Performance of different macrophytes in the decontamination of and electricity generation from swine wastewater via an integrated constructed wetland-microbial fuel cell process

Plants constitute a major element of constructed wetlands(CWs).In this study,a coupled system comprising an integrated vertical flow CW(IVCW) and a microbial fuel cell(MFC) for swine wastewater tre atment was developed to research the effects of macrophytes commonly employed in CWs,Canna indica,Acorus calamus,and Ipomoea aquatica,on decontamination and electricity production in the system.Because of the different root types and amounts of oxygen released by the roots,the rates of chemical oxygen demand(COD) and ammonium nitrogen(NH_4~+-N) removal from the swine wastewater differed as well.In the unplanted,Canna indica,Acorus calamus,and Ipomoea aquatica systems,the COD removal rates were 80.20%,88.07%,84.70%,and 82.20%,respectively,and the NH_4~+-N removal rates were 49.96%,75.02%,70.25%,and 68.47%,respectively.The decontamination capability of the Canna indica system was better than those of the other systems.The average output voltages were 520±42,715±20,660±27,and 752±26 mV for the unplanted,Canna indica,Acorus calamus,and Ipomoea aquatica systems,respectively,and the maximum power densities were 0.2230,0.4136,0.3614,and0.4964 W/m~3,respectively.Ipomoea aquatica had the largest effect on bioelectricity generation promotion.In addition,electrochemically active bacteria,Geobacter and Desulfuromonas,were detected in the anodic biofilm by high-throughput sequencing analysis,and Comamonas(Proteobacteria),which is widely found in MFCs,was also detected in the anodic biofilm.These results confirmed the important role of plants in IVCW-MFCs.     

Mechanism and catalytic performance for direct dimethyl ether synthesis by CO2 hydrogenation over CuZnZr/ferrierite hybrid catalyst

Direct synthesis of dimethyl ether(DME) by CO_2 hydrogenation has been investigated over three hybrid catalysts prepared by different methods:co-precipitation,sol-gel,and solid grinding to produce mixed Cu,ZnO,ZrO_2 catalysts that were physically mixed with a commercial ferrierite(FER) zeolite.The catalysts were characterized by N_2 physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),temperature programmed desorption of CO_2(CO_2-TPD),temperature programmed desorption of NH_3(NH_3-TPD),and temperature programmed H2 reduction(H_2-TPR).The results demonstrate that smaller CuO and Cu crystallite sizes resulting in better dispersion of the active phases,higher surface area,and lower reduction temperature are all favorable for catalytic activity.The reaction mechanism has been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Methanol appears to be formed via the bidentate-formate(b-HCOO) species undergoing stepwise hydrogenation,while DME formation occurs from methanol dehydration and reaction of two surface methoxy groups.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

Chemical characteristics of road dust PM2.5 fraction in oasis cities at the margin of Tarim Basin

In order to understand the compositions characteristics of particulate matter with aerodynamic diameter less than 2.5 μm (PM_2.5) fraction in road dust (RD_2.5) of oasis cities on the edge of Tarim Basin, 30 road dust (RD) samples were collected in Kashi, Cele, and Yutian in the spring, 2018, and RD_2.5 was collected using the resuspension approach. Eight water-soluble ions, 39 trace elements and 8 fractions of carbon-containing species in PM_2.5 were analyzed. Ca²⁺ and Ca were the most abundant ions and elements in RD_2.5 (7.1% and 9.5%). Cl^- in RD_2.5 was affected not only by attributed to saline-alkali soils in oasis cities of the Tarim Basin and dust from Taklimakan Desert but also by human activities. Moreover, the organic carbon/elemental carbon (OC/EC) ratio indicated that carbon components in RD_2.5 in Cele town mainly come from fossil fuel combustion, while those in Yutian and Kashi mainly come from biomass combustion. It is noteworthy that high Ca in RD_2.5 was seriously affected by anthropogenic emissions, and high Na and K contents in RD_2.5 could be derived from soil and desert dust. It was estimated that Cd, Tl, Sn and Cr were emitted from anthropogenic emissions using the enrichment factor. The coefficients of divergence (COD) result indicated that the influence of local emission on road dust emission is greater than that of long-distance transmission. This study is the first time to comprehensively analyze the chemical characteristics of road dust in oasis cities, and the results provides the sources of road dust at the margin of Tarim Basin.     

石期河流域地下水化学特征及物质来源分析

为明确典型岩溶溶丘洼(谷)地区域地下水化学特征及其成因,以石期河流域为研究对象,运用Gibbs图、Piper图、端元分析及离子比例系数等方法,对地下水水化学特征及物质来源进行了定性和定量分析.结果表明,研究区内地下水pH值介于6.06～8.07之间,Ca~(2+)、 Mg~(2+)和HCO~-_3是地下水中的主要离子,其质量浓度范围分别为2.61～108.7、 0.54～27.61和8.1～370.74mg·L~(-1),符合岩溶水高钙弱碱性特征;地下水物质成分中, Ca~(2+)和Mg~(2+)主要受到碳酸参与的灰岩和白云岩风化作用的控制, Na~+主要来源于硅酸盐岩的溶解,同时, Ca~(2+)和Na~+在地下水流动过程中进行阳离子交替吸附作用; K~+、 Cl~-和NO~-_3主要受到农业化肥施放和生活废水排放的影响.此外,大气降水作为该区域地下水的主要补给来源,对当地地下水化学特征和物质来源也有一定的影响.     

杭州湾北岸上海段石化集中区臭氧重污染过程研究

为研究杭州湾O₃污染的形成机制,采用在线监测系统对杭州湾北岸上海段石化集中区O₃及其前体物开展了为期1个月(2019年5月)的同步连续观测.采用OZIPR(臭氧等值线研究)模型分析O₃生成的敏感性.在O₃重度污染期间,利用PMF(正定矩阵因子分解)模型对O₃前体物——VOCs进行源解析,采用臭氧生成潜势及气团老化分别估算了VOCs的反应活性和化学消耗.结果表明:①2019年5月杭州湾北岸上海段石化集中区O₃的IAQI(空气质量分指数)优良率仅为61.3%,ρ(O₃)第90%分位值为173.0 μg/m3.5月22日、23日发生重度O₃污染,O₃日最大8 h滑动平均值分别为(284.4±19.2)(282.0±14.2)μg/m3,分别超过GB 3095—2012《环境空气质量标准》二级标准限值(160 μg/m3)的77.75%和76.25%.②O₃的生成受VOCs控制,降低VOCs的排放可在一定程度上降低O₃的生成,降低NO_x的排放反而会促进O₃的生成.③O₃重度污染期间,VOCs主要来自化工区排放(72.35%)和机动车尾气排放(27.65%).④O₃重度污染期间,烯烃、炔烃及芳香烃对O₃生成的贡献率之和在80.00%以上,其中丙烯、乙烯和甲苯的贡献率分别为29.97%、15.60%和14.16%;芳香烃及烯烃和炔烃是最主要的VOCs化学消耗物种,其中φ(丙烯)、φ(乙烯)和φ(1,2,4-三甲苯)的消耗量分别为13.57×10-9、4.93×10-9和3.55×10-9.研究显示,杭州湾北岸上海段5月O₃的生成受化工区影响显著,丙烯与乙烯是O₃重污染期间关键的O₃前体物.      

石油污染土壤多酚氧化酶的动力学及热力学特征

土壤多酚氧化酶是一种氧化还原酶,能够将土壤中芳香族化合物氧化成醌,促进土壤中石油类物质的分解转化.以距大庆油田工作区不同距离（1、5、15 km）的石油污染地为对象,研究不同温度下石油污染裸地及羊草（Leymus chinensis）修复地的土壤多酚氧化酶活性及其动力学和热力学特征的变化.结果表明:土壤多酚氧化酶活性随温度和底物浓度的增加而逐渐增大,在温度为30℃或40℃、底物浓度为80 mmol/L或160 mmol/L时达到最大值;各样地土壤酶的动力学参数K_m（Mihaelis常数）随温度的变化规律不同,V_max（酶促反应最大速度）和V_max/K_m（催化效率）随温度升高而逐渐增大,均在30℃或40℃时达到最大值;热力学参数Q₁₀（温度系数）、ΔH（活化焓）、ΔS（活化熵）随温度变化差异不显著,ΔG（活化自由能）随温度升高呈逐渐增加趋势.在同一温度下,石油污染裸地土壤多酚氧化酶活性高于羊草修复地;K_m和V_max/K_m在各样地均表现为无规律性变化,V_max最大值出现在距油田工作区5 km处的裸地（BMP）,最小值出现在距油田工作区5 km处的羊草修复地（LMP）;Q₁₀、E_a（活化能）、ΔH、ΔS的最大值均出现在距油田工作区1 km处的裸地（BVP）,最小值均出现在距油田工作区1 km处的羊草修复地（LVP）.研究显示,升温和植物修复对土壤多酚氧化酶活性的反应特征有较大影响.      

土壤调理剂对土壤-水稻系统Cd、Zn迁移累积的影响及健康风险评价

选取湖南省长沙市北山镇某中重度Cd污染稻田,研究了土壤调理剂(石灰石+偏高岭土+钙镁磷肥)对稻田土壤重金属Cd、Zn的钝化效果,以及对水稻各部位累积Cd和Zn的影响,并进行了Cd的健康风险评价.结果表明,使用土壤调理剂提高了稻田土壤p H值.Cd的CaCl_2提取态含量降低了0.9%~24.1%,Zn的CaCl_2提取态含量降低了22.5%~69.6%.土壤调理剂显著降低了水稻糙米中Cd与Zn的含量,与对照相比分别降低了10.8%~47.3%、10.3%~17.5%;土壤调理剂对水稻糙米Cd的吸收和累积的影响要远大于Zn,水稻糙米中的Cd/Zn比随着土壤调理剂施用量的增加而显著降低.研究区大米重金属Cd目标危害系数THQ值大于1,说明当地人群通过食用大米途径摄入重金属Cd存在健康风险.土壤调理剂有效地抑制了水稻植株对土壤中Cd的吸收,并降低了Cd/Zn比,使糙米中的Cd含量显著降低,从而降低了当地人群通过食用大米途径摄入重金属Cd的健康风险.     

模拟盐水入侵及Fe(III)浓度增强对河口感潮淡水沼泽湿地土壤反硝化速率及理化特征的影响

以闽江河口塔礁洲感潮淡水野慈姑(Sagittaria trifolia Linn.)湿地为研究对象,于2016年2、4、7和9月每月均在连续2个小潮日内向研究样地施加人造海水和Fe(OH)_3溶液,研究短期的盐水入侵及Fe(III)浓度增强对河口感潮淡水湿地土壤反硝化速率及理化特征的影响.结果表明,短期的盐水入侵、Fe(III)浓度增强对河口感潮淡水沼泽湿地土壤反硝化速率的影响不显著,然而,盐水和Fe(III)共同施加会显著提高湿地土壤反硝化速率,与对照(CK)相比,盐水和Fe(III)共同施加可使土壤反硝化速率提高270.9%.盐水入侵、盐水和Fe(III)共同施加均可显著提高湿地土壤、间隙水的电导率及Cl~-、SO_4~(2-)的含量;Fe(III)浓度增强可显著降低土壤和间隙水pH值,同时显著提高土壤三价铁含量.     

Nanoencapsulation of hexavalent chromium with nanoscale zero-valent iron: High resolution chemical mapping of the passivation layer

Solid phase reactions of Cr(Ⅵ) with Fe(0) were investigated with spherical-aberration-corrected scanning transmission electron microscopy(Cs-STEM) integrated with X-ray energy-dispersive spectroscopy(XEDS). Near-atomic resolution elemental mappings of Cr(Ⅵ)–Fe(0) reactions were acquired. Experimental results show that rate and extent of Cr(Ⅵ) encapsulation are strongly dependent on the initial concentration of Cr(Ⅵ) in solution. Low Cr loading in nZⅥ(1.0 wt%) promotes the electrochemical oxidation and continuous corrosion of n ZⅥ while high Cr loading(1.0 wt%) can quickly shut down the Cr uptake. With the progress of iron oxidation and dissolution, elements of Cr and O counter-diffuse into the nanoparticles and accumulate in the core region at low levels of Cr(Ⅵ)(e.g., 10 mg/L). Whereas the reacted n ZⅥ is quickly coated with a newly-formed layer of 2–4 nm in the presence of concentrated Cr(Ⅵ)(e.g., 100 mg/L). The passivation structure is stable over a wide range of pH unless pH is low enough to dissolve the passivation layer. X-ray photoelectron spectroscopy(XPS) depth profiling reconfirms that the composition of the newly-formed surface layer consists of Fe(Ⅲ)–Cr(Ⅲ)(oxy)hydroxides with Cr(Ⅵ) adsorbed on the outside surface. The insoluble and insulating Fe(Ⅲ)–Cr(Ⅲ)(oxy)hydroxide layer can completely cover the n ZⅥ surface above the critical Cr loading and shield the electron transfer. Thus, the fast passivation of nZⅥ in high Cr(Ⅵ) solution is detrimental to the performance of nZⅥ for Cr(Ⅵ) treatment and remediation.