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.     

Determination of photochemically-generated reactive oxygen species in natural water

Reactive oxygen species(ROS) can be produced by interactions between sunlight and light-absorbing substances in natural water environment.ROS may participate in the indirect photolysis of trace organic pollutants,therefore resulting in changes in their environmental fates and ecological risks in natural water systems.Bisphenol A(BPA),an endocrine-disrupting chemical,exits widely in natural waters.The photodegradation of BPA promoted by ROS(.OH,1O2,HO2./O2·-),which were produced on the excitation of ubiquito...     

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.     

Comparison of UV/PDS and UV/H2O2 processes for the degradation of atenolol in water

UV/H2O2 and UV/peroxodisulfate (PDS) processes were adopted to degrade a typical β-blocker atenolol (ATL). The degradation efficiencies under various operational parameters (oxidant dosage, pH, HCO3-, humic acid (HA), NO3- , and Cl-) were compared. Principal factor analysis was also performed with a statistical method for the two processes. It was found that increasing the specific dosage of the two peroxides ([peroxide]0/[ATL]0 ) ranging from 1:1 to 8:1 led to a faster degradation rate but also higher peroxide residual. Within the pH range 3-11, the optimum pH was 7 for the UV/PDS process and elevating pH benefitted the UV/H 2O2 process. The presence of HCO3- , HA, and Cl adversely affected ATL oxidation in both processes. The NO3- concentration 1-3 mmol/L accelerated the destruction of ATL by the UV/PDS process, but further increase of NO3- concentration retarded the degradation process, contrary to the case in the UV/H2O2 process. The rank orders of effects caused by the six operational parameters were pH ≈ specific dosage > [HA]0 > [NO3-]0 > [HCO3-]0 > [Cl-]0 for the UV/H2O2 process and specific dosage > pH > [HA]0 > [NO3-]0 > [HCO3-]0 >[Cl-]0 for the UV/PDS process. The UV/PDS process was more sensitive to changes in operational parameters than the UV/H2O2 process but more efficient in ATL removal under the same conditions.     

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.     

Involvements of chloride ion in decolorization of Acid Orange 7 by activated peroxydisulfate or peroxymonosulfate oxidation

The effects of Cl^- on the decolorization of AO7 by SO₄^·- based-peroxydisulfate or peroxymonosulfate oxidation under various activated conditions were different.     

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.     

固载化瓜环的制备及其对磺胺间甲氧嘧啶的吸附性能研究

在微波无极灯下将烯氧基瓜环固载到巯基硅胶(MSG)上,制得固载化瓜环(ACB[6]-SG).通过红外光谱表征固载产物,并研究固载化瓜环对磺胺间甲氧嘧啶(SMM)的吸附性能.结果表明,SMM在固载化瓜环上的吸附基本在2 min内即可达到平衡;Henry方程和Freundlich方程均能较好地拟合SMM在固载化瓜环和巯基硅胶上的等温吸附曲线,但是SMM在固载化瓜环上的吸附主要是在瓜环中的分配,而SMM在巯基硅胶上的吸附则主要是多分子层的表面吸附作用;SMM在固载化瓜环上的平衡吸附量远大于在巯基硅胶上的平衡吸附量;SMM在两者上的吸附过程是一个放热过程,温度越低吸附效果越好.     

Using a novel adsorbent macrocyclic compound cucurbit[8]uril for Pb removal from aqueous solution

In this study, cucurbit[8]uril (CB[8]) was utilized as a kind of new adsorbent to remove Pb^2 + ions from aqueous solution. With the solution pH increased from 2 to 6, the removal efficiency of adsorption increased from 55.6% to 74.5%correspondingly. The uptake of Pb^2 + increased rapidly in the initial 30 min, and then the adsorption rate became slower. The Pseudo-second order model could be used to interpret the adsorption kinetics satisfactorily; and the rate determining step in Pb^2 + adsorption onto CB[8] was the external mass transfer step. Equilibrium isotherm study reveals that the Langmuir model gave a better fitting result than Freundlich model. The maximum adsorption capacity calculated by the Langmuir model was 152.67 mg/g for 298 K, 149.70 mg/g for 313 K and 136.42 mg/g for 323 K, respectively. The adsorption is a spontaneous process of exothermic nature. The effect of the adsorbent dosage and the influences of solution pH and co-existing cations were also investigated. The CB[8] was synthesized and characterized by ¹H NMR, IR, ESI-MS spectra, SEM-EDAX, Zeta-potential and BET-analysis. The adsorption mechanism was due to the coordination between CB[8] molecule and Pb^2 + ions.     

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.     

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.     

典型可溶有机质与磺胺二甲嘧啶的络合作用研究

以藻源有机质(AOM)和腐殖酸(HA)作为典型生物大分子可溶有机质(DOM)和腐殖化DOM,采用荧光猝灭滴定和光谱分析考察磺胺二甲嘧啶(SMZ)与DOM的络合作用.三维荧光光谱结合平行因子分析显示AOM荧光组分主要由类酪氨酸和类色氨酸物质组成,而类富里酸和类腐殖酸物质是HA荧光组分的主要构成.4种荧光组分可与SMZ发生不同程度的静态猝灭,且猝灭过程中DOM分子构象改变.同步荧光光谱结合二维相关图谱进一步发现类酪氨酸优先于类色氨酸组分与SMZ发生络合作用.Ryan-Weber非线性模拟拟合表明AOM中各荧光组分与SMZ的络合稳定常数(logK)大小为:类富里酸(3.33)类酪氨酸(3.12)类色氨酸(2.15)类腐殖酸(1.57);而HA中大小为:类富里酸(3.06)类腐殖酸(2.02).总体上生物大分子DOM对SMZ的亲和力高于腐殖化DOM.DOM与SMZ的相互作用可改变水环境中抗生素的形态和归趋,影响其生物有效性和生态毒性.     

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.     

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).     

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.     

Two-dimensional correlation spectroscopic analysis on the interaction between humic acids and aluminum coagulant

In this study, two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy was employed to investigate the interaction between humic acids and aluminum coagulant at slightly acidic and neutral p H. Higher fluorescence quenching was produced for fulvic-like and humic-like fractions at p H 5. At p H 5, the humic-like fractions originating from the carboxylic acid, carboxyl and polysaccharide compounds were bound to aluminum first, followed by the fulvic-like fractions originating from the carboxyl and polysaccharide compounds. This finding also demonstrated that the activated functional groups of HA were involved in forming the Al-HA complex, which was accompanied by the removal of other groups by co-precipitation.Meanwhile, at p H 7, almost no fluorescence quenching occurred, and surface complexation was observed to occur, in which the activated functional groups were absorbed on the amorphous Al(OH)3. Two-dimensional FT-IR correlation spectroscopy indicated the sequence of HA structural change during coagulation with aluminum, with IR bands affected in the order of COOH COO-NH deformation of amide Ⅱ aliphatic hydroxyl C\OH at p H 5, and COO-aliphatic hydroxyl C\OH at p H 7. This study provides a promising pathway for analysis and insight into the priority of functional groups in the interaction between organic matters and metal coagulants.     

Flocculating characteristic of activated sludge flocs: Interaction between Al3+ and extracellular polymeric substances

Aluminum flocculant can enhance the flocculating performance of activated sludge.However,the binding mechanism of aluminum ion(Al 3+) and extracellular polymeric substances(EPS) in activated sludge is unclear due to the complexity of EPS.In this work,threedimensional excitation emission matrix fluorescence spectroscopy(3DEEM),fluorescence quenching titration and Fourier transform infrared spectroscopy(FT-IR) were used to explore the binding behavior and mechanism between Al 3+ and EPS.The results showed that two fluorescence peaks of tyrosineand tryptophan-like substances were identified in the loosely bound-extracellular polymeric substances(LB-EPS),and three peaks of tyrosine-,tryptophanand humic-like substances were identified in the tightly boundextracellular polymeric substances(TB-EPS).It was found that these fluorescence peaks could be quenched with Al 3+ at the dosage of 3.0 mg/L,which demonstrated that strong interactions took place between the EPS and Al 3+.The conditional stability constants for Al 3+ and EPS were determined by the Stern-Volmer equation.As to the binding mechanism,the-OH,N-H,C=O,C-N groups and the sulfurand phosphorus-containing groups showed complexation action,although the groups in the LB-EPS and TB-EPS showed different behavior.The TB-EPS have stronger binding ability to Al 3+ than the LB-EPS,and TB-EPS play an important role in the interaction with Al 3+.     

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.     

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...