Nanoparticles enter soils through various pathways. In the soil, they undergo various interactions with the solution and the solid phase. We tested the following hypotheses using batch experiments: ...i) the colloidal stability of Ag NP increases through sorption of soil-borne dissolved organic matter (DOM) and thus inhibits aggregation; ii) the presence of DOM suppresses Ag oxidation; iii) the surface charge of Ag NP governs sorption onto soil particles. Citrate-stabilized and bare Ag NPs were equilibrated with (colloid-free) soil solution extracted from a floodplain soil for 24h. Nanoparticles were removed through centrifugation. Concentrations of free Ag ions and DOC, the specific UV absorbance at a wavelength of 254nm, and the absorption ratio α254/α410 were determined in the supernatant. Nanoparticle aggregation was studied using time-resolved dynamic light scattering (DLS) measurement following the addition of soil solution and 1.5mM Ca2+ solution. To study the effect of surface charge on the adsorption of Ag NP onto soil particles, bare and citrate-stabilized Ag NP, differing in the zeta potential, were equilibrated with silt at a solid-to-solution ratio of 1:10 and an initial Ag concentration range of 30 to 320μg/L.
Results showed that bare Ag NPs sorb organic matter, with short-chained organic matter being preferentially adsorbed over long-chained, aromatic organic matter. Stabilizing effects of organic matter only come into play at higher Ag NP concentrations. Soil solution inhibits the release of Ag+ ions, presumably due to organic matter coatings. Sorption to silt particles was very similar for the two particle types, suggesting that the surface charge does not control Ag NP sorption. Besides, sorption was much lower than in comparable studies with sand and glass surfaces.
•Soil solution reduces the release of ionic silver from Ag NP.•The stabilizing effect of sorbed organic matter is dependent on Ag NP concentration.•Short-chained DOM is preferentially adsorbed over long-chained, aromatic DOM.•Ag NP may form a sink for Ag+ ions in the soil.
Nanoparticles serve various industrial and domestic purposes which is reflected in their steadily increasing production volume. This economic success comes along with their presence in the ...environment and the risk of potentially adverse effects in natural systems. Over the last decade, substantial progress regarding the understanding of sources, fate, and effects of nanoparticles has been made. Predictions of environmental concentrations based on modelling approaches could recently be confirmed by measured concentrations in the field. Nonetheless, analytical techniques are, as covered elsewhere, still under development to more efficiently and reliably characterize and quantify nanoparticles, as well as to detect them in complex environmental matrixes. Simultaneously, the effects of nanoparticles on aquatic and terrestrial systems have received increasing attention. While the debate on the relevance of nanoparticle-released metal ions for their toxicity is still ongoing, it is a re-occurring phenomenon that inert nanoparticles are able to interact with biota through physical pathways such as biological surface coating. This among others interferes with the growth and behaviour of exposed organisms. Moreover, co-occurring contaminants interact with nanoparticles. There is multiple evidence suggesting nanoparticles as a sink for organic and inorganic co-contaminants. On the other hand, in the presence of nanoparticles, repeatedly an elevated effect on the test species induced by the co-contaminants has been reported. In this paper, we highlight recent achievements in the field of nano-ecotoxicology in both aquatic and terrestrial systems but also refer to substantial gaps that require further attention in the future.
The application of engineered silver nanoparticles (AgNPs) in a considerable amount of registered commercial products inevitably will result in the continuous release of AgNPs into the natural ...aquatic environment. Therefore, native biofilms, as the prominent life form of microorganisms in almost all known ecosystems, will be subjected to AgNP exposure. Despite the exponentially growing research activities worldwide, it is still difficult to assess nanoparticle-mediated toxicity in natural environments. In order to obtain an ecotoxicologically relevant exposure scenario, we performed experiments with artificial stream mesocosm systems approaching low dose AgNP concentrations close to predicted environmental concentrations. Pregrown freshwater biofilms were exposed for 14 days to citrate-stabilized AgNPs at a concentration of 600 μg l-1 in two commonly used sizes (30 and 70 nm). Sublethal effects of AgNP treatment were assessed with regard to biofilm structure by gravimetric measurements (biofilm thickness and density) and by two biomass parameters, chlorophyll a and protein content. The composition of bacterial biofilm communities was characterized by t-RFLP fingerprinting combined with phylogenetic studies based on the 16S gene. After 14 days of treatment, the structural parameters of the biofilm such as thickness, density, and chlorophyll a and protein content were not statistically significantly changed by AgNP exposure. Furthermore, t-RFLP fingerprint analysis showed that the bacterial diversity was not diminished by AgNPs, as calculated by Shannon Wiener and evenness indices. Nevertheless, t-RFLP analysis also indicated that AgNPs led to an altered biofilm community composition as was shown by cluster analysis and multidimensional scaling (MDS) based on the Bray Curtis index. Sequence analysis of cloned 16S rRNA genes further revealed that changes in community composition were related with the displacement of putatively AgNP-sensitive bacterial taxa Actinobacteria, Chloroflexi, and Cyanobacteria by taxa known for their enhanced adaptability towards metal stress, such as Acidobacteria, Sphingomonadales, and Comamonadaceae. This measurable community shift, even after low dose AgNP treatment, causes serious concerns with respect to the broad application of AgNPs and their potentially adverse impact on the ecological function of lotic biofilms, such as biodegradation or biostabilization.
Silver nanoparticles (Ag NPs) could be found in aquatic systems in the near future. Although the interplay between aggregate formation and disaggregation is an important factor for mobility, ...bioavailability and toxicity of Ag NPs in surface waters, the factors controlling disaggregation of Ag NP homoaggregates are still unknown. In this study, we investigated the reversibility of homoaggregation of citrate coated Ag NPs in a Rhine River water matrix. We characterized the disaggregation of Ag NP homoaggregates by ionic strength reduction and addition of Suwannee River humic acid (SRHA) in the presence of strong and weak shear forces. In order to understand the disaggregation processes, we also studied the nature of homoaggregates and their formation dynamics under the influence of SRHA, Ca2+ concentration and nanoparticle concentration.
Even in the presence of SRHA and at low particle concentrations (10μgL−1), aggregates formed rapidly in filtered Rhine water. The critical coagulation concentration (CCC) of Ca2+ in reconstituted Rhine water was 1.5mmolL−1 and was shifted towards higher values in the presence of SRHA. Analysis of the attachment efficiency as a function of Ca2+ concentration showed that SRHA induces electrosteric stabilization at low Ca2+ concentrations and cation-bridging flocculation at high Ca2+ concentrations. Shear forces in the form of mechanical shaking or ultrasound were necessary for breaking the aggregates. Without ultrasound, SRHA also induced disaggregation, but it required several days to reach a stable size of dense aggregates still larger than the primary particles.
Citrate stabilized Ag NPs may be in the form of reaction limited aggregates in aquatic systems similar to the Rhine River. The size and the structure of these aggregates will be dynamic and be determined by the solution conditions. Seasonal variations in the chemical composition of natural waters can result in a sedimentation-release cycle of engineered nanoparticles.
•Citrate coated silver nanoparticles aggregate rapidly in Rhine River water matrix.•Aggregate morphology is determined by the Ca2+ concentration and NOM.•Silver nanoparticle aggregates can be fragmented only partially.•Mechanical forces plus NOM or low ionic strength are required for aggregate breakup.•Silver nanoparticle aggregate morphology changes with concentration of ions and NOM.
The sulfidized form represents an environmentally relevant transformation state of silver nanoparticles (Ag-NPs) released into natural systems via wastewater route. However, the detailed ...characterization of sulfidized silver nanoparticles (S-Ag-NPs) is missing and their colloidal stability in aquatic systems is only insufficiently studied. The aim of this study was to systematically evaluate the surface properties, morphology, structure, composition, as well as aggregation dynamics of S-Ag-NPs in synthetic and natural river water. The S-Ag-NPs were prepared by sulfidation of citrate-coated silver nanoparticles (Cit-Ag-NPs). The sulfidation of Ag-NPs was accompanied by the formation of fiber-like Ag2S nano-bridges, Ag0-Ag2S core-shell structures, and hollow regions. In contrast to the published literature, the nano-bridges were thinner (2–9 nm) and longer (up to 60 nm), they formed at higher S2−/Ag molar ratio (2.041), and the formation of the core-shell structures was observed even in the absence of natural organic matter (NOM). Furthermore, we observed selective sulfidation of nanoparticles which can induce the hot spots for the release of toxic Ag+ ions. The critical coagulation concentration (CCC) of Ca2+ determined for S-Ag-NPs in reconstituted river water was 2.47 ± 0.23 mmol/L and thus higher than the CCC obtained for Cit-Ag-NPs in our earlier study revealing higher colloidal stability of S-Ag-NPs. In natural river water, S-Ag-NPs were also colloidally more stable compared to the Cit-Ag-NPs. Furthermore, the stabilizing effect of NOM was much higher for S-Ag-NPs than for Cit-Ag-NPs. For S-Ag-NPs stabilized by a low amount of citrate, we expect longer residence times in the water phase of rivers and thus higher risk for aquatic organisms. In contrast to this, the pristine Cit-Ag-NPs are expected to be accumulated faster in the sediments representing higher risk for benthic organisms. This study contributes to better understanding of environmental fate and effects of Ag-NPs released via wastewater route.
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•Formation of thin and long silver sulfide nano-bridges for sulfidized Ag-NPs.•Nano-bridges are formed at a higher S2−/Ag molar ratio than reported in literature.•Ag0-Ag2S core-shell structures of sulfidized Ag-NPs are formed in absence of NOM.•Sulfidation enhances colloidal stability of citrate-coated Ag-NPs in river water.•Stabilizing effect of NOM is higher for sulfidized than for citrate-coated Ag-NPs.
Engineered inorganic nanoparticles (EINP) from consumers' products and industrial applications, especially silver and titanium dioxide nanoparticles (NP), are emitted into the aquatic and terrestrial ...environments in increasing amounts. However, the current knowledge on their environmental fate and biological effects is diverse and renders reliable predictions complicated. This review critically evaluates existing knowledge on colloidal aging mechanisms, biological functioning and transport of Ag NP and TiO2 NP in water and soil and it discusses challenges for concepts, experimental approaches and analytical methods in order to obtain a comprehensive understanding of the processes linking NP fate and effects.
Ag NP undergo dissolution and oxidation with Ag2S as a thermodynamically determined endpoint. Nonetheless, Ag NP also undergo colloidal transformations in the nanoparticulate state and may act as carriers for other substances. Ag NP and TiO2 NP can have adverse biological effects on organisms. Whereas Ag NP reveal higher colloidal stability and mobility, the efficiency of NOM as a stabilizing agent is greater towards TiO2 NP than towards Ag NP, and multivalent cations can dominate the colloidal behavior over NOM. Many of the past analytical obstacles have been overcome just recently. Single particle ICP-MS based methods in combination with field flow fractionation techniques and hydrodynamic chromatography have the potential to fill the gaps currently hampering a comprehensive understanding of fate and effects also at a low field relevant concentrations.
These analytical developments will allow for mechanistically orientated research and transfer to a larger set of EINP. This includes separating processes driven by NP specific properties and bulk chemical properties, categorization of effect-triggering pathways directing the EINP effects towards specific recipients, and identification of dominant environmental parameters triggering fate and effect of EINP in specific ecosystems (e.g. soil, lake, or riverine systems).
•Mechanisms of NOM sorption to NP and their effects on aggregation are largely unknown.•Masking, catching and dissolution processes determine nanoparticle fate & effect.•Assessment of environmental impacts on NP fate and effects needs further studies.•Single particle analytics enlighten nanoparticle speciation in the environment.•Still an analytical challenge: nanoparticle characterization in complex matrices
Studies assessing the acute and chronic toxicity of silver nanoparticle (nAg) materials rarely consider potential implications of environmental variables. In order to increase our understanding in ...this respect, we investigated the acute and chronic effects of various nAg materials on Daphnia magna. Thereby, different nanoparticle size classes with a citrate coating (20-, ~30-, 60- as well as 100-nm nAg) and one size class without any coating (140nm) were tested, considering at the same time two pH levels (6.5 and 8.0) as well as the absence or presence of dissolved organic matter (DOM; <0.1 or 8.0mg total organic carbon/L). Results display a reduced toxicity of nAg in media with higher pH and the presence of DOM as well as increasing initial particle size, if similarly coated. This suggests that the associated fraction of Ag species <2nm (including Ag+) is driving the nAg toxicity. This hypothesis is supported by normalizing the 48-h EC50-values to Ag species <2nm, which displays comparable toxicity estimates for the majority of the nAg materials assessed. It may therefore be concluded that a combination of both the particle characteristics, i.e. its initial size and surface coating, and environmental factors trigger the toxicity of ion-releasing nanoparticles.
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•Ag nanoparticle (nAg) coating and particle size drive the toxicity towards Daphnia.•pH and dissolved organic matter affect the ecotoxicological potential of nAg.•nAg toxicity is mainly driven by the released Ag ions.
The sulfidation and aging of silver nanoparticles (Ag‐NPs) with natural organic matter (NOM) are major transformation processes along their pathway in wastewater treatment plants and surface waters. ...Although soils appear to be a sink for disposed Ag‐NPs, the impact of variable saturation on the transport and retention behavior in porous media is still not fully understood. We studied the behavior of sulfidized silver nanoparticles (S‐Ag‐NPs, 1 mg L−1) in saturated and unsaturated sand columns regarding the effects of (i) the presence of NOM (5 mg L−1) in the aquatic phase on retention, transport, and remobilization of S‐Ag‐NPs and (ii) the distribution and quantity of air‐water and solid‐water interfaces for different flow velocities determined via X‐ray microtomography (X‐ray μCT). Unsaturated transport experiments were conducted under controlled conditions with unit gradients in water potential and constant water content along the flow direction for each applied flux. It was shown that (i) NOM in S‐Ag‐NP dispersion highly increased the NP‐mobility; (ii) differences between saturated and unsaturated transport were increasing with decreasing flux and, consequently, decreasing water contents; (iii) both, solid‐water and air‐water interfaces were involved in retention of S‐Ag‐NPs aged by NOM. Using numerical model simulations and X‐ray μCT of flow experiments, the breakthrough of Ag‐NP could be explained by a disproportional increase in air‐water interfaces and an increasing attachment efficiency with decreasing water content and flow velocity.
Key Points
The transformation of Cit‐Ag‐NPs to NOM‐S‐Ag‐NPs, as it is expected when released into the environment, decreases their mobility
The retardation of particles was mainly dependent on the interfacial areas between the solid‐water and air‐water phase
The decreasing amount of particle breakthrough at reduced saturation was dependent on the increasing AWI and the decreasing flow velocity
•Outdoor, large-scale column experiments and laboratory batch studies•Strong retention of Ag NP, but highest mobility of soil-aged Ag NP•50% of retained Ag is remobilizable by mechanical forces and ...hydrochemical changes.•NOM and ionic strength reduction enhances NP mobility, Ca reduces it.•Co-mobilization with natural colloids is an important remobilization mechanism.
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Riverbank filtration systems are important structures that ensure the cleaning of infiltrating surface water for drinking water production. In our study, we investigated the potential risk for a breakthrough of environmentally aged silver nanoparticles (Ag NP) through these systems. Additionally, we identified factors leading to the remobilization of Ag NP accumulated in surficial sediment layers in order to gain insights into remobilization mechanisms.
We conducted column experiments with Ag NP in an outdoor pilot plant consisting of water-saturated sediment columns mimicking a riverbank filtration system. The NP had previously been aged in river water, soil extract, and ultrapure water, respectively. We investigated the depth-dependent breakthrough and retention of NP. In subsequent batch experiments, we studied the processes responsible for a remobilization of Ag NP retained in the upper 10 cm of the sediments, induced by ionic strength reduction, natural organic matter (NOM), and mechanical forces. We determined the amount of remobilized Ag by ICP-MS and differentiated between particulate and ionic Ag after remobilization using GFAAS. The presence of Ag-containing heteroaggregates was investigated by combining filtration with single-particle ICP-MS.
Single and erratic Ag breakthrough events were mainly found in 30 cm depth and Ag NP were accumulated in the upper 20 cm of the columns. Soil-aged Ag NP showed the lowest retention of only 54%. Remobilization was induced by the reduction of ionic strength and the presence of NOM in combination with mechanical forces. The presence of calcium in the aging- as well as the remobilizing media reduced the remobilization potential. Silver NP were mainly remobilized as heteroaggregates with natural colloids, while dissolution played a minor role.
Our study indicates that the breakthrough potential of Ag NP in riverbank filtration systems is generally low, but the aging in soil increases their mobility. Remobilization processes are associated to co-mobilization with natural colloids.
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