滇池周边浅层地下水硝酸盐来源及转化过程识别

明确硝酸盐的主要来源及转化过程对地下水氮污染防治和水资源开发利用具有重要意义.为了探明滇池周边浅层地下水中硝酸盐污染现状及来源,于2020年雨季（10月）和2021年旱季（4月）在滇池周边共采集73个浅层地下水样,运用水化学和氮氧同位素（δ¹⁵N-NO₃^-、δ¹⁸O-NO₃^-）识别浅层地下水中硝酸盐的空间分布、来源及转化过程,并结合同位素混合模型（SIAR）定量评价不同来源氮对浅层地下水硝酸盐的贡献.结果表明,旱季浅层地下水中有40.5%的采样点ρ（NO₃^--N）超过地下水质量标准（GB/T 14848）Ⅲ类水质规定的20 mg·L^-1,雨季超过47.2%的采样点ρ（NO₃^--N）超过20 mg·L^-1.氮氧同位素和SIAR模型分析结果证明了土壤有机氮、化肥氮、粪肥和污水氮是浅层地下水硝酸盐的主要来源,以上氮源对旱季浅层地下水中硝酸盐的贡献率分别为13.9%、11.8%和66.5%,对雨季的贡献率分别为33.7%、31.1%和25.9%,而大气氮沉降贡献率仅为8.5%,对该区浅层地下水中硝酸盐来源贡献较小.硝化作用是旱季浅层地下水中硝态氮转化的主导过程,雨季以反硝化作用为主,且反硝化作用雨季比旱季明显.     

长江上游典型山地农业小流域浅层地下水硝态氮时空变异特征及影响因素

长江上游山区以浅层地下水作为主要供水水源,但其极易受到农业生产等活动所导致的硝态氮（NO₃^--N）污染.本文选取长江上游典型山区农业小流域作为研究对象,对土地利用与管理强度和水文地质条件等进行了野外调查,阐明其浅层地下水NO₃^--N时空变异特征并分析其影响因素.结果表明,研究小流域地下水中NO₃^--N质量浓度变化范围为0.40~12.51 mg ·L^-1,超标率近30%.受降雨和管理强度影响,丰水期降雨量和施肥量增加,土壤中氮素在降雨驱动下淋溶流失进入浅层地下水,呈现出丰水期NO₃^--N质量浓度（6.73 mg ·L^-1）高于枯水期NO₃^--N质量浓度（6.28 mg ·L^-1）的时间变异特征.在空间上,小流域地下水中NO₃^--N质量浓度呈现坡耕地和居民区集中分布的截留和大兴子流域中地下水NO₃^--N质量浓度（截留子流域：6.58mg ·L^-1;大兴子流域：6.34 mg ·L^-1）高于苏荣子流域（5.20 mg ·L^-1）的特征,主要由不同子流域地下水埋深和土地利用类型的空间分异特征导致.此外,浅层地下水NO₃^--N质量浓度与Cl^-、NH₄⁺-N、DOC和SO₄^2-质量浓度呈正相关,而与pH值呈负相关,表明地下水化学因子亦是其不可忽略的影响因素.因此,加强山地农业小流域浅层地下水NO₃^--N时空变异特征及其影响因素研究对防控山区农村浅层地下水硝态氮污染和保障饮用水安全十分必要.     

青岛市农区地下水硝态氮污染来源解析

为了提高作物产量,肥料大量投入在农业种植区日益普遍,导致了农区地下水硝态氮（NO₃^--N）污染.农业面源污染是地下水硝态氮污染的主要原因.为了保障饮用水安全,明确农区硝态氮污染的来源是十分必要的.本研究分别于2009年和2019年在青岛农区随机选取35个采样点,借助反距离加权法（IDW）对硝态氮含量进行空间分布分析,通过测定氮、氧同位素进行溯源,运用SIAR模型量化污染源的贡献率.结果表明,青岛市地下水硝态氮含量（平均值）由2009年的38.49 mg·L^-1降低为2019年的22.37 mg·L^-1,但仍高于世界卫生组织（WHO）规定的饮用水中硝态氮的最大允许含量.2009年和2019年硝态氮含量都呈现由南向北逐渐增加的趋势,南部污染轻,北部污染重.δ15N-NO₃^-和δ¹⁸O-NO₃^-的交叉图显示青岛市地下水硝态氮主要来源是化肥、土壤氮、粪肥和污水.水同位素表明降水是青岛市地下水的主要来源.贝叶斯混合模型（SIAR模型）表明污染源贡献率为：粪肥和污水（47.42%） > 土壤氮（27.80%） > 化肥（14.35%） > 大气氮沉降（10.43%）.从2009~2019年青岛市地下水质量得到了改善,但硝态氮污染状况仍不容忽视,应根据硝态氮污染来源,有针对性地防治以确保农区饮用水安全和农业的可持续发展.     

基于水化学及稳定同位素的岩溶山区城镇水体硝酸盐来源示踪

由于岩溶水文系统的地球化学敏感性和脆弱性,岩溶地下水NO₃^-污染已成为世界范围普遍存在的环境问题,而岩溶山区地下水硝酸盐来源解析对于保障区域供水安全和人体健康具有重要意义.因此,本文选取贵州中部典型岩溶山区城镇主要供水流域地表水和地下水为研究对象,基于土地利用类型,联合水化学分析及δ¹⁵N-NO₃^- 、δ¹⁸O-NO₃^-示踪技术对水体硝酸盐分布特征、来源贡献及迁移转化过程进行研究.结果表明,研究区水体溶解性无机氮以硝态氮为主,水体NO₃^-含量及分布与区域土地利用方式密切相关,硝酸盐污染主要集中于住宅用地和耕地 &林地区岩溶地下水中.水体NO₃^-主要来源于与农业活动和城镇化建设有关的土壤有机氮、化肥及粪便污水,水体氮循环主导过程为硝化作用,反硝化作用基本不存在.稳定同位素模型（SIAR）分析结果显示,区域水体硝酸盐主要受当地农业活动及城镇化过程影响,其中,土壤有机氮、化肥及粪便污水对地表水硝酸盐的贡献率分别为50.24%、27.97%和24.58%,对地下水硝酸盐的贡献率分别为54.58%、24.58%和20.15%,大气降水来源贡献率较低.     

联合PMF模型与稳定同位素的地下水污染溯源

基于传统水质监测与污染排放的污染源识别方法,存在监测频率与识别结果模糊等限制,难以实现污染源及迁移转化的准确量化.联合多元统计分析与稳定同位素技术,以成都平原典型混合用地区地下水污染为研究对象,提出利用正定矩阵因子分析（PMF）模型识别污染主控因子,减小环境因素对污染源判别的干扰,并基于水化学分析与土地利用构建贝叶斯稳定同位素混合模型,进一步量化不同污染源对地下水典型污染物硝酸盐氮（NO₃^-）的贡献率.结果表明,研究区地下水NO₃^-、NO₂^-、NH₄⁺、Mn、Fe、SO₄^2-和Cl^-均存在不同程度超标,且具有空间异质性.地下水中"三氮"主要以NO₃^-为主,NO₃^-浓度在菜地的地下水中普遍偏高（平均值为9.29 mg·L^-1）,其次是在养殖场（平均值为7.66 mg·L^-1）和耕地（平均值为7.09 mg·L^-1）,在工业区最低（平均值为2.20 mg·L^-1）.研究区地下水水质受原生地质作用、农业活动、水文地球化学演化、生活污染和工业污染的复合影响,且农业活动是研究区地下水NO₃^-增长的主要原因.研究区内农业区地下水NO₃^-的主要来源贡献为化肥（32%）和土壤氮（25%）;工业区地下水NO₃^-的主要来源贡献为污水排放（28%）和大气降雨（27%）.通过多元统计与稳定同位素技术的有机结合,有效识别了地下水污染来源及其贡献率,可为地下水污染源头防控提供科学依据.     

氮肥-垃圾渗滤液复合影响区非饱和-饱和带全剖面氮素分布特征及微生物响应

农田氮肥和垃圾填埋场渗滤液是我国地下水氮素污染的两大来源,从氮肥-垃圾渗滤液复合影响区域内采集6份土壤剖面-地下水样品,分析非饱和-饱和带全剖面中氮素的分布特征,来清晰判识该类典型区域的氮素跨介质污染特征和途径,同时通过高通量测序进行氮循环功能微生物分析,来解析氮循环功能微生物对氮素分布的响应.结果发现,在高施肥量采样点中,土壤中的硝态氮（NO₃^--N）和溶解性有机氮（Dissolved Organic Nitrogen,DON）含量均显著高于低施肥量采样点（p<0.01）,NO₃^--N大量分布在深度0~240 cm的土壤中（p<0.05）,部分NO₃^--N下渗进入地下水,高施肥量采样点地下水中NO₃^--N浓度在总溶解性氮（Total Dissolved Nitrogen,TDN）中占比达31.93%~84.70%,硝化菌在氮循环功能菌中占比为27.08%~87.99%,说明氮肥是该区域地下水NO₃^--N的主要来源.铵态氮（NH₄⁺-N）在非饱和带深度0~20 cm和400~460 cm的范围内含量较高（p<0.05）,垃圾填埋场下游的地下水NH₄⁺-N浓度均超标,在TDN中占比为26.40%~59.71%.统计分析表明,垃圾填埋场渗滤液可能是造成地下水中NH₄⁺-N浓度空间差异的重要因素,并很可能是导致地下水位波动带附近出现NH₄⁺-N高积累的主要原因（p<0.05）.这些结果将有助于复合影响区氮素的污染评估和防控.     

黄土高塬沟壑区典型城郊流域地表水硝酸盐来源示踪

随着工农业的快速发展,地表水硝酸盐污染已成为黄土高原地区严重的环境问题之一.以黄土高塬沟壑区典型城郊流域砚瓦川为研究区,采用水化学分析方法和氮氧双稳定同位素技术,并结合SIAR模型,定量识别旱季和雨季研究区地表水硝酸盐不同污染源的贡献率,阐明不同污染源季节性差异的主要原因.结果表明,流域地表水无机氮主要以NO₃^--N和NO₂^--N形态存在,NO₃^--N和NO₂^--N雨季浓度平均值均高于旱季,而NH₄⁺-N则呈现相反特征;流域内地表水硝酸盐的转化过程主要以硝化作用为主,雨季其主要来源是粪肥污水,而旱季主要为粪肥污水和土壤氮淋溶,铵肥次之;不同污染源对流域地表水硝酸盐的贡献比例具有显著的季节性差异,旱季与雨季城镇污水排放的贡献比例均为最高,分别为31.40%和65.66%,且雨季污水排放对NO₃^-的影响远高于旱季,夏季居民用水增加导致大量污水排放至流域内是引起这一现象的主要原因.     

河套灌区春小麦-萝卜复种模式下土壤NO3--N动态

研究了河套灌区春小麦-萝卜复种模式下,土壤、土壤溶液和地下水NO₃^--N浓度的动态变化.结果表明:随着试验时间的延长,土壤表层NO₃^--N含量降低,深层(100～150cm)增加;土壤溶液中、下层NO₃^--N浓度(70、120cm)显著高于上层(30cm),尤其是在萝卜生长季.当前的灌溉条件下,不同年度、不同生长季土壤NO₃^--N淋失量的多少与土壤水分的下渗量密切相关,且输入的氮素中有30%以上以NO₃^--N的形式淋失掉.施肥区地下水NO₃^--N浓度显著高于未施肥区,且65.5%的水样超过WHO规定的上限(11.3mg/L).总之,经过连续2a的春小麦与萝卜复种可使表层土壤NO₃^--N含量明显降低,但由于中、下层土壤剖面中残留大量的NO₃^--N,因此在当前灌溉措施下,短期内NO₃^--N淋失是不可避免的.     

雷州半岛岭北地区地下水水文地球化学特征

地下水是雷州半岛重要的供水水源.本研究在雷州半岛岭北地区开展了水化学和氢氧稳定同位素调查,报道了区域地下水水化学特征;基于水化学及同位素地球化学理论和方法揭示了控制水质的主要水文地球化学过程.结果表明,地下水pH、总硬度、TDS以及K⁺、Cl^-、SO₄^-质量浓度较低;H₂SiO₃和NO₃^-质量浓度较高.孔洞裂隙水水化学类型以Mg-Ca-HCO₃和Mg-Ca-HCO₃-Cl型为主,Cl^-沿径流方向增加明显;浅层孔隙水以Ca-Cl、Na-Ca-HCO₃-Cl和Na-Ca-Mg-HCO₃-Cl型为主;中深层孔隙水以Mg-Ca-HCO₃、Na-Ca-Mg-HCO₃和K-Na-HCO₃-SO₄型为主,K⁺、Na⁺、Cl^-和SO₄^-沿径流方向有所增加.地下水受大气降水补给,Cl^-和Na⁺起源于海洋性大气降水,Mg⁺、Ca²⁺和HCO₃^-源自硅酸盐矿物水解,NO₃^-主要来自化学肥料;浅层孔隙水、裂隙孔洞水受蒸发浓缩作用影响,中深层孔隙水受阳离子交换作用影响.计入硝酸盐后,50.85%的NO₃型水指示着地下水具有污染趋势.本研究结果为可持续开发利用区域地下水提供了依据.     

碳氮氧同位素解析典型岩溶流域地下水中硝酸盐来源与归趋

利用多同位素（C、N和O）和水化学方法解析贵州八步地下河流域水体中硝酸盐（NO₃^-）来源与转化过程,利用SIAR模型定量计算NO₃^-不同输入端的贡献比例.结果表明,研究区地下水NO₃^-污染严重,近38%的地下水样品NO₃^-超过饮用水限值.地下水的δ¹⁵N-NO₃值介于2.3‰~30.33‰,均值9.68‰,δ¹⁸O-NO₃值介于2.65‰~13.73‰,均值6.64‰,δ¹⁸O-H₂O值介于-8.83‰~-7.37‰,均值-8.18‰.同位素组成（δ¹⁵N-NO₃、δ¹⁸O-NO₃和δ¹⁸O-H₂O）指示硝化作用主导着流域内氮素循环.硝化作用产生的硝酸加速了碳酸盐岩溶解,导致地下水中δ¹³C_DIC与δ¹⁵N-NO₃存在显著负相关性（P<0.001）,说明δ¹³C_DIC与δ¹⁵N-NO₃相结合是判断岩溶水中NO₃^-转化的有效手段.地下水和地表水中NO₃^-主要来源于土壤氮、粪肥污水和铵态氮肥料,其对地下水中NO₃^-贡献率分别为36.19%、33.71%和30.1%,对地表水贡献率分别为39.15%、36.08%和24.77%.岩溶流域内污水处理应同时去除污水中的NO₃^-和NH₄⁺,农业区应科学施肥,以有效降低地下水中NO₃^-的补给通量.     

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.     

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.     

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.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.