Ultra-trace Levels Research Articles

Mapping elemental solutes at sub-picogram levels during aqueous corrosion of Al alloys using diffusive gradients in thin films (DGT) with LA-ICP-MS.

A novel approach using diffusive gradients in thinfilms (DGT) with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for two-dimensional mapping of elemental solute release at sub-picogram levels during aqueous corrosion of Al alloys is presented. Evaluation of different DGT gels with mixed micro-sized binding phases (polyacrylamide-Chelex-Metsorb, polyurethane (PU)-Chelex-Metsorb, PU-Chelex-Zr(OH)4) demonstrated the superior performance of PU gels due to their tear-proof handling, low shrinkage, and compliance with green chemistry. DGT devices containing PU-Chelex-Zr(OH)4 gels, which have not been characterized for Al sampling before, showed quantitative uptake of Al, Zn, and Cu solutes over time (t = 4-48h) with higher Al capacity (ΓDGT = 6.25µgcm-2) than different gels. Application of PU-Chelex-Zr(OH)4 gels on a high-strength Al-Cu alloy (Al2219) exposed to NaCl (w = 1.5%, pH = 4.5, T = 21°C) for 15min in a novel piston-type configuration revealed reproducible patterns of Al and Zn co-solubilization with a spatial expansion ranging between 50 and 1000µm. This observation, together with complementary solid-state data from secondary electron microscopy with energy-dispersive X-ray spectroscopy, showed the presence of localized pitting corrosion at the material surface. Detection limits for total solute masses of Al, Zn, and Cu were ≤0.72pg, ≤8.38pg, and ≤0.12pg, respectively, for an area of 0.01 mm2, demonstrating the method's unique capability to localize and quantify corrosion processes at ultra-trace levels and high resolution. Our study advances the assessment of Al alloy degradation in aqueous environments, supporting the design of corrosion-resistant materials for fostering technological safety and sustainability.

Advanced review of the contributing factors for the Microwave Digestion of food matrices for trace elemental analysis

Microwaves are electromagnetic waves which move at the speed of light. Samples directly exposed to this phenomenon are heated faster than conventional conduction heating methods. This is exploited in acid assisted digestion where a food sample in a suitable acid matrix can be completely destroyed leaving a clear solution of measurable elements. In pressurised systems the temperature can be rapidly increased far above the conventional boiling point of the solvent and the closed microwave vessel environment is ideal for volatile elements.There is a constant aspiration to achieve lower levels of detection and advances in instrument capabilities with specialised plasma based techniques for the identification and quantification of individual elements at ultra-trace levels have evolved. To realise this; sample preparation, digestion efficiency and sample introduction need to be optimised. Exogenous inputs such as preparation environment, reagent grade, the analyst and apparatus cleaning steps all have the potential to leave an elemental footprint on the sample and therefore contribute to the uncertainty of the analytical result. Knowledge of sample composition and subsequent interaction with microwaves and plasma are an important consideration for complete digestion without which the result is not accurate.

A highly sensitive electrochemical sensing probe incorporating classical Berthelot's reaction and glassy carbon electrode for measuring ultra-trace levels of ammonia/ NH4+ in water

In quantifying NH3 and/or NH4+ ions, the wavelength-based spectrochemical methods involving formation of colored products of the Berthelot’s or Nessler reactions might be challenging due to auto-self absorbance, spectral overlap, and background scattering noise. Thus, the current study reports a renewable glassy carbon electrode (GCE) sensing probe combined with Berthelot’s reaction (indophenol formation) and adsorptive square - wave-anodic stripping voltammetry (Ads SWSV) at pH = 10 for detection of NH3 and/or NH4+ in water. The redox characteristics and the high surface coverage of the oxidation product of indophenol on the sensing platform suggested its use for NH3 and/or NH4+ detection. The electrochemical sensing probe for NH4+ displayed good linear relationship between 5.56 nM and 55.6 μM of NH4+ with limits of detection (LOD) and quantitation (LOQ) of 4.83 × 10-9 and 1.47 × 10-8 M, and sensing probe sensitivity of 1.27μA/μM−1 cm−2,respectively. The probe was applied for measuring NH3/NH4+in fresh and seawater samples, and the results were validated using standard ion chromatography (IC) and micro spectrophotometry assays. The assembled probe was also tolerably selective against interfering of other contaminants in a comparable potential window. Additionally, the probe has exceptional selectivity, long-term stability, and repeatability, and has good capacity to detect NH3 and/or NH4+ ions with high accuracy (recovery range = 97.14 ± 4.12–102.9 ± 4.7) in environmental water samples. The calculated Student texp and Fexp values (n = 5) were less than the tabulated ttab (2.78) and Ftab (6.39) at 95 % probability (P = 0.05, n = 5). The study offer high reliability towards NH3 and/or NH4+ detection in complex environments.

Molecularly imprinted electrochemiluminescence sensor based on a novel luminol derivative for detection of human serum albumin via click reaction.

Anovel luminol derivative of N-(1,4-dioxo-1,2,3,4-tetrahydrophthalazin-5-yl)acrylamide (DTA) with excellent luminescence efficiency was designed and synthesized. Furthermore, a molecularly imprinted electrochemiluminescence sensor (MIECLS) was fabricated to detect ultratrace levels of human serum albumin (HSA) with high sensitivity and selectivity via a click reaction. The molecularly imprinted polymers (MIPs) were formed on the electrode surface via electropolymerization with HSA as a template molecule and catechol as a monomer. In the detection process, the -SH group of HSA on the electrode and the C = C bond of acryloyl group in DTA formed a new C-S bond via the Michael addition reaction to construct the MIECLS. The higher the concentration of HSA, the greater electrochemiluminescence (ECL) intensity measured. Taking advantage of MIECLS for ECL detection (scanning potential, - 0.4 to 0.5V), there was a good linear relationship between ECL intensity and the logarithm of HSA concentration in the range 5 × 10-9 to 1 × 10-13mgmL-1. The limit of detection (LOD) of the sensor was 1.05 × 10-15mgmL-1. The sensor exhibited outstanding selectivity and stability. Thesensor was applied to detect HSA in human serum with good recoveries of 97.7-105.2%. Theconcentration of HSA was detected by electrochemical method using the gating effect of MIP.

Strain-Modulated and Nanorod-Waveguided Fluorescence in Single Zinc Oxide Nanorod-Based Immunodetection.

Mechanical strain has been shown to be a versatile and tunable means to control various properties of nanomaterials. In this work, we investigate how strain applied to individual ZnO nanorods (NRs) can affect the fluorescence signals originated from external sources of bioanalytes, which are subsequently coupled and guided onto the NRs. Specifically, we determine how factors such as the NR length and protein concentration can influence the strain-induced changes in the waveguided fluorescence intensity along the NRs. We employ a protein of tumor necrosis factor-α (TNF-α) and a fluorophore-labeled antibody in a model immunoassay reaction, after which Alexa488-TNF-α immunocomplex is formed on ZnO NRs. We elucidate the relationships between the types as well as amounts of strain on the NRs and the fluorescence intensity originated from the Alexa488-TNF-α immunocomplexes. We show that tensile (compressive) strain applied to the NR leads to an increase (decrease) in the waveguided fluorescence signals. By assessing important optical phenomena such as fluorescence intensification on nanorod ends (FINE) and degree of FINE (DoF), we confirm their linear dependence with both the types and amounts of strain. Furthermore, the strain-induced changes in both FINE and DoF are found to be independent of protein concentration. We determine that NR length plays a critical role in obtaining high strain-dependence of the measured fluorescence signals. Particularly, we ascertain that longer NRs yield larger changes in both FINE and DoF in response to the applied strain, relative to shorter ones. In addition, longer NRs permit higher linear correlation between the protein concentration and the waveguided fluorescence intensity. These outcomes provide valuable insight into exploiting strain to enhance the detection of optical signals from bioanalytes, thus enabling their quantifications even at ultra-trace levels. Coupled with the use of individual ZnO NRs demonstrated in our measurements, this work may contribute to the development of a miniaturized, highly sensitive biosensor whose signal transduction is best optimized by the application of strain.

Determination of ultra-trace level 241Am in marine sediment and seawater by combining TK200-TK221 tandem-column extraction chromatography and SF ICP-MS

Sound strategies for marine chemical monitoring call for measurement systems capable of producing comparable analytical results with demonstrated quality. This work presents the development and validation of a new analytical procedure for the determination of the 241Am mass fraction in marine sediment and seawater samples at low levels. The procedure includes a tandem-column extraction chromatography for separation of 241Am and sector field-inductively coupled plasma mass spectrometry (SF ICP-MS) for its determination. The separation is based on the application of two new extraction resins, TK200 and TK221. The acid leaching method was employed for the pre-treatment of marine sediments, while Fe(OH)3 co-precipitation was used for Am pre-concentration in seawater samples. The extraction behaviors of Am on TK221 resins in the different acidic mediums were investigated. The removal capabilities of the tandem TK200-TK221 columns for the 241Am in the presence of interfering elements including Pu, Pb, Hg, Bi, Tl, Pt, Hf, U, and Th were carefully investigated and the corresponding decontamination factors (DFs) estimated to be in the range from 104 to 106. The main interfering element Pu was efficiently removed with a DF of about 6 × 105. Matrix rare earth elements (REEs) in marine sediments were further removed by the application of TEVA resins. 241Am mass fraction was quantified by the application of external calibration and SF ICP-MS. Following the recommendations of the ISO/IEC 17025 guidelines, the validation of the analytical procedure was accomplished by executing it on the certified reference material (CRM) IAEA-385 (marine sediment) and the seawater IAEA-443 reference materials (RM). The obtained results showed that 241Am mass fractions were accurately determined in both reference samples, with excellent reproducibility (2.1 % and 7.6 %) and low LODs (0.4 fg g−1 and 0.2 fg g−1). The relative expanded uncertainties (k = 2) obtained were 17.1 % and 29.0 %, respectively. The overall analytical times for the application of the proposed procedure on the marine sediment and seawater samples were evaluated to be only about 9 h and 6.5 h, respectively. It shows great advantages for its potential applications for emergency monitoring of 241Am contamination in the marine environment.

An overview of preconcentration techniques combined with inductively coupled plasma mass spectrometry for trace element determination in biological studies.

In the last decades, the determination of trace elements in biological materials has emerged as an important area of study because of its relevance to human health and the environment. Inductively coupled plasma mass spectrometry (ICP-MS) has proven to be a powerful tool for trace element analysis, owing to its high sensitivity and ability to determine several elements in a single measurement. However, given the complex nature of biological matrices and the presence of elements, most of them at ultratrace levels, it becomes crucial to complement ICP-MS with preconcentration techniques to increase the sensitivity and selectivity of analytical methods. This article presents an exhaustive overview of liquid- and solid-phase preconcentration techniques used in combination with ICP-MS for trace element determination in different biological samples from 2000 to the present. An in-depth discussion of the advances on the application of state-of-the-art solvents and materials in trace element extraction and preconcentration is presented. Special attention is given to different strategies for elemental speciation analysis, employing both chromatographic and non-chromatographic techniques. The role of automation in these methodologies is also described. Finally, future trends and challenges related to this topic are discussed.

Determination of ultra-trace level Cr(vi) in seawater using large-volume direct injection by LC-ICP-MS with in-line matrix elimination

A method to improve the sensitivity of LC-ICP-MS for the determination of hexavalent chromium (Cr(vi)) in seawater by using the large volume injection and in-line matrix elimination.

Interference free ultratrace beryllium determination in alkaline effluents of beryllium processing plants by graphite furnace atomic absorption spectrometry after a novel graphene oxide-assisted dispersive micro solid phase extraction without using a chelating agent

Ultratrace level determination of beryllium is carried out using graphene oxide as a dispersive micro solid phase extractant in alkaline beryllium processing plant effluents.

Integrated phase separation in microliter droplets for ultratrace-enriching biomarker analysis.

Ultratrace-enriching biomarker analysis is an effective method for achieving highly accurate and enhanced sensitive detection. In this study, we have developed an enrichment detection platform by combining a minipillar array with an aqueous two-phase system (ATPS) for ultratrace enriching biomarker analysis. After optimizing the enrichment conditions of ATPS, target miRNAs at ultratrace levels specifically accumulate in the DEX-rich phase, which significantly increases the target miRNA concentration-related fluorescence intensity. Compared to non-enriched miRNA in the single-phase PEG solution, the detection limit of ATPS-enriched miRNA had improved more than 200-fold. The ATPS-based enrichment detection strategy offers a novel and convenient approach for the simultaneous detection of biomarkers with ultratrace.

Application of traceable calibration for gaseous oxidized mercury in air

BackgroundThe current speciation methods for mercury (Hg) measurements are fraught with considerable uncertainty, from sample collection to calibration. High reactivity of gaseous oxidized Hg (GOM) species and their ultra-trace level presence makes them difficult to sample and calibrate. Given that improper calibration may lead to measurement biases, reliable and metrologically traceable calibration methods are required for accurately quantifying GOM in air. In the present study, we applied the recently developed calibration method based on non-thermal plasma oxidation of elemental Hg, to a commercially available Hg air speciation system for actual environmental measurements of GOM for the first time. ResultsHg species such as HgO, HgCl2, and HgBr2 were produced with trace amounts of reactant gases (oxygen and electrolytically produced chlorine and bromine) and the production was driven by plasma-assisted oxidation. The plasma oxidation efficiency of elemental Hg with oxygen was 98.5 ± 7.5 % (k = 2), while that for chlorine and bromine was 96.8 ± 6.9 % (k = 2) and 97.4 ± 9.6 % (k = 2), respectively. The calibration method was tested against the internal permeation (Hg0) source of the Tekran 2537B Hg analyzer on-field by loading HgO to different KCl-coated denuders using the plasma. GOM concentrations were measured using the Tekran speciation system. With internal calibration, concentrations were up to 9.1 % lower than those in plasma calibration, thereby emphasizing the importance of the calibration strategy. Measurement uncertainty (k = 2) further emphasizes this distinction. Internal calibration measurement uncertainty was 36.8 %, while plasma calibration boasted lower uncertainty at 13.8 %. SignificanceThe non-thermal plasma calibration strategy, as a unique and discrete calibration method traceable to the NIST SRM 3133 for ambient air GOM measurements, provide a higher level of confidence in the accuracy of GOM measurements with several advantages over other methods. Calibrations at extreme low concentrations (<100 pg) are possible with this method relevant to ambient air GOM concentrations.

Isotopic Analysis of Lead at Ultratrace Levels Using Thermal Ionization Mass Spectrometry (TIMS) Coupled with the Continuous Heating Method: Optimization of the Data Integration Range and Method.

This study systematically and experimentally evaluates data integration methods for the isotopic analysis of Pb at ultratrace levels using thermal ionization mass spectrometry (TIMS) with a continuous heating method. The evaluation utilized a certified reference material of Pb (SRM 981). The experimental evaluations encompass different data calculation methods (methods I, II, and III) and integration ranges (full, over 1%, 25%, and 75%). Method I, in which isotope ratios were calculated based on summed ion signal intensities compensating for mass fractionation, was consistent with the certified values for 10 and 1 ng standard samples across all integration ranges. For 100 pg samples, full range calculations failed for specific isotope ratios, but reduced ranges (over 1%, 25%, and 75%) yielded values overlapping with certified ones. Method II, in which isotope ratios were calculated by averaging the precalculated isotope ratios, exhibited inferior performance compared to method I. Method III, using weighted averaging to reduce anomalous values, showed results consistent with those of method I but was recommended only for single measurements. An integration range of over 1% or 25% is preferred to exclude anomalies while compensating for mass fractionation. The optimized method was validated by comparing two different instruments used for the isotopic analysis of the reference material. The enhanced accuracy and precision provide valuable insights for researchers working in ultratrace-level Pb isotopic analysis using TIMS.

Mechanisms of chemical vapor generation by aqueous boranes for trace element analysis: a rather long and unfinished story

Abstract This paper reports a summary of the studies on the mechanisms that govern the generation of hydrides and other volatile species through reaction with aqueous boranes (CVG). This derivatization reaction has been used since the early 1970s for elemental determination and speciation from the trace level down to the ultratrace level and below. An IUPAC project, concluded in 2011, reported on the mechanisms of hydrogen transfer from borane to the analytical substrate and served to remove erroneous concepts that had dominated CVG until the early 2000s. Following the conclusion of the IUPAC project, many studies have been published on the mechanisms of CVG under conditions approaching those of analyzes of real samples. These studies included the definition of more general reaction models, which valid under non-analytical conditions, the mechanism of action of additives and interferences in CVG of volatile hydrides. In addition to the analytical utility for CVG, the results represent a contribution to the knowledge of the chemistry of aqueous boranes. Other studies will be necessary to clarify still unknown aspects, among them the identity of volatile transition metal species formed by reaction of metal ions with aqueous boranes.

Total Reflection X-ray Fluorescence Spectrometric Analysis of Ten Lanthanides at the Ultratrace Level Having a High Degree of Overlap in the Emission Lines.

The extensive use of lanthanide elements in the medical, electrical, agricultural, and nuclear fields has increased their contamination in the environment. The detrimental effect of lanthanides on human health can be reduced or eliminated by their fast determination in the concerned specimen. For this purpose, an offline conjugation of the cloud point extraction (CPE) process with total reflection X-ray fluorescence (TXRF) spectrometry was done. This process was found to provide simple, quick, and precise simultaneous determination of ten lanthanides whose emission lines have a high degree of overlap at the ultratrace level. N,N,N',N'-tetra-octyl-diglycolamide in triton X-114 micelles was found to offer a selective CPE of all of the lanthanides in the presence of higher concentrations of naturally abundant cations and anions. A multivariative partial least-squares regression (PLSR) calibration approach was preferred due to the complex overlapped spectra of L lines of the lanthanides. Ten lanthanides, viz., La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, and Lu, were simultaneously determined by this method, having concentrations in the range from 10 to 5 × 103 μg L-1. The proposed method was validated by analyzing three certified reference materials (CRMs), viz., NASS-7 seawater, SRLS-6 river water, and NIST 1640a natural water, via standard addition with the relative standard deviations of ≤10%.

Dispersive solid phase microextraction (DSP-μE) by using nanodiamond@Bi2MoO6 composite for the separation-preconcentration of Pb(II) in food and water samples

A nanodiamond@Bi2MoO6 nanocomposite was synthesized using a hydrothermal procedure. The nanodiamond@Bi2MoO6 was characterized using various techniques like BET, FT-IR, FESEM, EDX, and XRD. It was used as an adsorbent for dispersive solid phase microextraction (DSP-μE) of Pb(II) at ultra-trace levels prior to its flame atomic absorption spectrometric detection. The analytical parameters such as pH values, adsorbent dose, eluent concentration, eluent volume, eluent time, and sample volume on the quantitative recoveries of lead(II) on nanodiamond@Bi2MoO6 were optimized. Additionally, matrix effects were investigated. The LOD, LOQ, and PF were calculated as 1.75 μg L-1, 5.85 μg L-1 and 16.7, respectively. The validation of the DSP-μE procedure was checked by using certificated reference material (CRM) Wheat Gluten RM8418 and BCR Estuarine water 505 for satisfactory with 98.5 to 102.4 % recovery results. The new DSP-μE procedure was applied to be successful for Pb determination in instant noodles and water samples. The concentration of Pb(II) in instant noodles samples ranged between 23 and 194 µg kg−1. In water samples, Pb(II) concentration was observed in the range of 7.95–8.05 and 123.3–142.7 µg/L, tap water, and industrial water respectively. The estimated daily intake of total Pb(II) in the food (noodles/serving i.e., noodles, seasoning spices, water) was come out as 4.27– 16.12 µg kg−1 day−1 and compared with PTDI level.

Ultra-sensitive detection and scavenging of arsenic ions and ciprofloxacin using 3D multipurpose hemicellulose based aerogel: Adsorption mechanism and RSM optimization

Trace level detection and efficient removal of arsenite ions (As (III)) and ciprofloxacin (CPR) antibiotic was achieved using hemicellulose based ratiometric fluorescent aerogel. Hemicellulose derived from rice straw was oxidised to dialdehyde hemicellulose followed by crosslinking using chitosan via a Schiff base reaction (C = N) yielding a highly porous 3D fluorescent aerogel (CS@DAHCA). Various factors governing adsorption were analyzed by applying response surface methodology (RSM) approach. CS@DAHCA exhibited ultra-trace level monitoring with the limit of detection of 3.529 pM and 55.2 nM for As (III) and CPR, respectively. The CS@DAHCA showed maximum adsorption capacity of 185 μg g−1 and 454 mg g−1 for As (III) and CPR, respectively. Finally, the feasibility of CS@DAHCA was ascertained for real water samples confirming it as promising candidate for remediation of As (III) and CPR.

Pre-concentration of pesticides in water using isophorone diamine multiwalled carbon nanotubes-based solid-phase extraction technique and analysis by gas chromatography–mass spectrometry

The existence of pesticides in water at ultra-trace levels necessitates the use of a suitable pre-concentration method for their detection. The objective of this study was to develop an ultra-synthetic adsorbent to extract chlorpyrifos (CPF) and imazalil (IMA) pesticides in water. X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy confirm that both oxidised and isophorone diamine multiwalled carbon nanotubes (IPD-MWCNTs) were successfully prepared with an intact structure; which was further confirmed by transmission electron microscopy (TEM) and energy-dispersive spectroscopy (EDS). The Brunauer–Emmet–Teller (BET) showed a high surface area of both oxidised and IPD-MWCNTs, which is linked to the formation of additional active sites. TGA further showed that the nanocomposites were highly stable within the pesticides quantification operating temperature. CPF and IMA were recovered using a low dosage of IPD-MWCNTs adsorbent (0.030 g) and eluted by a combined solvent (ethanol and chloroform (50:50, v/v)). The adsorbent was reusable over seven repeated cycles, with an acceptable percentage relative standard deviation (%RSD) ranging from 3 to 8%. The IPD-MWCNTs adsorption sites are highly stable and cannot be easily fouled, as compared to that of oxidised MWCNTs. Lower limits of detection (LOD) and quantification (LOQ) for CPF (0.026 and 0.078 µg.L−1) and IMA (0.033 and 0.100 µg.L−1) were achieved. Better recoveries for both analytes at low and high concentrations (as well as in real water samples) were obtained by IPD-MWCNTs whereas a conventional adsorbent (i.e. polymeric reverse phase) can only achieve better recoveries at high concentrations.

Metal-organic framework and porous polymer monolith as ion-receptor carrier templates for the solid-state naked-eye sensing of ultra-trace Cr(III) from aqueous medium

We report on an effective onsite optical sensor strategy using probe-decorated porous polymer monolith (PPM) and aluminum-based metal-organic framework (MIL-53 (Al) MOF) as a reliable colorimetric sensor for the detection of ultra-trace levels of Cr3+. MOFs and PPMs have attracted considerable interest in environmental applications due to their high surface area, perpetual porosity, and tunable structural network. Here, Al-MOF and PPM materials were used as porous templates for the uniform infusion of a chromoionophoric probe, i.e., (Z)-1,2-diphenyl-2-((4-(E)-phenyldiazenyl)phenyl)imino)ethan-1-ol (DPPE), for the solid-state colorimetric recognition and capturing of Cr3+ from aqueous medium. The structural morphology and surface topography of the sensor materials have been characterized using the transmission/scanning electron microscopy, optical spectroscopy, X-ray/electron diffraction, elemental mapping, surface area/pore volume and thermal analysis to understand the surface properties and stability features of the long-range ordered porous framework. The sensor's superior structural and surface features tender faster ion diffusion to the anchored probe sites within 60 s. The sensor induces a selective ligand-to-metal charge transfer (LMCT) chelation with Cr3+, resulting in a sequence of color transition from pale orange to sepia-brown, with incremental levels of Cr3+. The significance of physicochemical factors, such as pH, probe content, sensor dose, kinetics, temperature, reusability, selectivity, sensitivity, and stability, has been optimized to maximize the ion-sensing performance. The sensors' reusability has been tested by replicating the ion-sensing performance up to eight cycles. The solid-state sensor exhibited a linear range of 1.0–200 ppb for Cr3+, with a detection limit of 0.44 and 0.53 ppb and a quantification limit of 1.39 and 2.22 ppb for DPPE-loaded PPM and Al-MOF sensors, respectively. The practical utility of the sensor materials with industrial/environmental water samples reveals excellent data reliability/reproducibility (recovery ≥99.1 %; RSD ≤2.5 %) for real-time monitoring.

Deep Eutectic Solvent-Based Highly Sensitive Turn-On Fluorescent Probe for D2O.

Owing to the importance of heavy water in spectroscopy, nuclear energy generation, chemical characterization, and biological industry, a design of a robust, cheap, nontoxic, and sensitive D2O sensor is very important. In this work, taking advantage of the singular emission fluorescence of the deep eutectic solvent prepared in our laboratory, we propose a first of its kind highly sensitive turn-on fluorescent sensor to effectively sense D2O at an ultratrace level based on rapid exchange of the labile DES proton with deuterium. This method can be used as a full-range heavy water detection strategy with a limit of detection of 0.079% (v/v) or 870 ppm. The isotopic purity (IP) obtained from DES fluorescence measurements is also in close agreement with that of the conventional FT-IR method. The current DES-based sensor thus allows both sensing and isotopic purity of D2O and can serve as one of the most sensitive monitoring strategies for heavy water analysis.

Actinide Ion (Americium-241 and Uranium-232) Interaction with Hybrid Silica-Hyperbranched Poly(ethylene imine) Nanoparticles and Xerogels.

The binding of actinide ions (Am(III) and U(VI)) in aqueous solutions by hybrid silica-hyperbranched poly(ethylene imine) nanoparticles (NPs) and xerogels (XGs) has been studied by means of batch experiments at different pH values (4, 7, and 9) under ambient atmospheric conditions. Both materials present relatively high removal efficiency at pH 4 and pH 7 (>70%) for Am(III) and U(VI). The lower removal efficiency for the nanoparticles is basically associated with the compact structure of the nanoparticles and the lower permeability and access to active amine groups compared to xerogels, and the negative charge of the radionuclide species is formed under alkaline conditions (e.g., UO2(CO3)34- and Am(CO3)2-). Generally, the adsorption process is relatively slow due to the very low radionuclide concentrations used in the study and is basically governed by the actinide diffusion from the aqueous phase to the solid surface. On the other hand, adsorption is favored with increasing temperature, assuming that the reaction is endothermic and entropy-driven, which is associated with increasing randomness at the solid-liquid interphase upon actinide adsorption. To the best of our knowledge, this is the first study on hybrid silica-hyperbranched poly(ethylene imine) nanoparticle and xerogel materials used as adsorbents for americium and uranium at ultra-trace levels. Compared to other adsorbent materials used for binding americium and uranium ions, both materials show far higher binding efficiency. Xerogels could remove both actinides even from seawater by almost 90%, whereas nanoparticles could remove uranium by 80% and americium by 70%. The above, along with their simple derivatization to increase the selectivity towards a specific radionuclide and their easy processing to be included in separation technologies, could make these materials attractive candidates for the treatment of radionuclide/actinide-contaminated water.