Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al.

Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) report laser-assisted fluorination (LF) and secondary ionization mass spectrometry (SIMS) ¹⁸O/¹⁶O datasets for olivine grains from the Canary Islands of Gran Canaria, Tenerife, La Gomera, La Palma and El Hierro. As with prior studies of oxygen isotopes in Canary Island lavas (e.g. Thirlwall et al. Chem Geol 135:233–262, 1997; Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010), these authors find variations in δ¹⁸O_ol (~4.6–6.0 ‰) beyond that measured for mantle peridotite olivine (Mattey et al. Earth Planet Sci Lett 128:231–241, 1994) and interpret this variation to reflect contributions from pyroxenite-peridotite mantle sources. Furthermore, Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) speculate that δ¹⁸O_ol values for La Palma olivine grains measured by LF (Day et al. Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) may be biased to low values due to the presence of altered silicate, possibly serpentine. The range in δ¹⁸O_ol values for Canary Island lavas are of importance for constraining their origin. Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) took a subset (39 SIMS analyses from 13 grains from a single El Hierro lava; EH4) of a more extensive dataset (321 SIMS analyses from 110 grains from 16 Canary Island lavas) to suggest that δ¹⁸O_ol is weakly correlated (R ² = 0.291) with the parameter used by Gurenko et al. (Earth Planet Sci Lett 277:514–524, 2009) to describe the estimated weight fraction of pyroxenite-derived melt (Xpx). With this relationship, end-member δ¹⁸O values for HIMU-peridotite (δ¹⁸O = 5.3 ± 0.3 ‰) and depleted pyroxenite (δ¹⁸O = 5.9 ± 0.3 ‰) were defined. Although the model proposed by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) implicates similar pyroxenite-peridotite mantle sources to those proposed by Day et al. (Geology 37:555–558, 2009, Geochim Cosmochim Acta 74:6565–6589, 2010) and Day and Hilton (Earth Planet Sci Lett 305:226–234, 2011), there are significant differences in the predicted δ¹⁸O values of end member components in the two models. In particular, Day et al. (Geochim Cosmochim Acta 74:6565–6589, 2010) proposed a mantle source for La Palma lavas with low-δ¹⁸O (<5 ‰), rather than higher-δ¹⁸O (c.f. the HIMU-peridotite composition of Gurenko et al. in Contrib Mineral Petrol 162:349–363, 2011). Here we question the approach of using weakly correlated variations in δ¹⁸O_ol and the Xpx parameter to define mantle source oxygen isotope compositions, and provide examples of why this approach appears flawed. We also provide reasons why the LF datasets previously published for Canary Island lavas remain robust and discuss why LF and SIMS data may provide complementary information on oxygen isotope variations in ocean island basalts (OIB), despite unresolved small-scale uncertainties associated with both techniques.     

What’s Hiding Behind Ontogenetic δ<Superscript>13</Superscript>C Variations in Mollusk Shells? New Insights from the Great Scallop (<Emphasis Type="Italic">Pecten maximus</Emphasis>)

Mollusk shells contain geochemical information about environmental conditions that prevailed at the time of formation. We investigated ontogenetic and seasonal variations of δ¹³C in calcitic shells of Pecten maximus. Ontogenetic variations of δ¹³C_shell in three large specimens collected in Norway, France, and Spain exhibited a similar linear decrease with increasing shell height. We removed this linear drift (detrending). These three residual time series displayed variations that could be linked to environmental fluctuations. To check it, we reanalyzed the isotopic datasets of Lorrain et al. (Journal of Experimental Marine Biology and Ecology 275:47–61, 2002, Geochimica et Cosmochimica Acta 68:3509–3519, 2004), who worked on three scallops harvested in 2000 in the bay of Brest (France), a well-monitored ecosystem. Lowest values of δ¹³C_{shell detrended} were recorded in all shells in late spring–early summer, most likely reflecting corresponding variations in food availability. Our results indicate that ontogenetic and seasonal variations of δ¹³C_shell cannot be used as a proxy for past δ¹³C_DIC variations but should be considered as promising tools for ecophysiological studies.     

Food Web Structure of the Alaskan Nearshore Shelf and Estuarine Lagoons of the Beaufort Sea

The eastern Alaska Beaufort Sea coast is characterized by numerous shallow (2–5 m) estuarine lagoons, fed by streams and small rivers that drain northward from the Brooks Range through the arctic coastal plain, and bounded seaward by barrier islands and shoals. Millions of birds from six continents nest and forage during the summer period in this region using the river deltas, lagoons, and shoreline along with several species of anadromous and marine fish. We examined biogeochemical processes linking the benthic community to the overall food web structure of these poorly studied but pristine estuaries, which are largely covered by 1.8 m of ice for 10 months annually. In summer, these lagoons are relatively warm with brackish salinities (5–10°C, S = 10–25) compared to more open coastal waters (0–5°C, S > 27). The stable isotopic composition of organic materials in sediments (i.e., benthic particulate organic matter) and water column suspended particulate organic matter from both streams and lagoons are largely indistinguishable and reflect strong terrestrial contributions, based upon δ¹³C and δ¹⁵N values (−25.6‰ to −27.4‰ and 1.4‰ to 3.3‰, respectively). By comparison, shifts toward more heavy isotope-enriched organic materials reflecting marine influence are observed on the adjacent coastal shelf (−24.8‰ to −25.4‰ and 3.4‰ to 5.3‰, respectively). The isotopic composition of lagoon fauna is consistent with a food web dominated by omnivorous detritovores strongly dependent on microbial processing of terrestrial sources of carbon. Biomagnification of ¹⁵N in benthic organisms indicate that the benthic food web in lagoons support up to four trophic levels, with carnivorous gastropod predators and benthic fishes (δ¹⁵N values up to 14.4‰) at the apex.     

Isotopic and molecular distributions of biochemicals from fresh and buried <Emphasis Type="Italic">Rhizophora mangle</Emphasis> leaves†

Rhizophora mangle L. (red mangrove) is the dominant species of mangrove in the Americas. At Twin Cays, Belize (BZ) red mangroves are present in a variety of stand structures (tall >5 m in height, transition ~2–4 m and dwarf ~1–1.5 m). These height differences are coupled with very different stable carbon and nitrogen isotopic values[1] (mean tall δ ¹³C = -28.3‰, δ ¹⁵N = 0‰; mean tall δ ¹³C = -25.3‰, δ ¹⁵N = -10‰). To determine the utility of using these distinct isotopic compositions as 'biomarkers' for paleoenvironmental reconstruction of mangrove ecosystems and nutrient availability, we investigated the distribution and isotopic (δ ¹³C and δ ¹⁵N) composition of different biochemical fractions (water soluble compounds, free lipids, acid hydrolysable compounds, individual amino acids, and the residual un-extractable compounds) in fresh and preserved red mangrove leaves from dwarf and tall trees. The distribution of biochemicals are similar in dwarf and tall red mangrove leaves, suggesting that, regardless of stand structure, red mangroves use nutrients for biosynthesis and metabolism in a similar manner. However, the δ ¹³C and δ ¹⁵N of the bulk leaf, the biochemical fractions, and seven amino acids can be used to distinguish dwarf and tall trees at Twin Cays, BZ. The data support the theory that the fractionation of carbon and nitrogen occurs prior to or during uptake in dwarf and tall red mangrove trees. Stable carbon and nitrogen isotopes could, therefore, be powerful tools for predicting levels of nutrient limitation at Twin Cays. The δ ¹³C and δ ¹⁵N of biochemical fractions within preserved leaves, reflect sedimentary cycling and nitrogen immobilization. The δ ¹⁵N of the immobilized fraction reveals the overlying stand structure at the time of leaf deposition. The isotopic composition of preserved mangrove leaves could yield significant information about changes in ecosystem dynamics, nutrient limitation and past stand structure in mangrove paleoecosystems.     

Use of Multiple Chemical Tracers to Define Habitat Use of Indo-Pacific Mangrove Crab, <Emphasis Type="Italic">Scylla Serrata</Emphasis> (Decapoda: Portunidae)

The mangrove or mud crab, Scylla serrata, is an important component of mangrove fisheries throughout the Indo-Pacific. Understanding crab diets and habitat use should assist in managing these fisheries and could provide additional justification for conservation of the mangrove ecosystem itself. We used multiple chemical tracers to test whether crab movements were restricted to local mangrove forests, or extended to include adjacent seagrass beds and reef flats. We sampled three mangrove forests on the island of Kosrae in the Federated States of Micronesia at Lelu Harbor, Okat River, and Utwe tidal channel. Samples of S. serrata and likely food sources were analyzed for stable carbon (δ¹³C), nitrogen (δ¹⁵N), and sulfur (δ³⁴S) isotopes. Scylla serrata tissues also were analyzed for phosphorus (P), cations (K, Ca, Mg, Na), and trace elements (Mn, Fe, Cu, Zn, and B). Discriminant analysis indicated that at least 87% of the crabs remain in each site as distinct populations. Crab stable isotope values indicated potential differences in habitat use within estuaries. Values for δ¹³C and δ³⁴S in crabs from Okat and Utwe were low and similar to values expected from animals feeding within mangrove forests, e.g., feeding on infauna that had average δ¹³C values near −26.5‰. In contrast, crabs from Lelu had higher δ¹³C and δ³⁴S values, with average values of −21.8 and 7.8‰, respectively. These higher isotope values are consistent with increased crab foraging on reef flats and seagrasses. Given that S. serrata have been observed feeding on adjacent reef and seagrass environments on Kosrae, it is likely that they move in and out of the mangroves for feeding. Isotope mixing model results support these conclusions, with the greatest mangrove ecosystem contribution to S. serrata diet occurring in the largest mangrove forests. Conserving larger island mangrove forests (> 1 km deep) appears to support crab foraging activities.     

Carbon and oxygen isotope constraints on fluid sources and fluid–wallrock interaction in regional alteration and iron-oxide–copper–gold mineralisation, eastern Mt Isa Block, Australia

The source of metasomatic fluids in iron-oxide–copper–gold districts is contentious with models for magmatic and other fluid sources having been proposed. For this study, δ ¹⁸O and δ ¹³C ratios were measured from carbonate mineral separates in the Proterozoic eastern Mt Isa Block of Northwest Queensland, Australia. Isotopic analyses are supported by petrography, mineral chemistry and cathodoluminescence imagery. Marine meta-carbonate rocks (ca. 20.5‰ δ ¹⁸O and 0.5‰ δ ¹³C calcite) and graphitic meta-sedimentary rocks (ca. 14‰ δ ¹⁸O and −18‰ δ ¹³C calcite) are the main supracrustal reservoirs of carbon and oxygen in the district. The isotopic ratios for calcite from the cores of Na–(Ca) alteration systems strongly cluster around 11‰ δ ¹⁸O and −7‰ δ ¹³C, with shifts towards higher δ ¹⁸O values and higher and lower δ ¹³C values, reflecting interaction with different hostrocks. Na–(Ca)-rich assemblages are out of isotopic equilibrium with their metamorphic hostrocks, and isotopic values are consistent with fluids derived from or equilibrated with igneous rocks. However, igneous rocks in the eastern Mt Isa Block contain negligible carbon and are incapable of buffering the δ ¹³C signatures of CO₂-rich metasomatic fluids associated with Na–(Ca) alteration. In contrast, plutons in the eastern Mt Isa Block have been documented as having exsolved saline CO₂-rich fluids and represent the most probable fluid source for Na–(Ca) alteration. Intrusion-proximal, skarn-like Cu–Au orebodies that lack significant K and Fe enrichment (e.g. Mt Elliott) display isotopic ratios that cluster around values of 11‰ δ ¹⁸O and −7‰ δ ¹³C (calcite), indicating an isotopically similar fluid source as for Na–(Ca) alteration and that significant fluid–wallrock interaction was not required in the genesis of these deposits. In contrast, K- and Fe-rich, intrusion-distal deposits (e.g. Ernest Henry) record significant shifts in δ ¹⁸O and δ ¹³C towards values characteristic of the broader hostrocks to the deposits, reflecting fluid–wallrock equilibration before mineralisation. Low temperature, low salinity, low δ ¹⁸O (<10‰ calcite) and CO₂-poor fluids are documented in retrograde metasomatic assemblages, but these fluids are paragenetically late and have not contributed significantly to the mass budgets of Cu–Au mineralisation.     

Reply to “Oxygen isotope heterogeneity of the mantle beneath the Canary Islands: a discussion of the paper of Gurenko et al.”

The comment by Day et al. (Contrib Mineral Petrol, 2012) (1) discusses the validity of the previously obtained oxygen isotope data for El Hierro and La Palma (Canary Island) olivines, (2) questions the approach by Gurenko et al. (Contrib Mineral Petrol 162:349–363, 2011) of using weakly correlated variations of δ¹⁸O_olivine values with X _px (proportion of pyroxenite-derived melt in the parental magma), and (3) provides reasons why oxygen isotope data by secondary ion mass spectrometry (SIMS) “offer sensitive means for detecting melt-crust interactions.” We respond these comments and report a new set of oxygen isotope measurements performed by SIMS and single-grain laser fluorination methods. These measurements confirm our previous data and conclusions and demonstrate the ability of the SIMS technique to analyze O isotopes in terrestrial samples with 2-sigma uncertainty better than ±0.25 ‰.     

The application of δ13C and C/N ratios as indicators of organic carbon sources and paleoenvironmental change of the mangrove ecosystem from Ba Lat Estuary, Red River, Vietnam

In this study, two sediment cores (~70 cm) were collected from separate mangrove forests straddling the Ba Lat Estuary, Red River of northern Vietnam, to examine the origins of sedimentary organic carbon (SOC) and reconstruct the paleoenvironment. In addition, mangrove leaves and particulate organic matter were collected and measured for δ¹³C to trace the origins of SOC. The cores were analyzed by high-resolution sections for δ¹³C, TOC, C/N ratios, sediment grain size, water content, and porosity, with values of δ¹³C, TOC, and C/N ratios ranging from −28.19 to −22.5‰, 2.14–30.94 mg/g, and 10.29–18.32, respectively. The δ¹³C and TOC relationship indicated that there were some small residual effects of diagenetic processes on TOC and δ¹³C values in mangrove sediments. However, the shifts of δ¹³C and C/N ratios from the bottom to the surface sediment of the cores explained the change in organic matter sources, with values of C/N > 12 and δ¹³C < −25‰, and C/N < 12 and δ¹³C > −25‰ indicated terrestrial (e.g., mangrove litter) and marine phytoplankton sources, respectively. The covarying δ¹³C, C/N ratios, and sediment grain sizes during the past 100 years in sediment cores showed that the paleoenvironment may be reconstructed into three environments (subtidal, tidal flat, and intertidal mangrove). General trends in δ¹³C and C/N followed a gradual increase in the C/N ratio and a concomitant decrease in δ¹³C from the subtidal, through to tidal flat, and to the intertidal mangrove. δ¹³C and C/N ratios are therefore effective in measuring the continuum of environmental change in mangrove ecosystem.     

Prediction of the thermodynamic properties of metal–arsenate and metal–arsenite aqueous complexes to high temperatures and pressures and some geological consequences

The standard thermodynamic properties at 25°C, 1 bar (ΔG _f^o, ΔH _f^o, S ^o, C _P^o, V ^o, ω) and the coefficients of the revised Helgeson–Kirkham–Flowers equations of state were evaluated for several aqueous complexes formed by dissolved metals and either arsenate or arsenite ions. The guidelines of Shock and Helgeson (Geochim Cosmochim Acta 52:2009–2036, 1988) and Sverjensky et al. (Geochim Cosmochim Acta 61:1359–1412, 1997) were followed and corroborated with alternative approaches, whenever possible. The SUPCRT92 computer code was used to generate the log K of the destruction reactions of these metal–arsenate and metal–arsenite aqueous complexes at pressures and temperatures required by the EQ3/6 software package, version 7.2b. Apart from the AlAsO₄^o and FeAsO₄^o complexes, our log K at 25°C, 1 bar are in fair agreement with those of Whiting (MS Thesis, Colorado School of Mines, Golden, CO, 1992). Moreover, the equilibrium constants evaluated in this study are in good to fair agreement with those determined experimentally for the Ca–dihydroarsenate and Ca–hydroarsenate complexes at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) and for Fe(III)–hydroarsenate complex at 25°C (Raposo et al., J Sol Chem 35:79–94, 2006), whereas the disagreement with the log K measured for the Ca–arsenate complex at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) might be due to uncertainties in this measured value. The implications of aqueous complexing between dissolved metals and arsenate/arsenite ions were investigated for seawater, high-temperature geothermal liquids and acid mine drainage and aqueous solutions deriving from mixing of acid mine waters and surface waters. Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users.     

Comparing Lignin-Derived Phenols, δ13C Values, OC/N Ratio and 14C Age Between Sediments in the Kaoping (Taiwan) and the Kapuas (Kalimantan, Indonesia) Rivers

The Kaoping (Taiwan) and Kapuas (Indonesia) Rivers differ in hydrological cycle, topography and landscape. These differences strengthen the use of ¹⁴C dating, lignin-derived phenols, δ¹³C values and C/N ratios to determine the sources and diagenesis of surface sedimentary organic carbon (OC) in both rivers. The Kapuas River is surrounded by forest, resulting in sedimentary OC with a ¹⁴C age between 600 and 740 years, Λ (total lignin expressed as mg/100 mg OC) values from 0.94 to 3.70, δ¹³C values from −27.87 to −30.00‰, C/N ratios from 6.7 to 30.8, %OC from 0.63 to 9.24% and vanillic acid to vanillin ratio, (Ad/Al)v, values from 0.73 to 2.09, all of which indicate the presence of recent plant-derived organic matter. The tributaries and three locations upstream of the Kaoping River are also surrounded by forests, resulting in Λ values (0.51–4.80), δ¹³C values (−23.85 to −27.08‰), C/N ratios (14.1–28.7), %OC (1.01–7.86%) and (Ad/Al)v values (0.86–1.88), which are indicative of a terrestrial signal. No lignin oxidation products were detected in the mainstream of the Kaoping River or its coastal zone, hence the surface sediments OC with a ¹⁴C age between 4,915 and 15,870 years, enriched δ¹³C values (−23.30 and −26.54‰), lower C/N ratios (6.0–17.5) and lower %OC (0.15–2.24%) likely represent old rock and soil material. Massive floods during typhoons most probably cause plant materials from the Kaoping River and its coastal zone to be transported into the deep sea.     

A Preliminary Survey of the Nitrogen and Carbon Isotope Characteristics of Fish from the Lagoons of Egypt’s Nile Delta

The present study reports nitrogen and carbon stable isotope data (δ¹⁵N and δ¹³C) from four large (63–400 km²), shallow (∼1 m) coastal lagoons on Egypt’s Nile Delta. While the lagoons all receive sewage and agricultural drainage, the magnitude of loading varies. In this preliminary survey, we document wide variability in the δ¹⁵N and δ¹³C isotope values of major fish groups among these lagoons. There were no consistent or significant differences among the major groups of fish, including carp, catfish, mullet, and tilapia. There was a strong positive correlation (R ² = 0.84) between the average δ¹⁵N values of fish muscle and estimated water residence time among the lagoons. This preliminary evidence suggests that nitrogen cycle transformations may be more important than primary N source differences in determining N isotopic ratios of organisms in the lagoons. The δ¹³C results point to the probable importance of autochthonous particulate organic matter rather than terrestrial detritus or marine plankton in the diets of resident fish populations in the lagoons.     

Stable carbon isotope characteristics of different plant species and surface soil in arid regions

The stable carbon isotope composition in surface soil organic matter (δ¹³Csoil) contains integrative information on the carbon isotope composition of the standing terrestrial plants (δ¹³Cleaf). In order to obtain valuable vegetation information from the δ¹³C of terrestrial sediment, it is necessary to understand the relationship between the δ¹³C value in modern surface soil and the standing vegetation. In this paper, we studied the δ¹³C value in modern surface soil organic matter and standing vegetation in arid areas in China, Australia and the United States. The isotopic discrepancy between δ¹³Csoil and δ¹³Cleaf of the standing dominant vegetation was examined in those different arid regions. The results show that the δ¹³Csoil values were consistently enriched compared to the δ¹³Cleaf. The δ¹³Cleaf values were positively correlated with δ¹³Csoil, which suggests that the interference of microorganisms and hydrophytes on the isotopic composition of surface soil organic matter during soil organic matter formation could be ignored in arid regions. The averaged discrepancy between δ¹³Csoil and δ¹³Cleaf is about 1.71%in Tamarix L. in the Tarim Basin in China, 1.50% in Eucalytus near Orange in Australia and 1.22% in Artemisia in Saratoga in the United States, which are different from the results of other studies. The results indicate that the discrepancies in the δ¹³C value between surface soil organic matter and standing vegetation were highly influenced by the differences in geophysical location and the dominant species of the studied ecosystems. We suggest that caution should be taken when organic matter δ¹³C in terrestrial sediment is used to extract paleovegetation information (C₃/C₄ vegetation composition), as the δ¹³C in soil organic matter is not only determined by the ratio of C₃/C₄ species, but also profoundly affected by climate change induced variation in the δ¹³C in dominant species.     

Heat capacity,entropy and phase equilibria of stishovite

The low-temperature heat capacity (C _P) of stishovite (SiO₂) synthesized with a multi-anvil device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system (PPMS) and around ambient temperature using a differential scanning calorimeter (DSC). The entropy of stishovite at standard temperature and pressure calculated from DSC-corrected PPMS data is 24.94 J mol⁻¹ K⁻¹, which is considerably smaller (by 2.86 J mol⁻¹ K⁻¹) than that determined from adiabatic calorimetry (Holm et al. in Geochimica et Cosmochimica Acta 31:2289–2307, 1967) and about 4% larger than the recently reported value (Akaogi et al. in Am Mineral 96:1325–1330, 2011). The coesite–stishovite phase transition boundary calculated using the newly determined entropy value of stishovite agrees reasonably well with the previous experimental results by Zhang et al. (Phys Chem Miner 23:1–10, 1996). The calculated phase boundary of kyanite decomposition reaction is most comparable with the experimental study by Irifune et al. (Earth Planet Sci Lett 77:245–256, 1995) at low temperatures around 1,400 K, and the calculated slope in this temperature range is mostly consistent with that determined by in situ X-ray diffraction experiments (Ono et al. in Am Mineral 92:1624–1629, 2007).     

Fluid flow in marbles at Jervois, central Australia: oxygen isotope disequilibrium and zoning produced by decoupling of mineralogical and isotopic resetting

The Jervois region of the Arunta Inlier, central Australia, contains para- and orthogneisses that underwent low-pressure amphibolite facies metamorphism (P = 200–300 MPa, T = 520–600 °C). Marble layers cut by metre-wide quartz + garnet ± epidote veins comprise calcite, quartz, epidote, clinopyroxene, grandite garnet, and locally wollastonite. The marbles also contain locally discordant decimetre-thick garnet and epidote skarn layers. The mineral assemblages imply that the rocks were infiltrated by water-rich fluids (XCO₂ = 0.1–0.3) at ∼600 °C. The fluids were probably derived from the quartz-garnet vein systems that represent conduits for fluids exsolved from crystallizing pegmatites emplaced close to the metamorphic peak. At one locality, the marble has calcite (Cc) δ¹⁸O values of 9–18‰ and garnet (Gnt) δ¹⁸O values of 10–14‰. The δ¹⁸O(Gnt) values are only poorly correlated with δ¹⁸O(Cc), and the δ¹⁸O values of some garnet cores are higher than the rims. The isotopic disequilibrium indicates that garnet grew before the δ¹⁸O values of the rock were reset. The marbles contain  ≤15% garnet and, for water-rich fluids, garnet-forming reactions are predicted to propagate faster than O-isotopes are reset. The Sm-Nd and Pb-Pb ages of garnets imply that fluid flow occurred at 1750–1720 Ma. There are no significant age differences between garnet cores and rims, suggesting that fluid flow was relatively rapid. Texturally late epidote has δ¹⁸O values of 1.5–6.2‰ implying δ¹⁸O(H₂O) values of 2–7‰. Waters with such low-δ¹⁸O values are probably at least partly meteoric in origin, and the epidote may be recording the late influx of meteoric water into a cooling hydrothermal system. Received: 29 April 1996 / Accepted: 12 March 1997     

Climatic significance of D/H and13C/12C ratios in Irish oak cellulose

δD and δ¹³C analyses of cellulose nitrate from two modern Irish oak trees that form part of the 7400 year long chronology were carried out, covering a period of 123 years (1861–1983 A.D.) with a 5 year resolution so as to assess the potential of this long chronology for retrieval of palaeoenvironmental data. One of the trees (Q5293) showed significant correlations of δD, δ¹³ C and ring width with mean annual temperatures as recorded at the Armagh weather station nearby and the mean fall temperatures of Central England. The other tree (Q5296) did not exhibit any significant climatic correlations either because it grew utilizing a nearby permanent source of ground water or because the intra-ring isotopic variations in Irish oak are significant enough to mask the climatic signal. Whilst our results have given a positive indication of the usefulness of these trees for palaeoenvironmental information, more trees need to be analysed to confirm our findings. Even though one of the trees did not exhibit climatic correlations, both trees show a significant positive correlation of δ¹³C and a negative correlation of δD with ring width variations. Furthermore, two tree samples that grew during the 1620s B.C., when a volcano is thought to have erupted on the Aegean island of Santorini, show increased δD and decreased δ¹³C for one to two decades following the eruption, though the magnitudes of change seem to vary with site and trees. We have proposed a possible mechanism based on tree phenology to explain both the above effects.     

Can shells of freshwater mussels (Unionidae) be used to estimate low summer discharge of rivers and associated droughts?

This paper examines if shell oxygen isotope ratios (δ¹⁸O_ar) of Unio sp. can be used as a proxy of past discharge of the river Meuse. The proxy was developed from a modern dataset for the reference time interval 1997–2007, which showed a logarithmic relationship between discharge and measured water oxygen isotope ratios (δ¹⁸O_w). To test this relationship for past time intervals, δ¹⁸O_ar values were measured in the aragonite of the growth increments of four Unio sp. shells; two from a relatively wet period and two from a very dry time interval (1910–1918 and 1969–1977, respectively). Shell δ¹⁸O_ar records were converted into δ¹⁸O_w values using existing water temperature records. Summer δ¹⁸O_w values, reconstructed from δ¹⁸O_ar of 1910–1918, showed a similar range as the summer δ¹⁸O_w values for the reference time interval 1997–2007, whilst summer reconstructed δ¹⁸O_w values for the time interval 1969–1977 were anomalously high. These high δ¹⁸O_w values suggest that the river Meuse experienced severe summer droughts during the latter time interval. δ¹⁸O_w values were then applied to calculate discharge values. It was attempted to estimate discharge from the reconstructed δ¹⁸O_w values using the logarithmic relationship between δ¹⁸O_w and discharge. A comparison of the calculated summer discharge results with observed discharge data showed that Meuse low-discharge events below a threshold value of 6 m³/s can be detected in the reconstructed δ¹⁸O_w records, but true quantification remains problematic.     

Zr diffusion in titanite

Chemical diffusion of Zr under anhydrous, pO₂-buffered conditions has been measured in natural titanite. The source of diffusant was either zircon powder or a ZrO₂–Al₂O₃–titanite mixture. Experiments were run in sealed silica glass capsules with solid buffers (to buffer at NNO or QFM). Rutherford Backscattering Spectrometry (RBS) was used to measure diffusion profiles. The following Arrhenius parameters were obtained for Zr diffusion parallel to c over the temperature range 753–1,100°C under NNO-buffered conditions: D _Zr = 5.33 × 10⁻⁷ exp(−325 ± 30 kJ mol⁻¹/RT) m² s⁻¹ Diffusivities are similar for experiments buffered at QFM. These data suggest that titanite should be moderately retentive of Zr chemical signatures, with diffusivities slower than those for O and Pb in titanite, but faster than those for Sr and the REE. When applied in evaluation of the relative robustness of the recently developed Zr-in-titanite geothermometer (Hayden and Watson, Abstract, 16th V.M. Goldschmidt Conference 2006), these findings suggest that Zr concentrations in titanite will be less likely to be affected by later thermal disturbance than the geothermometer based on Zr concentrations in rutile (Zack et al. in Contrib Mineral Petrol 148:471–488, 2004; Watson et al. in Contrib Mineral. Petrol, 2006), but much less resistant to diffusional alteration subsequent to crystallization than the Ti-in-Zircon geothermometer (Watson and Harrison in Science 308:841–844, 2005).     

Salinization properties of a shallow groundwater in a coastal reclaimed area,Yeonggwang, Korea

The need for more agricultural or residential land has encouraged reclamation at the coastal areas of Korea since 1200 ad (approximately). The groundwaters of these reclaimed areas could be expected to reveal hydrogeochemical properties different from those of areas directly affected by seawater intrusion. The purpose of this study, therefore, was to examine the salinization of shallow groundwater in a coastal reclaimed area and to identify the effect of land reclamation on groundwater quality. Major cations and anions, iodide, total organic carbon, δD, δ ¹⁸O and δ ¹³C were measured to assist the hydrogeochemical analysis. Chloride, δD and δ ¹⁸O data clearly show that the Na–Cl type water results from mixing of groundwater with seawater. In particular, the δD and δ ¹⁸O of Ca+Mg–Cl+NO₃ type groundwaters are close to the meteoric water line, but Na–Cl type waters enriched in chloride are ¹⁸O-enriched with respect to the meteoric water line. Meanwhile, carbon isotopic data and I/Cl ratios strongly suggest that there are various sources of salinity. The δ ¹³C values of Na–Cl type groundwaters are generally similar to those of Ca+Mg–Cl+NO₃ type waters, which are depleted in ¹³C with respect to seawater. I/Cl ratios of Na–Cl type groundwater are 10–100 times higher than that of seawater. Because the reclamation has incorporated a large amount of organic matter, it provides optimum conditions for the occurrence of redox processes in the groundwater system. Therefore, the salinization of groundwater in the study area seems to be controlled not only by saltwater intrusion but also by other effects, such as those caused by residual salts and organic matter in the reclaimed sediments.     

In search of the mixed derivative ?2 M /? P ? T ( M = G , K ): joint analysis of ultrasonic data for polycrystalline pyrope from gas- and solid-medium apparatus

Elastic wave velocities for dense (99.8% of theoretical density) isotropic polycrystalline specimens of synthetic pyrope (Mg₃Al₂Si₃O₁₂) were measured to 1,000 K at 300 MPa by the phase comparison method of ultrasonic interferometry in an internally heated gas-medium apparatus. The temperature derivatives of the elastic moduli [(∂Ks/∂T) _P = −19.3(4); (∂G/∂T) _P = −10.4(2) MPa K⁻¹] measured in this study are consistent with previous acoustic measurements on both synthetic polycrystalline pyrope in a DIA-type cubic anvil apparatus (Gwanmesia et al. in Phys Earth Planet Inter 155:179–190, 2006) and on a natural single crystal by the rectangular parallelepiped resonance (RPR; Suzuki and Anderson in J Phys Earth 31:125–138, 1983) method but |(∂Ks/∂T) _P | is significantly larger than from a Brillouin spectroscopy study of single-crystal pyrope (Sinogeikin and Bass in Phys Earth Planet Inter 203:549–555, 2002). Alternative approaches to the retrieval of mixed derivatives of the elastic moduli from joint analysis of data from this study and from the solid-medium data of Gwanmesia et al. in Phys Earth Planet Inter 155:179–190 (2006) yield ∂² G/∂P∂T = [0.07(12), 0.20(14)] × 10⁻³ K⁻¹ and ∂² K _S /∂P∂T = [−0.20(24), 0.22(26)] × 10⁻³ K⁻¹, both of order 10⁻⁴ K⁻¹ and not significantly different from zero. More robust inference of the mixed derivatives will require solid-medium acoustic measurements of precision significantly better than 1%.     

Isotopic constraints on fluid evolution and precipitation mechanisms for the Boléo Cu–Co–Zn district, Mexico

Stable and radiogenic isotope composition of stratiform Cu–Co–Zn mineralization and associated sedimentary rocks within the Boléo district of the Miocene Santa Rosalía basin, Baja California Sur, constrains the evolution of seawater and hydrothermal fluids and the mechanisms responsible for sulfide and oxide deposition. Stable isotope geochemistry of limestone and evaporite units indicates a strong paleogeographic influence on the chemistry of the water column. Near-shore limestone at the base of the Boléo Formation is characterized by modified marine carbon (δ ¹³C_PDB=−6.0 to +4.4‰) and oxygen (δ ¹⁸O_SMOW=+19.5 to +26.2‰) isotope composition due to the influx of ¹³C- and ¹⁸O-depleted fluvial water. Sulfate sulfur isotope composition (δ ³⁴S_CDT=+17.21 to +22.3‰ and δ ¹⁸O_SMOW=+10.7 to +13.1‰) for basal evaporite and claystone facies are similar to Miocene seawater. Strontium isotopes are less radiogenic than expected for Miocene seawater due to interaction with volcanic rocks. Low S/C ratios, high Mn contents and sedimentological evidence indicate the basin water column was oxidizing. The oxygenated basin restricted sulfide precipitation to within the sedimentary pile by replacement of early diagenetic framboidal pyrite and pore-space filling by Cu–Co–Zn sulfides to produce disseminated sulfides. Quartz–Mn oxide oxygen isotope geothermometry constrains mineralization temperature between 18 and 118°C. Sulfur isotopes indicate the following sources of sulfide: (1) bacterial sulfate reduction within the sedimentary pile produced negative δ ³⁴S values (<−20‰) in framboidal pyrite; and (2) bacterial sulfate reduction at high temperature (80–118°C) within the sedimentary pile during the infiltration of the metal-bearing brines produced Cu–Co–Zn sulfides with negative, but close to 0‰, δ ³⁴S values. Isotope modeling of fluid-rock reaction and fluid mixing indicates: (1) sedimentary and marine carbonates (δ ¹³C=−11.6 to −3.2‰ and δ ¹⁸O=+19.0 to +21.8‰) precipitated from basin seawater/pore water that variably mixed with isotopically depleted meteoric waters; and (2) hydrothermal calcite (δ ¹³C=−7.9 to +4.3‰ and δ ¹⁸O=+22.1 to +25.8‰) formed by dissolution and replacement of authigenic marine calcite by downward-infiltrating metalliferous brine and brine-sediment exchange, that prior to reaction with calcite, had mixed with isotopically depleted pore water. The downward infiltration of metalliferous brine is inferred from lateral and stratigraphic metal distributions and from the concentration of Cu sulfides along the upper contact of pyrite-bearing laminae. The co-existence and textural relationships among framboidal pyrite, base metal sulfides, carbonate and Mn–Fe oxides (including magnetite) within mineralized units are consistent with carbonate replacement and high-temperature bacterial reduction within the sedimentary pile occurring simultaneously below a seawater column under predominantly oxygenated conditions.