Solid Samples Research Articles

Preparation of complex titanium-containing coagulants from large-scale mineral concentrates and their use in wastewater treatment

Relevance. Development of new, highly effective reagents for treatment of wastewater of various origins is a complex and extremely important task. An equally pressing issue remains the development of technologies for processing large-scale mineral products, which currently have not found an economically feasible technology for their processing and have received the status of “waste”. The development of a technology for producing reagents using waste as a raw material will not only have an economic effect but will also significantly minimize the level of negative impact on the environment and take a step towards the implementation of the Zero Waste concept. Aim. Development of technology for processing large-scale titanium-containing raw materials to obtain complex titanium-containing reagents and study of their effectiveness in wastewater treatment from various industries. Methods. To study the phase composition of the samples, the X-ray diffraction method was used, and the determination of metal content in acidic solutions and wastewater was carried out by atomic emission spectroscopy. Results and conclusions. The authors have proposed the technology for production of complex titanium-containing coagulants, which includes hydrometallurgical technology for sulfuric acid processing of large-capacity mineral raw materials – titanite. Aluminum hydroxide was introduced into the resulting solutions to adjust the chemical composition and neutralize free sulfuric acid. The resulting aluminum sulfate transforms into the most stable form of 18-aqueous crystalline hydrate, absorbing moisture from the solution, realizing chemical dehydration. The study of the composition of solid samples of coagulants showed that the predominant phase in the composition of the complex coagulant is aluminum sulfate, and the content of titanium compounds ranges from 1 to 14 wt %. It was established that by varying the ratio of mineral raw materials:sulfuric acid it is possible to vary the amount of modifying additive titanium compounds in the complex reagent. It was proven that the use of complex titanium-containing coagulants in wastewater treatment allows reducing the consumption of coagulants by 25–35%, increasing the efficiency of water purification, minimizing residual concentrations of pollutants, and also significantly increasing the rate of sedimentation of coagulation sludge in comparison with traditional sulfate aluminum.

Enhancing Competency-Based Education in Instrumental Analysis: A Novel Approach Using High-Performance Liquid Chromatography for Real-World Problem Solving

Curricula related to instrumental analysis aim for competency-based education to promote the development of teaching strategies that encourage students to successfully tackle the problem-solving and tasks inherent to their profession. However, this endeavor is constrained by the complexity of equipment and the lack of time in laboratory classes. The objective of this work is to present an alternative high-performance liquid chromatography (HPLC) practice that adapts the desired competencies to a shorter and more effective timeframe. It seeks more active participation from the student and contextualizes chromatographic analysis within a real-world problem that encompasses the entire analytical process, from sample to final result. In this scenario, the student receives a solid sample of spicy paprika from a supermarket and must report the level of spiciness in terms of the total amount of capsaicinoids. To achieve this, they must first apply different experimental conditions for extracting the analytes of interest (varying temperatures and solvents) and selecting the most optimal condition. This practice is designed for short sessions, specifically conducted in two 2.5 h laboratory sessions, and has been implemented in the subject “Advanced Techniques in Instrumental Analysis (ATIA)” in the fourth year of the Degree in Biotechnology at the University of Cadiz. The results obtained demonstrated a significant increase in student motivation and an improvement in the acquisition of skills; 100% of the students achieved a grade higher than seven in the final evaluation of their learning process.

Mechanical and thermal properties of Gyroid-based W[sbnd]Cu composites produced via laser powder bed fusion assisted by infiltration

Plasma-facing components for thermonuclear fusion reactors require the introduction of new materials due to outstanding demands in mechanical, thermal, and thermal cycle fatigue resistivity properties. One promising solution is the WCu composite material or multimaterial that combines the properties of both components. In the present work, WCu samples were obtained by laser powder bed fusion (LPBF) consolidation of a tungsten porous matrix followed by copper infiltration. A design of structures with ordered porosity was achieved by translation of skeletal gyroid unit cell (triply periodic minimal surface). A relative density of 96.7% was achieved for solid pure tungsten samples with optimized LPBF process conditions. As-built W gyroid samples had a 15–20% ultimate compressive strength (UCS) of the solid sample. After the infiltration with copper, the ductility of WCu composites increased drastically, i.e. the samples did not fracture at a strain of 35%. It was found that UCS, yield strength (YS), and thermal diffusivity were sensitive to gyroid unit cell size. The sample with the smallest cell size of 2 mm had superior YS of 626 MPa and thermal diffusivity of 76.4 mm2/s. The obtained results will shed light on the possibilities for further development of WCu manufacturing technology based on the LPBF method combined with subsequent infiltration.

The persistence of SARS-CoV-2 in tissues and its association with long COVID symptoms: a cross-sectional cohort study in China

Growing evidence suggests that symptoms associated with post-COVID-19 condition (also known as long COVID) can affect multiple organs and systems in the human body, but their association with viral persistence is not clear. The aim of this study was to investigate the persistence of SARS-CoV-2 in diverse tissues at three timepoints following recovery from mild COVID-19, as well as its association with long COVID symptoms. This single-centre, cross-sectional cohort study was done at China-Japan Friendship Hospital in Beijing, China, following the omicron wave of COVID-19 in December, 2022. Individuals with mild COVID-19 confirmed by PCR or a lateral flow test scheduled to undergo gastroscopy, surgery, or chemotherapy, or scheduled for treatment in hospital for other reasons, at 1 month, 2 months, or 4 months after infection were enrolled in this study. Residual surgical samples, gastroscopy samples, and blood samples were collected approximately 1 month (18-33 days), 2 months (55-84 days), or 4 months (115-134 days) after infection. SARS-CoV-2 was detected by digital droplet PCR and further confirmed through RNA in-situ hybridisation, immunofluorescence, and immunohistochemistry. Telephone follow-up was done at 4 months post-infection to assess the association between the persistence of SARS-CoV-2 RNA and long COVID symptoms. Between Jan 3 and April 28, 2023, 317 tissue samples were collected from 225 patients, including 201 residual surgical specimens, 59 gastroscopy samples, and 57 blood component samples. Viral RNA was detected in 16 (30%) of 53 solid tissue samples collected at 1 month, 38 (27%) of 141 collected at 2 months, and seven (11%) of 66 collected at 4 months. Viral RNA was distributed across ten different types of solid tissues, including liver, kidney, stomach, intestine, brain, blood vessel, lung, breast, skin, and thyroid. Additionally, subgenomic RNA was detected in 26 (43%) of 61 solid tissue samples tested for subgenomic RNA that also tested positive for viral RNA. At 2 months after infection, viral RNA was detected in the plasma of three (33%), granulocytes of one (11%), and peripheral blood mononuclear cells of two (22%) of nine patients who were immunocompromised, but in none of these blood compartments in ten patients who were immunocompetent. Among 213 patients who completed the telephone questionnaire, 72 (34%) reported at least one long COVID symptom, with fatigue (21%, 44 of 213) being the most frequent symptom. Detection of viral RNA in recovered patients was significantly associated with the development of long COVID symptoms (odds ratio 5·17, 95% CI 2·64-10·13, p<0·0001). Patients with higher virus copy numbers had a higher likelihood of developing long COVID symptoms. Our findings suggest that residual SARS-CoV-2 can persist in patients who have recovered from mild COVID-19 and that there is a significant association between viral persistence and long COVID symptoms. Further research is needed to verify a mechanistic link and identify potential targets to improve long COVID symptoms. National Natural Science Foundation of China, National Key R&D Program of China, Chinese Academy of Medical Sciences Innovation Fund for Medical Sciences, and New Cornerstone Science Foundation. For the Chinese translation of the abstract see Supplementary Materials section.

Rapid and sensitive determination of trace Cd in carbonate samples using direct solid sampling electrothermal vaporization atomic absorption spectrometry

The accurate determination of cadmium (Cd) hosted and accumulated in sedimentary carbonate remains challenging due to its low concentration (ng·g−1) and complex matrix. Conventional methods, such as inductively coupled plasma mass spectrometry (ICP-MS) and graphite furnace atomic absorption spectrometry (GF-AAS), which typically rely on liquid sampling and sample digestion, are tedious, labor-intensive and time-consuming. In this study, a rapid and sensitive method for the direct determination of carbonate-hosted Cd was developed based on solid sampling electrothermal atomic absorption spectrometry (SS-ETV-AAS). This method eliminates the need of acid digestion procedure, allowing the entire analysis, including sample preparation, to be completed within 10 min. To minimize the carbonate matrix effect, ethylene diamine tetra acetic acid disodium salt (EDTA-2Na) was proposed as matrix modifier to facilitate the release of Cd, enabling fast and accurate determination of trace Cd in carbonate samples. Under optimized conditions, the Cd detection limits was found to be as low as 0.17 ng·g−1, and repeatability (relative standard deviation, RSD) was better than 8 % (n = 7). The accuracy of the proposed SS-ETV-AAS was verified by analyzing five carbonate certified reference materials (GBW07127, GBW07129, GBW07130, GBW07135 and JDo-1), two soil certified reference materials (GBW07404a, GBW07405), as well as several actual carbonate samples. All these results demonstrate that the proposed SS-ETV-AAS method provides a simple, rapid and sensitive approach for measuring trace Cd in carbonates.

Rapid and Complete Digestion of Refractory Geological Samples Using Ultrafine Powder for Accurate Analyses of Trace Elements.

Complete sample digestion is a prerequisite for acquiring high-quality analytical results for geological samples. Closed-vessel acid digestion (bomb) has typically been used for the total digestion of refractory geological samples. However, the long digestion time (4-5 days) and insoluble fluoride complexes still pose challenges for digesting refractory geological samples using this approach. In this study, an efficient and simplified digestion technique combining ultrafine powders from planetary ball milling with bomb digestion was developed for trace element analysis of refractory geological samples: peridotite and granitoid. The method shows two significant improvements compared with previous approaches. (1) By performing dry planetary ultrafine milling, the initial 200 mesh peridotite (<74 μm) could be reduced to 800 mesh (<20 μm) in 6 min at a ball-to-powder mass ratio of approximately 15 using 3 mm tungsten carbide milling balls. (2) Complete peridotite and granitoid dissolution were achieved in approximately 2 h, 60 times faster than what is achievable using previous methods (2 h vs 120 h). Moreover, ultrafine powders effectively suppressed insoluble fluoride formation during bomb digestion. A suite of peridotite and granitoid reference materials were measured to evaluate the stability of this method. This efficient, simple, and reliable sample digestion method could benefit geological, food, environmental, and other fields requiring solid sample decomposition via wet acid, fusion, combustion, or dry ashing.

3D-printed bioinspired spicules: Strengthening and toughening via stereolithography

Recently, the replication of biological microstructures has garnered significant attention due to their superior flexural strength and toughness, coupled with lightweight structures. Among the most intriguing biological microstructures renowned for their flexural strength are those found in the Euplectella Aspergillum (EA) marine sponges. The remarkable strength of this sponge is attributed to its complex microstructure, which consists of concentric cylindrical layers known as spicules with organic interlayers. These features effectively impede large crack propagation, imparting extraordinary mechanical properties. However, there have been limited studies aimed at mimicking the spicule microstructure. In this study, structures inspired by spicules were designed and fabricated using the stereolithography (SLA) 3D printing technique. The mechanical properties of concentric cylindrical structures (CCSs) inspired by the spicule microstructure were evaluated, considering factors such as the wall thickness of the cylinders, the number of layers, and core diameter, all of which significantly affect the mechanical response. These results were compared with those obtained from solid rods used as solid samples. The findings indicated that CCSs with five layers or fewer exhibited a flexural strength close to or higher than that of solid rods. Particularly, samples with 4 and 5 cylindrical layers displayed architecture similar to natural spicules. Moreover, in all CCSs, the absorbed energy was at least 3–4 times higher than solid rods. Conversely, CCSs with a cylinder wall thickness of 0.65 mm exhibited a more brittle behavior under the 3-point bending test than those with 0.35 mm and 0.5 mm wall thicknesses. CCSs demonstrated greater resistance to failure, displaying different crack propagation patterns and shear stress distributions under the bending test compared to solid rods. These results underscore that replicating the structure of spicules and producing structures with concentric cylindrical layers can transform a brittle structure into a more flexible one, particularly in load-bearing applications.

Estimating bacterial breakthrough behaviors based on bacterial retention profiles in porous media

AbstractTraditional methods for assessing bacterial transport in soil or permeable sand aquifers, such as flow‐through experiments, breakthrough curve (BTC), and retention profile (RP) analysis, face challenges due to their complexity and the labor‐intensive nature of in situ implementations. This study seeks to address the question: How can the transport behavior of bacteria in soil be predicted in a simpler and more cost‐effective manner using RPs? We introduce an RP method designed to overcome these challenges by utilizing soil sampling at various depths to model bacterial breakthrough behaviors with greater efficiency. By employing the one‐site attachment/detachment model within the Hydrus 1D framework, our research compares the RP method (three RPs) against the conventional approach (BTC + RP), showcasing its efficacy through column experiments with bioluminescent Escherichia coli in humic acid‐coated sand. The results indicate that the accuracy of RP method aligns closely with traditional methods in predicting bacterial transport. This technique allows for the use of solid samples collected from a limited number of depths to predict breakthrough behaviors accurately, making it suitable for evaluating bacterial transport in settings such as farmlands, contaminated lands, riverbanks, and soil aquifer treatment systems. Our findings underscore the RP method's role in streamlining experimental procedures and its potential application in environmental science and agronomy.

Development of magnetic matrix solid phase dispersion method for the extraction of crystal violet and rhodamine B from sediments based on magnetic ZIF-8 and a deep eutectic solvent

A magnetic matrix solid phase dispersion (MSPD) method based on magnetic ZIF-8 (SDS@MZIF-8) and a deep eutectic solvent was developed and used to the extraction of crystal violet and rhodamine B in lake sediments. SDS@MZIF-8 was prepared and used as the extraction sorbent and dispersant in MSPD. The magnetic property of MZIF-8 facilitated the recovery of the extraction sorbent after the blending step. Hydrophilic deep eutectic solvents were prepared and used as efficient green dispersing solvents in MSPD. The use of magnetic sorbent in MSPD is simple and fast, eliminating some additional steps commonly used in the classical MSPD and shortening the extraction time. The parameters influencing the extraction efficiency were investigated and optimized. Under the optimized conditions, the intra- and inter-day relative standard deviations were less than 4.9 %. The linearity ranged from 2-400 µg g−1 with coefficients of determination higher than 0.9943. The detection and quantification limits of RB and CV varied between 0.3–0.5 μg g−1 and 1.0–1.8 μg g−1, respectively. Finally, the developed method was applied to the analysis of RB and CV in the sediment samples. The recoveries ranged from 93.2 to 107.3 % and the relative standard deviations ranged from 0.8 to 4.9 %. The results suggest a high potential use of the proposed method to determine the organic pollutants in solid samples. Compared with the conventional MSPD extraction technique, the developed method considerably reduced the sample and solvent consumption, offering important environmental benefits.

Combined leaching and steam explosion pretreatment of lignocellulosic biomass for high quality feedstock for thermochemical applications

A novel pretreatment approach was developed in the present study to simultaneously reduce the content of inorganic troubling elements (TEs) and improve biomass energy density, i.e., combined leaching and steam explosion (SE) pretreatment with mechanical pressing. Three different high-ash-containing biomass feedstocks were studied – wheat straw (WS), spruce bark (SB), and empty fruit bunches of oil palm (EFB). Before studying the combined pretreatment, the impact of individual pretreatment was determined in-depth on biomass composition and ash-transformation behaviour. In leaching pretreatment, the effect of leaching with steam explosion condensate (SEC), dilute acetic acid and water was studied comprehensively. The solid (raw and treated) and liquid samples (leachate, SEC, hydrolysate) were characterized for a detailed comparative analysis. The ash-fusion and −transformation behaviour of raw and pretreated biomass was studied in-depth using advanced multicomponent thermodynamic equilibrium modelling (TEM) and push-rod dilatometry. After combined pretreatment, a considerably high reduction in TEs content was noted: 82–98 % K, 93–99 % Na, 80–99 % Cl, 34–90 % S, 3–77 % Mg, ash 43–63 %, 26–67 % P, and 19–63 % Ca. Simultaneously, heating values of all three feedstocks increased by 1.3–2.3 MJ/kg, reaching up to 20–22 MJ/kg. TEM results reveal that much lesser amounts of molten slag and volatile inorganic compounds were formed in pretreated samples compared to raw and SE biomass, such as K2Si5MgO12, KCl, KPMgO4, K2Si2O5, CaSiO3, and MgSiO3 in WS; Na2CO3, K2CO3, K2CaC2O6, KPMgO4, and CaCO3 in SB. Due to higher energy density and lower propensity towards ash-related issues, combined pretreated WS and SB have a high potential to be used in large-scale thermochemical applications.

Chemical structure and characterization of bio-oils isolated from walnut shells by different processes

This study investigated the products and properties of bio-yields obtained from different types of processes using the extraction and pyrolysis of walnut shells. Pyrolysis experiments were carried out with 10 g walnut shells at a pyrolysis temperature of 550 °C, a heating rate of 10 °C /1 min, a particle size of 1-1.5 mm, and a specific nitrogen gas flow rate. Aqueous extracts were obtained by placing the solid sample in a glass jar with methanol-chloroform (1:1 v/w) solvent indoors and away from light for five days. The obtained liquid samples were analyzed by Gas chromatography-mass spectrometry (GC-MS), Liquid Chromatography Mass Spectrometry (LC/MS-MS), and Fourier Transform Infrared Spectroscopy (FT-IR). Chemical composition analysis of the bio-oils revealed that phenol compounds were more concentrated in the aqueous extract process and volatile oil compounds that were more dominant in the pyrolysis process. The structural analysis results of the bio-oil showed that bio-oil products obtained from walnut shells can be used as fuel, composite film for different purposes, and value-added products. It can be said that the content analysis of liquid samples obtained as a result of pyrolysis and extraction of walnut shells was elucidated with advanced analytical techniques such as LC-MS/MS and GC-MS. The test results revealed that these products will be used in different areas such as energy and high-value-added products. This study provides researchers with a concrete prediction about the suitability of content-analyzed walnut shells.

Ensuring the Quality of the Analytical Process in a Research Laboratory

This paper discusses approaches for verification of methods of measurements of chemical and physical characteristics of specific samples. The limitations of well-known approaches are discussed. Some examples of alternatives are given to demonstrate specific issues encountered in the research laboratory analyzing new materials or characterizing new properties of materials. Application of sequential procedure using lower quantities of samples and reagents is presented. A standard addition to solid samples is discussed. The approach of control charts for estimation of method uncertainty for determination of plant available phosphorus is presented. The method comparison is applied as an approach to verification of alkaline reactivity by inductively coupled plasma–optical emission spectroscopy (ICP-OES) measurement, as well as density of newly synthesized chalcogenide glass materials. The presented examples demonstrated that alternative approaches are needed in order to verify the methods applied due to the great variety of activities and corresponding tasks in a research laboratory.

Quantification of quaternary ammonium compounds by liquid chromatography-mass spectrometry: Minimizing losses from the field to the laboratory

Quaternary Ammonium Compounds (QACs) are widely used in household, medical and industrial settings. As a consequence, they are ubiquitously found in the environment. Although significant efforts have been put into the development of sensitive and reproducible analytical methods, much less effort has been dedicated to the monitoring of QACs upon sample storage and sample preparation. Here we studied the effect of storage, concentration, and extraction procedures on the concentrations of QACs in samples. Thirteen QACs selected amongst benzalkonium compounds (BACs), dialkyldimethylammonium compounds (DADMACs) and alkyltrimethylammonium compounds (ATMACs) were quantified in aqueous and solid samples using LC-MS/MS. Most QACs adsorbed on container walls could be recovered using a short washing step with MeOH containing 2 % v/v formic acid. Concentrations of QACs from aqueous solutions using solid phase extraction (SPE) with Strata-X cartridges and elution with acidified MeOH utilized to wash the emptied containers gave highly satisfactory recoveries (101–111 %). Good recoveries (89–116 %) were also obtained when extracting a spiked organic-rich synthetic soil using accelerated solvent extraction (ASE) with acidified MeOH at low solid/solvent ratio (0.4 g/20 mL). Applying the recommended methodologies to real samples collected from a Canadian wastewater treatment plant (WWTP) gave QAC concentrations in the ranges of 0.01–30 µg/L, < 1.2 µg/L, and 0.05–27 mg/kg for the influent, effluent and biosolids samples, respectively.

Physicochemical characteristics of grease-trap wastewater with different potential mechanisms of FOG solid formation, separation, and accumulation inside grease traps

This work investigates the physicochemical characteristics of grease-trap wastewater discharged from a large community market. It proposes potential mechanisms of fat, oil, and grease (FOG) solid formation, separation, and accumulation inside grease traps. Sixty-four samples, i.e., the floated scum, suspended solid-liquid wastewater, and settled sludge, were collected from the grease-trap inlet and outlet chambers. A lower pH of 5-6 at 25-29 °C inside the grease trap than those reported under the sewer conditions (pH 6-7) was revealed. A significant difference in solid and dissolved constituents was also discovered between the inlet and outlet chambers, indicating that the baffle wall could affect the separation mechanism. The sludge samples had 1.5 times higher total solids (TS) than the scum samples, i.e., 0.225 vs. 0.149 g g−1 TS, revealing that the sludge amount impacted more significantly the grease trap capacity and operation and maintenance. In contrast, the scum samples had 1.4 times higher volatile solids (VS) than the sludge samples, i.e., 0.134 vs. 0.096 g g−1 VS, matching with the 64.2 vs. 29.7% of carbon content from CHN analysis. About 2/3 of the free fatty acids (FFAs) with palmitic acids were the primary saturated FFAs, while the remaining 1/3 of unsaturated FFAs were found in the solid and liquid samples. Although up to 0.511 g g−1 FOG can be extracted from the scum samples, none from the sludge samples. More diverse minerals/metals other than Na, Cl, and Ca were found in the sludge samples than in the scum samples. Grease-trap FOG solids and open drain samples exhibited similar physicochemical properties to those reported in the literature. Four potential mechanisms (crystallization, emulsification, saponification, and baffling) were presented. This work offers insights into the physicochemical properties of grease-trap wastewater that can help explore its FOG solid formation, separation, and accumulation mechanisms inside a grease trap.

Depth profile analysis and high-resolution surface mapping of lithium isotopes in solids using laser-induced breakdown spectroscopy (LIBS)

Lithium isotopic analysis is of interest in various fields from biology to energy. In addition to analytical methods commonly used for that purpose, a new complementary method for determining the spatial resolution of isotopic ratio in solid samples was previously developed: laser induced self-reversal isotopic spectrometry (LIBRIS), derived from laser-induced breakdown spectroscopy (LIBS). In this paper, we present a proof of concept of fast spatially-resolved quantitative isotopic analysis of lithium by LIBS both in depth (z resolution) and in configuration of high-resolution surface mapping (x and y resolution). First, a depth profile measurement where a 9% relative uncertainty on the 6Li isotopic ratio and 0.74 μm depth resolution is obtained. Then, we introduce the first high-resolution lithium isotopic mapping obtained by LIBS with a 3.3 μm lateral resolution and a typical 40% relative uncertainty on the 6Li isotopic ratio is obtained. Those results could be applied in the future to a large number of solid samples where fast information on the lithium isotopic distribution are needed, for instance in solid-state batteries development.

Occurrence and abundance of microplastics and plasticizers in landfill leachate from open dumpsites in Sri Lanka

This is the first attempt that investigate the abundance of plasticizers in leachate sediment in the scientific literature, alongside the debut effort to explore the abundance of microplastics and plasticizers in landfill leachate and sediment in Sri Lanka. Microplastics in sizes ranging from ≥2.0–5.0, ≥1.0–2.0, and ≥ 0.5–1.0 mm were extracted from the leachate draining from ten municipal solid waste open dump sites and sediment samples covering seven districts. Microplastics were extracted by density separation (Saturated ZnCl2) followed by wet peroxide digestion and the chemical identification was conducted by Fourier Transform Infrared spectroscopy. Plasticizers were extracted to hexane and analyzed by high-performance liquid chromatography. The total mean microplastic abundance in leachate was 2.06 ± 0.62 mg/L whereas it was 363 ± 111 mg/kg for leachate sediments. The most frequently found polymer type was polyethylene (>50%), and white color was dominant. The average concentration of bisphenol A (BPA), benzophenone (BP) and diethyl-hydrogen phthalate (DHEP) in leachate was 158 ± 84.4, 0.75 ± 0.16 and 170 ± 85.8 μg/L respectively. Furthermore, BP and DHEP in leachate sediment was 100 ± 68.3 and 1034 ± 455 μg/kg respectively. As landfill leachate is directly discharged into nearby surface and groundwater bodies that serve as sources of drinking water, the study highlights the potential concerns of microplastic and plasticizer exposure to the surrounding Sri Lankan community through consumption of contaminated drinking water. Therefore, there is a timely need of develop the effective waste management and pollution control measures to minimize the possible threats to both the environment and human health.

Comparison of laser-induced breakdown spectroscopy (LIBS) and ICP analysis results for measuring Pb and Zn in soil

Context Laser-induced breakdown spectroscopy (LIBS) is a rapid, multielement analytical technique. It is particularly suitable for the qualitative and quantitative analyses of heavy metals in solid samples. Aims To validate the technique, the LIBS data were compared with the data obtained via conventional inductively coupled plasma (ICP) spectroscopy for the same soil samples. Methods In this study, standard and unknown soil samples from contaminated areas were prepared and fixed to an adhesive tape for LIBS analysis. The soils were also digested with acids for ICP analysis. The emission intensity of one selected line for each of the two analytes, i.e. lead (Pb) and zinc (Zn), was normalised to the background signal and plotted as a function of the concentration values previously determined via ICP analysis. Key results The data demonstrated good linearity for the calibration lines drawn, and the correlation between the ICP and LIBS data was confirmed by the satisfactory agreement between the corresponding values. Conclusions The concentration coefficient of determination (R2) between LIBS and ICP-aqua regia digestion analysis or ICP-total digestion analysis were &gt;0.86 and &gt;0.89 for Pb and Zn, respectively. The total analysis time for the LIBS method was 310 min, which was 54.40% shorter than that for the ICP method (680 min). Implications Consequently, LIBS can be used to measure Pb and Zn in soils without any chemical preparation.

Experimental study on the micro-mechanical parameters of Ni-based single-crystal superalloys using nanoindentation and element distribution analysis

Ni-based single-crystal superalloys are normally prepared by directional solidification. Due to different solidification sequences, Ni-based single-crystal superalloys exhibit a typical dendritic arm structure, and the element segregation in the dendritic arm can affect the high temperature mechanical properties of the alloy. Solid solution treatment has a certain extent to reduce the inter-dendritic and dendritic arm between the concentrations of the elements, thereby changing the alloy micro-nano view parameters to improve the high temperature mechanical properties of the alloy. In this study, nanoindentation experiments were carried out on the inter-dendritic and dendritic arm of the cast and solid solution samples. The micromechanical parameters were calculated. The amounts of changes in elemental concentration were discussed with the results of the energy dispersive spectroscopy and electron probe microanalysis, so as to analyse the relationship between the micromechanical parameters and the changes in elemental concentration. The results show that solid solution treatment has a significant impact on the elastic modulus, with an increase of 114.7% of the inter-dendritic region and an increase of 142.7% of the dendritic arm. However, solid solution treatment has little effect on the hardness, with no significant change in the hardness of the inter-dendritic region and an increase of 43.86% of the dendritic arm. Solid solution treatment has a more significant effect on improving the segregation behavior of Al and Co elements, with the segregation coefficients of Al and Co elements in the inter-dendritic region decreasing and increasing by 36% and 19%, and the segregation coefficients of Al and Co elements in the dendritic arm region decreasing and increasing by 29% and 34%.

Differential metamaterial based sensor for solid dielectric characterization with improved sensitivity

PurposeThe purpose of this study is to introduce a new type of sensor which uses microwave metamaterials and direct-coupled split-ring resonators (DC-SRRs) to measure the dielectric properties of solid materials in real time. The sensor uses a transmission line with a bridge-type structure to measure the differential frequency, which can be used to calculate the dielectric constant of the material being tested. The study aims to establish an empirical relationship between the dielectric properties of the material and the frequency measurements obtained from the sensor.Design/methodology/approachIn the proposed design, the opposite arm of the bridge transmission line is loaded by DC-SRRs, and the distance between DC-SRRs is optimized to minimize the mutual coupling between them. The DC-SRRs are loaded with the material under test (MUT) to perform differential permittivity sensing. When identical MUT is placed on both resonators, a single transmission zero (notch) is obtained, but non-identical MUTs exhibit two split notches. For the design of differential sensors and comparators based on symmetry disruption, frequency splitting is highly useful.FindingsThe proposed structure is demonstrated using electromagnetic simulation, and a prototype of the proposed sensor is fabricated and experimentally validated to prove the differential sensing principle. Here, the sensor is analyzed for sensitivity by using different MUTs with relative permittivity ranges from 1.006 to 10 and with a fixed dimension of 9 mm × 10 mm ×1.2 mm. It shows a very good average frequency deviation per unit change in permittivity of the MUTs, which is around 743 MHz, and it also exhibits a very high average relative sensitivity and quality factor of around 11.5% and 323, respectively.Originality/valueThe proposed sensor can be used for differential characterization of permittivity and also as a comparator to test the purity of solid dielectric samples. This sensor most importantly strengthens robustness to environmental conditions that cause cross-sensitivity or miscalibration. The accuracy of the measurement is enhanced as compared to conventional single- and double-notch metamaterial-based sensors.

Microbial induced wettability alteration with implications for Underground Hydrogen Storage

Characterization of the microbial activity impacts on transport and storage of hydrogen is a crucial aspect of successful Underground Hydrogen Storage (UHS). Microbes can use hydrogen for their metabolism, which can then lead to formation of biofilms. Biofilms can potentially alter the wettability of the system and, consequently, impact the flow dynamics and trapping mechanisms in the reservoir. In this study, we investigate the impact of microbial activity on wettability of the hydrogen/brine/rock system, using the captive-bubble cell experimental approach. Apparent contact angles are measured for bubbles of pure hydrogen in contact with a solid surface inside a cell filled with living brine which contains sulphate reducing microbes. To investigate the impact of surface roughness, two different solid samples are used: a “rough” Bentheimer Sandstone sample and a “smooth” pure Quartz sample. It is found that, in systems where buoyancy and interfacial forces are the main acting forces, the impact of biofilm formation on the apparent contact angle highly depends on the surface roughness. For the “rough” Bentheimer sandstone, the apparent contact angle was unchanged by biofilm formation, while for the smooth pure Quartz sample the apparent contact angle decreased significantly, making the system more water-wet. This decrease in apparent contact angle is in contrast with an earlier study present in the literature where a significant increase in contact angle due to microbial activity was reported. The wettability of the biofilm is mainly determined by the consistency of the Extracellular Polymeric Substances (EPS) which depends on the growth conditions in the system. Therefore, to determine the impact of microbial activity on the wettability during UHS will require accurate replication of the reservoir conditions including surface roughness, chemical composition of the brine, the microbial community, as well as temperature, pressure and pH-value conditions.