Determination of potential dermal exposure rates of phosphorus flame retardants via the direct contact with a car seat using artificial skin.

Dermal exposure to phosphorus flame retardants (PFRs) has received much attention as a major alternative exposure route in recent years. However, the information regarding dermal exposure via direct contact with a product is limited. In addition, in the commonly used dermal permeability test, the target substance is dissolved in a solvent, which is unrealistic. In this study, a dermal permeability test of PFRs in three car seats was performed using artificial skin. The PFR concentrations in the car seats are 0.12 wt% tris(2-chloroethyl) phosphate (TCEP), 0.030-0.25 wt% tris(2-chloroisopropyl) phosphate (TCPP), 0.15 wt% triphenyl phosphate (TPhP), 0.89 wt% cresyl diphenyl phosphate (CsDPhP), 0.074 wt% tricresyl phosphate (TCsP), and 0.46-4.7 wt% diethylene glycol bis [di (2-chloroisopropyl) phosphate (DEG-BDCIPP). The mean skin permeation rates for a contact time of 24 h are 14 (TCEP), 5.4-160 (TCPP), 0.67 (CsDPhP), 0.38 (TPhP), and 3.3-58 ng cm-2 h-1 (DEG-BDCIPP). The concentrations of TCsP in receptor liquid were lower than the limit of quantification at the contact time of 24 h. The skin permeation rates were significantly affected by the type of car seat (e.g., fabric or non-fabric). The potential dermal TCPP exposure rate for an adult via direct contact with the car seat during the average daily contact time (1.3 h), which was the highest value assessed in this study, was estimated to be 16,000 ng kg-1 day-1, which is higher than that related to inhalation and dust ingestion reported as significant exposure route of PFRs in previous studies. These facts reveal that dermal exposure associated with direct contact with the product might be an important exposure pathway for PFRs.

Formaldehyde-free and durable phosphorus-containing cotton flame retardant with -N=P-(N)3- and reactive ammonium phosphoric acid groups.

A flame retardant (FR) hexachlorocyclotriphosphazene diethylenetriamine ammonium phosphoric acid (HDAPA) was synthesized. Vertical flammability test and limiting oxygen index (LOI) results showed that cotton samples finished with HDAPA solutions (15 % and 20 %) could pass vertical flame retardancy test, and LOIs reached 30.1 % and 35.4 % even after 50 laundering cycles according to AATCC 61-2013 3A washing standard (3A), performing flame retardancy and washing durability. Meanwhile, Fourier transform infrared and X-ray photoelectron spectroscopy analyses suggested that HDAPA was grafted on cotton fibers through -P(=O)-O-C covalent bond. Total heat release (1.98 MJ/m2) and char residue (16.2 %) of HDAPA treated cotton were much lower than those (4.26 MJ/m2, 3.2 %) of untreated cotton. Thermogravimetry results showed HDAPA changed thermal decomposition pathway of cotton fabric, which was further supported by thermogravimetric-Fourier infrared spectrometer results, revealing HDAPA performed a condensed phase flame retardancy mechanism. Scanning electron microscopy implied HDAPA entered amorphous region of cotton fibers to react with cellulose. Mechanical properties of HDAPA treated cotton decreased a little. Although the synthesis process used formaldehyde but no free formaldehyde released. In consequence, the aforementioned results indicated that the introduction of -N=P-(N)3- and -P(=O)(O-NH4+)2 groups to FR was an viable method to improve flame retardancy and durability.

Organophosphate esters (OPEs) in plastic food packaging: non-target recognition, and migration behavior assessment.

Organophosphate esters (OPEs) are widely used as plasticizers in plastic food packaging; however, the migration of OPEs from plastic to food is largely unstudied. We do not even know the specific number of OPEs that exist in the plastic food packaging. Herein, an integrated target, suspect, and nontarget strategy for screening OPEs was optimized using ultrahigh-performance liquid chromatography-high-resolution mass spectrometry (UHPLC-HRMS). The strategy was used to analyze 106 samples of plastic food packaging collected in Nanjing city, China, in 2020. HRMS allowed full or tentative identification of 42 OPEs, of which seven were reported for the first time. Further, oxidation products of bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (AO626) in plastics were identified, implying that the oxidation of organophosphite antioxidants (OPAs) could be an important indirect source of OPEs in plastics. The migration of OPEs was examined with four simulated foods. Twenty-six out of 42 OPEs were detected in at least one of the four simulants, particularly isooctane, in which diverse OPEs were detected at elevated concentrations. Overall, the study supplements the list of OPEs that humans could ingest as well as provides essential information regarding the migration of OPEs from plastic food packaging to food.

Bioaccumulation and emission of organophosphate esters in plants affecting the atmosphere's phosphorus cycle.

The imbalance of atmospheric, terrestrial and aquatic phosphorus budgets remains a research conundrum and global concern. In this work, the uptake, distribution, bioaccumulation and emission of organophosphate esters (OPEs) by clove trees (Syzygium aromaticum), lemon trees (Citrus limon) and cape jasmine trees (Gardenia jasminoides var. fortuniana) was investigated as conduits for phosphorus transfer or sinks and sources. The objective was to assess the role OPEs in soils play as atmospheric phosphorus sources through plant bioaccumulation and emission. Results demonstrated OPEs in experimental soil plots ranging from 0.01 to 81.0 ng g-1 dry weight, were absorbed and transported through plants to the atmosphere. The total emission of OPEs varied greatly from 0.2 to 588.9 pg g-1 L-1 h-1, with a mean of 47.6 pg g-1 L-1 h-1. There was a negative linear relationship between the concentrations of total phosphorus and four OPEs, tri-iso-butyl phosphate, tri-n-butyl phosphate, tris (2-chloroisopropyl) phosphate and tripentyl phosphate. Trimethyl phosphate levels were positively correlated with total nitrogen, and the concentrations of tri-iso-butyl phosphate, tri-n-butyl phosphate, tris (2-chloroisopropyl) phosphate and tripentyl phosphate decreased along with available potassium in leaves after 72 h. There was a significantly positive linear relationship between higher emission concentrations of OPEs and the emission factor of OPEs concentration (F = 4.2, P = 0.002), with lower emissions of OPEs and the bioaccumulation of OPEs in leaves (F = 4.8, P = 0.004). OPEs releases to the atmosphere were enriched in aerosols, and participate in atmospheric chemical reactions like photolysis, thereby affecting the phosphorus balance and cycling in the atmosphere.

Synergistic Function between Phosphorus-Containing Flame Retardant and Multi-Walled Carbon Nanotubes towards Fire Safe Polystyrene Composites with Enhanced Electromagnetic Interference Shielding.

As a universal polymer material, polystyrene (PS) is widely applied in electrical devices and construction. Thus, it is necessary to improve the flame retardancy and electromagnetic shielding properties of PS material. In this work, PS/silicon-wrapped ammonium polyphosphate/Inorganic acid-treated multi-walled carbon nanotubes composites (PS/SiAPP/aMWCNT, abbreviated as PAC) were prepared via methods of filtration-induced assembly and hot-pressing. Morphology and structure characterization demonstrated that SiAPP and aMWCNT had good dispersion in PS and excellent compatibility with the PS matrix. Thermogravimetric analysis revealed that the addition of aMWCNT to PS improved its thermal stability and carbon-forming characteristics. The peak heat release rate, the peak carbon monoxide production rate, and the peak smoke production rate of the PAC10 composite decreased by 53.7%, 41.9%, and 45.5%, respectively, while its electromagnetic shielding effectiveness reached 12 dB. These enhancements were attributed to the reason that SiAPP and aMWCNT synergistically catalyzed the char generation and SiAPP produced free radical scavengers and numbers of incombustible gases, which could decrease the oxygen concentration and retard the combustion reaction. Therefore, the assembled PS/SiAPP/aMWCNT system provides a new pathway to improve the flame retardant and electromagnetic shielding properties of PS.

Spatial distribution, receptor modelling and risk assessment of organophosphate esters in surface water from the largest freshwater lake in China.

The occurrence and risk of organophosphate esters (OPEs) has become a global concern in recent years. This study investigated the occurrence, spatial distribution, and potential sources of thirteen OPEs and their associated ecological and human health risks in water samples from the largest freshwater lake, Poyang Lake, together with its five major inflow rivers and the water channel to Yangtze River. The total OPEs concentrations ranged from 38.44 ng/L to 428.94 ng/L, and the largest tributary Ganjiang River was much more polluted than other rivers. Chlorinated OPEs, such as tris (1-chloro­2-propyl) phosphate and tri (2-chloroethyl) phosphate occupied the dominant composition of OPEs in the research area. Principal component analysis with multiple linear regression, positive matrix factorization, and correlation analysis were used to apportion the potential sources of OPEs in surface water. The combined contribution of polyvinyl chloride, polyester resins, and polyurethane foam (68.64%), antifoam agent and hydraulic fluids (21.50%), and the release of decorative materials and electric equipment from indoor (9.86%) were identified as the OPEs sources in the study region. The risk quotients (RQs) showed the ecological risk was negligible, but 2-ethylhexyl diphenyl phosphate exposures posed medium ecological risk to aquatic organisms. The carcinogenic and non-carcinogenic risks of the target OPEs were below the theoretical risk threshold values, however, toddlers were much more sensitive to the OPEs exposure in surface water than teenagers and adults. Oral ingestion was the principal exposure pathway, and the health risk via oral ingestion was 1-2 orders of magnitude higher than dermal contact exposure route.

Formal waste treatment facilities as a source of halogenated flame retardants and organophosphate esters to the environment: A critical review with particular focus on outdoor air and soil.

Extensive use of halogenated flame retardants (HFRs) and organophosphate esters (OPEs) has generated great concern about their adverse effects on environmental and ecological safety and human health. As well as emissions during use of products containing such chemicals, there are mounting concerns over emissions when such products reach the waste stream. Here, we review the available data on contamination with HFRs and OPEs arising from formal waste treatment facilities (including but not limited to e-waste recycling, landfill, and incinerators). Evidence of the transfer of HFRs and OPEs from products to the environment shows that it occurs via mechanisms such as: volatilisation, abrasion, and leaching. Higher contaminant vapour pressure, increased temperature, and elevated concentrations of HFRs and OPEs in products contribute greatly to their emissions to air, with highest emission rates usually observed in the early stages of test chamber experiments. Abrasion of particles and fibres from products is ubiquitous and likely to contribute to elevated FR concentrations in soil. Leaching to aqueous media of brominated FRs (BFRs) is likely to be a second-order process, with elevated dissolved humic matter and temperature of leaching fluids likely to facilitate such emissions. However, leaching characteristics of OPEs are less well-understood and require further investigation. Data on the occurrence of HFRs and OPEs in outdoor air and soil in the vicinity of formal e-waste treatment facilities suggests such facilities exert a considerable impact. Waste dumpsites and landfills constitute a potential source of HFRs and OPEs to soil, and improper management of waste disposal might also contribute to HFR contamination in ambient air. Current evidence suggests minimal impact of waste incineration plants on BFR contamination in outdoor air and soil, but further investigation is required to confirm this.

Thermal treatment of decabrominated diphenyl ether in its highly contaminated soil in Taiwan.

Polybrominated diphenyl ethers (PBDEs) were commonly used flame retardants in the world, while some of PBDEs have been listed as persistent organic pollutants (POPs). Decabrominated diphenyl ether (BDE-209) was the most commercially used PBDEs. A farm near the factory located in Northern Taiwan was highly contaminated with BDE-209. Since PBDEs in the contaminated soils can be uptake by crops shown in our previous studies and could be potentially consumed by humans, it is very important to establish a feasible treatment method for PBDE remediation in this contaminated farm. Thermal treatment of PBDEs in soil was studied. The initial concentration of BDE-209 in contaminated soil was 1.472 mg/kg. A series of thermal experiments under different operating conditions including various temperature (105, 150, 200, 250, 300, 350, 400 and 450 °C), holding time (10, 20 and 30 min), heating rate (5, 10, 20 and 40 °C/min), and soil amount (10, 100, 1000 and 2000 g) were investigated. The optimal heating conditions for thermal treatment of contaminated soil were heating at 450 °C for 30 min with a heating rate of 10 °C/min. Under this condition, the removal of BDE-209 in the different weights of contaminated soil was tested. The soils in the contaminated farm were tested to further evaluate the feasibility of remediating the on-site PBDE contaminated soil through thermal treatment, suggesting that the holding time was extended to 2 h for the field-scale contaminated soil. The results showed that BDE-209 had been removed to below the detection limit in on-site soil. This investigation is the first study using thermal treatment to remediate soils really contaminated with PBDEs.

Vermiculite Filler Modified with Casein, Chitosan, and Potato Protein as a Flame Retardant for Polyurethane Foams.

In this study, polyurethane (PU) composite foams were modified with 2 wt.% of vermiculite fillers, which were themselves modified with casein, chitosan, and potato protein. The impact of the fillers on selected properties of the obtained composites, including their rheological (foaming behavior, dynamic viscosity), thermal (temperature of thermal decomposition stages), flame-retardant (e.g., limiting oxygen index, ignition time, heat peak release), and mechanical properties (toughness, compressive strength (parallel and perpendicular), flexural strength) were investigated. Among all the modified polyurethane composites, the greatest improvement was noticed in the PU foams filled with vermiculite modified with casein and chitosan. For example, after the addition of modified vermiculite fillers, the foams' compressive strength was enhanced by ~6-18%, their flexural strength by ~2-10%, and their toughness by ~1-5%. Most importantly, the polyurethane composites filled with vermiculite filler and modified vermiculite fillers exhibited improved flame resistance characteristics (the value of total smoke release was reduced by ~34%, the value of peak heat release was reduced by ~25%).

Phosphorus Deficiency Promoted Hydrolysis of Organophosphate Esters in Plants: Mechanisms and Transformation Pathways.

The biotransformation of organophosphate esters (OPEs) in white lupin (Lupinus albus) and wheat (Triticum aestivum L.) was investigated in hydroponic experiments with different phosphorus (P)-containing conditions. The hydrolysis rates of OPEs followed the order of triphenyl phosphate (TPHP) > tri-n-butyl phosphate (TnBP) > tris(1,3-dichloro-2-propyl) phosphate (TDCPP). Hydrolysis of OPEs was accelerated at P-deficient conditions, and faster hydrolysis took place in white lupin than in wheat. Coincidingly, the production of acid phosphatase (ACP) in both plants was promoted, and much higher intracellular and extracellular ACPs were observed in white lupin under P-deficient conditions. In vitro experiments revealed that ACP was a key enzyme to hydrolyze OPEs. The hydrolysis rates of OPEs were significantly correlated with the Hirshfeld charges, calculated by density functional theory, of the oxygen atom in the single P-O bond. Using ultra-high-performance liquid chromatography coupled with Orbitrap Fusion mass spectrometer, 30 metabolites were successfully identified. Some of these metabolites, such as sulfate-conjugated products, hydration of cysteine-conjugated products of TPHP, and reductively dechlorinated metabolites of TDCPP, were observed for the first time in plants. It is noteworthy that OPEs may transform into many hydroxylated metabolites, and special attention should be paid to their potential environmental effects.

Assessment of polybrominated diphenyl ethers and emerging brominated flame retardants in Pheretima (a Traditional Chinese Medicine): Occurrence, residue profiles, and potential health risks.

China produces and consumes large quantities of brominated flame retardants (BFRs) as well as several other unregulated electronic waste recycling activities, causing high BFR concentrations in the natural environment. Thus, Traditional Chinese Medicines (TCMs) may be contaminated by legacy BFRs (e.g. polybrominated diphenyl ethers (PBDEs)) and emerging BFRs (eBFRs, such as decabromodiphenyl ethane (DBDPE)) during growth, processing, packaging, and transportation. Pheretima, which is a typical animal drug recorded in Chinese Pharmacopoeia, was used as an example to evaluate human exposure to BFRs through TCM intake. This study is the first to determine 25 PBDEs and 5 eBFRs in Pheretima and estimate the daily BFR intake via Pheretima-containing TCMs. Twenty-seven Shanghai Pheretima and fifty-one Guang Pheretima samples were collected between March and June 2019 in southeast China. High BFR detection frequencies were found in Pheretima, of which BDE-209 and DBDPE were the most predominant analytes. The total PBDE contents ranged from 73 pg/g to 8,725 pg/g, while that of the eBFRs varied between 115 pg/g and 2,824 pg/g. The profiles and abundances were found to be species- and origin-dependent. However, the traditional processing of Pheretima may reduce BFR residues. Based on the usual clinical doses of Pheretima and the available chronic oral reference doses of BDE-47, 99, 153, and 209, the mean (95th percentile) of the total hazard quotient was estimated to be 9.1 × 10-5 (2.7 × 10-4). Therefore, there is little risk related to BFR exposure for patients taking formulated Pheretima-containing TCMs. However, it is necessary to establish routine monitoring programs for the co-existence of pollutants in TCMs to perform a systematic and comprehensive risk assessment.

Seasonal Impact of Phosphate-Based Fire Retardants on Soil Chemistry Following the Prophylactic Treatment of Vegetation.

A preventative treatment of fire retardants at high-risk locales can potentially stop a majority of wildfires. For example, over 80% of wildfire ignitions in California occur at high-risk locales such as adjacent to roadsides and utility infrastructure. Recently a new class of ammonium polyphosphate retardants was developed with enhanced adherence and retention on vegetation to enable prophylactic treatments of these high-risk locals to provide season-long prevention of ignitions. Here, we compare three different ammonium (poly)phosphate-based wildland retardant formulations and evaluate their resistance to weathering and analyze their seasonal impact on soil chemistry following application onto grass. Soil samples from all three treatments demonstrated no changes in soil pH and total soil carbon and nitrogen amounts. Total soil phosphorus amounts increased by ∼2-3× following early precipitation, always remaining within typical topsoil amounts, and returned to the same level as control soil before spring. Available indices of ammonium, nitrate, and phosphate levels for all groups were elevated compared to the untreated control samples, again remaining within typical topsoil ranges across all time points and rainfall amounts evaluated. Microbial activity was decreased, potentially because the addition of available nutrients from retardant application reduced the need for organic decomposition. These results demonstrate that the application of ammonium (poly)phosphate-based retardants does not alter soil chemistry beyond typical topsoil compositions and are thus suitable for use in prophylactic wildfire prevention strategies.

Construction of Charring-Functional Polyheptanazine towards Improvements in Flame Retardants of Polyurethane.

Nitrogen-containing flame retardants have been extensively applied due to their low toxicity and smoke-suppression properties; however, their poor charring ability restricts their applications. Herein, a representative nitrogen-containing flame retardant, polyheptanazine, was investigated. Two novel, cost-effective phosphorus-doped polyheptazine (PCN) and cobalt-anchored PCN (Co@PCN) flame retardants were synthesized via a thermal condensation method. The X-ray photoelectron spectroscopy (XPS) results indicated effective doping of P into triazine. Then, flame-retardant particles were introduced into thermoplastic polyurethane (TPU) using a melt-blending approach. The introduction of 3 wt% PCN and Co@PCN could remarkably suppress peak heat release rate (pHRR) (48.5% and 40.0%), peak smoke production rate (pSPR) (25.5% and 21.8%), and increasing residues (10.18 wt%→17.04 wt% and 14.08 wt%). Improvements in charring stability and flame retardancy were ascribed to the formation of P-N bonds and P=N bonds in triazine rings, which promoted the retention of P in the condensed phase, which produced additional high-quality residues.

Occurrence of chemical pollutants in major e-waste sites in West Africa and usefulness of cytotoxicity and induction of ethoxyresorufin-O-deethylase (EROD) in determining the effects of some detected brominated flame retardants and e-waste soil-derived extracts.

We investigated the occurrence of chemical pollutants in major e-waste sites in West Africa and usefulness of cytotoxicity and induction of ethoxyresorufin-O-deethylase (EROD) in determining the effects of some detected brominated flame retardants (BFRs) and e-waste soil-derived extracts. Analysis of the e-waste site samples using AAS and GC-MS techniques revealed the presence of a range of toxic metals as well as persistent and toxic organic pollutants, respectively, in the vicinity of the e-waste sites. As expected, the occurrence (%) of all the detected chemical pollutants in experimental soils significantly (P < 0.05) differs from occurrence (%) in control soil. The calculated LC50 values on RBL-2H3 cells of the detected tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD) were 3.75 µM and 4.2 µM, respectively. Tribromophenol (TBP), dibromobiphenyl (DBB), and decabromodiphenyl ether (DBDE) were remarkably less toxic on RBL-2H3 cells compared with TBBPA and HBCD as they did not reduce RBL-2H3 cell viability below 50% in the tested concentration range (0-20 µM). The study revealed that TBBPA and HBCD could induce significant RBL-2H3 cell death through caspase-dependent apoptosis. The study further shows that the cytotoxicity of some of these BFRs could increase synergistically when in mixtures and potentially activate inflammation through the stimulation of mast cell degranulation. The e-waste soil-derived extracts induced a concentration-dependent increase in EROD activity in the exposed RTG-W1 cells. Ultimately, nonpolar extracts had higher EROD-inducing potency compared with polar extracts and hence suggesting the presence in higher amounts of AhR agonists in nonpolar e-waste soil-derived extracts than polar extracts. Overall, there is urgent need for actions in order to improve the environmental quality of the e-waste sites.

Analysis of polybrominated diphenyl ethers, hexabromocyclododecanes, and legacy and emerging phosphorus flame retardants in human hair.

Human hair has been identified as a non-invasive alternative matrix for assessing the human exposure to specific organic contaminants. In the present study, a solvent-saving analytical method for the simultaneous determination of 8 polybrominated diphenyl ethers (PBDEs), 3 hexabromocyclododecanes (HBCDDs), 12 phosphorus flame retardants (PFRs), and 4 emerging PFRs (ePFRs) has been developed and validated for the first time. Hair sample preparation protocols include precleaning with Milli-Q water, digestion with HNO3/H2O2 (1:1, v/v), liquid-liquid extraction with hexane:dichloromethane (4:1, v/v), and fractionation and cleanup on a Florisil cartridge. The method was validated by using two levels of spiked hair samples of 3 replicates for each spiking group. Limits of quantification (LOQs) were 0.12-22.4 ng/g for all analytes, average values of accuracies were ranging between 88 and 115%, 82-117%, 81-128%, and 81-95% for PBDEs, HBCDDs, PFRs, and ePFRs, respectively; and precision was also acceptable (RSD < 20%) for all analytes. Eventually, this method was applied to measure the levels of the targeted analytes in hair samples of e-waste dismantling workers (n = 14) from Qingyuan, South China. Median values ranged between 3.00 and 18.1 ng/g for PBDEs, 0.84-4.04 ng/g for HBCDDs, 2.13-131 ng/g PFRs, and 1.49-29.4 ng/g for ePFRs, respectively. PFRs/ePFRs constitute the major compounds in human hair samples, implying the wide use of PFRs/ePFRs as replacements of PBDEs and HBCDDs, as well the potential high human exposure risks of PFRs/ePFRs. Overall, this work will allow to a comprehensive assessment of human exposure to multiple groups of FRs using hair as a non-invasive bioindicator.

Characterization of adipogenic, PPARγ, and TRß activities in house dust extracts and their associations with organic contaminants.

In this study, we sought to expand our previous research on associations between bioactivities in dust and associated organic contaminants. Dust samples were collected from central NC homes (n = 188), solvent extracted, and split into two fractions, one for analysis using three different bioassays (nuclear receptor activation/inhibition and adipocyte development) and one for mass spectrometry (targeted measurement of 124 organic contaminants, including flame retardants, polychlorinated biphenyls, perfluoroalkyl substances, pesticides, phthalates, and polycyclic aromatic hydrocarbons). Approximately 80% of dust extracts exhibited significant adipogenic activity at concentrations that are comparable to estimated exposure for children and adults (e.g. ~20 µg/well dust) via either triglyceride accumulation (65%) and/or pre-adipocyte proliferation (50%). Approximately 76% of samples antagonized thyroid receptor beta (TRß), and 21% activated peroxisome proliferator activated receptor gamma (PPARγ). Triglyceride accumulation was significantly correlated with TRß antagonism. Sixty-five contaminants were detected in at least 75% of samples; of these, 26 were correlated with adipogenic activity and ten with TRß antagonism. Regression models were used to evaluate associations of individual contaminants with adipogenic and TRß bioactivities, and many individual contaminants were significantly associated. An exploratory g-computation model was used to evaluate the effect of mixtures. Contaminant mixtures were positively associated with triglyceride accumulation, and the magnitude of effect was larger than for any individually measured chemical. For each quartile increase in mixture exposure, triglyceride accumulation increased by 212% (RR = 3.12 and 95% confidence interval: 1.58, 6.17). These results suggest that complex mixtures of chemicals present in house dust may induce adipogenic activity in vitro at environmental concentrations and warrants further research.

Animal-Derived and Plant-Derived Protein Supplement Feeds Are Important Sources of Organophosphate Esters in the Food Supply.

Animal protein supplement feeds (APFs) are important raw feed materials for livestock. APFs might be susceptible to organophosphate esters (OPEs) but have not been paid attention yet. In the present study, animal-derived (meat meal, feather meal, and blood meal) and plant-derived APFs were all found to contain detectable levels of OPEs, with 16 target OPEs ranging from 12.6 ng/g dry weight (dw) to 301 ng/g dw. Meat meal contained the highest OPE level (mean: 117 ± 75.6 ng/g dw), followed by feather meal (54.6 ± 30.0 ng/g dw), plant-derived feed (41.9 ± 16.0 ng/g dw), and blood meal (28.0 ± 12.0 ng/g dw). Considering its widespread consumption, plant-derived APFs might be an important source of OPE exposure for livestock. Dust adhesion contributed to OPE contamination both in feather meal and plant-derived APFs. Congener patterns varied among the different APFs. Tris(2-chloroisopropyl) phosphate dominated in the plant-derived feed and blood meal, while tris(2-chloroethyl) phosphate and triphenyl phosphate were the major contributors in meat meal and feather meal, respectively. Tributyl phosphate and tri-iso-butyl phosphate were found to be statistically correlated in all APFs (p < 0.01), indicating their similar behavior and common sources. The protein-associated transport pathways of OPEs need to be studied separately for different protein matrices in the future.

Optimization and validation of automated solid-phase microextraction arrow technique for determination of phosphorus flame retardants in water.

In the present work, a very sensitive and fully automated direct immersion PAL SPME Arrow procedure, coupled with GC-MS, has been developed and validated for determination of nine phosphorus flame retardants in different types of water samples (river, drinking and rainwater). PDMS/DVB was selected among three commercially available SPME Arrows (PDMS/DVB, DVB/PDMS/CWR and PDMS/CWR), since it resulted in the best sensitivity. The important experimental parameters were optimized via a central composite design response surface methodology and as result, extraction time of 65 min, extraction temperature of 80 °C and added salt concentration of 19% (w/v), were selected as the optimum values. The optimized method showed linear response over the calibration range (2 - 500 ng L-1), with R2-values higher than 0.9937. The precision (RSD%) measured by replicate analyses (n = 7) was estimated at 2 and 100 ng L-1 and was less than 29% and 21%, respectively. The LOQ of PAL SPME Arrow, calculated as S/N = 10, was between 0.2 and 1.2 ng L-1 (for triphenyl phosphate and tris-(1­chloro­2-propyl) phosphate, respectively) with extraction efficiencies between 5.9 and 31% (for tris-(1,3-dichloro-2-propyl) phosphate and tri-n­butyl phosphate, respectively). To assess the performance of the developed technique for real samples, two river water samples, tap water from two regions and a rainwater sample were analyzed. Most of the target analytes were observed in the river samples with concentrations of 1.0 - 250 ng L-1 and the obtained recoveries at 50 ng L-1 ranged between 60 and 107%. Considering the figures of merit of the optimized method, PAL SPME Arrow-GC-MS showed to be the most sensitive analytical approach for determination of phosphorus flame retardants in water, with satisfying precision and accuracy, compared with conventional SPME-NPD, LLE-GC-MS and SPE-LC-MS/MS.

Organic extract of indoor dust induces estrogen-like effects in human breast cancer cells.

Indoor dust often contains organic contaminants, which adversely impacts human health. In this study, the organic contaminants in the indoor dust from commercial offices and residential houses in Nanjing, China were extracted and their effects on human breast cancer cells (MCF-7) were investigated. Both dust extracts promoted proliferation of MCF-7 cells at ≤24 µg/100 µL, with cell viability being decreased with increasing dust concentrations. Based on LC50, house dust was less toxic than office dust. At 8 µg/100 µL, both extracts caused more MCF-7 cells into active cycling (G2/M + S) and increased intracellular Ca2+ influx, with house dust inducing stronger effects than office dust. Further, the expression of estrogen-responsive genes for TFF1 and EGR3 was enhanced by 3-9 and 4-9 folds, while the expression of cell cycle regulatory genes for cyclin D was enhanced by 2-5 folds. The results suggested that organic dust extract influenced cell viability, altered cell cycle, increased intracellular Ca2+ levels, and activated cell cycle regulatory and estrogen-responsive gene expressions, with house dust showing lower cytotoxicity but higher estrogenic potential on MCF-7 cells. The results indicate the importance of reducing organic contaminants in indoor dust to mitigate their adverse impacts on human health.

Flame Retardancy of Wood Fiber Materials Using Phosphorus-Modified Wheat Starch.

Biopolymer-based flame retardants (FR) are a promising approach to ensure adequate protection against fire while minimizing health and environmental risks. Only a few, however, are suitable for industrial purposes because of their poor flame retardancy, complex synthesis pathway, expensive cleaning procedures, and inappropriate application properties. In the present work, wheat starch was modified using a common phosphate/urea reaction system and tested as flame retardant additive for wood fibers. The results indicate that starch derivatives from phosphate/urea systems can reach fire protection efficiencies similar to those of commercial flame retardants currently used in the wood fiber industry. The functionalization leads to the incorporation of fire protective phosphates (up to 38 wt.%) and nitrogen groups (up to 8.3 wt.%). The lowest levels of burning in fire tests were measured with soluble additives at a phosphate content of 3.5 wt.%. Smoldering effects could be significantly reduced compared to unmodified wood fibers. The industrial processing of a starch-based flame retardant on wood insulating materials exhibits the fundamental applicability of flame retardants. These results demonstrate that starch modified from phosphate/urea-systems is a serious alternative to traditional flame retardants.