An update on sustainabilities and challenges on the removal of ammonia from aqueous solutions: A state-of-the-art review.

An insightful attempt has been made in this review and the primary objective was to meticulously provide an update on the sustainabilities, advances and challenges pertaining the removal of ammonia from water and wastewater. Specifically, ammonia is a versatile compound that prevails in various spheres of the environment, and if not properly managed, this chemical species could pose severe ecological pressure and toxicity to different receiving environments and its biota. The notorious footprints of ammonia could be traced to anoxic conditions, an infestation of aquatic ecosystems, hyperactivity, convulsion, and methaemoglobin, popularly known as the "blue baby syndrome". In this review, latest updates regarding the sustainabilities, advancements and challenges for the removal of ammonia from aqueous solutions, i.e., river and waste waters, are briefly elucidated in light of future perspectives. Viable routes and ideal hotspots, i.e., wastewater and drinking water, for ammonia removal under the cost-effective options have been unpacked. Key mechanisms for the removal of ammonia were grossly bioremediation, oxidation, adsorption, filtration, precipitation, and ion exchange. Finally, this review denoted biological nutrient removal, struvite precipitation, and breakpoint chlorination as the most effective and promising technologies for the removal of ammonia from aquatic environments, although at the expense of energy and operational cost. Lastly, the future perspective, avenues of exploitation, and technical facets that deserve in-depth exploration are duly underscored.

Effective removal of ammonia from aqueous solution through struvite synthesis and breakpoint chlorination: Insights into the synergistic effects of the hybrid system.

The ever-growing contamination of surface water due to various catchment activities poses threats and stress to downstream water treatment entities. Specifically, the presence of ammonia, microbial contaminants, organic matter, and heavy metals has been an issue of paramount concern to water treatment entities since stringent regulatory frameworks require these pollutants to be removed prior to water consumption. Herein, a hybrid approach that integrates struvite crystallization (precipitation) and breakpoint chlorination (stripping) for the removal of ammonia from aqueous solution was evaluated. To fulfil the goals of this study, batch experimental studies were pursued through the adoption of the well-known one-factor-at-a-time (AFAAT) method, specifically the effects of time, concentration/dosage, and mixing speed. The fate of chemical species was underpinned using the state-of-the-art analytical instruments and accredited standard methods. Cryptocrystalline magnesium oxide nanoparticles (MgO-NPs) were used as the magnesium source while the high-test hypochlorite (HTH) was used as the source of chlorine. From the experimental results, the optimum conditions were observed to be, i.e., Stage 1 - struvite synthesis, 110 mg/L of Mg and P dosage (concentration), 150 rpm of mixing speed, 60 min of contact time, and lastly, 120 min of sedimentation while optimum condition for the breakpoint chlorination (Stage 2) were 30 min of mixing and 8:1 Cl2:NH3 weight ratio. Specifically, in Stage 1, i.e., MgO-NPs, the pH increased from 6.7 to ≥9.6, while the turbidity was reduced from 9.1 to ≤1.3 NTU. Mn removal efficacy attained ≥97.70% (reduced from 174 µg/L to 4 µg/L) and Fe attained ≥96.64% (reduced from 11 mg/L to 0.37 mg/L). Elevated pH also led to the deactivation of bacteria. In Stage 2, i.e. breakpoint chlorination, the product water was further polished by eliminating residual ammonia and TPC at 8:1 Cl2-NH3 weight ratio. Interestingly, ammonia was reduced from 6.51 to 2.1 mg/L in Stage 1 (67.74% removal) and then from 2.1 to 0.002 mg/L post breakpoint chlorination (99.96% removal), i.e., stage 2. Overall, synergistic and complementary effects of integrating struvite synthesis and breakpoint chlorination hold great promise for the removal of ammonia from aqueous solutions thus confirming that this technology could potentially be used to curtail the effects of ammonia in the receiving environments and drinking water.

Emerging remediation potentiality of struvite developed from municipal wastewater for the treatment of acid mine drainage.

The valorisation of wastewaters for minerals recovery and their potential beneficiation has gained enormous attention recently. In this study the removal of phosphate and ammonia from municipal wastewater using activated magnesite resulted in the formation of struvite. The optimum conditions for the synthesis of struvite were 60 min of mixing, 300 rpm mixing speed, 1 g of activated magnesite and room temperature, whilst optimum conditions for the treatment of acid mine drainage (AMD) using the synthesized struvite were 45 min of mixing, 20 g of struvite dosage, 1000 mL, and 300 rpm mixing speed. The efficacy of struvite for neutralisation of AMD and attenuation of inorganic contaminants were ≥98.99% for metals (Al3+, Fe3+, and Mn2+) and ≥30% for SO42-. Traces of other metals such as Zn, Cu, Ni, Pb, and Cr were significantly attenuated. Phosphate was fully attenuated from the aqua-sphere. PHREEQC predicted the removal of minerals as oxy-(hydro)-sulphates, oxy-(hydro)-phosphate, metals hydroxides, and other complexes. FE-SEM equipped with FIB and an EDX, XRD, XRF, and FTIR confirmed the synthesis of struvite and fate of chemical species after treatment. This study confirmed the feasibility of recovering phosphate and ammonia as struvite which can be employed for the treatment of AMD.

Insights into mechanisms governing the passive removal of inorganic contaminants from acid mine drainage using permeable reactive barrier.

The permeable reactive barrier has been deemed as the most prudent and pragmatic way to passively manage and remediate acid mine drainage (AMD). Herein, insights into mechanisms governing the removal of inorganic contaminants from AMD using a permeable reactive barrier (PRB), i.e. pervious concrete, were reported. In particular, the effects of varying dosages, i.e., 6, 10, 30, and 60 g, of cementitious materials comprising CEM I 52.5R with or without fly ash, hydrated lime, and gypsum were evaluated whilst the fate of chemical species was underpinned using the state-of-the-art analytical techniques, along with PHREEQC geochemical modelling. The role of gypsum, a product formed from the interaction of PRB with AMD in heavy metals attenuation was also elucidated. Findings revealed cementitious materials to play an indispensable role in the removal of inorganic contaminants from AMD. Furthermore, alkalinity from used materials increases the pH (i.e. pH ≥ 12.5) of AMD leading to the precipitation of chemical species. Specifically, the efficacy registered the following sequence: Lime ≥ CEM I ≥ 30%FA ≥ Gypsum with ≥99 for Al and Fe except for Gypsum which attained ≥98 while the performance for Zn removal registered the following sequence, 97 ≥ 98 ≥ 88.8 ≥ 45% for CEM I ≥ Lime ≥30%FA ≥ Gypsum, respectively. Chemical species exist as divalent, trivalent, oxyanions, and other complexes in solution as predicted by PHREEQC. Moreover, they were removed as metal hydroxides, oxyhydrosulphates, and gypsum hence corroborating findings from XRD, SEM-EDS, and FTIR results. Mechanisms which were responsible for the removal of chemical species were precipitation, adsorption, co-adsorption, co-precipitation, ion exchange, and complexation. Henceforth, this study explicitly demonstrated mechanisms that underpin the removal of inorganic contaminants from AMD using PRB and findings from this study will be used to develop effective PRB for the management of acid mine drainage and the receiving environment.

Effective treatment of acid mine drainage using a combination of MgO-nanoparticles and a series of constructed wetlands planted with Vetiveria zizanioides: A hybrid and stepwise approach.

In this novel study, acid mine drainage (AMD) was treated using a hybrid approach comprising a nano-and-biotic system synergistically integrated in a step-wise and modular fashion. Specifically, the treatment chains were made up of different stages, which comprise, neutralization using activated magnesite or MgO-nanoparticles (NPs) (Stage 1) and polishing the product water using a series of wetlands (Stage 2) in a step-wise connection. In stage One (1), real AMD was treated with MgO-NPs at a ratio of 1:100 (1 g/100 mL - w/v ratio), 500 rpm of mixing speed, and One (1) hour of hydraulic retention time (HRT) whilst in stage 2, the final water was fed into constructed wetlands, i.e. Three (3) interconnected wetland with different flow modalities [(I) subsurface vertical flow (SSVF-CW), (II) free water surface flow (FWS-CW), and (III) subsurface horizontal flow (SSHF-CW)], for further purification and polishing to the desired product. In this stage, i.e. stage 2, the product water and substrate were collected daily at the outlet and bottom of each wetland. After the treatment process, the pH of the product water was observed to have increased from 2.6 to 10.4. Significant removal of inorganic contaminants was also observed and the following removal sequence was registered, Fe (99.8%) ≥ Al (99.5%) ≥ Mn (99.24%) ≥ Zn (98.36%) ≥ Cu (97.38%) ≥ Ni (97.7%) ≥ SO42─ (80.59%). Reduction in electrical conductivity (EC) was also observed (86%). Specifically, the nano-part removed the metals and sulphate partially whereas the bio-part effectively removed SO42─ and EC levels, thus denoting stellar combination and complementary performance for the hybrid system in integrated fashion. The state-of-the-art analytical instruments were used to underpin and succinct the fate of chemical species in raw and product MgO-NPs, substrates, and the grass. Finally, the product water conformed to the prescribed standards for effluent discharge hence proving that the synergy of neutralization and bio-remediation, i.e. nano-and-biotic system, could potentially yield the desired results in mine water management and afield. This will go a long way in curtailing ecological footprints associated with mining activities thus fostering the concept of sustainable development.

Facile thermal activation of non-reactive cryptocrystalline magnesite and its application on the treatment of acid mine drainage.

In this study, the authors report a facile thermal activation of non-reactive cryptocrystalline magnesite and explore its application on the treatment of acid mine drainage (AMD). The primary aim was to optimize the calcination-water interface reactive conditions. Parameters evaluated include calcination temperature, calcination time, AMD-calcination temperature interface, and AMD-calcination duration interface. PHREEQC geochemical modelling was also applied to substantiate obtained results. The results indicated that the formation of MgO and CaO increase with an increase in calcination temperature and time. The optimum temperature and calcination time were observed to be 800 °C and 30 min in the furnace. The pH was observed to increase with an increase in calcination temperature and time but reached equilibrium at 800 °C and 30 min respectively. Geochemical modelling validated the formation of gypsum with attenuation in Ca ions and predicted the formation of MgSO4(aq). Metal species were observed to precipitate with an increase in pH. At 700 °C, Fe was completely removed, while Al, and Mn were completely removed from an aqueous system at 800 °C. This novel study invented the new calcination condition for non-reactive cryptocrystalline magnesite and proved its potential application in wastewater treatment. The calcination conditions were very short and therefore will save industries energy due to replacement of uneconomical and less environmental friendly pre-treatment options that lead to environmental degradation.

An update on synthetic dyes adsorption onto clay based minerals: A state-of-art review.

Dyes are growing to be a problematic class of pollutants to the environment. The disposal of dyes in water resources has bad aesthetic and health effects, hence the need to remove them from the environment. The need for treatment methods that are effective and low in price is rising hence a lot of research interest is being diverted towards adsorbents that are cheap, preferable naturally occurring materials like clays. In most reported dye adsorption studies, limited information on the relationship between characterization results with adsorbent performance on dye removal has been given. This review article seeks to report on the link between the adsorption characteristics of the clays and their adsorption capacities and to gather information on the modifications done on clays to improve their adsorption capacities. A critical analysis of the different mechanisms involved during the decolouration process and their application for dye removal has been discussed in detail in this up-to-date review. From a wide range of consulted literature review, it is evident that some clays have appreciable adsorption capacities on top of being widely available. It was also noted that several parameters like contact time, dosage, concentration, temperature and pH affect the removal of dyes. Furthermore, the application of clay minerals for decolourising water represents economic viable and locally available materials that can be used substantially for pollution control and management. Conclusions were also drawn and suggestions for future research perspectives are proposed.

Occurrences and implications of pathogenic and antibiotic-resistant bacteria in different stages of drinking water treatment plants and distribution systems.

Different stages of drinking water treatment plants (DWTPs) play specific roles in diverse contaminants' removal present in natural water sources. Although the stages are recorded to promote adequate treatment of water, the occurrence of pathogenic bacteria (PB) and antibiotic-resistant bacteria (ARB) in the treated water and the changes in their diversity and abundance as it passed down to the end users through the drinking water distribution systems (DWDSs), is a great concern, especially to human health. This could imply that the different stages and the distribution system provide a good microenvironment for their growth. Hence, it becomes pertinent to constantly monitor and document the diversity of PB and ARB present at each stage of the treatment and distribution system. This review aimed at documenting the occurrence of PB and ARB at different stages of treatment and distribution systems as well as the implication of their occurrence globally. An exhaustive literature search from Web of Science, Science-Direct database, Google Scholar, Academic Research Databases like the National Center for Biotechnology Information, Scopus, and SpringerLink was done. The obtained information showed that the different treatment stages and distribution systems influence the PB and ARB that proliferate. To minimize the human health risks associated with the occurrence of these PB, the present review, suggests the development of advanced technologies that can promote quick monitoring of PB/ARB at each treatment stage and distribution system as well as reduction of the cost of environomics analysis to promote better microbial analysis.

Wastewater Treatment for Carbon Dioxide Removal.

Wastewater treatment is notorious for its hefty carbon footprint, accounting for 1-2% of global greenhouse gas (GHG) emissions. Nonetheless, the treatment process itself could also present an innovative carbon dioxide removal (CDR) approach. Here, the calcium (Ca)-rich effluent of a phosphorus (P) recovery system from municipal wastewater (P recovered as calcium phosphate) was used for CDR. The effluent was bubbled with concentrated CO2, leading to its mineralization, i.e., CO2 stored as stable carbonate minerals. The chemical and microstructural properties of the newly formed minerals were ascertained by using state-of-the-art analytical techniques. FTIR identified CO3 bonds and carbonate stretching, XRF and SEM-EDX measured a high Ca concentration, and SEM imaging showed that Ca is well distributed, suggesting homogeneous formation. Furthermore, FIB-SEM revealed rhombohedral and needle-like structures and TEM revealed rod-like structures, indicating that calcium carbonate (CaCO3) was formed, while XRD suggested that this material mainly comprises aragonite and calcite. Results imply that high-quality CaCO3 was synthesized, which could be stored or valorized, while if atmospheric air is used for bubbling, a partial direct air capture (DAC) system could be achieved. The quality of the bubbled effluent was also improved, thus creating water reclamation and circular economy opportunities. Results are indicative of other alkaline Ca-rich wastewaters such as effluents or leachates from legacy iron and steel wastes (steel slags) that can possibly be used for CDR. Overall, it was identified that wastewater can be used for carbon mineralization and can greatly reduce the carbon footprint of the treatment process, thus establishing sustainable paradigms for the introduction of CDR in this sector.

Effective Adsorption of Congo Red from Aqueous Solution Using Fe/Al Di-Metal Nanostructured Composite Synthesised from Fe(III) and Al(III) Recovered from Real Acid Mine Drainage.

This study presents the first known exploration of Congo red dye (CR) adsorption by a polycationic Fe/Al Di-metal nanostructured composite (PDFe/Al) synthesised using Fe(III) and Al(III) recovered from authentic acid mine drainage (AMD). The PDFe/Al successfully removed CR from the aqueous solution. The mineralogical, microstructural, and chemical properties of the synthesised PDFe/Al adsorbent (before and after adsorption) were studied using state-of-the-art analytical instruments. The optimum conditions were observed to be 100 mg·L-1 CR, 1 g of the PDFe/Al in 500 mL adsorbate solution, 20 min of shaking, pH = 3-8, and a temperature of 35 °C. At optimised conditions, the PDFe/Al showed ≥99% removal efficacy for CR dye and an exceptionally high Langmuir adsorption capacity of 411 mg·g-1. Furthermore, a diffusion-limited adsorption mechanism was observed, with two distinct surfaces involved in the adsorption of CR from an aqueous solution. It was determined that the adsorption of CR induced internal strain and deformation within the matrices and interlayers of the PDFe/Al which resulted in a marked increase in the adsorbent pore surface area and pore volume. The remarkably high adsorption capacity could be attributed to the high surface area. A regeneration study showed that the adsorbent could be reused more than four times for the adsorption of CR. The findings from this study demonstrated the feasibility of recovering valuable minerals from toxic and hazardous AMD and demonstrated their potential for the treatment of industrial wastewaters.

Systematic assessment of SARS-CoV-2 virus in wastewater, rivers and drinking water - A catchment-wide appraisal.

Human coronaviruses (HCoVs) attracted attention in 2002 with the severe acute respiratory syndrome (SARS) outbreak, caused by the SARS-CoV virus (mortality rate 9.6%), and gained further notoriety in 2012 with the Middle East respiratory syndrome (MERS) (mortality rate 34.3%). Currently, the world is experiencing an unprecedented crisis due to the COVID-19 global pandemic, caused by the SARS-CoV-2 virus in 2019. The virus can pass to the faeces of some patients, as was the case of SARS-CoV and MERS-CoV viruses. This suggests that apart from the airborne (droplets and aerosols) and person-to-person (including fomites) transmission, the faecal-oral route of transmission could also be possible for HCoVs. In this eventuality, natural water bodies could act as a virus reservoir of infection. Here, the temporospatial migration and attenuation of the SARS-CoV-2 virus in municipal wastewater, the receiving environment, and drinking water is evaluated, using the polymerase chain reaction (PCR), in the South African setting. SARS-CoV-2 viral RNA was identified in raw wastewater influent but was below the detection limit in the latter treatment stages. This suggests that the virus decays from as early as primary treatment and this could be attributed to wastewater's hydraulic retention time (2-4 h), composition, and more importantly temperature (>25 °C). Therefore, the probability of SARS-CoV-2 virus transportation in water catchments, in the eventuality that the virus remains infective in wastewater, appears to be low in the South African setting. Finally, catchment-wide monitoring offers a snapshot of the status of the catchment in relation to contagious viruses and can play a pivotal role in informing the custodians and downstream water users of potential risks embedded in water bodies.

Dataset on physicochemical and microbial properties of raw water in four drinking water treatment plants based in South Africa.

The present paper aims at determining the status of surface water quality by applying the treatability index for the raw water in four water treatment plants (WTPs), namely Vaalkop, Klipdrift, Wallmansthal, and Cullinan. These plants are based in South Africa. Sampling was conducted from July 2011 to June 2018 (7 years). The collected water samples were analysed on monthly basis over the specified period. Three Hundred and thirty six (336) water samples were collected and analysed. The Treatability Index (TI) was calculated for twenty-one physicochemical and microbial parameters, which include pH, conductivity, chloride, sodium, potassium, hardness, alkalinity, precipitation potential, turbidity, colour, E. coli, organic carbon, chlorophyll, nitrite, ammonia, nitrates, phosphate, iron, manganese, and sulphate. The computed TI values range from 0.1 to 1755.5 and the water quality was unsuitable for a number of defined uses. The data demonstrated high treatment demand for raw water. On that note, the surface water from the monitored places is not suitable for drinking purposes. The data and treatability index denoted the need for treatment prior consumption. The collected water quality data can be reused for future references, modelling, and trending of historic data to understand current and prospect future changes in the properties of our raw water qualities.

Innovative spherical biochar for pharmaceutical removal from water: Insight into adsorption mechanism.

In this study, we developed an innovative spherical biochar with high porosity and excellent paracetamol (PRC) adsorption capacity. The optimal pyrolysis temperatures for the preparation of spherical biochar (derived from pure glucose) and non-spherical biochar (from pomelo peel wastes) were obtained at 900 °C and 700 °C, respectively. Various advanced techniques were applied to characterize the prepared biochars. Spherical and non-spherical biochars exhibited large specific surface area (1292 and 1033 m2/g) and high total pore volume (0.704 and 1.074 cm3/g), respectively. The adsorption behavior of PRC onto two biochars was conducted utilizing batch experiments. Results demonstrated that the adsorption process was slightly affected by the change of solution pH (2-11) and addition of NaCl (0.05-1.0 M) and was able to achieve fast equilibrium (∼120 min). The maximum adsorption capacity of spherical biochar (286 mg/g) for PRC was approximately double that of non-spherical biochar (147 mg/g). The signal of thermodynamic parameters was negative ΔG° and ΔH° values, but positive ΔS° value. The adsorption mechanism consisted of pore-filling, hydrogen bonding formations, n-π and π-π interactions, and van der Waals force. The adsorption capacities of two biochars were insignificantly dependent on different real water samples containing PRC. Consequently, the biochars can serve as a green and promising material for efficiently removing PRC from water.

Assessing the sustainability of acid mine drainage (AMD) treatment in South Africa.

The environmental sustainability of acid mine drainage (AMD) treatment at semi-industrial scale is examined by means of the life cycle assessment (LCA) methodology. An integrated process which includes magnesite, lime, soda ash and CO2 bubbling treatment was employed to effectively treat, at semi-industrial scale, AMD originating from a coal mine in South Africa. Economic aspects are also discussed. AMD is a growing problem of emerging concern that cause detrimental effects to the environment and living organisms, including humans, and impose on development, health, access to clean water, thus also affect economic growth and cause social instability. Therefore, sustainable and cost effective treatment methods are required. A life cycle cost analysis (LCCA) revealed the viability of the system, since the levelized cost of AMD treatment can be as low as R112.78/m3 (€7.60/m3 or $9.35/m3). Moreover, due to its versatility, the system can be used both at remote locales, at stand-alone mode (e.g. using solar energy), or can treat AMD at industrial scale, thus substantially improving community resilience at local and national level. In terms of environmental sustainability, 29.6 kg CO2eq are emitted per treated m3 AMD or its environmental footprint amount to 2.96 Pt/m3. South Africa's fossil-fuel depended energy mix and liquid CO2 consumption were the main environmental hotspots. The total environmental footprint is reduced by 45% and 36% by using solar energy and gaseous CO2, respectively. Finally, AMD sludge valorisation, i.e. mineral recovery, can reduce the total environmental footprint by up to 12%.