Sample Preparation Research Articles

Application of convolutional long short-term memory for spatio-temporal forecastings of hydrocarbon saturations and pressure in oil fields

A machine learning architecture composed of convolutional long short-term memory (convLSTM) is developed to predict spatiotemporal parameters, that is, saturation and pressure in an oil & gas field namely, the SACROC field in Texas, USA. The spatial parameters are recorded at the end of each month for 360 months, approximately 83% of which is used for training and the rest 17% is kept for testing. The samples for the convLSTM models are prepared by choosing ten consecutive frames as input and ten consecutive frames shifted forward by one frame as output. A workflow is provided describing the entire process of data extraction, preprocessing, sample preparation, training, testing of machine learning models, and error analysis. The structural similarity index measure (SSIM) and normalized root mean squared error (NRMSE) are calculated during training and testing for quantitative error analysis. During the training phase, the predicted frames demonstrate a strong resemblance to the ground truth frames. Moreover, it exhibits superior performance during the initial months of testing. As testing progresses into the later months, deviations increase as errors accumulate over time for relying on past predictions. In summary, convLSTM for spatio-temporal prediction offers significant potential for forecasting and optimizing hydrocarbon recovery from porous media.

Optimization of structure, optical, magnetic, and radiation shielding properties of ZnO@xSrFe12O19 nanocomposites

In this work, the pristine ZnO, SrFe12O19 (SFO), and their nanocomposites (ZnO/x SFO: x = 1, 3 and 5%) were synthesized by co-precipitation and sonomechanical method. The x-ray diffraction data validate the preparation of ZnO, SFO, and nanocomposite samples with high phase purity. The optical band gap was calculated from UV–vis-NIR diffuse reflectance measurements, and it was modified by increasing SFO content. Adding 1, 3, and 5 wt% of SFO to the ZnO matrix showed ferromagnetic characteristics for the nanocomposites with a squareness ratio of around 0.49, which considered these nanocomposites as a magnetic semiconductor suitable for digital memory and spintronic applications. Additionally, the radiation shielding features of the prepared samples were evaluated. The shielding parameters for the studied samples were obtained using the Phy-X/PSD program. The fast neutron removal cross-section of SFO was 0.094 cm−1, the highest among the investigated samples, while the composites had similar values, about 0.083 cm−1. The results indicated that the γ--ray attenuation ability and the values of exposure buildup factor for the prepared samples were close. Therefore, ZnO, SFO, and their nanocomposites compared to stationary shielding materials (SMs), can be candidates for applications where radiation protection is needed.

Bullet-DNP Enables NMR Spectroscopy of Pyruvate and Amino Acids at Nanomolar to Low Micromolar Concentrations.

Hyperpolarized pyruvate is a widely used marker to track metabolism in vivo and a benchmark molecule for hyperpolarization methods. Here, we show how a combination of improved bullet-DNP instrumentation, an optimized sample preparation and a further sensitivity increase via a 13C-1H polarization transfer after dissolution enable the observation of pyruvate at a concentration of 250 nM immediately after dissolution. At this concentration, the experiment employs a total mass of pyruvate of only 20 ng or 180 pmol. If the concentration is increased to 45 μM, pyruvate may be detected 1 min after dissolution with a signal-to-noise ratio exceeding 50. The procedure can be extended to observe a mixture of amino acids at low micromolar concentrations.

New screening and quantification method by UHPLC-MS/MS of 36 new synthetic cathinones in hair. Application to real cases

A class of β-keto analogs of phenethylamine known as synthetic cathinones has been identified as the most emergent new class of psychoactive chemicals in the last ten years. Synthetic cathinones (SC) are becoming more varied, which represents a serious danger to social security and public health worldwide. In this work, an analytical technique based on UHPLC-MS/MS was developed for the simultaneously measurement of 36 synthetic cathinones and two metabolites in hair keratin samples. The separation was conducted by Atlantis Premier BEH C18 AX (2.5 μm, 2.1 × 100 mm) column using elution with 5 mM ammonium acetate in water with 0.1 % formic acid (v/v) (mobile phase A) and 2 mM ammonium formate in MeOH/Acetonitrile 50/50, +0.1 % formic acid (v/v) (mobile phase B). The analysis time was 11 min. Mass spectrometer was equipped with electrospray ionization (ESI). Multiple reaction monitoring (MRM) mode was used for the detection and quantification of the studied compounds. The methodology was successfully validated according to the Organization Scientific Area Committee guidelines, with linearity (r2 ≥ 0.99) from LOQ to 500 pg/mg concentrations for all the compounds investigated. This method was subsequently applied to nine hair samples positive for ten different synthetic cathinones. The most common SCs identified were 3,4-methylenedioxypyrovalerone (3,4-MDPV), in a concentration range 6.0–1000.0 pg/mg, along with alpha-pyrrolidinopentiophenone (α-PHP (54.0 and 554.0 pg/mg, respectively)), followed by the two positional isomers 3-MMC (556.0 and 5000.0 pg/mg) and 4-MMC (11.5 and 448.0 pg/mg). In conclusion, a validated LC-MS/MS method with high specificity was developed offering an easy and affordable sample preparation, and a run time that makes it suitable for use in a high throughput forensic laboratory for the multi-analyte quantification of 36 novel synthetic cathinones and 2 metabolites in hair.

Analysis of cell cycle stage, replicated DNA, and chromatin-associated proteins using high-throughput flow cytometry

Abstract Flow cytometry is a versatile tool used for cell sorting, DNA content imaging, and determining various cellular characteristics. With the possibility of high-throughput analyses, it combines convenient labelling techniques to serve rapid, quantitative, and qualitative workflows. The ease of sample preparation and the broad range of applications render flow cytometry a preferred approach for many scientific questions. Yet, we lack practical adaptations to fully harness the quantitative and high-throughput capabilities of most cytometers for many organisms. Here, we present simple and advanced protocols for the analysis of total DNA content, de novo DNA synthesis, and protein association to chromatin in budding yeast and human cells. Upon optimization of experimental conditions and choice of fluorescent dyes, up to four parameters can be measured simultaneously and quantitatively for each cell of a population in a multi-well plate format. Reducing sample numbers, plastic waste, costs per well, and hands-on time without compromising signal quality or single-cell accuracy are the main advantages of the presented protocols. In proof-of-principle experiments, we show that DNA content increase in S-phase correlates with de novo DNA synthesis and can be predicted by the presence of the replicative helicase MCM2-7 on genomic DNA.

Improved Liver Intravital Microscopic Imaging Using a Film-Assisted Stabilization Method.

Intravital microscopy (IVM) is a valuable method for biomedical characterization of dynamic processes, which has been applied to many fields such as neuroscience, oncology, and immunology. During IVM, vibration suppression is a major challenge due to the inevitable respiration and heartbeat from live animals. In this study, taking liver IVM as an example, we have unraveled the vibration inhibition effect of liquid bridges by studying the friction characteristics of a moist surface on the mouse liver. We confirmed the presence of liquid bridges on the liver through fluorescence imaging, which can provide microscale and nondestructive liquid connections between adjacent surfaces. Liquid bridges were constructed to sufficiently stabilize the liver after abdominal dissection by covering it with a polymer film, taking advantage of the high adhesion properties of liquid bridges. We further prototyped a microscope-integrated vibration-damping device with adjustable film tension to simplify the sample preparation procedure, which remarkably decreased the liver vibration. In practical application scenarios, we observed the process of liposome phagocytosis by liver Kupffer cells with significantly improved image and video quality. Collectively, our method not only provided a feasible solution to vibration suppression in the field of IVM, but also has the potential to be applied to vibration damping of precision instruments or other fields that require nondestructive ″soft″ vibration damping.

Local plastic deformation effects on the critical current of high-Jc Nb3Sn strands under uniaxial strain

Abstract In order to meet the target operating parameters of the toroidal field coils (TFC) for the next-generation Chinese compact burning plasma tokamak, high critical current density (Jc) Nb3Sn strand will be applied to the high-field winding-package (WP) of the TFC. To improve the transverse stiffness of the cable in withstanding the huge Lorentz force and avoiding conductor performance degradation, the Short-Twist-Pitch (STP) and Copper-Wound-Strand (CWS) cable patterns were taken into consideration. In the processes of cabling and compaction of the conductor, the tight cable configurations lead to severe local plastic deformation (LPD) within the strands. The strands in the conductor are subjected to strain caused by thermal contraction and Lorentz force during conductor cooling down and operation. So far it is unknown, whether the LPD could impact the critical current (Ic) versus uniaxial applied strain behaviour of high-Jc Nb3Sn strand. Aiming to investigate the effect of LPD on the Ic of strands under uniaxial strain, three types of high Jc Nb3Sn strand with different indentation depths were tested on a U-shaped bending spring. The axial strain ranges from -0.9% to +0.4% at 14 T and 4.2 K. The three types of strands showed more strain sensitivity and lower tensile irreversible strain limit with increasing LPD, while even irreversible degradation of the Ic could be observed in the compressive strain region. The sample preparation, test process, test results and analysis are reported.

Paper‐Based RNase Digestion toward Viral Nucleic Acid Self‐Tests

AbstractHome‐based Nucleic Acid Amplification Tests (NAATs) for viral infections would be an important step to improve public health, but sample preparation remains an important obstacle, particularly for the protection of target RNA from RNases in samples. Here, a new method for RNase deactivation in saliva samples is presented. This method uses Proteinase K (PK) immobilized on nitrocellulose membrane to store and deliver the enzyme, capable of digesting nucleases present in the sample. The immobilized PK is also separated from the amplification reagents, so that it does not disrupt DNA amplification, thus omitting the need for heat‐deactivation or dilution steps. Treatment by PK nitrocellulose at 50 °C dramatically decreases the RNase activity of RNase A, in diluted saliva samples, and even shows promising results at 42 °C. The potential of this method to protect RNA from digestion is further demonstrated, by pretreating diluted saliva samples spiked with Influenza Virus A (IVA) genomic RNA, which allows its amplification and colorimetric detection by lateral flow strips. In the absence of PK pretreatment, the RNA is digested by RNase, which leads to false negative results. These findings show that immobilized PK enables the integration of sample preparation of viral samples toward home‐based NAATs.

Influence of Reed Fiber Length and Dosage on the Properties of Reed-Fiber-Modified Bitumen and Bituminous Mortar

In order to explore the feasibility and efficacy of reed-fiber-modified bitumen (RFMB), three lengths and three dosages of reed fibers were selected to modify bitumen and bituminous mortar, while the physicochemical properties of RFMB and RFMB mortar were analyzed. In this work, FTIR spectroscopy was employed to characterize the chemical impact of fiber on bitumen. The viscidity and rheology of RFMB and the tensile strength of RFMB mortar were evaluated using a Brookfield viscometer, dynamic shear rheometer, and monotonic tensile test. The results showed that adding fibers primarily affects the physical structure rather than the chemical composition of bitumen, confirmed by FTIR spectroscopy. RFMB viscosity increased with higher fiber dosage and fiber length. Rheological evaluations showed an enhanced complex shear modulus for RFMB, suggesting improved performance at higher temperatures but increased stiffness at lower temperatures, with the latter indicating reduced flexibility. RFMB also demonstrated superior fatigue and rutting resistance, albeit with compromised stress sensitivity. Tensile tests on RFMB mortar highlighted significant improvements, especially with longer fibers, while shorter 0.4 mm fibers showed modest reinforcement effects, possibly due to uneven distribution during sample preparation.

Simultaneous observation of 2H and 13C enrichment of methyl phosphonic acid via Orbitrap-IRMS with applications to nerve agent forensics

Quantification of the stable isotopes within a compound aids forensic investigations as it provides a fingerprint which can determine that compound's source substrates, synthetic route, and possible mechanisms of degradation. Previous stable isotope studies have explored 13C and 2H measurements of the sarin precursors methylphosphonic dichloride (DC) and methylphosphonic difluoride (DF) as forensic signatures. However, these measurements required different sample preparations and measurement techniques. Orbitrap isotope ratio mass spectrometry (Orbitrap-IRMS) is a developing technique which can characterize multiple stable isotopes simultaneously. Here, we apply Orbitrap-IRMS to simultaneously observe the 13C and 2H content of methylphosphonic acid (MPA), the hydrolysis product of DC and DF, which can be used as a proxy for the isotopic content of DC and DF. Our method requires 20 min analyses and consumes ≈60 nmol of sample, with precisions of ≈0.9 ‰ (13C) and ≈3.6 ‰ (2H). We apply our method to both commercially acquired MPA and MPA obtained from the hydrolysis of commercially acquired DC. We validate our methods via comparison to elemental-analyzer isotope ratio mass spectrometry (EA-IRMS). The combined 13C and 2H measurement creates a more robust forensic tool than either isotope individually. Our results demonstrate the viability of Orbitrap-IRMS for chemical forensic measurements.

Ocular pharmacokinetics of acetazolamide from intravitreal implants by high-performance liquid chromatography coupled to tandem mass spectrometry

Glaucoma, a leading cause of irreversible blindness, affects about 70 million people globally. Its treatment focuses on reducing intraocular pressure. Acetazolamide, a potent anti-glaucoma drug, is currently used only systemically due to low solubility and permeation, which cause severe side effects. Developing topical medications with acetazolamide requires robust analytical methods for its detection in biological samples. In this context, this study aimed to develop a method to quantify acetazolamide in rabbit vitreous humor samples. The method involved a simple, fast, inexpensive, and environmentally friendly protein precipitation step for sample preparation, needing just 50 μL of sample and 200 μL of organic solvent, with adequate recovery. This was combined with high-performance liquid chromatography coupled to tandem mass spectrometry, enabling highly sensitive (LOQ of 5 ng/mL) quantification within only 5 min. The method proved to be selective, precise, and accurate, with well-fitted analytical curves, with no carryover, and no matrix effect impacting reliability. The method was successfully applied to analyze vitreous humor samples from rabbits in pharmacokinetic studies, monitoring drug release from intravitreal implants. Results showed a controlled release profile, with a maximum drug concentration (Cmax) of 426.01 ± 64.57 ng/mL, time to reach Cmax (Tmax) of 28 days, and area under the curve (AUC0–42 and AUC0-∞) of 7722.66 ± 1125.96 ng days/mL and 8998.11 ± 1311.92 ng days/mL, respectively. The device demonstrated significantly slower elimination, ensuring therapeutic levels for an extended period when compared to intravitreal injection.

Multi-class plant hormone HILIC-MS/MS analysis coupled with high-throughput phenotyping to investigate plant-environment interactions.

Plant hormones are chemical signals governing almost every aspect of a plant's life cycle and responses to environmental cues. They are enmeshed within complex signaling networks that can only be deciphered by using broad-scale analytical methods to capture information about several plant hormone classes simultaneously. Methods used for this purpose are all based on reversed-phase (RP) liquid chromatography and mass spectrometric detection. Hydrophilic interaction chromatography (HILIC) is an alternative chromatographic method that performs well in analyses of biological samples. We therefore developed and validated a HILIC method for broad-scale plant hormone analysis including a rapid sample preparation procedure; moreover, derivatization or fractionation is not required. The method enables plant hormone screening focused on polar and moderately polar analytes including cytokinins, auxins, jasmonates, abscisic acid and its metabolites, salicylates, indoleamines (melatonin), and 1-aminocyclopropane-1-carboxylic acid (ACC), for a total of 45 analytes. Importantly, the major pitfalls of ACC analysis have been addressed. Furthermore, HILIC provides orthogonal selectivity to conventional RP methods and displays greater sensitivity, resulting in lower limits of quantification. However, it is less robust, so procedures to increase its reproducibility were established. The method's potential is demonstrated in a case study by employing an approach combining hormonal analysis with phenomics to examine responses of three Arabidopsis ecotypes toward three abiotic stress treatments: salinity, low nutrient availability, and their combination. The case study showcases the value of the simultaneous determination of several plant hormone classes coupled with phenomics data when unraveling processes involving complex cross-talk under diverse plant-environment interactions.

The role of protein corona in advancing plasma proteomics.

The protein corona, a layer of biomolecules forming around nanoparticles in biological environments, critically influences nanoparticle interactions with biosystems, affecting pharmacokinetics and biological outcomes. Initially, the protein corona presented challenges for nanomedicine and nanotoxicology, such as nutrient depletion in cell cultures and masking of nanoparticle-targeting species. However, recent advancements have highlighted its potential in environmental toxicity, proteomics, and immunology. This viewpoint focuses on leveraging the protein corona to enhance the depth of plasma proteome analysis, addressing challenges posed by the high dynamic range of protein concentrations in plasma. The protein corona simplifies sample preparation, enriches low-abundance proteins, and improves proteome coverage. Innovations include using diverse nanoparticles and spiking small molecules to increase the number of quantified proteins. Reproducibility issues across core facilities necessitate standardized protocols. Moreover, top-down proteomics enables proteoform-specific measurements, providing deeper insights into protein corona composition. Future research should aim at improving top-down proteomics techniques and integrating protein corona studies and proteomics for personalized medicine and advanced diagnostics.

Performance Comparison of Ambient Ionization Techniques Using a Single Quadrupole Mass Spectrometer for the Analysis of Amino Acids, Drugs, and Explosives.

The utilization of ambient ionization (AI) techniques for mass spectrometry (MS) has significantly grown due to their ability to facilitate rapid and direct sample analysis with minimal sample preparation. This study investigates the performance of various AI techniques, including atmospheric solids analysis probe (ASAP), thermal desorption corona discharge (TDCD), direct analysis in real time (DART), and paper spray coupled to a Waters QDa mass spectrometer. The focus is on evaluating the linearity, repeatability, and limit of detection (LOD) of these techniques across a range of analytes, including amino acids, drugs, and explosives. The results show that each AI technique exhibits distinct advantages and limitations. ASAP and DART cover high concentration ranges, which may make them suitable for semiquantitative analysis. TDCD demonstrates exceptional linearity and repeatability for most analytes, while paper spray offers surprising LODs despite its complex setup (between 80 and 400 pg for most analytes). The comparison with electrospray ionization (ESI) as a standard method shows that ambient ionization techniques can achieve competitive LODs for various compounds such as PETN (80 pg ESI vs 100 pg ASAP), TNT (9 pg ESI vs 4 pg ASAP), and RDX (4 pg ESI vs 10 pg ASAP). This study underscores the importance of selecting the appropriate ambient ionization technique based on the specific analytical requirements. This comprehensive evaluation contributes valuable insights into the selection and optimization of AI techniques for diverse analytical applications.

Development of a high-throughput UHPLC-MS/MS method for the analysis of Fusarium and Alternaria toxins in cereals and cereal-based food.

A QuEChERS (quick, easy, cheap, effective, rugged, and safe)-based multi-mycotoxin method was developed, analyzing 24 (17 free and 7 modified) Alternaria and Fusarium toxins in cereals via ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). A modified QuEChERS approach was optimized for sample preparation. Quantification was conducted using a combination of stable isotope dilution analysis (SIDA) for nine toxins and matrix-matched calibration for ten toxins. Quantification via a structurally similar internal standard was conducted for four analytes. Alternariol-9-sulfate (AOH-9-S) was measured qualitatively. Limits of detection (LODs) were between 0.004µg/kg for enniatin A1 (ENN A1) and 3.16µg/kg for nivalenol (NIV), while the limits of quantification were between 0.013 and 11.8µg/kg, respectively. The method was successfully applied to analyze 136 cereals and cereal-based foods, including 28 cereal-based infant food products. The analyzed samples were frequently contaminated with Alternaria toxins, proving their ubiquitous occurrence. Interestingly, in many of those samples, some modified Alternaria toxins occurred, mainly alternariol-3-sulfate (AOH-3-S) and alternariol monomethyl ether-3-sulfate (AME-3-S), thus highlighting the importance of including modified mycotoxins in the routine analysis as they may significantly add to the total exposure of their parent toxins. Over 95% of the analyzed samples were contaminated with at least one toxin. Despite the general contamination, no maximum or indicative levels were exceeded.

A novel HPLC method for selexipag in human plasma and application to a prototype pharmacokinetic study

AbstractA novel simple and cost effective HPLC technique was presented for the quantification of selexipag (SLP) in human plasma sample and the technique's applicability to a pharmacokinetic investigation. Chromatographic separation was achieved with C18 (5 µm × 4.6 mm × 150 mm) column, at 30 °C with isocratic elution, mobile phase composed of solution A (acetonitrile), and solution B (0.5% formic acid) (65:35 v/v) at flow rate 1.2 mL min−1. The linearity range is 10–150 ng mL−1. As sample preparation step human plasma was precipitated with acetonitrile and the detection was provided at 300 nm. The retention time is 8.20 ± 0.02 min. LOD is found to be 3.3 ng mL−1 for drug. The method was applied to the analysis of SLP in human plasma with good recovery as 97.83%. Validation of the studied methods was carried out according to EMA guideline. The new method applied on a prototype pharmacokinetic study by administration of 800 μg SLP to a healthy volunteer and parameters like AUC0–24, AUC0–∞, Cmax, tmax, and t1/2 were assessed.

Assessment of portable X-ray fluorescence (pXRF) for plant-available nutrient prediction in biochar-amended soils

Portable X-ray Fluorescence probe (pXRF) is a tool used to measure many elements quickly and efficiently in soil with minimal sample preparation. Although this sensing technique has been widely used to determine total elemental concentrations, it has not been calibrated for plant-available nutrient predictions. We evaluated the potential of using pXRF for fast plant-available nutrient quantification. Two experiments were conducted in soils treated with two types of biochars to obtain a practical range of soil pH (5.5 − 8.0) and organic carbon (2.0 − 5.5%). Biochars applied were derived from switchgrass (SGB) and poultry litter (PLB). The first experiment received biochars at application rates up to 8% (w/w) and had no plants. The second experiment had up to 4% of SGB or PLB planted with ryegrass (Lolium perenne). Linear regression (LR), polynomial regression (PolR), power regression (PowR), and stepwise multiple linear regression (SMLR) were the models tested. Regardless of the extraction method, phosphorus (P) showed a strong relationship between pXRF and several laboratory extraction methods; however, K prediction via pXRF was sensitive to the plant factor. The optimum soil available-P corresponding to the maximum P uptake in plant tissues can be assessed with pXRF. The LR was inconsistent for calcium (Ca), sulfur (S), and copper (Cu) and non-significant for magnesium (Mg), iron (Fe), and zinc (Zn). Our results showed that pXRF is applicable to estimate P availability in soils receiving organic amendments. More evaluations are needed with diverse soil types to confirm the findings before using pXRF for fertilizer recommendation.

On-site extraction of phenoxycarboxylic acid herbicides in environmental waters utilizing monolith-based in-tip microextraction technique

On-site extraction plays a significant role in the reliable quantification of strong polar phenoxycarboxylic acid herbicides (PCAs) in aqueous samples. In current study, a new technique for the field sample preparation of PCAs was developed by means of three channels in-tip microextraction device (TCIM). To capture PCAs effectively, an extraction phase based on monolith (EPM) using vinylimidazole and divinylbenzene/ethylene dimethacrylate as monomer and cross-linkers, respectively, was in-situ synthesized in pipette tips. The EPM fabricated at optimal conditions were characterized by a series of techniques and employed as the adsorbent of TCIM for the on-site extraction of PCAs. The adsorption isotherm was studied so as to inspect the extraction behaviors of EPM towards PCAs. Results revealed that the proposed EPM/TCIM presented satisfactory extraction performance towards PCAs through multiple interactions. The enrichment factors and adsorption capacity were 74-277 and 20 mg/g, respectively. Under the most beneficial extraction parameters, the developed EPM/TCIM was successfully employed to on-site extract PCAs, and then combining with HPLC equipped with diode array detector to monitor trace PCAs in actual waters. The limits of detection (LODs) towards investigated PCAs varied from 0.071 μg/L to 0.30 μg/L. In addition, the accuracy of established approach was inspected with documented method. Compared with existing lab-based sample preparation approaches, the introduced field sample preparation technique exhibits some merits such as avoidance of transporting large volume of water, prevention of analytes loss during sampling procedure, less usage of organic solvent and achievement of satisfactory efficient in sample preparation.

Improving sample preparation by biochar-coated sampling tubes: proof-of-concept extraction of sex hormones from real waters

This work showcases a novel application of biochar for analytical sample treatment. The carbonaceous material, obtained by pyrolysis of orange peel waste (550°C) without any post-synthesis treatment or functionalization, was thoroughly characterized and easily immobilized on the inner wall of sampling tubes in order to perform a sort of “in-vial” solid-phase extraction (SPE). The as-obtained device was tested for the extraction of seven sexual steroids, as probe water pollutants, from tap, lake, river water and wastewater treatment plant effluent samples spiked with 0.2-5 µg L−1 of each compound. The sorption kinetics profiles showed quantitative uptake from the sample (25 mL) in 20 min contact time, followed by complete elution in pure ethanol (2 mL, 15 min), thanks to the proper balance between sorption affinity and ease of elution. Under the selected conditions, recovery was in the range 60-123%, with good inter-day precision (RSD 10-18%, n=3). As evidence of the excellent reproducibility, an overall RSD below 15% was observed from inter-day inter-batch recovery tests on three individually prepared sampling tubes. The procedure, carried out on a roller mixer, allows 10 samples to be extracted simultaneously, improving the sample throughput. Moreover, reusability tests showed that the same device maintains its efficiency for 10 consecutive sorption/desorption cycles. The greenness assessment, carried out by two dedicated software, further supported the sustainability of this biochar-based sample preparation as an alternative SPE.

Lastarria volcano, a major emitter of boron and chalcophiles in northern Chile and the Central Volcanic Zone

This study examines the trace element chemistry of fumarolic deposits and fumarolic plumes at Lastarria volcano, located in northern Chile. Fumarolic deposits were manually collected, while fumarolic plumes were sampled using the filter pack technique; after sample preparation, both sample types were analyzed by ICP-MS. The research focuses on chalcophile elements (As, Cd, Sb, Te, Cu, Zn, Tl, Pb, and Bi) and B, with the findings revealing significant enrichment of As and Pb in fumarolic deposit samples, especially in medium- and high-temperature fumarolic vents, respectively. On the other hand, filter pack measurements in the fumarolic plume indicate a notable enrichment in Te, B, As, and Tl, with Sc-normalized enrichment factors within the range of 104–106. From these elements, B, Tl, and Te appear to be less scavenged at the vent, presenting more significant enrichments in fumarolic plumes than in fumarolic deposits. By comparing our results with subduction-related volcanoes such as Etna, Stromboli, Lascar, Masaya, or La Soufrière de Guadeloupe, Lastarria fumarolic plume can be regarded as the one with the highest concentrations of B and As ever recorded. Moreover, Lastarria has chalcophile enrichments comparable to those volcanoes with shallower magma chambers and high-temperature magmatic emissions such as Stromboli. The higher abundance of chalcophiles suggests a significant magmatic influence feeding Lastarria fumaroles and the presence of ligands, such as Cl, which can transport significant amounts of chalcophiles at shallower levels of the crust during late-stage magma crystallization. Large amounts of chalcophiles released by Lastarria and Lascar volcanoes could be responsible for the naturally elevated concentrations of these elements in the Altiplano-Puna area. Future studies should focus on the lifetime of chalcophiles in the Central Andean atmosphere, where these elements could reside for a longer time given the dominant hyperarid environment.