Geogenic lead isotope signatures from meat products in Great Britain: potential for use in food authentication and supply chain traceability

This paper presents lead (Pb) isotope data from samples of farm livestock raised in three areas of Britain that have elevated natural Pb levels: Central Wales, the Mendips and the Derbyshire Peak District. This study highlights three important observations; that the Pb found in modern British meat from these three areas is geogenic and shows no clear evidence of modern tetraethyl anthropogenic Pb contribution; that the generally excellent match between the biological samples and the ore field data, particularly for the Mendip and Welsh data, suggests that this technique might be used to provenance biological products to specific ore sites, under favourable conditions; and that modern systems reflect the same process of biosphere averaging that is analogous to cultural focusing in human archaeological studies that is the process of biological averaging leading to an homogenised isotope signature with increasing Pb concentration

Insights into the transfer of silicon isotopes into the sediment record

The first δ30Sidiatom data from lacustrine sediment traps are presented from Lake Baikal, Siberia. Data are compared with March surface water (upper 180 m) δ30SiDSi compositions for which a mean value of +2.28‰ ±  0.09 (95 % confidence) is derived. This value acts as the pre-diatom bloom baseline silicic acid isotopic composition of waters (δ30SiDSi initial). Open traps were deployed along the depth of the Lake Baikal south basin water column between 2012 and 2013. Diatom assemblages display a dominance ( > 85 %) of the spring/summer bloom species Synedra acus var radians, so that δ30Sidiatom compositions reflect predominantly spring/summer bloom utilisation. Diatoms were isolated from open traps and, in addition, from 3-monthly (sequencing) traps (May, July and August 2012) for δ30Sidiatom analyses. Mean δ30Sidiatom values for open traps are +1.23‰ ±  0.06 (at 95 % confidence and MSWD of 2.9, n = 10). Total dry mass sediment fluxes are highest in June 2012, which we attribute to the initial export of the dominant spring diatom bloom. We therefore argue that May δ30Sidiatom signatures (+0.67‰ ±  0.06, 2σ) when compared with mean upper water δ30SiDSi initial (e.g. pre-bloom) signatures can be used to provide a snapshot estimation of diatom uptake fractionation factors (ϵuptake) in Lake Baikal. A ϵuptake estimation of −1.61 ‰ is therefore derived, although we emphasise that synchronous monthly δ30SiDSi and δ30Sidiatom data would be needed to provide more robust estimations and therefore more rigorously test this, particularly when taking into consideration any progressive enrichment of the DSi pool as blooms persist. The near-constant δ30Sidiatom composition in open traps demonstrates the full preservation of the signal through the water column and thereby justifies the use and application of the technique in biogeochemical and palaeoenvironmental research. Data are finally compared with lake sediment core samples, collected from the south basin. Values of +1.30‰ ±  0.08 (2σ) and +1.43‰ ±  0.13 (2σ) were derived for cores BAIK13-1C (0.6–0.8 cm core depth) and at BAIK13-4F (0.2–0.4 cm core depth) respectively. Trap data highlight the absence of a fractionation factor associated with diatom dissolution (ϵdissolution) (particularly as Synedra acus var radians, the dominant taxa in the traps, is very susceptible to dissolution) down the water column and in the lake surface sediments, thus validating the application of δ30Sidiatom analyses in Lake Baikal and other freshwater systems, in palaeoreconstructions

Optimisation of a current generation ICP-QMS and benchmarking against MC-ICP-MS spectrometry for the determination of lead isotope ratios in environmental samples

© 2018 The Royal Society of Chemistry. Novel ANOVA methodology was used to benchmark ICP-QMS against MC-ICP-MS for Pb isotope ratios, demonstrating "fitness-for-purpose" in environmental source apportionment. The precision and accuracy of lead (Pb) isotope measurements obtained from quadrupole-based mass spectrometers (ICP-QMS) are considered to be limited by a number of factors originating in different components of the instruments. In this study, experimental and instrumental protocols were optimised for determining lead isotope ratios in urban soil digests. Experimental measures included individual dilution of all samples and isotopic standards (SRM-981, NIST) to a single Pb concentration intended to produce an intensity which was high enough to negate blanks and interferences but low enough to ensure the detector operated only in pulse counting mode. Instrumental protocols included batch dead time correction, optimisation of dwell time and the number of scans employed and correction of mass discrimination by sequential application of both internal ( 203 Tl/ 205 Tl ratio) and external (SRM-981, NIST) standards. This optimised methodology was benchmarked against multi-collector mass spectrometer (MC-ICP-MS) measurements of Pb isotope ratios using replicate digest solutions of the same soil; but after these had been subjected to Pb separation using an ion-exchange procedure. On the assumption that MC-ICP-MS measurements are more accurate, small additive and multiplicative differences were observed in only the 4 th decimal place. ANOVA was used to compare the precisions of the two techniques demonstrating equal precisions c. 0.08% for 207 Pb/ 206 Pb, suggesting a sample heterogeneity limitation. By contrast, for 207 Pb/ 204 Pb, the worst-case ratio, ICP-QMS had a 10-fold poorer precision, despite negligible interference from 204 Hg, implying an instrumental limitation. The study concludes that ICP-QMS can provide valuable source apportionment information for most Pb isotope ratios but further efforts should focus on improving assay of the 207 Pb/ 204 Pb ratio

Spatial differences in dissolved silicon utilisation in Lake Baikal, Siberia: examining the impact of high diatom biomass events and eutrophication

Recent research has highlighted how Lake Baikal, Siberia, has responded to the direct and indirect effects of climate change (e.g., ice-cover duration), nutrient loading, and pollution, manifesting as changes in phytoplankton/zooplankton populations, community structure, and seasonal succession. Here, we combine and compare= analyses of chlorophyll a (an estimate of total algal biomass), carotenoid pigments (biomarkers of algal groups), and lake water silicon isotope geochemistry (d30SiDSi) to differentiate spatial patterns in dissolved silicon (DSi) uptake at Lake Baikal. A total of 15 sites across the three basins (south, central, and north) of Lake Baikal were sampled in August 2013 along a depth gradient of 0–180 m. Strong, significant correlations were found between vertical profiles of photic zone DSi concentrations and d30SiDSi compositions (r 5 20.81, p < 0.001), although these are strongest in the central basin aphotic zone (r 5 20.98, p < 0.001). Data refute the hypothesis of DSi uptake by picocyanobacteria. Algal biomass profiles and high surface d30SiDSi compositions suggest greater productivity in the south basin and more oligotrophic conditions in the north basin. d30SiDSi signatures are highest at depth (20 m) in central basin sites, indicating greater (10–40%) DSi utilization at deep chlorophyll maxima. DSi limitation occurs in the pelagic central basin, probably reflecting a high diatom biomass bloom event (Aulacoseira baicalensis). Meanwhile in the more hydrologically restricted, shallow Maloe More region (central basin), both high d30SiDSi compositions and picocyanobacteria (zeaxanthin) concentrations, respectively point to the legacy of an “Aulacoseira bloom year” and continuous nutrient supply in summer months (e.g., localized eutrophication)

Combining isotope ratios for provenancing Viking Age iron artefacts in the British Isles: a pilot study

Stable and radiogenic isotope analysis – particularly using lead isotope analysis (LIA) - has previously been shown to be a useful tool for the provenancing of ancient metal artefacts of silver and copper and its alloys, but less progress has been made in the provenancing of iron artefacts, despite their importance and frequency in the archaeological record. In this pilot study we investigate for the first time the possibilities of iron isotope analysis in combination with trace strontium isotope analysis and LIA for the provenancing of iron objects believed to be from the Viking Age in the British Isles. Previous studies have shown that analysis of each of these isotopes can contribute to provenancing iron artefacts, but they are not individually resolutory. In this proof-of-concept study, we examine the Fe, Sr and Pb isotopes of 7 artefacts believed to derive from the Viking Age: 3 from Meols - a former Viking seaport on Wirral and 4 samples from the probable location of the AD 1066 Battle of Fulford in North Yorkshire. We also examine an additional artefact of unknown antiquity from Bebington Heath – a possible location of the AD 937 Battle of Brunanburh. Although the pilot data set is too small to make definitive conclusions, it has paved the way for a fuller study involving 100 samples (including 30 from the former Viking camp of Torksey, Lincolnshire) funded by the NEIF fund of the UK National Environmental Research Council. The high range of 87Sr/86Sr values in the present data set of 8 is beyond what would be expected for bog iron (with a cut-off ~ 0.709) and suggests that mined ore was being used, a preliminary conclusion supported by the narrow range of Fe isotope data

Erosive cola-based drinks affect the bonding to enamel surface: an in vitro study

Objective: This study aimed to assess the impact of in vitro erosion provoked by different cola-based drinks (Coke types), associated or not with toothbrushing, to bonding to enamel. Material and methods: Forty-six bovine enamel specimens were prepared and randomly assigned into seven groups (N=8): C- Control (neither eroded nor abraded), ERO-RC: 3x/1-minute immersion in Regular Coke (RC), ERO-LC: 3x/1-minute immersion in Light Coke (LC), ERO-ZC: 3x/1-minute immersion in Zero Coke (ZC) and three other eroded groups, subsequently abraded for 1-minute toothbrushing (EROAB-RC, EROAB-LC and EROAB-ZC, respectively). After challenges, they were stored overnight in artificial saliva for a total of 24 hours and restored with Adper Single Bond 2/Filtek Z350. Buildup coronal surfaces were cut in 1 mm2 -specimens and subjected to a microtensile test. Data were statistically analyzed by two-way ANOVA/Bonferroni tests (α=0.05). Failure modes were assessed by optical microscopy (X40). The Interface of the restorations were observed using Confocal Laser Scanning Microscopy (CLSM). Results: All tested cola-based drinks significantly reduced the bond strength, which was also observed in the analyses of interfaces. Toothbrushing did not have any impact on the bond strength. CLSM showed that except for Zero Coke, all eroded specimens resulted in irregular hybrid layer formation. Conclusions: All cola-based drinks reduced the bond strength. Different patterns of hybrid layers were obtained revealing their impact, except for ZC

Nutrient utilization and diatom productivity changes in the low-latitude south-eastern Atlantic over the past 70 ka: response to Southern Ocean leakage

Eastern boundary upwellings (EBUs) are some of the key loci of biogenic silica (opal) burial in the modern ocean, representing important productive coastal systems that extraordinarily contribute to marine organic carbon fixation. The Benguela upwelling system (BUS), in the low-latitude south-eastern Atlantic, is one of the major EBUs and is under the direct influence of nutrient-rich Southern Ocean waters. Quantification of past changes in diatom productivity through time, in response to late Quaternary climatic change, feeds into our understanding of the sensitivity of EBUs to future climatic perturbations. Existing sediment archives of silica cycling include opal burial fluxes, diatom assemblages, and opaline silicon isotopic variations (denoted by δ30Si). Burial fluxes and siliceous assemblages are limited to recording the remains reaching the sediment (i.e. export), and δ30Si variations are complicated by species-specific influences and seasonality. Here, we present the first combined δ30Si record of two large centric diatoms from the BUS, encompassing full glacial conditions to the Holocene. In addition to export, our new data allow us to reconstruct the utilization of dissolved Si in surface waters in an area with strong input from Southern Ocean waters. Our new archives show that there was enhanced upwelling of Southern Ocean Si-rich water accompanied by strong silicic acid utilization by coastal dwelling diatoms during Marine Isotope Stage 3 (MIS3; 60–40 ka). This pulse of strong silicic acid utilization was followed by a weakening of upwelling and coastal diatom Si utilization into MIS2, before an increase in pelagic diatom Si utilization across the deglaciation. We combine our findings with mass balance model experiments to show that changes in surface water silica cycling through time are a function of both upwelling intensity and utilization changes, illustrating the sensitivity of EBUs to climatic change on glacial–interglacial scales

Tracking Roman lead sources using lead isotope analysis: a case study from the imperial rural estate at Vagnari (Puglia, Italy)

Recent studies have utilised isotopic analysis for an understanding of the supply sources of lead to major Roman cities in Italy to good effect. Far less attention has been focused on contemporary rural sites in Italy or on the evidence for lead ore sources and the use and processing of lead in such locations. Rather than the more common focus on the isotopic analysis of lead pipes and ingots, this study concentrates on the lead processing and recycling debris, as well as the finished utilitarian objects, excavated in the central village of an imperial estate at Vagnari in south-east Italy. The archaeological and isotopic evidence indicates that the source of lead used in the production of implements here was not uniform, rather the ores stem from various regions within the Roman empire ranging from Italy, Spain, and Greece, to France or possibly Britain