Tris 2-ethylhexyl Phosphate Research Articles

Studies in Solvent Extraction and Supported Liquid Membrane for Platinum Recovery from Chloride Media by Tris(2-ethylhexyl) Phosphate

ABSTRACTExtraction studies of platinum ions from chloride medium by solvent extraction (SX) and supported liquid membrane (SLM) using tris(2-ethylhexyl) phosphate (TEHP) were carried out. Platinum ions were extracted by TEHP in the presence of SnCl2 during SX and stripped by an aqueous mixture of 2 M HCl + 0.05 M NaClO3. The extraction was studied by varying Sn:Pt feed ratios and takes place through ion-pair association. Extraction studies with simulated spent catalyst dissolver solution containing Pt, Pd, Cr, Ni, Mn, and Fe showed high selectivity for Pt. The initial feed phase with platinum concentration of 5.1 × 10−4 M was effectively transported within 360 min using a polyvinylidene difluoride membrane with 0.45 µm pore size, dipped in 0.05 M TEHP/kerosene media. Permeability coefficient value of 1 × 10−3 cm/s was obtained at 3 M HCl (feed) across the membrane. Almost 96% of the platinum ions were recovered from a real spent autocatalyst solution.

Upgrading of the crude yellowcake to a highly purified form using tris(2-ethylhexyl) phosphate in presence of EDTA or CDTA

Purification of low grade uranium concentrate was carried out using 0.05molL−1 Tris 2-ethylhexyl Phosphate in kerosene from 5molL−1 nitrate solution. More than 98% of uranium extracted after 5 stages of contact, shaking time 5min, volume phase ratio 1/1 and at room temperature. Uranium stripping efficiency reached 99% using double distilled H2O, 10min shaking time, (O/A) ratio 4/1 and after three stripping stages. The masking agents used to improve the yellowcake purity compared to the experiment without additives, with Ethylene diaminetetracetic acid (EDTA) ensuring the highest purity. The result obtained can be attributed to complexation of impurity elements with EDTA, preventing their precipitation from the stripping solution.

Occurrences and distribution characteristics of organophosphate ester flame retardants and plasticizers in the sediments of the Bohai and Yellow Seas, China

Concentrations and distribution characteristics of organophosphate esters (OPEs) in surface sediment samples were analyzed and discussed for the first time in the open Bohai Sea (BS) and Yellow Sea (YS). Three halogenated OPEs [tris-(2-chloroethyl) phosphate (TCEP), tris-(1-chloro-2-propyl) phosphate (TCPP), and tris-(1,3-dichloro-2-propyl) phosphate (TDCPP)] and five non-halogenated OPEs [tri-isobutyl phosphate (TiBP), tri-n-butyl phosphate (TnBP), tripentyl phosphate (TPeP), triphenyl phosphate (TPhP) and tris-(2-ethylhexyl) phosphate (TEHP)] were detected in this region. The concentrations of eight OPEs in total (Σ8OPEs) ranged from 83 to 4552pgg−1dry weight (dw). The halogenated OPEs showed higher abundances than the non-halogenated ones did, with TCEP, TCPP, and TEHP the main compounds. Generally, concentrations of OPEs in the BS were higher than those in the YS. Riverine input (mainly the Changjiang Diluted Water (CDW)) and deposition effect in the mud areas might have influenced the spatial distributions of OPEs. Correlation between OPE concentrations and total organic carbon (TOC) indicated TOC was an effective indicator for the distribution of OPEs. Inventory analysis of OPEs implied that sea sediment might not be the major reservoir of these compounds.

Upgrading of the Crude Yellow Cake to a Highly Purified Form using Tris(2-ethylhexyl) Phosphate in Presence of EDTA or CDTA

Upgrading crude yellow cake was done by 0.05 M Tris 2-ethylhexyl Phosphate / kerosene from 5 M nitrate solution. More than 98 % of uranium extracted after 5 stages of contact, shaking time 5 minutes and volume phase ratio 1/1. Uranium stripping efficiency reached 99 % using distilled H2O, 10 minutes shaking time, (O/A) ratio 4/1 and three stripping stages. The purity of the produced cakes was enhanced by the addition of EDTA or CDTA. The produced cake using TEHP followed by EDTA addition to the stripping solution before uranium precipitation step was the most preferable cake with lower gangues.

Occurrence, Removal, and Environmental Emission of Organophosphate Flame Retardants/Plasticizers in a Wastewater Treatment Plant in New York State.

The occurrence and fate of 14 triester organophosphate flame retardants (OPFRs) and plasticizers and their two diester metabolites were investigated in a wastewater treatment plant (WWTP) in the Albany area of New York State. All target OPFRs were found in wastewater, with average concentrations that ranged from 20.1 ng/L for tris(methylphenyl) phosphate (TMPP) to 30 100 ng/L for tris(2-butoxyethyl)phosphate (TBOEP) in influents and from 7.68 ng/L for TMPP to 12 600 ng/L for TBOEP in final effluents. TBOEP was the dominant compound in influents (max: 69 500 ng/L) followed in decreasing order by tris(1-chloro-2-propyl)phosphate (TCIPP; max: 14 500 ng/L), bis(1,3-dichloro-2-propyl)phosphate (BDCIPP; max: 4550 ng/L), tris(1,3-dichloro-2-propyl)phosphate (TDCIPP; max: 3150 ng/L) and tris(2-chloroethyl)phosphate (TCEP; max: 8450 ng/L). The fraction of TMPP sorbed to suspended particulate matter (SPM) was 56.4% of the total mass in wastewater, which was the highest among the target chemicals analyzed. The average concentrations of OPFRs in sludge were between 4.14 ng/g dw for tripropyl phosphate (TPP) and 7290 ng/g dw for TBOEP; for ash, they were between 2.17 ng/g dw for TMPP and 427 ng/g dw for triphenyl phosphate (TPhP). The mass loadings of OPFRs into the WWTP ranged from 0.02 mg/day/person for TPP to 28.7 mg/day/person for TBOEP, whereas the emission from the WWTP ranged from 0.01 mg/day/person for 2-ethylhexyl diphenyl phosphate (EHDPP) to 5.12 mg/day/person for TCIPP. The removal efficiencies for OPFRs were slightly above 60% for TMPP, TBOEP, and tris(2-ethylhexyl)phosphate (TEHP) whereas those for other OPFRs were <40% (TPhP and BDCIPP) to negative values, suggesting incomplete removal in WWTPs.

Membranes based on polymer miscibility for selective transport and separation of metallic ions

Polymer inclusion membranes (PIM) used for selective transport and separation of metallic ions have emerged in recent times. Their expansion depends on the method of preparation and their suitable structure and physico-chemical characteristics.In this paper, a novel category of membranes for ions separation is reported. The membranes were synthesized by thermally induced phase separation using a mixture of polyvinylidene fluoride (PVDF) and cellulose triacetate (CTA) plasticized by tris(2-ethylhexyl) phosphate (TEHP) and with di-(2-ethylhexyl) phosphoric acid (D2EHPA) incorporated into the polymer as carrier to increase specific interactions between polymers. PIM membrane exhibited a hydrophobic (∼100°) and thermally stable up to ∼200°C porous homogenous structure.The transport of Ni(II), Zn(II) and Pb(II) from aqueous solutions was studied by competitive transport across polymer inclusion membranes (PIM). Competitive transport of ions in solution across PIM provide the selectivity order: Ni2+ (45%)>Pb2+ (35%)>Zn2+ (5%). A long-term transport experiment was carried out to study the durability of the system.

Organophosphate flame retardants in the indoor air and dust in cars in Japan.

The concentrations of organophosphate flame retardants (OPFRs) in the indoor air and dust were measured in 25 unoccupied cars in Japan. In the indoor air of the cars, most OPFRs were neither detected nor found at a concentration lower than the method quantification limit. The highest concentration (1500ngm-3) was obtained for tris(1-chloro-2-propyl) phosphate (TCIPP). By contrast, many OPFRs were detected in the dust samples collected from the interior of the cars. TCIPP and tris(2-ethylhexyl) phosphate (TEHP) were present at the highest concentrations at 390 μgg-1 (in dust from car seats) and 640μgg-1 (in dust from car floor mats), respectively. The highest median concentrations (35μgg-1 for car seats, 53μgg-1 for car floor mats) were obtained for tris(2-butoxyethyl) phosphate (TBOEP). According to the results of our exposure assessment, the typical exposures to OPFRs via inhalation in car cabins ranged from 9.0×10-4 to 7.8×10-1 ngkg-bw-1 day-1. The typical exposures to OPFRs via dust ingestion ranged from 9.2×10-4 to 8.8×10-1 ngkg-bw-1 day-1. We compared these results with the ref-erence doses for OPFRs and found that, based on cur-rent information about the toxicities of OPFRs, exposure to OPFRs in car cabins via inhalation and dust ingestion is unlikely to have adverse human health effects.

Integration of the free liquid membrane into electrokinetic supercharging – capillary electrophoresis for the determination of cationic herbicides in environmental water samples

A new approach based on the integration of the free liquid membrane (FLM) into electrokinetic supercharging (EKS) was demonstrated to be a new powerful tool used in order to enhance online preconcentration efficiency in capillary electrophoresis (CE). A small plug of water immiscible organic solvent was used as a membrane interface during the electrokinetic sample injection step in EKS in order to significantly enhance the analyte stacking efficiency. The new online preconcentration strategy was evaluated for the determination of paraquat and diquat present in the environmental water samples. The optimised FLM-EKS conditions employed were as follows: hydrodynamic injection (HI) of 20mM potassium chloride as leading electrolyte at 50mbar for 75s (3% of the total capillary volume) followed by the HI of tris(2-ethylhexyl) phosphate (TEHP) as FLM at a 1mm length (0.1% of the capillary volume). The sample was injected at 10kV for 360s, followed by the HI of 20mM cetyl trimethylammonium bromide (CTAB) as terminating electrolyte at 50mbar for 50s (2% of the total capillary volume). The separation was performed in 12mM ammonium acetate and 30mM NaCl containing 20% MeOH at +25kV with UV detection at 205nm. Under optimised conditions, the sensitivity was enhanced between 1500- and 1866-fold when compared with the typical HI at 50mbar for 50s. The detection limit of the method for paraquat and diquat was 0.15–0.20ng/mL, with RSDs below 5.5%. Relative recoveries in spiked river water were in the range of 95.4–97.5%. A comparison was also made between the proposed approach with sole preconcentration of the field-enhanced sample injection (FASI) and EKS in the absence of the FLM.

Dietary intake of phosphorus flame retardants (PFRs) using Swedish food market basket estimations

The occurrence of eight phosphorus flame retardants (PFRs) was investigated in 53 composite food samples from 12 food categories, collected in 2015 for a Swedish food market basket study. 2-ethylhexyl diphenyl phosphate (EHDPHP), detected in most food categories, had the highest median concentrations (9 ng/g ww, pastries). It was followed by triphenyl phosphate (TPHP) (2.6 ng/g ww, fats/oils), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) (1.0 ng/g ww, fats/oils), tris(2-chloroethyl) phosphate (TCEP) (1.0 ng/g ww, fats/oils), and tris(1-chloro-2-propyl) phosphate (TCIPP) (0.80 ng/g ww, pastries). Tris(2-ethylhexyl) phosphate (TEHP), tri-n-butyl phosphate (TNBP), and tris(2-butoxyethyl) phosphate (TBOEP) were not detected in the analyzed food samples. The major contributor to the total dietary intake was EHDPHP (57%), and the food categories which contributed the most to the total intake of PFRs were processed food, such as cereals (26%), pastries (10%), sugar/sweets (11%), and beverages (17%). The daily per capita intake of PFRs (TCEP, TPHP, EHDPHP, TDCIPP, TCIPP) from food ranged from 406 to 3266 ng/day (or 6–49 ng/kg bw/day), lower than the health-based reference doses. This is the first study reporting PFR intakes from other food categories than fish (here accounting for 3%). Our results suggest that the estimated human dietary exposure to PFRs may be equally important to the ingestion of dust.

Brominated, chlorinated and phosphate organic contaminants in house dust from Portugal

House dust is an important matrix to evaluate the human exposure to a large number of contaminants including organochlorine compounds and flame retardants. In this study, we measured the levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenyl ethane (DBDPE), polychlorinated biphenyls (PCBs) and several organophosphorus flames retardants (PFRs) in 28 house dust samples collected between 2010 and 2011 in two Portuguese cities, Aveiro and Coimbra. Among the measured compounds, PFRs, particularly tris(2-ethylhexyl) phosphate (TEHP), triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPP) and tris(methylphenyl) phosphate (TMPP), were the dominant group (median: 3200ngg−1). PBDE levels were the second highest (median: 340ngg−1) with great predominance of BDE 209 (median 270ngg−1), followed by HBCDDs (median: 150ngg−1), DBDPE (54ngg−1), PCBs (median: 6.3ngg−1) and BTBPE (median: 1.2ngg−1). Estimated daily intakes (EDIs) via dust ingestion showed a higher intake of PFRs (median: 4.6ngkg-bw−1day); however for all contaminants the EDIs were much lower than the established reference dose (RfD) values. Therefore, the studied population is exposed to non-hazardous levels of the target compounds when considering the exposure through house dust ingestion.

Organophosphate esters in dust samples collected from Danish homes and daycare centers

Organophosphates are used in a wide range of materials and consumer products and are ubiquitous in indoor environments. Certain organophosphates have been associated with various adverse health effects. The present paper reports mass fractions of organophosphates in dust samples collected from 500 bedrooms and 151 daycare centers of children living in Odense, Denmark. The identified compounds include: tris(isobutyl) phosphate (TIBP), tri-n-butyl phosphate (TNBP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP), tris(2-butoxyethyl) phosphate (TBOEP), triphenylphosphate (TPHP), 2-ethylhexyl-diphenyl phosphate (EHDPP), tris(2-ethylhexyl) phosphate (TEHP) and tris(methylphenyl) phosphate (TMPP). Both the number of organophosphates with median values above the limit of detection and the median values were higher for samples from daycare centers than for samples from homes. Organophosphates with median mass fractions above the limit of detection were: TCEP from homes (6.9 μg g−1), and TCEP (16 μg g−1), TCIPP (5.6 μg g−1), TDCIPP (7.1 μg g−1), TBOEP (26 μg g−1), TPHP (2.0 μg g−1) and EHDPP (2.1 μg g−1) from daycare centers. When present, TBOEP was typically the most abundant of the identified OPs. The sum of the organophosphate dust mass fractions measured in this study was roughly in the mid-range of summed mass fractions reported for dust samples collected in other countries. On a global scale, the geographical distribution of organophosphates in indoor dust is quite variable, with higher concentrations in industrialized countries. This trend differs from that for phthalate esters, whose geographic distribution is more homogeneous. Exposure to organophosphates via dust ingestion is relatively low, although there is considerable uncertainly in this assessment.

Can activated sludge treatments and advanced oxidation processes remove organophosphorus flame retardants?

This study aims to determine the occurrence of 10 OPFRs (including chlorinated, nonchlorinated alkyl and aryl compounds) in influent, effluent wastewaters and partitioning into sludge of 5 wastewater treatment plants (WWTP) in Catalonia (Spain). All target OPFRs were detected in the WWTPs influents, and the total concentration ranged from 3.67µgL−1 to 150µgL−1. During activated sludge treatment, most OPFRs were accumulated in the sludge at concentrations from 35.3 to 9980ngg−1dw. Chlorinated compounds tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP) and tris(2,3-dichloropropyl) phosphate (TDCPP) were not removed by the conventional activated sludge treatment and they were released by the effluents at approximately the same inlet concentration. On the contrary, aryl compounds tris(methylphenyl) phosphate (TMPP) and 2-ethylhexyl diphenyl phosphate (EHDP) together with alkyl tris(2-ethylhexyl) phosphate (TEHP) were not detected in any of the effluents. Advanced oxidation processes (UV/H2O2 and O3) were applied to investigate the degradability of recalcitrant OPFRs in WWTP effluents. Those detected in the effluent sample (TCEP, TCIPP, TDCPP, tributyl phosphate (TNBP), tri-iso-butyl phosphate (TIBP) and tris(2-butoxyethyl) phosphate (TBOEP)) had very low direct UV-C photolysis rates. TBOEP, TNBP and TIBP were degraded by UV/H2O2 and O3. Chlorinated compounds TCEP, TDCPP and TCIPP were the most recalcitrant OPFR to the advanced oxidation processes applied. The study provides information on the partitioning and degradability pathways of OPFR within conventional activated sludge WWTPs.

Uranium(VI) extraction from concentrated Egyptian wet-process phosphoric acid using a synergistic organophosphorous solvent mixture

Uranium(VI) recovery from concentrated Egyptian hemi-dihydrate wet-process phosphoric acid, 9.2 M, is investigated using synergistic organophosphorous solvent mixture of dinonyl phenyl phosphoric acid (DNPPA) and tris(2-ethylhexyl)phosphate (TEP). The effect of various factors such as [DNPPA] concentration, [TEP] concentration, phosphoric acid concentration, shaking time, aqueous: organic phase’s ratio (V aq/V org), stability of the solvent, the diluents effect, and temperature on the degree of extraction has been established. The effect of different stripping agents was investigated. The enthalpy change of the uranium extraction process was determined and the extracted uranium is further subjected to a second cycle of extraction [0.3 M D2EHPA + 0.075 M TOPO], scrubbing impurities (5 M sulfuric acid), and finally stripping with 1 M (NH4)2CO3 solution. Precipitation of uranium in highly pure UO3 product using hydrogen peroxide and heat treatment at 375 °C were carried out.

Organophosphorous flame retardants in biota from Svalbard, Norway

Eight arctic species, including fish, birds and mammals, from diverse habitats (marine and terrestrial) within the Svalbard Archipelago, Norway, were screened for 14 organophosphorus flame retardant (PFR) compounds. Ten PFRs were detected: tris(2-chloroethyl)phosphate (TCEP), tris(2-chloroisopropyl)phosphate (TCIPP), tris(1,3-dichloro-2-propyl)phosphate (TDCIPP), triphenyl phosphate (TPHP); 2-ethylhexyl diphenyl phosphate (EHDPP); tris(2-butoxyethyl)phosphate (TBOEP); tritolyl phosphate (TCrP); triisobutyl phosphate (TIBP); tris(2-ethylhexyl)phosphate (TEHP); and butyl diphenyl phosphate (DPhBP). The greatest number of different PFR compounds, and the highest detection frequency were measured in capelin (Mallotus villotus), and the lowest in Brünnich's guillemot (Uria lomvia). The highest concentrations of ΣPFR, as well as the highest concentration of a single PFR compound, TBOEP, were measured in arctic fox (Vulpes lagopus). The presence of PFR compounds in arctic biota indicates that these compounds can undergo long-range transport and are, to some degree, persistent and bioaccumulated. The potential for biomagnification from fish to higher trophic levels seems to be limited.

Removal of organophosphate esters from municipal secondary effluent by ozone and UV/H2O2 treatments

Organophosphate esters (OPEs) have emerged as a new class of contaminants due to their massive use as flame retardants and plasticizers. These contaminants are toxic to aquatic organisms and some of them are not biodegradable in wastewater treatment plants. This study investigated the degradation kinetics of eight typical OPEs during ozone and UV/H2O2 treatments in Milli-Q water, humic acid (HA) solution, and municipal secondary effluent. The studied OPEs included three chlorinated: tris(2-chloroethyl) phosphate (TCEP), tris(chloropropyl) phosphate (TCPP) and tris(dichloropropyl) phosphate (TDCP); two aromatic: triphenyl phosphate (TPhP) and tricresyl phosphate (TCrP); and three aliphatic: tri-n-butyl phosphate (TnBP), tris(2-butoxyethyl) phosphate (TBEP), and tris(2-ethylhexyl) phosphate (TEHP). Results indicate that the degradation of target OPEs conformed to the pseudo-first-order kinetics and UV/H2O2 was more effective than ozone for their elimination by comparing the overall removal efficiencies and energy consumptions. Two aromatic and two aliphatic OPEs (i.e., TPhP, TCrP, TnBP and TBEP) were effectively degraded by ozone and UV/H2O2 in the test water matrices, while all chlorinated and one aliphatic OPEs (i.e., TCEP, TCPP, TDCP and TEHP) were found to be recalcitrant to oxidation. Moreover, the presence of HA significantly enhanced the degradation of reactive OPEs in ozone treatment. (C) 2015 Elsevier B.V. All rights reserved.

Development and evaluation of electromembrane extraction across a hollow polymer inclusion membrane

In this work, a new variation of the electromembrane extraction (EME) approach employing a hollow polymer inclusion membrane (HPIM) was developed. In this method, a HPIM was prepared by casting a solution of the desired proportions of cellulose acetate (CTA), tris(2-ethylhexyl)phosphate (TEHP) and di-(2-ethylhexyl)phosphoric acid (D2EHPA) in dichloromethane on glass capillary tubing. Three basic drugs namely amphetamine, methamphetamine, and 3,4-methylenedioxy-N-methylamphetamine (MDMA) were selected as model analytes to evaluate the extraction performance of this new approach. The drugs were extracted from human plasma samples, through a 20μm thickness HPIM, to an aqueous acceptor solution inside the lumen of the hollow membrane. Parameters affecting the extraction efficiency were investigated in detail. Under the optimized conditions, enrichment factors in the range of 97–103-fold were obtained from 3mL of sample solution with a 10min extraction time and an applied voltage of 300V across the HPIM. The detection limits of the method for the three drugs were in the range of 1.0–2.5ng/mL (at a signal/noise ratio of three), with relative standard deviations of between 6.4% and 7.9%. When the method was applied to spiked plasma samples, the relative recoveries ranged from 99.2% to 100.8%. Enrichment factors of 103, 99 and 97 were obtained for amphetamine, methamphetamine, and MDMA, respectively. A comparison was also made between the newly developed approach and EME using supported liquid membranes (SLM) as well as standard sample preparation methods (liquid–liquid extraction) used by the Toxicology Unit, Department of Chemistry, Malaysia.

Assessment of human hair as an indicator of exposure to organophosphate flame retardants. Case study on a Norwegian mother–child cohort

A major challenge of non-invasive human biomonitoring using hair is to assess whether it can be used as an indicator of exposure to Flame Retardants, such as Organophosphate Flame Retardants (PFRs), since the contribution of atmospheric deposition (air and/or dust) cannot be neglected. Therefore, the aim of this study was to evaluate the suitability of using human hair more thoroughly by comparison of (i) levels of PFRs in human hair (from 48 mothers and 54 children), with levels measured in dust and air in their respective households; and (ii) levels of selected PFRs in hair with the levels of corresponding PFR metabolites in matching urine samples collected simultaneously. Most PFRs (tri-n-butyl phosphate (TNBP), 2-ethyl-hexyldiphenyl phosphate (EHDPHP), tri-phenyl phosphate (TPHP), tri-iso-butyl phosphate (TIBP), and tris(2-butoxyethyl) phosphate (TBOEP)) were detected in all human hair samples, tris(2-ethylhexyl) phosphate (TEHP) and tris(1,3-dichloro-iso-propyl) phosphate (TDCIPP) in 93%, tri-cresyl-phosphate (TCP) in 69% and tris(2-chloroethyl) phosphate (TCEP) in 21% of the samples. Levels of individual PFRs ranged between <1 and 3744ng/g hair and were lower than in indoor dust from the participants' homes. Several statistically significant associations between PFR levels in human hair and PFR levels in house dust and/or air were found, e.g. Spearman correlation (rS=0.561, p<0.05) between TBOEP in children's hair and in indoor air. Also, associations were found between TDCIPP in hair and its metabolite bis(1,3-dichloro-iso-propyl) phosphate (BDCIPP) in urine; they were stronger for children (e.g. Pearson correlation rP=0.475; p=0.001) than for mothers (rP=0.395, p=0.01). Levels of diphenyl phosphate (DPHP) in mothers' and children's urine were slightly correlated (rS=0.409, p=0.008), suggesting similar sources of exposure. To the best of our knowledge, this is the first study with such design and our findings might help to understand human exposure to and body burdens of PFRs.

Co-Extraction of U(VI) and HNO3 Using TBP and its Higher Homologues TiAP and TEHP: Comparison of Equilibria, Kinetics, and Rate of Extraction

In this work, bulk-liquid membrane (BLM) system is used to compare tri-n-butyl phosphate (TBP), tri-isoamyl phosphate (TiAP), and tris(2-ethylhexyl) phosphate (TEHP) for their relative ability to co-extract U(VI) and nitric acid from aqueous nitric acid feed-phase into water strip-phase, through hydrocarbon membrane-phase. The kinetics of extraction is modelled and the model is validated through experiments. The quantity which determines the efficiency of liquid emulsion membrane (LEM) process is the relative rate of extraction of U(VI) to nitric acid. This is in the order TiAP>TEHP>TBP, indicating that TiAP is most suitable for extraction of U(VI) from nitric acid using LEM.

ORGANOPHOSPHORUS FLAME RETARDANTS - TOXICITY AND INFLUENCE ON HUMAN HEALTH

Organophosphorus flame retardants (flame retardants, FRs) have been used for several decades in many industries, including the production of dyes, varnishes, adhesives, synthetic resins, polyvinyl chloride, hydraulic fluids, plastics and textiles. Their importance in recent times has increased due to i.a., significantly reduced use of polybrominated diphenyl ethers (PBDEs) - persistent organic pollutants, dangerous for the environment. The aim of this study was to review the available literature data concerning phosphorous FRs primarily for neurotoxic, fertility, reproductive and carcinogenic effects. The analysis concerned the following most commonly used substances: tris(2-ethylhexyl)phosphate (TEHP), tris(2-butoxyethyl)phosphate (TBEP), triphenyl phosphate (TPP), tris(2-chloroethyl)phosphate (TCEP), tetrakis(hydroxymethyl)-phosphonium chloride (THPC), tributyl phosphate (TBP), tricresyl phosphate (TCP), tris(2-chloroisopropyl)phosphate (TCPP), tris(1,3-dichloroisopropyl)phosphate (TDCP) and tetrakis(hydroxymethyl)phosphonium sulphate (THPS). In animal studies neurotoxic effects were found after exposure to TBEP, THPC, TBP and TCP, while in humans they were observed only after exposure to TCP. TCEP, THPS, TBP, TCP and TDCP caused disorders in fertility and/or fetal development of animals. Adverse effects on reproduction in humans may be caused by TPP, TCP, and TDCP. In laboratory animals the development of tumors was observed after high doses of TEHP, TCEP, TBP and TDCP. None of these compounds is classified as a human carcinogen. The environmental toxicity of phosphate FRs is low (except for TPP, TCEP and TBEP). They are not stable compounds, in living organisms they are metabolised and quickly excreted. Therefore, they can be used as an alternative to PBDEs.

OH-initiated heterogeneous oxidation of tris-2-butoxyethyl phosphate: implications for its fate in the atmosphere

Abstract. A particle-phase relative rates technique is used to investigate the heterogeneous reaction between OH radicals and tris-2-butoxyethyl phosphate (TBEP) at 298 K by combining aerosol time-of-flight mass spectrometry (C-ToF-MS) data and positive matrix factor (PMF) analysis. The derived second-order rate constants (k2) for the heterogeneous loss of TBEP is (4.44 ± 0.45) × 10−12 cm3 molecule−1 s−1, from which an approximate particle-phase lifetime was estimated to be 2.6 (2.3–2.9) days. However, large differences in the rate constants for TBEP relative to a reference compound were observed when comparing internally and externally mixed TBEP/organic particles, and upon changes in the RH. The heterogeneous degradation of TBEP was found to be depressed or enhanced depending upon the particle mixing state and phase, highlighting the complexity of heterogeneous oxidation in the atmosphere. The effect of gas-particle partitioning on the estimated overall lifetime (gas + particle) for several organophosphate esters (OPEs) was also examined through the explicit modeling of this process. The overall atmospheric lifetimes of TBEP, tris-2-ethylhexyl phosphate (TEHP) and tris-1,3-dichloro-2-propyl phosphate (TDCPP) were estimated to be 1.9, 1.9 and 2.4 days respectively, and are highly dependent upon particle size. These results demonstrate that modeling the atmospheric fate of particle-phase toxic compounds for the purpose of risk assessment must include the gas-particle partitioning process, and in the future include the effect of other particulate components on the evaporation kinetics and/or the heterogeneous loss rates.