Continuous microwave-assisted extraction, solvent changeover and preconcentration of monophenols in agricultural soils

An automatic extraction, preconcentration and clean-up module for the extraction of phenolic compounds from soils was developed; the separation and quantitation of each phenol is accomplished by GC-MS. The sorption-desorption of thirteen phenols on soils containing variable amounts of organic carbon (0.05-3.4%) and clay minerals (2-43%) at pH 5.7-8.6 was investigated. For this purpose, uncontaminated soils were spiked with 5 or 20 microg of each phenol per g of soil; the soils were then stored at 4 degrees C for at least 3 months prior to analysis in order to simulate analyte-matrix interactions other than material losses and environmental degradation in actual contaminated soils. The organic carbon content in acid and alkaline soils affects the sorption of chlorophenols but not that of alkylphenols. On the other hand, alkylphenols are preferentially sorbed by neutral soils, the process being influenced by the clay mineral content. Based on the results, alkylphenols interact more strongly with agricultural soils than do chlorophenols; also, both types of compound are less strongly sorbed by loamy sand soils owing to their increased sand contents.     

Determination of chlorinated toluenes in soils using gas chromatography tandem mass spectrometry

A method for the analysis of chlorotoluenes (CTs) in soil has been developed based on ultrasonic assisted extraction with a low volume of organic solvent and determination by gas chromatography-tandem mass spectrometry (GC–MS/MS). A simultaneous clean-up on an alumina–anhydrous sodium sulphate mixture was carried out to remove soil interferences. However, an additional clean-up with graphitised carbon was needed for some very dirty samples. Several solvents were assayed and a mixture of ethyl acetate:hexane (80?:?20, v/v) was selected to carry out soil extractions. Recovery studies were performed at 0.2, 0.1, 0.05 and 0.02?ng?g^?1 fortification levels, and recoveries obtained for all the compounds and concentrations were higher than 81% with standard deviations fulfilling the requirements of the IUPAC. LODs from 0.7 to 5.2?ng?kg^?1 and LOQs from 2.2 to 17.5?ng?kg^?1 were achieved for the analysed compounds, being pentachlorotoluene the compound with the highest limits, followed by the monochlorinated toluenes. The proposed analytical method was applied to determine CT levels in agricultural and industrial soils. These compounds were found in all the industrial soils analysed and some CTs were present in agricultural soils at lower levels.     

Sorption interactions of volatile organic compounds with organoclays under different humidities by using linear solvation energy relationships

Organoclays are usually used as sorbents to reduce the spread of organic compounds and to remove them at contaminated sites. The sorption equilibrium and the mechanisms of volatile organic compounds (VOCs) on organoclays under different humidities are helpful for developing efficient organoclays and for predicting the fate of VOCs in the environment. In this study, the organoclay was synthesized through exchanging inorganic cations by hexadecyltrimethyl ammonium (HDTMA) into montmorillonite, resulting in 12?% of organic content. The surface area of organoclay was smaller than the unmodified clay due to the incorporation of organic cations into the interlayer. Both adsorption on organoclay surface and partition into the incorporated HDTMA in organoclay played roles on the sorption process. Compared the sorption coefficients in montmorillonite and different modified clays, the incorporated organic cations overcame the inhibition effect of hydrophilic surface of clay on the sorption process of hydrophobic organic compounds from water. The sorption coefficients of VOC vapors on organoclay were further characterized using a linear solvation energy relationship (LSER). The fitted LSER equations were obtained by a multiple regression of the sorption coefficients of 22 probe chemicals against their solvation parameters. The coefficients of the five-parameter LSER equations showed that high HDTMA-content montmorillonite interacts with VOC molecules mainly through dispersion, partly through dipolarity/polarizability and hydrogen-bonds as well as with negative π-/n-electron pair interaction. The interaction analysis by LSERs suggests that the potential predominant factors governing the sorption of VOCs are dispersion interactions under all tested humidity conditions, similar with the lower level modified clay. The derived LSER equations successfully fit the sorption coefficients of VOCs on organoclay under different humidity conditions. It is helpful to design better toxic vapor removal strategy and evaluate the fate of organic contaminants in the environment.     

Molecular evaluation of soil organic matter characteristics in three agricultural soils by improved off-line thermochemolysis: The effect of hydrofluoric acid demineralisation treatment

The molecular composition of soil organic matter (SOM) in three agricultural fields under different managements, was evaluated by off-line thermochemolysis followed by gas chromatography mass spectrometry analysis (THM-GC-MS). While this technique enabled the characterization of SOM components in coarse textured soil, its efficiency in heavy textured soils was seriously affected by the interference of clay minerals, which catalyzed the formation of secondary artifacts in pyrolysates. Soil demineralization with hydrofluoric acid (HF) solutions effectively improved the reliable characterization of organic compounds in clayey soils by thermochemolysis, while did not alter significantly the results of coarse textured soil. A wide range of lignin monomers and lipids molecules, of plant and microbial origin, were identified in the pyrograms of HF treated soils, thereby revealing interesting molecular differences between SOM management practices. Our results indicated that clay removal provided by HF pretreatment enhanced the capacity of thermochemolysis to be a valuable and accurate technique to study the SOM dynamics also in heavy-textured and OC-depleted cultivated soils.     

Perfluorinated compounds (PFCs) in groundwater and aqueous soil extracts: using inline SPE-LC-MS/MS for screening and sorption characterisation of perfluorooctane sulphonate and related compounds

Perfluorinated compounds (PFCs) have been recognised as emerging pollutants of global relevance. A fully automated method with inline solid-phase extraction coupled to electrospray ionisation liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) is presented and used for characterisation of soil adsorption and desorption for six PFCs: perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorobutane sulphonate (PFBS), and perfluorooctane sulphonate (PFOS). The method reduces sample turnaround time and solvent consumption and is suitable for low volume sampling. The only sample preparation necessary for water samples was sedimentation by centrifugation. The method has a total runtime of 21 min including inline sample cleanup (2 min for injection and SPE, 14 min for the chromatographic separation, 5 min for reconditioning). Negative AP-ESI with selective reaction monitoring (SRM) was used and the method was documented for quantification of the six environmentally important PFCs in subsoil matrix and related aqueous matrixes (groundwater and drainage water). Linearity was demonstrated in the range 5 to 2,500 ng/l and the LOD was between 2 and 8 ng/l in groundwater. Adsorption was characterised by linear Freundlich isotherms for all six compounds in two agricultural top soils (A horizon, sandy and clayey soil).Variability in sorption characteristics for soil types as well as compound properties were found, and correlation between the organic carbon normalised sorption coefficient (K _OC) and PFC molecular weight was demonstrated. The K _d values were in the range 0.1 to 33 (l/kg), and 0.3 to 65 (l/kg) for sorption and desorption respectively.     

Fluorine sorption by soils developed from various parent materials in Galicia (NW Spain)

Fluorine is a phytotoxic element that can reach the soil from various industrial activities. Fluorine sorption by soil is crucial to protect water and food chain from fluorine pollution. In Galicia (NW Spain), various activities emit fluorine into the atmosphere, mainly ceramic industries and an aluminium smelter. This study, aiming to investigate fluorine sorption by Galician soils, was conducted on natural soil horizons representative of the area. Most soils were acid and rich in organic matter and showed strong fluorine sorption. The lowest sorptions were exhibited by a near-neutral serpentinite-derived soil (1001 mg kg(-1)) and the B horizons of soils developed from quartz schist (989 mg kg(-1)), and the highest by the A horizons of amphibolite-derived soils (1783 mg kg(-1)). In soils developed from quartz schist, biotitic schist and amphibolite, A horizons sorbed more fluoride than the corresponding B horizons (average 1621 and 1324 mg kg(-1), respectively), while the opposite is true in granite-derived soils (average 1644 and 1324 mg kg(-1), respectively). In the A horizons, the F sorption significantly correlated to soil pH (r=-0.79), pH in NaF (r=0.83) and oxalate Al (r=0.81). In the B horizons, sorption correlated to soil pH (r=-0.78), oxalate Fe (r=0.71) and organic C (r=0.66). F sorption can be described by both the Langmuir and Freundlich equations. The concentration of free fluoride in the equilibrium solutions increased above pH 6.     

Retention of Metamitron by Model and Natural Particulate Matter

Abstract

Adsorption isotherms of metamitron on model soil colloidal components: kaolinite, illite, montmorillonite, iron oxide and humic acid, and their binary associations were obtained using a batch equilibration procedure. Sorption parameters, K_f and n_f, were calculated by fitting the sorption data to the Freundlich equation and results obtained for binary associations were compared with those obtained for the individual model components. The sorption efficiency of the humic acids and their binary associations was measured as Koc. The adsorption behaviour of the < 2 μm fraction of two soils from Southern Spain was also studied as natural particulate matter. Montmorillonite and humic acids were found to be the most important components responsible for metamitron retention by the model adsorbents studied. On the contrary, metamitron showed little interaction with kaolinite, illite or iron oxide. These individual adsorption behaviours were reproduced in the montmorillonite-iron oxide-humic acid binary systems, but with differences suggesting changes on the surface properties upon association. Differences in Koc values of isolated humic acids and their associations indicate that the interaction transforms the humic acid surfaces and suggest different types of bonding between colloids and metamitron. The results obtained with model adsorbents and their associations were in agreement with the highest adsorption of metamitron found for the natural clay fraction of two soils which displayed the largest adsorption in that with the highest content in montmorillonite and organic carbon. The importance of organic matter and montmorillonite in metamitron adsorption by colloidal components was also shown by the decrease in K_f and the increase in Koc observed after removal of organic matter from the soil clay fraction with the highest organic carbon content.     

Determination of alachlor, metolachlor, and their acidic metabolites in soils by microwave-assisted extraction (MAE) combined with solid phase extraction (SPE) coupled with GC-MS and HPLC-UV analysis

A well-validated analytical method based on microwave-assisted extraction (MAE) and SPE is presented for the combined analysis of alachlor, alachlor-oxanilic acid (OXA), alachlor-ethanesulfonic acid (ESA), metolachlor, metolachlor-OXA, metolachlor-ESA residues in soils. Extraction of solutes by soil sample was carried out by MAE for 20 min at 100 degrees C in the presence of 50 mL solution (methanol/water 50:50), the extract was subsequently passed through C18 cartidges and fractionated into two fractions, the first with parent compounds (PCs) analyzed with GC-MS and the second one containing the metabolites analyzed with HPLC. For the SPE step, various types of sorbents (Environmental C18, tC18, Supelclean ENVI-carb, and LiChrolut EN) have been used, and their respective advantages and disadvantages are discussed. After the method optimization, average recovery values of all solutes were > 71% in the 50-500 microg/kg fortification range with RSD <10%. The LOQ and LOD were 10-50 and 5-10 microg/kg, respectively. The method was validated with two types of soils (1 and 2.4% organic matter) and in fresh (12 h aging), intermediate (1 wk aging), and aged (1 month aging) spiked samples. Moreover, residue levels determined after field application of alachlor or metolachlor were higher when soils were processed using this method than with a comparison method based on an overnight flask shaking (FS) of soil suspension.     

Static headspace analysis of volatile organic compounds in soil and vegetation samples for site characterization

Traditional methodologies for the characterization of volatile organic compounds (VOCs) in subsurface soil are expensive, time-consuming processes that are often conducted on samples collected at random. The determination of VOCs in near-surface soils and vegetation is the foundation for a more efficient sampling strategy to characterize subsurface soil and improve understanding of environmental problems.In the absence of a standard methodology for the determination of VOCs in vegetation and in view of the high detection limits of the method for soils, we developed a methodology using headspace gas chromatography with an electron capture detector for the determination of low levels (parts-per-billion to parts-per-trillion) of VOCs in soils and vegetation. The technique demonstrates good sensitivity, good recoveries of internal standards and surrogate compounds, good performance, and minimal waste. A case study involving application of this technique as a first-step vadose-zone characterization methodology is presented.     

Using mesoporous silica MCM-41 for in-line enrichment of atmospheric volatile organic compounds

A mesoporous silica MCM-41 with pore size of 29A was synthesized and assessed for its applicability as a sorbent for in-line trapping of volatile organic compounds (VOCs) from air samples. Several commercially available microporous carbon molecular sieves, i.e., Carbosieve SIII, Carboxen 1000, Carboxen 1003, and Carbotrap purchased from Supelco, were employed to form either single sorbent traps or multi-sorbent traps for comparing adsorption properties with those of the silica MCM-41. A standard gas mixture containing more than 50 target compounds with size varying from C(2) to C(12) was adsorbed by these sorbents and the per carbon response of flame ionization detection (FID) for the target compounds was calculated for obtaining the adsorption profiles. While the multi-carbon sorbents show very uniform adsorption ability across the entire carbon range from C(3) to C(12), the mesoporous silica MCM-41, however, shows little sorption for smaller molecules from C(3) to C(7), but exhibit comparable sorption ability for C(8)-C(12) compounds. Desorption at various temperatures indicates that C(8)-C(12) compounds once trapped can be easily released at moderate temperatures of about 150 degrees C, whereas for carbon sorbents the desorption temperatures for sufficient recovery need to go beyond 300 degrees C due to much tighter hold-up in the microporous structure. Sorption ability for MCM-41 is also reflected on linearity. Compounds with sufficient sorption as suggested by the adequate per carbon response also exhibit excellent precision and linearity with R(2) close to unity, an important requirement for quantitative analysis of ambient VOCs.     

Organoclay sorption of benzene as a function of total organic carbon content

The sorption of benzene to bentonite, activated carbon, and two organo-clays synthesized with the quaternary ammonium organic cations hexadecyltrimethylammonium (HDTMA) and benzyltriethylammonium (BTEA) was quantified as a function of total organic carbon content. The unmodified bentonite sorbed no benzene, while the activated carbon exhibited the strongest benzene uptake. For the organoclays, organic cations were exchanged onto Wyoming bentonite at four different percentages of the clay's cation exchange capacity. For HDTMA clay, in which partitioning is the dominant sorptive medium, it was determined that benzene sorption increased as the total organic carbon content increased (as the clay became more hydrophobic). In contrast, the sorption of benzene to BTEA clay, an adsorptive clay, decreased as the total organic carbon content of the clay was increased. It is believed that the sorptive capacity of BTEA clay decreases due to the formation of positively charged dimers on the clay's surface that block access to the sorptive sites. The organoclays sorbed more benzene than the unmodified bentonite, but less than the activated carbon.     

Competitive sorption between glyphosate and inorganic phosphate on clay minerals and low organic matter soils

Inorganic phosphate may influence the adsorption of glyphosate to soilsurface sites. It has been postulated that glyphosate sorption is dominatedby the phosphoric acid moiety, therefore, inorganic phosphate could competewith glyphosate for surface sorption sites. We examine sorption of glyphosatein low organic carbon systems where clay minerals dominate the available adsorptionsites using ³²P-labeled phosphate and ¹⁴C-labeled glyphosateto track sorption. We found glyphosate sorption strongly dependent on phosphateadditions. Isotherms were generally of the L type, which is consistent witha limited number of surface sites. Most sorption on whole soils could be accountedfor by sorption observed on model clays of the same mineral type as foundin the soils.     

The application of 1H high-resolution magic-angle spinning NMR for the study of clay-organic associations in natural and synthetic complexes

The preferential sorption of model compounds to calcium-exchanged montmorillonite surfaces was investigated using 1H high-resolution magic-angle spinning (HR-MAS) and liquid-state NMR. Synthetic mixtures, representing the major structural categories abundant in natural organic matter (NOM), and two soil extracts were sorbed to montmorillonite. The NMR spectra indicate that, of the organic components observable by 1H HR-MAS NMR, aliphatic components preferentially sorb to the clay surface, while carbohydrates and amino acids mainly remain in the supernatant. These results may help explain the highly aliphatic nature of organic matter associated with clay fractions in natural soils and sediments. Investigations using the synthetic mixtures demonstrate a specific interaction between the clay surface and the polar region in 1-palmitoyl-3-stearoyl-rac-glycerol. Similar observations were obtained with natural soil extracts. The results presented have important implications for understanding the role of organoclay complexes in natural processes, and provides preliminary evidence that HR-MAS NMR is a powerful analytical technique for the investigation of organoclay complex structure and conformation.     

Effect of phosphate on phenanthrene sorption in soils

Phosphate is ubiquitous in the environment. However, its impact on sorption of hydrophobic organic compounds in soils has received little attention. Some effects of phosphate on phenanthrene sorption were investigated in this study using two Chinese soils with contrasting properties. The presence of phosphate significantly decreased the capacity and increased the nonlinearity of phenanthrene sorption in the soils, and this sorption-inhibiting effect was more significant at high phosphate concentration. The influence of phosphate on phenanthrene sorption in the soils was governed by the release of dissolved organic carbon (DOC), particularly higher-molecular-weight and highly aromatic DOC, which tended to be enhanced in the presence of phosphate (p<0.01) as evidenced by size exclusion chromatography and specific UV absorbance analysis. Atomic force microscopy and ζ potential analysis reveal that the ringed microaggregates of DOC were disrupted into larger condensed microaggregates and the solid interfaces tended to be more hydrophilic in the presence of phosphate which also inhibited the accumulation of phenanthrene in the soils. This study for the first time points to an important role of phosphate in the sorption of phenanthrene in soils and provides substantial evidence for the mechanisms involved using a combination of microscopic and chromatographic techniques.     

Sorption, desorption and extraction of cadmium from some arable and forest soils

Summary The behavior of cadmium labeled with ¹⁰⁹Cd in different depth horizons of arable and forest soils were studied under static (batch) conditions in three interconnected processes, which consist of sorption, desorption and extraction. In the sorption, Cd²⁺ was applied in the aqueous calcium nitrate solution. Both untreated soils and peroxide treated soils were used in order to remove organic matter from some of the soil samples used in parallel. The influence of the V/m ratio on the sorption coefficients was investigated in preliminary experiments with untreated soils. Contrary to the usually short-term sorption, a long-term sorption of cadmium was investigated in untreated and treated soil horizons, which lasted more than fortnight. Kinetic studies of sorption were carried out and cadmium concentration dependence in aqueous phase of the second order kinetic constants was observed. For evaluation of sorption and desorption processes Freundlich isotherms were used. It was found that the Freundlich adsorption intensity coefficient is more time dependent than the absorption capacity coefficient, and the sorption itself consists of rapid and slow processes according to the soil constituents. Desorption and extraction processes revealed the possibility of cadmium recovery from various soil horizons. Based on the obtained results two- or three-stage theory of cadmium retention in soils was proposed. Some new insight into the role of organic matter in the sorption/desorption process of cadmium is also presented.     

Sorption of Cu(II) onto vineyard soils: macroscopic and spectroscopic investigations

The sorption of Cu on five vineyard soils was examined via macroscopic and spectroscopic investigations. The composition of the soils was previously determined using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). X-ray absorption spectroscopy (XAS) was employed to determine the metal environment with regard to the identity and interaction of the nearest atomic neighbors, the bond distances, and the coordination numbers. The five soils present similar sorption properties and there is no XAS evidence that the nature of the soil samples affects the local chemical environment of Cu(II). The kinetics of the Cu sorption reactions is rapid, with the equilibrium loading of Cu on the surface achieving approximately 200 mumol g(-1), i.e., 12.7 mg g(-1). The XAS data indicate that Cu is adsorbed in the form of inner-sphere complexes with first shell CuO parameters of four equatorial CuO bonds equal to 1.93 A and two axial CuO bonds at 2.43 A. This is in accordance with a Jahn-Teller distorted octahedron environment around copper. Our results provide evidence of the complexation of Cu(II) onto soil organic matter coated with an inorganic surface (quartz, clay, and goethite).     

Headspace solid phase microextraction (HSSPME) for the determination of volatile and semivolatile pollutants in soils

We have investigated the use of headspace solid phase microextraction (HSSPME) as a sample concentration and preparation technique for the analysis of volatile and semivolatile pollutants in soil samples. Soil samples were suspended in solvent and the SPME fibre suspended in the headspace above the slurry. Finally, the fibre was desorbed in the Gas Chromatograph (GC) injection port and the analysis of the samples was carried out. Since the transfer of contaminants from the soil to the SPME fibre involves four separate phases (soil-solvent-headspace and fibre coating), parameters affecting the distribution of the analytes were investigated. Using a well-aged artificially spiked garden soil, different solvents (both organic and aqueous) were used to enhance the release of the contaminants from the solid matrix to the headspace. It was found that simple addition of water is adequate for the purpose of analysing the target volatile organic chemicals (VOCs) in soil. The addition of 1 ml of water to 1 g of soil yielded maximum response. Without water addition, the target VOCs were almost not released from the matrix and a poor response was observed. The effect of headspace volume on response as well as the addition of salt were also investigated. Comparison studies between conventional static headspace (HS) at high temperature (95 degrees C) and the new technology HSSPME at room temperature ( approximately 20 degrees C) were performed. The results obtained with both techniques were in good agreement. HSSPME precision and linearity were found to be better than automated headspace method and HSSPME also produced a significant enhancement in response. The detection and quantification limits for the target VOCs in soils were in the sub-ng g(-1) level. Finally, we tried to extend the applicability of the method to the analysis of semivolatiles. For these studies, two natural soils contaminated with diesel fuel and wood preservative, as well as a standard urban dust contaminated with polyaromatic hydrocarbons (PAHs) were tested. Discrimination in the response for the heaviest compounds studied was clearly observed, due to the poor partition in the headspace and to the slow kinetics of all the processes involved in HSSPME.     

土壤有机质对菲的吸附-解吸平衡的影响

以自然土壤和过氧化氢分级土壤为实验模拟样品,测定了菲在这些样品上的吸附一解吸等温线,用线性和Freundlich模型拟合了这些等温线．^13C NMR谱表明,随着土壤有机质腐殖化程度的加深,有机质将含有较多的长链烷烃化合物,含氧、氮化合物有所减少,芳香环的数量变化不大．吸附实验结果表明,土壤有机质含量与菲的吸附容量存在一定的线性相关关系．有机质腐殖质化程度较深的样品比原土壤具有更大的吸附容量,其吸附等温线表现出更为明显的非线性,而且具有更明显的解吸滞后现象．说明土壤中一些结构紧密和含极性官能团较少的有机质是引起菲的非线性吸附过程和解吸滞后现象的主要原因。     

Sorption and partitioning parameters of benzotriazole compounds

Benzotriazole compounds have major commercial applications as anticorrosive agents in automotive antifreeze and airplane deicer fluids. This study assesses the sorption of benzotriazole (BT), 5-methylbenzotriazole (MBT), and 5-chlorobenzotriazole (CBT) from aqueous solutions to four top soils. The concentration range of 10-500 mg l⁻¹ was used with soils differing in total organic carbon content from 0.27 to 1.72%. Batch systems facilitated the equilibrium sorption with analysis by HPLC. The sorption of these compounds was as much as 60% by mass to a soil with 0.33% Org. C. The log octanol-water partition coefficients (log K_ow) were determined to be 1.23 for BT, 1.89 for MBT, and 2.17 for CBT. The relationship between the log of the sorption partition coefficient, log K_oc and log K_ow differed from previous correlations because hydrophobicity was not the only factor affecting sorption. These compounds have substantial permanent dipole moments as well as being hydrophobic. At high pH where CBT molecules approach their pK_a, sorption was approximately 50% less (by mass) than that of relatively non-ionized CBT molecules.     

Sorption and desorption of radiocesium on calcareous soil: Results from batch and column investigations

The sorption and desorption of radiocesium on a calcareous soil from Jiuqian County of Gansu Province (China) were studied by using batch and column experiments. The sorption-desorption isotherms and the breakthrough curves, displacement curves on the whole soil and two treated soils were determined. Based on these results, it was found that the sorption and retention of cesium are mainly determined by the clay minerals, that the sorption-desorption hysteresis of cesium on the calcareous soil is obvious and that the organic matter has a little positive contribution and the calcium carbonate has a little negative contribution to the sorption of cesium on the whole soil. The results from batch experiments were consistent with the results from column experiments.