Sensitivity of green and blue-green algae to methyl tert-butyl ether

The toxicity of methyl tert-butyl ether (MTBE) to Chlorella ellipsoidea and Aphanizomenon flos-aquae was tested and assessed for a 15-d incubation with concentrations of MTBE from high (2.00×104 mg/L) to low (2 mg/L). The results showed that the toxicity was low when the concentration of MTBE was in the range 1.00×104-2.00×104 mg/L (the greatest inhibition of growth-rate was 70%-71%, occurred during the day 1-5). Low concentrations (2-500 mg/L) stimulated algal growth up to the greatest effect of 85%-200% w...     

Effects of nitrogen and phosphorus concentrations on the bioaccumulation of polybrominated diphenyl ethers by Prorocentrum donghaiense

The growth, cellular total lipids, bioaccumulation amount, and bioaccumulation factors (BAFs) of 2,4,4 ′ -tribromodiphenyl ether (BDE28), 2,2 ′ ,4,4 ′ -tetrabromodiphenyl ether (BDE47), and 2,2 ′ ,4,4 ′ ,5-pentabromodiphenyl ether (BDE99) in a semi-continuous culture of Prorocentrum donghaiense were studied in relation to nitrate (0, 128, and 512 μmol/L) and phosphate (0, 8, and 32 μmol/L) concentrations. The BDE28, BDE47, and BDE99 content per cell under 0 μmol N/L were 3.77 × 10 6 , 3.95 × 10 6 , and 4.32 × 10 6 ng/cell, respectively, which were significantly higher than those under 128 and 512 μmol N/L. A nearly 5-fold increase in polybrominated diphenyl ether (PBDE) content per algal cell was found between 0 and 8 μmol P/L and between 8 and 32 μmol P/L. With increasing N and P concentrations, the PBDE content per volume of algal culture and the accumulation percentage of available PBDEs declined slightly. The BAFs for the PBDEs based on lipids showed that the logBAF lip under 0 μmol N/L was higher than those under 128 and 512 μmol N/L. The logBAF lip under 0 μmol P/L was higher than that under 8 μmol P/L but lower than that under 32 μmol P/L. Correlation analysis indicated a significant negative correlation between nutrient concentration and cellular total lipids, as well as the PBDE content per cell. The results indicate that different N and P concentrations change the total lipids content of P. donghaiense, thereby resulting in varying PBDE accumulation.     

Efficient visible light photo-Fenton-like degradation of organic pollutants using in situ surface-modified BiFeO3 as a catalyst

The visible light photo-Fenton-like catalytic performance of BiFeO₃ nanoparticles was investigated using Methyl Violet (MV), Rhodamine B (RhB) and phenol as probes. Under optimum conditions, the pseudo first-order rate constant (k) was determined to be 2.21×10^-2, 5.56×10^-2 and 2.01×10^-2 min^-1 for the degradation of MV (30 μmol/L), RhB (10 μmol/L) and phenol (3 mmol/L), respectively, in the BiFeO₃-H₂O₂-visible light (Vis) system. The introduction of visible light irradiation increased the k values of MV, RhB and phenol degradation 3.47, 1.95 and 2.07 times in comparison with those in dark. Generally, the k values in the BiFeO₃-H₂O₂-Vis system were accelerated by increasing BiFeO₃ load and H₂O₂ concentration, but decreased with increasing initial pollutant concentration. To further enhance the degradation of pollutants at high concentrations, BiFeO₃ was modified with the addition of surface modifiers. The addition of ethylenediamineteraacetic acid (EDTA, 0.4 mmol/L) increased the k value of MV degradation (60 μmol/L) from 1.01×10^-2 min^-1 in the BiFeO₃-H₂O₂-Vis system to 1.30 min^-1 in the EDTA-BiFeO₃-H₂O₂-Vis system by a factor of 128. This suggests that in situ surface modification can enable BiFeO₃ nano-particles to be a promising visible light photo-Fenton-like catalyst for the degradation of organic pollutants.     

Occurrence and infection risk of waterborne pathogens in Wanzhou watershed of the Three Gorges Reservoir, China

The Three Gorges Reservoir (TGR), formed by China’s Yangtze Three Gorges Project, is the largest lake in the world, but there is too little information available about fecal contamination and waterborne pathogen impacts on this aquatic ecosystem. During two successive 1-year study periods (July 2009 to July 2011), the water quality in Wanzhou watershed of the TGR was tested with regard to the presence of fecal indicators and pathogens. According to Chinese and World Health Organization water quality standards, water quality in the mainstream was good but poor in backwater areas. Salmonella, Enterohemorrhagic Escherichia coli (EHEC), Giardia and Cryptosporidium were detected in the watershed. Prevalence and concentrations of the pathogens in the mainstream were lower than those in backwater areas. The estimated risk of infection with Salmonella, EHEC, Cryptosporidium, and Giardia per exposure event ranged from 2.9 × 10 -7 to 1.68 × 10-5 , 7.04 × 10-10 to 2.36 × 10-7 , 5.39 × 10-6 to 1.25 × 10-4 and 0 to 1.2 × 10-3 , respectively, for occupational divers and recreational swimmers exposed to the waters. The estimated risk of infection at exposure to the 95% upper confidence limit concentrations of Salmonella, Cryptosporidium and Giardia may be up to 2.62 × 10-5 , 2.55 × 10-4 and 2.86 × 10-3 , respectively. This study provides useful information for the residents, health care workers and managers to improve the safety of surface water and reduce the risk of fecal contamination in the TGR.     

Temporal and spatial changes in nutrients and chlorophyll-a in a shallow lake, Lake Chaohu, China: An 11-year investigation

Temporal and spatial changes of total nitrogen (TN), total phosphorus (TP) and chlorophyll-a (Chl-a) in a shallow lake, Lake Chaohu, China, were investigated using monthly monitoring data from 2001 through 2011. The results showed that the annual mean concentration ranges of TN, TP, and Chl-a were 0.08-14.60 mg/L, 0.02-1.08 mg/L, and 0.10-465.90 μg/L, respectively. Our data showed that Lake Chaohu was highly eutrophic and that water quality showed no substantial improvement during 2001 through 2011. The mean concentrations of TP, TN and Chl-a in the western lake were significantly higher than in the eastern lake, which indicates a spatial distribution of the three water parameters. The annual mean ratio of TN:TP by weight ranged from 10 to 20, indicating that phosphorus was the limiting nutrient in this lake. A similar seasonality variation for TP and Chl-a was observed. Riverine TP and NH₄⁺ loading from eight major tributaries were in the range of 1.56×10⁴-5.47×10⁴ and 0.19×10⁴-0.51×10⁴ tons/yr over 2002-2011, respectively, and exceeded the water environmental capability of the two nutrients in the lake by a factor of 3-6. Thus reduction of nutrient loading in the sub-watershed and tributaries would be essential for the restoration of Lake Chaohu.     

Estrogenic activities of two synthetic pyrethroids and their metabolites

Synthetic pyrethroids(SPs) are among the most common pesticides in current use,and so far,several SPs have been assessed for their potential estrogenicities by various methods.Previous studies have shown that the estrogenicities partly come from their metabolites.Although considerable information is available with respect to the metabolism and environmental degradation of SPs,little is known about the estrogenicities of the metabolites.In this study,permethrin(PM) and β-cypermethrin(CP),as well as their metabolites(3-phenoxybenzoic alcohol(PBCOH),3-phenoxybenzaldehyde(PBCHO) and 3-phenoxybenzoic acid(PBCOOH) were evaluated for their estrogenic activities in the MCF-7 human breast carcinoma cell line.In the MCF-7 cell proliferation assay,PM and CP exhibited significant estrogenic activities at 10-7 mol/L,comparable to 17β-estradiol(E2 ) of 10-9 mol/L,with the relative proliferative effect ratios of 55.4% and 56.3%,respectively.The real-time quantitative polymerase chain reaction(qRT-PCR) results confirmed the estrogenicities of PM and CP with significant alteration of pS2 and ERα mRNA levels observed at 10-6 mol/L.For the three major metabolites,PBCOH and PBCOOH exhibited estrogenic activities in all assays,while no significant estrogenic responses was observed for PBCHO compared to the vehicle control.In particular,PBCOH had even slightly stronger estrogenic activity than its parent compounds,indicating that metabolism may be one of the reasons for the estrogenicities of the SPs.Given the widespread use of SPs,the toxicological effects of parent compounds and their metabolites should be taken into consideration in the risk assessment of SPs.     

Preparation, characterization and application of CuCrO2/ZnO photocatalysts for the reduction of Cr(VI)

The delafossite CuCrO₂ elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstructure is fairly homogenous with a mean crystallite size of ca. 2 μm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of -0.26 V_SCE. As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO₂/ZnO (1/1). CuCrO₂ is photoactivated by visible light and the electrons in the conduction band (-1.34 V_SCE) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25℃, 5×10^-4 mol/L) because of the HCrO₄^- dark adsorption onto ZnO (4HCrO₄^- + 3C₇H₆O₃ + 18O₂ + 16H⁺ → 4Cr³⁺ + 21CO₂ + 19H₂O, ΔG⁰ = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 μmol/(hr·g).     

Photodegradation of new herbicide HW-02 in organic solvents

HW-02 is a new organophosphates herbicide which is discovered and developed in China. The kinetics and mechanism of HW- 02 photodegradation in the organic solvents were studied at 25°C under the irradiation of ultraviolet light. The results showed that photochemical reaction of HW-02 in organic solvents such as n-hexane, methanol, dimethyl benzene and acetone under UV light could be well described by the first kinetic equation, and the photodegradation efficiency decreased with a order of n-hexane methanol xylene acetone. The photodegradation efficiency constant of HW-02 in n-hexane, methanol, xylene and acetone were 4.951 × 10 2 , 3.253 × 10 2 , 2.377 × 10 2 and 1.628 × 10 2 min 1 , and the corresponding half-lives were 13.99, 21.20, 29.15 and 42.56 min, respectively. By separation and identification of photoproducts using GC-MS, it could be concluded that HW-02 was photolyzed through ester cleavage, photo-dechlorination and photoisomerization of the molecule itself.     

Kinetics and mechanisms of p-nitrophenol biodegradation by Pseudomonas aeruginosa HS-D38

The kinetics and mecswithhanisms of p-nitrophenol (PNP) biodegradation by Pseudomonas aeruginosa HS-D38 were investigated. PNP could be used by HS-D38 strain as the sole carbon, nitrogen and energy sources, and PNP was mineralized at the maximum concentration of 500 mg/L within 24 h in an mineral salt medium (MSM). The analytical results indicated that the biodegradation of PNP fit the first order kinetics model. The rate constant k_PNP is 2.039 × 10⁻²/h in MSM medium, K_PNP+N is 3.603 × 10⁻²/h with the addition of ammonium chloride and K_PNP+C is 9.74 × 10⁻³/h with additional glucose. The addition of ammonium chloride increased the degradation of PNP. On the contrary, the addition of glucose inhibited and delayed the biodegradation of PNP. Chemical analysis results by thin-layer chromatography (TLC), UV-Vis spectroscopy and gas chromatography (GC) techniques suggested that PNP was converted to hydroquinone (HQ) and further degraded via 1,2,4-benzenetriol (1,2,4-BT) pathway.     

Environmental chamber study of the photochemical reaction of ethyl methyl sulfide and Nox

A series of experiments were conducted in a self-made smog chamber at 300 ± 1 K and 1.01×105 Pa to simulate the photochemical reaction of ethyl methyl sulfide (EMS) and NOx. The results show that the higher the initial concentration of EMS, the more ozone is generated in the simulative reactions. It is found that the light intensity plays a very important role in the evaluation of ozone formation potential for EMS. The parameters of d(O3-NO) and IR (incremental reactivity) were used to quantify the potential of EMS on ozone formation. The obtained maximum IR values in this paper for the five simulative reactions were 1.55×10-2, 0.99×10-2, 1.36×10-2, 2.47×10-2, and 1.65×10-2, respectively. Comparison between the results we obtained here and the results we obtained before for di-tert-butyl peroxide and acetylene was made and it showed that the potential reactivity of EMS on ozone formation is at a relatively low level.     

甲萘威的淡水水生生物水质基准研究

为保护我国淡水水生生物,收集、筛选出5门23科44个物种的急性毒性数据和1门1科2个物种的慢性毒性数据,分别采用毒性百分数排序法和物种敏感度分布法,对我国甲萘威的淡水水生生物水质基准进行推导. 结果表明:我国淡水水生生物物种的急性毒性平均值范围为2.25～27 609 μg/L,甲壳纲急性毒性平均值范围为2.25～1 000 μg/L,鱼纲急性毒性平均值范围为700～27 609 μg/L,最敏感的物种为棘爪网纹溞,最不敏感的物种为胡鲶. 毒性百分数排序法推导出的基准最大浓度和基准连续浓度均为2.6 μg/L,物种敏感度分布法推导出的短期危险浓度和长期危险浓度分别为3.3和1.6 μg/L. 中美甲萘威的水质基准值差异归因于两国生物区系的不同. 甲壳纲对甲萘威的敏感度大于鱼纲. 初步统计表明,在22个天然水体样品中,有50%样品的甲萘威浓度高于淡水水质基准,存在环境风险.      

Settling and dewatering characteristics of granulated methane-oxidizing bacteria

We evaluated the settling ability and dewaterability of granulated methane-oxidizing bacteria (GMOB) after granulation using a continuous-flow reactor. A comparative analysis on settling and dewatering characteristics due to changes in sludge retention time (SRT, 10, 15 and 20 days) during cultivation of GMOB was conducted. In assessing dewaterability, the specific resistance to filtration (SRF) of activated sludge and GMOB was found to be 8.21×1013-2.38×1014 and 4.88 × 1012-1.98×1013 m/kg, respectively. It was confirmed that as SRT decreased, SRF of GMOB increased. In the case of bound extracellular polymeric substance (EPS), activated sludge registered 147.5 mg/g-VSS while GMOB exhibited 171-177.2 mg/g-VSS. In the case of extracellular polymeric substance soluble EPS in effluent, activated sludge measured 62 mg/L and GMOB had 17.4-21.4 mg/L. The particle size analysis showed that mean particle diameters of GMOB were 402, 369, and 350 μm, respectively, at SRTs of 20, 15 and 10 days. In addition, it was found that GMOB had a larger mean particle diameter and exhibited much better settleability and dewaterability than activated sludge did.     

Determination of paraquat in water samples using a sensitive fluorescent probe titration method

Paraquat (PQ), a nonselective herbicide, is non-fluorescent in aqueous solutions. Thus, its determination through direct fluorescent methods is not feasible. The supramolecular inclusion interaction of PQ with cucurbit[7]uril was studied by a fluorescent probe titration method. Significant quenching of the fluorescence intensity of the cucurbit[7]uril-coptisine fluorescent probe was observed with the addition of PQ. A new fluorescent probe titration method with high selectivity and sensitivity at the ng/mL level was developed to determine PQ in aqueous solutions with good precision and accuracy based on the significant quenching of the supramolecular complex fluorescence intensity. The proposed method was successfully used in the determination of PQ in lake water, tap water, well water, and ditch water in an agricultural area, with recoveries of 96.73% to 105.77%. The fluorescence quenching values (ΔF) showed a good linear relationship with PQ concentrations from 1.0×10^-8 to 1.2× 10^-5 mol/L with a detection limit of 3.35×10^-9 mol/L. In addition, the interaction models of the supramolecular complexes formed between the host and the guest were established using theoretical calculations. The interaction mechanism between the cucurbit[7]uril and PQ was confirmed by ¹H NMR spectroscopy.     

Sunlight-driven reduction of silver ion to silver nanoparticle by organic matter mitigates the acute toxicity of silver to Daphnia magna

Due to the unique antibacterial activities, silver nanoparticles (AgNPs) have been extensively used in commercial products. Anthropogenic activities have released considerable AgNPs as well as highly toxic silver ion (Ag⁺) into the aquatic environment. Our recent study revealed that ubiquitous natural organic matter (NOM) could reduce Ag⁺ to AgNP under natural sunlight. However, the toxic effect of this process is not well understood. In this work, we prepared mixture solution of Ag⁺ and AgNPs with varied Ag⁺% through the sunlight-driven reduction of Ag⁺ by NOM and investigated the acute toxicity of the solutions on Daphnia magna. Formation of AgNPs was demonstrated and characterized by comprehensive techniques and the fraction of unconverted Ag⁺ was determined by ultrafiltration-inductively coupled plasma mass spectrometry determination. The formation of AgNPs enhanced significantly with the increasing of solution pH and cumulative photosynthetically active radiation of sunlight. The toxicity of the resulting solution was further investigated by using freshwater crustacean D. magna as a model and an 8 hr-median lethal concentration (LC₅₀) demonstrated that the reduction of Ag⁺ by NOM to AgNPs significantly mitigated the acute toxicity of silver. These results highlight the importance of sunlight and NOM in the fate, transformation and toxicity of Ag⁺ and AgNPs, and further indicate that the acute toxicity of AgNPs should be mainly ascribed to the dissolved Ag⁺ from AgNPs.     

Investigation of potential interferences on the measurement of dissolved reactive phosphate using zirconium oxide-based DGT technique

A diffusive gradients in thin films (DGT) technique based on hydrous zirconium oxide (Zr-oxide) has been recently developed for the measurement of dissolved reactive phosphate (DRP). In this study, the detailed performance of the DGT technique is reported. Spiking experiments revealed that several orthophosphate monoester compounds contributed to the Zr-oxide DGT measurements of DRP. However, such a phenomenon is unlikely to occur during field conditions due to the low concentration of organic P in typical natural waters. The presence of Cl- (up to 106 g/L), SO42- (up to 16 g/L), HCO3- (up to 817 g/L), and AsO2- and AsO 3 4 (both up to 1 mg As/L) in solutions had negligible effects on the measurement of DRP. The threshold concentrations of Cl-, SO42- and HCO3- have been increased from previous reports for the measurements of DRP using other adsorbent-based DGT techniques. The capacity for DGT measurements of DRP decreased with increasing solution pH (4.2-9.2). The lowest capacity (95 μg P/m2 at pH 9.2) was still greater than that of other DGT techniques that are usually used for the measurement of DRP (2-12 μg P/cm2 ). The Zr-oxide binding gel could be stored for up to 2 years without any aging effect. This period of validity was considerably longer than the ferrihydrite binding gel that is commonly used in present DGT devices (6 months). The field application revealed that the concentrations of DRP measured in three fresh water samples using the Zr-oxide DGT technique were in agreement with those of the traditional colorimetric method.     

Synergistic photocatalytic degradation of pyridine using precious metal supported TiO2 with KBrO3

A series of precious metals catalysts （M/TiO/, M = Ru, Rh, Pd, Ag, Ir, Pt or Au） were prepared by a light deposition method and the synergistic photocatalytic degradations of pyridine （20 mg/L） under UV irradiation （365 nm） using M/TiO2 with electron capture agent KBrO3 have been investigated. The results show that KBrO3 has a greatly synergistic role on M/TiO2 and the photocatalytic activity of M/TiO2 is closely related to its work function. Ag could greatly enhance the activity of TiO2 due to the binding characteristics of pyridine on Ag. Under the conditions of 0.5 wt.% Ag loading, Ag/TiO2 concentration of 0.1 g/L, KlrO3 concentration of 10 mmol/L and reaction liquid pH value at 9, the pyridine can be degraded by 64% within 3 hr, doubled than TiO2 photocatalytic system. The degradation kinetics of pyridine follows first-order kinetics and k = 5.53 × 10-3 min^-1.     

纳米氧化锌致大型溞的毒性效应特征

采用半静态暴露的方法,以大型溞的死亡率、显微结构损伤、蜕皮率、游泳行为等作为毒性测试终点,研究不同浓度纳米氧化锌(ZnONP)对大型溞(Daphnia magna)的毒性效应.结果显示,ZnONP水溶液稳定性差,在溶液中沉降率随着浓度增大而增大,Zeta电位降低.ZnONP对大型溞处理48 h的半数致死浓度LC_(50)为3 mg·L~(-1),ZnONP致大型溞的死亡率呈现一定的时间-效应关系;ZnONP暴露会使大型溞肠道和体表损伤.经显微结构观察发现,ZnONP可粘附在大型溞体表面,并引起大型溞游泳的垂直高度升高,大型溞蜕皮时间延迟,成功蜕皮率降低.结果表明ZnONP对大型溞个体和行为产生一定的毒性效应,其毒性效应的机理与其颗粒物对大型溞肠道和体表粘附有直接的关系,研究结果对合理地评价纳米材料对水生生物的影响有一定的理论参考价值.     

An improved GC-ECD method for measuring atmospheric N2O

Gas chromatography equipped with an electron capture detector (GC-ECD) has been widely used for measuring atmospheric N2O,but nonlinear response and the influence of atmospheric CO2 have been recognized as defects for quantification.An original GCECD method using N 2 as carrier gas was improved by introducing a small flow rate of CO2 makeup gas into the ECD,which could well remedy the above defects.The N2O signal of the improved method was 4-fold higher than that of the original method and the relative standard deviation was reduced from > 1% to 0.31%.N2O concentrations with different CO2 concentrations (172.2×10-6-1722×10-6mol/mol) measured by the improved GC-ECD method were in line with the actual N2O concentrations.However,the N2O concentrations detected by the original method were largely biased with a variation range of-4.5%～7%.The N2O fluxes between an agricultural field and the atmosphere measured by the original method were greatly overestimated in comparison with those measured by the improved method.Good linear correlation (R2=0.9996) between the response of the improved ECD and N2O concentrations (93×10-9-1966×10-9mol/mol) indicated that atmospheric N2O could be accurately quantified via a single standard gas.Atmospheric N2O concentrations comparatively measured by the improved method and a high precision GC-ECD method were in good agreement.     

Photocatalytic degradation of Rhodamine B bymicrowave-assisted hydrothermal synthesized N-doped titanate nanotubes

Microwave-induced nitrogen-doped titanate nanotubes（NTNTs） were characterized by transmission electron microscopy（TEM）, X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, Fourier transform infrared spectroscopy（FT-IR）, Zeta potential analysis,specific surface area（SBET）, and UV-Visible spectroscopy. TEM results indicate that NTNTs retain a tubular structure with a crystalline multiwall and have a length of several hundred nanometers after nitrogen doping. XRD findings demonstrate that the crystalline structure of NTNTs was dominated by anatase, which is favored for photocatalytic application. The Ti-O-N linkage observed in the XPS N 1s spectrum is mainly responsible for narrowing the band gap and eventually enhancing the visible light photoactivity. FT-IR results demonstrated the existence of H3O＋, which could be excited by photo-generated holes to form hydroxyl radicals and degrade environmental pollutants. After sintering at 350°C, the UV-Vis absorbance edges of NTNTs significantly shift to the visible-light region, which indicates N atom doping into the nanotubes. Photocatalytic degradation of Rhodamine B（RhB） via NTNTs show good efficiency, with pseudo first-order kinetic model rate constants of 3.7 × 10-3, 2.4 × 10-3and 8.0 × 10-4sec-1at pH 3, 7, and 11, respectively.