Speciation Of Trace Elements Research Articles

Chemical speciation of essential trace elements in edible bamboo shoots from different varieties and sampling locations by HPLC – ICP-MS and HPLC - electrospray MS/MS

Samples of five different commonly consumed bamboo species collected at five different locations in the State of Manipur, northeast India, were investigated for the concentrations and, for the first time, for the chemical forms of essential trace elements. Several elements were determined in the bamboo shoots of which Fe, Zn, Cu, Mn, and Ni were present above the 1 ppm level in bamboo juice. An analysis of data for the variability using the ANOVA method, indicated no statistically significant effect of the geographical location on the trace element pattern and speciation. However, nickel and, to lesser extent, zinc concentrations and speciation were affected by the bamboo variety. Speciation revealed the presence of metal complexes with nicotianamine (NA), deoxymugineic acid (DMA) and histidine.

Impact of sediment mobilization on trace elements release in Galician Rías (NW Iberian Peninsula): insights into aquaculture

In the latest years, the concentration levels of certain metals and metalloids in the sediments of the Galician Rías have shown an increasing trend (e.g., As, Zn, Cu, Pb, Hg). These areas are also characterized by their richness in nutrients and their great aquaculture or mariculture activity, with the presence of more than 3500 mussel rafts in the Rías Baixas. The inner areas of the Galician Rías are subjected to activities that resuspend the sediment such as high levels of maritime traffic and dredging or cleaning operations. It is likely that a transfer of these elements to the water column happens during the resuspension of sediments caused by natural events or anthropogenic activities. In this study, selected samples of surface sediments of the Ría de Pontevedra (NW Spain) were subjected to a procedure of aerobic oxidation to determine the concentration of some elements (Fe, Mn, Cu, Cr, Pb, Hg, and Zn) released from the sediment to the aqueous phase. The experiment was carried out within 5 days. Measurements of pH and total concentration were taken both in water and sediment samples. Furthermore, speciation of trace elements was carried out in the sediment samples. Trace element concentrations were lower in the sediments during aerobic oxidation, being released to the aqueous phase. From an environmental point of view, Cu was the only trace element released in quantities that may be toxic for the organisms in the area. This problem of sediment oxidation related to dredging activities or natural storm conditions should be considered in environmental impact studies and transferred to stakeholders.

Mobility of Trace Elements During Remediation of Oil Polluted Groundwater: A Case Study of Al Batinah Region, Northeast Oman

A study was carried on an area polluted by oil in Oman to determine the mobility of trace elements during each step of an ex-situ treatment process. Quality of groundwater following an air flotation treatment was investigated and discussed. About 15 water samples were collected from 7 monitoring wells which are under air sparging treatment for remediation of oil contamination in Al Batinah region (Northeast of Oman). Chemical composition of groundwater during and after the treatment was compared with chemical composition of groundwater before any treatment. Water samples were also collected from different monitoring wells in the same area. The investigated elements consist in Na, Mg, Ca, K, Fe, Cr, Ni, Cu, Zn, Ag, Cd, Sr, Ba, Pb and rare earth elements (REEs). Chemical composition of trace and major elements during each step of treatment revealed that Ni, Zn, Cu and Al have been increased relative to untreated water contrary to Ag which decreased. Major elements and Cr, Pb, and Cd remain unchanged during the treatment process. The REEs were significantly depleted during the last step of treatment relative to the raw water but their distribution did not reveal any fractionation. Trace elements such as Zn, Cu, Ni show an increase and Ag and REES a decrease relative to raw water before any treatment. For treatment of groundwater, chemical investigation of different agents used during the treatment and the speciation of each key trace elements should be investigated at each step of treatment procedure.

Identification of solid phase speciation of trace elements in dust dry deposition using focused ion beam and selected area electron diffraction

BackgroundFew studies have been conducted to identify solid phase speciation of trace elements within the interior of airborne particles, although the adverse effects of ambient particles are closely related to the speciation of toxic elements and therefore the identification of chemical binding sites and solid phase associations is essential for assessing the impacts of trace elements in ambient air on environmental quality and human health. ObjectiveA combined use of focused ion beam scanning electron microscopy (FIB-SEM) and selected area electron diffraction (SAED) patterns from transmission electron microscopy (TEM) was applied with an energy dispersive X-ray spectroscopy (EDS) to investigate the solid phase speciation of trace elements within the interior of dust dry deposition obtained from an urban area. ResultsThe study results using the high-resolution microscopic techniques for the characterization of nano- and micron-sized particles revealed lead chromate for Pb and Cr6+, barite for Ba, rutile for Ti, and calcite, gypsum, and quicklime for Ca within the carbon matrix, implying their traffic-related sources. Fe oxides were observed for Fe, Mn, Ni, and Cr3+, with cerianite and Fe-La alloys for rare earth elements (REEs). ConclusionsThree types of anthropogenic sources were inferred based on the morphology and texture of the solid phases, as well as their primary usage: traffic road marking paints for Pb, Cr6+, Ba, and Ti, cement materials for Ca, and industrial activities for Fe, Mn, Ni, Cr3+, and REEs. The presence of submicron-sized toxic metal-bearing particles in dust dry deposition indicated that the toxic metals (i.e., Pb, Cr6+) can penetrate into the respiratory system along with the nanoparticles. The study results demonstrate that the solid phase speciation of trace elements detected using FIB-SEM and TEM-SAED can be effectively utilized for the identification of sources and the assessment of chemical toxicity of atmospheric dust.

Chemometric Speciation of Trace Elements in Indonesian Coal Imported by Indian Thermal Power Stations - A Comparative Study with Indian Coals using SRXRF

ABSTRACT Imported Indonesian coal samples collected from thermal power plants were analyzed using Synchrotron Radiation X-ray Fluorescence (SRXRF). Sixteen inorganic elements As, Ca, Cr, Co, Cu, Fe, K, Mn, Ni, Pb, Rb, Se, Sr, Ti, V, and Zn were quantified. To ascertain the abundance in the analyzed samples compared to Clarke values for world coals, the enrichment factor for each element was measured. The analytical results were interpreted using chemometric techniques, namely Pearson’s correlation analysis, hierarchical cluster analysis, and principal component analysis. This study revealed three principal components contributing to 87.99% of the total variance in the data.

Chemical Speciation, Leaching Behavior, and Environmental Risk Assessment of Trace Elements in the Bottom Ash from Biomass Power Plant.

Biomass combustion for power generation stands as a pivotal method in energy utilization, offering a promising approach for renewable energy utilization. However, the substantial volume of slag produced by biomass burning plants poses environmental challenges, impeding sustainable energy practices. This article systematically studies the characteristics of ash generated from typical biomass direct combustion power plant ash and analyzes the chemical composition, trace element content characteristics, leaching characteristics, and chemical forms of biomass bottom ash. Furthermore, it assesses the environmental ecology and bioavailability of trace elements in bottom ash using the ecological risk assessment method and RAC method. The results demonstrate that the biomass bottom ash contains plant nutrients, such as K, Ca, Mg, and P, while the content of harmful trace elements is lower than the relevant Chinese standards. In dissolution experiments, the leaching rate of nearly all elements remains exceptionally low, primarily due to the distribution of trace elements within the lattice structure of stable minerals. Trace elements predominantly exist in the residual phase, Cu and Zn primarily found in organic compounds and sulfide bound states, while other elements mostly exist in the form of iron manganese oxide bound states. Ecological risk assessment indicates a significant risk level for Cd, contrasting with the slight risk associated with other elements. RAC results indicated no ecological risk of all of the trace elements. Consequently, the utilization of bottom ash in agricultural and forestry soils is deemed to be viable. These findings serve as a crucial foundation for biomass bottom ash resource utilization and underpin the sustainable utilization of biomass energy.

Carbon sequestration through mineral carbonation: Using commercial FGD-gypsum from a copper smelter for sustainable waste management and environmental impact mitigation

In this study, we conducted a comprehensive examination of a commercial FGD gypsum produced in a Copper (Cu) smelter process and delved into its potential use as a Calcium (Ca)-rich material for ex-situ mineral carbonation by exploring the partitioning and fate of these metal impurities. The resulting carbonation end-product displayed a calcium carbonate (CaCO3) content of 71.1%, featuring a relatively low CO2 conversion, which may be attributed to the presence of metallic impurities in the commercial FGD-gypsum. Most of these metallic impurities, acting as inputs to the carbonation process, originate from the parent FGD-gypsum matrix. This results in an increased ionic strength within the FGD gypsum, potentially impeding the diffusion of carbon dioxide (CO2) from the gas phase to the aqueous phase. The partitioning and examination of the speciation of major, minor, and trace elements at all stages of CO2 conversion allowed us to propose four potential reaction pathways influencing carbonation efficiency: (i) the formation of metal carbonates, (ii) the production of metal oxides and oxyhydroxides, (iii) the development of metal multiform compounds, and (iv) elements deviating from the outlined patterns. Commercial FGD-gypsum is suitable for acceptance at non-hazardous waste landfills. However, it's essential to highlight that leaching values of As exceed the inert range and non-hazardous waste standards in commercial FGD-gypsum. Although most heavy metal leaching values from the carbonate end-product stay below non-hazardous limits, the release of some heavy metal leachates from the carbonate end-product may limit reuse options for these materials.

Size-resolved distribution of trace elements in lysimeter soil solutions under contrasting long-term agricultural management to assess their bioavailability

The chemical species of trace elements (TEs) in agricultural soils is highly variable under diverse conditions, requiring tools with clear resolution and minimal disturbance for exploration. A novel surgical (316L) stainless steel (SS) lysimeter with a 5 μm pore size was developed to collect field soil solutions. The size-resolved distribution of TEs were characterized into total (nitric acid digestion), particulate (0.45–5 μm), dissolved (<0.45 μm), colloidal (1 kDa to 0.45 μm), and mainly ionic (<1 kDa) fractions in the lysimeter soil solutions. Total concentrations of TEs (dry weight basis) in acid digested Gray Luvisolic soils were analyzed. Most TEs in lysimeter soil solutions were present in particulate phases, relevant to their geochemical affinities and occurrences in soil minerals. Among dissolved fractions, As, Ba, Co, Li, Mn, Tl, and V existed as mainly ionic species in the soil solutions. Copper, Pb, Al, Th, and U showed variable associations with dissolved organic matter (DOM) and/or inorganic colloids among agricultural treatments. Inorganic NPKS or NKS fertilizer applications with lower pH (5.25–5.74) enhanced mobility and potential bioavailability of Ba, Co, Li, Mn, and Pb present in mainly ionic species, compared with other locations (pH 5.82–6.37). Manure application exhibited a dual effect, potentially increasing bioavailability for As, Tl, and V due to probably enhanced cation exchange capacity (CEC), while also facilitating specific adsorption of Cu and U on DOM, potentially reducing their bioavailability depending on DOM molecular weight. Colloidal and ionic Al and Th concentrations were higher in forest soils than agricultural soils, with extremely low potential bioavailability of Th attributed to strong precipitation with inorganic colloids and adsorption on DOM. The lysimeter sampling and size fractionation method provided a clear insight into agricultural effects on TE distributions and enhancing understanding of agricultural soil health in terms of TE bioavailability in situ.

Analytical Chemistry is like the Fruit of an Apple Tree

Analytical chemistry is deeply rooted in Europe. It started with the work of Liebig and Fresenius, among others. Then Kirchhoff, as father of spectroscopy, contributed to the development of the modern instrumental analysis techniques flourishing today. As soon as I started learning analytical chemistry at university, I fell in love with it. At that time, I could not explain why I wanted to become an analytical chemist. Having gained experience teaching and performing research in analytical chemistry, I know now that I am attracted to it because this branch of chemistry is what an apple means to an apple tree - the fruit of a myriad of results in fundamental research in chemistry, always offering solutions to real life problems. I always wanted to become an analyst and to work at the analytical chemistry department where I studied. One year ago, my life drastically changed at the institute when I was invited to apply to lead the analytical chemistry department where I have been working since 2007. I must admit that I had mixed feelings in the beginning. First of all, I was honored that my colleagues in the department fully expressed their support. At the same time, I was confused and scared. I felt that I am not the right person to lead a department with a history of almost 120 years, that I had no clear vision of what could I do for my colleagues and for the students choosing our department. However, I wanted to express my gratitude to my colleagues for their trust in me. In my application, I advocated to maintain the high-quality teaching of analytical chemistry at the department and offered to implement challenge-based learning for students choosing our department. In past years, I felt that the raison d'être of analytical chemistry departments as single entities would soon end. My colleagues working in other fields such as biology, geography and geology, pharmacy and medicine, all purchased instrumental analytical equipment and started performing research by themselves. Recently, analytical chemistry departments underwent important organizational and structural changes. Some of them disappeared, others incorporated into their name environmental chemistry, food chemistry, or biochemistry. Recent advances in instrumental analysis create the impression that conducting chemical analysis is an easy task that no longer requires the expertise of chemists devoted to this branch of chemistry. However, there is still a lot of work to do, especially in the field of organic analytical chemistry. Thanks to innovations in mass spectrometry and related techniques, infrared spectroscopy, miniaturization (lab-on-chips) and sensors, ultra trace analysis, green methodologies, and elemental speciation, analytical chemistry is experiencing a second Golden Era. In last year alone, I was surprised by the ever-increasing number of chemistry bachelor and major students knocking on my door asking me to provide them with analytical chemistry-related research topics. That led me to contact faculty working at the other institutes offering cooperation with the arsenal of our instruments to widen the research topic choices in our department, advocating that we should unite and complement our efforts to create synergies. Surprisingly, the response of those colleagues was very positive. In one year, I could almost double the number of research topics for diploma work in our department. This is something that makes me happy and optimistic. I am confident that the development of analytical methods together with proper sampling and sample preparation are still important and crucial steps to produce high quality and reliable results. Moreover, participation of analytical chemists in these tasks is indispensable. The recent success of the Brazilian Journal of Analytical Chemistry achieving an impact factor of 0.7 makes me also think that analytical method development has still a bright future ahead. Long live Analytical Chemistry! Long live Brazilian Journal of Analytical Chemistry!

Hydrochemical characteristics and water quality assessment of natural water in the South China Mountains: the case in Lianzhou.

South China Mountain Region has a well-developed water system with the most abundant water in China. Untreated natural water is the main source of drinking water for the local people. This study aimed to investigate the hydrochemical characteristics and trace element concentrations of natural water in the mountainous regions of South China. In this study, 116 water samples were collected. Traditional hydrochemical methods, water quality index (WQI), hazard index (HI), and nutrient speciation of trace elements (NSTE) were used for analysis. In general, the hydrochemical type was mainly Ca-HCO3- type. The hydrochemical characteristics were mainly influenced by the weathering of calcite and silicate rocks. Overall total dissolved solids (TDS) were low, indicating mainly soft and very soft water. The water that met the standards for mineral water had an average concentration of 59.69mg/L for Sr (strontium) and an average concentration of 0.46mg/L for H2SiO3 (silicic acid). Although the water quality index (WQI) indicated that 91.3% of the water samples in the study area were of good quality (WQI < 25), 2.58% of the water samples had significant non-carcinogenic risk (HI > 1) due to the high As and Pb concentrations. The water in the study area contributed significantly to human intake of Sr, Cr, and V, accounting for 8.4, 8.3, and 7.7% of the required daily intake for adults, respectively. It is recommended that a comprehensive water quality evaluation system be constructed to ensure that mountain water is managed for development and safe to drink.

Distribution and Speciation of Trace Elements in Soils of Four Land-Use Systems

Land use has a greater impact on trace element (TE) concentration present in soils. In mountainous regions of the western Himalayas, some dominating geogenic and human-dependent anthropogenic factors are involved in the spatial distribution of TEs in various land uses. Soil samples were collected from permafrost, pasture, forest, and agricultural land-use systems of Babusar Valley and Fairy Meadows in Diamer districts and the Rama region in Astore Districts in replications for investigation of three TEs, i.e., copper (Cu), zinc (Zn), and nickel (Ni). These samples were analyzed for exchangeable, adsorbed, organically bound, carbonate precipitated, and residual forms. Significant differences among these TEs were observed. Differences in the levels of TEs within soil samples were observed to be influenced by land usage patterns. The physicochemical properties of soil samples were also investigated. Additionally, the total metals (Ni, Zn, Cu) were extracted and their concentrations were measured in all samples. The concentration of soil TEs was observed in the following order: adsorbed &lt; organically bound &lt; exchangeable &lt; residual &lt; carbonate precipitated form across all the land uses. The results indicate that the contents of TEs (Ni, Zn, Cu) in agricultural soils were greater than in the permafrost pasture and forest soil samples. The total TE concentration varied as Zn &gt; Ni &gt; Cu irrespective of the area and land uses. We believe this work will open avenues for researchers to explore TEs in various regions of the world.

Nanoparticles as a younger member of the trace element species family — a food perspective

Speciation analysis plays a key role in understanding the biological activity and toxicity of an element. So far, classical speciation analysis focused only on the dissolved fraction of an elemental species, whereas nanoparticle forms of analytes are being widely found in consumer and industrial products. A significant contributor to human exposure to nanoparticles is through food into which nanoparticles can be incorporated from endogenous sources or they may be formed naturally in the living organisms. Nanoparticles often undergo changes in the food matrices and upon consumption, in the gastrointestinal tract, which present a significant challenge to their characterisation. Therefore, a combination of both classical and nanoparticle speciation analytical techniques is needed for the characterisation of both dissolved and particulate forms of the chemical species. This article presents and discusses the current trends in analysis of nanoparticle behaviour in the gastrointestinal tract and formation and characterisation of biogenic nanoparticles.Graphical

Potential hazards and road-source apportionment of toxic trace metals in the dust from residential buildings in typical coal-utilization cities

Toxic trace metals in dust from residential buildings are closely related to human health, but the transmission route and impact degree of dust from coal utilization sources are still unclear. A total of 158 dust samples from different floors of 31 residential buildings in a typical coal-utilization city were collected and analyzed. Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS) were used to analyze chemical speciation and sources of trace elements. Extremely high concentrations of Zn (14,308 mg/kg), Cu (553 mg/kg), Cr (319 mg/kg), Pb (1,208 mg/kg), As (30.8 mg/kg), and Cd (4.18 mg/kg) were found in the dust of residential buildings. Different trace elements tend to be enriched in different floor zones. The concentration of Zn was enriched in the low floor zone, while Cu and Pb were enriched in the middle floor zone, and Cd was enriched in the upper floor zone. The distribution of trace elements was found to be highly correlated between road dust and ground residential building dust, indicating that the input from road dust was the primary factor. Principal component analysis (PCA) combined with particle morphology and mineralogy study demonstrated that coal combustion, road and coal mining dust, and tire wear particles were likely sources of trace elements in dust. Risk assessments showed that As, Pb, and Cr in some samples were found to be harmful to children, particularly in high toxic forms of As (III) and PbO. This study provides systematic evidence for the transmission route and risk assessment of toxic trace metals in dust from residential buildings in coal-utilization cities.

Joanna Szpunar, a great chemical researcher internationally recognized, kindly spoke to BrJAC

Joanna Szpunar graduated from the Warsaw University of Technology in 1986 and obtained her Ph.D. (1992) and D.Sc. (Habilitation) (2000) from the University of Warsaw. Since 1997, she works at the National Research Council of France (CNRS). In 2007, she obtained in Poland the title of professor of chemistry. She has broad experience in the field of mass spectrometry-based bio-inorganic speciation analysis and metallomics with a focus on the identification and quantification of trace element species in biological systems and in the chemistry of metal-biomolecule interactions. She is the co-author of a book and approximately 250 scientific publications in peer-reviewed international journals. Joanna Szpunar is a fellow of the Royal Society of Chemistry (UK) and has been, for many years, a member of the boards of Journal of Analytical Atomic Spectrometry' and Metallomics. She regularly gives invited lectures at international analytical chemistry meetings and was the chairperson of the European Winter Conference on Plasma Spectrochemistry (Kraków, Poland) in 2013. The investigations carried out under her supervision and/or with her active participation resulted in the identification of a number of molecular targets of metals in biological systems, as well as contribute to selenometabolomics and selenoproteomics studies in bacteria and plants. In recent years, her interests were broadened to the environmental fate of metal-containing nanoparticles and nanoplastics. She has supervised 12 Ph.D. theses and several post-doctoral fellows. Joanna Szpunar is the laureate of the 2013 Jerzy Fijalkowski Award of the Committee of Analytical Chemistry of the Polish Academy of Sciences and the 2017 European Award for Plasma Spectrochemistry. In recent years, Joanna Szpunar has been involved in collaboration with analytical chemists in Brazil, hosting graduate students from the University of Campinas and the Federal University of Pelotas in the laboratory at the Institute of Analytical Sciences (IPREM) in Pau afiliated with the CNRS, lecturing at the Federal University of Santa Maria and co-supervising a Ph.D. student with work carried out at the University of Pau and the Federal University of Pelotas.

Development of High-Energy µ-X-ray Fluorescence and X-ray Absorption Fine Structure for the Distribution and Speciation of Rare Earth Elements in Natural Samples

Micro-X-ray fluorescence and X-ray absorption fine structure (µ-XRF-XAFS) is one of the most powerful tools to identify the distribution and speciation of trace elements in natural samples with µm spatial resolution. However, conventional µ-XRF-XAFS studies applied to rare earth elements (REEs: lanthanide elements + Y in this study) are mainly limited to their L-edges and L lines (except for Y) that are subject to strong interferences from other elements (mainly transition metals). In this study, we extend µ-XRF-XAFS to the higher energy region (HE-µ-XRF-XAFS) by using an incident X-ray microbeam (size: ca. 1 × 1 µm2) between 38 and 54 keV to realize K-edge excitation lanthanide analysis without interferences from other elements at the BL37XU beamline, SPring-8 (Japan). This method enables us to simultaneously analyze (i) REE patterns (from La to Dy), (ii) XAFS spectra, and (iii) µm-scale distribution of each REE in the natural sample. The proposed method also realizes the simultaneous application of µ-XAFS at low (e.g., Fe K-edge) and high (lanthanide K-edges) energy at the same spot without changing the setup of the µ-XRF-XAFS system using the detuning technique.

Geochemical Equilibrium Modelling of the Aqueous Speciation of Select Trace Elements in the Great Lakes

The behaviour and fate of trace elements in surface waters are greatly affected by their chemical form in solution, but the aqueous speciation of dissolved trace elements in the North American Great Lakes has received relatively little attention. Here, we present results from geochemical equilibrium modelling with 2021 surface water quality data to examine the spatiotemporal dynamics of trace element speciation in the Great Lakes. The relative abundance of aqueous trace element species appeared consistent with variability in solution chemistry and followed basin-wide trends in pH, alkalinity, salinity, and nutrient levels. The speciation of alkali metals was dominated by free monovalent cations, and that of oxyanion-forming elements by oxoacids, whereas significant fractions (&gt;1%) of other aqueous complexes were also evident for rare earth elements (e.g., Ce and Gd as carbonates), alkaline earth metals (e.g., Sr as sulfates), or transition metals (e.g., Zn as phosphates). Spatially, differences in the relative abundance of aqueous trace element species were &lt;2 orders of magnitude, with the highest variation (~50-fold) occurring for select chloride-complexes, resulting from upstream-to-downstream salinity increases in the basin. Finally, simulations of various future water quality scenarios (e.g., decreasing P levels, increasing temperature and salinity) suggest that the speciation of most trace elements is robust temporally as well. This study demonstrates how considering aqueous speciation may help improve the understanding of trace element dynamics and support water quality management in the Great Lakes.

Changes in Speciation and Bioavailability of Trace Elements in Sewage Sludge after the Ozonation Process

This work aimed to detect changes in trace element chemical speciation in sewage sludge (SS) after the ozonation process. The modified Community Bureau of Reference (BCR) sequential extraction procedure was performed to determine the chemical speciation of trace elements in SS after the ozonation process. To assess potential soil contamination with trace elements from sewage sludge after the ozonation process, the risk assessment code (RAC) coefficient was used. The bioaccumulation factor (BAF) and translocation factor (TF) values were also calculated to characterize the efficiency of trace element accumulation in the studied plant species from soil fertilized with sludges after the ozonation process. Generally, the mean concentration of total trace elements in the SS after the ozonation process was higher, but the differences were statistically significant only in the case of Mn, Cu, Pb, and Cd. The dominant fraction of Fe, Cr, Pb, and Cd was the residual fraction F4, while the extractable/exchangeable fraction F1 was present in the smallest amount. Therefore, in the case of Mn, Zn, and Ni, the ozonation process had a significant impact on the increase in the content of these elements in the F1 fraction. The application of the SS stabilized by ozonation process for maize and wheat fertilization did not significantly affect the bioaccumulation of most of the analyzed metals in aboveground biomass. Higher values of BAF coefficients after the application of ozonated SS were found only in the case of Cu and Ni. In turn, the determined TF coefficients were lower than 1 in most cases. The obtained results showed that the slight change in the concentration of Zn, Mn, and Ni in fraction F1 causes a specific risk of their mobility in the soil environment. It should be noted that due to the variable composition of sewage sludge, an analysis of the content of individual trace elements in chemical fractions should be carried out to assess its actual impact on the environment. This can help to indicate further actions that should be undertaken to limit their negative impact on the environment.

Chemical Speciation of Trace Elements in Soil Fertilized with Biomass Combustion Ash and Their Accumulation in Winter Oilseed Rape Plants

The impact of fertilization of fly ashes from biomass combustion (BAs) on the changes in the chemical speciation of trace elements (Zn, Cu, Cr, Ni, Pb, Cd) in Gleyic Chernozem soil was analyzed in field-experiment conditions, under cultivation of winter oilseed rape plants. The three-year field experiment was carried out in southeastern Poland (50°3′ N, 22°47′ E). The three-stage sequential extraction procedure developed by the Measurements and Testing Program (BCR) was used for the fractionation of trace elements in BAs and soil. The risk assessment code (RAC) coefficient was used to assess potential soil contamination with trace elements from Bas. The total content of Zn, Cu, Cr, Ni, Pb, and Cd in BAs used in the experiment was 470, 311, 29, 78, 38, and 3.7 mg kg−1, respectively. The present study showed that the application of BAs significantly increased the total concentration of Zn and Cu in the surface layer of the Gleyic Chernozem soil, and did not significantly increase the concentration of Cr, Ni, Pb, and Cd. Generally, using BAs does not significantly change the chemical speciation of trace elements in soil. Regardless of the applied fertilization, residual fraction (F4) was the most abundant, whereas the exchangeable/extractable (F1) fraction and reducible (F2) fraction were present in the smallest amounts. Due to the low share of exchangeable/extractable fraction (F1), the BAs used in the experiment were characterized by a low RAC coefficient; hence, their use as a soil fertilizer is relatively safe for the environment. The BAs fertilization did not cause significant changes in the content of trace elements in the different parts of the winter oilseed rape plants. Due to the relatively high content of trace elements in fly ashes from biomass combustion, an analysis of the content of individual trace element fractions should be carried out to assess their actual impact on the environment. This can help indicate further actions that should be taken to limit their negative environmental impact.

40 Years Old and Still Solving Problems: Evolution of the ICP-MS Application Landscape

The year 2023 marks the 40th anniversary of the commercialization of inductively coupled plasma mass spectrometry (ICP-MS). Today, there are close to 2000 ICP-MS systems installed worldwide every year, representing around $400M in annual sales. These instruments are used for a wide variety of applications, from routine, high-throughput multielement analysis to more complex tasks, such as trace element speciation studies with high-performance liquid chromatography and monitoring of nanoparticles. My column this month will look at the evolving ICP-MS marketplace, highlighting current application trends (compared to other analytical spectroscopy techniques), and where the technique might be heading 5–10 years from now.

Seasonal Variations of Mineralogical and Chemical Composition of Particulate Matter in a Large Boreal River and Its Tributaries

Despite the importance of river suspended matter (RSM) for carbon, nutrient, and trace metal transfer from the land to the ocean, the mineralogical control on major and trace element speciation in the RSM remains poorly constrained. To gain a better understanding of environmental and seasonal factors controlling the mineral and chemical composition of riverine suspended load, we studied, over several hydrological seasons, including winter baseflow, the RSM of a large boreal river in Western Siberia (Ob in its middle course) and its two small tributaries. The concentration of RSM increased from 2–18 mg/L in winter to 15–105 mg L−1 during the spring flood. Among the dominant mineral phases of the RSM in the Ob River, quartz (20–40%), albite (4–18%), smectite (2–14%), and chlorite (6–16%) increased their relative proportions with an increase in discharge in the order “winter ≤ summer &lt; spring flood”; illite (5–15%) was not affected by seasons or discharge, whereas the abundance of calcite (0–30%) decreased with discharge, from winter to summer and spring. Seasonal variation of elemental composition of the Ob River’s RSM allowed distinguishing three main groups of elements. Sodium, K, Si, Al, trivalent, and tetravalent hydrolysates increased their concentrations in the RSM with an increase in discharge, reflecting enhanced contribution of lithogenic material during high flow, whereas the concentration of alkaline-earth metals (Ca, Sr, Ba), P, Mn, and As decreased with discharge, reflecting accumulation of these elements in the suspended matter under ice. At the same time, a number of nutrients and trace elements demonstrated progressive accumulation in the RSM during winter (Ca, P, Cu, Zn, Mo, As, Cd, Sb). Micronutrients (V, Co), Fe, and Cr exhibited a minimum during summer, which could reflect both the uptake of these elements by the biota during baseflow (micronutrients) and their enhanced export during winter and spring compared to summer (Fe). The RSM of small tributaries demonstrated quite a different pattern compared to the Ob River main stem. Maximal concentration of suspended matter was observed at low discharges during the winter. During this period, the RSM was dominated by amorphous Fe hydroxides. Overall, the obtained results confirm the overwhelming impact of peatlands on element export in suspended form in small rivers of Western Siberia, and strong seasonal variations of both mineralogy and chemistry of the RSM in the Ob River main stem. Elemental yields (watershed-normalized export), assessed for the first time for the middle course of the Ob River and tributaries, were shifted towards the more important role of particulate vs. dissolved export for a number of trace elements, compared to that of the small and medium-sized rivers of Western Siberia, draining the taiga forest and peatlands of the boreal zone. The contrasting pattern of RSM chemical composition across the year demonstrated the importance of seasonal approach for sampling river suspended matter and calls a need for addressing strongly understudied RSM sources during winter baseflow, under ice.