A method for the analysis of methylmercury and total Hg in fungal matrices.

The aim of the study was to develop an efficient method for the determination of monomethyl-mercury (MeHg) and total mercury (THg) content in materials such as fungal sporocarps and sclerotia. Certified Reference Materials (CRMs) with the assigned values of MeHg and THg as well as the control materials (dried mushrooms) with known content of THg were evaluated for method validation. Recovery of MeHg from reference materials was at the following levels: from tuna fish at 87.0 ± 2.3% (THg at 101.9 ± 1.2%), from fish protein at 99.4 ± 1.3% (THg at 92.70 ± 0.41%), and from dogfish liver at 96.45 ± 0.73%. Recovery of THg from the fungal control material CS-M-5 was at 104.01 ± 0.60% (contribution of MeHg in THg content was at 6.2%), from CS-M-4 at 101.1 ± 2.0% (contribution at 3.2%), from CS-M-3 at 100.55 ± 0.67% (contribution at 0.6%), and from CS-M-2 at 101.5 ± 2.7% (contribution at 3.7%). The content of MeHg in randomly selected wild fungi and their morphological parts was in the range from 0.006 to 0.173 mg kg-1 dry weight (dw). In the case of THg, the concentration values were in the range from 0.0108 to 10.27 mg kg-1 dw. The MeHg content in the control materials with the assigned THg values was determined. Since the control materials play an important role in all elements of the quality assurance system of measurement results, they can be used to analyse MeHg as the first control material for fungi. KEY POINTS: • An extraction procedure for MeHg analysis in fungi was developed and optimized. • Recovery of MeHg from the certified reference non-fungal materials was > 87%. • Fungal control materials with assigned THg concentration can serve also for MeHg analysis.

Application of micellar electrokinetic chromatography for detection of silver nanoparticles released from wound dressing.

The recent emergence of nanotechnology has provided a new therapeutic modality in case of silver nanoparticles. Dressings containing silver form the basis for the treatment of burns and wounds, either acute or chronic ones. The aim of the study was to examine silver release from the different wound dressings: commercially available (Atrauman Ag, Aquacel Ag) and experimental (FKDP-AgNPs) using MEKC. In order to characterize prepared keratin based wound dressing before and after its modification with AgNPs, a compositional analysis was conducted using energy dispersive X-ray spectroscopy. Nanosilver toxicity was evaluated with the 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4 sulfophenyl)-2H-tetrazolium test. Silver release from wound dressings was assessed using MEKC. The best separation was observed for MEKC in 20 mM borate buffer at pH 9 with 20 mM SDS addition. In vitro studies showed silver at higher concentration than 10 ppm exerted a toxic effect on fibroblasts isolated from diabetic mice versus. NIH/3T3 and BJ cell lines (p < 0.05). We observed silver was released more gradually from experimental FKDP-AgNPs wound dressing, in compare to commercially available wound dressings. The fast and low-cost method utilizing MEKC can be used in clinical practice to detect silver release from the wound dressings.

A mixture of cellulose production waste with municipal sewage as new material for an ecological management of wastes.

Chemical contaminants present in cellulose production waste and municipal sewage sludge condition the necessity to treat these wastes before they are introduced into the environment. Environmental use of the these wastes appears to be justified owing to the content of organic substances as well as the considerable fertilising value. The aim of the study was to assess chemical composition and ecotoxicity of cellulose production waste and municipal sewage sludge in terms of their eco-friendly application. The assessment was done based on the established soil environment according to regulations in Poland. The research on the chemical composition of the wastes was conducted under laboratory conditions, determining the content of macroelements, microelements and heavy metals with respect to using these wastes in the environment. Phytotoxkit and Microtox tests were performed in order to determine the ecotoxicity of the wastes in the aspect of their environmental use. It was established that, compared to the cellulose production waste, the municipal sewage sludge used in the incubation experiment had a higher content of macroelements and microelements. The content of heavy metals in the waste did not exceed the permissible content that conditions their use in agriculture and reclamation. Based on the results of bioassays it was established that the cellulose production waste was toxic, whereas the combination of cellulose production waste and sewage sludge was found to be of low toxicity to test organisms. The applied wastes and their mixtures were ranked according to phytotoxicity in the following order: cellulose production waste > cellulose production waste + soil > cellulose production waste + sewage sludge. The research results indicate that waste mixtures qualify for environmental use. With respect to the variable chemical composition of cellulose production waste and municipal sewage sludge as well as their ecotoxicity, it was established that each batch intended for environmental use must be subjected to chemical analysis and ecotoxicological tests.

Organic Acids and Polyphenols Determination in Polish Wines by Ultrasound-Assisted Solvent Extraction of Porous Membrane-Packed Liquid Samples.

In the near future, Poland is going to have more and more favorable conditions for viticulture. Organic acids and polyphenols are among the most commonly analyzed compounds due to their beneficial properties for human health and their importance in the winemaking process. In this work, a new technique involving ultrasound-assisted solvent extraction of porous membrane-packed liquid samples (UASE-PMLS) was for the first time described and applied for real samples. The methodology based on UASE-PMLS for organic acids and polyphenols in wine samples was optimized and validated. Using the new technique coupled to GC-MS, organic acids and polyphenols were evaluated in Polish wine samples. Extraction solvent, extraction temperature, derivatization time and sample pH were optimized. Chemometric tools were used for data treatment. Good linearity was obtained for the concentration ranges evaluated with r values between 0.9852 and 0.9993. All parameters of method validation (intra- and inter-day precision and matrix effect) were over 80% with coefficient of variation (CV) up to 17%. Recovery was between (92.0 ± 8.5)% and (113 ± 16)%. Finally, green assessment was evaluated using Analytical Eco-Scale and Green Analytical Procedure Index (GAPI). The UASE-PMLS is characterized by many advantages, e.g., the extraction process is fast and easy coupled to GC-MS. Regarding other extraction techniques, the amount of used solvent is minimum, and no waste is generated. Therefore, it is an environmentally friendly technique.

Mercury concentration and the absolute and relative sizes of the internal organs in cormorants Phalacrocorax carbo (L. 1758) from the breeding colony by the Vistula Lagoon (Poland).

This work analyses the effect of mercury on the condition of cormorants (Phalacrocorax carbo) from an extensive breeding colony in northern Poland, the largest in Europe. A total of 55 birds (44 adults and 11 immature) were obtained. Total mercury (Hg) concentrations were measured in the liver, kidneys, breast muscles, heart, gullet (oesophagus), stomach, intestines, trachea, lungs and eyeballs. The total body mass (TBM) and empty body mass (EBM) were measured, and the body parts taken for analysis were weighed. The relative mass of the tissues and the L/K index were expressed as percentages. Based on the L/K index the birds were divided into three condition classes: (A) very good, (B) good and (C) moderate. The mean TBM and EBM in these cormorants were 2286 and 2184 g respectively. The greatest contributions to EBM were from the breast muscles (~11%), liver (3.7%) and intestines (3.0%). The stomach, gullet, lungs, heart and kidneys made up from ~1.0-2.8% EBM, and the trachea and eyeballs < 0.4%. 31 of the 55 birds analysed were allocated to class B; mean Hg levels in them were the highest in the kidneys, liver, lungs and muscles (18.3, 9.78, 2.70, 1.86 µg/g dw respectively); they were ≤ 1 µg/g in the other tissues. In ecotoxicology it is assumed that a hepatic concentration > 16.7 µg Hg/g dw can lead to adverse effects in the reproduction of non-marine birds. In the light of the present results, the reproductive parameters of the cormorants from the colony in northern Poland, though mostly in good or very good condition, may be depressed as a result of elevated Hg levels in their body tissues.

Comparison of Two Methods for the Determination of Selected Pesticides in Honey and Honeybee Samples.

Developed and validated analytical methods for the determination of a wide spectrum of pesticide residues in honey and honeybee samples after the modification of QuEChERS extraction in combination with gas chromatography⁻tandem quadrupole mass spectrometry (GC-MS/MS) and liquid chromatography⁻tandem quadrupole mass spectrometry (LC-MS/MS) were discussed and compared. The developed methods were evaluated regarding the utilized equipment and reagents using Eco-Scale and compared in terms of extraction time, accuracy, precision, sensitivity and versatility, with similar procedures. The results proved that the QuEChERS protocol in combination with LC and GC techniques fulfills the requirements of green analytical chemistry, so it can be used as a tool in environmental monitoring. The recovery was 85⁻116% for honey and 85.5⁻103.5% for honeybee samples. The developed methods were successfully applied in monitoring real samples collected from three districts of Pomerania in Poland. Analysis of real samples revealed the presence of the following pesticides: bifenthrin, fenpyroximate, methidathione, spinosad, thiamethoxam, triazophos, metconazole and cypermethrin at levels higher than the MRLs established by the EU.

Novel fast analytical method for indirect determination of MCPD fatty acid esters in edible oils and fats based on simultaneous extraction and derivatization.

A novel method for indirect determination of MCPD esters levels in lipid samples has been developed. The method is based on combination of extraction and derivatization in the same sample preparation step. It is achieved by the application of diethyl ether as extraction solvent for isolation of analytes released from esterified forms from the water phase and as dilution solvent for solid PBA - the derivatization agent. It is a noteworthy improvement of recommended indirect approaches available in the literature because such steps as sample clean-up, multiple liquid-liquid extractions, and preconcentration are excluded in the proposed solution. In this way, the developed procedure is shortened and simplified. Such an approach also minimizes the utilization of organic solvents; therefore, it is in accordance with the principles of "green analytical chemistry." In spite of the fact that the step of sample clean-up is omitted, no deterioration in GC-MS system performance was observed. Equivalence testing of the developed procedure and AOCS cd 29b-13 official method (SGS) has been conducted. It was concluded that results obtained by both methods do not significantly differ statistically. The procedure has been applied to determination of MCPD esters concentrations in lipid fractions isolated by accelerated solvent extraction technique from such foodstuffs as bakery products, salty deep-fried snacks, and instant products. In all investigated samples, the level of bound MCPD was elevated. Additionally, for both procedures, the environmental impact (with the use of analytical Eco-scale) and uncertainty budget have been assessed and compared.

Methods of Selenium Supplementation: Bioavailability and Determination of Selenium Compounds.

Selenium, a "dual-surface" element, maintains a very thin line between a level of necessity and harmfulness. Because of this, a deficiency or excess of this element in an organism is dangerous and causes health-related problems, both physically and mentally. The main source of selenium is a balanced diet, with a proper selection of meat and plant products. Meanwhile, the proper assimilation of selenium into these products depends on their bioavailability, bioaccessibility, and/or bioactivity of a given selenium compound. From the time when it was discovered that selenium and its compounds have a significant influence on metabolic processes and in many countries throughout the world, a low quantity of selenium was found in different parts of the environment, pressure was put upon an effective and fast method of supplementing the environment with the help of selenium. This work describes supplementation methods applied with the use of selenium, as well as new ideas for increasing the level of this element in various organisms. Based on the fact that selenium appears in the environment at trace levels, the determination of total amount of selenium or selenium speciation in a given sample demands the selection of appropriate measurement methods. These methods are most often comprised of a sample preparation technique and/or a separation technique as well as a detection system. The work presents information on the subject of analytical methods used for determining selenium and its compounds as well as examples in literature of their application.

Characteristics of odors emitted from municipal wastewater treatment plant and methods for their identification and deodorization techniques.

Odors emitted from municipal wastewater treatment plants belong to a group of pollutants, which is the main cause of people complaining about atmospheric air quality. The limitation of emissions of unpleasant odors generated by wastewater treatment plants by using appropriate deodorization methods is omitted on numerous occasions. This can have a negative influence on public trust and the quality of atmospheric air. The article presents basic information on the characteristics of odors from wastewater treatment lines and wastewater processing and management lines in a model biological wastewater treatment plant conducting the biogas recovery process and also information is provided on deodorization methods, such as odor masking, biofiltration, thermal disposal and diffusion through activated sludge dedicated to neutralization of odors in biological treatment plants. The main focus is on the field olfactometry technique, which is one of the tools used in environmental protection. Its application facilitates performance of tests concerning the assessment of olfactory properties of odorants in polluted air.

Exploration of optical fibres as a carrier for new benzene and toluene matrix-free reference materials.

To meet high expectations concerning precision and accuracy of reference materials, preparation of matrix-free reference materials using thermal decomposition-gas chromatography-mass spectrometry (TD-GC-MS) was proposed in this study. In the paper, the results obtained in preparation of the new reference materials for benzene and toluene are presented, based on the thermal decomposition technique of compounds chemically bound to the surface of optical fibre segments. The results obtained at various stages of the research procedure (homogeneity, stability) confirmed the possibility of using prepared laboratory samples of materials as reference materials for benzene and toluene. For the prepared batch of materials, reference values 1.26 ± 0.91 (ng/fibre) for benzene and 11.3 ± 7.4 (ng/fibre) for toluene were determined.

The influence of selenium addition during germination of Brassica seeds on health-promoting potential of sprouts.

The correlation among selenium uptake, the content of bioactive compounds in sprouts, and biological activities triggered in cultured human cells by sprout extracts was investigated. Seeds of Brassica crops and rye were treated with SeO2 water solution. The selenium levels in sprouts increased from 1.0-4.1 to 53.3-382 µg/g dw with no influence on plant physiology according to the indices used. Neither the composition of glucosinolates (GL) in Brassica sprouts nor the myrosinase activity nor the composition of GL breakdown lipophilic products were significantly affected. In all Brassica sprouts, conversion to health-promoting isothiocyanates (ITC) and indoles corresponded to only 1% of total GLs. Low ITC concentration may explain observed lack of induction of glutathione S-transferases (GST) and quinone oxidoreductase (NQO) detoxifying enzymes in HT29 cells exposed to sprout extracts. The insignificant impact on cell growth and genome function suggests that Brassica sprouts may be safe vehicle of selenium to combat its dietary deficiency.

Microextraction techniques used in the procedures for determining organomercury and organotin compounds in environmental samples.

Due to human activities, the concentrations of organometallic compounds in all parts of the environment have increased in recent decades. The toxicity and some biochemical properties of mercury and tin present in the environment depend on the concentration and chemical form of these two elements. The ever-increasing demand for determining compounds at very low concentration levels in samples with complex matrices requires the elimination of interfering substances, the reduction of the final extract volume, and analyte enrichment in order to employ a detection technique, which is characterised by high sensitivity at low limits of quantification. On the other hand, in accordance with current trends, the analytical procedures should aim at the miniaturisation and simplification of the sample preparation step. In the near future, more importance will be given to the fulfilment of the requirements of Green Chemistry and Green Analytical Chemistry in order to reduce the intensity of anthropogenic activities related to analytical laboratories. In this case, one can consider the use of solvent-free/solvent-less techniques for sample preparation and microextraction techniques, because the use of the latter leads to lowering the quantity of reagents used (including solvents) due to the reduction of the scale of analysis. This paper presents an overview of microextraction techniques (SPME and LPME) used in the procedures for determining different chemical forms of mercury and tin.

New matrix-free reference material for ethene in the form of optical fibres.

Reference materials are indispensable in the quality control and quality assurance of analytical measurements. One novel approach to the generation of standard gaseous mixtures of toxic, reactive, volatile, labile, and malodorous substances involves thermal decomposition or rearrangement, under defined temperature conditions, of compounds immobilized, by chemical bonding, on the surface of an appropriate carrier to release specific amounts of a volatile compound. In this technique the type of support used to immobilize the compound is extremely important, because the amount of analyte released depends directly on the choice of material. In this paper we report the novel preparation of a matrix-free ethene standard in the form of glass fibres coated with a thin layer of aluminium, the surface of which is modified by reaction with a specific compound. As a result of thermal decomposition of this compound, gaseous ethene is formed. In this paper we present the results obtained from tests of stability and homogeneity, two properties of crucial importance in the preparation of reference materials, by comparison of a series of results obtained for randomly chosen samples of the reference material. Interlaboratory comparative studies resulted in determination of a reference value for the ethene formed after thermal decomposition of the surface compound ((2.12 ± 0.14) ng per fibre).

The accessibility, necessity, and significance of certified reference materials for total selenium content and its species to improve food laboratories' performance.

Micronutrients are one of the most important groups of nutrients that our body needs daily in trace amounts to tackle deficiencies. Selenium (Se) is a mineral that occurs naturally in foods and is an essential component of selenoproteins that support the healthy functioning of the human body. Therefore, monitoring dietary Se concentrations must be a higher priority to meet daily intakes. Fulfillment can be addressed through applying various analytical techniques, and the certified reference materials (CRMs) tool plays a crucial role in quality assurance/quality control (QA/QC). The availability of certified CRMs for total Se content with addition to their species is presented. The review emphasizes the necessity of incorporating more food matrix CRMs certifying Se species, apart from total Se content, to meet method validation requirements for food analysis laboratories. This would help CRM producers bridge the gap between available food matrix materials that are not certified for Se species.

Estimation of smokers' exposure to mercury from combustible tobacco products, based on the approach used in food consumers' exposure estimation.

Smoking has been known to mankind for centuries, but it is only in recent decades that much attention has been paid to the harmfulness of this habit. Mercury inhalation is particularly dangerous in this respect and smoking creates extremely favorable conditions for the emission and targeted delivery of this element into the lungs. Despite this fact, a lack of a clear method for estimating the exposure of tobacco consumers to mercury was identified. This work shows justification to transfer the approach of estimating food product consumers' exposure to estimate the exposure of combustible tobacco product consumers to this element. In addition, it was noted that researchers' attention is mainly focused on cigarettes, while the tobacco market has a wide range of combustible products. Therefore, in this work, the mercury content of cigars (8.45 ± 0.18-41.02 ± 0.20 µg/kg), pipe tobaccos (8.03 ± 0.52-25.48 ± 0.50 µg/kg), bidis (14.93 ± 0.47-31.79 ± 0.26 µg/kg) and cigarette tobaccos (14.22 ± 0.71-34.5 ± 1.4 µg/kg) was analyzed. This study demonstrates that smoking can contribute significant total mercury exposure to consumers', although it is unlikely to cause mercury poisoning regardless of other exposure sources.

Evaluation of the Safety and Potential Benefits of Beetroot-Based Dietary Supplements According to Their Elemental Composition.

The study aimed to assess the health value and safety associated with the consumption of the chosen 37 beetroot-based dietary supplements (DSs). An optimized and validated analytical procedure, using a method called microwave plasma atomic emission spectrometry (MP-AES), was developed to determine the profiles of 19 elements (Na, K, Fe, Ca, Pt, Zn, Cd, Cu, V, Co, Ni, Pb, Mo, Mg, Al, Mn, Sr, Cr, Ba) in the DSs. The products were assessed for compliance with the recommended daily doses for the chosen elements, and any deviations were identified. Results showed that powders constituted a richer source of elements than capsules and tablets. The exception was iron-enriched products, which provided the highest dose of Fe (3.75 to 25 mg/daily dose). Safety assessment was evaluated in 3 steps, including (1) the determination of levels of Al, Ba, Cd, and Pb; (2) comparison of their content with the permissible contamination limits; and (3) comparison of the weekly or monthly intake of Al and Cd with the provisional tolerable weekly (PTWI) or monthly (PTMI) intake, respectively. The content of Ba was evaluated because of the oral reference dose (RfD). Five products were significantly contaminated with Cd (4-134% of PTMI Cd), two with Al (11-12%), and three with Ba (1.085-1.331 µg/d.d.). Lead was not detected above the LOQ (0.035 mg/kg). Factor analysis was employed to differentiate between the pharmaceutical forms (capsules, tablets, and powders) and determine the origin of the powder contained in the capsules. These results highlight the importance of implementing more stringent control measures and regulatory changes in the DSs market to ensure consumer safety.

The properties, functions, and use of selenium compounds in living organisms.

Selenium occurs in the environment in inorganic and organic compounds. For many years it was regarded as a toxic element, causing numerous illnesses and diseases. But research in the past 50 years has revealed a "bright side" to this element, especially as a component of selenoproteins, selenium makes a significant contribution to the health of humans and animals. The selenium content in an organism depends on its concentration and bioavailability in the soil, and the differences between its deficiency, appropriate intake, and excess are very slight. This article gathers information from the literature on: • the consequences of a deficiency and an excess of selenium in the body, as well as the health-promoting mechanisms of selenium, including the functions of selenoproteins • the uptake and transformation of selenium compounds by plants, because of the fact that selenium is better assimilated from plant food and also the classification of plants with respect to their ability to take up selenium from the soil and to accumulate it.

Mercury in different feather types from Great Cormorants (Phalacrocorax carbo L.) inhabiting the Vistula Lagoon ecosystem in Poland.

Total mercury levels in different feather types (down, contour, tail and flight) in Great Cormorants (Phalacrocorax carbo L.) were determined using CV-AAS. Feathers from Great Cormorants inhabiting the Vistula Lagoon ecosystem have an average Hg level of 7.14 ± 3.99 (µg/g w.w.). Age-dependent concentrations of Hg were statistically significant (ANOVA Kruskal-Wallis, p < 0.0001). There were also significant differences in Hg levels in different parts of feathers from adults and immature birds (ANOVA Kruskal-Wallis, p < 0.0001). Cormorant chick feathers appear to be a potential biomonitor of Hg pollution in the Vistula Lagoon ecosystem, but this subject requires further research.

Review of cigars and cigar-type products as potential sources of consumer exposure to heavy metals.

The popularity of cigars, growing since 1993, has not gone hand in hand with the increased interest of researchers in these products. Although the literature widely describes the harmfulness of tobacco and the content of toxic substances in tobacco products, the topic is often treated selectively as relating primarily to cigarettes and rarely extends to other products of the broadly defined tobacco industry. However, there is no reason to marginalize the harmful effects of other nicotine products, (which include tobacco products such as cigars). The study analyzed the available literature on the content of selected heavy metals in cigar tobacco. Among the heavy metals, the following contents of elements in tobacco were recorded in cigars: Fe (420-2200 µg/g), Mn (100-370 µg/g), Zn (14-180 µg/g), Cu (15-140 µg/g), Pb (not detected-32 µg/g), Cd (nd-19 µg/g), Ni (nd-13 µg/g), Cr (nd-10 µg/g), Co (0.65-1.0 µg/g), As (nd-0.66 µg/g), Hg (18-25 ng/g). Importantly, the values often differ between cigars of different origins and types, indicating the need for more extensive research.