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.

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.

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.

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.

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.

Influence of Organic Chemicals on Water Molecule Bridges in Soil Organic Matter of a Sapric Histosol.

Water molecules in soil organic matter (SOM) can form clusters bridging neighboring molecular segments (water molecule bridges, WaMBs). WaMBs are hypothesized to enhance the physical entrapment of organic chemicals and to control the rigidity of the SOM supramolecular structure. However, the understanding of WaMBs dynamics in SOM is still limited. We investigated the relation between WaMBs stability and the physicochemical properties of their environment by treating a sapric histosol with various solvents and organic chemicals. On the basis of predictions from molecular modeling, we hypothesized that the stability of WaMBs, measured by differential scanning calorimetry, increases with the decreasing ability of a chemical to interact with water molecules of the WaMBs. The interaction ability between WaMBs and the chemicals was characterized by linear solvation energy relationships. The WaMBs stability in solvent-treated samples was found to decrease with increasing ability of a solvent to undergo H-donor/acceptor interactions. Spiking with an organic chemical stabilized (naphthalene) or destabilized (phenol) the WaMBs. The WaMBs stability and matrix rigidity were generally reduced strongly and quickly when hydrophilic chemicals entered the soil. The physicochemical aging following this destabilization is slow but leads to successive WaMBs stabilization and matrix stiffening.

Diurnal Variations of Air-Soil Exchange of Semivolatile Organic Compounds (PAHs, PCBs, OCPs, and PBDEs) in a Central European Receptor Area.

Concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs) in air and soil, their fugacities, and the experimental soil-air partitioning coefficient (KSA) were determined at two background sites in the Gt. Hungarian Plain in August 2013. The concentrations of the semivolatile organic compounds (SOCs) in the soil were not correlated with the organic carbon content but with two indirect parameters of mineralization and aromaticity, suggesting that soil organic matter quality is an important parameter affecting the sorption of SOCs onto soils. Predictions based on the assumption that absorption is the dominant process were in good agreement with the measurements for PAHs, OCPs, and the low chlorinated PCBs. In general, soils were found to be a source of PAHs, high chlorinated PCBs, the majority of OCPs and PBDEs, and a sink for the low chlorinated PCBs and γ-hexachlorocyclohexane. Diurnal variations in the direction of the soil-air exchange were found for two compounds (i.e., pentachlorobenzene and p,p'-dichlorodiphenyldichloroethane), with volatilization during the day and deposition in the night. The concentrations of most SOCs in the near-ground atmosphere were dominated by revolatilization from the soil.

Effects of silver nanoparticle properties, media pH and dissolved organic matter on toxicity to Daphnia magna.

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 (140 nm) 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 8.0 mg 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 <2 nm (including Ag(+)) is driving the nAg toxicity. This hypothesis is supported by normalizing the 48-h EC50-values to Ag species <2 nm, 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.

Interactions of dissolved organic matter with natural and engineered inorganic colloids: a review.

This contribution critically reviews the state of knowledge on interactions of natural colloids and engineered nanoparticles with natural dissolved organic materials (DOM). These interactions determine the behavior and impact of colloids in natural system. Humic substances, polysaccharides, and proteins present in natural waters adsorb onto the surface of most colloids. We outline major adsorption mechanisms and structures of adsorption layers reported in the literature and discuss their generality on the basis of particle type, DOM type, and media composition. Advanced characterization methods of both DOM and colloids are needed to address insufficiently understood aspects as DOM fractionation upon adsorption, adsorption reversibility, and effect of capping agent. Precise knowledge on adsorption layer helps in predicting the colloidal stability of the sorbent. While humic substances tend to decrease aggregation and deposition through electrostatic and steric effects, bridging-flocculation can occur in the presence of multivalent cations. In the presence of DOM, aggregation may become reversible and aggregate structure dynamic. Nonetheless, the role of shear forces is still poorly understood. If traditional approaches based on the DLVO-theory can be useful in specific cases, quantitative aggregation models taking into account DOM dynamics, bridging, and disaggregation are needed for a comprehensive modeling of colloids stability in natural media.

Hydrodynamic chromatography coupled with single particle-inductively coupled plasma mass spectrometry for investigating nanoparticles agglomerates.

Studying the environmental fate of engineered or natural colloids requires efficient methods for measuring their size and quantifying them in the environment. For example, an ideal method should maintain its correctness, accuracy, reproducibility, and robustness when applied to samples contained in complex matrixes and distinguish the target particles from the natural colloidal background signals. Since it is expected that a large portion of nanoparticles will form homo- or heteroagglomerates when released into environmental media, it is necessary to differentiate agglomerates from primary particles. At present, most sizing techniques do not fulfill these requirements. In this study, we used online coupling of two promising complementary sizing techniques: hydrodynamic chromatography (HDC) and single-particle ICPMS analysis to analyze gold nanoparticles agglomerated under controlled conditions. We used the single-particle mode of the ICPMS detector to detect single particles eluted from an HDC-column and determine a mass and an effective diameter for each particle using a double calibration approach. The average agglomerate relative density and fractal dimension were calculated using these data and used to follow the morphological evolution of agglomerates over time during the agglomeration process. The results demonstrate the ability of HDC coupled to single-particle analysis to identify and characterize nanoparticle homoagglomerates and is a very promising technique for the analysis of colloids in complex media.

Sorption of silver nanoparticles to environmental and model surfaces.

The fate of engineered nanoparticles in environmental systems is controlled by changes in colloidal stability and their interaction with different environmental surfaces. Little is known about nanoparticle-surface interactions on the basis of sorption isotherms under quasi-equilibrium conditions, although sorption isotherms are a valuable means of studying sorbate-sorbent interactions. We tested the extent to which the sorption of engineered silver nanoparticles (nAg) from stable and unstable suspensions to model (sorbents with specific chemical functional groups) and environmental (plant leaves and sand) surfaces can be described by classical sorption isotherms. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) qualitative and quantitative analyses were also used to assess the morphology and nanomechanical parameters of the covered surfaces. The sorption of nAg from stable suspensions was nonlinear and best described by the Langmuir isotherm. Langmuir coefficients varied with sorbent surface chemistry. For nAg sorption from an unstable suspension, the sorption isotherms did not follow any classical sorption models, suggesting interplay between aggregation and sorption. The validity of the Langmuir isotherm suggests monolayer sorption, which can be explained by the blocking effect due to electrostatic repulsion of individual nanoparticles. In unstable suspensions, aggregates are instead formed in suspension and then sorbed, formed on the surface itself, or formed in both ways.

A case study and a computational simulation of the European Union draft technical guidance documents for chemical safety assessment of mixtures: limitations and a tentative alternative.

Two different methods, Key Critical Component (KCC) and Composite Reciprocal (CR), are used to derive Predicted No Effect Concentration (PNECs) and Derived No Effect Level (DNELs) that are employed in mixture risk assessment. A case study was conducted on coating products and a computational simulation of the KCC and CR methods. The KCC method considers only one key critical component as the whole mixture of equal danger, whereas the CR method indirectly considers the contribution of each component to mixture toxicity. Computational simulation is the first approach that adopts a theoretical perspective in discussing the causes of different outcomes between models and how the two methods should be applied for regulatory purposes in terms of concept, implementation, and performance. The deviation between the two models was highly dependent on the number of mixture components having similarly weighted DNELs (or PNECs). Therefore, if risk assessment using the KCC or CR method needs to be achieved, then the number of mixture components with similarly weighted DNELs (or PNECs) should be checked first. In this study, as a tentative alternative to the existing KCC and CR methods, a tiered approach combining Enhanced KCC (e-KCC) and CR methods was proposed and discussed.

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.

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.

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.

Development of antibody-labelled superparamagnetic nanoparticles for the visualisation of benzo[a]pyrene in porous media with magnetic resonance imaging.

Biogeochemical interfaces in soil are dynamic in the spatial and temporal domain and require advanced visualisation and quantification tools to link in vitro experiments with natural systems. This study presents the development, characterization and application of functional nanoparticles coated with monoclonal antibodies to visualise the distribution of benzo[a]pyrene in porous media using magnetic resonance imaging. The labelled particles are 450 nm in diameter and interact with benzo[a]pyrene covalently bound to silanized silica gel. They did not bind to benzo[a]pyrene adsorbed to plain silica gel. Although unspecific filtration was low, washing steps are required for visualisation. The ability to visualise benzo[a]pyrene is inversely correlated to the heterogeneity of the soil materials. There are access restrictions to narrow pore spaces which allow the visualisation of only those pathways which are also accessible to bacteria and hydrocolloids. The production of the particles is applicable to other antibodies which extends the range of potential target contaminants.

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.

Molecular dynamics simulations of water molecule-bridges in polar domains of humic acids.

The stabilizing effect of water molecule bridges on polar regions in humic substances (HSs) has been investigated by means of molecular dynamics (MD) simulations. The purpose of these investigations was to show the effect of water molecular bridges (WAMB) for cross-linking distant locations of hydrophilic groups. For this purpose, a tetramer of undecanoid fatty acids connected to a network of water molecules has been constructed, which serve as a model for spatially fixed aliphatic chains in HSs terminated by a polar (carboxyl) group. The effect of environmental polarity has been investigated by using solvents of low and medium polarity in force-field MD. A nonpolar environment simulated by n-hexane was chosen to mimic the stability of WAMB in a hydrophilic hotspot surrounded by a nonpolar environment, while the more polar acetonitrile environment was chosen to simulate a more even distribution of polarity around the carboxylic groups and the water molecules. The dynamics simulations show that the rigidity of the oligomer chains is significantly enhanced as soon as the water cluster is large enough to comprise all four carboxyl groups. Increasing the temperature leads to evaporization processes which destabilize the rigidity of the tetramer-water cluster. Embedding it into the nonpolar environment introduces a pronounced cage effect which significantly impedes removal of water molecules from the cluster region. On the other hand, a polar environment facilitates their diffusion from the polar region. One important consequence of these simulations is that although the local water network is the stabilizing factor for the organic matter matrix, the degree of stabilization is additionally affected by the presence of nonpolar surroundings.

Translocation of Sb and Ti in an undisturbed floodplain soil after application of Sb2O3 and TiO2 nanoparticles to the surface.

The pore water transport of antimony and titanium, applied as nanoparticles (NPs), was studied by spiking stable suspensions of two different nanomaterials on the surface of an undisturbed floodplain soil. For preparation of stable dispersions, two different strategies were followed. (i) Comparable to those used in industrial applications: titanium dioxide nanoparticles, with an average diameter of 99 nm, were prepared by high-energy ball milling in water, whereas for (ii) antimony trioxide (Sb(2)O(3); average diameter 121 nm) a dispersing agent (sodium salt of poly[(naphthaleneformaldehyde)sulfonate] (pNFS) in water) was used. The upper 17 cm of a floodplain soil (river Rhine, Germany) was sampled using the minimally invasive sediment or fauna incubation experiment (SOFIE® two compartment cell; 3 l volume each), which preserved the pore system of the soil. The cells were equipped with 450 and 100 nm filter probes at different depths providing a non-invasive sampling of the pore water. The pore water was sampled at different times (T = 0, 24, 48, 96 and 196 h) and analysed by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS). Sb and Ti were transported via the pore water of the floodplain soil to a depth of 14 cm, corresponding to the maximum cell depth. The highest Sb concentration in the pore water was detected after 24 h at a depth of 5.5-8 cm. Although the spiked concentration was higher for Ti than for Sb, the total Ti concentration in the pore water of the spiked cell was lower. This indicates a stronger agglomeration of TiO(2) NPs or a more intensive interaction of Ti with the solid matrix and a faster transport of Sb towards deeper soil layers. The results show that metal(loid)s from metal oxide NPs are transported in the soil pore water and, hence, have the potential to act as the source of contamination of deeper soil layers after soil surface contamination.

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.