A magnetic imprinted polymer nano-adsorbent with embedded quantum dots and mesoporous carbon for the microextraction of triazine herbicides.

A magnetic molecularly imprinted polymer (MMIP) adsorbent incorporating amino-functionalized magnetite nanoparticles, nitrogen-doped graphene quantum dots and mesoporous carbon (MIP@MPC@N-GQDs@Fe3O4NH2) was fabricated to extract triazine herbicides from fruit juice. The embedded magnetite nanoparticles simplified the isolation of the adsorbent from the sample solution. The N-GQDs and MPC enhanced adsorption by affinity binding with triazines. The MIP layer provided highly specific recognition sites for the selective adsorption of three target triazines. The extracted triazines were determined by high-performance liquid chromatography (HPLC) coupled with diode-array detection (DAD). The developed method exhibited linearity from 1.5 to 100.0 µg L-1 with a detection limit of 0.5 µg L-1. Recoveries from spiked fruit juice samples were in the range of 80.1- 108.4 %, with a relative standard deviation of less than 6.0 %. The developed MMIP adsorbent demonstrated good selectivity, high extraction efficiency, ease of fabrication and use, and good stability.

Migration of trace elements and radioisotopes to various fractions of solid wastes generated as a result of the sewage sludge incineration process.

The research was aimed at providing new knowledge in the field of chemical characteristics of solid waste generated in the process of combustion of sewage sludge in fluidized bed furnaces. The research material consisted of disposed fluidized beds (DFB), sewage sludge ash (SSA) and air pollution control residues (APC) from three Polish installations for the thermal treatment of sewage sludge. Natural radionuclides as well as anthropogenic isotope 137Cs were determined in the tested materials and the migration of a wide spectrum of trace elements to various waste fractions generated in the process of sewage sludge combustion was examined. It was observed that both radioisotopes and most of the trace elements determined accumulate in SSA and DFB, while the APC fraction contains a much smaller amount of them. The exceptions are mercury and selenium, whose volatile compounds migrate to the exhaust gas dedusting system and accumulate in the APC fraction (up to 40 mg/kg and 13 mg/kg, respectively). A potential threat from the 226Ra isotope in SSA is identified in the context of the management of this waste in the production of building materials because the typical activity of 226Ra in SSA collected from areas with very low Ra content in natural environment exceeds 1.5-6 times the activity of this isotope in conventional cement mixtures. When managing SSA and DFB, special attention should be paid to the content of metalloids such as As, B and Se, due to the high content of mobile forms of these elements in the mentioned materials.

Comparative Analysis of Laboratory-Made and Industrial-Made Sewage Sludge Ash: Implications for Effective Management Strategy Development.

In the pursuit of environmentally and economically sustainable sewage sludge ash (SSA) management methods, researchers often employ laboratory-made SSA (L-SSA) as a substitute for industrial-made SSA (I-SSA) produced in fluidized bed furnaces. To check whether L-SSA is a material that imitates I-SSA well, the fractionation of metals whose presence is a significant problem during SSA management was performed. In addition, the grain distribution, specific surface area, and textural properties of the tested materials were examined. Differences in total Pb and Hg content and mobility of Cu, Ni, Mn, and Zn were observed between I-SSA and L-SSA. Larger particle sizes of L-SSA compared to I-SSA were confirmed, while comparable textural properties and specific surface area of both types of materials were maintained. Based on the results, it was concluded that L-SSA is chemically different compared to I-SSA, and that L-SSA should not be used as a reference in research focused on the design of SSA management methods. Moreover, fractionation of metals was performed in disposed fluidized beds (FBs), which are diverted to non-hazardous waste landfills without prior analysis. It has been proven that studied metals are present in FBs as abundantly as in SSA, while Cu, Mn, and Ni may show higher mobility than in I-SSA.

Deep eutectic solvent-based shaking-assisted extraction for determination of bioactive compounds from Norway spruce roots.

Polyphenolic compounds play an essential role in plant growth, reproduction, and defense mechanisms against pathogens and environmental stresses. Extracting these compounds is the initial step in assessing phytochemical changes, where the choice of extraction method significantly influences the extracted analytes. However, due to environmental factors, analyzing numerous samples is necessary for statistically significant results, often leading to the use of harmful organic solvents for extraction. Therefore, in this study, a novel DES-based shaking-assisted extraction procedure for the separation of polyphenolic compounds from plant samples followed by LC-ESI-QTOF-MS analysis was developed. The DES was prepared from choline chloride (ChCl) as the hydrogen bond acceptor (HBA) and fructose (Fru) as the hydrogen bond donor (HBD) at various molar ratios with the addition of 30% water to reduce viscosity. Several experimental variables affecting extraction efficiency were studied and optimized using one-variable-at-a-time (OVAT) and confirmed by response surface design (RS). Nearly the same experimental conditions were obtained using both optimization methods and were set as follows: 30 mg of sample, 300 mg of ChCl:Fru 1:2 DES containing 30% w/w of water, 500 rpm shaking speed, 30 min extraction time, 10°C extraction temperature. The results were compared with those obtained using conventional solvents, such as ethanol, methanol and water, whereby the DES-based shaking-assisted extraction method showed a higher efficiency than the classical procedures. The greenness of the developed method was compared with the greenness of existing procedures for the extraction of polyphenolic substances from solid plant samples using the complementary green analytical procedure index (ComplexGAPI) approach, while the results for the developed method were better or comparable to the existing ones. In addition, the practicability of the developed procedure was evaluated by application of the blue applicability grade index (BAGI) metric. The developed procedure was applied to the determination of spruce root samples with satisfactory results and has the potential for use in the analysis of similar plant samples.

Assessment of baby disposable diapers application for urine collection and determination of phthalate metabolites.

The baby disposable diapers were investigated as a sampling material for urine collection and validated for the evaluation of the exposure of children to xenobiotics. Phthalate metabolites detected in urine samples were chosen as proof-of-concept analytes. For the determination of phthalate metabolites in children's urine samples, high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) was used. Two sampling approaches were compared, namely sterile containers and baby disposable diapers. Thirty urine samples from infants and toddlers were analyzed by both methods in parallel and the results were compared. It was found that for diaper sampling, lower concentrations of the metabolites were observed, however, the general distribution for particular metabolites remains the same for both methods. For most of the metabolites high determination coefficients were obtained, namely 0.9929 for MEHHP, 0.9836 for MMP, 0.9796 for MECPP, and 0.9784 for 2-cx-MMHP. For MEOHP the determination correlation coefficient was 0.9154, while for MBP was - 0.7771 and MEHP was - 0.5228. In general, for diaper sampling an underestimation for 2-cx-MMHP and MEOHP was observed, while for MMP diaper-based approach provides overestimation. However, the proposed procedure confirms the possibility of using baby disposable diapers as a material for the collection of urine samples for biomonitoring purposes and fast screening of phthalates exposure.

A magnetic stir bar sorbent of metal organic frameworks, carbon foam decorated zinc oxide and cryogel to enrich and extract parabens and bisphenols from food samples.

A porous composite magnetic stir bar adsorbent was fabricated for the extraction and enrichment of parabens and bisphenols from selected beverage samples. The adsorbent comprised a metal organic framework, carbon foam decorated zinc oxide and magnetic nanoparticles embedded in polyvinyl alcohol cryogel. The porous composite stir bar adsorbent could adsorb parabens and bisphenols via hydrogen bonding, π-π and hydrophobic interactions. In the best conditions, linearity was good from 5.0 to 200.0 µg/L for methyl paraben, ethyl paraben and bisphenol A and from 10.0 to 200.0 µg/L for bisphenol B and butyl paraben. Limits of detection ranged from 1.5 to 3.0 µg/L. The developed composite stir bar was successfully applied to extract and determine parabens and bisphenols in fruit juice, beer and milk. Recoveries ranged from 89.5 to 99.5 % with RSDs lower than 6 %. The developed sorbent and new methodology were evaluated in terms of its green character with satisfactory results.

Exposure scenario and risk assessment of infants and newborns to bisphenols and their derivatives from diapers.

Newborns and infants are more sensitive to harmful compounds such as bisphenols and their derivatives because of their not fully developed detoxification mechanism. Exposure to these substances can lead to developmental problems and health consequences in adulthood. Since disposable baby diapers are used from the first days of life and remain in contact with the baby skin, it seems important to monitor the levels of endocrine disrupting chemicals (EDCs) in such products. Ultrasound assisted solvent microextraction of porous membrane-packed solid sample (UASE-PMSS) was used in sample preparation. Liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) was used at determination step. Bisphenol A was quantified with the highest frequency at 81 % of samples tested, ranging from 5.0 to 520 ng/g. BADGE·2HCl was also quantified in high concentrations (from 6.8 to 530 ng/g), but was found in only 15 % of the tested samples. The daily exposure dose (DED) of bisphenols was calculated. In addition health risk assessment was conducted using previous (4 µg/kg BW) and actual (0.2 ng/kg BW) values of tolerable daily intake (TDI) of bisphenol A recommended by European Food Safety Authority (EFSA).

Insights into baby disposable diapers sustainable application.

The sustainable use of baby disposable diapers is one of the issues currently being discussed to reduce the undesirable impact on the environment and improve the public's understanding of the proper use of diapers. This issue is a step toward promoting a cleaner, greener, and waste-less environment. In this article, the authors discuss options for a viable future for both people and the planet. We believe that it inspire others in the field of sustainable use of diapers as well as future education in this area. In addition, we believe that it will be a motivation for a researchers working in industry to be focused on the production of new, biodegradable baby diapers as well as on recycling baby diapers waste (for example as composite material for a structural and architectural component of the building).

The presence of polycyclic aromatic hydrocarbons in disposable baby diapers: A facile determination method via salting-out assisted liquid-liquid extraction coupled with gas chromatography-mass spectrometry.

In this paper we demonstrate the development of the extraction procedure of polycyclic aromatic hydrocarbons from baby diapers along with their quantification by gas chromatography-mass spectrometry. Apart from covering plastic foil, disposable baby diapers contain sorbents intended to absorb urine and feces. A hygroscopic, adsorptive, and tough-to-homogenize fibrous sorbent, represents an analytical challenge to analytical chemists. To address this issue we optimized and validated a novel extraction protocol including cryogenic homogenization, liquid-liquid extraction and further preconcentration by evaporation. By using deuterated internal standards in conjunction with matrix-matched calibration, high precision and accuracy were achieved. The limit of detection is estimated in the range of 0.041-0.221 ng/g (for fluorene and fluoranthene, respectively), which is far below the concentration currently assumed to be dangerous for children. The method was successfully applied to real samples available on the Polish market, and it was found that the amount of PAH compounds varies between manufacturers. Most diapers do not have all 15 polycyclic aromatic hydrocarbons in their composition, but there is no diaper that is free of these compounds. The most abundant in diapers was acenaphthalene, where the concentration ranged from 1.6 ng/g diaper up to 362.4 ng/g. The lowest concentration in diapers is chrysene, which is not detected in most diapers. The article is a response to the lack of a harmonized analytical method for the determination of polycyclic aromatic hydrocarbons in disposable sanitary products for children.

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.

How pesticides affect neonates? - Exposure, health implications and determination of metabolites.

This review covers key information related to the effects of pesticides on fetal and child health. All humans are exposed to environmental toxicants, however child's health, due to their high vulnerability, should be of special concern. They are continuously exposed to environmental xenobiotics including a wide variety of pesticides, and other pollutants. These compounds can enter the child's body through various routes, both during fetal life, in the first days of life with breast milk, as well as during environmental exposure in later years of life. Consequently, in the body, some of them are metabolized and excreted with urine or faces, while others accumulate in tissues causing toxic effects. This review will provide information on the types of pesticides, their pathways of uptake and metabolism in children's bodies. Determination of the impact of them on children's organism performance is possible through effective identification of these compounds and their metabolites in children's tissues and biofluids. Therefore, the main procedures for the determination of pesticides are reviewed and future trends in this field are indicated. We believe that this comprehensive review can be a good starting place for the future readers interested in the impact of environmental xenobiotics on the health of children as well as the aspects relates with the analytical methods that can be used for analysis and monitoring of these pollutants in children's tissues and biofluids.

Multivariate Statistical Analysis for Mutual Dependence Assessment of Selected Polyphenols, Organic Acids and Metals in Cool-Climate Wines.

Polyphenols, organic acids and metal ions are an important group of compounds that affect the human health and quality of food and beverage products, including wines. It is known that a specific correlation between these groups exist. While wines coming from the New World and the Old World countries are extensively studied, wines coming from cool-climate countries are rarely discussed in the literature. One of the goals of this study was to determine the elemental composition of the wine samples, which later on, together as polyphenols and organic acids content, was used as input data for chemometric analysis. The multivariate statistical approach was applied in order to find specific correlations between the selected group of compounds in the cool-climate wines and the features that distinguish the most and differ between red and white wines and rosé wines. Moreover, special attention was paid to resveratrol and its correlation with selected wine constituents.

Profiling of polar ionogenic metabolites in Polish wines by capillary electrophoresis-mass spectrometry.

The composition of wine is determined by a complex interaction between environmental factors, genetic factors (i.e., grape varieties), and winemaking practices (including technology and storage). Metabolomics using NMR spectroscopy, GC-MS, and/or LC-MS has shown to be a useful approach for assessing the origin, authenticity, and quality of various wines. Nonetheless, the use of additional analytical techniques with complementary separation mechanisms may aid in the deeper understanding of wine's metabolic processes. In this study, we demonstrate that CE-MS is a very suitable approach for the efficient profiling of polar ionogenic metabolites in wines. Without using any sample preparation or derivatization, wine was analyzed using a 10-min CE-MS workflow with interday RSD values for 31 polar and charged metabolites below 3.8% and 23% for migration times and peak areas, respectively. The utility of this workflow for the global profiling of polar ionogenic metabolites in wine was evaluated by analyzing different cool-climate Polish wine samples.

End-of-life management of single-use baby diapers: Analysis of technical, health and environment aspects.

Single-use baby diapers belongs to an important group of products used in the parenting journey because of their high performance and convenience. Single-use baby diapers are normally thrown away after one-time use, resulting in a waste management problem. The goal of this paper was to better understand main environmental concerns of different types of diapers and address how to reduce them, with a special consideration of waste management strategies and user behaviour practices. Furthermore, health and environmental hazards potentially associated with materials included in diapers, or substances formed from diapers during the waste treatment stage, are also analysed (e.g., phthalates, pesticides, dioxins, pesticides). Three main types of baby diapers have been analysed: single-use baby diapers, reusable baby diapers, and biodegradable single-use diapers. Each type of diaper comes with technical characteristics and environmental concerns and challenges, which are discussed in this paper to support the development of measures for the safe(r) and sustainable design, use and end of life management of baby diapers.

A hierarchical porous composite magnetic sorbent of reduced graphene oxide embedded in polyvinyl alcohol cryogel for solvent-assisted-solid phase extraction of polycyclic aromatic hydrocarbons.

A hierarchical porouscomposite magnetic sorbent was fabricated and applied to the dispersive solvent-assisted solid-phase extraction of five polycyclic aromatic hydrocarbons. A sorbent was first prepared by incorporating graphene oxide, calcium carbonate, and magnetite nanoparticles into a polyvinyl alcohol cryogel. The graphene oxide was converted to reduced graphene oxide using ascorbic acid and a hierarchical porous structure was produced by reacting hydrochloric acid with incorporated calcium carbonate to generate carbon dioxide bubbles which created a second network. Before extracting the target analytes, the extraction solvent was introduced into the hierarchical pore network of the sorbent. The extraction was based on the partition between the analytes and introduced extraction solvent and the adsorption of analytes on reduced graphene oxide.The extraction efficiency was enhanced through π-π and hydrophobic interactions between polycyclic aromatic hydrocarbons and reduced graphene oxide and extraction solvent. The extracted polycyclic aromatic hydrocarbons were determined by using high-performance liquid chromatography coupled with a fluorescence detector. The developed method was applied to extract polycyclic aromatic hydrocarbons in disposable diaper, coffee, and tea samples and recoveries from 84.5 to 99.4% were achieved with relative standard deviations below 7%. The developed sorbent exhibited good reproducibility and could be reused for 10 cycles.The developed sorbent exhibited good reproducibility and could be reused for 10 cycles.The developed sorbent exhibited good reproducibility and could be reused for 10 cycles.

Green, simple analytical method for biogenic amines determination in fruit juice samples using salting-out assisted liquid-liquid microextraction andgas chromatography-mass spectrometry.

Salting-out assisted liquid-liquid microextraction (SALLME) was integrated withthederivatization procedure to establish a one-step sample pre-treatment approach for rapid analysis of14 biogenic amines (BAs) in fruit juices. The methodology consists of salting-out ofanalytes,derivatization with ethyl chloroformate (ECF), extraction with ethyl acetate (EtAc), andtheanalysis of the derivatized BAs using gas chromatography-mass spectrometry (GC-MS). Optimization oftheSALLME parameters, including the amount of sample, NaOH, and ECF was carried out through a Box-Behnken response surface design. The developed method exhibits satisfactory limits ofdetection (from 1.5 to 8.1 µg/L) andquantification (from 5.0 to 26.7 µg/L), and average recoveries between 84% and 108%. The developed procedure was used for BAs determination injuices ofdifferent berries withthe highest determined concentrations found for cadaverine, putrescine, tryptamine, andtyramine. Both GAPI and AGREE tools were used to assess the green character of the SALLME-GC-MS procedure.

The impact of cold plasma on the phenolic composition and biogenic amine content of red wine.

The effect of cold plasma (CP) on phenolic compound (PC) and biogenic amine (BA) contents of red wine was investigated for the first time. The influence of CP was compared with the effects of a wine preservation using potassium metabisulfite and a combined method. The PC profile was determined by UPLC-PDA-MS/MS while BAs using DLLME-GC-MS. Chemometric analysis also was used. The content of PCs was 3.1% higher in the sample preserved by CP treatment (5 min, helium/nitrogen) compared to a sample preserved by the addition of potassium metabisulfite (100 mg/L). On a positive note, CP treatment reduced the concentration of BAs in the wine samples. The lowest BA contents were recorded after 10 min of cold plasma (helium/oxygen) treatment with the addition of potassium metabisulfite (1120.85 µg/L). The results may promote interest in CP as a potential alternative method for the preservation of wine and other alcoholic beverages.

Nanosorbents as Materials for Extraction Processes of Environmental Contaminants and Others.

The aim of this work focuses on the application of nanomaterials (NMs) in different sorptive extraction techniques for the analysis of organic contaminants from environmental samples of distinct matrix compositions. Without any doubt, the integration of specific NMs such as carbonaceous nanomaterials, magnetic nanoparticles (MNPs), metal-organic frameworks (MOFs), silica nanoparticles, and ion-imprinted NPs with solid-phase extraction techniques counting d-SPE, solid-phase microextraction (SPME), and stir bar sorptive extraction (SBSE) impact on the improvements in analytical performance. The application of NMs as sorbents in the extraction of organic pollutants in environmental samples allows for providing better sensitivity, repeatability, reproducibility, and reusability.

The content of biogenic amines in Rondo and Zweigelt wines and correlations between selected wine parameters.

The purpose of this study was to evaluate the content of biogenic amines (BAs) in wines using dispersive liquid-liquid microextraction-gas chromatography-mass spectrometry (DLLME-GC-MS). An additional objective was to assess the correlations between selected parameters characterizing the samples such as the content of BAs, sugars, and organic acids, pH, and total acidity. Wines produced from the same grape variety in which alcoholic fermentation (AF) was carried out by different yeast strains and in which malolactic fermentation (MLF) was spontaneous, differed in the content of biogenic amines. The concentrations of putrescine, cadaverine and tryptamine were higher in the Rondo wines (237-405, 34.04-61.11,

Green analytical chemistry metrics: A review.

Green analytical chemistry encourages reducing the use of toxic chemicals/reagents, using energy-efficient equipment, and generating minimal waste. The recent trends in analytical method development focus on the miniaturization of the sample preparation devices, the development of solventless or solvent-minimized extraction techniques, and the utilization of less toxic solvents. The twelve principles of GAC serve as a basic guideline for inducing greenness in the analytical procedures. Despite these guidelines, in many conditions, some undesired steps are unavoidable. Therefore, it is important to evaluate the greenness of analytical procedures to assess and, if possible, reduce their impact on the environment and workers. Several metrics have been developed for the evaluation of the greenness of analytical procedures. Analytical Eco-Scale, Green Analytical Procedure Index, and Analytical Greenness Metric are among some important tools for assessing the greenness of analytical procedures. All these metrics take different aspects of the analytical procedure into account to provide the green index of the procedure. This review covered these metrics, their principles, and examples of their application to selected analytical procedures. The advantages and limitations of these metrics with the perspective of common reader/user are presented. We believe that this paper will inspire many new perspectives and developments in this area.