Structural equation modelling of mercury intra-skeletal variability on archaeological human remains.

Archaeological burial environments are useful archives to investigate the long-term trends and the behaviour of mercury. In order to understand the relationship between mercury, skeletons and soil, we applied Partial Least Squares - Structural Equation Modelling (PLS-SEM) to a detailed, multisampling (n = 73 bone samples +37 soil samples) design of two archaeological graves dating to the 6th to 7th centuries CE (A Lanzada site, NW Spain). Mercury content was assessed using a DMA-80, and data about bone structure and the grave soil/sediments were obtained using FTIR-ATR spectroscopy. The theoretical model is supported by proxies of bone structure, grave soil/sediments, and location of the bone within the skeleton. The general model explained 61 % of mercury variance. Additionally, Partial Least Square - Prediction Oriented Segmentation (PLS-POS) was also used to check for segmentation in the dataset. POS revealed two group of samples depending on the bone phase (hydroxyapatite or collagen) controlling the Hg content, and the corresponding models explained 86 % and 76 % of Hg variance, respectively. The results suggest that mercury behaviour in the graves is complex, and that mercury concentrations were influenced by i) the ante-mortem status of the bone matrix, related to the weight of each bone phase; ii) post-mortem evolution of bone crystallinity, where bone loses mercury with increasing alteration; and iii) the proximity of the skeletal pieces to mercury target organs, as decomposition and collapse of the thoracic and abdominal soft tissues causes a secondary mercury enrichment in bones from the body trunk during early post-mortem. Skeletons provide a source of mercury to the soil whereas soil/sediments contribute little to skeletal mercury content.

Understanding Necrosol pedogenetical processes in post-Roman burials developed on dunes sands.

In Archaeology much emphasis is dedicated to bone preservation, but less attention is paid to the burial soil (i.e., Necrosol), despite its crucial role in governing the geochemical environment. The interaction between human remains and sediments starts after inhumation, leading to bidirectional physico-chemical changes. To approach these complex, bidirectional processes, we sampled at high resolution (n = 46) two post-Roman wooden coffin burials (one single and another double), and the coeval paleosol (n = 20; nearby pedo-sedimentary sequence). The samples were analysed for physical (grain size, colour) and chemical (pH; LOI; elemental composition: FTIR-ATR, XRF, C, N) properties. Principal component analysis enabled to identify five main pedogenetical processes: decalcification, melanization, acidification, neoformation of secondary minerals (i.e., clays) and enrichment in phosphorus. Melanization, acidification and phosphorous enrichment seem to be convergent processes in Necrosols-irrespective of the parent material. Decalcification may be restricted to carbonate containing soil/sediments. Despite not mentioned in previous research, clay formation might also be an overall process. Compared to the local, coeval paleosol, pedogenesis in the studied burial soils was low (double burial) to moderate (single burial). Our results also emphasize the need to study the finer soil fractions, as they provide clues both on soil formation and bone diagenesis.

Approaching mercury distribution in burial environment using PLS-R modelling.

Mercury environmental cycle and toxicology have been widely researched. Given the long history of mercury pollution, researching mercury trends in the past can help to understand its behaviour in the present. Archaeological skeletons have been found to be useful sources of information regarding mercury loads in the past. In our study we applied a soil multi-sampling approach in two burials dated to the 5th to 6th centuries AD. PLRS modelling was used to elucidate the factors controlling mercury distribution. The model explains 72% of mercury variance and suggests that mercury accumulation in the burial soils is the result of complex interactions. The decomposition of the bodies not only was the primary source of mercury to the soil but also responsible for the pedogenetic transformation of the sediments and the formation of soil components with the ability to retain mercury. The amount of soft tissues and bone mass also resulted in differences between burials, indicating that the skeletons were a primary/secondary source of mercury to the soil (i.e. temporary sink). Within burial variability seems to depend on the proximity of the soil to the thoracic area, where the main mercury target organs were located. We also conclude that, in coarse textured soils, as the ones studied in this investigation, the finer fraction (i.e. silt + clay) should be analysed, as it is the most reactive and the one with the higher potential to provide information on metal cycling and incipient soil processes. Finally, our study stresses the need to characterise the burial soil environment in order to fully understand the role of the interactions between soil and skeleton in mercury cycling in burial contexts.

Human bones tell the story of atmospheric mercury and lead exposure at the edge of Roman World.

Atmospheric metal pollution is a major health concern whose roots pre-date industrialization. This study pertains the analyses of ancient human skeletons and compares them with natural archives to trace historical environmental exposure at the edge of the Roman Empire in NW Iberia. The novelty of our approach relies on the combination of mercury, lead and lead isotopes. We found over a 700-year period that rural Romans incorporated two times more mercury and lead into their bones than post-Romans inhabiting the same site, independent of sex or age. Atmospheric pollution sources contributed on average 57% (peaking at 85%) of the total lead incorporated into the bones in Roman times, which decreased to 24% after the decline of Rome. These values and accompanying changes in lead isotopic composition mirror changes in atmospheric Pb deposition recorded in local peatlands. Thus, skeletons are a time-transgressive archive reflecting contaminant exposure.