An experimental study on metal precipitation driven by fluid mixing: implications for genesis of carbonate-hosted lead–zinc ore deposits

A type of carbonate-hosted lead–zinc(Pb–Zn)ore deposits, known as Mississippi Valley Type(MVT)deposits, constitutes an important category of lead–zinc ore deposits. Previous studies proposed a fluid-mixing model to account for metal precipitation mechanism of the MVT ore deposits, in which fluids with metal-chloride complexes happen to mix with fluids with reduced sulfur, producing metal sulfide deposition. In this hypothesis, however, the detailed chemical kinetic process of mixing reactions, and especially the controlling factors on the metal precipitation are not yet clearly stated. In this paper, a series of mixing experiments under ambient temperature and pressure conditions were conducted to simulate the fluid mixing process, by titrating the metal-chloride solutions, doping withor without dolomite, and using NaHS solution. Experimental results, combined with the thermodynamic calculations, suggest that H_2S, rather than HS^-or S^(2-),dominated the reactions of Pb and/or Zn precipitation during the fluid mixing process, in which metal precipitation was influenced by the stability of metal complexes and the pH. Given the constant concentrations of metal and total S in fluids, the pH was a primary factor controlling the Pb and/or Zn metal precipitation. This is because neutralizing or neutralized processes for the ore-forming fluids can cause instabilities of Pb and/or Zn chloride complexes and re-distribution of sulfur species, and thus can facilitate the hydrolysis of Pb and Zn ions and precipitation of sulfides. Therefore, a weakly acidic to neutral fluid environment is most favorable for the precipitation of Pb and Zn sulfides associated with the carbonate-hosted Pb–Zn deposits.

Isotopic Compositions of Sulfur in the Jinshachang Lead–Zinc Deposit, Yunnan, China, and its Implication on the Formation of Sulfur-Bearing Minerals

The Jinshachang lead-zinc deposit is mainly hosted in the Upper Neoproterozoic carbonate rocks of the Dengying Group and located in the Sichuan-Yunnan-Guizhou （SYG） Pb-Zn-Ag multi- metal mineralization area in China. Sulfides minerals including sphalerite, galena and pyrite postdate or coprecipitate with gangue mainly consisting of fluorite, quartz, and barite, making this deposit distinct from most lead-zinc deposits in the SYG. This deposit is controlled by tectonic structures, and most mineralization is located along or near faults zones. Emeishan basalts near the ore district might have contributed to the formation of orebodies. The j34S values of sphalerite, galena, pyrite and barite were estimated to be 3.6‰-13.4‰, 3.7‰-9.0‰, -6.4‰ to 29.2‰ and 32.1‰34.7‰, respectively. In view of the similar δ34S values of barite and sulfates being from the Cambrian strata, the sulfur of barite was likely derived from the Cambrian strata. The homogenization temperatures （T ≈ 134--383℃） of fluid inclusions were not suitable for reducing bacteria, therefore, the bacterial sulfate reduction could not have been an efficient path to generate reduced sulfur in this district. Although thermochemical sulfate reduction process had contributed to the production of reduced sulfur, it was not the main mechanism. Considering other aspects, it can be suggested that sulfur of sulfides should have been derived from magmatic activities. The δ34S values of sphalerite were found to be higher than those of coexisting galena. The equilibrium temperatures calculated by using the sulfur isotopic composition of mineral pairs matched well with the homogenization temperature of fluid inclusions, suggesting that the sulfur isotopic composition in ore-forming fluids had reached a partial equilibrium.

Sulphidization flotation for recovery of lead and zinc from oxide-sulfide ores

A new flowsheet was developed to recover the valuable minerals from oxide or oxide-sulfide ores of lead and zinc. The flowsheet consisted of flotation of sulfide minerals, desliming and sulphidization-flotation of oxide minerals. The corresponding reagent system and techniques to the flowsheet were investigated. Batch and continuous tests show that the dosage of sodium sulfide, temperature, and collector type are main affecting factors on the recovery of smithsonite and cerussite. For the flotation of cerussite, there is an appropriate dosage of sodium sulfide at which the recovery reaches its maximum value. The required sodium sulfide for smithsonite flotation is higher than that for cerussite and the recovery of smithsonite flotation increases with the dosage of sodium sulfide at low level and becomes insensitive at high dosage. The appropriate temperature for smithsonite and cerussite flotation is found to be 2540℃. Amines are found to be the effective collectors for the flotation of smithsonite after sulphidization. Investigation also shows that desliming prior to sulphidization-flotation is essential to the effective recovery of smithsonite and cerussite, and the desliming process of two-stage hydrocyclon is well feasible and effective for the treatment of lead-zinc oxide ores. A further treatment on the cerussite flotation concentrate by shaking table is proposed to obtain higher lead grade.

Separation of sulfide lead-zinc-silver ore under low alkalinity condition

A complex lead-zinc-silver sulfide ore containing 2.98% Pb, 6.49% Zn and 116.32×10-4% Ag (mass fraction) from Yunnan Province, China, was subjected to this work. Research on mineral processing was conducted according to the properties of the lead-zinc-silver ore. Under low alkalinity condition, the lead minerals are successfully separated from the zinc minerals with new reagent YZN as zinc depressant, new reagent BPB as lead collector, CuSO4 as zinc activator and ethyl xanthate as zinc collector. The associated silver is mostly concentrated to the lead concentrate. With the process utilized in this work, a lead concentrate of 51.90% Pb with a recovery of 82.34% and a zinc concentrate of 56.96% Zn with a recovery of 81.98% are produced. The silver recovery in the lead concentrate is 80.61%. Interactions of flotation reagents with minerals were investigated, of which the results indicate that the presence of proper amount of Na2S can precipitate Pb2+ and has a sulfidation on oxidized lead minerals. The results also show that Na2CO3 and YZN used together as combined depressants for sphalerite can signally improve the depressing effect of new reagent YZN on sphalerite.

Heavy metal concentrations in soils and plants in the vicinity of Arufu lead-zinc mine, Middle Benue Trough, Nigeria

This study focused on the influence of base metal mining on heavy metal levels in soils and plants in the vicinity of Arufu lead-zinc mine, Nigeria. Soil samples (0-15 cm depth) and plant samples were collected from cul-tivated farmlands in and around the mine, the unmineralized site and a nearby forest (the control site). The samples were analyzed for heavy metals (Fe, Zn, Mn, Cu, Pb, Cr and Cd) by Atomic Absorption Spectrophotometry (AAS). The physical properties of soils (pH and LOI) were also measured. Results showed that soils from cultivated farm-lands have neutral pH values (6.5-7.5), and low organic matter contents (<10%). Levels of Zn, Pb and Cd in culti-vated soils were higher than the concentrations obtained from the control site. These heavy metals are most probably sourced from mining and agricultural activities in the study area. Heavy metal concentrations measured in plant parts decreased in the order of rice leaves>cassava tubers>peelings. In the same plant species, metal levels decreased in the order of Zn>Fe>Mn>Cu>Pb>Cr>Cd. Most heavy metals were found in plant parts at average concentrations normally observed in plants grown in uncontaminated soil, however, elevated concentrations of Pb and Cd were found in a few cassava samples close to the mine dump. A stepwise linear regression analysis identified soil metal contents, pH and LOI as some of the factors influencing soil-plant metal uptake.

Effects of field application of phosphate fertilizers on the availability and uptake of lead, zinc and cadmium by cabbage (Brassica chinensis L.) in a mining tailing contaminated soil

A field trial was conducted to evaluate the reduction of bioavailability of heavy metals including lead (Pb), zinc (Zn) and cadmium (Cd) in a soil contaminated by mining tailings in Shaoxing, Zhejiang, China. Three commercial phosphate (P) fertilizers including phosphate rock (PR), calcium magnesium phosphate (CMP), and single superphosphate (SSP) were applied to the plot at three P application rates, 50, 300, and 500 g/m2 with 9 treatments and control (CK). Plants, water soluble and exchangeable (WE) extra...

A Preliminary Study on Fluid Inclusions and Mineralization of Xitieshan Sedimentary-Exhalative (SEDEX) Lead-Zinc Deposit

The Xitieshan lead-zinc deposit is located at the northern margin of the Qaidam Basin, Qinghai Province, China, and had developed a complete marine sedimentary-exhalative system. Our preliminary study of ore-forming fluids shows that fluid inclusions in quartz from altered stockwork rocks that represent the pipe facies have a wide range of temperature and salinity. The intense fluid activities are characteristics of the pipe facies of the exhalative system. Fluid inclusions in carbonates near the unstratified ore bodies hosted in the thick-bedded marble which represents vent-proximal facies are large in size and have moderate to high temperatures. They represent unerupted sub-seafloor fluid activity. Fluids in altered stockwork rocks and carbonates have similar H20-NaCI-CO2 system, both belonging to the sedimentary-exhalative system. The fluids migrate from the pipe facies to the unstratified ore bodies. Boiling of the fluids causes the separation of CO2 vapor and liquid H2O. When the fluids migrate into the unconsolidated thick-bedded marble, the escape of CO2, decreasing temperature and pressure as well as some involvement of seawater into the fluids result in the unmixing of fluids with high and low salinity and deposition of ore-forming materials. The two unmixed fluids were trapped in unconsolidated carbonates and the ore-forming materials were deposited in the unconsolidated carbonates to form the sedimentary-exhalative type unstratified ore bodies. The oreforming temperature of unstratified ore bodies is up to high temperature indicating that there is a huge ore-forming potential in its deep.

Sulfidation roasting of lead and zinc carbonate with sulphur by temperature gradient method

In order to enhance the lead and zinc recovery from the refractory Pb-Zn oxide ore, a new technology was developed based on sulfidation roasting with sulphur by temperature gradient method. The solid-liquid reaction system was established and the sulfidation thermodynamics of lead and zinc carbonate was calculated with the software HSC 5.0. The effects of roasting temperature,molar ratio of sulphur to lead and zinc carbonate and reaction time in the first step roasting, and holding temperature and time in the second roasting on the sulfidation extent were studied at a laboratory-scale. The experimental results show that the sulfidation extents of lead and zinc are 96.50% and 97.29% under the optimal conditions, respectively, and the artificial galena, sphalerite and wurtzite were formed. By the novel sulfidizing process, it is expected that the sulphides can be recovered by conventional flotation technology.

Study on the multi-sources of ore-forming materials and ore-forming fluids in the Huize lead-zinc ore deposit

The Huize large-sized Pb-Zn deposit in Yunnan Province, China, is characterized by favorable metallogenic background and particular geological settings. This suggested that the ore-forming mechanism is relatively unique. On the basis of geological features such as the contents of mineralization elements, the REE concentrations of gangue calcites, the REE concentrations of calcite veins in the NE-trending tectonic zone and the Pb, Sr, C, H and O isotopic compositions of different minerals, this paper presents that the ore-forming materials and ore-forming fluids of the deposit were derived from various types of strata or rocks. This is a very significant conclusion for us to further discuss the mineralization mechanism of the deposit at depth and establish an available genetic model.

REE Geochemistry of the Lead-Zinc Ores from the Jinding Lead-Zinc Deposit, Lanping, Yunnan

Nineteen volcanic and magmatic rock samples were collected from the Jinding lead-zinc deposit and its surrounding areas in Yunnan. The ICP and AES analyses, referred to the previous results, show that the metal minerals and altered rocks in the Jinding lead-zinc deposit display a decreasing trend of ΣREE from the early to late stages of mineralization, and similarities in REE distribution patterns, indicating that the ore fluids are characterized by high LREE enrichment, markedly negative δCe anomaly and slight δEu anomaly. These REE distribution patterns exhibit striking similarities to those of the Pliocene trachyte in the study area, both of which are similar in ΣREE, LREE/HREE ratio, δEu and δCe. The ore fluids besides the basin fluids in the deposit are also closely related to those associated with Pliocene trachyte magmas.

Investigation on the deactivation cause of lead-zinc double oxide for the synthesis of diphenyl carbonate by transesterification

The deactivation cause of lead-zinc double oxide for synthesis of diphenyl carbonate （DPC） by transesterification of dimethyl carbonate （DMC） with phenol has been investigated. X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, infrared spectroscopy （IR）, thermogravimetry analysis （TG）, atomic absorption spectroscopy and elementary analysis are employed for the catalyst characterization. The results show that, the formation of Pb4O（OC6H5）6 through the reaction of phenol and lead species in the catalyst leads to the crystal phase change of active component and serious leaching of lead, which is the cause of the catalyst deactivation. In addition, the composition of the leached lead is ascertained to be a mixture of Pb4O（OC6H5）6 and PbO with the weight percentage of 62.7% and 37.3%, respectively.

Metallogeny of the Baiyangping Lead-Zinc Polymetallic Ore Concentration Area, Northern Lanping Basin of Yunnan Province, China

The Lanping Basin in the Nujiang-Lancangjiang-Jinshajiang （the Sanjiang） area of northeastern margin of the Tibetan Plateau is an important part of eastern Tethyan metallogenic domain. This basin hosts a number of large unique sediment-hosted Pb-Zn polymetallic deposits or ore districts, such as the Baiyangping ore concentration area which is one of the representative ore district. The Baiyangping ore concentration area can be divided into the east and west ore belts, which were formed in a folded tectogene of the India-Asia continental coUisional setting and was controlled by a large reverse fault. Field observations reveal that the Mesozoic and Cenozoic sedimentary strata were outcropped in the mining area, and that the orebodies are obviously controlled by faults and hosted in sandstone and carbonate rocks. However, the oreforming elements in the east ore belt are mainly Pb-Zn -Sr-Ag, while Pb-Zn-Ag-Cu-Co elements are dominant in the west ore belt. Comparative analysis of the C-O-Sr-S-Pb isotopic compositions suggest that both ore belts had a homogeneous carbon source, and the carbon in hydrothermal calcite is derived from the dissolution of carbonate rock strata; the ore- forming fluids were originated from formation water and precipitate water, which belonged to basin brine fluid system; sulfur was from organic thermal chemical sulfate reduction and biological sulfate reduction; the metal mineralization material was from sedimentary strata and basement, but the difference of the material source of the basement and the strata and the superimposed mineralization of the west ore belt resulted in the difference of metallogenic elements between the eastern and western metallogenic belts. The Pb-Zn mineralization age of both ore belts was contemporary and formed in the same metaliogenetic event. Both thrust formed at the same time and occurred at the Early Oligocene, which is consistent with the age constrained by field geological relationship.

The mechanisms of paragenesis and separation of silver, lead and zinc in hydrothermal solutions

On the basis of an experimental study and thermodynamic calculation, the mechanisms of paragenesis and separation of silver, lead and zinc in the hydrothermal system have been studied. At acidic to nearly neutral pH, their chloride complexes are stable, and among them the chloride complexes of zinc are most stable. And the sulfide complexes are the dominant species at nearly neutral to alkaline pH, while the sulfide complexes of silver are most stable. With decreasing temperature, , f-{O-2} and increasing pH, the solubilities of silver, lead and zinc will decrease, leading to their deposition and separation. For sulfide complexes, the concentrations of reduced sulfur and pH are two important factors affecting their stabilities. Complexes of different forms and stabilities respond to the variation of conditions to different extents, which gave rise to the paragenesis and separation of silver, lead and zinc in the whole ore-forming process of dissolution, transport and deposition.

Improvement of flotation behavior of Mengzi lead-silver-zinc ore by pulp potential control flotation

The electrochemical behavior of Mengzi lead-silver-zinc ore flotation system was studied. Based on the electrochemical characteristics of sulfide mineral flotation system, a stage potential control flotation was developed with the main parameters of pulp potential(φp), pH value and collector dosage. Using N,N’ diphenylamino-dithiolphosphoric acid(NNDDC) as a collector, which has good selectivity for galena flotation at pH 8.8 and pulp potential 330 mV, DDTC is used as secondary collector to improve both the grade and recovery of Pb and Ag. The pulp potential values significantly influence the floatability of practical minerals and single minerals when using NNDDC as the collector. The flotation recovery of galena reaches 85% at about 0.3 V and pH8.8. With the usage of pulp potential control during grinding and flotation, the new pulp electrochemical technology for Mengzi lead-silver-zinc ore flotation was developed. The results show that the grades of Pb and Ag of galena concentrate are 55% and 1 800 g/t, respectively, while the recoveries of Pb and Ag are 86.5% and 65%, respectively, the grade of Zn of marmatite concentrate is 42.5%, and the recovery of Zn is 91.25%.

Effects of Cadmium, Lead, and Zinc on Size of MicrobialBiomass in Red Soil

A laboratory incubation experiment was conducted to study the influence of cadmium (Cd), lead (Pb)and zinc (Zn) on the size of the microbial biomass in red soil. All the three metals were applied, separately,at five different levels that were: Cd at 5, 15, 30, 60 and 100 μg g-1; Pb at 100, 200, 300, 450 and 600 μg g-1 and Zn at 50, 100, 150, 200 and 250 μg g-1 soil. In comparison to uncontaminated soil, the microbial biomass carbon and biomass nitrogen decreased sharply in soils contaminated with Cd, Ph and Zn. A more considerable increase in the microbial biomass C: N ratio was observed in the metal contaminated soils than the non-treated control. Among the tested metals, Cd displayed the greatest biocidal effect followed by Zn and Pb, showing their relative toxicity in the order of Cd > Zn > Pb.

Study on experiment and mechanism of thermal dissolved sulfuration of low grade lead-zinc oxide ore in lanpin

The thermal dissolved sulfuration technology is brought forward and performed based on the characteristic of low grade lead-zinc oxide ore in lanpin. Using sulfur as the sulphidizing agent in the experiment, the oxides in the sandstone and ignimbrite are changed into sulfides. The disproportionation reaction of sulfur in a solution is confirmed as 4S＋3H2O=2S^2-＋S2O3^2--＋6H^＋. The dynamics process is studied and the first-order reaction rate equation -1n（1-a）=ktt is obtained. The effects of the reactive products, stirring speed, dosage of sulfuration agent, value of pH and sulphidizing temperature on the sulfuration of oxide ore are investigated. The results indicate that the reactive apparent activation energy is 100.8 kJ/mol and the sulfuration ratio of lead-zinc oxide ore reaches 60% under the conditions of pH 5.9-7.5, the sulfuration temperature of 130 ℃, sulfuration time of 180 min and the stirring speed of 800 r/min.

Study on the response of wheat to lead, cadmium and zinc

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Wetting agent investigation for controlling dust of lead-zinc ores

The purpose of this project is to control the pollution of dust,which occurred in a typical lead-zinc mine.Two kinds of surfactants and water glass were chosen as the wetting agents to study the behaviours of suppressing the dust.The performances of the wetting agents of various sizes and water content of dust and their compositions among different weting agents were investigated. Firstly,the chemical compounds,dispersity,water content,bulk density and other relevant physico-chemical properties of the choiced dust of lead-zinc ore were mensurated.A great number of down-ward penetrating tests were conducted to different partical sizes of dust and to analyze the dust wetting behaviour respectively.The optimal compositions of wetting agents were obtained in accordance with different water contents and partical sizes of the dust after analyzing and statisting the achieved experimental data. The data show that the efficiency of chemical dust suppression of weting agents is much better than that of water.The results of the research work prove that the partical size and the water content of the dust are very important factors to the dust suppression.The results are also proved validly by the dropping experiment,which takes the penetrating diameter and penetrating time as the major factors.The superfine dust is much more difficult to be wetted.Since increasing the water content of dust is the best approach to control it,the choice of wetting agents for improving dispensation is significant.

Recycle of Wastewater from Lead-Zinc Sulfide Ore Flo-tation Process by Ozone/BAC Technology

Lead-zinc sulphide ore contains lead sulphide (galena), and zinc sulphide (sphalerite). In the first flotation stage, galena is rendered hydrophobic with an organic collector such as xanthate, while sphalerite is kept from floating by depressants, and in the second flotation stage, activator was used to activated zinc flotation. Since the organic regent used are different in the two flotation stage, wastewater from the second zinc flotation stage can’t be directly recycled to the first lead flotation stage. Wastewater from flotation process for concentrating lead-zinc sulphide ore often containing organic compounds such as diethyldithiocarbamate(DDTC), xanthate, terpenic oil(2# oil) and thionocarbamate esters (Z-200), are environmentally hazardous. Their removal from contaminated water and the reuse of the water is one of the main challenges facing lead-zinc sulphide ore processing plants. In this study, synthetic wastewater containing DDTC, xanthate, 2# oil and Z-200 at concentrations ranging from 21 to 42 mg/L was fed into an Ozone/Biological activated carbon (BAC) reactor. Analyses of the effluent indicated a chemical oxygen demand (COD) removal over 86.21% and Total organic carbon (TOC) removal over 90.00% were achieved under Hydraulic retention time (HRT) of 4h and O3 feeding concentration of 33.3mg/L. The effluent was further recycled to the lab scale lead concentrating process and no significant difference was found in compare with fresh water. Furthermore, lead-zinc sulphide mineral concentrating process was carried out at lab scale. The produced wastewater was treated by Ozone/BAC reactor at O3 feeding concentration of 16.7mg/L and HRT of 4h. The effluent analysis showed that TOC removal was 74.58%. This effluent was recycled to the lab scale lead-zinc sulphide mineral concentrating process and the recovery of lead was not affected. The results showed that by using Ozone/BAC technology, the lead-zinc sulphide mineral processing wastewater could be recycled.