Trace metal nanoparticles in pyrite

Hydrothermal pyrite contains significant amounts of minor and trace elements including As, Pb, Sb, Bi, Cu, Co, Ni, Zn, Au, Ag, Se and Te, which can be incorporated into nanoparticles (NPs). NP-bearing pyrite is most common in hydrothermal ore deposits that contain a wide range of trace elements, especially deposits that formed at low temperatures. In this study, we have characterized the chemical composition and structure of these NPs and their host pyrite with high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), analytical electron microscopy (AEM), and electron microprobe analysis (EMPA). Pyrite containing the NPs comes from two types of common low-temperature deposits, Carlin-type (Lone Tree, Screamer, Deep Star (Nevada, USA)), and epithermal (Pueblo Viejo (Dominican Republic) and Porgera (Papua New-Guinea)).EMPA analyses of the pyrite show maximum concentrations of As (11.2), Ni (3.04), Cu (2.99), Sb (2.24), Pb (0.99), Co (0.58), Se (0.2), Au (0.19), Hg (0.19), Ag (0.16), Zn (0.04), and Te (0.04) (in wt.%). Three types of pyrite have been investigated: “pure” or “barren” pyrite, Cu-rich pyrite and As-rich pyrite. Arsenic in pyrite from Carlin-type deposits and the Porgera epithermal deposit is negatively correlated with S, whereas some (colloform) pyrite from Pueblo Viejo shows a negative correlation between As + Cu and Fe. HRTEM observations and SAED patterns confirm that almost all NPs are crystalline and that their size varies from 5 to 100 nm (except for NPs of galena, which have diameters of up to 500 nm). NPs can be divided into three groups on the basis of their chemical composition: (i) native metals: Au, Ag, Ag–Au (electrum); (ii) sulfides and sulfosalts: PbS (galena), HgS (cinnabar), Pb–Sb–S, Ag–Pb–S, Pb–Ag–Sb–S, Pb–Sb–Bi–Ag–Te–S, Pb–Te–Sb–Au–Ag–Bi–S, Cu–Fe–S NPs, and Au–Ag–As–Ni–S; and (iii) Fe-bearing NPs: Fe–As–Ag–Ni–S, Fe–As–Sb–Pb–Ni–Au–S, all of which are in a matrix of distorted and polycrystalline pyrite. TEM-EDX spectra collected from the NPs and pyrite matrix document preferential partitioning of trace metals including Pb, Bi, Sb, Au, Ag, Ni, Te, and As into the NPs. The NPs formed due to exsolution from the pyrite matrix, most commonly for NPs less than 10 nm in size, and direct precipitation from the hydrothermal fluid and deposition into the growing pyrite, most commonly for those > 20 nm in size. NPs containing numerous heavy metals are likely to be found in pyrite and/or other sulfides in various hydrothermal, diagenetic and groundwater systems dominated by reducing conditions.     

“Invisible” silver and gold in supergene digenite (Cu1.8S)

Despite its potential economic and environmental importance, the study of trace metals in supergene (secondary) Cu-sulfides has been seriously overlooked in the past decades. In this study, the concentration and mineralogical form of “invisible” precious metals (Ag, Au) and metalloids (As, Sb, Se, Te) in supergene digenite (Cu_1.8S) from various Cu deposits in the Atacama Desert of northern Chile, the world’s premier Cu province, were determined in detail using a combination of microanalytical techniques. Secondary ion mass spectrometry (SIMS) and electron microprobe analyzer (EMPA) measurements reveal that, apart from hosting up to ∼11,000 ppm Ag, supergene digenite can incorporate up to part-per-million contents of Au (∼6 ppm) and associated metalloids such as As (∼300 ppm), Sb (∼60 ppm), Se (∼96 ppm) and Te (∼18 ppm). SIMS analyses of trace metals show that Ag and Au concentrations strongly correlate with As in supergene digenite, defining wedge-shaped zones in Ag-As and Au-As log-log spaces. SIMS depth profiling and high-resolution transmission electron microscopy (HRTEM) observations reveal that samples with anomalously high Ag/As (>∼30) and Au/As (>∼0.03) ratios plot above the wedge zones and contain nanoparticles of metallic Ag and Au, while samples with lower ratios contain Ag and Au that is structurally bound to the Cu-sulfide matrix. The Ag-Au-As relations reported in this study strongly suggest that the incorporation of precious metals in Cu-sulfides formed under supergene, low-temperature conditions respond to the incorporation of a minor component, in this case As. Therefore, As might play a significant role by increasing the solubility of Ag and Au in supergene digenite and controlling the formation and occurrence of Ag and Au nanoparticles. Considering the fact that processes of supergene enrichment in Cu deposits can be active from tens of millions of years (e.g. Atacama Desert), we conclude that supergene digenite may play a previously unforeseen role in scavenging precious metals from undersaturated (or locally slightly supersaturated) solutions in near-surface environments.     

Exploitation of gold in an historic sewage sludge stockpile, Werribee, Australia: resource evaluation, chemical extraction and subsequent utilisation sludge

Sewage sludges are potential targets for economic extraction of Au because of the documented Au content of sewage sludges worldwide, which are of the order of some ore deposits currently mined for Au. The sewage of Melbourne, Australia, was stockpiled in large, closed, lagoonal tanks from 1898 until 1980. Reeves, Plimer and Foster, 1999, have conducted, and published, an extensive and exhaustive study of the Werribee sewage reserves utilising RNAA, INAA, GFAAS, ICPMS, and FLAAS to determine 31 elements, including Au, Ag, Sb, As, Cd, Hg, Zn, Cu, and Pb. The study was initiated to determine Au, Ag and other metal variations in both space and time and to investigate the economics of chemical extraction of the precious metals. A total of 149 samples from over 50 hand-auger drillholes to a depth up to 4m were analysed from the stockpiles, with Au assays yielding remarkably consistent results. Average grades of 0.77 g/t Au and 18.8 g/t Ag have been documented for a measured resource of 770,000 m³. Laboratory-based extractive metallurgy of the Werribee sludges has demonstrated that Au, Ag, and Zn can be removed with relative ease by heap-leaching using modified conventional technology, albeit with prohibitive reagent consumption. The extraction of the precious metals also results in the variable removal of contaminant metals such as Cd, As, Sb, Hg and Cr which may render the sludges fit for sale as agricultural fertiliser, provided organic pollutants and pathogenic organisms are below governmental environmental protection limits.     

湘西南元古宙高涧群微量元素主成分分析

主成分分析法（PCA）是多元样本数据的数理统计方法。本文结合湘西南元古宙高涧群地层剖面等离子光谱分析所得Au、Ag、As、Sb、Cu、Pb、Zn、Sr、Ba、Mn、Co、Ti、Cr共13个微量元素的主成分计算结果和图解,解释了主成分参数和图解的地质含义。在C剖面和L剖面上,主成分F1具有相似的信息量,反映高涧群“原始”沉积物以铁镁矿物为主要特征。F2的信息量不同,在L剖面上,F1－F2图解可以将13个“原”变量分为5组“原”变量的组合：Co-Zn-Cu(Mn、Ba)、Ti-Cr、As-Pb、Au-Pb-Sr和Ag,Ag主要来自碎屑沉积物;在C剖面上,“原”变量的组合特征不明显,As、Cr、Sb、Ti与F2呈正相关,Sr与F2呈负相关。在L剖面上,Au主要受氧化条件制约;在C剖面上,海水较深,还原条件有利于Au、Ag的沉积。由于沉积环境不同,研究区的南部和北部一些微量元素存在明显的差异。根据（di^k)^2计算值,Ag、Pb的分布部分与后期构造破坏有关。     

招远大尹格庄金矿床微量元素特征及其意义

该文以山东招远大尹格庄金矿床中微量元素为研究对象,通过对矿床围岩、矿石等微量元素的研究,表明大尹格庄金矿围岩中微量元素以富含 Bi,Au,Pb,W,Ag,Sn 为特点,矿体和矿化体中元素组合为 Au,Ag,As,Sb,Hg,B, Cu,Zn,Bi,Mo,Mn,Co,Ni,W。在5个成矿阶段中,第二阶段与第三阶段微量元素的富集程度较明显,表现为 Au, Ag,As,Co,Bi,Cu,Pb,Zn 等的富集,成矿元素可分为2个分带序列,主成矿元素为 Au Ag Cu Pb Zn Bi 组合、头晕元素 As Sb Hg 组合和尾晕元素 Co Ni 组合。     

Exploitation of gold in a historic sewage sludge stockpile, Werribee, Australia: resource evaluation, chemical extraction and subsequent utilisation of sludge

Sewage sludges are dewatered end products of human sewage waste and are recognised repositories of organic pollutants and heavy metals. They may be considered targets for economic extraction of Au because of the documented Au content of sewage sludges worldwide which are of the order of some ore deposits currently mined for Au. They are also highly nutrient enriched (nitrogen and phosphorus) and therefore amenable to use as agricultural fertiliser or as covers for mine wastes. The sewage of Melbourne, Australia, a city with a current population of 3.3 million, was stockpiled in large, closed, lagoonal tanks from 1898 until 1980. In 1995 Echidna Mining, an Australian gold exploration company, acquired the exploration rights to the ground surrounding the historic sludge reserves and commenced a program of resource evaluation, utilising RNAA, INAA, GFAAS, ICP–MS and FLAAS to determine 31 elements, including Au, Ag, Sb, As, Cd, Hg, Zn, Cu, and Pb. The study was initiated to determine Au, Ag and other metal variations in both space and time and to investigate the economics of chemical extraction of the precious metals. A total of 149 samples from over 50 hand-auger drillholes to a depth up to 4 m have been analysed from the stockpiles, with Au assays yielding remarkably consistent results. Average grades of 0.77 g/t Au and 18.8 g/t Ag have been documented for a measured resource of 770,000 m³ (of an estimated 1.6–2.5 million m³ contained) at a density of 1.0 g/cm³ and an average moisture content of around 40%. Laboratory-based extractive metallurgy of the Werribee sludges has demonstrated that Au, Ag and Zn can be removed with relative ease by heap-leaching using modified conventional technology, albeit with prohibitive reagent consumption. The extraction of the precious metals also results in the variable removal of contaminant metals such as Cd, As, Sb, Hg and Cr which may render the sludges fit for sale as agricultural fertiliser, provided organic pollutants and pathogenic organisms are below governmental environmental protection limits, an area beyond the scope of this paper. Another potential avenue of the exploitation of sewage sludges is discussed: that of the utilisation of sludges to extract contaminant metals from waste water and contaminated mine waters, which we demonstrate on pure aqueous synthetic samples. This paper presents a study of the exploitation of an historic sludge resource for its contained Au and residue post-metal extraction.     

陕西南秦岭南部褶皱带贵金属、有色金属成矿规律及找矿方向

南秦岭南部褶皱带是秦岭造山带的重要组成部分，随着找矿勘查工作的深入，相继发现了一系列金、银、锑、铅、锌、铜矿床（点），成为陕西省又一重要有色、贵金属成矿带。南秦岭南部元古宙至中生代多次发生火山成矿作用、沉积或喷流沉积成矿作用和构造-岩浆成矿作用，金、银、锑、铅、锌、铜成矿具有一定的规律，找矿前景好。从资源潜力及经济意义上来看，金应该是该区的主攻矿种。同时，应该兼顾银、锑、铅、锌、铜的找矿工作。开展自水江-留坝成矿带金、银锑找矿、牛山隆起北缘成矿带金铜多金属找矿和红椿坝断裂两侧铜金找矿是主要找矿方向。     

胶东山后金矿床地质体微量元素特征及找矿意义

对胶东招平断裂上的山后金矿34个钻孔进行了原生晕测量,分析了Au、Ag、cu、Pb、zn、As、Sb、Bi、Mo、Hg等10种元素,统计了胶东岩群、荆山群、玲珑花岗岩及招平断裂蚀变带中微量元素含量及变化.变质岩、花岗岩均富Bi、Ag,而贫Hg、Sb、Au、Cu、zn、As;胶东岩群、荆山群中金的丰度值相近,它们均为金矿的矿源岩;在招平断裂蚀变带中Au、Ag、Pb、Mo、Bi等元素出现了明显富集,而Cu、zn、Sb、Hg等元素没有富集,矿床多金属硫化物阶段不发育;根据聚类分析结果,Au与Ag、Cu、Pb、zn生成于不同的成矿期,招平断裂中的Au矿体形成于金成矿期,招平断裂上盘荆山群地层中的Au、Ag、cu、Pb、Zn多金属矿体形成于金银多金属成矿期;招平断裂北段的成矿条件要比南段好;根据As、Mo元素含量的变化,确定出山后金矿深部矿体预测的简单准则,并对金矿深部进行了简单成矿预测.     

Distribution Characteristics of Gold and Other Trace Elements in the Proterozoic Lengjiaxi Group,Northeastern Hunan Province

Systematic geochemical studies of the Proterozoic Lengjiaxi Group in northeastern Hunan Province suggest that the Lengjiaxi Group is a Au-As-Sb-W association-type Au-bearing turbidite formation.The contents of Au,As,Sb,W,Cr,Mn,Pb and Zn in the turbidite formation are more than two times as high as the average contents of trace elements in the upper continental crust.The low abundance of Ag and the close correlation between Au and As are two important characteristic features.In the Au-bearing turbidite formation the enrichment of gold is due to the extensive occurrence of Au-bearing pyrites.Higher contents of Au,W,Sb and Ag in the greywacke indicate that they also exist in the form of heavy minerals.Au,Ag,As,Sb,W and REE in the Au-bearing turbidite formation have a close genetic relation with the chemistry of the gold deposits.     

玲珑金矿大开头矿区47号脉微量元素特征

选择胶东玲珑金矿典型矿体47号脉为研究对象,应用基岩地球化学方法,测试微量元素含量,研究微量元素与金的相关关系、计算微量元素的浓集系数并确定其轴向分带,探讨微量元素对深部金成矿的指示意义,期待能对玲珑金矿深部找矿提供一些参考.初步认识如下:矿区金矿体的最佳指示元素依次为Au、Ag、Bi、As、Cu、Co、Mo、Sb;金矿体的轴向分带序列从上到下依次为As、Pb、Ag、Cu、Hg、Sb、Mo、Ni、Th、V、U、Mn、Zn、Bi、Co、Au;矿体中Au、Bi、Ag、As富集系数大,Cu、Co富集系数中等,而Zn在矿体中相对亏损.研究结果表明,在深部47号矿体仍有较好的成矿前景.     

西秦岭礼岷金矿带李坝群含金浊积岩建造地球化学特征

本文通过对李坝群含金浊积岩建造中金及其它微量元素的分布、地球化学特征及与金矿成因的关系研究，结果表明，李坝群含金浊积岩建造明显富集Ａｕ、Ａｓ、Ｓｂ、Ｂｉ和铁族元素Ｃｏ、Ｎｉ、Ｃｒ、Ｖ，且具有较高的ＡＵ/Ａｇ比值。李坝群含金浊积岩建造是衍生含金建造，对于金成矿来说，并非是主要的矿源层，而是赋矿岩系。     

Erosion level of the epithermal Rogovik deposit estimated from geochemical data,northeast Russia

The geochemical zoning of the Rogovik epithermal deposit in northeast Russia has been established on the basis of endogenic anomalous geochemical fields (AGCF) of Au–Ag zones, their qualitative and quantitative compositions, and spatial distribution of chemical element indicators of Au–Ag mineralization. The obtained geochemical data (monoelemental AGCF, associations of elements, their composition, contrast, and correlation) allowed us to estimate the erosion level of Au–Ag ore zones. It has been shown that AGCF related to Au–Ag mineralization are distinguished by simple component composition (Au, Ag, Hg, Sb, As, Cu, Pb, Zn) and regular spatial distribution of the elements. It has been established that the least eroded central part of the object is characterized by widespread and the most contrasting Au, Ag, Hg, Sb, and As AGCF closely related to the ore-bearing units of the deposit. The contrast of these fields gradually decreases with depth. Low-contrast Cu, Pb, and Zn AGCF typical of the footwall depth intervals and flanks of Au–Ag zones intervals appear at depth. The northern part of the area is eroded to the deepest level. The contrast of Ag, Hg, Sb, and As geochemical fields abruptly decreases here, and Cu, Pb, and Zn AGCF become widespread with depth. The relatively contrasting fields of anomalous Au concentrations develop here extremely locally and near the surface. It has been concluded that the as yet poorly explored southern part of the Rogovik deposit most likely is promising for further geological exploration and the discovery of new mineralized areas.     

Specific composition of native silver from the Rogovik Au–Ag deposit,Northeastern Russia

The first data on native silver from the Rogovik Au–Ag deposit in northeastern Russia are presented. The deposit is situated in central part of the Okhotsk–Chukchi Volcanic Belt (OCVB) in the territory of the Omsukchan Trough, unique in its silver resources. Native silver in the studied ore makes up finely dispersed inclusions no larger than 50 μm in size, which are hosted in quartz; fills microfractures and interstices in association with küstelite, electrum, acanthite, silver sulfosalts and selenides, argyrodite, and pyrite. It has been shown that the chemical composition of native silver, along with its typomorphic features, is a stable indication of the various stages of deposit formation and types of mineralization: gold–silver (Au–Ag), silver–base metal (Ag–Pb), and gold–silver–base metal (Au–Ag–Pb). The specificity of native silver is expressed in the amount of trace elements and their concentrations. In Au–Ag ore, the following trace elements have been established in native silver (wt %): up to 2.72 S, up to 1.86 Au, up to 1.70 Hg, up to 1.75 Sb, and up to 1.01 Se. Native silver in Ag–Pb ore is characterized by the absence of Au, high Hg concentrations (up to 12.62 wt %), and an increase in Sb, Se, and S contents; the appearance of Te, Cu, Zn, and Fe is notable. All previously established trace elements—Hg, Au, Sb, Se, Te, Cu, Zn, Fe, and S—are contained in native silver of Au–Ag–Pb ore. In addition, Pb appears, and silver and gold amalgams are widespread, as well as up to 24.61 wt % Hg and 11.02 wt % Au. Comparison of trace element concentrations in native silver at the Rogovik deposit with the literature data, based on their solubility in solid silver, shows that the content of chalcogenides (S, Se, Te) exceeds saturated concentrations. Possible mechanisms by which elevated concentrations of these elements are achieved in native silver are discussed. It is suggested that the appearance of silver amalgams, which is unusual for Au–Ag mineralization not only in the Omsukchan Trough, but also in OCVB as a whole, is caused by superposition of the younger Dogda–Erikit Hg-bearing belt on the older Ag-bearing Omsukchan Trough. In practice, the results can be used to determine the general line of prospecting and geological exploration at objects of this type.     

基于元素含量和空间变异系数的化探异常信息识别

化探异常信息识别是化探数据分析最重要的任务之一, 也是化探数据在资源勘查领域受到广泛关注的最重要原因, 前人对化探异常信息识别做过大量研究, 这些研究中的大多数主要关注化探示踪元素的含量, 近而根据含量指标计算异常阈值, 而对示踪元素在空间中的分布特征关注较少。本文选择 1: 20万比例尺的克拉玛依幅为研究区, 根据区内金矿的矿床地球化学特征选择Ag、As、Au和Sb等4种元素为本区内金矿的示踪元素, 以地球化学元素分散晕形成理论为依据, 使用GIS技术和Matlab软件绘制研究区内4种金矿示踪元素的综合地球化学异常图。结果表明, 与传统阈值方法得到的化探异常图相比, 本文得到的化探异常图能够更好地指示研究区内已知金矿。     

Trace metals in sediments near offshore oil exploration and production sites in the Alaskan Arctic

Increased offshore development in the Alaskan Arctic has stimulated interest in assessing potential impacts to the environment before the onset of any adverse effects. Concentrations of trace metals in sediments are used in this paper to provide one sensitive indicator of anthropogenic inputs from offshore activity over the past several decades. Sediments in coastal waters of the western Beaufort Sea are patchy with respect to sediment granulometry, organic carbon content, and concentrations of trace metals. However, results for surface sediments and age-dated cores show that nearly all samples contain natural concentrations of Ag, Ba, Be, Co, Cr, Cu, Hg, Ni, Pb, Sb, Tl, V and Zn, with metal/Al ratios that have been constant for many decades. Metal concentrations for incoming river-suspended matter compare well with sediment metal values and, along with vertical distributions in sediments, show no discernible diagenetic impacts that distort the sedimentary record for metals, except for Mn, As and possibly Cd. Slightly elevated concentrations of Ba, Hg, Ag, Sb and Zn were observed in a total of eight instances or in only 0.7% of the 1,222 data points for metals in surface sediments.     

玲珑金矿田东山矿床矿体空间分带模型及应用

根据玲珑金矿田东山矿床地表及浅部勘查工程与采矿资料, 确定了成矿成晕元素种类。对成晕元素侧向分带特征和垂向分带规律的研究结果表明, 矿体上盘晕元素异常组合为Cu-As-Ag, 下盘晕元素异常组合为Cu-Te-As, 由此确定Au /As、Au /Pb、Au /Ag、Ag/Pb比值具有成矿判别意义, 即判别式Y₁ = 0.000 5 Au /As + 0.037 6 Au /Ag + 0.085 7 Au /Pb - 0.045 4 Ag/Pb > 0.009 2时指示含矿, 否则不含矿; 同时建立了基于Sb /As比值和Au、Ag、As、Sb 含量特征的见矿深度估计模型(H₁ = 1.104 9 + 79.63 k ( Sb /As) ×102 ) , 并对东山矿床主要矿体的可能成矿地段、见矿部位做出预测评价, 提出东山矿床9号、18号、47号、50号和52号支脉在175～ - 70 m标高范围内赋存金矿化或工业矿体。     

福建紫金山矿田罗卜岭斑岩型铜钼矿地球化学立体探测示范

罗卜岭矿床是与晚中生代花岗闪长斑岩体有关的隐伏斑岩型铜钼矿床, 矿区位于紫金山矿田的东北部; 铜钼矿体主要产于绿泥石化-绢英岩化和(弱)钾化-绢英岩化带中, 矿石矿物组合为黄铜矿+辉钼矿; 少量过渡类型矿体产于高级泥化带中, 矿石矿物组合为蓝辉铜矿+铜蓝+辉钼矿。罗卜岭矿区的原生晕地球化学三维模型显示, 微量元素具有一定的分带特征, 低温元素Au与高温元素组合W、Sn、Bi分布于矿体上方, 中低温元素Pb、Zn、Ag分布于Cu、Mo元素之间; 元素直观垂向分带序列大致为: (As、Sb、Hg)-(W、Bi、Sn)-Ga-Au、Ba-Cu、Ag-Pb、Zn-Mn-Mo; 前缘晕的元素与氧化物组合为As、Sb、Au、Ga、Al2O3, 矿体近矿晕元素组合为Ag、Pb、Zn, 缺失尾晕元素组合; Cu、Mo可直接作为找矿指示元素, Au、Ag、Pb、Zn、As、Sb、Ga、Ba、Mn可作为间接指示元素, 矿床深部K2O正异常与Al2O3负异常可作为斑岩型铜钼矿的重要找矿标志, 这一规律对紫金山矿田深部和外围隐伏斑岩型矿体的勘查工作具有重要的参考意义。     

贵州开阳磷矿地区下寒武统牛蹄塘组地层层序及其As、Sb、Au、Ag丰度异常与赋存状态研究

贵州开阳磷矿地区出露较为完整的下寒武统黑色岩系层序,这套黑色岩系中富含多种金属元素,但目前对岩系中主要低温成矿元素As、Sb、Au、Ag的地球化学背景异常与分布规律了解极少,对其形成背景与赋存状态无法进行深入讨论。本文以开阳磷矿地区下寒武统牛蹄塘组黑色岩系剖面作为研究对象,通过详细的野外地质调查、系统采样并进行地球化学分析、全岩硫同位素分析及黄铁矿电子探针分析,划分了详细的牛蹄塘组地层层序,对主要低温成矿元素(As、Sb、Au、Ag)的丰度异常、富集特征及赋存状态进行了研究,结果表明,黑色岩系中普遍富集As、Sb、Ag三种主要低温成矿元素,Au也在大部分层位富集。四种元素具有层控性的特点,在牛蹄塘组下部有机质含量较高的黑色白云质粉砂质页岩和黑色页岩层位中具有较高的元素丰度异常,在泥岩和粉砂岩混合层位元素丰度异常较低,钙质成分含量较高的层位元素含量较低。黄铁矿是黑色页岩中金的主要赋存矿物,也是Sb的重要赋存矿物,同时是Ag和As的次要赋存矿物;不同类型的黄铁矿,元素富集规律也不相同:As、Ag更容易富集在不规则集合体和草莓状黄铁矿中,Sb和Au则在散布的单颗粒黄铁矿中富集系数最高。     

Application of enzyme leach soil analysis for epithermal gold exploration in the Andes of Ecuador

Enzyme Leach^SM (EL) soil surveys were undertaken over known epithermal Au mineralisation at El Mozo and Llano Largo, Azuay, Ecuador to assess the utility of the technique for identifying such deposits in the Ecuadorian Andes. The results indicate the development of both apical- and oxidation-type EL anomalies over auriferous structures at the two sites, the former systematically incorporating Au, and the latter Cl and Br. The spectrum of elements responsive to mineralisation at El Mozo (Cl, Br, I, La, Ce, Nd, Cu, Pb, Au, As, Sb, Ag, Zr, Sr) was found to be considerably greater than at Llano Largo (Cl, Br, Au, As, Sb, Ag, Zn), probably reflecting the contrasting high- and low-sulphidation assemblages of the two prospects. Ratios of EL versus aqua-regia extractable trace element concentrations ranged from 1:<100 for Mn to 1:>400 for chalcophile elements such as Pb, Sb, As, Bi and Ag. Strong correlations between the concentrations of several analytes (including Mn, Sr, Cu, Co, As) extracted by the two procedures indicate, however, that EL datasets are extensively influenced by bulk matrix composition. Spatial variations of EL extractable Mn were found to exert no major influence on apical or oxidation suite anomaly patterns at El Mozo. However, Mn-normalisation of halogen data for Llano Largo elucidated otherwise obscure oxidation features, potentially related to Au mineralisation. Ratios between elements subject to apical enrichment and those of the oxidation suite (e.g. Cl/Au and Bi/Br) were found to highlight known Au targets with improved clarity. The formation mechanism of the recorded Au anomalies is uncertain, but may involve physical enrichment of Au in the soil during pedogenesis with subsequent in-situ formation of (EL soluble) Au halide complexes. The strength of such apical features is, in part, probably a function of the minimal depths to mineralisation which characterise El Mozo and Llano Largo. Oxidation halos formed by volatile non-metallic elements such as Cl and Br may, therefore, provide more valuable EL pathfinders for more deeply concealed epithermal targets.