SME Annual Meeting

Feb. 28-Mar. 03, 2010, Phoenix, AZ

Preprint 10-036

STANDARDIZATION OF THE ACID NEUTRALIZATION POTENTIAL ACIDITY METHOD FROM ADTI-MMS THROUGH ASTM

C. H. Bucknam, Newmont Metallurgical Services, Englewood, CO

INTRODUCTION • Results are expressed in percent calcium carbonate to be

consistent with standard assay practices in the industry.
Acid neutralization titrations were applied to the characterization
• The method includes procedures for initial laboratory test method
of soil and overburden for the control and prediction of acid rock
performance demonstration before initial use and uses calcium
drainage in the coal fields of the eastern United States in the 1970’s
carbonate-silica calibration mixtures for routine quality control as
(1). These became known as the Sobek methods as a result of the
well as blanks, reference samples and standard addition samples.
early United States Environmental Protection Agency publication and
the methods have been modified (2) to be adapted to many INTERLABORATORY TESTING OF ANPA
applications in the metal mining sector (3,4,5,6,), and, as a result, there
are a large number of acid neutralization potential methods being used ASTM International was launching an ILS support service at the
that are referred to as Modified Sobek methods. time that the ANPA method was approved for interlaboratory testing,
so the ILS was part of the pilot program for the new service (ILS12). A
Standardization of neutralization potential methods for metal commercial laboratory was selected for preparation and distribution of
bearing ores and related materials based on carbonate carbon, rather the test sample; however, they were not successful in distribution of
than titration, commenced in the 1990’s through the American Society the samples to the participating Canadian laboratories. As a result, the
of Methods and Materials (ASTM) Committee E01 on Analytical commercial laboratory distributed the test materials to the labs in the
Chemistry for Metal Ores and Related Materials Subcommittee E01.02 US and Newmont Metallurgical Services (NMS) distributed the test
on Ores, Concentrates and Related Metallurgical Materials (7). A samples to the Canadian labs. The Participating laboratories are listed
subcommittee section, E01.02.05 on Environmental Methods, was in Table 1.
organized to coordinate the method and material standardization
efforts of ASTM and the Acid Drainage Technology Initiative Metal Table 1. Laboratories Participating in the ILS.
Mining Sector (ADTI-MMS) Prediction Committee (8), which took on Laboratory Location
the project of standardization of the acid neutralization potential acidity
titration method (ANPA) to supplement the carbonate carbon method ACZ Colorado, USA
in E1915 (9) for application to samples which have metal carbonates ALS Chemex Vancouver, BC
(10), in particular, which result in overestimation of the neutralization
potential using the carbonate carbon methods (11). CANMET Ontario, Canada
MODIFICATIONS TO THE SOBEK METHOD Cantest BC, Canada
The ANPA method is classified as a Modified Sobek method and Energy Labs Montana, USA
is intended to be a rapid automatable method for conducting
geochemical surveys on a large number of samples. The original NMS Colorado, USA
interlaboratory study (ILS) plan was to use an automatic titrator which
SGS Ontario, Canada
would facilitate the automation of the method. The task group,
however, was unable to find sufficient laboratories (8 minimum) to Sierra Environmental Monitoring Nevada, USA
complete the round-robin testing, so a manual titration method to an
8.3 pH endpoint was added as an option.
Testing materials were selected from commercially available silica
The ANPA method differs from the original Sobek method and certified reference materials were supplied by CANMET, Leco
including the following modifications: Corporation, the National Institute of Standards and Technology
(NIST), NMS and the United States Geological Survey (USGS). NMS
• A 1-g rather than a 2-g sample weight is used.
also purchased calibration mixtures composed of silica, calcium
• A finely ground assay pulp sample is used (-100 mesh or finer).
carbonate and ferrous sulfate, prepared by High Purity Standards.
• A fixed volume of sulfuric acid is added to the sample for Materials which were used as the test materials in the final ILS and the
digestion, rather than selecting hydrochloric acid volume and testing results are summarized in Table 2.
strength based on subjective fizz testing.
• A second higher concentration of sulfuric acid is added depending Table 2. ILS Materials and Results, % CaCO3.
on the pH of the slurry after acid addition or digestion and the Material Mean Min. SD R
slurry is re-digested. SRM-2780 Hard Rock Mine
•
o
Digestion is conducted in a water bath at 80 C for one hour. 0.241 0.102 0.89
Waste (NIST)
• The digestion slurry is filtered, treated with hydrogen peroxide, Ottawa Sand (NMS) 0.315 0.007 0.91
boiled to expel the excess hydrogen peroxide and diluted to the DGPM-1 Pinson Disseminated
initial volume before titration. 0.512 0.156 0.90
Gold Ore (USGS)
• The reacted solution is either automatically titrated to a strong SRM-331a Copper Mill Tails
acid endpoint or manually titrated to pH 8.3, using the strong base 2.15 0.107 1.09
(NIST)
titrant. SRM-886 Refractory Gold Ore
• Samples which indicate that more acid was titrated than was 45.5 0.967 6.83
(NIST)
added report negative results to indicate the concentration of Part 502-372 Limestone Tailings
acidity present. 57.2 1.47 9.45
(Leco)

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 SME Annual Meeting
Feb. 28-Mar. 03, 2010, Phoenix, AZ

ASTM Practice E 1601 (12) was used to design the ILS and decided to incorporate the method as a part of E 1915, so a revision
interpret the results. Within laboratory repeatability is expressed in the was prepared, approved and submitted to subcommittee
minimum standard deviation (Min.SD) shown in Table 2, this is the
precision expected when analyzing the material in sequential Table 4. Impurities Detected in Five Grams of Silica Digested and
replicates. The main purpose of the ILS, however, is to determine the Diluted According to the ANPA Method.
between laboratory reproducibility index, R. This value is the Impurity Unit Assay
maximum difference expected in results from two different laboratories Ag mg/l <0.050
at 95% confidence. E 1601 recommends setting the lower limit of the Al mg/L 11.6
method at 2R for the lowest concentration material, so the useful range As µg/L 9.4
of the method tested would be 1.8-100 % CaCO3, according to that B µg/L 30.5
convention. Ba mg/l 0.127
Be µg/L <0.1
The results of the interlaboratory testing were drafted by the task
Ca mg/l 3.220
group into a research report, which underwent consensus review by
Cd µg/L 0.51
the task group and then was approved by the Committee E01
statistical reviewer, which was facilitated by setting up a collaboration Co mg/l <0.050
site on the ASTM web site. The task group recommended allowing the Cr mg/l 2.590
user of the method to establish the lower limit of the method on a site Cu mg/l <0.050
specific basis by conducting an ILS with their own materials, as is Fe mg/l 62.200
allowed in E 1915, since the precision of the application of the method K mg/l 1.770
at a particular site is dependent on the mineralogy of the materials Li µg/L 12.7
originating from that site. However the user of the method is advised Mg mg/l 0.914
not to use the ANPA result below 1.8 % CaCO3 for the calculation of Mn mg/l 0.333
neutralization potential ratio (NPR). This is good agreement with the Mo µg/L 8.7
practice of classification of materials with neutralization potential (NP) Na mg/l 0.975
below 20 tons CaCO3/ton (2 % CaCO3) material as “uncertain” used by Ni mg/l 0.115
many practitioners. P mg/l 0.51
As a result of the ILS, the calibration mixtures between -1 % Pb µg/L 17.8
CaCO3 (ferrous sulfate and silica) and 1% CaCO3 (calcium carbonate S mg/l 147.00
and silica) were not included in the laboratory performance test and Sb µg/L 0.6
routine quality control during application of the method, since they Se µg/L 0.7
were two variable. The calibration materials means and acceptance Si mg/l 7.04
ranges determined during the ILS are shown in Table 3. Sn mg/l <0.050
Sr mg/l 0.050
Table 3. Acceptance Ranges for Calibration Mixtures, % CaCO3 Te µg/L <0.1
Calibration Mixture Mean Minimum Maximum Ti mg/l <0.050
-1.0 -0.64 -1.28 -0.01 Tl µg/L 0.3
1.0 1.01 0.64 1.38 V mg/l <0.050
10.0 10.5 8.62 12.4 Zn mg/l 0.164
20.0 20.7 18.0 23.3
CaCO3 97.9 92.9 103 Table 5. Comparison of ILS Results to ABA Certificates, % CaCO3.
Method NBM-1 KZK-1
The task group was concerned about the slight high bias in the ANPA 4.72 5.68
range of -1 to 20 % CaCO3 in the range of 0.4-0.7 % CaCO3. An Modified Sobek Slight Fizz 4.66 5.89
investigation was undertaken at NMS to see if the result could be
Sobek Slight Fizz 4.96 5.90
attributed to contamination in the silica used, which could possibly
Modified Sobek Moderate Fizz 5.23 6.16
consume some acid. A larger sample of 5 g was subjected to the
Sobek Moderate Fizz 7.21 6.48
ANPA digestion procedure in duplicate and one solution was titrated
and the other solution was assayed by inductively coupled plasma
emission and mass spectrometry. During subcommittee balloting it was realized that significant
reformatting would be required and several improvements were
The titration result was 0.05% CaCO3, confirming no significant proposed, so it took three subcommittee ballots to get the revision of E
bias and the elemental analysis results are shown in Table 4, 1915 to the Main Committee ballot and Society Review, that ballot is
confirmed no significant contamination. The result, suggests, however, due to close on November 2, 2009, the day after this manuscript it due.
that the results in the “uncertain” zone of the method, below 2 % Significant changes to the E 1915 method that resulted from the
CaCO3, can be improved by using a 5 g sample, reducing uncertainty if balloting include:
NPR values are needed in that region of concentration.
• The title is changed to Analysis of Metal Bearing Ores and
Due to the need to reduce the number of testing materials in order Related Materials for Carbon, Sulfur and Acid-Base
to expedite the final round- robin the CANMET certified acid-base Characteristics.
accounting reference materials NBM-1 and KZK-1 were not included in • Acid-base characteristics and leach residues are added to the
the final round of testing. A total of eight measurements were scope.
completed on the certified ABA materials and the results of the testing • Acid Neutralization Potential Acidity Titration -1.0 to 100% CaCO3
are shown in Table 5. Results are in good agreement with the is added after Hydrochloric Acid Loss Carbon in the scope.
certificate values; particularly with the lower range Modified Sobek, • Standardization and Standardization samples are defined.
which is the basis for the ANPA method. • Significance and use section is expanded to address speciation of
ASTM BALLOTING OF E 1915 STANDARD REVISION INCLUDING carbon sulfur, acid-base accounting and organic carbon.
THE ANPA METHOD • Warnings are added concerning decomposition of carbonate
minerals by the pyrolysis method.
At the conclusion of approval of the draft research report, ASTM • Apparatus, Reagents, Calibration and Standardization sections
E01 procedures require approval of the method or revision of an are transferred to the individual methods.
existing method to be approved by the Editorial Committee. It was • Drying precautions are added relating to sulfide oxidation.

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 SME Annual Meeting
Feb. 28-Mar. 03, 2010, Phoenix, AZ

• Acid Neutralization Potential Acidity Titration is added after 9. ASTM International (2009) E1915-07a Standard test methods for
Hydrochloric Acid Loss Carbon Method. analysis of metal bearing ores and related materials by
• Interpretation of Results Section is expanded to allow use of combustion infrared-adsorption spectrometry. In Annual Book of
ANPA titration instead of carbonate carbon for acid-base ASTM Standards, Vol. 03.05, 14 p. ASTM, West Conshohocken,
classification purposes. PA. www.astm.org
• Warnings are included that in addition to replacement of fizz tests
10. ADTI Prediction Workgroup (2000). Prediction of Water Quality at
with pH checks, some difficult to digest carbonate minerals should
Surface Coal Mines. NLMRC, Morgantown, WV pp 82-84.
have the higher acid addition if the hydrochloric acid loss exceeds
1% carbon. 11. Bucknam, C. H. (2002). Interpretation of the ASTM standard
• The use of the three traditional classifications is put into context of carbon-sulfur methods interlaboratory testing results using XRD-
the eight classifications used for net calcium carbonate. XRF analyses. SME Littleton, CO. www.onemine.org
• Conversions are provided to translate results to classical NP, AP
and NNP units. 12. ASTM International (2009) E1601-98(2003)e1 Standard practice
for conducting an interlaboratory study to evaluate the
• Differentiation of the inert and neutral classifications is clarified.
performance of an analytical method . In Annual Book of ASTM
• A section is added to clarify the use of acid-base classification
Standards, Vol. 03.05, 14 p. ASTM, West Conshohocken, PA.
and confirmation testing on a site specific basis, including the
www.astm.org
need to use separate methods for identifying samples containing
acidic salts.
CONCLUSIONS AND RECOMMENDATIONS
Standardization of the ANPA method has provided improved
modifications of the Sobek acid neutralization titration method for
potential automation of acid-base accounting surveys where they are
needed to replace carbonate carbon estimates of neutralization
potential due to metal carbonate mineralogy and also provides a new
tool for practitioners that prefer the use of titration to estimate acid
neutralization potential.
Analysis of results indicated that a high bias for silica could not be
confirmed, but that using a five gram sample in the “uncertain” range
may provide more useful results for those practitioners that prefer the
use of NPR under the lower limit of 1.8 % CaCO3. It is recommended
that a ruggedness test be carried out at several laboratories on the ILS
materials with concentrations below 2 % CaCO3, to determine if more
precise results can be obtained in that range using five gram samples,
prior to interlaboratory testing of the method option.
REFERENCES
1. Smith, R. M., W.E. Grube Jr., T. Arkle Jr. and A. Sobek (1974).
Mine spoil potentials for soil and water quality. EPA-670/2-74-070,
Washington, D. C., pp 50-51.
2. Sobek, A.A., W.A. Schuller, J.R. Freeman and R.M. Smith (1978)
Field and laboratory methods applicable to overburdens and
minesoils. EPA-600/2-78-054, Washington D. C. pp 47-50.
3. Reclamation Research Unit and Shafer and Associates (1987).
Laboratory analytical protocol for the stream bank tailings and
revegetation studies: Silver Bow Creek RI/FS, EPA Region VIII.
Document No. SBC-STARS-UP-F-RI-R1167. Appendix 16 Acid-
Base Account. P A115-A118.
4. MEND (1991). Acid rock drainage prediction manual: A manual of
chemical evaluation procedures for the prediction of acid drainage
from mine wastes, CANMET, Ottawa, Ontario, Canada.
5. White, W.W.III and T. H. Jeffers (1994) Chemical predictive
modeling of acid rock drainage from metallic sulfide-bearing
waste rock. In Environmental Geochemistry of Sulfide Oxidation,
ACS, Washington D.C.
6. Lawrence, R.W. and Y. Wang (1997). Determination of
neutralization potential in the prediction of acid rock drainage. In
th
Proc, 4 ICARD, Vancouver, BC, Canada.
7. Bucknam, C. H. and F.K. Tjong (1997). Application of
interlaboratory Statistics for carbon and sulfur to estimate
uncertainties in net carbonate values. SME Littleton, CO.
www.onemine.org
8. Bucknam, C.H., W.W. White III and K. Lapakko (2009).
Standardization of Mine Waste Characterization Methods by
th
ADTI-MMS. In Proc. 8 ICARD, www.securing.skelleftea.se/

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