Degradation of monofluorophenols in water irradiated with gaseous plasma

Decomposition of aqueous monofluorophenols (MFPs) was investigated by contact glow discharge electrolysis (CGDE). During CGDE, both MFPs and the corresponding total organic carbon (TOC) in water were consumed smoothly, suggesting that carbon atoms of benzene nucleus could be eventually mineralized to inorganic carbon (IC). And all the fluorine atoms in the MFPs were equally converted to fluoride ions. Based on the primary intermediates from each starting materials, it showed that aromatic hydroxylation preferentially occurred at the para- or ortho- position to the phenolic OH group of each MFPs. The disappearance of both MFPs and TOC followed the first-order rate law. The apparent rate constants for the decay of MFPs were independent from the pK_a values of MFPs.     

Exhaustive breakdown of aqueous monochlorophenols by contact glow discharge electrolysis

The aqueous monochlorophenols were degraded by contact glow discharge electrolysis (CGDE), in which plasma was generated in a localized zone between an electrolytic solution and an anode. With the decay of monochlorophenols, the amount of total organic carbon (TOC) also decreased smoothly, indicating that carbon atoms of benzene nucleus could be eventually converted to inorganic carbons. Meanwhile, it was also clarified that chlorine atoms in the organics were liberated as chloride ions. In addition, it was revealed that the disappearance of monochlorophenols obeyed the first-order rate law, depending on the isomeric structures.     

A high activity of Ti/SnO2-Sb electrode in the electrochemical degradation of 2,4-dichlorophenol in aqueous solution

Electrochemical degradation of 2,4-dichlorophenol (2,4-DCP) in aqueous solution was investigated over Ti/SnO₂-Sb anode. The factors influencing the degradation rate, such as applied current density (2-40 mA/cm²), pH (3-11) and initial concentration (5-200 mg/L) were evaluated. The degradation of 2,4-DCP followed apparent pseudo first-order kinetics. The degradation ratio on Ti/SnO₂-Sb anode attained > 99.9% after 20 min of electrolysis at initial 5-200 mg/L concentrations at a constant current density of 30 mA/cm² with a 10 mmol/L sodium sulphate (Na2SO4) supporting electrolyte solution. The results showed that 2,4-DCP (100 mg/L) degradation and total organic carbon (TOC) removal ratio achieved 99.9% and 92.8%, respectively, at the optimal conditions after 30 min electrolysis. Under this condition, the degradation rate constant (k) and the degradation half-life (t_1/2) were 0.21 min^-1 and (2.8±0.2) min, respectively. Mainly carboxylic acids (propanoic acid, maleic acid, propanedioic acid, acetic acid and oxalic acid) were detected as intermediates. The energy efficiencies for 2,4-DCP degradation (5-200 mg/L) with Ti/SnO₂-Sb anode ranged from 0.672 to 1.602 g/kWh. The Ti/SnO₂-Sb anode with a high activity to rapid organic oxidation could be employed to degrade chlorophenols, particularly 2,4-DCP in wastewater.     

贵州乌江渡水库沉积速率及碳氮埋藏通量估算

我国西南地区峡谷型梯级水库沉积物的碳汇效应对全球碳循环有着重要意义。为了探明该区域水库的碳汇强度,本研究选择乌江流域的乌江渡水库作为研究对象,于2015年5月对水库沉积物进行采样,并利用210Pbex核素计年技术,结合沉积物碳氮分析,估算乌江渡水库的碳埋藏量。结果表明:乌江渡水库沉积物平均沉积速率为0.155g/(cm~2·a),TOC沉降通量为70.85g/(m~2·a),堆积通量为29.14g/(m~2·a);TN沉降通量为8.22g/(m~2·a),堆积通量为2.79g/(m~2·a)。乌江渡水库沉积物年均TOC总埋藏通量为1.39×10~9g/a,其中82%来自水库内部光合作用形成的有机质。因此,依据保守的估算,乌江渡水库沉积物的净碳汇通量为23.9g/(m~2·a),保存的净碳汇量为1.1×10~9g/a。研究结果表明水库沉积物是一个重要的碳汇。     

基于呼吸强度和总有机碳综合评价存量生活垃圾好氧稳定化程度的方法研究

设计固定床好氧稳定化实验装置，在恒温、通风、含水量适宜条件下运行，研究东莞、厦门等地开采后的存量生活垃圾以及食堂餐厨垃圾样品稳定化过程中总有机碳（TOC）和4日呼吸强度（AT₄）随时间的变化规律以及两者变化趋势的相关性.优化了TOC和AT₄的检测方法，证明仪器法测定TOC结果更加合理；研究表明采用四分法取样、从迟滞期结束后开始计算得到的AT₄更有参考价值；4种垃圾样品TOC和AT₄之间具有良好的相关性，两者导数之间也具有良好的相关性，且相关系数均大于0.99（R²>0.99），证明了TOC和AT₄变化趋势的同步响应规律，说明可以利用能快速测定的TOC指标的变化趋势反映不能快速测定的AT₄指标的变化趋势，从而提出一种通过TOC的变化趋势和AT₄的数值综合评价存量垃圾好氧稳定化程度的新方法，既缩短了检测周期，又提高了好氧稳定性评价的客观性，为存量垃圾稳定化评价提供了新思路.     

Mineralization of aqueous pentachlorophenolate by anodic contact glow discharge electrolysis

Exhaustive mineralization of pentachlorophenolate ion (PCP) in phosphate buffer was carried out using anodic contact glow discharge electrolysis (CGDE), in which plasma was sustained between the electrolyte and anode. During CGDE, PCP degraded smoothly. The amount of total organic carbon decreased significantly, indicating the eventual conversion of the carbon atoms of benzene nucleus to inorganic carbons. Furthermore, chlorine atoms in PCP were liberated as chloride ions. As a primary intermediate product, 2,3,5,6- tetrachloro-1,4-benzoquinone was detected, and oxalate and formate as byproducts were also found. It was revealed that disappearance of PCP obeyed first-order kinetics. The reaction rate was generally unaffected by both O2 and inert gases in the cell, although it decreased by raising initial pH of solution. In addition, a plausible reaction pathway involving hydroxyl radical was proposed.     

Ti/Ti4O7阳极电化学氧化降解水中的美托洛尔

等离子喷涂法制备了钛基亚氧化钛电极(Ti/Ti_4O_7),以该电极为阳极,研究了电化学氧化法对水中美托洛尔的去除效果.考察了电流密度(5~25 mA·cm~(-2))、极板间距(5~25 mm)和初始浓度(3~50 mg·L~(-1))对美托洛尔电化学降解效率的影响;分析美托洛尔电化学降解过程中溶液总有机碳(TOC)和毒性的变化,鉴别反应中间产物并计算其毒性.研究表明:Ti/Ti_4O_7阳极电化学降解美托洛尔反应符合一级反应动力学规律(R20.95),降解效率随电流密度的增大而增大,随极板间距和初始浓度的增大而减小;TOC去除率在反应40 min后可达56.5%;反应过程中产生了质合比为266、250、223和207的中间产物,造成美托洛尔溶液的生物毒性在电化学反应过程中先升高后下降.     

热处理对SnO2/Ti电化学催化降解p-苯醌的影响

用热分解方法制备了钛基二氧化锡阳极(SnO₂/Ti),对比研究了空气/氧气2种热处理气氛对电极性能的影响.用扫描电镜(SEM)观察了电极表面形貌,对电极表面主要膜元素的化学状态进行了X射线光电子能谱(XPS)分析,对电极在不同溶液的动电位极化行为进行了测试,研究了2种电极在5mA/cm²恒电流状态下对p-苯醌的电解催化去除性能.SEM观察表明,2种电极表面都为典型的泥裂形貌,但在氧气气氛中退火处理的电极具有更大的活性表面积.XPS分析发现,在氧气气氛中退火处理的电极表面Sn3d_5/2、Sb3d_5/2电子的结合能较在空气气氛中退火处理的低0.15eV.动电位极化测试结果与恒电流电解实验结果都表明,在氧气气氛中退火处理的电极对水中p-苯醌具有更好的电化学催化去除性能.在电解进行至溶液完全脱色的情况下,氧气气氛中退火处理的电极对水中TOC的去除率为76.3%,而空气气氛中退火处理的电极对水中TOC的去除率为63.3%.在2种电极条件下,溶液中TOC浓度随电解时间的变化规律均符合指数变化规律.     

Visible light driven mineralization of spiramycin over photostructured N-doped TiO2 on up conversion phosphors

A novel visible light-active photocatalyst formulation(NdT/OP) was obtained by supporting N-doped TiO_2(NdT) particles on up-conversion luminescent organic phosphors(OP). The photocatalytic activity of such catalysts was evaluated for the mineralization process of spiramycin in aqueous solution. The effect of NdT loading in the range 15–60 wt.% on bulk and surface characteristics of NdT/OP catalysts was investigated by several chemicophysical characterization techniques. The photocatalytic performance of NdT/OP catalysts in the removal of spyramicin from aqueous solution was assessed through photocatalytic tests under visible light irradiation. Total organic carbon(TOC) of aqueous solution,and CO and CO_2 gas concentrations evolved during the photodegradation were analyzed. A dramatic enhancement of photocatalytic activity of the photostructured visible active NdT/OP catalysts,compared to NdT catalyst,was observed. Only CO_2 was detected in gas-phase during visible light irradiation,proving that the photocatalytic process is effective in the mineralization of spiramycin,reaching very high values of TOC removal. The photocatalyst NdT/OP at 30 wt.% of NdT loading showed the highest photocatalytic activity(58%of TOC removed after 180 min irradiation against only 31% removal after 300 min of irradiation of NdT). We attribute this enhanced activity to the high effectiveness in the utilization of visible light through improved light harvesting and exploiting. OP particles act as "photoactive support",able to be excited by the external visible light irradiation,and reissue luminescence of wavelength suitable to promote NdT photomineralization activity.     

Photocatalytic degradation of 4-tert-octylphenol in a spiral photoreactor system

A spiral photoreactor system (SPS) was developed for the degradation of 4-tert-octylphenol (4-t-OP) in aqueous phase. 4-t-OP was previously considered as a endocrine disrupting compound frequently present in water. The direct photodegradation reaction caused by the SPS was found to accord with the characteristic of apparent first-order reaction with reaction rate constantk= 4.8 × 10^-2 min^-1. However, the direct photodegradation reaction could not make the 4-t-OP mineralized. The photodegradation efficiency increased from 88% to 91.2% in 45 min irradiation period after the internal surface of SPS was sintered with TiO₂ thin film as catalyst. Catalyst concentration, number of catalyst coating layers and initial concentration of 4-t-OP were proven to be the factors affecting the photocatalytic degradation performance of the SPS on aqueous 4-t-OP. The degradation mechanism was investigated and the byproducts were analyzed using total organic carbon analyzer (TOC) and LC-MS. The possible chemical structures of the products were suggested. SPS with single layer of TiO₂ prepared by sintering 13.6% of TiO₂ precursor was proven to be more efficient than most of previous systems for removal of 4-t-OP from aqueous phase. 28.3% of the 4-t-OP was mineralized in 45 min according to the decreased amount of TOC value.     

Function of arsATorf7orf8 of Bacillus sp. CDB3 in arsenic resistance

Bacillus sp. CDB3 isolated from an arsenic contaminated cattledip site possesses an uncommon arsenic resistance (ars) operon bearing eight genes in the order of arsRYCDATorf7orf8. We investigated the functions of arsA, arsT, orf7 and orf8 in arsenic resistance using a plasmid-based gene knockout approach in the ars genedeficient Escherichia coli strain AW3110. The CDB3 arsA genewas shown to play a significant role in resistance, suggesting that the encoded ArsA may couplewith the arsenite transporter, forming an ArsAY complex that can enhance arsenite extrusion efficiency. Thedisruption of either arsT or orf7was not observed to affect arsenic resistance in the heterologous E. coli host, but their involvement in arsenic resistance can not be excluded. The orf8 gene is predicted to encode a putativedual-specificity protein phosphatasewhich also shares certain homology to arsenate reductases. The function loss of orf8 resulted in a remarkabledecrease in resistance to arsenate, though not arsenite. To examine if this effectwasdue to the reduction of arsenate by orf8, the arsC genewithin the 8-gene operonwasdisrupted. The resulting abolishment of arsenate resistance suggests that the involvement of orf8 in arsenic resistance is not via reductase activity.     

Reaction mechanism and metal ion transformation in photocatalytic ozonation of phenol and oxalic acid with Ag+/TiO2

Photocatalytic ozonation of phenol and oxalic acid （OA） was conducted with a Ag^＋/TiO2 catalyst and different pathways were found for the degradation of different compounds. Ag^＋ greatly promoted the photocatalytic degradation of contaminants due to its role as an electron scavenger. It also accelerated the removal rate of OA in ozonation and the simultaneous process for its complex reaction with oxalate. Phenol could be degraded both in direct ozonation and photolysis, but the TOC removal rates were much higher in the simultaneous processes due to the oxidation of hydroxyl radicals resulting from synergetic effects. The sequence of photo-illumination and ozone exposure in the combined process showed quite different effects in phenol degradation and TOC removal. The synergetic effects in different combined processes were found to be highly related to the properties of the target pollutants. The color change of the solution and TEM result confirmed that Ag＋ was easily reduced and deposited on the surface of Tit2 under photo-illumination, and dissolved again into solution in the presence of ozone. This simple cycle of enrichment and distribution of Ag^＋ can greatly benefit the design of advanced oxidation processes, in which the sequences of ozone and photo-illumination can be varied according to the needs for catalyst recycling and the different properties of pollutants.     

电化学还原-氧化工艺降解4-氯酚的毒性研究

采用紫外光还原法制备了Pd-Fe/石墨烯催化阴极,并以Ti/IrO_2/RuO_2为阳极,构成三电极体系(双阴极)和两电极体系(单阴极)的电化学还原-氧化降解工艺,分别对4-氯酚进行降解.采用离子色谱、高效液相色谱、TOC仪对4-氯酚降解过程中中间产物及其浓度进行测定.根据公式计算降解过程中理论计算毒性值,应用发光细菌法测定降解过程中的实际毒性值,对理论计算毒性值与实际毒性值进行比较,分析不同体系下降解过程中毒性的变化规律.结果表明,两种工艺体系在最佳降解条件下,阴极室毒性均呈下降的趋势,由于降解过程中在阳极室生成高毒性的苯醌,阳极室毒性均先升高后降低.通过相关性分析得到,两种体系理论计算毒性与实际毒性在P=0.01水平下,相关性系数均为1,显著相关,表明降解过程中实际毒性的测定结果真实可靠.降解至120 min时,三电极体系毒性小于两电极体系,表明三电极体系优于两电极体系.据此提出实际毒性测定方法在电化学还原-氧化工艺降解氯酚类有机废水毒性测试的工业应用中有着广泛的前景.     

不同TOC/NH4+-N对厌氧氨氧化脱氮效能的影响

采用SBR厌氧氨氧化反应器,研究了不同TOC与NH_4~+-N比值对厌氧氨氧化反应器的脱氮效能的长短期影响.结果表明,在有机物短期影响时,反应器所能承受的最大TOC/NH_4~+-N为1.4,总氮去除速率可达0.26 kg·(m~3·d)~(-1).长期影响下,在TOC/NH_4~+-N小于0.4时,反应器可获得最高脱氮效能,总氮去除率为0.34 kg·(m~3·d)~(-1),TOC/NH_4~+-N大于0.4后,反应器脱氮效能持续降低,并且短期内厌氧氨氧化菌难以迅速恢复活性.利用q PCR(定量PCR)技术对长期影响前后反应器内菌种群落变化做定量分析,结果表明随着有机物的增加,反应器中的ANAMMOX菌数量从2.9×10~(11)copies·mL~(-1)减少至3.15×10~(10)copies·mL~(-1),在TOC/NH_4~+-N大于1.6的环境中,NH_4~+-N未能由厌氧氨氧化菌去除,厌氧氨氧化菌不能表现出生物活性.此时测得反硝化菌数量为3.0×10~9copies·mL~(-1),反应器中的NO_2~--N绝大部分由反硝化去除,虽然反硝化菌数量远少于ANAMMOX菌,但能表现出远超ANAMMOX菌的活性.     

Ni2P/Bi2MoO6复合材料的制备及可见光催化活性

分别制备了花状Bi₂MoO₆和片状Ni₂P,采用研磨、水热及超声的方式将两种材料复合,考察了负载方式、负载率和溶液pH值对其可见光下降解亚甲基蓝（MB）的影响;利用XRD、XPS、FTIR、SEM、PL和UV-Vis等测试手段表征了样品的微观结构、形貌和光学性质;研究表明Ni₂P作为助催化剂,可加速电子空穴对分离,显著提高Bi₂MoO₆的光催化活性,其中当Ni₂P负载率为4%时,TOC去除率为64.28%,降解速率为纯Bi₂MoO₆的2倍,且将Ni₂P/Bi₂MoO₆复合催化剂循环利用3次后,同实验条件下降解率为94%,证明复合催化剂稳定性好.     

磺胺二甲基嘧啶在过硫酸盐存在下的辐照降解研究

本研究对磺胺二甲基嘧啶(SMT)在不同条件下的辐照降解进行了研究.SMT(20 mg·L~(-1),约0.072 mmol·L~(-1))在外加过硫酸根浓度为0、1、2、4、10和20 mmol·L~(-1)条件下分别进行辐照,发现伽马辐照可有效去除水中的SMT,并可极大地促进溶液TOC的去除,过硫酸盐与伽马辐照联合作用表现出明显的协同效应.在本研究中,各条件下的辐照降解反应均符合准一级反应动力学.在外加过硫酸盐的条件下,溶液的矿化度可以得到极大的提高,当吸收剂量为1 k Gy时,其矿化度由3.5%提高到22.8%,当吸收剂量为5 k Gy时,矿化度由14.1%提高到70.1%.在辐解后的溶液中,利用IC检测到硫酸根离子(SO_4~(2-))、甲酸根离子(HCOO~-)和乙酸根离子(CH_3COO~-)3种离子的存在,一部分中间产物通过GC-MS检测得到,常见的含氮离子(NO_2~-、NO_3~-和NH_4~++)并未在溶液中检测到.同时,本研究还深入探讨了SMT辐照降解机理和降解途径.     

硫代硫酸钠对排硫硫杆菌固碳能力的影响及其作用机制

通过测定不同浓度Na_2S_2O_3·5H_2O培养时排硫硫杆菌(DSM 505)菌液的总有机碳浓度(TOC),分析Na_2S_2O_3·5H_2O对排硫硫杆菌固碳能力的影响,并结合各浓度Na_2S_2O_3·5H_2O条件下固碳关键酶Rubis CO编码基因cbb的转录特性和胞外游离有机碳浓度(EFOC),阐明Na_2S_2O_3·5H_2O影响排硫硫杆菌固碳能力的作用机制.结果表明,适当范围内增加Na_2S_2O_3·5H_2O的浓度能显著提高排硫硫杆菌的固碳能力,降低胞外游离有机碳在总有机碳中所占的比例.cbb基因转录特性分析结果表明,Na_2S_2O_3·5H_2O浓度对cbb基因的转录效率和表达模式均无显著影响.因此推测Na_2S_2O_3·5H_2O影响排硫硫杆菌固碳能力的作用机制可能是作为电子供体提供能量,促进细胞骨架合成,从而削弱胞外游离有机碳对排硫硫杆菌自养过程的抑制作用,进而增强固碳能力.     

Evaluation of RothC model using four Long Term Fertilizer Experiments in black soils, India

Carbon content in soils changes depending on the land use system, type of management practice and time. There is an increasing concern about the soil quality vis-à-vis organic carbon content in soils due to global warming and enhanced CO₂ concentration in the atmosphere. This has led to estimate carbon stock in soils at global and regional levels. The objective of the present study was to evaluate RothC model to estimate total organic carbon (TOC) changes under four long term fertilizer experimental sites representing sub-humid moist (Sarol and Nabibagh), sub-humid dry (Panjri) and semi-arid (Teligi) climate in India. The plant carbon input rate was calibrated using organic carbon and other soil parameters using RothC. The results showed that RothC could simulate changes in TOC in two contrasting eco-sites for surface soil layers. The root mean square error (RMSE) considered as modelling error ranged from 11.50 to 15.01, 4.70 to 11.60, 2.14 to 6.52 and 1.45 to 13.74 in the surface layers of Sarol, Nabibagh, Panjri, and Teligi sites, respectively. The simulation biases expressed by M (relative error) by Student‘t’ value for all the treatments at these sites were non-significant with two exceptions. Observed trends in TOC consist of an increase for all the four treatments in the sub-humid site of Sarol and Nabibagh; while manures alone or in combination increase TOC appreciably in Teligi and Panjri. TOC remained, however, almost similar over years for the control (no fertilizer or manure) and NPK treatments in all the four sites. Analysis of RothC output data showed that this model could be used as a tool to arrive at different threshold values of rainfall to influence decomposition rate modifier and thus to find out rate of organic carbon sequestration in various bioclimatic systems.     

g-C3N4在可见光下协同PDS降解磺胺二甲嘧啶的机制研究

以二聚氰胺为前驱体合成光催化剂石墨相碳化氮(g-C_3N_4),通过透射电子显微镜(TEM)、X射线衍射(XRD)和紫外可见漫反射光谱(UV-vis DRS)等技术对g-C_3N_4材料进行形貌结构和光学性能的表征.实验过程中,以g-C_3N_4光催化降解磺胺二甲嘧啶(SMZ)中,加入过硫酸盐(PDS)联合效果的研究结果表明,PDS加快了g-C_3N_4对SMZ的光催化降解;通过荧光测试,表明了PDS使g-C_3N_4的光生空穴(h~+)与光生电子(e-)能够进行有效地分离,从而加强其光催化性能;实验同时研究了PDS/g-C_3N_4体系对磺胺二甲嘧啶(SMZ)光催化降解的影响机制.研究表明,SMZ的光催化降解反应符合准一级动力学规律;pH在酸性环境下有利于SMZ的降解;使用草酸钠作为光生空穴分子捕获剂,检测到h~+存在于PDS/g-C_3N_4光催化体系中,并计算得出h~+的贡献率为65.9%,表明h~+在降解中起到主要作用;TOC的检测表明,加入PDS有助于SMZ的矿化.     

碳底物含量对厌氧条件下水稻土N2、N2O、NO、CO2和CH4排放的影响

理解底物碳氮对厌氧条件下水稻土排放氮素气体——氮气(N2)、氧化亚氮(N2O)和一氧化氮(NO)以及二氧化碳(CO2)和甲烷(CH4)的影响,有助于制定合理的温室气体减排措施,定量了解反硝化产物组成对碳底物水平的依赖性,也有助于氮转化过程模型研发中制定正确的关键过程参数选取方法或参数化方案.本研究采用粉砂壤质水稻土为研究对象,设置对照(CK)和加碳(C+)两个处理,前者的初始硝态氮和可溶性有机碳(DOC)含量分别为~50 mg·kg-1和~28 mg·kg-1,后者的分别为~50 mg·kg-1和~300 mg·kg-1.采用氦环境培养-气体及碳氮底物直接同步测定系统,研究了完全厌氧条件下碳底物水平对上述气体排放的影响.结果表明,CK处理无CH4排放,而C+处理可观测到CH4排放;C+处理的综合增温潜势显著高于CK处理(P<0.01);NO、N2O和N2排放量占这3种氮素气体排放总量的比重,在CK处理分别约为9%、35%和56%,在C+处理分别约为31%、50%和19%,处理间差异显著(P<0.01).由此表明,碳底物水平可显著改变所排放氮素气体的组成;对于旱地阶段硝态氮比较丰富的水稻土,避免在淹水前或淹水期间施用有机肥,有利于削减温室气体排放.