An Assessment of HOx Chemistry in the Tropical Pacific Boundary Layer: Comparison of Model Simulations with Observations Recorded during PEM Tropics A

Reported are the results from a comparison of OH,H₂O₂CH₃OOH, and O₃ observationswithmodel predictions based on current HO_x–CH₄reaction mechanisms. The field observations are thoserecorded during the NASA GTE field program, PEM-Tropics A. The major focus ofthis paper is on thosedata generated on the NASA P-3B aircraft during a mission flown in the marineboundary layer (MBL) nearChristmas Island, a site located in the central equatorial Pacific (i.e.,2° N, 157° W). Taking advantage of thestability of the southeastern trade-winds, an air parcel was sampled in aLagrangian mode over a significantfraction of a solar day. Analyses of these data revealed excellent agreementbetween model simulated andobserved OH. In addition, the model simulations reproduced the major featuresin the observed diurnalprofiles of H₂O₂ and CH₃OOH. In the case ofO₃, the model captured the key observational feature whichinvolved an early morning maximum. An examination of the MBL HO_xbudget indicated that the O(¹D) + H₂Oreaction is the major source of HO_x while the major sinks involveboth physical and chemical processes involving the peroxide species,H₂O₂ and CH₃OOH. Overall, the generally goodagreement between modeland observations suggests that our current understanding ofHO_x–CH₄ chemistry in the tropical MBL isquite good; however, there remains a need to critically examine this chemistrywhen both CH₂O and HO₂are added to the species measured.     

Food webs and carbon flux in the Barents Sea

Within the framework of the physical forcing, we describe and quantify the key ecosystem components and basic food web structure of the Barents Sea. Emphasis is given to the energy flow through the ecosystem from an end-to-end perspective, i.e. from bacteria, through phytoplankton and zooplankton to fish, mammals and birds. Primary production in the Barents is on average 93 g C m⁻² y⁻¹, but interannually highly variable (±19%), responding to climate variability and change (e.g. variations in Atlantic Water inflow, the position of the ice edge and low-pressure pathways). The traditional focus upon large phytoplankton cells in polar regions seems less adequate in the Barents, as the cell carbon in the pelagic is most often dominated by small cells that are entangled in an efficient microbial loop that appears to be well coupled to the grazing food web. Primary production in the ice-covered waters of the Barents is clearly dominated by planktonic algae and the supply of ice biota by local production or advection is small. The pelagic–benthic coupling is strong, in particular in the marginal ice zone. In total 80% of the harvestable production is channelled through the deep-water communities and benthos. 19% of the harvestable production is grazed by the dominating copepods Calanus finmarchicus and C. glacialis in Atlantic or Arctic Water, respectively. These two species, in addition to capelin (Mallotus villosus) and herring (Clupea harengus), are the keystone organisms in the Barents that create the basis for the rich assemblage of higher trophic level organisms, facilitating one of the worlds largest fisheries (capelin, cod, shrimps, seals and whales). Less than 1% of the harvestable production is channelled through the most dominating higher trophic levels such as cod, harp seals, minke whales and sea birds. Atlantic cod, seals, whales, birds and man compete for harvestable energy with similar shares. Climate variability and change, differences in recruitment, variable resource availability, harvesting restrictions and management schemes will influence the resource exploitation between these competitors, that basically depend upon the efficient energy transfer from primary production to highly successful, lipid-rich zooplankton and pelagic fishes.     

Size matters more than method: Visual quadrats vs photography in measuring human impact on Mediterranean rocky reef communities

The performances of two commonly used non-destructive sampling procedures for rocky benthic assemblages (i.e. photography and visually assessed quadrats) were compared. A damaging human activity, date mussel (Lithophaga lithophaga) harvesting (DMH), was chosen. Directly impacted sites were compared with reference conditions (controls). Both visual quadrats and photography were equally able to detect differences between impacted situations and controls. However, visual quadrats showed high variability among replicates and estimated higher species richness for controls, while photography did so for impacts. Pooling photos in a ‘sum photo quadrat’ showed that differences between the two methods are due to sampling unit size rather than sampling procedure itself. As a small sampling unit is unavoidable with photography, visual quadrats should be preferred in investigating shallow rocky reefs for their larger size; however, longer working time underwater with quadrats does not allow for numerous replicates. Pooling many photos to reach sampling sizes comparable with those of quadrats may be a valid alternative to reconcile image resolution and areal coverage.     

A Comparison Between Machine Learning and Functional Geostatistics Approaches for Data-Driven Analyses of Sediment Transport in a Pre-Alpine Stream

Mathematical Geosciences - The problem of providing data-driven models for sediment transport in a pre-Alpine stream in Italy is addressed. This study is based on a large set of measurements...     

PEPSI: The high‐resolution échelle spectrograph and polarimeter for the Large Binocular Telescope

PEPSI is the bench‐mounted, two‐arm, fibre‐fed and stabilized Potsdam Echelle Polarimetric and Spectroscopic Instrument for the 2×8.4 m Large Binocular Telescope (LBT). Three spectral resolutions of either 43 000, 120 000 or 270 000 can cover the entire optical/red wavelength range from 383 to 907 nm in three exposures. Two 10.3k×10.3k CCDs with 9‐µm pixels and peak quantum efficiencies of 94–96 % record a total of 92 échelle orders. We introduce a new variant of a wave‐guide image slicer with 3, 5, and 7 slices and peak efficiencies between 92–96 %. A total of six cross dispersers cover the six wavelength settings of the spectrograph, two of them always simultaneously. These are made of a VPH‐grating sandwiched by two prisms. The peak efficiency of the system, including the telescope, is 15 % at 650 nm, and still 11 % and 10 % at 390 nm and 900 nm, respectively. In combination with the 110 m² light‐collecting capability of the LBT, we expect a limiting magnitude of ≈20th mag in V in the low‐resolution mode. The R = 120 000 mode can also be used with two, dual‐beam Stokes IQUV polarimeters. The 270 000‐mode is made possible with the 7‐slice image slicer and a 100‐µm fibre through a projected sky aperture of 0.74″, comparable to the median seeing of the LBT site. The 43 000‐mode with 12‐pixel sampling per resolution element is our bad seeing or faint‐object mode. Any of the three resolution modes can either be used with sky fibers for simultaneous sky exposures or with light from a stabilized Fabry‐Pérot étalon for ultra‐precise radial velocities. CCD‐image processing is performed with the dedicated data‐reduction and analysis package PEPSI‐S4S. Its full error propagation through all image‐processing steps allows an adaptive selection of parameters by using statistical inferences and robust estimators. A solar feed makes use of PEPSI during day time and a 500‐m feed from the 1.8 m VATT can be used when the LBT is busy otherwise. In this paper, we present the basic instrument design, its realization, and its characteristics. Some pre‐commissioning first‐light spectra shall demonstrate the basic functionality. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Urban seagrass: status of Posidonia oceanica facing the Genoa city waterfront (Italy) and implications for management

A system of five adjacent Posidonia oceanica meadows facing the waterfront of Genoa city (Ligurian Sea, NW Mediterranean) was investigated over different spatial scales (meters-kilometers) using three environmental indices: conservation index (CI), substitution index (SI) and phase-shift index (PSI). CI revealed differences mostly at large spatial scale, distinguishing the poor condition of the meadows closest to Genoa centre and harbour from the comparatively healthy condition of the farthest meadows. SI showed differences mostly at small spatial scale (i.e., within meadows), suggesting the influence of local factors in the re-colonisation of regressed meadows by the seagrass Cymodocea nodosa and/or the invasive alga Caulerpa racemosa. Mapping of PSI showed that the meadows closest to Genoa centre and harbour have undergone a nearly total phase shift and have no real potential for recovery: attempts to re-establish P. oceanica there might be a waste of time and money. On the contrary, the meadows farthest from Genoa centre and harbour showed a comparatively low level of phase shift and could still fully recover given specific management actions.     

Influence of salinity and fish species on PAH uptake from dispersed crude oil

The use of chemical oil dispersants to minimize spill impacts causes a transient increase in hydrocarbon concentrations in water, which increases the risk to aquatic species if toxic components become more bioavailable. The risk of effects depends on the extent to which dispersants enhance the exposure to toxic components, such as polycyclic aromatic hydrocarbons (PAH). Increased salinities can reduce the solubility of PAH and the efficiency of oil dispersants. This study measured changes in the induction of CYP1A enzymes of fish to demonstrate the effect of salinity on PAH availability. Freshwater rainbow trout and euryhaline mummichog were exposed to water accommodated fractions (WAF), and chemically-enhanced water accommodated fractions (CEWAF) at 0 per thousand, 15 per thousand, and 30 per thousand salinity. For both species, PAH exposure decreased as salinity increased whereas dispersant effectiveness decreased only at the highest salinity. Hence, risks to fish of PAH from dispersed oil will be greatest in coastal waters where salinities are low.     

Crystal chemistry, surface morphology and X-ray photoelectron spectroscopy of Fe-rich osumilite from Mt. Arci, Sardinia (Italy)

Microprobe analysis, single crystal X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray absorption spectroscopy were applied on Fe-rich osumilite from the volcanic massif of Mt. Arci, Sardinia, Italy. Osumilite belongs to the space group P6/mcc with unit cell parameters a = 10.1550(6), c = 14.306(1) Å and chemical formula (K_0.729)_C (Na_0.029)_B (Si_10.498 Al_1.502)_T1 (Al_2.706 Fe _0.294 ²⁺ )_T2 (Mg_0.735 Mn_0.091 Fe _1.184 ²⁺ )_AO₃₀. Structure refinement converged at R = 0.0201. Unit cell parameter a is related to octahedral edge length as well as to Fe²⁺ content, unlike the c parameter which does not seem to be affected by chemical composition. The determination of the amount of each element on the mineral surface, obtained through X-ray photoelectron spectroscopy high-resolution spectra in the region of the Si_2p, Al_2p, Mg_1s and Fe_2p core levels, suggests that Fe presents Fe²⁺ oxidation state and octahedral coordination. Two peaks at 103.1 and 100.6 eV can be related to Si⁴⁺ and Si¹⁺ components, respectively, both in tetrahedral coordination. The binding energy of Al_2p, at 74.5 eV, indicates that Al is mostly present in the distorted T2 site, whereas the Mg peak at 1,305.2 eV suggests that this cation is located at the octahedral site. X-ray absorption at the Fe L_2,3-edges confirms that iron is present in the mineral structure, prevalently in the divalent state and at the A octahedral site.