Aggregation and dissolution of silver nanoparticles in natural surface water

This study investigated aggregation and silver release of silver nanoparticles suspended in natural water in the absence and presence of artificial sun light. The influence of the capping layer was investigated using uncoated particles and particles coated with citrate or Tween 80. The experiments were conducted over 15 days in batch mode using a river water matrix. Silver release was monitored over this time while the aggregation state and morphological changes of the silver nanoparticles were tracked using dynamic light scattering and transmission electron microscopy. Results indicate sterically dispersed particles coated with Tween released silver quicker than did bare- and citrate-coated particles, which rapidly aggregated. A dissolved silver concentration of 40 μg/L was reached after just 6 h in the Tween-coated particle systems, accounting for ca. 3% of the total silver. Similar levels of dissolved silver were reached in the uncoated and citrate-coated systems at the end of the 15 days. Silver release was not significantly impacted by the artificial sun light; however, the light (and citrate) imparted significant morphological changes to the particles. Their impact was masked by aggregation, which seemed to be the controlling process in this study.     

Bioavailability of gold nanomaterials to plants: importance of particle size and surface coating

We used the model organisms Nicotiana tabacum L. cv Xanthi (tobacco) and Triticum aestivum (wheat) to investigate plant uptake of 10-, 30-, and 50-nm diameter Au manufactured nanomaterials (MNMs) coated with either tannate (T-MNMs) or citrate (C-MNMs). Primary particle size, hydrodynamic size, and zeta potential were characterized using transmission electron microscopy (TEM), dynamic light scattering (DLS), and electrophoretic mobility measurements, respectively. Plants were exposed to NPs hydroponically for 3 or 7 days for wheat and tobacco, respectively. Volume averaged Au concentrations were determined using inductively coupled plasma mass spectrometry (ICP-MS). Spatial distribution of Au in tissue samples was determined using laser ablation ICP-MS (LA-ICP-MS) and scanning X-ray fluorescence microscopy (μXRF). Both C-MNMs and T-MNMs of each size treatment bioaccumulated in tobacco, but no bioaccumulation of MNMs was observed for any treatment in wheat. These results indicate that MNMs of a wide range of size and with different surface chemistries are bioavailable to plants, provide mechanistic information regarding the role of cell wall pores in plant uptake of MNMs, and raise questions about the importance of plant species to MNM bioaccumulation.     

Hexabromocyclododecane: current understanding of chemistry, environmental fate and toxicology and implications for global management

Hexabromocyclododecane (HBCD) is a globally produced brominated flame retardant (BFR) used primarily as an additive FR in polystyrene and textile products and has been the subject of intensified research, monitoring and regulatory interest over the past decade. HBCD is currently being evaluated under the Stockholm Convention on Persistent Organic Pollutants. HBCD is hydrophobic (i.e., has low water solubility) and thus partitions to organic phases in the aquatic environment (e.g., lipids, suspended solids). It is ubiquitous in the global environment with monitoring data generally exhibiting the expected relationship between proximity to known sources and levels; however, temporal trends are not consistent. Estimated degradation half-lives, together with data in abiotic compartments and long-range transport potential indicate HBCD may be sufficiently persistent and distributed to be of global concern. The detection of HBCD in biota in the Arctic and in source regions and available bioaccumulation data also support the case for regulatory scrutiny. Toxicity testing has detected reproductive, developmental and behavioral effects in animals where exposures are sufficient. Recent toxicological advances include a better mechanistic understanding of how HBCD can interfere with the hypothalamic-pituitary-thyroid axis, affect normal development, and impact the central nervous system; however, levels in biota in remote locations are below known effects thresholds. For many regulatory criteria, there are substantial uncertainties that reduce confidence in evaluations and thereby confound management decision-making based on currently available information.     

Reduction and reoxidation of humic Acid: influence on speciation of cadmium and silver

Naturally occurring variations of redox conditions are considered to affect the interactions between trace metals and humic substances in a 2-fold manner. First, additional proton binding sites of humic substances formed under reducing conditions may also act as binding sites for trace metals. Second, reduced humic substances may transfer electrons to redox-active trace metals. In this study, we investigated the influence of electrochemical reduction of a purified soil humic acid on the binding of two chalcophile metal cations of environmental concern, Cd(2+) and Ag(+), with metal titrations conducted under monitored redox conditions. The binding of cadmium to reduced humic acid was slightly enhanced compared to humic acid reoxidized by O(2) and quantitatively in excellent agreement with the increase in binding sites formed upon reduction. Competitive experiments with calcium indicated that sulfur-containing sites played a minor role in cadmium binding, although sulfur K-edge XANES revealed that 36% of humic sulfur was in a reduced oxidation state. In all experiments with silver, the formation of Ag(0) was detected with transmission electron microscopy. Free Ag(+) activities under reducing conditions were controlled by Ag(0) formation rather than by binding to humic acid.     

Effects of surface ageing on wettability, surface chemistry, and adhesion of wood

The effects of ageing on the surface chemistry, wettability and the surface free energy were determined according to the acid base theory using contact angle measurements and x-ray photoelectron spectroscopy. Time is a significant variable affecting wettability and adhesion. All measured surface parameters of the wood surface were storage time dependent. It could be demonstrated that the effect of ageing on the adhesion of a coating on the wood surface depends not only on the properties of the wood surface, but also on the chemical nature of the coating. Therefore, measurements on wettability without considering the time dependence of surface energy and, above all, its components, are not sufficient to assess effects of ageing on adhesion.     

A review of nitrite and chloride chemistry: Interactions and implications for cured meats

Concerns for the health-related implications of sodium nitrite and sodium chloride in cured meats have lead to reductions in use of both ingredients and there is evidence of chemical interaction between nitrite and chloride in food systems which have implications for cured meats. This review considers the role of chloride in nitrite chemistry and extends this consideration to evaluation of potential changes in cured meat products. Microbiological control depends on nitrite reactivity and a chloride effect has been demonstrated in Clostridium botulinum spore outgrowth and toxin formation. Changes in flavour of cured meats or in development of cured colour are of lesser concern but may take place. More information on specific inhibitory mechanisms by nitrite is needed.     

Arsenic in rice: II. Arsenic speciation in USA grain and implications for human health

Rice is a potentially important route of human exposure to arsenic, especially in populations with rice-based diets. However, arsenic toxicity varies greatly with species. The initial purpose of the present study was to evaluate arsenic speciation in U.S. rice. Twenty-four samples containing high levels of arsenic and produced in different regions of the U.S were selected from a previous market-basket survey. Arsenite and dimethyl arsinic acid (DMA) were the major species detected. DMA increased linearly with increasing total As but arsenite remained fairly constant at approximately 0.1 mg kg(-1), showing that rice high in As was dominated by DMA. A similar result was obtained when our data was combined with other published speciation studies for U.S. rice. However, when all published speciation data for rice was analyzed a second population dominated by inorganic As and lower levels of DMA was found. We thus categorized rice into DMA and Inorganic As types. Rice from the U.S. was predominantly the DMA type, as were single samples from Australia and China, whereas rice from Asia and Europe was the Inorganic As type. We suggest that methylation of As occurs within rice and that genetic differences lead to the two rice types. Insufficient understanding of DMA toxicity precludes a firm assessment of the relative health risks associated with the two rice types but, based on current knowledge, we suggest that the DMA rice type is likely to be less of a health risk than the Inorganic As rice type and, on this basis, rice from the U.S. may be safer than rice from Asia and Europe.     

In situ trace metal speciation in lake surface waters using DGT,dialysis, and filtration

In situ measurements of Fe and Mn by dialysis and diffusive gradients in thin-films (DGT) in 5 lakes (pH 4.7-7.5, ionic strength 0.3-5 mmol l(-1)) and Cu and Zn in an acidic and circumneutral lake were compared to results from on site filtration. For the most acidic lake (pH 4.7) all measurements agreed, indicating an absence of colloids and negligible complexation by organic matter. There was little difference in the Mn concentrations measured by the three techniques for any lake, consistent with it being free from complexation. Zn measured by dialysis in circumneutral water was only slightly higher than DGT measurements, appropriate to only partial complexation. Substantial differences between dialysis and DGT for Cu were consistent with complexation by fulvic and humic substances, though not to the extent predicted by the speciation code WHAM. To achieve a good fit it was necessary to adjust the pK for Cu-fulvic binding from 0.8 to 1.3 and to assume that fulvic substances dominated. The presence of low molecular weight strong binding ligands would also be consistent with the data. Differences between the three measurement methods were greatest for Fe, attributable to the presence of large oxyhydroxide colloids, organic complexation and low molecular weight, reactive hydrolysis products. Fe and Mn concentrations measured by DGT on samples returned to the laboratory were much lower than in situ concentrations, illustrating the need for in situ measurements. While use of two in situ techniques provided useful information on the speciation of these natural waters, further refinements are required for unambiguous characterization of the solution. The use of DGT with a more restricted gel that excludes complexes with humic substances should provide complementary information to in situ dialysis.     

Concentration-dependent mobility, retardation, and speciation of iodine in surface sediment from the Savannah River Site

Iodine occurs in multiple oxidation states in aquatic systems in the form of organic and inorganic species. This feature leads to complex biogeochemical cycling of stable iodine and its long-lived isotope, (129)I. In this study, we investigated the sorption, transport, and interconversion of iodine species by comparing their mobility in groundwaters at ambient concentrations of iodine species (10(-8) to 10(-7) M) to those at artificially elevated concentrations (78.7 μM), which often are used in laboratory analyses. Results demonstrate that the mobility of iodine species greatly depends on, in addition to the type of species, the iodine concentration used, presumably limited by the number of surface organic carbon binding sites to form covalent bonds. At ambient concentrations, iodide and iodate were significantly retarded (K(d) values as high as 49 mL g(-1)), whereas at concentrations of 78.7 μM, iodide traveled along with the water without retardation. Appreciable amounts of iodide during transport were retained in soils due to iodination of organic carbon, specifically retained by aromatic carbon. At high input concentration of iodate (78.7 μM), iodate was found to be reduced to iodide and subsequently followed the transport behavior of iodide. These experiments underscore the importance of studying iodine geochemistry at ambient concentrations and demonstrate the dynamic nature of their speciation during transport conditions.     

Spatial variation of streamwater chemistry in two Swedish boreal catchments: implications for environmental assessment

To evaluate the scale-dependent spatial variability of water chemistry within two Swedish boreal catchments (subcatchment areas 0.01-78 km2), samples were taken at every junction in the stream network during June 2000 and August 2002. The values of most chemical constituents spanned more than an order of magnitude, and the range was similar to that found in all of Northern Sweden by the national stream survey in 2000. According to the official assessment tools used in Sweden, the entire range of environmental status (for pH, absorbance, alkalinity, dissolved organic carbon (DOC)) and human acidification influence existed within these two study catchments. The water chemistry parameters were relatively stable at catchment areas greater than 15 km2. Sampling at that scale may be adequate if generalized values for the landscape are desired. However the chemistry of headwaters, where much of the stream length and aquatic ecosystem is found would not be characterized. Map parameters correlated to the variability in a key chemical parameter, DOC, but the best predictive map parameters differed markedly between catchments. This study highlights the importance of accounting for headwater spatial variability in environmental assessments of running waters, even in relatively pristine areas. The nature of drainage networks with many headwaters and progressively fewer downstream watercourses makes this a considerable challenge.     

Baking performance of egg-yolk lipoproteins before and after surface modifications

Enzymatically modified yolk or yolk plasma and succinylated yolk plasma gave unacceptable Madeira cakes but good fatless sponges of reasonable cell structure although somewhat inferior to the control. Modified yolk plasma showed variable degrees of aggregation in response to various treatments but the overall integrity of lipoprotein structure was unaffected. It is thought that in addition to the macroscopic integrity of yolk lipoproteins, their interfacial molecular anatomy has a marked influence on baking performance in both Madeira cakes and fatless sponges.     

Impact of virus aggregation on inactivation by peracetic acid and implications for other disinfectants

Viruses in wastewater and natural environments are often present as aggregates. The disinfectant dose required for their inactivation, however, is typically determined with dispersed viruses. This study investigates how aggregation affects virus inactivation by chemical disinfectants. Bacteriophage MS2 was aggregated by lowering the solution pH, and aggregates were inactivated by peracetic acid (PAA). Aggregates were redispersed before enumeration to obtain the residual number of individual infectious viruses. In contrast to enumerating whole aggregates, this approach allowed an assessment of disinfection efficiency which remains applicable even if the aggregates disperse in post-treatment environments. Inactivation kinetics were determined as a function of aggregate size (dispersed, 0.55 and 0.90 μm radius) and PAA concentration (5-103 mg/L). Aggregation reduced the apparent inactivation rate constants 2-6 fold. The larger the aggregate and the higher the PAA concentration, the more pronounced the inhibitory effect of aggregation on disinfection. A reaction-diffusion based model was developed to interpret the experimental results, and to predict inactivation rates for additional aggregate sizes and disinfectants. The model showed that the inhibitory effect of aggregation arises from consumption of the disinfectant within the aggregate, but that diffusion of the disinfectant into the aggregates is not a rate-limiting factor. Aggregation therefore has a large inhibitory effect if highly reactive disinfectants are used, whereas inactivation by mild disinfectants is less affected. Our results suggest that mild disinfectants should be used for the treatment of water containing viral aggregates.     

Linking solid phase speciation of Pb sequestered to birnessite to oral Pb bioaccessibility: implications for soil remediation

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of lead-contaminated soils. In this study, Pb was sorbed to a model soil mineral, birnessite, and was placed in a simulated gastrointestinal tract (in vitro) to simulate the possible effects of ingestion of a soil contaminated with Pb. The changes in Pb speciation were determined using extended X-ray absorption fine structure and X-ray absorption near edge spectroscopy. Birnessite has a very high affinity for Pb with a sorption maximum of 0.59 mol Pb kg(-1) (approximately 12% Pb sorbed by mass) in which there was no detectable bioaccessible Pb (< 0.002%). Surface speciation of the birnessite Pb was determined to be a triple corner sharing complex in the birnessite interlayer. Lead sorbed to Mn oxide in contaminated media will have a very low (approximately equal to 0) Pb bioaccessibility and present little risk associated with incidental ingestion of soil. These results suggest that birnessite, and other Mn oxides would be powerful remediation tools for Pb-contaminated media because of their high affinity for Pb.     

Migration of silver from commercial plastic food containers and implications for consumer exposure assessment

Food storage containers with embedded silver as an antibacterial agent promise longer durability of food. For risk assessment the release of this silver into the stored food and resulting human exposure need to be known. For the purpose of exposure assessment, silver migration from commercial plastic containers with declared content of ‘nano-’ or ‘micro-silver’ into different food simulants (water, 10% ethanol, 3% acetic acid, olive oil) was quantitatively determined by ICP-MS and the form of the released silver was investigated. The highest migration of silver was observed for the acidic food simulant with 30 ng silver cm^?2 contact surface within 10 days at 20°C. In a second and third use cycle, migration dropped by a factor of up to 10, so that the maximum cumulated release over three use cycles was 34 ng cm^?2. The silver release over time was described using a power function and a numerical model that simulates Fickian diffusion through the plastic material. The released silver was found to be in ionic form, but also in the form of silver nanoparticles (around 12%). Consumer exposure to the total amount of silver released from the food containers is low in comparison with the background silver exposure of the general population, but since natural background concentrations are only known for ionic silver, the exposure to silver nanoparticles is not directly comparable with a safe background level.     

An FTIR-DRIFT study on river sediment particle structure: implications for biofilm dynamics and pollutant binding

Diffuse reflectance infrared Fourier transform (DRIFT) spectrometry was applied to a set of sediment samples collected by traps over one and a half years in a mid-mountainous river. Dynamic changes in hydrological and life-cycle conditions generated sediment particles of different C(org) content and organic composition. Periods in the midst of or shortly after flood events left particles poor in C(org) content with spectral features that were enriched in carboxylic and aromatic signals. These are characteristic of terrestrial oxidized vascular plant debris. Low-flow conditions saw the consequent build-up of amide, aliphatic, and polysaccharide moieties as expected for autochthonous biofilm derived material. A peak ratio of two bands representing the alternation of these two types of organic matter showed that flood particle C(org) had a higher affinity for metals than the high C(org) of mature biofilms, probably owing to higher COO- contents in the first. The relative dietary bioavailability of the metals from sediment C(org), which is related to the nutritional value of the substrate, is therefore probably lower in the aftermath of a flood than in prolonged low-flow situations. This needs to be accounted for in future metal speciation and bioavailability modeling approaches.     

Tobacco industry research and efforts to manipulate smoke particle size: implications for product regulation.

Over the past half-century of cigarette design, tobacco manufacturers have prioritized efficiency of delivery alongside ease of inhalation and use. As a result, the modern cigarette is uniquely effective at facilitating the absorption of nicotine as well as carcinogens and other toxins. The present study draws on internal tobacco company documents to assess industry consideration of the role of smoke particle size as a potentially controllable influence over inhalation patterns and lung exposure. Tobacco manufacturers evaluated particle size manipulation both as a means of controlling physical and sensory product attributes and as a possible approach to reducing health hazards related to exposure. Industry scientists concluded that the smoke aerosol particle distribution of conventional cigarettes, constructed within common parameters, falls within a narrow and effective inhalation range. However, the internal findings suggest that differences in smoke particle size distribution are possible through less conventional approaches to product design. We propose that particle size be included among the many design features to be considered in emerging tobacco product regulation. However, the present review does not address whether particle size regulation would be a plausible means of substantially reducing addictiveness or harmfulness of cigarettes, and therefore we do not propose it as a high-priority target for regulation.     

Cytotoxicity of carbon nanomaterials: single-wall nanotube, multi-wall nanotube, and fullerene

A cytotoxicity test protocol for single-wall nanotubes (SWNTs), multi-wall nanotubes (with diameters ranging from 10 to 20 nm, MWNT10), and fullerene (C60) was tested. Profound cytotoxicity of SWNTs was observed in alveolar macrophage (AM) after a 6-h exposure in vitro. The cytotoxicity increases by as high as approximately 35% when the dosage of SWNTs was increased by 11.30 microg/cm2. No significant toxicity was observed for C60 up to a dose of 226.00 microg/cm2. The cytotoxicity apparently follows a sequence order on a mass basis: SWNTs > MWNT10 > quartz > C60. SWNTs significantly impaired phagocytosis of AM at the low dose of 0.38 microg/cm2, whereas MWNT10 and C60 induced injury only at the high dose of 3.06 microg/cm2. The macrophages exposed to SWNTs or MWNT10 of 3.06 microg/cm2 showed characteristic features of necrosis and degeneration. A sign of apoptotic cell death likely existed. Carbon nanomaterials with different geometric structures exhibit quite different cytotoxicity and bioactivity in vitro, although they may not be accurately reflected in the comparative toxicity in vivo.     

Yerba Mate Tea (Ilex paraguariensis): a comprehensive review on chemistry, health implications, and technological considerations

ABSTRACT:  Yerba Mate tea, an infusion made from the leaves of the tree Ilex paraguariensis , is a widely consumed nonalcoholic beverage in South America which is gaining rapid introduction into the world market, either as tea itself or as ingredient in formulated foods or dietary supplements. The indigenous people have used it for centuries as a social and medicinal beverage. Yerba Mate has been shown to be hypocholesterolemic, hepatoprotective, central nervous system stimulant, diuretic, and to benefit the cardiovascular system. It has also been suggested for obesity management. Yerba Mate protects DNA from oxidation and in vitro low-density lipoprotein lipoperoxidation and has a high antioxidant capacity. It has also been reported that Yerba Mate tea is associated to both the prevention and the cause of some types of cancers. Yerba Mate has gained public attention outside of South America, namely the United States and Europe, and research on this tea has been expanding. This review presents the usage, chemistry, biological activities, health effects, and some technological considerations for processing of Yerba Mate tea. Furthermore, it assesses in a concise and comprehensive way the potential of Ilex paraguariensis as a source of biological compounds for the nutraceutical industry.     

Reduction of chlorinated ethanes by nanosized zero-valent iron: kinetics, pathways, and effects of reaction conditions

Nanosized iron (< 100 nm in diameter) was synthesized in the laboratory and applied to the reduction of eight chlorinated ethanes (hexachloroethane (HCA), pentachloroethane (PCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA), 1,1,2-trichloroethane (1,1,2-TCA), 1,1,1-trichloroethane (1,1,1-TCA), 1,2-dichloroethane (1,2-DCA), and 1,1-dichloroethane (1,1-DCA)) in batch reactors. Reduction of 1,1,1-TCA increased linearly with increasing iron loading between 0.01 and 0.05 g per 124 mL solution (0.08-0.4 g/L). Varying initial concentrations of PCA between 0.025 and 0.125 mM resulted in relatively constant pseudo-first-order rate constants, indicating PCA removal conforms to pseudo-first-order kinetics. The reduction of 1,1,2,2-TeCA decreased with increasing pH; however, dehydrohalogenation of 1,1,2,2-TeCA became important at high pH. All chlorinated ethanes except 1,2-DCA were transformed to less chlorinated ethanes or ethenes. The surface-area-normalized rate constants from first-order kinetics analysis ranged from < 4 x 10(-6) to 0.80 L m(-2) h(-1). In general, the reactivity increased with increasing chlorination. Among tri- and tetrasubstituted compounds, the reactivity was higher for compounds with chlorine atoms more localized on a single carbon (e.g., 1,1,1-TCA > 1,1,2-TCA). Reductive beta-elimination was the major pathway for the chlorinated ethanes possessing alpha,beta-pairs of chlorine atoms to form chlorinated ethenes, which subsequently reacted with nanosized iron. Reductive alpha-elimination and hydrogenolysis were concurrent pathways for compounds possessing chlorine substitution on one carbon only, forming less chlorinated ethanes.