The geochemistry of gem opals as evidence of their origin

Seventy-seven gem opals from ten countries were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) through a dilution process, in order to establish the nature of the impurities. The results are correlated to the mode of formation and physical properties and are instrumental in establishing the geographical origin of a gem opal. The geochemistry of an opal is shown to be dependant mostly on the host rock, at least for examples from Mexico and Brazil, even if modified by weathering processes. In order of decreasing concentration, the main impurities present are Al, Ca, Fe, K, Na, and Mg (more than 500 ppm). Other noticeable elements in lesser amounts are Ba, followed by Zr, Sr, Rb, U, and Pb. For the first time, geochemistry helps to discriminate some varieties of opals. The Ba content, as well as the chondrite-normalized REE pattern, are the keys to separating sedimentary opals (Ba > 110 ppm, Eu and Ce anomalies) from volcanic opals (Ba < 110 ppm, no Eu or Ce anomaly). The Ca content, and to a lesser extent that of Mg, Al, K and Nb, helps to distinguish gem opals from different volcanic environments. The limited range of concentrations for all elements in precious (play-of-color) compared to common opals, indicates that this variety must have very specific, or more restricted, conditions of formation. We tentatively interpreted the presence of impurities in terms of crystallochemistry, even if opal is a poorly crystallized or amorphous material. The main replacement is the substitution of Si⁴⁺ by Al³⁺ and Fe³⁺. The induced charge imbalance is compensated chiefly by Ca²⁺, Mg²⁺, Mn²⁺, Ba²⁺, K⁺, and Na⁺. In terms of origin of color, greater concentrations of iron induce darker colors (from yellow to “chocolate brown”). This element inhibits luminescence for concentrations above 1000 ppm, whereas already a low content in U (≤ 1 ppm) induces a green luminescence.     

Stable isotope study of the Archaean rocks of the Vredefort impact structure,central Kaapvaal Craton,South Africa

The Vredefort dome in the Kaapvaal Craton was formed as a result of the impact of a large meteorite at 2.02 Ga. The central core of Archaean granitic basement rocks is surrounded by a collar of uplifted and overturned strata of the Witwatersrand Supergroup, exposing a substantial depth section of the Archaean crust. Orthogneisses of the core show little variation in whole-rock δ ¹⁸O value, with the majority being between 8 and 10‰, with a mean of 9.2‰ (n = 35). Quartz and feldspar have per mil differences that are consistent with O-isotope equilibrium at high temperatures, suggesting minimal interaction with fluids during subsequent cooling. These data refute previous suggestions that the Outer Granite Gneiss (OGG) and Inlandsee Leucogranofels (ILG) of the core represent middle and lower crust, respectively. Granulite-facies greenstone remnants from the ILG have δ ¹⁸O values that are on average 1.5‰ higher than the ILG host rocks and are unlikely, therefore, to represent the residuum from the partial melting event that formed the host rock. Witwatersrand Supergroup sedimentary rocks of the collar, which were metamorphosed at greenschist-to amphibolite-facies conditions, generally have lower δ ¹⁸O values than the core rocks with a mean value for metapelites of 7.7‰ (n = 45). Overall, through an ∼20 km thick section of crust, there is a general increase in whole-rock δ ¹⁸O value with increasing depth. This is the reverse of what is normal in the crust, largely because the collar rocks have δ ¹⁸O values that are unusually low in comparison with metamorphosed sedimentary rocks worldwide. The collar rocks have δD values ranging from −35 to −115‰ (average −62‰, n = 29), which are consistent with interaction with water of meteoric origin, having a δD of about −25 to −45‰. We suggest that fluid movement through the collar rocks was enhanced by impact-induced secondary permeability in the dome structure. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Quantum yield for the photochemical production of dissolved inorganic carbon in seawater

The direct photooxidation of coloured dissolved organic matter (CDOM) to dissolved inorganic carbon (DIC) may provide a significant sink for organic carbon in the ocean. To calculate the rate of this reaction on a global scale, it is essential to know its quantum yield, or photochemical efficiency. We have determined quantum yield spectra, φ(λ), (moles DIC/mole photons absorbed) for 14 samples of seawater from environments ranging from a turbid, eutrophic bay to the Gulf Stream. The spectra vary among locations, but can be represented quite well by three pooled spectra for zones defined by location and salinity: inshore φ(λ)=e^{−(6.66+0.0285(λ−290))}; coastal φ(λ)=e^{−(6.36+0.0140(λ−290))}; and open ocean φ(λ)=e^{−(5.53+0.00914(λ−290))}. Production efficiency increases offshore, which suggests that the most highly absorbing and quickly faded terrestrial chromophores are not those directly responsible for DIC photoproduction.     

Hotspots in ambient noise caused by ice-edge eddies in the Greenland and Barents Seas

Mesoscale eddies are frequently observed in the Greenland and Barents Seas' marginal ice zone (MIZ). The objective of this study was to investigate the hypothesis that acoustic hotspots along the ice-edge region are due to mesoscale eddy currents interacting with the broken-up ice floes in the MIZ. To test this hypothesis, ambient-noise case studies were carried out during the MIZEX 85-87 and SIZEX 89 field experiments. In each experiment, ice-edge eddies were localized visually from aircraft and by use of satellite remote-sensing data obtained in near real time. Sonobuoys were, thereafter, deployed by fix-wing aircraft and helicopters in selected eddy areas. Ambient-noise data, recorded over several hours by aircraft, were analyzed estimating averaged ambient-noise levels at four selected frequencies: 40, 100, 315, and 1000 Hz. The analysis showed high mean levels and large gradients in ambient noise near ice-edge eddies and during strong wind and wave forcing against the ice edge. The conclusion of this study is that mapping of the ice edge and localization of mesoscale ocean processes using remote sensing from space will provide important input to ambient-noise prediction in the MIZ.     

Distribution of the Neogene Utsira Sand and the succeeding deposits in the Viking Graben area, North Sea

The sandy quartzose parts of the Utsira Formation, the Middle Miocene to mid Pliocene Utsira Sand, extends north–south along the Viking Graben near the UK/Norwegian median line for more than 450 km and 75–130 km east–west. The Utsira Sand is located in basin-restricted seismic depocentres, east of and below prograding sandy units from the Shetland Platform area with Hutton Sands. The Utsira Sand reaches thicknesses up to ca. 300 m in the southern depocentre and 200 m in the two northern depocentres with sedimentation rates up to 2–4 cm/ka. Succeeding Plio–Pleistocene is divided into seismic units, including Base Upper Pliocene, Shale Drape, Prograding Complex and Pleistocene. The units mainly consist of clay, but locally minor sands occur, especially at toes of prograding clinoforms (bottom-set sands) and in the Pleistocene parts, and the total thickness covering the Utsira Sand is in most places more than 800 m, but thins towards the margins.     

Shorelines of the Uppsala Esker East-Central Sweden: Their Use as Indicators of Regional Differences in Shore Displacement

About 750 different shoremarks, mainly shore terraces, have been levelled along the Uppsala esker. Using various methods it has been possible to arrange the shoremarks to shorelines or rather shoremark zones containing more shoremarks than intervening parts. The material was divided into two major parts, i.e. shoremarks below c . 15 m above sea level and shoremarks above c . 15 m. It was found that shorelines on the whole were sloping towards the north. This was expected because of the faster shore displacement in the northern part of the area. However, the shorelines below c . 15 m a.s.l. indicated a slower increase in shore displacement than those of higher altitudes. A conclusion drawn from this might be that the increase towards the north is retarded in the area around Lake Mälar. This result is in reasonable agreement with recent isobase systems constructed from the evidence of mareograph records and repeated precise levellings. On the other hand, the shoreline studies give evidence of more pronounced regional differences in shore displacement in earlier Litorina times than those found today.     

Coastal lagoons and beach ridges as complementary sedimentary archives for the reconstruction of Holocene relative sea‐level changes

Coastal lagoons and beach ridges are genetically independent, though non‐continuous, sedimentary archives. We here combine the results from two recently published studies in order to produce an 8000‐year‐long record of Holocene relative sea‐level changes on the island of Samsø, southern Kattegat, Denmark. The reconstruction of the initial mid‐Holocene sea‐level rise is based on the sedimentary infill from topography‐confined coastal lagoons (Sander et al., Boreas, 2015b). Sea‐level index points over the mid‐ to late Holocene period of sea‐level stability and fall are retrieved from the internal structures of a wide beach‐ridge system (Hede et al., The Holocene, 2015). Data from sediment coring, georadar and absolute dating are thus combined in an inter‐disciplinary approach that is highly reproducible in micro‐tidal environments characterised by high sediment supply. We show here that the commonly proximate occurrence of coastal lagoons and beach ridges allows us to produce seamless time series of relative sea‐level changes from field sites in SW Scandinavia and in similar coastal environments.     

Free allocation in the 3rd EU ETS period: assessing two manufacturing sectors

This article provides an analysis of the EU Emissions Trading Scheme (ETS) and the harmonized benchmark-based allocation procedures by comparing two energy-intensive sectors with activities in three Member States. These sectors include the cement industry (CEI) and the pulp and paper industry (PPI) in the UK, Sweden, and France. Our results show that the new procedures are better suited for the more homogeneous CEI, in which the outcome of stricter allocation of emissions allowances is consistent between Member States. For the more heterogeneous PPI – in terms of its product portfolios, technical infrastructures, and fuel mixes – the allocation procedures lead to diverse outcomes. It is the lack of product benchmark curves, and the alternative use of benchmark values that are biased towards a fossil fuel-mix and are based on specific energy use rather than emission intensity, which leads to allocations to the PPI that do not represent the average performance of the top 10% of GHG-efficient installations. Another matter is that grandfathering is still present via the historically based production volumes. How to deal with structural change and provisions regarding capacity reductions and partial cessation is an issue that is highly relevant for the PPI but less so for the CEI.

Policy relevance

After an unprecedented amount of consultation with industrial associations and other stakeholders, a harmonized benchmark-based allocation methodology was introduced in the third trading period of the EU ETS. Establishing a reliable and robust benchmark methodology for free allocation that shields against high direct carbon costs, is perceived as fair and politically acceptable, and still incentivizes firms to take action, is a significant challenge. This article contributes to a deeper understanding of the challenges in effectively applying harmonized rules in industrial sectors that are heterogeneous. This is essential for the debate on structural reformation of the EU ETS, and for sharing experiences with other emerging emissions trading systems in the world that also consider benchmark methodologies.