A rapid procedure for isotopic purification of copper and nickel from seawater using an automated chromatography system.

BACKGROUND: Trace metals such as iron, nickel, copper, zinc, and cadmium (Fe, Ni, Cu, Zn, and Cd) are essential micronutrients (and sometimes toxins) for phytoplankton, and the analysis of trace-metal stable isotopes in seawater is a valuable tool for exploring the biogeochemical cycling of these elements in the ocean. However, the complex and often time-consuming chromatography process required to purify these elements from seawater has limited the number of trace-metal isotope samples which can be easily processed in biogeochemical studies. To facilitate the trace-metal stable isotope analysis, here, we describe a new rapid procedure that utilizes automated chromatography for extracting and purifying Ni and Cu from seawater for isotope analysis using a prepFAST-MC™ system (Elemental Scientific Inc.). RESULTS: We have tested the matrix removal effectiveness, recoveries, and procedural blanks of the new purification procedure with satisfactory results. A nearly complete recovery of Ni and a quantitative recovery of Cu are achieved. The total procedural blanks are 0.33 ± 0.24 ng for Ni and 0.42 ± 0.18 ng for Cu, which is negligible for natural seawater samples. The new procedure cleanly separates Ni and Cu from key seawater matrix elements that may cause interferences during mass spectrometry analysis. When the new procedure was used to purify seawater samples for Ni and Cu stable isotope analysis by multi-collector ICP-MS, we achieved an overall uncertainty of 0.07 ‰ for δ60Ni and 0.09 ‰ for δ65Cu (2 SD). The new purification procedure was also tested using natural seawater samples from the South Pacific, for comparison of δ60Ni and δ65Cu achieved in the same samples purified by traditional hand columns. Both methods produced similar results, and the results from both methods are consistent with analyses of δ60Ni and δ65Cu from other ocean locations as reported by other laboratories. SIGNIFICANCE: This study presents a new rapid procedure for seawater stable-metal isotope analysis by automating the chromatography step. We anticipate that the automated chromatography described here will facilitate the rapid and accurate analysis of seawater δ60Ni and δ65Cu in future studies, and may be adapted in the future to automate chromatographic purification of Fe, Zn, and Cd isotopes from seawater.

Isotope geochemistry as a natural tag of fish in Patagonian freshwater environments: The invasive Chinook salmon case.

Patagonian aquatic environments have been invaded since the end of the last century by different species of salmonids. Knowing the natal origin and homing/straying rate of the salmonids in colonised environments is essential to understanding the dispersal mechanisms and developing management plans. In the last two decades, Chinook salmon Oncorhynchus tshawytscha showed the greatest natural dispersal capacity in Patagonia. The main goal of this study was to evaluate the environmental strontium isotope ratio (87Sr/86Sr) as a potential natural tag to infer the natal origin and ontogenetic habitat use of salmonids in Patagonia, specifically Chinook salmon. 87Sr/86Sr ratio was determined in water samples from 26 sites distributed in 14 Atlantic and Pacific basins in low and high water seasons. Environmental 87Sr/86Sr showed greater spatial than temporal variation, revealing great potential as a tool to infer the natal origin and life history of several migratory fish species in Patagonia. Otolith core-to-edge 87Sr/86Sr profiles were also analysed in 108 Chinook salmon from six basins. A cluster analysis based on the Unweighted Pair Group method (UPGMA) and Euclidean distances without prior classification grouped the sampled rivers into five main groups with significantly different (p < 0.05) isotopic ratios, sometimes integrated basins with different slopes (Atlantic or Pacific). The cluster analysis based on the natal 87Sr/86Sr period in otolith (∼natal origin) showed clear segregation between the Atlantic and Pacific samples. A mismatch between water and otolith natal 87Sr/86Sr ratio was detected in some Atlantic basins (e.g. De las Vueltas River in Santa Cruz Basin) and Pacific (e.g. Liquiñe Basin) and, which could be explained either by straying behaviours or by large geochemical variability between tributaries, within river systems. Our results showed that 87Sr/86Sr is a useful natural tag to trace the life history of migratory fishes in Patagonia, especially for invasive species such as Chinook salmon.

Natal origin and migration pathways of Mekong catfish (Pangasius krempfi) using strontium isotopes and trace element concentrations in environmental water and otoliths.

To improve our knowledge of the migration pathway of a highly threatened fish species along the Mekong River, strontium isotope ratios (87Sr/86Sr) and 18 trace element concentrations were measured in the water and in the otoliths of an anadromous catfish, Pangasius krempfi, to infer its natal origin and potential migration pathways. Water was sampled at 18 locations along the mainstream, tributaries and distributaries of the Mekong River. To check for accuracy and precision, measurements of the 87Sr/86Sr ratios and trace element concentrations were then compared in two laboratories that use different analytical methods. Differences in trace element concentrations between locations were not significant and could not, therefore, be used to discriminate between migration pathways. However, the Mekong mainstream, tributaries and distributaries could all be discriminated using Sr isotopes. The 87Sr/86Sr profiles recorded in P. krempfi otoliths showed that there were three contingents with obligate freshwater hatching and variable spawning sites along the Mekong mainstream, from Phnom Penh (Cambodia) to Nong Khai (Thailand) or further. After hatching, the fish migrated more or less rapidly to the Mekong Delta and then settled for most of their lifetime in brackish water. Spawning habitats and migration routes may be threatened by habitat shifts and the increasing number of hydropower dams along the river, especially the contingents born above Khone Falls (Laos). The conservation of P. krempfi, as well as other migratory fish in the Mekong River, requires agreements, common actions and management by all countries along the Mekong River. This study highlighted the importance of using both Sr/Ca and 87Sr/86Sr ratios to understand life history of anadromous fishes as the 87Sr/86Sr ratio in the water was shown to be less effective than the Sr/Ca ratio in identifying movements between different saline areas.

Tracing local sources and long-range transport of PM10 in central Taiwan by using chemical characteristics and Pb isotope ratios.

Central Taiwan is among the most heavily polluted regions in Taiwan because of a complex mixing of local emissions from intense anthropogenic activities with natural dust. Long-range transport (LRT) of pollutants from outside Taiwan also contributes critically to the deterioration of air quality, especially during the northeast monsoon season. To identify the sources of particulate matter < 10 µm (PM10) in central Taiwan, this study performed several sampling campaigns, including three local events, one LRT event, and one dust storm event, during the northeast monsoon season of 2018/2019. The PM10 samples were analyzed for water-soluble ion and trace metal concentrations as well as Pb isotope ratios. Local sediments were also collected and analyzed to constrain chemical/isotopic signatures of natural sources. The Pb isotope data were interpreted together with the enrichment factors and elemental ratios of trace metals in PM10, and reanalysis data sets were used to delineate the sources of PM10 in central Taiwan. Our results suggested that Pb in PM10 was predominantly contributed by oil combustion and oil refineries during the local events (48-88%), whereas the lowest contributions were from coal combustion (< 21%). During periods of high wind speed, the contribution from natural sources increased significantly from 13 to 31%. Despite Pb represented only a small portion of PM10, a strong correlation (r = 0.89, p < 0.001, multiple regression analysis) between PM10 mass and the concentrations of Pb, V, and Al was observed in the study area, suggesting that the sources of PM10 in central Taiwan can be possibly tracked by using chemical characteristics and Pb isotopes in PM10. Moreover, the Pb isotopic signals of PM10 collected during the LRT event confirmed the impact of LRT from Mainland China, and the chemical characteristics of the PM10 significantly differed from those of the PM10 collected during local events. This study demonstrates the robustness of using a combination of Pb isotopic compositions and chemical characteristics in PM10 for source tracing in complex and heavily polluted areas.

Publisher Correction: Glacial-interglacial Nd isotope variability of North Atlantic Deep Water modulated by North American ice sheet.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Glacial-interglacial Nd isotope variability of North Atlantic Deep Water modulated by North American ice sheet.

The Nd isotope composition of seawater has been used to reconstruct past changes in the contribution of different water masses to the deep ocean. In the absence of contrary information, the Nd isotope compositions of endmember water masses are usually assumed constant during the Quaternary. Here we show that the Nd isotope composition of North Atlantic Deep Water (NADW), a major component of the global overturning ocean circulation, was significantly more radiogenic than modern during the Last Glacial Maximum (LGM), and shifted towards modern values during the deglaciation. We propose that weathering contributions of unradiogenic Nd modulated by the North American Ice Sheet dominated the evolution of the NADW Nd isotope endmember. If water mass mixing dominated the distribution of deep glacial Atlantic Nd isotopes, our results would imply a larger fraction of NADW in the deep Atlantic during the LGM and deglaciation than reconstructed with a constant northern endmember.

A new anion exchange purification method for Cu stable isotopes in blood samples.

The isotopic composition of iron, zinc, copper, and cadmium (δ56Fe, δ66Zn, δ65Cu, and δ114Cd) are novel and promising tools to study the metabolism and homeostasis of trace metals in the human body. Serum δ65Cu has been proposed as a potential tool for diagnosis of cancer in liquid biopsy, and other metals may have similar utility. However, accurate analysis of trace metal isotopes is challenging because of the difficulties in purifying the metals from biological samples. Here we developed a simple and rapid method for sequential purification of Cu, Fe, Zn, and Cd from a single blood plasma sample. By using a combination of 11 M acetic acid and 4 M HCl in the first steps of column chemistry on AG-MP1 resin, we dramatically improve the separation of Cu from matrix elements compared to previous methods which use concentrated HCl alone. Our new method achieves full recovery of Cu, Fe, Zn, and Cd to prevent column-induced isotope fractionation effects, and effectively separates analytes from the matrix in order to reduce polyatomic interferences during isotope analysis. Our methods were verified by the analysis of isotope standards, a whole blood reference material, and a preliminary sample set including five plasma samples from healthy individuals and five plasma samples from cancer patients. This new method simplifies preparation of blood samples for metal isotope analysis, accelerating multi-isotope approaches to medical studies and contributing to our understanding of the cycling of Fe, Zn, Cu, and Cd in the human body. Graphical abstract ᅟ.

Ocean acidification affects coral growth by reducing skeletal density.

Ocean acidification (OA) is considered an important threat to coral reef ecosystems, because it reduces the availability of carbonate ions that reef-building corals need to produce their skeletons. However, while theory predicts that coral calcification rates decline as carbonate ion concentrations decrease, this prediction is not consistently borne out in laboratory manipulation experiments or in studies of corals inhabiting naturally low-pH reefs today. The skeletal growth of corals consists of two distinct processes: extension (upward growth) and densification (lateral thickening). Here, we show that skeletal density is directly sensitive to changes in seawater carbonate ion concentration and thus, to OA, whereas extension is not. We present a numerical model of Porites skeletal growth that links skeletal density with the external seawater environment via its influence on the chemistry of coral calcifying fluid. We validate the model using existing coral skeletal datasets from six Porites species collected across five reef sites and use this framework to project the impact of 21st century OA on Porites skeletal density across the global tropics. Our model predicts that OA alone will drive up to 20.3 ± 5.4% decline in the skeletal density of reef-building Porites corals.

Precise determination of seawater calcium using isotope dilution inductively coupled plasma mass spectrometry.

We describe a method for rapid, precise and accurate determination of calcium ion (Ca(2+)) concentration in seawater using isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS). A 10 µL aliquot of seawater was spiked with an appropriate (43)Ca enriched solution for (44)Ca/(43)Ca ID-ICP-MS analyses, using an Element XR (Thermo Fisher Scientific), operated at low resolution in E-scan acquisition mode. A standard-sample bracketing technique was applied to correct for potential mass discrimination and ratio drift at every 5 samples. A precision of better than 0.05% for within-run and 0.10% for duplicate measurements of the IAPSO seawater standard was achieved using 10 µL solutions with a measuring time less than 3 minutes. Depth profiles of seawater samples collected from the Arctic Ocean basin were processed and compared with results obtained by the classic ethylene glycol tetra-acetic acid (EGTA) titration. Our new ID-ICP-MS data agreed closely with the conventional EGTA data, with the latter consistently displaying 1.5% excess Ca(2+) values, possibly due to a contribution of interference from Mg(2+) and Sr(2+) in the EGTA titration. The newly obtained Sr/Ca profiles reveal sensitive water mass mixing in the upper oceanic column to reflect ice melting in the Arctic region. This novel technique provides a tool for seawater Ca(2+) determination with small sample size, high throughput, excellent internal precision and external reproducibility.

Precise determination of triple Sr isotopes (δ87Sr and δ88Sr) using MC-ICP-MS.

The non-traditional stable strontium (Sr) isotopes have received increasing attention recently as new geochemical tracers for studying Sr isotopic fractionation and source identification. This has been attributed to the advancement in multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), allows to determine precisely and simultaneously of the triple Sr isotopes. In this study, we applied a modified empirical external normalization (EEN) MC-ICPMS procedure for mass bias correction in Sr isotopic measurement using (92)Zr/(90)Zr. High-purity Zr Standard was spiked into sample solutions and the degree of fractionation was calculated off-line using an exponential law. The long-term external reproducibility for NIST SRM 987 δ(87)Sr and δ(88)Sr was better than 0.040‰ and 0.018‰ (2SD), respectively. The IAPSO standard seawater was used as a secondary standard to validate the analytical protocol and the absolute ratios measured were 0.709161±0.000018 for (87)Sr/(86)Sr, 0.177±0.021‰ for δ(87)Sr, and 0.370±0.026‰ for δ(88)Sr (2SD, n=7). These values are in good agreement with the literature data analyzed by thermal ionization mass spectrometry (TIMS) double spike technique. Rock standards, BHVO-2, BCR-2 and AGV-2 were also analyzed to validate the robustness of the methodology and showed identical results with literature data. Compared to previous (91)Zr/(90)Zr correction, we obtained improved results based on (92)Zr/(90)Zr, probably due to similar mass difference between (92)Zr/(90)Zr and measured Sr isotopes. The new analytical protocol presented in this study not only improves the analytical precision but also increases sample efficiency by omitting the use of the standard-sample bracketing (SSB) procedure.

Direct separation of boron from Na- and Ca-rich matrices by sublimation for stable isotope measurement by MC-ICP-MS.

An improved technique for precise and accurate determination of boron isotopic composition in Na-rich natural waters (groundwater, seawater) and marine biogenic carbonates was developed. This study used a 'micro-sublimation' technique to separate B from natural sample matrices in place of the conventional ion-exchange extraction. By adjusting analyte to appropriate pH, quantitative recovery of boron can be achieved (>98%) and the B procedural blank is limited to <8 pg. An additional mass bias effect in MC-ICP-MS was observed which could not be improved via the standard-sample-standard bracketing or the 'pseudo internal' normalization by Li. Therefore a standard other than NBS SRM 951 was used to monitor plasma condition in order to maintain analytical accuracy. An isotope cross-calibration with results from TIMS shows that the space-charge mass bias on MC-ICP-MS can be successfully corrected using off-line mathematical manipulation. Several reference materials, including the seawater IAPSO and two groundwater standards IAEA-B-2 and IAEA-B-3, were used to validate this approach. We found that the delta(11)B of the reference coral JCp-1 was 24.22+/-0.28 per thousand, corresponding to seawater pH based on the coral delta(11)B-pH function.