Rapid and precise analysis of rare earth elements in small volumes of seawater - Method and intercomparison

Behrens, Melanie; Muratli, Jesse M; Pradoux, Catherine; Wu, Yingzhe; Böning, Philipp; Brumsack, Hans‐Jürgen; Goldstein, Steven L.; Haley, Brian A.; Jeandel, Catherine; Paffrath, Ronja; Pena, Leopoldo D.; Schnetger, Bernhard; Pahnke, Katharina

doi:10.1016/j.marchem.2016.08.006

Cited by 44 publications

(40 citation statements)

References 27 publications

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“…In each REE measurement session, we adjust the gas flows to an optimal state to obtain the minimum oxide formation (0.0066 ± 0.0017, 1σ, for the Pr monitor solution) so that the oxide correction is extremely small. Our high-quality data for natural samples used for international calibration (Behrens et al, 2016;Pahnke et al, 2012; agree very well with results from different research groups in the world (section 5). In addition, the repeated analysis of samples yields very good long-term external reproducibility (section 5).…”

Section: 1029/2020gc009042supporting

confidence: 85%

A User‐Friendly Workbook to Facilitate Rapid and Accurate Rare Earth Element Analyses by ICP‐MS for Multispiked Samples

Pena

Goldstein

et al. 2020

Geochem Geophys Geosyst

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The rare earth elements (REEs) are widely used as geochemical tracers in the earth, planetary, and ocean sciences. Inductively coupled plasma‐mass spectrometry (ICP‐MS) has become the method of choice to analyze REE concentrations because it can rapidly measure the entire REE spectrum at the same time. This Technical Report presents a user‐friendly “REE Calculation Workbook” in Microsoft Excel to be used for calculating REE abundances in samples equilibrated with a multielement REE spike. This Workbook can be conveniently used to calculate REE concentrations in natural samples for spiked and unspiked elements measured by ICP‐MS. For the spiked elements, their concentrations are calculated using isotope dilution equations. Using these spiked elements as references, concentrations of the four mono‐isotopic REE elements, and other REE elements that are treated as mono‐isotopic elements (in our case, La and Lu), can be calculated. The REE Workbook can be easily set up for use with different REE spikes. Evaluation of our analytical quality using a quadrupole ICP‐MS on 10‐ml‐sized seawater samples shows that our analyses are comparable to high‐precision thermal ionization mass spectrometry (TIMS) studies, with much less time spent processing and analyzing, and with the added advantages of determining mono‐isotopic elements. An important result is the clear demonstration of enrichments in Gd and Er compared to neighboring elements in seawater samples. In addition, we compare and evaluate commonly used reference standards BCR‐1, Post‐Archean Australian Shale (PAAS), and North American Shale Composite (NASC).

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Section: 1029/2020gc009042supporting

confidence: 85%

A User‐Friendly Workbook to Facilitate Rapid and Accurate Rare Earth Element Analyses by ICP‐MS for Multispiked Samples

Pena

Goldstein

et al. 2020

Geochem Geophys Geosyst

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“…The method is intercalibrated with three other laboratories and agrees within analytical uncertainty with the intercalibration results from BATS (Pahnke et al, 2012;Behrens et al, 2016). The external reproducibility of the data presented here is <4% (RSD) except for La (5%) and Ce (8%).…”

Section: Methodssupporting

confidence: 71%

“…Rare earth elements concentrations were measured at the University of Oldenburg using an offline seaFAST isotope dilution ICP-MS method described in Behrens et al (2016). The method is intercalibrated with three other laboratories and agrees within analytical uncertainty with the intercalibration results from BATS (Pahnke et al, 2012;Behrens et al, 2016).…”

Section: Methodsmentioning

confidence: 89%

TAG Plume: Revisiting the Hydrothermal Neodymium Contribution to Seawater

et al. 2018

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We present results on the distribution of ε Nd and [Nd] from the TAG hydrothermal vent field and adjacent locations collected during the GEOTRACES GA03 cruise in October 2011. Our results show that Nd isotopes directly below and above the plume do not significantly deviate from average NADW (ε Nd = −12.3 ± 0.2). Within the plume, however, isotope values are shifted slightly toward more radiogenic values up to ε Nd = −11.4. Interestingly at the same time a significant decrease in [Nd] along with rare earth element (REE) fractionation is observed, indicating enhanced scavenging within the plume despite the change in Nd isotopes. Elemental concentrations of Nd are reduced by 19.6-18.5 pmol/kg, coinciding with the maximum increase of mantle derived helium (xs 3 He) from 0.203 to 0.675 fmol/kg, resulting in an average 1.8 pmol/kg decrease in [Nd] relative to an expected linear increase with depth. The inventory loss of Nd within the plume sums up to 614 nmoles/m 2 , or 6%, if a continuous increase of [Nd] with depth is assumed. Compared to BATS and the western adjacent station USGT11-14, the local inventory loss is even higher at 10%. The tight relationship of xs 3 He increase and [Nd] decrease allows us to estimate scavenging rates at TAG suggesting 40 mol/year are removed within the TAG plume. A global estimate using power output along ocean ridges yields an annual Nd removal of 3.44 × 10 6 mol/year, which is about 71% of riverine and dust flux combined or 6-8% of the estimated global flux of Nd into the ocean. The change in Nd isotopic composition of up to 0.7 more radiogenic ε Nd values suggests an exchange process between hydrothermally derived particles and seawater in which during the removal process an estimated 1.1 mol/year of hydrothermal Nd is contributed to the seawater at the TAG site. This estimate is only 0.1% of the global Nd signal added to the ocean by boundary exchange processes at ocean margins, limiting the ability of changing the Nd isotopic composition on a global scale in contrast to the more significant estimated sink of elemental Nd in hydrothermal plumes from this study.

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“…The importance of the monoisotopic element concentrations for quantifying the behavior of the 'anomalous' elements was enlightened when more LA data for seawater and hydrogenous sediments became available [116]. Utilizing multi-element isotope dilution inductively coupled plasma-mass spectrometry (ID ICP-MS), Behrens et al [117] reported the first application of the automated seaFAST-pico system in the offline mode for rapid and robust purification, pre-concentration, and analysis of dissolved LAs from small volumes (11 to 12 ml) of seawater. In extraction techniques (either solid phase extraction or liquid-liquid extraction), samples are exposed to other reagents, making it quite challenging to maintain process blanks below the levels required to quantify the LA accurately [118].…”

Section: Gd Determination In the Aqueous Environmentmentioning

confidence: 99%

Gadolinium as an Emerging Microcontaminant in Water Resources: Threats and Opportunities

Ebrahimi

Barbieri

2019

Geosciences

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As a result of high doses of paramagnetic gadolinium (Gd) chelates administered in magnetic resonance imaging (MRI) exams, their unmetabolized excretion, and insufficient removal in wastewater treatment plants (WWTPs), large amounts of anthropogenic Gd (Gdanth) are released into surface water. The upward trend of gadolinium-based contrast agent (Gd-CA) administrations is expected to continue growing and consequently higher and higher anthropogenic Gd concentrations are annually recorded in water resources, which can pose a great threat to aquatic organisms and human beings. In addition, the feasibility of Gd retention in patients administered with Gd-CAs repeatedly, and even potentially fatal diseases, including nephrogenic systemic fibrosis (NSF), due to trace amounts of Gd have recently arisen severe health concerns. Thus, there is a need to investigate probable adverse health effects of currently marketed Gd-CAs meticulously and to modify the actual approach in using Gd contrast media in daily practice in order to minimize unknown possible health risks. Furthermore, the employment of enhanced wastewater treatment processes that are capable of removing the stable contrast agents, and the evaluation of the ecotoxicity of Gd chelates and human exposure to these emerging contaminants through dermal and ingestion pathways deserve more attention. On the other hand, point source releases of anthropogenic Gd into the aquatic environment presents the opportunity to assess surface water—groundwater interactions and trace the fate of wastewater plume as a proxy for the potential presence of other microcontaminants associated with treated wastewater in freshwater and marine systems.

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Rapid and precise analysis of rare earth elements in small volumes of seawater - Method and intercomparison

Cited by 44 publications

References 27 publications

A User‐Friendly Workbook to Facilitate Rapid and Accurate Rare Earth Element Analyses by ICP‐MS for Multispiked Samples

A User‐Friendly Workbook to Facilitate Rapid and Accurate Rare Earth Element Analyses by ICP‐MS for Multispiked Samples

TAG Plume: Revisiting the Hydrothermal Neodymium Contribution to Seawater

Gadolinium as an Emerging Microcontaminant in Water Resources: Threats and Opportunities

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