纳米Fe3O4覆盖对沉积物-水界面砷释放的影响

为揭示纳米四氧化三铁（nFe₃O₄）覆盖对沉积物溶解态砷（As）和有效态As的钝化效果,在开展室内培养试验的基础上,利用微界面分析技术、高分辨率平衡式间隙水采集技术（HR-peeper）和薄膜扩散梯度技术（DGT）,探究nFe₃O₄覆盖下沉积物氧化还原环境、铁锰含量等因素对As的作用机制.结果表明：在nFe₃O₄覆盖下沉积物pH值较对照组逐渐增大,Eh先减小后增大;nFe₃O₄可以有效去除沉积物溶解态As,最大有效去除率为22%;nFe₃O₄覆盖使得有效态As的平均值降低了2.30mg/L;溶解态As与溶解态Fe （II）、溶解态As与溶解态Mn、有效态As与有效态Fe （II）、有效态As与有效态Mn均存在显著正相关关系（P<0.001）;nFe₃O₄的覆盖可以促进铁铝低结晶状无定形水合氧化态As含量的增加.     

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C1（E_x/E_m=270/304nm,类蛋白）,C2（E_x/E_m=285,235/360nm,类蛋白）和C3（E_x/E_m=270,340/442nm,类腐殖质）.荧光特征指数表明茜坑水库沉积物及其上覆水DOM受新生内源和陆源输入共同影响,但主要以内源为主.表层沉积物中的类蛋白质浓度和类腐殖质浓度均远高于上覆水体,表层沉积物可能向上覆水体释放小分子DOM.紫外可见光谱与三维荧光表征结果一致,表层沉积物DOM分子量、腐殖化程度、芳香性和疏水性均低于上覆水.相关性分析表明,上覆水C1组分与C2组分相关性显著（P<0.05）,表明其存在同源性.通过对茜坑水库沉积物及其上覆水DOM光谱特征的研究,可进一步分析水库有机质污染特征.     

KMnO4-PAC对高原喀斯特湖库DOM的DBPsFP控制

以云贵高原典型喀斯特湖库红枫湖取水口溶解性有机质（DOM）为研究对象,调查不同组合方式下高锰酸钾-聚合氯化铝（KMnO₄-PAC）对消毒副产物的生成潜能（DBPsFP）变化和平均组成分布,并通过红外光谱（FTIR）和三维荧光光谱（3D-EEM）对部分样品进行化学表征,推断其影响机制.结果表明：在0.1,0.2,0.4mg/L KMnO₄投加量下,DBPsFP降低17.5~73%,DOM的卤代活性化学结构和官能团部分被有效钝化;PAC的网捕和卷扫效应使DBPsFP进一步减少27.9~86.1%,组合工艺对DBPs的生成潜能影响大小为：三卤甲烷（THM₄） > 卤乙酸（HAA₉） > 卤乙腈（HAN₄）/卤代酮（HK₂）/三氯硝基甲烷（TCNM）.FTIR的结果表明预氧化后3300cm^-1处的透过率降低,指纹区1000~1300cm^-1处的峰频提升,表明分子中的O-H、COOH和C-O官能团增加,共轭不饱和结构在KMnO₄作用下部分消失.3D-EEM验证了外源有机物（腐殖酸）在DOM中占比随KMnO₄浓度梯度升高而下降,同时类蛋白结构的吸收峰强度增加,说明最终DBPs贡献可能源于DOM中剩余的小分子类蛋白（氨基酸）.     

2019年长江口及其邻近海域溶解有机物的分布和季节变化特征

2019年3月和7月分别采集长江口及其邻近海域表层和底层的海水样品,测定了其中溶解有机碳（DOC）浓度和有色溶解有机物（CDOM）的吸收光谱。本文根据DOC浓度和CDOM吸收系数a₂₅₄、比紫外吸光度SUVA₂₅₄、光谱斜率S_275-295等参数对该区域溶解有机物（DOM）的分布情况和季节变化进行了研究。结果表明,DOC浓度和a₂₅₄指征的CDOM丰度总体表现出近岸高、外海低的特点;指征CDOM芳香性的SUVA₂₅₄和指征CDOM平均分子量的S_275-295分别随着离岸距离的增加逐渐降低和升高,表明CDOM的芳香性和平均分子量均逐渐降低;两个航次表层的DOC浓度、CDOM丰度、芳香性及平均分子量均显著高于底层;7月和3月相比,DOC浓度、CDOM丰度及芳香性较高,但未发现平均分子量存在显著的季节变化;DOC浓度、a₂₅₄、SUVA₂₅₄、S_275-295均与盐度呈现显著的相关关系,其中,DOC浓度、a₂₅₄、SUVA₂₅₄呈现负相关关系,而S_275-295呈现正相关关系。上述参数与盐度的相关系数（R2）表明,DOC和CDOM在3月较为保守,而在7月（尤其是在表层）不保守程度明显升高。     

河口陆基养虾塘沉积物铁的含量和形态

为研究河口陆基养殖塘底泥中铁的迁移和转化机制,本文测定了福建省3个河口养虾塘养殖期表层和亚表层底泥沉积物中活性铁含量及间隙水的常见组分.结果表明,不同站点间晶质Fe（III）、非硫Fe（II）、有机铁、铁硫化物含量存在显著差异.间隙水SO₄^2-和Cl^-可能是影响不同站点间Fe的形态和分布存在异质性的主要环境影响因子之一.盐度较高的养虾塘,铁的硫化物含量较高,有机铁和晶质Fe（III）含量较少.陆基养虾塘底泥沉积物中活性铁含量按固相Fe（III） > 铁硫化物 > 非硫Fe（II） > 有机铁的顺序排列.养虾塘亚表层沉积物铁硫化物（FeS和FeS₂）含量高于表层沉积物,而表层沉积物有机铁含量与间隙水SO₄^2-和NH₄⁺浓度高于亚表层沉积物.铁硫化物的生成一定程度上降低河口陆基养虾塘沉积物营养盐污染的潜在风险.     

植物分布对洱海沉积物间隙水DOM光谱特征及对氮磷释放影响研究

沉水植物分解导致大量溶解性有机质(DOM)进入水环境,进而对水质产生重要影响.然而,关于沉水植物分布对沉积物间隙水DOM的变化特征及其对氮磷释放的影响研究较少.本研究利用紫外-可见吸收光谱(UV-vis)和三维荧光光谱结合平行因子(EEMs-PARAFAC)技术对比研究了洱海沉水植物分布/非分布区沉积物间隙水DOM组分变化特征,并探讨DOM变化对氮磷释放的影响.结果表明,沉水植物分布区沉积物间隙水DOM主要以富里酸为主,而沉水植物非分布区DOM则以腐殖酸为主.通过UV-vis分析发现,沉水植物分布区沉积物间隙水DOM a₃₅₅、a₄₄₀、SUVA₂₅₄、A₂₅₃/A₂₀₃、S_R平均值高于植物非分布区,这表明沉水植物分解作用能够促进沉积物间隙水DOM含量、芳香性、分子量、以及取代基数量增加.沉水植物分布区上覆水和间隙水氮磷浓度均高于沉水植物非分布区,这主要是由于沉水植物衰亡期腐烂分解释放氮磷.此外,DOM中的羟基和羧基能够与磷酸盐竞争沉积物颗粒上的吸附位点,...     

基于微尺度技术精准评估2种覆盖剂对砷的钝化效果

为探究原位覆盖材料对表层沉积物砷（As）的钝化效果,选择可推广应用的锁磷剂（LMB）和增氧剂（CaO₂+CaCO₃）,通过室内培养实验,应用微电极技术和高分辨率平衡式间隙水采集技术（HR-Peeper）,研究覆盖材料对沉积物中砷（As）钝化的影响机制。实验设置锁磷剂组、增氧剂组和对照组共3个处理组,分为4个实验阶段（分别以加入覆盖剂后的第4,30,90,150天为节点）。结果表明:锁磷剂与增氧剂可有效去除沉积物中的As。锁磷剂覆盖最高可降低50.86%的溶解态As,影响深度可达到-100 mm,有效期150 d。增氧剂覆盖最高可降低55.52%的溶解态As,影响深度为-100 mm,90 d后效果减弱。锁磷剂与增氧剂覆盖显著降低了溶解态As的释放通量。锁磷剂上的镧离子对砷酸盐有很强的亲和力,可去除溶液中的砷酸盐。此外,锁磷剂和增氧剂增加了沉积物-水界面中的Eh值,使Fe （Ⅱ）被氧化成Fe （Ⅲ）,吸附As从而降低As浓度。此外,溶解态As与Fe （Ⅱ）在沉积物剖面上同步变化且显著正相关（P<0.001）,证实了Fe和As的耦合释放机制。研究结果可为淡水生态系统中As污染的控制和治理提供支撑。     

典型喀斯特城市湖库溶解性有机质成分特征及来源解析

为探索喀斯特城市湖库溶解性有机质（DOM）成分特征及来源信息,以我国贵阳市重要喀斯特湖库——红枫湖、百花湖、松柏山水库和阿哈水库为研究对象,分析了表层水体溶解性有机碳（DOC）、叶绿素a（Chla）和DOM光学参数(a₂₅₄、a₂₈₀、a₃₅₀、 E2∶E3、S_275-295、 FI、β:α、 BIX、 HIX)的空间差异,同时利用荧光吸收峰（B、 T、 A、 M、 C、 D、 N）和三维荧光平行因子分析（EEM-PARAFAC）解释DOM各成分丰度及占比状况,并运用Spearman相关分析及主成分分析（PCA）揭示DOM参数的相关性和主要环境过程.结果表明,喀斯特城市湖库ρ（DOC）和ρ（Chla）范围分别为4.24～11.9 mg·L^-1和0.32～19.7μg·L^-1,松柏山水库腐殖质(a₂₅₄)和芳香类蛋白质(a₂₈₀)较高,导致相对分子质量(E2∶E3和S_275-295)高于其它湖...     

外加葡萄糖对洱海沉积物溶解性有机质光谱特征影响

利用三维荧光光谱(3DEEM)技术,研究了外加葡萄糖对洱海沉积物中DOM(溶解性有机质)释放和转化的影响以及DOM的光谱特征变化. 培养试验设4个处理(C₁、C₂、C₃、C₄),ρ(葡萄糖)分别为0、50、100和200mg/L. 结果表明:①洱海沉积物DOM出现了6种荧光峰,分别代表类蛋白荧光物质和类富里酸荧光物质,并且荧光峰位置在1~8d呈“蓝移”现象,8~17d呈“红移”现象. ②紫外区与可见区类富里酸(峰A和峰M)随培养时间延长逐渐升高,其中C₄处理的峰A荧光强度小于C₁处理;在培养初期C₄处理的峰M荧光强度小于C₁处理,培养后期则相反. ③随着培养时间延长,上覆水中类蛋白荧光强度呈“单峰”曲线变化,其峰值均出现在培养后第8天,在整个培养过程中,类蛋白荧光强度均表现为C₄处理>C₁处理. 外加葡萄糖可促进洱海沉积物DOM转化,使部分微生物难利用的DOM转化为易被微生物利用的类酪氨酸、类色氨酸等类蛋白物质.      

表层沉积物主要矿化组分对Mn(Ⅱ)的吸附特性与贡献

考察表层沉积物中主要矿化组分对Mn(Ⅱ)的吸附特性,能够更清楚地解释Mn(Ⅱ)在沉积物-水界面上的迁移转化机理. 以山东省即墨市王圈水库表层沉积物为例,采用化学选择性萃取方法将表层沉积物的主要矿化组分(Fe氧化物、Mn氧化物、有机质和黏土矿物)进行分离,研究这些矿化组分对Mn(Ⅱ)的吸附特性和贡献. 结果表明,表层沉积物中w(有机质)、w(TE-Fe)和w(TE-Mn)(TE-Fe、TE-Mn分别为总可萃取态Fe、Mn氧化物)分别为16.23、10.12和1.771 mg/g. Langmuir和Freundlich吸附等温方程均能较好地描述表层沉积物及其主要矿化组分吸附Mn(Ⅱ)的过程,Langmuir吸附等温方程拟合效果更好,相关系数达0.95以上. E-Mn、E-Fe(E-Mn、E-Fe分别为可萃取态、锰、铁氧化物)、有机质和黏土矿物对Mn(Ⅱ)的吸附能力分别为77 852.5、38 764.0、17 704.5和44.0 mg/g. 由于各主要矿化组分在表层沉积物中含量的差异,因此有机质的吸附贡献最大,为2.24 mg/g;其次是E-Fe和黏土矿物,分别为1.91和1.22 mg/g;E-Mn为0.62 mg/g.      

覆盖材料对洱海不同湖区沉积物溶解态有机磷和无机磷释放影响及差异

通过模拟实验探讨了4种覆盖材料对洱海不同湖区沉积物溶解态总磷（DTP）、溶解态有机磷（DOP）和溶解态无机磷（SRP）释放影响及差异.结果表明：①与无覆盖对照相比,覆盖材料通过改变洱海沉积物pH和Eh及溶解性有机质（DOM）特征,降低了沉积物DTP最大释放量,其中,覆盖氧化铁对洱海北部和南部沉积物DTP释放控制效果较好,与无覆盖对照相比,释放量分别减少了44.3%和35.71%;而覆盖氧化铝对中部湖区沉积物DTP释放控制效果较好,与无覆盖对照相比,释放量减少了29.6%.②覆盖铁铝氧化物对洱海不同湖区沉积物SRP和DOP释放量影响差异明显,北部湖区沉积物覆盖氧化铁后,SRP和DOP释放量分别降低了35.6%和36.2%,主要是因为其降低了沉积物pH和Eh,而增加了DOM活性所致;中部湖区沉积物覆盖氧化铝后,SRP和DOP释放量分别降低了28.9%和31.6%,与氧化铝促进了该湖区DOM活性密切相关;南部湖区沉积物覆盖氧化铁后,沉积物SRP和DOP释放量分别降低了47.4%和16.5%,则与覆盖氧化铁降低了该湖区沉积物pH和Eh有关.因此,如选择覆盖材料控制洱海不同湖区沉积物磷释放,北部和南部湖区应选择覆盖氧化铁,而中部湖区应选取氧化铝作为覆盖材料.     

连环湖牙门气泡沉积物重金属演化和污染研究

2010年8月在牙门气泡的湖心位置采集了柱状沉积岩心.采用HNO3-HClO4-HF联合消解并运用ICP-MS测试了柱状沉积岩心中金属元素Cr、Cu、Mn、Ni、Fe、Pb、Zn、Cd、Al、Ba、Ca、K、Li、Mg、Na和Sr的含量,结合沉积岩心年代测定,研究了该湖区沉积物重金属元素演化特征及污染历史.应用富集系数法探讨了湖泊重金属的污染特征.结果表明,1950年以前各元素含量变化趋势平稳,1950～1990年间波动较大,1990年以后金属元素Mn、Zn、Cd、Pb、Fe、Ni、Cr、Cu、Ca、Li和Sr浓度明显增加.牙门气泡重金属元素Mn、Zn、Cd、Pb存在轻微污染,而Ni、Cr和Cu无污染.     

Distribution of mercury and methylmercury in river water and sediment of typical manganese mining area

Manganese (Mn) ores contain substantial concentrations of mercury (Hg), and mining and smelting of Mn ores can bring Hg into the surrounding aquatic environment through atmospheric deposition, leaching of electrolytic Mn residue and Mn gangue dump. However, limited is known that how these processes influence the environmental behaviors of Hg in waterbody. Therefore, the seasonal distribution and existing form of Hg in water and sediment in one Mn ore area in Xiushan County, Chongqing were investigated. Our results showed that the mean Hg and methylmercury (MeHg) concentrations in water (n=35) were 5.8 ± 4.6 ng/L and 0.22 ± 0.14 ng/L, respectively. The mean Hg concentrations in retained riverbed and fluvial bank sediment (n=35) were 0.74 ± 0.26 mg/kg and 0.63 ± 0.27 mg/kg, respectively (the mean MeHg concentrations were 0.64 ± 0.40 µg/kg and 0.51 ± 0.30 µg/kg, respectively). It indicated that the mining and smelting of Mn ores were the main sources of anthropogenic Hg, and Mn may inhibit Hg methylation in rivers in Mn ore areas. Mercury in the bound to iron/ Mn (Fe/Mn) oxides of low crystallinity fraction (Hg-OX) accounted for 4.01% and 5.25% of the total Hg concentrations in the retained riverbed and fluvial bank sediment, respectively. The amount of Hg bound to Fe/Mn oxides in sediment increased significantly due to the manganese mining activities in the investigated area. Therefore, it could be hypothesized that high Hg concentrations in river sediment in Mn mining areas are closely related to high Mn concentration in sediment.     

氧化还原电位对土壤中重金属环境行为的影响研究进展

E_h（redox potential,氧化还原电位）代表土壤氧化性和还原性的相对程度,是以电位反映土壤所处氧化还原状态的指标.由于重金属易与对E_h敏感的组分发生吸附、络合、沉淀等化学反应,因此E_h的变化会直接/间接影响重金属形态从而决定其毒性和活性.E_h变化对重金属活性往往存在双向影响:①淹水环境使E_h降低,引发反硝化反应、铁锰氧化物和硫酸盐还原,使pH向中性靠拢,从而间接导致酸性土壤中游离态重金属沉淀或碱性土壤中吸附态重金属释放.②厌氧条件在使E_h发生变化的同时,会引起铁锰氧化物、有机质、硫化物的形态或含量发生改变,如铁锰氧化物还原、大分子有机质分解,分解产物与重金属离子结合增加了可溶性重金属的浓度,但厌氧条件也可以使重金属离子和硫化物产生沉淀,且还原Cr、Hg等元素,降低毒性;在氧化条件下,硫化物氧化形成硫酸盐促进了重金属释放;但铁锰离子沉淀及其氧化物形态变化形成的具有强吸附力的无定形铁锰氧化物可重新吸附游离态金属离子.这些复杂的化学变化对定量化研究E_h对重金属的影响造成困难,从而降低了E_h波动环境（水稻土、周期性覆水潮滩沉积物等）中重金属污染风险评价的准确性,也限制了通过改变E_h来原位修复重金属污染土壤的方法实施.因此,需进一步对E_h诱导下土壤颗粒界面上发生的与重金属行为相关的反应进行深入研究,并开发检测分析技术,如无损伤的物理探测方法或同位素稀释技术等,建立不同土壤中E_h与重金属形态、活性的定量关系,以揭示E_h对重金属形态的影响机制.      

Recent advances in catalytic decomposition of ozone

Ozone (O₃), as a harmful air pollutant, has been of wide concern. Safe, efficient, and economical O₃ removal methods urgently need to be developed. Catalytic decomposition is the most promising method for O₃ removal, especially at room temperature or even subzero temperatures. Great efforts have been made to develop high-efficiency catalysts for O₃ decomposition that can operate at low temperatures, high space velocity and high humidity. First, this review describes the general reaction mechanism of O₃ decomposition on noble metal and transition metal oxide catalysts. Then, progress on the O₃ decomposition performance of various catalysts in the past 30 years is summarized in detail. The main focus is the O₃ decomposition performance of manganese oxides, which are divided into supported manganese oxides and non-supported manganese oxides. Methods to improve the activity, stability, and humidity resistance of manganese oxide catalysts for O₃ decomposition are also summarized. The deactivation mechanisms of manganese oxides under dry and humid conditions are discussed. The O₃ decomposition performance of monolithic catalysts is also summarized from the perspective of industrial applications. Finally, the future development directions and prospects of O₃ catalytic decomposition technology are put forward.     

Adsorption of Pb, Cd to Fe, Mn oxides in natural freshwater surface coatings developed in different seasons

Metal oxides( Fe, Mn oxides) in natural surface coatings(biofilms and associated minerals) are believed to play a significant role n the fate and transport of trace metal in aquatic environments. Seasonal variation of Fe, Mn oxides and organic materials in surface oatings, which were developed periodically on glass slides in Nanhu Lake, Jilin Province, China over the time frame of three seasons,was investigated in order to understand the influence of metal oxides on Pb and Cd adsorption to heterogeneous surface coating materials(biofilm). Pb and Cd adsorption was measured under controlled laboratory conditions( mineral salts solution with defined speciation, ionic trength 0.05 mol/L, 25~C and pH 6.0). The classical Langmuir adsorption isotherm was applied to estimate equilibrium coefficients of Pb nd Cd adsorption to the surface coatings. In general, components in the surface coatings varied greatly with seasons altering and btained higher concentrations in summer while the content of iron oxides always exceeded that of manganese oxides. Correlation nalyses between the maximum adsorption of Pb and Cd and components in the surface coatings developed periodically indicated that Pb hase association with Mn oxides and Cd phase association with Fe oxides as well as Mn oxides were statistically significant. Effect of Mn xides on Cd adsorption was confirmed in view of its higher content in the surface coatings. The importance of ferromanganese oxides for b and Cd adsorption to the natural surface coatings developed in different seasons was evidenced.     

Speciation of organic phosphorus in a sediment profile of Lake Taihu I: Chemical forms and their transformation

Organic phosphorus(nonreactive P,NRP)is a major component of P in sediments,but information about its chemical forms and dynamic transformation is limited.The chemical forms and dynamic behaviors of NRP in a sediment profile from Lake Taihu,a freshwater and eutrophic lake in China,were investigated.Five forms of NRP in the sediments were extracted based on a chemical fractionation technique,including easily labile NRP(NaHCO3-NRP),reactive metal oxide-bound NRP(HCl-NRP),humic acid-associated NRP(NaOH-NRPHA),fulvic acid-associated NRP(NaOH-NRPFA)and residual NRP(Res-TP).There were notable transformations with increasing sediment depth from the labile NaHCO3-NRP and NaOH-NRP pools to the recalcitrant HCl-NRP and Res-TP pools,which caused the NRP to become increasingly recalcitrant as the early diagenetic processes proceeded.Further analyses showed that the relative changes in contents of organic matter and reactive Fe oxides in the sediment profile triggered a competition for binding NRP fractions and led to the transformation of NRP.The results highlighted the importance of abiotic processes in regulating the diagenesis of organic P and its stability in sediments.     

Removal of tetracycline from water by Fe-Mn binary oxide

Significant concerns have been raised over the presence of antibiotics including tetracyclines in aquatic environments. A series of Fe-Mn binary oxide with different Fe:Mn molar ratios was synthesized by a simultaneous oxidation and coprecipitation process for TC removal. Results showed that Fe-Mn binary oxide had higher removal efficiency than that of hydrous iron oxide and hydrous manganese oxide, and that the oxide with a Fe:Mn molar ratio of 5:1 was the best in removal than other molar ratios. The tetracycline removal was highly pH dependent. The removal of tetracycline decreased with the increase of initial concentration, but the absolute removal quantity was more at high concentration. The presence of cations and anions such as Ca²⁺, Mg²⁺, CO₃^2- and SO₄^2- had no significant effect on the tetracycline removal in our experimental conditions, while SiO₃^2- and PO₄^3- had hindered the adsorption of tetracycline. The mechanism investigation found that tetracycline removal was mainly achieved by the replacement of surface hydroxyl groups by the tetracycline species and formation of surface complexes at the water/oxide interface. This primary study suggests that Fe-Mn binary oxide with a proper Fe:Mn molar ratio will be a very promising material for the removal of tetracycline from aqueous solutions.     

铁铝复合氧化物对两种细菌的吸附作用研究

铁铝氧化物是土壤的重要组分之一,其对土壤中有机无机组分的迁移具有重要影响.本文以枯草芽孢杆菌和荧光假单胞菌为研究对象,通过批吸附实验和DLVO理论,探究铁铝复合氧化物对细菌的粘附作用及其作用机制.结果表明,铁铝复合氧化物对细菌的粘附随着平衡浓度的增加而增加,吸附过程可用Langmuir方程拟合.铁铝1∶3复合氧化物对枯草芽孢杆菌和荧光假单胞菌的最大吸附量分别为3717.43和2792.29 mg·g~(-1),铁铝3∶1复合氧化物对枯草芽孢杆菌和荧光假单胞菌的最大吸附量分别为3455.58和2760.33 mg·g~(-1).随着pH值的增大,两种铁铝复合氧化物对两种细菌的吸附量均呈下降趋势.铁铝1∶3复合氧化物对两种细菌的吸附量均大于铁铝3∶1复合氧化物.静电吸引力是铁铝复合氧化物与细菌之间相互作用的主要因素之一.