纳米铁对地下水中As(III)的吸附动力学

实验室合成制得的纳米铁BET比表面积为49.16 m2/g, 直径范围为20~40 nm.通过批实验考察纳米铁对As(Ⅲ)吸附动力学情况.结果表明, 在20℃、pH为7时, 纳米铁能够快速地去除As(Ⅲ), 在60 min内, 0.1 g纳米铁对起始浓度为910 μg/L溶液As(Ⅲ)去除率大于99%.反应遵循准一级反应动力学方程, 标准化后的As(Ⅲ)速率常数k_SA为2.6 mL/(m2·min).纳米铁对As(Ⅲ)的吸附等温曲线能够很好地满足Langmuir和Freundlich方程, 相关系数R2＞0.95, 由Langmuir模型获得单层纳米铁的最大吸附量为76.3 mg/g.0.1 mol/L NaOH对吸附在纳米零价铁(NZVI)的As(Ⅲ)解吸率为21%.在竞争阴离子中, SiO₃2-和H₂PO₄-对As(Ⅲ)的去除有明显阻碍作用, 而其他离子基本上没有影响.纳米铁对As(Ⅲ)的去除机理主要是吸附和共沉淀.      

膨润土负载纳米铁去除地下水中六价铬研究

随着人民生活水平的提高和城市化进程的加快,有机污染物及重金属高强度场地污染对人类健康、生态环境及社会安全构成了严重威胁。地下水中的重金属Cr(Ⅵ)污染逐渐受到重视,纳米零价铁可以有效地将六价铬还原成三价铬,使其沉淀固定下来,从而将污染源区的污染物消减固定,防止其向周围扩散。然而由于纳米铁颗粒微小,易被氧化,极易团聚,自身活性受到限制,因此,纳米铁的分散性、稳定性、良好活性研究至关重要。采用低成本环境友好型粘土矿膨润土作为负载材料制备膨润土负载纳米铁（B-NZVI）,批实验和柱实验研究B NZVI去除模拟地下水中Cr(Ⅵ)。结果表明：(1)自制的膨润土负载纳米铁个体呈球形,呈分散状负载于膨润土;(2)相同铁含量的B-NZVI处理Cr(Ⅵ)的效率远大于纳米铁,还原反应符合伪一级反应动力学模型,表观速率常数K随着B NZVI初始浓度的减小而减小;(3)B NZVI在石英砂柱中基本无迁移,适用于点源污染,Cr(Ⅵ)穿透曲线为B-NZVI的实际应用提供了理论和实验基础。     

羧甲基纤维素稳定纳米铁去除水中六价铬的研究

零价纳米铁(NZVI)具有较高活性,近年受到人们关注并将其应用于地下水污染原位修复,但在实际应用中NZVI易发生氧化与团聚,容易失活。因此尝试运用环境友好型材料对NZVI进行表面改性,选择羧甲基纤维素(CMC)对纳米铁进行表面包覆获得CNZVI,研究不同CMC含量包覆NZVI的分散稳定性和CNZVI对水中六价铬的去除效果。结果表明：经过改性后的CNZVI分散稳定性要明显优于商用纳米铁RNIP,包覆CMC的比例越高,CNZVI的稳定性越好,在较高的CMC包覆比例下,纳米铁不易失活并具有良好的反应活性,对溶液中六价铬有很好的去除效果。     

空气氛围制备核壳纳米零价铁实验研究及其对地下水原位修复的启示意义

运用纳米零价铁进行地下水污染原位处理是近年新发展的环境修复新技术,传统合成纳米零价铁一般多采用无氧条件(通氮气保护)液相法,操作繁琐,不适合批量生产。为了达到纳米零价铁液相法大规模制备和便于现场应用的目的,通过对比传统方法(通氮气除氧),提出在空气氛围中(有氧)制备纳米零价铁。透射电镜和X射线衍射分析表明,空气中直接制备的纳米零价铁Fe@Fe_2O_3有明显核壳结构,粒径40~100nm,内核零价铁,外壳氧化铁厚4~5nm。纳米铁降解水中甲基橙和去除六价铬的实验表明,空气氛围中制备的纳米铁反应活性最好,10min内0.4g/L(RO)Fe@Fe_2O_3能够把200mg/L甲基橙降解98.6%,30min内0.2g/L(RO)Fe@Fe_2O_3能够把20mg/L六价铬去除84.7%。因此,省略了氮气保护环节,成功合成核壳结构纳米零价铁,这有利于现场应用时现配现用,并降低运输保管纳米铁的成本和风险,对开展原位现场污染修复具有启示和应用价值。     

零价铁吸附-还原溶液中U(VI)的实验研究

研究零价铁(Zero-valent iron,ZVI)去除溶液中的U(VI),分析了pH值、反应时间、ZVI投加量、铀溶液初始浓度、其它离子(Mg2+、Mn2+、Cl-、NO-3、CO2-3和Cu2+)等条件因素对U(VI)去除效果的影响,并讨论其去除机理。结果表明:ZVI对溶液中U(VI)有较好的去除作用,在pH=4,振荡时间为120min,ZVI投加量为1.6g/L,铀溶液初始浓度为10mg/L,铀去除量为4mg/g时,U(VI)的去除率可达到63.7%。其它离子实验结果表明:Mg2+、Mn2+、Cl-、NO-3对ZVI去除U(VI)影响不超过3%,CO2-3和Cu2+影响相对较大。ZVI去除溶液中U(VI)以还原沉淀和吸附作用为主,吸附-还原反应遵循一级化学反应动力学方程。     

蒙脱石负载型零价铁纳米颗粒吸附水体中Cr(Ⅵ)污染物实验研究

零价铁纳米颗粒具有许多异于本体物质的独特性质,在废水处理方面应用潜力巨大。以蒙脱石为载体和分散剂,通过硼氢化钠液相还原法制备了零价铁纳米颗粒。采用电镜及多种谱学技术手段对所得铁纳米颗粒进行了表征。结果表明,铁纳米颗粒大致呈球状形貌,平均粒径约为55 nm,在蒙脱石表面分散良好,具有零价铁内核-铁氧化物外壳结构,提高了纳米铁在空气氛中的稳定性。通过批次实验考察了负载型铁纳米颗粒净化Cr(Ⅵ)的效率、过程及机理。净化效果受p H值影响显著,在最优p H值为1.0条件下,零价铁内核因其表面氧化膜酸溶而出露,可作为有效成分快速高效去除水体中Cr(Ⅵ)污染物,机理为零价铁将吸附至其表面的Cr(Ⅵ)异相还原为Cr(Ⅲ)而去除。属自发放热吸附过程,动力学行为符合准二级模型,吸附等温线可用Langmuir方程较好拟合。研究成果为新型纳米零价铁材料的制备及其铬污染治理提供了理论支撑。     

动态光散射技术原位表征天然有机质存在下纳米零价铁的团聚效应

纳米零价铁原位修复地下水污染是近年发展起来的新技术,通过改性合成不同种类纳米零价铁可以克服其易团聚易氧化的问题,水体中存在的天然有机质也会对纳米铁的分散性和反应活性产生影响,因此开展原位测试并研究不同种类纳米铁在水中的团聚效应具有重要意义。本文对实验合成的纳米零价铁、羧甲基纤维素包覆纳米零价铁、膨润土负载纳米零价铁以及商用纳米零价铁,基于动态光散射技术(DLS),运用纳米粒度/Zeta电位分析仪,结合透射电子显微镜(TEM)和沉降光谱曲线等手段,对比研究了天然有机质(腐植酸HA)对纳米铁团聚效应的影响。结果表明,羧甲基纤维素包覆或膨润土负载改性提高了纳米零价铁颗粒的分散稳定性,有效抑制了团聚沉降,团聚体粒径分布在1000 nm以下。HA会吸附在纳米铁颗粒表面,从而增加静电排斥力,进一步减缓了团聚效应,尤其是对膨润土负载纳米零价铁的影响最为显著,其团聚体粒径能降至100 nm以下,沉降速率也极大减缓,分散稳定性表现最佳。本研究表明DLS结合TEM表征纳米颗粒是获得更加丰富的微观粒子信息的一种非常重要的手段。     

有机小分子对膨润土负载钠米零价铁还原铬(Ⅵ)的实验研究

<正>零价铁作为一种还原剂,一直以来被用作含Cr(Ⅵ)等重金属废水的净化材料和地下水污染的修复材料。但是普通零价铁的还原速度慢、效率低;纳米零价铁由于尺寸极小、比表面积大,具有很大的反应活性,但是易团聚、易被氧化失去     

褐铁矿纳米结构化相变零价铁及其除磷性能

利用X射线粉末衍射仪、X射线荧光光谱仪、热分析仪、场发射扫描电镜表征手段研究了铜陵褐铁矿的矿物组成及其形貌形态特征,通过热处理方式获得褐铁矿纳米结构化相变零价铁作为动态柱填料并探究其除磷性能。结果表明,铜陵褐铁矿主要由针铁矿(90%)和石英组成,针铁矿晶体呈针状和片状,具纳米尺寸,集合体呈笋状和球状;热处理促使针铁矿进一步纳米结构化相变形成零价铁,具多孔结构、高比表面积特征;零价铁作为动态柱填料净化模拟含磷(5mg/L)废水可运行1年以上,磷去除效率超过99%,出水磷浓度达到城镇污水一级A排放标准(0.5mg/L)。研究结果可促进褐铁矿资源在保护环境中的应用,也为深度处理含磷废水提供一种新材料。     

联合脱氮法用于硝酸盐污染地下水修复的机理研究

地下水硝酸盐已经成为了世界性环境和健康问题。目前针对硝酸盐的化学还原脱氮、自养脱氮、异养脱氮等单一脱氮方法研究较多;联合脱氮体系包括化学还原、自养脱氮和异养脱氮三种脱氮途径,综合了单一脱氮法的优点,但研究甚少。本研究通过静态批试验,采用零价铁、甲醇和混合菌液研究了联合脱氮法的脱氮能力、脱氮产物、脱氮途径及脱氮机理。结果表明,5 d后单一的零价铁化学还原、自养脱氮和异养脱氮的去除率分别为5.79%、14.30%和63.03%;而联合脱氮的去除率接近100%,去除效果显著优于单一的化学还原脱氮、自养脱氮或异养脱氮。在联合脱氮法体系中,零价铁化学还原、自养脱氮未引起亚硝酸盐积累,而异养脱氮造成了亚硝酸盐积累;化学还原、自养脱氮和异养脱氮引起的铵盐增量均<0.6 mg/L,绝大部分硝酸盐未被还原成铵盐,进而省去了后续除铵工艺;零价铁化学还原、自养脱氮、异氧脱氮三者发生协同作用,表现于在厌氧环境下,零价铁发生腐蚀,产生阴极氢和二价铁,为自养脱氮菌提供了电子供体,从而促进了自养脱氮;异养脱氮不仅占主导地位,而且还会产生CO2,CO2被自养脱氮菌作为无机碳源加以利用,从而提高了体系中自养脱氮能力。这种协同作用表现为联合脱氮法的去除率增加,而在单一的异养脱氮或自养脱氮体系中则无法形成这一良性过程。实验表明联合脱氮法是一种潜在的有效可行的地下水原位修复方法。     

纳米铁还原脱氮动力学及其影响因素

饮用水中硝酸盐(NO3-)对人体健康有危害。为了去除水溶液中NO3-,在实验室制得纳米铁颗粒。它的粒径为20～40 nm,比表面积(BET)为49.16 m2/g。本研究通过批实验考察了纳米铁对NO3-还原脱氮动力学性质和影响NO3-脱氮快慢的主要因素,如反应pH、纳米铁投加量和NO3-起始浓度。实验结果表明,pH越低越有利于NO 3-还原。在一定范围内,NO 3-还原速率随纳米铁投加量增加而增大,而随NO 3-起始浓度升高而降低,反应遵循准一级反应动力学方程,表面吸附和氧化还原反应是纳米铁对NO3-脱氮的主要去除机理。纳米铁对NO3-还原过程中可能反应的途径进行了讨论,NO3-还原产物取决于反应条件。在本研究条件下,纳米铁对NO3-脱氮的最终产物主要为NH4+-N而不是N2,必须进行更多的研究来解决这一问题。     

The Importance of Microbial Iron Sulfide Oxidation for Nitrate Depletion in Anoxic Danish Sediments

Nitrate (NO₃ ^?) reduction processes are important for depleting the NO₃ ^? load from agricultural source areas before the discharge water reaches surface waters or groundwater aquifers. In this study, we experimentally demonstrate the co-occurrence of microbial iron sulfide oxidation by NO₃ ^? (MISON) and other NO₃ ^?-depleting processes in a range of contrasting sediment types: sandy groundwater aquifer, non-managed minerotrophic freshwater peat and two brackish muddy sediments. Approximately 1/3 of the net NO₃ ^? reduction was caused by MISON in three of the four environments despite the presence of organic carbon in the sediment. An apparent salinity limitation to MISON was observed in the most brackish environment. Addition of high surface area synthetically precipitated iron sulfide (FeS _x ) to the aquifer sediment with the lowest natural FeS _x reactivity increased both the relative fraction of NO₃ ^? reduction linked to MISON from approximately 30–100 % and the absolute rates by a factor of 17, showing that the potential for MISON-related NO₃ ^? reduction is environmentally significant and rate limited by the availability of reactive FeS _x .     

Nitrate removal from water using UV-M/S2O4 2− advanced reduction process

In this work, a new process called advanced reduction process (ARP) was used for nitrate removal from water. This ARP process combines sodium dithionite as reducing agent with ultraviolet irradiation using medium pressure lamps (UV-M) as an activating method. Experimental results showed that UV-M/S₂O₄ ^2? process achieved almost complete removal of nitrate from aqueous solutions containing 25 mg NO₃ ^?/L using stoichiometric dose of dithionite of 68.8 mg/L at neutral pH conditions. Analysis of final products and material balance confirmed that NO₃ ^? ions were reduced to ammonium with formation of nitrite as intermediates in addition to the formation of small amounts of volatile species, mainly ammonia and nitrogen gas. Effects of certain experimental parameters including dithionite dose, initial pH, initial nitrate concentration, and UV light source on the kinetics and efficiency of nitrate reduction were evaluated. Increasing dithionite dose augmented the rate of nitrate reduction and enhanced the efficiency of ARP process. Dithionite doses higher than stoichiometric ratios led to complete removal of nitrate in shorter reaction time. UV-M/S₂O₄ ^2? process was found to be effective only under neutral pH or alkaline conditions, and its removal efficiency is negligible in acidic medium (pH < 4). Irradiation with UV-M was more effective than low pressure or narrow band lamps. These results can be attributed to the contribution of several mechanisms for nitrate reduction to ammonium. These include the following: direct photolysis, chemical reduction of nitrate dithionite, and mediated reduction of nitrate by free reducing radicals.     

Early oxidation of organic matter in pelagic sediments of the eastern equatorial Atlantic: suboxic diagenesis

Pore water profiles of total-CO₂, pH, PO^3?₄, NO^?₃ plus NO^?₂, SO^2?₄, S^2?, Fe²⁺ and Mn²⁺ have been obtained in cores from pelagic sediments of the eastern equatorial Atlantic under waters of moderate to high productivity. These profiles reveal that oxidants are consumed in order of decreasing energy production per mole of organic carbon oxidized (O₂ > manganese oxides ~ nitrate > iron oxides > sulfate). Total CO₂ concentrations reflect organic regeneration and calcite dissolution. Phosphate profiles are consistent with organic regeneration and with the effects of release and uptake during inorganic reactions. Nitrate profiles reflect organic regeneration and nitrate reduction, while dissolved iron and manganese profiles suggest reduction of the solid oxide phases, upward fluxes of dissolved metals and subsequent entrapment in the sediment column. Sulfate values are constant and sulfide is absent, reflecting the absence of strongly anoxic conditions.     

Sugarcane waste straw biochar and its effects on calcareous soil and agronomic traits of okra

Biochar has been considered a safe soil additive to enhance soil fertility and agronomic traits of different crops. This study was conducted to explore the impacts of sugarcane waste straw biochar on soil characteristics and some agronomic traits of okra. The experiment was carried out with four treatments, i.e., control, sugarcane waste straw biochar (10 ton ha^?1), farmyard manure (FYM, 10 ton ha^?1), and chemical fertilizers (NPK; 120:100:80 kg ha^?1) having three replications of each treatment. Soil samples were tested for texture, bulk density, particle density, pH, electrical conductivity (EC), organic matter content, nitrate nitrogen (NO₃-N), and extractable-P. The sugarcane waste straw biochar was characterized for plant major nutrient elements. The impact of various treatments was observed on soils and agronomic traits of okra like plant height, fruit size, fruit length, and yield of okra. Results revealed that sugarcane waste straw biochar expressed higher EC value and noticeable amounts of nitrogen (N), phosphorus (P), potassium (K), sulfur (S), and magnesium (Mg). The sugarcane waste straw biochar, in comparison with FYM and NPK, significantly improved the NO₃-N, extractable-P, OM and EC of the calcareous soil, and reduced the soil bulk density. Furthermore, plant growth and yield parameters were significantly improved under biochar application over the control, FYM and NPK. Overall, sugarcane waste straw biochar proved to be a good alternative to conventional organic and inorganic fertilizers under calcareous soil conditions.     

宁东煤炭基地梅花井矿区地下水三氮特征及成因

为研究大规模综合机械化采煤氮污染来源及影响程度,选取宁东煤炭基地侏罗纪煤田鸳鸯湖矿区的梅花井井田为研究对象,通过调查取样分析,对梅花井井田地下水三氮污染分布、物源、水文地质条件进行研究。结果表明:(1)宁东煤炭基地鸳鸯湖矿区梅花井井田三氮NH4+、NO3-、NO2-含量范围分别为0.06～0.12mg/L、4.67～234mg/L、0.01～2.01mg/L,与国家地下水质量标准Ⅲ类水质限值对比,NO2-达到重度或极严重污染,主要分布在潜水含水层;NO3-污染级别为中度、轻度污染,超标样点占调查样点的75%,垂向上已延伸到承压含水层。水平空间上无论矿权范围还是矿权外,污染样点均有存在。(2)部分水样中NO3-毫克当量百分数超过25%,对水化学类型产生影响。(3)煤矿区NO3-、NO2-的污染首先与丰富的物源有关,还受煤矿开采扰动、地形地貌条件、垂向补给径流、水文地球化学条件等因素的影响。研究结果为风积沙大型机械化煤矿开采区地下水氮污染的防治提供了可参考依据。     

Groundwater nitrate contamination and risk assessment in an agricultural area,South Korea

The nitrate of groundwater in the Gimpo agricultural area, South Korea, was characterized by means of nitrate concentration, nitrogen-isotope analysis, and the risk assessment of nitrogen. The groundwaters belonging to Ca–(Cl + NO₃) and Na–(Cl + NO₃) types displayed a higher average NO₃ ⁻ concentration (79.4 mg/L), exceeding the Korean drinking water standard (<44.3 mg/L NO₃ ⁻). The relationship between δ¹⁸O–NO₃ ⁻ values and δ¹⁵N–NO₃ ⁻ values revealed that nearly all groundwater samples with δ¹⁵N–NO₃ ⁻ of +7.57 to +13.5‰ were affected by nitrate from manure/sewage as well as microbial nitrification and negligible denitrification. The risk assessment of nitrate for groundwater in the study area was carried out using the risk-based corrective action model since it was recognized that there is a necessity of a quantitative assessment of health hazard, as well as a simple estimation of nitrate concentration. All the groundwaters of higher nitrate concentration than the Korean drinking water standard (<44.3 mg/L NO₃ ⁻) belonged to the domain of the hazard index <1, indicating no health hazard by nitrate in groundwater in the study area. Further, the human exposure to the nitrate-contaminated soil was below the critical limit of non-carcinogenic risk.     

Two types of Archaean supracrustal belts in the Bundelkhand craton,India: Geology,geochemistry, age and implication for craton crustal evolution

Groundwater sampling was carried out in fast growing Vijayawada urban agglomeration in Andhra Pradesh state with a view to generate base line data and to assess groundwater quality, its variations vis-à-vis urbanization and hydrochemical characteristics. The groundwaters are found to be fresh to brackish, hard to very hard, often enriched with nitrate, phosphate,and faecal colliform indicating anthropogenic influence on groundwater on account of urbanization. Manganese and iron of geogenic origin are also found to be in high concentrations in some localities. The quality deterioration is more in shallow aquifers, as also in core urban and red soil covered areas. Spatial variations in groundwater quality are discernible, with high concentrations of SO₄^-4–,NO₃^- in core urban area suggesting the impact of urbanization. A wide range of chemical constituents indicate water rock interactions as influenced by anthropogenic activities controlling the urban aquifers. The order of abundance of cations is Na>Mg>Ca>K, while the order of abundance of anions is Cl>HCO₃>SO₄>NO₃. The baseline study suggests the need to protect the groundwater resource through sound environmental protection measures for the welfare of the inhabitants in the city around which the new capital is proposed to be constructed for newly formed Andhra Pradesh state in India.     

Nitrogen and oxygen isotopic compositions of water-soluble nitrate in Taihu Lake water system, China: implication for nitrate sources and biogeochemical process

The stable isotope nitrogen-15 (¹⁵N) is a robust indicator of nitrogen (N) source, and the joint use of δ¹⁵N and δ¹⁸O–NO₃ ^? values can provide more useful information about nitrate source discrimination and N cycle process. The δ¹⁵N and δ¹⁸O–NO₃ ^? values, as well as major ion tracers, from Taihu Lake in east China were investigated to identify the primary nitrate sources and assess nitrate biogeochemical process in the present study. The results show that the nitrate concentration in West Taihu Lake (WTL) was generally higher than those in East Taihu Lake (ETL) and its upstream inflow rivers. The NO₃ ^?/Cl^? value combined with mapping of δ¹⁵N–NO₃ ^? and NO₃ ^? concentration suggest that the mixing process should play a major effect in WTL, and denitrification was the dominant N transformation process in WTL. A linear relationship of close to ~1: 2 was observed between δ¹⁵N–NO₃ ^? and δ¹⁸O–NO₃ ^? values in WTL, confirming the occurrence of denitrification in WTL. The δ¹⁵N–NO₃ ^? data imply that sewage and manure were the principal nitrate sources in WTL and its feeder rivers, while the nitrate in ETL might derive from soil organic nitrogen and atmospheric deposition. The δ¹⁸O–NO₃ ^? data indicate most of nitrate from microbial nitrification of organic nitrogen matter possibly make a significant contribution to the lake.