Effect of fly ash on sorption behavior of metribuzin in agricultural soils

This investigation was undertaken to determine the effect of two different fly ashes [Kota and Inderprastha (IP)] amendment on the sorption behavior of metribuzin in three Indian soil types. The IP fly ash was very effective in increasing the metribuzin sorption in the soils. The sorption with IP amendment was increased by 15–92%, whereas with the Kota fly ash an increase in sorption by 13–38% was noted. The adsorption isotherms fitted very well to the Freundlich adsorption equation and, in general, slope (1/n) values less then unity were observed. Although both the fly ashes significantly decreased metribuzin desorption, the IP fly ash was comparatively more effective in retaining metribuzin in the soils. Metribuzin sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to K_f/K_d values, K_FA values (sorption normalized to fly ash content) showed less variation. Metribuzin sorption-desorption did not correlate to the organic carbon content of the soil-fly ash mixture. The study demonstrates that all coal fly ashes may not be effective in enhancing the sorption of metribuzin in soils to the same extent. However, among the fly ashes used in this study, the IP fly ash was observed to be significantly effective in enhancing the sorption of metribuzin in soils. This may play an important role in reducing the run off and leaching losses of the herbicide by retaining it in the soil.     

Effect of fly ash on metsulfuron-methyl sorption and leaching in soils

This investigation was undertaken to determine the effect of amendment of two fly ashes [Kota and Inderprastha (IP)] on sorption behavior of metsulfuron-methyl in three Indian soil types. Kota fly ash (5%) did not show any effect on herbicide sorption while IP fly ash significantly enhanced the sorption. Further studies on metsulfuron-methyl sorption-desorption behavior in 0.5, 1, 2, and 5% IP fly ash-amended soils suggested that effect of fly ash varied with soil type and better effect was observed in low organic carbon content soils. The sorption-desorption isotherms fitted very well to the Freundlich sorption equation and, in general, slope (1/n) values less than unity were observed. Metsulfuron-methyl sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to the Freundlich sorption constant (K _f), K _FA values (sorption normalized to fly ash content) showed less variation. Metsulfuron-methyl leaching studies suggested greater retention of herbicide in the application zone in IP fly ash-amended soils, but effect varied with soil type and no herbicide leaching was observed in 5% fly ash-amended soils. The study suggested that all coal fly ashes are not effective in enhancing the sorption of metsulfuron-methyl in soils. However, one which enhanced herbicide sorption, could play an important role in reducing its leaching losses.     

Reduced downward mobility of metribuzin in fly ash-amended soils

Metribuzin, a triazine herbicide, is poorly sorbed in the soils, therefore leaches to lower soil profile. Fly ash amendment, which enhanced metribuzin sorption in soils, may play a significant role in reducing the downward mobility of herbicide. Therefore, the present study reports the effect of Inderprastha fly ash amendment on metribuzin leaching in three soil types. Fly ash was amended at 1, 2 and 5% levels in the upper 15 cm of 30 cm long packed soil columns. Results suggested a significant reduction in the leaching losses of metribuzin in fly ash-amended columns of all the three soil types and effect increased with increase in the level of fly ash. Even after percolating water equivalent to 362 mm rainfall no metribuzin was recovered in the leachate of 5% fly ash-amended columns. Fly ash application affected both metribuzin breakthrough time and its maximum concentration in the leachate. Further, it resulted in greater retention of metribuzin in the application zone and better effect was observed in the organic carbon poor soils.     

Effect of soil amendments on sorption and mobility of metribuzin in soils

Metribuzin (4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one), is weakly sorbed to soil therefore, leaches easily to lower soil profiles. Soil amendments play a significant role in the management of leaching losses of pesticides. Therefore, present study reports the effect of organic manure and fly ash amendments on metribuzin downward mobility in sandy loam soil columns. Application of animal manure [T-1(OM) and T-2(OM)] and fly ash [T-1(FA) and T-2(FA)] at 2.5% and 5.0% levels increased the metribuzin retention in the soil. Freundlich constant [K(f)(1/n)] values of metribuzin for treatments T-1(OM) and T-2(OM) were 0.70 and 1.11, respectively, which were significantly higher than the value (0.27) in natural soil (T-0). The respective values for treatments T-1(FA) and T-2(FA) were 1.80 and 4.61. Downward mobility of metribuzin was studied in packed soil columns [300 mm (l)x59 mm (i.d.)]. Both the amendments significantly reduced the downward mobility of metribuzin and affected breakthrough time and maximum concentration of metribuzin in the leachate. Leaching losses of metribuzin were decreased from 97% in natural soil (T-0) column to 64% [T-1(OM)] and 42% [T-2(OM)] for animal manure-amended columns and 26% [T-1(FA)] to 100% [T-2(FA)] for fly ash-amended columns, as metribuzin did not leach out of 5% fly ash-amended column. Study indicates that both animal manure and fly ash were quite effective in reducing the downward mobility of metribuzin in packed soil columns of a sandy loam soil.     

Sorption of metolachlor and atrazine in fly ash amended soils: comparison of optimized isotherm models

Adsorption of metolachlor and atrazine was studied in the fly ash (Inderprastha and Badarpur)- amended Inceptisol and Alfisol soils using batch method. Results indicated that sorption of both the herbicides in soil+fly ash mixtures was highly nonlinear and sorption decreased with a higher herbicide concentration in the solution. Also, nonlinearity increased with an increase in the level of fly ash amendment from 0-5%. Three two-parameter monolayer isotherms viz. Langmuir, Temkin, Jovanovic and one imperical Freundlich models were used to fit the experimental data. Data analysis and comparison revealed that the Temkin and the Freundlich isotherms were best-suited to explain the sorption results and the observed and the calculated adsorption coefficient values showed less variability. The study suggested that sorption mechanism of metolachlor and atrazine involved the physical association at the sorbate surface and the nonlinearity in the sorption at higher pesticide or fly ash concentration was due to a decrease in the heat of adsorption and higher binding energy.     

Edaphological characteristics of unweathered and weathered fly ashes from Gondwana and lignite coal

Naturally weathered and unweathered samples of fly ashes produced from Gondwana and lignite coals were characterized for their edaphological properties. The particle size distribution in these fly ashes varied widely, and the percentage of [Formula: see text] size particles governed their water holding capacity. All fly ashes were noncoherent in the dry state and had lower particle density than quartz and mulite. The fly ashes were low in available N, but were sufficient in available P, K, Ca, Mg, S, Cu, Fe, Mn, Zn and B. Among the fly ashes, unweathered lignite fly ash was the richest source of K, Ca, Mg, S and Fe, while weathered lignite fly ash had the highest amounts of Mn, Zn and B. The pH of the fly ashes was closely related to the ratio of exchangeable Ca to exchangeable Al. The fly ashes were high in soluble salt, but were poor in cation exchange capacity. As an amendment to correct soil pH, the fly ashes had a poor buffering capacity. Weathering decreased the total Fe, available S and exchangeable Na percentages, but increased the organic C content of the fly ashes. Invariably, an excess of soluble salts and exchangeable Na could limit plant growth on fly ash dumps. Toxic levels of B and Al existed in only some fly ashes.     

Improving phosphate removal of sand infiltration system using alkaline fly ash

Septic tank effluent is customarily disposed of by soil infiltration. Coarse, sandy soil such as those found in Perth, Western Australia, exhibit low attenuation capabilities for phosphate (PO4(3-)) during effluent infiltration. Amendment of such soil with different amounts of alkaline precipitator and lagoon fly ashes was investigated as a means of reducing phosphorus (P) leakage to ground water. Alkaline precipitator fly ash possessed the highest P sorption capacity in terms of its Langmuir and Freundlich isotherm parameters during initial batch tests. The test materials were repeatedly contacted with fresh PO4(3-) solutions over 90 contacting cycles to gain a better indication of long-term P sorption capability. Again, precipitator fly ash exhibited higher P sorption capacity than lagoon fly ash and Spearwood sand. Column studies assessed the influence of various application rates of alkaline precipitator and lagoon fly ashes on the P removal of septic tank effluent. Septic tank effluent was applied at the rate of 4 cm/day to the column for 12 weeks. Concentrations of P were monitored in the column effluent. All the fly ash columns were more efficient in reducing P migration compared to the sand column. Increased levels of fly ash in the soil columns resulted in increased P attenuation. Lagoon fly ash was inferior to precipitator fly ash for P removal; high application rates of fly ash caused clogging of the infiltration bed apparently due to their lower permeability. It is reasoned that 5-15% precipitator fly ash, and less than 30% lagoon fly ash could be added to coarse sands to produce an infiltration bed, which would result in a better quality effluent than can be obtained with untreated sand alone.     

Effect of charcoal amendment on adsorption, leaching and degradation of isoproturon in soils

The effects of charcoal amendment on adsorption, leaching and degradation of the herbicide isoproturon in soils were studied under laboratory conditions. The adsorption data all fitted well with the Freundlich empirical equation. It was found that the adsorption of isoproturon in soils increased with the rate of charcoal amended (correlation coefficient r=0.957**, P<0.01). The amount of isoproturon in leachate decreased with the increase of the amount of charcoal addition to soil column, while the retention of isoproturon in soils increased with an increase in the charcoal content of soil samples. Biodegradation was still the most significant mechanism for isoproturon dissipation from soil. Charcoal amendment greatly reduced the biodegradation of isoproturon in soils. The half-lives of isoproturon degradation (DT(50)) in soils greatly extended when the rate of added charcoal increased from 0 to 50 g kg(-1) (for Paddy soil, DT(50) values increased from 54.6 to 71.4 days; for Alfisol, DT(50) from 16.0 to 136 days; and for Vertisol, DT(50) from 15.2 to 107 days). The degradation rate of isoproturon in soils was significantly negatively correlated with the amount of added charcoal. This research suggests that charcoal amendment may be an effective management practice for reducing pesticide leaching and enhancing its persistence in soils.     

Effect of wheat and rice straw biochars on pyrazosulfuron-ethyl sorption and persistence in a sandy loam soil

The objective of this research was to investigate the effect of wheat and rice biochars on pyrazosulfuron-ethyl sorption in a sandy loam soil. Pyrazosulfuron-ethyl was poorly sorbed in the soil (3.5–8.6%) but biochar amendment increased the herbicide adsorption, and the effect varied with the nature of the feedstock and pyrolysis temperature. Biochars prepared at 600°C were more effective in adsorbing pyrazosulfuron-ethyl than biochars prepared at 400°C. Rice biochars were better than wheat biochars, and higher herbicide adsorption was attributed to the biochar surface area/porosity. The Freundlich constant 1/n suggested nonlinear isotherms, and nonlinearlity increased with increase in the level of biochar amendment. Desorption results suggested sorption of pyrazosulfuron-ethyl was partially irreversible, and the irreversibility increased with increase in the level of biochar. Both sorption and desorption of pyrazosulfuron-ethyl correlated well with the content of biochars. The free energy change (ΔG) indicated that the pyrazosulfuron-ethyl sorption process was exothermic, spontaneous and physical in nature. Persistence studies indicated that biochar (0.5%) amendment did not have significant effect on herbicide degradation, and its half-life values in the control, 0.5% WBC600- and RBC600-amended rice planted soils were 7, 8.6, and 10.4 days, respectively.     

Adsorption of methabenzthiazuron on six allophanic and nonallophanic soils: effect of organic matter amendment

This article reports on methabenzthiazuron [1-(1,3-benzothiazol-2-yl)-1,3-dimethylurea] (MBT) adsorption process on six agricultural allophanic and nonallophanic soils. The effect of amendment with exogenous organic matter was also studied. Adsorption kinetic fits an hyperbolic model. MBT adsorption reached an apparent equilibrium within 2 h and followed a second-order reaction. The maximum adsorbed amounts for natural soils ranged from 32 to 145 microg g(-1). Rate constants were considered relatively low (0.27-1.5 x 10(-4) [microg g(-1)](1-n) s-1); the slow process was attributed to a combined effect of difussion and adsorption. MBT adsorption fits the Freundlich model with r values > or =0.998 at P < or = 0.001 significance levels. Kf and Freundlich exponents (l/n) ranged from 5.3 to 82.1 cm3 g(-1) and from 0.66 to 0.73, respectively. Kf values for soils with a low organic matter content were lower than that obtained from the only typical allophanic soil derived from volcanic ash under study. Lineal regression analysis between Kf and organic matter content of nonallophanic soils gave a correlation coefficient of 0.980 (P = 0.02). Dispersion of Kd values together with close values of K(OM) indicate that organic matter (OM) was the principal component responsible for MBT adsorption in unamended soils. Addition of peat decreased soil pH and increased adsorption capacity for allophanic and nonallophanic soils. Kinetic experiments showed enhancements of Xmax values and lower rate constants.     

Remediation of metal-contaminated soils with the addition of materials--part I: characterization and viability studies for the selection of non-hazardous waste materials and silicates

Contamination episodes in soils require interventions to attenuate their impact. These actions are often based on the addition of materials to increase contaminant retention in the soil and to dilute the contaminant concentration. Here, non-hazardous wastes (such as sugar foam, fly ash and a material produced by the zeolitization of fly ash) and silicates (including bentonites) were tested and fully characterized in the laboratory to select suitable materials for remediating metal-contaminated soils. Data from X-ray fluorescence (XRF), N₂ adsorption/desorption isotherms, X-ray diffraction (XRD) and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDX) analyses revealed the chemical composition, specific surface area and the phases appearing in the materials. A pH titration test allowed the calculation of their acid neutralization capacity (ANC). The metal sorption and desorption capacities of the waste materials and silicates were also estimated. Sugar foam, fly ash and the zeolitic material were the best candidate materials. Sugar foam was selected because of its high ANC (17 000 meq kg⁻¹), and the others were selected because of their larger distribution coefficients and lower sorption reversibilities than those predicted in the contaminated soils.     

Impact of redox conditions on metolachlor and metribuzin degradation in Mississippi flood plain soils

The effect of soil redox conditions on the degradation of metolachlor and metribuzin in two Mississippi soils (Forrestdale silty clay loam and Loring silt loam) were examined in the laboratory. Herbicides were added to soil in microcosms and incubated either under oxidized (aerobic) or reduced (anaerobic) conditions. Metolachlor and metribuzin degradation under aerobic condition in the Forrestdale soil proceeded at rates of 8.83 ngd(-1) and 25 ngd(-1), respectively. Anaerobic degradation rates for the two herbicides in the Forestdale soil were 8.44 ngd(-1) and 32.5 ngd(-1), respectively. Degradation rates for the Loring soil under aerobic condition were 24.8 ngd(-1) and 12.0 ngd(-1) for metolachlor and metribuzin, respectively. Metolachlor and metribuzin degradation rates under anaerobic conditions in the Loring soil were 20.9 ngd(-1) and 5.35 ngd(-1). Metribuzin degraded faster (12.0 ngd(-1)) in the Loring soil under aerobic conditions as compared to anaerobic conditions (5.35 ngd(-1)).     

Potential Use of Olive-Waste Ash from Cogeneration Plants as a Soil Amendment

A greenhouse study was conducted to evaluate the potential use of olive-cake ash as a soil amendment, using pepper (Capsicum annuum, L. cv Italian sweet). Three soils of different pH (acidic, neutral and calcareous) were used. Treatments included a control (no fertilizer application), NPK fertilizer, and two ash-application rates that provided a complete dose (equivalent to the K₂O amount in the fertilizer) and a half dose (equivalent to half the K₂O amount in the fertilizer), respectively. The ash was effective in raising soil pH. Ash treatments increased the pepper (stems and leaves) dry matter yield over control; although these increases were lower than treatment including NPK. Application of ash significantly increased leaf P concentration and AB-DTPA extractable P in soil, especially in the acidic and neutral soils. Leaf K concentrations and readily and slowly available K forms in soils were affected positively by the addition of the ash. These results demonstrate that ash from the combustion of wet olive cake can be used as a beneficial organic soil amendment.     

Speciation and mobility of cadmium in straw and wood combustion fly ash

Two fly ashes from biomass combustion have been analysed regarding cadmium speciation and mobility. A fly ash from straw combustion contained 10 mg Cd/kg dry matter, and around 50% of the cadmium was leachable in water. The possible main speciation of cadmium in this fly ash was CdCl2. When adding this fly ash to agricultural soil a threat for groundwater contamination and plant uptake is existing. A fly ash from wood chip combustion had 28.6 mg Cd/kg dry matter. In this fly ash, the cadmium was bound more heavily, with only small amounts of cadmium leached in mild extractants. A possible speciation of cadmium in this fly ash was as oxide or as CdSiO3. Long-term effects and accumulation of cadmium could be a problem when adding this fly ash to agricultural or forest soils.     

Influence of soil properties on heavy metal sequestration by biochar amendment: 1. Copper sorption isotherms and the release of cations

The amendment of carbonaceous materials such as biochars and activated carbons is a promising in situ remediation strategy for both organic and inorganic contaminants in soils and sediments. Mechanistic understandings in sorption of heavy metals on amended soil are necessary for appropriate selection and application of carbonaceous materials for heavy metal sequestration in specific soil types. In this study, copper sorption isotherms were obtained for soils having distinct characteristics: clay-rich, alkaline San Joaquin soil with significant heavy metal sorption capacity, and eroded, acidic Norfolk sandy loam soil having low capacity to retain copper. The amendment of acidic pecan shell-derived activated carbon and basic broiler litter biochar lead to a greater enhancement of copper sorption in Norfolk soil than in San Joaquin soil. In Norfolk soil, the amendment of acidic activated carbon enhanced copper sorption primarily via cation exchange mechanism, i.e., release of proton, calcium, and aluminum, while acid dissolution of aluminum cannot be ruled out. For San Joaquin soil, enhanced copper retention by biochar amendment likely resulted from the following additional mechanisms: electrostatic interactions between copper and negatively charged soil and biochar surfaces, sorption on mineral (ash) components, complexation of copper by surface functional groups and delocalized π electrons of carbonaceous materials, and precipitation. Influence of biochar on the release of additional elements (e.g., Al, Ca) must be carefully considered when used as a soil amendment to sequester heavy metals.     

Potential use of olive-waste ash from cogeneration plants as a soil amendment

A greenhouse study was conducted to evaluate the potential use of olive-cake ash as a soil amendment, using pepper (Capsicum annuum, L. cv Italian sweet). Three soils of different pH (acidic, neutral and calcareous) were used. Treatments included a control (no fertilizer application), NPK fertilizer, and two ash-application rates that provided a complete dose (equivalent to the K2O amount in the fertilizer) and a half dose (equivalent to half the K2O amount in the fertilizer), respectively. The ash was effective in raising soil pH. Ash treatments increased the pepper (stems and leaves) dry matter yield over control; although these increases were lower than treatment including NPK. Application of ash significantly increased leaf P concentration and AB-DTPA extractable P in soil, especially in the acidic and neutral soils. Leaf K concentrations and readily and slowly available K forms in soils were affected positively by the addition of the ash. These results demonstrate that ash from the combustion of wet olive cake can be used as a beneficial organic soil amendment.     

Comparative assessment of metribuzin sorption efficiency of biochar,hydrochar and vermicompost

Abstract

In this study, we used two biochars (BC) produced from grapevine pruning residues (BCgv) and red spruce wood (BCrs), two hydrochars (HC) from urban pruning residues (HCup) and the organic fraction of municipal solid wastes (HCuw), and two vermicomposts (VC) obtained vermicomposting digestates from buffalo manure (VCbm) and mixed feedstock (VCmf). Adsorption kinetics and isotherms of metribuzin onto these materials were performed. Sorption kinetics followed preferentially a pseudo-second-order model, thus indicating the occurrence of chemical interactions between the sorbate and the adsorbents. Adsorption constants were calculated using the Freundlich and Langmuir models. Metribuzin sorption data on BCgv and both HC fitted preferentially the Freundlich equation, whereas on the other materials data fitted both isotherms well (r?>?0.95). Metribuzin sorption capacity of the materials followed the trend BC?>?HC?>?VC. Sorption constants of metribuzin normalised per organic carbon content (K_OC) on BCgv, BCrs, HCup, HCuw, VCbm and VCmf were 561, 383, 251, 214, 102 and 84?L kg^?1, respectively. A significant positive correlation (P?=?0.016) was calculated between distribution coefficients (K_d) of all materials and the corresponding organic carbon contents, thus indicating a prominent role of the organic fraction of these materials in the adsorption of metribuzin.     

Lead sorption in calcareous soils

The sorption of lead by three soils that differed in texture and calcium carbonate content was studied at three different temperatures. Lead sorption was found to conform to both Freundlich and Langmuir isotherms. Soil adsorption maxima were derived from the reciprocal of the slope obtained by a least-squares fit of Langmuir plots for each soil. The highest adsorption capacity was exhibited by CaCO(3)-rich soil (773.55 mmol Pb kg(-1)). Raising the temperature from 298 K to 308 and 318 K increased the sorption capacity of all of the soils.     

Sorption-desorption behavior of metsulfuron-methyl and sulfosulfuron in soils

Sorption of metsulfuron-methyl and sulfosulfuron were studied in five Indian soils using batch sorption method. Freundlich adsorption equation described the sorption of herbicides with K(f) (adsorption coefficient) values ranging between 0.21 and 1.88 (metsulfuron-methyl) and 0.37 and 1.17 (sulfosulfuron). Adsorption isotherms were L-type suggesting that the herbicides sorption decreased with increase in the initial concentration of the herbicide in the solution. The K(f) for metsulfuron-methyl showed good positive correlation with silt content (significant at p = 0.01) and strong negative correlation with the soil pH (significant at p = 0.05) while sorption of sulfosulfuron did not correlate with any of the soil parameter. Desorption of herbicides was concentration dependent and, in general, sulfosulfuron showed higher desorption than the metsulfuron-methyl. The study indicates that these herbicides are poorly sorbed in the Indian soil types and there may be a possibility of their leaching to lower soil profiles.     

Determination of polychlorinated dibenzo-p-dioxins and dibenzo-furans in solid residues from wood combustion by HRGC/HRMS

PCDD/PCDF were determined in solid samples from wood combustion. The samples included grate ashes, bottom ashes, furnace ashes as well as fly and cyclone ashes. The solid waste samples were classified into bottom and fly ash from native wood and bottom and fly ash from waste wood. For each of the four classes concentration distribution patterns from individual congeners, the sums of PCDD/PCDF and the international toxicity equivalents (I-TEQ) values are given. The I-TEQ levels of fly ash from waste wood burning can be approximately up to two thousand times higher than the values from fly ashes of natural wood. The I-TEQ levels in bottom ashes from waste wood combustion systems are as low as the corresponding ashes from the combustion of native wood. Grate ash samples from waste wood combustion systems with low carbon burnout show high levels of PCDD/PCDF.