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Optimization and Validation of a Stir Bar Sorptive Extraction–HPLC–FLD Method for Monitoring PAHs in Water
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Polycyclic aromatic hydrocarbons (PAHs) are a class of persistent organic pollutants with known mutagenic and carcinogenic properties. They are commonly introduced into aquatic environments through industrial activities, fossil fuel combustion, and residential heating. Given their low concentrations and environmental relevance, the development of sensitive, selective, and cost-effective methods for their determination in water matrices is of critical importance. This study presents an optimized and validated analytical methodology for the simultaneous quantification of six priority PAHs—fluoranthene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, and indeno[1,2,3-cd]pyrene—in drinking water, groundwater, and surface water. The method employs stir bar sorptive extraction (SBSE) followed by high-performance liquid chromatography with fluorescence detection (HPLC–FLD). Key extraction parameters, including sample temperature, extraction time, stirring rate, matrix composition, and desorption time, were systematically optimized. The method demonstrated excellent linearity (R² > 0.998) across all analytes. Limits of detection ranged from 0.04 to 0.18 ng/L, while limits of quantification ranged from 0.13 to 0.61 ng/L. Recovery values were within 82–108%, with intra- and inter-day precision (RSD) below 10%. The total chromatographic runtime was 24 minutes, followed by a 2-minute post-run. Measurement uncertainty was also evaluated according to ISO/IEC 17025 guidelines.The validated SBSE–HPLC–FLD method provides a reliable, sensitive, and efficient approach for the monitoring of PAHs in environmental water matrices, contributing to improved risk assessment and regulatory compliance.

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Polymer Inclusion Membrane for Passive Sampling of Zn(II) in Water

Heavy metals, due to their toxicity, are known to cause various environmental and health issues; therefore, their monitoring is essential. Polymer inclusion membranes (PIMs) are innovative materials that can be utilized in passive sampling (PS) tools for monitoring heavy metals. Passive sampling is an integrative technique that has been developed over recent years and serves as a promising complementary tool to grab sampling. Its principle is based on the passive diffusion of contaminants through a membrane and their accumulation in a receiving phase. The concentration of pollutants in the studied system can thus be inferred from the amount of pollutant recovered from the binding phase. However, commercially available tools for passive sampling are quite limited. This work reports a preliminary application of a polymer inclusion membrane for potential integration into passive sampling tools. The PIM was prepared using 50% poly(vinyl chloride) (PVC) as the base polymer, 40% di(2-ethylhexyl) phosphoric acid (D2EHPA) as the carrier, and 10% dioctyl phthalate (DOP) as the plasticizer. Transport experiments through the PIM were conducted in a homemade permeation cell, using a Zn(II) solution at a concentration of 20 mg L−1 as the donor phase. The acceptor solution was 0.1 M HCl. The results indicated good performance regarding the transport of Zn(II) ions, with over 80% of the analyte being transported across the membrane.

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La2Ti2O7 doped with Pt, obtained by the sol--gel method, with photocatalytic activity in the oxidative degradation of ethanol

Introduction and Aim: Perovskites are materials with increasing applications in a variety of domains, including catalysis and photocatalysis [1-3]. The oxidation of organic compounds by sunlight is significant for several reasons, including its low cost, its ability to purify air and water [4], and its potential as an alternative to the selective synthesis of high-value oxygenated compounds [5]. The aim of this work is to study the synthesis of La2Ti2O7 perovskite through the sol--gel method and to test its photocatalytic activity in oxidative ethanol degradation under simulated solar light.

Methods: Materials used: lanthanum (III) nitrate hexahydrated [La(NO3)3x6H2O] and titanium (IV) isopropoxide [Ti[OCH(CH3)2]4] as precursors, glacial acetic acid (CH3COOH) and isopropanol (i-C3H7OH) as a solvents, and PtCl4 as a dopant. The reaction products of gas phase oxidation processes were analyzed by gas phase chromatography (GC-TCD and GC-FID).

Results: The structural and morphological comparison of nanopowders was accomplished by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) coupled with EDX, transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray fluorescence (XRF), ultraviolet-visible spectroscopy (UV–Vis), and specific surface area and porosity analysis (BET). Their photocatalytic activity was evaluated by the oxidative photodegradation of ethanol under simulated solar irradiation. The highest conversion of ethanol (29.75%) was obtained in the case of the Pt-doped sample.

Conclusions: Nanopowders of La2Ti2O7 (LTA) were prepared by the sol--gel method. The effect of the dopant on the properties of the Pt-doped powder was evaluated. The samples' morphology revealed nanoparticle aggregates with well-defined mesopores. The photocatalytic activity in terms of ethanol conversion and selectivity to CO2 was increased by the addition of platinum to the LTA catalyst. Consequently, these powders demonstrate potential applications for air depollution technologies.

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241Am in the bottom sediments of the southern Baltic Sea

Based on observations of 241Am in dated sediments, we studied the history of isotope accumulation in these sediments and evaluated their contamination level and distribution in the sediment cores. The fieldwork and sampling collection in the presented project were performed during a cruise on the r/v Oceania, which belongs to the Polish Academy of Sciences (IO PAN). Sediment cores were collected from various locations in the southern Baltic Sea: the Bornholm Deep, the Gdansk Deep, and the Gotland Deep.

An analytical method for determining Am was adapted to analyse 241Am in environmental and biological samples, which relies on the sequential use of ion exchange (Dowex 1x8) and extraction chromatography (UTEVA and TRU) to obtain a pure radioactive source of 241Am. The procedure was developed using the tracer 243Am isotope and alpha spectrometry. The accuracy of the procedure was tested using the reference materials IAEA-300, IAEA-384 and IAEA-385.

The results showed that in bottom sediment samples taken in 2010, the activity concentrations of 241Am in the Gdańsk Deep ranged from 0.009±0.003 (k=2) to 0.938±0.070 Bq∙kg-1, and those in the Gotland Deep ranged from 0.024±0.004 to 2.57±0.19 Bq∙kg-1. For bottom sediment samples collected in 2019, 241Am activity concentrations in samples from the Bornholm Deep ranged from 0.030±0.012 to 0.85±0.06 Bq∙kg-1, and those in the Gdańsk Deep ranged from 0.24±0.017 to 1.59±0.12 Bq∙kg-1, while those in the Gotland Deep ranged from 0.017±0.002 to 2.25±0.16 Bq∙kg-1.

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BEYOND THE BLOTTER: FORENSIC IDENTIFICATION OF NOVEL LSD ANALOGS VIA GC–QqQ–MS AND UHPLC–QqQ–MS/MS

Introduction: The proliferation of novel LSD analogs, often synthesized to circumvent existing legal regulations, presents a growing challenge for both forensic toxicology and public health. These so-called "designer psychedelics" often remain undetectable by routine screening methods and may exist in isomeric forms with different pharmacological profiles. As their availability rises, particularly via online markets, so does the urgency for accurate analytical methodologies that can distinguish known analogs and anticipate those yet to appear.

Methods: Two complementary analytical strategies were employed: GC–QqQ–MS and UV spectroscopy for analytical standards, and UHPLC–QqQ–MS/MS for biological matrices. The GC–QqQ–MS method was optimized for the separation and identification of 13 LSD analogs, including structural isomers, with attention paid in particular to solvent influence on compound stability. In parallel, the UHPLC–QqQ–MS/MS protocol was used to develop a comprehensive method for the determination of extremely low concentrations of analytes in biological material, as well as to investigate their stability over time under various storage conditions.

Results: GC–QqQ–MS with EI effectively differentiated critical isomer pairs (e.g., LSD vs. MiPLA, 1P-LSD vs. 1P-MiPLA) by unique ion fragmentation patterns and chromatographic separation. Solvent studies confirmed that methanol induces degradation in several analogs, whereas diethyl ether and acetone preserve compound integrity. The UHPLC–QqQ–MS/MS method demonstrated exceptional sensitivity (LOQ 0.5 pg/mL) and robustness, detecting analogs in forensic case samples and confirming degradation pathways, particularly for N1-substituted compounds converting to LSD or MiPLA.

Conclusions: This study highlights the necessity of robust, sensitive analytical methods to accurately identify LSD analogs and their isomers. Given their possible instability, ongoing method development is essential for reliable forensic interpretation and early detection of emerging substances.

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A Coastal Perspective on Air Quality Modelling

Introduction

Air quality in coastal cities is considerably affected by emissions from maritime transport in addition to land-based emissions. Pollutant emissions related to shipping, including particulate matter (PM), nitrogen oxides (NOx) and sulphur dioxide (SO2), can have adverse effects on ecosystem health by contributing to acid rain and eutrophication (Karl et al., 2019). Shipping emerges as a major source of ultrafine particle (UFP; diameter below 100 nm) emission and secondary formed aerosols in coastal cities. This presentation highlights various aspects of modelling air quality and exposure in coastal regions.

Methodology and Results

Impacts of ship emissions are assessed using a regional-to-local chemistry transport model chain with the EPISODE-CityChem model for the urban scale. Emissions from ocean-going ships are calculated using detailed emission models with ship positions based on data from the Automatic Identification System (AIS). The model chain is applied to simulate air quality concentrations and exposures in several European coastal cities, with more advanced modelling of secondary aerosol and UFP formation in Marseille (Karl et al., 2023), Athens and Hamburg. Local shipping significantly contributes to the UFP and NOx exposure in port environments and nearby residential areas but less to urban PM levels.

Conclusions

Modelling the fate of particles emitted from shipping demonstrates the much higher significance of UFP exposure compared to PM exposure, especially near the source of emissions. To assess health impacts of ship‐emitted particles with air quality models, it is crucial to include not just mass-based emission but also particle number and size distribution.

References

Karl, M.; Bieser, J.; Geyer, B.; Matthias, V.; Jalkanen, J.-P.; Johansson, L.; Fridell, E. Atmos. Chem. Phys. 2019, 19, 1721–1752, https://doi.org/10.5194/acp-19-1721-2019.

Karl, M.; Ramacher, M.O.P.; Oppo, S.; Lanzi, L.; Majamäki, E.; Jalkanen, J.-P.; Lanzafame, G.M.; Temime-Roussel, B.; Le Berre, L.; D’Anna, B. Toxics 2023, 11, 771, https://doi.org/10.3390/toxics11090771.

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Ion chromatographic profiling of major anions in sweet corn genotypes: implications for food safety and health risks

Sweet corn is an important crop and a high-demand commodity, generating substantial revenue in both its fresh and processed forms; it holds significant value in human nutrition due to its rich content of carbohydrates, dietary fiber, vitamins, and essential minerals, serving as a good source of energy while supporting digestive health. Monitoring the major inorganic anions in sweet corn kernels is essential for evaluating food safety compliance, quality attributes, and agricultural impact; while anions such as phosphate, sulfate, and chloride contribute to nutritional benefits, elevated levels of nitrate and nitrite pose potential health risks. Consequently, monitoring these anions is critical for consumer safety, supports quality control during processing, and provides insights into soil fertility and fertilizer efficiency. This study aimed to determine the major inorganic anions in twelve sweet corn genotypes from the University of Agricultural Sciences and Veterinary Medicine Cluj Napoca. Ion chromatographic analysis was performed using a Shimadzu instrument with non-suppressed conductivity detection, equipped with an Allsep Anion 7u column, achieving simultaneous determination of chloride, nitrite, nitrate, phosphate, and sulfate in under 15 minutes. Minimal sample preparation involved blending of representative kernels in ultrapure water, followed by membrane filtration. The results revealed distinct chromatographic fingerprints among genotypes: phosphate concentrations reached 58.65 mg/kg, chloride concentrations reached 27 mg/kg, sulphate concentrations reached 14.23 mg/kg, and nitrate concentrations reached 7.15 mg/kg, while nitrite was detected in only three samples, with a the maximum concentration of 0.41 mg/kg. These findings highlight significant variability in anion content across sweet corn genotypes, demonstrating that ion chromatography is a reliable and efficient tool for assessing sweet corn’s nutritional quality and safety. By identifying potential food hazards and promoting environmental sustainability, these findings support improved agricultural practices and breeding programs and the development of functional foods that cater to health-conscious consumers.

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Nanoparticle-Induced Oxidative Stress: Mechanisms and Implications for Human Health and Environmental Safety

Nanoparticles (NPs), which possess unique physicochemical qualities such as large surface area and reactivity, have brought about a revolution in a variety of sectors, including medicine and electronics. The growing ubiquity of these substances, on the other hand, has given rise to worries over the toxicological effects they have on human health and ecosystems. The condition known as oxidative stress, which is caused by an imbalance between the formation of reactive oxygen species (ROS) and antioxidant defenses, is one of the key processes that contribute to the toxicity of NPs. An excessive amount of ROS may cause damage to cellular components such as lipids, proteins, and DNA, which can result in detrimental consequences such as inflammation, apoptosis, and the development of cancer. NP-induced oxidative stress is investigated in this work, which focuses on the molecular mechanisms that are responsible for it. These processes include mitochondrial dysfunction, catalytic redox cycling, and the release of metal ions from particle disintegration. In addition, we investigate how the features of NPs, such as their size, shape, surface charge, and composition, affect their capacity to produce ROS. Additionally, the consequences of oxidative stress for both acute and chronic health effects are examined, in addition to the role that it plays in the toxicity of the environment. The use of antioxidants and alterations to the surface of NPs are two examples of mitigation measures that are discussed in this article. The findings of this study highlight the significance of gaining knowledge of the processes behind oxidative stress to ensure the safe design and deployment of nanoparticles.

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Dietary Exposure to Arsenic in the Cuban Population: Results from a Total Diet Study
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Arsenic (As), particularly in its inorganic form (iAs), is a toxic metalloid commonly found in food and associated with various health risks. This study assessed dietary exposure to total arsenic (t-As) and estimated inorganic arsenic intake in the Cuban adult population using a Total Diet Study (TDS). A 24-hour dietary recall survey was conducted with 450 individuals from different regions of Cuba. A total of 107 commonly consumed food items were purchased, prepared as typically consumed, and grouped into 17 categories. The samples were digested and analyzed by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) to quantify t-As. Estimated Daily Intake (EDI), Target Hazard Quotient (THQ), and Carcinogenic Risk (CR) were calculated. The highest concentrations of t-As were detected in the fish and seafood group (0.288 µg/g), followed by rice (0.032 µg/g) and vegetables (0.018 µg/g). The estimated intake of t-As was 54.6 µg/day. Assuming that 10% corresponds to iAs, the intake of inorganic arsenic was estimated at 5.46 µg/day. The THQ for iAs was 0.22, suggesting no significant non-carcinogenic risk. However, the CR for iAs was 1.0·10⁻⁴, indicating a potential lifetime cancer risk for 10 individuals per 100,000, which falls within the acceptable risk range. In conclusion, while total arsenic intake in the Cuban population complies with national limits, the presence of iAs may still pose a low but noteworthy cancer risk. Continued monitoring and public health interventions are recommended to minimize exposure through dietary sources.

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ARTERIAL DAMAGE ASSOCIATED WITH CHRONIC EXPOSURE TO GLYPHOSATE AND DICHLOROPHENOXYACETIC ACID: A STUDY IN RATS
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Introduction: Atherosclerosis is a chronic inflammatory disease which can culminate in significant cardiovascular manifestations. Some pesticides have been implicated in atherogenesis. Glyphosate and dichlorophenoxyacetic acid (2,4-D) are the most widely used herbicides in crops worldwide. The objective of this study was to compare the potential for arterial damage from chronic inhalation and oral exposure to the herbicide glyphosate and 2,4-D in rats. Methods: This study was approved by the Animal Use Ethics Committee of the proposing institution (Protocol 6724). Seventy adult male Wistar rats were distributed into 14 groups: 2 control groups (exposed to distilled water via inhalation and oral route), 6 groups exposed to glyphosate, and 6 exposed to 2,4-D (n=10/group). The animals were exposed to three doses of each herbicide via inhalation (inhalation groups) and in the diet (oral groups): low concentration, 3.71 x 10-3 grams of active ingredient per hectare (g.a.i./ha); medium concentration, 6.19 x 10-3 g.a.i./ha; and high concentration, 9.28 x 10-3 g.a.i./ha. The experiment lasted six months. The aorta was collected for histological analysis. Results: Fatty streaks were observed only in animals exposed to herbicides (p<0.0001), with no difference regarding the route of exposure (oral or inhalation) (p>0.05). Animals exposed to GBH had twice as many cases of cholesterol streaks than those exposed to 2,4-D (p<0.05). There was no significant difference in the thickness of the aorta between those exposed and those not exposed (p>0.05). Animals exposed to 2,4-D showed a greater fractal dimension of the nuclei when compared to animals exposed to GBH and those in the control group (p<0.05). Conclusions: Both herbicides have atherogenic potential, but this is greater in exposure to GBH. Animals exposed to 2,4-D have the largest nuclear fractal dimension, showing that this herbicide causes greater nuclear reactivity of the aortic wall.

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