Compounds In Environmental Water Research Articles

Continuous-flow analysis of nitrogen compounds in environmental water using a copper–zinc reduction coil

The copper–cadmium reduction method has been applied to determine nitrogen compounds in heavily contaminated environmental water. However, there is an international demand to reduce the use of cadmium because it is harmful to humans and environment. Hence, a copper–zinc reduction continuous flow analysis system without using cadmium was developed for nitrogen‐compound determination. However, the effects of seawater contaminants on this analytical method remains unknown. Therefore, in this study, the effects of contaminants on the developed method are investigated, and the applicability of the method to environmental water analysis is examined. Resultantly, interference due to magnesium precipitation is confirmed; however, this could be prevented by adjusting the concentration of the analytical reagent, i.e,. ethylenediaminetetraacetic acid disodium. The measurement of certified reference materials under the new conditions, with precipitation countermeasures, show good results, with an accuracy of over 96%. Additionally, a recovery study using actual environmental water afforded good results, with recovery of >95% for all samples. These results indicate that the proposed method is an excellent, cadmium-free analytical method capable of analyzing environmental water as effectively as conventional methods.

Comparative analysis of UV-initiated ARPs for degradation of the emerging substitute of perfluorinated compounds: Does defluorination mean the sole factor?

Due to the increasing attention for the residual of per- and polyfluorinated compounds in environmental water, Sodium p-Perfluorous Nonenoxybenzenesulfonate (OBS) have been considered as an alternative solution for perfluorooctane sulfonic acid (PFOS). However, recent detections of elevated OBS concentrations in oil fields and Frontal polymerization foams have raised environmental concerns leading to the decontamination exploration for this compound. In this study, three advanced reduction processes including UV-Sulfate (UV-SF), UV-Iodide (UV-KI) and UV-Nitrilotriacetic acid (UV-NTA) were selected to evaluate the removal for OBS. Results revealed that hydrated electrons (eaq−) dominated the degradation and defluorination of OBS. Remarkably, the UV-KI exhibited the highest removal rate (0.005 s−1) and defluorination efficiency (35 %) along with the highest concentration of eaq− (K = −4.651). Despite that nucleophilic attack from eaq− on sp2 carbon and H/F exchange were discovered as the general mechanism, high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (HPLC/Q-TOF-MS) analysis with density functional theory (DFT) calculations revealed the diversified products and routes. Intermediates with lowest fluorine content for UV-KI were identified, the presence nitrogen-containing intermediates were revealed in the UV-NTA. Notably, the nitrogen-containing intermediates displayed the enhanced toxicity, and the iodine poly-fluorinated intermediates could be a potential-threat compared to the superior defluorination performance for UV-KI.

Simultaneous and sensitive detection of methylparaben and its metabolites by using molecularly imprinted solid-phase microextraction fiber array technique

BackgroundMethylparaben (MP), a commonly used antibacterial preservative, is widely used in personal care products, foods, and pharmaceuticals. MP and its metabolites are easy to enter the water environment, and their exposure and accumulation have negative effects on the ecological environment and human health, and have endocrine disrupting activity and potential physiological toxicity. It is still the primary issue of environmental analysis and ecological risk assessment to develop simple and reliable methods for simultaneous sensitive detection of these compounds in environmental water. ResultsIn this paper, a flexible molecularly imprinted fiber array strategy is proposed for simultaneous enrichment and detection of trace MP and its four main metabolites. The experimental results showed that the three-fiber imprinted fiber array constructed by MP imprinted fiber had the best effect on the simultaneous enrichment of these five target analytes. The enrichment capacity of the imprinted fiber array was 214–456 times, 314–1201 times and 38–685 times that of commercial PA, PDMS and PDMS/DVB fiber arrays, respectively. The limit of detection (LOD) of this method was 0.033 μg L−1. The spiked recovery rate was 86.78–113.96 %, and RSD was less than 9.17 %. In addition, this molecularly imprinted SPME fiber array has good stability, long service life and can be used repeatedly at least 100 times. SignificanceThis molecularly imprinted fiber array strategy can flexibly assemble different molecularly imprinted SPME fibers together, effectively improve the enrichment ability and detection sensitivity, and achieve simultaneous selective enrichment and detection of several analytes. This is an easy, efficient and reliable method for monitoring several trace analytes simultaneously in intricate environmental matrices.

Real-Time and Online Monitoring of Hazardous Volatile Organic Compounds in Environmental Water by an Unmanned Shipborne Mass Spectrometer System.

Hazardous volatile organic compounds (VOCs) are one of the critical concerns in environmental water due to their toxicity to aquatic organisms and drinking water. Therefore, rapid detection of hazardous VOCs in environmental water is highly needed as many analytical methods are limited to on-site monitoring. In this work, we designed a novel unmanned shipborne mass spectrometer (US-MS) system for the real-time and online monitoring of hazardous VOCs in environmental water. The US-MS system consists of a miniaturized mass spectrometer, an automatic sampling device, a robust unmanned ship, and other monitoring and control devices. Along with the navigation route of the US-MS system, environmental water was continuously introduced into the MS system for the online and real-time detection of hazardous VOCs via a liquid/gas exchange membrane. Analytical performances of the US-MS system were investigated by a mixture of 10 VOCs showing low limits of detection (LODs: 0.31-1.26 ng/mL), good reproducibility (RSDs: 2.93-11.03%, n = 7), and excellent quantitative ability (R2 > 0.99). Furthermore, on-site detection and online monitoring of hazardous volatile contaminants such as benzene, chloroprene, and toluene in different aquatic environments such as rivers and lakes were successfully demonstrated, showing excellent field applicability of the US-MS system. Overall, the newly developed US-MS system could perform on-site, online, and real-time monitoring of complex VOCs in environmental water, showing good performances and versatile applications in water analysis.

Molecularly Imprinted Plasmonic Sensors for the Determination of Environmental Water Contaminants: A Review

The scarcity of clean water leads to the exploration of the possibility of using treated wastewater. However, monitoring campaigns have proven the presence of emerging contaminants, such as pharmaceuticals, pesticides and personal care products, not only in trace amounts. Various analytical methodologies have been developed over the last years for the quantification of these compounds in environmental waters. Facing the need to achieve a higher sensitivity, fast response and practical use via miniaturization, the potential of plasmonic sensors has been explored. Through the introduction of molecularly imprinted polymers (MIPs) as recognition elements, MIP-based plasmonic sensors seem to be a good alternative for monitoring a wide range of analytes in water samples. This work attempts to provide a general overview of this form of sensor, which has been reported as being able to sense different contaminants in waters using surface plasmon resonance (SPR) and surface-enhanced Raman-scattering (SERS) techniques. Particular emphasis is given to the fabrication/recognition procedure, including the preparation of MIPs and the use of metals and nanomaterials to increase the performance characteristics of the sensors.

The Separation of Chlorobenzene Compounds from Environmental Water Using a Magnetic Molecularly Imprinted Chitosan Membrane.

In this work, a magnetic molecularly imprinted chitosan membrane (MMICM) was synthesized for the extraction of chlorobenzene compounds in environmental water using the membrane separation method. The optimal extraction amount for chlorobenzene (9.64 mg·L−1) was found to be a 1:2 solid to liquid ratio, with a 20 min extraction time and 35 °C extraction temperature. This method proved to be successfully applied for the separation and trace quantification of chlorobenzene compounds in environmental water, with the limit of detection (LOD) (0.0016–0.057 ng·L−1), limit of quantification (LOQ) (0.0026–0.098 ng·L−1), and the recoveries ranging (89.02–106.97%).

Quantification of ultra-trace organolead species in environmental water by inductively coupled plasma mass spectrometry with online solid-phase extraction and high performance liquid chromatographic separation

Quantification of organolead compounds in environmental water is an essential task considering much higher toxicity and bioavailability of organolead species than inorganic plumbic ions. However, the speciation of ultra-trace organolead compounds at sub ng L−1 levels is challengeable for current instruments incorporating high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) and even offline enrichment that offer detection limits around several to tens of ng L−1. In this paper, an online solid-phase extraction (SPE) coupled HPLC-ICP-MS method was developed for speciation analysis of trace lead in water. Graphene oxide bounded silica particles (GO@SiO2) was utilized as the SPE adsorbent because of its superior performance over graphene bounded silica particles and commercial C18 packing particles. High enrichment factors (1603 for TML and 1376 for TEL) were obtained when lead species in 10 mL sample was adsorbed by 1 mM sodium dodecyl benzene sulfonate (SDBS) preconditioned GO@SiO2 at 10 mL min−1 and then eluted by 5 μL of 5 mM SDBS. Because of the highly efficient preconcentration, detection limits were downscaled to be 0.018 for TML and 0.023 ng L−1 for TEL with relative standard deviations below 5%. Additionally, the proposed method also yielded rapid separation of Pb(II), TML and TEL (8 min) by using green mobile phases (aqueous solutions of 5 mM sodium 1-pentanesulfonate at pH 2.5 with/without 4 mM tetrabutylammounium hydroxide). Upon successful application to fresh water, TML and TEL were only presented in the river water whereas Pb(II) was only existed in the tap water, along with accuracy validation by good spiked recoveries (93–106%).

Targeted and non-targeted analysis of organic compounds of moderate polarity in water using liquid chromatography-time of flight mass spectrometry in all ion mode with particular reference to analysis of pesticides

We have developed a novel yet efficient method for the multi residue analysis of organic compounds of diverse polarities in water using Liquid Chromatography-Time of Flight mass spectrometry (LC-MS-TOF) equipped with a jet stream Electrospray ionization (ESI) source. Use of three different fragmentor voltages (low, medium and high) enabled the qualitative and quantitative analysis of a diverse range of targeted organic compounds in environmental waters. No prior optimization of compounds being quantified was required, the limiting factors were ionization behaviour of compounds under conditions of ESI and good chromatography. Same data file could be subjected to repeated post-run data analysis to figure out the presence of non-targeted compounds, including designer drugs if any. The technique has been illustrated with reference to a group of pesticides having diverse chromatographic and ionization behaviours. The optimized Solid Phase Extraction (SPE) followed by method validation yielded a robust yet simple quantitative method for a group of fourteen pesticides. We were able to achieve quantitation at 10 ng/L or lower depending upon ionization behaviour of substrates against the usual regulatory requirement of 1000 ng/L. The method was used for targeted and non-targeted detection of pesticides in Nueces estuary waters, TX, USA, and several untargeted pesticides, pharmaceuticals and personal care products were identified.

Selective monitoring of acidic and basic compounds in environmental water by capsule phase microextraction using sol-gel mixed-mode sorbents followed by liquid chromatography-mass spectrometry in tandem

In addition to the diverse extraction techniques available, capsule phase microextraction (CPME), which uses a microextraction capsule (MEC), has recently been introduced as a sorptive-based sample preparation technique. In this study, two different MECs (MEC-C18/SAX and MEC-C18/SCX) based on mixed-mode ion-exchange technology were synthesized and evaluated for the selective extraction of a group of ionizable compounds, including acidic and basic analytes. A sulfonic acid was used as the cation-exchange group in MEC-C18/SCX, and a quaternary amine as the anion-exchange group in MEC-C18/SAX. The extraction parameters optimized were sample pH, elution solvent, sample/elution volume and extraction/elution time. The optimized CPME method followed by LC-MS/MS was used to determine the ionizable compounds in environmental water samples, including river water and effluent wastewater, with excellent selectivity and matrix effect values below -30% (except -33% for mephedrone) and apparent recovery results ranging from 40% to 69%, except for ibuprofen (< 35%) and atenolol (< 25%). The analytical method was validated for environmental water samples, and used in the analysis of several samples in which some of the target compounds were found at ng L-1 concentration levels.

Facile fabrication of functional groups-rich sorbent for the efficient enrichment of aromatic N- and S-containing compounds in environmental waters

Extraction strategy is designed for the pretreatment of low contents of aromatic N- and S-containing compounds (ANSCs) in environmental waters prior to chromatographic analysis. To enrich studied ANSCs effectively, poly (9-vinylanthracene/4-vinylphenylboronic acid-co-ethylene dimethacrylate/divinylbenzene) polymeric monolithic sorbent were facilely fabricated using the one-step free radical polymerization. Various technologies were employed to investigate the structure and morphology of the resultant monolith. Combining with solid-phase microextraction format, the sorbent exhibited satisfying concentrated performance for ANSCs through multiply interactions under the optimized conditions. After desorption with eluent, the retained analytes were analyzed by HPLC. Results showed that the extraction efficiencies ranged from 51.6 to 93.2%. The linear ranges and limits of detection were 0.01–150 μg/L and 0.63–2.64 ng/L, respectively. Furthermore, the precisions were all below 10%. The introduced approach was productively practiced on three real water samples for simultaneous quantification of studied ANSCs, and the fortified recoveries ranged from 81.5 to 118%. All the results well evidenced that prepared sorbent can enrich ANSCs effectively and the introduced method is reliable alternative for routine analysis of ANSCs in environmental waters.

Nonderivatization method for determination of glyphosate, glufosinate, bialaphos, and their main metabolites in environmental waters based on magnetic metal-organic framework pretreatment.

A novel magnetic metal-organic framework composite was prepared by a self-assembly approach. The material properties were characterized by Fourier-transform infrared spectroscopy, vibrating sample magnetometry, thermogravimetry and differential thermogravimetric analysis, and X-photoelectron spectroscopy. Then, the as-prepared material was used as an adsorbent and indicated great enrichment ability toward glyphosate, glufosinate, bialaphos, and their main metabolites aminomethylphosphonic acid and 3-methylphosphinicopropionic acid. Based on this, an efficient magnetic solid-phase extraction method combined with ultra high performance liquid chromatography with high-resolution mass spectrometry for the pretreatment and determination of five target compounds in environmental waters was established. Parameters that could impact on the adsorption performance had been studied in detail. The proposed method was successfully applied for the simultaneous determination of glyphosate, glufosinate, bialaphos, and their main metabolites aminomethylphosphonic acid and 3-methylphosphinicopropionic acid in environmental water with recoveries in range of 86.2-104.6% with relative standard deviations less than 10%. Desired linearity was achieved varying from 1 to 100μg/L for five target analytes, respectively. The limits of detection were between 0.01 and 0.03μg/L.

Analysis of Perfluorinated Compounds in Environmental Water Using Decyl-perfluorinated Magnetic Mesoporous Microspheres as Magnetic Solid-Phase Extraction Materials and Microwave-Assisted Derivatization Followed by Gas Chromatography-mass Spectrometry.

In this work, a new method was developed for perfluorinated compounds (PFCs) analysis in water samples based on decyl-perfluorinated magnetic mesoporous nanocomposites microspheres-assisted extraction and microwave-assisted derivatization followed by gas chromatography-mass spectrometry analysis. The decyl-perfluorinated magnetic mesoporous nanocomposites have several advantages such as fast separation ability, good dispersibility in water sample and high selective preconcentration of PFCs. Various parameters, including eluting solvent and volume, the amounts of absorbents, extraction time and elution time, the microwave-assisted derivatization conditions were optimized. Validation studies showed that this method has good linearity (r2 > 0.9970), satisfactory precision (RSD < 7.8%) and high recovery (93-107%). The limits of detection were found to be 0.055-0.086 μg/L and the limits of quantification be 0.18-0.28 μg/L, respectively. The results indicated that the proposed method has advantages of convenience, good sensitivity and high efficiency. The method has been applied successfully to analyze perfluorinated organic acids in real water samples.

Photocatalytic decomposition of selected biologically active compounds in environmental waters using TiO2/polyaniline nanocomposites: Kinetics, toxicity and intermediates assessment

A comprehensive study of the removal of selected biologically active compounds (pharmaceuticals and pesticides) from different water types was conducted using bare TiO2 nanoparticles and TiO2/polyaniline (TP-50, TP-100, and TP-150) nanocomposite powders. In order to investigate how molecular structure of the substrate influences the rate of its removal, we compared degradation efficiency of the initial substrates and degree of mineralization for the active components of pharmaceuticals (propranolol, and amitriptyline) and pesticides (sulcotrione, and clomazone) in double distilled (DDW) and environmental waters. The results indicate that the efficiency of photocatalytic degradation of propranolol and amitriptyline was higher in environmental waters: rivers (Danube, Tisa, and Begej) and lakes (Moharač, and Sot) in comparison with DDW. On the contrary, degradation efficacy of sulcotrione and clomazone was lower in environmental waters. Further, of the all catalysts applied, bare TiO2 and TP-100 were found to be most effective in the mineralization of propranolol and amitriptyline, respectively, while TP-150 appeared to be the most efficient in terms of sulcotrione and clomazone mineralization. Also, there was no significant toxicity observed after the irradiation of pharmaceuticals or pesticides solutions using appropriate catalysts on rat hepatoma (H-4-II-E), mouse neuroblastoma (Neuro-2a), human colon adenocarcinoma (HT-29), and human fetal lung (MRC-5) cell lines. Subsequently, detection and identification of the formed intermediates in the case of sulcotrione photocatalytic degradation using bare TiO2 and TP-150 showed slightly different pathways of degradation. Furthermore, tentative pathways of sulcotrione photocatalytic degradation were proposed and discussed.

Chemometrics-enhanced high performance liquid chromatography strategy for simultaneous determination on seven nitroaromatic compounds in environmental water

Nitroaromatic compounds pose a significant risk to human health and other living organisms. However, conventionally high performance liquid chromatography (HPLC) methods are complicated and time-consuming for complete separation of multiple nitroaromatic compounds due to their high structure-similarity. In the work, a facile yet effective strategy, which combines HPLC embedded by diode array detection (HPLC-DAD) with multivariate curve resolution-alternating least squares (MCR-ALS), is explored to improve the HPLC analysis. Based on the strategy, seven nitroaromatic compounds with similar structures could be rapidly quantified under a simple isocratic elution condition (acetonitrile/water: 65:35, v/v) within 10 min. With the aid of the second-order advantage of MCR-ALS, acceptable quantification results are still achieved for the real water samples, despite of significantly overlapping peaks resulted from the similar structures of the analytes and the unexpected interferences from the real water sample. The error analysis and the elliptical joint confidence region (EJCR) test further confirm the reliability of the predicted result. Thereby, the HPLC method coupled with the second-order calibration algorithm could provide a simple, quick and accurate strategy for simultaneous determination on the multiple nitroaromatic compounds in environmental monitoring.

Research Progresses of Determination of Perfluorinated Compounds in Environmental Water and Solid Samples

Abstract Perfluorinated compounds (PFCs), a group of persistent organic pollutants, have been widely detected in environmental media and posed great threats to human health. The researches on environmental pollution and health risk of PFCs have become the hot subject in recent years. The advanced and reliable analytical methods for determination of PFCs are urgently needed since various homologs and isomers of PFCs are detected at trace levels (ng g−1 or μg L−1) in environment. At present, studies on analytical methods of trace PFCs in environmental samples have been extensively carried out in China and abroad. However, reviews which systematically discuss the sample pretreatment, analytical method, and matrix effect of determination of PFCs in complex environmental matrixes are hardly available. Therefore, the present review highlights the pretreatment methods, matrix effects, and detection techniques (especially isomers) of PFCs in environmental samples (water, sediment, sludge, soil and plant). It hopes that this review will provide valuable references for the environmental researches on PFCs.

環境水・底質・魚類からの有機フッ素化合物の検出

環境水・底質・魚類からの有機フッ素化合物の検出

Single Drop Microextraction Analytical Technique for Simultaneous Separation and Trace Enrichment of Atrazine and its Major Degradation Products from Environmental Waters Followed by Liquid Chromatographic Determination

In this work, a method of single drop microextraction (SDME) combined with high performance liquid chromatography (HPLC) with diode array detection (DAD) was studied for trace level enrichment as well as simultaneous determination of atrazine (ATZ) and its major degradation products such as desethylatrazine (DEA) and desisopropylatrazine (DIA) in environmental waters. The main factors influencing the extraction procedure including types and volume of extraction solvent, sample stirring rate, sample solution pH, extraction temperature, extraction time, and salting out effect were optimized. The method detection limits were as low as 0.01 for ATZ and 0.05 for both DIA and DEA, with coefficients of determination better than 0.998 within a linear range of 0.5-150 μg L-1. Under the optimal conditions, the proposed method was applied for the analysis of real water samples and good spiked recoveries in the range of 65.6%-96.3% with relative standard deviation of less than 5% were obtained. The results confirmed that the proposed procedure provides reliable precision, linearity and sensitivity and is very effective for analyzing the target compounds in environmental waters. Therefore, the developed SDME method coupled with HPLC-DAD was found to be simple, inexpensive, and environmentally benign sample pretreatment technique.

Determination of Phenolic Compounds in Environmental Water by HPLC Combination with On-Line Solid-Phase Extraction Using Molecularly Imprinted Polymers.

A novel molecularly imprinted polymer (MIP) was synthesized using halloysite nanotubes (HNT) as matrix, β-cyclodextrin (β-CD) and methyl propyl acid (MAA) as functional monomers, and 2,4,6-TCP as template molecule by graft copolymerization. Infrared spectroscopy and transmission electron microscopy (TEM) were used to characterize the as-synthesized imprinted polymer. The selective recognizability of the MIP towards four phenolic analogs were determined and the recognition coefficients for 2,4,6-TCP, 2,6-DCP, 4-CP and phenol were found to be 2.17, 1.85, 2.02 and 1.36, respectively. Using as the packing material of solid-phase extraction, the imprinted polymer has been applied to on-line extraction of the four phenolic compounds in environmental water. The corresponding analytical methods to determine these four phenolic compounds have been developed. Good linear relationships were obtained over the range of 0.05-5.0 mg x L(-1). The average recoveries for spiked samples were in the range of 74.8-97.2%, and the detection limits for 2,4,6-TCP, 2,6-DCP, p-chlorophenol, phenol were 0.19, 0.20, 0.75, 0.73 mg x L(-1), respectively. The method is rapid, accurate and high selectivity. It was feasible for the determination of trace level phenolic compounds in environmental samples.

Rapid activity-directed screening of estrogens by parallel coupling of liquid chromatography with a functional gene reporter assay and mass spectrometry

In this study we developed a new LC nanofractionation platform that combines a human cell (BG1.Luc) gene reporter assay with a high resolution mass spectrometer for the detection and identification of estrogenic and anti-estrogenic compounds in environmental waters. The selection of this assay was based on its high sensitivity and selectivity, which is required for environmental trace level detection. We modified an autosampler and controlled it with in-house developed software to collect fractions in the low second range in microtiter plates. This ensured that chromatographic separation was maintained and allowed straightforward hyphenation with the bioassay. After bioassay testing, bioassay chromatograms were reconstructed and directly correlated with MS chromatograms that were obtained in parallel. This enabled to pinpoint bioactives in the MS chromatogram within a single fractionation cycle and results in a significant increase in throughput compared to traditional EDA studies. The sensitivity of the platform was low enough for environmental waters (80nM for bisphenol A and 320pM and 3.2nM for estradiol and estriol, respectively). In addition, the ability of the platform to detect anti-estrogens was successfully demonstrated as well. Finally, real samples were analysed.

Facile and robust dual interaction modification of hexadecyldimethyl amine magnetic nanoparticles for the ultrasensitive analysis of perfluorinated compounds in environmental water.

In this work, a novel extraction and enrichment technique based on hexadecyldimethyl amine functionalized magnetic nanoparticles has been successfully developed for the preconcentration and ultrasensitive detection of perfluorinated compounds in environmental water samples with high-performance liquid chromatography coupled with tandem triple quadrupole mass spectrometry. As a novel surfactant, hexadecyldimethyl amine functionalized on magnetic nanoparticles was realized through one-step facile and robust quaterization reaction, greatly superior to previous multiple-step and unstable modification. The functional nanoparticles of homogeneous nanospheres and excellent magnetic properties were characterized with scanning electron microscopy, X-ray diffraction patterns, Fourier transform infrared spectroscopy, and vibrating sample magnetometry. Dual mechanisms of both hydrophobic and electrostatic interactions were simultaneously introduced for anionic perfluorinated compounds effective enrichment. Under optimized extraction conditions, satisfactory precision and accuracy for anionic perfluorinated compounds analysis were achieved with good linear ranging from 0.5 to 20 ng/L, as well as fascinating sensitivity with low limits of detection up to 3.0 × 10(-2) -5.0 × 10(-2) ng/L. High preconcentration efficiency and extraction recoveries ranged from 81.04-103.2% with relative standard deviations (n = 5) less than 10% have also been realized. Thereby, our proposed method is convenient and efficient for enrichment, exhibiting good application prospect in future environmental perfluorinated compounds analysis.