Isotopic biographies reveal horse rearing and trading networks in medieval London.

This paper reports a high-resolution isotopic study of medieval horse mobility, revealing their origins and in-life mobility both regionally and internationally. The animals were found in an unusual horse cemetery site found within the City of Westminster, London, England. Enamel strontium, oxygen, and carbon isotope analysis of 15 individuals provides information about likely place of birth, diet, and mobility during the first approximately 5 years of life. Results show that at least seven horses originated outside of Britain in relatively cold climates, potentially in Scandinavia or the Western Alps. Ancient DNA sexing data indicate no consistent sex-specific mobility patterning, although three of the five females came from exceptionally highly radiogenic regions. Another female with low mobility is suggested to be a sedentary broodmare. Our results provide direct and unprecedented evidence for a variety of horse movement and trading practices in the Middle Ages and highlight the importance of international trade in securing high-quality horses for medieval London elites.

The Historic Built Environment As a Long-Term Geochemical Archive: Telling the Time on the Urban "Pollution Clock".

This study introduces a novel methodology for utilizing historic built environments as reliable long-term geochemical archives, addressing a gap in the reconstruction of past anthropogenic pollution levels in urban settings. For the first time, we employ high-resolution laser ablation mass spectrometry for lead isotope (206Pb/207Pb and 208Pb/206Pb) analysis on 350-year-old black crust stratigraphies found on historic built structures, providing insights into past air pollution signatures. Our findings reveal a gradual shift in the crust stratigraphy toward lower 206Pb/207Pb and higher 208Pb/206Pb isotope ratios from the older to the younger layers, indicating changes in lead sources over time. Mass balance analysis of the isotope data shows black crust layers formed since 1669 primarily contain over 90% Pb from coal burning, while other lead sources from a set of modern pollution including but not limited to leaded gasoline (introduced after 1920) become dominant (up to 60%) from 1875 onward. In contrast to global archives such as ice cores that provide integrated signals of long-distance pollution, our study contributes to a deeper understanding of localized pollution levels, specifically in urban settings. Our approach complements multiple sources of evidence, enhancing our understanding of air pollution dynamics and trends, and the impact of human activities on urban environments.

Laser ablation mass spectrometry blast through detection in R.

RATIONALE: Organisms that grow a hard carbonate shell or skeleton, such as foraminifera, corals or molluscs, incorporate trace elements into their shell during growth that reflect the environmental change and biological activity they experienced during life. These geochemical signals locked within the carbonate are archives used in proxy reconstructions to study past environments and climates, to decipher taxonomy of cryptic species and to resolve evolutionary responses to climatic changes. METHODS: Here, we use laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as a time-resolved acquisition to quantify the elemental composition of carbonate shells and skeletons. We present the LABLASTER (Laser Ablation BLASt Through Endpoint in R) package, which imports a single time-resolved LA-ICP-MS analysis, then detects when the laser has ablated through the carbonate as a function of change in signal over time and outputs key summary statistics. We provide two examples within the package: a fossil planktic foraminifer and a tropical coral skeleton. RESULTS: We present the first R package that automates the selection of desired data during data reduction workflows. This is achieved by automating the detection of when the laser has ablated through a sample using a smoothed time series, followed by removal of off-target data points. The functions are flexible and adjust dynamically to maximise the duration of the desired geochemical target signal, making this package applicable to a wide range of heterogenous bioarchives. Visualisation tools for manual validation are also included. CONCLUSIONS: LABLASTER increases transparency and repeatability by algorithmically identifying when the laser has either ablated fully through a sample or across a mineral boundary and is thus no longer documenting a geochemical signal associated with the desired sample. LABLASTER's focus on better data targeting means more accurate extraction of biological and geochemical signals.

Surface ocean warming and acidification driven by rapid carbon release precedes Paleocene-Eocene Thermal Maximum.

The Paleocene-Eocene Thermal Maximum (PETM) is recognized by a major negative carbon isotope (δ13C) excursion (CIE) signifying an injection of isotopically light carbon into exogenic reservoirs, the mass, source, and tempo of which continue to be debated. Evidence of a transient precursor carbon release(s) has been identified in a few localities, although it remains equivocal whether there is a global signal. Here, we present foraminiferal δ13C records from a marine continental margin section, which reveal a 1.0 to 1.5‰ negative pre-onset excursion (POE), and concomitant rise in sea surface temperature of at least 2°C and a decline in ocean pH. The recovery of both δ13C and pH before the CIE onset and apparent absence of a POE in deep-sea records suggests a rapid (< ocean mixing time scales) carbon release, followed by recovery driven by deep-sea mixing. Carbon released during the POE is therefore likely more similar to ongoing anthropogenic emissions in mass and rate than the main CIE.

The effect of matrix interferences on in situ boron isotope analysis by laser ablation multi-collector inductively coupled plasma mass spectrometry.

RATIONALE: Boron isotope analysis of marine carbonates by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) offers the potential for rapid sample throughput, and the means to examine micron-scale variations in the δ11 B signatures of fossil skeletons and shells/tests of marine organisms. Existing studies demonstrate an acceptable level of reproducibility is achievable, but also typically show a level of accuracy outside the limits required by most applications. Here we investigate matrix interference effects as a cause of inaccuracy and imprecision. METHODS: Analyses were performed on a standard format Thermo Scientific Neptune Plus MC-ICP mass spectrometer coupled to a New Wave Research 193 nm ArF laser ablation system. The effects of matrix interference on δ11 B analysis were investigated through analyses of a set of reference materials with differing B/Ca ratios. Three approaches to correct for matrix-induced effects were trialled: (1) use of matrix-matched standards, (2) utilisation of the relationship between δ11 B inaccuracy and11 B/43 Ca, 11 B/40 ArCa4+ or 11 B/Cainterference from three reference materials with known δ11 B values and varying B/Ca ratios, and (3) direct characterisation of the (sloping) interference itself. RESULTS: Matrix interference from scattered Ca ions on 10 B can impede both the accuracy and the reproducibility of δ11 B analysis by LA-MC-ICP-MS. Based on analyses of two in-house reference materials, deep sea coral PS69/3181 and inorganic calcite UWC-1, we find approach 2, following the 11 B/Cainterference relationship, gives the best mean accuracies (within 0.4‰ of solution values) and external reproducibilities (± 0.5‰ 2 SD for PS69/3181). This approach has been applied to analyses of an annual growth cycle of a Siderastrea siderea coral and eight Cibicidoides wuellerstorfi benthic foraminifera. Both coral and foraminifera data match solution MC-ICP-MS analyses within reported uncertainties. CONCLUSIONS: LA-MC-ICP-MS can produce accurate and precise δ11 B data to a 0.5‰ (2σ) level on <0.3 ng B after correction for Ca interference effects.

Progressive biogeochemical transformation of placer gold particles drives compositional changes in associated biofilm communities.

Biofilms on placer gold (Au)-particle surfaces drive Au solubilization and re-concentration thereby progressively transforming the particles. Gold solubilization induces Au-toxicity; however, Au-detoxifying community members ameliorates Au-toxicity by precipitating soluble Au to metallic Au. We hypothesize that Au-dissolution and re-concentration (precipitation) place selective pressures on associated microbial communities, leading to compositional changes and subsequent Au-particle transformation. We analyzed Au-particles from eight United Kingdom sites using next generation sequencing, electron microscopy and micro-analyses. Gold particles contained biofilms composed of prokaryotic cells and extracellular polymeric substances intermixed with (bio)minerals. Across all sites communities were dominated by Proteobacteria (689, 97% Operational Taxonomic Units, 59.3% of total reads), with ß-Proteobacteria being the most abundant. A wide range of Au-morphotypes including nanoparticles, micro-crystals, sheet-like Au and secondary rims, indicated that dissolution and re-precipitation occurred, and from this transformation indices were calculated. Multivariate statistical analyses showed a significant relationship between the extent of Au-particle transformation and biofilm community composition, with putative metal-resistant Au-cycling taxa linked to progressive Au transformation. These included the genera Pseudomonas, Leptothrix and Acinetobacter. Additionally, putative exoelectrogenic genera Rhodoferax and Geobacter were highly abundant. In conclusion, biogeochemical Au-cycling and Au-particle transformation occurred at all sites and exerted a strong influence on biofilm community composition.