution. The enhanced atrazine uptake results presumably from atrazine-Pb2+ complex formation. The reduced atrazine uptake, which occurred mainly at high atrazine concentrations, is attributed to atrazine toxicity that inhibited seedling growth and transpiration. Conclusion The formation of atrazine-Pb2+ complex both in the solution and within plant tissues may affect the accumulation of both contaminants by rice plants.     

Assessment of Antifouling Effectiveness of two Natural Product Antifoulants by Attachment Study with Freshwater Bacteria (7 pp)

- Goal, Scope, Background. The traditional solution for keeping unwanted organisms from attaching to submerged surfaces is to apply anti-fouling coatings. The most common antifoulant was tributyltin (TBT). TBT systems were highly effective but were also toxic to non-target organisms. The use of the TBT based coatings will be completely banned by January 1, 2008. Therefore, there is an urgent need to seek out suitable non-toxic alternatives. Methods The aim of this work was to evaluate the effectiveness of capsaicin and zosteric acid as natural product antifoulants (NPAs) in deterring bacterial attachment. Two fresh water bacteria systems Pseudomonas putida (Pp) and bacteria isolated from Lake Erie (LE) were used to assess the attachment when the NPAs dispersed in the water. Effectiveness was ascertained based on the decrease in microbial attachment, limited toxicity, and minimum alteration of the coatings properties. Results and Discussion A significant inhibition of bacteria attachment was achieved when aqueous capsaicin concentration was increased from 0 to 40 mg/L. For instance, after 14 days the LE system depicted 93.5% and 98.5% less biofilm coverage for 20 mg/L and 40 mg/L capsaicin, respectively when compared to systems without NPA. Biofilm coverage was reduced by 92.5% and 98.2%, respectively with 50 mg/L and 500 mg/L zosteric acid. Conclusions Both capsaicin and zosteric acid was effective at preventing bacteria attachment. As the NPA aqueous concentration increased, biofilm formation decreased. Evaluating changes in aqueous pH, conductivity, dissolved oxygen, aqueous microbial population and biofilm formation suggested that the primary antifoulant mechanism of these two NPAs was to block the bacteria's active sites versus posing a lethal level. Recommendation and Perspective From the attachment study, zosteric acid appeared to be more effective in preventing bacterial attachment when the NPAs were dispersed in the aqueous environment. For practical applications, the antifoulant needs to be incorporated into a coating and have a slow release rate. Thus the ability to successfully incorporate zosteric acid into a coating, without deterring bacterial attachment, needs to be investigated.     

Statistical Modelling of CO and NO2 Concentrations in the Athens Area - Evaluation of Emission Abatement Policies (7 pp)

- DOI: http://dx.doi.org/10.1065/espr2006.04.299 Goal, Scope and Background This paper describes a statistical modelling approach, suggested as a policy tool in the Athens area for the assessment of the emissions reduction level required to meet the air quality standards for two criteria air pollutants, namely CO and NO2. Methods. More than ten years of hourly CO and NOx-NO2 concentration data measured by the monitoring network of the Hellenic Ministry for the Environment, Physical Planning and Public Works were analyzed and the original dataset has been reduced using a data evaluation procedure. Results and Discussion Seasonal pollutant concentration trends suggested that the reduction of CO and NOx concentrations observed in the beginning of the '90s is almost entirely attributed to the increase of the catalyst-equipped cars during this period. The numerical parameters of an empirical model relating EU standard exceedances with mean annual concentrations were defined and the model was validated using datasets from years that were not used for the estimation of these parameters. This model was used in conjunction with a roll-back equation as a policy tool for the assessment of the effect of different CO and NOx emissions reduction scenarios on air quality standard compliance for CO and NO2. Results predicted with this empirical modelling approach were assessed with monitored data averaged over a 3-year period, giving satisfactory results. Conclusion A methodology suggested for assessing the effects of different emissions reduction scenarios on air quality standard attainment was successfully applied for CO and NO2 in the Athens area. Recommendation and Perspective The proposed methodology can provide a useful tool for the evaluation of policies already in progress as well as the development of future policies for emissions reduction in urban areas with similar characteristics, aiming at air quality standard compliance on a timely manner. Such a methodology could be applied in other urban areas of Greece characterized by dense traffic, therefore assisting the development of national policies in relation to air pollutants for which standard exceedances occur.     

Terbuthylazine Contamination of the Aquifer North of Vicenza (North-East Italy) (5 pp)

- DOI: http://dx.doi/10.1065/espr2006.01.016 Background and Goal Agricultural practices can affect the quality of aquifers given that they are often located in cropped areas, so significant amounts of pesticides can be found in the water. In particular, triazine herbicides are always carefully checked by the official monitoring systems. The goal of this study was to find the mean concentration of terbuthylazine in an Italian aquifer and to set up a mass balance of this compound. Methods Terbuthylazine concentrations in the aquifer were measured in various check-wells during 1998–2004, and the value of censored data were estimated using a Gompertz inverse in order to evaluate the overall mean concentration. The total terbuthylazine load in the recharge area was calculated on the basis of surveys of cropped land and the main weed control techniques applied in the area. Data on aquifer water balance were obtained from previous studies. Results and Discussion The herbicide terbuthylazine applied in the recharge zone can be transported by surface water and enter the aquifer. Detected concentrations were always well below the EU drinking water limit and the fraction that can reach the groundwater under normal cropping practices is small, very likely less than 0.2%. Recommendations and Outlook The use and application rates of pesticides should be strictly regulated in recharge areas. Vegetated buffer strips can mitigate the impact of herbicides on surface water through reducing drift and early-spring runoff. Attention should also be paid to the fate of the main metabolites from soil biochemical processes.     

Spatial and Geographical Variations of Urban, Suburban and Rural Atmospheric Concentrations of Phenols and Nitrophenols (7 pp)

Goal, Scope and Background Atmospheric sampling (gas and particles) of 5 phenols (phenol, m-cresol, p-cresol, o-cresol, pentachlorophenol) and 15 nitrophenols (3-methyl-2-nitrophenol, 3-nitrophenol, 4-methyl-2-nitrophenol, 5-methyl-2-nitrophenol, 2-methyl-3nitrophenol, 3-methyl-4-nitrophenol, 2,6-dinitrophenol, bromoxynil, 2,5-dinitrophenol, 2,6-dinitro-p-cresol, 2,4-dinitrophenol, ioxynil, DNOC, 3,4-dinitrophenol, dinoseb) on XAD-2 resin (20 gr) and glass fibre filters, respectively, were performed in 2002 by using 'Digitel DA80' high volume samplers. These measurements were undertaken in order to show spatial and geographical variations of concentrations and the role of traffic in the emissions of these compounds to the atmosphere. Methods Sampling were performed in Strasbourg (eastern France), in its vicinity (Schiltigheim) and in Erstein. Sites were chosen to be representative of urban (Strasbourg), suburban (Schiltigheim) and rural (Erstein) conditions. Field campaigns were undertaken simultaneously in urban and suburban sites during all the seasons during 4 hours at a flow rate of 60 m3.h-1, which gives a total of 240 m3 of air per sample. Period of sampling varied between 06h00 to 10h00, 11h00 to 15h00 and 18h00 to 22h00 in order to evaluate a variation of concentration during automobile traffic between urban, suburban and rural areas. Gas and particle samples were separately Soxhlet extracted for 12 h with a mixture of CH2Cl2 / n-hexane (50:50 v/v), concentrated to about 1 mL with a rotary evaporated and finally dried under nitrogen. Dry extracts were dissolved in 1 mL of CH3CN. Before analysis, extracts were sylilated by using MTBSTFA. Analysis was performed by GC/MSD in the SIM mode. Results and Discussion Partitioning of phenolic compounds between gas and particle phases seems to be mainly correlated with vapour pressure. Among phenolic compounds analysed, phenol, p-cresol, pentachlorophenol and 2.4-dinitrophenol were detected in all samples and emissions from traffic seems to be the major source for the presence of these compounds to the atmosphere. No increase of concentrations in autumn tend to confirm this hypothesis since, with the use of domestic heating in colder months, increases of PAHs concentrations were observed and these compounds are known to be emitted by all combustion processes. Pentachlorophenol is a special case since this molecule is only used as wood preservative. Its presence in all atmospheric samples, whatever the locations and the period of time is the consequence of its persistence. Conclusions and Perspectives These measurements demonstrate that phenols and nitrophenols are emitted to the atmosphere and further measurements, in order to confirm their sources, their behaviour and their potential impact to the air quality and to human health should be undertaken especially since the literature collected is relatively old. Concentrations of pentachlorophenol measured are very low and, due to its toxicity, further investigations should be undertaken. - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

The Influence of Mycorrhiza on Uranium and Phosphorus Uptake by Barley Plants from a Field-contaminated Soil (7 pp)

Background Recent studies indicated that arbuscular mycorrhizal fungi (AMF) play important roles in plant accumulation of uranium (U) from contaminated environments, but the impacts of fertilization practices on functioning of the symbiotic associations, which are crucial factors influencing plant nutrition and growth responses to mycorrhiza, have rarely been considered. Materials and Methods In a greenhouse experiment, a bald root barley mutant (brb) together with the wild type (wt) were used to test the role of root hairs and AMF in uranium (U) uptake by host plants from a U contaminated soil. Nil, 20 and 60 mg KH2PO4-P kg–1 soil were included to investigate the influences of phosphorus (P) fertilization on plant growth and accumulation of U. Results Dry matter yield of barley plants increased with increasing P additions and wt produced significantly higher dry weight than brb. Mycorrhiza markedly improved dry matter yield of both genotypes grown at nil P, whereas only brb responded positively to mycorrhiza at 20 mg P kg-1. At the highest P level, mycorrhiza resulted in growth depressions in both genotypes, except for the roots of wt. In general, plant P concentrations increased markedly with increasing P additions and in response to mycorrhiza. Mycorrhiza and P additions had no significant effects on shoot U concentrations. However, root U concentrations in both genotypes were significantly increased by mycorrhiza. On the other hand, shoot U contents increased with increasing P levels, while 20 mg P kg-1 stimulated, but 60 mg P kg-1 marginally affected the U accumulation in roots. Root length specific U uptake was moderately enhanced both by root hairs and strongly enhanced by mycorrhiza. Moreover, non-inoculated plants generally had higher shoot-root ratios of U content than the corresponding inoculated controls. Conclusion Our study shows that AMF and root hairs improves not only P acquisition but also the root uptake of U, and mycorrhiza generally decreases U translocation from plant root to shoot. Hence, mycorrhiza is of potential use in the phytostabilization of U contaminated environments. Perspectives The complex impacts of P on U accumulation by barley plants suggested that U behavior in mycorrhizosphere and translocation along the soil-fungi-plant continuum as affected by fertilization practices deserve extensive studies for optimizing the function of mycorrhizal associations for phytoremediation purposes.     

Measurement of the Oxygen Mass Transfer Through the Air-Water Interface (5 pp)

Goal, Scope and Background Gas mass transfer through the liquid-gas interface has enormous importance in various natural and industrial processes. Surfactants or insoluble compounds adsorbed onto an interface will inhibit the gas mass transfer through the liquid-gas surface. This study presents a technique for measuring the oxygen mass transfer through the air-water interface. Experimental data obtained with the measuring device were incorporated into a novel mathematical model, which allowed one to calculate diffusion conduction of liquid surface layer and oxygen mass transfer coefficient in the liquid surface layer. Methods A special measurement cell was constructed. The most important part of the measurement cell is a chamber containing the electrochemical oxygen sensor inside it. Gas exchange between the volume of the chamber and the external environment takes place only through the investigated surface layer. Investigated liquid was deoxygenated, which triggers the oxygen mass transfer from the chamber through the liquid-air interface into the liquid phase. The decrease of oxygen concentration in the cell during time was measured. By using this data it is possible to calculate diffusional parameters of the water surface layer.Results Diffusion conduction of oxygen through the air-water surface layer of selected wastewaters was measured. The diffusion conduction of different wastewaters was about 3 to 6 times less than in the unpolluted water surface. It was observed that the dilution of wastewater does not have a significant impact on the oxygen diffusion conduction through the wastewater surface layer. This fact can be explained with the presence of the compounds with high surface activity in the wastewater. Surfactants achieved a maximum adsorption and, accordingly, the maximum decrease of oxygen permeability already at a very low concentration of surfactants in the solution. Oxygen mass transfer coefficient of the surface layer of the water is found to be.Conclusion A simple technique for measuring oxygen diffusion parameters through the air-water solution surface has been developed. Derived equations enable the calculation of diffusion parameters of the surface layer at current conditions. These values of the parameters permit one to compare the resistances of the gas–liquid interface to oxygen mass transfer in the case of adsorption of different substances on the surface layer. Recommendation and Outlook This simple technique may be used for a determination of oxygen permeability of different water-solution surface layers. It enables one to measure the resistance to the oxygen permeability of all inflowing wastewater surface layers in the wastewater treatment plant, and to initiate a preliminary cleaning of this wastewater if required. Similarly, we can measure oxygen permeability of natural waterbodies. Especially in the case of pollution, it is important to know to what extent the oxygen permeability of the water surface layer has been decreased. Based on the tehnique presented in this research, fieldwork equipment will be developed.