Literature review of elasmobranch bycatch and retention rate

To address growing concern over the effects of fisheries non-target catch on elasmobranchs worldwide, the accurate reporting of elasmobranch catch is essential. This requires data on a combination of measures, including reported landings, retained and discarded non-target catch, and post-discard survival. Identification of the factors influencing discard vs. retention is needed to improve catch estimates and to determine wasteful fishing practices. To do this we compared retention rates of elasmobranch non-target catch in a broad subset of fisheries throughout the world by taxon, fishing country, and gear. A regression tree and random forest analysis indicated that taxon was the most important determinant of retention in this dataset, but all three factors together explained 59% of the variance. Estimates of total elasmobranch removals were calculated by dividing the FAO global elasmobranch landings by average retention rates and suggest that total elasmobranch removals may exceed FAO reported landings by as much as 400%. This analysis is the first effort to directly characterize global drivers of discards for elasmobranch non-target catch. Our results highlight the importance of accurate quantification of retention and discard rates to improve assessments of the potential impacts of fisheries on these species.

Highly stereoselective decarboxylation of (+)-1-Bromo-1-chloro-2,2,2-trifluoropropanoic acid gives (+)-1-Bromo-1-chloro-2,2,2-trifluoroethane ((+)-Halothane) with retention of configuration

The absolute configuration of the title acid (2) has been determined to be S by X-ray crystallography. Thus, decarboxylation of 2 produces (S)-(+)-halothane with 99% retention of configuration. This behavior is compared to other stereoselective decarboxylation reactions of ?-haloacids from the literature that also give high degrees of retention of configuration when in the form of their quaternary ammonium salts, which contain one proton. The proton of the ammonium salt is necessary to protonate the anionic intermediate formed from decarboxylation. In the absence of this relatively acidic proton, we had previously found that using triethylene glycol (TEG) as both solvent and proton source for the decarboxylation reaction of acid 2 caused poor stereoselectivity. This was in contrast to 1,2,2,2-tetrafluoro-1-methoxypropionic acid (6), which showed a high degree of retention of configuration in TEG. To rationalize this differing behavior we report DFT studies at PCM-B3LYP/6-31++G** level of theory (the results were additionally confirmed with 6-311++G** and aug-cc-pVDZ basis sets). The energy barrier to inversion of configuration of the anionic reaction intermediate of acid 2 (11) is 10.23 kcal/mol. However, we find that the anionic intermediate from acid 6 (10) would rather undergo ?-elimination instead of inversion of configuration. Thus the planar transition state required for inversion of configuration is never reached, regardless of the rate of proton transfer to the anion.

The glacier inventory of Salzburg, Austria, 2007/2009

A third glacier inventory (GI3) is presented for the province of Salzburg where 173 glaciers are located in the seven mountain ranges: Ankogel (47°4'N, 13°14'E), Glockner, Granatspitz, Sonnblick (Goldberg), Hochkönig, Venediger and Zillertal (47°8'N, 12°7'E). The basis for the new GI3 are orthophotos of 2007 and 2009 and the digital elevation model (DEM) of the southern part of Salzburg. On the basis of former inventories, area- and volume changes have been calculated. The biggest relative loss of glacier area per mountain range was found in the Ankogel range and on Hochkönig as a result of the disrupted structure of their small and thin glaciers. In terms of absolute values, the largest changes took place in the Glockner- and Venediger range with an area loss of -10.1 km**2 and -9.7 km**2 during the period between GI1 (1969) and GI3 (2007/2009), respectively. Volume changes have been calculated for nearly half of the glacier area in Salzburg, where DEMs were available. The Glockner, Granatspitz and Sonnblick mountain ranges showed a volume loss of -0.481 km**3 which corresponds to a mean thickness change of -10.5 m. An extrapolation of these changes to all of the 173 glaciers in Salzburg results in a loss of about 1.04 km**3 between GI1 and GI3 and 0.44 km**3 between GI2 and GI3. Overall annual changes in the province of Salzburg between GI2 and GI3 were higher than between GI1 and GI2 and show likewise changes such as those of Tyrol.

Fission track analyses of ODP Hole 129-800A samples

Four models of fission track annealing in apatite are compared with measured fission track lengths in samples from Site 800 in the East Mariana Basin, Ocean Drilling Program Leg 129, given an independently determined temperature history. The temperature history of Site 800 was calculated using a one-dimensional, compactive, conductive heat flow model assuming two end-member thermal cases: one for cooling of Jurassic ocean crust that has experienced no subsequent heating, and one for cooling of Cretaceous ocean crust. Because the samples analyzed were only shallowly buried and because the tectonic history of the area since sample deposition is simple, resolution of the temperature history is high. The maximum temperature experienced by the sampled bed is between 16°-21°C and occurs at 96 Ma; temperatures since the Cretaceous have dropped in spite of continued pelagic sediment deposition because heat flow has continued to decay exponentially and bottom-water temperatures have dropped. Fission tracks observed within apatite grains from the sampled bed are 14.6 +/- 0.1 µm (1 sigma) long. Given the proposed temperature history of the samples, one unpublished and three published models of fission track annealing predict mean track lengths from 14.8 to 15.9 µm. These models require temperatures as much as 40°C higher than the calculated paleotemperature maximum of the sampled bed to produce the same degree of track annealing. Measured and predicted values are different because annealing models are based on extrapolation of high temperature laboratory data to geologic times. The model that makes the closest prediction is based on the greatest number of experiments performed at low temperature and on an apatite having composition closest to that of the core samples.

Chronostratigraphy of sediments from the Bahamas

Continuous cores drilled during the Bahamas Drilling Project (BDP) and the Ocean Drilling Program (ODP) Leg 166 along a transect from the top of Great Bahama Bank to the basin in the Straits of Florida provide a unique data set to test the assumption in seismic stratigraphy that seismic reflections are time lines and, thus, have a chronostratigraphic significance. Seismic reflections that are identified as seismic sequence boundaries (SSBs) were dated by means of biostratigraphy in the five ODP sites and by a combination of biostratigraphy, magnetostratigraphy and Sr isotope stratigraphy in the two BDP sites. The seismic reflection horizons are carried across a variety of facies belts from shallow-water carbonates over slope carbonates to drift deposits in the Straits of Florida. Within this system 17 SSBs were identified and dated. Despite the fact that the seismic reflections cross several facies belts, their ages remain remarkably constant. The average offset in all sites is 0.38 Myr. In no cases do the seismic reflections cut across time lines. The age differences are the combined result of the biostratigraphic sampling frequency, the spacing of marker species that required extrapolation of ages, and the resolution of the seismic data. In addition, uncertainties of age determination in the proximal sites where age-diagnostic fauna are rare add to the age differences between sites. Therefore, it can be concluded that the seismic reflections, which mark the SSBs along the Bahamas Transect, are time lines and can be used as stratigraphic markers. This finding implies that depositional surfaces are preferentially imaged by reflected seismic waves and that an impedance contrast exists across these surfaces. Facies successions across the sequence boundaries indicate that the sequence boundaries coincide with the change of deposition from times of high to low sea level. In the carbonate setting of Great Bahama Bank, sea-level changes produce changes in sediment composition, sedimentation rate and diagenesis from the platform top to the basin. The combination of these factors generates differences in sonic velocity and, thus, in impedance that cause the seismic reflection. The impedance contrasts decrease from the proximal to the distal sites, which is reflected in the seismic data by a decrease of the seismic amplitude in the basinal area.

Maps and acoustic profiles of free gas distribution, Western Baltic Sea and Kattgat-Skagerrak area

A shallow gas depth-contour map covering the Skagerrak-western Baltic Sea region has been constructed using a relatively dense grid of existing shallow seismic lines. The digital map is stored as an ESRI shape file in order to facilitate comparison with other data from the region. Free gas usually occurs in mud and sandy mud but is observed only when sediment thickness exceeds a certain threshold value, depending on the water depth of the area in question. Gassy sediments exist at all water depths from approx. 20 m in the coastal waters of the Kattegat to 360 m in the Skagerrak. In spite of the large difference in water depths, the depth of free gas below seabed varies only little within the region, indicating a relatively fast movement of methane in the gas phase towards the seabed compared to the rate of diffusion of dissolved methane. Seeps of old microbial methane occur in the northern Kattegat where a relatively thin cover of sandy sediments exists over shallow, glacially deformed Pleistocene marine sediments. Previous estimates of total methane escape from the area may be correct but the extrapolation of local methane seepage rate data to much larger areas on the continental shelf is probably not justified. Preliminary data on porewater chemistry were compared with the free gas depth contours in the Aarhus Bay area, which occasionally suffers from oxygen deficiency, in order to examine if acoustic gas mapping may be used for monitoring the condition of the bay.

Geochemistry of Miocene "blue tuff" samples

Distinctive, massive to stratified, pale blue volcaniclastics, initially referred to as the "blue tuff," were encountered at all four sites drilled during ODP Leg 127 in the Japan Sea. Detailed vertical sequence analysis, plagioclase chemistry, plagioclase 87Sr/86Sr isotopic composition, and 40Ar/39Ar age dating indicate that thick sequences of the blue tuff are not genetically related. Blue tuffs at Hole 794B were apparently deposited by density flows at ambient temperature. Deposition was penecontemporaneous with a large submarine phreatomagmatic eruption at 14.9 Ma in bathyal or deeper water depths. The blue tuffs at this location comprise mostly reworked hydroclastic glass shards and lesser amounts of plagioclase crystals. Pyrogenic plagioclase has an average An mole% of 18±3. Comparison of blue tuff plagioclase compositions with the composition of plagioclase from acoustic basement at Site 794 suggests that these rocks are not genetically related. As such, the extrapolation of sediment accumulation rate data in conjunction with this more precise age for the blue tuff corroborates previous minimum age estimates of 16.2 Ma for acoustic basement at Site 794. Blue tuffs at Hole 796B were probably deposited at ambient temperatures by downslope slumping and density flow of reworked pyrogenic debris. This debris includes abundant bubble wall glass shards and plagioclase crystals, with variable admixture of volcanic lithic and intrabasinal fragments. Pyrogenic fragments were produced by subaerial or shallow submarine, magmatic eruptions dated at 7.6 Ma. Blue tuffs contain a heterogeneous mixture of unrelated fragments including a mixed population of plagioclase crystals. The average An mole% of the predominant, probable comagmatic, plagioclase population is 30±4. The two sequences of blue tuff studied are distinct in age, mineral composition, and the eruptive origin of pyroclastic fragments. Preliminary 87Sr/86Sr isotopic compositions of plagioclase, however, indicates that blue tuffs at both locations are the product of typical, subduction-related island arc magmatism. Based on the results of this study, there is no justification for stratigraphic correlation of widespread, Miocene, blue to blue-gray bentonitic tuff and tuffaceous sandstones nor the interpretation that these strata are indicative of regional, explosive submarine volcanism genetically related to rifting and formation of the Japan Sea. Rather, these reworked pyroclastic strata of intermediate composition were deposited over a protracted 6-8 m.y. period in association with widespread, subduction-related submarine to subaerial volcanism in the Japan Sea backarc basin.

U-Th dating of marine sediments from the Bahamas slope

In order to understand the driving forces for Pleistocene climate change more fully we need to compare the timing of climate events with their possible forcing. In contrast to the last interglacial (marine isotope stage (MIS) 5) the timing of the penultimate interglacial (MIS 7) is poorly constrained. This study constrains its timing and structure by precise U-Th dating of high-resolution delta18O records from aragonite-rich Bahamian slope sediments of ODP Leg 166 (Sites 1008 and 1009). The major glacial-interglacial cycles in delta18O are distinct within these cores and some MIS 7 substages can be identified. These sediments are well suited for U-Th dating because they have uranium concentrations of up to 12 ppm and very low initial 230Th contributions with most samples showing 230Th/232Th activity ratio of >75. U and Th concentrations and isotope ratios were measured by thermal ionisation mass spectrometry and multiple collector inductively coupled plasma mass spectrometry, with the latter providing dramatically better precision. Twenty-nine of the 41 samples measured have a delta234U value close to modern seawater suggesting that they have experienced little diagenesis. Ages from 27 of the 41 samples were deemed reliable on the basis of both their U and their Th isotope ratios. Ages generally increase with depth, although we see a repeated section of stratigraphy in one core. Extrapolation of constant sedimentation rate through each substage suggests that the peak of MIS 7e lasted from ~237 to 228 ka and that 7c began at 215 ka. This timing is consistent with existing low precision radiometric dates from speleothem deposits. The beginning of both these substages appears to be slightly later than in orbitally tuned timescales. The end of MIS 7 is complex, but also appears to be somewhat later than is suggested by orbitally tuned timescales, although this event is not particularly well defined in these cores.

Ages and two-way travel times of ODP Sites 180-1109, 180-1115 and 180-1118

Synthetic seismograms are constructed from check shot-corrected velocity and density measurements collected during Ocean Drilling Program (ODP) Leg 180 at Sites 1109, 1115, and 1118. The synthetic seismograms facilitate direct correlation of a coincident multichannel seismic (MCS) profile with borehole data collected at the three sites. The MCS data and the synthetic seismograms correlate very well, with most major reflectors successfully reproduced in the synthetics. Our results enable a direct calibration of the MCS data in terms of age, paleoenvironment, and subsidence history. Seismic reflectors are time correlative within stratigraphic resolution but are often observed to result from different lithologies across strike. Our results facilitate the extrapolation of the sedimentation history into an unsampled section of Site 1118 and enable a full correlation between the three sites using all the data collected during ODP Leg 180. This study forms the foundation for regionalizing the site data to the northern margin of the Woodlark Basin, where the transition from continental rifting to seafloor spreading is taking place.

Methane concentrations in sediments of ODP sites 186-1150 and 186-1151

Substantial amounts of adsorbed methane were detected in authigenic carbonate concretions recovered from sedimentary layers from depths between 245 and 1,108 m below seafloor during Ocean Drilling Program Leg 186 to ODP sites 1150 and 1151 on the deep-sea terrace of the Japan Trench. Methane contents were almost two orders of magnitude higher in the concretions (291-4,528 nmol/g wet wt) than in the surrounding bulk sediments (5-93 nmol/g wet wt), whereas methane/ethane ratios and stable carbon isotopic compositions were very similar. Carbonate content of surrounding bulk sediments (0.02-3.2 wet wt%) and methane content of the surrounding bulk sediments correlated positively. Extrapolation of the carbonate contents of bulk sediments suggests that 100 wt% carbonate would correspond to 1,886±732 nmol methane per g bulk sediment, which is similar to the average value observed in the carbonate concretions (1,321±1,067 nmol/g wet wt, n = 13). These data support the hypothesis that, in sediments, adsorbed hydrocarbon gases are strongly associated with authigenic carbonates.

Age determination and carbonate content of sediment core KH-79-3_L3

Laminated sediments deposited under anoxic bottom waters in the Japan Sea during the last glacial maximum (LGM) contain extremely well preserved calcareous microfossils and eolian carbonates. The radiocarbon age-difference between bulk sediment and monospecific planktonic foraminifera in discrete laminae from a core in the southern Japan Sea implies that ~40% of the total carbonates in the sediments at the LGM are of eolian origin. Extrapolation of this result yields a rate of supply of eolian carbonates of ~2800 tons/d to the entire Japan Sea during the LGM. The climatic significance of this flux potentially lies in its broader geographic extension, particularly in the interaction of the carbonate-bearing dust with shallow, corrosive North Pacific waters and with rain in the atmosphere. By increasing the alkalinity of such waters and by enhancing the biological pump the dust flux could have increased CO2 absorption by both the ocean and rain during the LGM.

Chemistry of altered basaltic glass shards and zeolites of volcaniclastic sediments from ODP Hole 157-953C

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.

Accumulation rates, carbon composition and Eocene carbonate compensation depths of ODP Sites 199-1218 and 199-1219

CaCO3, Corg, and biogenic SiO2 were measured in Eocene equatorial Pacific sediments from Sites 1218 and 1219, and bulk oxygen and carbon isotopes were measured on selected intervals from Site 1219. These data delineate a series of CaCO3 events that first appeared at ~48 Ma and continued to the Eocene/Oligocene boundary. Each event lasted 1-2 m.y. and is separated from the next by a low CaCO3 interval of a similar time span. The largest of these carbonate accumulation events (CAE-3) is in Magnetochron 18. It began at ~42.2 Ma, lasted until ~40.3 Ma, and was marked by higher than average productivity. The end of CAE-3 was abrupt and was associated with a large-scale carbon transfer to the oceans prior to warming of high-latitude regions. Changes in carbonate compensation depth associated with CAE excursions were small in the early part of the middle Eocene but increased to as much as 800 m by the late middle Eocene before decreasing into the late Eocene. Oxygen isotope data indicate that the carbonate events are associated with cooling conditions and may mark small glaciations in the Eocene.

Relative sea-level history of Marguerite Bay, Antarctic Peninsula derived from optically stimulated luminescence-dated beach cobbles

Calmette Bay within Marguerite Bay along the western side of the Antarctic Peninsula contains one of the most continuous flights of raised beaches described to date in Antarctica. Raised beaches extend to 40.8 m above sea level (masl) and are thought to reflect glacial isostatic adjustment due to the retreat of the Antarctic Peninsula Ice Sheet. Using optically stimulated luminescence (OSL), we dated quartz extracts from cobble surfaces buried in raised beaches at Calmette Bay. The beaches are separated into upper and lower beaches based on OSL ages, geomorphology, and sedimentary fabric. The two sets of beaches are separated by a prominent scarp. One of our OSL ages from the upper beaches dates to 9.3 thousand years ago (ka; as of 1950) consistent with previous extrapolation of sea-level data and the time of ice retreat from inner Marguerite Bay. However, four of the seven ages from the upper beaches date to the timing of glaciation. We interpret these ages to represent reworking of beaches deposited prior to the Last Glacial Maximum (LGM) by advancing and retreating LGM ice. Ages from the lower beaches record relative sea-level fall due to Holocene glacial-isostatic adjustment. We suggest a Holocene marine limit of 21.7 masl with an age of 5.5-7.3 ka based on OSL ages from Calmette Bay and other sea-level constraints in the area. A marine limit at 21.7 masl implies half as much relative sea-level change in Marguerite Bay during the Holocene as suggested by previous sea-level reconstructions. No evidence for a relative sea-level signature of neoglacial events, such as a decrease followed by an increase in RSL fall due to ice advance and retreat associated with the Little Ice Age, is found within Marguerite Bay indicating either: (1) no significant neoglacial advances occurred within Marguerite Bay; (2) rheological heterogeneity allows part of the Antarctic Peninsula (i.e. the South Shetland Islands) to respond to rapid ice mass changes while other regions are incapable of responding to short-lived ice advances; or (3) the magnitude of neoglacial events within Marguerite Bay is too small to resolve through relative sea-level reconstructions. Although the application of reconstructing sea-level histories using OSL-dated raised beach deposits provides a better understanding of the timing and nature of relative sea-level change in Marguerite Bay, we highlight possible problems associated with using raised beaches as sea-level indices due to post-depositional reworking by storm waves.

Bulk sediment parameter of three sediment cores from permafrost lowlands, Alaska Arctic Coastal Plain

Arctic lowland landscapes have been modified by thermokarst lake processes throughout the Holocene. Thermokarst lakes form as a result of ice-rich permafrost degradation and they may expand over time through thermal and mechanical shoreline erosion. We studied proximal and distal sedimentary records from a thermokarst lake located on the Arctic Coastal Plain of northern Alaska to reconstruct the impact of catchment dynamics and morphology on the lacustrine depositional environment and to quantify carbon accumulation in thermokarst lake sediments. Short cores were collected for analysis of pollen, sedimentological and geochemical proxies. Radiocarbon and Pb/Cs dating, as well as extrapolation of measured historic lake expansion rates, were applied to estimate a minimum lake age of ~ 1,400 calendar years BP. The pollen record is in agreement with the young lake age as it does not include evidence of the "alder high" that occurred in the region ~ 4.0 cal ka BP. The lake most likely initiated from a remnant pond in a drained thermokarst lake basin (DTLB) and deepened rapidly as evidenced by accumulation of laminated sediments. Increasing oxygenation of the water column as shown by higher Fe/Ti and Fe/S ratios in the sediment indicate shifts in ice regime with increasing water depth. More recently, the sediment source changed as the thermokarst lake expanded through lateral permafrost degradation, alternating from redeposited DTLB sediments, to increased amounts of sediment from eroding, older upland deposits, followed by a more balanced combination of both DTLB and upland sources. The characterizing shifts in sediment sources and depositional regimes in expanding thermokarst lakes were therefore archived in the thermokarst lake sedimentary record. This study also highlights the potential for Arctic lakes to recycle old carbon from thawing permafrost and thermokarst processes.