Temporal arsenic form changes dynamics and accumulation patterns in Tilia cordata Mill. seedlings: Insights into metalloid transformation and tolerance mechanisms in trees.

Arsenic (As) remediation is challenging due to the complex nature and the persistence of these metalloid compounds. While it may seem that differences between As forms influence have been extensively described, new findings challenge the previously accepted knowledge, particularly for woody plants. Therefore, this study focused on 2-year-old Tilia cordata Mill. seedlings early (0, 2, 4, 12, 24 h) and late (3, 7, 12, 18, 25, 33 days) responses during growth under: As(III), As(V) or dimethylarsinic acid (DMA) (0.3 mM). Time-dependent transformations of As forms, distribution in plants, and microbiological characteristics (actinobacteria, bacteria, fungi, enzyme activity) were investigated. The highest increase in total As content was observed in plants exposed to As(V) and As(III). Dynamic metalloid form changes in the solution and tree organs were indicated. The most phytotoxic was DMA. This form was the main factor limiting the growth and effective accumulation of As. Despite experimenting in hydroponics, microorganisms played an important role in As form transformations, suggesting the potential for microbial-assisted dendroremediation strategies. The study confirmed that trees can convert more toxic forms into less toxic ones (e.g. As(III) to phytochelatins - As(III)-(PC3)), whose presence in roots seedlings exposed to As(III) and As(V) has been identified. The formation of hydrophobic forms (e.g. dimethylarsinoyl lipid) in the roots of seedlings grown under As(V) was confirmed. It is the first discovery for trees, previously observed only in bacteria and algae. The dynamics of metalloid form changes indicated that T. cordata transforms As forms according to their needs, which may give tree species an advantage in phytoremediation techniques. It holds great promise for the potential of dendroremediation.

Leaves, Infusion, and Grounds-A Three-Stage Assessment of Element Content in Yerba Mate (Ilex paraguariensis) Based on the Dynamic Extraction and Mineralization of Residues.

The more yerba mate infusions that are consumed, the larger the amount of grounds generated. What is more, both the infusion and the residues after brewing remain rich elements. Therefore, a strategy for the three-stage assessment of the element content was presented. A new brewing method was based on dynamic extraction, ensuring both the ease of preparing the infusion and recovering the grounds. In turn, microwave-assisted acid mineralization was used to decompose the leaves and twigs of yerba mate before and after brewing. In total, 30 products were analyzed by ICP OES in three fractions each, i.e., dry yerba mate, infusion, and grounds, to determine up to 25 elements. The elemental composition was considered in terms of the country of origin, type, or composition of yerba mate. The extraction percentages obtained with dynamic extraction were comparable to previously used ultrasound-assisted extraction, as well as data from the literature. The three-stage strategy is a novel approach in yerba mate studies, and it may be a model procedure for the laboratory preparation of yerba mate grounds (waste that can be re-used, e.g., a natural fertilizer).

Chemical element distribution in Arctic soils: Assessing vertical, spatial, animal and anthropogenic influences in Elsa and Ebba Valleys, Spitsbergen, Svalbard.

The Arctic region is threatened by climate change and pollution caused by human activities which potentially influence the elemental concentrations available to and from the biota. To better understand this delicate balance, it is crucial to investigate the role of several factors. Therefore, we quantified the level of 43 chemical elements in soils from Elsa and Ebba Valleys, Petunia Bay, Spitsbergen, a region that has experienced lasting environmental impacts from historical mining activities. We evaluated the a) vertical sampling influence by examining the variation in element distribution between the soil upper and deeper layers, b) animal influence by verifying the role of native animals, particularly vertebrates, in introducing thought faeces elements to the soil and c) anthropogenic influence by studying the spatial geographical differences in element distribution based on the degree of human pressure between the valleys. Our analysis also includes data on soil organic matter (SOM) and mineral composition. Both valleys exhibited similar mineralogical composition, but Elsa Valley had higher concentrations of most analyzed elements compared to Ebba Valley. Despite the contribution of vertebrate feaces, no increase in element concentrations was observed in the animal-influenced soils. The sampled soil layers had similar chemical element profiles for most elements. SOM content tended to be higher in superficial soils and showed a strong positive correlation with most quantified elements. The higher concentrations in Elsa Valley reflect its past mining and mineral exploration, making this area more significantly impacted than Ebba Valley. Surprisingly, vertebrate animals do not appear to influence the concentrations of chemical elements or organic matter in soils. Our findings provide valuable insights into the legacy of past mining activities and mechanisms driving environmental change in the Arctic.

A Fast and Efficient Procedure of Iron Species Determination Based on HPLC with a Short Column and Detection in High Resolution ICP OES.

The optimization and application of a new hyphenated procedure for iron ionic speciation, i.e., high performance liquid chromatography (HPLC) with short cation-exchange column (50 mm × 4 mm) coupled to high resolution inductively coupled plasma optical emission spectrometry (ICP hrOES), is presented in this paper. Fe(III) and Fe(II) species were separated on the column with the mobile phase containing pyridine-2,6-dicarboxylic acid (PDCA). The total time of the analysis was approx. 5 min, with a significantly low eluent flow rate (0.5 mL min-1) compared to the literature. Additionally, a long cation-exchange column (250 mm × 4.0 mm) was used as reference. Depending on the total iron content in the sample, two plasma views were chosen, e.g., an attenuated axial (<2 g kg-1) and an attenuated radial. The standard addition method was performed for the method's accuracy studies, and the applicability was presented on three types of samples: sediments, soils, and archaeological pottery. This study introduces a fast, efficient, and green method for leachable iron speciation in both geological and pottery samples.

Influence of Brewing Method on the Content of Selected Elements in Yerba Mate (Ilex paraguarensis) Infusions.

In this paper, the effect of the extraction method on the concentrations of selected elements in yerba mate (Ilex paraguariensis) infusions is presented. Seven pure yerba mate samples (without additives) were selected, representing various types and countries of origin. An extensive sample preparation procedure was proposed: ultrasound-assisted extraction using two types of extractants (deionized and tap water) at two different temperatures (room and 80 °C). In parallel, the above extractants and temperatures were carried out for all samples by the classical brewing method (without ultrasound). In addition, microwave-assisted acid mineralization was carried out to determine the total content. All the proposed procedures were thoroughly investigated with certified reference material (tea leaves, INCT-TL-1). For the total content of all the determined elements, acceptable recoveries (80-116%) were obtained. All digests and extracts were analyzed by simultaneous ICP OES. For the first time, it was assessed how tap water extraction affects the percentage of extracted element concentrations.

Digestibility of Protein and Iron Availability from Enriched Legume Sprouts.

Plant ferritin is suggested as a good source of iron for human. Usually present in trace amounts, it was induced in legumes seeds by their sprouting in FeSO4 solution. Fortified sprouts were digested in the in vitro model of the human gastrointestinal tract. ~49% of lupine and ~ 45% of soy proteins were extracted into gastric fluid and next ~ 12% and only ~ 1% into intestine fluid from lupine and soybean, respectively. Gastric digestion released mainly ferrous iron (~ 85% from lupine and ~ 95% in soybean sprouts). Complexed iron constituted ~ 43% of total iron in intestine after lupine digestion and ~ 55% after soybean digestion. Intestine digestion doubled the total iron released from lupine sprouts (from ~ 21% up to 38%), while in soybean it increased from ~ 16% up to ~ 23%. Ferritin presence was confirmed by the specific antibodies in digestive fluids, but it is only partially extracted from sprouts during in vitro digestion.

Copper, lead and zinc interactions during phytoextraction using Acer platanoides L.-a pot trial.

Of the many environmental factors that modulate the phytoextraction of elements, little has been learnt about the role of metal interactions. The study aimed to show how different concentrations of Cu, Pb and Zn in the cultivation medium influenced the biomass, plant development and phytoextraction abilities of Acer platanoides L. seedlings. Additionally, the impact on the content and distribution of Ca, K, Mg and Na in plant parts was studied with an analysis of phenols. Plants treated with a mixture of two metals were characterised by lower biomass of leaves and higher major elements content jointly than those grown in the salt of one element. Leaves of A. platanoides cultivated in Pb5 + Zn1, Pb1 + Zn1 and Pb1 + Zn5 experimental systems were characterised by specific browning of their edges. The obtained results suggest higher toxicity to leaves of Pb and Zn present simultaneously in Knop solution than Cu and Pb or Cu and Zn, irrespective of the mutual ratio of the concentrations of these elements. Antagonism of Cu and Zn concerning Pb was clearly shown in whole plant biomass when one of these elements was in higher concentration (5 mmol L-1) in solution. In the lowest concentrations (1 mmol L-1), there was a synergism between Cu and Zn in plant roots. Plants exposed to Zn5, Cu1 + Pb5, Pb5 + Zn1 and Cu1 + Zn1 were characterised by higher total phenolic content than the rest plants. Both the presence and the concentration of other elements in the soil are significant factors that modulate element uptake, total phenolic content, and plant development.

FTIR as a Method for Qualitative Assessment of Solid Samples in Geochemical Research: A Review.

This study aims to collect information about soil investigation by FTIR. As we know, the FTIR technique is most often used in organic and bioorganic chemistry, while in geochemistry FTIR spectroscopy is not used very often. Therefore, there is a problem with the identification and interpretation of the IR spectra of minerals contained in sediments and soils. The reason for this is a deficiency of data about characteristic wavenumbers for minerals. Therefore, this study reviews and sums up, in one place, published articles that are connected to an investigation of minerals from 2002 to 2021 (based on the Scopus database). Additionally, the present review highlights various analytical techniques (ATR-FTIR, DRIFT, 2D-IR, and SR-FTIR) and discusses some of them for geochemical study. Additionally, the study describes helpful tools in the data pre-processing of IR spectra (normalization, baseline correction, and spectral derivatives).

Mycoremediation of Flotation Tailings with Agaricus bisporus.

Due to their enzymatic and bioaccumulation faculties the use of macromycetes for the decontamination of polluted matrices seems reasonable for bioremediation. For this reason, the aim of our study was to evaluate the mycoremediation ability of Agaricus bisporus cultivated on compost mixed with flotation tailings in different quantities (1, 5, 10, 15, and 20% addition). The biomass of the fruit bodies and the content of 51 major and trace elements were determined. Cultivation of A. bisporus in compost moderately polluted with flotation tailings yielded significantly lower (the first flush) and higher (the second flush) biomass of fruit bodies, compared with the control treatment. The presence of toxic trace elements did not cause any visible adverse symptoms for A. bisporus. Increasing the addition of flotation tailings to the compost induced an elevated level of most determined elements. A significant increase in rare earth elements (both flushes) and platinum group elements (first flush only) was observed. The opposite situation was recorded for major essential elements, except for Na and Mg in A. bisporus from the second flush under the most enriched compost (20%). Nevertheless, calculated bioaccumulation factor values showed a selective accumulation capacity-limited for toxic elements (except for Ag, As, and Cd) and the effective accumulation of B, Cu, K, and Se. The obtained results confirmed that A. bisporus can be used for practical application in mycoremediation in the industry although this must be preceded by larger-scale tests. This application seems to be the most favorable for media contaminated with selected elements, whose absorption by fruiting bodies is the most efficient.

Spatial heterogeneity of chemistry of the Small Aral Sea and the Syr Darya River and its impact on plankton communities.

The shrinking of the Aral Sea represents one of the greatest ecological disasters of modern time. The data on the surviving northern part (Small Aral) is scarce and requires an update. This study aimed to analyze the chemistry, phyto- and zooplankton composition, and their relation in the waters of the Small Aral and its tributary, Syr Darya River. The chemistry of both ecosystems was significantly different. Small Aral was characterized by higher ionic concentrations, salinity, and electric conductivity and more significant spatial variation of chemical properties. The area near the river mouth was more pristine, while the ions concentration and salinity in the distant bays were much higher (>10‰). The highest concentrations of nitrates and total phosphorus in the Syr Darya were observed near Kyzylorda, indicating urban pollution. Overall, 109 phytoplankton taxa were identified in both ecosystems, with diatoms, green algae, and cyanobacteria being most abundantly represented. Oligohalobes dominated, but no polyhalobes and euhalobes algal species were identified. In total, 27 taxa of zooplankton were identified in both studied ecosystems, with the domination of rotifers over microcrustaceans. An exceptionally high level of dominance (65-91%) of rotifer Keratella cochlearis in the Syr Darya was found. The phyto- and zooplankton species richness was higher in the Syr Darya. Plankton communities of the Small Aral reflected horizontal variability of chemical properties. The total phosphorus promoted the prevalence of diatoms, rotifers, and crustaceans. Increased nitrogen concentration promoted cyanobacteria, chlorophytes, cryptophytes and chrysophytes, and rotifers Keratella cochlearis and K. quadrata. The abundance of dinophytes, diatoms Navicula cryptotenella and Cocconeis placentula, green algae Mychonastes jurisii and rotifer Keratella tecta was driven by the higher alkalinity and conductivity/salinity levels. The results represent a reference point for future monitoring of the area and add to understanding the complexity of biological transformations in the Aral Sea and its tributary.

Environmental and Anthropogenic Factors Shape the Snow Microbiome and Antibiotic Resistome.

Winter tourism can generate environmental pollution and affect microbial ecology in mountain ecosystems. This could stimulate the development of antibiotic resistance in snow and its dissemination through the atmosphere and through snow melting. Despite these potential impacts, the effect of winter tourism on the snow antibiotic resistome remains to be elucidated. In this study, snow samples subjected to different levels of anthropogenic activities and surrounding forest were obtained from the Sudety Mountains in Poland to evaluate the impact of winter tourism on snow bacteria using a metagenomic approach. Bacterial community composition was determined by the sequencing of the V3-V4 hypervariable region of the 16S rRNA gene and the composition of the antibiotic resistome was explored by metagenomic sequencing. Whereas environmental factors were the main drivers of bacterial community and antibiotic resistome composition in snow, winter tourism affected resistome composition in sites with similar environmental conditions. Several antibiotic resistance genes (ARGs) showed a higher abundance in sites subjected to human activities. This is the first study to show that anthropogenic activities may influence the antibiotic resistome in alpine snow. Our results highlight the need to survey antibiotic resistance development in anthropogenically polluted sites.

Controls on coastal flooding in the southern Baltic Sea revealed from the late Holocene sedimentary records.

Climate change and related sea-level rise pose significant threats to lowland coasts. However, the role of key controlling factors responsible for the frequency and landward extent of extreme storm surges is not yet fully understood. Here, we present a high-resolution sedimentary record of extreme storm surge flooding from the non-tidal southern Baltic Sea, spanning two periods: 3.6-2.9 ka BP and 0.7 ka BP until present. Sediments from coastal wetland, including sandy event layers, were analyzed by sedimentological (grain size, loss-on-ignition, micromorphology), geochronological (14C), geochemical (XRF), mineralogical (heavy minerals) and micropaleontological (diatoms) methods. The results show that both periods were characterized by high-frequency of storm surge flooding, in order of 1.3-4.2 events per century. These periods correlate with phases of enhanced storminess in northwest Europe and took place during both rising and fluctuating sea levels. The study shows that the frequency and landward extent of coastal inundation, largely depended on the development of natural barriers (e.g. beach ridges and aeolian foredunes). Thus, in the context of the future coastal storm-surge hazard, the protection of existing coastal barriers and their morphology is essential.

Road traffic and abiotic parameters of underlying soils determine the mineral composition and nutritive value of the mushroom Macrolepiota procera (Scop.) Singer.

The effectiveness of accumulating mineral elements by wild-growing mushrooms depends mainly on species, their growth place, and the underlying soil's chemical characteristics. The aim of the study was to determine the effect of road traffic and the role of chemical characteristics of soil on the mineral composition of Macrolepiota procera fruit bodies growing in close proximity to a road and an adjacent forest during a four-year period. The concentrations of the majority elements (mainly Al, Cd, Co, Cr, Cu, Pb, Ti, and Zn) in the soil near the road were significantly higher than those in the forest soil, which was reflected in the fruit bodies which contained a higher amount of these elements. While the accumulation of heavy metals and other elements in the M. procera fruit bodies did not depend on the total soil organic carbon content, the degree of their decomposition determined by the C:N ratio and the individual fractions of organic carbon had a significant influence. Our studies show that soil properties are highly variable in the natural habitats of M. procera, which affects the efficiency of element accumulation. Macrolepiota procera fruit bodies growing in soil with similar chemical properties were characterized by different mineral compositions. Moreover, the obtained results indicate that the fruit bodies of edible M. procera, not only those close to roads but also at a greater distance, may contain significant amounts of toxic As and Cd, which could pose a health risk if consumed. Although most studies describing the mineral composition of M. procera fruit bodies have found no evidence to question the safety of their consumption, this species can effectively accumulate selected elements when growing immediately beside roads or in their close proximity.

The impact of iron coagulant on the behavior and biochemistry of freshwater mussels Anodonta cygnea and Unio tumidus during lake restoration.

Iron (Fe) treatment is one of the most commonly used methods to restore eutrophic lakes and reservoirs. The Fe-based coagulants dosage results in an almost immediate improvement in water quality at a relatively low cost. However, the effects of the application of coagulants are not always predictable, and the scale of the risks is not fully understood. The dosage of coagulants changes the chemical and physical properties of water, thereby affecting aquatic biocenoses. In this study, several laboratory experiments were conducted to evaluate the effects of Fe-based coagulant dosage on two bivalves species: Anodonta anatina and Unio tumidus. Their ability to efficiently filter water and reduce seston makes them a key component of aquatic ecosystems in terms of maintaining proper ecological health and stable functioning. Behavioral response, biochemical parameters, and body chemistry changes in mussels exposed to different doses of coagulant were surveyed. A dose-dependent reduction in filtration activity of both species was observed. As early as 10 g Fe m2 (which is a moderate dose used in lakes restoration), mussels of both species almost completely reduced their filtration activity and remained with closed valves for several subsequent days. Significant Fe accumulation in muscles of bivalves exposed to coagulant was also observed. This was particularly the case when very high doses of coagulant were applied. Then, the iron content in leg muscles of both species increased over fourfold. At the same time, a decrease in muscles calcium and phosphorus content was observed. No symptoms of oxidative stress (TBARS, H2O2) after mussels exposure to coagulants were found. The results suggest that the application of Fe-based coagulant for water ecosystem restoration may be a threat to the mussels population. These findings are significant for decisions on the selection of restoration methods for a specific lake.

Biofortification of Three Cultivated Mushroom Species with Three Iron Salts-Potential for a New Iron-Rich Superfood.

Mushrooms fortified with iron (Fe) can offer a promising alternative to counter the worldwide deficiency problem. However, the factors that may influence the efficiency of fortification have not yet been fully investigated. The aim of this study was to compare the effects of three Fe forms (FeCl3 6H2O, FeSO4 7H2O, or FeHBED) in three concentrations (5, 10, or 50 mM) for three mushroom species (Pleurotus eryngii, P. ostreatus, or Pholiota nameko) on their chemical composition, phenolic compounds, and organic acid production. The most effective metal accumulation of all the investigated species was for the 50 mM addition. FeCl3 6H2O was the most favorable additive for P. eryngii and P. nameko (up to 145 and 185% Fe more than in the control, respectively) and FeHBED for P. ostreatus (up to 108% Fe more than in control). Additionally, P. nameko showed the highest Fe accumulation among studied species (89.2 ± 7.51 mg kg-1 DW). The creation of phenolic acids was generally inhibited by Fe salt supplementation. However, an increasing effect on phenolic acid concentration was observed for P. ostreatus cultivated at 5 mM FeCl3 6H2O and for P. eryngii cultivated at 5 mM FeCl3 6H2O and 5 mM FeSO4 7H2O. In the case of organic acids, a similar situation was observed. For P. ostreatus, FeSO4 7H2O and FeHBED salts increased the formation of the determined organic acids in fruiting bodies. P. eryngii and P. nameko were characterized by a much lower content of organic acids in the systems supplemented with Fe. Based on the obtained results, we recommend starting fortification by preliminarily indicating which form of the element is preferred for the species of interest for supplementation. It also seems that using an additive concentration of 50 mM or higher is most effective.

Recent applications of continuous flow chemical vapor and hydride generation (CVG, HG) coupled to plasma-based optical emission spectrometry (ICP OES, MIP OES).

Chemical vapor or hydride generation (CVG/HG) still plays a significant role in continuous flow sample introduction system. The development and higher accessibility of new commercial CVG/HG accessories (especially modified spray chambers and nebulizers) improves the analytical possibilities of plasma-based optical emission spectrometry for determination of hydride forming analytes. These systems are still designed and widely applied despite the better availability of its alternatives. The commercialization of the first nitrogen microwave induced plasma optical emission spectrometry instrument (MIP OES) also contributes to the increase in popularity of these solutions. The latest achievements in commercial and laboratory-made generators and instruments, as well as new strategies in sample preparation for total content and speciation analysis, are discussed in the review.

Chronic Alcohol Abuse Alters Hepatic Trace Element Concentrations-Metallomic Study of Hepatic Elemental Composition by Means of ICP-OES.

Trace element accumulation varies in different human tissues. Distribution of several elements was found to be disrupted in the case of excessive alcohol consumption, causing negative effects and exacerbation of pathological processes in the liver. In this study, we analyzed the levels and interactions between seven trace elements including calcium (Ca), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), potassium (K), and magnesium (Mg), manganese (Mn), sodium (Na), zinc (Zn), and selenium (Se) in individuals with alcohol-use disorder (AUD) and patients without AUD (control group). The liver samples were collected during autopsy from 39 individuals with AUD and 45 control subjects. Elemental composition inductively coupled plasma optical emission spectrometry (ICP-OES) after wet mineralization by nitric acid was applied for the evaluation of the samples. Positive correlations dominated in the AUD group, mainly in relation to Mg, which strongly positively correlated with Ca, Mn, Fe; K correlated with Mn and Zn, and Cu positively correlated with K and Zn. The strongest positive correlation in the AUD group was observed for the Mg-Mn pair (r = 0.87). Significant statistical differences (p < 0.05) between the groups concerned the average concentration of Co, Cu, Mn, and Mg, which were lower in the AUD group, and Fe, the level of which was significantly higher in the AUD group compared to the control group. Evaluation of the chronic alcohol consumption effect on the accumulation of trace elements in the liver allows a better understanding of the pathological processes taking place in this organ.