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At least 1,009 records · Page 56

Phytoremediation of a nitrogen-contaminated desert soil by native shrubs and microbial processes

Here, we combined phytoremediation and soil microbial nitrification and denitrification cycles to reduce nitrate and ammonium levels at a former uranium mill site near Monument Valley, Arizona. Ammonia used in uranium extraction was present throughout the soil profile. Sulfate,applied as sulfuric acid to solubilize uranium, was also present in the soil. These contaminants were leaching from a denuded area where a tailings pile had been removed and were migrating away from the site in groundwater. We planted the source area with two deep-rooted native shrubs, Atriplex cansescens and Sarcobatus vermiculatus , and irrigated transplants for 11 years at 20% the rate of potential evapotranspiration to stimulate growth, then discontinued irrigation for 4 years. Over 15 years, total nitrogen levels dropped 82%, from 347 to 64 mg kg –1 . Analysis of δ 15 N supported our hypothesis that coupled microbial nitrification and denitrification processes were responsible for the loss of N. Soil sulfate levels changed little; however, evapotranspiration reduced sulfate leaching into the aquifer. For arid sites where traditional pump-and-treat methods are problematic, the Monument Valley data suggest that alternatives that incorporate native plants and rely on vadose zone biogeochemistry and hydrology could be a sustainable remediation for nitrogen contaminated soil.

54 ENVIRONMENTAL SCIENCES↗

Effects of spin contamination on estimating bond dissociation energies of polycyclic aromatic hydrocarbons

The objective of this work is to investigate the impact of spin contamination on the prediction of the enthalpies of formation of Polycyclic Aromatic Hydrocarbon (PAH) radicals and of the bond dissociation energies of their precursor molecule. These PAH radicals play a major role in the mass growth of soot precursors leading ultimately to the first soot particles. In this work, we highlights the errors due to spin contamination by comparing spin‐unrestricted open‐shell calculations (UHF, UMP2, and Quadratic CI singles and doubles [QCISD(T)]) with spin‐restricted open‐shell calculations (ROHF, ROMP2, and ROCCSD(T)). The results suggest that one should be very careful using any of the spin‐unrestricted methods (even QCISD (T)) unless the values are extremely close to the theoretical value. Following these observations, we propose a new set of best‐estimates for the enthalpies of formation of these critical PAH radicals using spin‐restricted open‐shell ROMP2 and RCCSD(T) calculations. © 2015 Wiley Periodicals, Inc.

Blanquart, Guillaume↗

Mechanisms of Interface Cleaning in Heterostructures Made from Polymer‐Contaminated Graphene

Abstract Heterostructures obtained from layered assembly of 2D materials such as graphene and hexagonal boron nitride have potential in the development of new electronic devices. Whereas various materials techniques can now produce macroscopic scale graphene, the construction of similar size heterostructures with atomically clean interfaces is still unrealized. A primary barrier has been the inability to remove polymeric residues from the interfaces that arise between layers when fabricating heterostructures. Here, the interface cleaning problem of polymer‐contaminated heterostructures is experimentally studied from an energy viewpoint. With this approach, it is established that the interface cleaning mechanism involves a combination of thermally activated polymer residue mobilization and their mechanical actuation. This framework allows a systematic approach for fabricating record large‐area clean heterostructures from polymer‐contaminated graphene. These heterostructures provide state‐of‐the‐art electronic performance. This study opens new strategies for the scalable production of layered materials heterostructures.

Huang, Zhujun↗

Extrapolating Contaminant Effects from Individuals to Populations: A Case Study on Nanoparticle Toxicity to Daphnia Fed Environmentally Relevant Food Levels

Ecological risk assessment (ERA) is charged with assessing the likelihood a chemical will have adverse environmental or ecological effects. When assessing the risk of a potential contaminant to biological organisms, ecologists are most concerned with the sustainability of populations of organisms, rather than protecting every individual. However, ERA most commonly relies on data on the effect of a potential contaminant on individuals because these experiments are more feasible than costly population-level exposures. In this work, we address the challenge of extrapolating these individual-level results to predict population-level effects. Previous per-capita population growth rate estimates calculated from individual-level exposures of Daphnia pulicaria to silver nanoparticles (AgNPs) at different food rations predict a critical daily food requirement for daphnid populations exposed to 200 μg/L AgNPs to avoid extinction. To test this, we exposed daphnid populations to the same AgNP concentration at three different food inputs, with the lowest ration close to the extinction threshold predicted from data on individuals. The two populations with the higher food inputs persisted, and the population with the lowest food input went extinct after 50 days but did persist through two generations. Further, we demonstrate that we can extrapolate between these levels of biological organization by parameterizing an individual-level biomass model with data on individuals’ response to AgNPs and using these parameters to predict the outcome for control and AgNP-exposed populations. Key to successful extrapolation is careful modeling of temporal changes in resource density, driven by both the experimental protocols and feedback from the consumer. The implication for ecotoxicology is that estimates of extinction thresholds based on studies of individuals may be reliable predictors of population outcomes, but only with careful treatment of resource dynamics.

54 ENVIRONMENTAL SCIENCES↗

Reducing host DNA contamination in 16S rRNA gene surveys of anthozoan microbiomes using PNA clamps

Efforts to study the microbial communities associated with corals can be limited by inefficiencies in the sequencing process due to high levels of host amplification by universal bacterial 16S rRNA gene primers. Here, we develop an inexpensive peptide nucleic acid (PNA) clamp that binds to a target sequence of host DNA during PCR and blocks amplification. We then test the ability of this PNA clamp to mitigate host contamination and increase overall microbial sequence coverage on samples from three coral species: the gorgonians Eunicea flexuosa and Gorgonia ventalina, and the scleractinian Porites panamensis. The 20-bp PNA clamp was designed using DNA from E. flexuosa. Adding the PNA clamp during PCR increased the percentage of microbial reads in E. flexuosa samples more than 11-fold. Microbial community diversity was similar without- and with-PNA clamps, as were the relative frequencies of the ten most abundant ASVs (amplicon sequence variants), indicating that the clamps successfully blocked host DNA amplification while simultaneously increasing microbial DNA amplification proportionally across the most abundant taxa. The reduction of E. flexuosa DNA correlated with an increase in the abundance of rarer taxa. The clamp also increased the average percentage of microbial reads in another gorgonian, G. ventalina, by 8.6-fold without altering the microbial community beta diversity, and in a distantly related scleractinian coral, P. panamensis, by nearly double. The reduction of host contamination correlated with the number of nucleotide mismatches between the host amplicon and the PNA clamp. The PNA clamp costs as little as $0.48 per sample, making it an efficient and cost-effective solution to increase microbial sequence coverage for high-throughput sequencing of coral microbial communities.

16S rRNA gene sequencing↗

Distribution of neptunium and plutonium in New Mexico lichen samples ( Usnea arizonica ) contaminated by atmospheric fallout

In this study, the concentrations of 237 Np, 239 Pu and 240 Pu were determined in lichen samples ( Usnea arizonica ) that were collected from ten locations in New Mexico between 2011 and 2013 using isotope dilution inductively-coupled plasma mass spectrometry (ID-ICP-MS). The observed isotopic ratios for 237 Np/ 239 Pu and 240 Pu/ 239 Pu indicate trace contamination from global and regional fallout (e.g. Trinity test and atmospheric testing at the Nevada Test Site). The fact that actinide contamination is detected in recent lichen collections suggests continuous re-suspension of fallout radionuclides even 50 years after ratification of the Limited Test Ban Treaty.

54 ENVIRONMENTAL SCIENCES↗

Chapter 12 - Addressing Groundwater Fluoride Contamination Using Inexpensively Processed Bauxite

Globally, 200 million people are at risk of adverse health effects from drinking groundwater contaminated with high fluoride concentrations that exceed the World Health Organization's maximum contaminant limit (WHO MCL=1.5ppmF-). Although many defluoridation technologies have been demonstrated to work in lab, most have proven inappropriate for impoverished rural regions of developing countries because they are cost-prohibitive, require skilled labor, or are difficult to scale. The authors submit evidence for the use of bauxite, an aluminum-rich ore, as a potentially inexpensive, effective, and scalable defluoridation technology. Specifically, we present results from experimental studies that characterize globally diverse bauxite ores, elucidate fluoride removal mechanisms, and establish proof of concept that mildly processed bauxite can cost-effectively remediate field-relevant fluoride concentrations in synthetic and real groundwater matrices at field-relevant kinetics. We discuss practical implications of these research findings and highlight remaining challenges and unknowns that need to be further studied before implementing the proposed defluoridation process in the field.

Gadgil, AJ↗

Integrating Analytical Solutions and U-Net Model for Predicting Groundwater Contaminant Plumes in Pump-and-Treat Systems

Pump-and-treat (P&T) is a common technique for groundwater remediation involving the extraction and treatment of contaminated water above ground. Optimizing the design and operation of the P&T well network is essential for maximizing the system’s effectiveness and efficiency. However, this optimization often necessitates many model evaluations, leading to computationally demanding tasks. This study introduces a novel approach that integrates analytical solutions for groundwater dynamics with the U-Net (Ronneberger et al., 2015) deep learning framework to predict groundwater contaminant plume migration under dynamic pumping conditions. By incorporating the Thiem equation (Thiem, 1906) into the input preprocessing, the U-Net model transforms sparse well data into a continuous spatial field that captures the hydraulic impacts of pumping activities. This integration enables the model to leverage both deep learning capabilities and classical physics-based groundwater theories, enhancing prediction accuracy and computational efficiency. These advancements can facilitate rapid, large-scale evaluations of P&T optimization simulations, allowing for timely and effective decision-making in well placement and system management. We demonstrate the model's robust performance across both simplified transient 2D models and a more complex 3D heterogeneous site model at the 200 West P&T facility at the Hanford Site. The U-Net-based model offers substantial computational advantages, reducing simulation times significantly compared to full physics-based models and providing a powerful tool for rapid site evaluation and P&T system optimization, such as evaluating alternative P&T well network designs. Our findings highlight the potential of advanced machine learning models to significantly enhance the efficiency and sustainability of groundwater remediation efforts, offering a novel application of U-Net architecture in environmental science.

Pump-and-treat↗

On silica's roles in controlling americium migration in contaminated sediments

Two studies in the early 1980s described the leaching behavior of americium (Am) disposed as part of acidic high-salt processing wastes from the Hanford Site’s Plutonium Finishing Plant to nearby ground sediments. Here these batch leach experiments showed that the Am concentrations followed a linear log [Am] versus pH relationship with a slope of –1. Column leach experiments in the second study, however, did not follow this relationship and only ~30% of the americium desorbed even after extensive column leaching. Here, the 1980s research is re-examined along with previously unpublished information and, in light of recent published work, a plausible mechanism is proposed to explain these phenomena. Amorphous silica in the contaminated sediments is postulated to be the substrate responsible for both the exchangeable Am available for leaching and the retained low-leachable Am made evident in the column leach experiments. The exchangeable Am 3+ in the contaminated sediment leach experiments behaves with pH dependence similar to that observed for uptake onto amorphous silica of sodium (Na + ), calcium (Ca 2+ ), barium (Ba 2+ ), cadmium (Cd 2+ ), uranyl (UO 2 2+ ), ferric (Fe 3+ ), chromic (Cr 3+ ), cupric (Cu 2+ ), plumbous (Pb 2+ ), uranium(IV) (U 4+ ), plutonium(IV) (Pu 4+ ), zirconium (Zr 4+ ), analogue lanthanide (gadolinium, Gd 3+ , europium, Eu 3+ , and lutetium, Lu 3+ ) and curium (Cm 3+ ) ions as well as other studies with Am 3+ . Correspondingly, the residual low-leachable Am 3+ revealed in the column leach experiments is attributed to incorporation of Am 3+ within amorphous silica by dynamic Am 3+ sorption and silica precipitation processes.

58 GEOSCIENCES↗

Development of ultralow-background cryogenic calorimeters for the measurement of surface α contamination

Next-generation experiments searching for rare events must satisfy increasingly stringent requirements on the bulk and surface radioactive contamination of their active and structural materials. The measurement of surface contamination is particularly challenging, as no existing technology is capable of separately measuring parts of the 232 Th and 238 U decay chains that are commonly found to be out of secular equilibrium. We will present the results obtained with a detector prototype consisting of 8 silicon wafers of 150mm diameter instrumented as bolometers and operated in a low-background dilution refrigerator at the Gran Sasso Underground Laboratory of INFN, Italy. Furthermore, the prototype was characterized by a baseline energy resolution of few keV and a background <100nBq/cm 2 in the full range of α energies, obtained with simple procedures for cleaning of all employed materials and no specific measures to prevent recontamination. Such performance, together with the modularity of the detector design, demonstrate the possibility to realize an alpha detector capable of separately measuring all alpha emitters of the 232 Th and 238 U chains, possibly reaching a sensitivity of few nBq/cm 2 .

07 ISOTOPE AND RADIATION SOURCES↗

Stannous chloride as a tool for mercury stripping in contaminated streams: Experimental assessment of toxicity in an invertebrate model species

In this work, the chronic toxicity of an innovative Hg water treatment system using tin (Sn) (II) chloride (SnCl 2 ) followed by air stripping was assessed through measurements of survival, growth, and reproduction rate in the freshwater cladoceran Ceriodaphnia dubia, a model species for toxicity testing. We first calculated the concentrations of Hg causing 25% reduction in survival and reproduction (Lethal or Inhibition Concentrations, or LC 25 and IC 25 , for survival and reproduction, respectively) through exposure to aqueous Hg at concentrations ranging from 0 to 25,000 ng L -1 . Then, we treated media (DMW and natural stream water) contaminated with Hg at LC 25 and IC 25 concentrations with SnCl 2 at a Sn:Hg stoichiometric ratio of 8:1 and air stripping and exposed C. dubia to this Sn-amended media. Our results showed that Hg significantly affected survival, reproduction rates and impaired growth. SnCl 2 -treatment removed 100% of the Hg from the media at all concentrations tested with no deleterious effects on survival, growth and reproduction. Our results confirmed the efficacy of SnCl 2 in removing aqueous Hg from stream water and showed that the added Sn did not impact C. dubia at the concentrations tested, supporting the suitability of SnCl 2 -based treatments in appropriate Hg-contaminated environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Failure analysis of solid oxide fuel cells nickel-yttria stabilized zirconia anode under siloxane contamination

In this study, the failure process of the solid oxide fuel cell (SOFC) Ni-yttria-stabilized zirconia (YSZ) anode is investigated with D4 siloxane (octamethylcyclotetrasiloxane) contamination. In order to evaluate the influence of the electrochemical reaction on the siloxane deposition process, the SOFC experiments were operated at open circuit voltage (OCV) and 50 mA cm -2 conditions at 800°C. During the failure process, electrochemical, morphology and exhaust gas component analysis testing are conducted at the critical points. An equivalent circuit model and corresponding microstructure parameter calculations for separated physicochemical processes were utilized for the quantitative analysis of the failure process. Further, the results confirm the siloxane chemical adsorption deposition mechanism proposed in previous work. As a result, the failure of the anode was attributed to the gas diffusion blockage by dense silicon dioxide layer formation. The anode failure process with siloxane contamination is faster when the anode is operated under polarization.

25 ENERGY STORAGE↗

Toxic elements and speciation in seafood samples from different contaminated sites in Europe

The presence of cadmium (Cd), lead (Pb), mercury (THg), methylmercury (MeHg), arsenic (TAs), inorganic arsenic (iAs), cobalt (Co), copper (Cu), zinc (Zn), nickel (Ni), chromium (Cr) and iron (Fe) was investigated in seafood collected from European marine ecosystems subjected to strong anthropogenic pressure, i.e. hotspot areas. Different species (Mytilus galloprovincialis, n=50; Chamelea gallina, n=50; Liza aurata, n=25; Platichthys flesus, n=25; Laminaria digitata, n=15; and Saccharina latissima, n=15) sampled in Tagus estuary, Po delta, Ebro delta, western Scheldt, and in the vicinities of a fish farm area (Solund, Norway), between September and December 2013, were selected to assess metal contamination and potential risks to seafood consumers, as well as to determine the suitability of ecologically distinct organisms as bioindicators in environmental monitoring studies. Species exhibited different elemental profiles, likely as a result of their ecological strategies, metabolism and levels in the environment (i.e. seawater and sediments). Higher levels of Cd (0.15–0.94 mg kg{sup −1}), Pb (0.37−0.89 mg kg{sup −1}), Co (0.48–1.1 mg kg{sup −1}), Cu (4.8–8.4 mg kg{sup −1}), Zn (75–153 mg kg{sup −1}), Cr (1.0–4.5 mg kg{sup −1}) and Fe (283–930 mg kg{sup −1}) were detected in bivalve species, particularly in M. galloprovincialis from Ebro and Po deltas, whereas the highest content of Hg was found in P. flesus (0.86 mg kg{sup −1}). In fish species, most Hg was organic (MeHg; from 69 to 79%), whereas lower proportions of MeHg were encountered in bivalve species (between 20 and 43%). The highest levels of As were found in macroalgae species L. digitata and S. latissima (41 mg kg{sup −1} and 43 mg kg{sup −1}, respectively), with iAs accounting almost 50% of the total As content in L. digitata but not with S. latissima nor in the remaining seafood samples. This work highlights that the selection of the most appropriate bioindicator species is a fundamental step in environmental monitoring of each contaminant, especially in coastal areas. Furthermore, data clearly shows that the current risk assessment and legislation solely based on total As or Hg data is limiting, as elemental speciation greatly varies according to seafood species, thus playing a key role in human exposure assessment via food.

54 ENVIRONMENTAL SCIENCES↗

Oral relative bioavailability of Dichlorodiphenyltrichloroethane (DDT) in contaminated soil and its prediction using in vitro strategies for exposure refinement

In this study, the bioavailability of DDTr (sum of DDT, DDD and DDE isomers) in pesticide-contaminated soil was assessed using an in vivo mouse model. DDTr relative bioavailability (RBA) ranged from 18.7±0.9 (As35) to 60.8±7.8% (As36) indicating that a significant portion of soil-bound DDTr was not available for absorption following ingestion. When DDTr bioaccessibility was assessed using the organic Physiologically Based Extraction Test (org-PBET), the inclusion of a sorption sink (silicone cord) enhanced DDTr desorption by up to 20-fold (1.6–3.8% versus 18.9–56.3%) compared to DDTr partitioning into gastrointestinal fluid alone. Enhanced desorption occurred as a result of the silicone cord acting as a reservoir for solubilized DDTr to partition into, thereby creating a flux for further desorption until equilibrium was achieved. When the relationship between in vivo and in vitro data was assessed, a strong correlation was observed between the mouse bioassay and the org-PBET+silicone cord (slope=0.94, y-intercept=3.5, r{sup 2}=0.72) suggesting that the in vitro approach may provide a robust surrogate measure for the prediction of DDTr RBA in contaminated soil. - Highlights: • An optimised mouse assay was used to quantify DDTr relative bioavailability in soil. • DDTr bioaccessibility was also determined using an in vitro sorption sink approach. • A strong correlation was observed between in vivo and in vitro data. • The sorption sink approach may be used to predict DDTr relative bioavailability.

54 ENVIRONMENTAL SCIENCES↗

Geochemistry and mercury contamination in receiving environments of artisanal mining wastes and identified concerns for food safety

Artisanal small-scale gold mining (ASGM) using mercury (Hg) amalgamation has been occurring on Buru Island, Indonesia since early 2012, and has caused rapid accumulation of high Hg concentrations in river, estuary and marine sediments. In this study, sediment samples were collected from several sites downstream of the Mount Botak ASGM site, as well as in the vicinity of the more recently established site at Gogrea where no sampling had previously been completed. All sediment samples had total Hg (THg) concentrations exceeding Indonesian sediment quality guidelines and were up to 82 times this limit at one estuary site. The geochemistry of sediments in receiving environments indicates the potential for Hg-methylation to form highly bioavailable Hg species. To assess the current contamination threat from consumption of local seafood, samples of fish, molluscs and crustaceans were collected from the Namlea fish market and analysed for THg concentrations. The majority of edible tissue samples had elevated THg concentrations, which raises concerns for food safety. This study shows that river, estuary and marine ecosystems downstream of ASGM operations on Buru Island are exposed to dangerously high Hg concentrations, which are impacting aquatic food chains, and fisheries resources. Considering the high dietary dependence on marine protein in the associated community and across the Mollucas Province, and the short time period since ASGM operations commenced in this region, the results warrant urgent further investigation, risk mitigation, and community education. - Highlights: • Mercury contamination of sediments and seafood due to artisanal gold mining. • Considerable risks to human and ecosystem health are identified. • Results emphasise the urgent need for risk mitigation and community education.

54 ENVIRONMENTAL SCIENCES↗

Remediation of contaminated soils by enhanced nanoscale zero valent iron

The use of nanoscale zero valent iron (nZVI) for in situ remediation of soil contamination caused by heavy metals and organic pollutants has drawn great concern, primarily owing to its potential for excellent activity, low cost and low toxicity. This reviews considers recent advances in our understanding of the role of nZVI and enhanced nZVI strategy in the remediation of heavy metals and persistent organic contaminants polluted soil. The performance, the migration and transformation of nZVI affected by the soil physical and chemical conditions are summarized. However, the addition of nZVI inevitably disturbs the soil ecosystem, thus the impacts of nZVI on soil organisms are discussed. In order to further investigate the remediation effect of nZVI, physical, chemical and biological method combination with nZVI was developed to enhance the performance of nZVI. From a high efficient and environmentally friendly perspective, biological method enhanced nZVI technology will be future research needs. Possible improvement of nZVI-based materials and potential areas for further applications in soil remediation are also proposed.

54 ENVIRONMENTAL SCIENCES↗

Selenium contamination, consequences and remediation techniques in water and soils: A review

Highlights: • Se contamination in environment emerged as a serious threat. • Se causes various several fatal diseases in human beings and animals. • Various treatment techniques for Se removal from water and soil are reviewed. • Adsorption and membrane separation are seemed to be suitable on a commercial scale. • The knowledge gaps to be addressed are proposed. Selenium (Se) contamination in surface and ground water in numerous river basins has become a critical problem worldwide in recent years. The exposure to Se, either direct consumption of Se or indirectly may be fatal to the human health because of its toxicity. The review begins with an introduction of Se chemistry, distribution and health threats, which are essential to the remediation techniques. Then, the review provides the recent and common removal techniques for Se, including reduction techniques, phytoremediation, bioremediation, coagulation-flocculation, electrocoagulation (EC), electrochemical methods, adsorption, coprecipitation, electrokinetics, membrance technology, and chemical precipitation. Removal techniques concentrate on the advantages, drawbacks and the recent achievements of each technique. The review also takes an overall consideration of experimental conditions, comparison criteria and economic aspects.

54 ENVIRONMENTAL SCIENCES↗

Soil contamination and sources of phthalates and its health risk in China: A review

Highlights: • PAE levels in soils of China were generally higher than the other countries. • DBP and DEHP are the dominant compounds in soil with obvious spatial distribution. • Urbanization and industrialization, application of plastic film and fertilizer are the major sources of PAEs in soil. • Uptake of PAEs by crops and human exposure to PAEs are reviewed. Phthalates (PAEs) are extensively used as plasticizers and constitute one of the most frequently detected organic contaminants in the environment. With the deterioration of eco-environment in China during the past three decades, many studies on PAE occurrence in soils and their risk assessments have been conducted which allow us to carry out a fairly comprehensive assessment of soil PAE contamination on a nation-wide scale. This review combines the updated information available associated with PAE current levels, distribution patterns (including urban soil, rural or agricultural soil, seasonal and vertical variations), potential sources, and human health exposure. The levels of PAEs in soils of China are generally at the high end of the global range, and higher than the grade II limits of the Environmental Quality Standard for soil in China. The most abundant compounds, di-n-butyl phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP), display obvious spatial distribution in different provinces. It is noted that urbanization and industrialization, application of plastic film (especially plastic film mulching in agricultural soil) and fertilizer are the major sources of PAEs in soil. Uptake of PAEs by crops, and human exposure to PAEs via ingestion of soil and vegetables are reviewed, with scientific gaps highlighted.

54 ENVIRONMENTAL SCIENCES↗