可变电荷及恒电荷土壤与H+反应的动态监测

动态监测了恒电荷及可变电荷土壤与H+反应的动力学过程,并进行了数学描述.结果表明,质子化过程为一相当快的过程,当氧化铁含量高时,质子化作用将消耗大量的H+.反应5s后,H+浓度随时间的变化可分为快速和慢速两个阶段.输入的H+浓度低时,质子化是矿物消耗H+最主要的机制;输入的H+浓度高时,除质子化作用外,矿物的溶解也是消耗H+的重要机制.就矿物本身消耗H+的能力而言,可变电荷土壤的消耗能力大于恒电荷土壤.     

松树近旁土壤酸化的二维特征

采用土壤酸中和能力的一种新定义方法：土壤水的pH值降低到4.7时100g土壤消耗的H⁺量,研究了土壤断面的酸化特征。选择了南方的红壤和北方的褐壤,详细研究了松树近旁土壤pH、酸中和能力、以及对SO²－₄吸附等断面的二维分布特征。结果表明,松树近旁土壤的pH、酸中和能力、SO²－₄吸附能力在水平层变化不明显,在垂直深度方向逐渐变大,表层小于下层。从土壤断面ANC的特征揭示出我国南北方土壤表层均受不同程度的酸化。     

丁基黄药对选矿区土壤吸附铅镉的影响

选矿废水排放和尾矿库溢流等会将大量残留的选矿药剂带入选矿区周边土壤和水环境.采用批处理实验,研究了不同pH、初始丁基黄药（PBX）、Pb²⁺和Cd²⁺浓度下,PBX对某铅锌选矿区土壤吸附Pb²⁺和Cd²⁺的影响;并通过BCR连续提取,研究了不同浓度PBX处理后土壤中铅镉形态变化.结果表明,PBX明显抑制了土壤对Pb²⁺和Cd²⁺的吸附.PBX浓度为40mg·L^-1时,土壤对Pb²⁺和Cd²⁺的吸附量分别由未经PBX处理时的3540 mg·kg^-1和387mg·kg^-1降至3085 mg·kg^-1和100mg·kg^-1.无论是否添加PBX,土壤对Pb²⁺和Cd²⁺的吸附动力学过程可用准二级动力学模型拟合,表明Pb²⁺和Cd²⁺在土壤上的吸附是以化学吸附为主.PBX与Pb²⁺、Cd²⁺形成疏水性难溶络合物以及在土壤表面存在竞争吸附是降低土壤Pb²⁺和Cd²⁺吸附量的主要原因,表明PBX能增加Pb²⁺和Cd²⁺在土壤中的迁移性.PBX对土壤Pb²⁺和Cd²⁺吸附的抑制作用随初始Pb²⁺和Cd²⁺浓度的增大而减弱,随初始PBX浓度及溶液pH值的增大而加强,Freundlich方程能较好描述其等温吸附特征.低含量PBX （100mg·kg^-1）下土壤中可交换态和可还原态镉含量有所增加,可导致土壤中镉的活化;但PBX可降低土壤中可交换态和可还原态铅含量,且随PBX含量升高,铅活性降低效果越显著,这与Pb （C₄H₉OCS₂）₂的络合能力比Cd （C₄H₉OCS₂）₂强有关.研究结果表明应加强选矿废水中残留药剂对土壤中铅镉等重金属潜在生态风险的防控.     

模拟酸雨对南方土壤硅铝释放的影响

通过模拟酸雨淋溶实验,分析了淋溶液pH值和硅铝离子释放规律和特点的关系．结果表明,模拟酸雨的酸度是决定土壤中硅铝淋溶释放量的主要因素．当pH＞3.0时释放量增幅较为缓慢,而pH＜3.0以后释放量骤增．土壤溶液中H⁺浓度的增加,使得以水解反应为主要过程的土壤矿物的风化作用加强,从而使硅铝释放量增大.     

紫色土丘陵区退耕还林对坡地土壤碳氮空间分布的影响

为了弥补我国四川盆地紫色土丘陵区退耕还林对坡地土壤碳（C）和氮（N）时空分布影响的研究不足,依托中国科学院盐亭紫色土农业生态试验站在万安小流域建立的长期观测样地,对比分析了约30年历史的退耕林地及其邻近的坡耕地不同坡面位置土壤的C、N形态、含量及其储量. 结果发现,退耕还林后,显著增加了剖面土壤有机碳（SOC）含量及储量（P< 0.05）,其中表层土壤（0~20 cm）SOC储量增加了25.86 t·hm^-2,年均SOC储量增加速率为0.89 t·hm^-2. 土壤总氮（TN）含量虽略有增加,但仅限于0~20 cm土层. 退耕林地与坡耕地相比,速效C、N养分如,土壤硝态氮（NO₃^--N）、铵态氮（NH₄⁺-N）和可溶性有机碳（DOC）含量在整个土壤剖面（0~70 cm）的差异性基本不显著（P> 0.05）. 此外,研究还发现空间位置对坡耕地土壤TN、SOC、NO₃^--N、NH₄⁺-N和DOC含量均有显著影响（P< 0.05）;土壤TN和SOC含量沿坡面的变化趋势大小为：下坡位>上坡位>中坡位,而土壤NO₃^--N、NH₄⁺-N和DOC含量沿坡面的变化趋势大小则为：上坡位<中坡位<下坡位. 退耕林地土壤仅DOC含量受坡位的显著影响,并沿坡面向下呈增加趋势. 结果表明,在评估紫色土丘陵区土地利用变化对土壤碳氮储量的影响时,不能忽视地形等因素的影响.     

模拟酸雨条件下Cd2+在土壤及其矿物表面的解吸动力学特征

利用流动搅动法研究在模拟酸雨条件下土壤和矿物表面Cd2+的解吸动力学特征,结果表明,Cd²⁺的解吸动力学能用一级动力学描述,红壤和针铁矿上Cd²⁺解吸率为70%～100%,砖红壤和高岭土上解吸率为25%～50%;砖红壤上Cd²⁺解吸动力学可用扩散方程描述,但该方程并不适合描述红壤、针铁矿和高岭土上Cd²⁺的解吸;Elovich方程在描述Cd²⁺解吸时比双常数方程和抛物线扩散方程要好,这也说明Cd²⁺的解吸为一非均相扩散过程.Cd²⁺的解吸过程分为快反应和慢反应,快反应过程在60min内完成(除砖红壤外),随后达到平衡状态.Cd²⁺在土壤表面的快反应与交换态Cd²⁺有关,边面羟基化的键合点位与Cd²⁺亲和力的不同是导致Cd²⁺解吸速率和解吸量差异的原因.流出液pH值的上升反映出土壤表面存在质子的消耗,这可能与硫酸根的专性吸附释放羟基和矿物表面的质子化有关,这在砖红壤上表现得特别明显.     

红壤中质子化及铝的溶解与质子缓冲之间的关系

 用平衡实验及动力学实验研究了我国南方4种红壤的表面质子化及铝的溶解与质子缓冲之间的关系.结果表明,由于游离氧化铁的含量、活性及对铝溶解反应位的掩盖程度等与质子化密切相关因素的不同影响,4种红壤的总H⁺消耗量和铝溶解量不同,宁海红壤和嵊县红壤的质子化程度及H⁺的总消耗量大于永春红壤和屯溪红壤;屯溪红壤铝的溶解量最大,宁海红壤铝的溶解量最小.尽管屯溪红壤铝的溶解量最大,但H⁺的总消耗量却最小.当红壤中氧化铁含量较高时,铝的溶解在H⁺消耗中只起次要作用,质子化过程是H⁺消耗的主要途径.     

阳离子强度和阳离子类型对诺氟沙星土壤吸附的影响

以OECD Guideline 106为基础,采用批平衡方法研究不同Ca²⁺离子强度（0.01、0.03、0.05、0.08和0.10 mol/L的CaCl₂溶液）和不同阳离子（0.01 mol/L的NaCl、KCl、NH₄Cl、MgCl₂、CaCl₂、ZnCl₂和AlCl₃溶液）对诺氟沙星在4种土壤（潮土、黄棕壤、水稻土和红壤）中的吸附-解吸影响.结果表明,随着溶液中Ca²⁺离子浓度的增加,诺氟沙星在土壤中的吸附参数K_f值逐渐减小并趋于稳定,两者间存在显著负相关（p≤0.05）.同时,Ca²⁺离子浓度的增加对低浓度诺氟沙星溶液的吸附影响相对高浓度而言不明显. 低pH下,诺氟沙星主要以阳离子形态存在,吸附以阳离子吸附或氢键为主;在兼性离子状态时,则主要以静电吸附和偶极力为主.这是造成4种土壤中诺氟沙星吸附差异的根本原因.在不同离子强度下,土壤溶液中二价Ca²⁺离子存在则对诺氟沙星的活性吸附位点造成竞争性吸附,从而降低诺氟沙星的土壤吸附量.同时,不同阳离子导致诺氟沙星的土壤吸附存在差异.其影响趋势主要为价态的影响,即价态越高,竞争吸附能力越强：M⁺（Na⁺、K⁺、NH^＋₄）2+（Ca²⁺、Mg²⁺、Zn²⁺）3+（Al³⁺）.     

太湖地区农田土壤中铵态氮和硝态氮的时空变异

对太湖地区农田土壤3种主要水稻土类型:白土、黄泥土和乌栅土在小麦和水稻生长期间土壤剖面中NH₄⁺-N和NO₃^--N含量的时空变异进行了研究.结果表明:NH₄⁺-N在1a中的2月份和9月含量较高;4月份和11月的含量较低.NH₄⁺-N在土壤剖面中的空间变异为土壤上层到土壤下层呈逐渐递减趋势,以表土层含量为最高,在40cm以下基本上趋于稳定.NO₃^--N的含量低于NH₄⁺-N,在1a中小麦生长季节(旱作)高于水稻生长季节(水作);NO₃^--N在土壤剖面中的空间变异为:旱作时的土壤表层到底层迅速下降;但在水稻生长季节土壤剖面中表层土壤的NO₃^--N含量低于底层的NO₃^--N的含量,出现明显的淋溶现象.在旱作期间NO₃^--N随NH₄⁺-N呈指数曲线变化,而在水稻生长期间没有这种关系.NH₄⁺-N和NO₃^--N含量与土壤有机质呈显著的直线线性正相关关系.但NH₄⁺-N和NO₃^--N仅在旱作时随土壤粘粒含量和土壤pH值的升高而呈对数曲线下降.     

上海市郊保护地土壤盐分研究

研究了上海市郊部分旱作农田土壤盐分特征.结果表明,上海市郊部分种植瓜果、蔬菜的土壤出现盐渍化趋势.其中,非盐化土壤占88.52%,轻度盐化土壤占10.37%,中度盐化土壤占0.74%,重度盐化土壤占0.37%.盐分组成中,阴离子以SO^2-₄为主,其次为Cl^-、NO^-₃,阳离子以Ca²⁺、Na⁺离子为主,其次为Mg²⁺、K⁺离子.这些离子成分除了少量的土壤原始沉积量外,大多为化肥的副成分或转化物.沪郊设施栽培土壤次生盐渍化的形成与化肥使用不当或过量施用密切相关.不同种植方式0～20 cm耕层土壤中盐分从高到低依次为：大棚菜地、大棚瓜地、大棚瓜-菜轮作地和露天菜地.随着设施利用时间的增长,同一区域设施土壤全盐量持续升高,下层土壤盐分逐步向上层富集,且这种自下而上的富集速度有加快的趋势.     

亚热带可变电荷土壤磷素淋失临界点及其与土壤特性的关系

选取我国亚热带地区16种典型可变电荷土壤,通过室内模拟试验测定其磷素(P)淋失临界点的Olsen-P含量,以及可能对其构成有影响的8个化学性质指标(pH、CEC、粘粒、有机质、交换性钙、镁和铁铝氧化物含量),以探讨可变电荷土壤P淋失临界点的特点及其与土壤相关性质的关系,并评价当前的P淋失潜在风险.结果表明:可变电荷土壤P淋失临界点的Olsen-P含量(56 ～ 123 mg·kg-1)差异很大,旱地土壤临界点Olsen-P含量主要集中在低值区间(＜60 mg·kg-1),而水稻土临界点Olsen-P含量集中在高值区间(＞80 mg·kg-1);旱地土壤P淋失风险高于水稻土.主成分分析显示,可变电荷土壤的pH、粘粒、CEC、有机质、交换性钙镁、氧化铁铝等化学性质同时对其临界点Olsen-P含量构成正的或负的影响.因此,临界点Olsen-P含量与单一因素的回归分析不仅不能够确切地反映临界点Olsen-P含量与这些化学性质的关系(与pH、CEC、粘粒、交换性钙镁含量无显著相关),甚至与理论上的关联相违(与氧化铁铝含量呈负相关).与以往研究结果比较,可变电荷土壤在旱作和稻作下的P淋失临界点的Olsen-P含量都普遍高于永久电荷土壤,研究的16种可变电荷土壤的实际Olsen-P含量也远低于临界点Olsen-P含量,由此推断南方地区耕作土壤的P淋失风险仍较小.     

低分子量有机酸对几种可变电荷土壤吸附氟的影响

用一次平衡法研究了四种低分子量有机酸对几种可变电荷土壤吸附氟的影响，结果表明，低分子量有机酸可以通过竞争吸附作用抑制土壤对氟的吸附，化学结构相对简单的草酸和丙二酸对氟吸附的抑制作用大于柠檬酸和苹果酸。有机酸对氟吸附的抑制作用随土壤氧化铁含量的增加而增加，并随体系pH的增加而增强。在低pH和氟加入量较高的情况下，有机酸通过与氟竞争可溶性铝而增加土壤对氟的吸附量，这在对铝溶解度较高的酸性土壤中尤为明显。     

Remediation of saline–sodic soil with flue gas desulfurization gypsum in a reclaimed tidal flat of southeast China

Salinization and sodicity are obstacles for vegetation reconstruction of coastal tidal flat soils. A study was conducted with flue gas desulfurization(FGD)-gypsum applied at rates of 0, 15, 30, 45 and 60 Mg/ha to remediate tidal flat soils of the Yangtze River estuary.Exchangeable sodium percentage(ESP), exchangeable sodium(ExNa), p H, soluble salt concentration, and composition of soluble salts were measured in 10 cm increments from the surface to 30 cm depth after 6 and 18 months. The results indicated that the effect of FGD-gypsum is greatest in the 0–10 cm mixing soil layer and 60 Mg/ha was the optimal rate that can reduce the ESP to below 6% and decrease soil p H to neutral(7.0). The improvement effect was reached after 6 months, and remained after 18 months. The composition of soluble salts was transformed from sodic salt ions mainly containing Na~+, HCO_3~-+ CO_3~(2-)and Cl-to neutral salt ions mainly containing Ca~(2+)and SO_4~(2-). Non-halophyte plants were survived at 90%. The study demonstrates that the use of FGD-gypsum for remediating tidal flat soils is promising.     

大气PM2.5中水溶性离子在线观测技术的应用研究

为了解北京大气PM2.5污染状况,评估大气细颗粒物快速捕集-化学成分在线分析系统(RCFP-IC)在追踪污染生成-消散过程中的适用性,于2011年3月对北京PM2.5中NO3-、SO24-、NH4+和Cl-这4种污染型水溶性离子浓度变化进行了连续高时间分辨率观测,并结合同期气象要素的变化,探讨了污染过程形成的原因.结果表明,一个月的观测期内捕捉到了5次较为明显的污染过程,4种水溶性离子的浓度变化趋于一致,并呈现出典型的"慢积累、快清除"的锯齿型污染物浓度时间序列变化特征.NO3-和NH4+在典型污染事件中峰值浓度是清洁时期浓度的10倍以上,而SO24-和Cl-污染峰值浓度仅为清洁时期的2～4倍.停暖后4种离子浓度较采暖期下降了15%～60%.RCFP-IC与高分辨率飞行时间气溶胶质谱(HR-TOF-AMS)同期观测结果变化趋势具有高度的一致性,但RCFP-IC定量水溶性离子浓度更为准确.     

Stability of the pH and the contents of ammonium and nitrate in precipitation samples

The changes in the pH and the contents of NH₄⁺, NO₃⁻ and 10 other components including trace elements were studied in precipitation samples for a period of up to 300 days. The concentration of free H⁺ ions is affected after deposition by several processes, the most important being bioconsumption of NH₄⁺ leading to an increase in the H⁺ ion level depending on the length of the sampling interval, the time of year and the way of storing the samples prior to their analysis. It is proposed that, for the purpose of comparing the acidities of precipitation waters and their effects on acidification of the environment, the corrected H⁺ ion concentration (H_c⁺) be calculated from the pH value and the concentrations of NH₄⁺ and NO₃⁻ (H_c⁺ = H⁺+NH₄⁺−NO₃⁻). The H_c⁺ value depends little on the bioconsumption of NH₄⁺ and NO₃⁻ after deposition and thus is not very sensitive to the way of storing the samples, the sampling interval and the time elapsed between deposition and the sample analysis. Dissolution of Fe, Al, Si and some trace elements from the particles scavenged during precipitation was slow in the studied samples; it is advantageous to digest the sample in a microwave oven prior to determination of these elements.     

Adsorption characteristic of bensulfuron-methyl at variable added Pb^2＋ concentrations on paddy soils

The combined pollution of heavy metal Pb²⁺ and bensulfuron-methyl (BSM), originating from chemical herbicides, in agroecological environments has become commonplace in southern China. The adsorption of BSM on three paddy soils in the presence of Pb²⁺ was examined using high-performance liquid chromatograph (HPLC). Results indicated that adsorption of BSM could accurately be described by a Freundlich isotherm equation with correlation constant (R) > 0.98, irrespective of the presence of spiked Pb²⁺. Of the various factors influencing BSM sorption, soil pH appeared to be the most influential. The constant K_f of Freundlich isotherm equation tended to increase with increasing Pb²⁺ concentration in soil which indicated that the spiked of Pb²⁺ in paddy soils would promote the sorption of BSM. ΔG^θ of BSM in three paddy soils was less than 40 kJ/mol in all treatments, indicating the adsorption of BSM is mainly physical in nature. The elution of soil dissolved organic matter (DOM) enhanced the adsorption of BSM in paddy soils. The mechanisms involved in the promotion effects of the spiked Pb²⁺ on BSM adsorption might be the modified surface characteristics of paddy soil solids due to the soil acidification and the increase of soil organic matter concentration because of DOM binding.     

The research of below-cloud scavengingof rainwater in Guilin City

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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.     

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。