Furan-Dihydroquinazolinone Based Fluorescent Nanoprobe for Selective Recognition of 4-Nitrophenol: A Spectofluorimetric Approach.

Fluorescent organic nanoparticles (FONPs) have attracted much attention as a practicable and effective platform for detection applications. The present article describes the preparation of FONPs derived from the quinazolinone-based 2-(furan-2-yl)-2,3-dihydroquinazolin-4(1H)-one derivative FHDQ. Self-assembly of FHDQ in an aqueous medium resulted in the formation of FONPs through H-type aggregation and showed excellent fluorescence properties. The presence of other coexisting species solutions did not affect the selective fluorescence quenching observed with the addition of 4-nitrophenol (4-NP). The photophysical properties, i.e., UV-Vis absorbance, fluorescence emission, and lifetime measurements together with zeta particle sizer, support excited-state complex formation followed by a dynamic fluorescence quenching phenomenon in the emission of FDHQNPs. In the concentration range of 0 to 36 µg.[Formula: see text], the detection limit of this turn-off sensor FDHQNPs against 4-NP was determined to be 0.01611 µM. Finally, the practicability of the FDHQNPs for the analysis of 4-NP in environmental samples was demonstrated.

Unveiling carcinogenic pollutant levels in environmental water samples through facile fabrication of gold nanoparticles on sulfur-doped graphitic carbon nitride.

Extensive utilization of pesticides and herbicides to boost agricultural production increased the environmental health risks, which can be mitigate with the aid of highly sensitive detection systems. In this study, an electrochemical sensor for monitoring the carcinogenic pesticides in the environmental samples has been developed based on sulfur-doped graphitic-carbon nitride-gold nanoparticles (SCN-AuNPs) nanohybrid. Thermal polycondensation of melamine with thiourea followed by solvent exfoliation via ultrasonication leads to SCN formation and electroless deposition of AuNPs on SCN leads to SCN-AuNPs nanohybrid synthesis. The chemical composition, S-doping, and the morphology of the nanohybrid were confirmed by various microscopic and spectroscopic tools. The as-synthesized nanohybrid was fabricated with glassy carbon (GC) electrode for determining the carcinogenic hydrazine (HZ) and atrazine (ATZ) in field water samples. The present sensor exhibited superior electrocatalytic activity than GC/SCN and GC/AuNPs electrodes due to the synergism between SCN and AuNPs and the amperometric studies showed the good linear range of detection of 20 nM-0.5 mM and 500 nM-0.5 mM with the limit of detection of 0.22 and 69 nM (S/N = 3) and excellent sensitivity of 1173.5 and 13.96 µA mM-1 cm-2 towards HZ and ATZ, respectively. Ultimately, the present sensor is exploited in environmental samples for monitoring HZ and ATZ and the obtained results are validated with high-performance liquid chromatography (HPLC) technique. The excellent recovery percentage and close agreement with the results of HPLC analysis proved the practicability of the present sensor. In addition, the as-prepared materials were utilized for the photocatalytic degradation of ATZ and the SCN-AuNPs nanohybrid exhibited higher photocatalytic activity with the removal efficiency of 93.6% at 90 min. Finally, the degradation mechanism was investigated and discussed.

Slice through the water-Exploring the fundamental challenge of water suppression for benchtop NMR systems.

Benchtop NMR provides improved accessibility in terms of cost, space, and technical expertise. In turn, this encourages new users into the field of NMR spectroscopy. Unfortunately, many interesting samples in education and research, from beer to whole blood, contain significant amounts of water that require suppression in 1H NMR in order to recover sample information. However, due to the significant reduction in chemical shift dispersion in benchtop NMR systems, the sample signals are much closer to the water resonance compared to those in a corresponding high-field NMR spectrum. Therefore, simply translating solvent suppression experiments intended for high-field NMR instruments to benchtop NMR systems without careful consideration can be problematic. In this study, the effectiveness of several popular water suppression schemes was evaluated for benchtop NMR applications. Emphasis is placed on pulse sequences with no, or few, adjustable parameters making them easy to implement. These fall into two main categories: (1) those based on Pre-SAT including Pre-SAT, PURGE, NOESY-PR, and g-NOESY-PR and (2) those based on binomial inversion including JRS and W5-WATERGATE. Among these schemes, solvent suppression sequences based on Pre-SAT offer a general approach for easy solvent suppression for samples with higher analyte concentrations (sucrose standard and Redbull™). However, for human urine, binomial-like sequences were required. In summary, it is demonstrated that highly efficient water suppression approaches can be implemented on benchtop NMR systems in a simple manner, despite the limited spectral dispersion, further illustrating the potential for widespread implementation of these approaches in education and research.

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 the extraction 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%.

A New Planar Potentiometric Sensor for In Situ Measurements.

A new construction of a potentiometric sensor was introduced for the first time. It relies on the use of two membranes instead of one, as in the well-known coated-disc electrode. For this purpose, a new electrode body was constructed, including not one, but two glassy carbon discs covered with an ion-selective membrane. This solution allows for the sensor properties to be enhanced without using additional materials (layers or additives) on the membrane. The new construction is particularly useful for in situ measurements in environmental samples. Two ion-selective polymeric membranes were used, namely H+ and K+-selective membranes, to confirm the universality of the idea. The tests conducted included chronopotentiometric tests, electrochemical impedance spectroscopy, and potentiometric measurements. The electrical and analytical parameters of the sensors were evaluated and compared for all tested electrodes to evaluate the properties of the planar electrode versus previously known constructions. Research has shown that the application of two membranes instead of one allows for the resistance of an electrode to be lowered and for the electrical capacitance to be elevated. Improving the electrical properties of an electrode resulted in the enhancement of its analytical properties. The pH measurement range of the planar electrode is 2-11, which is much wider in contrast to that of the single-membrane electrode. The linear range of the K+-selective planar electrode is wider than that of the coated-disc electrode and equals 10-6 to 10-1 M. The response time turned out to be a few seconds shorter, and the potential drift was smaller due to the application of an additional membrane in the electrode construction. This research creates a new opportunity to design robust potentiometric sensors, as the presented construction is universal and can be used to obtain electrodes selective to various ions.

The High Stability and Selectivity of Electrochemical Sensor Using Low-Cost Diamond Nanoparticles for the Detection of Anti-Cancer Drug Flutamide in Environmental Samples.

In this study, a novel electrochemical sensor was created by fabricating a screen-printed carbon electrode with diamond nanoparticles (DNPs/SPCE). The successful development of the sensor enabled the specific detection of the anti-cancer drug flutamide (FLT). The DNPs/SPCE demonstrated excellent conductivity, remarkable electrocatalytic activity, and swift electron transfer, all of which contribute to the advantageous monitoring of FLT. These qualities are critical for monitoring FLT levels in environmental samples. Various structural and morphological characterization techniques were employed to validate the formation of the DNPs. Remarkably, the electrochemical sensor demonstrated a wide linear response range (0.025 to 606.65 µM). Additionally, it showed a low limit of detection (0.023 µM) and high sensitivity (0.403 µA µM-1 cm-2). Furthermore, the practicability of DNPs/SPCE can be successfully employed in FLT monitoring in water bodies (pond water and river water samples) with satisfactory recoveries.

Determination of polyurethanes within microplastics in complex environmental samples by analytical pyrolysis.

Polyurethanes (PUR) are a group of polymers synthesized from different diisocyanate and polyol monomers resulting in a countless number of possible structures. However, the large market demand, and the variety of application fields justify the inclusion of PUR in microplastic (MP) investigation. This study aimed at providing comprehensive information on PUR within MP analysis by pyrolysis-gas chromatography-mass spectrometry to clarify whether (i) it is possible to make a reliable statement on the PUR content of environmental samples based on a few pyrolysis products and (ii) which restrictions are required in this context. PUR were managed as subclasses defined by the diisocyanates employed for polymer synthesis. Methylene diphenyl diisocyanate (MDI)- and toluene diisocyanate (TDI)-based PUR were selected as subclasses of greatest relevance. Different PUR were pyrolyzed directly and under thermochemolytic conditions with tetramethylammonium hydroxide (TMAH). Distinct pyrolytic indicators were identified. The study supported that the use of TMAH greatly reduced the interactions of pyrolytic MP analytes with the remaining organic matrix of environmental samples and the associated negative effects on analytical results. Improvements of chromatographic behavior of PUR was evidenced. Regressions (1-20 µg) showed good correlations and parallelism tests underlined that quantitation behavior of different MDI-PUR could be represented by the calibration of just one representative with sufficient accuracy, entailing a good estimation of the entire subclass if thermochemolysis were used. The method was exemplary applied to road dusts and spider webs sampled around a plastic processing plant to evaluate the environmental spread of PUR in an urban context. The environmental occurrence of MDI-PUR as MP was highly influenced by the proximity to a potential source, while TDI markers were not observed.

Natural deep eutectic solvent-based microextraction for mercury speciation in water samples.

A new natural deep eutectic solvent (NADES)-based analytical method for mercury speciation in water samples is presented. A NADES (i.e., decanoic acid:DL-menthol in a molar ratio of 1:2) is used as an environmentally friendly extractant for separation and preconcentration using dispersive liquid-liquid microextraction before LC-UV-Vis. Under optimal extraction conditions (i.e., NADES volume, 50 µL; sample pH, 12; volume of the complexing agent, 100 µL; extraction time, 3 min; centrifugation speed, 3000 rpm; and centrifugation time, 3 min), the limit of detection values were 0.9 µg L-1 for the organomercurial species and 3 µg L-1 for Hg2+, which had a slightly higher value. The relative standard deviation (RSD, n = 6) has been evaluated at two concentration levels (25 and 50 µg L-1) obtaining values for all the mercury complexes within the range of 6-12% and 8-12%, respectively. The trueness of the methodology has been evaluated using five real water samples from four different sources (i.e., tap, river, lake, and wastewater). The recovery tests have been performed in triplicate obtaining relative recoveries between 75 and 118%, with RSD (n = 3) between 1 and 19%, for all the mercury complexes in surface water samples. However, wastewater sample showed a significant matrix effect (recoveries ranged between 45 and 110%), probably due to the high amount of organic matter. Finally, the greenness of the method has also been evaluated by the analytical greenness metric for sample preparation (i.e., AGREEprep).

Novel fast pesticides extraction (FaPEx) strategy coupled with UHPLC-MS/MS for rapid monitoring of emerging pollutant fipronil and its metabolite in food and environmental samples.

In this work, we demonstrated a new, environmental-friendly and effective sample preparation strategy named 'in-syringe-assisted fast pesticides extraction (FaPEx)' technique coupled with LC-MS/MS for the rapid identification and monitoring of emerging pollutant fipronil and its metabolite fipronil sulfone in chicken egg and environmental soil samples. FaPEx strategy comprising of two simple steps. Firstly, the sample was placed in the syringe and extracted using low-volume acetonitrile with NaCl and anhydrous MgSO4 salts. Secondly, the extractant was passed through in-syringe-based solid-phase extraction (SPE) kit containing cleanup sorbents and salt combinations (C18, primary secondary amine, and anhydrous MgSO4) for the cleanup process. Then, the obtained clean extractant was injected into LC-MS/MS for the quantification of target analytes. Various important parameters influencing the FaPEx performances, such as solvent type, salt type, salt amount, sorbent type, and amount, were examined and optimized. The method validation results showed excellent linearity with high correlation coefficients were ≥ 0.99. The estimated LODs were between 0.05-0.07 µg/kg, and LOQs ranged between 0.1-0.25 µg/kg for target analytes in both egg and soil sample matrices, and precision values were ≤7.90%. The developed method was applied to commercial chicken egg samples and environmental soil samples analysis. Spiked recoveries ranged between 88.75-110.91% for egg samples with RSDs ≤7.42% and 82.47-107.46% for soil samples with RSDs <7.37%. These results proved that the developed sample preparation method is a simple, fast, green, low-cost, and efficient method for the analysis of fipronil and its metabolites in food and environmental samples. Thus, this method can be applied as an alternative analytical methodology in routine and standard food and environmental testing laboratories.

Distribution of Inorganic Contaminants Along the Coast of Ciudad de la Costa, Uruguay.

The aim of this work was to study the distribution of relevant inorganic contaminants in environmental samples from Ciudad de la Costa, the second most populated city of Uruguay. For this task aluminum (Al), cadmium (Cd), chromium (Cr), nickel (Ni) and lead (Pb) levels were determined in sand, water, and plant material from six beaches that are located in the area. Analytical methods were successfully validated. Accuracy was ensured by using certified reference materials and spiking procedures. Average metal concentrations in sand and water samples were compared with the maximum limits established by international or national regulations (when available), being far below these limits in all cases. This may indicate that the inorganic contamination in the studied area is rather low, despite the rapid increase in anthropic activities in recent years. To give a deeper characterization of the ecosystem, metal accumulation and mobility within a common plant of the zone, Ammophila arenaria, were studied. Results showed that concentrations in roots were one order of magnitude higher in comparison to aerial parts. In addition, the bioaccumulation coefficient (BAC) showed that the plant accumulates Cd, Cr and Ni, while a low accumulation for Pb was observed. Finally, a Cr(VI) speciation analysis in Ammophila arenaria was performed, showing Cr(VI) percentages below 4.6%, which is relevant from the (eco)toxicological point of view due to the high environmental mobility and bioavailability of this valence state. This work constitutes the first environmental surveillance report of this kind, regarding this populated area of the country.

Detection of Polonium-210 in Environmental, Biological and Food Samples: A Review.

Ingestion of polonium-210 from environmental media and food can cause serious health hazards (e.g., gastrointestinal symptoms, tumours, etc.) and has been a public health concern worldwide since the 2006 poisoning of Agent Litvinenko 210Po in Russia. With the development of uranium mining and applications of nuclear technology in recent decades, the radioactive hazards posed by 210Po to living organisms and the environment have become increasingly prominent. In order to strengthen the monitoring of environmental 210Po and protect both the environment and human health, a series of explorations on the methods of 210Po determination have been ongoing by researchers across the globe. However, previous reviews have focused on individual sample types and have not provided a comprehensive account of environmental, food, and biological samples that are closely related to human health. In this work, the sources, health hazards, chemical purification, and detection methods of trace 210Po in different sample types are systematically reviewed. In particular, the advantages and disadvantages of various pretreatment methods are compared, and relevant domestic and international standards are integrated, which puts forward a new direction for the subsequent establishment of rapid, simple, and efficient measurement methods.

Use of Trifluoro-Acetate Derivatives for GC-MS and GC-MS/MS Quantification of Trace Amounts of Stera-3ß,5α,6ß-Triols (Tracers of Δ5-Sterol Autoxidation) in Environmental Samples.

Stera-3ß,5α,6ß-triols make useful tracers of the autoxidation of Δ5-sterols. These compounds are generally analyzed using gas chromatography-mass spectrometry (GC-MS) after silylation. Unfortunately, the 5α hydroxyl groups of these compounds, which are not derivatized by conventional silylation reagents, substantially alter the chromatographic properties of these derivatives, thus ruling out firm quantification of trace amounts. In this work, we developed a derivatization method (trifluoroacetylation) that enables derivatization of the three hydroxyl groups of 3ß,5α,6ß-steratriols. The derivatives thus formed present several advantages over silyl ethers: (i) better stability, (ii) shorter retention times, (iii) better chromatographic properties and (iv) mass spectra featuring specific ions or transitions that enable very low limits of detection in selected ion monitoring (SIM) and multiple reaction monitoring (MRM) modes. This method, validated with cholesta-3ß,5α,6ß-triol, was applied to several environmental samples (desert dusts, marine sediments and particulate matter) and was able to quantify trace amounts of 3ß,5α,6ß-steratriols corresponding to several sterols: not only classical monounsaturated sterols (e.g., cholesterol, campesterol and sitosterol) but also, and for the first time, di-unsaturated sterols (e.g., stigmasterol, dehydrocholesterol and brassicasterol).

Current Methods and Prospects for Analysis and Characterization of Nanomaterials in the Environment.

Analysis and characterization of naturally occurring and engineered nanomaterials in the environment are critical for understanding their environmental behaviors and defining real exposure scenarios for environmental risk assessment. However, this is challenging primarily due to the low concentration, structural heterogeneity, and dynamic transformation of nanomaterials in complex environmental matrices. In this critical review, we first summarize sample pretreatment methods developed for separation and preconcentration of nanomaterials from environmental samples, including natural waters, wastewater, soils, sediments, and biological media. Then, we review the state-of-the-art microscopic, spectroscopic, mass spectrometric, electrochemical, and size-fractionation methods for determination of mass and number abundance, as well as the morphological, compositional, and structural properties of nanomaterials, with discussion on their advantages and limitations. Despite recent advances in detecting and characterizing nanomaterials in the environment, challenges remain to improve the analytical sensitivity and resolution and to expand the method applications. It is important to develop methods for simultaneous determination of multifaceted nanomaterial properties for in situ analysis and characterization of nanomaterials under dynamic environmental conditions and for detection of nanoscale contaminants of emerging concern (e.g., nanoplastics and biological nanoparticles), which will greatly facilitate the standardization of nanomaterial analysis and characterization methods for environmental samples.

Core-shell magnetic molecularly imprinted polymer for selective recognition and detection of sunset yellow in aqueous environment and real samples.

Magnetic Molecularly imprinted polymers (MMIPs) have been recently recognized as an exceptional tool for monitoring and decontamination of environmental and biological samples of diverse nature. Based on the potential applications as sorbents and biomimetic sensors, herein, a core-shell magnetic-molecularly imprinted polymer (MMIP) was developed as a selective material for separation and sensing of sunset yellow (SY) dye in an aqueous environment and real samples. The MMIP was synthesized via precipitation polymerization using SY as a template, MAA as a functional monomer (chosen based on simulation studies), EGDMA as a cross-linking agent, and AIBN as an initiator. To elaborate the specificity of MMIP, a comparative agent, magnetic non-imprinted polymer (MNIP) was also synthesized. The XRD results showed that the MMIP showed both crystalline and amorphous structure attributed to the presence and polymeric and non-polymeric groups. The FTIR spectra confirmed synthesis of intermediate and final MMIP product. The SEM results showed spherical morphology and porous structure of the MMIP with an average particle size of 0.636 µm in diameter. The MMIP was first employed as a sorbent for the removal of SY from the aqueous environment. The binding experiments performed at optimized operating conditions (pH 2; time 30 min; sorbent dosage 3 mg; sorbate concentration 80 ppm) showed more selectivity when compared with MNIP. The data fitted best to Langmuir's sorption isotherm (Qo 359.8 mg/g) and followed the pseudo-second-order kinetic model. The synthesized MMIP was also used as an electrochemical sensor for detection of SY dye in the aqueous environment, which exhibited a linear range of detection as (1.51 × 10-6 - 1.5 × 10-3 M). The limit of detection (LOD) and limit of quantification (LOQ) were found to be 0.00413 M and 0.0137 M, respectively. While the R2 value was found to be 0.997 at optimized analytical conditions. These results suggested that the synthesized MMIP can be applied for the selective separation and quantification of SY dye in sample of diverse nature.

Amino functionalized magnetic covalent organic framework for magnetic solid-phase extraction of sulfonylurea herbicides in environmental samples from tobacco land.

An amino-functionalized magnetic covalent organic framework composite TpBD-(NH2 )2 @Fe3 O4 (Tp=Tp1,3,5-triformylphloroglucinol, BD-(NH2 )2 is 3,3',4,4'-biphenyltetramine) was prepared by post-synthesis modification. Due to its abundant benzene rings and amino groups, large specific surface area and porous structure, the prepared TpBD-(NH2 )2 @Fe3 O4 exhibits high extraction efficiency toward sulfonylurea herbicides. Based on this, a new method of magnetic solid-phase extraction with TpBD-(NH2 )2 @Fe3 O4 as the sorbent combined with high-performance liquid chromatography and ultraviolet detection was developed for trace analysis of sulfonylurea herbicides in environmental water, soil and tobacco leaves samples from tobacco land. Under the optimized conditions, the limits of detection within 0.05-0.14 µg/L were achieved with a high enrichment factor of 217-260-fold, and the relative standard deviations were 4.9-7.5% (n = 7, c = 0.5 µg/L). The linear range was around three orders of magnitude with the square of correlation coefficient higher than 0.9936. The method was applied to analyze five sulfonylurea herbicides in the environmental water, soil, and tobacco leave samples collected from tobacco land. No sulfonylurea herbicides were detected in these samples. The recoveries of target sulfonylurea herbicides in spiked environmental water, soil, and tobacco leaf samples were found in the range of 90.7-104, 70.7-99.0, and 59.3-97.8%, respectively. The results illustrate that the established TpBD-(NH2 )2 @Fe3 O4 -magnetic solid-phase extraction- high-performance liquid chromatography-ultraviolet detection method is efficient for the analysis of trace sulfonylurea herbicides in environmental samples.

An electrochemical sensor-based carbon black associated with a modified mixed oxide (SiO2/TiO2/Sb2O5) for direct determination of thiamethoxam in raw honey and water samples.

The study aimed to develop an electrochemical sensor based on glassy carbon, mixed oxide (SiO2/TiO2/Sb2O5), and carbon black. The material was synthesized, characterized, and used to determine thiamethoxam in raw honey and water. The morphologic structure and electrochemical performance of the sensor was characterized by scanning electron microscopy and cyclic voltammetry. Differential pulse voltammetry with a concentration of 0.1 mol L-1 of Britton-Robinson buffer at pH 7.0 allowed the generation of a method to determine thiamethoxam in a linear range of 0.25 to 100.5 µmol L-1 and with a limit of detection of 0.012 µmol L-1. The system efficiently quantified traces of thiamethoxam in raw honey and tap water samples. The modified sensor did not present interferences of K+, Na+, Ca2+, Mg2+, glyphosate, imidacloprid, and carbendazim. In addition, the device showed good recovery values for thiamethoxam when applied directly to honey and water samples without any treatment, presenting an electrochemical sensor to monitor real-time hazardous substances in environmental and food matrices.

Electrochemical aptasensor based on electrodeposited poly(3,4-ethylenedioxythiophene)-graphene oxide coupled with Au@Pt nanocrystals for the detection of 17ß-estradiol.

An electrochemical aptasensor is reported for the sensitive and specific monitoring of 17ß-estradiol (E2) based on the modification of electrodeposited poly(3,4-ethylenedioxythiophene) (PEDOT)-graphene oxide (GO) coupled with Au@Pt nanocrystals (Au@Pt). With excellent conductivity, chemical stability and active sites, the PEDOT-GO nanocomposite film was firstly in situ polymerized on the glassy carbon electrode by cyclic voltammetry. Subsequently, one-step synthesized Au@Pt were decorated on the conductive polymer, providing a platform for immobilizing the aptamer and enhancing the detecting sensitivity. With the addition of E2, since the interfacial electron transfer process was retarded by the E2-aptamer complex, the differential pulse voltammetry signal decreased gradually. Under optimum conditions, the calibration curve of E2 exhibited a linear range between 0.1 pM and 1 nM, with a low detection limit (S/N = 3) of 0.08 pM. The developed aptasensor showed admiring selectivity, stability, and reproducibility. It was tested in human serum, lake water and tap water samples after low-cost and simple pretreatment. Consequently, the developed platform could provide a new design thought for ultrasensitive detection of E2 in clinical and environmental samples.

Green Extraction Techniques as Advanced Sample Preparation Approaches in Biological, Food, and Environmental Matrices: A Review.

Green extraction techniques (GreETs) emerged in the last decade as greener and sustainable alternatives to classical sample preparation procedures aiming to improve the selectivity and sensitivity of analytical methods, simultaneously reducing the deleterious side effects of classical extraction techniques (CETs) for both the operator and the environment. The implementation of improved processes that overcome the main constraints of classical methods in terms of efficiency and ability to minimize or eliminate the use and generation of harmful substances will promote more efficient use of energy and resources in close association with the principles supporting the concept of green chemistry. The current review aims to update the state of the art of some cutting-edge GreETs developed and implemented in recent years focusing on the improvement of the main analytical features, practical aspects, and relevant applications in the biological, food, and environmental fields. Approaches to improve and accelerate the extraction efficiency and to lower solvent consumption, including sorbent-based techniques, such as solid-phase microextraction (SPME) and fabric-phase sorbent extraction (FPSE), and solvent-based techniques (µQuEChERS; micro quick, easy, cheap, effective, rugged, and safe), ultrasound-assisted extraction (UAE), and microwave-assisted extraction (MAE), in addition to supercritical fluid extraction (SFE) and pressurized solvent extraction (PSE), are highlighted.

Chromium speciation by the combination of high-performance liquid chromatography and inductively coupled plasma-optical emission spectrometry.

A hyphenated instrumental method high-performance liquid chromatography-inductively coupled plasma-optical emission spectrometry (HPLC-ICP-OES) was used for the separation and determination of Cr(III) and Cr(VI). After the chromatographic separation of chromium species by anion exchange column, their spectrophotometric detection was carried out by ICP-OES system. Important instrumental and chromatographic parameters were investigated via univariate optimization approach to obtain high signal to noise ratio and good resolution for chromium species. Under the optimum HPLC-ICP-OES conditions, limit of detection (LOD) values for Cr(III) and Cr(VI) were found to be 0.27 and 0.05 mg/kg, respectively. In addition, accuracy and applicability of developed method were checked by recovery experiments performed with the spiked soil, grass, and water samples. High percent recovery results (88-104%) were achieved by utilizing matrix matching calibration strategy for the selected samples. The results showed that this method was accurate and applicable to soil, grass, and water samples.

Microbial bioassays in environmental toxicity testing.

Accidental spills and the misuse of chemicals may lead to current and legacy environmental contamination and pose concerns over possible (eco)toxicological secondary effects and risks toward non-target microbes and higher eukaryotes, including humans, in ecosystems. In the last decades, scientists and regulators have faced requests to thoroughly screen, prioritize and predict the possible deleterious effects of the huge numbers of existing and emerging xenobiotics, wastewaters and environmental samples on biological systems. In this context, it has become necessary to develop and validate (eco)toxicity bioassays based on microorganisms (e.g., bacteria, microalga, yeast, filamentous fungi, protozoa) as test-organisms whose data should be meaningful for environmental (micro)organisms that may be exposed to contaminated environments. These generally simple, fast and cost-effective bioassays may be preliminary and complementary to the more complex and long-term whole-organism animal-based traditional ecotoxicity tests. With the goal of highlighting the potential offered by microbial-based bioassays as non-animal alternatives in (eco)toxicity testing, the present chapter provides an overview of the current state-of-the art in the development and use of microbial toxicity bioassays through the examination of relatively recent examples with a diverse range of toxicity endpoints. It goes into the (eco)toxicological relevance of these bioassays, ranging from the more traditional microalga- and bacterial-based assays already accepted at regulatory level and commercially available to the more innovative microbial transcriptional profiling and gene expression bioassays, including some examples of biosensors.