土壤对铜的吸附-解吸特征及对土地利用的响应

用吸附平衡法研究黄河三角洲地区土壤对Cu2+的吸附和解吸特征,对比了农田和未利用地土壤吸附与解吸能力的差异,并分析了差异形成的原因。结果表明,土壤对Cu2+的吸附量随着平衡液Cu2+质量浓度的增加而增加,其吸附作用可用Langmuir,Temkin和Freundlich方程来拟合,以Langmuir方程拟合结果最佳。根据Langmuir方程计算出的两种土壤最大吸附量分别为3 961mg/kg和3 521mg/kg,农田土壤对Cu2+的吸附能力强于未利用地土壤;土壤Cu2+的解吸量远远小于土壤对Cu2+的吸附量,与农田土壤相比,未利用地土壤Cu2+的解吸有滞后现象;农田土壤和未利用地土壤Cu2+的解吸率变化范围分别为0.1%～0.35%和0.15%～1.8%,农田土壤的解吸率明显低于未利用地土壤。综合分析认为,两种土壤吸附—解吸特征的差异与农田土壤具有较高的有机质含量,从而在土壤胶体表面形成较多的吸附位点有关。     

SO42-和Cl-对稻田土壤养分及其吸附解吸特性的影响

利用长期定位试验 ,比较了长期施用含SO₄^2-和Cl^- 化肥 22年后稻田土壤的 pH值、养分状况及其吸附解吸特性。结果表明 ,长期施用含SO₄^2-化肥 ,土壤有机质、速效氮和速效钾的含量较高 ,但全量氮磷钾的含量较低 ;长期施用含Cl^- 化肥 ,土壤全量氮磷钾和速效磷的含量较高 ,但pH值相对较低。长期施用含上述二种阴离子的化肥后 ,土壤对H₂PO₄^-的最大吸附量均较大 ,且在Cl^- 处理下土壤对H₂PO₄^-吸附的结合能较大 ,而SO₄^2-处理下土壤在同等吸附量时对H₂PO₄^-的解吸量相应较多。长期施用含SO₄^2-的化肥亦使土壤对钾素的供应强度较大 (ΔK0的绝对值较大 )、缓冲能力增强 (AR0值较高 ) ,而长期施用含Cl^- 的化肥时则与SO₄^2-相反     

含Ni六方水钠锰矿的表征及其对Pb 2+ (Zn2+)环境行为的影响

六方水钠锰矿是土壤中普遍存在、活性最强的氧化锰矿物。它常常富集各种过渡金属如Ni等,对其地球化学行为具有重要影响。在六方水钠锰矿形成过程中加入Ni²⁺,Ni以+2价存在于矿物中。进入水钠锰矿结构中的Ni大部分以[NiO₆ ]八面体形式存在于层内;仅有小部分Ni存在于八面体空位上下方。含Ni水钠锰矿沿c轴方向堆叠锰氧八面体层数逐渐减小,而a-b板面晶体大小没有明显变化,即层片状晶体逐渐变薄,比表面积显著增大。随着Ni含量的增加,水钠锰矿结构中锰氧八面体空位数减少,而层边面吸附位点数基本保持不变,其对重金属离子(Pb²⁺/Zn²⁺)吸附去除能力逐渐降低。本文为明确过渡金属离子(Ni)对土壤中氧化锰矿物的形貌、结构及其性质的影响提供了参考。     

土壤对铜离子的专性吸附及其特征的研究

供试土壤专性吸附铜的等温线均符合Langmuir方程。红壤吸附量最低,砖红腹与黄泥土最大吸附量相近,但在铜浓度低时砖红壤吸铜量远低于黄泥土,而在高浓度则反之。土壤专性吸附铜是在溶液中Na⁺浓度比Cu²⁺高8.3—100倍条件下,Na⁺离子仍不足以与之竞争的那些专性吸附点所吸持的铜。按其解吸条件区分为松结合铜(可为N NH₄Cl解吸)和紧结合铜(仅能为0.1 N HCl解吸)两种。紧结合铜受平衡溶液铜浓度影响很小,所占据的吸附点对Cu²⁺有较强亲和力。松结合铜则随平衡铜溶液浓度增大而增加,符合Langmuir方程。对于砖红壤和黄泥土,在铜浓度低时紧结合铜>松结合铜;浓度高时则反之。红壤专性吸附铜始终以松结合铜为主。三种土壤比较,紧结合铜是砖红壤>黄泥土>红壤;松结合铜则是黄泥土>砖红壤>红壤。造成这些差别的原因可能与土壤性质、氧化物、有机质和粘土矿物组成等不同有关。用平衡法研究三种土壤专性吸附铜在不同浓度NH₄Cl和HCl溶液中的解吸表明,可进一步区分为三或四种不同的结合状况。红壤对铜吸附容量最小,且最易解吸。     

不同生物质炭对棕壤中磷素吸附解吸的影响

为了减少土壤磷素流失,提高磷肥利用效率,探究不同生物炭对棕壤中磷素吸附解吸行为的影响规律,以水稻秸秆、玉米秸秆和花生壳为原材料,利用限氧升温炭化法制备生物炭,通过批量吸附实验研究了生物炭种类和生物炭添加量对棕壤磷吸附解吸的影响。结果表明：水稻秸秆生物炭在添加量为0.4%时显著提高棕壤对磷的吸附量,花生壳生物炭和玉米秸秆生物炭则显著降低棕壤对磷的吸附量；等温吸附曲线表明,不同生物炭均未改变等温吸附曲线的变化趋势,均可用Langmuir方程和 Freundlich 方程进行描述(R²>0.93),其中 Langmuir 方程拟合效果更好,不同处理对磷的理论吸附量大小顺序为：水稻秸秆生物炭+棕壤>棕壤>花生壳生物炭+棕壤>玉米秸秆生物炭+棕壤；吸附动力学实验表明,不同生物炭均未改变磷吸附动力学曲线的变化趋势,在所有动力学模型中,准二级动力学模型最适合描述土壤对磷的吸附行为(R²>0.99),其次为准一级动力模型(R²>0.99)和Elovich动力学模型(R²>0.88)；三种生物炭均显著促进棕壤对磷的解吸,当生物炭添加量为≥0.2%时,水稻秸秆生物炭、玉米秸秆生物炭和花生壳生物炭,分别可提高棕壤对磷的解析率50%、70%和90%以上。由此可见,不同生物炭可提高棕壤对磷素的供应和利用,水稻秸秆生物炭在减少棕壤磷素流失、保护生态环境方面具有更大的应用价值。     

可变电荷土壤和矿物Pb2+ and Cu2+吸附动力学: Ⅶ. Pb2+吸附后H+释放的动力学

The kinetics of H⁺ releasing after Pb²⁺ adsorption was studied by the potentiometric method combined with the acid-base titration curve technique. Results showed that pH of latosol, red soil and kaolinite suspensions dropped sharply, and then decreased gradually. Most of the H⁺ exchanged, more than 60%, was displaced at the first minute after Pb²⁺ was added into the suspension. More H⁺ was released at a higher concentration of Pb²⁺ added for a given sample and the amount of H⁺ released decreased in the order of red soil > latosol > kaolinite at a given concentration. The time-dependent data of H⁺ releasing of latosol, red soil and kaolinite at two concentrations could be fitted best with the second-order equation among the six equations, including second-order equation, two-constant equation, Elovich equation, parabolic diffusion equation, first-order equation and exponential equation. The H⁺/Pb²⁺ exchange stoichiometry increased with time, and a stable ratio of H⁺/Pb²⁺, being 1.73, 1.92 and 2.01 for kaolinite, latosol and red soil, respectively, was reached 25 minutes later.     

NO-3胁迫下K+、Ca2+对黄瓜幼苗膜质过氧化及活性氧清除酶系统的影响

通过水培试验探讨了NO^-₃胁迫下K⁺、Ca²⁺对黄瓜幼苗膜质过氧化及活性氧清除酶系统的影响。结果表明，在相同NO^-₃浓度胁迫7d后， Ca²⁺浓度越大，膜脂过氧化产物丙二醛(MDA)含量越高，而K⁺浓度越大，电解质相对渗透率越高，由此说明K⁺、Ca²⁺对细胞膜造成伤害的机理不同。黄瓜幼苗活性氧清除酶系统对K⁺、Ca²⁺的响应亦不同，在一定程度上，K⁺和Ca²⁺ 可提高SOD、POD和CAT活性，保护植物免受自由基伤害，继而可增强植物对逆境的适应能力。     

柠檬酸对蒙山茶园土壤微团聚体吸附-解吸Cu2+的影响

以蒙山茶园土为对象,运用平衡液吸附法以及NaNO3溶液解吸法探讨了柠檬酸对原土及各粒径土壤微团聚体吸附-解吸Cu2+的特性,以期明确柠檬酸对土壤吸附解吸铜的过程中产生的影响。结果表明,加入柠檬酸后,随着Cu2+浓度的增加,原土和各粒径土壤微团聚体对Cu2+的吸附有所增加,吸附量大小顺序为:(0.002mm)(0.053~0.002)mm原土(2~0.25)mm(0.25~0.053)mm,与土壤微团聚体中游离氧化铁、阳离子交换量以及有机质含量大小顺序一致;柠檬酸对Cu2+的吸附既有促进作用又有抑制作用,低浓度(0~1mmol/L)的柠檬酸促进土壤微团聚体对Cu2+的吸附,而高浓度(1mmol/L)的柠檬酸则降低其吸附,吸附量在柠檬酸浓度为0.5mmol/L时达到最大;Langmuir、Freundlich、Temkin 3种方程对其等温吸附过程的拟合均达到了极显著水平(p0.01),其中以Langmuir方程的拟合效果最佳,说明加入柠檬酸后的原土及各粒径土壤微团聚体对Cu2+的吸附以单层吸附为主;随着铜浓度的上升,土壤微团聚体对Cu2+的易解吸率不断增加,柠檬酸的进一步加入使得土壤微团聚体对Cu2+的解吸率上升,而解吸大小顺序与吸附顺序相反。     

胶体存在时不同质地土壤对锌镉的吸附试验研究

以重金属离子Zn和Cd及胶体为对象,通过等温静态批量平衡吸附试验,分析了3种不同质地土壤对Zn、Cd单一吸附和等量竞争吸附特征,胶体对土壤吸附Zn、Cd的影响,并用Langmuir和Freundlich方程对试验结果进行了拟合。结果表明,随着平衡液中Zn2+、Cd2+浓度的增加,土壤对Zn、Cd的吸附量逐渐增大;3种质地土壤对Zn、Cd吸附量顺序为砂壤>粉壤>壤砂土;Zn2+、Cd2+共存时,土壤对这两种离子的吸附量比单一离子存在的情况下明显下降;胶体存在时抑制了土壤对Zn的吸附,促进了土壤对Cd的吸附;就本试验来说,Freundlich方程拟合效果优于Langmuir方程。     

利用15N揭示滴灌区盐旱胁迫对土壤氮素分布与棉花生长的影响

为了探究盐旱胁迫对土壤中氮素分布和棉花生长的影响,通过测坑试验研究滴灌区不同盐分、干旱条件下土壤全氮、硝氮、氨氮的分布和棉花生长情况。试验设置3种盐分梯度的土壤（电导率,EC）：3,6,9 dS/m,分别用T1、T2、T3表示;3个灌水量：2 700,3 600,4 500 m³/hm²,分别用W1、W2、W3表示（4 500 m³/hm²为当地推荐灌水量）。结果表明：当土壤盐分梯度> 3 dS/m时土壤全氮累积量显著高于低盐土壤（P<0.05）,且土壤盐分对棉花花期生长影响较大。土壤的氨氮挥发量和土壤盐分梯度成正比。土壤硝态氮的淋失与灌水量呈正比,与正常灌水量的硝态氮淋失相比,水分胁迫对棉花产量的影响更为严重（P<0.01）。随土层深度的增加,土壤碱解氮以每20 cm土层8%的速度减少。各处理土壤¹⁵N残留率为11%~40%,随土壤盐度增加而增加,随灌水量增加而减少,与土壤全氮含量呈正比,与棉花产量呈反比。综上所述,T1W3处理更有利于棉花对氮肥的利用和产量的提高,推荐滴灌区棉花土壤盐度<3 dS/m,灌水量4 500 m³/hm²,可在花期适当提高施肥量以稳定产量。     

Schwermetallanreicherung und Schwermetallverfügbarkeit im Einsickerungsbereich von Stammablaufwasser in Buchenwäldern (Fagus sylvatica) des Wienerwaldes

Heavy metal enrichment and mobility in the infiltration zone of stemflow from beech (Fagus sylvatica) in the Vienna woods Filtering action of beech crowns in a polluted atmosphere produces acidic stemflow enriched with heavy metals. Series of soil profiles through the infiltration zone of stemflow waters were analyzed in three old growth beech stands on pseudogley (aqualf) soils of the northeastern Vienna Woods to study soil acidification and heavy metal accumulation and mobility: + In the infiltration zone of stemflow soil pH can be less than pH 3 and thus more than 2 pH units lower than in profiles more distant from the stem base. + Heavy metal contents of the soil peaked near the stembase. Maximum values for lead were 500 to 1.200 mg·kg^?1 soil, for copper 70 to 150 mg·kg^?1 soil and for zinc 250 to 500 mg·kg^?1 soil. + Manganese was not enriched but leached out from the soil profile. + The proportion of AED-complexable lead and copper to total lead and copper decreased under stemflow influence in the topsoil but increased in the subsoil. These results indicate that significant amounts of heavy metals are deposited with stemflow in beech stands of the Vienna Woods. Strong soil acidification enhances heavy metal solubility and thus promotes leaching into deeper soil strata.     

Fraction Distributions of Lead,Cadmium, Copper,and Zinc in Metal‐Contaminated Soil before and after Extraction with Disodium Ethylenediaminetetraacetic Acid

Abstract: The fraction distributions of heavy metals have attracted more attention because of the relationship between the toxicity and their speciation. Heavy‐metal fraction distributions in soil contaminated with mine tailings (soil A) and in soil irrigated with mine wastewater (soil B), before and after treatment with disodium ethylenediaminetetraacetic acid (EDTA), were analyzed with Tessier's sequential extraction procedures. The total contents of lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) exceeded the maximum permissible levels by 5.1, 33.3, 3.1, and 8.0 times in soil A and by 2.6, 12.0, 0.2, and 1.9 times in soil B, respectively. The results showed that both soils had high levels of heavy‐metal pollution. Although the fractions were found in different distribution before extraction, the residual fraction was found to be the predominant fraction of the four heavy metals. There was a small amount of exchangeable fraction of heavy metals in both contaminated soils. Furthermore, in this study, the extraction efficiencies of Pb, Cd, and Cu were higher than those of Zn. After extraction, the concentrations of exchangeable Pb, Cd, Cu, and Zn increased 84.7 mg·kg^?1, 0.3 mg·kg^?1, 4.1 mg·kg^?1, and 39.9 mg·kg^?1 in soil A and 48.7 mg·kg^?1, 0.6 mg·kg^?1, 2.7 mg·kg^?1, and 44.1 mg·kg^?1 in soil B, respectively. The concentrations of carbonate, iron and manganese oxides, organic matter, and residue of heavy metals decreased. This implies that EDTA increased metal mobility and bioavailability and may lead to groundwater contamination.     

三峡库区土壤重金属背景值研究

在大规模、系统采样的基础上,通过不同均值计算方法的比较,提出了三峡库区土壤重金属含量背景值：As为5．835mg&#183;kg^-1,Cd为0．134mg&#183;kg^-1,Cr为78．03mg&#183;kg^-1,Cu为25．00mg&#183;kg^-1,Hg为0．046mg&#183;kg^-1,Ni为29．47mg&#183;kg^-1,Pb为23．88mg&#183;kg^-2,Zn为69．88mg&#183;kg^-1。与全国土壤背景值比较,三峡库区As、Hg背景含量低于全国背景值,Pb、Zn含量略低于全国背景值,Cd、Cr含量高于全国土壤背景值,Cu、Ni含量略高于全国背景值。根据本研究成果进行三峡库区环境质量评价,将能更加真实地反映三峡库区的实际情况,有利于库区土壤环境质量管理。     

KINETICS OF ION EXCHANGE IN SOIL ORGANIC MATTER. IV. ADSORPTION AND DESORPTION OF Pb2+, Cu2+, Cd2+, Zn2+ AND Ca2+ BY PEAT

The equilibria as well as the rates of adsorption and desorption of the ions Pb²⁺, Cu²⁺, Cd²⁺, Zn²⁺, and Ca²⁺ by soil organic matter were determined in batch experiments as a function of the amount of metal ions added to an aqueous suspension of HCl-washed peat. Simultaneous determination of the metal ions and hydrogen ions in the solution by atomic absorption spectrophotometry and pH-measurements showed that the adsorption of one divalent metal ion by peat was coupled with the release of two hydrogen ions. Since this equivalent ion-exchange process causes a corresponding increase of the electric conductivity of the solution, the rates of the adsorption and desorption processes were determined by an immersed conductivity electrode. The distribution coefficients show that the selective order for the metal adsorption by peat is Pb²⁺ > Cu²⁺ > Cd²⁺≌ Zn²⁺ > Ca²⁺ in the pH range of 3·5 to 4·5. The slope of -2, as observed in a double logarithmic plot of the distribution coefficients versus the total solution concentration confirms the equivalence of the ion-exchange process of divalent metal ions for monovalent H₃O⁺ -ions in peat. The absolute rates of adsorption, as well as the rates for the fractional attainment of the equilibrium, increase with increasing amounts of metal ions added. This behaviour is also observed for the subsequent desorption of the metal ions by H₃O⁺-ions. At a given amount of metal ions added, the absolute rates of adsorption decrease in the order Pb²⁺ > Cu²⁺ > Cd²⁺ > Zn²⁺ > Ca²⁺, while the rates for the fractional attainment of the equilibrium decrease in the order Ca²⁺ > Zn²⁺≌ Cd²⁺ > Pb²⁺ > Cu²⁺. The half times for adsorption and desorption were in the range of 5 to 15 sec.     

羟基磷灰石对铅锌矿区土壤吸附Zn2+、Cd2+的影响

为探究羟基磷灰石(HAP)对矿区土壤重金属的固化效果,采用吸附试验,研究施加HAP的铅锌矿区土壤对Cd~(2+)、Zn~(2+)的动力学吸附和等温吸附效果。结果表明:土壤对Cd~(2+)、Zn~(2+)的吸附量随Cd~(2+)、Zn~(2+)初始浓度的增加而增加;在酸性条件下,其吸附量随pH上升而上升;准二级动力学方程能很好地描述两者的吸附过程,土壤吸附能力随HAP的添加量增大而增强;在Zn—Cd共存体系中,当初始浓度为20mg/L时,土壤对Zn~(2+)、Cd~(2+)的吸附无明显差异,2种金属离子竞争力度小,随着初始浓度上升,竞争明显,对Zn~(2+)的最大吸附量能达到单一体系中的79%～87%,而Cd~(2+)的最大吸附量只有单一体系中的57%～72%,Zn~(2+)的竞争力优于Cd~(2+),Zn~(2+)对Cd~(2+)吸附产生严重的抑制。综上可知,HAP能提高矿区土壤的吸附性能,在Zn、Cd污染土壤中,更能提升土壤对Zn~(2+)的吸附固持能力。     

Study of the Transfer Coefficient of Cadmium and Lead in Ryegrass and Lettuce

Abstract

The aim of study was to find the correlation between the concentration of the total amount of heavy metals of soils and that of plants because it shows which elements can be accumulated by different plants. The transfer coefficient is the metal concentration in plant tissues aboveground divided by the total metal concentration of soil. Pot experiments were conducted under greenhouse conditions. The total lead (Pb) content (about 21 mg · kg^?1 soil) of soils was higher than the cadmium (Cd) content (about 0.21 mg · kg^?1 soil). The Cd concentration of lettuce (averaging 0.93 mg · kg^?1) was higher than that of ryegrass (averaging 0.20 mg · kg^?1). The transfer coefficient of Cd was lower in ryegrass (averaging 0.95) than in lettuce (4.47). In this experiment, the concentration of Cd was almost five times higher in the four‐leaf lettuce than the Cd content of soil. The transfer coefficient of Pb was generally 0.064 in both plants.     

Effect of the particle-size distribution on the adsorption of copper, lead, and zinc by Chernozemic soils of Rostov oblast

The parameters of adsorption of Cu²⁺, Pb²⁺, and Zn²⁺ cations by soils and their particle-size fractions were studied. The adsorption of metals by soils and the strength of their fixation on the surface of soil particles under both mono- and polyelement contamination decreased with the decreasing proportion of fine fractions in the soil. The adsorption capacity of the Lower Don chernozems for Cu²⁺, Pb²⁺, and Zn²⁺ depending on the particle-size distribution decreased in the following sequence: clay loamy ordinary chernozem ∼ clay loamy southern chernozem > loamy southern chernozem > loamy sandy southern chernozem. According to the parameters of the adsorption by the different particle-size fractions (C _max and k), the heavy metal cations form a sequence analogous to that obtained for the entire soils: Cu²⁺ ≥ Pb²⁺ > Zn²⁺. The parameters of the heavy metal adsorption by similar particle-size fractions separated from different soils decreased in the following order: clay loamy chernozem > loamy chernozem > loamy sandy chernozem. The analysis of the changes in the parameters of the Cu²⁺, Pb²⁺, and Zn²⁺ adsorption by soils and their particlesize fractions showed that the extensive adsorption characteristic, namely, the maximum adsorption (C _max), was a less sensitive parameter characterizing the soil than the intensive characteristic of the process—the adsorption equilibrium constant (k).     

Removal of Cu2+ and Cd2+ from Aqueous Solution by Bentonite Clay Modified with Binary Mixture of Goethite and Humic Acid

Pre-modification of bentonite clay with goethite, humic acid, and a binary mixture of goethite and humic acid reagents increased its cation exchange capacity from 95 to 105.32, 120.4, and 125.8 meq/100 g of bentonite clay, respectively. The effective pre-modification of bentonite clay with goethite, humic acid, and goethite–humic acid reagents was confirmed from their Fourier transform infrared spectra which suggested that modification was effective on the AlAlOH and Si–O sites for goethite and humic acid modification and AlAlOH for goethite–humic acid modification. The presence of 0.001 M NaNO₃ electrolyte increased the adsorption capacity of bentonite clay. Temperature was observed to favor the adsorption of Cu²⁺ and Cd²⁺ onto both the raw and modified bentonite clay samples. The goethite–humic acid-modified bentonite gave the best adsorption capacity of ≈10 and 16 mg/g at 30 and 50°C, respectively, for both metal ions. The inner sphere complexation mechanism was suggested for the adsorption of both metal ions onto the modified adsorbents. Modifying bentonite clay with a binary mixture of goethite and humic acid reduced the selectivity of bentonite clay for either Cu²⁺ or Cd²⁺. Preadsorbed goethite and humic acid on bentonite clay will further reduce the mobility of heavy metal ions in soils and in aquatic environments.     

重金属污染对水稻田土壤硫酸盐还原菌种群数量及其活性的影响

在实验室条件下,采用重金属Cd2+、As5+、Cu2+、Pb2+和Cr3+处理黄松稻田土壤、紫色稻田土壤和红壤稻田土,28d后分析重金属污染对水稻田土壤的硫酸盐还原菌(SRB)种群数量和硫酸盐还原活性(SRA)的影响。结果表明,在每千克干土中加入200mgPb2+时,对稻田土壤的SRB种群数量和SRA有促进作用;当加入的Cd2+、As5+、Cu2+、Pb2+和Cr3+每千克干土分别超过1.0、30、500、400和200mg时,对稻田土壤SRB种群数量和SRA有明显抑制作用。随着加入量的增加,重金属对水稻田土壤的SRB种群数量和SRA的抑制作用越来越强,水稻田土壤通过自身来恢复SRB种群数量和SRA所需的时间也越长。同一种重金属元素对不同土壤的SRB种群数量和SRA抑制的污染临界值也有差异。