Development of a certified reference material for the determination of polycyclic aromatic hydrocarbons (PAHs) in rubber toy

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. Graphical abstract

Determination of Background Concentrations of Ag, Pd, Pt and Au in Highly Mineralized Ground Waters at Sub-ng L–1 Concentrations by Online Matrix Separation/Pre-Concentration Coupled to ICP-SFMS

Though not regulated in directives such as the Water Framework Directive of the European Union, the investigation of geogenic background concentrations of certain elements such as precious metals is of increasing interest, in particular for the early detection of a potential environmental pollution due to the increased use in various industrial and technological applications and in medicine. However, the precise and accurate quantification of precious metals in natural waters is challenging due to the complex matrices and the ultra-low concentrations in the (sub-) ng L−1 range. A methodological approach, based on matrix separation and pre-concentration on the strong anion exchange resin TEVA® Resin in an online mode directly coupled to ICP-SFMS, has been developed for the determination of Ag, Pt, Pd and Au in ground water. Membrane desolvation sample introduction was used to reduce oxide-based spectral interferences, which complicate the quantification of these metals with high accuracy. To overcome errors arising from matrix effects—in particular, the highly varying major ion composition of the investigated ground water samples—an isotope dilution analysis and quantification based on standard additions, respectively, were performed. The method allowed to process four samples per hour in a fully automated mode. With a sample volume of only 8 mL, enrichment factors of 6–9 could be achieved, yielding detection limits <1 ng L−1. Validation of the trueness was performed based on the reference samples. This method has been used for the analysis of the total concentrations of Ag, Pt, Pd and Au in highly mineralized ground waters collected from springs located in important geological fault zones of Austria’s territory. Concentrations ranges of 0.21–64.2 ng L−1 for Ag, 0.65–6.26 ng L−1 for Pd, 0.07–1.55 ng L−1 for Pt and 0.26–1.95 ng L−1 for Au were found.

Species-specific isotope dilution analysis of monomethylmercury in sediment using GC/ICP-ToF-MS and comparison with ICP-Q-MS and ICP-SF-MS

A recently introduced inductively coupled plasma-time-of-flight-mass spectrometer (ICP-ToF-MS) shows enhanced sensitivity compared to previous developments and superior isotope ratio precision compared to other ToF and commonly used single-collector ICP-MS instruments. Following this fact, an improvement for isotope dilution ICP-MS using the new instrumentation has been reported. This study aimed at investigating whether this improvement also meets the requirements of species-specific isotope dilution using GC/ICP-MS, where short transient signals are recorded. The results of the analysis of monomethylmercury (MMHg) of a sediment reference material show that isotope ratio precision of ICP-MS instruments equipped with quadrupole, sector-field, and time-of-flight mass analyzers is similar within a broad range of peak signal-to-noise ratio when analyzing one isotopic system. The procedural limit of quantification (LOQ) for MMHg, expressed as mass fraction of Hg being present as MMHg, w(Hg)MMHg, was similar as well for all investigated instruments and ranged between 0.003 and 0.016 μg/kg. Due to the simultaneous detection capability, the ICP-ToF-MS might, however, be more favorable when several isotopic systems are analyzed within one measurement. In a case study, the GC/ICP-ToF-MS coupling was applied for analysis of MMHg in sediments of Finow Canal, a historic German canal heavily polluted with mercury. Mass fractions between 0.180 and 41 μg/kg (w(Hg)MMHg) for MMHg, and 0.056 and 126 mg/kg (w(Hg)total) for total mercury were found in sediment samples taken from the canal upstream and downstream of a former chemical plant. Graphical abstract

Identification of Rotundone as an Important Contributor to the Flavor of Oak-Aged Spirits

Experiments were conducted to identify a compound responsible for a spicy, woody, incense-like odor note in oak-aged spirits. The target compound was extracted from oak wood and various oak-aged spirits and analyzed by multidimensional (heart-cut) gas chromatography–mass spectrometry–olfactometry (MD–GC–MS–O), and was unambiguously identified as the sesquiterpene ketone, 5-isopropenyl-3,8-dimethyl-3,4,5,6,7,8-hexadydro-1(2H)-azulenone (rotundone). Quantitation of the trace-level target compound was done by stable isotope dilution analysis (SIDA) in a variety of oak-aged spirits, including bourbon, rye, Tennessee whiskey, scotch, rum, and tequila. The content of rotundone was found to increase as a function of years of barrel aging for 4-, 8-, and 12-year-old bourbons obtained from the same manufacturer, thus confirming its origin to be from oak. In addition, odor-activity values (OAVs) were compared for selected potent odorants, including rotundone, in the same 4-, 8-, and 12-year-old bourbons, which indicated the relative importance of rotundone in the overall flavor of oak-aged spirits.

Quantification of Volatile Compounds in Wines by HS-SPME-GC/MS: Critical Issues and Use of Multivariate Statistics in Method Optimization

The aim of this review is to explore and discuss the two main aspects related to a HeadSpace Solid Phase Micro-Extraction Gas-Chromatography/Mass-Spectrometry (HS-SPME-GC/MS) quantitative analysis of volatile compounds in wines, both being fundamental to obtain reliable data. In the first section, recent advances in the use of multivariate optimization approaches during the method development step are described with a special focus on factorial designs and response surface methodologies. In the second section, critical aspects related to quantification methods are discussed. Indeed, matrix effects induced by the complexity of the volatile profile and of the non-volatile matrix of wines, potentially differing between diverse wines in a remarkable extent, often require severe assumptions if a reliable quantification is desired. Several approaches offering different levels of data reliability including internal standards, model wine calibration, a stable isotope dilution analysis, matrix-matched calibration and standard addition methods are reported in the literature and are discussed in depth here.

Dried urine spots as sampling technique for multi-mycotoxin analysis in human urine

A simple and effective approach for HPLC-MS/MS based multi-mycotoxin analysis in human urine samples was developed by application of dried urine spots (DUS) as alternative on-site sampling strategy. The newly developed method enables the detection and quantitation of 14 relevant mycotoxins and mycotoxin metabolites, including citrinin (CIT), dihydrocitrinone (DH-CIT), deoxynivalenol (DON), fumonisin B1 (FB1), T-2 Toxin (T-2), HT-2 Toxin (HT-2), ochratoxin A (OTA), 2′R-ochratoxin A (2′R-OTA), ochratoxin α (OTα), tenuazonic acid and allo-tenuazonic acid (TeA + allo-TeA), zearalenone (ZEN), zearalanone (ZAN), α-zearalenol (α-ZEL), and β-zearalenol (β-ZEL). Besides the spotting procedure, sample preparation includes enzymatic cleavage of glucuronic acid conjugates and stable isotope dilution analysis. Method validation revealed low limits of detection in the range of pg/mL urine and excellent apparent recovery rates for most analytes. Stability investigation of DUS displayed no or only slight decrease of the analyte concentration over a period of 28 days at room temperature. The new method was applied to the analysis of a set of urine samples (n = 91) from a Swedish cohort. The four analytes, DH-CIT, DON, OTA, and TeA + allo-TeA, could be detected and quantified in amounts ranging from 0.06 to 0.97 ng/mL, 3.03 to 136 ng/mL, 0.013 to 0.434 ng/mL and from 0.36 to 47 ng/mL in 38.5%, 70.3%, 68.1%, and 94.5% of the samples, respectively. Additional analysis of these urine samples with an established dilute and shoot (DaS) approach displayed a high consistency of the results obtained with both methods. However, due to higher sensitivity, a larger number of positive samples were observed using the DUS method consequently providing a suitable approach for human biomonitoring of mycotoxin exposure.

Stable Isotope Dilution Analysis of the Major Prenylated Flavonoids Found in Beer, Hop Tea, and Hops

Prenylated flavonoids from hops (Humulus lupulus) have become of interest in recent years due to a range of bioactivities. The potential health benefits of prenylated flavonoids include anti-cancerous activities and treatment of the metabolic syndrome among others. Since prenylated flavonoids from hops have shown pharmaceutical potential in clinical trials, robust analytical methods to determine their concentrations in food, supplements, and beverages are required. One such, the gold standard of analytical methods, is stable isotope dilution analysis due to its ability to compensate matrix effects and losses during sample work-up. As no commercial standards were available, the synthesis of seven different prenylated flavonoid isotopes utilizing various strategies (microwave assistance, acid base catalyst in the presence of deuterated substance and lastly, the use of Strykers catalyst) is described. The produced prenylated flavonoid isotopes were then applied in the first stable isotope dilution analysis method that quantified six natural prenylated flavonoids (Isoxanthohumol, Isoxanthohumol-C, 8-Prenylnaringenin, 6- Prenylnaringenin, Xanthohumol, and Xanthohumol-C) in beer, hop tea and hops to prove its applicability. The SIDA-LC-MS/MS method was validated resulting in LODs and LOQs for all analytes between 0.04 and 3.2 μg/L. Moreover, due to the simple clean-up the developed method allows the prospect for measuring clinical samples in the future.

Key Aroma Compounds in Two Bavarian Gins

The characteristic, dominant flavor of gin is juniper, often within a complex aroma of other botanicals. The present study examined two gins from a distillery in the German state of Bavaria; one produced with 50 individual botanicals, the other with 15. The study focused on characterizing the aroma profiles and identifying the key aroma-active compounds of the gins. Comparative sensory evaluations of the gins revealed marked differences in their aroma profiles, with the botanical-rich gin exhibiting more citrusy, orangey and fruity notes than the gin containing fewer botanicals. Instrumental analyses by gas chromatography-mass spectrometry/olfactometry (GC-MS/O) using aroma extract dilution assays (AEDA) identified terpenes as the dominant key aroma compounds, specifically limonene, 1,8-cineole, linalool, estragole and trans-anethole, with additional contributions from aldehydes, such as nonanal, and phenylpropanoids, such as eugenol and estragole. Selected compounds were quantified using stir-bar sorptive extraction (SBSE) and stabile isotope dilution analysis (SIDA) with GC-MS analysis. Further, odor thresholds and corresponding odor activity values (OAVs) of these compounds were calculated, with linalool exhibiting the highest OAV in both gins. The present analyses revealed how different botanicals alter the concentrations of key aroma compound constituents and elicit a shift in the overall aroma profile of the final spirit.