Internal Standard Correction Research Articles

Determination and Identification of Antibiotic Residues in Fruits Using Liquid Chromatography-High-Resolution Mass Spectrometry (LC-HRMS).

Antibiotic residues may be present in fruit products from trees that were treated to combat bacterial diseases such as citrus greening or blight. A liquid chromatography-high-resolution mass spectrometry (LC-HRMS) method was developed for the simultaneous determination and identification of streptomycin, kasugamycin, penicillin, and oxytetracycline residues in fruit. Samples were extracted with acidic methanol and separation was optimized for a hydrophilic interaction LC column. A Q-Exactive HRMS instrument was used to obtain product ion spectra for analyte identification. Quantitation was performed with matrix-extracted calibration curves and internal standard correction. The method was tested on many different types of fruit. In general, fortified samples demonstrated acceptable recoveries (82-116%) and reproducibility (<15% RSD). Method detection limits for these analytes were well below the established US EPA tolerance levels. It was also possible to analyze the fruit extracts prepared using this method for additional chemical contaminants using LC-HRMS.

Determination of trace elements in superalloys by inductively coupled plasma mass spectrometry with micro-reaction pretreatment

Due to complex pretreatment processes and the consumption of large amounts of high-purity chemical reagents, traditional analytical methods for determining trace element concentrations in superalloys face severe challenges. In this paper, a micro-reaction pretreatment method was developed by using a micro-reaction sealed digestion vessel under micro-pressure. The mass of the samples and the volume of acid used to dissolve the superalloys were significantly reduced. The appropriate amount of digestive acid for micro-reaction and three generalized pretreatment methods were studied. The quantitative dilution process was optimized to minimize errors through meticulous weighing procedures using a high-precision balance, and the homogeneity of the samples was verified by using Ni-based superalloy standards and general samples. Sc, Rh, and Re were selected for internal standard correction, and the matrix effect was corrected by the matrix matching method. Moreover, the mass spectral interference caused by polyatomic ions was eliminated by He collision mode. The linear correlation coefficients of the calibration curves were above 0.9995, with linear coefficients ranging from 0.2 to 100 ng/g. The detection limits for the method ranged from 0.0042 to 0.13 μg/g, and the quantification limits ranged from 0.014 to 0.41 μg/g. The results showed the precision and reliability of the newly established green micro-reaction pretreatment scheme for the determination of Ga, As, In, Sn, Sb, Tl, Pb, and Bi in nickel-based superalloys together with inductively coupled plasma mass spectrometry. The micro-reaction test results of the various groups were consistent with those of the traditional methods, and the relative standard deviation (RSD, n = 11) was less than 10 %. In addition to reducing acid consumption and increasing the test solution utilization rate by ten times, the micro-reaction method was much more accessible from cross-contamination and intensive manual work, so it has shown great potential for application in intelligent and automatic batch testing of trace elements in superalloys.

Blank sample denoising algorithm (BSDA): An effective spectral noise reduction in water sample LIBS detection

Laser-induced breakdown spectroscopy (LIBS), as an elemental composition analysis technique, has many unique advantages and great potential for applications in water detection. However, the quality of LIBS spectral signals, such as signal-to-noise ratio and stability, is often poor due to the matrix effects of water, limiting its practical performance. To effectively remove the inherent weak radiation in experimental spectral data that can be easily mistaken for noise, this paper proposes a denoising algorithm for processing spectral data using a self-built blank sample spectral database of deionized water samples, and designs a complete data processing workflow. It includes steps such as blank sample data screening, internal standard correction, blank sample correction, and spectral smoothing. Against the backdrop of marine applications, experimental spectral data for target elements Na, Mg, Ca, K, Sr, and Li were processed with this algorithm. The results show that after algorithm processing, the spectral quality was significantly improved, with the signal-to-noise ratio and detection limits of various elements improved by at least one order of magnitude. The signal-for Li increased by up to 36 times, and the detection limit for K decreased by up to 25.2 times. Additionally, tiny spectral peaks that could not be observable in the original spectral data could be effectively extracted after processing. From a technical implementation perspective, the database establishment and data process are simple and practical, with universal applicability. Therefore, this method has good potential and wide foregrounds in many other water sample LIBS detection technologies.

Establishing performance metrics for quantitative non-targeted analysis: a demonstration using per- and polyfluoroalkyl substances

Non-targeted analysis (NTA) is an increasingly popular technique for characterizing undefined chemical analytes. Generating quantitative NTA (qNTA) concentration estimates requires the use of training data from calibration “surrogates,” which can yield diminished predictive performance relative to targeted analysis. To evaluate performance differences between targeted and qNTA approaches, we defined new metrics that convey predictive accuracy, uncertainty (using 95% inverse confidence intervals), and reliability (the extent to which confidence intervals contain true values). We calculated and examined these newly defined metrics across five quantitative approaches applied to a mixture of 29 per- and polyfluoroalkyl substances (PFAS). The quantitative approaches spanned a traditional targeted design using chemical-specific calibration curves to a generalizable qNTA design using bootstrap-sampled calibration values from “global” chemical surrogates. As expected, the targeted approaches performed best, with major benefits realized from matched calibration curves and internal standard correction. In comparison to the benchmark targeted approach, the most generalizable qNTA approach (using “global” surrogates) showed a decrease in accuracy by a factor of ~4, an increase in uncertainty by a factor of ~1000, and a decrease in reliability by ~5%, on average. Using “expert-selected” surrogates (n = 3) instead of “global” surrogates (n = 25) for qNTA yielded improvements in predictive accuracy (by ~1.5×) and uncertainty (by ~70×) but at the cost of further-reduced reliability (by ~5%). Overall, our results illustrate the utility of qNTA approaches for a subclass of emerging contaminants and present a framework on which to develop new approaches for more complex use cases.Graphical

A self-calibrating flexible SERS substrate incorporating PB@Au assemblies for reliable and reproducible detection.

The precise quantitative analysis using surface-enhanced Raman spectroscopy (SERS) in an uncontrollable environment still faces a significant obstacle due to the poor reproducibility of Raman signals. Herein, we propose a facile method to fabricate a self-calibrating substrate based on a flexible polyvinyl alcohol (PVA) film comprising assemblies of Prussian blue (PB) and Au NPs (PB@Au) for reliable detection. PB cores were coated with an Au shell through simple electrostatic interaction, forming core-shell nanostructure PB@Au assemblies within the PVA film. The outer Au layer provided identical trends in enhancement for both the PB core and neighboring targets while PB cores served as an internal standard (IS) to correct signal fluctuations. The prevention of competitive adsorption on the metal surface between targets and ISs was achieved. The proposed PVA/PB@Au film exhibited enhanced stability of Raman signals after IS correction, resulting in improved spot-to-spot and batch-to-batch reproducibility with significantly reduced standard deviation (RSD) values from 11.42% and 25.02% to 4.43% and 9.39%, respectively. Simultaneously, a higher accuracy in the quantitative analysis of 4-mercaptobenzoic acid (4-MBA) and malachite green (MG) was achieved with fitting coefficient (R2) values improving from 0.9675 and 0.9418 to 0.9974 and 0.9832, respectively. Moreover, the PVA/PB@Au film was successfully applied to detect residual MG in real fish samples. This work opens up an avenue to improve the reproducibility of Raman signals for flexible SERS substrates in the detection of residues under various complex conditions.

Investigation on pretreatment method for the determination of rare earth elements in polymetallic mineral samples in Pan-Xi region by ICP-MS.

The polymetallic mineral samples in Pan-Xi region are rich in rare earth resources, and exploring an efficient and accurate analysis method is of great significance for their comprehensive utilization. In this study, the samples were decomposed by three methods, namely closed acid dissolution, open acid dissolution with five acid and alkali fusion with sodium peroxide, and the 15 REE were determined by inductively coupled plasma mass spectrometry (ICP-MS) with Rh and Re as internal standard correction elements. The comparative experiments were conducted using standard substances, and the results showed: (1) The detection limit of closed acid dissolution method was low with relative standard deviation (RSD) ranging from 2.51% to 9.56% and the accuracy of method (ΔlgC) ranging from 0.006 to 0.073, while the sample processing was long, and the results of some REE were low. (2) The RSD of open acid dissolution with five acid method ranged from 1.93% to 7.96%, and ΔlgC ranged from 0.004 to 0.045 with low results of the determination results of REE. (3) The alkali fusion with sodium peroxide method eliminated the influence of matrix effects by selecting instrument optimization, sample dilution, appropriate internal standard elements, etc. The RSD ranged from 1.24% to 6.49%, and ΔlgC ranged from 0.001 to 0.032. In conclusion, alkali fusion with sodium peroxide method has a fast analysis process, complete sample dissolution, and the accuracy and precision of test results can meet the requirements of specification (DZ/T0011-2015), which is most suitable for the analysis of REE in polymetallic mineral samples from Pan-Xi region.

A comprehensive LC-MS/MS method for the simultaneous measurement of 24 adrenal steroids: From research to clinical practice

Steroids are essential in the differential diagnosis of congenital adrenal hyperplasia (CAH) subtypes; however, they may confuse physicians with multifarious results. In this study, we established a liquid chromatography tandem mass spectrometry (LC-MS/MS) method for the simultaneous measurement of 24 steroids and developed a steroid metabolite pathway-based report to aid physicians in understanding these results. Solid-phase extraction was used to concentrate and purify target plasma steroids. The linearity, precision, recovery, and matrix effects were thoroughly evaluated. PowerBuilder was used to transfer the results from LC-MS/MS to the graphic report in a laboratory information management system (LIS) and was applied to different subtypes of CAH. Twenty-four steroids were separated and analyzed in one sample preparation and two injections using LC-MS/MS. The linearity of the steroids was excellent, with coefficients of linear regression greater than 0.99. The relative recovery ranged from 90.0 to 107.1 %, whereas the intra- and total coefficient variations were 1.6 ∼ 8.7 % and 2.0 ∼ 9.9 %, respectively. Matrix effects were compensated after internal standard correction. A graphic combination report mode was established and used to effectively identify CAH subtypes. In conclusion, a useful LC-MS/MS method and graphic combination report of 24 steroids based on their metabolite pathways were established.

Isotopic internal standard correction for the determination of diludine residue in animal-derived matrix samples using enhanced matrix removal-lipid clean-up combined with ultra-performance liquid chromatography-tandem mass spectrometry

A robust method has been established for the successfully determination of diludine (DHP) levels in animal-derived matrix samples, utilizing enhanced matrix removal-lipid clean-up (EMR-lipid) combined with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC–MS/MS). DHP-13C4 was employed as an isotopically labeled internal standard to estimate the recovery, matrix effect, and process efficiency. The water-acetonitrile mixture was utilized to extract the edible tissues (muscle, fat, kidney, and liver) of cattle and chicken, while the salting out method was employed for extracting egg and milk. The extracts were then mixed with water and acetonitrile to a constant volume, and subjected to clean-up via cartridge. Subsequently, the analytes were transferred onto a reversed-phase C18 analytical column and quantified by triple-quadrupole tandem mass spectrometry in multiple-reaction monitoring mode. Quantification was accomplished using a solvent calibration curve in conjunction with an internal standard method. The proposed method showed good linearity in the range of 0.5–50 ng mL−1 (R2 ≥ 0.999), high sensitivity (the limit of detection was 2.5 μg kg−1, and the limit of quantification was 5 μg kg−1), a high spiked recovery rate (between 82.6% and 109.4%), and repeatability (the relative deviation within the batch and the relative deviation between batches were ≤ 7.5%).

Novel Isotope Dilution High-Performance Liquid Chromatography Quadrupole–Linear Ion Trap Tandem Mass Spectrometry Method for the Determination of Five Steroid Hormones in Human Serum

Accurate measurement of endogenous steroid hormones in serum is a powerful tool for understanding the status of human adrenal diseases. Isotope dilution–liquid chromatography–tandem mass spectrometry is the most commonly used method for determination of steroids in serum. In this study, we used a laboratory-constructed quadrupole-linear ion trap (Q-LIT) tandem mass spectrometer to develop a new method for the quantification of five steroid hormones in serum. A simple and efficient pretreatment was improved, wherein the serum was extracted once by a mixed solvent of 1.0 mL of ethyl acetate and n-hexane. Using the optimized method, the regression coefficients of the calibration curves were all higher than 0.99, the limits of detection were from 0.31 to 1.25 ng mL−1, and the limits of quantification were between 1.00 and 2.50 ng mL−1. The intra-day (n = 3) relative standard deviations ranged from 4.24% to 13.79%, and the inter-day (n = 3) relative standard deviations from 3.99% to 11.43%. After internal standard correction, the relative recoveries of all steroids were from 86.08% to 106.60%. Twenty-two serum samples were analyzed by Q-LIT, which was compared with commercial triple quadrupole mass spectrometer. The results of the instruments had high consistency. Therefore, Q-LIT accurately quantified steroid hormones in human samples and may be used for clinical diagnosis and monitoring of hormone-dependent diseases.

An Approach Based on an Increased Bandpass for Enabling the Use of Internal Standards in Single Particle ICP-MS: Application to AuNPs Characterization.

This paper proposes a novel approach to implement an internal standard (IS) correction in single particle inductively coupled plasma mass spectrometry (SP ICP-MS), as exemplified for the characterization of Au nanoparticles (NPs) in complex matrices. This approach is based on the use of the mass spectrometer (quadrupole) in bandpass mode, enhancing the sensitivity for the monitoring of AuNPs while also allowing for the detection of PtNPs in the same measurement run, such that they can serve as an internal standard. The performance of the method developed was proved for three different matrices: pure water, a 5 g L-1 NaCl water solution, and another water solution containing 2.5% (m/v) tetramethylammonium hydroxide (TMAH)/0.1% Triton X-100. It was observed that matrix-effects impacted both the sensitivity of the NPs and their transport efficiencies. To circumvent this problem, two methods were used to determine the TE: the particle size method for sizing and the dynamic mass flow method for the determination of the particle number concentration (PNC). This fact, together with the use of the IS, enabled us to attain accurate results in all cases, both for sizing and for the PNC determination. Additionally, the use of the bandpass mode provides additional flexibility for this characterization, as it is possible to easily tune the sensitivity achieved for each NP type to ensure that their distributions are sufficiently resolved.

Quantitative Separation of Unknown Organic-Metal Complexes by Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry.

Dissolved organic matter (DOM) is widely recognized to control the solubility and reactivity of trace metals in the environment. However, the mechanisms that govern metal-DOM complexation remain elusive, primarily due to the analytical challenge of fractionating and quantifying metal-organic species within the complex mixture of organic compounds that comprise DOM. Here, we describe a quantitative method for fractionation and element-specific detection of organic-metal complexes using liquid chromatography with online inductively coupled plasma mass spectrometry (LC-ICP-MS). The method implements a post-column compensation gradient to stabilize ICP-MS elemental response across the LC solvent gradient, thereby overcoming a major barrier to achieving quantitative accuracy with LC-ICP-MS. With external calibration and internal standard correction, the method yields concentrations of organic-metal complexes that were consistently within 6% of their true values, regardless of the complex's elution time. We used the method to evaluate the effects of four stationary phases (C18, phenyl, amide, and pentafluoroylphenyl propyl) on the recovery and separation of environmentally relevant trace metals (Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb) in Suwannee River Fulvic Acid and Suwannee River Natural Organic Matter. The C18, amide, and phenyl phases generally yielded optimal metal recoveries (>75% for all metals except Pb), with the phenyl phase separating polar species to a greater extent than C18 or amide. We also fractionated organic-bound Fe, Cu, and Ni in oxidized and reduced soils, revealing divergent metal-DOM speciation across soil redox environments. By enabling quantitative fractionation of DOM-bound metals, our method offers a means for advancing a mechanistic understanding of metal-organic complexation throughout the environment.

Correction of the urinary testosterone to epitestosterone ratio measurement in antidoping analyses by chromatographic and mass spectrometric techniques.

The ratio of testosterone (T) to epitestosterone (E) determined in urine samples is the main biomarker used to prove T and precursors abused by athletes. Analytically, the correction of the ratio is required by the World Anti-Doping Agency. This work describes a series of experiments aimed to study when it is appropriate to correct the T/E ratio value, using different mass spectrometric techniques since only reports on GC-MS exist. Analyses using external calibrators, controls, and routine samples were performed by three different techniques GC-MS, GC-MSn , and LC-MSn . A statistical comparison of the T/E was performed after the application of two corrections previously published: Isotopic contribution peak area correction (corr_1) and use of a verified internal deuterated internal standard (TD3/ED3) correction (corr_2) and the ratio based on T and E concentrations. The use of external calibration samples introduces biases that influence not only the T and E concentrations but also the T/E ratio, even when both methods of correction are applied. The correction after applying corr_1 method barely contributed to the accuracy of the T/E calculation. Nevertheless, the application of the corr_2 method increased the accuracy between 5% and 6% when comparing theoretical and experimental T/E values. Finally, the best results were obtained by the ratio calculated directly from the estimated concentrations of T and E. Attention must be paid when the T/E is measured by LC-MSn since different acquisition modes produced significantly different results, even in MS/MS when the same transition is used for T and E.

Development of a solid phase microextraction method for the determination of nicotine in dried mushrooms.

Official control of EU market foodstuffs repeatedly reports high nicotine levels in dried wild mushrooms without any clear scientific consensus about their origin. The advised constant monitoring calls for improvements to existing methods. For this purpose, our aim was to develop a headspace solid phase microextraction (HS-SPME) method coupled to gas chromatography with mass spectrometric detection (GC-MS) that would eliminate the need for extensive sample pre-treatment. The type of fiber coating, amount of sample, extraction temperature and time, desorption time and salt addition were investigated and optimized as parameters affecting the SPME procedure. The optimized conditions were used to validate a quantitative method for nicotine analysis by matrix-matched calibration and isotopically labelled internal standard correction. The method provided good linearity (r2 = 0.9994) over the tested concentration range (0.025-1 mg kg-1), low detection limit (0.005 mg kg-1) and low quantification limit (0.017 mg kg-1) for nicotine, being below the EU foodstuff regulations. For both of the tested concentration levels (0.050 and 0.200 mg kg-1), precision expressed as relative standard deviation was below 10% (4.5% and 8.5%, respectively), while accuracy was 98.2% and 100.3%. The optimized method was then used to determine nicotine levels in 18 samples of dried Boletus mushrooms from southeastern European countries entering the EU market. We demonstrated our HS-SPME procedure to be fast, simple, sensitive, solvent-free, cost-effective and thus suitable for controlling consumer safety regarding nicotine level in dried mushrooms.

In situ probing methanogenesis in anaerobic wastewater treatment using front-face excitation-emission matrix (FF-EEM) fluorescence

Global warming and the energy crisis give rise to increasing demand for renewable energy production and resource recovery. Anaerobic methanogenesis, which transforms organic matter to methane, is the pivotal step in most resource-sustainable applications in wastewater treatment, while its evaluation and monitoring are still challenging. This study proposed a novel approach for probing methanogenesis in anaerobic wastewater treatment by in situ determining coenzyme F420 using front-face excitation-emission matrix (FF-EEM) fluorescence spectroscopy. The results indicated that the proposed method was simpler and more accurate than the conventional F420 measurement. The parallel factor analysis (PARAFAC) and the internal standard correction were used to address the fluorescence overlap and the inner-filter issues, respectively. The F420 fluorescence determined by the FF-EEM correlated well with the methane yield rate (R2 = 0.882) and the mcrA gene (R2 = 0.847), and it could be associated with the methanogenic activity of the anaerobic sludge. This study demonstrated that the FF-EEM-based method was promising in evaluating methanogenesis in anaerobic process, and could assist in the optimization of bioresource recycling in wastewater treatment.

Establishing and Verifying a Robust Liquid Chromatography-Tandem Mass Spectrometry Method to Simultaneously Measure Seven Androgens Present in Plasma Samples

Objectives: To develop a robust liquid chromatography-tandem mass spectrometry (LC–MS/MS) method to simultaneously measure seven human plasma androgens, namely testosterone (T), dihydrotestosterone (DHT), androstenedione (A4), dehydroepiandrosterone sulfate (DHEAS), dehydroepiandrosterone (DHEA), 11-ketotestosterone (11-KetoT), and 11β-hydroxytestosterone (11β-OHT). Design and Methods: Plasma was extracted via a solid phase extraction method, and the analytical performance of the assay was validated according to the Clinical &amp; Laboratory Standards Institute guidelines. Overall, 73 apparently healthy volunteers were recruited to evaluate the distribution of these seven androgens; their levels in 25 females with acne and 33 obese females were also evaluated. Results: The developed method exhibited a good precision, with the total coefficient variations (CV) and the intra-assay CVs being within 10%. Furthermore, the recoveries of T, DHT, A4, DHEA, DHEAS, 11-KetoT, and 11β-OHT were 90.3–105.8, 88.7–98.1, 92.4–102.5, 90.5–106.7, 87.6–99.9, 93.3–105.3, and 90.2–104.4%, respectively, and no significant matrix effect was observed after internal standard correction (&lt;20%). Moreover, the limits of quantification were 0.01, 0.01, 0.01, 0.10, 5.00, 0.02, and 0.02 ng/mL for T, DHT, A4, DHEA, DHEAS, 11-KetoT, and 11β-OHT, respectively, which are adequate for their accurate measurement in human plasma samples. It was also determined that patients diagnosed with acne had significantly higher levels of DHT, A4, and DHEAS, while those suffering from obesity had significantly higher levels of T and A4 but lower levels of DHT. Conclusions: A robust LC-MS/MS method for the simultaneous determination of seven androgens in plasma samples was successfully established and validated, which plays important roles in clinical application.

Enhancement by Spark Discharge in LIBS Detection of Copper Particle Contamination in Oil-Immersed Transformer

The detection of copper particles in transformer oil based on laser-induced breakdown spectroscopy (LIBS) technology has been preliminarily studied, but its limit of detection (LOD) needs to be further strengthened. Therefore, spark-discharge assistant method was used to solve the problem, and its enhancement mechanism has been studied in the research. The study of the correlation between spark-discharge-assisted LIBS (SD-LIBS) spectral intensity and Cu concentration shows that spark discharge has a significant increase in plasma size and spectral intensity; for Cu atomic lines at 324.75 and 327.39 nm, the determination coefficient <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">${R}^{{2}}$ </tex-math></inline-formula> between their internal standard correction intensity and Cu concentration is promoted to 0.996 and 0.997, respectively; spark-discharge assistant method improves the LOD of LIBS from 0.775 to 0.112 <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\mu \text{g}$ </tex-math></inline-formula> /g. Due to the great improvement in detection performance, the application prospect of LIBS as fine particles detection method in transformer oil has become practical.

A simple method for rapid screening and diagnosis of common organic acidemias: quantitative detection of serum and urine organic acid profiles based on liquid chromatography-tandem mass spectrometry.

Organic acid (OA) analysis is a specific test for inherited metabolic disorders (IMDs); however, the previous detection methods are laborious and costly. This study aims to develop a rapid method for the simultaneous quantification of serum and urine OA profiles. The method was established based on the liquid chromatography-tandem mass spectrometry (LC-MS/MS) technique. The specificity, sensitivity, robustness, and accuracy of the established method were validated. Fifteen healthy subjects and nine IMD patients were measured for clinical validation. OAs with their intrinsic isomers were completely separated. The LC-MS/MS analysis time was 5.5min. Calibration curves were linear within the ranges of 27.00μg/g for all OAs. The average correlation relationship (R) varied from 0.9891 to 0.9998. The limit of detection and limit of quantification varied from 0.003 to 0.07μg/g and 0.006 to 0.08μg/g, respectively. No obvious carryover was observed. The intra-assay, inter-assay, and total imprecisions were 1.22-4.14%, 0.90-5.20%, and 1.67-5.90%, respectively. The mean spiked recovery at the three levels varied from 94.31 to 106.68%. The matrix effects can be compensated for by internal standard correction. Nine IMD patients were identified. A robust LC-MS/MS method for the rapid determination of serum and urine OA profiles without derivatization or liquid-liquid extraction was developed and validated. The analysis of five common OAs can be completed in short minutes. This innovative LC-MS/MS method for OA profiles may present its potential in future rapid screening and diagnosis of IMDs.

Can analyte protectants compensate wastewater matrix induced enhancement effects in gas chromatography – mass spectrometry analysis?

This study aimed to investigate the ability of analyte protectants to enhance GC-MS signals and compensate matrix effects for a range of micropollutants in pure standard, effluent, and influent wastewater samples during analysis and detection. Wastewater samples were prepared for analysis using multilayer solid phase extraction for the purpose of extracting sample components with a broad range of physical-chemical properties. The sample extracts were either spiked or not spiked with target compounds and four analyte protectants: 3-ethoxy-1,2-propanediol, D-sorbitol, gluconolactone, and shikimic acid. In this way, it was possible to evaluate the matrix effects of wastewater samples and compare the use of analyte protectants with the conventional correction method of allocating a best matching internal standard to each target compound. A relation was observed between level of wastewater treatment and matrix effects, with the largest effects observed for influent samples and the smallest effects for effluent samples. Compensation of matrix effects with analyte protectants gave comparable results with the conventional correction method of allocating a best matching internal standard to each of the 13 investigated micropollutants. The best overall compensation was observed using analyte protectants and the internal standard correction method in combination.

Quantitative analysis of hydrogen isotopes in hydrogen storage material using laser-induced breakdown spectroscopy

• The scanning-coaxial LIBS system is set up for in-situ measurements in fusion reactors. • Titanium foil with different hydrogen and deuterium contents is prepared and determined. • Hydrogen isotopes are analyzed quantitatively using the internal standard method (ISM) and the calibration free method (CF-LIBS). • The single sample correction calibration free method (SSCCF) is applied to improve the accuracy. The accurate determination of hydrogen isotopes in materials is always a challenge for laser-induced breakdown spectroscopy (LIBS). In this study, the content of hydrogen isotopes in hydrogen storage materials is quantitatively analyzed by LIBS using the internal standard method (ISM) and the calibration-free method (CF-LIBS), respectively. Based on the self-built LIBS system, the concentrations of hydrogen and deuterium in titanium hydride with various stoichiometric ratios are quantitatively analyzed. The local thermodynamic equilibrium (LTE) conditions of the plasma are evaluated by the calculation results of the plasma temperature and density: the plasma temperatures are 16000 ± 1000 K calculated by Boltzmann diagram of titanium, and the plasma electron densities are about 10 22 m −3 calculated by the H α line of spectra. Through integral intensity correction, the correlation coefficient of the calibration curves of hydrogen and deuterium is successfully increased by 3% in the internal standard method; The single sample correction is used in CF-LIBS to improve the accuracy of the measurement of hydrogen isotopes in titanium hydride, and the calibration results demonstrate that the average absolute errors are 8.3% and 3.2% for hydrogen and deuterium. We also compare the calculated contents of hydrogen isotopes in titanium hydride by integral intensity correction internal standard method (IICIS) and single sample correction calibration-free method (SSCCF). The SSCCF increases the accuracy of the hydrogen isotope contents compared with CF-LIBS in the range of 20 to 55 at.%. The results are not as precise as the IICIS but meet the ITER requirements in a way. The results provide a valuable reference for the precise measurement of hydrogen isotope content in materials for applications in hydrogen energy, nuclear energy, and nuclear technology.

Biocompatible SPME coupled to GC/MS for analysis of xenobiotics in blood plasma

This work proposes a new method for biomonitoring studies focused on the screening and quantification of xenobiotics in blood-derived samples. The performance of a polydimethylsiloxane/divinylbenzene/polydimethylsiloxane (PDMS/DVB/PDMS) biocompatible extraction phase was investigated for extraction of pesticides and pharmaceuticals from plasma samples via direct immersion solid-phase microextraction (SPME) prior to gas chromatography-mass spectrometry. Under the optimum extraction settings, which included an attentive optimization of the fiber rinsing conditions, the microextraction device was able to endure 100 consecutive extractions from undiluted and diluted plasma with an overall reproducibility up to 28% for all the analytes tested, except chlorpyrifos-methyl. Optimized conditions were used to validate a quantitative method using matrix-matched calibration with isotopically labeled internal standard correction. Accuracy and precision values obtained for analysis of bovine plasma were within 96–132% and 0.05–5.82% respectively. LLOQs for all the analytes were at 1 µg L−1 and LDR ranged within 1–100 µg L−1. The applicability of this method to plasma from different species (human, rat, rabbit) was also investigated. This work represents the first step toward broader use of the biocompatible PDMS/DVB/PDMS extraction phases for analysis of multiclass xenobiotics in plasma and other complex biofluids.