Integration of 103 Semivolatile Organic Compounds into One Multianalyte Method for Human Serum Analysis: An Innovative Approach within Exposure Assessment

Abstract

Semivolatile organic compounds (SVOCs) are frequently detected in the environment, and humans are exposed to a mixture of chemicals via multiple exposure pathways. However, there are few data on health outcomes caused by the cumulative exposure or toxicological interactions, due to the absence of simultaneous analytical methods. Herein, we present a method for simultaneous determination of 103 SVOCs, including seven phthalate esters, seven polychlorinated biphenyls, 16 polycyclic aromatic hydrocarbons, five polybromodiphenyl ethers, and 68 pesticides, in 0.5 mL of serum. The two-step extraction coupled with gas chromatography-tandem mass spectrometry was described with a single chromatographic run within 36.65 min. Methodological parameters such as recovery rates, matrix effects, and limits of detection were studied and complied with the validation guidelines. The absolute and relative recoveries ranged from 65.45% to 123.83%, and the relative standard deviations were ≤21.43%. The detection limits were <0.41 μg L–1. This method was then successfully applied to the analysis of 99 real serum samples. The developed protocol achieved a limit of quantification at a level of parts per billion for all compounds and presented benefits for the control of confounding factors, cumulative exposure, and risk assessment in population studies.

Tetraphenylphosphonium Chloride-Enhanced Ionization Coupled to Orbitrap Mass Spectrometry for Sensitive and Non-targeted Screening of Polyhalogenated Alkyl Compounds from Limited Serum

“…The MDL of CPs was 0.05–0.4 ng/mL, which was lower than the values reported in recent studies of CPs in human bloods (0.4–12.6 ng/mL in 1–6 mL of blood) (Table S5). The MDLs of OCPs, DPs, and BFRs were comparable to those obtained using GC–MS/MS analysis (0.01–0.53 ng/mL in 0.5 mL of blood) …”

“…Ph 4 PCl-enhanced ionization enabled the screening of 18 OCPs, namely, DDTs, HCHs, chlordanes, drins, endosulfans, mirex, chlordecone, dicofol, and toxaphene. The IDL of these compounds was 0.01–0.2 pg/μL; in particular, the IDL of DDTs, HCHs, mirex, and chlordecone was as low as 0.01 pg/μL, comparable to those of commonly used GC–MS (0.003–40 pg./μL) , or GC–MS/MS methods (0.001–4.1 pg./μL) ,, (Table S4).…”

“…Humans are continuously exposed to growing numbers of industrial chemicals, their impurities, and converted products from various environmental sources. , Among these chemicals, a large group of halogenated compounds, such as organochlorinated pesticides (OCPs), chlorinated paraffins (CPs), dechlorane plus (DPs), and brominated flame retardants (BFRs), has attracted global attention as most of these compounds are persistent organic pollutants (POPs). , Despite global regulatory bans or restrictions, such compounds are known to bioaccumulate in biotas at high concentrations . The high-throughput screening of halogenated compounds in biological samples is therefore vital for assessing exposure risks.…”

“…Various types of halogenated compounds (e.g., OCPs and BFRs) are determined in biotic samples using broadly applicable pretreatment procedures and subsequent group-specific instrumental analytical methods. , Gas chromatography (GC) coupled with mass spectrometry (MS) with different ion sources and corresponding parameters has been used for halogenated chemical analysis. , However, some halogenated compounds, such as long-chain chlorinated paraffins (LCCPs) and hexabromocyclododecanes (HBCDs), are not amenable to GC owing to their low vapor pressures and the tendency of their diastereomers to interconvert in the hot GC injectors. , Nevertheless, a recently developed method that couples chlorine ionization with liquid chromatography (LC)–MS offers the possibility of simultaneously scanning several polyhalogenated compounds as it involves the post-column addition of dichloromethane (DCM) coupled with LC–MS and enables the chlorine ionization of more than 200 CP congener groups . Compounds such as DPs and chlordane have also been chlorine-ionized using other mobile phase modifiers. ,, However, the chlorine-ionization efficiencies of the current methods are low.…”

The Potential of Sewage Sludge to Predict and Evaluate the Human Chemical Exposome

“…Biomonitoring provides an accurate method to estimate the exposure and bioaccumulation of organic chemicals through the direct measurement of the chemicals in the relevant biofluids and tissues. The analytical strategies (based on target screening) that have been commonly applied in human biomonitoring are biased because they only consider a very limited portion of the existing universe of chemicals. − Advances in high-resolution mass spectrometry (HRMS) have opened windows of opportunity for the identification of previously unknown chemicals of concern. The emergence of large chemical repositories, containing MS/HRMS data (e.g., Massbank, Massbank of North America, Metlin, HMDB, mzCloud), as well as tools for wide-scope suspect screening (e.g., NORMAN DSFP) or automatic annotation of unknowns (e.g., SIRIUS4, MetFrag), have provided an unprecedented possibility to perform large-scale investigations.…”