Complexation of copper by sewage sludge-derived dissolved organic matter: Effects on soil sorption behaviour and plant uptake

The complexation of Cu by sewage sludge-derived dissolved organic matter (SSDOM) is a process by which the environmental significance of the element may become enhanced due to reduced soil sorption and, hence, increased mobility. The work described in this paper used an ion selective electrode procedure to show that SSDOM complexation of Cu was greatest at intermediate pH values because competition between hydrogen ions and Cu for SSDOM binding sites, and between hydroxyl ions and SSDOM as Cu ligands, was lowest at such values. Batch sorption experiments further showed that the process of Cu complexation by SSDOM provided an explanation for enhanced desorption of Cu from the solid phase of a contaminated, organic matter-rich, clay loam soil, and reduced adsorption of Cu onto the solid phase of a sandy loam soil. Complexation of Cu by SSDOM did not affect uptake of Cu by spring barley plants, when compared to free ionic Cu, in a sand-culture pot experiment. However, it did appear to lead to greater biomass yields of the plant; perhaps indicating that the Cu-SSDOM complex had a lower toxicity towards the plant than the free Cu ion.

Zinc sorption in selected soils

The adsorption of nutrient elements is one of the most important solid- and liquid-phase interactions determining the retention and release of applied plant nutrients and the efficiency of fertilization. The study showed that the soils with high cation exchange capacity (CEC), CaCO3 , organic matter contents, and heavy texture adsorbed more zinc (Zn). The alkaline soils from Pakistan adsorbed more Zn than English acidic soils. Langmuir and Freundlich isotherm fit was excellent, and r(2) values for the Langmuir isotherm were highly significant (r(2) =0.84 to 0.99). The Langmuir b values, representing the adsorptive capacity of a soil, increased as the texture fineness increased in the soil, with increases in the concentration of adsorptive material (such as organic matter and CaCO3) and with increases in CEC and pH. The alkaline soils from Pakistan had higher bonding energy constant and higher log Kf values than the acidic English soils. Sequential extraction of Zn in these soils showed that most of the Zn was held in CaCO3 pool in the alkaline soils, whereas in acidic soils adsorbed Zn was in exchangeable form.

Phosphorus sorption and availability in soils amended with animal manures and sewage sludge

Soils that receive large applications of animal wastes and sewage sludge are vulnerable to releasing environmentally significant concentrations of dissolved P available to subsurface flow owing to the gradual saturation of the soil's P sorption capacity. This study evaluated P sorption (calculated from Langmuir isotherms) and availability of P (as CaCl2-P and resin P) in soils incubated for 20 d with poultry litter, poultry manure, cattle slurry, municipal sewage sludge, or KH2PO4, added on a P-equivalent basis (100 mg P kg(-1)). All the P sources had a marked negative effect on P sorption and a positive effect on P availability in all soils. In the cattle slurry- and KH2PO4- treated soils, the decreases in P sorption maximum (19-66%) and binding energy (25-89%) were consistently larger than the corresponding decreases (7-41% and 11-30%) in poultry litter-, poultry manure-, and sewage sludge-treated soils. The effects of cattle slurry and KH2PO4 on P availability were, in most cases, larger than those of the other P sources. In the poultry litter, poultry manure, and sewage sludge treatments, the increase in soil solution P was inversely related (R-2 = 0.75) to the input of Ca from these relatively high Ca (13.5-42 g kg(-1)) sources. Correlation analyses implied that the magnitude of the changes in P sorption and availability was not related to the water-extractable P content of the P sources. Future research on the sustainable application of organic wastes to agricultural soils needs to consider the non-P- as well as P-containing components of the waste.

Mutant alleles at the rugosus loci in pea affect seed moisture sorption isotherms and the relations between seed longevity and moisture content

Pea (Pisum sativum L.) mutant near-isogenic lines (RRrbrb, rrRbRb, rrrbrb) with lower starch but higher lipid contents, brought about by lesions in the starch biosynthetic pathway, had seed moisture sorption isotherms displaced below that of the wild type (RRRbRb). The negative logarithmic relationship between seed longevity and seed storage moisture content (%, f.wt basis), determined in hermetic storage at 65 degreesC, also differed: longevity in the mutant near-isogenic lines was poorer and less sensitive to moisture content than in the wild type (i.e. C-w was lower). The low-moisture-content limit (m(c)) to this relation also differed, being lower in the mutant near-isogenic lines (5.4-5.9%) than in the wild type (6.1%). In contrast, all four near-isogenic lines showed no difference (P >0.25) in the negative semilogarithmic relationship between equilibrium relative humidity (ERH) and seed longevity. It is concluded that the effect of these alleles at the r and rb loci on seed longevity. was largely indirect; a consequence of their effect on seed composition and hence on moisture sorption isotherms. However, this explanation could not be invoked at moisture contents below mc where differences in longevity remained substantial (RRRbRb double that of rrrbrb). Hence, these mutant alleles affected seed longevity directly at very low moisture contents.

Mutant alleles at the rugosus loci in pea affect seed moisture sorption isotherms and the relations between seed longevity and moisture content

Pea (Pisum sativum L.) mutant near-isogenic lines (RRrbrb, rrRbRb, rrrbrb) with lower starch but higher lipid contents, brought about by lesions in the starch biosynthetic pathway, had seed moisture sorption isotherms displaced below that of the wild type (RRRbRb). The negative logarithmic relationship between seed longevity and seed storage moisture content (%, f.wt basis), determined in hermetic storage at 65 °C, also differed: longevity in the mutant near-isogenic lines was poorer and less sensitive to moisture content than in the wild type (i.e. CW was lower). The low-moisture-content limit (mc) to this relation also differed, being lower in the mutant near-isogenic lines (5.4–5.9%) than in the wild type (6.1%). In contrast, all four near-isogenic lines showed no difference (P >0.25) in the negative semi-logarithmic relationship between equilibrium relative humidity (ERH) and seed longevity. It is concluded that the effect of these alleles at the r and rb loci on seed longevity was largely indirect; a consequence of their effect on seed composition and hence on moisture sorption isotherms. However, this explanation could not be invoked at moisture contents below mc where differences in longevity remained substantial (RRRbRb double that of rrrbrb). Hence, these mutant alleles affected seed longevity directly at very low moisture contents.

Biochar alteration of the sorption of substrates and products in Soil Enzyme Assays

Pine wood and barley straw biochar amendments to Kettering and Cameroon sandy silt loam soils (15, 30, or 150 mg biochar g−1 soil) caused significant reductions (up to 80%,

The release of silicon from amorphous silica and rice straw in Sri Lankan soils

Silicon release from rice straw and amorphous silica when shaken in solution with five Sri Lankan soils was studied indirectly using sorption isotherms and changes in concentration and directly using straw in dialysis bags examined using electron microscopy. The aim was to further our understanding of the processes and factors affecting the release of straw-Si in soils and its availability to rice. The soils (alfisols and ultisols) shaken with 0.1 M NaCl (5 g per 125 mL for 250 days) produced concentrations of 1 - 4 mg L-1 of monosilicic acid-Si. Amorphous silica added to these suspensions (36.5 mg, containing 17 mg Si) raised the concentrations to 20 - 40 mg L-1, and added rice straw (0.5 g, containing 17 mg Si) gave 10 - 25 mg L-1. Sorption isotherms (7 days equilibrations) were used to calculate from the concentrations the amounts of Si released ( 24 - 38% and 8 - 21%, respectively). Both materials gave about 40 mg L-1 of monosilicic acid-Si plus 30 mg L-1 of disilicic acid-Si when shaken in solution alone (5 g per 125 mL). Straw in dialysis bags ( 0.5 g per 25 mL in 0.1 M NaCl) was shaken in soil suspension ( 5 g per 100 mL) for 60 days. Similar concentrations and releases were measured to those obtained above. About one fifth of the mass of straw was lost by decomposition in the first 15 days. A chloroform treatment prevented decomposition, but Si release was unaffected. Disintegration continued throughout the experiments, with phytoliths being exposed and dissolved. Compared to the rate of release from straw into solution without soil, the release of Si into soil suspensions was increased during the first 20 days by adsorption on the soil, but was then reduced probably through the effect of Fe and Al on the phytolith surfaces. The extent of this blocking effect varied between soils and was not simply related to soil pH.

Transport and distribution of lindane and simazine in a riverine environment: measurements in bed sediments and modelling

Aquatic sediments often remove hydrophobic contaminants from fresh waters. The subsequent distribution and concentration of contaminants in bed sediments determines their effect on benthic organisms and the risk of re-entry into the water and/or leaching to groundwater. This study examines the transport of simazine and lindane in aquatic bed sediments with the aim of understanding the processes that determine their depth distribution. Experiments in flume channels (water flow of 10 cm s(-1)) determined the persistence of the compounds in the absence of sediment with (a) de-ionised water and (b) a solution that had been in contact with river sediment. In further experiments with river bed sediments in light and dark conditions, measurements were made of the concentration of the compounds in the overlying water and the development of bacterial/algal biofilms and bioturbation activity. At the end of the experiments, concentrations in sediments and associated pore waters were determined in sections of the sediment at 1 mm resolution down to 5 mm and then at 10 mm resolution to 50 mm depth and these distributions analysed using a sorption-diffusion-degradation model. The fine resolution in the depth profile permitted the detection of a maximum in the concentration of the compounds in the pore water near the surface, whereas concentrations in the sediment increased to a maximum at the surface itself. Experimental distribution coefficients determined from the pore water and sediment concentrations indicated a gradient with depth that was partly explained by an increase in organic matter content and specific surface area of the solids near the interface. The modelling showed that degradation of lindane within the sediment was necessary to explain the concentration profiles, with the optimum agreement between the measured and theoretical profiles obtained with differential degradation in the oxic and anoxic zones. The compounds penetrated to a depth of 40-50 rum over a period of 42 days. (C) 2004 Society of Chemical Industry.

A preliminary investigation into the use of ochre as a remedial amendment in arsenic-contaminated soils

Ochre is an unwanted waste product that accumulates in wetlands and streams draining abandoned coal and metal mines. A potential commercial use for ochre is to remediate As contaminated soil. Arsenic contaminated soil (605 mg kg(-1)) was mixed with different ochres (A, B and C) in a mass ratio of 1:1 and shaken in 20 mL of deionised water. After 72 h As concentration in solution was ca. 500 mu g kg(-1) in the control and 1-2.5 mu g kg(-1) in the ochre treated experiments. In a second experiment soil:ochre mixtures of 0.05-1:1 were shaken in 20 mL of deionised water for 24 h. For Ochres A and C, as Solution concentration was reduced to ca. 1 mu gkg(-1) by 0.2-1:1 ochre:soil mixtures. For Ochre B, as concentration only reached ca. 1 mu g kg(-1) in the 1:1 ochre:soil inix. Sorption of As was best modelled by a Freundlich isotherm using As sorption per mass of goethite in the ochre (log K= 1.64, n = 0.79, R-2 = 0.76, p <= 0.001). Efficiency of ochre in removing As from solution increased with increasing total Fe, goethite, citrate dithionite extractable Fe and surface area. (c) 2005 Elsevier Ltd. All rights reserved.

Modeling the mechanisms that control in-stream dissolved organic carbon dynamics in upland and forested catchments

[1] We present a new, process-based model of soil and stream water dissolved organic carbon (DOC): the Integrated Catchments Model for Carbon (INCA-C). INCA-C is the first model of DOC cycling to explicitly include effects of different land cover types, hydrological flow paths, in-soil carbon biogeochemistry, and surface water processes on in-stream DOC concentrations. It can be calibrated using only routinely available monitoring data. INCA-C simulates daily DOC concentrations over a period of years to decades. Sources, sinks, and transformation of solid and dissolved organic carbon in peat and forest soils, wetlands, and streams as well as organic carbon mineralization in stream waters are modeled. INCA-C is designed to be applied to natural and seminatural forested and peat-dominated catchments in boreal and temperate regions. Simulations at two forested catchments showed that seasonal and interannual patterns of DOC concentration could be modeled using climate-related parameters alone. A sensitivity analysis showed that model predictions were dependent on the mass of organic carbon in the soil and that in-soil process rates were dependent on soil moisture status. Sensitive rate coefficients in the model included those for organic carbon sorption and desorption and DOC mineralization in the soil. The model was also sensitive to the amount of litter fall. Our results show the importance of climate variability in controlling surface water DOC concentrations and suggest the need for further research on the mechanisms controlling production and consumption of DOC in soils.

Potassium leaching in undisturbed soil cores following surface applications of gypsum

Displacement studies on leaching of potassium (K+) were conducted under unsaturated steady state flow conditions in nine undisturbed soil columns (15.5 cm in diameter and 25 cm long). Pulses of K+ applied to columns of undisturbed soil were leached with distilled water or calcium chloride (CaCl2) at a rate of 18 mm h(-1). The movement of K+ in gypsum treated soil leached with distilled water was at a similar rate to that of the untreated soil leached with 15 mM CaCl2. The Ca2+ concentrations in the leachates were about 15 mM, the expected values for the dissolution of the gypsum. When applied K+ was displaced with the distilled water, K+ was retained in the top 10-12.5 cm depth of soil. In the undisturbed soil cores there is possibility of preferential flow and lack of K+ sorption. The application of gypsum and CaCl2 in the reclamation of sodic soils would be expected to leach K+ from soils. It can also be concluded that the use of sources of water for irrigation which have a high Ca2+ concentration can also lead to leaching of K+ from soil. Average effluent concentration of K+ during leaching period was 30.2 and 28.6 mg l(-1) for the gypsum and CaCl2 treated soils, respectively. These concentrations are greater than the recommended guideline of the World Health Organisation (12 mg K+ l(-1)).

The role of gypsum in the reactions of phosphate with soils

The aim of this study was to examine the mechanisms by which gypsum increases the sorption of fertilizer-P in soils of and and semi-arid regions. Either gypsum or soil (Usher from the UK; pH 7.8, 7% organic matter, 21% CaCO3: Yasouj from Iran; pH 8.2, 1.4% OM, 18% CaCO3: Ghanimeh from Saudi Arabia; pH 7.8, 1% OM, 26% CaCO3, 13% gypsum) was shaken for 24 It with KH2PO4 solutions in 10 mM CaCl2. With gypsum, grinding increased sorption by a factor of about 3, and increase in pH from 5.6 to 7.5 greatly increased sorption. Scanning electron micrographs (SEM) and EDX quantitative analysis showed that small crystals of gypsum disappeared and roughly spherical particles of dicalcium phosphate (DCPD) were formed. Analysis of equilibrium Solutions showed, using GEOCHEM, that octa-calcium phosphate (OCP) coated the DCPD. For the soils, sorption was in the order Ghanimeh > Yasouj > Usher. Removal of gypsum from Ghanimeh reduced sorption, with precipitated gypsum having a greater effect than gypsum mixed physically with the soil. Addition to Usher had no effect. SEM and EDX could not be used in the soil matrix, but solubility analysis again showed that solutions were close to equilibrium with OCP. Usher was unresponsive to added gypsum, presumably because of its small sorption capacity and high organic matter content. In Ghanimeh and Yasouj soils, gypsum increased sorption by being a source of readily available Ca2+ (c) 2005 Elsevier B.V. All rights reserved.

Laboratory simulation of terrestrial meteorite weathering using the Bensour (LL6) ordinary chondrite

Laboratory dissolution experiments using the LL6 ordinary chondrite Bensour demonstrate that meteoritic minerals readily react with distilled water at low temperatures, liberating ions into solution and forming reaction products. Three experiments were performed, all for 68 days and at atmospheric fO(2) but using a range of water/rock ratios and different ternperatures. Experiments I and 2 were batch experiments and undertaken at room temperature, whereas in experiment 3, condensed boiling water was dripped onto meteorite subsamples within a Soxhlet extractor. Solutions from experiment 1 were chemically analyzed at the end of the experiment, whereas aliquots were extracted from experiments 2 and 3 for analysis at regular intervals. In all three experiments, a very significant proportion of the Na, Cl, and K within the Bensour subsamples entered solution, demonstrating that chlorapatite and feldspar were especially susceptible to dissolution. Concentrations of Mg, Al, Si, Ca, and Fe in solution were strongly affected by the precipitation of reaction products and Mg and Ca may also have been removed by sorption. Calculations predict saturation of experimental solutions with respect to Al hydroxides, Fe oxides, and Fe (oxy)hydroxides, which would have frequently been accompanied by hydrous aluminosilicates. Some reaction products were identified and include silica, a Mg-rich silicate, Fe oxides, and Fe (oxy)hydroxides. The implications of these results are that even very short periods of subaerial exposure of ordinary chondrites will lead to dissolution of primary minerals and crystallization of weathering products that are likely to include aluminosilicates and silicates, Mg-Ca carbonates, and sulfates in addition to the ubiquitous Fe oxides and (oxy)hydroxides.

Wetland restoration within agricultural watersheds: Balancing water quality protection with habitat conservation

Peat wetlands that have been restored from agricultural Land have the potential to act as Long term sources of phosphorus (P) and, therefore have to potenital to accelerate freshwater eutrophication. During a two-year study the water table in a eutrophic fen peat that was managed by pump drainage fluctuated annually between +20 cm and -60 cm relative to ground Level. This precise management was facilitated by the high hydraulic conductivity (K) of the humified peat (1.1 x 10(-5) m s(-1)) below around 60 cm depth. However, during one week of intermittent pumping, as much as 50 g ha(-1) dissolved P entered the pumped ditch. Summer. rainfall events and autumn reflooding also triggered P losses. The P Losses were attributed to the low P sorption capacity (217 mg kg(-1)) of the saturated peat below 60 cm, combined with its high K and the reductive dissolution of Fe bound P.

Factors influencing the dissolution of phosphate rock in a range of high P-fixing soils from Cameroon

A laboratory incubation experiment was conducted to evaluate the soil factors that influence the dissolution of two phosphate rocks (PRs) of different reactivity (Gafsa, GPR, reactive PR; and Togo-Hahotoe, HPR, low reactivity PR) in seven agricultural soils from Cameroon having variable phosphorus (P)- sorption capacities, organic carbon (C) contents, and exchangeable acidities. Ground PR was mixed with the soils at a rate of 500 mg P kg 21 soil and incubated at 30 degrees C for 85 days. Dissolution of the PRs was determined at various intervals using the Delta NaOH-P method ( the difference of the amount of P extracted by 0.5 M NaOH between the PR-treated soils and the control). Between 4 and 27% of HPR and 33 and 50% of GPR were dissolved in the soils. Calcium (Ca) saturation of cation exchange sites and proton supply strongly affected PR dissolution in these soils. Acid soils with pH-(H2O), < 5 (NKL, ODJ, NSM, MTF) dissolved more phosphate rock than those with pH-(H2O) > 5 (DSC, FGT, BAF). However, the lack of a sufficient Ca sink in the former constrained the dissolution of both PRs. The dissolution of GPR in the slightly acidic soils was limited by increase in Ca saturation and that of HPR was constrained by limited supply in protons. Generally, the dissolution of GPR was higher than that of HPR for each soil. The kinetics of dissolution of PR in the soils was best described by the power function equation P At B. More efficient use of PR in these soils can be achieved by raising the soil cation exchange capacity, thereby increasing the Ca sink size. This could be done by amending such soils with organic materials.