Ferric citrate-induced photodegradation of dyes in aqueous solutions

The photooxidation of dye solutions containing Fe(III)-citrate complexes was studied. The photodegradation under near-UV light of the five dyes, C. I. reactive red 2, C. I. reactive blue 4, C. I. reactive black 8, C. I. basic red 13 and C. I. basic yellow 2, in aqueous solutions at pH2.0 containing Fe(III)-citrate complexes was found to follow pseudo-first order kinetics. The photodegradation rates of the dye, C. I. reactive red 2, decreased with increasing the initial dye concentration in range of 20 – 60 mg/L . A comparatively higher photodegradation efficiency of the dye was gained under the condition of pH2.0 and the Fe(III) to citrate ratio 1:2.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 × 10^{? 3} h^{? 1} to 7.0 × 10^{? 3} h^{? 1}. The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

Photodegradation of Dyes in Aqueous Solutions containing Fe(III) -hydroxy Complex II. Solar Photodegradation Kinetics

The solar photodegradation of five dyes, C.I. reactive red 2, C.I. reactive blue 4, C.I. reactive black 8, C.I. basic red 13, and C.I. basic yellow 2, were studied in a sunlight/Fe(III)-hydroxy system. It was observed that the photodegradation of these five dyes were pseudo-first order reactions, which has a little difference with the photodegradation kinetics of the dyes with UV-light as the irradiation source. The comparison between the two studies is also conducted.     

阳极添加三价铁离子对沉积型微生物燃料电池运行特性的影响

以剩余污泥为底物和接种物,借助电化学交流阻抗等电化学分析方法,研究了阳极投加三价铁离子对沉积型微生物燃料电池(sediment microbial fuel cell, SMFC)电能输出及内阻分布的影响.结果表明,500 mg/L铁离子可有效改善SMFC的运行特性,功率密度峰值、底物降解速率和阳极污泥絮体大小分别上升到103.09 mW/m2、35.68 mg VSS/(m3/h)和190.33 μm.电化学阻抗谱分析表明,阴极欧姆内阻及极化内阻随铁离子浓度增加而降低,阳极内阻则随铁离子浓度增加先降低后增加,当三价铁离子添加浓度为500 mg/L时,阳极欧姆内阻和活化内阻与对照组相比分别下降了45.28%和47.97%.     

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.     

Transformation and Ecotoxicity of Carbamic Pesticides in Water (5 pp)

Background N-methylcarbamate insecticides are widely used chemicals for crop protection. This study examines the hydrolytic and photolytic cleavage of benfuracarb, carbosulfan and carbofuran under natural conditions. Their toxicity and that of the corresponding main degradation products toward aquatic organisms were evaluated. Methods Suspensions of benfuracarb, carbosulfan and carbofuran in water were exposed to sunlight, with one set of dark controls, for 6 days, and analyzed by 1H-NMR and HPLC. Acute toxicity tests were performed on Brachionus calyciflorus, Daphnia magna, and Thamnocefalus platyurus. Chronic tests were performed on Pseudokirchneriella subcapitata, and Ceriodaphnia dubia. Results and Discussion Under sunlight irradiation, benfuracarb and carbosulfan gave off carbofuran and carbofuran-phenol, while only carbofuran was detected in the dark experiments. The latter was degraded to phenol by exposure to sunlight. Effects of pH, humic acid and KNO3 were evaluated by kinetics on dilute solutions in the dark and by UV irradiation, which evidenced the lability of the pesticide at pH 9. All three pesticides and phenol exhibited acute and higher chronic toxicity towards the aquatic organisms tested. Conclusion Investigation on the hydrolysis and photolysis of benfuracarb and carbosulfan under natural conditions provides evidence concerning the selective decay to carbofuran and/or phenol. Carbofuran is found to be more persistent and toxic. Recommendations and Outlook The decay of benfuracarb and carbosulfan to carbofuran and the relative stability of this latter pesticide account for many papers that report the detection of carbofuran in water, fruits and vegetables.     

Effects of Mn(II) and Fe(II) on microbial removal of arsenic (III)

Goal, scope, and background  Arsenic contamination in groundwater creates severe health problems in the world. There are many physiochemical and biological methods available for remediation of arsenic from groundwater. Among them, microbial remediation could be taken as one of the least expensive methods, though it takes longer treatment time. The main objective of this research was to study the improvement on remediation by addition of some essential ion salts such as Mn and Fe. Materials and methods   Staphylococcus aureus, Bacillus subtilis, Klebsiella oxytoca, and Escherichia coli were taken as model microbes from Dhulikhel, 30 km east from Kathmandu, Nepal. Results and discussion  Microbes used in this study showed different abilities in their removal of As(III) with and without addition of Mn and Fe salts. The trend of remediation increased with time. S. aureus was found to be the best among the microbes used. It showed almost 100% removal after 48-h culture, both with and without Fe and Mn salts. Rate of removal of As increased with addition of Fe and Mn for all microbes. Removal efficiency was found to increase by about 32% on average after addition of salts in 24-h cultures of S. aureus.     

Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: Divergent reactions in the presence of organic ligands

Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H₂O₂, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA < 1:1), contrasting with the rapid oxidation of Fe(II) by O₂ and H₂O₂ at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology.     

Determination of C(5)-C(12) perfluoroalkyl carboxylic acids in river water samples in the Czech Republic by GC-MS after SPE preconcentration

A method employing solid phase extraction followed by gas chromatography-mass spectrometry with negative chemical ionization has been developed for determination of ultratrace concentrations of perfluoroalkyl carboxylic acids in river water. The effects of the experimental parameters, such as the pH, additions of NaCl and an ion-pairing agent (tetraethylammonium bromide) and the kind of the elution agent, on the efficiency of the test acid extraction have been studied. The analyte extraction recoveries and the limits of detection and determination have been found. The method developed has been tested on determinations of perfluoroalkyl carboxylic acids in the waters of the two largest Czech rivers, Vltava and Labe (Elbe). The best extraction results have been attained without any alteration of the sample pH, with an addition of tetrabutylammonium bromide (a concentration of 50 μg mL⁻¹ in the sample) and using methanol as the elution agent. Under these conditions, the recoveries of the test acids in the spiked real samples are within ranges from 60% to 104% and 53% to 111% for analyte concentration levels of 1.40 ng mL⁻¹ and 0.14 ng mL⁻¹, respectively, depending on the lengths of the perfluorinated chains of the acids. In general, the recovery decreases with increasing length of this chain. The method developed exhibits very low limits of detection and determination and the results are fully comparable with those obtained when using more expensive HPLC-MS/MS instrumentation. Typical values amount to tenths to tens of pg mL⁻¹ and units to one hundred pg mL⁻¹ for the limits of detection and determination, respectively; the measuring sensitivity increases with increasing length of the analyte chain. The analyzes of real samples from the Vltava and Elbe rivers have demonstrated that the results obtained are similar to the values published for contamination of the Elbe and other rivers in western and central Europe. The concentrations determined are of the order of units to tens of pg mL⁻¹ and the C₈-C₁₀ acids occur most often.     

Distribution of PCDDs and PCDFs in Soils Collected from the Denver Front Range - Principal Components Analysis of Diffuse Dioxin Sources (10 pp)

Background, Aims and Scope The Rocky Mountain Arsenal (RMA) is a US Army facility located northeast of Denver, Colorado that has been listed on the National Priorities List (NPL). It is currently being re-mediated under the authority of the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) and the Superfund Amendments and Reauthorization Act of 1986 (SARA). As part of the remediation activities at RMA, indications were found that a source of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) had existed on the RMA. As a result, investigations were undertaken to assess the possible nature and extent of any potential sources of PCDDs and PCDFs on the RMA site. In addition, other studies were conducted that examined PCDD/PCDF contamination in the Denver area. The goal of these studies was to examine nature and extent of PCDD/PCDF contamination both on the RMA as well as in the surrounding Denver area. The intent of this study was to characterize sources of dioxins (PCDDs) and dibenzofurans (PCDFs) at low environmental concentrations which might have originated from diffuse sources in the Denver Colorado area and in particular, the Rocky Mountain Arsenal (RMA) using Principal Component Analysis (PCA). Methods Over 200 soil samples were collected from the RMA and the Denver area. From the RMA, soil was collected as part of three studies that included a (1) random site-wide sampling of the RMA, (2) soils from the Western Tier Parcel (WTP), and (3) soils from Historic Use areas. Denver area soil samples were collected from five different land use categories: Residential, Agricultural, Open Space, Commercial, and Industrial. PCA was conducted on concentrations of 17 2,3,7,8-substuituted PCDD and PCDF congeners in 220 soil samples collected from the RMA and the Denver Front Range region. Results and Discussion PCA demonstrated the presence of possible minor sources of dioxins on the RMA. Current remediation efforts on RMA will result in the removal of these sources. Samples from the RMA were identified by the presence of a congener profile containing higher chlorinated PCDFs while the Denver Front Range areas were characterized by the presence of higher chlorinated PCDD congeners. The presence of a PCDF signature for the RMA samples does not necessarily indicate a major source of these contaminants on-site. Indeed, the relatively diffuse nature of the sample clusters would argue strongly against the presence of a single large source. Instead, the predominance of the PCDF congeners probably indicates the mixed industrial activities that took place on and near the site. Conclusion PCA results indicate that PCDD/PCDF profiles in soils collected from the RMA differed from those collected from the outlying Denver areas but that a major source of these contaminants was not present. Rather, the diffuse nature of sample clusters from the PCA indicated that the congener profile of RMA samples was most likely a result of the mixed industrial activities that historically have taken place on and near the site. PCA also indicated that many of the 'open area' (peripheral site-wide) RMA soils samples did not differ from Denver are reference congener profiles. This finding was also true for samples collected from the WTP that were essentially indistinguishable from Off-RMA reference samples. In addition, total TEQ concentrations in soils collected from WTP were similar to those measured in soils collected from the Denver Front Range areas indicating that lack of a major source of PCDD/PCDF within the WTP zones of the RMA. Recommendation and Outlook Analytical as well as statistical results of the soil congener data indicate that the WTP soils are indistinguishable from soils collected from non-industrial areas in the Denver area. This finding would support the recent 'de-listing' of the WTP from the other RMA areas and its' transfer to other authorities in the Denver area.     

Ecotoxicological Assessment of Sediment, Suspended Matter and Water Samples in the Upper Danube River. A pilot study in search for the causes for the decline of fish catches (12 pp)

Goals, Scope and Background Fish populations, especially those of the grayling (Thymallus thymallus), have declined over the last two decades in the upper Danube River between Sigmaringen and Ulm, despite intensive and continuous stocking and improvement of water quality since the 1970s. Similar problems have been reported for other rivers, e.g. in Switzerland, Great Britain, the United States and Canada. In order to assess if ecotoxicological effects might be related to the decline in fish catch at the upper Danube River, sediment, suspended matter and waste water samples from sewage treatment plants were collected at selected locations and analyzed in a bioanalytical approach using a battery of bioassays. The results of this pilot study will be used to decide if a comprehensive weight-of-evidence study is needed. Methods Freeze-dried sediments and suspended particulate matters were extracted with acetone in a Soxhlet apparatus. Organic pollutants from sewage water were concentrated using XAD-resins. In order to investigate the ecotoxicological burden, the following bioassays were used: (1) neutral red assay with RTL-W1 cells (cytotoxicity), (2) comet assay with RTLW1 cells (genotoxicity), (3) Arthrobacter globiformis dehydrogenase assay (toxicity to bacteria), (4) yeast estrogen screen assay (endocrine disruption), (5) fish egg assay with the zebrafish (Danio rerio; embryo toxicity) and (6) Ames test with TA98 (mutagenicity). Results and Discussion The results of the in vitro tests elucidated a considerable genotoxic, cytotoxic, mutagenic, bacteriotoxic, embryotoxic and estrogenic burden in the upper Danube River, although with a very inhomogeneous distribution of effects. The samples taken from Riedlingen, for example, induced low embryo toxicity, but the second highest 17β-estradiol equivalent concentration (1.8 ng/L). Using the fish egg assay with native sediments, a broad range of embryotoxic effects could be elucidated, with clear-cut dose-response relationships for the embryotoxic effects of contaminated sediments. With native sediments, embryotoxicity was clearly higher than with corresponding pore waters, thus corroborating the view that – at least for fish eggs – the bioavailability of particle-bound lipophilic substances in native sediments is higher than generally assumed. The effect observed most frequently in the fish egg assay was a developmental delay. A comparison of our own results with locations along the rivers Rhine and Neckar demonstrated similar or even higher ranges of ecotoxicological burdens in the Danube River. Conclusions The complex pattern of ecotoxicological effects caused by environmental samples from the Danube River, when assessed in an in vitro biotest battery using both acute and more specific endpoints, showed that integration of different endpoints is essential for appropriate hazard assessment. Overall, the ecotoxicological hazard potential shown has indeed to be considered as one potential reason for the decline in fish catches at the upper Danube River. However, based on the results of this pilot study, it is not possible to elucidate that chemically induced alterations are responsible for the fish decline. Recommendations and Perspective . In order to confirm the ecological relevance of the in vitro results for the situation in the field and especially for the decline of the grayling and other fishes, further integrated investigations are required. For linking the weight of evidence obtained by in vitro assays and fish population investigations, the application of additional, more specific biomarkers (e.g. vitellogenin induction, EROD and micronucleus assay) has been initiated in fish taken from the field as well as in situ investigations.