Organic Contaminants In Soil Research Articles

Target and suspect screening analysis reveals persistent emerging organic contaminants in soils and sediments

An approach to identifying persistent organic contaminants in the environment was developed and executed for Switzerland as an example of an industrialized country. First, samples were screened with an in-house list using liquid chromatography high-resolution mass spectrometry (LC-HRMS/MS) and gas chromatography tandem mass spectrometry (GC–MS/MS) in 13 samples from the Swiss National Soil Monitoring Network and three sediment cores of an urban and agricultural contaminated lake. To capture a broader range of organic contaminants, the analysis was extended with a suspect screening analysis by LC-HRMS/MS of >500 halogenated compounds obtained from a Swiss database that includes industrial and household chemicals identified, by means of fugacity modeling, as persistent substances in the selected matrices. In total, the confirmation of 96 compounds with an overlap of 34 in soil and sediment was achieved. The identified compounds consist generally of esters, tertiary amines, trifluoromethyls, organophosphates, azoles and aromatic azines, with azoles and triazines being the most common groups. Newly identified compounds include transformation products, pharmaceuticals such as the flukicide niclofolan, the antimicrobial cloflucarban, and the fungicide mandipropamid. The results indicate that agricultural and urban soils as well as sediments impacted by agriculture and wastewater treatment plants (WWTPs) are the most contaminated sites. The plausibility of this outcome confirms the combination of chemical inventory, modeling of partitioning and persistence, and HRMS-based screening as a successful approach to shed light on less frequently or not yet investigated environmental contaminants and emphasizes the need for more soil and sediment monitoring in the future.

An Integrated Approach to Remove PAHs from Highly Contaminated Soil: Electro-Fenton Process and Bioslurry Treatment

A combined process comprised of electro-Fenton and bioslurry (EF–bioslurry) was developed at lab scale for remediating a real coking plant soil with an initial polycyclic aromatic hydrocarbons (PAHs) content of 3605 mg/kg. Sodium citrate was used as a complexant to keep the iron in solution at near-neutral pH conditions for increasing the reaction rate. The appropriate order of application was to perform EF process followed by bioslurry, which was evaluated through analysis of degradation characteristics of individual processes. The optimum EF duration was assessed through an analysis of the induced changes in PAHs degradation and bacterial counts. The optimum application time of EF process was determined to be 24 h. The removal of PAHs was 95.2% for EF–bioslurry after 40 days, and the efficiency was increased by almost 150%, compared with the individual bioslurry treatment. The EF reaction caused significant cell death and high inhibition to polyphenol oxidase (PPO) activity of soil. The bacterial activity and counts in the slurry recovered rapidly after EF oxidation through the addition of raw soil (2%, w/w). Therefore, the combined process of EF–bioslurry process may be an efficient and promising approach for the remediation of highly organic-contaminated soil.

Effects of soil properties on the remediation of diesel-contaminated soil by Triton X-100-aided washing.

Although nonionic surfactant is widely used for petroleum-contaminated soil washing, there is no definite conclusion on the main soil factors which determine the removal of petroleum hydrocarbons from the soil. In this study, the influences of soil properties on Triton X-100-aided soil washing were investigated using 12 soils in China. The sorption characteristic of Triton X-100 on soils was described as well. The sorption isotherms of Triton X-100 on 12 typical soils were fitted to the Langmuir adsorption model, and the maximum sorption amount of Triton X-100 (Qmax) varied from 1.54 to 15.15mg/g. The removal rates of diesel for 12 soils were well fitted to the modified Michaelis-Menten equation, and the maximum removal rate of diesel (φmax) ranged from 62.92 to 90.36%. The correlation analysis indicated that the φmax is significantly correlated with the Qmax. The soil factors affecting diesel removal from soils followed the order of sand content > cation exchange capacity (CEC) > organic matter (OM) content > silt and clay content > SSA >> pH. The prediction model based on CEC, silt content, and pH explained 83.1% of variance of diesel removal from soils. This study will have important implication for successfully remediating organic-contaminated soil using nonionic surfactant-based soil washing.

Viability and distribution of bacteria immobilized on Sawdust@silica: The removal mechanism of phenanthrene in soil.

Immobilized cells (ICs) have been widely used to enhance the remediation of organic-contaminated soil (e.g., polycyclic aromatic hydrocarbons, PAHs). Once ICs are added to the heterogeneous soil, degradation hotspots are immediately formed near the carrier, leaving the remaining soil lack of degrading bacteria. Therefore, it remains unclear how ICs efficiently utilize PAHs in soil. In this study, the viability of Silica-IC (Cells@Sawdust@Silica) and the distribution of inoculated ICs and phenanthrene (Phe) in a slurry system (soil to water ratio 1:2) were investigated to explore the removal mechanism of PAHs by the ICs. Results showed that the Silica-IC maintained (i) good reproductive ability (displayed by the growth curve in soil and water phase), (ii) excellent stability, which was identified by the ratio of colony forming units in the soil phase to the water phase, the difference between the colony number and the DNA copies, and characteristics of the biomaterial observed by the FESEM, and (iii) high metabolic activity (the removal percentages of Phe in soil by the ICs were more than 95% after 48h). Finally, the possible pathways for the ICs to efficiently utilize Phe in soil are proposed based on the distribution and correlation of Phe and ICs between the soil and water phase. The adsorption-degradation process was dominant, i.e., the enhanced degradation occurred between the ICs and carrier-adsorbed Phe. This study provided new insights on developing a bio-material for efficient bio-remediation of PAHs-contaminated soil.

A three-phase-successive partition-limited model to predict plant accumulation of organic contaminants from soils treated with surfactants

The application of surfactants is an effective way to inhibit the migration of organic contaminants (OCs) from soil to plants, and thus would be a great candidate method for producing safe agricultural products in organic-contaminated farmland. In this study, it was found that cetyltrimethyl ammonium bromide (CTMAB) reduced the OCs in cabbage by 22.0–64.1%, and those in lettuce by 18.8–36.5%. We developed a mathematical model to predict the accumulation of OCs in plants in the presence of surfactants. The successive partitioning of OCs among three phases, namely, soil, soil water and plant roots, was considered. The equilibrium of OC between the soil and soil water was scaled using the sorption coefficient of OCs on soils normalized by the soil organic carbon (Koc) and carbon-normalized OCs sorption coefficient with the sorbed surfactants (Kss). To precisely calculate the Koc and Kss, the bioavailable and bound OCs were measured using a sequential extraction method. Linear positive correlations between the logarithm of Koc (or Kss) and the logarithm of the octanol-water partition coefficient (log Kow) of OCs were established for laterite soils, paddy soils and black soils. In the presence of CTMAB, the equilibrium of OCs between the soil water and plant roots was scaled using the carbon-normalized OC sorption coefficient with the sorbed surfactants (Ksf), whose logarithmic value was linearly correlated with the log Kow of the OCs. A three-phase-successive partition-limited model was developed based on these relationships, demonstrating an average prediction accuracy of 76.6 ± 36.8%. Our results indicated that the decrease in bioavailable OCs in soils and the increase in sorption of OCs on roots should be taken into consideration when predicting plant uptake. This research provides a validated mathematical model for predicting the concentration of OCs in plants in the presence of surfactants.

Soil toxicants that potentially affect children's health

Soil pollution is a global phenomenon, and children are uniquely susceptible to the wide range of toxicants that persist in topsoil. Given their increased exposure through mouthing activities, increased body surface area, likelihood of breathing air closer to soil, and immature immune and elimination systems, it is essential to understand the mechanisms of children's exposure and the potential health effects of toxicants found in soil. Here we describe the sources and toxicological profiles of a range of inorganic and organic soil contaminants, including arsenic (As), cadmium (Cd), lead (Pb), mercury (Hg), benzene, toluene, ethylbenzene and xylenes, chlorinated dibenzo-p-dioxins, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), per and polyfluoroalkyl substances (PFAS), as well as agricultural and domestic sources of pollution. The aim of this article is to increase awareness regarding the risks and health impacts of contaminated soil, and to encourage further research and efforts aimed at mitigating children's exposure.

Effects of rice straw biochar on sorption and desorption of di-n-butyl phthalate in different soil particle-size fractions

Sorption of organic contaminants by biochar greatly affects their bioavailability and fate in soils. Nevertheless, very little information is available regarding the effects of biochar on sorption and desorption of organic contaminants in different soil particle-size fractions. In this study, di-n-butyl phthalate (DBP), a prevalent organic contaminant in agricultural soils, was taken as a model contaminant. The effects of biochar on DBP sorption and desorption in six particle-size fractions (i.e., coarse sand, fine sand, coarse silt, fine silt, clay, and humic acid fractions) of paddy soil were investigated using batch sorption-desorption experiments. A straw-derived biochar with high specific surface area (116 m2/g) and high content of organic matter (OM) rich in aromatic carbon (67%) was prepared. Addition of this biochar (1% and 5%) significantly promoted the sorption and retention of DBP in all the paddy soil particle-size fractions at environmentally relevant DBP concentrations (2–12 mg/L) with 1.2–132-fold increase of the Kd values. With increasing addition rates of biochar, DBP retention by the biochar enhanced. The biochar’s effectiveness was remarkably influenced by the physicochemical properties of the soil particle-size fractions, especially, the OM contents and pore size showed the most striking effects. A parameter (rkd) reflecting the biochar’s effectiveness showed negative and positive correlations with OM contents and pore size of the soil particle-size fractions, respectively. Accordingly, strong effect of the biochar was found in the soil fractions with low OM contents and high pore size. The findings of this study gave insight into the effects and influencing factors of biochar on sorption and desorption of organic contaminants in soils at scale of various particle-size factions.

Piece written by mother of 18 year old transgender male

Soil pollution is a global phenomenon, and children are uniquely susceptible to the wide range of toxicants that persist in topsoil. Given their increased exposure through mouthing activities, increased body surface area, likelihood of breathing air closer to soil, and immature immune and elimination systems, it is essential to understand the mechanisms of children's exposure and the potential health effects of toxicants found in soil. Here we describe the sources and toxicological profiles of a range of inorganic and organic soil contaminants, including arsenic (As), cadmium (Cd), lead (Pb), mercury (Hg), benzene, toluene, ethylbenzene and xylenes, chlorinated dibenzo-p-dioxins, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), per and polyfluoroalkyl substances (PFAS), as well as agricultural and domestic sources of pollution. The aim of this article is to increase awareness regarding the risks and health impacts of contaminated soil, and to encourage further research and efforts aimed at mitigating children's exposure.

Activation of persulfate with biochar for degradation of bisphenol A in soil

In this study, a new alternative activator, biochar (BC) pyrolyzed by waste biomass—lychee branch, was applied in persulfate (PS) -based remediation for bisphenol A (BPA) in soils. Radical species, solution pH, dose of PS and BC were studied to evaluate the performance of PS activation by BC to degrade BPA in aqueous solution. The results show that BC can efficiently activate PS to generate sulfate radicals and hydroxyl radicals to degrade BPA high efficiently. The increase of PS and BC dosage can increase BPA removal rate, and a lower pH is benefit for the BPA degradation in aqueous solution. In addition, the degradation intermediates of BPA were characterized and the degradation pathways were proposed. Furthermore, the PS/BC system is most efficient for BPA degradation compared with other oxidants. For soil spiked with 31.93 mg kg−1 BPA, BC can also activate PS and degrade BPA effectively. The increase of BC and PS dose cannot always increase BPA degradation because of the competition of readily oxidizable matter introduced by BC itself and/or quenching of sulfate radicals. During BPA degradation in soil, the pH value drops less than those in literatures on PS oxidation of organic contaminants in soil by other activation methods, which can alleviate soil acidification in the remediation process. The results of this study suggest a novel technique for potential application in in-situ remediation of organic contaminated sites.

Caracterización física y química de biochar de lodos residuales.

Pyrolysis treatment of sewage sludge to generate biochar is one of the current alternatives for environmental management of this waste. The treatment transforms sewage sludge into biochar, conserves some of the characteristics that give it an important agronomic value and reduces its pathogen content. The objective of this study was to analyze the potential use of the sewage sludge biochar obtained from the wastewater treatment plant (WWTP) of Morelia, Michoacán, México, as an agricultural soil improver considering the physical-chemical properties of the material and its content of nutrients and heavy metals as indicators. The sewage sludge was subjected to pyrolysis (SSB) in an experimental scale reactor that uses solar energy, with six residence times and temperature of 280 to 355 oC. The parameters analyzed were: pH EC, OM, Cu, Mn, Zn, Fe available (DTPA and EDTA), elemental composition (C, N, O, Ca, Mg, Na, K, P, S, Cl, Si, Al, Fe, Mn, Cu, Zn, Ti, Ni, Cr, Cd and Pb). The EC of the SSB obtained was from 592 to 5240 μS cm‑1, pH = 6.33 to 7.02, OM = 3.8 to 5.6%, high contents of C, N, P (31 to 38%, 6.5 to 7.7% and 37.7 to 48.8 g kg‑1, respectively), low Na/Ca ratio and a low content of total and available heavy metals. The properties of the SSB obtained indicate that it can be used as an agricultural soil improver since it is a material with high nutrient content and low environmental risk in terms of its low heavy metal content. These results should be complemented with studies on the response of plants to BLR, monitoring of physical-chemical conditions and analysis of organic contaminants in soil and water where this material is applied.

Environmental forensic characterization of former rail yard soils located adjacent to the Statue of Liberty in the New York/New Jersey harbor

Identifying inorganic and organic soil contaminants in urban brownfields can give insights into the adverse effects of industrial activities on soil function, ecological health, and environmental quality. Liberty State Park in Jersey City (N.J., USA) once supported a major rail yard that had dock facilities for both cargo and passenger service; a portion remains closed to the public, and a forest developed and spread in this area. The objectives of this study were to: 1) characterize the organic and inorganic compounds in Liberty State Park soils and compare the findings to an uncontaminated reference site (Hutcheson Memorial Forest); and 2) identify differences between the barren low-functioning areas and the forested high-functioning areas of the brownfield. Soil samples were solvent-extracted, fractionated, and analyzed by gas chromatography–mass spectrometry and subjected to loss-on-ignition, pyrolysis-gas chromatography–mass spectrometry, inductively-coupled-plasma mass spectrometry, and optical microscopy analyses. Compared to soil from the reference site, the forested soils in Liberty State Park contained elevated percentages of organic matter (30–45%) and more contaminants, such as fossil-fuel-derived hydrocarbons and coal particles. Microscopy revealed bituminous and anthracite coal, coke, tar/pitch, and ash particles. Barren and low-functioning site 25R had a similar organic contaminant profile but contained a higher metal load than other Liberty State Park sites and also lacked higher plant indicators. These can obscure the signatures of contaminants, and data from adjacent barren and vegetated sites are valuable references for soils studies. A deeper understanding of the chemistry, biochemistry, and ecology of barren soils can be leveraged to prevent land degradation and to restore dysfunctional and phytotoxic soils.

Metal-organic framework (MOF-5) coated SERS active gold gratings: A platform for the selective detection of organic contaminants in soil

In this work, we proposed the functionalization of a surface plasmon-polariton (SPP)-supported gold grating surface with the metal-organic framework (MOF-5) for sensitive, selective and reproducible surface-enhanced Raman scattering (SERS) detection of organophosphorus pesticides. Homogeneous distribution of plasmon intensity along the Au grating surface ensures the high reproducibility of SERS results (deviation of Raman peak intensity does not exceed the 4% along the sample). The surface-assisted growth of thin MOF-5 film was accomplished in two steps procedure: (i) covalent grafting by 4-carboxyphenyl groups and (ii) the immersion of samples in the mother liquid of MOF-5. Proposed SERS chip proved itself to be a perfect analytical probe for the detection of organophosphorus pesticides with high reliability and low detection limit up to 10−12 M. Moreover, selective detection and recognition of several relevant organic contaminants (azo-dye, mycotoxin, and pesticide) from the simulated soil was successfully demonstrated. All SERS measurements were performed using portable Raman spectrometer and can easily be expanded to environmental conditions. Our work combines the high affinity of organic contaminants to the MOF-5 with excellent plasmonic excitation on the surface plasmon-polariton supported structure and shows the way to the realization of closed-to-ideal analytical SERS chip.

Analysis and fate of 14 relevant wastewater-derived organic pollutants in long-term exposed soil.

The growing use of reclaimed water in agriculture worldwide calls for developing high-sensitivity methods to quantify wastewater-derived organic contaminants in soils so that the potential risk of this irrigation practice can be properly assessed. This work describes an analytical method for the determination of trace levels of 14 drugs that are known to be poorly removed during conventional wastewater treatment in soil. The analytes selected for investigation included ten pharmaceuticals from different therapeutic classes (carbamazepine, diclofenac, cis-diltiazem, lamotrigine, methadone, midazolam, oxcarbazepine, sulfamethoxazole, trimethoprim, valsartan), one illicit drug (cocaine), and three transformation products/metabolites (acridone, 4'-hydroxydiclofenac, and valsartan acid), thereby covering a broad range of physical-chemical properties. The methodology developed was based on ultrasonic solvent extraction (USE) of the analytes from the soil matrix, and subsequent clean-up and analysis of the USE extracts with a fully automated approach by means of solid-phase extraction and liquid chromatography-tandem mass spectrometry detection (online SPE-LC-MS/MS). The method was fully validated with affording method detection and quantification limits ranging from 0.03 to 1ngg-1 and from 0.09 to 3.3ngg-1, respectively. This method was applied to investigate the fate of the selected drugs in potting soil irrigated for a long term (60days) either with water containing the target compounds at a concentration of 200μgL-1 or with wastewater treatment plant effluent and thus, at real environmental concentrations. All investigated compounds were found to accumulate in soil irrigated with artificially fortified water. The highest accumulation potential was observed for cis-diltiazem followed by methadone and midazolam that presented average concentrations of 1517ngg-1, 1041ngg-1, and 962ngg-1 d.w., respectively. On the contrary, oxcarbazepine (5.8ngg-1) and sulfamethoxazole (22ngg-1) were the target drugs presenting the lowest accumulation potential. Only trace levels of ten drugs were measured in soil irrigated with regenerated water (average concentrations between 1.6 and 4.7ngg-1 d.w.). Graphical abstract.

Comparison of the bioavailability of benzo[a]pyrene (B[a]P) in a B[a]P-contaminated soil using the different addition approaches

Determination of the bioavailability of the hydrophobic organic contaminant benzo[a]pyrene (B[a]P) is extremely important for assessing its environmental risk. The effect of addition manner of B[a]P on the bioavailability and toxicity of B[a]P in soil remains unclear. In this study, soil samples, spiked with B[a]P by one-time or multiple-time additions, were tested to investigate the available fraction of B[a]P in soils, the uptake of B[a]P by red wiggler worms (Eisenia fetida), as well as superoxide dismutase (SOD) and peroxidase (POD) activities in earthworm coelomocytes at different periods. Results showed that the available fraction of B[a]P in soils and the amount of B[a]P assimilated by earthworms declined sharply from 1 d to 28 d during the incubation period and then decreased slowly from 28 to 56 d in both the one-time and the multiple-time addition tests. The available fraction of B[a]P in soils and its uptake by earthworms were significantly lower in multiple-time addition samples than those in one-time addition samples, a finding which was consistent with the SOD and POD activities in earthworms during the whole 56-d incubation period. These variations in the characteristics of the two addition treatments may be due to the differences in the way the B[a]P aged in the soil. These results indicated that the addition method was an important factor influencing the bioavailability of organic contaminants in soils.

Transfer of organic pollutants from sewage sludge to earthworms and barley under field conditions

We investigated dissipation, earthworm and plant accumulation of organic contaminants in soil amended with three types of sewage sludge in the presence and absence of plants. After 3 months, soil, plants and earthworms were analyzed for their content of organic contaminants. The results showed that the presence of plant roots did not affect dissipation rates, except for galaxolide. Transfer of galaxolide and triclosan to earthworms was significant, with transfer factors of 10–60 for galaxolide and 140–620 for triclosan in the presence of plants. In the absence of plants, transfer factors were 2–9 times higher. The reduced transfer to worms in the presence of plants was most likely due to roots serving as an alternative food source. Nonylphenol monoethoxylate rapidly dissipated in soil, but initial exposure resulted in uptake in worms, which was detected even 3 months after sewage sludge application. These values were higher than the soil concentration at the start of the exposure period. This indicates that a chemical's short half-life in soil is no guarantee that it poses a minimal environmental risk, as even short-term exposure may cause bioaccumulation and risks for chronic or even transgenerational effects.

Electrokinetic Remediation of a Soil Contaminated with Anthracene Using Different Surfactants

Abstract Electrokinetic technique is one of the common methods that can be used for removal of organic contaminants in soil. There are some organic contaminants with low solubility in water. To imp...

Reductive biotransformation as a pretreatment to enhance in situ chemical oxidation of nitroaromatic and nitroheterocyclic explosives

In Situ Chemical Oxidation (ISCO) is increasingly being used to remediate a variety of organic contaminants in soil and groundwater. Explosives, such as 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dintroanisole (DNAN), and 3-nitro-1,2,4-triazol-5-one (NTO), are not easily oxidized due to the presence of nitro groups in their structures. However, these nitro groups can be reduced to amino groups by soil microorganisms, making them more prone to oxidation. In this study, we propose bioreduction as a pretreatment to ISCO. The oxidation of DNAN, DNT, NTO, and their respective reduced transformation products, 2-methoxy-5-nitroaniline (MENA), 4-amino-2-nitrotoluene (NAT), and 3-amino-1,2,4-triazol-5-one (ATO), by potassium permanganate showed that lower permanganate concentrations and shorter time-scales are needed to oxidize the compounds once they are reduced. Significant fractions of the daughter products were mineralized to CO2 (30% and 22% for MENA and NAT, respectively, using 2.5 mM permanganate, and 48% for ATO using 1.0 mM permanganate). The bioreductive pretreatment was demonstrated by incubating 1.0 mM NTO anaerobically using soil as inoculum and pyruvate as electron donor. Once NTO was completely reduced to ATO, 1.0 mM permanganate was added, immediately oxidizing 86% of the compound. In controls without pretreatment, no oxidation was observed. NTO and ATO oxidation was tested in soils that differed in organic matter content. The results indicate that natural organic matter decreases the efficiency of NTO oxidation. However, ATO oxidation was not affected by the presence of soil. Our results suggest that the proposed reductive pretreatment followed by ISCO presents a safe and cost-effective alternative for explosives remediation.

Emergent functional behaviour of humic substances perceived as complex labile aggregates of small organic molecules and oligomers

Environmental contextThe correlation of physicochemical characteristics of humic substances with their function is crucial to our understanding of how environmental pollutants interact with humic substances. We have developed an approach that models emergent functions of fulvic and humic acids depending on sample characteristics. The results will be useful for predicting the sequestration of organic contaminants in soil under various conditions. AbstractThe structural organisation of humic substances (HS) has been a central question of earth sciences for several decades. The latest experimental results have led to the recognition of HS as complex mixtures of small molecules and oligomers. We investigate the correlation between the chemical composition of HS, perceived as labile aggregates, and the emergent functions. Computational modelling was used to help to understand the processes and mechanisms on the molecular scale that occur in different fractions of the HS, fulvic acids (FA) and humic acids (HA), as they interact with metal ions and organic pollutants. The importance of non-covalent interactions in the emergent functions of HS is highlighted. H-bonding, hydrophilic/hydrophobic surface areas and π-stacking interactions play a significant role in aggregation processes as well as in the sorption of environmental pollutants. In a highly hydrophilic system with small molecules (the SRFA-22 model), H-bonding is the main force that drives the aggregation process. However, in a highly aromatic and hydrophobic model with larger molecular fragments (SRHA-6), hydrophobic and π-stacking interactions dominate in the aggregation process. The chemical properties of contaminants significantly affect their mechanisms of sorption by HS. The interaction of a polar pollutant, phenol, with HS occurs through H-bonding, whereas non-polar benzene interacts through hydrophobic and π-stacking interactions. The non-polar pollutant results in a much stronger sorption by HS and causes an additional structural rearrangement of the aggregates, which make it more stable in the environment.

Polyethylene microplastics influence the transport of organic contaminants in soil

Plastics are now found in all natural environments including soil. The effects of microplastics in terrestrial systems, however, remain largely unexplored. Polyethylene is one of the mass-manufactured polymers found in terrestrial environments. It is used in many different sectors, for example in agricultural mulches, composite materials, and packaging. The presence of microplastics in soil, including polyethylene, can affect the transport of hydrophobic organic pollutants including pesticides. The objective of this study was to investigate the influence of polyethylene microplastics (<250 μm) on the transport of two selected organic plant-protection agents (atrazine and 4-(2,4-dichlorophenoxy) butyric acid) in soil under different aqueous conditions, using inverse liquid chromatography. The distribution coefficients for the sorbates that were sorbed to pure polyethylene microplastic were found to be significantly smaller than those for the sorbates sorbed to pure soil. The addition of 10% (w/w) polyethylene to the soil therefore led to an overall reduction in sorption, but the sorption trends due to variations in pH and ionic strength were not affected. The results imply that the presence of polyethylene microplastics in soil may therefore increase the mobility of organic contaminants by reducing the sorption capacity of natural soils, which must be validated by further research.

Multi-residue analysis of chiral and achiral trace organic contaminants in soil by accelerated solvent extraction and enantioselective liquid chromatography tandem–mass spectrometry

Reported here is the first analytical methodology for the enantiomeric determination of chiral trace organic contaminants (TOrCs) in soil. Direct enantioselective separations were achieved on a Chirobiotic V2® column operated in polar ionic mode. Initial screening of vancomycin stationary phases found Chirobiotic V2® better suited for multi-residue separation of chiral TOrCs than Chirobiotic V® due to differences in the ligand linkage chemistry. Simultaneous enantioseparation of beta-blockers, beta-agonists, anti-depressants, anti-histamines and stimulants was achieved for the first time. This included the first separation of chlorpheniramine enantiomers with a method suitable for environmental analysis (i.e., coupled to MS). Investigation of mobile phase composition found the concentration of liophilic ions had the greatest influence on enantioseparations and of most importance during method development. The optimized method achieved simultaneous separation of salbutamol, propranolol, atenolol, amphetamine, chlorpheniramine and fluoxetine enantiomers with satisfactory resolution (>1.0). For completeness, such methods also need to support analysis of achiral TOrCs. Therefore three achiral TOrCs (carbamazepine, carbamazepine 10,11 epoxide and triclocarban) were included to demonstrate the methods suitability. Method recoveries for all analytes ranged from 76 to 122% with method quantitation limits (MQLs) <1 ng g−1. Application of the method to soil microcosm studies revealed stereoselective degradation of chiral TOrCs for the first time. For example, S(+)-amphetamine degraded at a faster rate than its corresponding enantiomer leading to an enrichment of R(−)-amphetamine. Therefore to better understand the risk posed from TOrCs on the terrestrial environment, chiral species need profiled at the enantiomeric level. This can now be addressed using the proposed methodology whilst simultaneously profiling achiral TOrCs.