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The aim of this study is to assess the potential of charred archaeobotanical cereal grain and pulse seed δ13C and δ15N values to provide evidence of crop growing conditions and as a potential component of palaeodietary studies. In order to reliably interpret archaeobotanical δ13C and δ15N values it is necessary to take into account the impact of charring, burial and laboratory pre-treatment procedures. We examine the effects of charring and burial on bulk δ13C, δ15N, %C, %N and C:N ratios in modern cereal and pulse material, and of cleaning by acid–base–acid (ABA) pre-treatment on modern and archaeobotanical charred material. Our study utilised bulk grain and seed samples to help account for within-ear/pod and between-plant variability in δ13C and δ15N values. Heating at relatively low temperatures and for prolonged times (230 °C for up to 24 h) is conducive to the formation of well preserved, undistorted charred cereal grain and pulse seed. Heating for 24 h has a systematic and predictable effect on δ15N values, with increases of around 1‰ on average in cereal grains and pulse seeds, and no consistent impact on δ13C values. Increases in δ15N are likely due to the loss of lighter 14N via N-containing volatiles. Burial (for up to 2 years) and ABA pre-treatment have no significant effects on δ13C or δ15N values. After pre-treatment, however, the %C and %N contents of the archaeobotanical material more closely resembles that of the modern charred grains and seeds, suggesting that archaeobotanical remains accumulate non-structural material during burial but retain their original carbon and nitrogen content. Therefore %C, %N contents and C:N ratios can provide useful criteria for assessing archaeobotanical preservation.

Stable isotope analysis of charred archaeobotanical cereal grains has the potential to provide direct evidence of crop growing conditions in the past and to refine palaeodietary predictions. If isotope values of archaeobotanical material are to be considered robust, it is necessary to characterise the compositional changes associated with their charring and burial. This study used a suite of analytical techniques, including FT-IR and solid state 13C NMR, to characterise changes in the biochemical composition of modern einkorn grains with heating at 230 °C for 2 h, 4 h, 8 h and 24 h, encompassing conditions that replicate their undistorted ancient counterparts. The biochemical composition of archaeobotanical charred einkorn grains was also investigated by FT-IR and solid state 13C NMR in order to assess the changes in composition which occur during burial. Results of FT-IR and solid-state 13C NMR show that heating of modern einkorn grains resulted in Maillard reactions between cereal proteins and starch, forming high molecular weight melanoidins, which contain both alkyl and aromatic carbon. Loss of low molecular weight carbon and nitrogen-containing volatiles resulted in a slight but non-systematic increase in the δ13C values and a systematic increase of 0.8‰ in the δ15N values of the charred einkorn grains. Solid-state 13C NMR shows that the ancient charred einkorn grains consisted entirely of aromatic carbon and retained a similar proportion of nitrogen to their modern 24 h charred counterparts, despite a significantly lower concentration of amino acids. This indicates that the amino acid nitrogen in the ancient charred grains was retained in the stable melanoidins whose polymeric structure makes them resistant to subsequent degradation.

Stable carbon isotope time-series (δ13C) from tree-rings are capable of providing valuable palaeoclimatic information, but analysis of individual tree-rings is time consuming and expensive. Pooling material from several tree-rings prior to isotopic analysis reduces costs, but does not allow the magnitude of uncertainty in the mean δ13C chronology to be calculated unless the pool is broken and each tree-ring measured individually at regular intervals. Here we use a comparison of pooled and mean individual (the arithmetic mean of isotopic data from tree series measured individually) δ13C records between AD 1650 and 2007, comprising cores from 21 Scots pine (Pinus sylvestris L.) trees growing in the western Highlands of Scotland. The aim is to determine whether the true error structure of the time series is better captured by using the overall mean error estimate for the entire time series or by linear interpolation between the equally spaced measurements. We conclude that where autocorrelation exists within the error structure of a chronology, annual estimates of 95% confidence intervals, developed through linear interpolation at 5-year or 10-year intervals, are preferable to using the overall mean uncertainty. The method outlined increases the viability of pooled δ13C records for palaeoclimatic research by retaining error structure whilst reducing analytical time and costs. The method is applied here using tree-ring data, but could theoretically be applied to any well-replicated time-series.

Sewage contamination in shallow lake sediments is of concern because the pathogens, organic matter and nutrients contribute to the deterioration of the water-bodies' health and ecology. Sediment cores from three shallow lakes (Coneries, Church and Clifton Ponds) within Attenborough nature reserve located downstream of sewage treatment works were analysed for TOC, C/N, δ13C, δ15N, bacterial coliforms and faecal sterols. 210Pb and 137Cs activities were used to date the sediments. Elemental analysis suggests that the source of organic matter was algal and down profile changes in δ13C indicate a possible decrease in productivity with time which could be due to improvements in sewage treatment. δ15N for Coneries Pond are slightly higher than those observed in Church or Clifton and are consistent with a sewage-derived nitrate source which has been diluted by non-sewage sources of N. The similarity in δ15N values (+ 12‰ to + 10‰) indicates that the three ponds were not entirely hydrologically isolated. Analysis by gas chromatography/mass spectrometry (GC/MS) reveals that Coneries Pond had sterol concentrations in the range 20 to 30 μg/g (dry wt.), whereas, those from Clifton and Church Ponds were lower. The highest concentrations of the human-sourced sewage marker 5β-coprostanol were observed in the top 40 cm of Coneries Pond with values up to 2.2 μg/g. In contrast, Church and Clifton Pond sediments contain only trace amounts throughout. Down-profile comparison of 5β-coprostanol/cholesterol, 5β-coprostanol/(5β-coprostanol + 5α-cholestanol) and 5β-epicoprostanol/coprostanol as well as 5α-cholestanol/cholesterol suggests that Coneries Pond has received appreciable amounts of faecal contamination. Examination of 5β-stigmastanol (marker for herbivorous/ruminant animals) down core concentrations suggests a recent decrease in manure slurry input to Coneries Pond. The greater concentration of β-sitosterol in sediments from Church and Clifton Ponds as compared to Coneries is attri

The Maltese Islands are composed of two limestone aquifers, the Upper and Lower Coralline Limestone separated by an aquitard, the ‘Blue Clay’. The Lower Coralline Limestone is overlain in part by the poorly permeable Globigerina Limestone. The upper perched aquifers are discontinuous and have very limited saturated thickness and a short water level response time to rainfall. Frequent detections of coliforms suggest a rapid route to groundwater. However, the unsaturated zone has a considerable thickness in places and the primary porosity of the Upper Coralline Limestone is high, so there is likely to be older recharge by slow matrix flow as well as rapid recharge from fractures. Measurement of SF6 from a pumping station in a deep part of one of the perched aquifers indicated a mean saturated zone age of about 15 years. The Main Sea Level aquifers (MSL) on both Malta and Gozo have a large unsaturated thickness as water levels are close to sea level. On Malta, parts of the aquifer are capped by the perched aquifers and more extensively by the Globigerina Limestone. The limited detection of coliform bacteria suggests only some rapid recharge from the surface via fractures or karst features. Transmissivity is low and tritium and CFC/SF6 data indicate that saturated zone travel times are in the range 15-40 years. On Gozo the aquifer is similar but is more-extensively capped by impermeable Blue Clay. CFC data show the saturated zone travel time is from 25 years to possibly more than 60 years. Groundwater age is clearly related to the extent of low-permeability cover. The δ13C signature of groundwater is related to the geochemical processes which occur along the flowpath and is consistent with residence time ages in the sequence; perched aquifers

Variations in the 13C/12C ratios of wheat grain at different spatial and temporal scales are examined by analysis of modern samples, including harvests of einkorn and durum wheat from Greece, and serve as a guide to interpreting data for Bronze Age grains from Assiros Toumba. The normal distribution and low variability of δ13C values of einkorn from 24 containers in the Assiros storerooms are consistent with pooling of local harvests, but less likely to represent the harvest of several years or include grain imported from further afield. Correlation between emmer and spelt δ13C values provides strong support for other evidence that these were grown together as a maslin crop. 13C discrimination (Δ) for the Bronze Age samples is estimated to be 2.5‰ larger than at present, and would be consistent with an intensive, horticultural regime of cereal cultivation, possibly involving some watering.

Recent archaeological studies of human diet have used stable nitrogen isotope ratios (d15N) from human bone collagen to infer the relative importance of terrestrial plant and animal foods. This approach is based on widely observed enrichment of d15N up the food chain, plants having distinctly lower values than the herbivores that consume them. Studies of early farming diets in Britain, Denmark and Germany have tended to detect relatively high d15N values (e.g. c. +9‰), interpreted as evidence of a diet largely based on animal products, though archaeobotanical evidence for crop cultivation (e.g. carbonised cereal grain and chaff) is widespread. This paper investigates the impact of manuring on d15N values in modern cereals, and of charring on these cereal values. The results from two long-term experiments demonstrate that manuring significantly raises d15N in cereal grain and chaff. Depending on manuring levels and frequency, it appears that human diets with a major component of such grain would conventionally be interpreted as indicating a largely animal-based diet or a mixed plant/animal diet. Moreover, preliminary analyses of experimentally charred grain and chaff from manured and unmanured conditions are promising for the extraction of reliable ancient d15N values from archaeobotanical cereal remains. The wider implications of these results, and the need for further work, are discussed.

The stable-isotope and trace-element analysis of ostracod calcite are commonly used in palaeoenvironmental reconstruction. We tested the effects on shell composition of a number of methods for the pre-treatment of ostracod valves, including roasting in a vacuum; plasma ashing; and soaking in reagents including hydrogen peroxide, sodium hypochlorite, hydroxylamine hydrochloride solution and sodium dithionite complexing reagent. We found large differences in the geochemical effects of these methods and showed that all have the potential to alter the trace element and stable isotope composition of ostracod valves. We recommend that valves only be cleaned manually, with fine brushes, needles and deionised water whenever possible. However, we recognise that there will be occasions where manual cleaning will be insufficient to remove inorganic or organic contamination. In such cases, we recommend hydrogen peroxide and plasma ashing as good methods for oxygen isotope analysis, if no other analyses are to be performed. For carbon isotope analysis, only plasma ashing should be used. Hydroxylamine hydrochloride is a suitable method for the removal of aluminosilicate material, and sodium hypochlorite is a suitably non-invasive method for the removal of organic material, if subsequent trace element analysis is to be carried out.

The stable-isotope and trace-element analysis of ostracod calcite are commonly used in palaeoenvironmental reconstruction. We tested the effects on shell composition of a number of methods for the pre-treatment of ostracod valves, including roasting in a vacuum; plasma ashing; and soaking in reagents including hydrogen peroxide, sodium hypochlorite, hydroxylamine hydrochloride solution and sodium dithionite complexing reagent. We found large differences in the geochemical effects of these methods and showed that all have the potential to alter the trace element and stable isotope composition of ostracod valves. We recommend that valves only be cleaned manually, with fine brushes, needles and deionised water whenever possible. However, we recognise that there will be occasions where manual cleaning will be insufficient to remove inorganic or organic contamination. In such cases, we recommend hydrogen peroxide and plasma ashing as good methods for oxygen isotope analysis, if no other analyses are to be performed. For carbon isotope analysis, only plasma ashing should be used. Hydroxylamine hydrochloride is a suitable method for the removal of aluminosilicate material, and sodium hypochlorite is a suitably non-invasive method for the removal of organic material, if subsequent trace element analysis is to be carried out.

The authors present data for the chemical, stable isotope (13C/12C, 15N/14N and 34S/32S), and dissolved gas (N2, Ar, O2 and CH4) composition of groundwaters sampled in and around a landfill site in Cambridgeshire, England. Decomposition of 3 × 106 m3 of largely domestic waste, placed in unlined quarries, has given rise to the formation of an NH4-rich leachate dispersing as a plume into the surrounding Middle Chalk aquifer. In addition to identifying zones of methanogenesis and SO4 reduction, the data indicate processes of NH4 transformation by either assimilation or oxidation, and losses by formation of N2. Depending on the mixing ratio between leachate and background water, it may be possible to account for all NH4 loss by combined nitrification + denitrification in a system where there are abrupt temporal and spatial changes in redox conditions.

The authors present data for the chemical, stable isotope (13C/12C, 15N/14N and 34S/32S), and dissolved gas (N2, Ar, O2 and CH4) composition of groundwaters sampled in and around a landfill site in Cambridgeshire, England. Decomposition of 3 × 106 m3 of largely domestic waste, placed in unlined quarries, has given rise to the formation of an NH4-rich leachate dispersing as a plume into the surrounding Middle Chalk aquifer. In addition to identifying zones of methanogenesis and SO4 reduction, the data indicate processes of NH4 transformation by either assimilation or oxidation, and losses by formation of N2. Depending on the mixing ratio between leachate and background water, it may be possible to account for all NH4 loss by combined nitrification + denitrification in a system where there are abrupt temporal and spatial changes in redox conditions.