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Concept: Plasticizers

40

Phthalates are ubiquitous chemicals linked to hormonal disruptions that affect reproduction and development. Multiple anti-androgenic phthalates exposure during fetal development can have greater impacts than individual exposure; thus, the National Academy of Sciences (NAS) recommends them for cumulative assessment. Using National Health and Nutrition Examination Survey data (NHANES, 2001-2012), we developed a potency-weighted sum of daily intake (∑androgen-disruptor; µg/kg/day) of di-n-butyl phthalate (DnBP), diisobutyl phthalate (DiBP), butyl benzyl phthalate (BBzP), and di(2-ethylhexyl) phthalate (DEHP) based on NAS recommendations, and included diethyl phthalate (DEP) and diisononyl phthalate (DiNP) in additional metrics (2005-2012). We compared racial/ethnic differences in ∑androgen-disruptor among 2842 reproductive-aged women. In sensitivity analyses, we assessed the influence of potency assumptions, alternate urine dilution adjustment methods, and weighting phthalate metabolites directly rather than daily intake estimates of parent compounds. We found that DEHP contributed most to ∑androgen-disruptor (48-64%), and that ∑androgen-disruptor decreased over time. Black women generally had higher cumulative exposures than white women, although the magnitude and precision of the difference varied by model specification. Our approach provides a blueprint for combining chemical exposures linked to common adverse outcomes, and should be considered in future exposure, risk, and epidemiological studies.

Concepts: Phthalates, Phthalate, Diethyl phthalate, Plasticizer, Bis(2-ethylhexyl) phthalate, Plasticizers, Diisononyl phthalate, Diisoheptyl phthalate

29

Di-(2-ethylhexyl) phthalate (DEHP) is a plasticizer widely used in the production of poly-(vinyl) chloride (PVC) materials. It is a reproductive and developmental toxicant in animals and a suspected endocrine modulator in humans. DEHP is not covalently bound within the PVC molecule, which is why migration into a suitable medium can be expected. Since application of infusion solutions is one of the most common medical treatments, the objective of this study was to determine the migration of phthalates from softened PVC storage bags into infusion solution in different time periods within one year from date of production using a gas chromatography-mass spectrometry method. The measured values of DEHP ranged between 0.22 and 14.00 µg l(-1) , but the unexpected presence of other phthalate esters was also detected. It was concluded that values obtained in infusion solutions match the reference data and represent a minor risk for the patient. The presence of other phthalate esters leads to the conclusion that the pharmacopeic requirement for polymer cleanness was not fully met. Since phthalate esters are among the most extensively used industrial chemicals and are widely distributed in the environment, special precautions and further monitoring should be conducted to minimize any possible health risks.

Concepts: Chemistry, Plastic, Phthalates, Phthalate, Plasticizer, Bis(2-ethylhexyl) phthalate, Plasticizers, Diisononyl phthalate

29

This survey determined the levels of eight phthalates - i.e. dimethyl phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP), benzylbutyl phthalate (BzBP), di(2-ethylhexyl) phthalate (DEHP), dicyclohexyl phthalate (DCHP) and di-n-octyl phthalate (DnOP) - in several Belgian milk and dairy products. Samples were obtained from various farms, a dairy factory and from different shops in order to investigate phthalate contamination “from farm to fork”. At several stages in the milk chain, product contamination with phthalates - mostly DiBP, DnBP, BzBP and DEHP - was observed. At farm level, the mechanical milking process and the intake of phthalate containing feed by the cattle were found to be possible contamination sources. At industry and retail level, contact materials including packaging materials were additional contamination sources for phthalates in milk and dairy products.

Concepts: Milk, Cattle, Dairy, Phthalates, Phthalate, Diethyl phthalate, Plasticizers, Diisobutyl phthalate

28

A direct, sensitive and rapid method for the detection of smokeless powder components, from five different types of ammunition, is demonstrated using laser electrospray mass spectrometry (LEMS). Common components found in powder, such as ethyl centralite, methyl centralite, dibutyl phthalate and dimethyl phthalate, are detected under atmospheric conditions without additional sample preparation. LEMS analysis of the powders revealed several new mass spectral features that have not been identified previously. Offline principal component analysis and discrimination of the LEMS mass spectral measurements resulted in perfect classification of the smokeless powder with respect to manufacturer.

Concepts: Mass spectrometry, Multivariate statistics, Principal component analysis, Electrospray ionization, The Unscrambler, Plasticizers, Smokeless powder, Centralite

28

Food products can be contaminated with toxic compounds via the environment. Another possibility of food contamination is that toxicants are generated in foods or that chemicals migrate from food contact materials into foods during processing. In this study, the effect of cooking at home on the levels of phthalates - world’s most used group of plasticisers - in various food types (starchy products, vegetables and meat and fish) was examined. Eight compounds were considered, namely dimethyl phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP), benzylbutyl phthalate (BBP), di(2-ethylhexyl) phthalate (DEHP), dicyclohexyl phthalate (DCHP) and di-n-octyl phthalate (DnOP). Food products were analysed before as well as after cooking (boiling, steaming, (deep-)frying or grilling). In general, phthalate concentrations in foods declined after cooking, except in vegetables, where almost no effect was seen. Several factors influenced the degree of this decline (e.g. weight difference, fat uptake, etc.). Of all phthalates, DEHP, DiBP and BBP were affected the most. In conclusion, cooking at home definitely affected phthalate concentrations in foods and thus needs to be considered in order to correctly assess humans' dietary exposure to these contaminants.

Concepts: Nutrition, Food, Phthalates, Phthalate, Food safety, Cooking, Bis(2-ethylhexyl) phthalate, Plasticizers

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The daily intakes (DI) were estimated in a Belgian general population for 5 phthalates, namely diethyl phthalate (DEP), di-n-butyl phthalate (DnBP), di-iso-butyl phthalate (DiBP), butylbenzyl phthalate (BBzP) and di-2-ethylhexyl phthalate (DEHP), based on the urinary measurements of their corresponding metabolites. DI values ranged between

Concepts: Risk, Phthalates, Phthalate, Diethyl phthalate, Plasticizer, Intake, Bis(2-ethylhexyl) phthalate, Plasticizers

25

The purpose of this paper is to review exposure assessment issues that need to be addressed in designing and interpreting epidemiology studies of phthalates, a class of chemicals commonly used in consumer and personal care products. Specific issues include population trends in exposure, temporal reliability of a urinary metabolite measurement, and how well a single urine sample may represent longer-term exposure. The focus of this review is on seven specific phthalates: diethyl phthalate (DEP); di-n-butyl phthalate (DBP); diisobutyl phthalate (DiBP); butyl benzyl phthalate (BBzP); di(2-ethylhexyl) phthalate (DEHP); diisononyl phthalate (DiNP); and diisodecyl phthalate (DiDP).

Concepts: Phthalates, Phthalate, Plasticizer, Plasticizers, Dibutyl phthalate, Diisobutyl phthalate, Diisononyl phthalate, Diisoheptyl phthalate

14

In the last few years, the use of phthalates in perfumes has gained attention because these chemicals are sometimes added intentionally as a solvent and a fixative. Five phthalate esters, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), benzyl butyl phthalate (BBP), and diethyl hexyl phthalate (DEHP), were measured in 47 branded perfumes using headspace solid phase microextraction (SPME) followed by gas chromatography-mass spectrometry (GC-MS). The results revealed considerable amounts of phthalate in all 47 brands with detection frequencies > limit of quantitation in the following order: DEP (47/47) > DMP (47/47) > BBP (47/47) > DEHP (46/47) > DBP (23/45). Of the 47 brands, 68.1, 72.3, 85.1, 36.2, and 6.7 % had DEP, DMP, BBP, DEHP, and DBP levels, respectively, above their reported threshold limits. Of these phthalates, DEP was found to have the highest mean value (1621.625 ppm) and a maximum of 23,649.247 ppm. The use of DEP in the perfume industry is not restricted because it does not pose any known health risks for humans. DMP had the second highest level detected in the perfumes, with a mean value of 30.202 ppm and a maximum of 405.235 ppm. Although DMP may have some uses in cosmetics, it is not as commonly used as DEP, and again, there are no restrictions on its use. The levels of BBP were also high, with a mean value of 8.446 ppm and a maximum of 186.770 ppm. Although the EU banned the use of BBP in cosmetics, 27 of the tested perfumes had BBP levels above the threshold limit of 0.1 ppm. The mean value of DEHP found in this study was 5.962 ppm, and a maximum was 147.536 ppm. In spite of its prohibition by the EU, 7/28 perfumes manufactured in European countries had DEHP levels above the threshold limit of 1 ppm. The DBP levels were generally low, with a mean value of 0.0305 ppm and a maximum value of 0.594 ppm. The EU banned the use of DBP in cosmetics; however, we found three brands that were above the threshold limit of 0.1 ppm, and all were manufactured in European countries. The results of this study are alarming and definitely need to be brought to the attention of the public and health regulators. Although some phthalate compounds are still used in cosmetics, many scientists and environmental activists have argued that phthalates are endocrine-disrupting chemicals that have not been yet proven to be safe for any use, including cosmetics. Phthalates may also have different degrees of estrogenic modes of action. Furthermore, we should not dismiss the widespread use of phthalates in everyday products and exposure to these chemicals from sources such as food, medications, and other personal care products.

Concepts: European Union, Phthalates, Cosmetics, Perfume, Phthalate, Diethyl phthalate, Plasticizers, Dibutyl phthalate

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Context: There is evidence of declining trends in T levels among men in recent decades, as well as trends in related conditions at multiple life stages and in both sexes. There is also animal and limited human evidence that exposure to phthalates, chemicals found in plastics and personal care products, is associated with reduced androgen levels and associated disorders. Objective: To explore relationships between urinary concentrations of 13 phthalate metabolites and serum total T levels among men, women, and children when adjusting for important confounders and stratifying by sex and age (6-12, 12-20, 20-40, 40-60, and 60-80 y). Design: A cross-sectional study. Setting: US National Health and Nutrition Examination Survey, 2011-2012. Patients or Other Participants: US general population. Interventions: None Main Outcome Measures: Serum total T measured by isotope dilution-liquid chromatography-tandem mass spectrometry. Results: Multiple phthalates were associated with significantly reduced T in both sexes and in differing age groups. In females, the strongest and most consistent inverse relationships were found among women ages 40-60 years. In boys 6-12 years old, an interquartile range increase in metabolites of di-2-ethylhexyl phthalate was associated with a 29% (95% confidence interval, 6, 47) reduction in T. In adult men, the only significant or suggestive inverse associations between phthalates (metabolites of di-2-ethylhexyl phthalate and dibutyl phthalate) and T were observed among men ages 40-60 years. Conclusions: Because T plays an important role in all life stages for both sexes, future efforts should focus on better defining these relationships and their broader impacts.

Concepts: Male, Testosterone, Sex, Phthalates, Phthalate, Plasticizer, Bis(2-ethylhexyl) phthalate, Plasticizers

8

Phthalates are ubiquitous environmental contaminants. Because of potential adverse effects on human health, butylbenzyl phthalate (BBzP; metabolite = monobenzyl phthalate (MBzP)), di-n-butyl phthalate (DnBP; metabolite = mono-n-butyl phthalate (MnBP)), and di(2-ethylhexyl) phthalate (DEHP) are being replaced by substitutes including other phthalates, however little is known about consequent trends in population-level exposures.

Concepts: Health, Human, Nutrition, Phthalates, Phthalate, Plasticizer, Bis(2-ethylhexyl) phthalate, Plasticizers