Speciation Of Elements Research Articles

Rare earth element (REE) speciation in municipal solid waste incineration ash

A robust and sustainable supply of rare earth elements (REE) is critically needed for clean-energy technologies, which has stimulated substantial interests in REE recovery from waste streams. Municipal solid waste incineration ash (MSWIA) was recently recognized as a potentially important REE resource, yet REE speciation in MSWIA remains poorly understood. This study employed synchrotron X-ray spectroscopy and microscopy techniques to elucidate the speciation of representative REE (Y, Ce, and Nd) in different MSWIA samples. Linear combination fitting of bulk X-ray absorption near edge structure (XANES) data indicated that Y-bearing Al/Fe oxides and phosphates are the primary Y-hosting phases. Micro-XANES of individual Y-containing particles identified by micro X-ray fluorescence (μXRF) mapping revealed notably different Y speciation at micro-scale from the bulk, consistent with the highly heterogeneous nature of MSWIA samples. The main REE-bearing phases in different size-fractionated MSWIA are similar: Y and Nd as oxides and xenotime/monazite, and Ce as apatite and monazite. Our results provide important insights for designing pre-screening processes (e.g., density separation) and optimizing extraction methods (e.g., pH, use of ligands) for cost-effective REE recovery from MSWIA.

Insights into rare earth element speciation: unraveling sulfate and hydrolysis complexes through DFT calculations.

Rare earth elements (REE) are indispensable in numerous green technologies owing to their exceptional physical and chemical attributes. Separating REE is a pivotal process to meet the increasing demands of the high-tech industry. Understanding the hydrolysis of REE in aqueous environments marks the initial stride in comprehending their separation mechanisms. Sulfate commonly coexists in high-concentration solutions alongside REE, stemming from mineral processing. We analyzed the hydrolysis of REE and their complexes with sulfate using DFT methods. We present and discuss on the structural characteristics of hydrolysis species and sulfate complexes in alignment with existing experimental data. Estimates of Gibbs free energies for hydrolysis and sulfate complex formation were compared against literature values. REE pose challenges owing to the labile nature of aqua complexes and the pivotal role of system dynamics. We showed that hydrolysis reactions could be suitably modeled, yielding an error margin of approximately 5kcalmol-1 concerning experimental values, employing the M06 exchange-correlation functional with the SMD implicit solvation model. However, sulfate chemical species proved to be more challenging, exhibiting larger error margins with substantial variations across the REE series. The Raman spectrum analysis of lanthanum sulfate complexes demonstrated excellent agreement with experimental values. We applied the M06, PBE, and PBE0 exchange-correlation functionals combined with def2-TZVP basis sets and SMD to obtain the Gibbs free energies of hydrolysis and sulfate complexation with lanthanides in aqueous solution. The calculations were performed using the ORCA program.

Sequential Extraction Procedure for Elemental Speciation in Jordanian Oil Shale Ash

Sequential Extraction Procedure for Elemental Speciation in Jordanian Oil Shale Ash

Biogeochemical sulfur transformations in the cohesive and permeable tidal flat sediments of Jade Bay (North Sea)

Intertidal flats are highly productive coastal marine ecosystems which are affected by fast changes in environmental conditions and host dynamic biogeochemical cycles in their sediments. Bioturbation by burrowing organisms and roots of plants strongly affects speciation and cycling of redox-sensitive elements in intertidal sediments. In this work, we have studied the impact of sediment type and vegetation on the cycling of redox-sensitive elements including sulfur, iron, and manganese in sandy and muddy tidal flats sediments in the Jade Bay (North Sea) and adjacent area. The redox speciation of these elements was analyzed in the pore-waters and the total sediment. The isotopic compositions of sulfur species were measured in non-vegetated sediments and in sediments which are inhabited by various plants. In the cohesive sediments, which are not affected by vegetation, a decrease in sulfate concentration, coupled with the presence of relatively high concentrations of hydrogen sulfide in the pore-waters and the presence of sulfide minerals as well the isotopic compositions of sulfur species are consistent with fast rates of sulfate reduction in the sediments. In the cohesive sediments affected by roots of Salicornia stricta and sediments desiccation, a cryptic sulfur cycle, which is characterized by microbial sulfate reduction coupled to fast reoxidation of hydrogen sulfide by Fe(III) (hydr)oxides and, possibly, by oxygen is present. Below the roots penetration depth, speciation of redox-sensitive elements is similar to those in the baren sediments. In the cohesive sediments affected by the roots of Spartina anglica and Triglochin maritima, which have longer roots, a cryptic sulfur cycle was detected in the upper 30 cm of sediments. At the sites that are characterized by permeable surface sediments and alternating permeable and cohesive layers in the deeper sediments, the composition of the sediment has a similar or even more significant impact on the speciation of the redox-sensitive elements than penetration of relatively weak roots of Spartina anglica. These sediments are characterized by the formation of hydrogen sulfide and sulfide oxidation intermediates in the cohesive layers and their diffusion to (and oxidation at) the boundaries between cohesive and permeable sediments. We conclude that in the cohesive sediments, the penetration of roots and desiccation leads to the formation of overall oxidized conditions, while in the sediments with alternating layers, permeability may provide a more significant control for speciation of redox-sensitive elements.

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.

Rare Earth Element Speciation in Coal and Coal Combustion Byproducts: A XANES and EXAFS Study.

Transitioning to a low-carbon economy, necessary to mitigate the impacts of anthropogenic climate change, will lead to a significant increase in demand for critical minerals such as rare earth elements (REE). Meeting these raw materials requirements will be challenging, so there is increasing interest in new sources of REE including coal combustion byproducts (CCBs). Extraction of REE from CCBs can be advantageous as it involves reusing a waste product, thereby contributing to the circular economy. While a growing body of literature reports on the abundance of REE in CCBs globally, studies examining the key factors which control their recovery, including speciation and mode of occurrence, are lacking. This study employed synchrotron-based X-ray absorption spectroscopy to probe the speciation and local bonding environment of yttrium in coals and their associated CCBs. Linear Combination Fitting identified silicate and phosphate minerals as the dominant REE-bearing phases. Taken together with the results of extended X-ray absorption fine structure (EXAFS) curve fitting, we find there is minimal transformation in the REE host phase during combustion, indicating it is transferred in bulk from the coals to the CCBs. Accordingly, these findings can be incorporated into the development of an efficient, environmentally conscious recovery process.

Trace metal speciation trends in Mazowe dam, Zimbabwe, a typical sub-tropical dam ecosystem impacted by gold mining and agriculture.

The present study aimed to assess trace metal speciation trends in the water and sediments of Mazowe Dam, a typical sub-tropical dam ecosystem impacted by gold mining and agriculture in Zimbabwe. The elements studied include Al, As, Cd, Co, Cr, Cu, Hg, Fe, Mn, Ni, Pb, and Zn. Elemental speciation in the water column was determined using Visual MINTEQ version 3.1 geochemical computer modelling, while speciation in the sediment phase was determined using sequential extraction techniques. For each element, the data obtained were subjected to extensive correlation analysis to identify intra- and inter-metal species interactions in the water column and the sediment phase, as well as across the water-sediment interface. Possible mechanisms to account for the observed species interactions are proposed. In the water column, Co was predicted to have the highest number of chemical species (9), Cd and Zn (8), Mn and Fe (7), Ni (6), Pb (5), Al and Cu (3), Cr, Hg, and As have the least (2). In the sediment, Al, As, Co, Cr, Cu, Fe, Ni and Fe mainly exist in the residual fraction, while Zn and Mn concentrations in fractions vary per sampling site, with no fraction that is dominant across the sampling sites. Equilibrium exchange reactions across the water-sediment interface were observed e.g., for Cd species /FA2Cd (aq) and Co species /FACo+2G (aq), and /FA2Co (aq). This study is valuable in highlighting trace metal speciation in a tropical dam ecosystem in Africa and adds to the growing knowledge about the behaviour of trace metals in aquatic ecosystems in the region and globally.

Influence of environmental settings, including vegetation, on speciation of the redox-sensitive elements in the sediments of monomictic Lake Kinneret

AbstractThe redox conditions in the littoral limnic sediments may be affected by the penetration of plant roots which provide channels for oxygen transport into the sediment while decomposition of the dead roots results in consumption of oxygen. The goal of this work was to study the impact of environmental parameters including penetration of roots of Cyperus articulatus L. into the sediments on cycling of the redox-sensitive elements in Lake Kinneret. We measured roots content, porosity, and chemical parameters including pH, sulfur, iron and manganese speciation in the sediments from the shore, littoral and sublittoral zones with and without vegetation. Our results show that at ≥ 12 m water depth, the upper 10 cm of the sediments are affected by the active sulfur cycling with concentrations of hydrogen sulfide > 70 μM near the sediment–water interface. Speciation of sulfur, iron, and manganese in the upper 10 cm of littoral sediments, which are covered by < 20 cm of water, are affected by their permeability and, to a lesser extent, by roots penetration. In the case when sediments are not covered by water, oxygen penetration to the sediments by desiccation is an additional important control of the redox zonation in the surface sediments. In the shore sediments, despite relatively high concentrations of sulfate in the pore-waters, sulfur cycling may be described as “cryptic” as expressed by very low concentrations of hydrogen sulfide in the pore-waters. This is most likely a result of its fast reoxidation by the abundant highly reactive Fe(III) and Mn(IV) phases.

Bioavailability and ecological risk assessment of metal pollutants in ambient PM2.5 in Beijing

Metal pollutants in fine particulate matter (PM2.5) are physiologically toxic, threatening ecosystems through atmospheric deposition. Biotoxicity and bioavailability are mainly determined by the active speciation of metal pollutants in PM2.5. As a megacity in China, Beijing has suffered severe particulate pollution over the past two decades, and the health effects of metal pollutants in PM2.5 have received significant attention. However, there is a limited understanding of the active forms of metals in PM2.5 and their ecological risks to plants, soil or water in Beijing. It is essential that the ecological risks of metal pollutants in PM2.5 are accurately evaluated based on their bioavailability, identifying the key pollutants and revealing historic trends to future risks control. A two-year project measured the chemical speciation of pollution elements (As, Cd, Cu, Cr, Ni, Mn, Pb, Sb, Sr, Ti, and Zn) in PM2.5 in Beijing, in particular their bioavailability, assessing ecological risks and identifying key pollutants. The mass concentrations of total and active species of pollution elements were 199.12 ng/m3 and 114.97 ng/m3, respectively. Active fractions accounted for 57.7 % of the total. Cd had the highest active proportion. Based on the risk assessment code (RAC), most pollution elements except Ti had moderate or high ecological risk, with RAC exceeding 30 %. Cd, with an RAC of 70 %, presented the strongest ecological risk. Comparing our data with previous research shows that concentrations of pollution elements in PM2.5 in Beijing have decreased over the past decade. However, although the total concentrations of Cd in PM2.5 have decreased by >50 % over the past decade, based on machine model simulation, its ecological risk has reduced by only 10 %. Our research shows that the ecological risks of pollution elements remain high despite their decreasing concentrations. Controlling the active species of metal pollutants in PM2.5 in Beijing in the future is vital.

Speciation, phytoavailability, and accumulation of toxic elements and sulfur by humic acid-fertilized lemongrass and common sage in a sandy soil treated with heavy oil fly ash: A trial for management of power stations wastes

Globally, power stations generate huge amounts of the hazardous waste heavy oil fly ash (HOFA), which is rich in Ni, V, Fe, S, and dumped into landfills. Thus, exploring new approaches for a safe recycling and sustainable management of HOFA is needed and of great environmental interest. The potential application of HOFA as an amendment to sandy soils has not been studied yet. This is the first research investigating the potentiality of using HOFA as a soil conditioner. To this end, we conducted a greenhouse experiment in order to investigate the impacts of HOFA addition (1.2, 2.4, 3.6 t ha−1) to sandy soil on the total and available content of nutrients (e.g., S, Fe, Mn, Cu, Zn) and toxic elements (TEs; e.g., Cd, Co, Cr, Ni, Pb, V) in the soil and their phytoextraction and translocation by lemongrass (Cymbopogon citratus) and common sage (Salvia officinalis). We also assessed the impact of humic acid (HA) foliar application (50 and 100 l ha−1) on the growth and elements accumulation by the two plants. The studied HOFA was acidic and highly enriched in S (43,268.0), V (3,527.0), Ni (1774.0), and Fe (15,159.0) (units in mg kg−1). The X-ray absorption near edge structure (XANES) data showed that V in HOFA was composed primarily of V(IV) sorbed onto goethite, V(V) sorbed onto humic substances, in the forms of V2O3, and VCl4. Addition of the lower doses of HOFA (1.2 and 2.4 t ha−1) did not change significantly soil pH, salinity, and the total and available elements content compared to the unamended soil. Although the elements content in the 3.6 t ha−1 HOFA-treated soil was significantly higher than the untreated, the total content of all elements (except for Ni) was lower than the maximum allowable concentrations in soils. HOFA addition, particularly in the highest dose (3.6 t ha−1), decreased significantly the growth and biomass of both plants. Common sage accumulated more elements than lemongrass; however, the elements content in the plants was lower than the critical concentrations for sensitive plants. The foliar application of humic acid enhanced significantly the plant growth and increased their tolerance to the HOFA-induced stress. We conclude that the addition of HOFA up to 2.4 t ha−1 in a single application as amendment to sandy soils is not likely to create any TE toxicity problems to plants, particularly if combined with a foliar application of humic acid; however, repeated additions of HOFA may induce toxicity. These findings should be verified under field conditions.

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.

Speciation of vanadium and the interacted solid surface of δ-alumina adsorbent in aqueous media in presence of humic acid

Speciation of vanadium elements in the presence of δ-alumina in aqueous media was studied to simulate the environmental impact of soil/sediment–water interacted system. Factors affecting this process are pH, presence of humic acid, and δ-alumina concentrations as an abundant sediment/soil components. Different species of both vanadium and surface of δ-alumina were deduced theoretically using MintaqA2 programme. Due to the effect of pH, the anionic species of vanadium at pH 1–3 is prevailed and changed to cationic species at pH range 6–10 at different levels of alumina. Additionally, based on the effect of alumina concertation, high percent uptake, almost 100% was found at 10.0 g/1 concentration of alumina while at level of 0.2 g/1 alumina, the maximum adsorption of vanadium was become 91%. The effect of humic acid on the speciation behavior of vanadium (V) was also studied and compared with that of vanadium (IV) based on XANES (X-ray absorption near edge structure). Adsorption behaviors were studied at concentration 4.71E-4M for vanadium at 0.1M ionic strength. The mechanism of vanadium adsorption in the presence of alumina under the same working conditions was studied and explained based on TLM (Triple layer model) where the results proved good validation and verification of the practically produced data.

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.

Ferric Iron in Eclogitic Garnet and Clinopyroxene from the V. Grib Kimberlite Pipe (NW Russia): Evidence of a Highly Oxidized Subducted Slab

Abstract Estimates of oxygen fugacity of eclogitic rocks are linked to the redox evolution of the oceanic protolith during subduction and its residence in the lithospheric mantle, and, based on knowledge of pressures and temperatures, allow modelling of the speciation of volatile elements and diamond (or graphite) versus carbonate stability. To date, the oxygen fugacity of mantle eclogites has been shown to vary between −6 (Kasai, Congo and Udachnaya, Siberia) and −0.1 (Udachnaya, Siberia) log units (relative to the fayalite–magnetite–quartz buffer, FMQ), linked to the low Fe3+ contents of garnets. In this study, we investigated the Fe oxidation state of coexisting garnet and clinopyroxene hand-picked out of 17 diamond-free high-MgO and low-MgO mantle eclogites (dated at 2.84 Ga) from the Grib kimberlite pipe (East-European platform). Measured Fe3+/∑Fe values range between 0.03 and 0.19 for garnet and 0.18–0.38 for clinopyroxene, the former being higher than what was measured previously in garnets equilibrated at mantle conditions. The Fe3+/∑Fe of the reconstructed bulk rock ranges between 0.10 and 0.15 for high-MgO eclogites and 0.10 and 0.24 for low-MgO eclogites (with uncertainties of ± 0.02 and ± 0.03 in both cases). Thermobarometric calculations result in equilibration pressures and temperatures of 3.0–5.2 (± 0.4) GPa and 720–1050 (± 60) °C for both high-MgO and low-MgO eclogites, slightly lower than previous P–T estimates of mantle eclogites from the Udachnaya kimberlite pipe (Siberian craton). At these conditions, ∆logfo2 (FMQ) calculated using the available oxythermobarometric model varies from −1.7 to −0.6 log units for high-MgO eclogites and from −2.9 to 0.9 log units for low-MgO eclogites. Samples recording ∆logfo2 (FMQ) ≤ −1 log units overlap with North Slave, West Africa and Udachnaya eclogites, with no difference among eclogite types. The average values of −1.2 (± 0.4) log units for high-MgO and −0.6 (± 1.1) log units for low-MgO eclogites suggest different redox conditions of basaltic protoliths during subduction worldwide. Previous geochemical studies on the same rock samples reported evidence of cryptic metasomatism in both garnet and clinopyroxene that we demonstrate being not recorded by their major elements, while modal metasomatism evidenced by the presence of phlogopite as a product of interaction with a kimberlitic melt only affects the MgO of the bulk rock. Therefore, we suggest that high Fe3+/∑Fe ratios for garnet (> 0.10) and for reconstructed bulk rocks in the case of both low-MgO and high-MgO samples cannot be due to metasomatic interaction with an oxidized fluid, but rather are the consequence of Fe3+ redistribution in an unusually oxidized mafic protolith upon metamorphism. Our results highlight the redox variability of eclogites of Archaean age at conditions more oxidized than present-day mid-ocean ridge basalts (MORBs) and imply an oxidizing nature of the convective mantle source where magma was formed with consequent speciation of C in the form of carbonate fluid explaining, therefore, the lack of eclogitic diamonds in V. Grib kimberlite pipe.

Relation between solid phase speciation and oral/lung bioaccessibility of metal(loid)s polluted soils in inhabited area: Contribution of synchrotron-based experiment

The presence of contaminated sites/soils in or near cities can pose significant risks to public health. The city of Viviez (France) was taken in reference site bears significant industrial responsibility, particularly in zinc metallurgy, with the presence of a now rehabilitated smelter. This has led to soil contamination by zinc (Zn), lead (Pb), arsenic (As), and cadmium (Cd), with concentrations reaching up to 4856 mg kg−1, 1739 mg kg−1, 195 mg kg−1, and 110 mg kg−1, respectively. The aim of this study is to comprehend the contamination patterns of the site post-rehabilitation, the geochemical behavior of each element, and their speciation (analyzed through BCR, XRD, and XANES) in relation to associated health risks due to metals accessibility for oral ingestion and inhalation by the local population. The findings revealed that elements inducing health risks were not necessarily those with the highest metal contents. All results are discussed in terms of the relationship between element speciation, stability of bearing phases, and their behavior in different media. XANES is an important tool to determine and estimate the Pb-bearing phases in garden soils, as well as the As speciation, which consist of Pb-goethite, anglesite, and Pb-humate, with variations in proportions (the main phases being 66 %, 12 % and 22 % for Pb-goethite, anglesite, and Pb-humate, respectively) whereas As-bearing phase are As(V)-rich ferrihydrite-like. A new aspect lies in the detailed characterization of solid phases before and after bioaccessibility tests, to qualify and quantify the bearing phases involved in the mobility of metallic elements to understand the bioaccessibility behavior. Ultimately, the health risk associated with exposure to inhabitants, in terms of particle ingestion and inhalation, was assessed. Only ingestion-related risk was deemed unacceptable due to the levels of As and Pb.

Characterization, Concentration, and Speciation of Metal Elements in Copper Slag: Implications for Secondary Metal Recovery

The treatment of large amounts of copper slag is an unavoidable issue resulting from the high demand for copper during the global transition to a sustainable development path. Metal-rich copper slag might serve as a potential source of metals through secondary recovery. In this study, two copper slags (CS1 and CS2) with different metallurgical properties were characterized, focusing on secondary metal recovery. The X-ray diffraction (XRD) results show that fayalite (Fe2SiO4) and magnetite (Fe3O4) were the main crystalline phases in both CS1 and CS2. In addition, CS2 exhibited a more stable amorphous silicate network than CS1, which was attributed to the differences in the content of Si-O-3NBO linkages. The sequential extraction of Zn, Cu, Fe, and Pb from the slags was also explored, with the Cu content in CS1 being substantially lower than that in CS2. All metals were distributed in the F5 residue fraction. Cu was the most mobile metal as a result of the large proportion of soluble fractions (F1–F3), followed by Zn and Fe. This study explored the chemical speciation of Zn, Cu, Fe, and Pb from copper slags, which has practical implications for secondary metal recovery from such materials.

Environmental assessment of phosphogypsum: A comprehensive geochemical modeling and leaching behavior study

Understanding the variations in the geochemical composition of phosphogypsum (PG) destined for storage or valorization is crucial for assessing the safety and operational efficacy of waste management. The present study aimed to investigate the environmental behavior of PG using different leaching tests and to evaluate its geochemical behavior using geochemical modeling. Regarding the chemical characterization, the PG samples were predominantly composed of Ca (23.03–23.35 wt%), S (17.65–17.71 wt%), and Si (0.75–0.82 wt%). Mineralogically, the PG samples were primarily composed of gypsum (94.2–95.9 wt%) and quartz (1.67–1.76 wt%). Moreover, the automated mineralogy revealed the presence of apatite, fluorine and malladrite phases. The overall findings of the leaching tests showed that PG could be considered as non-hazardous material according to US Environmental Protection Agency limitations. However, a high leachability of elements at a L/S of 2 under acidic conditions ([Ca] = 166.52–199.87 mg/L, [S] = 207.9–233.59 mg/L, [F] = 248.62–286.65 mg/L) is observed. The weathering cell test revealed a considerable cumulative concentration over 90 days indicating potential adverse effects on the nearby environment (S: 8000 mg/kg, F: 3000 mg/kg, P: 700 mg/kg). Based on these results, it could be estimated that the surface storage of PG could have a serious impact on the environment. In this context, a simulation model was developed based on weathering cell results showed encouraging results for treating PG leachate using CaO before its disposal. Additionally, PHREEQC was used to analyze the speciation of major elements and calculate mineral phase saturation indices in PG leaching solutions. The findings revealed pH-dependent speciation for Ca, S, P, and F. The study identified gypsum, anhydrite, and bassanite as the key phases governing the dissolution of these elements.

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.