Oxidative removal of acetaminophen using zero valent aluminum-acid system: Efficacy, influencing factors, and reaction mechanism

Commercial available zero valent aluminum under air-equilibrated acidic conditions (ZVAl/H⁺/air system) demonstrated an excellent capacity to remove aqueous organic compounds. Acetaminophen (ACTM), the active ingredient of the over-the-counter drug Tylenol^®, is widely present in the aquatic environment and therefore the treatment of ACTM-contaminated water calls for further research. Herein we investigated the oxidative removal of ACTM by ZVAl/H⁺/air system and the reaction mechanism. In acidic solutions (pH < 3.5), ZVAl displayed an excellent capacity to remove ACTM. More than 99% of ACTM was eliminated within 16 hr in pH 1.5 reaction solutions initially containing 2.0 g/L aluminum and 2.0 mg/L ACTM at 25 ± 1\textcelsius. Higher temperature and lower pH facilitated ACTM removal. The addition of different iron species Fe⁰, Fe²⁺ and Fe³⁺ into ZVAl/H⁺/air system dramatically accelerated the reaction likely due to the enhancing transformation of H₂O₂ to HO. via Fenton's reaction. Furthermore, the primary intermediate hydroquinone and the anions formate, acetate and nitrate, were identified and a possible reaction scheme was proposed. This work suggested that ZVAl/H⁺/air system may be potentially employed to treat ACTM-contaminated water.     

O3/UV降解水中的乙酸和硝基苯

利用O3 /UV和O3/H2O2降解了水中的乙酸,结果表明,在相同条件下处理60min后,O3/UV对乙酸的去除率仅比单独臭氧化处理提高了3%,而O3/H2O2在此条件下完全降解乙酸.O3/UV在处理硝基苯过程中却显示较好的氧化降解能力,通过分析表明,硝基苯降解过程中所产生的副产物H2O2对有机物的去除具有很重要的作用.因此,O3/UV氧化降解能力的提高可能有2方面的原因,紫外光对有机物的活化作用;中间产物H2O2催化臭氧分解产生了高活性的羟基自由基. 单独紫外光催化臭氧分解产生羟基自由基的效率极低.     

三江平原湿地土壤活性有机碳组分特征及其与土壤酶活性的关系

对三江平原3种主要类型天然湿地(毛苔草湿地、小叶章湿地、岛状林湿地)O-20cm土壤活性有机碳(土壤微生物量碳、土壤可溶性有机碳)特征进行了研究,分析了不同湿地的土壤活性有机碳与土壤总有机碳及酶活性间的关系.结果表明:不同类型湿地的土壤活性有机碳组分含量存在较大的差异,土壤活性有机碳、土壤总有机碳及土壤脲酶、蔗糖酶、淀粉酶、过氧化氢酶的变化趋势具有基本近似的特征.表现为毛苔草湿地>小叶章湿地>岛状林湿地;土壤微生物量碳、可溶性有机碳与土壤总有机碳和酶活性存在显著正相关关系,其中,酶活性与土壤微生物量碳相关性最为显著.另外.毛苔草湿地土壤MBC/SOC、DOC/SOC的比值低于其它2种类型湿地,表明毛苔草湿地生物活性有机碳库的周转速率低.淹水抑制了微生物和酶的分解作用,有利于土壤有机碳的累积.因此,沼泽湿地水文条件的变化将会对土壤碳累积与分解过程产生较大的影响.     

“活性甲醛”与甲醛远距离毒性的初步研究

甲醛是否具备远距离毒性(distant-site toxicity)是揭示甲醛与白血病关系的关键问题.本研究采用DPC、MTT实验方法检测甲醛的远距离毒性,结果发现当把等剂量的甲醛与GSH联合作用对细胞进行染毒后细胞内产生的DPC系数比单独同剂量的甲醛组要高很多,在MTT实验中发现在单独甲醛组中加入等量的GSH后细胞活性也出现了显著下降;在动物实验中,当对小鼠肝染毒后脑组织中也同样出现了损伤.说明甲醛在机体内与GSH形成了结合物,这种结合物可能协助甲醛完成跨膜并进入到局部组织再次释放出游离态甲醛,实现了甲醛的远距离毒性,这种结合态的甲醛称之为"活性甲醛".     

外加碳源水淹条件下高硫土壤中铜的迁移转化

采用高硫低有机质酸性重金属污染土壤,通过研究外加碳源水淹条件下各层土壤中酸可挥发性硫化物(AVS)的产生以及各剖面层中Cu的总量分布、Cu在孔隙水中的浓度及存在形态的变化情况,探讨了水淹土壤中的AVS对Cu迁移转化的影响.结果表明,外加碳源水淹条件下,硫酸根被还原,产生的大量AVS可促使水相中游离活性Cu向惰性较高的硫化物结合态和残渣态转化而被固定;不同深度土壤中AVS产生情况不同,其含量由深层向浅层递增,并在顶层大量聚集,由此导致孔隙水中的Cu²⁺浓度由土壤深层向浅层递减,这种垂直浓度梯度差,趋动活性态Cu由深层向浅层的垂直迁移,在AVS大量富集的表层中形成丰富的铜硫化物沉淀,使土壤表层中惰性态铜及总量累积增加,底层活性铜及总量下降,从而使铜的生态风险和生物风险降低.     

Efficient adsorption of Mn(Ⅱ) by layered double hydroxides intercalated with diethylenetriaminepentaacetic acid and the mechanistic study

In this study, greatly enhanced Mn(II) adsorption was achieved by as-synthesized diethylenetriaminepentaacetate acid intercalated Mg/Al layered double hydroxides(LDHsDTPA). The adsorption capacity of LDHs-DTPA was 83.5 mg/g, which is much higher than that of LDHs-EDTA(44.4 mg/g), LDHs-Oxalate(21.6 mg/g) and LDHs(28.8 mg/g). The adsorption data of aqueous Mn(II) using LDHs-DTPA could be well described by the pseudosecond order kinetics and Langmuir isotherm model. Thermodynamics study results also showed that the adsorption process of Mn(II) by LDHs-DTPA was exothermic as indicated by the negative ΔH value. Furthermore, based on the structural, morphological and thermostable features, as well as FT-IR and XPS characterizations of LDHs-DTPA and the pristine LDHs, the adsorption mechanism of Mn(II) was proposed. The carboxyl groups of DTPA were proposed to be the main binding sites for Mn(II), and the hydroxyl groups of LDHs also played a minor role in the adsorption process. Among the three common regeneration reagents, 0.1 mol/L Na_2CO_3 was the best for reusing LDHs-DTPA in Mn(II)adsorption. Besides, the Mn(II) adsorption performance could be hindered in the presence of typical inorganic ions, especially cations. Further specific modifications of LDHs-DTPA are suggested to get more selective adsorption of Mn(II) in practical applications.     

水铁矿及其腐殖酸复合体对Sb(Ⅴ)的吸附行为研究

在实验室条件下制备了水铁矿和水铁矿与腐殖酸复合物,通过X射线衍射、傅里叶红外光谱、Zeta电位及比表面积的测定对其基本性质进行了表征,并采用静态批处理吸附试验研究了水铁矿及其腐殖酸复合物对Sb（V）的吸附行为特征,探讨了吸附时间、初始pH值、初始浓度、不同干扰离子（PO₄^3-、CO₃^2-、NO₃^-和Cl^-）对水铁矿及其复合物吸附Sb（V）的影响.结果表明：腐殖酸与水铁矿结合后未改变水铁矿的晶型结构,但降低了水铁矿的零电点与比表面积.水铁矿及其复合物对Sb（V）的吸附过程符合Langmuir和伪二级动力学模型,腐殖酸的加入抑制了水铁矿对Sb（V）的吸附.随着pH的上升,水铁矿与复合物的去质子化能力增强,对Sb（V）的吸附量减小;溶液中共存离子PO₄^3-、CO₃^2-对水铁矿及其腐殖酸复合物吸附Sb（V）有较强的抑制作用.     

The occurrence of per- and polyfluoroalkyl substances (PFASs) in fluoropolymer raw materials and products made in China

Perfluorooctanoic acid (PFOA), its salts, and related compounds were listed as new persistent organic pollutants by the Stockholm Convention in 2019. In this study, the occurrence of residues of PFOA and other per- and polyfluoroalkyl substances (PFASs) in raw materials and fluoropolymer products from the Chinese fluoropolymer industries are reported for the first time. The PFOA concentrations in raw materials and fluoropolymer products were in the range of 6.7 to 1.1 × 10⁶ ng/g, and <MDL (method detection limit) to 5.3 × 10³ ng/g, respectively. Generally, the levels of PFOA in raw materials were higher than in products, implying that PFOA in the emulsion/dispersion resin could be partly removed during the polymerization or post-processing steps. By tracking a company's polytetrafluoroethylene (PTFE) production line, it was found that over a 5 year period, the residual levels of PFOA in emulsion samples declined from 1.1 × 10⁶ to 28.4 ng/g, indicating that the contamination of PFOA in fluoropolymer products from production source gradually decreased after its use had been discontinued. High concentrations of HFPO-TrA (2.7 × 10⁵ to 8.2 × 10⁵ ng/g) were detected in some emulsion samples indicating this alternative has been widely applied in fluoropolymer manufacturing in China.     

Ultrafiltration with in-line coagulation for the removal of natural humic acid and membrane fouling mechanism

Experimental and theoretical analysis were made on the natural humic acid removal and the membrane fouling of ultrafiltration （UF） with in-line coagulation. The results showed dissolved organic carbon （DOC） and UV254 removals by the UF with in-line coagulation at pH 7 were increased from 28% to 53% and 40% to 78% in comparison with direct UF treatment respectively. At the same time, the analysis of high performance liquid chromatography showed that UF with coagulation had significant improvement of removal of humic acid with molecular weights less than 6000 Da in particular. Compared to direct UF, the in-line coagulation UF also kept more constant permeate flux and very slight increase oftransmembrane pressure during a filtration circle. Two typical membrane fouling models were used by inducing two coefficients Kc and Kp corresponding to cake filtration model and pore narrowing model respectively. It was found that membrane fouling by pore-narrowing effect was effectively alleviated and that by cake-filtration was much decreased by in-line coagulation. Under the condition of coagulation prior to ultrafiltration at pH 7, the cake layer formed on the membrane surface became thicker, but the membrane filtration resistance was lower than that at pH 5 with the extension of operation time.     

三段式硝化型生物接触氧化反应器的启动及特性

采用实际生活污水,研究了三段式串联的硝化型生物接触氧化反应器的挂膜启动及各段的硝化特性.试验结果表明:利用中间沉淀池出水作为生物接触氧化反应器的进水进行自然挂膜,在无需投加接种污泥的情况下,20d挂膜成熟,NH4+-N的去除率达到98%以上.反应器中随着沿程推流,三段的生物量和生物膜厚度逐渐降低,最大的生物量和生物膜厚度分别为1271.25mg/L和119.45μm.分析各段的硝化特性,发现三段在低温15℃条件下仍具有较高的比硝化速率,并且在同一温度下(15,23,32℃),第2、3段的比硝化速率均大于第1段.针对上述现象,根据比耗氧速率SOUR粗略估计了AOB和NOB在各段中的相对比例.3段AOB的百分比分别为(25.64+4.89)%, (34.59+5.02)%, (42.50+1.57)%,而NOB的百分比为(23.52+3.35)%, (39.65+4.26)%, (40.69+2.19)%. 此外,系统运行125d的FISH结果表明,3段的微生物菌群分布确实存在差异.与第1段相比,后2段的AOB和NOB更容易成为优势菌.     

高级氧化联合生物活性炭工艺深度净化污水中PPCPs研究进展

污水处理厂传统的二级生化处理对药品及个人护理用品(Pharmaceutical and Personal Care Products, PPCPs)等新兴污染物的去除率较低, PPCPs随出水排放会给生态环境带来较大的风险,并会经过生物富集最终危害到人体健康,因此需要通过进一步的深度净化以削减其风险.本文综述了常见PPCPs在污水处理系统的分布特征及生态风险,阐述了高级氧化工艺(Advanced oxidation processes, AOPs)、生物活性炭工艺(Biological activated carbon, BAC)以及高级氧化联合生物活性炭工艺(AOPs-BAC)深度净化PPCPs的净化原理,在此基础上,综述了AOPs-BAC工艺对污水中PPCPs的深度净化效果及主要影响因素,并探讨了AOPs-BAC工艺对污水中PPCPs的风险削减能力,为污水中PPCPs深度净化工艺的研发及PPCPs的生态风险控制提供了参考.     

聚硅氯化铝混凝剂中Al(Ⅲ)水解聚合历程及铝硅作用特性研究

采用共聚与复合两种制备工艺，制备出了系列具有不同碱化度和不同Ａｌ／Ｓｉ摩尔比的聚硅氯化铝混凝剂，分析研究了ＰＡＳＣ中Ａｌ（Ⅲ）的水解－聚合历程以及聚硅酸与铝水解聚合产物的相互作用，探讨了ＰＡＳＣ溶液的酸解聚。     

重金属汞对土壤酸性磷酸酶的影响及其机理

通过土壤培养试验、紫外吸收光谱和荧光光谱技术 ,研究了重金属汞对土壤酸性磷酸酶催化活性、动力学性质的影响及机理 .结果表明 ,汞对土壤酸性磷酸酶活性、酶促反应动力学性质均具有显著影响 .汞对土壤酸性磷酸酶的作用可能为非竞争与反竞争混合的抑制类型 .而汞对麦芽酸性磷酸酶的抑制作用为反竞争性抑制 .重金属汞通过改变土壤酸性磷酸酶分子色氨酸、酪氨酸残基的微环境致使酶活性中心的构象发生变化 ,进而对酶的催化活性产生影响     

酸雨对鼎湖山土壤的累积效应及荷木的反应

运用盆栽实验研究了酸雨对鼎湖山季风常绿阔叶林土壤危害的累积效应和优势树种荷木的一些生理反应.结果表明,在酸雨直接淋洗土壤的条件下,与对照相比,土壤酸度,土壤淋洗液酸度增加;土壤交换性K⁺、Na⁺上升,Ca²⁺、Mg²⁺和有效Mn、Zn下降;土壤淋洗液中K、Na含量下降,Ca、Mg、Cu、Fe、Mn和Al在pH3.05的酸雨处理下含量显著上升;但生长于模拟酸雨土壤中的荷木在土壤化学性质发生变化后仍能健康生长.     

腐植酸对nZVI去除水中Cr(VI)的抑制及抑制作用的消除

以纳米级零价铁(nZVI)为主要工具修复受污染水体中的Cr(VI),考察了腐植酸(HA)对nZVI去除水中Cr(VI)的抑制作用,并初步探讨了淀粉稳定化nZVI对HA抑制作用的消除.结果表明,随着HA初始浓度由0增加大5,10,15,20,30mg/L,反应10min nZVI对Cr(VI)的去除效率分别达到91.9%,82.6%,78.6%,70.4%,70.0 %和69.4 %.可见,HA对nZVI去除Cr(VI)的影响是双方面的,一方面,HA会吸附在nZVI的表面,占据nZVI表面的活性反应部位,导致反应速率的下降;另一方面,HA表面带有大量的活性基团, 有较大的负电性,会起到一定传递电子的作用,进一步促进反应的进行.由于nZVI的比表面积较大,HA的吸附作用占据主导地位, 导致HA的加入对nZVI去除Cr(VI)反应产生明显的抑制作用. 适量淀粉(0.5g/L)的加入确实能够起到阻碍nZVI颗粒团聚和HA在nZVI颗粒表面吸附的作用,从而维持nZVI较高的反应活性,消除HA对nZVI去除Cr(VI)的抑制作用.     

系列混合碳源条件下颗粒化EBPR系统菌群结构变化规律研究

在SBR反应器中接种富含聚磷菌的活性污泥,采用一系列不同丙酸/乙酸比例混合的碳源进行EBPR系统污泥的颗粒化培养,并考察了颗粒化进程中的系统菌群结构变化,以及不同混合碳源条件对系统功能菌种竞争的影响.结果表明,污泥颗粒化过程对EBPR系统菌群结构产生了较大的筛选作用.原本在系统中占优势的一类Uncultured bacterium被迅速淘汰;Uncultured Rhodocyclaceae bacterium、部分Candidatus Competibacter phosphatis、部分Denitrifying bacterium、Acinetobacter及部分Uncultured alpha proteobacterium分别逐渐被淘汰.在各个成熟的颗粒化EBPR系统中,除磷微生物主要为Uncultured Chlorobi bacterium与Uncultured alpha proteobacterium.不同混合碳源条件培养的颗粒化EBPR系统菌群结构差异主要表现为Candidatus Competibacter phosphatis(聚糖菌)与Uncultured Chlorobi bacterium(聚磷菌)菌群数量的不同.混合碳源中乙酸比例的提高可造成颗粒化EBPR系统中Candidatus Competibacter phosphatis的增长,使系统的除磷效率下降.而碳源中丙酸比例相对较高的条件有利于Uncultured Chlorobi bacterium增长,从而有助于颗粒化EBPR系统维持较好的除磷效率.     

生态承载力水平评价的动态模型及其应用——以洞庭湖生态经济区为例

生态承载力是可持续发展研究的核心.本文基于生态承载力的内涵,从4个方面构建了生态承载力的评价指标体系,并以最大信息熵原理(MIEP)为基础,自组织特征映射神经网络(SOFM)为算法,借助MATLAB数学软件为计算平台,从复杂系统结构演化的角度提出了生态承载力评价模型,并用MIEP模型对洞庭湖生态经济区2008—2012年的生态承载力进行评价,以指导当地生态建设.结果表明,5年间该地区的生态承载力呈总体上升的趋势,其中,2008年和2009年两年生态承载力水平基本一致,2010年呈现较明显的上升,2011年的生态承载力剧烈下降后在2012年呈现大幅回升.ξ值各分量的雷达图揭示出各指标逐年贡献程度的变化,结合准则层面的分析发现,水资源发展状况对该地生态承载力整体水平影响较大.与主成分分析法的比较表明了MIEP模型对生态承载力评价的可行性,同时其能更好地体现生态承载力发展演变的动力学特性,连接权值的获取避免了人为设定的主观性,在评价中有明显优势,且在预测上有一定潜力.