Arsenic immobilization in anaerobic soils by the application of by-product iron materials obtained from the casting industry

ABSTRACT

Reducing the arsenic (As) concentration in rice grains is of great interest from a human health perspective. Iron (Fe) materials immobilize As in soils, thereby effectively reducing the As concentration in rice grains. We investigated the effect of by-product Fe materials obtained from the casting industry on the As mobility in two soils (soil A and soil B) by a long-term (approximately 100 days) flooded soil incubation experiment. The examined Fe materials were spent steel shot (SSS), fine spent casting sand (SCS) containing steel shot, and two kinds of residual Fe materials (RIMs) from steel shot production. Commercial Fe materials used to immobilize As (zero-valent Fe and ferrihydrite) were tested for comparison. The dissolved As in soil solution of controls for soil A and soil B reached approximately 100 and 800 μg L^?1, respectively. The effect on As immobilization of all the by-product Fe materials increased with time and was comparable to or greater than that of commercial ferrihydrite, except for SCS. The additions of SSS and RIMs decreased by more than 90% of the dissolved As in soil A and decreased by more than 50% in soil B after 100 days incubation. Overall, the effect of the by-product Fe materials on the solubility of silicon and phosphorus was much less than that of the commercial Fe materials. Considering the cost advantage over commercial Fe materials, the Fe materials obtained from the casting industry as by-products are promising amendments for the immobilization of As in paddy soils.     

Extractors for barium,cadmium, copper,nickel, and zinc in tropical soils

ABSTRACT

The accumulation of potentially toxic elements (PTEs) in the soil can pose risks to human health, and precise risk assessment dealing with the production and consumption of plants is required. The 0.43 M of nitric acid (HNO?) solution was suggested by the International Organization for Standardization for reactive fraction of PTEs in the soil. The efficiency of some extractors was evaluated in tropical soils. Contents of barium (Ba), cadmium (Cd), copper (Cu), nickel (Ni) and zinc (Zn) were extracted in accordance with the methods of Environmental Protection Agency (EPA) 3051A, Aqua Regia, Diethylenetriaminepentaacetic acid (DTPA), Mehlich-1, Mehlich-3, 0.43 M HNO? and 0.01 M of calcium chloride (CaCl?), and these contents correlated with the contents of PTEs in roots, shoots, and fruits of vegetables. Mehlich-3 had the highest correlation with Ni and Zn contents extracted by the plants. Contents extracted with 0.43 M HNO? had high correlation with the amounts extracted by DTPA and Mehlich-3, as well as with the amounts of PTEs accumulated by plants.     

Orthophosphate and organic phosphate in the soil solution of four sandy soils in relation to pH‐evidence for humic‐FE‐(AL‐) phosphate complexes

Abstract

Soil from the Ap‐horizon of four acid sandy soils differing mainly in Corg content was adjusted to pH values between 3 and 7.5 with NaOH and HCl respectively and incubated for two weeks. Afterwards, displaced soil solution was obtained and analyzed.

The concentrations of Fe, Al, and P showed a broad minimum in the pH range from 4 to 6. The concentration of these elements strongly increased with the increase of pH to 7.5. Acidification below pH values of 4 led to a slight increase.

Separation of dissolved organic carbon by ultrafiltration before the photometric orthophosphate determination decreased measured concentrations in comparison to direct determination in two of the four soils. This decrease was more pronounced for soil solutions with higher concentrations of organic carbon. The effect of acid hydrolysis of organic phosphorus during orthophosphate determination can be explained by existence of humic‐Fe‐(Al phosphate complexes in the soil solution. These complexes can account for more than 50% of the total organic P in solution.     

Effects of iron,calcium, and organic matter on phosphorus behavior in fluvo-aquic soil: farmland investigation and aging experiments

Purpose

Excessive fertilization has led to a high risk of phosphorus (P) leaching and related problems in the North China Plain, where the most typical cropland soil is fluvo-aquic soil. The main factors controlling environmental P behavior and the acting time sequence of these factors in soil after long-term P fertilizer application have not been well recognized. A clear understanding is essential for effective P management.

Materials and methods

Effects of Fe minerals, calcium carbonate, and organic matter (OM) on P immobilization in fluvo-aquic soil were studied systematically through farmland investigation and aging experiments.

Results and discussion

Phosphorus associated with Ca was the primary fraction in fluvo-aquic soil. Even though there was no significant correlation between the total contents of P and Ca in soils, formation of P-Ca phases facilitated by Ca²⁺ in soil solution was a mechanism of P retention when soil received excess P fertilizer. Positive correlations between the contents of P and Fe and total organic carbon (TOC) indicate that Fe minerals and OM have significant effects on P immobilization. Through the aging experiments, P was found to primarily adsorb on goethite and gradually forms Ca-P compounds. Organic fertilizer caused P release and inhibition of P adsorption in the initial stages; however, OM derived from organic fertilizer might facilitate P immobilization in the long term through the formation of a P-Ca-OM complex.

Conclusions

Although superfluous application of P fertilizers leads to the gradual formation of Ca-P in fluvo-aquic soils, there is still a risk of P loss because P is not immediately adsorbed by Fe minerals. Moreover, application of organic fertilizers increases the risk of P loss. These results provide an important scientific basis for initiating P management policies for fluvo-aquic soils.

     

Micrometer-scale internal structure and element distribution of Fe-Mn nodules in Quaternary red earth of Eastern China

Purpose

Fe-Mn nodules are the common feature of tropical and subtropical soils and contain abundant information of pedogenic processes, palaeoenvironmental changes, and element geochemistry. The main aim of the present study was to determine the internal structure and spatial distribution of elements in the Fe-Mn nodules to better understand the 3D internal structure, enrichment, and dynamics of heavy metals in nodules and to provide more aspects to explore the possible heavy metal sequestration and pedoenvironmental implications of Fe-Mn nodules in soils.

Materials and methods

The studied Typic Plinthudult was developed on Quaternary red earths in Èastern China. The Fe-Mn nodules in the Bs horizon of soil were separated and classified into four size fractions (5–8, 3–5, 2–3, and 1–2 mm). The 3D microstructure of Fe-Mn nodules was examined by means of synchrotron radiation-based X-ray microcomputed tomography (SR-mCT), and the spatial distribution of Fe and Mn in nodules was studied by scanning electron microscopy (SEM) equipped with an energy-dispersive X-ray spectrometer (EDS). The association of heavy metals with Fe and Mn oxides in nodules was described by selective chemical dissolution, SEM/EDS, and principal component analysis.

Results and discussion

The SR-mCT images indicated that the 5–8, 3–5, and 2–3 mm nodules exhibited well-defined ring structures, while the 1–2 mm nodule exhibited homogeneous fabric. The internal microstructures of nodules could be divided into four parts: Fe-rich ring, Mn-rich ring, Fe and Mn overlapped ring, and the gap between ring structures. The Fe-Mn nodules were significantly enriched in Mn, Pb, Ni, Cu, and Zn relative to the soil matrix. In particular, the concentrations of Mn and Pb in the nodules were 150 and 90 times greater than those in the soil matrix, respectively. A clear partitioning of heavy metals between Mn and Fe oxide phases was observed in the nodules, indicating that Pb was mainly present in Fe oxides, while Ni, Cu, and Zn were mainly associated with Mn oxide phases.

Conclusions

The SR-mCT and SEM-EDS revealed the detailed internal microstructure of the Fe-Mn nodules and geochemical dynamics of heavy metals in the soil system. The Fe-Mn nodules have very high scavenging ability in sequestrating toxic heavy metals in soils, such as Pb and Ni. The microstructure and spatial distribution of Fe and Mn in nodules reflected the cycle of alternating drying and wetting conditions and served as an important basis for inferring the pedogenic processes and pedoenvironmental conditions.

     

Effect of pH on Potentially Toxic Trace Elements (Cd,Cu, Ni,and Zn) Solubility in Two Native and Spiked Calcareous Soils: Experimental and Modeling

The effect of soil pH on solubility of the potentially toxic trace elements (PTEs) [cadmium (Cd), copper (Cu), nickel (Ni), zinc (Zn)] was assessed using two native and spiked calcareous soils. Multiple PTEs solutions were added to soils and equilibrated (aged) for 40 days. Then, PTEs solubility was measured at different pH level (1–3 units below and above the pH of native soils). In native soils, all PTEs displayed a V-shaped pH-dependent solubility pattern with important releases at pH 4 and 10 (native soil 1) and 5 and 11 (native soil 2). In spiked soils, the general tendency for the pH where solubility started was in the order Cd > Ni > Zn > Cu. Solubility of added trace elements increased with a decrease in pH. Solubility of PTEs occurred at a lower pH in the soil with a higher carbonate content than the other soil (both native and spiked). In order to predict the effect of soil pH on solubility of PTEs, surface complexation and ions exchange models of PHREEQC program were used. The model simulated the PTEs solubility in soils very well. Comparison of experimental and simulated data indicated that ions exchange and surface complexation were the main mechanisms for predicting PTEs solubility in soils. Environmental implications concerning PTEs mobility might be derived from these findings.     

Geochemical behavior and fate of trace elements in naturally contaminated soils under projected land-use changes

Purpose

This paper focuses on determining the geochemical fractionation pattern of trace elements (As, Cd, Cu, Pb, Tl, and Zn) naturally occurring at elevated levels in chestnut grove soils of SW Spain. The goal was to explore how environmental changes triggered by land use and management decisions might affect the resilience and adaptive capacity of soil to retain geogenic trace elements.

Materials and methods

Two plausible scenarios were considered: conversion of forestland to cropland (scenario I) and mining area (scenario II). The potential for trace element removal under the assumed scenarios was assessed by chemical extraction procedures designed to simulate the combined effects of experimentally induced pH and redox changes. Trace elements were partitioned into residual and labile fractions using a five-step sequential extraction scheme optimized for soils enriched in well-crystallized Fe oxides, and their concentrations in the soil extract solutions were measured by inductively coupled plasma mass spectrometry.

Results and discussion

Most metals are tightly bonded to residual and reducible phases, indicating that silicate minerals and Fe oxy-hydroxides, respectively, played a remarkable role in the metal geo-accumulation. Limited mobilization and dispersion of exchangeable and acid-soluble contaminants would be expected to occur through releases or accidental spills from hazardous wastes. An increase in the oxidation state of the soil environment would affect the stability of the organic matter involving the release of the associated trace elements, particularly Cu. Upon reducing conditions induced by land-degradation processes, reductive dissolution of Fe oxy-hydroxides could release large proportions (45–60%) of adsorbed and occluded potentially harmful elements, notably As, Pb, and Cd.

Conclusions

The increasing abandonment of the chestnut groves constitutes a driving force for environmental changes that might affect the geochemical status of the trace elements stored in the soil. Soil could shift from a sink to a source of harmful contaminants over time. This fact should be considered by local stakeholders engaged in planning and decision-making on future land uses.

     

Effects of natural zeolites on ryegrass growth and bioavailability of Cd,Ni, Pb,and Zn in an Albanian contaminated soil

Purpose

The use of eco-friendly and cost-effective adsorbent materials in the remediation of soils contaminated by potentially toxic elements (PTE) is a sustainable way of reducing the transfer of these elements into the food chain. However, an evaluation of the potential of natural zeolites to immobilize toxic elements in contaminated soils was required to enable their efficient use.

Materials and methods

The effect of natural zeolite (Stilbite-Stellerite) from the Munella area (Northern Albania), added at rates ranging from 1.25 to 10 % w/w on a contaminated soil was investigated in a greenhouse pot experiment with ryegrass (Lolium multiflorum L.) and by selective extractions. PTE availability for plants was assessed either as their accumulation in plant tissue or by DTPA-extraction. Oral bio-accessibility was estimated by the in vitro PBET method and the mobility and consequent potential risk of leaching by the USEPA TLCP method. The effect of zeolites on soil properties (pH, electrical conductivity-EC, organic C, and total N) was also investigated. A five steps sequential extraction procedure (SEP) was applied to investigate the immobilization mechanism.

Results and discussion

The addition of 2.5% w/w of natural zeolites caused a significant decrease of PTE mobility, but to observe a significant reduction of DTPA-extractable metals, it was necessary to reach 10% addition rate. In contrast, plant growth showed a gradual increase with addition rate and a corresponding decrease of concentration of PTE in plant tissue. Correlation between DTPA-extractable PTE and their concentration in both root and shoot plant tissue was rather poor. Human hazard due to soil ingestion (PBET method) changed only for Cu and Zn in the gastric phase with 1.25 and 5% addition rate respectively, whereas decreased for Cu and Zn at 5% rate in the Intestinal phase. The results of SEP support the hypothesis that the main mechanism involved in metals fixation are as follows: (1) insolubilization by pH rise, (2) adsorption on Fe/Mn oxides (3) increase of cation exchange retention, (4) organic complexation.

Conclusions

The results of this work suggest that the addition of natural zeolites from the Munella area (AL) is a sustainable practice to reduce the environmental impact of PTE contaminated soils, but an assessment on the longevity of their immobilization need to be evaluated in the long-term perspectives.

     

Ferrihydrite in soils

Ferrihydrite—an ephemeral mineral—is the most active Fe-hydroxide in soils. According to modern data, the ferrihydrite structure contains tetrahedral lattice in addition to the main octahedral lattice, with 10–20% of Fe being concentrated in the former. The presence of Fe tetrahedrons influences the surface properties of this mineral. The chemical composition of ferrihydrite samples depends largely on the size of lattice domains ranging from 2 to 6 nm. Chemically pure ferrihydrite rarely occurs in the soil; it usually contains oxyanion (SiO1₄^4-, PO₄^3-) and cation (Al³⁺) admixtures. Aluminum replace Fe³⁺ in the structure with a decrease in the mineral particle size. Oxyanions slow down polymerization of Fe³⁺ aquahydroxomonomers due to the films at the surface of mineral nanoparticles. Si- and Al-ferrihydrites are more resistant to the reductive dissolution than the chemically pure ferrihydrite. In addition, natural ferrihydrite contains organic substance that decreases the grain size of the mineral. External organic ligands favor ferrihydrite dissolution. In the European part of Russia, ferrihydrite is more widespread in the forest soils than in the steppe soils. Poorly crystallized nanoparticles of ferrihydrite adsorb different cations (Zn, Cu) and anions (phosphate, uranyl, arsenate) to immobilize them in soils; therefore, ferrihydrite nanoparticles play a significant role in the biogeochemical cycle of iron and other elements.     

Mineralogical characterization related to physico-chemical conditions in the pyrite-rich tailings in Guryong Mine,Korea

The detailed characterization of mineralogical changes with depth in pyrite-rich tailings from an abandoned mine provides insight into the future geochemical progression of the tailings. Based on the pH and mineralogical characterization, the Guryong mine tailings can be divided into four zones: jarosite zone, iron (Fe)-sulfate zone, Fe-oxyhydroxide and gypsum-bearing pyrite zone, and calcite-bearing pyrite zone. The jarosite zone was approximately 50 cm deep from the surface and had secondary gypsum (CaSO₄·2H₂O) and jarosite [KFe₃(SO₄)₂(OH)₆]. The pH of the jarosite zone ranged from 2.3 to 4.0, and the ratio of total Fe to total sulfur (S) ranged from 0.7 to 4.3. These results show that the solid phase, schwertmannite or jarosite, is associated with the total sulfate (SO₄) content. The Fe-sulfate zone had low pH values caused by strong pyrite oxidation and greatest amounts of the secondary minerals and acid-leachable heavy metals. The Fe-oxyhydroxide and gypsum-bearing pyrite zone reflects partial alteration of pyrite resulting in the coexistence of secondary gypsum and primary pyrite. The calcite-bearing pyrite zone had pH values exceeding 7.0 at greater depths and contained primary calcite (CaCO₃). However, the GS6 and GS10 profiles, which contained coarse particles near the water table, were the most acidic and their calcite contents were not dectected. The oxidation of pyrite is the most important factor in the mineral cycling of Guryong mine tailings, controlling the changes in pH, the precipitation of secondary mineral phases, and the behavior of heavy metals through the profile.     

Coating a dredged sand with recycled ferrihydrites to create a functional material for plant substrate

Purpose

Urban greenery provides a series of benefits for the environment and inhabitants of cities. However, the substrate preparation mostly implies the mining and erosion of valuable natural soils (e.g., peat). Purpose-designed substrates, preferably made of waste materials, could avoid the extraction damage. The present work aims at improving the production and lowering the costs of a functional stably coated sand with ferrihydrite. This functional substrate combines the Fe (hydr)oxide sorptive capacities and the fast drainage of sand. Thus, secondary raw materials were tested: a dredged sand and three Fe (hydr)oxides; one from groundwater, an industrial intermediate product, and a mining by-product.

Materials and methods

Three Fe (hydr)-oxides were structurally characterized by XRD, XRF analysis, and SSA measurements. Further, amorphous Fe (hydr)oxide concentrations were determined. Sludges of these Fe (hydr)oxides in different concentrations were hand-mixed with a dredged and a mined sand, and dried at 35 °C. The stabilization of the coating was made by heavy shaking (250 rpm) the coated sand with water (3:1 w:w) for 0, 10, and 1000 min, washing and drying at 35 °C afterwards. Thereafter, the effectiveness of this treatment was determined by the Fe concentration and pH of the coated sand, along with the particle size of the detached aggregates during shaking, and the pH in the washing water. The morphology of the coating was observed by scanning electron microscopy.

Results and discussion

All Fe (hydr)oxides were 2-line ferrihydrites with large SSA, and coated both sands. Only after 1000 min shaking, homogeneous and small ferrihydrite aggregates covered the sands surfaces (verified by SEM and particle size). The impurities of the ferrihydrites affected the stabilization of the coating. Calcium carbonates enhanced the aggregation and reattachment of the Fe aggregates to the sand during shaking, while phosphate reduced the reattachment by stabilizing the aggregates in the suspension.

Conclusions

Two out of three ferrihydrites were suitable to develop a stable coating. To coat dredged sand with both ferrihydrites lowers the cost and production time to obtain a functional substrate. One ferrihydrite has a high pH due to its high CaCO3 content, and sand coated with it may be used as an amendment for acidic clayey soils.

     

沙壤性碳酸盐土壤上砷和重金属的运移

The continued effect of the pyrite-tailing oxidation on the mobility of arsenic, lead, zinc, cadmium, and copper was studied in a carbonated soil under natural conditions, with the experimental plot preserved with a layer of tailing covering the soil during three years. The experimental area is located in Southern Spain and was affected by a pyrite-mine spill. The climate in the area is typically Mediterranean, which determines the rate of soil alteration and element mobility. The intense alteration processes that occurred in the soil during three years caused important changes in its morphology and a strong degradation of the main soil properties. In this period, lead concentrated in the first 5 mm of the soil, with concentrations higher than 1500 mg kg^-1, mainly associated to the neoformation of plumbojarosite. Arsenic was partially leached from the first 5 mm and mainly concentrated between 5-10 mm in the soil, with maximum values of 1239 mg kg^-1; the retention of arsenates was related to the neoformation of iron hydroxysulfates (jarosite, schwertmannite) and oxyhydroxides (goethite, ferrihydrite), both with a variable degree of crystallinity. The mobility of Zn, Cd, and Cu was highly affected by pH, producing a stronger leaching in depth; their retention was related to the forms of precipitated aluminium and, in the case of Cu, also to the neoformation of hydroxysulfate.     

Stability in solution and reactivity with soils and soil components of iron and zinc complexes

Naturally derived complexes with the ability to complex (unidentate) or chelate (polydentate) metals are a cheaper alternative to synthetic chelates to correct micronutrient deficiencies, but despite their widespread use there is a lack of knowledge on their agronomic performance. The aim of this paper was to evaluate the stability of iron (Fe) and zinc (Zn) lignosulfonate, gluconate, amino acid, and humate complexes in solution over time and at different pH values. Also, their stability in a concentrated nutrient solution and their reactivity with soils and soil components was evaluated. In our experimental conditions, all the complexes (except Fe amino acid) remained stable in solution for an extended period of time. All Zn complexes and the Fe lignosulfonate were stable in solution up to pH 7.0–7.5, while Fe gluconate only maintained 20%–40% of the iron in solution in the pH range 5–11 and Fe amino acid and humate complexes barely maintained small concentrations of Fe in solution above pH 3. Most of the complexes maintained Fe and Zn in concentrated nutrient solutions for irrigation systems, but Fe amino acid only maintained around 70% of the iron added. In general, the interactions of complexes with soils and soil components produced a high retention. The interaction of Fe lignosulfonate with peat, illite, and ferrihydrite, and Fe gluconate with peat and illite resulted in significant amounts of Fe to remain in solution, while for the Fe amino acid and humate the Fe remaining in solution was low. All Zn complexes were highly retained in an acidic peat, illite, and montmorillonite clays and soils, while no retention was observed on ferrihydrite. In conclusion, the stability of complexes in different conditions is related to the percentage of complexed element in the products. While complexes can be used to maintain micronutrients in solution in aqueous media (foliar and fertigation), their application to soil should be considered as a measure to increase metal availabilities but not their solubility.     

Factors Affecting the Formation,Nature, and Properties of Iron Precipitation Products at the Soil–Root Interface

Abstract

A number of iron oxides (hematite, goethite, lepidocrocite, maghemite, and magnetite) or short‐range ordered precipitates (ferrihydrite) may be found in soil environments, but in the rhizosphere the presence of organic ligands released by plants (exudates) or microorganisms promote the formation of ferrihydrite. Iron ions are liberated into soil solution by acidic weathering of minerals and then precipitated either locally or after translocation in soil environments. Humic and fulvic acids as well as organic substances produced by plants and microorganisms are involved in the weathering of primary minerals. Organic compounds play a very important role in the hydrolytic reactions of iron and on the formation, nature, surface properties, reactivity, and transformation of Fe oxides. Organic substances present in the rhizosphere interact with Fe promoting the formation of ferrihydrite and organo‐mineral complexes. The solubility of Fe precipitation products is usually low. However, the formation of soluble complexes of Fe(II) or Fe(III) with organic ligands, usually present in the rhizosphere increases the solubility of Fe‐oxides. Mobilization of Fe from Fe oxides by siderophores is of great importance in natural systems. They can form stable Fe(III) complexes (pK up to 32) and thus mobilize Fe from Fe(III) compounds. These higher Fe concentrations are important for the supply of Fe to plant roots which excrete organic acids at the soil–root interface. Iron oxides adsorb a wide variety of organic and inorganic anions and cations, which include natural organics, nutrients, and xenobiotics. There is competition between anions and cations for the surfaces of Fe‐oxides. Root exudates suppress phosphate or sulfate adsorption on Fe‐oxides. This is a mechanism by which plant roots mobilize adsorbed phosphate and improve their phosphate supply. Anions adsorption on iron oxides modify their dispersion/flocculation behavior and thus their mobility in the soil system. That can increase or decrease the possibility of contact between Fe‐oxides and organics or organisms able to dissolve them.     

Speciation and sorption structure of diphenylarsinic acid in soil clay mineral fractions using sequential extraction and EXAFS spectroscopy

Purpose

The mobility of arsenic (As) in soils is fundamentally affected by the clay mineral fraction and its composition. Diphenylarsinic acid (DPAA) is an organoarsenic contaminant derived from chemical warfare agents. Understanding how DPAA interacts with soil clay mineral fractions will enhance understanding of the mobility and transformation of DPAA in the soil-water environment. The objective of this study was to investigate the speciation and sorption structure of DPAA in the clay mineral fractions.

Materials and methods

Twelve soils were collected from nine Chinese cities which known as chemical weapons burial sites and artificially contaminated with DPAA. A sequential extraction procedure (SEP) was employed to elucidate the speciation of DPAA in the clay mineral fractions of soils. Pearson’s correlation analysis was used to derive the relationship between DPAA sorption and the selected physicochemical properties of the clay mineral fractions. Extended X-ray absorption fine structure (EXAFS) L_III-edge As was measured using the beamline BL14W1 at Shanghai Synchrotron Radiation Facility (SSRF) to identify the coordination environment of DPAA in clay mineral fractions.

Results and discussion

The SEP results showed that DPAA predominantly existed as specifically fraction (18.3–52.8%). A considerable amount of DPAA was also released from non-specifically fraction (8.2–46.7%) and the dissolution of amorphous, poorly crystalline, and well-crystallized Fe/Al (hydr)oxides (20.1–46.2%). A combination of Pearson’s correlation analysis and SEP study demonstrated that amorphous and poorly crystalline Fe (hydr)oxides contributed most to DPAA sorption in the clay mineral fractions of soils. The EXAFS results further demonstrated that DPAA formed inner-sphere complexes on Fe (hydr)oxides, with As-Fe distances of 3.18–3.25 Å. It is likely that the steric hindrance caused by phenyl substitution and hence the instability of DPAA/Fe complexes explain why a substantial amount of DPAA presented as weakly bound forms.

Conclusions

DPAA in clay mineral fractions predominantly existed as specifically, amorphous, poorly crystalline, and crystallized Fe/Al (hydr)oxides associated fractions. Amorphous/poorly crystalline Fe rather than total Fe contributed more to DPAA sorption and DPAA formed inner-sphere complexes on Fe (hydr)oxides.

     

Formation of hydroxy‐sulfates from pyrite in coastal acid sulfate soil environments in Malaysia

Abstract

Pyrite in hydromorphic soils is oxidized when it is exposed to the atmosphere. The sulfide oxidation releases hydrogen (H⁺) ions and other ions into the aqueous solution, and subsequently hydroxy‐sulfates are formed. A laboratory aging experiment was conducted using coastal sulfate‐rich soils in Malaysia to identify and determine the nature and composition of the hydroxy‐sulfates and to explain the mechanism of their formation. Powder X‐ray diffraction (XRD) analysis showed that incubating the pyrite‐bearing soils in the presence of added electrolyte (KCl and NaCl) resulted in the formation of jarosite, natrojarosite, and/or alunite. Subsequent transmission electron microscopy‐energy dispersive X‐ray (TEM‐EDAX) analysis showed that a hydroxy‐sulfate crystal was composed mainly of hydrogen (H), oxygen (O), sodium (Na), aluminum (Al), sulfur (S), potassium (K), and iron (Fe) which was accounted for as jarosite, natrojarosite, and/or alunite by powder XRD. The small amount of fluorine (F), nickel (Ni), titanium (Ti), and manganese (Mn) occurring within the same hydroxy‐sulfate crystal was presumably originated from pyrite. This result points to the formation of hydroxy‐sulfates in acid sulfate soils via psuedomorphic replacement of pyrite under an oxidizing environment.     

Heavy‐metal toxicity in plants 1. A crisis in embryo

Abstract

Heavy metals are often added indiscriminantly to soils in pesticides, fertilizers, manures, sewage sludges, and mine wastes, causing an imbalance in nutrient elements in soils. Heavy‐metal toxicity causes plant stress in various degrees dependent on the tolerance of the plant to a specific heavy metal. The objectives of this study were (i) to show that plant species and soils respond differently to heavy metals and (ii) to show the necessity for proper quantity and balance of heavy metals in soils for plant growth.

Three Fe‐inefficient and three Fe‐efficient selections of soybean, corn, and tomato were grown on two alkaline soils with Cu and Zn ranging from 14 to 340 and Mn from 20 to 480 kg/ha. Heavy‐metal toxicity caused Fe deficiency to develop in these plants. The Fe‐inefficient T3238fer tomato and ys₁/ys₁ corn developed Fe deficiency on all treatments and both soils. T3238FER tomato (Fe‐efficient) did not develop heavy metal toxicity symptoms on any treatment or soil. The soybean varieties and WF9 corn were intermediate in their response.

The unpredictable response of both the soil and the plant to heavy metals make general recommendations difficult. In order to maintain highly productive soils, we need to know what we are adding to soils and the consequences. Without some control, the continued addition of heavy metals to soils is a crisis in embryo.     

Phytoavailability of lead altered by two Pelargonium cultivars grown on contrasting lead-spiked soils

Purpose

This study assesses the potential of two contrasted fragrant Pelargonium cultivars to induce pH and dissolved organic carbon (DOC) changes in the soil solution, Pb speciation, and their subsequent effects on rhizosphere phytoavailable Pb.

Materials and methods

Rooted plantlets were grown in special devices, floating on aerated nutrient solution in PVC tanks. This setup allows roots to be physically separated, through a mesh, from a 3-mm soil matrix layer that can be considered as rhizosphere soil. Two contrasted soils, each spiked with Pb-rich particles, emitted from a battery recycling industry, were used at total burdens of 500 and 1500 mg Pb kg^?1 in addition to a control unspiked soil. Soil solution pH, phytoavailable Pb, DOC, Pb adsorption, precipitation on roots, and Pb phases in soil and plant were investigated.

Results and discussion

Attar of Roses (Attar) cultivar acidified its rhizosphere by 0.4 pH units in both spiked soils. Concolor Lace (Concolor) was unable to change soil solution pH on soil-1 and increased it by 0.7 units on soil 2. Concentrations of Pb in soil solution from Attar plants were always higher than those of Concolor ones. DOC contents of both unspiked soil-1 and soil-2 without plants were not significantly different. In the case of spiked samples, DOC contents in the rhizosphere soil were increased by three and two times for Attar and Concolor, respectively, compared to the unspiked soil without plant. Both cultivars were able to increase DOC contents, independent of soil type and level of contamination. Accumulation of Pb in shoots and roots was higher in Attar as compared to Concolor due to enhanced available Pb as a result of pH and DOC modifications of the rhizosphere soil. Significant amounts of Pb were adsorbed on roots of both cultivars. X-ray elemental analysis of precipitates on roots revealed the association of Pb with P in cylinder-like structures. Extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that Pb was present, to a major extent in the inorganic form, mainly as PbSO₄ in the soil, whereas it was complexed with organic species within plant tissues. The conversion of Pb into organic species could decrease toxicity, may enhance plant tolerance, and could increase translocation.

Conclusions

Plant-induced changes were responsible for the modification of lead phases within the soil. Immobile forms present in the source leaded particles as well as in the soils were converted into soluble species, ultimately improving the phytoavailable or soil solubilized Pb.

     

Redox reactions and phosphorus release in re-flooded soils of an altered wetland

Phosphorus loss from land can be a major factor affecting surface water quality. We studied P‐release mechanisms in wetland soils that had been drained and cultivated for four decades and then re‐flooded. We measured redox, pH and solution composition in two sites in the field and in four peat and calcareous soils incubated in biogeochemical microcosms. The redox and pH measurements during the 120 days of incubation and the resulting soil solution composition indicated that the main process leading to P release is reductive dissolution of ferric hydroxides on which P was adsorbed and in which P was occluded. The molar Fe:P ratio increased with period of reduction from below 1 in the first week of re‐flooding to 15–60 after 120 days. This suggests an increased P‐retention capacity upon reoxidation of the soil solution, whether within the soil profile or in the drainage canals. Prolonged flooding of the calcite‐poor, gypsum‐rich peat soils increased the oversaturation of soil solutions with respect to hydroxyapatite and occasionally β‐Ca₃(PO₄)₂(c), indicating that in spite of the large Ca concentration, the rate of Ca‐P precipitation was insufficient to maintain the saturation status of the Ca‐P system. In the calcareous soils the Ca‐P system effectively controlled the P activity in soil solution throughout the incubation period. In both cases the precipitation of Ca‐P minerals could be an important P‐retention mechanism.     

Copper retention by Danish Spodosols in relation to contents of organic matter and aluminum,iron, and manganese oxides

Abstract

The importance of various soil components on copper (Cu) retention by Spodosois was investigated. Copper sorption and extraction were conducted on samples from the B horizon from six Danish Spodosois. The investigation was conducted on untreated samples, on hydrogen peroxide‐treated samples (to remove organic matter), on oxalate‐treated samples [to remove amorphous to poorly crystalline aluminum (Al) and iron (Fe) oxides], on hydroxylamine‐treated samples [to remove manganese (Mn) oxides]. Subfractions treated with hydrogen peroxide (H₂O₂) were further treated with oxalate and citrate‐bicarbonate‐dithionite (CBD). Sorption of Cu from an initial 10^‐6 M solution after 48 hours was determined in the pH range 3 to 7 using 0.1M sodium nitrate (NaNO₃) as the background electrolyte. The pH‐dependent sorption curve (sorption edge) was shifted to a higher pH with decreasing Al oxide content in the soils, and for the treated sample after removal of organic matter and Al and Fe oxides. A negligible effect was seen after removal of the Mn oxides because of their low abundance. Extraction of sorbed Cu at pH 4 to 6 with 0.1M nitric acid (HNO₃) for 24 hours confirmed the sorption results, in inasmuch as removal of the Al (and Fe) oxides increased Cu extractability. Therefore, it was concluded that in the soils investigated, Cu retention is mainly determined by the oxalate‐extractable Al fraction with a minor contribution due to crystalline Fe oxides.