An electrochemical nanocomposite modified carbon paste electrode as a sensor for simultaneous determination of hydrazine and phenol in water and wastewater samples

In this study, we report preparation of a high sensitive electrochemical sensor for determination of hydrazine in the presence of phenol in water and wastewater samples. In the first step, we describe synthesis and characterization of ZnO/CNTs nanocomposite with different methods such as transmission electron microscopy (TEM) and X-ray diffraction (XRD). In the second step, application of the synthesis nanocomposite describes the preparation of carbon paste electrode modified with n-(4-hydroxyphenyl)-3,5-dinitrobenzamide as a high sensitive and selective voltammetric sensor for determination of hydrazine and phenol in water and wastewater samples. The mediated oxidation of hydrazine at the modified electrode was investigated by cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy (EIS). Also, the values of catalytic rate constant (k) and diffusion coefficient (D) for hydrazine were calculated. Square wave voltammetry (SWV) of hydrazine at the modified electrode exhibited two linear dynamic ranges with a detection limit (3σ) of 8.0 nmol L^?1. SWV was used for simultaneous determination of hydrazine and phenol at the modified electrode and quantitation of hydrazine and phenol in some real samples by the standard addition method.     

Nanocellulosic fiber-modified carbon paste electrode for ultra trace determination of Cd (II) and Pb (II) in aqueous solution

In recent years, increasing awareness of the environmental impact of heavy metals has prompted a demand for monitoring and decontaminating industrial wastes prior to discharging into natural water bodies. This paper describes the preparation and electrochemical application of carbon paste electrode modified with nanocellulosic fibers for the determination of cadmium and lead in water samples using anodic stripping voltammetry. First, cadmium and lead were adsorbed on the carbon paste electrode surface at open circuit potential, followed by anodic stripping voltammetric scan from -1 to 0 V. Different factors affecting sensitivity and precision of the electrode, including accumulating solvent, pH of the accumulating solvent, accumulation time, supporting electrolyte, and scan rate were investigated. The proposed method was also applied to the determination of Cd (II) and Pb (II) in the presence of other interfering metal ions and cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, and Triton X-100 as a representative of cationic, anionic, and neutral surfactants. Linear calibration curves were obtained in the concentration ranges of 150–650 μg?L^?1 and 80–300 μg?L^?1, respectively, for cadmium and lead at an accumulated time of 10 min with limits of detection 88 and 33 μg?L^?1. Optimized working conditions are defined as acetate buffer of pH?5 as accumulating solvent, hydrochloric acid as supporting electrolyte, and scan rate 50 mV/s. This technique does not use mercury and therefore has a positive environmental benefit. The method is reasonably sensitive and selective and has been successfully applied to the determination of trace amounts of Cd (II) and Pb (II) in water samples.     

Hg<Superscript>2+</Superscript> detection using a disposable and miniaturized screen-printed electrode modified with nanocomposite carbon black and gold nanoparticles

A miniaturized screen-printed electrode (SPE) modified with a carbon black-gold nanoparticle (CBNP-AuNP) nanocomposite has been developed as an electrochemical sensor for the detection of inorganic mercury ions (Hg²⁺). The working electrode surface has been modified with nanocomposite constituted of CBNPs and AuNPs by an easy drop casting procedure that makes this approach extendible to an automatable mass production of modified SPEs. Square wave anodic stripping voltammetry (SWASV) was adopted to perform Hg²⁺ detection, revealing satisfactory sensitivity and detection limit, equal to 14 μA ppb^?1 cm^?2 and 3 ppb, respectively. The applicability of the CBNP-AuNP-SPE for the determination of inorganic mercury has been assessed in river water by a simple filtration and acidification of the sample as well as in soil by means of a facile acidic extraction procedure assisted by ultrasound.     

Electrochemical study of the fungicide acibenzolar-s-methyl and its voltammetric determination in environmental samples

The electrochemical behavior of new generation fungicide acibenzolar-s-methyl (S-methyl 1,2,3-benzothiadiazole-7-carbothioate, ASM) on the hanging mercury drop electrode (HMDE) was investigated using square wave adsorptive stripping voltammetry. This method of determination is based on the irreversible reduction of ASM at the HMDE. The well-defined ASM peak was observed at ?0.4 V (vs. Ag/AgCl) in BR buffer at pH 2.2. The reduction peak current was proportional to concentration of ASM from 1.0 × 10^?8 to 6.0 × 10^?8 mol L^?1 with detection and quantification limit 3.0 × 10^?9 and 1.0 × 10^?8 mol L^?1, respectively. The applicability of the developed method for analysis of spiked samples of tap water, river water, and soil is illustrated. The effect of adsorption on the mercury electrode was studied in detail using the AC impedance method. Possible interferences with other common pesticides and heavy metal ions were examined. Clarification of the electrode mechanism was made using cyclic voltammetry (CV) technique.     

The capability of estuarine sediments to remove nitrogen: implications for drinking water resource in Yangtze Estuary

Water in the Yangtze Estuary is fresh most of the year because of the large discharge of Yangtze River. The Qingcaosha Reservoir built on the Changxing Island in the Yangtze Estuary is an estuarine reservoir for drinking water. Denitrification rate in the top 10 cm sediment of the intertidal marshes and bare mudflat of Yangtze Estuarine islands was measured by the acetylene inhibition method. Annual denitrification rate in the top 10 cm of sediment was 23.1 μmol m^?2 h^?1 in marshes (ranged from 7.5 to 42.1 μmol m^?2 h^?1) and 15.1 μmol m^?2 h^?1 at the mudflat (ranged from 6.6 to 26.5 μmol m^?2 h^?1). Annual average denitrification rate is higher at mashes than at mudflat, but without a significant difference (p?=?0.084, paired t test.). Taking into account the vegetation and water area of the reservoir, a total 1.42?×?10⁸ g N could be converted into nitrogen gas (N₂) annually by the sediment, which is 97.7 % of the dissolved inorganic nitrogen input through precipitation. Denitrification in reservoir sediment can control the bioavailable nitrogen level of the water body. At the Yangtze estuary, denitrification primarily took place in the top 4 cm of sediment, and there was no significant spatial or temporal variation of denitrification during the year at the marshes and mudflat, which led to no single factor determining the denitrification process but the combined effects of the environmental factors, hydrologic condition, and wetland vegetation.     

Ultrasensitive determination of carbendazim in water and orange juice using a carbon paste electrode

A carbon paste electrode was used for the electrochemical quantification of carbendazim in water and orange juice samples. Carbendazim oxidation on the electrode surface was found to be controlled by adsorption. The novel electrochemical procedure for carbendazim quantification employed differential pulse voltammetry using a carbon paste electrode under optimal conditions. Carbendazim oxidation currents were linear at concentrations of 2.84 to 45.44 µg L^?1, with a limit of detection of 0.96 µg L^?1. The proposed method was applied to carbendazim quantification in ultrapurified water, river water, and orange juice. Recovery rates in water and orange juice samples were in the 97%–101% range, indicating that the method can be employed to determine carbendazim in these matrices, with advantages including shorter analysis time and lower cost than routine methods such as chromatography or spectroscopy. The electrode showed good reproducibility, remarkable stability, and especially good surface renewability by simple mechanical polishing. The recovery rates observed were highly concordant with those obtained for high-performance liquid chromatography, having a relative standard deviation of less than 1.3%.     

Dietary arsenic consumption and urine arsenic in an endemic population: response to improvement of drinking water quality in a 2-year consecutive study

We assessed the association between arsenic intake through water and diet, and arsenic levels in first morning-void urine under variable conditions of water contamination. This was done in a 2-year consecutive study in an endemic population. Exposure of arsenic through water and diet was assessed for participants using arsenic-contaminated water (≥50 μg L^?1) in a first year (group I) and for participants using water lower in arsenic (<50 μg L^?1) in the next year (group II). Participants with and without arsenical skin lesions were considered in the statistical analysis. Median dose of arsenic intake through drinking water in groups I and II males was 7.44 and 0.85 μg kg body wt.^?1 day^?1 (p <0.0001). In females, it was 5.3 and 0.63 μg kg body wt.^?1 day^?1 (p <0.0001) for groups I and II, respectively. Arsenic dose through diet was 3.3 and 2.6 μg kg body wt.^?1 day^?1 (p?=?0.088) in males and 2.6 and 1.9 μg kg body wt.^?1 day^?1 (p?=?0.0081) in females. Median arsenic levels in urine of groups I and II males were 124 and 61 μg L^?1 (p?=?0.052) and in females 130 and 52 μg L^?1 (p?=?0.0001), respectively. When arsenic levels in the water were reduced to below 50 μg L^?1 (Indian permissible limit), total arsenic intake and arsenic intake through the water significantly decreased, but arsenic uptake through the diet was found to be not significantly affected. Moreover, it was found that drinking water mainly contributed to variations in urine arsenic concentrations. However, differences between male and female participants also indicate that not only arsenic uptake, but also many physiological factors affect arsenic behavior in the body and its excretion. As total median arsenic exposure still often exceeded 3.0 μg kg body wt.^?1 day^?1 (the permissible lower limit established by the Joint Expert Committee on Food Additives) after installation of the drinking water filters, it can be concluded that supplying the filtered water only may not be sufficient to minimize arsenic availability for an already endemic population.     

Preliminary toxicological assessment of phthalate esters from drinking water consumed in Portugal

This paper reports, for the first time, the concentrations of selected phthalates in drinking water consumed in Portugal. The use of bottled water in Portugal has increased in recent years. The main material for bottles is polyethylene terephthalate (PET). Its plasticizer components can contaminate water by leaching, and several scientific studies have evidenced potential health risks of phthalates to humans of all ages. With water being one of the most essential elements to human health and because it is consumed by ingestion, the evaluation of drinking water quality, with respect to phthalate contents, is important. This study tested seven commercial brands of bottled water consumed in Portugal, six PET and one glass (the most consumed) bottled water. Furthermore, tap water from Lisbon and three small neighbor cities was analyzed. Phthalates (di-n-butyl phthalate ester (DnBP), bis(2-ethylhexyl) phthalate ester (DEHP), and di-i-butyl phthalate ester (DIBP)) in water samples were quantified (PET and glass) by means of direct immersion solid-phase microextraction and ionic liquid gas chromatography associated with flame ionization detection or mass spectrometry due to their high boiling points and water solubility. The method utilized in this study showed a linear range for target phthalates between 0.02 and 6.5 μg L^?1, good precision and low limits of detection that were between 0.01 and 0.06 μg L^?1, and quantitation between 0.04 and 0.19 μg L^?1. Only three phthalates were detected in Portuguese drinking waters: dibutyl (DnBP), diisobutyl (DIBP), and di(ethylhexyl) phthalate (DEHP). Concentrations ranged between 0.06 and 6.5 μg L^?1 for DnBP, between 0.02 and 0.16 μg L^?1 for DEHP, and between 0.1 and 1.89 μg L^?1 for DIBP. The concentration of DEHP was found to be up to five times higher in PET than in glass bottled water. Surprisingly, all the three phthalates were detected in glass bottled water with the amount of DnBP being higher (6.5 μg L^?1) than in PET bottled water. These concentrations do not represent direct risk to human health. Regarding potable tap water, only DIBP and DEHP were detected. Two of the cities showed concentration of all three phthalates in their water below the limits of detection of the method. All the samples showed phthalate concentrations below 6 μg L^?1, the maximum admissible concentration in water established by the US Environmental Protection Agency. The concentrations measured in Portuguese bottled waters do not represent any risk for adult's health.     

Determination of phenols and pharmaceuticals in municipal wastewaters from Polish treatment plants by ultrasound-assisted emulsification–microextraction followed by GC–MS

A method combining ultrasound-assisted emulsification–microextraction (USAEME) with gas chromatography–mass spectrometry (GC–MS) was developed for simultaneous determination of four acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, and diclofenac, as well as four phenols, 4-octylphenol, 4-n-nonylphenol, bisphenol A, and triclosan in municipal wastewaters. Conditions of extraction and simultaneous derivatization were optimized with respect to such aspects as type and volume of extraction solvent, volume of derivatization reagent, kind and amount of buffering salt, location of the test tube in the ultrasonic bath, and extraction time. The average correlation coefficient of the calibration curves was 0.9946. The LOD/(LOQ) values in influent and effluent wastewater were in the range of 0.002–0.121/(0.005–0.403) μg L^?1 and 0.002–0.828/(0.006–2.758) μg L^?1, respectively. Quantitative recoveries (≥94 %) and satisfactory precision (average RSD 8.2 %) were obtained. The optimized USAEME/GC–MS method was applied for determination of the considered pharmaceuticals and phenols in influents and treated effluents from nine Polish municipal wastewater treatment plants. The average concentration of acidic pharmaceuticals in influent and effluent wastewater were in the range of 0.06–551.96 μg L^?1 and 0.01–22.61 μg L^?1, respectively, while for phenols were in the range of 0.03–102.54 μg L^?1 and 0.02–10.84 μg L^?1, respectively. The removal efficiencies of the target compounds during purification process were between 84 and 99 %.     

Environmental effects of anticholinesterasic therapeutic drugs on a crustacean species,Daphnia magna

The presence of pharmaceutical drugs in the environment is an important field of toxicology, since such residues can cause deleterious effects on exposed biota. This study assessed the ecotoxicological acute and chronic effects of two anticholinesterasic drugs, neostigmine and pyridostigmine in Daphnia magna. Our study calculated 48 h-EC₅₀ values for the immobilization assay of 167.7 μg L^?1 for neostigmine and 91.3 μg L^?1 for pyridostigmine. In terms of feeding behavior, we calculated a 5 h-EC₅₀ for filtration rates of 7.1 and 0.2 μg L^?1 for neostigmine and pyridostigmine, respectively; for the ingestion rates, the calculated EC₅₀ values were, respectively, 7.5 and 0.2 μg L^?1 for neostigmine and pyridostigmine. In the reproduction assay, the most affected parameter was the somatic growth rate (LOECs of 21.0 and 2.9 μg L^?1 for neostigmine and pyridostigmine, respectively), followed by the fecundity (LOECs of 41.9 and 11.4 μg L^?1 for neostigmine and pyridostigmine, respectively). We also determined a 48 h-IC₅₀ for cholinesterase activity of 1.7 and 4.5 μg L^?1 for neostigmine and pyridostigmine, respectively. These results demonstrated that both compounds are potentially toxic for D. magna at concentrations in the order of the μg L^?1.     

Toxicity of atrazine and its bioaccumulation and biodegradation in a green microalga,Chlamydomonas mexicana

This study evaluated the toxicity of herbicide atrazine, along with its bioaccumulation and biodegradation in the green microalga Chlamydomonas mexicana. At low concentration (10 μg L^?1), atrazine had no profound effect on the microalga, while higher concentrations (25, 50, and 100 μg L^?1) imposed toxicity, leading to inhibition of cell growth and chlorophyll a accumulation by 22 %, 33 %, and 36 %, and 13 %, 24 %, and 27 %, respectively. Atrazine 96-h EC50 for C. mexicana was estimated to be 33 μg L^?1. Microalga showed a capability to accumulate atrazine in the cell and to biodegrade the cell-accumulated atrazine resulting in 14–36 % atrazine degradation at 10–100 μg L^?1. Increasing atrazine concentration decreased the total fatty acids (from 102 to 75 mg g^?1) and increased the unsaturated fatty acid content in the microalga. Carbohydrate content increased gradually with the increase in atrazine concentration up to 15 %. This study shows that C. mexicana has the capability to degrade atrazine and can be employed for the remediation of atrazine-contaminated streams.     

Direct electrochemical detection of glyphosate at carbon paste electrode and its determination in samples of milk,orange juice,and agricultural formulation

Abstract

This paper describes a simple, inexpensive, highly sensitive, selective, and efficient electrochemical method to determine glyphosate (GLY) in samples of milk, orange juice, and agricultural formulation. The oxidation reaction on the electrode surface was electrochemically characterised by cyclic voltammetry (CV) and square wave voltammetry (SWV). The investigation of GLY at carbon paste electrode revealed a non-reversible oxidation peak at +0.95 V versus Ag/AgCl, which was used for electrochemical detection of GLY. The operating parameters (pH, frequency, step potential, and amplitude) were optimised in relation to the peak current intensity, and a calibration curve was set up in a concentration range of 4.40?×?10^?8–2.80?×?10^?6 mol L^?1, with a detection limit of 2?×?10^?9 mol L^?1. After calibration curve was plotted, the developed procedure was applied to determine GLY in previously contaminated samples: milk and orange juice, and in a commercial formulation, obtaining recovery values between 98.31% and 103.75%. These results show that the proposed method can be used for GLY quantification in different samples with high sensitivity, specificity, stability, and reproducibility.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

Elevated water temperature reduces the acute toxicity of the widely used herbicide diuron to a green alga, Pseudokirchneriella subcapitata

In the actual environment, temperatures fluctuate drastically through season or global warming and are thought to affects risk of pollutants for aquatic biota; however, there is no report about the effect of water temperature on toxicity of widely used herbicide diuron to fresh water microalgae. The present research investigated inhibitory effect of diuron on growth and photosynthetic activity of a green alga Pseudokirchneriella subcapitata at five different temperatures (10, 15, 20, 25, and 30 °C) for 144 h of exposure. As a result, effective diuron concentrations at which a 50 % decrease in algal growth occurred was increased with increasing water temperature ranging from 9.2 to 20.1 μg L^–1 for 72 h and 9.4–28.5 μg L^–1 for 144 h. The photochemical efficiency of photosystem II (F _v/F _m ratio) was significantly reduced at all temperatures by diuron exposure at 32 μg L^–1 after 72 h. Inhibition rates was significantly increased with decreased water temperature (P?<?0.01). Intracellular H₂O₂ levels as an indicator of oxidative stress were also decreased with increasing temperature in both control and diuron treatment groups and were about 2.5 times higher in diuron treatment groups than that of controls (P?<?0.01). Our results suggest water temperatures may affect the toxicokinetics of diuron in freshwater and should therefore be considered in environmental risk assessment.     

Psychotropic drugs in mixture alter swimming behaviour of Japanese medaka (<Emphasis Type="Italic">Oryzias latipes</Emphasis>) larvae above environmental concentrations

Psychiatric pharmaceuticals, such as anxiolytics, sedatives, hypnotics and antidepressors, are among the most prescribed active substances in the world. The occurrence of these compounds in the environment, as well as the adverse effects they can have on non-target organisms, justifies the growing concern about these emerging environmental pollutants. This study aims to analyse the effects of six psychotropic drugs, valproate, cyamemazine, citalopram, sertraline, fluoxetine and oxazepam, on the survival and locomotion of Japanese medaka Oryzias latipes larvae. Newly hatched Japanese medaka were exposed to individual compounds for 72 h, at concentrations ranging from 10 μg L^?1 to 10 mg L^?1. Lethal concentrations 50 % (LC₅₀) were estimated at 840, 841 and 9,136 μg L^?1 for fluoxetine, sertraline and citalopram, respectively, while other compounds did not induce any significant increase in mortality. Analysis of the swimming behaviour of larvae, including total distance moved, mobility and location, provided an estimated lowest observed effect concentration (LOEC) of 10 μg L^?1 for citalopram and oxazepam, 12.2 μg L^?1 for cyamemazine, 100 μg L^?1 for fluoxetine, 1,000 μg L^?1 for sertraline and >10,000 μg L^?1 for valproate. Realistic environmental mixture of the six psychotropic compounds induced disruption of larval locomotor behaviour at concentrations about 10- to 100-fold greater than environmental concentrations.     

Trace analysis of parabens preservatives in drinking water treatment sludge,treated, and mineral water samples

Parabens have been widely used as antimicrobial agents, mainly in food products, pharmaceuticals, and cosmetics. Although they are known as safe preservatives, they also cause some harm to human health, which has been discussed lately. Therefore, the aim of this study was to evaluate the occurrence of nine parabens (including isomers) in mineral and drinking waters, besides in drinking water treatment sludge (DWTS) samples with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS). Both methods solid phase extraction (SPE) and QuEChERS were validated. Calibration curves showed a correlation coefficient of 0.99 for all compounds. LOQ values ranged from 0.04 to 4 μg L^?1 in aqueous matrices and from 5 to 500 ng g^?1 in DWTS. Recoveries between 70 and 115% were reached with RSD below 20% for all compounds in SPE whereas recoveries between 62 and 119% were found with RSD below 20% for almost all compounds in QuEChERS. Matrix effect had low values (<?20%); it was only above 20% for methylparaben in the SPE and for pentylparaben in the QuEChERS. Using a quick and simple extraction procedures with SPE, QuEChERS, and LC-MS/MS analyses, these methods proved to be selective and sensitive. They were successfully applied to real samples (treated water, mineral water, and sludge), and methylparaben was detected at concentration levels below 0.242 μg L^?1 in mineral and treated water samples and 10 ng g^?1 in DWTS samples.     

Characterization of carbonaceous aerosols over Delhi in Ganga basin: seasonal variability and possible sources

The mass concentration of carbonaceous species, organic carbon (OC), and elemental carbon (EC) using a semicontinuous thermo-optical EC-OC analyzer, and black carbon (BC) using an Aethalometer were measured simultaneously at an urban mega city Delhi in Ganga basin from January 2011 to May 2012. The concentrations of OC, EC, and BC exhibit seasonal variability, and their concentrations were ～2 times higher during winter (OC 38.1?±?17.9 μg m^?3, EC 15.8?±?7.3 μg m^?3, and BC 10.1?±?5.3 μg m^?3) compared to those in summer (OC 14.1?±?4.3 μg m^?3, EC 7.5?±?1.5 μg m^?3, and BC 4.9?±?1.5 μg m^?3). A significant correlation between OC and EC (R?=?0.95, n?=?232) indicate their common emission sources with relatively lower OC/EC ratio (range 1.0–3.6, mean 2.2?±?0.5) suggests fossil fuel emission as a major source of carbonaceous aerosols over the station. On average, mass concentration of EC was found to be ～38 % higher than BC during the study period. The measured absorption coefficient (b_abs) was significantly correlated with EC, suggesting EC as a major absorbing species in ambient aerosols at Delhi. Furthermore, the estimated mass absorption efficiency (σ_abs) values are similar during winter (5.0?±?1.5 m² g^?1) and summer (4.8?±?2.8 m² g^?1). Significantly high aerosol loading of carbonaceous species emphasize an urgent need to focus on air quality management and proper impact assessment on health perspective in these regions.     

Tea bag filter paper as a novel protective membrane for micro-solid phase extraction of butachlor in aqueous samples

An innovative, cost-effective, simple, and environmental friendly tea bag filter paper protected micro-solid phase extraction (μ-SPE) technique was developed for the first time with the aim to miniaturize and minimize the use of organic solvents for the extraction and determination of butachlor in aqueous samples. The μ-SPE device was produced by packing 3.0 mg of an easily synthesized new sorbent, hydroxyl-functionalized polypyrrole (OH-PPY), inside a small tea bag filter paper sachet (1.0 cm × 0.5 cm) that served as a protective envelope. Both the extraction and desorption procedures were facilitated by sonication. Due to the high porosity and the fast water absorption of the tea bag filter paper, the analyte could easily diffuse through and enhance the interaction with the sorbent. Under the optimized conditions for the GC-ECD and the μ-SPE, the limit of detection (S/N ≥ 3) was 2.0 μg L^?1 while the limit of quantitation (S/N ≥ 10) was 10.0 μg L^?1. The recoveries of the butachlor spiked at 0.050, 0.10, and 0.50 μg mL^?1 ranged from 77.9 ± 3.0 to 112.5 ± 2.9%. The proposed method was successfully applied for the determination of butachlor in water samples from paddy cultivation sites. The levels found were from non-detectable to 24.71 ± 0.37 μg L^?1.     

Mine water geochemistry and metal flux in a major historic Pb-Zn-F orefield, the Yorkshire Pennines, UK

Recent studies have shown up to 6 % of rivers in England and Wales to be impacted by discharges from abandoned metal mines. Despite the large extent of impacts, there are still many areas where mine water impact assessments are limited by data availability. This study provides an overview of water quality, trace element composition and flux arising from one such area; the Yorkshire Pennine Orefield in the UK. Mine drainage waters across the orefield are characterised by Ca–HCO₃–SO₄-type waters, with moderate mineralization (specific electrical conductance: 160–525 μS cm^?1) and enrichment of dissolved Zn (≤2003 μg?L^?1), Ba (≤971 μg?L^?1), Pb (≤183 μg?L^?1) and Cd (≤12 μg?L^?1). The major ion composition of the waters reflects the Carboniferous gritstone and limestone-dominated country rock, the latter of which is heavily karstified in parts of the orefield, while sulphate and trace element enrichment is a product of the oxidation of galena, sphalerite and barite mineralization. Contaminant flux measurements at discharge sites highlight the disproportionate importance of large drainage levels across the region, which generally discharge into first-order headwater streams. Synoptic metal loading surveys undertaken in the Hebden Beck sub-catchment of the river Wharfe highlight the importance of major drainage levels to instream baseflow contamination, with diffuse sources from identifiable expanses of waste rock becoming increasingly prominent as river flows increase.     

Remediation of acid mine drainage (AMD)-contaminated soil by Phragmites australis and rhizosphere bacteria

Experiments were conducted to assess the impact of citric acid (CA) and rhizosphere bacteria on metal uptake in Phragmites australis cultured in a spiked acid mine drainage (AMD) soil. Rhizosphere iron-oxidizing bacteria (Fe(II)OB) enhanced the formation of Fe plaque on roots, which decreased the uptake of Fe and Mn. CA inhibited the growth of Fe(II)OB, decreased the formation of metal plaque, raised the metal mobility in soil, and increased the accumulation of metals in all tissues of the reeds. The higher the CA dosage, the more metals accumulated into reeds. The total amount of metals in reeds increased from 7.8?±?0.5?×?10^?6 mol plant^?1 (Mn), 1.4?±?0.1?×?10^?3 mol plant^?1 (Fe), and 1.0?±?0.1?×?10^?4 mol plant^?1 (Al) in spiked soil without CA to 22.2?±?0.5?×?10^?6 mol plant^?1 (Mn), 3.5?±?0.06?×?10^?3 mol plant^?1 (Fe), and 5.0?±?0.2?×?10^?4 mol plant^?1 (Al) in soil added with 33.616 g C₆H₈O₇·H₂O for per kilogram soil. CA could be effective at enhancing the phytoremediation of metals from AMD-contaminated soil.