Chemometric Optimization of Solid-Phase Extraction Followed by Liquid Chromatography-Tandem Mass Spectrometry and Probabilistic Risk Assessment of Ultraviolet Filters in an Urban Recreational Lake

Abstract

Solid-phase extraction (SPE) of eleven ultraviolet filters (UVFs): benzophenone-1 (BP-1); benzophenone-3 (BP-3); benzophenone-4 (BP-4); isoamyl p-methoxycinnamate (IAMC), homosalate (HMS); 4-hydroxybenzophenone (4-HB); 4-methylbenzylidene camphor (4-MBC); octocrylene (OC); octyl dimethyl-p-aminobenzoate (OD-PABA); 2-ethylhexyl-4-methoxycinnamate (EHMC); and avobenzone (AVO), has been optimized using Plackett-Burman design, Box-Behnken design, and Derrindzer desirability function. Of the six SPE variables studied, the most influencing is the type of eluent followed by pH and the methanol content in the rinsing solvent. A method with good analytical performance was obtained by applying optimal SPE conditions and liquid chromatography-tandem mass spectrometry (LC-MS/MS), with the method detection limit ranging from 0.1 to 5 ng/L, recovery from 44% to 99%, and relative standard deviation (RSD) within 19%. This method was used to analyze the content of UVFs in an urban lake (Sava Lake, Serbia). UVFs occurrence, geostatistical distribution, and associated environmental risk are highly dependent on recreational activities. The average concentrations of UVFs ranged from 0.3 to 113 ng/L, and the most present substance was EHMC, followed by 4-MBC and BP-3. The spatial distribution of the risk quotient (RQ = 0.04–1.7) inside the lake is highly correlated with the number of people bathing and swimming. Human exposure through the dermal pathway is higher than ingestion for most UVFs. Monte Carlo simulation of probabilistic risk assessment estimated the percentile P10, P50, P90 of 12.7; 17.3; 47.5 and 20.1; 27.6; 77.5 ng/kg∙day for total human exposure of adults and children, respectively. The sensitivity analysis revealed that the health risk estimate depends mostly on the content of EHMC, HMS, and 4-MBC, while the most influential exposure variables were human body weight and skin surface area. There is no serious concern to human health due to UVFs in the short term; however, a high ecological risk in some parts of the lake is estimated.

Dispersive liquid–liquid microextraction and Monte Carlo simulation of margin of safety for octocrylene, EHMC, 2ES, and homosalate in sunscreens

“…EHMC was also reported as the most common organic UV filter in cosmetics (Chaiyabutr et al, 2021). Also, a study on the occurrence of 11 UVFs in an urban recreational lake in the same city where the studied sunscreen products were purchased revealed EHMC to have the highest concentrations of all UVFs in water (Lukić et al, 2022).…”

“…It was reported that potential health hazards and risks from UVFs in sunscreen PCPs are based mainly on the direct dermal exposure route (Raslan et al, 2020). However, different UVFs contribute vastly differently to potential health risks (Luki c et al, 2022). In addition, the combined risk depends on the concentration of different UVFs in sunscreens and human exposure.…”

Influence of Ultrasonic and Chemical Pretreatments on Quality Attributes of Dried Pepper (Capsicum annuum)

“…The desirability function [ 32 ] was used to find the optimal conditions of the examined factors to define the optimal quality levels for different responses. The desirability function is a quick transformation of different responses to one objective function [ 33 ]. The desirability function has two steps: (1) transformation of every individual response to an individual desirability function ( d i ) that ranges from 0 to 1 ( d i = 0 undesirable response; d i = 1 desirable response) and (2) calculating of overall desirability ( D ) by taking the geometric average of all individual desirability values (Equation (1)).…”

Benzophenones in the Environment: Occurrence, Fate and Sample Preparation in the Analysis

“…Additionally, after a comparison of the pressurized liquid extraction with Soxhlet and ultrasound-assisted methods, the recoveries were proved to be better with the pressurized liquid extraction (90.6–107.8%) compared with 83.5–88.7% and 81.4–85.2% for the other two methods, respectively [ 71 ]. Another SPE method using Oasis cartridges packed with 100 mg HLB sorbent was proposed by Luki et al to preconcentrate and detect four BPs [ 72 ]. The working parameters were optimized by an experimental design which revealed that the elution solvent and percentage of methanol and pH were the influencing factors.…”