Supercritical water oxidation of polyvinyl alcohol and desizing wastewater：Influence of NaOH on the organic decomposition

Polyvinyl alcohol is a refractory compound widely used in industry. Here we report supercritical water oxidation of polyvinyl alcohol solution and desizing wastewater with and without sodium hydroxide addition. However, it is difficult to implement complete degradation of organics even though polyvinyl alcohol can readily crack under supercritical water treatment. Sodium hydroxide had a significant catalytic effect during the supercritical water oxidation of polyvinyl alcohol. It appears that the OH ion participated in the C-C bond cleavage of polyvinyl alcohol molecules, the CO2-capture reaction and the neutralization of intermediate organic acids, promoting the overall reactions moving in the forward direction. Acetaldehyde was a typical intermediate product during reaction. For supercritical water oxidation of desizing wastewater, a high destruction rate (98.25%) based on total organic carbon was achieved. In addition, cases where initial wastewater was alkaline were favorable for supercritical water oxidation treatment, but salt precipitation and blockage issues arising during the process need to be taken into account seriously.     

Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.     

Photocatalytic degradation of carbofuran in TiO2 aqueous solution：Kinetics using design of experiments and mechanism by HPLC/MS/MS

The photocatalytic degradation kinetics of carbofuran was optimized by central composite design based on response surface methodology for the first time. Three variables, TiO2 concentration, initial pH value and the concentration of carbofuran, were selected to determine the dependence of degradation efficiencies on independent variables. Response surface methodology modeling results indicated that the degradation efficiency of carbofuran was highly affected by the initial pH value and the concentration of carbofuran. Then nine degradation intermediates were detected by HPLC/MS/MS. The Frontier Electron Densities of carbofuran were calculated to predict the active sites on carbofuran attacked by hydroxyl radicals and photoholes. Point charges were used to elucidate the chemisorption pattern on TiO2 catalysts during the photocatalytic process. By combining the experimental results and calculation data, the photocatalytic degradation pathways of carbofuran were proposed, including the addition of hydroxyl radicals and the cleavage of the carbamate side chain.     

Identification of key factors governing chemistry in groundwater near the water course recharged by reclaimed water at Miyun County, Northern China

Reclaimed water was successfully used to recover the dry Chaobai River in Northern China, but groundwater may be polluted. To ensure groundwater protection, it is therefore critical to identify the governing factors of groundwater chemistry. Samples of reclaimed water, river and groundwater were collected monthly at Chaobai River from January to September in 2010. Fifteen water parameters were analyzed. Two kinds of reclaimed water were different in type (Na-Ca-Mg-Cl-HCO3 or Na-Ca-Cl-HCO3 ) and concentration of nitrogen. The ionic concentration and type in river were similar to reclaimed water. Some shallow wells near the river bed had the same type (Na-Ca-Mg-Cl-HCO3 ) and high concentration as reclaimed water, but others were consistent with the deep wells (Ca-Mg-HCO3 ). Using cluster analysis, the 9 months were divided into two periods (dry and wet seasons), and all samples were grouped into several spatial clusters, indicating different controlling mechanisms. Principal component analysis and conventional ionic plots showed that calcium, magnesium and bicarbonate were controlled by water-rock interaction in all deep and some shallow wells. This included the dissolution of calcite and carbonate weathering. Sodium, potassium, chloride and sulfate in river and some shallow wells recharged by river were governed by evaporation crystallization and mixing of reclaimed water. But groundwater chemistry was not controlled by precipitation. During the infiltration of reclaimed water, cation exchange took place between (sodium, potassium) and (calcium, magnesium). Nitrification and denitrification both happened in most shallow groundwater, but only denitrification in deep groundwater.     

Soil microbial community structure and function responses to successive planting of Eucalyptus

Many studies have shown soil degradation after the conversion of native forests to exotic Eucalyptus plantations. However, few studies have investigated the long-term impacts of short-rotation forestry practices on soil microorganisms. The impacts of Eucalyptus successive rotations on soil microbial communities were evaluated by comparing phospholipid fatty acid （PLFA） abundances, compositions, and enzyme activities of native Pinus massoniana plantations and adjacent 1st, 2nd, 3rd, 4th generation Eucalyptus plantations. The conversion from P. massoniana to Eucalyptus plantations significantly decreased soil microbial community size and enzyme activities, and increased microbial physiological stress. However, the PLFA abundances formed ＂U＂ shaped quadratic functions with Eucalyptus plantation age. Alternatively, physiological stress biomarkers, the ratios of monounsaturated to saturated fatty acid and Gram＋ to Gram- bacteria, formed ＂∩＂ shaped quadratic functions, and the ratio of cy17：0 to 16： 1ω7c decreased with plantation age. The activities of phenol oxidase, peroxidase, and acid phosphatase increased with Eucalyptus plantation age, while the cellobiobydrolase activity formed ＂U＂ shaped quadratic functions. Soil N：P, alkaline hydrolytic nitrogen, soil organic carbon, and understory cover largely explained the variation in PLFA profiles while soil N：P, alkaline hydrolytic nitrogen, and understory cover explained most of the variability in enzyme activity. In conclusion, soil microbial structure and function under Eucalyptus plantations were strongly impacted by plantation age. Most of the changes could be explained by altered soil resource availability and understory cover associated with successive planting of Eucalyptus. Our results highlight the importance of plantation age for assessing the impacts of plantation conversion as well as the importance of reducing disturbance for plantation management.     

Waste oyster shell as a kind of active filler to treat the combined wastewater at an estuary

Estuaries have been described as one of the most difficult environments on Earth. It is difficult to know how to treat the combined wastewater in tidal rivers at the estuary, where the situation is very different from ordinary fresh water rivers. Waste oyster shell was used as the active filler in this study in a bio-contact oxidation tank to treat the combined wastewater at the Fengtang Tidal River. With a middle-experimental scale of 360 ma/day, the average removal efficiency of COD, BOD, NH3-N, TP and TSS was 80.05%, 85.02%, 86.59%, 50.58% and 85.32%, respectively, in this bio-contact oxidation process. The living microbes in the biofilms on the waste oyster shell in this bio-contact oxidation tank, which were mainly composed of zoogloea, protozoa and micro-metazoa species, revealed that waste oyster shell as the filler was suitable material for combined wastewater degradation. This treatment method using waste oyster shell as active filler was then applied in a mangrove demonstration area for water quality improvement near the experiment area, with a treatment volume of 5 × 10^3 m^3/day. Another project was also successfully applied in a constructed wetland, with a wastewater treatment volume of 1 ×10^3 m^3/day. This technology is therefore feasible and can easily be applied on a larger scale,     

Eutrophication development and its key regulating factors in a water-supply reservoir in North China

Yanghe Reservoir is an important source of drinking water for Qinhuangdao City,North China;however,in recent decades this water source has been eutrophic with recurrent summer cyanobacterial blooms.The trophic grade of the system in summer was mesotrophiceutrophic in 1990 and became hypertrophic in 2011.The nutrient availability is extremely high during the entire year,and the water temperature should be the primary driver of the summer blooms.In May-October of 2010 and 2011,abrupt variations were observed in the Secchi depth(SD) and chlorophyll a(Chl-a),and both the correlated analysis of Chl-a-SD and trophic status indices(TSI) deviation(TSI Chl-a-TSI SD) showed that algal cell density dominated light attenuation.During the algal bloom outbreak,the microcystin concentration was found to vary between 0.35-2.12 μg/L in 2010 and 0.11-1.86 μg/L in 2011.The maximum microcystin content was more than two times the safety limit required for drinking water.Inflow discharges were most concentrated in the summer,with periods of lower residence time and the largest water level fluctuation over the entire year.When a high availability of nutrients promoted a high Chl-a concentration in the whole system,it appeared that the instability caused by the decrease in residence time could not produce effective changes in the cyanobacterial abundance.The results indicated that nutrient enrichment in the aquatic systems of Yanghe Reservoir is the most serious problem and that the status would not been modified effectively by increasing hydrological fluctuations(e.g.,decreasing the residence time).Therefore,decreasing the nutrient concentrations is the only route to improve the water quality of this reservoir.     

Speciation of organic phosphorus in a sediment profile of Lake Taihu II. Molecular species and their depth attenuation

The understanding of organic phosphorus(P) dynamics in sediments requires information on their species at the molecular level,but such information in sediment profiles is scarce.A sediment profile was selected from a large eutrophic lake,Lake Taihu(China),and organic P species in the sediments were detected using solution phosphorus-31 nuclear magnetic resonance spectroscopy(31 P NMR) following extraction of the sediments with a mixture of 0.25 mol/L NaOH and 50 mmol/L EDTA(NaOH-EDTA) solution.The results showed that P in the NaOH-EDTA extracts was mainly composed of orthophosphate,orthophosphate monoesters,phospholipids,DNA,and pyrophosphate.Concentrations of the major organic P compound groups and pyrophosphate showed a decreasing trend with the increase of depth.Their half-life times varied from 3 to 27 years,following the order of orthophosphate monoesters > phospholipids DNA > pyrophosphate.Principal component analysis revealed that the detected organic P species had binding phases similar to those of humic acid-associated organic P(NaOH-NRP HA),a labile organic P pool that tends to transform to recalcitrant organic P pools as the early diagenetic processes proceed.This demonstrated that the depth attenuation of the organic P species could be partly attributed to their increasing immobilization by the sediment solids,while their degradation rates should be significantly lower than what were suggested in previous studies.     

铬(Ⅵ)土著还原菌筛选及初步鉴定实验研究

以重铬酸钾为供试物,用固体平板法和还原实验对铬(Ⅵ)土著还原菌进行筛选,用载片培养法、革兰氏染色法、鞭毛染色法、芽孢染色法对还原菌做初步的鉴定,共筛选出16株铬(Ⅵ)土著还原菌,并挑选出还原率相对较高的Z2(35.2%)、Z3(45.2%)、Z4(38.6%)、X8(30.4%)、X10(29.4%)作为铬(Ⅵ)的优势还原菌株。经初步鉴定,土著真菌Z2为黑曲霉(Aspergillusniger),Z3、Z4为镰刀菌属(Fusariumsp.),土著细菌X8、X10为芽孢杆菌(Bacillussp.)。实验的方法和成果将为铬(Ⅵ)污染土壤微生物治理技术的推广应用提供技术支持。     

小飞扬草(Euphorbia thymifolia L.)中镉的亚细胞分布及化学形态

采用差速离心法和逐步提取法,分析Cd超积累植物小飞扬草根、茎、叶中Cd的亚细胞分布和化学形态。培养液中Cd浓度5mg/L和10mg/L条件下,在小飞扬草根、茎、叶中,细胞壁和细胞膜是Cd主要的结合场所,含量分别占总量的47.1%～49.0%、39.7%～41.4%、42.9%～56.2%,其次是胞液组分,含量分别占37.5%～41.4%、28.2%～40.7%、35.2%～46.8%,细胞器组分中Cd含量较少。Cd在小飞扬草根、茎、叶中均以氯化钠提取态为主,含量分别占70.5%～84.8%、72.4%～83.0%、50.0%～74.8%。根部各提取态含量依次为CNaCl>CHAC>CEtOH>CHCl>CW>CR,茎、叶中各提取态含量依次为CNaCl>CHCl>CHAC>CEtOH>CW>CR。在小飞扬草中,Cd与细胞壁和细胞膜中的果胶酸和蛋白质等物质结合固定,而进入细胞的Cd大部分与有机酸络合而隔离于液泡内,这可能是小飞扬草忍耐并超积累Cd的机制。