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By A. B. Young

THERE were produced in this country in 1923 probably in the neighborhood of 12,000 or 13,000 tons of refined and crude arsenic, by far the greater portion coming as a by product of smelting operations. Early this year copper smelters were producing arsenic at the rate of about 425 tons per month and lead smelters at the rate of 7;0 tons per month. During the entire eighteen years prior to 1919, there were produced in the United States only 47,000 tons of arsenic, which amounts to only 25 per cent. of the present output. The great increased demand has come about through the augmented use of arsenates as insecticides and arsenates as weed killers. In an extract from "Mineral Resources of the United States" on "Arsenic in 1922," Messrs. Heikes and Loughlin say, "The minimum possible demand for arsenic in 1923 was estimated at the end of 1922 to be about 13,000 tons, including 2000 tons for plate glass manufacturers, 3000 tons for lead arsenate, 3500 tons for calcium arsenate, 1500 tons for weed killers, 1200 tons for Paris green, 1000 tons for sheep dips and 750 tons for proprietary mixtures. More recent information, however, indicates twice as great a demand for calcium arsenate." The latter has found great use in the last three or four years as a weapon to combat the boll weevil pest of the southern cotton belt. ~t the present writing refined white arsenic is being quoted on the New York market at from 13)d c. to 1455 c. per Ib., while the average price during the eighteen-year period just mentioned was 4.8 c.

Jan 1, 1924

By J Garritsen, P F. Wells, M Xu

IncoÆs Clarabelle mill currently processes ores from eight mines in the Sudbury basin area in Ontario, Canada. The ore from the Garson mine contains a much higher concentration of arsenic than the other ores. Adding this ore into the feed to the mill has resulted in an increase in arsenic content of the Cu-Ni bulk concentrate to a level that significantly affects the smelter operation, and more importantly the efficiency of Cu-Ni separation in the Matte separation plant. The arsenic occurs mainly as gersdorffite (NiAsS), with a small amount being in the form of cobaltite (CoAsS). Extensive laboratory tests on depressing arsenic in Garson ore flotation have been conducted and two reagent suites have been identified as effective arsenic depressants. One is the so called MAA depressant which is a mixture of magnesium chloride, ammonium chloride, and ammonium hydroxide. This reagent combination was reported to depress other arsenide minerals such as arsenopyrite (FeAsS) and enargite (Cu3AsS4). However, in this study for the first time it has been shown to have a depressing effect on gersdorffite. The other reagent suite, a mixture of triethylenetetramine (TETA) and sodium sulfite, that has been reported as an effective pyrrhotite (Fe1-xS) depressant in pentlandite ((NiFe)9S8) flotation, has not been reported as gersdorffite depressant before. The effectiveness of both reagent suites is more pronounced when the arsenic minerals are oxidised through pulp aeration or the addition of hydrogen peroxide. With a flow sheet consisting of a magnetic separation, rougher- scavenger flotation, followed by regrinding and cleaning of combined magnetic and scavenger concentrate, the arsenic recovery to the final Cu-Ni bulk concentrate was reduced from 73 per cent in baseline test to less than 30 per cent with either reagent suite at no decrease in nickel recovery. The TETA/sulfite reagent combination has the advantage over the MAA suite in that pyrrhotite is also depressed, rather than being activated, and the copper and nickel concentrate grades are therefore increased.

Jan 1, 2005

By Henk Dijkman, Wageningen University, Paula Gonzalez Contreras, Irene Sánchez-Andrea, Jan Weijma, Silvia Vega

"More than 20 years ago, Paques B.V. introduced innovative biotechnologies to recover metals and to remove sulfate from aqueous streams. These technologies find their origin in the exploration of microorganisms involved in the global sulfur cycle. Currently, several sulfur cycle biotechnologies are applied successfully at full-scale. The sulfur cycle is closely linked with the iron cycle, and also the latter offers opportunities for application of innovative biotechnology for the mining industry. Microorganisms of the natural iron cycle carry out reactions that are not feasible by chemical methods such as ferrous iron oxidation with oxygen at pH below 4. Iron oxidation with oxygen can be conducted using microorganisms living at pH between 0.5 and 7 and at temperatures between 0 and 95ºC. Remarkably these microorganisms can also carry out arsenite oxidation at similar acidic conditions and high temperatures. Making use of the extreme features of these microorganisms, Paques and Wageningen University have developed a biological process to precipitate arsenic as scorodite. This biological formation of scorodite is a novel combination of biological oxidation and biocrystallization. Depending on the level of saturation, biological oxidation rates and operational conditions, we could control the formation of the iron precipitates such as jarosite and scorodite. Currently new microorganisms have been harvested from hot springs and rock acid mine drainage to foster the growth of specialized microbial communities with potential high iron and arsenic oxidation capacities and higher resistance to other metals. In our paper we address the ongoing research and development of the bioscorodite process.THE USE OF IRON TO REMOVE ARSENIC In 2015 several environmental disasters related to the release of mine wastewater and tailings occurred. On August 5th, a waste water spill occurred from the Gold King Mine near Silverton, Colorado. A dam holding the tailing pond was damaged and spilled three million US gallons (11 ML) of mine wastewater and tailings, including elements such as cadmium, lead and arsenic, into Cement Creek, a tributary of the Animas River in Colorado. “At their peak, arsenic levels were 300 times the normal level and lead was 3,500 times the normal level” (The Guardian, 2015). In early November, another collapse of a mining dam in the Brazilian state of Minas Gerais spilled between ten and sixteen thousand US gallons of water and sediment after a dam failed from an iron ore mine. Arsenic and mercury polluted the Doce River, arsenic levels were found more than ten times above the legal limit in some places of the river (The Guardian, 2015). Waste production is inevitable during Mining. However, a preventive waste management strategy could have minimised waste production, maximised waste reuse and classified waste by their hazardous degree."

Jan 1, 2016

By José R. Parga

In some parts of the Comarca Lagunera with population of about 2.5 million people, situated in the central part of northern México, chronic arsenic poisoning is endemic and severe adverse effects attributed to As exposure have been reported. Lifetime exposure to arsenic will develop classical symptoms of arsenic poisoning such as skin pigmentation changes, gastrointestinal disturbances and neurological changes. There are several methods available for removal of arsenic from well water in large conventional treatment plants, however a very promising electrochemical treatment technique that does not require the addition of chemicals or regeneration is Electrocoagulation (EC). The EC operating conditions are highly dependent on the chemistry of the aqueous medium, especially conductivity and pH. In this study, Powder X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Transmission Mössbauer Spectroscopy (TMS) were used to characterize the solid products formed at iron electrodes during the EC process. This study will provide an introduction to the fundamental concepts of the EC method. Finally the results of this study suggest that the presence of maghemite and magnetite particles can be used to remove arsenic (III) and arsenic (V). In the field pilot plant scale study more than 99% removal of As species from groundwater is achieved.

Jan 1, 2005

By R. G. Rosehart, S. Y. Lee

"The current investigation concerns the removal of arsenic from waste waters using ion-exchange resin and activated carbon as sorption media. Use of certain weak and strong base anion exchange resins permits the removal of arsenic. Arsenic may be loaded on the weak base resin in the pH range of 2 to 3 and on the strong base resin above pH 5. The elution of arsenic is successfully achieved using 0.5 M NaCl or a mixture of NaCl and NaOH. The activated carbon investigated was less effective on loading arsenic, but the arsenic loaded was easily eluted by simple pH adjustments."

Jan 1, 1972

By Jun Wang, Bo Zhang, Wenqing Qin, Guanzhou Qiu, Xiaozhen Ma, Key Lab of Biohydrometallurgy of Ministry of Education, Fen Jiao, Central South University, Yansheng Zhang

"Arsenic contained in minerals sulphides such as enargite and tennantite can represent not only a significant penalty element in base metals production, but also a disadvantage to the environment through producing the toxic emissions to the atmosphere. The achieving separation of arsenic bearing minerals either at an early stage in floatation or from the floatation concentration is significantly beneficial to the economic. However, there was no feasible commercial method of separation at the flotation stage because of its similar flotation properties with many other copper sulphides. In this work, the selective floatation of enargite from copper sulphide concentrate containing maily covllite, chalcoctie, bornite and enargite was investigated. A low arsenic concentrate with As 0.2%, Cu 22% and a high arsenic bulk concentrate with As 7.65%,Cu 33.65% were obtained. It was indicated that Ca(ClO)2 is the effective depressor and the optimum floatation condition was obtained. Most enargite could be floated at pH 11 and controlling the pulp potential at 290 mV SHE. Furthermore, the arsenic removal from the high arsenic bulk concentrate by hydrometallurgy methods was study. The results showed that the reaction temperature and the concentrations of NaOH were the most important variables affecting the rate of arsenic removal. A low arsenic concentrate with As 0.24%, Cu 37.80% was obtained in the optimum leaching condition.INTRODUCTIONArsenic is mainly produced as a by-product of base metals smelting, in particular copper concentrate. China has imposed an upper limit of 0.50% arsenic for concentrates entering (Long et al., 2012). Arsenic amount of copper concentrate within 0.40% has also been imposed in China, and above which will be introduced about 50 RMB penalties per ton for each 0.10% increasing by smelters now. Therefore, it is necessary to remove arsenic from the copper concentrate.In copper concentrate, arsenic is mainly in the form of arsenopyrite (FeAsS), enargite (Cu3AsS4) or tennantite (Cu12As4S13). There are two types of arsenic in the separation of copper and arsenic: arsenopyrite and arsenic bearing copper mineral. It is easier to separate arsenopyrite from the copper sulphide by flotation in comparsion with the separation of enargite or tennantite from non-arsenic copper minerals (Pineda et al., 2015). The main difficulty in the separation of arsenic copper mineral from non-arsenic copper sulphides is their extremely similar floatability, which depends on the fact that tennantite and enargite contain high copper content (Pineda et al., 2015)."

Jan 1, 2016

By J. Pérez

A lead smelter slag with high copper, lead, arsenic and silver contents was treated at laboratory scale for arsenic removal. The slag was first leached at atmospberic pressure with sulfuric acid and oxygen. According to arsenic contents leaching of most of the arsenic was achieved in either one or two stages, producing a lead-silver rich residue and a solution high in copper and arsenic concentrations. Alternative routes were considered to treat the resulting solution. Firstly, solvent extraction of arsenic with a mixture of TBP and 2-etbyl-bexanol was tested and extractions of over 95 percent of arsenic were achieved. Secondly, a copper arsenate precipitation treatment was done to eliminate arsenic and copper from solution.

Jan 1, 1996

Roasting treatments were investigated to remove arsenic from a nickel concentrate. The main arsenic minerals and their proportions in the concentrate were niccolite (NiAs)-50%, gersdorffite (NiAsS)-40% and arsenopyrite (FeAsS)-10%. Thermal analysis showed that gersdorffite and niccolite began decomposing when heated above 640 and 830°C respectively. The maximum roasting temperature was limited by agglomeration of the concentrate above 900°C. A small vibrated bed reactor was used to investigate the effects of temperature and gas flowrate, the latter to sweep away evolved arsenic. At 900°C, 24% of the original arsenic remained in the concentrate. SEM examination of the calcine showed that the residual arsenic was associated with the calcium in the gangue minerals. Additions of sulphur (either as elemental sulphur or from pyrite) facilitated the decomposition of the arsenic-containing minerals, decreased reaction with calcium in the gangue and produced calcine containing 4-6% of the original arsenic. Treatment with chlorine during roasting was effective in reducing the arsenic content to similar levels. Generation of chlorine in the bed by sulphation of CaC12 also produced encouraging results. Arsenic, Nickel Concentrate, Roasting, Chlorine, Sulphur, Gersdorffite, Niccolite

Jan 1, 2005

By Zhihong Liu

In recent years, the removal of arsenic from different types of high arsenic containing materials produced in nonferrous metallurgical processes have been experimentally studied in the complex materials processing research group from Central South University. These materials include arsenic and antimony bearing flue dust, arsenic sulfide residue and arsenate bearing flue dust. The separation of arsenic from other valuable metals was carried out hydrometallurgically; for each type of arsenic bearing material, different processes have been employed individually to remove the arsenic effectively. In this paper, the flowsheets and typical experimental results have been summarized.

By Armstrong RW, Middlin B

The development, design, construction and operation of the new Solvent Extraction/BCA process plant at Copper Refineries Pty. Ltd., Townsville is described.The process offers substantial savings in electrical power costs, improvements in plant hygiene, and a lowering of materials handling costs compared with conventional electrowinning technology.The solvent extraction process extracts arsenic from copper Tank House electrolyte using a tributyl phosphate (TBP) - kerosene solvent. The plant incorporates fourextraction stages, two scrub stages, and three stripping stages to produce an arsenic-bearing low-acid strip liquor. This strip liquor is mixed with copper sulphate, and neutralized with ammonia to form a copper (II) arsenic (V) crystalline product, bicupric arsenate (BCA). This product is then used in the manufacture of chromated copper arsenate timber preservatives (Royston 1982).

Jan 1, 1985

By A. E. Isaacson, T. H. Jeffers

The U.S. Bureau of Mines (USBM) is investigating arsenic removal from dilute waters using a biological precipitation/chemical adsorption system. The method includes (1) inoculating water with ferrous salts to increase hydrogen sulfide generation by indigenous sulfate-reducing bacteria, (2) utilizing the hydrogen sulfide to precipitate the bulk of the arsenic as arsenic sulfide, and (3) using beads containing ferric oxyhydroxide to remove the remaining arsenic. This approach was applied to a contaminated water containing 13 mg/L As. Arsenic extractions up to 99% were achieved. The use of sulfate-reducing bacteria is particularly warranted in this situation since most of the required nutrients are present in the water. Based on successful initial efforts, planning is underway to conduct a pilot-scale test at the site.

Jan 1, 1995

By A. D. Davis, D. J. Dixon, J. L. Sorenson, C. J. Webb, S. Dawadi

Limestone-based material appears to be an effective arsenic removal process that has great potential for source reduction in drinking water. Limestone-based material offers several benefits to the drinking water community: 1) reasonable removal efficiency as compared to material cost, 2) broad geographic and water system applicability, 3) compatibility with other water treatment processes, 4) ease of technical use, and 5) low-cost disposal in ordinary landfills. Batch and column experiments have evaluated the removal efficiency of several limestone types. Additives and material alteration have increased the removal efficiency. Granulation of powdered limestone as a filter media currently is being investigated.

Jan 1, 2006

By T. Fujita

A high-grade fluorite ore is converted into hydrogen fluoride to produce many kinds of materials containing fluorine. Recently, it is becoming necessary to use low-grade fluorite ore due to the depletion of high grade ore. The low-grade fluorites usually have impurities such as SiO2, P, CaCO3 and arsenic. The most impurities such as SiO2, CaCO3 and P can be removed by using flotation method. However, the removal of arsenic is difficult, and the arsenic contamination decreases the hydrogen fluoride production percentage. The novel technologies for processing low-grade fluorite ore are urgently needed, in order to lower the arsenic concentration to less than 100 mg/kg. In this study, the removal of arsenic from low-grade fluorite ore has been investigated by means of an autogenous grinding using tower mill in sulfuric acid aqueous solution and 0.3 mm zirconia balls in water. The nano grinding in water can prevent the dissolution of 0.3 mm size zirconia balls as grinding media by sulfuric acid solution. Experimental results showed that the arsenic concentration was reduced from 260 mg/kg to 90 mg/kg and CaF2 recovery reached 90% by this process.

Sep 1, 2012

By Kazuteru Tozawa, Robert G. Robins

"The stability of calcium arsenate is discussed in relation to the possible misuse of lime in the treatment of gold processing waste waters. Stability diagrams have been derived and experimental results cited to show that calcium arsenate has a higher solubility in neutral to alkaline solution than has previously been recognized and this solubility is further enhanced by the presence of carbon dioxide, bicarbonate or carbonate.IntroductionThe removal of arsenic from gold mine waste waters has been of interest for more than thirty years, but with the recent emphasis on clean water standards there has been renewed activity in relation to that problem. The processing of gold-bearing sulphides which contain arsenopyrite and other complex arsenic sulphides is well established. Initial roasting to oxidize the sulphides leaves the arsenic in the form of both arsenic and arsenic, in which forms it is soluble in the subsequent leaching stage. Further oxidation of the leach liquors is required before the well-established procedure of precipitating calcium arsenate with lime, which is carried out despite an immense lack of knowledge of the calcium-arsenic-water system.The solubility product and free energy of formation for Ca3(AsO4)2, which are to be found in recent and reliable sources of data, originate from the work of Chukhlansev, whose experimental determination of the concentration of calcium from the solubility of calcium arsenate in solutions of various pH yields the results plotted in Figure 1. This is the work which has resulted in a wide acceptance of the ""insolubility"" of calcium arsenate and the use of lime to stabilize arsenic in that form.Laguitton attempted to further elucidate the chemistry of the lime addition method for treating arsenical waste waters from gold processing operations. The low solubility product for Ca3(AsO4)2 was the basis for his examination of likely chemical equilibria in the system. Laguitton and other workers have not considered atmospheric carbon dioxide as an important component in this system."

Jan 1, 1982

By D. Laguitton

The basic chemistry of a1•senic related to its dissolution and subsequent precipitation in gold-mine waste waters is discussed. The lime addition methods provides the most economic treatment of arsenical slurries, but requires a careful control of the oxidation of Asm into Asv, of the pH (>12) and the filtration of the precipitate. If arsenic levels below 0.5 mg/ l are required, a modification of the method by phosphate addition must be considered.

Jan 1, 1976

Datun Concentrator currently processes complex sulfide ores in Gejiu Municipality, Yunnan Province, China. The ore contains much higher arsenic than other ores. The run of mine ore is fed to the concentrator to recover copper and tin by bulk flotation and gravity concentration, and then the other sulphides, such as pyrite, arsenopyrite, etc. didn?t get utilized and are discarded as tailings due to the high arsenic content. In order to utilize the pyrites in the tailings, a series of tests have been conducted for finding the solution of arsenic removal from high arsenic-bearing pyrite concentrates through simple flotation process. By means of orthogonal experimental design, the optimized levels and main factors have been found out for the roughing stage. Through selection of the effective in-organic depressants for the arsenic-bearing minerals, the arsenic in the pyrite concentrate can be removed to meet the requirement of sulfuric acid plant (As%=0.5%) by the open flotation process, i.e., one-time roughing and two-time cleaning.

Jan 1, 2014

By Larry G. Twidwell

The removal of dissolved arsenic from mine waste waters utilizing a lime/phosphate precipitation technique has been studied on a laboratory scale at Montana Tech of The University of Montana and on a pilot scale at MSE Technology Applications as a wastewater treatment process potentially capable of removing dissolved arsenic to <50 µg/L. Arsenic bearing lime and lime/phosphate slurries were subjected to laboratory extended-time air-sparged aging for over four years. The lime slurries released their arsenic back into solution in a relatively short period of time, whereas the lime/phosphate slurries showed limited release of arsenic. The developed process has been pilot scale tested by MSE-TA for the EPA Mine Waste Technology Program on three waters, ASARCO smelter blowdown water, ASARCO thickener overflow water, and Mineral Hill Mine groundwater. The laboratory study results will be presented and discussed in this presentation. The pilot scale results will be presented and discussed in a companion presentation. Stability, Aging, Apatite, Johnbaumite

Jan 1, 2005

By C. M. Acuña

At the Chuquicamata Division of Codelco-Chile high arsenic concentrates are produced, which at the smelter are processed via the Outokumpu Flash Furnace and Teniente Converters to obtain copper mattes. In the case of the Teniente Converters the production of matte grade near white metal composition is a common practice since the eighties and provided in the pyrometallurgical route no appropiate measures are taken, penalties have to be paid because of arsenic content in the anodes. During smelting huge volume of slag is produced and elimination of arsenic by slagging at this step is not economically attractive. Although during fire refining is possible to eliminate arsenic by use of mixtures of calcium and sodium carbonates this alternative is expensive, takes long process time and decreases the lifetime of the refractory lining. In spite of these facts a reasonably way to control arsenic in metal, and therefore in the anode, is taking, action in the converting step. The effects of oxygen and arsenic content in metal, arsenic in white metal and basicity index of the slag upon the distribution coefficient of arsenic between metal and slag were investigated at pilot and industrial levels. The best results are obtained for metals around 7,000 ppm oxygen and 0.3 basicity index slag, which results in a 5.7 distribution coefficient for a 5,800 - 7,100 ppm arsenic content in white metal, 18%-24% CaO slag at 1473 - 1523K. Furthermore, no significant/visible refractory wear has been realized.

Jan 1, 1999

By K. Mayhew, R. Bruce, A. Heidel, G. P. Demopoulos

"Teck and Aurubis are working together to commercialize a technology for the processing of copper arsenic sulphide concentrates that is economic and sustainable with regards to the environment and community. The pressure hydrometallurgical approach is a desirable option as mineral extraction and arsenic fixation can take place in a single autoclave vessel. A test work program was carried out where a range of copper concentrates with varying arsenic grades was processed under CESL leach conditions. This paper discusses the stability character (in terms of arsenic) of the resulting residues and their mineralogy. The basic ferric arsenate sulphate phase (BFAS; otherwise known as type 2) was identified as the main arsenic carrier. All CESL residues demonstrated high stability (<1 mg/L As) through a range of aggressive (pH and ORP) environmental leach conditions.INTRODUCTIONArsenic deportment and control in the copper industry needs an integrated approach involving each stage of the value chain, i.e. exploration, mine operation, refining process and mine closure. Teck Resources Limited (Teck), Canada’s largest diversified mining company and Aurubis, Europe’s largest copper producer, have formed a partnership to advance the application of CESL copper-gold technology for the development of high arsenic bearing copper resources (Bruce et al., 2011).Among the options for arsenic control in the metallurgical treatment of copper concentrates is the precipitation of ferric arsenate, which is widely accepted as the most suitable method for stabilizing arsenic (Ferron and Wang, 2003). The pressure hydrometallurgical approach to processing arsenic bearing copper concentrates is a favorable option as mineral extraction and arsenic fixation can take place in a single autoclave vessel. Under CESL pressure leaching conditions (150 °C, 1380 kPa) high copper extraction and arsenic (V) fixation is possible.Within the pressure leach autoclave, arsenate and ferric iron react to form scorodite type phases. The precipitate formed under CESL conditions is dependent on the Fe (III) /As (V) ratio and the tenor of cations and anions, particularly excess sulphate (Gomez et al., 2011a). Previous studies on CESL residues have found arsenic to be present as crystalline scorodite (FeAsO4.2H2O) (Bruce et al., 2011), basic ferric arsenate sulphate (BFAS: Fe(AsO4)1-x(SO4)x(OH)x·(1-x)H2O, where 0.3<x<0.7), and/or arsenate adsorbed on to hematite (Gomez et al. 2011b). Although not a focus of previous work, scorodite was the predominant precipitate formed when the concentrate Fe/As was <1.5 (Mayhew et al., 2010), and BFAS was the predominant precipitate when the concentrate Fe/As was >10 (Gomez et al. 2011b)."

Jan 1, 2012

By R. N. Tempel, M. Lengke

Arsenic sulfide (orpiment, realgar, amorphous AsS and As2S3) oxidation rates were measured in mixed flow reactors at pH-2 and at temperatures of 25 ° to 30 °C. The measured oxidation rates for arsenic sulfide solids by dissolved oxygen are in the range of 10-11 to 10-10 mole m-2s-1 after being normalized to final surface area. The order of arsenic sulfide oxidation rates decreases at pH-2 from amorphous AsS > realgar > orpiment > amorphous As2S3. Compared to pyrite, arsenic sulfide oxidation rates are approximately 1.5 to 15 times slower than pyrite oxidation rates at pH-2.

Jan 1, 2003