降雨条件下典型岩溶流域地下水中的物质运移

通过对2008年4月下旬降雨期间,重庆青木关地下河系统出口姜家泉泉水的水文过程、浊度、悬浮颗粒物、主要阳离子和TOC浓度的监测,结合悬浮颗粒物的扫描电镜和能谱分析图,来研究岩溶流域地下水中悬浮颗粒物浓度、浊度、主要阳离子和TOC等物质的运移特征.结果表明,在单一岩溶管道较发育的地下河出口,泉水流量、浊度、悬浮颗粒物浓度、主要阳离子和TOC浓度对降雨事件响应迅速;与碳酸盐岩溶解有关的Ca2+、Mg2+和Sr2+等在流量上升的过程中表现为稀释效应;降雨期间,地下河中受雨水侵蚀的土壤输入量增大,引起泉水中浊度和悬浮颗粒物浓度的增大;泉水中Al3+、Fe、Mn、Ba2+和TOC等物质是悬浮颗粒物的伴生物,其浓度随浊度的增大而增大;在研究的2场降雨期间,地下水携带悬浮颗粒物(0.45μm)的总量约为9.7t;在泉水流量的上升和衰减的过程中,水质较差或极差;降雨期间流域内土壤侵蚀和养分的流失,不但严重破坏了脆弱的岩溶生态环境,而且极易造成地下水由土壤侵蚀引起的非点源污染,对当地居民的饮水安全造成严重的威胁.     

不同离子桥键的有机矿质复合体对菲的吸附-解吸研究

从自然土壤中有机质与矿物的结合方式出发,研究了Ca²⁺、Fe³⁺和Al³⁺桥键的有机矿质复合体对菲的吸附-解吸行为.结果表明,不同离子饱和的蒙脱石及其相应的胡敏酸-矿物复合体对菲的吸附-解吸数据都能用Freundlich模型较好地拟合,吸附容量（K_f）大小的顺序分别为Ca-Mont（0.184）>Fe-Mont（0.028）>Al-Mont（0.015）和Fe-Mont-HA（2.341）>Ca-Mont-HA（1.557）>Al-Mont-HA（1.136）.有机矿质复合体的K_f值远远高于相应的矿物,表明了复合体中的胡敏酸对菲的吸附容量贡献较大.但不同离子桥键的复合体K_f值的大小与它们有机质的含量高低次序不一致,表明了复合体中有机质的含量以及有机质与矿物结合方式的不同,都可能会影响它们对菲的吸附.Ca²⁺和Al³⁺桥键的有机矿质复合体对菲的解吸都有滞后现象,滞后现象主要来自有机质对菲的吸附,而矿物对菲的解吸滞后现象影响不明显.     

Surface Water Seepage Effects on Shallow Ground‐Water Quality Along the Rio Grande in Northern New Mexico1

Abstract: Interactions between surface irrigation water, shallow ground water, and river water may have effects on water quality that are important for both drinking water supplies and the ecological function of rivers and floodplains. We investigated water quality in surface water and ground water, and how water quality is influenced by surface water inputs from an unlined irrigation system in the Alcalde Valley of the Rio Grande in northern New Mexico. From August 2005 to July 2006, we sampled ground water and surface water monthly and analyzed for concentrations of major cations and anions, specific conductance, pH, dissolved oxygen, and water levels. Results indicate that irrigation ditch seepage caused an increase in ground water levels and that the Rio Grande is a gaining stream in this region. Temporal and spatial differences were found in ion concentrations in shallow ground water as it flowed from under the ditch toward the river. Ground‐water ion concentrations were higher when the ditch was not flowing compared with periods during peak irrigation season when the ditch was flowing. Ditch inputs diluted ion concentrations in shallow ground water at well positions near the ditch. Specifically, lower ion concentrations were detected in ground water at well positions located near the ditch and river compared with well positions located in the middle of an agricultural field. Results from this project showed that ditch inputs influenced ion concentrations and were associated with ground‐water recharge. In arid region river valleys, careful consideration should be given to management scenarios that change seepage from irrigation systems, because in some situations reduced seepage could negatively affect ground‐water recharge and water quality.     

Chemical characteristics of precipitation at metropolitan Newark in the US East Coast

To investigate the chemical characteristics of precipitation in the polluted coastal atmosphere, a total of 46 event-based precipitation samples were collected using a wet-only automatic precipitation collector from September 2006 to October 2007 at metropolitan Newark, New Jersey in the US East Coast. Samples were analyzed by ion chromatography for the concentrations of major inorganic ions (Cl⁻, NO₃⁻, SO₄²⁻, F⁻, NH₄⁺, Ca²⁺, Mg²⁺, Na⁺, K⁺) and organic acid species (CH₃COO⁻, HCOO⁻, CH₂(COO)₂²⁻, C₂O₄²⁻). Selected trace metals (Sb, Pb, Al, V, Fe, Cr, Co, Ni, Cu, Zn, Cd) in samples were determined by ICPMS. Mass concentration results show that SO₄²⁻ was the most dominant anion accounting for 51% of the total anions, controlling the acidity of the precipitation. NH₄⁺ accounted for 48.6% of the total cations, dominating the precipitation neutralization. CH₃COO⁻ and HCOO⁻ were the two dominant water-soluble organic acid species, accounting for 42% and 40% of the total organic acids analyzed, respectively. Al, Zn and Fe were the three major trace metals in precipitation, accounting for 34%, 27%, and 25% of the total mass of metals analyzed. The pH values in precipitation ranged from 4.4 to 4.9, indicating an acidic nature. Enrichment Factor (EF) Analysis showed that Na⁺, Cl⁻, Mg²⁺ and K⁺ in the precipitation were primarily of marine origin, while most of the Fe, Co and Al were from crust sources. Pb, V, Cr, Ni were moderately enriched with EFs ranging 43–410, while Zn, Sb, Cu, Cd and F⁻ were highly enriched with EFs > 700, indicating significant anthropogenic influences. Factor analysis suggests 6 major sources contributing to the observed composition of precipitation at this location: (1) nitrogen-enriched soil, (2) secondary pollution processes, (3) marine sources, (4) incinerations, (5) oil combustions, and (6) malonate–vanadium enriched sources. To further explore the source–precipitation event relationships and seasonality, cluster analysis was performed for all precipitation events. Results show that about half of the precipitation events were characterized by mixed sources. Significant influences of nitrogen-enriched soil and marine sources were associated with precipitation events in spring and autumn, while secondary pollution processes, incineration and oil combustion contributed greatly in summer.     

Study of sorption kinetics of some ionic liquids on different soil types

In the present contribution sorption kinetics experiments under static conditions were utilized in three selected ionic liquids cations (1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium chlorides) study with five type of soil, differing in total organic carbon (TOC) content. The experimental results indicate the sorption capacity growth with increase in TOC content and hydrophobicity of ionic liquid cation. The obtained kinetic sorption parameters as well as distribution coefficients (K_d) were used to estimate the sorption properties of the soil types towards the ionic liquids in question. The Gibbs free energy values indicate that ionic liquid cations sorption on soils could be generally considered as a physical adsorption with exothermic effect. But the values of −dG for studied cations sorption on soil with very high of TOC content in soil (45%) may testify to nature of chemical adsorption. Sorption of the analyzed compounds occurs probably by means of hydrogen bonds, electrostatic and π  π interaction with the organic matter and the clay minerals of the soils.     

青岛大气气溶胶水溶性无机离子研究:季节分布特征

为了全面了解当前青岛地区大气气溶胶中水溶性组分的特征及来源,于2008年1～12月在青岛市区连续采集了总悬浮颗粒物(TSP)样品,运用离子色谱法对其主要的水溶性阴阳离子进行了分析.结果表明,SO24-、NO3-、NH4+和Cl-是TSP中水溶性离子的主要成分,四者质量浓度之和占总水溶性离子质量浓度的86.9%.TSP及其水溶性组分存在明显的季节变化,其来源也存在多源性.Na+、NH4+、Ca2+、F-、Mg2+均为冬季最高,夏季最低,K+、PO34-为秋季最高,夏季最低,Cl-为冬季最高,秋季最低,NO3-则为春季最高,夏季最低,而SO24-为春季最高,秋季最低.不同天气对颗粒物和气溶胶中水溶性离子影响很大.颗粒物浓度在晴天时最低,其次是雾天,再次是烟雾和霾,沙尘天气下质量浓度最高.Na+、Mg2+、Ca2+、F-、Cl-和PO34-在烟雾天气下的平均浓度最高,而NH4+、K+、NO3-和SO24-则是在霾天气下质量浓度最高.     

无机钝化剂对镉污染酸性水稻土的修复效果及其机制

以浙江南部重金属镉（Cd）轻度污染酸性稻田为对象,以当地应用最广泛的3种无机钝化剂（硅钙镁钾肥、钙镁磷肥和石灰）为材料,通过田间试验研究了不同用量（750、1500和2250 kg ·hm^-2）钝化剂阻控土壤酸化与稻米Cd积累的效果与化学机制.结果表明,3种钝化剂可有效地改良土壤酸化和降低水稻稻米Cd积累,施用2250 kg ·hm^-2硅钙镁钾肥、钙镁磷肥和石灰分别增加土壤pH值0.62、0.65和0.86单位,减少交换性酸总量67%、69%和78%,降低糙米镉含量73%、68%和77%.施用2250 kg ·hm²钝化剂可使Cd轻度污染稻田上种植水稻糙米中ω（Cd）低于0.2 mg ·kg^-1,达到国家食品安全标准;与对照比较,3种钝化剂均显著降低土壤中DTPA提取有效态镉含量,降低弱酸提取态（F1）和可还原态（F2） Cd含量,增加残渣态（F4） Cd含量;相关分析表明糙米Cd含量与土壤pH与交换性阳离子含量呈显著负相关,与DTPA-Cd、F1-Cd、F2-Cd和交换铝含量呈显著正相关.应用最小二乘路径模型分析了糙米Cd含量、Cd有效性和化学形态与土壤性质的关系,土壤交换性阳离子对糙米Cd含量、有效镉和水稻产量直接影响的路径系数分别为-0.566、-0.866和0.873,土壤pH主要通过直接影响有效镉而间接影响糙米镉含量.田间试验证明,这3种钝化剂是实现镉污染酸性水稻土水稻安全生产的有效技术,它们主要通过影响土壤交换性阳离子而直接影响土壤镉生物有效性,进而影响糙米中镉的积累,研究结果可为受污染耕地水稻安全生产和酸化土壤改良提供科学依据.     

不同阳离子影响下小麦根吸收镉的动力学过程

生物配体模型(BLM)是基于稳定态假设的一个平衡模型,能够较准确地运用于预测重金属的毒性及其生物有效性.根据BLM模型的假设条件模拟土壤溶液,研究了Ca2+、Mg2+、Cu2+和Ni2+对小麦根吸收Cd2+动力学的影响,阐述了BLM在应用中存在的局限性.结果表明:在8h内的短期动力学吸收实验中,小麦根对Cd的吸收及吸附量呈线性增加,但未达到稳定值,这说明Cd2+在根-液界面未达到稳定平衡;并且小麦根对Cd的吸收是受溶液中Cd2+扩散速率影响的.小麦根对Cd的吸收通量与Cd2+浓度[Cd2+]和Cd与小麦根表上的配体结合浓度{Cd-Rcel}l都具有较好的线性关系,但随着Cd2+浓度的增加稳定常数KM-Rcell、渗透常数p和同化速率常数kint均呈降低趋势.Ca2+、Mg2+和Cu2+降低了小麦根对Cd2+的吸收通量,而Ni2+对Cd2+的竞争作用不显著.由于Cd与Ca、Ni有共同的吸收通道,Ca通道吸收达到饱和后可降低小麦根对Cd的吸收,但是Ca2+、Mg2+和Cu2+通过降低内化速率常数也可使小麦根对Cd的内化通量减少,因此不能完全用竞争效应解释其结果.另外,阳离子的存在会改变小麦根表的性质,Ca2+、Mg2+的存在会增加亨利系数KCd,即生物配体浓度{Rcel}l和(或)离子与生物配体结合稳定常数KCd-Rcell会增加,同时这些离子的存在还会降低渗透常数p和kint;Cu2+、Ni2+的存在会降低KCd;且p和k在低浓度Cd(0.01～0.05μM)条件下增加,在高浓度Cd条件下降低.     

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.     

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.