Mechanistic insights into stepwise activation of malachite for enhancing surface reactivity and flotation performance

Malachite is a common copper oxide mineral that is often enriched using the sulfidization-xanthate flotation method.Currently,the direct sulfidization method cannot yield copper concentrate products.Therefore,a new sulfidization flotation process was developed to promote the efficient recovery of malachite.In this study,Cu^(2+) was used as an activator to interact with the sample surface and increase its reaction sites,thereby strengthening the mineral sulfidization process and reactivity.Compared to single copper ion activation,the flota-tion effect of malachite significantly increased after stepwise Cu^(2+) activation.Zeta potential,X-ray photoelectron spectroscopy(XPS),time-of-flight secondary ion mass spectroscopy(ToF-SIMS),scanning electron microscopy and energy dispersive spectrometry(SEM-EDS),and atomic force microscopy(AFM)analysis results indicated that the adsorption of S species was significantly enhanced on the mineral surface due to the increase in active Cu sites after Cu^(2+) stepwise activation.Meanwhile,the proportion of active Cu-S spe-cies also increased,further improving the reaction between the sample surface and subsequent collectors.Fourier-transform infrared spec-troscopy(FT-IR)and contact angle tests implied that the xanthate species were easily and stably adsorbed onto the mineral surface after Cu^(2+) stepwise activation,thereby improving the hydrophobicity of the mineral surface.Therefore,the copper sites on the malachite sur-face after Cu^(2+) stepwise activation promote the reactivity of the mineral surface and enhance sulfidization flotation of malachite.

Preparation of K-doped g-C_(3)N_(4) composite loaded on magnetic attapulgite and its degradation performance for malachite green

Visible-light-driven photocatalysis is a promising technology for the treatment of dye wastewater.In this work,a novel photocatalyst of K-doped g-C_(3)N_(4) loaded on magnetic attapulgite(ATP)(Kω-g-C_(3)N_(4)@ATP-Fe_(3)O_(4))with excellent visible light photocatalytic properties and stability were successfully prepared and characterized.The removal efficiency of Kω-g-C_(3)N_(4)@ATP-Fe_(3)O_(4) for malachite green(MG)was studied,and the degradation mechanism was analyzed and proposed.It was found that the K_(5)-g-C_(3)N_(4)@ATP-Fe_(3)O_(4) photocatalyst possessed excellent degradation efficiency of over 98.0%for the MG dye wastewater under optimal conditions.Moreover,the K_(5)-g-C_(3)N_(4)@ATP-Fe_(3)O_(4) materials possessed good recyclability with a removal rate over 82%after 4 cycles.Under visible light condition,the K_(5)-g-C_(3)N_(4)@ATP-Fe_(3)O_(4) photocatalyst produce radicals of·OH and O_(2)^(-)to degrade the MG dyes,which was supported by electron paramagnetic resonance(EPR)and radical trapping experiments.In addition,the LC-MS analysis interpreted the degradation pathways and intermediates of MG in the solution.The findings in this work indicate that the prepared photocatalytic material has excellent degradation efficiency for MG and can be applied in dye wastewater treatment.

Effect of dissolved components of malachite and calcite on surface properties and flotation behavior

In general,malachite is recovered via sulfidization–xanthate flotation,although many unsatisfactory flotation indexes are frequently obtained as a result of the presence of associated calcite.This phenomenon occurs because the dissolved components of malachite and calcite affect the flotation behavior of both minerals.In this study,the effect of the dissolved components derived from malachite and calcite on the flotation behavior and surface characteristics of both minerals was investigated.Flotation tests indicated that malachite recovery decreased when the calcite supernatant was introduced,while the presence of the malachite supernatant increased the recovery of calcite.Dissolution and adsorption tests,along with zeta potential measurements,X-ray photoelectron spectroscopy,Fourier transform infrared spectrometry,and timeof-flight secondary ion mass spectrometry demonstrated that the Ca species in the calcite supernatant were adsorbed on the malachite surface,which hindered the interaction of Na2S with malachite,thereby resulting in the insufficient adsorption of sodium isoamyl xanthate(NaIX)on the surface of malachite.By contrast,the Cu species in the malachite supernatant were adsorbed on the calcite surface,and they provided active sites for the subsequent adsorption of Na_(2)S and NaIX.

Malachite Green Adsorption Using Carbon-Based and Non-Conventional Adsorbent Made from Biowaste and Biomass:A Review

Dyes are pervasive contaminants in wastewater,posing significant health risks to both humans and animals.Among the various methods employed for effective dye removal,adsorption has emerged as a highly promising approach due to its notable advantages,including high efficiency,cost-effectiveness,low energy consumption,and operational simplicity compared to alternative treatments.This comprehensive review focuses on investigating adsorbents derived from biowastes and biomass,specifically carbon-based and non-conventional adsorbents,for the removal of malachite green,a widely used dye known for its toxic and carcinogenic properties.Carbon-based adsorbents encompass two main types:activated carbon and biochar,while non-conventional adsorbents refer to powder sorbents without carbonaceous treatments.Extensive studies have reported remarkable findings,with achieved maximum removal percentages exceeding 98%and capacities reaching 250 mg/g.These results highlight the exceptional efficacy of the reviewed adsorbents in eliminating malachite green from wastewater.By exploring the potential of bio-based adsorbents,this review sheds light on sustainable and environmentally friendly solutions for mitigating dye pollution.

Insights into remediation technology for malachite green wastewater treatment

Malachite green (MG) dye is a common industrial dye and organic contaminant that can be found in (waste)water. Textile and food industries make use of MG as dyeing and food coloring agents, respectively. However, MG is both genotoxic and mutagenic. Hence, the elimination of MG from MG-laden-wastewater is germane. This review summarizes up-to-date researches that have been reported in literature as regards the decontamination of toxic MG wastewater. Various removal methods (adsorption, membrane, Fenton system, and heterogenous and homogeneous photodegradation) were discussed. Of the two basic technologies that are comprehensively explored and reviewed, chemical treatment methods are not as viable as physical removal methods, such as the adsorption technology, due to the lack of secondary pollutant production, simple design, low operation costs, and resource availability. This review also presents various practical knowledge gaps needed for large-scale applications of adsorptive removal methods for MG. It concludes by recommending further research on the techniques of cheap and simple decontamination of MG to get clean water.

Persistence of malachite green and leucomalachite green in perch (Lateolabrax japonicus)

The persistence of malachite green (MG), and its metabolite leucomalachite green (LMG), in fish tissues is still unclear, leading to many trade disputes. In this research, we established and evaluated an HPLC method that could detect MG and LMG simultaneously, and then investigated the persistence of these two toxins in the tissues of juvenile perch (Lateolabrax japonicus) post sub-chronic MG exposure at 1.0 mg/L. Exposure lasted for 2 h everyday and was repeated six times. The perch were then placed in MG-free seawater for 100 d to eliminate the toxins. Results show that MG accumulated in the tissues, including the gills, liver, muscle, blood and viscera, and then was metabolized rapidly to LMG. The concentrations of these two toxins increased significantly with the accumulation process. In general, the highest concentrations of MG and LMG in all tissue exceeded 1 000 μg/kg, except for MG in the muscle. The order of accumulation levels (highest to lowest) of MG was gill>blood>liver>viscera>muscle, while that of LMG was liver>blood>gill>viscera>muscle. High levels of MG or LMG could persist for several hours but decreased rapidly during the elimination process. The concentration of LMG was much higher than that of MG during the experiment, especially in the gill, liver and blood. Therefore, the three tissues play important roles in toxin accumulation, biotransformation, and elimination. Although the MG and LMG concentrations in muscle were much lower than in other tissues, the content still exceeded the European minimum required performance limit (MRPL), even after 2 400 h (100 d) of elimination. This demonstrates that it is extremely difficult to eliminate MG and LMG from tissues of perch, and therefore use of these toxins is of concern to public health.

Flotation performance and adsorption mechanism of novel 1-(2-hydroxyphenyl)hex-2-en-1-one oxime flotation collector to malachite

A novel collector 1-(2-hydroxyphenyl)hex-2-en-1-one oxime(HPHO)was synthesized from 2-hydroxy acetophenone and butyraldehyde.Its flotation performance and adsorption mechanism to malachite were investigated by flotation test,zeta potential,Fourier transform infrared(FTIR)and X-ray photoelectron spectroscopy(XPS)analysis techniques.Compared with benzohydroxamic acid(BA),1-(2-hydroxyphenyl)ethan-1-one oxime(HPEO)and sodium isobutyl xanthate(SIBX),HPHO exhibited excellent collecting power to malachite without additional reagents,such as Na2S regulator and methyl isobutyl carbinol(MIBC)frother.Results of zeta potential indicated that HPHO was coated on malachite surfaces through a chemisorption process.FTIR and XPS data gave clear evidence for the formation of Cu−oxime complex on malachite surfaces after HPHO adsorption through the linkage between C=C,—OH,N—OH group and Cu species.

A novel adsorbent of three-dimensional ordered macro/mesoporous carbon for removal of malachite green dye

Three-dimensional ordered macro/mesoporous carbon(3DOM/m-C)with high specific surface area was synthesized by colloid crystal template method with chemical activation by KOH and used as the adsorbent for removing malachite green(MG)in aqueous solution.The microstructures of the adsorbents were characterized by FESEM,TEM and BET,and the effects of initial dye concentration,contact time,solution pH,and temperature on adsorption performance were investigated.The results show that the 3DOM/m-C exhibits extremely high adsorption capacity of 3541.1 mg/g within 2 h,which could be attributed to the novel ordered hierarchical structure with mesopores on three-dimensional ordered macroporous carbon walls.And the adsorption behavior conforms to the pseudo-second-order kinetic and Langmuir adsorption isotherm.3DOM/m-C can be recycled after being desorbed by absolute ethanol,and still maintains a high capacity of 2762.06 mg/g after 5 cycles.

Investigation on leaching of malachite by citric acid

Leaching of an oxidized copper ore containing malachite, as a new approach, was investigated by an organic reagent, citric acid. Sulfuric acid is the most common reagent in the leaching of oxide copper ores, but it has several side effects such as severe adverse impact on the environment. In this investigation, the effects of particle size, acid concentration, leaching time, solid/liquid ratio, temperature, and stirring speed were optimized. According to the experimental results, malachite leaching by citric acid was technically feasible. Optimum leaching conditions were found as follows： the range of particle size, 105-150 μm; acid concentration, 0.2 M; leaching time, 30 min; solid/liquid ratio, 1：20 g/mL; temperature, 40℃; and stirring speed, 200 r/min. Under the optimum conditions, 91.61% of copper was extracted.

Adsorption behavior and mechanism of copper ions in the sulfidization flotation of malachite

Malachite is one of the main minerals used for the industrial enrichment and recovery of copper oxide resources, and copper ions are unavoidable metal ions in the flotation pulp. The microflotation, contact angle, and adsorption experiments indicated that pretreatment with an appropriate concentration of copper ions could improve the malachite recovery, and the addition of excess copper ions reduced the hydrophobicity of the malachite surface. The results of zeta potential tests indicated that sodium sulfide and butyl xanthate were also adsorbed on the surface of malachite pretreated with copper ions. X-ray photoelectron spectroscopy(XPS) results indicated that —Cu—O and —Cu—OH bonds were formed on the surface of the samples. After pretreatment with an appropriate concentration of copper ions, the number of —OH groups on the mineral surface decreased, whereas the number of Cu—S groups on the mineral surface increased, which was conducive to the sulfidization of malachite. After adding a high concentration of copper ions, the —OH groups on the mineral surface increased, whereas the number of Cu—S groups decreased, which had an adverse effect on the sulfidization flotation of malachite. Time-of-flight secondary ion mass spectrometry showed that pretreatment with copper ions resulted in a thicker sulfidization layer on the mineral surface.

Study on the mechanical activation of malachite and the leaching of complex copper ore in the Luanshya mining area, Zambia

Mechanical activation(MA) of malachite was carried out by dry planetary grinding(DPG) and wet Isa grinding(WIG) methods. When the rotational speed was increased to 400 r/min in DPG, the specific surface area of malachite reached the maximum and the particle size reached the minimum of 0.7–100 μm. Agglomeration occurred between mineral particles when the rotational speed was increased to 580 r/min in DPG.However, no agglomeration was observed among particles with sizes 0.4–3 μm in WIG. X-ray diffraction analysis showed that, at a 580 r/min rotational speed in DPG, the amorphization degree of malachite was 53.12%, whereas that in WIG was 71.40%, indicating that MA led to amorphization and distortion of crystal structures. In addition, in the Fourier transform infrared(FT-IR) spectra of activated malachite, the bands associated with –OH, CO_3^(2-)and metal lattice vibrations of Cu–O and Cu–OH were weakened, and a new H–O–H bending mode and peaks of gaseous CO_2 appeared, indicating that MA decreased the band energy, enhanced dihydroxylation, and increased the chemical reactivity of the malachite.Furthermore, the leaching behavior of copper ore was greatly improved by MA.

Fe Nanoparticles Synthesized by Pomegranate Leaves for Treatment of Malachite Green

A green and convenient pathway of preparing iron nanoparticles(FeNPs)with pomegranate leaf(PG)extract for highly effective removal of malachite green(MG)was proposed under ambient conditions.The materials were characterized by scanning electron microscope(SEM),X-ray energy-dispersive spectrometer(EDS),Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS)techniques.The results show that their surfaces are capped and stabilized by PG extract with amorphous nature and without any detection of zero-valent iron.The size and surface valence state of FeNPs are the key factors that affect the MG removal efficiency.As the reagent volume ratio of PG extract to FeCl_(3) increases greater than 1,the cross-linked FeNPs become more obvious,having a homogeneous distribution with the size range from 30 to 40 nm,and show an increasing ratio ofFe(Ⅱ)/Fe(Ⅲ),which is in proportion to the degradation efficiency of MG,reaching higher than 95%in only 2 min by using 50 mg Fe/L FeNPs and 200 mg/L MG.

Degradation of malachite green dye by Tenacibaculum sp. HMG1isolated from Pacific deep-sea sediments

A deep-sea bacterium from the Pacific Ocean identified as Tenacibaculum sp. HMG1 was found to have strong malachite green（MG） degradation activity. The MG tolerance and decolorizing activities of strain HMG1 were confirmed by bacterial growth and high-performance liquid chromatography（HPLC） analyses. Strain HMG1 was capable of removing 98.8% of the MG in cultures within 12 h and was able to grow vigorously at 20 mg/L MG. A peroxidase gene detected in the genome of strain HMG1 was found to be involved in the MG biodegradation process. The corresponding recombinant peroxidase（r POD） demonstrated high degradative activity at 1 000 mg/L MG. Based on the common candidate intermediates, strain HMG1 was inferred to have one primary MG degradation pathway containing r POD. In addition, five other candidate intermediates of the r POD-MG degradative process were detected. The optimal conditions for MG degradation were determined and showed that strain HMG1 and the r POD enzyme could maintain high bioactivity at a low temperature（20℃）, variable p H values（6.0–9.0）, higher salinities（100 mmol/L） and other factors, such as multiple metal ions, H2O2 and EDTA.MG-tolerant strain Tenacibaculum sp. HMG1 and its peroxidase have prospective applications as environmental amendments for MG degradation during coastal remediation.

Development of a Fast ELISA for the Specific Detection of both Leucomalachite Green and Malachite Green

Malachite green(MG), a dye, is an antifungal agent that has been used to treat and prevent fish diseases. It is metabolized into reduced leucomalachite green forms(LMG) that may reside in fish muscles for a long period, thus being harmful to human health. The aim of this study was to develop a competitive and direct enzyme-linked immunosorbent assay(ELISA) to detect MG and LMG specifically. The monoclonal antibody(m Ab) to LMG was generated using a hybridoma technique. The obtained m Ab showed good cross-reactivity(CR) to malachite green(MG), but not to crystal violet(CV) and Brilliant Green(BG). The m Ab was used to develop a fast detecting ELISA of MG and LMG in fish. By introducing the conjugation LMG-HRP, the detection capability was 0.37 ng m L-1 for MG and LMG. The mean recovery from spiked grass carp tissues ranged from 76.2% to 82.9% and the coefficients of variation varied between 1.8% and 7.5%. The stable and efficient monoclonal cell line obtained is a sustainable source of sensitive and specific antibody to MG and LMG.

Reactive species in resin supported heterogeneous Fenton-like oxidation of Malachite green solution

During the oxidative degradation of nonbiodegradable Malachite green (MG) by means of H2O2 /FeIIIR (iron supported on ion-exchage resin) in a dynamic column,the binding energy of the Fe(2p3/2) region for XPS spectra was found to be different between the top layer and the bottom layer in this column. Based on the data from XPS spectra and DMPO-OH·signal by EPR spectra,it is shown that the formation of ferryl (IV) is the key step for the oxidation of MG. The ferryl (IV) species can oxidize MG,and its redox potential is about 0. 739 - 0. 803 V measured by cyclic voltammograms (CV) . The catalytic capability of ferryl (IV) species was also evaluated,and it is found that it can promote the decomposition of H2O2 more efficiently than ferric iron. The removal rate of MG mainly depends on the adsorption of catalyst. Both ferryl (IV) and HO·radicals are the reactive species in the system. The oxidation of HO·is only a small part of the overall removal rate. Based on the obtained results,a possible mechanism for a resin-supported Fenton-like oxidation reaction is proposed.

Adsorption Characteristics of Activated Carbon Derived from Scrap Tires for Malachite Green:Influence of Small Organics

The influence of small organics on the adsorption characteristics of activated carbon produced from industrial pyrolytic tire char(APTC)for malachite green(MG) was investigated by a batch method. Phenol was chosen as the representative of small organics. The effects of phenol on adsorption equilibrium, kinetics and thermodynamics were studied systematically. The results indicate that APTC is a potential adsorbent for MG. The presence of phenol decreases the adsorption capacity of APTC for MG, but improves the rate of adsorption, while the adsorption characteristics, such as equilibrium, kinetics and thermodynamics are not affected by phenol. The adsorption equilibrium data follow Langmuir isotherm and the kinetic data are well described by the pseudo-second-order kinetic model. The adsorption process follows intra-particle diffusion model and the adsorption rate is determined by more than one process. Thermodynamic study shows that the adsorption is an endothermic and spontaneous physisorption process.

High-Pressure Behavior of Copper Carbonate:Data from Malachite

In-situ high-pressure energy dispersive X-ray diffraction experiments of malachite have been performed using diamond anvil cell and synchrotron radiation. The highest recorded pressure is up to 17.4 GPa. The experimental results reveal that malachite experienced two phase transitions at 0.7 and 7.8 GPa, and the last one is reversible.

Dissolution kinetics of malachite in ammonia/ammonium sulphate solution

The dissolution kinetics of malachite was investigated in ammonia/ammonium sulphate solution. The effects of ammonia and ammonium sulphate concentration, pH, leaching time, reaction temperature, and particle size were determined. The results show that the optimum leaching conditions for malachite ore with a copper extraction more than 96.8% are ammonia/ammonium concentration 3.0 mol/L NHaOH ＋ 1.5 mol/L （NH4）2SO4, liquid-to-solid ratio 25：1 mL/g, leaching time 120 min, stirring speed 500 r/rain, reaction temperature 25 ℃ and particle size finer than 0.045 mm. The dissolution process of malachite with an activation energy of 26.75 k J/tool is controlled by the interface transfer and diffusion across the product layer. A semi-empirical rate equation is obtained to describe the leaching process and the reaction orders with respect to concentration of ammonia and ammonium sulphate are 2.983 0 and 0.941 1, respectively.

Flow-injection spectrophotometric determination of vanadium with malachite green oxalate by bromate in acidic and micellar medium

A flow injection method is proposed for determining vanadium（V）. The method is based on its catalytic effect on the oxidation of malachite green oxalate by bromate. The reaction was monitored spectrophotometrically by measuring malachite green oxalate absorbance at λmax = 625 nm. The reagents and manifold variables, which have influences on the sensitivity, were investigated and the optimum conditions were established. The optimized conditions made it possible to determine vanadium in the ranges of 10-140 ng/mL with a detection limit of 5.2 ng/mL and a sample rate of 20 ± 5 samples/h.

Studies on the synthesis and properties of malachite green imprinted polymer

A new molecularly imprinted polymer was synthesized with malachite green (MG) as molecular template, methacrylic acid (MAA) as functional monomer, ethylene dimethacrylate (EDMA) as crosslinker, and azobisisobutyronitrile (AIBN) as initiator. Recognition properties of the MG imprinted polymer were studied by equilibrium adsorption and HPLC. The results showed that the imprinted polymer had good affinity and marked selectivity for MG, and can separate MG with its analogue commendably. The new polymer can be used for the enrichment of MG in complex sample, and can work as separation media to separate and detect MG by HPLC.