Prediction of zinc, cadmium, lead, and copper availability to wheat in contaminated soils using chemical speciation, diffusive gradients in thin films, extraction, and isotopic dilution techniques

To predict the availability of metals to plants, it is important to understand both solution- and solid-phase processes in the soil, including the kinetics of metal release from its binding agent (ligand and/or particle). The present study examined the speciation and availability of Zn, Cd, Pb, and Cu in a range of well-equilibrated metal-contaminated soils from diverse sources using several techniques as a basis for predicting metal uptake by plants. Wheat (Triticum aestivum L.) was grown in 13 metal-contaminated soils and metal tissue concentrations (Zn, Cd, Pb, and Cu) in plant shoots were compared with total soil metal concentrations, total soluble metal, and free metal activities (pM2+) in soil pore waters, 0.01 M CaCl2-extractable metal concentrations, E values measured by isotope dilution, and effective metal concentrations, C(E), measured by diffusive gradients in thin films (DGT). In the DGT technique, ions are dynamically removed by their diffusion through a gel to a binding resin, while E values represent the isotopically exchangeable (labile) metal pools. Free metal activities (Zn2+, Cd2+, and Pb2+) in soil pore waters were determined using a Donnan dialysis technique. Plant Zn and Cd concentrations were highly related to C(E), while relationships for Zn and Cd with respect to the other measures of metals in the soils were generally lower, except for CaCl2-extractable Cd. These results suggest that the kinetically labile solid-phase pool of metal, which is included in the DGT measurement, played an important role in Zn and Cd uptake by wheat along with the labile metal in soil solution. Plant Pb concentrations were highly related to both soil pore water concentrations and C(E), indicating that supply from the solid phase may not be so important for Pb. Predictions of Cu uptake by wheat from these soils by the various measures of Cu were generally poor, except surprisingly for total Cu.     

Theoretical comparison of how soil processes affect uptake of metals by diffusive gradients in thinfilms and plants

The theoretical basis for using measurements of metal uptake by the technique of diffusive gradients in thinfilms (DGT) to mimic processes in soils that affect uptake of metals by plants is examined. The uptake of metals by plants and DGT were compared conceptually and quantitatively by using the classic Barber model of plant uptake and the DIFS (DGT-induced fluxes in soils) model of uptake by DGT. For most metals and plants considered, uptake fluxes were similar to those induced by DGT using the most common gel layer thicknesses of 0.2 to 2 mm. Consequently DGT perturbs the chemical equilibrium of metals in the soil solution and between soil solution and solid phase, to a similar extent to plants, and therefore induces a similar balance in supply by diffusion and by release from the solid phase. DIFS was used to show that desorption kinetics, which are not considered by the plant uptake model, are likely important for uptake when the capacity of the soil solid phase is large. Model calculations showed that mass flow into a plant root would only contribute appreciably to the total flux of metal under circumstances when the solid phase reservoir of metal was very low. Generally, however, DGT is likely to emulate supply processes from the soil that govern uptake of metal by plants. Exceptions are likely to be found in poorly buffered soils (typically sandy and/or low pH), and at very high concentrations of metals in soil solution, such that the soil solution concentration at the plant root interface is higher than the Michaelis-Menten constant (Km).     

Relationships between bacterial tolerance levels and forms of copper and zinc in soils

The effects of various fractions of copper (Cu) and zinc (Zn) on soil bacteria were evaluated by the heavy metal tolerance level of the bacterial community (IC50) in soil samples collected near a mine. The IC50 values had no relationship with the total concentrations of Zn and Cu in the soils, but were weakly correlated with the 0.05 M CaCl2-extractable form of each metal in the soils (Cu: R2 = 0.670, p < 0.01; Zn: R2 = 0.453, p < 0.05). It was found that the IC50 correlated strongly with the total concentration of each metal in the extracts from water-saturated soil samples, described below as "soil solution" (Cu: R2 = 0.789, p < 0.01; Zn: R2 = 0.617, p < 0.01). The speciation of these metals in the soil solutions was estimated using an equilibrium thermodynamic computer model, SOILCHEM. Simulated free Cu ion ranged from 18 to 98% of total Cu, and organic complexes of Cu ranged from < 1 to 56%. In all samples, Zn existing as the free ion was estimated to be more than 80% of total Zn in the soil solutions. The IC50 values were also correlated with the estimated free metal ion activities, but with slightly lower correlation coefficients than found for total concentration in the soil solutions (Cu: R2 = 0.735, p < 0.01; Zn: R2 = 0.610, p < 0.01). The results suggest that not only high metal ion activities, but also total dissolved metal concentrations in soil solutions may affect the bacterial community.     

Adsorption of cadmium, copper, nickel, and zinc to a poly(tetrafluorethene) porous soil solution sampler

Suction cups made of poly(tetrafluorethene) (PTFE) are widely used for sampling of soil solution. A brand (Prenart) of PTFE cups was tested for adsorption of Cd, Cu, Ni, and Zn at low concentrations under different conditions. In a laboratory experiment adsorption from a 10 microg L(-1) heavy metal solution with a 0.01 M NaCl background electrolyte was investigated at pH 3.6, 4.5, and 5.8 by pumping the solutions through the cups. The effect of three different ionic compositions was also investigated using 0.01 M CaCl2, 0.01 M NaCl, and no background electrolyte at pH 4.5. In 0.01 M NaCl electrolyte at pH 5.8 the cups acted as effective filters. At pH 3.6 after 300 mL of solution had passed through the cup, equivalence between the Cd and Ni concentrations in influent and effluent was found. No equivalence between effluent and influent concentrations was found for Zn and Cu at pH 4.5 and 5.8. With Ca as the electrolyte, no adsorption of Cd, Ni, or Zn was found. In Na electrolyte, equivalence between influent and effluent concentrations for Cd, Ni, and Zn was reached. The difference between effluent and influent concentrations of Zn, Ni, and Cd remained significant in the absence of electrolyte. For all pH values and electrolytes the difference between effluent and influent concentrations of Cu was significant. It is concluded that PTFE cups affect the concentrations of heavy metals sampled at low soil solution concentrations. Cadmium, Cu, Ni, and Zn adsorb to the cup at pH > 4.5 and low ionic strength.     

Heavy metal release from contaminated soils: comparison of column leaching and batch extraction results

Heavy metals in soils may adversely affect environmental quality. In this study, we investigated the release of Zn, Cd, Pb, and Cu from four contaminated soils by column leaching and single and sequential batch extractions. Homogeneously packed soil columns were leached with 67 mL/g 10(-2) M CaCl2 to investigate the exchangeable metal pool and subsequently with 1400 mL/g 10(-2) M CaCl2 adjusted to pH 3 to study the potential of metal release in response to soil acidification. In two noncalcareous soils (pH 5.7 and 5.1), exchange by Ca resulted in pronounced release peaks for Zn and Cd that were coupled to the exchange of Mg by Ca, and 40 to 70% of total Zn and Cd contents were rapidly mobilized. These amounts compared well with exchangeable pools determined in single and sequential batch extractions. In two soils with near-neutral pH, the effluent concentrations of Zn and Cd were several orders of magnitude lower and no pronounced elution peaks were observed. This behavior was also observed for Cu and Pb in all four soils. When the soils were leached at pH 3, the column effluent patterns reflected the coupling of CaCO3 dissolution (if present) and other proton buffering reactions, proton-induced metal release, and metal-specific readsorption within the soil column. Varying the flow rate by a factor of five had only minor effects on the release patterns. Overall, Ca exchange and subsequent acidification to pH 3 removed between 65 and 90% of total Zn, Cd, Pb, and Cu from the four contaminated soils.     

In situ dynamics of phosphorus in the rhizosphere solution of five species

Root activity can modify the chemistry of the rhizosphere and alter phosphorus (P) availability and uptake. However, until recently, relatively little was known about the dynamics of soil solution P at the root surface because of our inability to measure in situ changes in solution P at the plant root. A mini-rhizotron experiment with corn (Zea mays L. cv. Stine 2250), soybean [Glycine max (L.) Merr. cv. Pioneer 3563), cottonwood (Populus deltoids L.), smooth brome (Bromus inermis Leyss.), and switchgrass (Panicum virgatum L.) was conducted to measure the spatial and temporal dynamics of P in the rhizosphere solution of a fine silty, P-rich calcareous soil (solid-phase total P concentration = 62 mg kg(-1), pH = 7.68) from western Iowa. Micro-suction cups were used to collect samples of soil solution from defined segments of the rhizosphere, and capillary electrophoresis (CE) was used to determine the P concentration of the soil solution. At the end of 10 d, a decreasing P concentration gradient in soil solution toward the root was observed in corn, cottonwood, and smooth brome. No clear rhizosphere effect was observed for soybean and switchgrass. Statistical analysis indicated significantly lower solution P concentrations in the rhizospheres of corn (p = 0.05), cottonwood (p = 0.01), and smooth brome (p = 0.01) compared with bulk soil solution. Results indicate that P depletion from rhizosphere soil solution depends on plant species. Under the conditions of this study, corn, cottonwood, and smooth brome were more effective in depleting solution P than soybean and switchgrass.     

Cobalt distribution and speciation: effect of aging, intermittent submergence, in situ rice roots

The speciation and distribution of Co in soils is poorly understood. This study was conducted using x-ray absorption spectroscopy (XAS) techniques to examine the influence of soluble cobalt in the +2 oxidation state (Co[II]) aging, submergence-dried cycling, and the presence of in vivo rice roots on the speciation and distribution of added Co(II) in soils. In the aging and submerged-dried cycling studies, Co was found to be associated with Mn oxide fraction (23 to 100% of total Co) and Fe oxide fractions (0 to 77% of total Co) of the soils as either Co(II) species or a mixed Co(II), and Co in the +3 oxidation state (Co[III]) species. The surface speciation of Co in the Mn oxide fraction suggests an innersphere complex was present and the speciation of Co in the Fe oxide fraction was an innersphere surface complex. The in vivo root box experiments showed similar Co speciation in the Mn oxide fraction (13 to 76% of total Co) as the aging and submerged-dried cycling studies. However, the Fe oxide fraction of the soil was unimportant in Co retention. A significant amount (24 to 87% of total Co) of the Co in root box treatments was identified as a Co precipitate. The importance of this finding is that in the presence of rice roots, the Co is redistributed to a Co precipitate. This work confirmed earlier macroscopic work that Mn oxides are important in the sequestration of Co in soils and the influence of roots needs to be taken into account when addressing Co speciation. The information gained from this study will be used to improve models to predict the lability and hence the availability of Co in terrestrial environments.     

Effects of dissolved organic carbon on sorption and mobility of imidacloprid in soil

To evaluate the effects of dissolved organic carbon on sorption and mobility of the insecticide imidacloprid [1-(6-chloro-3-pyridinyl) methyl-N-nitro-2-imidazolidinimine] in soils, adsorption and column experiments were performed by using a typical calcareous soil from southeastern Spain and two different types of dissolved organic carbon, that is, dissolved organic carbon extracts from a commercial peat (DOC-PE) and high-purity tannic acid (DOC-TA). The experiments were carried out from a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results obtained from the sorption experiments show that the presence of both DOC-PE and DOC-TA, over a concentration range of 15 to 100 mg L(-1), produces in all cases a decreasing amount of imidacloprid adsorbed in the soil studied. From the column experiments the retardation coefficients (RC) were calculated for imidacloprid by using either 0.01 M CaCl2 aqueous solution (RC = 2.10), 0.01 M CaCl2 DOC-PE solution (RC = 1.65), or 0.01 M CaCl2 DOC-TA solution (RC = 1.87). The results indicate that mobility of imidacloprid is increased 21.4 and 11.0% in the presence of DOC-PE and DOC-TA solutions, respectively. Dissolved organic carbon reduces imidacloprid sorption by competing with the pesticide molecules for sorption sites on the soil surface, allowing enhanced leaching of imidacloprid and potentially increasing ground water contamination.     

Phosphorus speciation in manure-amended alkaline soils

Two common manure storage practices are stockpiles and lagoons. The manure from stockpiles is applied to soils in solid form, while lagoon manure is applied as a liquid. Soil amendment with manure in any form introduces a significant amount of phosphorus (P) that exists in both organic and inorganic forms. However, little is known about P speciation in manure stored under different conditions, or the subsequent forms when applied to soils. We used solution (31)P nuclear magnetic resonance (NMR) spectroscopy and conventional P fractionation and speciation methods to investigate P forms in dairy manure and liquid lagoon manure, and to study how long-term amendment with these manures influenced surface and subsurface soil P speciation. Our results show that the P forms in solid and lagoon manure are similar. About 30% of the total P was organic, mostly as orthophosphate monoesters. On a dry weight basis, total P was much higher in the solid manure. In the manure-amended soils the total P concentrations of the surface soils were similar, regardless of manure type. Total P in the subsurface soil was greater in the lagoon-manure-amended soil than the solid-manure-amended subsurface soil. However, the fraction of organic P was greater in the subsurface of the solid-manure-amended soil. The NMR results indicate that the majority of organic P in the soils is phytic acid, which is enriched in the surface soils compared with the subsurface soils. These results provide insight into P speciation and dynamics in manure-amended soils that will further increase our understanding on how best to manage manure disposal on soils.     

Soil variables for predicting potential phosphorus release in Swedish noncalcareous soils

The accumulation of P in agricultural soils due to fertilization has increased the risk of P losses from agricultural fields to surface waters. In risk assessment systems for P losses, both P release from soil to solution and transport mechanisms need to be considered. In this study, the overall objective was to identify soil variables for prediction of potential P release from soil to solution. Soils from nine sites of the Swedish long-term fertility experiment were used, each with four soil P levels. Phosphorus extractable with CaCl2 was used as an estimate of potential P release from soil to solution. Ammonium lactate-extractable phosphorus (P-AL) or NaHCO3-extractable phosphorus (Olsen P) could not be used alone for prediction of potential P release since soils with high phosphorus sorption capacity (PSC) released less P than soils with low PSC at the same soil test phosphorus (STP) level. Degree of phosphorus saturation (DPS) was calculated as Olsen P or P-AL as a percentage of PSC derived from P sorption isotherms or from Fe and Al extractable in ammonium oxalate. The CaCl2-extractable total phosphorus (CaCl2-TP) was exponentially related to these DPS values (r2 > or = 0.79). The CaCl2-TP was also linearly related to ratios between Olsen P or P-AL and a single-point phosphorus sorption index (PSI; r2 > or = 0.86). These ratios, which are easily determined and gave good correlations with CaCl2-TP, seemed to be the most useful estimates of potential P release for risk assessment systems.     

Chromated copper arsenate-treated fence posts in the agronomic landscape: soil properties controlling arsenic speciation and spatial distribution

Soils adjacent to chromated copper arsenate (CCA)-treated fence posts along a fence line transecting different soil series, parent material, drainage classes, and slope were used to determine which soil properties had the most influence on As spatial distribution and speciation. Metal distribution was evaluated at macroscopic (total metal concentration contour maps) and microscopic scales (micro-synchrotron X-ray fluorescence maps), As speciation was determined using extended X-ray absorption fine structure spectroscopy, and redox status and a myriad of other basic soil properties were elucidated. All geochemical parameters measured point to a condition in which the mobilization of As becomes more favorable moving down the topographic gradient, likely resulting through competition (Meh-P, SOM), neutral or slightly basic pH, and redox conditions that are favorable for As mobilization (higher Fe(II) and total-Fe concentrations in water extracts). On the landscape scale, with hundreds of kilometers of fence, the arsenic loading into the soil can be substantial (～8-12 kg km). Although a significant amount of the As is stable, extended use of CCA-treated wood has resulted in elevated As concentrations in the local environment, increasing the risk of exposure and ecosystem perturbation. Therefore, a move toward arsenic-free alternatives in agricultural applications for which it is currently permitted should be considered.     

Surface runoff losses of copper and zinc in sandy soils

Increased anthropogenic inputs of Cu and Zn in soils have caused considerable concern relative to their effect on water contamination. Copper and Zn contents in surface soil directly influence the movement of Cu and Zn. However, minimal information is available on runoff losses of Cu and Zn in agricultural soils, and soil-extractable Cu and Zn in relation to runoff water quality. Field experiments were conducted in 2001 to study dissolved Cu and Zn losses in runoff in Florida sandy soils under commercial citrus and vegetable production and the relationship between soil-extractable Cu and Zn forms and dissolved Cu and Zn concentrations in runoff water. Five extraction methods were compared for extracting soil available Cu and Zn. Concentrations of dissolved Cu and Zn in runoff were measured and runoff discharge was monitored. Mean dissolved Cu in field runoff water was significantly correlated with the extractable Cu obtained only by 0.01 mol L(-1) CaCl2, Mehlich 1, or DTPA-TEA methods. Dissolved Zn in runoff water was only significantly correlated with extractable Zn by 0.01 mol L(-1) CaCl2. The highest correlations to dissolved Cu in runoff were obtained when soil-available Cu was extracted by 0.01 mol L(-1) CaCl2. The results indicate that 0.01 mol L(-1) CaCl2-extractable Cu and Zn are the best soil indexes for predicting readily released Cu and Zn in the sandy soils. Both runoff discharge and 0.01 mol L(-1) CaCl2-extractable Cu and Zn levels had significant influences on Cu and Zn loads in surface runoff.     

Effects of particle size on chemical speciation and bioavailability of copper to earthworms (Eisenia fetida) exposed to copper nanoparticles

To investigate the role of particle size on the oxidation, bioavailability, and adverse effects of manufactured Cu nanoparticles (NPs) in soils, we exposed the earthworm Eisenia ferida to a series of concentrations of commercially produced NPs labeled as 20- to 40-nm or < 100-nm Cu in artificial soil media. Effects on growth, mortality, reproduction, and expression of a variety of genes associated with metal homeostasis, general stress, and oxidative stress were measured. We also used X-ray absorption spectroscopy and scanning X-ray fluorescence microscopy to characterize changes in chemical speciation and spatial distribution of the NPs in soil media and earthworm tissues. Exposure concentrations of Cu NPs up to 65 mg kg(-1) caused no adverse effects on ecologically relevant endpoints. Increases in metallothionein expression occurred at concentrations exceeding 20 mg kg(-1) of Cu NPs and concentrations exceeding 10 mg kg(-1) of CuSO4. Based on the relationship of Cu tissue concentration to metallothionein expression level and the spatial distribution and chemical speciation of Cu in the tissues, we conclude that Cu ions and oxidized Cu NPs were taken up by the earthworms. This study suggests that oxidized Cu NPs may enter food chains from soil but that adverse effects in earthworms are likely to occur only at relatively high concentrations (> 65 mg Cu kg(-1) soil).     

Adsorption of 2,4-dichlorophenoxyacetic acid by an Andosol

To identify the important soil components involved in 2,4-dichlorophenoxyacetic acid (2,4-D) adsorption on Andosols, 2,4-D adsorption on a surface horizon of an Andosol was compared with that on hydrogen peroxide (H2O2)-treated (soil organic matter [SOM] was removed), acid-oxalate (OX)-treated (active metal hydroxides and SOM were removed), and dithionite-citrate-bicarbonate (DCB)-treated (free and active metal [hydr]oxides and SOM were removed) soil samples at equilibrium pHs ranging from 4 to 8. Although the untreated soil contained a large amount of organic C (71.9 g kg-1), removal of SOM had little effect on 2,4-D adsorption. Active surface hydroxyls, which were attached to the active and free metal (hydr)oxides and metal SOM complexes, were identified as the most important soil functional group for 2,4-D adsorption. The dominant mechanism of the 2,4-D adsorption was a ligand exchange reaction in which the carboxylic group of 2,4-D displaced the active surface hydroxyl associated with metals and formed a strong coordination bond between the 2,4-D molecule and soil solid phase. The ligand exchange reaction reasonably accounted for the selective adsorption of 2,4-D over Cl-, competitive adsorption of phosphate over 2,4-D, reduction in plant-growth-inhibitory activity of soil-adsorbed 2,4-D, and the high 2,4-D adsorption ability of Andosols. Although a humic acid purified from the soil did not adsorb 2,4-D, the presence of the humic acid increased 2,4-D adsorption on Al and Fe, probably by inhibiting the hydrolysis and polymerization of Al and Fe resulting in the preservation of available adsorption sites on these metals. The adsorption behavior of 2,4-D on soils could be a good index for predicting the adsorption behavior of other organic acids in soils.     

Cupric ion activity in peat soil as a toxicity indicator for maize

Copper phytotoxicity in soils is difficult to assess because Cu accumulates at and damages roots, and is not readily transferred to shoots. Soil chemical properties strongly influence Cu speciation, so that total soil Cu alone is not a broadly useful indicator of potential toxicity to plants. The present study measured free Cu2+ activity in Cu-enriched peat soils using the ion selective electrode. The soil Cu2+ activity was related to the severity of phytotoxicity as measured by several indicators in a maize (Zea mays L.) bioassay, including leaf chlorosis, root stunting, and reduced shoot growth and Fe concentration. A soil Cu2+ activity of 10(-7.0) to 10(-7.5), corresponding to total Cu of about 275 mg/kg in the peat soil, caused phytotoxicity in maize seedlings. It is proposed that Cu2+ activity is more directly related to phytotoxic effects than other soil tests, such as extractions with strong acids or chelating agents, because it is the free Cu2+ in soil solution that has the most direct toxic effects on roots. There was very limited uptake of Cu into maize shoots, and even when Cu2+ activity and total soil Cu were raised into the extreme toxicity range of 10(-5) and 4,000 mg/ kg, respectively, shoot Cu remained less than 35 mg/kg. These results indicate the inadequacy of the USEPA risk assessment of potential for Cu toxicity to crops amended with sewage sludge, which assumed a no-effect level of maize shoot Cu of 40 mg/kg.     

Phosphorus in surface runoff from calcareous arable soils of the semiarid Western United States

Management strategies that minimize P transfer from agricultural land to water bodies are based on relationships between P concentrations in soil and runoff. This study evaluated such relationships for surface runoff generated by simulated sprinkler irrigation onto calcareous arable soils of the semiarid western United States. Irrigation was applied at 70 mm h(-1) to plots on four soils containing a wide range of extractable P concentrations. Two irrigation events were conducted on each plot, first onto dry soil and then after 24 h onto wet soil. Particulate P (>0.45 microm) was the dominant fraction in surface runoff from all soils and was strongly correlated with suspended sediment concentration. For individual soil types, filterable reactive P (<0.45 microm) concentrations were strongly correlated with all soil-test P methods, including environmental tests involving extraction with water (1:10 and 1:200 soil to solution ratio), 0.01 M CaCl(2), and iron strips. However, only the Olsen-P agronomic soil-test procedure gave models that were not significantly different among soils. Soil chemical differences, including lower CaCO(3) and water-extractable Ca, higher water-extractable Fe, and higher pH, appeared to account for differences in filterable reactive P concentrations in runoff from soils with similar extractable P concentrations. It may therefore be possible to use a single agronomic test to predict filterable reactive P concentrations in surface runoff from calcareous soils, but inherent dangers exist in assuming a consistent response, even for one soil within a single field.     

Root growth and metal uptake in four grasses grown on zinc-contaminated soils

Depth and area of rooting are important to long-term survival of plants on metal-contaminated, steep-slope soils. We evaluated shoot and root growth and metal uptake of four cool-season grasses grown on a high-Zn soil in a greenhouse. A mixture of biosolids, fly ash, and burnt lime was placed either directly over a Zn-contaminated soil or over a clean, fine-grained topsoil and then the Zn-contaminated soil; the control was the clean topsoil. The grasses were 'Reliant' hard fescue (Festuca brevipila R. Tracey), 'Oahe' intermediate wheatgrass [Elytrigia intermedia (Host) Nevski subsp. intermedia], 'Ruebens' Canada bluegrass (Poa compressa L.), and 'K-31' tall fescue (Festuca arundinacea Schreb.). Root growth in the clean soil and biosolids corresponded to the characteristic rooting ability of each species, while rooting into the Zn-contaminated soil was related to the species' tolerance to Zn. While wheatgrass and tall fescue had the strongest root growth in the surface layers (0-5 cm) of clean soil or biosolids, wheatgrass roots were at least two times more dense than those of the other grasses in the second layer (5-27 cm) of Zn-contaminated soil. When grown over Zn-contaminated soil in the second layer, hard fescue (with 422 mg/kg Zn) was the only species not to have phytotoxic levels of Zn in shoots; tall fescue had the highest Zn uptake (1553 mg/kg). Thus, the best long-term survivors in high-Zn soils should be wheatgrass, due to its ability to root deeply into Zn-contaminated soils, and hard fescue, with its ability to effectively exclude toxic Zn uptake.     

Analysis of potentially mobile phosphorus in arable soils using solid state nuclear magnetic resonance

In many intensive agroecosystems continued inputs of phosphorus (P) over many years can significantly increase soil P concentrations and the risk of P loss to surface waters. For this study we used solid-state 31P nuclear magnetic resonance (NMR) spectroscopy, high-power decoupling with magic angle spinning (HPDec-MAS) NMR, and cross polarization with magic angle spinning (CP-MAS) NMR to determine the chemical nature of potentially mobile P associated with aluminum (Al) and calcium (Ca) in selected arable soils. Three soils with a range of bicarbonate-extractable Olsen P concentrations (40-102 mg P kg(-1)) were obtained from a long-term field experiment on continuous root crops at Rothamsted, UK, established in 1843 (sampled 1958). This soil has a threshold or change point at 59 mg Olsen P kg(-1), above which potentially mobile P (as determined by extraction with water or 0.01 M CaCl2) increases much more per unit increase in Olsen P than below this point. Results showed that CaCl2 and water preferentially extracted Al-P and Ca-P forms, respectively, from the soils. Comparison among the different soils also indicated that potentially mobile P above the threshold was largely present as a combination of soluble and loosely adsorbed (protonated-cross polarized) P forms largely associated with Ca, such as monetite (CaHPO4) and dicalcium phosphate dihydrate (CaHPO4-2H2O), and some Al-associated P as wavellite. The findings of this study demonstrate that solid-state NMR has the potential to provide accurate information on the chemical nature of soil P species and their potential mobility.     

Experimental investigation of adsorption capacity of anthill in the removal of heavy metals from aqueous solution

In the present work, the adsorption capacity of anthill was investigated as a low‐cost adsorbent to remove the heavy metal ions, lead (II) ion (Pb²⁺), and zinc (II) ion (Zn²⁺) from an aqueous solution. The equilibrium adsorption isotherms of the heavy metal ions were investigated under batch process. For the study we examined the effect of the solution's pH and the initial cations concentrations on the adsorption process under a fixed contact time and temperature. The anthill sample was characterized using a scanning electron microscope (SEM), X‐ray fluorescence (XRF), and Fourier transform infrared (FTIR) techniques. From the SEM analysis, structural change in the adsorbent was a result of heavy metals adsorption. Based on the XRF analysis, the main composition of the anthill sample was silica (SiO₂), alumina (Al₂O₃), and zirconia (ZrO₂). The change in the peaks of the spectra before and after adsorption indicated that there was active participation of surface functional groups during the adsorption process. The experimental data obtained were analyzed using 2‐ and 3‐parameter isotherm models. The isotherm data fitted very well to the 3‐parameter Radke–Prausnitz model. It was noted that Pb²⁺ and Zn²⁺ can be effectively removed from aqueous solution using anthill as an adsorbent.     

Trace metal leaching through a soil-grassland system after sewage sludge application

To determine whether sludge applications to soil would lead in the short term to toxicity to plants and trace metal leaching to ground water, we studied the fate of some trace and major elements in a brown soil-meadow system just after repeated sewage sludge applications. The main pathways were quantified over a 37-mo period with undisturbed monolith lysimeters including two controls, four lysimeters treated with 3 x 100 m3 ha-1, and four with 3 x 400 m3 ha-1 of sewage sludge. In drainage waters the effect was limited in time and, in the case of NO3-N and Cl, delayed by 1 to 4 mo and lasted several months before returning to background conditions. Nickel and Cu concentrations in solution increased also after sludge application and had not return to background conditions after 20 mo. Trace metal concentrations did not reach toxic levels in herbage and N, Cu, Cd, and Zn concentrations were correlated with the first sludge input only. Calculated over a 37-mo period, total element output was significantly increased for Ca, NO3-N, and Ni only, because of the time-dependent response to sludge application and high variability between replicates. Output was maximal for Cd, with 1.5% of total input for the 100 m3 ha-1 treatment. Particulate matter in drainage water accounted for an average of 20% of trace metal leaching. The main long-term risk was the rapid increase in trace metal concentrations in the topsoil, which may eventually lead to toxic levels in herbage.