Filling gaps between exposure modeling and the analysis of urinary biomarkers using personal air monitoring: An intervention study of permethrin used in home insecticide spray.

Permethrin is one of the most widely used active ingredients in spray-type home insecticides. However, indoor permethrin exposure resulting from the use of home insecticides is not well-characterized, as measured permethrin concentrations in indoor environmental and biological media with a known application rate are scarce. We conducted an intervention study with four participants for seven days. We conducted personal air monitoring and collected 24-h urine samples in which we quantified time-weighted average (TWA) permethrin concentrations in indoor air (Cair ) and urinary concentrations of two permethrin metabolites, 3-phenoxybenzoic acid (3-PBA) and cis/trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylic acid (cis/trans-DCCA). We also estimated (1) TWA Cair using a simple indoor air model and (2) urinary excreted (UE) mass using a simple excretion model with both estimated and measured TWA Cair . Measurements of TWA Cair from personal air monitoring were lower than those estimated from the indoor model by a factor of 2.9 to 49.4. The ratio of estimated to measured UE mass ranged 3.5-18.2 when using estimated TWA Cair and 1.1-2.9 when using measured TWA Cair . Smaller ratios in estimating internal permethrin exposure from personal air monitoring suggest that personal air monitoring could reduce uncertainties in permethrin exposure assessment resulting from the use of spray-type insecticides.

Target and suspect screening of (new) psychoactive substances in South Korean wastewater by LC-HRMS.

New psychoactive substances (NPS) are a type of abused drug designed to mimic the effects of the currently known illicit drugs, whose structures are constantly changing to escape surveillance. The quick identification of NPS use in the community therefore demands immediate action. This study aimed to develop a target and suspect screening method using LC-HRMS to identify NPS in wastewater samples. An in-house database of 95 traditional and NPS was built using the reference standards, and an analytical method was developed. Wastewater samples were collected from 29 wastewater treatment plants (WWTP) across South Korea, representing 50 % of the total population. The psychoactive substances in waste water samples were screened using in-house database and developed analytical methods. A total of 14 substances were detected in the target analysis, including three NPS (N-methyl-2-AI, 25E-NBOMe, and 25D-NBOMe) and 11 traditional psychoactive substances and their metabolites (zolpidem phenyl-4-COOH, ephedrine, ritalinic acid, tramadol, phenmetrazine, phendimetrazine, phentermine, methamphetamine, codeine, morphine, and ketamine). Out of these, N-methyl-2-AI, zolpidem phenyl-4-COOH, ephedrine, ritalinic acid, tramadol, phenmetrazine, and phendimetrazine were detected with a detection frequency of over 50 %. Primarily, N-methyl-2-Al was detected in all the wastewater samples. Additionally, four NPSs (amphetamine-N-propyl, benzydamine, isoethcathinone, methoxyphenamine) were tentatively identified at level 2b in a suspect screening analysis. This is the most comprehensive study to investigate NPS using target and suspect analysis methods at the national level. This study raises a need for continuous monitoring of NPS in South Korea.

Three years of wastewater surveillance for new psychoactive substances from 16 countries.

The proliferation of new psychoactive substances (NPS) over recent years has made their surveillance complex. The analysis of raw municipal influent wastewater can allow a broader insight into community consumption patterns of NPS. This study examines data from an international wastewater surveillance program that collected and analysed influent wastewater samples from up to 47 sites in 16 countries between 2019 and 2022. Influent wastewater samples were collected over the New Year period and analysed using validated liquid chromatography - mass spectrometry methods. Over the three years, a total of 18 NPS were found in at least one site. Synthetic cathinones were the most found class followed by phenethylamines and designer benzodiazepines. Furthermore, two ketamine analogues, one plant based NPS (mitragynine) and methiopropamine were also quantified across the three years. This work demonstrates that NPS are used across different continents and countries with the use of some more evident in particular regions. For example, mitragynine has highest mass loads in sites in the United States, while eutylone and 3-methylmethcathinone increased considerably in New Zealand and in several European countries, respectively. Moreover, 2F-deschloroketamine, an analogue of ketamine, has emerged more recently and could be quantified in several sites, including one in China, where it is considered as one of the drugs of most concern. Finally, some NPS were detected in specific regions during the initial sampling campaigns and spread to additional sites by the third campaign. Hence, wastewater surveillance can provide an insight into temporal and spatial trends of NPS use.

Evaluation of sample preparation methods for suspect and non-target screening in water, sediment, and biota samples using gas chromatography coupled to high-resolution mass spectrometry.

In this study, the sample preparation methods were proposed for the suspect and non-target screening (SNTS) using gas chromatography coupled to high-resolution mass spectrometry in the aquatic environment. The pretreatment methods were evaluated based on detection rates, recoveries, and screening detection limits (SDLs) for 316 substances spiked into surface water, sediment, and biota samples. The detection rates of the spiked compounds were 92.1 % and 98.7 % by the sample preparation methods for water (solid-phase extraction using HLB cartridge) and sediment (ultrasonic extraction (USE) with HLB cartridge clean-up), respectively. Similarly, USE with HLB cartridge clean-up gave the highest detection rate (87.9 %) for biota samples; however, additional pretreatment method using deactivated silica gel clean-up was necessary for the detection of persistent organic pollutants (POPs). The SDL ranges of spiked compounds by the suggested pretreatment methods were 0.01-23.5 ng/L for surface water, 0.02-37.5 ng/g dry weight for sediment, and 0.01-12.2 ng/g wet weight for biota. Although some pollutants, such as POPs had SDLs that were higher than the levels normally detected in the aquatic environment as reported in previous studies, the analytical methods suggested in the present study were satisfactory for the SNTS of most pollutants originated from anthropogenic sources.

Exposure to permethrin used as a home insecticide: A case study comparing model predictions and excretion of metabolites.

Pyrethroids have been widely used as an active ingredient in home insecticide products since the 1960 s. Although their occurrence in indoor environments has been studied, the contribution of home insecticide application to the aggregate exposure to pyrethroids is not well known. The objective of this study was to estimate the consumer exposure to permethrin, a representative pyrethroid, via the use of home insecticide spray during the summer season using biomonitoring and personal exposure modeling. Exposure to permethrin was assessed by analyzing its urinary metabolites, 3-phenoxybenzoic acid (3-PBA) and cis/trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropan carboxylic acid (cis/trans-DCCA), for a group of consumers (n = 27). The levels of metabolites were also compared with those predicted by a screening exposure model considering personal exposure parameters. The levels of metabolites in 15 participants increased significantly (p < 0.05) with the application of home insecticide products, thereby suggesting that the heavy use of home insecticides during summer could be an important exposure route of permethrin in addition to other sources, such as food consumption. The total amount of excreted 3-PBA and cis/trans-DCCA was lower than the amount estimated by the exposure model for most participants by a factor of 0.9-861.0. These differences could be attributed to the rapid loss of permethrin after application, including sorption to indoor surfaces, reaction with indoor substances, individual biological variations, and ventilation during application. However, the screening exposure model used for the initial safety assessment of biocidal products generally performed well because it did not underestimate the personal exposure to permethrin during the application of home insecticide spray.

Occurrences of microorganic pollutants in the Kumho River by a comprehensive target analysis using LC-Q/TOF-MS with sequential window acquisition of all theoretical fragment ion spectra (SWATH).

In this study, simultaneous identification and semi-quantification of hundreds of micropollutant compounds, including pharmaceutical and personal care products (PPCPs) and pesticides were performed in river and effluent samples from the Kumho River Basin using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-Q-TOF/MS) with sequential window acquisition of all theoretical fragment ion spectra (SWATH). In total, 85 compounds (29 pesticides and 56 PPCPs) were identified. The highest proportions of PPCP residues were detected in the downstream area of the Kumho River, close to the central city. On the other hand, the highest proportions of pesticide residues were observed upstream, near agricultural land and golf courses. Additionally, the highly exposable chemicals were prioritized using a scoring and ranking system based on their concentration and detection frequency. Thus, 20 compounds (7 pesticides and 13 PPCPs) with scores of 200 or higher were defined as highly exposable compounds in Kumho River basin.

Perfluoroalkyl substances and pharmaceuticals removal in full-scale drinking water treatment plants.

The concentrations of 14 perfluoroalkyl substances (PFASs) and 46 pharmaceuticals in raw water and drinking water from five drinking water treatment plants were determined to assess removal of the chemicals during treatment. 10 out of 14 PFASs were detected in the raw and drinking water samples. The mean perfluorohexane sulfonate concentrations in raw and drinking water were the highest with levels of 106 and 69.6 ng L-1, respectively and the other PFAS concentrations were lower. The ∑14PFAS and individual PFAS removal efficiencies for the treatment plants were -36.9% to 70.7% (mean 31.3%) but the granular activated carbon process removed >80% of the total amount of long-chain PFASs that was removed. The removal efficiency increased as the perfluorocarbon chain length increased. The removal efficiencies increased by 14.2% and 11.2% from the shortest to the longest perfluoroalkyl carboxylic acid and perfluoroalkyl sulfonic acid chain lengths, respectively. 20 out of 46 pharmaceuticals were detected in the raw water samples, but most were removed completely during treatment. Only caffeine, carbamazepine, crotamiton, fenbendazole, metformin, and sulfamethoxazole were detected in the drinking water samples. Oxidation processes contributed >90% of the overall treatment plant removal efficiency except for metformin.

Occurrence and distribution of pharmaceutical and personal care products, artificial sweeteners, and pesticides in groundwater from an agricultural area in Korea.

This study investigated the occurrence and distribution of 33 pharmaceutical and personal care products (PPCPs), five artificial sweeteners (ASs), and six pesticides in groundwater in rural agricultural and rural non-agricultural area in South Korea. A total of 31 target compounds (15 antibiotics, four anthelmintics, seven other PPCPs, four ASs, and one pesticide) were detected in agricultural groundwater at concentrations from not detected (ND) to 49.3 ng/L for PPCPs, ND to 1340 ng/L for ASs, and ND to 116 ng/L for pesticides. Four target compounds (two PPCPs and two ASs) were detected in rural non-agricultural groundwater in the range of 0.085-5.74 ng/L for PPCPs and 5.64-1330 ng/L for ASs. Among the target compounds, ASs, especially acesulfame (detection frequency 69% in rural agricultural areas and 100% in the rural non-agricultural area) were predominantly detected in both agricultural (mean: 32.9 ng/L) and non-agricultural (mean: 536 ng/L) groundwater, but different occurrence patterns were observed according to the sources of contamination. Known markers of sewage leakage were detected in both agricultural and non-agricultural groundwater samples (e.g., acesulfame (69% and 100%), caffeine (88% and 100%), and crotamiton (62% and 100%)), while compounds related to agricultural activities were only observed in agricultural groundwater (e.g., sulfathiazole (38%), sulfamethoxazole (31%), oxfendazole (69%), and carbofuran (42%)).

Occurrence and distribution of carbamazepine, nicotine, estrogenic compounds, and their transformation products in wastewater from various treatment plants and the aquatic environment.

The concentrations and fates of carbamazepine and metabolites (CBMs), nicotine and metabolites (NCTs), estrogenic compounds and metabolites (Es) in various water samples were investigated. Different concentrations were found for water from different sources. The concentrations of these pharmaceuticals and personal care products and their metabolites in human waste treatment plant (HTP) influents (0.08-173 µg L-1) were higher than in the other influent samples and the lowest levels were observed in hospital wastewater treatment plant influents (0.03-7.33 µg L-1). The concentrations were higher in HTP effluents (0.01-11.2 µg L-1) than in the other effluent samples and lowest in sewage treatment plant effluents (0.003-1.26 µg L-1). The NCTs were the most frequently detected pharmaceuticals and personal care products (concentration range 0.05-89.6 µg L-1) in the wastewater treatment plant influents, but the CBMs were found at the highest concentrations (0.003-6.88 µg L-1). 10, 11-Dihydro-10, 11-dihydroxycarbamazepine was the most abundant of the CBMs in the wastewater treatment plants and water samples. Trans-3'-hydroxycotinine was dominant in the HTP and hospital wastewater treatment plant influents, whereas the parent NCT was dominant in the sewage treatment plant influents and in all the effluent and other water samples. Estriol was the dominant estrogenic compound in the HTP and hospital wastewater treatment plant influents. Estriol and estrone were found in many of the HTP influents, but estrone was dominant in the effluent and other water samples. The total removal efficiencies for the CBMs, NCTs, and estrogenic compounds for the treatment plants were -101% to 56%, 2.9%-99%, and >98%, respectively.