Sunlight-driven reduction of silver ion to silver nanoparticle by organic matter mitigates the acute toxicity of silver to Daphnia magna

Due to the unique antibacterial activities, silver nanoparticles (AgNPs) have been extensively used in commercial products. Anthropogenic activities have released considerable AgNPs as well as highly toxic silver ion (Ag⁺) into the aquatic environment. Our recent study revealed that ubiquitous natural organic matter (NOM) could reduce Ag⁺ to AgNP under natural sunlight. However, the toxic effect of this process is not well understood. In this work, we prepared mixture solution of Ag⁺ and AgNPs with varied Ag⁺% through the sunlight-driven reduction of Ag⁺ by NOM and investigated the acute toxicity of the solutions on Daphnia magna. Formation of AgNPs was demonstrated and characterized by comprehensive techniques and the fraction of unconverted Ag⁺ was determined by ultrafiltration-inductively coupled plasma mass spectrometry determination. The formation of AgNPs enhanced significantly with the increasing of solution pH and cumulative photosynthetically active radiation of sunlight. The toxicity of the resulting solution was further investigated by using freshwater crustacean D. magna as a model and an 8 hr-median lethal concentration (LC₅₀) demonstrated that the reduction of Ag⁺ by NOM to AgNPs significantly mitigated the acute toxicity of silver. These results highlight the importance of sunlight and NOM in the fate, transformation and toxicity of Ag⁺ and AgNPs, and further indicate that the acute toxicity of AgNPs should be mainly ascribed to the dissolved Ag⁺ from AgNPs.     

Development and validation of abiotic ligand model for nickel toxicity to wheat (Triticum aestivum)

A terrestrial biotic ligand model (t-BLM) was developed to predict nickel toxicity to wheat (Triticum aestivum) root elongation in hydroponic solutions. The competitive effects of five major cations (Ca²⁺, Mg²⁺, Na⁺, K⁺ and H⁺) on Ni toxicity were investigated and Mg²⁺ was found to be a strong competitor, while H²⁺ showed less competing effect. Besides free Ni²⁺, the toxicity induced by the species NiHCO₃⁺ was non-neglect able at pH > 7 because NiHCO₃⁺ occupied a significant fraction of total Ni under such condition. Thus, a t-BLM including Ni²⁺, NiHCO₃⁺, Mg²⁺, and H⁺ could successfully predict the nickel toxicity to wheat root elongation and it performed better prediction than the conventional free ion activity model. In addition, the model was examined with two sets of independent experiments, which contained multiple cations and low-molecular-weight organic acids to mimic the rhizo-sphere condition. The developed t-BLM well predicted nickel toxicity in both experiments since it can account in both complexation and competition effects, suggesting its potential to be used in a complicated matrix like soil solution. This study provides direct evidence that the t-BLM is a reliable method for the risk assessment of nickel in terrestrial system.     

三种阳离子对地下水总硬度的影响

通过室内浸泡实验改变三种阳离子Na+、H+、NH+4浓度、浸泡时间,对其动力学和热力学行为进行研究,分析土壤浸出液总硬度变化情况,以找出地下水总硬度随外界条件的变化规律,探究地下水硬度变化机理,为减轻该区地下水硬度升高对人类健康、工农业生产的危害及深入研究地下水总硬度变化机理提供理论依据。实验结果表明:三种阳离子对土壤浸出液总硬度影响不同,NH+4交换出的总硬度最大,H+次之,Na+最小;对同一土层土壤,加入外界浸泡液的浓度越大,交换总硬度的速率越大,交换量也越大;三种阳离子的浸泡液可在1h内将土壤中大部分钙镁交换出,遇有长达1h的强降雨或漫灌,Ca2+、Mg2+会逐步向下迁移,最终引起地下水总硬度升高。     

酸性铬深蓝-示波吸附计时电位法快速测定土壤溶液中不同形态铝

报道了酸性铬深蓝-示波吸附计时电位法分别在酸性和碱性条件下直接检测土壤溶液中的无机单核铝[AIi]和总单核铝[AIa]浓度，并用该法测定了酸消化水样中的总铝[AIT]．由[AI8]-[AIi]间接得到有机单核铝[AIo]，[AIT]-[AIa]得到酸溶态铝[AIr]，从而实现了土壤溶液中5种AI形态的电化学测定测定了十多个实际土壤水样，与Driscoll方法所获结果进行了对照，结果基本一致。     

土壤对酸沉降缓冲机制探讨

一、前言 土壤对酸沉降具有一定的缓冲作用,不同土壤的缓冲能力也各不相同。那么,土壤缓冲作用的本质是什么,不同土壤为什么具有不同的缓冲能力,要解决这些问题,就必须要了解土壤的缓冲机制,了解土壤内部的化学过程。     

Modeling of acute cadmium toxicity in solution to barley root elongation using biotic ligand model theory

Protons（H⁺）as well as different major and trace elements may inhibit cadmium（Cd）uptake in aquatic organisms and thus alleviate Cd toxicity.However,little is known about such interactions in soil organisms.In this study,the independent effects of the cations calcium(Ca²⁺),magnesium(Mg²⁺),potassium（K⁺）,H+and zinc(Zn²⁺)on Cd toxicity were investigated with 5-day long barley root elongation tests in nutrient solutions.The tested concentrations of selected cations and trace metal ions were based on the ranges that occur naturally in soil pore water.The toxicity of Cd decreased with increasing activity of Ca²⁺,Mg²⁺,H⁺and Zn²⁺,but not K⁺.Accordingly,conditional binding constants were obtained for the binding of Cd²⁺,Ca²⁺,Mg²⁺,H⁺,and Zn²⁺ with the binding ligand:log K_CdBL5.19,logK_CaBL2.87,logK_MgBL2.98,logK_HBL5.13 and logK_ZnBL5.42,respectively.Furthermore,it was calculated that on average 29% of the biotic ligand sites needed to be occupied by Cd to induce a 50% decrease in root elongation.Using the estimated constants,a biotic ligand model was successfully developed to predict the Cd toxicity to barley root elongation as a function of solution characteristics.The feasibility and accuracy of its application for predicting Cd toxicity in soils were discussed.     

Towards a better hydraulic cleaning strategy for ultrafiltration membrane fouling by humic acid: Effect of backwash water composition

As a routine measurement to alleviate membrane fouling, hydraulic cleaning is of great significance for the steady operation of ultrafiltration (UF) systems in water treatment processes. In this work, a comparative study was performed to investigate the effects of the composition of backwash water on the hydraulic cleaning performance of UF membranes fouled by humic acid (HA). Various types of backwash water, including UF permeate, Milli-Q water, NaCl solution, CaCl₂ solution and HA solution, were compared in terms of hydraulically irreversible fouling index, total surface tension and residual HA. The results indicated that Milli-Q water backwash was superior to UF permeate backwash in cleaning HA-fouled membranes, and the backwash water containing Na⁺ or HA outperformed Milli-Q water in alleviating HA fouling. On the contrary, the presence of Ca^2 + in backwash water significantly decreased the backwash efficiency. Moreover, Ca^2 + played an important role in foulant removal, and the residual HA content closely related to the residual Ca^2 + content. Mechanism analysis suggested that the backwash process may involve fouling layer swelling, ion exchange, electric double layer release and competitive complexation. Ion exchange and competitive complexation played significant roles in the efficient hydraulic cleaning associated with Na⁺ and HA, respectively.     

纳米银和银离子对土壤中硝化微生物及其氨氧化速率的影响

为研究纳米银对土壤硝化微生物及其氮转化的影响,采用土壤培养方式,对不同剂量纳米银(10、50、100 mg·kg~(-1))和银离子(1、5、10 mg·kg~(-1))暴露下黄棕壤和水稻土硝化细菌数量、土壤酶活性、amoA基因丰度、NH_4~+-N与NO_3~--N含量变化以及土壤潜在氨氧化速率进行研究.结果表明,纳米银和银离子暴露后,2种土壤亚硝酸细菌和硝酸细菌数量显著减少;土壤酶活性受到抑制,对脲酶的影响大于过氧化氢酶;土壤氨氧化细菌(AOB)和氨氧化古菌(AOA)的amoA基因丰度均降低,对AOB基因丰度的影响大于AOA.在2种土壤中外源添加(NH_4)_2SO_4时,随着纳米银和银离子暴露剂量增加,土壤NH_4~+-N含量累积,NO_3~--N含量减少,氨氧化速率降低,铵态氮向硝态氮的转化受阻.综上所述,纳米银和银离子对土壤硝化微生物产生毒害作用并影响铵态氮转化,且影响程度与土壤理化性质有关.     

中亚热带常绿阔叶林湿沉降过程中盐基离子变化特征

基于野外实验和室内实验相结合的方法,于2012年9月至2013年8月对四面山常绿阔叶林大气降水、穿透水、地表枯透水、土壤渗滤液进行了持续一年的森林不同层次盐基离子季节动态变化特征的研究.结果表明,四面山大气降水全年pH平均值为4.90,最大值为5.14,大气降水明显偏酸性;土壤层和林冠层能使降雨的p H值有所升高,其中土壤层对p H值的调升幅度最大,其次为森林冠层;森林冠层只对Na~+有一定的截留作用,降雨能够淋溶森林冠层的Ca~(2+)、Mg~(2+)、K~+;研究结果也表明,枯枝落叶的降解是导致各盐基离子质量浓度在枯透水中增加的主要原因;枯透水下渗的过程淋溶了森林土壤中的Ca~(2+)、Mg~(2+)、Na~+.四面山大气降水经过森林生态系统后Ca~(~(2+))、Mg~(2+)、Na~+、K~+的总截留率分别为33.82%、-7.06%、74.36%、42.87%,森林生态系统对Ca~(2+)、Na~+、K~+表现出了截留作用,其中对Na~+截留率最大.     

Sorption of tetracycline to sediments and soils: assessing the roles of pH, the presence of cadmium and properties of sediments and soils

Batch sorption experiments were conducted to evaluate the sorption behavior of tetracycline (TC, H₃L) on sediments and soils in the presence and absence of cadmium (Cd), as affected by pH and properties of sediments and soils. The results indicated stronger nonlinearity and higher capacity of TC sorption on sediments than on soils. Sorption of TC also strongly depended on environmental factors and sediment/soil properties. Lower pH facilitated TC sorption through a cation exchange mechanism, which also took place at pH values above 5.5, where TC existed as a zwitterion (H₂L⁰) or anions (HL⁻ and L²⁻). When pH was above 7, however, ligand-promoted dissolution of TC might occur due to TC weakening the Al-O bond of aluminum oxide and the Fe-O bond of iron oxide. Natural organic matter (NOM) plays a more important role in TC sorption than cation exchange capacity (CEC) and clay contents. The presence of Cd (II) increased TC sorption on both sediments and soils, which resulted from the decrease of equilibrium solution pH caused by Cd²⁺ exchange with H⁺ ions of sediment/soil surfaces. The increase of TC sorption was also related to the formation of TC-Cd complexes, where Cd²⁺ acted as a bridge between the sediment/soil and TC.     

铊的水地球化学及环境影响

铊(Tl)是一个典型的毒害金属元素,其对哺乳动物的毒性高于Hg、Cd、Cu、Pb、Zn等元素。Tl在自然水体中存在两种氧化状态:Tl+和Tl3+,通常主要以Tl+形式存在。Tl+易随地下水或地表水的流动而迁移到更远的距离,但在较强的氧化环境中,Tl+能够氧化成Tl3+形成Tl(OH)3的沉淀,可以制约水环境中Tl的总含量。Tl可以通过饮用水进入人体,其中Tl+在人体的酶化反应过程中可以置换K+,并与酶产生很强的亲和力,从而诱发Tl的毒害效应。活性铝净化法、离子交换法和NaCl溶液可以用来去除饮用水中的Tl。基于Tl的毒害性,Tl所产生的水环境问题应该引起重视。     

可变电荷土壤和恒电荷土壤与氢离子的反应动力学

在研究可变电荷土壤和恒电荷土壤与H+的反应动力学中,重点考察了H⁺、表面正电荷和可溶性铝随时间变化的特征及影响因素.结果表明,1类土壤中H⁺消耗都可分快速反应和慢速反应2个阶段,但其具体表现和影响因素不同;因氧化铁含量不同,H⁺加入后2类土壤表面正电荷变化存在明显差异;可溶性铝随时间的变化主要受土壤粘土矿物组成、溶解度及溶解动力学控制;2类土壤的可溶性铝的变化可同时用修正的Elovich方程和双常数速率方程描述.     

红纺锤水蚤(Acartia erythraea)对Cu2+和Ag+的吸收

通过对桡足类动物红纺锤水蚤(Acartia erythraea)分别在Cu2 、Ag 、Cu2 Ag 混合溶液中的暴露实验,测定了其对Cu2 、Ag 的吸收速率常数、排出速率常数,并对Cu2 和Ag 在动物体内的分布状况进行了分析.结果表明,在单金属暴露的条件下,红纺锤水蚤对Cu2 、Ag 的吸收速度分别为1.09×104L·g-1·d-1、3.31×104L·g-1·d-1,排出速率常数分别为0.096 d-1、0.1056 d-1.而在Cu2 Ag 的混合暴露体系中,红纺锤水蚤对Cu2 、Ag 的吸收速率分别下降到9.17×103 L·g-1·d-1、2.87×104L·g-1-d-1,Cu2 和Ag 的排出速度常数则分别降到0.084 d-1和0.1008 d-1.动态模型的模拟结果表明,Cu2 和Ag 存在一定程度的拮抗作用.与暴露在单金属溶液中的红纺锤水蚤相比较,在暴露于Cu2 、Ag 混合体系中动物体内的非极性部分所占的比重明显增加,说明其在食物链中对于上一营养级的生物有效性将明显增加.     

重金属与富里酸的竞争络合作用对其在多孔介质中运移的影响

为了研究在土壤地下水环境中运移时,多种重金属在可溶性有机质上的竞争络合作用,于阜新彰武采集草炭土并提取富里酸(FA),通过柱实验,分析了重金属与FA在多孔介质(石英砂柱)中共同运移时,FA对重金属Zn~(2+)、Cd~(2+)和Pb~(2+)运移的促进或抑制作用,以及这些重金属在FA上的竞争作用。结果表明,FA与单一组分重金属(Zn~(2+)、Pb~(2+)、Cd~(2+))在多孔介质中共同运移时,运移能力大小排序为Zn~(2+)Cd~(2+)Pb~(2+);与两组分重金属(Zn~(2+)+Pb~(2+)、Zn~(2+)+Cd~(2+)、Pb~(2+)+Cd~(2+))共同运移时,Zn~(2+)会抑制Pb~(2+)和Cd~(2+)的运移,Cd~(2+)会抑制Zn~(2+)和Pb~(2+)的运移,Pb~(2+)会促进Zn~(2+)和Cd~(2+)的运移;与三组分重金属(Zn~(2+)+Pb~(2+)+Cd~(2+))共同运移时,竞争运移的能力大小为Zn~(2+)Cd~(2+)Pb~(2+)。     

UV/H2O2氧化降解克拉霉素的反应动力学及影响因素

克拉霉素用量大、检出频率高、生态风险大,已被欧盟列为优先监测污染物.针对传统污水处理厂难以完全去除克拉霉素的问题,主要研究了UV/H_2O_2降解克拉霉素的效果和反应动力学,探讨了pH、天然有机质(NOM)和水中共存阴、阳离子对UV/H_2O_2降解克拉霉素的影响.结果表明:单一UV对克拉霉素的光降解符合准一级反应动力学模型,其反应速率常数为0.0016 min~(-1).UV/H_2O_2对克拉霉素的降解符合准一级反应动力学模型,且克拉霉素的降解速率随H_2O_2浓度的增大而增大,在H_2O_2浓度为40 mmol·L~(-1)时,克拉霉素降解的反应速率常数为0.0284min~(-1).克拉霉素与·OH的二级反应速率常数为(2.36±0.20)×10~(10)L·mol~(-1)·s~(-1).碱性条件有利于克拉霉素的降解;NOM(2~10 mg·L~(-1))会抑制克拉霉素的降解,且随NOM浓度增大而增大;共存阴离子CO_3~(2-)对克拉霉素降解无影响,HCO_3~-、NO_3~-、Cl~-会抑制克拉霉素的降解,抑制程度的大小顺序为NO_3~-HCO_3~-Cl~-;共存阳离子Ca~(2+)、Mg2+、Cu~(2+)、Fe~(3+)会抑制克拉霉素的降解,抑制程度的大小顺序为Fe~(3+)Cu~(2+)Mg2+Ca~(2+).     

不同生物炭对酸性农田土壤性质和作物产量的动态影响

为研究不同原料生物炭对农田土壤酸度、交换性能、磷素养分以及作物产量的综合动态影响,试验设置空白（CK）、水稻秸秆生物炭（RSB）、玉米秸秆生物炭（MSB）、小麦秸秆生物炭（WSB）、稻壳生物炭（RHB）和竹炭（BCB）这6种处理,生物炭按质量分数0.1%施入农田进行长期定点试验,测定水稻、油菜和玉米这3季作物产量和作物收割后的土壤理化性质.结果表明,添加不同原料生物炭可有效提高土壤pH和交换性能,降低交换性酸含量,作用效果随时间下降.生物炭对盐基离子组成的影响为提高交换性K⁺、Ca²⁺和Mg²⁺含量,降低Na⁺含量.生物炭能不同程度地增加土壤有机质（SOM）、速效磷、总磷和无机磷（Al-P和Fe-P）含量,作物产量较当季对照显著提高（P<0.05）,稻壳生物炭在改良酸性土壤理化性质和提高作物产量方面效果较好.     

土壤胡敏酸的解离及其与Cu2+的络合特征

通过电位滴定法及恒定容量模式（CCM）研究了2种土壤胡敏酸的解离特性及其与Cu^2 的络合特征，结果证明在pH3－7范围内胡敏酸表现为2种一元酸组成的混合酸，实验数据适用于静电模式。胡敏酸的解离常数和Cu^2 的络合常数应用计算机程序FITEQL32表明，优化的解离常数pKHL1在3．50－4．89之间，pKHL2在6．17－8．38之间，2种形态一元胡敏酸解离常数之比小于10^5，与滴定曲线只有一个突跃区相一致。2种土壤胡敏酸与Cu^2 络合常数logK^intACu大小分别为Lou土HA1．346，黑垆土HA2．241，非静电模式的优化结果较好。     

南昌市土壤风沙尘PM2.5中水溶性离子分布特征及来源初探

为了解南昌市土壤风沙尘PM_(2.5)中水溶性离子的分布特征,利用颗粒物再悬浮采样器采集土壤风沙尘的PM_(2.5)样品,并采用离子色谱仪分析了9种水溶性离子的含量。结果表明,土壤风沙尘PM_(2.5)中9种水溶性离子的含量之和为11. 126±2. 703 mg/g,阳离子中平均含量最高的是Ca~(2+)(1. 684±0. 545 mg/g),阴离子中最高的是SO_4~(2-)(3. 568±1. 553 mg/g)。SO_4~(2-)、NO_3~-、Ca~(2+)和Cl~-是土壤尘PM_(2.5)中的主要离子组成,占总离子浓度的80. 60%。与其他城市对比,南昌市土壤风沙尘PM_(2.5)中离子基本处于较低水平。阴阳离子当量浓度比值为1. 26,表明土壤风沙尘的PM_(2.5)颗粒为弱酸性。空间插值分析表明南昌市西南部土壤尘PM_(2.5)中的离子含量分布相对较高,而东部及北部多处于较低水平。相关性分析表明Na~+、F~-和NH_4~+具有同源性,K~+与其他离子都不相关。NO_3~-/SO_4~(2-)的比值介于0. 26～0. 97间,整体上反映出固定源对土壤风沙尘PM_(2.5)的影响更显著。     

改性生物炭材料对稻田原状和外源镉污染土钝化效应

为研究改性处理后的生物炭对镉污染土壤钝化效应,以油菜秸秆制备的生物炭(BC)为原材料,通过不同处理(HNO_3氧化、NaOH碱化、KMnO_4浸渍、FeCl_3浸渍)制备改性炭材料,在室内连续培养试验中,分析了其对原土/外源镉污染土壤的钝化效应.结果表明,原炭及改性生物炭均降低了原状土壤有效态镉含量,其中Na OH和KMnO_4改性的炭材料钝化作用超过50%;在外源污染土壤中,NaOH、KMnO_4、FeCl_3改性炭材料均降低了土壤有效态镉含量,以添加10%的BC-KMnO_4较佳,降低作用超30%,HNO3改性炭却活化了3.8%~24.5%的土壤有效态镉.10%BC-KMnO_4显著降低原状土壤中可交换态镉含量达65.1%,而BC-HNO_3在外源污染土壤中活化可交换态镉含量高达20.2%.原炭及改性生物炭均增加了土壤中有机碳、盐基离子含量;原炭及NaOH、KMnO_4改性生物炭提高了土壤pH,HNO_3改性炭则降低了土壤p H;原状土中有效态镉含量与pH、交换性钠离子含量呈显著负相关,外源镉污染土中有效态镉含量则与pH、有机碳、交换性镁、钾、钠离子含量呈显著负相关.KMnO_4改性生物炭显著提高土壤pH,增加土壤有机碳和盐基离子含量,降低土壤镉活性形态含量,可作为优选的原位钝化修复材料,而HNO_3改性生物炭显著降低了土壤pH,提高了土壤有效态和可交换态镉含量,具有促进土壤镉生物有效性的风险.     

DMPP对氮素垂直迁移转化及淋溶损失的影响

采用自制模拟原状土柱装置,进行新型硝化抑制剂3,4-二甲基吡唑磷酸盐（3,4-dimethyl pyrazole phosphate ,DMPP）对氮素淋溶效应试验,探讨其对氮素垂直迁移转化及降低淋溶损失的影响.结果表明,尿素添加1%的DMPP后,与不添加DMPP尿素相比,在60 d内能有效抑制土壤铵氧化反应的发生,显著提高20 cm以上耕作层土壤水铵态氮的浓度,降低硝态氮和亚硝态氮的浓度;20 cm以下深层土壤水铵态氮的浓度与未加DMPP的处理无显著差异,并没有明显导致铵态氮的垂直迁移;深层土壤水硝态氮的浓度显著低于未加DMPP的处理,明显降低硝态氮垂直迁移的淋溶损失;随施氮量增加,添加DMPP尿素的处理,60 d内土壤水中铵态氮与硝态氮的浓度在40 cm以下深层剖面并没有明显增加,其垂直迁移的淋溶损失差别不大.常规尿素添加1%的DMPP,可以调控土壤氮素的迁移转化,有利于土水环境的保护,降低对地下水氮素污染的潜在风险,具有显著的生态效益.