Potential environmental influence of amino acids on the behavior of ZnO nanoparticles

The fate of nanomaterials when they enter the environment is an issue of increasing concern and thus it is important to know how they interact with natural organic molecules since this may have a significant impact on the particles' behavior. Because of our poor knowledge in this regard, the interaction of ZnO nanoparticles with amino acids of contrasting surface charge, including Histidine (HIS), Glycine (GLY), Aspartic acid (ASP) and Glutamic acid (GLU) which occur commonly in natural habitats, such as the plant root zone, was investigated over a range of pH conditions and concentrations. The addition of the individual amino acid led to significant changes in nanoparticle colloidal zeta potential stability, particle size distribution and the extent of agglomeration. Variations in pH resulted in considerable changes in nanoparticle surface charge and hydrodynamic size. In general, the particle size distribution decreased as the amino acid concentration increased, with more acidic conditions exacerbating this effect. In addition, increased concentrations of amino acids resulted in more stable nanoparticles in aqueous suspensions. Histidine had the greatest effect on colloidal stability, followed by Glycine, Aspartic acid and finally Glutamic acid. This study illustrates how nanoparticle behavior may change in the presence of naturally occurring amino acids, an important consideration when assessing the fate of nanoparticles in the environment. Additionally, utilization of amino acids in industrial processes could reduce particle agglomeration and it could lead to a way of employing more sustainable reagents.     

Occurrence, behavior and effects of nanoparticles in the environment

The increasing use of engineered nanoparticles (NP) in industrial and household applications will very likely lead to the release of such materials into the environment. Assessing the risks of these NP in the environment requires an understanding of their mobility, reactivity, ecotoxicity and persistency. This review presents an overview of the classes of NP relevant to the environment and summarizes their formation, emission, occurrence and fate in the environment. The engineered NP are thereby compared to natural products such as soot and organic colloids. To date only few quantitative analytical techniques for measuring NP in natural systems are available, which results in a serious lack of information about their occurrence in the environment. Results from ecotoxicological studies show that certain NP have effects on organisms under environmental conditions, though mostly at elevated concentrations. The next step towards an assessment of the risks of NP in the environment should therefore be to estimate the exposure to the different NP. It is also important to notice that most NP in technical applications are functionalized and therefore studies using pristine NP may not be relevant for assessing the behavior of the NP actually used.     

Assessment of the physico-chemical behavior of titanium dioxide nanoparticles in aquatic environments using multi-dimensional parameter testing

Assessment of the behavior and fate of engineered nanoparticles (ENPs) in natural aquatic media is crucial for the identification of environmentally critical properties of the ENPs. Here we present a methodology for testing the dispersion stability, ζ-potential and particle size of engineered nanoparticles as a function of pH and water composition. The results obtained from already widely used titanium dioxide nanoparticles (Evonik P25 and Hombikat UV-100) serve as a proof-of-concept for the proposed testing scheme. In most cases the behavior of the particles in the tested settings follows the expectations derived from classical DLVO theory for metal oxide particles with variable charge and an isoelectric point at around pH 5, but deviations also occur. Regardless of a 5-fold difference in BET specific surface area particles composed of the same core material behave in an overall comparable manner. The presented methodology can act as a basis for the development of standardised methods for comparing the behavior of different nanoparticles within aquatic systems.     

Interaction of engineered nanoparticles with various components of the environment and possible strategies for their risk assessment

Nanoparticles are the materials with at least two dimensions between 1 and 100 nm. Mostly these nanoparticles are natural products but their tremendous commercial use has boosted the artificial synthesis of these particles (engineered nanoparticles). Accelerated production and use of these engineered nanoparticles may cause their release in the environment and facilitate the frequent interactions with biotic and abiotic components of the ecosystems. Despite remarkable commercial benefits, their presence in the nature may cause hazardous biological effects. Therefore, detail understanding of their sources, release interaction with environment, and possible risk assessment would provide a basis for safer use of engineered nanoparticles with minimal or no hazardous impact on environment. Keeping all these points in mind the present review provides updated information on various aspects, e.g. sources, different types, synthesis, interaction with environment, possible strategies for risk management of engineered nanoparticles.     

Estimating the relevance of engineered carbonaceous nanoparticle facilitated transport of hydrophobic organic contaminants in porous media

Naturally occurring nanoparticles (NP) enhance the transport of hydrophobic organic contaminants (HOCs) in porous media. In addition, the debate on the environmental impact of engineered nanoparticles (ENP) has become increasingly important. HOC bind strongly to carbonaceous ENP. Thus, carbonaceous ENP may also act as carriers for contaminant transport and might be important when compared to existing transport processes. ENP bound transport is strongly linked to the sorption behavior, and other carbonaceous ENP-specific properties. In our analysis the HOC-ENP sorption mechanism, as well as ENP size and ENP residence time, was of major importance. Our results show that depending on ENP size, sorption kinetics and residence time in the system, the ENP bound transport can be estimated either as (1) negligible, (2) enhancing contaminant transport, or (3) should be assessed by reactive transport modeling. One major challenge to this field is the current lack of data for HOC-ENP desorption kinetics.     

Transport and deposition of functionalized CdTe nanoparticles in saturated porous media

Comprehensive understanding of the transport and deposition of engineered nanoparticles (NPs) in subsurface is required to assess their potential negative impact on the environment. We studied the deposition behavior of functionalized quantum dot (QD) NPs (CdTe) in different types of sands (Accusand, ultrapure quartz, and iron-coated sand) at various solution ionic strengths (IS). The observed transport behavior in ultrapure quartz and iron-coated sand was consistent with conventional colloid deposition theories. However, our results from the Accusand column showed that deposition was minimal at the lowest IS (1mM) and increased significantly as the IS increased. The effluent breakthrough occurred with a delay, followed by a rapid rise to the maximum normalized concentration of unity. Negligible deposition in the column packed with ultrapure quartz sand (100mM) and Accusand (1mM) rules out the effect of straining and suggests the importance of surface charge heterogeneity in QD deposition in Accusand at higher IS. Data analyses further show that only a small fraction of sand surface area contributed in QD deposition even at the highest IS (100mM) tested. The observed delay in breakthrough curves of QDs was attributed to the fast diffusive mass transfer rate of QDs from bulk solution to the sand surface and QD mass transfer on the solid phase. Scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) analysis were used to examine the morphology and elemental composition of sand grains. It was observed that there were regions on the sand covered with layers of clay particles. EDX spectra collected from these regions revealed that Si and Al were the major elements suggesting that the clay particles were kaolinite. Additional batch experiments using gold NPs and SEM analysis were performed and it was observed that the gold NPs were only deposited on clay particles originally on the Accusand surface. After removing the clays from the sand surface, we observed negligible QD deposition even at 100mM IS. We proposed that nanoscale charge heterogeneities on clay particles on Accusand surface played a key role in QD deposition. It was shown that the value of solution IS determined the extent to which the local heterogeneities participated in particle deposition.     

Biodegradability of organic nanoparticles in the aqueous environment

Synthetic nanoparticles have already been detected in the aquatic environment. Therefore, knowledge on their biodegradability is of utmost importance for risk assessment but such information is currently not available. Therefore, the biodegradability of fullerenes, single, double, multi-walled as well as COOH functionalized carbon nanotubes and cellulose and starch nanocrystals in aqueous environment has been investigated according to OECD standards. The biodegradability of starch and cellulose nanoparticles was also compared with the biodegradability of their macroscopic counterparts. Fullerenes and all carbon nanotubes did not biodegrade at all, while starch and cellulose nanoparticles biodegrade to similar levels as their macroscopic counterparts. However, neither comfortably met the criterion for ready biodegradability (60% after 28 days). The cellulose and starch nanoparticles were also found to degrade faster than their macroscopic counterparts due to their higher surface area. These findings are the first report of biodegradability of organic nanoparticles in the aquatic environment, an important accumulation environment for manmade compounds.     

Antibacterial activity of silver nanoparticles grafted on stone surface

Microbial colonization has a relevant impact on the deterioration of stone materials with consequences ranging from esthetic to physical and chemical changes. Avoiding microbial growth on cultural stones therefore represents a crucial aspect for their long-term conservation. The antimicrobial properties of silver nanoparticles (AgNPs) have been extensively investigated in recent years, showing that they could be successfully applied as bactericidal coatings on surfaces of different materials. In this work, we investigated the ability of AgNPs grafted to Serena stone surfaces to inhibit bacterial viability. A silane derivative, which is commonly used for stone consolidation, and Bacillus subtilis were chosen as the grafting agent and the target bacterium, respectively. Results show that functionalized AgNPs bind to stone surface exhibiting a cluster disposition that is not affected by washing treatments. The antibacterial tests on stone samples revealed a 50 to 80 % reduction in cell viability, with the most effective AgNP concentration of 6.7 μg/cm². To our knowledge, this is the first report on antimicrobial activity of AgNPs applied to a stone surface. The results suggest that AgNPs could be successfully used in the inhibition of microbial colonization of stone artworks.     

Influence of dissolved oxygen on aggregation kinetics of citrate-coated silver nanoparticles

Aggregation, an important environmental behavior of silver nanoparticles (AgNPs) influences their bioavailability and cytotoxicity. The work studied the influence of dissolved oxygen (DO) or the redox potential on the stability of AgNPs in aqueous environments. This study employed time-resolved dynamic light scattering (TR-DLS) to investigate the aggregation kinetics of citrate-coated AgNPs. Our results demonstrated that when DO was present, the aggregation rates became much faster (e.g., 3-8 times) than those without DO. The hydrodynamic sizes of AgNPs had a linear growth within the initial 4-6 h and after the linear growth, the hydrodynamic sizes became random for AgNPs in the presence of DO, whereas in the absence of DO the hydrodynamic sizes grew smoothly and steadily. Furthermore, the effects of primary particles sizes (20, 40, and 80 nm) and initial concentrations (300 and 600 μg/L) of AgNPs on aggregation kinetics were also investigated.     

Assessment of transport of two polyelectrolyte-stabilized zero-valent iron nanoparticles in porous media

This study investigated the breakthrough patterns of carboxymethyl cellulose- and polyacrylic acid-stabilized zero-valent iron (Fe(0)) nanoparticles (NZVI) from packed sand columns under a range of pore water velocities of 0.02, 0.2 and 1 cm min(-1) and NZVI influent concentrations of 0.1, 0.5 and 3 g L(-1). The NZVI effluent relative concentrations of both types of particles decreased with slower flow velocities and increasing particle concentrations. PAA-NZVI exhibited slower elution from the columns than CMC-NZVI under identical experimental conditions, and this is attributed to more rapid aggregation kinetics of PAA-NZVI. The elution patterns of PAA-NZVI showed a stronger trend of gradually increasing effluent concentrations with flushing of additional pore volumes, especially at low flushing velocities and higher influent particle concentrations and this phenomenon too can be attributed to increasing aggregate sizes with time which caused decreases in the values of the single collector efficiency and thus the deposition rate constant. A 7 nm increase in CMC-NZVI aggregate size over 60 min was observed using nanoparticle tracking analysis. The reduction in colloidal stability due to aggregation of CMC- and PAA-NZVI was verified using sedimentation tests, and it was found that PAA-NZVI were less stable than CMC-NZVI. There were also notable inherent differences in the two NZVI particles. The CMC-NZVI were monodisperse with a mean diameter of 5.7 ± 0.9 nm, whereas PAA-NZVI had a bimodal particle size distribution with a small sub-population of particles with mean size of 30 ± 21 nm and a more abundant population of 4.6 ± 0.8 nm diameter particles. Furthermore, PAA-NZVI had a lower surface potential. These characteristics are also responsible for the different elution patterns CMC- and PAA-NZVI.     

Combined biocidal action of silver nanoparticles and ions against Chlorococcales (S<Emphasis Type="Italic">cenedesmus quadricauda</Emphasis>, <Emphasis Type="Italic">Chlorella vulgaris)</Emphasis> and filamentous algae (<Emphasis Type="Italic">Klebsormidium sp.</Emphasis>)

Despite the extensive research, the mechanism of the antimicrobial and biocidal performance of silver nanoparticles has not been unequivocally elucidated yet. Our study was aimed at the investigation of the ability of silver nanoparticles to suppress the growth of three types of algae colonizing the wetted surfaces or submerged objects and the mechanism of their action. Silver nanoparticles exhibited a substantial toxicity towards Chlorococcales Scenedesmus quadricauda, Chlorella vulgaris, and filamentous algae Klebsormidium sp., which correlated with their particle size. The particles had very good stability against agglomeration even in the presence of multivalent cations. The concentration of silver ions in equilibrium with nanoparticles markedly depended on the particle size, achieving about 6 % and as low as about 0.1 % or even less for the particles 5 nm in size and for larger ones (40–70 nm), respectively. Even very limited proportion of small particles together with larger ones could substantially increase concentration of Ag ions in solution. The highest toxicity was found for the 5-nm-sized particles, being the smallest ones in this study. Their toxicity was even higher than that of silver ions at the same silver concentration. When compared as a function of the Ag⁺ concentration in equilibrium with 5-nm particles, the toxicity of ions was at least 17 times higher than that obtained by dissolving silver nitrite (if not taking into account the effect of nanoparticles themselves). The mechanism of the toxicity of silver nanoparticles was found complex with an important role played by the adsorption of silver nanoparticles and the ions released from the particles on the cell surface. This mechanism could be described as some sort of synergy between nanoparticles and ions. While our study clearly showed the presence of this synergy, its detailed explanation is experimentally highly demanding, requiring a close cooperation between materials scientists, physical chemists, and biologists.     

Adsorption of phosphate from aqueous solution onto alunite

The phosphate removal potential of alunite, a low cost and abundantly available material, has been investigated. The effects of calcination temperature and time of alunite, adsorbent particle size, pH and initial phosphate concentration on the phosphate adsorption by the calcined alunite have been studied. Phosphate removal was seen to increase with increasing calcination temperature, decreasing adsorbent particle size and pH. Adsorption of phosphate followed first-order rate kinetics. Langmuir and Freundlich adsorption isotherm constants and correlation coefficients were calculated and compared. It was concluded that the adsorption data of phosphate onto calcined alunite fitted to the Langmuir model more than Freundlich model. Specific surface areas of the calcined alunite were calculated at different calcination temperatures and particle sizes.     

The behavior of heavy metal release from sulfide waste rock under microbial action and different environmental factors

The dissolution of heavy metals from the waste rock is controlled by many factors. Herein, we investigated the release behavior of iron (Fe), chromium (Cr), copper (Cu), and zinc (Zn) from sulfide waste rock under the actions of microorganisms and different environmental factors (solution pH value, particle size of waste rock, temperature, Fe³⁺ concentration). The release quantity of heavy metals was negatively correlated with pH and particle size and positively correlated with ambient temperature and Fe³⁺ concentration. Under the experimental conditions of pH value of 3.0, temperature of 35°C, and waste stone particle size of less than 0.075 mm,, the release quantity of Fe, Cr, Cu, and Zn reached 3680, 18.32, 132.20, 26.60 mg·kg^?1 after 20 days of leaching, respectively. Rising the temperature to 45 °C, Fe, Cr, Cu, and Zn release quantities increased to 89.30, 5.81, 105.08, and 28.00 mg·kg^?1. Six hundred milligrams per liter Fe³⁺ increased the release of heavy metals considerably (2.63–65.48 folds). The presence of microorganisms can significantly facilitate the release of heavy metals. Compared to the control group, the release quantities of Fe, Cr, Cu, and Zn increased 4.29, 3.17, 1.54, and 2.39 times, respectively. In addition, the waste rock under microbial action was more seriously corroded than that under chemical factors. The release behavior of these four heavy metals was consistent with the interfacial chemical reaction control model, indicating that the reactions mainly occurred on the surface of the waste rock. This study provides an essential reference for the study of heavy metal leaching behavior.

     

The use of nanoparticles in polymeric and ceramic membrane structures: Review of manufacturing procedures and performance improvement for water treatment

Membrane separations are powerful tools for various applications, including wastewater treatment and the removal of contaminants from drinking water. The performance of membranes is mainly limited by material properties. Recently, successful attempts have been made to add nanoparticles or nanotubes to polymers in membrane synthesis, with particle sizes ranging from 4 nm up to 100 nm. Ceramic membranes have been fabricated with catalytic nanoparticles for synergistic effects on the membrane performance. Breakthrough effects that have been reported in the field of water and wastewater treatment include fouling mitigation, improvement of permeate quality and flux enhancement. Nanomaterials that have been used include titania, alumina, silica, silver and many others. This paper reviews the role of engineered nanomaterials in (pressure driven) membrane technology for water treatment, to be applied in drinking water production and wastewater recycling. Benefits and drawbacks are described, which should be taken into account in further studies on potential risks related to release of nanoparticles into the environment.     

Ecotoxicity of nanosized TiO2. Review of in vivo data

This report presents an exhaustive literature review of data on the effect of nanoparticulate TiO₂ on algae, higher plants, aquatic and terrestrial invertebrates and freshwater fish. The aim, to identify the biologically important characteristics of the nanoparticles that have most biological significance, was unsuccessful, no discernable correlation between primary particle size and toxic effect being apparent. Secondary particle size and particle surface area may be relevant to biological potential of nanoparticles, but insufficient confirmatory data exist. The nanotoxicity data from thirteen studies fail to reveal the characteristics actually responsible for their biological reactivity because reported nanotoxicity studies rarely carry information on the physicochemical characteristics of the nanoparticles tested. A number of practical measures are suggested which should support the generation of reliable QSAR models and so overcome this data inadequacy.     

Metal contamination of short-term snow cover near urban crossroads: correlation analysis of metal content and fine particles distribution

Snow samples were collected near crossroads in Novi Sad, Serbia, during December 2009 to assess metal concentrations (Ca, K, Zn, Fe, Cu, Mn, Al, Pb and Na), fine particle distribution and pH value. The filtered samples of melted snow were analysed, with a focus on particles smaller than a few μm. The most common values of the frequency number distribution curve were either in the range of 0.05-0.07 μm or one order of magnitude higher (0.2-0.5 μm). At examined locations metal concentrations varied from 0.0004 mg L⁻¹ for Pb to 18.9 mg L⁻¹ for Na. Besides Na, which mostly originated from de-icing salt, Ca is found to be the most abundant element in snow indicating the dominant influence of natural factors on snow chemistry. No significant difference was found in concentration of the elements at locations near crossroads with either low or high traffic volume, except for Na and Zn.To investigate how metals were related a correlation analysis was done for the concentrations of metals and with respect to the particle size distribution parameters and pH values. The major influence on the fine particle volume (mass) was concluded to be due to the elements from anthropogenic sources. This conclusion was based on the significant positive correlation between Fe, Zn and Al and the fine particle volume based distribution parameters.     

Thermal co-reduction approach to vary size of silver nanoparticle: its microbial and cellular toxicology

In recent years, silver nanoparticles (AgNPs) have attracted considerable interest in the field of food, agriculture and pharmaceuticals mainly due to its antibacterial activity. AgNPs have also been reported to possess toxic behavior. The toxicological behavior of nanomaterials largely depends on its size and shape which ultimately depend on synthetic protocol. A systematic and detailed analysis for size variation of AgNP by thermal co-reduction approach and its efficacy toward microbial and cellular toxicological behavior is presented here. With the focus to explore the size-dependent toxicological variation, two different-sized NPs have been synthesized, i.e., 60 nm (Ag60) and 85 nm (Ag85). A detailed microbial toxicological evaluation has been performed by analyzing minimum inhibitory concentration (MIC), minimum bactericidal concentration (MBC), diameter of inhibition zone (DIZ), growth kinetics (GrK), and death kinetics (DeK). Comparative cytotoxicological behavior was analyzed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. It has been concluded by this study that the size of AgNPs can be varied, by varying the concentration of reactants and temperature called as “thermal co-reduction” approach, which is one of the suitable approaches to meet the same. Also, the smaller AgNP has shown more microbial and cellular toxicity.     

Growth inhibition of bloom forming cyanobacterium Microcystis aeruginosa by green route fabricated copper oxide nanoparticles

The cyanobacterium Microcystis aeruginosa can potentially proliferate in a wide range of freshwater bionetworks and create extensive secondary metabolites which are harmful to human and animal health. The M. aeruginosa release toxic microcystins that can create a wide range of health-related issues to aquatic animals and humans. It is essential to eliminate them from the ecosystem with convenient method. It has been reported that engineered metal nanoparticles are potentially toxic to pathogenic organisms. In the present study, we examined the growth inhibition effect of green synthesized copper oxide nanoparticles against M. aeruginosa. The green synthesized copper oxide nanoparticles exhibit an excitation of surface plasmon resonance (SPR) at 270 nm confirmed using UV–visible spectrophotometer. The dynamic light scattering (DLS) analysis revealed that synthesized nanoparticles are colloidal in nature and having a particle size of 551 nm with high stability at ?26.6 mV. The scanning electron microscopy (SEM) analysis shows that copper oxide nanoparticles are spherical, rod and irregular in shape, and consistently distributed throughout the solution. The elemental copper and oxide peak were confirmed using energy dispersive x-ray analysis (EDAX). Fourier-transform infrared (FT-IR) spectroscopy indicates the presence of functional groups which is mandatory for the reduction of copper ions. Besides, green synthesized copper oxide nanoparticles shows growth inhibition against M. aeruginosa. The inhibition efficiency was 31.8 % at lower concentration and 89.7 % at higher concentration of copper oxide nanoparticles, respectively. The chlorophyll (a and b) and carotenoid content of M. aeruginosa declined in dose-dependent manner with respect to induction of copper oxide nanoparticles. Furthermore, we analyzed the mechanism behind the cytotoxicity of M. aeruginosa induced by copper oxide nanoparticles through evaluating membrane integrity, reactive oxygen species (ROS), and mitochondrial membrane potential (Δψm) level. The results expose that there is a loss in membrane integrity with ROS formation that leads to alteration in the Δψm, which ends up with severe mitochondrial injury in copper oxide nanoparticles treated cells. Hence, green way synthesized copper oxide nanoparticles may be a useful selective biological agent for the control of M. aeruginosa.     

Sulfadimethoxine and sulfaguanidine: their sorption potential on natural soils

Sulfonamides (SAs) are one of the oldest groups of veterinary chemotherapeutic agents. As these compounds are not completely metabolized in animals, a high proportion of the native form is excreted in feces and urine. They are therefore released either directly to the environment in aquacultures and by grazing animals, or indirectly during the application of manure or slurry. Once released into the environment, SAs become distributed among various environmental compartments and may be transported to surface or ground waters. The physicochemical properties of SAs, dosage and nature of the matrix are the factors mainly responsible for their distribution in the natural environment. Although these rather polar compounds have been in use for over half a century, knowledge of their fate and behavior in soil ecosystems is still limited. Therefore, in this work we have determined the sorption potential of sulfadimethoxine and sulfaguanidine on various natural soils. The influence on sorption of external factors, such as ionic strength and pH, were also determined. The sorption coefficients (K_d) obtained for the sulfonamides investigated were quite low (from 0.20 to 381.17 mL g⁻¹ for sulfadimethoxine and from 0.39 to 35.09 mL g⁻¹ for sulfaguanidine), which indicated that these substances are highly mobile and have the potential to run off into surface waters and/or infiltrate ground water. Moreover, the sorption of these pharmaceuticals was found to be influenced by OC, soil solution pH and ionic strength, with higher K_d values for soils of higher OC and lower K_d values with increasing pH and ionic strength.     

Detection of combustion formed nanoparticles

UV–visible extinction and scattering and two extra situ sampling techniques: atomic force microscopy (AFM) and differential mobility analysis (DMA) are used to follow the evolution of the particles formed in flames. These particle sizing techniques were chosen because of their sensitivity to detect inception particles, which have diameters, d<5 nm, too small to be observed with typical particle measurement instrumentation. The size of the particles determined by AFM and DMA compares well with the size determined by in situ optical measurements, indicating that the interpretation of the UV–visible optical signal is quite good, and strongly showing the presence of d=2–4 nm particles. UV–visible extinction measurements are also used to determine the concentration of d=2–4 nm particles at the exhausts of practical combustion systems. A numerical model, able to reproduce the experimentally observed low coagulation rate of nanoparticles with respect to soot particles, is used to investigate the operating conditions in the combustion chamber and exhaust system for which 2–4 nm particles survive the exhaust or grow to larger sizes. Combustion generated nanoparticles are suspected to affect human and environmental health because of their affinity for water, small size, low rate of coagulation, and large surface area/weight ratio. The ability to isolate nanoparticles from soot particles in hydrosols collected from combustion may be useful for future analysis by a variety of techniques and toxicological assays.