腐植酸中不同分子量组分与As(Ⅲ)的络合性能

采用超滤方法将腐植酸（HA）分成5个不同分子量组分,利用平衡透析法研究HA中不同分子量组分与As（III）的络合特征和作用机理,计算络合过程的条件分配系数、表观稳定常数.结果表明,腐植酸组分的分子量对HA与As（III）的络合过程有显著的影响,当分子量小于10kDa时,HA与As（III）络合能力明显强于其他条件.其中羧基和酚羟基在HA与砷络合中起重要作用,为主要络合位点.采用Scatchard分析和双位点配体模型对络合结果进行拟合,发现HA中不同分子量组分和As（III）的络合过程中均存在强和弱2种络合位点.     

腐植酸中不同分子量组分与As(Ⅲ)的络合性能

采用超滤方法将腐植酸（HA）分成5个不同分子量组分,利用平衡透析法研究HA中不同分子量组分与As（III）的络合特征和作用机理,计算络合过程的条件分配系数、表观稳定常数.结果表明,腐植酸组分的分子量对HA与As（III）的络合过程有显著的影响,当分子量小于10kDa时,HA与As（III）络合能力明显强于其他条件.其中羧基和酚羟基在HA与砷络合中起重要作用,为主要络合位点.采用Scatchard分析和双位点配体模型对络合结果进行拟合,发现HA中不同分子量组分和As（III）的络合过程中均存在强和弱2种络合位点.     

一种新的方便的测定天然水中三价砷的方法

介绍了测定天然水中三价砷的新方法．该方法是在测定无机砷（总砷）“标准方法”的基础上．对其进行修改而提出来的。实验中此方法能检出作品中平均96％的三价砷。结合通用的“标准方法”．则新提出的方法可以容易地把水中无机砷分为砷（＋3）、亚砷酸盐和砷（＋5）、砷酸盐。     

砷在三种紫色土中的化学行为及其与作物效应的关系

通过水稻在不同砷浓度处理过的三种紫色土的盆栽试验,研究了砷的吸附特征,形态变化及其与砷的作物效应的关系,揭示了砷在不同土壤中对水稻毒害和在水稻体内累积程度不一样的原因是由于不同土壤的性质影响到砷的吸附和形态变化。其中砷在土壤中的形态变化是最重要的因素之一。在诸形态中,以A-As和Ca-As最为重要。土壤的碳酸盐体系可能是影响三种紫色土砷的化学行为及其生态效应的一个重要因素。     

Fe(II)、Fe(III)对砷与不同分子量腐植酸络合性能的影响

以腐植酸（HA）代表天然有机质,采用平衡透析和超滤的方法研究铁离子（Fe （II）、Fe （III））对不同分子量HA与砷离子（As （V）、As （III））络合作用的影响,并利用红外光谱（FT-IR）表征其络合特征.结果发现,Fe （II）和Fe （III）均能增强HA络合As能力,且对As （V）络合能力的增强作用大于As （III）;pH值显著影响HA络合As能力;溶解性有机碳（DOC）浓度由5mg/L增大到200mg/L,As络合百分比随之增加,此时HA-Fe （III）络合As （III）百分比最大,为24.55%;初始As浓度由10μg/L增加1000μg/L,As络合百分比随之降低,其中HA-Fe （III）络合As （III）百分比最低,为3.11%.相同环境条件下,分子量>100kDa络合As百分比最大,其中HA-Fe （II）络合As （III）的百分比最高为26.43%;分子量小于10kDa的HA络合As百分比明显高于其他分子量的HA.Fe的增强作用主要源于Fe与羧基形成桥梁再与As络合形成三元络合物.     

桑沟湾总溶解态无机砷的分布与季节变化

:利用氢化物发生原子荧光光谱法对桑沟湾春、夏、秋、冬四个季节的总溶解态无机砷(TDIAs=[As3 ] [As3 ])进行了测定.TDIAs的浓度4月和7月较低,分别为9.3±1.6 nmol/L,8.3±2.2 nmol/L;而11月和1月浓度较高,分别为18.5±0.6 nmol/L,17.9±2.0 nmol/L.4到7月,湾内海带等生长旺盛,湾内水交换能力较差,湾内TDIAs浓度较低;秋季海带收获后和冬季海带苗刚人海且生长缓慢,湾内水交换能力比4月和7月高,此时海湾内TDIAs浓度也较高.TDIAs在桑沟湾的分布和季节变化受湾内海带、贝类养殖和水文环境的影响显著.     

缺氧条件下土壤砷的形态转化与环境行为研究

采集张士污灌区0～100 cm深的土壤并在实验室里负载低浓度的砷,采用不加硫和加硫对比研究了厌氧条件下土著微生物对土壤中砷的形态转化、环境行为影响及其机制.结果表明,在不外加硫酸盐条件下厌氧培养8 d后,微生物还原作用造成砷的大量还原和释放,释放的砷70%以上是以As(Ⅲ)形式存在,尤其20～40 cm深度土壤砷的释放量明显高于其它层土壤,As(Ⅲ)和As(T)分别达到892.8μg.L-1和1 240.6μg.L-1.与非生物对照相比每层土中盐酸可提取的砷总量都大大降低,且盐酸提取的As(T)几乎全部转化为As(Ⅲ).伴随砷的释放,铁发生还原和释放,溶解态的亚铁基本都在40 mg.L-1以上,不同土层固相中亚铁离子的量都在9.0～13.4 g.kg-1范围内,固相盐酸可提取态总铁中亚铁离子所占的比例基本都在50%以上,说明微生物还原作用造成固相中铁氧化物发生还原性溶解和矿物结构转化.当体系中添加10 mmol.L-1的硫酸盐时,每层土的生物培养体系中铁的释放几乎完全被抑制,砷和铁浓度也减少了50%.与不加硫生物培养体系相比,固相中盐酸可提取的砷量减少了50%,一部分砷被转化为稳定的硫化物As2S3而固定.可见在硫酸盐不足条件下微生物还原作用可造成砷被还原、活化和释放,而补充土壤中硫酸盐的量可促使微生物还原/活化的砷转化成更加稳定的形态,稳定的硫化物矿物As2S3是土壤微生物固定砷的重要途径.     

长江中下游两种典型水稻土微生物对砷污染的响应

基于温室盆栽实验,利用磷脂脂肪酸分析(PLFA)方法研究了As污染、土壤类型和水稻品种对水稻抽穗期土壤微生物群落的影响.结果表明,水稻土土壤中微生物生物总量(总PLFAs)以及微生物组成均不同程度的受到了As污染、土壤类型及水稻品种的影响;As污染增加了土壤总PLFAs,黄泥田的土壤总PLFAs、真菌/细菌(F/B)、革兰氏阳性细菌/阴性细菌(G+/G-)、腐生真菌/丛枝菌根真菌(SF/AMF)显著高于红泥田;在黄泥田中,种植籼稻品种的土壤总PLFAs较杂交稻和粳稻品种平均减少30.0%,而在红泥田中平均增加24.8%.偏Mantel检验和冗余分析(RDA)表明土壤pH值、DOC、NH4+和As浓度是驱动水稻土微生物群落演变的主控因子,其中受As影响较大的特征PLFAs包括20:0、i17:1ω9c、18:1ω9c、cy17:0和18:3ω6c;ABT预测模型显示水稻品种和土壤类型对总PLFAs、F/B、G+/G-和SF/AMF指标的贡献相对较大,而As处理的影响较小.     

珠三角典型区域农田小区尺度氮、磷、镉、砷输移特征与控制对策

区域氮、磷、镉、砷输移变化是影响农业生产、导致农田面源污染的主要因素。基于土壤表观平衡模型,以珠三角流域佛山市农业科学研究所试验农田为典型研究区域,构建农田小区尺度土壤表观氮、磷、镉、砷平衡模型,对4种元素在土壤中输移结构和平衡进行分析。结果表明：研究区域4种元素的主要输入途径是施肥,而输出的主要形式各有不同。其中,氮、磷主要输出形式是作物富集输出,输出占比分别为57.5%和39.0%;镉、砷主要输出形式分别是地表径流和作物富集输出,输出占比分别为66.7%和10.7%。研究区域4种元素均出现了不同程度土壤富集现象,农田小区尺度氮、磷平衡处于盈余状态,而镉、砷平衡处于亏损状态,4种元素的平衡强度分别为37.40、8.88、−1.35和−20.50 kg/(hm²·a),仅氮、磷未超过当地土壤环境安全阈值。分析试验农田中5类蔬菜各部位镉、砷富集情况发现,砷的富集系数均达到70.0%以上,而镉的富集只在辣椒叶中较为突出,富集系数达到57.5%。研究显示,应重视肥料输入的有效利用,加强农田灌溉水、农作物和地表径流中重金属的监测,以保障区域粮食安全和水环境安全。

     

Removal natural organic matter in typical south-China source water during enhanced coagulation of a with IPF-PACl

Systematic investigation on enhancing removal of natural organic matter （NOM） using inorganic polymer flocculant （IPF）, polyaluminum chloride（PACI） and polyacrylamide（PAM） was performed in a typical south-China source water. Enhanced coagulation and applying polymer flocculant-aid were compared through jar tests and pilot tests. Raw water and settled water were characterized and fractionated by resin adsorption. The results show that DOC composes major part of TOC. The DOC distribution keeps relatively stable all around the year with typical high amounts of the hydrophilic matter around 50%. The distribution between HoB, HoA and HoN varies and undergoes fluctuation with the year round. During the summer season, the HoN becomes gradually the major part in hydrophobic parts. PACI with the species being tailor-made shows little pH effect during coagulation. The enhanced coagulation dosage for PACI could be 4.5 mg/L for the typical source water. The highest TOC removal achieved 31%. To be economically, 3 mg/L dose is the optimum dosage. Although hydrophilic fractions of NOM of both treatment strategies are removed about 30%, NOM causing UV254 absorbance were well removed（about 90%）. Hydrophobic bases and acids fractions are much more removed under enhanced conditions. The hydrophilic fraction could be better removed using PAM, the polymer coagulant aid.     

Effects of ion concentration and natural organic matter on arsenic(V) removal by nanofiltration under different transmembrane pressures

The removal of As(V) from synthetic water was studied using four different nanofiltration (NF) membranes (ESNA-1-K1, NF270, ESNA-1-LF, and HODRA-CORE). The influences of ion concentration, transmembrane pressure (TMP), and the presence of natural organic matter (humic acid, HA) on the arsenic removal efficiency and permeate flux were investigated. The arsenic rejection of ESNA- 1-LF was higher than those of the other membranes in all experiments (> 94%), and the HODRA-CORE membrane gave the lowest removal of arsenic (< 47%). An increase in the ion concentration in the feed solution and addition of HA decreased the arsenic rejection of the HODRA-CORE membrane. However, both increasing of the ion concentration and addition of HA made the rejection increased for the other membranes (ESNA-1-K1, NF270, and ESNA-1-LF). With increasing TMP, for all four NF membranes, increases in both arsenic rejection and permeate flux were observed. The permeate fluxes of the four NF membranes decreased to some extent after addition of HA to the solutions for operating time of 6 hr.     

黄、东海溶解态无机砷的形态及其分布

利用氢化物发生原子荧光光谱法对2000年10月和2001年5月航次黄、东海的无机砷进行了测定.两个航次中黄、东海总溶解态无机砷(TDIA8)含量的变化范围分别为9.-21.和12.～23.nmoL,L,亚砷酸盐(As3 )含量的变化范围分别为0.2-2.4和0.1-9.2 nmoL/L,2000年秋季TDIAs和As3 的含量明显低于2001年春季.长江对黄、东海的影响非常显著,是主要的物质来源之一.黄海溶解态无机砷的平面分布表现为沿岸和东黄海交界处高,黄海中部冷水团区含量较低.东海自长江口向西南琉球群岛沿伸的PN断面中,TDIAs和As3 的分布存在明显的梯度,自长江口向中央海区递减,然后由于受到黑潮水入侵含量又开始升高.东海陆架区As3 的含量、分布受到浮游植物活动的影响,表现出与叶绿素含量存在相关关系.     

有机质和阳离子对氧化石墨烯团聚行为的影响

利用动态光散射技术分别考察了3种天然有机质（NOM）及其浓度和阳离子对纳米氧化石墨烯（GO）在水环境中团聚动力学的影响.无NOM存在时,GO团聚行为符合经典的Derjaguin-Landau-Verwey-Overbeek（DLVO）理论和舒尔采-哈迪准则.Na⁺溶液中,NOM显著增强GO稳定性,顺序为腐殖酸（HA） > 富里酸（FA） > 海藻酸钠（SA）,这主要是由于HA在GO之间产生了更强的空间位阻斥力.以HA为代表性有机质,2mg/L HA对GO在水溶液中的稳定性还受阳离子种类的影响：HA增强了GO在Na⁺和Mg²⁺溶液中的稳定性,然而对GO在Ca²⁺溶液中的稳定性几乎没有影响.提高HA浓度为5mg/L时：高浓度Mg²⁺溶液中,HA的盐析效应使得其未促进GO稳定性;Ca²⁺溶液中,HA与Ca²⁺发生了较强的桥联作用,使得HA促进了GO的团聚.     

Atomic force microscopy study on the microtopography of natural organic matter and newly formed hydrous MnO2

To understand the water purification mechanism of potassium permanganate as a coagulation-aid during the preoxidation process, the microtopography of its reductive products, the newly formed hydrous manganese dioxide and the aged hydrous manganese dioxide, was investigated. The morphology of natural organic matter (NOM) adsorbed by the newly formed hydrous manganese dioxide was also compared with that of NOM alone. By using the tapping mode atomic force microscopy (AFM), the observation results show that the newly formed hydrous manganese dioxide possess a perforated sheet (with a thickness of 0–1.75 nm) as well as some spherical particle structures compared with the hydrous manganese dioxide with 2 h aging time, which demonstrated that the newly formed hydrous manganese dioxide had a large surface area and adsorption capacity. When 1 mmol/L newly formed hydrous manganese dioxide was added, the microtopography of NOM molecules shifted from a loosely dispersed pancake shape (with adsorption height of 5–8.5 nm) to a densely dispersed and uniform spherical structure. These results provide a valid proof that it is the perfect adsorption capability of the newly formed hydrous manganese dioxide that might result in the coagulation aid effect of potassium permanganate preoxidation. Translated from Environmental Science, 2006, 27(5): 945–949 [译自: 环境科学]     

溶解有机质对微生物异化还原铁过程中砷含量及其形态赋存规律的影响

基于典型的希瓦氏金属还原菌(Shewanella decolorationis S12)和石英砂负载铁砷(As-IOCS)的相互作用,探讨了不同来源及组分溶解有机质和生物/非生物条件下对上述作用过程的影响.结果表明,不同类型及组分溶解有机质(DOM)均能使石英砂上负载的铁砷微生物还原解离/解吸程度得到一定程度的加强.而非生物反应体系中,只有含氧化还原敏感官能团结构的蒽醌类物质(0.1 mmol·L-1AQS)对铁砷的解离/解吸作用产生明显影响.在0.1 mmol·L-AQS和有机络合物(2 mmol·L-1 EDTA)的影响下,使得石英砂上负载铁的微生物异化还原程度加强,导致As(Ⅴ)从石英砂负载铁上的解吸程度也随之得到加强;在未加菌体系中,AQS和EDTA和不同组分的DOM类似,对As(Ⅴ)从IOCS上解吸程度影响微弱.对于As(Ⅲ)来说,只有在AQS的影响下,其含量得到显著增加,这可能是作为氧化还原中介体的AQS,在厌氧的生物/非生物条件下,能促进电子在As不同形态之间的转移,使得高价态As(Ⅴ)向还原态As(Ⅲ)的还原转变更易进行.当S12菌液接种含量增加时,在污泥不同组分DOM的影响下,As(Ⅴ)的解吸程度在反应300h前得到明显加强,而As(Ⅲ)的含量在整个反应期间,均快速上升,表明菌液含量高的体系,微生物铁异化还原过程得以持续进行,同时也促进了As(Ⅴ)向As(Ⅲ)的还原转变.     

Molecular characterization of transformation and halogenation of natural organic matter during the UV/chlorine AOP using FT-ICR mass spectrometry

UV/chlorine process, as an emerging advanced oxidation process (AOP), was effective for removing micro-pollutants via various reactive radicals, but it also led to the changes of natural organic matter (NOM) and formation of disinfection byproducts (DBPs). By using negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS), the transformation of Suwannee River NOM (SRNOM) and the formation of chlorinated DBPs (Cl-DBPs) in the UV/chlorine AOP and subsequent post-chlorination were tracked and compared with dark chlorination. In comparison to dark chlorination, the involvement of ClO^?, Cl^?, and HO^? in the UV/chlorine AOP promoted the transformation of NOM by removing the compounds owning higher aromaticity (AI_mod) value and DBE (double-bond equivalence)/C ratio and causing the decrease in the proportion of aromatic compounds. Meanwhile, more compounds which contained only C, H, O, N atoms (CHON) were observed after the UV/chlorine AOP compared with dark chlorination via photolysis of organic chloramines or radical reactions. A total of 833 compounds contained C, H, O, Cl atoms (CHOCl) were observed after the UV/chlorine AOP, higher than 789 CHOCl compounds in dark chlorination, and one-chlorine-containing components were the dominant species. The different products from chlorine substitution reactions (SR) and addition reactions (AR) suggested that SR often occurred in the precursors owning higher H/C ratio and AR often occurred in the precursors owning higher aromaticity. Post-chlorination further caused the cleavages of NOM structures into small molecular weight compounds, removed CHON compounds and enhanced the formation of Cl-DBPs. The results provide information about NOM transformation and Cl-DBPs formation at molecular levels in the UV/chlorine AOP.     

Molecular characterization of effluent organic matter in secondary effluent and reclaimed water: Comparison to natural organic matter in source water

Municipal wastewater reclamation is becoming of increasing importance in the world to solve the problem of water scarcity. A better understanding of the molecular composition of effluent organic matter(Ef OM) in the treated effluents of municipal wastewater treatment plants(WWTPs) is crucial for ensuring the safety of water reuse. In this study, the molecular composition of Ef OM in the secondary effluent of a WWTP in Beijing and the reclaimed water further treated with a coagulation–sedimentation–ozonation process were characterized using a non-target Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) method and compared to that of natural organic matter(NOM) in the local source water from a reservoir. It was found that the molecular composition of Ef OM in the secondary effluent and reclaimed water was dominated by CHOS formulas, while NOM in the source water was dominated by CHO formulas. The CHO formulas of the three samples had similar origins. Anthropogenic surfactants were responsible for the CHOS formulas in Ef OM of the secondary effluent and were not well removed by the coagulation-sedimentation-ozonation treatment process adopted.     

Characterization of natural organic matter in water for optimizing water treatment and minimizing disinfection by-product formation

正Introduction Natural organic matter(NOM)present in source water has significant impact on water treatment processes and on the quality of drinking water.NOM is a complex mixture of diverse groups of organic compounds,humic and fulvic acids,proteins,peptides,carbohydrates,and heterogeneous materials     

无机砷和甲基砷在水稻体内吸收运移的比较研究

由于含甲基砷的农药残留或土壤中微生物的砷甲基化作用,除了无机砷,水稻籽粒中也可以检测到相当含量的不同形态的甲基砷.通过水培试验研究了不同形态砷在水稻幼苗中的吸收、转运、转化和外排.结果表明,水稻中各形态砷的含量排序为:亚砷酸盐(As(Ⅲ))>单甲基砷盐(MMA(Ⅴ))>砷酸盐(As(Ⅴ))>二甲基砷盐(DMA(Ⅴ)),但从地下部向地上部的转运系数排序为:DMA(Ⅴ)>As(Ⅲ)>As(Ⅴ)>MMA(Ⅴ).实验中未发现水稻体内无机砷向甲基砷的转化,甲基砷向无机砷的转化比例也较低,但观察到MMA(Ⅴ)部分被还原为MMA(Ⅲ).相比其地上部和地下部的吸收量,DMA(Ⅴ)在水稻中通过木质部(向上)和韧皮部(向下)的转运比例在4种形态砷中最高.甲基砷(MMA(Ⅴ)和DMA(Ⅴ))通过根系外排的速率和比例明显的高于无机砷(As(Ⅲ)和As(Ⅴ)).实验结果表明,不同形态砷的累积与其在水稻体内的吸收、运移及砷的根系外排密切相关.