Historical salmon catch records suggest that climatic variability, and more recently human exploitation, control patterns of abundance in Atlantic salmon populations. We present the first long-term (2000-year) reconstruction of Atlantic Salmon population variations based on a Marine Derived Nutrient (MDN) lake sediment record. Our record is constructed from nitrogen isotopes (δ15N) measured from a lake sediment core, which we compare with an escapement index (EI) derived from historic net catch data on major Scottish salmon rivers. We used an isotope mixing model to demonstrate that the N isotope values are likely enriched with MDN and demonstrate that Loch Insh sediments are enriched compared with a control site (Loch Vaa) that has never had exposure to salmon. We demonstrate that current adult spawner returns are around half that of historic values prior to major human exploitation. Before the onset of widespread human exploitation and habitat degradation, large fluctuations in salmon abundance are attributed to variations in North Atlantic sea surface temperature. While our data support published reconstructions of declining Atlantic salmon stocks in Northwest European rivers over the last 1000 years, rather than point to a solely human cause, the human impact appears to be overprinted on larger-scale changes in marine habitat occurring at the transition from the warmer Medieval Climatic Anomaly (MCA) to the cooler Little Ice Age (LIA).

The measurement of sulphur isotope (δ34S) values in charred plant remains has the potential to inform understanding of the spatial configuration and ecology of crop production. We investigated the effects of charring, manuring, oxidation and anaerobic soil conditions on modern cereal grain/pulse seed δ34S values, and assessed the effect of chemical pre‐treatment on charred modern and archaeobotanical grain/seed δ34S values. We used these results to interpret δ34S values in archaeobotanical material from Neolithic Çatalhöyük. Our results suggest that δ34S values can be reliably preserved in charred grain/seeds but are subject to influence by anaerobic soil conditions, the effect depending on the timing of flooding in relation to S assimilation.

The need to reduce both point and diffuse phosphorus pollution to aquatic ecosystems is widely recognised and in order to achieve this, identification of the different pollutant sources is essential. Recently, a stable isotope approach using oxygen isotopes within phosphate (δ18OPO4) has been used in phosphorus source tracing studies. This approach was applied in a one-off survey in September 2013 to the River Taw catchment in south-west England where elevated levels of phosphate have been reported. River water δ18OPO4 along the main channel varied little, ranging from + 17.1 to + 18.8‰. This was no > 0.3‰ different to that of the isotopic equilibrium with water (Eδ18OPO4). The δ18OPO4 in the tributaries was more variable (+ 17.1 to + 18.8‰), but only deviated from Eδ18OPO4 by between 0.4 and 0.9‰. Several potential phosphate sources within the catchment were sampled and most had a narrow range of δ18OPO4 values similar to that of river Eδ18OPO4. Discharge from two waste water treatment plants had different and distinct δ18OPO4 from one another ranging between + 16.4 and + 19.6‰ and similar values to that of a dairy factory final effluent (+ 16.5 to + 17.8‰), mains tap water (+ 17.8 to + 18.4‰), and that of the phosphate extracted from river channel bed sediment (+ 16.7 to + 17.6‰). Inorganic fertilizers had a wide range of values (+ 13.3 to + 25.9‰) while stored animal wastes were consistently lower (+ 12.0 to + 15.0‰) than most other sources and Eδ18OPO4. The distinct signals from the waste water treatment plants were lost within the river over a short distance suggesting that rapid microbial cycling of phosphate was occurring, because microbial cycling shifts the isotopic signal towards Eδ18OPO4. This study has added to the global inventory of phosphate source δ18OPO4 values, but also demonstrated the limitations of this approach to identifying phosphate sources, especially at times when microbial cycling is high.

This paper introduces the treethresh package offering accurate estimation, via thresholding, of potentially sparse heterogeneous signals and the denoising of images using wavelets. It gives considerably improved performance over other estimation methods if the underlying signal or image is not homogeneous throughout but instead has distinct regions with differing sparsity or strength characteristics. It aims to identify these different regions and perform separate estimation in each accordingly. The base algorithm offers code which can be applied directly to any one-dimensional potentially sparse sequence observed subject to noise. Also included are functions which allow two-dimensional images to be denoised following transformation to the wavelet domain. In addition to reconstructing the underlying signal or image, the package provides information on the believed partitioning of the signal or image into its differing regions.

In order to investigate the effect of glaciation on mineral weathering, the stream water chemistry and the bacterial community composition were analysed in two catchments containing nominally identical sedimentary formations but which differed in the extent of glaciation. The stream waters were analysed for major ions, δ34S, δ18OSO4 and δ18OH2O and associated stream sediments were analysed by 16S rRNA gene tagged sequencing.Sulphate comprised 72–86% and 35–45% of the summer anion budget (in meq) in the unglaciated and glaciated catchments respectively. This indicates that sulfuric acid generated from pyrite weathering is a significant weathering agent in both catchments. Based on the relative proportions of cations, sulphate and bicarbonate, the stream water chemistry of the unglaciated catchment was found to be consistent with a sulphide oxidation coupled to silicate dissolution weathering process whereas in the glaciated catchment both carbonates and silicates weathered via both sulfuric and carbonic acids.Stable isotope measurements of sulphate, together with inferences of metabolic processes catalysed by resident microbial communities, revealed that the pyrite oxidation reaction differed between the two catchments. No δ34S fractionation relative to pyrite was observed in the unglaciated catchment and this was interpreted to reflect pyrite oxidation under oxic conditions. In contrast, δ34S and δ18OSO4 values were positively correlated in the glaciated catchment and were positively offset from pyrite. This was interpreted to reflect pyrite oxidation under anoxic conditions with loss of S intermediates.This study suggests that glaciation may alter stream water chemistry and the mechanism of pyrite oxidation through an interplay of biological, physical and chemical factors.

Eutrophication is a globally significant challenge facing aquatic ecosystems, associated with human induced enrichment of these ecosystems with nitrogen (N) and phosphorus (P). However, the limited availability of inherent labels for P and N has constrained understanding of the triggers for eutrophication in natural ecosystems and appropriate targeting of management responses. This paper proposes and evaluates a new multi-stable isotope framework that offers inherent labels to track biogeochemical reactions governing both P and N in natural ecosystems. The framework couples highly novel analysis of the oxygen isotope composition of phosphate (δ18OPO4) with dual isotope analysis of oxygen and N within nitrate (δ15NNO3, δ18ONO3) and with stable N isotope analysis in ammonium (δ15NNH4). The River Beult in England is used as an exemplar system for initial evaluation of this framework. Our data demonstrate the potential to use stable isotope labels to track the input and downstream fate of nutrients from point sources, on the basis of isotopic differentiation for both P and N between river water and waste water treatment work effluent (mean difference = +1.7‰ for δ18OPO4; +15.5‰ for δ15NNH4 (under high flow); +7.3‰ for δ18ONO3 and +4.4‰ for δ15NNO3). Stable isotope data reveal nutrient inputs to the river upstream of the waste water treatment works that are consistent with partially denitrified sewage or livestock sources of nitrate (δ15NNO3 range = +11.5 to +13.1‰) and with agricultural sources of phosphate (δ18OPO4 range = +16.6 to +19.0‰). The importance of abiotic and metabolic processes for the in-river fate of N and P are also explored through the stable isotope framework. Microbial uptake of ammonium to meet metabolic demand for N is suggested by substantial enrichment of δ15NNH4 (by 10.2‰ over a 100 m reach) under summer low flow conditions. Whilst the concentration of both nitrate and phosphate decreased substantially along the same reach, the stable isotope composition of these ions did not vary significantly, indicating that concentration changes are likely driven by abiotic processes of dilution or sorption. The in-river stable isotope composition and the concentration of P and N were also largely constant downstream of the waste water treatment works, indicating that effluent-derived nutrients were not strongly coupled to metabolism along this in-river transect. Combined with in-situ and laboratory hydrochemical data, we believe that a multi-stable isotope framework represents a powerful approach for understanding and managing eutrophication in natural aquatic ecosystems.

The stable carbon isotopic composition of dissolved organic matter (δ13C‐DOC) reveals information about its source and extent of biological processing. Here we report the lowest δ13C‐DOC values (−43.8‰) measured to date in surface waters. The streams were located in the High Arctic, a region currently experiencing rapid changes in climate and carbon cycling. Based on the widespread occurrence of methane cycling in permafrost regions and the detection of the pmoA gene, a proxy for aerobic methanotrophs, we conclude that the low δ13C‐DOC values are due to organic matter partially derived from methanotrophs consuming biologically produced, 13C‐depleted methane. These findings demonstrate the significant impact that biological activity has on the stream water chemistry exported from permafrost and glaciated environments in the Arctic. Given that the catchments studied here are representative of larger areas of the Arctic, occurrences of low δ13C‐DOC values may be more widespread than previously recognized, with implications for understanding C cycling in these environments.

Phosphate dosing of drinking water supplies, coupled with leakage from distribution networks, represents a significant input of phosphorus to the environment. The oxygen isotope composition of phosphate (δ(18)OPO4), a novel stable isotope tracer for phosphorus, offers new opportunities to understand the importance of phosphorus derived from sources such as drinking water. We report the first assessment of δ(18)OPO4 within drinking water supplies. A total of 40 samples from phosphate-dosed distribution networks were analyzed from across England and Wales. In addition, samples of the source orthophosphoric acid used for dosing were also analyzed. Two distinct isotopic signatures for drinking water were identified (average = +13.2 or +19.7‰), primarily determined by δ(18)OPO4 of the source acid (average = +12.4 or +19.7‰). Dependent upon the source acid used, drinking water δ(18)OPO4 appears isotopically distinct from a number of other phosphorus sources. Isotopic offsets from the source acid ranging from -0.9 to +2.8‰ were observed. There was little evidence that equilibrium isotope fractionation dominated within the networks, with offsets from temperature-dependent equilibrium ranging from -4.8 to +4.2‰. While partial equilibrium fractionation may have occurred, kinetic effects associated with microbial uptake of phosphorus or abiotic sorption and dissolution reactions may also contribute to δ(18)OPO4 within drinking water supplies.

This study examines the role of tree canopies in processing atmospheric nitrogen (Ndep) for four forests in the United Kingdom subjected to different Ndep: Scots pine and beech stands under high Ndep (HN, 13–19 kg N ha−1 yr−1), compared to Scots pine and beech stands under low Ndep (LN, 9 kg N ha−1 yr−1). Changes of NO3‐N and NH4‐N concentrations in rainfall (RF) and throughfall (TF) together with a quadruple isotope approach, which combines δ18O, Δ17O and δ15N in NO3− and δ15N in NH4+, were used to assess N transformations by the canopies. Generally, HN sites showed higher NH4‐N and NO3‐N concentrations in RF compared to the LN sites. Similar values of δ15N‐NO3− and δ18O in RF suggested similar source of atmospheric NO3− (i.e. local traffic), while more positive values for δ15N‐NH4+ at HN compared to LN likely reflected the contribution of dry NHx deposition from intensive local farming. The isotopic signatures of the N‐forms changed after interacting with tree canopies. Indeed, 15N‐enriched NH4+ in TF compared to RF at all sites suggested that canopies played an important role in buffering dry Ndep also at the low Ndep site. Using two independent methods, based on δ18O and Δ17O, we quantified for the first time the proportion of NO3− in TF, which derived from nitrification occurring in tree canopies at the HN site. Specifically, for Scots pine, all the considered isotope approaches detected biological nitrification. By contrast for the beech, only using the mixing model with Δ17O, we were able to depict the occurrence of nitrification within canopies. Our study suggests that tree canopies play an active role in the N cycling within forest ecosystems. Processing of Ndep within canopies should not be neglected and needs further exploration, with the combination of multiple isotope tracers, with particular reference to Δ17O.

In a large study on early crop water management, stable carbon isotope discrimination was determined for 275 charred grain samples from nine archaeological sites, dating primarily to the Neolithic and Bronze Age, from the Eastern Mediterranean and Western Asia. This has revealed that wheat (Triticum spp.) was regularly grown in wetter conditions than barley (Hordeum sp.), indicating systematic preferential treatment of wheat that may reflect a cultural preference for wheat over barley. Isotopic analysis of pulse crops (Lens culinaris, Pisum sativum and Vicia ervilia) indicates cultivation in highly varied water conditions at some sites, possibly as a result of opportunistic watering practices. The results have also provided evidence for local land-use and changing agricultural practices.

A tree ring oxygen isotope (δ18OTR) chronology developed from one species (Cedrela odorata) growing in a single site has been shown to be a sensitive proxy for rainfall over the Amazon Basin, thus allowing reconstructions of precipitation in a region where meteorological records are short and scarce. Although these results suggest that there should be large-scale (>100km) spatial coherence of δ18OTR records in the Amazon, this has not been tested. Furthermore, it is of interest to investigate whether other, possibly longer-lived, species similarly record interannual variation of Amazon precipitation, and can be used to develop climate sensitive isotope chronologies. In this study, we measured δ18O in tree rings from seven lowland and one highland tree species from Bolivia. We found that cross-dating with δ18OTR gave more accurate tree ring dates than using ring width. Our “isotope cross-dating approach” is confirmed with radiocarbon “bomb-peak” dates, and has the potential to greatly facilitate development of δ18OTR records in the tropics, identify dating errors, and check annual ring formation in tropical trees. Six of the seven lowland species correlated significantly with C. odorata, showing that variation in δ18OTR has a coherent imprint across very different species, most likely arising from a dominant influence of source water δ18O on δ18OTR. In addition we show that δ18OTR series cohere over large distances, within and between species. Comparison of two C. odorata δ18OTR chronologies from sites several hundreds of kilometres apart showed a very strong correlation (r=0.80, p<0.001, 1901–2001), and a significant (but weaker) relationship was found between lowland C. odorata trees and a Polylepis tarapacana tree growing in the distant Altiplano (r=0.39, p<0.01, 1931–2001). This large-scale coherence of δ18OTR records is probably triggered by a strong spatial coherence in precipitation δ18O due to large-scale controls. These results highlight the strength of δ18OTR as a precipitation proxy, and open the way for temporal and spatial expansion of precipitation reconstructions in South America.

The North York Moors National Park, in Northeast England, is one of the few upland areas of the United Kingdom located immediately downwind of major sulphur and nitrogen emission sources. Despite this, few studies of air pollution impacts have been undertaken, and there is no formal long-term upland water quality monitoring site. We examined the condition of surface waters in the National Park based on (1) a unique 20 year stream pH record from three locations; and (2) a snapshot survey of 51 surface waters draining moorland and conifer plantations. Interpretation was supported by sulphur isotope analysis of a subset of water samples, and a diatom survey of one of the monitoring streams. Long-term pH data for a stream draining the peat plateau demonstrate extreme, year-round acidification, with recovery only evident in the last few years. Lower-elevation sites are less acidic, but show similar temporal trends, and are characterised by frequent and severe acid episodes. The snapshot survey confirmed that acidification of the moorland area is widespread, to a degree observed in few other areas globally; out of 37 moorland streams sampled, 32 had an acid neutralising capacity (ANC) below −50μequiv.l−1. Sulphate was found to be (by far) the dominant cause of acidification, and sulphur isotope analysis confirmed that this derives primarily from atmospheric deposition. Nitrate concentrations remain low, indicating that the organic moorland soils continue to retain most incoming nitrogen. It appears that conifer planting has exacerbated acidification, leading to fivefold higher nitrate and threefold higher aluminium concentrations compared to the moorland sites. Available biological data suggest that waters in the region have been impoverished by acidification. We speculate that the slow recovery of surface waters in the North York Moors is due to the release of a legacy of stored sulphur from the peats, released during droughts. We conclude that: (1) acidification is far from being a solved problem in this sensitive near-source upland region, despite reductions in sulphur deposition; (2) plantation forestry has exacerbated the effects of atmospheric pollution, and triggered nitrogen saturation; (3) the lack of any formal long-term monitoring in the North York Moors represents a major gap in the current evidence base for the effects of long-range air pollutants on UK upland ecosystems.

In this report we outline a method to isolate phosphate as pure Ag3PO4 for waters with high C:P ratios for 18O analysis. This report details a method that can be used to minimise residual organic contamination of the final Ag3PO4, therefore significantly reducing uncertainties in the final interpretation of 18O results. This includes the use of column resins in series to (i) remove the majority of dissolved organic carbon and (ii) isolate/pre-concentrate PO4. This is followed by the use of a modified McLaughlin et al (2004) method for PO4 precipitation, with an additional final hydrogen peroxide clean-up step to remove residual organic matter following precipitation of Ag3PO4. The reagents required for this method are first listed, and then a step-by-step account of the process is outlined. Importantly, it contains adequate detail to be used by other researchers in this field or modified to suit their particular research objectives.

In this paper we reconstruct the palaeodietary setting of LBK Vaihingen an der Enz, south-west Germany (later sixth millennium cal. bc) using δ13C and δ15N values of human and faunal bone collagen and of charred plant remains from cereal crops (e.g. emmer and einkorn wheat) and pulses (lentil and pea). Our examination of this Neolithic dietary ‘food web’ incorporates crop δ15N values within a linear-mixing model to examine the estimated proportions of animal and plant protein in the human diet. We interpret the stable isotope dietary model outcomes together with accompanying archaeobotanical and zooarchaeological evidence to shed light on the role of crops in land use strategies and human diet, and conclude that (manured) crops probably formed the dominant protein source.

As a result of Pleistocene glaciations, many parts of the UK have a covering of glacial sands, gravels or clays. Where such deposits overlie aquifers, recharge may be impeded. This paper describes the use of sulphur and strontium isotope ratios to determine recharge routes through a thick boulder clay (‘till’) overlying the Chalk aquifer in a part of eastern England, UK. Sulphur isotopes show that two possible sources of S may be contributing to the recharge, but strontium isotopes are more definitive, indicating most interaction is with the unweathered till.

The spread of farming from western Asia to Europe had profound long-term social and ecological impacts, but identification of the specific nature of Neolithic land management practices and the dietary contribution of early crops has been problematic. Here, we present previously undescribed stable isotope determinations of charred cereals and pulses from 13 Neolithic sites across Europe (dating ca . 5900–2400 cal B.C.), which show that early farmers used livestock manure and water management to enhance crop yields. Intensive manuring inextricably linked plant cultivation and animal herding and contributed to the remarkable resilience of these combined practices across diverse climatic zones. Critically, our findings suggest that commonly applied paleodietary interpretations of human and herbivore δ 15 N values have systematically underestimated the contribution of crop-derived protein to early farmer diets.

The aim of this study is to assess the potential of charred archaeobotanical cereal grain and pulse seed delta C-13 and delta N-15 values to provide evidence of crop growing conditions and as a potential component of palaeodietary studies. In order to reliably interpret archaeobotanical delta C-13 and delta N-15 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 delta C-13, delta N-15, %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 delta C-13 and delta N-15 values. Heating at relatively low temperatures and for prolonged times (230 degrees 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 delta N-15 values, with increases of around 1 parts per thousand on average in cereal grains and pulse seeds, and no consistent impact on delta C-13 values. Increases in delta N-15 are likely due to the loss of lighter N-14 via N-containing volatiles. Burial (for up to 2 years) and ABA pre-treatment have no significant effects on delta C-13 or delta N-15 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. (C) 2013 Elsevier Ltd. All rights reserved.

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 C-13 NMR, to characterise changes in the biochemical composition of modern einkorn grains with heating at 230 degrees 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 C-13 NMR in order to assess the changes in composition which occur during burial. Results of FT-IR and solid-state C-13 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 delta C-13 values and a systematic increase of 0.8%. in the delta N-15 values of the charred einkorn grains. Solid-state C-13 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. (C) 2013 Elsevier Ltd. All rights reserved.

Stable carbon isotope analysis of plant remains is a promising tool for researchers studying palaeoclimate and past agricultural systems. The potential of the technique is clear: it offers a direct measure of the water conditions in which plants grew. In this paper, we assess how reliably stable carbon isotope discrimination can be used to infer water conditions, through the analysis of present-day crop plants grown at multiple locations across the Mediterranean and south-west Asia. The key findings are that: (1) C-13, as expected, provides an indication of water conditions, (2) even for plants grown in similar conditions there is variation in C-13 and (3) C-13 may reflect crop water status for a period beginning well before the grain filling period. A new framework is presented which increases the robustness with which C-13 values of plant remains can be interpreted in terms of the water conditions in which ancient crops grew.