Utilizing ion mobility spectrometry-mass spectrometry for the characterization and detection of persistent organic pollutants and their metabolites.

Persistent organic pollutants (POPs) are xenobiotic chemicals of global concern due to their long-range transport capabilities, persistence, ability to bioaccumulate, and potential to have negative effects on human health and the environment. Identifying POPs in both the environment and human body is therefore essential for assessing potential health risks, but their diverse range of chemical classes challenge analytical techniques. Currently, platforms coupling chromatography approaches with mass spectrometry (MS) are the most common analytical methods employed to evaluate both parent POPs and their respective metabolites and/or degradants in samples ranging from d rinking water to biofluids. Unfortunately, different types of analyses are commonly needed to assess both the parent and metabolite/degradant POPs from the various chemical classes. The multiple time-consuming analyses necessary thus present a number of technical and logistical challenges when rapid evaluations are needed and sample volumes are limited. To address these challenges, we characterized 64 compounds including parent per- and polyfluoroalkyl substances (PFAS), pesticides, polychlorinated biphenyls (PCBs), industrial chemicals, and pharmaceuticals and personal care products (PPCPs), in addition to their metabolites and/or degradants, using ion mobility spectrometry coupled with MS (IMS-MS) as a potential rapid screening technique. Different ionization sources including electrospray ionization (ESI) and atmospheric pressure photoionization (APPI) were employed to determine optimal ionization for each chemical. Collectively, this study advances the field of exposure assessment by structurally characterizing the 64 important environmental pollutants, assessing their best ionization sources, and evaluating their rapid screening potential with IMS-MS.

Exploring the binding mechanism and adverse toxic effects of persistent organic pollutant (dicofol) to human serum albumin: A biophysical, biochemical and computational approach.

The organochlorine pesticide dicofol (DCF), a persistent organic pollutant, is used as acaricide worldwide. Considering its large consumption in the agriculture sector and potential toxic effects such as endocrine disruption, carcinogenicity, and environmental persistence are detrimental to human health. To take an extensive evaluation of its potential toxicity, the current study was aimed to explore the binding mechanism and adverse effect of DCF on human serum albumin (HSA) by using an array of biophysical techniques (UV-visible, fluorescence, 3D fluorescence, and circular dichroism spectroscopy), isothermal titration calorimetric (ITC), computational methods and biochemical approaches. Fluorescence quenching and UV-Visible spectra of the HSA-DCF system confirmed static quenching mechanism and complex formation between HSA and DCF. The thermodynamics results from ITC revealed DCF-HSA interaction was exothermic and spontaneous and involved hydrophobic interactions and hydrogen bonding. The esterase activity of HSA displayed constant Vmax and elevated Km values confirming DCF-HSA competitive interaction. Circular dichroism spectra results revealed structural changes in HSA protein on interaction with DCF. Furthermore, molecular-specific site marker and molecular modelling results affirmed that the binding Site of DCF is Site I of HSA. A significant carbonyl content level in DCF-HSA system suggested protein structure damage. This work is likely to add a better understanding of DCF toxicity in human health and helpful in fortifying the check on food safety.

Comprehensive insights into the interactions of dicyclohexyl phthalate and its metabolite to human serum albumin.

Phthalate esters (PAEs) are a type of persistent organic pollutants and have received widespread concerns due to their adverse effects on human health. Dicyclohexyl phthalate (DCHP) and its metabolite monocyclohexyl phthalate (MCHP) were selected to explore the mechanism for interaction of PAEs with human serum albumin (HSA) through molecular docking and several spectroscopic techniques. The results showed that DCHP/MCHP can spontaneously occupy site I to form a binary complex with HSA, and DCHP exhibited higher binding affinity to HSA than MCHP. At 298 K, the binding constants (Kb) of DCHP and MCHP to HSA were 24.82 × 104 and 1.04 × 104 M-1, respectively. Hydrogen bonds and van der Waals forces were the major driving forces in DCHP/MCHP-HSA complex. The presence of DCHP/MCHP induced the secondary structure changes in HSA, and the pi electrons of the benzene ring skeleton of DCHP/MCHP played a key role in this binding processes. Exposure of DCHP/MCHP to TM4 cells revealed that interactions between PAEs and serum albumin can affect their cytotoxicity; DCHP showed higher toxicity than MCHP. The binding affinity of PAEs with HSA may be a valuable parameter for rapid assessment of their toxicity to organisms.

Software-Assisted Pattern Recognition of Persistent Organic Pollutants in Contaminated Human and Animal Food.

Persistent Organic Pollutants (POPs) are a serious food safety concern due to their persistence and toxic effects. To promote food safety and protect human health, it is important to understand the sources of POPs and how to minimize human exposure to these contaminants. The POPs Program within the U.S. Food and Drug Administration (FDA), manually evaluates congener patterns of POPs-contaminated samples and sometimes compares the finding to other previously analyzed samples with similar patterns. This manual comparison is time consuming and solely depends on human expertise. To improve the efficiency of this evaluation, we developed software to assist in identifying potential sources of POPs contamination by detecting similarities between the congener patterns of a contaminated sample and potential environmental source samples. Similarity scores were computed and used to rank potential source samples. The software has been tested on a diverse set of incurred samples by comparing results from the software with those from human experts. We demonstrated that the software provides results consistent with human expert observation. This software also provided the advantage of reliably evaluating an increased sample lot which increased overall efficiency.

Residues of Persistent Organic Pollutants (POPs) in Agricultural Soils Adjacent to Historical Sources of Their Storage and Distribution-The Case Study of Azerbaijan.

The aim of this study was to identify and examine the levels of organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) in soil collected from the surroundings of historical pesticide storage facilities on former agricultural aerodromes, warehouses, and pesticide distribution sites located in the most important agricultural regions in Azerbaijan. The conducted research included determination of three groups of POPs (occurring together), in the natural soil environment influenced for many years by abiotic and biotic factors that could have caused their transformations or decomposition. In this study, soil samples were collected in 21 georeferenced points located in the administrative area of Bilasuvar, Saatly, Sabirabad, Salyan and Jalilabad districts of Azerbaijan. Soil chemical analysis involved determination of organochlorine compounds (OCP): hexachlorocyclohexanes (HCHs) (three isomers α-HCH, ß-HCH and γ-HCH) and dichlorodiphenyltrichloroethanes (DDTs) (six congeners 2,4'DDT; 4,4'DDT; 2,4'DDE; 4,4'DDE; 2,4'DDE; and 4,4'DDE); polycyclic aromatic hydrocarbons (PAHs): 16 compounds from the United States Environmental Protection Agency US EPA list and, PCBs (seven congeners identified with the following IUPAC numbers: 28, 52, 101, 118, 138, 153, and 180). Our research showed that OCPs reached the highest concentration in the studied areas. The total concentrations of OCPs ranged from 0.01 to 21,888 mg∙kg-1 with significantly higher concentrations of Σ6DDTs (0.01 µg kg-1 to 21880 mg kg-1) compared to ΣHCH (0.14 ng kg-1 to 166.72 µg kg-1). The total concentrations of PCBs in the studied soils was varied from 0.02 to 147.30 µg·kg-1 but only PCB138 and PCB180 were detected in all analyzed samples. The concentrations of Σ16 PAHs were also strongly diversified throughout the sampling areas and ranged from 0.15 to 16,026 mg kg-1. The obtained results confirmed that the agricultural soils of Azerbaijan contained much lower (up to by three orders of magnitude) concentrations of PCBs and PAHs than DDT. It is supported by the fact that PCBs and PAHs were not directly used by agriculture sector and their content results from secondary sources, such as combustion and various industrial processes. Moreover, the high concentrations of PAHs in studied soils were associated with their location in direct neighborhood of the airport, as well as with accumulation of contaminants from dispersed sources and long range transport. The high concentrations of pesticides confirm that deposition of parent OCPs have occurred from obsolete pesticide landfills.

Environment-friendly PCN derivatives design and environmental behavior simulation based on a multi-activity 3D-QSAR model and molecular dynamics.

A multi-activity three-dimensional quantitative structure-activity relationship (3D-QSAR) model was established based on the comprehensive evaluation index (CEI) of polychlorinated naphthalenes (PCNs). The CEI values were calculated using the vector analysis method in combination with the following parameters: biological toxicity (predicted by logEC50), bioconcentration (predicted by logKow), long-distance migration (predicted by logPL), and biodegradation (predicted by total-score). Additionally, sixty-four CN-70 derivatives with lower CEI values were designed, among which three derivatives with reduced CEI values were selected for verification based on an evaluation of their persistent organic pollutant properties and practicability. Finally, an environmental behavior simulation was conducted via molecular dynamics simulation aided by the Taguchi experimental design by considering the degradation characteristics of the three aforementioned CN-70 derivatives as an example. Only two of the selected CN-70 derivatives were observed to be more easily degraded when compared with the CN-70 molecule (ascending range: 11.57 %-13.57 %) in a real-world setting, which was consistent with the biodegradability prediction results (ascending range: 14.94 %-22.49 %) obtained through the molecular docking studies. The multi-activity 3D-QSAR model established in this study overcame the limitations of generating molecular designs based on single-effect models from the source because it focused on the multiple effects of the pollutants.

Facile fabrication of silver iodide/graphitic carbon nitride nanocomposites by notable photo-catalytic performance through sunlight and antimicrobial activity.

Silver iodide/graphitic carbon nitride nanocomposites have been successfully fabricated through sonication-assisted deposition-precipitation route at room temperature and hydrothermal method. Varied mass ratios and preparation processes can modify the structure, purity, shape, and scale of specimens. The purity of the product was confirmed by Energy Dispersive X-Ray Spectroscopy (EDS) and X-ray crystallography. The morphology and size of specimens could be observed with transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). The bandgap was evaluated around 2.82 eV for pure g-C3N4. The bandgap has reduced to 2.70 eV by increasing the quantity of silver iodide in the nanocomposites. The photocatalytic activity of AgI/C3N4 has been studied over the destruction of rhodamine B (RhB) and methyl orange (MO) through visible radiation due to their suitable bandgap. The as-prepared AgI/C3N4 nanocomposites photocatalyst revealed better photocatalytic behavior than the genuine AgI and C3N4 which ascribed to synergic impacts at the interconnection of C3N4 and AgI. Furthermore, these nanocomposites have great potential for being a great antibacterial agent.

Enhanced visible-light photocatalytic degradation of tetracycline by a novel hollow BiOCl@CeO2 heterostructured microspheres: Structural characterization and reaction mechanism.

A high-efficiency hollow BiOCl@CeO2 heterostructured microspheres with type-II staggered-gap type was successfully synthesized by precipitation-hydrothermal process loaded with BiOCl nanoparticles on CeO2 microspheres. XRD, FT-IR, EDS, SEM, HRTEM and XPS results show that the prepared materials have good crystallization, morphology and retain hollow spherical structure of CeO2. Batch experiments indicate that the photocatalytic performance of BiOCl@CeO2 towards Tetracycline (TC) is superior to pure BiOCl or CeO2 owing to the distinctive hollow structures and the formed heterostructure between BiOCl and CeO2. Cyclic experiment exhibits that the optimal BiOCl@CeO2 photocatalyst can still photodegrade more than 80% of TC in 120 min after 4 cycles. Additionally, the reactive oxidation species (ROS) trapping experiments reveal that the critical ROS include photogenerated holes (h+) and superoxide radical anions (O2-). Finally, the possible degradation pathways of TC and enhanced photodegradation mechanism was systematically discussed. On this basis, the hollow BiOCl@CeO2 heterostructured microspheres provide a new alternative with great potential in efficient visible-light-driven photodegradation of persistent organic pollutants.