Facies development and sequence stratigraphy of the Ludfordian (Upper Silurian) deposits in the Zbruch River Valley, Podolia, western Ukraine: local facies overprint on the δ13Ccarb record of a global stable carbon isotope excursion

The Ludfordian (Upper Silurian) succession in Podolia, western Ukraine, represents a Silurian carbonate platform developed in an epicontinental sea on the shelf of the paleocontinent of Baltica. Coeval deposits throughout this basin record a positive stable carbon isotope excursion known as the Lau excursion. The record of this excursion in Podolia exhibits an unusual amplitude from highly positive (+6.9 ‰) to highly negative (?5.0 ‰) δ¹³C_carb values. In order to link δ¹³C_carb development with facies, five sections in the Zbruch River Valley were examined, providing microfacies characterization and revised definitions of the Isakivtsy, Prygorodok, and Varnytsya Formations. The Isakivtsy Fm. is developed as dolosparite replacing originally bioclastic limestone. The Prygorodok Fm., recording strongly depleted (down to ?10.53 ‰) to near zero (0.12 ‰) δ¹³C_carb values is developed as laminated, organic-rich dolomicrite with metabentonite and quartz siltstone beds. The Varnytsya Fm. is characterized by peritidal deposition with consistent, slightly negative δ¹³C_carb values (?0.57 to ?3.20 ‰). It is proposed that dolomitization of the Isakivtsy Fm. is associated with a sequence boundary and erosional surface. The overlying Prygorodok Fm. represents the proximal part of a TST deposited in restricted and laterally extremely variable environments dominated by microbial carbonate production. The transition to the overlying Varnytsya Fm. facies is marked by a maximum flooding surface. The SB and MFS are potentially correlative within the basin and support a global rapid sea-level fall previously proposed for this interval. The interpretation of the Prygorodok Fm. as coastal lake deposits may explain the unusual δ¹³C_carb values and constitute one of the few records of this type of environment identified in the early Paleozoic.     

Palaeozoic cold seep carbonates from Europe and North Africa—an integrated isotopic and geochemical approach

In this paper, we report the highest and lowest carbon isotope values known from Palaeozoic carbonate rocks. These unusual δ¹³C values (−50 to +23.5‰) are due to microbial methanogenesis and methanotrophy in Silurian to Carboniferous carbonates. Trace elements were used to decipher the primary mineralogy of the carbonate cements. Very high Sr values and low amounts of Mg, Fe and Mn point toward aragonite precursors, whereas high Fe and Mn values are indicative of primary calcites and allow reconstruction of the redox conditions. Four carbonate deposits are described from the Meseta and the Antiatlas of Morocco, the Pyrenees (France) and the Harz mountains (Germany). The highest δ¹³C values in concretion below the uppermost Silurian Spinatrypa Mound (Moroccan Meseta) give evidence, that CO₂ was produced during methanogenesis. δ¹³C values between −10 and −32‰indicate that the formation of microbial carbonates and cements in the Middle Devonian Hollard Mound (Antiatlas) and in the Lower Carboniferous sediments of the Iberg (Harz) formed at thermogenetic methane or petroleum seeps. The Late Bashkirian carbonate mound of the High Pyrenees (Tantes Mound) is the first Palaeozoic carbonate with seepage fluids being dominated by biogenic methane. Matrix carbonates exhibit δ¹³C values as low as −34‰. In some parts, voids make up more than 50 vol% of the mound. They are filled with several generations of cement. The earliest void filling is isopachous fibrous cement, which represents former aragonite. Most negative δ¹³C values of −50‰were measured in these isopachous fibrous cements. The difference of 55‰in δ¹³C values between normal sediments and early aragonite cements can only be explained by the contribution of CO₂ from anaerobic oxidation of biogenic methane in a cold seep setting.     

Biological and physical influences on the carbon isotope content of CO<Subscript>2</Subscript> in a subalpine forest snowpack,Niwot Ridge,Colorado

Considerable research has recently been devoted to understanding biogeochemical processes under winter snow cover, leading to enhanced appreciation of the importance of many winter ecological processes. In this study, a comprehensive investigation of the stable carbon isotope composition (δ¹³C) of CO₂ within a high-elevation subalpine forest snowpack was conducted. Our goals were to study the δ¹³C of biological soil respiration under snow in winter, and to assess the relative importance of diffusion and advection (ventilation by wind) for gas transport within snow. In agreement with other studies, we found evidence of an active microbial community under a roughly 1-m deep snowpack during winter and into spring as it melted. Under-snow CO₂ mole fractions were observed up to 3,500 μmol mol⁻¹, and δ¹³C of CO₂ varied from ~−22 to ~−8‰. The δ¹³C of soil respiration calculated from mixing relationships was −26 to −24‰, and although it varied in time, it was generally close to that of the bulk organic horizon (−26.0‰). Subnivean CO₂ and δ¹³C were quite dynamic in response to changes in soil temperature, liquid water availability, and wind events. No clear biologically-induced isotopic changes were observed during periods when microbial activity and root/rhizosphere activity were expected to vary, although such changes cannot be eliminated. There was clear evidence of isotopic enrichment associated with diffusive transport as predicted by theory, but simple diffusive enrichment (4.4‰) was not observed. Instead, ventilation of the snowpack by sustained wind events in the forest canopy led to changes in the diffusively-enriched gas profile. The isotopic influence of diffusion on gases in the snowpack and litter was greatest at greater depths, due to the decreased relative contribution of advection at depth. There were highly significant correlations between the apparent isotopic content of respiration from the soil with wind speed and pressure. In summary, physical factors influencing gas transport substantially modified and potentially obscured biological factors in their effects on δ¹³C of CO₂ within this subalpine forest snowpack.     

Controlling for anthropogenically induced atmospheric variation in stable carbon isotope studies

Increased use of stable isotope analysis to examine food-web dynamics, migration, transfer of nutrients, and behavior will likely result in expansion of stable isotope studies investigating human-induced global changes. Recent elevation of atmospheric CO₂ concentration, related primarily to fossil fuel combustion, has reduced atmospheric CO₂ δ¹³C (¹³C/¹²C), and this change in isotopic baseline has, in turn, reduced plant and animal tissue δ¹³C of terrestrial and aquatic organisms. Such depletion in CO₂ δ¹³C and its effects on tissue δ¹³C may introduce bias into δ¹³C investigations, and if this variation is not controlled, may confound interpretation of results obtained from tissue samples collected over a temporal span. To control for this source of variation, we used a high-precision record of atmospheric CO₂ δ¹³C from ice cores and direct atmospheric measurements to model modern change in CO₂ δ¹³C. From this model, we estimated a correction factor that controls for atmospheric change; this correction reduces bias associated with changes in atmospheric isotopic baseline and facilitates comparison of tissue δ¹³C collected over multiple years. To exemplify the importance of accounting for atmospheric CO₂ δ¹³C depletion, we applied the correction to a dataset of collagen δ¹³C obtained from mountain lion (Puma concolor) bone samples collected in California between 1893 and 1995. Before correction, in three of four ecoregions collagen δ¹³C decreased significantly concurrent with depletion of atmospheric CO₂ δ¹³C (n ≥ 32, P ≤ 0.01). Application of the correction to collagen δ¹³C data removed trends from regions demonstrating significant declines, and measurement error associated with the correction did not add substantial variation to adjusted estimates. Controlling for long-term atmospheric variation and correcting tissue samples for changes in isotopic baseline facilitate analysis of samples that span a large temporal range.     

Influence of substratum on the variability of benthic biofilm stable isotope signatures: implications for energy flow to a primary consumer

Benthic biofilms have been identified using stable isotope analysis (SIA) as an important resource supporting many freshwater food webs. However, biofilm δ¹³C signatures are highly variable in freshwaters, which may hamper our understanding of energy flow through food webs in these systems. There has been little consideration of the influence that substratum may have on biofilm δ¹³C signature variability and energy flows to primary consumers. We investigated the effect of organic and inorganic substrata on biofilm dynamics by examining: (1) temporal variability of biofilm stable isotope (δ¹³C, δ¹⁵N) signatures on allochthonous leaf-litter (Eucalyptus camaldulensis) and cobble substrata over 12 months in a lowland river in south-eastern Australia; and (2) the effect of substrata on biofilm energy flows to a grazer snail, Physa acuta (Gastropoda: Physidae), using SIA and ecological stoichiometry in a laboratory experiment. The temporal study indicated that cobble biofilm varied significantly in δ¹³C signature during the 12 months (up to 11‰), whereas the δ¹³C signature of leaf biofilm was less variable (less than 2‰). In contrast, biofilm δ¹⁵N signatures varied temporally on both cobble (2.6‰) and leaf (1‰) substrata. This suggests that leaf biofilm was more reliant on leaf tissue for carbon and therefore less limited by carbon supply than cobble biofilm whereas for nitrogen biofilm on both substrata was reliant on external sources. In the laboratory experiment, snails fed leaf biofilm reflected more of an allochthonous δ¹³C signature than cobble biofilm fed snails, suggesting assimilation of leaf carbon via the heterotrophic microbial community within the biofilm. Snails grew largest on cobble biofilm, which had lower C:N ratios than leaf biofilm. Our results demonstrate that the type of substratum can influence the temporal variability of biofilm δ¹³C signatures and energy flow to primary consumers.     

The carbon and nitrogen isotopic values of particulate organic material from the Florida Keys: a temporal and spatial study

The δ¹⁵N and δ¹³C values of particulate organic material (POM) were analyzed from 35 sites in the Florida Keys over the time interval 2000 to 2002. The sites within the study area were delineated into nine transects stretching from Key West to Key Largo. Each transect consisted of three to five sites extending from close to the Keys to the edge of the reef tract. The POM had mean δ¹⁵N and δ¹³C values of +3.6‰ (σ = ±3.2‰) and −19.9‰ (σ = ±0.6‰) respectively. Over the study period there were no statistically significant changes in δ¹⁵N, δ¹³C, or C:N. For the majority of the sampling dates, the δ¹³C values showed a distinct inshore (δ¹³C = −18.3‰, σ = ±1.0‰) to offshore gradient (δ¹³C = −21.4, σ = ±0.9‰). In contrast, the δ¹⁵N values showed no consistent patterns related to the distance from land. The more positive δ¹³C values of the nearshore samples suggest that the source of the carbon and the nitrogen in the POM in the nearshore was mainly derived from the degradation of seagrass detritus and not from the input of anthropogenically derived material from the Florida Keys. In contrast, the POM on the outer reef was dominated by marine plankton. As mineralization and nitrification of the organic nitrogen pool are major contributors to the dissolved inorganic nitrogen in the water column, it is unlikely that variations in the δ¹⁵N of the algae and other benthic organisms reported in the Florida Keys are related to the input of sewage.     

The Late Eocene ‘Whiskey Creek’ methane-seep deposit (western Washington State)

The Late Eocene ‘Whiskey Creek’ deposit (Pysht Formation, Olympic Penisula, Washington State) formed at a methane-seep. Early diagenetic micrites and aragonite cement have δ¹³C values as low as −36‰ indicating that the seepage fluids contained methane. With respect to micrite samples, low δ¹³C values correlate with relatively high δ¹³O values andvice versa. Ongoing micrite formation after the cessation of the seepage during increased burial might have altered the isotopic composition of the microcrystalline carbonates toward lower δ¹³O values and higher δ¹³C values. Alternatively, the trend in isotope values may reflect a change in the composition of seepage fluids. The principal difference between these scenarios is the duration of seepage with respect to micrite formation. Two petrographically similar varieties of blocky calcite spar are related to different carbonate sources. The δ¹³C values range from −32 to −29‰ for one type of blocky spar and are either the result of methane oxidation or indicate thermal decarboxylation of organic matter. Low δ¹⁸O values are in favour of the latter. For the other type of spar, δ¹³C values as high as +6‰ indicate carbonate formation within the zone of methanogensis. The ‘Whiskey Creek’ limestone exhibits a chaotic fabric produced by a variety of processes, including bioturbation, concretionary carbonate formation, earlyin situ brecciation, carbonate corrosion, and late fracturing of the rock. Two varieties of micrite aggregates are responsible for the nodular fabric of the limestone. Smoothly-shaped pyritiferous micrite nodules are of diagenetic origin and formed in a manner similar to that which produces carbonate concretions. Apart from being induced by anaerobic oxidation of methane, their formation is proposed to be linked to iron reduction and sulphide formation. The second, dominant variety is represented by irregularly-shaped, nodular to angular micrite aggregates surrounded by massive rims of pyrite, resulting from carbonate corrosion. A pure, fluorescent seam-micrite, constructive in origin, lines cavities or surrounds micritic aggregates.     

Carbon nutrition of mature green orchid <Emphasis Type="Italic">Serapias strictiflora</Emphasis> and its mycorrhizal fungus <Emphasis Type="Italic">Epulorhiza</Emphasis> sp.

We studied the nutritional modes of the orchid Serapias strictiflora and its mycorrhizal fungus Epulorhiza sp. using the differences in carbon isotopic composition (δ¹³C) of C₃ orchid and C₄ maize tissues. We found that if cultivated in substrate lacking any organic compounds, the mycorrhizal extraradical mycelia (δ¹³C = −26.3 ± 0.2 ‰) developed well, despite being fully dependent on nutrition from orchid roots (δ¹³C = −28.6 ± 0.1 ‰). If the mycorrhizal fungus had additional access to and colonized decaying maize roots (δ¹³C = −14.6 ± 0.1 ‰), its isotopic composition (δ¹³C = −21.6 ± 0.4 ‰) reflected a mixture of biotrophy and saprotrophy. No statistically significant differences in δ¹³C of new storage tubers were found between Epulorhiza-associated orchids with (δ¹³C = -28.2 ± 0.1 ‰) and without access to maize roots (δ¹³C = −28.6 ± 0.2 ‰). We conclude that autotrophy is the predominant nutritional mode of mature S. strictiflora plants and that they supply their mycorrhizal fungus with substantial amount of carbon (69 ± 3 % of the fungus demand), even if the fungus feeds saprotrophically.     

Carbon isotope ratio and photosynthetic activity of phytoplankton in the eutrophic Mikawa Bay,Japan

Primary production by phytoplankton in the eutrophic Mikawa Bay, Japan, was studied by simultaneous measurements of natural carbon isotope ratio (δ ¹³C) and short-term carbon uptake rates (¹³C tracer study) of size-fractionated nannoplankton (<10 μm) and net plankton (>10 μm) samples. Short-term photosynthetic rates, which represent the physiological state of algae, were variable regardless of standing stock sizes. Theδ ¹³C values of particulate organic carbon (POC) in June and July displayed horizontal variations for both the net plankton fraction (−19.8 to −12.7‰) and the nannoplankton fraction (−22.0 to −12.8‰). For both fractions, low concentrations of POC had more negativeδ ¹³C values (−22 to −18‰). Highδ ¹³C values for the net plankton were found when POC concentrations were much higher, due to red tide. This suggests that the increase in algal standing crop for the net plankton fraction resulted from accelerated photosynthetic activity. However the nannoplankton fractions with higher POC values have relatively lowδ ¹³C values.     

Stable isotope characteristics across narrow savanna/woodland ecotones in Wolfe Creek Meteorite Crater,Western Australia

The stable isotopic composition (δ¹³C) of sediments from lakes are frequently analyzed to reconstruct the proportion of the regional vegetation that used either the C₃ or C₄ photosynthetic pathways, often without conducting a detailed survey of the current local vegetation. We performed a study on the modern vegetation composition within the Wolfe Creek Meteorite Crater to complement our future paleoecological investigation of the crater. A bull’s-eye pattern exists where C₄ grasses dominate an outer ring and salt tolerant species, including shrubs, herbs, chenopods, and halophytic algae, dominate the inner pan of the crater. The ecotone between the inner and outer zones is narrow and occupied by tall (>7 m) Acacia ampliceps, with some C₄ grasses in the understory. Along with the highest water table and most saline soils the center of the crater has C₃ plants present with the highest δ¹³C and δ¹⁵N values. The range of δ¹³C and δ¹⁵N values from the analysis of surface soil organic matter (OM) was much smaller compared with the range of values from plant materials implying that either: (1) the current plant OM has not yet been integrated into the soils, or (2) processes within the soil have acted to homogenize isotopic variability within the crater. The application of a two end member mixing model to calculate %C₄ and %C₃ biomass from the δ¹³C of surface soil OM was complicated by: (1) the crater containing both a dry habitat with C₄ grasses and a central pan with C₄ halophytic plants and, (2) the large variation in the δ¹³C of the plants and soil OM.     

Stable carbon isotope development and sea-level changes during the Late Ludlow (Silurian) of the Łysogóry region (Rzepin section,Holy Cross Mountains,Poland)

The Ludlow deposits of the Winnica Formation in the Rzepin section (Holy Cross Mountains, Poland) have been studied with respect to their facies evolution and stable carbon isotope ratios from whole-rock samples. The C-isotope curve of the Rzepin section records a distinct positive excursion with maximal values of +8.9‰. A Late Ludlow positive isotope excursion is known from different paleocontinents and thus is regarded as a global isotope event. The presence of the event allows for a chemostratigraphic correlation of the Rzepin profile with the classical, biostratigraphically well-dated Gotland section. The Ludlow deposits of the Holy Cross Mountains are interpreted in terms of sea-level changes during the isotope excursion. Because the Rzepin and Gotland sections are positioned on the opposite sides of the same foreland basin, a comparison of their sequence stratigraphy allows to test the regularities of the sea-level changes on the shelf of Baltica. In the present paper, a modified view of the recently published sequence stratigraphy of the Gotland succession is presented. Our results indicate that the positive Ludlow δ¹³C excursion is connected with prolonged low-stand conditions with small, internal transgressive pulses.     

Between-tree variations in leaf δ13C of Quercus pubescens and Quercus ilex among Mediterranean habitats with different water availability

In this study, sun leaf carbon isotope composition (δ¹³C) of two co-occurring woody Mediterranean species (Quercus pubescens Willd., a deciduous oak, and Q. ilex L., an evergreen one) was investigated on four sites with different water availability. The total range of δ¹³C values was 4.4 and 3.1‰ for Q. pubescens and Q. ilex respectively. The intra-site variability was about 3‰. Total mean per species was equal. There were significant differences among sites, but at each site means of δ¹³C were not significantly different between species. A simple physiological model predicts no difference in intrinsic water-use efficiency (WUE_i) between evergreen and deciduous oaks. The relationship between site means of δ¹³C and water parameters suggests that there is a leaf functional adjustment with respect to available water resource. No correlation was found between δ¹³C and the contents of any mass-based biochemical constituent. Nevertheless there was a significant correlation between δ¹³C and leaf mass per area of Q. ilex. For both species, there is also a positive correlation between leaf δ¹³C and individual crown area, i.e. a structural characteristic at tree level. Causal relations between δ¹³C and plant-environment interactions are discussed. Received: 25 October 1996 / Accepted: 19 January 1997     

Mechanism for the small-scale movement of carbon among estuarine habitats: organic matter transfer not crab movement

In theory, carbon is highly mobile in aquatic systems. Recent evidence from carbon stable isotopes of crabs (Parasesarma erythrodactyla and Australoplax tridentata), however, shows that in subtropical Australian waters, measurable carbon movement between adjacent mangrove and saltmarsh habitats is limited to no more than a few metres. We tested whether the pattern in crab δ¹³C values across mangrove and saltmarsh habitats was explained by crab movement, or the movement of particulate organic matter. We estimated crab movement in a mark–recapture program using an array of pitfall traps on 13 transects (a total of 65 traps) covering an area of 600 m² across the interface of these two habitats. Over a 19-day period, the majority of crabs (91% for P. erythrodactyla, 93% for A. tridentata) moved <2 m from the place of initial capture. Crab movement cannot, therefore, explain the patterns in δ¹³C values of crabs. δ¹³C values of detritus collected at 2-m intervals across the same habitat interface fitted a sigmoidal curve of a similar form to that fitting the δ¹³C values of crabs. δ¹³C values of detritus were 2–4‰ more depleted in saltmarsh (−18.5±0.6‰), and 4–7‰ more depleted in mangroves (−25.9±0.1‰) than δ¹³C values of crabs recorded previously in each habitat. Assimilation by crabs of very small detrital fragments or microphytobenthos, more enriched in ¹³C, may explain the disparity in δ¹³C values. Nevertheless, the pattern in δ¹³C values of detritus suggests that crabs obtain their carbon from up to several metres away, but without themselves foraging more then a metre or so from their burrow. Such detailed measurements of carbon movement in estuaries provide a spatially explicit understanding of the functioning of food webs in saltmarsh and mangrove habitats.     

Stable carbon isotope characteristics of desert plants in the Junggar Basin, China

Desert plants have unique strategies for survival and growth to cope with the limited water availability in arid regions. The stable carbon isotope (δ ¹³C) provides an integrated measurement of internal plant physiological and external environmental properties affecting photosynthetic gas exchange and water use efficiency. The δ ¹³C values of 84 species in the Junggar Basin were categorized into two groups (ranged from −30.1 to −23.3‰ for C₃ and −14.9 to −9.9‰ for C₄ species, respectively). No life form differences in δ ¹³C values were detected in C₃ (p = 0.78) and C₄ plants (p = 0.63). Small differences among life forms were observed in δ ¹³C values in C₄ species with shrubs slightly depleted (−13.3‰) relative to perennials (−13.1‰) and annuals (−12.5‰). These differences suggested that δ ¹³C value could not represent a plant functional group classification based on life forms in C₄ plants in extremely arid regions. Ephemerals are all using C₃ photosynthetic pathway and no significant differences (p = 0.92) in δ ¹³C values were observed between annuals (−26.5‰) and perennials (−26.4‰). The δ ¹³C values of Tulipa iliensis (an important ephemeral species distributed widely in the Junggar Basin) among nine natural populations were positively correlated with leaf (r ² = 0.46, p = 0.046) and soil (r ² = 0.67, p = 0.007) total nitrogen content, and negatively correlated with leaf (r ² = 0.48, p = 0.039) and soil (r ² = 0.79, p = 0.001) water content. This indicated that the variation in δ ¹³C values of T. iliensis was probably caused by both water availability associated stomatal openness and nitrogen availability associated photosynthetic capacity. T. iliensis is very sensitive to water and nitrogen availability in soil.     

Vegetation control effects on untreated wood,crude cellulose and holocellulose δ<Superscript>13</Superscript>C of early and latewood in 3- to 5-year-old rings of Douglas-fir

The stable carbon (C) composition of tree rings expressed as δ¹³C, is a measure of intrinsic water-use efficiency and can indicate the occurrence of past water shortages for tree growth. We examined δ¹³C in 3- to 5-year-old rings of Douglas-fir (Pseudotsuga menziesii (Mirb) Franco) trees to elucidate if decreased water supply or uptake was a critical factor in the observed growth reduction of trees competing with understory herb and shrub vegetation compared to those growing without competition. We hypothesized that there would be no differences in δ¹³C of earlywood in trees growing in plots with competing vegetation and those in plots receiving complete vegetation control during 5 years because earlywood formed early in the growing season when soil water was ample. We also hypothesized that δ¹³C in latewood which was formed during the later half of the growing season when precipitation was low, would be greater (less negative) in trees in plots without vegetation control. We then separated early and latewood from rings for three consecutive years and analyzed their δ¹³C composition. No significant differences in earlywood δ¹³C in years 3–5 were observed for trees in the two vegetation control treatments. δ¹³C of untreated latewood separated from wood cores was greater in 4- and 5-year-old rings of trees growing with competing vegetation compared to trees growing without vegetation competition (i.e., −25.5 vs. −26.3‰ for year 4, and −26.1 vs. −26.8‰ for year 5). Results suggest that water shortages occurred in Douglas-fir trees on this coastal Washington site in the latewood-forming portion of the growing season of years 4 and 5 in the no-vegetation control treatment. We also compared δ¹³C from untreated wood, crude cellulose extracted with the Diglyme–HCl method, and holocellulose extracted with toluene–ethanol to see if the extraction method would increase the sensitivity of the analysis. δ¹³C values from the two extraction methods were highly correlated with those from untreated samples (r ² = 0.97, 0.98, respectively). Therefore, using untreated wood would be as effective as using crude cellulose or holocellulose to investigate δ¹³C patterns in young Douglas-fir.     

Preservation effects on stable isotope ratios and consequences for the reconstruction of energetic pathways

Stable isotope analysis provides a powerful tool for describing the energetic pathways in a variety of ecosystems. However, isotope ratios of animal tissues can be altered by preservation methods, potentially leading to biased estimates of energy pathways when they are not taken into account. Here, we investigated the direct preservation effects of formalin, ethanol, NaCl, and drying on the δ¹³C and δ¹⁵N of fish muscle tissues, as well as the ultimate effects on the reconstruction of the energy pathways. All preservation methods, except drying, had significant impacts on δ¹³C and δ¹⁵N values. The effects of preservation appear to be highly taxa-specific and no significant time-dependent variations in nearly 2-year duration of preservation. δ¹³C and δ¹⁵N values were generally changed dramatically within the early stage of the preservation process and became stable over a relatively long-term preservation. Using an isotopic balance mixing model, the isotope-based food web reconstruction reveals that, without preservation correction, the importance of the pelagic energetic pathways for the fishes could be misestimated, except for the drying preservation. These results highlight that preservation can bias the interpretation of food web reconstruction results.     

87Sr/86Sr Chronostratigraphy and dolomitization history of the Seroe Domi Formation,Curaçao (Netherlands Antilles)

Summary The Seroe Domi Formation is a 350 m-thick sequence of Neogene marine limestones and silicilastic sandstones cropping out on the leeward coast of Cura?ao, Netherlands Antilles. Integrated analyses of lithofacies, biostratigraphy, geochemistry and Sr isotope model age analyses indicate that Seroe Domi Formation has experienced three major episodes of limestone diagenesis and dolomitization (Dolomites I, I′, and II) that have taken place after successive Mio-Plio-Pleistocene depositional and subaerial exposure events (Subunits 1, 2, and 3). Subunit 1, the lowermost 30 to 100 m of the Seroe Domi Formation, is composed of interbedded coralgal grainstone gravity flows, pelagic wackestones, and allochthonous blocks deposited in Middle Miocene deep-water (>500 m) fore-reef and carbonate slope environments. Subunit 2, the uppermost 250 m of the Seroe Domi Formation, consists of coralgal packstones with basement-derived siliciclastic sands that were deposted in shallowing fore-reef to reef-front environments during the Late Miocene to Pliocene. Subunit 3 siliciclastic sandstones were deposited during the Early Pleistocene within erosional cavities in the Subunit 2 limestones, and are overlain by Late Pleistocene Quaternary Limestone Terraces. The petrography, distribution and geochemistry of Dolomites I, I′ and II indicate that they were precipitated from seawater-freshwater mixing zone fluid environments. Dolomite rhombs and meteoric calcite cements within biomolds illustrate that the host Seroe Domi Formation limestones were subaerially exposed prior to each dolomitization event. Dolomite I (δ¹⁸O = +1.04 to +2.46% PDB; δ¹³C = −2.55 to −6.79 PDB;⁸⁷Sr/⁸⁶Sr=0.708866 to 0.708915; Zn=0 ppm; Cu=0 ppm) was precipitated from mixtures of seawater with isotopically-depleted freshwater during the late Middle Miocene. Dolomite I′ (δ¹⁸O = +2.08 to +3.55 PDB, δ¹³C = −1.53 to 1.69 PDB,⁸⁷Sr/⁸⁶Sr=0.708981−0.709030; Zn=0 ppm; Cu=0 ppm) was also precipitated from mixtures of seawater with isotopically-depleted freshwater, but during late Late Miocene. In contrast, Dolomite II (δ¹⁸O = +2.69 to +3.51 PDB; δ¹³C = −0.34 to +1.53 PDB;⁸⁷Sr/⁸⁶Sr=0.708954 to 0.709088; Zn=20 ppm; Cu=20 ppm) precipitated from late Early Pliocene mixtures of seawater with isotopically-depleted freshwater that had derived Zn, Cu, and less-radiogenic Sr from basalts comprising the Cura?ao basement.     

Evaluating the utility of stable isotope analyses of archived freshwater sample materials

We evaluated the potential utility of stable isotope analysis of tissues commonly archived by aquatic biologists. Previous studies with chemically preserved samples have shown contradictory results, which present an obstacle for the use of archived sample materials. We tested the effects of ethanol and formalin preservation on zooplankton and of ethanol on benthic macroinvertebrate δ¹³C and δ¹⁵N values. We found that neither formalin nor ethanol had a significant effect on δ¹³C and δ¹⁵N values of preserved zooplankton. Nor did ethanol significantly affect δ¹³C or δ¹⁵N values of macroinvertebrates. However, ethanol preservation slightly, but significantly decreased C:N ratios of both zooplankton and macroinvertebrates, probably reflecting some extraction of lipids. Overall, the effects of preservatives on δ¹³C and δ¹⁵N values that we observed were minor. We also compared δ¹³C and δ¹⁵N values analysed from roach scales and perch operculum bones with those analysed from muscle tissue. Decalcification of scales and operculum bones only slightly improved our comparison to muscle tissue δ¹³C and δ¹⁵N values. Decalcified scales had slightly higher δ¹³C and lower δ¹⁵N values. Similarly, decalcified operculum bones showed slightly increased δ¹³C and decreased δ¹⁵N values to those for fish muscle. Our results confirm that scales and operculum bones can provide a suitable proxy for fish muscle in isotope studies with minor correction. We conclude that various archived sample materials can indeed be used with confidence for historical reconstructions of freshwater food webs by stable isotope analysis. Handling editor: K. Martens     

Predicting diet, trophic level and palaeoecology from bone stable isotope analysis: a comparative study of five red deer populations

C and N stable isotope ratios of red deer (Cervus elaphus) bone collagen (154 individuals) from five modern populations occupying geographically different habitats are reported. No significant difference was observed between deer occupying forested and non-forested environments subject to similar climatic conditions suggesting a simple “canopy effect” is not observed. Mean population δ¹³C is negatively correlated with temperature whereas mean population δ¹⁵N is positively correlated with temperature. A weak but significant positive correlation was observed between deer age and collagen δ¹³C values from the Isle of Rum population (Scotland). The amount of intra-population isotope variability is not consistent among populations; thus significant numbers of individuals from each species are required for modern food web studies, for palaeodietary baseline data, and for palaeoecological studies.     

Development of facies and C/O-isotopes in transects through the Ludlow of Gotland: Evidence for global and local influences on a shallow-marine environment

Summary The Silurian of Gotland is characterized by repeated changes in depositional facies development. The deposition of uniform sequences of micritic limestones and marls was interrupted four times by the growth of reef complexes and the formation of expanded carbonate platforms. Coinciding with these, often abrupt, facies changes extinction events occurred which predominantly affected nektonic and planktonic organisms. Ratios of carbon- and oxygen-isotopes covary with the facies development. Periods in which the deposition of limestonemarl alternations prevailed are characterized by relatively low C- and O-isotope values. During periods of enhanced reef growth isotope values are high. For these changes,Bickert et al. (1997) assume climatic changes between humid “H-periods”, with estuarine circulation systems and cutrophic surface waters with decreased salinity in marginal seas, and arid “A-periods”, with an antiestuarine circulation and oligotrophic, stronger saline surface waters. In order to separate local and regional influences on the isotopic development from the global trend, the interactions between facies formation and isotope record have to be clarified. For this purpose, the patterns of isotope values in the upper part of the Silurian sequence on Gotland (upper Wenlock —upper Ludlow) has been determined and stratigraphically correlated along four transects through different facies areas. Facies formation during this time interval was investigated by differentiation and mapping of twelve facies complexes in the southern part of Gotland. These include shelf areas, reef complexes with patch reefs and biostromes, backreef facies, and marginal-marine deposits. The good correspondence between the carbon-isotope records of the four transects suggests that local environmental conditions in the different facies areas did not influence the δ¹³C values. Therefore, a supra-regional or even global mechanism for the C-isotope variations is likely. In contrast to carbon istopes, the oxygen-isotope values of the four transects generally show parallel trends, but higher variabilities and in parts distinctly deviating developments with a trend to more negative values. These are interpreted as an effect of local warming in small shallow-water areas which developed during arid periods in reef complexes and backreef areas. The boundaries between A-periods and H-periods, as defined by δ¹³C values, which are interpreted as isochrones, can be mapped. From the upper Homerian to the Pridolian six parastratigraphic isotope zones are defined which only partly match the stratigraphic division ofHede (1942, 1960). The isotope stratigraphy results in an improved correlation between the shallow and marginal-marine areas in the eastern part of Gotland and the uniform shelf areas at the west coast of the island. Furthermore, a detailed relationship between the development of carbon and oxygen isotope ratios, the carbonate facies formation, and the succession of palaeontological events could be observed. At the transition from H-periods to A-periods, major extinction events occurred prior to the first increase of δ¹³C and δ¹⁸O values. Extinction events affected conodonts, graptolites, acritarchs, chitinozoans, and vertebrates and resulted in impoverished nektonic and planktonic communities. The reef-building benthos was less affected. Parallel to a first slight increase of isotope values, facies began to change, and reefs developed in suitable locations. The subsequent rapid increase of C- and O-isotope values occurred contemporarily with strong facies changes and a short-term drop of sea-level. Oligotrophic conditions in the later stages of A-periods led to strong reef growth and to an expansion of carbonate platforms. The transitions from A-periods to H-periods were more gradual. The δ¹³C values decreased slowly, but reef growth continued. Later the reefs retreated and were covered by the prograding depositional facies of shelf areas. The diversity of planktonic and nektonic communities increased again. The close relationship between facies formation, palaeontological events and isotope records in the Silurian suggests common steering mechanisms but gives no indication of the causes for the repeated extincion events related to H-period/A-period transitions. Especially the observation, that strong extinctions occurred prior to changes of isotope values and facies, points to causes that left no signals in the geological record. Hypothetical causes like collapse of trophical nets, anoxias, or cooling events are not evident in the sediment record or do not fit into the regular succession of period transitions.