Assessment of the application of selected metal-organic frameworks as advanced sorbents in passive extraction used in the monitoring of contaminants of emerging concern in surface waters.

Water pollution has become a critical global concern requiring effective monitoring techniques and robust protection strategies. Contaminants of emerging concern (CECs) are increasingly detected in various water sources, with their harmful effects on humans and ecosystems continually evolving. Based on literature reports highlighting the promising sorption properties of metal-organic frameworks (MOFs), the aim of this study was to evaluate the suitability of NH2-MIL-125 (Ti) and UiO-66 (Ce) as sorbents in passive sampling devices (MOFs-PSDs) for the collection and extraction of a wide group of CECs. Solvothermal methods were used to synthesize MOFs, and the characterization of the obtained materials was performed using field-emission scanning electron microscopy (FE-SEM), powder X-ray diffractometry (pXRD) and Fourier-transform infrared (FTIR) spectroscopy. The research demonstrated the sorption capabilities of the tested MOFs, the ease and rapidity of their chemical regeneration and the possibility of reuse as sorbents. Using chemometric analysis, the structural properties of CECs determining the sorption efficiency on the surface of NH2-MIL-125 (Ti) were identified. The MOFs-PSDs were lab-calibrated to examine the kinetics of analytes sorption and determine the sampling rates (Rs). MOFs-PSDs and CNTs-PSDs (PSDs containing carbon nanotubes as a sorbent) were then placed in the Elblag River and the Vistula Lagoon to sampling and extraction of the target compounds from the water. CNTs-PSDs were selected, based on our previous research, for the comparison of the effectiveness of the MOFs-PSDs in environmental monitoring. MOFs-PSDs were successfully used in monitoring of CECs in water. The time-weighted average concentrations (CTWA) of 2-hydroxycarbamazepine, carbamazepine-10,11-epoxide, p-nitrophenol, 3,5-dichlorophenol and caffeine were determined in the Elblag River and CTWA of metoprolol, diclofenac, 2-hydroxycarbamazepine, carbamazepine-10,11-epoxide, p-nitrophenol, 3,5-dichlorophenol and caffeine were determine in the Vistula Lagoon using MOFs-PSDs and a high-performance liquid chromatography coupled with triple quadrupole mass spectrometer.

Reusable passive sampler with carbon nanotubes for monitoring contaminants in wastewater: Application, regeneration and reuse.

Progress in excogitation suitable strategies for monitoring chemical compounds in wastewater is an essential step for further research into the occurrence, impact, and fate of the pollutants in the aquatic environment. At present, it is desirable to advance and use economical, environmentally friendly and non-labour intensive methods of environmental analysis. In this study, carbon nanotubes (CNTs) were successfully applied, regenerated, and reused as a sorbent in passive samplers for monitoring contaminants in treated and untreated wastewater at three wastewater treatment plants (WWTPs) located in different urbanization areas in northern Poland. Three cycles of chemical and thermal regeneration of used sorbents were performed. It was shown that it is possible to regenerate CNTs a minimum of three times and reuse them in passive samplers while maintaining the desired sorption properties. The obtained results confirm that the CNTs are perfectly in line with the main principles of green chemistry and sustainability. Carbamazepine, ketoprofen, naproxen, diclofenac, p-nitrophenol, atenolol, acebutolol, metoprolol, sulfapyridine and sulfamethoxazole were detected in each of the WWTPs, both in treated and untreated wastewater. The obtained data drastically show the inefficiency of the removal of contaminants by conventional WWTPs. More importantly, the results even indicate negative contaminant removal in most cases, i.e. higher concentrations (up to 863%) of these substances in the effluent compared to the influent.

Endocrine disrupting compounds in the baby's world - A harmful environment to the health of babies.

Globally, there has been a significant increase in awareness of the adverse effects of chemicals with known or suspected endocrine-acting properties on human health. Human exposure to endocrine disrupting compounds (EDCs) mainly occurs by ingestion and to some extent by inhalation and dermal uptake. Although it is difficult to assess the full impact of human exposure to EDCs, it is well known that timing of exposure is of importance and therefore infants are more vulnerable to EDCs and are at greater risk compared to adults. In this regard, infant safety and assessment of associations between prenatal exposure to EDCs and growth during infancy and childhood has been received considerable attention in the last years. Hence, the purpose of this review is to provide a current update on the evidence from biomonitoring studies on the exposure of infants to EDCs and a comprehensive view of the uptake, the mechanisms of action and biotransformation in baby/human body. Analytical methods used and concentration levels of EDCs in different biological matrices (e.g., placenta, cord plasma, amniotic fluid, breast milk, urine, and blood of pregnant women) are also discussed. Finally, key issues and recommendations were provided to avoid hazardous exposure to these chemicals, taking into account family and lifestyle factors related to this exposure.

Ionic liquid-based functionalized materials for analytical chemistry.

Inherent in the use of almost any analytical technique is the need to improve the separation efficiency and extract purity. One possibility for enhancing analytical methods is the application of substances / materials that functionalize components of the separation system. They interact with the material to be modified, either permanently or temporarily. Typically, organic solvents or salts are used for this purpose. The ionic liquids (ILs) are salts that remain in the liquid phase at temperatures below 100 ℃, what gives them advantage compared to traditional modifiers. This paper presents the range of applications of ILs in functionalized materials in analytical chemistry, as presented in publications from the last five years. Several types of techniques in which ILs are used are presented (HPLC, GC, electrophoresis, supported liquid membranes, passive sampling, various modification of solid-phase extraction), along with most interesting exemplary studies. As expected, imidazolium ILs are most commonly used. The application of ILs for functionalization in analytical techniques is extremely useful, but the problem is their cost and the low recovery rate. However, the rapid development in this field of science and the promising results encourage further work on the issue of ILs in functionalized materials.

Carbon nanotube-passive samplers as novel tools for sampling and determining micropollutants in the aquatic environment.

Passive sampling is an interesting and cost-effective strategy for the quantification of micropollutants in the aquatic environment. When combined especially with a sensitive analytical method such as liquid chromatography coupled with triple quadrupole mass spectrometry (LC-MS/MS), the use of passive sampling devices (PSDs) enables long-term and reliable determination of a wide range of chemicals. In this study, carbon nanotubes (CNTs) were used as an innovative sorbent in POCIS-like samplers (Polar Organic Chemical Integrative Sampler). The developed CNTs-PSDs were calibrated by the flow-through method and the obtained sampling rates (Rs) of analytes were compared with the previously obtained Rs values using the semi-static method. Subsequently, passive samplers were placed in the Baltic Sea, the Nogat River, and the Sztumskie Pole Lake in order to sample and concentrate 28 chemical compounds belonging to the group of contaminants of emerging concern (CECs). For the first time, the effectiveness of the use of CNTs-PSDs in the field was proven by the quantification of carbamazepine, diclofenac, p-nitrophenol, bisphenol A, 3,5-dichlorophenol, 17-ß-estradiol, 17-α-ethinylestradiol and metoprolol in the tested surface waters. The obtained time-weighted average (TWA) concentrations of analytes ranged from 0.22 ± 0.12 ng/L (for metoprolol in the Nogat River) to 32.1 ± 2.4 ng/L (for bisphenol A in the Sztumskie Pole Lake). More importantly, CNTs-PSDs determined a greater amount of micropollutants than grab sampling and solid-phase extraction (SPE), which proves the advantage of passive sampling over grab sampling, especially when monitoring contaminants in the aquatic environment at low concentration levels.

Impact of environmental factors on the sampling rate of ß-blockers and sulfonamides from water by a carbon nanotube-passive sampler.

Passive techniques are a constantly evolving approach to the long-term monitoring of micropollutants, including pharmaceuticals, in the aquatic environment. This paper presents, for the first time, the calibration results of a new CNTs-PSDs (carbon nanotubes used as a sorbent in passive sampling devices) with an examination of the effect of donor phase salinity, water pH and the concentration of dissolved humic acids (DHAs), using both ultrapure and environmental waters. Sampling rates (Rs) were determined for the developed kinetic samplers. It has been observed that the impact of the examined environmental factors on the Rs values strictly depends on the type of the analytes. In the case of ß-blockers, the only environmental parameter affecting their uptake rate was the salinity of water. A certain relationship was noted, namely the higher the salt concentration in water, the lower the Rs values of ß-blockers. In the case of sulfonamides, water salinity, water pH 7-9 and DHAs concentration decreased the uptake rate of these compounds by CNTs-PSDs. The determined Rs values differed in particular when the values obtained from the experiments carried out using ultrapure water and environmental waters were compared. The general conclusion is that the calibration of novel CNTs-PSDs should be carried out under physicochemical conditions of the aquatic phase that are similar to the environmental matrix.

Application of the Polar Organic Chemical Integrative Sampler for Isolation of Environmental Micropollutants - A Review.

Aquatic passive samplers have been extensively tested and deployed in the field over the past two decades. Among these devices is relatively recently developed the Polar Organic Chemical Integrative Sampler (POCIS) for isolation of hydrophilic organic micropollutants in aquatic environment. The use of POCIS allows the measurement of low and fluctuating trace concentrations of such micropollutants, which is often troublesome using classical sampling. In this review, POCIS applications based on numerous articles to assess the suitability of these devices for use in environmental analytics information were summarized. Additionally, the possibilities of using POCIS for the isolation of complex chemical mixtures in order to highlight the high potential of this devices were presented. The types of sorbents used in POCIS, exposure duration and sampling media are juxtapose in this review. Based on the existing literature, attention was paid to both promising opportunities but also to limitations of passive methods.