Characterisation of gas cell reactions for 70+ elements using N2O for ICP tandem mass spectrometry measurements.

One widely utilised method to reduce spectral interferences for measurements using inductively coupled plasma mass spectrometry (ICP-MS) is to employ the use of a reaction cell gas. Nitrous oxide (N2O) is a highly reactive gas typically used for mass-shifting only target analytes to a higher mass-to-charge ratio with increased sensitivity (e.g. +16, +32, +48 amu for monoxide, dioxide, and trioxide product ions respectively). Traditionally, the use of N2O was limited to selected applications due to the creation of new interferences that also interfere with the detected masses of interest. However, with the advent of inductively coupled plasma tandem mass spectrometry (ICP-MS/MS), the use of N2O has gained more traction, with a growing number of publications in recent years. Here, a comprehensive study of the use of N2O for the determination of 73 elements has been conducted, with a comparison to the most widely used mass-shift method using oxygen (O2) as a reaction gas. In total, 59 elements showed improved sensitivity when performing mass-shift with N2O compared to O2, with 8 elements showing no reaction with either gas. Additionally, N2O demonstrated a collisional focusing effect for 36 elements when measuring on-mass. This effect was not observed using O2. Monitoring asymmetric charge transfer reactions with N2O highlighted 14 elements, primarily non-metals and semi-metals, that enter the gas cell as metastable ions and could be used as an alternative mass-shift option. The results from this study highlight the high versatility of N2O as a reaction cell gas for routine ICP-MS/MS measurements.

Determination of 48 elements in 7 plant CRMs by ICP-MS/MS with a focus on technology-critical elements.

Seven plant certified reference materials (NIST SRM1515 Apple Leaves, NIST SRM1547 Peach Leaves, BCR-129 Hay Powder, BCR-670 Aquatic Plant, GBW07603 Bush Twigs and Leaves, GBW10015 Spinach Leaves and NCS ZC73036a Green Tea) were analysed for their mass fractions of 48 elements by inductively coupled plasma tandem-mass spectrometry (ICP-MS/MS): Li, Be, Na, Mg, Al, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Nb, Mo, Ag, Cd, Sb, Te, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ta, Tl, Pb, Bi, Th, U. Special focus was put on the determination of technology-critical elements (TCEs), to which, e.g. Li, Be, Ga, Ge, Nb, Sb, Ta, Tl, Bi, and the rare-earth elements (REEs, lanthanides and Y) are counted. Closed-vessel microwave digestion was performed using HNO3, H2O2 and HBF4. The average bias for certified values is - 1% ± 13% (SD). Limits of detection (xL) in the measured solutions lie between 13 fg g-1 (Tb) and 52 ng g-1 (Ca). This article seeks to provide an optimised measurement procedure for the determination of element mass fractions of emerging importance in environmental samples, which are challenging to analyse with more traditional techniques such as single-quad ICP-MS. In addition, it aims to improve the characterisation of commonly used plant reference materials by providing mass fraction data for rarely studied elements.

Low-level 40Ca determinations using nitrous oxide with reaction cell inductively coupled plasma-tandem mass spectrometry.

In inductively coupled plasma mass spectrometry, the most abundant Ca isotope (40Ca) suffers from isobaric interference with argon, hindering the potential for low detection limits of Ca. A powerful approach is to remove the interference by using a reaction gas in a reaction cell. Ammonia (NH3) has proven to be an effective reaction gas by process of a charge transfer reaction. However, NH3 is highly corrosive and toxic and cannot remove isobaric 40 K. Therefore, this work proposes the use of nitrous oxide (N2O) to mass shift the target analyte 40Ca to 40Ca16O+ as a non-corrosive and non-toxic alternative. Instrument performance testing demonstrated that N2O was capable of reaching equivalent detection limits (0.015 ng g-1) and background equivalence concentrations (0.041 ng g-1) to that of NH3 and limited by the blank only. Further investigation of matrix interferences with synthetic standards highlighted that the N2O approach supports the separation of potassium (K) and magnesium (Mg)-based interferences at tested concentrations of more than 600 times and almost 800 times higher than Ca respectively, whereas NH3 was found to only support the removal of Mg. This work highlights a clear advantage of N2O for low-level Ca determinations with high matrix loads, as well as compatibility with other instrumentation sensitive to corrosion that supports reaction cell technology.

Mercury speciation in Scottish raptors reveals high proportions of inorganic mercury in Scottish golden eagles (Aquila chrysaetos): Potential occurrence of mercury selenide nanoparticles.

Knowledge of the uptake and fate of mercury (Hg) compounds in biota is important in understanding the global cycling of Hg and its transfer pathways through food chains. In this study, we analysed total mercury (T-Hg) and methylmercury (MeHg) concentrations in 117 livers of Scottish birds of prey that were found across Scotland and submitted for post-mortem examination through the Raptor Health Scotland project between 2009 and 2019. Statistical comparisons focussed on six species (barn owl, Tyto alba; Eurasian common buzzard, Buteo buteo; golden eagle, Aquila chrysaetos; hen harrier, Circus cyaneus; Eurasian sparrowhawk, Accipiter nisus; and tawny owl, Strix aluco) and showed that golden eagles had a statistically lower fraction of MeHg compared to other raptor species. Further investigation using stable carbon and stable nitrogen isotope ratio measurements carried out for the golden eagles (n = 15) indicated that the increased presence of inorganic mercury (iHg) correlated with a marine influence on the primarily terrestrial diet. Additional bioimaging (n = 1) with laser ablation - inductively coupled plasma - mass spectrometry indicated the co-location of Hg and selenium (Se) within the liver tissue and transmission electron microscopy showed evidence of nanoparticles within the range of 10-20 nm. Further analysis using single particle - inductively coupled plasma - mass spectrometry (n = 4) confirmed the presence of Hg nanoparticles. Together, the evidence suggests the presence of mercury selenide (HgSe) nanoparticles in the liver of some golden eagles that, to our knowledge, has never been directly observed in terrestrial birds of prey. This study points to two alternative hypotheses: these golden eagles may be efficient at breaking down MeHg and form HgSe nanoparticles as a detoxification mechanism (as previously observed in cetaceans), or some golden eagles with elevated iHg may have accumulated these nanoparticles by foraging on stranded cetaceans or seabirds.

Higher zero valent iron soil amendments dosages markedly inhibit accumulation of As in Faya and Kilombero cultivars compared to Cd.

Impact of zero valent iron (Fe°) amendment on grain-yield (GY) and grain-As and Cd accumulation in rice (Oryza sativa L.) cultivars Kilombero and Faya were investigated. Rice plants were amended with Fe° dosages of 0, 3.1, 6.2, and 12.4 g Fe°/kg soil in pots in greenhouse experiments under continuous flooding water regime. GY in each treatment was determined at maturity, grain-As and Cd and arsenic species concentrations were determined using ICP-MS and HPLC tandem ICP-MS respectively. Mean GY in Faya (5.5 ± 1.0 g/plant) and Kilombero (4.2 ± 0.4 g/plant) amended with at least 6.2 g Fe°/kg soil were at least 57% and 22% respectively significantly higher (F = 11; p = 0.003) than that in controls (3.7 ± 0.6 and 3.4 ± 0.4 g/plant). For As bioaccumulation, mean grain-As concentration in Faya T2 (≤227 ± 32 µg/kg) and Kilombero (≤218 ± 25 µg/kg) amended with at least 6.2 g Fe°/kg soil in were at least 83% and 77% respectively significantly lower (F = 7; p = 0.004) than that in controls (973 ± 43 µg/kg and 1278 ± 208 µg/kg). Mean grain-Cd concentrations in Faya (10 ± 2 µg/kg) and Kilombero (13 ± 3 µg/kg) amended with corresponding Fe° dosages were at least 26% and 39% significantly lower (F = 4; p < 0.05) than that in controls (18 ± 3 and 23 ± 1 µg/kg). Results indicated that amending Kilombero with at least 6.2 g/kg Fe° effectively optimally regulated both grain-As and Cd accumulation to values lower than the European Commission's legislated maximum contaminant limits (MCL) of 200 µg/kg without negating grain yield benefits. Our results suggest that bioaccumulation of both As and Cd in rice grains may be completely circumvented by adopting cultivar-specific Fe° amendment dosage.

Stability, preservation and storage of As(iii), DMA, MMA and As(v) in water samples.

Correct handling and preservation of water samples is crucial to ensure their integrity for arsenic speciation measurements. ISO TS 19620:2018 is a method for the determination of arsenic(iii) and arsenic(v) species in waters by liquid chromatography (LC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) or hydride generation atomic fluorescence spectrometry (HG-AFS). During the development of this method, a study was performed to establish the best practices for storage and preservation of samples to maintain the integrity of the arsenic speciation and stability. Four arsenic species were studied: arsenite (As(iii)), arsenate (As(v)), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in three different water types: deionised water, mineral water and natural river water. The effect of sample bottle material, light, storage temperature, and acidification were evaluated. When samples are acidified and refrigerated, they can reliably be stored for up to 12 weeks without significantly affecting the arsenic concentration and speciation. The sample bottle material and light had no affect on the speciation integrity or stability.

Different weak inter-actions in the crystals of three isomeric (E)-N-methyl-N'-(nitro-benzyl-idene)-2-(thio-phen-2-yl)acetohydrazides.

The crystal structures of three isomeric (E)-N-methyl-N'-(nitro-benzyl-idene)-2-(thio-phen-2-yl)acetohydrazides (formula C14H13N3O3S) are described, with the nitro group in ortho, meta and para positions in the benzene ring. In each crystal structure, mol-ecules are linked by various weak inter-actions (C-H⋯O and C-H⋯π bonds, and π-π stacking), leading to three-dimensional networks in each case, but with little similarity between them.