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Eingeladener Vortrag
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Liquid chromatography coupled with tandem mass spectrometric detection has gained more importance for mycotoxin determination in recent years. In addition to instrumental improvements, the development of LC-MS-MS has also been a consequence of the availability of stable isotope internal standards, e.g., 13C-labelled mycotoxins. Thus, the LC-ESI-MS-MS method using a 13C15-deoxynivalenol internal standard as a state-of-the-art technique was selected as a reference procedure for an in-house method comparison study of the determination of deoxynivalenol (DON) in wheat materials. Alternative methods include LC-diode array detection, which is a frequently used routine procedure for DON-analysis, and gas chromatography after trimethylsilylation. For GC application, an electron capture detector and a negative chemical ionisation mass spectrometry detector were used, which have both been well described in the literature. The method comparison was conducted using t test statistics. Additionally, this study also calculates important method performance characteristics, including accuracy, linearity, limit of detection, limit of quantification, recovery, and variation coefficient. Furthermore, this is the first report of a GC-MS method for the determination of DON using a fully carbon-labelled 13C15-DON as an IS. The GC-MS using 13C15-DON as an IS has produced comparable results to the 13C-IS-LC-MS-MS reference method with a similar sensitivity. ECD detection was slightly less sensitive, but is also suited for DON analysis in wheat. Due to the high LOQ, the LC-DAD method seems highly applicable to the measurement of highly contaminated samples.
The aim of this study was to investigate the distribution of zearalenone in wheat kernels contaminated with this mycotoxin. Kernels from a sample of a wheat harvest affected by Fusarium culmorum were sorted into six groups according to their visual attributes. Milled portions of these groups were analysed by high-performance liquid chromatography with fluorescence and diode array detection. The clean-up was performed with an immunoaffinity column after methanol/water (4:1, v/v) extraction. The zearalenone content of the unsorted kernel fraction was 74 µg/kg. The group of healthy-looking kernels was contaminated with only 6 µg/kg of zearalenone. The groups of kernels that appeared shrunken and chalky white, damage routinely caused by Fusarium, were contaminated with 170 and 117 µg/kg, respectively. A remarkably high level of zearalenone contamination, 2,184 µg/kg, was observed for the group of reddish kernels. An association between the presence of the red pigment aurofusarin and high levels of zearalenone was found. Therefore, this pigment may be used as a marker of high zearalenone content.
Distribution of Trichothecenes, Zearalenone, and Ergosterol in a Fractionated Wheat Harvest Lot
(2008)
To investigate possible co-occurrences of type B trichothecenes and zearalenone within a Fusarium culmorum-infected wheat harvest lot, kernels were fractionated into six groups by visual criteria. The Fusarium-damaged kernels were subdivided into white, shrunken, and red kernel groups, and the remaining kernels were sorted into healthy, black spotted, and nonspecific groups. The distribution patterns of nivalenol, deoxynivalenol, zearalenone, and ergosterol were determined for possible correlations. Significant correlations between the distribution patterns were found for the mycotoxins and ergosterol for the grouped kernels (r = 0.997-0.999, p < 0.0001). Additionally, remarkably outstanding levels of nivalenol (24-fold more than the mean at 1.16 mg/kg), deoxynivalenol (27-fold more than the mean at 0.16 mg/kg), zearalenone (25-fold more than the mean at 77 µg/kg), and ergosterol (17-fold more than the mean at 13.4 mg/kg) were found in the red kernel group. Further, detailed mycotoxin and ergosterol analyses were carried out on various segments (kernel surface, conidia, bran, and flour) of the red kernels. However, the mycotoxin and ergosterol distribution profiles revealed nonsignificant correlations for these kernel segments, with the exception of deoxynivalenol and nivalenol, which were moderately correlated (r = 0.948, p = 0.035).
High-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) can be used for simultaneous quantification of various mycotoxins in contaminated food samples. Therefore, multi-mycotoxin methods have been developed in the last couple of years. To enlarge these methods for further analytes, we have developed a LC-MS/MS method for the quantification of the mycotoxin aurofusarin. Additionally, further LC-MSn experiments were performed to demonstrate the fragmentation pattern of aurofusarin. Applicable multiple reaction monitoring (MRM) transitions of aurofusarin were found and optimized by parameter variation of the tandem mass spectrometer. The applicability of the developed method was tested by analysis of naturally contaminated wheat.
For more than 110 years, BAM has been producing reference materials for a wide range of application fields. With the development of new analytical methods and new applications as well as continuously emerging more stringent requirements of laboratory accreditation with regard to quality control and metrological traceability, the demand and requirements for reference materials are increasing. This trend article gives an overview of general developments in the field of reference materials as well as developments in selected fields of application in which BAM is active. This includes inorganic and metal analysis, gas analysis, food and consumer products, and geological samples. In addition to these more traditional fields of application, developments in the areas of optical spectroscopy, particulary fluorescence methods, and nanomaterials are considered.
The article "Development of certified reference materials for the determination of cadmium and acrylamide in cocoa" was originally published in the journal "Analytical and bioanalytical chemistry" Online First without Open Access. After publication in volume 412, issue 19, page 4659–4668, the authors decided to opt for Open Choice and to make the article an Open Access publication. Therefore, the copyright of the article has been changed to ©The Author(s) 2021 and the article is forthwith distributed under the terms of the Creative Commons Attribution 4.0 International License.
Since 1 January 2019 a maximum content of 0.6 mg kg−1 cadmium (Cd) in cocoa powder sold to the final consumer or as an ingredient in sweetened cocoa powder sold to the final consumer (drinking chocolate) is set by the Commission Regulation (EU) No. 488/2014. Monitoring compliance with the specified limit value requires analytical measuring methods and reference materials for quality control. However, suitable certified reference materials intended for quality assurance and quality control purposes are still lacking. Therefore, three cocoa reference materials (ERM®-BD513, ERM®-514 and ERM®-515) were developed according to the requirements of ISO 17034 and the recommendations of ISO Guide 35. The whole process of reference material development, including material preparation, assessment of homogeneity and stability, characterisation and value assignment is presented. The assignment of the certified mass fractions was based upon an interlaboratory comparison study involving 19 expert laboratories for Cd and 12 laboratories for acrylamide. The certified mass fractions and expanded uncertainties (k = 2) of the reference materials were (0.181 ± 0.009) mg kg−1 Cd (ERM®-BD513), (0.541 ± 0.024) mg kg−1 Cd (ERM®-BD514) and (0.690 ± 0.029) mg kg−1 Cd (ERM®-BD515). Acrylamide contents are given for information.
Current trends in materials and life sciences are flanked by the need to push detection limits to single molecules or single cells, enable the characterization of increasingly complex matrices or sophisticated nanostructures, speed up the time of analysis, reduce instrument complexity and costs, and improve the reliability of data. This requires suitable analytical tools such as spectroscopic, separation and imaging techniques, mass spectrometry, and hyphenated techniques as well as sensors and their adaptation to application-specific challenges in the environmental, food, consumer product, health sector, nanotechnology, and bioanalysis. Increasing concerns about health threatening known or emerging pollutants in drinking water, consumer products, and food and about the safety of nanomaterials led to a new awareness of the importance of analytical sciences. Another important driver in this direction is the increasing demand by legislation, particularly in view of the 17 sustainable development goals by the United Nations addressing clean energy, industry, and innovation, sustainable cities, clean water, and responsible consumption and production. In this respect, also the development of analytical methods that enable the characterization of material flows in production processes and support recycling concepts of precious raw materials becomes more and more relevant. In the future, this will provide the basis for greener production in the chemical industry utilizing recycled or sustainable starting materials.
This makes analytical chemistry an essential player in terms of the circular economy helping to increase the sustainability of production processes. In the life sciences sector, products based on proteins, such as therapeutic and diagnostic antibodies, increase in importance. These increasingly biotechnologically produced functional biomolecules pose a high level of complexity of matrix and structural features that can be met only by highly advanced methods for separation, characterization, and detection. In addition, metrological traceability and target definition are still significant challenges for the future, particularly in the life sciences.
However, innovative reference materials as required for the health and food sector and the characterization of advanced materials can only be developed when suitable analytical protocols are available. The so-called reproducibility crisis in sciences underlines the importance of improved measures of quality control for all kinds of measurements and material characterization. This calls for thorough method validation concepts, suitable reference materials, and regular interlaboratory comparisons of measurements as well as better training of scientists in analytical sciences.
The important contribution of analytical sciences to these developments is highlighted by a broad collection of research papers, trend articles, and critical reviews from these different application fields. Special emphasis is dedicated to often-overlooked quality assurance and reference materials.
A method has been derived to completely recover mineral oil dispersed in water. The method involves three steps: the emulsification of the mineral oil by adding amphiphiles, the breaking of the emulsion by adding salts and the extraction of the mineral oil by a non-polar aprotic solvent. Various amphiphiles and types and concentrations of salts were tested. By using amphiphiles with HLB numbers in the range 4.7 to 40 a complete recovery of the mineral oil could be obtained for a combination of salts Na2SO4 + NaH2PO4 with total ionic strength of 6 mol/L.
Zearalenone (ZEN), an estrogenic mycotoxin produced by several species of Fusarium fungi, is a common contaminant of cereal-based food worldwide. Due to frequent occurrences associated with high levels of ZEN, maize oil is a particular source of exposure. Although a European maximumlevel for ZEN in maize oil exists according to Commission Regulation (EC) No. 1126/2007 along with a newly developed international standard method for analysis, certified reference materials (CRM) are still not available. To overcome this lack, the first CRM for the determination of ZEN in contaminated maize germ oil (ERM®-BC715) was developed in the frame of a European Reference Materials (ERM®) project according to the requirements of ISO Guide 35. The whole process of CRM development including preparation, homogeneity and stability studies, and value assignment is presented. The assignment of the certified mass fraction was based upon an in-house study using high-performance liquid chromatography isotope dilution tandem mass spectrometry. Simultaneously, to support the in-house certification study, an interlaboratory comparison study was conducted with 13 expert laboratories using different analytical methods. The certified mass fraction and expanded uncertainty (k=2) of ERM®-BC715 (362± 22) μg kg−1 ZEN are traceable to the SI. This reference material is intended for analytical quality control and contributes to the improvement of consumer protection and food safety.
Aim: To observe the variation in accumulation of Fusarium and Alternaria mycotoxins across a topographically heterogeneous field and tested biotic (fungal and bacterial abundance) and abiotic (microclimate) parameters as explanatory variables.
Methods and Results: We selected a wheat field characterized by a diversified topography, to be responsible for variations in productivity and in canopy-driven microclimate. Fusarium and Alternaria mycotoxins where quantified in wheat ears at three sampling dates between flowering and harvest at 40 points.
Tenuazonic acid (TeA), alternariol (AOH), alternariol monomethyl ether (AME), tentoxin (TEN), deoxynivalenol (DON), zearalenone (ZEN) and deoxynivalenol-3-Glucoside (DON.3G) were quantified. In canopy temperature, air and soil humidity were recorded for each point with data-loggers. Fusarium spp. as trichothecene producers, Alternaria spp. and fungal abundances were assessed using qPCR. Pseudomonas fluorescens bacteria were quantified with a culture based method. We only found DON, DON.3G, TeA and TEN to be ubiquitous across the whole field, while AME, AOH and ZEN were only occasionally detected. Fusarium was more abundant in spots with high soil humidity, while Alternaria in warmer and drier spots. Mycotoxins correlated differently to the observed explanatory variables: positive correlations between DON accumulation, tri 5 gene and Fusarium abundance were clearly detected.
The correlations among the others observed variables, such as microclimatic conditions, varied among the sampling dates. The results of statistical model identification do not exclude that species coexistence could influence mycotoxin production.
Conclusions: Fusarium and Alternaria mycotoxins accumulation varies heavily across the field and the sampling dates, providing the realism of landscapescale studies. Mycotoxin concentrations appear to be partially explained by biotic and abiotic variables.
Significance and Impact of the Study: We provide a useful experimental design and useful data for understanding the dynamics of mycotoxin biosynthesis in wheat.
Phomopsin A (PHO-A), produced by the fungus Diaporthe toxica, is a mycotoxin known to be responsible for fatal liver disease of lupin-fed sheep. The füll spectrum of the toxic secondary metabolites produced by D. toxica is still unknown. PHO-A and the naturally occurring derivatives B—E have been subject to several studies to reveal their structures as well as chemical and toxicological properties. In this work, a methylated derivative of PHO-Aisolated firom lupin seeds inoculated %vith D. toxica is described. It was characterized by high-resolution mass and NMR data and shown to be the N-methylated derivative of PHO-A 1 is cytotoxic againstHepG2 cells.
A novel method for the determination of phomopsin A (1) in lupin flour, pea flour, and bean flour as well as whole lupin plants was established based on stable isotope dilution assay (SIDA) LC-MS/MS using 15N6-1 as an isotopically labeled internal standard. Artificially infected samples were used to develop an optimized extraction procedure and sample pretreatment. The limits of detection were 0.5–1 µg/kg for all matrices. The limits of quantitation were 2–4 µg/kg. The method was used to analyze flour samples generated from selected legume seeds and lupin plant samples that had been inoculated with Diaporthe toxica and two further fungal strains. Finally, growing lupin plants infected with D. toxica were investigated to simulate a naturally in-field mycotoxicosis. Toxin levels of up to 10.1 µg/kg of 1 were found in the pods and 7.2 µg/kg in the stems and leaves.
The hepatotoxin phomopsin A (PHO-A), a secondary metabolite mainly produced by the fungus Diaporthe toxica, occurs predominantly on sweet lupins. Along with the growing interest in sweet lupins for food and feed commodities, concerns have been raised about fungal infestations, and consequently, about the determination of PHO-A.
High performance liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) represents the most suitable analytical technique for sensitive and selective detection of mycotoxins including PHO-A. However, isotopic labeled substances are needed as internal standards for a reliable and convenient quantification.
As no isotope standard for PHO-A is currently available, a biosynthesis of fully 15N6-labeled PHO-A was established by cultivation of D. toxica on defined media containing Na15NO3 and 15N-labeled yeast extract as the only nitrogen sources. The identity of 15N6-PHO-A was confirmed by high resolution mass spectrometry.
The new 15N6-labeled standard will facilitate the method development for PHO-A including a more accurate quantification by LC-MS/MS.
Mycotoxins are among the most abundant contaminants in food and feed worldwide. Therefore, in the EU maximum levels are established, e.g. for the frequently occurring Fusarium toxins deoxynivalenol (DON) and zearalenone (ZEA). Additional to DON and ZEA, modified mycotoxins are present in naturally contaminated grain products contributing significantly to the exposure of humans and animals with mycotoxins. Up to now data on the spatial distribution of many (masked) mycotoxins in the kernels of wheat are missing. The aim of the present study was to investigate the amounts of DON and ZEA as well as their most abundant derivatives DON-3-glucoside (DON-3G), 3- and 15-acetyl-DON, ZEA-14- and 16-glucoside and ZEA-14-sulphate (ZEA-14S) in mill fractions of naturally contaminated wheat batches using HPLC-MS/MS. The investigated distribution pattern in ten milling fractions is comparable among the three investigated different wheat batches. Interestingly, DON and DON-3G were found to be present to similar amounts in all fractions. In bran, the levels were only slightly higher than in the endosperm. By contrast, for ZEA and ZEA-14S a significantly higher amount of toxin is located in the fibre-rich fractions. The relative mass proportion of DON-3G comprises for only between 2.9 and 11.2% of the free DON, while the relative mass proportion of ZEA-14S is estimated to even exceed the amount of free ZEA in certain fractions. Acetylated DON derivatives and ZEA-glucosides were only detected in low amounts. The experimental results show that a significant reduction of the ZEA and ZEA-14S level in wheat flour is feasible by applying milling technology strategies. However, the almost evenly distribution of DON and DON-3G in all fractions does not allow for the technological removal of relevant toxin amounts. Furthermore, the relative share of masked forms was higher for ZEA derivatives than for the DON conjugates in the investigated wheat lots.
The ubiquitous Fusarium genus is responsible for the spoilage of vast amounts of cereals and fruits.
Besides the economic damage, the danger to human and animal health by the concomitant exposure to mycotoxins represents a serious problem. A large number of Fusarium species produce a variety of different mycotoxins of which the class of trichothecenes are of particular importance due to their toxicity.
Being identified as the common volatile precursor during the biosynthesis of trichothecenes, (−)-trichodiene (TD) is considered to be a biomarker for the respective mycotoxin content in food samples. We postulated that the development of a non-invasive, on-site GC-IMS method for the quantification of (−)-trichodiene supplemented with a stationary SIDA headspace GC-MS reference method would allow circumventing the laborious and expensive analyses of individual trichothecenes in large cereal samples.
In this work we present the syntheses of the required native calibration standard and an isotope labeled (TD-D3) internal standard.
Abstract Alternariol (AOH) and alternariol-9-monomethyl ether (AME) are two secondary metabolites of Alternaria fungi which can be found in various foodstuff like tomatoes, nuts, and grains. Due to their toxicity and potential mutagenic activity the need for the development of high-throughput methods for the supervision of AOH- and AME-levels is of increasing interest. As the availability of both native and labeled AOH and AME analytical standards is very limited we herein wish to present a novel concise approach towards their synthesis employing a ruthenium-catalyzed ortho-arylation as the key step. Finally, we demonstrate their suitability as internal standards in stable-isotope dilution assay (SIDA)-HPLC-MS/MS analysis commonly used for the quantification of the natural products in food and feed.
Metabolites from Alternaria fungi exhibit a variety of biological properties such as phytotoxic, cytotoxic, or antimicrobial activity. Optimization of a literature procedure culminated in an efficient total synthesis of (−)-altenuene as well as a stable isotope-labeled derivative suitable for implementation in a LC-MS/MS method for mycotoxin analysis.
A novel, cost-efficient method for the analytical extraction of the Fusarium mycotoxin zearalenone (ZON) from edible oils by dynamic covalent hydrazine chemistry (DCHC) was developed and validated for its application with high performance liquid chromatography-fluorescence detection (HPLC-FLD). ZON is extracted from the edible oil by hydrazone formation on a polymer resin functionalised with hydrazine groups and subsequently released by hydrolysis. Specifity and precision of this approach are superior to liquid partitioning or gel permeation chromatography (GPC). DCHC also extracts zearalanone (ZAN) but not α-/β-zearalenol or -zearalanol. The hydrodynamic properties of ZON, which were estimated using molecular simulation data, indicate that the compound is unaffected by nanofiltration through the resin pores and thus selectively extracted. The method's levels of detection and quantification are 10 and 30 µg/kg, using 0.2 g of sample. Linearity is given in the range of 10-20,000 µg/kg, the average recovery being 89%. Bias and relative standard deviations do not exceed 7%. In a sample survey of 44 commercial edible oils based on various agricultural commodities (maize, olives, nuts, seeds, etc.) ZON was detected in four maize oil samples, the average content in the positive samples being 99 µg/kg. The HPLC-FLD results were confirmed by HPLC-tandem mass spectrometry and compared to those obtained by a liquid partitioning based sample preparation procedure.
The stability of the Alternaria mycotoxins alternariol, alternariol monomethyl ether, and altenuene upon bread baking was investigated by model experiments using a spiked wholemeal wheat flour matrix. For alternariol and alternariol monomethyl ether, but not for altenuene, degradation products, formed through a sequence of hydrolysis and decarboxylation, could be identified in pilot studies. The simultaneous quantification of alternariol, alternariol monomethyl ether, altenuene, and the degradation products was achieved by a newly developed high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) multimethod. The obtained quantitative data indicate that the Alternaria mycotoxins are barely degraded during wet baking, while significant degradation occurs upon dry baking, with the stability decreasing in the order alternariol monomethyl ether > alternariol > altenuene. The novel degradation products could be detected after the wet baking of flour spiked with alternariol and in a sample survey of 24 commercial cereal based baking products.
Deacetyl tenuazonic acid
(2009)
The degradation kinetics of the Alternaria mycotoxin tenuazonic acid (l-TA) in aqueous buffer were studied over a period of 4 months at different pH levels (3.5 and 7.0) and temperatures (4, 25 and 40°C). l-TA and its degradation products were quantified by newly developed high-performance liquid chromatography methods with UV or electrospray multistage mass spectrometry detection. At pH 3.5, significant degradation occurred at 25 and 40°C, the respective l-TA half-lives being 73.8±0.4 and 14.0±0.1 days. Two degradation processes, epimerization and hydrolysis, were evaluated kinetically. The hydrolytically formed iso-deacetyl TA (iso-DTA, epimeric mixture) was found to be the stable end product of l-TA degradation under the conditions of this study. This indicates that iso-DTA as well as the l-TA epimer u-TA are formed in aqueous beverage matrices.
Tenuazonic acid (TA) is a major water soluble Alternaria mycotoxin. In the present work, a method for the quantification of TA in beer by liquid chromatography-ion-trap multistage mass spectrometry after derivatization with 2,4-dinitrophenylhydrazine is described. The method is based on a rapid workup procedure and features a LOD of 2 µg/kg without preconcentration using 400 mg of sample. Validation was performed for a working range of 8-500 µg/kg.
A total of 43 beers of different brewing styles (pilsener, wheat beer, bock beer, dark beer and alcohol free beer) was analysed. TA was detected in 37 samples, 16 samples were above the LOQ. An average content of 11 µg/kg was found, the highest incidence being 175 ± 13 µg/kg. To our knowledge, this is the first report on the occurrence of TA in beer and beverages in general.
Tenuazonic acid (TA) is a major Alternaria mycotoxin. In the present work a novel approach for the detection of TA in cereals by liquid chromatographyion-trap multistage mass spectrometry after derivatization with 2,4-dinitrophenylhydrazine is described. The product of the derivatization reaction and its major MS2 fragments were characterised by Fourier transform-ion cyclotron resonance tandem mass spectrometry. Without preconcentration, the established method features a limit of detection of 10 µg/kg using 2 g of sample in a rapid workup procedure. Accuracy, precision and linearity were evaluated in the working range of 505000 µg/kg. TA was detected in 13 and quantified in 3 out of 27 cereal samples obtained from a local supermarket, the average content being 49 µg/kg (highest incidence: 851 ± 41 µg/kg).
Polycyclic aromatic hydrocarbons (PAHs) are a large group of priority organic pollutants, which contaminate environmental compartments, food, and consumer products as well. Due to their frequent occurrence associated with elevated Levels of PAHs, plastic and rubber parts of consumer products and toys are particular sources of exposure. Although European maximum levels exist for eight carcinogenic PAHs in consumer products and toys according to REACH Regulation (EC) No. 1907/2006, certified reference materials (CRM) are still not available. To overcome this lack, the first CRM for the determination of PAHs in rubber toys (BAM-B001) was developed according to the requirements of ISO Guide 35. The whole process of CRM development including preparation, homogeneity and stability studies, and value assignment is presented.
The assignment of the certified mass fractions was based upon in-house study at BAM using stable isotope Dilution analysis (SIDA) gas chromatography mass spectrometry (GC–MS). The obtained values were confirmed by the results of two interlaboratory comparison (ILC) studies with more than 50 expert laboratories from Germany and China. The mass fractions of 14 PAHs including all REACH and GS mark regulated compounds were certified ranging between 0.2 and 15.4 mg/
kg accompanied by expanded uncertainties (coverage factor k = 2). In addition, informative values were determined for 4 PAHs, mainly due to higher uncertainties and/or lack of ILC data for confirmation. BAM-B001 is intended for analytical quality control particularly based on the AfPS GS 2019:01 PAK method and contributes to improve the chemical safety of consumer products including toys.
Polycyclic aromatic hydrocarbons (PAH) can contaminate plastic and rubber parts of consumer products including toys. PAH are present as impurities in some of the raw materials used for production of such articles, particularly in extender oils and in carbon black. Because PAH have negative effects on health (e.g. carcinogenic), standard methods have been developed in several countries to control PAH in consumer/toy products, mainly based on gas-chromatography mass-spectrometry (GC-MS).
To protect consumers from hazards of PAH, national regulations and maximum levels are already in force, for example in Germany. Recently, maximum levels for 8 PAH compounds (benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[j]fluoranthene, benzo[e]pyrene, benzo[a]pyrene and dibenz[a,h]anthracene) have been established by EC-regulation 1272/2013. This resulted in an urgent need for certified reference materials (CRM) to meet the requirements of the EC-regulation (1 mg/kg for each PAH compound in consumer products and 0.5 mg/kg in toys, respectively).
In 2016 BAM started a project to certify the PAH mass fractions in a toy CRM to fill the current gap of available reference materials. Several different toys from retailers were screened to obtain a real-life material representing PAH mass fractions in the range of the EC-maximum level. The finally selected material (rubber balls for children) was prepared and characterized with respect to homogeneity and stability of 18 PAH. The extension to other health-relevant PAH compounds, e.g. indeno[1,2,3-cd]pyrene and benzo[ghi]perylene, will increase the applicability of the CRM for costumers, e.g. from industry, conformity assessment bodies and private testing laboratories.
The poster will present the current status of the ongoing CRM project including preparation of the candidate material and results from homogeneity and stability studies. In addition, first results of a joint German-Chinese interlaboratory comparison study will be shown.
Data file (RData) containing measurement data recorded during the production process of the Certified Reference Material BAM-A001 containing Polycyclic Aromatic Hydrocarbons (PAH) in olive oil. The data can be most conveniently openend using the Shiny-App eCerto which is accessible at https://www.bam.de/eCerto.
Oxidative degradation processes of tetrabromobisphenol A (TBBPA), a brominated flame retardant (BFR) in wood, plastics and electronics, were investigated by electrochemistry (EC) coupled online to electrospray ionization mass spectrometry (ESI/MS). Oxidative phase I and II metabolites production was achieved using an electrochemical flow-through cell equipped with a boron doped diamond electrode. Structural elucidation and prediction of oxidative metabolism pathways of TBBPA according to type II ipso-substitution were based on retention time, m/z ratio in negative mode and fragmentation pattern. Using the data obtained through high resolution MS analysis and the identification of single electron transfer (SET) as the initial step of a two-electron oxidation provided the necessary information to propose a mechanism for the electrochemical oxidation of TBBPA. Oxidation reactions involving aromatic hydroxylation and β-scission were the main degradation observed when studying the electrochemical behavior of TBBPA. Computational chemistry experiments using density functional theory (DFT) allowed to identify mono-hydroxylated reaction intermediate and dismissed the mechanism involving two concurrent hydroxylation. TBBPA oxidation products were compared to known metabolites of its biological and environmental degradation confirming the ability of electrochemistry to simulate β-scission reactions.
Evaluation of methods for the analysis of soils according to § 8 of the German Federal Soil Protection Act (BBodSchG)
The German Federal Soil Protection Act establishes the conditions for effective soil protection and remediation of contaminated sites. In the German Federal Soil Protection and Contaminated Sites Ordinance (BBodSchV) limiting values and methods for the determination of environmentally harmful substances in soils are fixed. The aim of this project was to evaluate selected methods by comparative investigations and proficiency testing schemes. New methods for the determination of inorganic and organic pollutants should be developed and compared with the existing standard
methods. Despite the widespread use of ICP-OES up to now no national or international standard is available for the determination of heavy metals in soil extracts with this analytical method. The influence of spectral and non spectral interferences on the accuracy of the results was systematically investigated, especially based on aqua regia soil extracts. Analyte concentration equivalents were determined, too. Based on these results a proposal for a standard was submitted to the corresponding working group of ISO TC 190.[...]
The comparison required the assignment of the mass fraction of folic acid present as the main component in the comparison sample. Performance in the comparison is representative of a laboratory's measurement capability for the purity assignment of organic compounds of medium structural complexity [molecular weight range 300–500] and high polarity (pKOW < −2).
Methods used by the eighteen participating NMIs or DIs were based on a mass balance (summation of impurities) or qNMR approach, or the combination of data obtained using both methods. The qNMR results tended to give slightly lower values for the content of folic acid, albeit with larger associated uncertainties, compared with the results obtained by mass balance procedures. Possible reasons for this divergence are discussed in the report, without reaching a definitive conclusion as to their origin.
The comparison demonstrates that for a structurally complex polar organic compound containing a high water content and presenting a number of additional analytical challenges, the assignment of the mass fraction content property value of the main component can reasonably be achieved with an associated relative standard uncertainty in the assigned value of 0.5%
KEY COMPARISON
Under the auspices of the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM) a key comparison, CCQM K55.c, was coordinated by the Bureau International des Poids et Mesures (BIPM) in 2012. Twenty National Measurement Institutes or Designated Institutes and the BIPM participated. Participants were required to assign the mass fraction of valine present as the main component in the comparison sample for CCQM-K55.c. The comparison samples were prepared from analytical grade L-valine purchased from a commercial supplier and used as provided without further treatment or purification.
Valine was selected to be representative of the performance of a laboratory's measurement capability for the purity assignment of organic compounds of low structural complexity [molecular weight range 100300] and high polarity (pKOW > –2).
The KCRV for the valine content of the material was 992.0 mg/g with a combined standard uncertainty of 0.3 mg/g. The key comparison reference value (KCRV) was assigned by combination of KCRVs assigned from participant results for each orthogonal impurity class. The relative expanded uncertainties reported by laboratories having results consistent with the KCRV ranged from 1 mg/g to 6 mg/g when using mass balance based approaches alone, 2 mg/g to 7 mg/g using quantitative 1H NMR (qNMR) based approaches and from 1 mg/g to 2.5 mg/g when a result obtained by a mass balance method was combined with a separate qNMR result.
The material provided several analytical challenges. In addition to the need to identify and quantify various related amino acid impurities including leucine, isoleucine, alanine and a-amino butyrate, care was required to select appropriate conditions for performing Karl Fischer titration assay for water content to avoid bias due to in situ formation of water by self-condensation under the assay conditions. It also proved to be a challenging compound for purity assignment by qNMR techniques.
There was overall excellent agreement between participants in the identification and the quantification of the total and individual related structure impurities, water content, residual solvent and total non-volatile content of the sample. Appropriate technical justifications were developed to rationalise observed discrepancies in the limited cases where methodology differences led to inconsistent results.
The comparison demonstrated that to perform a qNMR purity assignment the selection of appropriate parameters and an understanding of their potential influence on the assigned value is critical for reliable implementation of the method, particularly when one or more of the peaks to be quantified consist of complex multiplet signals.