Photodegradation of a mixture of five pharmaceuticals commonly found in wastewater: Experimental and computational analysis.

Photochemical transformation of pharmaceuticals plays an important role in their natural attenuation, especially in lagoon-based wastewater treatment plants and surface waters receiving substantial sunlight. In this study, the photodegradation of five important pharmaceuticals was studied in samples obtained from a wastewater treatment plant and surface water sources. Batch photodegradation studies for a mixture of pharmaceuticals (diclofenac, sulfamethoxazole, acetaminophen, carbamazepine and gemfibrozil) were carried out in a photochemical reactor. Multiple aliquots of samples removed from the reactor during the experiment were analyzed through high-performance liquid chromatography (HPLC) coupled to a photodiode array (PDA) detector. Intermediate products formed due to photodegradation were identified by ultra-high-performance liquid chromatography coupled with a time-of-flight mass spectrometry (UHPLC-MS/MS). Diclofenac and sulfamethoxazole were found to undergo direct photodegradation due to strong light absorption, whereas the indirect route of photosensitized degradation in the presence of dissolved organic matter (DOM) and model humic acid was significant for acetaminophen, carbamazepine, and gemfibrozil. The reactive radicals such as hydroxyl (OH•), singlet oxygen (1O2) and excited states of DOM (*DOM) were predominantly responsible for the indirect photodegradation of acetaminophen, gemfibrozil and carbamazepine, respectively. Computational analysis revealed that chlorine and carbon atoms belonging to the benzene ring of diclofenac were more reactive to radical attack. Sulfamethoxazole photodegradation occurred through oxidation of the NH2 group. Acetaminophen was more susceptible to electrophilic radical attack at the O-11, and N-7 positions and carbon atoms ortho to the phenolic oxygen and the amine group. The double bonds between C-7, C-8 and C-13 were the most reactive sites for carbamazepine that participated in the phototransformation pathway. Organic matter plays a critical role in the photodegradation of emerging contaminants. The coupling of DFT calculations with UHPLC-MS/MS analysis provided insights on key functional groups participating in the phototransformation pathway. Thus, both parent pharmaceuticals and the photodegradation intermediates should be considered during wastewater treatment.

Surface modification of coconut shell activated carbon for efficient solid-phase extraction of N-nitrosodimethylamine from water.

A practical and cheap methodology in modifying commercial coconut shell activated carbon for solid-phase extraction of N-nitrosodimethylamine in water was developed through an understanding of activated carbon surface chemistry. In comparison with commercial activated carbon, extraction recoveries by activated carbon treated with sulfuric acid decreased by 50%, while those of activated carbon heated at 800°C improved by more than 100%. Acid treatment increased the oxygen content on the carbon's surface. In contrast, heat treatment decreased the surface oxygen content, resulting in a more hydrophobic surface, which favoured adsorption and extraction of N-nitrosodimethylamine. The influence of different activated carbon sizes, amount of modified activated carbon, and pH on the N-nitrosodimethylamine recoveries was assessed and compared with the commercial solid-phase extraction cartridge. The recommended amount of powder activated carbon treated at 800°C was 3 g to yield an optimum recovery of 130%, which was superior to the commercial solid-phase extraction cartridges. The method validation results confirmed the high accuracy, reproducibility, and precision of the method. The study indicated that chemisorption plays a significant role in the adsorption of N-nitrosodimethylamine on activated carbon, and the optimization of its surface chemistry can enhance N-nitrosodimethylamine adsorption/extraction from water.

Fate of pharmaceuticals and personal care products in a wastewater treatment plant with parallel secondary wastewater treatment train.

Seasonal variations in the concentrations and fate of 20 selected pharmaceuticals and personal care products (PPCPs) were investigated over one year in a wastewater treatment plant in New Zealand, which relies on a membrane bioreactor (MBR) and Bardenpho as parallel processes for its secondary treatment. Results showed that all of the monitored PPCPs were detected in the wastewater influent. Nonsteroidal anti-inflammatory drugs (NSAIDS) and caffeine were predominant in the influent, whereas in the effluent, ß-blockers and benzotriazole were present at significant concentrations. Total PPCPs' concentration in the influent was found to be 130 µg/L. Average removal efficiency was found to be ≥ 99% for acetaminophen, caffeine, TCEP, naproxen, and ibuprofen, whereas <50% of trimethoprim, metoprolol, and benzotriazole were removed. Contrary to the existing literature, no significant differences were found in the removal of PPCPs through MBR and Bardenpho processes, hinting that optimally operated Bardenpho can be equally effective in the removal of emerging contaminants as MBR. The occurrence and removal efficiencies of PPCPs were found to exhibit significant seasonal variations, with the highest influent concentrations of PPCPs reported in autumn and winter. Heavy rainfall had an insignificant impact on PPCPs' removal efficiencies although it resulted in much-diluted concentrations of PPCPs in the influent. Spearman's correlation analysis showed significant correlations between PPCPs' mass loads in the influent, wastewater quality parameters, and environmental factors. It was also found that, except sulfamethoxazole, ecotoxicity risks were minimal for the rest of the monitored PPCPs in wastewater effluent.

Fate of Environmental Pollutants.

This annual review covers the literature published in 2017 on topics related to the occurrence and fate of emerging environmental pollutants in wastewater. Due to the vast amount of literature published on this topic, we have discussed only a portion of the quality research publications, due to the limitation of space. The abstract search was carried out using Web of Science, and the abstracts were selected based on their relevance. In few cases, full-text articles were referred to better understand new findings. This review is divided into the following sections: antibioticresistant bacteria (ARBs) and antibiotic-resistant genes (ARGs), disinfection by-products (DBPs), estrogens, pesticides, pharmaceuticals and personal care products (PPCPs), and microplastics, a new section added this year.

Fate of Environmental Pollutants.

This annual review covers the literature published in 2016 on topics related to the occurrence and fate of emerging environmental pollutants in wastewater. Due to the vast amount of literature published on this topic, we have discussed only a portion of the quality research publications, due to limitation of space. The abstract search was carried out using Web of Science, and the abstracts were selected based on their relevance. In few cases, fulltext articles were referred to better understand new findings. This review is divided into the following sections: Antibiotic resistant bacteria (ARBs) and antibiotic resistant genes (ARGs), disinfection by-products (DBPs), estrogens, nanomaterials, pathogens, perfluorinated chemicals (PFCs), pharmaceuticals and personal care products (PPCPs), and other pollutants.

Membrane Processes.

This review, for literature published in 2016, contains information related to membrane processes for municipal and industrial applications. This review is a subsection of the Treatment Systems section of the annual Water Environment Federation literature review and covers the following topics: membrane bioreactor (MBR) configuration, design, nutrient removal, operation, industrial treatment, anaerobic membrane systems, reuse, microconstituents removal, membrane technology advances, membrane fouling, and modeling. Other sub-sections of the Treatment Systems section that might relate to this literature review include: Biological Fixed-Film Systems, Activated Sludge and Other Aerobic Suspended Culture Processes, Anaerobic Processes, and Water Reclamation and Reuse. The following sections might also have related information on membrane processes: Industrial Wastes, Hazardous Wastes, and Fate and Effects of Pollutants.

A review of polymeric membranes and processes for potable water reuse.

Conventional water resources in many regions are insufficient to meet the water needs of growing populations, thus reuse is gaining acceptance as a method of water supply augmentation. Recent advancements in membrane technology have allowed for the reclamation of municipal wastewater for the production of drinking water, i.e., potable reuse. Although public perception can be a challenge, potable reuse is often the least energy-intensive method of providing additional drinking water to water stressed regions. A variety of membranes have been developed that can remove water contaminants ranging from particles and pathogens to dissolved organic compounds and salts. Typically, potable reuse treatment plants use polymeric membranes for microfiltration or ultrafiltration in conjunction with reverse osmosis and, in some cases, nanofiltration. Membrane properties, including pore size, wettability, surface charge, roughness, thermal resistance, chemical stability, permeability, thickness and mechanical strength, vary between membranes and applications. Advancements in membrane technology including new membrane materials, coatings, and manufacturing methods, as well as emerging membrane processes such as membrane bioreactors, electrodialysis, and forward osmosis have been developed to improve selectivity, energy consumption, fouling resistance, and/or capital cost. The purpose of this review is to provide a comprehensive summary of the role of polymeric membranes in the treatment of wastewater to potable water quality and highlight recent advancements in separation processes. Beyond membranes themselves, this review covers the background and history of potable reuse, and commonly used potable reuse process chains, pretreatment steps, and advanced oxidation processes. Key trends in membrane technology include novel configurations, materials and fouling prevention techniques. Challenges still facing membrane-based potable reuse applications, including chemical and biological contaminant removal, membrane fouling, and public perception, are highlighted as areas in need of further research and development.

Fate of Environmental Pollutants.

This annual review covers the literature published in 2015 on topics related to the occurrence and fate of emerging environmental pollutants in wastewater. Due to the vast amount of literature published on this topic, I have discussed only a fraction of the quality research publications, up to maximum 20 relevant articles per section, due to limitation of space. The abstract search was carried out using Web of Science, and the abstracts were selected based on their relevance. In few cases, full-text articles were referred to better understand new findings. This review is divided into the following sections: biological agents, disinfection by-products (DBPs), halogenated compounds, pharmaceuticals and personal care products (PPCPs), and other emerging contaminants.

Membrane Processes.

This review, for literature published in 2015, contains information related to membrane processes for municipal and industrial applications. This review is a subsection of the Treatment Systems section of the annual Water Environment Federation literature review and covers the following topics: pretreatment, membrane bioreactor (MBR) configuration, design, nutrient removal, operation, industrial treatment, anaerobic membrane systems, reuse, microconstituents removal, membrane technology advances, membrane fouling, and modeling. Other sub-sections of the Treatment Systems section that might relate to this literature review include: Biological Fixed-Film Systems, Activated Sludge and Other Aerobic Suspended Culture Processes, Anaerobic Processes, Water Reclamation and Reuse. The following sections might also have related information on membrane processes: Industrial Wastes, Hazardous Wastes, and Fate and Effects of Pollutants.

Fate of Environmental Pollutants.

This annual review covers the literature published in 2014 on topics related to the occurrence and fate of emerging environmental pollutants in wastewater. Due to the vast amount of literature published on this topic, I have discussed only a fraction of the quality research publications, up to maximum 15 relevant articles per section, due to limitation of space. The abstract search was carried out using Web of Science, and the abstracts were selected based on their relevance. In few cases, full-text articles were referred to better understand new findings. This review is divided into the following sections: biological agents, disinfection by-products (DBPs), halogenated compounds, pharmaceuticals and personal care products (PPCPs), and other emerging contaminants.

Revealing the long-term impact of photodegradation and fragmentation on HDPE in the marine environment: Origins of microplastics and dissolved organics.

The extensive usage of high-density polyethylene (HDPE) materials in marine environments raises concerns about their potential contribution to plastic pollution. Various factors contribute to the degradation of HDPE in marine environments, including UV radiation, seawater hydrolysis, biodegradation, and mechanical stress. Despite their supposed long lifespans, there is still a lack of understanding about the long-term degradation mechanisms that cause weathering of seawater-exposed HDPE products. In this research, the impact of UV radiation on the degradation of HDPE pile sleeves was studied in natural as well as laboratory settings to isolate the UV effect. After nine years of exposure to the marine environment in natural settings, the HDPE pile sleeves exhibited an increase in oxygen-containing surface functional groups and more morphological changes compared to accelerated UVB irradiation in the laboratory. This indicated that combined non-UV mechanisms may play a major role in HDPE degradation than UV irradiation alone. However, UVB irradiation was found to release dissolved organic carbon and total dissolved nitrogen from HDPE pile sleeves, reaching levels of up to 15 mg/L and 2 mg/L, respectively. Our findings underscore the significance of taking into account both UV and non-UV degradation mechanisms when evaluating the role of HDPE in contributing to marine plastic pollution.

Quantification and characterization of microplastics in coastal environments: Insights from laser direct infrared imaging.

The study identified and quantified nine plastic polymers frequently detected in the environment by collecting sediment and seawater samples from coastal areas in Auckland, New Zealand. Polymer types, size distributions, and number of microplastics (MPs) were analyzed using a laser direct infrared (LDIR) imaging technique. Compared to conventional spectroscopic or microscopic methods, LDIR enabled capturing and quantifying MPs in much lower size ranges (20-5000 µm). The results demonstrated the widespread occurrence of MPs in the Auckland coastal environment, with polyethylene terephthalate (PET) being the most frequently detected plastic polymer. MP contamination levels ranged from 13 to 83 particles per liter of coastal water and from 1200 to 3400 particles/kg of dry sand in beach sediments. Six additional locations were investigated to assess the contribution of MPs from stormwater drains to the coastal environment. The total count of identified MPs extracted from sediments near stormwater drains reached a maximum of 18,000 particles/kg of dry sand, representing an order of magnitude increase compared to MP levels found in beach sediments at the same location. In contrast to the prevalence of PET and polyamide observed in beach sediments and coastal waters, polyurethane and polyethylene emerged as the predominant plastic polymers in the vicinity of stormwater drain sediments, implying that the variation could potentially stem from distinct sources of plastics. This significant disparity in quality and quantity underscored the potential link between urban runoff and MP pollution in marine ecosystems. A sample preparation method using 100 g sediment samples was developed and used to assess and compare MPs detection in sediment samples. The commonly used 5 g sample method showed higher extraction efficiency and better detection of the most abundant MPs, but the new 100 g method enabled the detection of previously missed, less abundant plastics.

Various additive release from microplastics and their toxicity in aquatic environments.

Additives may be present in amounts higher than 50% within plastic objects. Additives in plastics can be gradually released from microplastics (MPs) into the aquatic environment during their aging and fragmentation because most of them do not chemically react with the polymers. Some are known to be hazardous substances, which can cause toxicity effects on organisms and pose ecological risks. In this paper, the application of functional additives in MPs and their leaching in the environment are first summarized followed by their release mechanisms including photooxidation, chemical oxidation, biochemical degradation, and physical abrasion. Important factors affecting the additive release from MPs are also reviewed. Generally, smaller particle size, light irradiation, high temperature, dissolved organic matter (DOM) existence and alkaline conditions can promote the release of chemicals from MPs. In addition, the release of additives is also influenced by the polymer's structure, electrolyte types, as well as salinity. These additives may transfer into the organisms after ingestion and disrupt various biological processes, leading to developmental malformations and toxicity in offspring. Nonetheless, challenges on the toxicity of chemicals in MPs remain hindering the risk assessment on human health from MPs in the environment. Future research is suggested to strengthen research on the leaching experiment in the actual environment, develop more techniques and analysis methods to identify leaching products, and evaluate the toxicity effects of additives from MPs based on more model organisms. The work gives a comprehensive overview of current process for MP additive release in natural waters, summarizes their toxicity effects on organisms, and provides recommendations for future research.

A review on value-addition to plastic waste towards achieving a circular economy.

Plastic and mixed plastic waste (PW) has received increased worldwide attention owing to its huge rate of production, high persistency in the environment, and unsustainable waste management practices. Therefore, sustainable PW management and upcycling approaches are imperative to achieve the objectives of the United Nations Sustainable Development Goals. Numerous recent studies have shown the application and feasibility of various PW conversion techniques to produce materials with better economic value. Within this framework, the current review provides an in-depth analysis of cutting-edge thermochemical technologies such as pyrolysis, gasification, carbonization, and photocatalysis that can be used to value plastic and mixed PW in order to produce energy and industrial chemicals. Additionally, a thorough examination of the environmental impacts of contemporary PW upcycling techniques and their commercial feasibility through life cycle assessment (LCA) and techno-economical assessment are provided in this review. Finally, this review emphasizes the opportunities and challenges accompanying with existing PW upcycling techniques and deliver recommendations for future research works.

Bromine contamination and risk management in terrestrial and aquatic ecosystems.

Bromine (Br) is widely distributed through the lithosphere and hydrosphere, and its chemistry in the environment is affected by natural processes and anthropogenic activities. While the chemistry of Br in the atmosphere has been comprehensively explored, there has never been an overview of the chemistry of Br in soil and aquatic systems. This review synthesizes current knowledge on the sources, geochemistry, health and environmental threats, remediation approaches, and regulatory guidelines pertaining to Br pollution in terrestrial and aquatic environments. Volcanic eruptions, geothermal streams, and seawater are the major natural sources of Br. In soils and sediments, Br undergoes natural cycling between organic and inorganic forms, with bromination reactions occurring both abiotically and through microbial activity. For organisms, Br is a non-essential element; it is passively taken up by plant roots in the form of the Br- anion. Elevated Br- levels can limit plant growth on coastal soils of arid and semi-arid environments. Br is used in the chemical industry to manufacture pesticides, flame retardants, pharmaceuticals, and other products. Anthropogenic sources of organobromine contaminants in the environment are primarily wastewater treatment, fumigants, and flame retardants. When aqueous Br- reacts with oxidants in water treatment plants, it can generate brominated disinfection by-products (DBPs), and exposure to DBPs is linked to adverse human health effects including increased cancer risk. Br- can be removed from aquatic systems using adsorbents, and amelioration of soils containing excess Br- can be achieved by leaching, adding various amendments, or phytoremediation. Developing cost-effective methods for Br- removal from wastewater would help address the problem of toxic brominated DBPs. Other anthropogenic organobromines, such as polybrominated diphenyl ether (PBDE) flame retardants, are persistent, toxic, and bioaccumulative, posing a challenge in environmental remediation. Future research directives for managing Br pollution sustainably in various environmental settings are suggested here.

Contaminants of emerging concerns (CECs) in a municipal wastewater treatment plant in Indonesia.

This study provides the first set of quantitative data on the occurrence and fate of a wide range of contaminants of emerging concerns (CECs) in Indonesia's largest wastewater treatment plant (WWTP). The WWTP employs waste stabilization ponds (WSPs) as the secondary treatment before discharging the effluent to the Citarum River. Fourteen out of twenty-two monitored CECs were detected in the wastewater influent, and seven were present in the effluent, with a total concentration of 29.8 ± 0.4 µg/L and 0.5 ± 0.0 µg/L, respectively. The occurrence of the CECs in this study was found to be well correlated with their possible use and known detection in surface waters in Indonesia. Caffeine (CAF) at 12.2 ± 0.1 µg/L, acetaminophen (ACT) at 9.1 ± 0.1 µg/L, N,N-diethyl-m-toluamide (DEET) at 5.0 ± 0.1 µg/L, ibuprofen (IBU) at 2.3 ± 0.0 µg/L, and triclosan (TCS) at 470 ± 64 ng/L were discovered as the five most prevalent CECs, followed by bisphenol A (BPA), trimethoprim (TMP), Tris(2-chloroethyl) phosphate (TCEP), sulfamethazine (SMZ), carbamazepine (CBZ), fluoxetine (FLX), benzotriazole (BTA), sulfamethoxazole (SMX), and metformin (METF). Biodegradable CECs (SMX, SMZ, ACT, IBU, TCS, BPA, CAF, DEET, and TMP) were efficiently removed (83-100%) by the WSP. In contrast, recalcitrant CECs achieved poor removal efficiencies (e.g., FLX at 24%), and for others, treatment processes even resulted in elevated concentrations in the effluent (CBZ by 85%, TCEP by 149%, and BTA by 92%). The CECs' influent concentrations were determined to pose a moderate aquatic cumulative risk, while no such risk was associated with their effluent concentrations. The study demonstrates the importance of conventional WWTPs in reducing the concentrations of CECs to minimize their aquatic contamination risk. The findings are relevant for countries, such as Indonesia, with limited resources for advanced centralized wastewater treatments, and which are exploring the efficacy of centralized WSP against the existing decentralized treatments.

Surface-modified activated carbon for N-nitrosodimethylamine removal in the continuous flow biological activated carbon columns.

The carcinogenic nitrogenous disinfection by-product, N-nitrosodimethylamine (NDMA), is challenging to adsorb due to its high polarity and solubility. Our previous research demonstrated that the adsorptive removal of NDMA can be improved using surface-modified activated carbon (AC800). The current study evaluated the efficacy of AC800 in removing NDMA in a continuous-flow column over 75 days, using both granular activated carbon (GAC) and biologically activated carbon (BAC) columns. The AC800 GAC column demonstrated extended breakthrough and exhaustion times of 10 days and 22 days, respectively, compared to the conventional GAC column at 4 days and 10.5 days. The surface modification effect persisted for 25 days before the removal trends became indistinguishable. The AC800 BAC column outperformed the conventional BAC column with a longer breakthrough time of 11.3 days compared to 7.4 days. BAC columns consistently showed greater NDMA removal, emphasizing the role of biodegradation in NDMA removal on carbon. The higher NDMA removal in the inoculated columns was attributed to increased microbial diversity and the dominance of six specific genera, Methylobacterium, Phyllobacterium, Curvibacter, Acidovorax, Variovorax, and Rhodoferax. This study provides new insights into using modified activated carbon as GAC and BAC media in a real-world continuous-flow setup.

Formation of disinfection by-products from microplastics, tire wear particles, and other polymer-based materials.

Disinfection by-products (DBPs) are formed through the disinfection of water containing precursors such as natural organic matter or anthropogenic compounds (e.g., pharmaceuticals and pesticides). Due to the ever increasing use of plastics, elastomers, and other polymers in our daily lives, polymer-based materials (PBMs) are detected more frequently and at higher concentrations in water and wastewater. The present review provides a comprehensive and systematic analysis of the contribution of PBMs - including elastomers, tire waste, polyelectrolytes, and microplastics - as precursors of DBPs in water and wastewater. Literature shows that the presence of PBMs can lead to the leaching of dissolved organic matter (DOM) and subsequent formation of DBPs upon disinfection in aqueous media. The quantity and type of DBPs formed strongly depends on the type of polymer, its concentration, its age, water salinity, and disinfection conditions such as oxidant dosage, pH, temperature, and contact time. DOM leaching from elastomers and tire waste was shown to form N-nitrosodimethylamine up to concerning levels of 930 ng/L and 466,715 ng/L, respectively upon chemical disinfection under laboratory conditions. Polyelectrolytes can also react with chemical disinfectants to form toxic DBPs. Recent findings indicate trihalomethanes formation potential of plastics can be as high as 15,990 µg/L based on the maximum formation potential under extreme conditions. Our analysis highlights an overlooked contribution of DOM leaching from PBMs as DBP precursors during disinfection of water and wastewater. Further studies need to be conducted to ascertain the extent of this contribution in real water and wastewater treatment plants.

Soil acidification and the liming potential of biochar.

Soil acidification in managed ecosystems such as agricultural lands principally results from the increased releasing of protons (H+) from the transformation reactions of carbon (C), nitrogen (N) and sulphur (S) containing compounds. The incorporation of liming materials can neutralize the protons released, hence reducing soil acidity and its adverse impacts to the soil environment, food security, and human health. Biochar derived from organic residues is becoming a source of carbon input to soil and provides multifunctional values. Biochar can be alkaline in nature, with the level of alkalinity dependent upon the feedstock and processing conditions. This review covers the fundamental aspects of soil acidification and of the use of biochar to address constraints related to acidic soil. Biochar is increasingly considered as an effective soil amendment for reducing soil acidity owing to its liming potential, thereby enhancing soil fertility and productivity in acid soils. The ameliorant effect on acid soils is mainly because of the dissolution of carbonates, (hydro)-oxides of the ash fraction of biochar and potential use by microorganisms.

Surfactant-enhanced mobilization of persistent organic pollutants: Potential for soil and sediment remediation and unintended consequences.

This review aims to provide an overview of the sources and reactions of persistent organic pollutants (POPs) and surfactants in soil and sediments, the surfactant-enhanced solubilisation of POPs, and the unintended consequences of surfactant-induced remediation of soil and sediments contaminated with POPs. POPs include chemical compounds that are recalcitrant to natural degradation through photolytic, chemical, and biological processes in the environment. POPs are potentially toxic compounds mainly used in pesticides, solvents, pharmaceuticals, or industrial applications and pose a significant and persistent risk to the ecosystem and human health. Surfactants can serve as detergents, wetting and foaming compounds, emulsifiers, or dispersants, and have been used extensively to promote the solubilization of POPs and their subsequent removal from environmental matrices, including solid wastes, soil, and sediments. However, improper use of surfactants for remediation of POPs may lead to unintended consequences that include toxicity of surfactants to soil microorganisms and plants, and leaching of POPs, thereby resulting in groundwater contamination.