Assessing supercritical fluid extraction for the analysis of fipronil, kresoxim-methyl, acrinathrin, and pyridaben residues in melon

An analytical method, using supercritical fluid extraction (SFE), was assessed for residue analysis of the insecticides fipronil, acrinathrin and pyridaben and the fungicide kresoxim-methyl in melons. Extraction conditions were optimized on glass beads, as inert material, evaluating different pressures, temperatures, and CO(2) volumes. Also, the extractability of pesticides from hydromatrix and anhydrous magnesium sulfate was evaluated. Both adsorbents were evaluated for the preparation of SFE-spiked melon samples. Extractions of fortified samples were done using 20 mL of CO(2), 300 atm, and 50 degrees C. Different extraction conditions, including the addition of water and methanol as a static modifier, were used to assess the extractability of these pesticides, and the addition of methanol was demonstrated to improve the extraction of all the studied pesticides.     

Catalytic Gasification of Coal Using Eutectic Salts: Recovery,Regeneration, and Recycle of Spent Eutectic Catalysts

Abstract

Catalyst recovery studies were conducted for gasified chars produced from steam gasification of Illinois #6 coal catalyzed with two different catalyst systems. A ternary (43.5 mol% Li₂ CO₃ –31.5 mol% Na₂ CO₃ –25 mol% K₂ CO₃ ) and a binary (29 mol% Na₂ CO₃ –71 mol% K₂ CO₃ ) eutectic catalyst system were used for gasifying coal. Various extraction schemes, such as water extraction, H₂ SO₄ extraction, and acetic acid extraction, were evaluated with respect to their extraction efficiencies. Effects of major process variables, such as solvent-to-char ratio, mixing time, temperature, and concentration, on the extraction efficiency were evaluated. A process schematic for the entire catalyst recovery, regeneration, and recycle scheme was developed and the preliminary process economics were determined based on these extraction schemes. H₂ SO₄ extraction was found to be the most desirable. It also turned out to be more attractive than a once-through throwaway system.     

Hydroxypropyl-β-cyclodextrin as non-exhaustive extractant for organochlorine pesticides and polychlorinated biphenyls in muck soil

Hydroxypropyl-β-cyclodextrin (HPCD) was used as a non-exhaustive extractant for organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) in muck soil. An optimized extraction method was developed which involved using a HPCD to soil mass ratio of 5.8 with a single extraction period of 20 h. An aging experiment was performed by spiking a muck soil with ¹³C-labeled OCs and non-labeled PCBs. The soil was extracted with the optimized HPCD method and Soxhlet apparatus with dichloromethane over 550 d periodically. The HPCD extractability of the spiked OCs was greater than of the native OCs. A decreased in HPCD extractability was observed for the spiked OCs after 550 d of aging and their extractability approached those of the natives. The partition coefficient between HPCD and soil (log K_CD-Soil) was negatively correlated with the octanol-water partition coefficient (log K_OW) with r² = 0.67 and p < 0.05.     

Comparative studies of the fate of atrazine‐14C and pentachlorophenol‐14C in various laboratory and outdoor soil‐plant systems

Abstract

Mass balance and fate of atrazine‐ ¹⁴C and pentachlorophenol‐ ¹⁴C (PCP‐ ¹⁴C) were studied in short‐term tests in a closed aerated laboratory soil‐plant system, using two concentrations in soil and two plant species, as well as under outdoor conditions for one vegetation period. In the laboratory, for both pesticides bioaccu‐mulation factors of radiocarbon taken up by the roots into plants were low. They were higher for lower (1 ppm) than for higher soil concentrations (6 ppm for atra‐zine, 4 ppm for pentachlorophenol) and varied with the plant species. Mineralization to ¹⁴CO₂ in soil was negatively related to soil concentration only for PCP‐ ¹⁴C. Conversion rates in soil including the formation of soil‐bound residues were higher for the lower concentrations of both pesticides than for the higher ones; conversion rates in plants were species‐dependent. In 14 terms of CO₂ formation and of conversion rates, PCP was less persistent in soil than was atrazine. For both pesticides, laboratory data on conversion and mineralization gave a rough prediction of their persistence in soil under long‐term outdoor conditions, whereas bio‐accumulation factors in plants under long‐term outdoor conditions could not be predicted by short‐term laboratory experiments.     

The extractability and mineralisation of cypermethrin aged in four UK soils

Cypermethrin is a widely used insecticide that has caused concern due to its toxicity in the aquatic environment. As with all land applied pesticides, the most significant source of water pollution is from the soil, either due to leaching or washoff. The behaviour of cypermethrin in the soil controls the likelihood of future pollution incidents, with two of the most significant processes being the formation of bound residues and microbial degradation. The formation of bound residues and mineralisation was measured in four organically managed soils from the UK. The formation of bound residues was measured using three different extraction solutions, 0.01 M CaCl₂, 0.05 M HPCD and acetonitrile. Biodegradation was assessed by measurement of mineralisation of cypermethrin to CO₂. The formation of bound residues varied according to extraction method, soil type and length of ageing. In two of the four soils studied, acetonitrile extractability decreased from 100% initially to 12-14% following 100 d ageing. The extent of mineralisation increased after 10-21 d ageing, reaching 33% of remaining activity in one soil, however following 100 d ageing the extent of mineralisation was significantly reduced in three out of the four soils. As with the formation of bound residues, mineralisation was impacted by soil type and length of ageing.     

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.     

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.     

Multiresidue analysis of organophosphate and pyrethroid pesticides in duplicate-diet solid food by pressurized liquid extraction

An analytical method was developed for determining organophosphate pesticides (OPP) and pyrethroid pesticides (PYR) in duplicate-diet solid food. The method consisted of pressurized liquid extraction (PLE) with dichloromethane followed by cleanup with gel permeation and solid phase extraction columns and gas chromatography/mass spectrometry (GC/MS) analysis. Quantitative recoveries (73–117 %) of the target pesticides were obtained for spiked duplicate-diet food samples. The percent standard deviation (% RSD) of replicate food samples was within ± 20 %. Another method was developed for determining a common OPP metabolite, 3, 5, 6-trichloro-2-pyridinol (TCP) in duplicate-diet food. The method consisted of a PLE with methanol followed by liquid-liquid partitioning, derivatization, and GC/MS analysis. Recoveries of TCP ranged from 83 to 101 % for spiked duplicate-diet food samples. The % RSD of replicate food samples was within ± 15 %. The results confirmed that these methods are reliable and robust, and that they can be used in routine analysis. In addition, a storage stability study for a common OPP, chlorpyrifos (CPF), in solid food samples was performed. The fortified ¹⁵N-¹³C-labeled CPF was stable over 16 mo storage at ?20° C in the dark. The developed analytical methods were successfully applied to 278 duplicate-diet food samples from preschool children, demonstrating that these methods are robust and suitable for routine analysis in future exposure monitoring studies.     

Influence of benomyl and prometryn on the soil microbial activities and community structures in pasture grasslands of Slovakia

The effects of pesticides (a herbicide and a fungicide) on the microbial community structure and their activity were analyzed in soil from four alpine pasture grasslands in Slovakia. Specifically, the effects of the herbicide, Gesagard (prometryn active ingredient), and fungicide, Fundazol 50 WP (benomyl active ingredient), on the microbial respiration activity (CO₂ production), the numbers of selective microbial physiological groups (CFU.g^?1) and the structure (relative abundance) of soil microbial communities [(phospholipid fatty acid (PLFA)] were analyzed under controlled laboratory conditions. All treatments including the treatments with pesticides increased (statistically significantly) the production of CO₂ in all fields during 21 days of incubation and posed a statistically insignificant negative influence on the numbers of the observed physiological groups of microorganisms. The significantly negative influence was evaluated only in the numbers of two physiological groups; spores of bacteria utilizing organic nitrogen and bacteria, and their spores utilizing inorganic nitrogen. A shift in the microbial composition was evident when the PLFA patterns of samples from different sites and treatments were compared by the Principal Component Analysis (PCA). According to the second component PCA 2 (15.95 %) the locations were grouped into two clusters. The first one involved the Donovaly and Dubakovo sites and the second one contained the Velka Fatra and Mala Fatra locations. The PLFA composition of the soils showed important changes after the treatment with pesticides according to PCA 1 (66.06 %). Other treatments had not had a significant effect on the soil microbial community with the exception of the population of fungi. The lower relative abundance (significant effect) of Gram-positive bacteria, actinomycetes and general group of bacteria were determined in samples treated by the herbicide Gesagard. The application of fungicide Fundazol decreased (statistically significantly) the relative abundance of actinomycetes and general group of bacteria and paradoxically increased the population of fungi.     

Removing perfluorooctane sulfonate and perfluorooctanoic acid from solid matrices, paper, fabrics, and sand by mineral acid suppression and supercritical carbon dioxide extraction

The removal of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) from solid matrices has received considerable attention because of the environmental persistence, bioaccumulation, and potential toxicity of these compounds. This study presents a simple method using concentrated HNO₃ as a suppression agent, and methanol-modified supercritical carbon dioxide (Sc-CO₂) extraction for removing PFOS and PFOA from solid matrices. The optimal conditions were 16 M HNO₃ and 20% (v/v) methanol containing Sc-CO₂, under a pressure of 20.3 MPa and a temperature of 50 °C. Extraction time was set at 70 min (40 min for static and 30 min for dynamic extraction). PFOA and PFOS were identified and quantitated by liquid chromatography/mass spectrometry. The extraction efficiencies (with double extractions) were close to 100% for PFOA and 80% for PFOS for both paper and fabric matrices. The extraction efficiencies for sand were approximately 77% for PFOA and 59% for PFOS. The results show that this method is accurate, and effective, and that it provides a promising and convenient approach to remediate the environment of hazardous PFOA and PFOS contamination.     

Quality of roof runoff waters from an urban region (Gda sk, Poland)

The paper presents the results of testing of roof runoff waters from buildings in the city of Gda sk (Poland), carried out as a part of a broader research project aimed at the determination of pollutant levels in precipitation. The analytes determined included volatile organohalogen compounds, petroleum hydrocarbons, Na⁺, K⁺, NH₄⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, NO₂⁻, NO₃⁻, PO₄³⁻, SO₄²⁻ ions, as well as organonitrogen, organophosphorus and organochlorine pesticides. In addition, the toxicity and pH of the samples were examined. The samples were collected over a period of six months, during or immediately following precipitation events. More than half of the samples (25) were found to be toxic, with inhibition exceeding 20%. The toxicity was weakly correlated to the levels of organonitrogen and organophosphorus pesticides in runoff waters. It was established that at least in some cases the roofing material affected the levels of the pollutants found in the samples.     

A passive sampling method for radiocarbon analysis of atmospheric CO2 using molecular sieve

Radiocarbon (¹⁴C) analysis of atmospheric CO₂ can provide information on CO₂ sources and is potentially valuable for validating inventories of fossil fuel-derived CO₂ emissions to the atmosphere. We tested zeolite molecular sieve cartridges, in both field and laboratory experiments, for passively collecting atmospheric CO₂. Cartridges were exposed to the free atmosphere in two configurations which controlled CO₂ trapping rate, allowing collection of sufficient CO₂ in between 1.5 and 10 months at current levels. ¹⁴C results for passive samples were within measurement uncertainty of samples collected using a pump-based system, showing that the method collected samples with ¹⁴C contents representative of the atmosphere. δ¹³C analysis confirmed that the cartridges collected representative CO₂ samples, however, fractionation during passive trapping means that δ¹³C values need to be adjusted by an amount which we have quantified. Trapping rate was proportional to atmospheric CO₂ concentration, and was not affected by exposure time unless this exceeded a threshold. Passive sampling using molecular sieve cartridges provides an easy and reliable method to collect atmospheric CO₂ for ¹⁴C analysis.     

Biodegradation of malathion, α- and β-endosulfan by bacterial strains isolated from agricultural soil in Veracruz,Mexico

The objective of this study was to evaluate the capacity of two bacterial strains isolated, cultivated, and purified from agricultural soils of Veracruz, Mexico, for biodegradation and mineralisation of malathion (diethyl 2-(dimethoxyphosphorothioyl) succinate) and α- and β-endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6-9-methano-2,4,3-benzodioxathiepine-3-oxide). The isolated bacterial strains were identified using biochemical and morphological characterization and the analysis of their 16S rDNA gene, as Enterobacter cloacae strain PMM16 (E1) and E. amnigenus strain XGL214 (M1). The E1 strain was able to degrade endosulfan, whereas the M1 strain was capable of degrading both pesticides. The E1 strain degraded 71.32% of α-endosulfan and 100% of β-endosulfan within 24 days. The absence of metabolites, such as endosulfan sulfate, endosulfan lactone, or endosulfan diol, would suggest degradation of endosulfan isomers through non-oxidative pathways. Malathion was completely eliminated by the M1 strain. The major metabolite was butanedioic acid. There was a time-dependent increase in bacterial biomass, typical of bacterial growth, correlated with the decrease in pesticide concentration. The CO₂ production also increased significantly with the addition of pesticides to the bacterial growth media, demonstrating that, under aerobic conditions, the bacteria utilized endosulfan and malathion as a carbon source. Here, two bacterial strains are shown to metabolize two toxic pesticides into non-toxic intermediates.     

Influence of the operation conditions on CO2 capture by CaO-derived sorbents prepared from synthetic CaCO3

In this work, a statistical experimental design is performed in order to prepare CaCO₃ materials for use as CaO-based CO₂ sorbent precursors. The influence of different operational parameters such as synthesis temperature (ST), stirring rate (SR) and surfactant percent (SP) on CO₂ capture is studied by applying Response Surface Methodology (RSM). The samples were characterized using different analytical techniques including X-ray diffraction, N₂ adsorption isotherm analysis and Scanning Electron Microscopy–X-ray Energy Dispersive Spectroscopy (SEM-EDX). CO₂ capture capacity was determined by means of a thermogravimetric analyzer which recorded the mass uptake of the samples when these were exposed to a gas stream containing diluted (15%) CO₂. The statistical approach used in this work provides a rapid way of predicting and optimizing the main preparation variables of CaO-derived sorbents for CO₂ sorption. The results obtained clearly indicate that four parameters statistically influence CO₂ uptake: SR, the square of SR, its interaction with SP and the square of SP.     

Microbial metabolism of N-Phenyl-1-naphthylamine in soil, soil suspensions, and aquatic ecosystems

N-Phenyl-1-naphthylamine (PNA) was degraded and mineralized in nonsterile aquatic and terrestrial samples. Degradation in unsupplemented sewage and lake water was detected in 3 to 6 days with half-lives of 5 and 10 days, respectively. In sewage and lake water supplemented with a readily degradable carbon source, degradation began in 1 and 5 days with half-lives of 2 and 8 days, respectively. Sewage samples converted between 20 and 30% of labeled [¹⁴C]-PNA to ¹⁴CO₂ in 35 days while lake water samples reached 10% conversion to ¹⁴CO₂ in 12 days. Soil samples and soil suspensions converted from 15 to 35% of [¹⁴C]-PnA to ¹⁴CO₂ in 11 days. PNA was microbiologically converted in lake water to two products that were tentatively identified by gas-liquid chromatography and mass spectroscopy as dihydroxy and N-acetyl derivatives.     

纳米片自组装原位N掺杂(BiO)2CO3分级微球的可控合成及其优异可见光催化性能

以二氰二胺和柠檬酸铋为原料,采用一步水热法合成原位N掺杂(BiO)2CO3纳米片自组装分等级微球结构。采用XRD、SEM、XPS、FT-IR、UV-Vis DRS和PL等对合成的材料进行表征,结果表明,不同二氰二胺加入量会对(BiO)2CO3的形貌结构、禁带宽度以及电子-空穴复合率产生显著影响。二氰二胺在水热过程水解柠檬酸铋,同时N原子原位掺杂进入(BiO)2CO3晶格。N掺杂使(BiO)2CO3的光响应范围大幅拓展至可见光,通过价带XPS获得了掺杂N元素减小(BiO)2CO3禁带宽度的证据。在可见光照射下,原位N掺杂(BiO)2CO3分等级微球结构表现出对液相罗丹明B和气相NO优异的可见光催化降解活性,高于N掺杂TiO2和C掺杂TiO2。研究结果对拓展N掺杂作用向非TiO2体系的转变具有重要意义。     

Simultaneous determination of eight metabolites of organophosphate and pyrethroid pesticides in urine

A simultaneous method for quantifying eight metabolites of organophosphate pesticides and pyrethroid pesticides in urine samples has been established. The analytes were extracted using liquid–liquid extraction coupled with WCX solid phase extraction (SPE) cartridges. Eight metabolites were chemically derivatized before analysis using gas chromatography–tandem mass spectrometry (GC–MS–MS). The separation was performed on a HP-5MS capillary column (30 m × 0.25 mm × 0.25 µm) with temperature programming. The detection was performed under electro-spray ionization (ESI) in multiple reaction monitoring (MRM) mode. An internal standard method was used. The extraction solvent, types of SPE cartridges and eluents were optimized by comparing the sample recoveries under different conditions. The results showed that the calibration curves of the five organophosphorus pesticides metabolites were linear in the range of 0.2–200 μg/L (r² ≥ 0.992) and that of the three pyrethroid pesticides metabolites were linear in the range of 0.025–250 μg/L (r² ≥ 0.991). The limits of detection (LODs, S/N ≥ 3) and the limits of quantification (LOQs, S/N ≥ 10) of the eight metabolites were 0.008–0.833 μg/L and 0.25–2.5 μg/L, respectively. The recoveries of the eight metabolites ranged from 54.08% to 82.49%. This efficient, stable, and cost-effective method is adequate to handle the large number of samples required for surveying the exposure level of organophosphorus and pyrethroid pesticides in the general population.     

An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Abstract

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO₂) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography‐electron capture detector (GC‐ECD) indicated that the herbicide trifluralin (2,6‐dinitro‐N,N‐dipropyl‐4‐trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid‐phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low‐cost home‐made system that did not require the use of organic solvents.     

Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties

In order to evaluate the extraction of pesticide residues that are transferred to the brew during mate drinking process of P.U.1 yerba mate leaves (Ilex paraguariensis), a special device to simulate the way in which mate is drunk in Uruguay was developed. The transfer to the brew of 12 organophosphates, 5 synthethic pyrethroids and one organochlorine pesticide from spiked samples was studied. The relationship between the transfer data thus obtained and physicochemical properties like water solubility (Ws), octanol-water coefficient (Kow) and Henry's constant (H) was evaluated. The extractability of the pesticide residues from yerba mate can be correlated with log Ws and log Kow. These transfer values allowed the calculation of ARLs (acceptable residue level) for the pesticides following Food and Agriculture Organization (FAO), World Health Organizaion (WHO) guidelines. These results can help the future establishment of maximum residue levels (MRLs)     

Dry reforming of methane to syngas: a potential alternative process for value added chemicals—a techno-economic perspective

During the past decade, there has been increasing global concern over the rise of anthropogenic CO₂ emission into the Earth’s atmosphere (J Air Waste Manage Assoc 53:645–715, 2003). The utilization of CO₂ to produce any valuable product is need of the hour. The production of syngas from CO₂ and CH₄ seems to be one of the promising alternatives in terms of industrial utilization, as it offers several advantages: (a) mitigation of CO₂, (b) transformation of natural gas and CO₂ into valuable syngas, and (c) producing syngas with H₂/CO ratio 1 which may further be used for the production of valuable petrochemicals (J Air Waste Manage Assoc 53:645–715, 2003). A conceptual design for the production of synthesis gas by dry reforming of methane is presented here. An economic assessment of this process with an integrated methanol production section as a case was conceptualized and compared with the conventional steam methane reforming route to produce methanol. The economic study indicated that dry reforming of natural gas/methane is a competitive process with lower operating and capital costs in comparison with steam reforming assuming negligible cost of CO₂ import.