Absolute quantification of eleven A, D, E and K vitamers in human plasma using automated extraction and UHPLC-Orbitrap MS.

Fat-Soluble Vitamers [FSV] deficiencies and hypervitaminosis are associated with lifestyle diseases such as cardiovascular disease, diabetes, and cancer. Quantification of FSV and their metabolites in plasma has proved to be one of the most demanding analytical chemistry challenges. Current FSV quantification methods are compromises between breadth of coverage and sensitivity across the physiological range. Here, we developed and validated a sensitive, robust, semi-automated method using liquid-liquid extraction coupled with LC-ESI-MS/MS to quantify 11 FSV across their physiological concentrations in plasma. The addition of Phree® phospholipid removal plates as the last step in the extraction process reduced matrix effects, improving precision, recoveries, and the method's final sensitivity. This method can detect and quantify: retinol, retinoic acid, retinyl palmitate, 25 hydroxyvitamin D3 [25-OH-D3], 1-α-25-dihydroxy-D3, α-tocopherol, γ-tocopherol, α-tocotrienol, phylloquinone [K1], Menatetrenone [MK-4], and menaquinone-7 [MK-7].The Instrument Quantitation Limit [IQL]s for retinol (64.1 ng/mL), 25-OH-D3 (10.2 ng/mL), and α-tocopherol (3000 ng/mL) can detect clinical deficiencies. Our automated method will assist in the understanding of the complex interaction between these compounds and their possible role in health and disease.

Trace element concentrations, including Cd and Hg, in long-finned pilot whales (Globicephala melas edwardii) mass stranded on the New Zealand coast.

The Southern Hemisphere long-finned pilot whale (Globicephala melas edwardii) is a top predator in the New Zealand pelagic food web, feeding predominantly on arrow squids. This study quantified trace element concentrations (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Ni, Mn, Pb, Se, V, Zn) in four tissues (blubber, kidney, liver, muscle) from 21 individuals from stranding sites in New Zealand. Maximum Cd and Hg concentrations were measured in liver and kidney, respectively. Selenium had a positive correlation with Cd and Hg, suggesting the involvement of Se in Cd and Hg detoxification. Arrow squids from the whales' stomach contents were DNA barcoded and identified as Nototodarus sloanii. Trace element concentrations were measured in squid samples from the whale stomach contents. The significant correlation for Hg between the squid tissue and the whale tissue suggests that arrow squids play a major role in trace element uptake by G. m. edwardii.

LC-MS/MS quantification of fat soluble vitamers - A systematic review.

Fat soluble vitamers (FSV) are several biochemically diverse micronutrients essential for healthy development, growth, metabolism, and cell regulation. We cannot synthesize FSV completely or at the required concentrations. Deficiency or excess of FSV can result in many health problems. Plasma is the most accessible sample matrix for the quantification of FSV. However, due to its complexity and other analytical challenges (e.g., FSV sensitivity to light, oxygen, heat, pH, chemical heterogeneity, standard availability), developing a method for the simultaneous quantification of multiple FSV at physiological concentrations has been challenging. In this systematic review, we examine the parameters and criteria used in existing Liquid Chromatography with tandem Mass Spectrometry (LC-MS/MS) methods for FSV quantification to the extraction method, chromatographic resolution, matrix effects, and method validation as critical to a sensitive and robust method. We conclude that the final FSV method sensitivity is predominantly based on aforementioned criteria and future method development using LC-MS/MS will benefit from the application of this systematic review.

Regional assessment of trace element concentrations in arrow squids (Nototodarus gouldi, N. sloanii) from New Zealand waters: Bioaccessibility and impact on food web and human consumers.

The New Zealand arrow squids, Nototodarus gouldi and N. sloanii, play an important role in the marine food web, and are both economically important fishery species. This study compares trace element concentrations (As, Cd, Co, Cr, Cu, Fe, Hg, Ni, Mn, Pb, U, and Zn) in these animals from different fishing locations within New Zealand's Exclusive Economic Zone (Auckland Islands, Chatham Rise, Dunedin, Golden Bay, Taranaki, and West Coast of the South Island). Muscular mantle (the tissue usually consumed by humans) and digestive gland tissue (the primary organ for trace element accumulation) concentrations were compared among regions, revealing size, species, and sampling location effects. Overall, N. gouldi had higher concentrations of As and Zn. The Taranaki region had the highest concentrations for Cd, Co, Cu, and Zn in both tissues analysed. To assess the bioaccessibility of these trace elements to humans, an in-vitro digestion simulation experiment was conducted, revealing bioavailable concentrations overall below the maximum levels presently considered tolerable for human consumption. However, the in-vitro digestion had no observable effect upon Cd concentrations in arrow squid mantle tissue (implying that the measured concentrations are bioaccessible to humans), and revealed that Cd had the highest potential impact on marine food webs and human health. Digestive gland concentrations in particular indicate that arrow squids can be considered important vectors for trace element transfer to top predators (mean concentration for Cd: 123 ± 148 µg g-1 dw), with region-specific differences.