Fluorescence spectroscopic studies of the effect of granular activated carbon adsorption on structural properties of dissolved organic matter fractions

This work investigated the effect of granular activated carbon adsorption (GACA) on fluorescence characteristics of dissolved organic matter (DOM) in secondary effluent, by means of excitation–emission matrix (EEM) spectra, the fluorescence regional integration (FRI) method, synchronous spectra, the fluorescence index defined as the ratio of fluorescence emission intensity at wavelength 450 nm to that at 500 nm at excitation (λ_ex)=370 nm, and the wavelength that corresponds to the position of the normalized emission band at its half intensity (λ_0.5). DOM in the secondary effluent from the North Wastewater Treatment Plant (Shenyang, China) was fractionated using XAD resins into 5 fractions: hydrophobic acid (HPO–A), hydrophobic neutral (HPO–N), transphilic acid (TPI–A), transphilic neutral (TPI–N) and hydrophilic fraction (HPI). Results showed that fluorescent materials in HPO–N and TPI–N were less readily removed than those in the other fractions by GACA. The relative content of fluorescent materials in HPO–A, TPI–A and HPI decreased whereas that in HPO–N and TPI–N increased as a consequence of GACA. Polycyclic aromatics in all DOM fractions were preferentially absorbed by GACA, in comparison with bulk DOM expressed as DOC. On the other hand, the adsorption of aromatic amino acids and humic acid-like fluorophores exhibiting fluorescence peaks in synchronous spectra by GACA seemed to be dependent on the acid/neutral properties of DOM fractions. All five fractions had decreased fluorescence indices as a result of GACA. GACA led to a decreased λ_0.5 value for HPO–A, increased λ_0.5 values for HPO–N, TPI–A and HPI, and a consistent λ_0.5 value for TPI–N.     

Three-dimensional fluorescence spectral characterization of soil dissolved organic matters in the fluctuating water-level zone of Kai County, Three Gorges Reservoir

Three-dimensional fluorescence spectroscopy was used to investigate the fluorescent properties of soil dissolved organic matter (DOM) in the water-level-fluctuation zone (WLFZ) of Kai County, Three Gorges Reservoir (TGR). Most of the soil DOM analyzed in this study was found to contain four fluorescence peaks. Peaks A and C represent humic-like fluorescence, whereas peaks B and D represent tryptophan-like fluorescence. Peaks E and F, which represent tyrosine-like fluorescence, only appeared in certain soils. Soil humus was the main source of DOM in soil, and higher concentration of soil DOM was found in the exposed soil than submerged soil. Compared to the peaks A and B, the fluorescence intensities of peaks C and D were strongly influenced by the fluctuating water level. Analysis of fluorescence intensities of different peaks in soil DOM showed that WLFZ soil was not contaminated significantly. Soil DOM contained at least two types of humic-like fluorescence groups and two types of protein-like fluorescence groups. The proportion of the content of peak A in soil organic matter was quite stable. The soil DOM in exposed soil had relatively high humification and aromaticity, and periodic submerging and exposure of soil had an impact on the humification of soil DOM.     

Effects of dissolved organic matter on the desorption of Cd in freeze–thaw treated Cd-contaminated soils

Lab-scale experiments were conducted to investigate the effects of dissolved organic matter (DOM) on the desorption of Cd in freeze–thaw treated Cd-contaminated soils. The results indicated that DOM significantly facilitated the desorption of Cd from freeze–thaw treated soils when comparing with that of non-frozen soils. Effects of DOM on the Cd desorption were highly dependent on the soil type and contamination concentration. The maximum desorption ratios of Cd by DOM generated from straw and sludge were 15.6% and 13.65%, respectively, in brown soils, and the maximum desorption ratios reached 14.7% and 9.3%, respectively, when using black soils through the same treatment. The higher the Cd contamination concentration in soils, the higher the ratio of Cd desorption by DOM. This was because of the integrated effects of the soil properties changed by the freeze–thaw treatment and the species transformation of Cd. The characteristics of DOM, such as its concentration and properties, had shown obvious impacts on the Cd desorption by DOM. The desorption was promoted with the increased DOM concentration and the hydrophilic fraction, and lowered pH and the low-molecular-weight of DOM.     

The effect of humic substances on Cu migration in the soil profile

Humic substances (HS) are widely used for diverse purposes. The effect of HS on the metal’s status in contaminated soils is contradictory. The aim of this work was to investigate the Cu migration in soils treated with HS. A model field experiment with the addition of Cu (1.243?mg?Cu/kg) and HS Extra® (potassium humate) was performed. The Cu addition resulted in acidification (by 0.7 pH) after 3 months. The major part of the added Cu remained in the upper 7-cm-thick soil layer; 4% reached the lower soil layer, while only 0.1% were removed beyond the profile. The addition of HS mitigated soil acidification increased the content of Cu bound to solid-phase organic substances and abruptly reduced the Cu activity in the soil liquid phase. Simultaneously, the HS addition increased the water-soluble organic substances (WSOS) by four times, including those in the hydrophilic and hydrophobic fractions, resulting in a twofold increase in the content of soluble Cu. Copper complexes with hydrophilic WSOS mainly reached lysimeters, and hydrophobic organic substances were absorbed by the soil. The HS addition to a slightly acidic soil can accelerate the migration of Cu to adjacent environments.     

焦化废水中溶解性有机物组分的特征分析

焦化废水是典型的具有复杂有机质的工业废水,其复杂的有机构成制约了水处理的水质达标,且可能对排入水体构成危害.为了探明其溶解性有机物的组成,采用XAD-8大孔树脂将焦化废水中的溶解性有机物分为亲水性组分(HIS)、疏水酸性组分(HOA)、疏水碱性组分(HOB)和疏水中性组分(HON),分析了各组分的溶解性有机物(DOC)、紫外-可见光谱、色度,并采用GC/MS对各组分中有机物进行定性分析.结果表明,焦化废水中的有机物主要为HIS和HOA组分,其DOC含量分别占总DOC的44.3%和32.4%;焦化废水在200—250 nm和300—400 nm范围内有特征吸收峰,且吸收光强度顺序为HIS>HOA>HON>HOB;焦化废水的色度主要由HOA和HON构成,其在525 nm和436 nm处的吸光度分别占焦化废水吸光度的42.9%(HON)、42.1%(HON)和21.4%(HOA)、15.8%(HOA);焦化废水中亲水性物质主要是苯胺、苯酚、喹啉、异喹啉,疏水酸性物质中主要是各种甲基取代的酚类物质,疏水碱性物质主要是各种胺类和含氮杂环化合物,疏水中性物质主要是吲哚及其衍生物.     

溶解性有机物对土壤中重金属环境行为的影响

为揭示在溶解性有机物（DOM）作用下土壤中重金属的吸附和迁移规律并确定迁移数学模型,通过不同条件下的等温吸附实验和土柱淋滤实验,研究了溶解性有机物对重金属Cu,Cd,Pb,Zn在褐土中吸附和迁移行为的影响。结果表明DOM对Cu和Cd在土壤中的吸附促进作用较明显,对Pb有微弱的促进作用,对Zn的吸附影响不明显;随着pH的改变,25℃下Cu在土壤中的吸附高于15℃和35℃条件下。DOM质量浓度越高,Cd、Zn溶出的促进效果越明显,Cu、Pb则恰好相反。DOM对土壤中Cd、Zn的垂直迁移起着促进作用,而对Cu、Pb迁移起着一定的抑制作用;DOM对土壤重金属的平均迁移量随时间的延长而减少。此迁移模型能够定量计算并预测重金属质量浓度的时空分布。     

雄烯二酮在我国典型土壤中的吸附特性

采用批吸附室内模拟实验研究了雄烯二酮在我国红壤、潮土、黑土3种典型土壤中的吸附特征,以及牛粪溶解态有机质(DOM)对土壤吸附雄烯二酮的影响。结果表明,雄烯二酮在土壤中吸附动力学符合Elovch方程(R20.89),热力学特征可通过Freundlich等温吸附方程(R20.83)描述,土壤对雄烯二酮的吸附呈非线性吸附特征,其中潮土吸附等温线的非线性最强(n=0.37);吸附系数K f介于6.0~20.2,并与有机质含量呈显著正相关(p0.05)。雄烯二酮浓度较低时,共存牛粪DOM抑制其在土壤表面的吸附作用。研究认为,有机质是土壤吸附雄烯二酮的主要组分,共存牛粪DOM可促进雄烯二酮向地表水和地下水的迁移。     

黄浦江原水中各类有机物在铝盐混凝过程中的去除效果

通过XAD-8/XAD-4吸附树脂联用技术将黄浦江微污染原水中溶解性有机物分为疏水酸、非酸疏水物质、弱疏水物质及亲水物质4类有机物,研究了铝盐混凝工艺对黄浦江水中4类有机物的去除效果.硫酸铝在最佳混凝条件下,即投加量为8 mg·l~(-1)(以Al计),pH=5.5时,水中的DOC和UV_(254)的去除率分别达到23%和32%.有机物的亲疏水性对混凝工艺有较大影响,混凝法倾向于优先去除水中疏水性有机物,而疏水性有机物的酸碱性对混凝工艺没有明显影响,酸性和非酸类疏水物质均能破混凝工艺所去除.疏水酸是水中最主要的三氯甲烷类消毒副产物的前体物质,混凝工艺对于三氯甲烷类消毒副产物有良好的控制作用,总体减少了 39%的生成量.而不同类的有机物之间,混凝工艺对消毒副产物控制效果不同,其中对疏水酸的控制三氯甲烷消毒副产物的效果最好,减少了63%的生成量,亲水物质的控制效果最差,三氯甲烷生成量仪减少了3%.疏水酸表现出比亲水物质更强的生物毒性,混凝工艺能明显降低原水的毒性.     

Chemical identification and genotoxicity analysis of petrochemical industrial wastewater

The actual harmful effects of industrial wastewater can not be reflected by the conventional water quality index. Therefore, the change in dissolved organic matter and the genetic toxicity of petrochemical wastewater were observed in the current study by examining the wastewater treatment plant of a large petrochemical enterprise in Northwest China. Using XAD-8, MSC, and DA-7 resins, the wastewater was separated into six fractions, namely, hydrophobic acid (HOA), hydrophobic neutral (HOB), hydrophobic alkaline, hydrophilic acid, hydrophilic alkaline, and hydrophilic neutral. Umu-test was used to detect the genetic toxicity of the wastewater samples, and fluorescence spectra were also obtained to examine genetic toxic substances. The results show that wastewater treatment facilities can effectively reduce the concentration of organic matter in petrochemical wastewater (p<0.05). However, the mixing of aniline wastewater can increase the amount of organic carbon (p<0.05) and can overload facilities. This finding shows that the mixed collection and joint treatment of different types of petrochemical wastewater can affect the water quality of the effluent. Particularly, hydrophobic substances can be difficult to remove and account for a relatively large proportion of the effluent. The mixture of aniline wastewater can increase the genetic toxicity of the effluent (p<0.05), and biologic treatment can not effectively decrease the toxicity. Most of the genetic toxicology may exist in the HOA and HOB fractions. Fluorescence spectroscopy also confirms this result, and tryptophan-like substances may play an important role in genetic toxicity.     

可溶性有机质对芘在泥炭和高岭土上吸附和解吸的影响

为掌握可溶性有机质(DOM)对憎水性有机污染物吸附和解吸行为的影响,本研究选取四环多环芳烃——芘作为目标污染物,通过批平衡实验研究了不同分子量组分DOM对芘在泥炭和高岭土上吸附和解吸的影响.结果表明,吸附和解吸数据均可以用Freundlich模型很好地拟合(R²>0.93).DOM的添加抑制了泥炭对芘的吸附,并且分子量越大的DOM产生的抑制效应越明显,主要是由于DOM与芘分子的竞争、增溶作用及泥炭表面微孔的堵塞引起的.与之相反,DOM促进了芘在高岭土上的吸附,DOM分子量越大,促进效应越强,这是由于DOM与芘分子之间通过累积吸附或共吸附增加高岭土对芘的吸附.DOM促进了芘在泥炭和高岭土上的解吸,并且促进效应随分子量的增加而增强.此外,芘在泥炭和高岭土上的解吸均存在迟滞现象,均在低浓度时表现出更明显的效应.DOM_bulk和DOM_(>14000 Da)增加了芘在泥炭上的解吸迟滞现象,但降低了其在高岭土上的解吸迟滞现象.     

氯化消毒饮用水中强致突变物MX[3-氯-4-(二氯甲基)-5-羟基-2(5H)-呋喃酮]的形成

利用一系列XAD吸附树脂及大孔阴、阳离子交换树脂,将太湖水中溶解态有机物分离为溶解态富里酸类、腐殖酸类、憎水弱酸类、憎水碱类、憎水中性物类、亲水酸类、亲水碱类七种组分,分别对不同组分的有机物进行氯化处理后,用GC/MS选择离子峰面积法测定了产物中的MX[3-氯-4-（二氯甲基）-5-羟基-2（5H）-呋喃酮]。结果表明,太湖水体中的溶解态腐殖酸类可能是生成MX的重要前驱物。     

Characterization of the dissolved organic matter in sewage effluent of sequence batch reactor: the impact of carbon source

Dissolved organic matter (DOM) transformation in sequence batch reactor (SBR) fed with carbon sources of different biodegradability was investigated. During the biologic degradation process, the low molecular weight (MW) fraction (< 1 kDa) gradually decreased, while the refractory compounds with higher aromaticity were aggregated. Size exclusion chromatography (SEC) and fluorescence of excitation emission matrices (EEM) demonstrated that more biopolymers (polysaccharides or proteins) and humic-like substances were presented in the extracellular polymeric substance (EPS) extracted from the SBR fed with sodium acetate or glucose, while the EPS from SBR fed with slowly biodegradable dissolved organic carbon (DOC) substratestarch had relatively less biopolymers. Comparing the EfOM in sewage effluent of three SBRs, the effluent from SBR fed with starch is more aromatic. Organic carbon with MW>1 kDa as well as the hydrophobic fraction in DOM gradually increased with the carbon sources changing from sodium acetate to glucose and starch. The DOC fractionation and the EEM all demonstrated that EfOM from the effluent of the SBR fed with starch contained more fulvic acid-like substances comparing with the SBR fed with sodium acetate and glucose.     

水杉凋落物分解过程中溶解性有机质的分组组成变化

采用XAD-8树脂分组的方法研究水杉凋落物降解过程中DOM的含量及其组成的变化。结果表明，培养35天后DOC含量达到稳定值，而其组成仍未稳定。在整个培养过程中，HOA和HIM含量有明显变化；HON含量呈缓慢增加的趋势；AIM和HOB含量则没有明显变化。凋落物淋滤液DOM与表层土壤DOM组成相似，是土壤DOM的主要来源。土壤DOM中的AIM不是来源于凋落物淋滤液，而是主要来源于土壤腐殖质、根系分泌物等其它物质。     

膜下滴灌棉田不同土层盐分变化及其对棉花生长的影响

研究选择两种不同盐分含量土壤（中度盐渍化EC25：4-7 dS.m-1和轻度盐渍化EC25：1-4 dS.m-1）,通过对棉田整个生育期的土壤盐分含量测定,研究棉田不同土层盐分变化及其对棉花生长的影响。结果表明：两种不同盐分含量土壤,盐分降幅较大的在0-20、40-80 cm土层为膜下滴灌棉田盐分积聚区。整个生育期土壤盐分变化趋势相似,都表现为土壤盐分前期（现蕾期）快速下降后期有所增加;中度盐渍化和轻度盐渍化棉田的单株干物质积累量差异不显著,单位面积的干物质积累和籽棉产量差异显著,其主要原因是两种盐分土壤棉花的成活率差异较大。     

土壤溶解性有机质的生态环境效应

土壤生态环境是一个复杂的多介质多界面体系。现有的研究表明，DOM作为环境中重要的天然配位体和吸着载体，是一种非常活跃的化学物质，它将土壤中的矿物质、有机质与生物成分联系在一起，通过物理或化学作用改变金属与外源性化合物的环境行为，促进温室气体的排放，调节土壤养分流失，指示土壤质量，并对成土过程、微生物的生长代谢过程、土壤有机质分解和转化过程有着重要作用，已经成为土壤科学、生态科学和环境科学交叉领域的研究热点。文章系统地评述了DOM的组成特点及其环境效应，同时介绍了未来的研究方向及一些有待于进一步研究的问题。     

农田土壤中汞的吸附分配行为研究

汞是环境中毒性最强的重金属之一,由于具有持久性、长距离迁移性和生物累积性被列为全球性污染物。土壤是汞重要的源和汇,在汞的生物地球化学循环中发挥关键作用,其理化性质可以显著影响汞的吸附分配行为。本文基于采自全国各地的131份农业土壤样品考察了汞(Hg2+)在土壤中的吸附分配行为,测定了Hg2+的固液分配系数(Kd),并探讨其与p H、有机质(OM)、粒度组成、溶解性有机质(DOM)和总硫等土壤理化性质的关系。利用逐步多元线性回归的方法分析发现旱地土壤对汞Kd的主要影响因素是DOM和土壤粒度,而水田的主要影响因素是总硫。通过淹水实验,进一步探究了土壤氧化还原对Hg2+分配的影响。研究发现,旱地土壤中,大部分土壤在淹水30 d后Kd呈明显增大趋势,继续淹水至60 d的Kd表现为稳定或下降的趋势;大部分水田土壤在淹水条件下Kd未表现出增大的趋势,且随淹水时间呈稳定或下降的趋势。     

Quantitative characterization of Cu binding potential of dissolved organic matter （DOM） in sediment from Taihu Lake using multiple techniques

Dissolved organic matter （DOM） plays an important role in heavy metal speciation and distribution in the aquatic environment especially for eutrophic lakes which have higher DOM concentration. Taihu Lake is the third largest freshwater and a high eutrophic lake in the downstream of the Yangtze River, China. In the lake, frequent breakout of algae blooms greatly increased the concentration of different organic matters in the lake sediment. In this study, sediment samples were collected from various part of Taihu Lake to explore the spatial difference in the binding potential of DOM with Cu. The titration experiment was adopted to quantitatively characterize the interaction between Cu（II） and DOM extracted from Taihu Lake sediments using ion selective electrode （ISE） and fluorescence quenching technology. The ISE results showed that the exogenous DOM had higher binding ability than endogenous DOM, and DOM derived from aquatic macrophytes had a higher binding ability than that derived from algae. The fluorescence quenching results indicated that humic substances played a key role in the complexation between DOM and Cu（II） in the lake. However, because of the frequent breakout of algae blooms, protein-like matters are also main component like hnmic matters in Taihu Lake. Therefore, the metals bound by protein-like substances should be caused concern as protein-like substances in DOM were unstable and they will release bound metal when decomposed.     

Enrichment and solubility of trace metals associated with magnetic extracts in industrially derived contaminated soils

Magnetic fractions (MFs) in industrially derived contaminated soils were extracted with a magnetic separation procedure. Total, soluble, and bioaccessible Cr, Cu, Pb and Zn in the MFs and non-magnetic fractions (NMFs) were analyzed using aqua regia and extraction tests, such as deionized water, toxicity characteristic leaching procedure (TCLP), and gastric juice simulation (GJST) test. Compared with the non-magnetic fractions, soil MFs were enriched with Fe, Mn, Pb, Cd, Cr, Cu, and Ni. Extraction tests indicated that soil MFs contained higher water, TCLP, and GJST-extractable Cr, Cu, Pb, and Zn concentrations than the soil NMFs. The TCLP-extractable Pb concentration in the MFs exceeded the USEPA hazardous waste criteria, suggesting that soil MFs have a potentially environmental pollution risk. Solubility of trace metals was variable in the different extraction tests, which has the order of GJST?>?TCLP?>?water. TCLP test showed Cu and Zn were more mobile than Cr and Pb while bioaccessibility of trace metal defined by GJST test showed the order of Cu?≈?Cr?≈?Zn?>?Pb. These findings suggested that the MFs in the industrially derived contaminated soils had higher possibility of polluting water bodies, and careful environmental impact assessment was necessary.     

赤子爱胜蚓(Eisenia foetida)对三种土壤Zn、Pb有效态含量的影响

以褐土(Cinnamonsoil)、潮棕壤(Aquicbrownsoil)和酸性棕壤(Acidbrownsoil)为供试土壤,通过培养实验,研究了土壤中重金属Zn、Pb对赤子爱胜蚓(Eiseniafoetida)生长率的影响,赤子爱胜蚓(Eiseniafoetida)对不同土壤中有效态Zn、Pb含量的影响,并与野生环境中生长的灰暗异唇蚓(Allolobaphoracaliginosa)进行比较。结果表明:重金属的污染明显抑制了赤子爱胜蚓的生长;赤子爱胜蚓可以显著提高潮棕壤中DTPA-Pb的含量,对DTPA-Zn的含量影响不大;加赤子爱胜蚓,褐土中DTPA-Zn和Pb的含量显著高于加灰暗异唇蚓,潮棕壤中DTPA-Zn的含量和酸性棕壤中大DTPA-Pb的含量则相反。     

Application of portable X-ray fluorescence (pXRF) for heavy metal analysis of soils in crop fields near abandoned mine sites

To get representative soil samples, a sampling method was verified for crop fields in the vicinity of abandoned mine sites. Application of appropriate sampling or analytical methods is very important as it affects the costs, time, and accuracy of the refined investigation of soil contamination. Two-time sampling for each crop field was conducted to verify the reproducibility of a zigzag method for soil sampling. The soil analysis using a portable X-ray fluorescence (pXRF) device was conducted to measure concentrations of metal species in soils, and its results were compared to the extracted concentrations by the Korean Standard Test (KST) for soils. As a result, the determination coefficient (R ²) of linear regression analysis for data obtained by ex situ precise measurement or in situ field screening using pXRF was closely related with the ratio of the extracted concentration by KST to interference-free detection limits (IFDL) of pXRF (designated as KST/IFDL). As the specific metal species had a higher ratio of KST/IFDL, its R ² was even higher in the field screening tests. However, the slopes of linear regression analysis for most metal species extracted by aqua-regia were close to 1.0 so that extracted concentrations by aqua-regia were similar to the analytical values obtained by pXRF, whereas extraction using a weak acid (0.1 M HCl) had different slopes for soils contaminated with different ranges of concentrations of metal species. Especially Zn showed not only high ratios of KST/IFDL because of aqua regia extraction, but also high determination coefficients. Because of its simple, rapid, and accurate capacities for metal analysis, the pXRF analysis showed high applicability in ex situ precise measurements or in situ field screening of metal analysis. In terms of applicability for regulation, especially in situ pXRF field screening with the zigzag method could be effectively applied to achieve an economical survey by determining hot spots or non-contaminated areas if aqua-regia was applied as the extracting agent in the KST for soils.