外源铜和镍在土壤中的化学形态及其老化研究

采用连续提取法测定了外源铜和镍进入田间土壤后的化学形态分布,比较研究了这2种重金属在3种不同类型土壤(红壤,水稻土和潮土)中随老化时间的形态转化和分布.结果表明,外源铜以残留态(40%～60%)和EDTA可提取态(40%)为主;随老化时间,EDTA可提取态、易还原锰结合态及铁铝氧化态向残留态转化;外源镍在酸性红壤中以可交换态(40%)和残留态(30%～50%)为主,在中性水稻土中以EDTA可提取态(30%)和残留态(30%～50%)为主,在碱性潮土中以铁铝氧化态(20%)和残留态(40%)为主.随老化时间,水溶态、可交换态、EDTA可提取态等向残留态转化.土壤pH较低时水溶态和可交换态含量较高,但是同时随老化时间的降低量也明显;pH较高时有利于易还原锰结合态和有机质结合态的转化.     

碳酸钙和硼对棕红壤油菜锰毒缓解作用

对已酸化的棕红壤进行的油菜锰毒缓解研究表明,施用碳酸钙在提高土壤ＰＨ和降低土壤交换性锰的基础上,改善了土壤营养状况,其中施用０．５％碳酸钙处理的效果最好,在这一碳酸钙水平下,土壤硼处于较高的活性,土壤速效钾被油菜幼苗充分利用,油菜幼苗对营养元素具有最大吸收量,使植株生物学产量达到最大值。酸化的棕红壤只需施用０．５％的碳酸钙,其土壤酸碱度便可恢复到正常鲨和更多的碳酸钙。会造成土壤营养再度失调,油菜轩     

酸性土壤活性锰与pH、Eh关系及其生物反应

以灰潮土为对照研究了湖北省 3种有代表性的酸性土壤在盆栽条件下 ,不同酸化处理土壤pH、Eh与活性锰的动态变化关系。结果表明 ,供试的棕红壤和黄棕壤酸化后 ,在盆栽油菜生长的前 70d内 ,土壤交换性锰含量增加 ,土壤交换性锰与碳酸盐结合态锰呈一定负相关 ,且交换性锰含量增加明显滞后于碳酸盐结合态锰的增加 ;30～90d内 ,碳酸盐结合态锰与易还原性锰呈一定正相关。虽然土壤pH和Eh在作物生长季节不断变化 ,但其 pe +pH仍维持不变。土壤 pH、Eh与交换性锰的关系能较好地反映土壤锰的转化机制 ,在进一步酸化时 ,供试的棕红壤MnO2/Mn2+电对是该土壤锰化合物变化的主要形式 ,MnO2是变化过程的电子受体。供试的黄棕壤则以MnOOH MnO电对为其锰化合物氧化还原的主要形式 ,土壤酸化对其锰电对电位的影响没有直接引起Mn2+ 的变化 ;Mn2+的增加可能是MnO在该过程中进一步溶解所致。试验结果还表明 ,油菜体内的锰铁比随锰中毒程度的加强而急剧增加 ,这一趋势远高于土壤锰铁比的增加。     

有机物料对土壤中外源镉形态与生物有效性的影响研究

盆栽试验研究稻草与紫云英对土壤中外源Cd形态及其生物有效性的影响结果表明 ,添加稻草与紫云英可降低水稻分蘖期潮土和红壤交换态镉含量 ,且二者在不同土壤的影响不同。 2种有机物料在水稻分蘖期固定作用并不稳定 ,随时间的推移 ,氧化锰结合态和紧有机质结合态吸附的镉将随紧有机质的分解和活性锰的还原被释放出来 ,并向交换态镉转化 ,提高Cd的生物有效性。水稻对外源Cd吸收与Cd在土壤中形态密切相关 ,水稻分蘖期稻草与紫云英均可抑制水稻根和茎叶对外源Cd的吸收 ,至成熟期水稻根、茎叶和糙米中Cd含量迅速增加 ,其根本原因是由于土壤中交换态镉含量提高和紧有机质结合态镉含量降低所致     

再生水灌溉对4类土壤Cd生物有效性的影响

根据国家土壤环境质量标准,选取重金属Cd含量为二级水平的4类土壤（红壤、 潮土、 土、 黑土）进行土培试验,研究再生水灌溉与小白菜生物量及Cd含量、 土壤有效态Cd含量、 pH、 微生物群落的关系,以及不同类型土壤间的差异性。结果表明, 再生水灌溉在不同类型土壤上对小白菜生物量及Cd含量、 土壤有效态Cd含量、 土壤pH和微生物数量的影响不同: 1）红壤、 潮土、 土上小白菜生物量增加显著,分别增加9.09%、 16.08%、 9.92%,黑土上增加不显著; 2）小白菜Cd含量在红壤上显著降低,由对照的0.29 mg/kg降低到0.22 mg/kg,在黑土上比对照增加了18.75%,在潮土和土上影响不大; 3）有效态Cd含量在红壤没有变化,但在潮土、 土、 黑土上增加显著; 4） 4类土壤微生物数量增加显著; 5）潮土、 土、 黑土的pH值有所降低。     

污泥土地利用研究II. 连续化学提取法研究施污泥土壤重金属的有效性和环境风险

本文采用连续化学提取法研究了施用污泥土壤中重金属的形态分配及有效性。铜和锌在2种土壤上施用污泥前、后的形态分配都有所差异,铜在河湖相水稻土上以可氧化态为主;红壤性水稻土可氧化态和可还原态含量都较高。锌在河湖相水稻土以可还原态为主,在红壤性水稻土以醋酸溶解态为主。两种土壤上,铜和锌的3种不同形态含量与污泥施用量之间都有很好的相关性。连续提取对于研究重金属的形态分配比单独提取更有价值。     

施用高浓度Cu、Zn沼液盆栽对土壤理化性状及重金属含量的影响

以潮土、红壤为供试土壤,以玉米、小白菜和紫花苜蓿为供试作物,采用盆栽试验的方法,研究了高浓度的Cu、Zn猪场沼液施用30天后(盆栽开始30天)对几种土壤理化性质和不同形态重金属含量的影响。结果表明,与不施用沼液的对照相比,施用高浓度Cu、Zn猪场沼液使潮土p H下降、红壤pH显著升高,土壤p H值的这一变化在3种供试作物上表现相同;土壤脲酶、磷酸酶活性显著提高,而过氧化氢酶活性变化因土壤类型而异;土壤交换态和铁锰态Cu、Zn含量显著提高,且在红壤上的提高幅度显著大于潮土。研究认为,高浓度Cu、Zn猪场沼液施用于农田在改善土壤肥力性状的同时,也会使土壤重金属Cu、Zn含量特别是有效态含量增加,导致潜在环境风险增大。     

污泥土地利用研究：Ⅱ、连续化学提取法研究施污泥土壤重金属的有效性和环境风险

本文采用连续化学提取法研究了施用污泥土壤中重金属的形态分配及有效性。铜和在2种土壤上施用污泥前、后的形态分配都有所差异，铜在 湖相水稻土上可以氧化态为主：红壤性水稻土可氧化态和可还原态含量都较高。锌在河湖相水稻土以可还原态为主，在红壤性水稻土以醋酸溶解态为主，两种土壤上，铜和锌的3种不同形态含量与污泥施用量之间都有很好的相关性，连续提取对于研究重金属的形态分配比单独提取更有价值。     

黄土高原旱地连续施用锰肥的土壤效应研究

采用连续浸提形态分级方法，研究了连续施用锰肥17a后锰的土壤化学特性变化。结果表明：经过长期连续施用锰肥，土壤全锰和DTPA—Mn含量增加不多。土壤DTPA—Mn含量随试验时间的延长呈增加趋势，施锰土壤有效锰提高不多，土壤DTPA—Mn含量只增加了0．4～1．7mgkg^-1。土壤中的锰主要以矿物态存在，占土壤全锰含量的比例为87．3％～91.8％。碳酸盐态、氧化锰态和紧结有机态锰占全锰的比例相当，土壤中各形态锰按含量大致呈矿物态〉碳酸盐态〉氧化锰态〉紧结有机态〉松结有机态〉交换态的顺序。施入土壤的锰肥有91．1％～98．6％进入碳酸盐结合态、氧化锰结合态、紧结有机态和矿物态，只有很少一部分仍留在有效态锰库中。交换态和松结有机态锰对土壤锰的有效性起着主要作用，可以反映土壤锰的供给状况，碳酸盐态和紧结有机态锰不能反映土壤锰的有效性。     

施用猪粪对不同类型土壤中铜的赋存形态及小白菜吸收铜的影响

【目的】探讨猪粪中铜（Cu）的输入对土壤中Cu的赋存和生物有效性的影响。【方法】将1%和3%的腐熟猪粪（干猪粪∶秸秆=10∶1）添加到黄褐土、红壤、黑土、褐土中,分别老化0、1、2、3、5个月后,进行小白菜盆栽实验。【结果】与对照相比,施用猪粪使黄褐土、红壤、黑土和褐土土壤铜（Cu）全量分别显著增加了20.23%～50.43%、79.87%～142.6%、52.41%～76.43%和41.14%～92.24%。四种土壤中水溶态（F1）、碳酸盐结合态（F3）Cu占比均增加,施用3%猪粪的红壤未老化处理中F1-Cu和黄褐土未老化处理中F3-Cu增幅最大,分别达4.55%和16.47%。土壤铁锰氧化态（F5）、有机结合态（F6）Cu占比增加,残渣态（F7）占比降低。土壤有效态Cu的占比与猪粪老化时间呈显著负相关,3%猪粪老化5个月处理的黄褐土、黑土和褐土土壤有效态Cu占比分别降低12.85%、4.11%和3.68%,而红壤有效态Cu占比随老化时间变化不显著。在黄褐土中,腐殖酸结合态（F4）Cu的占比随猪粪老化时间的延长逐渐增加。施用猪粪显著增加小白菜对Cu的吸收,其中红壤的增幅最大,根系与地...     

LONG-TERM TRANSFORMATIONS AND REDISTRIBUTION OF POTENTIALLY TOXIC HEAVY METALS IN ARID-ZONE SOILS INCUBATED: I. UNDER SATURATED CONDITIONS

Solid-phase transformations of Cd, Cu, Cr, Ni and Zn, added as soluble salts at several levels to two arid-zone soils, were studied over a period of one year. The soils were maintained under a saturated-paste regime and sampled periodically. A selective sequential dissolution procedure was employed to determine the changes in metal distribution among six operationally defined solid-phase fractions. A function,U _ts was introduced to measure the fractional attainment of equilibrium of the soils following a perturbation. The direction and rate of redistribution of the added metals in the soils were affected by the nature of the metal, the soil properties and the metal loading level. Cd added to the soils was transferred from the exchangeable (EXC) into the carbonate (GARB) fraction. When soluble Cu, Cr, Ni and Zn were added at low loading levels, metals were transferred from the reducible oxides(RO) bound and easily reducible oxides (ERO) bound fractions and the EXC fraction, into the CARB fraction. However, at the higher loading level, metals were transferred from the EXC and CARB fractions into the organic matter bound (OM), ERO and RO fractions. TheU _ts function approached lower values as incubation continued but remained removed from 1. The overall flux of metals among fractions was the combined result of the readjustment of the metals in the native soil to changing conditions due to saturation, and the transfer of added soluble metals to the less labile fractions.     

石灰性土壤中锰素营养的研究——Ⅲ.土壤中MnSO4的转化及不同形态锰的含量变化

土壤中养分的存在形态不同对作物的可给性不同。从植物营养的角度虽然可将土壤中的锰分为三种形态:即速效锰(为作物直接吸收利用的二价锰)、缓效锰(主要为三价锰的氧化物,易于转化为二价锰)和无效锰(不易为作物吸收利用的四价锰),但用试验手段却很难获得这些结果。习用的方法是采用某种提取剂以提出某一形态的锰。本文根据盆栽试验和土壤测定的资料^[1,2],对易还原态、代换态、有机络合剂络合态、磷酸盐溶解态以及水溶态锰在石灰性土壤中的转化和含量变化进行了初步探讨。     

Long-Term Transformation and Redistribution of Potentially Toxic Heavy Metals in Arid-Zone Soils: II. Incubation at the Field Capacity Moisture Content

Solid-phase transformation of added Cd, Cu, Cr, Ni, Pb and Zn, in two arid-zone soils incubated in the field capacity moisture regime for one year, were studied. The heavy metals were fractionated into six empirically defined fractions using a selective sequential dissolution (SSD) protocol optimized for arid-zone soils. Each of these fractions was named based on the major soil component targeted for dissolution during the specific SSD step, but it is not assumed that they are mineralogically and chemically totally specific. The transformations of the metals in the two soils incubated at the field capacity regime were compared with those at the moisture saturation regime (Han and Banin, 1997). An initial fast stage of transformation of the soluble metals from the exchangeable (EXC) fraction to the less labile fractions (the carbonate (CARB) fraction for Cd, Pb, Zn, Ni and Cu, and the organic matter (OM) fraction for Cr, and to some extent Cu and Ni) occurred during the fractionation and within one hour after addition. This was followed by a second stage, involving long-term transformation processes of all metals: added Cd was transferred from the EXC into the CARB fraction; added Cr was transferred from the CARB to the OM fraction and Pb was transferred very slowly to the easily reducible oxide (ERO) fraction. Added Cu, Ni and Zn were transferred from the EXC and CARB fractions into the ERO fraction and to some extent OM and RO fractions. In Part I of this series, we reported that during incubation in the saturated moisture regime, Zn and Ni were transferred mainly into the RO and OM fractions. Cadmium, Cr and Pb underwent the same transformation pathways during the slow long-term process, with slightly different rates, in both water regimes. At low levels of addition, the incubated soils moved over one year towards a distribution similar to that of the native soil. At higher levels, the soils still remained removed from the quasi-equilibrium which characterized the native soil, even at the end of one year of incubation.     

水肥状况对土壤剖面中锰的移动和水稻吸锰的影响

水旱轮作条件下水麦缺锰是四川冲积性水稻土上主要的养分胁迫问题,为了深入探讨这一问题,作者利用模拟土柱试验研究了不同水肥状况对四川两种典型冲积土中锰的迁移,转化及其对水稻吸锰的影响。     

Zinc and copper in some soils of Egypt as related to other soil properties

Total Zn in alluvial and calcareous soils (average 138 and 70 ppm respectively) was significantly related to their contents of CaCO₃ (negatively), O.M. and clay (positively). Extracting Zn by Na₂EDTA gave the highest values for both soil types. Total Cu contents varied widely from 26 to 111 ppm in alluvial and from 15 to 30 ppm in calcareous soils. They were negatively correlated with the CaCO₃ contents. The pot experiments showed that EDTA(NH₄)₂CO₃, Na₂EDTA and DTPA are reasonable extractants for available Zn from both soil types. DTPA was efficient for all soils investigated, while Na₂ EDTA and EDTA-citrate were specific for extracting Cu from calcareous soils.     

Chemical Speciation of Heavy Metals in the Fractionated Rhizosphere Soils of Sunflower Cultivated in a Humic Andosol

Chemical speciation and bioaccumulation factor of iron (Fe), manganese (Mn), and zinc (Zn) were investigated in the fractionated rhizosphere soils and tissues of sunflower plants grown in a humic Andosol. The experiment was conducted for a period of 35 days in the greenhouse, and at harvest the soil system was differentiated into bulk, rhizosphere, and rhizoplane soils based on the collection of root-attaching soil aggregates. The chemical speciations of heavy metals in the soil samples were determined after extraction sequentially into fractions classified as exchangeable, carbonate bound, metal–organic complex bound, easily reducible metal oxide bound, hydrogen peroxide (H₂O₂)–extractable organically bound, amorphous mineral colloid bound, and crystalline Fe oxide bound. Iron and Zn were predominantly crystalline Fe oxide bound in the initial bulk soils whereas Mn was mainly organically bound. Heavy metals in the exchangeable form accumulated in the rhizosphere and rhizoplane soils, comprising <4% of the total content, suggesting their relatively low availability in humic Andosol. Concentrations of organically bound Fe and Mn in soils decreased with the proximity to roots, suggesting that organic fraction is the main source for plant uptake. Concentrations of Mn and Zn in the metal–organic complex also decreased, indicating a greater ability of sunflower to access Mn from more soil pools. Sunflower showed bioaccumulation factors for Zn, Fe, and Mn as large as 0.39, 0.05, and 0.04 respectively, defining the plant as a metal excluder species. This result suggests that access to multiple metal pools in soil is not necessarily a major factor that governs metal accumulation in the plant.     

添加物对土壤提取液中铜、镉生物毒性的影响

本文着重讨论添加物紫云英、CaCO₃、膨润土对土壤提取液中Cu、Cd的降毒效应及其金属形态的影响.测试结果表明,添加CaCO₃对降低红壤水溶态Cu、Cd和0.1mol/LHCl可提取态Cu、Cd含量及其毒性具有非凡的功能,并能使红壤中可溶态、交换态Cu、Cd明显向有机态、铁锰氧化物包被态和硫化物Cu、Cd转化.换言之,CaCO₃能使红壤中有效态金属向迟效态和无效态金属转化,致使其水、酸浸提液中Cu、Cd毒性被消除.     

SPECIFIC EFFECT OF MAGNESIUM ON THE HYDRAULIC CONDUCTIVITY OF SODIC SOILS

Exchangeable Mg does not have a specific effect on the hydraulic conductivity (HC) and clay dispersion in calcareous soils. Conversely, in well-weathered soils, which do not contain CaCO₃, a specific effect of exchangeable Mg is evident, on both HC losses and clay dispersion, when the Na/Mg soils are leached with distilled water (simulating rain water). Soil clays, when Mg-saturated, are chemically more stable and do not release electrolytes into the solutions: they thus disperse more easily when leached with distilled water. The presence of exchangeable Mg enhances the dissolution of CaCO₃ in calcareous soils, and the electrolytes prevent the dispersion of the clay and HC losses in the Na/Mg calcareous soils.     

Zinc Transformation in a Calcareous Soil as Affected by Applied Zinc Sulfate,Vermicompost, and Incubation Time

An experiment was conducted to evaluate the effect of zinc (Zn) rates and vermicompost levels on distribution of Zn forms of a calcareous soil. After incubation periods, soil samples were air dried, and a sequential extraction scheme was used to fractionate Zn into soluble and exchangeable, bound to carbonate, organically bound, bound to manganese (Mn) oxide, bound to amorphous iron (Fe) oxide, bound to crystalline Fe oxide, and residual forms. In untreated soil, Zn was mainly in the residual fraction. Increasing rates of applied Zn significantly increased all forms of Zn. Carbonate and residual forms showed the greatest increase. Application of vermicompost significantly increased all fractions except Mn-oxide form. This increase was more pronounced for organically bound, soluble, and exchangeable forms, indicating an increase in bioavailability of soil Zn. Incubation time significantly decreased soluble, exchangeable, and organically bound forms but increased other forms of Zn, meaning a significant reduction in Zn phytoavailability in soil with time.