Environmental remediation of Pb-Cd contaminated soil with organic phosphonic acids-saponin: Conditions, effectiveness, ecological risk and recovery.

Soil washing is a rapid and efficient method for heavy metals removal. In this study, a kind of novel environmentally friendly eluent is proposed, consisting of ethylenediamine tetra methylene phosphonic acid and saponin (E-S). In a response surface optimization design (RSOD), the operating parameters were optimized and ecological effects were investigated. Additionally, soil microbial diversity and composition were discussed. Finally, an optimal method for chelator recovery was presented. The single-factor and RSOD results showed that E-S had higher remediation efficiency for Pb-Cd contaminated soil with the best parameters of duration 240 min, temperature 40 °C, E/S ratio 1:1. Under these operating conditions, the removal rates of Pb and Cd were (72.2 ± 0.5)% and (61.2 ± 0.4)% for the artificially contaminated soil and (69.2 ± 0.1)% and (65.2 ± 0.2)% for in situ contaminated soil, respectively. The contents of Pb and Cd decreased from 562.36 mg/kg to 180.41 mg/kg and 80.96 mg/kg to 27.2 mg/kg respectively, and the soil ecological risk indexes reduced from 32% to 24% for Pb and 36%-27% for Cd. Owing to the efficient enrichment of Stenotrophomonas in soil, E-S has a potential of simultaneous removal effect on organic pollutants as well. Furthermore, the results revealed that E-S can be effectively recovered (>95%) by sodium sulfide precipitation.

Initial Steps of the Acid-Catalyzed Polyoxometalate-Functionalization with Phosphonic Acid Esters.

The organo-functionalization of metal oxides is a key strategy to introduce new functionalities. Often, phosphonates are used to anchor organic moieties to a range of metal oxides. Despite their widespread use, there is a lack of understanding of the parameters which enable selective and efficient formation of organophosphonate-metal oxide hybrids. Here, we report fundamental insights into the mechanism of phosphonate anchoring to a molecular metal oxide model. Specifically, we use in situ 31P NMR spectroscopy to follow the acid-catalyzed deprotection of a model phosphonate and its subsequent condensation to form a phosphonate-functionalized Dawson-polyoxometalate. Our study shows that the nucleophilicity of the acid anion is a key parameter which controls the clean and selective deprotection and polyoxometalate attachment of phosphonates. This insight will allow researchers to expand the scope of phosphonate anchoring to metal oxides by enabling the development of mild and scalable syntheses.

Novel Insight into the Mechanisms of Neurotoxicity Induced by 6:6 PFPiA through Disturbing the Gut-Brain Axis.

As alternatives to traditional per- and polyfluoroalkyl substances, perfluoroalkyl phosphonic acids (PFPiAs) are frequently detected in aquatic environments, but the neurotoxic effects and underlying mechanisms remain unclear. In this study, male zebrafish were exposed to 6:6 PFPiA (1 and 10 nM) for 28 days, which exhibited anxiety-like symptoms. Gut microbiome results indicated that 6:6 PFPiA significantly increased the abundance of Gram-negative bacteria, leading to enhanced levels of lipopolysaccharide (LPS) and inflammation in the gut. The LPS was delivered to the brain through the gut-brain axis (GBA), damaged the blood-brain barrier (BBB), stimulated neuroinflammation, and caused apoptosis as well as neural injury in the brain. This mechanism was verified by the fact that antibiotics reduced the LPS levels in the gut and brain, accompanied by reduced inflammatory responses and anxiety-like behavior. The BBB damage also resulted in the enhanced accumulation of 6:6 PFPiA in the brain, where it might bind strongly with and activate aryl hydrocarbon receptor (AhR) to induce brain inflammation directly. Additionally, as the fish received treatment with an inhibitor of AhR, the inflammation response and anxiety-like behavior decreased distinctly. This study sheds light on the new mechanisms of neurotoxicity-induced 6:6 PFPiA due to the interruption on GBA.

Benzyl trichloroacetimidates as derivatizing agents for phosphonic acids related to nerve agents by EI-GC-MS during OPCW proficiency test scenarios.

The use of benzyl trichloroacetimidates for the benzylation of phosphonic acid nerve agent markers under neutral, basic, and slightly acidic conditions is presented. The benzyl-derived phosphonic acids were detected and analyzed by Electron Ionization Gas Chromatography-Mass Spectrometry (EI-GC-MS). The phosphonic acids used in this work included ethyl-, cyclohexyl- and pinacolyl methylphosphonic acid, first pass hydrolysis products from the nerve agents ethyl N-2-diisopropylaminoethyl methylphosphonothiolate (VX), cyclosarin (GF) and soman (GD) respectively. Optimization of reaction parameters for the benzylation included reaction time and solvent, temperature and the effect of the absence or presence of catalytic acid. The optimized conditions for the derivatization of the phosphonic acids specifically for their benzylation, included neutral as well as catalytic acid (< 5 mol%) and benzyl 2,2,2-trichloroacetimidate in excess coupled to heating the mixture to 60 °C in acetonitrile for 4 h. While the neutral conditions for the method proved to be efficient for the preparation of the p-methoxybenzyl esters of the phosphonic acids, the acid-catalyzed process appeared to provide much lower yields of the products relative to its benzyl counterpart. The method's efficiency was tested in the successful derivatization and identification of pinacolyl methylphosphonic acid (PMPA) as its benzyl ester when present at a concentration of ~ 5 µg/g in a soil matrix featured in the Organisation for the Prohibition of Chemical Weapons (OPCW) 44th proficiency test (PT). Additionally, the protocol was used in the detection and identification of PMPA when spiked at ~ 10 µg/mL concentration in a fatty acid-rich liquid matrix featured during the 38th OPCW-PT. The benzyl derivative of PMPA was partially corroborated with the instrument's internal NIST spectral library and the OPCW central analytical database (OCAD v.21_2019) but unambiguously identified through comparison with a synthesized authentic standard. The method's MDL (LOD) values for the benzyl and the p-methoxybenzyl pinacolyl methylphosphonic acids were determined to be 35 and 63 ng/mL respectively, while the method's Limit of Quantitation (LOQ) was determined to be 104 and 189 ng/mL respectively in the OPCW-PT soil matrix evaluated.

Convergent and divergent biosynthetic strategies towards phosphonic acid natural products.

The phosphonate class of natural products have received significant interests in the post-genomic era due to the relative ease with which their biosynthetic genes may be identified and the resultant final products be characterized. Recent large-scale studies of the elucidation and distributions of phosphonate pathways have provided a robust landscape for deciphering the underlying biosynthetic logic. A recurrent theme in phosphonate biosynthetic pathways is the interweaving of enzymatic reactions across different routes, which enables diversification to elaborate chemically novel scaffolds. Here, we provide a few vignettes of how Nature has utilized both convergent and divergent biosynthetic strategies to compile pathways for production of novel phosphonates. These examples illustrate how common intermediates may either be generated or intercepted to diversify chemical scaffolds and provides a starting point for both biotechnological and synthetic biological applications towards new phosphonates by similar combinatorial approaches.

Which self-etch acidic composition may result in higher dental bonds at the long-term? A network meta-analysis review of in vitro studies.

OBJECTIVES: This review evaluated the effects of the acidic composition of self-etch (SE) adhesives at the long-term bond strengths to dentin and enamel. DATA: The review followed the PRISMA Extension Statement for network meta-analysis. Studies were identified by a systematic search in PubMed, Web of Science, and Scopus databases. STUDY SELECTION: The inclusion criteria were in vitro studies that evaluated bond strength data of samples analyzed at both immediate and long-term (after aging simulation) periods and that were bonded to sound dentin/enamel using SE adhesives, with at least one group of adhesives being based on 10-MDP (10-methacryloyloxy-decyl-dihydrogen-phosphate; control) and the other group being comprised of alternative acidic monomers. Statistical analyses were conducted using two methods: standard pairwise meta-analysis (SPMA) and Bayesian network meta-analysis (NMA). Heterogeneity was assessed by using the Cochran Q test and I² statistics. RESULTS: From 5220 studies identified, 87 met the eligibility criteria and 83 were meta-analyzed. Seventeen adhesives were based on 10-MDP and 44 systems were based on alternative acids. The resin-dentin/enamel bonds were predominantly reduced after aging (∼84% of cases). From the SPMA findings, the following acidic compositions showed lower bond strength values (effect size: mean difference [MD] with 95% confidence interval [95% CI]) than 10-MDP: 4-META (MD -4.99, 95% CI: -7.21, -2.78; p<0.001); sulfonic acids (MD -9.59, 95% CI -12.19, -6.98; p<0.001); unspecified phosphate esters (MD -8.89, 95% CI -17.50, -0.28; p = 0.04); or mixed acids (MD -11.0, 95% CI -13.62, -8.38; p<0.001). The dental bonds were benefited from the presence of 10-MDP upon longer aging (>6 months). From the NMA probabilistic findings, adhesives based on 10-MDP and phosphonic acids ranked as having the best and the worst bonding potential to dentin, respectively. More than one composition (phosphonic acids and mixed acids) ranked similarly to 10-MDP in enamel. The studies scored as having moderate risk of bias (58.6%), followed by low (39.1%) and high (2.3%) risk of bias. CONCLUSION: 10-MDP is an outstanding acidic monomer that contributes to higher bonds to dentin at the long-term. In enamel, there is no evidence that one acidic composition prevails over the other. CLINICAL SIGNIFICANCE: The acidic composition of SE adhesives affects the resistance of dental bonds after simulated aging, with 10-MDP playing a significant role in the adhesion to dentin but not to the enamel. REGISTRATION NUMBER: This report is registered at the Open Science Framework (osf.io/urtdf).

Comparison of Ion Chromatography Conductivity Detection (IC-CD) and Ion Chromatography Inductively Coupled Plasma Mass Spectrometry (IC-ICP-MS) for the Determination of Phosphonic Acid in Grapevine Plant Parts, Wine, and Soil.

Potassium dihydrogen phosphonate had been allowed as a plant strengthener in organic viticulture in the European Union only until 2013, supporting the control of grapevine downy mildew. Therefore, low or nondetectable levels are a prerequisite for marketing of organic wines and, consequently, validated analytical methods are of major interest. Herein, two methods based on ion chromatography conductivity detection (IC-CD) or ion chromatography inductively coupled plasma mass spectrometry (IC-ICP-MS) for the determination of phosphonic acid (H3PO3) from 14 different plant matrices of Vitis vinifera L., wine, and soil were developed, validated, and compared. Extraction recoveries ranged from 95.1 to 99.3%. Limits of quantification (LOQ) ranged in liquid and solid samples from 3.8 to 16.8 µg/kg and 0.08 to 2.41 mg/kg for ICP-MS detection and from 39.9 to 593.7 µg/kg and 3.51 to 58.7 mg/kg for CD, respectively. Data on a current anonymized selection of 100 conventionally and 30 organically produced wines are briefly presented to demonstrate the suitability of the method.

Europium radionuclides in samarium-153-Ethylene Diamine Tetramethylene phosphonic acid (153Sm-EDTMP) radiopharmaceutical waste.

153Sm-EDTMP is widely used as a palliative radiopharmaceutical for treatment of metastatic bone pain. It is produced by neutron activation of enriched 152Sm targets in a nuclear reactor. The long-lived europium radionuclides are co-produced along with production of 153Sm and it give rise to radioactive waste in 153Sm-EDTMP production. The gamma radiation dose rate was found significant on the radioactive waste generated during the production of 153Sm-EDTMP. Residual activity in six waste samples generated in different batches of 153Sm-EDTMP production were analysed for percentage contributions of 152,154,155Eu using gamma-ray spectrometry. 154Eu was a major contributor with around 62%, and the other radioisotopes, viz. 152Eu &155Eu contribution were ∼29% & ∼9% respectively. The activity concentration of these long-lived europium radionuclides in samarium radiopharmaceutical production waste may be utilised for the dose rate estimation, and vice versa.

The sensitive detection and mechanism of Fe-3,5-dimethyl pyrazole fluorescent sensor to diethylenetriamine pentamethylene phosphonic acid: Experimental study and quantum chemical calculation.

Diethylenetriamine pentamethylene phosphonic acid (DTPMP) is one of the most commonly used amino organic phosphonates. The existing methods for DTPMP detection are complicated, time-consuming, and cannot detect trace DTPMP in the natural environment. In the present work, the Fe-based 3,5-dimethyl pyrazole fluorescent sensor (Fe-DP) was constructed. The addition of Fe3+ to DP solution can greatly decrease the fluorescent intensity of DP, while the addition of different concentrations of DTPMP will restore the fluorescence intensity of DP to different degrees, to achieve quantitative detection of DTPMP, and the detection limit (LOD) of DTPMP was lower as 0.105 µΜ. The Fe-DP fluorescent sensor exhibited excellent anti-interference ability and good stability. Moreover, the fluorescence quenching mechanism of DP by Fe3+ was revealed by UV absorption spectrum and Multiwfn wavefunction analysis based on density function theory (DFT). The results revealed that the excitation of DP belonged to local excitation, in which the electrons were donated primarily by the N atom with double bond and redistributed within the pyrazole ring.The fluorescence quenching of adding Fe3+ was not caused by resonance energy transfer or charge transfer, which did not belong to dynamic quenching, but due to the ground state complex formed by the coordination of Fe3+ and the double bond N atom on the DP pyrazole ring.

Utilization of phosphonic acid compounds by marine bacteria of the genera Phaeobacter, Ruegeria, and Thalassospira (α-Proteobacteria).

Phosphonic acid (phosphonate) that possesses a carbon-phosphours bond is a chemically stable form of organic phosphorus. Various phosphonic acids are widely distributed in oceanic waters; in particular, methylphosphonic acid (namely methylphosphonate) is believed to be responsible for global methane production. To discuss the microbial degradation of phosphonic acids, we investigated the utilization of phosphonic acid compounds by cultures of marine bacteria, Phaeobacter sp., Ruegeria sp. (Rhodobacterales), and Thalassospira sp. (Rhodospirillales). These bacterial cultures were able to grow on methylphosphonic acid as well as on the tested alkyl-, carboxy-, aminoalkyl-, and hydroxyalkyl-phosphonic acid compounds. Cell yields and growth rates of Ruegeria and Thalassospira cultures grown on methyl-, ethyl-, propyl-, and butyl-phosphonic acid compounds tended to decrease with increasing alkyl chain length. In contrast, Phaeobacter sp. grew well on such alkyl-phosphonic acids. Our results suggest that these marine bacteria, which exhibit varied utilization, are involved in microbial degradation of various phosphonic acid compounds.

A phosphonic acid anion and acid dimer dianion stabilized by proton transfer in OHN hydrogen bonds - models of structural motifs in blend polymer membranes.

The structure of intermolecular hydrogen-bonded complexes formed between tert-butylphosphonic acid and trimethylpyridine molecules has been experimentally studied as the simplest model system of the structural motifs in blend proton-conducting polymer membranes based on phosphonic acid residues. The stoichiometry of the formed complexes and proton positions in OHO and OHN hydrogen bonds were established by the H/D isotope effects and temperature dependences of the signals in 1H and 31P NMR spectra. Two structural motifs, namely, 1 : 2 and 2 : 2 acid-base complexes, were identified at the low temperature in a polar aprotic environment. In the 1 : 2 complex, one proton has passed through the hydrogen bond center creating a chain of two cooperatively coupled OHN bonds, while in the 2 : 2 complex both OHN bonds are zwitterionic and anti-cooperatively coupled to each other via a dianionic cyclic dimer of phosphonic acid in the middle. The dianionic cyclic dimer is metastable by itself, but under the used experimental conditions it is stabilized by complexation with two trimethylpyridinium cations. Additionally, quantum chemical calculations using the DFT method were carried out to support the experimental data.

Chiral Fluorescence Recognition by Anthracene Fluorescent Dyes ⊂ Water-Soluble Pillar[5] arene containing Phosphonic Acid Group (PWP[5]).

Chirality plays a pivotal role in drugs, agrochemicals and food additives et al. The enantiomers of a chiral molecule often show huge difference in bioactivity, metabolism, and toxicity et al. thereby, the recognition of chiral molecules shows an increasingly important priority. In this paper, a novel method for chiral fluorescence recognition based on anthracene fluorescent dyes (AD) ⊂ water-soluble pillar[5] arene containing phosphonic acid group (PWP[5]) is developed. The AD as guest molecule can complex with PWP [5] to form 1:1 AD ⊂ PWP[5] assembly, and this assembly can be further used as a fluorescent probe to identify D/L-phenylalanine and D/L-phenylalaninol by fluorescent titration. The fluorescence intensity of the assembly was significantly reduced for D-phenylalanine and D-phenylalaninol, while L-phenylalanine or L-phenylalaninol was added to AD ⊂ PWP[5] assembly, the fluorescence intensity of the assembly almost unchanged. Hence, the chiral recognition based on assembly between the achiral fused ring fluorescent dye and achiral PWP[5] was developed.

Natural Product-Derived Phosphonic Acids as Corrosion Inhibitors for Iron and Steel.

Organic acids, typically derived from an oil-based value chain, are frequently used as corrosion inhibitors in industrial metal working fluids. The criteria for selection of these corrosion inhibitors have changed in the last decades, and are today not only performance-driven, but influenced by ecological considerations, toxicity and regulatory standards. We present scalable semisynthetic approaches to organic corrosion inhibitors based on phosphonic acids from renewable resources. They have been evaluated by chip filter assay, potentiodynamic polarization measurements, electrochemical impedance measurements and gravimetry for corrosion protection of iron and steel in an aqueous environment at slightly alkaline pH. The efficacy of several phosphonic acids tested was found to be strongly dependent on structural features influencing molecular self-assembly of protective layers, and the solubility of salts formed with di- and trivalent cations from the media or formed during corrosion. A carboxyphosphonic acid (derived from castor oil) was found to have remarkable anticorrosive effects in all media tested. We attribute the anticorrosion properties of this carboxyphosphonic acid to the formation of particularly stable protective layers on the metal surface. It might thus serve as a commercially attractive substitute for current acidic corrosion inhibitors, derived from renewable resources.

The association between urinary glyphosate and aminomethyl phosphonic acid with biomarkers of oxidative stress among pregnant women in the PROTECT birth cohort study.

BACKGROUND: Glyphosate is a widely used herbicide in global agriculture. Glyphosate and its primary environmental degradate, aminomethyl phosphonic acid (AMPA), have been shown to disrupt endocrine function and induce oxidative stress in in vitro and animal studies. To our knowledge, these relationships have not been previously characterized in epidemiological settings. Elevated urinary levels of glyphosate and AMPA may be indicative of health effects caused by previous exposure via multiple mechanisms including oxidative stress. METHODS: Glyphosate and AMPA were measured in 347 urine samples collected between 16 and 20 weeks gestation and 24-28 weeks gestation from pregnant women in the PROTECT birth cohort. Urinary biomarkers of oxidative stress, comprising 8-isoprostane-prostaglandin-F2α (8-iso-PGF2α), its metabolite 2,3-dinor-5,6-dihydro-15-F2 t-isoprostane (8-isoprostane metabolite) and prostaglandin-F2α (PGF2α), were also measured. Linear mixed effect models assessed the association between exposures and oxidative stress adjusting for maternal age, smoking status, alcohol consumption, household income and specific gravity. Potential nonlinear trends were also assessed using tertiles of glyphosate and AMPA exposure levels. RESULTS: No significant differences in exposure or oxidative stress biomarker concentrations were observed between study visits. An interquartile range (IQR) increase in AMPA was associated with 9.5% (95% CI: 0.5-19.3%) higher 8-iso-PGF2α metabolite concentrations. Significant linear trends were also identified when examining tertiles of exposure variables. Compared to the lowest exposure group, the second and third tertiles of AMPA were significantly associated with 12.8% (0.6-26.5%) and 15.2% (1.8-30.3%) higher 8-isoprostane metabolite, respectively. An IQR increase in glyphosate was suggestively associated with 4.7% (-0.9 to 10.7%) higher 8-iso-PGF2α. CONCLUSIONS: Urinary concentrations of the main environmental degradate of glyphosate, AMPA, were associated with higher levels of certain oxidative stress biomarkers. Associations with glyphosate reflected similar trends, although findings were not as strong. Additional research is required to better characterize the association between glyphosate exposure and biomarkers of oxidative stress, as well as potential downstream health consequences.

Recent advances in the synthesis of 4'-truncated nucleoside phosphonic acid analogues.

The synthesis of five series of 4'-truncated nucleoside phosphonic acid analogues is discussed in this review: (1) 4'-truncated furanose nucleoside phosphonic acid analogues; (2) 4'-truncated pyrrolidine nucleoside phosphonic acid analogues; (3) 4'-truncated carbocyclic nucleoside phosphonic acid analogues; (4) 4'-truncated isoxazole nucleoside phosphonic acid analogues; (5) 4'-truncated miscellaneous nucleoside phosphonic acid analogues. Five different ways are used to make the phosphonate moiety: (i) Michaelis-Arbuzov reaction of RX (X = Br, I, OTf) with trialkyl phosphate; (ii) Lewis acid catalyzed Michaelis-Arbuzov reaction of glycoside with trialkyl phosphite; (iii) nucleophilic addition of a dialkyl phosphite to a carbonyl group; (iv) direct coupling reaction with amino alkyl phosphonate; (v) de novo synthesis of phosphonated-isoxazole and 1,3-dioxolane heterocycles from phosphonated starting materials. Their biological activity results are briefly discussed.

Persistent luminescence nanoparticles functionalized by polymers bearing phosphonic acid anchors: synthesis, characterization, and in vivo behaviour.

Optical in vivo imaging has become a widely used technique and is still under development for clinical diagnostics and treatment applications. For further development of the field, researchers have put much effort into the development of inorganic nanoparticles (NPs) as imaging probes. In this trend, our laboratory developed ZnGa1.995O4Cr0.005 (ZGO) nanoparticles, which can emit a bright persistent luminescence signal through the tissue transparency window for dozens of minutes and can be activated in vivo with visible irradiation. These properties endow them with unique features, allowing us to recover information over a long-time study with in vivo imaging without any background. To target tissues of interest, ZGO must circulate long enough in the blood stream, a phenomenon which is limited by the mononuclear phagocyte system (MPS). Depending on their size, charge and coating, the NPs are sooner or later opsonized and stored into the main organs of the MPS (liver, spleen, and lungs). The NPs therefore have to be coated with a hydrophilic polymer to avoid this limitation. To this end, a new functionalization method using two different polyethylene glycol phosphonic acid polymers (a linear one, later named lpPEG and a branched one, later named pPEG) has been studied in this article. The coating has been optimized and characterized in various aqueous media. The behaviour of the newly functionalized NPs has been investigated in the presence of plasmatic proteins, and an in vivo biodistribution study has been performed. Among them ZGOpPEG exhibits a long circulation time, corresponding to low protein adsorption, while presenting an effective one-step process in aqueous medium with a low hydrodynamic diameter increase. This new method is much more advantageous than another strategy we reported previously that used a two-step PEG silane coating performed in an organic solvent (dimethylformamide) for which the final hydrodynamic diameter was twice the initial diameter.

Synthesis of hybrid phosphorated indenoquinolines and biological evaluation as topoisomerase I inhibitors and antiproliferative agents.

This work describes the first synthesis of diethyl 6,6a,7,11b-tetrahydro-5H-indeno[2,1-c]quinolinylphosphonates 5, diethyl 7H-indeno[2,1-c]quinolinylphosphonates 6 and diethyl 7-oxo-7H-indeno[2,1-c]quinolinylphosphonates 7, which were prepared in good to high overall yields. The synthetic route involves a multicomponent reaction of 2-phosphonateaniline, aldehydes and indene as olefin and allows the selective generation of three stereogenic centres in a short, efficient and reliable manner. The selective dehydrogenation of 1,2,3,4-tetrahydroindenoquinolines leads to the formation of corresponding indenoquinolines, and subsequent oxidation of methylene group of the indenoquinolines allows the access to indenoquinolinones.

Separation of fosetyl and phosphonic acid in food matrices with mixed-mode HPLC column coupled with tandem mass spectrometric detection and method application to other highly polar pesticides.

The aluminum salt of fosetyl (tris(ethyl phosphonate)) is an antifungal agrochemical. This paper presents a novel high performance liquid chromatography (HPLC) method for the simultaneous determination of fosetyl and the phosphonic acid, its main metabolite, in food samples. The method is based on an ion-displacement separation performed on the recently released Luna Omega PS C18 mixed-mode HPLC column. Baseline separation of fosetyl and phosphonic acid was feasible. This was achieved by optimizing the mobile phase composition and by introducing ethylenediaminetetraacetate for all matrices in the generally used extraction medium for polar pesticides and the injection solution. The binary mobile phase consisted of 10% (v/v) methanol in water and aqueous formate buffer (pH = 3.5) in gradient elution mode. The main advantages of the method over previous method include the stable retention time and peak resolution without the need for long column priming, conditioning or regeneration. Moreover, the approach was tested with other polar pesticides including glyphosate, glufosinate, and perchlorate and showed fit-for-purpose separation. The method was validated for spinach, cherry, and wheat flour samples, and was successfully applied on oat flour and arugula quality control samples. The results obtained for the five analytes met the requirements set by EU. The limit of quantifications was much lower than the maximum residue limits and ranged from 0.02 to 0.20 mg/kg.

Elimination of amino trimethylene phosphonic acid (ATMP) antiscalant in reverse osmosis concentrate using ozone: Anti-precipitation property changes and phosphorus removal.

Amino trimethylene phosphonic acid (ATMP) was widely used as an antiscalant in reverse osmosis (RO) systems to prevent membrane scaling, and entered RO concentrate at elevated levels. However, phosphonate antiscalants in RO concentrate might aggravate phosphorus pollution, remobilize heavy metals, and adversely affect the sedimentation treatment of RO concentrate. Ozonation was found an efficient method for ATMP treatment. The ATMP removal efficiencies with 8 mg/L ozone were 100% and 86.5% for ultrapure water and RO concentrate, respectively. The ATMP mineralization efficiency reached 46.5% with 8 mg/L ozone. The rate constant for the reaction between ATMP and ozone was 1.92 × 106 M-1 s-1. Increasing the pH from 3 to 9 decreased the ATMP removal efficiency from 90% to 30.9% but increased the orthophosphate formation to ATMP removal ratio from 0.11 to 0.48. The ATMP intermediates generated with low ozone dosages exhibited moderate chelation and anti-precipitation capacity, and their chelation and anti-precipitation capacity could be further attenuated by increasing the ozone dosage. Ozonation alone enhanced the growth potential for microalgae in RO concentrate because orthophosphate formed. Combining ozonation and coagulation effectively removed 83.0% of the total phosphorus from RO concentrate. The maximum algal density of Scenedesmus sp. LX1 decreased by 78.7% by ozonation and coagulation.

Facile immobilization of ethylenediamine tetramethylene-phosphonic acid into UiO-66 for toxic divalent heavy metal ions removal: An experimental and theoretical exploration.

By the facile immobilization of ethylenediamine tetramethylene-phosphonic acid (EDTMPA) onto the surface and into the defects of UiO-66, a stable and efficient adsorbent named UiO-66-EDTMPA was obtained for the first time. In terms of removing aqueous heavy metal ions (Pb2+, Cd2+, Cu2+), the maximum adsorption capacities of UiO-66-EDTMPA reached 558.67, 271.34 and 210.89 mg/g, which were 8.77 (Pb2+), 5.63 (Cd2+) and 5.19 (Cu2+) times higher than raw UiO-66 respectively. The adsorption behavior of three heavy metal ions on UiO-66 and UiO-66-EDTMPA were investigated and compared through batch control experiments and theoretical studies. The main factors on adsorption progress (i.e., the dosage of EDTMPA, pH, ionic strength, co-existing ions, initial concentration, contact time, temperature) were explored, and the critical characterization (i.e., SEM, TEM, XRD, FT-IR, TG-DTG, XPS, N2 adsorption-desorption test) were performed. Molecular dynamics (MD) simulation (radial distribution functions (RDF) and mean square displacement (MSD)) were also applied to reveal the adsorption behavior. Besides, two new quantum chemical analyses (Hirshfeld surface and independent gradient model (IGM)) were introduced into the interaction analysis between UiO-66 and EDTMPA. The complete results showed that (1) where the hydrogen bond and (vdW) connect EDTMPA to UiO-66. (2) The coordination between O, N atoms of EDTMPA and heavy metal ions (Pb2+, Cd2+, Cu2+) resulted in spontaneous adsorption. (3) The adsorption behavior agreed with Langmuir and pseudo-second-order model, endothermic reaction. In addition, the desorption and reusability study showed promising stable and sustainable performance. This work has some guiding significance for the experimental and theoretical study of removing heavy metal ions from aqueous solutions by MOF or modified MOF materials.