Assessment of trace metal concentrations in plant oils has been considered a crucial quality control marker for potential health risks, oil flavour, and oxidative stability. A straightforward inductively coupled plasma mass spectrometry (ICP-MS) methodology was developed and validated through introduction of argon:oxygen gas mixture into plasma, allowing for a direct elemental analysis of organic matrices. This approach offers the advantage of a simple one-step preparation of plant oil samples with negligible contamination risks. The complete solubilization of the oil matrix enables the determination of total metal content from a single test tube with low dilution factor of 5. The modified plasma conditions resulted in the development of a robust and accurate ICP-MS method providing limits of detection at sub ng·g-1 levels. The ICP-MS method allowed the determination of trace levels of Ba, Cd, Cu, Fe, Mn, Pb, Sn, V, and Zn in olive, sunflower and rapeseed oils.
- MeSH
- hmotnostní spektrometrie metody MeSH
- kovy MeSH
- kyslík * analýza MeSH
- oleje rostlin chemie MeSH
- stopové prvky * analýza MeSH
- Publikační typ
- časopisecké články MeSH
This unique study provides information on Cr species and their distribution in periprosthetic tissues of patients with metal-on-polyethylene joint implants. Co-Cr-Mo alloy has been widely used in joint replacement and represents a source of metal derived species. In the case of chromium, previous studies on periprosthetic tissues revealed mainly Cr(III) distribution, whereas the potential release of carcinogenic Cr(VI) species has been still a subject of debate. Here, an analytical approach utilizing speciation and fractionation was developed to analyze periprosthetic tissue samples collected from wide range of patients with failed total hip or knee replacements. The results reveal that Cr(III) is mainly released in the form of insoluble CrPO4 and Cr2 O3 particles. The highest Cr contents were found in periprosthetic tissues of patients suffering from aseptic loosening and having more Cr-based implants in the body. Cr species penetrated tissue layers, but their levels decreased with the distance from an implant. The detailed speciation/fractionation study carried out using the set of consecutive periprosthetic tissues of a patient with extensive metallosis showed the presence of trace amounts of free Cr(III), nanoparticles, and metal-protein complexes, but the majority of Cr still occurred in CrPO4 form. Carcinogenic Cr(VI) species were not detected. Up to date, there is no published human tissue study focused on the detailed speciation of both soluble and insoluble Cr-based species in the context of failing total hip and knee replacements.
- MeSH
- chrom MeSH
- kovy MeSH
- kyčelní protézy * MeSH
- lidé MeSH
- náhrada kyčelního kloubu * MeSH
- selhání protézy MeSH
- totální endoprotéza kolene * MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
A tutorial and spreadsheet for the validation and bottom-up uncertainty evaluation of quantifications performed by instrumental methods of analysis based on linear weighted calibrations is presented. The developed tool automatically assesses if calibrator values uncertainty is negligible given instrumental signal precision, assesses signal homoscedasticity by the Levene's test, guides the selection of weighting factors and evaluates the fitness of the regression model to define the calibration curve. The spreadsheet allows the use of the linear weighted regression model without the need for collecting many replicate signals of calibrators and sample by taking previously developed detailed models of signal precision variation in the calibration interval after adjustments to the daily precision conditions. This tool was successfully applied to the determination of the mass concentration of Cd, Pb, As, Hg, Co, V and Ni in a nasal spray by ICP-MS after samples dilution and acidification. The developed uncertainty models were checked through the analysis of nasal sprays after spiking with known analyte concentration levels. The metrological compatibility between estimated and reference analyte levels for 95% or 99% confidence level supports uncertainty model adequacy. The spiked samples were quantified from many replicate signals but uncertainty evaluation from duplicate calibrator and sample signals was assessed by randomly selecting calibrators and sample signals and by numerically defining a minimum acceptable success rate of the compatibility tests. The developed model was proven adequate to quantify the uncertainty of the studied measurements.
- MeSH
- kalibrace MeSH
- lineární modely MeSH
- nejistota MeSH
- nosní spreje * MeSH
- spektrální analýza MeSH
- Publikační typ
- časopisecké články MeSH
Due to the extensive use of antimicrobial agents in human and veterinary medicine, residues of various antimicrobials get into wastewater and, subsequently, surface water. On the one hand, a combination of processes in wastewater treatment plants aims to eliminate chemical and biological pollutants; on the other hand, this environment may create conditions suitable for the horizontal transfer of resistance genes and potential selection of antibiotic-resistant bacteria. Wastewater and surface water samples (Morava River) were analyzed to determine the concentrations of 10 antibiotics and identify those exceeding so-called predicted no-effect environmental concentrations (PNECs). This study revealed that residues of five of the tested antimicrobials, namely ampicillin, clindamycin, tetracycline, tigecycline and vancomycin, in wastewater samples exceeded the PNEC. Vancomycin concentrations were analyzed with respect to the detected strains of vancomycin-resistant enterococci (VRE), in which the presence of resistance genes, virulence factors and potential relationship were analyzed. VRE were detected in 16 wastewater samples (11%) and two surface water samples (6%). The PNEC of vancomycin was exceed in 16% of the samples. Since the detected VRE did not correlate with the vancomycin concentrations, no direct relationship was confirmed between the residues of this antimicrobials and the presence of the resistant strains.
- Publikační typ
- časopisecké články MeSH
BACKGROUND: The objective of the study was to determine the association between periprosthetic concentrations of selected metals and changes induced in periprosthetic tissues (PT). METHODS: PT from 24 patients with metal-on-polyethylene or ceramic-on-polyethylene total joint replacements (TJRs) were examined. Samples underwent histological examination including quantification of cellular populations. Determination of metals was performed according to the published methodology. Results were processed using correlation analysis and Principal Component Analysis (PCA), respectively. RESULTS: Growing concentration of metals in the PT was found as a function of length of exposure (LoE). Differences in Ti, Co, Cr and V concentrations (per α = 0.05) depended on the type of alloy the implants were made from. On the contrary, the implant composition did not reflect in the different numbers of immune cells per 1 high power field, not even in distribution of the membrane type according to the Krenn classification. PCA revealed several clusters in dependence on the LoE, type of the membrane and presence of immune cells. High representation of lymphocytes in the PT was typical for clusters with the longest LoE while a higher representation of neutrophils was typical for a shorter time to reoperation. CONCLUSIONS: Correlation between the LoE and concentrations of metals in its surroundings was demonstrated. However, the tissue image analysis cannot differentiate finer, potentially metal-induced tissue changes. Importantly, the tissues become more similar with an increasing LoE. We draw a conclusion about predominantly non-specific stimulation of the PT jointly by metal and polyethylene particles in non-metal-on-metal TJRs.
- MeSH
- kovy MeSH
- kyčelní protézy * MeSH
- lidé MeSH
- lymfocyty MeSH
- náhrada kyčelního kloubu * MeSH
- polyethyleny MeSH
- protézy - design MeSH
- reoperace MeSH
- selhání protézy MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
Releasing of metals from joint replacements represents one of the current topics of modern orthopedics. Determination of metals can contribute to understanding of patient's exposure to the metals and could be used as potential biomarker to detect the failure of joint replacements. This review focuses on materials used in production of joint replacements and their release into the human body. It provides an overview of the most frequently used sample preparation procedures, instrumental techniques including elemental speciation analysis, and the previously reported concentration levels of released metals in various clinical matrices, such as blood, serum, joint fluid or tissues. Quality of results, as a non-negligible part of analytical procedure, is also discussed.
- MeSH
- kovy * analýza krev moč škodlivé účinky MeSH
- lidé MeSH
- protézy kloubů * škodlivé účinky MeSH
- selhání protézy MeSH
- spektrální analýza metody MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- práce podpořená grantem MeSH
Pharmaceutical products as well as active pharmaceutical ingredients (APIs) are checked for levels of elemental contaminants to guarantee medicines administration will not involve the consumption of level of contaminants greater than their maximum admissible intake. However, the conformity decision is affected by the measurement uncertainty function of analytical steps performance, used standards quality and how measurement performance is assessed during method validation. When an ingredient is considered conform, since the measured concentration is lower than the maximum limit, the risk of a false acceptance depends on how close the measured concentration is from the limit and on the measurement uncertainty. The analytical methods used for pharmaceutical analysis should be validated by ICH and USP recommendations, in order to prove measurements are fit for purpose. The validation must also be economically feasible and have an acceptable duration. This work discusses how to evaluate the uncertainty of elemental analysis in pharmaceutical ingredients from data collected during the validation of the analytical method by following ICH guidelines and USP chapters. A top-down uncertainty evaluation based on results from the analysis of a model API intermediate, with the native analyte after spiking at three concentration levels, where analyses are performed by two analysts in two different days, is presented. The impact of the correlation of some uncertainty components of collected results on the uncertainty evaluation is discussed and considered in the calculations. The developed measurement model was checked by a cross-validation procedure where some validation data was randomly removed and used for an independent model control. The developed uncertainty evaluation methodology was successfully applied to the analysis of Pd in a model API intermediate by ICP-MS after a micro-wave assisted acid digestion, where the risk of a false acceptance of the pharmaceuticals is determined. The measurement performance data and used spreadsheet are made available as Supplementary Material.
- MeSH
- kontaminace léku MeSH
- léčivé přípravky * MeSH
- nejistota MeSH
- referenční standardy MeSH
- spektrální analýza MeSH
- Publikační typ
- časopisecké články MeSH
The presented work proposes a novel analytical ICP-MS-based approach for the accurate and precise chromium speciation in biological tissues. The determination of total Cr(VI) and soluble Cr(III) species was carried out by alkaline EDTA extraction followed by their separation using ion-exchange high-performance liquid chromatography inductively coupled plasma mass spectrometry (IE-HPLC-ICP-MS). The developed method was validated according to the procedure given in the United States Food and Drug Administration guideline on the validation of bioanalytical methods. Validation parameters included limit of detection (≤ 0.03 μg g-1), limit of quantification (≤ 0.08 μg g-1), linearity (r ≥ 0.9998), intra-day and inter-day accuracy (86-110%) and precision (≤ 10%), extraction recovery (89-110%), carry-over effect and sensitivity. In addition, special attention was paid to the study of chromium species interconversion and the elimination of spectral interferences. Moreover, the validated ICP-MS method employing microwave acid digestion was used to determine the total Cr content in collected fractions. Finally, the whole ICP-MS-based methodology was applied to the analyses of two certified reference materials of hepatopancreas tissue. Obtained results indicated that the majority of chromium in biological tissues is bound to the solid residue, Cr(VI) was determined in none of the samples investigated. This is the first study focusing on soluble Cr(III), total Cr(VI), and total bound Cr species in biological tissues. It is characterized by efficient sample preparation and fast simultaneous analysis of Cr species with parallel total Cr analysis serving for chromium balance evaluation.
This prospective study examined the content of metals released from total joint arthroplasty into joint fluid, whole blood and periprosthetic tissues. We determined the levels of Ti, V, Nb, Co, Cr, and Mo, using inductively coupled plasma mass spectrometry, in samples from patients who underwent reoperation of total hip or knee arthroplasty. All of the patients (n = 117) included in the study had either metal on polyethylene or ceramic on polyethylene-bearing pairs. First, our results conclusively showed that the majority of released metals were deposited in periprosthetic tissues. In this context, the bloodstream turned out to be an ineffective biomarker of the effects occurring in local tissues. Second, there was a clear time-dependent nature of metallic accumulation. Based on our extensive dataset, we found significantly elevated levels of the released metals in joint fluid and periprosthetic tissues originating from loosened implants compared to stable ones, as well as recognizable differences between the groups with stable implants and aseptic loosening. Finally, it was proved that the concentrations of metals decreased dependent on the distance of the tissue from the implant. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 107B: 454-462, 2019.
- MeSH
- dospělí MeSH
- kovy farmakokinetika MeSH
- kyčelní protézy škodlivé účinky MeSH
- lidé středního věku MeSH
- lidé MeSH
- náhrada kyčelního kloubu * MeSH
- prospektivní studie MeSH
- protézy kolene škodlivé účinky MeSH
- selhání protézy škodlivé účinky MeSH
- senioři nad 80 let MeSH
- senioři MeSH
- synoviální tekutina metabolismus MeSH
- totální endoprotéza kolene * MeSH
- Check Tag
- dospělí MeSH
- lidé středního věku MeSH
- lidé MeSH
- mužské pohlaví MeSH
- senioři nad 80 let MeSH
- senioři MeSH
- ženské pohlaví MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
The objective of this study was to develop and validate a novel analytical procedure for determination of total chromium and Cr(III) and Cr(VI) species released from metal implants into whole blood and joint effusion. Firstly, the ion-pair chromatographic method employing reversed-phase high-performance liquid chromatography inductively coupled plasma mass spectrometry (ICP-MS) for analysis of species was developed. Secondly, all samples, protein and low molecular fractions were analyzed for their total chromium content using ICP-MS. This new measurement procedure was validated by the following parameters: limit of detection (0.13 μg L-1 for Cr(III), 0.14 μg L-1 for Cr(VI)), linearity of calibration, trueness (recovery 84-92%), intermediate precision (RSD < 5%). We determined statistically significantly higher chromium levels in joint effusion samples obtained from patients in comparison with a control group. On the other hand, no relevant difference among the concentrations of both species and total chromium in blood was observed. Our results show that the majority of chromium is present in the trivalent form and bound to proteins. This speciation study is rare in the field of speciation analysis in clinical samples. It is characterized by very fast and simple sample preparation without any changes in distribution or stability of both Cr forms and efficient simultaneous analysis of Cr species.
- MeSH
- chrom analýza MeSH
- hmotnostní spektrometrie MeSH
- kolenní kloub chemie MeSH
- lidé MeSH
- vysokoúčinná kapalinová chromatografie MeSH
- zubní implantáty * MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
