Human exposure to particulate matter (PM) originating from air pollution is inevitable since more and more population is present in large cities that are characterized by poor air quality. The impact on human health is evident and we need to intensify research regarding this problem to get molecular insight into versatile effects of chronic exposure to PM inducing organism responses and initiating the development of selected disorders. Herein, the impact of standard PM representing urban pollution on the structure and function of human serum albumin (HSA) was evaluated by the application of various analytical techniques. HSA was selected due to its high likeliness of being exposed to PM because of the abundance of this protein in blood. The studies were focused mainly on the inorganic residue of PM resulting from removing organic components by a low-temperature plasma. To mimic physiological conditions, dialysis technique was used to simulate the release of nanoparticles and ions from PM to aqueous environment under, which in turn may interact with biomolecules inside the living system. Capture of metals from the bulk suspension was found for many metals like Al, Fe, Zn and Pb in quantities of more than 1 mol of metal ions per mole of HSA. No significant structural changes of the protein upon dialysis with PM were observed, however, an increase in the thermal stabilization of the HSA structure was observed. Moreover, the interaction of HSA dialyzed in the presence of PM with selected drugs (warfarin, aspirin) was negatively affected, indicating a lower affinity of drugs towards the protein, even though only small conformational changes of the PM exposed protein were observed. Our findings point to a possible interference of air pollutants with the drugs taken by patients living in highly polluted areas.

Warfarin-induced vitamin K (VK) recycling impairment is used worldwide as a rodenticide and human thromboembolic prophylactic. Since VK metabolism/signaling pathways have been conserved throughout vertebrate evolution, its release to the environment might impact on aquatic organisms. Present study assessed the toxic effect of warfarin (0, 5, 25 and 125 mg L−1) on zebrafish development and characterized underlying mechanisms of action through qPCR analysis of VK-related genes. Expression of pregnane X receptor (pxr), the nuclear receptor binding vitamin K, was ubiquitous in zebrafish and suggests that warfarin exposure may interfere with several biological processes. Indeed, warfarin exposure of zebrafish larvae caused hemorrhages in brain, skeletal deformities and triggered ectopic calcifications, which may be the consequence of an altered γ-carboxylation of VK-dependent proteins and/or pxr signaling. This study provides new insights into warfarin effects as a bone homeostasis disruptor and soft tissue calcification inductor, and its potential risk for aquatic environments.

A comprehensive analytical procedure for a reliable identification of nontarget polar contaminants in aquatic sediments was developed, based on the application of ultra-high-pressure liquid chromatography (UHPLC) coupled to hybrid quadrupole time-of-flight mass spectrometry (QTOFMS). The procedure was applied for the analysis of freshwater sediment that was highly impacted by wastewater discharges from the pharmaceutical industry. A number of different contaminants were successfully identified owing to the high mass accuracy of the QTOFMS system, used in combination with high chromatographic resolution of UHPLC. The major compounds, identified in investigated sediment, included a series of polypropylene glycols (n = 3–16), alkylbenzene sulfonate and benzalkonium surfactants as well as a number of various pharmaceuticals (chlorthalidone, warfarin, terbinafine, torsemide, zolpidem and macrolide antibiotics). The particular advantage of the applied technique is its capability to detect less known pharmaceutical intermediates and/or transformation products, which have not been previously reported in freshwater sediments.

The occurrence of 10 commonly used anticoagulant rodenticides in centrifuged sludge of 27 wastewater treatment plants was evaluated using solid-liquid extraction (SLE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Activated carbon, alumina, and Florisil cartridges with methanol/dichloromethane as eluting solvents were tested in combination with primary-secondary amine (PSA) to optimize an efficient sample cleanup. PSA in combination with Florisil was the best methodology to extract anticoagulant rodenticides in sludge providing recoveries between 42 ± 0.5 and 100 ± 2 %. Warfarin, bromadiolone, ferulenol, and coumachlor were the most ubiquitous compounds in sludge at concentrations up to 84.2 ng g⁻¹ for the latter. Coumatetralyl, dicoumarol, and brodifacoum were detected sporadically at levels between 6.1 and 17.4 ng g⁻¹. On the contrary, acenocoumarol, difenacoum, and flocoumafen were not detected in any sample. Finally, we estimated the amount of anticoagulant rodenticides discharged via sludge in order to determine the potential impact to agricultural soil according to different sludge usage practices in the region investigated. This study demonstrates that anticoagulant rodenticides are accumulated in sludge during activated sludge treatment and that the application of sludge as fertilizers may pose a future environmental risk, if not controlled.

Anticoagulants are biocides widely used as pest control agents in agriculture, urban infrastructures, and domestic applications for the control of rodents. Other anticoagulants such as warfarin and acenocoumarol are also used as drugs against thrombosis. After use, anticoagulants are discharged to sewage grids and enter wastewater treatment plants (WWTPs). Our hypothesis is that WWTP effluents can be a source of anticoagulants to receiving waters and that these can affect aquatic organisms and other nontarget species. Therefore, the objective of the present study was to determine the occurrence of 11 anticoagulants in WWTPs receiving urban and agricultural wastewaters. Warfarin was the most ubiquitous compound detected in influent waters and was partially eliminated during the activated sludge treatment, and low nanograms per liter concentration were found in the effluents. Other detected compounds were coumatetralyl, ferulenol, acenocoumarol, flocoumafen, brodifacoum, bromadiolone, and difenacoum at concentrations of 0.86–87.0 ng L⁻¹. Considering water volumes of each WWTP, daily emissions were estimated to be 0.02 to 21.8 g day⁻¹, and thus, WWTPs contribute to the loads of anticoagulants to receiving waters. However, low aquatic toxicity was observed using Daphnia magna as a model aquatic organism.

The photochemical fate of 16 pharmaceuticals and personal care products (PPCPs) found in the environment has been studied under controlled laboratory conditions applying a sunlight simulator. Aqueous samples containing PPCPs at environmentally relevant concentrations were extracted by solid-phase extraction (SPE) after irradiation. The exposed extracts were subsequently analysed by liquid chromatography combined with triple quadrupole mass spectrometry (HPLC-MS/MS) for studying the kinetics of photolytic transformations. Almost all exposed PPCPs appeared to react with a half-life time (τ ₁/₂) of less than 30 min. For ranitidine, sulfamethoxazole, diclofenac, warfarin, sulfamethoxazole and ciprofloxacin, τ₁/₂ was found to be even less than 5 min. The structures of major photolysis products were determined using quadrupole-time-of-flight mass spectrometry (QToF) and spectroscopic data reported in the literature. For diclofenac, the transformation products carbazol-1-yl-acidic acid and 8-chloro-9H-carbazol-1-yl-acetic acid were identified based on the mass/charge ratio of protonated ions and their fragmentation pattern in negative electrospray ionization (ESI⁻-QTOF). Irradiation of carbamazepine resulted in three known products: acridine, carbamazepine-10,11-epoxide, and 10,11-dihydro-10,11-dihydroxy-carbamazepine, whereas acetaminophen was photolytically transformed to 1-(2-amino-5 hydroxyphenyl) ethenone. These photochemical products were subsequently identified in seawater or fish samples collected at sites exposed to wastewater effluents on the Saudi Arabian coast of the Red Sea.