Mechanism development and modelling of tropospheric multiphase halogen chemistry: The CAPRAM Halogen Module 2.0 (HM2)

A new detailed multiphase halogen mechanism, the CAPRAM Halogen Module 2.0 (HM2), has been developed and coupled to the multiphase chemistry mechanism RACM-MIM2ext/CAPRAM 3.0n. The overall mechanism comprises 1,705 reactions including 595 reactions of the HM2. Halogen chemistry box model studies have been, for the first time, performed with a non-permanent cloud scenario for pristine open ocean regions in mid-latitudes. Moreover, detailed time-resolved reaction flux analysis has been used to investigate the multiphase halogen reaction cycles in more detail. Clouds significantly change the multiphase halogen chemical system and new reaction cycles are proposed for in-cloud conditions. While most gas phase concentrations are decreased for chlorine and iodine species, they are increased for bromine. Flux analyses determined the relative contributions of the methylene dihalides CH₂IX (X = Cl, Br, I) as the main I atom source with a contribution of about 80 % to the total iodocarbon sources. Furthermore, HOI was confirmed to be important for chlorine activation. It is shown that 25 % of the ozone loss can be attributed to halogens. VOC oxidation by halogens is important as halogens account for about 20 % of the methane oxidation and up to 80 % of the oxidation of other VOCs. In other cases, enhanced VOC and VOC oxidation product concentration levels were found. For example, 15 % of the methyl peroxyl radicals are formed after the reaction of chlorine atoms with methane or methyl hydroperoxide. In the aqueous phase, changes in the oxidation of organics do only occur for highly oxidised organics without a C-H bond. For example, over 80 % of oxalic acid are oxidised by electron transfer with Cl₂ ^? in deliquescent particles during non-cloud periods.     

Climate change in the Paraná state,Brazil: responses to increasing atmospheric CO 2 in reference evapotranspiration

The hydrological variable evapotranspiration (ET) is challenging to estimate because it cannot be measured directly in natural environments (except in small plots). The uncertainties associated with the models used for its prediction have increased under climate change conditions. We studied the influence of stomatal resistance on ET estimates using the Penman-Monteith method as projected by three general circulation models in two emission scenarios (RCP4.5 and RCP8.5) for future climates throughout the twenty-first century (2010–2039, 2040–2069, and 2070–2099). We also investigated the probable ET rate changes in relation to the current (30 years average, 1980–2009) climate conditions for the Paraná state in the southern region of Brazil. The results were regionalized to help policymakers assess climate change impacts and design adaptation measures. ET increases of up to 15% were found in future climate conditions, which may lead to a significant increase in the water demand for agricultural crops. However, we believe that plant morphophysiological changes may occur under atmospheric CO2 enrichment conditions and that a possible reduction in stomatal conductance will result in lower ET increases than those obtained with the traditional Penman-Monteith method. When considering future climate scenarios, we propose the equation be adjusted to consider stomatal resistance as a function of CO2 concentrations.     

Experimental reactions between olivine and orthopyroxene with phonolite melt: implications for the origins of hydrous amphibole + phlogopite + diopside bearing metasomatic veins

Amphibole + phlogopite + diopside bearing veins are observed in a large number of upper mantle xenoliths, but the composition of the melt that forms them is poorly constrained. Recent data from the Heldburg Phonolite, Central Germany, has shown that phonolite melt will react with olivine and orthopyroxene xenocrysts to form reaction rims of amphibole + phlogopite + diopside at mid-lower crustal pressures. This is the first example of where a melt has reacted with peridotite to form the mineralogy of the metasomatic veins. It is therefore necessary to explore whether a phonolite melt could be the parent melt that forms amphibole + phlogopite + diopside metasomatic veins. Experimental reactions between single crystals of olivine and orthopyroxene with phonolite melt were conducted at upper mantle conditions of 1.0–1.5 GPa and 900–1,000 °C. Melt water contents were varied from anhydrous to >12 wt. H₂O. Olivine reacts to form phlogopite reaction rims with overgrowths of diopside <1,000 °C or rims of secondary olivine >1,000 °C. Orthopyroxene reacts to form amphibole with epitaxial diopside overgrowths <1,000 °C. No reaction rims form when the bulk melt H₂O is lower than ~3.8 wt%. Pressure has little effect over the small range tested. These experiments reproduce reaction rims on olivine and orthopyroxene observed in the Heldburg Phonolite, Central Germany, and suggest that a relatively narrow range of temperatures and melt water contents is required for rim formation. The compositions of rim amphibole, phlogopite and diopside from the experiments have very similar compositions to those from Heldburg but do not match those from metasomatic veins. Phenocrysts from Heldburg are similar to the metasomatic veins, suggesting that a phonolite could potentially form the veins if vein formation is dominated by crystallization rather than reaction and replacement of wall rock phases.     

Be exposure dating of river terraces at the southern mountain front of the Dzungarian Alatau (SE Kazakhstan) reveals rate of thrust faulting over the past ~ 400 ka

The mountain belts of the Dzungarian Alatau (SE Kazakhstan) and the Tien Shan are part of the actively deforming India–Asia collision zone but how the strain is partitioned on individual faults remains poorly known. Here we use terrace mapping, topographic profiling, and ¹⁰Be exposure dating to constrain the slip rate of the 160-km-long Usek thrust fault, which defines the southern front of the Dzungarian Alatau. In the eastern part of the fault, where the Usek River has formed five terraces (T₁–T₅), the Usek thrust fault has vertically displaced terrace T₄ by 132 ± 10 m. At two sites on T₄, exposure dating of boulders, amalgamated quartz pebbles, and sand from a depth profile yielded ¹⁰Be ages of 366 ± 60 ka and 360 ^+ 77/_− 48 ka (both calculated for an erosion rate of 0.5 mm/ka). Combined with the vertical offset and a 45–70° dip of the Usek fault, these age constraints result in vertical and horizontal slip rates of ~ 0.4 and ~ 0.25 mm/a, respectively. These rates are below the current resolution of GPS measurements and highlight the importance of determining slip rates for individual faults by dating deformed landforms to resolve the pattern of strain distribution across intracontinental mountain belts.     

Airborne remote sensing of cloud radiative smoothing during the Baltex Bridge Cloud campaign

Based on airborne observations during the Baltex Bridge Cloud (BBC) campaign in September 2001, the impact of two layer cloud systems, gas absorption and surface albedo on cloud radiative smoothing is investigated. Multispectral nadir radiance measurements have been conducted which cover the visible and near infrared wavelength range. The observed radiances are transformed into Fourier space where ranges of scale-invariance are identified. Associated slopes and scale breaks are determined and used to characterize the impacts on cloud radiative smoothing. The results reveal that an increase of gas absorption reduces the small scale slope and the scale break due to a decreasing likelihood of horizontal photon transport. Another impact is that the increasing gas absorption reduces the cloud surface interaction, which is indicated by an increase of the large scale slope. An increasing surface albedo results in large scale cloud radiative smoothing and is associated with a decrease of the large scale slope. This effect depends on the cloud height and the cloud morphology. Two layer cloud systems exhibit a similar behaviour in Fourier space as large surface albedos beneath a single cloud deck. It is argued that the impact of two layer cloud systems on large scale cloud radiative smoothing may not be typical for two layer clouds.     

Crustal contamination of mafic magmas: evidence from a petrological, geochemical and Sr–Nd–Os–O isotopic study of the Proterozoic Isortoq dike swarm, South Greenland

The mid-Proterozoic Isortoq dike swarm in the Gardar Province, South Greenland, comprises a variety of alkaline rocks ranging from gabbroic to syenitic in composition. Major magmatic mineral phases are olivine, clinopyroxene, Fe–Ti oxides, amphibole, plagioclase and alkali feldspar. Quartz occurs in some samples as a late magmatic phase. Liquidus temperatures of olivine-bearing samples range between 1120 and 1145 °C and solidus temperatures are 850–930 °C. Calculated silica activities are highly variable between 0.53 and unity. Oxygen fugacities vary from −3 to +1 log units relative to the fayalite–magnetite–quartz buffer.

The rocks have MgO contents <6 wt.% with Mg# between 53 and 17. Primitive mantle-normalized trace element patterns show a relative enrichment of LIL elements with Ba peaks and Nb troughs. Clinopyroxenes show a general enrichment in REE relative to chondritic values with variable slightly positive to prominent negative Eu anomalies. Two of the dikes were dated with Sm–Nd three-point isochrons at 1190±44 and 1187±87 Ma, respectively. Initial ⁸⁷Sr/⁸⁶Sr ratios of mafic mineral separates range from 0.70289 to 0.70432 and initial _Nd values vary from +0.3 to −10.7. Whole-rock initial ¹⁸⁷Os/¹⁸⁸Os ratios are highly variable including very radiogenic values of up to 7.967. δ¹⁸O_v-smow values of separated clinopyroxene and amphibole range from +5.2‰ to +6.2‰ and fall within the range of typical mantle-derived rocks, although mixing with a lower crustal component is permitted by the data. Using energy-constrained assimilation-fractional crystallization (EC-AFC) modeling equations, the Sr–Nd isotope data of the more radiogenic samples can successfully be modeled by addition of up to 10% lower crustal granulite-facies Archean gneisses as contaminants. The Os isotopic data also suggest the involvement of old radiogenic crust. In accordance with seismic data, we conclude that a wedge of Archean crust extends from West Greenland further to the south below the present erosion level.     

Degradation of chlorinated ethylenes by Fe0: inhibition processes and mineral precipitation

. Granular zero-valent iron was used for the treatment of groundwater pollution caused by chlorinated ethylenes, mainly TCE, cis-DCE and VC at an industrial site. The rapidly decreasing rates of de-chlorination in the initial phase were attributed to the precipitation of carbonates and the development of hydrogen by anaerobic corrosion. After 70 pore volumes, sulphate was reduced by bacteria. From this point in time, the degradation of TCE was slightly accelerated whereas the de-chlorination rates of the other chlorinated ethylenes decreased only slowly. This relative improvement was assumed to be caused by the uptake of electron-transfer-blocking hydrogen by bacteria. Because the overall trend of the degradation rates is negative we conclude that the inhibitive effect of carbonate precipitation and hydrogen formation cannot be compensated for by the positive influence of the activity of sulphate-reducing bacteria.