The paper demonstrates the capability of using cockle shells as an adsorbent for phosphorus removal from simulated petrochemical wastewater, focusing on the actual condition of the petrochemical facultative pond. In this study, the physicochemical properties of shell powder were determined, such as the functional groups, surface morphology, crystalline structure, and surface area using FTIR, SEM, EDX, XRD, and BET. It was observed that the optimum conditions for effective phosphorus removal are under the presence of rotational speed (125 rpm), higher dosage (7 g/L), and larger surface area (smaller particle size) of the shell powder. Fine powder achieved up to 52.27% of phosphorus removal after 40 min compared to coarse powder which could only give 16.67% removal. Additionally, calcined shell powder demonstrated a higher phosphorus removal rate, i.e., up to 62.37%, compared to raw shell powders. The adsorption isotherm was studied using Langmuir and Freundlich models, but the isothermal data fit better for the Freundlich model (R2 = 0.9836). Overall, this study has successfully generated a greener and low-cost adsorbent.
The scarcity of water resources and environmental pollution have highlighted the need for sustainable wastewater treatment. Existing conventional treatment systems are energy-intensive and not always able to meet stringent disposal standards. Recently, algal-bacterial systems have emerged as environmentally friendly sustainable processes for wastewater treatment and resource recovery. The algal-bacterial systems work on the principle of the symbiotic relationship between algae and bacteria. This paper comprehensively discusses the most recent studies on algal-bacterial systems for wastewater treatment, factors affecting the treatment, and aspects of resource recovery from the biomass. The algal-bacterial interaction includes cell-to-cell communication, substrate exchange, and horizontal gene transfer. The quorum sensing (QS) molecules and their effects on algal-bacterial interactions are briefly discussed. The effect of the factors such as pH, temperature, C/N/P ratio, light intensity, and external aeration on the algal-bacterial systems have been discussed. An overview of the modeling aspects of algal-bacterial systems has been provided. The algal-bacterial systems have the potential for removing micropollutants because of the diverse possible interactions between algae-bacteria. The removal mechanisms of micropollutants - sorption, biodegradation, and photodegradation, have been reviewed. The harvesting methods and resource recovery aspects have been presented. The major challenges associated with algal-bacterial systems for real scale implementation and future perspectives have been discussed. Integrating wastewater treatment with the algal biorefinery concept reduces the overall waste component in a wastewater treatment system by converting the biomass into a useful product, resulting in a sustainable system that contributes to the circular bioeconomy.
Environmental exposure to active pharmaceutical ingredients (APIs) can have negative effects on the health of ecosystems and humans. While numerous studies have monitored APIs in rivers, these employ different analytical methods, measure different APIs, and have ignored many of the countries of the world. This makes it difficult to quantify the scale of the problem from a global perspective. Furthermore, comparison of the existing data, generated for different studies/regions/continents, is challenging due to the vast differences between the analytical methodologies employed. Here, we present a global-scale study of API pollution in 258 of the world's rivers, representing the environmental influence of 471.4 million people across 137 geographic regions. Samples were obtained from 1,052 locations in 104 countries (representing all continents and 36 countries not previously studied for API contamination) and analyzed for 61 APIs. Highest cumulative API concentrations were observed in sub-Saharan Africa, south Asia, and South America. The most contaminated sites were in low- to middle-income countries and were associated with areas with poor wastewater and waste management infrastructure and pharmaceutical manufacturing. The most frequently detected APIs were carbamazepine, metformin, and caffeine (a compound also arising from lifestyle use), which were detected at over half of the sites monitored. Concentrations of at least one API at 25.7% of the sampling sites were greater than concentrations considered safe for aquatic organisms, or which are of concern in terms of selection for antimicrobial resistance. Therefore, pharmaceutical pollution poses a global threat to environmental and human health, as well as to delivery of the United Nations Sustainable Development Goals.
Sustainable wastewater treatment is one of the biggest issues of the 21st century. Metals such as Zn2+ have been released into the environment due to rapid industrial development. In this study, dried watermelon rind (D-WMR) is used as a low-cost adsorption material to assess natural adsorbents' ability to remove Zn2+ from synthetic wastewater. D-WMR was characterized using scanning electron microscope (SEM) and X-ray fluorescence (XRF). According to the results of the analysis, the D-WMR has two colours, white and black, and a significant concentration of mesoporous silica (83.70%). Moreover, after three hours of contact time in a synthetic solution with 400 mg/L Zn2+ concentration at pH 8 and 30 to 40 °C, the highest adsorption capacity of Zn2+ onto 1.5 g D-WMR adsorbent dose with 150 μm particle size was 25 mg/g. The experimental equilibrium data of Zn2+ onto D-WMR was utilized to compare nonlinear and linear isotherm and kinetics models for parameter determination. The best models for fitting equilibrium data were nonlinear Langmuir and pseudo-second models with lower error functions. Consequently, the potential use of D-WMR as a natural adsorbent for Zn2+ removal was highlighted, and error analysis indicated that nonlinear models best explain the adsorption data.
Cylinder-shaped NaY zeolite was used as an adsorbent for eradicating both heavy metal ions (Cu2+, Zn2+, Ni2+, and Co2+) and proteins from the waste streams. As a pseudo-metal ion affinity adsorbent, NaY zeolite was used in the capture of heavy metal ions in the first stage. The amount (molar basis) of metal ions adsorbed onto NaY zeolite decreased in the order of Cu2+ > Zn2+ > Co2+ > Ni2+. Bovine serum albumin (BSA) was utilized as a model of proteins used in the waste adsorption process by NaY zeolite. The adsorption capacities of NaY zeolite and Cu/NaY zeolite for BSA were 14.90 mg BSA/g zeolite and 84.61 mg BSA/g zeolite, respectively. Moreover, Cu/NaY zeolite was highly stable in the solutions made of 2 M NaCl, 500 mM imidazole or 125 mM EDTA solutions. These conditions indicated that the minimal probability of secondary contamination caused by metal ions and soluble proteins in the waste stream. This study demonstrates the potential of Cu/NaY zeolite complex as an efficient pseudo-metal chelate adsorbent that could remove metal ions and water-soluble proteins from wastewater concurrently.
Water pollution caused by dyes has been a serious problem affecting human health and environment. The surface of polyacrylonitrile (PAN) nanofiber membranes was modified by mild hydrolysis and coupled with bovine serum albumin (BSA) obtained from the laboratory wastes, resulting in the synthesis of P-COOH and P-COOH-BSA nanofibers. The nanofibers with specific functional groups may enhance their potential applications toward the removal of ionic dyes in wastewater. Toluidine blue O (TBO) was applied as an example of cationic dye to evaluate the removal efficiency of P-COOH-BSA nanofiber. Results showed that the equilibrium dissociation constant and maximum removal capacity were 0.48 mg/mL and 434.78 mg/g, respectively, at pH 12, where the TBO removal can be explained based on Langmuir isotherm and pseudo-second-order model. Desorption studies have shown that TBO adsorbed on P-COOH-BSA protein membrane can be completely eluted with either 1 M NaCl or 50% glycerol. The results of repeated studies indicated that after five consecutive adsorption/desorption cycles, the removal efficiency of TBO can be maintained at ~97%. P-COOH-BSA has shown to be promising adsorbent in TBO dye removal from dye wastewater.
In this study, we assessed and optimized a low-dissolved-oxygen oxic-anoxic (low-DO OA) process to achieve a low-cost and sustainable solution for wastewater treatment systems in the developing tropical countries treating low chemical oxygen demand-to-nitrogen ratio (COD/N) wastewater. The low-DO OA process attained complete ammonia removal and the effluent nitrate nitrogen (NO3-N) was below 0.3 mg/L. The recommended hydraulic retention time and sludge retention time (SRT) were 16 h and 20 days, respectively. The 16S rRNA sequencing data revealed that long SRT (20 days) encouraged the growth of nitrite-oxidizing bacteria (NOB) affiliated with "Candidatus Nitrospira defluvii". Comammox made up 10-20% of the Nitrospira community. NOB and comammox related to Nitrospira were enriched at long SRT (20 days) to achieve good low-DO nitrification performance. The low-DO OA process was efficient and has simpler design than conventional processes, which are keys for sustainable wastewater treatment systems in the developing countries treating low COD/N wastewater.
The detection of phenolic compounds, i.e. resorcinol (RC) catechol (CC) and hydroquinone (HQ) are important due to their extremely hazardous impact and poor environmental degradation. In this work, a novel and sensitive composite of electrochemically reduced graphene oxide-poly(Procion Red MX-5B)/gold nanoparticles modified glassy carbon electrode (GCE/ERGO-poly(PR)/AuNPs) was assembled for voltammetric detection of benzenediol isomers (RC, CC, and HQ). The nanocomposite displayed high peak currents towards the oxidation of RC, HQ, and CC compared to non-modified GCE. The peak-to-peak separations were 0.44 and 0.10 V for RC-CC and CC-HQ, respectively. The limit of detections were 53, 53, and 79 nM for HQ, CC, and RC with sensitivities of 4.61, 4.38, and 0.56 μA/μM (S/N = 3), respectively. The nanocomposite displayed adequate reproducibility, besides good stability and acceptable recoveries for wastewater and cosmetic samples analyses.
As a remedy for environmental pollution, a versatile synthetic approach has been developed to prepare polyvinyl alcohol (PVA)/nitrogen-doped carbon dots (CDs) composite film (PVA-CDs) for removal of toxic cadmium ions. The CDs were first synthesized using carboxymethylcellulose (CMC) of oil palms empty fruit bunch wastes with the addition of polyethyleneimine (PEI) and then the CDs were embedded with PVA. The PVA-CDs film possess synergistic functionalities through increasing the content of hydrogen bonds for chemisorption compared to the pure CDs. Optical analysis of PVA-CDs film was performed by ultraviolet-visible and fluorescence spectroscopy. Compared to the pure CDs, the solid-state PVA-CDs displayed a bright blue color with a quantum yield (QY) of 47%; they possess excitation-independent emission and a higher Cd2+ removal efficiency of 91.1%. The equilibrium state was achieved within 10 min. It was found that adsorption data fit well with the pseudo-second-order kinetic and Langmuir isotherm models. The maximum adsorption uptake was 113.6 mg g-1 at an optimal pH of 7. Desorption experiments showhe that adsorbent can be reused fruitfully for five adsorption-desorption cycles using 0.1 HCl elution. The film was successfully applied to real water samples with a removal efficiency of 95.34% and 90.9% for tap and drinking water, respectively. The fabricated membrane is biodegradable and its preparation follows an ecofriendly green route.
This study investigated chlorinated transformation products (TPs) and their parent micropollutants, aromatic pharmaceuticals and personal care products (PPCPs) in the urban water bodies of two metropolitan cities. Nine PPCPs and 16 TPs were quantitatively or semi-quantitatively determined using isotope dilution techniques and liquid chromatography-tandem mass spectrometry. TPs and most PPCPs were effectively removed by conventional wastewater treatments in a wastewater treatment plant (WWTP). Chlorinated parabens and all PPCPs (at concentrations below 1000 ng/L) were present in the waters receiving treated wastewater. By contrast, the waters receiving untreated wastewater contained higher levels of PPCPs (up to 9400 ng/L) and more species of chlorinated TPs including chlorinated parabens, triclosan, diclofenac, and bisphenol A. The very different chemical profiles between the water bodies of the two cities of similar geographical and climatic properties may be attributed to their respective uses of chemicals and policies of wastewater management. No apparent increase in the number of species or abundances of TPs was observed in either the chlorinated wastewater or the seawater rich in halogens. This is the first study to elucidate and compare the profiles of multiple TPs and their parent PPCPs in the water bodies of coastal cities from tropical islands. Our findings suggest that chlorinated derivatives of bisphenol A, diclofenac, triclosan, and parabens in the surface water originate from sources other than wastewater disinfection or marine chlorination. Although further studies are needed to identify the origins, conventional wastewater treatments may protect natural water bodies against contamination by those chlorinated substances.
Oily wastewater, especially water-oil emulsion has become serious environmental issue and received global attention. Chemical demulsifiers are widely used to treat oil-water emulsion, but the toxicity, non-recyclable and non-environmental friendly characteristic of chemical demulsifiers had limited their practical application in oil-water separation. Therefore, it is imperative to develop an efficient, simple, eco-friendly and recyclable demulsifiers for breaking up the emulsions from the oily wastewater. In this study, a magnetic demulsifier, magnetite-reduced graphene oxide (M-rGO) nanocomposites were proposed as a recyclable demulsifier to break up the surfactant stabilized crude oil-in-water (O/W) emulsion. M-rGO nanocomposites were prepared via in situ chemical synthesis by using only one type Fe salt and GO solid as precursor at room temperature. The prepared composites were fully characterized by various techniques. The effect of demulsifier dosage and pH of emulsion on demulsification efficiency (ED) has been studied in detailed. The demulsification mechanism was also proposed in this study. Results showed that M-rGO nanocomposites were able to demulsify crude O/W emulsion. The ED reaches 99.48% when 0.050 wt.% of M-rGO nanocomposites were added to crude O/W emulsion (pH = 4). Besides, M-rGO nanocomposites can be recycled up to 7 cycles without showing a significant change in terms of ED. Thus, M-rGO nanocomposite is a promising demulsifier for surfactant stabilized crude O/W emulsion.
Methylene blue (MB) is a dye pollutant commonly present in textile wastewater. We investigate and critically evaluate the applicability of BaTiO3/GO composite for photodegradation of MB in synthetic wastewater under UV-vis irradiation. To enhance its performance, the BaTiO3/GO composite is varied based on the BaTiO3 weight. To compare and evaluate any changes in their morphologies and crystalline structures before and after treatment, BET (Brunauer-Emmett-Teller), XRD (X-ray diffraction), FTIR (Fourier transform infrared spectroscopy), SEM (scanning electron microscopy) and TEM (transmission electron microscopy) tests are conducted, while the effects of reaction time, pH, dose of photocatalyst and initial MB concentration on its photodegradation by the composite are also investigated under identical conditions. The degradation pathways and removal mechanisms of MB by the BaTiO3/GO are elaborated. It is evident from this study that the BaTiO3/GO composite is promising for MB photodegradation through ·OH. Under optimized conditions (0.5 g/L of dose, pH 9.0, and 5 mg/L of MB concentration), the composite with 1:2 dose ratio of BaTiO3/GO has the highest MB degradation rate (95%) after 3 h of UV vis irradiation. However, its treated effluents still could not comply with the discharge standard limit of less than 0.2 mg/L imposed by national environmental legislation. This suggests that additional biological treatments are still required to deal with the remaining oxidation by-products of MB, still present in the wastewater samples such as 3,7-bis (dimethyl-amino)-10H-phenothiazine 5-oxide.
The pollution of water resources due to the disposal of industrial wastes that have organic material like phenol is causing worldwide concern because of their toxicity towards aquatic life, human beings and the environment. Phenol causes nervous system damage, renal kidney disease, mental retardation, cancer and anaemia. In this study, magnetic palm kernel biochar is used for removal of phenol from wastewater. The effect of parameters such as pH, agitation speed, contact time and magnetic biochar dosage are validated using design of experiments. The statistical analysis reveals that the optimum conditions for the highest removal (93.39%) of phenol are obtained at pH of 8, magnetic biochar dosage of 0.6 g, agitation speed at 180 rpm and time of 60 min with the initial concentration of 10 mg/L. The maximum adsorption capacities of phenol were found to be 10.84 mg/g and Langmuir and Freundlich isotherm models match the experimental data very well and adsorption kinetic obeys a pseudo-second order. Hence, magnetic palm kernel can be a potential candidate for phenol removal from wastewater.
Many wastewater treatment plants (WWTPs) operating in biological nitrogen removal activated sludge process in the tropics are facing the pressure of increasingly stringent effluent standards while seeking solutions to reduce the plants' energy consumption and operating cost. This study investigated the feasibility of applying low-dissolved oxygen (low-DO) nitrification and utilizing slowly-biodegradable chemical oxygen demand (sbCOD) for denitrification, which helps to reduce energy usage and operating cost in treating low soluble COD-to-nitrogen tropical wastewater. The tropical wastewater was first characterized using wastewater fractionation and respirometry batch tests. Then, a lab-scale sequencing batch reactor (SBR) was operated to evaluate the long-term stability of low-DO nitrification and utilizing sbCOD for denitrification in an anoxic-oxic (AO) process treating tropical wastewater. The wastewater fractionation experiment revealed that particulate settleable solids (PSS) in the wastewater provided slowly-biodegradable COD (sbCOD), which made up the major part (51 ± 10%) of the total COD. The PSS hydrolysis rate constant at tropical temperature (30 °C) was 2.5 times higher than that at 20 °C, suggesting that sbCOD may be utilized for denitrification. During the SBR operation, high nitrification efficiency (93 ± 6%) was attained at low-DO condition (0.9 ± 0.1 mg O2/L). Utilizing sbCOD for post-anoxic denitrification in the SBR reduced the effluent nitrate concentration. Quantitative polymerase chain reaction, 16S rRNA amplicon sequencing and fluorescence in-situ hybridization revealed that the genus Nitrospira was a dominant nitrifier. 16S rRNA amplicon sequencing result suggested that 50% of the Nitrospira-related operational taxonomic units were affiliated with comammox, which may imply that the low-DO condition and the warm wastewater promoted their growth. The nitrogen removal in a tropical AO process was enhanced by incorporating low-DO nitrification and utilizing sbCOD for post-anoxic denitrification, which contributes to an improved energy sustainability of WWTPs.
One of the biggest challenges of using single-chamber microbial fuel cells (MFCs) that utilize proton-exchange membrane (PEM) air cathode for bioenergy recovery from recalcitrant organic compounds present in wastewater is mainly attributed to their high internal resistance in the anodic chamber of the single microbial fuel cell (MFC) configurations. The high internal resistance is due to the small surface area of the anode and cathode electrodes following membrane biofouling and pH splitting conditions as well as substrate and oxygen crossover through the membrane pores by diffusion. To address this issue, the fabrication of new PEM air-cathode single-chamber MFC configuration was investigated with inner channel flow open assembled with double PEM air cathodes (two oxygen reduction activity zones) coupled with spiral-anode MFC (2MA-CsS-AMFC). The effect of various proton-exchange membranes (PEMs), including Nafion 117 (N-117), Nafion 115 (N-115), and Nafion 212 (N-212) with respective thicknesses of 183, 127, and 50.08 μ, was separately incorporated into carbon cloth as PEM air-cathode electrode to evaluate their influences on the performance of the 2MA-CsS-AMFC configuration operated in fed-batch mode, while Azorubine dye was selected as the recalcitrant organic compound. The fed-batch test results showed that the 2MA-CsS-AMFC configuration with PEM N-115 operated at Azorubine dye concentration of 300 mg L-1 produced the highest power density of 1022.5 mW m-2 and open-circuit voltage (OCV) of 1.20 V coupled with enhanced dye removal (4.77 mg L h-1) compared to 2MA-CsS-AMFCs with PEMs N-117 and N-212 and those in previously published data. Interestingly, PEM 115 showed remarkable reduction in biofouling and pH splitting. Apart from that, mass transfer coefficient of PEM N-117 was the most permeable to oxygen (KO = 1.72 × 10-4 cm s-1) and PEM N-212 was the most permeable membrane to Azorubine (KA = 7.52 × 10-8 cm s-1), while PEM N-115 was the least permeable to both oxygen (KO = 1.54 × 10-4) and Azorubine (KA = 7.70 × 10-10). The results demonstrated that the 2MA-CsS-AMFC could be promising configuration for bioenergy recovery from wastewater treatment under various PEMs, while application of PEM N-115 produced the best performance compared to PEMs N-212 and N-117 and those in previous studies of membrane/membrane-less air-cathode single-chamber MFCs that consumed dye wastewater.
Hydrazine is an intermediate product of the anaerobic ammonium oxidation (Anammox) process where both ammonium and nitrite in wastewater are converted to nitrogen gas by bacteria. In this study the effect of external hydrazine addition (5, 10, 15, and 20 mg/L) on the start-up period of the Anammox process was studied using sequencing batch reactors (SBRs). The SBR with an addition of 10 mg/L hydrazine took only 7 weeks to stabilize and achieve the maximum removal of ammonium and nitrite, whereas the SBR without the addition of hydrazine took 12 weeks. The amount of Heme C extracted from the biomass indicated that externally added hydrazine accelerated the growth of Anammox bacteria and reduced the release of nitrous oxide gas from the reactors.
Production of Scenedesmus sp. biomass in chicken slaughterhouse wastewater (CSWW) is a promising alternative technique for commercial culture medium due to the high nutritional content of the generated biomass to be used as fish feeds. The current work deals with optimising of biomass production in CSWW using response surface methodology (RSM) as a function of two independent variables, namely temperature (10-30 °C) and photoperiod (6-24 h). The potential application of biomass yield as fish feeds was evaluated based on carbohydrate, protein and lipid contents. The results revealed that the best operating parameters for Scenedesmus sp. biomass production with high contents of carbohydrates, proteins and lipids were determined at 30 °C and after 24 h. The actual and predicted values were 2.47 vs. 3.09 g, 1.44 vs. 1.27 μg/mL, 29.9 vs. 31.60% and 25.75 vs. 28.44%, respectively. Moreover, the produced biomass has a high concentration of fatty acid methyl ester (FAME) as follows: 35.91% of C15:1; 17.58% of C24:1 and 14.11% of C18:1N9T. The biomass yields have 7.98% of eicosapentaenoic acid (EPA, C20:5N3) which is more appropriate as fish feeds. The Fourier transform infrared (FTIR) analysis of biomass revealed that the main functional groups included hydroxyl (OH), aldehyde (=C-H), alkanes and acyl chain groups. Scanning electron micrograph (SEM) and energy-dispersive X-ray spectroscopic analysis (EDS) indicated that the surface morphology and element distribution in biomass produced in BBM and CSWW were varied. The findings have indicated that the biomass produced in CSWW has high potential as fish feeds.
Bio-hydrogen production from wastewater using sludge as inoculum is a sustainable approach for energy production. This study investigated the influence of initial pH and temperature on bio-hydrogen production from dairy wastewater using pretreated landfill leachate sludge (LLS) as an inoculum. The maximum yield of 113.2 ± 2.9 mmol H2/g chemical oxygen demand (COD) (12.8 ± 0.3 mmol H2/g carbohydrates) was obtained at initial pH 6 and 37 °C. The main products of volatile fatty acids were acetate and butyrate with the ratio of acetate:butyrate was 0.4. At optimum condition, Gibb's free energy was estimated at -40 kJ/mol, whereas the activation enthalpy and entropy were 65 kJ/mol and 0.128 kJ/mol/l, respectively. These thermodynamic quantities suggest that bio-hydrogen production from dairy wastewater using pretreated LLS as inoculum was effective and efficient. In addition, genomic and bioinformatics analyses were performed in this study.
Microalgal biomass produced from the phycoremediation of wastewater represents an important protein source, lipids, and natural antioxidants and bioproducts. Therefore, the microalgal biomass and their derived compounds are used in animal and aquaculture feed as well as human nutrition and health products. Many microalgal species have shown promising potential for many bioproducts. However, significant processes to find the optimum quality and quantity of microalgal biomass are still required especially when it is used as a replacement for aquaculture feed. The limitations lie in the selection of microalgal species and their production. The present review discusses the potential generation of bioproducts from microalgal biomass resulting from the phycoremediation of wet market wastewater. The consortium approach in wastewater treatment and the comparison between biomass production and available common feeds for aquaculture were reviewed.
Reports of pharmaceuticals exist in surface water and drinking water around the world, indicate they are ineffectively remove from water and wastewater using conventional treatment technologies. The potential of adverse effect of these pharmaceuticals on public health and aquatic life, also their continuos accumulation have raised the development of water treatment technologies. Hybrid treatment processes like membrane filtration and advance oxidation processes (AOPs) are likely to give rise to efficient simultaneous degradation and separation mechanisms. Conventional membrane filtration techniques can remove the majority of contaminants, but the smallest, undegraded, and stabilized pharmaceutical wastes persist in the treated water. After some 20 years, researchers have recognized the important role of AOPs in the treatment of pharmaceutical wastewater because these technologies are capable of oxidizing recalcitrant, toxic, and non-biodigradable compounds into numerous by-products and finally, inert end-products via the intermediacy of hydroxyl and other radicals. Evidently, membranes are subjected to the fouling phenomenon by the contaminants in wastewater, hence resulting in a reduction of clean water flux and increase in energy demand. In such situations, these membrane hybrid AOPs exert a complementary effect in the elimination of membrane fouling, thus enhancing the performance of the membrane. Therefore, in this review, we describe the basic aspects of the removal and transformation of certain pharmaceuticals via membranes and AOPs. In addition, information and evidences on membrane hybrid AOPs in the field of pharmaceutical wastewater treatment is also presented.