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A multi-isotope and modelling approach for constraining hydro-connectivity in the East African Rift System, southern Ethiopia

Year: 2022
Products: prepFAST-MC™ system
Authors: Markowska, M;Martin, A;Vonhof, H;Guinoiseau, D;Fischer, M;Zinaye, B;Galer, S;Asrat, A;Junginger, A;
Application: isotope;

During the last African Humid Period (AHP; 15-5 ka), many lakes in the East African Rift System (EARS) experienced pronounced lake-level variations that dramatically transformed the hydrological landscape. Currently dry, saline or marshy-wetland terminal lakes became vast waterbodies, interconnected via overflow sills resulting in the formation of a several thousand-kilometre-long chain of lakes in the EARS. A quantitative, process-based understanding of these hydrological systems can advance our interpretation of past hydroclimate variability from proxy records. Here, we provide a critical modern hydrological dataset for the data-sparse Lake Chew Bahir basin in southern Ethiopia. Driven by modern data, an isotope-enabled hydro-balance model was developed to assess how increases in rainfall modulate δ18O and 87Sr/86Sr variability. Considering a terminal Lake Chew Bahir scenario, humid conditions resulted in higher lake δ18O (∼+14‰) due to increased evaporation and longer water residence times. At the same time 87Sr/86Sr decreased from 0.7064 to 0.7061 due to an increased riverine Sr flux characterised by lower, unradiogenic 87Sr/86Sr ratios. In a modelling scenario where Lake Chew Bahir became a flow-through system with interconnectivity between lakes Abaya, Chamo, Chew Bahir and Turkana, higher lake δ18O (∼+12‰) relative to present was found, but δ18O was lower than in the terminal lake scenario.

A new solid target design for the production of 89Zr and radiosynthesis of high molar activity [89Zr]Zr-DBN

Year: 2022
Products: Elemental Scientific Inc. (ESI) SC2-DX autosamplers
Authors: Pandey, MK;Bansal, A;Ellinghuysen, JR;Vail, DJ;Berg, HM;DeGrado, TR;
Application: Cells;

Due to the advent of various biologics like antibodies, proteins, cells, viruses, and extracellular vesicles as biomarkers for disease diagnosis, progression, and as therapeutics, there exists a need to have a simple and ready to use radiolabeling synthon to enable noninvasive imaging trafficking studies. Previously, we reported [89Zr]zirconium-p-isothiocyanatobenzyl-desferrioxamine ([89Zr]Zr-DBN) as a synthon for the radiolabeling of biologics to allow PET imaging of cell trafficking. In this study, we focused on improving the molar activity (Am) of [89Zr]Zr-DBN, by enhancing 89Zr production on a low-energy cyclotron and developing a new reverse phase HPLC method to purify [89Zr]Zr-DBN. To enhance 89Zr production, a new solid target was designed, and production yield was optimized by varying, thickness of yttrium foil, beam current, irradiation duration and proton beam energy. After optimization, 4.78±0.33 GBq (129.3±8.9 mCi) of 89Zr was produced at 40 µA for 180 min (3 h) proton irradiation decay corrected to the end of bombardment with a saturation yield of 4.56±0.31 MBq/µA. Additionally, after reverse phase HPLC purification the molar activity of [89Zr]Zr-DBN was found to be in 165-316 GBq/µmol range. The high molar activity of [89Zr]Zr-DBN also allowed radiolabeling of low concentration of proteins in relatively higher yield. The stability of [89Zr]Zr-DBN was measured over time with and without the presence of ascorbic acid. The newly designed solid target assembly and HPLC method of [89Zr]Zr-DBN purification can be adopted in the routine production of 89Zr and [89Zr]Zr-DBN, respectively.AJNMMI

A novel approach for adapting the standard addition method to single particle-ICP-MS for the accurate determination of NP size and number concentration in complex matrices

Year: 2022
Products: T piece
Authors: Aramendía, M;García-Mesa, J;Alonso, E;Garde, R;Bazo, A;Resano, J;Resano, M;
Application: ~

This paper presents a novel approach, based on the standard addition method, for overcoming the matrix effects that often hamper the accurate characterization of nanoparticles (NPs) in complex samples via single particle inductively coupled plasma mass spectrometry (SP-ICP-MS). In this approach, calibration of the particle size is performed by two different methods: (i) by spiking a suspension of NPs standards of known size containing the analyte, or (ii) by spiking the sample with ionic standards; either way, the measured sensitivity is used in combination with the transport efficiency (TE) for sizing the NPs. Moreover, such transport efficiency can be readily obtained from the data obtained via both calibration methods mentioned above, so that the particle number concentration can also be determined. The addition of both ionic and NP standards can be performed on-line, by using a T-piece with two inlet lines of different dimensions. The smaller of the two is used for the standards, thus ensuring a constant and minimal sample dilution. As a result of the spiking of the samples, mixed histograms including the signal of the sample and that of the standards are obtained. However, the use of signal deconvolution approaches permits to extract the information, even in cases of signal populations overlapping. For proofing the concept, characterization of a 50 nm AuNPs suspension prepared in three different media (i.e., deionized water, 5% ethanol, and 2.5% tetramethyl ammonium hydroxide-TMAH) was carried out. Accurate results were obtained in all cases, in spite of the matrix effects detected in some media. Overall, the approach proposed offers flexibility, so it can be adapted to different situations, but it might be specially indicated for samples for which the matrix is not fully known and/or dilution is not possible/recommended.

A Quantitative Method for Determining Uptake of Silica Nanoparticles in Macrophages by Single Particle Inductively Coupled Plasma-Mass Spectrometry

Year: 2022
Products: 96-well ICP-MS microtiter plate
Authors: Rogers, KL;Cruz-Hernandez, A;Brown, JM;
Application: Cells;Biological;Environmental;Food;nanoparticle;

Engineered nanomaterials are becoming increasingly ubiquitous in our society, with numerous applications in medicine, consumer products, bioremediation, and advanced materials. As these nanomaterials increase in variety, analyzing their characteristics is of great importance. Single particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) is a high-throughput, sensitive, and robust instrumental analysis method used to simultaneously characterize and quantify nanoparticles in a variety of matrices. One such type of nanoparticle of interest is amorphous silica nanoparticles (SiNPs). SiNPs have widespread use in consumer products such as food and cosmetics and are prime candidates for novel medical applications and uses in environmental bioremediation. Despite their increased use, SiNPs have been shown to have toxicological properties in vitro and in vivo, particularly with regard to the immune system. Because of the potential for increased SiNP exposure in the general public and in occupational settings, examining the relationship that SiNPs have with immune cells such as macrophages to elucidate mechanisms of toxicity is vital. To effectively determine the toxicity of nanoparticles, it is critical to examine dosimetry and the amount of nanoparticles taken up by the cell of interest. Different cell types have different uptake profiles, and varying physicochemical properties govern nanoparticle dosimetry and uptake in cells. Here, we describe a protocol using SP-ICP-MS to quantify and characterize the size, size distribution, and amount of SiNPs present in a cell and medium sample. We use a single-step digestion, which allows for the digestion of biological matrices while simultaneously keeping the SiNPs intact for SP-ICP-MS analysis. Clinically, this approach has the potential to be used as a method for analyzing SiNPs in other biological matrices, potentially as a way of defining SiNP uptake as a biomarker in immune-mediated diseases.

Administration of Silver Nasal Spray Leads to Nanoparticle Accumulation in Rat Brain Tissues

Year: 2022
Products: automatic sampler
Authors: Liu, N;Li, Y;Liu, L;Liu, X;Yin, Y;Qu, G;Shi, J;Song, M;He, B;Hu, L;Jiang, G;
Application: nanoparticle;

The use of commercial products containing engineered nanomaterials in realistic scenarios may lead to the accumulation of exogenous particles in brain tissues. In this study, we simulated the use of silver (Ag) nasal spray in humans using Sprague-Dawley rats at 0.04 mg/kg/day. Silver-containing particles were explicitly identified in the rat brain after the administration of nasal sprays containing colloidal Ag or silver ions (Ag+) for 2 weeks using multiple methods. The accumulation of Ag-containing particles showed a delayed effect in different brain regions of the rats, with the mass concentration of particles increasing continuously for 1-2 weeks after the termination of administration. The size of the observed Ag-containing particles extracted from the brain tissues ranged from 18.3 to 120.4 nm. Further characterization by high-resolution transmission electron microscopy with energy-dispersive spectroscopy showed that the nanoparticles comprised both Ag and sulfur (S), with Ag/S atomic ratios of 1.1-7.1, suggesting that Ag-containing particles went through a series of transformations prior to or during their accumulation in the brain. Collectively, these findings provide evidence for the accumulation and transformation of Ag-containing particles in the rat brain, indicating a realistic risk to brain health resulting from the application of Ag-containing commercial products.

Aerosol dilution for the introduction of complex matrix samples in plasma-based spectrometry techniques: a tutorial review

Year: 2022
Products: PC3
Authors: Duyck, C;Alves Peixoto, R;Rocha, A;Guilhermond de Souza Severino, H;Oliveira, P;Damasceno, R;Lorençatto, R;
Application: organic solvents;

Aerosol dilution (AD) is a sample introduction tool that allows the direct analysis of complex matrix samples by plasma-based analytical techniques.

An eclogitic component in the Pitcairn mantle plume: Evidence from olivine compositions and Fe isotopes of basalts

Year: 2022
Products: ESI 50 μL min−1 PFA MicroFlow Teflon nebulizer
Authors: Shi, J;Zeng, G;Chen, L;Hanyu, T;Wang, X;Zhong, Y;Xie, L;Xie, W;
Application: isotope;

Subducted oceanic crust can transform into eclogite in the upper mantle, and generate chemical heterogeneity of mantle plumes, as recorded by elemental and radiogenic isotopic variations in oceanic island basalts (OIBs). The secondary pyroxenite produced by the reaction between eclogite-derived melt and peridotite is increasingly regarded as a major source component of OIBs, as well as peridotite. However, it remains unclear whether eclogite can be a direct source component of OIBs. To test this possibility, we present high-precision whole-rock Fe isotopes and the chemical compositions of olivine phenocrysts from well-characterized EM1-type basalts from Pitcairn Island. The Pitcairn basalts are characterized by moderate 87Sr/86Sr, low 143Nd/144Nd and 206Pb/204Pb isotopic ratios, and lowest δ26Mg values among OIBs, suggesting a contribution from recycled ancient crustal components (oceanic crust plus sediment). For comparison, we also report the Fe isotope compositions of FOZO-type basalts (with low 87Sr/86Sr, moderately high 143Nd/144Nd and moderate 206Pb/204Pb ratios) from the Louisville hot spot track, which were suggested to be a typical peridotite-derived OIB. The Louisville basalts have MORB-like δ57Fe values (0.06‰-0.15‰), whereas the Pitcairn lavas have substantially heavier Fe isotopic compositions (δ57Fe = 0.17‰-0.31‰) than MORBs. Quantitative evaluations suggest that magmatic differentiation, partial melting, and elevated oxygen fugacity in the source are insufficient to generate the heavy Fe isotopic compositions of the Pitcairn basalts. A good correlation between δ57Fe and εNd(i) (or δ26Mg) values in the Pitcairn basalts indicates binary mixing, and the melts derived from the EM1 endmember have unusually heavy Fe and light Mg isotopic compositions. In order to explain the origin of the Fe and Mg isotopic compositions, we calculated the Fe, Mg, and Nd isotopic compositions of partial melts of eclogite, secondary pyroxenite and peridotite, respectively. The results indicate that eclogite is the only suitable candidate to generate melts with both heavy Fe and light Mg isotopes. This inference is strengthened by the major and minor elemental compositions of olivine phenocrysts from the Pitcairn basalts, which show low Fo (73.2-82.5) and Ni contents (620-1949 ppm), and low Mn/Fe (0.011-0.015) and Ni/(Mg/Fe) (524-1041) ratios. These characteristics are markedly different from those of olivines from MORBs and the Koolau lavas from Hawaii, which represent phenocrysts that equilibrated with peridotite-derived and secondary pyroxenite-derived melts, respectively. We therefore argue that eclogite is the source lithology of the EM1 endmember of the Pitcairn basalts. Binary mixing between our modelled eclogite- and peridotite-derived melts produced magmas with relatively low Mg# value, Mg/Fe ratios and moderate Ni contents characteristics, which are preserved in the low-Fo Pitcairn olivines. Our results highlight that, in addition to peridotite and secondary pyroxenite, eclogite may survive in mantle plumes at shallow depths and make a substantial contribution to the source of OIBs.

An evaluation of M2+ interference correction approaches associated with As and Se in ICP-MS using a multi-day dataset along with ICP-MS/MS/HR-ICP-MS based analysis and hierarchical modeling as a means of assessing bias in fortified drinking waters and single component matrices

Year: 2022
Products: cyclonic quartz spray chamber
Authors: Smith, S;Martin, R;Hanks, N;Creed, P;Kovalcik, K;Wilson, R;Kubachka, K;Brisbin, J;Landero Figueroa, J;Creed, J;
Application: ~

M2+ internal standard ions mimic the drift of other M2+ ions better than M1+. ICP-MS/MS and HR-ICP-MS are used to assess the bias of various M2+ corrections while a Bayesian hierarchical model is used to estimate day to day impacts on the correction.

Analysis of Seventeen Certified Water Reference Materials for Trace and Technology‐Critical Elements

Year: 2022
Products: seaFAST
Authors: Ebeling, A;Zimmermann, T;Klein, O;Irrgeher, J;Pröfrock, D;
Application: Environmental;seawater;

Concentrations of elements in the aquatic environment are a key parameter for various scientific fields such as biogeochemistry, biology and environmental science. Within this context, the scientific community asks for new analytical protocols to be able to quantify more and more elements of the periodic table. Therefore, the requirements for aqueous reference materials have increased drastically. Even though a wide variety of CRMs of different water matrices are available, certified values of many elements (e.g., rare earth elements (REE), technology-critical elements, such as Ga and In, and generally those elements which are not part of current monitoring regulations) do not yet exist. Therefore, the scientific community relies on published elemental concentrations of many CRMs provided by other researchers. Some elements of interest, such as the REE, are well studied and plenty of literature values exist. However, less studied elements, such as Ga and In, are rarely studied. In this study, an ‘externally’ calibrated quantification method based on an optimised online preconcentration method coupled with ICP-MS/MS was used for the quantification of thirty-four elements. The method was applied to seventeen water CRMs covering freshwater, brackish water and seawater. The measured data are combined with a comprehensive literature review on non-certified values in selected water CRMs, and new consensus values are suggested for various non-certified elements.

Application of Calcified Structures in Fish as Indicators of Metal Exposure in Freshwater Ecosystems

Year: 2022
Products: HR ICP-MS
Authors: Filipović Marijić, V;Mijošek, T;Dragun, Z;Retzmann, A;Zitek, A;Prohaska, T;Bačić, N;Redžović, Z;Grgić, I;Krasnići, N;Valić, D;Kapetanović, D;Žunić, J;Ivanković, D;Vardić Smrzlić, I;Erk, M;
Application: Tissue;Environmental;

Although there are common and well-established bioindicator organisms and tissues, there is still a need for reliable and sensitive bioindicators in aquatic environments. In the present pilot study, calcified structures in fish were applied as indicators of metal exposure in combination with commonly used fish soft tissues and intestinal parasites, therefore comprising short- and long-term indicators. Patterns of metal accumulation and distribution in soft (muscle, liver) and hard (scales, otoliths) tissues of brown trout (Salmo trutta Linnaeus, 1758) and their intestinal parasites, acanthocephalans (Dentitruncus truttae Sinzar, 1955), from the Krka River influenced by industrial and municipal wastewaters were estimated and compared. Most elements had higher levels in acanthocephalans, scales and liver than muscle and otoliths, possibly reflecting differences in metal uptake routes, tissue function and metabolic activity. Despite the recorded differences in metal contents, all applied bioindicators reflected environmental conditions in a similar way, indicating higher levels of most elements in fish from the contaminated rather than from the reference site. Acanthocephalans were confirmed as sensitive bioindicators due to effective metal accumulation capacity, while the combination of soft and hard tissues provided extended temporal information on metal exposure. Wastewater impact was evidenced as moderate metal pollution by all applied indicators and pointed to present but also long-term disturbances in the Krka River and the importance of continuous monitoring and protective actions.

Assessing the preservation of biogenic strontium isotope ratios (87 Sr/86 Sr) in the pars petrosa ossis temporalis of unburnt human skeletal remains; a case study from Saba

Year: 2022
Products: PFA-ST MicroFlow nebulizer
Authors: Kootker, LM;Hoogland, M;Laffoon, JE;
Application: isotope;

Strontium isotope (87 Sr/86 Sr) analysis of skeletal remains has become a powerful tool in archaeological studies of human migration and mobility. Owing to its resistance to post-mortem alteration dental enamel is the preferred sampling material used for 87 Sr/86 Sr analysis in bioarchaeological provenance research, although recent studies have demonstrated that cremated bone is also generally resistant to diagenesis. This paper presents the results of a pilot study exploring the potential of unburnt petrous bone (pars petrosa) as a reservoir of biogenic (diagenetically unaltered) strontium, as the otic capsule or bony labyrinth within the petrous bone is extremely dense and is thought to be unable to remodel after early childhood, potentially providing an alternative for dental enamel METHODS: From an individual from a colonial era (18th century) site on the island of Saba in the Caribbean for whom previous enamel 87 Sr/86 Sr results had indicated nonlocal origins, multiple locations (n = 4) on the petrous were sampled and measured for strontium isotope composition. Saba (13 km2 ) has been extensively mapped for baseline strontium isotopes (n = 50) with 87 Sr/86 Sr varying between ~0.7065 to 0.7090, whereas enamel 87 Sr/86 Sr (n= 3) ranged from 0.7104 to 0.7112.All four petrous 87 Sr/86 Sr (0.7111-0.7122) are consistently and considerably higher than the local bioavailable range, and very similar to the enamel 87 Sr/86 Sr. These results provide initial evidence that unburnt petrous bones may preserve biogenic strontium, at least in this specific burial context.While more research in diverse burial conditions is needed to validate this observation, if confirmed, it would have broader implications for sample selection strategies in bioarchaeological studies using the strontium isotope method.This article is protected by

Association Between Essential and Non-essential Metals, Body Composition, and Metabolic Syndrome in Adults

Year: 2022
Products: ESI SC-2 DX4
Authors: Ngu, YJ;Skalny, AV;Tinkov, AA;Tsai, CS;Chang, CC;Chuang, YK;Nikolenko, VN;Zotkin, DA;Chiu, CF;Chang, JS;
Application: Blood;

Growing evidence indicates that metal exposure is associated with metabolic syndrome (MetS); however, mixed results have been reported. The aim of this study was to clarify associations of exposure to essential and non-essential metals with body composition and risks of obesity and MetS. Anthropometry and blood biochemistry of metabolic parameters were obtained from 150 middle-aged Taiwanese adults. Plasma metals were assessed using inductively coupled plasma mass spectrometry, and body compositions were measured by a bioelectrical impedance analysis (BIA). The essential metals of copper (Cu), manganese (Mn), and chromium (Cr) were positively correlated with the body fat mass but inversely correlated with the skeletal muscle mass (all p < 0.05). An adjusted logistic regression showed that Mn [odds ratio (OR) = 1.624 (95% confidence interval 1.072, 2.462), p = 0.02] and, to a lesser extent, Cu [OR = 1.501 (0.985, 2.292), p = 0.059] predicted abdominal obesity, while plasma Cu [OR = 2.211 (1.146, 4.266), p = 0.02] and zinc (Zn) [OR = 2.228 (1.048, 4.736) p = 0.04] predicted MetS. Significant correlations between dyslipidemia and lithium [OR = 1.716 (1.080, 2.726)], Cu [OR = 2.210 (1.415, 3.454)], Mn [OR = 2.200 (1.320, 3.666)], molybdenum [OR = 1.853 (1.160, 2.958)], and Zn [OR = 1.993 (1.186, 3.349)], and between boron [OR = 2.583 (1.137, 5.868)] and hyperglycemia were observed (all p < 0.05). Exposure to essential metals may affect the body composition and metabolic profiles, exacerbating the risk of MetS.

Automated method for concurrent determination of thorium (230Th, 232Th) and uranium (234U, 235U, 238U) isotopes in water matrices with ICP-MS/MS

Year: 2022
Products: membrane desolvating system Apex Ω
Authors: Ni, Y;Bu, W;Ding, X;Xiong, K;Wang, H;Yang, C;Hu, S;Men, W;
Application: seawater;nuclear;

High-efficiency analysis of Th and U isotopes are important technical issues encountered in the fields such as environment monitoring and nuclear emergency responses.

Back-arc system formation and extinction in the southern Central Asian Orogenic Belt: New constraints from the Faku ophiolite in north Liaoning, NE China

Year: 2022
Products: NWR193 laser-ablation microprobe
Authors: Shi, Y;Shi, S;Liu, Z;Wang, L;Liu, J;Chen, J;Yang, F;Zhang, C;Li, B;Zhang, L;
Application: Laser;geochemistry;

Palaeozoic ophiolites are rare in the south-eastern Central Asian Orogenic Belt (CAOB) and are genetically significant for understanding the formation, evolution, and closure processes of the Palaeo-Asian Ocean (PAO). The Faku ophiolite is located in north Liaoning, NE China, and is dominated by the south-eastern CAOB within the Songliao Basin. It consists of several discontinuous tectonic blocks made up of serpentinised ultramafic rocks, gabbros, basalts, high-Mg andesites, marine and continental sedimentary formations, which are intruded by younger granites. We characterize the geochronology and geochemistry of the ophiolite. The ophiolite and granitic rocks have restricted εNd(t) (+2.60 to +6.08) and εNd(t) (+0.42 to +1.66). Zircons from the ophiolite and granite yielded weighted mean 206Pb/238U ages of 369-249 Ma and ca. 248.2 Ma, respectively, that we interpret as their crystallization (eruption) times. The ophiolitic rocks have a resemblance to enriched mid-ocean ridge basalts and within-plate basalts in terms of geochemistry, thereby representing a back-arc-type tectonic setting. The granite geochemically belongs to I-type, and formed in a syn-collisional orogenic environment. The sandstones from marine sediments are enriched with light rare earth elements and have low contents of SiO2 and MgO, and a positive zircon ɛHf(t) value indicating the affinities similar to those of ophiolitic rocks. The provenance of molasse is from the Baijiagou granites suggesting that the post-collisional orogeny and uplift occurred after the Early Triassic. We speculate that a juvenile intra-continental back-arc oceanic basin, which represents the southern affiliated branch of the PAO, might have formed by the continuous extension in southern CAOB since the late Devonian, and ultimately closed in the Early Triassic.

Bioaccumulation patterns of trace elements by native (M. galloprovincialis) and invasive (X. securis) mussels in coastal systems (Vigo Ria, NW Iberian Peninsula)

Year: 2022
Products: seaFAST
Authors: Rodríguez-Velarte, P;Babarro, JMF;Cobelo-García, A;
Application: Tissue;Dissolved;Species;

A number of trace elements (Mn, Fe, Co, Ni, Cu, Zn, As, Nb, Mo, Ag, Cd, Pb, U and the rare earth elements - REE) were analyzed in the dissolved phase, suspended particulate matter and in different organs (gills, hepatopancreas, and the rest of soft tissue) in mussels of the native Mytilus galloprovincialis and invasive Xenostrobus securis species in the Vigo Ria (NW Iberian Peninsula) in order to assess potential differences in their bioaccumulation patterns. Results obtained do not show significant differences in the bioaccumulation of trace elements by M. galloprovincialis and X. securis, except for Zn and Ag. In the case of Zn, a 4-fold enrichment in M. galloprovincialis compared to X. securis was found. The most important differences between species were observed for Ag, with approximately 40-fold higher concentrations in X. securis. Such elevated Ag bioaccumulation by X. securis can be useful for Ag biomonitoring using these invasive species in this area.

Bulk Aerosol Trace Element Concentrations and Deposition Fluxes During the U.S. GEOTRACES GP15 Pacific Meridional Transect

Year: 2022
Products: seaFAST
Authors: Marsay, C;Kadko, D;Landing, W;Buck, C;
Application: oil;

Atmospheric deposition of aerosols transported from the continents is an important source of nutrient and pollutant trace elements (TEs) to the surface ocean. During the U.S. GEOTRACES GP15 Pacific Meridional Transect between Alaska and Tahiti (September-November 2018), aerosol samples were collected over the North Pacific and equatorial Pacific and analyzed for a suite of TEs, including Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pb. Sampling coincided with the annual minimum in dust transport from Asia, providing an opportunity to quantify aerosol TE concentrations and deposition during the low dust season. Nevertheless, peak concentrations of “crustal” TEs measured at ∼40-50°N (∼145 pmol/m3 Fe) were associated with transport from northern Asia, with lower concentrations (36 ± 14 pmol/m3 Fe) over the equatorial Pacific. Relative to crustal abundances, equatorial Pacific aerosols typically had higher TE enrichment factors than North Pacific aerosols. In contrast, aerosol V was more enriched over the North Pacific, presumably due to greater supply to this region from oil combustion products. Bulk deposition velocity (Vbulk) was calculated along the transect using the surface ocean decay inventory of the naturally occurring radionuclide, 7Be, and aerosol 7Be activity. Deposition velocities were significantly higher (4,570 ± 1,146 m/d) within the Intertropical Convergence Zone than elsewhere (1,764 ± 261 m/d) due to aerosol scavenging by intense rainfall. Daily deposition fluxes to the central Pacific during the low dust season were calculated using Vbulk and aerosol TE concentration data, with Fe fluxes ranging from 19 to 258 nmol/m2/d.

Calcium isotope measurements using a collision cell (CC)-MC-ICP-MS

Year: 2022
Products: MicroFlow nebulizer
Authors: Dai, W;Moynier, F;Paquet, M;Moureau, J;Debret, B;Siebert, J;Gerard, Y;Zhao, Y;
Application: Biological;isotope;geochemistry;

Calcium is a major element in terrestrial planets and has six stable isotopes, including 40Ca which is a product of radioactive decay of 40K (T1/2 = 1.25 Gyrs). Calcium isotope geochemistry has therefore been used to trace biological and geological processes in various environments as well as radiogenic dating. However, it has been technically impossible to analyze stable and radiogenic isotopes simultaneously and high precision measurements usually require tens of micrograms of Ca. Here, we present high-precision Ca isotopic data, including the stable isotopes 42Ca, 43Ca and 44Ca as well as the radiogenic 40Ca using a Nu Sapphire multi-collector inductively-coupled-plasma mass-spectrometer (MC-ICP-MS), that is equipped with a collision cell to minimize Ar based interferences. The stable isotopic variations are reported using the delta notation (δ40/44Ca, δ42/44Ca, δ43/44Ca), which is the permil deviation of a given ratio from the NIST SRM 915b standard. The radiogenic excess is reported as ε40Ca, the per ten thousand deviation of the 40Ca/44Ca ratio from the same standard, after internal normalization to the 42Ca/44Ca ratio. We tested the influence of various parameters (Ca concentration, Ca and HNO3 concentration mismatch between sample and standard, effect of matrix elements) on the precision and accuracy of the measurements. We show that, using ~ 100 ng is sufficient to obtain high precision (

Carnelian beads in Mongolia: new perspectives on technology and trade

Year: 2022
Products: ESI-elemental scientific laser - NW213
Authors: Kenoyer, J;Cameron, A;Bukhchuluun, D;Amartuvshin, C;Byambatseren, B;Honeychurch, W;Dussubieux, L;Law, R;
Application: Laser;

This study was supported in part by grants to Honeychurch from the US National Endowment for the Humanities (Grant RZ-249831-16), the Wenner-Gren Foundation for Anthropological Research, and the Council on Archaeological Studies at Yale University. Funding for the SEM and LA-ICP-MS analysis and Kenoyer’s ongoing study of bead technology has been provided by numerous grants over the years, and most recently by the College of Letters and Sciences, Wisconsin Alumni Research Foundation Named Professorship Award in 2018 and the Hilldale Award in 2017-18, donations from [], and private donations. Partial funding for the LA-ICP-MS analysis at the Elemental Analytical Facility, The Field Museum, was provided by a grant from the National Science Foundation (Grant BCS 1321731).

Chemical composition and sources of organic aerosol on the Adriatic coast in Croatia

Year: 2022
Products: APEX Q nebulizer
Authors: Casotto, R;Cvitešić Kušan, A;Bhattu, D;Cui, T;Manousakas, M;Frka, S;Kroflič, A;Grgić, I;Ciglenečki, I;Baltensperger, U;Slowik, J;Daellenbach, K;Prévôt, A;
Application: Total;

Air pollution studies are still scarce in some areas in Europe like around the Adriatic Sea. Source apportionment of the fine particulate (PM2.5) organic aerosol (OA) was conducted near Rogoznica, a small touristic settlement on the Eastern Adriatic coast of Croatia, near Lake Rogoznica (43.53° N, 15.95° E). Filter-based offline analyses of PM by a high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) were used to apportion OA to its sources. We quantified the contributions of fresh biomass burning OA (BBOA) and three oxygenated OA (OOA), denoted as background OOA (bkgOOA), summer OOA (SOOA), and sulfur-containing OOA (SC-OOA). The bkgOOA component correlates with anthropogenically influenced secondary inorganic aerosol constituents (e.g. sulfate) and dominates OA both during the warm and cold seasons (44%). It exhibits characteristics of regional SOA and there are indications that during the warm season SOA from wildfires could be a substantial contributor. EESI-TOF measurements of the levoglucosan related ion showed a high correlation with the BBOA factor. Secondary OA has a similar molecular composition during the cold and warm seasons - in line with the large contribution of bkgOOA throughout the investigated seasons. SOOA comprises 19% of total OA and increases exponentially with the local temperature, consistent with SOA production by oxidation of biogenic emissions. In addition to biogenic precursors, other precursors (alkanes and aromatic) may contribute to the OOA enhancement during the warm season. SC-OOA is a minor contributor to OA (6%) and is most likely linked to emissions from a close-by marine lake.

Comparison of monosegmented flow analysis to flow injection for single particle inductively coupled plasma mass spectrometry

Year: 2022
Products: PFA nebulizer
Authors: Williams, A;Beauchemin, D;
Application: nanoparticle;

Monosegmented flow analysis doubles the sample throughput of flow injection, and provides accurate nanoparticle mass without measuring the transport efficiency.

Data set showing the development of a hyperspectral imaging technique using LA-ICP-MS to determine the spatial distribution of nutrients in soil cores

Year: 2022
Products: LA-ICP-MS
Authors: Zaeem, M;Nadeem, M;Pham, TH;Ashiq, W;Ali, W;Gillani, SSM;Moise, ERD;Leier, H;Kavanagh, V;Galagedara, L;Cheema, M;Thomas, R;
Application: soil;Laser;

This data in brief article represents the data set associated with a research article published in Geoderma [1]. The data set represents figures showing the spatial distribution of selected macro and micronutrients, and their quantification in different crop or nutrient management systems practiced in the boreal ecosystem. Spatial distribution of nutrients was measured by laser ablation inductively coupled plasma mass spectrometry (LA‒ICP‒MS), using the new techniques we developed to visualize nutrient distribution in intact soil cores representative of the root rhizosphere. This data article supports the findings published in the main article [1]. This work also demonstrates that LA-ICP-MS is a valuable technique to image the spatial distribution of macro and micronutrients in intact soil cores as affected by different crop management practices.

Determination of inert and labile copper on GEOTRACES samples using a novel solvent extraction method

Year: 2022
Products: seaFAST
Authors: Moriyasu, R;Moffett, J;
Application: Speciation;seawater;geochemistry;

Copper, in seawater, is predominantly bound by organic ligands of unknown composition. Complexation has been thermodynamically characterized using synthetic ligand competition experiments which assumes equilibrium among all chelators within the system. However, equilibration times are constrained by wall loss issues with the synthetic ligands. Here, a solvent extraction methodology, was utilized to avoid the wall-loss problems. Using an exceptionally high concentration of a strong copper chelator, oxine (8-hydroxyquinoline), at least six hours of equilibration time is required to reach steady state between the competing ligand and the labile copper in seawater. This is much longer than equilibration times used in previously published works. Our method was optimized by using samples from GEOTRACES expeditions in the North Pacific and North Atlantic Oceans. Surprisingly, 60-90% of the copper was not exchangeable with oxine under these conditions. We define this fraction as “inert”, and these data, which include profiles as deep as 1000 m in the North Pacific, suggest that this is a widespread feature. Our results suggest that there are two distinct pools of labile and inert copper, rather than an assemblage of similar complexes with incremental differences in stability constants. The results have important implications for the marine geochemistry of copper and its bioavailability. Complexation has been shown to limit copper bioavailability and influences scavenging and residence time. Moreover, a basic paradigm of copper speciation methodologies, that even strong Cu complexes are relatively labile, is likely incorrect.

Determination of the zirconium isotopic composition of the new isotopic standard NRC ZIRC-1 using MC-ICP-MS

Year: 2022
Products: APEX HF desolvating nebulizer
Authors: Tian, S;Moynier, F;Inglis, E;Jensen, N;Deng, Z;Schiller, M;Bizzarro, M;
Application: ~

First cross-calibration of all existing Zr isotopic standards and two certified reference materials to a new commercially available standard NRC ZIRC-1, and the first report of the Zr isotopic composition of Allende chondrite.

Detrital Zircon Provenance in the Sediments in the Southern Okinawa Trough

Year: 2022
Products: NWR 193UC laser ablation system
Authors: Zhu, B;Zeng, Z;
Application: isotope;Laser;

The provenance of sediments in the Southern Okinawa Trough since the late Holocene has been a controversial scientific issue during the past 20 years. Previous studies based on isotope proxies generally indicated Taiwanese rivers as the primary source in the Southern Okinawa Trough since the late Holocene. Based on the zircon U-Pb geochronology, this study identified how sediments from the Yangtze River/East China Sea shelf had contributed significantly to the Southern Okinawa Trough in the past 624 a BP. Notably, this study found two Paleoarchean zircon grains, which indicated they originated from older orogenic belts. These data shed new light on the provenance of sediments, and a partial supply from the mainland of China cannot be excluded.

Development of mini column experiments (MCE) by coupling microliter flow HPLC with ICP MS for the analysis of metal retention under conditions close to nature

Year: 2022
Products: PFA
Authors: Kautenburger, R;Brix, K;Baur, S;Sander, J;
Application: ~

The development and implementation of mini column experiments (MCE) can be of great importance to improve existing analytical methods such as highly standardised but unrealistic batch laboratory experiments or lengthy long-term diffusion experiments to study metal sorption/desorption properties. One envisaged application would be to test the retention of repository-relevant metals in claystone, which is a promising candidate for the host rock of a final repository site for high-level radioactive waste (HLW). The used MCE setup is derived from classical high performance liquid chromatography (HPLC). On this basis, coupling of MCE to ICP-MS (inductively coupled plasma mass spectrometry) detection was realised. This online separation enables the dynamic monitoring of metal sorption and desorption experiments on clay minerals (kaolinite), natural clay (Opalinus Clay) and mixtures with quartz sand in background solutions close to nature, and without the common use of metal complexing ligands, other reaction partners or buffers for the analysed metal ions. The optimised method allows the analysis of the retention of various contaminants in real groundwater solutions and compact clay samples in a reasonable amount of time and a small amount of sample. In addition, the coupling to the unspecific mass detector of ICP-MS enables the study of different radionuclides and homologues rather than the limited UV detection of a common HPLC.

Disentangling the Ecological Processes Shaping the Latitudinal Pattern of Phytoplankton Communities in the Pacific Ocean

Year: 2022
Products: seaFAST
Authors: Xu, Z;Cheung, S;Endo, H;Xia, X;Wu, W;Chen, B;Ho, NHE;Suzuki, K;Li, M;Liu, H;
Application: Environmental;Dissolved;Species;

Phytoplankton diversity and community compositions vary across spaces and are fundamentally affected by several deterministic (e.g., environmental selection) and stochastic (e.g., ecological drift) processes. How this suite of different processes regulates the biogeography of phytoplankton remains to be comprehensively explored. Using high-throughput sequencing data and null model analysis, we revealed the ecological processes shaping the latitudinal community structure of three major phytoplankton groups (i.e., diatoms, Synechococcus, and haptophytes) across the Pacific Ocean (70°N, 170°W to 35°S, 170°W). At the basin scale, heterogeneous selection (selection under heterogeneous environmental conditions) dominated the assembly processes of all phytoplankton groups; however, its relative importance varied greatly at the climatic zonal scale, explaining the distinct latitudinal α- and β-diversity among phytoplankton groups. Assembly processes in Synechococcus and haptophyte communities were mainly controlled by physical and nutrient factors, respectively. High temperature drove Synechococcus communities to be more deterministic with higher diversity, while haptophyte communities were less environmentally selected at low latitudes due to their wide niche breadth and mixotrophic lifestyle. Diatom communities were overwhelmingly dominated by the selection process but with low correlation of measured environmental factors to their community compositions. This could be attributed to the high growth rate of diatoms, as indicated by their lower site occupation frequency than predicted in the neutral community model. Our study showed that heterogeneous selection is the main force that shaped the biogeography of three key phytoplankton groups in the Pacific Ocean, with a latitudinal variation of relative importance due to the distinct traits among phytoplankton. IMPORTANCE Phytoplankton are diverse and abundant as primary producers in the ocean, with diversity and community compositions varying spatially. How fundamental processes (e.g., selection, dispersal, and drift) regulate their global biogeography remains to be comprehensively explored. In this study, we disentangled the ecological processes of three key phytoplankton groups (i.e., diatoms, Synechococcus, and haptophytes) along the same latitudinal gradients in the Pacific Ocean. Heterogeneous selection, by promoting species richness and reducing similarity between communities, was the dominant process shaping the communities of each phytoplankton group at the basin scale. However, its relative importance varied greatly among different phytoplankton groups in different climate zones, explaining the uneven latitudinal α- and β-diversity. We also highlight the importance of identifying key factors mediating the relative importance of assembly processes in phytoplankton communities, which will enhance our understanding of their biogeography in the ocean and future patterns under climate changes.

Distribution and accumulation of mercury in pot-grown African rice cultivars (Oryza glaberrima Steud. and Oryza sativa L.) determined via LA-ICP-MS

Year: 2022
Products: 10 cm × 10 cm sample chamber
Authors: Punshon, T;Jackson, BP;Donohue, A;Hong, C;Rothenberg, SE;
Application: Total;Species;soil;Laser;

There is limited information concerning the distribution of mercury in rice, particularly in African rice. The objective was to compare the distribution of total mercury (THg) and methylmercury (MeHg) in African rice (Oryza glaberrima Steud.) and Asian rice (O. sativa L.). It is hypothesized that increased mineral accumulation and greater stress tolerance in O. glaberrima will affect the uptake and distribution of THg and MeHg, compared to O. sativa. Rice varieties from the Republic of Mali, including O. glaberrima (n =1) and O. sativa (n = 2), were cultivated in a greenhouse, in mercury-spiked soil (50 mg/kg) (n =3 replicates/variety). THg and MeHg concentrations were analyzed in the grain (brown rice), and the THg distribution was analyzed using laser ablation inductively coupled-plasma mass spectrometry (LA-ICP-MS). THg and MeHg concentrations did not differ between O. glaberrima and O. sativa grain. However, in both O. sativa varieties, THg was highly concentrated in the scutellum, which surrounds the embryo and is removed during polishing. Conversely, in O. glaberrima grain, THg was widely distributed throughout the endosperm, the edible portion of the grain. Differences in the THg distribution in O. glaberrima grain, compared to O. sativa, may elevate the risk of mercury exposure through ingestion of polished rice. The novelty of this study includes the investigation of a less-studied rice species (O. glaberrima), the use of a highly sensitive elemental imaging technique (LA-ICP-MS), and its finding of a different grain THg distribution in O. glaberrima than has been observed in O. sativa.

Distribution and source of plutonium in sediments from the southern Gulf of Mexico

Year: 2022
Products: self-aspirating PFA-ST-nebuliser
Authors: Corcho-Alvarado, JA;Díaz-Asencio, M;Röllin, S;Herguera, JC;
Application: Dissolved;Total;isotope;

Here, we report on new data (75 analyses) of plutonium (Pu) isotopes to elucidate activity concentrations, inventories, sources, and their transport from the ocean surface to the seafloor from a collection of six deep-sea sediment cores (depths ranging from 257 to 3739 m) in the southern Gulf of Mexico. Sediment cores collected from the continental shelf and upper slope region of the Gulf of Mexico showed 240Pu/239Pu ratios of 0.15 to 0.26, and 239+240Pu-inventories ranging from 14.7 to 33.0 Bq m-2. Inventories and ratios are consistent with global fallout Pu for this tropical region. In contrast, sediment cores collected from the lower slope region and abyssal plain showed low 240Pu/239Pu ratios of 0.07 to 0.13 and much lower 239+240Pu inventories below 6.8 Bq m-2. This implies that only a small fraction of the expected global fallout Pu has reached the deep-sea sediments. The low 240Pu/239Pu isotope ratios indicate that fallout from the Nevada testing site was an important source of Pu in deep-sea sediments, and that this Pu was likely more efficiently scavenged from the water column than Pu from global fallout. We estimated that up to 44% of the total inventory of 239+240Pu in deep-sea sediments is due to the Nevada source. Low values and a progressive decrease of 240Pu/239Pu ratios and 239+240Pu inventories with increasing water depth have been previously reported for the Gulf of Mexico. Analysis of Pu isotopes in two sediment traps from the upper slope regions shows 240Pu/239Pu ratios comparable to those observed in global fallout. These results indicate that global fallout Pu is currently the main source of Pu in sinking particles in the water column. Therefore, a significant fraction of global fallout Pu must still be present, either in a dissolved phase, or as biologically recycled material in the water column, or scavenged on the shelf and shelf break. Our results bring to light important questions on the application of Pu isotopes to establish sediment chronologies in deep-sea sediments, since global fallout features such as the 1963 maximum are not available.

Distribution of 26 major and trace elements in edible seaweeds from the US market

Year: 2022
Products: Elemental Scientific SC-DX4 fast autosampler, peltier-cooled sample chamber
Authors: Todorov, TI;Wolle, MM;Conklin, SD;
Application: Species;Food;

In this study we present an elemental profile of 46 edible seaweed samples purchased in the United States. The seaweeds were grouped in 13 subgroups/species based on DNA barcoding analysis. The seaweeds were decomposed by microwave accelerated acid digestion followed by quantification of 26 elements by ICP-MS. Elements were grouped into macronutrient (Na, K, Ca, S, Mg and P), essential (Fe, Zn, Mn, V, Cu, Cr, Ni, Mo and Se), non-essential including toxic elements (Sr, Ba, Th, Sn and Sb As, Cd, Pb, U, W and Hg). The highest levels were found for Na and the lowest were for Hg. The elemental profiles depended on the taxonomy of the species and several elements (Fe, Ba, Cr, Pb, W and Th) also exhibited high intraspecies variations, likely due to geographic origin or food processing conditions. Higher Cd and Pb accumulation was observed in wakame, hijiki and nori, with Cd as high 4.05 mg/kg and Pb as high as 2.85 mg/kg in kombu. A study of correlation between the elements using Pearson's coefficients revealed multiple pairs of highly correlated elements in seaweed, as well as triple and quintuple correlations of certain elements.

Drinking Water Quality and Public Health in the Kathmandu Valley, Nepal: Coliform Bacteria, Chemical Contaminants, and Health Status of Consumers

Year: 2022
Products: Fluoride anion FAAS
Authors: Sarkar, B;Mitchell, E;Frisbie, S;Grigg, L;Adhikari, S;Maskey Byanju, R;
Application: Total;drinking water;

Residents of Nepal's Kathmandu Valley draw drinking water from tube wells, dug wells, and stone spouts, all of which have been reported to have serious water quality issues. In this study, we analyzed drinking water samples from 35 tube wells, dug wells, stone spouts, and municipal tap water for bacterial and chemical contaminants, including total and fecal coliform, aluminum, arsenic, barium, beryllium, boron, cadmium, cobalt, chromium, copper, fluoride, iron, mercury, manganese, molybdenum, nickel, lead, antimony, selenium, thallium, uranium, vanadium, and zinc. We also asked a sampling of households who used these specific water sources to rate the taste of their water, list any waterborne diseases they were aware of, and share basic health information about household members. This survey provided us with information from 146 households and 603 individuals. We found widespread bacterial contamination of water sources, with 94% of sources having detectable total or fecal coliform. Nepal Drinking Water Quality Standards and World Health Organization (WHO) Drinking-Water Guidelines or health-based values were exceeded for aluminum (max = 0.53 mg/L), arsenic (max = 0.071 mg/L), iron (max = 7.22 mg/L), and manganese (max = 3.229 mg/L). The distribution of water sources with high arsenic, iron, and manganese appeared to be associated with floodplain deposits. Mixed effects logistic regression models were used to examine the interactions between social factors and water contaminants and their effects on household members' health. Consumers of water sources with both high and low concentrations of manganese were less likely to have a positive attitude towards school than those whose water sources had moderate concentrations of manganese. Social factors, especially education, played a large role in predicting individual health outcomes. Household taste ratings of drinking water were not correlated with iron or manganese concentrations, suggesting that WHO's reliance on aesthetic criteria for these contaminants instead of formal drinking-water guidelines may not be sufficient to protect public health.


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