A multi-spatial scale assessment of land-use stress on water quality in headwater streams in the Platinum Belt, South Africa.

River water quality is affected by various stressors (land-uses) operating at different hydrological spatial scales. Few studies have employed a multi-scaled analyses to differentiate effects of natural grasslands and woodlands, agriculture, impoundments, urban and mining stressors on headwater streams. Using a multi-scaled modeling approach, this study disentangled the distinct spatial signatures and mechanistic effects of specific stressors and topographic drivers on individual water quality parameters in tributaries of the Gwathle River Catchment in the Platinum Belt of South Africa. Water samples were collected on six occasions from 15 sites on three rivers over 12-months. Physio-chemical parameters as well as major anions, cations and metals were measured. Five key water quality parameters were identified using principal components analysis: sulfate, ammonium, copper, turbidity, and pH to characterise catchment water quality conditions. Using class-level composition (PLAND) and connectedness (COHESION) metrics together with topographic data, generalized linear mixed models were developed at multiple scales (sub-basin, cumulative catchment, riparian buffers) to identify the most parsimonious model with the dominant drivers of each water quality parameter. Ammonium concentrations were best explained by urban stress, Cu increased with mining and agriculture, turbidity increased with elevation heterogeneity, agriculture, urbanisation and fallow lands all at the sub-basin scale. River pH was positively predicted by slope heterogeneity, mining cover and impoundment connectivity at the catchment scale. Sulfate increased with mining and agriculture composition in the 100 m riparian buffer. Hierarchical cluster analysis of water quality and scale-dependent parsimonious drivers separated the river sites into three distinct groups distinguishing pristine, moderately impacted, and heavily mined sites. By demonstrating stressor- and scale-dependent water quality responses, this multi-scale nested modeling approach reveals the importance of developing adaptive, targeted management plans at hydrologically meaningful scales to sustain water quality amid intensifying land use.

Removal of per- and polyfluoroalkyl substances from aqueous media using synthesized silver nanocomposite-activated carbons.

PURPOSE: Per- and polyfluoroalkyl substances (PFAS) have been found to be widespread, extremely persistent and bioaccumulative with toxicity tendencies. Pre-synthesized nanocomposite-activated carbons, referred to, as physically activated maize tassel silver (PAMTAg) and chemically activated maize tassel silver (CAMTAg) were utilized in the present study. They were used for the removal of 10 PFAS from aqueous solutions. METHODS: The nanocomposite-activated carbons were characterized via scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, Brunauer Emmett Teller (BET) and other techniques. Batch equilibrium experiments were conducted in order to investigate the effects of solution pH, adsorbent dosage, initial PFAS concentration and temperature on the removal of PFAS using PAMTAg and CAMTAg. Langmuir and Freundlich adsorption isotherm models were used to analyse the equilibrium data obtained. RESULTS: Maximum adsorption capacities of 454.1 mg/g (0.91 mmol/g) and 321.2 mg/g (0.78 mmol/g) were recorded for perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA), respectively using CAMTAg. The values recorded for the Gibbs' free energy (ΔG°) for the adsorption of PFOS and PFOA onto PAMTAg and CAMTAg were negative; PFOS (-9.61, -9.99 and - 10.39), PFOA (-8.77, -9.76 and - 10.21) using PAMTAg; and PFOS (-13.70, -12.70 and - 12.37), PFOA (-12.86, -12.21 and - 11.17) using CAMTAg. Therefore, the adsorption processes were spontaneous and feasible. The values recorded for enthalpy (ΔH°) (kJ/mol) for the adsorption of PFOS (-26.15) and PFOA (-35.86) onto CAMTAg were negative, indicating that the adsorption mechanism is exothermic in nature. Positive values were recorded for ΔH° for the adsorption of PFOS (2.32) and PFOA (12.69) onto PAMTAg, indicative of an endothermic adsorption mechanism. Positive entropy (ΔS°) values (0.04 and 0.07) were recorded for PFOS and PFOA using PAMTAg; whereas negative values (-0.04 and - 0.08) were recorded for ΔS° using CAMTAg. A positive ΔS° indicates an increase in randomness of the adsorbate at the solid-solution interface and the reverse is the case for a negative ΔS°. CONCLUSION: The interplay of electrostatic attraction and hydrophobic interactions enabled the removal of PFAS using PAMTAg and CAMTAg. Findings suggest that PAMTAg and CAMTAg are effective for the removal of PFAS from aqueous media and are good alternatives to commercially available activated carbons. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40201-020-00597-3.

Natural archives of long-range transported contamination at the remote lake Letseng-la Letsie, Maloti Mountains, Lesotho.

Naturally accumulating archives, such as lake sediments and wetland peats, in remote areas may be used to identify the scale and rates of atmospherically deposited pollutant inputs to natural ecosystems. Co-located lake sediment and wetland cores were collected from Letseng-la Letsie, a remote lake in the Maloti Mountains of southern Lesotho. The cores were radiometrically dated and analysed for a suite of contaminants including trace metals and metalloids (Hg, Pb, Cu, Ni, Zn, As), fly-ash particles, stable nitrogen isotopes, polycyclic aromatic hydrocarbons (PAHs) and persistent organic pollutants such as polychlorinated biphenyls (PCBs), polybrominated flame retardants (PBDEs) and hexachlorobenzene (HCB). While most trace metals showed no recent enrichment, mercury, fly-ash particles, high molecular weight PAHs and total PCBs showed low but increasing levels of contamination since c.1970, likely the result of long-range transport from coal combustion and other industrial sources in the Highveld region of South Africa. However, back-trajectory analysis revealed that atmospheric transport from this region to southern Lesotho is infrequent and the scale of contamination is low. To our knowledge, these data represent the first palaeolimnological records and the first trace contaminant data for Lesotho, and one of the first multi-pollutant historical records for southern Africa. They therefore provide a baseline for future regional assessments in the context of continued coal combustion in South Africa through to the mid-21st century.

Assessment of occupational exposure to BTEX compounds at a bus diesel-refueling bay: A case study in Johannesburg, South Africa.

Of increasing concern is pollution by volatile organic compounds, with particular reference to five aromatic hydrocarbons (benzene, toluene, ethyl benzene and two isomeric xylenes; BTEX). These pollutants are classified as hazardous air pollutants. Due to the potential health risks associated with these pollutants, BTEX concentrations were monitored at a bus diesel-refueling bay, in Johannesburg, South Africa, using gas chromatography, coupled with a photo-ionization detector. Results indicate that o-xylene (29-50%) and benzene (13-33%) were found to be the most abundant species of total BTEX at the site. Benzene was within South African occupational limits, but above international occupational exposure limits. On the other hand, occupational concentrations of toluene, ethyl-benzene and xylenes were within national and international occupational limits throughout the monitoring period, based on 8-hour workday weighted averages. Ethyl-benzene and p-xylene concentrations, during winter, correspond to activity at the site, and thus idling of buses during refueling may elevate results. Overall, occupational air quality at the refueling bay is a matter of health concern, especially with regards to benzene exposure, and future reduction strategies are crucial. Discrepancies between national and international limit values merit further investigation to determine whether South African guidelines for benzene are sufficiently precautionary.

Occupational exposure of diesel station workers to BTEX compounds at a bus depot.

Diesel fuel is known to emit pollutants that have a negative impact on environmental and human health. In developing countries like South Africa, attendants are employed to pump fuel for customers at service stations. Attendants refuel vehicles with various octane unleaded fuel, lead-replacement petrol and diesel fuel, on a daily basis. Attendants are at risk to adverse health effects associated with the inhalation of volatile organic compounds released from these fuels. The pollutants released include benzene, toluene, ethylbenzene and xylenes (BTEX), which are significant due to their high level of toxicity. In this study, a risk assessment of BTEX was conducted at a diesel service station for public buses. Using Radiello passive samplers, it was found that benzene concentrations were above recommended international standards. Due to poor ventilation and high exposure duration, the average benzene concentration over the sampling campaign exceeded the US Environmental Protection Agency's chronic inhalation exposure reference concentration. Lifetime cancer risk estimation showed that on average there is a 3.78 × 10-4 cancer risk, corresponding to an average chronic daily intake of 1.38 × 10-3 mg/kg/day of benzene exposure. Additionally, there were incidences where individuals were at potential hazard risk of benzene and toluene that may pose non-carcinogenic effects to employees.