CLASSIFICATION:OLDTIMERS AND NEWCOMERS

Classification and regression techniques are among the most used tools by chemometricians.Withclassification,the two classic methods are discriminant analysis and SIMCA.In this paper we discuss theconnection between these two methods and introduce two new ones of the same family:DASCO(discriminantanalysis with shrunken covariances)and RDA(regularized discriminant analysis).We demonstrate on bothsimulated and real data sets that their performance is superior to the old favorites.This is especially truein small-sample/high-dimension settings typical in chemistry.     

Metamorphic, Thermal, and Tectonic Evolution of Central New England

A new, detailed tectonic model is presented for the Acadianorogenic belt of central New England (Vermont and New Hampshire)that accounts for a wide range of petrological and structuralobservations. Three belts are considered: the Eastern Vermont,Merrimack, and intervening Bronson Hill belts. Specific observationsin eastern Vermont that are accounted for in the model includethe following. P–T paths are clockwise with maximum pressuresnear the Athens, Chester, and Strafford domes of 8–11kbar, but with maximum pressures decreasing to 3–5 kbarat the boundary with the Bronson Hill belt. Differential exhumationof the Vermont domes relative to the rocks in easternmost Vermontis required by the recorded differences in maximum pressure(5–6 kbar; 15–20 km) and the present-day geographicalseparation (7–10 km). Specific observations in New Hampshirethat are explained include the following. P–T paths inthe Merrimack belt are counter-clockwise with maximum pressuresof 4–5 kbar and are related to high regional heat flowand heat transfer by early Acadian plutons. P–T pathsin the Bronson Hill belt are intimately associated with structuralposition. An early contact metamorphism is evidenced in theSkitchewaug and Fall Mountain nappes near contacts with theearly Acadian Bethlehem gneiss (     

Late Holocene climatic history of northern Germany and Denmark: peat macrofossil investigations at Dosenmoor, Schleswig-Holstein, and Svanemose, Jutland

Plant macrofossil remains have been analysed from two raised peat bogs in northern Germany and Denmark. The quantified vegetation reconstructions of each profile were subjected to multivariate analyses to extract records of changing bog surface wetness (BSW), which are interpreted in these rain-fed bogs as being proxy climate signals. Age/depth models were constructed using radiocarbon dates and a number of drier and wetter phases were defined. The records both register cooler/wetter conditions around 2700, 1800 and 1400 cal. yr BP, and at the beginning of the Little Ice Age around AD 1250–1350. These rising bog water tables must have been reflected in poorer conditions for agriculture, and in particular near Dosenmoor where the profile records a catastrophic change to such conditions culminating at 2750–2600 cal. yr BP.     

Open-System Magma Chamber Evolution: an Energy-constrained Geochemical Model Incorporating the Effects of Concurrent Eruption, Recharge, Variable Assimilation and Fractional Crystallization (EC-E'RA{chi}FC)

Significant petrogenetic processes governing the geochemicalevolution of magma bodies include magma Recharge (includingformation of ‘quenched inclusions’ or enclaves),heating and concomitant partial melting of country rock withpossible ‘contamination’ of the evolving magma body(Assimilation), and formation and separation of cumulates byFractional Crystallization (RAFC). Although the importance ofmodeling such open-system magma chambers subject to energy conservationhas been demonstrated, the effects of concurrent removal ofmagma by eruption and/or variable assimilation (involving imperfectextraction of anatectic melt from wall rock) have not been considered.In this study, we extend the EC-RAFC model to include the effectsof Eruption and variable amounts of assimilation, A. This model,called EC-E'RAFC, tracks the compositions (trace elements andisotopes), temperatures, and masses of magma body liquid (melt),eruptive magma, cumulates and enclaves within a composite magmaticsystem undergoing simultaneous eruption, recharge, assimilationand fractional crystallization. The model is formulated as aset of 4 + t + i + s coupled nonlinear differential equations,where the number of trace elements, radiogenic and stable isotoperatios modeled are t, i and s, respectively. Solution of theEC-E'RAFC equations provides values for the average temperatureof wall rock (T_a), mass of melt within the magma body (M_m),masses of cumulates (M_ct), enclaves (M_en) and wall rock () and the masses of anatectic melt generated () and assimilated (). In addition, t trace element concentrations and i + s isotopic ratios inmelt and eruptive magma (C_m, _m, _m), cumulates (C_ct, _m, _m), enclaves(C_en, , ) and anatectic melt (C_a, , ) as a function of magma temperature (T_m) are also computed. Input parametersinclude the (user-defined) equilibration temperature (T_eq),a factor describing the efficiency of addition of anatecticmelt () from country rock to host magma, the initial temperatureand composition of pristine host melt (, , , ), recharge melt (, , , ) and wall rock (, , , ), distribution coefficients (D_m, D_r, D_a) and their temperaturedependences (H_m, H_r, H_a), latent heats of transition (meltingor crystallization) for wall rock (h_a), pristine magma (h_m)and recharge magma (h_r) as well as the isobaric specific heatcapacity of assimilant (C_p,a), pristine (C_p,m) and recharge(C_p,r) melts. The magma recharge mass and eruptive magma massfunctions, M_r(T_m) and M_e(T_m), respectively, are specified apriori. M_r(T_m) and M_e(T_m) are modeled as either continuous orepisodic (step-like) processes. Melt productivity functions,which prescribe the relationship between melt mass fractionand temperature, are defined for end-member bulk compositionscharacterizing the local geologic site. EC-E'RAFC has potentialfor addressing fundamental questions in igneous petrology suchas: What are intrusive to extrusive ratios (I/E) for particularmagmatic systems, and how does this factor relate to rates ofcrustal growth? How does I/E vary temporally at single, long-livedmagmatic centers? What system characteristics are most profoundlyinfluenced by eruption? What is the quantitative relationshipbetween recharge and assimilation? In cases where the extractionefficiency can be shown to be less than unity, what geologiccriteria are important and can these criteria be linked to fieldobservations? A critical aspect of the energy-constrained approachis that it requires integration of field, geochronological,petrologic, and geochemical data, and, thus, the EC-ERAFC ‘systems’approach provides a means for answering broad questions whileunifying observations from a number of disciplines relevantto the study of igneous rocks. KEY WORDS: assimilation; energy conservation; eruption; open system; recharge     

Magmatic Evolution of the Skye Igneous Centre, Western Scotland: Modelling of Assimilation, Recharge and Fractional Crystallization

The Skye igneous centre, forming part of the British Tertiarymagmatic province, developed over a 7 Myr period (61–54Ma) and is characterized by a complex suite of lavas, hypabyssaland intrusive rocks of picritic to granitic composition. Theintrusion of magma from mantle to crust at 2x10^–3km³/yr(6 Mt/yr) advected magmatic heat of roughly 0·2 GW averagedover the period of magmatism supporting an ‘excess’heat flux of about 130 mW/m², or about twice the present-dayaverage continental heat flow. The volume of new crust generatedat Skye (15000 km³) spread over the present-day area of Skyecorresponds to 9 km of new crust. The geochemical evolutionof the Skye magmatic system is constrained using the Energy-ConstrainedRecharge, Assimilation, and Fractional Crystallization (EC-RAFC)model to understand variations in the Sr- and Pb-isotopic andSr trace-element composition of the exposed magmatic rocks withtime. The character (composition and specific enthalpy) of bothassimilant and recharge magma appears to change systematicallyup-section, suggesting that the magma reservoirs migrated toprogressively shallower levels as the system matured. The modelof the magma transport system that emerges is one in which magmabatches are stored initially at lower-crustal levels, wherethey undergo RAFC evolution. Residual magma from this stagethen migrates to shallower levels, where mid-crustal wall rockis assimilated; the recharge magma at this level is characterizedby an increasingly crustal signature. For some of the stratigraphicallyyoungest rocks, the data suggest that the magma reservoirs ascendedinto, and interacted with, upper-crustal Torridonian metasediments. KEY WORDS: assimilation; EC-RAFC model; geochemical modelling; magma recharge; Skye magmatism     

Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons

Measurements of aerosol formation during thephotooxidation of -pinene, -pinene,d-3-carene, d-limonene, ocimene, linalool, terpinene-4-ol, andtrans-caryophyllene were conducted in anoutdoor smog chamber. Daylight experiments in thepresence of and dark experiments withelevated ozone concentrations were performed. Theevolution of the aerosol was simulated by theapplication of a gas/particle absorption model inconnection with a chemical reaction mechanism. Thefractional aerosol yield is shown to be a function ofthe organic aerosol mass concentration andtemperature. Ozone and, for selected hydrocarbons, theNO₃ reaction of the compounds were found torepresent efficient routes to the formation ofcondensable products. For initial hydrocarbon mixingratios of about 100 ppb, the fractional aerosol yieldsfrom daylight runs have been estimated to be 5%for open-chain hydrocarbons, such as ocimene andlinalool, 5–25% for monounsaturated cyclicmonoterpenes, such as -pinene, d-3-carene, orterpinene-4-ol, and 40% for a cyclic monoterpenewith two double bonds like d-limonene. For the onlysesquiterpene investigated, trans-caryophyllene, afractional aerosol yield of close to 100% wasobserved. The majority of the compounds studied showedan even higher aerosol yield during dark experimentsin the presence of ozone.     

Properties of dust aerosol particles transported to Portugal from the Sahara desert

Aerosol properties of mineral particles in the far field of an African desert dust outbreak were investigated that brought Saharan dust over the Mediterranean in different layers to Portugal. The measurements were performed inside the project Desert Aerosols over Portugal (DARPO) which was linked to the Saharan Mineral Dust Experiment (SAMUM). The maximum particle mass concentration was about 150 μg m⁻³ and the corresponding scattering coefficient was 130 M m⁻¹ which results in a mass scattering efficiency of 0.87 m² g⁻¹. The aerosol optical depth reached values up to 0.53 and the lidar ratio was between 45 and 50 in the whole dust loaded column. A comparison between particle size distributions and refractive indices derived from different instruments and models showed a general good agreement but some minor differences could also be observed. Measurements as well as calculations with a particle transport model suggest that there is a relatively higher concentration of very large particles in the upper region of the dust layer than on the surface which is likely connected with meteorological conditions at the observational site (Évora, Portugal).     

Diagenetic processes in carbonate mound sediments at the south‐west Rockall Trough margin

Cold water coral covered carbonate mounds at the south‐west margin of the Rockall Trough form ridges several kilometres long and up to 380 m high. Piston cores obtained at three mound crests reveal the complex internal structure of the mound build up, with alternating unlithified coral‐dominated intervals and lithified intervals. The most recent lithified interval is covered by corals embedded in a fine‐grained matrix, comprising ca 11 000 years of continuous mound evolution. Before this time ²³⁰Th/U dating shows the presence of several hiatuses in mound build‐up. Aragonitic coral material is absent or only present as mouldic porosity in the lithified intervals and coccoliths display widespread overgrowth. Downcore X‐ray fluorescence scanning, computer tomography scan images and petrographic observations indicate different degrees of diagenetic alteration. The upper boundary of the most recent lithified interval shows some erosional features, but petrographic observations indicate that initial lithification of the sediments is not related to this erosive event or to long‐term non‐sedimentation, but to earlier sub‐surface diagenesis. Organic matter oxidation and the subsequent lowering of the saturation state of the carbonate system drives dissolution of the unstable aragonitic coral skeletons. Depending on the openness of the system, this can lead to precipitation of a more stable low‐magnesium carbonate. A model is presented describing the sedimentary and diagenetic processes leading to the formation of lithified intervals.     

A 12.5-kyr history of vegetation dynamics and mire development with evidence of Younger Dryas larch presence in the Verkhoyansk Mountains, East Siberia, Russia

Werner, K., Tarasov, P. E., Andreev, A. A., Müller, S., Kienast, F., Zech, M., Zech, W. & Diekmann, B. 2009: A 12.5‐kyr history of vegetation dynamics and mire development with evidence of Younger Dryas larch presence in the Verkhoyansk Mountains, East Siberia, Russia. Boreas, 10.1111/j.1502‐3885.2009.00116.x. ISSN 0300‐9483. A 415 cm thick permafrost peat section from the Verkhoyansk Mountains was radiocarbon‐dated and studied using palaeobotanical and sedimentological approaches. Accumulation of organic‐rich sediment commenced in a former oxbow lake, detached from a Dyanushka River meander during the Younger Dryas stadial, at ～12.5 kyr BP. Pollen data indicate that larch trees, shrub alder and dwarf birch were abundant in the vegetation at that time. Local presence of larch during the Younger Dryas is documented by well‐preserved and radiocarbon‐dated needles and cones. The early Holocene pollen assemblages reveal high percentages of Artemisia pollen, suggesting the presence of steppe‐like communities around the site, possibly in response to a relatively warm and dry climate ～11.4–11.2 kyr BP. Both pollen and plant macrofossil data demonstrate that larch woods were common in the river valley. Remains of charcoal and pollen of Epilobium indicate fire events and mark a hiatus ～11.0–8.7 kyr BP. Changes in peat properties, C31/C27 alkane ratios and radiocarbon dates suggest that two other hiatuses occurred ～8.2–6.9 and ～6.7–0.6 kyr BP. Prior to 0.6 kyr BP, a major fire destroyed the mire surface. The upper 60 cm of the studied section is composed of aeolian sands modified in the uppermost part by the modern soil formation. For the first time, local growth of larch during the Younger Dryas has been verified in the western foreland of the Verkhoyansk Mountains (～170 km south of the Arctic Circle), thus increasing our understanding of the quick reforestation of northern Eurasia by the early Holocene.