[Characterization of Dissolved Organic Matter Fractions in the Ning-Meng Section of the Yellow River and Relationship with Metal Ions].

Dissolved organic matter(DOM)is an important element of natural aquatic systems. Due to differences in their hydrophobic/hydrophilic properties and various functional groups, chemical appearances of DOM fractions also vary. In this study, seven natural waters, extending from Xiaheyan to Toudaoguai along the Ning-Meng section of the Yellow river, were sampled in April 2015. Four DOM fractions were obtained by pumping through XAD-4 and XAD-8 resins, i.e., hydrophobic acid (HOA), hydrophobic base (HOB), weak hydrophobic acid (WHOA), and hydrophilic matter (HYI). Based on detection by three-dimensional excitation-emission matrix fluorescence (EEM) and correlation analysis, relationships with five metal ions (Pb, Zn, Cu, Cr, As) were analyzed. Results show that DOC gradually increased along an upstream to downstream continuum in the Ning-Meng section. HYI (small molecular proteins) was the main DOM fraction present, followed by HOA, suggesting enhanced microbial-sourced impact from industrial sewage discharges. The significant peaks of humic-like (A, C) and protein-like compounds (T1) in the EEM chart further highlight the effect of endogenous pollution caused by wastewater. Furthermore, SPSS fitting results indicate that DOM is correlated with all five metal ions, especially with Cu. In terms of the four DOM fractions, HYI showed the strongest correlation with Cu, illustrating the significant relationship between HYI and Cu during the migration and transformation process. Moreover, the fluorescence intensity of protein-like compounds decreased with increasing Cu concentration, possibly due to fluorescence quenching caused by complexation between Cu and proteins in HYI.

[Influence of Current Densities on Mineralization of Indole by BDD Electrode].

Electrochemical oxidation by boron-doped diamond (BDD) electrode is an effective method of degrading refractory organics. Compared with TOC detection, the amount of gas escape can more effectively and intuitively reflect the mineralization and the removal extent. In this study, indole is chosen as a typical pollutant and the detection of its removal rate was compared at current densities of 10, 20, and 30 mA·cm-2. Meanwhile, the degradation mechanism was analyzed based on the changes in the carbon and nitrogen forms and conservation status. As a result, BDD electrodes displayed a higher removal efficiency to indole, which can completely be removed after 8 h, 5 h, and 4 h with current densities of 10, 20 and 30 mA·cm-2, respectively. Changes in TOC removal and CO2 generation were both increased with increasing the current densities, suggesting that the mineralization extent was in accordance with current densities. Furthermore, the escaped CO2, combined with TOC and TIC constituted a conservative carbon system. The byproduct isatin was stable and accumulated at 4-5 h, as TOC, TON, and CO2 generation was unchanged at this stage. Finally, the XPS analysis suggested the adsorption by-products such as isatin and benzoquinone on the BDD surface, which can further be removed by increasing the electrolysis time. This study demonstrated the mineralization process of indole based on the escaped gas detection and the changes in the carbon and nitrogen forms, which will increase the understanding of the electrolysis process.

[Comparative Study of Benzotriazole Electrochemical Oxidation at Boron-doped Diamond and PbO2 Anodes].

Electrochemical systems were built to investigate the degradation of benzotriazole (BTA) on boron-doped diamond (BUU) and PbO2 anodes and give an insight into the mineralization ability of two electrodes in terms of the amount and activity of hydroxyl radicals. Results of bulk electrolysis showed that both BDD and PbO2 displayed perfect BTA degradation performance after 12 hours' electrolysis, with the removal percentages of 99. 48% and 98. 36%, respectively, while the mineralization ability of BDD was much stronger than that of PbO2, with the efficiency of 87. 69% for BDD and 35. 96% for PbO2. Less hydroxyl radical and hydrogen production in BDD system suggested the less amount of active sites on BDD surface, thus further verified that the generated hydroxyl radical amount was not the primary factor determining the mineralization ability of anodes. However, BDD displayed larger binding energy of adsorbed oxygen and thinner adsorption layer than those of PbO2, indicating that the BDD electrode surface was of greater catalytic activity, thus the generated hydroxyl radicals were more free, which was the key to its better mineralization ability.

Removal of copper from aqueous solution by electrodeposition in cathode chamber of microbial fuel cell.

Based on energetic analysis, a novel approach for copper electrodeposition via cathodic reduction in microbial fuel cells (MFCs) was proposed for the removal of copper and recovery of copper solids as metal copper and/or Cu(2)O in a cathode with simultaneous electricity generation with organic matter. This was examined by using dual-chamber MFCs (chamber volume, 1L) with different concentrations of CuSO(4) solution (50.3 ± 5.8, 183.3 ± 0.4, 482.4 ± 9.6, 1007.9 ± 52.0 and 6412.5 ± 26.7 mg Cu(2+)/L) as catholyte at pH 4.7, and different resistors (0, 15, 390 and 1000 Ω) as external load. With glucose as a substrate and anaerobic sludge as an inoculum, the maximum power density generated was 339 mW/m(3) at an initial 6412.5 ± 26.7 mg Cu(2+)/L concentration. High Cu(2+) removal efficiency (>99%) and final Cu(2+) concentration below the USA EPA maximum contaminant level (MCL) for drinking water (1.3mg/L) was observed at an initial 196.2 ± 0.4 mg Cu(2+)/L concentration with an external resistor of 15 Ω, or without an external resistor. X-ray diffraction analysis confirmed that Cu(2+) was reduced to cuprous oxide (Cu(2)O) and metal copper (Cu) on the cathodes. Non-reduced brochantite precipitates were observed as major copper precipitates in the MFC with a high initial Cu(2+) concentration (0.1M) but not in the others. The sustainability of high Cu(2+) removal (>96%) by MFC was further examined by fed-batch mode for eight cycles.

[Treatment of Cu(2+)-containing wastewater by microbial fuel cell with excess sludge as anodic substrate].

The two-chamber microbial fuel cells (MFCs) were constructed with excess sludge as the anodic substrate and CuSO4 solution as the catholyte. The start up method, degradation of the anodic sludge, removal of the Cu2+ and products on cathode were investigated in the study. The results of batch experiments showed that Cu2+ can be used as cathodic electron acceptors, e. g. a stable voltage output of 0.478 V and a maximum power density of 536 mW/m3 were obtained at external resistance of 1 000 omega and Cu2+ concentration of 6 400 mg/L. The Cu2+ contained in wastewater could be removed effectively by the MFC process, e. g. 97.8% of Cu2+ was removed in a MFC reactor at the end of 288 h with initial Cu2+ concentration of 1 000 mg/L and external resistance of 0 omega. The cathodic products depended on cathodic reducibility, most of Cu2+ was deposited as Cu2O and a small part as Cu4 (OH), 6SO4 with lower cathodic reducibility, metal copper deposited on the cathode with higher cathodic reducibility. Using excess sludge as anodic substrate could support the MFCs for long-term operation. The acclimation stage of the exoelectrogenic bacteria on the anode had an impact on MFC performance and cathodic reduction of Cu2+, and the stability of exoelectrogenic biofilm on anode could be determined by monitoring the anode potential. The MFC with excess sludge as anodic substrate can degrade organic matter in sludge and accomplish Cu(2+) -containing wastewater treatment and copper recovery simultaneously.

[Electricity generation and contaminants degradation performances of a microbial fuel cell fed with Dioscorea zingiberensis wastewater].

The electricity generation performance of a microbial fuel cell (MFC) utilizing Dioscorea zingiberensis wastewater was studied with an H-shape reactor. Indexes including pH, conductivity, oxidation peak potential and chemical oxygen demand (COD) of the anolyte were monitored to investigate the contaminants degradation performance of the MFC during the electricity generation process, besides, contaminant ingredients in anodic influent and effluent were analyzed by GC-MS and IR spectra as well. The maximum power density of the MFC could achieve 118.1 mW/m2 and the internal resistance was about 480 omega. Connected with a 1 000 omega external resistance, the output potential was about 0.4 V. Fed with 5 mL Dioscorea zingiberensis wastewater, the electricity generation lasted about 133 h and the coulombic efficiency was about 3.93%. At the end of electricity generation cycle, COD decreased by 90.1% while NH4(+) -N decreased by 66.8%. Furfural compounds, phenols and some other complicated organics could be decomposed and utilized in the electricity generation process, and the residual contaminants in effluent included some long-chain fatty acids, esters, ethers, and esters with benzene ring, cycloalkanes, cycloolefins, etc. The results indicate that MFC, which can degrade and utilize the organic contaminants in Dioscorea zingiberensis wastewater simultaneously, provides a new approach for resource recovery treatment of Dioscorea zingiberensis wastewater.

A membrane-free baffled microbial fuel cell for cathodic reduction of Cu(II) with electricity generation.

A membrane-free baffled microbial fuel cell (MFC) was developed to treat synthetic Cu(II) sulfate containing wastewater in cathode chamber and synthetic glucose-containing wastewater fed to anode chamber. Maximum power density of 314 mW/m(3) with columbic efficiency of 5.3% was obtained using initial Cu(2+) concentration of 6400 mg/L. Higher current density favored the cathodic reduction of Cu(2+), and removal of Cu(2+) by 70% was observed within 144 h using initial concentration of 500 mg/L. Powder X-ray diffraction (XRD) analysis indicated that the Cu(2+) was reduced to Cu(2)O or Cu(2)O plus Cu which deposited on the cathode, and the deficient cathodic reducibility resulted in the formation of Cu(4)(OH)(6)SO(4) at high initial Cu(2+) concentration (500-6400 mg/L). This study suggested a novel low-cost approach to remove and recover Cu(II) from Cu(2+)-containing wastewater using MFC-type reactor.

[Ecological characteristics of phytoplankton in Shenzhen Bay].

Based on the data of surface phytoplankton investigated by Hong Kong Environmental Protection Department in Shenzhen Bay in 2006, variation characteristics of phytoplankton communities and the relationship between the phytoplankton diversity indices and environmental factors were analyzed in the present paper. Results showed that a total of 27 genera and 34 species of phytoplankton were identified. Of these, 18 were diatoms (52.94%), 10 were dinoflagellates (29.41%), 6 were from other minor groups (17.65%). The cell abundance was estimated to be from 2.13 x 10(6) to 4.15 x 10(6) cells/L, with an average of 2.92 x 10(6) cells/L. The maximum cell abundance appeared in the autumn (October), followed in spring (May). The cell abundance showed double abundance peaks annually. The cell abundance of phytoplankton decreased from the middle bay to the bay mouth. In the marine area, the diversity index of the phytoplankton ranged from 0.76 to 2.52; the evenness of phytoplankton ranged from 0.29 to 0.74; the diversity and evenness of phytoplankton community were rather low, which indicated that the relative abundances of the species diverged from evenness, phytoplankton community were not steady, and only few dominant species increased rapidly. The species richness index ranged from 0.57 to 2.17, the high eutrophic water body caused the species richness index declined. Better relationship was found between phytoplankton diversity indices and nutrient, salinity, dissolved oxygen.

Production of diosgenin from Dioscorea zingiberensis tubers through enzymatic saccharification and microbial transformation.

In order to develop a clean and effective approach for producing the valuable drug diosgenin from Dioscorea zingiberensis tubers, two successive processes, enzymatic saccharification and microbial transformation, were used. With enzymatic saccharification, 98.0% of starch was excluded from the raw herb, releasing saponins from the network structure of starch. Subsequently, the treated tubers were fermented with Trichoderma reesei under optimal conditions for 156 h. During microbial transformation, glycosidic bonds, which link beta-D-glucose or alpha-L-rhamnose with aglycone at the C-3 position in saponins, were broken down effectively to give a diosgenin yield of 90.6+/-2.45%, 42.4% higher than that obtained from bioconversion of raw tubers directly. Scaled up fermentation was conducted in a 5.0-l bioreactor and gave a diosgenin yield of 91.2+/-3.21%. This is the first report on the preparation of diosgenin from herbs through microbial transformation as well as utilizing other available components in the raw material, providing an environmentally friendly alternative to diosgenin production.

Removal of Acid Orange 7 in simulated wastewater using a three-dimensional electrode reactor: removal mechanisms and dye degradation pathway.

The removal of Acid Orange 7 (AO7) in simulated wastewater was experimentally investigated using a three-dimensional electrode reactor with granular activated carbon as the particle electrode, ACF (activated carbon fiber)/Fe as the anode, and ACF/Ti as the cathode. Particular attention was paid to the reaction mechanisms and the dye degradation pathway in the system. The removal of AO7 in the system was mainly dependent on the oxidation by the produced active substances (()OH, etc.) and the coagulation by Fe(II) or Fe(III) dissolved from the anode. The former mechanism was predominant. A possible pathway for AO7 degradation was proposed by monitoring the temporal evolution of intermediates in the solution, with the use of some techniques including GC/MS, FTIR and HPLC. The AO7 molecule was observed to be firstly decomposed to aromatic intermediates, further degraded to ring opening products and finally mineralized to CO(2), H(2)O and inorganic salts. The intermediates increased the biodegradability of the wastewater, which was proved by the increase of the BOD/COD value after electrolysis treatment. The three-dimensional electrode method can be considered an effective alternative to dye wastewater pretreatment prior to the biological process.

Bioelectricity generation by a Gram-positive Corynebacterium sp. strain MFC03 under alkaline condition in microbial fuel cells.

This work studied an alkalophilic Gram-positive bacterium, Corynebacterium sp. strain MFC03, for its ability to produce electricity in the absence of an exogenous mediator under alkaline pH in microbial fuel cells (MFCs). The experimental results demonstrated that the strain MFC03 was capable of utilizing organic acids, sugars and alcohols as electron donors to generate electricity under above desired conditions. At an optimal pH of 9.0, the glucose-fed MFC achieved a maximum power density of 7.3 mW/m(2) and a Coulombic efficiency (CE) of 5.9%. In the presence of 0.1mM anthroquinone-2,6-disulfonate (AQDS), the maximum power density was enhanced to 41.8 mW/m(2) and CE was increased to 18.4%. The cyclic voltammetry measurements revealed that the electron transfer mechanism in the strain MFC03-based MFC was mainly via the excreted redox compounds in the medium solution.

Factors affecting the performance of microbial fuel cells for sulfide and vanadium (V) treatment.

Sulfide and vanadium (V) are pollutants commonly found in wastewaters. A novel approach has been investigated using microbial fuel cell (MFC) technologies by employing sulfide and V(V) as electron donor and acceptor, respectively. This results in oxidizing sulfide and deoxidizing V(V) simultaneously. A series of operating parameters as initial concentration, conductivity, pH, external resistance were carefully examined. The results showed that these factors greatly affected the performance of the MFCs. The average removal rates of about 82.2 and 26.1% were achieved within 72 h operation for sulfide and V(V), respectively, which were accompanied by the maximum power density of about 614.1 mW m(-2) under all tested conditions. The products generated during MFC operation could be deposited, resulting in removing sulfide and V(V) from wastewaters thoroughly.

[Status analysis of nutrients and eutrophication assessment in Shenzhen coastal waters].

Based on the field data of Shenzhen coastal water quality in 2002-2007, variation characteristics of nutrients including NH4+ -N, NO3- -N, NO2- -N, PO4(3-) -P and DIN were presented. And the correlationships between nutrients and pH, salinity were also investigated. Furthermore, eutrophication index (E), organic pollution index (A) and potential eutrophication were employed to assess the eutrophication degree of Shenzhen coastal waters. Results show that the nutrient levels of east coast are higher than that of west coast. And the peak year of nutrients are 2002 and 2006. The average concentrations of PO4(3-) -P and DIN are 0.007 mg/L and 0.078 mg/L for Shenzhen east coast while 0.090 mg/L and 1.544 mg/L for west coast. Nutrients in Shenzhen coastal waters have negative correlations with pH and salinity. The N/P ratios are all far more than 16 indicating that Shenzhen coast belongs to seriously P-limiting water. Eutrophication degree of Shenzhen east coast is far lower than that of west coast, and the average eutrophication index of east coast is 0.11 while 42.15 for west coast. Furthermore, west coast is classified as P-limiting moderate level potential eutrophication area and even as P-limiting potential eutrophication level.

[Performance of a single chamber microbial fuel cell utilizing Dioscorea zingiberensis C. H. Wright wastewater].

The possibility of electricity generation in a single chamber microbial fuel cell fed with Dioscorea zingiberensis C. H. Wright wastewater was demonstrated, and the effects of COD and SO4(2-) concentration on MFC performance were investigated. Under the same conductivity and COD concentration, the power density generated from wastewater equaled to 80.3% of that from glucose. At low COD concentration, the electricity generation increased with increasing COD loading rates, and the maximum power density was 322 mW/m2; while the COD concentration was enhanced over 2766 mg/L, the stable times for electricity generation was reduced and the MFC could not recover to previous performance as refueling. That indicates high COD loading rates would inhibit microbial activity. The COD removal rates varied from 68.2% to 84.8%, and it decreased when COD concentration climbed up. The power density was enhanced with SO4(2-) concentration increasing up to 7716 mg/L (Conductivity > 8.19 mS/cm) after which no further improvements in power density were observed. The maximum power density of the wastewater containing SO4(2-) was lower by 14.5% on average than that of the wastewater which removed SO4(2-). And its coulombic efficiencies declined substantially as SO4(2-) concentration increasing, which imply that the SO4(2-) is deoxidized as the electron acceptor, which takes the MFC efficiency down.

[Enhanced visible-light absorbance of nanosized AgI/TiO2 by using calcination combined with light irradiation].

With the aim to enhance visible-light absorbance, calcination combined with light irradiation was used to modify nanosized AgI/TiO2. UV-Vis spectrum curves indicated that the modified sample exhibited an intense absorption in the whole visible light range and a spectrum shifted from 465 nm to 800 nm, and that absorbance at 500 nm was improved three times as much as that of the reported pertinent material. XRD analytic results demonstrated that calcined AgI/TiO2 possessed more rutile phase with reduced band gap from 2.89 eV to 2.81 eV, and that the following xenon-light irradiation further enhanced the relative contents of anatase TiO2, rutile TiO2 and AgI accompanied with produced AgCl phase, leading to the decrease in band gap to 1.55 eV. Formation of AgCl and increases in the relative contents of rutile TiO2 and AgI should take the main responsibilities for the decrease in the band gap and enlargement of visible-light absorbance. Additionally, it was confirmed that only the spectrum absorption of the calcined AgI/TiO2 could be improved by light irradiation, and that ultraviolet light played more role than visible part during the light irradiation. Moreover, it was proposed here that two or more silver halides supported on TiO2 could show more capabilities to stimulate visible-light activation of TiO2.

[Effect of temperature on the Pb2+ biosorption with aerobic granules].

Experimental studies were conducted on the effect of temperature on the Pb2+ biosorption with aerobic granules seeding with floccular activated sludge. The results showed that the aerobic granules manly comprised the elements of C, H, N, O and P. According to the elemental compositions of the microbial granules, the corresponding empirical formula of the granules can be determined as C5.7 H10.9 O3.9 NS0.04. ESEM results showed many coccoid bacteria were visiable on the granule surface with porous structure. Both Freundlich and Langmuir isotherm equations could describe the biosorption process well (R2 > 0.914)under various temperature (20-40 degrees C). The maximum biosorption capacity (Q(max)) increased from 80.65 mg x g(-1) (20 degrees C) to 97.09 mg x g(-1) (40 degrees C). The values of thermodynamic parameters (deltaG < 0, deltaH > 0, deltaS > 0) indicated the biosorption process was spontaneous and endothermic in nature. Moreover, the Fourier transform infrared spectroscopy (FTIR) results demonstrated that such active groups as -OH, -COOH and P = O were involved in Pb2+ biosorption but nothing to do with nitrogen-containing groups.

[Mechanisms of bioelectricity generation in Enterobacter aerogenes-based microbial fuel cells].

Microbial fuel cells (MFCs) using hydrogen-producing bacteria (HPB) could utilize a large number of substrates to generate power. However, the coulombic efficiency is limited by the fact that only suspended cells are used as biocatalyst in anodic medium. MFCs using Fe (III)-reducing bacteria have high energy recovery efficiency, but can only utilize some simple organic matters. In this study, Enterobacter aerogenes XM02, a hydrogen-producing strain with Fe(III)-reducing activity, was selected as biocatalyst for MFCs, which could produce electricity by digesting lots of carbohydrates even starch. Graphite felt, a material with high specific surface area and hydrogen catalysis, instead of carbon paper supported platinum, was used as anode material. The coulombic efficiency had been substantially improved from 1.68% to 42.49%, higher than other HPB-based MFCs previously reported. The SEM image proved the ability of XM02 strain to colonize on the anode surface. Power generation of MFCs could restore quickly when anodic medium was completely replaced with non-growth medium containing glucose. This suggested that the attached cells contributed to electricity production because planktonic cells had been removed during the medium replacement. This study proposed the mechanism of power generated from in situ oxidation of hydrogen produced by the XM02 strain biofilm.

[Electricity generation from corn steepwater using microbial fuel cell technology].

Corn steepwater containing 49,732.2 mg/L of chemical oxygen demand (COD) was used as fuel for a membrane electrode assembly microbial fuel cell (MEA-MFC), which could generate electricity and treat the wastewater at the same time. During a batch experiment of 94 days with a fixed 1,000 Omega external resistance, the maximum voltage output of 525.0 mV and power density of 169.6 mW/m2 were obtained after 17 days, corresponding to the current density, internal resistance and open voltage of 440.2 mA/m2, 350 Omega and 619.5 mV, respectively. However, data showed that the coulombic efficiency was only 1.6%, suggesting very limited COD was utilized for electricity generation. At the conclusion of the test, the removals of COD and ammonia-nitrogen were achieved 51.6% and 25.8%, respectively. This study demonstrates that corn steepwater can be used for power generation in MFC with simultaneous accomplishments of wastewater treatment, providing a novel approach for the safe disposal and recycle of corn steepwater.

Defluoridation of drinking water by combined electrocoagulation: effects of the molar ratio of alkalinity and fluoride to Al(III).

The defluoridation efficiency (epsilon(F)) of electrocoagulation (EC) is closely related to the pH level of the F(-)-containing solution. The pH level usually needs to be adjusted by adding acid in order to obtain the highest epsilon(F) for the F(-)-containing groundwater. The use of combined EC (CEC), which is the combination of chemical coagulation with EC, was proposed to remove fluoride from drinking water for the first time in this study. The optimal scheme for the design and operation of CEC were obtained through experiments on the treatment of F(-)-containing groundwater. It was found, with OH(-) being the only alkalinity of the raw water, that the highest efficiency would be obtained when the molar ratio of alkalinity and fluoride to Al(III) (gamma(Alkalinity+F)) was controlled at 3.0. However, when the raw water contained HCO(3)(-) alkalinity, a correction coefficient was needed to correct the concentration of HCO(3)(-) to obtain the optimal defluoridation condition of gamma(Alkalinity+F)=3.0 for CEC. The correction coefficient of HCO(3)(-) concentration was concluded as 0.60 from the experiment. For the practical F(-)-containing groundwater treatment, CEC can achieve similar epsilon(F) as an acid-adding EC process. The consumption of aluminum electrode was decreased in CEC. The energy consumption also declined greatly in CEC, which is less than one third of that in the acid-adding EC process.

Variation of natural streamflow since 1470 in the middle Yellow River, China.

Nowadays, as the available water resources throughout the World are becoming depleted, in order to manage and plan water resource better, more and more attention is being paid into the fluctuating characteristics of water discharges. However, the preexisting research was mainly focused on the last half century. In this paper, the natural streamflow observed since 1470 at the Sanmenxia station in the middle Yellow River basin was collected, and the methods of variation coefficient, moving average, Mann-Kendall test and wavelet transform were applied to analyze the dynamic characteristics of the streamflow. The results showed that, (1) between 1470 and 2007, the natural streamflow changed 200-919 x 10(8) m(3), and water discharge varied moderately; (2) in the middle Yellow River basin, it appears that the most severe and most persistent droughts during circa 1868-1990, the periods of 1470s-1490s, 1920s-1930s and 1990s-2000s also presented the condition of sustained low flows; (3) the natural streamflow series shows increasing and decreasing trends during the periods of 1470-1880 and 1881-2007, respectively, but both trends are not significant at >95% confidence; in addition, it is still found the streamflow series shows abrupt changes circa 1845, 1935 and 1960, respectively; (4) within a 250-year scale, there are circa 11, 26, 67 and 120-year periods for natural streamflow at the Sanmenxia station, and the periodicity of the 120-year one is the strongest. The dynamic characteristics of natural streamflow is the comprehensive result by many influencing factors, such as precipitation, temperature, El Niño-Southern Oscillation, sunspots, human activity, etc.