Di-(2-ethylhexyl) Phosphate Research Articles

Electromembrane extraction of human chorionic gonadotropin – A case study on mass transfer of intact protein versus signature peptide

For the first time, we present targeted protein detection by tryptic digestion of human chorionic gonadotropin (hCG) followed by electromembrane extraction (EME). Operational parameters were optimized, and urine and serum samples spiked with hCG underwent tryptic digestion followed by EME of the βT5 signature peptide. The liquid membrane comprised nitrophenyl octyl ether (NPOE), carvacrol, and di(2-ethyl hexyl) phosphate (DEHP) at ratios of 49:49:2 (w/w/w). Extractions were performed in a conductive vial format for 45 min at 5 V. Even from highly complex digested samples of serum and urine, the signature peptide βT5 was extracted by EME and detected by LC-MS/MS. While attempts to extract intact hCG protein were unsuccessful, the extraction of the signature peptide was efficient. The extraction recovery from undigested and digested urine was 71 % (RSD = 17 %) and 116 % (RSD = 17 %), respectively. For serum, the extraction recoveries were 11 % (RSD = 23 %) for undigested samples and 110 % (RSD = 14 %) for digested samples. This study demonstrates both the potential and challenges of EME for protein analysis. Experiments regarding EME of intact proteins provided new insights into protein phase distribution. This fundamental case study underscores the potential of EME as a sample preparation technique for the targeted determination of protein biomarkers and drugs.

Fluorescent MnO2@DEHP Nanoprobe for Rapid and Selective Detection of Fe(III) ions.

Particle extraction via the liquid-liquid interface (PELLI) method has been utilized to produce Di-(2-ethylhexyl) phosphate (DEHP) coated MnO2 fluorescent nanoprobe denoted as MnO2@DEHP for the selective detection of Fe3+ ions. The synthesized MnO2@DEHP nanoprobe was characterized by various instrumental techniques such as FT-IR, PXRD, TEM, EDAX, HRTEM, DLS, and XPS. Since the high concentration of Fe3+ in waste water leads to water pollution, which in turn affects the ecosystem, and causes severe health hazards. Therefore, accurate detection of Fe3+ ions in the aqueous systems is essential as they are involved in various chemical and biological processes in living things. Here, the synthesized MnO2@DEHP nanoprobe selectively detects Fe3+ ions in the presence of various metal ions in an aqueous media by fluorescence quenching (turn-off) mechanism. The limit of detection (LOD) of MnO2@DEHP nanoprobe for Fe3+ was found to be 0.49µM. The test-strip method and real water sample analysis were also used to demonstrate the viability of MnO2@DEHP as a fluorescent nanoprobe to detect Fe3+ ions visually and in environment monitoring applications.

Parallel electromembrane extraction of peptides with monoterpene and medium-length fatty acid deep eutectic solvents

BackgroundElectromembrane extraction (EME) involves the process of mass transfer of charged analytes from an aqueous sample through an organic liquid membrane into an aqueous acceptor medium under the influence of an electrical field. Successful solvation of the analyte within the liquid membrane is of paramount importance and involves molecular interactions with the liquid membrane. In this comprehensive investigation, parallel EME was examined using a training set of 13 model peptides employing deep eutectic solvents as the liquid membrane. These deep eutectic solvents were formulated by mixing specific monoterpenes (thymol, menthol, camphor) with medium-chain fatty acids (1-octanoic acid and 1-decanoic acid). ResultsFrom an array of different liquid membrane compositions explored, it was revealed that the combination of camphor and 1-decanoic acid (in a 1:1 w/w ratio) with 2% di (2-ethylhexyl) phosphate (DEHP) delivered the most efficient extraction system. The solvation of the model peptides within this liquid membrane predominantly relied on ionic interactions between protonated basic functionalities and DEHP, along with hydrogen bond interactions between the deprotonated acid functionalities (hydrogen bond acceptor) and 1-decanoic acid (hydrogen bond donor). Selectivity was modulated by the pH of the sample and acceptor solutions, with a direct correlation to the polarity and net charge of the model peptides. The ionization of 1-decanoic acid in the interfacial region between the sample and liquid membrane emerged as an important factor influencing the selectivity. Significance and noveltyAlthough parallel EME of peptides has been reported previously, the current liquid membrane provides an extraction system with sufficient stability for the first time. Selective extraction of peptides through EME holds substantial promise within the realm of next-generation environmentally-friendly sample preparation methodologies. The findings presented in this paper contribute significantly to our fundamental understanding of these processes, and may serve as an important reference for the development of future methods in this field.

Generic conditions for electromembrane extraction of polar bases

The current paper reports the first generic conditions for electromembrane extraction (EME) of polar bases within −2.0 < log P < 1.0 from human plasma. Generic conditions are important for inter-lab transferability and reproducibility, and were accordingly developed in commercially available EME equipment. In previous work, generic methodology was proposed for the extraction of bases of moderate and low polarity in the range 1.0 < log P < 6.0. The current paper extends this range of hydrophobicity downward. For polar bases, the composition of the liquid membrane is critical, in order to obtain high extraction recoveries, and to keep the extraction current as low as possible. The final liquid membrane was based on the deep eutectic solvent formed upon mixing 6-methyl coumarin and thymol in a 1:2 w/w ratio. The deep eutectic solvent was mixed with 2-undecanone in a 1:1 volumetric ratio. The latter decreased the extraction current, and improved the stability of the EME system. Finally, di(2-ethylhexyl) phosphate (DEHP) was added as ionic carrier to the liquid membrane to improve the mass transfer of polar bases. With this liquid membrane, the following generic conditions were established for mono- and dibases in the range −2.0 < log P < 4.5; plasma samples were diluted with an equal volume of 900 mM HCOOH, the acceptor was 450 mM HCOOH, voltage was 40 V, and the extraction time was 30 min. With this development, generic EME methods are now available for mono- and dibases in the polarity range −2.0 < log P < 6.0.

Selective Solvent Extraction of Vanadium Over Chromium from Alkaline Leaching Solution of Vanadium Slag by D2EHPA/TBP

ABSTRACT A selective extraction process for recovering vanadium (IV) over chromium was proposed with use of a mixed extractant consisting of di(2-ethylhexyl) phosphate (D2EHPA) and tri-n-butyl phosphate (TBP). The influence of various factors, which included the initial aqueous pH value, the concentration of leach solution and D2EHPA, phase ratio (O/A), extraction equilibrium time and extraction temperature in the extraction process on the separation of V and Cr was investigated. Under the condition of the optimum extraction, vanadium extraction was above 94.0%. Meanwhile, under the optimum stripping conditions, the vanadium stripping was above 93.0% utilizing 1.5 mol/L sulfuric acid as the effective stripping reagent. The regeneration and reusability of the loaded organic phases after stripping were discussed. In addition, continuous three-stage extraction and stripping strategy indicated that the aggregate loss of vanadium was 0.885% and that the purity of vanadium was more than 99.9%. Under the condition of the optimum precipitation, when the pH value of the stripping solution was adjusted to 7.0 with ammonia water, the precipitation efficiency reached 99.93%. The calcination conditions (above 680 °C in air) were finally determined by TG-DTA and TG-MS experiments, and the V2O5 obtained by calcination was characterized by XRD. Additionally, a method for detecting impurity elements in vanadium matrix without interference was established. The recovery technology has practical significance in enlarging production scale, reducing specific energy consumption and cost, and realizing automatic control in vanadium leaching process.

Membrane-based liquid-phase microextraction of basic pharmaceuticals – A study on the optimal extraction window

The present paper defines the optimal extraction window (OEW) for three-phase membrane-based liquid-phase microextraction (MP-LPME) in terms of analyte polarity (log P), and anchors this to existing theories for equilibrium partitioning and kinetics. Using deep eutectic solvents (DES) as supported liquid membranes (SLM), we investigated how the OEW was affected by ionic-, hydrogen bond and π-π interactions between the SLM and analyte. Eleven basic model analytes in the range -0.4 < log P < 5.0 were extracted by MB-LPME in a 96-well format. Extraction was performed from 250 µL standard solution in 25 mM phosphate buffer (pH 7.0) into 50 µL of 10 mM HCl acceptor solution (pH 2.0) with mixtures of coumarin, camphor, DL-menthol, and thymol, with and without the ionic carrier di(2-ethylhexyl) phosphate (DEHP), as the SLM. The OEW with pure DES was in the range 2 < log P < 5, and low SLM aromaticity was favorable for the extraction of non-polar analytes. Here, extraction recoveries up to 98% were obtained. Upon addition of DEHP to the SLMs, the OEW shifted to the range -0.5 < log P < 2, and a combination of 5% DEHP and moderate aromaticity resulted in extraction recoveries up to 80% for the polar analytes. Extraction with ionic carrier was inefficient for the non-polar analytes, due to excessive trapping in the SLM. The results from our study show that LPME performs optimally in a relatively narrow log P-window of ≈ 2–3 units and that the OEW is primarily affected by ionic carrier and aromaticity.

Electromembrane extraction of peptides using deep eutectic solvents as liquid membrane

For the first time, we report electromembrane extraction (EME) of peptides using deep eutectic solvent (DES) as supported liquid membrane (SLM). DES were mixtures of coumarin, camphor, DL-menthol and thymol. Sixteen model peptides were extracted from 100 μL 50 mM phosphate buffer solution (pH 3.0), through the SLM, and into 100 μL acceptor solution consisting of 50 mM phosphoric acid (pH 1.8). EME was performed in 96-well format with 30 V to facilitate extraction of positively charged peptides. The model peptides comprised three to 13 amino acids, and differed significantly in terms of acid/base functionalities and polarity. We found pure DES to be inefficient for EME of peptides. However, with addition of a small amount of the ionic carrier di(2-ethylhexyl) phosphate (DEHP) to the DES, the extraction efficiency increased due to ionic interactions. With the most efficient SLM; coumarin and thymol mixed in molar ratio (1:2) with 2.0% (v/v) DEHP, average recovery after 15 min was 55%; five peptides were extracted with recovery > 80%, nine peptides with recoveries in the range 40–80%, and two peptides were not extracted (recovery < 5%). When extraction time was extended to 45 min, average extraction recovery increased to 83%. Extraction recoveries with DES were higher than previously reported in the literature for the same model peptides.

Equilibrium analysis of neodymium - yttrium extraction in nitric acid media with D2EHPA as solvent

This study aimed to develop the liquid-liquid equilibrium models to predict neodymium (Nd) and yttrium (Y) distribution in the extraction system. Feed solution (solution of Nd and Y in the 1 M nitric acid media) was mixed with solvent (di-2-ethyl-hexyl-phosphate (D2EHPA) diluted in kerosene) with volume ratio of 1:1 using a mechanical shaker for 25 min. The solution was settled to separate the aqueous and organic phase. Neodymium and yttrium concentrations in the aqueous phase were analyzed by using X-Ray Fluorescence - Ortec 7010 with Am 241. Meanwhile, the concentration of Nd and Y in the organic phase were evaluated by using mass balance. The results showed that the separation of Y from Nd was successfully carried out using 0.30 M D2EHPA diluted in kerosene. The Y extraction efficiency of 93% was obtained. To predict Nd and Y distributions, two mathematical equilibrium models were formulated: (i) the stoichiometric model derived from the reaction mechanism by considering the available reaction coefficients and (ii) the non-stoichiometric model is proposed to obtain approximate equilibrium data of Nd – Y extraction. The models were validated using experimental data. Neodymium and yttrium equilibrium distribution with D2EHPA as the solvent was better approximated using the non-stoichiometric than the stoichiometric equilibrium model as shown by the lower of mean relative errors.

Food emulsifier polysorbate 80 promotes the intestinal absorption of mono-2-ethylhexyl phthalate by disturbing intestinal barrier

Di-2-ethylhexyl phosphate (DEHP) and its main toxic metabolite mono-2-ethylhexyl phthalate (MEHP) are the typical endocrine disrupting chemicals (EDCs) and widely affect human health. Our previous research reported that synthetic nonionic dietary emulsifier polysorbate 80 (P80, E433) had the promotional effect on the oral absorption of DEHP in rats. The aim of this study was to explore its mechanism of promoting oral absorption, focusing on the mucus barrier and mucosal barrier of the small intestine. A small molecule fluorescent probe 5-aminofluorescein-MEHP (MEHP-AF) was used as a tracker of MEHP in vivo and in vitro. First of all, we verified that P80 promoted the bioavailability of MEHP-AF in the long-term and low-dose exposure of MEHP-AF with P80 as a result of increasing the intestinal absorption of MEHP-AF. Afterwards, experimental results from Western blot, qPCR, immunohistochemistry, and immunofluorescence showed that P80 decreased the expression of proteins (mucus protein mucin-2, tight junction proteins claudin-1 and occludin) related to mucus barrier and mucosal barrier in the intestine, changed the integrity of intestinal epithelial cell, and increased the permeability of intestinal epithelial mucosa. These results indicated that P80 promoted the oral absorption of MEHP-AF by altering the intestinal mucus barrier and mucosal barrier. These findings are of great importance for assessing the safety risks of some food emulsifiers and clarifying the absorption mechanism of chemical pollutants in food, especially for EDCs.

A comparative investigation into floatability of bastnaesite with three di/trialkyl phosphate surfactants

Flotation separation and recovery of rare earth minerals (REM) have returned to an important position due to the growing strategy demand for rare earth elements (REE). In this paper, a comparative investigation into the floatability of bastnaesite ((Ce,La)FCO3) was conducted by using three di/trialkyl phosphate collectors, di(2-ethylhexyl) phosphate (DEHPA), dibutyl phosphate (DBP) and tributyl phosphate (TBP). The density functional theory (DFT) computation recommends that the chemical activity of the three phosphate collectors is in order of DEHPA ≥ DBP >> TBP, and their hydrophobization as-suggested by the lgP (oil-water partition coefficient) value is in the order of DEHPA > TBP > DBP. The micro-flotation indicates that the preferable pH values for flotation of bastnaesite with the three phosphate collectors are 7.0–8.0, and DEHPA achieves much higher flotation recovery of bastnaesite, followed by DBP, and then TBP, which coincides with their reactivity and hydrophobicity, the two prerequisites for froth flotation. The contact angle, zeta potential, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) deduce that DEHPA likely reacts with the Ce(Ⅲ) atoms of bastnaesite interface through its O atom(s) of the P(=O)–O– group to generate the Ce–O–P bonds, and its two 2-ethylhexyl groups orient outside for attaching bubbles, resulting in flotation enrichment of bastnaesite. Furthermore, this investigation offers a novel strategy for developing collectors in selective beneficiation of REM.

Solvent Extraction of Sc(III) by D2EHPA/TBP from the Leaching Solution of Vanadium Slag

The solvent extraction of scandium by the mixture of di-(2-ethylhexyl) phosphate (D2EHPA) and tri-n-butyl phosphate (TBP) has been investigated in the acidic leaching solution of vanadium slag. Thermodynamic analysis of the species distribution diagrams on the Sc-S-H2O system showed that scandium mainly exists as Sc3+ and Sc(SO4)+, and sulfur mainly exists as HSO4− in the actual leaching solution of vanadium slag (pH = −0.75). The extraction process was studied to optimize various parameters such as the extractant concentration, dosage of TBP, phase ratio, and stirring speed. The results indicated that 83.64% of scandium and less than 2% of co-extracted elements were extracted under optimal conditions. Then, over 95% of the co-extracted elements and less than 1.1% of scandium were scrubbed from the loaded organic phase by 4.0 mol/L of HCl. Finally, 87.20% of scandium was stripped with 2 mol/L of NaOH and 1 mol/L of NaCl at a stripping O/A of 1:1.

Impact of ion balance in electromembrane extraction

Electromembrane extraction (EME) involves transfer of analyte ions from aqueous sample, through a supported liquid membrane (SLM), and into an aqueous acceptor solution under the influence of an external electrical field. In addition to target analyte ions, the sample also contains matrix ions, and both the sample and acceptor contains background buffer ions to control pH. The ratio between the total amount of ions in sample and acceptor defines the ion balance (χ). Previous publications have discussed the impact of ion balance, but conclusions are contradictory. Therefore, the current paper investigated the ion balance in more detail. From a theoretical point of view, low χ-values favor EME; buffer anions at high concentration in the acceptor migrate into the SLM, while target cations enters the SLM from the sample to maintain electroneutrality. A large number of experiments was performed in this paper to investigate the practical impact of ion balance. Twelve basic drugs were used as model analytes (0.0 < log P < 5.0), and 2-nitrophenyl octyl ether (NPOE) and NPOE + 5% di(2-ethylhexyl) phosphate (DEHP) were used as SLM. With formate buffer pH 3.75 as sample and acceptor, the impact of χ in the range 0.01–10 was studied without bias from differences in pH. Here model analytes were unaffected by ion balance. Buffers containing propionic, butyric, and valeric acid were also tested. These buffer ions migrated more into the SLM, and affected recoveries in several cases. However, this was due to ion pairing rather than effects of ion balance. Similar behaviors from sodium chloride and urine samples were observed with different χ-values. Thus, in the systems tested, almost no impact of ion balance was found, and this was attributed to very low partition of background buffer and matrix ions into the SLM. On the other hand, extractions were in several cases influenced by ion pairing phenomena.

Influence of Different Carriers in Polymer Inclusion Membranes for Desalination of Seawater

Desalination of seawater using various polymer inclusion membranes was carried out. Polymer inclusion membrane (PIM) is known to have the highest stability, able to overcome liquid membrane instability and was placed in between two phases: the source phase is seawater and the receiving phase is the micro-filtered water. Determination of salinity levels in the feed phase and the receiving phase was carried out using a salinity meter, while membrane characterization was done using FTIR and SEM techniques. Polyvinyl chloride (PVC) based PIM membranes were prepared using different single and mixed synergtic carriers ratio of 1:1 viz. dibutyl ether, methyltrioctylammonium chloride (Aliquat 336), di-(2-ethylhexyl)-phosphate (D2EHPA), thenoyl trifluoroacetone (HTTA), tributyl phosphate (TBP) and eugenol (PE). The results showed the salinity value for single HTTA carriers had a greater salinity value in comparison to mixed carriers (HTTA:TBP; HTTA:Aliquat; D2EHPA:TBP; and D2EHPA:Aliquat) gave different salinity value towards the desalination process.

Modeling the Extraction Rate Coefficient for the Extraction of Yttrium by DEHPA Using Organic-Phase Recycle

ABSTRACTExtraction of yttrium (Y) from sulfuric acid was studied using di(2-ethylhexyl) phosphate (DEHPA). A portion of the organic phase was recycled back into the mixer after extraction for the mixer to operate at a moderate organic-to-aqueous volumetric phase ratio while processing at a low organic-to-aqueous flow rate ratio. The effective performance of the mixer was evaluated when operating at different organic-phase flow fractions. To model the extraction rate coefficient, a 2-factor designed experiment was performed by conducting both equilibrium and mixer-settler tests. The organic-phase flow fraction was varied over four discrete levels while the extractant concentration was varied over three discrete levels. Increasing the organic-phase flow fraction yielded a continual increase in the extraction rate coefficient. In contrast, increasing the extractant concentration yielded an initial increase followed by a subsequent decrease in the extraction rate coefficient. The decline in the extraction rate coefficient was attributed to a decrease in the yttrium-extractant complex’s diffusion coefficient. High metal loading caused an elevated organic-phase viscosity and thus the low diffusion coefficient. An extraction rate coefficient model is proposed to describe the effects of extractant concentration, viscosity and organic-phase flow fraction. Mass transfer resistance was largely in the organic phase.

Biomonitoring of organophosphate triesters and diesters in human blood in Jiangsu Province, eastern China: Occurrences, associations, and suspect screening of novel metabolites

Since organophosphate (OP) triesters are ubiquitous in environmental matrices, there is an increasing concern regarding human exposure to OP triesters or their metabolites. In this study, we measured levels of 16 OP triesters and 4 OP diesters in n = 99 human blood samples of non-occupationally exposed adults (aged 18–87) from Jiangsu Province, eastern China. Based on the measured concentrations, statistical difference and correlativity were calculated to characterize the population diversity and potential sources of OP triester and diester. Di (2-ethylhexyl) phosphate (DEHP) and 2-ethylhexyl diphenyl phosphate (EHDPP) were found in many participants' blood, with median concentrations of 1.2 (range: n.d. – 44.7, detection frequency: 99%) and 0.85 (n.d. – 28.8, 68%) ng mL−1, respectively. Blood samples of older participants contained significantly lower concentrations of OP diesters or triesters than their younger counterparts (p < 0.01). Regional- and age-specific differences in the blood concentrations of OP triesters and diesters were attributed to disparities in environmental exposure intensity. EHDPP and tris (phenyl) phosphate (TPHP), the predominant OP triesters, exhibited significant positive correlation (p < 0.01, r = 0.84) suggestive of analogous transport behavior from similar exposure sources to humans. The increased correlations between diphenyl phosphate (DPHP) and TPHP as well as with EHDPP as observed from the multivariate regression suggests that DPHP could be derived from the metabolism of both TPHP (the crucial precursor) and EHDPP. When the blood samples were subsequently screened using high-resolution spectrometry, we detected five novel OP metabolites: glucuronide conjugates of hydroxylated DEHP (OH-DEHP glucuronide conjugate), 2-ethylhexyl monophenyl phosphate (EHMPP), hydroxylated EHMPP (OH-EHMPP), dihydroxylated bis(2-butoxyethyl) phosphate (di-OH-BBOEP), and dihydroxylated tris(butyl) phosphate (di-OH-TNBP). Overall, this study provides novel information regarding the occurrence of OP triesters and diesters, and further suggested several novel OP metabolites in human blood.

Extraction Separation of Sc(III) and Fe(III) from a Strongly Acidic and Highly Concentrated Ferric Solution by D2EHPA/TBP

The solvent extraction and separation process of Sc(III) and Fe(III) from a strongly acidic and highly concentrated ferric solution using mixtures of di(2-ethylhexyl) phosphate (D2EHPA) and tri-n-butyl phosphate (TBP) in sulfonated kerosene was studied. The effects of various parameters, including D2EHPA concentration, dosage of TBP, and phase ratio, were investigated for the extraction process. The results indicated that the extraction rate of Sc(III) was 99.72% with 1.09% Fe(III) co-extracted after two stages of counter-current extraction under optimal conditions. Moreover, saturation capacity and slope analysis were used to determine the reaction mechanism. Sc(III) is extracted in the form of HSc(SO4)2·4HL. Further separation of Sc(III) and Fe(III) was realized in a scrubbing and stripping process. First, 98.67% of the co-extracted iron in the loaded organic phase was scrubbed with a dilute HCl solution by a three-stage counter-current scrubbing. Then, 85.00% of Sc(III) can be stripped efficiently with a 2-mol/L NaOH solution saturated in 1-mol/L NaCl by three-stage cross-current stripping.

Effect of Temperature to Adsorption Capacity and Coefficient Distribution on Rare Earth Elements Adsorption (Y, Gd, Dy) Using SIR

The use of REE like element of Yttrium (Y) as a superconducting material requires a purity of more than 90%, so it needs to increase the purity of Y from the settling process. The purpose of this research is to study the separation process of REE that is Y, Gd, Dy elements from REE hydroxide (REE(OH)3) using SIR method are consisting of Amberlite XAD-16 resin impregnated with Di-(2-ethylhexyl) phosphate ( D2EHPA) and Tributyl Phosphate (TBP) and determine the isotherm model on REE adsorption and determine the kinetic model of pseudo adsorption reaction. This research was started by activating XAD-16 resin and is mixed with TBP-D2EHPA solvents so it will form SIR, then it is conducted on variation of SIR composition, temperature variation of adsorption process, determination of equilibrium equation and kinetic sorption occurring in SIR adsorption based on experimental data of liquid concentration as function of time. Based on the calculation result, the most effective SIR composition for REE separation is 0.75 g, the equilibrium equation for Y, Gd and Dy follows the Henry equilibrium model and the pseudo kinetic model of the reaction order Y, Gd, and Dy is followed by the pseudo reaction of order 2 The result of separation of LTJ with SIR is said to be effective from another method because purity is obtained that is 96.73% and qualify as a super conductor material.

Comparative study on Ce (III) and La (III) solvent extraction and separation from a nitric acid medium by D2EHPA and Cyanex272

The solvent extraction of Cerium(III) and Lanthanum(III) from nitric acid solution using the organophosphorous extractants Di-(2-ethyl hexyl) phosphate (D2EHPA) and di-2,4,4- trimethylpentyl phosphoric acid (Cyanex272) in kerosene was investigated. In this study, the magnitude of the extraction of Ce(III) was found to be more significant with Cyanex272 than D2EHPA. D2EHPA was found to be a better extractant for La(III). Among the two extractants, Cyanex272 was used for the separation of Ce from La in three stages with an extraction efficiency of 90.2% for Ce. A 556 mg/L Ce solution was used for the scrubbing of La with an efficiency of ≈34%, which required multi stage scrubbing. The study of thermodynamic parameters such as enthalpy, entropy, and Gibbs free energy impart the exothermic and non-spontaneous process. The chemical speciation curves for lanthanum and cerium in the aqueous phase as a function of pH showed that the free La(III) and Ce(III) metal ion species were largely predominate between a pH = 0 and pH = 7.

Occurrence and distribution of organophosphate triesters and diesters in sludge from sewage treatment plants of Beijing, China

The occurrence and distribution of 14 organophosphate (OP) triesters and 5 diesters were investigated in sludge from eight sewage treatment plants (STPs) in Beijing, China, during 2008–2014. Tri(2-ethylhexyl) phosphate (TEHP) and tri-m-cresyl phosphate (TCrP) were the predominant triesters with the average concentration of 233–137μg/kg, respectively. Also, the polar and hydrophilic trimethyl phosphate (TMP) and triethyl phosphate (TEP) were detected in 19% and 74% of sludge samples, respectively. Three of five diesters were detected in sludge samples, and di(2-ethylhexyl) phosphate (DEHP) revealed the highest average concentration of 96.0μg/kg, followed by diphenyl phosphate (DPhP, 18.0μg/kg). The levels of OP triesters in sludge varied with the compositions of the sewage and treatment capacity of STPs, as well as the adjacent sources. In comparison with that in the former years, relatively higher concentration of total OP triesters in sludge was observed in 2014, which is consistent with the rapid growth in consumption of these chemicals in China. Finally, environmental risk assessment indicated potential harmful effects of OP triesters on soil microorganisms after sludge landfill or fertilization.

Determination of organophosphate diesters in urine samples by a high-sensitivity method based on ultra high pressure liquid chromatography-triple quadrupole-mass spectrometry

Organophosphate (OP) diesters in urine samples have potential use as biomarkers of organism exposure to environmentally relevant OP triester precursors and in particular OP triester flame retardants. This present study developed a quantitatively sensitive ultra high pressure liquid chromatography (UHPLC–MS) based method for urine and the determination of OP diesters (i.e. diphenyl phosphate (DPHP), bis(2-chloroethyl) phosphate (BCEP), bis(2-chloroisopropyl) phosphate (BDCIPP), di-n-butyl phosphate (DNBP), di(2-ethylhexyl) phosphate (DEHP), bis(1-chloro-2-propyl) phosphate (BCIPP), and bis(2-butoxyethyl) phosphate (BBOEP)). Fortified with the 7 OP diesters, 1mL of human urine sample was cleaned up using weak anion exchange solid phase extraction and eluted with high ionic strength ammonium acetate buffer. Subsequently, 4 non-chlorinated OP diesters were directly determined using UHPLC–electrospray(−)-triple quadrupole–MS (UHPLC–ESI(−)–QqQ–MS), and UHPLC–ESI(+)–QqQ–MS was used for determination of 3 chlorinated OP diesters after methylation using diazomethane. Recovery efficiencies of OP diesters ranged from 88 to 160% at three spiking levels (0.4, 2 and 10ng/mL urine). Matrix effects (MEs) and method limits of quantification (MLOQs) were 15-134% and 0.10–0.32ng/mL urine, respectively. Concentrations of OP diesters in n=12 urine samples (from 4 Canadian residents, 2014) varied as follows, nd-<0.28 (DNBP), nd-1.29 (DPHP), nd-<0.28 (DEHP), <0.16–12.33 (BCEP), nd-1.17 (BCDIPP) and nd-0.68ng/mL (BCIPP).