The impact of gas purity on observed reactivity with NO using inductively coupled plasma tandem mass spectrometry.

Interference removal in inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) is strongly dependent on the gas selected for use within the collision/reaction cell. There has been little investigation on the effects that reaction gas impurities may have on the resulting spectra. The reactivity of 60 elements was evaluated using nitric oxide (NO 99.5%) with and without a gas purifier to reduce H2O impurities to <100 pptV. Experiments were performed using V, Ce, Tl and Th to investigate the effects of purified NO at various flowrates (0.22-1.49 mL min-1). Purified NO was shown to significantly mitigate oxy-hydride interferences, improve total ion sensitivity (notable at high gas flows), and shift product distributions advantageously. The reduction in oxy-hydride species results in a product distribution favoring the major expected products, where signals were shown to increase by an order of magnitude. Reduced background and increased signal for the major expected products provides avenues for improving various analytical applications of ICP-MS/MS.

The Curious Case of Pu+: Insight on 5f Orbital Activity from Inductively Coupled Plasma Tandem Mass Spectrometry (ICP-MS/MS) Reactions.

A comprehensive understanding of when and how 5f orbitals participate in complex chemical bonding is important for a variety of applications. The actinides are unique in that they possess 5f orbitals and can access high oxidation states, which make them attractive for use in catalysis. Fundamental studies of actinide-ligand interactions offer a mechanism to examine the activation of the 5f orbitals so that the selectivity of 5f orbitals can be assessed. A previous study examined the reaction of Pu+ + CO2 and determined that the reaction efficiency is restricted by a barrier, namely, promotion from the Pu+ ground-state configuration, 5f67s, to a reactive-state configuration, 5f56d2. The present study illustrates the benefit of activation of Pu's 5f orbitals when studying the reaction of Pu+ + NO. In this reaction, PuO+ forms in an exothermic, barrierless process. The 5f orbitals can and do participate in forming a linear intermediate, [N-Pu-O]+, and this drives the exothermic reaction. Understanding the conditions under which 5f orbitals are active in chemical bonding is the key to exploiting the actinides' selective catalytic capabilities.

Assessing Gas-Phase Ion Reactivity of 50 Elements with NO and the Direct Application for 239Pu in Complex Matrices Using ICP-MS/MS.

Understanding the reactivity of metal cations with various reaction gases in inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) is important to determine the best gas to use for a given analyte/interference pair. In this study, nitric oxide (NO) was investigated as the reaction gas following previous experimental designs. The reactions with 50 elements were investigated to examine periodic trends in reactivity, validate theoretical modeling of reaction enthalpies as a method to screen reactant gases, and provide a baseline data set for potential in-line gas separation methods. ICP-MS/MS studies involving actinides are typically limited to Th, U, and Pu, with analyses of Np and Am rarely reported in the literature. To date, only two previous methods have investigated the use of NO in ICP-MS/MS analyses. To showcase the utility of NO, a method was developed to measure 239Pu in the presence of environmental matrix constituent and other actinides, like what could be expected from postdetonation debris, with no chemical separation prior to analysis. 239Pu+ was reacted to form 239Pu16O+, eliminating interferences derived from the sample matrix by measuring the 239Pu+ intensity at m/z = 255 (239Pu16O+). To validate NO for 238U1H+ interference removal in environmental matrices, standard reference materials were diluted to 1 mg/g of solution and spiked to 0.05 pg/g of 239Pu and 1 µg/g 238U (Pu/U = 5 × 10-8). Measured 239Pu concentrations were within 6% of the spiked value. These results demonstrate that reliable 239Pu measurements can be made at levels relevant to nuclear forensics without the need for extensive chemical matrix separation prior to analysis.

The importance of ion kinetic energy for interference removal in ICP-MS/MS.

The effect of ion kinetic energy on gas phase ion reactivity with ICP-MS/MS was investigated in order to explore tuning strategies for interference removal. The collision/reaction gases CO2, N2O and O2 were used to observe the ion product distribution for 48 elements using an Agilent tandem ICP-MS (ICP-MS/MS) as a function of reaction gas flow rate (pressure) and ion kinetic energy. The kinetic energy of the incident ion was varied by adjusting the octopole bias (Voct). The three gases all form oxides (MO+) as the primary product with differing reaction enthalpies that result in distinct differences in the ion energies required for reaction with product ion distributions that vary with Voct. Consequently, by varying the ion kinetic energy (i.e., Voct), differences in interference reactivity can be used to achieve maximum separation. Three practical application examples were reported to demonstrate how the ion kinetic energy can be varied to achieve the ideal ion product distribution for interference resolution: CO2 for the removal of 238U in Pu analyses, CO2 for the removal of 40Ar16O vs. 56Fe, and O2 for the removal of Sm in Eu analyses, analogous to Pu/Am. The results demonstrate how the starting ion energy defined by Voct is an important factor to fully leverage the utility of any given reaction gas to remove interferences in the mass spectrum using ICP-MS/MS.

Graphical Discrimination of New Zealand Honey from International Honey Using Elemental Analysis.

This study investigated the potential of utilising the elemental fingerprinting of honey to differentiate New Zealand (NZ) honey from that of international origin. Twenty elements were analysed by ICP-MS in 352 honeys from 34 various countries. Of these, 323 honeys (245 New Zealand honeys, 78 international) and two subsets of data (NZ and European origin, n = 306, and, NZ and Denmark/Germany, n = 280) were visualised using principal component analysis (PCA). For the NZ/Europe subset, 42.2% of data was explained in the first two principal components. Statistical classification rules were also derived using linear discriminant analysis (LDA) and decision tree analysis. Various combinations of elements were explored for classification, considering the effect of soil-derived elements and those from anthropogenic sources. A high degree of accuracy (at least 90%) for the characterisation of New Zealand honey was observed for all statistical models, showing the robustness of these analyses. When using decision tree analysis to distinguish New Zealand samples from international samples, a tree with five terminal nodes (using Cs, Ba and Rb) was created with 92.4% accuracy. This work has demonstrated that elemental fingerprints of honey are a promising tool for categorising New Zealand honey from other geographical locations.

f-Block reactions of metal cations with carbon dioxide studied by inductively coupled plasma tandem mass spectrometry.

f-Block chemistry offers an opportunity to test current knowledge of chemical reactivity. The energy dependence of lanthanide cation (Ln+ = Ce+, Pr+, Nd+-Eu+) and actinide cation (An+ = Th+, U+-Am+) oxidation reactions by CO2, was observed by inductively coupled plasma tandem mass spectrometry. This reaction is commonly spin-unallowed because the neutral reactant (CO2, 1Σ+g) and product (CO, 1Σ+) require the metal and metal oxide cations to have the same spin state. Correlation of the promotion energy (Ep) to the first state with two free d-electrons with the reaction efficiency indicates that spin conservation is not a primary factor in the reaction rate. The Ep likely influences the reaction rate by partially setting the crossing between the ground and reactive states. Comparison of Ln+ and An+ congener reactivity indicates that the 5f-orbitals play a small role in the An+ reactions.

Deciphering local and regional hydroclimate resolves contradicting evidence on the Asian monsoon evolution.

The winter and summer monsoons in Southeast Asia are important but highly variable sources of rainfall. Current understanding of the winter monsoon is limited by conflicting proxy observations, resulting from the decoupling of regional atmospheric circulation patterns and local rainfall dynamics. These signals are difficult to decipher in paleoclimate reconstructions. Here, we present a winter monsoon speleothem record from Southeast Asia covering the Holocene and find that winter and summer rainfall changed synchronously, forced by changes in the Pacific and Indian Oceans. In contrast, regional atmospheric circulation shows an inverse relation between winter and summer controlled by seasonal insolation over the Northern Hemisphere. We show that disentangling the local and regional signal in paleoclimate reconstructions is crucial in understanding and projecting winter and summer monsoon variability in Southeast Asia.

Development of Online pH Monitoring for Lactic, Malonic, Citric, and Oxalic Acids Based on Raman Spectroscopy Using Hierarchical Chemometric Modeling.

Online spectroscopic measurements can be used to provide unique insight into complex chemical systems, enabling new understanding and optimization of chemical processes. A key example of this is discussed here with the monitoring of pH of various acid systems in real-time. In this work the acids used in multiple chemical separations processes, such as TALSPEAK (Trivalent Actinide-Lanthanide Separation by Phosphorus reagent Extraction from Aqueous Komplexes) and oxalate precipitation, were characterized. Raman spectroscopy, a robust optical approach that can be integrated in corrosive processes, was used to follow the unique fingerprints of the various protonated and deprotonated acid species. This data was analyzed using a hierarchical modeling approach to build a consolidated model scheme using optical fingerprints from all weak acids to measure pH associated with any of the weak acid systems studied here. Validation of system performance included utilizing Raman spectroscopy under dynamic flow conditions to monitor solution pH under changing process conditions in-line. Overall, the Raman based approach provided accurate analysis of weak acid solution pH.

Investigation of inorganic elemental content of honey from regions of North Island, New Zealand.

Determination of geographical origin of honey is important to consumers to confirm authenticity. This study investigated the elemental fingerprint of 181 honey samples collected from apiary sites in six regions of North Island, New Zealand to determine if differences were observed due to region of collection or land use surrounding the hive (e.g. agricultural, rural, urban). Using principal component analysis, soil related elements (Ca, K, Mg, Mn, Na) provided 75.2% discrimination of samples in the first two principal components. Overall, low concentrations of heavy metals were observed; lead was present in close proximity to highly trafficked roads (28.1% of samples; 9.50-76.5 µg kg-1) and cadmium was primarily present in honey collected from agricultural land in the Waikato (<51.6 µg kg-1). The use of an elemental fingerprint of New Zealand honey may be advantageous to determine the geographical origin compared to honey produced from other countries.

Balancing essential and non-essential metal bioavailability during hatchery rearing of Greenshell mussel (Perna canaliculus) larvae.

The use of ethylenediaminetetraacetic acid (EDTA) during bivalve hatchery production is thought to improve larval yields due to the reduced exposure to toxic metals (such as Cu); however, few studies have focused on the bioavailability of metals during the rearing process. Greenshell™ mussels (Perna canaliculus) were reared for 48 h with and without EDTA (12 µM) exposure and larvae were subsequently raised to 21 days post-fertilisation with and without EDTA exposure. Survival, shell length, algal ingestion rate, swimming activity, total metal concentration in water, bioavailable metal concentrations and larval metal accumulation were monitored for the 21 day period. Larval fitness (specifically D-yields) was improved on day 2 in the EDTA treatment, whereas an overall negative effect of EDTA treatment on fitness was observed on day 10 and 21. During the first 48 h, increased survival in the EDTA treatment is believed to be due to the reduction of bioavailable Zn concentrations in the rearing seawater. No other metal (essential or non-essential) displayed a consistent trend when comparing metal bioavailability to any of the fitness parameters measured throughout the experiment. Though the measured metal bioavailability was not clearly linked to fitness, the uptake of Al, P, Cr, Fe, Co, Ni, Zn, As, Cd, and Hg by P. canaliculus was reduced during the first 48 h, suggesting that the biological regulation of these elements is just as important as the bioavailability. Overall, treatment of the rearing seawater with 12 µM EDTA is effective for improving Greenshell™ mussel larval yields by decreasing metal bioavailability during the first two days of development but has minimal benefit between day 2 and 21.

Trace Element Concentrations in Blood and Scute Tissues from Wild and Captive Hawaiian Green Sea Turtles (Chelonia mydas).

Sea turtles are exposed to trace elements through water, sediment, and food. Exposure to these elements has been shown to decrease immune function, impair growth, and decrease reproductive output in wildlife. The present study compares trace element concentrations in green turtles in captivity at Sea Life Park Hawaii (n = 6) to wild green turtles in Kapoho Bay, Hawaii, USA (n = 5-7). Blood and scute samples were collected and analyzed for 11 elements via inductively coupled plasma-mass spectrometry (ICP-MS). Selenium was significantly greater (p < 0.05) in the blood of captive turtles compared with wild turtles, whereas V, Ni, and Pb were significantly greater in the blood of wild turtles. In scute, V, Cu, Se, and Cr were significantly greater in captive turtles, whereas As was significantly greater in wild turtles. Pelleted food fed to the captive turtles and representative samples of the wild turtle diet were analyzed via ICP-MS to calculate trophic transfer factors and daily intake values. Wild turtles had greater estimated daily intake than captive turtles for all elements except Cu and Se. Because captive turtles are fed a diet very different from that of their wild counterparts, captive turtles do not represent control or reference samples for chemical exposure studies in wild turtles. No toxic thresholds are known for sea turtles, but rehabilitation and managed care facilities should monitor sea turtle elemental concentrations to ensure the animals' health. Environ Toxicol Chem 2021;40:208-218. © 2020 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.

Optimised approach for small mass sample preparation and elemental analysis of bees and bee products by inductively coupled plasma mass spectrometry.

The elemental fingerprint of honey, pollen and bees are useful biomonitors of anthropogenic activities across the world. Elements in honey and pollen may also be analysed for their nutritional value and potential toxicity. There are currently limited studies that address the use of small sample masses while retaining good reproducibility and detection limits during elemental analysis. The aim of this study was to develop a simple analytical method to quantify 39 major, minor, trace and rare earth elements in small mass samples of bees, honey and pollen by inductively coupled plasma mass spectrometry. The final method was validated for 20-200 mg bee, 20-100 mg pollen or 50-200 mg of honey with 0.2 mL nitric acid followed by 0.1 mL hydrogen peroxide in a digestion block (80 °C, 2 h total); samples were made up to a final volume of approximately 6 mL. The method reduces the volume of chemicals used, limits sample manipulation and improves detection limits over traditional digestion methods. The sample preparation and analysis method were deemed to be satisfactory for the three matrices examined, with spike recoveries ranging from 96 (B) to 129% (As) for trace elements and 91 (Pr) to 112% (La) for rare earth elements, and acceptable detection limits (down to 5.07 µg kg-1 for Co using 30 mg sample mass, pollen). Precision was acceptable with the relative percent standard deviation of fully homogenised samples ranging from 0.53 (K, bee, 20 mg) to 24% (As, 30 mg, bee) across the three matrices and all masses analysed. This small mass digestion method enables the analysis of a single bee allowing a more distinctive elemental signature to be determined. Similarly, pollen from fewer flowers of the same species can be pooled together which is advantageous for analysis of flowers that produce little pollen.

Bioaccessibility of antimony and other trace elements from lead shot pellets in a simulated avian gizzard environment.

Many studies have used grit (in the form of lead (Pb) pellets) presence in avian gizzards as an indicator of Pb shot exposure. However, due to nearly complete pellet absorption in gizzards or rapid passage of pellets, the absence of Pb shot presence in a gizzard does not confirm lack of Pb shot exposure. This study provides the basis for an additional technique to identify if elevated tissue Pb concentration is due to Pb shot exposure. Bioaccessibility of Pb and trace elements (Sb, As, and Sn) present in Pb shot were quantified to determine if any of these elements would be useful as a secondary marker of Pb shot exposure. An avian physiologically based extraction test (PBET) was used to determine pellet dissolution rate and bioaccessible concentrations of Pb, Sb, As, and Sn in a simulated gizzard environment. Of the three trace elements, only Sb concentrations (44-302 µg/mL) extracted into the gizzard solution were greater than environmental background levels (US soil average 0.48 µg/g); thus, no natural source likely provides this amount of Sb. Therefore, there is evidence that Sb can be extracted from Pb shot in bird gizzards at detectable concentrations (above natural background). While further studies are needed to delineate the mechanisms of absorption and distribution, this study lends credence to the hypothesis that Sb may be a useful marker of Pb shot exposure in biological tissues, particularly when Pb pellets are not present nor observed in avian tissues.

Anchored Aluminum Catalyzed Meerwein-Ponndorf-Verley Reduction at the Metal Nodes of Robust MOFs.

Catalytic Meerwein-Ponndorf-Verley reductions of ketones and aldehydes in the presence of isopropyl alcohol were performed at aluminum alkoxide sites that were postsynthetically introduced into robust metal-organic frameworks (MOFs). The aluminum was anchored at the bridging hydroxyl sites inherent in some MOFs. MOFs in the UiO-66/67 family as well as DUT-5 were successfully adapted to this strategy. Incorporation of catalytically active aluminum species greatly enhanced the reactivity of the native MOF at 80 °C in the case of both UiO-66, and was almost solely responsible for catalytic activity in the case of metalated UiO-66 and DUT-5. The site isolation of the catalyst prevented aggregation and complete deactivation of the molecular aluminum catalyst, allowing it to be recovered and recycled in the case of UiO-67. This catalyst also proved to be moderately tolerant to wet isopropyl alcohol.

In Situ Spectroscopic Analysis and Quantification of [Tc(CO)3]+ in Hanford Tank Waste.

The quantitative conversion of nonpertechnetate [Tc(CO)3]+ species in nuclear waste storage tank 241-AN-102 at the Hanford Site is demonstrated. A waste sample containing the [Tc(CO)3]+ species is added to a developer solution that rapidly converts the nonemissive species into a luminescent complex, which is detected spectroscopically. This method was first demonstrated using a [Tc(CO)3]+ sample of nonwaste containing matrix to determine a detection limit (LOD), resulting in a [Tc(CO)3]+ LOD of 2.20 × 10-7 M, very near the LOD of the independently synthesized standard (2.10 × 10-7 M). The method was then used to detect [Tc(CO)3]+ in a simulated waste using the standard addition method, resulting in a [Tc(CO)3]+ concentration of 1.89 × 10-5 M (within 27.7% of the concentration determined by ß liquid scintillation counting). Three samples from 241-AN-102 were tested by the standard addition method: (1) a 5 M Na adjusted fraction, (2) a fraction depleted of 137Cs, and (3) an acid-stripped eluate. The concentrations of [Tc(CO)3]+ in these fractions were determined to be 9.90 × 10-6 M (1), 0 M (2), and 2.46 × 10-6 M (3), respectively. The concentration of [Tc(CO)3]+ in the as-received AN-102 tank waste supernatant was determined to be 1.84 × 10-5 M.

In Situ Quantification of [Re(CO)3]+ by Fluorescence Spectroscopy in Simulated Hanford Tank Waste.

A pretreatment protocol is presented that allows for the quantitative conversion and subsequent in situ spectroscopic analysis of [Re(CO)3]+ species in simulated Hanford tank waste. In this test case, the nonradioactive metal rhenium is substituted for technetium (Tc-99), a weak beta emitter, to demonstrate proof of concept for a method to measure a nonpertechnetate form of technetium in Hanford tank waste. The protocol encompasses adding a simulated waste sample containing the nonemissive [Re(CO)3]+ species to a developer solution that enables the rapid, quantitative conversion of the nonemissive species to a luminescent species which can then be detected spectroscopically. The [Re(CO)3]+ species concentration in an alkaline, simulated Hanford tank waste supernatant can be quantified by the standard addition method. In a test case, the [Re(CO)3]+ species was measured to be at a concentration of 38.9 µM, which was a difference of 2.01% from the actual concentration of 39.7 µM.

Trophic Transfer and Accumulation of Multiwalled Carbon Nanotubes in the Presence of Copper Ions in Daphnia magna and Fathead Minnow (Pimephales promelas).

The increase in use of nanomaterials such as multiwalled carbon nanotubes (MWCNTs) presents a need to study their interactions with the environment. Trophic transfer was measured between Daphnia magna and Pimephales promelas (fathead minnow, FHM) exposed to MWCNTs with different outer diameter (OD) sizes (MWCNT1 = 8-15 nm OD and MWCNT2 = 20-30 nm OD) in the presence and absence of copper. Pristine FHM were fed D. magna, previously exposed for 3 d to MWCNT1 or MWCNT2 (0.1 mg/L) and copper (0.01 mg/L), for 7 d. D. magna bioaccumulated less MWCNT1 (0.02 µg/g) than MWCNT2 (0.06 µg/g), whereas FHM accumulated more MWCNT1 (0.81 µg/g) than MWCNT2 (0.04 µg/g). In the presence of copper, MWCNT bioaccumulation showed an opposite trend. Mostly MWCNT1 (0.03 µg/g) bioaccumulated in D. magna, however less MWCNT1 (0.21 µg/g) than MWCNT2 (0.32 µg/g) bioaccumulated in FHM. Bioaccumulation factors were higher for MWCNT1s than MWCNT2. However, an opposite trend was observed when copper was added. Plasma metallothionein-2 was measured among treatments; however concentrations were not statistically different from the control. This study demonstrates that trophic transfer of MWCNTs is possible in the aquatic environment and further exploration with mixtures can strengthen the understanding of MWCNT environmental behavior.

Exposure, Effects and Absorption of Lead in American Woodcock (Scolopax minor): A Review.

Due to long term declines of American Woodcock (Scolopax minor) and widespread distribution of environmentally available lead (Pb) throughout their geographic range, it is important to assess if Pb exposure is a potential contributor to these declines. Woodcock are exposed to Pb through various environmental sources and are known to exhibit relatively high bone-Pb concentrations. Absorption of Pb by birds, and woodcock specifically, is not well understood. Some studies show that interactions among calcium, phosphorus, iron, zinc, and vitamin D levels may play an important role in Pb absorption. Therefore, when future Pb studies are performed for woodcock, and other birds, interactions among these elements should be considered. For example, these interactions are relevant in the acquisition and mobilization of calcium in female birds during egg development and shell calcification. These factors should be considered to understand potential mechanisms of Pb exposure, Pb absorption, and subsequent Pb toxicity to birds in general, and woodcock specifically. This review discusses Pb exposure routes, effects of Pb toxicity, and the distribution of Pb in American woodcock and identifies areas for future research in woodcock and other avian species.

Cadmium Compartmentalization in the Pulmonate Snail Lymnaea stagnalis: Improving Our Understanding of Exposure.

In ecotoxicology, analytical compartmentalization analysis can be used to better understand metal sequestration and detoxification. Metals are typically found in two main compartments, biologically detoxified metal (BDM) and metal sensitive fractions (MSF). The purpose of this study was to analyze the subcellular distribution of cadmium (Cd) in Lymnaea stagnalis. Adult snails were exposed to three concentrations of Cd for 56 days as part of a global ring test for L. stagnalis. At the end of the 56-day exposure, organisms were separated in two sections (viscera and foot). Each section was subsequently divided by differential centrifugation into five total fractions including (metal rich granules, debris, Organelles, heat denatured proteins, and heat stable proteins) followed by Cd analysis. The concentration in each compartment, BDM, MSF, and bioconcentration factors were estimated as well. There was significantly higher bioconcentration of Cd in the viscera section compared with the foot. Cadmium accumulation in all five fractions also increased with increasing exposure concentrations. Cadmium accumulated the most in the heat denatured protein fraction (enzymes) and accumulated the least in the heat stable protein fraction (metallothionein-like proteins). The MSF compartment (~65%) was in higher proportion than the BDM (~30%), but only in the lowest Cd exposure concentration was there a significant difference between these compartments. The results indicated that, in general, there was more Cd accumulated in the metal sensitive fractions, and that the detoxification mechanisms were not efficient enough to avoid toxicity at the two highest concentrations. This study provides evidence that improves our understanding of Cd tissue distribution in freshwater gastropods.

Arsenic Uptake by Muskmelon (Cucumis melo) Plants from Contaminated Water.

Arsenic is a carcinogenic element that occurs naturally in the environment. High levels of arsenic are found in water in some parts of the world, including Texas. The aims of this study were to determine the distribution of arsenic in muskmelon (Cucumis melo) plants accumulated from arsenic spiked water and to observe effects on plant biomass. Plants were grown and irrigated using water spiked with variable concentrations of arsenic. Inductively coupled plasma mass spectrometry was used to quantify arsenic in different parts of the plant and fruit. Under all conditions tested in this study, the highest concentrations of arsenic were found in the leaves, soil, and roots. Arsenic in the water had no significant effect on plant biomass. Fruits analyzed in this study had arsenic concentrations of 101 µg/kg or less. Consuming these fruits would result in less arsenic exposure than drinking water at recommended levels.