道路雨水径流溶解性有机物与重金属结合作用分析

为了解道路雨水径流溶解性有机物(DOM)与重金属的相互作用,采用荧光激发-发射矩阵光谱、超滤、离子选择电极法及红外光谱等技术对道路雨水径流溶解性有机物及其组分同Cu~(2+)、Pb~(2+)和Cd~(2+)的络合作用进行了研究.结果表明,道路雨水径流DOM与3种重金属离子的络合作用由强到弱依次是:Cu~(2+)Pb~(2+)Cd~(2+),4种分子量DOM组分与重金属之间均发生了络合反应,且DOM组分分子量越小,与重金属之间的络合作用越强.4个不同分子量区间的DOM组分与Cu~(2+)、Pb~(2+)和Cd~(2+)之间的络合作用由强到弱的顺序为:1 kDa组分、1~10 kDa组分、10~30kDa组分、30 kDa~0.45μm组分.     

典型城市河流底泥溶解性有机质与重金属响应机制研究

应用三维荧光光谱(EEMs)结合平行因子(PARAFAC)分析、典范对应分析(CCA)和结构方程模型(SEM),以沈阳市建城区黄泥河、新开河、满堂河为研究对象,测定河流底泥营养盐和重金属浓度,检测溶解性有机质(DOM)三维荧光光谱,研究城市河流底泥DOM与重金属响应机制。总氮(TN)和总磷(TP)的平均浓度均为新开河>黄泥河>满堂河,TP平均浓度均大于650 mg/kg,根据US EPA底泥分类标准属于重度污染。基于相关性分析,黄泥河Cu、Ni、Cr具有同源性,新开河As、Cd和Hg具有同源性,满堂河As和Zn具有同源性。基于PARAFAC分析,DOM含有5个荧光组分,即陆源类腐殖质(C1)、类富里酸(C2和C3)、类胡敏酸(C4)和类色氨酸(C5)。C1的丰度占总丰度的30.31%,C2和C3占37.76%,显示陆源类腐殖质和类富里酸为DOM的主要组分。黄泥河与新开河DOM受外源影响较大,而满堂河受内源影响较大。CCA分析表明:C3、C5、Cr和Pb是影响黄泥河底泥的特征因子,Hg是影响新开河底泥的特征因子,TP、As和Zn是影响满堂河底泥的特征因子。基于SEM分析,TN、TP、C1、C2、C3和C5对重金属的权重分别为25.46%、22.16%、17.52%、15.42%、9.11%和10.33%,表明TN和TP是3条河底泥重金属的主要影响因子。营养盐对重金属的路径系数为-0.18,重金属对Hg、As、Zn、Cd路径系数分别为-2.83、-1.69、-1.91和-3.24,表明它们具有同源性;此外,DOM与重金属路径系数为0.11,重金属对Pb和Cr的路径系数为1.58和1.00,表明DOM与Pb和Cr具有同源性。     

水溶性有机质对土壤及底泥中汞吸附行为的影响

以重庆市2种耕作土(黄壤和中性紫色土)及鱼塘底泥为试验材料,分别添加提取自腐殖土的DOM(DOMh),提取自稻草的DOM(DOM)和提取自污泥堆肥的DOM(DOMa),研究DOM对土壤及底泥中Hg的吸附行为的影响.结果表明.DOM对土壤及底泥中汞的吸附行为均有一定的抑制作用,这种抑制作用与DOM种类和试验材料的性质有关.添加不同来源的DOM,对Hg的抑制作用具体表现为:DOMh>DOMr>DOMa;添加同一种DOM时,对Hg吸附的抑制作用表现为鱼塘底泥>紫色土>黄壤.     

沱江流域水系沉积物重金属的潜在生态风险评价

通过对沱江流域水系沉积物的系统研究,查明了重金属元素含量的空间分布特征,进行了潜在生态风险质量评价。研究结果显示,在两支流交汇之前,沉积物中重金属的污染水平从上游到下游呈上升趋势,矿业活动是水环境中重金属的主要来源,两支流交汇之后元素含量有较明显升高,显示两河汇流叠加对沱江下游水系沉积物有较大的影响;与前人研究相比,各元素含量有较明显的增加;沱江水系沉积物中重金属的潜在生态风险水平较低,大多属于轻微生态风险,Cd的潜在生态危害程度最严重;多种重金属的潜在生态风险指数(R1)表明河流重金属污染属于轻微生态危害,其受危害程度由大到小的顺序为:沱江>石亭江>绵远河。     

蘑菇湖沉积物间隙水溶解性有机质紫外可见光谱研究

从蘑菇湖选取7个采样点,提取沉积物间隙水DOM样本,运用主成分分析与聚类分析方法对蘑菇湖沉积物间隙水紫外可见光谱进行解析,识别光谱组分与主控因子,并研究DOM的组成、腐殖化程度及空间变化。结果表明,DOM组分为木质素和奎宁、羧酸基团及多烷基腐殖质等,在外围区与深湖区2个区域存在明显差异。从吸收光谱推演出具有良好相关性的S_r、SUVA₂₅₄、E₂/E₃、E₂/E₄、E₂₅₃/E₂₀₃、A₂/A₁ 6个光谱指标,可以用于表征DOM的分子量大小和腐殖化水平,外围区DOM的分子量和腐殖化程度皆高于深湖区,并且在区域内呈现随水深增加而递减的趋势。光谱指标聚类分析结果表明,与腐殖化水平呈正相关的指标(E₂₅₃/E₂₀₃、SUVA₂₅₄、A₂/A₁)在表征DOM腐殖化水平时更具有代表性。根据光谱指标聚类结果将7个采样点分为2类,该结果与主成分分析一致。通过DOM腐殖化程度可以在一定程度上判断其空间变化规律。     

水源水库沉积物及其上覆水DOM光谱特征

为探究水源水库溶解性有机质(DOM)组成结构及来源,以深圳市茜坑水库为例,采用紫外-可见光谱技术(UV-Vis)并结合平行因子分析法三维荧光光谱技术(EEMs-PARAFAC)对水库表层沉积物及其上覆水的DOM光谱特征进行分析.结果表明:PARAFAC识别出3类荧光组分,分别是Cl(Ex/Em=270/304nm,类蛋...     

Toxicities and risk assessment of heavy metals in sediments of Taihu Lake, China, based on sediment quality guidelines

The occurrence, toxicities, and ecological risks of five heavy metals(Pb, Cu, Cd, Zn and Ni) in the sediment of Taihu Lake were investigated in this study. To evaluate the toxicities caused by the heavy metals, the toxicities induced by organic contaminants and ammonia in the sediments were screened out with activated carbon and zeolite. The toxicities of heavy metals in sediments were tested with benthic invertebrates(tubificid and chironomid).The correlations between toxicity of sediment and the sediment quality guidelines(SQGs)derived previously were evaluated. There were significant correlations(p 0.0001) between the observed toxicities and the total risk quotients of the heavy metals based on SQGs,indicating that threshold effect level(TEL) and probable effect level(PEL) were reliable to predict the toxicities of heavy metals in the sediments of Taihu Lake. By contrast, the method based on acid volatile sulfides(AVS) and simultaneously extracted metals(SEM),such as ∑SEM/AVS and ∑SEM-AVS, did not show correlations with the toxicities. Moreover,the predictive ability of SQGs was confirmed by a total predicting accuracy of 77%. Ecological risk assessment based on TELs and PELs showed that the contaminations of Pb, Cu, Cd and Zn in the sediments of Taihu Lake were at relatively low or medium levels. The risks caused by heavy metals in the sediments of northern bay of the lake, which received more wastewater discharge from upper stream, were higher than other area of the lake.     

Co-transport of dissolved organic matter and heavy metals in soils induced by excessive phosphorus applications

To evaluate the e ects of long-term applications of phosphorus fertilizers on mobility of dissolved organic matter (DOM) and heavy metals in agricultural soils, a sandy soil and a loamy soil were spiked with ammonium phosphate at application rates of 0, 25, 50, 100, 250, and 500 mg P per kilogram of soil. A series of 15-cm long soil columns were constructed by packing incubated soils of varying concentrations of P. The soil columns were consecutively leached by simulated rainfalls for six cycles. The contents of water extractable organic carbon in both sandy and loamy soils increased significantly with increasing rates of P applications. Relatively high rates of P applications could induce a marked increase in DOM concentrations in the leachates, the e ects were larger with the sandy soil rather than with the loamy soil. Applications of P changed the partitioning of trace metals in the soil solids and the soil solutions. The increased P application rates also seemed to elevate the leaching of Cu, Cd, and Zn from soils. The concentrations of Cu, Cd, and Zn in the leachates were positively correlated with DOM, probably due to the formation of metal-DOM complexes. In contrast, Pb concentrations in the leachates were negatively correlated with DOM, and decreased with increasing rates of P applications. The boosted leaching of DOM induced by high rates of P applications was probably due to the added phosphate ions competing for adsorption sites in the soil solids with the indigenous DOM.     

pH modeling for maximum dissolved organic matter removal by enhanced coagulation

Correlations between raw water characteristics and pH after enhanced coagulation to maximize dissolved organic matter (DOM) removal using four typical coagulants (FeCl₃, Al₂(SO₄)₃, polyaluminum chloride (PACl) and high performance polyaluminum chloride (HPAC)) without pH control were investigated. These correlations were analyzed on the basis of the raw water quality and the chemical and physical fractionations of DOM of thirteen Chinese source waters over three seasons. It was found that the final pH after enhanced coagulation for each of the four coagulants was influenced by the content of removable DOM (i.e. hydrophobic and higher apparent molecular weight (AMW) DOM), the alkalinity and the initial pH of raw water. A set of feed-forward semi-empirical models relating the final pH after enhanced coagulation for each of the four coagulants with the raw water characteristics were developed and optimized based on correlation analysis. The established models were preliminarily validated for prediction purposes, and it was found that the deviation between the predicted data and actual data was low. This result demonstrated the potential for the application of these models in practical operation of drinking water treatment plants.     

湿地植物生物炭衍生DOM与氯霉素的络合机制

了解生物炭溶解性有机质（BDOM）与污染物的络合机制对生物炭的应用具有重要意义.选取天然湿地植物灰化苔草为生物炭原料,利用荧光猝灭法及多种光谱分析技术和方法,分析了植物不同部位、不同热解温度下BDOM与氯霉素（CAP）的络合机制,以期为生物炭的生态修复提供理论支持.紫外-可见吸收光谱分析结果表明,BDOM与CAP的荧光猝灭属于静态猝灭,300 ℃制备的BDOM与CAP络合体系的芳香性化合物含量和分子量比500 ℃更大. 同步荧光光谱分析结果发现类络氨酸和类色氨酸物质与CAP的络合能力更强.二维相关图谱分析结果表明植物根与叶的BDOM分别以类蛋白和类腐殖物质对CAP的猝灭更强,其中苔草根BDOM与CAP的猝灭优先发生于类蛋白物质中,但苔草叶BDOM以类腐殖物质为先.此外,通过三维荧光光谱结合平行因子分析法共解析出1个类蛋白荧光组分和5个类腐殖质荧光组分.总体来说,就单一组分而言,BDOM类蛋白组分与CAP的络合强度高于类腐殖质组分.     

In-situ observations of internal dissolved heavy metal release in relation to sediment suspension in lake Taihu, China

Despite laboratory experiments that have been performed to study internal heavy metal release, our understanding of how heavy metals release in shallow eutrophic lakes remains limited for lacking in-situ evidence. This study used automatic environmental sensors and a water sampling system to conduct high-frequency in-situ observations(1-hr intervals) of water environmental variables and to collect water samples(3-hr intervals), with which to examine the release of internal heavy metals in Lake T...     

蒙脱石/DOM复合体对菲的吸附

以垃圾渗滤液为水溶性有机质(DOM)提取原料,通过与吸附载体蒙脱石的有机-无机复合制得蒙脱石/DOM复合体,研究其对菲的吸附作用以及温度、pH值、固液比等不同因素对吸附过程的影响.结果表明,相比蒙脱石原土,蒙脱石/DOM复合体对菲的吸附能力得到显著提高;随着温度升高吸附量呈下降趋势;介质pH值对吸附影响不大;随着固液比的增大,平均吸附量逐渐减小,吸附率逐渐增大.动力学研究表明,菲在蒙脱石/DOM复合体上的吸附等温线与Henry线性方程和Freundlich经验方程的线性拟合较好.另外,对菲在蒙脱石/DOM复合体上的解吸实验表明,菲在蒙脱石/DOM复合体上的吸附有较好的稳定性.     

应用多元统计研究城市河流沉积物孔隙水中DOM紫外光谱特征

应用紫外-可见光吸收光谱研究白塔堡河丰水期沉积物孔隙水中水溶性有机物(DOM)的来源、结构及腐殖化程度.采集白塔堡河干流13个沉积物孔隙水样品,分析DOM紫外光谱特性,推演出9个紫外光谱指数(SUVA254、E2/E4、E4/E6、E2/E3、S275~295、S350~400、A2/A1、A3/A1和A3/A2),研究DOM的组成与结构特征,评价DOM的腐殖化水平.白塔堡河沉积物孔隙水中DOM组成、机构及腐殖化水平呈现沿农村河段向城镇与城市河段递变,农村河段DOM分子量大于城镇与城市河段的,农村河段的DOM分子的聚合度、芳化度、腐殖化水平高于城镇与城市河段的,而DOM中富里酸的含量沿农村河段向城镇与城市河段增加.A2/A1、A3/A1和A3/A2和其它6个指标呈负相关,表明DOM的腐殖化水平随着A2/A1、A3/A1和A3/A2的值增大而升高,而随着其它指标的增大而降低.A2/A1、A3/A1和A3/A2更加精确地评价DOM腐殖化水平,辨识不同采样点DOM腐殖化进程.     

Effect of dissolved organic matter on adsorption and desorption of mercury by soils

Effects of dissolved organic matter (DOM) on adsorption and desorption of Hg were investigated in two kinds of soils, Xanthi-Udic Ferralosols (XUF) and Typic Purpli-Udic Cambosols (TPUC). The DOM was obtained from humus soil (DOMH), rice straw (DOMR), and pig manure (DOMP). The presence of DOM obviously reduced Hg maximum adsorption capacity with up to 40% decreases over the control, being an order of DOMH (250.00 mg/kg)< DOMR (303.03 mg/kg) < DOMP (322.58 mg/kg) < CK (control 416.67 mg/kg) for the XUF and ...     

Interactions between lead(II) ions and dissolved organic matter derived from organic fertilizers incubated in the field

This work was to study composition characteristics and the subsequent effect on the lead (Pb) binding properties of dissolved organic matter (DOM) derived from seaweed-based (SWOF) and chicken manure organic fertilizers (CMOF) during a one-year field incubation experiment using the excitation-emission matrix-parallel factor (EEM-PARAFAC) and two-dimensional correlation spectroscopy (2DCOS) analysis. Results showed that high aromatic and hydrophobic fluorescent substances were enriched in CMOF-derived DOM and SWOF-derived DOM and enhanced over time. And phenolic groups in the fulvic-like substances for SWOF-derived DOM and carboxyl groups in the humic-like substances for CMOF-derived DOM had the fastest responses over time, respectively. Moreover, both non-fluorescent polysaccharides and fluorescent humic-like substances or fulvic-like substances with aromatic (C=C) groups first participated in the binding process of Pb to SWOF-derived DOM on day 0 and 180 during the lead binding process. In contrast, humic-like substances associated with aromatic (C=C) and phenolic groups gave a faster response to Pb binding on day 360. Regarding CMOF-derived DOM, the fulvic-like substances associated with aromatic (C=C) and carboxylic groups displayed a faster response to Pb ions on day 0. Nonetheless, polysaccharides and humic-like associated with phenolic groups had a faster response on days 180 and 360. It is noteworthy that the polysaccharides, which participated in Pb binding to CMOF-derived DOM, posed a higher risk of Pb in the environment after 360 days. Therefore, these findings gave new insights into the long-term applications of commercial organic fertilizers for the amendment of soil.     

DOM对纳滤膜去除磺胺甲恶唑效果影响研究

试验研究几种不同可溶性有机物(DOM)对纳滤膜(NF)去除抗生素磺胺甲恶唑(SMZ)的影响效果.试验所用DOM选定腐殖酸(HA)、单宁酸(TA)和海藻酸钠(SA).结果显示3种DOM对SMZ去除率和通量影响迥异,并与DOM的亲疏水性有密切的关系.为更好了解DOM对NF去除SMZ的影响机理,试验对臭氧化HA也进行了研究.臭氧化HA相对于臭氧前HA亲水性显著提高,对SMZ去除率的影响相应提高.结果表明在有多种DOM共同存在的天然原水中,SMZ的去除机理十分复杂,DOM的本身物理化学性质对于目标物的去除效果十分重要.     

垃圾渗滤液中溶解性有机质与重金属络合机制研究现状及展望

垃圾渗滤液中富含的溶解性有机质（DOM）包含羟基、羧基、羰基等多种活性官能团,是重金属在环境介质中迁移的重要载体。垃圾渗滤液因来源不同,其中的DOM组分与重金属种类、含量也存在显著差异。 DOM 与重金属之间常见的反应以络合作用为主,该作用是影响渗滤液中DOM和重金属形态及环境行为效应的关键。然而,DOM络合过程十分复杂,为了解析络合作用,有效的表征方法及据此建立的络合模型,是厘清垃圾渗滤液DOM与重金属络合机制的重要技术手段。重点介绍了荧光技术、紫外-可见光谱法、红外光谱法等DOM表征方法以及常用的络合模型,综述了络合过程中pH、DOM组成、重金属离子等影响因素,以期揭示渗滤液中重金属的形态转化规律,为污染修复技术提供理论指导。

     

小球藻来源溶解有机质的光化学降解特性

利用三维荧光光谱-平行因子分析(EEM-PARAFAC)手段结合吸收光谱分析,研究了小球藻指数期和稳定期培养液中溶解有机物(DOM)在秋季天然太阳辐射作用下的光降解动力学特征.结果表明,小球藻生长过程中除能产生短波激发类腐殖质组分C1(其荧光峰的激发/发射波长位置为240,335 nm /406 nm)及类蛋白质组分C3(225,275 nm/334 nm)外,还会形成长波激发类腐殖质组分C2(260,395 nm /502 nm),表明C2组分并非仅有传统认为的陆源属性,同时也具有自生源属性.稳定期培养液的吸收光谱在250~300 nm范围内出现的肩峰,可用于指示水环境中现场自生源的贡献.不同生长时期培养液中DOM的吸收系数和荧光组分的降解动力学都符合一级反应方程.稳定期类腐殖质荧光组分(C1和C2)的光降解程度略高于指数期,但指数期类色氨酸组分(C3)的光降解程度略高于稳定期.经太阳辐照6 d后,小球藻培养液的吸收系数a₃₅₀及各荧光组分的平均损失率分别达到83.0%、84.0%、64.8%和80.0%,对应的半衰期只有1.6~5.0 d,揭示出藻类自生来源的DOM具有很强的光化学降解活性.     

南漪湖上覆水溶解性有机质的光谱特征

为考察南漪湖上覆水中溶解性有机质(DOM)的光谱特征与来源,采用紫外-可见光吸收光谱(UV-Vis)与三维荧光光谱(EEMs)为工具,并结合平行因子分析(PARAFAC)、荧光区域积分分析(FRI)、相关性分析、主成分分析与聚类分析对DOM进行定性与定量分析.结果显示,UV-Vis参数a(440)、E₂/E₃、E₃/E₄、S_R表明DOM具有腐殖化特征与自生源特征,且E₂/E₃、E₃/E₄与a(440)呈显著正相关关系(P<0.01,P<0.05),S_R与a(440)无显著相关关系(P>0.05),说明腐殖酸浓度越高则DOM相对分子量越大,但无法依据腐殖酸浓度大小判断DOM来源.根据a(440)计算获得溶解性有机碳(DOC)平均浓度为26.79mg/L,且该湖泊出口附近DOC浓度为10.15mg/L.荧光指数(β:α、FI、BIX、HIX、Fn (280)、Fn (355))显示该湖泊DOM具有腐殖化程度较低及强自生源特征,类蛋白组分(Fn (280))相对浓度的空间分布上由西向东逐渐增大,而腐殖酸类组分(Fn (355))相对浓度峰值出现在入湖口与出湖口.通过PARAFAC解析出3种组分,分别为类富里酸(C1)、类色氨酸(C2)和类腐殖酸(C3),且C1、C2、C3含量分别占总组分强度21.96%、13.36%、84.21%.FRI法分析显示类蛋白物质所占比例之和(区域I+II)为49.65%,该结果说明水体已受到了人为因素影响.通过相关性分析结果显示,C1、C3与β:α、BIX呈显著负相关系(P<0.001),C2与β:α、BIX、Fn (355)呈正相关系(P<0.001).通过主成分分析与聚类分析,南漪湖上覆水中DOM在16个位点间呈现不同特征,但整体上水体中DOM来源受内源输入影响较为显著,应加强该湖泊内源释放污染物控制与管理.     

水溶性有机物对菲的表观溶解度和正辛醇/水分配系数的影响

以农业上常用有机物料绿肥、猪粪和污泥作为水溶性有机物(DOM)的提取材料,以菲(Phe)作为多环芳烃(PAHs)的代表,通过摇瓶法研究了不同来源的DOM对菲在水中的表观溶解度和正辛醇/水分配系数的影响.结果表明,菲在超纯水中的溶解近似一级反应动力学过程.超纯水体系中添加了DOM后,菲溶解的平衡时间相对滞后,但却明显增加了菲的表观溶解度.当DOM浓度为150 mg·L-1(以DOC计)时,在含Tween-80、猪粪DOM、污泥DOM和绿肥DOM的体系中菲的表观溶解度分别是纯水体系的20.39、2.082、1.838和1.549倍.菲的表观溶解度随着外加DOM浓度的增加而增大,它们之间存在着明显的线性关系.回归直线的斜率可以用来表征DOM对菲的增溶效果,本试验4种体系中DOM的增溶效果大小依次为表面活性剂Tween-80＞猪粪DOM＞污泥DOM＞绿肥DOM.同时,DOM可降低菲的正辛醇/水溶液分配系数,各体系中logKow值的高低顺序与增溶效果的顺序恰好相反.研究结果显示,DOM的存在可明显地改变PAHs在水相中的溶解度和正辛醇/水溶液分配系数.