Development of a novel LED-IoT photoreactor for enhanced removal of carbamazepine waste driven by solar energy.

This study introduces an innovative LED-IoT photoreactor, representing a significant advancement in response to the demand for sustainable water purification. The integration of LED-IoT installations addresses the challenge of intermittent sunlight availability, employing LEDs with a spectrum mimicking natural sunlight. Passive Infra-Red (PIR) sensors and Internet of things (IoT) technology ensure consistent radiation intensity, with the LED deactivating in ample sunlight and activating in its absence. Utilizing a visible light-absorbing photocatalyst developed through sol-gel synthesis and mild-temperature calcination, this research demonstrates a remarkable carbamazepine removal efficiency exceeding 95% under LED-IoT system illumination, compared to less than 90% efficiency with sunlight alone, within a 6-h exposure period. Moreover, the designed photocatalytic system achieves over 60% mineralization of carbamazepine after 12 h. Notably, the photocatalyst demonstrated excellent stability with no performance loss during five further cycles. Furthermore, integration with renewable energy sources facilitated continuous operation beyond daylight hours, enhancing the system's applicability in real-world water treatment scenarios. A notable application of the LED-IoT system at an operating sewage treatment plant showed nearly 80% efficiency in carbamazepine removal from sewage in the secondary settling tank after 6 h of irradiation, coupled with nearly 40% mineralization efficiency. Additionally, physicochemical analyses such as XPS and STA-FTIR confirm that the carbamazepine photooxidation process does not affect the surface of the photocatalyst, showing no adsorption for degradation products.

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.

Retracted: Atomic Absorption Spectrometry Analysis of Trace Elements in Degenerated Intervertebral Disc Tissue.

Medical Science Monitor is retracting the following publication on the basis of duplicated published content. 1) Kubaszewski L, Ziola-Frankowska A, Frankowski M, Rogala P, Gasik Z, Kaczmarczyk J, Nowakowski A, Dabrowski M, Labedz W, Miekisiak G, Gasik R. Comparison of trace element concentration in bone and intervertebral disc tissue by atomic absorption spectrometry techniques. J Orthop Surg Res. 2014 Oct 25;9: 99. doi: 10.1186/s13018-014-0099-y. PMID: 25342441; PMCID: PMC4220064. 2) Kubaszewski L, Ziola-Frankowska A, Frankowski M, Nowakowski A, Czabak-Garbacz R, Kaczmarczyk J, Gasik R. Atomic absorption spectrometry analysis of trace elements in degenerated intervertebral disc tissue. Med Sci Monit. 2014 Nov 4;20: 2157-64. doi: 10.12659/MSM.890654. PMID: 25366266; PMCID: PMC4301216. 3) Nowakowski A, Kubaszewski L, Frankowski M, Wilk-Franczuk M, Ziola-Frankowska A, Czabak-Garbacz R, Kaczmarczyk J, Gasik R. Analysis of trace element in intervertebral disc by Atomic Absorption Spectrometry techniques in degenerative disc disease in the Polish population. Ann Agric Environ Med. 2015;22(2): 362-7. doi: 10.5604/12321966.1152096. PMID: 26094540. We have reviewed the content of all three similar publications. We note that Medical Science Monitor was the second to publish this study, in November 2014. At that time, the Corresponding Author gave no declaration of submitting this study to any other journal, nor of previously publishing this study. Reference: Lukasz Kubaszewski, Anetta Ziola-Frankowska, Marcin Frankowski, Andrzej Nowakowski, Róza Czabak-Garbacz, Jacek Kaczmarczyk, Robert Gasik. Atomic Absorption Spectrometry Analysis of Trace Elements in Degenerated Intervertebral Disc Tissue. Med Sci Monit, 2014; 20: 2157-2164. DOI: 10.12659/MSM.890654.

New Method for Simultaneous Arsenic and Selenium Speciation Analysis in Seafood and Onion Samples.

This paper presents a new method for the simultaneous speciation analysis of arsenic (As(III)-arsenite, As(V)-arsenate, DMA-dimethylarsinic acid, MMA-methylarsonic acid, and AsB-arsenobetaine) and selenium (Se(IV)-selenite, Se(VI)-selenate, Se-Methionine, and Se-Cystine), which was applied to a variety of seafood and onion samples. The determination of the forms of arsenic and selenium was undertaken using the High-Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS) analytical technique. The separation of both organic and inorganic forms of arsenic and selenium was performed using two analytical columns: an anion exchange column, Dionex IonPac AS22, containing an alkanol quaternary ammonium ion, and a double bed cation-anion exchange guard column, Dionex Ion Pac CG5A, containing, as a first layer, fully sulfonated latex for cation exchange and a fully aminated layer for anion exchange as the second layer. The ammonium nitrate, at pH = 9.0, was used as a mobile phase. The method presented here allowed us to separate the As and Se species within 10 min with a suitable resolution. The applicability was presented with different sample matrix types: seafood and onion.

The Role of Sulphate and Phosphate Ions in the Recovery of Benzoic Acid Self-Enhanced Ozonation in Water Containing Bromides.

The ozonation of aromatic compounds in low-pH water is ineffective. In an acidic environment, the decomposition of ozone into hydroxyl radicals is limited and insufficient for the degradation of organic pollutants. Radical processes are also strongly inhibited by halogen ions present in the reaction medium, especially at low pH. It was shown that even under such unfavorable conditions, some compounds can initiate radical chain reactions leading to the formation of hydroxyl radicals, thus accelerating the ozonation process, which is referred to as so-called "self-enhanced ozonation". This paper presents the effect of bromides on "self-enhanced ozonation" of benzoic acid (BA) at pH 2.5. It is the first report to fully and quantitatively describe this process. The presence of only 15 µM bromides in water inhibits ozone decomposition and completely blocks BA degradation. However, the effectiveness of this process can be regained by ozonation in the presence of phosphates or sulphate. The addition of these inorganic salts to the bromide-containing solution helps to recover ozone decomposition and BA degradation efficiency. As part of this research, the fractions of hydroxyl, sulphate and phosphate radicals reacting with benzoic acid and bromides were calculated.

Chemical Speciation of Aluminum in Wine by LC-ICP-MS.

Aluminum is very common in the natural environment and in everyday human life. We are living in the "aluminum age." Its average daily intake should not exceed a few mg/day. Unfortunately, despite the growing number of alarming data about the toxicity of this element, human exposure to aluminum is constantly increasing. The toxicity and bioavailability of aluminum depends mainly on the form in which it occurs. The main variables conditioning the form are the concentration, the type, the molar ratio of aluminum to ligand, the pH value, and the temperature. This research presents a new method for speciation analysis of both inorganic and organic aluminum complexes in model solutions by LC-ICP-MS. Different solutions with variable pH values and different Al/ligand molar ratios (fluorides and several organic ligands, e.g., citrates and oxalates ions) were used. The chromatographic separation process was carried out based on isocratic and gradient elution, using a cation exchange analytical column. All determinations have been confirmed based on chemical equilibrium modeling programs. The new developed method was successfully applied for the first time in speciation analysis of real samples: white and red wine.

Analysis of Hazardous Elements in Children Toys: Multi-Elemental Determination by Chromatography and Spectrometry Methods.

This paper presents the results of determination of hazardous metal (Cd, Cu, Cr, Hg, Mn, Ni, Pb, Zn) and metalloid (As, Sb) levels in toys available in the Polish market. Two independent sample preparation methods were used to determine the concentration and content of the metals and metalloids. The first one is defined by the guidelines of the EN-71 standard and undertook extraction in 0.07 mol/L HCl. This method was used to conduct speciation analysis of Cr(III) and Cr(VI), as well as for the determination of selected metals and metalloids. The second method conducted mineralization in a HNO3 and H2O2 mixture using microwave energy to determine the content of metals and metalloids. Determination of chromium forms was made using the high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) method, while those of metals and metalloids were made using the ICP-MS technique. Additionally, in order to determine total content of chromium in toys, an energy dispersive X-ray fluorescence spectrometer (EDX) was used. The results of the analyses showed that Cr(VI) was not detected in the toys. In general, the content of heavy metals and metalloids in the studied samples was below the migration limit set by the norm EN-71.

Determination of Metals Content in Wine Samples by Inductively Coupled Plasma-Mass Spectrometry.

Knowledge about the metal content of wine is very important, for many reasons. Depending on the element, its quantity varies in wine from ng/L to mg/L. Despite the fact that metals are not directly connected to the taste and aroma of the wine, their content should be determined and controlled, because excess is undesirable, and in some cases prohibited, due to potential toxicity. Several analytical procedures for metal determination are applied. However, due to sensitivity, low limit of detection and speed of analysis, inductively coupled plasma-mass spectrometry (ICP-MS) is one of the most frequently used techniques. The aim of this study was to reveal specific relationships between the wine samples or between the chemical variables in order to classify the wines according to their metal content by application of chemometric analysis. For metals content determination, two techniques, ICP-MS and inductively coupled plasma-optical emission spectrometry (ICP-OES), were applied. Data obtained showed that none of the wine samples surpassed the toxic levels reported for metals in the literature, thus, these wines appeared to be safe as regards the risk associated with the potentially toxic metals intake. However, specific correlations between metals and specific aspects of the wines themselves have been found.

Speciation analysis of aluminium in plant parts of Betula pendula and in soil.

The research presents the first results of aluminium speciation analysis in aqueous extracts of individual plant parts of Betula pendula and soil samples, using High Performance Ion Chromatography with Diode Array Detection (HPIC-DAD). The applied method allowed us to carry out a full speciation analysis of aluminium in the form of predominant aluminium-fluoride complexes: AlF(x=2,3,4)(3-x) (first analytical signal), AlF2+ (second analytical signal) and Al3+ (third analytical signal) in samples of lateral roots, tap roots, twigs, stem, leaf and soil collected under roots of B. pendula. Concentrations of aluminium and its complexes were determined for two types of environment characterised by different degree of human impact: contaminated site of the Chemical Plant in Lubon and protected area of the Wielkopolski National Park. For all the analysed samples of B. pendula and soil, AlF(x=2,3,4)(3-x) had the largest contribution, followed by Al3+ and AlF2+. Significant differences in concentration and contribution of Al-F complexes and Al3+ form, depending on the place of sampling (different anthropogenic pressure) and plant part of B. pendula were observed. Based on the obtained results, it was found that transport of aluminium is "blocked" by lateral roots, and is closely related to Al content of soil.

Simultaneous speciation analysis of inorganic nitrogen with the use of ion chromatography in highly salinated environmental samples.

We present the development of a method for the simultaneous determination of inorganic nitrogen species in oxidized (NO2 (-) , NO3 (-) ) and reduced (NH4 (+) ) forms using ion chromatography with diode-array detection (205, 208, and 425 nm, respectively). The oxidized forms were determined directly after the separation in the anion exchanger, while the reduced form was determined in the column hold-up time after derivatization with the Nessler reagent. The use of an appropriate modifier (Seignette reagent) and mobile phase (NaCl) enabled the determination of inorganic nitrogen species in highly salinated environmental samples (water, sediments). Moreover, low detection limits were obtained of 0.04 mg/L for NH4 (+) and 0.006 and 0.005 mg/L for NO2 (-) and NO3 (-) , respectively. The analysis of environmental samples indicated NH4 (+) contents of up to 1161 ± 47 mg/kg and NO3 (-) of up to 148 ± 6 mg/kg for sediment samples, as well as the NH4 (+) concentrations of up to 0.98 ± 0.10 mg/L, NO2 (-) of up to 24 ± 1 mg/L and NO3 (-) of up to 20 ± 1 mg/L for water samples.

Levels and potential health risks of mercury in prescription, non-prescription medicines and dietary supplements in Poland.

Determination of mercury is important in the case of pharmaceuticals for which the European Union regulations have not defined the maximum permissible concentration of this metal. The aim of the study was to determine the levels of mercury in the following groups of drugs (n = 119): analgesics, diuretics, cardiacs, antihypertensives, anti-influenza, antibiotics, anti-allergics, tranquilizers, antibacterials and in dietary supplements (n = 33) available on the Polish market. Mercury was analyzed using cold vapor atomic fluorescence spectrometry CV-AFS. Its content in the samples varied in the range of 0.9-476.1 ng g(-1). Higher mercury concentrations were reported for prescription drugs (Rx): 0.9-476.1 ng g(-1) (median: 7.4 ng g(-1)), lower--for non-prescription medicines (OTC): 1.2-45.8 ng g(-1) (median: 6.0 ng g(-1)). In the analyzed dietary supplements the concentrations were: 0.9-16.7 ng g(-1) (median: 5.9 ng g(-1)). On the basis of the information contained in the leaflet accompanying the medicine, a daily dose of mercury taken into the body with an analyzed medicament was estimated and the health risk posed by using such medicines was assessed. The study indicates that it is justified to carry out measurements of mercury in pharmaceuticals due to its high, potentially harmful.

Trace element distribution in the snow cover from an urban area in central Poland.

This work presents the first results from winter field campaigns focusing on trace metals and metalloid chemistry in the snow cover from an urbanized region in central Poland. Samples were collected between January and March 2013 and trace element concentrations were determined using GF-AAS. A large inter-seasonal variability depending on anthropogenic emission, depositional processes, and meteorological conditions was observed. The highest concentration (in µg L(-1)) was reported for Pb (34.90), followed by Ni (31.37), Zn (31.00), Cu (13.71), Cr (2.36), As (1.58), and Cd (0.25). In addition, several major anthropogenic sources were identified based on principal component analysis (PCA), among which the most significant was the activity of industry and coal combustion for residential heating. It was stated that elevated concentrations of some trace metals in snow samples were associated with frequent occurrence of south and southeast advection of highly polluted air masses toward the sampling site, suggesting a large impact of regional urban/industrial pollution plumes.

Atomic absorption spectrometry analysis of trace elements in degenerated intervertebral disc tissue.

BACKGROUND: Few studies have investigated trace elements (TE) in human intervertebral disc (IVD) tissue. Trace element presence can have diverse meanings: essential TE show the metabolic modalities of the tissue, while environmentally-related TE indicate pollution and tissue-specific absorption and accumulation. IVD is a highly specific compartment with impaired communication with adjacent bone. Analysis of TE in IVD provides new insights regarding tissue metabolism and IVD communication with other tissues. MATERIAL/METHODS: Thirty intervertebral discs were acquired from 22 patients during surgical treatment for degenerative disease. Atomic absorption spectrometry was used to evaluate the concentrations of Al, Cd, Pb, Cu, Ni, Mo, Mg, and Zn. RESULTS: Al, Pb, Cu, Mg, and Zn were detected in all samples. Pb was significantly positively correlated with age, and Ni concentration was weakly correlated with population count in the patient's place of residence. Only Cu was observed in higher concentrations in IVD compared to in other tissues. Significant positive correlations were observed between the following pairs: Mg/Zn, Mg/Al, Mg/Pb, Zn/Al, Zn/Pb, and Al/Pb. Negative correlations were observed between Mg/Cd, Zn/Cd, Mg/Mo, and Mo/Pb. CONCLUSIONS: This study is one of few to profile the elements in intervertebral discs in patients with degenerative changes. We report significant differences between trace element concentrations in intervertebral discs compared to in other tissues. Knowledge of the TE accumulation pattern is vital for better understanding intervertebral disc nutrition and metabolism.

Comparison of the level of boron concentrations in black teas with fruit teas available on the Polish market.

The determination of boron by inductively coupled plasma-atomic emission spectrometry has been carried in water-soluble and acid soluble (total content) fractions of 36 samples of traditional black tea and fruit brew. The estimation of the impact of the type of tea on the concentration of boron in water-soluble and acid extracts and potential human health risk from the daily intake of boron was carried out in this study. The levels of boron differed significantly in black and fruit tea types. The mean total content of boron ranged from 8.31 to 18.40 mg/kg in black teas, from 12.85 to 15.13 mg/kg in black tea with fruit flavor, and from 12.09 to 22.77 mg/kg in fruit brews. The degree of extraction of boron in black tea ranged from 8% to 27% and for fruit tea from 17% to 69%. In addition, the values below 25% were of black teas with fruit flavors. The daily intake of B from tea infusions (three cups/day) is still within the average daily intake except for some of the fruit brews which exceed acceptable regulations of the daily intake of total boron by humans. Hence, it may not produce any health risks for human consumption, if other sources of metal contaminated food are not taken at the same time.

Seasonality of water chemistry, carbonate production, and biometric features of two species of Chara in a shallow clear water lake.

The objective of this study was to analyze the temporal variability of biometric features and the carbonate production of two charophytes: Chara polyacantha A. Braun and Chara rudis A. Braun against the background of the physical-chemical properties of water. The investigation was carried out in a small, mid-forest Lake Jasne (western Poland). It is a polymictic, mesotrophic, hardwater ecosystem dominated by charophyte vegetation. Each month, 10 individuals of each species were characterized in terms of morphometric features, fresh and dry weight, and the percentage of calcium carbonate. Additionally, physical-chemical parameters of the water were studied. The results of physical-chemical analyses indicated similar habitat conditions for both species. Despite smaller dry weight C. polyacantha was characterized by greater morphological variability and higher rates of growth and percentage share of calcium carbonate in dry mass than C. rudis. The percentage of calcium carbonates in dry mass did not differ significantly between the species and exceeded 60%, reaching the maximum (76% in C. polyacantha) in July and August. For both species, distinct correlations between the structure of biomass and morphological features were found. The obtained results show the great importance of charophyte vegetation in carbon cycling and functioning of lake ecosystems.

The toxicological analysis and assessment of essential elements (Cu, Fe, Mn, Zn) in Food for Special Medical Purposes (FSMP) dedicated to oncological patients available in Polish pharmacies.

Foods for Special Medical Purposes (FSMP) for oncology patients, available in pharmacies, play a crucial role in providing nutrition and supplementation. However, the scientific literature lacks comprehensive research on the safety of essential trace elements in these products. This study aimed to assess Cu, Fe, Mn and Zn levels in commonly prescribed FSMPs (n = 23) from Polish pharmacies. Using ICP-MS after microwave-induced digestion (using concentrated nitric acid and hydrogen peroxide), we evaluated element levels. Our research used three approaches: the raw score for Cu, Fe, Mn, and Zn; single intake per serving; and the daily ration, compared with the reference values of the European Food Safety Authority. Discrepancies were found between the actual and declared product compositions, influenced by the route of administration and the recommended intake. Despite variations, all products were considered safe for oncological patients based on current evidence. However, it is recommended to have clear guidelines for FSMPs in cancer care. This pioneering study evaluates the safety and quality of prescription FSMPs for cancer patients from toxicological and nutritional perspectives, highlighting the need for standardised protocols in pharmacy-dispensed FSMPs.

Copper(II) phosphate as a promising catalyst for the degradation of ciprofloxacin via photo-assisted Fenton-like process.

This work aims to unravel the potential of copper(II) phosphate as a new promising heterogenous catalyst for the degradation of ciprofloxacin (CIP) in the presence of H2O2 and/or visible light (λ > 400 nm). For this purpose, copper(II) phosphate was prepared by a facile precipitation method and fully characterized. Of our particular interest was the elucidation of the kinetics of CIP degradation on the surface of this heterogeneous catalyst, identification of the main reactive oxygen species responsible for the oxidative degradation of CIP, and the evaluation of the degradation pathways of this model antibiotic pollutant. It was found that the degradation of the antibiotic proceeded according to the pseudo-first-order kinetics. Copper(II) phosphate exhibited ca. 7 times higher CIP degradation rate in a Fenton-like process than commercial CuO (0.00155 vs. 0.00023 min-1, respectively). Furthermore, the activity of this metal phosphate could be significantly improved upon exposure of the reaction medium to visible light (reaction rate = 0.00445 min-1). In a photo-assisted Fenton-like process, copper(II) phosphate exhibited the highest activity in CIP degradation from among all reference samples used in this study, including CuO, Fe2O3, CeO2 and other metal phosphates. The main active species responsible for the degradation of CIP were hydroxyl radicals.

Speciation analysis of arsenic in honey using HPLC-ICP-MS and health risk assessment of water-soluble arsenic.

It is well known that arsenic is one of the most toxic elements. However, measuring total arsenic content is not enough, as it occurs in various forms that vary in toxicity. Since honey can be used as a bioindicator of environmental pollution, in the present study the concentration of arsenic and its species (As(III), As(V), DMA, MMA and AsB) was determined in honey samples from mostly Poland and Ukraine using HPLC-ICP-MS hyphenated technique. The accuracy of proposed methods of sample preparation and analysis was validated by analyzing certified reference materials. Arsenic concentration in honey samples ranged from 0.12 to 13 µg kg-1, with mean value of 2.3 µg kg-1. Inorganic arsenic forms, which are more toxic, dominated in honey samples, with Polish honey having the biggest mean percentage of inorganic arsenic species, and Ukrainian honey having the lowest. Furthermore, health risks resulting from the consumption of arsenic via honey were assessed. All Target Hazard Quotient (THQ) values, for total water-soluble arsenic and for each form, were below 1, and all Carcinogenic Risk (CR) values were below 10-4, which indicates no potential health risks associated with consumption of arsenic via honey at average or recommended levels.

Three musketeers of PDA-based MRI contrasting and therapy.

Polydopamine (PDA) stands as a versatile material explored in cancer nanomedicine for its unique properties, offering opportunities for multifunctional drug delivery platforms. This study explores the potential of utilizing a one-pot synthesis to concurrently integrate Fe, Gd and Mn ions into porous PDA-based theranostic drug delivery platforms called Ferritis, Gadolinis and Manganis, respectively. Our investigation spans the morphology, magnetic properties, photothermal characteristics and cytotoxicity profiles of those potent nanoformulations. The obtained structures showcase a spherical morphology, robust magnetic response and promising photothermal behaviour. All of the presented nanoparticles (NPs) display pronounced paramagnetism, revealing contrasting potential for MRI imaging. Relaxivity values, a key determinant of contrast efficacy, demonstrated competitive or superior performance compared to established, used contrasting agents. These nanoformulations also exhibited robust photothermal properties under near infra-red irradiation, showcasing their possible application for photothermal therapy of cancer. Our findings provide insights into the potential of metal-doped PDA NPs for cancer theranostics.

Association of Metallic and Nonmetallic Elements with Fibrin Clot Properties and Ischemic Stroke.

Objectives-Metallic elements and fibrin clot properties have been linked to stroke. We examined metallic and nonmetallic elements, fibrin clot lysis time (CLT), and maximum absorbance (Absmax) in relation to ischemic stroke. Design-A case-control study of ischemic stroke patients vs. healthy individuals. Subjects and Methods-Plasma and serum were collected from 260 ischemic stroke patients (45.0% women; age, 68 ± 12 years) and 291 healthy controls (59.7% women; age, 50 ± 17 years). Fibrin CLT and Absmax were measured using a validated turbidimetric assay. Serum elements were quantified by inductively coupled plasma mass spectrometry (ICP-MS) and optical emission spectrometry (ICP-OES). Data were analyzed by bivariate correlations and multiple or logistic regression. Results-In female stroke patients, copper, lithium, and aluminum were significantly lower compared with controls; in male stroke patients, potassium was lower, and beryllium was elevated. In female and male stroke patients, iron, zinc, nickel, calcium, magnesium, sodium, and silicon were significantly lower, while strontium was elevated. Positive correlations between fibrin clot properties and metals, observed in healthy controls, were lost in ischemic stroke patients. In multivariate regression analysis, fibrin CLT and/or Absmax was associated with zinc, calcium, potassium, beryllium, and silicon in stroke patients and with sodium, potassium, beryllium, and aluminum in controls. In logistic regression analysis, stroke was independently associated with lithium, nickel, beryllium, strontium, boron, and silicon and with sodium, potassium, calcium, and aluminum but not with fibrin CLT/Absmax. Conclusions-Various elements were associated with fibrin clot properties and the risk of ischemic stroke. Lithium, sodium, calcium, and aluminum abrogated the association of fibrin clot properties with ischemic stroke.