Leaching of carbonated air pollution control residues using compliance leaching tests

The leaching characteristics of air pollution control (APC) residues collected in Shanghai, China, were compared by performing three compliance leaching tests. These were the standard Chinese method for determining the leaching toxicity of solid waste (GB 5086.1-1997), the USEPA's Toxicity Characteristic Leaching Procedure (TCLP), and the new European shake test (EN 12457-3). In particular, behaviors of raw samples and samples that had been subjected to natural aging were compared. Both the leaching tests and natural aging substantially affected the leaching results concerning the APC residue samples. Most importantly, EN and GB tests classified the raw APC residues as hazardous, but the residues passed the TCLP test as nonhazardous. After it had been naturally aged for 720 h, however, the aged sample was classified as hazardous by the TCLP and EN tests, but as nonhazardous by the GB test. Metals that are thought to have been immobilized by carbonation were released at pH 6.3. Model calculations based on the geochemical thermodynamic equilibrium model MINTEQA2 revealed that the formation of metal carbonates did not correspond to the noted change in the leaching behaviors in the three leaching tests. Rather, the partial neutralization of alkaline ash by dissolved CO2 changing the final pH of the leachate dominated the leaching characteristics. The leaching results showed a change in leachate pH.     

Leaching mechanisms of Cr(VI) from chromite ore processing residue

Batch leaching tests, qualitative and quantitative x-ray powder diffraction (XRPD) analyses, and geochemical modeling were used to investigate the leaching mechanisms of Cr(VI) from chromite ore processing residue (COPR) samples obtained from an urban area in Hudson County, New Jersey. The pH of the leaching solutions was adjusted to cover a wide range between 1 and 12.5. The concentration levels for total chromium (Cr) and Cr(VI) in the leaching solutions were virtually identical for pH values >5. For pH values <5, the concentration of total Cr exceeded that of Cr(VI) with the difference between the two attributed to Cr(III). Geochemical modeling results indicated that the solubility of Cr(VI) is controlled by Cr(VI)-hydrocalumite and Cr(VI)-ettringite at pH >10.5 and by adsorption at pH <8. However, experimental results suggested that Cr(VI) solubility is controlled partially by Cr(VI)-hydrocalumite at pH >10.5 and by hydrotalcites at pH >8 in addition to adsorption of anionic chromate species onto inherently present metal oxides and hydroxides at pH <8. As pH decreased to <10, most of the Cr(VI) bearing minerals become unstable and their dissolution contributes to the increase in Cr(VI) concentration in the leachate solution. At low pH ( <1.5), Cr(III) solid phases and the oxides responsible for Cr(VI) adsorption dissolve and release Cr(III) and Cr(VI) into solution.     

Properties of steel foundry electric arc furnace dust solidified/stabilized with Portland cement

Electric arc furnace dust from steel production is generated in considerable amounts worldwide and needs to be treated as hazardous waste. The aim of this study was to investigate the properties of electric arc furnace dust solidified/stabilized by using Portland cement. Mortar and paste samples were prepared with varying waste-to-binder ratios between 0% and 90%. A comprehensive experimental program was designed including XRF characterization, setting time, unconfined compressive strength, and toxicity characteristics leaching procedure (TCLP), synthetic precipitation leaching procedure (SPLP), and acid neutralization capacity (ANC) tests. The results were evaluated in order to determine if the solidified /stabilized product can be disposed of at a landfill site with domestic waste or at a segregated landfill. The effect of using sand on S/S performance was also investigated. The results indicated that the solidification /stabilization process using PC helps the heavy metals to be bound in the cement matrix, but the TCLP leaching results exceeded the EPA landfilling limits. The SPLP leaching results conformed to the limits implying that the waste or S/S products can be disposed of at a segregated landfill; however the low ANC of the S/S products reveals that there may be leaching in the long-term. The sand used in the mortar samples adversely affected the S/S performance, causing higher heavy metal leaching levels, and lower pH levels in the leachate after the TCLP extraction than those measured in the leachate of the paste samples.     

Rainfall timing and frequency influence on leaching of Escherichia coli RS2G through soil following manure application

The time between swine (Sus scrofa) manure application to soil as a crop fertilizer, the first rainfall event, and the frequency of rainfall events should influence leaching potential of fecal pathogens. Soil microcosms were inoculated in the lab with a swine manure isolate of Escherichia coli, strain RS2G, expressing green fluorescent protein, to examine how timing and frequency of rainfall events influences RS2G leaching and survival in soil. Liquid swine manure inoculated with RS2G was applied to intact soil cores (20 cm in diameter x 30 cm long) 4, 8, or 16 d before the first rainfall event (50.8 mm over a 4-h period), and each core received one to three rainfall events. Manure application methods (no-till surface-broadcast, broadcast and incorporated, and tilled before broadcast) had no affect on leaching, although there was greater survival in soils when the manure had been incorporated. Most of the RS2G in the leachate appeared following the first rainfall event and RS2G leaching decreased with increasing time between manure application and the first rainfall, although leachates contained as much as 3.4 to 4.5 log colony forming units (CFU) 100 mL(-1) of RS2G when the first rainfall occurred 16 d after manure application. With increasing frequency of rainfalls there was a decrease in subsequent concentrations of RS2G in the leachate. There was no correlation between leachate RS2G and total coliforms or fecal streptococci concentrations. Soil RS2G numbers were 1 to 10% of the inoculum regardless of the length of time between manure application and the first rainfall. RS2G leaching was mostly influenced by the time between manure application and first rainfall event, and significant leaching and survival in soil was possible even if the first rain occurred 16 d after manure application.     

Mechanisms controlling the leaching kinetics of fixated flue gas desulfurization (FGD) material under neutral and acidic conditions

A number of agricultural and engineering uses for fixated flue gas desulfurization (FGD) material exist; however, the potential for leaching of hazardous elements has limited widespread application and the processes controlling the leaching of this material are poorly understood. In this study, a flow-through rotating-disk system was applied to elucidate the relative importance of bulk diffusion, pore diffusion, and surface chemical reaction in controlling the leaching of fixated FGD material under pH conditions ranging from 2.2 to 6.8. Changing the hydrodynamics in the rotating disk system did not affect the leaching kinetics at both pH 2.2 and 6.8, indicating that bulk diffusion was not the kinetic-limiting step. Application of the shrinking core model (SCM) to the data suggested a surface reaction-controlled mechanism, rather than a pore diffusion mechanism. The leaching of fixated FGD material increased with decreasing pH, suggesting it can be described by a combination of an intrinsic hydration reaction and a proton-promoted dissolution reaction. X-ray diffraction (XRD) and elemental composition analyses before and after leaching suggests that for most elements a number of solid phases controlled the leaching process.     

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.     

Quantification of uncertainty of experimental measurement in leaching test on cement-based materials

When mineral wastes are reused in construction materials, a current practice is to evaluate their environmental impact using standard leaching test. However, due to the uncertainty of the measurement, it is usually quite difficult to estimate the pollutant potential compared to other materials or threshold limits. The aim of this paper is to give a quantitative evaluation of the uncertainty of leachate concentrations of cement-based materials, as a function of the number of test performed. The relative standard deviations and relative confidence intervals are determined using experimental data in order to give a global evaluation of the uncertainty of leachate concentrations (determination of total relative standard deviation). Various combinations were realized in order to point out the origin of large dispersion of the results (determination of relative standard deviation linked to analytical measured and to leaching procedure), generalisation was suggested and the results were compared to literature. An actual example was given about the introduction of residue (meat and bone meal bottom ash--MBM-BA) in mortar, leaching tests were carried out on various samples with and without residue MBM-BA. In conclusion large dispersion were observed and mainly due to heterogeneity of materials. So heightened attention needed to analyse leaching result on cement-based materials and further more other tests (e.g. ecotoxicology) should be performed to evaluate the environmental effect of these materials.     

Colloid mobilization and arsenite transport in soil columns: effect of ionic strength

Colloid generation and transport in soils is of significance because of suspected colloid-facilitated transport of contaminants to the groundwater. In this study, colloid mobilization and its effect on the transport of arsenite [As(III)] were investigated in Olivier (fine-silty, mixed, active, thermic Aquic Fraglossudalfs) and Windsor (mixed, mesic typic Udipsamments) soil columns. Input solution of 10 mg L(-1) As(III) in 0.01 M NaCl was applied to water-saturated columns, and followed by leaching with deionized water (DIW). Flow interruptions were performed during the As(III) input and DIW leaching phases. Turbidity, electrical conductivity (EC), and pH of column effluents were monitored with time. Total and dissolved concentrations of As, Fe, and Al were analyzed. Effluent results demonstrated that colloid-facilitated transport contributed little to arsenic movement when the solution ionic strength was maintained constant. Mobilization of colloidal amorphous material and enhanced transport of As(III) were observed as a result of changes in ionic strength of the input solution. The peak of colloid generation coincided with peak concentrations of Fe, suggesting mobilization of Fe oxides and facilitated transport of As(III) adsorbed on oxide surfaces. Colloid mobilization was enhanced due to flow interruption in the Olivier column, which suggests slow dissociation of aggregated colloidal particles. Moreover, effluent results indicate significant effect of organic matter in stabilizing aggregates of colloidal particles.     

The effect of olive mill wastewater on seed germination after various pretreatment techniques

Olive mill wastewater (OMW) management has been a major issue of environmental concern for olive oil producing countries. OMW can be a serious nuisance, when disposed of untreated, due to its significantly high organic load, its phytotoxic properties and its relatively low biodegradability. Field and plant irrigation with raw or pretreated OMW is an easy and relatively inexpensive method to treat and dispose of OMW. Typical pretreatment techniques could be comprised of phase separation through a settling basin, dilution with water, aeration to promote biological degradation and pH neutralization. A full factorial experimental design approach was used here to study the main effects and interactions of the above four pretreatment techniques on the germination of tomato and chicory seeds. Results of the study showed that the most statistically significant technique affecting OMW phytotoxicity is water dilution. The next most significant technique was aeration. In particular, phytotoxicity decreased with increased OMW dilution with water, when OMW was aerated and without pH adjustment. pH neutralization resulted in increased phytotoxicity. Settling did not significantly decrease the phytotoxicity of settled OMW and is therefore not considered necessary in an OMW management system in which plant irrigation is the goal. The interaction of aeration and pH was, marginally, the most significant two-way interaction for tomato seeds, while no interactions were significant when chicory seeds were used.     

Sorption of MS2 bacteriophage to layered double hydroxides: effects of reaction time, pH, and competing anions

Batch sorption and column breakthrough studies were conducted to investigate the potential of layered double hydroxides (LDHs) to remove bacteriophage MS2 from contaminated waters. All four of the LDHs evaluated in this study had very high retention capacities for MS2. Sorption results showed that MS2 could be completely removed from 5.2 x 10(2) plaque-forming units (pfu)/mL solution by Mg-Al LDH 2 (i.e., 2:1 Mg to Al ratio LDH), with the highest sorption capacity observed in this study of 1.51 x 10(10) pfu/g. Attachment of MS2 to LDHs was a rapid process and reached quasi-equilibrium after a 1-h reaction time. Within the pH range studied (pH 4-9), Mg-Al LDH 2 showed high sorption potential for MS2 at all pH values but sorption decreased slightly with increasing solution pH. Background solution anions influenced virus sorption, with SO4(2-) and HPO4(2-) decreasing sorption significantly whereas the presence of NO3- had little effect on the attachment of MS2 to Mg-Al LDH 2. The addition of another virus (phiX174) only caused a slight decrease in the retention of MS2 by Mg-Al LDH 2, suggesting that there was insignificant competitive sorption between MS2 and phiX174 on LDH surfaces. Results from column experiments indicate that there was no MS2 breakthrough from columns packed with Mg-Al LDH 2-coated sand, suggesting complete MS2 retention at the virus concentration tested. The high mass recovery by beef extract solution revealed that the removal of viruses by the LDH was due to sorption of MS2 to LDH surfaces, rather than inactivation.     

Ethylenediaminedissuccinate as a new chelate for environmentally safe enhanced lead phytoextraction

Using a soil column experiment, we compared the effect of a single dose and weekly additions of ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedissuccinate (EDDS) on the uptake of Pb, Zn, and Cd by Chinese cabbage [Brassica rapa L. subsp. pekinensis (Lour.) Hanelt], and on the leaching of heavy metals through the soil profile. The analysis of plant material revealed that both chelates increased the concentrations of Pb and, to a lesser extent, also of Zn and Cd in the leaves of the test plant. The most effective applications were single doses of 10 mmol EDTA and EDDS kg(-1) soil, which caused the concentrations of Pb in the shoots to increase 94.2- and 102.3-fold, respectively, relative to the control. The same dose of EDTA increased the concentration of Zn and Cd in the leaves 4.3- and 3.8-fold and of EDDS 4.7- and 3.5-fold, respectively. In treatments with weekly additions and lower concentrations of both chelates, EDTA was more effective than EDDS in increasing the plant uptake of Pb. In soil columns treated with weekly additions of 10 mmol kg(-1) EDTA, on average 22.7, 7.0, and 39.8% of initial total Pb, Zn, and Cd in the soil were leached through the soil profile. The same amount of EDDS caused much lower leaching of Pb and Cd--only 0.8 and 1.5% of initial total concentrations. Leaching of Zn, 6.2% of the total concentration, was comparable with the EDTA treatment. A biotest with red clover (Trifolium pratense L.) indicated a greater phytotoxic effect of EDTA than EDDS addition. EDDS was also less toxic to soil fungi, as determined by phospholipid fatty acid (PLFA) analysis, and caused less stress to soil microorganisms, as indicated by the trans to cis PLFA ratio. Chelate addition did not prevent the development of arbuscular mycorrhiza on red clover.     

Decontamination of Fly Ash and Used Lime from Municipal Waste Incinerator Using Thiobacillus ferrooxidans

Thiobacillus ferrooxidans to leach metals from APCR to render them nonhazardous. The multistage solubilization process involves an alkaline aqueous phase that removes some Pb. In the second phase, the APCR are acidified to pH 4 with H₂SO₄, then inoculated with a bacterial culture that has been acclimated in the presence of 2% Fe (FeCl₃). Several rinses and decantings achieve removal of the leachable metals. The final step involves the addition of Ca(H₂PO₄)₂ and an increase in the treatment pH prior to the final filtration. Viability of thiobacilli in APCR was poor. Despite this problem, the removal of Pb was 35.9%, 46.0%, and 68.7% (for APCR containing 1594, 3026, and 5038 mg Pb/kg, respectively), which demonstrates greater metal removal with increased APCR contamination. Zn removal varied from 68.2% (8273 mg Zn/kg APCR) to 79.5% (16,873 mg Zn/kg APCR), which was positively correlated to the level of residue contamination, whereas Cu was removed in the proportions of 26.9% (495 mg Cu/kg APCR) to 68.2% (465 mg Cu/kg APCR). Cadmium removal appeared to be independent of the level of Cd in the APCR; Cd was removed to the greatest degree, with a variation of 92.0% (129 mg Cd/kg APCR) to 94.7% (267 mg Cd/kg APCR). The treated APCR were tested using four different leachate tests. The APCR released 43 mg Pb/liter during contact with water, and 7.40 mg Cd/liter during TCLP [the toxicity characterization leaching procedure of the United States Environmental Protection Agency (US EPA)]. After biological treatment, the leachate from TCLP was within the acceptance criteria of the US EPA, if the pH of the APCR was increased to pH 5 after the biological treatment. In the case of the Transport Canada leaching test, a betterment of the process is required in order to satisfy the stringent regulatory level of 0.5 mg Cd/liter (0.68 and 0.57 mg/liter).     

Effect of tomato packinghouse wastewater properties on phosphorus and cation leaching in a spodosol

Land application of wastewater is a common practice. However, coarse-textured soils and shallow groundwater in Florida present favorable conditions for leaching of wastewater-applied constituents. Our objective in this study was to determine phosphorus (P) and associated cations (Ca, Mg, K, Na) leaching in a Spodosol irrigated with tomato packinghouse wastewater. We packed 12 polyvinyl chloride soil columns (30 cm internal diameter × 50 cm length) with two soil horizons (Ap and A/E) and conducted 30 sequential leaching events by irrigating with wastewater at low (0.84 cm d), medium (1.68 cm d), and high (2.51 cm d) rates. The control treatment received deionized water at 1.68 cm d Leachate pH was lower (6.4-6.5) and electrical conductivity (EC) was higher in the wastewater-treated columns (0.85-1.78 dS m) than in the control treatment (pH 6.9; EC, 0.12 dS m) due to the low pH (6.2) and high EC (2.16 dS m) of applied wastewater. Mean leachate P concentrations were greatest in the control treatment (0.70 mg L), followed by the high (0.60 mg L) and low and medium wastewater-treated columns (0.28-0.33 mg L). Leachate concentrations of Na, Ca, Mg, and K were significantly ( < 0.05) greater in wastewater-treated columns than in the control. Concentrations of P, Na, and K in leachate remained lower than the concentrations in the applied wastewater, indicating their retention in the soil profile. In contrast, leachate Ca and Mg concentrations were greater than in applied wastewater during several leaching events, suggesting that additional Ca and Mg were leached from the soil. Our results suggest that tomato packinghouse wastewater can be beneficially land-applied at 1.68 cm d in Florida's Spodosols without significant P and cation leaching.     

Metal immobilization in soils using synthetic zeolites

In situ immobilization of heavy metals in contaminated soils is a technique to improve soil quality. Synthetic zeolites are potentially useful additives to bind heavy metals. This study selected the most effective zeolite in cadmium and zinc binding out of six synthetic zeolites (mordenite-type, faujasite-type, zeolite X, zeolite P, and two zeolites A) and one natural zeolite (clinoptilolite). Zeolite A appeared to have the highest binding capacity between pH 5 and 6.5 and was stable above pH 5.5. The second objective of this study was to investigate the effects of zeolite addition on the dissolved organic matter (DOM) concentration. Since zeolites increase soil pH and bind Ca, their application might lead to dispersion of organic matter. In a batch experiment, the DOM concentration increased by a factor of 5 when the pH increased from 6 to 8 as a result of zeolite A addition. A strong increase in DOM was also found in the leachate of soil columns, particularly in the beginning of the experiment. This resulted in higher metal leaching caused by metal-DOM complexes. In contrast, the free ionic concentration of Cd and Zn strongly decreased after the addition of zeolites, which might explain the reduction in metal uptake observed in plant growth experiments. Pretreatment of zeolites with acid (to prevent a pH increase) or Ca (to coagulate organic matter) suppressed the dispersion of organic matter, but also decreased the metal binding capacity of the zeolites due to competition of protons or Ca.     

Solution chemistry influence on metal mobility in biosolids-amended soils

Many studies have implicated dissolved organic carbon (DOC) as an important contributor to the elevated mobility of trace metals in soils amended with biosolids. Few of these studies, however, have quantified both DOC and metal concentrations. We completed laboratory leaching column studies on a dryland Platner loam (fine, smectitic, mesic Aridic Paleustoll) and an irrigated Osgood sand (loamy, mixed, mesic Arenic Ustollic Haplargid), both with a history of biosolids application. The soils were neutral to slightly alkaline in pH prior to amendment. We performed an additional application of biosolids to one set of columns in the laboratory at a rate of 28 Mg ha(-1) to investigate the effect of time following application on metal mobility. The effect of electrolyte concentration was studied by using both distilled water and simulated irrigation water. Biosolids application increased both DOC and Cu in the column effluents resulting in a positive correlation between Cu and DOC across application treatments for both soils. Both Cu and Pb were mobilized under conditions of low electrical conductivity (EC). This may be the result of the release of a strong metal-binding component of DOC under these conditions. Conversely, Zn mobility was positively correlated with EC, suggesting that either cation exchange or the formation of inorganic complexes influences Zn mobility. Anodic stripping voltammetry measurements indicated that only a small percentage of the total dissolved metals existed as free ions or inorganic complexes; the remainder appears to be complexed to DOC.     

Effect of liquid cow manure on andisol properties and atrazine adsorption

Application of animal manure amendments to agricultural soils is a common practice to improve soil fertility through the addition of essential plant nutrients. This practice may increase the potential for atrazine (2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-triazine) leaching due to competition for adsorption sites between the pesticide and dissolved organic carbon (DOC) added through manure. We evaluated the influence of liquid cow manure (LCM) application on soil properties, atrazine adsorption, and the physicochemical controlling mechanisms in an Andisol. The LCM was applied at rates equivalent to 0, 100,000, 200,000, and 300,000 L ha(-1), resulting in treatments S-0, S-100, S-200, and S-300, respectively. The LCM application increased DOC and pH of the soils immediately on addition, but pH returned to S-0 values 30 d after application. The LCM application did not modify atrazine adsorption with the two lowest application rates (S-100 and S-200), but atrazine adsorption was decreased in S-300 (K(f) = 0.96) compared with the control (S-0) (K(f) = 1.19), possibly due to the competitive adsorption of DOC with the pesticide. The Fourier-transformed infrared analysis showed that LCM increased aliphaticity and presence of N-containing groups and polysaccharide-like groups in amended soils; however, these properties did not modify the atrazine interaction in the studied amended soils. Interestingly the addition of DOC to soil at the high application rate (S-300) reduced atrazine adsorption in this rich OM Andisol despite the LCM not raising the concentration of stable organic matter. The application of high rates of liquid manure containing DOC incurs an increased risk of pesticide leaching.     

The US freshwater supply shortage: Experiences with desalination as part of the solution

Parts of the USA are facing impending shortages of freshwater. One proposed solution is the construction of desalination plants to turn seawater into freshwater. Although seawater desalination plants are widely used in the Middle East, especially Saudi Arabia, there are few desalination plants in the USA. In 2003, Tampa Bay Water built the largest desalination plant in North America. Persistent operating problems and escalating costs have caused the utility to re-evaluate its reliance on the seawater desalination plant as part of a long-term regional water supply strategy. In addition, environmental effects of the plant are uncertain. Advances in reverse osmosis technology have significantly reduced desalination costs. However, desalination of seawater is still more expensive than other freshwater supply sources and demand management measures. With time and research, seawater desalination may prove to be a sustainable, cost-effective source of new freshwater supplies, especially if plants are coupled with renewable energy sources. Until then, the development of small-scale groundwater desalination plants, the re-use of water, water conservation, and a more efficient allocation of water through higher prices and rising block rates will be important strategies in meeting growing water demand. Moreover, it is important to improve the coordination between water supply planning and land use planning as populations continue to increase.     

Kinetic research on the sorption of aqueous lead by synthetic carbonate hydroxyapatite

The sorption of aqueous lead on carbonate-hydroxyapatite (CHAp) is a complicated non-homogeneous solid/water reaction, which from the kinetic point of view has two stages. In the first stage, the reaction rate is so fast and the kinetic pathway so intricate that further research is required. In the second stage, the reaction rate slows down and the reaction process follows that of a first-order kinetic equation. Experimental results show that the relationship between the reaction rate constant k(1) and temperature T agrees with the Arrhenius equation, and that the activation energy of sorption (E(a)) is 11.93 kJ/mol and the frequency factor (A) is 2.51/s. The reaction rate constant k(1) increases with the Pb(2+) initial concentration and decreasing pH, but with increasing CHAp dosage. X-ray diffraction (XRD), scanning electron microscopy with energy dispersion spectrum (SEM-EDS) and toxicity characteristic leaching procedure (TCLP) tests indicate that the main sorption mechanism is dissolution-precipitation, in conjunction with surface sorption.     

Phosphate treatment of firing range soils: lead fixation or phosphorus release?

Phosphate treatment of lead (Pb)-contaminated soils relies on the premise that Pb converts to the thermodynamically stable, insoluble mineral class of pyromorphites. Recent research showed that treatment performance is kinetically controlled and strongly dependent on soil pH; this study employed an acidic phosphate (P) form, monobasic calcium phosphate (MCP), to investigate treatment performance of Pb occurring in an alkaline-buffered and an acidic firing range soil. The results of leaching, X-ray powder diffraction (XRPD), and modeling analyses showed that P and Pb dissolution in the alkaline soil and transformation reactions were kinetically controlled, so that: (i) TCLP (toxicity characteristic leaching procedure) and SPLP (synthetic precipitation leaching procedure) results were poor to marginal even at high MCP dosages; (ii) brushite (Ca(HPO(4)).2H(2)O) and cerussite (PbCO(3)) persisted in XRPD patterns; and, (iii) geochemical modeling failed to predict leaching and phase assemblages. In the acidic soil, Pb-P reactions promoted further soil acidification, improved TCLP performance, and generated better agreement with the equilibrium-based model; however, SPLP and modeling results showed that Pb concentrations could not be reduced below 15 microg/L mainly due to the low soil pH. The marginal or inadequate Pb immobilization was observed in both soils despite the elevated MCP dosages, which were well in excess of the pyromorphite stoichiometric ratio (P/Pb = 0.6). Additionally, P leaching concentrations and rates were extremely high (>300 mg/L), under both SPLP and deionized (DI) water extraction conditions, and as predicted by thermodynamic equilibrium. The performance and sustainability of phosphate-based treatment therefore seem questionable.     

Effect of biochar amendment on tylosin adsorption-desorption and transport in two different soils

The role of biochar as a soil amendment on the adsorption-desorption and transport of tylosin, a macrolide class of veterinary antibiotic, is little known. In this study, batch and column experiments were conducted to investigate the adsorption kinetics and transport of tylosin in forest and agricultural corn field soils amended with hardwood and softwood biochars. Tylosin adsorption was rapid at initial stages, followed by slow and continued adsorption. Amounts of adsorption increased as the biochar amendment rate increased from 1 to 10%. For soils with the hardwood biochar, tylosin adsorption was 10 to 18% higher than that when using the softwood biochar. Adsorption kinetics was well described by Elovich equation ( ≥ 0.921). As the percent of biochar was increased, the rates of initial reactions were generally increased, as indicated by increasing α value at low initial tylosin concentration, whereas the rates during extended reaction times were generally increased, as indicated by decreasing β value at high initial tylosin concentration. A considerably higher amount of tylosin remained after desorption in the corn field soil than in the forest soil regardless of the rate of biochar amendment, which was attributed to the high pH and silt content of the former. The breakthrough curves of tylosin showed that the two soils with biochar amendment had much greater retardation than those of soils without biochar. The CXTFIT model for the miscible displacement column study described well the peak arrival time as well as the maximum concentration of tylosin breakthrough curves but showed some underestimation at advanced stages of tylosin leaching, especially in the corn field soil. Overall, the results indicate that biochar amendments enhance the retention and reduce the transport of tylosin in soils.