Tris 2-ethylhexyl Phosphate Research Articles

Occurrence, Distribution, and Exposure Risk of Organophosphate Esters in Street Dust from Chengdu, China.

Street dust samples were collected from 31 sampling sites in urban area of Chengdu. The distribution characters of OPEs were analyzed in line with functional districts and industrial layout of the city. The results showed that the detection frequency was tris(2-carboxyethyl) phosphine (TCEP), trichloropropyl phosphate (TCPP), triphenyl phosphate (TPhP), and tributoxyethyl phosphate (TBEP) (100%) > tris(2-ethylhexyl) phosphate (TEHP) (93.5%) > tri-n-butyl phosphate (TnBP) (83.9%) > tridichloropropyl phosphate (TDCPP) (74.2%). The ∑7OPEs concentrations ranged from 94.0 to 1484.6ng/g (mean 512.9 ± 417.5ng/g), and TBEP was the predominant pollutant, accounting for 27.9% of the ∑7OPEs. The highest concentrations were observed in the center, west, and northwest sides of the city. Besides, compared with outer area, the higher concentration in the 1st Ring Road reflected that emissions of OPEs might be associated with the population and consumption of commercial products. The correlations between monomers were statistically significant (p < 0.05) for TnBP/TCPP (p = 0.002), TCEP/TCPP (p = 0.026), and TCEP/TPhP (p = 0.033). The exposure level in adults was 0.11ng/(kg bw day), and in children was 0.20ng/(kg bw day) while hand-to-mouth was the primary mode of transmission. The Risk Quotients (RQs) of OPEs were 5.35 × 10-10-1.46 × 10-5 and 4.99 × 10-10-2.82 × 10-5 for adults and children respectively, with no potential risk.

Organophosphate flame retardants in college dormitory dust of northern Chinese cities: Occurrence, human exposure and risk assessment

Organophosphate flame retardants (OPFRs) are widely added to consumer products and building materials, which may pose potential health risk to humans. But information on their contamination and human exposure in the indoor environment especially dormitories in northern China is rare. In this study, twelve OPFRs were investigated in college dormitory dust that collected from Harbin, Shenyang, and Baoding, in northern China. Indoor dust samples were also collected from homes and public microenvironments (PMEs) in Harbin for comparison. The median ∑OPFR concentrations in dormitory dust in Shenyang samples (8690 ng/g) were higher than those in Baoding (6540 ng/g) and Harbin (6190 ng/g). The median ∑OPFR concentrations in home dust (7150 ng/g) were higher than in dormitory and PME dust (5340 ng/g) in Harbin. Tris(2‑chloroethyl) phosphate (TCEP) and tris (2-chloroisopropyl) phosphate (TCIPP) were the most abundant chlorinated OPFRs, while triphenyl phosphate (TPHP) and tris(2‑butoxyethyl) phosphate (TBOEP) were the dominant non-chlorinated OPFRs. The daily intakes of ∑OPFR were estimated, with the median values for female students (2.45 ng/kg-day) higher than those for male students (2.15 ng/kg-day) while were similar to adults (2.45 ng/kg-day) in homes. The estimated daily intakes (EDI) of these OPFRs from indoor dust in Harbin were all below the recommended values. The calculated non-carcinogenic hazard quotients (10−8–10−3) from OPFRs were much lower than the theoretical risk threshold. Meanwhile, carcinogenic risk (CR) of tri‑n‑butyl phosphate (TNBP), TCEP, tris(2‑ethylhexyl) phosphate (TEHP), and tris(1,3‑dichloroisopropyl) phosphate (TDCIPP) were also estimated. The highest carcinogenic risk of TCEP for gender-specific and age-specific category range from 1.75 × 10−7 to 2.46 × 10−7 from exposure to indoor dust indicated a low potential carcinogenic risk for human exposure.

Organophosphorus flame retardants in fish from Rivers in the Pearl River Delta, South China

Twelve organophosphorus flame retardants (PFRs) were detected in the muscle of 3 species of fish, mud carp (Cirrhinus molitorella), tilapia (Tilapia nilotica), and plecostomus (Hypostomus plecostomus), from rivers in the Pearl River Delta (PRD) region. The total concentrations of PFRs in the mud carp, tilapia, and plecostomus ranged from 2.3 to 16, 3.4 to 16, and 3.5 to 30 ng/g wet weight (ww), respectively. Generally, tris(2-ethylhexyl) phosphate (TEHP), tris (2-chloro-isopropyl) phosphate (TCPP), tris (2-chloroethyl) phosphate (TCEP), and tri-n-butyl phosphate (TnBP) were the dominant compounds of the PFRs, collectively accounting for up to 90% of the total PFR levels. Concentrations of PFRs were significantly higher in the plecostomus than in the mud carp and tilapia (p < 0.05), which could be explained by differences in habitat and feeding habits of the fish species. High concentrations of PFRs were found mainly in the Guangzhou section of the Pearl River (site P1, P2, and P3) and site B3, which was similar to our previous study of PFRs in sediment from the Pearl River Delta, indicating a relatively high level of PFRs pollution in these regions. The estimated daily intake (EDI) of total PFRs from consumption of fish was 17 ng/kg bw/day to 98 ng/kg bw/day for adults and children, which was three to four orders of magnitude lower than reference dose values.

Occurrence, distribution and ecological risk assessment of organophosphorus flame retardants and plasticizers in sediment samples along the Vaal River catchment, South Africa

Abstract The occurrence, distribution and ecological risk assessment of twelve (12) organophosphorus flame retardants (OPFRs) were investigated in sediments from the Vaal River, South Africa. Six halogenated OPFRs [tris-(2-chloroethyl) phosphate (TCEP), three isomers of tris-(chloropropyl) phosphate (TCiPPs), tris-(1, 3-dichloro-2-propyl) phosphate (TDCiPP) and tris-(2, 3 dibromopropyl) phosphate (TDBPP)] and six non-halogenated OPFRs [tris-(n-butyl) phosphate (TBP), tris-(phenyl) phosphate (TPhP), tris-(butyl ethoxy) phosphate (TBOEP), tris-(2-ethylhexyl) phosphate (TEHP), diphenyl- 2-ethylhexyl phosphate (DPEHP) and tris-(m-cresyl) phosphate (m-TCP)] were detected in this study. The concentrations of twelve OPFRs in total (Σ12OPFRs) ranged from 68 to 278 ng g−1 dry weight (dw) with the mean and median of 138 and 120 ng g−1; respectively. The non-halogenated OPFRs showed more abundances than the halogenated OPFRs with TDBPP, TBP, and TBOEP the most abundant compounds. Generally, concentrations of OPFRs in more urbanized region were higher than those in less urbanized regions. When the concentrations of OPFRs and total organic carbon (TOC) were correlated, a moderate and significant correlation (p 1) while TBOEP, TPhP, and TBP posed medium risk (0.1

Measurement of legacy and emerging flame retardants in indoor dust from a rural village (Kopawa) in Nepal: Implication for source apportionment and health risk assessment

Under the Stockholm Convention, signatory countries are obliged to direct source inventories, find current sources, and provide ecological monitoring evidence to guarantee that the encompassing levels of persistent organic pollutants (POPs) are declining. However, such monitoring of different types of POPs are to a great degree constrained in most developing countries including Nepal and are primarily confined to suspected source area/ densely populated regions. In this study, 9 polybrominated diphenyl ethers (PBDEs), 2 dechlorane plus (DPs), 6 novel brominated flame retardants (NBFRs) and 8 organophosphate ester flame retardants (OPFRs) were investigated in indoor dust from a rural area (Kopawa) in Nepal in order to evaluate their occurrence/level, profile, spatial distribution and their sources. Additionally, health risk exposure was estimated to anticipate the possible health risk to the local population. The results showed that OPFRs was the most abundant FR measured in the dust. The concentration of ∑8OPFRs was about 2, 3 and 4 orders of magnitude higher than the ∑6NBFRs, ∑9PBDEs, and ∑2DPs, respectively. Tris (methylphenyl) phosphate (TMPP) and Tris (2-ethylhexyl) phosphate (TEHP) were the most abundant OPFRs analyzed in the dust; while decabromodiphenyl ethane (DBDPE) exceeded among NBFRs. Likewise, 2,2′,3,3′,4,4′,5,5′,6,6′-decabromodiphenylether (BDE-209) was the most identified chemical among PBDEs. The total organic carbon (TOC) content in dust was significantly and positively connected with octa-BDEs (Rho = 0.615, p < 0.01), BTBPE (Rho = 0.733, p < 0.01), TPHP (Rho = 0.621, p < 0.01), TEHP (Rho = 0.560, p < 0.01) and TMPPs (Rho = 0.550, p < 0.01), while black carbon (BC) was either weakly related or not related, suggesting little or no impact of BC in the distribution of FRs. Principal component analysis indicated the contribution from commercial penta-, octa- and deca-BDEs formulation, the adhesive substance, food packaging and paints, and degradation of BDE-209 as the essential sources of FRs. Health risk exposure estimates showed that dermal absorption via dust as the primary route of FRs intake. The estimated daily exposure of PBDEs, NBFRs and OPFRs were 2–10 orders of magnitude lower than their corresponding reference dose (RfD), suggesting insignificant risk. However, other routes such as inhalation and dietary intake might still be significant in the case of Kopawa which should be tested in future.

Surfactant-based modification of sodic-Algerian illite clay for the preparation of polymeric membranes: application for separation of iron and zinc ions from aqueous solutions

In the present work, polymer solutions of cellulose triacetate (CTA) and tris-ethylhexyl phosphate (TEHP) mixed with Algerian green illite clay were used to prepare selective filtration membranes by the phase inversion technique via immersion precipitation. The effect of a local clay additive on the structure and performances of the membranes was studied. Algerian clay was characterized by x-ray diffraction (XRD), thermogravimetric analysis (TGA), x-ray fluorescence (XRF) and scanning electron microscopy (SEM). The obtained hybrid membranes were characterized by XRD, Fourier transform infrared spectroscopy (FTIR-ATR), TGA and contact angle measurements. All the synthesized membranes had an amorphous structure without any diffraction peak. This could be due to the absence of crystallization within the membrane. As the plasticizer molecules were hydrophobic, their location at the surface of the modified polymeric membranes is expected to modify the contact angle. Overall, our results show that the addition of plasticizer to the hybrid material (polymer and clay) results in homogeneous and hydrophobic membranes of which the physical properties were ameliorated compared to (CTA + Clay) membranes. As applications, transport of Zn(II) and Fe(III) in polymeric membranes using (CTA + TEHP + Clay) membranes was studied.

Measurement and prediction of bioconcentration factors of organophosphate flame retardants in common carp (Cyprinus carpio)

The increase in the production and usage plus the toxicity nature of organophosphate flame retardants (OPFRs) has become a concern. However, limited information is available about the bioaccumulation potential of OPFRs in fish. In this study, we determined the 96 h LC50 s, and evaluated the bioaccumulation potential of six most frequently reported OPFRs in gill, kidney, liver, and muscle tissues of common carp (Cyprinus carpio) for 48 d, and a quantitative structure-activity relationship (QSAR) model was developed to predict bioconcentration factors (BCFs) for the remaining 16 OPFRs. The BCFs and half-lives (t1/2) in the tissues ranged from 6.54 (Tris (2-chloroisopropyl) phosphate, (TCPP)) to 528.15 (Tris (2-ethylhexyl) phosphate (TEHP)), and 2.25–5.78 days, respectively. The tissue-specific concentration and BCFs values followed the order of liver > kidney ≥ intestine >> muscle. The proposed QSAR model with a high cross-validated value (Q2(cum)) of 0.930 and a correlation coefficient of 0.94 was obtained and was able to predict log BCF from parameters related to molar volume and isotropic average static field polarizability. The results show that the model has a high level of accuracy, making the proposed approach a suitable method for predicting the log BCF.

A green approach for organophosphate ester determination in airborne particulate matter: Microwave-assisted extraction using hydroalcoholic mixture coupled with solid-phase microextraction gas chromatography-tandem mass spectrometry

Particulate matter (PM) is among the most dangerous air pollutants, and there is a growing concern related to the effects of airborne particles on human health. Their harmful effects can be derived are directly linked to the size of particles themselves and the associated pollutants after they have been taken up by inhalation. In this work was developed a new analytical method for the quantification of organophosphorus esters (OPE) bound to airborne PM. The proposed protocol provides for the microwave-assisted extraction (MAE) of the analytes from the PM followed by solid-phase microextraction gas chromatography-tandem mass spectrometry determination (SPME-GC-MS/MS). Unlike to the traditional protocol, which provides for the use of tedious Soxhlet extraction with environmentally damaging organic solvents, the proposed method allows for a reliable quantification by using an eco-friendly hydroalcoholic mixture (water/ethanol; 50:50, v/v). The method was developed using as target compounds ten organophosphate esters, namely tripropyl phosphate (TPP), tri-n-butyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), tributoxyethyl phosphate (TBEP), triphenyl phosphate (TPhP), 2-ethylhexyl-diphenyl phosphate (EHDPP), tris(2-ethylhexyl) phosphate (TEHP) and tricresyl phosphate (TCP). The extraction performance of five SPME fibers was evaluated and the DVB/CAR/PDMS coating demonstrated to be the most suitable for the extraction of the target analytes. Experimental Design was used for the multivariate optimization of the parameters affecting the MAE process as well as the SPME extraction, and the optimal working conditions were determined by using Derringer's desirability function. The developed method was validated in terms of linearity, sensitivity (LLOQ values of 0.5 ng/mL for TDCPP and 0.1 ng/mL for the other analytes), matrix effect (81–117%), intra and inter day accuracy (83–115% and 80–115%, respectively), and precision (repeatability and reproducibility in the range 1.0–12.4% and 2.3–15.2%, respectively). The satisfactory performances reached make the proposed protocol a green and high-throughput alternative for OPE quantification in particulate matter.

Synthesis and Characterization of Molecularly Imprinted Polymer for Tramadol Hcl Using Acryl Amide and 2-Hydroxyethyl Meth Acrylate as Monomers

Abstract Four electrodes were synthesized based on molecularly imprinted polymers (MIPs). Two MIPs were prepared by using tramadol hydrochloride (TRH) as the template, acryl amide (AA) and 2-hydroxy ethyl meth acrylate (2-HEMA) as monomers, divinyl benzene as a cross linker, and benzoyl peroxide as initiator, respectively. The same composition was used to prepare non-imprinted polymers (NIPs), but without the template (Tramadol hydrochloride). Different plasticizers were employed to prepare the membranes; tris (ethyl hexyl) phosphate (TEHP), tri Butyl phosphate (TBP), di-octyl phthalate (DOP) and nitrobenzene (NB) in PVC matrix. The electrode characteristics and properties were studied, including: slope, detection limit, life time and linearity range. The results of selectivity coefficient measurements using amino acids as interfering species showed no effect on tramadol electrode response. The prepared electrodes were intended for use in determining tramadol in pharmaceutical samples

The Mode of Action of Adjuvants-Relevance of Physicochemical Properties for Effects on the Foliar Application, Cuticular Permeability, and Greenhouse Performance of Pinoxaden.

We comprehensively studied the complexity of the mode of action of adjuvants by uncoupling the parameters contributing to the spray process during foliar application of agrochemicals. The ethoxylated sorbitan esters Tween 20 and Tween 80 improved the efficiency of pinoxaden (PXD) in controlling grass-weed species in greenhouse experiments by aiding retention, having humectant properties, maintaining the bioavailability, and increasing the cuticular penetration of PXD. The nonethoxylated sorbitan esters Span 20 and Span 80 showed minimal effects on retention, droplet hydration, or cuticular penetration, resulting in reduced PXD effects in the greenhouse. Tris(2-ethylhexyl)phosphate (TEHP) does not contribute much to retention and spreading but strongly enhances the diffusion of PXD across isolated P. laurocerasus cuticular membranes. As TEHP was most efficient in controlling the growth of grass-weed species, we propose that the direct effect of penetration aids on cuticular permeation plays a key role in the efficiency of foliar-applied agrochemicals.

A Sensitive Electrochemical Sensor for Rapid Determination of Mebeverine Hydrochloride and Metronidazole Benzoate Selective Molecular Imprinted Polymer in the PVC Membrane

By using precipitation polymerization, liquid electrodes of polymers imprinted with Mebeverine hydrochloride and metronidazole benzoate were created whereas the imprinted polymer (MIP) and non imprinted (NIP) polymers were prepared by using Mebeverine hydrochloride and Metronidazole benzoate qua a template. In the polymerization process, 2-Acrylamido-2-methyl-1-propane Sulphonic acid (AMPS) or 1-Vinylimidazole (VIZ) was used qua monomer, pentaerythritol triacrylate (PETRA) or Divinylbanzene (DVB) was used qua a cross-linker while benzoyl peroxide (BPO) was used as an initiator. The MIP membranes and the membranes of NIP were created by using Dibutyl Sebacate (DBS) and Tris(2-ethylhexyl)phosphate(TEHP) qua plasticizers in PVC matrix. The response time of the liquid electrodes was 1min. whereas their slopes and detection limits reached to 19.62 – 57.36 mV per decade and 1.2 x 10-6 – 2.0 x 10-5 M, respectively. Filling with standard solution of drug (0.1M), the liquid electrodes response -with suitable No.( selectivity for numerous of species - was suitable No.( since pH reached to 1.5 – 12. The developed electrodes were successfully applied for the analyte determination in preparation pharmaceutical sample without any time consuming pretreatment steps.

Neodymium‐based catalysts bearing phosphate ligands for ring‐opening polymerization of ɛ‐caprolactone

ABSTRACTNeodymium‐based catalysts coordinated with phosphate ligands (NdCl3·3L), where L = triethyl phosphate (TEP) or tris(2‐ethylhexyl) phosphate (TEHP), were synthesized. The ring‐opening polymerizations (ROP) of ɛ‐caprolactone (ɛ‐CL) with these catalysts in the presence of benzyl alcohol initiator were performed, yielding polymers with well‐defined molecular weights and relatively narrow polydispersity index (PDI = 1.22–1.65). In situ NMR analysis of the reaction between NdCl3·3TEP and benzyl alcohol indicated that ROP proceeds through a coordination‐insertion mechanism. The end groups of the resultant polymers were determined using MALDI‐ToF mass spectrometry and NMR spectroscopy. The quasi‐living nature of this catalytic system was demonstrated by kinetic studies and the successful synthesis of the block copolymer poly(ɛ‐caprolactone)‐block‐poly(l‐lactide) by sequential monomer addition. Kinetic studies revealed that the catalyst with the bulkier TEHP ligand increased the rate of ROP of ɛ‐CL as compared to the TEP ligand. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1289–1296

Occurrence and partitioning behavior of organophosphate esters in surface water and sediment of a shallow Chinese freshwater lake (Taihu Lake): Implication for eco-toxicity risk

Organophosphate esters (OPEs) are ubiquitous in the aquatic environment, which have been considered or suspected as carcinogens and neurotoxicants. In this study, the occurrence, spatial distribution, potential sources, partitioning character and potential risks of OPEs in the surface water and sediment collected from Taihu Lake were investigated. The concentrations of ∑12 OPEs varied from 1.0 × 102 to 1.7 × 103 ng/L for the surface water and from 8.1 to 4.2 × 102 ng/g dw for the sediment. Trimethyl phosphate (TEP) was the predominant congener in the surface water, while Tris(2-ethylhexyl) phosphate (TEHP) in the sediment. Positive correlations between OPEs indicated that they may have the same sources and/or similar environmental behavior. The pseudo-partitioning values of OPEs ranged from 0.59 to 6.5 × 104 L/kg. TEHP has the highest pseudo-partitioning coefficient, which indicated that TEHP inclined to be enriched in the sediment in Taihu Lake. Risk assessment (RQ) showed that individual OPEs in the surface water and sediment posed no/low risk to aquatic organisms, except 2-Ethylhexyl diphenyl phosphate (EHDPP) (moderate risk) in water.

Synthesis and Characterization of a Molecularly Imprinted Polymer for Diclofenac Sodium Using (2-vinylpyridine and 2-hydroxyethyl metha acrylate) as the Complexing Monomer

Four electrodes were synthesized based on molecularly imprinted polymers (MIPs). Two MIPs were prepared by using the diclofenac sodium (DFS) as the template, 2-hydroxy ethyl metha acrylate(2-HEMA) and 2-vinyl pyridine(2-VP) as monomers as well as divinyl benzene and benzoyl peroxide as cross linker and initiator respectively. The same composition used for prepared non-imprinted polymers (NIPs) but without the template (diclofenac sodium). To prepared the membranes electrodes used different plasticizers in PVC matrix such as: tris(2-ethyl hexyl) phosphate (TEHP), tri butyl phosphate (TBP), bis(2-ethyl hexyl) adipate (BEHA) and tritolyl phosphate (TTP). The characteristics studied the slop, detection limit, life time and linearity range of DFS–MIPs electrodes. The results were obtained from selectivity measurements on amino acids showed good response as well as pharmaceuticals analysis.

Occurrence of Organophosphorus Flame Retardants and Plasticizers (PFRs) in Belgian Foodstuffs and Estimation of the Dietary Exposure of the Adult Population.

The occurrence of 14 organophosphorus flame retardants and plasticizers (PFRs) was investigated in 165 composite food samples purchased from the Belgian market and divided into 14 food categories, including fish, crustaceans, mussels, meat, milk, cheese, dessert, food for infants, fats and oils, grains, eggs, potatoes and derived products, other food (stocks), and vegetables. Seven PFRs [namely, tri-n-butyl phosphate (TnBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), triphenyl phosphate (TPHP), 2-ethylhexyldiphenyl phosphate (EHDPHP), and tris(2-ethylhexyl) phosphate (TEHP)] were detected at concentrations above quantification limits. Fats and oils were the most contaminated category, with a total PFR concentration of 84.4 ng/g of wet weight (ww), followed by grains (36.9 ng/g of ww) and cheese (20.1 ng/g of ww). Our results support the hypothesis that PFR contamination may occur during industrial processing and manipulation of food products (e.g., packaging, canning, drying, etc.). Considering the daily average intake of food for the modal adult Belgian (15-64 years of age), the dietary exposure to sum PFRs was estimated to be ≤7500 ± 1550 ng/day [103 ± 21 ng/kg of body weight (bw)/day]. For individual PFRs, TPHP contributed on average 3400 ng/day (46.6 ng/kg of bw/day), TCIPP 1350 ng/day (18.5 ng/kg of bw/day), and EHDPHP 1090 ng/day (15 ng/kg of bw/day), values that were lower than their corresponding health-based reference doses. The mean dietary exposure mainly originated from grains (39%), followed by fats and oils (21%) and dairy products (20%). No significant differences between the intakes of adult men and women were observed.

Solvent-stir bar microextraction system using pure tris-(2-ethylhexyl) phosphate as supported liquid membrane: A new and efficient design for the extraction of malondialdehyde from biological fluids

A novel and efficient device of solvent stir-bar microextraction (SSBME) system coupled with GC-FID detection was introduced for the pre-concentration and determination of malondialdehyde (MDA) in different biological matrices. In the proposed device, a piece of porous hollow fiber was located on a magnetic rotor by using a stainless steel-wire (as a mechanical support) and the whole device could stir with the magnetic rotor in sample solution cell. The device provided higher pre-concentration factor and better precision in comparison with conventional SBME due to the reproducible, stable and high contact area between the stirred sample and the hollow fiber. Organic solvent type, donor and acceptor phase pH, temperature, electrolyte concentration, agitation speed, extraction time, and sample volume as the effective factors on the SSBME efficiency, were examined and optimized. Pure tris-(2-ethylhexyl) phosphate (TEHP) was examined for the first time as supported liquid membrane (SLM) for the determination of MDA by SSBME method. In contrast to the conventional SLMs of SBME in the literature, the SLM of TEHP was highly stable in contact with biological fluids and provided the highest extraction efficiency. Under optimized extraction conditions, the method provided satisfactory linearity in the range 1–500 ng mL−1, low LODs (0.3–0.7 ng mL−1), good repeatability and reproducibility (RSD% (n = 5) < 4.5) with the pre-concentration factors higher than 130-fold. To verify the accuracy of the proposed method, the traditional spectrophotometric TBA (2-thiobarbituric acid) test was used as a reference method. Finally, the proposed method was successfully applied for the determination and quantification of MDA in biological fluids.

Synthesis and Characterization of a Molecularly Imprinted Polymer for Diclofenac Sodium Using (2-vinylpyridine and 2-hydroxyethyl metha acrylate) as the Complexing Monomer

Four electrodes were synthesized based on molecularly imprinted polymers (MIPs). Two MIPs were prepared by using the diclofenac sodium (DFS) as the template, 2-hydroxy ethyl metha acrylate(2-HEMA) and 2-vinyl pyridine(2-VP) as monomers as well as divinyl benzene and benzoyl peroxide as cross linker and initiator respectively. The same composition used for prepared non-imprinted polymers (NIPs) but without the template (diclofenac sodium). To prepared the membranes electrodes used different plasticizers in PVC matrix such as: tris(2-ethyl hexyl) phosphate (TEHP), tri butyl phosphate (TBP), bis(2-ethyl hexyl) adipate (BEHA) and tritolyl phosphate (TTP). The characteristics studied the slop, detection limit, life time and linearity range of DFS–MIPs electrodes. The results were obtained from selectivity measurements on amino acids showed good response as well as pharmaceuticals analysis.

Organophosphate ester (OPEs) flame retardants and plasticizers in air and soil from a highly industrialized city in Turkey

Passive air samples were collected at eight sites in Bursa, Turkey during five sampling periods between February–December 2014. Locations encompassed urban, suburban, industrial, rural and background environments. Soil samples (n=8) were collected at each site during February 2014. Six OPEs were detected in samples: tris(2-chloroethyl) phosphate (TCEP), tris(chloropropyl) phosphate (TCPP), triphenyl phosphate (TPHP), tris(2-butoxyethyl) phosphate (TBOEP), tris(2-ethylhexyl) phosphate (TEHP), and tris(2-isopropylphenyl) phosphate (T2iPPP). Frequency of detection in air samples was TCPP and TPHP (100%)>TBOEP (88%)>TCEP (85%)>TEHP (78%)>T2iPPP (20%). Total OPEs in air per site by sampling period (excluding non-detects) ranged from 529 to 19,139pg/m3. In soil, total OPEs ranged from 38 to 468ng/g dw. In air, alkylated OPEs dominated followed by halogenated and aryl OPEs. In air, annual mean concentrations were TBOEP>TCPP>TPHP>T2iPPP>TEHP>TCEP. In soils, alkylated OPEs were dominant at six sites and chlorinated OPEs at two sites. A comparison of OPE profiles between air and soil suggests that soils may be partly a source of OPEs to air. Mean concentrations in air were not directly proportional to temperature, and there were differences between alkylated compared to halogenated and aryl OPEs. In air, total and alkylated OPEs levels were fairly uniform, whereas more variability was found for the halogenated and aryl compounds. The relative contribution to total OPEs decreases for alkylated OPEs and increases for halogenated OPEs in samples going from background to suburban to urban and industrial sites. Levels of individual OPEs were all positively correlated between air and soils. In air, correlations between individual compounds were weak to moderate and were only statistically significant for TBOEP and TPHP. In soils, correlations were generally stronger and statistically significant only for TPHP and T2iPPP.

Organophosphate esters in East Greenland polar bears and ringed seals: Adipose tissue concentrations and in vitro depletion and metabolite formation

East Greenland is a contamination “hot spot” for long-range transported anthropogenic chemicals, including organophosphate esters (OPEs). High concentrations of OPEs have been reported in arctic air while very little is known for wildlife where OPE tissue residues levels appear to be strongly influenced by biotransformation. In the present study, the hepatic in vitro metabolism of six environmentally relevant organophosphate (OP) triesters and corresponding OP diester formation were investigated in East Greenland polar bears (PBs) and ringed seals (RSs). The in vitro metabolism assay results were compared to adipose levels in field samples from the same individuals. In vitro OP triester metabolism was generally rapid and structure-dependent, where PBs metabolized OPEs more rapidly than RSs. Exceptions were the lack of triethyl phosphate (TEP) metabolism and slow metabolism of tris(2-ethylhexyl) phosphate (TEHP) in both species. OP diester metabolites were also formed with the exception of TEP which was not metabolized at all. Tris(1,3-dichloro-2-propyl) phosphate was completely converted to its corresponding diester. However, the mass balances showed that OP diester formation corresponding to TEHP, tri(n-butyl) phosphate, and tris(2-butyoxyethyl) phosphate did not account for 100% of the OP triester depletion, which indicated alternate pathways of OP triester metabolism had occurred. Triphenyl phosphate was completely converted to its OP diester metabolite in PBs but not in RSs suggesting species-specific differences. The results demonstrated that OP triester bioaccumulation and fate in PBs versus their RS prey is substantially influenced by biotransformation.

Legacy and emerging organophosphοrus flame retardants in car dust from Greece: Implications for human exposure

Organophosphorus flame retardants (PFRs) and emerging PFRs (ePFRs) are two groups of compounds used as replacements for brominated flame retardants (BFRs). They have already been detected in indoor dust (mainly in homes and offices). To date, few studies investigated the occurrence of FRs in car dust and the information of possible health risks is still limited. The present study reports on the investigation of the levels and profiles of eight target PFRs: tris(2-ethylhexyl) phosphate (TEHP), tris(2-chloroethyl) phosphate (TCEP), tris(2-butoxyethyl) phosphate (TBEP), triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPHP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri cresyl phosphate (TCP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and four target ePFRs; 2,2-bis(chloromethyl)propane-1,3-diyltetrakis(2-chloroethyl)bisphosphate (V6), isodecyl diphenyl phosphate (iDDPHP), resorcinol bis(diphenylphosphate) (RDP) and bisphenol A-bis(diphenyl phosphate) (BDP) in car dust from Greece. The samples were collected from the interior of 25 private cars in Thessaloniki, Greece, with different years of manufacture (1997–2015) and continents of origin. After ultrasonic extraction and Florisil fractionation, the PFR analysis was carried out by GC-EI/MS, whereas the ePFRs were analyzed by LC-MS/MS. Levels of Σ8PFRs varied from 2000 to 190,000 ng g−1, with mean and median concentrations of 20,000 and 11,500 ng g−1, respectively. The concentrations of Σ4ePFRs ranged from 44 to 8700 ng g−1, with mean and median values at 1100 and 190 ng g−1, respectively. Estimations of human exposure showed that toddlers are more exposed than adults to both PFRs and ePFRs. Yet, the intake via dust ingestion and dermal absorption was several orders of magnitude lower than the corresponding reference doses.