Convergence of dissolving and melting at the nanoscale.

Phase transitions of water and its mixtures are of fundamental importance in physical chemistry, the pharmaceutical industry, materials sciences, and atmospheric sciences. However, current understanding remains elusive to explain relevant observations, especially at the nanoscale. Here, by using molecular dynamics simulations, we investigate the dissolution of sodium chloride (NaCl) nanocrystals with volume-equivalent diameters from 0.51 to 1.75 nm. Our results show that the dissolution of NaCl in aqueous nanodroplets show a strong size dependence, and its solubility can be predicted by the Ostwald-Freundlich equation and Gibbs-Duhem equation after considering a size-dependent solid-liquid surface tension. We find that the structure of dissolved ions in the saturated aqueous nanodropplet resembles the structure of a molten NaCl nanoparticle. With decreasing nanodroplet size, this similarity grows and the average potential energy of NaCl in solution, the molten phase and the crystal phase converges.

Water-driven microbial nitrogen transformations in biological soil crusts causing atmospheric nitrous acid and nitric oxide emissions.

Biological soil crusts (biocrusts) release the reactive nitrogen gases (Nr) nitrous acid (HONO) and nitric oxide (NO) into the atmosphere, but the underlying microbial process controls have not yet been resolved. In this study, we analyzed the activity of microbial consortia relevant in Nr emissions during desiccation using transcriptome and proteome profiling and fluorescence in situ hybridization. We observed that < 30 min after wetting, genes encoding for all relevant nitrogen (N) cycling processes were expressed. The most abundant transcriptionally active N-transforming microorganisms in the investigated biocrusts were affiliated with Rhodobacteraceae, Enterobacteriaceae, and Pseudomonadaceae within the Alpha- and Gammaproteobacteria. Upon desiccation, the nitrite (NO2-) content of the biocrusts increased significantly, which was not the case when microbial activity was inhibited. Our results confirm that NO2- is the key precursor for biocrust emissions of HONO and NO. This NO2- accumulation likely involves two processes related to the transition from oxygen-limited to oxic conditions in the course of desiccation: (i) a differential regulation of the expression of denitrification genes; and (ii) a physiological response of ammonia-oxidizing organisms to changing oxygen conditions. Thus, our findings suggest that the activity of N-cycling microorganisms determines the process rates and overall quantity of Nr emissions.

Membranes Are Decisive for Maximum Freezing Efficiency of Bacterial Ice Nucleators.

Ice-nucleating proteins (INPs) from Pseudomonas syringae are among the most active ice nucleators known, enabling ice formation at temperatures close to the melting point of water. The working mechanisms of INPs remain elusive, but their ice nucleation activity has been proposed to depend on the ability to form large INP aggregates. Here, we provide experimental evidence that INPs alone are not sufficient to achieve maximum freezing efficiency and that intact membranes are critical. Ice nucleation measurements of phospholipids and lipopolysaccharides show that these membrane components are not part of the active nucleation site but rather enable INP assembly. Substantially improved ice nucleation by INP assemblies is observed for deuterated water, indicating stabilization of assemblies by the stronger hydrogen bonds of D2O. Together, these results show that the degree of order/disorder and the assembly size are critically important in determining the extent to which bacterial INPs can facilitate ice nucleation.

Electrostatic Interactions Control the Functionality of Bacterial Ice Nucleators.

Bacterial ice-nucleating proteins (INPs) promote heterogeneous ice nucleation more efficiently than any other material. The details of their working mechanism remain elusive, but their high activity has been shown to involve the formation of functional INP aggregates. Here we reveal the importance of electrostatic interactions for the activity of INPs from the bacterium Pseudomonas syringae by combining a high-throughput ice nucleation assay with surface-specific sum-frequency generation spectroscopy. We determined the charge state of nonviable P. syringae as a function of pH by monitoring the degree of alignment of the interfacial water molecules and the corresponding ice nucleation activity. The net charge correlates with the ice nucleation activity of the INP aggregates, which is minimal at the isoelectric point. In contrast, the activity of INP monomers is less affected by pH changes. We conclude that electrostatic interactions play an essential role in the formation of the highly efficient functionally aligned INP aggregates, providing a mechanism for promoting aggregation under conditions of stress that prompt the bacteria to nucleate ice.

Nanomaterial-microbe cross-talk: physicochemical principles and (patho)biological consequences.

The applications of nanoparticles (NPs) are increasing exponentially in consumer products, biotechnology and biomedicine, and humans, as well as the environment, are increasingly being exposed to NPs. Analogously, various (pathogenic) microorganisms are present at all the major exposure and entry sites for NPs in the human body as well as in environmental habitats. However, the field has just started to explore the complex interplay between NPs and microbes and the (patho)biological consequences. Based on recent insights, herein, we critically reviewed the available knowledge about the interaction of NPs with microbes and the analytical investigations including the latest intravital imaging tools. We have commented on how the NPs' characteristics influence complex formation with microorganisms, presented the underlying physicochemical forces, and provided examples of how this knowledge can be used to rationally control the NP-microbe interaction. We concluded by discussing the role of the biomolecule corona in NP-microbe crosstalk and speculated the impact of NP-microbe complex formation on the (patho)biological outcome and fate of microbial pathogens. The presented insights will not only support the field in engineering NPs with improved anti-microbial activity but also stimulate research on the biomedical and toxicological relevance of nanomaterial-microbiome complex formation for the anthropocene in general.

Allergenic Asteraceae in air particulate matter: quantitative DNA analysis of mugwort and ragweed.

Mugwort (Artemisia vulgaris) and ragweed (Ambrosia artemisiifolia) are highly allergenic Asteraceae. They often cause pollen allergies in late summer and fall. While mugwort is native to Europe, ragweed reached Europe as a neophyte from North America about 150 years ago and continued spreading ever since. To understand possible relationships between the spread of ragweed, its abundance in air, and to judge possible health risks for the public, we quantified ragweed DNA in inhalable fine as well as in coarse air particulate matter. Mugwort was chosen for comparison, as it is closely related to ragweed and grows in similar, though mainly not identical, habitats but is native to Germany. The DNA quantification was performed on atmospheric aerosol samples collected over a period of 5 years in central Europe. The DNA concentrations were highest during the characteristic pollination periods but varied greatly between different years. In the inhalable fine particle fraction, ragweed exceeds the mugwort DNA concentration fivefold, while the coarse particle fraction, bearing intact pollen grains, contains more mugwort than ragweed DNA. The higher allergenic potential of ragweed might be linked to the humidity or long-range transport-induced bursting of ragweed pollen into smaller allergenic particles, which may reach the lower airways and cause more intense allergic reactions. Airborne ragweed DNA was detected also outside the local pollination periods, which can be explained by atmospheric long-range transport. Back-trajectory analyses indicate that the air masses containing ragweed DNA during winter had originated in regions with milder climate and large ragweed populations (Southern France, Carpathian Basin).

Chemical kinetics of multiphase reactions between ozone and human skin lipids: Implications for indoor air quality and health effects.

Ozone reacts with skin lipids such as squalene, generating an array of organic compounds, some of which can act as respiratory or skin irritants. Thus, it is important to quantify and predict the formation of these products under different conditions in indoor environments. We developed the kinetic multilayer model that explicitly resolves mass transport and chemical reactions at the skin and in the gas phase (KM-SUB-Skin). It can reproduce the concentrations of ozone and organic compounds in previous measurements and new experiments. This enabled the spatial and temporal concentration profiles in the skin oil and underlying skin layers to be resolved. Upon exposure to ~30 ppb ozone, the concentrations of squalene ozonolysis products in the gas phase and in the skin reach up to several ppb and on the order of ~10 mmol m-3 . Depending on various factors including the number of people, room size, and air exchange rates, concentrations of ozone can decrease substantially due to reactions with skin lipids. Ozone and dicarbonyls quickly react away in the upper layers of the skin, preventing them from penetrating deeply into the skin and hence reaching the blood.

High potential for weathering and climate effects of non-vascular vegetation in the Late Ordovician.

It has been hypothesized that predecessors of today's bryophytes significantly increased global chemical weathering in the Late Ordovician, thus reducing atmospheric CO2 concentration and contributing to climate cooling and an interval of glaciations. Studies that try to quantify the enhancement of weathering by non-vascular vegetation, however, are usually limited to small areas and low numbers of species, which hampers extrapolating to the global scale and to past climatic conditions. Here we present a spatially explicit modelling approach to simulate global weathering by non-vascular vegetation in the Late Ordovician. We estimate a potential global weathering flux of 2.8 (km(3) rock) yr(-1), defined here as volume of primary minerals affected by chemical transformation. This is around three times larger than today's global chemical weathering flux. Moreover, we find that simulated weathering is highly sensitive to atmospheric CO2 concentration. This implies a strong negative feedback between weathering by non-vascular vegetation and Ordovician climate.

Direct imaging of changes in aerosol particle viscosity upon hydration and chemical aging.

Organic aerosol particles (OA) play major roles in atmospheric chemistry, climate, and public health. Aerosol particle viscosity is highly important since it can determine the ability of chemical species such as oxidants, organics or water to diffuse into the particle bulk. Recent measurements indicate that OA may be present in highly viscous states, however, diffusion rates of small molecules such as water are not limited by these high viscosities. Direct observational evidence of kinetic barriers caused by high viscosity and low diffusivity in aerosol particles were not available until recently; and techniques that are able to dynamically quantify and track viscosity changes during atmospherically relevant processes are still unavailable for atmospheric aerosols. Here we report quantitative, real-time, online observations of microscopic viscosity changes in aerosol particles of atmospherically relevant composition, using fluorescence lifetime imaging (FLIM) of viscosity. We show that microviscosity in ozonated oleic acid droplets and secondary organic aerosol (SOA) particles formed by ozonolysis of myrcene increases substantially with decreasing humidity and atmospheric oxidative aging processes. Furthermore, we found unexpected heterogeneities of microviscosity inside individual aerosol particles. The results of this study enhance our understanding of organic aerosol processes on microscopic scales and may have important implications for the modeling of atmospheric aerosol growth, composition and interactions with trace gases and clouds.

HONO emissions from soil bacteria as a major source of atmospheric reactive nitrogen.

Abiotic release of nitrous acid (HONO) in equilibrium with soil nitrite (NO2(-)) was suggested as an important contributor to the missing source of atmospheric HONO and hydroxyl radicals (OH). The role of total soil-derived HONO in the biogeochemical and atmospheric nitrogen cycles, however, has remained unknown. In laboratory experiments, we found that for nonacidic soils from arid and arable areas, reactive nitrogen emitted as HONO is comparable with emissions of nitric oxide (NO). We show that ammonia-oxidizing bacteria can directly release HONO in quantities larger than expected from the acid-base and Henry's law equilibria of the aqueous phase in soil. This component of the nitrogen cycle constitutes an additional loss term for fixed nitrogen in soils and a source for reactive nitrogen in the atmosphere.

Standard states and thermochemical kinetics in heterogeneous atmospheric chemistry.

The significance of the (often implicit) choice of standard state in the analysis and interpretation of heterogeneous chemical processes is not well acknowledged. This paper attempts to illuminate how the specific choice of standard state influences the numerical values of the parameters obtained from such analysis. Examples are drawn from air-solution and air-surface equilibria.

Rainforest aerosols as biogenic nuclei of clouds and precipitation in the Amazon.

The Amazon is one of the few continental regions where atmospheric aerosol particles and their effects on climate are not dominated by anthropogenic sources. During the wet season, the ambient conditions approach those of the pristine pre-industrial era. We show that the fine submicrometer particles accounting for most cloud condensation nuclei are predominantly composed of secondary organic material formed by oxidation of gaseous biogenic precursors. Supermicrometer particles, which are relevant as ice nuclei, consist mostly of primary biological material directly released from rainforest biota. The Amazon Basin appears to be a biogeochemical reactor, in which the biosphere and atmospheric photochemistry produce nuclei for clouds and precipitation sustaining the hydrological cycle. The prevailing regime of aerosol-cloud interactions in this natural environment is distinctly different from polluted regions.

Nitration enhances the allergenic potential of proteins.

BACKGROUND: Recent investigations have shown that proteins, including Bet v 1a, are nitrated by exposure to polluted urban air. We have investigated immunogenic and allergenic properties of in vitro nitrated allergens in in vivo models. METHODS: Untreated and nitrated samples of ovalbumin or Bet v 1a were compared for their ability to stimulate proliferation and cytokine secretion in splenocytes from DO11.10 or from sensitized BALB/c mice, and for their ability to induce specific immunoglobulin (Ig)G1, IgG2a and IgE in sensitized mice. Additionally, sera from birch pollen-allergic individuals were analysed for IgE and IgG specific for nitrated Bet v 1a. RESULTS: Upon splenocyte stimulation with nitrated as compared with unmodified allergens, proliferation as well as interleukin 5 and interferon-gamma production were enhanced. Sera of mice sensitized with nitrated allergens showed elevated levels of specific IgE, IgG1 and IgG2a, compared with sera from mice sensitized with unmodified allergens. Moreover, cross-reactivity of antibodies against unrelated, nitrated allergens was observed in mice. We also found higher amounts of functional, specific IgE against nitrated than against untreated Bet v 1a in sera from birch pollen-allergic patients. CONCLUSIONS: Our findings suggest that nitration enhances allergic responses, which may contribute to an increased prevalence of allergic diseases in polluted urban environments.

Phenyl-modified reversed-phase liquid chromatography coupled to atmospheric pressure chemical ionization mass spectrometry: a universal method for the analysis of partially oxidized aromatic hydrocarbons.

A new liquid chromatographic method for the efficient separation of aromatic compounds having a wide range of sizes, molecular structures, and polarities has been developed. Based on a phenyl-modified silica reversed stationary phase and a methanol-water solvent gradient, it allows the separation of mono- and polycyclic aromatic hydrocarbons (PAHs) having up to five condensed aromatic rings and partially oxidized derivatives within a single chromatographic run of 40-min duration. The applicability of the method is demonstrated using 81 reference substances (PAHs, phenols, quinones, acids, lactones, esters, etc.) and real samples of environmental, medical, and technical relevance (ozonized PAHs, lake water, human urine, diesel exhaust condensates). The retention times of the investigated aromatics exhibit a regular increase with molecular mass and a systematic decrease with increasing number and polarity of functional groups. In case of intramolecular hydrogen bonding, a positive shift of retention time provides additional structural information. The combination of chromatographic retention time with the molecular mass and structural information from mass spectrometric detection allows the tentative identification of unknown aromatic analytes at trace levels, even without specific reference substances. With atmospheric pressure chemical ionization (APCI), low detection limits and highly informative fragmentation patterns can be obtained by in-source collision-induced fragmentation in a single-quadrupole LC-APCI-MS system as applied in this study, and multidimensional MS experiments are expected to further enhance the potential of the presented method.

In-source fragmentation of partially oxidized mono- and polycyclic aromatic hydrocarbons in atmospheric pressure chemical ionization mass spectrometry coupled to liquid chromatography

Partially oxidized derivatives of polycyclic aromatic hydrocarbons (PAHs) are known to be important environmental pollutants. For the identification of these substances in complex mixtures, e.g. atmospheric aerosol samples, liquid chromatography/mass spectrometry with atmospheric pressure chemical ionization (LC/APCI-MS) has been found to be a suitable analytical technique. In this study 31 derivatives of mono- and polycyclic aromatic hydrocarbons with up to five condensed aromatic rings carrying different functional groups (carboxyl, dicarboxylic anhydride, lactone, hydroxyl, and carbonyl) were characterized by LC/APCI-MS. Each substance was measured in positive and negative ion detection mode at four different fragmentor voltages (90 to 190 V). For the first time, the results show that characteristic and well-interpretable fragmentation patterns can be obtained for these classes of compounds by in-source collision-induced dissociation in a single quadrupole LC/APCI-MS system. For each class of compounds typical spectral features and optimum measurement conditions are reported, and fragmentation pathways are proposed. The study demonstrates the applicability of LC/APCI-MS for the determination of most of the investigated compounds at trace levels, and it provides a database for the identification of unknown partially oxidized aromatic hydrocarbons. Copyright 1999 John Wiley & Sons, Ltd.

Arctic ozone loss due to denitrification

Measurements from the winter of 1994-95 indicating removal of total reactive nitrogen from the Arctic stratosphere by particle sedimentation were used to constrain a microphysical model. The model suggests that denitrification is caused predominantly by nitric acid trihydrate particles in small number densities. The denitrification is shown to increase Arctic ozone loss substantially. Sensitivity studies indicate that the Arctic stratosphere is currently at a threshold of denitrification. This implies that future stratospheric cooling, induced by an increase in the anthropogenic carbon dioxide burden, is likely to enhance denitrification and to delay until late in the next century the return of Arctic stratospheric ozone to preindustrial values.

The vertical birthing position of the Trobrianders, Papua New Guinea.

During an ethnomedical field study the author succeeded in participating and photographing 4 traditional birthgivings among the Trobrianders/Papua New Guinea. Their various vertical postures are described with special reference to specific Trobriand practices and discussed by literature review. The results suggest that vertical birthing positions are advantageous to horizontal ones and should be reconsidered by modern Western obstetrics.

Childbirth on Kiriwina, Trobriand Islands, Milne Bay Province.

This study presents the first true documentation of birthgiving among the Trobriand Islanders of Papua New Guinea. In contrast to other research projects where interviews only provide a rather imprecise and partly contradictory picture of childbirth, the information here is based upon participant observation and photographs taken of three birthing processes. The advantages and disadvantages of both the traditional and Western birthing systems are compared and analyzed. Suggestions for a Traditional Birth Attendant programme are presented with the aim of improving village deliveries in ways that are consistent with deeply ingrained aspects of culture. They are meant to initiate further discussions based on this topic and do not provide a final structure of such a Traditional Birth Attendant programme.

[Electrostimulation of the neurogenic bladder (author's transl)]. / Elektrostimulation der neurogenen Blase.

Six children with neurogenic disorders of micturition are stimulated by Katona's method. The evaluation of the clinical and cystometric results carried out every 4 weeks shows the contradictoriness of this method. The clinical results show an unequivocal improvement in micturition behavior, whereas checking the objective cystomanometric results only suggests an increasing tonicity of the detrusor and suppression of the uninhibited detrusor contractions. The urgency for carrying out cystomanometric measurements during Katona's electrostimulation therapy is pointed out.

[Iatrogenic urinary tract infection in cystometry (author's transl)]. / Der iatrogene Harnwegsinfekt bei der Zystometrie.

The present paper reviews the risk of infection with particular reference to cystometry. Cystomanometric studies were performed in 71 children with chronic recurrent urinary tract infections and 40 children with neurogenic micturition disorders with meningomyelocele. Our results show that short-term catheterization in cystometry leads to a considerable risk of infection. In 10% of the cystometries children developed new infections. The infection risk decidedly depends less on the nature of the intervention than on the individual disposition. Antibiotic therapy seems to have little influence on the risk of infection.