Real Soil Samples Research Articles

Colorimetric Nanozyme Sensor Array Based on Metal Nanoparticle-Decorated CNTs for Quantification of Pesticides in Real Water and Soil Samples

Colorimetric Nanozyme Sensor Array Based on Metal Nanoparticle-Decorated CNTs for Quantification of Pesticides in Real Water and Soil Samples

Simultaneous determination of 13 sulfonamides at trace levels in soil by modified QuEChERS with HPLC-MS/MS.

The pretreatment of samples was vital for enhancing the sensitivity and accuracy of analytical methods. An efficient and sensitive method, based on modified QuEChERS with high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) for the simultaneous determination of the 13 sulfonamides (SAs) in soil, was developed. After extraction by sonication with methanol, the clean-up procedure was achieved using QuEChERS with a primary secondary amine (PSA). The quantification of the 13 SAs was performed by HPLC-MS/MS in electrospray ionization (ESI) and multiple reaction monitoring (MRM) modes. Under optimized conditions, the standard solution exhibited good linearity within the range of 0.01-0.5 μg mL-1. The limits of detection and the limits of quantification of the developed method were 0.007-0.030 μg kg-1 and 0.022-0.101 μg kg-1, respectively. The spiked recoveries for the 13 SAs were in the range of 74.5-111.7% with RSD less than 15%. Furthermore, the developed method was successfully applied for the determination of SAs in real soil samples. The above results showed that the proposed method would be an ideal analytical method for SAs in environmental ecological research.

Extraction Method for Determining Dinotefuran Insecticide in Soil Samples

Dinotefuran is a third-generation neonicotinoid insecticide that has a broad action spectrum in agriculture pests. Dinotefuran was authorized in Brazil in 2019, being classified as a very dangerous product for the environment. Therefore, this study aimed to optimize and validate the solid-liquid extraction with low temperature purification to determine dinotefuran in soil samples using high-performance liquid chromatography coupled diode array detection. The results showed that the best extracting phase was acetonitrile:water (8:2 v/v), followed by the clean-up with 50 mg of primary-secondary amine. The method under these conditions has a linear range of 15.0 to 140 µg kg-1 and reached limits of detection and quantification of 10.0 and 15.0 µg kg-1, respectively. The validation revealed that the method was selective, precise, accurate, and presented a matrix effect of 15%. Although dinotefuran was not detected in real soil samples, the proposed method proved to be an efficient alternative for monitoring dinotefuran in soil samples.

A ratiometric fluorescent probe with a large Stokes shift for the detection of Hg2+ and its applications in environmental sample and living system analysis.

Toxic mercury ions (Hg2+) can cause serious environmental pollution and accumulate in living organisms via the food chain. Therefore, monitoring Hg2+ is crucial in ensuring the safety of ecosystems and organisms. In this work, a novel ratiometric fluorescent probe CMT (5-(4-(diphenylamino)phenyl)-1-(7-hydroxy-coumarin-3-yl)-4-pentene-1,3-dione) based on coumarin was developed for detecting Hg2+, which displayed obvious fluorescence changes, a low detection limit (2.24 × 10-7 M), good selectivity, and a large Stokes shift (255 nm). The CMT probe could detect Hg2+ in real environmental soil and water samples. Furthermore, the CMT probe enabled the naked-eye detection of Hg2+ using test paper experiments. CMT was also applied for fluorescence imaging in living zebrafish and plants. This work provides a highly efficient tool for monitoring Hg2+ in environmental samples and biological systems.

Direct quantification of 1,1-dimethylhydrazine transformation products in sandy soil by thermal desorption gas chromatography – Tandem mass spectrometry

The use of rocket propellants based on unsymmetrical dimethylhydrazine (UDMH) in launch vehicles and boosters poses a threat to the environment due to the release of UDMH into soils and its subsequent transformation into a variety of nitrogen-containing compounds, including toxic and carcinogenic ones. The present proof-of-concept study proposes a novel approach to screening and simultaneous determination of a wide range of nitrogen-containing UDMH transformation products in soils, based on direct thermal desorption (TD) as a solvent-free sample extraction technique coupled with GC–MS/MS analysis.Optimal TD conditions consisting of the incubation of 5 mg sample at 300 °C for 30 min, allowed attaining high recoveries (80–100 %) for the most tested compounds and developing the method for quantification of fifteen acyclic and heterocyclic UDMH transformation products in sandy soil with LODs of 0.3–7.8 µg kg−1. The matrix matched calibration and introduction of the internal standard (pyridine‑d5) ensured high accuracy (75–100 %) and precision (RSD < 15 %) of the analysis. Along with high sensitivity and accuracy, the main advantages of the developed method are exceptional simplicity of sample preparation, low amount of toxic sample, high automation degree, and environmental friendliness.The developed method was successfully tested in the analysis of seven real soil samples taken from the Baikonur cosmodrome operational zone (Kazakhstan). The use of TD-GC–MS analysis in full spectrum scanning mode allowed for tentative identification of 62 UDMH transformation products including several compounds not yet described in the literature.

Speciation of Selenium Nanoparticles and Other Selenium Species in Soil: Simple Extraction Followed by Membrane Separation and ICP-MS Determination.

The application of selenium nanoparticle (SeNP)-based fertilizers can cause SeNPs to enter the soil environment. Considering the possible transformation of SeNPs and the species-dependent toxicity of selenium (Se), accurate analysis of SeNPs and other Se species present in the soil would help rationally assess the potential hazards of SeNPs to soil organisms. Herein, a novel method for speciation of SeNPs and other Se species in soil was established. Under the optimized conditions, SeNPs, selenite, selenate, and seleno amino acid could be simultaneously extracted from the soil with mixtures of tetrasodium pyrophosphate (5 mM) and potassium dihydrogen phosphate (1.2 μM), while inert Se species (mainly metal selenide) remained in the soil. Then, extracted SeNPs can be effectively captured by a nylon membrane (0.45 μm) and quantified by inductively coupled plasma mass spectrometry (ICP-MS). Other extracted Se species can be separated and quantified by high-performance liquid chromatography coupled with ICP-MS. Based on the difference between the total Se contents and extracted Se contents, the amount of metal selenide can be calculated. The limits of detection of the method were 0.02 μg/g for SeNPs, 0.05 μg/g for selenite, selenate, and selenocystine, and 0.25 μg/g for selenomethionine, respectively. Spiking experiments also showed that our method was applicable to real soil sample analysis. The present method contributes to understanding the speciation of Se in the soil environment and further estimating the occurrence and application risks of SeNPs.

A Formyl Chromone Based Schiff Base Derivative: An Efficient Colorimetric and Fluorescence Chemosensor for the Selective Detection of Hg2+ Ions.

A novel chromone-based Schiff base L was designed and synthesized by condensing an equimolar amount of 3-formyl chromone and 2,4-dinitro phenyl hydrazine. Schiff base L was developed as a potent colorimetric and fluorescent molecular probe to recognize Hg2+ ions over other competitive metal ions. In the presence of Hg2+, Schiff base L displays a naked-eye detectable color change under day and UV365 nm light. Various UV-Vis and fluorescence studies of L were performed in the absence and presence of Hg2+ to determine the sensitivity and the sensing mechanism. With high selectivity and specificity, the detection limit and association constant of L for Hg2+ were estimated at 1.87 µM and 1.234 × 107M-1, respectively. The developed sensor L was applied to real soil samples for the detection of Hg2+.

Naphthalene derived Schiff base as a reversible fluorogenic chemosensor for aluminium ions detection

Schiff base (HNPD) was achieved by reacting 2-hydroxy-1-naphthaldehyde with N-phenyl-o-phenylenediamine in enthanol medium. The spectroscopic analyses were done to establish the formation of Schiff base apparently. Further, synthesized Schiff base conjugate was successfully used as a fluorogenic chemosensor to detect aluminium ions (Al3+) with high fluorescence amplification among the other interfering various metal ions. The limit of detection of 0.0248 × 10−6 M and a binding constant of 6.19 × 103 M−1 were obtained by the receptor HNPD for Al3+ detection. A high influence of intramolecular charge transfer kinetics was established to realize the selective responsiveness towards Al3+ ions. Density functional theory approximation formulated the band energy modulation and localization and delocalization of electron density for the HNPD and Al3+ complexation. The developed sensor ultimately inspected on the real soil and water samples and ascertained the practical ability of Al3+ ions detection of HNPD chemosensor.

Development of smartphone-controlled and machine-learning-powered integrated equipment for automated detection of bioavailable heavy metals in soils

Rapid and accurate on-site detection of crop-absorbable cadmium (Cd) and lead (Pb) in soils is important for food security and human health. The automated soil sample pretreatment method, including the ultrasonic extraction of weakly acid-soluble heavy metals, suction-filtration, and UV photolysis, was proposed to achieve the high-efficiency preparation from soil sample to extract solution. Bismuth-film-modified glass carbon electrode combined with the homemade potentiostat was fabricated to implement the square-wave anodic stripping voltammetry (SWASV) measurements of soil extracts. The peak-information-acquisition algorithm was designed to automatically obtain peak heights and widths of Zn2+, Cd2+, Pb2+, Bi3+, and Cu2+ stripping currents, and then which were used as input variables for establishing machine-learning models to enhance the detection accuracy of SWASV to Cd2+ and Pb2+ under the coexistence of multiple heavy metal ions. Eventually, the smartphone-controlled integrated-automated detection equipment was developed and successfully applied to the automatic pretreatment of soil samples and the determination of weakly acid-soluble Cd2+ and Pb2+ in real soil samples. The detection speed was 75 min/sample, and the detection results were close to the standard method (BCR-ICP-MS). This equipment can provide powerful technical support for on-site rapid and accurate determination of crop-absorbable heavy metals in soils.

Dual-channel fluorescent probe for discriminative detection of H2S and N2H4: Exploring sensing mechanism and real-time applications

A highly efficient system incorporates the real-time visualization of the two toxic molecules (H2S and N2H4) and the recognition of corresponding transforms using a fluorescent sensor. In this paper, a dual-responsive probe (QS-DNP) based on methylquinolinium-salicyaldehyde-2,4-dinitrophenyl was developed that can simultaneously detect H2S and N2H4 at two independent fluorescent channels without signal crosstalk. QS-DNP showed excellent anti-interference, high selectivity, outstanding water solubility, low LOD values (H2S: 51 nM; N2H4: 40 nM), low cytotoxicity, and mitochondrial localization properties. The 2,4-dinitrophenyl site was sensitive to H2S, and the CC bridge was reactive to N2H4, with strong fluorescence at 680 and 488 nm, respectively. The wavelength gap between these two channels is 192 nm; verify that there is no signal crosstalk throughout detection. By this means, the probe was used to simultaneously detect H2S and N2H4 in real soil samples, food samples, and living cells. The endogenous H2S and N2H4 were monitored in HeLa cells and investigated the mitochondria organelle of living cells with a positive charge on QS-DNP. Overall, all results emphasize that the QS-DNP probe is a powerful tool for the simultaneous detection of H2S and N2H4 and presents a potential new sensing approach.

Magnetic porous carbon material derived from imine-linked covalent organic frameworks for magnetic solid phase extraction of trace chlorine-containing herbicides in soil

Here, imine-linked covalent organic frameworks coated Fe3O4 microspheres were fabricated and employed as the self-template to prepare magnetic porous carbon material. The magnetic solid phase extraction (MSPE) performance of such magnetic covalent organic frameworks derived porous carbons (CMCOFs) were studied for the first time, and the improved MSPE performance was verified. The variations of chemical and material properties in the carbonization processes were studied, and it was found that the CMCOFs carbonated at 400°C exhibited highest adsorption efficiencies for chlorine-containing herbicides due to the formation of nitrile components at this stage. The CMCOFs retained high adsorption efficiencies (above 90 %) to chlorine-containing herbicides at wide pH range (3–12) and high salt concentration. The CMCOFs-based MSPE coupled with HPLC technique was in good potential for analysis of trace chlorine-containing herbicides in soil samples. Under the optimized conditions, this approach displayed short extraction and elution time (5 and 8 min) and low limits of detection (0.35–5.5 ng/mL) for chlorine-containing herbicides. The recoveries of spiked analytes and the relative standard deviations in real soil samples were 81.86 %–110.9 % and less than 5.92 %, respectively. This study provides an efficient method for the analysis of trace chlorine-containing herbicides in complex samples, as well as give some inspiration on material modulation by controlled carbonization to achieve improved sorption performances.

A facile and sensitive hexahomotrioxacalix[3]arene-based fluorescent sensor for the detection of trace amounts of 2,4,6-trinitrophenol

Nitroaromatic compounds are common explosives and toxic pollutants, the selective and sensitive detection of which is of great importance. Herein, a facile and sensitive fluorescent sensor L was constructed for the sensing of TNP based on the hexahomotrioxacalix[3]arene skeleton. The fluorescence emission of L was drastically quenched in the presence of 2,4,6-trinitrophenol (TNP), while other tested NACs, metal ions, and anions induced negligible changes. Under the optimized conditions, the spectroscopic studies revealed that L exhibited extremely sensitive and selective TNP recognition, with a detection limit of 9.17 × 10−7 M and a quenching constant of 2.44 × 104 M−1. The sensitivity of sensor L for TNP was attributed to the formation of a ground-state charge-transfer complex and an inner filter effect, which also contributed to the special selectivity of the sensor among the various nitroaromatic analogues. Compared with previous reports, L can serve as a highly efficient sensor for the sensing of TNP and can be employed over a wide pH range of 2 to 12. Sensor L was effectively used to quantify TNP in real water and soil samples. Additionally, fluorescent test strips were also developed for visual and rapid detection of TNP in both the solution and vapour phases.

E-SCAN: Electrochemical Scanning of Carbonates, an In Situ Approach for Screening and Quantifying Inorganic Carbon in Soil.

A modified three-electrode system was utilized with a correlated ion-capture film that is functional to changes in soil carbonate moieties to determine an understudied pool of soil carbon that is vital toward holistic carbon sequestration─carbonous soil minerals (CSM). This composite sensor was tested on soils with varying carbonate contents using cyclic voltammetry, chromatocoulometry (DC-based), and electrochemical impedance spectroscopy to determine signal output as a function of increasing dose. To determine the in-field capability, a portable potentiostat device was integrated into a probe head setup that could be inserted into soil for testing. The results from these experiments showed a linearity of R2 > 0.97 and a measurable sensing range from 0.01% (100 ppm) to 1% (10 000 ppm). Therefore, a first-of-a-kind in-soil sensor system was developed for determining carbonate content in real soil samples using electrochemistry that can be tested in-field to survey the field-deployable and point-of-use capability of the system.

Determination of glyphosate and aminomethylphosphonic acid residues in Finnish soils by ultra‐high performance liquid chromatography–tandem mass spectrometry

Glyphosate [N-(phosphonomethyl) glycine] (GLY) adsorbs strongly in Finnish soils. A new method for GLY and its main degradation product, aminomethylphosphonic acid (AMPA) residues in clay soils (Protovertic Luvisol) was developed and validated. A new method was necessary because the previous one required laborious cleaning pre-treatments, and its recovery was quite poor (<40%–70%). In the new method, the earlier method's extraction solvent, 0.1 M potassium hydroxide (KOH), was replaced by more effective 0.6 M KOH. The old post-column high-performance liquid chromatography and fluorescence (HPLC-FLD) method was replaced by the ultra-high performance liquid chromatography–tandem mass spectrometry (UHPLC-MS/MS) method. Compounds were identified as their fluorenyl methyl chloroformate (FMOC) derivatives by a multiple reaction monitoring (MRM) technique and quantified by an internal standard method utilising multipoint matrix-matched calibration. Glufosinate-ammonium (GLUF) was used to monitor the effectiveness of extraction with good recovery (80–119%). All calibration curves were found to be linear (R2 ≥ 0.98) in the studied calibration range (0.01–3.31 mg kg−1 in fresh soil). The repeatability and reproducibility were 25% and 28% for GLY, and 20% and 24% for AMPA in real research soil samples. The method was effective throughout the calibration range in all the studied Finnish agricultural soils.•An improved method was created to analyse glyphosate (GLY) and AMPA in Finnish clay soil.•The challenge caused by strong GLY adsorption on soil was solved by using multipoint matrix-matched calibration curve samples which were prepared identically with the research samples.•The method performed well in all tested clay, loam and sandy loam soils.

A highly porous fiber coating based on a Zn-MOF/COF hybrid material for solid-phase microextraction of PAHs in soil

This study involved the development of a novel adsorbent by combining a Zn-based MOF with a melamine-based COF, resulting in the formation of a hybrid material known as Zn-MOF/COF. The adsorbent was characterized using FT-IR, SEM, XRD, EDX, and BET analysis techniques. The resulting Zn-MOF/COF sorbent was employed to prepare solid-phase microextraction (SPME) fibers for the extraction and enrichment of polycyclic aromatic hydrocarbons (PAHs) in contaminated soil samples, after coupling with GC-FID. A Box-Behnken design (BBD) was used to optimize key variables of SPME conditions.Under optimal conditions of 85 °C for 30 min extraction with 23 μL g−1 sample's moisture level, linear responses of six PAHs were ranging from 1 to 20000 ng g⁻1 with determination coefficients greater than 0.99. Limits of detection (LODs) were over the ranges of 0.1–1 ng g-1. The RSDs for intra-fiber and inter-fiber analyses were obtained 2.2–6.6% and 5.2–11.6%, respectively. Relative recoveries values for real soil samples were found to be 91.1–110.2%. The results showed lower cost and higher extraction efficiency for the Zn-MOF/COF fiber, compared with commercial and homemade adsorbents.

New 1,8-naphthalimide-based colorimetric fluorescent probe for specific detection of hydrazine and its multi-functional applications

Detection of hydrazine is particularly important given its toxicity and extensive application in various industries. In the present paper, a colorimetric fluorescent probe NI-CIN based on 1,8-naphthalimide derivative was rationally designed and simply synthesized for specific detection of hydrazine based on the intramolecular charge transfer (ICT) mechanism. Upon the addition of hydrazine, a significant fluorescence enhancement at 556 nm could be observed within 4 min with a distinct color change from colorless to bright yellow, readily observed by naked eye. Except for HRMS and 1H NMR, density functional theory (DFT) calculations were also performed to support the sensing mechanism. In addition, eco-friendly paper test strips were easily prepared by NI-CIN for selective and real-time detection of hydrazine under aqueous and vapor phases. Furthermore, NI-CIN shows many potential applications for detecting hydrazine in real water and soil samples along with bio-imaging in HepG-2 cells and zebrafish.

A highly selective fluorescence turn-on sensor for Hg2+ based on quinolimide in aqueous media and its applications

Herein, a novel fluorescent sensor QPE based on quinolimide was developed, which displayed the highly selective response to Hg2+ through the turn-on signal in aqueous media. The corresponding recognition mechanism of QPE for Hg2+ was investigated by the titration experiments, Job’s plots, HRMS, and DFT calculations analysis. QPE could detect Hg2+ in a broad pH range (pH = 4–9) with the LOD of 20 nM and the LOQ of 66 nM. Meanwhile, QPE-loaded test strips were demonstrated in the visual detection of Hg2+. Importantly, QPE exhibited the reliable capability to track Hg2+ in real water and soil samples and yeast cells, indicating that QPE could be used as a prospective tool for monitoring Hg2+ in wide fields.

A novel acetylcholinesterase inhibition based colorimetric biosensor for the detection of paraoxon ethyl using CUPRAC reagent as chromogenic oxidant

A novel colorimetric biosensor for the sensitive and selective detection of an organophosphate pesticide, paraoxon ethyl (POE), was developed based on its inhibitory effect on the acetylcholine esterase (AChE) enzyme. The bis-neocuproine copper (II) complex ([Cu(Nc)2]2+) known as the CUPRAC reagent, was used as a chromogenic oxidant in the AChE inhibition-based biosensors for the first time. To initiate the biosensor, an enzymatic reaction takes place between AChE and its substrate acetylthiocholine (ATCh). Then, enzymatically produced thiocholine (TCh) reacts with the light blue [Cu(Nc)2]2+ complex, resulting in the oxidation of TCh to its disulfide form. On the other hand, [Cu(Nc)2]2+ reduces to a yellow-orange cuprous complex ([Cu(Nc)2]+) which gives maximum absorbance at 450 nm. However, the absorbance of [Cu(Nc)2]+ proportionally decreased with the addition of POE because the inhibition of AChE by the organophosphate pesticide reduced the amount of TCh that would give a colorimetric reaction with the CUPRAC reagent. Based on this strategy, the linear response range of a colorimetric biosensor was found to be between 0.15 and 1.25 μM with a detection limit of 0.045 μM. The fabricated biosensor enabled the selective determination of POE in the presence of some other pesticides and metal ions. The recovery results between 92% and 104% were obtained from water and soil samples spiked with POE, indicating that the determination of POE in real water and soil samples can be performed with this simple, accurate, sensitive, and low-cost colorimetric biosensor.

HS-SPME-GC-MS analysis of Cyprus vineyard soil for VOCs determination

In line with green chemistry principles, a headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC-MS) method was developed and optimized to study the profile of biogenic volatile organic compounds (BVOCs) in soil samples from vineyards. The 75 µm CAR/PDMS fiber was selected for the identification of BVOCs in soil. The analytical method showed very good linearity (R2 ≥ 0.9914), sensitivity, and precision. Subsequently, soil matrix effect (ME) was examined on the BVOCs emission, through combined standard addition and internal standard (IS) calibration curves. The validated and optimized method was further applied in real soil samples from three vineyard areas of Cyprus (Omodos, Polemi, and Agros). Thirty-eight BVOCs were identified in total; among them acetone (0.65–5.96 μg/kg), hexane (0–0.50 μg/kg), heptane (0–0.18 μg/kg), trichloromethane (0.13–0.21 μg/kg), 1,2-dichloropropane (0.05–1.37 μg/kg), cyclohexane (0–0.26 μg/kg), benzene (0–0.51 μg/kg), toluene (0–0.54 μg/kg), p-xylene (0.15–0.97 μg/kg), and 1,3-di-tert-butyl-benzene (7.91–29.55 μg/kg) were quantified. The results revealed that the sampling vineyard location affects the BVOCs emissions in each soil. Also, vineyard elevation, soil pH, Ca, N, Zn, and Fe showed a significant correlation with the BVOCs emissions, which explains why vineyard soil regions are distinguished from each other, concluding that sample from Agros is the most abundant in BVOCs emissions.

Application of magnetic-nanoparticle functionalized whole-cell biosensor array for bioavailability and ecotoxicity estimation at urban contaminated sites

The bioavailability and ecotoxicity of pollutants are important for urban ecological systems and human health, particularly at contaminated urban sites. Therefore, whole-cell bioreporters are used in many studies to assess the risks of priority chemicals; however, their application is restricted by low throughput for specific compounds and complicated operations for field tests. In this study, an assembly technology for manufacturing Acinetobacter-based biosensor arrays using magnetic nanoparticle functionalization was developed to solve this problem. The bioreporter cells maintained high viability, sensitivity, and specificity in sensing 28 priority chemicals, seven heavy metals, and seven inorganic compounds in a high-throughput manner, and their performance remained acceptable for at least 20 d. We also tested the performance by assessing 22 real environmental soil samples from urban areas in China, and our results showed positive correlations between the biosensor estimation and chemical analysis. Our findings prove the feasibility of the magnetic nanoparticle-functionalized biosensor array to recognize the types and toxicities of multiple contaminants for online environmental monitoring at contaminated sites.