Aquatic photolysis of high-risk chemicals of emerging concern from secondary effluent mediated by sunlight irradiation for ecological safety and the enhanced methods.

Natural sunlight can reduce the chemicals of emerging concern (CECs) and biological effects from the discharged domestic wastewater. But the aquatic photolysis and biotoxic variations of specific CECs detected in secondary effluent (SE) were not clear. In this study, 29 CECs were detected in the SE, and 13 medium- and high-risk CECs were identified as target chemicals based on their ecological risk assessment. To comprehensively explore the photolysis properties of the identified target chemicals, the direct and self-sensitized photodegradation of the target chemicals, even the indirect photodegradation in the mixture, were investigated and compared with these photodegradation in the SE. Of the 13 target chemicals, only five chemicals (including dichlorvos (DDVP), mefenamic acid (MEF), diphenhydramine hydrochloride (DPH), chlorpyrifos (CPF), and imidacloprid (IMI)) underwent direct and self-sensitized photodegradation processes. The removal of DDVP, MEF, and DPH was attributed to self-sensitized photodegradation, which was mainly mediated by •OH; CPF and IMI primarily relied on direct photodegradation. Synergistic and/or antagonistic actions that occurred in the mixture improved/decreased the rate constants of five photodegradable target chemicals. Meanwhile, the biotoxicities (acute toxicity and genotoxicity) of the target chemicals (including individual chemicals and the mixture) were significantly reduced, which can explain the reduction of biotoxicities from SE. For the two refractory high-risk chemicals, atrazine (ATZ) and carbendazim (MBC), algae-derived intracellular dissolved organic matter (IOM) on ATZ, and IOM and extracellular dissolved organic matter (EOM) on MBC had slightly promotion for their photodegradation; while peroxysulfate, and peroxymonosulfate served as sensitizers were activated by natural sunlight and effectively improved their photodegradation rate, and then reduced their biotoxicities. These findings will promote the development of CECs treatment technologies based on sunlight irradiation.

The impact of inorganic ions on the solar photolysis of chlorinated dissolved organic matter from different sources: Spectral characteristics, disinfection byproducts, and biotoxicities.

Dissolved organic matter (DOM) from wastewater treatment plant (WWTP) effluent is chlorinated and then discharged into natural waters, where it is subject to solar irradiation. However, the impacts of inorganic ions in natural waters on the photochemical transformations of the chlorinated DOM (DOM-Cl) have not been studied comprehensively. In this study, variations in the spectral characteristics, disinfection byproducts (DBPs), and biotoxicities of DOM-Cl under solar irradiation at different pH values and in the presence of NO3- and HCO3- were revealed. Three sources of DOM, including DOM from a WWTP effluent, natural organic matter from the Suwannee River, and DOM from plant leaf leachate, were investigated. Solar irradiation resulted in the oxidation of the highly reactive aromatic structures and then reduced the amounts of chromophoric and fluorescent DOM, especially under alkaline conditions. Moreover, alkaline conditions significantly promoted the detected DBPs degradation and the biotoxicities attenuation, while NO3- and HCO3- generally impeded them (or did not work). Dehalogenation of the unknown halogenated DBPs and photolysis of the nonhalogenated organics were the main mechanisms for the DOM-Cl biotoxicity reductions. Hence, improving the ecological safety of WWTP effluents could be achieved through solar irradiation by removing the DBPs formed.

The impact of natural sunlight irradiation on the biotoxicities of different molecular sizes EfOM/SRNOM and its relationship with spectral and molecular level parameters.

Natural sunlight irradiation is regarded as an efficient and low-carbon method for controlling the biotoxicity of effluents from domestic wastewater treatment plants (WWTPs). Dissolved organic matter in WWTPs effluent (EfOM) is responsible for the non-specific biotoxicity of effluent. In the present study, the variation in spectral characteristics, molecular composition, luminescent bacteria toxicity, and genotoxicity of EfOM of different molecular sizes (MOSs) during natural sunlight irradiation were investigated from a systematic perspective, and the standard natural organic matter from the Suwannee River (SRNOM) was synchronously assessed for comparative purposes. To further explore the cause of the biotoxicity changes, the relationships between the spectral or molecular level parameters (obtained from FT-ICR MS analysis) and biotoxicity were assessed using correlation analysis. The molecules in <1 kDa EfOM with lower molecular weight, higher unsaturation degree, and higher humification and fluorescence had higher luminescent bacteria toxicity under sunlight irradiation. However, in the <1 kDa SRNOM, the molecules which were characterized by higher humification and fluorescence had higher luminescent bacteria toxicity. The notable genotoxicity reduction of EfOM under sunlight irradiation was attributed to the photochemical degradation of components with a high unsaturation degree. Such findings could enable ecological safety improvement of aquatic environments using natural sunlight.

Micropollutants and biological effects as control indexes for the operation and design of shallow open-water unit ponds to polish domestic effluent.

Additional control indexes should be considered for the operation and design of post-treatment systems, as the wastewater treatment objectives are developing toward protecting the safety of ecological environments. In this study, two control indexes were selected and examined systematically in pilot-scale shallow open-water unit (SOWU) ponds for domestic effluent polishing: micropollutants and biotoxicities. The total risk quotient (RQTotal ≤ 1) and effect-based trigger value (EBT) were set as the thresholds for known micropollutants and biological effects, respectively. The results showed that RQTotal of micropollutants (n = 46) could be mitigated to an acceptable level and the luminescent bacteria toxicity was in compliance with the EBT after SOWU polishing in the warm season. The reduction of micropollutants and biotoxicities in the SOWUs both fit the k-C* model well (R2 > 0.9) in the warm and cold seasons. Finally, the k-C* model integrated with the control indexes was developed to design the SOWU dimensions, and the results indicated that a pond area of 21.7-108.5 m2 was required for every 1 m3/d of effluent when micropollutants were set as the control index, while a pond area of 3.6-18.2 m2 was required when luminescent bacteria toxicity was set as the control index.

Sunlight-induced changes in naturally stored reclaimed water: Dissolved organic matter, micropollutant, and ecotoxicity.

Natural sunlight is a vital environmental element and plays a significant role in the ecological storage of reclaimed water (RW), but its impacts on RW quality are poorly understood. In this study, sunlight-induced changes in RW with a focus on dissolved organic matter (rDOM) and 52 residual micropollutants were investigated in the field during the summer and winter seasons. The results indicated that sunlight exposure led to the dissipation of chromophoric DOM (CDOM) in the summer (55% loss) and winter (19% loss) after 14 consecutive sunny days. During open storage of RW, CDOM absorption in UVC regions was preferentially removed in the summer, while during the winter there was preferential removal of CDOM in UVA regions. The results also showed higher fluorescent DOM (FDOM) removal in summer than in winter (49% and 28%, respectively). Results in both seasons indicated that humic acid-like compounds were the most photolabile fractions and were preferentially removed under sunlight exposure. Sunlight also induced attenuation of micropollutants in the summer and winter at reductions of 66% and 24% from the initial values, respectively. Significant attenuation (>75%) was only observed for endocrine-disrupting chemicals, pharmaceuticals, and sunscreens in the summer, but they accounted for 76% of the total concentrations. Vibrio fischeri toxicity tests demonstrated that sunlight constantly decreased the luminescent bacteria acute toxicity of RW, which was estimated to be caused mainly by the sunlight-induced changes of FDOM and CDOM, while the detected micropollutants could only explain 0.02%-2% of acute toxicity. These findings have important implications regarding our understanding of the ecological storage of reclaimed water and the contribution of management strategies.

Removal of trace organic pollutants (pharmaceuticals and pesticides) and reduction of biological effects from secondary effluent by typical granular activated carbon.

Residual trace organic pollutants (TOPs) and associated biological effects from secondary effluent (SE) are attracting much attention because of their safety concerns. Granular activated carbon (GAC) adsorption, due to its low cost and high efficiency, is widely applied for further wastewater treatment, but its selective removals of TOPs and biological effects are poorly understood. In the present study, the surface physicochemical characteristics of four types of typical GACs were investigated, and their correlation with luminescent bacteria toxicity was discussed. Based on the biological effect control, shell GAC, with a great adsorption capacity and high functional group contents was selected for further study, including for the removal of fluorescent dissolved organic matter (DOM), 21 TOPs, and 3 biological effects. The shell GAC showed a promising property of removing fluorescent DOM and TOPs. The total concentration of 21 detected TOPs, including 12 pesticides and 9 pharmaceuticals, achieved 82% removal when 30 g/L shell GACs was added. Individual chemicals removal by GAC adsorption was not well described by an individual parameter (e.g., logD, molecular size, charge, functional groups), but rather by a variety of physical and chemical interactions among TOPs, DOM, and GAC. The biological effects from SE were mainly caused by TOPs and DOM. Hence, shell GACs also showed high removal efficiencies of luminescent bacteria toxicity, genotoxicity, and photosynthetic inhibition effect. The removal mechanisms of the three biological effects from SE were deeply discussed. Therefore, the GAC treatment is considered to be one of the most suitable options to ensure the ecological safety of discharged wastewater, because it can effectively control DOM, TOPs, and associated biological effects.

Investigation and assessment of micropollutants and associated biological effects in wastewater treatment processes.

Currently, the wastewater treatment plants (WWTPs) attempt to achieve the shifting from general pollution parameters control to reduction of organic micropollutants discharge. However, they have not been able to satisfy the increasing ecological safety needs. In this study, the removal of micropollutants was investigated, and the ecological safety was assessed for a local WWTP. Although the total concentration of 31 micropollutants detected was reduced by 83% using the traditional biological treatment processes, the results did not reflect chemicals that had poor removal efficiencies and low concentrations. Of the five categories of micropollutants, herbicides, insecticides, and bactericides were difficult to remove, pharmaceuticals and UV filters were effectively eliminated. The specific photosynthesis inhibition effect and non-specific bioluminescence inhibition effect from wastewater were detected and evaluated using hazardous concentration where 5% of aquatic organisms are affected. The photosynthesis inhibition effect from wastewater in the WWTP was negligible, even the untreated raw wastewater. However, the bioluminescence inhibition effect from wastewater which was defined as the priority biological effect, posed potential ecological risk. To decrease non-specific biological effects, especially of macromolecular dissolved organic matter, overall pollutant reduction strategy is necessary. Meanwhile, the ozonation process was used to further decrease the bioluminescence inhibition effects from the secondary effluent; ≥ 0.34 g O3/g DOC of ozone dose was recommended for micropollutants elimination control and ecological safety.

Investigating the origins of acute and long-term toxicity posed by municipal wastewater using fractionation.

It has been proven that the raw wastewater, secondary effluent and even reclaimed water may have toxic effects on aquatic organisms. In the present study, fractionation procedures combined with bioassays using luminescent bacteria were conducted to identify the fractions that contributed to the acute and long-term toxicity of municipal wastewater. Solid phase extraction was used to divide dissolved organic matter from the wastewater into three fractions, including non-polar, medium-polar and polar fraction. Among these fractions, although the acute toxicity of municipal wastewater was mainly caused by polar and medium-polar chemicals, the acute toxicity induced by the unit mass of the medium-polar fraction was the greatest. Using three kinds of resins, the organic substances in municipal wastewater were classified into six fractions, and the long-term toxicity of these fractions was further identified. The long-term toxicity of the hydrophobic neutrals, which were the primary toxic substances in raw wastewater, decreased after the conventional secondary biological treatment. Hydrophilic neutrals, which accounted for the majority of organic substances in the secondary effluent, were the main substances with long-term toxicity in the secondary effluent. The identification of fractions with acute and long-term toxicity in municipal wastewater is beneficial for further treatment to attenuate the ecotoxicity of wastewater before discharge into the aquatic environment.

The treatability of trace organic pollutants in WWTP effluent and associated biotoxicity reduction by advanced treatment processes for effluent quality improvement.

As increasing attention is paid to surface water protection, there has been demand for improvements of domestic wastewater treatment plant (WWTP) effluent. This has led to the application of many different advanced treatment processes (ATPs). In this study, the treatability of trace organic pollutants in secondary effluent (SE) and associated biotoxicity reduction by four types of ATPs, including coagulation, granular activated carbon (GAC) adsorption, ultraviolet (UV) photolysis and photocatalysis, and ozonation, were investigated at the bench-scale. The ATPs showed different removal capacity for the 48 chemicals, which were classified into seven categories. EDCs, herbicides, bactericides and pharmaceuticals were readily degraded, and insecticides, flame retardants, and UV filters were relatively resistant to removal. During these processes, the efficiency of the ATPs in reducing four biological effects were investigated. Of the four biological effects, the estrogenic activity from SE was not detected using the yeast estrogen screen. In contrast with genotoxicity and photosynthesis inhibition, bacterial cytotoxicity posed by SE was the most difficult biological effect to reduce with these ATPs. GAC adsorption and ozonation were the most robust treatment processes for reducing the three detected biotoxicities. UV photolysis and photocatalysis showed comparable efficiencies for the reduction of genotoxicity and photosynthesis inhibition. However, coagulation only performed well in genotoxicity reduction. The effect-based trigger values for the four bioassays, that were derived from the existing environmental quality standards and from HC5 (hazardous concentration for 5% of aquatic organisms), were all used to select and optimize these ATPs for ecological safety. Conducting ATPs in more appropriate ways could eliminate the negative effects of WWTP effluent on receiving water bodies.

Effect of elevated benzophenone-4 (BP4) concentration on Chlorella vulgaris growth and cellular metabolisms.

Benzophenone-4 (BP4), as the raw material of common sunscreen products, usually shows strong eco-toxicity and endocrine-disrupting activity in aquatic animals. However, the potential adverse effect of BP4 on aquatic vegetation is still unclear. In order to evaluate the inhibitory effect of BP4 on phytoplankton, wild and acclimated Chlorella vulgaris was used as representative aquatic plant cells and experimental studies were conducted on the characteristics of its growth and cellular metabolisms upon exposure to elevated BP4 concentrations (1, 5, 10, 20, 50, and 100 mg L-1). C. vulgaris basically appeared low sensitivity to BP4 exposure because the 96-h EC50 was measured as 65.16 mg L-1 for its wild type. The 96-h EC50 of the acclimated type, which was pre-exposed to 10 mg L-1 of BP4 and transferred twice, was 140.76 mg L-1. By cellular response tests regarding non-enzymatic antioxidants carotenoid content, malondialdehyde (MDA), enzyme antioxidant superoxide dismutase (SOD) activity, and the photosynthetic efficiency, it was clarified that increasing exposure concentration elevated the hindrance to cellular metabolism. However, the rate of BP4 utilization as substrates for C. vulgaris growth showed a trend of decreasing with increasing BP4 concentration. The higher 96-h EC50 value of the acclimated C. vulgaris to BP4 inhibition than the wild C. vulgaris showed the enhanced tolerance capability; however, the continuous stress response of acclimated type should be taken into account when using microalgae species for toxicity assessment.

Micropollutants removal and health risk reduction in a water reclamation and ecological reuse system.

As reclaimed water use is increasing, its safety attracts growing attention, particularly with respect to the health risks associated with the wide range of micropollutants found in the reclaimed water. In this study, sophisticated analysis was conducted for water samples from a water reclamation and ecological reuse system where domestic wastewater was treated using an anaerobic-anoxic-oxic unit followed by a membrane bioreactor (A2O-MBR), and the reclaimed water was used for replenishing a landscape lake. A total of 58 organic micropollutants were detected in the system, consisting of 13 polycyclic aromatic hydrocarbons (PAHs), 16 phenols, 3 pesticides, and 26 pharmaceuticals and personal care products (PPCPs). After treatment by the A2O-MBR process, effective removal of pesticides and phenols was achieved, while when the reclaimed water entered the landscape lake, PPCPs were further removed. From the physicochemical properties of micropollutants, it could be inferred that phenols and dichlorphos (the only pesticide with considerable concentration in the influent) would have been mainly removed by biodegradation and/or volatilization in the biological treatment process. Additionally, it is probable that sludge adsorption also contributed to the removal of dichlorphos. For the predominant PPCP removal in the landscape lake, various actions, such as adsorption, biodegradation, photolysis, and ecologically mediated processes (via aquatic plants and animals), would have played significant roles. However, according to their logKoc, logKow and logD (pH = 8) values, it could be concluded that adsorption by suspended solids might be an important action. Although carcinogenic and non-carcinogenic risks associated with all the detected micropollutants were at negligible levels, the hazard quotients (HQs) of PPCPs accounted for 92.03%-97.23% of the HQTotal. With the significant removal of PPCPs through the ecological processes in the landscape lake, the safety of reclaimed water use could be improved. Therefore, the introduction of ecological unit into the water reclamation and reuse system could be an effective measure for health risk reduction posed by micropollutants.

Function of a landscape lake in the reduction of biotoxicity related to trace organic chemicals from reclaimed water.

The storage of water in a landscape lake can act as a buffer zone between reclaimed water production and reuse, but there is still uncertainty about the variation of water quality and toxic effects during the open-storage process. In this study, long-term sample collection, chemical analyses and biotoxicity assessments were conducted on reclaimed water before and after open storage in a landscape lake. The organic contents, in terms of chemical oxygen demand and total organic carbon, were found to be slightly higher in the lake water than that in the reclaimed water, but substantial reduction of the total concentration of 52 trace organic chemicals was obtained and microorganism toxicity, phytotoxicity, aquatic vertebrate toxicity and genotoxicity, were significantly weakened after open storage. Furthermore, the total risk quotient (RQTotal) decreased from 5.12 (potential ecological risk level) in the reclaimed water to 0.18 (negligible ecological risk level) in the lake water. The removal of chlorpyrifos, dichlorphos and tetracycline was identified as the main reason for biotoxicity reduction after open storage. The seminatural environment of the landscape lake would have provided a favorable condition for the decay of toxic trace organic chemicals so that the stored water turned to be safer for further reuse.

Assessment of multiple hormone activities of a UV-filter (octocrylene) in zebrafish (Danio rerio).

In this study, zebrafish (Danio rerio) were exposed to a UV-filter-octocrylene (OCT) with elevated concentrations for 28 d. The total body accumulation of OCT in zebrafish was found to reach 2321.01 ("L" level), 31,234.80 ("M" level), and 70,593.38 ng g(-1) ("H" level) when the average OCT exposure concentration was controlled at 28.61, 505.62, and 1248.70 µg L(-1), respectively. Gross and histological observations as well as RT-qPCR analysis were conducted to determine the effects of OCT accumulation on zebrafish. After exposure, the gonad-somatic index and percentage of vitellogenic oocytes were found to increase significantly in the ovaries of female zebrafish at the H accumulation level. Significant up-regulation of esr1 and cyp19b were observed in the gonads, as well as vtg1 in the livers for both female and male zebrafish. At M and H accumulation levels, apparent down-regulation of ar was observed in the ovaries and testis of the female and male zebrafish, respectively. Although the extent of the effects on zebrafish differed at different accumulation levels, the induction of vtg1 and histological changes in the ovaries are indications of estrogenic activity and the inhibition of esr1 and ar showed antiestrogenic and antiandrogenic activity, respectively. Thus, as OCT could easily accumulate in aquatic life such as zebrafish, one of its most of concern hazards would be the disturbance of the histological development and its multiple hormonal activities.

Bioassay based luminescent bacteria: interferences, improvements, and applications.

Due to the merits of being time-saving, cost effective and simple operation, the luminescent bacteria toxicity assay (LBTA) has been widely used for environmental pollution monitoring. Based on numerous studies since 2007, this critical review aims to give an overview on the mechanisms, developments and applications of LBTA. Firstly, based on the introduction of the mechanisms of LBTA, this review shows the interferences from the characteristics of testing samples (such as inorganic nutrients, color, turbidity) and summarizes the improvements on pretreatment method, test methods and test systems in recent years. Regarding the factors that affect the toxicity prediction of single chemicals, the correlation between the toxicity index expressed as median effective concentration (EC50) and characters (such as Kow, the alkyl chain length, the anion and the cation) of known chemicals, especially the emerging ionic liquids (ILs), were given an in-depth discussion. The models for predicting the joint effect of mixtures to luminescent bacteria were also presented. For the factors that affect the toxicity of actual waters, the correlation of toxicity of actual samples to luminescent bacteria and their conventional indexes were discussed. Comparing the sensitivity of the LBTA with other bioassays could indicate the feasibility of the LBTA applied on specific samples. The summary on the application of LBTA to environmental samples has been made to find the future research direction.

Reverse osmosis pretreatment method for toxicity assessment of domestic wastewater using Vibrio qinghaiensis sp.-Q67.

Luminescent bacterial test is a fast and sensitive method for acute toxicity assessment of water and wastewater. In this study, an improved toxicity testing method was developed using the freshwater luminescent bacteria Vibrio qinghaiensis sp.-Q67 that involved pretreatment of water samples with reverse osmosis (RO) to eliminate the interferences caused by nutrients in concentrated samples and to improve the reliability and sensitivity of the analysis. Because water samples contain low concentrations of several target toxic substances, rapid acute toxicity testing method that is commonly employed does not achieve enough sensitivity. The proposed RO pretreatment could effectively enrich organic and inorganic substances in water samples to enable a more effective and sensitive toxicity evaluation. The kinetic characteristics of toxicity of raw sewage and secondary effluent were evaluated based on the relative luminescence unit (RLU) curves and time-concentration-effect surfaces. It was observed that when the exposure time was prolonged to 8-h or longer, the bacteria reached the logarithmic growth stage. Hence, the stimulating effects of the coexisting ions (such as Na(+), K(+), NO3(-)) in the concentrated samples could be well eliminated. A 10-h exposure time in proposed Q67 test was found to quantitatively evaluate the toxicity of the organic and inorganic pollutants in the RO-concentrated samples.

Characteristics of THMFP increase in secondary effluent and its potential toxicity.

Chlorination of the secondary effluent from domestic wastewater treatment plants (WWTP) is suspicious of toxic effects due to the formation of trihalomethanes (THMs). In order to clarify this mechanism, samples were collected from the inlet and outlet of a WWTP, and a series of analyses were conducted on the relationship between THMs formation and the toxicity of the secondary effluent after chlorination. By three-dimensional fluorescence spectrometry it was clarified that the biological wastewater treatment process was accompanied with the formation of humic- and fulvic-like substances which were typical THMs precursors as shown by their high thihalomethane formation potential (THMFP) as well as high specific ultraviolet absorbance (SUVA). As a result of bioassay using a freshwater luminescent bacterium Vibrio-qinghaiensis sp.-Q67, a linear relationship was obtained between the concentration of THMs after chlorinating the effluent and its toxicity expressed as the inhibition of the luminescent light. The effective THMs concentration corresponding to a 50% inhibition was 318 µg/L at a chlorine dose of 19.6 mg/L as Cl2. THMs formation may be the direct reason for the increase of toxicity in the secondary effluent when chlorine was used as disinfectant.

Study of the variation of ecotoxicity at different stages of domestic wastewater treatment using Vibrio-qinghaiensis sp.-Q67.

A bioassay using the luminescent bacterium Vibrio-qinghaiensis sp.-Q67 associated with solid-phase extraction (SPE) was developed for evaluating the variation of ecotoxicity along with the reduction of organic substances in a domestic wastewater treatment plant employing an oxidation ditch process. With effective elimination of the interference from all inorganic substances by the SPE operation, the ecotoxicity of the water, as expressed by the toxicity impact index, TII(50) (%) after a model-based regression and parameter transformation, was found to decrease from 50.51% in the influent to 25.84% after the grid chamber and then to 1.38% for the secondary effluent, but the final chlorination stage resulted in a slight TII(50) increase. Of the two typical tertiary treatment processes, coagulation could not assist further reduction of the ecotoxicity while carbon adsorption could reduce the TII(50) to as low as 0.96%. When enhanced primary treatment was conducted, the influent TII(50) could be directly reduced to 7.36%. A good correlative relationship was found between the total COD concentration and the TII(50) value at different stages of the wastewater treatment process.