A new approach to precious metals recovery from brown coals: Correlation of recovery efficacy with the mechanism of metal-humic interactions

The presence of gold and platinum group elements (PGE) in low-rank brown coals around the world has promoted interest in the industrial exploitation of this alternative source of precious metals. However, due to low efficacy of the methods traditionally used for the processing of mineral ores, there exists a high demand for new strategies of precious metal recovery from refractory carbonaceous materials that could significantly increase the economic potential of gold- and PGE-bearing organic resources. Here we discuss the possibility of gold and PGE recovery from alkaline extracts of brown coals using the difference in colloidal stability of bulk organic matter and its fractions enriched with precious metals. This approach enables one to avoid complete oxidation or combustion of brown coals prior to gold recovery, to minimize organic content in gold concentrate, and to obtain a valuable by-product - humic extracts. Using gold-bearing brown coals from several deposits located in the South Far East of Russia, we show that up to 95% of gold can be transferred to alkaline extracts of humic acids (HA) and up to 85% of this gold can be recovered by centrifugation at pH 4.0-6.0, when only 5-15% of HA precipitated simultaneously. We have shown that the high efficacy of gold recovery can be attributed to the occurrence of fine-dispersed elemental gold particles stabilized by HA, which differ significantly in colloidal stability from the bulk organic matter and, thus, can be separated by centrifugation.     

Anomalous gold contents in brown coals and peat in the south-eastern region of the Western-Siberian platform

One hundred twenty-two samples of Jurassic and Paleogene brown coals and 1254 peat samples from the south-eastern region of the Western-Siberian platform were analyzed for gold by the neutron-activation method. Mean content of Au in Jurassic coals is 30 ± 8 ppb, in Paleogene coals is 10.6 ± 4.8 ppb, and in peat is 6 ± 1.4 ppb. Concentrations of gold as high as 4.4 ppm were found in coal ash and 0.48 ppm in the peat ash. Coal beds with anomalous gold contents were found at Western-Siberian platform for the first time.Negative correlation between gold and ash yield in coals and peat and highest gold concentrations were found in low-ash and ultra-low-ash coals and peat. Primarily this is due to gold's association with organic matter.For the investigation of mode of occurrence of Au in peat the bitumen, water-soluble and high-hydrolyzed substances, humic acids, cellulose and lignin were extracted from it. It was determined that in peat about 95% of gold is combined with organic matter. Forty to sixty percent of Au is contained in humic acids and the same content is in lignin. Bitumens, water-soluble and high-hydrolyzed substances contain no more than 1% of general gold quantity in peat.The conditions of accumulation of high gold concentrations were considered. The authors suggest that Au accumulation in peat and brown coals and the connection between anomalous gold concentrations and organic matter in low-ash coals and peat can explain a biogenic–sorption mechanism of Au accumulation. The sources of formation of Au high concentration were various Au–Sb, Au–Ag Au–As–Sb deposits that are abundant in the Southern and South-Eastern peripheries of the coal basin.     

土壤腐殖物质特征及其对有机碳长时间尺度稳定性的指示：以陕西洛川黄土剖面为例

在长时间尺度上研究土壤中腐殖物质的组成和腐殖化特征对于正确评价土壤有机质的稳定性具有重要意义。文中对洛川黄土/古土壤剖面S8以上的17个黄土和古土壤样品中的胡敏酸（HA）、富里酸（FA）和胡敏素（HM）进行定量研究,并对HA和FA的E465、E665值等进行了测定。结合该课题组对矿物组成、总有机碳（TOC）及其各组分含...     

First finds of native palladium,platinum, gold,and silver in brown coals of the Erkovets field (upper Amur region)

Minerals of native elements (Pd, Pt, Au, Ag, and Au-Ag solid solutions) as well as Pb, Zn, Cu, Bi, Fe, Cr, Ni, W, Al, and their intermetallides, and a number of other ore minerals were discovered in brown coals of the Erkovets field. The structural reorganization of the noble metal grains and most of the other minerals found in the brown coals suggest their authigenic paragenesis. The input of noble metals in brown coals is possible in an ionic mode from the surface and underground waters as mineral particles transported by wind from goldfields.     

Thermal analysis (TG–DTA) and isotopic characterization (13C–15N) of humic acids from different origins

Thermal analyses (TG–DTA), elemental composition and isotope analyses (¹³C and ¹⁵N) were performed on humic acids (HA) from peats, leonardites and lignites, in order to investigate their structure and the changes taking place during the humification process. Thermal analyses showed structural differences between HA samples in relation to their coalification rank. In particular the lignite HA were characterized by a more stable chemical composition at high temperatures.The δ¹³C and δ¹⁵N values can provide information on the biogeochemical processes involved in HA formation. In particular, peat HA were linked to anoxic environments that enable plant residues to persist in their structure. In contrast, leonardite and lignite HA formation seems to be governed by different biogeochemical processes from those responsible for peat diagenesis. However, the isotopic analyses did not provide any distinction between leonardite and lignite HA. On the basis of the data presented in this study, it may be concluded that TG–DTA and isotope ratio measurements are powerful tools for investigating the formation pathway of humic substances from coals.     

Germanium speciation in lignite from a germanium-bearing deposit in Primorye

We studied a number of chemical characteristics in the coals of the Spetsugli germanium-bearing area of the Pavlovskoe coalfield in southern Primorye. It was found that the coals show variable contents of ash, extractable organic matter (OM), and germanium. No less than 60% germanium in the coals are bound to mobile OM, including 25–60% in complex compounds of humic acids and 8–39% in the low-molecular-weight fraction of OM not precipitated by acids. It was shown that germanium can be partly accumulated in coals as organic compounds owing to the dissolution of the mineral forms of germanium by humic acids.     

Dualistic distribution coefficients of elements in the system mineral-hydrothermal solution. I. Gold accumulation in pyrite

The use of trace elements (TE) as geochemical indicators is complicated by the dualism of their distribution coefficients D due to the additional (i.e., above the concentrations of an isomorphic component) incorporation of elements at structural defects of various nature (including the surface of the crystal). A pressing problem in this situation is to determine the true D values that pertain to the structural component of an admixture D ^str and evaluate effects of other modes of TE occurrence. Only upon distinguishing D ^str in the bulk coefficient D ^bulk it is possible to evaluate the ore potential of fluid in terms of certain TE from the composition of a mineral containing the TE. Pyrite synthesized in solutions of variable pH at 450°C and 1 kbar (100 MPa) at fluid portions sampled in a trap is utilized to demonstrate the role of a surface nonautonomous phase (NP) in the incorporation of gold in this mineral. The distribution coefficient of gold between pyrite and hydrothermal solution is 0.14 for “pure” pyrite and 0.05 for As-bearing pyrite (containing 0.02–0.05 wt % As), and these coefficients for NP are 310 and 170, respectively. This increases the D ^bulk for evenly distributed (“invisible”) gold by factors of four and nine. In contrast to the results of earlier studies conducted at room temperature and pressure or parameters close to them, our data demonstrate that the accumulation of “invisible” Au in pyrite is controlled not only by reducing adsorption with the development of Au(0) particles and films but also by Au incorporation in NP developing in the surface layer of the crystal approximately 500 nm thick as chemically bound Au [most likely as Au(I)]. The possible reason for the high absorption capacity of NP is the defect (pyrrhotite-like) structure, which is not saturated with bonds of excess S and sulfoxi onions.     

Molecular weight distribution,analytical and spectroscopic characterization of humic fractions sequentially isolated by organic solvents from a brown coal humic acid

A sequential fractionation procedure employing a series of selected mild organic solvents of different polarity has been applied for the isolation of chemically different organic fractions from a brown coal humic acid. Elemental composition, molecular weight distribution, i.r. and electron spin resonance analysis were carried out on the isolated humic fractions. They were characterized by: (a) a low polydispersity, (b) a decreasing aliphatic and increasing aromatic character along the series, (c) very different molecular weight which significantly correlated with E₄/E₆ ratios (particle aggregation and molecular association) and free radical concentrations (chemical and biochemical activity). Significant correlations were found between physico-chemical parameters of the isolated humic fractions, i.e. M_n, M_w, E₄/E₆ ratios, spins/g contents and the dielectric constants of the solvents used. This suggested the efficiency of the applied procedure in isolating chemically different organic fractions from the bulk, original humic acid.     

热泉热液金矿化中嗜热微生物——有机质的地球化学作用

本文主要通过对热泉热液金成矿过程中的热泉水化学成分和组分的分析,得出泉水中金与氮磷硫、氟硅碳两组组分有很好的相关性。嗜热硫酸盐还原菌能使［Ａｕ（ＨＳ）２］－和［Ａｕ（Ｓ２Ｏ３）２］３－都氧化还原成硫化物,从而使金由热水溶液中沉淀。热泉沉积软泥的有机质中的含硫氨基酸、含硫芳烃也起到了一定的聚金作用。     

Phosphorus in marine and non-marine humic substances

The phosphorus content of marine humic acids (HA) is in the range of 0.1–0.2%. The C/P ratios of the HA are 300 to 400. Marine fulvic acids (FA) contain 0.4–0.8% P and have C/P ratios of 80 to 100. High molecular weight organic matter dissolved in pore waters (DOM) contains 0.5% P and has C/P of 90. The data suggest that during the formation sequence: Plankton → DOM → FA → HA → Kerogen, phosphorus is lost, mainly in the FA → HA (and possibly also in the HA → Kerogen) step. Diagenesis of sedimentary humic acids is accompanied by loss of phosphorus (as well as of nitrogen) to form HA with C/P ratios of 1000.Soil humic substances resemble marine humates in P content (0.3%) and soil FA's are about three to fivefold enriched in P relative to HA. C/P ratios are lower in soil HA (ca. 200) as compared with marine HA. Humic acids from diagenetic products such as peat and lignite are highly depleted in P. Rough calculations indicate that humate bound P may account for 20–50% of the organic phosphorus reservoir in sediments. The chemical speciation of this P is unknown, but lack of correlation with ash, Fe, Ca or Al content (in marine humates, at least) indicates that it is organically bound.     

东北寨金矿床成矿机制：地球化学热力学研究

本文依据地球化学热力学方法圈定了东北寨微细浸染型金矿床的成矿条件，探讨了热液中金的溶解迁移形式及成矿过程。研究结果表明，Au（HS）-2和AuH3SiO04为金的主要迁移形式，随着主期硅化的发生，金的有效载体从AuH3SiO04转为Au（HS）-2；而AuCl-2的作用始终微不足道。石英及黄铁矿、辉锑矿等硫化物的沉淀是导致金成矿的主要因素。有机质对金成矿的贡献具有阶段性的意义。     

Transport and Concentration of Gold in Metamorphic—hosted Reworked Gold Deposits,China

Calculations based on the available thermodynamic data of AuCl ₂ ⁻ and Au (HS) ₂ ⁻ indicate that AuCl ₂ ⁻ is responsible for the transport and enrichment of gold during the stage of pre-concentration in the source bed while Au (HS) ₂ ⁻ is the main gold species involved in the formation of gold deposits in response to hydrothermal reworking. Acid chloride solutions witha _Cl ⁻ > 10° and sulfur-rich solutions with a_Σs in excess of 10⁻² are held as important criteria for gold enrichment in the source bed and for the formation of gold deposits by subsequent hydrothermal event, respectively.     

Diagenetic trends of a tertiary low-rank coal series

The Mahakam delta (Kalimantan, Indonesia) coals represent all the evolution stages between freshly-deposited plant/peat material, lignites and bituminous coals. The geochemical techniques used to study this coal series included elemental analysis, extraction of humic compounds, infrared spectroscopy and ¹³C nuclear magnetic resonance of the total coal.The main mechanisms of early maturation in this series are loss of oxygenated compounds, aromatisation and condensation of the organic matter. These changes, which have already been suggested for other coal series and partially reported for sedimentary organic matter, were confirmed and described in more detail for the Mahakam coal series.     

有机质在微细浸染型金矿化中的作用—以黔桂地区为例

黔桂地区微细浸染型金矿主要产于碳酸盐岩—碎屑岩混合沉积层序中,溶矿岩石以泥质岩、粉砂岩和碳酸盐岩为主,富含有机质。矿石中有沥青分布,含金石英中存在有机质裹体。碳质含金量较高,可达53.60×10~(-6),在黄铁矿型矿石中,碳质含量与金的富集具有同步消长的正相关关系,有机质与金矿化关系密切。有机质中对金的迁移和富集起主要作用的是Au(CN)_2~-,Au(CN)_1~-,Au(HS_2)~-等化合物,含金有机络合物在岩石的孔隙或裂隙中运移沉淀。     

Rapid quantification of humic and fulvic acids by HPLC in natural waters

A simple method based on high-performance size-exclusion chromatography (HPSEC) has been developed for rapid quantification of humic and fulvic acids (HA and FA) in stream waters. A Tsk-gel column was used to separate natural dissolved organic matter (DOM) into two components: peak A and B. In terms of HPSEC chromatograms and fluorescence patterns, peak A and B were similar to the corresponding XAD-extracted HA and FA, respectively. It is suggested that peak A fraction mainly consisted of HA, and peak B fraction FA. The similar separation of HA and FA using HPSEC and a conventional XAD method suggests the consistency of molecular size distribution and physical–chemical properties of DOM. HPSEC offers a simple and rapid method for the quantification of HA and FA instead of tedious extractions of humic substances. Analyses of natural water samples show that the calculation of HA/FA based on UV absorbance was under- or over-estimated, the calibration using the extracted HS allows a more accurate quantification. The fast screening of HA and FA provides useful quantitative and qualitative information that can be used in environmental or monitoring studies.     

Structural investigations of Australian coals—III. A 13C-NMR study on the effects of variation in rank on coal humic acids

A quantitative ¹³C-NMR technique was applied to humic acids, isolated from total solvent extracts obtained from coals, varying in rank from lignite to medium volatile bituminous. The results from elemental analysis and ¹³C-NMR structural ratios are interpreted in the form of three distinct structural phases in the maturation of coal humic acids. These phases reflect the rank of the parent coals. A decrease in polar functional group content and corresponding increase in aromaticity is observed with increasing maturation of humic acid chemical structure. Limits are postulated for the oxygen content and level of aromaticity for humic acids derived from higher rank coals.     

Mercury speciation in soil in vicinity of coal beds using sequential extraction

The sequential extraction procedure was proposed and used to study of mercury speciation in real samples of soil. Samples of soil profiles together with bedrock and coal were taken from sampling spots in the vicinity of surficial coal beds in an area with natural coal outcrops. The proposed sequential extraction procedure involves the following fractionation: organic mercury compounds, extractable mercury in an acidic medium, mercury bound to humic substances, elemental Hg and mercury bound to complexes, HgS and residual mercury. The significant distribution of mercury between the two portions—mercury bound to humic substance and HgS was determined in the majority of samples. The mercury bound to humic substances created a significant contribution, especially to the top layer of soil. On the other hand, HgS was the dominant form in the samples from lower layers of the soil profile. The mercury content in the samples did not show a distinct mobility. The influence of soil parameters on the mercury distribution in the studied samples was investigated and discussed.     

Mercury mobility and bioavailability in soil from contaminated area

The mobility and bioavailability of mercury in the soil from the area near a plant using elemental mercury for manufacturing thermometers, areometers, glass energy switches and other articles made of technical glass has been evaluated. Mercury has been determined by sequential extraction method and with additional thermo desorption stage to determine elemental mercury. The procedure of sequential extraction involves five subsequent stages performed with the solutions of chloroform, deionized water, 0.5 M HCl, 0.2 M NaOH and aqua regia. The mean concentration of total mercury in soil was 147 ± 107 μg g⁻¹ dry mass (range 62–393), and the fractionation revealed that mercury was mainly bound to sulfides 56 ± 8% (range 45–66), one of the most biounavailable and immobile species of mercury in the environment. The fractions that brought lower contribution to the total mercury content were semi-mobile humic matter 22 ± 9% (range 11–34) and elemental mercury 17 ± 5% (range 8–23). The contributions brought by the highly mobile and toxic organomercury compounds were still lower 2.3 ± 2.7% (range 0.01–6.5). The lowest contributions brought the acid-soluble mercury 1.5 ± 1.3% (range 0.1–3.5) and water-soluble mercury 1.0 ± 0.3% (range 0.6–1.7). The surface layer of soil (0–20 cm) was characterized by higher mercury concentrations than that of the subsurface soil (60–80 cm), but the fractional contributions were comparable. The comparison of mercury fractionation results obtained in this study for highly polluted soils with results of fractionation of uncontaminated or moderately contaminated samples of soil and sediments had not shown significant statistical differences; however, in the last samples elemental mercury is usually present at very low concentrations. On the basis of obtained correlation coefficients it seems that elemental mercury soils from “Areometer” plant are contaminated; the main transformation is its vaporization to atmosphere and oxidation to divalent mercury, probably mainly mediated by organic matter, and next bound to humic matter and sulfides.     

Speciation of gold in hydrosulphide-rich ore-forming fluids: Insights from first-principles molecular dynamics simulations

To shed light on gold speciation in sulfur-containing ore-forming fluids, we perform first principles molecular dynamics (FPMD) simulations to investigate gold-hydrosulphide complexing under representative geological conditions. With this advanced technique, the electronic structures of solutes and solvents are calculated with density functional theory and the thermal motions are sampled with molecular dynamics. The molecular structures, solvated structures and stabilities of possible complexes are characterized in detail and the following insights have been gained. (1) The previously hypothesized species Au(HS)(H₂S)₃ and Au(HS) are found unstable under ore-forming conditions. Au(HS)(H₂S)₃ would dissociate to LAu(HS) (L = H₂S or H₂O) and free H₂S molecules spontaneously. Au(HS) is highly reactive and tends to capture a second ligand to form a double-coordinated complex. (2) In the thin vapor-like phases of low pressures, the stable complexes include Au(HS)(H₂O), Au(HS)(H₂S) and Au(HS)₂⁻ and their relative stability is Au(HS)₂⁻ > Au(HS)(H₂S) > Au(HS)(H₂O). In dense aqueous phases of high pressures, Au(HS)(H₂S) would spontaneously deprotonate to Au(HS)₂⁻ and thus Au(HS)(H₂O) and Au(HS)₂⁻ are the stable forms. All of these complexes can retain to the upper-limit of ore-forming temperatures. (3) The gold ions in the complexes do not favor coordinating more molecules and therefore the solvations happen mainly through H-bonding interactions between the ligands and environmental waters. H-bonds are found in vapor, liquid, and dense supercritical phases, whereas in the thin supercritical phase the hydration is very weak. These results provide quantitative and microscopic basis for understanding the speciation of gold in hydrothermal fluids.