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Seasonal Metal Speciation in the Sabie River Catchment, Mpumalanga, South Africa

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Seasonal Metal Speciation in the Sabie River Catchment, Mpumalanga, South Africa 18th JOHANNESBURG Int'l Conference on Science, Engineering, Technology & Waste Management (SETWM-20) Nov. 16-17, 2020 Johannesburg (SA) Seasonal Metal Speciation in the Sabie River Catchment, Mpumalanga, South Africa 1,2R. Lusunzi, 1E. Fosso-Kankeu, 1F. Waanders of water. Abstract - The present study investigated the hydrochemical Various anthropogenic sources which include mining, characteristic changes of the Sabie River catchment. Water sampling agricultural activities and industrial wastewater contribute to was done in November and December (wet season, 2019) and July pollution of surface water [1], [2]. Various factors that influence (Dry season, 2020). Physicochemical parameters and metal speciation were analyzed to assess their impact on water quality and fitness for the mobility of the likely or definite contaminants from human consumption. The hydrochemical characteristics of Sabie anthropogenic activities such as mining and mineral processing catchment showed variation of quality with seasons when compared activities had been described [3] and [4]. These factors include with drinking water guidelines. Seepage from Nestor tailings storage occurrence, abundance, reactivity and hydrology. The term facility (TSF) was also collected during wet season. In both season, species had been defined as different forms of a particular aqueous metal speciation was done using the PHREEQC geochemical 2+ 2- element or its compounds [5]. For this study, the term speciation modelling code. Higher concentrations of Ca and SO4 were found in mine water while the dominant anion and cation were Mg2+ and Cl- had been used to indicate the distribution of species in samples in surface water samples. Additionally, the seasonal variation in the from the Sabie catchment. For a system containing both metal Sabie catchment quality characteristics was attributed to various and ligand, the distribution of species will depend on the activities taking place around the catchment and except for mine water, concentrations, pH, Eh, stoichiometry and ionic strength [6]. the water quality in the Sabie catchment did satisfy the guidelines The subject of chemical speciation had gained favor in the field postulated. of environmental geochemistry because toxicity, availability and reactivity of element depend on chemical forms in which it Keywords— wet and dry seasons, Sabie River, metal speciation, surface water, tailings storage facility, geochemical modeling occur [7]. Also, the bioavailability and toxicity of an element are highly influenced by the change in oxidation state. For I. INTRODUCTION example, Cr(III) is essential for regular glucose metabolism but Cr(VI) is genotic and may cause cancer [8], [6]; the more Originating in the upper reaches of the town Sabie in reduced form of As, As(III) had been described as more toxic Mpumalanga Province of South Africa, the Sabie River passes than As(V) [6], [9]; Ba2+ is highly toxic while BaSO is through Sabie where entities such as York Timber Sawmills, 4 harmless and can be consumed [10]. wastewater treatment works and now-defunct underground Various studies had been undertaken in South Africa to mines of Transvaal Gold Mining Estate (TGME) are situated. determine speciation in surface water [11], [12], [13], [14], The river further flows through Hazyview and Mkhuhlu and [15]. The present study was aimed at assessing the speciation of other residential areas before entering Kruger National Park metal pollutants and impact on their potential dispersion. (KNP), Mozambique and Indian Ocean respectively. The Sabie-Pilgrim‟s Rest goldfields have rich history of gold II. MATERIALS AND METHODS mining dating back to 1872. Currently, there are no mining activities except for illegal (artisanal) mining on old diggings A. Site Description and tailings storage facilities (TSFs). Apart from mining, there There are various activities within the Sabie catchment area are other different activities that are taking place within the including agriculture, forestry and mining (abandoned TSFs and Sabie catchment area ranging from commercial forestry, illegal mining). Located within Inkomati water Management agricultural, and wastewater treatment works. There are also Area, the Sabie River system is one of the largest rivers in residential areas along the catchment (Simile, Hazyview and Mpumalanga Province. It originates at an altitude of 2207 Mkhuhlu) which are also having potential impact to the quality m.a.s.l., and enters Kruger National Park (KNP) 81.3 km downstream from its source (Fig. 1). The upper reaches are Manuscript received September 22, 2020. This work was supported in part dominated with commercial forestry, sawmills, trout farms and by the Council for Geoscience (sponsor and financial support acknowledgment fishing areas, Sabie town area, agricultural and industrial goes here). R. Lusunzi, E Fosso-Kankeu and F. Waanders are with Water Pollution activities to a small extent. There are also abandoned mines Monitoring and Remediation Initiatives, Research Group (WPMRIRG) in the located in the upper reaches of the Sabie catchment with illegal CoE of C-Based Fuels, School of Chemical and Minerals Engineering, mining taking place. North-West, University, Potchefstroom, South Africa R. Lusunzi is with the Council for Geoscience, Economic Geology & Geochemistry Unit, 280 Pretoria Road, Silverton, 0184. https://doi.org/10.17758/EARES10.EAP1120251 76 18th JOHANNESBURG Int'l Conference on Science, Engineering, Technology & Waste Management (SETWM-20) Nov. 16-17, 2020 Johannesburg (SA) III. RESULTS AND DISCUSSION Seasonal variation of parameters analyzed onsite and alkalinity are presented in Table 1. For both seasons, the pH values were alkaline in all surface water samples with mean values of 7.5 in wet season and 7.9 in dry season respectively. However, seepage collected from Nestor TSF had low pH of 2.5, high EC and Eh recorded at 3890 µS/cm and 270.2 mV respectively (SB00). All pH values recorded in both seasons were within acceptable limit for [17] with the exception of mine water. The values of pH measured from Sabie catchment area is a direct function of its total dissolved solids (TDS) and indicates concentrations of soluble salts in water. All values recorded in the Sabie River were within SANS (2015) limits. However, values recorded at SB11 located next to Glynn‟s Lydenburg TSF and SB12 (Klein Sabie River) were slightly above Fig. 1 : Location of Sabie catchment area (CGS 1: 250 000) recommended limits with higher values recorded at Nkambeni B. Sample collection and analyses and Bega Rivers (295 µS/cm and 547 µS/cm respectively). High values of EC in these sites can be attributed to human activities A total of 22 surface water samples were collected from the as there was evidence of dumping of waste at those sites. The Sabie River including its tributaries during wet season values of DO were above recommended limit by WHO (2011) (November/December, 2019) and dry season (July/August for both seasons and this can be attributed to aerobic conditions 2020). Seepage from Nestor TSF was also collected during wet prevailing in the Sabie catchment area. According to [18] the season. Sampling sites were predetermined and covered concentrations of DO indicate changes in the redox state and upstream to downstream of the Sabie River to Kruger National microbial activity of water samples. The values of Eh ranged Park as well as connected streams. The sampling sites were from -75.9 to -2.6 in both seasons with the mean of -35.9 during chosen to determine the contribution of anthropogenic activities wet season and -47.41 in dry season. These low values of Eh can such as mining, forestry and agriculture, to the pollution of the be attributed to the alkaline pH within the Sabie catchment. This Sabie catchment area. Sampling was done according to standard is supported by high values (270.2 mV) recorded at Nestor TSF procedures [16] during dry and wet seasons. Water samples seepage sample which had acidic pH (2.5). were collected using 100 mL polyethylene bottles. Sample TABLE I: SEASONAL VARIATION OF PARAMETERS MEASURED IN SITU AND bottles were rinsed at least three times using the water that is to ALKALINITY (MG/L CACO3) MEASURED IN SURFACE WATER IN THE VICINITY OF be sampled. The samples were filtered using 0.45 μm filter SABIE CATCHMENT membrane for elemental (major, minor and trace element) and Alkalinity anion analyses. Elemental analysis samples were acidified using Sample pH EC (µS/cm) Eh (mV) DO (mg/L) (mg/L CaCO3) number 3M nitric acid (HNO3 for preservation purpose. Immediately Wet Dry Wet Dry Wet Dry Wet Dry Wet Dry upon collection samples were placed in a cooler at 4 C for SB01 7.8 8.3 78.3 64.7 -37.0 -64.5 7.5 9.5 33.6 29.1 transportation and storage. The following key variables were SB02 7.9 7.8 130.0 105.0 -46.2 -40.0 7.4 8.5 55.2 49.8 SB03 8.1 8.3 153.1 149.1 -50.5 -64.2 7.3 8.7 61.1 60.4 analyzed on-site, as they are likely to change with time or during SB04 8.3 8.2 168.0 141.0 -66.9 -64.5 7.8 8.3 59.5 54.6 transportation: pH, redox-potential (Eh), electrical conductivity SB05 8.0 8.2 142.4 101.0 -55.0 -63.2 7.2 9.6 56.2 52.1 SB06 7.3 8.0 120.0 120.5 -41.4 -49.8 6.8 9.1 47.1 50.7 (EC), temperature (T), dissolved oxygen (DO), total dissolved SB07 8.0 8.1 135.4 125.1 -45.9 -50.2 7.1 9.2 37.1 126.0 solids (TDS) and salinity following the South African National SB08 7.7 8.1 108.0 119.1 -16.2 -58.4 7.3 9.5 49.9 46.8 Standard (SANS) 5011 method. These variables were measured SB09 8.0 8.1 128.0 238.0 -55.4 -60.5 6.7 8.3 47.0 87.2 SB10 7.3 8.5 83.7 67.4 -3.6 -75.9 7.1 8.6 39.1 20.0 using a WTW multi 3430 measurement meter.
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