Emerging Contaminants Research Articles

ZrO2@chitosan composite for simultaneous photodegradation of three emerging contaminants and antibacterial application

Emerging contaminants (ECs) are often detected in water bodies due to their prevalent use combined with inefficiency of the conventional wastewater treatment plants for their complete removal. Elimination of ECs using photocatalysis as a tertiary treatment can be a sustainable option for the reuse wastewater. Reported herewith is a photocatalyst, chitosan-based zirconia hybrid composite (ZrO2CTS-HC) for the individual/ simultaneous degradation of multiple ECs like Congo red (CR), Methyl orange (MO) and 4-hydroxybenzoic acid (4-HA) under visible light irradiation. Successfully synthesized ZrO2CTS-HC as confirmed by theoretical and various characterization techniques depicted photodegradation efficiency of 91.11, 69.11 and 78.40% for CR, MO and 4-HA respectively (SD 0.5–0.95; HPLC) aided by the reactive hydroxyl radical. Probable degradation mechanism supported by LC-MS/MS, COD and TOC along with reusability and antibacterial ability towards E.Coli & S.aureus is also reported. ZrO2CTS-HC can be a good option for elimination of residual ECs during tertiary treatment.

Effects of interactions between quorum sensing and quorum quenching on microbial aggregation characteristics in wastewater treatment: A review.

Due to the increasingly urgent demand for effective wastewater denitrification and dephosphorization systems, there is a need to improve the performance of existing biological treatment technologies. As a bacteria-level communication mechanism, quorum sensing (QS) synchronizes gene expression in a density-dependent manner and regulates bacterial physiological behavior. On this basis, the QS-based bacterial communication mechanism and environmental factors affecting QS are discussed. This paper reviews the influence of QS on sludge granulation, biofilm formation, emerging contaminants (ECs) removal, and horizontal gene transfer in sewage treatment system. Furthermore, the QS inhibition strategies are compared. Based on the coexistence and balance of QQ and QS in the long-term operation system, QQ, as an effective tool to regulate the growth density of microorganisms, provides a promising exogenous regulation strategy for residual sludge reduction and biofilm pollution control. This paper reviews the potential of improving wastewater treatment efficiency based on QS theory and points out the feasibility and prospect of exogenous regulation strategy. PRACTITIONER POINTS: The mechanism of bacterial communication based on QS and the environmental factors affecting QS were discussed. The application of QS and QQ in improving the sludge performance of biological treatment systems was described. The significance of QS and QQ coexistence in sewage treatment process was described.

Bicarbonate-enhanced iron-based Prussian blue analogs catalyze the Fenton-like degradation of p-nitrophenol

P-nitrophenol (PNP), a widely used compound, is harmful to the environment and human health. In this study, four iron-based Prussian blue analogs (PBAs) were prepared by coprecipitation (Co-Fe PBA, Mn-Fe PBA, Cu-Fe PBA and Fe-Fe PBA). The Co-Fe PBA exhibited high peroxymonosulfate (PMS) activation performance for PNP degradation, removing over 90% of PNP in 60 min at an optimal pH of 7, temperature at 30 ℃, initial concentration of 20 mg/L, PBA dose of 0.2 g/L and PMS dose of 1 g/L. The physicochemical properties of the Co-Fe PBA were investigated by various characterization methods. The catalytic activity of PBA and the influence of various process parameters and water quality on the catalytic reaction were investigated to elucidate the mechanism of p-nitrophenol degradation by PBA-activated persulfate. Moreover, the mechanism of accelerated degradation of PNP under HCO3– conditions and the role of major reactive oxides were determined by EPR measurement methods and free radical trapping experiments. HCO3– was found to directly activate PMS to produce reactive oxygen species, and 1O2, ∙OH and SO4∙- were all greatly increased. This work presents a promising green heterogeneous catalyst for the degradation of emerging contaminants (ECs) in real wastewater with natural organic matter and coexisting anions by PMS activation.

Trends in microbial degradation and bioremediation of emerging contaminants

Abstract Modernization and modern ways of living demands more improved products from pharmaceuticals, cosmetics, and food processing industries. Moreover, industries like pesticides, fertilizers, dyeing, paints, detergent etc., also needs improvised products as per demand. As the new product emerges, the pollutants from these industries also constitute new type of danger to the environment and serious health risks to the living organisms. These emerging contaminants (ECs) are from different category of sources such as personal care products (PCPs), pharmaceuticals (Phcs), endocrine disrupting chemicals (EDCs), etc. These ECs can easily escape from the conventional water treatment and eventually get discharged in to the surface water and thus enters in to the ground water, soil, sediments, and also into the oceans. When these contaminants emerge we also require progress in tremendous process for preventing these hazardous chemicals by effective removal and treatment. For the past 50 years, both developed and developing countries are working on this treatment process and found that Microbial degradation and bioremediation are very useful for effective treatment to prevent their emissions. This treatment can be designed for any sort of ECs since the microbial members are so versatile to redesign their metabolic pathways when subject to exposure. However, implementing bioremediation is not alone efficient to degrade ECs and hence, combination of bioremediation, nanotechnology and physical treatment method will also provide sustainable, potent and fast degradation process. In this Book Chapter, we discuss in detail about the ECs, sources of microbial degradation process and its usefulness in the bioremediation of these ECs.

Accumulation of chemical elements and occurrence of microplastics in small pelagic fish from a neritic environment

The assessment of contaminant exposure in marine organisms often focuses on the most toxic chemical elements from upper trophic level species. Information on mid-trophic level species and particularly on potentially less harmful elements is lacking. Additionally, microplastics have been considered emergent contaminants in aquatic environments which have not been extensively studied in species from mid-trophic levels in food chains. This study aims to contribute to an overall assessment of environmental impacts of such chemicals in a community of small pelagic fish in the North Atlantic. The concentrations of 16 chemical elements, rarely simultaneously quantified (including minerals, trace elements and heavy metals), and the presence of microplastics were analysed in sardines (Sardina pilchardus) and mackerels (Scomber spp. and Trachurus trachurus) sampled along the Portuguese coast. Biochemical stress assessments and stable isotope analyses were also performed. The chemical element concentrations in S. pilchardus, T. trachurus, and Scomber spp. were relatively low and lower than the levels reported for the same species in the North Atlantic and adjacent areas. No clear relationships were found between chemical elements and oxidative damage in fish. However, the concentration of several chemical elements showed differences among species, being related with the species’ habitat use, trophic niches, and specific feeding strategies. The presence of plastic pieces in the stomachs of 29% of the sampled fishes is particularly concerning, as these small pelagic fish from mid-trophic levels compose a significant part of the diet of humans and other top predators. This study highlights the importance of multidisciplinary approaches focusing on the individual, including position data, stable isotopes, and oxidative stress biomarkers as complementary tools in contamination assessment of the marine mid-trophic levels in food chains.

Effect of benzotriazole on oxidative stress response and transcriptional gene expression in Oryzias latipes and Danio rerio embryo

Emerging contaminants (EC) such as benzotriazole are being released into the environment in various ways, therefore it is necessary to understand how organisms are affected by EC. In this study, we exposed medaka (Oryzias latipes) and zebrafish (Danio rerio) during their embryonic period (1 day after hatching) to benzotriazole to investigate its effects on oxidative stress (ROS, GSH, GST, SOD, CAT and MDA) and changes in gene expression patterns. In both medaka and zebrafish, the influence of oxidative stress was confirmed through an increased MDA level and changes in the ROS and GSH levels. Antioxidant enzymes such as GST, CAT, and SOD were affected by benzotriazole; however, medaka and zebrafish showed different patterns in the effects by benzotriazole. Results of oxidative stress genes expression showed that medaka had either no influence or had a decrease in the gene expression profile, whereas zebrafish had a statistically significant increase in the expression of some genes. The cyp1a gene expression was increased in both species. However, vtg gene expression was increased only in zebrafish but decreased in medaka, indicating no estrogenic effects in medaka. Apoptosis genes showed changes in expression in both the species but was these changes were not dose-dependent. However, zebrafish caspase-9 gene expression was increased in all of the exposed groups, suggesting the effects on the intrinsic pathway associated with caspase-9. In conclusion, the results indicate that the toxic effects of benzotriazole differ at various levels in the two small fish medaka and zebrafish embryos.

Pharmaceutical Products and Pesticides Toxicity Associated with Microplastics (Polyvinyl Chloride) in Artemia salina.

Pharmaceutical products, as well as insecticides and antimicrobials, have been extensively studied, but knowledge of their effects—especially those caused by their mixtures with microplastics—on aquatic organisms remains limited. However, it should be borne in mind that the state of knowledge on acute and chronic effects in aquatic organisms for pharmaceuticals and pesticides is not similar. In response, this investigation analyzed the presence of microplastics (polyvinyl chloride) and their impacts on the toxicity of chlorpyrifos (an insecticide) and triclosan (an antibacterial) when they coincide in the environment, alongside the two most consumed drugs of their type (hypolipemic and anticonvulsant, respectively), namely simvastatin and carbamazepine, in Artemia salina. LC50 and cholinesterase enzyme activity were calculated to determine the possible neurotoxicity associated with emergent contaminants in the treatments. The LC50 values obtained were 0.006 mg/dm3 for chlorpyrifos, 0.012 mg/dm3 for chlorpyrifos associated with microplastics, 4.979 mg/dm3 for triclosan, 4.957 mg/dm3 for triclosan associated with microplastics, 9.35 mg/dm3 for simvastatin, 10.29 mg/dm3 for simvastatin associated with microplastics, 43.25 mg/dm3 for carbamazepine and 46.50 mg/dm3 for carbamazepine associated with microplastics in acute exposure. These results indicate that the presence of microplastics in the medium reduces toxicity, considering the LC50 values. However, exposure to chlorpyrifos and carbamazepine, both alone and associated with microplastics, showed a decline in cholinesterase activity, confirming their neurotoxic effect. Nevertheless, no significant differences were observed with the biomarker cholinesterase between the toxicant and the toxicant with microplastics.

Occurrence, fate, and toxicity of emerging contaminants in a diverse ecosystem

Abstract Activities that were developed for better/modern living conditions of humans are the primary source of contaminants to the natural ecosystem. Some of the compounds involved in urbanization and industrialization are termed emerging contaminants (ECs) or contaminants of emerging concern. ECs are either chemical or derived from natural sources which environmental concerns and public health have been raised in recent years. ECs enter wastewater treatment systems and migrate from here to different ecosystems as direct or by-products. They are persistent and also stay for a long duration due to their less biodegradation and photodegradation nature. Also, ECs accumulated in living cells and transformed through trophic levels. Technological developments and their application/utility in daily life led to the production of various components that are being added to the natural ecosystem. The treated/untreated wastewater enters into fresh/marine water bodies and gets accumulated into fauna, flora, and sediments. These pollutants/contaminants that are getting added on an everyday basis bring about changes in the existing ecosystem balances. ECs have been found in almost every country’s natural environment, and as a result, they became a global issue. The present review discusses the route and transport of selected ECs into the terrestrial ecosystem through water and other means and how they influence the natural process in an ecosystem. The ECs such as personal care products, pharmaceuticals, polyaromatic hydrocarbons, endocrine disruptors, nanoparticles, and microplastics are highlighted in this review.

Techniques for the detection and quantification of emerging contaminants

Abstract In recent years, the diverse industrial practices and human inputs widely disseminated emerging contaminants (ECs) throughout environmental matrices, which is of great concern. Even at low concentrations, ECs pose major ecological problems and threaten human health and the environment’s biota. Consequently, people’s interest and concerns on the widespread dissemination of environmentally connected ECs of great concern as developed due to their scientific understanding, technical innovation, and socioeconomic awareness. Increased detection of contaminants may occur from climatic, socioeconomic, and demographic changes and the growing sensitivity of analytical techniques. Hence, this article reviews the determination of ECs in ecological specimens, from aquatic setup (river water, marine water, and wastewater), sludge, soil, sediment, and air. Sample collection and the quality measures are summarized. The preparation of samples, including extraction and cleanup and the subsequent instrumental analysis of ECs, are all covered. Traditional and recent extraction and cleanup applications to analyze ECs in samples are reviewed here in this paper. The detection and quantification of ECs using gas chromatography (GC) and liquid chromatography (LC) linked with various detectors, particularly mass spectrometry (MS), is also summarized and explored, as are other possible techniques. This study aims to give readers a more excellent knowledge of how new and improved approaches are being developed and serve as a resource for researchers looking for the best method for detecting ECs in their studies.

Comparison of POCIS and grab sampling techniques for monitoring PPCPs in vernal pools in central Pennsylvania

Active ingredients in pharmaceuticals and personal care products (PPCPs) can persist through wastewater treatment plants and be released into the environment where they can inadvertently pose risks to non-target organisms. Emerging contaminants (ECs), including PPCPs, are commonly detected in wastewater effluent. With the increasing beneficial re-use of treated wastewater globally, there is a need to understand how spray-irrigation activities affect the occurrence and persistence of ECs in the environment to which they are introduced. Here, we explore the impacts of wastewater spray-irrigation on nearby ephemeral wetlands (e.g., vernal pools) through the use of grab and Polar Organic Chemical Integrative Sampling (POCIS) techniques. This study sought to determine whether integrative sampling techniques are better suited than traditional grab sampling techniques in assessing the presence and concentrations of ECs in vernal pools by evaluating 34 ECs in six vernal pools in central Pennsylvania. Three pools were impacted by wastewater spray-irrigation activities and three were in a nearby forested area. Results of this study found that POCIS detected a wide range of 25 ECs (log Kow between −2.6 and 9.37) more or, in some cases, equally frequently, relative to grab samples. Additionally, grab samples were found to best capture short-lived elevated inputs of ECs (from irrigation events) while POCIS were found to best capture ECs that were present in vernal pools over a longer period of time (weeks to months). For ECs detected more frequently in grab samples, concentrations were higher compared to time weighted average aqueous concentrations estimated from POCIS. This study advances understanding of the potential impact of wastewater beneficial reuse on vernal pools and informs how best to monitor the presence of ECs in vernal pools using integrative and grab sampling techniques.

Occurrence, bioaccumulation and potential risk of polyhalogenated carbazoles in marine organisms from the East China Sea

As well-known emergent environmental contaminants, polyhalogenated carbazoles (PHCZs) have recently received increasing attention. In this study, we investigated the concentrations of carbazole (CZ) and PHCZs in 70 marine organisms from the East China Sea (ECS). CZ and 9–11 PHCZs were detected in organisms from the ECS, with concentrations in the range of 0.75–33 ng/g lipid weight, lw and 4.3–113 ng/g lw, respectively. Among the PHCZs, there were 3–4 major components in zooplankton, fish, shrimp, crabs, snails and shellfish, and the sum of these major components accounted for 59% to 67% of ∑PHCZs. The bioaccumulation potentials of 1,3,6,8-tetrachlorocarbazole (1368-CCZ) and 3-chlorocarbazole (3-CCZ) from water were observed. The logarithmic bioaccumulation factor (logBAF) values of the CZ and PHCZs increased significantly with increasing logKOW values (R = 0.449–0.784, p < 0.01). The trophic magnification factor (TMF) values of the CZ, 9 PHCZs and ∑PHCZs were calculated to be 3.32, 1.87–4.06 and 2.36, respectively, indicating the potential biomagnification of the CZ and PHCZs in the zooplankton-shrimp-fish food web. The toxic equivalents (TEQs) of PHCZs in organisms from the ECS were in the range of 0.78–36 pg TEQ/g lw. Overall, for the first time, this study systematically examined the occurrence, bioaccumulation and potential risk of PHCZs in the marine food web of the East China Sea.

Modular stand-alone photoelectrocatalytic reactor for emergent contaminant degradation via solar radiation

The development of new materials and prototypes with a sustainable approach to allow an efficient removal from water sources of emergent contaminants, such as drugs and antibiotics, currently represents the next challenging task in the water decontamination field. A modular photoelectrocatalytic reactor composed by single-element devices is here presented. Each single device is a stand-alone system based on a photoelectrochemical cell, which is composed by a WO3 photoanode integrated in a tandem cell configuration with photovoltaic solar cells. Outstanding abatement results of different emerging contaminants (Atenolol, Carbamazepine, and Levofloxacin) in aqueous solution were obtained through photoelectrochemical degradation tests using the single stand-alone device. In addition, 4-Hydroxybenzaldehyde was selected as representative of natural organic matter, usually present in a real matrix. Herein, it has been proved that the system performance was optimal also for complex mixtures.

Occurrence and distribution of emerging contaminants in mine-impacted lake water and potential use as co-tracers of anthropogenic activity in the subarctic region, Northwest Territories, Canada

The emerging contaminant (EC) perchlorate (ClO4−), a blasting agent widely used in mining and refining operations, has been used as a practical indicator of mining activities. Widespread occurrence of ECs, such as pharmaceutical compounds, artificial sweeteners, and perfluoroalkyl substances, and their use as co-tracers of wastewater associated with anthropogenic activities in the urban and Arctic environments have been previously investigated. However, limited studies have reported the occurrence of these ECs and the feasibility of their use as co-tracers of anthropogenic activities in pristine waterbodies (e.g., continuous permafrost region) that receive effluent from mine sites. In this study, water samples were collected from the surface of 10 lakes within the Coppermine and Lockhart Watersheds in the continuous permafrost region in the Northwest Territories, Canada during the open water seasons of 2016, 2017, and 2018. Concentrations of 16 ECs were determined to delineate the spatial and temporal distribution of these compounds in waterbodies receiving effluent from mine sites. Slightly elevated concentrations of ClO4− (100–700 ng L−1), caffeine (0.2–5.9 ng L−1), acesulfame-K (0.5–1.5 ng L−1), perfluorooctanoic acid (PFOA; 5–34 ng L−1), perfluorooctane sulfonic acid (PFOS; 11–40 ng L−1), chloride (1.5–2.3 mg L−1), and sulfate (1.0–3.6 mg L−1) were observed across the two investigated watersheds, especially downstream of the mining sites. The concurrence of elevated concentrations of these target ECs combined with other dissolved constituents (chloride and sulfate) may indicate the influence of mining activity on the receiving waterbodies and the potential use of these compounds as co-indicators of anthropogenic activity. Results from this study provide novel information on the distribution of 16 ECs in pristine waterbodies that receive effluents from mining sites in the Canadian subarctic in advance of more expansive human development and increased warming and melting of mine sites, including mine wastes.

Artificial Intelligence Meets Marine Ecotoxicology: Applying Deep Learning to Bio-Optical Data from Marine Diatoms Exposed to Legacy and Emerging Contaminants.

Simple SummaryOur work is motivated by the increasing production of chemicals with environmentally harmful effects to our aquatic ecosystems. We show that it is possible to detect and distinguish the presence of several different emerging contaminants, using the photochemical responses of a microalgae species, which is among the most abundant phytoplankton group in the oceans. We use several machine learning and deep learning models that operate on chlorophyll fluorescence induction curves, which are composed of fluorescence values taken at different time steps from the microalgae exposure trials, achieving up to 97.65% accuracy when predicting the type of contaminant, and up to 100% in several cases when predicting the exposure concentration. Our results show the combination of these models with the fluorescence induction curves creates a powerful tool for ecotoxicity assessment, capable of classifying model organisms for their contaminant exposure, both in terms of type and concentration, opening new doors for toxicophenomics developments.Over recent decades, the world has experienced the adverse consequences of uncontrolled development of multiple human activities. In recent years, the total production of chemicals has been composed of environmentally harmful compounds, the majority of which have significant environmental impacts. These emerging contaminants (ECs) include a wide range of man-made chemicals (such as pesticides, cosmetics, personal and household care products, pharmaceuticals), which are of worldwide use. Among these, several ECs raised concerns regarding their ecotoxicological effects and how to assess them efficiently. This is of particular interest if marine diatoms are considered as potential target species, due to their widespread distribution, being the most abundant phytoplankton group in the oceans, and also being responsible for key ecological roles. Bio-optical ecotoxicity methods appear as reliable, fast, and high-throughput screening (HTS) techniques, providing large datasets with biological relevance on the mode of action of these ECs in phototrophic organisms, such as diatoms. However, from the large datasets produced, only a small amount of data are normally extracted for physiological evaluation, leaving out a large amount of information on the ECs exposure. In the present paper, we use all the available information and evaluate the application of several machine learning and deep learning algorithms to predict the exposure of model organisms to different ECs under different doses, using a model marine diatom (Phaeodactylum tricornutum) as a test organism. The results show that 2D convolutional neural networks are the best method to predict the type of EC to which the cultures were exposed, achieving a median accuracy of 97.65%, while Rocket is the best at predicting which concentration the cultures were subjected to, achieving a median accuracy of 100%.

A review on recent trends in the removal of emerging contaminants from aquatic environment using low-cost adsorbents

Emerging contaminants (ECs), a class of contaminants with low concentrations but significant harm, have received a lot of attention in recent times. ECs comprises of various chemicals that enter the environment every day. In today's modern lifestyle, we use many chemical-based products. These persist in wastewater and ultimately enter the water bodies, causing serious problems to the human and aquatic ecosystem. This is because the conventional wastewater treatment methods are inefficient in identifying and removing such contaminants. Aiming for a long-term, effective solution to this issue, Adsorption was proposed. Although several adsorbents are already present in the market, which have proved beneficial in removing such ECs, not all are affordable. This article reviews replacing costly adsorbents with agriculture-based biomass that are abundant, inexpensive, and biodegradable and possess excellent adsorption capacity. The objectives of this article is to look at adsorption as a viable treatment option for emerging pollutants, as well as sophisticated and cost-effective emerging contaminants treatment options.

Evaluation of per- and poly-fluorinated alkyl substances (PFAS) in livers of bottlenose dolphins (Tursiops truncatus) found stranded along the northern Adriatic Sea.

Per-and poly-fluorinated alkyl substances (PFAS) are a group of chemicals used in a wide variety of commercial products and industrial applications. These chemicals are persistent, can accumulate in humans' and animals' tissues and in the environment, representing an increasing concern due to their moderate to highly toxicity. Their global distribution, persistence and toxicity led to an urgent need to investigate bioaccumulation also in marine species. In 2013 PFAS contamination was detected in a vast area in Veneto region, mainly in Adige and Brenta rivers. In order to investigate any relevant presence of these substances in marine vertebrates constantly living in the area, PFAS were measured in hepatic tissue samples of 20 bottlenose dolphins (Tursiops truncatus) stranded along the northern Adriatic Sea coastline between 2008 and 2020. Using high performance liquid chromatography-mass spectrometry, 17 target PFAS (PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA, PFTrDA, PFTeDA, PFBS, PFHxS, PFOS, PFDS, PFHpS, PFPeS), were quantified in the samples. PFAS profiles were generally composed of the same five dominant PFAS (PFOS > PFUnA > PFDA ≈ PFDoA ≈ PFTrDA). The greatest PFOS concentration found was 629,73 ng/g wet weight, and PFOS accounted until 71% in the PFAS profiles. No significant differences between sexes were found, while calves showing higher mean values than adults, possibly indicating an increasing ability in the elimination of PFAS with age. Finally, a temporal analysis was carried out considering three different periods of time, but no temporal differences in concentrations were found. The results suggest that long-chain PFAS are widespread in bottlenose dolphins along the North Adriatic Sea. Furthermore, they represent a baseline to investigate the impact of PFAS on marine mammals’ conservation and health. Filling an important gap in the knowledge of PFAS accumulation in bottlenose dolphins, this study highlights the relevant role of Environmental and Tissue Banks for retrospective analyses on emergent contaminants.

Role of bioelectrochemical systems for the remediation of emerging contaminants from wastewater: A review.

Bioelectrochemical systems (BESs) are a unique group of wastewater remediating technology that possesses the added advantage of valuable recovery with concomitant wastewater treatment. Moreover, due to the application of robust microbial biocatalysts in BESs, effective removal of emerging contaminants (ECs) can be accomplished in these BESs. Thus, this review emphasizes the recent demonstrations pertaining to the removal of complex organic pollutants of emerging concern present in wastewater through BES. Owing to the recalcitrant nature of these pollutants, they are not effectively removed through conventional wastewater treatment systems and thereby are discharged into the environment without proper treatment. Application of BES in terms of ECs removal and degradation mechanism along with valuables that can be recovered are discussed. Moreover, the factors affecting the performance of BES, like biocatalyst, substrate, salinity, and applied potential are also summarized. In addition, the present review also elucidates the occurrence and toxic nature of ECs as well as future recommendations pertaining to the commercialization of this BES technology for the removal of ECs from wastewater. Therefore, the present review intends to aid the researchers in developing more efficient BESs for the removal of ECs from wastewater.

An expected formation of TCNM from chlorination of bisphenol A with ultrasonic pretreatment: A new nitrogen source for N-DBP from N2 in air

Ultrasonic irradiation has been widely adopted to remove emerging contaminants (ECs) in water, while little attention has been given to the impact of ultrasonic pretreatment on the downstream formation of disinfection byproducts (DBPs). In this study, bisphenol A (BPA), a typical EC that is frequently detected in water, was selected as a model contaminant to investigate the influence of ultrasonic pretreatment on DBP formation during the chlorination process. The ultrasonic degradation behaviors of BPA fit the heterogeneous Langmuir-Hinshelwood (L-H) model well, indicating that BPA undergoes decomposition by free radical reactions predominantly at the water-bubble interface. Interestingly, compared to direct chlorination, the ultrasonic pretreatment obviously enhanced trichloronitromethane (TCNM) formation from subsequent chlorination. The LC/MS/MS technique was applied to analyze the transformation products of BPA. In addition to hydroxyl radicals (OH) dominating hydroxylation of the aromatic ring and cleavage of the CC bond, an ultrasonic-induced nitration mechanism was also involved in BPA degradation, and the formed nitration products may be responsible for TCNM formation during subsequent chlorination. Factors affecting the ultrasonic degradation rate of BPA as well as DBP formation were also investigated. Generally, dissolved O2, higher ultrasonic frequency and higher power favored BPA degradation, whereas the presence of HCO3− and HA hindered BPA degradation, and Cl− showed a minor influence. TCNM formation was largely diminished by sparging with O2 or N2 alone. Higher ultrasonic frequency and power enhanced the TCM and TCNM formation. The presence of HA promoted THM formation, while HCO3− inhibited TCNM formation. Therefore, once ultrasonic treatment is adopted as an alternative water treatment, its impact on subsequent DBP formation requires further study.

Removal of emerging contaminants (bisphenol A and antibiotics) from kitchen wastewater by alkali-modified biochar

Using current wastewater treatment technologies, it can be challenging to remove the emerging contaminants (ECs) present in kitchen wastewater (KW) of complex compositions and high organic content. In this study, biochar, derived from straw, was modified as an adsorbent to remove ECs such as bisphenol A (BPA), tetracycline (TC) and ofloxacin (OFL) from a complex KW system. An alkali-modified biochar, having larger specific surface areas and stronger hydrophobicity, was found to exhibit a higher adsorption capacity, with more than 95% of the target ECs being removed. Indeed, in a static operation mode, the alkali-modified biochar had maximum adsorption capacities of 71.43, 101.01 and 54.05 mg/g for BPA, TC, and OFL, respectively. The adsorption kinetics and isotherms models indicated that the adsorption process was controlled by chemisorption, as well as the monolayer adsorption of contaminants onto the external and internal surfaces of the alkali-modified biochar. The adsorption of TC and OFL was significantly affected by the initial pH values of KW. However, the presence of different environmental factors (COD, NH4+ and PO43−) had little effects on the adsorption of the contaminants. The alkali-modified biochar was further tested in a fixed-bed column where the maximum dynamic adsorption capacities for BPA and OFL were 55 and 45 mg/g, representing about 75% and 83% of the static saturated adsorption capacities. These findings can be of major significance for the application of alkali-modified biochar in the removal of ECs from complex KW systems.

Degradation of high concentrations of azithromycin when present in a high organic content wastewater by using a continuously fed laboratory-scale UASB bioreactor

As the presence of emergent contaminants in wastewater, such as antibiotics, has become a threat for public health, the evaluation of strategies to treat them has been gaining importance. A critical example of this situation can be found in wastewaters coming from the pharmaceutical industry, where high concentrations of antibiotics are sometimes accompanied by high organic contents. Even the agroindustry can be affected by a similar problem when cattle infections are treated with antibiotics and part of the antibiotic-contaminated milk has to be wasted. With these situations in mind, in the present study we evaluated a progressive acclimation strategy for a granular sludge in a UASB reactor treating a high organic-content synthetic wastewater contaminated with azithromycin. In parallel, we tested a previously reported low-cost method for azithromycin determination by spectrophotometry, obtaining results comparable with liquid chromatography coupled to mass spectrometry. Although azithromycin has been reported as recalcitrant and resistant to biological degradation, the antibiotic was removed with efficiencies over 50% for wastewater with 10 mg L−1 of azithromycin and a COD of more than 4000 mgO2 L−1. Furthermore, efficiencies over 40% were achieved for wastewater with higher azithromycin concentrations (80 mg L−1) and a COD of 20,000 mgO2 L−1. A careful acclimation strategy permitted the partial removal of azithromycin from wastewater when treating concentrations comparable and higher than what would be expected for domestic and hospital wastewaters, even when its chemical oxygen demand is considerably higher than the average maximum of around 1000 mgO2 L−1.