Strontium isotope stratigraphy in the Late Cretaceous: intercontinentaI correlation of the Campanian/ Maastrichtian boundary

In the Boreal Chalk of northwestern Europe the base of the Maastrichtian Stage is defined by entry of the belemnite Belemnella . In the Kronsmoor section, in northwestern Germany, which is a standard section for the European Chalk, ⁸⁷Sr/⁸⁶Sr at the Campanian/ Maastrichtian (C/M) boundary is 0.707723±9 (10). An isotopic correlation of this boundary to the US Western Interior, for which a highly refined cephalopod biostratigraphy exists, suggests that this boundary, as defined at Kronsmoor, occurs within the Baculites jenseni zone. This correlationagrees with the latest placement based on biostratigraphic criteria. On⁸⁷Sr/⁸⁶Srcriteria the boundary at Kronsmoor correlates to the English Chalk at Trunch, Norfolk, UK, at a level 3.5 m lower than its position based on biostratigraphic criteria.
At Kronsmoor, ⁸⁷Sr/⁸⁶Sr increases in a quasi-linear manner through much of the section, suggesting that, averaged over intervals of 1 Myr, the gross sedimentation rate and temporal rate of change of ⁸⁷Sr/⁸⁶Sr were approximately constant through the section. For US samples, zonally-plotted values of ⁸⁷Sr/⁸⁶Sr define a quasi-linear trend, which suggests a moderate uniformity of zonal duration from the Baculites compressus zone (73.2±0.7 Ma, 10) to the Baculites grandis zone (70.1±0.7 Ma, 10).     

Terrestrial carbon-isotope records from coastal deposits (Algarve, Portugal): a tool for chemostratigraphic correlation on an intrabasinal and global scale

ABSTRACT The carbon-isotope signature of terrestrial organic matter (OM) offers a valuable tool to develop stratigraphic correlations for near-shore deposits. A mid-Cretaceous coastal succession of the western Algarve Basin, Portugal, displays a marked negative δ¹³C excursion ranging from − 21.2‰ to − 27.8‰ in the Early Aptian followed by two shifts towards higher values (up to − 19.3‰) during the Early and Late Aptian, respectively. The dominance of cuticle and leaf debris in the bulk OM fraction is confirmed by optical studies, Rock-Eval pyrolysis and by comparison with the δ¹³C signature of four different types of fossilized land-plant particles. Correlation of two terrestrial δ¹³C_bulk OM records from different study sites leads to a significant enhancement of the intrabasinal stratigraphic correlation within the Algarve Basin. Three prominent excursions in the Portuguese records can be correlated with existing δ¹³C curves from pelagic and terrestrial environments. The general carbon-isotope pattern is superimposed by small-scale fluctuations which can be explained by compositional variations within the OM.     

Thermochemical sulphate reduction in the Upper Devonian Cairn Formation of the Fairholme carbonate complex (South-West Alberta, Canadian Rockies): evidence from fluid inclusions and isotopic data

The Fairholme carbonate complex is part of the extensively dolomitized Upper Devonian carbonate reefs in west-central Alberta. The studied formations contain moulds (up to 10 cm in diameter), which are filled partially with (saddle) dolomite, quartz and calcite cements. These cements precipitated from a mixture of brines that acquired high salinity by dissolution of halite and brines derived from evaporated sea water. The fluids were warm (homogenization temperature of primary fluid inclusions of 76 to 200 °C) and saline (20 to 25 wt% NaCl equivalent) and testify to thermochemical sulphate reduction processes. The latter is deduced from S in solid inclusions, CO₂ and H₂S in volatile-rich aqueous inclusions and depleted δ¹³C values down to −26‰ Vienna Pee Dee Belemnite. High ⁸⁷Sr/⁸⁶Sr values (0·7094 to 0·7110) of the cements also indicate interaction of the fluids with siliciclastic sequences. The thermochemical sulphate reduction-related cements probably formed during early Laramide burial. Another (younger) calcite phase, characterized by depleted δ¹⁸O values (−23·9‰ to −13·9‰ Vienna Pee Dee Belemnite), low Na (27 to 37 p.p.m.) and Sr (39 to 150 p.p.m.) concentrations and non-saline (∼0 wt% NaCl equivalent) fluid inclusions, is attributed to post-Laramide meteoric water.     

A 3.1 billion year old marble and the 87Sr/86Sr of late-Archean seawater

A marble band in the ≈ 2.75 Gyr old Ramagiri schist belt in the Dharwar craton of south India gave a Pb–Pb age of 3.075 ± 0.095 Gyr. The geochemical data, including high Sr and low Ba and Mn indicate seawater origin for the parent rock, and that there was insignificant geochemical exchange between the marble and the surrounding rocks. The calculated initial Nd isotopic composition and μ₁ indicate an older continental crustal source for the Nd and Pb. The initial ⁸⁷Sr/⁸⁶Sr of the marble is 0.70128, which is higher than the calculated mantle value at ≈ 3 Ga. Although pre-3 Gyr old marine carbonate rocks are thought to be buffered by mantle Sr, the Ramagiri marble contains evolved, crustal Sr. Despite this, the marble has the lowest measured ⁸⁷Sr/⁸⁶Sr among carbonates and represents one of the least radiogenic periods in seawater Sr isotope composition.     

Astronomical tuning of the Tortonian 87Sr/86Sr curve in the Mediterranean basin

ABSTRACT This work presents a detailed ⁸⁷Sr/⁸⁶Sr isotope curve for the interval 7.5–9.7 Ma obtained by a high-resolution analysis (sampling spacing of about 40 kyr) of an astronomically calibrated land-based sedimentary sequence exposed in the central Mediterranean area (Gibliscemi section, southern Sicily). The main aim is to verify a synchronous response of the Mediterranean seawater Sr isotope record to the oceanic forcing on the basis of multiple comparisons of the Gibliscemi record with published coeval ⁸⁷Sr/⁸⁶Sr curves. A good correlation with the ⁸⁷Sr/⁸⁶Sr data from the ODP site 926 (equatorial Atlantic ocean), considered to be the Sr chemostratigraphic reference section for the Late Miocene, and from the Pacific DSDP site 590B was registered. Conversely, the comparison of the Gibliscemi Sr isotope data with ⁸⁷Sr/⁸⁶Sr ratios from the coeval segment of the land-based Sardella section (eastern Mediterranean) shows important differences highlighting a local control on the seawater Sr isotope changes in semi-isolated subbasins within the Late Miocene Mediterranean.     

Sr isotope evolution of Maastrichtian seawater, determined from the chalk of Hemmoor, NW Germany

In 140 metres of Maastrichtian White Chalk (nannofossil chalk) exposed near Hemmoor, NW Germany, values of ⁸⁷Sr/⁸⁶Sr increase from 0.707760 in the Belemnella sumensis Zone (Lower Maastrichtian) at the base of the section (-54.5 m; referred to 0 m at a prominent marl, M900) to 0.707821 in the Belemnella baltica/danica Zone (Upper Maastrichtian) at the top of the section (+84.5 m). A plateau in ⁸⁷Sr/⁸⁶Sr occurs between -5m and +50m in the section, probably as a result of a very high rate of sedimentation in this interval. A belemnite and associated nannofossil chalk have similar ⁸⁷Sr/⁸⁶Sr values, suggesting that there has been little diagenetic alteration of the ⁸⁷Sr/⁸⁶Sr ratios in the chalk, which therefore preserves its original ⁸⁷Sr/⁸⁶Sr. Comparison of ⁸⁷Sr/⁸⁶Sr and nannofossil zonations for sequences at Bidart, France, and DSDP Sites reveals discordance and so possible diachronism of the basal boundaries of nannofossil Zones CC25B and CC25C.     

Magma homogenization during anatexis,ascent and/or emplacement? Constraints from the Variscan Weinsberg Granites

Recent studies have shown that melts and residues may not equilibrate during anatexis, and uncertainty exists about the scale on which magmas can be homogenized. This study of elemental and isotopic homogeneity of the South Bohemian Weinsberg granites (˜ 5000 km²) identifies three voluminous, relatively homogeneous magma batches. Each batch has different ⁸⁷Sr/⁸⁶Sr_init (0.7080, 0.7093 and 0.7106), but all equilibrated at ˜ 327–329 Ma, very similar to the time of monazite crystallization. The data cannot entirely prove melt/residue equilibration during anatexis. However, elemental and isotopic compositions imply magma generation by partial melting of heterogeneous South Bohemian crust and chemical differentiation subsequent to Sr-isotope equilibration. Assuming relatively rapid ascent and solidification rates, magma homogenization must have occurred mostly just after partial melting, during melt segregation and accumulation in the deeper crust with slow prograde heating. Models of rapid crustal heating and instantaneous melt extraction are incompatible with the data.     

Petrochemical constraints for dual origin of garnet peridotites from the Dabie-Sulu UHP terrane, eastern-central China

Garnet peridotites occur as lenses, blocks or layers within granulite–amphibolite facies gneiss in the Dabie-Sulu ultra-high-pressure (UHP) terrane and contain coesite-bearing eclogite. Two distinct types of garnet peridotite were identified based on mode of occurrence and petrochemical characteristics. Type A mantle-derived peridotites originated from either: (1) the mantle wedge above a subduction zone, (2) the footwall mantle of the subducted slab, or (3) were ancient mantle fragments emplaced at crustal depths prior to UHP metamorphism, whereas type B crustal peridotite and pyroxenite are a portion of mafic–ultramafic complexes that were intruded into the continental crust as magmas prior to subduction. Most type A peridotites were derived from a depleted mantle and exhibit petrochemical characteristics of mantle rocks; however, Sr and Nd isotope compositions of some peridotites have been modified by crustal contamination during subduction and/or exhumation. Type B peridotite and pyroxenite show cumulate structure, and some have experienced crustal metasomatism and contamination documented by high ⁸⁷Sr/⁸⁶Sr ratios (0.707–0.708), low ε_Nd( t ) values (−6 to −9) and low δ¹⁸O values of minerals (+2.92 to +4.52). Garnet peridotites of both types experienced multi-stage recrystallization; some of them record prograde histories. High- P–T  estimates (760–970 °C and 4.0–6.5±0.2 GPa) of peak metamorphism indicate that both mantle-derived and crustal ultramafic rocks were subducted to profound depths >100 km (the deepest may be ≥180–200 km) and experienced UHP metamorphism in a subduction zone with an extremely low geothermal gradient of <5 °C km⁻¹.     

Zircon U–Pb age, trace element and Hf isotope composition of Kongling terrane in the Yangtze Craton: refining the timing of Palaeoproterozoic high-grade metamorphism

U–Pb age, trace element and Hf isotope compositions of zircon were analysed for a metasedimentary rock and two amphibolites from the Kongling terrane in the northern part of the Yangtze Craton. The zircon shows distinct morphological and chemical characteristics. Most zircon in an amphibolite shows oscillatory zoning, high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, high formation temperature, high trace element contents, clear negative Eu anomaly, as well as HREE-enriched patterns, suggesting that it is igneous. The zircon yields a weighted mean ²⁰⁷Pb/²⁰⁶Pb age of 2857 ± 8 Ma, representing the age of the magmatic protolith. The zircon in the other two samples is metamorphic. It has low Th/U ratios, low trace element concentrations, variable HREE contents (33.8 ≥ Lu_N≥2213; 14.7 ≤ Lu_N/Sm_N ≤ 354) and ¹⁷⁶Lu/¹⁷⁷Hf ratios (0.000030–0.001168). The data indicate that the zircon formed in the presence of garnet and under upper amphibolite facies conditions. The metamorphic zircon yields a weighted mean ²⁰⁷Pb/²⁰⁶Pb age of 2010 ± 13 Ma. These results combined with previously obtained Palaeoproterozoic metamorphic ages suggest a c. 2.0 Ga Palaeoproterozoic collisional event in the Yangtze Craton, which may result from the assembly of the supercontinent Columbia. The zircon in two samples yields weighted mean two-stage Hf model ( T _DM2) ages of 3217 ± 110 and 2943 ± 50 Ma, respectively, indicating that their protoliths were mainly derived from Archean crust.     

Dating cleavage formation in slates and phyllites with the 40Ar/39Ar laser microprobe: an example from the western New England Appalachians, USA

Determinations of the absolute age of cleavage formation can provide fundamental information about the evolution of orogenic belts. However, when applied to cleavages in slates and phyllites, conventional dating methods are complicated by problems related to mineral separation and the presence of multiple cleavage generations. In situ high-spatial-resolution ⁴⁰Ar/³⁹Ar laser microprobe geochronology and microstructural observations indicate that the age of cleavage formation in slates and phyllites can be constrained by analysing zones of tightly packed cleavage domains. Three regionally developed cleavages (S₂, S₃, and S₄) are present in the northern Taconic Allochthon of Vermont and New York. Representative samples were studied from a variety of localities where these cleavages, which are defined by white micas, are well developed. In the suite of samples, only S₃ and S₄ are expressed as domains that are sufficiently wide and spatially isolated in thin section to permit quantitative ⁴⁰Ar/³⁹Ar geochronology. Mean ⁴⁰Ar/³⁹Ar laser microprobe ages for these domains are 370.7 ± 1.0 Myr for S₃ and 345.5 ± 1.7 Myr for S₄. Because estimates of the Ar closure temperature for white micas are substantially higher than the inferred growth temperatures of the micas defining S₃ and S₄, these values are interpreted as periods since cleavage formation. This interpretation is consistent with independent geochronological constraints on the age of the Acadian orogeny in the region.     

1994 REPORT ON WHIN SILL DOLERITE WS-E FROM ENGLAND AND PITSCURRIE MICROGABBRO PM-S FROM SCOTLAND: ASSESSMENT BY ONE HUNDRED AND FOUR INTERNATIONAL LABORATORIES

This compilation report describes the field location, mineralogy, preparation and homogeneity testing of two new GIT-IWG reference materials: Whin Sill dolerite (WS-E) from England and Pitscurrie microgabbro (PM-S) from Scotland. The elemental composition of these two new reference materials has been established by an international cooperative analysis programme involving participation by 104 laboratories. A full assessment of these analytical results is presented, from which working values have been derived for the major elements as well as for 45 trace elements in WS-E and 44 trace elements in PM-S. Furthermore, isotopic ratios are presented for both samples, particularly for ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd.     

Chemostratigraphy of Neoproterozoic carbonates: implications for 'blind dating'

The δ¹³C_carb and ⁸⁷Sr/⁸⁶Sr secular variations in Neoproteozoic seawater have been used for the purpose of 'isotope stratigraphy' but there are a number of problems that can preclude its routine use. In particular, it cannot be used with confidence for 'blind dating'. The compilation of isotopic data on carbonate rocks reveals a high level of inconsistency between various carbon isotope age curves constructed for Neoproteozoic seawater, caused by a relatively high frequency of both global and local δ¹³C_carb fluctuations combined with few reliable age determinations. Further complication is caused by the unresolved problem as to whether two or four glaciations, and associated negative δ¹³C_carb excursions, can be reliably documented. Carbon isotope stratigraphy cannot be used alone for geological correlation and 'blind dating'. Strontium isotope stratigraphy is a more reliable and precise tool for stratigraphic correlations and indirect age determinations. Combining strontium and carbon isotope stratigraphy, several discrete ages within the 590–544 Myr interval, and two age-groups at 660–610 and 740–690 Myr can be resolved.     

Early Himalayan exhumation: Isotopic constraints from the Indian foreland basin

Nd- and Sr-isotopic compositions of Palaeogene foreland basin sediments are used to provide insights into early Himalayan evolution, particularly the timing of exposure of high ⁸⁷Sr/⁸⁶Sr units, erosion of which may have caused the late Tertiary increase in oceanic Sr-isotopic ratios. During the late Palaeocene–early Eocene, erosion was from mixed sources including suture zone rocks. Exhumation of the High Himalaya was occurring by the time of deposition of alluvial sediments after mid-Oligocene times and this source has dominated Himalayan sediments from at least this time until the present day. The transition is interpreted to reflect exhumation of 'basement rocks' of the Indian plate, when the High Himalaya became a sufficient topographic barrier to separate suture zone rocks from the foreland basin. The marked rise in seawater ⁸⁷Sr/⁸⁶Sr from 40 Ma is consistent with the erosion of a Himalayan source with a high ⁸⁷Sr/⁸⁶Sr ratio.     

10Be chronology of the last deglaciation of County Donegal, northwestern Ireland

A well-preserved moraine on the northern coast of County Donegal, Ireland, has played a critical role in our understanding of the glacial history of this sector of the Irish Ice Sheet (IIS). Because of a lack of numerical dating of the moraine, however, previous interpretations of its age and significance to the glacial history of this region have varied widely. Here we report eight in situ cosmogenic ¹⁰Be ages on boulders sampled from the moraine. Two of these ages are outliers, with the remaining six ranging from 18.8±1.0 ¹⁰Be kyr to 20.9±1.3 ¹⁰Be kyr, with an uncertainty-weighted mean age of 19.4±0.3 ¹⁰Be kyr (19.4±1.2 kyr accounting for production rate uncertainty). Our results confirm one previous ¹⁰Be age obtained from the moraine, with the combined data ( n =7) constraining the age of initial deglaciation of the IIS from its LGM position on the continental shelf to be 19.3±0.3 ¹⁰Be kyr (19.3±1.2 kyr accounting for production rate uncertainty). These ages are in excellent agreement with calibrated ¹⁴C ages that constrain retreat of the IIS margin from the continental shelf elsewhere in northwestern and western Ireland and the Irish Sea Basin associated with the start of the Cooley Point Interstadial (≥20–≤18.2 cal. kyr BP), suggesting widespread deglaciation of the IIS ∼19.5–20 kyr ago.     

Rate of late Quaternary ice-cap thinning on King George Island, South Shetland Islands, West Antarctica defined by cosmogenic 36Cl surface exposure dating

Glacial landforms on the Barton and Weaver peninsulas of King George Island in the South Shetland Islands, West Antarctica were mapped and dated using terrestrial cosmogenic ³⁶Cl methods to provide the first quantitative terrestrial record for late Quaternary deglaciation in the South Shetland Islands. ³⁶Cl ages on glacially eroded and striated bedrock surfaces range from 15.5±2.5 kyr to 1.0±0.7 kyr. The ³⁶Cl ages are younger with decreasing altitude, indicating progressive downwasting of the southwestern part of the Collins Ice Cap at a rate of ∼12 mm yr⁻¹ since 15.5±2.5 kyr ago, supporting the previously published marine records for the timing and estimate of the rate of deglaciation in this region.     

Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses

We have measured ⁸⁷Sr/⁸⁶Sr and ¹⁴³ Nd/¹⁴⁴ Nd isotope ratios in different batches and aliquots of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1 and GSP-1 by thermal ionisation mass spectrometry. In addition, we also analysed the eight Max-Planck-Institut-Dingwell (MPI-DING) reference glasses. Nearly all isotope ratios obtained in the different aliquots and batches agree within uncertainty limits indicating excellent homogeneity of the USGS powders and the MPI-DING glasses. With the exception of GSP-2, the new USGS RMs are also indistinguishable from the ratios found in the original USGS RMs (⁸⁷Sr/⁸⁶Sr: 0.704960, 0.704958 (BCR-1, -2), 0.703436, 0.703435 (BHVO-1, -2), 0.703931, 0.703931 (AGV-1, -2); ¹⁴³ Nd/¹⁴⁴ Nd: 0.512629, 0.512633 (BCR-1, -2), 0.512957, 0.512957 (BHVO-1, -2); 0.512758, 0.512755 (AGV-1, -2)). This means that for normalisation purposes in Sr and Nd isotope geochemistry BCR-2, BHVO-2 and AGV-2 can well replace BCR-1, BHVO-1 and AGV-1 respectively.     

Mo-related Adakitic Granitoids from Non-island-arc Setting: Jecheon Pluton of South Korea

Abstract. The Jecheon granitoids, having an elongated shape of NE-SW 27 km and NW-SE 13 km (190 km²), are composed mostly of magnetite-series hornblende-biotite granodiorite and biotite granite, which intrude into the Neoproterozoic metamor-phic and Paleozoic sedimentary rocks of the Ogcheon Belt. The granitoids have Triassic-Jurassic age of 202.7 ±1.9 Ma with very high ⁸⁷Sr/⁸⁶Sr initial ratio of 0.7140. The granodiorite has 63–69 % SiO₂, 15.1–17.3 % Al₂O₃, <1.6 % MgO, 6–15 ppm Y and Sr/Y ratios of 24–76, and is depleted in HREE. Biotite granite together, the Jecheon pluton has adakitic characteristics, which are unique in a continental tectonic setting. The granitoids may have been generated by partial melting of an older adakitic granitoid of I-type basement, or by separation of early crystallized garnet and hornblende from an anatectic melt.     

Measurement of SIMS Instrumental Mass Fractionation of Pb Isotopes During Zircon Dating

An igneous zircon reference material (OG1) was characterised for U-Pb isotopes by ID-TIMS, and utilised to evaluate SIMS (SHRIMP) instrumental mass fractionation (IMF) of radiogenic Pb isotopes (²⁰⁷Pb*/²⁰⁶Pb*). The TIMS ²⁰⁷Pb*/²⁰⁶Pb* reference value for OG1 was 0.29907 ± 0.00011 (95% confidence limit), 3465.4 ± 0.6 Ma. The high ²⁰⁷Pb* (∼ 30 μg g⁻¹), negligible common Pb, and isotopic homogeneity permitted precise (± 1–2‰) ²⁰⁷Pb*/²⁰⁶Pb* measurements within the analytical sessions. External reproducibility of mean ²⁰⁷Pb*/²⁰⁶Pb* ratios between sessions was demonstrated for one instrument, yielding a mean IMF of +0.87 ± 0.49‰. The mean ²⁰⁷Pb*/²⁰⁶Pb* ratios between instruments were dispersed beyond uncertainties, with session IMF values from +3.6 ± 1.7‰ to −2.4 ± 1.3‰, and a grand mean IMF value (twenty-six sessions) of +0.70 ± 0.52‰, indicating a tendency towards elevated ²⁰⁷Pb*/²⁰⁶Pb*. The specific causes of variability in IMF are unclear, but generally reflect subtle differences in analytical conditions. The common practice in SIMS of assuming that IMF for Pb⁺ is insignificant could result in systematic age biases and underestimated uncertainties, of critical importance for precise correlation of Precambrian events. Nevertheless, a zircon RM such as OG1 can be readily incorporated into routine dating to improve ²⁰⁷Pb*/²⁰⁶Pb* accuracy and external reproducibility.     

Structurally controlled fluid flow associated with breccia vein formation

A breccia vein sampled from a shear zone in greenschist facies metapelites at Mount Isa, Queensland, Australia, shows a systematic variation in vein geometry that is related to the geometry of folding and faulting within the sample. Calcite vein-fill is coarse grained and equigranular, suggesting precipitation in a fluid-filled space. Partially folded veins suggest that veining occurred during folding and faulting. The breccia vein contains a central zone in which dilation has occurred simultaneously in all directions in the plane of section, implying that this was a zone of high fluid pressure and nearly isostatic differential stress during folding and faulting. From these observations, it can be inferred that the breccia vein was a zone of high permeability and a likely fluid channel during deformation. This hypothesis was tested by stable isotope analysis of veins and host rocks. The calcite veins have δ¹³C values of -11.1 ± 0.1% and δ¹⁸O values of 6-10%_o, whereas the host metapelite has δ¹³C values of -10.62 and -10.11% and δ¹⁸O values of 14-15%_o. These values are consistent with an igneous-derived, H₂O-dominated fluid that exchanged little oxygen with the host rocks, but derived much of its carbon from the wall rock. The isotopic disequilibrium between the veins and the wall rock confirms that the fluid was externally derived, and that the breccia vein acted as a channel for large-volume fluid flow within the shear zone.     

Metamorphic decarbonation, silicate weathering and the long-term carbon cycle

The seawater ⁸⁷Sr/⁸⁶Sr curve implies a 50–100 Myr episodicity in weathering rate which requires a corresponding variation in CO₂ degassing from the solid earth to the atmosphere. It is proposed that this is caused by orogenesis, which both produces CO₂ as a result of metamorphic decarbonation reactions, and consumes extra CO₂ as a consequence of erosion-enhanced weathering. Global climate on the geological time-scale is therefore contTolled by the difference between the relatively large and variable orogenic-moderated degassing and weathering CO₂ fluxes.