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Phthalates or phthalic acid esters (PAE) and bis(2-ethylhexyl)adipate (DEHA) are ubiquitous chemicals often used as plasticisers and additives in many industrial products and are classified as both persistent organic pollutants (POPs) and new emerging pollutants (NEPs). Exposure to these chemicals, especially through inhalation, is linked to a wide range of negative health effects, including endocrine disruption. Air particulate matter (PM) with an aerodynamic diameter ≤ 2.5 μm can be enriched with PAEs and DEHA and if inhaled can cause multi-system human toxicity. Therefore, proper monitoring of PAEs and DEHA in PM is required to assess human exposure to these pollutants. In this work, we developed and validated a new and sensitive gas-chromatography high-resolution mass spectrometry (GC-HRMS) method for targeted analysis of PAEs including dimethyl phthalate (DMP), diethyl phthalate (DEP), di- n -butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis(2-ethylhexyl)adipate (DEHA), bis(2-ethylhexyl)phthalate (DEHP), di- n -octyl phthalate (DOP), in PM. Analytical aspects including sample preparation steps and GC-HRMS parameters, e.g. , quadrupole isolation window, to enhance method sensitivity have been assessed. The estimated limit of detection (LODs) of target PAEs and DEHA ranged from 5.5 to 17 pg μL -1 , allowing their trace-level detection in PM. Extraction efficiencies of 78-101% were obtained for the target compounds. Low DMP and DEP extraction efficiencies from the spiked filter substrates indicated that significant losses of higher volatility PAEs can occur during the sample collection when filter-based techniques are used. This work is the first targeted method based on GC-Orbitrap MS for PAEs and DEHA in environmental samples. The validated method was successfully applied for the targeted analysis of PAEs and DEHA in PM 2.5 samples from the eighth most populous city in Brazil, Curitiba. This work is the first to report DBP, DEHA, DEHP, and DOP in urban PM from Brazil. The observed concentrations of PAEs (up to 29 ng m -3 ) in PM 2.5 from Curitiba may not represent the extent of pollution by these toxic compounds since the analysed samples were collected during a COVID-19 restriction when anthropogenic activities were reduced.

NPPs (Non-phthalate plasticizers) are used as alternative plasticizers to phthalate esters, but there is limited knowledge on environmental residues, and they have not been reported in Japan. A method to analyze NPPs in seawater using solid-phase extraction was developed, and the residual burden of Diisobutyl adipate (DIBA), Acetyl tributyl citrate (ATBC), Di-(2-ethylhexyl) adipate (DEHA), Di-(2-ethylhexyl) sebacate (DEHS) and Trioctyl trimellitate (TOTM) in seawater and sediment from the Osaka Bay was measured. Using an Oasis Max column and acetone as the eluting solvent, the recovery of the target substances in seawater is >68 %. In Osaka Bay, no NPPs were detected in seawater. On the other hand, ATBC and TOTM were detected in the sediment at 36-69 ng/g and 47-131 ng/g, respectively, from about half of the 14 sites, while DEHA and DEHS were detected at 83 ng/g and 181 ng/g, respectively, from only one site., Competing Interests: Declaration of competing interest The authors declare they have no known competing financial interests or personal relationships that could have appeared to influence the research work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

In this work, an evaluation of the occurrence of fifteen phthalates, four metabolites and one adipate in different groundwater, seawater and wastewater samples has been carried out due to their relevance on human health as they act as endocrine disruptors. For this purpose, a sustainable, fast and easy-handling vortex-assisted liquid-liquid microextraction method using a natural hydrophobic deep eutectic solvent based on menthol and carvacrol as extraction agent, combined with ultra-high performance liquid chromatography-mass spectrometry technique, has been developed and applied for the first time. An optimization was performed to evaluate four important factors affecting the extraction performance, and an analytical validation was carried out in terms of matrix effect, linearity, extraction efficiency, and sensitivity. Recovery values were obtained in the range 72-119% for all analytes (except for monoethyl phthalate: 61.1-72.3%) with relative standard deviation values lower than 17%. Limits of quantification were found between 0.91 and 8.09 μg L -1 . As a result of the assessment of 31 different environmental water samples, monoethyl phthalate, diethyl phthalate, dibutyl phthalate and bis (2-ethylhexyl) phthalate were detected and quantified at different concentrations in the range 2.59-21.17 μg L -1 in 6 samples, and diallyl phthalate, butyl benzyl phthalate, dipentyl phthalate, dicyclohexyl phthalate, dihexyl phthalate and bis (2-ethylhexyl) adipate were detected in 20 more, showing the exposition of the population to these hazardous substances., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

In this work, a natural deep eutectic solvent was used for the liquid-liquid microextraction of fourteen phthalates and one adipate from bottled waters. The methodology was validated in terms of matrix effect, linearity, recovery, and limits of quantification (LOQs). Optimum extraction conditions (10 mL of water at pH 8.0 with 100 μL of thymol: menthol 2:1 (n/n) as solvent) provided satisfactory determination coefficients (≥ 0.9977), recovery values (82-127%), and LOQs (0.018-0.523 μg/L). The effects of temperature and storage time on plasticizer presence were studied for 36 different brands stored at 4 °C, room temperature, and 45 °C, and analyzed at 0, 24, 48, 72 h, and 1 week. Only diethyl-, dibutyl-, bis-(2-ethylhexyl) phthalates, and bis-(2-ethylhexyl) adipate were detected. The results showed that there is no relationship between the storage conditions, the bottle material or water carbonation, and the occurrence of these plasticizers, suggesting that residues are introduced during production or by the water supply. The estimated daily intake was lower than the total daily intake set by the European Food Safety Authority., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Bioplastics are materials that are biobased and/or biodegradable, but not necessarily both. Concerns about environmental plastic pollution are constantly growing with increasing demand for substituting fossil-based plastics with those made using renewable resource feedstocks. For many conventional bioplastics to completely decompose/degrade, they require specific environmental conditions that are rarely met in natural ecosystems, leading to rapid formation of micro-bioplastics. As global bioplastic production and consumption/use continue to increase, there is growing concern regarding the potential for environmental pollution from micro-bioplastics. However, the actual extent of their environmental occurrence and potential impacts remains unclear, and there is insufficient mass concentration-based quantitative data due to the lack of quantitative analytical methods. This study developed and validated an analytical method coupling pressurized liquid extraction and pyrolysis-gas chromatography-mass spectrometry combined with thermochemolysis to simultaneously identify and quantify five targeted micro-bioplastics (i.e., polylactic acid (PLA), polyhydroxyalkanoate, polybutylene succinate, polycaprolactone, and polybutylene adipate terephthalate (PBAT)) in environmental samples on a polymer-specific mass-based concentration. The recovery of spiked micro-bioplastics in environmental samples (biosolids) ranged from 74 to 116%. The limits of quantification for the target micro-bioplastics were between 0.02 and 0.05 mg/g. PLA and PBAT were commonly detected in wastewater, biosolids, and sediment samples at concentrations between 0.07 and 0.18 mg/g. The presented analytical method enables the accurate identification, quantification, and monitoring of micro-bioplastics in environmental samples. This study quantified five micro-bioplastic types in complex environmental samples for the first time, filling in gaps in our knowledge about bioplastic pollution and providing a useful methodology and important reference data for future research.

Autism is a kind of biologically based neurodevelopmental condition, and the coexistence of atopic dermatitis (AD) is not uncommon. Given that the gut microbiota plays an important role in the development of both diseases, we aimed to explore the differences of gut microbiota and their correlations with urinary organic acids between autistic children with and without AD. We enrolled 61 autistic children including 36 with AD and 25 without AD. The gut microbiota was sequenced by metagenomic shotgun sequencing, and the diversity, compositions, and functional pathways were analyzed further. Urinary organic acids were assayed by gas chromatography-mass spectrometry, and univariate/multivariate analyses were applied. Spearman correlation analysis was conducted to explore their relationships. In our study, AD individuals had more prominent gastrointestinal disorders. The alpha diversity of the gut microbiota was lower in the AD group. LEfSe analysis showed a higher abundance of Anaerostipes caccae , Eubacterium hallii , and Bifidobacterium bifidum in AD individuals, with Akkermansia muciniphila , Roseburia intestinalis , Haemophilus parainfluenzae , and Rothia mucilaginosa in controls. Meanwhile, functional profiles showed that the pathway of lipid metabolism had a higher proportion in the AD group, and the pathway of xenobiotics biodegradation was abundant in controls. Among urinary organic acids, adipic acid, 3-hydroxyglutaric acid, tartaric acid, homovanillic acid, 2-hydroxyphenylacetic acid, aconitic acid, and 2-hydroxyhippuric acid were richer in the AD group. However, only adipic acid remained significant in the multivariate analysis (OR = 1.513, 95% CI [1.042, 2.198], P = 0.030). In the correlation analysis, Roseburia intestinalis had a negative correlation with aconitic acid (r = -0.14, P = 0.02), and the latter was positively correlated with adipic acid (r = 0.41, P = 0.006). Besides, the pathway of xenobiotics biodegradation seems to inversely correlate with adipic acid (r = -0.42, P = 0.18). The gut microbiota plays an important role in the development of AD in autistic children, and more well-designed studies are warranted to explore the underlying mechanism., Competing Interests: Authors J-dL and GT were employed by the company Geneis (Beijing) Co., Ltd. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Hong, Hou, Xu, Lang, Jin, Zeng, Zhang, Tian and You.)

Biopolymers based on polylactic acid (PLA) and starch have numerous advantages, such as coming from renewable sources or being compostable, though they can have deficiencies in mechanical properties, and for this reason, polyester resins are occasionally added to them in order to improve their properties. In this work, migration from a PLA sample and from another starch-based biopolymer to three different food simulants was studied. Attention was focused on the determination of oligomers. The analysis was first performed by ultraperformance liquid chromatography quadrupole-time-of-flight mass spectrometry (UPLC-Q-TOF-MS), which allowed the identification of the oligomers present in migration. Then, the samples were analyzed by two ambient desorption/ionization techniques directly coupled to mass spectrometry (ADI), direct analysis in real-time coupled to standardized voltage and pressure (DART-MS) and atmospheric pressure solids analysis probe (ASAP-MS). These methodologies were able to detect simultaneously the main oligomers migrants and their adducts in a very rapid and effective way. Nineteen different polyester oligomers, fourteen linear and five cyclic, composed of different combinations of adipic acid [AA], propylene glycol [PG], dipropylene glycol [DPG], 2,2-dibutyl-1,3-propanediol [DBPG], or isobutanol [i-BuOH] were detected in migration samples from PLA. In migration samples from starch-based biopolymer, fourteen oligomers from poly(butylene adipate co-terephthalate) polyester (PBAT) were identified, twelve cyclic and two linear. The results from ADI techniques showed that they are a very promising alternative tool to assess the safety and legal compliance of food packaging materials., (© 2021. The Author(s).)

Background: Adipic acid, a six-carbon platform chemical mainly used in nylon production, can be produced via reverse β-oxidation in microbial systems. The advantages posed by Corynebacterium glutamicum as a model cell factory for implementing the pathway include: (1) availability of genetic tools, (2) excretion of succinate and acetate when the TCA cycle becomes overflown, (3) initiation of biosynthesis with succinyl-CoA and acetyl-CoA, and (4) established succinic acid production. Here, we implemented the reverse β-oxidation pathway in C. glutamicum and assessed its functionality for adipic acid biosynthesis., Results: To obtain a non-decarboxylative condensation product of acetyl-CoA and succinyl-CoA, and to subsequently remove CoA from the condensation product, we introduced heterologous 3-oxoadipyl-CoA thiolase and acyl-CoA thioesterase into C. glutamicum. No 3-oxoadipic acid could be detected in the cultivation broth, possibly due to its endogenous catabolism. To successfully biosynthesize and secrete 3-hydroxyadipic acid, 3-hydroxyadipyl-CoA dehydrogenase was introduced. Addition of 2,3-dehydroadipyl-CoA hydratase led to biosynthesis and excretion of trans-2-hexenedioic acid. Finally, trans-2-enoyl-CoA reductase was inserted to yield 37 µg/L of adipic acid., Conclusions: In the present study, we engineered the reverse β-oxidation pathway in C. glutamicum and assessed its potential for producing adipic acid from glucose as starting material. The presence of adipic acid, albeit small amount, in the cultivation broth indicated that the synthetic genes were expressed and functional. Moreover, 2,3-dehydroadipyl-CoA hydratase and β-ketoadipyl-CoA thiolase were determined as potential target for further improvement of the pathway., (© 2021. The Author(s).)

Phthalic acid esters (PAEs) and adipates are plasticizers with high applicability in several products and building materials (e.g. cosmetics, packing) very persistent in the environment, features which render them ubiquitous pollutants. These substances can contaminate food through the environment (water, air, and soil) and/or migration from packaging materials, which creates a health concern due to their toxicity. This paper describes an eco-friendly dispersive liquid-liquid microextraction (DLLME) procedure to extract five phthalates and bis(2-ethylhexyl) adipate (DEHA) from bottled herbal-based beverages followed by GC-MS/MS quantification. The method showed low limits of detection (5.0-13 μg L -1 ) and quantification (20-35 μg L -1 ), good inter- and intraday precision (RSD < 19%), and recoveries ranging from 82 to 111%. It was applied to 16 real samples, of which 13 showed the presence of at least one of the analytes under study. Additionally, an exposure assessment was performed, and resulted in a hazard quotient less than 1 (HQ < 1) for all analytes. Therefore, PAEs and DEHA found in samples do not pose a health issue.

Background: Although more information has become available on the occurrence of phthalates and di(2-ethylhexyl) adipate (DEHA) in foods including cow's milk, information on their presence in human milk, the important and recommended sole diet for infants up to six months of age, is very limited, especially for DEHA., Objective: To develop a GC-MS method for simultaneous analysis of DEHA and phthalates in human milk samples and generate occurrence data for exposure assessment., Method: Human milk samples were extracted with acetonitrile followed by dispersive solid-phase extraction and GC-MS analysis., Results: Among the 305 human milk samples collected from the Canadian Maternal-Infant Research on Environmental Chemicals Study, some phthalates (DHxP, BBzP, and DOP) were not detected in any of the samples, while DEHA and the other phthalates (DMP, DEP, DBP, DiBP, and DEHP) were detected at low frequencies with levels from 30.4-237 ng/g in up to 31 of the 305 human milk samples., Conclusions: In general, DEHA and phthalates were detected at low frequencies and low levels in the 305 human milk samples., Highlights: A GC-MS method based on dispersive solid phase extraction was developed for analysis of DEHA and eight phthalates in 305 human milk samples for exposure assessment., (© AOAC INTERNATIONAL 2020. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Di(2-ethylhexyl) adipate (DEHA) is a widely used plasticizer and prevalent environmental contaminant. In this study, DEHA concentrations in the milk, cheese, and butter samples wrapped with food-grade commercial polyethylene films and stored at 4 °C for 30 days were detected using gas chromatographic analysis. Also, the effects of exposure to a high dose of DEHA for a long duration on the liver, brain, and heart of Wistar rats were assessed. Besides, the possible beneficial effect of Peganum harmala oil (PGO), in relieving DEHA induced adverse effects was explored. For this purpose, four groups (8 rats/group) were orally given physiological saline, PGO (320 mg/kg bwt), DEHA (2000 mg/kg bwt), or PGO + DEHA for 60 days. The results revealed that the DEHA concentrations in the tested dairy products were ordered as follows: (butter > cheese > milk). Notably, the detected levels in butter were higher than the specific migration limit in foods. DEHA induced a significant increase in the serum levels of glucose, alanine transaminase, aspartate transaminase, acetylcholine esterase, creatine kinase-myocardium bound, malondialdehyde, tumor necrosis factor-α, and interleukin-1β. But, significant hypoproteinemia, hypoalbuminemia, hypoglobulinemia, and hypocholesterolemia were evident following DEHA exposure. A significant reduction in the serum level of superoxide dismutase, reduced glutathione, and brain-derived neurotrophic factor was recorded. Besides, a significant downregulation in hepatic CYP2E1, brain glial fibrillary acidic protein, and cardiac troponin I gene expression was noticed. Moreover, DEHA exposure induced a significant decrease in Bcl-2 immunolabeling, but Caspase-3 immunoexpression was increased. On the contrary, PGO significantly recused DEHA injurious impacts. Therefore, PGO could represent a promising agent for preventing DEHA-induced hepatotoxicity, neurotoxicity, and cardiotoxicity., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

Continuous venovenous hemofiltration (CVVH) is widely used in intensive care units to treat patients with acute kidney injury requiring renal replacement therapy. The medical devices (MD) used for CVVH include a hemofilter and tubings made of plasticized PVC. Due to its known reprotoxicity, diethylhexyl phthalate (DEHP) has been replaced by alternatives such as diethylhexyladipate (DEHA) in some of these tubings. The migration of DEHA from hemofiltration systems has not been assessed and thus the level of patient exposure to this DEHP-alternative remains unknown. In this study, 2 CVVH models were used to evaluate the potential migration of DEHA from PVC tubings, allowing the determination of (Rachoin and Weisberg, 2019) the highest rates of DEHA able to migrate into a simulant flowing in a marketed adult CVVH circuit by disregarding any metabolisation and (Krieter et al., 2013) the clinical-reflecting exposure of patients to this plasticizer and its metabolites by assessing their migration into blood. In the first model, we showed that patients undergoing a CVVH procedure may be exposed to high rates of DEHA. Moreover, DEHA is continuously hydrolyzed into its primary metabolite MEHA (monoethylhexyladipate), which may reach cytotoxic level in the patients' blood. When looking from a « safer » MD perspective, DEHA might not be the best alternative plasticizer for CVVH tubings. However, to reflect clinical conditions, this study should be completed by an in-vivo evaluation (biomonitoring) of the oxidized metabolites of DEHA in urines of inpatients undergoing CVVH., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

With regard to the application of semi-volatile organic compounds (SVOCs) in products for indoor use, a distinct trend towards substitutions can currently be observed. Among the possible phthalate alternatives, in particular the adipic acid esters have gained in market importance. The chemical-physical and thermodynamic properties of the phthalates and adipates allow the conclusion to be drawn that they are distributed between different compartments (gas phase, particle phase, dust, material surfaces) of the indoor space. There are, however, hardly any data in existence which were collected in a real environment over six months and longer. Diisobutyl adipate (DiBA), di-n-butyl adipate (DnBA), dipentyl phthalate (DPP), butyl benzyl phthalate (BBzP) and di-2-ethylhexyl adipate (DEHA) were selected as model substances. By means of spiked latex paint and spiked house dust, these SVOCs were introduced into two identically equipped test rooms. One room was cleaned regularly, whilst the reference room was not entered for a 133 day experimental period. The concentrations of the five target substances were determined in the air and in material samples (carpet, vacuum-cleaner bags, filters). During the operation of an air purifier, the air concentration of the target substances in a room could be reduced by more than 50%. In the reference room, a correlation between the logarithmic air concentration and the reciprocal room temperature was found. The results show with great clarity the complexity of the conditions in an indoor room. Models can therefore depict the exposure as a statistical average but not, however, describe the individual case.

Plastic food contact materials (FCM)-based products were widely used in everyday life. These products were normally imposed to strict regulations in order to pass the enforcement tests of compliance as a prefix condition. However, even in these "qualified" materials, unknown chemical substances, not involving in legislation lists, could migrate from FCM. In this perspective, the present work aims to thoroughly analyze by means of Gas Chromatography-Mass Spectrometry (GC-MS) the different substances/migrants in 120 qualified FCM plastic products. Unexpectedly, among the identified compounds (nearly 100), only 13% was included in the permitted list of Commission Regulation EU No 10/2011. All the identified compounds were classified into 11 categories according to their chemical structure and the FCM type, whereas toxicology data were in addition analyzed. Each plastic type exhibited different preferences of chemical migrants. Fortunately, most of the compounds identified were of low toxicity, and only 4 chemicals were included in priority lists and previous literature reports as potential risk factors. Subsequently, the accurate amount of these 4 chemicals was determined. The amount of Bis(2-ethylhexyl) adipate (DEHA) and Bis(2-ethylhexyl) phthalate (DEHP) were lower than the SML in Commission Regulation EU No 10/2011, and that of stearamide was under the recommended use quantity. The 2,4-di-tert-butylphenol (2,4-DTBP) was widely exist in the investigated FCM products. Among them, the highest level is obtained in polypropylene/low density polyethylene (BOPP/LDPE) materials, up to 45.568±31.513 mg/kg. In summary, a panel of unlisted chemical migrants were discovered and identified by GS-MS screening. The results implied that plastic FCMs were not so "inert" as they usually considered, and further safety evaluation should be performed toward the complete identification of new substances in FCM products., Competing Interests: The authors have declared that no competing interests exist.

In terms of risk assessment especially for known and unknown substances migrating from food contact materials, quantification without corresponding reference substances currently poses a challenge. In the present study, the opportunity of a universal response quantification approach was evaluated by using a corona charged aerosol detector (CAD) for liquid chromatography combined with inverse gradient compensation. Characteristics of CAD detection in dependence of substance properties were analyzed with 46 randomly chosen reference substances. An almost equal CAD response (±20%) was achieved for non-volatile substances with a molecular weight of minimum 400 g/mol and a vapor pressure of maximum 10 -8 Torr. We empirically defined an analytical parameter, Q 50/35 , the quotient of CAD peak areas at CAD evaporator temperatures of 50 °C and 35 °C, to predict the adequacy of the CAD universal response approach for quantification of known and unknown analyte substances. Exemplarily, we applied the CAD universal quantification approach for the determination of extractable oligomers below 1000 g/mol from a variety of food contact polycondensate plastic materials (e.g. polyesters like polyethylene terephthalate, polybutylene terephthalate, Tritan copolyester, polyamides 6, 6.6 and 6 T/6I and polyarylsulfones polyphenylsulfone and polyethersulfone). Quantitative results for in total 44 oligomers out of 11 materials were compared with established material-specific quantification methods using extracted oligomer mixtures as well as individual oligomers isolated from the mixtures. CAD-based quantification results were generally in accordance to published quantification approaches for polyamide oligomers and oligomers from polyarylsulfones. For oligomers extracted and isolated from polyester materials a slight underestimation was determined by CAD universal response approach. In terms of detection limits and accuracy, the universal CAD approach exhibits no advantages compared to established UV-methods, to date., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The quality of indoor environment has received considerable attention owing to the declining outdoor human activities and the associated public health issues. The prolonged exposure of children in childcare facilities or the occupational exposure of adults to indoor environmental triggers can be a culprit of the pathophysiology of several commonly observed idiopathic syndromes. In this study, concentrations of potentially toxic plasticizers (phthalates as well as non-phthalates) were investigated in 28 dust samples collected from three different indoor environments across the USA. The mean concentrations of non-phthalate plasticizers [acetyl tri-n-butyl citrate (ATBC), di-(2-ethylhexyl) adipate (DEHA), and di-isobutyl adipate (DIBA)] were found at 0.51-880 μg/g for the first time in indoor dust samples from childcare facilities, homes, and salons across the USA. The observed concentrations of these replacement non-phthalate plasticizer were as high as di-(2-ethylhexyl) phthalate, the most frequently detected phthalate plasticizer at highest concentration worldwide, in most of indoor dust samples. The estimated daily intakes of total phthalates (n = 7) by children and toddlers through indoor dust in childcare facilities were 1.6 times higher than the non-phthalate plasticizers (n = 3), whereas estimated daily intake of total non-phthalates for all age groups at homes were 1.9 times higher than the phthalate plasticizers. This study reveals, for the first time, a more elevated (∼3 folds) occupational intake of phthalate and non-phthalate plasticizers through the indoor dust at salons (214 and 285 ng/kg-bw/day, respectively) than at homes in the USA., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

This study evaluated the influence of parameters such as temperature and type of low-density polyethylene (LDPE) film on the log Kp/f values of seven model migrants in food simulants. Two different types of LDPE films contaminated by extrusion and immersion were placed in contact with three food simulants including 20% ethanol, 50% ethanol and olive oil under several time-temperature conditions. Results suggest that most log Kp/f values are little affected by these parameters in this study. In addition, the relation between log Kp/f and log Po/w was established for each food simulant and regression lines, as well as correlation coefficients, were calculated. Correlations were compared with data from real foodstuffs. Data presented in this study could be valuable in assigning certain foods to particular food simulants as well as predicting the mass transfer of potential migrants into different types of food or food simulants, avoiding tedious and expensive laboratory analysis. The results could be especially useful for regulatory agencies as well as for the food industry.

In this study, for the first time, a dispersive liquid-liquid microextraction technique using a ternary solvent mixture is reported. In order to extract five phthalate esters and di(2-ethylhexyl) adipate with different polarities from aqueous samples, a simplex centroid experimental design method was used to select an optimal mixture of ternary solvents prior to gas chromatographyflame ionization detection. In this work, dimethyl formamide as a disperser solvent containing dichloromethane, chloroform, and carbon tetrachloride as a ternary extraction solvent mixture is injected into sample solution and a cloudy solution is formed. After centrifuging, 250μL of the obtained sedimented phase was transferred into another tube and 5μL DMF was added to it. Then, the tube was heated in a water bath at 75°C for 5min in order to evaporate the main portion of the extraction solvents. Finally, 2μL of the remained phase is injected into the separation system. Under the optimum extraction conditions, the method shows wide linear ranges and low limits of detection and quantification between 0.03-0.15 and 0.09-0.55μgL(-1), respectively. Enrichment factors and extraction recoveries are in the ranges of 980-4500 and 20-90%, respectively. The method is successfully applied in the determination of the target analytes in mineral water, soda, lemon juice, vinegar, dough, and yogurt packed in plastic packages., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A sensitive and selective GC-MS method was developed and used for simultaneous analysis of di-(2-ethylhexyl) adipate (DEHA) and 20 selected phthalates in the food samples from the 2013 Canadian Total Diet Study. At least one of the 21 target chemicals was detected in 141 of the 159 different food composite samples analysed. However, only seven of the 21 target chemicals were detected, with di-(2-ethylhexyl) phthalate (DEHP) and DEHA being detected most frequently, in 111 and 91 different food composite samples, respectively, followed by di-n-butyl phthalate (DBP) (n = 44), n-butyl benzyl phthalate (BBzP) (32), di-iso-butyl phthalate (DiBP) (27), di-ethyl phthalate (DEP) (3), and di-cyclohexyl phthalate (DCHP) (1). Levels of DEP (di-ethyl phthalate), DiBP, DBP, BBzP and DCHP were low, in general, with average concentrations of 9.63, 8.26, 23.2, 12.4 and 64.9 ng g(-1), respectively. Levels of DEHA and DEHP varied widely, ranging from 1.4 to 6010 ng g(-1) and from 14.4 to 714 ng g(-1), respectively. High levels of DEHA were found mainly in the composite samples where the individual food items used to prepare the composite were likely packaged in polyvinyl chloride (PVC) wrapping film, while the highest DEHP levels were found in the vegetable and fruit samples.

The β-ketoadipate pathway is a major pathway involved in the catabolism of the aromatic compounds in microbes. The recent progress in genome sequencing has led to a rapid accumulation of genes from the β-ketoadipate pathway in the available genetic database, yet the functions of these genes remain uncharacterized. In this study, the protocatechuate branch of the β-ketoadipate pathway of Rhodococcus jostii was reconstituted in vitro. Analysis of the reaction products of PcaHG, PcaB, and PcaL was achieved by high-performance liquid chromatography. These reaction products, β-ketoadipate enol-lactone, 3-carboxy-cis,cis-muconate, γ-carboxymuconolactone, muconolactone, and β-ketoadipate, were further characterized using LC-MS and nuclear magnetic resonance. In addition, the in vitro reaction of PcaL, a bidomain protein consisting of γ-carboxy-muconolactone decarboxylase and β-ketoadipate enol-lactone hydrolase activities, was demonstrated for the first time. This work provides a basis for analyzing the catalytic properties of enzymes involved in the growing number of β-ketoadipate pathways deposited in the genetic database.

The C6 dicarboxylic acid, adipic acid, is an important platform chemical in industry. Biobased production of adipic acid is a promising alternative to the current petrochemical route. Here, we report biosynthesis of adipic acid using an artificial pathway inspired by the reversal of beta-oxidation of dicarboxylic acids. The biosynthetic pathway comprises condensation of acetyl-CoA and succinyl-CoA to form the C6 backbone and subsequent reduction, dehydration, hydrogenation, and release of adipic acid from its thioester. The pathway was first tested in vitro with reconstituted pathway enzymes and then functionally introduced into Escherichia coli for the biosynthesis and excretion of adipic acid into the culture medium. The production titer was increased by approximately 20-fold through the combination of recruiting enzymes that were more suitable to catalyze the synthetic reactions and increasing availability of the condensation substrates. This work demonstrates direct biosynthesis of adipic acid via non-natural synthetic pathway, which may enable its renewable production., (© 2014 Wiley Periodicals, Inc.)

A new approach for the development of a dispersive liquid-liquid microextraction followed by GC with flame ionization detection was proposed for the determination of phthalate esters and di-(2-ethylhexyl) adipate in aqueous samples. In the proposed method, solid and liquid phases were used as the disperser and extractant, respectively, providing a simple and fast mode for the extraction of the analytes into a small volume of an organic solvent. In this method, microliter levels of an extraction solvent was added onto a sugar cube and it was transferred into the aqueous phase containing the analytes. By manual shaking, the sugar was dissolved and the extractant was released into the aqueous phase as very tiny droplets to provide a cloudy solution. Under optimized conditions, the proposed method showed good precision (RSD less than 5.2%), high enrichment factors (266-556), and low LODs (0.09-0.25 μg/L). The method was successfully applied for the determination of the target analytes in different samples, and good recoveries (71-103%) were achieved for the spiked samples. No need for a disperser solvent and higher enrichment factors compared with conventional dispersive liquid-liquid microextraction and low cost and short sample preparation time are other advantages of the method., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Di-(2-ethylhexyl) adipate (DEHA) and phthalates are commonly used as plasticizers to soften polyvinyl chloride products. Because both DEHA and certain phthalates have been identified as priority chemicals for assessment of human health risk under the Government of Canada's Chemicals Management Plan, a comprehensive targeted survey was conducted to investigate the occurrence of DEHA and eight phthalates (di-methyl phthalate, di-ethyl phthalate, di-n-butyl phthalate, di-iso-butyl phthalate, butyl benzyl phthalate, di-n-hexyl phthalate, d-(2-ethylhexyl) phthalate, and di-n-octyl phthalate) in a total of 118 samples of meat (beef, pork, and chicken), fish, and cheese packaged mostly in cling films. The eight phthalates were not detected in any of the food packaging, but DEHA was detected in most of the cling films, indicating that although DEHA-plasticized films (e.g., polyvinyl chloride film) are currently being used by most grocery stores, nonplasticized cling films such as polyethylene film, are also being used by some stores. DEHA was not detected in any of the 10 cheese samples packaged in nonplasticized rigid plastics but was detected in all 30 cheese samples packaged in DEHA-plasticized cling films at levels from 0.71 to 879 μg/g, with an average of 203 μg/g. Only DEHA was detected in the beef, pork, chicken, and fish samples packaged in DEHA-plasticized cling films but at considerably lower levels than those found in cheese, with averages of 6.3, 9.1, 2.5, and 5.9 μg/g, respectively. Among the eight phthalates, only di-(2-ethylhexyl) phthalate (DEHP) was detected in a few cheese samples at levels from 0.29 to 15 μg/g, with an average of 2.8 μg/g; these levels were very likely due to environmental contamination. Levels of DEHA found in most of the cheese samples from this study are above the European specific migration limit of 18 mg/kg for DEHA in food or food simulants, and levels of phthalates (i.e., DEHP) were low.

A method for simultaneous determination of 12 priority phthalates, adipate and polycyclic aromatic hydrocarbons (PAHs) in edible oils by isotope dilution-gas chromatography-mass spectrometry (ID-GC-MS) was developed for fast, accurate and trace analysis. The extraction and clean-up procedures were optimised, and using stable isotope-labelled internal standards for each analyte, relative standard deviations (RSDs) of 0.92-10.6% and spiked sample recoveries of 80.6-97.8% were obtained. Limits of detection for PAHs were in the range of 0.15-0.77 µg/kg and those for phthalates were in the range of 4.6-10.0 µg/kg. The calibration curves exhibited good linearities with regression coefficients of R(2) ≥ 0.99. Twelve edible oils were examined to evaluate the efficiency of this method. Among the 12 analytes, dibutyl phthalates (DBP), diethylhexyl phthalates (DEHP), diethylhexyl adipate (DEHA), benzo[a]anthracene (B[a]A), chrysene (Chry) and benzo[b]fluoranthene (B[b]F) were detected in the range of 1.17-806 µg/kg.

Today most foods are available in a packed form. During storage, the migration of chemical substances from food packaging materials into food may occur and may therefore be a potential source of consumer exposure. To protect the consumer, standard migration tests are laid down in Regulation (EU) No. 10/2011. When using those migration tests and applying additional conservative conventions, estimated exposure is linked with large uncertainties including a certain margin of safety. Thus the research project FACET was initiated within the 7th Framework Programme of the European Commission with the aim of developing a probabilistic migration modelling framework which allows one (1) to calculate migration into foods under real conditions of use; and (2) to deliver realistic concentration estimates for consumer exposure modelling for complex packaging materials (including multi-material multilayer structures). The aim was to carry out within the framework of the FACET project a comprehensive systematic study on the solubility behaviour of foodstuffs for potentially migrating organic chemicals. Therefore a rapid and convenient method was established to obtain partition coefficients between polymer and food, KP/F. With this method approximately 700 time-dependent kinetic experiments from spiked polyethylene films were performed using model migrants, foods and ethanol-water mixtures. The partition coefficients of migrants between polymer and food (KP/F) were compared with those obtained using ethanol-water mixtures (KP/F's) to investigate whether an allocation of food groups with common migration behaviour to certain ethanol-water mixtures could be made. These studies have confirmed that the solubility of a migrant is mainly dependent on the fat content in the food and on the ethanol concentration of ethanol-water mixtures. Therefore dissolution properties of generic food groups for migrants can be assigned to those of ethanol-water mixtures. All foodstuffs (including dry foods) when allocated to FACET model food group codes can be classified into a reduced number of food categories each represented by a corresponding ethanol-water equivalency.

Polyvinyl chloride (PVC) food-wrapping films plasticized with di-(2-ethylhexyl) adipate (DEHA) are commonly used by grocery stores in Canada to rewrap meat, poultry, fish, cheese, and other foods. DEHA was assessed as part of the Government of Canada's Chemicals Management Plan. The main source of exposure for most age groups was expected to be food. Although the margin of exposure from food and beverages is considered to be adequately protective, the Government of Canada committed to performing targeted surveys of DEHA in foods and food packaging materials to better define Canadian exposure to DEHA through dietary intake. In order to determine whether more-comprehensive targeted surveys on DEHA in foods should be conducted, 26 food composite samples from the 2011 Canadian total diet study were selected and analyzed for DEHA using a method based on solvent and dispersive solid-phase extraction and gas chromatography-mass spectrometry. These 26 food composites include cheese, meat, poultry, fish, and fast foods, and PVC films were likely used in packaging the individual foods used to make the composites. DEHA was detected in most of the meat, poultry, and fish composite samples, with the highest concentration found in ground beef (11 μg/g), followed by beef steak (9.9 μg/g), freshwater fish (7.8 μg/g), poultry liver pâté (7.4 μg/g), fresh pork (6.9 μg/g), cold cuts and luncheon meats (2.8 μg/g), veal cutlets (2.1 μg/g), roast beef (1.3 μg/g), lamb (1.2 μg/g), and organ meats (0.20 μg/g). Targeted surveys should be conducted to investigate the presence of DEHA in various foods packaged with PVC films in more detail and provide updated occurrence data for accurate human exposure assessment.

A simple and sensitive single step electro membrane extraction (EME) procedure was demonstrated for biological organic anions with determination by ion chromatography (IC). Nitrite, adipate, oxalate, iodide, fumarate, thiocyanate and perchlorate were extracted from aqueous donor solutions, across a supported liquid membrane (SLM) consisting of methanol impregnated in the walls of a porous polypropylene membrane bag and into an alkaline aqueous acceptor solution in the lumen of the propylene envelope by the application of potential of 12V applied across the SLM. The acceptor solution was analyzed by IC. Parameters affecting the extraction performance such as type of SLM, extraction time, pH of the donor and acceptor solution, and extraction voltage were studied. The most favorable EME conditions were methanol as the SLM, extraction time of 5min, pH of acceptor and sample solutions of 12 and 4, respectively, and a voltage of 12V. Portable 12V batteries were used in the study. Under these optimized conditions, all anions had enrichment factors ranging from 3.6 to 36.2 with relative standard deviations (n=3) of between 6.6 and 17.5%. Good linearity ranging from 0.1 to 10μgmL(-1) with coefficients of correlation (r) of between 0.9981 and 0.9996 were obtained. The limits of detection of the EME-IC method were from 0.01 to 0.14μgmL(-1). The developed methodology was applied to amniotic fluid samples to evaluate the feasibility of the method for real applications., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Human scent can be collected by either contact or non-contact sampling mode. The most frequently used human scent evidence collection device known as the Scent Transfer Unit (STU-100) is a dynamic sampling device and is often used in a non-contact mode. A customized human scent collection chamber was utilized in combination with controlled odor mimic permeation systems containing five standard human scent volatiles to optimize the flow rate, collection material and geometry of the absorbent material. The scent collection method which yielded the greatest amount of volatile organic compounds (VOCs) detected included the use of a single layer of Johnson and Johnson gauze/multiple layers of Dukal gauze with the STU-100 on the lowest flow rate setting. The correlation of the resulting VOC profiles demonstrate that collection of standard VOCs in controlled conditions yielded reproducible VOC profiles on all materials studied with the exception of polyester. Finally, the method was tested using actual human subjects under optimized set of conditions., (Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.)

The aim of this study was to determine the concentrations of six phthalic acid diesters (PAEs) [di(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBP), diisononyl phthalate (DINP), di-n-octyl phthalate (DNOP), and diisodecyl phthalate (DIDP)], two non-phthalic plasticizers [di(2-ethylhexyl) adipate (DEHA), 2,2,4-trimethyl-1,3-pentanediol diisobutylate (TMPDIB)], and mono 2-ethylhexyl phthalate(MEHP) in polyvinyl chloride (PVC) household products that children often places in their mouths and/or contact with their skin (41 products, 47 samples) in Japan. The detection frequencies of the studied compounds were as follows: DEHP (79 %), DINP-2 (13 %), DINP-1 (11 %), DBP (8.5 %), DEHA (8.5 %), DIDP (4.3 %), and DNOP (2.1 %). Concentrations of these compounds ranged from 0.021 % to 48 %. BBP and TMPDIB were not detected in the all samples. Most samples contained DEHP and DINP at high concentrations over 0.1 %. High concentrations of PAEs were detected in PVC household products that appear appealing to children and can possibly be licked and chewed by them. Di(2-ethylhexyl) terephtalete, diisononyl 1,2-cyclohexanedicarboxylic acid, acetyl tributyl citrate, and di(2-ethylhexyl) 4-cyclohexene-1,2-dicarboxylate used as substitute plasticizers were also detected in several samples. MEHP was present in 70 % of the samples, with concentrations ranging from trace amounts to 140 μg/g. The ratios of MEHP against DEHP were 6.2 × 10(-4) to 1.6 × 10(-1) %. MEHP in the household products investigated in this study was most probably an impurity in DEHP. The high concentrations of PAEs detected in products that children often place in their mouth reveal the importance of replacing plasticizers in common household products, and not just children's toys, with safer alternatives.

Polyadipate plasticizers can be present in the polyvinylchloride (PVC) gaskets used to seal the lids of glass jars. As the gaskets can come into direct contact with the foodstuffs inside the jar, the potential exists for polyadipate migration into the food. The procedure and performance characteristics of a test method for the analysis of polyadipates in food simulants (3% aqueous acetic acid and 10% aqueous ethanol) and the volatile test media used in substitute fat tests (isooctane and 95% aqueous ethanol) are described. The PVC gaskets were exposed to the food simulants or their substitutes under standard test conditions. Studies were initially carried out using direct measurement of the polyadipate oligomers by liquid chromatography with time-of-flight mass spectrometric detection (LC-TOF-MS) but this was not practical due to the number of peaks detected. Instead, the migrating polyadipates were hydrolysed to adipic acid and measured by liquid chromatography with tandem mass spectrometric detection (LC-MS/MS). The amount of polyadipate that this measurement of adipic acid represents was then calculated. Method performance was assessed by analysis of gaskets from two types of jar lids by single-laboratory validation. Linearity, sensitivity, repeatability, intermediate reproducibility and recovery were determined to be suitable for checking compliance with the 30 mg/kg specific migration limits for polyesters of 1,2-propane diol and/or 1,3- and/or 1,4-butanediol and/or polypropylene-glycol with adipic acid, which may be end-capped with acetic acid or fatty acids C(12)-C(18) or n-octanol and/or n-decanol. The method was found to be much quicker than previous methods involving extraction, clean-up, hydrolysis, esterification, derivatisation and GC measurement, consequently saving time and money.

This study describes an analytical methodology developed for determination of phthalate esters (di-n-butyl, butylbenzyl and di-2-ethylhexyl phthalate) and adipate (di-n-ethylhexyl adipate) by solid-phase microextraction (SPME) and gas chromatography in normal saline solutions and, in bi-distilled water used to reconstitute medicines. An 85-microm-polyacrylate SPME fiber was selected and used in all analyses. The parameters affecting extraction efficiency were simultaneously optimized, firstly by means of a two-level full factorial design including a center point and subsequently through a Doehlert design for two-variables. Satisfactory detection limits in the range of 0.18 to 0.75 microg L(-1) and excellent precision, with relative standard deviation values being lower than 15.1% (n = 6), were obtained. Relative sensitivities of between 72.3 and 124.3% were obtained.

A GC/MS method was developed and successfully validated for the determination of adipate plasticizers in ham sausage migrated from polyvinylidene chloride (PVDC) packaging film. The sample pretreatment includes liquid extraction, solvent evaporation, and reconstitution before and after solid phase extraction (SPE). For the 5 adipate plasticizers studied, the SPE process with Oasis MAX cartridge showed an extraction efficiency from 85.7% to 106%, and the calibration curves are all linear in the range of 5 to 1000 ng/g with correlation coefficients greater than 0.998. The method proved to be accurate and precise; the average intraday recovery ranges from 85.4% to 114.6% with a %CV value from 2.5 to 11.3, and the average interday recovery from 83.6% to 118.5% with a %CV value from 2.8 to 15.6, respectively, for the adipate plasticizers. The method is sensitive and was effectively applied in the kinetic and penetration studies of the adipate plasticizers migrating from food-grade PVDC packaging film into ham sausage. The experimental data showed that approximately 6.8% of dibutyl adipate (DBA) in the packaging film migrated into the ham sausage in 4 mo and the migration reached the innermost portion of the sausage in 6 mo.

The performance of three fibres for the headspace solid-phase microextraction (SPME) of di-2-ethylhexyl adipate (DEHA) and eight phthalates in water was investigated systematically under different extraction conditions. Good responses on the 65 microm polydimethylsiloxane/divinylbenzene (PDMS/DVB) SPME fibre were observed for DEHA and all phthalates. The polydimethylsiloxane (PDMS) SPME fibre had very poor responses for the lighter and slightly polar phthalates, dimethyl phthalate (DMP) and diethyl phthalate (DEP), while the divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) SPME fibre had very poor responses for the heavier and non-polar adipate and phthalates. The salt (NaCl) was found to increase the partitioning of DMP, DEP, diisobutyl phthalate (DiBP), di-n-butyl phthalate, and benzyl butyl phthalate (BBP) from water into the headspace, while partitioning of heavier adipate and phthalates from water into headspace was suppressed when the concentration of NaCl was above 10%. The automated headspace SPME methods were developed and validated under two different salting conditions (30% NaCl for DMP, DEP and BBP, and 10% for DEHA, DiBP, DBP, di-n-hexyl phthalate (DHP), di-2-ethylhexyl phthalate (DEHP), and di-n-octyl phthalate (DOP)). Linearity with R(2) values better than 0.9949 was observed for DEHA and eight phthalates over the range from 0.1 to 20 microg L(-1). Method detection limits ranged from 0.003 microg L(-1) for DOP to 0.085 microg L(-1) for BBP. Good repeatability was observed for DEHA and most phthalates with relative standard deviation (RSD) values less than 10%. The methods were used to analyse bottled water samples for DEHA and eight phthalates. DMP, DHP, BBP, DEHA and DOP were not detected in any samples. Concentrations of the other phthalates were low (around sub-ppb) except for DBP in the water from a polycarbonate bottle at 1.72 microg L(-1).

The plasticizers bis (2-ethylhexyl) phthalate (BEHP), bis (2-ethylhexyl) terephthalate (BEHTP) and bis (2-ethylhexyl) adipate (BEHA) were found in significant quantities in the influents, process streams, treated effluent and solid residues of a large physicochemical treatment plant in Montreal, Canada. Of these plasticizers, BEHA was the most abundant in the influent but most was removed during primary treatment. Evidence indicated that significant biodegradation occurred within the sewers and during treatment resulting in the formation of three biodegradation products that had been reported in earlier laboratory studies; namely, 2-ethylhexanol, 2-ethylhexanal and 2-ethylhexanoic acid. Significantly greater concentrations of 2-ethylhexanal were found in process streams than had been reported in earlier laboratory work. This was attributed to the fact that there were fewer opportunities for losses of this volatile compound over the course of wastewater treatment. The plasticizers were removed from the aqueous phase to varying degrees during treatment, with most ending up in the solid residues. All three metabolites and the parent plasticizers were observed in the effluent and most were found in the solids that were analyzed. Results suggest that the treatment plant does not effectively remove plasticizers from the influent and represents a significant source of these compounds and their degradation products in the environment.

Phthalates are ubiquitous environmental chemicals with potential detrimental health effects. The purpose of our study was to quantify dietary intake of phthalates and of DEHA (Di-ethylhexyl adipate) using duplicate diet samples and to compare these data with the calculated data based on urinary levels of primary and secondary phthalate metabolites. 27 female and 23 male healthy subjects aged 14-60 years collected daily duplicate diet samples over 7 consecutive days. Overall, 11 phthalates were measured in the duplicates by GC/MS and LC/MS methods. Urinary levels of primary and secondary phthalate metabolites are also available. The median (95th percentile) daily intake via food was 2.4 (4.0) microg/kg b.w. (Di-2-ethylhexyl phthalate, DEHP), 0.3 (1.4) microg/kg b.w. (Di-n-butyl phthalate, DnBP), 0.6 (2.1) microg/kg b.w. (Di-isobutyl phthalate, DiBP) and 0.7 (2.2) microg/kg b.w. for DEHA. MEPH (Mono-2-ethylhexyl phthalate) was detectable only in minor concentrations in the samples, thus conversion of DEHP to MEHP and dietary intake of MEHP were negligible. When comparing back-calculated intake data of the DEHP metabolites with dietary DEHP intake from the day before significant correlations were observed for most of the metabolites. No correlation was found for DnBP and only a weak but significant correlation for DiBP. The median and 95th percentile daily dietary intake of all target analytes did not exceed the recommended tolerable daily intake. Our data indicated that food was the predominant intake source of DEHP, whilst other sources considerably contributed to the daily intake of DnBP and DiBP in an adult population.

A method for trace analysis of two plasticizers, di-2-ethylhexyl phthalate (DEHP) and di-2-ethylhexyl adipate (DEHA), contaminated in packaged curry paste were investigated by gas chromatography with flame ionization detector (GC-FID). Curry paste samples were extracted by ultrasonic and solid phase extraction using Florisil(R) cartridge. Analysis by the GC-FID system provided limits of detection for DEHA and DEHP at 12 and 25 microg L(- 1) and a linear dynamic range between 25 microg L(- 1) to 60 mg L(- 1) with a coefficient of determination (R(2)) greater than 0.99. High recoveries were obtained, ranged from 91 to 99% and 88 to 98% for DEHP and DEHA with RSD lower than 7 and 10% respectively. The method detection limit and limits of quantitation were ranged from 27 to 30 and 90 to 100 microg L(- 1). The analysis of curry paste samples showed concentrations of DEHP and DEHA in the range of 4.0 ng g(- 1) to 0.61 microg g(- 1).

Pseudomonas aeruginosa, isolated from soil near tannery effluent was able to degrade 8-anilino-1-naphthalenesulfonic acid (ANSA), a sulfonated aromatic amine. The organism degraded this amine up to a concentration of 1,200 mg l(-1) using glucose and ammonium nitrate as carbon and nitrogen sources respectively. The degradation started when the organism reached its late exponential growth phase. Salicylic acid and beta-ketoadipic acid were identified as intermediate compounds using HPLC and GC-MS and provide evidence for ortho pathway reactions. Further proof for the pathway is obtained from the dioxygenase activity of the strain growing exponentially in medium with ANSA and glucose.

The plasticizers di-2-ethylhexyl phthalate (DEHP) and di-2-ethylhexyl adipate (DEHA) are ubiquitous in the environment and undergo partial biodegradation in the presence of soil micro-organisms. The validity of a proposed pathway for the degradation of these plasticizers by Rhodococcus rhodochrous has been confirmed by the identification of 2-ethylhexanal in gas phase emissions. Complete analyses of the aqueous and gas phases were able to account for more than 98% of the 2-ethylhexanol component of the DEHA added at the beginning of a growth study. Of this, 25% was either 2-ethylhexanol or 2-ethylhexanal that had been stripped into the gas phase and, at most, only 2% of the 2-ethylhexanol component could have been removed by mineralization. It is concluded that plasticizers are of significant environmental concern due to the resistance of the metabolites to biodegradation and their known health impacts. Two of the metabolites are of added concern due to their volatility and their potential impact on indoor air quality.

Stir bar sorptive extraction with liquid desorption followed by large volume injection and capillary gas chromatography coupled to mass spectrometry (SBSE-LD/LVI-GC-MS), had been applied for the determination of ultra-traces of seven-phthalates (dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, butyl benzyl phthalate, bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate and bis(1-octyl) phthalate) in drinking water samples, which are included in the priority lists set by several international regulatory organizations. Instrumental calibration under the selected-ion monitoring mode acquisition (LVI-GC-MS(SIM)), experimental parameters that could affect the SBSE-LD efficiency, as well as, the control of the contamination profile are fully discussed. Throughout systematic assays on 30 mL water samples spiked at the 0.40 microg/L level, it had been established that stir bars coated with 47 microL of polydimethylsiloxane, an equilibrium time of 60 min (1,000 rpm) and methanol as back extraction solvent, allowed the best analytical performance to monitor phthalates in water matrices. From the data obtained, good accuracy and a remarkable reproducibility (< 14.8%) were attained, providing experimental recovery data in agreement with the theoretical equilibrium described by the octanol-water partition coefficients (K(PDMS/W) approximately K(O/W)), with the exception of bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate and bis(1-octyl) phthalate, for which lower yields were measured. Additionally, a remarkable linear dynamic range between 25 and 2,000 ng/L (r(2)>0.99) and low detection limits (3-40 ng/L) were also achieved for the seven-phthalates studied. The application of the present method to monitor phthalates in tap and bottled mineral water samples, allowed convenient selectivity and high sensitivity up to 1.0 microg/L level, using the standard addition methodology. The proposed method showed to be feasible and sensitive with a low sample volume requirement to monitor phthalates in drinking water matrices at the ultra-trace level, in compliance with international regulatory directives on water quality.

Packaging materials intended for direct food contact were acquired on the Brazilian retail market and analysed for their plasticizer content. Analyses were carried out by gas chromatography with flame ionization detection. Di-2-ethyl-hexyl adipate (DEHA), di-2-ethyl-hexyl phthalate (DEHP) and di-iso-decyl phthalate (DIDP) plasticizers were identified in films and closure seals in concentrations ranging from 12 to 19% (w/w), 15 to 44% (w/w) and 10 to 11% (w/w), respectively. Brazilian regulations state that for use with foods with a fat content above 5%, the levels of DEHP and DIDP in the plastic material should be no greater than 3%. The results obtained demonstrate a lack of conformity. It would be advisable to include information on the labels of packaging materials about their restrictions of use in order to advise manufacturers and consumers about their proper usage.

The determination of commercial plasticizers (di-(2-ethylhexyl)adipate (DEHA) and acetyl tributyl citrate (ATBC)) in aqueous solutions is described. The newly proposed technique of applying microwaves to cloud point extracts in order to enable combination with gas chromatographic analysis has been used for this purpose. Both plasticizers were entrapped in the micelles of the non-ionic surfactant Triton X-114 and removed from the bulk phase by centrifugation. Micellization was enhanced by increasing the ionic strength of the solution with concentrated NaCl. Extraction recoveries of the proposed method were over 95% for water and 3% (w/v) aqueous acetic acid and over 85% for 10% (v/v) aqueous ethanol, respectively. The calibration curves obtained, following the proposed methodology have a linear range between 50 and 2000 microg/L for each analyte while the detection limits were as low as 15 and 19 microg/L for DEHA and ATBC, respectively, with an RSD below 5% even for low concentrations. As an analytical demonstration the proposed methodology was applied for the determination of the migration levels of the selected plasticizers from a PVC food packaging film into aqueous simulants.

We monitored 26 compounds known or suspected to be endocrine disruptors in several environmental water samples from a river, the sea, and an irrigation canal. Because of the various chemical properties of the compounds monitored, analyses were carried out by using two different methods. One method is based on solid-phase extraction (SPE) on-line coupled to gas chromatography-mass spectrometry through an on-column interface. Another is based on high-performance liquid chromatography-(electrospray) mass spectrometry working in negative ionization mode and using off-line SPE. The limits of detection for the two methods were at levels of low microg/L. Phthalates and bis-(2-ethylhexyl) adipate were found at levels between 0.05 and 13 microg/L in all of the water samples analyzed. Some pesticides, alkylphenols, and estrogens were determined in a few samples at levels below 0.1 microg/L.

Atomic force microscopy (AFM) has been used to investigate the (1 0 0) face of crystalline adipic acid, both in air and liquid environments. In air, surface reorganization occurred during scanning of the AFM probe, which has been investigated using single point force-distance analysis under a controlled relative humidity (RH) environment. We suggest such reorganization can be attributed to the influence of a network of water molecules bound to the hydrophilic (1 0 0) surface permitting local AFM tip-enhanced dissolution and reorganization of the solute. In situ imaging was also carried out on the crystals, revealing etch-pit formation during dissolution, and rapid growth at higher levels of supersaturation (sigma), both of which are direct consequences of the hydrophilic nature of the (1 0 0) face. Also presented here are nanoscale observations of the effect of octanoic acid, a structurally-related habit modifier, on crystalline adipic acid. Using AFM, we have been able to show that the presence of octanoic acid at low concentration has little observable affect on the development of the (1 0 0) face; however, as this concentration is increased, there are clear changes in step morphology and growth mode on the (1 0 0) face of the crystal. At a concentration of 1.26 mmol dm(-3) (a concentration corresponding to a molar ratio of approximately 1:175 octanoic acid:adipic acid), growth on the (1 0 0) face is inhibited, with in situ AFM imaging indicating this is a direct consequence of octanoic acid binding to the surface, and pinning the monomolecular growth steps.

In this work, PM(10) samples were collected in a winter and a summer in Christchurch, a New Zealand city having intensive wood and coal burning and a serious air pollution problem in winter. Oxalic, malonic, succinic, maleic, glutaric and adipic acids in the samples were analysed using ion chromatography. It was suggested that solid fuel burning had large influence on the occurrence of these low molecular weight dicarboxylic acids resulting in significantly higher wintertime concentrations of maleic acid, oxalic acid and glutaric or adipic acid. The most pronounced feature observed was that maleic acid was the second most abundant species of the detected DCAs in the winter (with a mean of 74 ngm(-3) and the highest concentration ever reported of 231 ngm(-3)). In contrast, malonic acid experienced a low abundance in both seasons. The observed seasonal patterns and molecular distribution were inconsistent with those in most other urban areas. On an average, the total detected dicarboxylic acids accounted for about 0.5% of PM(10) mass with a maximum of 1.4% in the winter. The relative importance of different sources to individual dicarboxylic acids varied with seasons and is discussed in detail.

In this survey magnesium sails in the form of solid dispersions were studied to examine the interaction of the drug and lecithin or Tego Betain L-7. The results of thermal analysis of solid dispersions containing magnesium adipate Mg[Adip] and compounds of this salt with glycine substituent, and the partition coefficient (logP) of this salts applied for solid dispersion, have been presented in this paper. Lecithin (45% phosphatidylcholine) or Tego Betain L-7 (30% solution of amide betaine) have been added to magnesium salts to obtain a solid dispersion. The influence of auxiliary substances: Tego Betain L-7 and lecithin on physicochemical properties of the examined preparations has been assessed. The results of thermal analysis (DTA, DSC, TG) of magnesium complexes indicated their good thermal resistance up to the temperature of 375 K.

A solid-phase extraction (SPE) method was developed for the simultaneous extraction of dicarboxylic acids and diols formed during hydrolysis of poly(butylene succinate), PBS, and poly(butylene adipate), PBA. Four commercial non-polar SPE columns, three silica based: C8, C18, C18 (EC), and one resin based: ENV+, were tested for the extraction of succinic acid, adipic acid and 1,4-butanediol, the expected final hydrolysis products of PBS and PBA. ENV+ resin was chosen as a solid-phase, because it displayed the best extraction efficiency for 1,4-butanediol and succinic acid. Linear range for the extracted analytes was 1-500 ng/microl for adipic acid and 2-500 ng/microl for 1,4-butanediol and succinic acid. Detection and quantification limits for the analytes were between 1-2 and 2-7 ng/microl, respectively, and relative standard deviations were between 3 and 7%. Good repeatability and low detection limits made the developed SPE method and subsequent gas chromatography-mass spectrometry (GC-MS) analysis a sensitive tool for identification and quantification of hydrolysis products at early stages of degradation.

We investigated the labeling and content of plasticizers of soft plastic toys. First, we investigated material labeling in 96 products purchased in fiscal years 2000 and 2001. Among these products, 43% of those purchased in fiscal 2000 and 68% of those purchased in fiscal 2001 were labeled. We then investigated the kinds and amounts of plasticizers in 73 soft polyvinyl chloride (PVC) toys. Three kinds of phthalates and six other kinds of plasticizers were detected in the soft PVC toys. Diisononyl phthalate, di(2-ethylhexyl) phthalate, diisononyl adipate, and O-acetyl tributyl citrate were detected at high frequency, and in large amounts. The average total content of all plasticizers was 280 mg/g for the products purchased in fiscal 2000 and 227 mg/g for those in fiscal 2001. In fiscal 2001, antioxidants, 4-nonylphenol, and bisphenol A were investigated in addition to plasticizers.