Ralph J.

Holmes CSIRO Minerals Down Under National Research Flagship, Australia

Challenges of developing ISO sampling standards

ABSTRACT

The standards developed by the International Standards Organisation (ISO) for sampling mineral commodities receive more than their fair share of criticism for being inadequate and not conforming to the Theory of Sampling developed by Pierre Gy. However, is this fully justified? While there is always scope for improving ISO sampling standards, many elements of the Theory of Sampling and the requirements for correctly designing sample cutters to ensure that they collect representative samples are incorporated into the current ISO standards for sampling iron ore, coal and coke, and copper, lead, zinc and nickel concentrates. In addition, these standards are continually being reviewed and improved, but this is no easy task because they are developed by technical committees on an international consensus basis, and commercial issues or plain ignorance can often get in the way of technical correctness. Hence, the introduction and adoption of new concepts and procedures can be a lengthy process, but persistence usually pays off particularly if the proposed changes are backed up by hard data. Examples are provided of correct sampling theory and practice that have been incorporated into ISO sampling standards for the international trade of mineral commodities. In addition, areas requiring improvement are identified.

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INTRODUCTION The development of ISO standards for mineral commodities is a relatively long process. technical committees (TC) have been established to develop standards for specific commodities, e.g., committees ISO/TC 27 (solid mineral fuels), ISO/TC 102 (iron ores) and ISO/TC 183 (copper, lead, zinc and nickel ores and concentrates). Sub-committees and working groups are then established on a needs basis to develop specific standards for sampling, analysis, physical testing, etc. of selected mineral commodities. Countries electing to participate in the development of these standards nominate representatives to become members of these sub-committees and working groups, which progress draft standards through a number of stages from working draft (WD) to committee draft (CD) to draft international standard (DIS), and finally publication as an international standard. Focussing on sampling standards, the representatives on these sub-committees and working groups usually have some expertise and experience in sampling, but this is not always the case and commercial issues, lack of knowledge or resistance to change can sometimes get in the way of technical correctness. The approval process at each of the development and final publication stages is based on majority consensus, initially by members of the relevant working group or sub-committee, but final approval is determined by a formal voting process involving the standards organisations in the member countries of the appropriate technical committee. The internal consultative process within each country prior to casting votes is quite varied and can range from detailed consultation with technical experts in the field to casting of votes by non-specialist representatives of member countries. Consequently, on some occasions the technical experts can be out-voted, leading to the publication of ISO standards that may contain flaws. Persistence is then required to systematically address these flaws when such standards are next revised, usually within five years of publication by ISO. Examples are provided below where correct sampling theory and practice have been incorporated into ISO sampling standards and areas requiring improvement are discussed.

KEY REQUIREMENTS FOR Sampling CORRECTNESS There are a number of key requirements that need to be met to ensure that the samples collected from a process stream are representative and that the overall precision is adequate. These requirements are as follows:

The number of increments taken from the process stream must be sufficient to obtain the desired sampling and overall precision. All particles in the process stream or stratum must have an equal probability of being selected and appearing in the final sample for analysis. Any deviation from this basic requirement can result in bias and consequently the sample extracted will not be representative. This requirement can be met largely through correct design of the sampling equipment. For a given nominal top size of the material being sampled, there is an absolute minimum mass of sample that must be retained after division to control the fundamental sampling error at each sampling stage and obtain the desired division precision (Gy, 1982).

If these key requirements are incorporated into ISO standards for sampling mineral commodities, then the standard conforms to correct sampling principles and representative samples should be obtained.

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Sampling precision The most comprehensive treatment of sampling precision in ISO standards for mineral commodities is provided in ISO 12743 (ISO, 2006a) for sampling copper, lead, zinc and nickel concentrates. In this standard, the overall variance of the final analysis for the lot, 2 denoted by sT , consists of the sum of the variances of sampling and analysis as follows:

where:
2 sS 2 sA

2 2 2 sT = sS + sA

(1)

= =

the sampling variance (including sample processing) the analytical variance

The sampling variance in Equation 1 includes the variances due to all sampling (and sample processing) steps except selection of the test portion, while the variance due to selection of the test portion is included in the analytical variance, because it is difficult to determine separately the true analytical variance. When replicate analyses are carried out, the total variance can be reduced as follows:
2 2 sT = sS + 2 sA r

where: r =

(2)

number of replicate analyses

In ISO 12743 (ISO, 2006a), the sampling variance is broken up into its components for each sampling stage (Gy, 1982; Pitard, 1993) as follows:
2 2 2 2 sT = sS + .... + s S +.... + s S + 1 i u 1 2 sA r

where:

(3)

2 sS = the sampling variance for stage 1, the primary sampling variance 1 2 sS = the sampling variance for stage i i 2 sS = the sampling variance for stage u-1, the second last stage u 1

the number of sampling stages, stage u corresponding to selection of the test portion

This approach is particularly useful for designing and assessing sampling schemes. However, to obtain the maximum benefit, it is necessary to determine the variance between increments for each sampling stage using the following equation in ISO 12743 (ISO, 2006a):

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where:

2 sb = i

(x
j =1

x) 2
2 sPA P A

ni 1

(4)

2 sb = the variance between increments for stage i i x j = the test result for increment j

x s
2 PA P A

= =

the mean test result for all increments the variance of subsequent sample processing and analysis steps

The sampling variance for stage i is then given by:

where: ni =

s =

2 Si

2 sb i

ni

(5)

the number of increments taken at stage i

2 2 sb i

Combining Equations 3 and 5 gives the overall variance sT as follows:

2 = sT i =1 u 1

ni

2 sA r

(6)

This is a comprehensive approach to designing a sampling scheme and determining the overall variance of the final analysis for the lot, although quite a lot of work is required to determine the variance of the intermediate stages. A simpler approach used in ISO 3082 (ISO, 2009) and ISO 13909-2 (ISO, 2001) for sampling iron ore and coal respectively is to break up the overall variance into the primary sampling, sample processing and analytical variances only as follows:

where:

2 2 2 = sS + sP + sT 1

2 sA r

(7)

2 = the primary sampling variance sS 1 2 s P = the variance due to all subsequent sample processing stages, except for selection of

the test portion

The primary sampling variance is estimated using a similar process to that described above for each sampling stage, while the sample processing variance is usually determined experimentally by processing duplicate samples. The relative magnitudes of the variance components in Equation 7 indicate where additional effort is required to reduce the overall variance.

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Both approaches are valid ways of estimating and subsequently controlling the short- and long-range quality fluctuation errors set out in Gys sampling theory (Gy, 1982; Pitard, 1993). The fundamental error is addressed by specifying the minimum mass of divided sample, which is discussed below. On the other hand, a number of ISO standards developed more recently for sampling copper, lead, zinc and nickel concentrate slurries (ISO, 2010) and coal slurries (ISO, 2006b) start off by explicitly discussing all the components of overall sampling error TE defined by Gy (1982) as follows:

where: QE1 = QE2 = QE3 = WE = DE = EE = PE =

TE = QE1+ QE2+ QE3+ WE+ DE+ EE+ PE

(8)

the short-range quality fluctuation error associated with short-range variations in quality the long-range quality fluctuation error associated with long-range variations in quality the periodic quality fluctuation error associated with periodic variations in quality the weighting error associated with variations in flow rate the increment delimitation error introduced by incorrect increment delimitation the increment extraction error introduced by incorrect increment extraction the preparation error (also known as accessory error) introduced by departures (usually unintentional) from correct practices, e.g., during constitution of the lot sample, sample transfer and drying QE1 = FE + GE
(9)

The short-range quality fluctuation error consists of two components as follows:

where: FE = GE =

the fundamental error due to variation in quality between particles the segregation and grouping error

These two ISO standards then point out which components can be essentially eliminated by correct design of the sampling equipment, i.e., the delimitation, extraction and preparation errors, and which components need to be reduced to acceptable levels through careful design of the sampling regime, i.e., the fundamental error, the segregation and grouping error, the long-range and periodic quality fluctuation errors, and the weighting error. This is a good example of being able to better align ISO sampling standards with Gys Theory of Sampling (Gy, 1982) when new standards are developed in the absence of previous standards and entrenched existing procedures. Sample cutter design The key requirement for correctly designing sample cutters and dividers is the elimination of the increment delimitation and extraction errors defined by Gy (1982). While these terms may not be explicitly mentioned in a number of ISO sampling standards, e.g., ISO 3082 (ISO, 2009), ISO 12743 (ISO, 2006a) and ISO 13909-2 (ISO, 2001), the requirements for eliminating

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delimitation and extraction errors are clearly stated. For example, ISO 12743 (ISO, 2006a) states that the sampling system shall be designed to avoid and/or minimise the following:

Spillage of the sample Restriction of the flow of concentrate through the system Contamination of the sample Change in moisture content Loss of dust Degradation of the constituent particles if the sample is taken for particle size determination

Lists of more detailed design criteria for falling-stream cutters are provided in all the key ISO standards for sampling mineral commodities, i.e., ISO 3082 (ISO, 2009), ISO 12743 (ISO, 2006a) and ISO 13909-2 (ISO, 2001), and a comparison of these criteria for sampling copper, lead, zinc and nickel concentrates (ISO, 2006a) and iron ores (ISO, 2009) is shown in Table 1. The importance of cutter speed is also covered, because too high a cutter speed will lead to biasing of the sample due to deflection of the larger particles, excessive turbulence and shock load problems, and difficulties in maintaining constant speed while cutting the stream. Reference is therefore made to the experimental work undertaken by Gy (1982), which showed that significant bias can be introduced when the cutter speed exceeds 0.6m/s or the cutter aperture is less than three times the nominal top size of the material being sampled. However, when the effective aperture (l1) exceeds three times the nominal top size of (d), the maximum cutter speed (VC) can be increased according to Equation 10, subject to a maximum of 1.5m/s:

VC = 0.3 (1 +

l1 ) 3d

(10)

Provided all these requirements are met, increment delimitation and extraction errors will be eliminated and representative samples obtained.

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Table 1 Comparison of cutter design criteria in ISO 12743 and ISO 3082 ISO 12743 (copper, lead, zinc and nickel concentrates) There shall be no impediment to the flow of concentrate into the cutter at the maximum flow rate of the concentrate. The cutter shall be of the self-clearing type, e.g., stainless steel or polythene lined, discharging each increment completely. Discharge chute angles shall be a minimum of 60 to the horizontal. There shall be no significant change in the quality of the sample while taking increments, e.g., degradation of the constituent particles if the sample is taken for size determination or change in moisture content if the sample is taken for moisture determination. No materials other than the concentrate sample shall be introduced into the cutter, e.g., dust must be prevented from accumulating in the cutter when in the parked position. The cutter shall collect a complete crosssection of the concentrate stream, both the leading and trailing edges completely clearing the stream at the two limits of the cutter path. The cutter shall intersect the concentrate stream either in a plane normal to, or along an arc normal to the mean trajectory of the stream. The cutter shall travel through the concentrate stream at a uniform speed, not deviating by more than 5% at any point. The geometry of the cutter opening shall be such that the cutting time at each point in the stream is equal, not deviating by more than 5%, i.e., straight path cutter shall have parallel cutter lips and radial cutters shall have radial cutter lips. The cutting aperture of the cutter shall be not less than 30mm or, if agglomerates are present, three times the nominal top size of the concentrate, whichever is larger, noting that the cutter aperture may need to be increased above 30mm if blockages occur for wet concentrates. Bucket cutters shall be of sufficient capacity to accommodate the increment mass obtained at the maximum flow rate of the concentrate. There shall be no contamination or introduction of material other than the sample into the sample cutter. ISO 3082 (iron ore) There shall be no impedance to flow of sample materials through the sample cutter at the maximum flow rate. There shall be no clogging or retention of residual material in the sample cutter, i.e., the cutter shall be self-clearing.

The sample cutter shall take a complete crosssection of the ore stream, both the leading and trailing edges clearing the stream in one path. The sample cutter shall intersect the ore stream either in a plane perpendicular to or along an arc normal to the mean trajectory of the stream. The sample cutter shall travel through the ore stream at a uniform speed, not deviating by more than 5% at any point. The geometry of the cutter aperture shall be such that the cutting time at each point in the stream is equal, not deviating by more than 5%, e.g., straight-path cutters shall have parallel cutter lips and rotary cutter shall have radial cutter lips. The cutting aperture of the primary sampler shall be at least three times the nominal top size of the ore, or 30mm, whichever is the greater. However, with certain ores, e.g., sticky ores, bridging and consequent bias may occur for a cutter aperture of three times the nominal top size. In these instances, larger cutter apertures shall be used to prevent the introduction of significant bias. Bucket type cutters shall be of sufficient capacity to accommodate the increment mass obtained at the maximum flow rate of ore.

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Design criteria are also provided for cross-belt cutters in the ISO standards for sampling copper, lead, zinc and nickel concentrates (ISO, 2006a) and coal (ISO, 2001), largely because these cutter types are widely used in industry. Provided all the design criteria are satisfied religiously, representative samples should be obtained, but it is rare for the entire increment to be fully extracted from the conveyor belt, e.g., due to wear of the brushes on the bottom of the cutter or maintenance staff deliberately leaving a gap between the bottom of the cutter and the conveyor belt to eliminate possible damage to the conveyor. Hence, the author does not favour cross-belt cutters and they are not included in the ISO standard for sampling iron ore due to the much large masses, flow rates and particle densities involved. Minimum sample mass In recent years ISO standards for sampling mineral commodities have moved away from the concept of minimum increment mass to the concept of minimum sample mass that must be retained after division to obtain the desired division precision. This mass is determined by Gys fundamental error (Gy, 1982), which arises from the differences in composition of the individual particles in the material being sampled. This error can be reduced by taking more particles, thereby increasing the sample mass, or crushing/grinding the material prior to division, which increases the number of particles taken for a given sample mass. Unfortunately, this requirement is often ignored in industry when designing sampling and sample processing schemes, which impacts adversely on sampling precision. The requirements for minimum sample mass as a function of particle size are most commonly dealt with via a table of minimum sample masses in ISO sampling standards. However, the masses specified in these tables are not always well founded, particularly for the larger particle sizes where the masses can become quite large. The best example of addressing this is the ISO/TC 102/SC 1 sub-committee, which is responsible for developing ISO standards for sampling iron ores. A comprehensive international test programme was conducted to investigate the relationship between division precision, sample mass and particle size (ISO, 1995), and the results were fitted to the minimum mass equation developed by Gy (1982). The resultant equation for the minimum mass of divided sample mS, in kilograms, was as follows:

where: mS =

mS =

0.00032 0.0003 2 d 2 ,5
2 D

(11)

the nominal top size of the sample (mm)

D = the desired standard deviation of sample division, in %Fe

Examples of minimum divided gross sample masses given by Equation 11 for a division standard deviation of 0.1% Fe and 0.05% Fe and typical nominal top sizes are given in Table 2. The corresponding minimum mass table for sampling hard coal in ISO 13909-2 (ISO, 2001) is not well established. The minimum masses for the coarser particle sizes are based on experimental work similar to that performed for iron ore, which investigated the relationship between division precision, sample mass and particle size (Holmes, 1987). However, the minimum sample masses for the smaller particle sizes were increased above the masses indicated by various fits of the experimental data to Gys equation as an additional precaution. At least this is a safe approach.

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Table 2 Examples of minimum mass of divided gross sample for chemical analysis of iron ore Nominal top size (mm) 40 31.5 22.4 10 6.3 2.8 1.4 0.50 0.25 Minimum mass of divided gross sample (kg)

D = 0.1% Fe
325 180 75 10 3.2 0.5 0.5 0.5 0.5

D = 0.05% Fe
1300 710 300 40 13 1.7 0.5 0.5 0.5

Conclusion While there is always scope for improvement, it has been demonstrated that the main elements of the Theory of Sampling and the requirements for correctly designing sample cutters have been incorporated into the key ISO standards for sampling mineral commodities, including iron ore, coal and copper, lead, zinc and nickel concentrates. In some instances, the connection to Gys Theory of Sampling is abundantly clear, while in other instances the relationship is less direct, although the key elements of correct sampling practices are still included. ISO standards are continually being reviewed and improved, so progress will continue to be made to improve them. However, this is not an easy task, because they are developed by technical committees on an international consensus basis, and reaching international consensus is always a challenge. Consequently, the introduction and adoption of new concepts and procedures can be a lengthy process, but persistence usually pays off.

References
Gy, P. (1982) Sampling of particulate materials Theory and practice, 2nd edn, Elsevier, Amsterdam. Holmes, R.J. (1987) Assessment of minimum sample mass for coal, Mineral Engineering Communication, MIE/C23, CSIRO Division of Mineral Engineering, Australia. International Organization for Standardization (ISO) (1995) Results of testwork on sample division for iron ores, ISO/TC 102 Technical Committee Report No. 9, Japan Iron and Steel Federation, Tokyo, Japan. International Organization for Standardization (ISO) (2001) Hard coal and coke Mechanical sampling Part 2: Coal Sampling from moving streams, ISO 13909-2, ISO, Geneva. International Organization for Standardization (ISO) (2006a) Copper, lead, zinc and nickel concentrates Sampling procedures for determination of metal and moisture content, ISO 12743, ISO, Geneva.

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International Organization for Standardization (ISO) (2006b) Hard coal Sampling of slurries, ISO 20904, ISO, Geneva. International Organization for Standardization (ISO) (2009) Iron ores Sampling and sample preparation procedures, ISO 3082, ISO, Geneva. International Organization for Standardization (ISO) (2010) Copper, lead, zinc and nickel concentrates Sampling of slurries, ISO 11794, ISO, Geneva Pitard, F.F. (1993) Pierre Gys sampling theory and sampling practice, 2nd edn, CRC Press, Boca Raton, Florida.

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