Operational Constraints of Detecting SARS-CoV-2 on Passive Samplers using Electronegative Filters: A Kinetic and Equilibrium Analysis.

In developing an effective monitoring program for the wastewater surveillance of SARS-CoV-2 ribonucleic acid (RNA), the importance of sampling methodology is paramount. Passive sampling has been shown to be an effective tool to detect SARS-CoV-2 RNA in wastewater. However, the adsorption characteristics of SARS-CoV-2 RNA on passive sampling material are not well-understood, which further obscures the relationship between wastewater surveillance and community infection. In this work, adsorption kinetics and equilibrium characteristics were evaluated using batch-adsorption experiments for heat-inactivated SARS-CoV-2 (HI-SCV-2) adsorption to electronegative filters. Equilibrium isotherms were assessed or a range of total suspended solids (TSS) concentrations (118, 265, and 497 mg L-1) in wastewater, and a modeled qmax of 7 × 103 GU cm-2 was found. Surrogate adsorption kinetics followed a pseudo-first-order model in wastewater with maximum concentrations achieved within 24 h. In both field and isotherm experiments, equilibrium behavior and viral recovery were found to be associated with wastewater and eluate TSS. On the basis of the results of this study, we recommend a standard deployment duration of 24-48 h and the inclusion of eluate TSS measurement to assess the likelihood of solids inhibition during analysis.

Analysis of human serum and urine for tentative identification of potentially carcinogenic pesticide-associated N-nitroso compounds using high-resolution mass spectrometry.

Human serum and urine samples were analyzed for a suite of nitrosatable pesticides and potentially carcinogenic pesticide-associated N-nitroso (PANN) compounds. Formation of PANN compounds may occur in vivo after consumption of food or water containing trace amounts of nitrosatable pesticide residues and nitrate. Using a modified version of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method, nine nitrosatable pesticides and byproducts were extracted from serum and urine from 64 individuals from two different sample populations in Atlantic Canada: (i) Prince Edward Island, a region where nitrate and trace amounts of nitrosatable pesticides have been detected in groundwater; and (ii) Halifax, Nova Scotia, a non-agricultural urban area. Samples were then analyzed using ultra-high pressure liquid chromatography (UHPLC) coupled with high-resolution accurate mass (HRAM) single-stage orbitrap mass spectrometry (MS), which allows for semi-targeted analysis and tentative identification of a virtually limitless number of exposure biomarkers. Two nitrosatable target analytes, ethylenethiourea (ETU) and 3,5,6-trichloro-2-pyridinol (TCPy) were found in serum, while atrazine (ATR) and ETU were detected in urine. Five and six PANN compounds were tentatively identified in serum and urine, respectively. The two PANN compounds that were most frequently tentatively identified in serum were N-nitroso dimethoate (N-DIM) and N-nitroso omethoate (N-OME) with detection frequencies of 78% and 95%, respectively. This is the first biomonitoring study of its kind to investigate PANN compounds in human serum and urine.

Specificity of UV-C LED disinfection efficacy for three N95 respirators.

The recent surge in the use of UV technology for personal protective equipment (PPE) has created a unique learning opportunity for the UV industry to deepen surface disinfection knowledge, especially on surfaces with complex geometries, such as the N95 filter facepiece respirators (FFR). The work outlined in this study addresses the interconnectedness of independent variables (e.g., UV Fluence, respirator material) that require consideration when assessing UV light efficacy for disinfecting respirators. Through electron microscopy and Fourier-transform infrared (FTIR) spectroscopy, we characterized respirator filter layers and revealed that polymer type affects disinfection efficacy. Specifically, FFR layers made from polypropylene (PP) (hydrophobic in nature) resulted in higher disinfection efficiency than layers composed of polyethylene terephthalate (PET-P) (hygroscopic in nature). An analysis of elastic band materials on the respirators indicated that silicone rubber-based bands achieved higher disinfection efficiency than PET-P bands and have a woven, fabric-like texture. While there is a strong desire to repurpose respirators, through this work we demonstrated that the design of an appropriate UV system is essential and that only respirators meeting specific design criteria may be reasonable for repurposing via UV disinfection.

Assessing the impact of multiple ultraviolet disinfection cycles on N95 filtering facepiece respirator integrity.

During the COVID-19 pandemic, N95 filtering facepiece respirators (FFRs) were recommended to protect healthcare workers when providing care to infected patients. Despite their single-use disposable nature, the need to disinfect and repurpose FFRs is paramount during this global emergency. The objectives of this study were to (1) determine if UV treatment has an observable impact on respirator integrity; (2) test the impact of UV treatment on N95 FFR user fit; and (3) test the impact of UV treatment on FFR integrity. Ultraviolet (UV) disinfection was assessed in maintaining N95 FFR integrity. Two models of FFRs were exposed to UV fluences ranging from 0 to 10,000 mJ cm-2 per side and subsequently tested for fit, respirator integrity, and airflow. Inspection of N95 FFRs before and after UV treatment via microscopy methods showed no observable or tactile abnormalities in the integrity of respirator material or straps. Tensile loading tests on UV-treated and untreated respirator straps also demonstrated no impact on breaking strength. Standardized fit test methods showed no compromise in user fit following UV treatment. Evaluation of particle penetration and airflow through N95 FFRs showed no impact on integrity, and average filtration efficiency did not fall below 95% for any of the respirator types or fluence levels. This work provides evidence that UV disinfection does not compromise N95 FFR integrity at UV fluences up to 10,000 mJ cm-2. UV disinfection is a viable treatment option to support healthcare professionals in their strategy against the spread of COVID-19.

Validation of a QuEChERS method for extraction of estrogens from a complex water matrix and quantitation via high-performance liquid chromatography-mass spectrometry.

The traditional approach to extracting estrogens from water matrices, solid-phase extraction (SPE), presents a number of challenges when applied to complex wastewater matrices. Conversely, the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) clean-up method offers an alternative sample preparation approach that omits sample filtration and overcomes additional challenges associated with SPE. The objective of this study was to implement and validate a scaled QuEChERS method, using a standard addition approach, for extracting estrone (E1), 17ß-estradiol (E2), and estriol (E3) from the estrogenic influent of a recirculating aquaculture system containing American eels (Anguilla rostrata). While traditional QuEChERS protocols do not facilitate considerable sample concentration, a 500-fold concentration factor was implemented for reliable quantitation of parts-per-trillion concentrations of estrogens from an initial sample volume of 20 mL to a final extract volume of 40 µL. Following analysis via high-performance liquid chromatography-mass spectrometry, excellent process efficiencies were observed at spiked concentrations of 10 and 50 ng L-1 for E2 and E1 (101 to 111%; %RSD ≤ 16), and moderate to acceptable process efficiencies were achieved for E3 (75 to 87%; %RSD ≤ 16). Validation of method parameters, including specificity, linearity, accuracy (recovery and process efficiencies), precision (intra-day precision, and inter-day precision), matrix effects, method detection limit, and limit of quantitation, led to reliable quantitation of unknown concentrations of E1, E2, and E3 in the aquaculture influent as low as 52, 20, and 33 ng L-1, respectively. This study provides a validated analytical method for waste systems requiring quantitation of estrogens in their complex wastewater matrices.

N-nitrosoethylenethiourea formation at environmentally-relevant concentrations of ethylenethiourea in a pooled groundwater sample.

N-nitroso compounds form from the interaction between nitrosatable precursors and nitrite under acidic conditions. A majority of N-nitroso compounds tested show evidence of carcinogenicity in animal models. Formation of N-nitroso compounds may occur from exposure to precursors in drinking water, but the extent of formation depends on a number of factors, including concentration of substrates, presence of catalysts and inhibitors, and pH. The objective of this study was to examine these factors in pesticide-associated N-nitroso (PANN) compound formation in drinking water. In preliminary screening experiments, nine nitrosatable pesticides and degradation products were individually reacted at environmentally-relevant concentrations (≤ 20 µg L--1) with sodium nitrite (NaNO2) and hydrochloric acid (HCl) in ultra-pure water. Only ethylenethiourea (ETU) showed evidence of PANN compound formation in initial experiments and was further tested for N-nitrosoethylenethiourea (N-ETU) formation in a pooled groundwater sample (comprised of five tap water samples combined into one homogenous sample) collected from an agricultural region of Prince Edward Island in Canada, where nitrate contamination is a known concern. Evidence of N-ETU formation in the groundwater sample was observed within 30 min at concentrations 7.5, 10, and 20 µg L-1. Analysis of target compounds and semi-target PANN compounds was performed using ultra-high pressure liquid chromatography coupled with high resolution orbital ion trap mass spectrometry. These preliminary experiments serve to inform about potential PANN compound formation in groundwater. The results of this study suggest that ETU is capable of forming potentially carcinogenic N-ETU in water containing nitrite/nitrate at trace concentrations under acidic conditions. Thus, these findings suggest that N-ETU formation may be a concern for individuals exposed to low concentrations of ETU in groundwater.