Contribution, Composition, and Structure of EPS by In Vivo Exposure to Elucidate the Mechanisms of Nanoparticle-Enhanced Bioremediation to Metals.

Bacterial extracellular polymeric substances (EPS) have been recently found to contribute most for metal removal in nanoenhanced bioremediation. However, the mechanism by which NPs affect EPS-metal interactions is not fully known. Here, Halomonas sp. was employed to explore the role of EPS after in vivo exposure to Cd/Pb and polyvinylpyrrolidone (PVP) coated iron oxide nanoparticles (IONPs, 20 mg L-1) for 72 h. Cd-IONPs produced the highest concentrations of EPS proteins (136.3 mg L-1), while Cd induced the most production of polysaccharides (241.0 mg L-1). IONPs increased protein/polysaccharides ratio from 0.2 (Cd) to 1.2 (Cd-IONPs). The increased protein favors the formation of protein coronas on IONPs surface, which would promote Cd adsorption during NP-metal-EPS interaction. FTIR analysis indicated that the coexistence of Cd and IONPs interacted with proteins more strongly than with polysaccharides. Glycosyl monomer analyses suggested mannose and glucose as target sugars for EPS complexation with metals, and IONPs reduced metal-induced changes in monosaccharide profiles. Protein secondary structures changed in all treatments, but we could not distinguish stresses induced by metals from those by IONPs. These findings provide greater understanding of the role of EPS in NP-metal-EPS interaction, providing a better underpinning knowledge for the application of NP-enhanced bioremediation.

How Do African-American Community Members' Perceptions About Environmental Risks of Breast Cancer Compare with the Current State of the Science?

African-American (AA) women experience higher mortality from breast cancer than any other racial group. Understanding community-held perceptions of environmental contaminants as risk factors for breast cancer can inform the development of tailored prevention and education efforts for improve health outcomes. Six focus groups were conducted with AA participants in two counties in South Carolina, and themes were identified using open and axial coding. Perceived environmental risks for breast cancer most frequently discussed by participants were compared to findings from published systematic reviews. Frequently discussed environmental risk factors by participants were deodorants containing aluminum, plastics, pesticides, and air and water pollution. While perceptions of aluminum and air pollution as risk factors did not align with the state of the science, perceived risk factors of chemicals in plastics and pesticides were found to be in alignment. There is some congruence between perceived environmental risks for breast cancer within the AA community and the current state of the science; however, there is a need to communicate information that reflects current science regarding commonly held misconceptions. Development of evidence-based, clear, and culturally appropriate messaging that reflects the current state of the science is warranted.

"Talk About Cancer and Build Healthy Communities": How Visuals Are Starting the Conversation About Breast Cancer Within African-American Communities.

African-American (AA) women are at higher risk of breast cancer mortality than women of other races. Factors influencing breast cancer risk, including exogenous environmental exposures, and debate around timing of exposure and dose-response relationship, can cause misunderstanding. Collaboration with priority populations encourages culturally relevant health messaging that imparts source reliability, influences message adoption, and improves understanding. Through six focus groups with AA individuals in rural and urban counties in the southeastern United States, this study used a community-engaged participatory approach to design an innovative visual tool for disseminating breast cancer information. Results demonstrated that participants were generally aware of environmental breast cancer risks and were willing to share new knowledge with families and community members. Recommended communication channels included pastors, healthcare providers, social media, and the Internet. Participants agreed that a collaboratively designed visual tool serves as a tangible, focused "conversation starter" to promote community prevention and education efforts.

Health impacts of environmental contamination of micro- and nanoplastics: a review.

Plastics are extensively used in our daily life. However, a significant amount of plastic waste is discharged to the environment directly or via improper reuse or recycling. Degradation of plastic waste generates micro- or nano-sized plastic particles that are defined as micro- or nanoplastics (MNPs). Microplastics (MPs) are plastic particles with a diameter less than 5 mm, while nanoplastics (NPs) range in diameter from 1 to 100 or 1000 nm. In the current review, we first briefly summarized the environmental contamination of MNPs and then discussed their health impacts based on existing MNP research. Our review indicates that MNPs can be detected in both marine and terrestrial ecosystems worldwide and be ingested and accumulated by animals along the food chain. Evidence has suggested the harmful health impacts of MNPs on marine and freshwater animals. Recent studies found MPs in human stool samples, suggesting that humans are exposed to MPs through food and/or drinking water. However, the effect of MNPs on human health is scarcely researched. In addition to the MNPs themselves, these tiny plastic particles can release plastic additives and/or adsorb other environmental chemicals, many of which have been shown to exhibit endocrine disrupting and other toxic effects. In summary, we conclude that more studies are necessary to provide a comprehensive understanding of MNP pollution hazards and also provide a basis for the subsequent pollution management and control.

A Comparison between the Oil Removal Capacity of Polymer-Coated Magnetic Nanoparticles in Natural and Synthetic Environmental Samples.

Oil spills can have dramatic impacts on the environment. The limitations of current oil remediation techniques have inspired researchers to study the application of nanotechnology for oil cleanup. Previously, we reported essentially 100% removal of a reference MC252 oil using polyvinylpyrrolidone (PVP)-coated iron oxide nanoparticles (NPs) from oil-water mixtures under a wide range of environmentally relevant conditions. Our previous results showed that in the synthetic water samples, the concentration of cations and natural organic macromolecules (NOM) can significantly affect the oil removal efficiency of NPs. Here, we studied the application of these NPs for oil removal from natural freshwater samples and compared the results with the synthetic water samples with the same concentrations of major ions and NOM. For both natural and synthetic samples, concentrations of NOM, calcium, and magnesium were positively correlated with oil removal ( p-value <0.05). NPs show an average of 30% higher oil removal efficiency from natural samples compared to the synthetic samples. Using up to 50 ppm of NP, essentially 100% oil removal was observed under most conditions specially hardwater samples (initial 0.15 g L-1 oil concentration). Results show that these NPs are a facile and reliable technique for removing oil under realistic conditions.

Size and coating of engineered silver nanoparticles determine their ability to growth-independently inhibit aflatoxin biosynthesis in Aspergillus parasiticus.

Recent studies from our laboratory indicate that engineered silver nanoparticles can inhibit aflatoxin biosynthesis even at concentrations at which they do not demonstrate antifungal activities on the aflatoxin-producing fungus. Whether such inhibition can be modified by altering the nanoparticles' physical properties remains unclear. In this study, we demonstrate that three differently sized citrated-coated silver nanoparticles denoted here as NP1, NP2, and NP3 (where, sizes of NP1 < NP2 < NP3) inhibit aflatoxin biosynthesis at different effective doses in Aspergillus parasiticus, the plant pathogenic filamentous fungus. Recapping NP2 with polyvinylpyrrolidone coating (denoted here as NP2p) also altered its ability to inhibit aflatoxin production. Dose-response experiments with NP concentrations ranging from 10 to 100 ng mL-1 indicated a non-monotonic relationship between aflatoxin inhibition and NP concentration. The maximum inhibitory concentrations differed between the NP types. NP1 demonstrated maximum inhibition at 25 ng mL-1. Both NP2 and NP3 showed maximum inhibition at 50 ng mL-1, although NP2 resulted in a significantly higher inhibition than NP3. While both NP2 and NP2p demonstrated greater aflatoxin inhibition than NP1 and NP3, NP2p inhibited aflatoxin over a significantly wider concentration range as compared to NP2. Our results, therefore, suggest that nano-fungal interactions can be regulated by altering certain NP physical properties. This concept can be used to design NPs for mycotoxin prevention optimally.

Nanosilver inhibits nitrification and reduces ammonia-oxidising bacterial but not archaeal amoA gene abundance in estuarine sediments.

Silver nanoparticles (AgNPs) enter estuaries via wastewater treatment effluents, where they can inhibit microorganisms, because of their antimicrobial properties. Ammonia-oxidising bacteria (AOB) and archaea (AOA) are involved in the first step of nitrification and are important to ecosystem function, especially where effluent discharge results in high nitrogen inputs. Here, we investigated the effect of a pulse addition of AgNPs on AOB and AOA ammonia monooxygenase (amoA) gene abundances and benthic nitrification potential rates (NPR) in low-salinity and mesohaline estuarine sediments. Whilst exposure to 0.5 mg L-1 AgNPs had no significant effect on amoA gene abundances or NPR, 50 mg L-1 AgNPs significantly decreased AOB amoA gene abundance (up to 76% over 14 days), and significantly decreased NPR by 20-fold in low-salinity sediments and by twofold in mesohaline sediments, after one day. AgNP behaviour differed between sites, whereby greater aggregation occurred in mesohaline waters (possibly due to higher salinity), which may have reduced toxicity. In conclusion, AgNPs have the potential to reduce ammonia oxidation in estuarine sediments, particularly where AgNPs accumulate over time and reach high concentrations. This could lead to long-term risks to nitrification, especially in polyhaline estuaries where ammonia-oxidation is largely driven by AOB.

A High Resolution Study of Dynamic Changes of Ce2O3 and CeO2 Nanoparticles in Complex Environmental Media.

Ceria nanoparticles (NPs) rapidly and easily cycle between Ce(III) and Ce(IV) oxidation states, making them prime candidates for commercial and other applications. Increased commercial use has resulted in increased discharge to the environment and increased associated risk. Once in complex media such as environmental waters or toxicology exposure media, the same redox transformations can occur, causing altered behavior and effects compared to the pristine NPs. This study used high resolution scanning transmission electron microscopy and electron energy loss spectroscopy to investigate changes in structure and oxidation state of small, polymer-coated ceria suspensions in complex media. NPs initially in either the III or IV oxidation states, but otherwise identical, were used. Ce(IV) NPs were changed to mixed (III, IV) NPs at high ionic strengths, while the presence of natural organic macromolecules (NOM) stabilized the oxidation state and increased crystallinity. The Ce(III) NPs remained as Ce(III) at high ionic strengths, but were modified by the presence of NOM, causing reduced crystallinity and degradation of the NPs. Subtle changes to NP properties upon addition to environmental or ecotoxicology media suggest that there may be small but important effects on fate and effects of NPs compared to their pristine form.

Citrate-Coated Silver Nanoparticles Growth-Independently Inhibit Aflatoxin Synthesis in Aspergillus parasiticus.

Manufactured silver nanoparticles (Ag NPs) have long been used as antimicrobials. However, little is known about how these NPs affect fungal cell functions. While multiple previous studies reveal that Ag NPs inhibit secondary metabolite syntheses in several mycotoxin producing filamentous fungi, these effects are associated with growth repression and hence need sublethal to lethal NP doses, which besides stopping fungal growth, can potentially accumulate in the environment. Here we demonstrate that citrate-coated Ag NPs of size 20 nm, when applied at a selected nonlethal dose, can result in a >2 fold inhibition of biosynthesis of the carcinogenic mycotoxin and secondary metabolite, aflatoxin B1 in the filamentous fungus and an important plant pathogen, Aspergillus parasiticus, without inhibiting fungal growth. We also show that the observed inhibition was not due to Ag ions, but was specifically associated with the mycelial uptake of Ag NPs. The NP exposure resulted in a significant decrease in transcript levels of five aflatoxin genes and at least two key global regulators of secondary metabolism, laeA and veA, with a concomitant reduction of total reactive oxygen species (ROS). Finally, the depletion of Ag NPs in the growth medium allowed the fungus to regain completely its ability of aflatoxin biosynthesis. Our results therefore demonstrate the feasibility of Ag NPs to inhibit fungal secondary metabolism at nonlethal concentrations, hence providing a novel starting point for discovery of custom designed engineered nanoparticles that can efficiently prevent mycotoxins with minimal risk to health and environment.

A content analysis of Internet resources about the risks of seafood consumption.

Seafood consumption is a main source of human exposure to certain environmental contaminants. Therefore, it is valuable to assess the online health risk messages focused on this topic, as people in the US are increasingly accessing the Internet for health-related information. Previous research indicates that online health information tends to be written at a reading level that is more advanced than ability of the general population. The purpose of this research was to examine the content and readability of Internet resources targeted toward consumers in the US regarding the health risks from consumption of contaminated seafood. Sources for analysis were gathered through a targeted search of state and national government websites, as well as through a Google search. The overall mean readability level was Grade 9.21, which is slightly above the average reading level of US adults. Future research should evaluate the accuracy of the health risk messages, as well as consumer perceptions of risk.

Oil Recovery from Water under Environmentally Relevant Conditions Using Magnetic Nanoparticles.

Large oil spills and oily wastewater discharges from ships and industrial activities can have serious impacts on the environment with potentially major economic impacts. Current oil remediation techniques are inefficient and may have deleterious environmental consequences. However, nanotechnology offers a new route to potentially remediate oil pollution. In this study, a cheap and facile hydrothermal method was developed to synthesize polyvinylpyrrolidone-coated magnetite nanoparticles to separate a reference MC252 oil from oil-water mixture under environmentally relevant conditions. Fluorescence and Proton nuclear magnetic resonance spectroscopy results showed near 100% oil removal from oil-water mixture in the ultrapure water under optimum condition. Based on gas chromatography-mass spectrometry data, approximately 100% of lower molecular mass alkanes (C9-C21) were removed within 10 min of magnetic separation and by increasing the separation time to 40 min, greater than 67% of C22-25 alkanes were removed. Moreover, nanoparticles removed near 100% oil from synthetic seawater solutions in the presence and absence of fulvic acid showing excellent oil removal capacity of the nanoparticles under different conditions. Results show that these nanoparticles can be utilized to remove oil over a short time with a high removal efficiency under environmentally relevant conditions.

Modeling nanomaterial environmental fate in aquatic systems.

Mathematical models improve our fundamental understanding of the environmental behavior, fate, and transport of engineered nanomaterials (NMs, chemical substances or materials roughly 1-100 nm in size) and facilitate risk assessment and management activities. Although today's large-scale environmental fate models for NMs are a considerable improvement over early efforts, a gap still remains between the experimental research performed to date on the environmental fate of NMs and its incorporation into models. This article provides an introduction to the current state of the science in modeling the fate and behavior of NMs in aquatic environments. We address the strengths and weaknesses of existing fate models, identify the challenges facing researchers in developing and validating these models, and offer a perspective on how these challenges can be addressed through the combined efforts of modelers and experimentalists.

Accumulation dynamics and acute toxicity of silver nanoparticles to Daphnia magna and Lumbriculus variegatus: implications for metal modeling approaches.

Frameworks commonly used in trace metal ecotoxicology (e.g., biotic ligand model (BLM) and tissue residue approach (TRA)) are based on the established link between uptake, accumulation and toxicity, but similar relationships remain unverified for metal-containing nanoparticles (NPs). The present study aimed to (i) characterize the bioaccumulation dynamics of PVP-, PEG-, and citrate-AgNPs, in comparison to dissolved Ag, in Daphnia magna and Lumbriculus variegatus; and (ii) investigate whether parameters of bioavailability and accumulation predict acute toxicity. In both species, uptake rate constants for AgNPs were ∼ 2-10 times less than for dissolved Ag and showed significant rank order concordance with acute toxicity. Ag elimination by L. variegatus fitted a 1-compartment loss model, whereas elimination in D. magna was biphasic. The latter showed consistency with studies that reported daphnids ingesting NPs, whereas L. variegatus biodynamic parameters indicated that uptake and efflux were primarily determined by the bioavailability of dissolved Ag released by the AgNPs. Thus, principles of BLM and TRA frameworks are confounded by the feeding behavior of D. magna where the ingestion of AgNPs perturbs the relationship between tissue concentrations and acute toxicity, but such approaches are applicable when accumulation and acute toxicity are linked to dissolved concentrations. The uptake rate constant, as a parameter of bioavailability inclusive of all available pathways, could be a successful predictor of acute toxicity.

A facile and cost-effective method for separation of oil-water mixtures using polymer-coated iron oxide nanoparticles.

Catastrophic oil spills and oil from waste waters such as bilge and fracking waters pose major environmental concerns. The limitations of existing cleanup techniques for benign oil remediation has inspired a recent scientific impetus to develop oil-absorbing smart nanomaterials. Magnetic nanocomposites were here designed to allow easy recovery from various systems. In this study, sorption of reference MC252 oil with easy-to-synthesize and low-cost hydrophilic polyvinylpyrrolidone-coated iron oxide nanoparticles is reported for the first time. The one-step modified polyol synthesis in air directly generates water-soluble nanoparticles. Stable polyvinylpyrrolidone-coatings are known to minimize environmental alterations of nanoparticles from aggregation and other processes. Iron oxide provides effective magnetic actuation, while both PVP and iron oxide have low toxicity. These nanoparticles gave quantitative (near 100%) oil removal under optimized conditions. The facile synthesis and ease of use represents a significant improvement over existing techniques.

Synthesis and characterization of polyvinylpyrrolidone coated cerium oxide nanoparticles.

There is a pressing need for the development of standard and reference nanomaterials for environmental nanoscience and nanotoxicology. To that aim, suspensions of polyvinylpyrrolidone (PVP)-coated ceria nanoparticles (NPs) were produced. Four differently sized monodispersed samples were produced by using different PVP chain lengths. The chemical and physical properties of these NPs were characterized as prepared and in different ecotoxicology exposure media. Dynamic light scattering analysis showed that the samples were monodispersed, with an unchanged size when suspended in the different media over a 72 h period. Electron microscopy confirmed this and revealed that the larger (ca. 20 nm) particles were aggregates composed of the smaller individual particles (4-5 nm). Electron energy loss spectroscopy (EELS) showed that the smallest and largest samples were composed almost entirely of cerium(III) oxide, with only small amounts of cerium(IV) present in the largest sample. Dissolved cerium concentrations in media were low and constant, showing that the NPs did not dissolve over time. The simple synthesis of the these NPs and their physical and chemical stability in different environmental conditions make them potentially suitable for use as reference materials for (eco)toxicology and surface water environmental studies.

Characterization of suboxic groundwater colloids using a multi-method approach.

Anoxic groundwater colloid properties were measured using a minimally perturbing procedure for sampling, processing, and analysis. Analytical methods included atomic force microscopy (AFM), flow field flow fractionation (FlFFF), and transmission and scanning electron microscopy (TEM and SEM). Shallow groundwater samples showed abundant iron rich nanoparticles (NP) with diameters of 10-30 nm as well as a smaller heterogeneous polydisperse dissolved organic matter (DOM) fraction. AFM results showed NP with average heights of 10 ± 2 nm, which was corroborated by high-resolution TEM and SEM. FlFFF with UV254 nm detection found particles with number average diffusion coefficients of 2-3 × 10(-10) m(2) s(-1) and hydrodynamic diameters between 1.5 and 2 nm probably representing smaller organic macromolecules. Aeration of the samples resulted in extensive agglomeration of NP to form larger (>50 nm) colloids, and a reduction of UV-absorbing material in the 0.5-4 nm range. The complementary methods described have potential applications for investigating the fate and transport of NP in suboxic hotspots such as leachate plumes, wastewater treatment plants, and within the hyporheic mixing zone.

Pseudomonas fluorescens with Nitrogen-Fixing Function Facilitates Nitrogen Recovery in Reclaimed Coal Mining Soils.

Coal mining has caused significant soil nitrogen loss in mining areas, limiting reclamation and reuse in agriculture. This article studies the effects of organic fertilizer, inorganic fertilizer, and the combined application of Pseudomonas fluorescens with the ability of nitrogen fixation on soil nitrogen accumulation and composition in the reclamation area of the Tunlan Coal Mine from 2016 to 2022 under the conditions of equal nitrogen application, providing a scientific basis for microbial fertilization and the rapid increase in nitrogen content in the reclaimed soil of mining areas. The results showed that as the reclamation time increased, the nitrogen content and the composition and structure of the soil treated with fertilization rapidly evolved toward normal farmland soil. The soil nitrogen content increased most rapidly in the presence of added P. fluorescens + organic fertilizer (MB). Compared to other treatments (inorganic fertilizer (CF), organic fertilizer (M), and P. fluorescens + inorganic fertilizer (CFB)), MB increased total nitrogen (TN) to normal farmland soil levels 1-3 years earlier. The comprehensive scores of MB and CFB on the two principal components increased by 1.58 and 0.79 compared to those of M and CF treatments, respectively. This indicates that the combination of P. fluorescens and organic fertilizer improves soil nitrogen accumulation more effectively than the combination of P. fluorescens and inorganic fertilizer. In addition, the application of P. fluorescens increases the content of unknown nitrogen (UN) in acid-hydrolysable nitrogen (AHN) and decreases the content of amino acid nitrogen (AAN) and ammonia nitrogen (AN). However, there was no significant effect on the content of ammonium nitrogen (NH4+-N) and nitrate nitrogen (NO3--N) in soil-mineralized nitrogen (SMN). When combined with inorganic fertilizer, the contribution of SMN to TN increased by 14.78%, while when combined with organic fertilizer, the contribution of AHN to TN increased by 44.77%. In summary, the use of P. fluorescens is beneficial for nitrogen recovery in the reclaimed soil of coal-mining areas. The optimal fertilization method under the experimental conditions is the combination of P. fluorescens and organic fertilizer.

Stability of citrate, PVP, and PEG coated silver nanoparticles in ecotoxicology media.

Silver nanoparticles (AgNPs) are present in the environment and a number of ecotoxicology studies have shown that AgNPs might be highly toxic. Nevertheless, there are little data on their stability in toxicology media. This is an important issue as such dynamic changes affect exposure dose and the nature of the toxicant studied and have a direct impact on all (eco)toxicology data. In this study, monodisperse citrate, PVP, and PEG coated AgNPs with a core size of approximately 10 nm were synthesized and characterized; their behavior was examined in standard OECD media used for Daphnia sp. acute and chronic tests (in the absence of Daphnia). Surface plasmon resonance, size, aggregation, and shape were monitored over 21 days, comparable to a chronic exposure period. Charge stabilized particles (citrate) were more unstable than sterically stabilized particles. Replacement of chloride in the media (due to concerns over chloride-silver interactions) with either nitrate or sulfate resulted in increased shape and dissolution changes. PVP-stabilized NPs in a 10-fold diluted OECD media (chloride present) were found to be the most stable, with only small losses in total concentration over 21 days, and no shape, aggregation, or dissolution changes observed and are recommended for exposure studies.

Transformations of nanomaterials in the environment.

Increasing use of engineered nanomaterials with novel properties relative to their bulk counterparts has generated a need to define their behaviors and impacts in the environment. The high surface area to volume ratio of nanoparticles results in highly reactive and physiochemically dynamic materials in environmental media. Many transformations, e.g. reactions with biomacromolecules, redox reactions, aggregation, and dissolution, may occur in both environmental and biological systems. These transformations and others will alter the fate, transport, and toxicity of nanomaterials. The nature and extent of these transformations must be understood before significant progress can be made toward understanding the environmental risks posed by these materials.

Sequestration of zinc from zinc oxide nanoparticles and life cycle effects in the sediment dweller amphipod Corophium volutator.

We studied the effects of ZnO nanoparticles [ZnO NPs, primary particle size 35 ± 10 nm (circular diameter, TEM)], bulk [160 ± 81 nm (circular diameter, TEM)], and Zn ions (from ZnCl(2)) on mortality, growth, and reproductive endpoints in the sediment dwelling marine amphipod Corophium volutator over a complete lifecycle (100 days). ZnO NPs were characterized by size, aggregation, morphology, dissolution, and surface properties. ZnO NPs underwent aggregation and partial dissolution in the seawater exposure medium, resulting in a size distribution that ranged in size from discrete nanoparticles to the largest aggregate of several micrometers. Exposure via water to all forms of zinc in the range of 0.2-1.0 mg L(-1) delayed growth and affected the reproductive outcome of the exposed populations. STEM-EDX analysis was used to characterize insoluble zinc precipitates (sphaerites) of high sulfur content, which accumulated in the hepatopancreas following exposures. The elemental composition of the sphaerites did not differ for ZnO NP, Zn(2+), and bulk ZnO exposed organisms. These results provide an illustration of the comparable toxicity of Zn in bulk, soluble, and nanoscale forms on critical lifecycle parameters in a sediment dwelling organism.