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

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.     

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.     

Heavy metal sequential extraction methods--a modification for tropical soils

Sequential extractions of metals can be useful to study metal distributions in various soil fractions. Although several sequential extraction procedures have been suggested in the literature, most were developed for temperate soils and may not be suitable for tropical soils with high contents of Mn and Fe oxides. The objective of this study was to develop a sequential fractionation procedure for Cu and Zn in tropical soils. Extractions were performed on surface (0–20 cm) samples of ten representative soils of Sao Paulo State, Brazil. Chemically reactive Mn forms were satisfactorily assessed by the new modified procedure. Amorphous and crystalline Fe oxides were more selectively extracted in a new two-step extraction. Soil-born Zn and Cu were primarily associated with recalcitrant soil fractions. The proposed procedure provided more detailed information on metal distribution in tropical soils and better characterization of the various components of the soil matrix. The new procedure is expected to be an important tool for predicting the potential effects of environmental changes and land application of metals on the redistribution of chemical forms of metals in tropical soils.     

Investigating differential binding of polychlorinated dibenzo-p-dioxins/dibenzofurans in soil and soil components using selective supercritical fluid extraction

Supercritical fluid extraction (SFE) with pure carbon dioxide was performed at increasingly strong conditions to investigate differential binding of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in two impacted soils, in their sieved size fractions, and in small (a few mg) samples of industry-related waste products separated from impacted soil. The binding strengths of PCDD/Fs were shown to be different in the two soils, and in their different soil particle size fractions. As might be expected based on surface area considerations, one soil showed the strongest binding in the smallest (<5 μm) sieved fraction. However, the other soil showed the strongest binding in the larger sized fractions, possibly indicating that process-related particles could be controlling PCDD/F binding. Selective SFE of various types of particles including black carbon and charcoal (separated from soil), and from a suspected process anode residue did show different PCDD/F binding behavior ranging from quite weak binding (charcoal) to very strong binding (anode particles). Shifts to the stronger SFE fractions in the soils after activated carbon treatment agreed well with the decreases previously found in the uptake of PCDD/Fs by earthworms, as well as decreases in their freely-dissolved aqueous concentrations in soil/water slurries. These results show that, as previously demonstrated for PAHs and PCBs, selective SFE can be a useful tool to investigate differences in PCDD/F binding behaviors in impacted soils and sediments and their component parts, as well as a rapid tool for estimating the effectiveness of activated carbon treatments on decreasing the bioavailability of PCDD/Fs in soils and sediments.     

Modelling the extraction of soil contaminants with supercritical carbon dioxide

Extractions of volatile organic compounds (VOC’s) in contaminated soil from petroleum site were performed with supercritical carbon dioxide at different temperatures, pressures, extraction times, solvent flow rates, soil moisture contents and soil acidity. Three soil systems were investigated in order to compare the best parameters for extraction. A central composite rotatable design has been used to evaluate the influence of operation conditions on the extraction efficiency to generate model equations representing the types of soil. The results indicate that at least 70-80% of the initial amount of VOC’s can be removed at moderate temperatures even at very high moisture content. Supercritical extraction is best suited to silt type soils which have a low adsorption capacity. VOC’s recoveries from the artificial contaminated soil samples were higher in comparison with real contaminated soils. At moderate temperatures, the extraction efficiency for real soils is low because pollutants bind strongly to the soil.     

Metal extractability patterns to evaluate (potentially) mobile fractions in periurban calcareous agricultural soils in the Mediterranean area—analytical and mineralogical approaches

A set of periurban calcareous agricultural Mediterranean soils was spiked with a mixture of Cd, Cu, Pb and Zn at two levels within the limit values proposed by current European legislation, incubated for up to 12 months, and subjected to various one-step extraction procedures to estimate mobile (neutral salts) and potentially mobile metal fractions (complexing and acidic extraction methods). The results obtained were used to study metal extractability patterns according to the soil characteristics. The analytical data were coupled with mineralogical investigations and speciation modelling using the Visual Minteq model. The formation of soluble metal-complexes in the complexing extracts (predicted by the Visual Minteq calculations) led to the highest extraction efficiency with complexing extractants. Metal extractability patterns were related to both content and composition of carbonate, organic matter, Fe oxide and clay fractions. Potentially mobile metal fractions were mainly affected by the finest soil fractions (recalcitrant organic matter, active lime and clay minerals). In the case of Pb, scarce correlations between extractable Pb and soil constituents were obtained which was attributed to high Pb retention due to the formation of 4PbCO₃·3PbO (corroborated by X-ray diffraction). In summary, the high metal proportion extracted with complexing agents highlighted the high but finite capacity to store potentially mobilizable metals and the possible vulnerability of these soils against environmental impact from metal accumulation.     

Age-dating Diesel Fuel Spills: Using the European Empirical Time-based Model in the U.S.A.

In 1993, a paper was published by Christensen and Larsen that offered a method for determining the age of diesel oil spills in soil (Christensen and Larsen, 1993 Ground Water Mount. R . Fall , 142-149). It presented an empirical time-based model of the degradation of diesel fuel in soils using chemical data gathered at petroleum release sites in Denmark and the Netherlands. Now, evaluation of the validity of the application of this work to subsurface petroleum releases in other countries remains. In the U.S.A., investigations assessing date(s) of release of diesel fuel in soils, e.g. age dating of subsurface petroleum contamination, have considerable interest. Litigation-driven scientific investigations with accompanying expert testimony in a court of law are underway. The number of instances where application of the Christensen and Larsen empirical time-based model to petroleum-contaminated properties is growing in the U.S.A. This paper presents two case studies which evaluate the applicability of the Christensen and Larsen empirical time-based model to petroleum-contaminated properties in general. It illustrates the approach using gas chromatographic data from two recently-completed projects evaluating the applicability of the Christensen and Larsen model to a No. 2 fuel oil/diesel fuel surface spill in the U.S.A. Results showed that the application of the model to petroleum-contaminated soils was scientifically valid, provided its applicability was evaluated using hypothesis testing for specific changes in the characteristics of the petroleum hydrocarbon distribution in a number of soil samples collected over time at one site. The paper offers observations on the application of the Christensen and Larsen model to petroleum found in the light non-aqueous phase liquid (LNAPL) phase and groundwater.     

Distribution coefficient of selenium in Japanese agricultural soils

In order to evaluate the selenium (Se) sorption level in Japanese soils, soil/soil solution distribution coefficients (K(d)s) were obtained for 58 agricultural soil samples (seven soil classification groups) using 75Se as a tracer. Although several chemical forms of Se are present in agricultural fields, selenite was used, because it is the major inorganic Se form in acid soils such as found in Japan. The Kd values obtained covered a wide range, from 12 to 1060l/kg, and their arithmetic mean was 315l/kg. Among the soil groups, Andosols had higher Kd values. The Kd values for all samples were highly correlated with soil active-aluminum (Al) and active-iron (Fe) contents. Thus, active-Al and active-Fe were considered to be the major adsorbents of Se. Then, a new sequential extraction procedure was applied to 12 soil samples in order to quantify the effect of soil components on Se adsorption. The sequential extraction results showed that 80-100% of the adsorbed Se was recovered as Al-bound Se and Fe-bound Se. The amount of Al-bound Se was the highest in the soils that showed high Kd values, though the relative contribution of Fe-bound Se tended to increase with decreasing Kd values. The high values of Kd seemed to be caused mainly by the adsorption of Se onto active-Al in Japanese soils.     

Measuring bioavailability of polychlorinated biphenyls in soil to earthworms using selective supercritical fluid extraction

If the release mechanisms during selective chemical extraction of persistent organic pollutants (POP) mimic release mechanisms in natural systems during biological uptake, then a selective non-exhaustive extraction could give a quantitative measure of the bioavailable POP fraction. Supercritical fluid extraction (SFE) is suggested as a possible technique to estimate the amount of bioavailable polychlorinated biphenyls (PCBs) at contaminated sites and hence serve as a new tool in risk assessment. The uptake of PCBs by earthworm (Eisenia foetida) was investigated. PCB contaminated soil was pre-extracted with selective non-exhaustive SFE (50 degrees C, 350 bar, 1h), which removed on average 70% of the individual PCBs. Earthworms were placed in this pre-extracted soil, as well as in untreated soil. After 10 days, the PCB uptake by earthworms in the two systems was compared. The bioaccumulation factor (BAF) was 83% lower in the pre-extracted system than in the untreated system, demonstrating that SFE extracts primarily bioavailable contaminants. From the data, the bioavailable fraction could also be calculated to be 75%, which is very close to the 70% removed by SFE under the applied conditions. This suggests that the chemical methodology is capable of measuring the bioavailable fraction very accurately in this system.     

Risk-based Decision Process for Arsenic in Soils: Implications of Conservative Protocols

Making defensible risk-based decisions is a complex process that incorporates risk assessment into a risk management framework. Many site investigations require additional study, negotiations and/or actions for arsenic detected in soil samples, in many cases where no process related sources are identified and no other chemicals of concern are identified. Regulatory agencies develop guidance to standardize approaches to risk-based site investigations that focus on achieving “safe” concentrations. For arsenic, the action level is frequently in the “gray region”, a U.S. Environmental Protection Agency (USEPA) term associated with a region of high uncertainty for risk management decisions in the “decision performance curve” associated with the data quality objective (DQO) process. Recognizing the conservative nature of the risk-based screening value for arsenic, approaches to enforce this level (or proof of comparability to natural background) may have numerous consequences including ineffective use of resources, stigmas on properties or actions at industrial or hazardous sites that are inconsistent with their regional setting. Florida has developed regulations and guidance on investigation of brownfield sites and has supported a study by the University of Florida (UF) to evaluate natural background concentrations in Florida soils. This paper discusses the sources of uncertainty near the soil cleanup target levels (SCTLs) in the Florida decision-making framework.     

Comparative study of accessibility of distinctive pesticides

Interactions of micro-contaminants with soil may play a crucial role in their environmental fate and possible harmful effects. Major goals of our investigations were to model the availability of widely used pesticides and characterize adsorption capabilities of distinctive soil types by the accomplishment of extensive comparative studies and application of several extraction methods. Environmental and biological relevance of these examinations is enhanced by the fact that intrinsic features and specific details of pesticide accessibility have not been revealed so far by a comparative approach. Five different experimental methods were assessed for modelling accessibility of five selected pesticides. The applied models for regaining the pesticides showed diverse efficiency in extraction capability in cases of the different soil types (sandy, brown forest and alluvial soils). The amounts of the obtained pesticides were determined by using gas-chromatography coupled to mass spectrometry (GC-MS) and high pressure liquid chromatography coupled to mass spectrometry (HPLC-MS). Accessibility of pesticides was also compared in cases of sterilized and real soil samples in order to estimate the extent of the influence of microflora. Aqueous extraction solvents proved to be suitable for accurate assessment of the accessible amounts of pesticides, as their effectivity was at least as high as that of the applied organic solvents. In our studies pesticide-soil interactions have comprehensively been characterized, and possible influences of environmental factors on the accessibility have also been revealed. Our study might be regarded as a tentative approach to model some significant circumstances playing key roles in pesticides' possible bioavailability.     

Age-dating Diesel Fuel Spills: Using the European Empirical Time-based Model in the U.S.A.

In 1993, a paper was published by Christensen and Larsen that offered a method for determining the age of diesel oil spills in soil (7Ground Water Mount.R . Fall, 142–149). It presented an empirical time-based model of the degradation of diesel fuel in soils using chemical data gathered at petroleum release sites in Denmark and the Netherlands. Now, evaluation of the validity of the application of this work to subsurface petroleum releases in other countries remains.In the U.S.A., investigations assessing date(s) of release of diesel fuel in soils, e.g. age dating of subsurface petroleum contamination, have considerable interest. Litigation-driven scientific investigations with accompanying expert testimony in a court of law are underway. The number of instances where application of the Christensen and Larsen empirical time-based model to petroleum-contaminated properties is growing in the U.S.A.This paper presents two case studies which evaluate the applicability of the Christensen and Larsen empirical time-based model to petroleum-contaminated properties in general. It illustrates the approach using gas chromatographic data from two recently-completed projects evaluating the applicability of the Christensen and Larsen model to a No. 2 fuel oil/diesel fuel surface spill in the U.S.A. Results showed that the application of the model to petroleum-contaminated soils was scientifically valid, provided its applicability was evaluated using hypothesis testing for specific changes in the characteristics of the petroleum hydrocarbon distribution in a number of soil samples collected over time at one site. The paper offers observations on the application of the Christensen and Larsen model to petroleum found in the light non-aqueous phase liquid (LNAPL) phase and groundwater.     

Persistence of LNAPL sources: relationship between risk reduction and LNAPL recovery

Light nonaqueous phase liquids (LNAPLs), such as fuels, are the source of much soil and groundwater contamination. Though the mobility of LNAPLs is limited in many environments, dissolved-phase components, such as benzene, can produce groundwater plumes that are more mobile than the LNAPL source. In such a setting, it is commonly assumed that recovery of the LNAPL will result in a reduction in risk associated with the dissolved phase. This paper synthesizes several existing multiphase and chemical transport solutions into a single linked methodology that predicts concentrations of soluble constituents within and downgradient of LNAPL source zones from dissolution of those constituents into groundwater flowing through and below LNAPL sources. This approach has been applied to a variety of LNAPL spill conditions. For biodegradable compounds, these analyses show that the period of time where the dissolved-phase plume is expanding is very small compared to the duration of most LNAPL sources, and that the downgradient extent is generally less than about 100 m for BTEX compounds. Therefore, the risk to receptors, as measured by the maximum downgradient extent of dissolved-phase plume or the maximum concentration of these compounds at a downgradient receptor, is generally unrelated to the longevity of the LNAPL sources. The maximum downgradient extent of the dissolved-phase plume is determined almost entirely by the groundwater velocity and the biodegradation rate. These analyses further demonstrate that recovery of LNAPL by hydraulic methods is often ineffective at reducing risk. Except in coarse-grained soils or intermediate soils with significant LNAPL saturations, free-product recovery approaches do not result in significant reductions in the longevity of downgradient dissolved-phase contamination. Further, for biodegradable constituents, remediation does not result in a near-term decrease in the downgradient extent of contamination. Cleanup methods that act to change the composition of the LNAPL source are more effective at reducing the downgradient concentrations, particularly for fine-grained soils or when LNAPL saturations are low.     

Detection of indoor PCB contamination by thermal desorption of dust. A rapid screening method?

Although PCB in caulking materials has been forbidden for many years in most of Europe, including Denmark, there has been continued interest to measure PCB levels in the air of contaminated buildings and blood of the occupants (Mengon and Schlatter 1993, Fromme et al. 1996, Ewers et al. 1998, Currado and Harrad 1998, Gabrio et al. 2000). The relatively low priority for investigations of this contamination is probably due to the small quantities inhaled compared to exposure via food, and the rapid metabolism of the most volatile congeners demonstrated by low concentrations of all congeners in the blood of exposed persons (Ewers et al. 1998, Gabrio et al. 2000). There is, however, evidence that PCB containing caulking materials have been used even during the '90s (Fromme et al. 1996). In Denmark, it is estimated that 75 t PCB is still in buildings (Organization of Sealant Branch's Manufacturers and Distributors 2000). During an investigation of dust from buildings with excessive microbial growth (including 35 rooms from 9 buildings), the analysis of semivolatile compounds by thermal desorption-GC/MS of samples from a single building surprisingly revealed large amounts of PCBs containing 3, 4 and 5 chlorine atoms, 10-20 times the amounts found in samples from other buildings. Extraction of the dust by SFE followed by GC/ECD analysis for 12 PCB congeners showed that there was approximately 20 times the total PCB concentrations in dust from the polluted building compared to the levels in the other buildings. Subsequent headspace analysis of caulking material from the polluted building revealed this to be the source. Shelf dust functions as a passive sampling medium and, thus, can be used as a screening method to detect PCB and other semivolatile pollution indoors.     

Spiking solvent, humidity and their impact on 2,4-D and 2,4-DCP extractability from high humic matter content soils

The 2,4-dichlorophenoxyacetic acid (2,4-D) is a hormone-like herbicide widely used in agriculture. Although its half life in soil is approximately two weeks, the thousands of tons introduced in the environment every year represent a risk for human health and the environment. Considering the toxic properties of this compound and its degradation products, it is important to assess and monitor the 2,4-D residues in agricultural soils. Furthermore, experiments of phyto/bioremediation are carried out to find economic and environmental friendly tools to restore the polluted soils. Accordingly, it is essential to accurately measure the amount of 2,4-D and its metabolites in soils. There is evidence that 2,4-D extraction from soil samples seriously depends on the physical and chemical properties of the soil, especially in those soils with high content of humic acids. The aim of this work was to assess the variables that influence the recovery and subsequent analysis of 2,4-D and its main metabolite (2,4-dichlorophenol) from those soils samples. The results showed that the recovery efficiency depends on the solvent and method used for the extraction, the amount and kind of solvent used for dissolving the herbicide and the soil water content at the moment of spiking. An optimized protocol for the extraction and quantification of 2,4-D and its main metabolite from soil samples is presented.     

Studies of toxaphene in technical standard and extracts of background air samples (Point Petre, Ontario) using multidimensional gas chromatography-electron capture detection (MDGC-ECD)

MDGC-ECD procedures have been used to provide insight into the compositional complexity of some of the specific peaks or clusters observed in the gas chromatographic analysis of a technical toxaphene standard, with reference to individual toxaphene congeners (Parlar # components) that are flow commercially available. These investigations have focussed initially upon those peaks and clusters recently identified (Shoeib. M., Brice, K.A., Hoff, R., 1999. Chemosphere 39, 849-871) as dominant constituents of background ambient air. Multiple electron-capturing components have been found to be present in all the species studied: the available individual toxaphene congeners have been matched against these components where possible. In similar fashion, the responses obtained in equivalent gas chromatographic elution windows from the analysis of typical processed air sample extracts have been investigated, with the results showing clear differences relative to the patterns found in the technical toxaphene standard. In most cases, the air sample shows reduced complexity with fewer components present in the cluster. Also, the presence of interfering responses (due to PCBs and other organochlorines) is quite apparent and significant, showing that major problems and errors could arise when using single-column GC-ECD procedures for quantitation of toxaphene in environmental samples. The presence of certain of the Parlar species in the air samples has been confirmed and in most cases these represent the dominant toxaphene component found in the targeted cluster. Furthermore, the persistence of certain congeners in the atmospheric samples appears to be strongly dependent upon chemical structure, since the congeners in question possess an alternating exo-endo chlorine substitution pattern around the six-membered ring in the bornane skeleton. Such persistence is probably the result of lower metabolization of toxaphene residues in soils, water and sediments leading to a similar pattern in the atmosphere following volatilization.     

Heavy metal contamination from mining sites in South Morocco: 1. Use of a biotest to assess metal toxicity of tailings and soils

Our work was conducted to investigate the heavy metal toxicity of tailings and soils collected from five metal mines located in the south of Morocco. We used the MetPAD biotest Kit which detects the toxicity specifically due to the heavy metals in environmental samples. This biotest initially developed to assess the toxicity of aquatic samples was adapted to the heterogeneous physico-chemical conditions of anthropogenic soils. Contrasted industrial soils were collected from four abandoned mines (A, B, C and E) and one mine (D) still active. The toxicity test was run concurrently with chemical analyses on the aqueous extracts of tailings materials and soils in order to assess the potential availability of heavy metals. Soil pH was variable, ranging from very acidic (pH 2.6) to alkaline values (pH 8.0-8.8). The tailings from polymetallic mines (B and D) contained very high concentrations of Zn (38,000-108,000 mg kg(-1)), Pb (20,412-30,100 mg kg(-1)), Cu (2,019-8,635 mg kg(-1)) and Cd (148-228 mg kg(-1)). Water-extractable metal concentrations (i.e., soil extracts) were much lower but were highly toxic as shown by the MetPAD test, except for soils from mines A, E and site C3 from mine C. The soil extracts from mine D were the most toxic amongst all the soils tested. On this site, the toxicity of soil water extracts was mainly due to high concentrations of Zn (785-1,753 mg l(-1)), Cu (1.8-82 mg l(-1)) and Cd (2.0-2.7 mg l(-1)). The general trend observed was an increase in metal toxicity measured by the biotest with increasing available metal contents in tailings materials and soils. Therefore, the MetPAD test can be used as a rapid and sensitive predictive tool to assess the heavy metal availability in soils highly contaminated by mining activities.     

Release of vanadium from oxidized sediments: insights from different extraction and leaching procedures

Although the attention for vanadium (V) as a potentially harmful element is growing and some countries adopted threshold values for V in soils, sediments, groundwater, or surface water, V is generally of little importance in environmental legislation and the knowledge about the behavior of V in the environment is still limited. In the present study, the release of V from oxidized sediments, sediment-derived soils, and certified reference materials was investigated by means of several types of leaching tests and extractions that are frequently used for soil and sediment characterization. The pH_stat leaching tests and single and sequential extractions applied in this study show that V generally displays a very limited actual and potential mobility in sediment. “Mobile” V concentrations, as estimated by the amount of V released by a single extraction with CaCl₂ 0.01 mol L^?1, were low, even in the most contaminated sediment samples. Only under strongly acidifying conditions (pH 2), such as in the case of ingestion of soil or sediment or in accidental spills, a substantial release of V can be expected.     

Development of supercritical carbon dioxide extraction with a solid phase trap for dioxins in soils and sediments

A method involving supercritical fluid extraction (SFE) with a solid phase trap containing activated alumina was investigated for the rapid analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin like polychlorinated biphenyls (DL-PCBs) in soils and sediments. The samples were extracted by using supercritical carbon dioxide with water (2% versus CO(2) flow velocity) being used as an entrainer at a pressure of 30 MPa and a temperature of 130 degrees C for 50 min. The extracts were adsorbed on an activated alumina trap that was maintained at a temperature of 150 degrees C, and then, PCDD/DFs and DL-PCBs were eluted with 20 ml of hexane at 60 degrees C. After concentration, they were measured with a high-resolution gas chromatograph interfaced to a high-resolution mass spectrometric detector. The average concentrations of PCDD/DFs and DL-PCBs corresponded to the results obtained by the conventional method, and the reproducibility of this SFE method was below 21% of the relative standard deviations for all samples. The total time required for the analysis of the pretreatment of this method was only 2 h.