The Perils of Pits: further research at Durrington Walls henge (2021–2025)

Vincent Gaffney; Eamonn Baldwin; Robin Allaby; Martin Bates; Richard Bates; Alex Finlay; Christopher Gaffney; Teri Hansford; Timothy Kinnaird; Wolfgang Neubauer; Klaus Löcker; Tom Sparrow; Immo Trinks; Mario Wallner; Eugene Ch'ng

doi:10.11141/ia.69.19

7.1 Geochemical analysis

Geochemical analysis was undertaken by X-ray Mineral Services Ltd (Colwyn Bay) on 94 samples selected from three cores (Table 7.1). Samples were provided by Dr Tim Kinnaird (University of St Andrews) from material previously collected for OSL dating (see Section 8). Data analysis and interpretation was undertaken by Dr Alexander Finlay (X-ray Mineral Services Ltd).

Table 7.1: Core window samples (WS) analysed by ICP techniques for this study. Cores were selected from both northern and southern 'arcs' based on sample availability and where possible, overlap with other analyses
Core (window sample)	Samples analysed by ICP MS & ICP OES	Sample depth range (m)
WS 8A (2019-BH2)	38	0.50–4.93
WS 16D	37	0.96–5.85
WS 13D (core 1)	19	1.89–4.86

7.2 Geochemical analysis method

Elemental analysis was conducted using inductively coupled plasma-optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS), which were used to analyse material, and produce elemental data from samples relating to three cores.

The ICP-MS detects the mass of the ions hitting its detector and provides a mass spectrum for the sample, with the intensity of each mass peak in the spectrum being directly proportional to the concentration of an element of the same mass within the sample. The mass is quantified by comparing the intensities of the mass spectrum to known calibration standards (Tyler and Jobin Yvon 1995).

The ICP-OES differs in that it measures the effect of the ions in the sample on the plasma itself. When the sample solution is introduced to the plasma the elements contained within lose electrons and give off radiation with wavelengths characteristic of the element itself. The optical spectrometer detects this radiated energy and, through comparison with the intensities of known calibration standards, the elemental abundance can be quantified within the sample (Jarvis and Jarvis 1992a and 1992b; Olesik 1991; Tyler and Jobin Yvon 1995).

Bulk samples were oven dried at 50°C to preserve the makeup and matrix of the samples and passed through a 2mm sieve before being ground to a fine powder in an agate mill. Following this, the samples were prepared for ICP analyses by using the lithium metaborate (alkali) fusion procedure, as advocated by Jarvis and Jarvis (1992a). Separate aliquots of the prepared samples were analysed using a ThermoFischer iCAP ICP-OES and ThermoFisher X-Series II ICP-MS instruments.

The combined use of ICP-MS and ICP-OES enables the quantification of major elements (greater than one weight per cent of the sample; Al, Si, Ti, Fe, Mn, Mg, Ca, Na, K and P reported as oxides) and trace elements (typically down to parts per billion level; Ba, Be, Ce, Co, Cr, Cs, Cu, Dy, Er, Ga, Gd, Eu, Hf, Ho, La, Lu, Mo, Nb, Nd, Ni, Pb, Pr, Rb, S, Sc, Sm, Sr, Ta, Tb, Tl, Th, Tm, U, V, W, Y, Yb, Zn and Zr; Jarvis and Jarvis 1992a), see Table 7.3.

The precision of the geochemical data acquired by the ICP analyses is determined by replicate analyses of multiple preparations of certified rock standard reference materials (SRMs), along with duplicate preparations of three unknown samples, which are analysed on a routine basis along with each of the samples. With reference to the SRMs, the absolute accuracy of all the data is generally considered to lie within the range of error achieved for multi-determinations of the same sample.

7.3 Chemostratigraphy

Chemostratigraphy (chemical stratigraphy) is the application of whole rock or sediment geochemistry to understand the composition, depositional history and palaeoenvironment of a core. It is commonly utilised in geological (rock) stratigraphy for the petroleum, quarrying and mining industries and has recently been shown to be applicable in sub-marine Holocene sediment cores (Gaffney et al. 2020; Finlay et al. 2022). Chemostratigraphy involves building a chemostratigraphic zonation (chemo zone) of the analysed material and, where there is the need, correlating similar chemo zones between different cores and/or outcrops to produce a chemostratigraphic correlation (Ellwood et al. 2008). It is also possible to provide compositional information on the analysed material by interrogation of its elemental make up.

While elementary geochemistry can provide an excellent analytical tool for archaeological and palaeoenvironmental research (see for example Finlay et al. (2022) for the provenance and identification of anthropogenic material), it may also provide the foundation for constructing a chemical stratigraphy (chemostratigraphy) of a fill or layer (see Finlay et al. 2022).

7.4 Chemostratigraphic correlation

The results of the elemental analysis provided the foundation for constructing a chemical stratigraphy (chemostratigraphy) for each of the three cores in order to understand their composition, depositional history and palaeoenvironment. This involved building a chemostratigraphic zonation (chemo zone) of the analysed material and, where necessary, correlating similar chemo zones between different cores and/or outcrops to produce a chemostratigraphic correlation (Ellwood et al. 2008). Data were interpreted following the method of Finlay et al. (2022). Data from the ICP analysis underwent Principal Component Analysis (Fig. 7.1) to confirm the likely mineralogical controls on elemental data, which revealed seven clusters of elements (groups).

Following PCA, the data were loaded into Tibelco Spotfire to enable visual inspection of down-core variation in elemental concentration. Three elemental ratios were then selected to produce four chemo zones (CZ1 -blue, CZ2 - green, CZ3 - red, CZ4 - orange) reflecting similarities in soil texture and mineral content. All three cores analysed in this study display the same elemental profiles enabling the chemo zones discussed above to be correlated across several of the Durrington Walls pit-features (Fig. 7.1).

7.5 Interpretation of elemental composition of chemo zones

Elemental data can be utilised to understand the composition of sediments (however, without data to confirm the control on each element, this is only proxy data and may be controlled by other, unconsidered, component parts of the sediment). Therefore, the elemental composition of the analysed material is currently being utilised to hypothesise changes in the composition of each core to aid the archaeological evaluation of the material (see Finlay et al. 2022).

Results: Hypothesised proxies currently under consideration:

Calcium/potassium levels are a proxy for chalk/clay content
Rubidium/potassium levels are a proxy for different clay mineralogy
Phosphorous/Potassium levels are a proxy for proxy for bone/clay content

Note – As stated above, all samples in this study have been passed through a 2mm sieve and large clasts of material removed; the interpretation of the chemical data refers therefore to the finer grained soil matrix.

A summary of results and interpretation for this study is given in Table 7.2 and provides a possible interpretation of the geochemical data.

Table 7.2: Summary and interpretation of the chemostratigraphic analysis of core samples from WS 8A, WS13D (1) and WS 16D. Colour shading: blue = chemo zone 1, green = 2, red = chemo zone 3 and orange = chemo zone 4
Chemo Zone	Depth (m) – core window sample			Interpretation
Chemo Zone	WS 8A	WS 13D (1)	WS 16D	Chalk content	Likely bone content	Flint content	Interpretation
CZ1				Low	Low	Low	Organic-rich chalk-poor soil
Boundary (m)	~2.38	~2.26	~3.22
CZ2				Rising down Hole	High	Low	Bone-rich unit with distinct clay mineralogy
Boundary (m)	~2.75	~2.81	~3.96
CZ3				High	Low	Low with some at base	Moderate chalk content increasing at base of zone, mirrored by clay content. Some excess silica at base - flint?
Boundary (m)	~2.9	?	?
CZ4				Increasing down hole	Very Low	Low	Boundary with natural chalk basement

7.6 Summary conclusion

Chemostratigraphic analysis of core material from WS-8A, -13D, and Anomaly v (16D), identified three distinct chemo zones (CZ-1, CZ-2, CZ-3, see Fig. 7.2), which correlate well with the sediment logs.

The chemostratigraphy shows that every analysed pit has the same sequence of chemically distinct fills comprising:

Surface of core
CZ1 - Organic-rich chalk-poor soil
CZ2 - Bone-rich unit with distinct clay mineralogy
CZ3 - Moderate chalk content increasing at base of zone, mirrored by clay content. Some excess silica at base - flint?
CZ4 – Boundary with natural chalk basement
Base of core

From chemistry alone it is not possible to distinguish with confidence whether these fills are formed by natural infilling or by anthropogenic processes. However, the fact that there are three distinct zones present that correlate across the selected pits suggests that the zones were not formed by the natural infilling of geological features. If this was the case, it is hypothesised that each fill would be expected to be different, reflecting local processes and natural geomorphological material, as well as not displaying the same internal layering. As the fills occur in the same order across all analysed pits it is further suggested that the pits may have been deliberately filled using a similar manner or process during at least some point in their history.

Figures

Figure 7-1 — Figure 7.1: Principal Component Analysis (PCA) of all geochemical data in this study. Highlighted are clusters of elements likely associated with the labelled mineral. CaO, Sr and MgO likely associated with carbonate (e.g. chalk) minerals. SiO2 likely associated with quartz or chert (e.g. flint). Rb, Al2O3, Fe2O3, TiO2, Ga and Th likely associated with clay mineral 1 whereas Na₂O and K₂O are likely associated with clay mineral 2. The exact clay minerals are unknown. Hf and Zr are highly likely to be associated with zircon. P₂O₅ may be associated with phosphatic minerals. MnO is unknown but may be Redox sensitive

Figure 7-2 — Figure 7.2: Chemostratigraphic correlation across anomalies WS8A, WS13D1 and WS16D. The chemostratigraphy reveals three correlate zones based on changes in CaO/K₂O (carbonate minerals/clay; track 1), Rb/K₂O (changes in clay mineralogy; track 2) and P₂O₅/K₂O (phosphatic/clay minerals; track 3). Colour shading: blue = chemo zone 1, green = chemo zone 2, red = chemo zone 3 and orange = chemo zone 4

7.9. Raw geochemistry data

Table 7.3: Major and trace element geochemical data for cores WS8A, WS13D1 and WS16. [Download .csv]

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