Impact Of nZVI Research Articles

Impact of nZVI and nZVI/BC on the anaerobic digestion of piggery wastewater

In this study, nanoscale zero valent iron (nZVI) and biochar supported zero valent iron (nZVI/BC) mediated anaerobic digestion of piggery wastewater were investigated. The variation of COD removal rate, methane yield, kinetics modeling and microbial community analysis was analyzed. COD removal rate was increased by 7.46–14.79% respectively for 1, 2, 3 and 4 g nZVI. While COD removal rate was increased by 7.90–12.83% respectively for 1, 2, 3 and 4 g nZVI/BC. Compared with the control group, the accumulated methane yield was increased by 24.17–30.22% and 29.2–46.7% respectively for nZVI and nZVI/BC. Meanwhile, the accumulated hydrogen sulfide concentration was greatly reduced which was decreased from 8.32 ml (control group) to 0.40 ml (nZVI) and 0.22 ml (nZVI/BC). The variation of microbial community showed that nZVI could increase the relative abundance of Methanobacterium, longlinea and syntrophobacter, while nZVI/BC provides a more suitable environment for the growth of Mesotoga, Pertrimonas and Longilinea.

Nano zero-valent iron-induced changes in soil iron species and soil bacterial communities contribute to the fate of Cd

Nano zero-valent iron (nZVI) is used for soil remediation; however, the impact of nZVI on soil solid iron phases and its interactions with soil microorganisms in relation to the fate of Cd in soil remains unclear. In the current study, we investigated the mechanisms underlying the change in mobility of Cd in exogenous Cd-contaminated soil with nZVI and γ radiation treatments. The results showed that nZVI treatment decreased Cd availability but also increased the soil pH and dissolved Mn and poorly crystalline Fe contents. However, the increased poorly crystalline Fe(II) levels contributed to a reduction in Cd availability in soils treated with nZVI by immobilizing Cd associated with Fe oxides, rather than by increasing pH or Mn oxide levels. Moreover, Cd stabilization efficiency was higher in γ-irradiated soils than in non-irradiated soils regardless of the Cd level, with noticeable differences in bacterial community composition between the non-irradiated and irradiated soils. The genera Bacillus, Pullulanibacillus, and Alicyclobacillus are important in the redox of poorly crystalline Fe(II)-containing minerals in non-irradiated soil. This research provides a new method for further improving the Cd stabilization efficiency of nZVI in combination with microbial iron oxidization inhibitors.

In Vitro Study of the Toxicity Mechanisms of Nanoscale Zero-Valent Iron (nZVI) and Released Iron Ions Using Earthworm Cells.

During the last two decades, nanomaterials based on nanoscale zero-valent iron (nZVI) have ranked among the most utilized remediation technologies for soil and groundwater cleanup. The high reduction capacity of elemental iron (Fe0) allows for the rapid and cost-efficient degradation or transformation of many organic and inorganic pollutants. Although worldwide real and pilot applications show promising results, the effects of nZVI on exposed living organisms are still not well explored. The majority of the recent studies examined toxicity to microbes and to a lesser extent to other organisms that could also be exposed to nZVI via nanoremediation applications. In this work, a novel approach using amoebocytes, the immune effector cells of the earthworm Eisenia andrei, was applied to study the toxicity mechanisms of nZVI. The toxicity of the dissolved iron released during exposure was studied to evaluate the effect of nZVI aging with regard to toxicity and to assess the true environmental risks. The impact of nZVI and associated iron ions was studied in vitro on the subcellular level using different toxicological approaches, such as short-term immunological responses and oxidative stress. The results revealed an increase in reactive oxygen species production following nZVI exposure, as well as a dose-dependent increase in lipid peroxidation. Programmed cell death (apoptosis) and necrosis were detected upon exposure to ferric and ferrous ions, although no lethal effects were observed at environmentally relevant nZVI concentrations. The decreased phagocytic activity further confirmed sublethal adverse effects, even after short-term exposure to ferric and ferrous iron. Detection of sublethal effects, including changes in oxidative stress-related markers such as reactive oxygen species and malondialdehyde production revealed that nZVI had minimal impacts on exposed earthworm cells. In comparison to other works, this study provides more details regarding the effects of the individual iron forms associated with nZVI aging and the cell toxicity effects on the specific earthworms’ immune cells that represent a suitable model for nanomaterial testing.

Impact of nZVI on the formation of aerobic granules, bacterial growth and nutrient removal using aerobic sequencing batch reactor

Abstract The aim of this study was to investigate the effect of nanoscale zero-valent iron (nZVI) on the formation of aerobic granules, nutrient removal and bacterial growth during the treatment process of the municipal wastewater. For this purpose, two sequencing batch reactors (SBR) were simultaneously and automatically operated in a cyclic batch mode with four phases per cycle: feed, react, settle and decant. The sequancial operation of the reactors consisted four cycles per day and lasted for sixty days in which 10 mg/L of nZVI particles were added to the infflent of reactor 2. The reactors were fed with synthetic wastewater (3 liters per cycle) and acclimated with seed sludge collected from a full-scale municipal wastewater treatment plant in Istanbul. The effluent of the reactors was regularly analyzed for nitrate, nitrite, ammonia, phosphate and COD concentrations. In addtion to that, their removal pathways including the direct adsorption to nZVI, utilization by microorganisms and adsorption within the generated granules were discussed. The removal efficiency of COD, ammonia and phosphate kept increasing, and almost a complete removal was observed after the formation of aerobic granules on day 50. Furthermore, after the addition of nZVI to R2 on day 24th, the removal efficiency of ammonia, COD and phosphate slightly improved. The addition of nZVI stimulated the production of Extracellular Polymeric Substances (EPS) in R2 including protein and carbohydrate generation. NGS analysis showed that the addition of nZVI into R2 increased the growth rate of some bacterial species such as Rhizobiales and Xanthomonadales and decreased others such as Clostridiales, confirming that the effect of nZVI on the bacterial growth was genera dependent. The aerobic granules were successfully formed in the reactors in less than 50 days and the addition of nZVI improved to some extent the size and settling rate of the formed granules in R2.

Evaluating phytotoxicity of bare and starch-stabilized zero-valent iron nanoparticles in mung bean

Zero-valent iron nanoparticles (nZVI) are among the most widely used nanoparticles in nanoremediation of various environmental pollutants. Environmental fate and impact of nZVI has attracted increasing concerns due to their potential risks. However, phytotoxicity of nZVI still remains poorly understood. Here, the phytotoxic effects of bare nZVI (B-nZVI) and starch-stabilized nZVI (S-nZVI) were evaluated on the germination of mung bean seeds exposed to suspensions with different doses of 0–1000 mg/L and the growth of hydroponically cultured seedling at 600 mg/L. In most cases, B-nZVI had no inhibition on seed germination, and even promotion on shoot and root elongation. However, S-nZVI displayed dose-dependent effects, with a decreased germination rate at 600–750 mg/L. B-nZVI at 600 mg/L showed no obvious phytotoxic but even stimulatory effects on seedling growth. Comparatively, S-nZVI at 600 mg/L produced significant phytotoxicity on mung bean plants, leading to decreased seedling growth, altered nutritional balance, and excess Fe accumulation in roots (>400 mg/kg). S-nZVI were observed to form a coating of insoluble Fe(III) compounds on root surface. Simultaneously, some nZVI penetrated and accumulated into root cells, but did not move to shoots. In conclusion, B-nZVI easily aggregate into larger particles in solution, leading to decreased adhesion to root surface and lower uptake by roots, whereas the higher dispersity and hydrophilicity of S-nZVI makes them more readily be adhered to root surface forming a coating, and penetrated into roots, resulting in excess Fe accumulation, consequently interfering with root functions such as the adsorption and transport of water and nutrients.

New insights into the impact of nZVI on soil microbial biodiversity and functionality

Nanoscale zero-valent iron (nZVI) is a strong reducing agent used for in situ remediation of soil. The impacts of nZVI (5–10% w/w) on the soil microbial biodiversity and functionality of two soils (Lufa 2.2 and 2.4) were assessed. Illumina MiSeq technology was used to evaluate the structure of soil microbiomes after 21 days of exposure. Proteobacteria, Verrucomicrobia, Firmicutes and Actinobacteria were the most abundant phyla in both soils. However, the dynamics of bacterial community composition following nZVI addition differed. nZVI exposure induced pronounced shifts in the microbial composition of soil 2.4, but not in soil 2.2; an increase in Verrucomicrobia abundance was the unique common taxonomic pattern observed in both soils. The PICRUSt approach was applied to predict the functional composition of each metagenome. Environmental information processing function (membrane transport) was decreased in both nZVI-spiked soils, although soil 2.4 samples were enriched in functions involved in cellular processes and metabolism. The effects of nZVI on autochthonous bacterial communities clearly varied with the soil type assessed; changes at the phylogenetic level appeared to be more abundant than those observed at the functional level, and thus, the overall effort of the soil ecosystem might involve the maintenance of functionality following nZVI exposure.

The impact of nanoscale zero-valent iron particles on soil microbial communities is soil dependent.

The application of nanoscale zero-valent iron particles (nZVI) for the remediation of contaminated sites is very promising. However, information concerning the ecotoxicity of nZVI on soil microbial communities and, hence, soil quality, is still scarce. We carried out a three-month experiment to evaluate the impact of the application of different concentrations of nZVI (from 1 to 20 mg g DW soil-1) on soil microbial properties in a clay-loam versus a sandy-loam soil. Data on microbial biomass (total bacteria and fungi by qPCR, microbial biomass carbon), activity (β-glucosidase, arylsulphatase and urease activities), and functional (Biolog Ecoplates™) and structural (ARISA, 16S rRNA amplicon sequencing) diversity evidenced that the sandy-loam soil was more vulnerable to the presence of nZVI than the clay-loam soil. In the sandy-loam soil, arylsulphatase activity and bacterial abundance, richness and diversity were susceptible to the presence of nZVI. The high content of clay and organic matter present in the clay-loam soil may explain the observed negligible effects of nZVI on soil microbial properties. It was concluded that the impact of nZVI on soil microbial communities and, hence, soil quality, is soil dependent.

Three Functional Biomarkers for Monitoring the Nanoscale Zero-Valent Iron (nZVI)-Induced Molecular Signature on Soil Organisms

Currently, there are increasing efforts to utilize nanoremediation as an environmental technology for cleaning up polluted environments using nanoscale zero-valent iron (nZVI); however, concerns exist regarding the long-term environmental impact of this strategy. In this study, an innovative methodology for evaluating nZVI impact on soil bacteria is utilized, based on transcriptional analysis of three novel biomakers: tnaA, sodB and trx genes. At the same time, classical toxicological bioassays with the nematode Caenorhabditis elegans were performed. Microcosms treated with 1, 5 and 10 % w/w of nZVI were set up using a commercial standard soil and incubated for 21 days. The tnaA gene, involved in indole production, was significantly upregulated at all assessed nZVI concentrations, suggesting that bacterial cells used this molecule to inform the rest of the community about the changes produced upon nZVI soil treatment. The higher the exposure time, the lower nZVI concentration needed to detect these changes. Consequently, soil bacteria activate a cellular adaptive response to cope with the nZVI-induced oxidative stress, increasing the expression of genes encoding key reactive oxygen species (ROS)-scavenging enzymes; in fact, an upregulation of the sodB and katB genes was recorded upon nZVI exposure. On the contrary, C. elegans survival and growth endpoints were not affected at any nZVI concentration whereas the exposure time significantly increased nematode growth in the soil. Therefore, despite the lack of toxicity revealed by the classical conducted tests, the transcriptional analyses demonstrated the usefulness of combining the set of proposed biomarkers for early detection and monitoring the impact of nZVI on soil bacteria after environmentally important periods of exposure.

Immobilization and Leaching of Pb and Zn in an Acidic Soil Treated with Zerovalent Iron Nanoparticles (nZVI): Physicochemical and Toxicological Analysis of Leachates

A column experiment was conducted to evaluate the effectiveness of nanoscale zerovalent iron (nZVI) for the in situ immobilization of Pb and Zn in an acidic soil. The impact of nZVI on soil was evaluated by monitoring the physicochemical characteristics of the leachates and their ecotoxicological effects on three species, Vibrio fischeri, Artemia franciscana, and Caenorhabditis elegans. Treatment with nZVI resulted in more effective Pb immobilization in comparison to Zn and reduced the leachability by 98 and 72 %, respectively; the immobilization was stable throughout the experiment. Leachates from nZVI-treated soils showed lower toxicity than leachates from untreated ones. The highest toxicity in treated soils was observed in the first leachate, which presented high values of electrical conductivity due to the leachability of soil ions and those provided by the commercial nanoparticle suspension (Na and Fe). V. fischeri and C. elegans were more sensitive to leachates from nZVI-treated soils polluted with Zn than those from soils polluted with Pb; A. franciscana showed the opposite trend.

Nanoscale Zero‐Valent Iron for Sulfide Removal from Digested Piggery Wastewater

The removal of dissolved sulfides in water and wastewater by nanoscale zero‐valent iron (nZVI) was examined in the study. Both laboratory batch studies and a pilot test in a 50,000‐pig farm were conducted. Laboratory studies indicated that the sulfide removal with nZVI was a function of pH where an increase in pH decreased removal rates. The pH effect on the sulfide removal with nZVI is attributed to the formation of FeS through the precipitation of Fe(II) and sulfide. The saturated adsorption capacities determined by the Langmuir model were 821.2, 486.3, and 359.7 mg/g at pH values 4, 7, and 12, respectively, for nZVI, largely higher than conventional adsorbents such as activated carbon and impregnated activated carbon. The surface characterization of sulfide‐laden nZVI using XPS and TGA indicated the formation of iron sulfide, disulfide, and polysulfide that may account for the high adsorption capacity of nZVI towards sulfide. The pilot study showed the effectiveness of nZVI for sulfide removal; however, the adsorption capacity is almost 50 times less than that determined in the laboratory studies during the testing period of 30 d. The complexity of digested wastewater constituents may limit the effectiveness of nZVI. Microbial analysis suggested that the impact of nZVI on the change of microbial species distribution was relatively noticeable after the addition of nZVI.

The impact of zero-valent iron nanoparticles upon soil microbial communities is context dependent

Nanosized zero-valent iron (nZVI) is an effective land remediation tool, but there remains little information regarding its impact upon and interactions with the soil microbial community. nZVI stabilised with sodium carboxymethyl cellulose was applied to soils of three contrasting textures and organic matter contents to determine impacts on soil microbial biomass, phenotypic (phospholipid fatty acid (PLFA)), and functional (multiple substrate-induced respiration (MSIR)) profiles. The nZVI significantly reduced microbial biomass by 29 % but only where soil was amended with 5 % straw. Effects of nZVI on MSIR profiles were only evident in the clay soils and were independent of organic matter content. PLFA profiling indicated that the soil microbial community structure in sandy soils were apparently the most, and clay soils the least, vulnerable to nZVI suggesting a protective effect imparted by clays. Evidence of nZVI bactericidal effects on Gram-negative bacteria and a potential reduction of arbuscular mycorrhizal fungi are presented. Data imply that the impact of nZVI on soil microbial communities is dependent on organic matter content and soil mineral type. Thereby, evaluations of nZVI toxicity on soil microbial communities should consider context. The reduction of AM fungi following nZVI application may have implications for land remediation.

Stabilization or Oxidation of Nanoscale Zerovalent Iron at Environmentally Relevant Exposure Changes Bioavailability and Toxicity in Medaka Fish

Nanoscale zerovalent iron (nZVI)-based nanotechnologies are increasingly being used for environmental remediation; however, the fate and ecotoxicologic effects of nZVI remain unclear. Larvae of medaka fish (Oryzias latipes) underwent 3-14 days' aqueous exposure to thoroughly characterized solutions containing carboxymethyl cellulose (CMC)-stabilized nZVI, bare nZVI, nanoscale iron oxide (nFe(3)O(4)) or ferrous ion [Fe(II)(aq)] at μg/L-mg/L levels to assess the causal toxic effect(s) of iron nanoparticles (NPs). Acute larval mortality was decreased in the order of Fe(II)(aq) > CMC-nZVI > nZVI > nFe(3)O(4). CMC-nZVI (100 mg/L) increased hypoxia and reactive oxygen species (ROS) and Fe(II)(aq) production, thus increasing mortality and oxidative stress response as compared with unstabilized nZVI. Additionally, nFe(3)O(4) and nZVI were more bioavailable than suspended CMC-nZVI or Fe(II)(aq). Antioxidant activities were significantly altered by induced intracellular ROS levels in larvae with subchronic exposure to nFe(3)O(4) or Fe(II)(aq) at environmentally relevant concentrations (0.5-5 mg/L). We report on different organizational biomarkers used for rapidly assessing the lethal and sublethal toxicity of nZVI and its stabilized or oxidized products. The toxicity results implicate a potential ecotoxicological fate and impact of nZVI on the aquatic environment.