key: cord-0922130-rrm4vxxe authors: Pacheco, Claudia Andrea Revilla; Hilares, Ruly Teran; de Jesús Colina Andrade, Gilberto; Mogrovejo-Valdivia, Alejandra; Tanaka, David Alfredo Pacheco title: EMERGING CONTAMINANTS, SARS-COV-2 AND WASTEWATER TREATMENT PLANTS, NEW CHALLENGES TO CONFRONT: A SHORT REVIEW date: 2021-06-07 journal: Bioresour Technol Rep DOI: 10.1016/j.biteb.2021.100731 sha: 32654cb1af23797d22912836114dfa81b8408568 doc_id: 922130 cord_uid: rrm4vxxe The current pandemic caused by SARS-CoV-2 has put public health at risk, being wastewater-based epidemiology (WBE) a potential tool in the detection, prevention, and treatment of present and possible future outbreaks, since this virus enters wastewater through various sources such as feces, vomit, and sputum. Thus, advanced technologies such as advanced oxidation processes (AOP), membrane technology (MT) are identified through a systematic literature review as an alternative option for the destruction and removal of emerging contaminants (drugs and personal care products) released mainly by infected patients. The objectives of this review are to know the implications that the new COVID-19 outbreak is generating and will generate in water compartments, as well as the new challenges faced by wastewater treatment plants due to the change in a load of contaminants and the solutions proposed based on the aforementioned technologies to be applied to preserve public health and the environment. Until now, seven types of coronaviruses that infect humans are known and some of them are present in the common cold. The coronavirus named SARS-CoV produces severe acute respiratory syndrome (SARS), in which incubation time is 3 to 7 days. Symptoms of infection include fever, cough, shortness of breath, potential pneumonia, acute respiratory syndrome, kidney damage, and even death. Simple measures have been recommended by the WHO to prevent its proliferation: social distancing, selfisolation, respiratory hygiene, and the quite common hand hygiene. The population that is most vulnerable to this virus is usually those over 65 years old and with concomitant diseases, so greater caution and care must be taken with them. Its structure consists of 4 types of variable proteins: envelope protein (E), nucleocapsid protein (N), spike protein (S), and membrane protein (M) (Chaudhry and Sachdeva, 2020; Daverey and Dutta, 2021; Lesimple et al., 2020; Wathore et al., 2020) . Coronaviruses have the characteristic of being enveloped viruses, with one of the longest RNA genomes, which gives great plasticity to accommodate, modify and acquire genes to adapt to various species (Jones et al., 2020) . The factor that is relevant for receptor recognition and allows the entry into the host cell is the S-glycoprotein, allowing then cross-species transmission. Its physiopathology is still being studied, but it is known that these viruses are usually very contagious when the patient is symptomatic also including the incubation period (days 1-14) when the person is usually asymptomatic. The most common pathways of transmission are aerosol; when the person talks, exhales, coughs, or sneezes, and fomites (objects that carry the pathogens); when the droplets are heavy and cant remain in the air, following then on floors or surfaces (Achak et al., 2021; El-Baz et al., 2020; Nghiem et al., 2020) . These J o u r n a l P r e -p r o o f viruses can enter into sewage through various sources such as sputum, vomit, faeces, even the already mentioned handwashing (Amoah et al., 2020; Nghiem et al., 2020) , and they tend to be more resistant than bacteria to free chlorine according to the World Health Organization (WHO) (La . However, the scientific community is using this type of wastewater entry as an opportunity to conduct epidemiological studies, since monitoring and study of this magnitude could show much more representative results of patients that are not being detected due to the absence or scarcity of symptoms, and thus use it as a warning system of future new COVID-19 outbreaks (Chaudhry and Sachdeva, 2020; Mallapaty, 2020) . Viruses can survive in wastewater because they attach to solid surfaces such as sludge, which acts as an indicator of biosolids concentration in sewage; these biosolids are classified according to the US-EPA in 2 classes: Class A (used for gardening) and Class B (used in agriculture and forestry) (Mohan et al., 2021) . Therefore, sludges also represent an epidemiological advantage/opportunity for wastewater-based epidemiology (WBE) since the viral sample is usually even more concentrated in comparison to wastewater (Langone et al., 2021; Sharma et al., 2020) . Finally, in recent months people are much more aware of hygiene, also isolation and quarantine centers have been constructed by the government of the majority of countries, so the use of water has increased significantly reaching very high peaks contribute to the emission of emerging contaminants (such as pharmaceuticals and their transformation products), through feces or urine of their patients, but also through direct disposal of expired drugs, detergents, and antiseptics that are part of this category. These contaminants could be detected in trace concentrations of ug/L to ng/L, so, inadequate treatment and transport of these compounds either in wastewater or solids, could generate a risk to public health and the environment due to its potential charge of toxic chemicals, pathogenic microorganisms, and radioactive elements (Achak et al., 2021; Khan et al., 2021; Kumari and Kumar, 2021) . Drugs can reach the groundwater and threaten the quality of drinking water, additionally; they could reach and accumulate in the food chain through the sludge used for agriculture purposes. Antibiotics are a special group of drugs that should be targeted because in combination with high microbial biomass, could cause potential damage and also become a reservoir of antimicrobial-resistant bacteria. As a result, patients who were infected by accidental ingestion of contaminated food and/or contaminated water may host multidrug-resistant bacteria (Khan et al., 2021; Kumari and Kumar, 2021) . The WHO recommends regular hand washing in conjunction with the use of hand sanitizers that have alcohol by principal component as prophylaxis ," 2020). These soaps will inactivate and encapsulate the viral molecules inside the formed micelles that will then be carried away by the action of water by dissolving the lipid bilayer of SARS-CoV-2 (Usman et al., 2020) . Keeping in mind the abovementioned, it is logical to think that the increasing use of antibacterial soaps and chemical biocides in these last months could threaten the ecosystem (Usman et al., 2020) . Many soaps and detergents present as part of their composition linear alkylbenzene sulfonates (LAS) used as surfactants, hand sanitizers by its part have J o u r n a l P r e -p r o o f Journal Pre-proof ethanol, iso-propyl alcohol, glycerol, and hydrogen peroxide, which once they enter to the sewage might damage the soil and be toxic to aquatic animals. Apart from the mentioned components; chlorhexidine, triclosan, and some quaternary ammonium compounds employed can be persistent in the environment increases the risk of multiantibiotic resistance caused by genetic mutations (Daverey and Dutta, 2021) . Personal protective equipment (PPE), equipment, and reagents used for the COVID-19 test are also an important topic in emerging contaminants because of the increasing use of masks and its inadequate disposal of, which leads to microplastics that could threaten ecosystems and marine wildlife (Ji et al., 2021; Michael-Kordatou et al., 2020) . Because of the outbreak of SARS-CoV-2, several medicines are being repurposed (repositioned drugs); for example, ribavirin, lopinavir, ritonavir, chloroquine, and rapamycin, and have been used as part of the treatment or as selfmedication (especially in places where the healthcare systems are not adequate) constituting one of the most common emerging contaminants in aquatic systems (Kumari and Kumar, 2021; Usman et al., 2020) causing serious damage to aquatic compartments and biota ( Table 1) . This is the case of antiviral compounds, anticancer drugs, antihypertensive drugs, immunosuppressants, antipsychotics and antihistamines, antifungal agents, antibacterial agents, and therapeutic antibodies (Batalha et al., 2021) . Here it should be noted that, antiviral and antibiotics drugs have to be specially mentioned since their use in the past years has been increased and with that, the antiviral and antibiotic resistance as already mentioned (Cela-Dablanca et al., 2021 ). An article that reports the ecotoxicological effects of some of the repositioned drugs (drugs that are used to treat similar viruses) used for COVID-19 has been recently published; the important points considered were: a) surface water, which is often used for drinking J o u r n a l P r e -p r o o f Journal Pre-proof purposes might be contaminated with some antiviral drugs that are difficult to remove such as oseltamivir, b) ivermectin is expected to produce a high risk due to its indiscriminate use triggered by some "fake news", c) "one health" and " sustainability" are some terms that require to be considered in Public Health.. (Kumari and Kumar, 2021; Tarazona et al., 2021) Hydroxychloroquine and chloroquine have also been widely used despite their unproven effect against COVID-19, increasing as a consequence of their presence in wastewater. On the other hand, chlorine-based disinfectants can be transformed into highly toxic products leading to bladder cancer and reproductive problems due to their residual chlorine and/or monochloramine (Ji et al., 2021) . In wastewater treatment plants, it is important to know the viability of the virus in: a) wastewater from effluents that can be re-used, b) sludge from biosolids, c) other by-products and d) formation of aerosols by aeration, or forced pumping (Foladori et al., 2020; Ji et al., 2021) . Because of this, the Center for Disease Control and Prevention (CDC) of the United States acclaims that workers in treatment plants must have protocols to prevent possible occupational transmission due to the aforementioned causes (Amirian, 2020) . The WHO indicates the management that should be taken with waste, water, sanitation, and hygiene by a standardized treatment process that should be applied to reduce the potential risks that this virus could cause due to its presence in excreta and wastewater (WHO, 2020) . Frequently the quality and efficacy of a disinfection process in water are judged considering only the level of turbidity or the specific action to one indicator bacteria (Adelodun et al., 2020; Kataki et al., 2021) , however, it is also relevant to contemplate the wide microbial and viral load that it brings. A publication made by Corpuz et al.(2020) , shows that some wastewater Table 2 , however, retention time, the quantity of organic matter and light exposure, as well as the aerobics organisms that might be present in the environment should be also considered (Achak et al., 2021; Kataki et al., 2021) . Low-income countries usually have a deficiency in the regulation, normative, and treatment of emerging contaminants, so are the ones that could suffer the most serious consequences of releasing these contaminants into their aquatic environment, depending on their toxicity, chemical composition, and possible bioaccumulation in the food chain. (Bandala et al., 2021; Khan et al., 2021; Michael-Kordatou et al., 2020) . As the vaccines cannot be afforded by all of the countries, at least not immediately, many of them are going to continue their use generating and contributing in that way to the over-use, accumulation, and increase of pharmaceutical drugs and their load in water bodies, plants and aquatic organisms (Kumari and Kumar, 2021) . As aforementioned, emerging contaminants in wastewater threaten human health and aquatic environments due to their persistence, mobility, and activity in the environment. Especially in the current context in which we find ourselves where the quantity of medicines is being considerably incremented in the effort to control COVID-19 symptoms such as dyspnea or fever. These drugs are usually metabolized in small portions, being the rest released by the patient organism into sewage by urine and feces (Bandala et al., 2021) . ). Linear alkylbenzene sulfonates (LAS) and anionic surfactants present in soaps and detergents are degradable in their majority just aerobically, but the non-ionic surfactants have low degradation in aerobic treatment. Despite this, there is not much information about the increment of drugs, hygiene J o u r n a l P r e -p r o o f products and so the presence of emerging contaminants in water, leaving a gap for the wastewater treatment plants that might not have taken conscience yet of the change of load that the current sewage brings (Bandala et al., 2021; Daverey and Dutta, 2021 these sensors are reported to be easy to prepare from using cheap materials (Bandala et al., 2021) . Wastewater treatment can be performed by several methods including the use of chemical disinfectants (chlorine-based disinfectants, peroxyacetic acid, hydrogen peroxide, povidone-iodine), advanced oxidation processes, ultraviolet irradiation, coagulation-filtration, and membranes ( Table 3) which are used in the three disinfection steps, that include a combination of physical, chemical and biological processes, to avoid the spread of different pathogens (Achak et al., 2021; Ji et al., 2021) . These steps are a) primary grade: to separate organic and inorganic solids; not effective at all for SARS-CoV-2 because of its size, b) secondary grade: removes solids that are dissolved, dispersed, or suspended c) tertiary grade: improves the water quality featuring advanced oxidation processes (AOPs), filtrations and chlorination and with the combination of disinfection in an increased dosage could enhance the inactivation of COVID-19 in wastewater. (Almeida et al., 2020; Ji et al., 2021; Nghiem et al., 2020; Patel et al., 2020; Venugopal et al., 2020) ;. Journal Pre-proof The most common chlorine treatments need a contact time and a dose demand to achieve the efficacy of the disinfection since many times its action is neutralized by organic matter. ClO 2 seems to be really helpful in the deactivation of this virus by passing through the capsomere and reacting the with RNA inside the virus, nonetheless; hypochlorite (ClO -) has demonstrated to have a better action against SARS-CoV (Kataki et al., 2021; Mohan et al., 2021; Sharma et al., 2020) . Even though chlorine-based disinfectants are widely mentioned in wastewater disinfection strategies, they generate about 600 types of by-products that are highly toxic (Table 3 Table 4 ). The wastewater treatment industry faces the constant challenges of foaming, inhibition of the biodegradation of organic compounds, interruption in oxygen diffusion, and denitrification process due to the presence of chemical detergents, soaps. That is why the aforementioned technologies need to be optimized and new J o u r n a l P r e -p r o o f technologies are being developed in the effort to find an effective alternative to treat wastewater such as supercritical water oxidation and constructed wetlands (Achak et al., 2021; Daverey and Dutta, 2021) . To show the relevance of a correct wastewater treatment process and some issues, is the case of Wuchang stadium, in Wuhan which was designated as a temporary hospital for COVID-19 patients, where certain actions were applied as a method of disinfection for the sewage systems to reduce the viral load of SARS-CoV-2 (Venugopal et al., 2020 ). An absence of SARS-CoV-2 RNA was found when 800 mg/L of sodium hypochlorite, with free chlorine > 6.5 mg/L was used satisfying the protocols developed in China by the CDC. Despite this, after 12 hours there was a presence of SARS-CoV-2 RNA in effluent when free chlorine was undetectable, which can be explained by the presence of feces that are very rich in organic matter which changes the composition of wastewater as well as interfering with the chemical components that should deactivate the virus, such as ClO 2 (Daughton, 2020; Venugopal et al., 2020) . SARS-CoV-2 was identified in wastewater at the beginning of the outbreak, suggesting that it can be used for surveillance and population monitoring (Wastewater-Based Epidemiology (WBE)), as this is an entry to human habits and health through feces, sputum, or nasal secretion that are discharged into sewage, detecting the virus in individuals who have not yet been identified as positive either because they are likely to be asymptomatic, pre-symptomatic, or have mild symptoms providing an advantage over individual testing (Kataki et al., 2021; Michael-Kordatou et al., 2020; Mohan et al., 2021) . This WBE can be applied at a municipal level, especially in those communities where access to molecular and serological testing is quite scarce and restricted, but can also be very useful in the detection of some variations that may occur in viral strains, to make many copies of DNA, however, it requires complex equipment, requires at least 4−6 hours to complete and it is expensive. Therefore, Pointof-care testing (POCT) is advantageous (Song et al., 2021) . Loop-mediated isothermal amplification (LAMP) is similar to RT-PCR but the difference is that the process is carried out at one temperature (60 to 65 °C) making the detection quicker, easy to use, and do not require expensive reagents or instruments (Thompson and Lei, 2020) . Biosensors can also be especially useful in the detection of the virus in aquatic compartments since they are analytical devices with biological elements that generate physicochemical signals, and according to recent studies, they have great advantages such as the use of small sample quantities, cost-effectiveness, and prompt response, The detection of COVID-19 on time, could decrease the transmission of the disease providing accurate information that would help considerably the eradication (Mao et al., 2020; Song et al., 2021) . More information can be found in the article "Point-of-care testing detection methods for COVID-19" (Song et al., 2021) However, there are some limitations in the detection: a) the complexity of the wastewater load (location of specific sites and the very nature of the diluted biomarker), making difficult to establish accurate quantitative predictions of infected patient cases (Mohan et al., 2021; Zhu et al., 2021) , which could be solved by sampling campaigns that would first identify infected areas and then identify infected individuals in hotspots (Langone et al., 2021) Low-income populations are one of the most affected by this new outbreak because some of them have little or no access to safe and properly treated water. No studies are being conducted on the level of contamination of rivers and lakes as possible risks to public health, thereby attempting to those populations that need more attention. It is also important to quote a phrase mentioned in an article published by Neal, 2020: "Countries will be emerging from the impacts of COVID-19 at different times and via different pathways, creating an opportunity for countries that are able to assist and support other countries in human and humane ways. Because water provides an entry point into every aspect of human life and every sector of our globalized and interconnected world, we should take this opportunity to fully embrace a human rights approach in our immediate, medium-term and long-term water-related responses to COVID-19." There is a need for alternatives for the use of wastewater treatment technologies that are cost-effective and that do not have the risk of generating long-term repercussions, such as chlorine-based disinfectants which are highly toxic, and the J o u r n a l P r e -p r o o f scientific community is very concerned about the environmental damage that this will cause in the long term. The limited knowledge of SARS-CoV-2 behavior in wastewater difficult for the proper treatment in wastewater, leaving a gap that should be taken and studied to improve the technologies proposed to eliminate the presence of the virus in aquatic compartments. COVID-19 has forced the population to be more aware of their hygiene, as well as disinfection in fomites and all kind of superficies where the virus could be attached, so repercussions will be reflected in Wastewater Treatment Chemicals and Global Water according to a report made in the UK (Kataki et al., 2021) . Natural compounds such as microbial and plant-derived surface-active agents, natural humectant-viscosity enhancers, essential oils, and phenolic compounds are innovative and eco-friendly solutions to decrease the charge of the emerging contaminants caused by hygiene products. Nonetheless, economic aspects need to be evaluated and solved through new technologies that increase productivity and reduce the cost by bioprocess optimization, separation processes, or any other innovative technique (Daverey and Dutta, 2021) . Regions with a lack of regulations and poor infrastructure to treat wastewater need help to solve their problem, some treatment alternatives are advanced oxidation processes and membrane technology, which are characterized by their environmental compatibility, versatility, high efficiency, and safety. Wastewater-based epidemiology (WBE) can be applied at a municipal level for virus detection, especially in communities where access to molecular and serological testing is quite scarce and restricted. The pathogens and organic pollutants can be inactivated and removed in wastewater thougth promising technologies as AOPs and J o u r n a l P r e -p r o o f membranes, respectively. The WHO recomend short-term solutions as UV radiation and solar irradiation tend to cause less damage to the environment. Finally, new cheap (POCT) techniques of detection and quantification in water should be developed and implemented to have information on the human health risk assessment of SARS-CoV-2. All the Authors declare no conflict interests. (Amoah et al., 2020; Carraturo et al., 2020; Collivignarelli et al., 2020; Kataki et al., 2021) Factor Description Viral structure The characteristic of coronaviruses of being enveloped viruses, makes them prone to have shorter survival periods due to the action of proteolytic enzymes and detergents in the external lipid layer of the virus. Characteristics/ composition of wastewater The inactivation of the virus is influenced by the presence of chemicals with antiviral activity, proteolytic enzymes present in the bacteria, also the high molecular weight present in the matter dissolved in the wastewater and the inhibition of the matrix of the native flora. The temperature increase causes a protein and nucleic acid denaturation, as well as an increase in the activity of the extracellular enzymes. pH An acidic pH generates an RNA denaturation, by the protonation of guanine-cytosine base pairs and the formation of Hoogsteen base pairs. J o u r n a l P r e -p r o o f (Lesimple et al., 2020; Mohan et al., 2021; Patel et al., 2020) . Chlorine treatment It acts as a selective oxidant, reacting in this way with the capsid protein and damaging the Cys, Trp and Tyr, causing the inhibition of replication and injection of the genome as well as UV treatment. Sedimentation, temperature increase, degradation by sunlight is part of the treatment mechanism of these systems. UV inactivation 200 to 300 nm is the active UV wavelength range that can damage the bacteria or virus, nonetheless; ~254 nm is recognized as the best one for microbial disinfection. Its efficiency depends of the contact time, temperature and the presence of organic matter. Usually inactivates the virus by damaging the RNA, so on the replication through oxidation processes, altering the permeability and damaging the capsid proteins. They include the use of photocatalysts and membranes which incorporate nanomaterials. Metal oxide semiconductors utilized are for example TiO 2 and ZnO. A certain amount of contact time is needed to achieve the disinfection. Usually used as part of pre-treatment systems, in order to remove particles and post-treatment in order to complete the removal of emerging contaminants that may remain after a water treatment process. The pore sizes present in these membranes are much smaller than the viruses that are present as common contaminants in water. Usually used as a pre-treatment before reverse osmosis, however; it has also been used by several authors in the removal of bacteria and viruses. They are mostly used for the removal of protozoa and bacteria. They have been used for filtration in combination with ozonation and coagulation as a pre-treatment for virus removal. J o u r n a l P r e -p r o o f Two boron-doped diamond diodes (BDD) are used as part of the oxidation that will degrade the drugs into CO 2 and intermediates that are usually no longer stable compounds due to a big production of OH* radicals form the electrochemical oxidation of water at the surface of these two BDD. Chloroquine Electro-Fenton oxidation BDD anodes are used with the addition of FeSO 4 in the solution in order to generate a greater number of free radicals in the AOP and thus improving the cost-effectiveness, even though, the pH has to be controlled. Virus Photocatalyst The photocatalyst Ag 3 PO 4 /g-C 3 N 4 synergizes the effects of Ag 3 PO 4 with those of g-C 3 N 4 achieving and improving the efficiency of the absorption of visible light; consequently, a greater destruction of the viruses by means of the ROS. (Cheng et al., 2018) Ozone The is a powerful oxidant which, by generating ROS, could attack the virus in different places of its structure, especially the S-glycoprotein, inhibiting the infection process. (Tizaoui, 2020) Flat-sheet polyvinylidene fluoride (PVDF) and filters based on PVDF coated with multiwalled carbon nanotubes layer (MWCNTs) A flat-sheet of PVDF is employed, showing a bacteriophage photocatalysis inactivation where the membrane acted as a fence. MWCNTs functionalized with different silver-based filters demonstrated to remove effectively viral bacteriophages but with a virus retention limitation after the filtration. (Mohan et al., 2021) Cold plasma (CP) The plasma acts facilitating the production of UV radiation with reactive oxygen and/or nitrogen species (RONS) that are also the limiting factor and acts damaging the nucleic acids, oxidizing nucleic acids, proteins and lipids. (Mohan et al., 2021) SARS-CoV-2 in hospital wastewater during outbreak of COVID-19: A review on detection, survival and disinfection technologies Snowballing transmission of COVID-19 (SARS-CoV-2) through wastewater: Any sustainable preventive measures to curtail the scourge in low-income countries? 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