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Evaluation of pH Testing Methods for Sulfidic Mine Waste

Bewertung von pH Prüfverfahren für sulfidische Abfälle

Evaluación de los métodos de medida de pH para residuos mineros sulfurados

硫化物废矿石的pH值测定方法

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Abstract

Environmental assessment of solid mine waste is required throughout the life of a mine. This has driven the need for tools and practices to understand the current state of net acidity in mine wastes. Rinse and paste pH tests are commonly used in the initial screening of waste to provide a preliminary evaluation of its current net acidity. Such pH tests are particularly useful for assessing the chemistry of first flush waters draining sulfidic rocks and wastes. In this study, we compared nine different pH tests (rinse and paste pH tests as well as soil tests of the International Organization for Standardization ISO 10390:2005; American Society for Testing and Materials ASTM D4972-01 2007; Standards Australia AS4969.2-2008), using three different sulfidic rock samples and the acid–base accounting standard KZK-1. We observed significant variability in measured pH for the same samples using the different test methods. We show that different rinse and paste pH methods using different grain sizes and extraction solutions can result in different risk classification for ARD assessments. We recommend carrying out pH measurements using 0.01 M CaCl2 solution, which results in more rapid, reproducible, and precise analyses than using deionised water.

Zusammenfassung

Die Umweltprüfung von festen bergbaulichen Abfällen ist während der gesamten Betriebsdauer eines Bergwerks notwendig. Dies hat die Entwicklung von Werkzeugen und Methoden zur Ermittlung des aktuellen Zustands der Nettoacidität in Bergbauabfällen vorangetrieben. Die pH-Wert-Messung in Bodenlösungen wird üblicherweise in der ersten Untersuchung von Feststoffen angewandt, um die Nettoacidität abzuschätzen. Solche pH-Wert-Messungen sind besonders hilfreich für die Abschätzung der Hydrochemie in sogenannten First-Flush-Wässern aus sulfidischen Gesteinen und Abfällen. In der vorliegenden Studie wurden neun verschiedene pH-Verfahren (in der Bodenlösung sowie Bodentests der Internationalen Organisation für Normung ISO 10390:2005; der Amerikanischen Gesellschaft für Prüfungen und Materialien ASTM D4972-01 2007; der Australischen Normenorganisation AS4969.2-2008) verglichen. Die pH-Verfahren wurden an drei verschiedenen sulfidischen Gesteinsproben sowie an dem Säure-Base-Bilanz-Standard KZK-1 durchgeführt. Wir beobachteten bei den unterschiedlichen Prüfverfahren signifikante Unterschiede der gemessenen pH-Werte für gleiche Proben. Wir zeigen, dass die Verwendung unterschiedlicher Korngrößen und Extraktionslösungen bei den pH-Verfahren in der Bodenlösung zu Differenzen in der Abschätzung des Versauerungspotentials führt. Wir empfehlen die Verwendung von 0.01 M CaCl2-Lösung zur Herstellung der Bodenlösung, da gegenüber destilliertem Wasser die pH-Wert-Messung schneller, reproduzierbarer und präziser ist.

Resumen

Durante la vida de una mina, se requiere realizar permanentes relevamientos ambientales de los residuos mineros sólidos. Esto conlleva el uso de herramientas y prácticas para evaluar la acidez neta de los residuos mineros. Los ensayos de pH en pasta son comúnmente usados en el análisis inicial de los residuos para proporcionar una evaluación preliminar de su acidez neta. Tales ensayos de pH son particularmente útiles para indicar la química de los primeros flujos de agua que drenan las rocas sulfuradas y los residuos. En este estudio comparamos nueve diferentes ensayos de pH (ensayos de pH en pasta y ensayos de la International Organization for Standardization ISO 10390:2005; American Society for Testing and Materials ASTM D4972-01 2007; Standards Australia AS4969.2-2008), usando tres diferentes muestras de roca sulfurada y normas de cuantificación ácido-base KZK-1. Se observó una significativa variabilidad en la medida de pH para las mismas muestras empleando diferentes métodos. Mostramos que los diferentes métodos de pH en pasta, usando diferentes tamaños de grano y soluciones extractivas, pueden resultar en clasificaciones diferentes para el riesgo de ARD. Recomendamos realizar las medidas de pH utilizando solución 0.01 M CaCl2 que resulta en análisis más rápidos, reproducibles y precisos que usando agua desionizada.

摘要

矿山固体废矿石的环境影响评价贯穿整个采矿生产过程,推动着矿山废矿石净酸度评价方法的发展。废矿石的冲洗液和糊状物pH试验(rinse and paste pH tests)用以评价废矿石现状净酸度特征,尤其适于初期流经硫化物废矿石的冲洗液的水化学特征分析,能够为矿山废矿石的初步产酸风险分类提供重要试验依据。利用3种不同的硫化物废矿石样品,采用KZK-1酸-碱平衡计算方法,比较了冲洗液和糊状物pH试验及国标 (ISO 10390:2005)、美国试验与材料协会标准 (ASTM D4972-01 2007) 和澳大利亚标准 (AS4969.2-2008) 的土壤pH试验等9种不同的pH试验结果。结果显示,相同样品、不同pH测试方法的实测pH值明显不同。冲洗液和糊状物pH试验 (rinse and paste pH tests) 会因试验颗粒粒径和浸取液等试验条件变化而导致废矿石产酸风险分类不同。建议使用0.01 M的CaCl2溶液进行pH试验;因为它比去离子水试验速度更快、试验可重复性更好、试验精度更高。

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Acknowledgments

The authors acknowledge the support of CRC ORE, established and supported by the Australian Government’s Cooperative Research Centres Programme. Copper Mines of Tasmania and the Queensland Dept. of Natural Resources and Mines are thanked for access to sulfidic rocks. Dr. Daniel Gregory is thanked for initial sample preparation. Mr. John Aalders is acknowledged for his support in the laboratory and with sample preparation. Dr. Stafford McKnight (Federation University) is acknowledged for his expertise in QXRD.

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Authors and Affiliations

  1. School of Physical Sciences, University of Tasmania, Private Bag 79, Hobart, TAS, 7001, Australia

    Taryn L. Noble & Anita Parbhakar-Fox

  2. Institute of Sustainable Resource Extraction, RWTH Aachen, Wuellnerstrasse 2, 52062, Aachen, Germany

    Bernd G. Lottermoser

Authors
  1. Taryn L. Noble
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  2. Bernd G. Lottermoser
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  3. Anita Parbhakar-Fox
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Correspondence to Taryn L. Noble.

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Supplementary Fig. 1

Risk classification of the bulk samples based on the total metal and metalloid concentrations and the rinse and paste pH values from this study. The pH data plotted are from methods using DI water and 0.01 M CaCl2. The classification is based on the risk of acid rock drainage (ARD) and high metal loading (ML) for RG-WRD1, CMT-WRD1 and CMT-ROM1. (PDF 314 kb)

Supplementary Fig. 2

pH data for waste rock samples from Croydon, Queensland. Two size fractions, <0.075 mm and <2 mm were compared following ASTM D4972-01(2007)(E) (ASTM; + for <0.075 mm and × for <2 mm) and ISO 10390:2005(E) (ISO; circles) methods using 0.01 M CaCl2. Paste pH data measured using Smart et al. (2002) based on distilled water as the extraction solution are also shown (diamond). The pH data measured using 0.01 M CaCl2 are clustered according to grain size despite differences in the methodological procedures. The pink shaded area below pH 5.5 highlights the paste pH cut-off criterion used by Parbhakar-Fox et al. (2014) in ARD risk classification of the waste rock samples into non-acid forming (NAF) and potentially acid forming (PAF) materials. (PDF 324 kb)

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Noble, T.L., Lottermoser, B.G. & Parbhakar-Fox, A. Evaluation of pH Testing Methods for Sulfidic Mine Waste. Mine Water Environ 35, 318–331 (2016). https://doi.org/10.1007/s10230-015-0356-2

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