Differential diagenesis of strontium in archaeological human dental tissues

The investigation of prehistoric human migration from the measurement of Sr-isotope ratios within preserved tissue is critically dependent on the preservation of biogenic Sr. A number of recent studies have involved isotope ratio measurements on samples of archaeological tooth and bone, but doubt remains as to the extent of diagenesis in various skeletal tissues and the effectiveness of procedures designed to decontaminate them. The authors have compared Sr abundance and isotope ratios in enamel and dentine from archaeological teeth in order to assess the integrity of the biogenic Sr signal preserved within the respective tissues. It is concluded that enamel appears, in most cases, to be a reliable reservoir of biogenic Sr, but that dentine, and by implication bone, is not. The diagenesis of dentine is highly variable even between burials within a single site. For the majority of teeth, dentine diagenesis was not simply by addition of soil-derived Sr, but involved substantial, sometimes complete, turnover of the original biogenic material. It is suggested that, for most of the samples investigated, current decontamination techniques may not have been effective in isolating biogenic Sr from dentine. Similar considerations are likely to apply to archaeological and fossil bone, but the possibility arises to use dentine and enamel measurements to assess the effectiveness of decontamination procedures which may then be used for bone.     

Determination of Sr isotopes in calcium phosphates using laser ablation inductively coupled plasma mass spectrometry and their application to archaeological tooth enamel

The determination of accurate Sr isotope ratios in calcium phosphate matrices by laser ablation multi-collector ICP-MS is demonstrated as possible even with low Sr concentration archaeological material. Multiple on-line interference correction routines for doubly-charged REE, Ca dimers and Rb with additional calibration against TIMS-characterised materials are required to achieve this. The calibration strategy proposed uses both inorganic and biogenic apatite matrices to monitor and correct for a ⁴⁰Ca-³¹P-¹⁶O polyatomic present at levels of 0.3-1% of the non-oxide peak, which interferes on ⁸⁷Sr causing inaccuracies of 0.03-0.4% in the ⁸⁷Sr/⁸⁶Sr isotope ratio. The possibility also exists for synthetic materials to be used in this calibration. After correction for interferences total combined uncertainties of 0.04-0.15% (2SD) are achieved for analyses of 13-24 μg of archaeological tooth enamel with Sr concentrations of ca. 100-500 ppm using MC-ICP-MS. In particular, for samples containing >300 ppm Sr, total uncertainties of ∼0.05% are possible utilising 7-12 ng Sr. Data quality is monitored by determination of ⁸⁴Sr/⁸⁶Sr ratios.When applied to an archaeological cattle tooth this approach shows Sr-isotope variations along the length of the tooth in agreement with independent TIMS data. The ⁴⁰Ca-³¹P-¹⁶O polyatomic interference is the root cause of the bias at mass 87 during laser ablation ICP-MS analysis of inorganic and biogenic calcium phosphate (apatite) matrices. This results in inaccurate ⁸⁷Sr/⁸⁶Sr ratios even after correction of Ca dimers and doubly charged rare earth elements. This interference is essentially constant at specific ablation conditions and therefore the effect on ⁸⁷Sr/⁸⁶Sr data varies in proportion to changes in the Sr concentration of the ablated material. Complete elimination of this interference is unlikely through normal analytical mechanisms and therefore represents a limitation on the achievable accuracy of LA-(MC-)ICP-MS ⁸⁷Sr/⁸⁶Sr data without rigorous calibration to known reference materials.     

Analysis of coupled Sr/Ca and Sr/Sr variations in enamel using laser-ablation tandem quadrupole-multicollector ICPMS

We present in this study results obtained with a laser-ablation coupled with both a quadrupole and a multi-collector ICPMS. The simultaneous in situ Sr/Ca and ⁸⁷Sr/⁸⁶Sr measurements along growth profiles in enamel allows the concomitant diet and migration patterns in mammals to be reconstructed. Aliquots of the powdered international standard NIST “SRM1400 Bone Ash” with certified Sr and Ca contents, was sintered at high pressure and temperature and was adopted as the reference material for external reproducibility and calibration of the results. A total of 145 coupled elemental and isotopic measurements of herbivores enamel from the Kruger National Park, South Africa, gives intra-tooth Sr/Ca and ⁸⁷Sr/⁸⁶Sr variations that are well larger than external reproducibility. Sr/Ca profiles systematically decrease from the dentine-enamel junction to the outer enamel whereas ⁸⁷Sr/⁸⁶Sr profiles exhibit variable patterns. Using a simple geometric model of hypsodont teeth growth, we demonstrate that a continuous recording of the ⁸⁷Sr/⁸⁶Sr variations can be reconstructed in the tooth length axis. This suggests that the mobility of a mammal can be reconstructed over a period of more than a year with a resolution of a ten of days, by sampling enamel along growth profiles. Our geometric model of hypsodont teeth growth predicts that an optimal distance between two successive profiles is equal to the enamel thickness. However, this model does not apply to the Sr/Ca signal which is likely to be altered during the enamel maturation stage due to differential maturation processes along enamel thickness. Here, the observed constant decreases of the Sr/Ca ratios in the ungulates of Kruger National Park suggests that they did not changed of diet, while some of them were migrating.     

山西省襄汾县陶寺遗址出土动物牙釉质的锶同位素比值分析

锶同位素分析技术已经成为国际考古学界用于探索人和动物迁移活动的主要方法.陶寺遗址位于山西省襄汾县陶寺镇,距今4500～3900年,是目前我国规模最大的、显现文明化程度最高的史前聚落遗址之一.文章通过热电离质谱分析方法对山西襄汾县陶寺镇陶寺遗址龙山晚期出土动物的14个动物牙釉质的锶同位素比值进行了测定.研究结果表明,5个...     

87Sr/86Sr isotope composition of bottled British mineral waters for environmental and forensic purposes

Mineral waters in Britain show a wide range of ⁸⁷Sr/⁸⁶Sr isotope compositions ranging between ⁸⁷Sr/⁸⁶Sr = 0.7059 from Carboniferous volcanic rock sources in Dunbartonshire, Scotland to ⁸⁷Sr/⁸⁶Sr = 0.7207 in the Dalradian aquifer of Aberdeenshire, Scotland. The ⁸⁷Sr/⁸⁶Sr composition of the waters shows a general correlation with the aquifer rocks, resulting in the waters from older rocks having a more radiogenic signature than those from younger rocks. This wide range of values means that the Sr isotope composition of mineral water has applications in a number of types of studies. In the modern commercial context, it provides a way of fingerprinting the various mineral waters and hence provides a method for recognising and reducing fraud. From an environmental perspective, it provides the first spatial distribution of bio-available ⁸⁷Sr/⁸⁶Sr in Britain that can be used in modern, historical and archaeological studies.     

Sr/Sr isotope fingerprinting of Scottish and Icelandic migratory shorebirds

Biosphere Sr isotope composition data from Iceland and Scotland suggest that terrestrially feeding birds from these two countries will have significantly different ⁸⁷Sr/⁸⁶Sr isotope composition in their tissues. The aim of this study is to test if these differences can be measured within the bone and feather of migratory wading birds, who feed terrestrially as juveniles, thus providing a provenance tool for these birds.     

Determination of Sr/Sr mass-dependent isotopic fractionation and radiogenic isotope variation of Sr/Sr in the Neoproterozoic Doushantuo Formation

We measured both mass-dependent isotope fractionation of δ⁸⁸Sr (⁸⁸Sr/⁸⁶Sr) and radiogenic isotopic variation of Sr (⁸⁷Sr/⁸⁶Sr) for the Neoproterozoic Doushantuo Formation that deposited as a cap carbonate immediately above the Marinoan-related Nantuo Tillite. The δ⁸⁸Sr and ⁸⁷Sr/⁸⁶Sr compositions showed three remarkable characteristics: (1) high radiogenic ⁸⁷Sr/⁸⁶Sr values and gradual decrease in the ⁸⁷Sr/⁸⁶Sr ratios, (2) anomalously low δ⁸⁸Sr values at the lower part cap carbonate, and (3) a clear correlation between ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr values. These isotopic signatures can be explained by assuming an extreme greenhouse condition after the Marinoan glaciation. Surface seawater, mixed with a large amount of freshwater from continental crusts with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios, was formed during the extreme global warming after the glacial event. High atmospheric CO₂ content caused sudden precipitation of cap carbonate from the surface seawater with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios. Subsequently, the mixing of the underlying seawater, with unradiogenic Sr isotope compositions and normal δ⁸⁸Sr ratios, probably caused gradual decrease of the ⁸⁷Sr/⁸⁶Sr ratios of the seawater and deposition of carbonate with normal δ⁸⁸Sr ratios. The combination of ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr isotope systematics gives us new insights on the surface evolution after the Snowball Earth.     

The Origin of Paleokarst in the Huanglong Formation of the Eastern Sichuan Basin: Evidence from δ13C, δ18O and 87Sr/86Sr

Karst rocks from the Huanglong Formation exposed at the margin of the Eastern Sichuan Basin can be divided into four types:slightly corroded, moderately corroded porous, intensely corroded brecciated and intensely corroded and replaced secondary calcic karstic rocks. The carbon, oxygen and strontium isotope compositions of the various karst rocks are analyzed systematically and compared to rocks without karst corrosion. The results indicate that(1) the Huanglong Formation in the eastern Sichuan Basin was a restricted bay supplied and controlled by freshwater in which mudmicrite and mud-dolomicrite exhibit low δ13C and δ18O values and high 87Sr/86 Sr ratios;(2) all types of karstic rocks in the paleokarst reservoirs of the Huanglong Formation in the research area are affected by atmospheric freshwater with the δ13C and δ18O values and 87Sr/86 Sr ratios in the original formation approaching those of atmospheric freshwater, which reflects ancient hydrological conditions, fluid properties, isotopic source and the fractionation effect;(3) the intensely corroded and replaced secondary limestone is affected by a variety of diagenetic fluids, often reflected by δ13C and δ18O values, while the 87Sr/86 Sr ratios exhibit the strong degree of the corrosion;(4) after comparing the 87Sr/86 Sr ratios of each type of karst rock, the diagenetic fluids are determined to be mainly atmospheric freshwater, and depending on the strength of corrosion, and the low 87Sr/86 Sr ratio fluids in the layer will participate in the karst process. The carbon, oxygen, and strontium isotopes of different karstic reservoirs can provide meaningful geochemical information for forecasting and evaluating the development and distribution rules of the Huanglong Formation at the margin of the eastern Sichuan Basin in time and space.     

Enamel diagenesis at South African Australopith sites: Implications for paleoecological reconstruction with trace elements

Elemental ratio data from archaeological and paleontological bone have often been used for paleoecological reconstruction, but recent studies have shown that, even when solubility profiling techniques are employed in an attempt to recover biogenic signals, bone is an unreliable material. As a result, there has been renewed interest in using enamel for such studies, as it is known to be less susceptible to diagenesis. Nevertheless, enamel is not immune from diagenetic processes, and several studies have suggested that paleoecologically relevant elements may be altered in fossil enamel. Here, we investigate Sr, Ba, Zn, and Pb compositions of enamel from South African karstic cave sites in an effort to ascertain whether or not this material provides reliable paleoecological information. We compared enamel data for mammals from three fossil sites aged 1.8-3.0 Ma, all of which are on dolomites, with data from modern mammals living on dolomitic and granitic substrates. Sr/Ca and Ba/Ca are about three times higher in enamel from modern mammals on granites than those living on dolomites, stressing the need for geologically appropriate modern/fossil comparisons. After pretreatment with dilute acid, we found no evidence of increased Sr/Ca, Ba/Ca, or Pb/Ca in fossil enamel. In contrast, Zn/Ca increased by over five times at one site (Makapansgat), but much more subtly elsewhere. Ecological patterning in Sr/Ca, Ba/Ca, and Sr/Ba ratios was also retained in fossil enamel. This study suggests that Sr/Ca, Ba/Ca, and Pb/Ca data likely preserve paleoecological information from these sites, but also demonstrates that geologically similar sites can differ in the degree to which they impart certain elements (Zn in this case) to fossils. Thus, screening is probably necessary on a site-by-site basis. Lastly, further investigation of elemental distributions in modern foodwebs is necessary before elemental ratio analysis can become a common tool for paleoecological reconstruction.     

Comparative behaviour of recently deposited radiostrontium and atmospheric common strontium in soils (Vosges mountains,France)

The vertical distribution of atmospheric ⁸⁷Sr/⁸⁶Sr isotope ratios in soil is compared to the distribution of recent atmospheric ⁹⁰Sr deposition. ⁸⁷Sr/⁸⁶Sr isotope ratios of soil leachates are correlated with ⁹⁰Sr activities. Samples from the uppermost part of a soil profile have low ⁸⁷Sr/⁸⁶Sr ratios and high ⁹⁰Sr activities. Samples from the deeper part of the soil profile, however, have high ⁸⁷Sr/⁸⁶Sr but low ⁹⁰Sr activities. This points to mixing between an atmospheric and a geogenic component. Mixing calculations indicate that 50–80% of the Sr in the topsoil of a small catchment in the Vosges mountains is of atmospheric origin. Similarly ⁸⁷Sr/⁸⁶Sr of roots point to the presence of an atmospheric and geogenic component. ⁸⁷Sr/⁸⁶Sr ratios of soil leachates and corresponding roots are very similar indicating, that the roots integrate at each level of the soil profile the leachable Sr of the corresponding soil.     

Resolving archaeological populations with Sr-isotope mixing models

Strontium isotope analysis of tooth enamel is a useful provenancing technique to investigate the childhood origins and residential mobility of ancient people. However, where different geographical target regions have similar biosphere ⁸⁷Sr/⁸⁶Sr it is often difficult to resolve the ⁸⁷Sr/⁸⁶Sr ranges of two different groups of people and establish what constitutes the local range at each site. Here a multi-period study is presented from the Outer Hebrides, Scotland and an investigation of Neolithic and Early Bronze Age populations from the Yorkshire Wolds, NE England. The aim is to demonstrate that, despite complex human dietary strategies, simple mixing systems with only two end-members do occur in archaeological human populations in certain geological provinces and, despite overlapping ⁸⁷Sr/⁸⁶Sr ranges, it is possible to separate two populations based on the structure within the data set.     

贾湖史前人类迁移行为的初步研究——锶同位素分析技术在考古学中的运用

位于河南省舞阳县的贾湖遗址是一处著名的新石器时代遗址,距今7800～9000年。遗址中出土了大量的人和动物的骨骼与牙齿,这为研究史前时期中国中部地区人类的迁移情况提供了很好的材料。在本次研究中,共分析了26个人和动物样品,包括12个人体骨密质样品、9个人牙釉质样品和5个猪牙釉质样品。测定了每个样品的锶同位素浓度和87Sr/86Sr比值,结果表明猪牙釉质的锶同位素浓度（平均值为196±51ppm,n=5,1σ）高于人牙釉质的浓度（平均值为110±61ppm,n=9,1σ）,人骨骼的锶同位素浓度（平均值为444±173ppm,n=12,1σ）明显地高于人牙釉质的浓度。根据5个猪牙釉质样品87Sr/86Sr平均值±2倍的标准偏差确定的当地锶同位素比值范围（0.712205～0.712420）,发现14个人类个体中有5个是外来迁入的,并且从第1期到第3期人口的迁移率有增加的趋势。这是在国内首次利用锶位素分析方法对古人类的迁移现象进行研究,同时也表明此方法可以很好地判断古人类迁移行为。     

Non-uniqueness and interpretation of the seawater Sr/Sr curve

Variations in the seawater ⁸⁷Sr/⁸⁶Sr curve through time can be caused by fluctuations in the strontium flux or variations in the isotopic ratio from at least six different sources and sinks. Thus, 12 or more parameters control each single measurement although widely accepted assumptions allow this to be reduced to typically six unknowns. Interpreting the causes of time-variation in the seawater ⁸⁷Sr/⁸⁶Sr curve is therefore hampered by inherent non-uniqueness. However, this problem is under-constrained rather than unconstrained. As a result, whilst there are an infinite number of possible interpretations, these all come from a few families of very similar solutions. Using this insight, it is possible to find solutions having the smallest possible variations in source flux or source ⁸⁷Sr/⁸⁶Sr ratio. Thus, lower-bounds can be placed upon the source variations responsible for the observed fluctuations in the seawater ⁸⁷Sr/⁸⁶Sr curve. When applied to the evolution of the Early Jurassic ⁸⁷Sr/⁸⁶Sr seawater curve, this approach demonstrates that a short-lived Toarcian event is genuine since it is present in all models, regardless of the values chosen for the unknown source fluxes and unknown source isotope ratios. However, the variations in strontium flux or isotopic ratio necessary to explain the Toarcian event may be significantly smaller than would be predicted assuming modern values for the unknown parameters.     

Sr and Sr/Sr in the Yamuna River System in the Himalaya: sources, fluxes, and controls on sr isotope composition

Sr and ⁸⁷Sr/⁸⁶Sr have been measured in the Yamuna river headwaters and many of its tributaries (YRS) in the Himalaya. These results, with those available for major ions in YRS rivers and in various lithologies of their basin, have been used to determine their contributions to riverine Sr and its isotopic budget. Sr in the YRS ranges from 120 to 13,400 nM, and ⁸⁷Sr/⁸⁶Sr from 0.7142 to 0.7932. Streams in the upper reaches, draining predominantly silicates, have low Sr and high ⁸⁷Sr/⁸⁶Sr whereas those draining the lower reaches exhibit the opposite resulting from differences in drainage lithology. ⁸⁷Sr/⁸⁶Sr shows significant co-variation with SiO₂/TDS and (Na^* + K)/TZ⁺ (indices of silicate weathering) in YRS waters, suggesting the dominant role of silicate weathering in contributing to high radiogenic Sr. This is also consistent with the observation that streams draining largely silicate terrains have the highest ⁸⁷Sr/⁸⁶Sr, analogous to that reported for the Ganga headwaters. Evaluation of the significance of other sources such as calc-silicates and trace calcites in regulating Sr budget of these rivers and their high ⁸⁷Sr/⁸⁶Sr needs detailed work on their Sr and ⁸⁷Sr/⁸⁶Sr. Preliminary calculations, however, indicate that they can be a significant source to some of the rivers.It is estimated that on an average, ∼25% of Sr in the YRS is derived from silicate weathering. In the lower reaches, the streams receive ∼15% of their Sr from carbonate weathering whereas in the upper reaches, calc-silicates can contribute significantly (∼50%) to the Sr budget of rivers. These calculations reveal the need for additional sources for rivers in the lower reaches to balance their Sr budget. Evaporites and phosphorites are potential candidates as judged from their occurrence in the drainage basin. In general, Precambrian carbonates, evaporites, and phosphorites “dilute” the high ⁸⁷Sr/⁸⁶Sr supplied by silicates, thus making Sr isotope distribution in YRS an overall two end member mixing. Major constraints in quantifying contributions of Sr and ⁸⁷Sr/⁸⁶Sr from different sources to YRS rivers are the wide range in Sr and ⁸⁷Sr/⁸⁶Sr of major lithologies, limited data on Sr and ⁸⁷Sr/⁸⁶Sr in minor phases and on the behavior of Sr, Na, and Ca during weathering and transport.The Ganga and the Yamuna together transport ∼0.1% of the global Sr flux at the foothills of the Himalaya which is in the same proportion as their contribution to global water discharge. Dissolved Sr flux from the Yamuna and its mobilization rate in the YRS basin is higher than those in the Ganga basin in the Himalaya, a result consistent with higher physical and chemical erosion rates in the YRS.     

Sr/Sr and Sr/Ca in speleothems for paleoclimate reconstruction in Central China between 70 and 280 kyr ago

Limestone cave deposits (speleothems) provide archives for past changes in regional climates over a range of timescales. While δ¹⁸O and δ¹³C in speleothem calcite have been commonly used for reconstruction of paleoclimates, we report here further efforts in the use of ⁸⁷Sr/⁸⁶Sr and Sr/Ca signals in speleothem calcite to deduce paleomonsoon variability near the Loess Plateau of central China. A two end-member mass-balance model of concentration and isotopic composition of strontium in a cave system is used to estimate variation of the ⁸⁷Sr/⁸⁶Sr ratio in sediments overlying a limestone cave. We show that this ratio reflects climate-driven variations in the provenance and the extent of chemical weathering of the epikarstic sediments. The measurements of ⁸⁷Sr/⁸⁶Sr made on a well-dated stalagmite, SFL, from Buddha Cave (33^o40N′ 109^o05′E) show ratios of 0.71092 to 0.71133 (±0.00001 as 2σ) during relatively cold periods (e.g., Marine Isotope Stage (MIS) 5b, 5d, and 8), lower than ratios of 0.71133 to 0.71194 during relatively warm periods (e.g., MIS 5a, 5c, 5e, and 7). As changes in the Sr/Ca ratio may affect speleothem ⁸⁷Sr/⁸⁶Sr, we show that the direct use of speleothem ⁸⁷Sr/⁸⁶Sr is less ideal than our modeled ⁸⁷Sr/⁸⁶Sr for the exogenic Sr source above the cave as a paleomonsoon proxy. Using the δ¹⁸O, δ¹³C, Sr/Ca, and ⁸⁷Sr/⁸⁶Sr records of the stalagmite, we reconstruct the variability of the East Asian monsoon for the time period between 70 and 280 kyr ago. The results show that summer monsoons were more intense during interglacial periods than during glacial periods.     

Initial 87Sr/86Sr ratios of plutonic rocks from Japan

Initial ⁸⁷Sr/⁸⁶Sr rations were determined for more than 80 plutonic rocks in Japan. The ⁸⁷Sr/⁸⁶Sr ratios of gabbroic and granitic rocks show no significant difference in plutonic terranes where both rocks occur closely associated, implying a genetic relationship between them (e.g., Green Tuff belt) or reequilibration at deep level (e.g., Ryoke belt). Wherever granitic rocks occur independently from gabbroic rocks, the granites have higher ratios than the gabbros.Initial ⁸⁷Sr/⁸⁶Sr ratios of the granitic rocks are low (<0.706) in Northeast Japan but high (<0.706) in Southwest Japan, the boundary being the Tanakura Tectonic Line. Within Southwest Japan, the ratios are low along the Japan Sea side of the southernmost area. This regional variation is generally correlated with thickness of the continental crust as deduced from the Bouguer anomaly.Initial ⁸⁷Sr/⁸⁶Sr ratios of the granitic rocks vary from 0.7037 to 0.7124. The low group (<0.706) is considered to consist of essentially mantle-derived magmas contaminated by crustal material in lesser but varying degree, because of its geological setting and initial ⁸⁷Sr/⁸⁶Sr values. The high group may have been formed by contamination of a deep-seated magmas by crustal material or by generation of the main part of the magmas within the continental crust. The ratios of individual belts reflect their own history depending upon age and Rb/Sr ratio of the crustal material.Initial ⁸⁷Sr/⁸⁶Sr ratios of granitic rocks are generally low for the magnetite-series but high for the ilmenite-series. Thus, a negative correlation is observed between initial ratios and ³⁴S for most Cretaceous-Paleogene granites. However, Neogene ilmenite-series granites are low in both initial ⁸⁷Sr/⁸⁶Sr and ³⁴S indicating interaction of the granitic magma with young sedimentary rocks enriched in ³²S.     

87Sr/86Sr in waters from the Lincolnshire Limestone aquifer,England, and the potential of natural strontium isotopes as a tracer for a secondary recovery seawater injection process in oilfields

The Sr isotope composition of formation waters is a sensitive indicator of diagenetic processes in the host sediments, mixing processes between different bodies of water, and the connectivity of hydrological systems. The⁸⁷Sr/⁸⁶Sr ratio of present seawater is constant worldwife, while formation waters in hydrocarbon reservoirs have various values, depending on the aforementioned effects, in most cases different from modern seawater. This forms the basis of anatural tracer technique for seawater injection projects, involving characterization of the⁸⁷Sr/⁸⁶Sr ratios and Sr contents of formation waters in the reservoir before injection commences, followed by monitoring of these parameters in the produced water as injection proceeds. This method is best suited to reservoirs in which the formation waters have low Sr concentrations and⁸⁷Sr/⁸⁶Sr ratios much higher or lower than seawater. Available data for reservoir formation waters suggest that breakthrough recognition could be expected at <10% seawater in many sandstone reservoirs, while the method would be less sensitive in carbonate reservoir or situations where the formation waters had interacted with evaporites, as the associated waters tend to have high Sr contents. In heterogeneous but well-mapped reservoirs, it may be possible to obtain information about flow paths/mechanismsbefore breakthrough. Combination with other chemical and isotopic tracers creates a very powerful tool, the Sr method acting as a safeguard should the batch of water containing the conventional tracers be overtaken by subsequently injected seawater. The Sr method could also be used for injection projects that were begun without the addition of tracers. A natural analogue of a water injection process is found in the Jurassic Lincolnshire Limestone aquifer in England, where rapidly moving fresh meteoric water mixes progressively with an older saline formation water. The⁸⁷Sr/⁸⁶Sr data enable quantitative modelling of this mixing process. The infiltrating fresh water becomes progressively modified by dissolution of detrital carbonate and calcite cement in the limestone, with depth becoming increasingly dominated by Sr derived from the more soluble detrital components. The saline formation water contains water molecules of meteoric origin and an⁸⁷Sr/⁸⁶Sr ratio much higher than Jurassic seawater or marine carbonate; the solute content has been influence by interaction of the water with non-carbonate phases.     

Ca/Sr and Sr isotope systematics of a Himalayan glacial chronosequence: carbonate versus silicate weathering rates as a function of landscape surface age

We explored changes in the relative importance of carbonate vs. silicate weathering as a function of landscape surface age by examining the Ca/Sr and Sr isotope systematics of a glacial soil chronosequence located in the Raikhot watershed within the Himalaya of northern Pakistan. Bedrock in the Raikhot watershed primarily consists of silicate rock (Ca/Sr ≈ 0.20 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.77 to 1.2) with minor amounts of disseminated calcite (Ca/Sr ≈ 0.98 to 5.3 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.79 to 0.93) and metasedimentary carbonate (Ca/Sr ≈ 1.0 to 2.8 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.72 to 0.82). Analysis of the exchangeable, carbonate, and silicate fractions of seven soil profiles ranging in age from ∼0.5 to ∼55 kyr revealed that carbonate dissolution provides more than ∼90% of the weathering-derived Ca and Sr for at least 55 kyr after the exposure of rock surfaces, even though carbonate represents only ∼1.0 wt% of fresh glacial till. The accumulation of carbonate-bearing dust deposited on the surfaces of older landforms partly sustains the longevity of the carbonate weathering flux. As the average landscape surface age in the Raikhot watershed increases, the Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios released by carbonate weathering decrease from ∼3.6 to ∼0.20 μmol/nmol and ∼0.84 to ∼0.72, respectively. The transition from high to low Ca/Sr ratios during weathering appears to reflect the greater solubility of high Ca/Sr ratio carbonate relative to low Ca/Sr ratio carbonate. These findings suggest that carbonate weathering controls the dissolved flux of Sr emanating from stable Himalayan landforms comprising mixed silicate and carbonate rock for tens of thousands of years after the mechanical exposure of rock surfaces to the weathering environment.     

87Sr/86Sr in kimberlitic carbonates by ion microprobe: Hydrothermal alteration,crustal contamination and relation to carbonatite

Carbonates in a 30 cm wide zoned kimberlite dyke from the De Beers Mine, Kimberley, S. Africa were studied by cathodoluminescence and electron microprobe techniques and their ⁸⁷Sr/⁸⁶Sr ratios were measured using an AEI-IM20 ion microprobe. Primary carbonates (including calcite dendrites, rhombohedral calcites in segregation vesicles and mosaic dolomite) have high Sr (0.69–1.35 wt.% SrO) and Ba (0.24–0.44% BaO) and ⁸⁷Sr/⁸⁶Sr ratios in the range 0.7046 to 0.7056. Secondary sparry calcite in amygdales and veins is characterised by low Ba (<0.05% BaO) and ⁸⁷Sr/⁸⁶Sr near 0.72. Rhombohedral calcite 0.5 cm from a contact with 2,900 my. old biotite-gneiss has minor element chemistry like that of primary carbonate, but an elevated ⁸⁷Sr/⁸⁶Sr ratio of 0.7103, possibly indicating crustal contamination in a boundary layer of the kimberlite magma. Amygdale-like segregations of carbonate and/or serpentine originated as gas-cavities and were not formed by liquid immiscibility. They are now filled either by secondary calcite or by minerals precipitated from residual kimberlite liquid. However, dendritic calcite and primary dolomite and calcite with high Sr, Ba and low ⁸⁷Sr/⁸⁶Sr demonstrate shared chemical characteristics between these carbonates and carbonatite. The primary kimberlite magma had initial ⁸⁷Sr/⁸⁶Sr close to 0.7046.     

The geographic distribution of Sr isotopes from surface waters and soil extracts over the island of Bornholm (Denmark) – A base for provenance studies in archaeology and agriculture

In this paper we report the Sr isotope signatures, and Sr, Al and Na concentrations of 30 surface waters (lakes/ponds and rivers/creeks) and 19 soil sample extracts from the island of Bornholm (Denmark) and present a categorized ⁸⁷Sr/⁸⁶Sr value distribution map that may serve as a base for provenance studies, including archaeological migration and authenticity proof for particular food products. The Sr isotopic compositions of surface waters range from ⁸⁷Sr/⁸⁶Sr = 0.7097–0.7281 (average 0.7175 ± 0.0049; 1σ), whereas 0.1 M HNO₃, 0.05 M HNO₃, and 0.01 M CaCl₂ soil extracts range from ⁸⁷Sr/⁸⁶Sr = 0.7095–0.7197 and define somewhat lower but statistically indistinguishable averages of 0.7125 ± 0.003 (1s). These compositions are lower than the values expected from the Precambrian granitoid basement (⁸⁷Sr/⁸⁶Sr = 0.758–0.944), and from the overlying, mainly clastic Paleozoic sediments. Combined Sr isotope composition vs. Sr, Na and Al concentration relationships of soil extracts imply that lowering of the isotopic composition of leachable Sr on Bornholm results as a consequence of significant admixture to this fraction of Sr deposited as marine salts (aerosols), and that rainwater only has a minor influence on the Sr budget of the surface waters. Positively correlated Al/Na and [1/Sr] vs. ⁸⁷Sr/⁸⁶Sr relationships in soil extracts and surface waters indicate that the surface run-off on Bornholm is characterized by two predominant sources, namely marine aerosols (sea salts) with high Sr and low ⁸⁷Sr/⁸⁶Sr values, and a source with lower [Sr] delivering radiogenic Sr to the surface waters, which we equate with Sr leached from the products of mineral weathering (soils).A feasibility study for using Sr isotopic compositions of surface waters and soil extracts as a proxy for bioavailable Sr signatures was performed with a few samples collected in the vicinity of the eleventh century AD Ndr. Grødbygård cemetery site in SW Bornholm, from where Sr isotope compositions of modern fauna samples and tooth enamel of humans buried in the cemetery have been reported. Waters and soil extracts studied herein from around this site range from ⁸⁷Sr/⁸⁶Sr = 0.7104–0.7166 and correspond to Sr compositions extracted from snail shells in this area which span a range of ⁸⁷Sr/⁸⁶Sr = 0.7095–0.7160. Some human tooth enamel is characterized by more radiogenic values (⁸⁷Sr/⁸⁶Sr up to 0.718) which points to a possible provenance of these humans from the granite–gneiss terrain in the north of the island and/or to immigration of these humans in their childhood from other places (for example from mainland Sweden) to Bornholm. If the total compositional range of ⁸⁷Sr/⁸⁶Sr = 0.709–0.718 (n = 44) recorded in human enamel from the Ndr. Grødbygård site is considered representative for the variation of bioavailable Sr on Bornholm, then our soil leachate and surface water data entirely covers this range. We therefore propose that the combination of Sr isotope analyses of surface waters and soil leachates are an easy, fast and relatively cost efficient way to characterize a local bioavailable ⁸⁷Sr/⁸⁶Sr signature, and consequently propose that the overall average of ⁸⁷Sr/⁸⁶Sr = 0.7153 ± 0.0048 (1σ; n = 50) can be taken as a band for bioavailable Sr fractions suitable to discriminate between local and non-local signatures in provenance studies in the field of archaeology and for food and plant authenticity control in agricultural applications.