钙质土颗粒咬合作用机制

形状不规则的钙质土在剪切应力作用下土颗粒之间存在咬合作用,从而使抗剪强度显著提高。为研究钙质土颗粒的咬合作用机制,针对不同粒径的钙质土开展三轴固结不排水和固结排水试验,并对颗粒形状进行了分析,揭示了钙质土咬合力的形成机制和表现形式。研究表明：①不规则的颗粒形状是钙质土产生咬合力的前提条件;②在不同粒径的钙质土中,因不同形状颗粒的含量存在差异导致咬合力大小也不同;③咬合力大小受应力水平影响较为明显,在低围压下咬合作用导致剪胀而提高内摩擦角;在高围压下咬合作用克服颗粒强度做功,造成颗粒破碎,提高黏聚力值而降低有效内摩擦角。钙质土颗粒之间的咬合对强度有明显增强作用,在工程设计中应充分考虑咬合力的影响。     

钙质砂颗粒的形状分析

钙质砂是一种含碳酸钙达50 %以上的海洋生物成因的粒状材料。颗粒棱角度高、形状不规则,影响钙质砂的压缩、填充等力学性能。通过光学显微镜获取钙质砂颗粒的几何投影图像,借助Matlab图像处理软件,分别运用常规统计方法和分形理论对钙质砂颗粒的几何形态进行了描述,并结合钙质砂特殊的生物成因对其表现出的特性进行了分析。结果表明：钙质砂颗粒的形状具有分形特性,且随着颗粒粒径的减小,分形特性越明显。     

北京平原区两年内土壤中五种重金属元素化学形态变化及生物有效性

为了监测北京市平原区2015年和2016年土壤中5种重金属As、Cd、Hg、Pb、Zn化学形态的变化趋势,运用Tessier连续提取法对土壤重金属进行了形态分析,并对影响重金属元素生物有效性的因素进行研究。结果表明,2年内研究区表层土壤重金属元素的形态变化微弱,有效态含量以Cd元素最高,达到45.67%,故潜在生态危害性最大;其次为Zn元素,达12.16%,其中碳酸盐结合态占比虽大,但由于研究区土壤呈偏碱性,Zn元素的迁移能力较弱,潜在危害性较小;As、Hg、Pb均以难迁移态存在,故潜在危害性也较小。土壤重金属元素的生物活性系数及迁移系数分别为:CdZnPbAsHg和CdAsZnPb=Hg,其中Cd元素2年的生物活性系数和迁移系数最高,展现出较强的生物活性和迁移能力,其余重金属元素的活性系数和迁移系数较低,潜在危害性较弱。影响重金属元素生物有效性的因素较复杂,以重金属元素全量为主,p H、有机质、CEC等理化性质次之。     

天然胶结钙质土强度及微观结构研究

自20世纪80年代起,国内就开展了关于岛礁钙质土岩土工程性质的研究工作,至今已经取得了大量的研究成果,但上述研究工作均是针对松散钙质土进行的,针对岛礁上广泛分布的胶结钙质土的研究工作尚未系统开展。而国外大量工程实践表明,胶结钙质土具有完全不同于松散钙质土的工程性状。针对天然胶结钙质土的空间各向异性,从微观角度研究影响其强度的主要参数,为今后的胶结钙质土的分类研究提供理论指导。文中采用多种试验研究方法,最后建立了天然胶结钙质土的密度、胶结度、孔隙度、颗粒大小等参数与强度间的对应关系,当前的研究结果表明,天然胶结钙质土的密度及胶结度与强度间存在良好的相关性。     

钙质土的剪切特性试验研究

钙质土因其颗粒形状不规则、易破碎、高孔隙比等特征,其力学性质较为特殊。采用室内大型直接剪切试验设备,对取自南海珊瑚礁和三亚岸礁的粗颗粒钙质土进行了直剪试验,研究了粗颗粒钙质土在不同含水率、不同密度和不同矿物组成条件下的钙质土剪切特性。结果表明,粗颗粒钙质土表现出与常规无黏性土截然不同的力学性质,即（1）与石英砂相比,表观黏聚力较大,内摩擦角较高,软化性较弱;（2）表观黏聚力随着平均粒径的增大而增大,内摩擦角随着干密度的增大而增大;（3）与峰值强度相比,土体剪切破坏后其残余强度的表观黏聚力锐减而内摩擦角仅略有减小。研究成果可为岛礁工程建设提供借鉴,也可为其他粗颗粒土的研究提供参考。     

石灰性土壤中有效磷的电感耦合等离子体发射光谱法测定

方法采用0.5 mol/L NaHCO3浸提石灰性土壤中的有效磷,电感耦合等离子体原子发射光谱法测定。研究了土壤滤液的酸化、颜色、浸提温度以及振荡时间等对浸提结果的影响,方法检出限(3s)为0.18 mg/kg,定量限(6s)为0.36 mg/kg,通过对石灰性土壤有效态标准物质GBW07413a、GBW07459和GBW07460的12次测定,方法准确度和精密度均小于4.5%。     

Chemical speciation of trace metals at the air-sea interface: The application of an equilibrium model

Air-sea interfacial solutions have characteristically high concentrations of trace metals, microorganisms, organic compounds, and solids relative to bulk solutions. The potential for the chemical interaction of an array of trace metals in the interfacial regions with complexing organic ligands and adsorbing solid surfaces has been evaluated through the use of an equilibrium computer model. Computations suggest that higher interfacial accumulations of copper and lead may occur relative to cadmium and mercury. These results are found to be generally compatible with available field data describing trace metal interfacial accumulation. The forms of metals found to be partitioned between bulk and interfacial solutions are consistent with the hypothesis that solid surface adsorption and dissolved organic complexation reactions bring about metal enrichment at the surface microlayer.     

Using chemical analysis and modeling to enhance the understanding of soil solution of some calcareous soils

The chemistry of soil solutions can be altered by human activities, due to the intense agricultural and husbandry, leading to leaching of nutrients and subsequently elevating ground water levels. Multivariate statistical and inverse geochemical modeling techniques were used to determine the main factors controlling soil solution chemistry of calcareous soils. In this research, a total of 21 calcareous soils was characterized and assessed for soil solution using soil column. The major cations in the studied soil solutions were in the decreasing order as Ca²⁺ > Mg²⁺ > Na⁺ > K⁺. The anions were also arranged in decreasing order as HCO $ _{3}^{ - } $  > Cl $ ^{ - } $  > SO $ _{4}^{2 - } $  > NO $ _{3}^{ - } $ . Concentrations of NO $ _{3}^{ - } $ , P, and K⁺ in soil solutions were in the range of 6.8–307.5 mg l^?1 (mean 63.2 mg l^?1), 5.0–10.4 mg l^?1 (mean 5.9 mg l^?1), and 2.8–54.6 mg l^?1 (mean 11.3 mg l^?1), respectively. Results suggest that the concentration of P in the soil solutions could be primarily controlled by the solubility of dicalcium phosphate dihydrate and dicalcium phosphate. Interactions between soil properties and observed solubility of nutrients were described, and put into empirical multivariate formulations. Obtained equations contained electrical conductivity (EC) as a key factor in determining nutrients solubility. Inverse geochemical modeling of soil solution using PHREEQC indicates the dissolution of calcite, anhydrite, halite, CO₂ (g), N₂ (g), and hydroxyapatite, and precipitation of sulfur. Cation exchange between Ca²⁺, Mg²⁺, K⁺ and Na⁺ occurred with Mg²⁺ and K⁺ into the solution, and Ca²⁺ and Na⁺ out of the solution. Determination of soil solution will improve soil management in the area, and preventing groundwater deterioration.     

Chemical speciation of fine particle bound trace metals

This study reported quantifications of fine particle bound trace metals and their potential health risks for residents in Guangzhou, a rapidly developing and most populated city in South China. The fine particle samples were collected from October 29^th. to November 8^th. of 2006 at two different elevations in a mainly residential area and analyzed for the total concentration of aluminum, iron, zinc, lead, manganese, copper, arsenic, chromium, nickel, cadmium, molybdenum and cobalt. Results showed that the fine particle concentrations ranged from 95.8μg/m³to 194.7 μg/m³ at the ground and 83.3-190.0 μg/m³ on the roof, which were much higher than the 24 h fine particle standard (35 μg/m³) recommended by USEPA. The total concentrations of zinc, lead, arsenic, chromium and cadmium in fine particle were 504.8, 201.6, 24.3, 7.7 and 4.4 ng/m³, respectively, which were comparable to other major cities of China, but much higher than major cities outside of China. A sequential extraction procedure was used to fractionate these fine particle bound metals into four different fractions. Results indicated that most toxic metals were mainly distributed in bioavailable fractions. For instance, about 91 % of cadmium, 85 % of lead and 74 % of arsenic were in bioavailable forms. Risk calculations with a simple exposure assessment model showed that the cancer risks of the bioavailable fractions of arsenic, chromium and cadmium were 3 to 33 times greater than usual goal, indicating serious health risks to the residents in this urban area.     

扁铲侧胀试验在浅海钙质土力学特性评价中的应用

利用扁铲侧胀仪对海底浅层钙质土进行原位测试,能够一次获得多个评价土性的试验参数。试验表明,由于波浪循环动荷载的作用使得海底表层（深1～2 m）钙质砂的密实度比其紧邻的下部偏大,以珊瑚礁为主要胶结物的钙质土,内部具有大的孔隙或松散堆积体结构是造成海底浅层钙质砂表层与浅部土体的扁铲侧胀压力明显变化的主要原因。扁铲试验结果与现场标准贯入试验具有较好的相关性,基于Seed公式推导的适合于计算水下平均动应力比的简化公式能够较好地用于对不同地震烈度下海底浅层钙质土液化可能性的判别。     

钙质砂的休止角研究与工程应用

砂土的天然休止角对土堆设计、基坑设计和边坡稳定性研判有重要的指导意义。砂土的天然休止角受土颗粒的摩擦特性、颗粒形状、粒径和含水状态等诸多因素的影响。开展了钙质砂的天然休止角试验,研究了多种因素对钙质砂天然休止角的影响规律。结果表明：钙质砂3种常见颗粒形状中,片状休止角最大,枝棒状次之,块状最小;钙质砂天然休止角随着粒径的增大而增大;当平均粒径相同时,天然休止角随着不均匀系数的增大而增大,随着曲率系数的增大而减少;通过与标准石英砂的对比试验发现,石英砂的天然休止角小于钙质砂天然休止角。对现场钙质砂边坡测量后表明,钙质砂地基经过振冲挤密后基坑开挖最大坡角略大于室内测得的天然休止角。研究结果对钙质砂土堆和基坑设计等工程实践有一定指导意义。     

饱和钙质砂爆炸密实动力特性试验研究

开展饱和钙质砂爆炸密实动力特性试验研究,探索饱和钙质砂爆炸密实机制和密实效果,对钙质砂地层中进行的工程建设有重要的理论意义和工程实用价值。通过控制爆炸参数,测试不同参数作用时钙质砂爆炸前后声波特性和表面沉降规律,揭示饱和钙质砂爆炸密实动力特性。试验结果表明：钙质砂高孔隙比和颗粒破碎特性对爆炸密实效果有重要影响。爆炸密实作用后,在爆炸近区,钙质砂颗粒受到较强爆炸冲击作用,导致钙质砂颗粒破碎而形成破碎区和压缩区,压缩区随着时间的推移有松弛的趋势,钙质砂颗粒结构重新固结过程在爆炸后2 h内基本完成。     

Heavy metal accumulation in soil after application of organic wastes

Municipal solid waste compost and cattle manure are used as organic fertilizers in agriculture and horticulture. These wastes, however, may also have some negative effects on the agricultural environment. This study investigates the effects of municipal solid waste compost of Kerman (MSC) and cattle manure (CM) on availability of the heavy metal in calcareous soil (extractable with EDTA) in greenhouse conditions. The MSC and CM were mixed thoroughly with soil at rates of 0%, 2%, and 4% of dry matter. After 90 days of incubation, the soil samples were analyzed. Addition of levels of each two organic wastes into soil significantly decreased the soil pH and increased the soil EC as compared with control (unamended soil).The available contents (EDTA-extractable) of Cd, Pb, Cu, Zn, and Cu in the soil samples were increased because of each two organic treatments applied. The heavy metal contents in the soil samples amended with MSC were more than CM. The heavy metal contents of organic wastes were well below the maximum allowed by USEPA. It is recommended that in Iran, the legal maximum permissible limit for heavy elements in organic wastes must be determined.     

Nickel speciation in Sebertia acuminata,a plant growing on a lateritic soil of New Caledonia

Nickel speciation in a nickel hyperaccumulating plant (Sebertia acuminata) and its associated soil of southern New Caledonia was studied using various analytical methods. The soil is formed of iron oxides (goethite, hematite), which contain almost all the nickel. The available nickel is probably linked to the organic matter in the litter. Sebertia acuminata, acts as a nickel pump, and concentrates the metal in its leaves. It partitions nickel and silica; nickel is concentrated in the cells (probably in the vacuoles) as organometallic complexes, whereas silica forms the framework of the cells, and the phytolithes. A thorough study of these plants seems essential in order to define the soil–plant relations, and to propose appropriate ways for ecological restoration. To cite this article: N. Perrier et al., C. R. Geoscience 336 (2004).     

Transport and fate of nitrate within soil units of glacial origin

Questions concerning the influence of soil type and crop cover on the fate and transport of nitrate (NO₃⁻) were examined. During a growing season, soils derived from glacial material underlying either corn or soybeans were sampled for levels of NO₃⁻ within the pore water. Measured levels of NO₃⁻ ranged from below detection limit to 14.9 g NO₃⁻ per kilogram of soil (g/kg). In fields with the same crop cover, the silty-clayey soil exhibited a greater decrease in NO₃⁻ levels with depth than the sandier soil. Crop uptake of NO₃⁻ occurs within the root zone; however, the type of crop cover did not have a direct impact on the fate or transport during the growing season. The soils underlying soybeans had an increase in NO₃⁻ levels following harvest, suggesting that the decomposition of the soybean roots contributed to the net gain of NO₃⁻ in the shallow soil. For all of the soil types, conditions below 100 cm are conducive for microbial denitrification, with both a high water saturation level (>60%) and moderate organic carbon content (1–2%). At depths below 100 cm, temporal differences in NO₃⁻ levels of over a magnitude, up to a 95% reduction, were recorded in the soil units as the growing season progressed. Physical properties that control the transport of NO₃⁻ or denitrification have a larger influence on NO₃⁻ levels than crop type.

The impact of acid rain on phosphorus leaching from a sandy loam calcareous soil of western Iran

Simulated acidic precipitation (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 and 7.0 were conducted using column leaching to determine impacts of simulated acid rain on phosphorus (P) leaching from a calcareous sandy loam soil over a 40-day period. Soil columns were irrigated every day to make a total of 1,061 mm, equivalent to 3.5 years of rainfall (based on average annual rainfall). Leachates were collected and analyzed for anions and cations. There was significant nonlinear correlation between the amount of P leached and the simulated acid rain (R ² = 0.61). Losses of P from the pH 2.5 and 7.0 treatments were 1.23, and 1.32 mg kg⁻¹, respectively. The results showed that the amount of P leached from pH 4 (1.46 mg kg⁻¹) and 5 treatments (1.52 mg⁻¹ kg⁻¹) were significantly larger than other treatments. Linear equation adequately described leaching of P in different treatments. The slope (mg kg⁻¹ day⁻¹) in the linear equation was defined as the leaching rate and for the pH 2.5 was 0.0354, and 0.0382 and 0.0406 for pH 4.5 and 7.0, respectively. The geochemical code Visual MINTEQ was used to calculate saturation indices. Leaching of P in different treatments was controlled by rate-limited dissolution of hydroxyapatite, β-tricalcium phosphate and to some extent octacalcium phosphate. The results indicate that acid rain in calcareous sandy loam soils may pose a risk in terms of groundwater contamination with P.     

Metal speciation in rivers affected by enhanced soil erosion and acidity

Dissolved (<1 kDa), colloidal (1 kDa–0.45 μm) and particulate (>0.45 μm) size fractions of 30 elements were determined for four rivers (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), including 12 low-order inflow streams, largely affected by soil erosion and acidity in SW Finland. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these rivers. Total metal concentrations were relatively high but most of the elements occurred mainly in a colloidal or particulate form and even elements expected to be very soluble occurred to a large extent in colloidal form. According to geochemical modelling these patterns could be explained by in-stream metal complexation/adsorption only to a limited extent. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of acid sulphate (AS) soils, known to exist in the catchment, could be clearly distinguished in Sirppujoki river as it had very high concentrations of dissolved metals, while in the two nearby rivers (Laajoki and Mynäjoki) the influence of AS soils was largely masked by eroded phyllosilicates. In Paimionjoki river the colloidal and particulate fractions dominated very strongly, indicating that total metal concentrations are almost solely controlled by erosion of phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high “background” metal concentrations due to erosion of relatively non-toxic colloidal/particulate phyllosilicates. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring and/or speciation modelling can lead to a great overestimation of the water toxicity in this environment.     

土壤和沉积物中元素的化学形态及其顺序提取法

介绍了形态分析的概念和化学形态分析方法,探讨了广泛应用于土壤、沉积物重金属形态分析中的Tessier和BCR顺序提取方案及其异同,综述了顺序提取方法在地球化学、环境科学、农业科学等方面的应用及中国相关标准物质的研制现状。