Jenny Nelson

Advantages of reaction cell ICP-MS on doubly charged interferences for arsenic and selenium analysis in foods

Recent reports of As concentrations in certain food and drinks have garnered public concern and led to a lowering of the US guideline maximum concentration for inorganic As in apple juice and proposed limits for As in rice products. In contrast Se is an essential micro-nutrient that can be limiting when Se-poor soils yield Se-poor food crops. Rare earth element (REE) doubly charged interferences on As and Se can be significant even when initial ICP-MS tuning minimizes doubly charged formation. We analyzed NIST 1547 (peach leaves) and 1515 (apple leaves), which contain high levels of REEs, by quadrupole ICP-MS with (He) collision mode, H2 reaction mode or triple quadrupole ICP-MS (ICP-QQQ) in mass-shift mode (O2 and O2/H2). Analysis by collision cell ICP-MS significantly over-estimated As and Se concentration due to REE doubly charged formation; mathematical correction increased the accuracy of analysis but is prone to error when analyte concentration and sensitivity is low and interferent is high. For Se, H2 reaction mode was effective in suppressing Gd2+ leading to accurate determination of Se in both SRMs without the need for mathematical correction. ICP-QQQ using mass-shift mode for As+ from m/z 75 to AsO+ at m/z 91 and Se+ from m/z 78 to SeO+ at m/z 94 alleviated doubly charged effects and resulted in accurate determination of As and Se in both SRMs without the need for correction equations. Zr and Mo isobars at 91 and 94 were shown to be effectively rejected by the MS/MS capability of the ICP-QQQ.

The combined impact of vineyard origin and processing winery on the elemental profile of red wines

The combined effects of vineyard origin and winery processing have been studied in 65 red wines samples. Grapes originating from five different vineyards within 40 miles of each other were processed in at least two different wineries. Sixty-three different elements were determined with inductively coupled-plasma mass spectrometry (ICP-MS), and wines were classified according to vineyard origin, processing winery, and the combination of both factors. Vineyard origin as well as winery processing have an impact on the elemental composition of wine, but each winery and each vineyard change the composition to a different degree. For some vineyards, wines showed a characteristic elemental pattern, independent of the processing winery, but the same was found for some wineries, with similar elemental pattern for all grapes processed in these wineries, independent of the vineyard origin. Studying the combined effects of grapegrowing and winemaking provides insight into the determination of geographical origin of red wines.

Arsenic speciation in rice cereals for infants.

The aim of this study was to conduct a survey of arsenic (As) content in rice cereals for infants. The analysis was based on the FDA Elemental Analysis Manual (EAM 4.11). An inductively coupled plasma mass spectrometer (ICP-MS) was used to determine total As. Due to the different toxicities of the chemical forms of arsenic, the ICP-MS coupled to a high-performance liquid chromatograph (HPLC) was used to perform As speciation. The total and speciated arsenic was determined in 31 different infant rice cereals sold in U.S. supermarkets. The mass fraction of total inorganic As (iAs; sum of arsenite As(III) and arsenate As(V)) concentrations ranged between 55.5 ± 1.3 and 158.0 ± 6.0 μg/kg. The average total arsenic and iAs concentrations in infant rice cereal were 174.4 and 101.4 μg/kg, respectively. There was no substantial difference in iAs levels between organic and conventional rice cereals. The mixed-grain rice cereal contained the least total (105 μg/kg) and inorganic arsenic (63 μg/kg). The major detected organoarsenical species was dimethylarsinic acid (DMA). Monomethylarsonic acid (MMA) was not detected, or only trace levels were found. Spiked sample percent recoveries for iAs, DMA, and MMA ranged from a low of 97.3% for iAs to a high of 115.0% for DMA. Results for speciated and total As in the National Institute of Standards and Technology standard reference material rice flour (NIST SRM 1568) were in good agreement with certified values. In the NIST SRM 1568 sample (n = 5) repeatability (%RSD) was 2.8% for iAs, 1.7% for DMA and species sum, and 5.3% for the total arsenic by As total method. The average percent mass balance was 99.9 ± 6.3% for the NIST SRM 1568 sample. This study provides new and much needed information on arsenic levels in rice-based infant cereals.

Profiling the trace metal composition of wine as a function of storage temperature and packaging type

The effect of wine packaging and storage temperature on the elemental profile of a commercial Cabernet Sauvignon wine was studied using inductively coupled plasma-mass spectrometry (ICP-MS). In the method, 14 trace elements were monitored in a concentration range between 0.1 and 500 μg L−1, with five of these elements showing significant concentration differences among the samples as a result of the different wine packaging and storage temperatures. Among others, increased tin levels were found in screw capped samples, probably originating from the tin liner used inside the screw caps.

Evaluation of GC-ICP-MS/MS as a New Strategy for Specific Heteroatom Detection of Phosphorus, Sulfur, and Chlorine Determination in Foods.

For the first time in the literature, application of a GC-ICP-MS/MS method for the selective and sensitive detection of specific heteroatoms of phosphorus, sulfur, and chlorine has been accomplished. As a proof of concept, organophosphorus, organosulfur, and organochlorine pesticides in various food matrices have been studied. For the detection of organophosphorus and organosulfur pesticides, oxygen was used in the collision reaction cell (CRC) to convert P (m/z 31) to PO(+) (m/z 47) and S (m/z 32) to SO(+) (m/z 48). Similarly, ClH2(+) (m/z 37) was monitored after the reaction of Cl (m/z 35) with hydrogen in the CRC for the determination of organochlorine pesticides. Real food samples (baby food purees, fresh vegetables, loose tea) were screened for their pesticide content, following preparation of triplicate extracts using QuEChERS (quick, easy, cheap, effective, rugged, and safe). Excellent linearity with correlation coefficients R ≥ 0.997 was achieved, and the lowest detection limits obtained for the organophosphorus, organosulfur, and organochlorine pesticides were 0.0005, 0.675, and 0.144 μg/kg, respectively.

Total arsenic analysis in Californian wines with hydride generation – microwave plasma – atomic emission spectroscopy (HG-MP-AES)

The total arsenic concentrations of forty Californian wine samples were analyzed using a novel hydride generation-microwave plasma atomic emission spectroscopy (HG-MP-AES). Prior to analysis, various arsenic species were reduced with potassium iodide, and detected as gaseous arsenic trihydride. The method detection limit was determined to be 0.38 μg L−1. Total arsenic levels of the different tested wine styles (white, rose, red, Port, sparkling) ranged from below the detection limit to 43.8 μg L−1. The developed method provides quick and reliable quantitation of total arsenic content for a variety of wine styles down to levels below the EPA drinking water limit (10 μg L−1). This is the first report of HG-MP-AES, utilizing the Multimode Sample Introduction System (MSIS), for the determination of total arsenic.

Correlating Wine Quality Indicators to Chemical and Sensory Measurements

Twenty-seven commercial Californian Cabernet Sauvignon wines of different quality categories were analyzed with sensory and chemical methods. Correlations between five quality proxies—points awarded during a wine competition, wine expert scores, retail price, vintage, and wine region—were correlated to sensory attributes, volatile compounds, and elemental composition. Wine quality is a multi-faceted construct, incorporating many different layers. Depending on the quality proxy studied, significant correlations between quality and attributes, volatiles and elements were found, some of them previously reported in the literature.

Elemental Profiling of Malbec Wines under Controlled Conditions Using Microwave Plasma-Atomic Emission Spectroscopy

Microwave plasma-atomic emission spectrometry (MP-AES) was used for elemental analysis of Malbec wines from Argentina and the US. Using results from the analysis of six elements (Sr, Rb, Ca, K, Na, and Mg), Malbec wines from Mendoza, Argentina, and California were compared. The Malbec wines from these two countries were distinguished based on the results of their elemental profiles in a partial least squares-discriminant analysis. To our knowledge, this is the first time that MP-AES was used to determine the geographical origin of Malbec wines using six different elements.

Comparison of Dilution, Filtration, and Microwave Digestion Sample Pretreatments in Elemental Profiling of Wine by ICP-MS

Wine elemental composition varies by cultivar, geographic origin, viticultural and enological practices, and is often used for authenticity validation. Elemental analysis of wine by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is challenging due to the potential for non-spectral interferences and plasma instability arising from organic matrix components. Sample preparation mitigates these interferences, however, conflicting recommendations of best practices in ICP-MS analysis of wine have been reported. This study compared direct dilution, microwave-assisted acid digestion, and two filtration sample pretreatments, acidification prior to filtration and filtration followed by acidification, in elemental profiling of one white and three red table wines by ICP-MS. Of 43 monitored isotopes, 37 varied by sample preparation method, with significantly higher results of 17 isotopes in the microwave-digested samples. Both filtration treatments resulted in lower results for 11 isotopes compared to the other methods. Finally, isotope dilution determination of copper based on natural abundances and the 63Cu:65Cu instrument response ratio agreed with external calibration and confirmed a significant sample preparation effect. Overall, microwave digestion did not compare favorably, and direct dilution was found to provide the best compromise between ease of use and result accuracy and precision, although all preparation strategies were able to differentiate the wines.

Profiling extractable and leachable inorganic impurities in ophthalmic drug containers by ICP-MS

Abstract In this study, we investigated the elemental impurities present in the plastic material of ophthalmic eye drop bottles using inductively coupled plasma-mass spectrometry (ICP-MS). Metallic contaminations, especially localized within the small cavity of the eye, can significantly perturb the ocular metallome. The concern is two-fold: first certain elements, for example heavy metals, can be toxic to humans at even trace levels, and second, these contaminations can have adverse reactions with other medicines or enzymatic processes in the eye. The implication of redox-active metals in cataract formation is one such biological consequence. The analysis demonstrated the effect of aggressive storage and transportation conditions on elemental extractable and leachable contamination, and posits that release of these elemental impurities can disrupt metallome equilibrium in the ocular compartment, leading to toxicity and disease.