Reactivity between PbSO4 and CaCO3 particles relevant to the modification of mineral particles and chemical forms of Pb in particles sampled at two remote sites during an Asian dust event

During the transboundary transport of anthropogenic heavy metals by mineral particles providing reaction sites, the divalent metal salt PbSO₄ can be converted to PbCO₃ in the presence of water. We carried out laboratory experiments to study the transformation process under various conditions by incorporating test particles comprising CaCO₃ of a particulate mineral component, PbSO₄, and NaCl. After the immersion of PbSO₄ particles in contact with CaCO₃ particles in a water droplet, the conversion of PbSO₄ into PbCO₃ was confirmed by the change in morphology of the original particles to stick or needle form; the percentages of the chemical forms relative to the total Pb were determined by X-ray absorption near edge structure (XANES) analysis. Approximately 60–80% of PbSO₄ was converted to PbCO₃ after 24 h. A small amount of stick particles was detected when NaCl particles attached to PbSO₄/CaCO₃ particles were exposed to air with a relative humidity (RH) of 80–90% for 24 h. XANES measurements of the samples revealed that the molar percentage of PbCO₃ relative to the total Pb content was 4%.Field experiments were also conducted to determine the chemical forms of the Pb particles during the Kosa (Asian dust storm) event. Samples were collected from two remote sites in Japan and Korea. The mass size distribution of Pb aerosols collected in Japan was bimodal with two peaks in the coarse mode; the enrichment factor of Pb suggested that its source was anthropogenic. Pb L3 edge XANES measurements of both samples indicated that they had similar shapes. These measurements also indicated that the major Pb components for the samples collected in Japan were PbO, PbSO₄ PbCl₂, and PbCO₃, with molar percentages of 44%, 30%, 21%, and 5%, respectively. No significant differences were found between the component ratios of the samples collected in Japan and Korea, suggesting that definite transformation did not occur during the transport of the Kosa particles from Korea to Japan. On the basis of these observations, we postulate that the transformation process either occurred mainly before the particles arrived at Korea or did not take place after the particles left continental Asia.     

Synthesis and optimization of spherical nZVI (20–60 nm) immobilized in bio-apatite-based material for efficient removal of phosphate: Box-Behnken design in a fixed-bed column

In the present study, bio-apatite/nZVI composite was synthesized through Fe(III) reduction with sodium borohydride and was fully characterized by FTIR, XRD, SEM–EDX, TEM, BET, BJH, and pH_PZC. Column experiments were carried out for the removal of phosphate as a function of four operational parameters including initial phosphate concentration (100–200 mg L^?1), initial solution pH (2–9), bed height (2–6 cm), and influent flow rate (2.5–7.5 mL min^?1) using a response surface methodology (RSM) coupled with Box-Behnken design (BBD). 2D contour and 3D surface plots were employed to analyze the interactive effects of the four operating parameters on the column performance (e.g., uptake capacity and saturation time). According to ANOVA analysis, the influent flow rate and bed height are the most important factor on phosphate uptake capacity and saturation time, respectively. A quadratic polynomial model was excellently fitted to experimental data with a high coefficient of determination (>?0.96). The RSM-BBD model predicted maximum phosphate adsorption capacity of 85.71 mg g^?1 with the desirability of 0.995 under the optimal conditions of 135.35 mg L^?1, 2, 2 cm, and 7.5 mL min^?1 for initial phosphate concentration, initial solution pH, bed height, and influent flow rate, respectively. The XRD analysis demonstrated that the reaction product between bio-apatite/nZVI composite and phosphate anions was Fe₃ (PO₄)₂. 8H₂O (vivianite). The suggested adsorbent can be effectively employed up to five fixed-bed adsorption–desorption cycles and was also implemented to adsorb phosphate from real samples.

     

Influence of flooding and metal immobilising soil amendments on availability of metals for willows and earthworms in calcareous dredged sediment-derived soils

Soil amendments previously shown to be effective in reducing metal bioavailability and/or mobility in calcareous metal-polluted soils were tested on a calcareous dredged sediment-derived soil with 26 mg Cd/kg dry soil, 2200 mg Cr/kg dry soil, 220 mg Pb/kg dry soil, and 3000 mg Zn/kg dry soil. The amendments were 5% modified aluminosilicate (AS), 10% w/w lignin, 1% w/w diammonium phosphate (DAP, (NH₄)₂HPO₄), 1% w/w MnO, and 5% w/w CaSO₄. In an additional treatment, the contaminated soil was submerged. Endpoints were metal uptake in Salix cinerea and Lumbricus terrestris, and effect on oxidation-reduction potential (ORP) in submerged soils. Results illustrated that the selected soil amendments were not effective in reducing ecological risk to vegetation or soil inhabiting invertebrates, as metal uptake in willows and earthworms did not significantly decrease following their application. Flooding the polluted soil resulted in metal uptake in S. cinerea comparable with concentrations for an uncontaminated soil.     

Pb remobilization by bacterially mediated dissolution of pyromorphite Pb5(PO4)3Cl in presence of phosphate-solubilizing Pseudomonas putida

Remediation of lead (Pb)-contaminated sites with phosphate amendments is one of the best studied and cost-effective methods for in situ immobilization. In this treatment, a very stable mineral, pyromorphite Pb₅(PO₄)₃Cl, is formed. Several studies propose to improve this treatment method with the addition of phosphate-solubilizing bacteria (PSB). The effect of bacteria on solubilization of pyromorphite is unknown. In this study, the effect of the soil microorganisms on the stability of pyromorphite Pb₅(PO₄)₃Cl has been investigated in a set of batch solution experiments. The mineral was reacted with Pseudomonas putida, a common soil microorganism. Dissolution of pyromorphite was enhanced by the presence of P. putida, resulting in an elevated Pb concentration in the solution. This occurred even when the bacteria were provided with an additional source of phosphate in the solution. Pyromorphite has been shown to be a potential source of nutrient phosphorus for common soil bacteria. Thus, the use of PSB in remediation treatments of Pb contaminated sites may have adverse long-term impacts on Pb immobilization. Conscious phosphate management is suggested for long-term sustainability of the in situ Pb immobilization by pyromorphite formation.     

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.     

Impact of phosphate additive on organic carbon component degradation during pig manure composting

Phosphate, as an additive to composting, could significantly reduce ammonia emission and nitrogen loss but may also cause adverse effects on the degradation of organic matter. However, there is little information about the influence of pH change, salt content, and phosphate on different organic fraction degradation during composting with the addition of phosphate at a higher level. In this study, the equimolar phosphoric acid (H₃PO₄), sulfuric acid (H₂SO₄), and dipotassium phosphate (K₂HPO₄) were added into pig manure composting with 0.25 mol mass per kilogram of dry matter basis addition amount to evaluate the effect of H⁺, PO₄^3?, and salinity on carbon component transformation and organic matter degradation. The results showed that both H₃PO₄ and K₂HPO₄ additives could lead to shorter duration in the thermophilic phase, lower degradation of lignocellulose, and lesser carbon loss compared to CK, even though had different pH, i.e., acidic and alkaline conditions, respectively. Besides, the addition of H₃PO₄, H₂SO₄, and K₂HPO₄ could increase the degradation of soluble protein and lipid during composting. Redundancy analysis demonstrated that the variation in different organic carbon fractions was significantly correlated with the changes of pH and the presence of PO₄^3?, but not with SO₄^2? and electrical conductivity, suggesting that pH and phosphate were the more predominant factors than salinity for the inhibition of organic matter degradation. Taken together, as acidic phosphate addition produces a true advantage of controlling nitrogen loss and lower inhibition of organics transformation during composting, the expected effects may result in more efficient composting products.

     

Characterization of endophytic Rahnella sp. JN6 from Polygonum pubescens and its potential in promoting growth and Cd,Pb, Zn uptake by Brassica napus

Microbe-assisted phytoremediation has been considered as a promising measure for the remediation of heavy metal-polluted soils. In this study, a metal-tolerance and plant growth-promoting endophytic bacterium JN6 was firstly isolated from roots of Mn-hyperaccumulator Polygonum pubescens grown in metal-contaminated soil and identified as Rahnella sp. based on 16S rDNA gene sequence analysis. Strain JN6 showed very high Cd, Pb and Zn tolerance and effectively solubilized CdCO₃, PbCO₃ and Zn₃(PO₄)₂ in culture solution. The isolate produced plant growth-promoting substances such as indole-3-acetic acid, siderophore, 1-aminocyclopropane-1-carboxylic deaminase, and also solubilized inorganic phosphate. Based upon its ability in metal tolerance and solubilization, the isolate JN6 was further studied for its effects on the growth and accumulation of Cd, Pb and Zn in Brassica napus (rape) by pot experiments. Rape plants inoculated with the isolate JN6 had significantly higher dry weights, concentrations and uptake of Cd, Pb and Zn in both above-ground and root tissues than those without inoculation grown in soils amended with Cd (25 mg kg^?1), Pb (200 mg kg^?1) or Zn (200 mg kg^?1). The isolate also showed a high level of colonization in tissue interior of rapes. The present results demonstrated that Rahnella sp. JN6 is a valuable microorganism, which can cost-effectively improve the efficiency of phytoremediation in soils contaminated by Cd, Pb and Zn.     

Metal stabilization mechanism of incorporating lead-bearing sludge in kaolinite-based ceramics

The feasibility and mechanism of incorporating simulated lead-laden sludge into low-cost ceramic products was investigated by observing the reaction of lead with two kaolinite-based precursors under sintering conditions. To investigate the phase transformation process of lead, lead oxide (PbO) mixed with a kaolinite or mullite precursor were fired at 500-950 °C for 3 h. Detailed X-ray diffraction analysis of sintered products revealed that both precursors had crystallochemically incorporated lead into the lead feldspar (PbAl₂Si₂O₈) crystalline structure. By mixing lead oxide with kaolinite, lead feldspar begins to crystallize at 700 °C; maximum incorporation of lead into this structure occurred at 950 °C. However, two intermediate phases, Pb₄Al₄Si₃O₁₆ and a polymorph of lead feldspar, were detected at temperatures between 700 and 900 °C. By sintering lead oxide with the mullite precursor, lead feldspar was detected at temperatures above 750 °C, and an intermediate phase of Pb₄Al₄Si₃O₁₆ was observed in the temperature range of 750-900 °C. This study compared the lead leachabilities of PbO and lead feldspar using a prolonged leaching test (at pH 2.9 for 23 d) modified from the toxicity characteristic leaching procedure. The results indicate the superiority of lead feldspar in stabilizing lead and suggest a promising and reliable strategy to stabilize lead in ceramic products.     

Highly efficient biosorptive removal of lead from industrial effluent

This study has been focused on the efficient removal of Pb (II) from contaminated waters by biosorption using plant derived material. Accordingly an indigenous shrub, Tinospora cordifolia has been identified as the most suitable biosorbent. The plant biomass was subjected to optimization of various parameters such as the pH, equilibrium time, dosage, concentration, temperature and the applicable adsorption models. The optimum pH identified was 4.0 with a contact time of 60 min at room temperature (27 ± 2 °C). The experimental data fitted well to adsorption isotherms and the uptake capacity of Pb (II) was found to be 20.83 and 63.77 mg/g in batch mode and column mode, respectively. The high correlation factors obtained for Langmuir and Freundlich models indicated that both models were obeyed by the system. Kinetic study for adsorption of Pb (II) follow only pseudo second order rate of reaction. The accumulation of lead in biomass was confirmed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis. The FTIR analysis indicated the involvement of hydroxyl (−OH), alkenes (=CH) and carbonyl group (C = O) chelates in metal binding. The SEM and EDX analysis showed the structural changes and the filling of voids in the biomass thus, it indicated the metal-binding mechanism. In elution studies, the 0.1 M Na₂CO₃ was found to be the best with about 71% elution of the adsorbed metal. The biomass was then used for the removal of Pb (II) in synthetic and real wastewater samples from a lead-acid battery industry. It is also noteworthy that even at a very high concentration of 450 mg/L, the biomass was showing about 92% removal. The result is to establish the efficacy of T. cordifolia as a very good bioadsorbent for the Pb (II) removal from contaminated water.

     

危险废物焚烧飞灰中重金属的稳定化处理

以上海市某危险废物焚烧厂飞灰为研究对象,采用Na2S、FeSO4、Na3PO4、和Na3C3N3S34种不同类型化学稳定药剂对飞灰进行了稳定化处理,并应用XRD、IR、SEM和连续化学提取法等仪器和手段对Na3C3N3S3处理焚烧飞灰的产物进行分析研究。研究结果表明,Na3C3N3S3对飞灰中的重金属Cr、Pb、Zn的稳定效果最好,Na3PO4对Cr无明显稳定效果。稳定后产物表面变得致密化,Na3C3N3S3与重金属离子生成的沉淀物干燥后无明显晶型存在。经稳定处理后飞灰中的重金属形态由弱酸提取态转化为可氧化态,减少了飞灰中重金属的浸出毒性。     

Development of steady-state phosphate concentrations in septic system plumes

Long-term monitoring of PO₄⁻³ behaviour in a well-defined septic system plume on calcareous sand (Cambridge site) shows that, after 17 yr of system operation, a distinct PO₄⁻³ plume (PO₄⁻³−P > 1 mg L⁻¹) is present extending 20 m downgradient from the infiltration bed. The PO₄³⁻ plume migration velocity is 1 m yr⁻¹, reflecting retardation by a factor of 20 compared to the groundwater velocity. During monitoring between years 10 to 17, an expanding steady-state zone was noted below the infiltration bed where PO₄³⁻ −P levels remained consistently near 4 mg L⁻¹, a value 25% lower than the average effluent value (6.3 mg L⁻¹). The pattern of attenuation — a 25% mass loss in the 2-m-thick vadose zone, then little further attenuation along the flowpath — is suggestive of a condition of equilibrium with a controlling phosphate mineral phase. Chemical equilibrium modelling shows supersaturation with respect to hydroxylapatite and variscite. Four other field sites are identified from the literature and from our work where similar steady-state PO₄³⁻ zones are present in septic system plumes. In these, steady-state levels range from 15% to 68% of effluent values, with lower concentrations observed in the more acidic plumes, again indicative of a mineral solubility control, possibly variscite.PO₄³⁻ behaviour in these plumes suggests that, although P migration velocity is controlled by the processes of sorption, the magnitude of PO₄³⁻ that is present is governed by the constraints of phosphate mineral solubility. When septic systems on sands are located relatively close to sensitive surface water bodies and when long-term downgradient impact is the primary concern, more attention should be focused on the geochemical conditions that control PO₄³⁻ mineral solubility rather than only on the sorption characteristics of the sediment.     

Study of lead phytoavailability for atmospheric industrial micronic and sub-micronic particles in relation with lead speciation

Particles from channelled emissions of a battery recycling facility were size-segregated and investigated to correlate their speciation and morphology with their transfer towards lettuce. Microculture experiments carried out with various calcareous soils spiked with micronic and sub-micronic particles (1650 ± 20 mg Pb kg⁻¹) highlighted a greater transfer in soils mixed with the finest particles. According to XRD and Raman spectroscopy results, the two fractions presented differences in the amount of minor lead compounds like carbonates, but their speciation was quite similar, in decreasing order of abundance: PbS, PbSO₄, PbSO₄·PbO, α-PbO and Pb⁰. Morphology investigations revealed that PM_2.5 (i.e. Particulate Matter 2.5 composed of particles suspended in air with aerodynamic diameters of 2.5 μm or less) contained many Pb nanoballs and nanocrystals which could influence lead availability. The soil-plant transfer of lead was mainly influenced by size and was very well estimated by 0.01 M CaCl₂ extraction.     

Application of chemical oxidation to remediate HCH-contaminated soil under batch and flow through conditions

This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with β-HCH (45 mg kg^?1) and γ-HCH (lindane, 25 mg kg^?1) was sampled from former lindane waste storage site. Efficiency of following treatments was tested at circumneutral pH: H₂O₂ alone, H₂O₂/Fe^II, Na₂S₂O₈ alone, Na₂S₂O₈/Fe^II, and KMnO₄. Experimental conditions (oxidant dose, liquid/solid ratio, and soil granulometry) were first optimized in batch experiments. Obtained results revealed that increasing dose of H₂O₂ improved the oxidation efficiency while in Na₂S₂O₈ system, maximum HCHs were removed at 300 mM. However, oxidation efficiency was slightly improved by Fe^II-activation. Increasing the solid/liquid ratio decreased HCH removal in soil samples crushed to 500 μm while an opposite trend was observed for 2-mm samples. Dynamic column experiments showed that oxidation efficiency followed the order KMnO₄ > Na₂S₂O₈/Fe^II > Na₂S₂O₈ whatever the flow condition, whereas the removal extent declined at higher flow rate (e.g., ~50% by KMnO₄ at 0.5 mL/min as compared to ~30% at 2 mL/min). Both HCH removal and oxidant decomposition extents were found higher in saturated columns than the unsaturated ones. While no significant change in relative abundance of soil mineral constituents was observed before and after chemical oxidation, more than 60% of extractable organic matter was lost after chemical oxidation, thereby underscoring the non-selective behavior of chemical oxidation in soil. Due to the complexity of soil system, chemical oxidation has rarely been reported under flow through conditions, and therefore our findings will have promising implications in developing remediation techniques under dynamic conditions closer to field applications.     

诱导结晶法去除地下水中氟离子简

针对现行高氟地下水处理工艺中存在的工艺复杂、运行管理困难等问题，提出采用诱导结晶法除氟。其技术核心是在高氟水中投加氟磷灰石作为晶种，并投加磷酸盐和钙盐使水中氟离子在晶种表面生成氟磷酸钙（Ca₁₀（PO₄） ₆F₂）结晶。通过单因素实验得出最佳工艺条件：投加8g/L氟磷灰石，并投加NaH₂PO₄和CaCl₂，使钙离子、磷酸根离子和氟离子的摩尔比为10：5：1，搅拌速度为100 r/min，反应时间1 h。反应中磷酸根离子和钙离子的利用率分别达到98%和25%以上。电子扫描显微镜（SEM）表征晶种在参与反应后，表面有结晶生成。研究表明，采用诱导结晶法可将水中氟离子浓度从5~10 mg/L降至1 mg/L以下，达到饮用水水质标准。     

Phosphate Recovery from Greenhouse Wastewater

A study was conducted to investigate the suitability of phosphate recovery from greenhouse wastewaters by using precipitation/crystallization process. More than 90% of the phosphate could be removed from the greenhouse wastewater. Various calcium phosphate salts were obtained in the process; hydroxyapatite [Ca₅(PO₄)₃OH] could be the main product from the precipitates. Phosphate removal was affected by the presence of magnesium ion in wastewaters. An increase of magnesium concentrations in wastewaters decreased phosphate removal rates. The chemical contents of precipitates in terms of calcium, magnesium and phosphate were affected by calcium to magnesium molar ratio. Higher calcium contents were obtained at wastewaters with high calcium to magnesium molar ratio. An addition of magnesium did not affect the potassium contents in the precipitates. K‐struvite, MgKPO₄·6H₂O, was not the major product in the precipitate, even with addition of a large quantity of magnesium.     

Heavy metal availability,bioaccessibility, and leachability in contaminated soil: effects of pig manure and earthworms

A pot experiment and a leaching experiment were conducted to investigate the effects of earthworms and pig manure on heavy metals (Cd, Pb, and Zn) immobility, in vitro bioaccessibility and leachability under simulated acid rain (SAR). Results showed manure significantly increased soil organic carbon (SOC), dissolved organic carbon (DOC), available phosphorus (AP), total N, total P and pH, and decreased CaCl₂-extractable metals and total heavy metals in water and SAR leachate. The addition of earthworms significantly increased AP (from 0.38 to 1.7 mg kg^?1), and a downward trend in CaCl₂-extractable and total leaching loss of heavy metals were observed. The combined earthworm and manure treatment decreased CaCl₂-extractable Zn, Cd, and Pb. For Na₄P₂O₇-extractable metals, Cd and Pb were decreased with increasing manure application rate. Application of earthworm alone did not contribute to the remediation of heavy metal polluted soils. Considering the effects on heavy metal immobilization and cost, the application of 6% manure was an alternative approach for treating contaminated soils. These findings provide valuable information for risk management during immobilization of heavy metals in contaminated soils.

     

Enhanced-electrokinetic remediation of copper–pyrene co-contaminated soil with different oxidants and pH control

Electrokinetic (EK) remediation has potential to simultaneously remove heavy metals and organic compounds from soil, but the removal percent of these pollutants is very low in general if no enhancing treatment is applied. This study developed a new enhanced-EK remediation technology to decontaminate a heavy metal–organic compound co-contaminated soil by applying different oxidants and pH control. A red soil was used as a model clayed soil, and was spiked with pyrene and Cu at about 500 mg kg^?1 for both to simulate real situation. Bench-scale EK experiments were performed using four oxidants (H₂O₂, NaClO, KMnO₄, and Na₂S₂O₈) and controlling electrolyte pH at 3.5 or 10. After the treatments with 1.0 V cm^?1 of voltage gradient for 335 h, soil pH, electrical conductivity, and the concentrations and chemical fractionations of soil pyrene and Cu were analyzed. The results showed that there was significant migration of pyrene and Cu from the soil, and the removal percent of soil pyrene and Cu varied in the range of 30–52% and 8–94%, respectively. Low pH favoured the migration of soil Cu, while KMnO₄ was the best one for the degradation of pyrene among the tested oxidants, although it unfortunately prevented the migration of soil Cu by forming Cu oxide. Application of Na₂S₂O₈ and to control the catholyte pH at 3.5 were found to be the best operation conditions for decontaminating the Cu-pyrene co-contaminated soil.     

废铅酸蓄电池铅膏性质分析

为给废旧铅蓄电池铅膏的湿法回收工艺提供理论依据,对湖北金洋冶金股份有限公司破碎分选后的废铅膏进行了XRF、XRD、物理分析及化学分析等,确定了废铅膏的主要成分、理化性质等特性。结果表明,废铅膏粒径细小,碾钵磨细后能过120目的筛下物超过77.4%,这对湿法转化是有利的。废铅膏主要组成为64.5%PbSO4、29.5%PbO2、4.5%PbO、0.8%Pb及其他微量杂质元素,杂质主要包括Fe、Sb和Si等。因此,铅膏湿法处理时应该采取合适的净化工艺。     

Characterization of Fugitive Material within a Primary Lead Smelter

ABSTRACT

The primary production of Pb via the sinter plant-blast furnace method resulted in a large number of Pb and other phases, reflecting the complex reactions occurring within each of the processes. Optical microscopy and X-ray diffraction (XRD) techniques have been used to characterize fugitive emissions and dusts generated during sintering, smelting, Cu drossing, refining, and slag fuming at a primary Pb-Zn smelter. The results displayed a complex array of phases, with the mineralogy of the dusts and fume reflecting conditions of the particular metallurgical operation. The principal Pb species followed a transformation from PbS through PbSO₄ and PbO to Pb° (metal) from raw materials to the refinery. The fugitive emissions generated by the blast furnace were of a finer size with more complex chemistry than fugitive material from other source areas. XRD identified a mixture of PbS, ZnO, and ZnS, associated with one or more of the Cl-bearing phases Pb(OH)Cl, PbCl₂, Pb₄O₃Cl₂, Na₃Pb₂(SO₄)₃Cl, Pb₁₀(SO₄)Cl₂O₈, Pb₄SCl₆, and Pb₇S₂Cl₁₀. The presence of Cl-bearing phases in the fume has possible health implications.     

Degradation of tris(1-chloro-2-propanyl) phosphate by the synergistic effect of persulfate and zero-valent iron during a mechanochemical process

This study revealed a dual pathway for the degradation of tris(1-chloro-2-propanyl) phosphate (TCPP) by zero-valent iron (ZVI) and persulfate as co-milling agents in a mechanochemical (MC) process. Persulfate was activated with ZVI to degrade TCPP in a planetary ball mill. After milling for 2 h, 96.5% of the TCPP was degraded with the release of 63.16, 50.39, and 42.01% of the Cl^?, SO₄^2?, and PO₄^3?, respectively. In the first degradation pathway, persulfate was activated with ZVI to produce hydroxyl (·OH) radicals, and ZVI is oxidized to Fe(II) and Fe(III). A substitution reaction occurred as a result of the attack of ·OH on the P–O–C bonds, leading to the successive breakage of the three P–O–C bonds in TCPP to produce PO₄^3?. In the second pathway, a C–Cl bond in part of the TCPP molecule was oxidized by SO₄·^? to carbonyl and carboxyl groups. The P–O–C bonds continued to react with ·OH to produce PO₄^3?. Finally, the intermediate organochloride products were further reductively dechlorinated by ZVI. However, the synergistic effect of the oxidation (·OH and SO₄·^?) and the reduction reaction (ZVI) did not completely degrade TCPP to CO₂, resulting in a low mineralization rate (35.87%). Moreover, the intermediate products still showed the toxicities in LD₅₀ and developmental toxicant. In addition, the method was applied for the degradation of TCPP in soil, and high degradations (>?83.83%) were achieved in different types of soils.