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CHAPTER 3.

geochemical Prospecting
Jeffrey A. Jaacks, L. Graham Closs, and J. Alan Coope

Exploration geochemistry, or geochemical prospecting, development of analytical and computer technology, and
includes any method of mineral exploration based on the sys- improvements in field transportation have made geochemis-
tematic measurement of one or more chemical or chemically try one of the more effective and widely applied exploration
influenced properties of a naturally occurring material. The disciplines. Analytical capability is such that relatively rapid,
property measured is most commonly the trace concentration sensitive analysis can be achieved for virtually all metals of
of some chemical element or group of elements. The naturally economic interest. New technological advances are expanding
occurring material may be rock, soil, stream sediment, glacial our established capability to cost-effectively detect and inter-
sediment, surface water, groundwater, vegetation, microor- pret dispersion patterns related to mineral deposits in a wide
ganisms, animal tissues, particulates, or gases. variety of environments. Recent geochemical research has
focused on detecting ore bodies hidden beneath transported
hiSToRy of geoCheMiCAl PRoSPeCTing overburden and development of geochemical dispersion mod-
It is clear from historical records that the principles of geo- els to aid in the interpretation of anomalies developed in these
chemical exploration have been applied in prospecting over environments (Cameron et al. 2004).
several thousand years. The prospector who panned for gold Through multielement analysis, geochemical data can
and traced the colors upstream to a bedrock source used miner- reveal signatures related to distinct geological units and geo-
alogical observations in a similar way to the modern geochem- chemical processes. This capability, when applied to rock
ist who utilizes sensitive chemical analyses to outline patterns samples, permits geological correlation as well as the more
of dispersion in the surficial environment. Geobotanical indi- precise delineation of otherwise invisible alteration features
cators were recognized as early as the eighth and ninth centu- related to mineralization. When applied to soil and other types
ries. The mid-16th century work by Agricola (1556) describes of samples, multielement data can help outline major geologi-
the analysis of natural waters, springs, and their residues. cal units and the extent of alteration systems, and identify the
Modern methods of exploration geochemistry were first presence of mineralization buried under extensive cover.
used in the early 1930s in the Soviet Union. Shortly thereaf-
ter, the methods were applied in the Scandinavian countries, geoCheMiCAl PRoSPeCTing MeThoDS
particularly Sweden. In North America, the earliest geo- The various components of a geochemical exploration pro-
chemical surveys were carried out between 1938 and 1940 by gram include sampling design, choice of sample media, sam-
H. Lundberg in Newfoundland and in 1944 by H. Warren in ple collection, sample analysis, quality control of analyses,
British Columbia. The first comprehensive geochemical explo- data visualization and evaluation, and interpretation. These
ration studies commenced at the U.S. Geological Survey under components of a geochemical survey are interdependent and
the leadership of H.E. Hawkes in 1947 and at the Geological should be focused on the geologic objective to be achieved.
Survey of Canada with R.W. Boyle in the early 1950s. The Good design and planning (including orientation) and well-
Applied Geochemical Research Group was established at the conducted sampling programs constitute the foundation of
Imperial College of Science and Technology in London in all sound geochemical exploration work (Closs and Nichol
1954 under the direction of J.S. Webb, and in France, research 1989). Inappropriate sample preparation prior to analysis
related to exploration geochemistry began in 1955. can destroy the integrity of the well-chosen sample. It fol-
The successful application and adaptation of geochemi- lows that no matter how accurate and precise the techniques
cal exploration techniques in all parts of the world, the rapid used for analysis or how advanced the statistical treatments

Jeffrey A. Jaacks, President, Geochemical Applications International, Inc., Centennial, Colorado, USA
L. Graham Closs, Associate Professor, Department of Geology and Geological Engineering, Colorado School of Mines, Golden, Colorado, USA
J. Alan Coope, Former Director of Geochemistry, Newmont Exploration Ltd., Denver, Colorado, USA

127
128 SMe Mining engineering handbook

and computer programs used for data handling and interpreta- of dispersion patterns is to conduct an orientation survey.
tion, they cannot resurrect the lost quality and representativity The objective of orientation sampling is to determine and
and restore the decreased probability of exploration success outline the existence and characteristics of dispersion pat-
caused by poor planning, improper field sampling, faulty terns or anomalies associated with mineralization and also
sample preparation, or mismatch between sample media and background levels in similar environmental conditions. The
digestion method. specific sample media used are dependent on a knowledge
of the field area, the prospecting problem, and, if available,
geoCheMiCAl PRogRAM PlAnning previous experience, but may include any of the following:
Experience has confirmed that the success of a geochemical rocks, soils, stream sediments, surface waters, groundwater,
survey depends largely on the correct assessment of all the glacial sediment, lake sediment, vegetation, soil gases, and
natural factors that influence the mobility and dispersion of microorganisms.
the metallic elements of interest. These natural factors, which The orientation survey commonly involves the collection
are described more fully in textbooks by Rose et al. (1979) of a number of relatively closely spaced samples over and in
and Levinson (1974, 1980), are the vicinity of known but preferably undisturbed mineraliza-
tion with the express purpose of outlining the dispersion pat-
Physical and chemical properties of the elements or
terns in the available sampling media. This information can
parameters of interest,
then be used to select the most reliable sampling method,
Nature of the geology and mineralization,
sample preparation, and analytical techniques capable of
Geomorphological history of the field area,
detecting similar anomalies under similar environmental con-
Vegetation, and
ditions. The detailed examination of the nature and shape of
Topographic and climatic conditions.
the dispersion patterns invariably yields information on the
These factors are completely interrelated, and any change in principal natural factors responsible for the observed distribu-
one conditionsuch as a geologic change from an acidic to a tion of anomalies. This is a significant aid in the development
basic environment, a local climatic change caused by eleva- of interpretation procedures.
tion, or a topographic change from rolling to mountainous Table 3.4-1 is a synthesis of the important parameters that
terraincan significantly influence element mobilities and can be derived from a properly planned and executed orienta-
the lateral extent of the dispersion from any mineralization tion survey. Based on this information, the optimum physical
type. Consequently, procedures for sampling, sample prepa- parameters (sample depth, sample interval, analytical tech-
ration, and analysis that prove to be satisfactory in one field nique, etc.) for routine surveying can be chosen that neces-
area may be inadequate and unreliable in an adjacent region. sarily take into account the defined dispersion characteristics
The processes of oxidation, weathering, erosion, trans- as well as the physical, logistical, and economic conditions
portation, sedimentation, and diagenesis that characterize the pertaining to the project. Large samples should be taken to
surficial environment are too complex to describe in detail provide sufficient material for the full evaluation of the param-
in this summary. The physiochemical conditions determine eters listed in Table 3.4-1, and representative samples should
whether the weathering products of mineralization disperse be collected from nonmineralized areas to adequately define
either in solution in a hydromorphic form or in a solid or background conditions and contrast of anomalies, where con-
clastic form. The low pH, high Eh conditions of the acid- trast is defined as the ratio between background and threshold
weathering environment (e.g., oxidizing massive sulfides) value of anomalous samples.
promotes the solubilization of many base metal and other A survey conducted over gold-silver vein mineralization
elements and their more widespread hydromorphic disper- at Mount Nansen in the Yukon Territory of Canada (Coope
sion in surface and groundwaters. Alkaline conditions devel- 1966) illustrates the application of the orientation approach.
oped over a weathering limestone or in a semiarid climatic Detailed profile sampling of soil and overburden exposed in a
condition prohibit or arrest this hydromorphic dispersion. trench across virgin mineralization produced patterns of lead,
Under these conditions, the insoluble metal particles dis- antimony, and zinc, as illustrated in Figure 3.4-1. It is apparent
perse mechanically to form clastic patterns. from these patterns that the dispersion behavior of lead and
A series of publications sponsored by the Association antimony is similar but quite contrasting with the patterns for
of Exploration Geochemists develops conceptual models zinc. All metals have been influenced by downslope move-
based on conditions in Canada (Bradshaw 1975), Scandinavia ment in the overburden, but the zinc pattern is compatible with
(Kauranne 1976), the Basin and Range province of the western dispersion in solution along the bedrock surface. Examination
United States (Lovering and McCarthy 1978), Australia (Butt of the patterns also indicates that near-surface sampling (0 to
and Smith 1980), tropical and subtropical terrains (Butt and 300 mm, or 0 to 12 in.) would not reliably indicate the min-
Zeegers 1992), and arctic and temperate terrains (Kauranne et eralized vein. It was concluded that a sample depth of 460 to
al. 1992). These conceptual models describe the principles and 610 mm (18 to 24 in.) and a sample interval of one-third the
mechanisms of formation and configuration of anomalies and anomaly width at this depth (5 m, or 15 ft) were the optimum
dispersion patterns revealed through geochemical exploration parameters necessary for routine surveying (Figure 3.4-2).
surveys in these regions. This format has been expanded in the Observation of these sampling criteria led to the discovery of
Handbook of Exploration and Environmental Geochemistry several previously unknown veins.
published by Elsevier, currently with 11 volumes covering The soil profile interval in an orientation survey over
many aspects of geochemical exploration. more extensive types of mineralization will be proportion-
ately larger than the intervals chosen for narrow-vein-type
geoCheMiCAl oRienTATion SuRveyS mineralization.
When contemplating a geochemical survey in a new region, The sample intervals employed in orientation sur-
the most reliable method of determining the extent and nature veys will vary according to the anticipated size of the target
geochemical Prospecting 129

Table 3.4-1 Parameters to be derived from a properly planned orientation survey


Rock Soil Sediment Water Biogeochemical gas
Shape, extent, reproducibility, homogeneity, and controls of geochemical patterns
Most suitable indicator elements and best analytical methods
Reproducibility of sampling and analysis
Sampling pattern and density
Amount of sample required
Required field observations
Possible contamination sources
Effects of topography, drainage, vegetation, geology
Seasonal or temporal variations
Optimum sampling depth or horizon Sampling depth
Optimum sampling fraction Sampling volume
(size, heavy minerals, organic fraction)
Sample material Nature of overburden Correlation with Fe-Mn Optimum material (ground Optimum species Effect of soil type
(rock, vein, etc.) (residual vs. transported) oxides or surface) (distribution, ease of
Mechanism and direction anomaly recognition, Effect of soil depth
ease of sampling, and
depth of root system)
Type of sample Soil profile development Correlation with Control of water flow Effect of temperature
(grab, channel, organic matter
etc.) Depth variation of indicator Difference in aquifers Effect of soil moisture
elements
Effects of Relation to recharge areas Part of plant to be
weathering and sampled
alteration
Applicability Variation with depth Effect of aspect (sunlight,
of mineral shading)
separations
Mineralogy Variation with type of lake
(sulfides, biotite,
limonite, calcite,
etc.)
Source: Adapted from W.B. Coker, personal communication.

NE 10 Surface Slope SW

100
Pb 100
100
500 1,000 Amphibolite
500 500 500
1,000 ?
Acidic Schist 100 0 5 10 ft

Scale
0 1 2 3m

100 100
100

500
Zn 100 1,000
1,000
Acidic Schist 500
1,000 1,000 Amphibolite
? ?

5
Sb
5 5
18 36
36 18 Amphibolite
Acidic Schist ? 5
?

Surface of Bedrock Geochemical Contour (Pb, Zn, and Sb Values in ppm) 100
Sample Location
Location of Mineralization as Indicated by Picket Marker

Source: Coope 1966.


figure 3.4-1 Profile distribution of lead, zinc, and antimony over mineralized vein, Mount
nansen area, yukon Territory
130 SMe Mining engineering handbook

0 5 10 ft
x Location of Mineralization as Scale
1,100
Indicated by Picket Marker 0 1 2 3m
1,000 (80 mesh analyzed)
18
800 16
Pb and Zn, ppm

14

Sb, ppm
600 12
10
400 Zn 8
5 ppm Sb Pb 6
200 150 ppm Pb + Zn 4
100 x 2
x Sb

Source: Coope 1966.


figure 3.4-2 Profiles of lead, zinc, and antimony concentrations in soil over a mineralized vein at
45- to 60-cm depth, Mount nansen, yukon Territory

mineralization and the dispersion characteristics of the metals for larger samples. More rigid polypropylene bottles can be
of interest. In areas where no previous experience exists, a utilized in water sampling, and a variety of sampling devices
short interval is recommended so that three or more samples are available for the sampling of gases and particulates.
are collected within the distance spanning the zone of miner-
alization. This interval should then be progressively expanded Collecting Different Sample Media
with distance from the metal source to the limits of the known
Soil
or anticipated dispersion pattern. Samples must also be col-
Soils vary considerably in composition and appearance
lected from nonmineralized areas to establish the background
according to their genetic, climatic, and geographic environ-
range, and sufficient material should be collected at each site
ment. Classified into residual and transported types according
to allow for the determination of optimum size fractions, ana-
to their relationship to their substrate, soils are mixtures of
lytical techniques, and other factors listed in Table 3.4-1.
mineral and biologic matter and may be distinctively differ-
entiated into a series of soil horizons. Residual soils charac-
SAMPle ColleCTion AnD hAnDling
teristically contain detectable dispersion patterns developed
Effective sampling of all surficial media requires well-trained
during the weathering of mineralization in the underlying
personnel capable of recognizing and describing the correct
bedrock, and these patterns are revealed by careful sampling
sample material and the sample site characteristics. Samplers
of appropriate soil horizons. Transported soils present more
should be able to recognize and, if possible, avoid situations
difficult sampling problems, but meaningful sampling is pos-
where contamination from human activity or changes in the
sible in many areas after the genetic origins of the transported
natural physiochemical conditions can produce spurious or
cover are understood.
unusual results. In most situations, these sampling duties
With all but a few exceptions, soils are sampled along tra-
can be undertaken by trained technical personnel with geo-
verses or grids in the follow-up or detailed prospecting stage
chemical exploration experience. For some specialized types
of a geochemical program. Orientation programs define crite-
of surveys, where identification of the correct sample mate-
ria such as sample depth or soil horizon to be sampled, sam-
rial is critical (as in biogeochemical or glacial till sampling
ple interval, and the size fraction for analysis. It is essential
programs), it is prudent to employ qualified specialists (e.g.,
that these criteria be applied consistently through the survey
botanists and quaternary geologists) to conduct orientation
(Hoffman and Thomson 1987).
surveys and instruct and supervise the sampling teams.
Sampling tools vary according to the medium and the
Stream Sediments and Surface Water
field situation. Non-contaminating equipment is essential, and
Stream sediment is one of the more commonly used media
care should be exercised in not only choosing noncontami-
for geochemical reconnaissance surveys. The sediment at any
nating steels for shovels, trowels, augers, and so forth, but in
point in a stream is a natural composite sample of erosional
ensuring that lubricants and adhesives, weldings, and solders
materials from upstream in the drainage basin and will include
are metal free too. This awareness of geochemical cleanliness
clastically, hydromorphically, and biogenically derived prod-
extends to the dress of the sampler, who should avoid wear-
ucts from weathering mineralization. The length of anomalous
ing metal buckles, gold rings, and so forth, and avoid han-
dispersion trains will vary with the nature of the mineraliza-
dling coins, which might lead to contamination by chipping or
tion, source, and physiochemical environment of the field area
transfer of metal on fingers.
or drainage basin. In humid, actively oxidizing environments,
The same caution is necessary in the choice of sample con-
dispersion trains from sulfide-rich base metal deposits may
tainers. Kraft paper (with noncontaminating waterproof glue
extend downstream for several kilometers.
and closures), olefin, and plastic bag containers of appropriate
Active stream sedimentmaterial constantly or most
size are frequently used. Kraft and olefin allow samples to be
frequently washed by stream watersis collected from the
dried without transfer, while plastic bags are commonly used
geochemical Prospecting 131

center of a drainage, avoiding sites that may be contaminated for sampling tills in the 1950s, and this technique is now the
or influenced by bank collapse. In most survey programs, preferred sampling method in modern geochemical explora-
approximately 500 to 1,000 g (1.1 to 2.2 lb) of fine-grained tion programs. Approximately 70% of lodgment till is locally
material are collected from the upper few tens of millimeters derived, and most of the early success with till sampling was
of the sediment. If heavy minerals are to be examined, larger in areas of shallow till cover (<10 m [30 ft]) where the sample
samples from deeper in the streambed are collected from care- medium is reasonably accessible. In the 1960s, lightweight
fully selected sites. In all surveys in new areas, the critical percussion drills, such as the Pionjar and Cobra models,
parameters of sample interval, sediment size fraction, appro- were adapted to collect small samples of till from immedi-
priate analytical procedures, significant anomaly contrasts, ately above the suboutcropping bedrock to geochemically
and background levels are determined through orientation categorize anomalous geophysical features at depths of up to
surveys (Hale and Plant 1994). 2124 m (7080 ft).
In the regional reconnaissance prospecting mode, stream Overburden drilling technology, particularly reverse cir-
sediment surveys can be designed to systematically cover areas culation and sonic drilling, advanced rapidly with the utiliza-
up to several hundred square kilometers. To pinpoint source tion of larger drills in programs for uranium and gold deposits
areas in more detail, anomalous indications of mineralization in glaciated areas. Because most types of gold deposits are not
can be followed up with more detailed sediment sampling. detectable by conventional geophysical methods, lodgment till
Follow-up sampling of seepage areas is particularly effective sampling using overburden drills to depths of 100 m (330 ft)
in delimiting anomalous groundwater sources containing metal has been used routinely in prospecting for gold in the Canadian
derived from oxidizing mineralization. If appropriate, soil Shield through the 1980s. Large samples of till (~10 kg [20 lb])
sampling can be used to define suboutcropping mineralization are recovered in these programs from which the heavy mineral
in the anomalous source areas defined by the sediment survey. fraction is separated and examined both visually and chemi-
Regional reconnaissance can also be achieved by sam- cally for gold and other metals (Averill 2001).
pling the waters of actively flowing streams where metal is The correct interpretation of these data is dependent on
dispersing in solution. A prospecting approach similar to the an understanding of the till stratigraphy and provenance of the
sampling of stream sediments is necessary, collecting waters transported material. The technique is expensive, with com-
in clean 250-mL (0.07-gal) polypropylene or glass bottles. bined drilling, sample treatment, and analytical costs ranging
Sampling of groundwater seepage sites is an integral part from $20 to $50/m ($60 to $100/ft), but it is cost-effective
of stream water surveys. To keep the dissolved metals from in this deep overburden-covered environment where other
adhering to the bottle walls, a few milliliters of acid is routinely methods in gold exploration have not been as successful. In
added to the water samples after collection. Temperature, pH, contrast with the heavy mineral sampling of tills practiced in
total dissolved solids, conductivity, and certain other measure- Canadian exploration, Scandinavian explorers place a greater
ments are commonly made at the sample site. reliance on the 63 m (240 mesh) fraction of till. This frac-
tion has successfully indicated the presence of several types of
Lake Sediments and Lake Water mineralization, including gold.
Lake sediments and lake water sampling have been developed
into effective geochemical reconnaissance techniques in areas Rocks
of Canada and Scandinavia where lakes are common, condi- Rock sampling, or lithogeochemical surveys, comprise sys-
tions are swampy, and/or where stream drainages are inac- tematic sampling of outcrops, trenches, drill cores, or drill
cessible or poorly developed. In low-relief regions, the lake cuttings. As with other types of geochemical surveys, the sam-
sediment medium is dependent on the hydromorphic disper- pling procedures and the sample material collected in litho-
sion of metals into the lake environment through groundwaters geochemical work should be standardized as much as possible.
and the adsorption of this metal onto hydrous oxides and the Lithogeochemical sampling necessarily must take into
organic-rich muds deposited on the lake bottoms. The sam- account the geological environment and the type of mineral
pling focuses on the collection of these organic muds using deposit of interest to the explorer. Very briefly, syngenetic
specially designed sampling devices. In more mountainous lithogeochemical patterns (which developed at the same time
areas, fine-grained clastic dispersion into the lake sediment as the rocks that enclose them) can develop, for example, in (1)
becomes a more important factor. In all areas, satisfactory intrusives genetically associated with specific mineral deposit
sample locations are found well away from lake shores and are types, (2) volcanic stratigraphy where exhalative activity has
reached using boats, float planes, or helicopters. Lake waters dispersed detectable quantities of metals during the formation
are commonly collected at the same sites as the lake sediments of volcanogenic massive sulfide deposits, or (3) the vicinity
(Coker et al. 1979). of sedimentary deposits. The scale of sampling necessary for
detection of these and other types of patterns will be deter-
Glacial Deposits mined by orientation surveys but may include the regional
Extensive quaternary glacial deposits occurring over most of sampling of individual plutons or more detailed sampling of
Canada and the northern United States, northern Europe, and specific parts of an exposed stratigraphic section.
northern Asia have presented major challenges to exploration. Epigenetic lithogeochemical patterns (those developed
As a better understanding of the origin and formation of these long after the rocks that enclose them) can develop as diffu-
glacial sediments has grown, their blanketing presence has sion aureoles in the rocks hosting epigenetic mineral depos-
become progressively less formidable, and effective explora- its or as leakage aureoles along fractures and other structures
tion techniques have been developed. that mark the pathways followed by hydrothermal or ground-
Mineralized boulder tracing in glaciated regions is water fluids prior to and subsequent to the deposition of the
an established technique of the traditional prospector in significant mineral deposits. Both these processes introduce
Scandinavia and parts of Canada. Methods were developed the concept of mineral zoning of geochemical aureoles. The
132 SMe Mining engineering handbook

ratios of the different elements introduced during the mineral- spring growth following a dormant winter season. In hot des-
ization period varies with distance from the principal deposit ert regions, following the exhaustion of available near-surface
according to the properties of these elements and the host water during the dry season, deep-rooted plants will tap the
rocks and the physiochemical conditions at the time of depo- deeper, more metal-rich groundwater.
sition. Leakage anomalies can extend for hundreds of meters These variables make biogeochemical sampling a special-
or feet from a deposit, whereas diffusion anomalies rarely ized exercise. The expertise of an experienced geochemist or
exceed 30 m (100 ft). The scale of dispersion, the presence of botanist is essential during orientation studies and the supervi-
zoning patterns, and the sampling parameters for epigenetic sion of vegetation surveys. Because of the seasonal variations,
geochemical patterns are determined by appropriate lithogeo- biogeochemical surveys must be completed quickly, and sam-
chemical orientation surveys. pling in the spring and fall is generally avoided.
It is clear that surveys designed to detect leakage anoma- The same complexities do not affect the humus or mull
lies will focus on a standardized collection of fault or frac- medium. Dead tissues are not subject to seasonal varia-
ture zones and, possibly, bedding structures. In contrast, the tions, and annual accumulation has an integrating effect.
preferred lithogeochemical sample material for the detection Weathering, leaching, and bacterial decomposition will work
of syngenetic haloes is likely to be unfractured and the scale to diminish the metal contents, but signatures in mull are gen-
of sampling much more detailed. In all instances, geochemi- erally preserved.
cal analysis of lithogeochemical material has the potential of
delimiting dispersion patterns associated with mineralization Soil Gas
beyond visible alteration. Under certain conditions, weathering mineral deposits pro-
duce gaseous emanations that can be detected by specialized
Vegetation and Humus measurements. Radon, for example, is produced during the
Early scientific observers dating from the eighth and ninth radioactive decay of uranium and radium. Survey techniques
centuries recorded that the morphology and distribution of measuring the alpha particle emissions during radon decay
certain plants were affected by the presence of metals in the have been used extensively in the search for uranium. Helium
soils. Such visible variations in a plant species are referred is another gas produced during radiogenic decay and is consid-
to as geobotanical indicators. Many other plants, while not ered by many to be also of deep-seated origin. Mercury-bearing
showing any visible variations, are capable of concentrating minerals, which can include sphalerite and other sulfides, often
metals in their tissues, and the presence of anomalous met- release mercury vapor during oxidation.
als in the soils or groundwater is often reflected in the metal The oxidation of sulfides leads to the generation of sul-
content of leaves, twigs, or other plant organs. These invisible fur dioxide, dihydrogen sulfide (H2S), and carbon dioxide
metal concentrations are known as biogeochemical indicators (CO2). Because of the consumption of oxygen in the oxidation
(Brooks 1983). process, the atmospheric proportions of carbon dioxide and
The seasonal fall of leaves and needles transfers some of oxygen change in the vicinity of oxidizing sulfides, and these
the accumulated metals to the surface soil where they are incor- imbalances can be measured in the soil gas to detect buried
porated in the humus layer. Sampling of this humus (alterna- mineralization. More recently, organic gases have been used
tively known as mull, Ao, or Ah material) by Scandinavians in to define mineralized and alteration zones located beneath
the 1930s revealed its potential for geochemical prospecting. transported cover. Organic gas species are zoned relative to
This is especially true in areas of transported material where mineralization, with heavier reduced compounds occurring
the root penetration of the plant exceeds the thickness of this over ore and lighter, more oxidized gas species occurring at
cover and obtains nutrients from the underlying mineralized the boundaries of mineralization (Klusman 1994).
bedrock and groundwater.
In addition to the direct recognition of geobotanical indi- SAMPle PRePARATion
cators, the most attractive feature of vegetation sampling is Inappropriate sample preparation can completely nullify the
the ability of biogeochemical and mull prospecting to see careful work of the sampler who has invested time and exper-
through thicknesses of barren transported overburden. tise in the selection and collection of representative material.
Plants are complex organisms and so is their metabolism. Furthermore, it is impossible to restore the integrity of the
Different species respond differently to the same conditions, poorly prepared sample by enterprising analytical treatments
and, consequently, some species are more effective biogeo- and interpretational procedures.
chemical indicators than others. Deep-rooted plants (e.g., the
mesquite) are much more effective prospectors of the deeper Drying
groundwater than the shallow-rooted flora of the southwestern Prior to mechanical treatment, surficial and rock geochemi-
U.S. deserts and are, therefore, preferred species in biogeo- cal samples have to be dried. In some climates, this can be
chemical work. Evapotranspiration has been suggested as a achieved by exposure to the sun, but most samples are dried in
mechanism for movement of metals into the nutrient depth of drying ovens. Heating these ovens to temperatures in excess
these plants. of 70C (160F) can lead to the loss of volatile elements (Hg,
Some species preferentially concentrate metals in specific As, Sb) that may be of value to the exploration program.
tissues such as leaves, twigs, bark, or wood. It is therefore Organic samples, including humus, may be dried in a conven-
important to establish the most favorable tissues for sam- tional drying oven or in a microwave oven at temperatures not
pling after a useful species has been identified (Dunn 2007). to exceed 70C (160F).
This complexity is accentuated by the fact that metal uptake
may vary with aspect, and degree of uptake commonly var- Sieving and Crushing
ies with the seasons. In temperate forest regions, accelerated After drying, surficial samples should be agitated and dis-
uptake and higher concentration commonly occur during the aggregated to achieve complete separation of component
geochemical Prospecting 133

particles without crushing. This can be done with a pestle metals of interest are heterogeneously distributed (e.g., as
and mortar or other suitable non-contaminating mechani- with coarse gold), the principles of sampling theory must be
cal device that can be thoroughly cleaned between samples. observed (Pitard 1993). The pulverized whole rock product
In earlier geochemical prospecting work, orientation stud- that is commonly analyzed has a grain size of less than 150
ies on soils, stream sediments, and other surficial materials to 200 mesh. The sample is rarely reduced to this fine grain
revealed that the separation of 80 mesh material for analysis size in its entirety, but, as a general rule, the finer the sample
was appropriate in many surveys. With some elements, such can be crushed or ground prior to sample splitting, the more
as those commonly concentrated in residual minerals (W, Sn) representative the split is likely to be.
and other elements dispersed in weathering products in arid/ The emphasis on gold exploration in recent years has
semi-arid environments, fractions coarser than 80 mesh give focused attention on sample heterogeneity. This has stimu-
superior geochemical patterns with better contrasts. Surveys lated some significant developments in the design and adap-
in glacial till environments benefit from the analysis of the tation of crushing and grinding equipment for improved
240 mesh (63 m) or even finer fractions. Careful size frac- sample preparation. In addition to sample representativity,
tion analysis during orientation will not only indicate the most the geochemist must be concerned with sources of contami-
appropriate fraction for routine work, but the metal distribu- nation in the sample preparation equipment. Grinding plates
tion throughout the sample reveals invaluable information on and blades of different composition are available so that the
metal behavior for interpretation purposes. Sieves must have a obvious contamination from chrome steel, tungsten carbide,
non-contaminating composition. Those most frequently used and other materials can be avoided. Similarly, loss of sample
are made from stainless steel. representivity through smearing of native copper, native gold,
molybdenite, or other soft material on pulverizer plates can
heavy Mineral Separations be avoided in many instances by the selection of alternative
Heavy mineral separations from stream sediment, glacial till, equipment with a different comminuting action.
and rock samples commonly utilize the liquids tetrabromo- Because sample weights analyzed in geochemical work
ethane (specific gravity [sp gr] 2.9) and methylene iodide are small (0.1 to 50 g [0.0002 to 0.1 lb]) compared with
(sp gr 3.3). More recently, solutions of sodium polytungstate, the original sample size, sample homogeneity is important.
with specific gravity ranging from 1.0 to 3.1 according to dilu- Improved mixing can be achieved, when necessary, by care-
tion, can also be used to avoid the disposal issues associated ful blending and the pulverization of coarser fractions to the
with tetrabromoethane and methlyene iodide. Usually these 200 mesh size.
liquid separations are carried out on coarser sample size frac-
tions (e.g., 30 + 80 mesh), but separations can be made on AnAlyTiCAl TeChniQueS
material down to 200 mesh if the metal of interest is present
Analytical Methods
in the finer size fractions. If necessary, heavy mineral concen-
A prime requirement for cost-effective geochemical explo-
trates can be further subdivided by electromagnetic separation
ration surveys is the availability of analytical procedures
into magnetic, paramagnetic, and nonmagnetic fractions and
capable of high productivity, low detection limits, high pre-
analyzed separately.
cision, and acceptable accuracy. These criteria were met in
the 1950s by a series of colorimetric analytical techniques
vegetation Samples
with productivities ranging from 20 to 100 samples per day.
Ideally, vegetation and humus samples should contain no
Technological developments have subsequently led to the
clastic material. Dust on leaves and twigs can be removed by
introduction of atomic absorption spectrophotometry (AAS),
rinsing with demineralized water, but humus material is rarely
inductively coupled plasma (ICP) spectrometry , X-ray fluo-
100% organic. The presence of excessive clastic material may
rescence (XRF), and instrumental neutron activation analy-
dilute or contaminate the metal content of the organic material
sis (INAA) with far greater analytical sensitivity and vastly
and adversely interfere with lower detection limits possible
increased productivity.
on organic material using the neutron activation analytical
These analytical techniques provide accurate, pre-
technique.
cise determinations with detection limits of less than 5 ppb
After drying at temperatures of less than 70C (160F) in
to 1 ppm for many of the elements commonly measured in
a standard drying or microwave oven, vegetation samples are
exploration geochemical surveys. The ICP-mass spectrometer
macerated in a Wiley mill to a 2 mm mesh size. This material
instrument is capable of even greater sensitivity. Comparison
is compressed into either 8.0- or 30.0-g pellets for direct anal-
of some of these analytical methods is shown in Table 3.4-2.
ysis by neutron activation or can be ashed in a muffle furnace
In the minds of the inexperienced, the spectacular ana-
at 450 to 470C (842 to 878F) for approximately 15 hours.
lytical capabilities of these instruments often overshadow
The plant ash is then analyzed in a similar manner to clastic
the critical importance of the sample preparation and sample
sample material.
decomposition stages of sample treatment.
It was emphasized in the preceding section on sample
Rock Samples
preparation that the most informative fraction of a geochemical
Some surveys call for the analysis of specific minerals in
sample may be the heavy mineral fraction, a relatively coarse
rock samples. Such minerals may include magnetite, biotites,
fraction (30 + 80 mesh), a fine fraction (80 mesh), or a very
feldspars, and sulfides that may be concentrated by magnetic
fine fraction (250 mesh), depending on the material being
separation or with heavy liquids from the most suitable size
analyzed or the particular property of interest in a sample. If an
fraction, after appropriate sample treatment (Govett 1983).
improperly chosen solid sample material is correctly analyzed,
Most rock samples collected in geochemical programs
the results can be no better than mediocre in the context of the
are analyzed for their whole rock or trace element contents.
exploration program and may even be misleading.
This requires crushing and pulverizing and, if the contained
134 SMe Mining engineering handbook

Table 3.4-2 Comparison of characteristics of analytic methods


Determinations
Method Capital, $ Multielement per Day Comments
Colorimetry 1 103 No 20100 Very simple; adaptable to field
AAS 2 104 No 500 Easy to set up; several elements can be determined on same solution but not
simultaneously
ICP 13 105 Yes >2,000 Requires skilled analyst to supervise plus computer; sample in solution
XRF 15 105 Yes >1,000 Requires skilled analyst to supervise plus computer; solid sample analyzed
INAA 0.820 106 Yes <3,500 Requires skilled analyst to supervise plus computer; solid or liquid sample analyzed
Source: Adapted from Fletcher 1987.

Increasing Proportion of Total Mineral + Metal Content Dissolved

Organics

Adsorbed
Soluble Mn-oxides and Crystalline Resistate
and Exchanged Carbonates Silicates
Phases Amorphous Fe-oxides Minerals
Species
Fe-oxides

Distilled Water

Mobile Metal Ion Leach

NH4+-acetate

Na-pyro/H2O2

NaAc/HOAc

Enzyme Leach/H2O2
Inc
re
as Weak NH4OH
in
g
St
re EDTA/H+
ng
th
of
Di Regoleach
ge
sti
on Strong NH4OH

Dilute HCl

Aqua Regia

Mixed Acids

HF/Fusion

figure 3.4-3 Relationship between various selective geochemical extractions and the extent of regolith
mineral components attacked

Digestion Methods their mixtures is not total and will vary with the mineralogy
Sample decomposition presents even greater complexities. The of the sample. Hydrofluoric acid is the only acid decomposi-
newer analytical methods require that elements of interest be tion medium that will dissolve silicate minerals in the typical
introduced to the instruments in solution. The choice of method clastic or lithogeochemical sample. Even with acid mixtures,
to take elements into solution requires careful consideration of extraction efficiency will vary with the acid, sample-to-acid
the mineralogy of the material (Figure 3.4-3). Strong decom- ratio, and the duration and temperature of extraction (Fletcher
positions of a geochemical sample can be achieved through 1981). Of the fusion techniques, lithium metaborate can be
treatment with hot concentrated acids or by fusion. Some resis- effective in attacking resistant minerals and extracting specific
tant minerals (e.g., chromite) may not be soluble in hot concen- elements.
trated acids but are broken down by fusion. Comparison of the quantities of metals extracted by
The amount of metal extracted by the strong decomposi- techniques capable of different degrees of decomposition can
tions achieved with nitric, hydrochloric, or perchloric acids or be informative. Metals in silicate lattices of rock-forming
geochemical Prospecting 135

minerals commonly constitute the background or threshold


level of the geochemical sample material. The mineralization
3,500
component of an anomalous sample is generally contained in
sulfides, iron or manganese oxides, or in adsorbed positions 3,300
on clay minerals. The metal on the clays, and that contained 3,100
in the sulfides and hydroxides, is more easily extractable than 2,900 +2 Standard

Parts per Million


the background/threshold component contained in the rock- 2,700 Deviation
forming minerals. Stronger decompositions, which break True Value
2,500
down the rock-forming minerals, will effectively dilute the
anomalous metal components by releasing the lower con- 2,300 2 Standard
centrations of metal in the background/threshold component. 2,100 Deviation
Partial decomposition techniques utilizing cold or weaker 1,900
acids and other reagents that do not break down the rock- 1,700
forming silicates enhance the more readily extractable min-
1,500
eralization component, resulting in a much greater contrast
0 5 10 15 20 25 30 35 40 45 50
between the anomalous and background values in the survey.
Sequence Number
In numerous geochemical surveys, therefore, the data from
partial decompositions, when ratioed against total decomposi-
tions, can be much more definitive in target delineation than
figure 3.4-4 Standard quality control chart
data from strong or total decompositions. Examples of differ-
ent decomposition techniques and the corresponding mineral
phases digested into solution are shown in Figure 3.4-3. comparable without any significant bias between analytical
Sequential extractions are series of digestions of progres- batches. The reference materials should be prepared from a
sively increasing strength, which can be used to selectively similar matrix as the project samples using a vendor accus-
remove mineral phases in succession within a sample. This tomed to preparing certified reference materials. Failing that,
protocol has been used to successfully delineate copper min- personnel responsible for monitoring QC programs should
eral phases in copper deposits and delineate ore types for min- acquire certified reference materials (standards) from a repu-
eral processing (Parkison and Bhappu 1995). table source.
Duplicate sampling can be used at every level where the
gold Analyses sample volume is reduced and then subsampled to measure
Gold can be analyzed using geochemical or assay methods. For sample, sample preparation, and analytical reproducibility.
reconnaissance and follow-up programs, gold can be analyzed Duplicate sampling of the designated material at the same
using geochemical methods including aqua regia digestion with sample site produces two samples (sample duplicates) that
an inductively coupled plasmaoptical emission spectrometry will give a measure of the sample reproducibility. Splitting of
(ICP-OES) finish. For resource evaluations, gold should be ana- a subsample after the appropriate sample preparation (prepa-
lyzed using traditional assay methods, including 30-g fire assay ration or crush duplicates and pulp or analytical duplicates)
digestion followed by an ICP-OES or AAS finish if the grades will provide information on sample preparation reproducibil-
are below 2 ppm and by gravimetric finish if grades exceed ity and analytical variance.
2 ppm. This would be true for any element of ore grade con- The accepted practice is to include a suite of standard
centrations. If the samples are to be analyzed and incorporated reference samples, as well as sample, preparation, and ana-
into a resource evaluation, the assay methods are the preferred lytical duplicates, to provide a 10% QC volume within every
method to determine concentrations for the element(s) of choice analytical batch. For each batch, the client should include a
in the resource determination. If a nugget effect exists, metallics higher-grade standard, a lower-grade standard, a coarse blank
assays should be used to establish grades. that needs to undergo sample preparation, a sample duplicate,
and an analytical duplicate as a minimum. Where samples are
QuAliTy ConTRol being submitted to determine ore reserves, the frequency of
In addition to observing the basic principles of orientation, standard insertion should be greater.
sampling, sample preparation and analysis, adequate assur- Routine scanning of results from these standards and
ance of analytical quality, representativity, accuracy, and pre- duplicates will give an immediate indication of unsatisfac-
cision are essential when all data are evaluated. The term QA/ tory accuracy and precision and sample inhomogeneity. A
QC is used in discussing quality control programs. QA indi- set of pass/fail criteria should be established for the project.
cates quality assurance, which is the plan for implementing a Acceptable industry practice recommends that standards
quality control program. Quality control is the analysis and should report within 2 standard deviations of the mean using
evaluation of the results of the analytical control program. the mean and standard deviations determined from the refer-
Quality controls should be introduced at all stages in ence material (standard) certification process. Figure 3.4-4
the geochemical program. Specially prepared certified refer- illustrates a QC chart for presenting standard analyses.
ence samples (standards) with known metal contents provide Samples can be arranged by analytical sequence number or
essential material for checking the accuracy of an analytical datein this illustration by sequence numberto display
laboratory on a batch basis and also for monitoring analyti- accuracy. Lines indicating the certificate value (solid line) and
cal drift with time when numerous batches are forwarded to 2 standard deviations (dashed lines) are also plotted. Those
the same laboratory over the life of a project. It is important analyses that exceed the +2 standard deviation pass/fail cri-
to know that analytical data from all stages of a project are teria are considered failures, which need to be investigated.
136 SMe Mining engineering handbook

dispersion models have certain common features (Hoffman


2,500
and Thomson 1987):
+10% A body of mineralization or another source that may
2,000 1:1 Line mimic mineralization
The relative distribution of bedrock, overburden, soil,
10%
groundwater, surface water, vegetation, and other factors
Duplicate Analysis

1,500 Highlighted dispersion pathways related to mineraliza-


tion and anomaly formation
Preferential sites or geochemical barriers, where metals
1,000 concentrate to form anomalies
Portrayal by each model of dispersion as a series of pat-
terns related to and controlled by a variety of identifiable
500 natural factors
Fundamentally, geochemical interpretation involves the
0 recognition of these patterns, the identification of the factors
0 500 1,000 1,500 2,000 2,500 causing them, and the extrapolation of the patterns back to a
Original Analysis mineralized or other source.
The importance of the preferred emphasis on patterns of
figure 3.4-5 Duplicates quality control chart dispersion rather than the magnitude of the geochemical values
in units of parts per million or parts per billion can be illus-
Generally, sample duplicates should be reproducible to within trated by reference to Figure 3.4-7. Precipitation and accumu-
20%, preparation duplicates to within 15%, and analytical lation of hydromorphically transported metal in the seepage
duplicates to within 10%. Figure 3.4-5 illustrates a QC chart anomaly area adjacent to the stream channel can invariably
used for presenting results of duplicate analysesin this case, result in concentrations markedly higher than in the surface
for analytical duplicates with a precision envelope of 10%. horizons of a residual soil anomaly on a well-drained slope.
Any control samples exceeding the pass/fail criteria should be In such a situation, reference only to the magnitude of values
reanalyzed and reevaluated. would result in first priority for follow-up being assigned to
Because it is the objective of the geochemical laboratory the seepage anomaly, whereas recognition of the location and
to produce good and reliable data and maintain an ongoing, shape of the seepage anomaly would immediately indicate its
profitable customer relationship, quality control is of concern origin and direct the interpretation to the source areas upslope.
to both the laboratory and the exploration client. If irregulari- In parallel with pattern recognition, geochemical inter-
ties are noted, the laboratory should be contacted immediately pretation requires a knowledge of the anomalous, threshold,
and the discrepancies discussed. Every reputable laboratory and background values of the elements of interest in the
will have its own standard reference samples and other con- survey. The fundamental observations leading to the iden-
trols and should rerun samples if the quality of its output is tification of these values come from the orientation survey.
questioned. If erratic analytical results are experienced with In the simplest orientation scenario, background values
the duplicate and batch samples but not with the standard are not influenced by the presence of mineralization and in
reference materials, sample inhomogeneity (nugget effect) is Figure 3.4-7 are represented by the relatively homogeneous
indicated. Experienced commercial laboratory personnel can areas of low values at the extremities of the hypothetical soil
assist with these problems by utilizing special preparation traverse. Anomalous values are, in this example, the higher
techniques designed to overcome sample inhomogeneity. values peaking a short distance downslope of the subout-
cropping vein zone. Weaker mineralization, disseminated in
inTeRPReTATion PRinCiPleS the rocks on either side of the vein zone, also gives rise to
Geochemical interpretation does not begin only after all sam- anomalous but less spectacular values, which are also influ-
ples have been collected, prepared, and analyzed. Interpretive enced by the topographic slope.
methodologies develop progressively throughout a geochemi- The upper limit of the background population is referred
cal project. The patterns observed during the orientation pro- to as the threshold, and it is clear that contouring this data at
gram are directly related to the dispersion characteristics of the threshold level will outline an anomalous pattern related
the metallic elements, the nature of the overburden, and the to the mineralization in the bedrock. It is common for back-
overall general geochemical environment. Such recognition ground levels to shift with changes in lithology or alteration
contributes to the formulation of interpretation procedures, systems, which also need to be determined during interpreta-
and this understanding directly affects the sampling, sample tion of the data, such as the lower and the elevated background
preparation, and analytical procedures that are selected for the of the volcanic rocks illustrated in Figure 3.4-7. Introduction
geochemical program. of geological and geomorphological complexities such as
The cumulative experience of geochemical behavior those shown in Figure 3.4-7 can also produce spurious anoma-
gained from orientation surveys and case histories in a broad lies, which need to be considered during interpretation.
spectrum of environments has enabled geochemists to com- Conversely, during mineralization processes, some ele-
pile models that represent dispersion behavior in a wide vari- ments may be leached from the host rocks by the mineraliz-
ety of landscape configurations. The simplified example in ing fluids. In such a situation, a depletion in values below the
Figure 3.4-6 illustrates the formation of geochemical anomaly regional background for the element will cause an anomalous
as patterns related to natural factors within the landscape. All low that is geochemically and economically significant.
geochemical Prospecting 137

Groundwater Movement

Ore-Body Length

Residual Anomaly

Seepage Anomaly

Stream Sediment Anomaly


Soi
l

Ore Body
Soil
Bedrock
Bedrock

Anomalous metal, derived by a


combination of natural weathering
and mechanical movement
Anomalous metal, largely derived
from solution
Biogeochemical anomalies

Source: Hoffman and Thomson 1987.


figure 3.4-6 Simplified model showing formation of geochemical anomalies

Geochemical Soil Profile

Transported Anomaly
in Alluvium
Residual
Lower Background
Anomaly Elevated Background
of Intrusive
of Volcanics
Background ppm Values
Values

Geology and Topography


Weaker, Disseminated
Mineralization
Vein
Groundwater Seepage Area

figure 3.4-7 hypothetical soil profile illustrating anomalies related to geological and geomorphologi-
cal complexities

The interpretation of geochemical data and the correct geology, and the chemistry of the elements as described in
identification of significant anomalies therefore require a fun- the preceding paragraphs but also an understanding of the sta-
damental awareness of the geochemical environment as pre- tistical technique employed. In addition, this effectiveness is
sented in the geochemical model (Figure 3.4-6); a knowledge also dependent on correct design, representativity, and quality
of the geology, structure, and other characteristics of the type of the sampling and analytical phases of the program. Given
of deposit sought; and an underlying understanding of the these essential understandings, statistical techniques provide
geochemical behavior of the elements of interest. This proce- useful and often powerful tools for geochemical data analysis.
dure is clearly described and illustrated with numerous actual They can assist in explaining previously unrecognized char-
examples in a workbook format by Levinson et al. (1987). acteristics in a data set and making significant anomalous pat-
During the past several decades, geochemists have terns more easily recognizable.
adapted statistical methods of evaluation to assist in geochem- A basic assumption applied in the statistical treatment of
ical interpretation. Effective application of statistical meth- geochemical data is that the data are unbiased and continuous.
ods, whether univariate or multivariate, requires not only the Most geochemical data are discrete, but fortunately, in prac-
same full appreciation of the geochemical environment, the tice these discrete values commonly are sufficiently abundant
138 SMe Mining engineering handbook

Figure 3.4-9 illustrates the principles discussed previously


for a property prospective for sediment-hosted gold mineral-

Threshold C
50 ization. Figure 3.4-9A displays the anomalous population of
gold from a soil grid. Several gold anomalies occur through-
out the survey area. Figure 3.4-9B displays an imaged gold
40
Background geochemical signature (of Au+As+Sb+Hg) as determined by

Threshold B
principal component analysis of multielement analyses on soil
Number of Samples

Population
samples. The geochemical anomaly presented in the images

Threshold A
30
is controlled by fault intersections, which acted as conduits
for mineralizing fluids and favorable stratigraphy where min-
20 eralization was deposited. The gold geochemical signature
(Figure 3.4-9B) indicates the extent and controls of the min-
Ore
Population
eralizing system. The anomalous gold image (Figure 3.4-9A)
10 indicates that the highest population represents gold deposited
at structural intersections of northwest- and northeast-trending
faults.
0
0.5 1.0 1.5 2.0 2.5 3.0
oTheR geoCheMiCAl PRoSPeCTing TeChniQueS
Log, ppm
The remarkable advances in new technology have provided
numerous avenues of research and the development of new
Source: Rose et al. 1979. methods that can be applied in mineral prospecting. Usually,
figure 3.4-8 histogram with overlap of values in background each new method experiences a breaking-in period during
and ore populations which the technology is applied in a variety of situations,
leading to a better understanding of the properties being
and close that they can be assumed to be continuous. A review investigated and refinements in interpretation procedures.
of basic statistics is beyond the scope of this presentation, but Before these methods are described briefly, it is appropri-
a comprehensive treatment is covered by Howarth (1983). ate to note that certain well-established techniques of pros-
Univariate statistics allow the geochemist to quickly pecting are still as effective today as they were in the earlier
become familiar with voluminous sets of data. Histograms are days of mining. Such techniques include the skillful use of
used to provide visual information on the total range of val- heavy mineral panning, particularly in the search for gold,
ues, the existence of one or more populations, and possible platinum, cassiterite, tungsten, barite, and other resistant met-
thresholds separating background and anomalous values, as als and minerals of high specific gravity. Although undocu-
illustrated in Figure 3.4-8. Probability plots are used to deter- mented, panning may be responsible for the discovery of more
mine partitioning of populations and the estimation of thresh- ore and mineral occurrences than any other technique.
old values, as well as to detect outliers that can bias the initial The ultraviolet light, or blacklight, method is another
statistical analyses (Sinclair 1976). established technique with specific application in the search
The significance of identifying populations is that individ- for naturally fluorescent minerals such as scheelite, willemite,
ual populations represent geologic or geochemical processes. and fluorite.
One can often separate lithology, alteration, and ore signatures Portable XRF analyzers, initially developed in the 1960s,
by isolating individual populations and plotting these samples today use both radioisotope sources and excitation tubes to
spatially on maps with an appropriate scale to identify a given irradiate the sample material with gamma rays (Glanzman and
geologic or geochemical process within the survey area. Closs 2007). The resultant X-ray spectrum is selectively fil-
Multielement chemical analysis of samples is extremely tered, and specific elements can be measured directly at the out-
cost-effective, and the resulting data sets provide the opportu- crop, the drill site, or the underground face in concentrations as
nity to more specifically characterize features in the data based little as in the low parts-per-million range for selected elements.
on their multielement geochemical signature. Correlation The penetration of the sample surface by X-rays emitted
analysis is used to determine intraelement relationships, by the radioactive source is limited and generally less than
which are examined visually using scatter diagrams showing 3 mm (0.1 in.). The accuracy of any determination is depen-
the relationships between individual element pairs. dent, therefore, on the sample surface exposed to the detec-
Multivariate data analysis is used to investigate rela- tor. Measurements on unprepared rock surfaces, whether the
tionships between elements and can include other types sample is a rock face, a hand specimen, or piece of drill core,
of exploration parameters based on geological, geophysi- display greater variation and represent, at best, a semiquanti-
cal, or other data. Based on this information, it is possible tative measurement. To obtain quantitative results, it is nec-
to investigate intraelement relationships using a variety of essary to homogenize and mix the sample through grinding
techniques (principal component, factor analysis, cluster and pulverization. The sensitivity of the portable XRF analyz-
analysis, multiple regression, discriminate and characteriza- ers is generally less than more conventional geochemical or
tion analysis) (Howarth 1983). Elements that are highly cor- assay techniques, but nevertheless, the positive identification
related with one another represent geochemical associations, of metals of interest in the field contributes to an increased
which indicate geologic or geochemical processes. Plotting prospecting effectiveness. The metals that can be identified
coincident anomalies of these highly correlated elements and quantitatively measured by the portable analyzers include
spatially on maps shows where the process is operative in barium, copper, iron, lead, molybdenum, nickel, silver, tita-
the survey area. nium, tungsten, tin, zinc, and zirconium.
geochemical Prospecting 139

(A) (B)

figure 3.4-9 Contoured images of (A) anomalous gold population and


(B) multielement Au+As+Sb+hg geochemistry association, as determined by
principal component analysis

Portable infrared mineral analyzers are field spectrom- value), elements that may be penalty metals during processing
eters that measure infrared reflectance spectra of core and or be environmental liabilities, and input to overall mine plan-
crushed rock samples, which allows the identification of min- ning and scheduling. Initial investigations of mineralization
erals. These instruments have been used extensively by those types should be assessed via high-quality multielement data
exploring alteration systems associated with porphyry copper to identify those elements that may be either value enhancers
deposits and epithermal gold deposits. (depending on deposit typee.g., silver or cadmium) or poten-
tially penalty constituents (e.g., arsenic, mercury, or cadmium).
Mine SiTe APPliCATionS of geoCheMiSTRy Analytical methods can be selected to aid in assessment of
This section provides an overview of applied geochemistry mine designfor example, fire assay data to obtain estimates
and highlights specific aspects of geochemistry that impact of total metal versus cyanide extraction of goldto address the
resource development and mine site responsibilities of geolo- options of either milling or heap leaching plant design.
gists and mining engineers. Mineralogy, particularly clay mineralogy, is also impor-
tant to assess. It can affect rock competency and stability, mill-
Sampling ing and heap leach plant design, and degree of weathering and
Representative sampling of mine materials is one of the most oxidation in mine and tailings facilities.
important and difficult tasks. When done poorly, it generally
leads to erratic and noisy data, and poor decisions. The pur- Quality Assurance and Quality Control
pose of sampling is to provide a representative estimate from As noted earlier, QA deals with selecting the appropriate ana-
which valid decisions follow. Appropriate sampling starts with lytical method for the issue at hand. An example is the choice
geology and encompasses both what and how. It also includes of selecting total analysis of gold via fire assay versus cyanide
mining considerationsfor example, the bench height and extractable gold as input to plant type selection. QC of analyti-
block size used to estimate the deposit characteristics for mine cal assessment of data is essential in making initial production
planning purposes. and development decisions, in construction of the database on
Once the initial sample is obtained, subsampling aspects which project economics and financing are based, and in rec-
need to be considered to maintain the representativity of the onciliation and ongoing project management. Typically, pro-
sample prior to the measurements of properties under consid- duction analyses are carried out on-site. QC responsibilities
eration (Springett 1984; Pitard 1993). Alternatively, sample often fall on mine staff geologists and mining engineers who
separation of the original material collected can be undertaken use these data on a daily basis. External independent checks
for specific informational purposes. For example, when a new should be a routine part of this process. Properly designed QA
section of the mine is opened, samples from the new section and QC protocols quantify, monitor, and document how well
should be tested to determine if any changes in ore mineral- important variables are known and where corrective action is
ogy or metal content might affect recovery. This process must required.
also follow protocols that ensure the representative aspect of
the subsample. Deposit zoning and Mine Sequencing
The distribution of mineralization types in an ore deposit is
Chemical Analysis significant in mine planning. This knowledge allows for con-
Chemical analysis of samples can provide information about sideration of ore blending during mine extraction sequencing
the anticipated commodities to be recovered, elements that to potentially mitigate the negative impact of included penalty
may potentially provide by-products (thereby enhancing metals.
140 SMe Mining engineering handbook

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Initial exploration and development studies, ongoing assess- chemical programs. In Proceedings, Exploration 87, 3rd
ment during production and reclamation, and monitoring Decennial International Conference on Geophysical and
during postproduction to satisfy environmental regulatory Geochemical Exploration for Minerals and Groundwater,
requirements are all based on correct assessment of the site Paper 43. Special Volume 3. Edited by G.D. Garland.
before, during, and after mining. A departure point for these Ontario Geological Survey. pp. 569587.
studies is the geological and geochemical nature of the mate- Coker, W.B., Hornbrook, E.H.W., and Cameron, E.M. 1979.
rial being mined. Geoenvironmental models developed ini- Lake sediment geochemistry applied to mineral explora-
tially by the U.S. Geological Survey (du Bray 1995; Filipek tion. In Geophysics and Geochemistry in the Search for
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Range. Min. Cong. J. 25(5):6269.
Communication du Bray, E.A., ed. 1995. Preliminary compilation of descrip-
Applied geochemistry has a great deal to offer to the efficient, tive geoenvironmental mineral deposit models. Open-
effective, and profitable execution and ongoing operation of File Report 95-831. Reston, VA: U.S. Geological Survey.
a mine. Many different professional skills are required. Each Dunn, C.E. 2007. Biogeochemistry in mineral explora-
professional has a responsibility to appreciate the contribution tion. In Handbook of Exploration and Environmental
of fellow professionals. The overall management and respon- Geochemistry, Vol. 9. Amsterdam: Elsevier.
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