Hydrothermal Syntheses, Structure Characteristics and Magnetic Properties of a Series of New Molybdenum Arsenates Based on {(As3O3)2(Mo6O18)(MO6)}(M = Ni, (1); Co, (2); Zn, (3))

Three new polyoxometalates K2[H2（As3O3）2（Mo6O18）（NiO6）]？H2O （1）, K2[H2-（As3O3）2（Mo6O18）（CoO6）]？H2O （2） and [Zn（H4,4？-bpy）2（H2O）4][（As3O3）2（Mo6O18）（ZnO6）]？4H2O （3） （4,4？-bpy = 4,4？-bipyridine） have been synthesized under hydrothermal conditions and characterized by IR, elemental analyses, XPS and single-crystal X-ray diffraction analyses, respectively. Compound 1 represents a new 3D framework structure constructed from polyoxoanion [（As3O3）2（Mo6O18）（NiO6）]4- via covalent bond. Compound 2 has an identical structure with 1. Compound 3 represents a new 2D layer structure constructed from transition metal coordination cations [Zn（H4,4？-bipy）2（H2O）4]4＋, lattice water molecules and polyoxoanions [（As3O3）2- （Mo6O18）（ZnO6）]4- via multi-point N–H？？？O and O–H？？？O hydrogen bonding interactions. Crystal data： for 1, cubic, space group Pa-3, a = 15.0022（8） ？, V = 3376.5（3） ？3, Z = 24; for 2, cubic space group Pa-3, a = 15.1596（10）, V = 3483.88 ？3, Z = 24; for 3, monoclinic, space group C2/m, a = 19.699（4）, b = 14.223（3）, c = 9.1455（18） ？, β = 106.80（3）o, V = 2453.0（9） ？3, Z = 8. In addition, the magnetic behaviors for compounds 1 and 2 have been investigated.

The long-term stability of calcium arsenates:Implications for phase transformation and arsenic mobilization

It is well known that calcium arsenates may not be a good choice for arsenic removal and immobilization in hydrometallurgical practices.However,they are still produced at some plants in the world due to various reasons.Furthermore,calcium arsenates can also naturally precipitate under some specific environments.However,the transformation process of poorly crystalline calcium arsenates(PCCA)and the stability of these samples under atmospheric CO2 are not yet well understood.This work investigated the transformation process of PCCA produced by using different neutralization reagents(CaO vs.NaOH)with various Ca/As molar ratios at pH 7-12 in the presence of atmospheric CO2.After aging at room temperature for a period of time,for samples neutralized with NaOH and precipitated at pH 10 and 12,release of arsenic back into the liquid phase occurred.In contrast,for the samples precipitated at pH 8,the aqueous concentration of arsenic was observed to decrease.XRD,Raman,and SEM results suggested that the formation of various types of crystalline calcium carbonates and/or calcium arsenates controls the arsenic behavior.Moreover,the application of lime may enhance the stability of the generated PCCA.However,no matter what neutralization reagent is used,the stability of the generated PCCA is still of concern.

Recycling arsenic-containing bio-leaching residue after thermal treatment in cemented paste backfill:Structure modification,binder properties and environmental assessment

The substantial arsenic(As)content present in arsenic-containing bio-leaching residue(ABR)presents noteworthy environ-mental challenges attributable to its inherent instability and susceptibility to leaching.Given its elevated calcium sulfate content,ABR exhibits considerable promise for industrial applications.This study delved into the feasibility of utilizing ABR as a source of sulfates for producing super sulfated cement(SSC),offering an innovative binder for cemented paste backfill(CPB).Thermal treatment at varying temperatures of 150,350,600,and 800℃ was employed to modify ABR’s performance.The investigation encompassed the examination of phase transformations and alterations in the chemical composition of As within ABR.Subsequently,the hydration characteristics of SSC utilizing ABR,with or without thermal treatment,were studied,encompassing reaction kinetics,setting time,strength development,and microstructure.The findings revealed that thermal treatment changed the calcium sulfate structure in ABR,consequently impacting the resultant sample performance.Notably,calcination at 600℃ demonstrated optimal modification effects on both early and long-term strength attributes.This enhanced performance can be attributed to the augmented formation of reaction products and a densified micro-structure.Furthermore,the thermal treatment elicited modifications in the chemical As fractions within ABR,with limited impact on the As immobilization capacity of the prepared binders.

Multiple roles of arsenic compounds in phase separation and membraneless organelles formation determine their therapeutic efficacy in tumors

Arsenic compounds are widely used for the therapeutic intervention of multiple diseases.Ancient pharmacologists discovered the medicinal utility of these highly toxic substances,and modern pharmacologists have further recognized the specific active ingredients in human diseases.In particular,Arsenic trioxide(ATO),as a main component,has therapeutic effects on various tumors(including leukemia,hepatocellular carcinoma,lung cancer,etc.).However,its toxicity limits its efficacy,and controlling the toxicity has been an important issue.Interestingly,recent evidence has pointed out the pivotal roles of arsenic compounds in phase separation and membraneless organelles formation,which may determine their toxicity and therapeutic efficacy.Here,we summarize the arsenic compoundsregulating phase separation and membraneless organelles formation.We further hypothesize their potential involvement in the therapy and toxicity of arsenic compounds,highlighting potential mechanisms underlying the clinical application of arsenic compounds.

A new approach for recycling arsenic and tin from low-grade tin middlings using a self-sulfurization roasting

Massive amounts of low-grade tin middlings have been produced from tin tailings,in which arsenic and tin are worthy to be recycled.Owing to high sulfur content in these tin middlings,a novel self-sulfurization roasting was proposed to transform,separate and recover arsenic and tin in this research.There was no extra curing agent to be added,which decreased the formation of pollutant S-containing gas.The self-sulfurization process involved a two-stage roasting of reduction followed by sulfurization.First in reduction roasting,FeAsS decomposed to FeS and As and the As then transformed to As_(4)(g)and As_(4)S_(4)(g),via which the arsenic was separated and recovered.The arsenic content in the first residue could be decreased to 0.72 wt.%.Accompanied with it,the FeS was firstly oxidized to Fe_(1−x)S and then to SO_(2)(g)by the coexisted Fe_(2)O_(3),and finally reduced and combined with the independent Fe_(2)O_(3)to form Fe_(1−x)S.In the followed sulfurization roasting,the Fe_(1−x)S sulfurized SnO_(2)to SnS(g),due to which tin could be recovered and its content in the second residue decreased to 0.01 wt.%.This study provided an efficient method to separate and recover arsenic and tin from low-grade tin middlings.

Arsenic and fluoride co-enrichment of groundwater in the loess areas and associated human health risks:A case study of Dali County in the Guanzhong Basin

This study aims to reveal the occurrence and origin of typical groundwater with high arsenic and fluoride concentrations in the loess area of the Guanzhong Basin—a Neogene faulted basin.Key findings are as follows:(1)Groundwater samples with high arsenic and fluoride concentrations collected from the loess area and the terraces of the Weihe River accounted for 26%and 30%,respectively,of the total samples,with primary hydrochemical type identified as HCO_(3)-Na.The karst and sand areas exhibit relatively high groundwater quality,serving as preferred sources for water supply.It is recommended that local governments fully harness groundwater in these areas;(2)groundwater with high arsenic and fluoride concentrations in the loess area and the alluvial plain of rivers in Dali County is primarily distributed within the Guanzhong Basin,which represents the drainage zone of groundwater;(3)arsenic and fluoride in groundwater originate principally from natural and anthropogenic sources;(4)the human health risk assessments reveal that long-term intake of groundwater with high arsenic and fluoride concentrations pose cancer or non-cancer risks,which are more serious to kids compared to adults.This study provides a theoretical basis for the prevention and treatment of groundwater with high arsenic and fluoride concentrations in loess areas.

Feasibility Evaluation of Using Biochar-based Permeable Reactive Barrier for the Remediation of Mercury and Arsenic Composite Polluted Water Bodies

This study employed a modified biochar material to construct a permeable reactive barrier(PRB)for the treatment of water bodies polluted with mercury and arsenic.The experimental results demonstrated that the addition of goethite-modified biochar significantly enhanced the remediation efficiency of As(III),achieving a maximum removal rate of 100%.Conversely,pure biochar exhibited high efficiency in the removal of Hg(II),with a maximum removal rate approaching 100%.Furthermore,the pH level of the water significantly influenced the adsorption efficiency of heavy metal ions,with the optimal removal performance observed at a pH of 6.0.The PRB system demonstrated excellent removal rates under low concentrations of heavy metals.However,as the concentration increased,the remediation efficiency exhibited a slight decrease.In summary,the findings of this study provide compelling evidence for the use of modified biochar in the construction of PRBs for the remediation of mercury and arsenic-polluted water bodies.Furthermore,the study reveals the mechanism by which pH and heavy metal concentration influence remediation efficiency.

Distribution and Contamination of Arsenic in Fish, Gastropods and Bivalves in the Aby and Tendo Lagoons in East of Ivory Coast

Lagoons are ecosystems for biodiversity and the livelihoods of coastal communities. The main objective of the study was to analyze the variability of arsenic concentrations in gastropods and bivalves in the Aby and Tendo lagoons, taking into account spatial, seasonal and hydrological variations. The study was carried out in four stages spread over two successive hydroclimatic cycles, including two seasons during the rainy season and two more during the dry season. The samples were taken in two areas of the Aby and Tendo lagoons. Arsenic levels were measured by ICP-MS. The results showed that mean arsenic concentrations in the muscles of organisms in Aby Lagoon ranged from 0.01 to 1.26 μg As/g, with a mean and median of 0.17 and 0.06 μg As/g, respectively. Fish had the highest levels of arsenic, followed by crustaceans, while molluscs and plants had lower and comparable concentrations of As. Arsenic concentrations in tilapia and jawbones varied significantly between sites and seasons, with higher concentrations at Tendo and during the rainy season. Arsenic concentrations in gastropods and bivalves were significantly higher than those of other species, with averages of 0.74 and 1.03 mg As/kg, respectively.

Roles of Aqueous Extract of Marigold on Arsenic-Induced Oxidative Damage in Pancreatic Islet β-Cells

Roles of Marigold extracts (ME) on arsenic trioxide (ATO)-induced oxidative damage to pancreatic β-cells need to be further elucidated. In this study, NIT-1 cells were treated with different concentrations of and/or ATO, following by the cell viability was detected by CCK8 assay. Then, intracellular reactive oxygen species (ROS) levels, lipid peroxide (MDA) contents and superoxide dismutase (SOD) activity were measured with a fluorescence probe method and colorimetric assay, respectively. The apoptosis rate and morphology was detected and observed with hoechst 33,258 staining assay. The mRNA levels and protein expressions of nuclear factor E2-related factor 2 (Nrf2) and heme oxygenase-1 (HO-1) were measured by real-time fluorescence quantitative polymerase chain reaction and protein immunoblotting assay, respectively. Our results indicated that Co-treatment with ME and ATO exacerbated the cell viability decreasing reduced by ATO, while the addition of ME after ATO treatment effectively promote the recovery of ATO reduced survival rates. The ATO group increased apoptosis (P P β-cells by modulating the activation of the Nrf2 signaling pathway.

The Secret Toxic Legacies of Chemical Warfare: Agent Blue Use during the 2nd Indochina and Vietnam Wars in Laos, Cambodia, and Vietnam (1961 to 1971)

During the 2nd Indochina War which started in 1959, the United States Central Intelligence Agency (CIA), Air America, and the Air Force waged a secret and unconventional air war in Laos from Udorn Air Force base located in Thailand and across the Mekong River from Vientiane, Laos. Starting in 1961, four years before the official start of the American-Vietnam War, Agent Blue, the arsenic-based herbicide used to kill rice and other food crops, was used extensively in Laos, Vietnam and to a lesser extent in Cambodia. During the secret 2nd Indochina War and the Vietnam Civil War the public knew little about the use of Agent Blue. After the official start of the American-Vietnam War in 1965, the United States media news reports, about chemical warfare were dominated by the story of Agent Orange and its devastating impacts. The public knew very little about the previous use of Agent Blue in both wars. The first known media pick up of the Agent Blue (arsenic based) and Agent Pink, Agent Green, and Agent Purple (all three contain 2, 4, 5-T and unknown amounts of dioxin TCDD) was in May of 1964. Jim G. Lucas, a Scripps-Howard staff reporter submitted an article that was published as an editorial in Washington Post on May 26, 1964. The next news reference to this chemical weapon was a Letter to the Editor published in the New York Times titled “Agent Blue” in Vietnam by Arthur H. Westing in (1971). The use of herbicides, including Agent Blue in Laos during the 2nd Indochina War, was kept a secret until 1982, when a draft of Buckingham’s study of Operation Ranch Hand was made public. Much about the U.S. war effort in Laos is still classified. In a 2014 issue of the VVA Veteran magazine, Loana Hoylman published an article on “Today’s Blue Arsenic in the Environment”. The first refereed journal article on this topic, “The Fate of Agent Blue, the Arsenic-Based Herbicide, Used in South Vietnam during the Vietnam War” was published in 2020 in the Open Journal of Soil Science by Kenneth R. Olson and Larry Cihacek. In 2021 the Asia Times (print) and VietnamVeteranNews (radio podcast) picked up the Agent Blue story. During the early 2020s, Olson published six additional refereed journal articles on Agent Blue, cacodylic acid, and arsenic. The primary objective is to determine why no major news organization in the United States, including the New York Times and Washington Post, have never investigated Agent Blue use during the 2nd Indochina and Vietnam wars? Why did the use of Agent Blue story, used to destroy Laotian and South Vietnamese civilian food (rice) sources and production sites, received only very limited coverage by US print media news organizations during the last 64 years?

Review and Analysis: Evaluation of the Impacts and Consequences of Using Agricultural Herbicides as Military Chemical Weapons in Second Indochina War

The legacy of the human misery caused by the application of the herbicides including Agent Purple and Agent Orange contaminated with unknown amounts of dioxin TCDD and Agent Blue, the arsenic-based herbicide, sprayed over the jungles, rice fields, and hamlets of Vietnam is still haunting us today. Why did this happen? Could it have been prevented? Was it necessary United States military strategy? Was it an intentional decision to inflict this blight on the enemy soldiers and the Vietnamese, Cambodian, and Laotian civilians, to poison their land and cause generations of harm? Alternatively, was it an unpreventable accident in the march of military history? What patterns in the U.S. government’s thought process could be identified as the cause, which led to the decision to use these herbicides as tactical chemical weapons? If the introduction of herbicide (chemical) weapons had not been made, would the outcome of the Vietnam War and the Secret Wars in Laos and Cambodia have been any different? The objective of this treatise is to outline the role of world events and backgrounds and the role of the leaders, U.S. military, CIA, USDA, U.S. State Department, the U.S. President appointed Ambassadors to Vietnam and Laos, chemical companies, and President Diệm’s Republic of Vietnam (RVN) government and military. Their collective advice led to the decision to use herbicides as military and environmental chemical weapons in the Second Indochina War. Were the National interests achieved by U.S. military strategy in the RVN using herbicide weapons worth the long-term environmental and human health consequences in Vietnam, Cambodia, and Laos? Did it impact the outcome of the Second Indochina War?

Removal and stabilization of arsenic from anode slime by forming crystal scorodite

A process was proposed for removing and stabilizing arsenic(As) from anode slime. The anode slime with high arsenic concentration was pretreated by circular alkaline leaching process. Then, the arsenic in the leaching solution can be further precipitated as a form of scorodite crystalline(FeAsO4·2H2O). In the precipitating arsenic reaction, in which ferrous ions were oxidized by air gas, the effects of acidity(p H), reaction temperature, air flow rate, initial concentration of arsenic and initial molar ratio of Fe(II) to As(V) on arsenic precipitation were investigated. The results showed that sufficiently stable crystal scorodite could be achieved under the condition of initial arsenic concentration of 10 g/L, pH 3.0-4.0, Fe/As molar ratio of 1.5, the temperature of 80-95 °C, and the air flow rate higher than 120 L/h. Under the optimal condition, more than 78% of arsenic could be precipitated as a form of scorodite crystalline. The As leaching concentration of the precipitates was less than 2.0 mg/L and the precipitates may be considered to be safe for disposal.

Leaching behavior of metals from high-arsenic dust by NaOH-Na_2S alkaline leaching

Arsenic is selectively extracted from high-arsenic dust by NaOH-Na2S alkaline leaching process. In the leaching arsenic process, the effects of alkali-to-dust ratio, sodium sulfide addition, leaching temperature, leaching time and liquid-to-solid ratio on metals leaching efficiencies were investigated. The results show that the arsenic can be effectively separated from other metals under the optimum conditions of alkali/dust mass ratio of 0.5, sodium sulfide addition of 0.25 g/g, leaching temperature of 90 ℃, leaching time of 2 h, and liquid-to-solid ratio of 5：1 （mL/g）. Under these conditions, the average leaching efficiencies of arsenic, antimony, lead, tin and zinc are 92.75%, 11.68%, 0.31%, 29.75% and 36.85%, respectively. The NaOH-Na2S alkaline leaching process provides a simple and highly efficient way to remove arsenic from high-arsenic dust, leaving residue as a suitable lead resource.

Extraction of arsenic from arsenic-containing cobalt and nickel slag and preparation of arsenic-bearing compounds

The arsenic extraction from the arsenic-containing cobalt and nickel slag,which came from the purification process of zinc sulfate solution in a zinc smelting factory,was investigated.The alkaline leaching method was proposed according to the mode of occurrence of arsenic in the slag and its amphoteric characteristic.The leaching experiments were conducted in the alkaline aqueous medium,with bubbling of oxygen into the solution,and the optimal conditions for leaching arsenic were determined.The results showed that the extraction rate of arsenic was maximized at 99.10%under the optimal conditions of temperature 140 ℃,NaOH concentration 150 g/L,oxygen partial pressure 0.5 MPa,and a liquid-to-solid ratio 5：1.Based on the solubilities of As2O5,ZnO and PbO in NaOH solution at 25 ℃,a method for the separation of As in the form of sodium arsenate salt from the arsenic-rich leachate via cooling crystallization was established,and the reaction medium could be fully recycled.The crystallization rate was confirmed to reach 88.9%（calculated on the basis of Na3AsO4） upon a direct cooling of the hot leachate down to room temperature.On the basis of redox potentials,the sodium arsenate solution could be further reduced by sulfur dioxide（SO2） gas to arsenite,at a reduction yield of 92%under the suitable conditions.Arsenic trioxide with regular octahedron shape could be prepared successfully from the reduced solution,and further recycled to the purification process to purify the zinc sulfate solution.Also,sodium arsenite solution obtained after the reduction of arsenate could be directly used to purify the zinc sulfate solution.Therefore,the technical scheme of alkaline leaching with pressured oxygen,cooling crystallization,arsenate reduction by SO2 gas,and arsenic trioxide preparation,provides an attractive approach to realize the resource utilization of arsenic-containing cobalt and nickel slag.

Determination of arsenic speciation in secondary zinc oxide and arsenic leachability

The species of arsenic in secondary zinc oxide generated from fuming furnace were investigated. The results revealed that there are mainly three types of secondary zinc oxide based on three arsenic species. The main phase of As is As2O3 in type Ⅰ, zinc arsenite （Zn（AsO2）2） in type Ⅱ and lead arsenate （Pb（As206）, Pb4As2O9） in type Ⅲ, respectively. Selective leaching of zinc oxide of type Ⅱ was carried out. The leaching rate of As kept at 65%-70% with 30 g/L NaOH and L/S ratio of 3 at 20 ℃ for 1 h, while the losses of Pb and Zn were both below 1%.

Separation and recovery of Cu and As during purification of copper electrolyte

Cu, As, Sb and Bi in copper electrolyte could be efficiently removed by reducing with SO2 followed by evaporative crystallization. As2O3 and CuSO4·5H2O were obtained after crystallized product was treated by dissolution, oxidation, neutralization, sedimentation, filtration and evaporative crystallization. The removal rates of Cu, As, Sb and Bi are 87.1%, 83.9%, 21.0% and 84.7%, respectively, when As （Ⅴ） in copper electrolyte is fully reduced to As （Ⅲ） by SO2, and the H2SO4 in concentrated copper electrolyte is 645 g/L. The removal rate of As is 92.81% when 65 g crystallized product is dissolved in 200 mL water at 30 ℃. The CuSO4·5H2O content is 98.8% when the filtrate is purified under the conditions that n（Fe）：n（As） is 1.2, the dosage of H2O2 is 19 times the stoichiometric needed, temperature is 45 ℃, time is 40 min, pH is 3.7, and then is evaporation crystallized.

Separation and recovery of Cu and As from copper electrolyte through electrowinning and SO_2 reduction

Cu and As were separated and recovered from copper electrolyte by multiple stage electrowinning, reduction with SO2and evaporative crystallization. Experimental results showed that when the current density was 200 A/m2, the electrolyte temperature was 55 °C, the electrolyte circulation rate was about 10 mL/min and the final Cu concentration was higher than 25.88 g/L, the pure copper cathode was recovered. By adjusting the current density to 100 A/m2 and the electrolyte temperature to 65 °C, the removal rate of As was 18.25% when the Cu concentration decreased from 24.69 g/L to 0.42 g/L. After As（V） in Cu-depleted electrolyte was fully reduced to As（Ⅲ） by SO2, the resultant solution was subjected to evaporative crystallization, then As2O3 was produced, and the recovery rate of As was 59.76%. The cathodic polarization curves demonstrated that both Cu2＋ concentration and As（V） affect the limiting current of Cu2＋ deposition.

Reduction and deposition of arsenic in copper electrolyte

The influences of temperature, H2SO4 concentration, CuSO4 concentration, reaction time and SO2 flow rate on the reduction of arsenic（V） with SO2 were studied and the deposition behavior of arsenic （III） under the effect of concentration and co-crystallization was investigated in copper electrolyte. The results indicate that reduction rate of arsenic （V） decreases with increasing temperature and H2SO4 concentration, but increases with increasing SO2 flow rate and reaction time, and it can reach 92% under appropriate conditions that reaction temperature is 65 °C, H2SO4 concentration is 203 g/L, CuSO4 concentration is 80 g/L, reaction time is 2 h and SO2 gas flow rate is 200 mL/min. To remove arsenic in the copper electrolyte, arsenic （V） is reduced to trivalence under the appropriate conditions, the copper electrolyte is concentrated till H2SO4 concentration reaches 645 g/L, and then the removal rates of As, Cu, Sb and Bi reach 83.9%, 87.1%, 21.0% and 84.7%. The XRD analysis shows that crystallized product obtained contains As2O3 and CuSO4·5H2O.

Determination of Arsenic and Mercury in Soil by Microwave Digestion and Hidride GenerationAtomic Fluorescence Spectrometry

[Objective] The aim was to develop a rapid, simple method for determina- tion of arsenic and mercury in soil samples by atomic fluorescence spectrometry. [Method] The method for determination of As and Hg in soil by combined atomic fluorescence spectrometry and microwave digestion was used. [Result] The concentration curve was linear within the range of 0-80.0μg/L of As and 0-8.0 μg/L of Hg, and the detection limits of As and Hg was 0.036 μg/L and 0.015 μg/L, respectively. The precision for elevenfold determination of As at 40.0 ug/L level and Hg at 4.0μg/L level were 1.1% and 2.2%（RSD）, respectively. Recoveries of 103.0%-106.6% for As and 90.0%-95.0% for Hg were obtained for there soil samples. [Conclusion] The proposed method has the advantages of simple operation, high sensitivity, and high efficiency; it was successfully used for determination of As and Hg in soil samples.

Preparation and evaluation of As_2O _3 nanoparticles for treatment of human liver cancer cells in vitro

This paper studies the preparation method of As_2O_3 nanoparticles and theirantitumor effect on human liver cancer cells. As_2O_3 nanoparticles were prepared by sol-gel method.As_2O_3 nanoparticles were characterized by transmission electron microscope ( TEM), energydispersive spectrometer ( EDS) and computer color magic image analysis system (CMIAS). A methylthiazolyl tetrazolium (MTT) assay and a flow cytometry (FCM) assay were performed to examine theantitumor effect of As_2O_3 nanoparticlesat various concentrations(1, 2, 5, 10 mumol/L). We alsocompared the antitumor effect of As_2O_3 nanoparticles with that of As_2O_3 solution. The averagediameters of two kinds of As_2O_3 nanoparticles prepared were about 80 nm and 40 nm. It wasidentified that the prepared nanoparticles were As_2O_3 and there were no other components by EDS.After 48 h of treatment with As_2O_3 nanoparticles, the survival ratio of cells was significantlylower than that of the As2O3 solution with the same concentration(P < 0. 05). Experimental resultsdemonstrate that by sol-gel method As_2O_3 can be prepared into nanoparticles. As_2O_3 nanoparticlescan produce a better cytotoxic effect on tumor cells than the As_2O_3 solution.