Determination of 16 ultraviolet-absorbing compounds in marine invertebrates by using LC-USI-MS/MS coupled with QuEChERS.

In this study, we examined multiple endocrine-disrupting ultraviolet-absorbing compounds (UVACs) in marine invertebrates used in personal care products and packaging. Modified QuEChERS and liquid chromatography UniSpray ionization tandem mass spectrometry were used to identify 16 UVACs in marine invertebrates. Matrix-matched calibration curves revealed high linearity (r ≥ 0.9929), with limits of detection and quantification of 0.006-1.000 and 0.020-3.000 ng/g w.w., respectively. In oysters, intraday and interday analyses revealed acceptable accuracy (93%-120%) and precision (≤18%), except for benzophenone (BP) and ethylhexyl 4-(dimethylamino) benzoate. Analysis of 100 marine invertebrate samples revealed detection frequencies of 100%, 98%, 89%, 64%, and 100% for BP, 4-hydroxybenzophenone, 4-methylbenzophenone, 4-methylbenzylidene camphor, and benzophenone-3 (BP-3), respectively. BP and BP-3 were detected at concentrations of 4.40-27.39 and < 0.020-0.560 ng/g w.w., respectively, indicating their widespread presence. Overall, our proposed method successfully detected UVACs in marine invertebrates, raising concerns regarding their potential environmental and health effects.

Distribution and accumulation of UV filters (UVFs) and conservation status of Posidonia oceanica seagrass meadows in a prominent Mediterranean coastal tourist hub.

This study investigates the presence and impact of UV filters in Posidonia oceanica meadows in Formentera, a Mediterranean tourist hotspot. It highlights the distribution of inorganic (TiO2 and ZnO) and organic UV filters (UVFs) in different environmental matrices, their accumulation in seagrass tissues and their impact on the seagrass health. In the overlying and canopy waters of P. oceanica, Zn concentrations surpassed Ti, with three organic UVFs (benzophenone-3 [BP-3], avobenzone and homosalate [HMS]) consistently detected. Ti concentrations were generally higher than Zn in rhizosphere sediments, along with recurrent presence of octocrylene, HMS, 2-ethylhexyl methoxycinnamate (EHMC), and 4-methylbenzylidene camphor (4-MBC). Maximum Zn concentrations were found in canopy waters (3052.9 ng L-1). Both Ti and Zn were found in all P. oceanica tissues and leaf epiphytes across all study sites. Additional UVFs like octocrylene, avobenzone, and BP-8 were also detected in P. oceanica tissues and epiphytes. Elevated levels of octocrylene in leaf epiphytes (2112.1 ng g-1 dw) and avobenzone in leaves (364.2 ng g-1 dw) and leaf epiphytes (199.6 ng g-1 dw) were observed in the Port of La Savina, the island's main entry port. Octocrylene concentrations (up to 2575 ng g-1 dw) in rhizosphere sediments near sewage discharge points exceeded reported maxima, highlighting wastewater treatment plants as significant sources of organic UVFs. Correlational analyses suggested that the accumulation of octocrylene, avobenzone, and BP-3 negatively impacted P. oceanica's conservation status, affecting global density, density at 100 % cover, and leaf morphometry. Positive correlations were observed between leaf polyphenols (antioxidants) and concentrations of avobenzone, benzophenone-8 (BP-8), and BP-3, indicating potential oxidative stress induced by UVFs in P. oceanica. Our study underscores the pervasive presence of UV filters in P. oceanica habitats, with implications for seagrass health and conservation, especially in areas of high tourism and sewage discharge.

Falcon Probe: A High-Pressure and Robust Sampling Interface for Coupling Lossless Liquid Chromatography Injection with In Situ Nanoliter-Scale Sample Pretreatment.

With the increasing demand for trace sample analysis, injecting trace samples into liquid chromatography-mass spectrometry (LC-MS) systems with minimal loss has become a major challenge. Herein, we describe an in situ LC-MS analytical probe, the Falcon probe, which integrates multiple functions of high-pressure sample injection without sample loss, high-efficiency LC separation, and electrospray. The main body of the Falcon probe is made of stainless steel and fabricated by the computer numerical control (CNC) technique, which has ultrahigh mechanical strength. By coupling a nanoliter-scale droplet reactor made of polyether ether ketone (PEEK) material, the Falcon probe-based LC-MS system was capable of operating at mobile-phase pressures up to 800 bar, which is comparable to those of conventional ultraperformance liquid chromatography (UPLC) systems. Using the probe pressing microamount in situ (PPMI) injection approach, the Falcon probe-based LC-MS system showed high separation efficiency and good repeatability with relative standard deviations (RSDs) of retention time and peak area of 1.8% and 9.9%, respectively, in peptide mixture analysis (n = 6). We applied this system to the analysis of a trace amount of 200 pg of HeLa protein digest and successfully identified an average of 766 protein groups (n = 5). By combining in situ sample pretreatment at the nanoliter range, we further applied the present system in single-cell proteomic analysis, and 241 protein groups were identified in single 293 cells, which preliminarily demonstrated its potential in the analysis of trace amounts of samples with complex compositions.

Prevalence of selected UV filter compounds in Biscayne National Park.

This research was carried out in order to assess a baseline occurrence in Biscayne National Park, Florida, of four organic contaminants: the UV filters oxybenzone, dioxybenzone, and benzophenone, as well as the topical pain reliever benzocaine. A total of 35 samples were taken from five locations within the park, four near barrier islands, and one at a coral reef. Analyses were carried out using liquid chromatography coupled to high-resolution mass spectrometry. Oxybenzone was detected in 26% of samples from the park at concentrations up to 31 ng/L. Benzophenone was detected in 49% of samples from the park at concentrations up to 131 ng/L. Benzocaine and dioxybenzone were not detected in any of the samples.

Analysis of the UV filter Benzophenone-3 assimilation in Crossostrea gigas oysters post-exposure in a controlled environment by LC-MS/MS.

Benzophenone-3 (BP-3), utilized as a UV filter in cosmetic products, is an emerging contaminant that constitutes a threat to natural resources and environmental health. This study investigated the assimilation of the UV filter BP-3 in Crassostrea gigas oysters collected in Florianópolis, Santa Catarina, Brazil. Lyophilized oyster tissue extracts were prepared using the QuEChERS method, and LC-MS/MS was employed to determine the BP-3 concentration in the samples. The method was applied to specimens intentionally exposed to two concentrations of the contaminant, for different periods of exposure (1 and 7 days). Samples from treatment 1 (T1) were exposed to a concentration of 1 µg L-1 of the BP-3 standard, and samples from treatment 2 (T2) were exposed to a concentration of 100 µg L-1 of the BP-3 standard. The results revealed rapid absorption of BP-3, with an increase of 126% for lower concentrations, reaching 1.13 µg of BP-3 per gram of oyster tissue, and 17% for higher concentrations, reaching 34.6 µg of BP-3 per gram of oyster tissue after 7 days. The presence of BP-3 even in samples not directly exposed to the contaminant indicates its widespread environmental distribution. The rapid bioaccumulation suggests the need to consider seasonal variations, such as increased tourism in the summer. The validated analytical method demonstrated efficacy in quantifying BP-3, providing an integrated approach for long-term monitoring of pollution levels and their dynamic variations over time. In addition, variation in BP-3 levels in the samples may be related to transport patterns influenced by tides and discharges from septic system, highlighting the need to improve wastewater treatment. These findings underscore the necessity for continuous biomonitoring and effective environmental management to safeguard the health of marine ecosystems and humans.

Concentrations, compositional profiles, and health risks of benzophenones among the Taiwanese population based on analysis of 23 daily consumed foods.

In this study, we analyzed the occurrence and distribution of 11 benzophenone-type ultraviolet filters (BPs) in 893 food samples spanning 7 food categories in Taiwan. We conducted a Monte Carlo simulation to determine the carcinogenic and noncarcinogenic risks of BPs. The results indicated that cornflakes had the highest mean level of BPs (103 ng/g), followed by bread (101 ng/g) and pastries (59 ng/g). BP was the most prevalent category, followed by 4-methylbenzophenone (4-MBP), 2-hydroxybenzophenone, and benzophenone-3. Estimation of the lifetime cancer risk (LTCR) of BP (average life expectancy of 80 years) placed them in the 50th and 97.5th percentiles [P50 (P97.5)] LTCR of 1.9 × 10-7 (5.7 × 10-6), indicating that BP in food poses a low renal hazard to the Taiwanese population. The noncarcinogenic risk of BPs was evaluated using a hazard quotient and combined margin of exposure (MOET), revealing a P50 (P97.5) hazard index of < 1 for BP, 4-MBP, and methyl-2-benzoylbenzoate. Although the P50 MOET values for all age groups were within the moderate range of concern, with a more conservative extreme (P2.5), the MOET values for the 0-3, 3-6, and 6-12 age groups fell below 100, indicating a high concern for renal degeneration and hyperplasia.

Occurrence and abundance of microplastics and plasticizers in landfill leachate from open dumpsites in Sri Lanka.

This is the first attempt that investigate the abundance of plasticizers in leachate sediment in the scientific literature, alongside the debut effort to explore the abundance of microplastics and plasticizers in landfill leachate and sediment in Sri Lanka. Microplastics in sizes ranging from ≥2.0-5.0, ≥1.0-2.0, and ≥ 0.5-1.0 mm were extracted from the leachate draining from ten municipal solid waste open dump sites and sediment samples covering seven districts. Microplastics were extracted by density separation (Saturated ZnCl2) followed by wet peroxide digestion and the chemical identification was conducted by Fourier Transform Infrared spectroscopy. Plasticizers were extracted to hexane and analyzed by high-performance liquid chromatography. The total mean microplastic abundance in leachate was 2.06 ± 0.62 mg/L whereas it was 363 ± 111 mg/kg for leachate sediments. The most frequently found polymer type was polyethylene (>50%), and white color was dominant. The average concentration of bisphenol A (BPA), benzophenone (BP) and diethyl-hydrogen phthalate (DHEP) in leachate was 158 ± 84.4, 0.75 ± 0.16 and 170 ± 85.8 µg/L respectively. Furthermore, BP and DHEP in leachate sediment was 100 ± 68.3 and 1034 ± 455 µg/kg respectively. As landfill leachate is directly discharged into nearby surface and groundwater bodies that serve as sources of drinking water, the study highlights the potential concerns of microplastic and plasticizer exposure to the surrounding Sri Lankan community through consumption of contaminated drinking water. Therefore, there is a timely need of develop the effective waste management and pollution control measures to minimize the possible threats to both the environment and human health.

Biomonitoring of benzophenones in guano samples of wild bats in Poland.

Benzophenones (BPs) are substances used in the production of sunscreens, cosmetics, and personal care products. However, there is a lack of knowledge of BPs in wild animals. Therefore, the study aimed to assess the concentration of selected BPs commonly used in the cosmetic industry in guano samples collected from 4 colonies of greater mouse-eared bats (Myotis myotis). Liquid chromatography with tandem mass spectrometry (LC-MS/MS) was used to determine guano concentrations of benzophenone 1 (BP-1), benzophenone 2 (BP-2), benzophenone 3 (BP-3) and benzophenone 8 (BP-8). BP-1 levels above the method quantification limit (MQL) were noted in 97.5% of samples and fluctuated from <0.1 ng/g to 259 ng/g (mean 41.50 ng/g, median 34.8). The second most common was BP-3, which fluctuated from <0.1 ng/g to 19 ng/g (mean 6.67 ng/g, median 5.05), and its levels higher than MQL were observed in 40% of samples. BP-2 and BP-8 concentrations did not exceed the method detection limit (0.04 ng/g) in any analyzed sample. There were visible differences in the BP-1 and BP-3 levels among the studied bat colonies. Mean BP-1 concentration fluctuated from 11.23±13.13 ng/g to 76.71±65.51 ng/g and differed significantly between the colonies. Mean BP-3 concentration fluctuated from 5.03±6.03 ng/g to 9.18±7.65 mg/g, but it did not differ significantly between the colonies. The results show that guano is a suitable matrix for the assessment of wildlife exposure to BPs. This could be particularly advantageous in protected species, where not disturbing and stressing the animals are crucial.

A multiplex approach of MS, 1D-, and 2D-NMR metabolomics in plant ontogeny: A case study on Clusia minor L. organs (leaf, flower, fruit, and seed).

INTRODUCTION: The genus Clusia L. is mostly recognised for the production of prenylated benzophenones and tocotrienol derivatives. OBJECTIVES: The objective of this study was to map metabolome variation within Clusia minor organs at different developmental stages. MATERIAL AND METHODS: In total 15 organs/stages (leaf, flower, fruit, and seed) were analysed by UPLC-MS and 1H- and heteronuclear multiple-bond correlation (HMBC)-NMR-based metabolomics. RESULTS: This work led to the assignment of 46 metabolites, belonging to organic acids(1), sugars(2) phenolic acids(1), flavonoids(3) prenylated xanthones(1) benzophenones(4) and tocotrienols(2). Multivariate data analyses explained the variability and classification of samples, highlighting chemical markers that discriminate each organ/stage. Leaves were found to be rich in 5-hydroxy-8-methyltocotrienol (8.5 µg/mg f.w.), while flowers were abundant in the polyprenylated benzophenone nemorosone with maximum level detected in the fully mature flower bud (43 µg/mg f.w.). Nemorosone and 5-hydroxy tocotrienoloic acid were isolated from FL6 for full structural characterisation. This is the first report of the NMR assignments of 5-hydroxy tocotrienoloic acid, and its maximum level was detected in the mature fruit at 50 µg/mg f.w. Seeds as typical storage organ were rich in sugars and omega-6 fatty acids. CONCLUSION: To the best of our knowledge, this is the first report on a comparative 1D-/2D-NMR approach to assess compositional differences in ontogeny studies compared with LC-MS exemplified by Clusia organs. Results derived from this study provide better understanding of the stages at which maximal production of natural compounds occur and elucidate in which developmental stages the enzymes responsible for the production of such metabolites are preferentially expressed.

Urinary concentrations and elimination half-lives of parabens, benzophenones, bisphenol and triclosan in Japanese young adults.

Environmental phenols are widely distributed in the environment and human samples, suggesting potential exposure to these chemicals. We designed an intervention trial with 30 participants over 6 days to assess the urinary concentrations and half-lives of environmental phenols in Japanese young people. The target environmental phenols include three parabens (methyl paraben, ethyl paraben, and propyl paraben), two benzophenones (benzophenone 1 and 3), two bisphenols (bisphenol F and bisphenol S), and triclosan. Throughout the intervention, the participants consumed the same food and drinks and used personal care products provided by the project. The target phenols were measured in urine from the participants using a liquid chromatography-tandem mass spectrometer. We compared the measured concentrations between the study periods to better understand the exposure tendency. Some statistically significant differences were observed. All target analytes were detected in more than 50% of samples collected on Day 0 (the day before the intervention). Methyl paraben was the dominant phenol detected in urine (1640 µg/g-creatinine), followed by ethyl paraben (119 µg/g-creatinine). Downward trends in creatinine-corrected concentrations were observed for all target analytes in some instances. Non-compartment analysis was performed to estimate urinary excretion parameters. The estimated half-lives ranged from 7.69 to 20.3 h. Use of paraben-free products during the intervention period reduced the body burden.

Dietary risk assessment of benzophenone derivatives using bread consumption estimates in a Taiwanese population.

Listed as endocrine-disrupting chemicals, benzophenone (BP) and its nine analogues (BPs) are an emerging group of contaminants. The migration of BPs from ultraviolet inks to food has been investigated in many studies; however, few studies have investigated BPs in foods and the risks of human exposure to BPs. We validated a trace and multi-residue method for simultaneously determining 10 BPs, including BP, BP-1, BP-2, BP-3, BP-8, 4-MBP, 2-OHBP, 4-OHBP, M2BB, and PBZ. Eighty-one bread samples were analyzed using stable isotope labeling and ultrahigh-performance liquid chromatography-electrospray ionization tandem mass spectrometry with solid-liquid extraction. We determined the estimated daily intake of BPs, non-cancer risks, and lifetime cancer risks (LTCRs) from daily bread consumption for seven age groups using a Monte Carlo simulation. The method demonstrated robust linearity (R2 ≥ 0.991), low limits of detection (0.04-2 ng/g), and satisfactory precision. The intra- and interday relative standard deviation ranges were 0.6%-9% and 3%-20%, respectively. BP, 4-MBP, 2-OHBP, BP-1, and BP-3 were detected in 97%, 67%, 59%, 24%, and 23% of the samples, respectively. 2-OHBP had the highest mean (range) value of 18.3 (

Role of soil organic matter on the retention and mobility of common plastic additives, Di(2-ethylhexyl) phthalate, bisphenol A and benzophenone, in soil.

The objectives of this study were to assess the role of soil organic matter on retaining plastic additives, Di(2-ethylhexyl) phthalate (DEHP), Bisphenol A (BPA) and Benzophenone (BP), to postulate the retention mechanisms and mobility in soil. Batch experiments were conducted for red yellow podzolic soil (OM) and soil subjected to high temperature oxidation at 600 °C for 2 h to remove total organic matter (OMR). Pristine soil, which contains organic matter abbreviated as OM (soil with organic matter) whereas total organic matter removed soil is abbreviated as OMR (organic matter removed soil). The pH edge and kinetic experiments were conducted with 20 g/L soil suspension spiked with 10 mg/L of each additive, whereas 1-20 mg/L concentration range was used in isotherm experiments and analyzed using high performance liquid chromatography. DEHP demonstrated the highest retention, 331 and 615.16 mg/kg in OM and OMR soils respectively, at pH 6.6. However, BPA and BP showed highest retentions of 132 and 128 mg/kg, respectively around pH 4.3 in pristine soil. DEHP interaction with soil OM indicated weak physical bonding whereas chemisorption to OMR soil. In the case of BPA, physisorption governed its interaction with both soil organic matter and mineral fraction. Nevertheless, BP demonstrated chemical interactions with OM and minerals. Desorption of DEHP was close to 100% however, BPA and BP were <15%. Overall, DEHP and BPA could be easily released into soil water and possibly be available for plant uptake while, BP is immobilized in soil.

Benzophenone-3: Comprehensive review of the toxicological and human evidence with meta-analysis of human biomonitoring studies.

BACKGROUND: Benzophenone-3 (BP-3) and its major metabolite benzophenone-1 (BP-1) are widely used as UV filters in sunscreens and cosmetics to prevent sunburn and skin damage, or as stabilizers to prevent photodegradation in many commercial products. As a result, their presence is ubiquitous in the environment, wildlife and humans. Based on endocrine disruption concerns, international regulatory agencies are performing a closer evaluation. OBJECTIVE AND METHODS: This work aimed to comprehensively review the available human relevant evidence for safety issues in MEDLINE/PubMed in order to create a structured database of studies, as well as to conduct an integrative analysis as part of the Human Biomonitoring for Europe (HBM4EU) Initiative. RESULTS: A total of 1,635 titles and abstracts were screened and 254 references were evaluated and tabulated in detail, and classified in different categories: i) exposure sources and predictors; ii) human biomonitoring (HBM) exposure levels to perform a meta-analysis; iii) toxicokinetic data in both experimental animals and humans; iv) in vitro and in vivo rodent toxicity studies; and v) human data on effect biomarkers and health outcomes. Our integrative analysis showed that internal peak BP-3 concentrations achieved after a single whole-body application of a commercially available sunscreen (4% w/w) may overlap with concentrations eliciting endocrine disrupting effects in vitro, and with internal concentrations causing in vivo adverse female reproductive effects in rodents that were supported by still limited human data. The adverse effects in rodents included prolonged estrous cycle, altered uterine estrogen receptor gene expression, endometrium hyperplasia and altered proliferation and histology of the mammary gland, while human data indicated menstrual cycle hormonal alterations and increased risk of uterine fibroids and endometriosis. Among the modes of action reported (estrogenic, anti-androgenic, thyroid, etc.), BP-3 and especially BP-1 showed estrogenic activity at human-relevant concentrations, in agreement with the observed alterations in female reproductive endpoints. The meta-analysis of HBM studies identified a higher concern for North Americans, showing urinary BP-3 concentrations on average 10 and 20 times higher than European and Asian populations, respectively. DISCUSSION AND CONCLUSIONS: Our work supports that these benzophenones present endocrine disrupting properties, endorsing recent European regulatory efforts to limit human exposure. The reproducible and comprehensive database generated may constitute a point of departure in future risk assessments to support regulatory initiatives. Meanwhile, individuals should not refrain from sunscreen use. Commercially available formulations using inorganic UV filters that are practically not absorbed into systemic circulation may be recommended to susceptible populations.

Influence of mobile phase composition on the analytical sensitivity of LC-ESI-MS/MS for the concurrent analysis of bisphenols, parabens, chlorophenols, benzophenones, and alkylphenols.

Phenols are significant environmental endocrine disruptors that can have adverse health effects on exposed individuals. Correlating phenol exposure to potential health implications requires the development of a comprehensive and sensitive analytical method capable of analyzing multiple phenols in a single sample preparation and analytical run. Currently, no such method is available for multiple classes of phenols due to electrospray ionization (ESI) limitations in concurrent ionization and lack of sensitivity to certain phenols, particularly alkylphenols. In this study, we investigated the influence of mobile phase compositions in ESI on concurrent ionization and analytical sensitivity of liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) during the analysis of multiple classes of phenols, and we propose a comprehensive and sensitive analytical method for various classes of phenols (i.e., bisphenols, parabens, benzophenones, chlorophenols, and alkylphenols). The proposed method was affected by 0.5 mM ammonium fluoride under methanol conditions. It enabled the concurrent ionization of all the phenols and significantly improved the analytical sensitivity for bisphenols and alkylphenols, which typically have poor ionization efficiency. This method, combined with a "dilute and shoot" approach, allowed us to simultaneously quantify 38 phenols with good chromatographic behavior and sensitivity. Furthermore, the method was successfully applied to the analysis of 61 urine samples collected from aquatic (swimming) and land (indoor volleyball and outdoor football) athletes.

Layered Double Hydroxide/Graphene Quantum Dots as a New Sorbent for the Dispersive Solid-Phase Microextraction of Selected Benzophenones, Phenols, and Parabens.

In this study, the synthesis of a layered double hydroxide (LDH) composite with graphene quantum dots (GQDs) and its utilization for the development of a dispersive solid-phase extraction procedure are described. To this end, a carbonate-free Mg-Al LDH was synthesized. The development of the composite material made feasible the use of GQDs in a sample preparation procedure, while the incorporation of the GQDs in the LDH structure resulted in an 80% increase in extraction efficiency, compared to the bare LDH. As a proof of concept, the composite material was used for the development of an analytical method for the extraction, and preconcentration, of benzophenones, phenols, and parabens in lake water using high-performance liquid chromatography, coupled to a diode array detector. The analytical method exhibits low limits of quantification (0.10-1.33 µg L-1), good recoveries (92-100%), and satisfactory enrichment factors (169-186). Due to the abovementioned merits, the easy synthesis and simple extraction, the developed method can be used for the routine analysis of the target compounds.

Comparative transcriptome analysis reveals immunotoxicology induced by three organic UV filters in Manila clam (Ruditapes philippinarum).

Benzophenone-3 (BP-3), 4-methyl-benzylidene camphor (4-MBC) and 2-ethyl-hexyl-4-trimethoxycinnamate (EHMC) are commonly used organic ultraviolet (UV) filters and are frequently detected in water environments. In the present study, we studied the potential adverse impacts of UV filter exposures in Ruditapes philippinarum by investigating transcriptomic profiles and non-specific immune enzyme activities. Transcriptome analysis showed that more genes were differentially regulated in EHMC-treated group, and down-regulated genes (2009) were significantly more than up-regulated ones (410) at day 7. Function annotation revealed that pathways "immune system", "cell growth and death" and "infectious diseases" were significantly enriched. Generally, combined qPCR and biochemical analyses demonstrated that short-term exposure to low dose of UV filters could activate immune responses, whereas the immune system would be restrained after prolonged exposure. Taken together, the present study firstly demonstrated the immunotoxicology induced by BP-3, 4-MBC and EHMC on R. philippinarum, indicating their potential threats to the survival of marine bivalves.

Mechanochemically synthesized zeolitic imidazolate framework-8 as sorbent for dispersive solid-phase extraction of benzophenone-type ultraviolet filters in aqueous samples.

Benzophenone-type ultraviolet filters (BP-UVFs) are a group of emerging contaminants, which found in various environmental aqueous samples raising potential risks for public health concern and could bioaccumulate in the food chain. This study describes a simple and "green" method to rapidly analyze five BP-UVFs that are frequently found in surface water and in seawater samples. Dispersive solid-phase extraction (DSPE) using a zeolitic imidazolate framework­8 (ZIF-8) as the sorbent was applied to efficiently extract the BP-UVFs from aqueous samples, and they were then detected and quantified by UHPLC-electrospray ionization (+)-quadrupole time-of-flight mass spectrometry (UHPLC-ESI (+)-QTOF-MS). The ZIF-8 sorbent was synthesized by a green one-step mechanochemical process using water-assisted grinding and a stoichiometric reaction. The Box-Behnken Design coupled with the response surface method was applied to optimize the main DSPE extraction factors. The developed method was fully validated, showing low limits of quantification (LOQs; 0.3-20 ng L-1), satisfactory mean spiked recoveries (72-105%), and a high level of precision (3-9%). A preliminary analysis of the surface water and seawater samples revealed that 2-hydroxy-4-methoxybenzophenone (BP-3) was the most common BP-UVF present in our aquatic environment, likely due to its widespread applications and slow rate of degradation.

Environmental contamination status with common ingredients of household and personal care products exhibiting endocrine-disrupting potential.

The continuous use of household and personal care products (HPCPs) produces an immense amount of chemicals, such as parabens, bisphenols, benzophenones and alkylphenol ethoxylates, which are of great concern due to their well-known endocrine-disrupting properties. These chemicals easily enter the environment through man-made activities, thus contaminating the biota, including soil, water, plants and animals. Thus, on top of the direct exposure on account of their presence in HPCPs, humans are also susceptible to secondary indirect exposure attributed to the ubiquitous environmental contamination. The aim of this review was therefore to examine the sources and occurrence of these noteworthy contaminants (i.e. parabens, bisphenols, benzophenones, alkylphenol ethoxylates), to summarise the available research on their environmental presence and to highlight their bioaccumulation potential. The most notable environmental contaminants appear to be MeP and PrP among parabens, BPA and BPS among bisphenols, BP-3 among benzophenones and NP among alkylphenols. Their maximum detected concentrations in the environment are mostly in the range of ng/L, while in human tissues, their maximum concentrations achieved µg/L due to bioaccumulation, with BP-3 and nonylphenol showing the highest potential to bioaccumulate. Finally, of another great concern is the fact that even the unapproved parabens and benzophenones have been detected in the environment.

Long-term stability of several endocrine disruptors in the first morning urine samples and their associations with lifestyle characteristics.

Parabens, triclosan (TCS), bisphenols, benzophenones, and phthalates are typical endocrine disruptors (EDs) with short half-lives in the human body. The concentration levels of those EDs in a spot urine sample are frequently used in exposure assessment studies, and the reproducibility of urinary levels of these nonpersistent EDs should be considered. In the present study, we consecutively collected 45-day first morning void (FMV) urine samples, as well as daily questionnaires, in six recruited participants and measured the urinary concentrations of six parabens, TCS, nine bisphenols, five benzophenones, and ten phthalate metabolites by using high-performance liquid chromatography-tandem mass spectrometry. MeP, EtP, PrP, TCS, BPA, BPS, BPF, and most phthalate metabolites were frequently detected (over 62 % of samples). The intraclass correlation coefficients (ICCs) for ED concentrations in FMV urine samples ranged from fair to excellent for MeP (0.683), EtP (0.702), BPA (0.505), BPS (0.908), BPF (0.887), BP-3 (0.712), mMP (0.661), mEP (0.523), mBP (0.500), miBP (0.724), mBzP (0.961) and all metabolites of DEHP (0.867-0.957), whereas they were low for PrP (0.321) and TCS (0.306). After creatinine adjustment, the values of ICCs for most target EDs were increased with mild to significant improvement. The stability of ED concentrations was affected by daily diet (MeP, TCS, BPA, mMP, miBP, mBP and mBzP), food containers (PrP and mECPP), use of personal care products (HMWP metabolites), pharmaceuticals (EtP) and recorded activities (BPS, mEHP, mBzP, mEHHP and mEOHP), as confirmed by a general linear mixed model. Furthermore, extending the FMV sampling period improved the probability of acceptable reproducibility (ICCs > 0.40) of MeP, EtP, BP-3 and mEP concentrations. For BPS, BPF and HMWP metabolite concentrations showed high probabilities (>80 %) of acceptable reproducibility in the last three days, and the increasing sample size slowly improved the ability to discriminate the subjects. The results were exactly the opposite for BPA concentrations.

Associations between concentrations of typical ultraviolet filter benzophenones in indoor dust and human hair from China: A human exposure study.

Benzophenone-3 (BP-3) has been widely used as a typical ultraviolet (UV) filter in various personal care products. While BP-3 and its derivatives (BPs) have been detected in various environmental matrices, very little is known about the concentration profile of BPs in human hair. The associations of BPs in human hair with those in indoor dust samples collected from the same locations remain largely unclear. In this study, a total of 258 indoor dust samples and 66 human hair samples were collected across China and analyzed to determine the presence of BP-3 and its derivatives. The BP-3 concentrations ranged from 0.386 to 1230 ng/g dw in indoor dust and from 0.149 to 696 ng/g dw in human hair. No difference was found between BPs in indoor dust samples from different geographic regions (p > 0.05), whereas relatively higher BP concentrations were observed for dust from urban regions than dust from rural ones (p < 0.05). A positive correlation was found between the BP-3 concentrations of indoor dust and human hair samples (p < 0.05). The estimated daily intake (EDI) of BPs for humans from indoor dust showed a gender difference (females > males; p < 0.05), with the highest EDI value being found in Southwest China (males: 35.5 pg/kg bw/day; females: 40.6 pg/kg bw/day). This study provides the concentration profiles of BPs in human hair and elucidates the associations between the BP concentrations in indoor dust samples and human hair samples collected across China.