Environmental Soil Samples Research Articles

Dietary and terrestrial exposure to methoxylated polybrominated diphenoxybenzene contaminants in Great Lakes herring gulls

Methoxylated polybrominated diphenoxybenzenes (MeO-PB-DPBs) are little known contaminants except in North American Great Lakes herring gull tissues and egg samples. MeO-PB-DPBs in gulls originate not via aquatic bioaccumulation pathways but instead likely via transformation of the tetradecabromo-1,4-diphenoxybenzene (TDB-DPB) flame retardant (FR). TDB-DPB was formerly produced as SAYTEX-120 in North America and is still produced in Asia. This study investigates the terrestrial exposure pathway of MeO-PB-DPBs and other FRs in herring gulls. Gull regurgitant and faeces, soil, and earthworms were collected from Channel Shelter Island (Saginaw Bay, Lake Huron), and analyzed for 3 MeO-PB-DPBs, 25 polybrominated diphenyl ethers (PBDEs), and 22 non-PBDE halogenated FRs. MeO-PB-DPBs in soil varied from non-detect to 4 ng/g dw per pentabrominated congener to a remarkably high 53 ng/g dw for the hexabrominated congener and comparable to BDE-209 which accumulates to high levels in Great Lakes sediment. MeO-hexa- to penta-brominated-DPB congener ratios were much greater (> 10x vs. ∼ 2x) than in herring gull tissues or eggs, suggesting possible differences in bioavailability. PB-DPB congeners were detected for the first time in environmental soil samples and confirmed via standard addition of the 2,2′,4,4″- and 2,2′,2″,4-tetrabromodiphenoxybenzene standards. MeO-PB-DPBs were mostly absent from faeces and not detected in earthworm samples. Combined with the finding of detection in regurgitant samples, indicating dietary intake, this suggests that gull exposure is via terrestrial bioaccumulation of MeO-PB-DPBs.

Potentially Pathogenic Free-Living Amoebae Isolated from Soil Samples from Warsaw Parks and Squares.

Free-living amoebae (FLA) are prevalent in diverse environments, representing various genera and species with different pathogenicity. FLA-induced infections, such as the highly fatal amoebic encephalitis, with a mortality rate of 99%, primarily affect immunocompromised individuals while others such as Acanthamoeba keratitis (AK) and cutaneous amebiasis may affect immunocompetent individuals. Despite the prevalence of FLA, there is a lack of standardized guidelines for their detection near human habitats. To date, no studies on the isolation and identification of FLA in environmental soil samples in Warsaw have been published. The aim of this study was to determine the presence of amoebae in soil samples collected from Warsaw parks and squares frequented by humans. The isolated protozoa were genotyped. Additionally, their pathogenic potential was determined through thermophilicity tests. A total of 23 soil samples were seeded on non-nutrient agar plates (NNA) at 26 °C and monitored daily for FLA presence. From the total of 23 samples, 18 were positive for FLA growth in NNA and PCR (78.2%). Acanthamoeba spp. was the most frequently isolated genus, with a total of 13 positive samples (13/18; 72.2%), and the T4 genotype being the most common. Moreover, Platyamoeba placida (3/18; 16.7%), Stenamoeba berchidia (1/18; 5.6%) and Allovahlkampfia sp. (1/18; 5.6%), also potentially pathogenic amoebae, were isolated. To our knowledge, this is the first report of FLA presence and characterization in the Warsaw area.

A three-dimensional nitrogen-rich conjugated microporous polymer for solid-phase microextraction of nitroaromatic compounds from environmental water and soil samples

Nitroaromatic compounds (NACs), as a kind of important chemical intermediates, are widely used in industrial productions. However, NACs have carcinogenic effect and their residues may pose harm to human health. Therefore, there is necessity to set up effective analytical method to monitor them in some environmental samples. However, because of their low concentrations in real samples, they need to be enriched by an effective adsorbent before the subsequent instrumental detection. In this work, a three-dimensional nitrogen-rich conjugated microporous polymer (DCT-Try-CMP) was synthesized with 3,6-dichloro-1,2,4,5-tetrazine and triptycene as monomers via Friedel-Crafts reaction. It presented a good adsorption capability for the NACs. After optimization, a solid-phase microextraction with DCT-Try-CMP fiber combined with gas chromatography-flame ionization detection for the quantitation of trace NACs in environmental water and soil samples was developed. The limits of detection of the method (S/N = 3) for environmental water and soil samples were 0.08–0.30 μg L-1 and 1.00–5.00 ng g-1, and the limits of quantification (S/N = 9) were 0.27–0.90 μg L-1 and 3.00–15.0 ng g-1, respectively. The linear quantification response ranges for the analytes were 0.27–200 μg L-1 and 3.00–1000 ng g-1 for water and soil samples, respectively. For water samples at the analytes concentrations of 5.00, 50.0 and 100 μg L-1, the method recoveries ranged from 82.2% to 120% and for soil samples at the concentrations of 15.0, 200 and 400 ng g-1, the method recoveries fell in the range from 80.2% to 120%. The method provides a sensitive and effective approach for monitoring trace NACs in environmental water and soil samples.

A novel fluorescent probe for fast detection of sulfur dioxide derivatives in water, soil, food samples and its applications in biological imaging

Sulfur dioxide (SO2) has a wide range of applications in food additives and industrial production, and it is one of the main substances that form acid rain, causing serious harm to ecosystems and human health. Hence, it is necessary to construct an effective tool to quickly and accurately detect SO2 derivatives in environmental, food, and biological samples. In this study, fluorescent probe NPMQ was built to detect SO2 derivatives from nopinone with the merits of superior water solubility, high sensitivity (12nM), excellent specificity, large Stokes shift (180nm), and rapid response time (within 5s). NPMQ was used to qualitatively and quantitatively detect SO2 derivatives in environmental water, soil and food samples. In addition, an electrospinning film was prepared with the probe NPMQ to image SO2 derivatives, and test strips are capable of rapidly, sensitively, and selectively detecting SO2 derivatives with the naked eye. Moreover, the probe NPMQ was used to visualize endogenous SO2 derivatives in Arabidopsis thaliana under Cd2+ stress. Furthermore, the probe NPMQ was employed to image exogenous and endogenous SO2 derivatives in living Hela, HepG-2 cells, and zebrafish. This study develops an effective tool for monitoring SO2 derivatives in the environmental, food, and biological systems.

An optimised molecular-based method for ecological study of tardigrades in soils

To improve approaches for studying soil tardigrades, we compared three tardigrade extraction methods, including centrifugal flotation, Baermann funnel, and Whitehead tray, and found that the Whitehead tray method outperformed the two others. We optimised the Whitehead tray extraction condition under various soil pre-treatment processes, sample sizes, light exposure, and extraction time. We found that extending light exposure of non-sieved soils facilitates the extraction of tardigrades. We sequenced the DNA extracted from isolated tardigrade individuals and environmental soil samples, and found that tardigrade DNA extracts yielded a 173-fold increase in the proportion of tardigrade sequences and a 12-fold improvement in the estimation of tardigrade diversity.

Fingerprinting DNAzyme Cross-Reactivity for Pattern-Based Detection of Heavy Metals.

Heavy metal contamination in food and water is a major public health concern because heavy metals are toxic in minute amounts. DNAzyme sensors are emerging as a promising tool for rapid onsite detection of heavy metals, which can aid in minimizing exposure. However, DNAzyme activity toward its target metal is not absolute and has cross-reactivity with similar metals, which is a major challenge in the wide-scale application of DNAzyme sensors for environmental monitoring. To address this, we constructed a four DNAzyme array (17E, GR-5, EtNA, and NaA43) and used a pattern-based readout to improve sensor accuracy. We measured cross-reactivity between three metal cofactors (Pb2+, Ca2+, and Na+) and common interferents (Mg2+, Zn2+, Mn2+, UO22+, Li+, K+, and Ag+) and then used t-SNE analysis to identify and quantify the metal ion. We further showed that this method can be used for distinguishing mixtures of metals and detecting Pb2+ in environmental soil samples at micromolar concentrations.

Pyrazole probes for the detection of N2H4 with ICT properties in live cells and soils

Here, the two novel fluorescent probes Z1 and Z2 have been designed and synthesized based on pyrazole derivative to recognize hydrazine, and the molecular structure was determined by 1H NMR, 13C NMR, and ESI-MS. The obtained probe molecules have AIE and ICT characteristics. Nuclear magnetic resonance analysis (NMR) and theoretical calculations were used to confirm the identification mechanism. Probes Z1 and Z2 have good selectivity, low detection limits (0.197 µM and 0.185 µM, respectively), and high sensitivity. Probes Z1 and Z2 have large Stokes shifts of 198 nm and 211 nm, respectively. The probes also could be made into test paper strips for the detection of hydrazine. Furthermore, the probes can be used in the detection of N2H4 in environmental soil samples and cell imaging. The results showed that the synthetic probe had good biocompatibility. Cell imaging experiments were performed to apply probes to the detection of hydrazine hydrate in HeLa cells.

PFAS Porewater concentrations in unsaturated soil: Field and laboratory comparisons inform on PFAS accumulation at air-water interfaces

Poly- and perfluoroalkyl substance (PFAS) leaching from unsaturated soils impacted with aqueous film-forming foams (AFFFs) is an environmental challenge that remains difficult to measure and predict. Complicating measurements and predictions of this process is a lack of understanding between the PFAS concentrations measured in a collected environmental unsaturated soil sample, and the PFAS concentrations measured in the corresponding porewater using field-deployed lysimeters. The applicability of bench-scale batch testing to assess this relationship also remains uncertain. In this study, field-deployed porous cup suction lysimeters were used to measure PFAS porewater concentrations in unsaturated soils at 5 AFFF-impacted sites. Field-measured PFAS porewater concentrations were compared to those measured in porewater extracted in the laboratory from collected unsaturated soil cores, and from PFAS concentrations measured in the laboratory using batch soil slurries. Results showed that, despite several years since the last AFFF release at most of the test sites, precursors were abundant in 3 out of the 5 sites. Comparison of field lysimeter results to laboratory testing suggested that the local equilibrium assumption was valid for at least 3 of the sites and conditions of this study. Surprisingly, PFAS accumulation at the air-water interface was orders of magnitude less than expected at two of the test sites, suggesting potential gaps in the understanding of PFAS accumulation at the air-water interface at AFFF-impacted sites. Finally, results herein suggest that bench-scale testing on unsaturated soils can in some cases be used to inform on PFAS in situ porewater concentrations.

Plasmid size determines adsorption to clay and breakthrough in a saturated sand column

Horizontal gene transfer (HGT) is a major factor in the spread of antibiotic resistant genes (ARG). Transformation, one mode of HGT, involves the acquisition and expression of extracellular DNA (eDNA). eDNA in soils is degraded rapidly by extracellular nucleases. However, if bound to a clay particle, eDNA can persist for long periods of time without losing its transformation ability. To better understand the mechanism of eDNA persistence in soil, this experiment assessed the effects of 1) clay mineralogy, 2) mixed salt solution, 3) plasmid size on DNA adsorption to clay and 4) breakthrough behavior of three differently sized plasmids in an environmentally relevant solution. Batch test methods were used to determine adsorption trends of three differently sized DNA plasmids, pUC19, pBR322, and pTYB21, to several pure clay minerals, goethite (α-FeOOH), illite, and kaolinite, and one environmental soil sample. Results show not all sorbents have equal adsorption capacity based on surface area with adsorption capacities decreasing from goethite > illite = kaolinite > bulk soil, and low ionic strength solutions will likely not significantly alter sorption trends. Additionally, plasmid DNA size (i.e., length) was shown to be a significant predictor of adsorption efficiency and that size affects DNA breakthrough, with breakthroughs occurring later with larger plasmids. Given that DNA persistence is linked to its adsorption to soil constituents and breakthrough, eDNA size is likely an important contributor to the spread of ARG within natural microbial communities.

Selective visual staining of polyurethane microplastics by novel colorimetric and near-infrared (NIR) fluorescent dye: Application to environmental water and natural soil samples

Microplastics can cause environmental pollution and ecosystem destruction as well as human health problems. Among the types of microplastics, polyurethane (PU) is particularly resistant to heat and difficult to decompose, causing disposal problems, and is evaluated as one of the most hazardous polymers. We present a novel colorimetric and near-infrared (NIR) fluorescence dye, (E)-N-(2-((4-(diphenylamino)benzylidene)amino)phenyl)− 7-nitrobenzo[c][1,2,5]oxadiazol-4-amine (DPNA), designed for selective visual PU microplastic staining. The intramolecular charge transfer (ICT) properties of DPNA are demonstrated through density functional theory (DFT) calculations along with solvatochromic shift. DPNA exhibits red color and red fluorescence emission, showing promising potential as a staining dye. To achieve selective PU microplastic staining, we establish an optimized experimental procedure with the staining dye DPNA by evaluating the staining efficiency under different staining solvent compositions and staining times. DPNA can distinguish PU by both red fluorescence signal and red coloration among different types of microplastics. In addition, DPNA well stain fresh PUs with diverse sizes and at various pH range of 5–9, and the aged PUs can also be dyed as effectively as the fresh PU. Most importantly, DPNA selectively stains PU among 11 types of microplastics and 5 types of natural particles in environmental water and soil with and without any pre-treatments. The adsorption mechanism of DPNA on PU microplastic is demonstrated through field emission scanning electron microscopes (FE-SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and non-covalent interaction (NCI)-reduced density gradient (RDG) analyses, and proposed that intermolecular hydrogen bonding has a significant effect.

A novel albumin-based supramolecular biosensor for ratiometric on-site determination of buprofezin

Buprofezin (BUP) is an effective insecticide against Homopteran and Thysanoptera pests. However, exposure to BUP may result in several harmful effects on the non-target organism including human body, such as hepatotoxicity and DNA damage. Therefore, development of a reliable analytical method for BUP holds paramount importance. This study presents a novel albumin-based supramolecular biosensor, DPP@ALB, designed for the sensitive detection of BUP in environmental matrices, including water, soil, and real food samples. The features of this biosensor include a fast response, high sensitivity, and visually detectable fluorescence color change, enabling on-site detection of BUP based on the portable paper strips and 3D-printed miniaturized testing system. Overcoming challenges associated with the low chemical reactivity of BUP, this supramolecular biosensor emerges as the very first fluorescent sensor for efficient and reliable monitoring of BUP with applications in broader areas of environmental analysis and food safety.

Diversity of Collembola on Various Post-Rehabilitation Land Covers

The success of rehabilitation has altered environmental conditions from critical land to new habitats for living organisms. One of the representative and sensitive mesofauna to environmental changes is Collembola. Various vegetation cover almost all of the rehabilitation area, which has impacts on microclimate and soil quality as important factors to Collembola existence. This study investigated the diversity and abundance of Collembola and its relation to environmental factors on various land covers, including teak, grass, and mixed stand land cover. Data were collected in an observation plot of 20 m × 20 m using purposive samples, including environmental measurements, Collembola collection, and soil samples for physical and chemical analysis. The results showed that different land covers affected the abundance and diversity of Collembola, even though the statistical analyses of TLC, GLC, and MLC were not significantly different. However, TLC has a higher litter thickness and organic material than the other land cover types. A few families of Collembola, such as Cyphoderidae, Brachystomellidae, Katiannidae, Isotomidae, Oncopoduridae, and Isotogastruridae, show their correlation to climatic and edaphic factors in a certain land cover.

Synthesis and Application of 3-[3-Phenylpyrazylazo]-2,7-Naphthalendiol for Improved Palladium Determination in Environmental Samples and Enhanced ZnO Nanoparticle Performance

In this study, a spectrophotometric method for the determination of low levels of palladium (II) was developed by forming a complex with the new reagent 3-(3-phenyl pyrazyl azo)-2,7-naphthalendiol (3PPAN). The complex showed maximum absorption at 612 nm with a maximum molar absorptivity of 4.911?104 L/mol/cm, and a linear correlation was established between absorbance and concentration. The accuracy and repeatability of the method were evaluated and found to be precise (RSD 1.22%) and accurate (relative error 0.157%). The method?s selectivity was also tested by evaluating the effect of various ions. The stability constant of the complex was determined to be 2.759?107 L/mol. The method was successfully applied to the determination of Pd (II) ions in environmental samples of water and soil. In addition, the new ligand (3PPAN) was used to improve the properties of nano ZnO through a ligand exchange reaction on nanoparticles.. KEYWORDS :Azo, Palladium, Spectrophotometric, ZnO nanoparticles.

Unique Reaction-Based Polynorbornene Sensing Probes for Ultrasensitive Detection of Hydrazine in Both Environmental and Biological Systems.

Hydrazine-mediated formation of 1,4-phthalazinedione analogues from phthalimide-like components has been utilized to formulate fluorescent probe NorTh. A turn-on fluorescent process has been evaluated to detect hydrazine in a highly selective manner by a small molecular probe NorTh and its homopolymer Poly-NorTh. Both these probes have been evaluated as excellent candidates for nanomolar level detection of hydrazine with a time frame of <15 min, which is rapid in terms of real application. Due to the reaction-based detection process, we have achieved high selectivity for our probes toward the identification of hydrazine in the presence of metal ions, anions, amino acids, and various amines. Limit of detection values are 16 and 35 nM for NorTh and Poly-NorTh, respectively, which are well below the permissible limit given by WHO and EPA. Poly-NorTh has been utilized to detect hydrazine in environmental water samples, soil samples, and biological samples to establish the applicability of our probes in real-field scenarios. We introduce an easy-to-synthesize, cheap, and small molecular probe and its polymer for ultrafast, highly selective, and sensitive detection of hydrazine in all possible mediums to counter the hydrazine toxicity through fluorescence turn-on signal output.

Fe3O4@nitrogen-doped carbon core-double shell nanotubes as a novel and efficient nanosorbent for ultrasonic assisted dispersive magnetic solid phase extraction of heterocyclic pesticides from environmental soil and water samples.

Fe3O4@nitrogen-doped carbon core-double shell nanotubes (Fe3O4@N-C C-DSNTs) were successfully synthesized and applied as a novel nanosorbent in ultrasonic assisted dispersive magnetic solid phase extraction (UA-DMSPE) of tribenuron-methyl, fenpyroximate, and iprodione. Subsequently, corona discharge ion mobility spectrometry (CD-IMS) was employed for the detection of the extracted analytes. Effective parameters on theextraction recovery percentage (ER%) were systematically investigated and optimized. Under optimal conditions, UA-DMSPE-CD-IMS demonstrated remarkable linearity in different ranges within 1.0 - 700 ng mL-1 with correlation coefficients exceeding 0.993, repeatability values below 6.9%, limits of detection ranging from 0.30 to 0.90 ng mL-1, high preconcentration factors (418 - 435), and ER%values (83 - 87%). The potential of the proposed method was further demonstrated by effectively determining the targeted pesticides in various environmental soil and water samples, exhibiting relative recoveries in the range 92.1 - 102%.

Viability of elutriation for the extraction of microplastics from environmental soil samples.

In this study, we evaluated the suitability of elutriation, a method successfully employed in the extraction of microplastics from marine sediments, for the extraction of microplastics from freshwater and terrestrial soils. Five soils were sampled throughout Oklahoma, USA in order to capture a range of sand, silt, clay, and organic matter composition. Each soil was subjected to microplastic extraction with and without elutriation, followed by digestion in 7.5% NaOCl, and then flotation in 6 M ZnCl2. The mass of each soil was measured after elutriation to determine sample mass reduction, and multiple methods including fluorescence imaging and automated particle counting through ImageJ, Attenuated Total Reflectence-Fourier Transfor Infrared Spectroscopy (ATR-FTIR), and Pyrolysis-coupled Gas Chromatography/Mass Spectrometry (py-GC/MS) were used to determine microplastic quantity, mass, and characteristics. T-test was used to check for statistically-significant differences between methods in terms of mass or particle quantity. For all tested soils, elutriation resulted in greater sample mass reduction than non-elutriated samples, and was between 59.0-97.3% for the tested soils. Furthermore, no statistically significant (p < 0.05) differences were observed in particle quantification or polymer mass between methods, and no differences were observed for polymer or size distribution. Additionally, 33% more polymers were positively identified (R 2 = 70%) by ATR-FTIR analysis in elutriated samples compared to non-elutriated soils. The mass reduction provided by elutriation allows for the processing of larger sample volumes, leading to greater accuracy and sensitivity in detecting microplastics. As such, we recommend elutriation be performed as a pretreatment step to extract microplastics from soils.

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.

Hollow CoZnSe@CN nanocage with enzymatic activity for determination of tetracycline using smartphone platforms and virtual reality revealing.

Antibiotic residues in the environment pose a serious threat to ecosystems and human health. Therefore, it is important to develop sensitive and rapid in situ detection methods. In this work, the designed nanozymes, with excellent four enzyme activities, were proved to be constituted ofunique hollow nanocage structures (CoZnSe@CN HCs). Based on the peroxidase-like enzymes, a portable colorimetric sensor was constructed for the on-site determinationof tetracycline (TC) in real samples. The linear range of TC detection was 0.1-100μM, and the detection limit was 0.02μM. At the same time, colorimetric detection and smartphones have also been combined for on-site colorimetric detection of TC. In-depth exploration of the detection mechanism showed that TC could be bound with the material, inhibiting the production of oxidized 3,3',5,5'-tetramethylbenzidine. The sensor was also used for the detection of TC in environmental soil and water samples. This study can provide an intelligent detection method for environmental monitoring.

Complete genome sequence of Bacillus thuringiensis strain RC340, isolated from a temperate forest soil sample in New England.

The complete genome sequence of Bacillus thuringiensis strain RC340, isolated from an environmental microbiology experiment soil sample is presented here. B. thuringiensis strain RC340 sequenced by GridION consists of a single genome consisting of 5.86 million bases, 8,152 predicted genes, and 0.23% contamination.

Application of UHPLC-MS/MS method to monitor the occurrence of sulfonamides and their transformation products in soil in Silesia, Poland

Sulfonamides circulating in the environment lead to disturbances in food chains and local ecosystems, but most importantly contribute to development of resistance genes, which generate problems with multidrug-resistant bacterial infections treatment. In urban areas, sources of sulfonamide distribution in soils have received comparatively less attention in contrast to rural regions, where animal-derived manure, used as a natural fertilizer, is considered the main source. The aim of this study was to determine eight sulfonamides (sulfadiazine, sulfamerazine, sulfamethazine, sulfamethizole, sulfamethoxazole, sulfapyridine, sulfathiazole, and sulfisoxazole) in environmental soil samples collected from urbanized regions in Silesian Voivodeship with increased animal activity. These soils were grouped according to the organic carbon content. It was necessary to develop versatile and efficient extraction and determination method to analyze selected sulfonamides in various soil types. The developed LC–MS/MS method for sulfonamides analyzing was validated. The obtained recoveries exceeded 45% for soil with medium organic carbon content and 88% for sample with a very low organic carbon content (arenaceous quartz). The obtained results show the high impact of organic matter on analytes adsorption in soil, which influences recovery. All eight sulfa drugs were determined in environmental samples in the concentration range 1.5–10.5 ng g-1. The transformation products of the analytes were also identified, and 29 transformation products were detected in 24 out of 27 extracts from soil samples.