Accurate rotational constant and bond lengths of hexafluorobenzene by femtosecond rotational Raman coherence spectroscopy and ab initio calculations

The gas-phase rotational motion of hexafluorobenzene has been measured in real time using femtosecond (fs) time-resolved rotational Raman coherence spectroscopy (RR-RCS) at T = 100 and 295 K. This four-wave mixing method allows to probe the rotation of non-polar gas-phase molecules with fs time resolution over times up to ∼5 ns. The ground state rotational constant of hexafluorobenzene is determined as B 0 = 1029.740(28) MHz (2σ uncertainty) from RR-RCS transients measured in a pulsed seeded supersonic jet, where essentially only the v = 0 state is populated. Using this B 0 value, RR-RCS measurements in a room temperature gas cell give the rotational constants B v of the five lowest-lying thermally populated vibrationally excited states ν7/8, ν9, ν11/12, ν13, and ν14/15. Their B v constants differ from B 0 by between −1.02 MHz and +2.23 MHz. Combining the B 0 with the results of all-electron coupled-cluster CCSD(T) calculations of Demaison et al. [Mol. Phys.111, 1539 (2013)] and of our own allow to determine the C-C and C-F semi-experimental equilibrium bond lengths r e(C-C) = 1.3866(3) Å and r e(C-F) = 1.3244(4) Å. These agree with the CCSD(T)/wCVQZ r e bond lengths calculated by Demaison et al. within ±0.0005 Å. We also calculate the semi-experimental thermally averaged bond lengths r g(C-C)=1.3907(3) Å and r g(C-F)=1.3250(4) Å. These are at least ten times more accurate than two sets of experimental gas-phase electron diffraction r g bond lengths measured in the 1960s.

Temperature Prediction Model for Bone Drilling Based on Density Distribution and In Vivo Experiments for Minimally Invasive Robotic Cochlear Implantation

Surgical robots have been proposed ex vivo to drill precise holes in the temporal bone for minimally invasive cochlear implantation. The main risk of the procedure is damage of the facial nerve due to mechanical interaction or due to temperature elevation during the drilling process. To evaluate the thermal risk of the drilling process, a simplified model is proposed which aims to enable an assessment of risk posed to the facial nerve for a given set of constant process parameters for different mastoid bone densities. The model uses the bone density distribution along the drilling trajectory in the mastoid bone to calculate a time dependent heat production function at the tip of the drill bit. Using a time dependent moving point source Green's function, the heat equation can be solved at a certain point in space so that the resulting temperatures can be calculated over time. The model was calibrated and initially verified with in vivo temperature data. The data was collected in minimally invasive robotic drilling of 12 holes in four different sheep. The sheep were anesthetized and the temperature elevations were measured with a thermocouple which was inserted in a previously drilled hole next to the planned drilling trajectory. Bone density distributions were extracted from pre-operative CT data by averaging Hounsfield values over the drill bit diameter. Post-operative [Formula: see text]CT data was used to verify the drilling accuracy of the trajectories. The comparison of measured and calculated temperatures shows a very good match for both heating and cooling phases. The average prediction error of the maximum temperature was less than 0.7 °C and the average root mean square error was approximately 0.5 °C. To analyze potential thermal damage, the model was used to calculate temperature profiles and cumulative equivalent minutes at 43 °C at a minimal distance to the facial nerve. For the selected drilling parameters, temperature elevation profiles and cumulative equivalent minutes suggest that thermal elevation of this minimally invasive cochlear implantation surgery may pose a risk to the facial nerve, especially in sclerotic or high density mastoid bones. Optimized drilling parameters need to be evaluated and the model could be used for future risk evaluation.

Temperature-dependent phenology of Plutella xylostella (Lepidoptera: Plutellidae)

Temperature-dependent population growth of diamondback moth (DBM) Plutella xylostella (L.), a prolific insect pest of crucifer vegetables, was studied under six constant temperatures in the laboratory. The objective of the study was to predict the impacts of temperature changes on the population of DBM at high-resolution scales along altitudinal gradients and under climate change scenarios. Non-linear functions were fitted on the data for modeling the development, mortality, longevity and oviposition of the pest. The best-fitted functions for each life stage were compiled for estimating the life table parameters of the species by stochastic simulations. To quantify the impacts on the pest, three indices (establishment, generation and activity) were computed using the estimates of life table parameters and temperature data obtained at local scale (current scenario 2013) and downscaled climate change data (future scenario 2055) from the AFRICLIM database. To measure and represent the impacts of temperature change along the altitude on the pest; the indices were mapped along the altitudinal gradients of Kilimanjaro and Taita Hills, in Tanzania and Kenya, respectively. Potential impact of the changes between climate scenarios 2013 and 2055 was assessed. The data files included in this database were utilized for the above analysis to develop temperature dependent phenology of Plutella xylostella to assess current and future distribution along eastern African Afromontanes.

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.

Pyrolyzable carbon, temperature maximum, production index and lithology for DSDP Leg 96 holes

Sediments from Deep Sea Drilling Project Sites 615, 617, 618, 619, and 620-623 were subjected to pyrolysis. The sediments are immature with respect to petroleum generation as determined by production index values of less than 0.1 and Tmax values of 460-480°C. The amount of pyrolyzable organic matter was moderately low as compared to typical petroleum source rocks. The immature organic matter present does not appear to contain a significant proportion of woody material as shown by the low gas-generating potential. Typical overbank sediments from Sites 617 and 620 generally show higher P2 values (500-800 µg hydrocarbon per g dry weight sediment) than typical channel-fill sediments from Sites 621 and 622 (P2 = 450-560 µg/g). Tmax for both types of sediment remained very constant (462-468 °C) with a slight elevation (+ 15°C) occurring in samples containing lignite. The highest P2 values occurred in sections described as turbidites. Very low P2 values (about 50 µg/g) occurred in sands. P2 values for shallower sections of basin Sites 618 and 619 tended to be higher (900-1000 µg/g) and decreased in deeper, more terrigenous sections of Site 619. Preliminary experiments indicate that microbiological degradation of sediment organic matter causes a decrease in P2. Pyrolyzable organic matter from lower fan Site 623 appears to increase with depth in two different sediment sequences (40-85 and 95-125 m sub-bottom). Organic matter type, as shown by pyrolysis capillary gas chromatography (GC) patterns, was generally the same throughout the well, with much more scatter occurring in the deepest sections (130-155 m sub-bottom). One major and two minor organic matter types could be recognized in both fan and basin sites drilled on Leg 96.

Marine meso-herbivore consumption scales faster with temperature than seaweed primary production, supplementary material

Respiration of ectotherms is predicted to increase faster with rising environmental temperature than photosynthesis of primary producers because of the differential temperature dependent kinetics of the key enzymes involved. Accordingly, if biological processes at higher levels of complexity are constrained by underlying metabolic functions food consumption by heterotrophs should increase more rapidly with rising temperature than photo-autoptrophic primary production. We compared rates of photosynthesis and growth of the benthic seaweed Fucus vesiculosus with respiration and consumption of the isopod Idotea baltica to achieve a mechanistic understanding why warming strengthens marine plant-herbivore interactions. In laboratory experiments thallus pieces of the seaweed and individuals of the grazer were exposed to constant temperatures at a range from 10 to 20°C. Photosynthesis of F. vesiculosus did not vary with temperature indicating efficient thermal acclimation whereas growth of the algae clearly increased with temperature. Respiration and food consumption of I. baltica also increased with temperature. Grazer consumption scaled about 2.5 times faster with temperature than seaweed production. The resulting mismatch between algal production and herbivore consumption may result in a net loss of algal tissue at elevated temperatures. Our study provides an explanation for faster decomposition of seaweeds at elevated temperatures despite the positive effects of high temperatures on algal growth.

Interacting effects of CO2 partial pressure and temperature on photosynthesis and calcification in a scleractinian coral, 2003

We show here that CO2 partial pressure (pCO2) and temperature significantly interact on coral physiology. The effects of increased pCO2 and temperature on photosynthesis, respiration and calcification rates were investigated in the scleractinian coral Stylophora pistillata. Cuttings were exposed to temperatures of 25°C or 28°C and to pCO2 values of ca. 460 or 760 muatm for 5 weeks. The contents of chlorophyll c2 and protein remained constant throughout the experiment, while the chlorophyll a content was significantly affected by temperature, and was higher under the 'high-temperature-high-pCO2' condition. The cell-specific density was higher at 'high pCO2' than at 'normal pCO2' (1.7 vs. 1.4). The net photosynthesis normalized per unit protein was affected by both temperature and pCO2, whereas respiration was not affected by the treatments. Calcification decreased by 50% when temperature and pCO2 were both elevated. Calcification under normal temperature did not change in response to an increased pCO2. This is not in agreement with numerous published papers that describe a negative relationship between marine calcification and CO2. The confounding effect of temperature has the potential to explain a large portion of the variability of the relationship between calcification and pCO2 reported in the literature, and warrants a re-evaluation of the projected decrease of marine calcification by the year 2100.

Grazing under experimental hypercapnia and elevated temperature does not affect the radula of a chiton (Mollusca, Polyplacophora, Lepidopleurida)

Chitons (class Polyplacophora) are benthic grazing molluscs with an eight-part aragonitic shell armature. The radula, a serial tooth ribbon that extends internally more than half the length of the body, is mineralised on the active feeding teeth with iron magnetite apparently as an adaptation to constant grazing on rocky substrates. As the anterior feeding teeth are eroded they are shed and replaced with a new row. The efficient mineralisation and function of the radula could hypothetically be affected by changing oceans in two ways: changes in seawater chemistry (pH and pCO2) may impact the biomineralisation pathway, potentially leading to a weaker or altered density of the feeding teeth; rising temperatures could increase activity levels in these ectothermic animals, and higher feeding rates could increase wear on the feeding teeth beyond the animals' ability to synthesise, mineralise, and replace radular rows. We therefore examined the effects of pH and temperature on growth and integrity in the radula of the chiton Leptochiton asellus. Our experiment implemented three temperature (10, 15, 20 °C) and two pCO2 treatments (400 µatm, pH 8.0; 2000 µatm, pH 7.5) for six treatment groups. Animals (n = 50) were acclimated to the treatment conditions for a period of 4 weeks. This is sufficient time for growth of ca. 7-9 new tooth rows or 20% turnover of the mineralised portion. There was no significant difference in the number of new (non-mineralised) teeth or total tooth row count in any treatment. Examination of the radulae via SEM revealed no differences in microwear or breakage on the feeding cusps correlating to treatment groups. The shell valves also showed no signs of dissolution. As a lineage, chitons have survived repeated shifts in Earth's climate through geological time, and at least their radulae may be robust to future perturbations.

Uncalibrated temperature measurement during R/V Maria S. Merian cruise MSM21/1b

GEOMAR's autonomous underwater vehicle (AUV Abyss REMUS 6000) was deployed within the framework of a multi-platform experiment in June 2012 with R/V Maria S. Merian cruise MSM21/1b at about 180 km downstream of Denmark Strait. The scientific payload included a pumped Seabird 49 FastCAT CTD system, a paroscientific pressure sensor, and shear and temperature microstructure profiler from Rockland Scientific Inc.. In total, six of eight AUV dives were carried out successfully. Aborts on three dives were caused by strong counter currents the AUV experienced in the Denmark Strait Overflow plume, which made the AUV fail to reach its waypoints on schedule. During all missions the AUV was programmed to dive at constant depth levels along? straight legs approximately parallel to chosen isobaths with a constant speed of 1.6 m s-1 through the water.

Seasonality in pH and temperature for shallow zones of the Bering Sea from measurements of coral Clathromorphum nereostratum

Increasing atmospheric CO2 concentrations are potentially affecting marine ecosystems twofold, by warming and acidification. The rising amount of CO2 taken up by the ocean lowers the saturation state of calcium carbonate, complicating the formation of this key biomineral used by many marine organisms to build hard parts like skeletons or shells. Reliable time-series data of seawater pH are needed to evaluate the ongoing change and compare long-term trends and natural variability. For the high-latitude ocean, the region facing the strongest CO2 uptake, such time-series data are so far entirely lacking. Our study provides, to our knowledge, the first reconstruction of seasonal cycle and long-term trend in pH for a high-latitude ocean obtained from 2D images of stable boron isotopes from a coralline alga.

Limited effects of increased CO2 and temperature on metal and radionuclide bioaccumulation in a sessile invertebrate, the oyster Crassostrea gigas

This study investigated the combined effects of reduced pH and increased temperature on the capacities of the Pacific cupped oyster Crassostrea gigas to bioconcentrate radionuclide and metals. Oysters were exposed to dissolved radiotracers (110mAg, 241Am, 109Cd,57Co,54Mn, and 65Zn) at three pH (7.5, 7.8, 8.1) and two temperatures (21 and 24°C) under controlled laboratory conditions. Although calcifying organisms are recognized as particularly vulnerable to ocean acidification, the oyster did not accumulate differently the studied metals when exposed under the different pH conditions. However, temperature alone or in combination with pH somewhat altered the bioaccumulation of the studied elements. At pH 7.5, Cd was accumulated with an uptake rate constant twofold higher at 24°C than 21°C. Bioaccumulation of Mn was significantly affected by an interactive effect between seawater pH and temperature, with a decreased uptake rate at pH 7.5 when temperature increased (27 ± 1 vs. 17 ± 1 /day at 21 and 24°C, respectively). Retention of Co and Mn tended also to decrease at the same pH with decreasing temperature. Neither pH nor temperature affected strongly the elements distribution between shell and soft tissues. Significant effects of pH were found on the bioaccessibility of Mn, Zn, and 241Am during experimental in vitro simulation of human digestion.

High resolution in situ microsensor measurements of oxygen and temperature at a vesicomyid clam colony in the Japan Deep Sea Trench

Oxygen penetration depth and temperature at the rim of the clam colony was measured with a small deep-sea microprofiler module (Treude et al., 2009), carrying 3 oxygen Clark-type microelectrodes (Revsbech et al., 1980) and one temperature sensor (Pt100, UST Umweltsensorentechnik GmbH, Germany). High-resolution microprofiles across the sediment-water interface were measured with a vertical resolution of 100 µm on a total length of 15 cm. Oxygen electrodes had a linear response to the oxygen concentration in seawater and were calibrated in situ using constant readings in the bottom water (oxygen concentration determined by Winkler titration) and the anoxic parts of the sediment.

(Table 1) Oxygen isotope composition and comparison between ages and sea surface temperature from sediment core KH-79-3_L-3

The Japan Sea experienced bottom water anoxia at the last glacial maximum (LGM) since it is surrounded by four shallow straits, the sill depths of which are close to, or shallower than, the drop in sea level (~120 m) that occurred then. A distinctive negative d18O excursion of planktonic foraminifera also took place during the LGM. This excursion has been interpreted from foraminiferal data as recording a drop in the paleosalinity of surface waters on the assumption of a constant low sea surface temperatures between 34 and 11 ka. We present here a profile of alkenone-based sea surface temperatures (alkenone-SSTs) over the past 36 kyr. Our results suggest that SSTs during the LGM were much higher than those previously assumed. After considering the factors that might affect estimation of alkenone-SSTs and comparisons of core-top alkenone-SSTs values with values for modern seawater we conclude that the higher alkenone-SSTs during the LGM are reliable and reasonable. These warm SSTs were probably caused by radiative equilibrium associated with the development of stable water stratification in the Japan Sea during the LGM.

Sea surface temperature and age analysis from sediment core KT94-15_PC-9, XP98-PC-4 and XP98-PC-2

The Japan Sea experienced bottom water anoxia at the last glacial maximum (LGM) since it is surrounded by four shallow straits, the sill depths of which are close to, or shallower than, the drop in sea level (~120 m) that occurred then. A distinctive negative d18O excursion of planktonic foraminifera also took place during the LGM. This excursion has been interpreted from foraminiferal data as recording a drop in the paleosalinity of surface waters on the assumption of a constant low sea surface temperatures between 34 and 11 ka. We present here a profile of alkenone-based sea surface temperatures (alkenone-SSTs) over the past 36 kyr. Our results suggest that SSTs during the LGM were much higher than those previously assumed. After considering the factors that might affect estimation of alkenone-SSTs and comparisons of core-top alkenone-SSTs values with values for modern seawater we conclude that the higher alkenone-SSTs during the LGM are reliable and reasonable. These warm SSTs were probably caused by radiative equilibrium associated with the development of stable water stratification in the Japan Sea during the LGM.