Using Focused Ion Beam Time-of-Flight Secondary Ion Mass Spectrometry to Depth Profile Nanoparticles in Polymer Nanocomposites.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a versatile surface-sensitive technique for characterizing both hard and soft matter. Its chemical and molecular specificity, high spatial resolution, and superior sensitivity make it an ideal method for depth profiling polymeric systems, including those comprised of both inorganic and organic constituents (i.e., polymer nanocomposites, PNCs). To best utilize ToF-SIMS for characterizing PNCs, experimental conditions must be optimized to minimize challenges such as the matrix effect and charge accumulation. Toward that end, we have successfully used ToF-SIMS with a Xe+ focused ion beam to depth profile silica nanoparticles grafted with poly(methyl methacrylate) (PMMA-NP) in a poly(styrene-ran-acrylonitrile) matrix film by selecting conditions that address charge compensation and the primary incident beam angles. By tracking the sputtered Si+ species and fitting the resultant concentration profile, the diffusion coefficient of PMMA-NP was determined to be D = 2.4 × 10-14 cm2/s. This value of D lies between that measured using Rutherford backscattering spectrometry (6.4 × 10-14 cm2/s) and the value predicted by the Stokes-Einstein model (2.5 × 10-15 cm2/s). With carefully tuned experimental parameters, ToF-SIMS holds great potential for quantitatively characterizing the nanoparticles at the surfaces and interfaces within PNC materials as well as soft matter in general.

Potential output and risk of commonly administered veterinary antibiotics from small-scale livestock farms to surrounding areas in Northwest China.

The concern over antibiotic pollution from animal husbandry has significantly increased over recent years. However, few studies on output and environmental risk of veterinary antibiotics (VAs) throughout different exposure matrices from small-scale livestock farms (SSLFs) have been explored. This study explored the output and environmental risk of three classes of VAs (sulfonamides (SAs), tetracyclines (TCs), fluoroquinolones (FQs)) in three different types of environmental media (manure, soil, and plants/vegetables) derived from four livestock feedlots in the Hexi Corridor of Northwest China. Following, a risk assessment was conducted to identify the hazardous potential of these VAs on the ecological health of the surrounding environment. A total of 108 soil, 36 manure, 12 plants/vegetables, and 15 animal product samples were collected from the animal feedlots for analysis. The results showed that each of the three groups of VAs were detected in the soil, manure and plant samples derived from all four feedlots in varying levels. In the soil samples, the detection rate of SAs (68%) was higher than the TCs (57%) and the FQs (27%). The total concentration of VAs ranged from not detected (n.d.) to 275 ng/g, while chlortetracycline (CTC) was the most abundant (275 ng/g) of the VAs in soil samples. The SAs had the highest detection rate (100%), followed by TCs (89%), and FQs (78%) in manure samples. The total concentration of VAs residues ranged from n. d. to 105 ng/g, of which CTC was as high as 91 ng/g in manures. In the plant/vegetable samples, the TCs had the highest detection rate (58%), while sulfamethazine (SDM) was the most abundant (32 ng/g). The total concentration of the VAs ranged from n. d. to 65 ng/g in the plant/vegetable samples. The target VAs were not detected in animal products. Measurements of the composition of VAs in soil samples at different vertical depths as well as horizontal distances from the manure accumulation sites showed that VAs were partially retained in the soil of the feedlots and were distributed into the surrounding environment both horizontally and vertically. It is suspected that the detected VAs could be accumulated in agricultural soils since they could be found in most of the sampled manures and soils in SSLFs. These results highlighted the necessity of considering SSLF practices to mange the accumulation and disposal of manure mitigating and controlling VA pollution.

Evolution of the magnetic hyperfine field profiles in an ion-irradiated Fe60Al40 film measured by nuclear resonant reflectivity.

Nuclear resonant reflectivity (NRR) from an Fe60Al40 film was measured using synchrotron radiation at several grazing angles near the critical angle of total external reflection. Using laterally resolved measurements after irradiation with 20 keV Ne+ ions of gradually varying fluence of 0-3.0 × 1014 ions cm-2, the progressive creation of the ferromagnetic A2 phase with increasing ion fluence was confirmed. The observed depth selectivity of the method has been explained by application of the standing wave approach. From the time spectra of the nuclear resonant scattering in several reflection directions the depth profiles for different hyperfine fields were extracted. The results show that the highest magnetic hyperfine fields (∼18-23 T) are initially created in the central part of the film and partially at the bottom interface with the SiO2 substrate. The evolution of the ferromagnetic onset, commencing at a fixed depth within the film and propagating towards the interfaces, has been directly observed. At higher fluence (3.0 × 1014 ions cm-2) the depth distribution of the ferromagnetic fractions became more homogeneous across the film depth, in accordance with previous results.

Profiles of paint layer samples obtained in the fringe field of a high field magnet by means of very short broadband frequency-modulated pulses.

In this article, we describe the acquisition of depth profiles, in particular of paint layers, in the static gradient of a high field magnet, providing a superior sensitivity. The main objective are reference profiles that help to understand scans made with noninvasive unilateral nuclear magnetic resonance (NMR), which often suffers from poor signal-to-noise ratio when working with real samples. Various technical aspects like the coil geometry and the limit of resolution are investigated. A major advancement is the use of frequency-modulated pulses that are very broadband and at the same time very short (25 µs). The latter is necessary to allow the acquisition of a CPMG echo train of old, rigid paint material. Despite being far from adiabatic, they provide uniform excitation and refocusing over 1 MHz, which corresponds to about 400 µm with the used gradient. We show that the uniformity is even sufficient to obtain biexponential relaxation profiles. With these tools, a paint sample from a restoration campaign is analyzed with different contrast criteria: The original and two layers from former restoration attempts can be visualized, and furthermore, the relaxation profiles allow to study the migration of plasticizing molecules.

Few-layer Graphene Lithiophilic and Sodiophilic Diffusion Layer on Porous Stainless Steel as Lithium and Sodium Metal Anodes.

In order to subdue the obvious problem of uneven electric field distribution on regularly used copper/aluminum current collectors for alkali metal batteries, graphene on porous stainless steel (pSS_Gr) was fabricated using the ion etching technique that is employed as an effective host for lithium and sodium metal anodes. The binder-free pSS_Gr demonstrated stable Li plating and stripping at areal current and capacity of 6 mA cm-2 and 2.54 mAh cm-2 , respectively, for over 1000 cycles with 98% coulombic efficiency (C.E.). Also, in the case of Na metal anode, the host has shown stable performance at 4 mA cm-2 and 1 mAh cm-2 over 1000 cycles with ∼100% C.E.. Further, a full cell composed of Li-plated pSS_Gr as an anode and LiFePO4 as a cathode is electrochemically tested at 50 mA g-1 current density with stable 100 cycles.

Quantification of skin penetration of caffeine and propylene glycol applied topically in a mixture by tailored multivariate curve resolution-alternating least squares of depth-resolved Raman spectra.

The quantitative determination of topically applied substances in the skin is severely limited and represents a challenging task. The porcine skin ex vivo was topically treated with a gel containing caffeine (CF) and propylene glycol (PG), and depth-resolved Raman spectra were recorded with two confocal Raman microscopes. We applied a novel tailored multivariate curve resolution-alternating least squares method to the selected spectral regions (512-604 and 778-1148 cm-1 ) of gel-treated skin and quantitatively determined the concentrations of CF and PG in the stratum corneum (SC). The highest concentration of CF (181 mg/cm3 ) was found at the surface, while PG (384 mg/cm3 ) was found at 10% SC depth, indicating the formation of a reservoir at the superficial SC. The concentrations of CF and PG decreased monotonically and reached the detection limit at ≈60% and ≈80% SC depth, respectively, indicating that neither permeate the SC.

Depth profiles of soil organic carbon isotopes across a lithosequence: implications for drivers of soil δ13C vertical changes.

To addresshow parent materials are affecting organic carbon dynamics in a soil profile, soils from a lithosequence comprising six parent lithologies under a rangeland ecosystem have been explored at three depth intervals for soil organic carbon (SOC) content and its 13C depth trends. Studied parent materials ranged from metamorphic (foliated: FM and non-foliated: NFM) to sedimentary (clastic carbonate: CCS) to plutonic (intermediate: IP, felsic: FP and intermediate felsic: IFP) geological contexts. The relationship between SOC concentration and its isotopic signatures to a depth of 50 cm in FM, NFM, FP and IFP profiles was well described by the kinetic fractionation of SOC during biodegradation. For CCS and IP lithologies, strong divergence from the Rayleigh equation was observed suggesting that the 13C enrichments in these soils resulted from both mixing different SOC pools and isotope fractionation related to the C mineralization. Results suggest that SOC across the lithosequence goes through different isotopic evolutions resulting from different 13C-enriched inputs and pedogenic properties as described by the extended Rayleigh equation (0 ≤ ßC ≤ 0.80). These are presumably caused by the bedrock lithology implying that parent material affects C storage and dynamics.

Ion specificity in the measured concentration depth profile of ions at the Vapor-Glycerol interface.

HYPOTHESIS: Specific ion effects are manifest universally across many systems and solvents. Whilst broad understanding of these effects is emerging particularly for bulk effects, the perturbation introduced by the interfaces are generally not understood. We hypothesise that through a careful investigation of the distribution of ions at the glycerol-vapor interface we can better understand specific ion effects in this system and at interfaces. EXPERIMENTS: Neutral impact collision ion scattering spectroscopy (NICISS) is used to obtain and compare individual ion concentration depth profiles (CDP) for a range of monovalent inorganic anions and cations at 12 glycerol electrolyte solutions surfaces. FINDINGS: The distribution of ions at the vapor - glycerol interface is non-monotonic. Broadly, anions are concentrated at the outermost region of the interface and cations are depleted from the interface. The distribution of Cl- and I- is mostly independent of the counterion. However, for Br- ions the distribution depends on the counterion where Cs+, K+, and Na+ ions lead to a desorption of Br- ions from the interface. This is favoured by the large solvation energy of Br- ions and consistent with the law of matching effective ion sizes.

Distribution and correlation of radon and uranium and associated hydrogeochemical processes in alluvial aquifers of northwest India.

The spatial and vertical distributions of radon and uranium are evaluated in relation to the hydrogeology, geomorphology, and hydrochemistry of southwest Punjab. Radon activity of the groundwater ranges from 580 to 3633 Bq/m3 (shallow groundwater 580 to 2438 Bq/m3 and deep groundwater 964 to 3633 Bq/m3), and uranium concentration varies from 24.4 to 253 µg/L (shallow groundwater 24.4 to 253 µg/L and deep groundwater 27.6 to 76.3 µg/L). Shallow groundwater shows higher U concentration compared with deeper ones, which can be attributed to the presence of dissolved oxygen (DO) and NO3- as oxidants and HCO3- as stabilizing agent in shallow zone. Unlike uranium, the radon activities were found to be similar in both shallow and deep groundwater. Rnexcess over secular equilibrium was used to confirm the possibility of additional sources of radon, such as secondary minerals present in the subsurface. Surface manifestations show significant influence on radon and uranium distributions in the shallow zone but not in deep zone due to limited hydraulic connectivity. Depth profiles and correlations of radon and uranium with trace elements and hydrochemical parameters indicate that groundwater exhibits different redox characteristics in shallow (younger and oxidizing) and deep zones (older and reducing). The present study provides critical information that can be helpful for planning sustainable groundwater development in this region and other similar regions without contaminating the relatively safer deep aquifers.

Diverse Bacterial Communities From Qaidam Basin of the Qinghai-Tibet Plateau: Insights Into Variations in Bacterial Diversity Across Different Regions.

The Qaidam Basin of the Qinghai-Tibet Plateau is a cold, hyper-arid desert that presents extreme challenges to microbial communities. As little is known about variations between surface and subsurface microbial communities, high-throughput DNA sequencing was used in this study to profile bacterial communities of the soil samples collected at different depths in three regions in the Qaidam Basin. The α-diversity indices (Chao, Shannon, and Simpson) indicated that bacterial abundance and diversity were higher in the east and the high-elevation regions compared to the west region. In general, Firmicutes was dominant in the west region, while Proteobacteria and Acidobacteria were dominant in the east and the high-elevation regions. The structure of the bacterial communities differed greatly across regions, being strongly correlated with total organic carbon (TOC) and total nitrogen (TN) content. The differences in bacterial communities between the surface and the subsurface soil samples were smaller than the differences across the regions. Network analyses of environmental factors and bacterial genera indicated significant positive correlations in all regions. Overall, our study provides evidence that TOC and TN are the best predictors of both surface and subsurface bacterial communities across the Qaidam Basin. This study concludes that the bacterial community structure is influenced by both the spatial distance and the local environment, but environmental factors are the primary drivers of bacterial spatial patterns in the Qaidam Basin.

Sediment water (interface) mobility of metal(loid)s and nutrients under undisturbed conditions and during resuspension.

The contribution of the release from sediments to the overall river Trave budget was evaluated with respect to 16 metal(loid)s, three non-metals and the ions PO43- and NH4+. To consider undisturbed conditions and sediment resuspension in-situ dialyses-based and ex-situ suction-based pore water sampling was complemented by sequential extraction and suspension reactor experiments. In the investigated sediments, representative for the study area, metal(loid) partitioning between the different geochemical fractions was very similar despite some higher contaminated spots. Pore water investigations emphasis that profiling and peeper based analyses are comparable and deliver an indication that sediment dwelling organisms are exposed to elevated metal(loid) concentrations. However, higher toxicity of the contaminated sediments compared to the sediment treated as background reference was not revealed. During resuspension only few metal(loid)s exceeded specified guideline values. The maximum amounts released, were only between 10-5 and 10-1% of the average daily load of the river Trave per ton of suspended sediment. Overall the "most pristine sediments" and not the potentially hazardous materials in the study area are found to be from highest concern. The results support requests to better include fractionation and speciation demands in legal assessments of sediments.

Determination of traffic-related palladium in tunnel dust and roadside soil.

Roadside dust and soil samples were collected at different sites in the area of Ulm and Munich in Germany. Road dust samples were collected in tunnels where the traffic-related dust is less influenced by atmospheric conditions. Soil samples were taken with a drill bar at varying distances to motorways, district and regional roads with different traffic densities. The soil cylinders of 30cm length were divided into four sections in order to obtain depth profiles for palladium (Pd) distribution. Determination of Pd in total digests of the samples was performed by ligand-assisted selective separation and preconcentration of Pd(II) using solid phase extraction followed by high-resolution continuum source graphite furnace spectrometry. The analytical procedure was successfully validated using the certified reference material BCR-723 Road Tunnel Dust and by recovery experiments in spiked soil samples. The average Pd concentration found in the road dusts was 311µgkg-1, the maximum Pd concentration in the topsoil layer was 193µgkg-1. Pd depth profiles reveal transportation of Pd into deeper soil layers, where even at a depth of 25 to 30cm a Pd concentration of 19µgkg-1 was found, proving the high mobility of Pd. Different factors like traffic density and age of the soils are discussed in the context of the found Pd depth profiles.

Correlating species and spectral diversities using hyperspectral remote sensing in early-successional fields.

Advances in remote sensing technology can help estimate biodiversity at large spatial extents. To assess whether we could use hyperspectral visible near-infrared (VNIR) spectra to estimate species diversity, we examined the correlations between species diversity and spectral diversity in early-successional abandoned agricultural fields in the Ridge and Valley ecoregion of north-central Virginia at the Blandy Experimental Farm. We established plant community plots and collected vegetation surveys and ground-level hyperspectral data from 350 to 1,025 nm wavelengths. We related spectral diversity (standard deviations across spectra) with species diversity (Shannon-Weiner index) and evaluated whether these correlations differed among spectral regions throughout the visible and near-infrared wavelength regions, and across different spectral transformation techniques. We found positive correlations in the visible regions using band depth data, positive correlations in the near-infrared region using first derivatives of spectra, and weak to no correlations in the red-edge region using either of the two spectral transformation techniques. To investigate the role of pigment variability in these correlations, we estimated chlorophyll, carotenoid, and anthocyanin concentrations of five dominant species in the plots using spectral vegetation indices. Although interspecific variability in pigment levels exceeded intraspecific variability, chlorophyll was more varied within species than carotenoids and anthocyanins, contributing to the lack of correlation between species diversity and spectral diversity in the red-edge region. Interspecific differences in pigment levels, however, made it possible to differentiate these species remotely, contributing to the species-spectral diversity correlations. VNIR spectra can be used to estimate species diversity, but the relationships depend on the spectral region examined and the spectral transformation technique used.

A strategy for in-silico prediction of skin absorption in man.

For some time, in-silico models to address substance transport into and through the skin are gaining more and more importance in different fields of science and industry. In particular, the mathematical prediction of in-vivo skin absorption is of great interest to overcome ethical and economical issues. The presented work outlines a strategy to address this problem and in particular, investigates in-vitro and in-vivo skin penetration experiments of the model compound flufenamic acid solved in an ointment by means of a mathematical model. Experimental stratum corneum concentration-depth profiles (SC-CDP) for various time intervals using two different in-vitro systems (Franz diffusion cell, Saarbruecken penetration model) were examined and simulated with the help of a highly optimized three compartment numerical diffusion model and compared to the findings of SC-CDPs of the in-vivo scenario. Fitted model input parameters (diffusion coefficient and partition coefficient with respect to the stratum corneum) for the in-vitro infinite dose case could be used to predict the in-use conditions in-vitro. Despite apparent differences in calculated partition coefficients between in-vivo and in-vitro studies, prediction of in-vivo scenarios from input parameters calculated from the in-vitro case yielded reasonable results.

Effects of the temperature and beam parameters on depth profiles in X-ray photoelectron spectrometry and secondary ion mass spectrometry under C60(+)-Ar(+) cosputtering.

Polymethylmethacrylate (PMMA) is widely used in various fields, including the semiconductor, biomaterial and microelectronic fields. Obtaining the correct depth profiles of PMMA is essential, especially when it is used as a thin-film. There have been many studies that have used earlier generation of cluster ion (SF5(+)) as the sputtering source to profile PMMA films, but few reports have discussed the use of the more recently developed C60(+) in the PMMA sputtering process. In this study, X-ray photoelectron spectroscopy (XPS) and dynamic secondary ion mass spectroscopy (D-SIMS) were used concurrently to monitor the depth profiles of PMMA under C60(+) bombardment. Additionally, the cosputtering technique (C60(+) sputtering with auxiliary, low-kinetic-energy Ar(+)) was introduced to improve the analytical results. The proper cosputtering conditions could eliminate the signal enhancement near the interface that occurred with C60(+) sputtering and enhance the sputtering yield of the characteristic signals. Atomic force microscopy (AFM) was also used to measure the ion-induced topography. Furthermore, the effect of the specimen temperature on the PMMA depth profile was also examined. At higher temperatures (+120°C), the depolymerization reaction that corresponded to main-chain scission dominated the sputtering process. At lower temperatures (-120°C), the cross-linking mechanism was retarded significantly due to the immobilization of free radicals. Both the higher and lower sample temperatures were found to further improve the resulting depth profiles.