Soil Chemical Analysis

Preface.- Contributors.- List of Abbreviations.- Section 1: Basic Principles: Introduction.-Sources of Heavy Metals and Metalloids in Soils.- Chemistry of Heavy Metals and Metalloids in Soils.- Methods for the Determination of Heavy Metals and Metalloids in Soils.- Effects of Heavy Metals and Metalloids on Soil Organisms.- Soil-Plant Relationships of Heavy Metals and Metalloids.- Heavy Metals and Metalloids as Micronutrients for Plants and Animals.-Critical Loads of Heavy Metals for Soils.- Section 2: Key Heavy Metals And Metalloids: Arsenic.- Cadmium.- Chromium and Nickel.- Cobalt and Manganese.- Copper.-Lead.- Mercury.- Selenium.- Zinc.- Section 3: Other Heavy Metals And Metalloids Of Potential Environmental Significance: Antimony.- Barium.- Gold.- Molybdenum.- Silver.- Thallium.- Tin.- Tungsten.- Uranium.- Vanadium.- Glossary of Specialized Terms.- Index.

Heavy metals in soils : trace metals and metalloids in soils and their bioavailability

Transformation of halogenated organic compounds (HOCs) by zero-valent iron represents one of the latest innovative technologies for environmental remediation. For example, iron can be used to construct a reactive wall in the path of a contaminated groundwater plume to degrade HOCs. In this paper, an efficient method of synthesizing nanoscale (1−100 nm) iron and palladized iron particles is presented. Nanoscale particles are characterized by high surface area to volume ratios and high reactivities. BET specific surface area of the synthesized metal particles is 33.5 m2/g. In comparison, a commercially available Fe powder (<10 μm) has a specific surface area of just 0.9 m2/g. Batch studies demonstrated that these nanoscale particles can quickly and completely dechlorinate several chlorinated aliphatic compounds and a mixture of PCBs at relatively low metal to solution ratio (2−5 g/100 mL). Surface-area-normalized rate constants (KSA) are calculated to be 10−100 times higher than those of commercially availa...

Synthesizing Nanoscale Iron Particles for Rapid and Complete Dechlorination of TCE and PCBs

Über die Adsorption in Lösungen

Positive ions that are available in soils absorb on grain surfaces. The total sum of cations that can be absorbed bij a soil/sediment at a certain PH is defined by the cation-exchange capacity (CEC, in meq g-1: mol equivalents per gram). The uptake of cations is an important parameter in agriculture and the larger the CEC, the more cations can be absorbed to the soil. The CEC depends highly on the pH of soil and sediments, where the CEC decreases with decreasing PH (increasing acidity). The exchange of ions on sediments occurs commonly fast on geological time scales, but the kinetics of adsorption in natural environments is still poorly understood. The strength of the bonding between the cations and the sediments varies from weak Van der Waals bondings (physical adsorption) to strong chemical bonds. The CEC is widely used for agricultural assessment because it is a measure of general soil fertility as well as an indicator of structural stability because CED is capabel of enhancing development of shrinkage cracks. The list below shows the CEC for different types of minerals. The data indicate that the CEC can vary over 2 orders of magnitude for various types of , minerals and can vary one order of magnitude within one soil type. Cation exchange capacity for different types of sediment (Eisma, 1992; Locher and de Bakker, 1990):

Cation exchange capacity.

Zero-valent iron for the in situ remediation of selected metals in groundwater

Paucity of understanding mechanisms relevant to the generation of subsurface mobile colloids is a major limitation to our current knowledge of colloid-facilitated contaminant transport. To evaluate the roles of natural organic materials and pore water velocity on mobile colloid generation, colloids generated from 14-m{sup 3} lysimeters containing reconstructed soil profiles were collected and characterized. Colloids generated during low flow rates were 1030% less abundant, contained at least 65% more iron oxides and gibbsite, were 80% smaller, and had 40% greater electrophoretic mobility than colloids generated during higher flow rates. Quartz, kaolinite, and hydroxy-interlayered vermiculite were enriched by at least 32% in colloids generated during faster flow rates. Mobile colloid surface charge was greatly enhanced by organic carbon (OC) coatings. Concentrations of OC associated with mobile colloids were higher than or equal to the OC concentrations existing in the bulk soils from which the mobile colloids were derived. The profound effects of pore water flow rate and OC on mobile colloid generation introduces complexity to this potentially critical, yet poorly understood, component of subsurface contaminant transport. 41 refs., 8 figs., 1 tab.

Soil-borne mobile colloids as influenced by water flow and organic carbon

Laboratory studies were conducted to quantify and understand the processes by which iodide (I-) adsorbs to subsurface arid sediments. A surprisingly large amount of I- sorbed (distribution coefficients [Kd?s] ranged from 1 to 10 mL/g and averaged 3.3 mL/g) to three alkaline subsurface sediments that were low in organic matter content. Experiments with pure mineral isolates, similar to the minerals identified in the clay fraction of the sediments, showed that there was little or no I- sorption. The pure minerals that had low iodide sorption include montmorillonite (Kd = -0.42 +/- 0.08 mL/g), quartz (Kd = 0.04 +/- 0.02 mL/g), vermiculite (Kd = 0.56 +/- 0.21 mL/g), calcite (Kd = 0.04 +/- 0.01 mL/g), goethite (Kd = 0.10 +/- 0.03 mL/g), or chlorite (Kd = -0.22 +/- 0.06 mL/g). Conversely, a significant amount of I- sorbed to illite (Kd = 15.14 +/- 2.84 mL/g). Upon treating the iodide-laden illite with dissolved F-, Cl-, Br-, or I-127, desorption (or isotopic exchange in the case of I-127) removed, respectively, 57 +/- 3%, 55 +/- 0%, 48 +/- 3, and 17 +/- 1% of the I- originally adsorbed to the illite. The fact that such large amounts of I- could be desorbed suggestsmore » that the I- was weakly adsorbed, and not chemically bonded to a soft metal, such as mercury or silver, that may have existed in the illite structure as trace impurities. Finally, I- sorption to illite was strongly pH-dependent; the Kd values decreased from 46 to 22 mL/g as the pH increased from 3.6 to 9.4. Importantly, I- sorbed to illite even under alkaline conditions. Together, these experiments suggest that illite removed I- from the aqueous phase predominantly by reversible physical adsorption to the pH-dependent edge sites. Illites may constitute a substantial proportion of the clay-size fraction of many arid sediments and therefore may play an important role in retarding I- movement in these sediments.« less

Iodide Sorption to Subsurface Sediments and Illitic Minerals

Changes in aqueous- and solid-phase Pu oxidation state were monitored over time in magnetite (Fe3O4) suspensions containing 239Pu(V)-amended 0.01 M NaCl. Oxidation state distribution was determined by leaching of Pu into an aqueous phase followed by an ultrafiltration/solvent extraction technique. The capability of the technique to measure Pu oxidation state distribution was verified using 230Th(IV), 237Np(V), and 233U(VI) as oxidation state analogues. Reduction of Pu(V) was observed at all pH values (pH 3 to 8) and magnetite concentrations (10 to 100 m2 L-1). In the pH range 5 to 8, adsorption was a rate-limiting step, and reduction was mediated by the solid phase; at pH 3 reduction occurred in the aqueous phase. The overall reaction (describing both adsorption and reduction of Pu(V)) was found to be approximately first order with respect to the magnetite concentration and of order −0.34 ± 0.02 with respect to the hydrogen ion concentration. Assuming first order dependence with respect to Pu, the overall...

Pu(V)O2+ adsorption and reduction by synthetic magnetite (Fe3O4).

Changes in aqueous- and solid-phase plutonium oxidation state were monitored over time in hematite (alpha-Fe2O3) and goethite (alpha-FeOOH) suspensions containing 239Pu(V)-amended 0.01 M NaCl. Solid-phase oxidation state distribution was quantified by leaching plutonium into the aqueous phase and applying an ultrafiltration/solvent extraction technique. The technique was verified using oxidation state analogues of plutonium and sediment-free controls of known Pu oxidation state. Batch kinetic experiments were conducted at hematite and goethite concentrations between 10 and 500 m2 L(-1) in the pH range of 3-8. Surface-mediated reduction of Pu(V) was observed for both minerals at pH values of 4.5 and greater. At pH 3 no adsorption of Pu(V) was observed on either goethite or hematite; consequently, no reduction was observed. For hematite, adsorption of Pu(V) was the rate-limiting step in the adsorption/reduction process. In the pH range of 5-8, the overall removal of Pu(V) from the system (solid and aqueous phases) was found to be approximately second order with respect to hematite concentration and of order -0.39 with respect to the hydrogen ion concentration. The overall reaction rate constant (k(rxn)), including both adsorption and reduction of Pu(V), was 1.75+/-2.05 x 10(-10) (m(-2) L)(-2.08) (mol(-1) L)(-0.39) (s(-1)). In contrast to hematite, Pu(V) adsorption to goethite occurred rapidly relative to reduction. At a given pH,the reduction rate was approximately independent of the goethite concentration, although the hydrogen ion concentration (pH) had only a slight effect on the overall reaction rate. For goethite, the overall reaction rates at pH 5 and pH 8 were 6.0 x 10(-5) and 1.5 x 10(-4) s(-1), respectively. For hematite, the reaction rate increased by 3 orders of magnitude across the same pH range.

Daniel I. Kaplan

Papers

Zero-valent iron for the in situ remediation of selected metals in groundwater

Soil-borne mobile colloids as influenced by water flow and organic carbon

Iodide Sorption to Subsurface Sediments and Illitic Minerals

Pu(V)O2+ adsorption and reduction by synthetic magnetite (Fe3O4).

Pu(V)O2+ adsorption and reduction by synthetic hematite and goethite.