Streptomyces are important soil bacteria used for bioremediation of metal-contaminated soils, however, it is still unknown how metal-selective Streptomyces are and which mechanisms are involved during their capture. In this work, we exposed S. coelicolor spores to environmentally relevant concentrations (0.1, 1, 10, 100 μM) of Ce, U and Cd in solid medium for one week to investigate the uptake behaviour of hyphae in the newly formed spores. Additionally, metal adsorption onto the spores was explored by incubating inactive, ungerminated spores for one day in aqueous metal solution. The spore-washing treatment was key to distinguishing between strongly spore-associated (e.g. incorporation; Tris-EDTA buffer) and weakly spore-associated metals (Tris buffer alone minus Tris-EDTA). Single cell (sc) ICP-MS was used to quantify metal-associated content in individual spores. Our results revealed element-specific adsorption onto inactive spores showing that out of the total metal exposure, both strongly (Ce: 58%; U: 54%; Cd: 28%) and weakly (Ce: 12%; U: 1%; Cd: 18%) adsorbed metals occur. However, scICP-MS showed that from metal-amended solid medium, only Ce and U were strongly spore-associated (averages 0.040 and 0.062 fg spore−1 for 10 μM exposures, respectively) while Cd was below the limit of detection (< 0.006 fg spore−1). We propose that hyphae only metabolically interact with Ce in a controlled manner but uncontrolled with U, as 66–73% Ce and only 2–4% U were inherited from adsorbed content. We conclude that Streptomyces spore-metal interaction starts with a relevant adsorption step of Ce, U and Cd as presented for aqueous conditions. If spores start to germinate, hyphae are capable of effectively encapsulating Ce and U, but not Cd. This study brings light into the still unknown field of metal interactions with Streptomyces and applied understanding for more efficient and metal-specific use of Streptomyces in bioremediation of metal-polluted soils.

Single particle inductively coupled plasma mass spectrometry (spICP-MS) is a well-established technique to characterize the size, particle number concentration (PNC), and elemental composition of engineered nanoparticles (NPs) and colloids in aqueous suspensions. However, a method capable of directly analyzing water-sensitive or highly reactive NPs in alcoholic suspension has not been reported yet. Here, we present a novel spICP-MS method for characterizing the main cement hydration product, i.e., calcium-silicate-hydrate (C-S-H) NPs, in ethanolic suspensions, responsible for cement strength. The method viability was tested on a wide range of NP compositions and sizes (i.e., from Au, SiO2, and Fe3O4 NP certified reference materials (CRMs) to synthetic C-S-H phases with known Ca/Si ratios and industrial cement hardening accelerators, X-Seed 100/500). Method validation includes comparisons to nanoparticle tracking analysis (NTA) and transmission/scanning electron microscopy (TEM/SEM). Results show that size distributions from spICP-MS were in good agreement with TEM and NTA for CRMs ≥ 51 nm and the synthetic C-S-H phases. The X-Seed samples showed significant differences in NP sizes depending on the elemental composition, i.e. CaO and SiO2 NPs were bigger than Al2O3 NPs. PNC via spICP-MS was successfully validated with an accuracy of 1 order of magnitude for CRMs and C-S-H phases. The spICP-MS Ca/Si ratios matched known ratios from synthetic C-S-H phases (0.6, 0.8, and 1.0). Overall, our method is applicable for the direct and element-specific quantification of fast nucleation and/or mineral formation processes characterizing NPs (ca. 50-1000 nm) in alcoholic suspensions.

Pseudomonas alloputida KT2440 is a ubiquitous, soil-dwelling bacterium that metabolizes recalcitrant and volatile carbon sources. The latter is utilized by two redundant, Ca- and lanthanide (Ln)-dependent, pyrroloquinoline quinone-dependent alcohol dehydrogenases (PQQ ADH), PedE and PedH, whose expression is regulated by Ln availability. P. alloputida KT2440 is the best-studied non-methylotroph in the context of Ln-utilization. Combined with microfluidic cultivation and single-cell elemental analysis, we studied the impact of light and heavy Ln on transcriptome-wide gene expression when growing P. alloputida KT2440 with 2-phenylethanol as the carbon and energy source. Light Ln (La, Ce, and Nd) and a mixture of light and heavy Ln (La, Ce, Nd, Dy, Ho, Er, and Yb) had a positive effect on growth, whereas supplementation with heavy Ln (Dy, Ho, Er, and Yb) exerted fitness costs. These were likely a consequence of mismetallation and non-utilizable Ln interfering with Ln sensing and signaling. The measured amounts of cell-associated Ln varied between elements. Gene expression analysis suggested that the Ln sensing and signaling machinery, the two-component system PedS2R2 and PedH, responds differently to (non-)utilizable Ln. We expanded our understanding of the lanthanide (Ln) switch in P. alloputida KT2440, demonstrating that it adjusts the levels of pedE and pedH transcripts based on the availability of Ln. We propose that the usability of Ln influences the bacterium's response to different Ln elements.IMPORTANCEThe Ln switch, the inverse regulation of Ca- and Ln-dependent PQQ ADH in response to Ln availability in organisms featuring both, is central to our understanding of Ln utilization. Although the preference of bacteria for light Ln is well known, the effect of different Ln, light and heavy, on growth and gene expression has rarely been studied. We provide evidence for a fine-tuning mechanism of Ca- and Ln-dependent PQQ ADH in P. alloputida KT2440 on the transcriptome level. The response to (non-)utilizable Ln differs depending on the element. Ln commonly co-occur in nature. Our findings underline that Ln-utilizing microbes must be able to discriminate between Ln to use them effectively. Considering the prevalence of Ln-dependent proteins in many microbial taxa, more work addressing Ln sensing and signaling is needed. Ln availability likely necessitates different adaptations regarding Ln utilization.

The rheological properties of fresh concrete are a direct function of the interaction behaviour of the granular inventory of the concrete (i.e., gravel, sand and cement) and especially of the colloidal fractions of cement. Under low shear stresses, agglomeration of colloidal particles is observed, while at high shear stresses, dispersion of these agglomerates occurs. Besides the agglomeration state, the formation of shear banding, zones with concentrated shear flow, is another controlling mechanism of the flow behaviour of cement suspensions. Rheological creep tests in this study are focused on investigating the influence of shear history and hydration process on thixotropy of cement suspension. In this paper, the meaning of the word thixotropy is slightly extended to additionally encompass rheological aging and hydration effects. Selected samples were analyzed by coupling a rheometer to synchrotron X-ray tomography to gain insight into the shear-induced microstructural changes during shear start-up tests. The observations show heterogeneities in the velocity profile in the shear gap and the development of shear banding.

A thorough characterization of base materials is the prerequisite for further research. In this paper, the characterization data of the reference materials (CEM I 42.5 R, limestone powder, calcined clay and a mixture of these three components) used in the second funding phase of the priority program 2005 of the German Research Foundation (DFG SPP 2005) are presented under the aspects of chemical and mineralogical composition as well as physical and chemical properties. The data were collected based on tests performed by up to eleven research groups involved in this cooperative program.

Anthropogenic phosphorus (P) input from fertilised and unfertilised topsoils into surface water and re-dissolution from sediments can be key drivers of eutrophication. This study aimed to (1) analyse the P input processes into streams/rivers particularly via erosion from fertilised and unfertilised fields and (2) study the effectiveness of the riparian strip in reducing P emissions from diffuse sources. For the investigation, Cambisol-Tschernosem and Luvisol samples from Loess were taken from Thuringian test fields (Germany). Three laboratory simulations were designed to analyse P re-dissolution and leaching behaviour from topsoils and sediments and further extrapolated to a realistic scenario based on the P input path into receiving waters via erosion. Organic bonded phosphorus and orthophosphate were leached out at the beginning. Upscaling to a realistic scenario showed that the main source of P in receiving waters was leaching from sediment interstitial sites (57.5%) via percolation while the P re-dissolution via diffusion (13%), due to two heavy rain events (17%), and leaching from soil interstitial sites (12.5%) only played a minor role. The risk of eutrophication exceeded the threshold total P of 0.10 mg L -1 given as an orientation value by the Federal/State water consortium (LAWA). This was observed in percolates from all sandy soils (0.17–0.85 mg L -1 ), only slightly in the clayey soils (≤ 0.11 mg L -1 ) but not in either streambed sediment (≤ 0.08 mg L -1 ). However, local differences such as steeper slope, different soil compositions such as higher sand and lower clay percentages, and poorer buffering due to lower lime and aluminium content were identified as reasons for a higher risk of eutrophication.

In order to trace the sources of sediment materials and trace metals in the Weser River system (Germany), and the riverine input to the North Sea, Sr, Nd and Pb isotopes, together with multi-elemental compositions, were measured for sediments collected over the entire Weser River Basin, from headwaters to the estuary. Mass fractions of metals, including Ag, Cd, and Pb, and of one metalloid, Sb, higher than their crustal abundance, were observed within the entire Weser Basin. Isotope-amount ratio n(87Sr)/n(86Sr) and εNd ranged from 0.71182 ± 0.00005 to 0.72880 ± 0.00009 and −11.3 ± 0.3 to −21.0 ± 0.3, respectively. n(206Pb)/n(204Pb), n(207Pb)/n(204Pb), and n(208Pb)/n(204Pb) ranged from 18.226 ± 0.008 to 18.703 ± 0.012, 15.613 ± 0.007 to 15.653 ± 0.012 and 38.14 ± 0.02 to 38.84 ± 0.02, respectively. Sr and Nd isotope compositions reflected primarily a mixture of natural materials derived from the Weser Basin. Pb isotope signatures indicated strong anthropogenic influences in the middle-lower Weser region. Pb isotopic compositions in the sediments from the Aller (tributary of the Weser) and its tributary suggested influence from historical Pb-Zn ore mining in the Harz Mountains that might contribute to the observed elevated mass fractions of Ag, Cd, Sb and Pb in that region. K-means cluster and principal component analysis of the Sr, Nd, and Pb isotope data yielded results consistent with their isotope systematics, supporting statistical analysis as an unsupervised tool in isotope fingerprinting studies. Sr, Nd, and Pb isotopic signatures in the sediments of the Weser were distinctively different from those of another major river discharging into the North Sea, the Elbe. This suggested that this Sr, Nd, and Pb isotope dataset can be used to distinguish riverine input of sediment materials and metals between the two rivers, thereby assessing their individual contribution to materials transported into the North Sea.

This study presents a novel method for fluorine quantification determination by microwave-induced plasma optical emission spectrometry (MIP-OES). Due to the low temperature of this plasma, atomic emission of fluorine could not be measured, instead CaF molecular emissions were measured by using a calcium solution mixed in the spray chamber with the sample using a T-piece. Several wavelengths were studied to find the best signal to noise ratio for fluorine determination and 530.45 nm was chosen. The limit of detection for the determination of fluorine via CaF using MIP-OES was 1.1 mg L-1. A linear response was observed over two orders of magnitude (R-2 = 0.998). The developed method was applied to ten tea infusion samples from the UK and Saudi Arabia. The results were not significantly different (paired Student's t-test, p = 0.97) to the results obtained using the reference method, high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-GF MAS). The total fluorine in the tea infusions varied between 2.7 and 7.8 mg L-1; all of which were above the WHO recommended level of fluoride (0.8-1.5 mg L-1) in drinking water. This method can potentially be used for total fluorine determination and might be useful for fluorine speciation analysis when coupled with HPLC.