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At least 19 records

Preparation of high density heavy metal fluoride glasses with extended ultraviolet and infra red ranges, and such high density heavy metal fluoride glasses

A heavy metal fluoride glass composition range (in mol percent) consisting essentially of: (16-30)BaF.sub.2.(8-26)HfF.sub.4.(6-24)InF.sub.3 or GaF.sub.3.(4-16)CdF.sub.2.(6-24)YbF.sub.3.(4-22)ZnF.sub.2. In an alternative embodiment, a heavy metal fluoride glass composition range (in mol percent) comprises (16-30)BaF.sub.2.(8-26)HfF.sub.4.(6-24) of (0-24)InF.sub.3, (0-24)GaF.sub.3 and (0-19)AlF.sub.3.(1-16)CdF.sub.2.(6-24)YbF.sub.3.(4-26)ZnF.sub.2. A preferred heavy metal fluoride glass produced in accordance with the present invention comprises a composition (in mol %) and comprises about 26BaF.sub.2.18HfF.sub.4.7InF.sub.3.5GaF.sub.3.10CdF.sub.2.18YbF.sub.3. 16ZnF.sub.2. A preferred heavy metal fluoride glass has maximum thickness of most preferably about 3 mm. Another preferred heavy metal fluoride glass comprises a composition (in mol %) and comprises about 26BaF.sub.2.18HfF.sub.4.12AlF.sub.3.10CdF.sub.2.18YbF.sub.3.16ZnF.sub.2.

Martin, Steven W.↗

Enhancing the Phytoremediation of Heavy Metals by Combining Hyperaccumulator and Heavy Metal-Resistant Plant Growth-Promoting Bacteria

Heavy metals (HMs) have become a major environmental pollutant threatening ecosystems and human health. Although hyperaccumulators provide a viable alternative for the bioremediation of HMs, the potential of phytoremediation is often limited by the small biomass and slow growth rate of hyperaccumulators and HM toxicity to plants. Here, plant growth-promoting bacteria (PGPB)-assisted phytoremediation was used to enhance the phytoremediation of HM-contaminated soils. A PGPB with HM-tolerant (HMT-PGPB), Bacillus sp. PGP15 was isolated from the rhizosphere of a cadmium (Cd) hyperaccumulator, Solanum nigrum . Pot experiments demonstrated that inoculation with strain PGP15 could significantly increase the growth of S. nigrum . More importantly, strain PGP15 markedly improved Cd accumulation in S. nigrum while alleviating Cd-induced stress in S. nigrum . Specifically, PGP15 inoculation significantly decreased the contents of H 2 O 2 , MDA, and O 2 · − in S. nigrum , while the activities (per gram plant fresh weight) of SOD, APX, and CAT were significantly increased in the PGP15-inoculated plants compared with the control sample. These results suggested that the interactions between strain PGP15 and S. nigrum could overcome the limits of phytoremediation alone and highlighted the promising application potential of the PGPB-hyperaccumulator collaborative pattern in the bioremediation of HM-contaminated soils. Furthermore, the PGP15 genome was sequenced and compared with other strains to explore the mechanisms underlying plant growth promotion by HMT-PGPB. The results showed that core genes that define the fundamental metabolic capabilities of strain PGP15 might not be necessary for plant growth promotion. Meanwhile, PGP15-specific genes, including many transposable elements, played a crucial role in the adaptive evolution of HM resistance. Overall, our results improve the understanding of interactions between HMT-PGPB and plants and facilitate the application of HMT-PGPB in the phytoremediation of HM-contaminated soils.

Zhang, Yong↗

Amidoxime-Functionalized Macroporous Carbon Self-Refreshed Electrode Materials for Rapid and High-Capacity Removal of Heavy Metal from Water

Heavy metal pollution continues to be one of the most serious environmental problems which has attracted major global concern. Here, a rapid, high-capacity, yet economical strategy for deep cleaning of heavy metals ions in water is reported based on amidoxime-functionalized macroporous carbon electrode materials. The active sites of our material can be self-refreshed during the electrochemical removal process, which is different from traditional methods. The novel filter device in this work can purify contaminated water very rapidly (3000 L h –1 m –2 ), and can decrease heavy metal ion concentrations to below 5 ppb with a very short contact time (only 3 s). The original treatment efficiency of the device can be retained even after 1 week of continuous device operation. An extremely high removal capacity of over 2300 mg g –1 can be achieved with 2–3 orders of magnitude higher efficiency than that of surface adsorption-based commercial filters without any decay. Additionally, the cost of energy consumed in our method is lower than $6.67 × 10 –3 per ton of wastewater. We envision that this approach can be routinely applied for the rapid, efficient, and thorough removal of heavy metals from both point-of-use water and industrial wastewater.

36 MATERIALS SCIENCE↗

The Effects of Gravity on the Crystallization Behavior of Heavy Metal Fluoride Glasses

Heavy metal fluoride glasses are used in such applications as fiber lasers and laser amplifiers. ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) is one of the more commonly used heavy metal fluoride glasses. ZBLAN is an infrared transmitter and has a theoretical attenuation coefficient of 0.002 db/km. However, due to impurities and small crystallites this attenuation coefficient has not been achieved to date. ZBLAN is a fragile glass which can lead to rapid crystallization, if the glass is not cooled rapidly to below the glass transition temperature or if the glass is reheated near the crystallization temperature for any period of time. Studies carried on at Marshall Space Flight Center and the University of Alabama in Huntsville since 1993 have shown that heating ZBLAN glass at the crystallization temperature in reduced gravity results in a suppression of crystallization when compared to ZBLAN processed in unit gravity. These studies utilized NASA's KC-135 aircraft and the Conquest sounding rocket. In the first series of experiments, short lengths of ZBLAN fiber were heated to the crystallization temperature in reduced gravity on board the KC- 135 and the Conquest sounding rocket and compared with fibers heated in unit gravity. The fibers processed in reduced gravity showed no evidence of crystallization when studied with x-ray diffraction and scanning electron microscopy. However, the fibers processed in unit gravity were completely crystallized. Subsequent experiments included heating small pieces of ZBLAN glass at the crystallization temperature while viewing with a video camera to follow the crystallization phenomenon. In this experiment crystallization was observed in reduced gravity, however, it was suppressed when compared to heating in unit gravity. In the most recent experiment on board the KC-135, rapid thermal analysis of ZBLAN was performed. A mechanism to explain the observations has been proposed. This mechanism is based on shear thinning whereby, the glass undergoes a reduction in viscosity in the 10(exp 5) - 10(exp 7) poise range, allowing more rapid diffusion and thus crystallization. It is proposed that this mechanism is suppressed in reduced gravity. An experiment is presently being conducted to test this theory. With increased knowledge of ZBLAN behavior in reduced gravity, three low earth orbit tiber drawing facilities have been designed. One would be suitable for use on the International Space Station, another while aboard the Space Shuttle and the third system is a fully automated facility which would operate independently of the ISS or Shuttle in a free float mode. The primary benefits of free floating a facility in LEO includes a higher quality of microgravity and reduced safety concerns since it is not in a manned environment.

Tucker, Dennis S.↗

A compact dication source for Ba 2+ tagging and heavy metal ion sensor development

Here, we present a tunable metal ion beam that delivers controllable ion currents in the picoamp range for testing of dry-phase ion sensors. Ion beams are formed by sequential atomic evaporation and single or multiple electron impact ionization, followed by acceleration into a sensing region. Controllability of the ionic charge state is achieved through tuning of electrode potentials that influence the retention time in the ionization region. Barium, lead, and cadmium samples have been used to test the system, with ion currents identified and quantified using a quadrupole mass analyzer. Realization of a clean Ba 2+ ion beam within a bench-top system represents an important technical advance toward the development and characterization of barium tagging systems for neutrinoless double beta decay searches in xenon gas. This system also provides a testbed for investigation of novel ion sensing methodologies for environmental assay applications, with dication beams of Pb 2+ and Cd 2+ also demonstrated for this purpose.

47 OTHER INSTRUMENTATION↗

Post-synthetically modified metal-organic frameworks for selective binding of heavy metal ions in water

A composition of matter for selective binding of at least one heavy metal comprising at least one porous metal-organic framework (MOF) with unsaturated coordination sites, at least one organic ligand functionalized with at least one functional group tailored to bind to the at least one MOF, and at least one separate functional group tailored to bind to the at least one heavy metal.

Britt, David↗

Direct/Alternating Current Electrochemical Method for Removing and Recovering Heavy Metal from Water Using Graphene Oxide Electrode

Treatment of heavy-metal pollution in both point-of-use water and industrial wastewater is critical in protecting human health and the environment. Current methods for heavy-metal treatment in both sources have limitations. For point-of-use water, current methods usually suffer from limited capacity and difficulties in spontaneously removing multiple heavy metals. For industrial wastewater, current methods greatly reduce the value of heavy metal by precipitating them as sludge which requires further treatment. Here we developed an electrochemical method that can treat both low-concentration and high-concentration heavy-metal pollution using either direct current (DC) or alternating current (AC) electrodeposition with graphene-oxide-modified carbon felt electrode (CF-GO). The graphene oxide provides a high density of surface functional groups to assist the electrodeposition. The electrodeposition method showed 2 orders of magnitude higher capacity (>29 g heavy metal for 1 g of graphene oxide) compared with traditional adsorption methods. For low levels of heavy-metal pollution in point-of-use water, DC electrodeposition with a CF-GO electrode can reduce single heavy-metal ion pollution (Cu, Cd, and Pb) as well as multiple ion mixtures to below safe water drinking levels. This method can tolerate a much wider range of heavy-metal pollution in point-of-use water than traditional adsorption methods. For high-level pollution in industrial wastewater, AC electrodeposition can recover >99.9% heavy-metal ions. Finally, by tuning the AC frequency and voltage, the electrodeposition method can further selectively recover Cu, Cd, and Pb separately, which adds values to the heavy-metal removal process.

36 MATERIALS SCIENCE↗

Organic compounds alter the preference and rates of heavy metal adsorption on ferrihydrite

The availability of heavy metals in terrestrial environments is largely controlled by their interactions with minerals and organic matter, with iron minerals having a particularly strong role in heavy metal fate. Because soil organic matter contains a variety of compounds that differ in their chemical properties, the underlying impact organic matter-soil mineral associations bestow on heavy metal binding is still unresolved. Here, we systematically examine the binding of Cd, Zn and Ni by a suite of organic-ferrihydrite assemblages, chosen to account for various compound chemistries within soil organic matter. We posited that organic compound functionality would dictate the extent of association with the organic-ferrihydrite assemblages. Increased heavy metal binding to the assemblages was observed and attributed to the introduction of additional binding sites by the organic functional groups with differing metal affinities. Furthermore, the relative increase depended on the metal's Lewis acidity and followed the order Cd > Zn > Ni, whereas the reverse order was obtained for metal binding by pristine ferrihydrite (Ni > Zn > Cd). Citric acid-, aspartic acid- and cysteine-ferrihydrite assemblages also enhanced the metal binding rate. X-ray absorption spectroscopy revealed that the organic coating contributed significantly to Zn binding by the assemblages, despite relatively low organic surface coverage. Our findings provide valuable information on the nature of heavy metal-organic-mineral interactions and metal adsorption processes regulating their bioavailability and transport.

54 ENVIRONMENTAL SCIENCES↗

Plant genotype and rhizobia strain combinations strongly influence the transcriptome under heavy metal stress conditions in Medicago truncatula

Heavy metals such as cadmium (Cd) and mercury (Hg) pose significant threats to plant health and food safety as they are absorbed from the environment. Legumes are generally considered sensitive to heavy metals but possess standing genetic variation for accumulation and tolerance to toxic ions. We conducted a transcriptomic analysis on hydroponically and soil grown Medicago truncatula plants to investigate gene expression responses to Cd and Hg exposure in roots, leaves, and nodules. By using plant genotypes with varying metal tolerance or accumulation levels, we observed distinct clustering of gene ontologies, indicating tissue-specific, genotype-specific, and metal-specific gene expression patterns. Considering the symbiotic relationship between legumes and nitrogen-fixing bacteria, we further examined plant phenotypes and transcriptomes of plant genotypes with contrasting Hg accumulation levels and inoculated them with high or low Hg-tolerant Sinorhizobium medicae strains that have presence-absence variation for a mercury reductase (Mer) operon. Host plants inoculated with the Hg-tolerant rhizobia strain possessing a Mer operon exhibited less reduction in nodule number and plant biomass. A smaller reduction in iron (Fe) distribution in nodules after Hg stress was measured using X-ray Fluorescence (XRF) imaging. Dual transcriptome (host plant and bacteria) analysis of nodules revealed a remarkable decrease in the number of differentially expressed genes (DEGs) and clustering of gene ontologies in plants inoculated with the Hg-tolerant rhizobia strain, including symbiosis related genes. This finding suggests that the Hg-tolerant rhizobia strain has the potential to mitigate Hg stress in host plants. Furthermore, we observed genotype by-genotype interactions between the high Hg accumulating plant genotype and the Hg-tolerant rhizobia strain. These findings provide insights into enhancing plant resilience in contaminated environments through optimizing legume-rhizobia interactions for heavy metal tolerance.

59 BASIC BIOLOGICAL SCIENCES↗

Mixed heavy metal stress induces global iron starvation response

Abstract Multiple heavy metal contamination is an increasingly common global problem. Heavy metals have the potential to disrupt microbially mediated biogeochemical cycling. However, systems-level studies on the effects of combinations of heavy metals on bacteria are lacking. For this study, we focused on the Oak Ridge Reservation (ORR; Oak Ridge, TN, USA) subsurface which is contaminated with several heavy metals and high concentrations of nitrate. Using a native Bacillus cereus isolate that represents a dominant species at this site, we assessed the combined impact of eight metal contaminants, all at site-relevant concentrations, on cell processes through an integrated multi-omics approach that included discovery proteomics, targeted metabolomics, and targeted gene-expression profiling. The combination of eight metals impacted cell physiology in a manner that could not have been predicted from summing phenotypic responses to the individual metals. Exposure to the metal mixture elicited a global iron starvation response not observed during individual metal exposures. This disruption of iron homeostasis resulted in decreased activity of the iron-cofactor-containing nitrate and nitrite reductases, both of which are important in biological nitrate removal at the site. We propose that the combinatorial effects of simultaneous exposure to multiple heavy metals is an underappreciated yet significant form of cell stress in the environment with the potential to disrupt global nutrient cycles and to impede bioremediation efforts at mixed waste sites. Our work underscores the need to shift from single- to multi-metal studies for assessing and predicting the impacts of complex contaminants on microbial systems.

59 BASIC BIOLOGICAL SCIENCES↗

Thiol-Functionalized Adsorbents through Atomic Layer Deposition and Vapor-Phase Silanization for Heavy Metal Ion Removal

The removal of toxic heavy metal ions from water resources is crucial for environmental protection and public health. In this study, we address this challenge by developing a surface functionalization technique for the selective adsorption of these contaminants. Our approach involves atomic layer deposition (ALD) followed by vapor-phase silanization of porous substrates. We utilized porous silica gel powder (similar to 100 mu m particles, 89 m 2 /g surface area, similar to 30 nm pores) as an initial substrate. This powder was first coated with similar to 0.5 nm ALD Al 2 O 3 , followed by vapor-phase grafting of a thiol-functional silane. The modified powder, particularly in acidic conditions (pH = 4), showed high selectivity in adsorbing Cd(II), As(V), Pb(II), Hg(II), and Cu(II) heavy metal ions in mixed ion solutions over common benign ions (e.g., Na, K, Ca, and Mg). Langmuir adsorption isotherms and breakthrough adsorption studies were conducted to assess heavy metal binding affinity and revealed the order of Cd(II) < Pb(II) < Cu(II) < As(V) < Hg(II), with a significantly higher affinity for As(V) and Hg(II) ions. Time-dependent uptake studies demonstrated rapid removal of heavy metal ions from aqueous environments, with Hg(II) exhibiting the fastest adsorption kinetics on thiol-modified surfaces. Finally, these findings highlight the potential of ALD and vapor-phase silanization to create effective adsorbents for the targeted removal of hazardous contaminants from water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Resistance of Resting Eggs of Cladoceran Moina macrocopa to the Effect of Heavy Metals

The research aimed to determine critical concentrations of heavy metals at which survival of resting eggs of the cladoceran Moina macrocopa is negatively affected. Resting eggs’ viability was not affected over a 30-days exposure towards copper, cadmium, zinc or nickel at concentrations up to 60–70 g/L. When resting eggs were exposed to sediment contaminated with heavy metals for 8 months, the hatching success was affected at 30 g copper/kg. Thus, resting eggs of Cladocera can tolerate heavy metals at concentrations that far exceed lethal concentrations of heavy metals to active life stage and exceed low or moderate levels of environmental pollution. Follow up investigation of life table parameters of hatchlings from resting eggs exposed to heavy metals demonstrated that neither lifespan nor fecundity of hatchlings differ from control animals. These results demonstrate that zooplankton may rapidly recover from resting egg bank once aquatic habitat becomes unpolluted.

54 ENVIRONMENTAL SCIENCES↗

Shotgun metagenomics analysis indicates Bradyrhizobium spp. as the predominant genera for heavy metal resistance and bioremediation in a long-term heavy metal-contaminated ecosystem

ABSTRACT Ten soil cores were collected from the long-term heavy metal-contaminated Savannah River Site (SRS) and studied using shotgun metagenomics. In-line with our previous reports, Bradyrhizobium spp. dominated the SRS soils, and thus we recommend that SRS bioremediation studies target the Bradyrhizobium genus.

Agashe, Rohan↗