Geochemical prospecting in complex sample media-multivariate data analysis of indirect observations (PLS-regression between modal mineralogy and geochemistry)

Geochemical exploration in secondary environments can be viewed as a particular manifestation of indirect geological observation. Geochemical anomalies in complex sample media reflect dispersion signatures, generally much disguised by secondary or higher-order mechanical and physico-chemical processes such as mixing, comminution, dilution, (re)transportation, weathering etc. Such complexities often make a thorough understanding of the origin of any particular sample type difficult ot obtain. The objective of data analysis in this context is to convert the geochemical data into a meaningful “signal”, particularly useful for prospecting, and other, in this case irrelevant, variability or “noise”. The experience of the last decades of practical exploration has clearly shown that statistical as well as geographical geochemical anomaly patterns are multi-element signatures. Using suitable multivariate statistical procedures (in the present case principal components modelling), it is possible to simultaneously define both a background data model and to quantify multivariate geochemical anomalies. This type of data analysis is guided very strongly by geological interaction, in which the emphasis is on modelling the background population(s), coupled with geographic plotting facilities. This outlier-screening facility is critical for many types of geochemical data evaluation. An example of this approach is described below. Another application of indirect multivariate data analysis is represented by PLS (Partial Least Squares) regression, which is a supervised pattern recognition and regression technique. We use it here to predict modal scheelite occurrences from regional stream-sediment data.     

The partitioning of copper among selected phases of geologic media of two porphyry copper districts, Puerto Rico

In experiments designed to determine the manner in which copper is partitioned among selected phases that constitute geologic media, we have applied the five-step sequential extraction procedure of Chao and Theobald to the analysis of drill core, soils, and stream sediments of the Rio Vivi and Rio Tanama porphyry copper districts of Puerto Rico. The extraction procedure affords a convenient means of determining the trace-metal content of the following fractions: (1) Mn oxides and “reactive” Fe oxides; (2) “amorphous” Fe oxides; (3) “crystalline” Fe oxides; (4) sulfides and magnetite; and (5) silicates. An additional extraction between steps (1) and (2) was performed to determine organic-related copper in stream sediments.The experimental results indicate that apportionment of copper among phases constituting geologic media is a function of geochemical environment. Distinctive partitioning patterns were derived from the analysis of drill core from each of three geochemical zones: (a) the supergene zone of oxidation; (b) the supergene zone of enrichment; and (c) the hypogene zone; and similarly, from the analysis of; (d) soils on a weakly leached capping; (e) soils on a strongly leached capping; and (f) active stream sediment.The experimental results also show that geochemical contrasts (anomaly-to-background ratios) vary widely among the five fractions of each sampling medium investigated, and that at least one fraction of each medium provides substantially stronger contrast than does the bulk medium. Fraction (1) provides optimal contrast for stream sediments of the district; fraction (2) provides optimal contrast for soils on a weakly leached capping; fraction (3) provides optimal contrast for soils on a strongly leached capping.Selective extraction procedures appear to have important applications to the orientation and interpretive stages of geochemical exploration. Further investigation and testing of a similar nature are recommended.     

Petrologic and geochemical characteristics of “barkinite” from the Dahe mine, Guizhou Province, China

Although “barkinite” has long been studied by many geologists, its geochemical characteristics and environment of deposition are still not known in detail. In order to study the petrography and geochemical characteristics of “barkinite”, coal samples from two Permian coal seams were taken from the Dahe mine, Guizhou Province. The samples were separated into maceral fractions, and then analyzed by microscopical, isotopic, Rock-Eval, and geochemical methods. The microscopical results indicate that “barkinite” occurs as four main types. According to their relationship to other maceral groups, “barkinite” is ostensibly formed under variably dry–wet or oxidizing–reducing conditions. The extract yield, isotope data and Rock-Eval values of “barkinite” are different from other macerals. Microscopical and geochemical results indicate that “barkinite” forms part of the liptinite group.     

Magma in forearcs: implication for ophiolite generation

Forearc areas (“non-volcanic” arcs) of contemporary island arcs at convergent plate boundaries contain magmatic rocks. Geological evidence, seismic profiles, heat flow data, density considerations and petrological and geochemical arguments suggest that a forearc tholeiitic association (FAT) (containing high-Mg calc-alkaline andesites) is present in “non-volcanic” arcs at some stage of island-arc development. The fractionated, as well as primitive magma, is unable to penetrate low-density sediments and underplates thick piles of unconsolidated accreting rocks. The underplating causes upwelling. The occurrence of magma in forearcs provides an alternative interpretation for the tectonic setting of some ophiolitic masses. Rather than “ocean-ridge formation” and later “obduction” it offers an autochthonous (island-arc bound and geologically-substantiated) interpretation for the ophiolite suite.     

Identification of diagnostic geochemical alteration in the wallrocks of archean volcanic-exhalative massive sulfide deposits

The present investigation is concerned with the identification of diagnostic lithogeochemical alteration signatures around volcanic-exhalative massive sulfide deposits in the Superior Province, with the overall objective of deriving lithogeochemical criteria, applicable in the search for new deposits of this type.Previous work on these deposits has indicated that, in general, the footwall alteration halo is marked by iron and magnesium enrichment, and calcium and sodium depletion. These features are often only detectable if the over-riding effects of igneous differentiation are compensated. It is apparent that the relative contribution of individual elements to the geochemical alteration varies from deposit to deposit, preventing the recognition of any universal geochemical alteration criterion.The role of discriminant analysis has been examined to establish the possibility of the technique indicating a more reliable expression of geochemical alteration. Discriminant analysis establishes the optimum weighted combination of variables to distinguish two or more populations from each other, in this case mineralized from barren environments. The application of the procedure to the data relating to the composition of wall rock associated with eight volcanic-exhalative massive sulfide deposits has drawn attention to the existence of two distinct types of alteration. The Joutel and Poirier deposits are characterized by Fe₂O₃, MgO, Zn and Ag enrichment, and CaO and Na₂O depletion; this alteration style has been termed the “Joutel” type. At the South Bay, Sturgeon Lake and Mobrun deposits, Na₂O is also strongly depleted, but Fe₂O₃ and MgO are usually depleted and K₂O is strongly enriched; this alteration style has been termed the “South Bay” type. Both of these alteration styles are displayed at the Mattabi and East Waite deposits. “Joutel” type alteration appears to be in close spatial association with discharge vents, while “South Bay” alteration is more laterally widespread and is representative of at least one deposit thought to be formed distally from its associated discharge vent.These geochemical signatures are more strongly expressed in pyroclastic rocks, and andesites, relative to massive rocks, and rhyolites.The geochemical alteration patterns delineated in this way constitute significantly larger exploration targets than the readily observable mineralogical alteration haloes.Results of the current investigations indicate that the mineralizing processes associated with Archean volcanic-exhalative massive sulfide deposits have given rise to more than oversimplification to aim exploration at the detection of a single type of response. The application of discriminant analysis provides a potential means of identifying and comparing as many responses as are present at the deposits studied. In this respect it is superior to any univariate statistical method, and has considerable application in exploration.     

Geochemical hydrocarbon exploration — a new/old exploration tool

The search for petroleum has evolved into a highly sophisticated technology where today almost every scientific discipline known is being brought to bear upon the endeavour. Yet, the use of geochemical hydrocarbon exploration remains a peripheral exploration tool. The trend toward scientific integration has led the petroleum explorationist to the point of being a specialist. It would seem that our petroleum scientists have focussed their interests mainly on the investigation of principles and less on their ultimate purpose of discovering new and larger oil and gas reserves. So, it is not by chance, that leading geochemists have been speaking more and more freely of the necessity to integrate our tools of exploration and thereby do a better job. The theoretical basis for hydrocarbon geochemistry is complex, and, as with all exploration tools, the problems and difficulties of interpreting the data will never be completely eliminated.This article considers the importance of using the ΔC method in geochemical hydrocarbon exploration which has been employed successfully for over 40 years. The addition of carbon-isotope ratios and trace-element analysis to this method has added a new dimension to geochemical hydrocarbon exploration. The theoretical basis of the ΔC method has been presented earlier by the author and will only be touched upon briefly here.Very simply, the basis of all geochemical hydrocarbon exploration is based on the much debated premise that the lighter hydrocarbon gases and their components migrate vertically from a trap through the overlying sedimentary pile to the surface. Upon reaching the surface, through oxidation, they leave their signatures in one form or another that can be detected by physicochemical methods. These physicochemical signatures are discernable as “geochemical haloes”.From soil samples, collected from 2–3 m deep, what is measured is the result of absorption and adsorption by soil particles that are altered to CO₂ by oxidation and form a unique, stable, carbonate system with the surface and near-surface material. This is unlike other carbonate systems and when subjected to a differential thermal technique, dissociates into CO₂ surface material is cumulative and indicates where maximum hydrocarbon leakage has taken place over the life span of the material sampled. It is durable and unaffected by pressure and temperature variation or recent hydrocarbon contamination.Values are expressed in terms of millivolts which are proportional to the CO₂ given off by the dissociation of the carbonate system under standard conditions. Frequency curves are constructed for all values for the determination of significant contour levels above the normal geochemical background for mapping.After significant ΔC anomalies are located, they can be further verified by use of carbon-isotope ratios. As methane migrates to the surface from underlying hydrocarbon accumulations, there is a progressive selection or fractionation that causes enrichment of the carbon-13 isotope. The methane, thus reaching the near-surface, is isotopically lighter. When oxidized in accordance with the equation CH₄ + 2O₂ → 2H₂O + CO₂, the carbon having been converted to carbon dioxide, is taken up in the pore-filling carbonate cements that are found in the near-surface soils and sediments.High carbon dioxide values (ΔC) in the geochemical halo are related the δ ¹³C carbon-isotope ratios from underlying hydrocarbon accumulations. This is observed over fields containing hydrocarbon accumulations where δ ¹³C values in the pore-filling carbonate cements become increasingly negative (lighter) toward the crests of traps (i.e. exhibiting lower ΔC values). This indicates enrichment of ¹²C relative to the PDB standard. Whereas, positive values of δ ¹³C indicate depletion in ¹²C or enrichment in ¹³C (i.e. exhibiting higher ΔC values away from the crests of the traps).The observed ΔC anomalies and δ ¹³C anomalies leave an indelible pattern in the near-surface sediments and soils which are herein referred to as geochemical hydrocarbon haloes.Trace-element associations, that form organometallic compounds, are found “haloed” or concentrated over or around underlying hydrocarbon reservoirs. These associations seem to have occurred from vertically migrating methane that has acted as a “carrier” sweeping up the trace elements on the pathways to the surface. Vanadium, nickel, chromium, iron, cobalt, copper, manganese, strontium, barium are various trace element ratios seen to also halo and indicate subsurface hydrocarbon accumulations.An example presented from the Ocho-Juan Field, a producing reef field, located in Scurry and Fisher Counties, Texas shows that the combination of ΔC, δ ¹³C and trace-element analysis from near-surface soil sampling is a significant step forward in improving geochemical hydrocarbon exploration methods.     

Surface organic geochemical prospecting for hydrocarbons: multivariate analysis

A database of analyses of C₁ and C₇ hydrocarbons from an oil and gas producing region in Mexico has been assembled from gas samples collected at depths of 3, 15 and 30 meters from surficial holes drilled in traverses over producing and barren structures. The surface consisted of subtropical swamps; depth to structure was 3500 to 5800 meters.Hydrocarbon analysis from six structures (three producing and three barren) selected from the database were subjected to multiple discriminant function analysis to produce a retrospective statistical test of the ability of geochemical prospecting to distinguish producing from non-producing structures. The hydrocarbon spectra from 3 meters depth yielded ambiguous results; those from 30 meters produced clear distinction between barren and producing structures. Further, the discriminant functions established a base of geochemical characteristics, founded on known areas (retrospective), to which additional unknown areas (prospective) may be compared for classification. This suggests a bootstrapping approach to exploration in which an increasing number of “known” results can be used to continually update and refine the predictive power of the discriminant function.This indicates the practical ability of a combined geochemical-multivariate statistical prospecting approach as an exploration tool, particularly within a single geochemical/geological province. Geochemical prospecting, perhaps with relatively deep (30 m) penetration, combined with multivariate data analysis is a rapid, potent and relatively inexpensive additional tool for petroleum exploration.     

Alluvial gold in Kalimantan, Indonesia: A colloidal origin?

Extensive placer gold deposits occur in Quaternary palaeochannels in the Ampalit and Cempaga Buang drainage basins near Kasongan, Central Kalimantan, Indonesia. Broad interfluvial Pleistocene terraces surrounding the drainages also contain significant amounts of placer gold. The “channel” and “terrace” gold deposits together cover an area in excess of 180 km².Exploration for gold at Ampalit followed traditional alluvial methods, and assumed that mechanical and gravitational factors were the principal mechanisms affecting gold accumulation and concentration. Gold was considered to be physically reworked from terraces and redeposited in the present drainage channels or underlying, laterally displaced, palaeochannels. However, a comparison of gold grains from the Ampalit drainage channel and adjacent terraces indicates that gold grains in the drainage channels are possibly of colloidal origin and not mechanically transported to their present domain.The morphology of gold grains from the Ampalit drainage is compared with grains from adjacent terraces, using scanning electron microscopy and atomic force microscopy. The latter procedure allows for nondestructive analysis to give true three dimensional surface topography down to nanometre resolution. Evidence from force microscopy supports a colloidal origin for gold aggregates.The average purity of gold produced from the Ampalit dredging operation is 970 fine (970/1000) and the majority of examined gold grains extracted from beneath the drainage channel have a purity of 998 fine. This unusually high degree of purity suggests a selective dissolution/aggregation mechanism. We propose that gold is transported downward and laterally in groundwater percolating through the terrace sands and gravels to the current drainage as a humic acid-stabilised colloid. As the pregnant groundwater migrates toward the present drainage channels, it encounters a sleep chemical gradient and the colloid aggregates. The aggregation process occurs near clay zones within palaeochannel sands and gravels beneath the present river sediments. Here the colloidal aggregates form small grains (usually <1 mm) of extremely high purity.Today, the inherently unstable gold deposits at Ampalit are in a state of both aggregation and dissolution. Identification of low energy zones, location of point bar lags in palaeo and recent drainage channels, and the extrapolation of areas of low energy are not solely valid as exploration guides for gold accumulation in this environment. Exploration methods that also recognise ground water migration and composition, and the geochemical controls of dissolution and aggregation, will improve the ability to identify ore accumulations, thus contributing to improved economics of mining these deposits.     

Characterisation of brown coal humic acids and modified humic acids using pyrolysis gcms and other techniques

It has been proposed that Victorian brown coal can be considered as a two-component structure — a lignocellulosic “host”, containing various amounts of weakly bound or entrapped “guest” material together with very small amounts of inorganic and/or mineral matter. The latter predominantly consists of wax esters and/or terpenoid material. In this paper we describe attempts to gain structural information regarding the more complex, “host” component of the coal. Our initial model compound has been humic acid that can be readily obtained from the coal by alkaline extraction. It has been found that “pure” humic acid, free from material associated with the “guest” components of the coal, can be obtained by a highly selective, low-yielding alkaline extraction. This humic acid has been studied by nmr spectroscopy and pyrolysis gas chromatography-mass spectroscopy (py-gc/ms). The products arising from py-gc/ms have been compared with those obtained from similar pyrolysis of whole coals. Alkylation of humic acids using alkyl halides in the presence of base has been successfully carried out and reactivity of the resulting materials compared with those of the parent coal and humic acid.     

Comment on “Reinterpretation of Cl data: physical processes, hydraulic interconnections and age estimates in groundwater systems” by E. Mazor

Mazor (1992) has reinterpreted several previous ³⁶Cl studies. The studies he revised used extensive physical hydrogeological data to aid in interpretation of the ³⁶Cl measurements. Major ion chemistry and other isotope tracers were considered in order to evaluate the groundwater geochemistry. The studies then used simple geochemical models to account for Cl behavior in the subsurface. The result of these ³⁶Cl dating studies was in reasonable agreement with both numerical models of the aquifer systems and with independent geochemical studies.Mazor (1992) has reinterpreted these studies based on the assumption that spatial variation in chemical and isotope data should be attributed to unspecified “discontinuities” in the flow regime. The conceptual models of aquifer hydrodynamics resulting from this approach differ radically not only from the previous ³⁶Cl interpretations, but also from the findings of virtually all previous hydrogeological and geochemical investigations. Although Mazor's “reinterpretations” are provocative, he does not show how they explain the data of the numerous previous studies better than the conceptual models presented by the authors of those studies, nor has he demonstrated that his new models are consistent with the fundamental physical laws governing groundwater flow. Until this is satisfactorily accomplished I will continue to prefer the original ³⁶Cl interpretations.     

Geochemical exploration for uranium and other metals in tropical and subtropical environments using heavy mineral concentrates

The problems of carriage mechanisms have for long bedevilled the exploration geochemist, and only recently has sequential analysis indicated the relative importance of various mechanisms. A commonly held view is that metals are somehow scavenged by clay minerals. This is demonstrably not so. There is no “plating” process possible. The importance of coatings and heavy mineral species is illustrated with reference to existing literature and other short case studies.A general view of geochemistry in mineral exploration is presented, with particular reference to uranium exploration in the wet tropical environment. Examples are taken from Indonesia and Sri Lanka. These are complemented by results of various short projects in North Queensland, New South Wales and in Timor. A variety of elements has been examined, notably Au, Sn, Ag, As and Cu, Pb, Zn and some of the more interesting behavioural characteristics have been reported.These data indicate that a great enhancement of the anomalies for most of these elements can be expected from heavy mineral concentrates, relative to the convential minus 80 mesh fraction or the like. In fact, U, Sn and Au anomalies may be lost in the sieving process. Many failures of exploration geochemistry may be explained by referring to the role of heavy minerals. Resampling of areas, which have not originally shown anomalies with conventional methods, has produced anomalies using heavy minerals. Hitherto unsuspected gold provinces have been shown to exist, and areas within historically goldbearing regions have been found to be anomalous where no pre-existing workings occurred.Previous areas not showing positive results might well be favourably resampled. The elements from a weathering deposit must go somewhere. It is not the principle which fails, but the failure to select the most suitable medium or the most appropriate or enlightened analytical technique.Some careful field procedures are described and a few practical hints are given, predominantly with reference to broad reconnaissance and early follow-up phases of exploration, (the “super-stratégique” and “stratégique” phases).It is suggested that combinations of techniques will produce a better understanding of elemental dispersal patterns. No single approach can be expected to be adequate considering the number of parameters — some not fully understood — which operate on the sampling medium.     

Extraction of uranium ions from water: a rapid and convenient method using prepackaged ion exchange resins

Ion exchange resins are used successfully to extract and concentrate uranium ions from aqueous solutions although the procedures are time consuming. They utilize rather cumbersome resin columns, and consequently they have found little practical application in large geochemical surveys of isolated areas. An alternative approach using resin packages is proposed. The “package” is a teabag — convenient, cheap, disposable, and readily sealed. Laboratory and field tests indicate that the method combines simplicity, speed and economy with excellent precision and detection limits. Although the packaging procedure was designed specifically for the extraction of uranium from natural waters under field conditions, the method can be modified to extract elements other than uranium and presents a viable alternative to resin columns in a standard laboratory.     

Evaluation of lake sediment surveys using the relationship of metal tenor to organic content

In geochemical surveys, including those of lake sediments, it is convenient to classify logarithmic cumulative frequency distributions of elements as anomalous, background, or intermediate. The third, and commonest, group presents the dilemma - Is a given distribution in that group tending towards an anomalous or a background distribution? Data from a series of surveys suggest that the relationship of loss on ignition to metal tenor can be used as an indicator of an element's “potential” or “availability” in the region of the survey. In turn, increased availability implies an anomalous source, such as an ore deposit. Areas with the best potential are considered to be those where logarithmic cumulative distributions of particular elements have the same or greater positive slopes than the associated loss on ignition distribution. The method does not define areas within the survey that can be considered more anomalous, only whether or not the given survey area exhibits a greater than expected concentration of a given element.     

Application of limited fuzzy clusters to anomaly recognition in complex geological environments

In stream sediment and soil surveys, samples represent mixtures of components from different geological environments. Such mixed samples are misclassified when using conventional “hard” cluster methods. In fuzzy clustering, each sample is allowed to belong to several clusters. Similar to element concentrations, these cluster contributions can be displayed in contour maps (e.g. kriging maps). The amount of an element that is explained by the cluster contribution and element residuals can be calculated. The modified fuzzy clustering algorithm called “limited fuzzy clusters” used in this paper avoids negative residuals.Stream sediment data of Sierra de San Carlos, Tamaulipas, Mexico are used to demonstrate the possibilities of limited fuzzy clustering in geochemical exploration and mapping. From the different drainage systems, 681 stream sediment samples were taken and analyzed for 24 elements. A nineteen-element data set was used to calculate limited fuzzy clusters and element residuals. The contribution values for the clusters and element residuals are displayed in contour maps. All geological units were outlined by the cluster contributions. Extended anomalies are characterized by their own cluster. Small anomalies are clearly identified from the element residuals.     

Stromatolites — the challenge of a term in space and time

Several definitions of stromatolites are discussed and Kalkowsky's most important statements about stromatolites are translated from German to English. A new definition for stromatolites is proposed, namely “Stromatolites are laminated rocks, the origin of which can clearly be related to the activity of microbial communities, which by their morphology, physiology and arrangement in space and time interact with the physical and chemical environment to produce a laminated pattern which is retained in the final rock structure”. Unconsolidated laminated systems, clearly related to the activity of microbial communities and often called “recent stromatolites” or “living stromatolites”, are defined as “potential stromatolites”.The main microbial activities which are important in the formation of potential stromatolites and stromatolites are described and examples of stromatolites of various types, including iron stromatolites, are also described.     

A study of the kinetic parameters of individual macerals from Upper Permian coals in South China via open-system pyrolysis

A unique Upper Permian coal, Leping coal, is widely distributed in South China. The coal samples studied in the paper were collected from two mines in the Shuicheng coalfield of Guizhou Province, southwest China. The geochemical works including coal petrography, maceral content, Rock–Eval pyrolysis, and kinetic modelling of hydrocarbon-generating have been carried out on whole coal and individual macerals. The higher contents of volatile matter, elemental hydrogen, and tar yield, and the high hydrocarbon generation potential of the Leping coals are attributed to their high content of “barkinite”, a special liptinite maceral.The hydrocarbon generation potential of “barkinite” (S₂=287 mg/g, hydrogen index (HI)=491 mg/g TOC) is greater than that of vitrinite (S₂=180 mg/g, HI=249 mg/g TOC), and much higher than that of fusinite (S₂=24 mg/g, HI=35 mg/g TOC). At the same experimental conditions, “barkinite” has a higher threshold and a narrower “oil window” than those of vitrinite and fusinite, and consequently, can generate more hydrocarbons in higher coalification temperature and shorter geological duration. Data from the activation energy distributions indicate that “barkinite” has a more homogenous chemical structure than that of vitrinite and fusinite. The above-mentioned characteristics are extremely important for exploring hydrocarbon derived from the Leping coals in South China.     

An investigation of Malaysian granitic rocks as suitable sources of feldspar

Medium- to coarse-grained leucocratic granitic bodies containing more than 60% feldspar and less than 10% mafic minerals are found to be appropriate and potential source materials of local feldspar. Out of the 72 granite quarries/outcrops studied in Peninsular Malaysia, 31 have been identified as “ideal” sources of feldspar conforming to the “preferred” feldspar specification of >18% Al₂O₃, >11% (Na₂O+K₂O) and <0.3% Fe₂O₃. A feldspar recovery efficiency exceeding 60% was achieved in this study. Despite the positive and encouraging indication that the extracted feldspar samples of different chemical composition are found to be suitable for the general purpose of making ceramic bodies and glaze, the chemical content of the feldspar, nevertheless, could be critical for the manufacture of specific end products. At 1250°C all extracted feldspar samples were fused; however, at the lower temperature of 1170°C feldspar samples extracted from some “Central Belt granites” remained unfused. The Eastern Province granites generally yielded feldspars which show better fusion characteristics i.e. (unblemished) than those extracted from the Main Range Province. A valuable by-product of the feldspar extraction process is silica sand.     

Evaluation of biogeochemical prospecting methods in the search for sulfide deposits in the Appalachian piedmont, Virginia, U.S.A.

Soil and stream sediment sampling have been the primary geochemical exploration tools in the Appalachian piedmont to date. However, the great thicknesses of soil and saprolite found in the region coupled with the dense vegetation frequently encountered favor biogeochemistry as an alternative or supplemental method since deep-rooted plants sample closer to bedrock. To evaluate this method, an orientation survey was performed in which soils and vegetation at 17 sites north of Mineral, Virginia, were sampled and analyzed for Ag, Cd, Cu, Pb and Zn. The traverse included stations over the host rocks of massive sulfide mineralization, as well as over apparent “barren” country rock. Samples were analyzed by atomic absorption spectrophotometry using standard digestion and analytical techniques.Both A- and B-horizon soil metals generally appear to be reliable indicators of mineralization, with soils developed over sulfides showing up to three-fold enrichment in metal content relative to the average soils developed on the country rock. Correlation of metal concentrations in vegetation to soil metal concentrations reveal plant concentrations expressed on a dry-weight basis correlate stronger and more frequently to soil metals than do ash-weight concentrations. Copper shows some promise in selected organs and species, Ag appears fair but data are limited to one organ of one species, and plant Pb seems totally unresponsive to soil metal concentrations perhaps because foliar absorption is an important plant uptake mechanism here. However, Zn and Cd in organs of the oak group, especially mature leaves and twigs of the current year's growth show the greatest promise as prospecting tools. They correlate well with soil metals and when compared directly to the geology they reliably reflect mineralization. Although results using White oak were slightly less profound than those obtained from the Black-Red oak group, White oak may be preferred as it is a single, more widespread, easily-identifiable species. Copper and especially Zn although essential elements to plants, do not appear to be “difficult” elements for biogeochemical prospecting in the Appalachian piedmont.     

Porphyry copper deposits of the CIS and the models of their formation

Deposits of the “porphyry” family (essentially porphyry copper and gold-porphyry copper, gold-bearing porphyry molybdenum-copper, gold-containing porphyry copper-molybdenum and porphyry molybdenum deposits) are associated in time and space with granitoid magmatism mainly in Phaerozoic volcano-plutonic belts. Whatever their age, the deposits belong to two types of belts: basaltic belts, representing axial zones of island arcs, or andesitic belts formed within active continental (Andean-type) margins.The petrochemistry of ore-bearing magmatism related to the nature of the substratum of volcano-plutonic belts, reveals a number of essential characteristics, both in composition and zonation of wallrock alteration and ore mineralization. These characterisics enabled previous researchers to establish four models of porphyry copper deposits based on their lithologic associations, e.g., “diorite”, “granodiorite”, “monzonite” and “granite”.Pophyry copper deposits are thought to be the product of self-generating “two-fluid mixing” ore-magmatic systems. Porphyry intrusions are pathways for energy and metals from deep-seated magma chambers, of which the upper mineralized parts are accessible for observation. The relationship between magmatic fluids and meteoric water participating in the ore-forming processes (dependent on the structural-petrophysical conditions of formation), provide a subdivision for the porphyry copper ore-magmatic systems into three types: “open”, “closed” and “transitional”.Concurrently, a common trend in the evolution of the systems has been established, from a nearly autoclave regime of structural-and ore-forming processes to a gradual increase in the importance of hydrothermal recycling. The completeness of the OMS (ore-magmatic system) development according to this scheme, which determines the existence of various OMS types, depends on many factors, the most important being the depth of formation of porphyry intrusive bodies, the petrophysical peculiarities of the host rocks and the palaeohydrogeological conditions of ore deposition.Although rock fracturing (especially defluidization: second boiling) and contraction are caused by the same mechanisms, the stockwork growth in “open” and “closed” systems, relative to the wall rock, takes place in opposite directions, primarily due to different petrophysical parameters of the near-stock environment.In “open” systems structural and ore metasomatic processes are finalized. Fractures extend progressively from porhyry stocks into the marginal parts of the intrusive framework and extension of large-scale recycling of magmatic and activated meteoric water, in the same direction, result in the formation of ore-bearing stockworks. These are large in all dimensions, cover mainly hanging-wall zones and are characterized by clearly defined concentric mineral zoning and extensive geochemical haloes.In a “closed” OMS with centripetal growing fractures, hydrothermal convection is stunted. The vertical extension of recycling cells is restricted and the volume of meteoric water involved in circulation during the period of ore deposition is relatively small. As a result, relatively small intra-intrusive lenticular stockworks are developed which are characterized by close co-existence of several generations of mineralization with fragmentary preservation of the earliest ones. These are characterized by the elements of “reverse” zoning, increased density of the veinlets and metal content, as well as poorly developed hanging-wall dispersion haloes.