•Automation of mass spectral matching for GC×GC/TOF-MS nontargeted and suspect screening analyses.•Algorithmic and machine learning approaches used for EI mass spectral matching degrees.•Provides ...mirror plots of observed mass spectra and best NIST library hit matches.•Obtains acceptable agreement rates between manual reviews and model predictions.
Nontargeted analysis based on mass spectrometry is a rising practice in environmental monitoring for identifying contaminants of emerging concern. Nontargeted analysis performed using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC/TOF-MS) generates large numbers of possible analytes. Moreover, the default spectral library similarity score-based search algorithm used by LECO® ChromaTOF® does not ensure that high similarity scores result in correct library matches. Therefore, an additional manual screening is necessary, but leads to human errors especially when dealing with large amounts of data. To improve the speed and accuracy of the chemical identification, we developed CINeMA.py (Classification Is Never Manual Again). This programming suite automates GC×GC/TOF-MS data interpretation by determining the confidence of a match between the observed analyte mass spectrum and the LECO® ChromaTOF® software generated library hit from the NIST Electron Ionization Mass Spectral (NIST EI-MS) library. Our script allows the user to evaluate the confidence of the match using an algorithmic method that mimics the manual curation process and two different machine learning approaches (neural networks and random forest). The script allows the user to adjust various parameters (e.g., similarity threshold) and study their effects on prediction accuracy. To test CINeMA.py, we used data from two different environmental contaminant studies: an EPA study on household dust and a study on stormwater runoff. Using a reference set based on the analysis performed by highly trained users of the ChromaTOF and GC×GC/TOF-MS systems, the random forest model had the highest prediction accuracies of 86% and 83% on the EPA and Stormwater data sets, respectively. The algorithmic approach had the second-best prediction accuracy (82% and 79%), while the neural network accuracy had the lowest (63% and 67%). All the approaches required less than 1 min to classify 986 observed analytes, whereas manual data analysis required hours or days to complete. Our methods were also able to detect high confidence matches missed during the manual review. Overall, CINeMA.py provides users with a powerful suite of tools that should significantly speed-up data analysis while reducing the possibilities of manual errors and discrepancies among users, and can be applicable to other GC/EI-MS instrument based nontargeted analysis.
Thirdhand smoke (THS) is the persistent and toxic residue from tobacco smoke in indoor environments. A comprehensive understanding of the chemical constituents of THS is necessary to assess the risks ...of long-term exposure and to establish reliable THS tracers. The objective of this study was to investigate compounds associated with THS through nontargeted analysis (NTA) of settled house dust samples from smokers' and non-smokers’ homes, using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOF-MS). Compounds that were either only present in dust from smokers' homes or that had significantly larger abundance than in non-smokers’ homes were termed qualified compounds. We identified 140 qualified compounds, and of these, 42 compounds were tentatively identified by searching matching mass spectra in NIST electron impact (EI) mass spectral library including 20 compounds confirmed with their authentic standards. Among the 42 compounds, 26 compounds were statistically more abundant (p < 0.10) in dust from homes of smokers; seven were tobacco-specific compounds, two of which (nornicotyrine, 3-ethenylpyridine) have not been reported before in house dust. Two compounds, tris (2-chloroethyl) phosphate (a toxic compound used as a flame retardant and reported in tobacco) and propanoic acid, 2-methyl-, 1-(1,1-dimethylethyl)-2-methyl-1,3-propanediyl ester (highly abundant and reported in exhaled air of smokers), were found in dust from all smokers' homes and in zero non-smokers’ homes, making these potential THS tracers, possibly associated with recent smoking. Benzyl methyl ketone was significantly higher in dust in smokers’ homes, and was previously reported not as a product of tobacco but rather as a form of methamphetamine. This compound was recently reported in mainstream tobacco smoke condensate through NTA as well. These identified potential tracers and chemical components of THS in this study can be further investigated for use in developing THS contamination and exposure assessments.
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•Dust from smoker's and non-smoker's homes were compared.•Identified 2 potential markers of indoor third hand smoke contamination.•Identified 2 tobacco constituents that were previously unreported in house dust.
Cigarette butts are one of the most prevalent forms of litter worldwide and may leach toxic compounds when deposited in aquatic environments. Previous studies demonstrated that smoked cigarette ...leachate is toxic toward aquatic organisms. However, the specific bioavailable chemicals from the leachate and the potential for human and wildlife exposure through the food chain were unknown. Using a nontargeted analytical approach based on GC×GC/TOF-MS, 43 compounds were confirmed to leach from smoked cigarettes when exposed to a water source. Additionally, the bioaccumulation potential of organic contaminants in an edible fish, rainbow trout (Oncorhynchus mykiss), was assessed through direct exposure to the leachate of smoked cigarettes at 0.5 CB/L for 28 days. There was a significant reduction in fish mass among the exposed rainbow trout vs the control group (χ2 (1) = 5.3, p = 0.021). Both nontargeted and targeted chemical analysis of representative fish tissue identified four tobacco alkaloids, nicotine, nicotyrine, myosmine, and 2,2′-bipyridine. Their average tissue concentrations were 466, 55.4, 94.1, and 70.8 ng/g, respectively. This study identifies leached compounds from smoked cigarettes and demonstrates the uptake of specific chemicals in rainbow trout, thus suggesting a potential for accumulation in food webs, resulting in human and wildlife exposure.
Smoked cigarettes are the most prevalent form of litter worldwide, often finding their way into oceans and inland waterways. Cigarette smoke contains more than 4000 individual chemicals, some of them ...carcinogenic or otherwise toxic. We examined the cytotoxicity, genotoxicity, aryl hydrocarbon receptor (AhR), estrogen receptor (ER), and p53 response pathways of smoked cigarette leachate in vitro. Both seawater and freshwater leachates of smoked cigarettes were tested. Cytotoxicity and genotoxicity were negligible at 100 smoked cigarettes/L, while statistically significant AhR, ER, and p53 responses were observed in the extracts of both leachates, suggesting a potential risk to human health through exposure to cigarette litter in the environment. To identify responsible chemicals for the AhR response, an effect directed analysis approach was coupled with nontargeted chemical analysis based on comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC/TOF-MS). Eleven compounds potentially responsible for the AhR response were identified. Among them, 2-methylindole was partially responsible for the AhR response.
The persistence and transformation of water soluble chemical constituents derived from surface oil from the 2015 Refugio Oil Spill and from a nearby natural seep were evaluated under simulated ...sunlight conditions. Photoirradiation resulted in enhanced oil slick dissolution, which was more pronounced in spill oil compared to seep oil. Nontargeted analysis based on GC × GC/TOF-MS revealed that photoirradiation promoted oil slick dissolution, and more water soluble compounds were released from spill oil (500 compounds) than from seep oil (180 compounds), most of them (488 in spill oil and 150 in seep oil) still persisting in solution after 67 days of photoirradiation. First-order degradation rate coefficients of humic-like water soluble constituents were found to be 0.26 day−1 and 0.29 day−1 for irradiated spill and seep samples, respectively. The decreases in humic-like fluorescence, specific UV absorbance, and aromatic compounds without corresponding decreases in DOC concentration support indirect photochemical transformation in addition to complete photomineralization.
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•Oil from a spill and a natural seep were abiotically exposed to simulated sunlight.•Most soluble constituents detected were present after 67 d of sunlight exposure.•Photoirradiation promoted dissolution of surface oil-derived compounds.•Phototransformations occurred in addition to photooxidation.•A new, photolabile fluorescent component was identified in spill oil.
The persistence of trace organic chemicals in treated effluent derived from both centralized wastewater treatment plants (WWTPs) and decentralized wastewater treatment systems (DEWATS) is of concern ...due to their potential impacts on human and ecosystem health. Here, we utilize non-targeted analysis (NTA) with comprehensive two-dimensional gas chromatography coupled with time of flight mass spectrometry (GC × GC/TOF-MS) to conduct an evaluation of the common persistent and removed compounds found in two centralized WWTPs in the USA and South Africa and one DEWATS in South Africa. Overall, removal efficiencies of chemicals were similar between the treatment plants when they were compared according to the number of chemical features detected in the influents and effluents of each treatment plant. However, the DEWATS treatment train, which has longer solids retention and hydraulic residence times than both of the centralized WWTPs and utilizes primarily anaerobic treatment processes, was able to remove 13 additional compounds and showed a greater decrease in normalized peak areas compared to the centralized WWTPs. Of the 111 common compounds tentatively identified in all three influents, 11 compounds were persistent in all replicates, including 5 compounds not previously reported in effluents of WWTPs or water reuse systems. There were no significant differences among the physico-chemical properties of persistent and removed compounds, but significant differences were observed among some of the molecular descriptors. These results have important implications for the treatment of trace organic chemicals in centralized and decentralized WWTPs and the monitoring of new compounds in WWTP effluent.
•Non-targeted analysis (NTA) identified 111 common WWTP influent compounds.•11 of the common influent compounds were persistent in the studied WWTP effluents.•Anaerobic treatment reduced chemical peak areas more than conventional treatment.•NTA revealed 5 new compounds not previously reported in WWTP effluent.•Physico-chemical properties did not differ among persistent and removed compounds.
The present study, conducted at the Kendall-Frost Mission Bay Marsh Reserve in San Diego, California, aimed to assess tobacco-related pollutants in urban waters, a topic with limited prior research. ...Across 26 events occurring between November 2019 and February 2022, encompassing both wet and dry seasons at two outfall sites (Noyes St. and Olney St.), water and sediment samples were subjected to analysis for nicotine and cotinine levels, with Noyes St. displaying wide variation in nicotine concentrations, reaching a peak of 50.75 ng/L in water samples, whereas Olney St. recorded a peak of 1.46 ng/L. Wet seasons consistently had higher nicotine levels in water, suggesting the possibility of tobacco litter entering the reserve through stormwater runoff. Cotinine was detected in both sites in both water and sediment samples; however, these levels were considerably lower in comparison to nicotine concentrations.
Limited research assesses aquatic environmental pollution from tobacco use and disposal, especially in protected areas like urban natural reserves. This study was conducted at the Kendall-Frost Mission Bay Marsh Reserve in San Diego, California, to evaluate tobacco-related pollutants in San Diego's urban waters. Twenty-six sampling events between November 2019 and February 2022, spanning wet and dry seasons at two outfall sites, were conducted. Nicotine and cotinine, a major ingredient of tobacco and its metabolite, were analyzed in the collected water and sediment samples. Nicotine concentrations differed substantially between the outfall locations (Noyes St. and Olney St.), with Noyes St. displaying wide variations, averaging at 9.31 (±13.24) ng/L with a maximum concentration of 50.75 ng/L, and Olney St. at 0.53 (±0.41) ng/L with a maximum concentration of 1.46 ng/L in water samples. In both locations, the nicotine concentrations in water samples were higher during wet seasons than dry seasons, and this pattern was more significant at Noyes St. outfall than at Olney St. outfall, which received not only stormwater runoff but also was connected to Mission Bay. Although this pattern did not directly align with sediment nicotine levels at both sites, maximum nicotine concentration in Noyes St. sediments during wet seasons was approximately 120 times higher than in Olney St. sediments. Regarding cotinine, Noyes St. outfall water averaged 3.17 ng/L (±1.88), and Olney St. water averaged 1.09 ng/L (±1.06). Similar to nicotine, the cotinine concentrations were higher in Noyes St. water and sediment compared to Olney St., but overall, the cotinine concentrations in both water and sediment were much lower than the corresponding nicotine concentrations. The study identifies urban stormwater runoff as a potential source of nicotine and cotinine pollution in a protected reserve, implicating tobacco product litter and human tobacco use as contributing factors.
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•Tobacco-related contamination studies in natural reserves are rare.•26 samplings occurred in two seasons, targeting water and sediment between 2019 and 2022.•Nicotine and cotinine in water and sediment indicate tobacco pollution in the reserve.•Rainfall and stormwater drainage could be sources of reserve nicotine.•Cotinine in the reserve could result from stormwater runoff or nicotine degradation.
The recent rediscovery of offshore DDT waste dumping in the Southern California Bight (SCB) has led to questions about the extent and type of pollution in deep ocean environments. We used a ...nontargeted analysis to identify halogenated organic compounds (HOCs), including DDT+, in sediment in the San Pedro Basin. Additionally, we examined the chemical profiles of deep ocean biota inhabiting the SCB to assess the bioavailability of DDT+ and HOCs to the deep ocean food web. We detected 49 HOCs across all samples, including 15 DDT+ compounds in the sediment and 10 DDT+ compounds in the biota. Compounds included tris(4-chlorophenyl)methane (TCPM) and its isomers and three unknown DDT-related compounds previously identified in marine mammals. No clear trends were identified regarding DDT+ distribution in sediments. High DDT+ body burdens were found in biota irrespective of collection location, indicating widespread DDT+ contamination in the deep ocean of the SCB. TCPMs were detected in all biota samples except a single surface species, indicating that deep ocean sediment may be a source of DDT+ to the marine food web. This study demonstrates that the analysis of the larger suite of DDT+ is critical to trace deep ocean pollution of DDT in the SCB.
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