Rapid Screening of Urinary 1-Hydroxypyrene Glucuronide by Multisegment Injection–Capillary Electrophoresis–Tandem Mass Spectrometry: A High-Throughput Method for Biomonitoring of Recent Smoke Exposures

Abstract

Urinary 1-hydroxypyrene (HP) is a widely used biomarker of polycyclic aromatic hydrocarbon exposure relevant for biomonitoring the deleterious health impacts from tobacco smoke and ambient air pollution, as well as the hazards of certain occupations. Conventional methods for urinary HP analysis based on liquid chromatography with native fluorescence detection or tandem mass spectrometry (MS/MS) and gas chromatography–mass spectrometry (GC–MS) are limited by low sample throughput and complicated sample workup protocols that are prone to bias. Herein, we introduce a high throughput method to directly analyze the intact glucuronide conjugate of HP (HP-G) in human urine after a simple acidified ether extraction procedure when using multisegment injection–capillary electrophoresis–tandem mass spectrometry (MSI–CE–MS/MS). Multiplexed analyses of 13 independent urine extracts are achieved in a single run (<3 min/sample) with stringent quality control while avoiding enzyme deconjugation and precolumn chemical derivatization. Method validation demonstrates good technical precision (CV = 7.7%, n = 45) and accuracy with a mean recovery of (93 ± 3%) for urinary HP-G at three concentration levels with adequate detection limits (7 ng/L, S/N = 3). An interlaboratory method comparison of urine samples collected from firefighters deployed in the 2016 Fort McMurray wildfire also confirms good mutual agreement with an acceptable negative bias (mean bias = 15%, n = 55) when measuring urinary HP-G by MSI–CE–MS/MS as compared to total hydrolyzed urinary HP by GC–MS due to the low residual levels of free HP and its sulfate conjugate. This multiplexed separation platform is optimal for large-scale biomonitoring studies of air pollution relevant to global health as well as occupational smoke exposures in firefighters susceptible to dermal PAH absorption when using personal protective equipment.

Unearth the Luminescence Potential of Metal–Organic Frameworks: Adopting a Feasible Strategy to Fabricate One Ratiometric Fluorescence Sensor for Monitoring Both 1-Hydroxypyrene and Cu2+

“…From Figure d, we can see that I 613nm / I 465nm exhibit a good linear relationship with the concentration of 1-HP within 0–1 mg/mL, and the correlation can be rationalized by the equation I 613nm / I 465nm = 0.52783 – 0.94255 log­[1-HP] ( R 2 = 0.98909), where [1-HP] represents the concentration of 1-HP. Based on eq S1 shown in the SI, the detection limit (LOD) of the sensor Eu­(TTA) 0.2 @9-1-UMOF toward 1-HP is calculated to be 4.06 × 10 –6 mg/mL, which is close to or better than that of some determination methods reported in previous literature works ,− (Table S4).…”

“…Polycyclic aromatic hydrocarbons (PAHs) are a class of organic contaminants existing in the environment ubiquitously and persistently, which can easily enter the human body through intact skin, respiratory tract, and digestive tract . Over the past years, because of their strong carcinogenic, teratogenic, and mutagenic nature, evaluating the PAH content in the body of occupationally exposed people has been a widespread concern . According to some studies, 1-hydroxypyrene (1-HP) is a specific metabolite of PAHs in urine, thereby we can use it as a reliable and valuable biomarker to estimate the degree of human exposure to PAHs. , Owing to possessing catalytic and oxidative properties, Cu 2+ is confirmed as an essential trace element in fundamental physiological processes .…”

Current applications of capillary electrophoresis‐mass spectrometry for the analysis of biologically important analytes in urine (2017 to mid‐2021): A review

“…Valuable data were obtained for phenylketonuria [ 77 ], rheumatoid arthritis [ 78 ], systematic lupus erythematosus [ 79 , 80 ], chronic obstructive pulmonary disease [ 81 ], chronic graft‐versus‐host disease [ 82 ], liver fibrosis [ 83 ], and periprosthetic joint infection [ 84 ]. Besides the study of various diseases, this technique allowed the generation of the biomarker classifier of mice aging applicable to humans [ 85 ], the prediction of 1‐year mortality after discharge from the intensive care [ 86 ], and rapid screening of biomarkers indicating recent smoke exposure [ 87 ].…”

Reliability of urinary charged metabolite concentrations in a large-scale cohort study using capillary electrophoresis-mass spectrometry

“…We have already reported the reliability and accuracy of plasma metabolites in cohort studies through another study conducted by us 13 . Previous studies have investigated the measurement reliability for urinary iodine 20 or urinary hydroxypyrene glucuronide 21 by CE-MS. However, there are few studies which comprehensively evaluate validation for urinary metabolites in large-scale epidemiological studies.…”