Limitations of wastewater treatment plants in removing trace anthropogenic biomarkers and future directions: A review.

This review highlights the limitations faced by conventional wastewater treatment plants (WWTPs) in effectively removing contaminants of emerging concern (CECs), heavy metals (HMs), and Escherichia coli (E. coli). This emphasises the limitations of current treatment methods and advocates for innovative approaches to enhance the removal efficiency. By following the PRISMA guidelines, the study systematically reviewed relevant literature on detecting and remedying these pollutants in wastewater treatment facilities. Conventional wastewater treatment plants struggle to eliminate CECs, HMs, and E. coli owing to their small size, persistence, and complex nature. The review suggests upgrading WWTPs with advanced tertiary processes to significantly improve contaminant removal. This calls for cost-effective treatment parameters and standardised assessment techniques to enhance the fate of MPs in WWTPs and WRRFs. It recommends integrating insights from mass-balance model studies on MPs in WWTP to overcome modelling challenges and ensure model reliability. In conclusion, this review underscores the urgent need for advancements in wastewater treatment processes to mitigate the environmental impact of trace anthropogenic biomarkers. Future efforts should focus on conducting comprehensive studies, implementing advanced treatment methods, and optimising management practices in WWTPs and WRRFs.

Nano-TiO2, ultrasound and sequential nano-TiO2/ultrasonic degradation of N-acetyl-para-aminophenol from aqueous solution.

The application of nano-TiO2 as adsorbent combined with ultrasound for the degradation of N-acetyl-para-aminophenol (AAP) from aqueous solution was investigated. The nano-TiO2 was characterized by means of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR). Experimental results revealed that the adsorption of AAP by nano-TiO2 fitted the pseudo-second-order kinetic model, the equilibrium could be explained by the Freundlich isotherm and the treatment process is exothermic. The optimum removal efficiency of AAP (128.89 mg/g (77.33%)) was achieved at pH 4 when 0.03 g of nano-TiO2 was mixed with 50 mL of 100 mg/L AAP aqueous solution at ambient temperature, 60 min contact time, and a stirring speed of 120 rpm. Ultrasound at 20 kHz and pH 3 was favorable and it resulted in 52.61% and 57.43% removal efficiency with and without the addition of nano-TiO2, respectively. The degradation of AAP by ultrasound followed by nano-TiO2 treatment resulted in approximately 99.50% removal efficiency. This study showed that a sequential ultrasound and nano-TiO2 treatment process could be employed for the removal of AAP or other emerging water and wastewater contaminants.

Synthesis of zeolite NaA membrane from fused fly ash extract.

Zeolite-NaA membranes were synthesized from an extract of fused South African fly ash on a porous titanium support by a secondary growth method. The influence of the synthesis molar regime on the formation of zeolite NaA membrane layer was investigated. Two synthesis mixtures were generated by adding either aluminium hydroxide or sodium aluminate to the fused fly ash extract. The feedstock material and the synthesized membranes were characterized by X-diffraction (XRD), scanning electron microscopy (SEM) and X-ray fluorescence spectroscopy (XRF). It was found by XRD and SEM that the cubic crystals of a typical zeolite NaA with a dense intergrown layer was formed on the porous Ti support. The study shows that the source of Al used had an effect on the membrane integrity as sodium aluminate provided the appropriate amount of Na(+) to form a coherent membrane of zeolite NaA, whereas aluminium hydroxide did not. Morphological, the single hydrothermal stage seeded support formed an interlocked array of zeolite NaA particles with neighbouring crystals. Also, a robust, continuous and well-intergrown zeolite NaA membrane was formed with neighbouring crystals of zeolite fused to each other after the multiple stage synthesis. The synthesized membrane was permeable to He (6.0 × 10(6) L m(-2)h(-1) atm(-1)) and CO2 (5.6 × 10(6) L m(-2)h(-1) atm(-1)), which indicate that the layer of the membrane was firmly attached to the porous Ti support. Membrane selectivity was maintained showing membrane integrity with permselectivity of 1.1, showing that a waste feedstock, fly ash, could be utilized for preparing robust zeolite NaA membranes on Ti support.

Leaching and antimicrobial properties of silver nanoparticles loaded onto natural zeolite clinoptilolite by ion exchange and wet impregnation.

This study aimed to compare the leaching and antimicrobial properties of silver that was loaded onto the natural zeolite clinoptilolite by ion exchange and wet impregnation. Silver ions were reduced using sodium borohydride (NaBH4). The leaching of silver from the prepared silver-clinoptilolite (Ag-EHC) nanocomposite samples and their antimicrobial activity on Escherichia coli Epi 300 were investigated. It was observed that the percentage of silver loaded onto EHC depended on the loading procedure and the concentration of silver precursor used. Up to 87% of silver was loaded onto EHC by wet impregnation. The size of synthesized silver nanoparticles varied between 8.71-72.67 nm and 7.93-73.91 nm when silver was loaded by ion exchange and wet impregnation, respectively. The antimicrobial activity of the prepared nanocomposite samples was related to the concentration of silver precursor used, the leaching rate and the size of silver nanoparticles obtained after reduction. However, only in the case of the nanocomposite sample (Ag-WEHC) obtained after loading 43.80 ± 1.90 µg of Ag per gram zeolite through wet impregnation was the leaching rate lower than 0.1 mg L-1 limit recommended by WHO, with an acceptable microbial killing effect.

Evaluation of cytotoxicity and inflammatory activity of wastewater collected from a textile factory before and after treatment by coagulation-flocculation methods.

Effective treatment of textile effluent prior to discharge is necessary in order to avert the associated adverse health impacts on human and aquatic life. In the present investigation, coagulation/flocculation processes were evaluated for the effectiveness of the individual treatment. Effectiveness of the treatment was evaluated based on the physicochemical characteristics. The quality of the pre-treated and post-flocculation treated effluent was further evaluated by determination of cytotoxicity and inflammatory activity using RAW264.7 cell cultures. Cytotoxicity was determined using WST-1 assay. Nitric oxide (NO) and interleukin 6 (IL-6) were used as biomarkers of inflammation. NO was determined in cell culture supernatant using the Griess reaction assay. The IL-6 secretion was determined using double antibody sandwich enzyme linked immunoassay (DAS ELISA). Cytotoxicity results show that raw effluent reduced the cell viability significantly (P < 0.001) compared to the negative control. All effluent samples treated by coagulation/flocculation processes at 1 in 100 dilutions had no cytotoxic effects on RAW264.7 cells. The results on inflammatory activities show that the raw effluent and effluent treated with 1.6 g/L of Fe-Mn oxide induced significantly (P < 0.001) higher NO production than the negative control. The inflammatory results further show that the raw effluent induced significantly (P < 0.001) higher production of IL-6 than the negative control. Among the coagulants/flocculants evaluated Al2(SO4)3.14H2O at a dosage of 1.6 g/L was the most effective to remove both toxic and inflammatory pollutants. In conclusion, the inflammatory responses in RAW264.7 cells can be used as sensitive biomarkers for monitoring the effectiveness of coagulation/flocculation processes used for textile effluent treatment.

Fate of the naturally occurring radioactive materials during treatment of acid mine drainage with coal fly ash and aluminium hydroxide.

Mining of coal is very extensive and coal is mainly used to produce electricity. Coal power stations generate huge amounts of coal fly ash of which a small amount is used in the construction industry. Mining exposes pyrite containing rocks to H2O and O2. This results in the oxidation of FeS2 to form H2SO4. The acidic water, often termed acid mine drainage (AMD), causes dissolution of potentially toxic elements such as, Fe, Al, Mn and naturally occurring radioactive materials such as U and Th from the associated bedrock. This results in an outflow of AMD with high concentrations of sulphate ions, Fe, Al, Mn and naturally occurring radioactive materials. Treatment of AMD with coal fly ash has shown that good quality water can be produced which is suitable for irrigation purposes. Most of the potentially toxic elements (Fe, Al, Mn, etc) and substantial amounts of sulphate ions are removed during treatment with coal fly ash. This research endeavours to establish the fate of the radioactive materials in mine water with coal fly ash containing radioactive materials. It was established that coal fly ash treatment method was capable of removing radioactive materials from mine water to within the target water quality range for drinking water standards. The alpha and beta radioactivity of the mine water was reduced by 88% and 75% respectively. The reduced radioactivity in the mine water was due to greater than 90% removal of U and Th radioactive materials from the mine water after treatment with coal fly ash as ThO2 and UO2. No radioisotopes were found to leach from the coal fly ash into the mine water.

The leaching behaviour and geochemical fractionation of trace elements in hydraulically disposed weathered coal fly ash.

A five-step sequential extraction (SE) procedure was used to investigate the leaching behaviour and geochemical partitioning of the trace elements As, Zn, Pb, Ni, Mo, Cr and Cu in a 20-year-old fly ash (FA) dump. The weathered FA, which was hydraulically co-disposed with salt laden brine in slurry form (FA: brine ratio of 1:5), was analyzed and compared with fresh FA. The weathered FA samples were collected from three cores, drilled at a coal-fired power station in the Republic of South Africa while the fresh FA sample was collected from the hoppers in the ash collection system at the power station. The FA samples were sequentially leached using: ultrapure water; ammonium acetate buffer solution (pH 7); ammonium acetate buffer solution (pH 5); hydroxylamine hydrochloride in nitric acid (pH 2) and finally the residues were digested using a combination of HClO4: HF: HNO3 acids. Digestion of as received (unleached) FA samples was also done using a combination of HClO4: HF: HNO3 acids in order to determine the total metal content. The trace element analysis was done using ICP-OES (Varian 710-ES). The SE procedure revealed that the trace elements present in the fresh FA and the weathered FA samples obtained from the three cores could leach upon exposure to different environmental conditions. The trace elements showed continuous partitioning between five geochemical phases i.e., water soluble fraction, exchangeable fraction, carbonate fraction, Fe and Mn fraction and residual fraction. Although the highest concentration of the trace elements (ranging 65.51%-86.34%) was contained in the residual fraction, a considerable amount of each trace element (ranging 4.42%-27.43%) was released from the labile phases (water soluble, exchangeable and carbonate fractions), indicating that the trace species readily leach from the dumped FA under environmental conditions thus pose a danger to the receiving environment and to groundwater.

Factors in the decline of the African penguin: Are contaminants of emerging concern (CECs) a potential new age stressor?

The African penguin is currently experiencing a significant decline, with just over 10,000 breeding pairs left. A substantial body of research reflects the impacts of contaminants of emerging concern (CECs) on the marine environment, with wastewater treatment plants reported as one of the main sources of CEC release. In South Africa, CECs were identified contaminating the marine environment and bioaccumulating in several marine species. Approximately 70 % of all African penguin colonies breed in close proximity to cities and/or harbors in South Africa. Currently, the impact of CECs as a stressor upon the viability of African penguin populations is unknown. Based on the search results there was a clear lack of information on CECs' bioaccumulation and impact on the African penguin. This narrative review will thus focus on the prevalent sources and types of CECs and examine the reported consequences of constant exposure in seabirds, particularly African penguins.

Iron nanoparticles prepared from South African acid mine drainage for the treatment of methylene blue in wastewater.

In this study, three acid mine drainage (AMD) sources were investigated as potential sources of iron for the synthesis of iron nanoparticles using green tea extract (an environmentally friendly reductant) or sodium borohydride (a chemical reductant). Electrical conductivity (EC), total dissolved solids (TDS), dissolved oxygen (DO), oxidation-reduction potential (ORP), ion chromatography (IC), and inductively coupled plasma-mass spectroscopy (ICP-MS) techniques were used to characterize the AMD, and the most suitable AMD sample was selected based on availability. Additionally, three tea extracts were characterized using ferric-reducing antioxidant power (FRAP) and 2,2-diphenyl-1-picryl-hydrazine-hydrate (DPPH), and the most suitable environmentally friendly reductant was selected based on the highest FRAP (1152 µmol FeII/g) and DPPH (71%) values. The synthesized iron nanoparticles were characterized and compared using XRD, STEM, Image J, EDS, and FTIR analytical techniques. The study shows that the novel iron nanoparticles produced using the selected green tea (57 nm) and AMD were stable under air due to the surface modification by polyphenols contained in green tea extract, whereas the nanoparticles produced using sodium borohydride (67 nm) were unstable under air and produced a toxic supernatant. Both the AMD-based iron nanoparticles can be used as Fenton-like catalysts for the decoloration of methylene blue solution. While 99% decoloration was achieved by the borohydride-synthesized nanoparticles, 81% decoloration was achieved using green tea-synthesized nanoparticles.

Chemometrics, health and environmental risk assessments of commonly consumed biscuits in Lagos and Ibadan metropolises, Southwestern Nigeria.

The United Nations' Agenda 2030 for sustainable development calls, amongst others, for universal action toward ending malnutrition and ensuring healthy living and well-being for all. So, efforts have intensified to attain the sustainable development goal-2 targets on stunting and wasting in children. Reported herein, therefore, is the quantification of metals in biscuits. Biscuits are commonly consumed snacks world-over and have become sources of nourishment for children and adults due to growing sedentary lifestyles and hectic school/work schedules. Nine metals (Pb, Ni, Cu, Co, Zn, Fe, Na, Mg and Ca) were assayed in six biscuit types (crackers, cookies, shortcakes, digestives, cabins and wafers) via wet digestion and flame atomic absorption spectrophotometry, and the ensuing data subjected to multivariate analyses (analysis of variance, Tukey's test, Pearson correlation, and principal component and hierarchical cluster analyses). The highest concentrations of macrominerals were found in the wafers (Ca), crackers (Na) and cabins (Mg) whereas the micronutrients peaked in the cookies (Fe, Zn), crackers (Cu), shortcake (Co) and wafers (Ni), respectively. The metal levels in the sampled biscuits were all safe for consumption, except for Pb at 0.83 ± 0.76-2.3 ± 1.3 mg/kg. Similarly, the health risk assessments of ingesting metals from the biscuits exposed Pb as potentially liable to cause adverse non-carcinogenic and carcinogenic health effects in children (aged 4-20 years) but Co and Ni exhibited borderline non-carcinogenic and carcinogenic health risks, respectively, in children. Gratifyingly, the ecological risk assessments to evaluate the likelihood of wastes, from expired and/or egested potentially toxic metals-contaminated biscuits, to cause damage to ecology were categorized as low. Nonetheless, constant evaluation and monitoring remain germane.

Chemical, mineralogical and morphological changes in weathered coal fly ash: a case study of a brine impacted wet ash dump.

The mobility of species in coal fly ash (FA), co-disposed with brine using a wet ash handling system, from a coal fired power generating utility has been investigated. The study was conducted in order to establish if the wet ash dump could act as a salt sink. The ash was dumped as a slurry with 5:1 brine/ash ratio and the dam was in operation for 20 years. Weathered FA samples were collected along three cores at a South African power station's wet ash dump by drilling and sampling the ash at 1.5 m depth intervals. A fresh FA sample was collected from the hoppers in the ash collection system at the power station. Characterization of both fresh FA and weathered FA obtained from the drilled cores S1, S2 and S3 was done using X-ray diffraction (XRD) for mineralogy, X-ray fluorescence (XRF) for chemical composition and scanning electron microscopy (SEM) for morphology. Analysis of extracted pore water and moisture content determination of the fresh FA and the weathered FA obtained from the drilled cores S1, S2 and S3 was done in order to evaluate the physico-chemical properties of the FA. The XRD analysis revealed changes in mineralogy along cores S1, S2 and S3 in comparison with the fresh FA. The SEM analysis revealed spherical particles with smooth outer surfaces for the fresh FA while the weathered ash samples obtained from cores S1, S2 and S3 consisted of agglomerated, irregular particles appearing to be encrusted, etched and corroded showing that weathering and leaching had occurred in the ash dump. The moisture content (MC) analysis carried out on the fresh FA (1.8%) and the weathered FA obtained from the drilled cores S1 (41.4-73.2%), S2 (30.3-94%) and S3 (21.7-76.2%)indicated that the ash dump was water logged hence creating favourable conditions for leaching of species. The fresh fly ash (n = 3) had a pH of 12.38 ± 0.15, EC value of 4.98 ± 0.03 mS/cm and TDS value of 2.68 ± 0.03 g/L, the pH of the drilled core S1 (n = 45) was 10.04 ± 0.50, the EC value was 1.08 ± 0.14 mS/cm and the TDS value was 0.64 ± 0.08 g/L. Core S2 (n = 105) had pH of 10.04 ± 0.23; EC was 1.08 ± 0.06 mS/cm and TDS was 0.64 ± 0.04 g/L, while core S3 (n = 66) had pH of 11.04 ± 0.09; EC was 0.99 ± 0.03 mS/cm and TDS was 0.57 ± 0.01 g/L. The changes in pH values can be attributed to the dissolution and flushing out of alkaline oxides like CaO and MgO from the dumped ash. The variations in pH values shows that the fly ash is acidifying over time and metal mobility can be expected under these conditions. The large decrease of EC in the drilled ash cores S1, S2 and S3 compared to the fresh ash indicated a major loss of ionic species over time in the ash dump. The XRF analysis showed the progressive dissolution of the major aluminosilicate ash matrix which influenced the release of minor and trace elements into the pore water enhancing their mobility as the ash dam acidified over time. Brine co-disposal on the ash may have been responsible for the slight enrichment of some species such as Na (0.27-0.56%), SO4(2-) (0.06-0.08%), Mg (0.57-0.96 %) and K (0.02-0.34%) in the disposed weathered FA. However, there was no significant accumulation of these species in the disposed FA despite continuous addition of large volumes of highly saline brine over the 20 year period that the dump existed, indicating that the ash dam was incapable of holding salts and continually released elements to the environment over the lifetime of the dam.

Comparison of CO2 capture by ex-situ accelerated carbonation and in in-situ naturally weathered coal fly ash.

Natural weathering at coal power plants ash dams occurs via processes such as carbonation, dissolution, co-precipitation and fluid transport mechanisms which are responsible for the long-term chemical, physical and geochemical changes in the ash. Very little information is available on the natural carbon capture potential of wet or dry ash dams. This study investigated the extent of carbon capture in a wet-dumped ash dam and the mineralogical changes promoting CO2 capture, comparing this natural phenomenon with accelerated ex-situ mineral carbonation of fresh fly ash (FA). Significant levels of trace elements of Sr, Ba and Zr were present in both fresh and weathered ash. However Nb, Y, Sr, Th and Ba were found to be enriched in weathered ash compared to fresh ash. Mineralogically, fresh ash is made up of quartz, mullite, hematite, magnetite and lime while weathered and carbonated ashes contained additional phases such as calcite and aragonite. Up to 6.5 wt % CO2 was captured by the fresh FA with a 60% conversion of calcium to CaCO3 via accelerated carbonation (carried out at 2 h, 4Mpa, 90 °C, bulk ash and a S/L ratio of 1). On the other hand 6.8 wt % CO2 was found to have been captured by natural carbonation over a period of 20 years of wet disposed ash. Thus natural carbonation in the ash dumps is significant and may be effective in capturing CO2.

Fabrication and Characterization of Electrospun Waste Polyethylene Terephthalate Blended with Chitosan: A Potential Single-Use Material.

Textile single-use products are dominantly used for hygiene and personal care, many of which are non-biodegradable and are frequently discarded into sewerage systems, thus causing blockages. Thus, there is a need to move towards water-soluble textiles. This research study focuses on transforming or repurposing biomass material and synthetic reusable waste plastic materials to improve waste. Chitosan (CS) nanofibers could be used in single-use nonwoven fabric or biodegradable tissues, as the water-soluble properties of chitosan nanofibers make them the perfect material for single-use applications. Furthermore, CS was blended with polyethylene terephthalate (PET) polymer and PET-based waste plastic (CS-WPET) to slow the CS nanofibers' water degradability and strengthen the durability of the nanofiber which could be used as air filters. The CS-TFA and CS-TFA/DCM nanofiber diameters were 95.58 ± 39.28 nm or 907.94 ± 290.18 nm, respectively, as measured from the HRSEM images. The CS-PET and CS-WPET hybrid nanofibers had fiber diameters of 246.13 ± 96.36 or 58.99 ± 20.40 nm, respectively. The thermal durability of the nanofibers was tested by TGA, which showed that CS-TFA/DCM nanofibers had sufficient thermal stability up to 150 °C, making them suitable for filter or fabric use at moderate temperatures. The blended nanofibers (CS-PET and CS-WPET) were thermally stable up to 160 °C. In the aqueous medium stability test, CS-PET and CS-WPET hybrid nanofibers had a slower degradation rate and were easily dissolved, while the CS nanofibers were rapidly and completely dissolved in an aqueous medium. Blending waste PET with CS allows it to be recycled into a useful single-use, non-woven textile, with greater water solubility than unmodified PET nanofibers but more durability than CS nanofibers on their own.

Contaminants of Emerging Concern (CECs) and Male Reproductive Health: Challenging the Future with a Double-Edged Sword.

Approximately 9% of couples are infertile, with half of these cases relating to male factors. While many cases of male infertility are associated with genetic and lifestyle factors, approximately 30% of cases are still idiopathic. Contaminants of emerging concern (CECs) denote substances identified in the environment for the first time or detected at low concentrations during water quality analysis. Since CEC production and use have increased in recent decades, CECs are now ubiquitous in surface and groundwater. CECs are increasingly observed in human tissues, and parallel reports indicate that semen quality is continuously declining, supporting the notion that CECs may play a role in infertility. This narrative review focuses on several CECs (including pesticides and pharmaceuticals) detected in the nearshore marine environment of False Bay, Cape Town, South Africa, and deliberates their potential effects on male fertility and the offspring of exposed parents, as well as the use of spermatozoa in toxicological studies. Collective findings report that chronic in vivo exposure to pesticides, including atrazine, simazine, and chlorpyrifos, is likely to be detrimental to the reproduction of many organisms, as well as to sperm performance in vitro. Similarly, exposure to pharmaceuticals such as diclofenac and naproxen impairs sperm motility both in vivo and in vitro. These contaminants are also likely to play a key role in health and disease in offspring sired by parents exposed to CECs. On the other side of the double-edged sword, we propose that due to its sensitivity to environmental conditions, spermatozoa could be used as a bioindicator in eco- and repro-toxicology studies.

Effects of Film Thickness of ALD-Deposited Al2O3, ZrO2 and HfO2 Nano-Layers on the Corrosion Resistance of Ti(N,O)-Coated Stainless Steel.

The goal of this stydy was to explore the potential of the enhanced corrosion resistance of Ti(N,O) cathodic arc evaporation-coated 304L stainless steel using oxide nano-layers deposited by atomic layer deposition (ALD). In this study, we deposited Al2O3, ZrO2, and HfO2 nanolayers of two different thicknesses by ALD onto Ti(N,O)-coated 304L stainless steel surfaces. XRD, EDS, SEM, surface profilometry, and voltammetry investigations of the anticorrosion properties of the coated samples are reported. The amorphous oxide nanolayers homogeneously deposited on the sample surfaces exhibited lower roughness after corrosion attack compared to the Ti(N,O)-coated stainless steel. The best corrosion resistance was obtained for the thickest oxide layers. All samples coated with thicker oxide nanolayers augmented the corrosion resistance of the Ti(N,O)-coated stainless steel in a saline, acidic, and oxidising environment (0.9% NaCl + 6% H2O2, pH = 4), which is of interest for building corrosion-resistant housings for advanced oxidation systems such as cavitation and plasma-related electrochemical dielectric barrier discharge for breaking down persistent organic pollutants in water.

Optimization of hydrothermal synthesis of pure phase zeolite Na-P1 from South African coal fly ashes.

This study was aimed at optimizing the synthesis conditions for pure phase zeolite Na-P1 from three coal fly ashes obtained from power stations in the Mpumalanga province of South Africa. Synthesis variables evaluated were: hydrothermal treatment time (12-48 hours), temperature (100-160°C) and varying molar quantities of water during the hydrothermal treatment step (H(2)O:SiO(2) molar ratio ranged between 0-0.49). The optimum synthesis conditions for preparing pure phase zeolite Na-P1 were achieved when the molar regime was 1 SiO(2): 0.36 Al(2)O(3): 0.59 NaOH: 0.49 H(2)O and ageing was done at 47°C for 48 hours. The optimum hydrothermal treatment time and temperature was 48 hours and 140°C, respectively. Fly ashes sourced from two coal-fired power plants (A, B) were found to produce nearly same high purity zeolite Na-P1 under identical conditions whereas the third fly ash (C) lead to a low quality zeolite Na-P1 under these conditions. The cation exchange capacity for the high pure phase was found to be 4.11 meq/g. These results highlight the fact that adjustment of reactant composition and presynthesis or synthesis parameters, improved quality of zeolite Na-P1 can be achieved and hence an improved potential for application of zeolites prepared from coal fly ash.

Integrated acid mine drainage management using fly ash.

Fly Ash (FA) from a power station in South Africa was investigated to neutralise and remove contaminants from Acid Mine Drainage (AMD). After this primary treatment the insoluble FA residue namely solid residue (SR) was investigated as a suitable mine backfill material by means of strength testing. Moreover, SR was used to synthesise zeolite-P using a two-step synthesis procedure. Furthermore, the zeolite-P was investigated to polish process water from the primary FA-AMD reaction. The main objective of this series of investigations is to achieve zero waste and to propose an integrated AMD management using FA. Fly Ash was mixed with AMD at various predetermined FA-AMD ratios until the mixtures achieved circumneutral pH or higher. The supernatants were then analyzed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Ion Chromatography (IC) for cations and anions respectively. The physical strength testing of SR was carried out by mixing it with 3% Ordinary Portland Cement (OPC) and curing for 410 days. Synthesis of zeolite-P using SR was carried out by two step synthesis procedure: ageing for 24 hours followed by a mild hydrothermal synthesis at 100°C for 4 days. The polishing of process water from primary AMD treatment using FA was ascertained by mixing the process water with zeolite at a liquid to solid ratio of 100:1 for 1 hour. The results indicated that FA can be successfully used to ameliorate AMD. High removal of major AMD contaminants Fe, Al, Mg, Mn and sulphate was achieved with the ash treatment and trace elements such as Zn, Ni, Cu and Pb were also removed by the FA. Strength testing over 410 days indicated that the material gained strength over the testing period. The maximum unconfined compressive strength and elastic modulus was observed to be approximately 0.3 MPa and 150 Mpa respectively. The X-ray diffraction (XRD) analysis of the synthesized product indicated that SR was successfully converted into zeolite-P with some mullite phase remaining as a result of incomplete conversion of the feedstock SR. The zeolite-P was used as an ion exchange material to remove selective elements from the process water. Elements such as Ca, Sr, Ba and V were successfully removed from the process water with the zeolite-P. Only marginal removal of Mo was observed during the experiments. It was also observed that Na was exchanged into the solution. This study successfully demonstrated zero waste concepts and an integrated AMD management scheme using FA was developed in this study. The implementation of this technology will address FA storage problem as well as costs associated with AMD treatment.

Pharmaceuticals and Personal Care Products in the Marine Environment Around False Bay, Cape Town, South Africa: Occurrence and Risk-Assessment Study.

Pollution of the marine environment has been increasing as a result of anthropogenic activities. The preservation of marine ecosystems as well as the safety of harvested seafood are nowadays a global concern. In the present study, levels of pharmaceuticals and personal care products were assessed in different environmental compartments in the near-shore marine environment of False Bay, Cape Town, South Africa. The study revealed the presence of these persistent chemical compounds in different environmental samples from this location. Diclofenac was the most dominant compound detected, with higher concentration than the other pharmaceutical compounds, as well as being present in almost all the samples from the different sites (seawater, 3.70-4.18 ng/L; sediment, 92.08-171.89 ng/g dry wt; marine invertebrates, 67.67-780.26 ng/g dry wt; seaweed, 101.50-309.11 ng/g dry wt). The accumulation of pharmaceuticals and personal care products in the different species of organisms reflects the increasing anthropogenic pressure taking place at the sampling sites along the bay, as a result of population growth, resident lifestyle as well as poorly treated sewage effluent discharge from several associated wastewater-treatment plants. The concentration of these contaminants is in the order marine biota > sediments > seawater. The contaminants pose a low acute and chronic risk to the selected trophic levels. A public awareness campaign is needed to reduce the pollution at the source, as well as wastewater discharge limits need to be more stringent. Environ Toxicol Chem 2022;41:614-634. © 2021 SETAC.

Synthesis of Stabilized Iron Nanoparticles from Acid Mine Drainage and Rooibos Tea for Application as a Fenton-like Catalyst.

Intensive mining activities generate toxic acid mine drainage (AMD) effluents containing a high concentration of metals, including iron. The chemical synthesis of iron nanoparticles from this waste could lead to further environmental concerns. Therefore, the green synthesis of nanoparticles using plants has gained significant interest because of several benefits, including being eco-friendly. The current study reports a novel approach involving the synthesis of stabilized iron nanoparticles from AMD using rooibos tea extract. An aqueous solution of rooibos tea was prepared and titrated with AMD to reduce Fe2+/Fe3+. The samples synthesized under optimum conditions were characterized by TEM, XRD, FTIR, UV-Vis, and EDS. The results revealed that the nanoparticles had an average particle size of 36 nm with a spherical shape. These particles showed promising application as a Fenton-like catalyst for the degradation of textile dye (orange II sodium salt) with a removal efficiency of 94% within 30 min. Thus, the stabilized iron nanoparticles synthesized here performed in higher ranges than the currently reported Fenton-like catalysts regarding dye removal efficiency and reaction time.

The burden of emerging contaminants upon an Atlantic Ocean marine protected reserve adjacent to Camps Bay, Cape Town, South Africa.

The presence and levels of fifteen chemicals of emerging concerns, including five perfluorinated compounds (PFCs), two industrial chemicals, seven pharmaceuticals and one personal care product, were evaluated in biota, seawater and sediments obtained from near-shore coastal zone in Camps Bay, Cape Town, South Africa. Eight compounds were found in seawater, and between nine to twelve compounds were quantified in marine invertebrates, sediment and seaweed. Diclofenac was the prevalent pharmaceutical with a maximum concentration of 2.86 ng/L in seawater, ≥110.9 ng/g dry weight (dw) in sediments and ≥67.47 ng/g dw in marine biotas. Among PFCs, perfluoroheptanoic acid was predominant in seawater (0.21-0.46 ng/L). Accumulation of perfluorodecanoic acid (764 ng/g dw) as well as perfluorononanoic acid and perfluorooctanoic acid (504.52 and 597.04 ng/g dw, respectively) was highest in samples of seaweed. The environmental risk assessment carried out in this study showed that although individual pollutants pose a low acute and chronic risk, yet individual compounds each had a high bioaccumulation factor in diverse marine species, and their combination as a complex mixture in marine organisms might have adverse effects upon aquatic organisms. Data revealed that this Atlantic Ocean marine protected environment is affected by the presence of numerous and diverse emerging contaminants that could only have originated from sewage discharges. The complex mixture of persistent chemicals found bioaccumulating in marine organisms could bode ill for the propagation and survival of marine protected species, since many of these compounds are known toxicants.