Satellite-Detected Fluorescence Reveals Global Physiology of Ocean Phytoplankton

Phytoplankton photosynthesis links global ocean biology and climate-driven fluctuations in the physical environment. These interactions are largely expressed through changes in phytoplankton physiology, but physiological status has proven extremely challenging to characterize globally. Phytoplankton fluorescence does provide a rich source of physiological information long exploited in laboratory and field studies, and is now observed from space. Here we evaluate the physiological underpinnings of global variations in satellite-based phytoplankton chlorophyll fluorescence. The three dominant factors influencing fluorescence distributions are chlorophyll concentration, pigment packaging effects on light absorption, and light-dependent energy-quenching processes. After accounting for these three factors, resultant global distributions of quenching-corrected fluorescence quantum yields reveal a striking consistency with anticipated patterns of iron availability. High fluorescence quantum yields are typically found in low iron waters, while low quantum yields dominate regions where other environmental factors are most limiting to phytoplankton growth. Specific properties of photosynthetic membranes are discussed that provide a mechanistic view linking iron stress to satellite-detected fluorescence. Our results present satellite-based fluorescence as a valuable tool for evaluating nutrient stress predictions in ocean ecosystem models and give the first synoptic observational evidence that iron plays an important role in seasonal phytoplankton dynamics of the Indian Ocean. Satellite fluorescence may also provide a path for monitoring climate-phytoplankton physiology interactions and improving descriptions of phytoplankton light use efficiencies in ocean productivity models.

Measurement of the jet radius and transverse momentum dependence of inclusive jet suppression in lead-lead collisions at sqrtsNN=2.76 TeV with the AT detector

Measurements of inclusive jet suppression in heavy ion collisions at the LHC provide direct sensitivity to the physics of jet quenching. In a sample of lead-lead collisions at root S-NN = 2.76 TeV corresponding to an integrated luminosity of approximately 7 mu b(-1), ATLAS has measured jets with a calorimeter system over the pseudorapidity interval vertical bar eta vertical bar < 2.1 and over the transverse momentum range 38 < pT <210 GeV. Jets were reconstructed using the anti-k(t) algorithm with values for the distance parameter that determines the nominal jet radius of R = 0.2, 0.3, 0.4 and 0.5. The centrality dependence of the jet yield is characterized by the jet "central-to-peripheral ratio," R-CP. Jet production is found to be suppressed by approximately a factor of two in the 10% most central collisions relative to peripheral collisions. R-CP varies smoothly with centrality as characterized by the number of participating nucleons. The observed suppression is only weakly dependent on jet radius and transverse momentum. These results provide the first direct measurement of inclusive jet suppression in heavy ion collisions and complement previous measurements of dijet transverse energy imbalance at the LHC.

Measurement of the Azimuthal Angle Dependence of Inclusive Jet Yields in Pb+Pb Collisions at sqrts_NN= 2.76 TeV with the ATLAS detector

Measurements of the variation of inclusive jet suppression as a function of relative azimuthal angle, Delta phi, with respect to the elliptic event plane provide insight into the path-length dependence of jet quenching. ATLAS has measured the Delta phi dependence of jet yields in 0.14 nb(-1) of root s(NN) = 2.76 TeV Pb + Pb collisions at the LHC for jet transverse momenta p(T) > 45 GeV in different collision centrality bins using an underlying event subtraction procedure that accounts for elliptic flow. The variation of the jet yield with Delta phi was characterized by the parameter, nu(jet)(2), and the ratio of out-of-plane (Delta phi similar to pi/2) to in-plane (Delta phi similar to 0) yields. Nonzero nu(jet)(2) values were measured in all centrality bins for p(T) < 160 GeV. The jet yields are observed to vary by as much as 20% between in-plane and out-of-plane directions.

Assembling Multiporphyrin Stacks Inside the DNA Double Helix

Double stranded DNA hybrids containing up to four consecutive, face-to-face stacked porphyrins are described. Non-nucleosidic, 5,15-bisphenyl-substituted porphyrin building blocks were incorporated into complementary oligonucleotide strands. Upon hybridization multiple porphyrins are well accommodated inside the DNA scaffold without disturbing the overall B-DNA structure. The formation of double strands containing up to four free base porphyrins is enabled without compromising duplex stability. UV/vis, fluorescence, and CD spectroscopy demonstrate the formation of porphyrins H-aggregates inside the DNA double helix and provide evidence for the existence of strong excitonic coupling between interstrand stacked porphyrins. H-aggregation results in considerable fluorescence quenching. Most intense CD effects are observed in stacks containing four porphyrins. The findings demonstrate the value of DNA for the controlled formation of molecularly defined porphyrin aggregates.

A relation between screening masses and real-time rates

Thermal screening masses related to the conserved vector current are determined for the case that the current carries a non-zero Matsubara frequency, both in a weak-coupling approach and through lattice QCD. We point out that such screening masses are sensitive to the same infrared physics as light-cone real-time rates. In particular, on the perturbative side, the inhomogeneous Schrödinger equation determining screening correlators is shown to have the same general form as the equation implementing LPM resummation for the soft-dilepton and photon production rates from a hot QCD plasma. The static potential appearing in the equation is identical to that whose soft part has been determined up to NLO and on the lattice in the context of jet quenching. Numerical results based on this potential suggest that screening masses overshoot the free results (multiples of 2πT) more strongly than at zero Matsubara frequency. Four-dimensional lattice simulations in two-flavour QCD at temperatures of 250 and 340 MeV confirm the non-static screening masses at the 10% level. Overall our results lend support to studies of jet quenching based on the same potential at T ≳ 250 MeV.

Excited state interactions between the chiral Au 38 L 24 cluster and covalently attached porphyrin

A protected S-acetylthio porphyrin was synthesized and attached to the Au38(2-phenylethanethiolate)24 cluster in a ligand exchange reaction. Chiral high performance liquid chromatography of the functionalized cluster yielded enantiomeric pairs of clusters probably differing in the binding site of the porphyrin. As proven by circular dichroism, the chirality was maintained. Exciton coupling between the cluster and the chromophore is observed. Zinc can be incorporated into the porphyrin attached to the cluster, as evidenced by absorption and fluorescence spectroscopy, however, the reaction is slow. Quenching of the chromophore fluorescence is observed, which can be explained by energy transfer from the porphyrin to the cluster. Transient absorption spectra of Au38(2-phenylethanethiolate)24 and the functionalized cluster probe the bleach of the gold cluster due to ground state absorption and the characteristic excited state absorption signals. Zinc incorporation does not have a pronounced effect on the photophysical behaviour. Decay times are typical for the molecular behaviour of small monolayer protected gold clusters.

Thermal dependence of luminescence lifetimes and radioluminescence in quartz

During time-resolved optical stimulation experiments (TR-OSL), one uses short light pulses to separate the stimulation and emission of luminescence in time. Experimental TR-OSL results show that the luminescence lifetime in quartz of sedimentary origin is independent of annealing temperature below 500 °C, but decreases monotonically thereafter. These results have been interpreted previously empirically on the basis of the existence of two separate luminescence centers LH and LL in quartz, each with its own distinct luminescence lifetime. Additional experimental evidence also supports the presence of a non-luminescent hole reservoir R, which plays a critical role in the predose effect in this material. This paper extends a recently published analytical model for thermal quenching in quartz, to include the two luminescence centers LH and LL, as well as the hole reservoir R. The new extended model involves localized electronic transitions between energy states within the two luminescence centers, and is described by a system of differential equations based on the Mott–Seitz mechanism of thermal quenching. It is shown that by using simplifying physical assumptions, one can obtain analytical solutions for the intensity of the light during a TR-OSL experiment carried out with previously annealed samples. These analytical expressions are found to be in good agreement with the numerical solutions of the equations. The results from the model are shown to be in quantitative agreement with published experimental data for commercially available quartz samples. Specifically the model describes the variation of the luminescence lifetimes with (a) annealing temperatures between room temperature and 900 °C, and (b) with stimulation temperatures between 20 and 200 °C. This paper also reports new radioluminescence (RL) measurements carried out using the same commercially available quartz samples. Gaussian deconvolution of the RL emission spectra was carried out using a total of seven emission bands between 1.5 and 4.5 eV, and the behavior of these bands was examined as a function of the annealing temperature. An emission band at ∼3.44 eV (360 nm) was found to be strongly enhanced when the annealing temperature was increased to 500 °C, and this band underwent a significant reduction in intensity with further increase in temperature. Furthermore, a new emission band at ∼3.73 eV (330 nm) became apparent for annealing temperatures in the range 600–700 °C. These new experimental results are discussed within the context of the model presented in this paper.

Inhibition of photosynthesis by high temperature in oak (Quercus pubescens L.) leaves grown under natural conditions closely correlates with a reversible heat-dependent reduction of the activation state of ribulose-1,5-bisphosphate carboxylase/oxygenase

Inhibition of the net photosynthetic CO2 assimilation rate (Pn) by high temperature was examined in oak (Quercus pubescens L.) leaves grown under natural conditions. Combined measurements of gas exchange and chlorophyll (Chl) a fluorescence were employed to differentiate between inhibition originating from heat effects on components of the thylakoid membranes and that resulting from effects on photosynthetic carbon metabolism. Regardless of whether temperature was increased rapidly or gradually, Pn decreased with increasing leaf temperature and was more than 90% reduced at 45 °C as compared to 25 °C. Inhibition of Pn by heat stress did not result from reduced stomatal conductance (gs), as heat-induced reduction of gs was accompanied by an increase of the intercellular CO2 concentration (Ci). Chl a fluorescence measurements revealed that between 25 and 45 °C heat-dependent alterations of thylakoid-associated processes contributed only marginally, if at all, to the inhibition of Pn by heat stress, with photosystem II being remarkably well protected against thermal inactivation. The activation state of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) decreased from about 90% at 25 °C to less than 30% at 45 °C. Heat stress did not affect Rubisco per se, since full activity could be restored by incubation with CO2 and Mg2+. Western-blot analysis of leaf extracts disclosed the presence of two Rubisco activase polypeptides, but heat stress did not alter the profile of the activase bands. Inhibition of Pn at high leaf temperature could be markedly reduced by artificially increasing Ci. A high Ci also stimulated photosynthetic electron transport and resulted in reduced non-photochemical fluorescence quenching. Recovery experiments showed that heat-dependent inhibition of Pn was largely, if not fully, reversible. The present results demonstrate that in Q. pubescens leaves the thylakoid membranes in general and photosynthetic electron transport in particular were well protected against heat-induced perturbations and that inhibition of Pn by high temperature closely correlated with a reversible heat-dependent reduction of the Rubisco activation state.

Excitonic splittings in molecular dimers: why static ab initio calculations cannot match them

After decades of research on molecular excitons, only few molecular dimers are available on which exciton and vibronic coupling theories can be rigorously tested. In centrosymmetric H-bonded dimers consisting of identical (hetero)aromatic chromophores, the monomer electronic transition dipole moment vectors subtract or add, yielding S0 → S1 and S0 → S2 transitions that are symmetry-forbidden or -allowed, respectively. Symmetry breaking by 12C/13C or H/D isotopic substitution renders the forbidden transition weakly allowed. The excitonic coupling (Davydov splitting) can then be measured between the S0 → S1 and S0 → S2 vibrationless bands. We discuss the mass-specific excitonic spectra of five H-bonded dimers that are supersonically cooled to a few K and investigated using two-color resonant two-photon ionization spectroscopy. The excitonic splittings Δcalc predicted by ab initio methods are 5–25 times larger than the experimental excitonic splittings Δexp. The purely electronic ab initio splittings need to be reduced (“quenched”), reflecting the coupling of the electronic transition to the optically active vibrations of the monomers. The so-called quenching factors Γ < 1 can be determined from experiment (Γexp) and/or calculation (Γcalc). The vibronically quenched splittings Γ·Δcalc are found to nicely reproduce the experimental exciton splittings.

(Table 2) Chemical composition of quenched glasses from the Mohns and Knipovich Ridges

The aim of this project was a petrogeochemical study of igneous rocks in the areas of the Mohns and Knipovich Ridges, both being the northern extensions of the Mid-Atlantic Ridge (MAR), using data available for quenching glass samples collected during Cruises 36 and 38 of R/V Akademic Mstislav Keldysh and during Cruise 15 of R/V Professor Logachev. Results of igneous rock studying from the Mohns and Knipovich Ridges at the background of evolution of the total North Atlantic Province, which had been identified earlier from tectonic and geophysical data, showed that igneous rocks of the Knipovich Ridge can be ranked as shallow tholeiites, primary melts of which were relatively rich in Na and Si and poor in Fe. This type of magma is characteristic of colder regions of the oceanic lithosphere. Its occurrence in the Knipovich Ridge and its potential propagation up to the Gakkel Ridge suggest that igneous rocks of this region originated under conditions of passive spreading in contrast to the MAR region in vicinity of Iceland and Azores, where substantial contribution of hotter material of a rising plume contributed to formation of the oceanic crust. The North Atlantic Ocean is the youngest province in terms of ocean-floor opening. Geologically and geophysically it is one of well studied regions of the World Ocean. Nevertheless some basic key items of its origin still remain to be clarified. In 1975 Scatler et al. proved specifics of this region manifested in growth of the gravity field, and also in relative height of the ocean floor in the region of 33-70°N, which was associated by them with rise of the hotter mantle, as compared with common regions of the Mid-Atlantic Ridge. Later this view was confirmed by character of magmatism, which differed in depth of generation and by melting degree of the resulting primary magma. Uniqueness of the North Atlantic region was also proved by the fact that this region was marked by extensive geochemical anomalies associated with Azores, Iceland, and Jan Mayen. All of these data allow to consider the northern part of the MAR (north of 33°N) as an united global geotectonic province. The Mohns and Knipovich Ridges located north of Iceland locate at the northern end of this province. This is the least known region. Therefore, new data for ridge areas of 73-77°N are needed for more complete geologic history of the Arctic Basin. The aim of this study was to carry out a complex comparison of magmatism at the Mohns and Knipovich Ridges with magmatism at large segments of the MAR northern province and to reconstruct mechanisms of primary magma formation, as well as conditions of their fractionation. This paper was based on results of studying quenched glasses, which reflect evolution of melt in the course of its formation.

Temperature tolerance of western Baltic Sea Fucus vesiculosus - growth, photosynthesis and survival

Fucus vesiculosus L. (Phaeophyceae) is the most abundant and hence ecologically most important primary producer, carbon sink and habitat provider in the western Baltic Sea. All F. vesiculosus L. specimens were collected on 23 April 2014 from a depth of 0.2-1 m in the non-tidal Kiel Fjord, western Baltic Sea (54°27'N; 10°12'E), where this species forms dense and almost monospecific stands on stones. After sampling the algal thalli were stored in a refrigerator box with water from the sampling site, transported to Bremerhaven and stored at 10 °C for one day in filtered seawater. Experiments were conducted with vegetative apical tips (6.7±0.5 cm length), the actively growing region of F. vesiculosus, which were randomly selected and cut from 144 different individuals prior to the experiments. These tips were acclimated to laboratory conditions for three days in filtered seawater at 10 °C before the start of the experiment. Furthermore, 30 additional vegetative apices were freeze-dried to document the initial biochemical status of F. vesiculosus in its native habitat. A temperature gradient was installed in a walk-in constant cooling chamber (15 °C) in nine water baths (5, 10, 15, 20, 24, 26, 27, 28 and 29 °C ± 0.1 °C) which were tempered by thermostats (5, 10 and 15 °C: Huber Variostat CC + Pilot ONE, Peter Huber Kältemaschinen GmbH, Offenburg, Germany; 20 and 28 °C: Haake DC3, Thermo Fisher Scientific Inc., Waltham, USA; 24, 26, 27 and 29 °C: Haake DC10). Every temperature treatment consisted of four 2 L glass beakers (n = 4). In each beaker four F. vesiculosus apices were grown in 2 µm-filtered North Sea water diluted with demineralized water in a ratio of 1:1 and enriched with nutrients after Provasoli (1968; 1/10 enrichment), leading to a salinity of about 15.6 which equaled habitat conditions. The algae were exposed to an irradiance of 130 µmol photons m-2 s-1 ±10 % (Powerstar HGI-TS 150 W, OSRAM GmbH, Bad Homburg, Germany) measured at the top of the beaker under a 16:8 h L:D cycle. The media in the beakers was changed every third or fourth day and aerated with artificial air containing 380 ppm CO2 (gas mixing device; HTK Hamburg GmbH, Hamburg, Germany). Before the experiment, the algae were acclimated to the final temperatures in steps of 5 °C for 2 days each, beginning at 10 °C. After 21 days exposure time, three out of four samples per replicate were freeze-dried for further biochemical analyses, and afterwards the thermostats were turned off to reduce the temperature to 16±0.4 °C for another 10 days permitting growth under post-culture conditions.

(Table 1) Effects of desiccation on photochemical processes and nitrogenase activity in Nostoc commune s.l. colonies

The effects of desiccation on photochemical processes and nitrogenase activity were evaluated in Nostoc commune s.l. colonies in situ from a wet thufur meadow at Petuniabukta, Billefjorden, Central Svalbard, during the 2009 arctic summer. The colonies were collected in the fully hydrated state, and were subjected to slow desiccation at ambient temperatures (5 - 8°C) and low light (30 - 80 µmol/m**2/s). For each colony the weight, area, photochemical performance, and nitrogenase activity were determined at the beginning, as well as on every day during the first four days of the experiment; thereafter, on every second day until desiccation was complete. The photochemical performance was evaluated from variable chlorophyll fluorescence parameters (FV/FM, Phi(PSII) , qP, and NPQ), and the nitrogenase activity was estimated by an acetylene-ethylene reduction assay. A significant decrease in the photochemically active area was recorded from the third day, when the colony had lost approximately 40% of its original weight indicating some changes in the extracellular matrix, and stopped on the 14th to 18th day. No effects of the desiccation on the main photochemical parameters (FV/FM, Phi(PSII), qP) were observed up to the sixth to eighth days of desiccation. Slightly lower values of FV/FM and Phi(PSII) recorded in fully-hydrated colonies could be caused by impaired diffusion of CO2 into cells. The steep reduction of photochemical activity occurred between the eighth and tenth day of the experiment, when the colony had lost approximately 80% of its fully-hydrated weight. The nitrogenase activity was highest on the first day, probably due to improved diffusion of N2 into cells, then declined, but was detectable until the sixth day of the experiment. Since Nostoc commune s.l. colonies were capable of photosynthesis and nitrogen fixation to the level of ca. 60% of its fully-hydrated weight, even partly-hydrated colonies contribute substantially to carbon and nitrogen cycling in the High Arctic wet meadow tundra ecosystem.

Mineral chemistry of primary and secondary phases in basaltic rocks

Primary magmatic phases (spinel, olivine, plagioclase, clinopyroxene, amphibole, and biotite) and secondary phyllosilicates (smectite, chlorite-smectite, and celadonite) were analyzed by electron microprobe in alkalic and tholeiitic dolerites and basalts from Ocean Drilling Program Sites 800, 801, and 802. Aphyric alkalic dolerite sills (Hole 800A) and basalt flows (Holes 801B and 801C) share common mineralogical features: matrix feldspars are strongly zoned from labradorite cores to discrete sodic rims of alkali feldspar with a high Or component, which overlaps that of quench microlites in glassy mesostasis; little fractionated clinopyroxenes are Ti-rich diopsides and augites (with marked aegirine-augite rims at Site 801); rare, brown, Fe**3+-rich amphibole is winchite; and late biotites exhibit variable Ti contents. Alkalic rims to feldspars probably developed at the same time as quenched mesostasis feldspars and late-stage magmatic biotite, and represent the buildup of K-rich hydrous fluids during crystallization. Phenocryst phases in primitive mid-ocean ridge tholeiites from Hole 801C (Mg numbers about 70) have extreme compositions with chrome spinel (Cr/Cr + Al ratios about 0.2-0.4), Ni-rich olivine (Fo90), and highly calcic plagioclase (An90). Later glomerophyric clumps of plagioclase (An75-80) and clinopyroxene (diopside-augite) are strongly zoned and probably reflect rapidly changing melt conditions during upward transport, prior to seafloor quenching. In contrast, phenocryst phases (olivine, plagioclase, and clinopyroxene) in the Hole 802A tholeiites show limited variation and do not have such primitive compositions, reflecting the uniform and different chemical composition of all the bulk rocks. Replacive phyllosilicates in both alkalic and tholeiitic basalts include various colored smectites (Fe-, Mg-, and Al-saponites), chlorite-smectite and celadonite. Smectite compositions typically reflect the replaced host composition; glass is replaced by brown Fe-saponites (variable Fe/Mg ratios) and olivine by greenish Mg-saponites (or Al-rich chlorite-smectite).