Diundecyl Phthalate Research Articles

Sensitivity comparison of gas chromatography-mass spectrometry with Cold EI and standard EI.

Gas chromatography-mass spectrometry (GC-MS) with Cold EI is based on interfacing GC and MS with supersonic molecular beams (SMBs) along with electron ionization of vibrationally cold sample compounds in SMB in a fly-through ion source (hence the name Cold EI). Cold EI improves all the central performance aspects of GC-MS, and in this paper, we focus on its improvement of signal-to-noise ratio (S/N) and limits of detection (LODs). We found that the harder the compound for analysis with standard EI, the greater the Cold EI gain in S/N and LOD. The lower LOD and higher S/N of Cold EI emerge from a few reasons: (a) similar ionization yield as standard EI, (b) enhanced abundance of molecular ions, (c) elimination of vacuum background noise, (d) elimination of ion source-related peak tailing and degradation, (e) ability to lower the elution temperatures via the use of high column flow rates, and (f) greater range of thermally labile and low-volatility compounds that can be analyzed. We demonstrate the superior S/N and lower LOD of Cold EI versus standard EI in a range of compounds, from the simple-to-analyze octafluoronaphthalene all the way to reserpine and an organo-metallic compound that cannot be analyzed by standard EI. These compounds include methyl stearate, cholesterol, n-C32 H66 , large polycyclic aromatic hydrocarbons, dioctyl phthalates, diundecyl phthalate, pentachlorophenol, benzidine, lambda-cyhalothrin, and methidathion. The significantly lower Cold EI LODs that can be over 1000 times better than in standard EI further result in far superior response linearity and greater measurement dynamic range.

Identification of high-concern organic pollutants in tap waters from the Yangtze River in China based on combined screening strategies

Recently, numerous organic pollutants have been detected in water environment. The safety of our drinking water has attracted widespread attention. Effective methods to screen and identify high-concern substances are urgently needed. In this study, the combined workflow for the detection and identification of high-concern organic chemicals was established and applied to tap water samples from the Yangtze River Basin. The solid phase extraction (SPE) sorbents were compared and evaluated and finally the HLB cartridge was selected as the best one for most of the contaminants. Based on target, suspect and non-target analysis, 3023 chemicals/peaks were detected. Thirteen substances such as diundecyl phthalate (DUP), 2-hydroxyatrazine, dioxoaminopyrine and diethyl-2-phenylacetamide were detected in drinking water in the Yangtze River Basin for the very first time. Based on three kinds of prioritization principles, 49 ubiquitous, 103 characteristic chemicals and 13 inefficiently removed chemicals were selected as high-concern substances. Among them, 8, 31, 9, 3, 4 substances overlapped with the toxic, risky or high-concern chemicals lists in China, America, European Union, Japan, Korea, respectively. Specific management and removal strategies were further recommended. The workflow is efficient for identification of key pollutants.

Health risk assessment of exposures to a high molecular weight plasticizer present in automobile interiors

This study provides an exposure and risk assessment of diundecyl phthalate (DUP), a high molecular weight phthalate plasticizer present in automobile interiors. Total daily intake of DUP was calculated from DUP measured in wipe samples from vehicle seats from six automobiles. Four of the vehicles exhibited atypical visible surface residue on the seats. Two vehicles with no visible surface residue were sampled as a comparison. DUP was the predominant organic compound identified in each of the wipes from all seats. A risk assessment of DUP via oral, dermal, and inhalation routes resulting from contact with automobile seats was conducted. The mean, standard deviation, and maximum DUP concentrations on the seats with visible surface residue were 6983 ± 7823 μg/100 cm2 and 38300 μg/100 cm2, respectively. The mean and 95th percentile of the mean for daily cumulative dose of DUP for all exposure routes for the seats with no visible surface residue ranged from 7 × 10−4 to 4 × 10−3 mg/kg-day and from 8 × 10−4 to 5 × 10−3 mg/kg-day, respectively. For seats with visible surface residue, cumulative doses ranged from 2 × 10−3 to 2 × 10−2 mg/kg-day and from 4 × 10−3 to 2 × 10−2 mg/kg-day, respectively. The estimated daily intake (contact or absorbed dose) of DUP from automobile seats were far lower than the NOAELs reported in and derived from animal studies, and are well below the reported Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) Derived No Effect Levels (DNELs) for the general population. Based on this analysis, using virtually any benchmark for evaluating safety, exposure to DUP via automobile seat covers did not pose a measureable increased health-risk in any population under any reasonably plausible exposure scenario.

Identification of potential biomarkers of exposure to diundecyl phthalate

Diundecyl phthalate (DUP) is a high production volume chemical used as a plasticizer in polyvinyl chloride and other plastics. Specific biomarkers of DUP would be useful for human exposure assessment. To identify such biomarkers, we investigated the in vitro metabolism of DUP with human liver microsomes using online solid phase extraction coupled to HPLC-mass spectrometry. Using high resolution mass spectrometry, we conclusively confirmed the structures of four DUP specific metabolites: monoundecyl phthalate (MUP), mono-hydroxyundecyl phthalate (MHUP), mono-oxoundecyl phthalate (MOUP), and mono-carboxydecyl phthalate (MCDP). We also used high resolution mass spectrometry to isolate MCDP and MHUP from co-eluting isobaric metabolites of diisononyl phthalate (i.e., monocarboxyisononyl phthalate) and diisododecyl phthalate (i.e., monohydroxyisododecyl phthalate), respectively, that could not be separated with low resolution tandem mass spectrometry. To evaluate the potential usefulness of the newly identified DUP metabolites as exposure biomarkers, we analyzed 36 human urine samples by high resolution mass spectrometry. We detected MHUP and MCDP in >83% of the samples; median concentrations were 0.21ng/mL and 0.36ng/mL, respectively. MOUP was detected only in 14% of the samples analyzed, and MUP was not detected. All three metabolites eluted as peak clusters likely because of the presence of multiple oxidation sites and multiple isomers in DUP technical mixtures. Taken together, these findings suggest that with the appropriate mass spectrometry quantification techniques, MHUP and MCDP may serve as suitable biomarkers for assessing background exposure to DUP.

Prenatal developmental toxicity studies on diundecyl and ditridecyl phthalates in Sprague-Dawley rats

This study evaluates the developmental toxicity of two high molecular weight dialkyl phthalate esters, diundecyl phthalate (DUDP) and ditridecyl phthalate (DTDP). Sprague-Dawley rats were administered 0, 0.25, 0.50, or 1g/kg/day of DUDP or DTDP, by gavage, on gestation days 6–20. DUDP and DTDP had no adverse effects on maternal body weight and food consumption. The number of live fetuses, percent of post-implantation loss and of resorptions, fetal sex, and fetal body weights were not affected by either phthalate. There was no evidence of teratogenicity, whatever treatment. Small decreases in the anogenital distance of male fetuses were noted at 0.5 and 1g DUDP/kg/day. The incidence of fetuses with supernumerary lumbar ribs was significantly higher than control at 0.5 and 1g DUDP/kg/day. Thus, DTDP was not developmentally toxic up to 1g/kg/day and there were signs of DUDP-induced fetal effects at 0.5 and 1g/kg/day.

Comparison of the Short Term Toxicity of Phthalate Diesters and Monoesters in Sprague-Dawley Male Rats

This study was carried out to investigate the short term toxicity of nine phthalate diesters including di-2 (ethylhexyl) phthalate (DEHP) , di (n-butyl) phthalate (DBP) , di-n-octyl phthalate (DnOP) , diethyl phthalate (DEP) , butylbenzyl phthalate (BBP) , dimethyl phthalate (DMP) , di-isodecyl phthalate (DIDP) , diundecyl phthalate (DUP) , and di-isononyl phthalate (DINP) and five phthalate monoesters including mono- (2-ethylhexyl) phthalate (MEHP) , monobutyl phthalate (MBuP) , monobenzyl phthalate (MBeP) , monoethyl phthalate (MEP) , monomethyl phthalate (MMP) and phthalic acid (PA) in Sprague-Dawley male rats. Animals were administered 250 mg/kg/day (monoesters and PA) or 500 mg/kg/day (diesters) of phthalate for two weeks. All animals were examined for body and organ weights, blood hematology, serum biochemistry, and urine analysis. The body weight gain was significantly lower in rats treated with BBP, DBP, DINP, MEHP, MBuP, and PA than that of control. Liver weights were significantly increased in the DEHP,DBP, DnOP, DIDP, and MEHP groups as compared to the control group. Testes weights were significantly decreased only in the DEHP-, DnOP-, and DIDP-treated groups as compared to the control. Significant differences in hematological changes were not observed in any treatment groups. Significant increases in blood glucose levels were observed in the DEHP, MEHP, and MBeP groups. Aspartate aminotransferase (AST) levels were significantly increased in the DBP, DUP, DINP, MBuP, and MBeP groups, whereas alanine aminotransferase (ALT) levels were significantly increased only in the DEHP and MEHP groups. Serum ALP levels were significantly higher in phthalate diester (500 mg/kg/day) -treated rats as compared to control. However, the total cholesterol level was significantly reduced in the DEHP- and DIDP-treated groups, whereas serum triglyceride (TG) levels were higher in the DINP-, MEHP-, and MBuP-treated groups. These results suggest that short term toxicity of phthalate monoesters produces adverse effects as similar to phthalate diesters in Sprague-Dawley rats.

Comparative Toxicological Evaluation of Phthalate Diesters and Metabolites in Sprague-Dawley Male Rats for Risk Assessment

In order to comparatively assess the systemic toxicity and sperm parameters, nine phthalate diesters, including di(2-ethylhexyl) phthalate (DEHP), di(n-butyl) phthalate (DBP), di-n-octyl phthalate (DnOP), diethyl phthalate (DEP), butylbenzyl phthalate (BBP), dimethyl phthalate (DMP), di-isodecyl phthalate (DIDP), diundecyl phthalate (DUP), and di-isononyl phthalate (DINP), and five phthalate monoesters, including mono(2-ethylhexyl) phthalate (MEHP), monobutyl phthalate (MBuP), monobenzyl phthalate (MBeP), monoethyl phthalate (MEP), monomethyl phthalate (MMP), and phthalic acid (PA) were administered orally to Sprague-Dawley male rats at 250 (phthalate monoesters and PA) or 500 mg/kg body weight (bw)/d (phthalate diesters) for 4 wk. Liver weights were significantly increased in g roups treated with DEHP, DBP, BBP, DIDP, DINP, MEHP, and MBuP compared to the control. Testes weights were significantly reduced only in DEHP, DBP, and MEHP-treated groups compared to the control. Significant decreases in red blood cell (RBC) and hematocrit (Ht) levels were observed in DEHP-treated rats, whereas significant increases in mean corpuscular hemoglobin (MCH), mean corpuscular hemoglobin concentration (MCHC), and platelet (PLT) levels were found in the DEHP-treated group. Hemoglobin (Hb) level was reduced only in the DMP group. Similar to effects on testis and epididymal weights, DEHP and MEHP significantly reduced sperm numbers and motility. In particular, DnOP, DBP, BBP, MEP, MBuP, DUP, DINP, and MBeP significantly lowered the sperm counts and sperm motility of epididymal sperm, detected by a change in the sperm motion parameters. The strongest to the weakest adverse effects for sperm motility were as follows: DEHP > DBP > DnOP > DUP > DIDP > BBP among diesters and MBuP > MEP > MEHP among monoesters, respectively. These results suggest that the adverse effects of phthalate esters (PEs) on sperm parameters in male rats are greater with phthalate diesters than monoesters, which may be useful for the risk assessment of phthalates.

Injector‐internal thermal desorption from edible oils. Part 2: Chromatographic optimization for the analysis of migrants from food packaging material

Injector-internal thermal desorption from edible oil or fat is a convenient sample preparation technique for the analysis of solutes in lipids or extracts from fatty foods. The injector temperature is selected to vaporize the solutes of interest while minimizing evaporation of the bulk material of the oil. This technique has been in routine use for pesticides for some time. Now its potential is explored for migrants from food contact materials, such as packaging, into simulant D (olive oil) or fatty/oily food, which means extending the range of application towards less volatile compounds. The performance for high boiling components was investigated for diisodecyl phthalate (DIDP) and diundecyl phthalate (DUP). Since the injector temperature needs to be as high as 260degreesC, some bulk material of the oil enters the column and must be removed after every analysis. This is achieved by a coated precolumn backflushed towards the end of each analysis. Desorption of the solutes is particularly efficient in the initial phase, when a thin sample film is spread on the liner wall, and is largely determined by the diffusion speed in the oil after the latter has contracted to droplets. An increased carrier gas flow rate during the splitless period supports the transfer into the column. It is concluded that the technique is attractive for migrant analysis, with DUP being at the upper limit of the boiling point.

Correlation of the glass transition temperature of plasticized PVC using a lattice fluid model

A model has been developed to estimate the glass transition temperature of polymer+plasticizer mixtures (up to 30wt% plasticizer). The model is based on the Sanchez–Lacombe equation of state and the Gibbs–DiMarzio criterion, which states that the entropy of a mixture is zero at the glass transition. The polymers studied included polystyrene and poly(vinyl chloride). The plasticizers studied included a wide range of chemicals from methyl acetate to di-undecyl phthalate. The model qualitatively accounted for the effect of different plasticizers on the mixture glass transition temperature.

Results of the L5178Y mouse lymphoma assay and the Balb/3t3 cell in vitro transformation assay for eight phthalate esters.

Eight phthalate esters, with alcohol chain lengths of 1-11 carbon atoms and with various degrees of branching, were tested in vitro in the L5178Y mouse lymphoma mammalian cell mutation assay and in the Balb/3T3 cell transformation assay. The tests were performed as part of a voluntary testing agreement between the Chemical Manufacturers Association's Phthalate Esters Panel and the United States Environmental Protection Agency (US EPA). The esters tested were: dimethyl phthalate (DMP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBP), di-¿n-hexyl, n-octyl, n-decyl¿ phthalate (610P), di-isononyl phthalate (DINP), di-¿heptyl, nonyl, undecyl¿ phthalate (711P), di-isodecyl phthalate (DIDP) and di-undecyl phthalate (DUP). Both DMP and DBP were found to produce significant increases in the mutant frequency in the mouse lymphoma assay in the presence but not in the absence of an Aroclor-induced rat liver activation system (S-9). Ester 610P gave equivocal results in the mouse lymphoma assay in the presence and absence of rat liver S-9. There was no indication of mutagenic potential for any of the other test materials in the mouse lymphoma assay, and none of the test materials increased transformation frequency in the Balb/3T3 cell transformation assay. Aldehyde metabolites of the de-esterified alcohols are postulated to play a role in the positive results for DMP and DBP.

The effect of phthalate ester plasticisers tested as surfactant stabilised dispersions on the reproduction of the Daphnia magna

The phthalate ester plasticisers, di-2-ethylhexyl phthalate (DEHP), di-iso-nonyl phthalate (DINP), DINP produced by the “polygas” process (DINP-PG), di-n-nonyl/n-undecyl phthalate (L911 P), di-n-octyl/n-decyl phthalate (L810P), di-iso-decyl phthalate (DIDP), di-iso-heptyl phthalate (DIHP), di-n-hexyl/n-decyl phthalate (L610P), di-undecyl phthalate (DUP), di-heptyl/nonyl phthalate (L791), di-iso-undecyl phthalate (DIUP) and di-iso-tridecyl phthalate (DTDP) have been tested for acute and chronic toxicity to Daphnia magna. In addition, di-2-propylheptyl phthalate (DPHP) has been tested for chronic toxicity to Daphnia magna. The test organisms were exposed at a nominal concentration of 1 mg phthalate per litre presented as a dispersion with either “Tween 20” or “Marlowet R40”. For the chronic studies, the nominal concentrations were verified by analysis, except for the L911P where, due to chromatographic difficulties, the test concentration could not be determined and this was estimated as 56% of nominal by analysis of the stock. The exposure period for the acute studies was 48 hours and the test organisms were monitored for flotation in the surface layer and mortalities. The chronic studies were conducted over 21 days. The end points were the numbers of young produced, survival of the parent animals and the length of the parent animals at the end of the 21 day exposure period. No significant negative effects, relative to the controls, were seen in either the acute or the chronic studies.

Chronic toxicity of 14 phthalate esters to Daphnia magna and rainbow trout (Oncorhynchus mykiss)

AbstractChronic toxicity studies were performed with commercial phthalate esters and Daphnia magna (14 phthalates) and rainbow trout (Oncorhynchus mykiss) (six phthalates). For the lower‐molecular‐weight phthalate esters–dimethyl phthalate (DMP), diethyl phthalate (DEP), di‐n‐butyl phthalate (DBP), and butylbenzyl phthalate (BBP)–the results of the studies indicated a general trend in which toxicity for both species increased as water solubility decreased. The geometric mean maximum acceptable toxicant concentration (GM‐MATC) for D. magna ranged from 0.63 to 34.8 mg/L. For the higher‐molecular‐weight phthalate esters–dihexyl phthalate (DHP), butyl 2‐ethylhexyl phthalate (BOP), di‐(n‐hexyl, n‐octyl, n‐decyl) phthalate (610P), di‐(2‐ethylhexyl) phthalate (DEHP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), di‐(heptyl, nonyl, undecyl) phthalate (711P), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), and ditridecyl phthalate (DTDP)‐the GM‐MATC values ranged from 0.042 to 0.15 mg/L. Survival was equally sensitive and sometimes more sensitive than reproduction. The observed toxicity to daphnids with most of the higher‐molecular‐weight phthalate esters appeared to be due to surface entrapment or a mode of toxicity that is not due to exposure to dissolved aqueous‐phase chemical. Early life‐stage toxicity studies with rainbow trout indicated that survival (DMP) and growth (DBP) were affected at 24 and 0.19 mg/L, respectively. This pattern of observed toxicity with the lower‐molecular‐weight phthalate esters and not the higher‐molecular‐weight phthalate esters is consistent with previously reported acute toxicity studies for several aquatic species.

A summary of the acute toxicity of 14 phthalate esters to representative aquatic organisms

AbstractAcute aquatic toxicity studies were performed with 14 commercial phthalate esters and representative freshwater and marine species. The 14 esters were dimethyl phthalate; diethyl phthalate; di‐n‐butyl phthalate; butyl benzyl phthalate; dihexyl phthalate; butyl 2‐ethylhexyl phthalate; di‐(n‐hexyl, n‐octyl, n‐decyl) phthalate; di‐(2‐ethylhexyl) phthalate; diisooctyl phthalate; diisononyl phthalate; di‐(heptyl, nonyl, undecyl) phthalate; diisodecyl phthalate; diundecyl phthalate; and ditridecyl phthalate. Phthalate esters with alkyl chain lengths of four carbon atoms or fewer were determined to be acutely toxic at concentrations ranging from 0.21 to 377 mg/L depending on the ester and the solubility of the test chemical in water. There was a general trend for the lower‐molecular‐weight phthalate esters (C1 to C4 alkyl chain lengths: dimethyl phthalate; diethyl phthalate; di‐n‐butyl phthalate; and butyl benzyl phthalate) to become more toxic with decreasing water solubility for all species tested. There were only minor differences in species sensitivity to each of the phthalate esters. Phthalate esters with alkyl chain lengths of six carbon atoms or more were not acutely toxic at concentrations approaching their respective aqueous solubilities. Insufficient mortality occurred to calculate either LC50 or EC50 values or acute no‐observed‐effect concentrations for these higher‐molecular‐weight phthalate esters. The lack of toxicity observed for the higher‐molecular‐weight phthalate esters resulted from their limited water solubility (≤1.1 mg/L).

A monomeric plasticizer for high temperature applications

AbstractThe results of this study demonstrate that high molecular weight and predominantly linear diundecyl phthalate (DUP) provide improved performance properties and cost savings when used as a partial or total replacement for trimellitate plasticizers in critical applications such as vinyl electrical insulations and crashpad covers. DUP is shown to be a permanent and stable plasticizer with a high efficiency in improving low‐temperature flexibility of formulated vinyls.

Radiation crosslinking of poly(vinyl chloride) with trimethylolpropanetrimethacrylate. IV. Effect of diundecyl phthalate: Dependence of physical properties on composition

AbstractBlends of poly(vinyl chloride) (PVC) with polyfunctional monomers may be crosslinked by ionizing radiation. The physical properties of PVC blended with trimethylolpropanetrimethacrylate (TMPTMA) and diundecyl phthalate (DUP) were studied. The TMPTMA monomer crosslinked the blend by homopolymerization and/or grafting to PVC. The plasticizer, DUP, was chemically inert under irradiation but, by plasticizing the macromolecules and diluting the monomer, changed the kinetics extensively. Characteristics of the glass transitions and the tensile mechanical properties have been correlated with blend composition and radiation dose. Before irradiation, poly(vinyl chloride) was plasticized by both DUP and TMPTMA monomer. The increase in glass transition temperature and mechanical strength following irradiation to 5 Mrad was correlated with the TMPTMA content of the blend. Both the molecular structure of the network and the DUP content of the blend were factors in determining the physical properties of the final crosslinked blend. The molecular structure was determined by the kinetics of the crosslinking reactions, which in turn were determined by the blend composition. A molecular interpretation consistent with the physical properties, chemical kinetics, and mechanism of the crosslinking system has been presented.

The radiation crosslinking of poly(vinyl chloride) with trimethylolpropanetrimethacrylate. III. Effect of diundecyl phthalate: Chemical kinetics of a three‐component system

AbstractThe radiation chemistry of poly(vinyl chloride) (PVC) blended with trimethylolpropanetrimethacrylate (TMPTMA) and diundecyl phthalate (DUP) has been examined. This three‐component mixture contains a base resin (PVC), a crosslinking sensitizer (TMPTMA), and a physical modifier (DUP). These are the basic components in any radiation‐curable coating. The kinetics and mechanism of the crosslinking reactions were studied with reference to the dependence on radiation dose and blend composition. The polyfunctional TMPTMA underwent polymerization incorporating the PVC into a 3‐dimensional network. DUP remained chemically inert during the irradiation, not being bound to the network. However, DUP by plasticizing the macromolecules and diluting the monomer, changed the kinetics extensively. DUP enhanced TMPTMA homopolymerization, TMPTMA grafting, and PVC crosslinking reaction rates. The effect on the competition between polymerization, grafting, and degradation reactions was examined in terms of enhanced mobility of the reacting species. The influence of these kinetic considerations in selecting a blend composition for a coating application was discussed.