Gas-Phase OH Oxidation of Monoterpenes: Gaseous and Particulate Products

Smog chamber experiments have beenconducted in which cyclic monoterpenes were oxidisedin the gas phase by OH. The evolved secondary organicaerosol (SOA) was analysed by LC-MSⁿ and thegas-phase products were analysed by FT-IR. Theconcentrations of the identified compoundscorresponded to carbon mass balances in the range of40%–90%. The identified compounds in the particularphase corresponded to 0.5%–4.2% of the reactedcarbon. The most abundant compounds in SOA fromterpenes with an endocyclic C=C double bond wereC₁₀-keto-aldehydes, C₁₀-keto-carboxylicacids, C₁₀-hydroxy-keto-carboxylic acids, andC₁₀-hydroxy-keto-aldehydes (pinonaldehyde,pinonic acid, hydroxy-pinonic acid isomers, andhydroxy-pinonaldehyde isomers from -pinene;3-caronaldehyde, 3-caronic acid, hydroxy-3-caronicacid isomers, and hydroxy-3-caronaldehyde isomers from3-carene). The most abundant compounds in SOA fromterpenes with an exocyclic C=C double bond wereC₉-ketones, C₉-dicarboxylic acids, andC₁₀-hydroxy-keto-carboxylic acids (nopinone,pinic acid, and hydroxy-pinonic acid isomers from-pinene; sabinaketone, sabinic acid andhydroxy-sabinonic acid isomers from sabinene).Decarboxylated analogues of most of the compounds werepresent in SOA in minor concentrations, such asC₉-keto-carboxylic acids (norpinonic acid,nor-3-caronic acid) and C₈-dicarboxylic acids(norpinic acid, nor-3-caric acid, norsabinic acid). InSOA from limonene, which contains an endocyclic aswell as an exocyclic C=C double bond, the mostabundant compounds were a C₁₀-keto-aldehyde andits oxo-derivative (limononaldehyde and keto-limononaldehyde) together with hydroxy-derivatives of aC₁₀-keto-carboxylic acid (isomers ofhydroxy-limononic acid). Also aC₁₀-keto-carboxylic acid (limononic acid) waspresent together with minor concentrations of aC₉-dicarboxylic acids (limonic acid), itsoxo-derivative (keto-limonic acid), and itsdecarboxylated analogue (norlimonic acid). Mechanisticpathways for the formation of these products, some ofwhich are identified here for the first time, areproposed.     

Oxygen-isotope systematics of a strongly recrystallized granitic rock complex,Grenvillian Belt,SW Sweden

In the eastern, external part of the Grenvillian Belt in SW Sweden, five formations of granitic rocks were found in the basement of the Dalslandian Supracrustal Group. The granitic rocks have been strongly recrystallized but have preserved most of their granitic texture in the process. Most magmatic crystals have been pseudomorphed by metamorphic minerals: quartz, albite, chlorite, biotite, white mica, epidote, titanite, hematite, pyrite and carbonate. Two of the formations have subsequently been affected by a cataclastic deformation and at present consist of mylogneisses. ¹⁸O whole-rock values for the granitic rocks vary from +3.0 to +11.1. Quartz-apatite, quartz-zircon and quartz-titanite pairs show ¹⁸O/¹⁶O fractionations corresponding to equilibrium temperatures of 550–700° C, which are believed to reflect in the main continued closed-system isotopic exchange at high temperatures following solidification. In contrast highly positive ¹⁸O/¹⁶O fractionations for quartz-K-feldspar, quartz-biotite, quartz-chlorite and quartz-sericite pairs in some granitic samples indicate that these rocks have exchanged oxygen with heated, meteoric, H₂O dominated fluids. Other granitic samples, however, show virtually undisturbed magmatic ¹⁸O/¹⁶O fractionation values for the same mineral pairs, even though these rocks are equally altered.It is concluded that all granitic rock units recrystallized under greenschist facies conditions during the infiltration of fluids under the influence of hydrothermal convection systems set up by the intrusion of the granitic plutons. The fluids probably had a range of ¹⁸O values from ca. -14 to ca. +10, indicating the mixing of distinct fluid reservoirs, one of meteoric origin and the others of magmatic and/or metamorphic origin. The temperature of alteration is estimated at 450–500° C.Estimation of pre-alteration ¹⁸O whole rock values for the five granitic units suggests that three units should be assigned a dominantly S-type origin, where as the other two units may partly or wholly have an I-type origin.     

Palaeomagnetic timing of the rotation and translation of Cyprus

The geological evolution of the Mesozoic Troodos Ophiolite Complex in Cyprus, and the tectonic nature and timing of the palaeomagnetically indicated anticlockwise rotation of Cyprus of some 80° and ca. 15° northward translation, have been open for debate for some time. New palaeomagnetic data from 18 sites ( 180samples) in the post-ophiolite sediments, ranging in age from Upper Cretaceous to Upper Miocene, are presented. Most of the sites are of normal geomagnetic polarity, but indications of reversed polarity have been found in an older group of sediments (the Lefkara Formation of Upper Palaeocene age).Six sites from the older group of sediments (Upper Cretaceous to Eocene in age) give a site mean direction of the AF cleaned sediments of (D, I) = (323°, 29°) with α₉₅ = 18°, while 5 sites from a younger group of sediments (Oligocene to Miocene in age) give a cleaned site mean direction of (D, I) = (334°, 58°) with α₉₅ = 9°. These and published data suggest that an anticlockwise rotation of Cyprus of 60 ± 10° occurred early during the post-igneous evolution of the Cyprus oceanic crust between 90 and 50Ma, leaving only a minor anticlockwise rotation of 20 ± 10° to occur during the last 50 Ma. It is furthermore concluded that the northward translation of Cyprus of 15° mostly took place during the last 30Ma.It thus appears that a fairly rapid rotation of the Cyprus microplate first took place in the Late Cretaceous and Early Tertiary time with an average angular velocity of 1–2°/Ma, during which the northward translation was minor or negligible. In the latter half of the Tertiary, the sense of movement appears to have radically changed, the northward translation now being dominant with an average velocity of 5–6cm/yr. This temporal evolution is found to be in good agreement with the Mesozoic and Tertiary movements of the African lithospheric plate relative to Europe, as evidenced from the Atlantic sea-floor magnetic anomaly spreading history.     

The effectiveness of communicative tools in addressing barriers to municipal climate change adaptation: lessons from the Netherlands

Little research has been done on the effectiveness of communicative tools for climate change adaptation. Filling this knowledge gap is relevant, as many national governments rely on communicative tools to raise the awareness and understanding of climate impacts, and to stimulate adaptation action by local governments. To address this knowledge gap, this study focuses on the effectiveness of communicative tools in addressing key municipal barriers to climate change adaptation, by conducting a large N-size empirical study in the Netherlands. This study explores the effectiveness of these tools in theory, by checking whether their goals match the perceived barriers to municipal climate change adaptation, and the effectiveness in practice by analysing whether they are used and perceived as useful. Document analyses have clarified the assumptions underlying the tools. By conducting semi-structured interviews with 84 municipalities the key barriers to climate change adaptation and the use and usefulness of the tools in practice were analysed. The research revealed that the key barriers experienced by municipalities are a lack of urgency, a lack of knowledge of risks and measures, and limited capacity, the first being the primary one. Communicative tools, while being effective in theory, are not sufficiently effective in practice in addressing the key barriers. Municipalities that are not experiencing a sense of urgency to take on adaptation planning are not likely to be activated by the tools. Advanced municipalities need more sophisticated tools. This article concludes with some suggestions to improve the effectiveness of communicative tools.

Key policy insights

• Although effective in theory in addressing key barriers to municipal adaptation planning, the effectiveness in practice of communicative tools is limited.

• To increase their effectiveness in practice, municipalities’ awareness of the existence of the communicative tools needs to be raised.

• Advanced municipalities need more sophisticated tools that are context-specific and address a wide range of climate risks.

• The effectiveness of communicative tools can be improved by embedding them in a wider mix of policy instruments.

     

Statistical EOF analysis of spatiotemporal glacier mass-balance variability: a case study of Mittivakkat Gletscher,SE Greenland

An Empirical Orthogonal Function (EOF) variance analysis was performed to map in detail the spatiotemporal variability in individual stake mass-balances (ba) on Mittivakkat Gletscher (MG) – in a region where at present five out of ~20.000 glaciers have mass-balance observations. The EOF analysis suggested that observed ba was summarized by two modes: EOF1 and EOF2 represented 80% (significant) and 6% (insignificant) of the explained variance, respectively. EOF1 captured a decline in ba that was uniformly distributed in space at all stakes. The decline was correlated with albedo observations and air temperature observations from nearby stations. EOF2, however, described variations in ba that were heterogeneously distributed among stakes and associated with local slope and aspect. Low elevation stakes (~<400 m a.s.l.) showed relatively negative (out of phase) correlation and higher elevated stakes relatively positive (in phase) eigenvector correlation values with EOF2. Such relatively negative and positive eigenvector correlation values were present where the constituted of exposed glacier ice or snow cover, respectively. The results from this study show how EOF analyses can provide information on spatiotemporal patterns of glacier mass-balance. Understanding such detailed variabilities in mass-balance on a Greenlandic glacier is of interest because a fifth of the Arctic contribution from glaciers and ice caps to sea-level rise originates from Greenland.     

Assessing climate change impacts on the Iberian power system using a coupled water-power model

Climate change is expected to have a negative impact on the power system of the Iberian Peninsula; changes in river runoff are expected to reduce hydropower generation, while higher temperatures are expected to increase summer electricity demand, when water resources are already limited. However, these impacts have not yet been evaluated at the peninsular level. We coupled a hydrological model with a power market model to study three impacts of climate change on the current Iberian power system: changes in hydropower production caused by changes in precipitation and temperature, changes in temporal patterns of electricity demand caused by temperature changes, and changes in irrigation water use caused by temperature and precipitation changes. A stochastic dynamic programming approach was used to develop operating rules for the integrated system given hydrological uncertainty. We found that changes in precipitation will reduce runoff, decrease hydropower production (with accompanying increases in thermal generation), and increase irrigation water use, while higher temperatures will shift power demand from winter to summer months. The combined impact of these effects will generally make it more challenging to balance agricultural, power, and environmental objectives in the operation of Iberian reservoirs, though some impacts could be mitigated by better alignment between temporal patterns of irrigation and power demands.     

Fluid flow and methane occurrences in the Disko Bugt area offshore West Greenland: indications for gas hydrates?

The present study is the first to directly address the issue of gas hydrates offshore West Greenland, where numerous occurrences of shallow hydrocarbons have been documented in the vicinity of Disko Bugt (Bay). Furthermore, decomposing gas hydrate has been implied to explain seabed features in this climate-sensitive area. The study is based on archive data and new (2011, 2012) shallow seismic and sediment core data. Archive seismic records crossing an elongated depression (20×35 km large, 575 m deep) on the inner shelf west of Disko Bugt (Bay) show a bottom simulating reflector (BSR) within faulted Mesozoic strata, consistent with the occurrence of gas hydrates. Moreover, the more recently acquired shallow seismic data reveal gas/fluid-related features in the overlying sediments, and geochemical data point to methane migration from a deeper-lying petroleum system. By contrast, hydrocarbon signatures within faulted Mesozoic strata below the strait known as the Vaigat can be inferred on archive seismics, but no BSR was visible. New seismic data provide evidence of various gas/fluid-releasing features in the overlying sediments. Flares were detected by the echo-sounder in July 2012, and cores contained ikaite and showed gas-releasing cracks and bubbles, all pointing to ongoing methane seepage in the strait. Observed seabed mounds also sustain gas seepages. For areas where crystalline bedrock is covered only by Pleistocene–Holocene deposits, methane was found only in the Egedesminde Dyb (Trough). There was a strong increase in methane concentration with depth, but no free gas. This is likely due to the formation of gas hydrate and the limited thickness of the sediment infill. Seabed depressions off Ilulissat Isfjord (Icefjord) previously inferred to express ongoing gas release from decomposing gas hydrate show no evidence of gas seepage, and are more likely a result of neo-tectonism.     

How many predictors in species distribution models at the landscape scale? Land use versus LiDAR-derived canopy height

At the local spatial scale, land-use variables are often employed as predictors for ecological niche models (ENMs). Remote sensing can provide additional synoptic information describing vegetation structure in detail. However, there is limited knowledge on which environmental variables and how many of them should be used to calibrate ENMs. We used an information-theoretic approach to compare the performance of ENMs using different sets of predictors: (1) a full set of land-cover variables (seven, obtained from the LGN6 Dutch National Land Use Database); (2) a reduced set of land-cover variables (three); (3) remotely sensed laser data optimized to measure vegetation structure and canopy height (LiDAR, light detection and ranging); and (4) combinations of land cover and LiDAR. ENMs were built for a set of bird species in the Veluwe Natura 2000 site (the Netherlands); for each species, 26–214 records were available from standardized monitoring. Models were built using MaxEnt, and the best performing models were identified using the Akaike’s information criterion corrected for small sample size (AICc). For 78% of the bird species analysed, LiDAR data were included in the best AICc model. The model including LiDAR only was the best performing one in most cases, followed by the model including a reduced set of land-use variables. Models including many land-use variables tended to have limited support. The number of variables included in the best model increased for species with more presence records. For all species with 33 records or less, the best model included LiDAR only. Models with many land-use variables were only selected for species with >150 records. Test area under the curve (AUC) scores ranged between 0.72 and 0.92. Remote sensing data can thus provide regional information useful for modelling at the local and landscape scale, particularly when presence records are limited. ENMs can be optimized through the selection of the number and identity of environmental predictors. Few variables can be sufficient if presence records are limited in number. Synoptic remote sensing data provide a good measure of vegetation structure and may allow a better representation of the available habitat, being extremely useful in this case. Conversely, a larger number of predictors, including land-use variables, can be useful if a large number of presence records are available.     

Early Eocene magnetostratigraphy and tectonic evolution of the Xining Basin,NE Tibet

The Cenozoic strata of the Xining Basin, NE Tibet, have provided crucial records for understanding the tectonic and palaeo-environmental evolution of the region. Yet, the age of the lower part of the sedimentary stratigraphy and, consequently, the early tectonic evolution of the basin remain debated. Here, we present the litho- and magnetostratigraphy of various early Eocene sections throughout the Xining Basin independently constrained by the U–Pb radiometric age of a carbonate bed. Our study extends the dated stratigraphy down to 53.0 Ma (C24n.1r) and reveals highly variable accumulation rates during the early Eocene ranging from 0.5 to 8 cm/ka. This is in stark contrast to the low but stable accumulation rates (2–3 cm/ka) observed throughout the overlying Palaeogene and Neogene strata. Such a pattern of basin infill is not characteristic of flexural subsidence as previously proposed, but rather supports an extensional origin of the Xining Basin with multiple depocentres, which subsequently coalesced into a more stable and slowly subsiding basin. Whether this extension was related to the far-field effects of the subducting Pacific Plate or the India–Asia collision remains to be confirmed by future studies.