Toxicological Analysis Research Articles

Biochar-bacteria coupling system enhanced the bioremediation of phenol wastewater-based on life cycle assessment and environmental safety analysis

The efficient treatment of phenol wastewater is of great necessity since it induces serious pollution of water and soil ecosystems. Using biochar-immobilized functional microorganisms can innovatively and sustainably deal with the existing problem. In this study, we utilized response surface methodology (RSM) combined with life cycle assessment (LCA) to improve phenol biodegradation rate through a novel separated alkali-resistant and thermophilic strain Bacillus halotolerans ACY. Bioinformatic analysis revealed the genetic foundation of ACY to adapt to harsh environments. The characteristics of pig manure biochar (PMB) produced at varying pyrolysis temperatures (300-700 ℃) and adsorption experiment were investigated, immobilization of the phenol-degrading ACY on PMB600 under alkaline and high pollution load promoted phenol removal and extreme environment resistance, and the phenol removal rate reached 99.5% in 7d in actual phenol wastewater, which increased compared with those achieved by PMB (50.6%) and free bacteria (80.5%) alone. Scanning Electron Microscope (SEM) and Fourier transform infrared spectrometry (FTIR) observations indicated the successful bacterial immobilization on PMB600. Reusability and economic cost study further demonstrated PMB600 as an excellent carrier for wastewater treatment. LC-MS, toxicology and carbon footprint analyses demonstrated that bacterial metabolism exerted synergy with adsorption for phenol removal, while biodegradation exerted the predominant impact on the immobilized bacterial system. This study provides an eco-friendly and effective approach to treat phenol wastewater.

Environmental triggers and future risk of developing autoimmune diseases: Molecular mechanism and network toxicology analysis of bisphenol A

Environmental triggers and future risk of developing autoimmune diseases: Molecular mechanism and network toxicology analysis of bisphenol A

The role of antibiotic-derived mycobacterial vesicles in tuberculosis pathogenesis.

Pulmonary tuberculosis (TB) causes progressive and irreversible damage to lung tissue, a damage that may not fully resolve after treatment. Mycobacterial vesicles (MVs), which are poorly understood, may contribute to TB pathology. This study investigated the effects of stress, such as treatment with conventional TB antibiotics rifampicin, isoniazid, ethambutol, or treatment with an antimycobacterial peptide (NZX), on mycobacterial vesiculation. Stress from minimal inhibitory concentrations of antibiotics, or peptide all increased MV formation. Electron microscopy and lipid profiling revealed that these vesicles, about 40nm in size, were released from the bacterial inner membrane and consisted of apolar lipids. Using mass spectrometry, the study identified key differences in MVs protein cargo dependent on the antibiotic used, especially with ethambutol-induced MVs that contained proteins from several mycobacterial pathways. Additionally, toxicology analysis using different concentrations of MVs on primary human macrophages and the monocytic cells indicated that MVs from the different treatments were not toxic to human cells, however induced specific inflammatory profiles. In conclusion, this study identified mycobacterial vesicles to be a potential contributor to tuberculosis pathology.

The Correlation of Bile Duct Dilatation in Postmortem Computed Tomography of Lethal Intoxication Cases for Different Drug Types—A Retrospective Study

Purpose: To assess (I) whether, in autopsy-proven lethal intoxications with opiates/opioids, a dilatation of the common bile duct (CBD) is still visible in postmortem computed tomography (PMCT) and (II) if a dilatation of the CBD might also be measurable for other substance groups (e.g., stimulants, hypnotics, antipsychotics, etc.). Methods: We retrospectively measured the CBD using PMCT in cases with lethal intoxication (n = 125) and as a control group in cases with a negative toxicological analysis (n = 88). Intoxicating substances were classified into the subgroups (opiates, opioids, stimulants, hypnotics, antipsychotics, gasses, and others). Significance between the study and control groups was tested with the Mann–Whitney U test, and correlations were examined by using crosstables. Results: There was a statistically significant difference between the CBD diameters in the intoxication group overall, when compared to the CBD diameter in the control group (p < 0.001). For both subgroups of “opiates” and “opioids”, there was a strong statistically significant difference between the CBD diameter (being wider) in those groups compared to the control group (both p = 0.001). For the three subgroups “hypnotics”, “stimulants”, and “psychotropic drugs”, there was no statistically significant difference between the CBD diameters in the intoxication subgroups when compared with the control group. The other subgroups were too small for statistical analysis. Conclusion: A dilated common bile duct in postmortem computed tomography might be used as an indication for a lethal opioid or opiate intoxication only in regard to the specific case circumstances or together with other indicative findings in a postmortem investigation.

Forensic issues in autoerotic deaths: A 44-year systematic review and a case series from the legal medicine institutes of Bologna and Milan, Italy.

Autoerotic deaths, defined as accidental fatalities occurring during solitary sexual activities, show complex forensic challenges due to their different mechanisms and variable death scene presentations. This study combines a systematic review of global literature spanning 44 years (from 1980 to 2024) with a detailed case series analysis from the Legal Medicine Institutes of Bologna and Milan, Italy, to provide comprehensive insights into this phenomenon.The systematic review identified 67 relevant reports from databases namely Scopus, Web of Science, and PubMed. In parallel, a case series of 7 autoerotic fatalities was analyzed, highlighting victims' demographics, causes of death, and associated factors.Findings from 101 cases of autoerotic deaths included in the systematic review indicate a predominant prevalence of asphyxial deaths, with hanging being the most common method, followed by intoxication. The study underscores significant gender disparities, with men comprising most cases (n = 91), spanning a broader age range (12-87 y.o.) compared to women (17-48 y.o.). The findings are fully consistent with the Italian case series presented here, in which all the subjects were men aged 18 to 72 years, and the cause of death was asphyxia in 6 cases.Toxicological analyses played a crucial role in elucidating the cause and manner of death in most cases, yet their utilization varies widely, impacting data reliability and evaluation of the cause of death. Notably, the evidence of volatile substances, especially inhalants, creates an emerging area of interest with potential epidemiological and preventive implications. The systematic analysis revealed substantial variability in death scene characteristics and forensic procedures, emphasizing the need for standardized investigative protocols.This study highlights the multifaceted nature of autoerotic deaths and the importance of a holistic forensic approach encompassing death scene investigation, autopsy, and toxicological analysis. By enhancing the understanding and awareness about this phenomenon, this research aims to inform evidence-based practices in forensics, mitigate diagnostic uncertainties, and facilitate preventive interventions.

Benchmark dose modeling for epidemiological dose-response assessment using case-control studies.

Following a previous article that focused on integrating epidemiological data from prospective cohort studies into toxicological risk assessment, this paper shifts the focus to case-control studies. Specifically, it utilizes the odds ratio (OR) as the main epidemiological measure, aligning it with the benchmark dose (BMD) methodology as the standard dose-response modeling approach to determine chemical toxicity values for regulatory risk assessment. A standardized BMD analysis framework has been established for toxicological data, including input data requirements, dose-response models, definitions of benchmark response, and consideration of model uncertainty. This framework has been enhanced by recent methods capable of handling both cohort and case-control studies using summary data that have been adjusted for confounders. The present study aims to investigate and compare the "effective count" based BMD modeling approach, merged with an algorithm used for converting odds ratio to relative risk in cohort studies with partial data information (i.e., the Wang algorithm), with the adjusted OR-based BMD analysis approach. The goal is to develop an adequate BMD modeling framework that can be generalized for analyzing published case-control study data. As in the previous study, these methods were applied to a database examining the association between bladder and lung cancer and inorganic arsenic exposure. The results indicate that estimated BMDs and BMDLs are relatively consistent across both methods. However, modeling adjusted OR values as continuous data for BMD estimation aligns better with established practices in toxicological BMD analysis, making it a more generalizable approach.

Toxicological analysis and anti-inflammatory and antioxidant evaluations of extract, fractions and secoxyloganin obtained from Guettarda viburnoides Cham. & Schltdl. in mice

Ethnopharmacological relevanceGuettarda viburnoides, "veludinho do campo," is traditionally used for the treatment of pain and inflammatory conditions in humans; however, only one scientific study has reported this effect in an ear inflammatory model. Therefore, it is necessary to explore other in vivo models and the chemical composition of this medicinal plant. Aim of the studyA chemical investigation of methanolic extract of G. viburnoides (MEGV) (leaves) led to the isolation of secoxyloganin (GV-1). In addition, the preclinical safety of MEGV (in acute and subacute toxicological models, gavage = p.o.), antioxidants of MEGV, ethyl acetate (EAFGV) and hydromethanolic (HMFGV) fractions were tested using free radical scavenging and lipid peroxidation methodologies, and the anti-inflammatory effects of MEGV, HMFGV and GV-1 (p.o.) were evaluated on carrageenan and complete Freund's adjuvant (CFA) models of inflammation in mice. Materials and MethodsMEGV was obtained from air-dried leaves by maceration with methanol at room temperature. MEGV was then purified by liquid-liquid partitioning, to obtain the EAFGV and HMFGV fractions. Purification of HMFGV afforded GV-1. The quantification of total phenols, flavonoids, flavonols, and condensed tannins was subsequently performed for MEGV. The antioxidant activity of 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2, 2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid (ABTS) and oxidation of β-carotene were evaluated in MEGV and its fractions. The anti-inflammatory activity of MEGV (3, 30, and 100 mg/kg, p.o.) was assayed in carrageenan-induced models, followed by assessments of MEGV (100 mg/kg, p.o.), HMFGV (3 and 30 mg/kg, p.o.) and GV-1 (3 mg/kg, p.o.) in CFA- induced models in mice (including paw oedema, mechanical allodynia and cold sensitivity). Acute (14 days of MEGV, 2000 mg/kg, p.o.) and subacute (28 days, MEGV 30, 100, and 300 mg/kg, p.o.) toxicity was assessed in female Swiss mice. ResultsThe major compound was secoxyloganin (GV-1). The oral acute toxicity test of MEGV revealed no evidence of toxicity, indicating low toxicity according to the Organization for Economic Cooperation and Development (OECD) guidelines. In the subacute toxicity group, no clinical signs of toxicity or changes in body weight, water consumption, food consumption, or organ weight or morphology were observed after 28 days of gavage with MEGV (30, 100, and 300 mg/kg) compared with those in the control group. MEGV, EAFGV, and HMFGV showed significant free-radical scavenging and lipid peroxidation activities, with IC50 values ≤ 26.38 ± 4.56 μg/mL. In in vivo anti-inflammatory assays, MEGV (3, 30 and 100 mg/kg) reduced carrageenan-induced oedema (2 and 4 h) and hyperalgesia (3 and 4 h). In the CFA model, MEGV (100 mg/kg), HMFGV (30 mg/kg) and GV-1 (3 mg/kg) reduced inflammation (at 3, 4 and 24 h) in all parameters (oedema, mechanical allodynia and cold sensitivity). ConclusionThis study revealed that G. viburnoides has antioxidant and anti-inflammatory properties, and no toxicity was detected after acute or subacute gavage with MEGV, validating its traditional use in the treatment of inflammatory conditions.

Determination of endogenous GHB in ante-mortem whole blood, urine, and oral fluid by LC–MS/MS: The effect of different additives and storage conditions on the stability of GHB in blood

Two challenges in detecting γ-hydroxybutyric acid (GHB) intake are its endogenous presence and in vitro production after sampling. This study developed an LC–MS/MS method for selective GHB determination in human antemortem blood, urine, and oral fluid at endogenous concentrations. Furthermore, the stability of GHB in blood samples and its endogenous concentrations in samples taken under controlled circumstances were investigated. Samples were extracted in methanol/acetonitrile and processed by anion exchange solid-phase extraction. GHB was separated from structural isomers using a reversed–phase LC column with anion properties. The validated limit of quantification was 0.005 µg/mL in blood and 0.010 µg/mL in urine and oral fluid, at which the relative reproducibility standard deviation and bias were <15 %. The mean extraction recovery was ≥90 %. The average GHB concentration increased by 1.2 µg/mL in fluoride/citrate- preserved blood after 28 days of storage at 4°C; however, in fluoride/oxalate (FX)-preserved blood, the mean concentration increased by only 0.055 µg/mL. No change was observed at −20°C. In 105 randomly selected samples of FX-preserved blood collected for forensic antemortem toxicological analysis, all concentrations were <0.066 µg/mL, even after long-term storage at −20°C. In blood, urine, and oral fluid samples from a clinical study of GHB intake, endogenous baseline levels from 30 participants ranged from 0.0069–0.050, 0.024–0.38, and 0.034–0.93 µg/mL, respectively. These results demonstrate that the current cut-off level of 5 µg/mL for discriminating between endogenous and exogenous GHB in antemortem blood could be considerably lower for FX-preserved blood stored at −20°C.

Drug-induced QT interval prolongation. Evaluating the prevalence of potentially fatal cardiac arrhythmias in a specific cohort of patients

Some drugs prolong the QT interval, which can be fatal in the presence of other risk factors. In the 3040 forensic autopsy cases that underwent toxicological analysis over the past five years, in which no certain cause of death could be identified, at least one drug with QT interval prolonging potential was detected in 188 individuals (6%). Risk factors for cardiac events, incl. a history of drug and/or alcohol abuse (45%), pathological cardiovascular changes (66%), and more than one QT-prolonging drug (64%) pointed toward fatal arrhythmic events resulting from the drug, of which antipsychotics were the most prevalent in our cohort.

Functional properties and toxicological analysis of nanocellulose-based aerogels loaded with polyphenols from Hyeronima macrocarpa berries

Functional properties and toxicological analysis of nanocellulose-based aerogels loaded with polyphenols from Hyeronima macrocarpa berries

A Stability Study of Atropine in Post-Mortem Peripheral Blood and Liver at -20°C, +4°C, +10°C and +20°C Over 12 Months. Peripheral Blood and Liver Concentration Ratios

At the judicial inquiry of a criminal case involving atropine, we were required to carry out toxicological analyses on a body exhumed 31 months after death. It was obviously not possible to take samples of peripheral blood or any other fluid at the autopsy of the victim.

Investigation of removing orange II azo dye from wastewater through an oxidation process

Rapid industrial growth in Bangladesh, especially in the textile industry, has led to water pollution from toxic azo dyes like orange-II, which are harmful to ecosystems and enter the food chain via irrigation. This study examined the use of chemical coagulation (using C6H11NO4X2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{C}}_{6} {\ ext{H}}_{11} {\ ext{NO}}_{4} {\ ext{X}}_{2}$$\\end{document} and FeCl3·6H2O\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{FeCl}}_{3} \\cdot 6{\ ext{H}}_{2} {\ ext{O}}$$\\end{document}) and advanced oxidation process (using NaOCl\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{NaOCl}}$$\\end{document}) to treat orange-II dye for irrigation. However, C6H11NO4X2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{C}}_{6} {\ ext{H}}_{11} {\ ext{NO}}_{4} {\ ext{X}}_{2}$$\\end{document} and FeCl3·6H2O\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{FeCl}}_{3} \\cdot 6{\ ext{H}}_{2} {\ ext{O}}$$\\end{document} showed limited effectiveness in removing orange-II dye across various pH (3, 6, 9, and 12) levels. In contrast, NaOCl\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{NaOCl}}$$\\end{document} achieved significant dye removal rates of over 90–99%. The study focused on high color removal, limited ClO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{ClO}}_{2}$$\\end{document} and neutral pH after the test. Variables included NaOCl\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{NaOCl}}$$\\end{document} doses (0.5 ml, 2.5 ml, and 5 ml), orange II dye doses (50 mg, 100 mg, and 150 mg) under different pH (3, 6, 8, 9 and 12) conditions. The manuscript is the first to assess orange-II dye using higher doses (2.5 ml and 5 ml) of NaOCl\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{NaOCl}}$$\\end{document} compared to other studies, as an alkaline chemical to neutralize pH levels post-test. The highest dye removal occurred at pH 9 with similar results at other pH levels except pH 12. However, despite effective color removal, the pH remained alkaline at pH 8, 9, and 12 after the test. Hence, optimal experimental conditions of operational parameters were pH = 3 or 6, 2.5 ml NaOCl\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{NaOCl}}$$\\end{document} dose with 100 mg/L or 150 mg/L dye doses. Further research is recommended on the degradation process, toxicological analysis of the final product, and cost-effectiveness for safe irrigation water.

Leveraging genetics to support forensic toxicology analysis: Demonstrating concordance among marijuana samples

Cannabis sativa is an important plant for industrial purposes. Indeed, it is legal to cultivate and supply authorized low level Δ9-tetrahydrocannabinol (THC) cannabis plants for fiber and seeds (i.e., 0.2 % according to the European Union regulation on drugs). Today, chromatography/mass spectrometry-based procedures are successfully applied to determine THC concentration. Unfortunately, when cannabis samples have been degraded because wrongfully stored, toxicological results were affected, altering the final status of legal sample or illegal sample. Rather, genetic identification could give more information about the identity of these plants. For this reason, a degradation study was run to support how genetics can help to detect concordance in cannabis highly-degraded samples. Forty cannabis sub-samples were stored (for one week, two weeks, one month and two months) in auto-sealing bag to assess the effects of a wrong cannabis storage on weight reduction, genomic DNA changes, and corresponding STR profiles. Once respective time-period elapsed, each sub-sample’s weight was measured, the percentage weight loss calculated, and the genomic DNA was extracted and quantified, obtaining a complete STR profile for all samples. Furthermore, the aim of this study was to assess the same 13-loci short tandem repeat (STR) multiplex system used for the degradation experiment and evaluate the power of such markers in the identification and discrimination of highly degraded cannabis samples coming from real cases. The results of this study demonstrated that the 13-loci STR multiplex system successfully achieved the objective both for industry and forensic purposes. For each sample, all 13 loci were amplified, and degraded samples were correctly identified, suggesting that genetic typification could be a useful tool. The proposed procedure could be parallelly applied to toxicology analysis to detect if vegetable sample become from authorized plant, to help courts track back illegal samples or to achieve illegal cannabis genetic profiles for further comparison.

Accidental Detection of Cocaine in Urine in Pediatric Patients: Case Series and Literature Review

Infantile occult exposure to cocaine in domestic environments represents a complex clinical and medico-legal problem, which can be associated with abuse and neglect and with potential short- and long-term health risks for children. The authors present a retrospective study on 764 children under 14 years old who accessed the Emergency Department of IRCCS Meyer from 2016 to 2023 and were included in the GAIA (Child and Adolescent Abuse Group) protocol for suspected maltreatment and abuse, and for which a urine toxicology analysis was performed. The aim is to discuss the medico-legal implications and highlight the need for a thorough evaluation and management of such situations. Urine screening tests for substances of abuse (e.g., cocaine, opiates, etc.) were performed with an EMIT® Siemens VIVA-E drug testing system (Siemens, Newark DE) in 124 cases for which the child’s clinical condition raised suspicion of intoxication, or the family context indicated distress or substance abuse dependency. The screening results revealed the presence of cocaine and its main metabolite, benzoylecgonine, in the urine of 11 children. In one case, a single girl was brought to the Emergency Department by staff from the facility where she and her mother were staying. In most of the cases, children were brought to the Emergency Department by their parents who accessed the Emergency Department due to various clinical manifestations (drowsiness, agitation, seizures, hypotonia, diarrhea, vomiting, etc.), except for one case of eye trauma suspected to be caused by abuse or neglect by one of the parents. Three of the children did not have signs or symptoms attributable to substance exposure, whilst eight of the cases presented some of the symptoms associated with occult infant exposure to cocaine, such as neurological manifestations, seizures, gastrointestinal symptoms, and respiratory depression. The probable mode of intake was mostly through breastfeeding and continuous environmental exposure due to domestic contamination or inhalation of “crack”. In the case of a 12-hour-old infant, there was probable prenatal in utero exposure. All the children were hospitalized, some for medical reasons and others solely as a precautionary measure for proper care. In all cases, a report was made to the Prosecutors as required by the Italian Penal Code, as well as to the Court of Minor. The study highlighted the importance of a multidisciplinary approach involving pediatricians, social workers, and forensics, as well as close collaboration with the relevant authorities, as the Gaia service at IRCCS Meyer offers. The occasional detection of cocaine in cases that showed no suspicion of intoxication led to a modification of the procedure and the development of a standardized protocol at IRCCS Meyer both in terms of prevention and in the detection and interception of hidden cases, in order to intervene early and initiate the necessary care pathways (secondary prevention). This protocol includes routine toxicological urine testing in all suspected or confirmed cases of child abuse, not just in those where symptoms might suggest a suspicion of intoxication.

Insights into the Phytochemical Profile and Therapeutical Potential of Withania Somnifera (L.) Dunal

Abstract: Withania somnifera (L.) Dunal (W. somnifera) is an herb commonly known by its English name Winter Cherry, and Ashwagandha in Hindi. It has been used as a traditional Rasayana herb for a long time. It is a rich reservoir of bioactive compounds known as withanolides, namely, withaferin-A and withanolide-D. Its current research covers many aspects of human health, which include anti-stress, anti-tumor, 9immuno-modulatory, hypocholesterolemic, hepatoprotective, hypoglycemic, diuretic, anti-convulsant, neurotropic, adaptogenic, and cardioprotective properties. This overview W. somnifera traditional uses, phytochemical, and pharmacological activities. However, in-depth studies are needed on the clinical use of W. somnifera against human diseases. Besides, detailed toxicological analysis is also to be performed for its safe and efficacious use in preclinical and clinical studies and as a health-promoting herb.

Mechanism of β-MnO2 particle for the peroxymonosulfate activation under electric field: the promoting effect of carbamazepine on Mn(III) and reactive oxygen species production

In this study, β-MnO2 was introduced into electro-peroxymonosulfate process as particle electrodes (E/PMS/β-MnO2) to reveal the pathway of reactive manganese species (RMnS) and its promoting effect on reactive oxygen species (ROS) production. A significant synergistic was observed in the E/PMS/β-MnO2 process, the reaction constant was 3 times higher than that in the E/PMS process. The mechanism experiments revealed the generation pathway of Mn(III)aq during the E/PMS/β-MnO2 process. The pyrophosphate complex experiments and electrochemical analysis demonstrated that Mn(III)aq was dominantly generated through the electron transfer between carbamazepine (CBZ) and Mn(IV) under electric field conditions, rather than the reduction process in the cathode area. Furthermore, quenching experiments and competition kinetics method demonstrated the production of Mn(III)aq has the potential to enhance the formation of reactive oxygen species (ROS), especially •OH and SO4•−. In addition, Mn(V)aq and Mn(VI)aq was proved unable to be produced during the E/PMS/β-MnO2 process. Different from other similar electrochemical studies, 1O2 was mainly generated by the reaction betweenO2•− and •OH in this research. It was observed that the inclusion of Cl— facilitated the removal of CBZ, whereas the addition of humic acid (HA) had negligible impact on CBZ removal during the E/PMS/β-MnO2 process. At last, the results of various water matrices effects and toxicology analysis showed that the E/PMS/β-MnO2 process has satisfactory performance in practical application. This study could provide new insights for electro-persulfate treatment processes.

Impact of PM2.5 filter extraction solvent on oxidative potential and chemical analysis

ABSTRACT Fine particulate matter (PM2.5) is hypothesized to induce oxidative stress, and has been linked to acute and chronic adverse health effects. To better understand the risks and underlying mechanisms following exposure, PM2.5 is collected onto filters but prior to toxicological analysis, particles must be removed from filters. There is no standard method for filter extraction, which creates the possibility that the methods of extraction selected can alter the chemical composition and ultimately the biological implications. In this study, comparisons were made between extraction solvents (methanol (MeOH), dichloromethane (DCM), 0.9% saline, and Milli-Q water) and the results of oxidative potential and elemental concentration analysis of PM2.5 collected across sites in Arkansas, USA. Significant differences were observed between solvents, with DCM having significantly different results compared to all other extraction solvents (p ≤ 0.001). Significant correlations between element, black carbon, and PM2.5 concentrations and oxidative potential were observed. The observed correlations were extraction solvent dependent. For example, in saline extracted samples, oxidative potential had significant negative correlations with: Ba, Cd, Ce, Co, Ga, Mn and significant positive correlations with: Cr, Ni, Th, U. While in MeOH extracted samples, significant positive correlations were only between oxidative potential and Ga, U and significant negative correlations with V. This indicates that PM2.5 samples extracted with different solvents will yield different conclusions about the causal components. This study highlights the importance of filter extraction methods in interpretation of oxidative potential results and comparisons between studies. Implications While there is no standard method for PM2.5 filter extraction, variation of extraction methods impact analytical results. This project identifies that extraction method variation, particularly extraction solvent selection, leads to discrepancies in chemical and toxicological analysis for PM2.5 collected on the same filter. This work highlights the need for methods standardization to support accurate comparisons between PM2.5 research studies, thus providing better understanding of PM2.5 across the globe.

Toxicological characterization of the insecticide metofluthrin and assessment of the carcinogenic risk to human health due to its chronic inhalation effect

The aim of the investigation is the toxicological characterization and analysis of the danger criteria of the insecticide metofluthrin with an assessment of the carcinogenic risk to health caused by chronic inhalation exposure to the substance at the level of the maximum possible concentrations in the air environment of human life. The analysis of scientific reports of the US Environmental Protection Agency (US EPA) and the European Chemicals Agency (ECHA) on the toxicological properties of metofluthrin was carried out. The assessment of the risk of the development of carcinogenic effects due to chronic inhalation exposure to metofluthrin was carried out taking into account the average daily dose of the substance that can enter the human body during the natural life span (LADD) and the carcinogenic potential factor (SF) in accordance with domestic guidelines. Classification of levels of carcinogenic risk was carried out using domestic and international approaches. It was established that the limiting criteria for the danger of metofluthrin are the average lethal concentration in air (LC50 =1080 mg/m³) and the size of the zone of chronic action (Zch=7.46), which characterizes the danger of occurrence of chronic intoxication due to long-term inhalation exposure. According to these indicators, metofluthrin is classified as a dangerous substance (hazard class 2). The key effects of the toxic action of metofluthrin are determined – neurotoxicity, hepatotoxicity and nephrotoxicity. The threshold non-genotoxic oncogenic potential of metofluthrin according to the phenobarbital type was established. Individual carcinogenic risk under different scenarios of chronic inhalation exposure to metofluthrin was calculated. The substance concentration of 3.54 mg/m³ leads to a high level of risk (1.5×10-3), which is considered unacceptable for production conditions and the population. At concentrations of 0.28 mg/m³ and 1.0 mg/m³, the risk is estimated as average and acceptable for production conditions (1.1-4.1×10-4). The risk of exposure to a concentration of 0.14 mg/m³ is classified as low and acceptable for the population (5.7×10-5). Thus, the results obtained in the study indicate that such concentrations of metofluthrin in the air as 0.14 – 0.28 – 1.0 mg/m³ are safe for human health, subject to compliance with medical and sanitary regulations at the stage of production and application of insecticides based on metofluthrin as prescribed.

Classics in Chemical Neuroscience: Medetomidine.

Medetomidine is an FDA-approved α2-adrenoreceptor (α2-AR) agonist used as a veterinary sedative due to its analgesic, sedative, and anxiolytic properties. While it is marketed for veterinary use as a racemic mixture under the brand name Domitor, the pharmacologically active enantiomer, dexmedetomidine, is approved for sedation and analgesia in the hospital setting. Medetomidine has recently been detected in the illicit drug supply alongside fentanyl, xylazine, cocaine, and heroin, producing pronounced sedative effects that are not reversed by naloxone. The pharmacological effects along with the low cost of supply and lack of regulation for medetomidine has made it a target for misuse. Since 2022, medetomidine has been found as an adulterant in samples of seized drugs, as well as in toxicological analyses of patients admitted to the emergency department after suspected overdoses across several U.S. states and Canada. This Review will discuss the history, chemistry, structure-activity relationships, drug metabolism and pharmacokinetics (DMPK), pharmacology, and emergence of medetomidine as an adulterant in drug mixtures in the context of the current opioid drug crisis.

Incidental detection of aluminum phosphide in abdominal subcutaneous fat- a rare reporting of chemical analysis findings in poisoning cases.

Aluminum phosphide (AlP) poses a significant health challenge in developing countries, primarily because of its accessibility to the unregulated market and the absence of specific antidotes. Although chemical analysis of routine viscera can provide valuable information regarding the type of poison present in the body during poisoning incidents, numerous factors can alter the test results of chemical analysis, such as decomposition changes, postmortem redistribution, and the chemical nature of drugs. Analytical methods are frequently impeded by the interference caused by coextracted putrefactive compounds, which can mask or alter the detection of drugs. This series of three cases is particularly noteworthy because it involves the postmortem detection of AlP in the abdominal subcutaneous fat of the deceased, a previously unreported occurrence. In the first case, the body showed findings of late postmortem changes, with stomach mucosa being congested and hemorrhagic, along with routine viscera, and abdominal subcutaneous fat was sent for toxicological analysis. To confirm these findings, in two further cases of suspected AlP poisoning, subcutaneous fat was sent along with routine viscera. Stomach mucosa in the other two cases showed findings similar to those in the first. In the third case, black paste-like material was noted as stomach content. All the cases revealed the presence of AlP in routine viscera samples and abdominal subcutaneous fat on gas chromatography-mass spectrometry (GC‒MS) analysis. Therefore, abdominal fat can serve as a suitable sample for toxicological analysis to identify the presence of AlP, even in cases with advanced putrefactive changes.