Alternative methods of monitoring emerging contaminants in water: a review.

Anthropogenic activities have steadily increased the release of emerging contaminants (ECs) in aquatic bodies, and these ECs may have adverse effects on humans even at their trace (µg L-1) levels. Their occurrence in wastewater systems is more common, and the current wastewater treatment facilities are inefficient in eliminating many of such persistent ECs. "Gold standard" techniques such as chromatography, mass spectrometry, and other high-resolution mass spectrometers are used for the quantification of ECs of various kinds, but they all have significant limitations. This paper reviews the alternative methods for EC detection, which include voltammetry, potentiometry, amperometry, electrochemical impedance spectroscopy (EIS) based electrochemical methods, colorimetry, surface-enhanced Raman spectroscopy (SERS), fluorescence probes, and fluorescence spectroscopy-based optical techniques. These alternative techniques have several advantages over conventional techniques, including low sample volume, excludes solid phase extraction procedure, high sensitivity, selectivity, portability, reproducibility, rapidity, low cost, and the ability to monitor ECs in real time. This review summarises each of the alternative methods for detecting ECs in water samples and their respective limits of detection (LODs). The sensitivity of each technique varied depending on the type of EC measured, type of electrochemical probe and electrode, substrates, type of nanoparticle (NP), the physicochemical parameters of water samples tested, and more. Nevertheless, this paper also focuses on some of the current challenges encountered by these alternative methods in monitoring ECs.

Submicron polymer particles may mask the presence of toxicants in wastewater effluents probed by reporter gene containing bacteria.

Microplastics are ubiquitous in aquatic systems and break down into submicron particles that can interact with aquatic toxic chemicals. These interactions may affect the detection of toxicants when using bacteria as a biomonitoring tool. This study examined the effects of model polystyrene (PS)-based submicron particles on the detection of aqueous geno- and cytotoxicity by genetically modified bioluminescent (GMB) bacteria. The toxicities were tested in three treated wastewater (TWW) effluents before and after chlorination. The PS plastics included negatively charged sulfate-coated (S-PS) and pristine (P-PS) particles of different sizes (0.1, 0.5, and 1.0 µm) that were present at different concentrations. Chlorinated or not, the S-PS and P-PS particles per se were not toxic to the GMB bacteria. However, exposure of PS particles to TWW effluents can significantly reduce the measured geno- and cytotoxicity. Adsorption of toxic compounds to polymer particles can limit the ability of the bacteria to detect those compounds. This masking effect may be mitigated by TWW chlorination, possibly due to the formation of new toxic material. Due to interactions between toxic TWW constituents and the plastics particles, water samples containing particle-associated contaminants and/or their transformation products may be declared non-toxic, based on bacterial tests as a biomonitoring tool.

Water toxicity evaluations: Comparing genetically modified bioluminescent bacteria and CHO cells as biomonitoring tools.

The use of water for drinking and agriculture requires knowledge of its toxicity. In this study, we compared the use of genetically modified bioluminescent (GMB) bacteria whose luminescence increases in the presence of toxicants and Chinese Hamster Ovary (CHO) cells for the characterization of the toxicity of water samples collected from a lake and streams, hydroponic and aquaponic farms, and a wastewater treatment plant. GMB bacteria were used to probe genotoxicity, cytotoxicity and reactive oxygen species-induced effects in the whole water samples. Unlike GMB bacteria, the use of CHO cells requires XAD resin-based pre-concentration of toxic material present in water samples for the subsequent cytotoxicity assay. In addition to the examination of the toxicity of the water from the different sources, the GMB bacteria were also used to test the XAD extracts diluted to the concentrations causing 50% growth inhibition of the CHO cells. The two biomonitoring tools provided different results when they were used to test the above-mentioned diluted XAD extracts. A pre-concentration procedure based on adsorption by XAD resins with subsequent elution was not sufficient to represent the material responsible for the toxicity of the whole water samples toward the GMB bacteria. Therefore, the use of XAD resin extracts may lead to major underestimates of the toxicity of water samples. Although the toxicity findings obtained using the GMB bacteria and CHO cells may not correlate with each another, the GMB bacteria assay did provide a mechanism-specific biomonitoring tool to probe the toxicity of water samples without a need for the pre-concentration step.

Strengths of correlations with formation of chlorination disinfection byproducts: effects of predictor type and other factors.

Measurements of the UV-Vis absorbance (Abs) and intensity of fluorescence emission (Fluor), as well as of concentrations of total or dissolved organic carbon (OC) in aqueous samples are commonly used to estimate the potential for disinfection byproducts (DBPs) formation during water chlorination. In this work, based on 574 linear associations collected from 70 experimental research papers published over the period of 1997-2019, the strengths of the correlations of Abs, Fluor, and OC with DBPs concentrations are compared. The correlations were expressed as approximately normally distributed Z-scores using Fisher variance-stabilizing transformation. The effects of specific prediction method, chlorination agent, water source, and DBPs type, with consideration of possible effects due to the presence of bromide, are examined against Z-scores by ANOVA, testing main effects and some variables interactions. The performed analysis is a first attempt to expose differences and patterns in correlation strengths associated with DBPs formation, based on systematically covered broad existing literature. Abs and OC concentration of water samples tend to demonstrate the strongest correlations with DBPs formation as compared with specific UV absorbance (SUVA) or intensity of fluorescence emission. Correlations of DBPs formation during chloramination demonstrated weaker strengths as compared with other chlorination agents, suggesting more caution in predicting DBPs concentrations, based on simple descriptors such as Abs, OC, and Fluor. In a series of different water types, the correlations with DBPs formation are expected to be enhanced, when wastewater is chlorinated. Non-fluorescent matter may be an important contributor to DBPs formation during water chlorination. When fluorescence intensity is considered as a predicting tool, choosing humic-like rather than proteinaceous fluorescence may enhance the strengths of the correlations with DBPs formation. Different performances of Abs, OC, and Fluor in correlating with DBPs formation may be beneficial for their concurrent use helping to optimize removal of different DBPs precursors.

Toxicity, uptake, and accumulation of nano and bulk cerium oxide particles in Artemia salina.

Although the toxicological impact of metal oxide nanoparticles has been studied for the last few decades on aquatic organisms, the exact mechanism of action is still unclear. The fate, behavior, and biological activity of nanoparticles are dependent on physicochemical factors like size, shape, surface area, and stability in the medium. This study deals with the effect of nano and bulk CeO2 particles on marine microcrustacean, Artemia salina. The primary size was found to be 15 ± 3.5 and 582 ± 50 nm for nano and bulk CeO2 (TEM), respectively. The colloidal stability and sedimentation assays showed rapid aggregation of bulk particles in seawater. Both the sizes of CeO2 particles inhibited the hatching rate of brine shrimp cyst. Nano CeO2 was found to be more toxic to A. salina (48 h LC50 38.0 mg/L) when compared to bulk CeO2 (48 h LC50 92.2 mg/L). Nano CeO2-treated A. salina showed higher oxidative stress (ROS) than those treated with the bulk form. The reduction in the antioxidant activity indicated an increase in oxidative stress in the cells. Higher acetylcholinesterase activity (AChE) was observed upon exposure to nano and bulk CeO2 particles. The uptake and accumulation of CeO2 particles were increased with respect to the concentration and particle size. Thus, the above results revealed that nano CeO2 was more lethal to A. salina as compared to bulk particles.