Trends in selected fields of reference material production.

For more than 110 years, BAM has been producing reference materials for a wide range of application fields. With the development of new analytical methods and new applications as well as continuously emerging more stringent requirements of laboratory accreditation with regard to quality control and metrological traceability, the demand and requirements for reference materials are increasing. This trend article gives an overview of general developments in the field of reference materials as well as developments in selected fields of application in which BAM is active. This includes inorganic and metal analysis, gas analysis, food and consumer products, and geological samples. In addition to these more traditional fields of application, developments in the areas of optical spectroscopy, particularly fluorescence methods, and nanomaterials are considered.

Triple Isotope Fractionation Exponents of Elements Measured by MC-ICP-MS-An Example of Mg.

In most chemical reactions, stable isotopes are fractionated in a mass-dependent manner, yielding correlated isotope ratios in elements with three or more stable isotopes. The proportionality between isotope ratios is set by the triple isotope fractionation exponent θ that can be determined precisely for, e.g., sulfur and oxygen by IRMS, but not for metal(loid) elements due to the lower precision of MC-ICP-MS analysis and smaller isotopic variations. Here, using Mg as a test case, we compute a complete metrologically robust uncertainty budget for apparent θ values and, with reference to this, present a new measurement approach that reduces uncertainty on θ values by 30%. This approach, namely, direct educt-product bracketing (sample-sample bracketing), allows apparent θ values of metal(loid) isotopes to be determined precisely enough to distinguish slopes in three-isotope space. For the example of Mg, we assess appropriate quality control standards for interference-to-signal ratios and report apparent θ values of carbonate-seawater pairs. We determined apparent θ values for marine biogenic carbonates, where the foraminifera Globorotalia menardii yields 0.514 ± 0.005 (2 SD), the coral Porites, 0.515 ± 0.006 (2 SD), and two specimens of the giant clam Tridacna gigas, 0.508 ± 0.007 (2 SD) and 0.509 ± 0.006 (2 SD), documenting differences in the uptake pathway of Mg among marine calcifiers. The capability to measure apparent θ values more precisely adds a new dimension to metal(loid) δ values, with the potential to allow us to resolve different modes of fractionation in industrial and natural processes.

Boron isotope variability related to boron speciation (change during uptake and transport) in bell pepper plants and SI traceable n(11 B)/n(10 B) ratios for plant reference materials.

RATIONALE: Boron (B) is an essential micronutrient in plants and its isotope variations are used to gain insights into plant metabolism, which is important for crop plant cultivation. B isotope variations were used to trace intra-plant fractionation mechanisms in response to the B concentration in the irrigation water spanning the range from B depletion to toxic levels. METHODS: A fully validated analytical procedure based on multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), sample decomposition and B matrix separation was applied to study B isotope fractionation. The validation was accomplished by establishing a complete uncertainty budget and by applying reference materials, yielding expanded measurement uncertainties of 0.8‰ for pure boric acid solutions and ≤1.5‰ for processed samples. With this validated procedure SI traceable B isotope amount ratios were determined in plant reference materials for the first time. RESULTS: The B isotope compositions of irrigation water and bell pepper samples suggest passive diffusion of the heavy 11 B isotope into the roots during low to high B concentrations while uptake of the light 10 B isotope was promoted during B depletion, probably by active processes. A systematic enrichment of the heavy 11 B isotope in higher located plant parts was observed (average Δ11 Bleaf-roots = 20.3 ± 2.8‰ (1 SD)), possibly by a facilitated transport of the heavy 11 B isotope to growing meristems by B transporters. CONCLUSIONS: The B isotopes can be used to identify plant metabolism in response to the B concentration in the irrigation water and during intra-plant B transfer. The large B isotope fractionation within the plants demonstrates the importance of biological B cycling for the global B cycle.

A validated analytical procedure for boron isotope analysis in plants by MC-ICP-MS.

Boron (B) is an essential micronutrient for plant growth. Lack of valid methods for pretreatment and measurement of δ11B in plant restrict applications of it in the biosphere. Dry ashing, one step cation exchange and micro-sublimation were combined to separate and purify boron (B) in plant tissues. The low procedure blank, high B recovery and the accurate δ11B values of the plant reference materials demonstrate that this method is suitable and valid for B pretreatment and δ11B measurement in plant samples by MC-ICP-MS. Based on this method, the δ11B in different plants (Brassica napus, Chenopodium album L, moss, lichen, and Nostoc commune) was analyzed. For Brassica napus, δ11B increased gradually from root to leaf, and then decreased to rapeseed. For the same parts, the δ11B increased from the lower parts to the higher parts. This variation may be due to the B(OH)3 transporter of NIP6;1 and the incorporation of B into the cell. The reason for lower δ11B values in shell and rapeseed compared to those in leaves presumably is to the preferred transport of borate in the phloem. The largest δ11B fractionation between leaf and root in Brassica napus and Chenopodium album L was + 24.2‰ and + 26.6‰, respectively. The large variation and fractionation of δ11B within plants indicates that δ11B is a good tracer to study the B translocation mechanisms and metabolism within plants. The δ11B in Nostoc commune, lichen, and moss showed variations of -4.1‰ to + 21.5‰, - 9.4‰ to + 7.3‰, and - 18.3‰ to + 11. 9‰, respectively. In the same site, δ11B in different plants ranked Nostoc commune>moss>lichen and δ11B in mosses growing in different environment ranked soil>tree>rock. Rain and soil available B are the main B sources for these plants. The δ11B in Nostoc commune, lichen, and moss may be a useful tracer to study the atmospheric B input. In the future, plants culture experiments under certain environments and studies from molecular level are necessary to decipher the variation of δ11B and fractionation mechanisms within plants.

The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile - Marine sources and diagenetic effects.

Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very heavy values generate a compositionally unique material. These compositions trace the presence of guano in natural ecosystems and its use as fertilizer in present and past agriculture.

Lombards on the move--an integrative study of the migration period cemetery at Szólád, Hungary.

In 2005 to 2007 45 skeletons of adults and subadults were excavated at the Lombard period cemetery at Szólád (6th century A.D.), Hungary. Embedded into the well-recorded historical context, the article presents the results obtained by an integrative investigation including anthropological, molecular genetic and isotopic (δ(15)N, δ(13)C, (87)Sr/(86)Sr) analyses. Skeletal stress markers as well as traces of interpersonal violence were found to occur frequently. The mitochondrial DNA profiles revealed a heterogeneous spectrum of lineages that belong to the haplogroups H, U, J, HV, T2, I, and K, which are common in present-day Europe and in the Near East, while N1a and N1b are today quite rare. Evidence of possible direct maternal kinship was identified in only three pairs of individuals. According to enamel strontium isotope ratios, at least 31% of the individuals died at a location other than their birthplace and/or had moved during childhood. Based on the peculiar 87 Sr/86 Sr ratio distribution between females, males, and subadults in comparison to local vegetation and soil samples, we propose a three-phase model of group movement. An initial patrilocal group with narrower male but wider female Sr isotope distribution settled at Szólád, whilst the majority of subadults represented in the cemetery yielded a distinct Sr isotope signature. Owing to the virtual absence of Szólád-born adults in the cemetery, we may conclude that the settlement was abandoned after approx. one generation. Population heterogeneity is furthermore supported by the carbon and nitrogen isotope data. They indicate that a group of high-ranking men had access to larger shares of animal-derived food whilst a few individuals consumed remarkable amounts of millet. The inferred dynamics of the burial community are in agreement with hypotheses of a highly mobile lifestyle during the Migration Period and a short-term occupation of Pannonia by Lombard settlers as conveyed by written sources.

The need for new isotope reference materials.

Isotope reference materials are needed to calibrate and validate analytical procedures used for the determination of isotope amount ratios, procedurally defined isotope ratios or so-called δ values. In contrast to the huge analytical progress in isotope ratio analytics, the production of isotope reference materials has not kept pace with the increasing needs of isotope analysts. Three representative isotope systems are used to explain the technical and non-technical difficulties and drawbacks, on one hand, and to demonstrate what can be achieved at its best, on the other hand. A clear statement is given that new isotope reference materials are needed to obtain traceable and thus comparable data, which is essential for all kinds of isotope research. The range of available isotope reference materials and δ reference materials should be increased and matrix reference materials certified for isotope compositions or δ values, which do not exist yet, should be provided.

Development and validation of a method to determine the boron isotopic composition of crop plants.

We present a comprehensive chemical and mass spectrometric method to determine boron isotopic compositions of plant tissue. The method including dry ashing, a three-step ion chromatographic boron-matrix separation, and (11)B/(10)B isotope ratio determinations using the Cs(2)BO(2)(+) graphite technique has been validated using certified reference and quality control materials. The developed method is capable to determine δ(11)B values in plant tissue down to boron concentrations of 1 mg/kg with an expanded uncertainty of ≤1.7‰ (k = 2). The determined δ(11)B values reveal an enormous isotopic range of boron in plant tissues covering three-quarters of the natural terrestrial occurring variation in the boron isotopic composition. As the local environment and anthropogenic activity mainly control the boron intake of plants, the boron isotopic composition of plants can be used for food provenance studies.

First investigation of the microbiology of the deepest layer of ocean crust.

The gabbroic layer comprises the majority of ocean crust. Opportunities to sample this expansive crustal environment are rare because of the technological demands of deep ocean drilling; thus, gabbroic microbial communities have not yet been studied. During the Integrated Ocean Drilling Program Expeditions 304 and 305, igneous rock samples were collected from 0.45-1391.01 meters below seafloor at Hole 1309D, located on the Atlantis Massif (30 °N, 42 °W). Microbial diversity in the rocks was analyzed by denaturing gradient gel electrophoresis and sequencing (Expedition 304), and terminal restriction fragment length polymorphism, cloning and sequencing, and functional gene microarray analysis (Expedition 305). The gabbroic microbial community was relatively depauperate, consisting of a low diversity of proteobacterial lineages closely related to Bacteria from hydrocarbon-dominated environments and to known hydrocarbon degraders, and there was little evidence of Archaea. Functional gene diversity in the gabbroic samples was analyzed with a microarray for metabolic genes ("GeoChip"), producing further evidence of genomic potential for hydrocarbon degradation--genes for aerobic methane and toluene oxidation. Genes coding for anaerobic respirations, such as nitrate reduction, sulfate reduction, and metal reduction, as well as genes for carbon fixation, nitrogen fixation, and ammonium-oxidation, were also present. Our results suggest that the gabbroic layer hosts a microbial community that can degrade hydrocarbons and fix carbon and nitrogen, and has the potential to employ a diversity of non-oxygen electron acceptors. This rare glimpse of the gabbroic ecosystem provides further support for the recent finding of hydrocarbons in deep ocean gabbro from Hole 1309D. It has been hypothesized that these hydrocarbons might originate abiotically from serpentinization reactions that are occurring deep in the Earth's crust, raising the possibility that the lithic microbial community reported here might utilize carbon sources produced independently of the surface biosphere.

Air handling in clean laboratory environments: the reason for anomalously high boron background levels.

The isotopic analysis of boron from material that carries only trace amounts of boron requires low boron blank levels. Large efforts are taken to keep blank levels low by purifying reagents. We performed exposure experiments and determined procedure blanks before and after the air-handling system was modified from silicate glass filters to polyethylene/polystyrole and active carbon filters. Our investigations demonstrate that the air-handling system may be the major source of boron blank in many laboratories, as the widely used silicate glass filters, which contain boron as a major component, in the form of borax and boric acid, release significant amounts of boron to the air.

Influence of increasing zinc contents in brass in the early stages of corrosion investigated by in-situ TM-AFM and SIMS.

In-situ tapping mode atomic force microscopy (TM-AFM), a powerful, high-resolution imaging technique for determining the structure of surfaces and ex-situ secondary ion mass spectroscopy (SIMS), a multielement, high-depth-resolution method, were used to examine the influence of increasing zinc contents in brass in the early stages of corrosion. Four different samples (pure Cu, pure Zn, Cu/Zn=90/10 wt% and Cu/Zn=70/30 wt%) were studied in order to determine their chemical behaviour under various atmospheric conditions. The in-situ TM-AFM investigations were carried out in synthetic air with 60% relative humidity (RH) and 80% RH with 250 ppb SO(2). The samples for the ex-situ SIMS experiments were weathered over a period of 60 h in 80% RH and 250 ppb SO(2). The in-situ TM-AFM investigations have shown that an increasing Zn content in brass increases the corrosion rate.