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.     

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.     

Luftreinhaltung oder Klimakontrolle?

Ohne Zusammenfassung     

Fate and transport of N-nitrosamines under conditions simulating full-scale groundwater recharge operations.

The key objective of this study was to investigate the attenuation mechanisms of seven N-nitrosamine compounds at environmental concentrations and under conditions relevant to groundwater recharge operations. The study used a combination of controlled laboratory-scale soil-column experiments and groundwater monitoring at a full-scale river-bank filtration facility. Findings of the controlled column experiments suggest that N-nitrosodimethylamine and six other N-nitrosamines (N-nitrosodiethylamine, N-nitrosomethylethylamine, N-nitroso-n-propylamine, N-nitrosodi-n-butylamine, N-nitrosopiperidine, and N-nitrosopyrrolidine) are biodegradable under oxic and anoxic oxidation-reduction conditions. Half lives determined in this study for the targeted compounds varied between 1.3 and 7 days, which will ensure a removal to below detection limits (< 2 ng/L) within short travel times in groundwater recharge systems. Findings of this study suggest that complete removal of N-nitrosamines requires the presence of an adapted biocommunity, which will be established over several weeks to months.     

不同管材水管与静态自来水水质间的相互影响

对比了铝塑复合管(PAP)、铜管、不锈钢管和镀锌铁管对静态自来水的总有机碳(TOC)、溶解氧(DO)、浊度、细菌总数和大肠菌群等水质指标的影响。实验结果表明,铜管对自来水水质指标影响最小,且具有良好的卫生性能。同时,通过场发射扫描电子显微镜(FESEM)的观察,对比分析了铜管和铝塑复合管在浸泡实验前后其内表面形态特征的变化,结果显示自来水中浸泡10个月以后,铜管内表面密集地分布着块状的孔雀石晶体,而铝塑复合管内表面已严重变形,产生很多褶皱。     

Cumulative and Residual Effects of Repeated Sewage Sludge Applications: Forage Productivity and Soil Quality Implications in South Florida,USA (9 pp)

Background, Aim and Scope The cow-calf (Bos taurus) industry in subtropical United States and other parts of the world depends almost totally on grazed pastures. Establishment of complete, uniform stand of bahiagrass (BG) in a short time period is important economically. Failure to obtain a good BG stand early means increased encroachment of weeds and the loss of not only the initial investment costs, but production and its cash value. Forage production often requires significant inputs of lime, N fertilizer, and less frequently of P and K fertilizers. Domestic sewage sludge or biosolids, composted urban plant debris, waste lime, phosphogypsum, and dredged materials are examples of materials that can be used for fertilizing and liming pastures. Perennial grass can be a good choice for repeated applications of sewage sludge. Although sewage sludge supply some essential plant nutrients and provide soil property-enhancing organic matter, land-application programs still generate some concerns because of possible health and environmental risks involved. The objectives of this study were to evaluate the cumulative and residual effects of repeated applications of sewage sludge on (i) bahiagrass (BG, Paspalum notatum Flügge) production over years with (1997–2000) and without (2001–2002) sewage sludge applications during a 5-yr period, and (ii) on nutrients status of soil that received annual application of sewage sludge from 1997 to 2000 compared with test values of soils in 2002 (with no sewage sludge application) in South Florida.Methods The field experiment was conducted at the University of Florida Agricultural Research and Education Center, Ona, FL (27o26’N, 82o55’W) on a Pomona fine sandy soil. With the exception of the control, BG plots received annual sewage sludge and chemical fertilizers applications to supply 90 or 180 kg total N ha–1 yr–1 from 1997 to 2000. Land application of sewage sludge and fertilizer ceased in 2001 season. In early April 1998, 1999, and 2000, plots were mowed to 5-cm stubble and treated with the respective N source amendments. The experimental design was three randomized complete blocks with nine N-source treatments: ammonium nitrate (AMN), slurry biosolids of pH 7 (SBS7), slurry biosolids of pH 11 (SBS11), lime-stabilized cake biosolids (CBS), each applied to supply 90 or 180 kg N ha–1, and a nonfertilized control (Control). Application rates of sewage sludge were calculated based on the concentration of total solids in materials as determined by the American Public Health Association SM 2540G method and N in solids. The actual amount of sewage sludge applications was based on the amount required to supply 90 and 180 kg N ha–1. Sewage sludge materials were weighed in buckets and uniformly applied to respective BG plots. Soil samples were collected in June 1997, June 1999, and in June 2002 from 27 treatment plots. In 1997 and 1999, soil samples were collected using a steel bucket type auger from the 0- to 20-, 20- to 40-, 40- to 60-, and 60- to 100-cm soil depths. Forage was harvested on 139, 203, 257, and 307 day of year (DOY) in 1998; 125, 202, 257, and 286 DOY in 1999; 179, 209, 270, and 301 DOY in 2000; and on 156 and 230 DOY in 2002 (no sewage sludge applications) to determine the residual effect of applied sewage sludge following repeated application. Forage yield and soils data were analyzed using analysis of variance (PROC ANOVA) procedures with year and treatment as the main plot and sub-plot, respectively. As a result of significant year effects on forage yield, data were reanalyzed annually (i.e., 1998, 1999, 2000, and 2002).Results and Discussion All sewage sludges used in this study were of class B in terms of USEPA’s pathogens and pollutant concentration limit. Pathogen and chemical composition of the class B sewage sludge that were used in the study were all in compliance with the USEPA guidelines. The liquid sludge (SBS11) had the lowest fecal coliform counts (0.2 x 106 CFU kg–1) while the cake sewage sludge (CBS) had the greatest coliform counts of 178 x 106 CFU kg–1. The fecal coliform counts for SBS7 was about 33 x 106 CFU kg–1. Average soil test values in June 2002 exhibited: i) decrease in TIN (NO3-N + NH4-N), TP, K, Ca, Mg, Mn, and Fe; and ii) slight increase in Zn and Cu when compared with the June 1997 soil test results. The overall decrease in soil test values in 2002 might be associated with nutrient cycling and plant consumption. Although the average BG forage yield in 2002 (2.3 ± 0.7 Mg ha–1) was slightly lower than in 2000 (3.5 ± 1.2 Mg ha–1), yield differences in 2002 between the control (1.2 + 0.2 Mg ha–1) and treated plots (2.3 ± 0.5 Mg ha–1 to 3.3 ± 0.6 Mg ha–1) were indicative of a positive residual effect of applied sewage sludge. This study has shown that excessive build up of plant nutrients may not occur in beef cattle pastures that repeatedly received sewage sludge while favoring long-term increased forage yield of BG. All sources of N (sewage sludge and AMN) gave better forage production than the unfertilized control during years with sewage sludge application (1997–2000) and also during years with no sewage sludge application (2001–2002). The favorable residual effects of applied sewage sludge in 2002 may have had received additional boost from the amount of rainfall in the area.Conclusions Repeated applications of sewage sludge indicate no harmful effects on soil quality and forage quality. Our results support our hypothesis that repeated land application of sewage sludge to supply 90 and 180 kg N ha–1 would not increase soil sorption for nutrients and trace metals. Results have indicated that the concentrations of soil TIN and TP declined by almost 50% in plots with different nitrogen sources from June 1997 to June 2002 suggesting that enrichment of nitrogen and phosphorus is insignificant. The concentrations of soil nitrogen and phosphorus in 2002 following repeated application of sewage sludge were far below the contamination risk in the environment. The residual effect of these sewage sludge over the long term can be especially significant in many areas of Florida where only 50% of the 1 million ha of BG pastures are given inorganic nitrogen yearly.Recommendation and Outlook Successive land application of sewage sludge for at least three years followed by no sewage sludge application for at least two years may well be a good practice economically because it will boost and/or maintain sustainable forage productivity and at the same time minimize probable accumulation of nutrients, especially trace metals. Consecutive applications of sewage sludge may result in build up of some trace metals in some other states with initial high metallic content, but in this study, no detrimental effects on soil chemical properties were detected. The possibilities for economically sound application strategies are encouraging, but more and additional research is required to find optimal timing and rates that minimizes negative impacts on soil quality in particular or the environment in general. For proper utilization of sewage sludge, knowledge of the sewage sludges’ composition, the crop receiving it, are absolutely crucial, so that satisfactory types and rates are applied in an environmentally safe manner. There is still much to be learned from this study and this investigation needs to continue to determine whether the agricultural and ecological objectives are satisfied over the longer term.     

Ecotoxicology,where do you come from and where do you go? (2 pp)

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Does ecotoxicology really contribute to our knowledge about the function of an ecosystem or environment? Is ecotoxicology really a science of its own? The answers to these questions must be NO. The reasons lie in the origin and past of ecotoxicology.Like medicine, ecotoxicology does not have its own scientific theory, but rather borrows from other disciplines: the scientific theory of medicine is biology, and that of ecotoxicology is ecology and pharmacology. Neither medicine nor ecotoxicology see the normal status and routine function of their objects under study. Ecotoxicology regards the environment as being adversely impacted by anthropogenic noxes, mainly chemicals, perhaps based on a paradigm of permanent guilt.

     

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 &#181;g/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.     

Ferrioxalate-mediated photodegradation and mineralization of 4-Chlorophenol

INTENTION, GOAL, SCOPE, BACKGROUND: Advanced oxidation processes are powerful methods which are capable of transforming refractory, nonbiodegradable and/or toxic organic compounds into harmless end products such as carbon dioxide and water. However, one commen problem of all advanced oxidation processes is the high demand of electrical energy for ultraviolet lamps, which causes high operational costs. Minimization of the required irradiation time, and therefore the energy consumption, by optimization of other reaction conditions such as catalyst-oxidant type and concentration, pH, temperature, pollutant/oxidant ratio etc., therefore continues to gain importance. OBJECTIVE: The main objective of this study was the minimization of the required irradiation time through optimization of the use of a newly patented catalyst, ferrioxalate, and also to compare the performance of this catalyst with the performance of other AOPs. METHODS: Oxidation of 4-chlorophenol by photo-Fenton process using potassium ferrioxalate as a mediator was studied in a lab scale photoreactor. The influence of parameters such as hydrogen peroxide and ferrioxalate concentrations, initial pH, power-output, oxalate/iron ratio and different iron sources was evaluated. An upflow photoreactor equipped with a 1000 Watt high-pressure mercury vapour lamp and operating in a recirculation mode was used during photodegradation experiments. The extent of the reduction of 4-chlorophenol, Total Organic Carbon and Chemical Oxygen Demand was used to evaluate the photodegradation reaction. RESULTS AND DISCUSSION: The optimum pH range observed was found to be 2.7-3. The efficiency of 4-chlorophenol oxidation increased with increasing concentrations of hydrogen peroxide and ferrioxalate, reaching a plateau after the addition of 10 and 0.072 mM of those reagents, respectively. Using an Oxalate/iron ratio of 12 was 18% less efficient than using a ratio of 3:1. The efficiency increased with increasing radiation power. However, this increase was not linear. The UV/ferrioxalate/H2O2 process, by which complete mineralization of 100 mg l(-1) 4-chlorophenol was achieved in 20 min of total reaction time, was the most efficient process among the alternatives applied. CONCLUSIONS: The use of ferrioxalate as the catalyst was found to be more efficient than the use of Fe(II) and Fe(III) iron species. It was possible to completely mineralize 4-chlorophenol. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate that the ferrioxalate-mediated degradation of 4-chlorophenol requires less irradiation times than other advanced oxidation processes. There are mainly 19 phenol isomers and other toxic and nonbiodegradable organic compounds. We recommend that similar studies should be performed on many such compounds in order to attain a clear understanding of the performance of this catalyst. Because of its light sensitivity, this catalyst should be used immediately after its preparation. The use of low pressure mercury vapour lamps in this process should also be considered, since low power outputs may be enough for the process.     

Effect of arsenic and mercury speciation on inhibition of respiration rate in activated sludge systems

The inhibition effect of arsenite, As(III), arsenate, As(V), inorganic mercury, Hg(II) and methylmercury, MeHg, on the respiration rate of activated heterotrophic sludge microorganisms was evaluated. As(III) and MeHg were much more toxic to activated sludge than As(V) and Hg(II) respectively. The effect of various experimental parameters on the toxicity, such as sludge age, concentration of suspended solids and exposure time, was investigated. An increase of sludge age or the concentration of suspended solids reduces the observed inhibition. Longer exposure seems to dramatically increase the inhibition of As(III), MeHg and Hg(II) during the first hours of exposure, while the later inhibition increases at a slower rate. On the contrary, in the presence of As(V), 24 hours after exposure, the respiration rate was similar to that of the control biomass.