Characteristics of the natural organic matter sorption affects of organic contaminants

Several soil samples were used to study how the characteristics of natural organic matter (NOM) affect sorption of organic compounds. These soils contains different amounts and types of NOM. Aromaticity of NOM (percentage of aromatic carbons) was determined from solid state CPMAS 13 C NMR spectra and the soil effective polarity was computed from the equation developed by Xing et al . Naphthalene was used to examine the sorption characteristics of NOM. Both aromaticity and polarity of NOM strongly affected sorption of naphthalene. Old NOM showed higher affinity than that in the surface, young soils. Sorption increased with increasing aromaticity and decreasing polarity. Thus, the sorption coefficients of organic contaminants cannot be accurately predicted without some consideration of NOM characteristics.

Effects of nature organic matters and hydrated metal oxides on the anaerobic degradation of lindane,p,p'-DDT and HCB in sediments

Effects of natural organic matters(NOM) and hydrated metal oxides(HMO) in sediments on the anaerobic degradation of γ 666, p,p' DDT and HCB were investigated by means of removing NOM and HMO in Liaohe River sediments sequentially. The results showed that the anaerobic degradation of γ 666, p,p' DDT and HCB followed pseudo first order kinetics in different sediments. But, the extents and rates of degradation were different, even the other conditions remained the same. Anaerobic degradation rates of γ 666, p,p' DDT and HCB were 0 020 d -1 , 0 009 d -1 and 0 035 month -1 respectively for the sediments without additional carbon resources. However, with addition of carbon resources, the anaerobic degradation rates of γ 666, p, p ' DDT and HCB were 0 071 d -1 , 0 054 d -1 and 0 088 month -1 in the original sediments respectively. After removing NOM, the rates were decreased to 0 047 d -1 , 0 037 d -1 and 0 066 month -1 ; in the sediments removed NOM and HMO, the rates were increased to 0 067 d -1 , 0 059 d -1 and 0 086 month -1 . These results indicated that NOM in the sediments accelerated the anaerobic degradation of γ 666, p,p' DDT and HCB; the HMO inhibited the anaerobic degradation of γ 666, p,p' DDT and HCB.

Reduction of Trihalomethanes Forming Potential by Adsorption of Natural Organic Matter on Ionic Exchange Resins

In a sanitation process of drinking water, carbon from the organic matter reacts with chlorine, forming by-products, among which are trihalomethanes (THM). These substances are carriers of mutagenic and can-cerogenic potential and hence should be removed in drinking water treatment. Since the natural organic mat-ters are precursors of THM formation, their removal from the water decreases the concentration of THMs. The THM forming potential is the most reliable indicator in evaluation of organic matter removal during drinking water treatment processes. The results have shown that the reaction producing THMs follows sec-ond order kinetics. The second order rate constant ranged from 0.024 M-1s-1 to 0.065 M-1s-1 at 22 °C and pH = 8.2 for 96 hours. The removal of 78.4% of natural organic matter, by adsorption on anionic exchange res-ins, resulted in the THM forming potential reduction by 63.1%. Various fractions of natural organic matter differ in their reactivity with chlorine, which is important when it comes to selection of the adsorption me-dium in the drinking water treatment processes.

Use of Natural Coagulants in Removing Organic Matter, Turbidity and Fecal Bacteria from Hospital Wastewater by Coagulation-Flocculation Process

Hospital wastewater represents an infectious and toxic risk to human health and the environment due to its contents. Most hospitals in developing countries, including Benin, do not have a wastewater treatment plant. In this study, the wastewater from two hospitals in northern Benin was characterized and then treated with Azadirachta indica leaves, Moringa oleifera and Luffa cylindrica seeds by coagulation/flocculation process. The wastewater characteristics showed that the collected samples are greatly polluted by organic matter and fecal bacteria such as Escherichia coli, Enterococcus fecal and Total coliforms. Jar-test results revealed that 95.74%, 78%, 49.19% of turbidity, 51.35%, 38.32%, 22.19% of COD, 93.16%, 85.26%, 83.30% against Escherichia coli, 92.11%, 90.93%, 94.60% against total Coliforms and 99.37%, 91%, 99%, 55.07% against Enterococcus were removed from hospital wastewater using Moringa oleifera, Luffa cylindrica seed and Azadirachta indica leaves respectively at dose of 100 mg/L. The results highlighted that the natural coagulants could be successfully used for the removal of turbidity and fecal bacteria from hospital wastewater.

Microbial Changes in the Fluorescence Character of Natural Organic Matter from a Wastewater Source

Natural Organic Matter (NOM) is a mixture of aromatic and aliphatic organic compounds of natural origin in any type of aquatic system. Human activities impact the constituents of NOM, from its production to its fate, particularly in the treatment of domestic waste waters. In this work, the impact of microorganisms isolated from a Waste Water Treatment Plant (WWTP) was investigated to determine the fate of NOM fractions in raw sewage, using fluorescence spectroscopy. Wastewater samples were taken at three different times from a WWTP, and incubated for 4 days under two treatments: 1) “raw sewage”, and 2) “spiked”, i.e., the same raw sewage, spiked with bacteria previously isolated from the WWTP. The incubated waters were analyzed by fluorescence spectroscopy, digitally resolved into NOM components: humic- and fulvic-like, and two types of protein-like, i.e., tryptophan- and tyrosine-like, using a Parallel Factor Analysis routine (PARAFAC). The results demonstrate that the “spiked” samples showed the largest changes with incubation time. The signals of the tryptophan- and tyrosine-like components decreased, suggesting a net microbial digestion of proteinaceous material. In contrast, the fulvic-like signals, and to some extent, the humic-like signals increased, suggesting the production of the associated molecular materials during the incubation period. This study provides direct evidence of human impact on the make-up of NOM: the cultures of microbes found at a WWTP consume the proteinaceous material, whereas humic-like and fulvic-like materials are produced.

Investigation of the Photosensitized Mechanisms of PCBs in the Presence of Natural Organic Matter

The structures of 26 different congeners of polychlorinated biphenyls（PCBs, including monothrough deca-chlorinated） were optimized using density functional theory（DFT） calculations with the 6-31＋G（d,p） basis set. The activation energies for the dechlorination of these systems were calculated for direct photodegradation and photosensitized degradation reaction pathways in the presence of natural organic matter（NOM）. The dechlorination mechanism of these PCBs and the ring-opening reaction mechanisms（using QST3 method） of the photosensitive degradation products were analyzed. The results showed that（i） the activation energy for the photosensitized degradation of PCBs was much lower than that of direct photodegradation;（ii） the degradation activities（i.e., C–Cl bond cleavage energies） were the same for both degradation pathways and followed the order ortho 〉 meta 〉 para;（iii） the degradation activities of asymmetric PCBs were higher than those of the corresponding symmetrical PCBs for the direct photodegradation and it was completely opposite in the photosensitive degradation;（iv） there was no correlation between the dissociation energy and the number of C–Cl bonds for the direct photodegradation and dechlorination products were all biphenyl;（v） the degradation activity of PCBs decreased as the number of C–Cl bonds increased in the presence of NOM; and（vi） even when the dechlorination reaction was incomplete, it produced chlorophenol. Furthermore, the free radicals of NOM led to the ring-opening reactions of PCBs via an initial addition step. The main site of these ring-opening reactions was the ortho position. Notably, the likelihood of ring-opening reactions occurring involving the degradation products increased as the degradation degree of PCBs increased.

土壤中铬价态转化的影响因素与作用机制研究进展

土壤中铬(Cr)污染是全球性环境问题,六价铬Cr(Ⅵ)因其高毒性及致癌性而成为关注焦点。土壤中的Cr主要以Cr(Ⅲ)和Cr(Ⅵ)的形式存在,两者之间的转化受到诸如土壤pH值、氧化还原电位(Eh)、天然氧化还原剂、有机质和微生物的影响。随着工农业活动的增多,土壤中的Cr浓度不断增加,并通过植物吸收进入食物链等多种途径,对生态系统和人体健康构成威胁。本文对Cr在全球范围内的污染现状及来源、土壤中Cr的不同价态及其毒性特征进行了评述,并分析了pH、Eh对土壤中Cr的具体存在形态与价态的影响,及天然氧化还原剂、有机质等因素利用自身化学性质充当电子供体或受体的角色对土壤中Cr价态进行转化的氧化还原机理,以及不同影响因素之间的相互作用关系,从而可以全面理解土壤中Cr价态转化的行为机制。此外,在对Cr价态影响因素深入了解的基础上,总结了以生物炭和纳米材料为代表的先进修复技术方法,这些材料和方法由于能够将Cr(Ⅵ)有效地还原为毒性较小的Cr(Ⅲ),从而降低生态环境风险,因而是一类具有巨大潜在应用价值的修复材料和修复方法,但大规模应用的可行性及其修复效果仍需要进一步验证。

ATR-FTIR and XPS study on the structure of complexes formed upon the adsorption of simple organic acids on aluminum hydroxide

Information on the binding of organic ligands to metal （hydr）oxide surfaces is useful for understanding the adsorption behaviour of natural organic matter on metal （hydr）oxide. In this study, benzoate and salicylate were employed as the model organic ligands and aluminum hydroxide as the metal hydroxide. The attenuated total reflectance Fourier transform infrared （ATR-FTIR） spectra revealed that the ligands benzoate and salicylate do coordinate directly with the surface of hydrous aluminum hydroxide, thereby forming innersphere surface complexes. It is concluded that when the initial pH is acidic or neutral, monodentate and bridging complexes are to be formed between benzoate and aluminum hydroxide while bridging complexes predominate when the initial pH is alkalic. Monodentate and bridging complexes can be formed at pH 5 while precipitate and bridging complexes are formed at pH 7 when salicylate anions are adsorbed on aluminum hydroxide. The X-ray photoelectron （XP） spectra demonstrated the variation of C 1 s binding energy in the salicyate and phenolic groups before and after adsorption. It implied that the benzoate ligands are adsorbed through the complexation between carboxylate moieties and the aluminum hydroxide surface, while both carboxylate group and phenolic group are involved in the complexation reaction when salicylate is adsorbed onto aluminum hydroxide. The information offered by the XPS confirmed the findings obtained with ATR-FTIR.

Investigation on Fe,Mn,Zn,Cu,Pb and Cd fractions in the natural surface coating samples and surficial sediments in the Songhua River,China

Natural surface coating samples （NSCSs） from the surface of shingles and surficial sediments （SSs） in the Songhua River, China were employed to investigate the relationship between NSCSs and SSs in fractions of heavy metals （Fe, Mn, Zn, Cu, Pb, and Cd） using the modified sequential extraction procedure （MSEP）. The results show that the differences between NSCSs and SSs in Fe fi＇actions were insignificant and Fe was dominantly present as residual phase （76.22% for NSCSs and 80.88% for SSs） and Fe-oxides phase （20.33% for NSCSs and 16.15% for SSs）. Significant variation of Mn distribution patterns between NSCSs and SSs was observed with Mn in NSCSs mainly present in Mn-oxides phase （48.27%） and that in SSs present as residual phase （45.44%）. Zn, Cu, Pb and Cd were found dominantly in residual fractions （〉48%）, and next in solid oxides/hydroxides for Zn, Pb and Cd and in easily oxidizable solids/compounds form for Cu, respectively. The heavy metal distribution patterns implied that Fe/Mn oxides both in NSCSs and SSs were more important sinks for binding and adsorption of Zn, Pb and Cd than organic matter （OM）, and inversely, higher affinity of Cu to OM than Fe/Mn oxides in NSCSs and SSs was obtained. Meanwhile, it was found that the distributions of heavy metals in NSCSs and SSs were similar to each other and the pseudo-total concentrations of Zn, Cu, Pb and Cd in NSCSs were greater than those in SSs, highlighting the more importance for NSCSs than SSs in controlling behaviours of heavy metals in aquatic environments.

Effects of pre-ozonation on organic matter removal by coagulation with IPF-PACl

Ozone plays an important role as a disinfectant and oxidant in potable water treatment practice and is increasingly being used as a pre-oxidant before coagulation. The purpose of this study is to obtain insight into the mechanisms that are operative in pre-ozonized coagulation. Effects ofpre-ozonation on organic matter removal during coagulation with IPF-PAC1 were investigated by using PDA （photometric disperse analysis）, apparent molecular weight distribution and chemical fractionation. The dynamic formation of flocs during coagulation process was detected. Changes of aquatic organic matter （AOM） structure resulted from the influence of pre-ozonation were evaluated. Results show that dosage of O3 and characteristics of AOM are two of the major factors influencing the performance of O3 on coagulation. No significant coagulation-aid effect of O3 was observed for all experiments using either A1C13 or PAC1. On the contrary, with the application of pre-ozonation, the coagulation efficiency of A1C13 was significantly deteriorated, reflected by the retardation of floc formation, and the removal decreases of turbidity, DOC, and UV254. However, if PACl was used instead of AlCl3, the adverse effects of pre-ozonation were mitigated obviously, particularly when the O3 dosage was less than 0.69 （mg O3/mg TOC）. The difference between removals of UV254, and DOC indicated that pre-ozonation greatly changed the molecular structure of AOM, but its capability of mineralization was not remarkable. Only 5% or so DOC was removed by pre-ozonation at 0.6--0.8 mg/L alone. Fractionation results showed that the organic products of pre-ozonation exhibited lower molecular weight and more hydrophilicity, which impaired the removal of DOC in the following coagulation process.

Adsorption kinetics of platinum group elements onto macromolecular organic matter in seawater

Adsorption kinetics of the interaction between Pt, Pd and Rh(defined here as platinum group elements, PGEs)ions and macromolecular organic compounds(MOCs,>10 kDa), including humic acid, carrageenan and bovine serum albumin, and different cutoff fractions of natural organic matter(>1 kDa and >3 kDa) obtained from seawater using centrifugal ultrafiltration devices were investigated. For a given element, all the adsorption kinetics did not reach equilibrium except the interaction between Pt and >1 kDa cutoff, and between Pd and humic acid.For all the tested MOCs, the adsorption kinetics could be divided into two stages, a rapid adsorption process in the first 8 h and the desorption stage after the first 8 h until the equilibrium. The change trend of partition coefficient(log10Kd) values with experiment time was consistent with that of the kinetic curves. However, in the interaction between PGE ions and natural dissolved organic matter(NDOM), an obvious difference in the change trends of log10Kd and kinetic curves was observed. It indicated that the partition behavior of PGE ions interacting with NDOM in seawater was a combined effect of different organic constituents. The adsorption and log10Kd of PGEs in the >1 kDa NDOM fraction were higher and more stable than those in the >3 kDa NDOM fraction. The results also indicated that the 1–3 kDa NDOM may dominate the interaction between PGEs ions and NDOM. Moreover, no kinetic model could perfectly simulate the adsorption process. It indicated that the colloidal struction and morphology of MOCs or NDOM in seawater might be inhomogeneous. Hence, the interaction between PGE ions and organic matter in seawater was a complicated process and needs further research.

Investigation of organic fouling of microfiltration membrane

Because the natural organic matters (NOMs) and proteins are the principal foulants of microfiltration membranes in drinking water, the primary aim of this paper is to obtain a better understanding of the interactions between those foulants and the microfiltration membrane from a novel view of coagulation. Based on reviewed literature and our own analysis, the authors consider that the behaviors of NOMs in the fouling of microfiltration membrane are like a form of crystal growth, and we recognize that the extent of the membrane hydrophobicity plays an essential role in NOMs fouling. However, proteins’ fouling is more affected by intermolecular interaction. Additionally, the effect of membrane surface chemistry is not as essential as it is in the situation of NOMs.

饮用水处理过程中天然有机物引起的超滤膜污染机制研究进展

天然有机物(NOM)存在于地表水、地下水和土壤水中。超滤(UF)膜技术具有运行压力小、设备集成化程度高和占地面积小等优势,但NOM造成的复合污染使超滤膜在水处理的应用管理变得复杂。本文在概述NOM的来源、组成和化学性质的基础上,通过分析不同结构特征的NOM间的相互作用机制,阐述了不同结构特征的NOM的复合膜污染。从离子与NOM络合的影响因素、络合对NOM理化性质的影响等,分析了离子与NOM的复合膜污染。最后,分析了目前研究面临的挑战,并对未来的发展方向进行了展望。

环境炭质介导胞外电子传递转化污染物的机制

环境炭质可作为电子穿梭体,介导微生物胞外电子传递行为,调控着生物地球化学循环过程.直接和间接电子传递是微生物胞外电子传递过程的两种形式.在间接电子传递中,微生物利用电子穿梭体实现电子从胞内到胞外的迁移,除了微生物自身分泌的穿梭体之外,外源性电子穿梭体也被发现可以促进胞内外的电子转移过程,其中天然和人工的电子穿梭体(如腐殖质、生物炭等)在微生物胞外电子传递过程中均发挥着重要的介导作用,改变了胞外电子转移途径.环境炭质的微尺度结构决定了其介导电子转移的功能.于此,本文以两种外源性电子穿梭体的介导表现为研究主体,系统归纳了以腐殖质、生物炭为代表的环境炭质具有的氧化还原活性基团(如醌/酚类基团)和石墨化芳香炭结构(稠环芳香区域)、以及富碳介质的电子穿梭性能和机制;详述了环境炭质介导胞外电子转化典型的污染物(重金属和有机物)的效果;最后,总结了环境炭质(天然有机质和人工有机炭)在土壤、沉积物或水体系统参与介导胞外电子转移过程,并展望了当前研究所面临的挑战,这为新型电子穿梭介质的设计研发和工程应用提供技术支撑.

闽江河口湿地土壤磷形态变化对盐度增加的响应及其影响因素

以闽江河口湿地为研究对象,沿自然盐度梯度分别采集不同盐度区的短叶茳芏湿地(有植被)和光滩(无植被)土壤样品,对不同盐度条件下土壤理化性质、植物生物量及土壤磷形态等进行研究,以评估盐度增加对湿地土壤磷形态变化的影响及其调控因子。结果表明:①不同盐度条件下,土壤全磷和各形态磷含量大体表现为短叶茳芏湿地高于无植被的光滩,尤其在淡水条件下最为显著。总体上,随盐度增加,土壤全磷和有机磷含量逐渐减低,无机磷和氢氧化钠磷含量表现为先降低后增加,而盐酸磷含量则逐渐增加。无机磷是闽江河口不同盐度湿地土壤全磷的主要赋存形态,分别占全磷的74%、77%和83%,占比随盐度增加而增大。②不同植被条件下,短叶茳芏湿地土壤全碳、全氮含量和氮磷比均显著高于光滩土壤(P<0.05)。不同盐度条件下,淡水区土壤全碳、全氮含量和碳氮比均显著高于咸水湿地,并且高盐区大于中盐区(P<0.05)。③地上和地下植物生物量沿盐度梯度呈现明显不同的趋势,地上生物量表现为随盐度增加而增大,地下生物量在淡水区高于咸水区,尤其是显著高于中等盐度区。④相关分析显示,盐度及其关联的地上/地下生物量、全碳、全氮和有机质含量等的变化共同调控了土壤磷形态和有效性的变化。研究表明,滨海河口湿地盐度的增加通过改变土壤有机质含量和地上/地下植物生物量,调控了土壤磷的形态和转化,进而影响湿地生态系统的养分循环和化学计量平衡。

DCMC/PEI涂层改性PVDF超滤膜的分离和抗污染性能研究

为了减轻膜污染和提高膜的分离性能,采用一步沉积法将双醛羧甲基纤维素(DCMC)和聚乙烯亚胺(PEI)涂覆在聚偏氟乙烯(PVDF)超滤膜的表面.DCMC上的醛基可以和PEI上的氨基在膜表面发生席夫碱反应,形成化学交联.与纯PVDF膜相比,DCMC/PEI涂层改性膜具有更高的亲水性(水接触角<40°)和收缩的孔径(平均孔径≈20.32 nm).以腐殖酸(HA)、牛血清白蛋白(BSA)和海藻酸钠(SA)为代表,研究DCMC/PEI涂层改性膜的分离和抗污染性能.涂层膜对HA、BSA和SA具有超过93%的截留率和通量恢复率(FRR),相比原PVDF膜提升了38%.这种兼具高分离和抗污染性能的纤维素涂层膜,为废水净化提供了新的思路.