Federal Institute For Materials Research and Testing

Microplastics can affect biophysical properties of the soil. However, little is known about the cascade of events in fundamental levels of terrestrial ecosystems, i.e., starting with the changes in soil abiotic properties and propagating across the various components of soil-plant interactions, including soil microbial communities and plant traits. We investigated here the effects of six different microplastics (polyester fibers, polyamide beads, and four fragment types: polyethylene, polyester terephthalate, polypropylene, and polystyrene) on a broad suite of proxies for soil health and performance of spring onion ( Allium fistulosum). Significant changes were observed in plant biomass, tissue elemental composition, root traits, and soil microbial activities. These plant and soil responses to microplastic exposure were used to propose a causal model for the mechanism of the effects. Impacts were dependent on particle type, i.e., microplastics with a shape similar to other natural soil particles elicited smaller differences from control. Changes in soil structure and water dynamics may explain the observed results in which polyester fibers and polyamide beads triggered the most pronounced impacts on plant traits and function. The findings reported here imply that the pervasive microplastic contamination in soil may have consequences for plant performance and thus for agroecosystems and terrestrial biodiversity.

Soils are essential components of terrestrial ecosystems that experience strong pollution pressure. Microplastic contamination of soils is being increasingly documented, with potential consequences for soil biodiversity and function. Notwithstanding, data on effects of such contaminants on fundamental properties potentially impacting soil biota are lacking. The present study explores the potential of microplastics to disturb vital relationships between soil and water, as well as its consequences for soil structure and microbial function. During a 5-weeks garden experiment we exposed a loamy sand soil to environmentally relevant nominal concentrations (up to 2%) of four common microplastic types (polyacrylic fibers, polyamide beads, polyester fibers, and polyethylene fragments). Then, we measured bulk density, water holding capacity, hydraulic conductivity, soil aggregation, and microbial activity. Microplastics affected the bulk density, water holding capacity, and the functional relationship between the microbial activity and water stable aggregates. The effects are underestimated if idiosyncrasies of particle type and concentrations are neglected, suggesting that purely qualitative environmental microplastic data might be of limited value for the assessment of effects in soil. If extended to other soils and plastic types, the processes unravelled here suggest that microplastics are relevant long-term anthropogenic stressors and drivers of global change in terrestrial ecosystems.

Abstract There is little consensus within the fire science community on interpretation of cone calorimeter data, but there is a significant need to screen new flammability modified materials using the cone calorimeter. This article is the result of several discussions aiming to provide guidance in the use and interpretation of cone calorimetry for those directly involved with such measurements. This guidance is essentially empirical, and is not intended to replace the comprehensive scientific studies that already exist. The guidance discusses the fire scenario with respect to applied heat flux, length scale, temperature, ventilation, anaerobic pyrolysis and set‐up represented by the cone calorimeter. The fire properties measured in the cone calorimeter are discussed, including heat release rate and its peak, the mass loss and char yield, effective heat of combustion and combustion efficiency, time to ignition and CO and smoke production together with deduced quantities such as FIGRA and MARHE. Special comments are made on the use of the cone calorimeter relating to sample thickness, textiles, foams and intumescent materials, and the distance of the cone heater from the sample surface. Finally, the relationship between cone calorimetry data and other tests is discussed. Copyright © 2007 John Wiley & Sons, Ltd.

Surface enhanced Raman scattering (SERS) at extremely high enhancement level turns the weak inelastic scattering effect of photons on vibrational quantum states into a structurally sensitive single-molecule and nanoscale probe. The effect opens up exciting opportunities for applications of vibrational spectroscopy in biology. The concept of SERS can be extended to two-photon excitation by exploiting surface enhanced hyper-Raman scattering (SEHRS). This critical review introduces the physics behind single-molecule SERS and discusses the capabilities of the effect in bioanalytics (100 references).

Additive manufacturing ( AM ) is a technology which has the potential not only to change the way of conventional industrial manufacturing processes, adding material instead of subtracting, but also to create entirely new production and business strategies. Since about three decades, AM technologies have been used to fabricate prototypes or models mostly from polymeric or metallic materials. Recently, products have been introduced into the market that cannot be produced in another way than additively. Ceramic materials are, however, not easy to process by AM technologies, as their processing requirements (in terms of feedstock and/or sintering) are very challenging. On the other hand, it can be expected that AM technologies, once successful, will have an extraordinary impact on the industrial production of ceramic components and, moreover, will open for ceramics new uses and new markets.

We report measurements of the optical breakdown threshold and ablation depth in dielectrics with different band gaps for laser pulse durations ranging from 5 ps to 5 fs at a carrier wavelength of 780 nm. For $\ensuremath{\tau}<100\mathrm{fs}$, the dominant channel for free electron generation is found to be either impact or multiphoton ionization (MPI) depending on the size of the band gap. The observed MPI rates are substantially lower than those predicted by the Keldysh theory. We demonstrate that sub-10-fs laser pulses open up the way to reversible nonperturbative nonlinear optics (at intensities greater than ${10}^{14}\mathrm{W}/{\mathrm{cm}}^{2}$ slightly below damage threshold) and to nanometer-precision laser ablation (slightly above threshold) in dielectric materials.

Laser-induced periodic surface structures (LIPSS, ripples) are a universal phenomenon and can be generated on almost any material upon irradiation with linearly polarized radiation. With the availability of ultrashort laser pulses, LIPSS have gained an increasing attraction during the past decade, since these structures can be generated in a simple single-step process, which allows a surface nanostructuring for tailoring optical, mechanical, and chemical surface properties. In this study, the current state in the field of LIPSS is reviewed. Their formation mechanisms are analyzed in ultrafast time-resolved scattering, diffraction, and polarization constrained double-pulse experiments. These experiments allow us to address the question whether the LIPSS are seeded via ultrafast energy deposition mechanisms acting during the absorption of optical radiation or via self-organization after the irradiation process. Relevant control parameters of LIPSS are identified, and technological applications featuring surface functionalization in the fields of optics, fluidics, medicine, and tribology are discussed.

In biological fluids, proteins associate with nanoparticles, leading to a protein "corona" defining the biological identity of the particle. However, a comprehensive knowledge of particle-guided protein fingerprints and their dependence on nanomaterial properties is incomplete. We studied the long-lived ("hard") blood plasma derived corona on monodispersed amorphous silica nanoparticles differing in size (20, 30, and 100 nm). Employing label-free liquid chromatography mass spectrometry, one- and two-dimensional gel electrophoresis, and immunoblotting the composition of the protein corona was analyzed not only qualitatively but also quantitatively. Detected proteins were bioinformatically classified according to their physicochemical and biological properties. Binding of the 125 identified proteins did not simply reflect their relative abundance in the plasma but revealed an enrichment of specific lipoproteins as well as proteins involved in coagulation and the complement pathway. In contrast, immunoglobulins and acute phase response proteins displayed a lower affinity for the particles. Protein decoration of the negatively charged particles did not correlate with protein size or charge, demonstrating that electrostatic effects alone are not the major driving force regulating the nanoparticle-protein interaction. Remarkably, even differences in particle size of only 10 nm significantly determined the nanoparticle corona, although no clear correlation with particle surface volume, protein size, or charge was evident. Particle size quantitatively influenced the particle's decoration with 37% of all identified proteins, including (patho)biologically relevant candidates. We demonstrate the complexity of the plasma corona and its still unresolved physicochemical regulation, which need to be considered in nanobioscience in the future.

The ubiquity of polymeric materials in daily life comes with an increased fire risk, and sustained research into efficient flame retardants is key to ensuring the safety of the populace and material goods from accidental fires. Phosphorus, a versatile and effective element for use in flame retardants, has the potential to supersede the halogenated variants that are still widely used today: current formulations employ a variety of modes of action and methods of implementation, as additives or as reactants, to solve the task of developing flame-retarding polymeric materials. Phosphorus-based flame retardants can act in both the gas and condensed phase during a fire. This Review investigates how current phosphorus chemistry helps in reducing the flammability of polymers, and addresses the future of sustainable, efficient, and safe phosphorus-based flame-retardants from renewable sources.

The formation of laser-induced periodic surface structures (LIPSS) in different materials (metals, semiconductors, and dielectrics) upon irradiation with linearly polarized fs-laser pulses (τ ∼ 30–150 fs, λ ∼ 800 nm) in air environment is studied experimentally and theoretically. In metals, predominantly low-spatial-frequency-LIPSS with periods close to the laser wavelength λ are observed perpendicular to the polarization. Under specific irradiation conditions, high-spatial-frequency-LIPSS with sub-100-nm spatial periods (∼λ/10) can be generated. For semiconductors, the impact of transient changes of the optical properties to the LIPSS periods is analyzed theoretically and experimentally. In dielectrics, the importance of transient excitation stages in the LIPSS formation is demonstrated experimentally using (multiple) double-fs-laser-pulse irradiation sequences. A characteristic decrease of the LIPSS periods is observed for double-pulse delays of less than 2 ps.

Abstract Traditionally, the selective preservation of certain recalcitrant organic compounds and the formation of recalcitrant humic substances have been regarded as an important mechanism for soil organic matter (SOM) stabilization. Based on a critical overview of available methods and on results from a cooperative research program, this paper evaluates how relevant recalcitrance is for the long‐term stabilization of SOM or its fractions. Methodologically, recalcitrance is difficult to assess, since the persistence of certain SOM fractions or specific compounds may also be caused by other stabilization mechanisms, such as physical protection or chemical interactions with mineral surfaces. If only free particulate SOM obtained from density fractionation is considered, it rarely reaches ages exceeding 50 y. Older light particles have often been identified as charred plant residues or as fossil C. The degradability of the readily bioavailable dissolved or water‐extractable OM fraction is often negatively correlated with its content in aromatic compounds, which therefore has been associated with recalcitrance. But in subsoils, dissolved organic matter aromaticity and biodegradability both are very low, indicating that other factors or compounds limit its degradation. Among the investigated specific compounds, lignin, lipids, and their derivatives have mean turnover times faster or similar as that of bulk SOM. Only a small fraction of the lignin inputs seems to persist in soils and is mainly found in the fine textural size fraction (<20 µm), indicating physico‐chemical stabilization. Compound‐specific analysis of 13 C : 12 C ratios of SOM pyrolysis products in soils with C3‐C4 crop changes revealed no compounds with mean residence times of > 40–50 y, unless fossil C was present in substantial amounts, as at a site exposed to lignite inputs in the past. Here, turnover of pyrolysis products seemed to be much longer, even for those attributed to carbohydrates or proteins. Apparently, fossil C from lignite coal is also utilized by soil organisms, which is further evidenced by low 14 C concentrations in microbial phospholipid fatty acids from this site. Also, black C from charred plant materials was susceptible to microbial degradation in a short‐term (60 d) and a long‐term (2 y) incubation experiment. This degradation was enhanced, when glucose was supplied as an easily available microbial substrate. Similarly, SOM mineralization in many soils generally increased after addition of carbohydrates, amino acids, or simple organic acids, thus indicating that stability may also be caused by substrate limitations. It is concluded that the presented results do not provide much evidence that the selective preservation of recalcitrant primary biogenic compounds is a major SOM‐stabilization mechanism. Old SOM fractions with slow turnover rates were generally only found in association with soil minerals. The only not mineral‐associated SOM components that may be persistent in soils appear to be black and fossil C.

The determination of the fluorescence quantum yields (QY, Φ(f)) of a series of fluorescent dyes that span the absorption/excitation and emission ranges of 520-900 and 600-1000 nm is reported. The dyes encompass commercially available rhodamine 101 (Rh-101, Φ(f) = 0.913), cresyl violet (0.578), oxazine 170 (0.579), oxazine 1 (0.141), cryptocyanine (0.012), HITCI (0.283), IR-125 (0.132), IR-140 (0.167), and four noncommercial cyanine dyes with specific spectroscopic features, all of them in dilute ethanol solution. The QYs have been measured relative to the National Institute of Standards and Technology's standard reference material (SRM) 936a (quinine sulfate, QS) on a traceably characterized fluorometer, employing a chain of transfer standard dyes that include coumarin 102 (Φ(f) = 0.764), coumarin 153 (0.544), and DCM (0.435) as links between QS and Rh-101. The QY of Rh-101 has also been verified in direct measurements against QS using two approaches that rely only on instrument correction. In addition, the effects of temperature and the presence of oxygen on the fluorescence quantum yield of Rh-101 have been assessed.

Abstract Since the early 1950s, the number of international measurement standards for anchoring stable isotope delta scales has mushroomed from 3 to more than 30, expanding to more than 25 chemical elements. With the development of new instrumentation, along with new and improved measurement procedures for studying naturally occurring isotopic abundance variations in natural and technical samples, the number of internationally distributed, secondary isotopic reference materials with a specified delta value has blossomed in the last six decades to more than 150 materials. More than half of these isotopic reference materials were produced for isotope-delta measurements of seven elements: H, Li, B, C, N, O, and S. The number of isotopic reference materials for other, heavier elements has grown considerably over the last decade. Nevertheless, even primary international measurement standards for isotope-delta measurements are still needed for some elements, including Mg, Fe, Te, Sb, Mo, and Ge. It is recommended that authors publish the delta values of internationally distributed, secondary isotopic reference materials that were used for anchoring their measurement results to the respective primary stable isotope scale.

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTA Selective and Sensitive Fluoroionophore for HgII, AgI, and CuII with Virtually Decoupled Fluorophore and Receptor UnitsKnut Rurack, Matthias Kollmannsberger, Ute Resch-Genger, and Jörg DaubView Author Information Federal Institute for Materials Research and Testing (BAM) Richard-Willstaetter Str. 11 D-12489 Berlin, Germany Institute of Organic Chemistry University of Regensburg D-93040 Regensburg, Germany Cite this: J. Am. Chem. Soc. 2000, 122, 5, 968–969Publication Date (Web):January 25, 2000Publication History Received26 July 1999Revised18 October 1999Published online25 January 2000Published inissue 1 February 2000https://doi.org/10.1021/ja992630aCopyright © 2000 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views4277Altmetric-Citations636LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (42 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Cations,Fluorescence,Ions,Mercury,Solvents Get e-Alerts

Different kinds of additive and reactive flame retardants containing phosphorus are increasingly successful as halogen-free alternatives for various polymeric materials and applications. Phosphorus can act in the condensed phase by enhancing charring, yielding intumescence, or through inorganic glass formation; and in the gas phase through flame inhibition. Occurrence and efficiency depend, not only on the flame retardant itself, but also on its interaction with pyrolysing polymeric material and additives. Flame retardancy is sensitive to modification of the flame retardant, the use of synergists/adjuvants, and changes to the polymeric material. A detailed understanding facilitates the launch of tailored and targeted development.

Although gold nanoparticles (GNP) are among the most intensely studied nanoscale materials, the actual mechanisms of GNP formation often remain unclear due to limited accessibility to in situ-derived time-resolved information about precursor conversion and particle size distribution. Overcoming such limitations, a method is presented that analyzes the formation of nanoparticles via in situ SAXS and XANES using synchrotron radiation. The method is applied to study the classical GNP synthesis route via the reduction of tetrachloroauric acid by trisodium citrate at different temperatures and reactant concentrations. A mechanism of nanoparticle formation is proposed comprising different steps of particle growth via both coalescence of nuclei and further monomer attachment. The coalescence behavior of small nuclei was identified as one essential factor in obtaining a narrow size distribution of formed particles.

The formation of nearly wavelength-sized laser-induced periodic surface structures (LIPSSs) on single-crystalline silicon upon irradiation with single or multiple femtosecond-laser pulses (pulse duration τ=130 fs and central wavelength λ=800 nm) in air is studied experimentally and theoretically. In our theoretical approach, we model the LIPSS formation by combining the generally accepted first-principles theory of Sipe and co-workers with a Drude model in order to account for transient intrapulse changes in the optical properties of the material due to the excitation of a dense electron-hole plasma. Our results are capable to explain quantitatively the spatial periods of the LIPSSs being somewhat smaller than the laser wavelength, their orientation perpendicular to the laser beam polarization, and their characteristic fluence dependence. Moreover, evidence is presented that surface plasmon polaritons play a dominant role during the initial stage of near-wavelength-sized periodic surface structures in femtosecond-laser irradiated silicon, and it is demonstrated that these LIPSSs can be formed in silicon upon irradiation by single femtosecond-laser pulses.

SASfit is one of the mature programs for small-angle scattering data analysis and has been available for many years. This article describes the basic data processing and analysis workflow along with recent developments in the SASfit program package (version 0.94.6). They include (i) advanced algorithms for reduction of oversampled data sets, (ii) improved confidence assessment in the optimized model parameters and (iii) a flexible plug-in system for custom user-provided models. A scattering function of a mass fractal model of branched polymers in solution is provided as an example for implementing a plug-in. The new SASfit release is available for major platforms such as Windows, Linux and MacOS. To facilitate usage, it includes comprehensive indexed documentation as well as a web-based wiki for peer collaboration and online videos demonstrating basic usage. The use of SASfit is illustrated by interpretation of the small-angle X-ray scattering curves of monomodal gold nanoparticles (NIST reference material 8011) and bimodal silica nanoparticles (EU reference material ERM-FD-102).

Despite the increasing use of semiconductor nanocrystals (quantum dots, QDs) with unique size-controlled optical and chemical properties in (bio)analytical detection, biosensing and fluorescence imaging and the obvious relevance of reliable values of fluorescence quantum yields for these applications, evaluated procedures for the determination of the fluorescence quantum yields (Φf) of these materials are still missing. This limits the value of literature data of QDs in comparison to common organic dyes and hampers the comparability of the performance of QDs from different sources or manufacturers. This encouraged us to investigate achievable uncertainties for the determination of Φf values of these chromophores and to illustrate common pitfalls exemplarily for differently sized water-soluble CdTe QDs. Special attention is dedicated to the colloidal nature and complicated surface chemistry of QDs thereby deriving procedures to minimize uncertainties related to these features.

The strategy of utilizing mechanochemical synthesis to obtain metal−organic frameworks (MOFs) with high surface areas is demonstrated for two model systems. The compounds HKUST-1 (Cu 3 (BTC) 2, BTC = 1,3,5-benzenetricarboxylate) and MOF-14 (Cu 3 (BTB) 2, BTB = 4,4′,4′′-benzenetribenzoate) were synthesized by ball milling and characterized by powder X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and thermal analysis (DTA/DTG/MS). The specific surface area (SSA) of both compounds was characterized by nitrogen adsorption. To verify these results and to understand how the synthetic conditions influence the pore structure and the surface area, additional small-angle X-ray scattering (SAXS) experiments were carried out. Our investigations confirm that this synthesis approach is a promising alternative method for distinct MOFs. This facile method leads to materials with surface areas of 1713 m 2 /g, which is comparable to the highest given values in the literature for the respective compounds.