AU AND TECHNOLOGY (UMaT), TARKWA FACULTY OF MINERAL RESOURCES TECHNOLOGY Lecture Notes on GL 374 EXPLORATION GEOCHEMISTRY Compiled by: Dr G. M. Tetteh January 2013 | UNIVERSITY OF MINESTABLE OF CONTENTS Scope of Geochemical Exploration Orientation Surveys Geochemical Analysis: Accuracy and Precision, Sample Collection and Preparation, Analytical Methods, Mean and Median Metal Concentrations Trace Elements Geochemical Data Interpretation: Statistics and Anomalies Scales and Sampling Media in Geochemical Exploration Geochemical Dispersion - Primary and Secondary Dispersion Reconnaissance Surveys and Detailed Surveys Techniques for Reconnaissance Surveys - Stream Sediment Sampling, Lake Sediment Sampling Overburden/Soil Geochemistry: Surface Soil Sampling, Transported Overburden Geochemistry of Vegetation: Geobotany, Biogeochemistry, Elemental Cycling via Plant Absorption Follow Up Sampling Mine Scale Uses Pitting and Trenching Drilling: Auger Drilling, Rotary Air Blast (RAB), Reverse Circulation (RC), Diamond (Core) Drilling ‘Natural Occurrence of Metals In The EnvironmentSCOPE OF GEOCHEMICAL EXPLORATION Geochemistry is now used in virtually every exploration program and particularly applies to the use of material such as soil, or vegetation from the surface of the earth (in areas where there is little outerop). The purpose of of measurements is the discovery of abnormal chemical pattems, or geochemical anomalies, related to mineralization. Exploration geologists are likely to be more directly involved in geochemistry than with geophysics which is usually conducted by contractors and supervised by specialist geophysicists. A geochemical program can be divided into the following phases: 1 Planning; 2 Sampling: 3 Chemical analysis; 4 Interpretations; 5 Follow up. The field geologist will probably carry out phases 1, 2, 4, and 5, while analysis is normally performed by a commercial laboratory.PLANNING The choice of the field survey technique and the analytical methods depends on the commodity sought and its location. In the same way as geological and grade-tonnage models are generated modelings can be extended to include geochemical factors, summarised in Barton (1986). Thus the geologist will start with knowledge of the elements associated with a particular deposit type, an idea of the economic size of the deposit to be sought, the mineralogical form of the elements, and the probable size of the elemental anomalies around it. The outline of a deposit is defined by economic criteria and the mineable material is surrounded by lower concentrations of the mined elements which are however substantially enriched compared with unmineralized rock. Orientation surveys One of the key aspects of planning is to evaluate which techniques are effective for the commodity sought and in the area of search. This is known as an orientation survey. The best orientation survey is that in which a variety of sampling methods is tested over a prospect or deposit of similar geology to the target and in similar topographical conditions to determinethe method which yields the best results. A checklist for an orientation study is given below (Closs and Nichol 1989): 1 Clear understanding of target deposit type; 2 Understanding of environment of the search area; 3 Nature of primary and secondary dispersion from the mineralization; 4 Sample types available; 5 Sample collection procedures; 6 Sample size requirements; 7 Sample interval, orientation, and areal density; 8 Field observations required; 9 Sample preparation procedures; 10 Sample fraction for analysis; 11 Analytical method required; 12 Elemental suite to be analysed; 13 Data format for interpretation. The relatively small cost involved in undertaking an orientation survey compared with that of a major geochemical survey is always justified and whenever possible this approach should be used. However, if a physicalorientation survey is not possible, then a thorough review of the available literature and discussion with geochemical experts is a reasonable alternative option. Of particular use in orientation studies are the models of dispersion produced for various parts of the world; Canadian Shield and Canadian Cordillera (Bradshaw 1975), Western USA (Lovering & McCarthy 1977), and Australia (Butt & Smith, 1980). Particularly useful discussion on orientation procedures is provided by Thomson (1987) and Closs and Nichol (1989). After the orientation survey has been conducted the logistics of the major survey need to be planned. The geologist should devise a checklist similar to that of Thomson (1987). 1 Hire field crew with appropriate experience and training; 2 Obtain base maps and devise simple sample numbering scheme; 3 Designate personnel for communication with the laboratory; 4 Arrange quality control of laboratory; 5 Arrange for data handling and interpretation; 6 Organise archive of samples and data; 7 Liaise with other project staff (e.g. geophysicists) and arrange reporting to management.Reporting of geochemical surveys is important and geologists should consult the short booklet by Bloom (2001). This provides a wealth of information as well as the basis for fulfilling legal requirements in Canada. ANALYSIS ‘As the geologist generally sees little of the process of analysis, which is usually done at some distance from the exploration project, analytical data tend to be used uncritically. While most laboratories provide good quality data they are usually in business to make a profit and it is up to the geologist to monitor the quality of data produced and investigate the appropriateness of the analytical methods used. Accuracy and precision The critical question for the geologist is how reproducible the analysis is and how representative of the “correct” concentration the concentration is, as shown in Figure below. The reproducibility of an analysis is termed the precision and its relation to the expected or consensus value the accuracy. For most purposes in exploration geochemistry it is vitally important that an analysis is precise but the accuracy is generally not so crucial, although some indication of the accuracy is needed. At the evaluation stage theanalyses must be precise and accurate. The measurement of accuracy and precision requires careful planning and an understanding of the theory involved. A number of schemes have been devised but the most comprehensive is that of Thompson (1982). Precision is measured by analysing samples in duplicate whereas accuracy requires the analysis of a sample of known composition, a reference material. The use of duplicate samples means that precision is monitored across the whole range of sample compositions. Reference materials can be acquired commercially but they are exceedingly expensive (US$100 per 250 g) and the usual practice is to develop in-house materials which are then calibrated. against international reference materials. The in-house reference materials can be made by thoroughly mixing and grinding weakly anomalous soils from a variety of sites. The contents should be high enough to give some indication of accuracy in the anticipated range but not so high as to require special treatment (for copper, materials in the range 30-100 ppm are recommended). If commercial laboratories are used then the reference materials and duplicates should be included at random; suggested frequencies are 10% for duplicates and 4% for reference materials. If the analyses are in-house then checks can be made on the purity of reagents byrunning blank samples, i.e. chemicals with no sample. Samples should if possible be run in a different and random order to that in which they are collected. This enables the monitoring of systematic drift. In practice this is often not easy and it is not desirable to operate two numbering systems, so some arrangement should be made with the laboratories to randomise the samples within an analytical batch. The results can then easily be re-sorted by computer. When laboratory results become available the data should be plotted batch by batch to examine the within- and between-batch effects. The effects observable within a batch are precision and systematic instrumental drift. Precision should be monitored by calculating the average and difference between duplicates on a chart such as is detailed by Thompson (1982). The precision for most applications should be less than about 20%, although older methods may reach 50 %. If precision is worse than anticipated then the batch should be re-analysed. Systematic drift can be monitored from the reference materials within a batch and the reagent blanks. Between-batch effects represent the deviation from the expected value of the reference material and should be monitored by control charts. Any batch with results from reference materials outside the mean +2 standard deviations should bere-analysed; commercial laboratories normally do this at no further charge. Long-term monitoring of drift can show some interesting effects. Coope (1991) was able to demonstrate the disruption caused by the moving of laboratories in a study of the gold reference materials used by Newmont Gold Inc. n n Conen Precise, accurate Imprecise, accurate n n Precise, inaccurate Imprecise, inaccurate FIG Schematic representation of precision and accuracy assuming normal distribution of analytical error.Sample collection and preparation Samples should be collected in nonmetallic containers to avoid contamination. Kraft paper bags are best suited for sampling soils and stream sediments because the bags retain their strength if the samples are wet and the samples can be oven dried without removing them from their bags. Thick gauge plastic or cloth is preferred for rock samples. All samples should be clearly labeled by pens containing nonmetallic ink. Most sample preparation is carried out in the field, particularly when it involves the collection of soils and stream sediments. The aim of the sample preparation is to reduce the bulk of the samples and prepare them for shipment. Soils and stream sediments are generally dried either in the sun, in low temperature ovens, or freeze dried. The temperature should be below 65 °C in order that volatile elements, such as mercury, are not lost. Drying is generally followed by gentle disaggregation and sieving to obtain the desired size fraction. Care should be taken to avoid the use of metallic materials and to avoid carryover from highly mineralized to background samples.Preparation of rocks and vegetation is usually carried out in the laboratory and care should be taken in the selection of crushing materials. For example, in a rock geochemical program a company searching for volcanic-associated massive sulphides found manganese anomalies associated with a hard amphibolite. They were encouraged by this and took it as a sign of exhalative activity. Unfortunately further work showed that the manganese highs were related to pieces of manganese steel breaking off the jaw crusher and contaminating the amphibolite samples. Other less systematic variation can be caused by carryover from high grade samples, for example not cleaning small grains of mineralized vein material (e.g. 100,000 ppb Au) will cause significant anomalies when mixed with background (1 ppb Au) rock. Contamination can be eliminated by cleaning crushing equipment thoroughly between samples and by checking this by analysing materials such as silica sand. The Bre-X scandal, in which alluvial gold was added to drill pulps before sending the samples for analysis , emphasises the importance of recording the methods of sample preparation and controlling access to the samples.Analytical methods Most analysis is aimed at the determination of the elemental concentrations in a sample and usually of trace metals. At present it is impossible to analyse all elements simultaneously at the required levels, so some compromises have to be made (Figure below). In exploration for base metals it is usual to analyse for the elements sought, e.g. copper in the case of a copper deposit, and as many useful elements as possible at a limited extra cost. With modern techniques it is often possible to get 20-30 extra elements, including some that provide little extra information but a lot of extra data for interpretation. ‘The major methods are as shown in the Table below. ‘The reader should consult Fletcher (1981, 1987) and Thompson and Walsh (1989). The differences between the methods shown are cost, the detection limits of analysis, speed of analysis, and the need to take material into solution. Most general analysis in developed countries is carried out by inductively coupled plasma emission spectrometry (ICP-ES), often in combination with inductively coupled plasma mass spectrometry (ICP-MS), or X-ray fluorescence (XRF). All three methods require highly sophisticated laboratories, pure chemicals, continuous, non-fluctuating power supplies,4 He c[N| 0 Bee Ne Mg | Cid At ee | — . a RUN RN PS ts Bal ta Hi 7, OSE Fr Raga i] re Newton actvaton analysis 2] ieducsvety coupled mass spectomery N ray nccescence SR se assay eeconceraton vas tnsnes 7] Atomic asorpton specropnotreaty Cotner methods EBB coxcraty coupi emssonspscremeny Fig. Summary periodic table showing cost-effective methods of elemental analysis at levels encountered in background exploration samples. Summary of the main methods used in exploration cochemistry. Method CCapitalcost$Mukticlement Precision Samplerype Cost per commentssample (enprox) (sus) Colerimetey 5000) No Poor Solution «2-10 Goolfor eld we aod W, Mo Awmicabsortion 60000 No Good Solution 1-5 Cheap and precise spectrophotormetry Xvaydunnescence 200000 Yes Good Solid 2 Coodtor refractory clement icr-as. Yes Gool Solution = «10S Gaod fur ‘tansition metals ices Yes Gool Solution 10 Good forheavy smectals. High ‘resolution love detection limits 13and readily available service personnel, features not always present in developing countries, In less sophisticated environments, high quality analysis can be provided by atomic absorption spectrophotometry (AAS), which was the most commonly used method in developed countries until about 1980. Another method which is widely used in industry is neutron activation analysis (NAA) but its use is restricted to countries with cheap nuclear reactor time, mainly Canada. Precious metals (gold and platinum group elements) have been extremely difficult to determine accurately at background levels. The boom in precious metal exploration has, however, changed this and commercial laboratories are able to offer inexpensive gold analysis at geochemical levels (5 ppb to 1 ppm) using solvent extraction and AAS, ICP-ES or alternatively NAA on solid samples. For evaluation the method of fire assay is still without equal: in this the precious metals are extracted into a small button which is then separated from the slag and determined by AAS, ICP-ES, or ICP-MS. The analysis of precious metals is different from most major elements and base metals in that large subsamples are preferred to overcome the occurrence ofgold as discrete grains. Typically 30 or 50 g are taken in contrast to 0.25-1 for base metals; in Australia, 8 kg are often leached with cyanide to provide better sampling statistics. Elements which occur as anionic species are generally difficult to measure, especially the chloride, bromide, and iodide ions which serve as some of the ore transporting ligands. Although some of these elements can be determined by ICP-ES or XRF, the most useful method is ion chromatography. Isotopic analysis is not yet widely used in exploration although some pilot studies, such as that of Gulson (1986), have been carried out. The main reason for this is the difficulty and cost of analysis. Although high resolution ICP sourced mass spectrometers are finding their way into commercial laboratories and are the main hope for cheap analysis, they are not yet routine. The choice of analytical method will aim at optimising contrast of the main target element. For example, it is little use determining the total amount of nickel in an ultramafic rock when the majority of nickel is in olivine and thetarget sought is nickel sulphides. It would be better in this case to choose a reagent which will mainly extract nickel from sulphides and little from olivine. In soils and stream sediments, optimum contrast for base metals is normally obtained by a strong acid (e.g. nitric + hydrochloric acids) attack and does not dissolve all silicates, and an ICP-ES or AAS finish. Most rock analysis use total analysis by XRF or by ICP-ES/ICP-MS following a fusion or nitric-perchloric—hydrofluoric acid attack. Table Composition of the Layers of the EarthMayor cloene aries Ct %3) 50, avi 489 as om 20 590 ous 62 on 10038 ass 4525 os on 2 66 on 295 695 ons 005, oon 60s at os v9.00 ato 6m 029 sor Ls 370 on 2621 oat ZH we we Sele tae elements (pom) Sm 0 2090 a 28 0% 110 mo wo ‘ we Le me aw 1 oes Rog aatepe rain ond Sede 0.7056 4 24 oust Stabe spe ratios (*/4) 50 473 0 Mean and Median Metal Concentrations 230 us 4 ey aa 231 oss 25 70501 +68 Though metal concentrations in the environment can range widely, it is still useful to consider their mean and median values in waters and soils and the Earth’s crust. It is often assumed that species present in water at less than I milligram per liter (mg/L) but more than 1 microgram per liter (g/L) are minor species, while those present at below 1 :g/L are termed trace species (Langmuir, 1997a). Based on these definitions, most of the metals of concern are minor species and some are trace species, particularly in surface waters which are in general more dilute than soil or ground waters. 7