可降解微塑料对铜和锌离子的吸附解吸特性

为了评估可降解微塑料对共存污染物的载体效应,对可降解微塑料PLA（聚乳酸）对重金属污染物（Cu²⁺、Zn²⁺）的吸附和解吸行为进行了探究,同时选择常规微塑料PP（聚丙烯）进行对照实验.在紫外老化过程中,微塑料（MPs）均表现为表面出现裂纹、凹坑,比表面积增大,负电荷增多,含氧官能团强度增强,亲水性增强.较之PP,PLA在紫外老化过程中理化性质的改变尤为明显.老化后MPs的吸附能力远大于老化前,老化PLA对Cu²⁺的最大吸附量可达5.56mg/g,约为新制PLA（2.27mg/g）的2.5倍;老化前后PLA对重金属的吸附量均高于PP.解吸实验表明,老化后MPs对重金属的解吸率均低于老化前,而老化前后PLA对Cu²⁺、Zn²⁺的解吸量及解吸率均高于PP.较之胃液环境,老化前后MPs对金属离子的解吸更易在肠液环境中进行.说明PLA相对于PP对重金属具有更强的载体作用,且PLA更容易将重金属污染物释放到人体内,进而对人体健康造成威胁.     

MOFs材料在废水污染物吸附治理中的应用研究进展

介绍了国内外MOFs材料吸附去除废水中各种污染物的研究进展,主要针对重金属离子(Hg²⁺、U⁶⁺、Cr⁶⁺、Cd²⁺、Pb²⁺、Co²⁺、Sb⁵⁺、Sr²⁺)及类金属离子(As³⁺、As⁵⁺)、有机污染物(染料分子、芳香化合物)等的去除,分析了MOFs及改性MOFs材料对废水中污染物的吸附性能;展望了MOFs材料在废水污染物吸附治理中的应用前景,提出高稳定性及具有催化性质的MOFs材料是用于废水中污染物吸附治理的理想材料。     

微塑料老化对其理化性质和盐酸四环素吸附行为的影响研究

微塑料(MPs)是一种新型污染物,因广泛存在于水体环境中而备受关注.为了探明微塑料的老化过程及与共存有机污染物的相互作用,本研究以高密度聚乙烯(HDPE)和聚氯乙烯(PVC)为目标微塑料,探究了紫外辐照(UV：照度135.8μW·cm^-2,λ=340 nm)和紫外活化过氧化氢(UV+30%H₂O₂) 2种老化方式对微塑料(MPs)理化性质及对盐酸四环素(TH)吸附性能的影响,并分析了pH和盐度等环境因素对其吸附性能的影响.结果表明,2种老化方式均使HDPE和PVC微塑料产生大量裂纹和褶皱,结晶度增加,含氧官能团增多,疏水性减弱.原始MPs对TH的吸附动力学与准一级动力学模型相吻合,而老化MPs则更符合准二级动力学模型,且它们的主要吸附模式均为液膜扩散和颗粒内扩散.老化MPs对TH的吸附符合Freundlich模型,属于非均匀表面的多层吸附.老化处理增强了MPs对TH吸附能力,其中,HDPE-UV和HDPE-UV/H₂O₂的平衡吸附量(Q_e)分别为2.023...     

光老化对聚丁二酸丁二醇酯基可降解微塑料吸附Pb(Ⅱ)的影响及其机制

微塑料可以在水中吸附重金属并作为载体共同迁移,且微塑料会在水中受光照而老化,影响其吸附能力和吸附机制.本研究通过XRD、FTIR、SEM/EDS等分析手段对聚丁二酸丁二醇酯基可降解微塑料(PBS-MPs)进行了表征,探究了光老化过程对PBS-MPs吸附水中Pb(Ⅱ)的影响及其机制.结果表明,光老化能增加PBS-MPs表面亲水性含氧基团及活性吸附位点数量,对Pb(Ⅱ)的最大吸附容量从64.13μg·g^-1提升至362.06μg·g^-1;Pb(Ⅱ)在P-PBS上的吸附符合Elovich动力学模型,吸附机制包括表面络合、静电作用和孔填充/扩散作用.光老化会强化可降解微塑料对水中Pb(Ⅱ)的吸附,从而促进Pb(Ⅱ)的迁移,二者共存可对水环境带来更为严重的生态风险.     

介质阻挡放电等离子体老化微塑料及对Zn (II)吸附的影响

为了在实验中缩短微塑料的老化时间,更真实地模拟自然老化条件,采用介质阻挡放电（DBD）等离子体老化聚乙烯微塑料（PE-MP）和聚丙烯微塑料（PP-MP）,同时研究了老化前后PE-MP和PP-MP对Zn （II）的吸附过程和机理.随着放电时间延长和输入电压升高,微塑料表面出现微小裂纹或孔洞,形成含氧官能团.老化后PE-MP和PP-MP对Zn （II）的吸附容量分别提高了22.7%和14.8%.老化前后微塑料对Zn （II）的吸附均符合准二级动力学模型.颗粒内扩散模型表明,Zn （II）在微塑料上的吸附过程可分为快速吸附,慢速吸附和吸附平衡3个阶段.同时,老化前后微塑料对Zn （II）的吸附均符合Langmuir吸附等温线模型.热力学结果表明,微塑料对Zn （II）的吸附是自发的吸热过程.Ca²⁺、腐殖酸和低pH值不利于微塑料对Zn （II）的吸附.     

PE微塑料对土壤吸附镉的影响及机理研究

微塑料影响土壤对重金属的吸附,改变重金属在土壤中的迁移转化。该文采用批量实验研究了3种粒径(13、48、150μm)聚乙烯微塑料(PE-MPs)存在时土壤对Cd的吸附解吸行为,同时借助扫描电子显微镜-X射线能谱、X射线衍射、X射线光电子能谱和傅里叶变换红外光谱等测试方法探究了相关机理。结果表明,PE-MPs对土壤吸附Cd²⁺的影响表现为：抑制Cd²⁺的吸附,促进Cd²⁺的解吸,且当PE-MPs剂量较高或粒径较大时,这种影响更明显。无论是否存在PE-MPs,土壤对Cd²⁺的吸附过程均更符合准二级动力学和Freundlich模型,说明其过程均为受化学吸附控制的多层吸附。土壤对Cd²⁺的吸附机制主要为表面络合和沉淀作用,PE-MPs能覆盖土壤表面的活性位点,干扰Cd²⁺与土壤中含氧官能团相互作用,进而减弱土壤对Cd²⁺的化学吸附。PE-MPs能增强土壤中Cd的流动性,增加Cd对土壤生态系统污染的风险。     

SnS2/α-Al2O3对酸性废水中汞离子的去除机制

基于硫化物与汞亲和性较强的特性,构建了SnS₂/α-Al₂O₃复合型除汞吸附剂材料.实验结果表明,该复合材料对Hg²⁺的最大吸附容量可达950mg/g,其吸附效果不受pH值（酸性pH=1~6）影响,汞浓度为65mg/L时,均能达到近100%的汞去除效率.同时,吸附过程不会受其他金属离子（Cd²⁺、Cr³⁺、Zn²⁺、Cu²⁺、Pb²⁺、Ni²⁺、Co²⁺等）的强烈干扰,汞浓度为1mmol/L条件下,汞的去除速率及效率均未有很大差距.吸附过程未有大量Sn²⁺析出,证明了该复合材料的酸性稳定性.通过吸附动力学以及吸附机制研究表明,该吸附过程为单层化学吸附.通过盐酸溶液浸泡洗涤,可以实现SnS₂/α-Al₂O₃复合材料的再生和循环使用.     

模拟环境老化对PE微塑料吸附Zn(II)的影响

探讨了酸处理（1mol/L HCl）、碱处理（1mol/L NaOH）、氧化处理（30% H₂O₂）和高温-冻融处理（70℃和-22℃交替）4种老化方式对聚乙烯（PE）微塑料表面性质和Zn（II）吸附行为的影响.结果表明,4种老化方式均使PE微塑料表面出现大量的粗糙褶皱结构,但未改变表面化学结构.4种老化方式均导致PE微塑料Zn（II）吸附量的增加,其顺序为：碱处理 > 酸处理 > 氧化处理 > 高温-冻融处理 > 原样.PE微塑料吸附Zn（II）的动力学过程符合Lagrange准二级吸附动力学和W-M颗粒扩散模型,说明吸附过程是多个吸附阶段共同作用的结果,吸附等温线符合Langmuir和D-R模型,证实PE微塑料对Zn（II）的吸附属于物理吸附,老化使PE微塑料表面出现的大量褶皱是其Zn（II）吸附量增加的主要原因.     

微塑料老化对水土环境中磷吸附行为的影响

作为一种具有吸附能力的新型污染物，微塑料对环境中污染物的吸附作用会加剧其对环境的污染。该文通过紫外灯照射120 d对聚乙烯（PE）、聚苯乙烯（PS）和聚氯乙烯（PVC）3种微塑料进行老化处理，研究老化作用对微塑料吸附水土环境中磷的影响。结果表明，老化过程使微塑料表面出现大量褶皱、碎片和沟壑，比表面积增大，含氧官能团数量显著增加。相比于原始塑料，老化微塑料对磷的吸附量均有所增加，由此说明老化过程提高了微塑料的吸附能力。老化前后微塑料对磷吸附行为均较好地符合准二级动力学模型（R2>0.964），表明老化前后微塑料对磷的吸附是以化学吸附为主。老化前后的微塑料更符合Langmuir等温吸附模型（R2>0.961），表明磷在各微塑料上吸附以单层吸附为主。p H对微塑料吸附磷影响显著，老化前后的微塑料随pH的增加对磷的单位吸附量均呈“U型”趋势，且老化后微塑料的吸附量均高于老化前。在pH为9时老化PE、PS、PVC对磷的吸附量达到最大，分别为0.752、0.758、0.896 mg/g。随土壤中微塑料添加比例的增大，土壤-微塑料体系对磷的吸附量提升有限；相较于添加原始微塑料的土壤-微塑...     

老化前后聚苯乙烯微塑料对天然有机物的吸附

随着地表水环境中微塑料的不断检出,微塑料污染受到广泛关注.微塑料是一类比表面积较大的疏水性物质,具有一定的吸附作用,其势必对地表水中的天然有机物产生影响.此外,暴露于自然环境下的微塑料也会受到紫外辐射或氧化等过程的影响,从而改变其物理化学性质,影响其对天然有机物的作用.本文开展了聚苯乙烯微塑料(mPS)经紫外和过氧化氢老化前后吸附腐殖酸(HA)和富里酸(FA)的对比研究.结果表明,老化过程使微塑料的孔隙和表面粗糙度明显增加,比表面积有大幅提高,但结晶度减小,官能团没有明显变化.疏水性的mPS微塑料对HA的吸附效果好于FA,且老化微塑料对两种有机物的吸附能力皆高于老化前,微塑料的吸附能力与比表面积大小呈正相关关系.吸附试验数据皆较好地拟合了准二级动力学模型(R²>0.93)和Freundlich模型(R²>0.91),微塑料对HA和FA的吸附以多层不均匀的物理吸附为主,两者在微塑料上的吸附分别为自发的放热和吸热反应过程.试验微塑料对HA和FA的吸附能力皆随着pH的增加呈先降低后增加的趋势.两种有机物在超纯水和地表水介质中的解吸率具有...     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.