Scientific Publications

Adrenocortical carcinoma (ACC) has a poor prognosis, and no new drugs have been identified in decades. The absence of drug development can partly be attributed to a lack of preclinical models. Both animal models and 2D cell cultures of ACC fail to accurately mimic the disease, as animal physiology is inherently different than humans, and 2D cultures fail to represent the crucial 3D architecture. Organoids are small 3D in vitro models of tissues or tumors, which can model certain complexities of human in vivo biology; however, this technology has yet to be applied to ACC. In this study, we describe the generation of organoids from an established ACC cell line, H295R. H295R cells were encapsulated to generate ACC organoid constructs. Organoids were assessed for biomarker expression, viability, proliferation, and cortisol production. In addition, matrix metalloproteinase (MMP) functionality was assessed directly using fluorogenic MMP-sensitive biosensors and through infusion of H295R cell...

Refractory Black carbon (rBC) emitted from the combustion of biomass and fossil fuels plays an important role in the climate system. In this study, we established a record of the rBC concentration spanning 1932-2013 from an ice core retrieved from the Chongce ice cap of the West Kunlun Mountains in the western Tibetan Plateau. The record showed an increasing trend since the 1980s. The mean concentration of rBC was 2.66 ng g−1 before 1980 and 5.33 ng g−1 since 1980. The significant increase since the 1980s was very different from similar records from European ice cores. An analysis of atmospheric circulation and backward trajectories suggested that former USSR, the Middle East, and South Asia were the most likely source regions for the rBC deposited at the Chongce ice cap. This conclusion was also supported by the historical emission data in these regions. Phase analysis indicated that high rBC concentrations were closely associated with drought-induced biomass burning in the rBC so...

We present a new analytical method for accurately measuring femtogram amounts of Pu in environmental swipe samples using a high-purity 244Pu spike and multi-collector inductively-coupled-plasma mass spectrometry. The method was validated by comparative measurements of samples that were previously analysed using a 242Pu spike. The 244Pu spike allows direct normalization of all Pu isotopes to both 244Pu and 239Pu, along with online monitoring of PbAr interferences, resulting in highly-sensitive and accurate Pu assay and isotope ratio measurements. Expanded uncertainties were typically?...

A highly selective and efficient method based on the use of graphene oxide (GO) and a magnetic ionic liquid (MIL) for dispersive micro-solid phase extraction (D-μ-SPE) was developed for inorganic Sb speciation analysis. In this work, Sb(III) species was selectively complexed with sodium diethyldithiocarbamate (DDTC) and retained on 3 mg of GO. Afterwards, 40 μL of the MIL trihexyl(tetradecyl)phosphonium hexachlorodysprosiate(III) ([P6,6,6,14]3DyCl6) were added to instantly magnetize the sorbent surface followed by its separation using a magnetic rod. Then, the aqueous phase containing only Sb(V) was directly analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Total Sb concentration was obtained by direct introduction of the sample into ICP-MS instrument. Thus, Sb(III) was calculated based on the difference between the concentrations of total inorganic Sb and Sb(V). Extraction conditions were optimized by a multivariate study yielding a 99.7% extraction efficiency for S...

Strontium isotopes (87Sr / 86Sr) are useful in the Earth sciences as well as in forensic, archaeological, palaeontological, and ecological sciences. As very few large-scale Sr isoscapes exist in Australia, we have identified an opportunity to determine 87Sr / 86Sr ratios on archive fluvial sediment samples from the low-density National Geochemical Survey of Australia (www.ga.gov.au/ngsa; last access: 15 December 2022). The present study targeted the northern parts of Western Australia, the Northern Territory and Queensland, north of 21.5° S. The samples were taken mostly from a depth of ~60-80 cm in floodplain deposits at or near the outlet of large catchments (drainage basins). A coarse (< 2 mm) grain-size fraction was air-dried, sieved, milled then digested (hydrofluoric acid + nitric acid followed by aqua regia) to release total Sr. The Sr was then separated by chromatography and the 87Sr / 86Sr ratio determined by multicollector-inductively coupled plasma mass spectrometry. Pre...

A systematic approach towards high resolution quantitative multi-element imaging of biological tissue by ICP-TOFMS....

In the last years, LA-ICP-MS has become an attractive technique for analyzing solid samples from various research fields. However, application in material science is often hampered by the limited availability of appropriate certified reference materials, which are a precondition for accurate quantification. Thus, frequently in-house prepared standards are used, which match the sample's composition and include all elements of interest at the required concentration levels. However, preparing and characterizing such standards is often labor-intensive and time-consuming. This work proposes a new approach for the fabrication of matrix-matched standards based on the concept of standard addition. In the first step, the analytes of interest are homogeneously deposited onto the sample surface using liquid standards and a spraying device. For analysis, the generated thin layer is ablated simultaneously with the underlying sample. Thereby deviations in the ablation process and particle transport ...

. Estuaries are dominant conduits of mercury (Hg) to the coastal ocean and the salt marshes within play an important role in coastal Hg cycling. While Hg cycling in upland terrestrial systems has been well studied, processes in salt marsh ecosystems are poorly characterized. We investigated Hg dynamics in vegetation and soils in the Plum Island Sound estuary in Massachusetts, USA and specifically assessed the role of marsh vegetation for Hg deposition and turnover. Monthly quantitative harvesting of aboveground biomass showed strong linear seasonal increases in plant Hg, with a four-fold increase in Hg concentration and an eight-fold increase in standing Hg mass between June (3.9?0.2 ?g kg-1 and 0.7?0.4 ?g m-2, respectively) and November (16.2?2.0 ?g kg-1 and 5.7?2.1 ?g m-2, respectively). Hg ceased to increase in aboveground biomass after plant senescence, indicating physiological controls of vegetation Hg uptake in salt marsh plants. Hg concentrations in live roots and live rhizomes ...

A fully automated, closed-column chromatographic system with parallel multi-channel has been developed. This system is established with seven reagent reservoirs, one multi-channel syringe pump, eight 10-port valves, forty sample tubes, 40 columns, and a fraction collection tray. Four samples can be purified simultaneously at a time, and 40 samples can be purified in one batch. Each sample can be purified by an independent channel, avoiding cross-contamination. The sample tubes can be flipped upside down for automatic cleaning, which eliminates the residue of samples. Moreover, the fraction collection tray can collect up to 104 different target components. The key performance of the system has been investigated. The results show that the sample tubes are well-cleaned, the bubble does not affect the chemical behavior of columns, the consistency of the parallel channels is excellent and the blank of the system is negligible. The system was demonstrated by the purification of Sr from refer...

Continental carbonates, such as travertines and tufas, formed from CO2-rich groundwater degassing as it emerges at the Earth’s surface, are often associated with major crustal-scale faults. The Carraclaca site, in the Lorca-Totana section of the Alhama de Murcia Fault, Spain, presents a complex geomorphological landscape controlled by active tectonics. The geology here records the interaction between Quaternary alluvial fans, travertines, and a pop-up structure developed in a transpressional section of the fault. The Alhama de Murcia Fault is an 80 km long left-lateral strike-slip fault that is one of the main seismogenic structures in the Iberian Peninsula. In this work, we examined the relation between travertine precipitation in the Carraclaca site and the tectonic activity of this fault zone through morphological and geochemical studies. The δ13C and δ18O isotopic signals indicate that the carbonate deposits are hydrothermal. In addition, the 87Sr/86Sr ratios in the samples su...

Inductively coupled plasma-optical emission spectra were modeled with partial least squares regression models to quantify trace elements in uranium (20-5000 μg per g U) without chemical separations or matrix matched calibration standards....

The determination of silver nanoparticles (Ag NPs) with single-particle inductively coupled plasma mass spectrometry can be severely interfered with coexisting dissolved silver causing high background signals, which can lead to inaccurate quantification of NP size and particle concentration. In this paper, chemically active and reusable 3D printed scavengers are applied for highly efficient dissolved silver removal in Ag NP dispersions, allowing more accurate determination of particle concentration and size. Selective laser sintering was used for constructing the porous 3D scavengers constituting of polystyrene used as a supporting material and ion-exchange material SiliaBond Tosic acid (TA), which were chosen based on their high dissolved silver extraction efficiency and ability to maintain original NP properties. The macroporous structure of the final 3D TA scavengers allowed Ag NPs to pass freely through the object without affecting their original properties. The efficient contact b...

In this study, laser ablation-inductively coupled plasma-mass spectrometry was used to characterize the growth patterns of otolith of Micropogonias furnieri from southeastern Brazil under the influence of coastal marine upwelling. Archaeological fish sagittae otoliths of M. furnieri recovered from Brazilian shell mounds (5820?4980?cal BP) were analysed and compared with those of modern specimens. Otolith Sr/Ca analysis indicated that off southeastern Brazil, M. furnieri shifted from freshwater/brackish in archaeological specimens to brackish/marine in modern times. Regular core-to-edge Sr/Ca oscillations suggest that both modern and archaeological M. furnieri are resident estuarine fish that also use the marine waters adjacent to the coastal zone. Based on analyses of a wide range of otolith edge Sr/Ca values measured in archaeological samples, pre-colonial fishing activities in the coastal regions of Guanabara Bay occurred throughout the year. This study reinforces the importance of M...

Insights into past marine carbon cycling and water mass properties can be obtained by means of geochemical proxies calibrated through controlled laboratory experiments with accurate seawater carbonate system (C-system) manipulations. Here, we explored the use of strontium/calcium ratio (Sr/Ca) of the calcite shells of benthic foraminifera as a potential seawater C-system proxy through a controlled growth experiment with two deep-sea species (Bulimina marginata and Cassidulina laevigata) and one intertidal species (Ammonia T6). To this aim, we used two experimental set-ups to decouple as much as possible the individual components of the carbonate system, i.e., changing pH at constant dissolved inorganic carbon (DIC) and changing DIC at constant pH. Four climatic chambers were used with different controlled concentrations of atmospheric pCO2 (180 ppm, 410 ppm, 1000 ppm, 1500 ppm). Our results demonstrated that pH did not influence the survival and growth of the three species. However, lo...

Antimony (Sb) concentrations were measured in wet atmospheric deposition at 10 high-elevation sites in the Czech Republic (Central Europe) during three winter seasons (2009-2011). Soluble and insoluble Sb forms were quantified in snow (vertical deposition) and rime (horizontal deposition) on mountain summits located equidistantly near the Czech borders with Austria, Germany and Poland. The highest Sb concentrations were found in the soluble form in rime (0.47 μg L-1), while the lowest Sb concentrations were those in the insoluble form in snow (0.017 μg L-1). The estimated average Sb deposition rate in Central Europe amounted to 1.3. 10-4 g m-2 yr-1. Most Sb was deposited in the soluble form in snow (7.9. 10-5 g m-2 yr-1), followed by the soluble form in rime (3.5. 10-5 g m-2 yr-1). The corresponding insoluble fraction contained less Sb, namely 1.2. 10-5 g m-2 yr-1 in snow and 2.3. 10-6 g m-2 yr-1 in rime. The average Sb deposition in Central Europe, measured at an altit...

Constraining the role of dust deposition in regulating the concentration of the essential micronutrient iron in surface ocean waters requires knowledge of the flux of seawater-soluble iron in aerosols and the replacement time of dissolved iron (DFe) in the euphotic zone. Here we estimate these quantities using seasonally resolved DFe data from the Bermuda Atlantic Time-series Study region and weekly-scale measurements of iron in aerosols and rain from Bermuda during 2019. In response to seasonal changes in vertical mixing, primary production and dust deposition, surface DFe concentrations vary from ∼0.2 nM in early spring to >1 nM in late summer, with DFe inventories ranging from ∼30 to ∼80 μmol/m2, respectively, over the upper 200 m. Assuming the upper ocean approximates steady state for DFe on an annual basis, our aerosol and rainwater data require a mean euphotic-zone residence time of ∼0.8-1.9 years for DFe with respect to aeolian input....

There has been increased interest in dissolved gallium (Ga) in natural waters due to its long residence time and its usefulness in tracking water masses; however, current analytical approaches are time consuming and labor intensive (e.g., magnesium hydroxide co-precipitation method, (Mg(OH)2)) or have concerns such as carryover and sample recovery (automated resin column extraction). Ocean observing programs, such as GEOTRACES, recover hundreds of samples per expedition. There are both logistical (sample volume) and analytical (person-hour) demands to economically collect and analyze Ga. We present an automated isotope dilution method (using 99.8% enriched 71Ga) to determine Ga in seawater utilizing commercially available equipment while addressing the challenges of a) sample volume and sample pre-concentration factor, b) instrumental interferences, c) sample-sample carryover, d) sample recovery variability, and e) improving sample detection limits, accuracy and precision. A seaFAST SC...

Biofilm formation can lead to tolerance against stressors like antibiotics, toxic metals, salts, and other environmental contaminants. Halo- and metal-tolerant bacilli and actinomycete strains isolated from a former uranium mining and milling site in Germany were shown to form biofilm in response to salt and metal treatment; specifically, Cs and Sr exposition led to biofilm formation. Since the strains were obtained from soil samples, a more structured environment was tested using expanded clay to provide porous structures resembling the natural environment. There, accumulation of Cs could be shown for Bacillus sp. SB53B, and high Sr accumulation ranging from 75% to 90% was seen with all isolates tested. We could, therefore, show that biofilms in a structured environment like soil will contribute to the water purification obtained by the passage of water through the critical zone of soil, providing an ecosystem benefit that can hardly be overestimated....

Background The application of isotopes of metals in medical science (isotope metallomics) has shown significant growth in the last few years, specifically with respect to the study of metal cycles in the body and/or their use as diagnostic tools for diseases that affect metal homeostasis. Given the great potential for Ca stable isotopes to identify changes in Ca metabolism and bone metabolism, there have been major applications of Ca metallomics?and isotope metallomics. However, reliable and high precision Ca isotopic analysis is challenging considering the limited Ca amounts in some soft tissues compared to e.g., bones and the related interference effect during measurement. Furthermore, there is a lack of Ca isotopic data in widely available biological reference materials with various matrices. Method The development of collision-cell multi-collection inductively-coupled-plasma mass-spectrometers (CC-MC-ICP-MS), such as the Nu Instrument Sapphire, has revolutionized Ca isotope analysi...

One widely utilised method to reduce spectral interferences for measurements using inductively coupled plasma mass spectrometry (ICP-MS) is to employ the use of a reaction cell gas. Nitrous oxide (N2O) is a highly reactive gas typically used for mass-shifting only target analytes to a higher mass-to-charge ratio with increased sensitivity (e.g. +16, +32, +48 amu for monoxide, dioxide, and trioxide product ions respectively). Traditionally, the use of N2O was limited to selected applications due to the creation of new interferences that also interfere with the detected masses of interest. However, with the advent of inductively coupled plasma tandem mass spectrometry (ICP-MS/MS), the use of N2O has gained more traction, with a growing number of publications in recent years. Here, a comprehensive study of the use of N2O for the determination of 73 elements has been conducted, with a comparison to the most widely used mass-shift method using oxygen (O2) as a reaction gas. In total, 59 ele...

The Mg ( ), Ca ( ), and Sr ( ) isotopic compositions of pore fluids, bulk carbonates, planktonic foraminiferal tests, and bulk clays from ODP Site 762 Hole B are presented, as are pore fluid and bulk carbonate and from ODP Site 806 Hole B and pore fluid from ODP Site 807 Hole A. The primary objective of the study is to elucidate the major processes controlling marine pore fluid , specifically the effects of calcite recrystallization and authigenic clay precipitation in sedimentary sections with relatively high carbonate contents. Such studies are critical for evaluating the potential of pore fluids in carbonate section to drive diagenetic alteration, which can compromise applications of geochemical proxies to the past. Pore fluid values at all three sites range from −0.83 to −0.13‰ and exhibit a systematic increase with depth. Bulk carbonate generally decrease with depth, ranging from −3.60 to −5.27‰, at Sites 762 and 806, while mixed species foraminiferal tests (∼250-500...

To account for the potential biogeochemical significance of N2 fixation in the ETSP, we compared reported estimates of N loss in the ETSP (range 9-25 Tg N yr−1, Kalvelage et al., 2013; Karthäuser et al., 2021) to N2 fixation rates measured during our study. We applied a similar approach to Karthäuser et al. (2021) and Bonnet et al. (2013) by considering the same spatial extent of N2 fixation as for N loss to extrapolate our rates and roughly estimate annual N2 fixation inputs over the entire area of the coastal OMZ susceptible to N loss (3.26 × 1011 m2). Using an integrated N2 fixation rate of 69.46 ± 120.02 μmol N m−2 d−1 averaged from 25 stations within 175 km from the coast, total N2 fixation potentially amounts to ∼0-0.32 Tg N yr−1, replenishing ∼0 to 1.3% of the N lost. Based on these estimates, N2 fixation rates from the region would need to be 10-100-fold higher to balance the N loss, therefore demonstrating the low potential for austral ...

A new methodology based on the fluorescence of Cu(II) ternary system with o-phenanthroline (o-Phen) and eosin (Eo) dyes is proposed. The metal was selectively retained on Nylon membranes and the solid surface fluorescence (SSF) was used for anayte quantification. Experimental variables that influence the formation of Cu(II)-o-Phen-eo system and retention step were studied and optimized. At optimal experimental conditions, an adequate tolerance to foreign species was shown with a LOD of 1.18 ng L-1 and a LOQ of 3.57 ng L-1. The methodology was evaluated for their greenness profile and successfully applied to analyte determination in bee's products of West-Center Argentina. Recovery studies showed values near to 100% being satisfactorily validated by ICP-MS....

The expansive Wari state of the Middle Horizon (600-1000 CE) was the first political structure to unify the south-central and north-central Andes. Simultaneously, Wari’s political and cultural influence was not uniform across the diverse populace whom they sought to integrate. In this paper, we propose that a localized view of cosmopolitanism is apt for analyzing heterogenous Wari politics and its impacts on social identities and economies. Rather than assuming cosmopolitan worlds were constituted only in elite contexts, we consider how Wari cosmopolitanism was born out of the everyday and influenced by the localized practices, concerns, and motives of differing groups. We apply this perspective to the study of ceramic production and exchange across disparate Andean regions. Here we integrate new laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) data with previously published data to assess ceramic compositional variability across three regions: Ancash, Arequipa...

The paleostress history and associated deformation mechanisms affecting passive margins are seldom studied, as access to offshore parts is rather limited. We analyze an offshore wellbore core of the Albian, post-rift carbonates of the Sendji Fm which directly overlies the salt of the Aptian Loeme Fm in the Lower Congo Basin. Paleopiezometry based on stylolite roughness inversion (SRIT) and calcite twin inversion (CSIT) was combined with fracture analysis, U-Pb geochronology of calcite cement and burial modeling to unravel the orientations and magnitudes of horizontal and vertical stresses affecting the Sendji Fm over time, with a focus on the impact of salt tectonics on stress records. The results of SRIT on bedding-parallel stylolites constrain the range of depths over which the Sendji Fm strata deformed under a vertical principal stress to 650-2800 m (median ∼1300 m). Once projected onto the burial model derived from TemisFlow™ software, the range of depths converts to a peri...

Las rocas ?gneas son aquellas que se producen a partir del enfriamiento y la solidificaci?n del magma. Es muy importante poder caracterizar qu?micamente este tipo de rocas ya que esto hace posible: clasificarlas, modelar los procesos de g?nesis y evoluci?n de los magmas que llevaron a su formaci?n y determinar el ambiente tect?nico generador. La composici?n qu?mica de las rocas es evaluada mediante la utilizaci?n de diagramas espec?ficos y es relevante para el mapeo geol?gico b?sico, para estudios petrogen?ticos y de evoluci?n tect?nica y para la prospecci?n de recursos minerales. Desde hace muchos a?os se utiliza la informaci?n de la composici?n qu?mica de las rocas para caracterizar los diferentes tipos de rocas e identificar sus or?genes. Elementos qu?micos mayoritarios, as? como otros presentes en concentraciones trazas son seleccionados de acuerdo a sus caracter?sticas de movilidad y representatividad del tipo de roca. Por este motivo, varios elementos han sido estudiados por dife...

The half-life of the alpha-emitter 148Gd was measured using the "direct method", in which the number of atoms is directly determined and their activity is then measured. Pure Gd samples containing megabecquerels of 148Gd were obtained by reprocessing proton-irradiated tantalum material. Multicollector-inductively coupled plasma mass spectrometry was performed to determine the amount of 148Gd atoms retrieved. The activity of the 148Gd atoms contained in the Gd sample was measured by means of alpha-spectrometry. The half-life of 148Gd was deduced to be 86.9 years, with a combined uncertainty of 4.5%....

This work provided a novel analytical procedure for rapid and precise uranium isotopic determination in marine sediment and seawater, using a new type of extraction resin, TK200 resin, in combination with microwave digestion (for marine sediments), Fe(OH)3 co-precipitation (for seawater), and single collector sector field-inductively coupled plasma mass spectrometry (SF ICP-MS) measurement. The removal ability of TK200 extraction chromatography for the interfering elements (IEs) Hg, Pb, Th, Pt, Tl, and the matrix rare earth elements (REEs) was carefully investigated. High decontamination factors (DFs) were obtained for IEs and REEs. Accurate quantification of uranium isotope ratios was accomplished based on a "double-cycle" ICP-MS measurement method. The analytical method was optimized and validated with isotopic standards (IRMM-187), matrix-containing certified reference marine sediments (IAEA-384, IAEA-385, and IAEA-412), and seawater reference material (IAEA-443). A stable chemical ...

Soil health is an important aspect for maintaining adequate crop production, but the specifics of what entails a healthy soil can vary from region to region and crop to crop. In highly managed agricultural systems, unhealthy soil can be masked by intensive management practices, yet there must be detrimental cutoff points in various characteristics, such as soil organic matter (SOM) concentrations, where even highly managed systems start to lose productivity. This negative impact was observed in a Florida citrus grove containing Valencia orange trees with observable differences in tree size yet were otherwise managed identically. A soil health index demonstrated that the areas with smaller trees had a significantly lower index score and those soils contained significantly less SOM (average SOM ?= ?0.57%) compared to areas with larger trees (average SOM ?= ?0.94%). The areas of lower crop productivity also had less enzymatic activity of common carbon-cycling enzymes and different microbi...

The great majority of infant formula (FM) for neonate’s nutrition are produced using ingredients from cow milk. Recently, some countries, such as China and New Zealand, are turning their attention to the use of ovine milk ingredients for FM production. In this study, a pilot plant process has been set up to produce infant formula ingredients from Sarda sheep milk. To meet the nutritional needs of neonates (0-6 and 6-12 months of age) two different liquid milk-derived formulations (IF1 and IF2, respectively) obtained mixing whole milk, skimmed milk, and whey milk ultrafiltration concentrate (retentate) were produced. Compositional analysis of milk, retentate, and the final IFs showed that the two formulations contain elements of nutritional interest, such as well-balanced content of high biological value proteins (casein:whey proteins ratio of 30:70 and 60:40 for IF1 and IF2, respectively), vitamin A, E and B5, cholesterol, minerals, nucleotides, free amino acids and essential fatty a...