Environmental Water Samples Research Articles

Assessment of PCR Inhibitor Removal Methods to Monitor Viruses in Environmental Water Samples: DAX-8 Outperforms Competitors

Complex water matrices or viral elution buffers can interfere with the qPCR leading to an underestimation of the potential public health hazards of waterborne viral pathogens. Here, we assessed different approaches to mitigate inhibitory impact of complex water samples during RT-qPCR of murine norovirus (MNV), as an inhibition control. The dilution of extracted samples, the use of qPCR additives, a commercial PCR inhibitor removal kit, and polymeric adsorbents such as Supelite DAX-8 and polyvinylpyrrolidone (PVP) were all investigated in this context. Data indicated that the maximum amplification of MNV by RT-qPCR could be obtained by pre-dilution of samples. However, the dilution factor may depend on inhibitors concentration, primer length, probe sequence, and binding capacity. Interestingly, PCR inhibitor removal kits do not seem to be adequate for removing all PCR inhibitors. In comparison to other approaches studied here, the application of 5% DAX-8 led to an increase in MNV qPCR concentrations. DAX-8 can permanently eliminate humic acids from the extracted nucleic acids from the environmental water samples, and it has the potential to considerably improve the accuracy of the obtained non-detects and measured concentrations by qPCR. Further research is required to understand the performance of polymeric adsorbents with enveloped viruses.

Smartphone readable three dimensional printed analytical kit for on-site detection of Cr(VI)

A rapid and easy-used colorimetric method was developed for on-site and rapid analysis of Cr(VI). Under acidic condition, Cr(VI) was reacted with 1, 5-diphenylcarbazide (DPC) and a purple-red complex was formed subsequently, inducing the color changed from colorless to purple-red, this color variance can be detected by ultraviolet–visible spectrophotometer (UV–Vis), smartphone and even naked-eye. For realizing the goal of on-site analysis, this method was integrated in a three dimensional (3D) printed analytical kit, smartphone was used as a portable detector. Under the optimized conditions, limit of detections (LODs) of 0.0014 μg/mL and 0.0016 μg/mL were obtained by smartphone and UV–Vis, respectively. Concentration of Cr(VI) as low as 0.05 μg/mL was still visible by naked-eye. This colorimetric system was further applied to the analysis of several environmental water samples, recoveries of 90–107 % were obtained. It is a promising portable analytical device/system for Cr(VI) on-site and rapid analysis.

Supercritical CO2 mediated construction of aluminium waste recovered γ-Al2O3 impregnated Dracaena trifasciata biomass-derived carbon composite: A robust electrocatalyst for mutagenic pollutant detection

Inspired by the waste-to-wealth concept, we have recovered the gamma phase aluminium oxide nanoparticles (γ-Al2O3 NPs) from waste aluminium (Al) foils and fabricated a composite with Dracaena trifasciata biomass-derived activated carbon matrix (DT-AC) using supercritical carbon-di-oxide (SC-CO2) pathway. The prepared samples are characterized altogether by various micro- and spectroscopic analyses. Based on the results, the recovered γ-Al2O3 NPs are well impregnated in the DT-AC surface by the action of the microbubble effect from the SC-CO2. The higher D-band and ID/IG value of 1.07 in the Al2O3/DT-AC nanocomposite indicate increased defects and the amorphous nature of the carbon materials. The effect of scan rate (ν) demonstrated greater linearity in ν1/2 vs peak current in the electrochemical detection study of the mutagenic pollutant 4-(methylamino) phenol hemi sulfate, showing a quasi-reversible electron transfer process undergoing diffusion-controlled kinetics. Furthermore, the limit of detection is determined to be 3.2 nM L–1 with an extensive linear range, spanning from 0.05 to 618.25 µM/L. The incredible sensitivity of 2.117 μA μM−1 cm−2, along with excellent selectivity, repeatability, and stability, is observed. Further, the respectable recovery percentage of 98.61 % in the environmental water sample is perceived. The observed outcomes suggest that the prepared Al2O3/DT-AC composite performs as an excellent electrocatalyst material, and the processing techniques used are thought to be sustainable in nature.

Voltammetry for quantitative determination of trace mercury ions in water via acetylene black modified carbon paste electrode

A sensitive acetylene black modified carbon paste electrode was fabricated for the determination of trace mercury ions in water samples. Nitric acid treatment of acetylene black (TAB) produced a porous structure with large surface area and defects, improving its performance as an electrode modifier. Under optimized conditions, the TAB/CPE showed good selectivity and sensitivity towards mercury ions. The peak current exhibited a linear relationship with mercury ion concentration from 10 nM to 0.1 mM, with a detection limit of 8.8 nM. The enhanced sensitivity results from a synergistic effect between the properties of TAB and carbon paste. The porous structure, large surface area and defects in TAB improve mercury ion adsorption and electron transfer kinetics. Meanwhile, the carbon paste provides a stable and conductive electrode base. The developed sensor showed good stability, repeatability and reproducibility, as well as acceptable recovery results when applied to detect mercury ions in simulated water samples. This simple and rapid electrochemical method holds potential for the determination of trace mercury ions in environmental water samples.

Magnetic Persimmon Leaf Composite: Preparation and Application in Magnetic Solid-Phase Extraction of Pesticides in Water Samples.

In recent years, the utilization of biomass materials for the removal and detection of water pollutants has garnered considerable attention. This study introduces, for the first time, the preparation of Fe3O4/persimmon leaf magnetic biomass composites. The magnetic composites were employed in a magnetic solid-phase extraction method, coupled with gas chromatography-electron capture detection (GC-ECD), for the analysis of four pesticides (trifluralin, triadimefon, permethrin, and fenvalerate) in environmental water samples. The innovative magnetic persimmon leaf composites were synthesized by in situ generation of Fe3O4 nanoparticles through coprecipitation and loaded onto persimmon leaves. These composites exhibit superparamagnetism with a saturation magnetization of 12.8 emu g-1, facilitating rapid phase separation using a magnetic field and reducing the extraction time to 10 min. Desorption can be achieved within 30 s by aspirating 20 times, eliminating the need for time-consuming and labor-intensive experimental steps like filtration and centrifugation. The specific surface area of the magnetic composite adsorbent increased from 1.3279 m2 g-1 for the original persimmon leaf to 5.4688 m2 g-1. The abundant hydroxyl and carboxyl groups on the composites provide ample adsorption sites, resulting in adsorption capacities ranging from 55.056 mg g-1 to 73.095 mg g-1 for the studied pesticides. The composites exhibited extraction recoveries ranging from 80% to 90% for the studied pesticides. Compared to certain previously reported MSPE methods, this approach achieves equivalent or higher extraction recoveries in a shorter operation time, demonstrating enhanced efficiency and convenience. Good linearity of the target analytes was obtained within the range of 0.75-1500 μg L-1, with a determination of coefficient (R2) greater than 0.999. These findings contribute to the use of magnetic persimmon leaf biomass materials as effective and environmentally friendly adsorbents for pollutant determination in water samples.

Fabrication of a porous Urea@MIL-100(Fe)/CI-MCC/SA hydrogel for All-In-One adsorption, removal and fluorescence monitoring of nitrite

In this paper, a novel All-In-One Urea@MIL-100(Fe)/CI-MCC/SA hydrogel platform was generated by microcrystalline cellulose (MCC) functionalized with pH-response probe (CI), MIL-100 (Fe) and sodium alginate (SA), which was as a carrier of urea to adsorb, remove and monitor NO2-. Under acidic condition, the fluorescent hydrogel platform could produce N2, CO2 and H2O through the diazotization and redox reaction between urea and NO2- with a removal efficiency up to 99.8%, and could also character a good adsorption property for NO2- due to the positive charges of protonation (the maximum adsorption capacity was 21.67 mg g−1), and the adsorption kinetics conformed to pseudo-second-order model. By carried out the NO2- removal step in fluorescent hydrogel platform, NO2- could also be detected indirectly by sensing the changes of pH within 15 min. The linear response range was 0–0.005 M, and the detection limit (LOD) was 74 μM. These results demonstrated that this All-In-One Urea@MIL-100(Fe)/CI-MCC/SA hydrogel platform had great potential in environment. This strategy for the removal and monitoring of NO2- could be employed to related applications in water purification and environmental protection. Environmental implicationNitrite is one of the important indicators of water monitoring, which is harmful to human and environment. The removal and monitoring of nitrite in industrial wastewater and surface water is very important, but there are no studies about it at present. Based on the fact that urea can react with nitrite to produce green products, we synthesized a novel functional hydrogel to achieve adsorption, removal and fluorescence monitoring of nitrite for the first time. Besides, the practicability of the material in environmental water samples was verified through the detection of nitrite in simulated wastewater.

A POM/viologen-based supramolecular fluorescent probe for Ag+ detection and application of visible hydrogel based intelligent sensing system

Silver (Ag+) as a typical heavy metal ion has significant impacts on human health, so monitoring Ag+ level is an important issue. In this work, a new POM (polyoxometalates)/viologen-based supramolecular compound, [(HMSBP)2(γ-Mo8O26)]·4H2O (1) has been synthesized by hydrothermal method (MSBP = 1-(4-Methanesulfonyl-benzyl)-[4,4']bipyridinyl-1-ium). This POM/viologen-based supramolecular compound exhibits the unique supramolecular structure, excellent optical stability and superior fluorescence intensity, which is expected to become a promising fluorescent sensor. The coordination reaction between SO, pyridine N atom and Ag+ in compound 1 makes the detection of Ag+ achieved and the limit of detection (LOD) is 0.0411 μM in the range of 0.1–3 μM. Moreover, this supramolecular fluorescent probe has successfully realized the quantitative monitoring of Ag+ concentration in environmental water samples and commercially available disinfectant spray. Viologen is regarded as a good external stimulus responsive material, while its discoloration behavior can be exploited as an intelligent sensor system. The platform based on hydrogel and smartphones realizes the visualization and real-time quantification of Ag+, which provides an effective way for the rapid and convenient determination of Ag+. This provides a feasible way to promote the qualitative/semi quantitative detection of visual fluorescence POM/viologen sensors.

Ecofriendly ratiometric colorimetric determination of mercury(II) ion in environmental water samples using gallic acid-capped gold nanoparticles

Today, the monitoring and determination of heavy metal pollutants in the environment is an essential requirement for the environmental and research communities. Mercury ion is one of the most hazardous heavy metals, and scientists are trying to develop new methods for its detection. In this study, a new colorimetric sensor based on aggregation gallic acid-capped gold nanoparticles (GA-AuNPs) for the determination of mercury ions in environmental water samples was presented. The green synthesized GA-AuNPs exhibited a sharp surface plasmon resonance peak at 515 nm. The addition of mercury ions changed the surface properties of GA-AuNPs, resulting in the formation of a new peak near 670 nm due to the aggregation of GA-AuNPs, and an obvious color change from red to purple occurred. Thus, mercury ions were detected based on the change in the absorbance ratio (A670/A515). The developed sensor can determine the mercury ions in the concentration range of 78.0 nM to 8.3 µM with a detection limit of 5.5 nM. Based on the Environmental Protection Agency (EPA) and the World Health Organization (WHO) reports, the amount of Hg2+ ions in fresh water should be between 10.0 and 30.0 nM. The results indicate that the developed sensor can detect and determine trace amounts of Hg2+ ions in environmental water samples.

Synergetic impact of copper nanoparticles and polyaniline reinforced graphene oxide nanocomposite on the sequestration of tetracycline antibiotic from milk and wastewaters samples

Tetracycline pollution poses a serious threat to both human and animal health, even at very low concentrations. The removal of these antibiotics from ecosystems has gained significant academic and public attention. Herein, tetracycline (TC) antibiotic in different environmental water samples were successfully extracted using copper nanoparticles immobilized-polyaniline modified graphene oxide (Cu/PANI/GO) nanocomposite. The structure and physicochemical properties of the new fabricated nanocomposite were investigated by various analytical techniques including SEM, TEM, EDX, FTIR, Raman spectra, and zeta-potential. It has been found that TC removal efficiency onto Cu/PANI/GO was greatly improved when compared to the native GO, and that it could even achieve a record-high value of 99.6% with 434.78 mg g−1 adsorption capacity. The synergic effect of the supported Cu-NPs and PANI moieties for the TC removal efficiency is about 51.5 ± 3.9% compared to that for GO. The pseudo-second-order (PSO) kinetic model and the Langmuir model, respectively, can provide excellent fits for the adsorption kinetics and isotherms of TC onto Cu/PANI/GO. Five adsorption-desorption cycles resulted in a 4.1% reduction in the removal effectiveness. Through the surface complexation by the Cu-nanoparticles, in addition to the potent hydrogen bond formation with PANI and GO moieties and the π-π interactions of graphene oxide, TC were firmly trapped in the structure of the Cu/PANI/GO nanocomposite. The Cu/PANI/GO nanocomposite was utilized to remove TCs from samples of milk and wastewater.

Efficient adsorption of fluorescent whitening agent 351 from high salinity environmental water by polymer supported hydroxyl functional ionic liquid

Fluorescent whitening agent 351 (FWA351) is an emerging highly persistent pollutant with potentially harmful effects on human health and aquatic ecosystem. However, developing highly effective adsorbents for the pre-treatment of environmental water samples containing FWA351 remains a problem. In this study, a novel polymer supported hydroxyl-functionalized ionic liquid (PS-[HMMim][Cl]) was prepared via a simple one-step method and used for the removal of FWA351 from water. It was found that the PS-[HMMim][Cl] exhibited an ultrahigh adsorption capacity of 1203.6 mg/g for FWA351 and maintained high removal efficiency in a wide pH range (2.0–9.0). Notably, even the concentration of FWA351 was as low as 0.005 mg/L (5 ppb), FWA351 could be effectively removed by the adsorbent, achieving an enrichment factor as high as 447.8. Various inorganic salts (such as KCl, NaCl and MgCl2) at the concentration up to 1.0 mol/L had no obvious effect on the removal efficiency. The PS-[HMMim][Cl] also displayed outstanding adsorption performance towards fluorescent whitening agents (FWAs) with similar structure to FWA351 and could be regenerated and reused for at least 8 cycles. Finally, the adsorbent was applied for the pre-treatment and then detection of FWA351 in six kinds of environmental water samples. Mechanism studies suggest that the synergistic driving forces of electrostatic attraction, hydrogen bonding, π-π interaction and ion exchange are responsible for the efficient adsorption of FWA351. This work provides a new strategy for efficient adsorption and analysis of FWA351.

Determination of MCPA in environmental samples using an analytical on-line system based on imprinted poly[2-(3-butenyl)-2-oxazoline] and ambient ionization mass spectrometry

Monitoring and quantifying organic chemicals in the environment play a vital role in understanding their behavior and ensuring environmental safety. MCPA (2-methyl-4-chlorophenoxyacetic acid) is a commonly used phenoxy herbicide that poses potential risks to aquatic life. In this study, we present an innovative analytical approach for MCPA quantification, employing molecularly imprinted polymers (MIPs) for selective extraction and ambient plasma mass spectrometry for direct on-line analysis. To synthesize functional MIPs, we employed a post-polymerization strategy based on a thiol-ene click reaction conducted on a short-chain poly[2-(3-butenyl)-2-oxazoline] (poly(ButenOx)) that allowed attachment of 3-mercaptopropionic acid (MPA) to polymer side chains. The incorporation of MPA groups into polymer structure enabled the attainment of elevated maximum adsorption capacities and enhanced selectivity towards MCPA. Utilizing a specially designed ambient plasma mass spectrometry setup, we successfully quantified MCPA in water samples, achieving significantly improved detection limits compared to conventional solution-based analysis, whereas the quantification of MCPA in real-life river water samples demonstrated excellent recoveries. In conclusion, this novel analytical method employing MIPs and ambient plasma mass spectrometry provides an effective and sensitive approach for accurate MCPA detection in environmental water samples. The technique holds promise for facilitating reliable monitoring and management of MCPA levels in aquatic ecosystems.

Application of sol‐gel universal sorbent coated fabric phase sorptive extraction membranes in combination with high‐performance liquid chromatography‐ultraviolet detection to monitor endocrine‐disrupting chemicals in milk and environmental water samples

AbstractHere, we deployed sol‐gel universal sorbent‐coated fabric phase sorptive extraction membranes in tandem with high‐performance liquid chromatography equipped with an ultraviolet detector (HPLC‐UV) for the analysis of 10 endocrine‐disrupting chemicals (EDCs). Due to the varying polarities of the studied compounds indicated by their octanol/water partition coefficient ‘log Kow’ (1.47–5.07), the extraction membrane was designed with different functionalities that are capable of simultaneous interaction with compounds of diverse natures including polar, non‐polar, and ionic species via sol‐gel sorbent coating technology. An isocratic mode of HPLC‐UV at 55:45% acetonitrile:water (v/v) on a reverse phase C18 Zorbax column (5 μm, 150 mm, 4.6 mm) was used for the separation and quantitation. Calibration curves were found linear between 25 and 2000 ppb for all compounds except cortisone in the range of 25–1000 ppb which provided an R2 value above 0.9940 in all cases. The intra‐day reproducibility and inter‐day reproducibility were found in the range of 1.2–12.8 and 0.2–14.1 (expressed as percent relative standard deviation), respectively. The validated method was finally deployed for the analysis of environmental water and milk samples with estradiol showing the highest concentrations among the studied compounds.

A novel magnetic porous organic cage adsorbent for high-efficient removal of endocrine disrupting chemicals from environmental water

Endocrine disrupting chemicals (EDCs) are pervasive emerging pollutants found in environmental water, stemming from their widespread use in personal consumer products. This study presents a novel magnetic Porous organic cage (POC) material, Fe3O4-COOH@CC3R-OH, which has been proven to be highly effective in eco-friendly eliminating EDCs. Featuring a tetrahedral morphology with core–shell structure, the new magnetic adsorbent boasts a substantial Brunauer-Emmett-Teller surface area of 94.02 m2/g and a particle pore size of 1.14 nm. Rigorous optimization of adsorption conditions for eight specific EDCs was conducted, complemented by insightful molecular docking simulations shedding light on the adsorption mechanisms. Furthermore, the developed Fe3O4-COOH@CC3R-OH magnetic solid phase extraction-assisted high performance liquid chromatography-tandem mass spectrometry (MSPE-HPLC-MS/MS) method exhibits good sensitivity and precision in the quantitative detection of EDCs in environmental water samples. This integrated approach provides a robust platform for both efficient removal and accurate detection of EDCs, advancing water quality control and safeguarding human health.

Peptide-based probe for colorimetric and fluorescent detection of Cu2+ and S2- in environmental and biological systems

Pollution caused by Copper and hydrogen sulfide pollution has severe adverse effects on the environment and organisms. Real-time, fast and accurate monitoring of Cu2+ and S2- faces serious challenges. In this study, we designed a novel biosensor and synthesized it by mimicking the structure of the main Cu(II)-binding site on bovine serum albumin. As a peptide-based sensor, FGGH (FITC-Gly-Gly-His-NH2) can perform the sequential detection of Cu2+ and S2– by fluorescence and colorimetry. The high water solubility and selectivity make it suitable for monitoring Cu2+ and S2– in environmental water samples with high sensitivity; its limit of detection (LOD) is as low as 1.42 nM for Cu2+ and 22.2 nM for S2–. The paper-based sensing platform of this probe was found to be a promising tool for the on-site visualization of real-time quantitative analysis of Cu2+ and S2– due to its rapid response and recyclable detection characteristics. Additionally, FGGH was successfully used to image Cu2+ and S2– in living cells and zebrafish models with adequate fluorescence stability and low cytotoxicity, providing the first visual evidence of the effect of the interactions between Cu2+ and S2– on the redox homeostasis of organisms.

Synthesis of ion-imprinted polymers for speciation analysis of chromium(III)

A new sorbent based on ion-imprinted polymers has been successfully synthesized to examine chromium(III) in environmental water samples. In this study, Cr(III)−IIPs was synthesized using Cr(III)−DPCO complex as a templating molecule, and ethylene glycol dimethacrylate (EGDMA), methacrylic acid (MAA), and benzoyl peroxide (BPO) as crosslinking agent, functional monomer, and radical initiator, respectively. The fabricated Cr(III)−IIPs polymer was characterized using Fourier transform infrared (FTIR) spectroscopy and Scanning electron microscope (SEM). The FTIR results confirm that Cr(III)−IIPs has been successfully synthesized. A peak at 495 cm-1 indicated the stretching vibrations of Cr−N. The firm peaks at 1732 cm-1 and 1163 cm-1 are assigned to C=O and C−O stretching vibrations of methacrylic acid. The broad and strong peak at 3483 cm-1 corresponded to hydroxyl bonds between the templating molecule and functional monomer. The SEM images revealed that the morphology of the polymer was irregular and large. The Imprinting factor (IF) values of Cr(III)−IIPs/NIPs−DPCO and Cr(III)−IIPs/NIPs were 3.12 and 1.53, respectively. The sorbent developed by this technique can be selective to the target ions.

Characterizations of novel broad-spectrum lytic bacteriophages Sfin-2 and Sfin-6 infecting MDR Shigella spp. with their application on raw chicken to reduce the Shigella load

The evidence and prevalence of multidrug-resistant (MDR) Shigella spp. poses a serious global threat to public health and the economy. Food- or water-borne MDR Shigella spp. demands an alternate strategy to counteract this threat. In this regard, phage therapy has garnered great interest from medical practitioners and researchers as a potential way to combat MDR pathogens. In this observation, we isolated Shigella phages from environmental water samples and tested against various clinically isolated MDR Shigella spp. In this study, we have defined the isolation and detailed physical and genomic characterizations of two phages Sfin-2 and Sfin-6 from environmental water samples. The phages exhibited potent lytic activity against Shigella flexneri, Shigella dysenteriae, and Shigella sonnei. They showed absorption within 5–10 min, a burst size ranging from ~74 to 265 PFU/cell, and a latent period of 5–20 min. The phages were stable at a broad pH range and survived an hour at 50°C. The purified phages Sfin-2 and Sfin-6 belong to the Siphoviridae family with an isometric head (64.90 ± 2.04 nm and 62.42 ± 4.04 nm, respectively) and a non-contractile tail (145 ± 8.5 nm and 148.47 ± 14.5 nm, respectively). The in silico analysis concluded that the size of the genomic DNA of the Sfin-2 phage is 50,390 bp with a GC content of 44.90%, while the genome size of the Sfin-6 phage is 50,523 bp with a GC content of 48.30%. A total of 85 and 83 putative open reading frames (ORFs) were predicted in the Sfin-2 and Sfin-6 phages, respectively. Furthermore, a comparative genomic and phylogenetic analysis revealed that both phages represented different isolates and novel members of the T1-like phages. Sfin-2 and Sfin-6 phages, either individually or in a cocktail form, showed a significant reduction in the viable Shigella count on raw chicken samples after 72 h of incubation. Therefore, these results indicate that these phages might have a potential role in therapeutic approaches designed for shigellosis patients as well as in the biological control of MDR Shigella spp. in the poultry or food industry during the course of meat storage.

Assessment of crAssphage as a human fecal source tracking marker in the lower Great Lakes

CrAssphage or crAss-like phage ranks as the most abundant phage in the human gut and is present in human feces-contaminated environments. Due to its high human specificity and sensitivity, crAssphage is a potentially robust source tracking indicator that can distinguish human fecal contamination from agricultural or wildlife sources. Its suitability in the Great Lakes area, one of the world's most important water systems, has not been well tested. In this study, we tested a qPCR-based quantification method using two crAssphage marker genes (ORF18-mod and CPQ_064) at Toronto recreational beaches along with their adjacent river mouths. Our results showed a 71.4 % (CPQ_064) and 100 % (ORF18-mod) human sensitivity for CPQ_064 and ORF18-mod, and a 100 % human specificity for both marker genes. CrAssphage was present in 57.7 % or 71.2 % of environmental water samples, with concentrations ranging from 1.45 to 5.14 log10 gene copies per 100 mL water. Though concentrations of the two marker genes were strongly correlated, ORF18-mod features a higher human sensitivity and higher positive detection rates in environmental samples. Quantifiable crAssphage was mostly present in samples collected in June and July 2021 associated with higher rainfall. In addition, rivers had more frequent crAssphage presence and higher concentrations than their associated beaches, indicating more frequent and greater human fecal contamination in the rivers. However, crAssphage was more correlated with E. coli and Enterococcus at the beaches than in the rivers, suggesting human fecal sources may be more predominant in driving the increases in E. coli and Enterococcus at the beaches when impacted by river plumes.

Long-lasting developmental effects in rat offspring after maternal exposure to acetamiprid in the drinking water during gestation.

Neonicotinoids (NNTs) are a class of insecticides proposed to be safe for pest control in urban, suburban, and agricultural applications. However, little is known about their developmental effects after repeated low-dose exposures during gestation. Here, we tested a dose considered subthreshold for maternal toxicity in rats (6 mg/kg/day) by assessing several morphological, biochemical, and neurobehavioral features in preterm fetuses and developing pups after maternal administration of the NTT acetamiprid (ACP) dissolved in the drinking water during gestational days (GD) 2-19. The exploratory evaluation included monitoring maternal body weight gain, fetal viability, body weight and sex ratio, cephalic length, neonatal body weight and sex ratio, metabolic enzymes in the placenta, maternal blood and fetal liver, and anogenital distance and surface righting response during infancy. We also used the circling training test to study the integrity of the associative-spatial-motor response in adolescence. Results showed no consistent findings indicating maternal, reproductive or developmental toxicity. However, we found ACP effects on maternal body weight gain, placental butyrylcholinesterase activity, and neurobehavioral responses, suggestive of a mild toxic action. Thus, our study showed a trend for developmental susceptibility at a dose so far considered subtoxic. Although the ACP concentration in environmental samples of surface water and groundwater has been mostly reported to be much lower than that used in our study, our results suggest that the ACP point of departure used in current guidelines aimed to prevent developmental effects may need to be verified by complementary sensitive multiple-endpoint testing in the offspring.

Cysteine-functionalized selenium nanoparticles for efficient extraction and preconcentration of cadmium, copper, lead, and zinc ions from environmental water samples

This study aimed to develop cysteine-functionalized selenium nanoparticles (SeNPs) supported by γ-alumina (Al2O3@Se@Cys) for the effective extraction and preconcentration of cadmium, copper, lead, and zinc ions from river water and seawater samples. This one-pot synthesis method produced and functionalized SeNPs using L-cysteine as a green reducing agent. The different properties of Al2O3@Se@Cys were analyzed using various techniques, including Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), and X-ray diffraction (XRD). Several experiments were conducted to identify and optimize the key variables influencing extraction efficiencies, such as the pH, ascorbic acid concentration, Al2O3@Se@Cys amount, solution volume, salinity, and elution and matrix clean-up conditions. The results showed that the proposed method provided detection limits ranging from 0.25 to 1.00 µg/L, relative standard deviations (RSDs, n = 5) between 1.1 % and 4.5 %, dynamic linear ranges within 10–200 µg/L (R2 ≥ 0.995), and enrichment factors >85. Moreover, the recoveries of the spiked standard solutions in river water and seawater samples were at least 94.0 %, with negligible interference from most major and minor ions commonly found in environmental water samples. The study demonstrated the successful development and application of Al2O3@Se@Cys, which exhibits a sustainable and eco-friendly approach to addressing environmental contamination challenges and highlights the expanding utility of SeNPs.

Hydrophobic deep eutectic solvent-based vortex assisted liquid–liquid microextraction for the determination of famciclovir in water samples coupled with high performance liquid chromatography

Deep eutectic solvents (DESs), as a new generation of green solvents, have the advantages of simple preparation procedure, low toxicity, non-volatility and good extraction performance in replacing traditional volatile organic solvents. In this work, a series of hydrophobic DESs were prepared and used as extraction solvent for the vortex-assisted liquid–liquid micro-extraction and determination of famciclovir in environmental water samples coupled with high performance liquid chromatography. The key factors affecting the extraction efficiency were investigated by using single-factor test and response surface methodology. The optimized conditions were as follows: the DES type (thymol: ethyl aniline formate, molar ratio 3:1), DES dosage 50 mg, extraction time 1.5 min, solution pH 6.0, diluent volume 100 µL. Under the optimal conditions, calibration curve of the proposed method was in the range of 0.7–2000 μg/L with correlation coefficient (r2) higher than 0.9997. The limit of detection (LOD, S/N = 3) and the limit of quantitation (LOQ, S/N = 10) were 0.2 and 0.7 μg/L, and the intra-day and inter-day precision were less than 2.3 % and 1.6 %, respectively. Finally, this method was successfully used for the determination of trace famciclovir in environmental water samples with recoveries in the range of 86 %-118 %.