Comparison of automated mixer-assisted mini-scale liquid-liquid extraction coupled with full evaporation dynamic headspace extraction with United States Environmental Protection Agency methods for the gas chromatography-mass spectrometric analysis of chlorinated benzenes.

Three modes of facilitating mini-scale-liquid-liquid-extraction (msLLE) prior to automated integration with full evaporation dynamic headspace (FEDHS) extraction were evaluated in this work. For msLLE, 1.2 mL of dichloromethane (DCM) was added to a conical-bottomed vial containing 7 mL of aqueous sample. The solution was then subjected to three different mixing modes, namely vortex-assistance (where a "whirlpool" was created in the solution), agitation-assistance (where the vial was rotated in circular motion) and quickMix-assistance (where the vial was shaken at a high speed). Vortex-assistance was performed manually while the other two modes were automated using a commercial autosampler. Following this, the DCM extract was transferred automatically to another vial and was then vaporized and sent through a Tenax TA sorbent tube in the FEDHS step. Due to the stronger π interaction between the sorbent and the analytes of interest, the analytes were selectively concentrated while the DCM vapor passed through unhampered. After FEDHS, the analytes were thoroughly desorbed into a gas chromatography-mass spectrometric system for analysis. The applicability of this procedure was validated in the extraction of six chlorinated benzenes (CBs) (1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzne and hexachlorobenzene) from aqueous samples. The quickMix-assisted msLLE-FEDHS approach achieved good absolute extraction recoveries (between 74.2% and 88.7%), low limits of detection (between 0.0006 and 0.0116 µg/L), good linearity (r2≥0.9920), good repeatability (between 1.9% and 8.4%, and good reproducibility (between 9.0% and 13.6%). It was found to be superior to the methods published by the United States Environmental Protection Agency. Five consecutive fully automated quickMix-assisted-msLLE-FEDHS-GC-MS runs spanned only ca. 4 hr.

Deep eutectic solvent dependent carbon dioxide switching as a homogeneous extracting solvent in liquid-liquid microextraction.

A miscible-immiscible deep eutectic solvent (DES) containing monoethanolamine/4-methoxyphenol was used as an extraction solvent in a homogeneous liquid-liquid microextraction (HLLME). The method was used to preconcentrate chlorobenzenes in water samples followed by separating and analyzing them by gas chromatography-mass spectroscopy (GC-MS). A special feature of the new extraction method is that a green miscible solvent was used as an extractant in the HLLME method. The developed extraction technique provided enrichment factors in the range of 13.1-42.1 for extraction from only 1.0 mL of the aqueous sample solution. The effects of various experimental parameters were investigated and optimized. The optimal conditions were as follows: vortex time: 30.0 s, bubbling CO2 gas: 1.0 min, salt concentration: 5.0% w/v, rate and time of centrifuge: 4000.0 rpm and 3.0 min, respectively, and DES volume: 30.0 µL. The limit of detections and the limit of quantifications for the four targeted analytes varied from 0.01-0.15 and 0.025-0.5 µg L-1, respectively. The precision and long-term precision tests for the developed method were found to be less than 11.0%. Two real samples, including toilet air freshener and car perfume, were analyzed. The applied DES in the HLLME method provides a fast means of sample preparation for environmental aqueous sample solutions.

The geometrical characteristics of nickel-based metal organic framework on its entrapment capability.

Here, a three dimensional nickel-based metal organic framework (MOF) was synthesized via solvothermal and room temperature protocols. In order to study the effects of the synthesis conditions on the physical properties such as pore sizes and shapes of the prepared MOFs, their extraction capabilities were examined. Both MOFs were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, Brunauer-Emmett-Teller and thermogravimetric analyses. Brilliant properties such as porous structure, high surface area and considerable thermal stability make them reasonable candidates to be employed as efficient extractive phases. The efficiency of the superior nickel-based MOF was evaluated for headspace needle trap extraction of chlorobenzenes as model compounds in conjunction with gas chromatography-mass spectrometry (GC-MS). The MOF-based extractive phase was conveniently packed in a needle trap device and after extraction, the desorption process was performed via direct insertion of needle into the GC inlet. After optimizing the extraction/desorption conditions, the figures of merit such as linear dynamic range was in the range of 5-1000 ng L-1 (R2 > 0.987) while the limits of detection and quantification values were 2-10 and 6-30 ng L-1, respectively. The intra- and inter-day relative standard deviations for three replicates at the concentration level of 50 ng L-1 were in the range of 7-9% and 9-12%, respectively. The needle-to-needle reproducibility was also found to be in the range of 5-11%. Acceptable relative recovery values at the concentration level of 50 ng L-1 ranged from 85 to 96%, showing no significant matrix effect.

Removal of dimethachlon from soils using immobilized cells and enzymes of a novel potential degrader Providencia stuartii JD.

The first potential degrader capable of detoxifying dimethachlon (NDPS) was isolated and identified as Providencia stuartii JD, whose free cells and freely crude enzymes degraded more than 80% and 90% of 50 mg L-1 NDPS in liquid culture within 7 d and 2 h, respectively. Strain JD metabolized NDPS through the typical pathway, in which NDPS was firstly transformed into succinic acid and 3, 5-dichloroanilin, and the latter was then converted to phenol, which was subsequently degraded to muconic acid further subjected to the mineralization. The immobilization obviously improved the stability and adaptability of cells and enzymes. In laboratory non-sterile soils treated by free or immobilized cells and enzymes, 50 mg kg-1 NDPS decreased to 15.66 and 13.32 mg kg-1, or 8.32 and 2.18 mg kg-1 within 7 d, respectively. In field, immobilized cells and enzymes exhibited significantly higher efficiencies in removing 20.250 kg a.i. ha-1 NDPS wettable powder from soils after 9 d (96.02% and 98.56%) than free cells and enzymes (79.35% and 66.45%). This study highlights that strain JD promises the great potential to remove hazardous NDPS residues and its immobilized cells and enzymes possess the more promising advantages in the bioremediation of NDPS-contaminated soils in situ.

Co- and self-activated synthesis of tailored multimodal porous carbons for solid-phase microextraction of chlorobenzenes and polychlorinated biphenyls.

Highly sensitive solid-phase microextraction (SPME) of broad-spectrum organic micropollutants is a significant challenge due to the limited available pore sizes and pore size distributions (PSDs) of the probes. In this work, we synthesized novel multimodal porous carbons (MPCs) using facile and environment-friendly route for the first time, through direct carbonization of a potassium citrate and calcium citrate mixture. The co-carbonization process formed hierarchical structures with super-high specific surface areas (up to 3270 m2 g-1) and pore volumes (up to 1.79 cm3 g-1). The PSD was easily controlled through adjustment of the mixture ratios of potassium citrate to calcium citrate. Moreover, the MPCs were partly graphitized, and showed great thermal stability (>450 ℃). MPC-coated probes were prepared and applied to extract chlorobenzenes (CBs) and polychlorinated biphenyls (PCBs) with improved performance, higher extraction capacity than commercial carboxen/polydimethylsiloxane probe. Under optimized conditions, a sensitive detection method for CBs and PCBs was developed by a MPC-coated probe coupled with gas chromatography-electron capture detector. Finally, this method was successfully applied to analyze real environmental water samples with satisfactory recoveries (85.56%-104.30%). The findings are expected to broaden our perspectives for improved design of efficient porous materials for broad-spectrum SPME and other applications.

Simultaneous removal of hexavalent chromium and o-dichlorobenzene by isolated Serratia marcescens ZD-9.

Heavy metals-organics mixture pollution is increasingly concerned and simultaneous removal of organic pollutants and heavy metals is becoming significant. In this study, a strain was isolated from the sediment of a tannery effluent outfalls, which can remove o-dichlorobenzene (o-DCB) and Cr(VI) simultaneously. The bacterial isolate was identified as Serratia marcescens by the 16S rRNA gene sequences. The strain removed about 90% of o-DCB and more than 80% of Cr(VI) at the concentration of 1.29 g L-1 o-DCB and 20 mg L-1 Cr(VI). In the presence of concomitant pollutant o-DCB, the optimal pH (8.0) and temperature (30 °C) were determined for Cr(VI) removal. Changes of the bacterial cells and intracellular black Cr(III) sediments were observed by the TEM auxiliary analysis. The results of the FTIR spectroscopy analysis indicated that hydroxyl, amide and polysaccharides were involved in the process of Cr(VI) removal.

Electrochemical sensing of 4-nitrochlorobenzene based on carbon nanohorns/graphene oxide nanohybrids.

Owing to the harmful nature of 4-nitrochlorobenzene (4-NCB, one toxic organic pollutant) and the low cost, high sensitivity and ease of operation of electrochemical method, it is highly desirable to develop effect electrochemical sensor for the detection of 4-NCB. Herein, by partially unzipping carbon nanohorns (CNHs) via a simple wet-chemistry method, CNHs and graphene oxide (GO) (CNHs/GO) nanohybrids were produced for sensing 4-NCB with synergistic properties. While the retained CNHs offer a path for rapid electron transport, the GO sheets formed by partially unzipping CNHs provide abundant active sites, further increase in surface area as well as improved dispersibility of the CNHs/GO. Our results show that the CNHs/GO modified electrode has excellent sensitivity to 4-NCB with a wide linear response range and a detection limit as low as 10 nM.

Characterization and application of a lanthanide-based metal-organic framework in the development and validation of a matrix solid-phase dispersion procedure for pesticide extraction on peppers (Capsicum annuum L.) with gas chromatography-mass spectrometry.

The metal-organic framework [(La0.9 Sm0.1 )2 (DPA)3 (H2 O)3 ]∞ was synthetized and characterized by X-ray diffractometry, differential thermogravimetric analysis, and infrared spectroscopy. The material was tested for the development and validation of a matrix solid-phase dispersion procedure for extraction of atrazine, bifenthrin, bromuconazole, clofentezine, fenbuconazole, flumetralin, procymidone, and pirimicarb, from peppers, with analysis using gas chromatography with mass spectrometry in the selected ion monitoring mode. The method developed was linear over the range tested (50.0-1000.0 µg/kg for procymidone and 200.0-1000.0 µg/kg for all other pesticides), with correlation coefficients ranging from 0.9930 to 0.9992. Experiments were carried out at 250.0, 500.0, and 1000.0 µg/kg fortification levels, and resulted in recoveries in the range of 52.7-135.0%, with coefficient of variation values between 5.2 and 5.4%, respectively, for [(La0.9 Sm0.1 )2 (DPA)3 (H2 O)3 ]∞ sorbent. Detection and quantification limits ranged from 16.0 to 67.0 µg/kg and from 50.0 to 200.0 µg/kg, respectively, for the different pesticides studied. The results were compared with literature data. The developed and validated method was applied to real samples. The analysis detected the presence of residues of pesticides procymidone, fenbuconazole, flumetralin, clofentezine, atrazine, and bifenthrin.

Hydrophilic magnetic ionic liquid for magnetic headspace single-drop microextraction of chlorobenzenes prior to thermal desorption-gas chromatography-mass spectrometry.

A new, fast, easy to handle, and environmentally friendly magnetic headspace single-drop microextraction (Mag-HS-SDME) based on a magnetic ionic liquid (MIL) as an extractant solvent is presented. A small drop of the MIL 1-ethyl-3-methylimidazolium tetraisothiocyanatocobaltate(II) ([Emim]2[Co(NCS)4]) is located on one end of a small neodymium magnet to extract nine chlorobenzenes (1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,2,3,4-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, and pentachlorobenzene) as model analytes from water samples prior to thermal desorption-gas chromatography-mass spectrometry determination. A multivariate optimization strategy was employed to optimize experimental parameters affecting Mag-HS-SDME. The method was evaluated under optimized extraction conditions (i.e., sample volume, 20 mL; MIL volume, 1 µL; extraction time, 10 min; stirring speed, 1500 rpm; and ionic strength, 15% NaCl (w/v)), obtaining a linear response from 0.05 to 5 µg L-1 for all analytes. The repeatability of the proposed method was evaluated at 0.7 and 3 µg L-1 spiking levels and coefficients of variation ranged between 3 and 18% (n = 3). Limits of detection were in the order of nanograms per liter ranging from 4 ng L-1 for 1,4-dichlorobenzene and 1,2,3,4-tetrachlorobenzene to 8 ng L-1 for 1,2,4,5-tetrachlorobenzene. Finally, tap water, pond water, and wastewater were selected as real water samples to assess the applicability of the method. Relative recoveries varied between 82 and 114% showing negligible matrix effects. Graphical abstract Magnetic headspace single-drop microextraction followed by thermal desorption-gas chromatography-mass spectrometry.

Construction of a hydrazone-linked chiral covalent organic framework-silica composite as the stationary phase for high performance liquid chromatography.

Covalent organic frameworks (COFs), as an emerging class of crystalline porous organic polymers, have great potential for applications in chromatographic separation owning to their fascinating crystalline structures and outstanding properties. However, development of COF materials as novel stationary phases in high performance liquid chromatography (HPLC) is just in its infancy. Herein, we report the design and construction of a new hydrazone-linked chiral COF, termed BtaMth COF, from a chiral hydrazide building block (Mth) and present a one-pot synthetic method for the fabrication of BtaMth@SiO2 composite for HPLC separation of isomers. The as-synthesized BtaMth chiral COF displays good crystallinity, high porosity, as well as excellent chemical stability. Meanwhile, the fabricated HPLC column by using BtaMth@SiO2 composite as the new stationary phase exhibits high resolution performances for the separation of positional isomers including nitrotoluene and nitrochlorobenzene, as well as cis-trans isomers including beta-cypermethrin and metconazole. Additionally, some effects such as the composition of the mobile phase and column temperature for HPLC separations on the BtaMth@SiO2 packed column also have been studied in detail. The successful applications indicate the great potentials of hydrazone-linked chiral COF-silica composite as novel stationary phase for the efficient HPLC separation.

Organochlorine pesticides accumulation and breast cancer: A hospital-based case-control study.

The aim of this study is to detect the accumulation status of organochlorine pesticides in breast cancer patients and to explore the relationship between organochlorine pesticides contamination and breast cancer development. We conducted a hospital-based case-control study in 56 patients with breast cancer and 46 patients with benign breast disease. We detected the accumulation level of several organochlorine pesticides products (ß-hexachlorocyclohexane, γ-hexachlorocyclohexane, polychlorinated biphenyls-28, polychlorinated biphenyls-52, pentachlorothioanisole, and pp'-dichlorodiphenyldichloroethane) in breast adipose tissues of all 102 patients using gas chromatography. Thereafter, we examined the expression status of estrogen receptor, progesterone receptor, human epidermal growth factor receptor-2 (HER2), and Ki-67 in 56 breast cancer cases by immunohistochemistry. In addition, we analyzed the risk of breast cancer in those patients with organochlorine pesticides contamination using a logistic regression model. Our data showed that breast cancer patients suffered high accumulation levels of pp'-dichlorodiphenyldichloroethane and polychlorinated biphenyls-52. However, the concentrations of pp'-dichlorodiphenyldichloroethane and polychlorinated biphenyls-52 were not related to clinicopathologic parameters of breast cancer. Further logistic regression analysis showed polychlorinated biphenyls-52 and pp'-dichlorodiphenyldichloroethane were risk factors for breast cancer. Our results provide new evidence on etiology of breast cancer.

Rods-on-sphere silica particles for high performance liquid chromatography.

Silica spheres covered with rods perpendicular to the particle surface were prepared by a simple one-pot sol-gel process. Thus prepared rods-on-sphere silica particles possessed core-shell structure. Compared to other core-shell silica particles in which the shell was synthesized by the time-consuming multiple-step layer-by-layer coating technique, the shell of our rods-on-sphere particles was formed by directly grown rods from the silica spheres. The coverage of the rods on the particle surface could be tuned by changing the amount of water in the reaction. The rods on the particle surface increased the surface roughness which may help decreasing the A-term. Therefore, the calcined and modified rods-on-sphere silica particles were packed into stainless steel columns and then assessed for the separation of various samples including small molecules and proteins. In comparison with a commercially available Kromasil column, the pressure of the rods-on-sphere column is much lower under the same separation conditions, while the column efficiency was comparable. The separation results demonstrate that rods-on-sphere silica particles are a type of new and highly promising packing stationary phase for high performance liquid chromatography.

Kinetic analysis and degradation pathway for m-dichlorobenzene removal by Brevibacillus agri DH-1 and its performance in a biotrickling filter.

A strain, Brevibacillus agri DH-1, isolated from dry lands was used to remove m-dichlorobenzene. After 48h culturing, the concentrations of m-dichlorobenzene decreased from 26-130 to 7.87-28.87mg/L and dry cell weight for bacterial growth reached 52.43-75.05mg/L. The growth and degradation kinetics were analyzed by the fitting of Haldane-Andrews model and pseudo first-order model. A degradation pathway was proposed according to major intermediates (phenol), chloride ion variation, ring-opening enzyme activity, and high mineralization (0.47gCl-/gm-dichlorobenzene, 0.65 gco2/gm-dichlorobenzene, 0.15 gDCW/gm-dichlorobenzene). In addition, the performance in a biotrickling filter (BTF) was evaluated through removal efficiency and pressure drop values with increasing inlet loading rate from 4.10 to 122.57g/m3/h at three empty bed residence time points (30s, 60s, and 90s). The results demonstrated that strain DH-1 possessed high removal efficiency and stable operation in a BTF.

Dechlorination of three tetrachlorobenzene isomers by contaminated harbor sludge-derived enrichment cultures follows thermodynamically favorable reactions.

Dechlorination patterns of three tetrachlorobenzene isomers, 1,2,3,4-, 1,2,3,5-, and 1,2,4,5-TeCB, were studied in anoxic microcosms derived from contaminated harbor sludge. The removal of doubly, singly, and un-flanked chlorine atoms was noted in 1,2,3,4- and 1,2,3,5-TeCB fed microcosms, whereas only singly flanked chlorine was removed in 1,2,4,5-TeCB microcosms. The thermodynamically more favorable reactions were selectively followed by the enriched cultures with di- and/or mono-chlorobenzene as the main end products of the reductive dechlorination of all three isomers. Based on quantitative PCR analysis targeting 16S rRNA genes of known organohalide-respiring bacteria, the growth of Dehalococcoides was found to be associated with the reductive dechlorination of all three isomers, while growth of Dehalobacter, another known TeCB dechlorinator, was only observed in one 1,2,3,5-TeCB enriched microcosm among biological triplicates. Numbers of Desulfitobacterium and Geobacter as facultative dechlorinators were rather stable suggesting that they were not (directly) involved in the observed TeCB dechlorination. Bacterial community profiling suggested bacteria belonging to the phylum Bacteroidetes and the order Clostridiales as well as sulfate-reducing members of the class Deltaproteobacteria as putative stimulating guilds that provide electron donor and/or organic cofactors to fastidious dechlorinators. Our results provide a better understanding of thermodynamically preferred TeCB dechlorinating pathways in harbor environments and microbial guilds enriched and active in anoxic TeCB dechlorinating microcosms.

Dual degradation of gaseous 1,2-dichlorobenzene and PCDD/Fs using Ce doped VxOy/TiO2 immobilized on cordierite.

The photocatalytic film Ce doped VxOy/TiO2 was loaded on cordierite honeycomb (CHC), and this composite was prepared by sol-gel and dipping method, with Ce, oxides of V and TiO2 as dopant and key substances, respectively. Using gaseous 1,2-dichlorobenzene to replace dioxin as target pollutant, dual degradation experiments at 140-280 °C were carried out (thermal decomposition and photodegradation), and the effects of preparation conditions on catalytic activity were investigated: doping amount of Ce, dipping time in the gel, the concentration of ammonium metavanadate (NH4VO3) solution, dipping time in NH4VO3 solution, sintering temperature. The gaseous samples were taken before and after the reactor and analyzed by gas chromatography. According to the results, the optimal preparation conditions were determined, and the corresponding removal rate was above 95% after 90 min of degradation at 280 °C. The composite was examined by ultrasonic to analyze the adhesive strength between the film and CHC, and further characterized by XRD and SEM. Furthermore, flue gas from waste incinerator was chosen as target pollutant, which contained PCDD/Fs, the industrial sidestream degradation experiment was carried out and showed excellent removal efficiency of the composite, the removal rate of PCDD/Fs reached ca. 90% after 90 min of degradation.

The dynamics of low-chlorinated benzenes in a pilot-scale constructed wetland and a hydroponic plant root mat treating sulfate-rich groundwater.

A rarely used hydroponic plant root mat filter (PRMF, of 6 m(2)) and a horizontal subsurface flow constructed wetland (HSSF CW, of 6 m(2)), operating in continuous flow and discontinuous outflow flushing modes, were investigated for treating sulfate-rich and organic carbon-lean groundwater contaminated with monochlorobenzene (MCB); 1,2-dichlorobenzene (1,2-DCB); 1,4-dichlorobenzene (1,4-DCB); and 2-chlorotoluene. Whereas the mean inflow loads ranged from 1 to 247 mg m(-2) days(-1), the range of mean inflow concentrations of the chlorobenzenes recorded over a period of 7 months was within 0.04 and 8 mg L(-1). A hydraulic surface loading rate of 30 L m(-2) days(-1) was obtained in both systems. The mean load removal efficiencies were found to vary between 87 and 93 % in the PRMF after a flow path of 4 m, while the removal efficiencies were found to range between 46 and 70 % and 71 to 73 % in the HSSF CW operating in a continuous flow mode and a discontinuous outflow flushing mode, respectively. Seasonal variations in the removal efficiencies were observed for all low-chlorinated hydrocarbons both in the PRMF and the HSSF CW, whereby the highest removal efficiencies were reached during the summer months. Sulfide formation occurred in the organic carbon-lean groundwater particularly in summer, which is probably due to the plant-derived organic carbon that fostered the microbial dissimilatory sulfate reduction. Higher redox potential in water was observed in the PRMF. In conclusion, the PRMF could be an option for the treatment of water contaminated with compounds which in particular need oxic conditions for their microbial degradation, such as in the case of low-chlorinated benzenes.

Optimization of headspace solid phase microextraction based on nano-structured ZnO combined with gas chromatography-mass spectrometry for preconcentration and determination of ultra-traces of chlorobenzenes in environmental samples.

In this study, a simple, novel and efficient preconcentration method for the determination of some chlorobenzenes (monochlorobenzene (MCB), three isomeric forms of dichlorobenzene (diCB), 1,3,5-trichlorobenzene (triCB) and hexachlorobenze (hexaCB)) has been developed using a headspace solid phase microextraction (HS-SPME) based on nano-structured ZnO combined with capillary gas chromatography-mass spectrometry (GC-MS). ZnO nanorods have been grown on fused silica fibers using a hydrothermal process. The diameter of ZnO nanorods was in the range of 50-80 nm. The effect of different variables on the extraction efficiency was studied simultaneously using an experimental design. The variables of interest in the HS-SPME were stirring rate, desorption time and temperature, ionic strength, extraction time and temperature. For this purpose, a multivariate strategy was applied based on an experimental design using a Plackett-Burman design for screening and a Box-Behnken design for optimizing of the significant factors. The detection limit and relative standard deviation (RSD) (n=5) for the target analytes were in the range of 0.01-0.1 ng L(-1) and 4.3-7.6%, respectively. The developed technique was found to be successfully applicable to preconcentration and determination of the target analytes in environmental water and soil samples.

The operating performance of a biotrickling filter with Lysinibacillus fusiformis for the removal of high-loading gaseous chlorobenzene.

Removal of gaseous chlorobenzene (CB) by a biotrickling filter (BTF) filled with modified ceramics and multi-surface hollow balls during gas-liquid mass transfer at the steady state was by microbial degradation rather than dissolution in the spray liquid or emission into the atmosphere. The BTF was flexible and resistant to the acid environment of the spray liquid, with the caveat that the spray liquid should be replaced once every 6-7 days. The BTF, loaded with Lysinibacillus fusiformis, performed well for purification of high-loading CB gas. The maximum CB gas inlet loading rate, 103 g m(-3) h(-1), CB elimination capacity, 97 g m(-3) h(-1), and CB removal efficiency, 97.7 %, were reached at a spray liquid flow rate of 27.6 ml min(-1), an initial CB concentration of up to 1,300 mg m(-3), and an empty bed retention time of more than 45 s.

Optimization of supercritical fluid extraction method for detection of fluquinconazole and tetraconazole in soil using gas chromatography and confirmation using GC-MS: application to dissipation kinetics.

The aim of this study was to establish an analytical method to detect fluquinconazole and tetraconazole in soil using supercritical fluid extraction (SFE) and gas chromatography (GC). The optimal extraction conditions for SFE were: temperature, 60 °C; pressure, 280 kg/cm(2) ; extraction time, 50 min; and a 10% modifier ratio. The linearity of the calibration curves was good and yielded a determination coefficient (R(2) ) ≥ 0.995. The soil samples were fortified with known quantities of the analytes at three different concentrations (0.01, 0.02 and 0.1 µg/g for fluquinconazole; 0.05, 0.1 and 0.5 µg/g for tetraconazole), and the recoveries ranged between 83.7 and 94.1%. The intra- and inter-day relative standard deviations were 1.3-10.6 and 2.2-11.9% for fluquinconazole and tetraconazole, respectively. The limit of detection and limit of quantitation were 0.002 and 0.01 µg/g for fluquinconazole and 0.01 and 0.05 for tetraconazole, respectively. The method was successfully applied to the analysis of soil residues collected from an onion field. The results show that a combination of SFE and GC can be used as an environmentally friendly technique to detect fungicides in soil.

Effect of copper oxide concentration on the formation and persistency of environmentally persistent free radicals (EPFRs) in particulates.

Environmentally persistent free radicals (EPFRs) are formed by the chemisorption of substituted aromatics on metal oxide surfaces in both combustion sources and superfund sites. The current study reports the dependency of EPFR yields and their persistency on metal loading in particles (0.25, 0.5, 0.75, 1, 2, and 5% CuO/silica). The EPFRs were generated through exposure of particles to three adsorbate vapors at 230 °C: phenol, 2-monochlorophenol (2-MCP), and dichlorobenzene (DCBz). Adsorption resulted in the formation of surface-bound phenoxyl- and semiquinoine-type radicals with characteristic EPR spectra displaying a g value ranging from ∼ 2.0037 to 2.006. The highest EPFR yield was observed for CuO concentrations between 1 and 3% in relation to MCP and phenol adsorption. However, radical density, which is expressed as the number of radicals per copper atom, was highest at 0.75-1% CuO loading. For 1,2-dichlorobenzene adsorption, radical concentration increased linearly with decreasing copper content. At the same time, a qualitative change in the radicals formed was observed--from semiquinone to chlorophenoxyl radicals. The two longest lifetimes, 25 and 23 h, were observed for phenoxyl-type radicals on 0.5% CuO and chlorophenoxyl-type radicals on 0.75% CuO, respectively.