Detection of phthalates migration from disposable tablewares to drinking water using hexafluoroisopropanol-induced catanionic surfactant coacervate extraction

Hexafluoroisopropanol(HFIP)-induced sodium dodecyl sulfate/dodecyltrimethylammonium bromide(SDS/DTAB) catanionic surfactant coacervate extraction method coupled with high performance liquid chromatography(HPLC) was used to detect the migration of phthalates from disposable tablewares to drinking water. The concentration factors are larger than 82 and extraction recoveries over 53% for water samples spiked with 100 or 200 ng/m L phthalates. Limit of detection is in the range of 1.0–2.6 ng/m L.Good linearity with correlation coefficients larger than 0.9985 is obtained in the concentration of20–1500 or 40–3000 ng/m L. Relative recoveries are from 82.4% to 123.6% for water samples spiked with30/60, 250/500, and 1500/3000 ng/m L phthalates, respectively. Relative standard deviations(RSDs) are0.4%–7.4% for intraday precision(n = 5) and 0.6%–7.8% for interday precision(n = 3). Four of studied phthalates are found in the drinking water samples prepared from four kinds of tablewares.

Preparation of polypyrrole/nanosilica composite for solid-phase microextraction of bisphenol and phthalates migrated from containers to eye drops and injection solutions

This paper describes the electrodeposition of polyphosphate-doped polypyrrole/nanosilica nano-composite coating on steel wire for direct solid-phase microextraction of bisphenol A and five phthalates. We optimized influencing parameters on the extraction efficiency and morphology of the nanocomposite such as deposition potential, concentration of pyrrole and polyphosphate, deposition time and the nanosilica amount. Under the optimized conditions, characterization of the nanocomposite was inves-tigated by scanning electron microscopy and Fourier transform infra-red spectroscopy. Also, the factors related to the solid-phase microextraction method including desorption temperature and time, extrac-tion temperature and time, ionic strength and pH were studied in detail. Subsequently, the proposed method was validated by gas chromatography-mass spectrometry by thermal desorption and acceptable figures of merit were obtained. The linearity of the calibration curves was between 0.01 and 50 ng/mL with acceptable correlation coefficients (0.9956-0.9987) and limits of detection were in the range 0.002-0.01 ng/mL. Relative standard deviations in terms of intra-day and inter-day by five replicate analyses from aqueous solutions containing 0.1 ng/mL of target analytes were in the range 3.3%-5.4% and 5%-7.1%, respectively. Fiber-to-fiber reproducibilities were measured for three different fibers prepared in the same conditions and the results were between 7.3% and 9.8%. Also, extraction recoveries at two different concentrations were ≥96%. Finally, the suitability of the proposed method was demonstrated through its application to the analysis of some eye drops and injection solutions.

Presence of phthalates in gastrointestinal medications: Is there a hidden danger?

Pharmaceutical companies that produce gastrointestinal(GI)medications often utilize phthalates for their ability to localize medication release.Commonly prescribed GI medications that may utilize phthalates are 5-Aminosalicylates,proton pump inhibitors,and pancreatic enzymes.Our understanding of the cumulative health effects of phthalates from medications remains unclear,and there is increasing evidence that phthalates are not harmless.Experimental studies in animals have shown that phthalates,specifically dibutyl phthalate and Di-(2-ethyl-hexyl)phthalate,have the potential to alter and/or inhibit reproductive biology and in utero development.Despite the lack of definitive human data,many cohort and cross-sectional studies demonstrate concerning associations between phthalates and poor health status,specifically developmental problems.Longitudinal studies and studies with larger sample sizes are required to determine whether phthalates actually cause negative health consequences.It is also important that physicians regularly review and discuss with patients the medicinal ingredients in their medications and supplements,specifically in pregnant woman with inflammatory bowel disease.

Phthalates in Commercial Chinese Rice Wines: Concentrations and the Cumulative Risk Assessment to Adult Males in Shanghai

The concentrations of 16 phthalates in 164 commercial Chinese rice wines （CRW） were detected by GC-MS, and consumption data on CRW in different packaging types was investigated from 634 adult males in Shanghai using a food frequency questionnaire. Based on the prinq：iples of probabilistic modelling and cumulative risk assessment, the exposure and health risk of phthalates from CRW to adult males in Shanghai was evaluated. DMP, DEP, DIBP, DnBP, BBP, and DEHP were detected in the samples, thE： range of detection frequency of individual phthalates varied from 6.10% for BBP to 15.24% for DIBP, and the detected concentrations were 51.06-200.34 ng/mL. All the respondents consumed CRW, 90.69% of them consumed CRW 0.01-49.9 mL/d, the minimum value of the average daily intake of CRW was 6.25 mL/d, the median was 13.72 mL/d and the maximum was 300 mL/d. The median exposure level of the 6 detected Phthalates to adult males in Shanghai were 6.58-7.10 ng/（d.kg）, and the maximum exposure level were 137.38-540.47 ng/（d.kg）. The cumulative exposure health risk index （HI） based on the median and maximum exposure level of the 6 Phthalates （DMP, I~）EP, DIBP, DnBP, BBP, and DEHP） were 0.001147 ancl 0.063396, both were far less than 1. In conclusion, CRW were generally consumed by the adult males in Shanghai.

2D-and 3D-QSBR Studies on the Relationship between Structure and Biodegradability of Phthalates

Nine phthalates were calculated at the B3LYP/6-311G＊＊ level using DFT method. The corresponding linear relationship equations （R2 were 0.853 and 0.936 respectively） for the biodegradation rate （Kb） and half-life time （h/2） of biodegradation were obtained with the structural parameters as theoretical descriptors. Furthermore, CoMFA method was also applied to establish 3D models which revealed the fields influencing these properties. The relationship between the properties and the structure was obtained. The correlation coefficients of the models were 0.992 and 0.999, respectively. Analyses of 2D and 3D models demonstrated that the molecular volume was an important factor affecting the biodegradability of these compounds.

Ovarian Toxicity and Epigenetic Mechanisms of Phthalates and Their Metabolites

Ovary plays an important role in the female reproductive system.The maintenance and regulation of ovarian function are affected by various physical and chemical factors.With the development of industrialization,environmental pollutants have caused great harm to public health.Phthalates,as a class of endocrine-disrupting chemicals(EDCs),are synthesized and used in large quantities as plasticizers due to their chemical properties.They are easily released into environment because of their noncovalent interactions with substances,causing human exposure and possibly impairing ovary.In recent years,more and more attention has been paid to the role of epigenetics in the occurrence and development of diseases.And it is urgent to study the role of methylation,gene imprinting,miRNA,and other epigenetic mechanisms in reproductive toxicology.

High Performance Liquid Chromatographic Identification and Estimation of Phthalates in Sewer Waste and a Receiving River in Ibadan City, Southwestern Nigeria

Medical wastes have been implicated in river pollution in developing countries and most often people depend on water from such rivers for sources of livelihood. Phthalates (endocrine disruptors) are major components in medical wastes and are commonly found contaminants in aquatic environment. Most sewage treatment facilities handling medical waste are inefficient due to overuse and poor maintenance and discharge directly into rivers. This study aimed to investigate the identity and estimates the concentration of phthalates in supposed treated medical wastes from a hospital sewer and water from a receiving river. Samples were randomly collected before and after treatment by the sewer plants, while samples were randomly collected along the course of the river starting from point of discharge. Control samples were taken from upstream about 500 m along the river course. The samples were extracted by liquid-liquid chroma- tographic process using dichloromethane, after which they were cleaned up in a column of silica gel using hexane as the mobile solvent. The cleaned extracts were analyzed by HPLC. The concentrations (μg/L) of dimethyl-, diethyl-, diphenyl-, dibutyl- and di-(2-ethyl)hexyl phthalates ranged from 62.81 ± 18.53;4.74 ± 3.57;2.05 ± 1.80;11.40 ± 5.58 to 141.92 ± 35.8 respectively in the sewer waste. The receiving river had a concentration (μg/L) of 9.17 ± 14.02;0.18 ± 0.31;0.48 ± 0.84;2.84 ± 1.21;61.72 ± 38.35 respectively for dimethyl-, diethyl-, diphenyl-, dibutyl- and di-(2-ethyl) hexyl phthalates. These concentrations were higher than control and far exceeded the USEPA limits of 3 μg/l recom- mended for phthalates in water. Contaminants of aquatic environment by untreated wastes from hospitals has serious implications on public health and environment as human risks for phthalate esters downstream are high and this calls for urgent need to develop strategy to build incentives for compliance in treatment and discharge of wastes into river waters.

Sorption and desorption kinetics of phthalates and phenol on water/sediment interface

The sorption and desorption kinetics of dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP) and phenol on water and sediment interface were studied using two compartment model in this paper. The results showed that the sorption coefficients of DMP, DEP, DBP and phenol measured by batch equilibrium method were 16.79, 24.55, 132 and 0.65μg 1-1/n · g -1 · ml -1/n , the sorption and desorption kinetic constants of DMP, DEP, DBP, phenol were 0.0248, 0.0357, 0.0727, 0.014ml·cm -2 ·h -1 and 0.000512, 0.000754, 0.00127, 0 000899h -1 at static condition respectively; and the sorption and desorption kinetics constants of above chemicals were 0 279, 0.382, 0.496, 0.0904ml·cm -2 ·h -1 and 0.0442, 0.0031, 0.00116, 0.00247h -1 at flow water condition respectively.

Validated Method for the Detection of Three Phthalates Derived from Marine Invertebrates

This study represents, detailly, the validated method for the extraction and quantification of widespread phthalic acid esters (PAEs) bis(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DBP) and di-n-octyl phthalate (DnOP) from solitary ascidians collected from a marine environment. The extraction was based on a pressurized liquid extraction method, using n-hexane as the solvent to extract the target PAEs from dry biological tissues, and was performed in an accelerated solvent extraction instrument. The average recovery of 89.2% was obtained from samples subjected to a pressure of ~1500 psi and 120°C in two 10-min cycles. GC-MS was used for quantification, conducted in single-ion monitoring mode. Following careful and rigorous cleanup procedures to prevent cross-contamination from laboratory glassware, PAE standards showed signals with good specificity. The obtained limits of detection were 130, 122 and 89 ng/g for DEHP, DBP and DnOP, respectively. Accordingly, the calculated limits of quantification were 394, 370 and 270 ng/g for DEHP, DBP and DnOP, respectively. The obtained linearity ranged from 5.4 to 269 ng/ml (equivalent to 135 - 6725 ng/g dry weight), with R2 ≥ 0.998. Concentrations in the range of 200 to 9000 and 400 to 5000 ng/g sample dry weight, for DEHP and DBP, respectively, were obtained from the ascidians. No DnOP was detected in any of the samples. These results indicate that the method presented in this study is applicable for detection of low and trace concentrations of the target PAEs in samples collected from a marine organism, which can serve as a bioindicator of plastic contamination.

Characteristics and health risks of population exposure to phthalates via the use of face towels

The production of face towels is growing at an annual rate of about 4%in China,reaching 1.13 million tons by 2021.Phthalates(PAEs)are widely used in textiles,and face towels,as an important household textile,may expose people to PAEs via the skin,further leading to health risks.We collected new face towels and analyzed the distribution characterization of PAEs in them.The changes of PAEs were explored in a face towel use experiment and a simulated laundry experiment.Based on the use of face towels by 24 volunteers,we calculated the estimated daily intake(EDI)and comprehensively assessed the hazard quotient(HQ),hazard index(HI),and dermal cancer risk(DCR)of PAEs exposure in the population.PAEs were present in new face towels at total concentrations of<MDL–2388 ng/g,with a median of 173.2 ng/g,which was a lower contamination level compared with other textiles.PAE contents in used face towels were significantly higher than in new face towels.The concentrations of PAEs in coral velvet were significantly higher than those in cotton.Water washing removed some PAEs,while detergent washing increased the PAE content on face towels.Gender,weight,use time,and material were the main factors affecting EDI.The HQ and HIwere less than 1,which proved PAEs had no significant non-carcinogenic health risks.Among the five target PAEs studied,DEHPwas the only carcinogenic PAE andmay cause potential health risks after long-term exposure.Therefore,we should pay more attention to DEHP.

Cooperation between Pt and Ru on RuPt/AC bimetallic catalyst in the hydrogenation of phthalates

RuPt/AC bimetallic catalysts were pre pared by two-step incipient impregnation method and evaluated in the hydrogenation of phthalates.According to the characterization results,well dispersed Ru Pt bimetallic nanoparticles were formed on the catalyst,and the strong interaction between the two metals resulted in the formation of RuPt alloy.It was found that Ru can donate electrons to Pt on RuPt alloy nanoparticles,leading to the formation of electron-deficient Ru which significantly promotes the hydrogenation rate of dioctyl phthalate and improves the selectivity of dioctyl di-2-ethylhexylcyclohexane-1,4-dicarboxylate by accelerating the further hydrogenation of intermediate products.The bimetallic RuPt catalyst also presented excellent stability and versatility in the hydrogenation of phthalates,demonstrating its prospective future in the hydrogenation of aromatic ring contained compounds.

Modeled exposure to phthalates via inhalation and dermal pathway in children's sleeping environment: A preliminary study and its implications

In this study,exposure to phthalates during children’s sleeping time was evaluated based on a mechanistic model.Airborne phase-specific concentrations in this model were estimated taking into account kinetic partitioning,particle dynamics and time-varying ventilation.Exposure pathways considered were inhalation exposure to airborne phases,dermal absorption from "air-to-skin" transport and direct contact.By taking di(n-butyl)phthalate(DnBP)and bis(2-ethylhexyl)phthalate(DEHP)as two representative pollutants,inhalation exposure accounted for>90%when children wore clean pajamas before going to bed.Dermal uptake significantly increased when children's pajamas had absorbed DnBP before putting them on,whereas dermal uptake of DEHP was relatively lower and insensitive to the condition of clothing.Increasing air exchange rate at night and keeping clothes cleaner were effective for reducing children's exposures during sleeping period.Further studies are necessary taking into account source-proximity effect,particle emissions and refined dermal exposure routes.

Research Progress on Distribution,Sources and Ecological Effects of Phthalate in Soil

Phthalate esters(PAEs)are widely used as main plasticizers in plastic products,agricultural regulators,toys,and other fields.This paper reviewed the research progress on the distribution,sources,and ecological effects of PAEs.The effects of PAEs on soil microorganisms,animals,plants and soil properties were explored in sequence,providing effective theoretical basis for future research on PAEs.

Recent Advances of Sensitive Electrochemical Sensing Platforms for Rapid Detection of Phthalate Acid Esters

As a kind of plasticizer,phthalic acid esters(PAEs)are often added to plastics to enhance elasticity,transparency,durability and prolong service life.However,it does not chemically bind to plastics and is easy to migrate to the environment.It is difficult to degrade in the environment,and it is also enriched in the human body through the food chain and respiration,which will lead to obvious adverse reactions such as decreased learning and memory function and neurobehavioral disorders.Due to the toxicity,universality and low concentration limitations of PAEs in the environment and food,it is essential to achieve rapid and sensitive detection of PAEs in soil,atmosphere,water and food.Electrochemical(EC)sensors have the advantages of simplicity,fast,low cost,portability,easy operation,high specificity and high sensitivity,so they are applied for the detection of PAEs.Although there are a large number of studies on the detection of PAEs by EC sensors,there is no review on this aspect.In this review,we introduce the detection of PAEs from classical EC sensors,electrochemiluminescence(ECL)sensors and photo-electrochemical(PEC)sensors in the past five years.This review is beneficial to understanding the construction of EC sensors and the detection mechanism of PAEs.We also propose that the development of rapid,accurate and real-time detection methods of PAEs is key to assessing risk and preventing related diseases.

Pollution characteristics of 15 gas- and particle-phase phthalates in indoor and outdoor air in Hangzhou

Phthalate esters(PAEs),typical pollutants widely used as plasticizers,are ubiquitous in various indoor and outdoor environments.PAEs exist in both gas and particle phases,posing risks to human health.In the present study,we chose four typical kinds of indoor and outdoor environments with the longest average human residence times to assess the human exposure in Hangzhou,including newly decorated residences,ordinary residences,offices and outdoor air.In order to analyze the pollution levels and characteristics of 15 gasand particle-phase PAEs in indoor and outdoor environments,air and particulate samples were collected simultaneously.The total PAEs concentrations in the four types of environments were 25,396,25,466.8,15,388.8 and 3616.2 ng/m^3,respectively.DEHP and DEP were the most abundant,and DMPP was at the lowest level.Distinct variations in the distributions of indoor/outdoor,gas/particle-phase and different molecular weights of PAEs were observed,showing that indoor environments were the main sources of PAEs pollution.While most PAEs tended to exsit in indoor sites and gas-phase,the high-molecular-weight chemicals tended to exist in the particle-phase and were mainly found in PM2.5.PAEs were more likely adsorbed by small particles,especially for the indoor environments.There existed a good correlation between the particle matter concentrations and the PAEs levels.In addition,neither temperature nor humidity had obvious effects on the distributions of the PAEs concentrations.

High Efficient Extraction of Phthalates in Aquatic Products by a Modified QuEChERS Method

A simple, environmentally friendly and high efficient extraction method was proposed for the determina- tion of five phthalates in aquatic products by gas chromatography combined with mass spectrometry detector （GC-MS）. When this method was adopted, samples were pretreated by modified QuEChERS（quick, easy, cheap, effective, rugged and safe） method. An environmentally friendly extractant（ethanol aqueous solution） replaced toxic acetonitrile for extracting phthalates in the protein-matrix samples. Fluorescence quenching spectra of bovine serum albumin（BSA） with phthalates show that there was a high-affinity interaction between phthalate and protein, de- creasing the extraction efficiency of phthalates from fish samples. However, in the 80%（volume fraction, ~） ethanol aqueous solution, a slow but full protein denaturation takes place, which would cause the unfolding of protein and the release of phthalates. Meanwhile, the fat-soluble impurities are extracted less in ^（ethanol） 80% aqueous solution than in either ~p（ethanol） 100% or hydrophobic solvents in the liquid-liquid extraction procedure. Therefore the puri- fication steps were greatly simplified. Overall recoveries were 81.77%--90.5% with limits of detection between 2.53 and 9.61 ~tg/L, and relative standard deviation values at 1.15%---4.85%. The proposed approach was satisfactorily applied to the determination of phthalates in real aquatic products, such as fish, shrimp and oyster.

Food emulsifier glycerin monostearate aggravates phthalates'testicular toxicity by disrupting tight junctions'barrier function in rats

Objectives:This study aimed to investigate the effect of the widely used food emulsifier glycerin monostearate(GM)on testicular toxicity caused by the mixture of three commonly used phthalate esters(MPEs)in rats,and further to explore the underlying mechanism.Materials and Methods:Thirty male Sprague-Dawley rats were randomly divided into three groups.Rats were orally treated with 160 mg/kg/d MPEs in the MPEs group;coinstantaneously treated with 160 mg/kg/d MPEs and 200 mg/kg/d GM in the MPEs+GM group;and treated with the excipient in the control group.The intervention lasted for 5 weeks.Testis weight,epididymis weight,testicular histopathology,and serum testosterone were detected for testicular toxicity evaluation.The testicular ultrastructure,the tight junction proteins zonula occluden(ZO)-1,and claudin were measured for the mechanism exploration.Results:The body weight,epididymis,serum testosterone level,and anogenital distance in the MPEs+GM group were significantly decreased compared with control group(P<0.05);Testicular histopathological observation showed that shed spermatids were observed in the MPEs+GM group.Ultrastructural observation of testicular cells showed that the cristae number was decreased in some mitochondria in the MPEs group,whereas the cristae were fused and disappeared in most mitochondria in the MPEs+GM group.The tight junctions were broken in the MPEs+GM group;meanwhile,the expression of ZO-1 and claudin were altered in the MPEs+GM group(P<0.01).Conclusions:The results from this study indicated that GM aggravated MPEs'testicular toxicity,which might relate to the injured mitochondria and damaged tight junctions in testicular tissue.

Concentrations of phthalates metabolites in blood and semen and the potential effects on semen concentration and motility among residents of the Pearl River Delta region in China

Exposure to phthalate acid esters(PAEs)has been found to have adverse effects on reproduction of human and animal.However,the effects on the semen quality are controversial.In this study,we have collected paired blood and sperm samples from patients(n=103)at a medical clinic in Guangzhou,China,to determine the concentrations of eight phthalate metabolites∑8m-PAEs).The concentration ranges of P8m-PAEs were 2.7-55 and 0.99-17 ng/mL in blood and semen samples,respectively.MEHP(median,3.6 ng/mL in blood and 0.55 ng/mL in semen)and MnOP(median,3.4 ng/mL in blood and 0.69 ng/mL in semen)were the predominant analytes in both blood and semen samples.However,analytes were not correlated in paired blood and semen.Semen motility was significantly associated to the concentrations of∑8m-PAEs in semen,but it did not associate to the concentrations of PAEs in blood.Multi-linear regression analysis,including concentrations of PAEs in both blood and semen,as well as BMI,occupation,living habits,suggested that exposure to PAEs at current environmental levels had very limited effects on semen quality of population in Guangzhou,China.

Food contaminants and potential risk of diabetes development:A narrative review

The number of people diagnosed with diabetes continues to increase,especially among younger populations.Apart from genetic predisposition and lifestyle,there is increasing scientific and public concern that environmental agents may also contribute to diabetes.Food contamination by chemical substances that originate from packaging materials,or are the result of chemical reactions during food processing,is generally recognized as a worldwide problem with potential health hazards.Phthalates,bisphenol A(BPA)and acrylamide(AA)have been the focus of attention in recent years,due to the numerous adverse health effects associated with their exposure.This paper summarizes the available data about the association between phthalates,BPA and AA exposure and diabetes.Although their mechanism of action has not been fully clarified,in vitro,in vivo and epidemiological studies have made significant progress toward identifying the potential roles of phthalates,BPA and AA in diabetes development and progression.These chemicals interfere with multiple signaling pathways involved in glucose and lipid homeostasis and can aggravate the symptoms of diabetes.Especially concerning are the effects of exposure during early stages and the gestational period.Well-designed prospective studies are needed in order to better establish prevention strategies against the harmful effects of these food contaminants.

Bis(2-butoxyethyl) Phthalate Delays Puberty Onset by Increasing Oxidative Stress and Apoptosis in Leydig Cells in Rats

Objective This study investigated the effects of bis(2-butoxyethyl) phthalate(BBOP) on the onset of male puberty by affecting Leydig cell development in rats.Methods Thirty 35-day-old male Sprague-Dawley rats were randomly allocated to five groups mg/kg bw per day that were gavaged for 21 days with BBOP at 0, 10, 100, 250, or 500 mg/kg bw per day. The hormone profiles;Leydig cell morphological metrics;mRNA and protein levels;oxidative stress;and AKT,mTOR, ERK1/2, and GSK3β pathways were assessed.Results BBOP at 250 and/or 500 mg/kg bw per day decreased serum testosterone, luteinizing hormone, and follicle-stimulating hormone levels mg/kg bw per day(P < 0.05). BBOP at 500 mg/kg bw per day decreased Leydig cell number mg/kg bw per day and downregulated Cyp11a1, Insl3, Hsd11b1,and Dhh in the testes, and Lhb and Fshb mRNAs in the pituitary gland(P < 0.05). The malondialdehyde content in the testis significantly increased, while Sod1 and Sod2 mRNAs were markedly downregulated, by BBOP treatment at 250–500 mg/kg bw per day(P < 0.05). Furthermore, BBOP at 500mg/kg bw per day decreased AKT1/AKT2, mTOR, and ERK1/2 phosphorylation, and GSK3β and SIRT1levels mg/kg bw per day(P < 0.05). Finally, BBOP at 100 or 500 μmol/L induced ROS and apoptosis in Leydig cells after 24 h of treatment in vitro(P < 0.05).Conclusion BBOP delays puberty onset by increasing oxidative stress and apoptosis in Leydig cells in rats.The graphical abstract is available on the website www.besjournal.com.