Identification and Quantification of Micro-Bioplastics in Environmental Samples by Pyrolysis-Gas Chromatography-Mass Spectrometry.

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.

Comparison of LC-ESI, DART, and ASAP for the analysis of oligomers migration from biopolymer food packaging materials in food (simulants).

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.

Exploring functionality of the reverse ß-oxidation pathway in Corynebacterium glutamicum for production of adipic acid.

BACKGROUND: Adipic acid, a six-carbon platform chemical mainly used in nylon production, can be produced via reverse ß-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 ß-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 ß-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 ß-ketoadipyl-CoA thiolase were determined as potential target for further improvement of the pathway.

Phthalic acid esters and adipates in herbal-based soft drinks: an eco-friendly method.

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.

Di(2-ethylhexyl) adipate plasticizer triggers hepatic, brain, and cardiac injury in rats: Mitigating effect of Peganum harmala oil.

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-1ß. 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.

In vitro reconstitution of the catabolic reactions catalyzed by PcaHG, PcaB, and PcaL: the protocatechuate branch of the ß-ketoadipate pathway in Rhodococcus jostii RHA1.

The ß-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 ß-ketoadipate pathway in the available genetic database, yet the functions of these genes remain uncharacterized. In this study, the protocatechuate branch of the ß-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, ß-ketoadipate enol-lactone, 3-carboxy-cis,cis-muconate, γ-carboxymuconolactone, muconolactone, and ß-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 ß-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 ß-ketoadipate pathways deposited in the genetic database.

Direct biosynthesis of adipic acid from a synthetic pathway in recombinant Escherichia coli.

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.

Solid-based disperser liquid-liquid microextraction for the preconcentration of phthalate esters and di-(2-ethylhexyl) adipate followed by gas chromatography with flame ionization detection or mass spectrometry.

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.

Residues of non-phthalate plasticizers in seawater and sediments from Osaka Bay, Japan.

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.

Development and validation of a GC Orbitrap-MS method for the analysis of phthalate esters (PAE) and bis(2-ethylhexyl)adipate (DEHA) in atmospheric particles and its application for screening PM2.5 from Curitiba, Brazil.

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 PM2.5 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 PM2.5 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.

Monitoring of the presence of plasticizers and effect of temperature and storage time in bottled water using a green liquid-liquid microextraction method.

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.

Assessment of endocrine disruptor pollutants and their metabolites in environmental water samples using a sustainable natural deep eutectic solvent-based analytical methodology.

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.

The Difference of Gut Microbiota and Their Correlations With Urinary Organic Acids Between Autistic Children With and Without Atopic Dermatitis.

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.

Analysis of phthalic acid diesters, monoester, and other plasticizers in polyvinyl chloride household products in Japan.

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.

GC-MS Analysis of Phthalates and Di-(2-thylhexyl) Adipate in Canadian Human Milk for Exposure Assessment of Infant Population.

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.

How does continuous venovenous hemofiltration theoretically expose (ex-vivo models) inpatients to diethylhexyladipate, a plasticizer of PVC medical devices?

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 ¼ 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.

Distribution of five SVOCs in a model room: effect of vacuuming and air cleaning measures.

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.

Determination of phthalates and adipate in bottled water by headspace solid-phase microextraction and gas chromatography/mass spectrometry.

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).

Plasticizers and their degradation products in the process streams of a large urban physicochemical sewage treatment plant.

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.

Detection and quantification analysis of chemical migrants in plastic food contact products.

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.