The planning and development of new chiral stationary phases (CSPs) for liquid chromatography (LC) are considered as continuous and evolutionary issues since the introduction of the first CSP in 1938. The main objectives of the development strategies were to attempt the improvement of the chromatographic enantioresolution performance of the CSPs as well as enlarge their versatility and range of applications. Additionally, the transition to ultra-high-performance LC were underscored. The most recent strategies have comprised the introduction of new chiral selectors, the use of new materials as chromatographic supports or the reduction of its particle size, and the application of different synthetic approaches for preparation of CSPs. This review gathered the most recent developments associated to the different types of CSPs providing an overview of the relevant advances that are arising on LC.

Occupational exposure as a firefighter is a complex activity that continuously exposes subjects to several health hazards including fire emissions during firefighting. Firefighters are exposed to polycyclic aromatic hydrocarbons (PAHs), known as toxic, mutagenic, and carcinogenic compounds, by inhalation, dermal contact, and ingestion. In this work, a literature overview of firefighters’ dermal exposure to PAHs after firefighting and data retrieved from skin in vitro/in vivo studies related to their dermal absorption, bioavailability, and associated toxicological and carcinogenic effects are reviewed. The evidence demonstrates the contamination of firefighters’ skin with PAHs, mainly on the neck (2.23–62.50 ng/cm²), wrists (0.37–8.30 ng/cm²), face (2.50–4.82 ng/cm²), and hands (1.59–4.69 ng/cm²). Concentrations of possible/probable carcinogens (0.82–33.69 ng/cm²), including benzopyrene isomers, were found on firefighters’ skin. PAHs penetrate the skin tissues, even at low concentrations, by absorption and/or diffusion, and are locally metabolized and distributed by the blood route to other tissues/organs. Lighter PAHs presented increased dermal permeabilities and absorption rates than heavier compounds. Topical PAHs activate the aryl hydrocarbon receptor and promote the enzymatic generation of reactive intermediates that may cause protein and/or DNA adducts. Future research should include in vitro/in vivo assays to perform a more realistic health risk assessment and to explore the contribution of dermal exposure to PAHs total internal dose.

Firefighters’ occupational activity causes cancer, and the characterization of exposure during firefighting activities remains limited. This work characterizes, for the first time, firefighters’ exposure to (coarse/fine/ultrafine) particulate matter (PM) bound polycyclic aromatic hydrocarbons (PAHs) and metal(loid)s during prescribed fires, Fire 1 and Fire 2 (210 min). An impactor collected 14 PM fractions, the PM levels were determined by gravimetry, and the PM-bound PAHs and metal(loid)s were determined by chromatographic and spectroscopic methodologies, respectively. Firefighters were exposed to a total PM level of 1408.3 and 342.5 µg/m³ in Fire 1 and Fire 2, respectively; fine/ultrafine PM represented more than 90% of total PM. Total PM-bound PAHs (3260.2 ng/m³ in Fire 1; 412.1 ng/m³ in Fire 2) and metal(loid)s (660.8 ng/m³ versus 262.2 ng/m³), distributed between fine/ultrafine PM, contained 4.57–24.5% and 11.7–12.6% of (possible/probable) carcinogenic PAHs and metal(loid)s, respectively. Firefighters’ exposure to PM, PAHs, and metal(loid)s were below available occupational limits. The estimated carcinogenic risks associated with the inhalation of PM-bound PAHs (3.78 × 10⁻⁹ − 1.74 × 10⁻⁶) and metal(loid)s (1.50 × 10⁻² − 2.37 × 10⁻²) were, respectively, below and 150–237 times higher than the acceptable risk level defined by the USEPA during 210 min of firefighting activity and assuming a 40-year career as a firefighter. Additional studies need to (1) explore exposure to (coarse/fine/ultrafine) PM, (2) assess health risks, (3) identify intervention needs, and (4) support regulatory agencies recommending mitigation procedures to reduce the impact of fire effluents on firefighters.

Enantioselective chromatography is one of the most used techniques for the separation and purification of enantiomers. The most important issue for a specific successful enantioseparation is the selection of the suitable chiral stationary phase (CSP). Different synthetic approaches have been applied for the preparation of CSPs, which embrace coating and immobilization methods. In addition to the classical and broadly applied coating and immobilization procedures, innovating strategies have been introduced recently. In this review, an overview of different methods for the preparation of coated and immobilized CSPs is described. Updated examples of CSPs associated with the various strategies are presented. Considering that after the preparation of a CSP its characterization is fundamental, the methods used for the characterization of all the described CSPs are emphasized.

The concentrations of respirable particulate matter (PM) and the impact on indoor air quality in occupational settings remains poorly characterized. This study assesses, for the first time, the cumulative and non-cumulative concentrations of 14 fractions of coarse (3.65-9.88 μm), fine (0.156-2.47 μm), and ultrafine (0.015-0.095 μm) PM inside the garage of heavy vehicles, firefighting personal protective equipment' storage room, bar, and a common area of seven Portuguese fire stations. Sampling campaigns were performed during a regular work week at the fire stations. Levels of daily total cumulative PM ranged from 277.4 to 413.2 μg/m³ (maximum values of 811.4 μg/m³), with the bar (370.1 μg/m³) and the PPE' storage room (361.3 μg/m³) presenting slightly increased levels (p > 0.05) than the common area (324.8 μg/m³) and the garage (339.4 μg/m³). The location of the sampling site, the proximity to local industries and commercial activities, the layout of the building, the heating system used, and indoor sources influenced the PM concentrations. Fine (193.8-301.0 μg/m³) and ultrafine (41.3-78.2 μg/m³) particles were predominant in the microenvironments of all fire stations and accounted for 71.5% and 17.8% of daily total cumulative levels, respectively; coarse particles (23.3-47.1 μg/m³) represented 10.7% of total PM. The permissible exposure limit (5.0 mg/m³) defined by the Occupational Safety and Health Organization for respirable dust was not overcome in the evaluated fire stations. Results suggest firefighters' regular exposure to fine and ultrafine PM inside fire stations which will contribute to cardiorespiratory health burden. Further studies are needed to characterize firefighters' exposure to fine and ultrafine PM inside fire stations, identify main emission sources, and evaluate the contribution of exposures at fire stations to firefighters' occupational health risks.