Modular, Scalable, and Customizable LC-HRMS for Exposomics.

In this chapter, we describe a multi-purpose, reversed-phase liquid chromatography-high-resolution mass spectrometry (LC-HRMS) workflow for acquiring high-quality, non-targeted exposomics data utilizing data-dependent acquisition (DDA) combined with the use of toxicant inclusion lists for semi-targeted analysis. In addition, we describe expected retention times for >160 highly diverse xenobiotics in human plasma and serum samples. The method described is intended to serve as a generic LC-HRMS exposomics workflow for research and educational purposes. Moreover, it may be employed as a primer, allowing for further adaptations according to specialized research needs, e.g., by including reference and/or internal standards, by expanding to data-independent acquisition (DIA), or by modifying the list of compounds prioritized in fragmentation experiments (MS2).

Assessment of internal exposure risk from metals pollution of occupational and non-occupational populations around a non-ferrous metal smelting plant.

Non-ferrous metal smelting poses significant risks to public health. Specifically, the copper smelting process releases arsenic, a semi-volatile metalloid, which poses an emerging exposure risk to both workers and nearby residents. To comprehensively understand the internal exposure risks of metal(loid)s from copper smelting, we explored eighteen metal(loid)s and arsenic metabolites in the urine of both occupational and non-occupational populations using inductively coupled plasma mass spectrometry with high-performance liquid chromatography and compared their health risks. Results showed that zinc and copper (485.38 and 14.00 µg/L), and arsenic, lead, cadmium, vanadium, tin and antimony (46.80, 6.82, 2.17, 0.40, 0.44 and 0.23 µg/L, respectively) in workers (n=179) were significantly higher compared to controls (n=168), while Zinc, tin and antimony (412.10, 0.51 and 0.15 µg/L, respectively) of residents were significantly higher than controls. Additionally, workers had a higher monomethyl arsenic percentage (MMA%), showing lower arsenic methylation capacity. Source appointment analysis identified arsenic, lead, cadmium, antimony, tin and thallium as co-exposure metal(loid)s from copper smelting, positively relating to the age of workers. The hazard index (HI) of workers exceeded 1.0, while residents and control were approximately at 1.0. Besides, all three populations had accumulated cancer risks exceeding 1.0 × 10-4, and arsenite (AsIII) was the main contributor to the variation of workers and residents. Furthermore, residents living closer to the smelting plant had higher health risks. This study reveals arsenic exposure metabolites and multiple metals as emerging contaminants for copper smelting exposure populations, providing valuable insights for pollution control in non-ferrous metal smelting.

Development and validation of multiresidue analysis method for biomonitoring of pesticides and metabolites in human blood and urine by LC-QToF-MS.

The widespread use of pesticides and their consequential presence in the environment is a growing concern due to the harmful health effects associated with pesticide exposure. For clinical and toxicology laboratories, a method for simultaneously determining these compounds and their metabolic products in body fluids, such as blood and urine, is important. In the present study, a rapid, sensitive and simultaneous LC-QToF-MS method for detecting multiclass pesticides and metabolites in blood and urine samples has been developed and validated. Four sample preparation procedures, protein precipitation and three different variants of QuEChERS-based extraction were evaluated to find a suitable, simple, and effective sample pretreatment technique. The final optimized sample preparation method (acetonitrile; 400 µl, MgSO4; 40 mg and NaCl; 10 mg) was validated for accuracy, precision, matrix effect, recovery, stability, carryover, and dilution integrity. Analyte recoveries ranged from 75.40 to 113.54 % while accuracy was evaluated in the range of 71.41-108.26 % and precision (%RSD) in the range of 0.01 %-16.85 %. The limit of quantification (LOQ) for all compounds was established in the range of 0.82-7.05 ng mL-1. The developed reliable, robust, and sensitive method was successfully applied for the quantification of target pesticides and metabolites in human blood and urine samples. Evaluated samples resulted in detection of eleven analytes (seven pesticides and four metabolites).

Pilot study on neonicotinoids in Finnish waterbirds: no detectable concentrations in common goldeneye (Bucephala clangula) plasma.

Neonicotinoids have been detected in farmland-associated birds and exposure to these insecticides has been linked to adverse effects. Even though neonicotinoids are mobile and persistent and have been detected in surface waters and aquatic invertebrates, there is a considerable lack of knowledge on their occurrence in waterbirds. Here we investigated the occurrence of seven neonicotinoids and some of their transformation products (imidacloprid, thiacloprid, thiamethoxam, acetamiprid, clothianidin, dinotefuran, nitenpyram, 6-chloronicotinic acid, hydroxy-imidacloprid, imidacloprid-urea, imidacloprid-olefin, thiamethoxam-urea, thiacloprid-amide, acetamiprid-acetate, and acetamiprid-desmethyl) in blood plasma of 51 incubating female common goldeneyes (Bucephala clangula). We collected samples from five different regions from southern to northern Finland encompassing rural and urban settings in coastal and inland areas. Surprisingly, none of the targeted neonicotinoids was found above the limit of detection in any of the samples. As neonicotinoid concentrations in wild birds can be very low, a likely reason for the nil results is that the LODs were too high; this and other possible reasons for the lack of detection of neonicotinoids in the goldeneyes are discussed. Our results suggest that neonicotinoid exposure in their breeding areas is currently not of major concern to female goldeneyes in Finland. Even though this study did not find any immediate danger of neonicotinoids to goldeneyes, further studies including surface water, aquatic invertebrates, and other bird species could elucidate potential indirect food chain effects.

Microplastics in marine sponges (Porifera) along a highly urbanized estuarine gradient in Santos, Brazil.

Microplastics (MPs) are ubiquitously found in environmental matrices, particularly affecting aquatic systems. While several marine species have been widely used to assess MP contamination, sponges (Porifera) are less used. The MPs contamination was assessed in the sun sponge (Hymeniacidon heliophila) along a gradient at the Santos Estuarine System (Brazil). A 14-fold difference between concentrations (particles g-1) was verified between the most (1.40 ± 0.81) and least (0.10 ± 0.12) contaminated sites, confirming the local contamination gradient. The MPs found were primarily polypropylene, small (1.2-1000 µm), fibrous, and colored. Considering total concentrations, sizes and shapes these spatial patterns were similar those previously detected in molluscs obtained in the same sites. On the other hand, they differed in polymeric composition and color categories. Such findings give important initial insights into the potential role of marine sponges as putative sentinels of MPs contamination.

A DNA barcode reference library for the Tipulidae (Insecta, Diptera) of Germany.

Tipulidae, commonly known as true crane flies, represent one of the most species-rich dipteran families, boasting approximately 4,500 known species globally. Their larvae serve as vital decomposers across diverse ecosystems, prompting their frequent and close observation in biomonitoring programs. However, traditional morphological identification methods are laborious and time-consuming, underscoring the need for a comprehensive DNA barcode reference library to speed up species determination. In this study, we present the outcomes of the German Barcode of Life initiative focused on Tipulidae. Our DNA barcode library comprises 824 high-quality cytochrome c oxidase I (COI) barcodes encompassing 76 crane fly species, counting for ca. 54% of the German tipulid fauna. Our results significantly increased the number of European tipulid species available in the Barcode of Life Data System (BOLD) by 14%. Additionally, the number of barcodes from European tipulid specimens more than doubled, with an increase of 118%, bolstering the DNA resource for future identification inquiries. Employing diverse species delimitation algorithms - including the multi-rate Poisson tree processes model (mPTP), Barcode Index Number assignments (BIN), Assemble Species by Automatic Partitioning (ASAP), and the TaxCI R-script - we successfully match 76-86% of the morphologically identified species. Further validation through neighbor-joining tree topology analysis and comparison with 712 additional European tipulid barcodes yield a remarkable 89% success rate for the species identification of German tipulids based on COI barcodes. This comprehensive DNA barcode dataset not only enhances species identification accuracy but also serves as a pivotal resource for ecological and biomonitoring studies, fostering a deeper understanding of crane fly diversity and distribution across terrestrial landscapes.

Mosquitoes on a chip-environmental DNA-based detection of invasive mosquito species using high-throughput real-time PCR.

The monitoring of mosquitoes is of great importance due to their vector competence for a variety of pathogens, which have the potential to imperil human and animal health. Until now mosquito occurrence data is mainly obtained with conventional monitoring methods including active and passive approaches, which can be time- and cost-consuming. New monitoring methods based on environmental DNA (eDNA) could serve as a fast and robust complementary detection system for mosquitoes. In this pilot study already existing marker systems targeting the three invasive mosquito species Aedes (Ae.) albopictus, Ae. japonicus and Ae. koreicus were used to detect these species from water samples via microfluidic array technology. We compared the performance of the high-throughput real-time PCR (HT-qPCR) system Biomark HD with real-time PCR (qPCR) and also tested the effect of different filter media (Sterivex® 0.45 µm, Nylon 0.22 µm, PES 1.2 µm) on eDNA detectability. By using a universal qPCR protocol and only 6-FAM-MGB probes we successfully transferred these marker systems on the HT-qPCR platform. All tested marker systems detected the target species at most sites, where their presence was previously confirmed. Filter media properties, the final filtration volume and observed qPCR inhibition did not affect measured Ct values via qPCR or HT-qPCR. The Ct values obtained from HT-qPCR were significantly lower as Ct values measured by qPCR due to the previous preamplification step, still these values were highly correlated. Observed incongruities in eDNA detection probability, as manifested by non-reproducible results and false positive detections, could be the result of methodological aspects, such as sensitivity and specificity issues of the used assays, or ecological factors such as varying eDNA release patterns. In this study, we show the suitability of eDNA-based detection of mosquito species from water samples using a microfluidic HT-qPCR platform. HT-qPCR platforms such as Biomark HD allow for massive upscaling of tested species-specific assays and sampling sites with low time- and cost-effort, thus this methodology could serve as basis for large-scale mosquito monitoring attempts. The main goal in the future is to develop a robust (semi)-quantitative microfluidic-based eDNA mosquito chip targeting all haematophagous culicid species occurring in Western Europe. This chip would enable large-scale eDNA-based screenings to assess mosquito diversity, to monitor species with confirmed or suspected vector competence, to assess the invasion progress of invasive mosquito species and could be used in pathogen surveillance, when disease agents are incorporated.

A direct immersion-solid-phase microextraction method for the automated determination of 3- to 6-ring polycyclic aromatic hydrocarbons in saliva by gas-chromatography-tandem mass spectrometry.

This work presents a novel method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in saliva samples using solid phase microextraction (SPME) coupled with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS). The protocol utilizes the latest commercially available overcoated fiber (PDMS/DVB/PDMS) for direct immersion extraction of the target analytes, enabling the determination of thirteen PAHs, including low-volatile compounds. The SPME extraction method was optimized using a central composite design (CCD). The evaluation of the fiber coating's robustness over time demonstrated excellent extraction performance with no significant degradation. The validation procedure confirmed good performance for all parameters, with LOQ values (100 ng/L for ten analytes and 500 ng/L for three analytes) comparable to other chromatographic methods. The environmental impact of the protocol was objectively assessed using two recently proposed metrics: the Green Analytical Procedure Index (GAPI) and the Analytical Greenness metric for sample preparation (AGREEprep). Both metrics indicated good overall environmental friendliness, with AGREEprep providing a satisfactory comprehensive score despite the use of highly impactful instrumentation. These characteristics make the developed method suitable for routine analysis in environmental and epidemiological monitoring.

The development of rapid immunoassays for the urinary analysis of 1-hydroxypyrene glucuronide facilitate both laboratory and on-site polycyclic aromatic hydrocarbon biomonitoring.

Polycylic Aromatic Hydrocarbons (PAHs) are produced during the incomplete burning of organic materials. PAH sources include vehicle exhaust, tobacco smoke and waste incineration. Environmental and occupational exposures to PAHs are known to occur. Cancer is a significant endpoint of PAH exposure and several occupations associated with high PAH exposure have been classified by IARC as carcinogenic to humans (Group 1). Pyrene is a common component of PAH mixtures and metabolism of pyrene leads to the excretion of 1-hydroxypyrene glucuronide (1-OHPyrG) in urine. Laboratory measurement of urinary 1-OHPyrG is employed in occupational and environmental biomonitoring programmes. The production of an anti-1-OHPyrG monoclonal antibody would allow the development of a PAH biomonitoring ELISA facilitating large scale laboratory screening and routine testing. The development of a lateral flow immunoassay and the production of a field test (point of use test) would greatly increase the value of biomonitoring. A novel Lateral Flow has been developed which employs an anti-1-OHPyrG sheep monoclonal antibody (Mab) to capture the PAH metabolite. The captured metabolite is visualised through a second Mab raised against the Mab-1-OHPyrG immune complex. This sandwich assay provides a positive correlation between the assay signal and biomarker concentration. A Smartphone camera allows signal measurement and a carefully considered 'app' provides result interpretation and data analysis. Results are provided in an exposed/not-exposed format. Performance of the lateral flow was confirmed through a comparative study and field trial. The development of a lateral flow test provides "real-time" analysis to occupational health professionals. On-site screening allows the immediate confirmation of safe working practice, provides immediate reassurance to those involved in potentially hazardous activities and greatly increases the efficacy of biomonitoring.

Current exposure to environmental pollutants in the general adult population of Kinshasa, Democratic Republic of Congo (DRC): A cross-sectional study.

BACKGROUND: Environmental pollution is a serious public health problem because of its adverse effects on both human health and biodiversity. In Western countries, many human biomonitoring (HBM) studies are conducted to assess population exposure to pollutants. In contrast, the number of HBM studies in Africa is very low. OBJECTIVE: To measure contamination by arsenic, lead, 4,4'-dichlorodiphenyldichloroethylene (4,4'-DDE) and polychlorobiphenyls (PCBs) in the adult population of Kinshasa and to identify the susceptible population. METHODS: In the present work, we measured the contamination by arsenic in urine and lead in blood and by 4,4'-DDE and polychlorobiphenyls (PCBs) in serum in samples collected from 151 volunteers recruited in Kinshasa, the capital of the Democratic Republic of Congo (DRC). RESULTS: The PCBs 180, -153 and -138 were detected in most samples with median concentrations of 0.04, 0.05 and 0.04 ng/ml, respectively. The median concentration of 4,4'-DDE was 0.83 ng/ml and 12.7% of our population showed contamination above the threshold of 3.675 ng/ml, which is associated with a significantly higher risk of cancer. Arsenic concentrations were also high (median: 48.1 µg/L in urine). Finally, exposure to lead is problematic: the median blood concentration was 54.9 µg/L, which is above the thresholds proposed by the WHO and the US CDC (50 µg/L and 35 µg/L respectively) to initiate clinical intervention, and 12.6% of the population had a lead level above 100 µg/L, which is associated with several health outcomes. CONCLUSIONS: Our results highlight the need for further HBM studies in Africa and should encourage the authorities of the DRC to implement laws and regulations to reduce pollution and population exposure.

Liquid crystal monomers in human, dog and cat feces from the United States.

Little is known about exposure of humans and companion animals to liquid crystal monomers (LCMs), which are extensively used in digital displays. We determined the concentrations of 52 LCMs in feces of humans, pet dogs and cats from New York State, USA, using gas chromatography-high resolution mass spectrometry (GC-HRMS). Twenty-four, eight, and six LCMs, that were mainly fluorinated, were detected in human, dog, and cat feces, respectively. ∑LCMs concentrations in the feces of humans (mean: 8.01 ng/g dry weight [dw]) were significantly higher (p < 0.05) than those of dogs (mean: 1.82 ng/g dw) and cats (mean: 1.24 ng/g dw) and with concentrations measured as high as 39.8 ng/g dw. Rel-4'-((1r,1'r,4 R,4'R)-4'-ethyl-[1,1'-bi(cyclohexan)]-4-yl)-3,4-difluoro-1,1'-biphenyl (RELEEBCH or 2bcHdFB) was found at the highest detection frequency (DF) among LCMs analyzed in human (DF: 89 %), dog (DF: 28 %), and cat (DF: 50 %) feces, although this compound accounted only < 4 % of ∑LCM concentrations. The mean cumulative daily intakes of ∑LCMs, calculated through a reverse dosimetry approach, were 71.7, 87.5, and 10.7 ng/kg body weight (bw)/day for humans, dogs, and cats, respectively. This study provides evidence of exposure of both humans and pets to LCMs, highlighting the importance of assessing sources of exposure and associated health risks.

Metabolomics and proteomics in occupational medicine: a comprehensive systematic review.

BACKGROUND: Occupational biomonitoring is essential for assessing health risks linked to workplace exposures. The use of 'omics' technologies, such as metabolomics and proteomics, has become crucial in detecting subtle biological alterations induced by occupational hazards, thereby opening novel avenues for biomarker discovery. AIMS: This systematic review aims to evaluate the application of metabolomics and proteomics in occupational health. METHODS: Following the PRISMA guidelines, we conducted a comprehensive search on PubMed, Scopus, and Web of Science for original human studies that use metabolomics or proteomics to assess occupational exposure biomarkers. The risk of bias was assessed by adapting the Cochrane Collaboration tool and the Newcastle-Ottawa Quality Assessment Scale. RESULTS: Of 2311 initially identified articles, 85 met the eligibility criteria. These studies were mainly conducted in China, Europe, and the United States of America, covering a wide range of occupational exposures. The findings revealed that metabolomics and proteomics approaches effectively identified biomarkers related to chemical, physical, biomechanical, and psychosocial hazards. Analytical methods varied, with mass spectrometry-based techniques emerging as the most prevalent. The risk of bias was generally low to moderate, with specific concerns about exposure measurement and confounding factors. CONCLUSIONS: Integrating metabolomics and proteomics in occupational health biomonitoring significantly advances our understanding of exposure effects and facilitates the development of personalized preventive interventions. However, challenges remain regarding the complexity of data analysis, biomarker specificity, and the translation of findings into preventive measures. Future research should focus on longitudinal studies and biomarker validation across diverse populations to improve the reliability and applicability of occupational health interventions.

Factors influencing metal concentrations in hair and nails during longitudinal follow-up of apprentice welders.

The aim of this study was to determine factors influencing observed increased metal biomarkers of exposure levels in a group of 116 Quebec apprentice welders during a longitudinal follow-up of exposure. Analysis of 14 metals was carried out in hair, fingernail, and toenail samples taken from participants over the course of their welding curriculum at 6 different times. Personal and socio-demographic characteristics, lifestyle habits, and other potential confounding factors were documented by questionnaire. Multivariate linear mixed-effect models were used to assess main predictors of metal concentrations in each biological matrix including increasing time of exposure throughout the curriculum (defined as the repeated measure "time" variable"). Significant associations between repeated measure "time" variable and metal levels in hair, fingernails, and toenails were found for chromium, iron, manganese and nickel. Significant associations with "time" were also noted for arsenic levels in hair and fingernails, and for barium, cobalt and vanadium levels in fingernails and toenails. The repeated measure "time" variable, hence increasing time of exposure throughout the curriculum, was the predominant predictor of elevated biological metal levels. Reduced spaces and simultaneous activities such as oxyfuel-cutting and welding in the same welding room were suspected to contribute to higher metal levels. Age, ethnicity, and annual household income exerted an effect on metal levels and considered as confounders in the models. Variations observed in metal levels between hair and nails of apprentice welders also emphasized the relevance and importance of performing multi-matrix and multi-element biomonitoring to assess temporal variations in biological metal concentrations during welding curriculum.

Accumulation of heavy metals in the leaves of different tree species and its association with the levels of atmospheric PM2.5-bond heavy metals in Isfahan.

This study aimed to biomonitor air pollution by measuring heavy metals (HMs) accumulation levels in the leaves of common urban trees, Cupressus arizonica Greene, Melia azedarach L., Morus alba L. and Buxus colchica in different regions of Isfahan. Their association with the levels of PM2.5 and PM2.5-bond HMs was also investigated. PM2.5 were collected on a glass-fiber filter and measured by gravimetric method. The HM contents of the PM2.5 and tree leaves were extracted and analyzed by ICP-OES. The average PM2.5 concentrations in ambient air of all areas varied from 52.34 to 103.96 µg/m3. The mean HMs levels in the leaves were in the following orderZn(31.2) > Cu(11.04) > Pb(4.38) > Ni(4.01) > Cr(3.03) > Co(0.61) > Cd(0.04) (µg/g). The highest level of HMs was detected in the leaves of Morus alba L., followed by Buxus colchica, Melia azedarach L. and Cupressus arizonica Greene. There was a significant correlation between the amounts of Pb and Cu in tree leaves and those in ambient PM2.5 (p value ≤ 0.05). In conclusion, tree leaves can be used as a suitable bioindicator in the evaluation of air pollution. Morus alba L. compared to the other species can be confidently used for green space development.

Isfahan is one of the most populated, industrialized cities in Iran experiencing serious air pollution. The currently operated air pollution monitoring stations in the city do not measure atmospheric heavy metals, a hazardous component of PM_2.5. To assess air pollution and level of exposure, biomonitor species such as tree leaves are the best tool due to their availability and low cost. Tree leaves can absorb and retain air pollutants. In this study, we found a good correlation between the concentration of heavy metals especially Pb and Cu in the leaves of commonly used tree species and their concentration in the airborne PM_2.5. Also, the results revealed that among the tree species, Morus alba L. retains more heavy metals followed by Buxus colchica, Melia azedarach L., and Cupressus arizonica Greene, which can be used for green space development.

Key recommendations and research priorities of the 2021 AMAP human health assessment.

Over the last three decades, the Arctic Monitoring and Assessment Programme has published five human health assessments. These assessments have summarised the current state of the science regarding environmental contaminants and human health in the Arctic. The 2021 Human Health Assessment Report had a particular focus on dietary transitions, in addition to human biomonitoring levels and trends, health effects, risk assessment methodologies, risk communication and multi-disciplinary approaches to contaminants research. The recommendations and research priorities identified in the latest assessment are summarised here to assist decision- and policy-makers in understanding and addressing the impacts of contaminants on human populations in the Arctic.

How can exposure assessment for pesticides in epidemiological studies be improved? Insights from the IMPRESS project.

The IMPRoving Exposure aSSessment Methodologies for Epidemiological Studies on Pesticides (IMPRESS) project (http://www.impress-project.org/) aimed to further the understanding of the performance of pesticide exposure assessment methods (EAMs). To achieve this the IMPRESS project used two approaches to assess EAM performance, using existing and newly collected data from five studies from three different countries and use of published secondary data to undertake three meta-analyses for selected chronic health outcomes. Based on the findings of the IMPRESS project we provide in this paper insights on the overarching research question "How can exposure assessments for pesticides in epidemiological studies be improved"? Exposure assessment is a critical component of pesticide epidemiological studies. EAMs used and epidemiological practices employed need to reflect the changing nature and complexities of pesticide exposure in various occupational settings. To properly assess the association between exposure and selected health outcomes, the choice of EAM should provide a clear exposure contrast within the study population. Acquiring a practical understanding of the pesticide use practices is crucial to determine whether factors such as frequency or intensity of exposure have to be considered in planned analyses. Biomonitoring may be more beneficially applied intensively in a focussed exposure assessment analysis of a particular cohort, which can be used to determine the most relevant exposure factors within that cohort-specific context. Overall, improving pesticide exposure assessment in epidemiological studies requires a multi-disciplinary approach. A next step for the wider scientific community may be to consider the development of a decision tree to aid the selection of suitable EAMs. Such a decision tree would need to consider and be based on multiple parameters including, but not limited to, study type, health endpoint, socio-demographic context, farming system, pesticide used, and application methods.

Kinetic Considerations in the Interpretation of Biomonitoring of 1,3-Butadiene Exposure by Determination of Urinary Mercapturic Acids.

1,3-Butadiene (BD) is classified as a human carcinogen, and occupational exposure should be minimized. This study examined the effectiveness of personal protective equipment (PPE) during the clean-up and repair of a storage tank containing sludge contaminated with BD. A total of 66 workers participated, providing repeat urine samples before and after the shift. Overall, 1286 samples were analyzed for 1,2-dihydroxy-4-(N-acetylcysteinyl)butane (DHBMA) and the isomers 2-hydroxy-1-(N-acetylcysteinyl)-3-butene and 1-hydroxy-2-(N-acetylcysteinyl)-3-butene (MHBMA). Both DHBMA and MHBMA are urinary metabolites of BD and serve as biomarkers for recent BD exposure. Established correlations between the urinary concentrations of these biomarkers and airborne BD levels allowed for exposure assessment. However, conclusions regarding the exceedances of occupational exposure limits can vary depending on whether DHBMA or MHBMA levels are considered. This study investigated this discrepancy by estimating the apparent urinary half-lives of DHBMA and MHBMA using sequential individual post- and pre-shift samples. The results indicated that the longer urinary half-life of MHBMA (19.7 ± 3.1 h) led to its accumulation during the work week, in contrast to DHBMA, which has a shorter half-life (10.3 ± 1.9 h) and showed limited accumulation. When the kinetic information was used to adjust for the MHBMA build-up over the week, the discrepancy with DHBMA resolved, confirming that exposure limit values were not exceeded and validating the effectiveness of the PPE used. In the context of biomonitoring, this study provides valuable insights into biomarker selection based on specific objectives. MHBMA is recommended for scenarios with uncertain exposure timing and activities, whereas DHBMA is the preferred biomarker for evaluating the effectiveness of protective measures in known exposure settings.

Morphophysiological and Histopathological Effects of Ammonium Sulfate Fertilizer on Aporrectodea trapezoides (Dugès, 1828) Earthworm.

The present study used the adult earthworm Aporrectodea trapezoides as a bioindicator species to look into the possible dangers of ammonium sulfate (AS) fertilizer. Two complementary toxicity tests were conducted to determine the LC50values, growth rate inhibition, morphological alterations, and histopathological texture of worms. The lethality test included four increasing concentrations of AS fertilizer (ranging from 2500 to 7500 mg/kg of dry soil weight (d.w.)), while sub-lethal concentrations were based on 10%, 30%, 40%, and 50% of the 14-day median lethal concentration (LC50), with a control group included for both tests. The LC(50) values for AS fertilizer were significantly higher at 7 days (4831.13 mg/kg d.w.) than at 14 days (2698.67 mg/kg d.w.) of exposure. Notably, earthworms exhibited significant growth rate inhibition under exposure to various concentrations and time durations (14/28 exposure days). Morphological alterations such as clitellar swelling, bloody lesions, whole body coiling and constriction, body strangulation, and fragmentation were accentuated steadily, with higher concentrations. Histopathological manifestations included severe injuries to the circular and longitudinal muscular layers, vacuolation, muscle layer atrophy, degradation of the chloragogenous tissue in the intestine, collapsed digestive epithelium of the pharynx with weak reserve inclusion, and fibrosis of blood vessels. These effects were primarily influenced by increasing concentrations of fertilizer and time exposure. The study highlights the strong relationship between concentration and exposure time responses and underscores the potential of A. trapezoides earthworms as valuable biological control agents against acidic ammonium sulfate fertilizer. Importantly, this research contributes to the use of such biomarkers in evaluating soil toxicity and the biological control of environmental risk assessment associated with chemical fertilizers.

Beekeeping breakthrough: unveiling hive health with a portable membrane inlet mass spectrometry detection method.

Supporting bee populations is essential considering threats posed by human activities like pesticide usage and habitat destruction. However, the current methods for monitoring and analyzing beehives and their surrounding environments are invasive, complex, and time-consuming. These methods often rely heavily on laboratory analyses, making them difficult to implement independently in the field. This study explores the application of portable membrane inlet mass spectrometer (MIMS) for noninvasive hive analysis, demonstrating its ability to detect various compounds indicative of hive conditions and environmental stressors. In addition to the expected compounds found in beehives, such as α-bergamotene, hexadecanoic acid, heptadecane, hexadecanamide, α-bisabolol-, 9-octadecenamide, (Z) - , and benzaldehyde, unexpected compounds, pollutants, like indane (polycyclic aromatic hydrocarbon) and carbofuran (pesticide), were also detected. The MIMS detection method provides rapid, accurate, and real-time results, making it suitable for preventive measures against bee diseases and integral to environmental biomonitoring. This integration of technology represents a significant advancement in bee conservation efforts, offering hope for the future of both bees and ecosystems.