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.

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.

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.

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.

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.

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.

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.

Antimicrobial and cytotoxic activity of electrosprayed chitosan nanoparticles against endodontic pathogens and Balb/c 3T3 fibroblast cells.

The aims of this study were to synthesize highly positively charged chitosan nanoparticles (Ch-Np) using the electrospraying technique, and to test their antimicrobial activity against endodontic pathogens, and cytotoxicity against fibroblast cells. Ch-Np were synthesized from low molecular weight chitosan (LMW-Ch) using the electrospraying technique, and characterized. The antimicrobial activity was evaluated against Streptococcus mutans, Enterococcus faecalis, and Candida albicans in their planktonic state using a Time-Kill Test performed by using broth micro-dilution technique, and against biofilm biomass using a microtiter plate biofilm assay. The cytotoxicity was evaluated using Balb/c 3T3 fibroblast cells with the standard MTT assay. Electrospraying of LMW-Ch produced Ch-Np with an average size of 200 nm, and a surface charge of 51.7 mV. Ch-Np completely eradicated S. mutans and E. faecalis in the planktonic state and showed fungistatic activity against C. albicans. Furthermore, it significantly reduced the biofilm biomass for all the tested microbial species [S. mutans (p = 0.006), E. faecalis (p < 0.0001), and C. albicans (p = 0.004)]. When tested for cytotoxicity using 3T3 cells, Ch-Np showed no cytotoxicity. In conclusion, the highly positively charged, colloidal dispersion of Ch-Np are effective as a biocompatible endodontic antimicrobial agent.

Acylation of Anisole With Benzoyl Chloride Over Rapidly Synthesized Fly Ash-Based HBEA Zeolite.

Stable HBEA zeolite with high surface area and strong acid sites was synthesized from coal fly ash-based silica extract via indirect hydrothermal synthesis. The rapid HBEA hydrothermal crystallization times of 8, 10, and 12 h were achieved through a reduced molar water fraction in the synthesis composition. The HBEA zeolites prepared from fly ash silica extract exhibited well-defined spheroidal-shaped crystal morphology with uniform particle sizes of 192, 190, or 239 nm obtained after 8, 10, or 12 h of synthesis time, respectively. The high surface area and the microporous area of 702 and 722 m2/g were achieved as a function of shorter hydrothermal synthesis durations (10 and 24 h, respectively) compared to 48 or 72 h, which resulted in HBEA zeolites with lower surface areas of 538 and 670 m2/g. Likewise, temperature-programmed desorption measurements of fly ash-based HBEA zeolites revealed the presence of weak and strong acid sites in the zeolite. The submicron crystal sizes with a well-defined porosity of HBEA zeolites enhanced the diffusion of anisole and benzoyl chloride molecules toward the active acid sites and hence showed better conversion and selectivity in acylation products. High conversion of benzoyl chloride with anisole was achieved, reaching up to 83% with a 93-96% selectivity toward 4-methoxyacetophenone.

Isolation and characterization of nanocrystalline cellulose from cocoa pod husk (CPH) biomass wastes.

In this paper, cellulose nanocrystals (CNCs) were isolated from the cellulose extracted from cocoa pod husk waste, followed by characterization using XRD, FT-IR, TGA, SEM and TEM to determine its crystallinity, structural properties, thermal characteristics, morphology and dimensions respectively. The result revealed that the cocoa pod husk amorphous segments containing hemicelluloses and lignin were extensively removed with increasing chemical treatments leading to increased purity, crystallinity index and thermal stability of the extracted materials. The diameter, length and crystallinity index of the CNC isolated from the CPH are 10-60 nm, 41-155 nm and 67.60% respectively.

Herbicides in Camps Bay (Cape Town, South Africa), supplemented.

During 2017 the herbicides alachlor, atrazine, butachlor, metolachlor, and simazine were detected in water samples, beach sediments and marine biota collected at Camps Bay, Cape Town, South Africa. During that period, the annual rain catchment record was 77,000 m3, whereas the volume of chemically laden sewage discharged via the marine outfall was 693,500 m3 making the marine sewage outfall by far the most predominant source for these herbicides in the bay. The chemical load in the discharged sewage was not removed by the applied pre-treatment step, which only uses a 3 mm screen to eliminate plastic, paper, rags and other foreign materials. After passing through the Camps Bay pump station, the sewage is released to the bay at the following GPS position 33°56'42.214″ S 18°21'59.257″ E (Colenbrander et al., 2021) and at a discharge depth of 23 m and 1497 m from the beach. In our study the presence in marine biota of atrazine and simazine were taken as being indicative of the chemical signature of the sewage being released through the outfall, since these compounds were detected previously in the sewage prior to discharge. To our knowledge, our studies of the herbicides in diverse benthic organisms found in the near shore environment of Camps Bay are the first of their kind for this Western Cape region.

Removal of Pharmaceutical Residues from Water and Wastewater Using Dielectric Barrier Discharge Methods-A Review.

Persistent pharmaceutical pollutants (PPPs) have been identified as potential endocrine disruptors that mimic growth hormones when consumed at nanogram per litre to microgram per litre concentrations. Their occurrence in potable water remains a great threat to human health. Different conventional technologies developed for their removal from wastewater have failed to achieve complete mineralisation. Advanced oxidation technologies such as dielectric barrier discharges (DBDs) based on free radical mechanisms have been identified to completely decompose PPPs. Due to the existence of pharmaceuticals as mixtures in wastewater and the recalcitrance of their degradation intermediate by-products, no single advanced oxidation technology has been able to eliminate pharmaceutical xenobiotics. This review paper provides an update on the sources, occurrence, and types of pharmaceuticals in wastewater by emphasising different DBD configurations previously and currently utilised for pharmaceuticals degradation under different experimental conditions. The performance of the DBD geometries was evaluated considering various factors including treatment time, initial concentration, half-life time, degradation efficiency and the energy yield (G50) required to degrade half of the pollutant concentration. The review showed that the efficacy of the DBD systems on the removal of pharmaceutical compounds depends not only on these parameters but also on the nature/type of the pollutant.

PM2.5 chemical composition and geographical origin of air masses in Cape Town, South Africa.

PM2.5 in the indoor and outdoor environment has been linked in epidemiology studies to the symptoms, hospital admissions and development of numerous health outcomes including death. The study was conducted during April 2017 and April 2018. PM2.5 samples were collected over 24 h and every third day. The mean PM2.5 level was 13.4 µg m-3 (range: 1.17-39.1 µg m-3). PM2.5 levels exceeded the daily World Health Organization air quality guideline (25 µg m-3) on 14 occasions. The mean soot level was 1.38 m-1 × 10-5 (range: 0 to 5.38 m-1 × 10-5). Cl-, NO3 -, SO4 2-, Al, Ca, Fe, Mg, Na and Zn were detected in the PM2.5 samples. The geographical origin of air masses that passed Cape Town was estimated using the Hybrid Single Particle Lagrangian Integrated Trajectory software. Four air masses were identified in the cluster analysis: Atlantic-Ocean-WSW, Atlantic-Ocean-SW, Atlantic-Ocean-SSW and Indian-Ocean. The population of Cape Town may experience various health outcomes from the outdoor exposure to PM2.5 and the chemical composition of PM2.5.

Fly Ash-Based Geopolymer Building Materials for Green and Sustainable Development.

This study reports on formulations and conditions for producing fly ash-based geopolymers with a view to showing that the compressive strength required for construction applications can be obtained without the addition of aggregates, sand, and/or cement. It was shown in a series of experiments constituting at least 73% fly ash that a compressive strength of up to 90 MPa can be obtained depending on the curing conditions. While high alkalinity resulted in stronger materials, the results showed about 40% savings in CO2 emissions without using sand and cement. Such materials are suited for construction applications with minimal environmental impact.

Anticorrosion Coated Stainless Steel as Durable Support for C-N-TiO2 Photo Catalyst Layer.

The development of durable photocatalytic supports resistant in harsh environment has become challenging in advanced oxidation processes (AOPs) focusing on water and wastewater remediation. In this study, stainless steel (SS), SS/Ti (N,O) and SS/Cr-N/Cr (N,O) anticorrosion layers on SS meshes were dip-coated with sol gel synthesised C-N-TiO2 photo catalysts pyrolysed at 350 °C for 105 min, using a heating rate of 50 °C/min under N2 gas. The supported C-N-TiO2 films were characterised by scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and Raman spectroscopy. The results showed that C-N-TiO2 was successfully deposited on anticorrosion coated SS supports and had different morphologies. The amorphous C and TiO2 were predominant in C-N-TiO2 over anatase and rutile phases on the surface of SS and anticorrosion supports. The C-N-TiO2 coated films showed enhanced photocatalytic activity for the decolouration of O.II dye under both solar and UV radiation. The fabricated C-N-TiO2 films showed significant antibacterial activities in the dark as well as in visible light. Herein, we demonstrate that SS/Ti(N,O) and SS/Cr-N/Cr(N,O) anticorrosion coatings are adequate photocatalytic and corrosion resistant supports. The C-N-TiO2 photo catalytic coatings can be used for water and wastewater decontamination of pollutants and microbes.

Presence and risk assessment of herbicides in the marine environment of Camps Bay (Cape Town, South Africa).

The present study was conducted during a time of drought to assess the concentration of herbicides and their potential for accumulation in marine biota found in the near shore marine environment of an urban setting (Camps Bay, Cape Town, South Africa). The purpose was to establish whether raw sewage containing selected persistent chemicals that are released through a local marine outfall would be sufficiently diluted by the ocean to prevent impact on the near-shore marine environment of the suburb Camps Bay. Samples of seawater, sediment, seaweed, and selected marine organisms present in the near shore environment, such as limpets (Cymbula granatina), mussels (Mytilus galloprovincialis), and sea urchins (Parechinus angulosus), were analysed for five indicator herbicides, namely atrazine, alachlor, simazine, metolachlor, and butachlor, with gas chromatography coupled with a mass spectrometer. The concentration of the compounds detected ranged from below the limit of detection (

Characterization of electron beam deposited Nb2O5 coatings for biomedical applications.

Niobium oxide coatings deposited on Ti6Al4V substrates by electron beam deposition and annealed in air at 600 °C and 800 °C were evaluated for their suitability towards dental, maxillofacial or orthopaedic implant applications. A detailed physico-chemical properties investigation was carried out in order to determine their elemental and phase composition, surface morphology and roughness, mechanical properties, wettability, and corrosion resistance in simulated body fluid solution (pH = 7.4) at room temperature. The biocompatibility of the bare Ti6Al4V substrate and coated surfaces was evaluated by testing the cellular adhesion and viability/proliferation of human osteosarcoma cells (MG-63) after 72 h of incubation. The coatings annealed at 800 °C exhibit more phase pure nanocrystalline Nb2O5 surfaces with enhanced wettability, reduced porosity and enhanced corrosion resistance properties making them good candidate for dental, maxillofacial or orthopaedic implant applications.

Occurrences, levels and risk assessment studies of emerging pollutants (pharmaceuticals, perfluoroalkyl and endocrine disrupting compounds) in fish samples from Kalk Bay harbour, South Africa.

A comprehensive analysis of 15 target chemical compounds (pharmaceuticals and personal care product, perfluoroalkyl compounds and industrial chemicals) were carried out to determine their concentrations in selected commercially exploited, wild caught small and medium sized pelagic fish species and their organs (Thyrsites atun (snoek), Sarda orientalis (bonito), Pachymetopon blochii (panga) and Pterogymnus laniarius (hottentot)) obtained from Kalk Bay harbour, Cape Town. Solid phase extraction (SPE) method based on Oasis HLB cartridges were used to concentrate and clean-up the samples. Liquid chromatography-mass spectrometry analysis of these chemical compounds revealed the simultaneous presence of at least 12 compounds in different parts of the selected fish species in nanogram-per-gram dry weight (ng/g dw) concentrations. The results revealed that perfluorodecanoic acid, perfluorononanoic acid and perfluoroheptanoic acid were the most predominant among the perfluorinated compounds and ranged between: (20.13-179.2 ng/g), (21.22-114.0 ng/g) and (40.06-138.3 ng/g). Also, diclofenac had the highest concentration in these edible fish species out of all the pharmaceuticals detected (range: 551.8-1812 ng/g). The risk assessment values were above 0.5 and 1.0 for acute and chronic risk respectively which shows that these chemicals have a high health risk to the pelagic fish, aquatic organisms and to humans who consume them. Therefore, there is an urgent need for a precautionary approach and the adequate regulation of the use and disposal of synthetic chemicals that persist in aquatic/marine environment in this province and other parts of South Africa, to prevent impacts on the sustainability of our marine environment, livelihood and lives.