Hypertonic stress induced changes of Pseudomonas fluorescens adhesion towards soil minerals studied by AFM.

Studying bacterial adhesion to mineral surfaces is crucial for understanding soil properties. Recent research suggests that minimal coverage of sand particles with cell fragments significantly reduces soil wettability. Using atomic force microscopy (AFM), we investigated the influence of hypertonic stress on Pseudomonas fluorescens adhesion to four different minerals in water. These findings were compared with theoretical XDLVO predictions. To make adhesion force measurements comparable for irregularly shaped particles, we normalized adhesion forces by the respective cell-mineral contact area. Our study revealed an inverse relationship between wettability and the surface-organic carbon content of the minerals. This relationship was evident in the increased adhesion of cells to minerals with decreasing wettability. This phenomenon was attributed to hydrophobic interactions, which appeared to be predominant in all cell-mineral interaction scenarios alongside with hydrogen bonding. Moreover, while montmorillonite and goethite exhibited stronger adhesion to stressed cells, presumably due to enhanced hydrophobic interactions, kaolinite showed an unexpected trend of weaker adhesion to stressed cells. Surprisingly, the adhesion of quartz remained independent of cell stress level. Discrepancies between measured cell-mineral interactions and those calculated by XDLVO, assuming an idealized sphere-plane geometry, helped us interpret the chemical heterogeneity arising from differently exposed edges and planes of minerals. Our results suggest that bacteria may have a significant impact on soil wettability under changing moisture condition.

FTIR spectroscopy and molecular level insight of diluted aqueous solutions of acetic acid.

Aqueous solutions of acetic acid (AA) have been intensively explored for decades with a particular attention addressed to the hydrogen bond network generated by COOH group at different concentrations. In majority of studies conducted so far the envelope originated from νCO is decomposed into two bands assigned to differently hydrated monomers: the one presumably to AA···H2O, and another one to AA···(H2O)2. In order to examine if species other than the mentioned monomers produce this spectral signature, we performed computational and FTIR spectroscopic study of AA in aqueous solutions. Dilute solutions of deuterated acetic acid (CD3COOD) in D2O and in C2Cl4 as a reference were prepared (c0 = 0.001, 0.01 and 0.1 mol dm-3) as well as of deuterated sodium acetate (CD3COONa) in D2O. CD3COOD in 0.1 mol dm-3 solution in D2O displays a feature that separated in two signals with maxima at 1706 cm-1 and 1687 cm-1. A combined DFT and molecular dynamics study performed in this work showed the assignation of those spectral bands to be a more complex problem than previously thought, with syn-anti isomerism and hydration contributing to the experimentally observed broad νCO envelope.

Purification effects show seed and root mucilage's ability to respond to changing rhizosphere conditions.

Mucilage, a polysaccharide-containing hydrogel, is hypothesized to play a key role in the rhizosphere as a self-organized system because it may vary its supramolecular structure with changes in the surrounding solution. However, there is currently limited research on how these changes are reflected in the physical properties of real mucilage. This study examines the role of solutes in maize root, wheat root, chia seed, and flax seed mucilage in relation to their physical properties. Two purification methods, dialysis and ethanol precipitation, were applied to determine the purification yield, cation content, pH, electrical conductivity, surface tension, viscosity, transverse 1 H relaxation time, and contact angle after drying of mucilage before and after purification. The two seed mucilage types contain more polar polymers that are connected to larger assemblies via multivalent cation crosslinks, resulting in a denser network. This is reflected in higher viscosity and water retention ability compared to root mucilage. Seed mucilage also contains fewer surfactants, making them better wettable after drying compared to the two root mucilage types. The root mucilage types, on the other hand, contain smaller polymers or polymer assemblies and become less wettable after drying. However, wettability not only depends on the amount of surfactants but also on their mobility, as well as the strength and mesh size of the network structure. The changes in physical properties and cation composition observed after ethanol precipitation and dialysis suggest that the polymer network of seed mucilage is more stable and specialized in protecting the seeds from unfavorable environmental conditions. In contrast, root mucilage is characterized by fewer cationic interactions and its network relies more on hydrophobic interactions. This allows root mucilage to be more flexible in responding to changing environmental conditions, facilitating nutrient and water exchange between root surfaces and the rhizosphere soil.

Changes in cell surface properties of Pseudomonas fluorescens by adaptation to NaCl induced hypertonic stress.

Determination of the effect of water stress on the surface properties of bacteria is crucial to study bacterial induced soil water repellency. Changes in the environmental conditions may affect several properties of bacteria such as the cell hydrophobicity and morphology. Here, we study the influence of adaptation to hypertonic stress on cell wettability, shape, adhesion, and surface chemical composition of Pseudomonas fluorescens. From this we aim to discover possible relations between the changes in wettability of bacterial films studied by contact angle and single cells studied by atomic and chemical force microscopy (AFM, CFM), which is still lacking. We show that by stress the adhesion forces of the cell surfaces towards hydrophobic functionalized probes increase while they decrease towards hydrophilic functionalized tips. This is consistent with the contact angle results. Further, cell size shrunk and protein content increased upon stress. The results suggest two possible mechanisms: Cell shrinkage is accompanied by the release of outer membrane vesicles by which the protein to lipid ratio increases. The higher protein content increases the rigidity and the number of hydrophobic nano-domains per surface area.

Water Stress-Driven Changes in Bacterial Cell Surface Properties.

Increased drought intensity and frequency exposes soil bacteria to prolonged water stress. While numerous studies reported on behavioral and physiological mechanisms of bacterial adaptation to water stress, changes in bacterial cell surface properties during adaptation are not well researched. We studied adaptive changes in cell surface hydrophobicity (CSH) after exposure to osmotic (NaCl) and matric stress (polyethylene glycol 8000 [PEG 8000]) for six typical soil bacteria (Bacillus subtilis, Arthrobacter chlorophenolicus, Pseudomonas fluorescens, Novosphingobium aromaticivorans, Rhodococcus erythropolis, and Mycobacterium pallens) covering a wide range of cell surface properties. Additional physicochemical parameters (surface chemical composition, surface charge, cell size and stiffness) of B. subtilis and P. fluorescens were analyzed to understand their possible contribution to CSH development. Changes in CSH caused by osmotic and matric stress depend on strain and stress type. CSH of B. subtilis and P. fluorescens increased with stress intensity, R. erythropolis and M. pallens exhibited a generally high but constant contact angle, while the response of A. chlorophenolicus and N. aromaticivorans depended on growth conditions and stress type. Osmotically driven changes in CSH of B. subtilis and P. fluorescens are accompanied by increasing surface N/C ratio, suggesting an increase in protein concentration within the cell wall. Cell envelope proteins thus presumably control bacterial CSH in two ways: (i) by increases in the relative density of surface proteins due to efflux of cytoplasmic water and subsequent cell shrinkage, and (ii) by destabilization of cell wall proteins, resulting in conformational changes which render the surface more hydrophobic. IMPORTANCE Changes in precipitation frequency, intensity, and temporal distribution are projected to result in increased frequency and intensity of droughts and heavy rainfall events. Prolonged droughts can promote the development of soil water repellency (SWR); this impacts the infiltration and distribution of water in the soil profile, exposing soil microorganisms to water stress. Exposure to water stress has recently been reported to result in increased cell surface hydrophobicity. However, the mechanism of this development is poorly understood. This study investigates the changes in the physicochemical properties of bacterial cell surfaces under water stress as a possible mechanism of increased surface hydrophobicity. Our results improve understanding of the microbial response to water stress in terms of surface properties, the variations in stress response depending on cell wall composition, and its contribution to the development of SWR.

Fusarium Mycotoxins in Maize Field Soils: Method Validation and Implications for Sampling Strategy.

While mycotoxins are generally regarded as food contamination issues, there is growing interest in mycotoxins as environmental pollutants. The main sources of trichothecene and zearalenone mycotoxins in the environment are mainly attributed to Fusarium infested fields, where mycotoxins can wash off in infested plants or harvest residues. Subsequently, mycotoxins inevitably enter the soil. In this context, investigations into the effects, fate, and transport are still needed. However, there is a lack of analytical methods used to determine Fusarium toxins in soil matrices. We aimed to validate an analytical method capable of determining the toxins nivalenol (NIV), deoxynivalenol (DON), 15-acetyl-deoxynivalenol (15-AcDON), and zearalenone (ZEN), at environmentally relevant concentrations, in five contrasting agricultural soils. Soils were spiked at three levels (3, 9 and 15 ng g-1), extracted by solid-liquid extraction assisted with ultrasonication, using a generic solvent composition of acetonitrile:water 84:16 (v:v) and measured by LC-HRMS. Method validation was successful for NIV, DON, and 15-AcDON with mean recoveries > 93% and RSDr < 10%. ZEN failed the validation criteria. The validated method was applied to eight conventionally managed maize field soils during harvest season, to provide a first insight into DON, NIV, and 15-AcDON levels. Mycotoxins were present in two out of eight sampled maize fields. Soil mycotoxin concentrations ranged from 0.53 to 19.4 ng g-1 and 0.8 to 2.2 ng g-1 for DON and NIV, respectively. Additionally, we found indication that "hot-spot" concentrations were restricted to small scales (<5 cm) with implications for field scale soil monitoring strategies.

Validation of a Simple and Reliable Method for the Determination of Aflatoxins in Soil and Food Matrices.

Aflatoxins (AFs) are toxic fungal secondary metabolites that are commonly detected in food commodities. Currently, there is a lack of generic methods capable of determining AFs both at postharvest stages in agricultural products and preharvest stages, namely, the agricultural soil. Here, we present a simple and reliable method for quantitative analysis of AFs in soil and food matrices at environmentally relevant concentrations for the first time, using the same extraction procedure and chromatography, either by HPLC-FLD or LC-MS. AFs were extracted from matrices by ultrasonication using an acetonitrile/water mixture (84:16, v + v) without extensive and time-consuming cleanup procedures. Food extracts were defatted with n-hexane. Matrix effects in terms of signal suppression/enhancement (SSE) for HPLC-FLD were within ±20% for all matrices tested. For LC-MS, the SSE values were mostly within ±20% for soil matrices but outside ±20% for all food matrices. The sensitivity of the method allowed quantitative analysis even at trace levels with quantification limits (LOQs) between 0.04 and 0.23 µg kg-1 for HPLC-FLD and 0.06-0.23 µg kg-1 for LC-MS. The recoveries ranged from 64 to 92, 74 to 101, and 78 to 103% for fortification levels of 0.5, 5, and 20 µg kg-1, respectively, with repeatability values of 2-18%. The validation results are in accordance with the quality criteria and limits for mycotoxins set by the European Commission, thus confirming a satisfactory performance of the analytical method. Although reliable analysis is possible with both instruments, the HPLC-FLD method may be more suitable for routine analysis because it does not require consideration of the matrix.

Quality control of direct cell-mineral adhesion measurements in air and liquid using inverse AFM imaging.

The study of interaction forces between biological and non-living systems requires in-house production of probes modified with, e.g., bacterial cells or with minerals, in order to map irregularly shaped natural surfaces. In order to avoid artifacts, it is essential to control the functionality of the modified probes. Current methods for this purpose require removing the modified probe from the liquid-cell, inserting it into another device and/or have a too low resolution to detect local changes within the interacting areas. Therefore, we present a fast and cost-effective method that overcomes the above mentioned problems by the inverse AFM imaging principle. First, the 3-D shape of a fresh sharp AFM tip is modeled by measuring the shape of a standard rough pattern and post blind tip reconstruction analysis. The so calibrated characterizer tip was extracted and upside-down fixed rigidly on a disc together with the sample. Before and after the cell-mineral interaction, the modified probe is then inversely imaged by the fixed characterizer controlling changes in finest 3-D details of the modified probe. The characterization of probes modified with kaolinite and P. fluorescens cells and their interactions with R. erythropolis and montmorillonite samples show that the method allows a fast precise investigation of tip modifications before and after cell-mineral interactions in air and liquid such that artifacts in adhesion between cell and mineral at the single-cell level can be excluded.

Morphology, structure, and composition of sulfidized silver nanoparticles and their aggregation dynamics in river water.

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.

A new approach for repeated tip-sample relocation for AFM imaging of nano and micro sized particles and cells in liquid environment.

The ability to repeatedly find exact the same nano region-of-interest (nROI) is essential for atomic force microscopy (AFM) studies of heterogeneous environmental samples. The large variety of methods makes it difficult to find the most suitable one for a specific research question. We thus conducted a literature research for nROI relocation methods and organized the found references in order to give an overview over relocation methods including the advantages, limitations and documented applications. This survey of nROI relocation methods and their key information facilitates the selection of appropriate methods with respect to a specific research question. Based on this survey, we developed a new AFM relocation approach urgently needed for the study of nano and micro sized particles and cells in air and aqueous environment. This approach uses commercially available TEM grids fully embedded in a semitransparent resin as a glue body on top of which particles and cells are fixed. Relocation of nROI within one grid is based on easily recognizable sample features in micro and nanometer scale. The stable sticking of the studied mineral particles and bacterial cells allows repeated measurements of the same nROI with differently functionalized tips in air as well as in water. Our simple, fast, and cost-effective method allows relocation with an accuracy of 10-40 nm and enables the implementation of AFM/ESEM correlative microscopy.

Biodegradation and photooxidation of phenolic compounds in soil-A compound-specific stable isotope approach.

Phenolic compounds occur in a variety of plants and can be used as model compounds for investigating the fate of organic wastewater, lignin, or soil organic matter in the environment. The aim of this study was to better understand and differentiate mechanisms associated with photo- and biodegradation of tyrosol, vanillin, vanillic acid, and coumaric acid in soil. In a 29 d incubation experiment, soil spiked with these phenolic compounds was either subjected to UV irradiation under sterile conditions or to the native soil microbial community in the dark. Changes in the isotopic composition (δ13C) of phenolic compounds were determined by gas chromatography-isotope ratio mass spectrometry and complemented by concentration measurements. Phospholipid-derived fatty acid and ergosterol biomarkers together with soil water repellency measurements provided information on soil microbial and physical properties. Biodegradation followed pseudo-first-order dissipation kinetics, enriched remaining phenolic compounds in 13C, and was associated with increased fungal rather than bacterial biomarkers. Growing mycelia rendered the soil slightly water repellent. High sample variation limited the reliable estimation of apparent kinetic isotope effects (AKIEs) to tyrosol. The AKIE of tyrosol biodegradation was 1.007 ±â€¯0.002. Photooxidation kinetics were of pseudo-zero- or first-order with an AKIE of 1.02 ±â€¯0.01 for tyrosol, suggesting a hydroxyl-radical mediated degradation process. Further research needs to address δ13C variation among sample replicates potentially originating from heterogeneous reaction spaces in soil. Here, nuclear magnetic resonance or nanoscopic imaging could help to better understand the distribution of organic compounds and their transformation in the soil matrix.

Introducing a soil universal model method (SUMM) and its application for qualitative and quantitative determination of poly(ethylene), poly(styrene), poly(vinyl chloride) and poly(ethylene terephthalate) microplastics in a model soil.

Methods for analysis of microplastic in soils are still being developed. In this study, we evaluated the potential of a soil universal model method (SUMM) based on thermogravimetry (TGA) for the identification and quantification of microplastics in standard loamy sand. Blank and spiked soils (with amounts of one of four microplastic types) were analyzed by TGA. For each sample, thermal mass losses (TML) in 10 °C intervals were extracted and used for further analysis. To explain and demonstrate the principles of SUMM, two scenarios were discussed. The first refers to a rare situation in which an uncontaminated blank of investigated soil is available and TML of spiked and blank soils are subtracted. The results showed that the investigated microplastics degraded in characteristic temperature areas and differences between spiked and blank soils were proportional to the microplastics concentrations. The second scenario reflects the more common situation where the blank is not available and needs to be replaced by the previously developed interrelationships representing soil universal models. The models were consequently subtracted from measured TML. Sparse principal component analysis (sPCA) identified 8 of 14 modeled differences between measured TMLs and the universal model as meaningful for microplastics discrimination. Calibrating various microplastics concentrations with the first principal component extracted from sPCA resulted in linear fits and limits of detection in between environmentally relevant microplastics concentrations. Even if such an approach using calculated standards still has limitations, the SUMM shows a certain potential for a fast pre-screening method for analysis of microplastics in soils.

Formation of Water Molecule Bridges Governs Water Sorption Mechanisms in Soil Organic Matter.

Adsorption is the main mechanism of capturing water in soil organic matter (SOM) under arid conditions. This process is governed by hydrophilic sites, which are gradually bridged via water molecule bridges (WaMB). Until now, the link between WaMB and other types of water molecules occurring in SOM during sorption has not been systematically investigated. In this work, we compared the formation and stability of WaMB simultaneously with the total water content, strength of water binding, and kinetics of water sorption in a vacuum-dried model SOM (sapric histosol) exposed to different relative water pressures. The same parameters were then determined in SOM exposed to reduced relative pressures. The adsorption resulted in an adsorption isotherm with a Langmuir-like part below a relative pressure of 0.5 and a Brunauer-Emmett-Teller-like isotherm at higher relative pressures. The WaMB formation was observed at a relative pressure of 0.32, which represented the pressure at which Langmuir-like part reached a plateau. The binding energy showed a linear decrease with an increasing pressure; the slope increased at a relative pressure of 0.46. Reduction of relative pressures above 0.46 showed that the water content remained constant, but the binding energy was lowered. In contrast, below a relative pressure of 0.46, the water content decreased, but the binding energy was not changed. The results indicate that in SOM exposed to different relative pressures, water exists in three types: first, it is strongly bound to primary sorption sites (Langmuir-like), second, it occurs in the form of WaMB water, which bridges functional groups and where predominates water-water interactions, and third, it occurs in the form of phase water, which is located in larger pores similar to the pure water phase. The latter either surrounds the WaMB and destabilizes it or, for higher water content, links individual WaMB and successively reduces their stabilizing effect. Formation of phase water leads to swelling processes including plasticizing effects and potential volume changes of SOM. Accordingly, the results suggest that at lower water relative pressures WaMB stabilizes the SOM structure, whereas at higher water relative pressures, it influences the formation of phase water and thereby the total water content in SOM.

Retention and remobilization mechanisms of environmentally aged silver nanoparticles in an artificial riverbank filtration system.

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.

Quantitative Analysis of Poly(ethylene terephthalate) Microplastics in Soil via Thermogravimetry-Mass Spectrometry.

The use of plastic materials in daily life, industry, and agriculture can cause soil pollution with plastic fragments down to the micrometer scale, i.e., microplastics. Quantitative assessment of microplastics in soil has been limited so far. Until now, microplastic analyses in soil require laborious sample cleanup and are mostly restricted to qualitative assessments. In this study, we applied thermogravimetry-mass spectrometry (TGA-MS) to develop a method for the direct quantitative analysis of poly(ethylene terephthalate) (PET) without further sample pretreatment. For this, soil samples containing 1.61 ± 0.15 wt % organic matter were spiked with 0.23-4.59 wt % PET bottle recyclate microplastics. dl-Cysteine was used as the internal standard (IS). Sample mixtures were pyrolyzed with a 5 K min-1 ramp (40-1000 °C), while sample mass loss and MS signal intensity of typical PET pyrolysis products were recorded. We found MS signal intensities linearly responding to microplastic concentrations. The most-promising results were obtained with the IS-corrected PET pyrolysis product vinylbenzene/benzoic acid ( m/ z = 105, adj. R2 = 0.987). The limits of detection and quantification were 0.07 and 1.72 wt % PET, respectively. Our results suggest that TGA-MS can be an easy and viable complement to existing methods such as pyrolysis or thermogravimetry-thermal desorption assays followed by gas chromatography/mass spectrometry detection or to spectral microscopy techniques.

Effects of low dose silver nanoparticle treatment on the structure and community composition of bacterial freshwater biofilms.

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.

Nanoparticles in the environment: where do we come from, where do we go to?

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.

Links between nanoscale and macroscale surface properties of natural root mucilage studied by atomic force microscopy and contact angle.

Soil water repellency originating from organic coatings plays a crucial role for soil hydraulics and plant water uptake. Focussing on hydrophobicity in the rhizosphere induced by root-mucilage, this study aims to explore the link between macroscopic wettability and nano-microscopic surface properties. The existing knowledge of the nanostructures of organic soil compounds and its effect on wettability is limited by the lack of a method capable to assess the natural spatial heterogeneity of physical and chemical properties. In this contribution, this task is tackled by a geostatistical approach via variogram analysis of topography and adhesion force data acquired by atomic force microscopy and macroscopic sessile drop measurements on dried films of mucilage. The results are discussed following the wetting models given by Wenzel and Cassie-Baxter. Undiluted mucilage formed homogeneous films on the substrate with contact angles >90°. For diluted samples contact angles were smaller and incomplete mucilage surface coverage with hole-like structures frequently exhibited increased adhesion forces. Break-free distances of force curves indicated enhanced capillary forces due to adsorbed water films at atmospheric RH (35 ±â€¯2%) that promote wettability. Variogram analysis enabled a description of complex surface structures exceeding the capability of comparative visual inspection.

Ion-induced modification of the sucrose network and its impact on melting of freeze-dried liposomes. DSC and molecular dynamics study.

Disaccharides play an important role in survival of anhydrobiotic organisms during extreme environmental conditions. A key protection feature is their capability to form the hydrogen bond (HB) network in a similar fashion as the one made by water. Since various ions also affect the HB network in completely hydrated systems, it is of a great interest to understand how they impact preservation when incorporated in a disaccharide network. To address this, we employ a combination of experimental and modeling techniques to study behavior of multilamellar 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) liposomes freeze-dried with sucrose in presence of NaCl or NaH2PO4·H2O at various concentrations (0.01-1M). Differential scanning calorimetry (DSC) was employed in order to determine the cooperative unit size (CUS), the number of lipid molecules that constitute a domain of cooperative motion in the liposome, and the melting temperature (Tm). In the absence of salt CUS was estimated to be 122±12, whereas in the presence of NaCl CUS increases more (347±34 for c=1M) than for NaH2PO4·H2O (193±26 for 1M). When it comes to Tm, the situation is reversed; NaCl induces increase by about 1K, while NaH2PO4·H2O by about 10K. These findings clearly demonstrate how different interaction forces-hydrogen bonding, charge pairing, and van der Waals interactions between acyl chains-affect CUS and Tm. Their interplay and contribution of particular interaction was further analyzed with molecular dynamics (MD) simulations. This analysis demonstrated that the HB network of DMPC and sucrose is partially disrupted in the presence of NaCl ions, and even to a greater extent in the case of NaH2PO4·H2O ions. Notably, H2PO4- ions outcompete and replace the sucrose molecules at the DMPC surface, which in turn alters the nature of the DMPC-surrounding interactions, from a weaker HB-dominated to a stronger CP-dominated interaction network.

Implications of Pony Lake Fulvic Acid for the Aggregation and Dissolution of Oppositely Charged Surface-Coated Silver Nanoparticles and Their Ecotoxicological Effects on Daphnia magna.

Citrate (Cit) and polyethylenimine (BPEI)-coated silver nanoparticles (AgNPs) were used to understand how the type of capping agents and surface charge affect their colloidal stability, dissolution, and ecotoxicity in the absence/presence of Pony Lake Fulvic Acid (PLFA). In the presence of PLFA, Cit-AgNPs were stabilized, while BPEI-AgNPs were aggregated. The aggregation of BPEI-AgNPs decreased with the time, and their stabilizing effect increased at high PLFA concentration. The dissolution also differed between both AgNPs and was influenced by the PLFA concentration. Generally, BPEI-AgNPs showed a lower amount of dissolved Ag than Cit-AgNPs. The dissolved Ag concentration decreased for both AgNPs at low PLFA concentration (5 mg/L). In contrast, the extent of nanoparticle dissolution increased at high PLFA concentration (30 mg/L) but only for BPEI-AgNPs. In the absence of PLFA, the ecotoxicity of Cit-AgNPs to Daphnia magna was higher than that of BPEI-AgNPs. However, the ecotoxicity of AgNPs in the presence of PLFA was up to 70% lower than in their absence. We demonstrated that the differences in colloidal stability, dissolution, and ecotoxicity may be attributed to the different capping agents, surface charge, and concentration of natural organic matter (NOM) as well as to the formation of dissolved Ag complexes with NOM.