Studies in the Biodegradation of 5 PAHs (Phenanthrene,Pyrene, Fluoranthene,Chrysene und Benzo(a)pyrene) in the Presence of Rooted Poplar Cuttings

Cuttings of Populus nigra L. cv. Loenen were cultivated in sand treated with one of the following PAHs: phenanthrene (Phen), fluoranthene (Flt), pyrene (Pyr), chrysene (Chr) and benzo[a]pyrene (BaP). The PAHs were applied at varying levels of concentration to each test series. After 6 weeks the concentration and the distribution of the PAHs in the substrate of the various sets of tests were compared with the concentration in the substrate of the control. Additionally the substrate and the plant roots were tested for evidence of degradation products of PAHs. The results revealed that the levels of concentration of Phen and Pyr detected in the substrate surrounding the roots was in some cases significantly lower than in the corresponding section of substrate in the unplanted set (= control). This phenomenon did not occur for Flt and BaP and in the case of Chr only in those substrates, which had been treated with the highest levels of concentration. As the presence of lesser amounts of Phen and Pyr in the plant pots cannot only be attributed to their accumulation and metabolism in the roots, it is fair to assume that the chemical transformation of these three PAHs took place outside the roots. The set of tests treated with Phen revealed the presence of 2- or 3-hydroxy-Phen (main components), a hydroxy-methoxy-Phen, 9,10-Phenanthrenequinone and one unidentified compound in metabolite form. Altogether eleven metabolites of Pyr were identified in the root extracts, which can be divided into three groups: 1-Hydroxy-Pyr and derivatives, dihydroxy-Pyr and derivatives and ring fission products (4-Hydroxy-Pyr and a derivative of the 4-Phen-carbonic acid). However, the metabolite mass detected for Phen and Pyr represents only an insignificant percentage in comparison with the lesser amounts of PAHs observed in the planted set of tests. This indicates that the three PAHs were reduced to lower molecular compounds, which are methodically impossible to record, and subsequently translocated to other parts of the plant and integrated into the biomass. Although no lesser amount for Flt and BaP was found in the plant pots, 1-Hydroxy-Flt, an unidentified compound of Flt and 1-Methoxy-BaP were detected. These are presumably end products which were enhanced in the roots. It was not possible to identify any transformation products of Chr. It can be assumed that the majority of metabolites were not synthesised in the roots but are a result of microbial degradation in the rhizosphere. The test plants improved the conditions for the biotransformation of Phen and Pyr significantly and accumulated Flt, Pyr, Chr and BaP in their roots. It can therefore be concluded that the use of plants in the bioremediation of contaminated soils is a promising option.     

Sensitivity analyses of woody species exposed to air pollution based on ecophysiological measurements

GOAL, SCOPE AND BACKGROUND: Air pollution has been of a major problem in the Pearl River Delta of south China, particularly during the last two decades. Emissions of air pollutants from industries have already led to damages in natural communities and environments in a wide range of the Delta area. Leaf parameters such as chlorophyll fluorescence, leaf area (LA), dry weight (DW) and leaf mass per area (LMA) had once been used as specific indexes of environmental stress. This study aims to determine in situ if the daily variation of chlorophyll fluorescence and other ecophysiological parameters in five seedlings of three woody species, Ilex rotunda, Ficus microcarpa and Machilus chinensis, could be used alone or in combination with other measurements for sensitivity indexes to make diagnoses under air pollution stress and, hence, to choose the correct tree species for urban afforestation in the Delta area. METHODS: Five seedlings of each species were transplanted in pot containers after their acclimation under shadowing conditions. Chlorophyll fluorescence measurements were made in situ by a portable fluorometer (OS-30, Opti-sciences, U.S.A). Ten random samples of leaves were picked from each species for LA measurements by area-meter (CI-203, CID, Inc., U.S.A). DW was determined after the leaf samples were dried to a constant weight at 65 degrees C. LMA was calculated as the ratio of DW/LA. Leaf N content was analyzed according to the Kjeldhal method, and the extraction of pigments was carried out according Lin et al. RESULTS AND DISCUSSION: The daily mean Fv/Fm (Fv is the variable fluorescence and Fm is the maximum fluorescence) analysis showed that Ilex rotunda and Ficus microcarpa were more highly resistant to pollution stress, followed by Machilus chinensis, implying that the efficiency of photosystem II in I. rotunda was less affected by air pollutants than the other two species. Little difference in daily change of Fv/Fm in I. rotunda between the polluted and the clean site was also observed. However, a relatively large variation of Fv/Fm appeared in the other two species, particularly in M. chinensis, suggesting that they were more sensitive to air pollutants than I. rotunda. The mean LA was reduced for all species growing at the polluted site. The mean LMA for all species exceeded the sclerophylly threshold given by Cowling and Campbell and increased for those under pollution stress, which could be explained as one of the acclimation strategies for plants to air pollution stress. Little difference in leaf chlorophyll content was observed in F. microcarpa and M. chinensis, while remarkable differences were found in I. rotunda growing at the polluted and the clean site. Content of leaf carotenoids was largely reduced in I. rotunda growing at the polluted site, but increased in F. microcarpa and M. chinensis, compared with plants growing at the clean site. Plants growing at the clean site had a lower leaf N content than those growing at the polluted site. In addition, species with a higher resistance to pollution stress showed less difference in leaf N content than those sensitive species. CONCLUSION: Based on Fv/Fm measurements of the three woody species, I. rotunda showed the highest resistance to air pollutants from ceramic industries, followed by F. microcarpa. M. chinensis was the most sensitive species to air pollution, had lowest capacities to cope with the air pollution stress, which was consistent with visual injury symptoms observed in the crown profiles of plants at the polluted site. Fv/Fm, LAM, LA, leaf pigments and N content could be used alone or in combination to diagnose the extent of the physiological injury. The ratio of Fv/Fm, however, was the best and most effective parameter. RECOMMENDATION AND OUTLOOK: Tree species which have higher air-pollutant resistance, as diagnosed by such ecophysiological parameters, should be considered first and planted widely for urban afforestation or forest regeneration in areas where the forest was seriously degraded or forest health was markedly effected by the same kind of air pollutants.     

Formation and emission of chloroanisoles as indoor pollutants

GOAL, SCOPE AND BACKGROUND: Complaints by residents of frame-houses about musty odour in the houses has become an increasing problem within the last years. An additional problem is that the odour is transferred to clothes and skin. The persons themselves do not recognize the smell after a while because of adaptation. Serious social problems are the result. For a long time, the smell was explained to be from mould due to construction-based humidity problems. However, in an increasing number of houses, no indications were found for elevated levels of mould growth. METHODS: Air and material samples were taken from 5 houses, which show typical musty odours, and analysed with respect to chlorophenols and chloroanisoles. Additionally, some samples were analysed for lindane and its metabolites, because lindane was commonly used together with pentachlorophenol (PCP) for wood protection. RESULTS AND DISCUSSION: Meticulous analysis resulted in the identification of chloroanisoles, mainly 2,3,4,6-tetrachloroanisole. These substances are known from corky wines and from contamination of food from pentachlorophenol (PCP) treated pallets and result from microbiological metabolic processes. Pentachlorophenol was commonly used to protect wood from fungi in Germany mainly in the later 60s and 70s. Details of these processes, as well as effective methods to identify chloroanisoles in the problem houses, are described. CONCLUSIONS: Chloroanisoles formed by metabolism of PCP have been well known to contaminate food or wine. Here, they were identified and are probably responsible for the musty odours in the frame houses. Since it is quite clear that these substances were not components of building materials used in the houses, an explanation for chloroanisole formation is proposed. Localized dampness probably favours microbial growth associated with metabolic conversion of chlorophenols to the corresponding chloroanisoles, primarily 2,3,4,6-tetrachloroanisol, which spread throughout the buildings, resulting in the observed odours. RECOMMENDATIONS AND OUTLOOK: The group of chloroanisoles has been recognized as important indoor pollutants as they possess musty odours at extremely low concentrations, e.g. for 2,4,6-trichloroanisole in a range of 5-10 ppt in air (Staples 2000). On the basis of currently available toxicological data, exposure of the occupants to the concentrations of chloroanisoles measured is not associated with a health risk. No correlation could be observed between concentrations of chloroanisoles and PCP in house dust and indoor air. However, chloroanisoles are good indicators for possible PCP-treatment of wood in frame houses and their detection should initiate investigations on PCP contamination. Research is continuing to identify the microorganisms involved and to devise a remediation procedure for affected houses.     

Photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in soil with vegetable oil

GOAL, SCOPE AND BACKGROUND: This study was carried out to investigate the effect of olive oil on the photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in contaminated sawmill soil. Previous studies had shown that the solubility of PCDD/Fs in olive oil is high and a rapid photodegradation of PCDD/Fs takes place in olive oil when irradiated with ultraviolet (blacklight) lamps. The efficiency of this treatment method was evaluated under more practical conditions. These included the use of sunlight irradiation and a lower-grade olive oil, without a preliminary extraction of soil with olive oil. METHODS: A 1-cm layer of contaminated sawmill soil was blended with 20 weight-% of olive oil and exposed to sunlight for four weeks. In another experiment, a new dose of olive oil was added at the middle of the exposure period. The PCDD/F concentrations of the soils were monitored periodically. RESULTS AND DISCUSSION: A reduction in the concentration of 2,3,7,8-chlorinated PCDD/Fs by 59% and in WHO-TEQ in contaminated sawmill soil by 48% was attained after blending the soil with two doses (20 + 20%) of olive oil and exposing the mixture to sunlight for four weeks. Photodegradation with only one dose of olive oil was less efficient. This suggests that periodical additions of olive oil would be needed to maintain a proper degradation rate. After the oil additions, the WHO-TEQ content of the soil declined with first order reaction half-lives of 19.2 to 19.7 d. The overall half-life during the four-week treatment, however, was 30 d. CONCLUSION: A significant reduction in the PCDD/F concentration of aged sawmill soil can be achieved with a relatively simple olive oil-sunlight treatment. RECOMMENDATIONS AND OUTLOOK: Some theoretical and technological questions need to be solved before using the investigated soil decontamination method in larger-scale applications. The functions of vegetable oils in photodegradation processes should be studied in more detail. The amount of oil that is needed for a proper solubilisation and photodegradation of PCDD/Fs should be minimised. Moreover, special care should be taken to prevent mobilisation of PCDD/Fs to the surrounding environment and to avoid leaving bioavailable residuals of PCDD/Fs in soil.     

Phytoremediation of petroleum hydrocarbons in tropical coastal soils II. microbial response to plant roots and contaminant

GOAL, SCOPE AND BACKGROUND: The goal of this study was to understand the interaction between plants and microorganisms during petroleum-hydrocarbon bioremediation in Pacific Islands coastal soils. Total bacteria and hydrocarbon-degrading microorganisms population dyanamics were examined in the rhizospheres of tropical trees and shrubs, which were evaluated for their phytoremediation potential in a greenhouse experiment. The respective and combined effects of plant roots and diesel contaminant on the microbial populations were determined in relation to diesel fuel depletion. An increase in the grading populations size of the hydrocarbon-degrading populations of microbes, elicited by rhizodeposition, is generally regarded as conducive to an enhanced degradation of petroleum hydrocarbon pollutants in vegetated soil. METHODS: The soil was a coastal sandy loam (pH 7.8) which was artificially contaminated with 10 g of No. 2 diesel fuel/kg soil or left uncontaminated. The pots were irrigated with fertilizer and 1% NaCl. The enumerations were carried out in the contaminated and uncontaminated rhizospheres of three trees, kiawe (Prosopis pallida), milo (Thespesia populnea), and kou (Cordia subcordata) and three shrubs, beach naupaka (Scaevola sericea), false sandalwood (Myoporum sandwicense), and oleander (Nerium oleander). Unplanted control soils were included in the experiment. Total bacteria and phenanthrene-degrading bacteria were enumerated on plates. Diesel- and pristane-degrading microorganisms were enumerated by the most-probable-number technique in tissue-culture plates. RESULTS AND DISCUSSION: All four types of microorganisms responded to the rhizosphere of the 6 plants in uncontaminated soil and to the diesel contaminant in unplanted soil. In contaminated rhizospheres, no effect of the plant on the hydrocarbon-degrader numbers was visible. Total bacteria responded more to the plant roots than to the contaminant. The phenanthrene-degrading bacteria and pristane-degrading microorganisms were more influenced by the contaminant than by the plants. The diesel-degrading microorganisms were equally stimulated by the plants and the contaminant. The numbers of hydrocarbon degraders were similar in the contaminated rhizospheres of the three effective plants (kiawe, kou, and milo) and in those of the three ineffective shrubs. CONCLUSION: The results suggest the quality of the rhizodeposition is plant-dependent and governs the type of diesel-degrader populations that will be enhanced by a given plant. RECOMMENDATIONS AND OUTLOOK: In the proposed phytoremediation-benefit model plant roots maintain high levels of hydrocaron degraders in uncontaminated soil. When the root enters a contaminated zone of soil, those hydrocarbon degraders that prefer the contaminant would switch to the contaminant as a carbon source, effectively removing the hydrocarbons. If the root exudates and the contaminant are equally attractive to the hydrocarbon degraders, the contaminant degradaton would be less effective.     

Decolorization and biodegradation of dye wastewaters by a facultative-aerobic process

BACKGROUND: Dye wastewater is one of the main pollution sources of water bodies in China. Conventional biological processes are relatively ineffective for color removal, the development of alternative treatment methods will become important. Our subjective was that of introducing a new biotreatment technology which combined a facultative biofilm reactor (FBR) with an aerobic reactor (AR) to treat a dye wastewater. The efficiencies of color and chemical oxygen demand (COD) removal and the mechanism of dye degradation were investigated. METHODS: The anthraquinone acid dye (acid blue BRLL) concentration, organic loading rate (OLR) and hydraulic retention time (HRT) were varied in the experiments to evaluate the treatment efficiency and process stability. The biodegradation products were detected by infrared (IR) and high performance liquid chromatography and mass spectrometry (HPLC-MS). RESULTS AND DISCUSSION: The results demonstrated that the facultative biofilm process was more effective for decolorization than the anaerobic stage of an anaerobic-aerobic process. Most color removal occurred in the facultative reaction (maximum to 88.5%) and the BOD (biochemical oxygen demand): COD of the FBR effluent increased by 82.2%, thus improving the biodegradability of dyes for further aerobic treatment. The dye concentration, OLR and HRT will be the factors affecting decolorization. Color removal efficiency falls as the influent dye concentration increases, but rises with increased HRT. The infrared and HPLC-MS analyses of the effluents of FBR and AR reveal that the dye parent compound was degraded in each reactor during the process. CONCLUSION: The Facultative-aerobic (F-A) system can effectively remove both color and COD from the dye wastewater. The FBR played an essential role in the process. The average overall color and COD in the system were removed by more than 93.9% and 97.1%, respectively, at an OLR of 1.1 kg COD m(-3) d(-1) and at the HRT of 18-20 hours in the FBR and 4-5 hours in the AR. The color removal mechanism in each reactor was not only a sort of biosorption on the floc materials, but even more an effect of biodegradation, especially in the facultative process. Recommendation and Outlook. In applying the F-A system to treat a dye wastewater, the control of facultative processes and the set up of appropriate operation conditions appear to be critical factors. Also, it is suggested a moderate COD loading rate and about a 24-hour HRT will favor the F-A system.     

Dendroremediation of trinitrotoluene (TNT) Part 2: Fate of radio-labelled TNT in trees

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 of 14C were determined in sand/soil, roots, stem-wood, stem-bark, branches, leaves, needles, and Picea May sprouts. Root extracts were analysed by radio TLC. RESULTS: 60 days after [14C]-TNT application, recovered 14C is accumulated in roots (70% for sand variants, 34% for AP-soil variant). 15-28% of 14C remained in sand and 61% in AP-soil. 3.3 to 14.4% of 14C were located in aboveground tree portions. Above-ground distribution of 14C differed considerably between the angiosperm Salix and the gymnosperm Picea. In Salix, nearly half of above-ground-14C was detected in bark-free wood, whereas in Picea older needles contained most of the above-ground-14C (54-69%). TNT was readily transformed in tree tissue. Approximately 80% of 14C was non-extractably bound in roots, stems, wood, and leaves or needles. Only quantitatively less important stem-bark of Salix and Picea and May shoots of Picea showed higher extraction yields (up to 56%). 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-dinitrotoluenes (ADNT), diaminonitrotoluenes (DANT), trinitrobenzene (TNB) and no dinitrotoluenes (DNTs) were present. Extractable portions of 14C were small and contained at least three unknown metabolites (or groups) for Salix. In Picea, four extractable metabolites (or groups) were detected, where only one metabolite (or group) seemed to be identical for Salix and Picea. 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-exposed Salix and Populus clones. It is concluded that 'cold' tissue analysis of tree organs is not suited for quantitative success control of phytoremediation in situ. RECOMMENDATIONS AND OUTLOOK: Both short rotation Salicaceae trees 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.     

The importance of biological factors affecting trace metal concentration as revealed from accumulation patterns in co-occurring terrestrial invertebrates

As physicochemical properties of the soil highly influence the bioavailable fraction of a particular trace metal, measured metal body burdens in a particular species are often assumed to be more reliable estimators of the contamination of the biota. To test this we compared the Cd, Cu and Zn content of three spiders (generalist predators) and two amphipods (detritivores), co-occurring in seven tidal marshes along the river Schelde, between each other and with the total metal concentrations and the concentrations of four sequential extractions of the soils. Correlations were significant in only one case and significant site x species interactions for all metals demonstrate that factors affecting metal concentration were species and site specific and not solely determined by site specific characteristics. These results emphasize that site and species specific biological factors might be of the utmost importance in determining the contamination of the biota, at least for higher trophic levels. A hypothetical example clarifies these findings.     

Wissenschaftstheoretische Grundlagen der Beobachtung von GVO-Umweltwirkungen

Zusammenfassung Hintergrund und Ziel  Die Exposition gentechnisch ver?nderter Kulturpflanzen erfordert die Beobachtung ihrer Umweltwirkungen. Ziel der Beitragsserie über die Beobachtung ?kologischer Wirkungen von GVO ist es, den hierzu erreichten Stand der Wissenschaft vorzustellen. Da bei einem Bundesl?nder und ggf. europ?ische Staaten übergreifenden Monitoring besonders auf methodisch vergleichbare und r?umlich aussagekr?ftige Daten zu achten ist, werden in diesem einführenden Beitrag wissenschaftstheoretische und statistische Grundlagen des Monitoring sowie die Standardisierung der Beobachtungsverfahren behandelt. Schwerpunkte  Im Mittelpunkt stehen zun?chst ?kologische Anforderungen an das GVO-Monitoring. Um mit GVO ggf. zusammenh?ngende Umweltver?nderungen ermitteln zu k?nnen, ist eine Eingliederung in bestehende Umweltbeobachtungsprogramme erforderlich. GVO-Exposition und-Wirkung sind aufeinander bezogen über die Organisationsstufen ?kologischer Systeme hinweg zu erfassen. Ein effizientes und suffizientes Monitoring bedarf eines wissenschaftstheoretisch und statistisch soliden Designs. Deshalb werden einem weiteren Schwerpunkt dieses Beitrags wissenschaftstheoretische Grundlagen der Hypothesenbildung und-prüfung behandelt. Hierfür bedarf es Daten, die mehreren, im Einzelnen behandelten Qualit?tskriterien entsprechen müssen. Eines dieser Kriterien ist die r?umliche und zeitliche Verallgemeinerungsf?higkeit der Monitoring-Befunde, die in dem dritten Schwerpunkt des Beitrags dargestellt wird. Schlussfolgerungen  Für die Prüfung von Hypothesen über Umweltfolgen von GVO sind konsequent ?kosystemforschung und Monitoring eng miteinander zu vernetzen. Denn sie erfüllen komplement?re Funktionen, die für das Monitoring der Umweltwirkungen von GVO von gro?er praktischer und wissenschaftlicher Bedeutung sind. Empfehlungen  Das GVO-Monitoring sollte in bestehende Programme der ?kosystemforschung und der Umweltbeobachtung eingebettet werden und die ?kologischen Organisationsstufen sowie GVO-Exposition und-Wirkung einschlie?en. Die Lokalisierung der Messorte sollte die erwartete Exposition oder Wirkung berücksichtigen. Perspektiven  Weitere Beitr?ge dieser Serie werden die Messplanung, das Pollenmonitoring und die r?umliche Verallgemeinerung von Ergebnissen standortspezifischer Messungen oder Modellierungen behandeln.

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Environmental monitoring of ecological impacts of GMOs

Goal, Scope and Background  The release of genetically modified organisms (GMOs) may result in ecological impacts to be monitored. This series presents the state-of-art concerning the environmental monitoring of ecological impacts of GMOs. Since this monitoring is conducted by several authorities, the methodical comparability and spatial validity of the monitoring data is crucial. Thus, the respective fundamentals of philosophy of science and of statistics as well as the methodical standardisation form the focus of this article. Main Features  At first, the monitoring requirements will be described from the viewpoint of ecology. Consequently, the GMO monitoring needs to be integrated into existing programmes. Exposure and effects of GMOs have to be monitored across the hierarchy of ecological organisation. For monitoring to be efficient and sufficient, the design must be founded in terms of philosophy of science and statistics. Hence the fundamentals concerning the verification of hypotheses represent another feature of this article. The data used for the verification of hypotheses must comply with quality criteria. One of these criteria is the spatial and temporal extrapolation of the monitoring results, which is the third feature in this introductory article. Conclusions  The evaluation of hypotheses on GMO impacts requires the linkage to ecosystems research and environmental monitoring. These both are, in terms of methodology, complementary and of significant technical and scientific value for GMO monitoring. Recommendations  GMO-monitoring should closely be connected with ecosystems research and environmental monitoring. The levels of ecological organisation should be covered as well as the exposure and the effects of GMOs. The expected GMO exposure and effects should be considered by localising the monitoring sites. Perspectives  Further articles of this series will deal with network designing, GMO pollen monitoring and extrapolation of site-specific measurements and modelling results.

     

Adsorption of Disperse Blue SBL dye by synthesized poorly crystalline hydroxyapatite

The present study has been undertaken to evaluate the adsorption in batch mode of a disperse dye (Disperse Blue SBL) by poorly crystalline hydroxyapatite synthesized by coprecipitation between Ca(NO_3)_2 and (NH_4)_2HPO4 reagents in aqueous solution at room temperature. The adsorption experiments were carried out to investigate the factors that influence the dye uptake by the adsorbent, such as the contact time under agitation, adsorbent dosage, initial dye concentration, solution temperature, and pH. The e...