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Geochemical evidence of Milankovitch cycles in Atlantic Ocean ferromanganese crusts

Year: 2021
Products: Elemental Scientific Lasers NWR193UC laser ablation system
Authors: Josso, Pierre, P
Application: seawater;isotope;Laser;

Hydrogenetic ferromanganese crusts are considered a faithful record of the isotopic composition of seawater influenced by weathering processes of continental masses. Given their ubiquitous presence in all oceans of the planet at depths of 400–7000 meters, they form one of the most well-distributed and accessible records of water-mass mixing and climate. However, their slow accumulation rate and poor age constraints have to date limited their use to explore 100 ka paleoclimatic phenomena. Here it is shown how the Pb isotope signature and major element content of a Fe-Mn crust from the north-east Atlantic responded to changes in the intensity and geographic extent of monsoonal rainfall over West Africa, as controlled by climatic precession during the Paleocene. The studied high-spatial resolution (4 μm) laser-ablation multi-collector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) Pb isotope data is a nearly 2 order of magnitude improvement in spatial and temporal resolution compared to micro-drill subsamples. The record demonstrates cyclicity of the 206Pb/204Pb and 208, 207Pb/206Pb ratios at the scale of single Fe-Mn oxide laminae, in conjunction with variations in the Fe/Mn ratio, Al, Si and Ti content. Time-frequency analysis and astronomical tuning of the Pb isotope data demonstrates the imprint of climatic precession (∼20 ka) modulated by eccentricity (∼100 and 405 ka), yielding growth rates of 1.5–3.5 mm/Ma consistent with previous chemostratigraphic age models. In this context, boreal summer at the perihelion causes stronger insolation over West Africa, resulting in more intense and geographically extended monsoonal rainfalls compared to aphelion boreal summer conditions. This, in turn, influences the balance between the weathering endmembers feeding the north-east Atlantic basin. These results provide a new approach for calibrating Fe-Mn crust records to astronomical solutions, and allow their isotopic and chemical archive to be exploited with an improved temporal resolution of 1000–5000 years.

Dissolved neodymium and hafnium isotopes and rare earth elements in the Congo River Plume: Tracing and quantifying continental inputs into the southeast Atlantic

Year: 2021
Products: aSeaFAST system
Authors: Rahlf, Peer, P
Application: Dissolved;seawater;isotope;

The Congo River is the second largest river by discharge in the world and a major source of element inputs into the South Atlantic Ocean. Yet, the element fluxes and transport mechanisms across and beyond its estuary and their impacts on the marine distribution and cycling of many major and trace elements are not well understood. We present the first combined dissolved neodymium (Nd) and hafnium (Hf) isotope and rare earth element (REE) concentration distributions following the Congo River plume along its flow path off the West African coast and along a connected offshore latitudinal section at 3°S. The Congo River freshwater itself is characterized by extraordinarily high Nd and Hf concentrations of up to 4000 pmol/kg and 54 pmol/kg, and by Nd (εNd) and Hf (εHf) isotope compositions that range between −15.6 and −16.4 and between 0.35 and −1.4, respectively. Our near- and offshore data indicate that at salinities above 23 conservative mixing of Congo-derived Nd and Hf concentrations and isotopic signatures with ambient surface seawater occurs for at least 1000 km to the northwest of the river mouth. This demonstrates a large spatial extent of the influence of the Congo plume on trace metal distributions in the eastern south Atlantic surface waters. A comparison between dissolved Nd and Hf fluxes from the Congo River and the shelf zone estimated based on radium isotope compositions indicate that release from Congo-derived particulate phases likely balances strong estuarine REE and Hf removal in the low salinity zone. The combined riverine and shelf zone flux for Nd is almost twice as high as that estimated for the Amazon River, despite that the Amazon discharge is about five times higher than that of the Congo River. Even the offshore Nd flux estimated for the 3 °S transect based on radium isotope compositions still corresponds to ∼40% of the Congo-shelf-zone flux and reaches 150 ± 50 Mg/year for Nd. Moreover, intermediate waters below the plume are strongly affected by exchange with particulate inputs from the Congo River given that Nd isotope signatures are inconsistent with values expected from large-scale water mass mixing and instead support unradiogenic Nd release either from sinking or deposited Congo-derived detrital material. Deep and bottom water isotopic signatures are also slightly affected by interaction with particles and benthic Nd release.

Intestine of invasive fish Prussian carp as a target organ in metal exposure assessment of the wastewater impacted freshwater ecosystem

Year: 2021
Products: autosampler
Authors: Mijošek, Tatjana, T
Application: Tissue;Environmental;Total;Species;

The application of invasive fish Prussian carp (Carassius gibelio Bloch, 1782) as bioindicator organism, using intestine as bioindicator tissue of anthropogenic influence in the lowland Ilova River was estimated. Intestinal tissue enables the investigation of dietborne metal uptake, so the first record on intestinal metal levels in Prussian carp was presented, as total and cytosolic fraction, which indicates the proportions of potentially toxic and bioavailable metals. Pollution impact was also estimated by analyses of biomarkers of oxidative stress (malondialdehyde), antioxidative capacity (catalase and glutathione) and of metal exposure (metallothioneins). All analyzed parameters were compared in the intestine of fish from the reference site and contaminated site impacted by technological and municipal wastewaters in two seasons. Both total and cytosolic As, Ca, Cd, Cs, Cu, Mg, Na and Rb levels were significantly higher at contaminated than the reference site in at least one season, whereas Mn and V had higher concentrations at the reference site. Despite differences in concentrations, average proportions of total metal levels in cytosolic fraction were comparable at two sites, i.e. over 70% for Na, K, Rb, Se, Cd, Cs, As and Mo, indicating their high possibility of binding to important biomolecules. In addition, higher levels of malondialdehyde in both seasons and enhanced catalase activity in spring, indicated disturbed environmental conditions near the contaminated site and need of continuous monitoring of this region. Finally, our research represents successful application of widely distributed invasive species in ecotoxicological studies, whereas intestine was shown as a suitable bioindicator tissue, clearly reflecting dietary metal uptake.

Carboniferous–Permian transgression/regression mechanisms in the Eastern Ordos Basin and their sea-level spatiotemporal variability: Insights from source-to-sink systems

Year: 2021
Products: NWR193UC 193 nm deep ultraviolet laser ablation sampling system
Authors: Fu, Chao, C
Application: Laser;

Developed on the North China Craton, the intracratonic Ordos Basin contains a complete Paleozoic-to-Cenozoic sediment record, allowing for long-term paleoenvironmental and climate change investigation. During the Carboniferous–Permian period, convergence between the North China block and the paleo-Yangtze plate to the south resulted in a general marine regression characterized by a series of second-order transgression/regression cycles diachronous along the eastern margin of the Ordos. However, the detailed mechanisms that induced these cycles, as well as the associated paleoecological changes, remain unknown. In this study, we integrate multiple indices, including δ18O and δ13C, rare earth element (REE), paleontological assemblages, and clay content (w (chlorite + kaolinite)/w((Illite) ratio) planar distribution, to restore the paleo-water depth distribution. These parameters are then used to reconstruct the paleo-sea level from the Pennsylvanian to the middle Permian. We conclude that the direction of second-order transgression/regression was mainly toward the east during the Pennsylvanian–early Permian and switched clockwise toward the north during the middle Permian. We suggest that the second-order cycles, diachronous in space and time, are mainly linked to local variations in sediment supply and regional uplift. Using detrital zircon U–Pb data and the REE and trace element content and heavy mineral assemblages (HMA), we estimate the sediment provenance area. The sediment volumes deposited in the basin through time are obtained using 2D seismic data. During the Carboniferous, the coarse-grained sediments deposited in the eastern Ordos were derived from the uplifting Helan Mountain (Qiandam–Qilian orogenic belt). By the middle Permian, the detrital material became multi-sourced, thus issuing the Yinshan range to the north and the Qinling range to the south. We then integrate the description of numerous core samples with electric log and 2D seismic data to reconstruct the sediment facies associations across the first-order regression from the Carboniferous tidal flat depositional system to the middle Permian prograding fluvial delta system. According to the transfer of the glacial epoch, the sedimentation rate, and the transgression/regression rate above, we classify the evolution process into three patterns: low-transgression rate and less-sediment supply pattern (the late Carboniferous), high regression rate and mass sediment supply pattern (the north block during the early Permian), and low regression rate and mass sediment supply pattern (the south block during the Sakmarian stage). Lastly, with the quantitative calculation of the source-to-sink (S2S) parameters, including the S2S system volume and the elevated height of regional uplift with the 2D seismic data, we propose the mechanism of transgression/regression in the Ordos Basin, responding to the above three pattern s. The first pattern was controlled by regional uplift, whereas the second pattern was controlled by sediment supply. As to the third one, uplift and sediment supply could affect the transgression/regression process.

Chromium mobility in ultramafic areas affected by mining activities in Barro Alto massif, Brazil: An isotopic study

Year: 2021
Products: desolvating nebulization system (APEX-IR)
Authors: Bolaños-Benítez, Viviana, V
Application: Environmental;Dissolved;Species;soil;

This work studies the potential release of Cr from solids to surface water and groundwater, and the related isotopic compositions, in a nickel laterite ore deposit from Barro Alto in Brazil (in the State of Goiás). This ultramafic system is characterized by elevated concentrations of chromium (Cr). Even largely immobile Cr may be naturally leached from weathering profiles such as laterite to the surface and groundwater. This system is exploited for metal production, and both mining and metallurgical activities result in a significant increase in the trivalent (Cr(III)) and hexavalent chromium (Cr(VI)) concentrations released into the environment via runoff. Among all the samples collected, ores contained higher amounts of chemically and isotopically exchangeable Cr(VI) (ECr(VI)) with values as high as 104 (± 8) mg kg−1. δ53Cr increased from −0.28 (± 0.01)‰ to −0.05 (± 0.01)‰ and the ECr(VI) value was up to 30 times higher in deep soils than at the surface (up to 7 (± 1) mg kg−1). Chemically extracted Cr(VI) (ECr(VI)-KH2PO4) displayed positive δ53Cr value (1.69 (±0.03) ‰) with a similar Cr isotopic composition as the ones measured in freshwater sampled in and around the mine area. It appears that Cr is primarily released as Cr(VI), i.e. the toxic species, and becomes increasingly more available as it moves from the soil profile to the ores and mining residues. Based on the differences in the Cr isotopic composition, this study proves that δ53Cr can be used in environmental studies to trace Cr leaching.

Simultaneous determination of platinum group elements and rhenium mass fractions in road dust samples using isotope dilution inductively coupled plasma-tandem mass spectrometry after cation exchange separation

Year: 2021
Products: ESI SC-2 auto sampler
Authors: Mitra, Arijeet, A
Application: Environmental;soil;isotope;

Measurement of Platinum Group Element (PGE: Ru, Rh, Pd, Os, Ir, and Pt) and Rhenium (Re) in environmental samples is a difficult task due to their ultra-trace level concentrations, and these metals suffer from severe isobaric and polyatomic interference. These kinds of issues have been solved for environmental samples having simple matrices such as tunnel dust and moss. However, a scope of improvement still exists in challenging sample matrices such as road dust, soil, and rocks. In this study, a method that enables measurement of PGE and Re mass fractions in road dust and rock samples is proposed. The method involves matrix removal using a cation-exchange column followed by measurement using inductively coupled plasma tandem mass spectrometry (ICP-MS/MS, also known as ICP- QQQ-MS) with 10% NH3 in He as reactive gas in Collision/Reaction Cell. This study emphasizes that the usage of a simple cation-exchange column is an important step over the framework developed by Suoranta et al., 2012, which was developed to measure PGE and Re fractions in environmental samples having a simpler matrix such as moss samples. The method combines high pressure (130 bars) and high temperature (220 °C) digestion procedure in combination with isotope dilution (ID) as a calibration strategy, PGE and Re separation using cation exchange resin, and their measurements using ICP-MS/MS. The method was validated with road dust (BCR-723) and ultramafic komatiite (OKUM) having a complex matrix. The measured PGE and Re mass fractions of the two-measured reference material show excellent agreement with their certified values and have intermediate precisions ranging from 0.4–7.7% RSD. We conclude that the combination of single-stage cation-exchange chromatography with ID-ICP-MS/MS measurements enables measurement results with uncertainties fit for purpose for PGE and Re mass fractions in environmental samples with a complex matrix.

Simultaneous lead isotope ratio and gold-lead-bismuth concentration analysis of silver by laser ablation MC-ICP-MS

Year: 2021
Products: NWR193 excimer laser ablation system
Authors: Standish, Christopher D., C
Application: isotope;Laser;

A new approach is presented for the simultaneous analysis of lead isotope ratios and gold, lead, and bismuth concentrations in metallic silver using nanosecond laser ablation multi-collector inductively-coupled plasma mass spectrometry (LA-MC-ICP-MS). Corrections for both isotope and concentration analyses are performed using an in-house matrix matched silver reference material RM3834. Accuracy and external reproducibility are demonstrated by repeat analyses of a further seven silver reference materials all characterised by solution (MC)-ICP-MS approaches. Typical internal precisions, expressed as two relative standard errors (S.E.) of the mean of the cycles comprising one analysis, are

Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Imaging in Biology

Year: 2021
Products: Elemental Scientific Lasers
Authors: Doble, PA;de Vega, RG;Bishop, DP;Hare, DJ;Clases, D;
Application: Cells;Laser;

Elemental imaging gives insight into the fundamental chemical makeup of living organisms. Every cell on Earth is comprised of a complex and dynamic mixture of the chemical elements that define structure and function. Many disease states feature a disturbance in elemental homeostasis, and understanding how, and most importantly where, has driven the development of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) as the principal elemental imaging technique for biologists. This review provides an outline of ICP-MS technology, laser ablation cell designs, imaging workflows, and methods of quantification. Detailed examples of imaging applications including analyses of cancers, elemental uptake and accumulation, plant bioimaging, nanomaterials in the environment, and exposure science and neuroscience are presented and discussed. Recent incorporation of immunohistochemical workflows for imaging biomolecules, complementary and multimodal imaging techniques, and image processing methods is also reviewed.

Plant flavones enrich rhizosphere Oxalobacteraceae to improve maize performance under nitrogen deprivation

Year: 2021
Products: SC-2 DX Autosampler
Authors: Yu, P;He, X;Baer, M;Beirinckx, S;Tian, T;Moya, YAT;Zhang, X;Deichmann, M;Frey, FP;Bresgen, V;Li, C;Razavi, BS;Schaaf, G;von Wiren, N;Su, Z;Bucher, M;Tsuda, K;Goormachtig, S;Chen, X;Hochholdinger, F;
Application: soil;

Beneficial interactions between plant roots and rhizosphere microorganisms are pivotal for plant fitness. Nevertheless, the molecular mechanisms controlling the feedback between root architecture and microbial community structure remain elusive in maize. Here, we demonstrate that transcriptomic gradients along the longitudinal root axis associate with specific shifts in rhizosphere microbial diversity. Moreover, we have established that root-derived flavones predominantly promote the enrichment of bacteria of the taxa Oxalobacteraceae in the rhizosphere, which in turn promote maize growth and nitrogen acquisition. Genetic experiments demonstrate that LRT1-mediated lateral root development coordinates the interactions of the root system with flavone-dependent Oxalobacteraceae under nitrogen deprivation. In summary, these experiments reveal the genetic basis of the reciprocal interactions between root architecture and the composition and diversity of specific microbial taxa in the rhizosphere resulting in improved plant performance. These findings may open new avenues towards the breeding of high-yielding and nutrient-efficient crops by exploiting their interaction with beneficial soil microorganisms.

Two chemically distinct root lignin barriers control solute and water balance

Year: 2021
Products: Elemental Scientific Inc. autosampler
Authors: Reyt, G;Ramakrishna, P;Salas-Gonzalez, I;Fujita, S;Love, A;Tiemessen, D;Lapierre, C;Morreel, K;Calvo-Polanco, M;Flis, P;Geldner, N;Boursiac, Y;Boerjan, W;George, MW;Castrillo, G;Salt, DE;
Application: Cells;

Lignin is a complex polymer deposited in the cell wall of specialised plant cells, where it provides essential cellular functions. Plants coordinate timing, location, abundance and composition of lignin deposition in response to endogenous and exogenous cues. In roots, a fine band of lignin, the Casparian strip encircles endodermal cells. This forms an extracellular barrier to solutes and water and plays a critical role in maintaining nutrient homeostasis. A signalling pathway senses the integrity of this diffusion barrier and can induce over-lignification to compensate for barrier defects. Here, we report that activation of this endodermal sensing mechanism triggers a transcriptional reprogramming strongly inducing the phenylpropanoid pathway and immune signaling. This leads to deposition of compensatory lignin that is chemically distinct from Casparian strip lignin. We also report that a complete loss of endodermal lignification drastically impacts mineral nutrients homeostasis and plant growth.

Anthropogenic lead pervasive in Canadian Arctic seawater

Year: 2021
Products: Apex
Authors: De Vera, J;Chandan, P;Pinedo-Gonzalez, P;John, SG;Jackson, SL;Cullen, JT;Colombo, M;Orians, KJ;Bergquist, BA;
Application: Dissolved;seawater;

Anthropogenic Pb is widespread in the environment including remote places. However, its presence in Canadian Arctic seawater is thought to be negligible based on low dissolved Pb (dPb) concentrations and proxy data.

Salp fecal pellets release more bioavailable iron to Southern Ocean phytoplankton than krill fecal pellets

Year: 2021
Products: SeaFAST
Authors: Bockmann, S;Koch, F;Meyer, B;Pausch, F;Iversen, M;Driscoll, R;Laglera, LM;Hassler, C;Trimborn, S;
Application: Dissolved;Species;seawater;

Over the last decades, it has been reported that the habitat of the Southern Ocean (SO) key species Antarctic krill (Euphausia superba) has contracted to high latitudes, putatively due to reduced winter sea ice coverage, while salps as Salpa thompsoni have extended their dispersal to the former krill habitats. To date, the potential implications of this population shift on the biogeochemical cycling of the limiting micronutrient iron (Fe) and its bioavailability to SO phytoplankton has never been tested. Based on uptake of fecal pellet (FP)-released Fe by SO phytoplankton, this study highlights how efficiently krill and salps recycle Fe.

70-Year Anthropogenic Uranium Imprints of Nuclear Activities in Baltic Sea Sediments

Year: 2021
Products: seaFAST
Authors: Lin, M;Qiao, J;Hou, X;Dellwig, O;Steier, P;Hain, K;Golser, R;Zhu, L;
Application: Dissolved;Total;nuclear;

A strongly stratified water structure and a densely populated catchment make the Baltic Sea one of the most polluted seas. Understanding its circulation pattern and time scale is essential to predict the dynamics of hypoxia, eutrophication, and pollutants. Anthropogenic 236U and 233U have been demonstrated as excellent transient tracers in oceanic studies, but unclear input history and inadequate long-term monitoring records limit their application in the Baltic Sea. From two dated Baltic sediment cores, we obtained high-resolution records of anthropogenic uranium imprints originating from three major human nuclear activities throughout the Atomic Era. Using the novel 233U/236U signature, we distinguished and quantified 236U inputs from global fallout (45.4-52.1%), Chernobyl accident (0.3-1.8%), and discharges from civil nuclear industries (46.1-54.3%) to the Baltic Sea. We estimated the total release of 233U (7-15 kg) from the atmospheric nuclear weapon testing and pinpointed the 233U peak signal in the mid-to-late 1950s as a potential time marker for the onset of the Anthropocene Epoch. This work also provides fundamental 236U data on Chernobyl accident and early discharges from civil nuclear facilities, prompting worldwide 233U-236U tracer studies. We anticipate our data to be used in a broader application in model-observation interdisciplinary research on water circulation and pollutant dynamics in the Baltic Sea.

Uranium Isotope Fractionation during the Anoxic Mobilization of Noncrystalline U(IV) by Ligand Complexation

Year: 2021
Products: perfluoroalkoxy alkane (PFA) nebulizer
Authors: Roebbert, Y;Rosendahl, CD;Brown, A;Schippers, A;Bernier-Latmani, R;Weyer, S;
Application: isotope;

Uranium (U) isotopes are suggested as a tool to trace U reduction. However, noncrystalline U(IV), formed predominantly in near-surface environments, may be complexed and remobilized using ligands under anoxic conditions. This may cause additional U isotope fractionation and alter the signatures generated by U reduction. Here, we investigate the efficacy of noncrystalline U(IV) mobilization by ligand complexation and the associated U isotope fractionation. Noncrystalline U(IV) was produced via the reduction of U(VI) (400 uM) by Shewanella oneidensis MR-1 and was subsequently mobilized with EDTA (1 mM), citrate (1 mM), or bicarbonate (500 mM) in batch experiments.

Using Sr-Nd-Pb isotope systems to trace sources of sediment and trace metals to the Weser River system (Germany) and assessment of input to the North Sea

Year: 2021
Products: Elemental Scientific APEX Omega desolvation system
Authors: Deng, F;Hellmann, S;Zimmermann, T;Profrock, D;
Application: isotope;

In order to trace the sources of sediment materials and trace metals in the Weser River system (Germany), and the riverine input to the North Sea, Sr, Nd and Pb isotopes, together with multi-elemental compositions, were measured for sediments collected over the entire Weser River Basin, from headwaters to the estuary. Mass fractions of metals, including Ag, Cd, and Pb, and of one metalloid, Sb, higher than their crustal abundance, were observed within the entire Weser Basin.

Assessing variability in the ratio of metal concentrations measured by DGT-type passive samplers and spot sampling in European seawaters

Year: 2021
Products: online pre-concentration seaFAST system
Authors: Rodriguez, JG;Amouroux, I;Belzunce-Segarra, MJ;Bersuder, P;Bolam, T;Caetano, M;Carvalho, I;Correia Dos Santos, MM;Fones, GR;Gonzalez, JL;Guesdon, S;Larreta, J;Marras, B;McHugh, B;Menet-Nedelec, F;Menchaca, I;Millan Gabet, V;Montero, N;Nolan, M;Regan, F;Robinson, CD;Rosa, N;Rodrigo Sanz, M;Schintu, M;White, B;Zhang, H;
Application: Environmental;Dissolved;Total;Speciation;seawater;

The current study evaluates the effect of seawater physico-chemical characteristics on the relationship between the concentration of metals measured by Diffusive Gradients in Thin films (DGT) passive samplers (i.e., DGT-labile concentration) and the concentrations measured in discrete water samples. Accordingly, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to measure the total dissolved metal concentrations in the discrete water samples and the labile metal concentrations obtained by DGT samplers; additionally, lead and cadmium conditional labile fractions were determined by Anodic Stripping Voltammetry (ASV) and total dissolved nickel was measured by Cathodic Stripping Voltammetry (CSV).

Distinctive distribution and migration of global fallout plutonium isotopes in an alpine lake and its implications for sediment dating

Year: 2021
Products: APEX-Q high-efficiency sample introduction system
Authors: Guo, H;Xu, Y;Pan, S;Liu, Z;
Application: Total;

This work investigated plutonium (Pu) isotopes in sediment cores collected from an alpine lake (Lake Heinongpo with 3779 m above sea level) in Southwestern China. 240Pu/239Pu atom ratios in all sediment samples showed the typical global fallout values of ~0.18 without any influences from other Pu contaminant sources. 239+240Pu activities with surface and subsurface maximums followed by exponential decline with sediment depth were respectively observed in the two sediment cores. The distinctive depth distributions of 239,240Pu in the lake sediments was attributed to the very slow sediment deposition rate due to the lack of terrestrial sediment input, while the alpine snowmelt input was the primary source of Pu in the lake sediments in addition to the direct atmospheric deposition.

Development of an Automatic Column Chromatography Separation Device for Metal Isotope Analysis Based on Droplet Counting

Year: 2021
Products: commercialized fully automated ion exchange chromatography system prepFAST-MC
Authors: Zhou, FY;He, D;Miao, X;Yang, C;Dong, JH;Zheng, HT;Cheng, Z;Liu, X;Zhu, ZL;
Application: isotope;

A novel, simple, cost-effective, reliable, and practical automatic column chromatography separation device capable of simultaneously purifying samples for radiogenic and non-traditional stable isotope analysis has been developed. The device avoids the use of any pump and features eluent driving by the siphon effect (gravity) and quantitative control by infrared droplet counting. Several factors affecting the control of droplets were investigated, including types and concentrations of eluents and the height of the liquid level. Results showed that accurate dripping of the eluent could be readily achieved by controlling the number of droplets under selected conditions. The separation performance of the device was first demonstrated by the elution of Sr and Cd in synthetic matrix solutions. The recoveries of Sr and Cd samples were better than 87.6 and 95.0%, respectively, and the whole procedure blank was about 0.3 ng for Sr and 0.1 ng for Cd. Finally, the reliability of the device was further validated by the purification of Sr and Cd from different geological reference materials (NIST 2711a, Nod-A-1, BCR-2, and BHVO-2). The determined Cd and Sr isotope values agree well with their reference values within the uncertainty range. All these results clearly demonstrate the reliability and practicability of the proposed device, which provides a promising method for the automated purification of isotope samples.

Determination of Vanadium Isotope Compositions in Carbonates Using an Fe Coprecipitation Method and MC-ICP-MS

Year: 2021
Products: PFA MicroFlow Teflon nebulizer
Authors: Dong, LH;Wei, W;Yu, CL;Hou, ZH;Zeng, Z;Chen, T;Huang, F;
Application: isotope;high matrix;

Vanadium isotope compositions (δ(51V)) in marine carbonates are a potential proxy to trace global redox states of ancient oceans. Although high-precision δ(51V) analyses are available for many geological materials, carbonate-hosted δ(51V) data have not been reported yet due to extremely high matrix elements and low V contents (generally below 10 ug g-1). In this study, we developed an Fe coprecipitation method combined with an Fe column to preconcentrate V from the major matrix elements and subsequent four-step chromatographic procedures to further purify V in carbonates. The δ(51V) values were measured using a sample-standard bracketing method by MC-ICP-MS. The robustness of this method was assessed by analyzing element-doped and matrix-spiked synthetic carbonate solutions containing an in-house δ(51V) standard, USTC-V. The mean δ(51V) value of the synthetic carbonate solutions (0.06 ± 0.08‰; 2SD, n = 33) is in good agreement with the recommended value of the USTC-V relative to the Oxford AA solution (0.07 ± 0.08‰; 2SD, n = 347). In addition, the consistency in the δ(51V) value of the igneous carbonatite standard, COQ-1, which was processed in parallel with the whole purification (-0.48 ± 0.04‰; 2SD, n = 3) and a four-step chromatographic procedure (-0.43 ± 0.08‰; 2SD, n = 3), further validates the robustness of our method. For the first time, we obtained δ(51V) values of four carbonate reference materials: JDo-1, -0.56 ± 0.09‰ (2SD, n = 27); JLs-1, -0.61 ± 0.14‰ (2SD, n = 33); GBW07217a, -0.79 ± 0.09‰ (2SD, n = 6); GBW07214a, -0.51 ± 0.13‰ (2SD, n = 48). The long-term external precision of carbonate-hosted δ(51V) analyses is better than ± 0.14‰ (2SD). Our method can be applied to measure carbonate-hosted δ(51V) to trace the evolution in global marine redox states throughout the Earth's history.

Activated Carbon Electrode Tip for Heavy Metal Capture and In Situ Analysis by Microplasma Optical Emission Spectrometry

Year: 2021
Products: NWR266 laser ablation system
Authors: Liu, S;Xue, XX;Yu, YL;Wang, JH;
Application: Laser;detection limits;

The miniaturized optical emission spectrometry (OES) devices based on various microplasma excitation sources provide reliable tools for on-site analysis of heavy metal pollution, while the development of convenient and efficient sample introduction approaches is essential to improve their performances for field analysis. Herein, a small activated carbon electrode tip is employed as solid support to preconcentrate heavy metals in water and subsequently served as an inner electrode of the coaxial dielectric barrier discharge (DBD) to generate microplasma. In this case, heavy metal analytes in water are first adsorbed on the surface of the activated carbon electrode tip via a simple liquid-solid phase transformation during the sample loading process, and then, fast released to produce OES during the DBD microplasma excitation process. The corresponding OES signals are synchronously recorded by a charge-coupled device (CCD) spectrometer for quantitative analysis. This activated carbon electrode tip provides a new tool for sample introduction into the DBD microplasma and facilitates 'insert-and-go' in subsequent DBD-OES analysis. With a multiplexed activated carbon electrode tip array, a batch of water samples (50 mL) can be loaded in parallel within 5 min. After drying the activated carbon electrode tips for 5 min, the DBD-OES analysis is maintained at a rate of 6 s per sample. Under the optimized conditions, the detection limits of 0.03 and 0.6 ug L-1 are obtained for Cd and Pb, respectively. The accuracy and practicability of the present DBD-OES system have been verified by measuring several certified reference materials and real water samples. This analytical strategy not only simplifies the sample pretreatment steps but also significantly improves the sensitivity of the DBD-OES system for heavy metal detection. By virtue of the advantages of high sensitivity, fast analysis speed, simple operation, low cost, and favorable portability, the upgraded DBD-OES system provides a more powerful tool for on-site analysis of heavy metal pollution.

Technical note: Sea salt interference with black carbon quantification in snow samples using the single particle soot photometer

Year: 2021
Products: Apex Q
Authors: Zanatta, M;Herber, A;Juranyi, Z;Eppers, O;Schneider, J;Schwarz, J;
Application: Laser;

After aerosol deposition from the atmosphere, black carbon (BC) takes part in the snow albedo feedback contributing to the modification of the Arctic radiative budget. With the initial goal of quantifying the concentration of BC in the Arctic snow and subsequent climatic impacts, snow samples were collected during the research vessel (R/V) Polarstern expedition of PASCAL (Physical Feedbacks of Arctic Boundary Layer, Sea Ice, Cloud and Aerosol; Polarstern cruise 106) in the sea-ice-covered Fram Strait in early summer 2017. The refractory BC (rBC) content was then measured in the laboratory of the Alfred Wegener Institute with the single particle soot photometer (SP2). Based on the strong observational correlations between both rBC concentration and rBC diameter with snow salinity, we hypothesize a salt-induced matrix effect interfering with the SP2 analysis.

AF4-UV-ICP-MS for detection and quantification of silver nanoparticles in seafood after enzymatic hydrolysis

Year: 2021
Products: SeaFast SC2 DX autosampler
Authors: Taboada-Lopez, MV;Bartczak, D;Cuello-Nunez, S;Goenaga-Infante, H;Bermejo-Barrera, P;Moreda-Pineiro, A;
Application: Total;

A method based on asymmetric flow field-flow fractionation (AF4) coupled to ultraviolet-visible (UV-vis) spectroscopy and inductively coupled plasma mass spectrometry (ICP-MS) has been developed for silver nanoparticles (Ag NPs) detection and quantification in bivalve molluscs. Samples were pre-treated using a conventional enzymatic (pancreatin and lipase) hydrolysis procedure (37 °C, 12 h). AF4 was performed using a regenerated cellulose (RC) membrane (10 kDa, 350 um spacer) and aqueous 5 mM Tris-HCl pH = 7.4 as carrier. AF4 separation was achieved with a program that included a focusing step with tip and focus flows of 0.20 and 3.0 mL min-1, respectively, and an injection time of 4.0 min. Elution of different size fractions was performed using a cross flow of 3.0 mL min-1 for 15 min, followed by linear cross flow decrease for 7.5 min, and a washing step for 9.4 min with no cross flow. Several bivalve molluscs (clams, oysters and variegated scallops) were analysed for total Ag content (ICP-MS after microwave assisted acid digestion), and for Ag NPs by the method presented here. Results show that Ag NPs are detected at the same elution time than proteins (UV monitoring at 280 and 405 nm), which suggests a certain interaction occurred between Ag NPs with proteins in the enzymatic extracts. AF4-UV-ICP-MS fractograms also suggest different Ag NPs size distributions for selected samples. Membrane recoveries, determined by peak area comparison of fractograms with and without application of cross flow, were within the 49-121% range. Confirmation of the presence Ag NPs in the investigated enzymatic extracts was demonstrated by SEM after an oxidative pre-treatment based on hydrogen peroxide and microwave irradiation.

A novel copper (II) binding peptide for a colorimetric biosensor system design

Year: 2021
Products: auto sampler SC-E2 DX
Authors: Korkmaz, N;Hwang, C;Kessler, KK;Silina, YE;Muller, L;Park, J;
Application: ~

Filamentous bacteriophages are viruses infecting only bacteria. In this study, phage display technique was applied to identify highly selective Cu(II) binding peptides. After five rounds of positive screening against Cu(II) and various rounds of negative screenings against competitive metal ions (Al(III), Co(II), Fe(III), Ni(II) and Zn(II)), bacteriophages were enriched. Selective Cu(II) binding of final phages was confirmed by Enzyme Linked Immunosorbent Assay (ELISA), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray spectroscopy (EDX) analyses. 15 phage plaques were randomly selected and sequenced. Cu-5 peptide (HGFANVA) with the highest frequency of occurrence and the strongest Cu(II) affinity was chosen for further Cu(II) detection and removal tests. Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) confirmed the strong Cu(II) binding potential of engineered viruses. Cu-5 peptides were synthetically synthesized with three Cysteine units at C-terminal and a AuNP-peptide biosensor system was developed based on aggregation behavior of AuNPs upon Cu(II) ion treatment.

A rapid, automated system for the separation, preconcentration and measurement of 90Sr, and U, Am and Pu isotopes

Year: 2021
Products: Product Unavailable
Authors: Wang, W;Evans, R;Evans, H;
Application: Urine;seawater;detection limits;

An online separation and preconcentration method, using an automated flow injection setup and solid phase extraction followed by ICP-MS/MS, was developed for the analysis of 90Sr, and U, Am and Pu isotopes in various liquid sample matrices. The radionuclide analytes were separated from interferences and complex matrices using DGA-branched resin and Sr resin, then specific gases were used in the reaction/collision cell in the ICP-MS/MS to measure the different analytes. The system requires smaller sample volumes (10 mL), less sample preparation and shorter processing time (46 min per sample) compared to traditional radiometric and other MS techniques. Based on a 10 mL sample, the limits of detection were 1.48 pg L-1 (8257 mBq L-1) for 90Sr, 1.75 pg L-1 (0.40 mBq L-1) for 234U, 0.65 pg L-1 (77.65 mBq L-1) for 241Am, and 0.56 pg L-1 (1.25 mBq L-1) for 239Pu when all target analytes were measured in one analysis. The analytical figures of merit were evaluated for a range of sample matrices including lake water, seawater and urine and were comparable to those reported in the literature. This online system thus provides a novel, fully automated analytical tool with faster analysis time, smaller sample requirements, minimum sample preparation, low detection limits and the flexibility to handle single and multiple measurements of various radionuclides.

On the origin of high-pressure mafic granulite in the Eastern Himalayan Syntaxis: Implications for the tectonic evolution of the Himalayan orogen

Year: 2021
Products: NWR 193 UC laser ablation system
Authors: Zhang, Z;Ding, H;Palin, R;Dong, X;Tian, Z;Kong, D;Jiang, Y;Qin, S;Li, W;
Application: Laser;

The Himalayan orogen, resulting from the Early Cenozoic collision of the Indian and Asian plates, is an ideal vehicle to study active orogenic processes and test geodynamic models of how the crust responds to collisional orogeny. This paper focused on migmatitic high-pressure (HP) mafic granulite and associated leucosome from the Greater Himalayan Crystallines (GHC) in the Eastern Himalayan Syntaxis (EHS) in order to understand the conditions and timescales over which high-grade rocks and partial melts were produced during the Himalayan orogeny. Combining with previous study results from the Western and Central Himalayas and Trans-Himalayan magmatic arc, we obtained the following conclusions: (1) The mafic granulites from the EHS underwent HP and high-temperature (HT) granulite facies metamorphism and partial melting, with peak metamorphic conditions of 15-17 kbar and 820-880 °C. The GHC, at least its western part of the EHS, underwent coherent HP granulite-facies metamorphism. (2) The HP mafic granulites experienced long-lived dehydration melting of amphibole from ~40 Ma to ~20 Ma during prograde metamorphism and generated up to ~16 vol% partial melt. The variable degrees of dehydration melting of the HP mafic, pelitic and felsic granulites in the EHS generated voluminous granitic melts with distinct compositions, and provided the source for the Himalayan granites. (3) Peak metamorphic pressure of the GHC gradually decreases, whereas the metamorphic temperature progressively increases from the Western to Eastern Himalayas. This indicates that the Indian continental crust deeply subducted into the mantle in the Western Himalaya after the Indo-Asia collision, whereas the Indian crust underthrusted or relaminated beneath the Asian continental crust, and formed the thickened lower crust in the Central and Eastern Himalayas and Gangdese arc. (4) The melts derived from the underthrusted Indian crust probably resulted in isotopic compositional enrichment of the Early Cenozoic mantle- and juvenile crust-derived magmatic rocks of the Gangdese arc.

Provenance of the Phuquoc Basin fill, southern Indochina: Implication for Early Cretaceous drainage patterns and basin configuration in Southeast Asia

Year: 2021
Products: Elemental Scientific Lasers
Authors: Nguyen, T;Fyhn, M;Kristensen, J;Nielsen, L;Thomsen, T;Keulen, N;Lindstrom, S;Boldreel, L;
Application: Laser;

Cretaceous basins cover large parts of mainland SE Asia. Yet, the development during the Cretaceous is poorly understood including the establishment of the Cretaceous basin configuration. Based on detrital zircon and heavy mineral analysis, this study investigates the provenance of Lower Cretaceous deposits in the Phuquoc Basin, exposed in Cambodia and SW Vietnam and extending into the Gulf of Thailand. Our results document five major zircon populations with 130-145 Ma, 145-200 Ma, 200-270 Ma, 420-470 Ma, 1800-1900 Ma ages and two subordinate 2400-2700 Ma, 750-1000 Ma age clusters. These ages resemble those of the Qinling-Dabie and the Songpan-Ganzi orogenic belts and differ from other Asian terranes. These ages suggest that the Qinling-Dabie and Songpan-Ganzi orogenic belts were major sources of sediment for the Phuquoc Basin in the Early Cretaceous. Heavy mineral compositions including the presence of almandine, often co-occurring with silimanite and epidote, suggest metamorphic and granitic constituents in the hinterland, compatible with these orogenic belts being the source.

Trace element analysis of human seminal plasma: A cautionary tale of preanalytical variation and use of non-traditional matrices in human biomonitoring studies

Year: 2021
Products: ultra-low particulate arrester (UPLA) air filter
Authors: Galusha, AL;Farnsworth, AC;Bloom, MS;Kruger, PC;McGough, A;Lenhart, N;Wong, R;Fujimoto, VY;Mok-Lin, E;Parsons, PJ;
Application: ~

Ensuring harmonization of (ultra-)trace element measurements in non-traditional matrices is a particular analytical challenge that is highlighted in this work for seminal plasma as part of the developmental core at the Wadsworth Center Human Health Exposure Analysis Resource Targeted Laboratory. Seminal plasma was collected from 39 male partners of women undergoing in vitro fertilization and analyzed by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) following deproteinization with concentrated HNO3. Validation was accomplished using: 1) two aqueous NIST SRMs; 2) a seminal plasma QC pool, characterized via standard additions; 3) standard additions on a subset of samples; and 4) sample duplicates. Agreement with NIST certified or reference values were obtained to within ±15% for the SRMs, and agreement between aqueous calibration values and standard additions values agreed to within ±10-20% for all elements. Standard additions of seminal plasma samples revealed varying matrix effects for Cu and Cr that were not found for the pooled samples. Duplicate analyses agreed to within ±10-30% depending on element. A potential source of contamination in colloidal silica used for processing seminal plasma was identified that requires further study. Comparisons with literature indicate lack of consensus for As, Cd, Cr, Mn, Pb, and V content in seminal plasma. Further work is needed to improve harmonization of future studies.

Evaluation of Zn, Cu, and Se Levels in the North American Autism Spectrum Disorder Population

Year: 2021
Products: Elemental Scientific Inc. (ESI) SC2-DX autosamplers
Authors: Mehta, SQ;Behl, S;Day, PL;Delgado, AM;Larson, NB;Stromback, LR;Huebner, AR;DeGrado, TR;Davis, JM;Jannetto, PJ;Howie, F;Pandey, MK;
Application: Serum;Blood;Total;

Metal ion dyshomeostasis and disparate levels of biometals like zinc (Zn), copper (Cu), and selenium (Se) have been implicated as a potential causative factor for Autism Spectrum Disorder (ASD). In this study, we have enrolled 129 children (aged 2-4 years) in North America, of which 64 children had a diagnosis of ASD and 65 were controls. Hair, nail, and blood samples were collected and quantitatively analyzed for Zn, Cu and Se using inductively coupled plasma mass spectrometry (ICP-MS). Of the analyzed biometals, serum Se (116.83 ± 14.84 mcg/mL) was found to be significantly lower in male ASD cases compared to male healthy controls (128.21 ± 9.11 mcg/mL; p < 0.005). A similar trend was found for nail Se levels in ASD (1.01 ± 0.15 mcg/mL) versus that of controls (1.11 ± 0.17 mcg/mL) with a p-value of 0.0132 using a stratified Wilcoxon rank sum testing. The level of Se in ASD cohort was co-analyzed for psychometric correlation and found a negative correlation between total ADOS score and serum Se levels. However, we did not observe any significant difference in Zn, Cu, and Zn/Cu ratio in ASD cases versus controls in this cohort of North American children. Further studies are recommended to better understand the biology of the relationship between Se and ASD status.

Proteomic response of the marine ammonia-oxidising archaeon Nitrosopumilus maritimus to iron limitation reveals strategies to compensate for nutrient scarcity

Year: 2021
Products: Elemental Scientific Flow Injection Auto-sampler (FIAS)
Authors: Shafiee, RT;Snow, JT;Hester, S;Zhang, Q;Rickaby, REM;
Application: Cells;Environmental;Dissolved;Species;

Dissolved iron (Fe) is vanishingly low in the oceans, with ecological success conferred to microorganisms that can restructure their biochemistry to maintain high growth rates during Fe scarcity. Chemolithoautotrophic ammonia-oxidising archaea (AOA) are highly abundant in the oceans, constituting ~30% of cells below the photic zone. Here we examine the proteomic response of the AOA isolate Nitrosopumilus maritimus to growth-limiting Fe concentrations. Under Fe limitation, we observed a significant reduction in the intensity of Fe-dense ferredoxins associated with respiratory complex I whilst complex III and IV proteins with more central roles in the electron transport chain remain unchanged. We concomitantly observed an increase in the intensity of Fe-free functional alternatives such as flavodoxin and plastocyanin, thioredoxin and alkyl hydroperoxide which are known to mediate electron transport and reactive oxygen species detoxification, respectively. Under Fe limitation, we found a marked increase in the intensity of the ABC phosphonate transport system (Phn), highlighting an intriguing link between Fe and P cycling in N. maritimus. We hypothesise that an elevated uptake of exogenous phosphonates under Fe limitation may either supplement N. maritimus' endogenous methylphosphonate biosynthesis pathway - which requires Fe - or enhance the production of phosphonate-containing exopolysaccharides known to efficiently bind environmental Fe.

Genome-wide imaging screen uncovers molecular determinants of arsenite-induced protein aggregation and toxicity

Year: 2021
Products: SC-FAST automated sample introduction system
Authors: Andersson, S;Romero, A;Rodrigues, JI;Hua, S;Hao, X;Jacobson, T;Karl, V;Becker, N;Ashouri, A;Rauch, S;Nystrom, T;Liu, B;Tamas, MJ;
Application: Cells;

The toxic metalloid arsenic causes widespread misfolding and aggregation of cellular proteins. How these protein aggregates are formed in vivo, the mechanisms by which they affect cells and how cells prevent their accumulation is not fully understood. To find components involved in these processes, we performed a genome-wide imaging screen and identified Saccharomyces cerevisiae deletion mutants with either enhanced or reduced protein aggregation levels during arsenite exposure. We show that many of the identified factors are crucial to safeguard protein homeostasis (proteostasis) and to protect cells against arsenite toxicity. The hits were enriched for various functions including protein biosynthesis and transcription, and dedicated follow-up experiments highlight the importance of accurate transcriptional and translational control for mitigating protein aggregation and toxicity during arsenite stress. Some of the hits are associated with pathological conditions, suggesting that arsenite-induced protein aggregation may affect disease processes. The broad network of cellular systems that impinge on proteostasis during arsenic stress identified in this current study provides a valuable resource and a framework for further elucidation of the mechanistic details of metalloid toxicity and pathogenesis. This article has an associated First Person interview with the first authors of the paper.


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