Incorporation of Cu-TATAB metal-organic framework within polyurethane nanocomposite for enhanced thin film microextraction of some chlorinated pesticides.

In this research, electrospun nanofibers based on copper-based metal organic framework (MOF)/polyurethane (PU) were prepared in order to achieve an applicable and superior extractive phase. The incorporation of MOF, in the synthesized nanocomposite contributed to the enhanced sorption efficiency. The prepared sorbent was implemented for the thin film microextraction (TFME) of target compounds with subsequent quantification using gas chromatography-mass spectrometry (GC-MS). To obtain the maximum efficiency of the synthesized sorbent, the influential parameters on extraction and desorption steps, including the MOF percentage in nanocomposite, desorption solvent type and its volume, desorption time, solution ionic strength and extraction time were optimized. After method development, the linear dynamic range (0.02-700 µg L-1), limits of detection (LODs) (0.005-0.1 µg L-1) and limits of quantification (LOQs))0.02-0.33 µg L-1(were calculated. The relative standard deviations values for intra-day and inter-day analysis were found to be in the range of 4.3-5.3 % and 6.2-8.1 %, respectively. The developed method was validated for the TFME of model organochlorine (OC) pesticide residues in fish, soil and water samples. the recovery values for the spiked samples at two concentration levels of 5 and 100 µg l-1 were found in the range of 72-110 %.

Identification of ∼200 transformation products of polyhalogenated compounds to characterize their transformation pathways in sludges.

Sewage sludge adsorbs a large amount of harmful organic pollutants, particularly the persistent and hydrophobic polyhalogenated compounds (PHCs). PHCs have been subjected to biological and chemical oxidation treatments during wastewater treatment processes; however, the species and concentrations of their transformation products (TPs) in sludge remain unknown, and the transformation pathways are unclear. In this study, 234 TPs of PHCs, including 77 TPs of chlorinated paraffins (CPs-TPs), 102 TPs of organochlorine pesticides (OCPs-TPs), 45 TPs of dechlorane plus (DPs-TPs), and 10 TPs of brominated flame retardants (BFRs-TPs), were identified in sludge through Ph4PCl-enhanced ionization coupled with ultra-performance liquid chromatography-Orbitrap-mass spectrometry. Based on the chemical structures of the identified TPs, we identified three major transformation pathways: dehalogenation-hydroxylation, carbon chain decomposition, and desulfurization. Approximately 97 TPs were newly discovered through the pathways. Carbon chain decomposition products of OCPs and DPs were detected for the first time at relatively high abundances. More hydroxylation products of DPs and hexabromocyclododecane (HBCD) and multi-dehalogenation products of heptachlor, toxaphene, DPs and HBCDs were detected at relative intensities higher than those of the known TPs. The oxidation treatment of sludge achieved up to 13 %-94 % of PHCs to be removed, with dehalogenation-hydroxylation as the main transformation pathway. Advanced treatment technologies are needed for degradation of both PHCs and their TPs.

Comparing Cell Penetration of Biotherapeutics across Human Cell Lines.

A major obstacle in biotherapeutics development is maximizing cell penetration. Ideally, assays would allow for optimization of cell penetration in the cell type of interest early in the drug development process. However, few assays exist to compare cell penetration across different cell types independent of drug function. In this work, we applied the chloroalkane penetration assay (CAPA) in seven mammalian cell lines as well as primary cells. Careful controls were used to ensure that data could be compared across cell lines. We compared the nuclear penetration of several peptides and drug-like oligonucleotides and saw significant differences among the cell lines. To help explain these differences, we quantified the relative activities of endocytosis pathways in these cell lines and correlated them with the penetration data. Based on these results, we knocked down clathrin in a cell line with an efficient permeability profile and observed reduced penetration of peptides but not oligonucleotides. Finally, we used small-molecule endosomal escape enhancers and observed enhancement of cell penetration of some oligonucleotides, but only in some of the cell lines tested. CAPA data provide valuable points of comparison among different cell lines, including primary cells, for evaluating the cell penetration of various classes of peptides and oligonucleotides.

A fungal hyphae-derived biomass carbon for magnetic solid-phase extraction of the organochlorine pesticides in water samples, tea beverages, and Chinese traditional medicines before gas chromatography-tandem mass spectrometry determination.

A magnetic biochar nanomaterial derived from fungal hyphae was introduced into the sample preparation field. The magnetic fungal hyphae-derived biomass carbon (MFHBC) could be produced by a controllable hydrothermal method. In order to obtain the best sorbent for magnetic solid-phase extraction (MSPE), the reaction conditions containing temperature, time and the consumption of fungal hyphae were investigated. A series of MFHBC materials were characterized by vibrating sample magnetometers, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy. A material with a satisfactory saturation magnetization (21.58 emu g-1) and largest surface area (88.06 m2 g-1) was selected as the sorbent to extract ten typical organochlorine pesticides (OCPs). The extraction conditions were optimized as 20 mL of sample solution with 70 mg of sorbent and 2.0 g of NaCl oscillated at 50 °C for 5.0 min. And the optimum desorption was performed by oscillating sorbent in 1.0 mL acetonitrile for 5.0 min. Then, the MFHBC-based MSPE-GC-MS/MS methods were established for different samples including water samples, tea beverages, and Chinese traditional medicines. The linearities were 10-2500 ng L-1 or 100-25,000 ng kg-1, and the limits of detection were 0.3-13.9 ng L-1 for water sample, 0.1-9.7 ng L-1 for tea beverage samples, 0.1-21.4 ng L-1 for Shenqi Fuzheng injection samples, and 7.2-278.3 ng kg-1 for Astragali Radix decoction pieces. Except for satisfactory repeatability (RSDs ≤13.8%) in intra-day and inter-day tests (n = 3), the reproducibility (RSDs ≤13.5%, n = 3) of MFHBC was acceptable. The methods were applied in the determination of OCPs from above real samples, with the recoveries of 80.5-117.2% and the RSDs (n = 3) <8.9%. The methods were suitable in the sensitive determination of OCPs from simple to complex matrix samples.

A combined experimental and computational investigation on the OH radical and Cl atom-initiated reaction of 2,3-dichloropropene in troposphere.

Temperature-dependent kinetics of OH radical and Cl atom-initiated reaction of an important halogenated alkene, 2,3-Dichloropropene (23DCP), were investigated using absolute and relative methods over 278-363 K. Pulsed laser photolysis - laser induced fluorescence technique and relative rate method using gas chromatography with flame ionization detector were employed for studying the kinetics of 23DCP with OH radical and Cl atom, respectively. The obtained Arrhenius expressions were kOH(expt)=(4.08 ± 1.63) × 10-13exp{(1043 ± 124)/T} cm3 molecule-1 s-1 and kCl(expt)=(1.54 ± 0.24) × 10-11exp{(705 ± 48)/T} cm3 molecule-1 s-1. Computational calculations were conducted to validate our experimental kinetic results and provide new insights into the importance of a particular pathway among all based on thermodynamic parameters. The addition of OH/Cl to the terminal carbon of the double bond present in 23DCP proved to be the predominant pathway across the selected temperature range for the present study (200-400 K). The degradation mechanism of these reactions was proposed by analyzing the products with the aid of gas chromatography with mass spectrometry. Calculating various atmospheric implication parameters can help to understand how the release of 23DCP may affect the troposphere.

Simultaneous effervescence-assisted microextraction and magnetic adsorbent generation for rapid and cost-effective organochlorine pesticides analysis.

This study introduced an innovative magnetic effervescence-assisted microextraction method, streamlining the preparation of effervescent tablets through a one-pot method that blends a CO2 donor (Na2CO3) and an H+ donor (NaH2PO4) with bare magnetic particles (Fe3O4) and an adsorbent (hydroxylated multi-walled carbon nanotubes), followed by pressing. During the extraction process, the bare magnetic particles and adsorbent undergo in-situ self-assembly to create a magnetic adsorbent. The effervescence generates bubbles that enhance effective extraction and magnetism facilitates the easy separation of the magnetic adsorbent from the sample solution, completing the process within 4 min. Applied to organochlorine pesticide analysis in fruit juices and herbal extracts, the method exhibits excellent linearity (R2 > 0.993), sensitivity (detection limits: 0.010-0.125 ng/mL), accuracy (recoveries: 85.8-99.9%), and precision (RSDs < 9.7%) with GC-ECD. Overall, this approach stands out for its simplicity, cost-effectiveness, and suitability for on-site analysis, owing to its operational ease and independence from specialized equipment.

Biochar-derived organic carbon promoting the dehydrochlorination of 1,1,2,2-tetrachloroethane and its molecular size effects: Synergies of dipole-dipole and conjugate bases.

The environmental effects of biochar-derived organic carbon (BDOC) have attracted increasing attention. Nevertheless, it is unknown how BDOC might affect the natural attenuation of widely distributed chloroalkanes (e.g., 1,1,2,2-tetrachloroethane (TeCA)) in aqueous environments. We firstly observed that the kinetic constants (ke) of TeCA dehydrochlorination in the presence of BDOC samples or their different molecular size fractions (<1 kDa, 1∼10 kDa, and >10 kDa) ranged from 9.16×103 to 26.63×103 M-1h-1, which was significantly greater than the ke (3.53×103 M-1h-1) of TeCA dehydrochlorination in the aqueous solution at pH 8.0, indicating that BDOC samples and their different molecular size fractions all could promote TeCA dehydrochlorination. For a given BDOC sample, the kinetic constants (ke) of TeCA dehydrochlorination in the initial pH 9.0 solution was 2∼3 times greater than that in the initial pH 8.0 solution due to more formation of conjugate bases. Interestingly, their DOC concentration normalized kinetic constants (ke/[DOC]) were negatively correlated with SUVA254, and positively correlated with A220/A254 and the abundance of aromatic protein-like/polyphenol-like matters. A novel mechanism was proposed that the CH dipole of BDOC aliphatic structure first bound with the CCl dipole of TeCA to capture the TeCA molecule, then the conjugate bases (-NH-/-NH2 and deprotonated phenol-OH of BDOC) could attack the H atom attached to the ß-C atom of bound TeCA, causing a CCl bond breaking and the trichloroethylene formation. Furthermore, a fraction of >1 kDa had significantly greater ke/[DOC] values of TeCA dehydrochlorination than the fraction of <1 kDa because >1 kDa fraction had higher aliphiticity (more dipole-dipole sites) as well as more N-containing species and aromatic protein-like/polyphenol-like matters (more conjugate bases). The results are helpful for profoundly understanding the BDOC-mediated natural attenuation and fate change of chloroalkanes in the environment.

Determination of hazardous vapors from the thermal decomposition of organochlorinated silica xerogels with adsorptive properties.

The incorporation of organic groups into sol-gel silica materials is known to have a noticeable impact on the properties and structure of the resulting xerogels due to the combination of the properties inherent to the organic fragments (functionality and flexibility) with the mechanical and structural stability of the inorganic matrix. However, the reduction of the inorganic content in the materials could be detrimental to their thermal stability properties, limiting the range of their potential applications. Therefore, this work aims to evaluate the thermal stability of hybrid inorganic-organic silica xerogels prepared from mixtures of tetraethoxysilane and organochlorinated triethoxysilane precursors. To this end, a series of four materials with a molar percentage of organochlorinated precursor fixed at 10%, but differing in the type of organic group (chloroalkyls varying in the alkyl-chain length and chlorophenyl), has been selected as model case study. The gases and vapors released during the thermal decomposition of the samples under N2 atmosphere have been analyzed and their components determined and quantified using a thermogravimetric analyzer coupled to a Fourier-transform infrared spectrophotometer and to a gas chromatography-mass spectrometry unit. These analyses have allowed to identify up to three different thermal events for the pyrolysis of the organochlorinated xerogel materials and to elucidate the reaction pathways associated with such processes. These mechanisms have been found to be strongly dependent on the specific nature of the organic group.

Characteristics and degradation mechanisms of polychlorinated naphthalenes in surface soil in Yangtze River Delta, China.

Both thermal and environmental processes are significant factors influencing the existing characteristics, e.g., congener distributions, and existing levels, of polychlorinated naphthalenes (PCNs) in the environment. Soil plays an important role in the life cycle of PCNs, but degradation of PCNs in soils has never been reported. In this study, we collected surface soil samples from 13 cities in the Yangtze River Delta, which is one of the most crowded areas of China and analyzed the samples for 75 PCNs. The long-range transportation from polluted areas was the major source for PCNs in remote areas, but the PCN profiles in remote areas reported in our previous studies were different from those in human settlement in this study, indicating there is a transformation of PCNs after emissions from anthropogenic activities. Two experiments were then designed to reveal the degradation mechanisms, including influencing factors, products, and pathways, of PCNs in surface soils. Based on the experiments, we found that the major factor driving the losses of PCNs in surface soils was volatilization, followed by photo irradiation and microbial metabolism. Under photo-irradiation, the PCN structures would be destroyed through a process of dechlorination followed by oxidation. In addition, the dechlorination pathways of PCNs have been established and found to be significantly influenced by the structure-related parameters.

Chlorobenzoquinones Aggravate RSL3-Induced Ferroptosis in ROS-Dependent Manner.

Chlorobenzoquinones (CBQs) are a class of emerging water disinfection byproducts that pose significant risks to public health. In this study, we found that three CBQs (tetrachloro-1,4-benzoquinone, 2,5-dichloro-1,4-benzoquinone, and 2-chloro-1,4-benzoquinone) can significantly aggravate cell death caused by Ras-selective lethal small molecule 3 (RSL3). Further study showed that the cell death caused by CBQs, either alone or in combination with RSL3, was related to iron accumulation and GPX4 inactivation, suggesting the occurrence of ferroptosis. Furthermore, reactive oxygen species are found to play a potential key role in mediating the toxicity of CBQs in CBQs and RSL3-induced ferroptosis. These findings will be helpful in understanding the toxic mechanism of CBQs to mammalian cells.

Vortex-assisted dispersive micro-solid-phase extraction using silica-supported Fe2O3-modified khat (Catha edulis) biochar nanocomposite followed by GC-MS for the determination of organochlorine pesticides in juice samples.

In this paper, dispersive micro-solid phase extraction technique was developed for the purpose of extracting and preconcentrating organochlorine pesticide residues in juice samples before their separation and quantitative analysis by gas chromatography-mass spectrometry. A sorbent composed of a silica-supported Fe2O3-modified khat leftover biochar nanocomposite (SiO2-Fe2O3-KLBNC) was implemented in the process. To improve the dispersion of the sorbent in the solution, vortex mixer was employed. Experimental parameters influencing the performance of the method were optimized, and the optimal conditions were established. With these conditions, linear dynamic ranges ranged from 0.003 to 100.0 ng/mL were achieved, with a correlation coefficient (r2) ≥ 0.9981. The limits of detection and quantification, determined by signal-to-noise ratios of 3 and 10, respectively, were found to be in the ranges of 0.001-0.006 ng/mL and 0.003-0.020 ng/mL. Intra- and inter-day precision, values ranging from 0.3-4.8% and 1.7-5.2% were obtained, respectively. The matrix-matched extraction recoveries demonstrated favorable outcomes, falling within the range of 83.4-108.3%. The utilization of khat leftover as an adsorbent in contemporary sample preparation methodologies offers a cost-effective alternative to the currently available, yet expensive, adsorbents. This renders it economically viable, particularly in resource-constrained regions, and is anticipated to witness widespread adoption in the coming future.

A field study of a novel permeable-reactive-biobarrier to remediate chlorinated hydrocarbons contaminated groundwater.

Chlorinated hydrocarbons (CHs) pose significant health risks due to their suspected carcinogenicity, necessitating urgent remediation efforts. While the combination of zero-valent iron (Fe0) and microbial action shows promise in mitigating CH contamination, field studies on this approach are scarce. We devised a novel three-layer permeable reactive barrier (PRB) material incorporating Fe0 and coconut shell biochar, effectively implemented at a typical CH-contaminated site. Field monitoring data revealed conducive conditions for reductive dechlorination of CHs, characterized by low oxygen levels and a relatively neutral pH in the groundwater. The engineered PRB material consistently released organic carbon and iron, fostering the proliferation of CH-dechlorinating bacteria. Over a 250-day operational period, the pilot-scale PRB demonstrated remarkable efficacy in CH removal, achieving removal efficiencies ranging from 21.9% to 99.6% for various CH compounds. Initially, CHs were predominantly eliminated through adsorption and iron-mediated reductive dechlorination. However, microbial reductive dechlorination emerged as the predominant mechanism for sustained and long-term CHs removal. These findings underscore the economic viability and effectiveness of our approach in treating CH-contaminated groundwater, offering promising prospects for broader application in environmental remediation efforts.

Effects of organochlorine pesticides on human and rat 17ß-hydroxysteroid dehydrogenase 1 activity: Structure-activity relationship and in silico docking analysis.

The objective of this study was to examine the effect of 11 organochlorine pesticides on human and rat 17ß-Hydroxysteroid dehydrogenase 1 (17ß-HSD1) in human placental and rat ovarian microsome and on estradiol production in BeWo cells. The results showed that the IC50 values for endosulfan, fenhexamid, chlordecone, and rhothane on human 17ß-HSD1 were 21.37, 73.25, 92.80, and 117.69 µM. Kinetic analysis revealed that endosulfan acts as a competitive inhibitor, fenhexamid as a mixed/competitive inhibitor, chlordecone and rhothane as a mixed/uncompetitive inhibitor. In BeWo cells, all insecticides except endosulfan significantly decreased estradiol production at 100 µM. For rats, the IC50 values for dimethomorph, fenhexamid, and chlordecone were 11.98, 36.92, and 109.14 µM. Dimethomorph acts as a mixed inhibitor, while fenhexamid acts as a mixed/competitive inhibitor. Docking analysis revealed that endosulfan and fenhexamid bind to the steroid-binding site of human 17ß-HSD1. On the other hand, chlordecone and rhothane binds to a different site other than the steroid and NADPH-binding site. Dimethomorph binds to the steroid/NADPH binding site, and fenhexamid binds to the steroid binding site of rat 17ß-HSD1. Bivariate correlation analysis showed a positive correlation between IC50 values and LogP for human 17ß-HSD1, while a slight negative correlation was observed between IC50 values and the number of HBA. ADMET analysis provided insights into the toxicokinetics and toxicity of organochlorine pesticides. In conclusion, this study identified the inhibitory effects of 3-4 organochlorine pesticides and binding mechanisms on human and rat 17ß-HSD1, as well as their impact on hormone production.

Impact of repeated fumigant applications on soil properties, crop yield, and microbial communities in a plastic-mulched tomato production system.

Pre-plant soil fumigation is widely applied to control nematodes, soil-borne fungal pathogens, and weeds in vegetable crops. However, most of the research evaluating the effect of fumigants on crop yield and soil microbial communities has been done on single compounds despite growers mainly applying fumigant combinations. We studied the effect of different fumigant combinations (chloropicrin, 1,3-dichloropropene, and metam potassium) on soil properties, crop yield, and the soil bacterial and fungal microbiome for two consecutive years in a plastic-mulched tomato production system in Florida (United States). While combinations of fumigants did not improve plant productivity more than the individual application of these products, application of fumigants with >60 % chloropicrin did significantly increase yield. Fumigant combinations had no significant effect on bacterial diversity, but fumigants with >35 % chloropicrin reduced soil fungal diversity and induced temporary changes in the soil bacterial and fungal community composition. These changes included short-term increases in the relative abundance of Firmicutes and Ascomycota, as well as decreases in other bacterial and fungal taxa. Repeated fumigation reduced network complexity and the relative abundance of several predicted bacterial functions and fungal guilds, particularly after fumigation and at end of harvest (3-months post fumigation). A structural equation model (SEM) showed fumigants not only directly impact crop yield, but they can also indirectly determine variations in plant productivity through effects on the soil microbiome. Overall, this study increases our understanding of the environmental and agricultural impacts of fumigants in a plastic-mulched tomato production system.

Efficient composite chlorinated ethenes removal using gallic acid to enhance Fe/Ni nanoparticles activated persulfate.

As the representative volatile chlorinated hydrocarbons detected in wastewater, the removal of composite chlorinated ethenes is a major challenge in wastewater treatment. In the present study, an efficient removal system for composite chlorinated ethenes was reported, in which gallic acid was used to enhance the activation of persulfate by Fe/Ni nanoparticles. The influences of gallic acid-Fe/Ni and persulfate concentrations, initial pH value, reaction temperature, inorganic anions, and natural organic matters were evaluated in the composite chlorinated ethenes removal. Our results showed that the gallic acid-Fe/Ni-persulfate system with 9.0 mM of gallic acid-Fe/Ni and 30.0 mM of persulfate yielded about 100% trichloroethylene removal and 97.3%-98.6% perchloroethylene removal in the pH range of 3.0-12.0. Electron paramagnetic resonance analysis and radical quenching experiments indicated that SO4•- and •OH were the predominant radical species under acidic and alkaline conditions. Ultraviolet visible spectroscopy and inductively coupled plasma optical emission spectrometer tests revealed the Fe-gallic acid chelation could regulate the concentration of iron ions and improve the reactivity of gallic acid-Fe/Ni. These results demonstrated that the gallic acid-Fe/Ni-persulfate system was a promising strategy for treating composite chlorinated ethenes-containing wastewater.

Identification and oxidation of chlorinated paraffins containing nitrate esters, aliphatic sulfates, and thioether amino acids in sewage sludges.

Owing to the extensive production and widespread use of chlorinated paraffins (CPs), various CP structural analogs (CPSAs) have been detected in the environment, and these hydrophobic pollutants preferentially adsorb onto sludge during treatment. However, the species and sources of CPSAs in sludge and their subsequent fate during sludge oxidation treatments remain unclear. In this study, 320 nitrogen- or sulfur-containing CPs (205 CPs-N and 115 CPs-S) were detected in sludge through an analysis of Ph4PCl-enhanced ionization coupled with ultra-performance liquid chromatography (UPLC)-orbitrap-mass spectrometry (MS). The intensities of the newly found CPSAs were approximately 3.9-4.1 times those of CPs. Among these CPSAs, 273 previously unknown compounds, namely, 184 CPs-NO3, 63 CPs-SO4H, and 26 CPs-SH, were identified based on the characteristic fragments of NO3, SO4H, and SH, respectively. MS/MS analysis showed that the identified CPs-NO3 included 74 CPs-NO3, 71 CPs-NO3-NH2, 23 CPs-NO3-OH, and 16 CPs-NO3-NH2-OH; CPs-SO4H included 40 CPs-SO4H and 23 CPs-SO4H-OH; and CPs-SH could be divided into 19 2-(methylthio)acetamide-, 6 2-(methylthio)acetamide-cysteine-, and 1 N-acetylcysteine- containing CPs. High abundances of CPs-NO3 and CPs-SO4H were found in both sludge and CP commercial mixtures, indicating that these CPSAs likely originated from the production or use of industrial products. CPs-SH, which were present only in the sludge, were potentially derived from the biotransformation of CPs with amino acids. The oxidation of sludge resulted in the removal of 20.4-60.7 % of the newly identified CPSAs. The oxidation of CPs-NO3 and CPs-SO4H involved both carbon chain decomposition and hydroxylation processes, whereas CPs-SH underwent oxidation through carbon chain decomposition.

Chlorinated Paraffin Pollution in the Marine Environment.

Chlorinated paraffins (CPs) are ubiquitous in the environment due to their large-scale usage, persistence, and long-range atmospheric transport. The oceans are a critical environment where CPs transformation occurs. However, the broad impacts of CPs on the marine environment remain unclear. This review describes the sources, occurrence and transport pathways, environmental processes, and ecological effects of CPs in the marine environment. CPs are distributed in the global marine environment by riverine input, ocean currents, and long-range atmospheric transport from industrial areas. Environmental processes, such as the deposition of particle-bound compounds, leaching of plastics, and microbial degradation of CPs, are the critical drivers for regulating CPs' fate in water columns or sediment. Bioaccumulation and trophic transfer of CPs in marine food webs may threaten marine ecosystem functions. To elucidate the biogeochemical processes and environmental impacts of CPs in marine environments, future work should clarify the burden and transformation process of CPs and reveal their ecological effects. The results would help readers clarify the current research status and future research directions of CPs in the marine environment and provide the scientific basis and theoretical foundations for the government to assess marine ecological risks of CPs and to make policies for pollution prevention and control.

Visible-Light-Induced Aminochlorination of Alkenes.

Photoinduced N-internal vicinal aminochlorination of styrene-type terminal alkenes was developed. The reaction proceeded without any catalyst, and the use of N-chloro(fluorenone imine) as both a photoactivatable aminating agent and a chlorinating agent was essential. The imine moiety, introduced at the internal position of the alkenes, could be hydrolyzed under mild conditions to provide versatile ß-chlorinated primary amines, the synthetic utility of which was demonstrated by several transformations.

In Vivo Profiling and Quantification of Chlorinated Paraffin Homologues in Living Fish.

Herein, we demonstrate the ability of a dual-purpose periodic mesoporous organosilica (PMO) probe to track the complex chlorinated paraffin (CP) composition in living animals by assembling it as an adsorbent-assisted atmospheric pressure chemical ionization Fourier-transform ion cyclotron resonance mass spectrometry (APCI-FT-ICR-MS) platform and synchronously performing it as the in vivo sampling device. First, synchronous solvent-free ionization and in-source thermal desorption of CP homologues were achieved by the introduction of the PMO adsorbent-assisted APCI module, generating exclusive adduct ions ([M - H]-) of individual CP homologues (CnClm) with enhanced ionization efficiency. Improved detection limits of short- and medium-chain CPs (0.10-24 and 0.48-5.0 pg/µL) were achieved versus those of the chloride-anion attachment APCI-MS methods. Second, the dual-purpose PMO probe was applied to extract the complex CP compositions in living animals, following APCI-FT-ICR-MS analysis. A modified pattern-deconvolution algorithm coupled with the sampling-rate calibration method was used for the quantification of CPs in living fish. In vivo quantification of a tilapia exposed to technical CPs for 7 days was successfully achieved, with ∑SCCPs and ∑MCCPs of the sampled fish calculated to be 1108 ± 289 and 831 ± 266 µg/kg, respectively. Meanwhile, 58 potential CP metabolites were identified in living fish for the first time during in vivo sampling of CPs, a capacity that could provide an important tool for future study regarding its expected risks to humans and its environmental fate.

Validation of a Modified QuEChERS Method for the Determination of Selected Organochlorine Compounds in Honey.

Honey is considered to be a health-promoting food product. Therefore, it is assumed that it should be free of contaminants. Although the use of organochlorine pesticides (OCPs) was banned a few decades ago in developed countries, persistent organic pollutants (POPs) are still detected in various environmental and biological matrices, including food. These contaminants exhibit toxic properties and bioaccumulate in some food chains. The validation of a modified QuEChERS extraction method was successfully performed for o,p'-DDT, o,p'-DDE, o,p'-DDD, p,p'-DDT, p,p'-DDE, p,p'-DDD, heptachlor and dieldrin. 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153) was used as an internal standard. The modification involved changing the solvent from acetonitrile to n-hexane after extraction. Quantitation was carried out using gas chromatography with an electron capture detector (µECD). The mean recovery values for o,p'-DDT, o,p'-DDE, o,p'-DDD, p,p'-DDT, p,p'-DDE, p,p'-DDD and dieldrin, spiked at 2.9 ng/g and 20 ng/g, ranged from 64.7% to 129.3%, and, for heptachlor spiked at 5.6 ng/g and 20 ng/g, ranged from 68.0% to 88.3%. The relative standard deviation (RSD) for these concentrations did not exceed 20%, and the within-laboratory reproducibility was below 20%, except o,p'-DDE and p,p'-DDT, which were 25.2% and 20.7%, respectively. This modified QuEChERS extraction method for selected organochlorine compounds was demonstrated as effective for routine testing in honey.