Ontogenetic variations in Sr/Ca and Ba/Ca ratios of dental bioapatites from Bos taurus and Odocoileus virginianus

Sr/Ca and Ba/Ca ratios of bone are commonly used as biochemical indicators of trophic level in modern and fossil mammals. Concerns over the effects of diagenesis on Sr/Ca and Ba/Ca ratios of bone led archaeologists and paleontologists to favor tooth enamel, which is less prone to alteration. Sr/Ca and Ba/Ca ratios of bone, enamel, and dentin from three farm-raised steers (Bos taurus) and five wild white-tailed deer (Odocoileus virginianus) from central Missouri were compared. Our results show that changes in diet, discrimination, and growth rate during ontogeny can lead to significant differences in Sr/Ca and Ba/Ca ratios of different bioapatite types as well as significant differences within the same bioapatite forming at different times. Early- and late-forming tooth enamel can have significant differences in Sr/Ca and Ba/Ca ratios equivalent to almost one full trophic step. Although differences between early- and late-forming dentin are typically not significant, dentin Sr/Ca and Ba/Ca ratios are significantly greater than enamel values. This difference in Sr/Ca or Ba/Ca ratios between enamel and dentin from the same tooth can be greater than one full trophic step. These results have profound implications for the use of dental bioapatites in trophic level reconstructions. They highlight the importance of consistency in bioapatite selection, tooth selection, and relative location of sampling within the enamel cap. Furthermore, this expected difference in Sr/Ca and Ba/Ca ratios could be used as another means of checking for diagenetic alteration in ancient samples.     

Allometric constraints on Sr/Ca and Ba/Ca partitioning in terrestrial mammalian trophic chains

In biological systems, strontium (Sr) and barium (Ba) are two non-essential elements, in comparison to calcium (Ca) which is essential. The Sr/Ca and Ba/Ca ratios tend to decrease in biochemical pathways which include Ca as an essential element, and these processes are termed biopurification of Ca. The quantitative pathway of the biopurification of Ca in relation to Sr and Ba between two biological reservoirs (R _n and R_{n -1}) is measured with an observed ratio (OR) expressed by the (Sr/Ca) _Rn /(Sr/Ca) _Rn-1 and (Ba/Ca) _Rn /(Ba/Ca) _Rn-1 ratios. For a mammalian organism, during the whole biopurification of Ca starting with the diet to the ultimate reservoir of Ca which is the bone, the mean values for OR_Sr and OR_Ba are 0.25 and 0.2, respectively. In this study, published Sr/Ca and Ba/Ca ratios are used for three sets of soils, plants, and bones of herbivorous and carnivorous mammals, each comprising a trophic chain, to illustrate the biopurification of Ca at the level of trophic chains. Calculated OR_Sr and OR_Ba of herbivore bones in relation to plants and of bones of carnivores in relation to bones of herbivores give OR_Sr=0.30±0.08 and OR_Ba=0.16±0.08, thus suggesting that trophic chains reflect the Sr/Ca and Ba/Ca fluxes that are prevalent at the level of a mammalian organism. The slopes of the three regression equations of log(Sr/Ca) vs. log(Ba/Ca) are similar, indicating that the process of biopurification of Ca with respect to Sr and Ba is due to biological processes and is independent of the geological settings. Modifications of the logarithmic expression of the Sr/Ca and Ba/Ca relationship allow a new formula of the biopurification process to be deduced, leading to the general equation OR_Ba=OR_Sr^1.79±0.33,where the allometric coefficient is the mean of the slopes of the three regression equations. Some recent examples are used to illustrate this new analysis of predator-prey relations between mammals. This opens up new possibilities for the utilization of Ba/Ca and Sr/Ca in addition to stable isotope ratios (¹³C and ¹⁵N) for the determination of the relative contribution of different food sources to an animals diet.     

Use of foliar Ca/Sr discrimination and <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr ratios to determine soil Ca sources to sugar maple foliage in a northern hardwood forest

Calcium/strontium and ⁸⁷Sr/⁸⁶Sr ratios in foliage can be used to determine the relative importance of different soil sources of Ca to vegetation, if the discrimination of Ca/Sr by the plant between nutrient sources and foliage is known. We compared these tracers in the foliage of sugar maple (Acer saccharum) to the exchange fraction and acid leaches of soil horizons at six study sites in the White Mountains of New Hampshire, USA. In a previous study, sugar maple was shown to discriminate for Ca compared to Sr in foliage formation by a factor of 1.14 ± 0.12. After accounting for the predicted 14% shift in Ca/Sr, foliar Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios closely match the values in the Oie horizon at each study site across a 3.6-fold variation in foliar Ca/Sr ratios. Newly weathered cations, for which the Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios are estimated from acid leaches of soils, can be ruled out as a major Ca source to current foliage. Within sites, the ⁸⁷Sr/⁸⁶Sr ratio of the soil exchange pool in the Oa horizon and in the 0–10 cm and 10–20 cm increments of the mineral soil are similar to the Oie horizon and sugar maple foliar values, suggesting a common source of Sr in all of the actively cycling pools, but providing no help in distinguishing among them as sources to foliage. The Ca/Sr ratio in the soil exchange pool, however, decreases significantly with depth, and based on this variation, the exchange pool below the forest floor can be excluded as a major Ca source to the current sugar maple foliage. This study confirms that internal recycling of Ca between litter, organic soil horizons and vegetation dominate annual uptake of Ca in northern hardwood ecosystems. Refinement of our understanding of Ca and Sr uptake and allocation in trees allows improvement in the use of Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios to trace Ca sources to plants.     

Otolith Sr/Ca ratio complements Sr isotopes to reveal fish migration in large basins with heterogeneous geochemical landscapes

Environmental Biology of Fishes - The potential use of Sr/Ca and Ba/Ca ratios in fish otolith, as a complement to 87Sr/86Sr to study movements of Prochilodus lineatus, was evaluated in the La Plata...     

The relative uptake of Ca and Sr into tree foliage using a whole-watershed calcium addition

The use of strontium isotopes and ratios of alkaline earth elements (i.e., ⁸⁷Sr/⁸⁶Sr and Ca/Sr) to trace Ca sources to plants has become common in ecosystem studies. Here we examine the relative uptake of Ca and Sr in trees and subsequent accumulation in foliage. Using a whole-watershed Ca addition experiment at the Hubbard Brook Experimental Forest in N.H., we measured the uptake of Ca relative to Sr in foliage and roots of sugar maple (Acer saccharum), yellow birch (Betula alleghaniensis), American beech (Fagus grandifolia), and red spruce (Picea rubens). Vegetation was analyzed for Ca and Sr concentrations and the ⁸⁷Sr/⁸⁶Sr ratio. A comparison of the Ca/Sr ratio in the vegetation and the Ca/Sr ratio of the applied mineral allows for the calculation of a discrimination factor, which defines whether Ca and Sr are incorporated and allocated in the same ratio as that which is available. A discrimination factor greater than unity indicates preferential uptake of Ca over Sr; a factor less than unity reflects preferential uptake of Sr over Ca. We demonstrate that sugar maple (SM) and yellow birch (YB) have similar and small discrimination factors (1.14 ± 0.12,1σ and 1.16 ± 0.09,1σ) in foliage formation and discrimination factors of less than 1 in root formation (0.55–0.70). Uptake into beech suggests a larger discrimination factor (1.9 ± 1.2) in foliage but a similar root discrimination factor to SM and YB (0.66 ± 0.06,1σ). Incorporation into spruce foliage occurs at a much slower rate than in these other tree species and precludes evaluation of Ca and Sr discrimination in spruce foliage at this time. Understanding the degree to which Ca is fractionated from Sr in different species allows for refinement in the use of ⁸⁷Sr/⁸⁶Sr and Ca/Sr ratios to trace Ca sources to foliage. Methods from this study can be applied to natural environments in which various soil cation pools have different ⁸⁷Sr/⁸⁶Sr and Ca/Sr ratios. The results reported herein have implications for re-evaluating Ca sources and fluxes in forest ecosystems.     

A comparison between Ca and Sr cycling in forest ecosystems

In favourable conditions, the ⁸⁷Sr/⁸⁶Sr isotope ratios of the Sr delivered by rain and soil mineral weathering differ. Assuming that Ca and Sr behave similarly in forest ecosystems, several authors have used the ⁸⁷Sr/⁸⁶Sr variation in forest compartments to calculate the contribution of rain and mineral weathering to Ca fluxes and pools. However, there are a number of experimental reports showing that Ca and Sr may behave differently in the soil and in the plant. We have tested this Ca–Sr analogy in the field by measuring the variation of Sr and Ca concentrations, fluxes and pools in spruce, beech and maple stands on granite, sandstone and limestone. Results show that (1) variations of Ca and Sr concentrations are generally correlated at each level of the ecosystems. (2) In spruce on acid soils, a preferential uptake of Ca over Sr occurs (Aubure spruce Sr/Ca = 0.8×10⁻³; soil exchangeable Sr/Ca between 2 and 6×10⁻³). On calcareous soils, a preferential uptake of Sr over Ca by spruce may occur. (3) In spruce and beech on acid and calcareous soils, a preferential translocation of Ca over Sr from roots to leaves occurs ((Sr/Ca) in leaves was between 10 and 90% of that in roots). (4) The biological cycling of Ca and Sr leads to an enrichment of the upper soil layers in Ca and Sr. Compared to Sr, Ca accumulates in the upper layer of acid soils because Ca cycling through litterfall is favoured over Sr cycling, and possibly because of the selectivity of acid organic exchangers for Ca. This revised version was published online in June 2006 with corrections to the Cover Date.     

Variations of bioavailable Sr concentration and 87Sr/86Sr ratio in boreal forest ecosystems

The mean depth of Sr and water uptake in mixed Norway spruce (Picea abies) and Scots pine (Pinus sylvestris) stands was investigated, using natural variations of ⁸⁷Sr/⁸⁶Sr and ¹⁸O/¹⁶O in soils in relation to depth. Three spruce-pine pairs were studied on a podzol and a peat site in Northern Sweden. Tree leaf and wood, as well as soils, soil solutions and roots below each tree were analysed for Sr and Ca concentrations and ⁸⁷Sr/⁸⁶Sr ratio. The ¹⁸O/¹⁶O ratio was also determined in xylem sap and soil solutions in relation to depth. Soil solution ¹⁸O/¹⁶O decreased in relation to depth. Comparing with xylem sap ¹⁸O/¹⁶O data indicated a deeper uptake of soil water by pine than spruce on the podzol site and a superficial uptake by both species on the peat. The ⁸⁷Sr/⁸⁶Sr ratio of bioavailable Sr generally increased in soils in relation to depth. Contrastingly, the ⁸⁷Sr/⁸⁶Sr ratio in spruce wood was generally higher than in pine wood suggesting a deeper uptake of Sr by spruce. But the ⁸⁷Sr/⁸⁶Sr ratio and concentrations of bioavailable Sr were systematically higher below spruce than below pine. In order to explain these unexpected results, we built a simple flux model to investigate the possible effects of interspecific variations in Sr cycling, soil mineral weathering and depth of Sr uptake on soil and tree ⁸⁷Sr/⁸⁶Sr ratio. At the study sites, spruce cycled in litterfall up to 12 times more strontium than pine. The use of the model showed that this difference in Sr cycling could alone explain higher isotopic signatures of trees and topsoils below spruce. Besides, high isotopic signatures of roots in the A/E horizons below spruce led us to hypothesise a species-specific weathering process. Finally, the comparison between the ⁸⁷Sr/⁸⁶Sr ratios in wood and root or soil solutions below each species suggested that the average depth of Sr and water uptake were close, but irregular variations of the Sr isotopic ratio with depth reduce the accuracy of the results. Tree species strongly influence Sr isotopic ratios in boreal forest soils through differences in Sr cycling, and possibly through specific mineral weathering.     

Do deep tree roots provide nutrients to the tropical rainforest?

The contribution of deep tree roots to the nutrition of a tropicalrainforest were studied along an edaphic transect in French Guyana. Soil typeswere mapped in relation to the texture of the upper horizons and the depth ofoccurrence of the loamy saprolite. The position of mature individuals of fourcommon species, differing by they rooting depth, was identified and tree leaveswere analysed for major nutrients and strontium (Sr) isotopic ratios.On average, the range of leaf isotopic ratio (⁸⁷Sr/⁸⁶Sr= 0.714–0.716) was narrow compared to that of bulk soils(⁸⁷Sr/⁸⁶Sr = 0.72–0.77). Steep gradients ofincreasing ⁸⁷Sr/⁸⁶Sr in roots with soil depth were foundin all investigated profiles, which indicated that the flux of Sr deposited inrain and leached from the litter layer was tightly retained in the upper soillayers. Over the whole of the site, as well as within each soil unit, tree⁸⁷Sr/⁸⁶Sr ratios were very similar whatever the species,and close to litter and near-surface roots ⁸⁷Sr/⁸⁶Srratios, suggesting no or very little Sr contribution from deep tree roots.Variations of Ca and Sr concentrations in leaves were strongly correlated butnot with leaf ⁸⁷Sr/⁸⁶Sr ratios. These results support thetheory that Sr and Ca uptake and cycling are mostly superficial in tropicalrainforests.     

Determining the sources of calcium for migratory songbirds using stable strontium isotopes

We investigated natural variations in the stable isotopic composition of strontium (a surrogate for calcium) in the bones of a single species of breeding migratory songbird, as well as in their eggshells, egg contents, and food sources. We use this information to determine the sources of calcium to these migratory songbirds and their offspring. Samples were collected from two locations in the northeastern USA (Hubbard Brook, NH, and Downer Forest, VT.) that differed in soil geochemistry. The mean ⁸⁷Sr/⁸⁶Sr ratios of food items (caterpillars and snails), eggshells, and egg contents were indistinguishable within each site, but significantly different between the two sites. Mean ⁸⁷Sr/⁸⁶Sr ratios for the bones of adult females were significantly different between the two sites, but values were significantly lower than those of food items and eggshells at each site. Two of four adult individuals studied at each site had ⁸⁷Sr/⁸⁶Sr ratios lower than the entire range of values for local food sources. Mixing calculations indicate that up to 60% of skeletal strontium and calcium was derived from foods consumed in the winter grounds where lower ⁸⁷Sr/⁸⁶Sr ratios predominate. At each study site, the ⁸⁷Sr/⁸⁶Sr ratio of eggshells differed significantly between clutches, but the mean clutch ⁸⁷Sr/⁸⁶Sr ratios were unrelated to the skeletal ⁸⁷Sr/⁸⁶Sr ratio of the laying adult. These findings suggest that strontium (and hence calcium) for eggshell production in this species is derived predominantly from local food sources in breeding areas. Thus, reductions in available calcium in northern temperate ecosystems due to the influences of acid deposition could be potentially harmful to this and other species of migratory bird.     

Spatial and temporal variations in otolith chemistry and relationships with water chemistry: a useful tool to distinguish Atlantic salmon Salmo salar parr from different natal streams

Otolith elemental (Sr:Ca, Ba:Ca, Mn:Ca, Mg:Ca and Rb:Ca) and isotopic (⁸⁷Sr:⁸⁶Sr) profiles from several annual cohorts of juvenile Atlantic salmon Salmo salar were related to the physico‐chemical characteristics (chemical signatures, flow rate, temperature and conductivity) of their natal rivers over an annual hydrological cycle. Only Sr:Ca, Ba:Ca and ⁸⁷Sr:⁸⁶Sr in otoliths were determined by their respective ratios in the ambient water. Sr:Ca ratios in stream waters fluctuated strongly on a seasonal basis, but these fluctuations, mainly driven by water flow regimes, were not recorded in the otoliths. Otolith Sr:Ca ratios remained constant during freshwater residency at a given site and were exclusively related to water Sr:Ca ratios during low flow periods. While interannual differences in otolith elemental composition among rivers were observed, this variability was minor compared to geographic variability and did not limit classification of juveniles to their natal stream. Success in discriminating fish from different sites was greatest using Sr isotopes as it remained relatively constant across years at a given location.     

Determination of foliar Ca/Sr discrimination factors for six tree species and implications for Ca sources in northern hardwood forests

Plant and Soil - Discrimination during foliar uptake between the alkaline earth elements Ca and Sr must be understood to fully utilize Ca/Sr and 87Sr/86Sr ratios as a monitor of Ca sources to...     

Identifying calcium sources at an acid deposition-impacted spruce forest: a strontium isotope,alkaline earth element multi-tracer approach

Depletion of calcium from forest soils has important implications for forest productivity and health. Ca is available to fine feeder roots from a number of soil organic and mineral sources, but identifying the primary source or changes of sources in response to environmental change is problematic. We used strontium isotope and alkaline earth element concentration ratios of trees and soils to discern the record of Ca sources for red spruce at a base-poor, acid deposition-impacted watershed. We measured ⁸⁷Sr/⁸⁶Sr and chemical compositions of cross-sectional stemwood cores of red spruce, other spruce tissues and sequential extracts of co-located soil samples. ⁸⁷Sr/⁸⁶Sr and Sr/Ba ratios together provide a tracer of alkaline earth element sources that distinguishes the plant-available fraction of the shallow organic soils from those of deeper organic and mineral soils. Ca/Sr ratios proved less diagnostic, due to within-tree processes that fractionate these elements from each other. Over the growth period from 1870 to 1960, ⁸⁷Sr/⁸⁶Sr and Sr/Ba ratios of stemwood samples became progressively more variable and on average trended toward values that considered together are characteristic of the uppermost forest floor. In detail the stemwood chemistry revealed an episode of simultaneous enhanced uptake of all alkaline earth elements during the growth period from 1930 to 1960, coincident with reported local and regional increases in atmospheric inputs of inorganic acidity. We attribute the temporal trends in stemwood chemistry to progressive shallowing of the effective depth of alkaline earth element uptake by fine roots over this growth period, due to preferential concentration of fine roots in the upper forest floor coupled with reduced nutrient uptake by roots in the lower organic and upper mineral soils in response to acid-induced aluminum toxicity. Although both increased atmospheric deposition and selective weathering of Ca-rich minerals such as apatite provide possible alternative explanations of aspects of the observed trends, the chemical buffering capacity of the forest floor-biomass pool limits their effectiveness as causal mechanisms.     

Strontium isotopes (87Sr/86Sr) in terrestrial ecological and palaeoecological research: empirical efforts and recent advances in continental‐scale models

Strontium (Sr) isotope analysis can provide detailed biogeographical and ecological information about modern and ancient organisms. Because Sr isotope ratios (⁸⁷Sr/⁸⁶Sr) in biologically relevant materials such as water, soil, vegetation, and animal tissues predominantly reflect local geology, they can be used to distinguish geologically distinct regions as well as identify highly mobile individuals or populations. While the application of Sr isotope analysis to biological research has been steadily increasing, high analytical costs have prohibited more widespread use. Additionally, accessibility of this geochemical tool has been hampered due to limited understanding of (i) the degree to which biologically relevant materials differ in their spatial averaging of ⁸⁷Sr/⁸⁶Sr ratios, and (ii) how these differences may be affected by lithologic complexity. A recently developed continental‐scale model that accounts for variability in bedrock weathering rates and predicts Sr isotope ratios of surface water could help resolve these questions. In addition, if this ‘local water’ model can accurately predict ⁸⁷Sr/⁸⁶Sr ratios for other biologically relevant materials, there would be reduced need for researchers to assess regional Sr isotope patterns empirically. Here, we compile ⁸⁷Sr/⁸⁶Sr data for surface water, soil, vegetation, and mammalian and fish skeletal tissues from the literature and compare the accuracy with which the local water model predicts Sr isotope data among these five materials across the contiguous USA. We find that measured Sr isotope ratios for all five materials are generally close to those predicted by the local water model, although not with uniform accuracy. Mammal skeletal tissues are most accurately predicted, particularly in regions with low variability in ⁸⁷Sr/⁸⁶Sr predicted by the local water model. Increasing regional geologic heterogeneity increases both the offset and variance between modelled and empirical Sr isotope ratios, but its effects are broadly similar across materials. The local water model thus provides a readily available source of background data for predicting ⁸⁷Sr/⁸⁶Sr for biologically relevant materials in places where empirical data are lacking. The availability of increasingly high‐quality modelled Sr data will dramatically expand the accessibility of this geochemical tool to ecological applications.     

Asteriscus v. lapillus: comparing the chemistry of two otolith types and their ability to delineate riverine populations of common carp Cyprinus carpio

The chemical composition of common carp Cyprinus carpio asteriscus (vaterite) and lapillus (aragonite) otoliths from the same individual and reflecting the same growth period was measured to (1) determine whether there are differences in the uptake of trace metals (Mg:Ca, Mn:Ca, Sr:Ca and Ba:Ca ) and Sr isotope ratios (⁸⁷Sr:⁸⁶Sr) in co‐precipitating lapilli and asterisci and (2) compare the ability of multi‐element and isotopic signatures from lapilli, asterisci and both otolith types combined to discriminate C. carpio populations over a large spatial scale within a river basin. Depth profile analyses at the otolith edge using laser‐ablation inductively coupled plasma mass spectrometry showed that asterisci were enriched in Mg and Mn and depleted in Sr and Ba relative to lapilli, whilst ⁸⁷Sr:⁸⁶Sr values were nearly identical in both otolith types. Significant spatial differences among capture locations were found when all trace element and Sr isotope ratio data were aggregated into a multi‐element and isotopic signature, regardless of which otolith type was used or if they were used in combination. Discriminatory power was enhanced, however, when data for both otolith types were combined, suggesting that analysis of multiple otolith types may be useful for studies attempting to delineate C. carpio populations at finer spatial or temporal scales.     

Membrane Currents Carried by Ca, Sr, and Ba in Barnacle Muscle Fiber During Voltage Clamp

Membrane currents associated with voltage clamp of the giant muscle fibers of a barnacle, Balanus nubilus, were analyzed in terms of currents of the Ca and K channels. Although the activation of the K channel occurs more slowly than that of the Ca channel, both currents show a significant temporal overlap. The currents carried by Ca⁺⁺, Sr⁺⁺, or Ba⁺⁺ through the Ca channel were compared under the conditions at which this overlap was the least. When only one divalent cation is present in the solution, Ba⁺⁺ carries more current than Ca⁺⁺ or Sr⁺⁺ and the sequence of the current is Ba > Sr ≈ Ca. When the external solution contains a relatively high concentration of Co⁺⁺, which is a blocking agent for the Ca channel, inversion of the sequence occurs, to Ca > Sr > Ba. This is due to the fact that the blocking effect differs depending on which ion carries current through the Ca channel. The Ba current is most sensitive and the Ca current is least affected. Ba suppresses the current of the K channel, independently of its current-carrying function through the Ca channel.     

Test of soil extractants for their suitability in predicting Ca/Sr ratios in leaves and stems of sugar maple seedlings

Differential uptake and translocation of Ca and Sr in organisms have been reported, calling into question the use of Sr to track Ca cycling in the environment. We investigated the relationship between Ca/Sr ratios in soil extracts of various strengths (H₂O, NH₄Cl, and NH₄EDTA) and seedlings of sugar maple (Acer saccharum Marsh.) grown from natural regeneration on 37 sites. Our objectives were to determine if Ca/Sr ratios in soil extracts are correlated with those in sugar maple tissues, and what soil extractant best duplicate plant tissue Ca/Sr ratios. Leaves had higher Ca/Sr ratios than stems and the extractants did not produce equal Ca/Sr ratios: H₂O had the lowest Ca/Sr, and NH₄EDTA the highest. The relationships between soil extract Ca/Sr ratios and leaf and stem Ca/Sr ratios were significant and linear, but the slopes differed among extractants. The lowest slope (0.45) was observed for the water extract/leaves and the highest (2.15) for the NH₄EDTA extract/stem with discrimination factors ranging from 0.22 with NH₄EDTA to 1.59 for water. Leaf extracts were more strongly correlated with soil Ca/Sr than stem extracts (R ² of 0.57–0.7 vs. R ² of 0.45–0.6, respectively). These findings support the use of Ca/Sr ratios in plants to track their source of soil Ca, but they highlight the need to calibrate the relationships for the plant tissue and soil extractant used.     

Distinguishing sources of base cations in irrigated and natural soils: evidence from strontium isotopes

Strontium isotope ratios (⁸⁷Sr/⁸⁶Sr) of soil solids, soil cation extracts, irrigation water and plant material are used to determine strontium and therefore cation sources and fluxes in irrigated and natural soil–plant systems. Strontium isotopes of soil solids from four soil profiles (two irrigated vineyard soils and two 'natural' profiles from nearby reserves) show large differences between soil horizons with depth. These differences are not reflected in ⁸⁷Sr/⁸⁶Sr ratios of soil labile cations, which show both little variation down-profile and much lower ratios than soil solids. In the undisturbed, natural soil profiles, labile cation ⁸⁷Sr/⁸⁶Sr ratios are close to the ratio of modern seawater, indicating that solutes of marine origin from precipitation are the primary input of strontium (and calcium) to the labile cation pool. In the irrigated soil profiles, ⁸⁷Sr/⁸⁶Sr ratios of labile cations are consistently shifted towards that of the irrigation water. Mass-balance calculations using ⁸⁷Sr/⁸⁶Sr ratios of the different inputs to the labile cation pool indicate more than 90% of labile strontium is derived from precipitation solutes in unirrigated soils, and up to 44% from irrigation water solutes as an additional source in irrigated soils. The ⁸⁷Sr/⁸⁶Sr ratios of grapes grown in irrigated soils match precisely with those of the labile soil cations, demonstrating that cation nutrients are drawn wholly from the labile cation pool and have the same mix of precipitation, irrigation, and soil solid sources. The ⁸⁷Sr/⁸⁶Sr ratios of grapes grown in the irrigated soils may therefore vary over time depending on (1) the changing mix of irrigation water and local precipitation and (2) potential change to irrigation water. These findings suggest limitations to the use of strontium isotopes in the tracing of grapes and wines to their soil of origin.     

Paleoceanography of the Late Cretaceous (Maastrichtian) Western Interior Seaway of North America: evidence from Sr and O isotopes

Well-preserved fossils of the Late Cretaceous Western Interior Seaway (WIS) of North America have been analyzed for Sr concentration and Sr and O isotopes in order to decipher paleosalinities and paleotemperatures. The samples are from four biofacies within the Seaway (late Maastrichtian): offshore Interior (Pierre Shale), nearshore Interior (Fox Hills Formation), brackish (reduced salinity; Fox Hills Formation) and freshwater (Hell Creek Formation). Samples were also obtained from the Severn Formation of Maryland (considered to be representative of the open ocean). All biofacies (except the freshwater) are demonstrably within the Jeletzkytes nebrascensis ammonite zone (<1 Ma duration). The ⁸⁷Sr/⁸⁶Sr ratios show significant and systematic decreases from marine (mean±1 S.D.=0.707839±0.000024) to brackish facies (mean±1 S.D.=0.707677±0.000036), consistent with dilution by freshwater with a lower ⁸⁷Sr/⁸⁶Sr ratio than seawater. Such variation disallows using the ⁸⁷Sr/⁸⁶Sr ratios of fossil shell material to assign ages to fossils from the Late Cretaceous WIS without knowledge of the salinity in which the organism grew. The Sr isotope ratios for scaphitid ammonites within a single biofacies are similar to each other and different from those for scaphites in other biofacies, implying that these organisms are restricted in their distribution during life. The ⁸⁷Sr/⁸⁶Sr values of freshwater unionid mussels range widely and are not compatible with the freshwater endmember ⁸⁷Sr/⁸⁶Sr ratio required by the trend in ⁸⁷Sr/⁸⁶Sr vs. biofacies established from the other samples. Paleosalinities for the biofacies are estimated to range from 35‰ in the open marine to a minimum of 20‰ in the brackish, based on the presence of cephalopods in all four facies and the known salinity tolerance of modern cephalopods. Producing reasonable ⁸⁷Sr/⁸⁶Sr values for the freshwater endmember of a ⁸⁷Sr/⁸⁶Sr vs. 1/[Sr] plot requires a Sr concentration 0.2-0.5 that of seawater for the dominant freshwater input to the WIS. Such high Sr concentrations (relative to seawater) are not observed in modern rivers, and we suggest that the brackish environment in the WIS arose through the mixing of freshwater and seawater in a nearshore aquifer system. Reactions of the solution with aquifer solids in this ‘subterranean estuary’ [Moore, Mar. Chem. 65 (1999) 111-125] produced brackish water with the Sr concentration and isotopic composition recorded in the brackish biofacies. δ¹⁸O values of the fossils show decreases from the marine to brackish biofacies consistent with increasing temperatures (from ∼13 to 23°C) or, if temperatures were relatively constant, to a decrease in the δ¹⁸O of the water in which the shell formed. The latter interpretation is consistent with less-than-fully marine salinities in the nearshore biofacies, but both changes in temperature and the isotopic composition of the water may have occurred in this environment.     

Evaluation of the mobility and discrimination of Ca, Sr and Ba in forest ecosystems: consequence on the use of alkaline-earth element ratios as tracers of Ca

A comprehensive understanding of Ca cycling in an ecosystem is desirable because of the role of this element in tree mineral nutrition and its status as a major base cation on the soil exchange complex. The determination of the origin of Ca in forests is particularly indicated in regard of important changes linked to acid inputs and intensive logging. Natural strontium isotopes are increasingly used as tracers of Ca in forest ecosystems for qualitative and quantitative assessments. Nevertheless this method is limited to relatively simple systems with two sources of nutrients. Some recent studies coupled Sr/Ca or Sr/Ba ratios to Sr isotopic measurements in order to solve more complex systems. Such method has however associated with it some uncertainties: this approach assumed that Ca, Sr and Ba behave similarly throughout the ecosystem and does not take into account the Ca biopurification processes occurring in some tree’s organs which can alter element ratio. The present work focuses on two deciduous species covering large areas in Europe: European beech (Fagus sylvatica L.) and pedunculate oak (Quercus robur L.). In order to test the similarity of behaviour between Ca, Sr and Ba, their concentrations were measured extensively in the major compartments of two forest ecosystems. In parallel, the discrimination process inside tree organs was studied in 23 stands for beech and 10 stands for oak. We found that Sr and Ca behave similarly in all soil and tree compartments. By contrast, Ba and Ca appear to have contrasting behaviours, especially in streams, soil solution and soil exchange complex (no correlations between element concentrations). Sr/Ba and Ba/Ca ratios must therefore be used with care as tracer of Ca. The Ca biopurification is absent in roots and slight in bole wood but is large in bark, twigs and leaves. The discrimination factors (DF) between wood and leaves are characteristic of the two species studied and do not change significantly as a function of the soil Ca status (acidic or calcareous soils). Therefore, strontium–calcium DF can be used as a correction factor of the Sr/Ca ratio of leaves when this ratio is used in connection with Sr isotopic ratios. This correction allows to solve systems of tree nutrition with more than two sources of Ca.