Investigation of the Ablation Behaviour of Andradite-Grossular Garnets and Rutile with Implications for U-Pb Geochronology

U-Pb dating of andradite-grossular garnet (grandite) and rutile by LA-ICP-MS can be used to constrain various metamorphic, metasomatic and igneous geological processes. In this study, we examine and compare the impact of different analytical conditions (fluence, pulse width, laser beam size and ablation frequency) on the ablation crater morphology, ablation rates, down-hole fractionation and U-Pb ages of grandite and rutile samples of different compositions. The shapes of grandite ablation craters suggest the mineral ablates by classical evaporation with significant melting that cannot be eliminated even at fluences just above the ablation threshold. Grandite garnets with higher andradite proportions have faster ablation rates. The overall low U contents of grandite require using large laser beam sizes to obtain acceptable precision of U-Pb ages. At such conditions and crater depths < 10 μm, fluences of 2.1 and 3.5 J cm^-2, laser pulse width of 5 ns and 20 ns, and ablation frequencies between 3.5 and 6.5 Hz, obtain similar and reproducible ages when the proportion of grossular is < 35%. Rutile ablation crater morphology shows evidence of melt splashing and thermal stress cracking. They have significant crater bottom features, which increase in relief with lower fluences and a higher number of laser shots, indicating the features are probably energy-related and making higher fluences, such as 5 J cm^-2, necessary for uniform ablation when using 193 nm excimer lasers. The slow ablation rate at low fluences and then steep increase at around 2.0 J cm^-2 suggests a transition in the ablation mechanism from exfoliation to classical vaporisation. Crater bottom features and other ablation behaviour vary between samples, which could be related to their difference in colour. Although the down-hole fractionation patterns of the samples are similar at 5 J cm^-2, the U-Pb ages of some samples vary significantly with different analytical conditions and/or measurement sessions, particularly when using laser beam sizes of 30 μm, suggesting differences in mass bias and more variable ablation behaviour. A laser beam size of at least 60 μm is recommended for reproducible U-Pb dating of rutile.     

STDGL3, a Reference Material for Analysis of Sulfide Minerals by Laser Ablation ICP-MS: An Assessment of Matrix Effects and the Impact of Laser Wavelengths and Pulse Widths

A new reference material, STDGL3, for the calibration of in situ analyses of sulfide minerals by LA-ICP-MS has been developed and characterised. It represents a lithium-borate-based glass containing a mixture of Zn- and Fe-sulfide concentrates doped with several chalcophile elements as well as Zr, Gd, Hf and Ta required for assessing common interferences on Ag, Au and Pt. STDGL3 has a wider range of elements and a better homogeneity compared with existing reference materials for LA-ICP-MS analysis of sulfides. Compositional variations for most elements are below 3% RSD, below 5% RSD for Ag, Au and Pt, and below 7% RSD for Se, when performing spot analyses with a 50 μm beam size. Its preparation recipe is reproducible allowing for multiple batches to be made. Use of STDGL3 significantly improves accuracy of sulfide mineral analysis by LA-ICP-MS when compared with use of other available reference materials. Performance of STDGL3 was evaluated using several different laser systems. No significant change was observed between 193 nm ArF excimer lasers with 5 and 20 ns pulse widths, but use of 213 and 248 nm lasers displays more systematic differences, especially when analysing galena. Correction coefficients are needed for some elements (Zn and Cd in particular) when analysing sulfide minerals using STDGL3 as a calibration reference material.     

Assessing vertical diffusion in a stratified lake using a three-dimensional hydrodynamic model

Vertical turbulent diffusivity (K_z), which can be estimated from water temperature, is a key factor in the evolution of water quality in lentic waters. In this study, we analysed the capability of a three-dimensional hydrodynamic model (EFDC) to capture water temperature and vertical diffusivity in Lake Arendsee in the Northern German plain. Of particular interest to us is to evaluate the model performance for capturing the diffusion minimum within the metalimnion and analyse the response of the metalimnetic K_z to meteorological forcing, namely changing wind speed and warming. The comparison confirmed that the calibrated model could reproduce both stratification dynamics and vertical diffusion profiles in the lake. The model was also shown to be able to capture the duration and vertical extent of the metalimnetic diffusion minimum. The scenario results illustrate that, compared to air temperature, wind velocity appeared to be the more influential meteorological variable on the vertical exchange within the metalimnion. While increasing wind velocities mostly affected the minimum values of K_z in the metalimnion and thus led to intensified vertical exchange, the reduction of wind velocity mostly affected the depth of minimal K_z, but not its absolute value.     

Tectonic controls on Miocene sedimentation in the Southern Taranaki Basin and implications for New Zealand plate boundary deformation

Miocene strata in the southern Taranaki Basin (STB), up to 3 km thick, provide a distal record of erosion associated with plate boundary deformation in New Zealand. 2D and 3D seismic reflection data tied to drillhole stratigraphy have been used to constrain four main phases of basin development. These are: (a) Early Miocene (22–19 Ma) subsidence, dominantly bathyal water depths and deposition of minor submarine fans along the eastern basin margin. (b) Middle Miocene (19–14 Ma) widespread submarine fan deposition on a bathyal basin floor in the central STB. (c) Rapid Middle–Late Miocene (14–7 Ma) progradation of the shelf break northwards across the STB. (d) Widespread uplift and erosion of the STB during the latest Miocene–Pliocene (7–4.5 Ma). Bathyal water depths and fan deposition in the Early Miocene were influenced by vertical motions on major reverse faults and regional subsidence produced by subduction of the Pacific plate beneath northern New Zealand. Subsequent submarine fan deposition and northward shelf‐break progradation reflect increasing input of terrigenous material, primarily eroded from an uplifting region to the south of the STB. Sedimentation patterns in the STB are consistent with the age and locations of conglomerates deposited in onshore West Coast basins, related to this uplift and erosion. Sediment transport in the West Coast region was mainly parallel to NNE trending active reverse faults, and in the STB was perpendicular to the NE‐SW orientated shelf break, especially from ca. 14–7 Ma, when sedimentation rates exceeded fault‐displacement rates. Increases in sedimentation rates in the STB coincide with regional increases in the rates of shortening that appear to reflect plate boundary‐wide events and have been attributed to, or correlated with, increases in the plate convergence rate. Miocene sedimentation patterns in the STB thus reflect both intra‐basinal deformation and tectonic signals from the wider developing New Zealand plate boundary.     

Long-term displacement of intertidal seagrass and mussel beds by expanding large sandy bedforms in the northern Wadden Sea

On aerial photographs, sandy tidal flats display (1) large sandy bedforms (> 10 m long, > 3 m wide), indicating effects of strong hydrodynamics on sediment relief, and (2) beds of seagrass and mussels, indicating stable sediment conditions. These physical and biogenic structures have been mapped from aerial photographs taken in a back-barrier tidal basin of the North Sea coast at low tide between 1936 and 2005. Fields of large intertidal sandy bedforms show a consistent spatial distribution in the central part of the basin, and have increased in area from 7.2 to 12.8 km², corresponding now to 10% of the tidal flats. Areal expansion may be linked to a rise in average high tide level and an increase of the expansion rate from the 1960s to the mid 1990s might be traced back to an increased frequency of storm tides during this period. It is shown that expanding fields of large sandy bedforms have replaced mussel beds in the low tidal zone and displaced seagrass beds in the mid tidal zone. Fields of intertidal large sandy bedforms are expected to expand further with an accelerating rise in sea level, and it is recommended to monitor these physical indicators of sediment instability and disturbance of biogenic benthic structures by analysing aerial photographs.     

DMS oxidation and turbulent transport in the marine boundary layer: A numerical study

DMS oxidation in the marine boundary layer has been simulated with a mesoscale meteorological model including detailed physical parameterizations. The impact of vertical turbulent transport on the DMS and SO₂ diurnal cycles with and without in-cloud SO₂ oxidation has been studied in a one-dimensional version of the model and compared to results obtained with a zero-dimensional box model. Initialisation has been done using balanced values issued from the imposed sea-air fluxes, dry deposition fluxes and chemical source/sink terms. Particular emphasis has been put on the important role played by evolving vertical mixing in the marine boundary layer.     

Olivine [100] normal to foliation: lattice preferred orientation in prograde garnet peridotite formed at high H<Subscript>2</Subscript>O activity,Cima di Gagnone (Central Alps)

Automated electron backscattered diffraction (EBSD) was applied using a scanning electron microscope to obtain lattice preferred orientation (LPO) data for olivine in garnet peridotites of the Central Alps. As a reference frame, the LPOs of enstatite were also investigated. In the garnet peridotite at Cima di Gagnone (CDG), a weak foliation carrying a distinct lineation is present. The lineation is characterized by elongated enstatite, olivine and poikiloblastic garnet. Olivine shows a very unusual LPO with [100] normal to foliation and [001] parallel to lineation. Achsenverteilungsanalyse (AVA) maps demonstrate that [001] of olivine grains corresponds quite well to their maximum length axes which are preferentially parallel to the lineation. Numerous planar hydrous defects within (001) planes of olivine are marked by palisades of ilmenite rods and show a preferred orientation normal to lineation. Calculated P-wave velocities for CDG are fastest (8.32 km s^у) normal to foliation with a relatively low anisotropy (2.9%). Compared to mantle peridotites with the usual (010)[100] LPO where the fastest Vp direction is towards the lineation, the relationship between flow geometry and seismic anisotropy is significantly different at CDG. Several mechanisms for the formation of the LPO type at CDG are considered, with glide possible on (100)[001] of olivine. On the basis of field data as well as petrographic and petrologic evidence, it has been demonstrated that the CDG garnet peridotite formed by prograde metamorphism from a hydrous protolith at pressures and temperatures of about 3.0 GPa and 750 °C, respectively. The CDG LPO is interpreted to have formed during hydrous subduction zone metamorphism. The same interpretation may hold for the previously investigated olivine LPO at Alpe Arami, which is similar to that at the nearby CDG. The observed anomalous LPO is no proof for ultradeep (>3.0 GPa) conditions.     

A study of lignin degradation in leaf and needle litter using C-labelled tetramethylammonium hydroxide (TMAH) thermochemolysis: Comparison with CuO oxidation and van Soest methods

We studied the degradation of lignin in leaf and needle litter of ash, beech, maple, pine and spruce using ¹³C-labelled tetramethylammonium hydroxide (¹³C TMAH) thermochemolysis. Samples were allowed to decompose for 27 months in litter bags at a German spruce forest site, resulting in a range of mass loss from 26% (beech) to 58% (ash). In contrast to conventional unlabelled TMAH thermochemolysis, ¹³C-labelling allows thermochemolysis products from lignin, demethylated lignin and other polyphenolic litter compounds (e.g. tannins) to be distinguished. Proxies for lignin degradation (phenol yield; acid/aldehyde ratio of products) changed considerably upon correction for the contribution of non-lignin sources to the thermochemolysis products. Using the corrected values, we found increasing acid/aldehyde values as well as decreasing or constant yield of lignin derived phenols normalised to litter carbon, suggesting pronounced lignin degradation by wood-rotting fungi. No indication for build up of demethylated lignin through the action of brown rot fungi on ring methoxyls was found. The results were compared with those of other analytical techniques applied in previous studies. Like ¹³C-TMAH thermochemolysis, CuO oxidation showed increasing lignin oxidation (acid/aldehyde ratio) and no/little enrichment of lignin derived phenols in the litter. Molecular lignin degradation patterns did not match those from analysis of total acid unhydrolysable residues (AURs). In particular, the long assumed selective preservation of lignin during the first months of litter decomposition, based on AUR analysis, was not supported by results from the CuO and ¹³C TMAH methods.     

Cenozoic development of northern Svalbard based on thermochronological data

Northern Svalbard represents a basement high surrounded by the Norwegian‐Greenland Sea/Fram Strait, Eurasian Basin, the Barents Shelf and the onshore Central Tertiary Basin (CTB). Published apatite fission track (AFT) data indicate Mesozoic differential, fault‐controlled uplift and exhumation of the region. Thermal history modelling of published and new AFT and (U–Th–Sm)/He ages of 51–153 Ma in the context of regional stratigraphy and geomorphology implies at least two, possibly three, uplift and exhumation stages since late Mesozoic, separated by episodes of subsidence and sediment deposition. Late Cretaceous/Palaeocene exhumation and subsequent burial appear to be related with the transition of compressional to transpressional collision of Svalbard and Greenland during the Eurekan Orogeny. Renewed exhumation since the Oligocene probably results from passive margin formation after the separation of Svalbard and Greenland, when a new offshore sedimentary basin opened west of Svalbard. Final uplift since the Miocene eventually re‐exposed the palaeosurface of northern Svalbard.