Soluble Pb Research Articles

Comparative study on different organic acids for promoting Solanum nigrum L. hyperaccumulation of Cd and Pb from the contaminated soil

Organic acids-assisted phytoremediation is a promising strategy to remove metal pollutants from the soil. However, few reports have focused on the mechanisms of organic acids promoting the uptake of heavy metals by hyperaccumulators. In this study, 5 types of organic acids, namely polybasic carboxylic acids, acidic amino acids, acidic plant growth regulators, phosphoric and gluconic acids, were comprehensively investigated the effects on the solubility of Cd and Pb in the soil along with their uptake by Cd hyperaccumulator Solanum nigrum L. The results indicated that the addition of Hydroxyethylidene-1,1-diphosphonic acid (HEDP) and d-Gluconic acid (D-GA) effectively extracted the most of acid-extractable and some of reducible and oxidizable fractions of Cd and Pb in the soil, with the extraction rates of 64.8% and 34.4% for total Cd and 53.6% and 30.0% for total Pb, respectively. HEDP and D-GA significantly increased the accumulations of Cd (57.1% and 35.0%) and Pb (43.4% and 31.9%) by S. nigrum without the inhibition of its biomass, making the great removal efficiencies of Cd (1.35% and 1.16%) and Pb (0.039% and 0.036%) from the soil. The enhanced phytoremediation efficiency of S. nigrum was due to the increase of the extractable Cd and Pb in the rhizosphere but little changes of soil pH and enzyme activities (catalase and urease). Among all of organic acids, HEDP may be an alternative to EDTA because of its characteristics of environmental friendliness and high efficiency.

Effect of Water Regimes on Pb and Cd Immobilization by Biochar in Contaminated Paddy Soil

An incubation experiment was conducted to explore the influence of 30% water holding capacity (WHC), flooding, and alternate dry-wet conditions on changes in heavy metal fractions with 1% rice straw biochar in Pb and Cd co-contaminated paddy soils, to provide a scientific basis for a water regime of biochar remediation on heavy metal contaminated paddy soil. Results showed that flooding and alternating wet-dry conditions could significantly increase soil pH, the contents of dissolved organic carbon (DOC), and amorphous iron oxide (Feo) after adding biochar. Compared with a 30% WHC treatment, when the soil is flooded and alternating wet-dry conditions, the content of the TCLP extractable Pb decreased by 31.87% and 20.33%, respectively, and the content of the TCLP extraction Cd decreased by 25.29% and 16.07%, respectively. Under flooding, the acid soluble Pb and Cd content decreased by 24.78% and 20.14%, respectively, and the acid soluble Cd content decreased over time. The decreasing order of available Pb and Cd content was flooding > alternating dry-wet > 30% WHC. Correlation analysis results showed that soil pH and Feo have significant negative correlation with available heavy metals, which means flooding with biochar could effectively immobilize Pb and Cd by increasing soil pH and Feo content. Flooding and biochar have a synergistic interaction on promoting the transformation of Pb and Cd to more stable fractions in acidic co-contaminated heavy metal polluted paddy soil.

Soil remediation approach and bacterial community structure in a long-term contaminated soil by a mining spill (Aznalcóllar, Spain)

The Aznalcóllar accident, which occurred in 1998, spilled 36 × 105 m3 of pyritic sludge and 9 × 105 m3 of acidic water around an area of 43 km2 in the south of Spain. This spill is considered one of the most important metal-mining associated accidents worldwide. In this study, two soil remediation techniques were evaluated: the addition of marble sludge (liming treatment, LS) and the mixing of recovered soils (RC) with contaminated soils (CT) (biopile treatment, BS). Both LS and BS significantly reduce the solubility of Cu, Zn, As, and Pb mainly due to the increase in pH and organic matter content, respectively. Soil basal respiration rate and the seed germination and root elongation bioassay with Lactuca sativa were used to evaluate the toxicity of the potential pollution in the sampled soils. Both bioassays showed that the CT soils exhibited the highest toxicity with a significant reduction in the toxicity of the amended soils (LS and BS). The abundance and structure of microbial communities in the soils were determined by qPCR and Illumina 16S rRNA sequencing, respectively. The absolute abundances of total bacterial and archaeal populations, ammonium oxidising bacteria, and denitrifiers in the CT soils were statistically lower than these found in the other three soils. Similarly, the structure of the bacterial community was highly different in the CT soils. Our results underline the persistence of the detrimental effect of pollutants in CT soils compared to the recuperated (RC) and amended soils (LS and BS). We also highlight the uses of liming or biopile as remediation techniques as satisfactory tools to reduce the impact of heavy metals in the contaminated Aznalcóllar soils.

Aqueous solubility of Pb at equilibrium with hydroxypyromorphite over a range of phosphate concentrations.

Hydroxypyromorphite (HPM) is a low-solubility Pb phosphate mineral that has the potential to limit solubility and bioavailability of Pb in soils and water. Because of reported uncertainty regarding the solubility product of this important mineral, we re-evaluated the solubility of Pb and activity of the free Pb2+ ion in aqueous suspensions of microcrystalline HPM equilibrated up to 30 days over a wide range of added soluble phosphate. A small addition of phosphate (0.1 mM) reduced Pb solubility as measured by ICP-OES, but greater phosphate additions (up to 50 mM) had no further effect in lowering HPM solubility. However, free Pb2+ ion activity measured by ion-selective electrode progressively decreased from about 10-6.5 with no added phosphate to 10-9 as soluble phosphate was increased. The effect of soluble phosphate in lowering Pb2+ activity is attributed to inhibited dissolution of HPM as well as increased Pb2+-phosphate ion pair formation in solution at higher solution concentrations of phosphate. Measurement of the ion activity products (IAP) of the solutions at equilibrium with HPM gave highly variable IAP values that were sensitive to pH and were generally not consistent with the reported solubility product of this mineral. The high variability of the IAPs for solutions with variable pH and phosphate concentrations indicates that dissolution-precipitation reactions of HPM are not described by a constant solubility product at equilibrium, possibly because of the incongruent dissolution behavior of this mineral at near-neutral pH.

Rhizosphere effect on Pb solubility and phytoavailability in Pb-Contaminated soils.

The effect of plant roots in modifying Pb solubility and bioavailability in an historically contaminated orchard (Hudson) and a Pb phosphate-spiked (Arkport) soil was determined by measuring soluble Pb in the soil solutions as well as content of Pb in radish shoots grown in these soils. Soluble Pb and dissolved organic carbon (DOC) contents were greater in the rhizospheres of both Pb-contaminated soils than in the unplanted high-Pb soils. The rhizosphere effect increased soluble Pb 15-fold in the field-contaminated orchard soil, whereas the effect was much smaller in the Pb phosphate-spiked soil. The rhizosphere effect persisted in the Pb-phosphate spiked soil after adjustment of the soil pH from 7.8 to 6.7. The results indicate that Pb phosphate added to a non-acid soil has lower solubility than Pb in an orchard soil contaminated by historical Pb arsenate applications; nevertheless, some uptake of Pb into plant shoots resulted from both sources of soil Pb contamination. The rhizosphere effect was observed for trace metals in addition to Pb, with the solubility of Al, Fe, Cu and Ni all increasing in the rhizosphere soil. In contrast, the solubility of alkali and alkaline earth metals (K, Ca, Mg, Sr, Ba) all decreased in the rhizosphere soil. The results indicate that the rhizosphere effect associated with plant roots can raise the solubility of Pb in soils contaminated by legacy Pb and by insoluble Pb phosphate.

Metal solubility in the rhizosphere of a co-cropping system. The role of total carbon exudation, soluble proteins and plant interaction

In the present study we assessed how modified rhizosphere pH and root exudation (total carbon (C) and soluble proteins released) affected lead (Pb) solubility as well as plant growth and Pb accumulation. A pot experiment with Pb polluted agricultural soils was performed, which involved growing two species, Capsicum annum (pepper) and Tagetes minuta, with the latter being a native herb indicated as potential phytoextractor of Pb, in monocrop and co-cropping conditions. Changes in plant growth, metal uptake as well as rhizosphere soil parameters (pH, EC) and total C and protein exudation were determined. In addition, the metal extraction efficiency of exudates released under mono- and co-cropped conditions were investigated. Results showed that in contrast to the control soil (with low Pb concentration), total C exudation was higher in co-cropping systems in Pb contaminated soils which lead to increases in Pb uptake in both species. Exudates originating from T. minuta were more efficient in solubilizing Pb than exudates from pepper when grown under mono-cropping conditions. Exudates derived from co-cropping both species were either equally or less efficient in mobilizing Pb than exudates from T. minuta. The capacity of exudates to mobilize metals was dependent not only on the species specific quality of root exudates released, but also on its quantity, with the metal extraction efficiency increasing with C concentration in exudates. However, the role of exuded proteins in Pb solubilization was found to be negligible. Biochemical interactions in the rhizosphere under co-cropping conditions favored metal solubilization, and consequently Pb accumulation. The co-cropping conditions could allow accumulation of Pb to levels in pepper that pose risks when the plants are used as a food source.

Synthesis and characterization of stable lead (II) orthophosphate nanoparticle suspensions

There is great interest in producing nanoparticles for various applications. The objective of this work was to develop a procedure for reproducibly creating stable lead (Pb) phosphate nanoparticle aqueous suspensions. A stable 5 mg/L Pb-phosphate nanoparticle “stock” suspension was synthesized via chemical precipitation of Pb and orthophosphate in water at pH 7.5 with 4.4 mg soluble PO4/L and 7 mg C/L dissolved inorganic carbon. The stock suspension was subsequently diluted to produce stable 0.10 mg/L Pb “challenge” water suspensions without compromising the nanoparticle size, structure, mineralogy and solubility. Specifically, the hexagonal hydroxypyromorphite nanoparticles had an average diameter of 38 nm based on transmission electron microscopy analysis and an associated Pb solubility of 0.001 mg/L. The properties of the stock suspensions were not impacted by further dilutions, and the challenge water suspensions remained stable for 24 hours. In the context of drinking water, a protocol to produce such a stable Pb nanoparticle challenge water suspension would be very useful in evaluating Pb bioavailability, identifying Pb remediation strategies, and testing filter effectiveness to remove Pb from water.

Phase diagram of Ag–Pb–Sn system

The Ag–Pb–Sn ternary system is an important material system for both electronic packaging and thermoelectric applications. However, there is no experimental phase equilibria information of the ternary system. Ag–Pb–Sn alloys are prepared and their phase equilibria at various temperatures were determined. The focus was on the 500, 350, and 200 °C isothermal sections. Additional information was also obtained for 400, and 300 °C. Several samples were studied by DSC studies. No ternary compounds were found in the ternary system. The Ag–Sn binary compounds, Ag3Sn(ε) and Ag4Sn(ζ) at 350 °C and Ag4Sn(ζ) at 500 °C, exhibit very small Pb solubility. The thermodynamic assessment of the ternary Ag–Pb–Sn system was carried out using the above mentioned experimental data.

PbS biomineralization using cysteine: Bacillus cereus and the sulfur rush.

Bacillus sp. Abq, belonging to Bacillus cereus sensu lato, was isolated from an aquifer in New Mexico, USA and phylogenetically classified. The isolate possesses the unusual property of precipitating Pb(II) by using cysteine, which is degraded intracellularly to hydrogen sulfide (H2S). H2S is then exported to the extracellular environment to react with Pb(II), yielding PbS (galena). Biochemical and growth tests showed that other sulfur sources tested (sulfate, thiosulfate, and methionine) were not reduced to hydrogen sulfide. Using equimolar concentration of cysteine, 1mM of soluble Pb(II) was removed from Lysogeny Broth (LB) medium within 120h of aerobic incubation forming black, solid PbS, with a removal rate of 2.03µg L-1 h-1 (∼8.7µM L-1 h-1). The mineralogy of biogenic PbS was characterized and confirmed by XRD, HRTEM and EDX. Electron microscopy and electron diffraction identified crystalline PbS nanoparticles with a diameter <10nm, localized in the extracellular matrix and on the surface of the cells. This is the first study demonstrating the use of cysteine in Pb(II) precipitation as insoluble PbS and it may pave the way to PbS recovery from secondary resources, such as Pb-laden industrial effluents.

ACID RESIDUES REMEDIATION FROM MINES USING BIOCHAR, MONOPOTASSIUM PHOSPHATE AND LIME

The Zimapan mining district in the state of Hidalgo (Mexico) generates residues with high content of Cu, Pb and Zn which have been disposed for decades on sites that could cause toxicity to the surrounding area. Simultaneously, district’s water dams have been affected by an invasive plant called water hyacinth ( Eichhornia crassipes ), both of problems require attention and remediation treatments. The objectives of this research were: a) to evaluate biochar derived from water hyacinth (H) in mining acid residues; and b) to compare its performance vs monopotassium phosphate (F), lime (L) and the phosphates mixtures with biochar (FH) or with lime (FL) by a bioassay of barley root growth, soluble metal and pH. In this investigation four substrates was used to emulate pollution gradients: 100 %-neutral pristine soil (M1); 100 %-acid mine residues (M4); and two mixtures soil: residues (w/w) of 65:35 (M2) and 35:65 (M3). The substrates were treated with the amendment (dose w/w): H (10 %-substrate), L (3.4 %-residues), F (0.06 %-soil + 0.6 %-residues), FH (0.06 %-soil + 0.6 %-residues + 10 %-substrate) y FL (0.06 %-soil + 0.6 %-residues + 3.4 %-residues) (22 total-treatments, blanks-included). This study shows that water hyacinth could be utilized as an acid mine residues treatment by converting it to biochar. It caused the increase of root length, pH and reduce the soluble Cu and Zn as with the others amendments when the residues were present. Although the reduction of soluble Pb with biochar was considerably lower than with lime in the residues-substrates.

Characterization of dissolved organic matter in the rhizosphere of phytostabilizer Athyrium wardii (Hook.) involved in enhanced metal accumulation when exposed to Cd and Pb co-contamination

The characterization of DOM and its effect on heavy metal solubility in soils have been widely concerned, while few concerns on the phytostabilization of multi-metal contaminated soils. A pot experiment was performed to characterize dissolved organic matter (DOM) in the rhizosphere of the mining ecotype (ME) and non-mining ecotype (NME) of Athyrium wardii (Hook.) when exposed to Cd and Pb simultaneously, and investigate its effect on Cd and Pb solubility in soils. The ME presented more DOM in the rhizosphere when exposed to Cd and Pb simultaneously than that exposed to single Cd or Pb, and also than the NME. The acid fractions (hydrophilic acid, hydrophobic acid) and hydrophilic fractions (hydrophilic acid, hydrophilic neutral, and hydrophilic base) were the dominant parts of DOM in the ME rhizosphere. The ME presented more acid and hydrophilic fractions in the rhizosphere when exposed to Cd and Pb simultaneously. Meanwhile, there were more O–H, C–O, N–H and C–H, assigned to carboxylic groups, phenolic groups, hydroxyl groups, and/or amino groups, present in DOM from the rhizosphere of ME when exposed to Cd and Pb simultaneously. These results highlighted the acid characteristics of DOM in the rhizosphere of ME when exposed to Cd and Pb simultaneously. DOM in the rhizosphere of ME thereby showed greater complexation degree for Cd (68%) and Pb (77%), thus showing greater ability to enhance Cd and Pb solubility in soils when exposed to Cd and Pb simultaneously. This is thereby considered to be one of the key processes for enhancing Cd and Pb uptake by the ME when exposed to Cd and Pb simultaneously.

An Accelerated, On-Site Bottom Ash Aging and Washing Treatment and Its Effect for Long-Term Leaching

Ash stabilization is important for realizing safe and reliable disposal sites and promoting MSW bottom ash (BA) recycling. An on-site technology that uses a modified detachable container and stabilizes BA with sprinkling water (watering) and flowing 100% CO2 through the ash layer (carbonation) was developed. Experimental verification of this technology was undertaken (Treatment condition: L/S = 0.6–0.7, 24 h duration, 2.2 t/time). Two treatment methods were investigated using unsieved BA: (1) sprinkling water only (2) sprinkling water combined with carbonation. In the verification test, the chlorine (Cl) content of the BA decreased by up to 72% after the watering treatment. The BA treated by watering and carbonation showed reduction in solubility of Pb by up to 90%. An exothermic reaction due to carbonation was also confirmed. In the lysimeter test (column size: o104 × 400 mmH) conducted to evaluate the long-term leaching performance of the BA treated to promote stabilization, leachate data was acquired over 400 days from both treated and untreated BA. It was confirmed that the leachate of BA treated with watering showed lower EC, cumulative Cl and TOC than untreated BA. The leachate of BA treated with watering and carbonation showed lower pH, Pb concentration and higher cumulative Cl, Ca after 400 days than the one treated with watering alone.

Evaluating controls on potentially toxic element release in circum-neutral mine water: a case study from the abandoned Pb\u2013Zn mines of Leadhills and Wanlockhead, South of Scotland, United Kingdom

Historic sulphidic Pb–Zn mining catchments at Leadhills and Wanlockhead, in the south of Scotland, UK have a legacy of mining of PbS (galena) and ZnS (sphalerite) from the twelfth century to the 1930s. The mining activities created tailing piles, ponds, adits and contaminated soils that contribute leaching and surface runoff of potentially toxic elements, particularly lead (Pb), which impact on the surface water and groundwater and are rapidly diluted in the wider catchment area. Studies by environmental regulators have shown that Pb, Cd and Zn in water can locally exceed the Environmental Quality Standards (EQS), particularly at Leadhills. To evaluate geochemical controls on release, 20 water sources (adits, surface water and near-surface groundwater) were sampled over four seasons (spring, summer, autumn and winter) over a 1-year period and characterized. Samples were circum-neutral pH from 6.3 to 7.9 (with average total dissolved solids < 55.0 mg/L), with no characteristics of acid mine drainage. The concentrations of PTEs in the water exceed UK EQS and WHO standards (and non-compliance on the Water Framework Directives). Geochemical modelling (GWB and PHREEQCv2) predicted mineral control on solubility which identified PbSO4 (anglesite), Fe2O3 ferric oxide (haematite), Fe3O4 (magnetite), FeCO3 (siderite), CaMg(CO3)2 (dolomite), CaCO3 (calcite) and Ca(Fe·Mg)(CO3)2 (ankerite) to be important. These were confirmed in solid phases analysed from tailings and sediments in contact with the hydrological cycle at the sites. Multivariate statistical analysis (PCA) of water samples associated with leaching through mine tailings showed strong seasonal variation with some elements (Fe, Cu, Cd, Pb, Na, Ca and Zn) with higher variance. The strong negative association of pH with soluble Zn, Cu, As, Cd and Pb highlights typical sulfide oxidation processes are taking place and supported by a positive correlation with temperature. Dissolution processes of mineral phases indicated by positive association of TDS and EC with Na, Ca and Zn. The data from PCA suggest contributions with potential for active generation of acid mine drainage and dissolution of solid phases influencing the release of PTEs into surface waters.

Algae (Raphidocelis subcapitata) mitigate combined toxicity of microplastic and lead on Ceriodaphnia dubia

They not only directly impact aquatic organisms, but also indirectly impact these organisms by interacting with background toxins in the environment. Moreover, under realistic environmental conditions, algae, a natural food for aquatic organisms, may alter the toxicity pattern related to MPs. In this research, we first examined the toxicity of MPs alone, and their effect on the toxicity of lead (Pb) on Ceriodaphnia dubia (C. dubia), a model aquatic organism for toxicity survey. Then, we investigated the effect of algae on the combined toxicity of MPs and Pb. We observed that, MPs significantly increased Pb toxicity, which was related to the increase in soluble Pb concentration and the intake of Pb-loaded MPs, both of which increased the accumulation of Pb in C. dubia. The presence of algae mitigated the combined toxicity of MPs and Pb, although algae alone increased Pb accumulation. Therefore, the toxicity mitigation through algae uptake came from mechanisms other than Pb accumulation, which will need further investigation.

Phase Diagram of the Pb-Se-Sn System

The Pb-Se-Sn ternary system is of interest to thermoelectric applications. Nevertheless, no phase diagram exists for the entire compositional regime at any temperature. Ternary Pb-Se-Sn alloys are equilibrated at 350°C and 500°C, and their equilibrium phases are determined. The isothermal sections of the equilibrium Pb-Se-Sn phase diagram at 350°C and 500°C are proposed based on the phase diagrams of the three constituent binary systems and ternary phase equilibria results in the literature and those determined in this study. No ternary compound is found. The phase relationships are similar at 350°C and 500°C. At both temperatures, binary compounds, α-PbSe and γ-SeSn, have very significant ternary solubility, but the ternary solubility of Pb in the Se2Sn phase is negligible. There are still unresolved questions about the type and shape of the liquid phase at the Se corner.

A consecutive 4-year elevated air temperature shaped soil bacterial community structure and metabolic functional groups in the rhizosphere of black locust seedlings exposed to lead pollution

Global warming may influence the bioavailability and mobility of heavy metals by stimulating or inhibiting plant growth, thereby influencing rhizosphere soil chemistry and microbial characteristics. Black locust has been widely planted in China as a promising species for afforestation programs, farmland shelterbelt projects, and soil restoration in mined areas because of its rapid growth and adaptability to environmental stressors. Here, we examined soil bacterial community structure and predicted bacterial metabolic function in the rhizosphere of black locust exposed to elevated temperature (+1.99 °C) and Pb for 4 years. Elevated temperature significantly (p < 0.05) reduced total carbon (TC), total nitrogen (TN), and total sulfur (TS) contents in above-ground parts but increased TC and TN contents in roots and seedling height under Pb exposure. Elevated temperature significantly (p < 0.05) increased Pb availability and raised pH, TC, TN, TS and water-soluble organic carbon (WSOC) contents, and the C:H ratio in rhizosphere soils under Pb exposure. The interactive effects between Pb and temperature on pH, TC, TH, TS, WSOC, and the C:H ratio were significant (p < 0.05). Elevated temperature significantly (p < 0.05) reduced the diversity and the richness of bacterial community, altered genus-level bacterial community composition, and improved (p < 0.05) the relative abundances of some bacteria involving in terpenoids and polyketides and xenobiotics biodegradation metabolism under Pb exposure. Canonical correspondence analysis indicated that pH, WSOC, C:N ratio, and soluble Pb were significant (p < 0.05) factors on the relative abundance of bacterial genera, such as Ochrobactrum and Sphingomnas. Overall, long-term elevated temperature resulted in changes in rhizosphere soil characteristics and Pb availability, thus affecting the bacterial community structure and metabolic functional groups. The conclusion helps us understand the response mechanism of soil bacteria in the rhizosphere to heavy metals under global warming scenarios.

An elastic semi IPN polymer hybrid for enhanced adsorption of heavy metals

An elastic semi IPN from guar gum (GG), xanthan gum (XG) and poly(acrylic acid) (PAA) was developed and used as a bioadsorbent for soluble Pb(II) and Hg(II) from water. The IPNs were developed using a photo-initiated crosslinking cum polymerization approach (benzophenone was used as an initiator) with a variable composition of the biopolymers (GG:XG fixed at 20:80 by mass) to PAA by mass (Biopolymers: PAA as 90:10, 80:20, 70:30 and 50:50, respectively). The hybrids were extensively characterized for microstructure, morphology, swelling, porosity and rheological behavior, both in dry and swelled conditions. Three grades of biosorbents namely 90:10, 80:20 and 70:30 showed an enhanced adsorption efficiency compared to the remaining ternary grades as well as the crosslinked binary grade of GG:XG (20:80 mass composition, used as a control), respectively. It was primarily due to high network strength (elasticity) cum flexibility (more liquid like behavior) of those three ternary grades under swollen condition followed by their higher swelling capacity and strongly negative zeta potential to attract the positively charged Pb(II) and Hg(II), respectively. The 80:20 grade (80 parts was the mass composed of XG:GG in 80:20 mass ratio and 20 parts was the mass of PAA) exhibited the maximum molecular effect and thus recorded the highest adsorption efficiency (93 % for Pb(II) with an adsorption capacity of 111.6 and 72 % of Hg(II) with an adsorption capacity of 86.4). Nevertheless, all the hybrids showed a strong pH dependant adsorption as the –COOH unit present in the network displayed a pH sensitive ionization. The adsorption was lower below the pH level of 4.0 (pKa of PAA at 4.5) while drastically improved beyond that. On additional note, the adsorbate dose was also found to affect the adsorption efficiency whereby a maximum dose of 300 ppm of both Pb(II) and Hg(II) was found to be most effective for adsorption.

Development of Al-Based Metallic Glass Composites Containing Pb-Rich Crystalline 2&lt;sup&gt;nd&lt;/sup&gt; Phase

Liquid immiscible alloy systems present a unique opportunity for designing composites with sphere-dispersed and/or interconnected microstructures. Herein, we demonstrate that the addition of Pb in Al&lt;sub&gt;84&lt;/sub&gt;TM&lt;sub&gt;10&lt;/sub&gt;RE&lt;sub&gt;6&lt;/sub&gt; (TM=Ni,Co,Fe,Ti, RE=La,Ce,Nd,Gd,Y) metallic glasses can result in liquid-liquid phase separation in a liquid immiscibility gap and substantially solidifies into a Pb-rich crystalline phase and Al-rich amorphous phase. The Pb-rich phase has a spherical shape and is dispersed in the Al-based metallic glass matrix. The average diameter of the Pb-rich spheres changed from 75 ± 10 nm near the wheel side (fastest cooling region) to 138 ± 32 nm near the center of the ribbon (slowest cooling region), which exhibited a melting temperature of about 599 K, close to that of pure Pb (Tm = 600.5 K), due to the low solubility of Pb and other constituent elements. Interestingly, the dispersed Pb-rich 2&lt;sup&gt;nd&lt;/sup&gt; phase in the Al-based metallic glass matrix causes delayed crack propagation and enhanced fatigue lifetime due to crack blocking and filling by partial liquifaction. These results provide a guideline for how to design promising Al-based metallic glasses containing sphere-dispersed 2&lt;sup&gt;nd&lt;/sup&gt; phase with low melting temperature, which is a key step in developing damage-tolerant metallic glass composites with a liquid-based healing mechanism.

Effect of Bi doping on thermoelectric properties of Ge0.90−xPb0.10BixTe compounds

Doping is an effective way to optimize the performance of thermoelectric materials. In order to investigate the effect of Bi doping on microstructures and thermoelectric properties of Ge0.90Pb0.10Te, a series of Ge0.90−xPb0.10BixTe compounds were prepared by a melting-quenching-annealing process followed by spark plasma sintering. The Bi doping on Ge site acts as an electron donor, which effectively optimized the carrier concentration from 1.1 × 1021 cm−3 to 3.5 × 1020 cm−3. Besides, the lattice distortions originated from Bi doping further promoted the solubility of Pb in the GeTe matrix, which have great advantage for obtaining lower thermal conductivity compared with pristine Ge0.90Pb0.10Te sample. Low lattice thermal conductivity of about 0.77 W/mK was obtained in Ge0.86Pb0.10Bi0.04Te owing to the additional lattice defects introduced by Bi doping. Consequently, the highest ZT of 1.1 was obtained in Ge0.86Pb0.10Bi0.04Te at 600 K with an average ZT of 0.6. These results have confirmed that Bi doing is an efficient way to boost the thermoelectric performance of GeTe-based alloys.

Exposure to Pb-halide perovskite nanoparticles can deliver bioavailable Pb but does not alter endogenous gut microbiota in zebrafish.

Lead-halide perovskite nanoparticles (NPs) are a new technology, and investigation of toxicity is of considerable importance due to the potential lead (Pb) release into the environment. The aim of the study was to investigate aqueous and dietary toxicity of Pb-halide perovskite NP and Pb in zebrafish Danio rerio. Perovskite NP toxicity was evaluated in zebrafish by mortality, gene expression, histopathology, and phylogenetic analysis of gut microbiota. Zebrafish larvae were exposed to five Pb-halide perovskite NPs in parallel with Pb(NO3)2 exposures, and zebrafish adults were exposed to the three perovskite NPs that caused the strongest effect and Pb(NO3)2. No median lethal concentration (LC50) was observed for zebrafish larvae exposed to up to 200mg/L of perovskite NPs for 96h. Mortality, metallothionein 2 (mt2) and δ-aminolevulinic acid dehydratase (ala-d) gene expression (24-h exposure) in zebrafish larvae after aqueous perovskite NPs exposures did not differ from total Pb concentration - response curves. The lack of differences in mortality and gene expression between perovskite NPs and soluble Pb after aqueous exposure suggest that toxicity from perovskite NPs can be attributed to bioavailable Pb rather than nano-specific effects. Induction of mt2 and reduction of ala-d expression levels in liver tissues showed Pb bioavailability after 2-d and 4-d dietary exposure to perovskite-spiked feeds. Changes in gut microbiota of adult zebrafish were detected after 14-d exposure to Pb-spiked food, but no changes were detected from perovskite-NP spiked food. The phylogenetic analysis identified different microbiome profiles of Pb-fed fish compared to perovskite-fed fish suggesting a different mechanism of toxicity. Exposure to Pb-halide perovskite NPs led to absorption of Pb likely from release of Pb ions rather than absorption of NPs. Pb-halide perovskite NPs can release bioavailable Pb and this needs to be considered during the development of this technology.