Analysis of brominated and chlorinated flame retardants, organophosphate esters, and polycyclic aromatic hydrocarbons in silicone wristbands used as personal passive samplers

Abstract

For the first time, we present an analytical method to simultaneously extract, fractionate, and quantify four groups of semi-volatile organic compounds (SVOCs) in silicone wristbands, including 35 polybrominated diphenyl ethers (PBDEs), 10 novel flame retardants (NFRs), 19 organophosphate esters (OPEs), and 13 polycyclic aromatic hydrocarbons (PAHs). Wristbands were extracted using ultrasonication, and cleaned and fractionated on two multi-layer columns: one consisting of neutral alumina, neutral silica and Florisil, and the other consisting of neutral alumina, neutral silica, and acidic silica. Method accuracy and precision were validated using spiked wristband samples (n = 8) and procedural blanks (n = 7). Average matrix spike percent recoveries for all target analytes were within 57 -107% with relative standard errors < 20%, with a few exceptions. This method was applied to analyze thirteen wristbands worn by ten participants for seven days; three participants wore two wristbands to evaluate duplicate samples. Percent recoveries of surrogate standards for all four groups of analytes in these wristbands were all within the 80 -120% range with a few exceptions: recoveries for 13 C 12 BDE-209 and for 13 C 12 -triphenyl phosphate ranged from 35 -62% and 69 -176%, respectively. The majority of target analytes were detected in at least half of worn wristbands. The levels of total PBDEs, NFRs, OPEs and PAHs in deployed wristbands ranged from 28.4 to 412 ng, 40.7 to 625 ng, 2,440 to 9,580 ng, and 76.2 to 1,240 ng, respectively.We developed an efficient method for the determination of a total of 77 analytes, including 35 PBDEs, 10 NFRs, 19 OPEs, and 13 PAHs, in silicone wristbands. This method offers a solution to chromatographic interferences associated with siloxanes from the wristband Romanak et al. Highlights •Silicone wristbands are a novel tool for assessing personal exposures • This is the first method for simultaneous quantitative analysis of 77 SVOCs 35 PBDEs, 9 NFRs, 19 OPEs, and 13 PAHs were simultaneously extracted and analyzed Romanak et al. •

Optimized workflow for unknown screening using gas chromatography high‐resolution mass spectrometry expands identification of contaminants in silicone personal passive samplers

“…In many instances, the cleanup of complex matrices is necessary to provide a viable sample that produces accurate and reproducible results for compounds that are well recovered in a particular sample cleanup condition. For silicone wristbands, many studies have optimized sample cleanup procedures that involve labor‐intensive steps including gel permeation chromatography, or multiple SPE procedures to accommodate a wide range of contaminants for targeted analysis or qualitative screenings 11,12,17 . Therefore, we investigated results from wristbands prepared without cleanup and compared them with samples that were passed through an SPE cartridge to remove some of the unwanted matrix.…”

“…For silicone wristbands, many studies have optimized sample cleanup procedures that involve labor-intensive steps including gel permeation chromatography, or multiple SPE procedures to accommodate a wide range of contaminants for targeted analysis or qualitative screenings. 11,12,17 Therefore, we investigated results from wristbands prepared without cleanup and compared them with samples that were passed through an SPE cartridge to remove some of the unwanted matrix. The MS data for the final extracts were processed following Figure 1 and the total number of features were recorded as well as features after filtering (Table 2).…”

“…Silicone wristbands have become a popular noninvasive technique for assessing personal exposure to environmental organic contaminants in children 1–6 and adults 7–28 . The wristband samplers are generally worn for a 7‐day period to capture a wide range of chemicals that represent typical environmental exposures.…”

“…The wristband samplers are generally worn for a 7‐day period to capture a wide range of chemicals that represent typical environmental exposures. Despite their promise, there remain unresolved challenges surrounding sample preparation and chemical analysis to extract and analyze potentially thousands of chemicals from the wristband in a single analytical method 12 . Current methods analyzing silicone wristbands primarily use targeted analysis 1–4 which limits the number of compounds detected in a single run to those that are previously selected for analysis.…”

“…Despite their promise, there remain unresolved challenges surrounding sample preparation and chemical analysis to extract and analyze potentially thousands of chemicals from the wristband in a single analytical method. 12 Current methods analyzing silicone wristbands primarily use targeted analysis [1][2][3][4] which limits the number of compounds detected in a single run to those that are previously selected for analysis. Gas chromatography (GC) coupled to high-resolution mass spectrometry (HRMS) is well suited to address these limitations due to the high mass resolving power that allows for non-target analysis to detect a greater number of compounds in a single run.…”