Accurate prediction bioaccessibility of PAHs in soil-earthworm system by novel magnetic solid phase extraction technique.

Conventional chemical extraction methods may lead to overestimate or underestimate bioaccessibility due to their inability to provide realistic kinetic information regarding PAHs in soils. In this study, we propose the use of magnetic solid phase extraction (MSPE) technique for assessing the bioaccessibility of PAHs in the soil-earthworm system. Firstly, a novel polydopamine-coated magnetic core-shell microspheres (Fe3O4-C16@PDA) was developed by a one-pot sol-gel and self-polymerization method. The PDA coatings not only enhance the hydrophilicity of material surfaces but also exhibit excellent biocompatibility. The maximum adsorption capacity of Fe3O4-C16@PDA for 16 PAHs was 52.72 mg g-1, indicating that the proposed material fulfills the assessment requirements for highly contaminated soil. To compare the measurement of PAHs and their uptake by earthworms (Eisenia fetida), experiments were conducted using four different soils with varying properties. The desorption kinetics data obtained from these experiments demonstrated that the capability of the MSPE in accurately predicting the bioavailable portions of PAHs. After a 28-day exposure, the best predictor of bioavailable PAHs in earthworms was MSPE method exhibited the highest correlation coefficient (R2 > 0.90), and its slopes in the four soils were 0.972, 0.961, 1.012, and 0.962, respectively, all close to 1. These results demonstrate that the MSPE method successfully mimics the conditions encountered in soil-earthworm systems and effectively assess bioaccessibility of PAHs in soils.

Magnetic poly(ß-cyclodextrin) combined with solubilizing agents for the rapid bioaccessibility measurement of polycyclic aromatic hydrocarbons in soils.

The rapid determination of the bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in soils is challenging due to their slow desorption rates and the insufficient extraction efficiency of the available methods. Herein, magnetic poly(ß-cyclodextrin) microparticles (Fe3O4@PCD) were combined with hydroxypropyl-ß-cyclodextrin (HPCD) or methanol (MeOH) as solubilizing agents to develop a rapid and effective method for the bioaccessibility measurement of PAHs. Fe3O4@PCD was first validated for the rapid and quantitative adsorption of PAHs from MeOH and HPCD solutions. The solubilizing agents were then coupled with Fe3O4@PCD to extract PAHs from soil-water slurries, affording higher extractable fractions than the corresponding solution extraction and comparable to or higher than single Fe3O4@PCD or Tenax extraction. The desorption rates of labile PAHs could be markedly accelerated in this process, which were 1.3-12.0 times faster than those of single Fe3O4@PCD extraction. Moreover, a low HPCD concentration was sufficient to achieve a strong acceleration of the desorption rate without excessive extraction of the slow desorption fraction. Finally, a comparison with a bioaccumulation assay revealed that the combination of Fe3O4@PCD with HPCD could accurately predict the PAH concentration accumulated in earthworms in three field soil samples, indicating that the method is a time-saving and efficient procedure to measure the bioaccessibility of PAHs.

Assessment of commercial porous polyethylene frit for extraction of polycyclic aromatic hydrocarbons from water.

Exploring commercial and inexpensive sorbents for extraction of organic pollutants is still an active area of research. Ultrahigh molecular weight polyethylene sieve plate (UMPESP) is a commercially available, low-cost, and porous frit, which has been widely used in solid-phase extraction cartridges to fix the filling materials. In this work, UMPESP was investigated for the extraction of polycyclic aromatic hydrocarbons (PAHs) from water samples. The desorption and sorption efficiencies of UMPESP were first evaluated and compared with two previously reported sorbents, low-density polyethylene plastic pellet (LDPEP) and silicone rod (SR). The comparative results showed that quantitative desorption of analytes from UMPESP, which could be easily achieved with 2 × 1.5 mL n-hexane, was more effective than that of LDPEP (>6 × 1.5 mL n-hexane) and comparable to that of SR. Additionally, shorter equilibrium time was rendered by UMPESP (shaking for 120 min) compared with SR (>480 min), due to the porous structure and larger surface area of the former. Different parameters that affect the extraction efficiency, including organic modifier, ionic strength, and pH value, were then studied. The optimized method coupled with gas chromatography-mass spectrometry afforded good linearity in a concentration range of 10-5000 ng L-1 (except acenaphthene in the range of 25-5000 ng L-1) with coefficients of determination ranging from 0.9957 to 0.9995 and relative standard deviations below 13.8%. The limits of detection and quantification were 0.04-3.35 ng L-1 and 0.13-11.16 ng L-1, respectively. Finally, the method was successfully applied to determine PAHs in real water samples, and the results showed no statistically significant difference with the concentrations derived from liquid-liquid extraction.

Magnetic solid-phase extraction as a novel method for the prediction of the bioaccessibility of polycyclic aromatic hydrocarbons.

Chemical methods used to predict the bioaccessibility of hydrophobic organic compounds (HOCs) still need further development and improvement. In this work, magnetic solid-phase extraction (MSPE) based on poly(ß-cyclodextrin)-coated magnetic polydopamine (Fe3O4@PDA@PCD) was first introduced to assess the bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in soils. Due to its good hydrophilicity and submicrometer scale, Fe3O4@PDA@PCD displayed a higher extraction rate for PAHs in an aqueous solution (equilibrium time < 5 min) than Tenax resin, which had an equilibrium time longer than 30 min. The merits of Fe3O4@PDA@PCD are beneficial to accelerate the desorption of PAHs from soil, especially for high molecular weight PAHs, in which the amounts extracted by Fe3O4@PDA@PCD were 1.2-2.8 times higher than those extracted by Tenax resin. The desorption kinetics data were well fitted with a two- or three-fraction model. The fitting results indicated that the MSPE method can be used to predict the bioaccessible fractions of PAHs. By comparing the prediction results obtained from the MSPE method with bioassays using earthworms, a significant linear correlation (R2 = 0.98) with a slope statistically close to 1 was obtained. These results suggested that the MSPE method can act as a simple and efficient method to measure the bioaccessibility of PAHs in soil.

Facile synthesis of polydivinylbenzene coated magnetic polydopamine coupled with pressurized liquid extraction for the extraction and cleanup of polycyclic aromatic hydrocarbons in soils.

Due to the trace levels of polycyclic aromatic hydrocarbons (PAHs) in soil and the complexity of soil matrices, effective sample pretreatment methods are of great significance to obtain accurate analytical results. In this paper, polydopamine (PDA) encapsulated Fe3O4 particles were used as seeds for in situ polymerization of divinylbenzene (DVB) to derive magnetic hybrid material Fe3O4@PDA@PDVB. Coupled with pressurized liquid extraction, Fe3O4@PDA@PDVB was investigated as a selective adsorbent for the extraction and cleanup of PAHs in soil. The prepared magnetic material was characterized and demonstrated to possess strong hydrophobicity and superparamagnetism. Under optimal conditions, Fe3O4@PDA@PDVB can effectively extract 15 PAHs from a 30% methanol solution within 2 min, and it is more selective for PAHs than for n-alkane in soil extracts. The matrix effect significantly decreased after extraction by the prepared material, which showed superiority to a silica gel column method (EPA 3630C Method). The developed method was linear (5-1000 ng g-1) with coefficient of determination (R2) ranging from 0.9986-0.9998, and the limits of detection were 0.13-0.54 ng g-1. Additionally, repetitive experiments indicated that the prepared material was reproducible and reusable with relative standard deviations below 8.4% and 8.6%, respectively. Finally, the new method was successfully employed to determine the concentrations of PAHs in genuine soil and standard reference material, and the results were comparable to those of widely utilized EPA methodology.

Polydopamine-coated polyethylene sieve plate as an efficient and convenient adsorption sink for the bioaccessibility prediction of PAHs in soils.

Bioaccessibility measurements of polycyclic aromatic hydrocarbons (PAHs) in soils are significant for exposure risk assessment. The current physicochemical methods require tedious operation processes, underestimate the actual risks, or are unsuitable for high organic content soils. In this work, an efficient and convenient method based on polydopamine-coated polyethylene sieve plate (PDA@PESP) and hydroxypropyl-ß-cyclodextrin (HPCD) was developed to predict the bioaccessibility of PAHs in multi-type soils. The PDA@PESP can be prepared via in situ self-polymerization, allowing to extract PAHs from HPCD solution quantitatively and rapidly. When applied to evaluate the bioaccessibility with PDA@PESP as an adsorption sink and HPCD as a diffusive carrier, the proposed method can significantly improve the extractable fraction of PAHs compared to single HPCD extraction in particular for high organic carbon content soil and high-ring PAHs. The desorption kinetics data indicated that the method can predict the bioaccessible fraction of PAHs. In addition, the method predicted a satisfactory accumulation into earthworms (Eisenia fetida) with a slope statistically approximated to 1. A highly significant linear regression (R2 = 0.95) was also found between the proposed method and Tenax desorption in historically contaminated soils, demonstrating that the method is an efficient and convenient approach for the bioaccessibility prediction of PAHs in soils.

Study on four metal organic frameworks as cleanup adsorbents for polycyclic aromatic hydrocarbons determined by GC-MS/MS.

A new application of MOFs as adsorbents in the cleanup procedure of polycyclic aromatic hydrocarbons (PAHs) in soils was explored. Four MOFs, specifically MIL-101(Cr), MIL-125(Ti), MIL-100(Fe) and UiO-66(Zr), were synthesized and characterized. A screening study was carried out to select the best adsorbent for the purification of sixteen PAHs in complex soil extract. It is found that the nature of metal ion, pore size, surface area and surface charge affect the purification efficiencies of the various MOFs. MIL-101(Cr) was then selected because of its best purification efficiency. The effects of amount of adsorbent, cleanup solvent and cleanup time on cleanup efficiency were investigated. Under the optimum conditions, the matrix effect of the target analytes was reduced by more than 65%. The method was then combined with ultrasonic extraction and quantitation by gas chromatography with triple quadrupole mass spectrometric detection. The method allows for the determination of PAHs in soils with linear in the range of 5-5000 ng g-1 and with LODs between 50 and 420 pg g-1. The method was applied to the analysis of (spiked) soil samples, and results compared well with the established EPA method. Graphical abstract Schematic presentation of metal organic frameworks (MOF) as cleanup adsorbents for purifying polycyclic aromatic hydrocarbons in soil organic matter (SOM) and further determined by gas chromatography with triple quadrupole mass spectrometry detection (GC-MS/MS).

Preparation of phenyl-modified magnetic silica as a selective magnetic solid-phase extraction adsorbent for polycyclic aromatic hydrocarbons in soils.

Accurate analysis of polycyclic aromatic hydrocarbons (PAHs) in soils remains a challenge due to the complexity of sample matrices. In this paper, phenyl-modified magnetic mesoporous silica (Fe3O4@mSiO2-Ph-PTSA) was synthesized with p-toluenesulfonic acid (PTSA) as the catalyst and used as a selective adsorbent for the clean-up of PAHs extracted from soils. The material prepared without PTSA as the catalyst (Fe3O4@mSiO2-Ph) was synthesized for comparison. The synthesized materials were first systematically characterized and evaluated. It was found that the grafting amount of the phenyl group onto Fe3O4@mSiO2-Ph-PTSA was higher than that onto Fe3O4@mSiO2-Ph. The extraction efficiency obtained by extracting PAHs from the extracted soil matrix solution demonstrated that Fe3O4@mSiO2-Ph-PTSA possessed a much higher extraction efficiency than that of Fe3O4@mSiO2-Ph, which can be attributed to the greater amount of phenyl groups grafted on Fe3O4@mSiO2 in the presence of the PTSA catalyst. Moreover, contrast experiments showed that Fe3O4@mSiO2-Ph-PTSA displayed higher selectivity towards PAHs than towards n-alkanes and that the π-π interaction played a key role in the adsorption process. In the presence of the soil extract matrix, the parameters affecting the extraction efficiency of Fe3O4@mSiO2-Ph-PTSA for PAHs were optimized. Under the optimal conditions, coupled with pressurized liquid extraction and gas chromatograph-mass spectrometer, the proposed method for the determination of PAHs in soils was linear in the range of 5-500 ng g-1, and the correlation coefficients (R) ranged between 0.9994 and 0.9999. The limits of detection (LODs) and limits of quantification (LOQs), which were based on signal-to-noise ratios of 3 and 10, respectively, were in the range of 0.07-0.41 ng g-1 and 0.24-1.37 ng g-1. The developed method displayed a better clean-up effect than that for silica gel column method, and the matrix effect markedly decreased compared to that of the uncleaned condition. Finally, the developed method was successfully applied for the detection of PAHs in environmental soils, and the data were consistent with the results obtained by the silica gel column method. The analytical results were also consistent with those for the real environment.