Photocatalytic bacterial inactivation by polyoxometalates

The photocatalytic inactivation (PCI) of Escherichia coli (Gram-negative) and Bacillus subtilis (Gram-positive) was performed using polyoxometalate (POM) as a homogeneous photocatalyst and compared with that of heterogeneous TiO₂ photocatalyst. Aqueous suspensions of the microorganisms (10⁷–10⁸ cfu ml⁻¹) and POM (or TiO₂) were irradiated with black light lamps. The POM-PCI was faster than (or comparable to) TiO₂-PCI under the experimental conditions employed in this study. The relative efficiency of POM-PCI was species-dependent. Among three POMs (H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, and H₄SiW₁₂O₄₀) tested in this study, the inactivation of E. coli was fastest with H₄SiW₁₂O₄₀ while that of B. subtilis was the most efficient with H₃PW₁₂O₄₀. Although the biocidal action of TiO₂ photocatalyst has been commonly ascribed to the role of photogenerated reactive oxygen species such as hydroxyl radicals and superoxides, the cell death mechanism with POM seems to be different from TiO₂-PCI. While TiO₂ caused the cell membrane disruption, POM did not induce the cell lysis. When methanol was added to the POM solution, not only the PCI of E. coli was enhanced (contrary to the case of TiO₂-PCI) but also the dark inactivation was observed. This was ascribed to the in situ production of formaldehyde from the oxidation of methanol. The interesting biocidal property of POM photocatalyst might be utilized as a potential disinfectant technology.     

Biotransformation of ethinylestradiol by microalgae

The capability of biotransformation of 11 microalgae strains was tested on ethinylestradiol (EE). Seven strains were ineffective whilst Selenastrum capricornutum, Scenedesmus quadricauda, Scenedesmus vacuolatus and Ankistrodesmus braunii biotransformed the substrate. EE was converted by S. capricornutum in three products (ethinylestradiol glucoside, 3-β-d-glucopyranosyl-2-hydroxyethinylestradiol, and 3-β-d-glucopyranosyl-6β-hydroxyethinyl estradiol) in 40%, 5%, and 5% yields, respectively. S. quadricauda transformed EE into 17-ethinyl-1,4-estradien-10,17β-diol-3-one (12%) and A. braunii transformed EE into 6--hydroxy-ethinylestradiol (25%).

It is noteworthy that EE is converted in 92% yield in ethinylestradiol glucoside by S. capricornutum when using optimal algal density conditions.     

Organically bound halogens in coniferous forest soil -Distribution pattern and evidence of in situ production

We examined organically bound halogens in a coniferous soil profile and in Norway spruce litter enclosed in litter bags and subjected to degradation in field. Throughout the soil profile the total amount of organically bound halogens (TOX, μg Cl/g soil) was related to organic matter, i.e. amounts decreased with increasing depth. In contrast, the organic chlorine to organic carbon ratio (mg Cl_org:g C_org) increased with increasing depth, and a pronounced increase in this ratio was observed in the transition between the O-horizon and the A-horizon, strongly indicating that in situ production of organically bound halogens occur in soil. This conclusion was strengtened by the results of the litter bag study, which clearly showed that a net-production of organically bound halogens occurred during decomposition of the spruce needle litter. Furthermore, this part of the study showed that organically bound halogens are not a static factor of organic matter. On the contrary, the results strongly indicated that during decomposition of organic matter, organically bound halogens are subjected to both production, i.e. incorporation of inorganic halides into organic matter, and mineralisation, i.e. release of inorganic halides from organic matter. A method previously developed in our laboratory to determine TOX in soil was further evaluated; there were no indications that inorganic halides interfere with the determination.     

Organochlorine pesticides accumulation and degradation products in vegetation samples of a contaminated area in Galicia (NW Spain)

The content of 21 organochlorine pesticides were studied in vegetation samples of a highly contaminated area by isomers of hexachlorocyclohexane (HCH) located close to a former industrial area in Galicia (NW Spain). Five species of plants were collected at different points of the contaminated area and the different parts of the plants were separated in order to study differences in accumulation capabilities. Samples were extracted employing microwave energy followed by a clean-up step using solid phase extraction and finally determined by GC–ECD. The results obtained show that the most abundant pesticides are HCHs isomers, being the main isomers β-HCH and -HCH in all samples whereas δ-HCH and γ-HCH were at lower levels. Some other pesticides such as p,p′-DDT, p,p′-DDD and p,p′-DDE were also present in much lower amount in some of the samples. Several degradation products of HCH were also identified in some samples by GC–MS.     

Screening 31 endocrine-disrupting pesticides in water and surface sediment samples from Beijing Guanting reservoir

For screening 31 potential or suspected endocrine-disrupting pesticides in water and surface sediments, a multiresidue analysis method based on gas chromatography with electron capture detection (GC/ECD) was developed. Solid phase extraction (SPE) technology with Oasis^® HLB cartridge was also applied in sample extraction. The relevant mean recoveries were 70–103% and 71–103% for water and sediment, respectively. Relative standard deviations (RSD) are 2.0–7.0%, 4.0–8.0% for water and sediment, respectively. Thirty one pesticides (-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene (HCB), aldrin, heptachlor, endosulfan I & II, p,p′-DDD, o,p′-DDT, p,p′-DDT, p,p′-DDE, endrin aldehyde, endosulfan sulphate, methoxychlor, hepachlor epoxide, -chlordane, γ-chlordane, dieldrin, endrin, dicofol, acetochlor, alachlor, metolachlor, chlorpyriphos, nitrofen, trifluralin, cypermethrin, fenvalerate, deltamethrin) in water and surface sediment samples from Beijing Guanting reservoir were analyzed. Concentrations of pesticides ranged from 7.59 to 36.0 ng g⁻¹ on a dry wt. basis for sediment samples, from 279.3 to 2740 ng l⁻¹ for pore waters and from 48.8 to 890 ng l⁻¹ for water samples, respectively, with a mean concentration of 10.7 ng g⁻¹ in sediment, 735 ng l⁻¹ in pore water and 295 ng l⁻¹ in water, respectively. The data obtained provides information on the levels and sources of endocrine-disrupting pesticides in Guanting reservoir. These results underscore the need to improved environmental protection measures in order to reduce the exposure of the population and aquatic biota to these endocrine-disrupting compounds.     

Growth, photosynthetic and respiratory responses to sub-lethal copper concentrations in Scenedesmus incrassatulus (Chlorophyceae)

In the present paper we investigated the effects of sub-lethal concentrations of Cu²⁺ in the growth and metabolism of Scenedesmus incrassatulus. We found that the effect of Cu²⁺ on growth, photosynthetic pigments (chlorophylls and carotenoids) and metabolism do not follow the same pattern. Photosynthesis was more sensitive than respiration. The analysis of chlorophyll a fluorescence transient shows that the effect of sub-lethal Cu²⁺ concentration in vivo, causes a reduction of the active PSII reaction centers and the primary charge separation, decreasing the quantum yield of PSII, the electron transport rate and the photosynthetic O₂ evolution. The order of sensitivity found was: Growth > photosynthetic pigments content = photosynthetic O₂ evolution > photosynthetic electron transport > respiration. The uncoupled relationship between growth and metabolism is discussed.     

The acute toxicity of chlorobenzenes for earthworms (Eisenia andrei) in different exposure systems

Earthworms (Eisenia andrei) were exposed to different concentrations of two chlorobenzenes (1,2,3-trichloro- and pentachlorobenzene) using different routes of administration: in water, in soil, via food and on filter paper. Except for the contact paper toxicity test, lethal body burdens (LBBs) measured in these different exposure systems were similar for the same test chemical. LBBs for 1,2,3-trichlorobenzene varied between 0.44 and 2.1 μmol/g and for pentachlorobenzene between 1.29 and 2.34 μmol/g. These values correspond with literature data for fish. For 1,4-dichloro- and 1,2,3,4-tetrachlorobenzene LBBs measured with the contact paper toxicity test were 0.33 and 3.2 μmol/g, respectively. Exposure to hexachlorobenzene and hexabromobenzene using the contact toxicity test did not result in death within 48 hours.     

Biofiltration of trimethylamine, dimethylamine, and methylamine by immobilized Paracoccus sp. CP2 and Arthrobacter sp. CP1

A biofilter using granular activated carbon with immobilized Paracoccus sp. CP2 was applied to the elimination of 10–250 ppm of trimethylamine (TMA), dimethylamine (DMA), and methylamine (MA). The results indicated that the system effectively treated MA (>93%), DMA (>90%), and TMA (>85%) under high loading conditions, and the maximum degradation rates were 1.4, 1.2, and 0.9 g-N kg⁻¹ GAC d⁻¹. Among the three different amines treated, TMA was the most difficult to degrade and resulted in ammonia accumulation. Further study on TMA removal showed that the optimal pH was near neutral (6.0–8.0). The supply of high glucose (>0.1%) inhibited TMA removal, maybe due to substrate competition. However, complete TMA degradation was achieved under the co-immobilization of Paracoccus sp. CP2 and Arthrobacter sp. CP1 (96%). Metabolite analysis results demonstrated that the metabolite concentrations decreased by a relatively small 27% while the metabolite apparently increased by heterotrophic nitrification of Arthrobacter sp. CP1 in the co-immobilization biofilter.     

Sorption of As, Cd and Tl as influenced by industrial by-products applied to an acidic soil: equilibrium and kinetic experiments

In situ stabilization of toxic elements in contaminated soils by the addition of amendments is being considered as an effective technique for remediation. In this paper, we performed both kinetics and equilibrium-based sorption experiments of three toxic elements (As, Cd and Tl) in soils amended with two by-products (phosphogypsum and sugar foam, rich in gypsum and calcium carbonate, respectively) to ascertain the feasibility of their application for improving the sorption capacity of As, Cd and Tl from the soil at 25, 35 and 50 °C. Kinetic studies indicated that the sorption follows a pseudo-second-order (PSO) kinetics and the sorption is a two-step diffusion process where both film and intraparticle diffusion played important roles in the sorption mechanisms of the elements. The Langmuir isotherms applied for sorption studies showed that the estimated maximum sorption capacity of the elements in control and amended soils decreased in the order of Cd > As > Tl. Using the thermodynamic equilibrium parameters obtained at different temperatures, the thermodynamic constants of sorption (ΔG, ΔH and ΔS) were also evaluated, indicating spontaneous and endothermic nature of the process, except Tl which was exothermic. An optimal scaling procedure was undertaken to determine the relationships between the kinetic and equilibrium sorption parameters. By means of statistical analysis it was seen that these inter-parametric relationships are dependent on the element nature.     

O3/H2O2法去除浮选药剂丁基黄药

采用O3/H2O2法去除水中丁基黄药,考察了H2O2/O3摩尔比、pH值、丁基黄药初始浓度、温度和自由基抑制剂对丁基黄药的去除效果的影响。结果表明,在相同O3投加量下,H2O2量越大,丁基黄药去除率越高。pH值为7～9,温度在293～303 K的范围内,O3/H2O2对丁基黄药都有很高的去除率。碳酸氢根和叔丁醇能在一定程度上降低丁基黄药的降解效率。研究还发现,在O3和H2O2投加量相同的条件下,H2O2多次投加对水中丁基黄药的处理效果明显优于一次性投加。GC/MS分析表明,O3/H2O2氧化丁基黄药氧化产物为羧酸类物质。     

Degradation of 1,4-dioxane in water with heat- and Fe2+-activated persulfate oxidation

This research investigated the 1,4-dioxane (1,4-D) degradation efficiency and rate during persulfate oxidation at different temperatures, with and without Fe²⁺ addition, also considering the effect of pH and persulfate concentration on the oxidation of 1,4-D. Degradation pathways for 1,4-D have also been proposed based on the decomposition intermediates and by-products. The results indicate that 1,4-D was completely degraded with heat-activated persulfate oxidation within 3–80 h. The kinetics of the 1,4-D degradation process fitted well to a pseudo-first-order reaction model. Temperature was identified as the most important factor influencing the 1,4-D degradation rate during the oxidation process. As the temperature increased from 40 to 60 °C, the degradation rate improved significantly. At 40 °C, the addition of Fe²⁺ also increased the 1,4-D degradation rate. Interestingly, at 50 and 60 °C, the 1,4-D degradation rate decreased slightly with the addition of Fe²⁺. This reduced degradation rate may be attributed to the rapid conversion of Fe²⁺ to Fe³⁺ and the production of an Fe(OH)₃ precipitate which limited the ultimate oxidizing capability of persulfate with Fe²⁺ under higher temperatures. Higher persulfate concentrations led to higher 1,4-D degradation rates, but pH adjustment had no significant effect on the 1,4-D degradation rate. The identification of intermediates and by-products in the aqueous and gas phases showed that acetaldehyde, acetic acid, glycolaldehyde, glycolic acid, carbon dioxide, and hydrogen ion were generated during the persulfate oxidation process. A carbon balance analysis showed that 96 and 93 % of the carbon from the 1,4-D degradation were recovered as by-products with and without Fe²⁺ addition, respectively. Overall, persulfate oxidation of 1,4-D is promising as an economical and highly efficient technology for treatment of 1,4-D-contaminated water.     

Study on the fluorescence characteristics of bromadiolone in aqueous and organized media and application in analysis

The fluorescence spectroscopic behavior of bromadiolone (anticoagulant rodenticide), a substituted 4-hydroxycoumarin derivative, was investigated in water and in organized media like micelles and cyclodextrins. A detailed study on various photophysical parameters like fluorescence intensity (I_F), quantum yield (), lifetime (τ) and steady state fluorescence anisotropy (r) of bromadiolone in aqueous and in organized media was carried out. Bromadiolone in aqueous solution was observed to be in an aggregated state, thereby showing weak emission due to self-quenching. Marked enhancement of fluorescence intensity was observed in organized media like micelles and β-cyclodextrin. A preliminary investigation has been done to find out whether this enhancement of fluorescence can be used to develop a sensitive analytical method for determination of bromadialone in aqueous media. A linear relationship between the fluorescence intensity and concentration of bromadiolone was observed in the range of 0.15–7.9 μg ml⁻¹ in cetyltrimethylammonium bromide (CTAB) and 0.5–26.4 μg ml⁻¹ in β-cyclodextrin medium. The lower detection limit was found to be 37 ng ml⁻¹ in presence of CTAB and 23 ng ml⁻¹ in β-cyclodextrin. Comparison with 4-hydroxycoumarin, an unsubstituted analogue, was made.     

Combined steam distillation and electrochemical peroxidation (ECP) treatment of river sediment contaminated by PCBs

A combined treatment process utilizing steam distillation followed by electrochemical peroxidation (ECP) has been utilized to remove >90% of the polychlorinated biphenyls (PCBs) in St. Lawrence River sediment and destroy 95% of the PCBs recovered in the condensate. 2 l of condensate were collected by boiling 500 grams of sediment containing 4.3 mg PCBs. Most of the PCBs (82.3%) were recovered as a small volume (<1 ml) of yellow oil floating on the condensate and coating glassware surfaces. The aqueous phase PCBs (182 μg/l) were destroyed (95%) by three sequential ECP treatments at 16.8°C and pH 5, utilizing 1 ml of H₂O₂ (3%) and periodically reversed current (0.75–1.0 A @ 10 volts). Oxidation is primarily mediated by hydroxyl radicals produced by the reaction of hydrogen peroxide with electrochemically generated ferrous iron (Fenton's reagent). This work suggests steam extraction, in combination with advanced oxidation technologies, provides an effective treatment strategy for contaminated solids.     

Iron-loaded mangosteen as a heterogeneous Fenton catalyst for the treatment of landfill leachate

Iron-loaded mangosteen shell powder (Fe-MSP) was found as an effective heterogeneous Fenton catalyst for the treatment of stabilized landfill leachate. Sonolytically produced catalyst has higher efficiency than other catalysts. At the optimal conditions (pH 3, catalyst concentration of 1,750 mg/L and hydrogen peroxide concentration of 0.26 M), 81 % of the chemical oxygen demand (COD) was removed effectively from the landfill leachate. But, the efficiency of Fe-MSP was reduced in the first recycling due to the poisoning of active sites. A metal leaching study indicated that the degradation of the pollutant is mainly due to solid Fe ions present in Fe-MSP rather than the leached ferrous and ferric ions. Hydroxyl radical production in the system was confirmed by the Fenton oxidation of benzoic acid. Compared to the homogeneous Fenton process, the heterogeneous Fenton process using Fe-MSP had higher COD removal efficiency, indicating the practical applicability of the prepared catalyst.     

CuO/γ-Al_2O_3类Fenton试剂降解丁基黄药

CuO/γ-Al2O3类Fenton试剂是降解丁基黄药的优良试剂。该试剂与传统的Fenton试剂相比,提高了反应的pH值,可在较高pH（4~5）条件下反应,而传统的Fenton试剂的适宜pH值一般在3以下。采用单因素实验和正交实验相结合的方法研究了pH、催化剂投加量、过氧化氢投加量以及反应时间对丁基黄药降解效果的影响,并对催化剂的使用寿命进行了探讨。研究结果表明,反应的最佳条件为：pH为4~5,催化剂投加量为6 g/L,过氧化氢用量为30 mg/L,反应30min。在此反应条件下,丁基黄药的降解率达98%以上;影响丁基黄药降解效果的因素大小顺序为：pH〉反应时间〉H2O2用量〉催化剂投加量,其中pH对CuO/γ-Al2O3类Fenton试剂降解丁基黄药的影响最为显著。     

Evaluation of an SOS-Chromotest-based approach for the isolation and detection of sediment-associated genotoxins

A series of experiments was conducted to evaluate an approach advanced by the St. Lawrence Centre (SLC) of Environment Canada for assessing the genotoxic potential of sediments. The SLC method entails the extraction, isolation and solvent exchange of the organic constituents in sediment, and the testing of these solubilized extracts with the SOS Chromotest (Escherichia coli PQ37). A total of five sediments, three variously contaminated by organic compounds and two reference materials certified for persistent organic chemicals, were Soxhlet-extracted. Each of the five extracts was then split, with a portion remaining in crude form and another portion fractionated into two molecular-weight classes of organic contaminants, thus yielding a total of 15 extract samples. The ability of the SOS Chromotest to detect genotoxins in the various organic extracts was evaluated and compared with that of the Ames Fluctuation Assay (Salmonella typhimurium, strain TA100). The intra-laboratory variance associated with the SOS Chromotest was also assessed. Procedural details are presented and results are discussed. The SOS Chromotest results were in good agreement with those of the Ames Fluctuation Assay, especially after metabolic activation. However, the E. coli PQ37 system was slightly more sensitive than the Salmonella assay for detecting genotoxins in the sediment extracts. The SOS Chromotest was also the most discriminating of the two assays, generating SOS-induction factors that were consistent with the organic contamination gradient reported in the sediment samples. The removal of macromolecules from the dichloromethane extracts by size-exclusion chromatography prior to testing enhanced the sensitivity of both test systems. The intra-laboratory variance of the SOS Chromotest ranged from 0.24% to 23.82%, depending on the extract sample. As applied in this study, the SOS Chromotest can serve as a sensitive test for screening the genotoxic potential of uncharacterized sediment extracts. A more sensitive assay would be appropriate, however, as a confirmation for definitive investigations, especially for the detection of direct-acting genotoxins.     

Possible involvement of frontier (π) electrons in the metabolism of poly-chlorinated biphenyls (PCBs)

The electron density, at each carbon atom, of the highest occupied π orbital of thirteen polychlorinated biphenyl (PCB) and one polychlorinated dibenzofuran (PCDF) molecules were calculated and the result was compared with their in vitro and/or in vivo metabolism. We noted that 1. the carbon position at which the frontier electron density was highest was most readily hydroxylated or sulfonated, 2. if the carbon with the highest frontier (π) electrons was occupied by chlorine, either a replacement occurred or the carbon with the next highest electron density was activated for metabolism, 3. due to steric hinderance ‘ortho’ carbons in PCBs were least preferred for such reactions inspite of possessing favorable electron density, 4. this was applicable to both phenobarbitol (PB) - type and 3-methyl cholanthrene (3 MC) - type PCB inducers. Frontier (π) electron density could be an easy guide for understanding the metabolic products of persistent and toxic environmental pollutants in vitro or in vivo and in understanding their environmental fate.     

Climate simulations using the GCRC 2-D zonally averaged statistical dynamical climate model

The two-dimensional statistical dynamical climate model, recently developed at the Global Change Research Center (GCRC 2D climate model) is presented and discussed. The model solves the 2-D primitive equations in finite difference form (mass continuity, Newton's second law, and the first law of thermodynamics) for the prognostic variables zonal mean density, zonal mean zonal velocity, zonal mean meridional velocity, and zonal mean temperature on a grid that has 18 nodes in latitude and 9 vertical nodes (plus the surface). The equation of state, p = ρRT and an assumed hydrostatic atmosphere, δp = −ρgδz, are used to diagnostically calculate the zonal mean pressure and vertical velocity for each grid node, and the moisture balance equation is used to estimate the precipitation rate.

The performance of the model at simulating the two-dimensional temperature, zonal winds, and mass stream function is discussed here. The strengths and weaknesses of the model are highlighted and plans for future model experiments and improvements are given. The parameterization of the transient eddy fluxes of heat and momentum developed by Stone and Yao (1987 and 1990) are used with small modifications. These modifications are shown to improve the performance of the model at simulating the observed climate system as well as increase the model's computational stability.     

Modified Fenton reaction for trichlorophenol dechlorination by enzymatically generated H2O2 and gluconic acid chelate

Glucose oxidase is a well-known enzyme that catalyzes the oxidation of β-d-glucose to produce gluconic acid and hydrogen peroxide. Fenton reaction is a powerful oxidation technology used for the oxidation of groundwater pollutants. For the application of Fenton reaction in groundwater remediation, successful operation of Fenton reaction near neutral pH, and on-site generation of both H₂O₂ and chelate will be beneficial. The focus of this experimental study was to couple the glucose oxidation reaction with chelate-based Fenton reaction. The idea was to use the hydrogen peroxide and chelate gluconic acid generated during glucose oxidation for the dechlorination of 2,4,6-trichlorophenol (TCP) by Fenton reaction. The oxidation of glucose was achieved using the enzyme in free and immobilized forms. The rate of production of hydrogen peroxide was determined for each system, and was used to estimate the time required for complete consumption of glucose during the process, thus avoiding any traces of glucose in the Fenton reaction. In the case of free enzyme reaction, separation of the enzyme was achieved using an ultrafiltration membrane before initiating the Fenton reaction. The oxidation of TCP by Fenton reaction was performed at varying ratios of gluconic acid/Fe, and its effect on the decomposition of TCP and H₂O₂ was studied. TCP degradation was studied both in terms of parent compound degradation and free chloride generation.     

Anaerobic biodegradation of 4-alkylphenols in a paddy soil microcosm supplemented with nitrate

Anaerobic degradation of phenol, p-cresol, 4-n-propylphenol (n-PP), 4-i-propylphenol (i-PP), 4-n-butylphenol (n-BP) and 4-sec-butylphenol (sec-BP) was observed in a paddy soil supplemented with nitrate. We detected the metabolites 4′-hydroxypropiophenone (HPP) from n-PP, 4-i-propenylphenol from i-PP, and 4-(1-butenyl)phenol and 4′-hydroxybutyrophenone (HBP) from n-BP. Compared with the original soils, Betaproteobacteria became predominant in the microcosm during the degradation of phenol and p-cresol whereas no remarkable change was observed in the community degrading propylphenols and butylphenols. The microcosm, however, did not degrade 4-t-butylphenol (t-BP), 4-t-octylphenol (t-OP) and 4-n-octylphenol (n-OP). Paddy soil supplemented with sulfate or iron (III) as electron acceptors did not degrade phenol and 4-alkylphenols with the exception of the degradation of p-cresol in sulfate-reducing conditions. It was demonstrated for the first time that anaerobic microbial degradation of alkylphenols, in a paddy soil supplemented with nitrate as an electron acceptor, occurred via oxidation of the alpha carbon in the alkyl chain.