Magma chamber evolution prior to the Campanian Ignimbrite and Neapolitan Yellow Tuff eruptions (Campi Flegrei,Italy)

The Campi Flegrei (Campanian Region, Italy) experienced two cataclysmic caldera-forming eruptions which produced the Campanian Ignimbrite (39 ka, CI) and the Neapolitan Yellow Tuff (15 ka, NYT). We studied the minor eruptions before both these large events to understand magma chamber evolution leading towards such catastrophic eruptions. Major, trace element, and Sr and Nd isotope compositions of pre-Campanian Ignimbrite and pre-Neapolitan Yellow Tuff products define distinct geochemical groups, which are here interpreted as distinct magma batches. These batches do not show any transitional trend towards the CI and NYT eruptions. The CI and NYT systems are decoupled geochemically and isotopically. At least one of the pre-CI and one of the pre-NYT erupted magma batches qualifies as mixing endmembers for the large CI and NYT eruptions, and thus, must have been stored in reservoirs for some time to remain available for the CI and NYT eruptions. The least evolved, isotopically distinct magma compositions that are typical of the last phases of the NYT and CI eruptions did not occur before caldera-forming events. Based on the new data, we propose the following scenario: Multiple magma chambers with distinct compositions existed below the Campi Flegrei before the CI and NYT eruptions and remained generally separated for some time unless new magma was recharged. In each case, one of the residing magma reservoirs was recharged by a new large-volume magma input of intermediate composition from a deeper differentiating magma reservoir. This may have triggered the coalescence of the previously separated reservoirs into one large chamber which fed the cataclysmic caldera-forming eruption. Large magma chambers in the Campi Flegrei may therefore be ephemeral features, interrupted by periods of evolution in individual, separated magma reservoirs.     

Laminated tufa sediments formed from overflow karst springs: Controls on their deposition and carbon–oxygen isotope records

Tufa sediments are freshwater carbonates that precipitate in karst regions after degassing of carbon dioxide from groundwater in contact with the atmosphere. When laminated, these carbonates can provide high‐resolution records for the study of climate, hydrological and environmental conditions at the time of their precipitation. The formation of these carbonates directly depends on the hydrological regime, and in karst regions discontinuous discharges are often recorded. This study investigates the record of recent laminated tufa sediments precipitated downstream overflow springs in Trabaque Canyon (central Spain). The hydrological dynamics of the karst system were monitored for over three years and a stable isotope record was obtained from laminated tufa carbonates precipitated from an overflow spring. Additionally, a hydrological model of overflow springs was generated and a tufa δ¹⁸O record under constrained parameters was simulated. Temperature is the dominant control of the variation in tufa δ¹³C and δ¹⁸O values within each lamina, although when comparing different laminae, δ¹³C_DIC and δ¹⁸O of river water are also major controls. The positive correlation between tufa δ¹³C values and water temperature is caused by the fractionation occurred by carbon dioxide degassing due to the thermal dependence of carbon dioxide solubility. Additionally, the system recorded a temperature‐independent degassing process caused by the large gradient between groundwater and atmospheric carbon dioxide that is limited to the proximity of the spring. This study cautions on the risk of assuming continuous deposition when studying laminated tufa sediments and highlights the potential of their stable isotope records to provide hydrological information of their aquifers during the past.     

Internal flow structures in columnar jointed basalt from Hrepphólar, Iceland: II. Magnetic anisotropy and rock magnetic properties

The anisotropy of magnetic susceptibility (AMS) and rock magnetic properties were measured on specimens from a basalt plate that was cut from a vertical section of a basalt column from Hrepphólar, Iceland. Macroscopic structures are clearly distinguishable in the plate, including banding inferred to represent viscous fingering parallel to the vertical axis of the column. Rock magnetic experiments indicate that the dominant ferromagnetic (sensu lato) mineral is titanomagnetite, Fe _3?x Ti _x O₄, with a Ti-composition of x?=?~0.6. Magnetic properties are related to the position within the plate and reveal a dominant volume fraction of single domain titanomagnetite in the center of the basalt column, with multidomain titanomagnetite away from the center. The AMS determined by low-field measurements shows an inconclusive relationship with the visual structures, which arises from variation of the grain size (i.e., single domain versus multidomain) across the column. In contrast, the AMS measured with a high-field torsion magnetometer avoids the complication of magnetic domain state, as is demonstrated in this contribution, and additionally allows for the separation of ferrimagnetic from paramagnetic sub-fabrics. Both sub-fabrics display a clear relationship with the macroscopic structures and support the hypothesis that vertical flow of melt took place during development of the Hrepphólar columnar basalt. Maximum susceptibility axes of the ferrimagnetic sub-fabric are grouped near the vertical axis of the column. The paramagnetic sub-fabric varies systematically across the column in coincidence with internal structure. The shape of the magnetic susceptibility ellipsoid varies across the basalt column, showing an increasingly prolate fabric toward its center.     

Continuous 60-year stable isotopic and earth-alkali element records in a modern laminated tufa (Jaruga,river Krka,Croatia): Implications for climate reconstruction

A continuous 60-year record (1938–1998) of stable isotope compositions of carbon and oxygen, as well as trace metal (Mg, Sr, Ba) concentrations in a laminated calcite crust precipitated in a short artificial tunnel on a non-equilibrium groundwater-fed karstic river is presented. Chemical and isotopic records have been compared to hydrometeorological data, available for the last 48 years. An attempt is made to relate isotopic and geochemical variations in the crust to environmental parameters, such as temperature, precipitation and changes in vegetation cover, as well as to postdepositional recrystallisation of the older crust material. Isotopic composition of the crust is largely influenced by non-equilibrium precipitation, which favours the incorporation of isotopically depleted C and O into the carbonate. Furthermore, because of the complicated hydrological situation, there is no observable correlation between the stable oxygen isotope composition of water and temperature. The result is that the ¹⁸O isotopic thermometers overestimate the measured precipitation temperatures. Temperatures calculated from Mg/Ca ratios of water and the carbonate match the δ¹⁸O palaeotemperatures within ± 2.4 °C in the older part of the crust, precipitated before the onset of industrial pollution of the river. It was demonstrated that the application of Mg palaeothermometry in natural systems, where the Mg/Ca ratio of water is influenced not only by temperature, but also by other environmental parameters such as precipitation, surface runoff, groundwater retention time and anthropogenic influences, is subject to a large uncertainty, up to 10 °C.     

Isotopic fractionation and reaction kinetics between Cr(III) and Cr(VI) in aqueous media

The redox-sensitive stable isotope geochemistry of chromium bears the potential to monitor the attenuation of chromate pollution and to investigate changes in environmental conditions in the present and the past. The use of stable Cr isotope data as a geo-environmental tracer, however, necessitates an understanding of the reaction kinetics and Cr fractionation behaviour during redox transition and isotope exchange. Here, we report stable chromium isotope fractionation data for Cr(VI) reduction, Cr(III) oxidation and isotopic exchange between soluble Cr(III) and Cr(VI) in aqueous media. The reduction of Cr(VI) to Cr(III) with H₂O₂ under strongly acidic conditions shows a near-equilibrium isotope fractionation of Δ^53/52Cr_{(Cr(III)-Cr(VI))} of −3.54 ± 0.35‰. At pH neutrality, however, the reduction experiments show a kinetic isotope fractionation Δ^53/52Cr_{(Cr(III)-Cr(VI))} of −5‰ for the extent of reduction of up to 85% of the chromium. The oxidation of Cr(III) to Cr(VI) in alkaline media, using H₂O₂ as the oxidant, cannot be explained by a single, unidirectional reaction. Our experiments indicate that the involvement of the unstable intermediates Cr(IV) and Cr(V) and their disproportionation during redox reactions between Cr(III) and Cr(VI) influence the overall fractionation factor, depending on the prevailing pH conditions and the reaction rates. No detectable isotope exchange between soluble Cr(VI) and Cr(III) species at pH values of 5.5 and 7 was revealed over a timescale of days to weeks. This means that, at least within such a time frame, the isotopic composition of Cr(VI) in a natural system will not be influenced by equilibration with any Cr(III) and thus reveal the true extent of reduction, given that the Cr isotope composition of the source Cr(VI) and the fractionation factor for the prevailing conditions are known.     

Origins of non-equilibrium lithium isotopic fractionation in xenolithic peridotite minerals: Examples from Tanzania

Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ⁷Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ⁷Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ⁷Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ⁷Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ⁷Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ⁷Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ⁷Li), while non mantle-like, low δ⁷Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.     

Seasonal climate inferences from high-resolution modern diatom data along a climate gradient: a case study

This study represents a step towards developing seasonal climate inferences by using high-resolution modern data sets. The importance of seasonal climate changes is highlighted by the instrumental record of a meteorological station close to our study site (lac du Sommet in the Laurentian Mountains, Québec, Canada): Between 1966 and 2001, May temperatures increased significantly by 3.1°C (r = 0.41, n = 35, p < 0.01) but annual mean temperatures only by 0.6°C (r = 0.21, n = 35, p > 0.05). Comparison of this instrumental record with fossil diatom assemblages in a sediment core from lac du Sommet showed that axis one of a principal component analysis (PCA) of the fossil diatoms was best correlated with wind velocity in June (r = 0.62, n = 19, p < 0.005) and that past diatom production was significantly enhanced in periods with colder July temperatures (r =  ?0.77, n = 19, p < 0.0005) and higher wind velocity in June (r = 77, n = 19, p < 0.0005). The strong impact of the spring and summer conditions on overall diatom composition and productivity suggests that seasonal lake responses to climate are more important than annual mean temperatures. However, the seasonal dynamics of diatom communities are not well understood, and seasonality is rarely inferred effectively from lake sediment studies. Our research presents a pilot study to answer a twofold question: Is it possible to identify diatom communities which are typical for warmer or colder seasonal climate using sediment traps, and if it is, can this knowledge be used to infer seasonal climate conditions from fossil diatom assemblages? To address these questions, the seasonal dynamics of diatom communities and water chemistry were studied using sediment traps and water samples at biweekly intervals in four lakes distributed along an altitudinal gradient in the Laurentian Mountains from May through October 2002. Date of ice break-up was significantly related to the diatom assemblages taken in spring and uncorrelated to other significant environmental variables. Summer water temperature, circulation of the water column and pH explained a significant part of the biological variance in summer, and total nitrogen (TN) explained most of the biological variance in autumn. To infer these variables, weighted averaging partial least squares models were applied to the seasonal data sets. Inferred ice break-up dates were significantly correlated with number of days below 0°C in April (r = 0.52, n = 19, p < 0.025), inferred circulation of the water column was significantly related to measured wind velocity in June (r = 0.64, n = 19, p < 0.005), inferred summer water temperature and inferred pH was significantly related to measured July air temperature (r = 0.50, r =  ?53, n = 19, p < 0.025) and inferred TN autumn concentrations had an inverse relationship to August temperatures (r =  ?0.53, n = 19, p < 0.01). This comparison of the historical record with diatom-inferred seasonal climate signals, based on the comparison of fossil diatom assemblages with modern sediment trap data of high temporal resolution, provides a promising new approach for the reconstruction of seasonal climate aspects in paleolimnological studies.     

Scales of columnar jointing in igneous rocks: field measurements and controlling factors

Columnar jointing is a common feature of solidified lavas, sills and dikes, but the factors controlling the characteristic stoutness of columns remain debated, and quantitative field observations are few in number. In this paper, we provide quantitative measurements on sizing of columnar joint sets and our assessment of the principal factors controlling it. We focus on (1) chemistry, as it is the major determinant of the physical (mechanical and thermal) properties of the lava, and (2) geology, as it influences the style of emplacement and lava geometry, setting boundary conditions for the cooling process and the rate of heat loss. In our analysis, we cover lavas with a broad range of chemical compositions (from basanite to phonolite, for six of which we provide new geochemical analyses) and of geological settings. Our field measurements cover 50 columnar jointing sites in three countries. We provide reliable, manually digitized data on the size of individual columns and focus the mathematical analysis on their geometry (23,889 data on side length, of which 17,312 are from full column sections and 3,033 data on cross-sectional area and order of polygonality). The geometrical observations show that the variation in characteristic size of columns between different sites exceeds one order of magnitude (side length ranging from 8 to 338 cm) and that the column-bounding polygons’ average order is less than 6. The network of fractures is found to be longer than required by a minimum-energy hexagonal configuration, indicating a non-equilibrium, geologically quick process. In terms of the development and characteristic sizing of columnar joint sets, our observations suggest that columns are the result of an interplay between the geological setting of emplacement and magma chemistry. When the geological setting constrains the geometry of the emplaced body, it exerts a stronger control on characteristic column stoutness. At unconstrained geometries (e.g. unconfined lava flows), chemistry plays the major role, resulting in stouter columns in felsic lavas and slenderer columns in mafic lavas.