Endocrine Disruptors Research Articles

Advancements and Challenges in Nanoscale Zero-Valent Iron-Activated Persulfate Technology for the Removal of Endocrine-Disrupting Chemicals

Endocrine-disrupting chemicals are a new class of pollutants that can affect hormonal metabolic processes in animals and humans. They can enter the aquatic environment through various pathways and gradually become enriched, thus posing a serious threat to the endocrine and physiological systems of both animals and humans. Nano zero-valent iron has promising applications in endocrine disruptor removal due to its excellent reducing properties and high specific surface area. However, given the dispersed focus and fragmented results of current studies, a comprehensive review is still lacking. In this paper, it was analyzed that the types of endocrine disruptors and their emission pathways reveal the sources of these compounds. Then, the main technologies currently used for endocrine disruptor treatment are introduced, covering physical, chemical, and biological treatment methods, with a special focus on persulfate oxidation among advanced oxidation technologies. Also, the paper summarizes the various activation methods of persulfate oxidation technology and proposes the nZVI-activated persulfate technology as the most promising means of treatment. In addition, this paper reviews the research progress of different modification methods of nZVI in activating persulfate for the removal of EDCs. Finally, the discussion includes recycling studies of nZVI/PS technology and emphasizes the urgency and importance of endocrine disruptor treatment. The review of this paper provides further scientific basis and technical support for nZVI/PS technology in the field of endocrine disruptor management.

Maintaining the physiological stability during artificial spawning of Liza ramada in captivity

AbstractIn captivity, the physiological condition of mature brood fish has a vital role for a successful artificial spawning. Therefore, the current study aimed to minimize endocrine and metabolic disruptions during routine handling, transportation, and acclimatization during artificial spawning in L. ramada. Here, we determined the impacts of transportation and handling, as well as the acclimation to different salinities on the levels of total thyroxine (T4), triiodothyronine (T3), cortisol, and glucose in the mature L. ramada females. The transportation procedures of cultured mature females of L. ramada without anesthesia induced physiological stress as reflected with a rapid elevation in serum cortisol and glucose concomitant with a decrease in T4 within 3 h. However, the anesthesia protocol and the gradual acclimatization to seawater (24 h) were successful in maintaining baseline concentrations of the measured hormones in mature L. ramada females. The recorded levels of thyroid hormones (T4 and T3) and cortisol proved that 40 mg l−1 of clove oil was superior to anesthetic tricaine methane sulfonate (MS-222). In parallel, clove oil as an anesthetic has a rapid induction time and longer recovery time compared to MS-222 in L. ramada anesthesia. So, the slow acclimation and clove oil anesthesia were crucial during the induction of spawning in L. ramada. Indeed, all injected females were physiologically stable and spawned within the appropriate time consistent with the histological observation of both ovary and liver. Together, these findings recommend that maintaining the physiological stability of broodstock is critical for the successful artificial spawning of mullet.

Can Mammalian Reproductive Health Withstand Massive Exposure to Polystyrene Micro- and Nanoplastic Derivatives? A Systematic Review

The widespread use of plastics has increased environmental pollution by micro- and nanoplastics (MNPs), especially polystyrene micro- and nanoplastics (PS-MNPs). These particles are persistent, bioaccumulative, and linked to endocrine-disrupting toxicity, posing risks to reproductive health. This review examines the effects of PS-MNPs on mammalian reproductive systems, focusing on oxidative stress, inflammation, and hormonal imbalances. A comprehensive search in the Web of Science Core Collection, following PRISMA 2020 guidelines, identified studies on the impact of PS-MNPs on mammalian fertility, including oogenesis, spermatogenesis, and folliculogenesis. An analysis of 194 publications revealed significant reproductive harm, such as reduced ovarian size, depleted follicular reserves, increased apoptosis in somatic cells, and disrupted estrous cycles in females, along with impaired sperm quality and hormonal imbalances in males. These effects were linked to endocrine disruption, oxidative stress, and inflammation, leading to cellular and molecular damage. Further research is urgently needed to understand PS-MNPs toxicity mechanisms, develop interventions, and assess long-term reproductive health impacts across generations, highlighting the need to address these challenges given the growing environmental exposure.

Sustainability assessment in food analysis: the application of Green Analytical Chemistry tools to phthalate residue analysis in edible oils

Edible oils are essential in daily diet due to their high contribution of fatty acids, fat-soluble vitamins, and triglycerides. During the processes of growing, processing, storage, transport, or packaging, they can be contaminated by ubiquitous phthalate esters, considered endocrine disruptors. Thus, analytical methodologies to allow tight control of their presence are mandatory. Several sample treatments have been considered in this study: microwave-assisted extraction (MAE), liquid-liquid extraction (LLE), dispersive solid phase extraction (DSPE), magnetic SPE (MSPE), solid phase microextraction (SPME), Surface-enhanced Raman spectroscopy (SERS) or its combinations. However, the selection of an analytical procedure is usually performed from an Analytical Chemistry perspective, without considering factors such as the sustainability of the selected methodology and/or its impact on the environment. In this sense, the Green Analytical Chemistry strategy can play an important role. To demonstrate this fact, six different analytical procedures have been evaluated in terms of sustainability by using several greenness evaluation tools. Procedures from MAE-gel permeation chromatography (GPC)-SPE till SERS, showing adequate analytical characteristics, have been selected. The application of Analytical GREEnness calculator (AGREE), AGREE preparation (AGREE prep), and blue applicability grade index (BAGI) tools showed that MAE-GPC-SPE was the less green analytical procedure while SERS was the greener one. The BAGI evaluation showed that headspace (HS) and SERS were the most applicable procedures.

Endocrine Disruptors Attitude Scale: A Scale Development Study

Endocrine Disruptors Attitude Scale: A Scale Development Study

Susceptibility of Human Spermatozoa to Titanium Dioxide Nanoparticles: Evaluation of DNA Damage and Biomarkers

Nowadays, developing countries have seen a reduction in male reproductive parameters, and it has been linked to the exposure of endocrine disrupting chemicals (EDCs), which are able to mimic or disrupt steroid hormone actions. Also, nanoparticles have shown effects on the male reproductive system, in particular the use of TiO2-NPs in drugs, cosmetics, and food as pigment additives, and, thanks to their small size (1–100 nm), provide themselves the opportunity to be internalized by the body and pass the blood–testis barrier (BTB). Therefore, TiO2-NPs can act on spermatogenesis and spermatozoa. In this study, we carried out an in vitro assay on human spermatozoa to evaluate the effects of TiO2-NPs at the concentrations of 500, 250, 100, and 50 ppm. Exposure did not statistically alter sperm parameters (e.g., motility and viability) but induced damage to sperm DNA and the expression of biomarkers by spermatozoa. This immunofluorescence investigation showed a positivity for biomarkers of stress (HSP70 and MTs) on the connecting piece of spermatozoa and also for sex hormone binding globulin (SHBG) biomarkers. The SHBG protein acts as a carrier of androgens and estrogens, regulating their bioavailability; therefore, its expression in the in vitro assay did not rule out the ability of TiO2-NPs to act as endocrine disruptors.

Maternal probiotic supplementation protects against PBDE-induced developmental, behavior and metabolic reprogramming in a sexually dimorphic manner: Role of gut microbiome

AbstractPolybrominated diphenyl ethers (PBDEs) are endocrine-disrupting persistent organic pollutants (POPs) used as flame retardants in a wide range of commercial applications. We have previously reported neurobehavioral and metabolic reprogramming produced by developmental PBDEs. PBDEs perturb the microbiome, an influencer of life-long health, while probiotic supplementation with Limosilactobacillus reuteri (LR) can avert neurobehavioral and endocrine disruption. We, therefore, tested the hypothesis that perinatal maternal LR supplementation would protect gut microbiome richness and diversity, developmental milestones, adult neurobehavior and metabolic homeostasis in PBDE-exposed offspring. C57BL/6N dams were orally exposed to a commercial penta-mixture of PBDEs, DE-71, at 0.1 mg/kg/day, or corn oil vehicle (VEH/CON) during gestation and lactation. Mice offspring received DE-71 or VEH/CON with or without co-administration of LR (ATCC-PTA-6475) indirectly via their mother from gestational day (GD) 0 until postnatal day (P)21 (Cohort 1), or continued to receive LR directly from P22 through adulthood (Cohort 2). Results of fecal 16S rRNA sequencing indicated age- and sex-dependent effects of DE-71 on gut microbial communities. Maternal LR treatment protected against DE-71-induced reduction in α-diversity in P22 females and against β-diversity alterations in P30 males. In females, DE-71 changed the relative abundance of specific bacterial taxa, such as Tenericutes and Cyanobacteria (elevated) and Deferribacterota (reduced). In males, several Firmicutes taxa were elevated, while Proteobacteria, Chlamydiae, and several Bacteroidota taxa were reduced. The number of disrupted taxa normalized by maternal LR supplementation was as follows: 100% in P22 females and 33% in males at P22 and 25% at P30. Maternal LR treatment protected against DE-71-induced delay of postnatal body weight gain in males and ameliorated the abnormal timing of incisor eruption in both sexes. Further, DE-71 produced exaggerated digging in both sexes as well as locomotor hyperactivity in females, effects that were mitigated by maternal LR only in females. Other benefits of LR therapy included normalization of glucose tolerance, insulin-to-glucose ratio and plasma leptin in adult DE-71 females (Cohort 2). This study provides evidence that probiotic supplementation can mitigate POP-induced reprogramming of neurodevelopment, adult neurobehavior, and glucose metabolism in association with modified gut microbial community structure in a sex-dependent manner.

Identification of Estrogen-Responsive Proteins in Mouse Seminal Vesicles Through Mass Spectrometry-Based Proteomics

Background: Although estrogenic compounds promise therapeutic potential in treating various conditions, concerns regarding their endocrine-disrupting effects have been raised. Current methodologies for screening estrogenicity in rodent models are limited to the female-specific uterotrophic bioassay. Studies have reported enlargement of the seminal vesicles in orchiectomized males treated with estrogens. However, identifying estrogenicity strictly through changes in wet weights is uninformative regarding the molecular mechanisms of these agents. Therefore, protein-based biomarkers can complement and improve the sensitivity of weight-based assessments. To this end, we present a discovery-driven proteomic analysis of 17β-estradiol’s effects on the seminal vesicles. Methods: We treated orchidectomized mice with the hormone for five days and used the vehicle-treated group as a control. Seminal vesicles were analyzed by shotgun approach using data-dependent nanoflow liquid chromatography–tandem mass spectrometry and label-free quantification. Proteins found to be differentially expressed between the two groups were processed through a bioinformatics pipeline focusing on pathway analyses and assembly of protein interaction networks. Results: Out of 668 identified proteins that passed rigorous validation criteria, 133 were regulated significantly by 17β-estradiol. Ingenuity Pathway Analysis® linked them to several hormone-affected pathways, including those associated with immune function such as neutrophil degranulation. The altered protein interaction networks were also related to functions including endocrine disruption, abnormal metabolism, and therapeutic effects. Conclusions: We identified several potential biomarkers for estrogenicity in mouse seminal vesicles, many of them not previously linked with exogenous 17β-estradiol exposure.

Association of joint exposure to organophosphorus flame retardants and phthalate acid esters with gestational diabetes mellitus: a nested case-control study

BackgroundOrganic phosphate flame retardants (OPFRs) and phthalate acid esters (PAEs) are common endocrine-disrupting chemicals that cause metabolic disorders. This study aimed to assess the association between joint exposure to OPFRs and PAEs during early pregnancy in women with gestational diabetes mellitus (GDM).MethodsSeven OPFRs and five PAEs were detected in the urine of 65 GDM patients and 100 controls using gas chromatography-tandem triple quadrupole mass spectrometry (GC-MS). The association of OPFRs and PAEs with GDM was assessed using logistic regression, weighted quantile sum (WQS) regression, and Bayesian kernel machine regression (BKMR) models.ResultsLevels of dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DEHP), diethyl phthalate (DEP), dimethyl phthalate (DMP), tris (2-butoxyethyl) phosphate (TBEP), tributyl phosphate (TBP), tris (2-chloroethyl) phosphate (TCEP), tris (1,3-dichloro-2-propyl) phosphate (TDCPP), tri-ortho-cresyl phosphate (TOCP), and triphenyl phosphate (TPHP) increased in the GDM group, and the OPFRs and PAEs, except for BBP and TMCP, were associated with GDM in the logistic regression analysis. In the WQS model, the mixture of OPFRs and PAEs was significantly positively associated with GDM (OR = 3.29, 95%CI = 1.27–8.51, P = 0.014), with TDCPP having the highest WQS index weight. BKMR analysis reinforced these results, showing that the overall association of joint exposure to the OPFRs and PAEs with GDM increased at exposure levels of the 55th to 75th percentiles. Independent exposure to TDCPP (OR = 1.42, 95%CI = 1.09–1.86, P = 0.011) and TBEP (OR = 1.29, 95%CI = 1.04–1.60, P = 0.023) were associated with an increased risk of GDM.ConclusionsEnvironmental exposure to OPFRs and PAEs is significantly associated with GDM. These findings provide evidence for the adverse effects of exposure to OPFRs and PAEs on the health of pregnant women.

Intercontinental Insights into Autism Spectrum Disorder: A Synthesis of Environmental Influences and DNA Methylation

Abstract Autism Spectrum Disorder (ASD) is a complex neurodevelopmental disorder characterized by a broad range of symptoms. The etiology of ASD is thought to involve complex gene-environment interactions, which are crucial to understanding its various causes and symptoms. DNA methylation is an epigenetic mechanism that potentially links genetic predispositions to environmental factors in the development of ASD. This review provides a global perspective on ASD, focusing on how DNA methylation studies may reveal gene-environment interactions characteristic of specific geographical regions. It delves into the role of DNA methylation in influencing the causes and prevalence of ASD in regions where environmental influences vary significantly. We also address potential explanations for the high ASD prevalence in North America, considering lifestyle factors, environmental toxins, and diagnostic considerations. Asian and European studies offer insights into endocrine-disrupting compounds (EDC), persistent organic pollutants (POP), maternal smoking, and their associations with DNA methylation alterations in ASD. In areas with limited data on DNA methylation and ASD, such as Africa, Oceania, and South America, we discuss prevalent environmental factors based on epidemiological studies. Additionally, the review integrates global and country-specific prevalence data from various studies, providing a comprehensive picture of the variables influencing ASD diagnoses over region and year of assessment. This prevalence data, coupled with regional environmental variables and DNA methylation studies, provides a perspective on the complexities of ASD research. Integrating global prevalence data, we underscore the need for a comprehensive global understanding of ASD’s complex etiology. Expanded research into epigenetic mechanisms of ASD is needed, particularly in underrepresented populations and locations, to enhance biomarker development for diagnosis and intervention strategies for ASD that reflect the varied environmental and genetic landscapes worldwide.

Characterization of Chemical Exposome in A Paired Human Preconception Pilot Study.

Parental preconception exposure to synthetic chemicals may have critical influences on fertility and reproduction. Here, we present a robust LC-MS/MS method covering up to 95 diverse xenobiotics in human urine, serum, seminal and follicular fluids to support exposome-wide assessment in reproductive health outcomes. Extraction recoveries of validated analytes ranged from 62% to 137% and limits of quantification from 0.01 to 6.0 ng/mL in all biofluids. We applied the validated method to a preconception cohort of Australian couples (n = 30) receiving fertility treatment. In total, 36 and 38 xenobiotics were detected across the paired biofluids of males and females, respectively, including PFAS, parabens, organic UV-filters, plastic additives, antimicrobials, and other industrial chemicals. Results showed 39% of analytes in males and 37% in females were equally detected in paired serum, urine, and reproductive fluids. The first detection of the sunscreen ingredient avobenzone and the industrial chemical 4-nitrophenol in follicular and seminal fluids suggests it can cross both blood-follicle/testis barriers, indicating potential risks for fertility. Further, the blood-follicle transfer of perfluorobutanoic acid, PFOA, PFHxS, PFOS, and oxybenzone corroborate that serum concentrations can be reliable proxies for assessing exposure within the ovarian microenvironment. In conclusion, we observed significant preconception exposure to multiple endocrine disruptors in couples and identified potential xenobiotics relevant to male and female fertility impairments.

Endocannabinoid System and Metabolism: The Influences of Sex

The endocannabinoid system (ECS) is a lipid signaling system involved in numerous physiological processes, such as endocrine homeostasis, appetite control, energy balance, and metabolism. The ECS comprises endocannabinoids, their cognate receptors, and the enzymatic machinery that tightly regulates their levels within tissues. This system has been identified in various organs, including the brain and liver, in multiple mammalian and non-mammalian species. However, information regarding the sex-specific regulation of the ECS remains limited, even though increasing evidence suggests that interactions between sex steroid hormones and the ECS may ultimately modulate hepatic metabolism and energy homeostasis. Within this framework, we will review the sexual dimorphism of the ECS in various animal models, providing evidence of the crosstalk between endocannabinoids and sex hormones via different metabolic pathways. Additionally, we will underscore the importance of understanding how endocrine-disrupting chemicals and exogenous cannabinoids influence ECS-dependent metabolic pathways in a sex-specific manner.

A 2024 inventory of test methods relevant to thyroid hormone system disruption for human health and environmental regulatory hazard assessment

Thyroid hormone system disruption (THSD) is a growing concern in chemical hazard assessment due to its impact on human and environmental health and the scarce methods available for assessing the THSD potential of chemicals. In particular, the general lack of validated in silico and in vitro methods for assessing THS activity is of high concern. This manuscript provides an inventory of test methods relevant to THSD. Building on the Organisation for Economic Co-operation and Development (OECD) Guidance Document 150 and recent international developments, we highlight progress in in silico and in vitro methods, as well as in vivo assays. The provided inventory categorizes available methods according to the levels of the OECD Conceptual Framework, with an assessment of the validation status of each method. At Level 1, 12 in silico models that have been statistically validated and are directly related to THSD have been identified. At Level 2, 67 in vitro methods have been listed including those assessed in key initiatives such as the European Union Network of Laboratories for the Validation of Alternative Methods (EU-NETVAL) validation study to identify potential thyroid disruptors. At Levels 3-5, THSD-sensitive endpoints are being included in existing fish-based OECD Test Guidelines to complement amphibian assays. In total, the inventory counts 108 entries comprising established methods (e.g., OECD Test Guidelines) as well as citable methods that are under further development and in some cases are ready for validation or in the initial stages of validation. This work aims to support the ongoing development of strategies for regulatory hazard assessment, such as integrated approaches to testing and assessment (IATAs), for endocrine disruptors, addressing critical gaps in the current testing landscape for THSD in both human and environmental health contexts.

Editorial: Environmental endocrine disruptors: mechanisms, implications, and advances in detection and mitigation in endocrinology

Editorial: Environmental endocrine disruptors: mechanisms, implications, and advances in detection and mitigation in endocrinology

Research status of anti-obesogenic functional foods: mechanism of endocrine-disrupting chemicals and glucocorticoid receptor pathway

Research status of anti-obesogenic functional foods: mechanism of endocrine-disrupting chemicals and glucocorticoid receptor pathway

Role of HOXA10 in pathologies of the endometrium.

HOXA10 belongs to the homeobox gene family and is essential for uterine biogenesis, endometrial receptivity, embryo implantation, and stromal cell decidualization. Available evidence suggests that the expression of HOXA10 is dysregulated in different endometrial disorders like endometrial hyperplasia, endometrial cancer, adenomyosis, endometriosis, recurrent implantation failure, and unexplained infertility. The downregulation of HOXA10 occurs by genetic changes in the HOXA10 gene, methylation of the HOXA10 locus, or selected miRNAs. Endocrine disruptors and organic pollutants also cause the reduced expression of HOXA10 in these conditions. In vivo experiments in mouse models and in vitro studies in human cell lines demonstrate that downregulation of HOXA10 leads to endometrial epithelial cell proliferation, failure of stromal cell decidualization, altered expression of genes involved in cell cycle regulation, immunomodulation, and various signaling pathways. These disruptions are speculated to cause infertility associated with the disorders of the endometrium.

Additives in Processed Foods as a Potential Source of Endocrine-Disrupting Chemicals: A Review

Processed foods, accounting for most consumable food categories today, contain considerable amounts of food additives. Food additives are substances added to food products to improve taste, consistency, appearance, or shelf life. Various food additives, such as phthalates, bisphenol A, tartrazine, erythrosine, artificial sweeteners, and parabens, have been identified as potential sources of endocrine-disrupting chemicals (EDCs) in processed foods. EDCs are substances that frequently interfere with the regular functioning of the endocrine system, creating an unusual environment in the biological system, which leads to adverse health effects such as the disruption of hormone synthesis, receptor binding, and signal transduction pathways, as well as energy metabolic homeostatic disorders which potentially increasing the risk of obesity, type-2 diabetes, cardiometabolic diseases and may also trigger allergic reactions. Consequently, they can also impact mammary gland development, and reproductive function, further leading to developmental abnormalities. This review aims to insights into the various food additives that act as potential endocrine-disrupting chemicals (EDCs) and to describe their applications in the food industry, as well as the failure of hormonal homeostatic mechanisms, which eventually result in hazardous health effects. It also outlines strategies to reduce the use of food additives and suggests alternative additives with minimal or no endocrine-disrupting properties, highlighting their importance for maintaining human health.

17α-Ethynylestradiol alters testicular epigenetic profiles and histone-to-protamine exchange in mice

Spermatogenesis starts with the onset of puberty within the seminiferous epithelium of the testes. It is a complex process under intricate control of the endocrine system. Physiological regulations by steroid hormones in general and by estrogens in particular are due to their chemical nature prone to be disrupted by exogenous factors acting as endocrine disruptors (EDs). 17α-Ethynylestradiol (EE2) is an environmental pollutant with a confirmed ED activity and a well-known effect on spermatogenesis and chromatin remodeling in haploid germ cells. The aim of our study was to assess possible effects of two doses (2.5ng/ml; 2.5 μg/ml) of EE2 on both histone-to-protamine exchange and epigenetic profiles during spermatogenesis performing a multi/transgenerational study in mice. Our results demonstrated an impaired histone-to-protamine exchange with a significantly higher histone retention in sperm nuclei of exposed animals, when this process was accompanied by the changes of histone post-translational modifications (PTMs) abundancies with a prominent effect on H3K9Ac and partial changes in protamine 1 promoter methylation status. Furthermore, individual changes in molecular phenotypes were partially transmitted to subsequent generations, when no direct trans-generational effect was observed. Finally, the uncovered specific localization of the histone retention in sperm nuclei and their specific PTMs profile after EE2 exposure may indicate an estrogenic effect on sperm motility and early embryonic development via epigenetic mechanisms.

Covalent Organic Framework Packed Nanoporous Membrane for Continuous Removal of Bisphenol A from Agricultural Irrigation Wastewater.

BPA, a typical endocrine disruptor, poses a significant threat to the growth of crops and thereby jeopardizes sustainable agriculture products and human health. In this work, a water-stabilized imine covalent organic framework (TpBD-COF) packed nanochannel membrane was constructed. The TpBD-COF membrane achieves high selective removal of BPA attributed to the subdivision of the pores by the filled COF, which further reduces the porous size and effectively eliminates the distance barrier between the selective sites of TpBD-COF membranes and BPA. The selective removal ratio of BPA was 5.79 times higher than that of the bare membrane, while the removal capacity reached 6.78 nM cm-2 min-1. It can eliminate BPA from irrigation wastewater and ensure crop growth. The application of COF-filled nanoporous membrane provides not only a size-matching strategy for the development of specific continuous removal of BPA but also a theoretical reference for membrane removal of other organic pollutants in agricultural irrigation water environment.

Harnessing the resolution power of two-dimensional liquid chromatography (2D-LC) for the screening of bisphenol contaminants in canned food items

Overlapping peaks can be difficult to avoid in 1D-LC, which make the identification and quantification of compounds ambiguous, especially if the only available detector is a UV/DAD. To overcome this, a two-dimensional liquid chromatography (2D-LC) method to monitor Bisphenols (BPs), and particularly the chosen analogues BPA, BPB, BPF, BPS, BPZ, and BPAF, in a complex matrix (canned food) was developed and validated. BPs are endocrine disruptors present in the lining of the can, which may leach into the content of canned food. It is essential to continuously identify and monitor bisphenols that are unintentionally ingested using newly available and highly efficient methods such as 2D-LC. The coefficient of variation (CV) of peak areas and retention times for all analytes in both dimensions ranged from 0.050 to 2.960 %. The recovery of the whole procedure was determined to be 67.4 ± 0.1 % in the first dimension, and 64.3 ± 0.1 % in the second dimension. The limit of detection (LOD) determined in the second dimension for the analytes ranged from 0.075 to 0.301 ppm. Finally, four canned food samples were prepared by solid-liquid extraction, and surveyed for BPA, BPB, BPF, BPS, BPZ, and BPAF. BPF (0.093 ppm) and BPAF (2.656 ppm) were accurately detected in two separate samples. This report highlights the first successful application of 2D-LC to bisphenol compounds, an important class of emerging contaminants.