Dissolution of zinc oxide nanoparticles in exposure media of algae,daphnia, and fish embryos for nanotoxicological testing

Zinc oxide nanoparticles (ZnO NPs) are being widely investigated in a bioassay due to potential negative effects to biological receptor. The dissolution of metal nanoparticles such as ZnO NPs is crucial to interpret nanotoxicity results because ZnO NPs can release toxic-free ions in exposure media. In the present study, dissolution of ZnO NPs was evaluated in three selected synthetic media for aquatic toxicological testing: Elendt M4 daphnia medium, OECD algal medium, and fish embryo rearing solution. Both media are currently recommended for OECD testing for daphnia and algae. Time-dependent dissolution of ZnO NPs has been investigated in terms of sonication time to be used for the preparation of aqueous NPs suspension, and dissolution time corresponding to exposure period in toxicity testing. Since sonication is widely applied for NPs dispersion in the most of nanotoxicological testing, the emphasis of this study was on the dissolution of NPs as a function of sonication time. We also investigated the concentration-dependent dissolution of ZnO NPs. Our results demonstrated that dissolution of ZnO NPs was significantly affected by sonication and dissolution time, as well as NPs concentration. This study showed that parameters affecting dissolution of ZnO NPs should be considered in nanotoxicological testing.     

电镀污泥中重金属溶出动力学及其在土壤中的归趋

电镀污泥是电镀工业中重金属的"汇",在降水的作用下可能向环境释放大量的重金属.本文通过连续浸出实验和动力学拟合探究了电镀污泥中重金属的溶出特性,并分析了重金属在土壤中的吸附、迁移转化及淋出行为.结果表明,在淋溶初期,重金属从电镀污泥中大量释放,且土壤中Cr （Ⅵ）、Ni的淋出浓度分别高达0.102、0.222 mg·L^-1.淋溶后,表层土壤中Ni、Cu的总量及可交换态/碳酸盐结合态含量均显著增加;由于专性吸附作用,Cu的铁锰氧化物结合态含量也大量增加,Cu在土壤中的吸附率高达89.32%~97.67%,降低了其从土壤中的淋出风险.Cr、Ni、Cu更易在红壤中发生吸附并转化为稳定的有机结合态,降低了重金属的潜在迁移性;相应地,电镀污泥中释放的Cr、Ni、Cu在栗钙土中具有较高的淋出风险.     

煤矸石中铅、铬、镉的溶出性能

以滕南煤田某煤矿风化煤矸石为研究对象,应用主成分分析法分析了煤矸石粒径对Pb,Cr,Cd溶出浓度的影响,应用回归分析法分析了浸溶时间与Pb,Cr,Cd溶出浓度的关系特征。实验结果表明：模拟湿地浸溶条件下,煤矸石中Pb,Cd,Cr溶出浓度均超出或接近Ⅲ类水体水质标准,对水环境存在污染风险;煤矸石粒径对Pb,Cd,Cr溶出浓度存在影响,粒径越小则Pb、Cr、Cd溶出浓度越大,粒径小于8.0 cm的煤矸石浸溶贡献较大。建立了表征Pb,Cr,Cd溶出浓度与浸溶时间对数（以10为底）关系的一元三次多项式回归方程,经检验均具有显著性。     

表面活性剂溶液中多氯联苯溶解的特性

对表面活性剂溶液中多氯联苯的溶解特性进行了研究.发现非离子型表面活性剂对多氯联苯增溶效果优于阴离子型表面活性剂;在浓度大于临界胶束浓度(CMC)范畴,不但表面活性剂的增溶效果远较其浓度低于CMC时为佳,而且表面活性剂浓度与多氯联苯的溶解度成正比地线性相关,此结果说明,表面活性剂主要通过形成胶束来增加多氯联苯的溶解度.多氯联苯在非离子型表面活性剂胶束溶液中与在正己烷中的紫外-可见光谱相似,进一步说明胶束内的多氯联苯分子主要分布于类似正己烷的疏水胶核区域.在十二烷基醇聚氧乙烯(10)醚溶液中,所试多氯联苯的辛醇-水分配系数(K_ow)与其胶束-水分配系数(K_m)存在很好的线性相关关系.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Impact of urbanization on hydrochemical evolution of groundwater and on unsaturated-zone gas composition in the coastal city of Tel Aviv, Israel

The coastal city of Tel Aviv was founded at the beginning of the 20th century. The number of its inhabitants and its water consumption increased rapidly. This study analyses a 15-year record (1934-1948) of pre-industrial development of groundwater chemistry in the urban area. Archive data on concentrations of major ions, dissolved gases (CO2 and O2), organic matter, and pH were available for each half-year during the period of 1934-1948. The major factors causing changes in the chemistry of groundwater flowing in three sandy sub-aquifers have been seawater encroachment due to overpumping, and infiltration of effluents from pit-latrine collectors. Influence of these factors decreases with depth. Landward-penetrating seawater passed through clayey coastal sediments, interbedded among sands and calcareous sandstones, and spread into the Kurkar Group aquifer. This has led to exchange of sodium (dominant in seawater) with calcium adsorbed on clay particles, enriching groundwater with calcium. Intensity of cation exchange decreases inland and with depth. Infiltration of pit-latrine effluents has introduced large amounts of ammonium into the unsaturated zone. Its rapid oxidation in unsaturated sediments has caused massive nitrate production, accompanied by pore-water acidification. This process induces dissolution of vadose carbonate, resulting in enrichment of groundwater recharge in calcium. Anthropogenically induced dissolution of calcite in the unsaturated zone has been the major factor for the increase of Ca2+ concentration in groundwater, accounting for about 80% of this increase. In the interface zone, an additional 20% of calcium has been supplied by cation exchange. Owing to pH increase caused by denitrification in the aquifer, Ca(2+)-rich waters supersaturated with calcite could be formed, especially in the capillary fringe of the uppermost sub-aquifer, which could induce calcite precipitation and ultimately lead to the cementation of sandy aquifers. Urban development has caused drastic changes in the gas content in the unsaturated zone and in groundwater. Carbon dioxide was intensively generated by nitrification-denitrification processes, by hydration of urea, to a lesser degree by oxidation of organic matter, and probably by anoxic biodegradation of organics. Between 1934 and 1948, concentrations of CO2 in unsaturated sediment air rose from 3.2% to 7.6%. In the unsaturated zone, oxygen consumption for oxidation of ammonium and organic matter lowered O2 concentrations in sediment air to unusually low values of 3.9-12.9%. Nitrification in the urban unsaturated zone could thus serve as a pump, sucking in atmospheric oxygen at a rate of about 0.3-0.5 g m-2 day-1. The extreme concentrations of CO2 and O2 in unsaturated sediments have been preserved due to production and consumption of gas under conditions of diminishing areas open to the atmosphere, uncovered by buildings and by roads.     

自硬性玻璃基生物水泥的结构研究

利用X射线衍射和扫描电镜研究了玻璃基生物水泥在生理模拟液中羟基磷灰石（HAP）晶相的形成和长大，应用溶解－析晶理论，阐述了玻璃粉末与调和液及表面活性剂反应，形成HAP的动力学观点，实验结果表明，玻璃基生物水泥在调和液作用下，会形成HAP晶相，在生理模拟液中，随着时间的延长，晶体逐渐长大，图3表1参5     

草酸盐介导下含As(V)黄钾铁矾的相转化过程与As(V)的再分配行为

黄钾铁矾能够通过吸附和共沉淀作用固定酸性矿山废水（AMD）中的重（类）金属（如砷）,降低其迁移性和生物可利用性.草酸盐广泛存在于天然水环境中,其具有的羧酸官能团能改变铁矿物的稳定性,进而影响吸持的重（类）金属的再分配行为.利用水热法合成含As（V）黄钾铁矾,探究其在不同草酸盐浓度与pH条件下的溶解、重结晶和共沉淀As（V）的行为.研究结果表明,草酸盐与含As（V）黄钾铁矾表面Fe（III）活性位点配位形成的可溶性强络合物是促进矿物溶解的第一步和关键;在pH 2.5时,含As（V）黄钾铁矾的溶解速率随草酸盐浓度增加而增加,伴随大量As（V）释放到溶液,反应过程中只有少量As（V）重新吸附到固相上,这是由于草酸盐与As（V）竞争矿物表面的同一活性位点;在pH 6.5条件下,草酸盐促进含As（V）黄钾铁矾的重结晶,经X射线衍射分析表明针铁矿和纤铁矿为主要产物,能有效地吸附释放的As（V）.研究结果有助于揭示在AMD环境下黄钾铁矾沉积物与含羧酸官能团有机酸共存时对As（V）的释放和固定机理,对AMD环境中As（V）污染控制有重要意义.     

小球藻对土壤-水稻系统砷化学形态转化的影响

为揭示绿藻对土壤-水稻系统砷形态转化的影响特征,系统分析了不同浓度小球藻共存条件下水稻土砷氧化还原与溶解释放行为的变化,并结合水稻培育试验,对小球藻影响水稻砷吸收与体内砷形态的发生机制进行探讨.试验设置对照组及小球藻浓度（以体积分数计）分别为1%、5%、10%的处理,研究了小球藻对溶液体系、淹水土壤体系和淹水土壤-水稻体系中砷的化学形态转化的作用.结果表明:加藻组使As（Ⅲ）溶液和淹水土壤E_h（氧化还原电位）与pH均普遍高于对照组.在As（Ⅲ）溶液体系中,加藻组As（Ⅲ）氧化转化率较对照组升高2.38%~4.95%,该作用在淹水土壤中得到印证,小球藻的共存使土壤孔隙水ρ[As（Ⅴ）]较对照组升高129.22%~221.41%,而ρ（甲基砷）出现显著下降（5.25%~53.31%）.水稻栽培试验进一步发现,小球藻明显促进土壤中晶体态铁铝氧化物向弱结晶与无定形铁铝氧化物结合态砷等的转化,导致水稻幼苗对砷的吸收积累量增加-3.4%~23.11%,推测这与小球藻作用下土壤孔隙水ρ（DOC）的增加密切相关.研究显示,尽管小球藻有利于提高淹水土壤体系E_h并加速As（Ⅲ）的氧化转化,但小球藻可能通过有机酸等分泌物的竞争吸附作用促进铁铝氧化物结合态砷的溶解释放,从而增加水稻砷吸收;淡水藻类对土壤-水稻体系砷吸收积累的风险值得引起高度关注,并需要在大田试验中进一步加以验证.      

低分子量有机化合物对MnO_2和土壤氧化锰的还原溶解作用

为考察土壤锰氧化物的还原溶解行为,本文选取常见的根系分泌的8种有机酸(抗坏血酸、香草酸、柠檬酸、草酸、酒石酸、水杨酸、半胱氨酸和邻苯二甲酸)和1种酚类化合物(邻苯二酚),人工合成的Mn O2和5种富含氧化锰的土壤(广东徐闻的砖红壤、海南澄迈的砖红壤、云南昆明的砖红壤、浙江嵊县的红壤和江苏南京的黄棕壤),研究了有机化合物对氧化锰的还原溶解作用.结果表明,较低p H和较高温度有利于有机化合物对Mn O2的还原溶解.在p H 4.5—5.5和温度5—45℃范围内,不同有机化合物还原溶解Mn O2能力的大小顺序为:邻苯二酚半胱氨酸抗坏血酸香草酸柠檬酸草酸≈酒石酸水杨酸≈邻苯二甲酸.邻苯二酚、半胱氨酸和抗坏血酸对土壤中氧化锰也有较强的还原溶解能力.当5种土壤比较时,徐闻砖红壤中还原溶解出的锰量最高,其次为昆明砖红壤,嵊县红壤中还原溶解出的锰量最小.当有还原性有机化合物存在时徐闻砖红壤、昆明砖红壤和澄迈砖红壤中的氧化锰容易发生还原溶解反应,增加土壤中可溶态和交换态Mn2+的含量,并可能对植物产生锰毒害.