Calculation and Experimental Validation of a Novel Approach Using Solubility Parameters as Indicators for the Extraction of Additives in Plastics.

Accurately quantifying chemical additives with adverse health effects in plastic products is critical for environmental safety and risk assessment. In this work, a novel approach using solubility parameters (δ) as indicators for the extraction of additives in plastics was developed. The mechanism was evaluated by using 10 organic solvents with different solubility parameters to extract brominated flame-retardant-decabrominated diphenyl ether (BDE-209) in polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET). Certified reference materials (CRMs) or CRM candidate materials were applied as matrix materials. The extracted BDE-209 and solubility parameters of solvents could fit into a curve of a quadratic function. The value of abscissa corresponding to the vertex of the function was close to the solubility parameter of plastic calculated by the group contribution method (Δδ < 0.37). Toluene, n-hexane, and acetone were the solvents with high extraction efficiency for PE, PP, and PET, confirming the feasibility of the developed approach. The results of ethyl acetate and acetone indicated the high weight of functional groups affecting the dissolution behavior. The developed approach was further verified by analyzing penta-/octa-BDE and phthalate esters in PET and polyvinyl chloride (PVC) and finally applied to analyze 15 plastic products made of PP, PE, PET, polystyrene, and PVC. The detected tetrabromodiphenyl ether (BDE-47), BDE-209, decabromodiphenyl ethane, and di(2-ethylhexyl) terephthalate all matched the approach and verified its practicability for field sample analysis.

Simultaneous determination of polybrominated diphenyl ethers and hydroxylated analogues in human serum using high-performance liquid chromatography-inductively coupled plasma mass spectrometry.

Polybrominated diphenyl ethers (PBDEs) and their hydroxylated (OH-BDE) analogues are known as contaminants with potential risks to human health. In this work, a HPLC-ICP-MS method was developed for simultaneous determination of four polybrominated diphenyl ethers (BDE-47, -99, -153 and -209) and four hydroxylated analogues (3-OH-BDE-47, 5-OH-BDE-47, 6-OH-BDE-47, 5'-OH-BDE-99) in human serum. Solid-phase extraction (SPE) was employed as the primary extraction and purification procedure. By using mixtures of acetone and hexane with different rations, OH-PBDEs and PBDEs were efficiently recovered during elution procedure. With additional ultrasonic assisted extraction of PBDEs from solid residue after protein precipitation, the recoveries of investigated analytes ranged from 79.1 %to 89.9%. Due to the characteristics of inductively coupled plasma (ICP), organic matrix effects were effectively eliminated. Good sensitivity and precision were also obtained. The limits of quantification ranged from 0.060 to 0.081 ng mL-1 and inter-/intra-day relative standard deviations were all below 4%. In addition, compound-independent calibration (CIC) was investigated and the spray chamber efficiency might be a key factor for CIC application among different kinds of brominated chemicals. Finally, the developed method was successfully applied for analysis of 20 human serum samples collected from the Tianjin city. This work provided an alternative approach for simultaneous determination of halogenated chemicals by quantification of halogen element with one-time pretreatment, especially for human serum samples with limited sample volume.

Determination of bisphenol analogues in food-contact plastics using diode array detector, charged aerosol detector and evaporative light-scattering detector.

Freshness protection packages and preservative films are widely used food-contact plastic made of polyethylene. Diode array detector (DAD), charged aerosol detector (CAD) and evaporative light-scattering detector (ELSD) were evaluated for determination of 6 bisphenols (bisphenol A, bisphenol S, bisphenol F, bisphenol B, bisphenol AF and tetrabromobisphenol A.) in polyethylene. DAD presented better parameters including limit of quantification (LOQs) ranging from 0.05 to 0.5 µg/g with relative standard deviations (RSDs, n = 5) lower than 1% at two concentration levels. CAD and ELSD are universal detectors with relative consistent response parameters for different analogues which have potential application by using single calibrant for quantification of multiple analytes. Matrix effects were barely observed on three detectors. Samples of freshness protection packages and preservative films were further analyzed and preliminary profiles of bisphenols in products from Beijing market was obtained. Bisphenol S have become most abundant analogue instead of bisphenol A in investigated products.

Development and evaluation of microwave-assisted and ultrasound-assisted methods based on a quick, easy, cheap, effective, rugged, and safe sample preparation approach for the determination of bisphenol analogues in serum and sediments.

Microwave- and ultrasound-assisted methods based on a quick, easy, cheap, effective, rugged, and safe sample preparation approach followed by high-performance liquid chromatography with tandem mass spectrometry were developed for the simultaneous determination of eight bisphenol analogues in serum and sediment. The developed methods provided satisfactory extraction efficiency for the energy provided by microwaves and ultrasound. Compositions of commercial sorbents (primary secondary amine, MgSO4 , octadecyl-modified silica, and graphitized carbon black) were evaluated. The ultrasound-assisted method was suited for serum using primary secondary amine, MgSO4 , and octadecyl-modified silica as sorbents and a mixture of hexane and ethyl acetate as extraction solvent. The microwave-assisted method worked better for sediment with tetrahydrofuran and methanol as solvents and primary secondary amine, MgSO4 , octadecyl-modified silica, and graphitized carbon black as sorbents. Other experimental parameters, such as extraction temperature and time, were also optimized. The inter- and intraday relative standard deviations ranged from 2.7 to 5.5%. The limits of detection were between 0.1 and 1.0 ng/mL for serum and between 0.1 and 0.5 ng/g dry weight for sediment. The proposed methods were successfully applied to seven sediment and 20 human serum samples. The results showed that the developed methods were practical for the analysis and biomonitoring of bisphenols in sera and sediment.

Development, comparison and application of sorbent-assisted accelerated solvent extraction, microwave-assisted extraction and ultrasonic-assisted extraction for the determination of polybrominated diphenyl ethers in sediments.

Fast and selective analytical methods were developed based on sorbent-assisted mechanism and microwave-assisted extraction (SA-MAE), accelerate solvent extraction (SA-ASE) and ultrasonic-assisted extraction (SA-UAE) for the determination of polybrominated diphenyl ethers (PBDEs) in sediments. The experimental parameters, such as extraction conditions and sorbent amounts, were optimized according to Taguchi Orthogonal Arrays. The accuracy of developed SA-methods was a satisfactory ranging from 71% to 118%. The inter/intra-day RSDs were <10% indicating a good method precision. The limits of quantification (LOQ) for target BDEs were ≤1.0ng/g dry weight (dw) with an exception of BDE 209 which was 10.0ng/g dw. The proposed methods were validated by the analysis of PBDEs in standard reference materials (SRM 1944) and the method performances were compared with each other. The results approved the feasibility of SA-methods for PBDEs analysis in sediments. Meanwhile, the optimization processes indicated the mixed sorbents mainly worked on matrix effects elimination. The compositions of sorbents deserved careful optimization because different characteristics of the matrix and extraction intensity may produce various matrix effects. In addition, the developed SA-ASE method was successfully applied on real environmental samples collected from a typical polluted area. The data and calculation suggested local environmental contamination pattern and potential pollution source.

Certified reference materials (GBW09170 and 09171) of creatinine in human serum.

Creatinine is the most widely used clinical marker for assessing renal function. Concentrations of creatinine in human serum need to be carefully checked in order to ensure accurate diagnosis of renal function. Therefore, development of certified reference materials (CRMs) of creatinine in serum is of increasing importance. In this study, two new CRMs (Nos. GBW09170 and 09171) for creatinine in human serum have been developed. They were prepared with mixtures of several dozens of healthy people's and kidney disease patient's serum, respectively. The certified values of 8.10, 34.1 mg/kg for these two CRMs have been assigned by liquid chromatography-isotope dilution mass spectrometry (LC-IDMS) method which was validated by using standard reference material (SRM) of SRM909b (a reference material obtained from National Institute of Standards and Technology, NIST). The expanded uncertainties of certified values for low and high concentrations were estimated to be 1.2 and 1.1%, respectively. The certified values were further confirmed by an international intercomparison for the determination of creatinine in human serum (Consultative Committee for Amount of Substance, CCQM) of K80 (CCQM-K80). These new CRMs of creatinine in human serum pool are totally native without additional creatinine spiked for enrichment. These new CRMs are capable of validating routine clinical methods for ensuring accuracy, reliability and comparability of analytical results from different clinical laboratories. They can also be used for instrument validation, development of secondary reference materials, and evaluating the accuracy of high order clinical methods for the determination of creatinine in human serum.