Correction: Precise measurement of selenium isotopes by HG-MC-ICPMS using a 76-78 double-spike.

[This corrects the article DOI: 10.1039/C9JA00331B.].

In situ Mg isotope measurements of biogenic carbonates using laser ablation multi-collector inductively coupled plasma mass spectrometry: A new tool to understand biomineralisation.

RATIONALE: Magnesium is one of the most abundant elements in the earth's crust and in seawater. Fractionation of its stable isotopes has been shown to be a useful indicator of many geological, chemical, and biological processes. For example, biogenic carbonates display an ~5‰ range of δ26 Mg values, which is attributed to variable degrees of biological control on Mg ions during biomineralisation. Understanding this biological control is essential for developing proxies based on biogenic carbonates. METHODS: In this work, we present a new approach of measuring Mg isotopes in biogenic carbonates using Laser Ablation Multi-Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICPMS). RESULTS: Our results show that this microanalytical approach provides relatively fast, high spatial resolution (<0.2 µm) measurements with high precision and accuracy down to 0.2‰ (2SE). To achieve high levels of precision and accuracy, baseline interferences need to be monitored and a carbonate standard with a relatively low trace metal composition similar to biogenic carbonates should be used. We also demonstrate that the matrix effect on Mg isotopes in carbonates with low Fe and Mn is limited to less than 0.2‰ fractionation under different laser parameters and low oxide condition (<0.3% ThO/Th). CONCLUSIONS: Our newly developed LA-MC-ICPMS method and its applications to biogenic carbonates show significant advantages provided by the microanalytical approach in understanding complex processes of biomineralisation in marine calcifiers.

Application of 1013 ohm Faraday cup current amplifiers for boron isotopic analyses by solution mode and laser ablation multicollector inductively coupled plasma mass spectrometry.

RATIONALE: Boron isotope ratios (δ11 B values) are used as a proxy for seawater paleo-pH, amongst several other applications. The analytical precision can be limited by the detection of low intensity ion beams from limited sample amounts. High-gain amplifiers offer improvements in signal/noise ratio and can be used to increase measurement precision and reduce sample amounts. METHODS: 1013 ohm amplifier technology has previously been applied to several radiogenic systems, but has thus far not been applied to non-traditional stable isotopes. Here we apply 1013 ohm amplifier technology for the measurement of boron isotope ratios using solution mode MC-ICP-MS and laser ablation mode (LA-)MC-ICP-MS techniques. Precision is shown for reference materials as well as for low-volume foraminifera samples. RESULTS: The baseline uncertainty for a 0.1 pA 10 B+ ion beam is reduced to <0.1 ‰ for a typical measurement period. The external precision is better than 0.2 ‰ (2SD) for δ11 B measurements for solution samples containing as little as 0.8 ng total boron. For in situ microanalyses with LA-MC-ICP-MS, the external precision of 11 B/10 B from an in-house calcite standard was 1 ‰ (2SD) for individual spot analyses, and 0.3 ‰ for the mean of ≥10 replicate spot analyses. CONCLUSIONS: 1013 ohm amplifier technology is demonstrated to offer advantages for the determination of δ11 B values by both MC-ICP-MS and LA-MC-ICP-MS for small samples of biogenic carbonates, such as foraminifera shells. 1013 ohm amplifier technology will also be of benefit to other non-traditional stable isotope measurements.

High-precision determination of lithium and magnesium isotopes utilising single column separation and multi-collector inductively coupled plasma mass spectrometry.

RATIONALE: Li and Mg isotopes are increasingly used as a combined tool within the geosciences. However, established methods require separate sample purification protocols utilising several column separation procedures. This study presents a single-step cation-exchange method for quantitative separation of trace levels of Li and Mg from multiple sample matrices. METHODS: The column method utilises the macro-porous AGMP-50 resin and a high-aspect ratio column, allowing quantitative separation of Li and Mg from natural waters, sediments, rocks and carbonate matrices following the same elution protocol. High-precision isotope determination was conducted by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) on the Thermo Scientific™ NEPTUNE Plus™ fitted with 1013  Ω amplifiers which allow accurate and precise measurements at ion beams ≤0.51 V. RESULTS: Sub-nanogram Li samples (0.3-0.5 ng) were regularly separated (yielding Mg masses of 1-70 µg) using the presented column method. The total sample consumption during isotopic analysis is <0.5 ng Li and <115 ng Mg with long-term external 2σ precisions of ±0.39‰ for δ7 Li and ±0.07‰ for δ26 Mg. The results for geological reference standards and seawater analysed by our method are in excellent agreement with published values despite the order of magnitude lower sample consumption. CONCLUSIONS: The possibility of eluting small sample masses and the low analytical sample consumption make this method ideal for samples of limited mass or low Li concentration, such as foraminifera, mineral separates or dilute river waters.

Determination of low concentrations of iron, arsenic, selenium, cadmium, and other trace elements in natural samples using an octopole collision/reaction cell equipped quadrupole-inductively coupled plasma mass spectrometer.

RATIONALE: Accurate determination of trace metals has many applications in environmental and life sciences, such as constraining the cycling of essential micronutrients in biological production and employing trace metals as tracers for anthropogenic pollution. Analysis of elements such as Fe, As, Se, and Cd is challenged by the formation of polyatomic mass spectrometric interferences, which are overcome in this study. METHODS: We utilized an Octopole Collision/Reaction Cell (CRC)-equipped Quadrupole-Inductively Coupled Plasma Mass Spectrometer for the rapid analysis of small volume samples (~250 µL) in a variety of matrices containing HNO3 and/or HCl. Efficient elimination of polyatomic interferences was demonstrated by the use of the CRC in Reaction Mode (RM; H2 gas) and in Collision-Reaction Mode (CRM; H2 and He gas), in addition to hot plasma (RF power 1500 W) and cool plasma (600 W) conditions. RESULTS: It was found that cool plasma conditions with RM achieved the greatest signal sensitivity while maintaining low detection limits (i.e. (56) Fe in 0.44 M HNO3 has a sensitivity of 160,000 counts per second (cps)-per-1 µg L(-1) and a limit of detection (LoD) of 0.86 ng L(-1) ). The average external precision was ≤ ~10% for minor (≤10 µg L(-1) ) elements measured in a 1:100 dilution of NIST 1643e and for iron in rainwater samples under all instrumental operating conditions. CONCLUSIONS: An improved method has been demonstrated for the rapid multi-element analysis of trace metals that are challenged by polyatomic mass spectrometric interferences, with a focus on (56) Fe, (75) As, (78) Se and (111) Cd. This method can contribute to aqueous environmental geochemistry and chemical oceanography, as well as other fields such as forensic chemistry, agriculture, food chemistry, and pharmaceutical sciences.

Entrapment of atmospheric particle bound heavy metals by ferns as evidenced by lead (Pb) isotope and MixSIAR: Implications for improving air quality.

Plant metal uptake can occur through both soil-root and atmospheric transfer from leaves. The latter holds potential implications for development of biofiltration systems. To explore this potential, it is crucial to understand entrapment capacity and metal sources within plants. As ferns absorb materials from atmosphere, this study focuses on two abundant fern species growing in densely populated and highly polluted regions of Eastern India. Gravimetric quantification, elemental concentration and Pb isotopic analyses were performed by segregating the ferns into distinct components: foliage dusts (loose dust (LD) and wax-bound dust (WD)) and plant tissue (leaves and roots). To understand metal sources, the study analyzes soil, and atmospheric particulates (PM10 and dust fall (DF)). Results indicate that, while LDs have soil dust influence, wax entraps atmospheric particulates and translocates them inside the leaves. Furthermore, roots demonstrate dissimilar isotopic ratios from soil, while displaying close association with atmospheric particulates. Isotopic composition and subsequent mixing model reveal dominant contribution from DF in leaves (53-73%) and roots (33-86%). Apart from DF, leaf Pb is sourced from PM10 (21-38%) with minimal contribution from soil (6-10%). Conversely, in addition to dominance from DF, roots source Pb primarily from soil (12-62%) with a meagre 2-8% contribution from PM10.

Thermal stress reduces pocilloporid coral resilience to ocean acidification by impairing control over calcifying fluid chemistry.

The combination of thermal stress and ocean acidification (OA) can more negatively affect coral calcification than an individual stressors, but the mechanism behind this interaction is unknown. We used two independent methods (microelectrode and boron geochemistry) to measure calcifying fluid pH (pHcf) and carbonate chemistry of the corals Pocillopora damicornis and Stylophora pistillata grown under various temperature and pCO2 conditions. Although these approaches demonstrate that they record pHcf over different time scales, they reveal that both species can cope with OA under optimal temperatures (28°C) by elevating pHcf and aragonite saturation state (Ωcf) in support of calcification. At 31°C, neither species elevated these parameters as they did at 28°C and, likewise, could not maintain substantially positive calcification rates under any pH treatment. These results reveal a previously uncharacterized influence of temperature on coral pHcf regulation-the apparent mechanism behind the negative interaction between thermal stress and OA on coral calcification.

Tracking suspended particle transport via radium isotopes ((226)Ra and (228)Ra) through the Apalachicola-Chattahoochee-Flint River system.

Suspended particles in rivers can carry metals, nutrients, and pollutants downstream which can become bioactive in estuaries and coastal marine waters. In river systems with multiple sources of both suspended particles and contamination sources, it is important to assess the hydrologic conditions under which contaminated particles can be delivered to downstream ecosystems. The Apalachicola-Chattahoochee-Flint (ACF) River system in the southeastern United States represents an ideal system to study these hydrologic impacts on particle transport through a heavily-impacted river (the Chattahoochee River) and one much less impacted by anthropogenic activities (the Flint River). We demonstrate here the utility of natural radioisotopes as tracers of suspended particles through the ACF system, where particles contaminated with arsenic (As) and antimony (Sb) have been shown to be contributed from coal-fired power plants along the Chattahoochee River, and have elevated concentrations in the surficial sediments of the Apalachicola Bay Delta. Radium isotopes ((228)Ra and (226)Ra) on suspended particles should vary throughout the different geologic provinces of this river system, allowing differentiation of the relative contributions of the Chattahoochee and Flint Rivers to the suspended load delivered to Lake Seminole, the Apalachicola River, and ultimately to Apalachicola Bay. We also use various geochemical proxies ((40)K, organic carbon, and calcium) to assess the relative composition of suspended particles (lithogenic, organic, and carbonate fractions, respectively) under a range of hydrologic conditions. During low (base) flow conditions, the Flint River contributed 70% of the suspended particle load to both the Apalachicola River and the bay, whereas the Chattahoochee River became the dominant source during higher discharge, contributing 80% of the suspended load to the Apalachicola River and 62% of the particles entering the estuary. Neither of these hydrologic scenarios, which were moderately low flow regimes, appeared to transport particles contaminated with arsenic and antimony to Apalachicola Bay.

Lithium isotope history of Cenozoic seawater: changes in silicate weathering and reverse weathering.

Weathering of uplifted continental rocks consumes carbon dioxide and transports cations to the oceans, thereby playing a critical role in controlling both seawater chemistry and climate. However, there are few archives of seawater chemical change that reveal shifts in global tectonic forces connecting Earth ocean-climate processes. We present a 68-million-year record of lithium isotopes in seawater (δ(7)Li(SW)) reconstructed from planktonic foraminifera. From the Paleocene (60 million years ago) to the present, δ(7)Li(SW) rose by 9 per mil (‰), requiring large changes in continental weathering and seafloor reverse weathering that are consistent with increased tectonic uplift, more rapid continental denudation, increasingly incongruent continental weathering (lower chemical weathering intensity), and more rapid CO(2) drawdown. A 5‰ drop in δ(7)Li(SW) across the Cretaceous-Paleogene boundary cannot be produced by an impactor or by Deccan trap volcanism, suggesting large-scale continental denudation.