Contribution of sewage organic matter to the diet of the common limpet near the former outflow at Blackhead, Northern Ireland

Stable isotopes (δ13C, δ15N) have been used to document the utilisation of sewage effluent in coastal marine foodwebs in a number of studies (e.g. Rau et al. 1981; Risk et al. 2009; Rogers 1999; 2003). δ13C and, especially, δ15N showed clear differences in the diet of common limpets (Patella vulgata) collected in June 2010 near the untreated sewage outfall at Blackhead, Northern Ireland and a ‘clean’ site nearby. Because sewage contains a significant portion of fossil-fuel derived compounds (Law et al. 2013), 14C measurements enabled us to estimate the contribution of fossil carbon to the effluent and to the foodweb and hence of the level of sewage contamination. The effluent was found to contain 12.2 ± x % fossil carbon on the day sampled. The modern marine carbon endmember is enriched by the discharge from the Sellafield nuclear fuel reprocessing plant across the Irish Sea (c.f. Cook et al. 2004) so 14C analyses of samples from the ‘clean’ site were needed. We found that 38.5 ±x % of the diet of common limpets collected near the sewage was derived from fossil fuel. We plan to collect samples from the same two sites in June 2014 to establish whether the 2012 relocation of the outfall, with preliminary treated discharge farther out to sea has eliminated the contamination at Blackhead

A multi-proxy chronological reconstruction of palaeosalinity in the eastern Limfjord, Denmark

The Jutland peninsula in northern Denmark is home to the Limfjord, one of the largest estuarine bodies of water in the region. Human inhabitance of the Limfjord’s surrounding coastlines stretches back further than 7,800 cal BP, with anthropogenic influence on the landscape beginning approximately 6,000 cal BP. Understanding how the Limfjord as a system has changed throughout time is useful in comprehending subsistence patterns and anthropogenic influence. This research is part of a larger project aimed at discerning subsistence patterns and environmental change in the region. Following the Younger Dryas, as the Fennoscandian ice sheet began to melt, Denmark experienced isostatic rebound, which contributed to the complex sea level history in the region. Between ice melt and isostatic rebound, the Jutland peninsula experienced many transgression and regression events. Connections to surrounding seas have shifted throughout time, with most attention focused on the western connection of the Limfjord with the North Sea, which has experienced numerous closures and subsequent re-openings throughout the Holocene. Furthermore, the Limfjord-North Sea connection has been the focal point of research because of the west to east water flow in the system, and the present day higher salinity in the west compared to the east. Little to no consideration has been paid to the influence of the Kattegat and Baltic on the Limfjord until now. A 10m sediment core was taken from Sebbersund (near Nibe, Limfjord), along the connection between the Limfjord and the Kattegat in the east to understand how the eastern part of the system has changed and differed from changes observed in the west. The Sebbersund sequence spans a majority of the Holocene, from 9600 cal BP to 1030 cal BP, determined via radiocarbon dating of terrestrial macrofossils and bulk sediment. Over this time period palaeoenvironmental conditions were reconstructed through the use of geochemical analyses (13C, 15N, C:N), physical sediment analyses, dinoflagellate cyst abundances and molluscan analyses. apart from two instances of low salinity, one at the top and one at the bottom of the core, the sequence has a strong marine signal for a majority of the Holocene. Radiocarbon dating of bulk sediment samples showed the presence of old carbon in the system, creating an age offset between 1,300 ± 200 and 2,800 ± 200 calibrated 14C years compared to the age-depth curve based on the terrestrial macrofossils. This finding, along with the strong marine influence in the system, discerned through geochemical data, dinoflagellate cyst and mollusc counts, is important for obtaining accurate radiocarbon ages in the region and stresses the importance of understanding both the marine and freshwater reservoir effects. The marine dominance in the eastern Limfjord differs from the west, which is characterized by a number of freshwater events when the North Sea connection was closed off during the Holocene. The eastern connection was open to the Kattegat throughout a large portion of the Holocene, with influx of open ocean water entering the system during periods of higher sea level.

North Atlantic surface ocean 14C variability between 30 – 40 kyr. BP

The Faroe-Shetland channel is situated in the main path of the inflow of warm North Atlantic surface water to the Nordic seas and further provides an escape route for the cold Norwegian Sea Deep Water. AMS 14C dates of planktonic foraminifera covering Marine Isotope Stage 3 from two cores in the Faroe-Shetland channel will be used to trace past variability of the Atlantic Meridional Overturning Circulation (AMOC). The reservoir age R shows considerable variability ranging between 50 to 2750 14C years. In particular high R values are observed during Heinrich event 4 (H4) with values around 1550 14C years and during the Laschamp magnetic excursion with R values as high as 2700 14C years. The period between Greenland interstadial 8 (GI8) and GI5 show highly variable R values with interstadial R values around 500 – 650 14C years, i.e. slightly higher than ‘normal’, whereas stadials show either significantly higher or lower R values. From GI5 towards the Last Glacial Maximum R values are generally around 1000 14C years or higher. Using magnetic susceptibility, IRD and δ13C and δ18O values measured on the planktic foraminifera species Neogloboquadrina pachyderma, we compare the observed R variability with reconstructed changes in the Atlantic Meridional Overturning Circulation (AMOC). Furthermore a climate model of intermediate complexity (GENIE) including 14C is used as conceptual tool for identifying oceanographic configuration explaining the observed R variability.

Freshwater reservoir effect (FRE) on re-dating of the prehistoric Eurasian Steppe cultures

There is a major problem with dating human skeletal material in Eurasian
steppe, possibly due to the freshwater reservoir effects (FRE). The goal of the
project is to examine the extent of the FRE in key areas of Siberia and
Kazakhstan through AMS 14C dating and stable isotope (δ13C, δ15N, δ34S)
analysis of c. 150 archaeological and modern samples. Here, we present the
very first results of the tests. We hope that within next years the study will
provide advanced knowledge of FRE across the region; improved 14C sampling
protocols for 14C and isotopic studies; new data on the chronology, diet and
isotopic ecology of particular archaeological sites, and a database on the
extent and variability of the FRE in the region

Using radiocarbon and stable isotopes to identify sediment carbon sources in an alkaline, humic lake.

We present a pilot study that uses the radiocarbon (∆14C) method to determine the source of carbon buried in the surface sediment of Lough Erne, a humic, alkaline lake in northwest Ireland. ∆14C, δ13C and δ15N values were measured from phytoplankton, dissolved inorganic, dissolved organic and particulate organic carbon. A novel radiocarbon method, Stepped Combustion1 was used to estimate the degree of the burial of terrestrial carbon in surface sediment. The ∆14C values of the low temperature fractions were comparable to algal ∆14C, while the high temperature fractions were 14C-depleted (older than bulk sediment). The ∆14C end-member model indicated that ~64% of carbon in surface sediment was derived from detrital terrestrial carbon. The use of ∆14C in conjunction with stepped combustion allows the quantification of the pathways of terrestrial carbon in the system, which has implications for regional and global carbon burial.
1McGeehin, J., Burr, G.S., Jull, A.J.T., Reines, D., Gosse, J., Davis, P.T., Muhs, D., and Southon, J.R., 2001, Stepped-combustion C-14 dating of sediment: A comparison with established techniques: Radiocarbon, v. 43, p. 255-261.

14C as a tool to trace terrestrial carbon in a complex lake system: implications for foodweb structure and carbon cycling

Carbon and nitrogen stable isotope analysis (SIA) has identified the terrestrial subsidy of freshwater food-webs but relies on different 13C fractionation in aquatic and terrestrial primary producers. However dissolved inorganic carbon (DIC) is partly comprised of 13C depleted respiration of terrestrial C and ‘old’ C derived from weathering of catchment geology. SIA thus fails to differentiate between the contribution of old and recently fixed terrestrial C. DIC in alkaline lakes is partially derived from weathering of 14C-free carbonaceous bedrock This
yields an artificial age offset leading samples to appear significantly older than their actual age. As such, 14C can be used as a biomarker to identify the proportion of autochthonous C in the food-web. With terrestrial C inputs likely to increase, the origin and utilisation of ‘old’ or ‘recent’ allochthonous C in the food-web can also be determined. Stable isotopes and 14C were measured for biota, particulate organic matter (POM), DIC and dissolved organic carbon (DOC) from Lough Erne, Northern Ireland, a humic but alkaline lake. High winter δ15N values in calanoid zooplankton (δ15N =24‰) relative to phytoplankton and POM (δ15N =6‰ and 12‰ respectively) may reflect several microbial trophic levels between terrestrial C and calanoids. Furthermore winter calanoid 14C ages are consistent with DOC from inflowing rivers (87 and 75 years BP respectively) but not phytoplankton (355 years BP). Summer calanoid δ13N, δ15N and 14C (312 years BP) indicate greater reliance on phytoplankton. There is also temporal and spatial variation in DIC, DOC and POM C isotopes.

Freshwater Reservoir Effect on Re-Dating of Eurasian Steppe Cultures: First Results for Eneolithic and Early Bronze Age North-East Kazakhstan

Freshwater reservoir effects (FRE) can cause a major problem with radiocarbon dating human skeletal material in the Eurasian steppe. We present the first results of research into the extent of the FRE in the sites of Borly 4 (Eneolithic), and Shauke 1 and 8b (Early Bronze Age), North-Eastern Kazakhstan. AMS 14C dating and stable isotope (δ13C, δ15N) analysis of associated groups of samples (32 samples, 11 groups in total) demonstrate that: a) the diet of the humans and fauna analysed was based on the C3 foodchain with no evidence of a C4 plant (such as millet) contribution; aquatic resources apparently were a continuous dietary feature for the humans; b) the first 14C dates obtained for the Upper and Middle Irtysh River region attribute the Eneolithic period of the area to the 34th-30th c. BC, and the Early Bronze Age – to the 25th-20th c. BC; there is a ca. 450 years hiatus between the two periods; c) the maximum fish-herbivore freshwater reservoir offset observed equals 301±47 14C yrs. As such, 14C dates from aquatic and human samples from the area need to be interpreted with caution as they are likely to be affected by the offset (i.e. appear older).
The paper also discusses the effect of a sodium hydroxide (NaOH) wash on δ13C, δ15N, C:Natomic levels and collagen yields of the bone samples. Our results indicate a minor but significant effect of NaOH treatment only on C:Natomic ratios of the samples.

14C as a tool to trace terrestrial carbon in a complex lake system: implications for food-web structure and carbon cycling

Globally lakes bury and remineralise significant quantities of terrestrial C, and the associated flux of terrestrial C strongly influences their functioning. Changing deposition chemistry, land use and climate induced impacts on hydrology will affect soil biogeochemistry and terrestrial C export¹ and hence lake ecology with potential feedbacks for regional and global C cycling. C and nitrogen stable isotope analysis (SIA) has identified the terrestrial subsidy of freshwater food webs. The approach relies on different ¹³C fractionation in aquatic and terrestrial primary producers, but also that inorganic C demands of aquatic primary producers are partly met by ¹³C depleted C from respiration of terrestrial C, and ‘old’ C derived from weathering of catchment geology. SIA thus fails to differentiate between the contributions of old and recently fixed terrestrial C. Natural abundance ¹⁴C can be used as an additional biomarker to untangle riverine food webs² where aquatic and terrestrial δ ¹³C overlap, but may also be valuable for examining the age and origin of C in the lake. Primary production in lakes is based on dissolved inorganic C (DIC). DIC in alkaline lakes is partially derived from weathering of carbonaceous bedrock, a proportion of which is¹⁴C-free. The low ¹⁴C activity yields an artificial age offset leading samples to appear hundreds to thousands of years older than their actual age. As such, ¹⁴C can be used to identify the proportion of autochthonous C in the food-web. With terrestrial C inputs likely to increase, the origin and utilisation of ‘fossil’ or ‘recent’ allochthonous C in the food-web can also be determined. Stable isotopes and 14C were measured for biota, particulate organic matter (POM), DIC and dissolved organic carbon (DOC) from Lough Erne, Northern Ireland, a humic alkaline lake. Temporal and spatial variation was evident in DIC, DOC and POM C isotopes with implications for the fluctuation in terrestrial export processes. Ramped pyrolysis of lake surface sediment indicates the burial of two C components. ¹⁴C activity (507 ± 30 BP) of sediment combusted at 400˚C was consistent with algal values and younger than bulk sediment values (1097 ± 30 BP). The sample was subsequently combusted at 850˚C, yielding 14C values (1471 ± 30 BP) older than the bulk sediment age, suggesting that fossil terrestrial carbon is also buried in the sediment. Stable isotopes in the food web indicate that terrestrial organic C is also utilised by lake organisms. High winter δ ¹⁵N values in calanoid zooplankton (δ ¹⁵N = 24%¸) relative to phytoplankton and POM (δ ¹⁵N = 6h and 12h respectively) may reflect several microbial trophic levels between terrestrial C and calanoids. Furthermore winter calanoid 14C ages are consistent with DOC from an inflowing river (75 ± 24 BP), not phytoplankton (367 ± 70 BP). Summer calanoid δ ^13C, δ ¹⁵N and ¹⁴C (345 ± 80 BP) indicate greater reliance on phytoplankton.

¹ Monteith, D.T et al., (2007) Dissolved organic carbon trends resulting from changes in atmospheric deposition chemistry. Nature, 450:537-535

² Caraco, N., et al.,(2010) Millennial-aged organic carbon subsidies to a modern river food web. Ecology,91: 2385-2393.

Determining adsorbate configuration on alumina surfaces with 13C nuclear magnetic resonance relaxation time analysis

Relative strengths of surface interaction for individual carbon atoms in acyclic and cyclic hydrocarbons adsorbed on alumina surfaces are determined using chemically resolved 13C nuclear magnetic resonance (NMR) T1 relaxation times. The ratio of relaxation times for the adsorbed atoms T1,ads to the bulk liquid relaxation time T1,bulk provides an indication of the mobility of the atom. Hence a low T1,ads/T1,bulk ratio indicates a stronger surface interaction. The carbon atoms associated with unsaturated bonds in the molecules are seen to exhibit a larger reduction in T1 on adsorption relative to the aliphatic carbons, consistent with adsorption occurring through the carbon-carbon multiple bonds. The relaxation data are interpreted in terms of proximity of individual carbon atoms to the alumina surface and adsorption conformations are inferred. Furthermore, variations of interaction strength and molecular configuration have been explored as a function of adsorbate coverage, temperature, surface pre-treatment, and in the presence of co-adsorbates. This relaxation time analysis is appropriate for studying the behaviour of hydrocarbons adsorbed on a wide range of catalyst support and supported-metal catalyst surfaces, and offers the potential to explore such systems under realistic operating conditions when multiple chemical components are present at the surface.

Carbon and nitrogen uptake of calcareous benthic foraminifera along a depth-related oxygen gradient in the OMZ of the Arabian Sea

Foraminifera are an important faunal element of the benthos in oxygen-depleted settings such as Oxygen Minimum Zones (OMZs) where they can play a relevant role in the processing of phytodetritus. We investigated the uptake of phytodetritus (labeled with 13C and 15N) by cal-careous foraminifera in the 0-1 cm sediment horizon under different oxygen concentrations within the OMZ in the eastern Arabian Sea. The in situ tracer experiments were carried out along a depth transect on the Indian margin over a period of 4 to 10 days. The uptake of phy-todetrital carbon within 4 days by all investigated species shows that phytodetritus is a rele-vant food source for foraminifera in OMZ sediments. The decrease of total carbon uptake from 540 to 1100 m suggests a higher demand for carbon by species in the low-oxygen core region of the OMZ or less food competition with macrofauna. Especially Uvigerinids showed high uptake of phytodetrital carbon at the lowest oxygenated site. Variation in the ratio of phytodetrital carbon to nitrogen between species and sites indicates that foraminiferal carbon and nitrogen use can be decoupled and different nutritional demands are found between spe-cies. Lower ratio of phytodetrital carbon and nitrogen at 540 m could hint for greater demand or storage of food-based nitrogen, ingestion or hosting of bacteria under almost anoxic condi-tions. Shifts in the foraminiferal assemblage structure (controlled by oxygen or food availabil-ity) and in the presence of other benthic organisms account for observed changes in the pro-cessing of phytodetritus in the different OMZ habitats. Foraminifera dominate the short-term processing of phytodetritus in the OMZ core but are less important in the lower OMZ bounda-ry region of the Indian margin as biological interactions and species distribution of foraminifera change with depth and oxygen levels.

Validating the use of intrinsic markers in body feathers to identify inter‑individual differences in non‑breeding areas of northern fulmars

Many wildlife studies use chemical analyses to explore spatio-temporal variation in diet, migratory patterns and contaminant exposure. Intrinsic markers are particularly valuable for studying non-breeding marine predators, when direct methods of investigation are rarely feasible. However, any inferences regarding foraging ecology are dependent upon the time scale over which tissues such as feathers are formed. In this study, we validate the use of body feathers for studying non-breeding foraging patterns in a pelagic seabird, the northern fulmar. Analysis of carcasses of successfully breeding adult fulmars indicated that body feathers moulted between September and March, whereas analyses of carcasses and activity patterns suggested that wing feather and tail feather moult occurred during more restricted periods (September to October and September to January, respectively). By randomly sampling relevant body feathers, average values for individual birds were shown to be consistent. We also integrated chemical analyses of body feather with geolocation tracking data to demonstrate that analyses of δ13C and δ15N values successfully assigned 88 % of birds to one of two broad wintering regions used by breeding adult fulmars from a Scottish study colony. These data provide strong support for the use of body feathers as a tool for exploring non-breeding foraging patterns and diet in wide-ranging, pelagic seabirds.

Living to the range limit: consumer isotopic variation increases with environmental stress

Background: Theoretically, each species’ ecological niche is phylogenetically-determined and expressed spatially as the species’ range. However, environmental stress gradients may directly or indirectly decrease individual performance, such that the precise process delimiting a species range may not be revealed simply by studying abundance patterns. In the intertidal habitat the vertical ranges of marine species may be constrained by their abilities to tolerate thermal and desiccation stress, which may act directly or indirectly, the latter by limiting the availability of preferred trophic resources. Therefore, we expected individuals at greater shore heights to show greater variation in diet alongside lower indices of physiological condition.

Methods: We sampled the grazing gastropod Echinolittorina peruviana from the desert coastline of northern Chile at three shore heights, across eighteen regionally-representative shores. Stable isotope values (δ13C and δ15N) were extracted from E. peruviana and its putative food resources to estimate Bayesian ellipse area, carbon and nitrogen ranges and diet. Individual physiological condition was tracked by muscle % C and % N.

Results: There was an increase in isotopic variation at high shore levels, where E. peruviana’s preferred resource, tide-deposited particulate organic matter (POM), appeared to decrease in dietary contribution, and was expected to be less abundant. Both muscle % C and % N of individuals decreased with height on the shore.

Discussion: Individuals at higher stress levels appear to be less discriminating in diet, likely because of abiotic forcing, which decreases both consumer mobility and the availability of a preferred resource. Abiotic stress might be expected to increase trophic variation in other selective dietary generalist species. Where this coincides with a lower physiological condition, this may be a direct factor in setting their range limit.