Determination of commonly used herbicides in surface water using solid-phase extraction and dual-column HPLC-DAD

The present study describes the application of different solid-phase extraction techniques for the extraction, separation, and quantitative determination of 10 commonly used herbicides with different chemical structures (chlorsulfuron, diuron, bentazone, linuron, chlorpropham, fenoxoprop-ethyl, MCPA, diclofop-methyl, fluazifop-butyl, trifluraline) in water. Octadecyl (C(18)) Empore extraction disks, octadecyl (C(18)), and stryene divinylbenzene (SDB) Bond Elut Env cartridges were compared for solid-phase extraction efficiency. Herbicides were separated and quantified by reversed-phase high performance liquid chromatography with diode-array detection (HPLC-DAD) with simultaneous separation on two columns of differing polarity (C(18) and CN) to confirm identification. Analytical separation was performed simultaneously on C(18) and CN columns. Reanalysis of the sample extracts on a (cyano) CN column were used to confirm the identity of these compounds. Method optimization and validation parameters were presented in this work. Recoveries varied from 76.0% to 99.0% for C(18) disks, from 75.1% to 100.0% for C(18) cartridges, and from 54.0% to 98.0% for SDB cartridges over concentrations at 0.025--0.4 microg L(-1). The limits of detection were 0.012--0.035 microg L(-1).     

Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

Quantitative determination of fluorochemicals in municipal landfill leachates

Twenty-four fluorochemicals were quantified in landfill leachates recovered from municipal refuse using an analytical method based on solid-phase extraction, dispersive-carbon sorbent cleanup, and liquid chromatography/tandem mass spectrometry. The method was applied to six landfill leachates from four locations in the US as well as to a leachate generated by a laboratory bioreactor containing residential refuse. All seven leachates had the common characteristic that short-chain (C₄-C₇) carboxylates or sulfonates were greater in abundance than their respective longer-chain homologs (?C₈). Perfluoroalkyl carboxylates were the most abundant (67 ± 4% on a nanomolar (nM) basis) fluorochemicals measured in leachates; concentrations of individual carboxylates reaching levels up to 2800 ng L⁻¹. Perfluoroalkyl sulfonates were the next most abundant class (22 ± 2%) on a nM basis; their abundances in each of the seven leachates derived from municipal refuse were greater for the shorter-chain homologs (C₄ and C₆) compared to longer-chain homologs (C₈ and C₁₀). Perfluorobutane sulfonate concentrations were as high as 2300 ng L⁻¹. Sulfonamide derivatives composed 8 ± 2.1% (nM basis) of the fluorochemicals in landfill leachates with methyl (C₄ and C₈) and ethyl (C₈) sulfonamide acetic acids being the most abundant. Fluorotelomer sulfonates (6:2 and 8:2) composed 2.4 ± 1.3% (nM basis) of the fluorochemicals detected and were present in all leachates.     

Spatio-temporal variations of selected pesticide residues in the Kurose River in Higashi-Hiroshima city,Japan

ABSTRACT

This study investigated spatio-temporal variations of selected pesticide residues in the Kurose River in Higashi-Hiroshima city (Hiroshima Prefecture), Japan. Water samples were collected from the river at seven sites every month for 1 year (March 2016 to February 2017). Pesticide residues were extracted from the samples by a solid phase extraction using Sep Pack C₁₈ cartridges. Once extracted, the samples were analyzed for cyanazine, simetryn, fenarimol, isoprothiolane, and diazinon using a reversed-phase high-performance liquid chromatography ultraviolet visible (HPLC-UV Vis) system. The limits of detection were 3.60, 4.10, 2.80, 6.50, and 7.30 ng L^-1 for cyanazine, simetryn, fenarimol, isoprothiolane, and diazinon, respectively. Good recovery rates (88%–102%), and mean percent relative standard deviation range (1.00%–5.70%) (n = 6) were obtained with a spiking at 0.20 µg L^-1. The maximum concentrations of 282, 391, 60, 1086, and 1194 ng L^-1 were obtained for cyanazine, simetryn, isoprothiolane, fenarimol, and diazinon, respectively. Cyanazine was the most frequently detected pesticide (64% of the samples, n = 84), followed by simetryn (58%), and then diazinon (57%). The highest and lowest pesticide concentrations were measured during the periods May–June, and January–February, respectively. Principal component analysis revealed three principal components in which the pesticides were linked to dissolved organic matter and total suspended solids. The major water quality parameters (electrical conductivity, pH, Na⁺, K⁺, Mg²⁺, Ca²⁺, NH₄⁺, NO₃^?, Cl^?, SO₄^2?, NO₂^?, and temperature) showed no clear trends for these pesticides. The presence of simetryn and isoprothiolane was largely attributed to rice paddy farms, whereas diazinon was associated mostly with vegetable farms and orchards. The diazinon and isoprothiolane patterns were consistent with their use of controlling insects and fungi in the prefecture. The maximum diazinon concentration detected was higher than the human safe level specified by the European Union (100 ng L^-1) in Council Directive 98/83/EC. This is of concern because of the bioconcentration potential of these residues in fish and other marine animals consumed by humans.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO₄ plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO₄ plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg^?1, respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Extraction of Sudan dyes from environmental water by hemimicelles-based magnetic titanium dioxide nanoparticles

A novel method for the extraction of Sudan dyes including Sudan I, II, III, and IV from environmental water by magnetic titanium dioxide nanoparticles (Fe₃O₄@TiO₂) coated with sodium dodecylsulfate (SDS) as adsorbent was reported. Fe₃O₄@TiO₂ was synthesized by a simple method and was characterized by transmission electron microscopy, Fourier-transform infrared spectrometry, and vibrating sample magnetometer. The magnetic separation was quite efficient for the adsorption and desorption of Sudan dyes. The effect of the amount of SDS, extraction time, pH, desorption condition, maximal extraction volume, and humic acid on the extraction process were investigated. This method was employed to analyze three environmental water samples. The results demonstrated that our proposed method had wide linear range (25–5,000 ng L^?1) with a good linearity (R ²?>?0.999) and low detection limits (2.9–7.3 ng L^?1). An enrichment factor of 1,000 was achieved. In all three spiked levels (25, 250, and 2,500 ng L^?1), the recoveries of Sudan dyes were in the range of 86.9–93.6 %. The relative standard deviations obtained were ranging from 2.5 to 9.3 %. That is to say, the new method was fast and effective for the extraction of Sudan dye from environmental water.     

High-performance liquid chromatography (HPLC) as a tool for monitoring the fate of fluazinam in soil

Fluazinam is a widely used pesticide employed against the fungal disease late blight in potato cultivation. A specific, repeatable, and rapid high-performance liquid chromatography (HPLC) method utilizing a diode array detector (DAD) was developed to determine the presence of fluazinam in soil. The method consists of acetonitrile (ACN) extraction, clean-up with solid-phase extraction (SPE), and separation using a mobile phase consisting of 70% ACN and 30% water (v/v), including 0.02% acetic acid. HPLC was performed with a C18 column and the detection wavelength was 240 nm. The method was successfully applied to an incubation experiment and to soil samples taken from potato fields where fluazinam had been applied two to three times during the on-going growing season. In the 90-day incubation experiment, analytical standard fluazinam and the commercial fungicide Shirlan^® were added to soil samples that had never been treated with fluazinam, and were then extracted with ACN and 0.01 M calcium chloride (CaCl₂). Fluazinam was not extractable with CaCl₂, indicating that it does not leach to watercourses in the dissolved form. Recovery with ACN extraction for sandy soils was 72–95% immediately after application and 53–73% after 90 days of incubation. Out of the eight potato field soil samples, fluazinam was found in two samples at concentrations of 2.1 mg kg^?1 and 1.9 mg kg^?1, well above the limit of quantification (0.1 mg kg^?1).     

Multiresidue method for high-performance liquid chromatography determination of carbamate pesticides residues in tea samples

A multiresidue method was developed to determine 19 carbamate pesticides in tea samples. Optimizations of different parameters, such as the type of extraction solvents, clean-up cartridges, and elution solvents were carried out. The developed method used acetonitrile as extraction solvent, amino cartridge for adsorbents and acetone-n-hexane as the eluting solution. Nineteen carbamate residues were then analyzed by high-pressure liquid chromatography (HPLC) with fluorescence detector. The present results showed good linearity by correlation coefficients of more than 0.9999 for all analyses. Limits of detection and quantification varied from 0.0005–0.023 mg L^{? 1}, 0.008–0.077 mg L^{? 1}, respectively. Recoveries of sixteen carbamate pesticides ranged from 65% to 135% at the spiked level of 0.5, 1.0 and 2.0 mg L^{? 1}. The relative standard deviations were lower than 20% and coefficient of variations were lower than 15%. The results indicate that the proposed method provides an effective multi and trace level screening determination of carbamate pesticides residues for tea samples.     

Distribution,source, and environmental risk assessment of phthalate esters (PAEs) in water,suspended particulate matter,and sediment of a typical Yangtze River Delta City,China

Phthalates (PAEs) in drinking water sources such as the Yangtze River in developing countries had aroused widespread concern. Here, the water, suspended particulate matter (SPM), and sediment samples were collected from 15 sites in wet and dry seasons in Zhenjiang, for the determination of six PAEs (DMP, DEP, DIBP, DBP, DEHP, and DOP) using the solid-phase extraction (SPE) or ultrasonic extraction coupled with gas chromatography-mass spectrometry (GC-MS). The total concentrations of six PAEs (Σ₆PAEs) spanned a range of 2.65–39.31 μg L^?1 in water, 1.97–34.10 μg g^?1 in SPM, and 0.93–34.70 μg g^?1 in sediment. The partition coefficients (K_d1) of PAEs in water and SPM phase ranged from 0.004 to 3.36 L g^?1 in the wet season and from 0.12 to 2.84 L g^?1 in the dry season. K_d2 of PAEs in water and sediment phase was 0.001–9.75 L g^?1 in the wet season and 0.006–8.05 L g^?1 in the dry season. The dominant PAEs were DIBP, DBP, and DEHP in water and SPM, DIBP, DEHP, and DOP in sediment. The concentration of DBP in water exceeded the China Surface Water Standard. The discharge of domestic sewage and industrial wastewater might be the main potential sources of PAEs. The risk quotient (RQ) method used for the risk assessment revealed that DBP (0.01 < RQ < 1) posed a medium risk, while DIBP and DEHP (RQ > 1) posed a high environmental risk in water, DIBP (RQ > 1) also showed a high risk in sediment.

     

Monitoring of pesticide residues in a cotton crop soil

Abstract

This paper reports on the residues of methyl parathion (O,O‐dimethyl O‐4‐nitrophenyl phosphorothioate), trifluralin (α, α, α‐trifluoro‐2, 6‐dinitro‐N, N‐dipropyl‐p‐toluidine), endosulfan [(1, 4, 5, 6, 7, 7‐hexachloro‐8, 9, 10‐trinorborn‐5‐en‐2, 3‐ylenebismethylene) sulfite] and dimethoate (O, O‐dimethyl S‐methylcarbamoylmethyl phosphorodithioate) in a cotton crop soil. Soil samples (0–15 cm) were collected at different periods from the cotton crop farm and subjected to Soxhlet extraction. The extracted material was analysed after clean‐up by a HP5890 II gas Chromatograph equipped with a ⁶³Ni electron‐capture detector (ECD‐⁶³Ni) and fitted with a 25m x 0,2mm i.d. fused silica capillary column [Ultra‐2 (5% phenylmethyl polysiloxane)]. The recoveries of the pesticide residues from the spiked control soil were determined after Soxhlet extraction and C₁₈ cartridges clean‐up by using radiotracer techniques with the corresponding ¹⁴C‐pesticides. The results show that in the cotton crop soil the pesticide residues under study were present in the range of 0.1 to 0.4 mg ? kg^‐1. Endosulfan was found to be rapidly degraded in the soil and formed a sulfate metabolite.     

Occurrence of cyclophosphamide and epirubicin in wastewaters by direct injection analysis–liquid chromatography–high-resolution mass spectrometry

Background, aim, and scope

According to the high incidence of cancer worldwide, the amount of cytostatic drugs administered to patients has increased. These compounds are excreted to wastewaters, and therefore become potential water contaminants. At this stage, very little is known on the presence and elimination of cytostatic compounds in wastewater treatment plants (WWTP). The aim of this study was to develop a liquid chromatography?Chigh-resolution mass spectrometry (LC?COrbitrap?CMS) method for the determination of cyclophosphamide and epirubicin in wastewaters. These compounds represent two outmost used cytostatic agents.

Materials and methods

Extraction and analytical conditions were optimized for cyclophosphamide and epirubicin in wastewater. Both solid-phase extraction using Oasis 200?mg hydrophilic?Clipophilic balanced (HLB) cartridges and direct injection analysis were evaluated. Mass spectral characterization and fragmentation conditions were optimized at 50,000 resolving power (full width at half maximum, m/z 200) to obtain maximum sensitivity and identification performance. Quality parameters (recoveries, limits of detection, and repetitivity) of the methods developed were determined, and best performance was obtained with direct water analysis of the centrifuged wastewater. Finally, this method was applied to determine the presence of cyclophosphamide and epirubicin in wastewaters from a hospital effluent, an urban effluent, and influents and effluents from three WWTP.

Results and discussion

Cyclophosphamide and epirubicin were recovered after 50?mL preconcentration on solid-phase extraction 200?mg Oasis HLB cartridges (87% and 37%, respectively), and no breakthrough was observed by extracting 500?mL of water. Limits of detection were of 0.35 and 2.77?ng/L for cyclophosphamide and epirubicin, respectively. On the other hand, direct injection of water spiked at 1???g/L provided recoveries of 107% for cyclophosphamide and 44% for epirubicin and limits of detection from 3.1 to 85?ng?L^?1, respectively. The analysis of wastewaters using direct injection analysis revealed the presence of cyclophosphamide and epirubicin in WWTP influents and hospital and urban effluents at levels ranging from 5.73 to 24.8???g?L^?1.

Conclusions

The results obtained in this study demonstrate the capability of LC?COrbitrap?CMS for accurate trace analysis of these very polar contaminants. This method permitted to identify cyclophosphamide and epirubicin in wastewaters and influents of WWTP, but no traces were detected in WWTP effluents. The methodology herein developed is sensitive and robust and applicable for screening of a large number of samples since no preconcentration is needed.     

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 %.     

Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC

The present study describes the application of different extraction techniques for the preconcentration of ten commonly found acidic and non-acidic polar herbicides (2,4-D, atrazine, bensulfuron-methyl, clomazone, dicamba, diuron, MCPA, metolachlor, simazine and triclopyr) in the aqueous environment. Liquid-liquid extraction (LLE) with dichloromethane, solid-phase extraction (SPE) using Oasis HLB cartridges or SBD-XC Empore disks were compared for extraction efficiency of these herbicides in different matrices, especially water samples from contaminated agricultural drainage water containing high concentrations of particulate matter. Herbicides were separated and quantified by high performance liquid chromatography (HPLC) with an ultraviolet detector. SPE using SDB-XC Empore disks was applied to determine target herbicides in the Murrumbidgee Irrigation Area (NSW, Australia) during a two-week survey from October 2005 to November 2005. The daily aqueous concentrations of herbicides from 24-h composite samples detected at two sites increased after run-off from a storm event and were in the range of: 0.1-17.8 microg l(-1), < 0.1-0.9 microg l(-1) and 0.2-17.8 microg l(-1) at site 1; < 0.1-3.5 microg l(-1), < 0.1-0.2 microg l(-1) and < 0.2-3.2 microg l(-1) at site 2 for simazine, atrazine and diuron, respectively.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

Rapid metal extractability tests from polluted mining soils by ultrasound probe sonication and microwave-assisted extraction systems

Ultrasonic probe sonication (UPS) and microwave-assisted extraction (MAE) were used for rapid single extraction of Cd, Cr, Cu, Ni, Pb, and Zn from soils polluted by former mining activities (Mónica Mine, Bustarviejo, NW Madrid, Spain), using 0.01 mol L^?1 calcium chloride (CaCl₂), 0.43 mol L^?1 acetic acid (CH₃COOH), and 0.05 mol L^?1 ethylenediaminetetraacetic acid (EDTA) at pH 7 as extracting agents. The optimum extraction conditions by UPS consisted of an extraction time of 2 min for both CaCl₂ and EDTA extractions and 15 min for CH₃COOH extraction, at 30% ultrasound (US) amplitude, whereas in the case of MAE, they consisted of 5 min at 50 °C for both CaCl₂ and EDTA extractions and 15 min at 120 °C for CH₃COOH extraction. Extractable concentrations were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). The proposed methods were compared with a reduced version of the corresponding single extraction procedures proposed by the Standards, Measurements and Testing Programme (SM&T). The results obtained showed a great variability on extraction percentages, depending on the metal, the total concentration level and the soil sample, reaching high values in some areas. However, the correlation analysis showed that total concentration is the most relevant factor for element extractability in these soil samples. From the results obtained, the application of the accelerated extraction procedures, such as MAE and UPS, could be considered a useful approach to evaluate rapidly the extractability of the metals studied.     

Measuring Concentrations of Volatile Organic Compounds in Vinyl Flooring

ABSTRACT

The initial solid-phase concentration of volatile organic compounds (VOCs) is a key parameter influencing the emission characteristics of many indoor materials. Solid-phase measurements are typically made using solvent extraction or thermal headspace analysis. The high temperatures and chemical solvents associated with these methods can modify the physical structure of polymeric materials and, consequently, affect mass transfer characteristics.

To measure solid-phase concentrations under conditions resembling those in which the material would be installed in an indoor environment, a new technique was developed for measuring VOC concentrations in vinyl flooring (VF) and similar materials. A 0.09-m² section of new VF was punched randomly to produce ~200 0.78-cm² disks. The disks were milled to a powder at -140 °C to simultaneously homogenize the material and reduce the diffusion path length without loss of VOCs. VOCs were extracted from the VF particles at room temperature by fluidized-bed desorption (FBD) and by direct thermal desorption (DTD) at elevated temperatures. The VOCs in the extraction gas from FBD and DTD were collected on sorbent tubes and analyzed by gas chromatog-raphy/mass spectrometry (GC/MS). Seven VOCs emitted by VF were quantified. Concentration measurements by FBD ranged from 5.1 |ig/g VF for n-hexadecane to 130 |Jg/g VF for phenol. Concentrations measured by DTD were higher than concentrations measured by FBD. Differences between FBD and DTD results may be explained using free-volume and dual-mobility sorption theory, but further research is necessary to more completely characterize the complex nature of a diffusant in a polymer matrix.     

Detection of fullerenes (C60 and C70) in commercial cosmetics

Detection methods are necessary to quantify fullerenes in commercial applications to provide potential exposure levels for future risk assessments of fullerene technologies. The fullerene concentrations of five cosmetic products were evaluated using liquid chromatography with mass spectrometry to separate and specifically detect C₆₀ and C₇₀ from interfering cosmetic substances (e.g., castor oil). A cosmetic formulation was characterized with transmission electron microscopy, which confirmed that polyvinylpyrrolidone encapsulated C₆₀. Liquid-liquid extraction of fullerenes from control samples approached 100% while solid-phase and sonication in toluene extractions yielded recoveries of 27-42%. C₆₀ was detected in four commercial cosmetics ranging from 0.04 to 1.1 μg/g, and C₇₀ was qualitatively detected in two samples. A single-use quantity of cosmetic (0.5 g) may contain up to 0.6 μg of C₆₀, demonstrating a pathway for human exposure. Steady-state modeling of fullerene adsorption to biosolids is used to discuss potential environmental releases from wastewater treatment systems.     

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.     

Gas Chromatographic Analysis of Ambient Halogenated Compounds

Abstract

Fugitive dust emission from limestone extraction areas is a significant pollution source. The cracking operation in limestone extraction areas easily causes high total suspended particulate (TSP) concentrations in the atmosphere, occasionally exceeding the 1-hr national emission standard of Taiwan (500 μg/m³). The concentration and size distribution were measured at different distances (0.05–15 km) in the extraction areas. The highest hourly concentrations of TSP, PM₁₀ (suspended particulate matter [PM] smaller than 10 μm), and PM_2.5 (suspended PM smaller than 2.5 μm) are 1111, 825, and 236 μg/m³, respectively, during the cracking process. Measurement results obtained from the Micro-Orifice Uniform Deposit Impactor indicated that the mass median aerodynamic diameter is ～0.7 μm, with the geometric standard deviation exceeding 7. In addition, the emission factors are 0.143 and 0.211 kg/t for both vertical well and stair extraction operations, respectively. Experimental results demonstrate that the corresponding TSP control efficiencies for spraying water, planting grass, setting short walls, paving gravel roads, and establishing vertical well transportation are ～55, 50, 44, 22, and 30%, respectively. Furthermore, the PM₁₀ control efficiencies are ～45, 41, 54, 35, and 30%, respectively, whereas the PM_2.5 control efficiencies are roughly 23, 31, 15, 11, and 10%, individually.