Evaluation of the use of photochemical indicators to assess ozone—NOx—VOC sensitivity in the Southwestern Iberian Peninsula

Understanding the chemical links between ozone (O₃) and its two main precursors, nitrogen oxides (NOx) and volatile organic compounds (VOC), is important for designing effective photochemical smog reduction strategies. This chemical relationship will determine which precursor (NOx or VOC) emission reduction will be more effective for decreasing the ozone formation. Under certain conditions, ozone levels decrease as a result of a reduction in NOx emissions but do not respond significantly to changes in VOC emissions (NOx-sensitive condition), while under other conditions ozone concentrations decrease in response to reductions in VOCs and may even increase when NOx emissions are reduced (VOC-sensitive conditions). Indicator species can be used to assess the sensitivity of ozone to changes in the emissions of its precursors. These indicators are species or species ratios involved in ozone photochemistry which reflect the primary chemical process through which the ozone was formed. In this work we use the MM5-CAMx model system to explore the behaviour of various indicator species during two meteorological situations featuring different atmospheric conditions in a complex terrain area. The results show that indicators based on nitrogen compounds (i.e,. NOy and NOz) are suitable for defining the transition range from VOC- to NOx-sensitive chemistry, and that despite the uncertainties associated with the use of chemical indicators, the ratios O₃/NOy and O₃/NOz may provide a simple and useful way to summarize the response of ozone to changes in NOx and VOC emissions in Southwestern Spain.     

Variation of Mo isotopes from molybdenite in high-temperature hydrothermal ore deposits

Measurable molybdenum isotope fractionation in molybdenites from different ore deposits through time provides insights into ore genesis and a new technique to identify open-system behavior of Re–Os in molybdenites. Molybdenite samples from six porphyry copper deposits, one epithermal polymetallic vein deposit, four skarns, and three Fe-oxide Cu–Au deposits were analyzed. The δ⁹⁷Mo‰ (where ) for all samples varied from 1.34 ± 0.09‰ to −0.26 ± 0.04‰. This is the largest molybdenum isotopic variation in molybdenite from high-temperature ore deposits recorded to date. δ⁹⁷Mo‰ of molybdenite varies as a function of the deposit type and the rhenium and osmium concentrations of the samples. Isotope values for Mo also vary within the individual deposits. In general, molybdenites from porphyry copper deposits have the lightest values averaging 0.07 ± 0.23‰ (1σ). Molybdenites from the other deposit types average 0.49 ± 0.26‰ (1σ). The variations could be related to the fractionation of Mo into different mineral phases during the ore-forming processes. A comparison of the Mo isotope ratios and the Re–Os ages obtained from the same aliquot may possess a geochronological evaluation tool. Samples that yielded robust ages have different Mo isotopic compositions in comparison to samples that yielded geologically unreasonable ages. Another observed relationship between the Re–Os and Mo isotope data reveals a weak correspondence between Re concentration and Mo isotope composition. Molybdenites with higher concentrations of Re correspond to lighter Mo isotope values.     

Experimental investigation of the kinetics of Ostwald ripening of quartz in silicic melts

To characterise the kinetics of Ostwald ripening of quartz, we conducted four series of experiments in systems consisting of quartz, with an initial grain size of ƹ.3 to 6 µm, in equilibrium with hydrous silicic liquids. Two series were performed with a haplogranitic liquid containing 6.5 wt% H₂O at 900 °C and 1 GPa. The third series was made in the quartz-anorthite system at water saturation, 900 °C, and 1 GPa. The last series was made in the quartz-albite system at water saturation, 800 °C, and 0.2 GPa. In all series, we observed a relatively small but systematic increase of the mean grain size of quartz, % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBae % bbnrfifHhDYfgasaacH8YjY-vipgYlH8Gipec8Eeeu0xXdbba9frFj % 0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs0dXdbPYxe9 % vr0-vr0-vqpWqaaeaabiGaciaacaqabeaabaqaamaaaOqaaiqbdsga % Kzaaraaaaa!29AA! [`(d)] \bar d , with increasing run duration, t. The largest increase was in the quartz-anorthite system: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBae % bbnrfifHhDYfgasaacH8YjY-vipgYlH8Gipec8Eeeu0xXdbba9frFj % 0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs0dXdbPYxe9 % vr0-vr0-vqpWqaaeaabiGaciaacaqabeaabaqaamaaaOqaaiqbdsga % Kzaaraaaaa!29AA! [`(d)] \bar d increased by a factor of 4.3 after 326 h; the smallest increase was measured in the quartz-albite system: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBae % bbnrfifHhDYfgasaacH8YjY-vipgYlH8Gipec8Eeeu0xXdbba9frFj % 0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs0dXdbPYxe9 % vr0-vr0-vqpWqaaeaabiGaciaacaqabeaabaqaamaaaOqaaiqbdsga % Kzaaraaaaa!29AA! [`(d)] \bar d increased by a factor of only ƹ.6 after 1,173 h. The experimental data yield very good linear fits in both ln t vs ln% MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBae % bbnrfifHhDYfgasaacH8YjY-vipgYlH8Gipec8Eeeu0xXdbba9frFj % 0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs0dXdbPYxe9 % vr0-vr0-vqpWqaaeaabiGaciaacaqabeaabaqaamaaaOqaaiqbdsga % Kzaaraaaaa!29AA! [`(d)] \bar d and ln t vs % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBae % bbnrfifHhDYfgasaacH8YjY-vipgYlH8Gipec8Eeeu0xXdbba9frFj % 0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs0dXdbPYxe9 % vr0-vr0-vqpWqaaeaabiGaciaacaqabeaabaqaamaaaOqaaiqbdsga % Kzaaraaaaa!29AA! [`(d)] \bar d diagrams. The slopes in the ln t vs ln% MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBae % bbnrfifHhDYfgasaacH8YjY-vipgYlH8Gipec8Eeeu0xXdbba9frFj % 0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs0dXdbPYxe9 % vr0-vr0-vqpWqaaeaabiGaciaacaqabeaabaqaamaaaOqaaiqbdsga % Kzaaraaaaa!29AA! [`(d)] \bar d diagrams, between 1/5 and 1/7, are, however, much smaller than the value of 1/3 predicted by the Lifshitz-Slyozov-Wagner theory for diffusion-controlled Ostwald ripening. A possible explanation for this discrepancy is that the diffusion-controlled regime in our experiments is only attained after a transient regime lasting from 20 h in series III to 100 h in series IV. A more straightforward explanation of the experimental results is that the rate-limiting mechanism for Ostwald ripening is quartz growth by surface nucleation not diffusion in the silicic liquid. Finally, we extrapolated our data to geological time scales to evaluate the importance of Ostwald ripening in natural quartz-bearing magmatic systems: (1) quartz cannot coarsen measurably by Ostwald ripening over reasonable time scales if the initial grain size is ƹ mm or more; and (2) Ostwald ripening may be very active at the end of nucleation events and result in the consumption of a significant proportion of crystalline nuclei.     

Process identification and search for optimal differentiation parameters from major element data. General presentation with emphasis on the fractional crystallization process

Different igneous differentiation processes result in various evolution trends in a certain composition space Rⁿ. Almost every genetic process can be described as a single two-pole mixing process, which leads to a straight evolution line in Rⁿ; or as a series of two-pole mixing processes, which in the general case leads to a broken curved evolution line.When a fundamental two-pole mixing process clearly prevails over one or several secondary processes in the genesis of a volcanic suite, a ‘best’ mixing line in Rⁿ can be computed with due attention to experimental uncertainties. A number of statistical tools are available for testing the data-uncertainties-linear model consistency and for pointing out a few dubious data, or the influence of a few secondary processes.The best mixing line and its associated error volumes serve to quantify the trend, and then can be used to get some ‘best’ estimate (or competitive acceptable estimates) of the mineralogical parameters that control the genetic process.Any mineral assemblage defines a continuous composition family in Rⁿ which can be characterized by its gaussian distance to the best mixing line. In the framework of a fractional crystallization model, that distance serves as a test for accepting or rejecting the mineral assemblage as a likely candidate for representing the crystallizing solid.In favorable situations the minimization procedure used to compute the distance also determines both the mineral proportions in the crystallizing solid and their compositions. In less favorable situations it may leave us with some indeterminacy among a small number of acceptable interpretations.The mixing line calculation and the mineralogical inversion procedure are applied to the classical Kilauea Iki Lava Lake (Hawaii) example, where olivine and chromite crystallization with incomplete solid-liquid separation is shown to be a likely explanation for the observations, along with near-surface iron oxidation as a secondary process.The origin of volcanic rocks from Terceira Island (Azores) is less clear. It is shown that the simultaneous crystallization of olivine, Ti-augite and plagioclase can be retained as an acceptable interpretation for the least differentiated rocks, but that substantial secondary processes are also involved.     

Hornblende Ar/Ar geochronology across terrane boundaries in the Sveconorwegian Province of S. Norway

Hornblende incremental heating ⁴⁰Ar/³⁹Ar data were obtained from augen gneiss and amphibolite of the Sveconorwegian Province of S. Norway. In the Rogaland-Vest Agder and Telemark terranes, four pyroxene-rich samples, located close (≤ 10 km) to the anorthosite-charnockite Rogaland Igneous Complex, define an age group at 916 + 12/ − 14 Ma and six samples distributed in the two terranes yield another group at 871 + 8/ − 10 Ma. The first age group is close to the reported zircon U---Pb intrusion age of the igneous complex (931 ± 2 Ma) and the regional titanite U---Pb age (918 ± 2 Ma), whereas the second group overlaps reported regional mineral Rb---Sr ages (895-853 Ma) as well as biotite K---Ar ages (878-853 Ma). In the first group, the comparatively dry parageneses of low-P thermal metamorphism (M2) associated with the intrusion of the igneous complex are well developed, and hornblende ⁴⁰Ar/³⁹Ar ages probably record a drop in temperature shortly after this phase. In other hornblende + biotite-rich samples, with presumably a higher fluid content, the hornblende ages are probably a response to hornblende-fluid interaction during a late Sveconorwegian metamorphic or hydrothermal event. A ca 220 m.y. diachronism in hornblende ⁴⁰Ar/³⁹Ar ages is documented between S. Telemark (ca 870 Ma) and Bamble (ca 1090 Ma). Differential uplift between these terranes was mostly accommodated by shearing along the Kristiansand-Porsgrunn shear zone. The final stage of extension along this zone occurred after intrusion of the Herefoss post-kinematic granite at 926 ± 8 Ma. On the contrary, the southern part of the Rogaland-Vest Agder and Telemark terranes share a common cooling evolution as mineral ages are similar on both sides of the Mandal-Ustaoset Line the tectonic zone between them. The succession within 20 m.y. of a voluminous pulse of post-tectonic magmatism at 0.93 Ga, a phase of high-T-low-P metamorphism at 0.93-0.92 Ga, and fast cooling at a regional scale ca 0.92 Ga, suggests that the southern parts of Rogaland-Vest Agder and Telemark were affected by an event of post-thickening extension collapse at that time. This event is not recorded in Bamble.     

Climate and Rural Income

This paper tests whether climate has an impact on per capita rural income. The study finds that total (agricultural and nonagricultural) income in rural counties and municipios in the US and Brazil are affected by climate. The study demonstrates that this income effect is due to changes in the net value of agriculture. Regions with better climates for agriculture support higher rural incomes and regions with poor climates have more rural poverty. The results also suggest that global warming will likely increase rural poverty.     

The power spectrum of flux-limited X-ray galaxy cluster surveys

We compute the redshift space power spectrum of two X-ray cluster samples: the X-ray Brightest Abell Cluster Sample (XBACS) and the Brightest Cluster Sample (BCS) using the method developed by Feldman, Kaiser & Peacock. The power spectra derived for these samples are in agreement with determinations of other optical and X-ray cluster samples. For XBACS we find the largest power spectrum amplitude expected, given the high richness of this sample ( R ≥2) . In the range 0.05< k <0.4  h  Mpc⁻¹ the power spectrum shows a power-law behaviour P ( k )∝ k ⁿ with an index n ≃−1.2 . In a similar range, 0.04< k <0.3  h  Mpc⁻¹ , the BCS power spectrum has a smaller amplitude with index n ≃−1.0 . We do not find significant evidence for a peak at k ≃0.05  h  Mpc⁻¹ , suggesting that claims such of feature detections in some cluster samples could rely on artificial inhomogeneities of the data. We compare our results with power spectrum predictions derived by Moscardini et al. within current cosmological models (LCDM and OCDM). For XBACS we find that both models underestimate the amplitude of the power spectrum but for BCS there is reasonably good agreement at k ≳0.03  h  Mpc⁻¹ for both models.     

An experimental study of Ostwald ripening of olivine and plagioclase in silicate melts: implications for the growth and size of crystals in magmas

We carried out an experimental study to characterize the kinetics of Ostwald ripening in the forsterite-basalt system and in the plagioclase (An₆₅)-andesite system. Eight experiments were done in each system to monitor the evolution of mean grain size and crystal size distribution (CSD) with time t; the experiments were performed in a 1-atmosphere quench furnace, at 1,250°C for plagioclase and 1,300°C for olivine. Very contrasted coarsening kinetics were observed in the two series. In the plagioclase series, the mean grain size increased as log(t), from ≈3 μm to only 8.7 μm in 336 h. The kinetic law in log(t) means that Ostwald ripening was rate-limited by surface nucleation at plagioclase-liquid interfaces. In the olivine series, the mean grain size increased as t ^1/3, from ≈3 μm to 23.2 μm in 496 h. A kinetic law in t ^1/3 is expected when Ostwald ripening is rate-limited either by diffusion in the liquid or by grain growth/dissolution controlled by a screw dislocation mechanism. The shape of olivine CSDs, in particular their positive skewness, indicates that grain coarsening in the olivine experiments was controlled by a screw dislocation mechanism, not by diffusion. As the degrees of undercooling ΔT (or supersaturation) involved in Ostwald ripening are essentially <1°C, the mechanisms of crystal growth identified in our experiments are expected to be those prevailing during the slow crystallisation of large magma chambers. We extrapolated our experimental data to geological time scales to estimate the effect of Ostwald ripening on the size of crystals in magmas. In the case of plagioclase, Ostwald ripening is only efficient for mean grain sizes of a few microns to 20 μm, even for a time scale of 10⁵ years. It can, however, result in a significant decrease of the number of small crystals per unit volume, and contribute to the development of convex upwards CSDs. For olivine, the mean grain size increases from 2–3 μm to ≈70 μm in 1 year and 700 μm in 10³ years; a mean grain size of 3 mm is reached in 10⁵ years. Accordingly, the rate of grain size-dependent processes, such as compaction of olivine-rich cumulates or melt extraction from partially molten peridotites, may significantly be enhanced by textural coarsening.     

Estimation of nearshore groundwater discharge and its potential effects on a fringing coral reef

Radon (²²²Rn) measurements were conducted in Shiraho Reef (Okinawa, Japan) to investigate nearshore submarine groundwater discharge (SGD_nearshore) dynamics. Estimated average groundwater flux was 2-3 cm/h (maximum 7-8 cm/h). End-member radon concentration and gas transfer coefficient were identified as major factors influencing flux estimation accuracy. For the 7-km long reef, SGD_nearshore was 0.39-0.58 m³/s, less than 30% of Todoroki River’s baseflow discharge. SGD_nearshore was spatially and temporally variable, reflecting the strong influence of subsurface geology, tidal pumping, groundwater recharge, and hydraulic gradient. SGD_nearshore elevated nearshore nitrate concentrations (0.8-2.2 mg/l) to half of Todoroki River’s baseflow -N (2-4 mg/L). This increased nearshore Chl-a from 0.5-2 μg/l compared to the typically low Chl-a (<0.1-0.4 μg/l) in the moat. Diatoms and cyanobacteria concentrations exhibited an increasing trend. However, the percentage contributions of diatoms and cyanobacteria significantly decreased and increased, respectively. SGD may significantly induce the proliferation of cyanobacteria in nearshore reef areas.     

Transcrystalline melt migration in clinopyroxene

Glass inclusions in clinopyroxene phenocrysts from La Sommata (Vulcano Island, Aeolian Arc) were reheated and submitted to a sustained thermal gradient. Each remelted inclusion undergoes a transient textural and chemical reequilibration and concomitantly begins to migrate along a crystallographic direction, at a small angle with the thermal gradient. The completion of morphological evolution requires a characteristic time that is governed by chemical diffusion. Chemical reequilibration results in the formation of a colored halo that delineates the former location and shape of the inclusion after it has migrated away. Transcrystalline migration proceeds by dissolution of the host clinopyroxene ahead and precipitation astern. Its rate is not limited by Fick’s law, but by the crystal-melt interface kinetics. Clinopyroxene dissolution and growth are slower than for olivine in similar conditions but obey the same analytical law, which can be transposed to equally or more sluggish melting or crystallization events in nature. When a gas bubble is initially present, it responds to elastic forces by quickly shifting toward the cold end of the inclusion, where it soon becomes engulfed as an isolated fluid inclusion in the reprecipitated crystal. This study confirms that transcrystalline melt migration, beside its possible implications for small-scale melt segregation and fluid-inclusion generation in the Earth’s mantle, provides an experimental access to interfacial kinetic laws in near-equilibrium conditions.