Feasibility of bioleaching integrated with a chemical oxidation process for improved leaching of valuable metals from refinery spent hydroprocessing catalyst

Bioleaching is considered an eco-friendly technique for leaching metals from spent hydroprocessing catalysts; however, the low bioleaching yield of some valuable metals (Mo and V) is a severe bottleneck to its successful implementation. The present study reported the potential of an integrated bioleaching-chemical oxidation process in improved leaching of valuable metals (Mo and V) from refinery spent hydroprocessing catalysts. The first stage bioleaching of a spent catalyst (coked/decoked) was conducted using sulfur-oxidizing microbes. The results suggested that after 72 h of bioleaching, 85.7% Ni, 86.9% V, and 72.1% Mo were leached out from the coked spent catalyst. Bioleaching yield in decoked spent catalyst was relatively lower (86.8% Ni, 79.8% V, and 59.8% Mo). The low bioleaching yield in the decoked spent catalyst was attributed to metals’ presence in stable fractions (residual + oxidizable). After first stage bioleaching, the integration of a second stage chemical oxidation process (1 M H₂O₂) drastically improved the leaching of Ni, Mo, and V (94.2–100%) from the coked spent catalyst. The improvement was attributed to the high redox potential (1.77 V) of the H₂O₂, which led to the transformation of low-valence metal sulfides into high-valence metallic ions more conducive to acidic bioleaching. In the decoked spent catalyst, the increment in the leaching yield after second stage chemical oxidation was marginal (<5%). The results suggested that the integrated bioleaching-chemical oxidation process is an effective method for the complete leaching of valuable metals from the coked spent catalyst.

     

Application of different single extraction procedures for assessing the bioavailability of heavy metal(loid)s in soils from overlapped areas of farmland and coal resources

Heavy metal(loid) extraction from soils in overlapped areas of farmland and coal resources (OAFCR) is crucial in understanding heavy metal bioavailability in soil and the subsequent risks to crops and consumers. However, limited attention has been paid to the extraction procedure of heavy metal(loid)s in OAFCR soils in the research. This study therefore explored different single and mixed extraction procedures, such as acetic acid (HOAc), citric acid, ammonium bicarbonate-diethylenetriaminepentaacetic acid (AB-DTPA), ethylene diamine tetraacetic acid + ammonium acetate (EDTA+NH₄OAc), and total digestion (HNO₃-HClO₄-HF) to determine the bioavailability of As, Cd, Cr, Cu, Pb, and Zn in OAFCR soil in Xuzhou, China. The results showed the metal(loid) extraction capacity from soil of the different procedures could be ranked as AB-DTPA > EDTA+NH₄OAc > HOA_C > citric acid. The transfer ability of heavy metal(loid)s from soil to wheat tissues and from wheat roots to aerial parts was analyzed by calculating the bioconcentration factor and transfer factor, respectively. Transfer factors of all metal(loid)s were < 1 except Cr whose transfer factor from root to shell and straw were > 1. It is suspected that foliar uptake plays a dominant role in Cr uptake. Correlation analysis between the bioavailability of heavy metal(loid)s in soil and uptake in respective wheat tissues was performed to recommend the best extraction procedures for different studies. The results show that AB-DTPA extraction is recommended for Cu uptake to wheat roots, straws, shells and grains, Zn uptake to roots, and Cd uptake to roots and straws.

     

Catalytic Gasification of Coal Using Eutectic Salts: Recovery,Regeneration, and Recycle of Spent Eutectic Catalysts

Abstract

Catalyst recovery studies were conducted for gasified chars produced from steam gasification of Illinois #6 coal catalyzed with two different catalyst systems. A ternary (43.5 mol% Li₂ CO₃ –31.5 mol% Na₂ CO₃ –25 mol% K₂ CO₃ ) and a binary (29 mol% Na₂ CO₃ –71 mol% K₂ CO₃ ) eutectic catalyst system were used for gasifying coal. Various extraction schemes, such as water extraction, H₂ SO₄ extraction, and acetic acid extraction, were evaluated with respect to their extraction efficiencies. Effects of major process variables, such as solvent-to-char ratio, mixing time, temperature, and concentration, on the extraction efficiency were evaluated. A process schematic for the entire catalyst recovery, regeneration, and recycle scheme was developed and the preliminary process economics were determined based on these extraction schemes. H₂ SO₄ extraction was found to be the most desirable. It also turned out to be more attractive than a once-through throwaway system.     

IV. Recovery of Flue Gas Sulfur as Ammonium Phosphate

The present development in industry has greatly increased the consumption of fossil fuel all over the world. The sulfur present in these fuels on combustion impairs the atmosphere and has to be removed before or after combustion. Direct desulfurization is still in its initial stage of commercial application and is thought to be rather expensive. Most projects today are concerned with flue gas desulfurization and a few people have been successful in the pilot plant scale. Flue gas sulfur is usually recovered as sulfuric acid or ammonium sulfate. The Kiyoura-T.I.T. process employs a completely dry method to recover this sulfur as ammonium sulfate. However, the present trends in fertilizers show that there is a marked drop in the consumption of this type of fertilizer except for China and other Asian countries.

Experiments were carried out to produce a high grade phosphatic fertilizer with a larger field of application. The authors were successful in rendering the phosphate in phosphate rock water soluble by reacting it with the sulfate radical of the ammonium sulfate. Ammonium acid sulfate was used in the experiments and the phosphate radical was determined by a colorimeter utilizing the ammonium molybdate method.

The results showed a conversion and an extractability of 98%, when the molecular ratio of ammonium acid sulfate to the CaO in phosphate rock was in the vicinity of 1:1.4-1.5. The reaction time was 120-180 minutes.

The extracted liquid was crystallized and put through X ray diffractometer experiments which showed that most of the crystals were ammonium phosphate containing about 15% N and 39% P₂O₅ on a dry basis. Thus, it is evident that this could be effectively applied in a commercial scale plant, recovering the flue gas sulfur as ammonium phosphate. The Kiyoura-T.I.T. process can be utilized to recover the flue gas sulfur either as the sulfate or as the phosphate.     

The efficient removal of thallium from sintering flue gas desulfurization wastewater in ferrous metallurgy using emulsion liquid membrane

The removal of thallium ions in flue gas desulfurization wastewater from ferrous metallurgic industry was studied by emulsion liquid membrane (ELM) method using 2-ethylhexyl phosphoric acid-2-ethylhexyl ester (P507) as carrier, aviation kerosene (AK) as organic solvent, polyisobutylene succinimide (T154) as surfactant, polyisobutylene (PIB) as additive, and sulfuric acid as internal reagent. Some important influence parameters such as concentrations of carrier, surfactant and stripping agent, agitation speed, extraction time, volume ratios of feed solution to emulsion phase and internal phase to membrane phase, and their effects on the removal efficiency of Tl in the ELM process were investigated and optimized. Under the optimum operating conditions of 2% of carrier, 5% of surfactant, 0.5 M of stripping agent, 350 rpm of agitation speed, 12.5:1 of volume ratio of feed solution to emulsion phase, and 3:1 volume ratio of membrane to internal phase, the maximum extraction efficiency of thallium reached 99.76% within 15-min reaction time. The ICP-MS analysis indicated that the thallium concentration in treated wastewater was below 5 μg/L and could meet the emission standard demand for industrial wastewater enacted by the local government of Hunan province of China. Meanwhile, the extraction of impurity ions calcium and magnesium in the ELM system was investigated. The result showed that an acidic environment would be in favor of the removal of Tl from calcium and magnesium contained in wastewater.

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Removal of mixed pesticides from drinking water system by photodegradation using suspended and immobilized TiO2

Lindane (1α, 2α, 3β, 4α, 5α, 6β-hexachloro cyclohexane), methyl parathion (O,O-dimethyl-O-4-nitrophenyl phosphorothioate) and dichlorvos (2,2-dichlorovinyl-O-O-dimethyl phosphate) are removed from water individually and as a mixture by photo degradation using suspended and immobilized forms of TiO₂ (Degussa P-25). Studies were conducted to optimize the coating thickness of immobilized photo catalyst. The rate of degradation of pesticides was compared in both suspended and immobilized TiO₂ systems. Degradation studies of mixed pesticides were carried out with low concentrations (1.0 and 2.5 mg/L) of pesticides. Only three intermediate byproducts such as methyl paraoxon, O,O,O-trimethyl phosphonic thionate and p-nitrophenol were observed during the methyl parathion degradation in suspended, immobilized TiO₂ systems and mixed pesticides degradation studies. At the end of the reaction methyl parathion and its by-products were completely degraded. During lindane degradation hexachloro cyclohexane, pentachloro cyclohexane, hexachloro benzene, 1-hydroxy 2,3,4,5,6-chlorocyclohexane, 1-hydroxy 2,3,4,5,6-chlorobenzene, pentachloro cyclopentadiene, 1,2,3,4,5-hydroxy cyclopentene and 1,2,3-hydroxy cyclobutane were identified in suspended and immobilized TiO₂ systems, whereas only hexachloro cyclohexane, pentachloro cyclohexane, hexachloro benzene and pentachloro cyclopentadiene were observed during mixed pesticides degradation. No intermediate by-product was observed during the photo degradation of dichlorvos. Langmuir-Hinshelwood pseudo first order kinetic equation showed that there was not much change in the rates of degradation in both suspended and immobilized TiO₂ systems irrespective of the pesticide. During mixed pesticides degradation, the degradation pattern was not similar to that of single pesticide.     

Nitrogen and phosphorus removal for swine wastewater by ammonium crystallization and intermittent aeration process

Abstract

A process on crystallized precipitation of ammonium by adding magnesium salt and phosphate was carried out to improve C/N ratio in swine wastewater. After completion of crystallized precipitation of ammonium, an intermittent aeration process with aeration and non‐aeration periods alternated at interval of 1:1 hr day^‐1 is used for the improved swine wastewater (T‐N/BOD=0.14: BOD=8200 mg/liter and T‐N=1166 mg/liter). The results obtained from the experiment show that the removal ratios of T‐N and NH₄‐N are 91% and 99%, respectively. T‐P is not removed, while the removal ratio of PO₄‐P is 60% as 3% of CaCl₂ liquid is added. The results also indicate that dilution with water is effective to improve the removal of phosphorus even if raw swine wastewater contains high concentrations of T‐N, T‐P, BOD, and TOC.     

Comparison of titania nanotubes and titanium dioxide as supports of low-temperature selective catalytic reduction catalysts under sulfur dioxide poisoning

A series of iron–manganese oxide catalysts supported on TiO₂ and titanium nanotubes (TNTs) were studied for low temperature selective catalytic reduction (SCR) of NO with NH₃ in the presence of SO_2. The results showed that the specific surface area and the amount of Brønsted acid sites were highly correlated. The results also demonstrated that higher Mn⁴⁺/Mn³⁺ ratios and larger specific surface areas might be the main reasons for the excellent performance of MnFe-TNTs catalyst after SO₂ poisoning. The SO₂ poisoning effect could be minimized by reducing the GHSV, increasing the reaction temperature, or increasing the [NH₃]/[NO] molar ratio. The results also indicated that the formation of ammonium sulfate had a stronger effect on the NO conversion efficiency as compared to the formation of metal sulfate. Thus operating the low temperature SCR at above 230 ^oC to avoid the formation of ammonium sulfate would be the priority choice when SO₂ poisoning is a concerned issue.?Implications: Low-temperature selective catalytic reduction (SCR) has attracted increasing attention due to that it can reduce the energy consumption for the SCR process employed in industries such as steel plants and glass manufacturing plants. However, it also suffers from the sulfur dioxide (SO₂) poisoning problem. This study investigates the possibility of using titania nanotubes (TNTs) as the support of Mn/Fe bimetal oxide catalysts for low-temperature SCR to reduce the SO₂ poisoning. The results indicated that the MnFe-TNT catalyst can tolerate SO₂ for a longer time as compared with the MnFe-TiO₂ catalyst.     

Effects of acidifying reagents on microwave treatment of dairy manure

Dairy manure, acidified using organic acids (acetic, oxalic, and citric acid) were treated with microwave enhanced advanced oxidation process (MW/H₂O₂-AOP). The effect of a mixture of oxalic acid and commonly used mineral acids (sulfuric and hydrochloric acid) on MW/H₂O₂-AOP was also examined. Substantial amounts of phosphorus were released under MW/H₂O₂-AOP, regardless of organic acid or mineral acid used. All three organic acids were good acidifying reagents; however, only oxalic acid could remove free calcium ion in the solution, and improve settleability of dairy manure. The MW/H₂O₂-AOP and calcium removal process could be combined into a single-stage process, which could release phosphate, solubilize solids and remove calcium from dairy manure at the same time. A mixture of oxalic acid and mineral acid produced the maximum volume of clear supernatant and had an ideal molar ratio of calcium to magnesium for effective struvite (magnesium ammonium phosphate) crystallization process. A single-stage MW/H₂O₂-AOP would simplify the process and reduce mineral acid consumption compared to a two-stage operation. The results of a pilot scale study demonstrate that MW/H₂O₂-AOP is effective in treating manure and recovering resource from dairy farms.     

Nickel Speciation of Residual Oil Fly Ash and Ambient Particulate Matter Using X-ray Absorption Spectroscopy

ABSTRACT

The chemical speciation of Ni in fly ash produced from ~0.85 wt % S residual (no. 6 fuel) oils in laboratory (7 kW)- and utility (400 MW)-scale combustion systems was investigated using X-ray absorption fine structure (XAFS) spectroscopy, X-ray diffraction (XRD), and acetate extraction [1 M NaOAc-0.5 M HOAc (pH 5) at 25 °C]-anodic stripping voltammetry (ASV). XAFS was also used to determine the Ni speciation of ambient particulate matter (PM) sampled near the 400-MW system. Based on XAFS analyses of bulk fly ash and their corresponding acetate extraction residue, it is estimated that >99% of the total Ni (0.38 wt %) in the experimentally produced fly ash occurs as NiSO₄-xH₂O, whereas >95% of the total Ni (1.70 and 2.25 wt %) in two fly ash samples from the 400-MW system occurs as NiSO₄-xH₂O and Ni-bearing spinel, possibly NiFe₂O₄. Spinel was also detected using XRD. Acetate extracts most of the NiSO₄-xH₂O and concentrates insoluble NiFe₂O₄ in extraction residue. Similar to fly ash, ambient PM contains NiSO₄-xH₂O and NiFe₂O₄;

however, the proportion of NiSO₄-xH₂O relative to NiFe₂O₄ is much greater in the PM. Results from this and previous investigations indicate that residual oil ash produced in the 7-kW combustion system lack insoluble Ni (e.g., NiFe₂O₄) but are enriched in soluble NiSO₄-xH₂O relative to fly ash from utility-scale systems. This difference in Ni speciation is most likely related to the lack of additive [e.g., Mg(OH)₂] injection and residence time in the 7-kW combustion system.     

Simultaneous removal of phosphorus and potassium from synthetic urine through the precipitation of magnesium potassium phosphate hexahydrate

This study investigated the simultaneous removal of P and K from synthetic urine through the precipitation of magnesium potassium phosphate hexahydrate (MPP, MgKPO₄·6H₂O) in bench-scale experiments. Results show that the removal efficiencies of P and K are mainly determined by the solution pH and the molar ratio of Mg:K:P. Co-precipitation of struvite-type compounds, i.e., magnesium ammonium phosphate hexahydrate (MAP, MgNH₄PO₄·6H₂O), magnesium sodium phosphate heptahydrate (MSP, MgNaPO₄·7H₂O), and MPP, was confirmed by analysis of the solid precipitates using a Scanning Electron Microscope/Energy Dispersive X-ray Apparatus and an X-ray Diffractometer. The co-precipitation significantly influenced the removal of K. As much ammonium as possible should be removed prior to MPP precipitation because MAP had higher tendency to form than MPP. The inevitable co-precipitation of MPP and MSP resulted in the addition of more MgCl₂·6H₂O and Na₂HPO₄·12H₂O to obtain the high removal of K. In total, the removal efficiencies of P and K were 77% and 98%, respectively, in the absence of ammonium when pH was 10 and the molar ratio of Mg:K:P was 2:1:2. The results indicate that the MPP precipitation is an efficient method for the simultaneous removal of P and K to yield multi-nutrient products.     

The study of operating variables in soil washing with EDTA

This study discusses the operating variables for removal of metals from soils using EDTA, including the type of EDTA, reaction time, solution pH, dose, temperature, agitation, ultrasound and number of extractions. For As, Cd, Cu, Pb and Zn, the removal efficiency order was: H₄-EDTA > Na₂EDTA > (NH₄)₂EDTA. At low EDTA concentrations the removal increased progressively with increasing dose while above 0.4 mmol/g only small increases in extraction efficiency were observed. EDTA induced a two-step process including a rapid desorption within the first hour, and a gradual release in the following hours. The extraction efficiency of metals decreased with increasing pH in the range of 2-10. Consecutive extractions using low concentrations were more effective than a single extraction with concentrated EDTA if the same dose of EDTA was used.     

Improving the activity of Mn/TiO2 catalysts through control of the pH and valence state of Mn during their preparation

In this study, the authors investigated the influence of the valence state of Mn on the efficacy of selective catalytic reduction using a Mn-based catalyst. The nitrogen oxides (NO_x) conversion rate of the catalyst was found to be dependent on the type of TiO₂ support employed and on the temperature, as the catalyst showed an excellent conversion of > 80% at a space velocity of 60,000 hr^?1 when the temperature was above 200 °C. Brunauer-Emmett-Teller, X-ray diffraction, and X-ray photoelectron spectroscopy analyses confirmed that catalyst displaying the highest activity contained the Mn⁴⁺ species and that its valence state was highly dependent on the pH during the catalyst preparation.

Implications Recently, various Mn catalysts have been evaluated as selective catalyst reduction (SCR) catalysts. However, in these previous studies, only the reaction characteristics and catalytic activity on the NH₃ SCR over Mn catalysts were evaluated. There have been no studies on the effect of pH during catalyst preparation. Therefore, in this study, the effect of pH during the catalyst preparation process was examined and a new application of the Mn catalysts was proposed based on the current findings.     

反渗透处理稀土氨氮废水试验研究

根据稀土冶炼厂排放的碳铵沉淀洗涤废水的水质情况,采用NH4Cl和 NaCl模拟废水进行了反渗透可行性对比实验。模拟实验发现,在相同条件下反渗透对NaCl 较NH₄Cl 有着更高的去除率,而NH₄Cl 相对NaCl则有着更高的产水速率。实际废水试验结果表明,在恒定操作压力范围内回收率为65%的条件下,NH₄Cl浓度为2.85 g/L的碳铵沉淀洗涤废水经反渗透处理其NH₄Cl去除率为77.3%,可作为氨氮废水的预处理。对该废水处理成本进行了分析,得出其约为2.7元/m³,比相近浓度氨氮废水的氨吹脱处理成本节省约26%。     

Catalytic oxidation for air pollution control

Bench-scale experiments have been conducted to evaluate a series of titania-supported Pt-Pd (as oxides) catalysts in the presence and absence of MoO₃ and Fe₂O₃ additives for their effectiveness in the complete catalytic oxidation of volatile organic compounds (VOCs) in air likely to be found in waste gases. Under oxidizing conditions, all of the catalysts promoted the complete oxidation of VOCs to CO₂ and H₂O. 99 % Conversion was achieved with a C₂H₄-C₂H₆ gas mixture in air at temperatures between about 160–450 °C and at a space velocity of 20,000 h^?1. Oxidation activity for the titania supported catalysts were found to decrease in the order Pt-Pd-Mo-Fe > Pt-Pd-Mo > Pt-Pd-Fe > Pt-Pd. However, the addition of MoO₃ and Fe₂O₃ increase the catalyst activity and reduce the reaction temperature for the complete destruction. Ageing was also performed in order to study the stability of the most active catalyst. Pt-Pd-Mo-Fe (as oxides) on titania catalyst is effective in oxidizing a wide range of volatile organic compounds at relatively low temperatures (220–405 °C) and and at a space velocity of 40,000 h^?1 and is resistant to poisoning by halogenated and amine volatile organic compounds.     

Absorption of NO and NO2 in Caprolactam Tetrabutyl Ammonium Halide Ionic Liquids

ABSTRACT

To explore environmentally benign solvents for the absorption of NO and NO₂, a series of caprolactam tetrabutyl ammonium halide ionic liquids were synthesized. The solubility of NO and NO₂ was measured at temperatures ranging from 298.2 to 363.2 K and atmospheric pressure, and the following trend in the solubility of NO and NO₂ in ionic liquids with various halide anions was observed, respectively: F > Br > Cl and Br > Cl > F. Moreover, as the temperature increased from 308.15 to 363.15 K and the mole ratio of caprolactam increased from 2:1 to 6:1, the solubility of NO increased. Alternatively, the solubility of NO₂ decreased as the temperature increased from 298.15 to 363.15 K, and the mole ratio of caprolactam increased from 2:1 to 6:1. The absorption and desorption of NO and NO₂ was practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. The method, which is at least partially reversible, offers interesting possibilities for the removal of NO and NO₂.

IMPLICATIONS Basic ionic liquids with amino groups were synthesized and used to capture CO₂, SO₂, and H₂S, and to promote hydrogenation of CO₂. In this paper, the authors used caprolactam tetrabutyl ammonium halide ionic liquid (IL) as absorbing medium in which NO_x could be absorbed. NO_x desorbed from the absorbent could be efficiently reduced by right catalysts at high temperature. The absorbed NO and NO₂ gas could be desorbed at higher temperature, allowing the ionic liquids to be reused several times without loss of capability. It was believed that caprolactam tetrabutyl ammonium bromide (CPL-TBAB) ILs may be useful for NO_x removal reagent for pollution control.     

In situ immobilization of cadmium in soil by stabilized biochar-supported iron phosphate nanoparticles

The potential for nanoscale phosphate amendments to remediate heavy metal contamination has been widely investigated, but the strong tendency of nanoparticles to form aggregates limits the application of this technique in soil. This study synthesized a composite of biochar-supported iron phosphate nanoparticle (BC@Fe₃(PO₄)₂) stabilized by a sodium carboxymethyl cellulose to improve the stability and mobility of the amendment in soil. The sedimentation test and column test demonstrated that BC@Fe₃(PO₄)₂ exhibited better stability and mobility than iron phosphate nanoparticles. After 28 days of simulated in situ remediation, the immobilization efficiency of Cd was 60.2 %, and the physiological-based extraction test bioaccessibility was reduced by 53.9 %. The results of sequential extraction procedures indicated that the transformation from exchangeable (EX) Cd to organic matter (OM) and residue (RS) was responsible for the decrease in Cd leachability in soil. Accordingly, the pot test indicated that Cd uptake by cabbage mustard was suppressed by 86.8 %. Compared to tests using iron phosphate nanoparticles, the addition of BC@Fe₃(PO₄)₂ to soil could reduce the Fe uptake of cabbage mustard. Overall, this study revealed that BC@Fe₃(PO₄)₂ could provide effective in situ remediation of Cd in soil.     

The enhancement of photodegradation efficiency using Pt–TiO2 catalyst

This study investigates the mechanism of photosensitization and the recombination of excited electron–hole pairs affected by depositing platinum (Pt) on the surface of titanium dioxide (TiO₂). A new catalyst of Pt–TiO₂ was prepared by a photoreduction process. Being model reactions, the photocatalytic oxidation of methylene blue (MB) and methyl orange (MO) in aqueous solutions using the Pt–TiO₂ catalyst was carried out under either UV or visible light irradiation. The experimental results indicate that an optimal content of 0.75%Pt–TiO₂ achieves the best photocatalytic performance of MB and MO degradation and that the Pt–TiO₂ catalyst can be sensitized by visible light. The interaction of Pt and TiO₂ was investigated by means of UV–Vis absorption spectra, photoluminescence emission spectra, and X-ray photoelectron emission spectroscopy. The Pt⁰, Pt²⁺ and Pt⁴⁺ species existing on the surface of Pt–TiO₂, and the Ti³⁺ species existing in its lattice may form a defect energy level. The Pt impurities, including Pt, Pt(OH)₂, and PtO₂, and the defect energy level absorb visible light more efficiently in comparison with the pure TiO₂ and hinder the recombination rate of excited electron–hole pairs.     

Photocatalytic mineralization of glyphosate in a small-scale plug flow simulation reactor by UV/TiO2

The present work involves the photocatalytic mineralization of glyphosate on a plug flow reactor by UV/TiO₂. The effect of catalyst loading shows an optimal value (0.4 g L^?1) which is necessary to mineralize glyphosate. The kinetic rate of glyphosate mineralization decreases with the increasing initial concentration of glyphosate, and the data can be described using the first-order model. An alkaline environment is conducive to glyphosate mineralization. The mineralization efficiency increases with elevated flow rate to 114 mL min^?1, which is followed by a decrease with a further increase in flow rate due to the reduction of the residence time. The presence of external oxidants (K₂S₂O₈, H₂O₂ and KBrO₃) and photosencitizer (humic acid) can significantly enhance glyphosate mineralization. Photocatalysis oxidation ability of the three studied oxidants decrease in the order of: S₂O₈ ^2? > BrO₃ ^? > H₂O₂. Finally, the Langmuir–Hinshelwood (L-H) model was used to rationalize the mechanisms of reactions occurring on TiO₂ surfaces and L-H model constants were also determined.     

Degradation of organophosphoric esters in leachate from a sea-based solid waste disposal site

Degradation of organophosphoric esters (OPEs) in leachate from a sea-based solid waste disposal site was investigated by laboratory experiment. Aryl-phosphates, tricresyl phosphate and triphenyl phosphate, in leachate rapidly decreased to less than the detection limit within 20 days under aerobic condition, suggesting high biodegradability. These phosphates also decreased in sterilized leachate, which suggested a contribution to degradation by reactions (adsorption and chemical degradation) with chemicals in the leachate. Concerning alkyl-phosphates, tributyl phosphate decreased rapidly after one week, which is considered to have been caused by biodegradation. Tris-2-ethylhexyl phosphate and tris-2-butoxyethyl phosphate decreased slowly in all samples but that of sterilized distilled water. This however, suggested contribution of biodegradation because the velocity of decrease in the leachate was higher than in control samples. Among chloro alkylphosphates, decrease of tris-2-chloroethyl phosphate and tris-dichloropropyl phosphate were observed though it was not obvious whether by biodegradation or not. Decrease of tris-2-chloropropyl phosphate (TCPP) was not observed for 80 days suggesting that TCPP remains in the leachate over a long period of time. Except for aryl-phosphates decrease of OPEs was not observed under anaerobic condition. It was considered that the composition ratio and the behavior of OPEs in leachate in the field reflects the biological and chemical degradation as well as the chemical properties of OPEs.