珠江三角洲潜在生态风险:土壤重金属活化

珠江三角洲典型土壤模拟酸雨提取实验表明，土壤酸缓冲能力为菜园土大于水稻土大于赤红壤。酸化过程早期，铝铁胶体吸附共沉淀导致重金属溶出量增长不明显甚至下降；进一步酸化时，多数元素溶出量与加入酸量呈显著正相关。计算表明，在pH=4．5的酸雨作用下，溶液中Hg、Mn、Pb、Fe(以Fe2O3表示)浓度已超出Ⅱ级地表水标准，Cu、Zn大大高于渔业用水标准。可见，土壤元素活化溶出对水体生态环境有潜在的危害。     

江汉平原不同利用方式下土壤有机质与粘粒矿物的交互作用

以江汉平原四湖地区果园、旱地、水旱轮作、水田等利用方式下的土壤为研究材料,通过分析有机质质量分数、粘土矿物与铁铝氧化物的组成特点,探讨了该区土壤有机质与粘粒矿物之间的交互作用。结果表明各土地利用方式下表层土壤的粘土矿物均以2∶1型矿物为主,约占70%~80%;不同土地利用方式下表层土壤有机质质量分数、非晶质铁铝氧化物及铁的活化度大小顺序均为:水田水旱轮作旱田果园;土壤非晶质氧化铁(Feo)质量分数和粘土矿物中高岭石的质量分数分别与土壤有机质质量分数呈极显著正相关和显著正相关,且Feo与高岭石质量分数呈显著正相关。江汉平原四湖地区不同土地利用方式下,表层土壤中的Feo与高岭石强烈作用,利于土壤对有机碳的固定。研究结果有助于理解人为干扰下区域土壤的固碳机制。     

中国南方红壤中稀土元素分布的研究

中国南方红壤中稀土元素总量主要集中在１５０￣２００μｇ／ｇ范围内,且土壤剖面层的底土层含量较高;稀土元素分布模式表明,红壤中轻稀土元素间略有分异,而轻,重稀土元素间以及重稀土元素间没有明显分异,稀土元素含量与红壤中有机质,粘粒含量及阳离子交换量间的相关性很弱,而与红壤中铁锰氧化物及磷酸岩呈显著的正相关关系。     

土壤理化参数的反射光谱分析

土壤可见光和近红外波段(400~2 500 nm)反射光谱信息包含了大量土壤物理化学参数,土壤反射光谱测量简单、快速,无需破坏样品,而且还可以通过高光谱遥感方法制图。文中使用江苏国土生态地球化学调查中获取的大量土壤样品,研究了土壤阳离子交换量(CEC)、有机质含量、pH值、铁氧化物类型、铁铝硅等常量元素含量等重要土壤生态地球化学参数的光谱反应。结果显示,土壤CEC是进行光谱预测非常成功的参数,1 400、1 900和2 200 nm附近一阶导数光谱(FD)值或短波方向反射率值均可以很好地反映土壤CEC的大小;土壤有机质含量、铁氧化物类型、铁铝硅含量均可以在反射率光谱或其一阶导数(FD)值找到相关波段;土壤导数光谱存在的A、B、C和D峰使反射光谱方法不仅能够定量铁氧化物总量,还能鉴别铁氧化物矿物类型(针铁矿和赤铁矿)及其相对含量;江都土壤光谱的656 nm附近FD值与pH有很大相关性,但是江苏样品显示pH值光谱经验预测具有区域依赖性,可能与土壤类型有关,说明pH与光谱参数之间的关系并非一般的线性关系,而有更复杂的机制。     

长沙地区地表红壤铁氧化物矿物胶膜的矿物学

<正>在干旱—半干旱环境中的岩石表面常有黑色薄膜状岩石漆发育,在内陆沙漠、海滨沙漠、南北极地、高山、洞穴、岩石裂隙等陆生风化环境中皆有分布,其主要包含黏土矿物、铁锰氧化物、有机质等成分。无独有偶,在亚热带地区的表层红壤中也存在着类似的"薄膜",其中的铁锰氧化物矿物晶粒小至纳米级,这些矿物"薄膜"多附着于土壤基质表面,亦被称为矿物胶膜。本研究采用同步辐射微区X射线衍射和透射电子显微镜技术对表层红壤铁氧化物矿物胶膜中铁氧化物矿物的成分与结构进行了矿物学表征。     

石灰岩发育土壤团聚体形成机制研究

土壤团聚体是土壤最基本的结构单元。为了解岩溶地区石灰岩发育土壤团聚体的形成机制,选择贵阳市花溪区花溪水库石灰岩所发育的土壤为材料,采用干、湿筛法,分析团聚体颗粒的分级情况,并比较拆分有机质与钙镁铁铝离子间连接后四种离子含量的变化以及团聚体各粒级含量的变化。结果显示:团聚体是由细小颗粒在胶结物质有机质与钙镁铁铝离子结合下形成微团聚体,进一步形成更大粒级的团聚体,最后在分子力的作用下粘结土粒或者其他团聚体形成完整的团聚体结构;有机质与钙离子的结合是团聚体形成的主要胶结物质,其次为有机质与镁铁离子的结合,有机制与铝离子的结合作用不大,这与石灰岩矿物主要是碳酸钙有关;研究区发育土壤大粒级水稳性团聚体含量相对较高,土壤抗蚀性好,抵抗侵蚀能力强。      

铁铝复合氧化物对土壤Mn、Pb和Cd有效性的影响

利用氧化物对土壤重金属的吸附特性,研究了添加铁铝复合氧化物对土壤Mn、Pb和Cd有效性的影响。结果表明,在土壤中添加氧化物后,土壤中3种重金属的交换态含量明显降低。14天时间,添加铁铝氧化物后,土壤中交换态Mn、Pb和Cd的含量分别降低了64.8%、52.9%和89.51%,可见铁铝氧化物明显降低了土壤中Mn、Pb和Cd的有效性。通过方程拟合,建立了氧化物对土壤中交换态Mn、Pb和Cd的吸附模型,其中以Elovich方程和权函数方程拟合度较好,其次是抛物线扩散方程。     

H+和有机酸对可变电荷土壤铝释放的动力学研究

利用流动搅动法研究了在模拟酸雨和低分子量有机酸条件下可变电荷土壤铝释放的动力学特征,结果表明,在pH3.5的模拟酸雨作用下,红壤和黄壤中流出液铝的浓度范围约为15～40μmol/L,铝的释放快反应来源于土壤交换性铝和有机络合态铝,铝的释放慢反应对应于含铝矿物的溶解。赤红壤和砖红壤上在0～300min内流出液铝的浓度范围约为1～5μmol/L,流出液pH值大于4.5,对H 的缓冲作用表现为阳离子交换、SO24-的专性吸附释放OH-和矿物表面的质子化;当流出液pH值小于4.5时,H 开始溶解土壤中的含铝固相,铝释放的最后浓度为20～30μmol/L。用相近pH值的有机酸溶出土壤铝的浓度比pH3.5的模拟酸雨要高,特别是在砖红壤上,开始就有大量铝的释放,其浓度为20～75μmol/L,红壤上是70～150μmol/L,随时间延长,流出液中的铝浓度分别为10～20μmol/L和20～30μmol/L。有机酸作用下铝的释放机制主要是有机酸被土壤吸附后,有机酸与位于表面晶格中的铝原子形成络合体,促进了铝的溶解;其次是有机酸的吸附掩盖了土壤表面的质子化过程,增强了酸的溶解,以及有机配体对铝的络合作用,增加了铝的释放量。不同有机酸对铝的溶出能力也有不同,其释放铝能力的大小为:柠檬酸>酒石酸>苹果酸,这取决于有机配体与铝的络合能力。     

广西贵港地区富硒土壤地球化学特征及成因探讨

文章针对广西贵港地区富硒土壤的地球化学特征及富硒成因进行分析探讨,发现该区土壤不仅具有富Se特征,同时还富集其他多种微量元素;该地区的富硒土壤主要与泥盆系、石炭系和二叠系碳酸岩岩层合Se高,以及与原始海洋环境形成的海洋生物有机质和酸性环境下的铁铝氧化物有关。     

土壤矿物学特征在华南赤红壤有机质稳定中的调控作用研究

以广州市从化的赤红壤剖面为研究对象,系统测定了土壤的pH值和机械组成,土壤剖面中有机质含量、氧化铁矿物和粘土矿物的含量及分布特征,并进行了相关性分析。研究结果表明,赤红壤剖面的总有机质、稳定有机质含量、矿物稳定有机质含量和生化稳定有机质含量的变化趋势在整体上是一致的,均随深度的增加而降低。其中,矿物稳定有机质主要存在于土壤剖面的中间层,氧化铁矿物则大都集中在土壤剖面的中上层;赤红壤剖面各层位中高岭石含量都占绝对优势,为58.7%~84%,蒙脱石的含量次之,为8.5%~16.8%,除此之外,还含有较多的三水铝石。蒙脱石的含量随深度增加而降低,高岭石和三水铝石的含量随深度增加而升高。土壤有机质与氧化铁矿物的相关性较之与粘土矿物、三水铝石要大得多,有机质含量与无定形铁含量的相关系数均高于0.90,与蒙脱石、高岭石、三水铝石的相关系数分别为0.697 1、-0.681 2、-0.049 8,可见无定形铁在土壤有机质稳定中起着重要作用,提醒应更加关注土壤中有机质碳库稳定锁定中的矿物学机制及其影响因素。     

Toluene sorption behavior on soil organic matter and its composition using three typical soils in China

The effect of soil organic matter (SOM) content and composition on sorption behavior of toluene for fluvo-aquic, red and black soils in China was investigated in batch experiments. Tested SOM was fractionated into two primary sorptive domains (‘soft’ and ‘hard’) to explain the dependence of sorption behavior on SOM composition. All the tested soils exhibited similar sorption kinetics and nonlinear sorption isotherms. Soils with high SOM content possessed a high sorptive capacity. Clay minerals also contributed to the sorptive capacity, especially for fluvo-aquic and red soils with low SOM content. In comparison, after removing most ‘soft’ SOM fraction from soils through hydrogen peroxide treatment, the residual ‘hard’ SOM fraction of three soil samples exhibited a slower sorption rate and a less sorption capacity compared to the untreated soil samples. The nonlinear degree of sorption was positively correlated with the content of ‘hard’ SOM for all soil samples. This is explained by the combined effect of SOM content and the composition on toluene sorption rates, sorption capacity and nonlinear degree of sorption of three typical soils in China.     

Stable carbon isotopic composition of soil organic matter in the karst areas of Southwest China

This study dealt with the distribution characteristics of soil organic carbon （SOC） and the variation of stable carbon isotopic composition （δ^13C values） with depth in six soil profiles, including two soil types and three vegetation forms in the karst areas of Southwest China. The δ^13C values of plant-dominant species, leaf litter and soils were measured using the sealed-tube high-temperature combustion method. Soil organic carbon contents of the limestone soil profiles are all above 11.4 g/kg, with the highest value of 71.1 g/kg in the surface soil. However, the contents vary between 2.9 g/kg and 46.0 g/kg in three yellow soil profiles. The difference between the maximum and minimum δ^13C values of soil organic matter （SOM） changes from 2.2‰ to 2.9‰ for the three yellow soil profiles. But it changes from 0.8‰ to 1.6‰ for the limestone soil profiles. The contrast research indicated that there existed significant difference in vertical pattems of organic carbon and δ^13C values of SOM between yellow soil and limestone soil. This difference may reflect site-specific factors, such as soil type, vegetation form, soil pH value, and clay content, etc., which control the contents of different organic components comprising SOM and soil carbon turnover rates in the profiles. The vertical variation patterns of stable carbon isotope in SOM have a distinct regional character in the karst areas.     

The effect of silica and natural organic matter on the Fe(II)-catalysed transformation and reactivity of Fe(III) minerals

The Fe(II)-catalysed transformation of synthetic schwertmannite, ferrihydrite, jarosite and lepidocrocite to more stable, crystalline Fe(III) oxyhydroxides is prevented by high, natural concentrations of Si and natural organic matter (NOM). Adsorption isotherms demonstrate that Si adsorbs to the iron minerals investigated and that increasing amounts of adsorbed Si results in a decrease in isotope exchange between aqueous Fe(II) and the Fe(III) mineral. This suggests that the adsorption of Si inhibits the direct adsorption of Fe(II) onto the mineral surface, providing an explanation for the inhibitory effect of Si on the Fe(II)-catalysed transformation of Fe(III) minerals. During the synthesis of lepidocrocite and ferrihydrite, the presence of equimolar concentrations of Si and Fe resulted in the formation of 2-line ferrihydrite containing co-precipitated Si in both cases. Isotope exchange experiments conducted with this freeze-dried Si co-precipitated ferrihydrite species (Si-ferrihydrite) demonstrated that the rate and extent of isotope exchange between aqueous Fe(II) and solid ⁵⁵Fe(III) was very similar to that of 2-line ferrihydrite formed in the absence of Si and which had not been allowed to dry. In contrast to un-dried ferrihydrite formed in the absence of Si, Si-ferrihydrite did not transform into a more crystalline Fe(III) mineral phase over the 7-day period of investigation. Reductive dissolution studies using ascorbic acid demonstrated that both dried Si-ferrihydrite and un-dried 2-line ferrihydrite were very reactive, suggesting these species may be major contributors to the rapid release of dissolved iron following flooding and the onset of conditions conducive to reductive dissolution in acid sulphate soil environments.     

Fe–Al–organic Colloids Control of Trace Elements in Peat Soil Solutions: Results of Ultrafiltration and Dialysis

Size fractionation of ~40 major and trace elements (TE) in peat soil solutions from the Tverskaya region (Russia) has been studied using frontal filtration and ultrafiltration through a progressively decreasing pore size (5, 2.5, 0.22 μm, 100, 10, 5, and 1 kD) and in situ dialysis through 6–8 and 1 kD membranes with subsequent analysis by ICP-MS. In (ultra) filter-passed permeates and dialysates of soil solutions, Fe, Al, and organic carbon (OC) are well correlated, indicating the presence of mixed organo-mineral colloids. All major anions and silica are present in “dissolved” forms passed through 1 kD membrane. According to their behavior during filtration and dialysis and association with mineral or organic components, three groups of elements can be distinguished: (i) species that are weakly affected by size separation operations and largely (>50–80%) present in the form of dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, As, Mn) with some proportion of small (1–10 kD) organic complexes (Ca, Mg, Sr, Ba), (ii) biologically essential elements (Co, Ni, Zn, Cu, Cd) mainly present in the fraction smaller than 1 kD and known to form strong organic complexes with fulvic acids, and, (iii) elements strongly associated with aluminum, iron and OC in all ultrafiltrates and dialysates with 30–50% being concentrated in large (>10 kD) colloids (Ga, Y, REEs, Pb, Cd, V, Nb, Sn, Ti, Zr, Hf, Th, U). For most trace metals, the proportion in the colloidal fraction correlates with their first hydrolysis constant. This implies a strong control of negatively charged oxygen donors present in inorganic/organic colloids on TE distribution between aqueous solution and colloid particles. It is suggested that these colloids are formed during plant uptake of Al, Fe, and TE from mineral matrix of deep soil horizons and their subsequent release in surface horizons after litter degradation and oxygenation on redox or acid/base fronts. Dissolved organic matter stabilizes Al/Fe colloids and thus enhances trace elements transport in soil solutions.     

Fe–S mineralization in the Jurassic biogenic remains (Częstochowa,Poland)

Various Fe–S minerals of the mackinawite–greigite–pyrite association, ubiquitous in biogenic remains from Jurassic mudstones, have been described in detail in an SEM–EDS study. Two diagenetic stages of Fe sulphide formation and preservation in the Jurassic organic skeletons are identified. In the first stage, pyrite formed as euhedra and framboids shortly after deposition, mainly in the interiors of the skeletons which still contained labile organic matter. The second stage of iron sulphide formation was related to the later stages of diagenesis, when the influence of the surrounding sediment was more dominant, although some organic matter was still present in the biogenic skeletons. A Fe-rich carbonate–aluminosilicate cement was then introduced between the earliest iron sulphides and later subsequently sulphidized, to form a metastable iron monosulphide of mackinawite composition and then greigite.     

Effects of Soil Composition on Zn Speciation in Drainage Waters from Agricultural Soils

The influence of Zn speciation on Zn transport by drainage from different soils to surface water is examined in a stream catchment in an agricultural area. Drainage waters were collected from two types of soils, a mineral soil (MS) and a soil rich in organic matter (OS) by means of artificial drainage pipes. The speciation of dissolved Zn in the stream and the drainage waters was determined using ligand-exchange and voltammetry. About 50–95% of dissolved Zn is bound in strong complexes, and the free Zn²⁺ ion concentration is in the range of 1–16% of dissolved Zn. A substantial part of Zn is present in weaker organic or inorganic complexes. The simulated Zn speciation using the WHAM VI model is compared to the determined speciation. Free Zn²⁺ concentrations predicted by the WHAM VI model are generally higher than the analytically determined free Zn²⁺, but are mostly within the same order of magnitude. Effects of different soil organic matter content on Zn speciation and transport are discussed. Zn speciation in the drainage at the OS site is influenced by the distribution of organic matter between the solid and solution phase. The abundant organic Zn complexes in solution contribute to facilitate Zn transport from soil into surface waters, through the drainage at the OS site. Drainage from the OS site contributes about twice as much Zn input to the receiving water as the MS soil, as related to specific area. The mineral soil contains much lower organic matter, and a part of Zn bound with inorganic phases can hardly be released by dissolved organic ligands, leading to much higher Zn retention at the MS site.     

黔西北地区二叠纪玄武岩古风化壳常量元素的地球化学特征

通过对峨眉山玄武岩古风化壳进行野外调查、取样和分析测试工作,认为: ①贵州西部广泛出露峨眉山玄武岩,晚二叠世古气候温润潮湿,利于峨眉山玄武岩风化形成含Fe、Ti的黏土矿物和铝质黏土矿物的古风化壳,该风化壳受古地理环境和峨眉山玄武岩控制。②相对玄武岩而言,铝质黏土岩主量元素含量特征表现为富TiO₂、Al₂O₃,轻度亏损SiO₂,明显亏损TFe,其他主量元素大量流失; 铁质黏土岩主量元素含量特征表现为富TFe、TiO₂, 轻度富Al₂O₃,但相对于铝质黏土岩,TiO₂的富集程度偏低,SiO₂亏损明显,其他元素亦大量流失。③由于晚二叠世频繁的海侵作用,水位较高的区域,风化壳下部处于较还原的条件下,Fe被还原成易溶的二价状态或在有机质的作用下迁出风化壳,而Ti由于存在形式较为稳定,继续保存在黏土矿物中,与Fe发生分异; 局部水位较浅的氧化环境及重力分异作用下,黏土矿物与铁矿物由于比重差异而分选开来,形成Fe与Al、Ti的分异,并伴随铁矿、钛矿和铝土矿的富集。该富集规律的发现对寻找该区铁、钛和铝土矿有一定的理论指导意义。     

加积型网纹红土网纹化机制及形成环境

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有机质对海相软土物理力学特性的影响效应分析

有机质是海相软土的重要组成部分,其对土体物理力学性质的影响有待深入研究。以连云港地区全新世海相软土为例,进行百组土体有机质物理力学试验。结果表明,研究区软土有机质含量平均值为0.98%,在0.90%～1.00%这个区间分布最为广泛。有机质含量在空间上分布不均,平行海岸线较垂直海岸线土体有机质含量变化小,自上向下变化规律...