Phthalate esters: occurrence, toxicity, bioremediation, and advanced oxidation processes.

Phthalic acid esters are emerging pollutants, commonly used as plasticizers that are categorized as hazardous endocrine-disrupting chemicals (EDCs). A rise in anthropogenic activities leads to an increase in phthalate concentration in the environment which leads to various adverse environmental effects and health issues in humans and other aquatic organisms. This paper gives an overview of the research related to phthalate ester contamination and degradation methods by conducting a bibliometric analysis with VOS Viewer. Ecotoxicity analysis requires an understanding of the current status of phthalate pollution, health impacts, exposure routes, and their sources. This review covers five toxic phthalates, occurrences in the aquatic environment, toxicity studies, biodegradation studies, and degradation pathways. It highlights the various advanced oxidation processes like photocatalysis, Fenton processes, ozonation, sonolysis, and modified AOPs used for phthalate removal from the environment.

Does Using Corsi-Rosenthal Boxes to Mitigate COVID-19 Transmission Also Reduce Indoor Air Concentrations of PFAS and Phthalates?

The COVID-19 pandemic brought new emphasis on indoor air quality. However, few studies have investigated the impact of air filtration, a COVID-mitigation approach, on indoor air concentrations of semivolatile organic compounds (SVOCs). Using a quasi-experimental design, we quantified the impact of a relatively low-cost "do-it-yourself" air filter (Corsi-Rosenthal Box; CR Box) on indoor air concentrations of 42 PFAS and 24 other SVOCs. We sampled air before (October-November 2021) and during (February-March 2022) deployment of CR Boxes in 17 rooms located in an occupied Providence, Rhode Island office building. We measured sound levels in rooms with CR Boxes operating and not operating. While CR Boxes were deployed, concentrations of seven PFAS (N-EtFOSE, N-EtFOSA, FBSA, PFBS, PFHxS, PFOS, PFNA) were 28-61% lower and concentrations of five phthalates (DMP, DEP, DiBP, BBzP, DCHP) were 29-62% lower. Concentrations of five PFAS and one phthalate increased 23-44% during the intervention period, but the 95% CI of most of these estimates included the null. Daytime sound levels increased 5.0 dB when CR Boxes were operating. These results indicate that CR Boxes reduced exposure to several lower-volatility phthalates and sulfonated PFAS previously reported to be found in office building materials and products, with potentially distracting increases in sound levels.

Determination and risk assessment of phthalates in face masks. An Italian study.

Serious human health concerns have been recently raised from daily use of face masks, due to the possible presence of hazardous compounds as the phthalic acid esters (PAEs). In this study, the content of 11 PAEs in 35 commercial masks was assessed by applying a specific and accurate method, using Gas Chromatography/Mass Spectrometry. Surgical, FFP2 and non-surgical models, for both adults and children were collected from the Italian market. Analyses showed that four of the target analytes were detected in all tested samples with median total concentrations ranging between 23.6 mg/kg and 54.3 mg/kg. Results obtained from the experimental analysis were used in the risk assessment studies carried out for both carcinogenic and non-carcinogenic effects. Doses of exposure (Dexp) of PAEs ranged from 6.43 × 10-5 mg/kg bw/day to 1.43 × 10-2 mg/kg bw/day. Cumulative risk assessment was performed for non-carcinogenic and carcinogenic effects. No potential risk was found for non-carcinogenic effects, yet the 20% of the mask samples showed potential carcinogenic effects for humans. A refined exposure assessment was performed showing no risk for carcinogenic effects. This paper presents a risk assessment approach for the identification of potential risks associated to the use of face masks.

Evaluating Indoor Air Phthalates and Volatile Organic Compounds in Nail Salons in the Greater New York City Area: A Pilot Study.

The Greater New York City area ranks highest in the United States in the number of nail salon technicians, primarily Asian immigrant women. Nail salon technicians are exposed to toxic phthalates and volatile organic compounds daily in nail salons. The purpose of this pilot study was to measure a mixture of phthalates and volatile organic compounds in nail salons in the Greater New York City area, and to characterize work-related determinants of indoor air quality in these nail salons. Working with four Asian nail salon organizations in the Greater New York City area, we measured indoor air phthalates and volatile organic compounds at 20 nail salons from February to May 2021 using silicone wristbands and passive samplers, respectively. Nail salon characteristics were also examined. We measured six phthalates and 31 volatile organic compounds. Di(2-ethylhexyl) phthalate and Diethyl phthalate had the highest concentrations among the six phthalates measured. Concentrations of toluene, d-limonene, methyl methacrylate, and ethyl methacrylate were higher than that of the rest. Manicure/pedicure tables, the number of customers per day, and application of artificial nail (acrylic) services were positively associated with the levels of phthalates and volatile organic compounds. Given the large number of people employed in the nail industry and the even larger number of customers visiting such establishments, exposures to these toxic chemicals are likely to be widespread.

Cyclic Phthalate Esters as Liver X Receptor Antagonists with Anti-hepatitis C Virus and Anti-severe Acute Respiratory Syndrome Coronavirus 2 Properties.

The liver X receptor is a nuclear hormone receptor that regulates lipid metabolism. Previously, we had demonstrated the antiviral properties of a liver X receptor antagonist associated with the hepatitis C virus and severe acute respiratory syndrome coronavirus 2. In this study, we screened a chemical library and identified two potential liver X receptor antagonists. Spectroscopic analysis revealed that the structures of both antagonists (compounds 1 and 2) were cyclic dimer and trimer of esters, respectively, that consisted of phthalate and 1,6-hexane diol. This study is the first to report the structure of the cyclic trimer of phthalate ester. Further experiments revealed that the compounds were impurities of solvents used for purification, although their source could not be traced. Both phthalate esters exhibited anti-hepatitis C virus activity, whereas the cyclic dimer showed anti-severe acute respiratory syndrome coronavirus 2 activity. Cyclic phthalate derivatives may constitute a novel class of liver X receptor antagonists and broad-spectrum antivirals.

Release of phthalate esters (PAEs) and microplastics (MPs) from face masks and gloves during the COVID-19 pandemic.

Marine pollution with personal protective equipment (PPE) has recently gained major attention. Multiple studies reported the release of microplastics (MPs) and chemical contaminants from face masks, the most used PPE type. However, not much is known concerning the release of phthalate esters (PAEs) in aquatic media, as well as the hazard posed by other types of PPE. In the present study, we investigated the release of MPs and PAEs from face masks and gloves recovered from the environment. The results indicated that both PPEs release MPs comparable to the literature, but higher concentrations were presented by face masks. In turn, the total concentration of six PAEs was higher in gloves than in face masks. The release of these contaminants is exacerbated over time. The present study allows researchers to understand the contribution of PPE to marine pollution while accounting for gloves, a generally overlooked source of contaminants.

Zirconium-Based Metal-Organic Frameworks as Acriflavine Cargos in the Battle against Coronaviruses─A Theoretical and Experimental Approach.

In this study, we present a complementary approach for obtaining an effective drug, based on acriflavine (ACF) and zirconium-based metal-organic frameworks (MOFs), against SARS-CoV-2. The experimental results showed that acriflavine inhibits the interaction between viral receptor-binding domain (RBD) of spike protein and angiotensin converting enzyme-2 (ACE2) host receptor driving viral cell entry. The prepared ACF@MOF composites exhibited low (MOF-808 and UiO-66) and high (UiO-67 and NU-1000) ACF loadings. The drug release profiles from prepared composites showed different release kinetics depending on the local pore environment. The long-term ACF release with the effective antiviral ACF concentration was observed for all studied ACF@MOF composites. The density functional theory (DFT) calculations allowed us to determine that π-π stacking together with electrostatic interaction plays an important role in acriflavine adsorption and release from ACF@MOF composites. The molecular docking results have shown that acriflavine interacts with several possible binding sites within the RBD and binding site at the RBD/ACE2 interface. The cytotoxicity and ecotoxicity results have confirmed that the prepared ACF@MOF composites may be considered potentially safe for living organisms. The complementary experimental and theoretical results presented in this study have confirmed that the ACF@MOF composites may be considered a potential candidate for the COVID-19 treatment, which makes them good candidates for clinical trials.

Significant changes in follicular fluid phthalate metabolite levels reflect the lifestyle changes brought about by the strict COVID-19 lockdown in India.

OBJECTIVE: To assess if the unprecedented changes in lifestyle because of the lockdown initiated by the COVID-19 pandemic, which altered human behavior, and influenced purchase and consumption patterns, may have had an impact on the exposure to phthalates in Indian women undergoing in vitro fertilization/intracytoplasmic sperm injection (IVF/ICSI). To evaluate if the effects of the strict and lengthy lockdown in India, which promoted the new norms of stay-at-home and work-from-home, closure of beauty parlors, and restriction on public gatherings, may have contributed to a decrease in the exposure to phthalates like dibutyl phthalate and diethyl phthalate. These chemicals are found in many personal care products (PCPs) which include cosmetics and fragrances. To investigate if the extensive use of flexible single-use plastic in personal protective equipment like face masks/gloves and in plastic packaging used for online purchases, food takeaways, and home deliveries of essentials and groceries during the COVID-19 pandemic, in an attempt to provide a contact-free delivery system may have inadvertently led to an increase in exposure to phthalates like di(2-ethylhexyl) phthalate, di-isononyl phthalate, and di-isodecyl phthalate which are plasticizers used in manufacturing flexible plastic. DESIGN: A comparative study of the levels of six phthalate metabolites detected in follicular fluid (FF) of Indian women undergoing IVF/ICSI 1 year before and immediately after the lockdown initiated by the COVID-19 pandemic. SETTING: In vitro fertilization center in a large referral hospital in India. PATIENT(S): A total of 176 Indian women seeking treatment for infertility and undergoing oocyte retrieval were included after obtaining consent. Each woman contributed one FF sample to the study. Group A (n = 96) women (mean age, 34.0 [±3.9] years, and mean BMI, 25.4 [±4.8]) had their FF samples collected and screened between January 2019 and mid-March 2020, 1 year before the lockdown. Group B (n = 80) women (mean age, 33.9 [±4.1] years, and mean BMI, 25.0 [±4.4]) had their FF collected and screened post the lockdown between October 2020 and June 2021. Both groups were matched by age and BMI. INTERVENTION(S): The cryopreserved FF samples of 176 women were processed using enzymatic deconjugation as well as the solid-phase extraction technique, and analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) to detect the total levels of six phthalate metabolites. MAIN OUTCOME MEASURE(S): To evaluate the impact of the COVID-19 lockdown on the change in the phthalate metabolite levels in the FF of Indian women undergoing IVF/ICSI pre and post the lockdown. RESULT(S): The median levels of mono-n-butyl phthalate (1.64 ng/ml in group A vs. 0.93 ng/ml in group B; P<.001) and mono-ethyl phthalate (5.25 ng/ml in group A vs. 3.24 ng/ml in group B; P<.001) metabolites of dibutyl phthalate and diethyl phthalate found in PCPs including cosmetics and fragrances were significantly higher in the FF of 96 women (group A) compared with the levels seen in the FF of 80 women (group B). However, the median levels of mono-isononyl phthalate (0.11ng/ml in group A vs. 0.13 ng/ml in group B; P<.001), mono-isodecyl phthalate (0.11 ng/ml in group A vs. 0.14 ng/ml in group B; P<.001), and mono(2-ethyl-5-oxohexyl) phthalate (0.13 ng/ml in group A vs. 0.14 ng/ml in group B; P=.023) metabolites of di-isononyl phthalate, di-isodecyl phthalate, and di(2-ethylhexyl) phthalate used as plasticizers were significantly higher in the FF of women in group B compared with women in group A. CONCLUSION(S): The significant drop in mono-n-butyl phthalate and mono-ethyl phthalate levels, accumulated in the FF of 80 Indian women in group B reflects a decrease or absence of usage patterns of PCPs, including cosmetics and fragrances, thereby suggesting that these women may have deprioritized their use during the COVID-19 pandemic giving preference to personal hygiene and safety. Whereas the unprecedented increase in the use of flexible single-use plastic that became our first line of defense against the coronavirus during the COVID-19 pandemic might be responsible for the accumulation of significantly higher levels of mono-isononyl phthalate, mono-isodecyl phthalate, and mono(2-ethyl-5-oxohexyl) phthalate in FF of the same group.

Di-(2-ethylhexyl) Phthalate Triggers Proliferation, Migration, Stemness, and Epithelial-Mesenchymal Transition in Human Endometrial and Endometriotic Epithelial Cells via the Transforming Growth Factor-ß/Smad Signaling Pathway.

Di-(2-ethylhexyl) phthalate (DEHP) is a frequently used plasticizer that may be linked to the development of endometriosis, a common gynecological disorder with a profound impact on quality of life. Despite its prevalence, vital access to treatment has often been hampered by a lack of understanding of its pathogenesis as well as reliable disease models. Recently, epithelial-mesenchymal transition (EMT) has been suggested to have a significant role in endometriosis pathophysiology. In this study, we found that DEHP treatment enhanced proliferation, migration, and inflammatory responses, along with EMT and stemness induction in human endometrial and endometriotic cells. The selective transforming growth factor-ß (TGF-ß) receptor type 1/2 inhibitor LY2109761 reversed the DEHP-induced cell proliferation and migration enhancement as well as the increased expression of crucial molecules involved in inflammation, EMT, and stemness, indicating that DEHP-triggered phenomena occur via the TGF-ß/Smad signaling pathway. Our study clearly defines the role of DEHP in the etiology and pathophysiological mechanisms of endometriosis and establishes an efficient disease model for endometriosis using a biomimetic 3D cell culture technique. Altogether, our data provide novel etiological and mechanistic insights into the role of DEHP in endometriosis pathogenesis, opening avenues for developing novel preventive and therapeutic strategies for endometriosis.

Electrochemical immunosensor for rapid and highly sensitive detection of SARS-CoV-2 antigen in the nasal sample.

A label-free electrochemical biosensing approach as an appropriate analysis technique for SARS-CoV-2 spike protein (SARS-CoV-2 S-protein) was investigated to facilitate the diagnosis of coronavirus in real samples. It is crucial to construct diagnostic features that can rapidly identify infected individuals to limit the spread of the virus and assign treatment choices. Therefore, a novel and selective method using SiO2@UiO-66 and a label-free electrochemical immunoassay for rapidly detecting spike protein. The development of innovative approaches for direct viral detection employing simplified and ideally reagent-free assays is a pressing and difficult topic. The absence of speedy and effective ways to diagnose viral diseases especially SARS-CoV-2 on demand has worsened the issue of combating the COVID-19 pandemic. The developed electrode illustrated a wide dynamic range of 100.0 fg mL-1 to 10.0 ng mL-1 with low limit detection. Therefore, the as-fabricated electrochemical SARS-CoV-2 S-protein sensor suggests an appropriate perspective in the point-of-care system, within 5.0 min, in nasal samples with satisfactory recovery.

Widespread occurrence of phthalate and non-phthalate plasticizers in single-use facemasks collected in the United States.

Single-use or disposable facemasks have been widely used by the public for personal protection against the spread of COVID-19. The majority of disposable facemasks are made of synthetic polymers such as polypropylene, polyethylene terephthalate (as polyester), and polystyrene, and could therefore be a source of human exposure to plasticizers that are incorporated into these polymers during production. Little is known, however, about the occurrence of plasticizers in facemasks. In this study, we determined the concentrations of nine phthalate diesters and six non-phthalate plasticizers in 66 facemasks purchased in the United States. Among phthalate diesters, dibutyl phthalate, di(2-ethylhexyl)phthalate, di-iso-butyl phthalate, and butyl benzyl phthalate were found in all facemask samples, at median concentrations of 486, 397, 254, and 92 ng/g, respectively. Among non-phthalate plasticizers, dibutyl sebacate (median: 3390 ng/g) and di(2-ethylhexyl)adipate (352 ng/g) were found at notable concentrations. Inhalation exposure to select phthalate and non-phthalate plasticizers from the use of facemasks was estimated to range from 0.1 to 3.1 and 3.5 to 151 ng/kg-bw/d, respectively. To our knowledge, this is the first study to report the occurrence of phthalate and non-phthalate plasticizers in facemasks collected from the United States.

Phthalate esters in face masks and associated inhalation exposure risk.

This study assessed the composition of single-use face mask materials, quantified the concentration of phthalate esters in masks and evaluated associated inhalation exposure risk. All the mask samples, including 12 surgical and four N95/P1/P2 masks, were identified to be made of polypropylene, with polyethylene terephthalate present in the N95/P1/P2 masks. Di-methyl phthalate, di-n-butyl phthalate, di-ethyl phthalate, di-isobutyl phthalate and di(2-ethylhexyl) phthalate were frequently detected and their concentration summed up 55 ± 35 ~ 1700 ± 140 ng per surgical mask and 2300 ± 150 ~ 5200 ± 800 ng per N95/P1/P2 mask. Our simulation experiment suggested a mean loss of 13 - 71% of phthalate mass depending on compounds, during 5-hour wearing of these masks. This resulted in an estimated daily intake of individual compounds no higher than 20 ng/kg/day for adults and 120 ng/kg/day for toddlers, which were at least 80 times lower compared to relevant tolerable daily intake values. Two interventional trials were conducted where a volunteer wore a mask for four hours and urine samples were collected before and after the mask wearing. No obvious increase was observed for the urinary concentration of any phthalate metabolite, indicating minimal contribution to overall exposure to phthalate esters.

Face mask-A potential source of phthalate exposure for human.

Face masks are necessary for fighting against the coronavirus disease 2019 around the world. As the face mask is usually made from polymers and phthalates are widely-used additives into the polymers, the face mask could be a potential source of phthalate exposure to humans. However, limited knowledge is available on the occurrence and risks of the phthalates from the face mask. In this study, twelve phthalates were determined in 56 mask samples collected from different countries. The phthalates were detected in all the samples with total levels ranging from 115 ng/g to 37,700 ng/g. Estimated daily intakes (EDIs) of the phthalates from the masks ranged from 3.71 to 639 ng/kg-bw/day, and the EDIs of the phthalates from masks for toddlers were approximately 4-5 times higher than those for adults. Non-carcinogenic risks in relation to the phthalates in masks were found to be within safe levels, yet 89.3% of the mask samples exhibited potential carcinogenic effects to humans. The extent of the risks for wearing masks located at a moderate level comparing with other skin-contacted products. This study unveiled a potential source of phthalate exposure to human, and indicated necessity of managing types and levels of additives in the face masks.

Rapid in-situ analysis of phthalates in face masks by desorption corona beam ionization tandem mass spectrometry.

Phthalates (PAEs) are known as endocrine disruptors that can have adverse effects on human hormonal balance and development. Due to PAEs being semi-volatile chemical compounds, they can sustainably emit from the surfaces of objects containing PAEs. Face masks are commonly used to safeguard human health especially during periods of high prevalence of infectious diseases. As masks come into direct contact with the human respiratory system, PAEs from masks will enter the human body directly from the respiratory system thus potentially threatening human health. In this study, the desorption corona beam ionization (DCBI)-MS/MS method for the rapid in-situ detection of PAEs in face masks was established, which could perform ultra-fast, high-throughput identification and quantitative analysis on 13 kinds of PAEs, and the limits of detection (LODs) were 0.7 µg m-2 for DAP, BBP, DBP, DPP, DHXP, DEHP, DINP and DDP, 1.4 µg m-2 for DMEP, DEP, DPhP, DBEP and DNOP. Compared with the traditional liquid chromatography tandem mass spectrometry, this study shows that the DCBI-MS/MS method has the following advantages: 1) short analysis time, less than 1 min; 2) small solvent consumption, less than 10 µL; 3) the PAEs in face masks can be quickly in-situ screened.

Cracking the Chloroquine Conundrum: The Application of Defective UiO-66 Metal-Organic Framework Materials to Prevent the Onset of Heart Defects-In Vivo and In Vitro.

In this study, we present a modulated synthesis nanocrystalline defective UiO-66 metal-organic framework as a potential chloroquine diphosphate (CQ) delivery system. Increasing the concentration of hydrochloric acid during the modulated synthesis resulted in a considerable increase of pore volume, which enhanced the CQ loading in CQ@UiO-66 composites. Drug release tests for CQ@UiO-66 composites have confirmed prolonged CQ release in comparison with pure CQ. In vivo tests on a Danio reiro model organism have revealed that CQ released from CQ@UiO-66 25% showed lower toxicity and fewer cardiotoxic effects manifested by cardiac malformations and arrhythmia in comparison to analogous doses of CQ. Cytotoxicity tests proved that the CQ loaded on the defective UiO-66 cargo resulted in increased viability of cardiac cells (H9C2) as compared to incubation with pure CQ. The experimental results presented here may be a step forward in the context of reducing the cardiotoxicity CQ.