Reactive transport of Cd2+ in porous media in the presence of xanthate: Experimental and modeling study.

In mining regions, flotation reagents can interact with heavy metals, thereby increasing the complexity of their migration. However, most current studies solely focus on the migration of heavy metals, neglecting the influence of flotation reagents in their models concerning mining area pollution. This study developed the reactive transport model, Multisurface Speciation Model (MSM), which integrated the reaction processes of the three main soil components (iron oxides, organic matter, clay minerals) and ethyl xanthate (EX), a typical flotation reagent, with cadmium (Cd²âº) to investigate the effects of EX on the transport and retention of Cd²âº in natural porous media under varying pH conditions. The study revealed that EX formed new adsorption sites for Cd²âº, enhancing its retention and inhibiting transport with increased EX loading (0 to 2.5 mmol·L-1), while higher pH levels (ranging from 4 to 8) further strengthened the retention capability of Cd²âº. The MSM further predicted the solid-phase concentration distribution of Cd²âº among various components. With increasing EX-loaded concentrations, xanthate became the dominant adsorbing component, accounting for 48.93 % to 95.31 % of adsorption, and competitively interacted with other components. Xanthate retention was lower under acidic conditions compared to neutral and alkaline environments. Sensitivity analysis highlighted the concentrations of iron oxide adsorption sites (SurfaOH, SurfbOH) as critical parameters in the models, underscoring the need for precise determination of soil physicochemical indicators. This study stressed the crucial role of flotation reagents and pH conditions in controlling heavy metal mobility, offering important insights for environmental management in mining regions.

Expedient Synthesis of Alkyl and Aryl Thioethers Using Xanthates as Thiol-Free Reagents.

Thioethers are critical in the fields of pharmaceuticals and organic synthesis, but most of the methods for synthesis alkyl thioethers employ foul-smelling thiols as starting materials or generate them as by-products. Additionally, most thiols are air-sensitive and are easily oxidized to produce disulfides under atmospheric conditions; thus, a novel method for synthesizing thioethers is necessary. This paper reports a simple, effective, green method for synthesizing dialkyl or alkyl aryl thioether derivatives using odorless, stable, low-cost ROCS2K as a thiol surrogate. This transformation offers a broad substrate scope and good functional group tolerance with excellent selectivity. The reaction likely proceeds via xanthate intermediates, which can be readily generated via the nucleophilic substitution of alkyl halides or aryl halides with ROCS2K under transition-metal-free and base-free conditions.

Mining flotation reagents: Quantitative and robust analysis of metal-xanthate complexes in water.

Xanthates, common mining flotation reagents, strongly bind thiophilic metals such as copper (Cu), lead (Pb), cadmium (Cd), and zinc (Zn) and consequentially change their bioavailability and mobility upon their discharge into the environment. However, accurate quantification of the metal-xanthate complexes has remained elusive. This study develops a novel and robust method that realizes the accurate quantification of the metal-xanthate complexes resulted from single and multiple reactions of three typical xanthates (ethyl, isopropyl, and butyl xanthates) and four thiophilic metals (Cu, Pb, Cd, and Zn) in water samples. This method uses sulfur (S2-) dissociation, followed by tandem solid phase extraction of C18 + PWAX and subsequent LC-MS/MS analysis. It has a wide linearity range (1-1000 µg/L, R2 ≥ 0.995), low method detection limits (0.002-0.036 µg/L), and good recoveries (70.6-107.0 %) at 0.01-10 mg/L of xanthates. Applications of this method showed ubiquitous occurrence of the metal-xanthate complexes as the primary species in flotation wastewaters, which the concentrations were 4.6-28.9-fold higher than those previously determined. It is the first quantitative method established for the analysis of metal-xanthate complexes in water samples, which is of great importance to comprehensively understand the fate and risks of xanthates in the environment.

Electronic analysis of n-propyl xanthate complexes with group 12 metals: a theoretical-experimental study.

CONTEXT: Xanthates are organic compounds of great interest in coordination chemistry due to their different basic sites, which allow them to form complexes with different coordination modes and geometries. These compounds are relevant in the environment and act as heavy metal collectors in aqueous environments. In this theoretical-experimental work, electronic spectroscopy studies of n-propyl xanthate complexes with group 12 metals were performed. This study verified structural differences in these systems, depending on the environment in which they are inserted. In addition, structural differences were observed when the solid was changed to an n-hexane solution. Thus, it was observed that the complexes assume a mononuclear structure in solution, while they present a polymeric form in the solid phase. The electronic spectra obtained through TD-DFT calculations were compared to those of the previously synthesized complexes. In the final theoretical analysis, the main orbitals involved in these transitions were assigned using population analysis calculations. The synthesis of the complexes was confirmed through infrared (MID and FAR), UV‒Vis, Raman, and NMR-1H spectroscopic analyses. METHODS: The structures of the mononuclear and polymeric complexes were optimized in vacuum and n-hexane. Under vacuum, DFT levels M06L/6-311 + + G** + LANL2TZ and M06L/def2-TZVP were used for the mononuclear complexes, and M06L/LANL2DZ + LANL2 were used for the polymer complexes. For the calculations of the mononuclear complexes in n-hexane, the same level of theory was used for the solid state. TD-DFT calculations for 300 excited states were performed with the same levels of theory and used the optimized structures of the complexes. Furthermore, population analysis was carried out on all the systems studied. Gaussian 09 software was used for the structure optimization, TD-DFT, and population analysis calculations. GaussSum software was used to evaluate the molecular orbitals and electronic spectra.

Resource utilization of MSWI fly ash supporting TiO2/BiOCl nanocomposite for enhanced photocatalytic degradation of sodium isopropyl xanthate: Mechanism and performance evaluation.

The removal of organic pollutants in water environments and the resource utilization of solid waste are two pressing issues around the world. Facing the increasing pollution induced by discharge of mining effluents containing sodium isopropyl xanthate (SIPX), in this work, municipal solid waste incineration fly ash (MSWI FA) was pretreated by hydrothermal method to produce stabilized FA, which was then innovatively used as support for the construction of FA/TiO2/BiOCl nanocomposite (FTB) with promoted photocatalytic activity under visible light and natural sunlight. When the content of FA was 20 wt% and the mass ratio of TiO2 to BiOCl was 4:6, a remarkable performance for the optimal FTB (20-FTB-2) was achieved. Characterizations demonstrated that TiO2 and BiOCl uniformly dispersed on FA contributing to high surface area and broad light adsorption of FTB, which exhibits excellent adsorption capacity and light response ability. Build in electric field formed in the interface of TiO2/BiOCl heterojunction revealed by density functional theory calculations accelerated the separation of photoinduced e- and h+, leading to high efficiency for SIPX degradation. The synergetic effect combined with adsorption and photocatalytic degradation endowed 20-FTB-2 superior SIPX removal efficiency over 99% within 30 min under visible light and natural sunlight irradiation. The photocatalytic degradation pathways of SIPX were determined through theoretical calculations and characterizations, and the toxic byproduct CS2 was effectively eliminated through oxidation of •O2-. For 20-FTB-2, reusability of photocatalyst was showed by cycle tests, also the concentrations of main heavy metals (Pb, Zn, Cu, Cr, and Cd) in the liquid phases released during photocatalyst preparation process (< 1 mg/L) and photodegradation process (< 8.5 µg/L) proved the satisfactory stability with low toxicity. This work proposed a novel strategy to develop efficient and stable support-based photocatalysts by utilizing MSWI FA and realize its resource utilization.

α-Amido Trifluoromethyl Xanthates: A New Class of RAFT/MADIX Agents.

Xanthates have long been described as poor RAFT/MADIX agents for styrene polymerization. Through the determination of chain transfer constants to xanthates, this work demonstrated beneficial capto-dative substituent effects for the leaving group of a new series of α-amido trifluoromethyl xanthates, with the best effect observed with trifluoroacetyl group. The previously observed Z-group activation with a O-trifluoroethyl group compared to the O-ethyl counterpart was quantitatively established with Cex = 2.7 (3-4 fold increase) using the SEC peak resolution method. This study further confirmed the advantageous incorporation of trifluoromethyl substituents to activate xanthates in radical chain transfer processes and contributed to identify the most reactive xanthate reported to date for RAFT/MADIX polymerization of styrene.

Micro-Spherical BiOI Photocatalysts for Efficient Degradation of Residual Xanthate and Gaseous Nitric Oxide.

BiOI microspheres were synthesized using the solvothermal method for the degradation of residual xanthate and gaseous nitric oxide (NO) under visible light irradiation. The as-prepared BiOI nanomaterials were then characterized using various technologies, including XRD, FE-SEM, TEM, UV-Vis DRS, and XPS. The photodegradation results show that the removal efficiency of isobutyl sodium xanthate can reach 98.08% at an initial xanthate concentration of 120 mg/L; that of NO is as high as 96.36% at an inlet NO concentration of 11 ppm. Moreover, the effects of operational parameters such as catalyst dosage, initial xanthate concentration, and pH value of wastewater on the removal of xanthate were investigated. The results of scavenging tests and full-spectrum scanning indicate that ·O2- radicals are the main active species in xanthate degradation, and peroxide xanthate is an intermediate. The reusability of BiOI was explored through cyclic experiments. Furthermore, the reaction path and the mechanism of NO removal using BiOI were analyzed, and the main active species was also ·O2-. It is concluded that BiOI photocatalysts have high potential for wastewater treatment and waste gas clean-up in the mineral industry.

Dansyl-tagged xanthate ester as a capping agent to synthesize fluorescent silver nanoparticles with binding affinity toward serum albumin.

Developing multifunctional nanomaterials with distinct photochemical properties, such as high quantum yield, improved photostability, and good biocompatibility is critical for a wide range of biomedical applications. Motivated by this, we designed and synthesized a dansyl-tagged xanthate-based capping agent (DX) for the synthesis of fluorescent silver nanoparticles (AgNPs). The capping agent DX was characterized by 1H and 13C-NMR, LC-MS, and FT-IR. The synthesized DX-capped fluorescent AgNPs were thoroughly characterized by UV-visible spectroscopy, fluorescence spectroscopy, field emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), dynamic light scattering (DLS), and zeta potential. The fluorescent AgNPs showed distinct surface plasmon resonance absorption at λmax = 414 nm, fluorescence at λmax = 498 nm, quantum yield = 0.24, zeta potential = +18.6 mV, average size = 18.2 nm. Furthermore, the biological activity of the fluorescent AgNPs was validated by its interaction with the most abundant protein in the blood, that is, BSA (Bovine serum albumin) and HSA (Human serum albumin) with binding constant of 2.34 × 104 M-1 and 2.14 × 104 M-1 respectively. Interestingly, fluorescence resonance energy transfer (FRET) was observed between the fluorescent AgNPs and BSA/HSA with a FRET efficiency of 77.23% and 56.36%, respectively, indicating strong interaction between fluorescent AgNPs and BSA/HSA.

Potassium Amyl Xanthate (PAX) as an alternative organic reactive for mercury removal from cyanidation process of amalgamation tailing.

Mercury is the heavy metal that is most difficult to remove from cyanide solution. This situation brings with it many environmental, health and economic problems. This study aims to effectively utilize xanthate by presenting a new strategy for purifying mercury in the cyanidation process of amalgamation residues. In the study, the removal of mercury by precipitation using PAX from cyanidation leach solutions of a well-characterized amalgamation residue was investigated. The dosage of the precipitation reagent is the most important parameter in the removal of mercury. The mercury removal efficiency increases with the increase in the PAX/Hg ratio, and when the removal ratio is 60, the precipitation efficiency reaches a value of 66.7%. Applying coagulation and flocculation procedures after the precipitation process increases the mercury removal efficiency. It is seen that with this application, mercury can be removed with an efficiency of 95.6% at the same reagent rate. With this application, the particle sizes of the precipitates are enlarged and their filtration properties are improved. It has also been determined that the precipitates formed are in the form of HgS, a stable mercury compound. These results indicate that mercury can be effectively removed in its steady state. It was found that the concentration of Au and Cu did not change significantly, while the concentration of Ag decreased during the precipitation processes.

Ultra-Sensitive Determination of Cadmium in Food and Water by Flame-AAS after a New Polyvinyl Benzyl Xanthate as an Adsorbent Based Vortex Assisted Dispersive Solid-Phase Microextraction: Multivariate Optimization.

Background: Cadmium (Cd) is a very toxic and carcinogenic heavy metal even at low levels and it is naturally present in water as well as in food. Methods: A new polyvinyl benzyl xanthate (PvbXa) was synthesized and used as a new adsorbent in this work. It contains pendant sulfide groups on the main polystyryl chain. Using this new adsorbent, PvbXa, a vortex-assisted dispersive solid-phase microextraction (VA-dSPµE) procedure was developed for the determination of cadmium from food and water samples via flame atomic absorption spectrophotometry (FAAS). Synthesized PvbXa was characterized by 1H Nuclear magnetic resonance (NMR) Spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), and X-ray Photoelectron Spectroscopy (XPS). The different parameters of pH, sample volume, mixing type and time, sorbent amount, and eluent time were optimized using standard analytical methods. Results: The optimized method for assessment of Cd in food and water samples shows good reliability. The optimum conditions were found to be a 0.20-150 µg L-1 linear range, 0.06 µg L-1 LOD, 0.20 µg L-1 LOQ, 4.3 RSD %, and a preconcentration factor of 160. Conclusions: The statistically experimental variables were utilized using a central composite design (CCD). The present method is a low-cost, simple, sensitive, and very effective tool for the recovery of Cd.

Charge transfer mechanism through S-scheme heterojunction in in-situ synthesized TiO2/Fe-doped hydroxyapatite for improved photodegradation of xanthate.

The heterojunction structure of the photocatalyst composite, which necessitates a robust interface and sufficient contact areas, holds the key to obtaining high charge carrier migration efficiency. Here, a novel composite, TiO2 nanoparticles/Fe-doped hydroxyapatite (TONPs/FH_CS), is fabricated using a two-step synthetic technique, in which FH_CS is synthesized from artificial converter slag enriched with Fe and Ca. The unique nanorod@plate structure of FH_CS enables the uniform immobilization of TONPs onto FH_CS. Thereby, an n-n type heterojunction exhibits a highly intimate Ti-O-Fe heterointerface. Kelvin probe testing demonstrates the formation of an interfacial electric field oriented from FH_CS to TONPs, which serves as the driving force for interfacial electron transfer through the Ti-O-Fe channels. The photoacoustic signals provide information on electron trap levels and densities, indicating the formation of the electron transfer channels. •O2- and •OH species are responsible for being the active species in this system. A photoexcited carrier transfer pathway exhibiting an S-scheme mechanism with high separation efficiency significantly enhances the utilization of charge carriers in each phase. Thus, improved xanthate degradation has been achieved using a heterojunction containing a photocatalyst derived from industrial solid waste. This work demonstrates the significant potential of steel-making byproduct utilization in industrial wastewater treatment.

Photoinduced Electron Transfer from Xanthates to Acyl Azoliums: Divergent Ketone Synthesis via N-Heterocyclic Carbene Catalysis.

Considering the prevalence of alcohols and carboxylic acids, their fragment cross-coupling reactions could hold significant implications in organic synthesis. Herein, we report a versatile method for synthesizing a diverse range of ketones from alcohols and carboxylic acid derivatives via N-heterocyclic carbene (NHC) catalysis. Mechanistic investigations revealed that photoexcited xanthates and acyl azoliums undergo single electron transfer (SET) under photocatalyst-free conditions, generating NHC-derived ketyl radicals and alkyl radicals. These open-shell intermediates subsequently undergo the radical-radical cross-coupling reaction, yielding valuable ketones. Furthermore, this approach can be employed in three-component reactions involving alkenes and enynes, resulting in structurally diverse cross-coupled ketones. The unified strategy offers a unique opportunity for the fragment coupling of a diverse range of alcohols and carboxylic acid derivatives, accommodating diverse functional groups even in complex settings.

Determination of xanthates as Cu(II) complexes by high-performance liquid chromatography - Inductively coupled plasma tandem mass spectrometry.

The present study provides a novel, selective analysis method for the determination of low xanthate concentrations. The rising concern over the environmental effects of xanthates demands the development of analysis methods which this study answers. Complex formation in aqueous solution between xanthates and an excess of Co(II), Ni(II), Pb(II), Cd(II), Cu(II), and Zn(II) ions was utilized to selectively determine xanthates by high-performance liquid chromatography-inductively coupled plasma tandem mass spectrometry for the first time. The complexes that were formed were extracted to ethyl acetate using liquid-liquid extraction and separated by high-performance liquid chromatography technique before the quantitative determination of metal ions and sulfur in the xanthate complexes. Good separation and high measurement sensitivity were achieved using Cu(II) as the complex metal ion. The analysis method was optimized for the determination of sodium isopropyl xanthate and sodium isobutyl xanthate with detection limits of 24.7 and 13.3 µg/L, respectively. With a linear calibration range of 0.1-15 mg/L and a total analysis time of 4-5 min, the present method is a fast and sensitive option for selective xanthate determination.

[Direct determination of five xanthic acids in water by ultra performance liquid chromatography-tandem mass spectrometry].

Xanthates with different alkyl groups, such as ethyl, propyl, butyl, and amyl groups, are widely used in large quantities in the mining flotation of metallic minerals. Xanthates enter environmental waters through mineral processing wastewater discharge and are ionized or hydrolyzed into ions or molecules of xanthic acids (XAs) in water. XAs endanger aquatic plants and animals, as well as human health. To the best of our knowledge, XA analysis is mainly limited to butyl xanthate. Moreover, the isomers and congeners of XAs cannot be determined separately using the existing methods. Herein, a novel method based on ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to separate and analyze five XAs, namely, ethyl-, isopropyl-, n-butyl-, isobutyl-, and amyl-XAs, in water. Water samples were filtered through a 0.22 µm hydrophilic polytetrafluoroethylene (PTFE) membrane and directly injected into the UPLC-MS/MS instrument. Separation was performed using a Waters Acquity UPLC BEH C18 column (100 mm×2.1 mm, 1.7 µm) with ammonia solution (pH 11)-acetonitrile (9∶1, v/v) as the mobile phase for isocratic elution. The five XAs were detected in the negative electrospray ionization (ESI-) and multiple reaction monitoring (MRM) modes. An internal standard method was used for quantification. The pretreatment and UPLC-MS/MS conditions were comprehensively optimized to achieve the separation and analysis of the five XAs via direct injection. The XAs showed negligible adsorption on hydrophobic PTFE, hydrophilic PTFE, hydrophilic polypropylene, and polypropylene membranes during filtration. However, the amyl-XA showed obvious adsorption on nylon and polyether sulfone membranes. The five XAs mainly formed [M-H]- parent ions in the ESI- mode and the main daughter ions obtained following collisional fragmentation depended on the alkyl groups of the XAs. Increasing the pH of the ammonia solution in the mobile phase to 11 led to the isomeric separation of n-butyl- and isobutyl-XAs. The optimized mobile phase inhibited the tailing of the chromatographic peak of amyl-XA and effectively improved all the chromatographic peak shapes of XAs. The BEH C18 column was selected as the chromatographic column owing to its better compatibility with high-pH solutions compared with the T3 C18 column. Preservation experiments conducted over 8 d showed that the concentration of all five XAs decreased over time at room temperature; among the XAs analyzed, the concentration of ethyl-XA revealed the most significant decrease. However, the recoveries of the five XAs at 4 and -20 ℃ remained high, ranging from 101% to 105% and from 100% to 106%, respectively, on the 8th day. The preservation observed with a high concentration of XAs was similar to that found with a low concentration. The preservation time was extended to 8 days at pH 11 and 4 ℃ away from the light. No significant matrix effects were observed for the five XA samples in surface water and groundwater, but industrial sewage exerted obvious matrix inhibitory effects on ethyl- and isopropyl-XAs. Owing to the short retention times of ethyl- and isopropyl-XAs, the co-fluxed interferents in the industrial sewage depressed the MS signals. The five XAs showed good linearity in the range of 0.25-100 µg/L, with correlation coefficients greater than 0.9996. The method detection limits were as low as 0.03-0.04 µg/L, and the intra- and inter-day precisions were 1.3%-2.1% and 3.3%-4.1%, respectively. The recoveries obtained under low, medium, and high spiked levels (1.00, 20.0, 80.0 µg/L) were 96.9%-133%, 100%-107%, and 104%-112%, respectively. The corresponding RSDs were 2.1%-3.0%, 0.4%-1.9%, and 0.4%-1.6%, respectively. The optimized method was successfully applied to the analysis of XAs in surface water, groundwater, and industrial sewage. The method could separate and detect various congeners and isomers of XAs without the need for cumbersome pretreatment processes, and its advantages include smaller sample requirements, simpler operation, higher sensitivity, and longer preservation time. The proposed technique presents excellent application potential in XA environmental monitoring and water evaluation, and mineral flotation studies.

Interplay of electrolyte concentration and molecular weight of polyDADMAC on cellulose surface adsorption.

Cationic polyelectrolytes (PEs) are commonly used additives in manufacturing of cellulose based products such as regenerated fibers and paper to tailor their product properties. Here we are studying the adsorption of poly(diallyldimethylammonium chloride), PD, on cellulose, using in situ surface plasmon resonance spectroscopy (SPR) measurements. We employ model surfaces from regenerated cellulose xanthate (CX) and trimethylsilyl cellulose (TMSC), mimicking industrially relevant regenerated cellulose substrates. The effects of the PDs molecular weight were strongly depending on the ionic strength and type of electrolyte (NaCl vs CaCl2). Without electrolytes, the adsorption was monolayer-type, i.e. independent of molecular weight. At moderate ionic strength, adsorption increased due to more pronounced PE coiling, while at high ionic strength electrostatic shielding strongly reduced adsorption of PDs. Results exhibited pronounced differences for the chosen substrates (cellulose regenerated from xanthate (CXreg) vs. regenerated from trimethylsilyl cellulose, TMSCreg). Consistently higher adsorbed amounts of the PD were determined on CXreg surfaces compared TMSC. This can be attributed to a more negative zeta potential, a higher AFM roughness and a higher degree of swelling (investigated by QCM-D) of the CXreg substrates.

Enhancement of Xanthate Adsorption on Cerussite Surfaces by Pb(II) Activation and Its Effect on Floatability.

Cerussite is a lead oxide mineral resource that is typically enriched through sulfidization flotation. The surface sulfidation degree and the high solubility of cerussite strongly affect the flotation ability of cerussite. In the current work, lead ions were used to pretreat cerussite to intensify its sulfidization flotation. The sulfidization mechanism regulating the lead ions pretreatment on cerussite was investigated by the micro-flotation test, ToF-SIMS, zeta potential measurement, adsorption test, and XPS. The results from the micro-flotation test demonstrated that the floatability of cerussite could be improved by adding an appropriate amount of lead ions. Compared with the treatment involving only Na2S, the maximum recovery increased by 17.57%. Adsorption experiments showed that lead modification improved the stability of xanthate products on the surface of cerussite. According to the measurement of zeta potential and the results of ToF-SIMS, the addition of lead ion Pb pretreatment increased the number of active Pb sites adsorbed by xanthate, thereby improving the formation of hydrophobic Pb-dilute precipitate. Therefore, the interaction between lead ions and the surface of cerussite enhances the strength and stability of the hydrophobic layer, resulting in enhanced hydrophobicity of cerussite.

Tailor-Made Poly(vinylamine) via Purple LED-Activated RAFT Polymerization of N-vinylformamide.

Photo-iniferter reversible addition-fragmentation chain transfer (PI-RAFT) polymerization of N-vinylformamide (NVF) is demonstrated by using purple light. PNVFs with predetermined molar masses and narrow molar mass distributions are obtained. High RAFT chain-end fidelity is confirmed by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) and electrospray-ionization time-of-flight mass spectrometry (ESI-TOF-MS), and chain extension experiment. To demonstrate the potential of this approach, an original poly(N-vinylpyrrolidone)-b-poly(N-vinylformamide) (PVP-b-PNVF) diblock copolymer is synthesized and characterized by aqueous size-exclusion chromatography (SEC), asymmetric flow field-flow fractionation (A4F), and 1 H diffusion-ordered spectroscopy nuclear magnetic resonance (1 H DOSY NMR). Finally, selective hydrolysis of PNVF block to corresponding pH-responsive poly(N-vinylpyrrolidone)-b-poly(N-vinylformamide) (PVP-b-PVAm) is performed.

A novel method based on solid phase extraction and liquid chromatography-tandem mass spectrometry warrants occurrence of trace xanthates in water.

Huge volumes of wastewater containing organic flotation reagents such as xanthates have been released into the environment via mining activities, greatly threatening the eco-environment safety. A simple and fast method is urgently needed for accurate analysis of various xanthates in mining and environmental water. Here, a robust method is realized for simultaneous determination of three trace xanthates (i.e., potassium ethyl xanthate, potassium butyl xanthate, and potassium isopropyl xanthate) in environmental water samples, including eutrophic water and flotation wastewater using solid phase extraction (SPE) and HPLC-MS/MS. HPLC-MS/MS parameters, SPE cartridges and eluting solvents, pH values, and SPE procedures were optimized. The new method had an excellent linearity in the range of 1-1000 µg/L (R2 ≥ 0.998), low limits of detection (0.02-0.68 µg/L), and satisfactory accuracy and precision (72.9%-107.6% of average recoveries and <5% of relative standard deviations at 1, 10, 50, and 500 µg/L of xanthates). This is a first method developed for determination of trace xanthates in water samples. It was successfully applied to determine the target analytes in outdated flotation wastewater and river water samples, warranting the occurrence of trace xanthates (0.13-16.9 µg/L) in water and necessity of systematic investigation on environmental fate and risk of xanthates.

[Effect of Butyl Xanthate on Pb2+ and Cd2+ Adsorption by Soil Around a Dressing Plant].

Flotation agents can enter the soil and water environment around mining areas through beneficiation wastewater discharge and overflow from tailings ponds. The adsorption of Pb2+ and Cd2+ on soil around a lead-zinc dressing plant was investigated in the presence of potassium butyl xanthate (PBX). Batch experiments were conducted with different initial pH, PBX, Pb2+, and Cd2+solution concentrations. The fractions of lead and cadmium were altered after treatment with different concentrations of PBX. The results showed that adsorption of Pb2+and Cd2+ on soil was seriously inhibited by PBX. When PBX concentration was 40 mg·L-1, the adsorption capacity of Pb2+ and Cd2+ decreased from 3540 mg·kg-1 and 387 mg·kg-1 to 3085 mg·kg-1 and 100 mg·kg-1, respectively. The Pb2+ and Cd2+ adsorption kinetic process was best fitted by the quasi-second-order kinetic model, which indicated that the adsorption process of Pb2+ and Cd2+ on soil was mainly chemical adsorption. The formation of a hydrophobic and insoluble complex and competitive adsorption between PBX, Pb2+, and Cd2+ on the soil surface was the main reason for reducing the adsorption capacity. The results showed that PBX could increase the mobility of Pb2+ and Cd2+ on soil. The degree of impact improved with increasing initial concentration of PBX and pH but decreased with increasing initial concentration of Pb2+ and Cd2+, and the adsorption isotherms conformed to the Freundlich isotherm. Under low PBX content (100 mg·kg-1), exchangeable and reducible cadmium contents in the soil increased, which could lead to the activation of cadmium in soil. However, the addition of PBX to the treated soil could reduce the content of exchangeable and reducible lead. As the concentration of PBX increased, the reduction effect also increased, which was related to the stronger complex stability of Pb(C4H9OCS2)2 than that of Cd(C4H9OCS2)2. The results showed that residual flotation reagents in beneficiation wastewater may increase the potential ecological risk of heavy metals such as Pb and Cd in soil, and the prevention and control of the potential ecological risk should be strengthened.

Preparation of a novel photocatalytic catalyst PW9@ZnO/Ag and the photocatalytic degradation of butyl xanthate under visible light.

Photocatalytic technology is attracting considerable attention for the advantages of low cost and environmentally friendly properties. In this study, a novel photocatalyst PW9@ZnO/Ag (PZA) was synthesized hydrothermally and characterized by a variety of means. The results indicated that ZnO and Ag NPs were successfully decorated and uniformly dispersed on PW9 to form the composites. The prepared PZA was applied in the degradation of simulated butyl xanthate (BX) beneficiation wastewater both under the UV light and the xenon lamp, and a maximum degradation of 99.83% was obtained under the visible light with 10% ZnO loading, 1 g/L PZA, initial BX concentration of 20 mg/L, and pH 5.5. The PZA was recovered and reused for 5 times, and the degradation rates remained above 70%. Superoxide radical (·O2-) was the main active species for the photocatalytic degradation of BX. The experimental results demonstrate that PZA is a promising photocatalyst, making it a prospective strategy to overcome current challengers in the use of xanthate degradation and beneficiation wastewater treatment under visible light.