Diel cycling of trace elements in streams draining mineralized areas: a review

USGS Publications Warehouse

Gammons, Christopher H.; Nimick, David A.; Parker, Stephen R.

2015-01-01

Many trace elements exhibit persistent diel, or 24-h, concentration cycles in streams draining mineralized areas. These cycles can be caused by various physical and biogeochemical mechanisms including streamflow variation, photosynthesis and respiration, as well as reactions involving photochemistry, adsorption and desorption, mineral precipitation and dissolution, and plant assimilation. Iron is the primary trace element that exhibits diel cycling in acidic streams. In contrast, many cationic and anionic trace elements exhibit diel cycling in near-neutral and alkaline streams. Maximum reported changes in concentration for these diel cycles have been as much as a factor of 10 (988% change in Zn concentration over a 24-h period). Thus, monitoring and scientific studies must account for diel trace-element cycling to ensure that water-quality data collected in streams appropriately represent the conditions intended to be studied.

Methane fluxes from the mound-building termite species of North Australian savannas

NASA Astrophysics Data System (ADS)

Jamali, H.; Livesely, S. J.; Arndt, S. K.; Dawes-Gromadzki, T.; Cook, G. D.; Hutley, L.

2009-04-01

Termites are estimated to contribute 3-19% to the global methane emissions. These estimates have large uncertainties because of the limited number of field-based studies and species studied, as well as issues of diel and seasonal variation. We measured methane fluxes from four common mound-building termite species (Microcerotermes nervosus, n=26; M. serratus, n=4; Tumulitermes pastinator, n=5; and Amitermes darwini, n=4) in tropical savannas near Darwin in the Northern Territory, Australia. Methane fluxes from replicated termite mounds were measured in the field using manual chambers with fluxes reported on a mound volume basis. Methane flux was measured in both wet and dry seasons and diel variation was investigated by measuring methane flux every 4 hours over a 24 hour period. Mound temperature was measured concurrently with flux to examine this relationship. In addition, five M. nervosus mounds removed from the field and incubated under controlled temperature conditions over a 24 hour period to remove the effect of varying temperature. During the observation campaigns, mean monthly minimum and maximum temperatures for February (wet season) were 24.7 and 30.8°C, respectively, and were 20.1 to 31.4 °C in June (dry season). Annual rainfall in 2008 for Darwin was 1970.1 mm, with a maximum of 670 mm falling in February and no rain in May and June. Methane fluxes were greatest in the wet season for all species, ranging from 265.1±101.1 (T. pastinator) to 2256.6±757.1 (M. serratus) µg CH4-C/m3/h. In the dry season, methane fluxes were at their lowest, ranging from 10.0±5.5 (T. pastinator) to 338.0±165.9 (M. serratus) µg CH4-C/m3/h. On a diel basis, methane fluxes were smallest at the coolest time of the day (~0700 hrs) and greatest at the warmest (~1400 hrs) for all species, and for both wet and dry seasons. Typical diel variation in flux from M. serratus dominated mounds ranged from 902.6±261.9 to 1392.1±408.1 µg CH4-C/m3/h in wet season and 99.6±57.4 to 556.2±254.9 µg CH4-C/m3/h in dry season. While mounds of M. nervosus had diel variations in methane fluxes in the field, no diel variation was observed when incubated under constant laboratory temperature for 24 hours. This demonstrates that diel variation was not due to the movement of termites in and out of the mounds, but was due to temperature variation. Methane flux varied significantly according to termite species and at seasonal and diel time scales which, if not accounted for, could result in large under- or over-estimation of methane emissions from termites when flux data are extrapolated to landscape scales.

Diel and seasonal variation of a molluscan taxocoenosis associated with a Zostera marina bed in southern Spain (Alboran Sea)

NASA Astrophysics Data System (ADS)

Rueda, Jose L.; Urra, Javier; Salas, Carmen

2008-09-01

The diel and seasonal variation of molluscs living in a Zostera marina bed (12-14 m depth) from southern Spain have been studied for one year using a small Agassiz trawl for collecting the samples (222 m2). The frequent and dominant species were very similar in both diurnal and nocturnal samples, including mainly gastropods such as Jujubinus striatus, Nassarius pygmaeus, Mitrella minor, Calliostoma planatum, Rissoa membranacea or Smaragdia viridis. Nevertheless, a significant increase of abundance of scavengers (e.g. Nassarius spp.) and carnivores (e.g. cephalopods) was registered in nocturnal samples. The abundance was maximal in spring and summer in diurnal and nocturnal samples and also in autumn for nocturnal ones, displaying significantly higher values in nocturnal samples. The species richness, diversity and evenness displayed a similar seasonal trend for diurnal and nocturnal samples, with maximum values during summer months. Monthly variation of the molluscan composition (species presence-absence data) was more acute than diel variation, according to the Cluster, MDS and ANOSIM results. Nevertheless, both monthly and diel changes in the structure (species abundance data) of the molluscan taxocoenosis were important throughout the year. Diel changes in the structure of the molluscan fauna are related to an increase of abundance of some species at nighttime due to vertical movements from the sediment to the shoots or along them (e.g. J. striatus, Nassarius spp.) or due to horizontal movements from adjacent habitats (e.g. cephalopods). Nevertheless, some species such as Rissoa spp. or Bittium spp. stay on the leaves of Z. marina during day as well as nighttime.

Diel Surface Temperature Range Scales with Lake Size

PubMed Central

Woolway, R. Iestyn; Jones, Ian D.; Maberly, Stephen C.; French, Jon R.; Livingstone, David M.; Monteith, Donald T.; Simpson, Gavin L.; Thackeray, Stephen J.; Andersen, Mikkel R.; Battarbee, Richard W.; DeGasperi, Curtis L.; Evans, Christopher D.; de Eyto, Elvira; Feuchtmayr, Heidrun; Hamilton, David P.; Kernan, Martin; Krokowski, Jan; Rimmer, Alon; Rose, Kevin C.; Rusak, James A.; Ryves, David B.; Scott, Daniel R.; Shilland, Ewan M.; Smyth, Robyn L.; Staehr, Peter A.; Thomas, Rhian; Waldron, Susan; Weyhenmeyer, Gesa A.

2016-01-01

Ecological and biogeochemical processes in lakes are strongly dependent upon water temperature. Long-term surface warming of many lakes is unequivocal, but little is known about the comparative magnitude of temperature variation at diel timescales, due to a lack of appropriately resolved data. Here we quantify the pattern and magnitude of diel temperature variability of surface waters using high-frequency data from 100 lakes. We show that the near-surface diel temperature range can be substantial in summer relative to long-term change and, for lakes smaller than 3 km2, increases sharply and predictably with decreasing lake area. Most small lakes included in this study experience average summer diel ranges in their near-surface temperatures of between 4 and 7°C. Large diel temperature fluctuations in the majority of lakes undoubtedly influence their structure, function and role in biogeochemical cycles, but the full implications remain largely unexplored. PMID:27023200

Variation in diel activity of ground beetles (Coleoptera: Carabidae) associated with a soybean field and coal mine remnant

USGS Publications Warehouse

Willand, J.E.; McCravy, K.W.

2006-01-01

Diel activities of carabids (Coleoptera: Carabidae) associated with a coal mine remnant and surrounding soybean field were studied in west-central Illinois from June through October 2002. A total of 1,402 carabids, representing 29 species and 17 genera, were collected using pitfall traps. Poecilus chalcites (Say) demonstrated roughly equal diurnal and nocturnal activity in June, but greater diurnal activity thereafter. Pterostichus permundus (Say), Cyclotrachelus seximpressus (LeConte), Amara obesa (Say), and Scarites quadriceps Chaudoir showed significant nocturnal activity. Associations between habitat and diel activity were found for three species: P. chalcites associated with the remnant and edge habitats showed greater diurnal activity than those associated with the soybean field; C. seximpressus was most active diurnally in the remnant, and Harpalus pensylvanicus (DeGeer) showed the greatest nocturnal activity in the remnant and edge habitats. We found significant temporal and habitat-related variation in diel activity among carabid species inhabiting agricultural areas in west-central Illinois.

Diel variations in the assemblage structure and foraging ecology of larval and 0+ year juvenile fishes in a man-made floodplain waterbody.

PubMed

Tewson, L H; Cowx, I G; Nunn, A D

2016-04-01

This study investigated diel variations in zooplankton composition and abundance, and the species composition, density, size structure, feeding activity, diet composition and prey selection of larval and 0+ year juvenile fishes in the littoral of a man-made floodplain waterbody over five 24 h periods within a 57 day period. There was a significant difference in the species composition of diurnal and nocturnal catches, with most species consistently peaking in abundance either during daylight or at night, reflecting their main activity period. There were no consistent diel patterns in assemblage structure or the abundance of some species, however, most likely, respectively, due to the phenology of fish hatching and ontogenetic shifts in diel behaviour or habitat use. There were few clear diel patterns in the diet composition or prey selection of larval and 0+ year juvenile roach Rutilus rutilus and perch Perca fluviatilis, with most taxa consistently selected or avoided irrespective of the time of day or night, and no obvious shift between planktonic and benthic food sources, but dietary overlap suggested that interspecific interactions were probably strongest at night. It is essential that sampling programmes account for the diel ecology of the target species, as diurnal surveys alone could produce inaccurate assessments of resource use. The relative lack of consistent diel patterns in this study suggests that multiple 24 h surveys are required in late spring and early summer to provide accurate assessments of 0+ year fish assemblage structure and foraging ecology. © 2016 The Fisheries Society of the British Isles.

Diel variation of the cellular carbon to nitrogen ratio of Chlorella autotrophica (Chlorophyta) growing in phosphorus- and nitrogen-limited continuous cultures.

PubMed

Ng, Wai Ho Albert; Liu, Hongbin

2015-02-01

We investigated the relationship between daily growth rates and diel variation of carbon (C) metabolism and C to nitrogen (N) ratio under P- and N-limitation in the green algae Chlorella autotrophica. To do this, continuous cultures of C. autotrophica were maintained in a cyclostat culture system under 14:10 light:dark cycle over a series of P- and N-limited growth rates. Cell abundance, together with cell size, as reflected by side scatter signal from flow cytometric analysis demonstrated a synchronized diel pattern with cell division occurring at night. Under either type of nutrient limitation, the cellular C:N ratio increased through the light period and decreased through the dark period over all growth rates, indicating a higher diel variation of C metabolism than that of N. Daily average cellular C:N ratios were higher at lower dilution rates under both types of nutrient limitation but cell enlargement was only observed at lower dilution rates under P-limitation. Carbon specific growth rates during the dark period positively correlated with cellular daily growth rates (dilution rates), with net loss of C during night at the lowest growth rates under N-limitation. Under P-limitation, dark C specific growth rates were close to zero at low dilution rates but also exhibited an increasing trend at high dilution rates. In general, diel variations of cellular C:N were low when dark C specific growth rates were high. This result indicated that the fast growing cells performed dark C assimilation at high rates, hence diminished the uncoupling of C and N metabolism at night. © 2014 Phycological Society of America.

Diel time-courses of leaf growth in monocot and dicot species: endogenous rhythms and temperature effects.

PubMed

Poiré, Richard; Wiese-Klinkenberg, Anika; Parent, Boris; Mielewczik, Michael; Schurr, Ulrich; Tardieu, François; Walter, Achim

2010-06-01

Diel (24 h) leaf growth patterns were differently affected by temperature variations and the circadian clock in several plant species. In the monocotyledon Zea mays, leaf elongation rate closely followed changes in temperature. In the dicotyledons Nicotiana tabacum, Ricinus communis, and Flaveria bidentis, the effect of temperature regimes was less obvious and leaf growth exhibited a clear circadian oscillation. These differences were related neither to primary metabolism nor to altered carbohydrate availability for growth. The effect of endogenous rhythms on leaf growth was analysed under continuous light in Arabidopsis thaliana, Ricinus communis, Zea mays, and Oryza sativa. No rhythmic growth was observed under continuous light in the two monocotyledons, while growth rhythmicity persisted in the two dicotyledons. Based on model simulations it is concluded that diel leaf growth patterns in mono- and dicotyledons result from the additive effects of both circadian-clock-controlled processes and responses to environmental changes such as temperature and evaporative demand. Apparently very distinct diel leaf growth behaviour of monocotyledons and dicotyledons can thus be explained by the different degrees to which diel temperature variations affect leaf growth in the two groups of species which, in turn, depends on the extent of the leaf growth control by internal clocks.

Linking benthic microbial community dynamics to diel redox variations in a near shore costal environment, Héeia Fishpond

NASA Astrophysics Data System (ADS)

Frank, K. L.; Rogers, K. L.; Wheat, C. G.; Alegado, R.

2016-12-01

Microbes play crucial roles in mediating biogeochemical cycling in coastal marine habitats. In shallow coastal ecosystems, excess primary productivity and respiration of pelagic phototrophic organisms generate striking diel variations in dissolved oxygen concentrations, leading to substantial vertical migration of redox transition zones in the sediment. However, the relationship between microbial community dynamics and the establishment of these geochemical gradients, especially over a diel time frame, remains poorly constrained. Here we examine the biogeochemical drivers of diel redox dynamics by integrating comprehensive geochemical, taxonomic, functional gene abundance, and thermodynamic datasets from Héeia Fishpond (HFP) sediment cores. HFP, an 88-acre tidally-influenced, shallow Hawaiian coastal estuarine system, is analogous to a large mesocosm embedded in a natural coastal environment, making it an ideal site for coastal biogeochemical studies. Taxonomic assessments of bacterial diversity via 16S rRNA genes revealed centimeter- scale variability with depth, with similar taxa present in all samples, but their relative abundances varied substantially among horizons. There were significant correlation between changes in geochemical composition and changes in community structure. Additionally, functional gene abundance was correlated with energy potential and aligned with activity. The taxanomic data and porewater geochemistry from HFP sediments suggest that redox variations observed in iron and sulfur speciation result from depth-related changes in microbial activity and community structure over a diel period. By linking community diversity to metabolic activity in the context of the geochemical environment, this research provides valuable insight into the connectivity of iron and sulfur metabolic modes.

Biogeochemical controls on diel cycling of stable isotopes of dissolved 02 and dissolved inorganic carbon in the Big Hole River, Montana

USGS Publications Warehouse

Parker, Stephen R.; Poulson, Simon R.; Gammons, Christopher H.; DeGrandpre, Michael D.

2005-01-01

Rivers with high biological productivity typically show substantial increases in pH and dissolved oxygen (DO) concentration during the day and decreases at night, in response to changes in the relative rates of aquatic photosynthesis and respiration. These changes, coupled with temperature variations, may impart diel (24-h) fluctuations in the concentration of trace metals, nutrients, and other chemical species. A better understanding of diel processes in rivers is needed and will lead to improved methods of data collection for both monitoring and research purposes. Previous studies have used stable isotopes of dissolved oxygen (DO) and dissolved inorganic carbon (DIC) as tracers of geochemical and biological processes in streams, lakes, and marine systems. Although seasonal variation in δ18O of DO in rivers and lakes has been documented, no study has investigated diel changes in this parameter. Here, we demonstrate large (up to 13‰) cycles in δ18O-DO for two late summer sampling periods in the Big Hole River of southwest Montana and illustrate that these changes are correlated to variations in the DO concentration, the C-isotopic composition of DIC, and the primary productivity of the system. The magnitude of the diel cycle in δ18O-DO was greater in August versus September because of the longer photoperiod and warmer water temperatures. This study provides another biogeochemical tool for investigating the O2 and C budgets in rivers and may also be applicable to lake and groundwater systems.

Diel Variations in Optical Properties of Micromonas pusilla, a Prasinophyte

NASA Technical Reports Server (NTRS)

DuRand, Michele D.; Green, Rebecca E.; Sosik, Heidi M.; Olson, Robert J.

2001-01-01

A laboratory experiment was conducted on cultures of Micromonas pusilla, a marine prasinophyte, to investigate how cell growth and division affect the optical properties over the light:dark cycle. Measurements were made of cell size and concentration, attenuation and absorption coefficients, flow cytometric light scattering (in forward and side directions), chlorophyll and carbon content. Refractive index was calculated using the anomalous diffraction approximation Cells were about 1.5 micrometers in diameter and exhibited phased division, with the major division burst occurring during the night. Typical diel variations were observed, with cells increasing in size and light scattering during the day as they photosynthesize and decreasing at night upon division. The cells were in ultradian growth, with more than one division per day, at a light level of 120 Mu-mol photons m/sq/sec. Since these cells are similar in size to small phytoplankton that are typically abundant in field samples, these results can be used in the interpretation of diel variations in light scattering in natural populations of phytoplankton.

Contrasting diel hysteresis between soil autotrophic and heterotrophic respiration in a desert ecosystem under different rainfall scenarios

PubMed Central

Song, Weimin; Chen, Shiping; Zhou, Yadan; Wu, Bo; Zhu, Yajuan; Lu, Qi; Lin, Guanghui

2015-01-01

Diel hysteresis occurs often between soil CO2 efflux (RS) and temperature, yet, little is known if diel hysteresis occurs in the two components of RS, i.e., autotrophic respiration (RA) and heterotrophic respiration (RH), and how diel hysteresis will respond to future rainfall change. We conducted a field experiment in a desert ecosystem in northern China simulating five different scenarios of future rain regimes. Diel variations of soil CO2 efflux and soil temperature were measured on Day 6 and Day 16 following the rain addition treatments each month during the growing season. We found contrasting responses in the diel hysteresis of RA and RH to soil temperature, with a clockwise hysteresis loop for RH but a counter-clockwise hysteresis loop for RA. Rain addition significantly increased the magnitude of diel hysteresis for both RH and RA on Day 6, but had no influence on either on Day 16 when soil moisture was much lower. These findings underline the different roles of biological (i.e. plant and microbial activities) and physical-chemical (e.g. heat transport and inorganic CO2 exchange) processes in regulating the diel hysteresis of RA and RH, which should be considered when estimating soil CO2 efflux in desert regions under future rainfall regime. PMID:26615895

Diel and seasonal variation in food habits of Atlantic salmon parr in a small stream

USGS Publications Warehouse

Grader, M.; Letcher, B.H.

2006-01-01

The diel and seasonal food habits of young-of-year (YOY) and post-young-of-year (PYOY) Atlantic salmon (Salmo salar) parr were assayed over the course of 11 months in the West Brook, Massachusetts USA. Gut fullness of YOY salmon did not vary significantly among months. PYOY salmon exhibited significant seasonal differences in gut fullness, with peak fullness occurring in the spring and late fall. Significant diel differences in PYOY gut fullness occurred in June and April, with peak fullness always occurring at dawn. Prey composition varied substantially among months. Dominant prey items of PYOY salmon were baetid mayflies in June, July, and August, limnephilid caddisflies in October and November, and ephemerellid mayflies in February and April. Few differences in prey composition between PYOY and YOY salmon were observed. Fish growth was unrelated to prey availability, but gut fullness explained up to 97% of growth variation across seasons. Results suggest that spring and fall are critical periods of feeding for PYOY salmon and that diel feeding intensity shifts seasonally.

Processes controlling dissolved oxygen and pH in the upper Willamette River basin, Oregon, 1994

USGS Publications Warehouse

Pogue, Ted R.; Anderson, Chauncey W.

1995-01-01

In July and August of 1994, the U. S. Geological Survey in cooperation with the Oregon Department of Environmental Quality (ODEQ) collected data to document the spatial extent and diel variability of dissolved oxygen (DO) concentrations and pH levels in selected reaches of streams in the upper Willamette River Basin. These data were also collected to identify primary factors that control DO concentrations downstream from major point sources as well as to provide ODEQ with data to refine calibration of their steady-state DO and nutrient models for the upper Willamette River Basin. All of the reaches studied had diel variations in DO and pH. The magnitude of the diel variations in DO ranged from 0.2 to 3.9 milligrams per liter (7 to 50 percent-saturation units based on ambient water temperature and barometric pressure) and in pH from 0.3 to 1.4 units. However, of the reaches studied, only the Coast Fork Willamette River from river mile (RM) 21.7 to 12.5 and the Willamette River from RM 151 to 141.6 had field measured violations of State standards for DO and pH. DO concentration and pH in water depend on many factors. Data were collected to examine several major factors, including BOD (biochemical oxygen demand), carbonaceous BOD, nitrogenous BOD, and measures of photosynthetic activity. Of the four study reaches, only a short stretch of the Coast Fork Willamette River has potential for important levels of oxygen consumption from BOD or nitrification. Additionally, water-column primary-productivity measurements indicated that respiration and photosynthesis by free-floating algae did not explain the observed diel variations in DO in the study reaches. Results from a simple mathematical model incorporating measures of community respiration and net primary productivities indicated that periphyton are capable of producing a diel variation of the order of magnitude observed during the August study period. In the Willamette River near Peoria, the combined periphyton DO consumption and production estimate at RM 151 (2.4 mg/L) and RM 144.6 (1.7 mg/L) would account for 90 and 63 percent, respectively, of the observed diel fluctuation. The estimates for the Corvallis reach at RM 132.6 (0.4 mg/L) and RM 130.7 (2.9 mg/L) had a considerably larger range of 36 to 264 percent of DO saturation, respectively. Therefore, because BOD and phytoplankton do not appear to be important contributors to diel DO fluctuations, periphyton are likely the primary contributor to diel fluctuations in the upper Willamette River Basin during July and August.

Diel biogeochemical processes and their effect on the aqueous chemistry of streams: A review

USGS Publications Warehouse

Nimick, David A.; Gammons, Christopher H.; Parker, Stephen R.

2011-01-01

This review summarizes biogeochemical processes that operate on diel, or 24-h, time scales in streams and the changes in aqueous chemistry that are associated with these processes. Some biogeochemical processes, such as those producing diel cycles of dissolved O2 and pH, were the first to be studied, whereas processes producing diel concentration cycles of a broader spectrum of chemical species including dissolved gases, dissolved inorganic and organic carbon, trace elements, nutrients, stable isotopes, and suspended particles have received attention only more recently. Diel biogeochemical cycles are interrelated because the cyclical variations produced by one biogeochemical process commonly affect another. Thus, understanding biogeochemical cycling is essential not only for guiding collection and interpretation of water-quality data but also for geochemical and ecological studies of streams. Expanded knowledge of diel biogeochemical cycling will improve understanding of how natural aquatic environments function and thus lead to better predictions of how stream ecosystems might react to changing conditions of contaminant loading, eutrophication, climate change, drought, industrialization, development, and other factors.

Diel variation in fig volatiles across syconium development: making sense of scents.

PubMed

Borges, Renee M; Bessière, Jean-Marie; Ranganathan, Yuvaraj

2013-05-01

Plants produce volatile organic compounds (VOCs) in a variety of contexts that include response to abiotic and biotic stresses, attraction of pollinators and parasitoids, and repulsion of herbivores. Some of these VOCs may also exhibit diel variation in emission. In Ficus racemosa, we examined variation in VOCs released by fig syconia throughout syconium development and between day and night. Syconia are globular enclosed inflorescences that serve as developing nurseries for pollinating and parasitic fig wasps. Syconia are attacked by gallers early in their development, serviced by pollinators in mid phase, and are attractive to parasitoids in response to the development of gallers at later stages. VOC bouquets of the different development phases of the syconium were distinctive, as were their day and night VOC profiles. VOCs such as α-muurolene were characteristic of the pollen-receptive diurnal phase, and may serve to attract the diurnally-active pollinating wasps. Diel patterns of release of volatiles could not be correlated with their predicted volatility as determined by Henry's law constants at ambient temperatures. Therefore, factors other than Henry's law constant such as stomatal conductance or VOC synthesis must explain diel variation in VOC emission. A novel use of weighted gene co-expression network analysis (WGCNA) on the volatilome resulted in seven distinct modules of co-emitted VOCs that could be interpreted on the basis of syconium ecology. Some modules were characterized by the response of fig syconia to early galling by parasitic wasps and consisted largely of green leaf volatiles (GLVs). Other modules, that could be characterized by a combination of syconia response to oviposition and tissue feeding by larvae of herbivorous galler pollinators as well as of parasitized wasps, consisted largely of putative herbivore-induced plant volatiles (HIPVs). We demonstrated the usefulness of WGCNA analysis of the volatilome in making sense of the scents produced by the syconia at different stages and diel phases of their development.

Landscape-level variation in disease susceptibility related to shallow-water hypoxia.

PubMed

Breitburg, Denise L; Hondorp, Darryl; Audemard, Corinne; Carnegie, Ryan B; Burrell, Rebecca B; Trice, Mark; Clark, Virginia

2015-01-01

Diel-cycling hypoxia is widespread in shallow portions of estuaries and lagoons, especially in systems with high nutrient loads resulting from human activities. Far less is known about the effects of this form of hypoxia than deeper-water seasonal or persistent low dissolved oxygen. We examined field patterns of diel-cycling hypoxia and used field and laboratory experiments to test its effects on acquisition and progression of Perkinsus marinus infections in the eastern oyster, Crassostrea virginica, as well as on oyster growth and filtration. P. marinus infections cause the disease known as Dermo, have been responsible for declines in oyster populations, and have limited success of oyster restoration efforts. The severity of diel-cycling hypoxia varied among shallow monitored sites in Chesapeake Bay, and average daily minimum dissolved oxygen was positively correlated with average daily minimum pH. In both field and laboratory experiments, diel-cycling hypoxia increased acquisition and progression of infections, with stronger results found for younger (1-year-old) than older (2-3-year-old) oysters, and more pronounced effects on both infections and growth found in the field than in the laboratory. Filtration by oysters was reduced during brief periods of exposure to severe hypoxia. This should have reduced exposure to waterborne P. marinus, and contributed to the negative relationship found between hypoxia frequency and oyster growth. Negative effects of hypoxia on the host immune response is, therefore, the likely mechanism leading to elevated infections in oysters exposed to hypoxia relative to control treatments. Because there is considerable spatial variation in the frequency and severity of hypoxia, diel-cycling hypoxia may contribute to landscape-level spatial variation in disease dynamics within and among estuarine systems.

Assessment of diel chemical and isotopic techniques to investigate biogeochemical cycles in the upper Klamath River, Oregon, USA

USGS Publications Warehouse

Poulson, S.R.; Sullivan, A.B.

2009-01-01

The upper Klamath River experiences a cyanobacterial algal bloom and poor water quality during the summer. Diel chemical and isotopic techniques have been employed in order to investigate the rates of biogeochemical processes. Four diel measurements of field parameters (temperature, pH, dissolved oxygen concentrations, and alkalinity) and stable isotope compositions (dissolved oxygen-??18O and dissolved inorganic carbon-??13C) have been performed between June 2007 and August 2008. Significant diel variations of pH, dissolved oxygen (DO) concentration, and DO-??18O were observed, due to varying rates of primary productivity vs. respiration vs. gas exchange with air. Diel cycles are generally similar to those previously observed in river systems, although there are also differences compared to previous studies. In large part, these different diel signatures are the result of the low turbulence of the upper Klamath River. Observed changes in the diel signatures vs. sampling date reflect the evolution of the status of the algal bloom over the course of the summer. Results indicate the potential utility of applying diel chemical and stable isotope techniques to investigate the rates of biogeochemical cycles in slow-moving rivers, lakes, and reservoirs, but also illustrate the increased complexity of stable isotope dynamics in these low-turbulence systems compared to well-mixed aquatic systems. ?? 2009 Elsevier B.V.

Diel variation in summer habitat use, feeding periodicity, and diet of subyearling Atlantic salmon in the Salmon River Basin, New York

USGS Publications Warehouse

Johnson, James H.

2013-01-01

The habitat use, diet composition, and feeding periodicity of subyearling Atlantic salmon (Salmo salar) was examined during both day and night periods during summer in tributaries of Lake Ontario. The amount of cover used was the major habitat variable that differed between day and night periods in both streams. At night subyearling Atlantic salmon were associated with significantly less cover than during the day. Principal Component Analysis showed that habitat selection of subyearling Atlantic salmon was more pronounced during the day in both streams and that salmon in Orwell Brook exhibited more diel variability in habitat use than salmon in Trout Brook. Subyearling salmon fed primarily from the benthic substrate on baetids, chironomids, and leptocerids. There was a substantial amount of diel variation in diet composition with peak feeding occurring from 0400 h to 0800 h on July 21–22, 2008.

Seasonal and diel variations of ammonia and methane emissions from a naturally ventilated dairy building and the associated factors influencing emissions.

PubMed

Saha, C K; Ammon, C; Berg, W; Fiedler, M; Loebsin, C; Sanftleben, P; Brunsch, R; Amon, T

2014-01-15

Understanding seasonal and diel variations of ammonia (NH3) and methane (CH4) emissions from a naturally ventilated dairy (NVD) building may lead to develop successful control strategies for reducing emissions throughout the year. The main objective of this study was to quantify seasonal and diel variations of NH3 and CH4 emissions together with associated factors influencing emissions. Measurements were carried out with identical experimental set-up to cover three winter, spring and summer seasons, and two autumn seasons in the years 2010, 2011, and 2012. The data from 2010 and 2011 were used for developing emission prediction models and the data from 2012 were used for model validation. The results showed that NH3 emission varied seasonally following outside temperature whereas CH4 emission did not show clear seasonal trend. Diel variation of CH4 emission was less pronounced than NH3. The average NH3 and CH4 emissions between 6a.m. and 6p.m. were 66% and 33% higher than the average NH3 and CH4 emissions between 6p.m. and 6a.m., respectively for all seasons. The significant relationships (P<0.0001) between NH3 and influencing factors were found including outside temperature, humidity, wind speed and direction, hour of the day and day of the year. The significant effect (P<0.0001) of climate factors, hours of the day and days of the year on CH4 emission might be directly related to activities of the cows. © 2013.

Vertical patterns of ichthyoplankton at the interface between a temperate estuary and adjacent coastal waters: Seasonal relation to diel and tidal cycles

NASA Astrophysics Data System (ADS)

Primo, Ana Lígia; Azeiteiro, Ulisses M.; Marques, Sónia C.; Ré, Pedro; Pardal, Miguel A.

2012-07-01

Vertical distribution and migration pattern of ichthyoplankton assemblage in the Mondego estuary were investigated in relation to diel and tidal cycle. Summer and winter communities were sampled, at surface and bottom, over a diel cycle during spring and neap tides at a fixed station at the mouth of the estuary. Summer presented higher larvae density mainly of Pomatoschistus spp., Gobius niger and Parablennius pilicornis. Main species in winter assemblages were Pomatoschistus spp. and Sardina pilchardus. There were no differences between depth stratums across diel or tide cycle. Nevertheless, main species larval densities showed significant periodic variation associated with tide (M2) and diel (K1) cycles presenting generally, higher density at night and around low tide. Conversely, vertical patterns observed could not be related with diel or tidal cycle. Tough, main species presented some extent of vertical migration. Vertical patterns observed appear to be related to seasonal stratification and river flow, increasing amplitude during periods of less stratification and lower water currents. Present study provides a better understanding of ichthyoplankton vertical movement patterns and of small scale dynamics at the interface of two coastal European systems.

Diel fluctuations of viscosity-driven riparian inflow affect streamflow DOC concentration

NASA Astrophysics Data System (ADS)

Schwab, Michael P.; Klaus, Julian; Pfister, Laurent; Weiler, Markus

2018-04-01

Diel fluctuations of stream water DOC concentrations are generally explained by a complex interplay of different instream processes. We measured the light absorption spectrum of water and DOC concentrations in situ and with high frequency by means of a UV-Vis spectrometer during 18 months at the outlet of a forested headwater catchment in Luxembourg (0.45 km2). We generally observed diel DOC fluctuations with a maximum in the afternoon during days that were not affected by rainfall-runoff events. We identified an increased inflow of terrestrial DOC to the stream in the afternoon, causing the DOC maxima in the stream. The terrestrial origin of the DOC was derived from the SUVA-254 (specific UV absorbance at 254 nm) index, which is a good indicator for the aromaticity of DOC. In the studied catchment, the most likely process that can explain the diel DOC input variations towards the stream is the so-called viscosity effect. The water temperature in the upper parts of the saturated riparian zone is increasing during the day, leading to a lower viscosity and therefore a higher hydraulic conductivity. Consequently, more water from areas that are rich in terrestrial DOC passes through the saturated riparian zone and contributes to streamflow in the afternoon. We believe that not only diel instream processes, but also viscosity-driven diel fluctuations of terrestrial DOC input should be considered to explain diel DOC patterns in streams.

Diel cycles in dissolved metal concentrations in streams: Occurrence and possible causes

USGS Publications Warehouse

Nimick, David A.; Gammons, Christopher H.; Cleasby, Thomas E.; Madison, James P.; Skaar, Don; Brick, Christine M.

2003-01-01

Substantial diel (24‐hour) cycles in dissolved (0.1‐μm filtration) metal concentrations were observed during low flow for 18 sampling episodes at 14 sites on 12 neutral and alkaline streams draining historical mining areas in Montana and Idaho. At some sites, concentrations of Cd, Mn, Ni, and Zn increased as much as 119, 306, 167, and 500%, respectively, from afternoon minimum values to maximum values shortly after sunrise. Arsenic concentrations exhibited the inverse temporal pattern with increases of up to 54%. Variations in Cu concentrations were small and inconsistent. Diel metal cycles are widespread and persistent, occur over a wide range of metal concentrations, and likely are caused primarily by instream geochemical processes. Adsorption is the only process that can explain the inverse temporal patterns of As and the divalent metals. Diel metal cycles have important implications for many types of water‐quality studies and for understanding trace‐metal mobility.

Diel CO2 cycles reduce severity of behavioural abnormalities in coral reef fish under ocean acidification.

PubMed

Jarrold, Michael D; Humphrey, Craig; McCormick, Mark I; Munday, Philip L

2017-08-31

Elevated CO 2 levels associated with ocean acidification (OA) have been shown to alter behavioural responses in coral reef fishes. However, all studies to date have used stable pCO 2 treatments, not considering the substantial diel pCO 2 variation that occurs in shallow reef habitats. Here, we reared juvenile damselfish, Acanthochromis polyacanthus, and clownfish, Amphiprion percula, at stable and diel cycling pCO 2 treatments in two experiments. As expected, absolute lateralization of A. polyacanthus and response to predator cue of Am. percula were negatively affected in fish reared at stable, elevated pCO 2 in both experiments. However, diel pCO 2 fluctuations reduced the negative effects of OA on behaviour. Importantly, in experiment two, behavioural abnormalities that were present in fish reared at stable 750 µatm CO 2 were largely absent in fish reared at 750 ± 300 µatm CO 2 . Overall, we show that diel pCO 2 cycles can substantially reduce the severity of behavioural abnormalities caused by elevated CO 2 . Thus, past studies may have over-estimated the impacts of OA on the behavioural performance of coral reef fishes. Furthermore, our results suggest that diel pCO 2 cycles will delay the onset of behavioural abnormalities in natural populations.

Diel Variation in Beaked Whale Diving Behavior

DTIC Science & Technology

2008-01-01

While our results are only from a single study area and our sample size is small, diving patterns of these two species appear very stereotypic ...sharks of the genus Isistius (McSweeney et al. 2007). Cookie-cutter sharks are thought to exhibit diel vertical migrations, spending time near the...Mar. Mamm. Sci. 23: 666-687. 17 Mead, J.G. 1989. Beaked whales of the genus Mesoplodon. Pages 349-430 In S.H. Ridgway and R. Harrison

Genetically Regulated Temporal Variation of Novel Courtship Elements in the Hawaiian Cricket Genus Laupala

PubMed Central

deCarvalho, Tagide N.; Shaw, Kerry L.

2011-01-01

The Hawaiian cricket genus Laupala (Gryllidae: Trigonidiinae) has undergone rapid and extensive speciation, with divergence in male song and female acoustic preference playing a role in maintaining species boundaries. Recent study of interspecific differences in the diel rhythmicity of singing and mating, suggests that temporal variation in behavior may reduce gene flow between species. In addition, Laupala perform an elaborate and protracted courtship, providing potential for further temporal variation. However, whether these behavioral differences have a genetic basis or result from environmental variation is unknown. We observed courtship and mating in a common garden study of the sympatric species, Laupala cerasina and Laupala paranigra. We document interspecific differences in the onset and duration of courtship, spermatophore production rate, and diel mating rhythmicity. Our study demonstrates a genetic contribution to interspecific behavioral differences, and suggests an evolutionary pathway to the origins of novel timing phenotypes. PMID:20878226

Feeding ecology of lake whitefish larvae in eastern Lake Ontario

USGS Publications Warehouse

Johnson, James H.; McKenna, James E.; Chalupnicki, Marc A.; Wallbridge, Tim; Chiavelli, Rich

2009-01-01

We examined the feeding ecology of larval lake whitefish (Coregonus clupeaformis) in Chaumont Bay, Lake Ontario, during April and May 2004-2006. Larvae were collected with towed ichthyoplankton nets offshore and with larval seines along the shoreline. Larval feeding periodicity was examined from collections made at 4-h intervals over one 24-h period in 2005. Inter-annual variation in diet composition (% dry weight) was low, as was spatial variation among collection sites within the bay. Copepods (81.4%), primarily cyclopoids (59.1%), were the primary prey of larvae over the 3-year period. Cladocerans (8.1%; mainly daphnids, 6.7%) and chironomids (7.3%) were the other major prey consumed. Larvae did not exhibit a preference for any specific prey taxa. Food consumption of lake whitefish larvae was significantly lower at night (i.e., 2400 and 0400 h). Substantial variation in diet composition occurred over the 24-h diel study. For the 24-h period, copepods were the major prey consumed (50.4%) and their contribution in the diet ranged from 29.3% (0400 h) to 85.9% (1200 h). Chironomids made up 33.4% of the diel diet, ranging from 8.0% (0800 h) to 69.9% (0400 h). Diel variation in the diet composition of lake whitefish larvae may require samples taken at several intervals over a 24-h period to gain adequate representation of their feeding ecology.

Diel plant water use and competitive soil cation exchange interact to enhance NH 4 + and K + availability in the rhizosphere

DOE PAGES

Espeleta, Javier F.; Cardon, Zoe G.; Mayer, K. Ulrich; ...

2016-11-12

Hydro-biogeochemical processes in the rhizosphere regulate nutrient and water availability, and thus ecosystem productivity. We hypothesized that two such processes often neglected in rhizosphere models — diel plant water use and competitive cation exchange — could interact to enhance availability of K + and NH 4 +, both high-demand nutrients. A rhizosphere model with competitive cation exchange was used to investigate how diel plant water use (i.e., daytime transpiration coupled with no nighttime water use, with nighttime root water release, and with nighttime transpiration) affects competitive ion interactions and availability of K + and NH 4 +. Competitive cation exchangemore » enabled lowdemand cations that accumulate against roots (Ca 2+, Mg 2+, Na +) to desorb NH 4 + and K + from soil, generating non-monotonic dissolved concentration profiles (i.e. ‘hotspots’ 0.1–1 cm from the root). Cation accumulation and competitive desorption increased with net root water uptake. Daytime transpiration rate controlled diel variation in NH 4 + and K + aqueous mass, nighttime water use controlled spatial locations of ‘hotspots’, and day-to-night differences in water use controlled diel differences in ‘hotspot’ concentrations. Finally, diel plant water use and competitive cation exchange enhanced NH 4 + and K + availability and influenced rhizosphere concentration dynamics. Demonstrated responses have implications for understanding rhizosphere nutrient cycling and plant nutrient uptake.« less

Fall field crickets did not acclimate to simulated seasonal changes in temperature.

PubMed

Niehaus, Amanda C; Wilson, Robbie S; Storm, Jonathan J; Angilletta, Michael J

2012-02-01

In nature, many organisms alter their developmental trajectory in response to environmental variation. However, studies of thermal acclimation have historically involved stable, unrealistic thermal treatments. In our study, we incorporated ecologically relevant treatments to examine the effects of environmental stochasticity on the thermal acclimation of the fall field cricket (Gryllus pennsylvanicus). We raised crickets for 5 weeks at either a constant temperature (25°C) or at one of three thermal regimes mimicking a seasonal decline in temperature (from 25 to 12°C). The latter three treatments differed in their level of thermal stochasticity: crickets experienced either no diel cycle, a predictable diel cycle, or an unpredictable diel cycle. Following these treatments, we measured several traits considered relevant to survival or reproduction, including growth rate, jumping velocity, feeding rate, metabolic rate, and cold tolerance. Contrary to our predictions, the acclimatory responses of crickets were unrelated to the magnitude or type of thermal variation. Furthermore, acclimation of performance was not ubiquitous among traits. We recommend additional studies of acclimation in fluctuating environments to assess the generality of these findings.

On diel variability of marine sediment backscattering properties caused by microphytobenthos photosynthesis: Impact of environmental factors

NASA Astrophysics Data System (ADS)

Gorska, Natalia; Kowalska-Duda, Ewa; Pniewski, Filip; Latała, Adam

2018-06-01

The study has been motivated by the development of the hydroacoustic techniques for mapping and classifying the benthic habitats and for the research of the microbenthos photosynthesis in the semi-enclosed Baltic Sea, particularly sensitive to human activity. The investigation of the effect of the benthic microalgal photosynthesis on the echo signal from the Baltic sandy sediments is continuing. The study clarifies the impact of the abiotic and biotic factors on the diel variation of the backscattering caused by the benthic microalgal photosynthetic activity. Five multiday laboratory experiments, different in hydrophysical or biological conditions, were conducted. During each measurement series, the "day" (illumination) and "night" (darkness) conditions (L:D cycle) were simulated and the diel variations of the echo energy of the backscattered signal were analyzed. The hydroacoustic data were acquired along with measuring biological and biooptical parameters and oxygen concentration. The study demonstrated the impact of microphytobenthos photosynthesis on the backscattering properties of the marine sediment which is sensitive to the illumination level, benthic microalgal biomass and macrozoobenthos bioturbation.

In-stream biotic control on nutrient biogeochemistry in a forested sheadwater tream, West Fork of Walker Branch

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roberts, Brian J; Mulholland, Patrick J

2007-01-01

A growing body of evidence demonstrates the importance of in-stream processing in regulating nutrient export, yet the influence of temporal variability in stream metabolism on net nutrient uptake has not been explicitly addressed. Streamwater DIN and SRP concentrations in Walker Branch, a first-order deciduous forest stream in eastern Tennessee, show a repeated pattern of annual maxima in summer and biannual minima in spring and autumn. Temporal variations in catchment hydrologic flowpaths result in lower winter and higher summer nutrient concentrations, but do not explain the spring and autumn nutrient minima. Ambient nutrient uptake rates were measured 2-3 times per weekmore » over an 18-mo period and compared to daily rates of gross primary production (GPP) and ecosystem respiration (ER) to examine the influence of in-stream biotic activity on nutrient export. GPP and ER rates explained 85% of the variation in net DIN retention with high net NO3- uptake (and lower net NH4+ release) rates occurring during spring and autumn and net DIN release in summer. Diel nutrient concentration patterns were examined several times throughout the year to determine the relative importance of autotrophic and heterotrophic activity on net nutrient uptake. High spring GPP corresponded to daily decreases in NO3- over the illuminated hours resulting in high diel NO3- amplitude which dampened as the canopy closed. GPP explained 91% of the variance in diel NO3- amplitude. In contrast, the autumn nutrient minima was largely explained by heterotrophic respiration since GPP remained low and little diel NO3- variation was observed during the autumn.« less

Seasonal variation in diel behaviour and habitat use by age 1+ steelhead (Oncorhynchus mykiss) in Coast and Cascade Range streams in Oregon, U.S.A

Treesearch

Gordon H. Reeves; Jon B. Grunbaum; Dirk W. Lang

2009-01-01

The seasonal diel behaviour of age 1+ steelhead from Coast and Cascade Range streams in Oregon was examined in the field and in laboratory streams. During the summer, fish from both areas were active during the day in natural streams: they held position in the water column in moderate velocities and depths. At night, fish were in slower water, closer to the bottom...

Diel biogeochemical processes in terrestrial waters

USGS Publications Warehouse

Nimick, David A.; Gammons, Christopher H.

2011-01-01

Many biogeochemical processes in rivers and lakes respond to the solar photocycle and produce persistent patterns of measureable phenomena that exhibit a day–night, or 24-h, cycle. Despite a large body of recent literature, the mechanisms responsible for these diel fluctuations are widely debated, with a growing consensus that combinations of physical, chemical, and biological processes are involved. These processes include streamflow variation, photosynthesis and respiration, plant assimilation, and reactions involving photochemistry, adsorption and desorption, and mineral precipitation and dissolution. Diel changes in streamflow and water properties such as temperature, pH, and dissolved oxygen concentration have been widely recognized, and recently, diel studies have focused more widely by considering other constituents such as dissolved and particulate trace metals, metalloids, rare earth elements, mercury, organic matter, dissolved inorganic carbon (DIC), and nutrients. The details of many diel processes are being studied using stable isotopes, which also can exhibit diel cycles in response to microbial metabolism, photosynthesis and respiration, or changes in phase, speciation, or redox state. In addition, secondary effects that diel cycles might have, for example, on biota or in the hyporheic zone are beginning to be considered.This special issue is composed primarily of papers presented at the topical session “Diurnal Biogeochemical Processes in Rivers, Lakes, and Shallow Groundwater” held at the annual meeting of the Geological Society of America in October 2009 in Portland, Oregon. This session was organized because many of the growing number of diel studies have addressed just a small part of the full range of diel cycling phenomena found in rivers and lakes. This limited focus is understandable because (1) fundamental aspects of many diel processes are poorly understood and require detailed study, (2) the interests and expertise of individual scientists typically do not encompass the wide diversity and range of processes that produce diel cycles, and (3) the logistics of making field measurements for 24-h periods has limited recognition and understanding of these important cycles. Thus, the topical session brought together hydrologists, biologists, geochemists, and ecologists to discuss field studies, laboratory experiments, theoretical modeling, and measurement techniques related to diel cycling. Hopefully with the cross-disciplinary synergy developed at the session as well as by this special issue, a more comprehensive understanding of the interrelationships between the diel processes will be developed. Needless to say, understanding diel processes is critical for regulatory agencies and the greater scientific community. And perhaps more importantly, expanded knowledge of biogeochemical cycling may lead to better predictions of how aquatic ecosystems might react to changing conditions of contaminant loading, eutrophication, climate change, drought, industrialization, development, and other variables.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Espeleta, Javier F.; Cardon, Zoe G.; Mayer, K. Ulrich

Hydro-biogeochemical processes in the rhizosphere regulate nutrient and water availability, and thus ecosystem productivity. We hypothesized that two such processes often neglected in rhizosphere models — diel plant water use and competitive cation exchange — could interact to enhance availability of K + and NH 4 +, both high-demand nutrients. A rhizosphere model with competitive cation exchange was used to investigate how diel plant water use (i.e., daytime transpiration coupled with no nighttime water use, with nighttime root water release, and with nighttime transpiration) affects competitive ion interactions and availability of K + and NH 4 +. Competitive cation exchangemore » enabled lowdemand cations that accumulate against roots (Ca 2+, Mg 2+, Na +) to desorb NH 4 + and K + from soil, generating non-monotonic dissolved concentration profiles (i.e. ‘hotspots’ 0.1–1 cm from the root). Cation accumulation and competitive desorption increased with net root water uptake. Daytime transpiration rate controlled diel variation in NH 4 + and K + aqueous mass, nighttime water use controlled spatial locations of ‘hotspots’, and day-to-night differences in water use controlled diel differences in ‘hotspot’ concentrations. Finally, diel plant water use and competitive cation exchange enhanced NH 4 + and K + availability and influenced rhizosphere concentration dynamics. Demonstrated responses have implications for understanding rhizosphere nutrient cycling and plant nutrient uptake.« less

Influence of in-stream diel concentration cycles of dissolved trace metals on acute toxicity to one-year-old cutthroat trout (Oncorhynchus clarki lewisi)

USGS Publications Warehouse

Nimick, D.A.; Harper, D.D.; Farag, A.M.; Cleasby, T.E.; MacConnell, Elizabeth; Skaar, D.

2007-01-01

Extrapolating results of laboratory bioassays to streams is difficult, because conditions such as temperature and dissolved metal concentrations can change substantially on diel time scales. Field bioassays conducted for 96 h in two mining-affected streams compared the survival of hatchery-raised, metal-nai??ve westslope cutthroat trout (Oncorhynchus clarki lewisi) exposed to dissolved (0.1-??m filtration) metal concentrations that either exhibited the diel variation observed in streams or were controlled at a constant value. Cadmium and Zn concentrations in these streams increased each night by as much as 61 and 125%, respectively, and decreased a corresponding amount the next day, whereas Cu did not display a diel concentration cycle. In High Ore Creek (40 km south of Helena, MT, USA), survival (33%) after exposure to natural diel-fluctuating Zn concentrations (range, 214-634 ??g/L; mean, 428 ??g/L) was significantly (p = 0.008) higher than survival (14%) after exposure to a controlled, constant Zn concentration (422 ??g/L). Similarly, in Dry Fork Belt Creek (70 km southeast of Great Falls, MT, USA), survival (75%) after exposure to diel-fluctuating Zn concentrations (range, 266-522 ??g/L; mean, 399 ??g/L) was significantly (p = 0.022) higher than survival (50%) in the constant-concentration treatment (392 ??g/L). Survival likely was greater in these diel treatments, both because the periods of lower metal concentrations provided some relief for the fish and because toxicity during periods of higher metal concentrations was lessened by the simultaneous occurrence each night of lower water temperatures, which reduce the rate of metal uptake. Based on the present study, current water-quality criteria appear to be protective for streams with diel concentration cycles of Zn (and, perhaps, Cd) for the hydrologie conditions tested. ?? 2007 SETAC.

Vertical distributions and diel migrations of Euthecosomata in the northwest Sargasso Sea

NASA Astrophysics Data System (ADS)

Wormuth, John H.

1981-12-01

Vertical distributions and seasonal variations in abundance of nine abundant or frequent pteropod species or subspecies in the northwest Sargasso Sea are described. Factor analyses yielded two groups, diel migrators and non-migrators. In terms of water column abundances, tows taken in August and November are similar, as are tows in December and April. Most species show significant within-species agreement in depth distribution over the year but high variability in abundance. Regression analyses using environmental parameters as independent variables show significant correlations of species abundances with temperature.

Rate variations of a hetero-Diels--Alder reaction in supercritical fluid CO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, R.L.; Glaeser, R.; Bush, D.

1999-11-01

The hetero-Diels-Alder reaction between anthracene and excess 4-phenyl-1,2,4-triazoline-3,5-dione has been investigated in supercritical CO{sub 2} at 40 C and pressures between 75 and 216 bar. Biomolecular reaction rate constants have been measured via fluorescence spectroscopy by following the decrease in anthracene concentration with reaction time. The reaction rate is elevated in the vicinity of the critical pressure. This difference is consistent with local composition enhancement and can be modeled with the Peng-Robinson equation of state.

Use of acoustic backscatter and vertical velocity to estimate concentration and dynamics of suspended solids in Upper Klamath Lake, south-central Oregon: Implications for Aphanizomenon flos-aquae

USGS Publications Warehouse

Wood, Tamara M.; Gartner, Jeffrey W.

2010-01-01

Vertical velocity and acoustic backscatter measurements by acoustic Doppler current profilers were used to determine seasonal, subseasonal (days to weeks), and diel variation in suspended solids in a freshwater lake where massive cyanobacterial blooms occur annually. During the growing season, the suspended material in the lake is dominated by the buoyancy-regulating cyanobacteria, Aphanizomenon flos-aquae. Measured variables (water velocity, relative backscatter [RB], wind speed, and air and water temperatures) were averaged over the deployment season at each sample time of day to determine average diel cycles. Phase shifts between diel cycles in RB and diel cycles in wind speed, vertical water temperature differences (delta T(degree)), and horizontal current speeds were found by determining the lead or lag that maximized the linear correlation between the respective diel cycles. Diel cycles in RB were more in phase with delta T(degree) cycles, and, to a lesser extent, wind cycles, than to water current cycles but were out of phase with the cycle that would be expected if the vertical movement of buoyant cyanobacteria colonies was controlled primarily by light. Clear evidence of a diel cycle in vertical velocity was found only at the two deepest sites in the lake. Cycles of vertical velocity, where present, were out of phase with expected vertical motion of cyanobacterial colonies based on the theoretical cycle for light-driven vertical movement. This suggests that water column stability and turbulence were more important factors in controlling vertical distribution of colonies than light. Variations at subseasonal time scales were determined by filtering data to pass periods between 1.2 and 15 days. At subseasonal time scales, correlations between RB and currents or air temperature were consistent with increased concentration of cyanobacterial colonies near the surface when water column stability increased (higher air temperatures or weaker currents) and dispersal of colonies throughout the water column when the water column mixed more easily. RB was used to estimate suspended solids concentrations (SSC). Correlations of depth-integrated SSC with currents or air temperatures suggest that depth-integrated water column mass decreased under conditions of greater water column stability and weaker currents. Results suggest that the use of measured vertical velocity and acoustic backscatter as a surrogate for suspended material has the potential to contribute significant additional insight into dynamics of Aphanizomenon flos-aquae colonies in Upper Klamath Lake, south-central Oregon.

Seasonal and diel variation in xylem CO2 concentration and sap pH in sub-Mediterranean oak stems.

PubMed

Salomón, Roberto; Valbuena-Carabaña, María; Teskey, Robert; McGuire, Mary Anne; Aubrey, Doug; González-Doncel, Inés; Gil, Luis; Rodríguez-Calcerrada, Jesús

2016-04-01

Since a substantial portion of respired CO2 remains within the stem, diel and seasonal trends in stem CO2 concentration ([CO2]) are of major interest in plant respiration and carbon budget research. However, continuous long-term stem [CO2] studies are scarce, and generally absent in Mediterranean climates. In this study, stem [CO2] was monitored every 15min together with stem and air temperature, sap flow, and soil water storage during a growing season in 16 stems of Quercus pyrenaica to elucidate the main drivers of stem [CO2] at different temporal scales. Fluctuations in sap pH were also assessed during two growing seasons to evaluate potential errors in estimates of the concentration of CO2 dissolved in xylem sap ([CO2*]) calculated using Henry's law. Stem temperature was the best predictor of stem [CO2] and explained more than 90% and 50% of the variability in stem [CO2] at diel and seasonal scales, respectively. Under dry conditions, soil water storage was the main driver of stem [CO2]. Likewise, the first rains after summer drought caused intense stem [CO2] pulses, suggesting enhanced stem and root respiration and increased resistance to radial CO2 diffusion. Sap flow played a secondary role in controlling stem [CO2] variations. We observed night-time sap pH acidification and progressive seasonal alkalinization. Thus, if the annual mean value of sap pH (measured at midday) was assumed to be constant, night-time sap [CO2*] was substantially overestimated (40%), and spring and autumn sap [CO2*] were misestimated by 25%. This work highlights that diel and seasonal variations in temperature, tree water availability, and sap pH substantially affect xylem [CO2] and sap [CO2*]. © The Author 2016. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Diurnal patterns of methane flux from a seasonal wetland: mechanisms and methodology

USGS Publications Warehouse

Bansal, Sheel; Tangen, Brian; Finocchiaro, Raymond

2018-01-01

Methane emissions from wetlands are temporally dynamic. Few chamber-based studies have explored diurnal variation in methane flux with high temporal replication. Using an automated sampling system, we measured methane flux every 2.5 to 4 h for 205 diel cycles during three growing seasons (2013–2015) from a seasonal wetland in the Prairie Pothole Region of North America. During ponded conditions, fluxes were generally positive (i.e., methanogenesis dominant, 10.1 ± 0.8 mg m−2 h−1), had extreme range of variation (from −1 to 70 mg m−2 h−1), and were highest during late day. In contrast, during dry conditions fluxes were very low and primarily negative (i.e., oxidation dominant, −0.05 ± 0.002 mg m−2 h−1), with the highest (least negative) fluxes occurring at pre-dawn. During semi-saturated conditions, methane fluxes also were very low, oscillated between positive and negative values (i.e., balanced between methanogenesis and methane oxidation), and exhibited no diel pattern. Methane flux was positively correlated with air temperature during ponded conditions (r = 0.57) and negatively during dry conditions (r = −0.42). Multiple regression analyses showed that temperature, light and water-filled pore space explained 72% of variation in methane flux. Methane fluxes are highly temporally dynamic and follow contrasting diel patterns that are dependent on dominant microbial processes influenced by saturation state.

Syntheses of the Stemona Alkaloids (±)-Stenine, (±)-Neostenine, and (±)-13-Epineostenine Using a Stereodivergent Diels-Alder/Azido-Schmidt Reaction

PubMed Central

Frankowski, Kevin J.; Golden, Jennifer E.; Zeng, Yibin; Lei, Yao; Aubé, Jeffrey

2009-01-01

A tandem Diels-Alder/azido Schmidt reaction sequence provides rapid access to the core skeleton shared by several Stemona alkaloids including stenine, neostenine, tuberstemonine, and neotubererostemonine. The discovery and evolution of inter- and intramolecular variations of this process and their applications to total syntheses of (±)–stenine and (±)–neostenine is described. The stereochemical outcome of the reaction depends on both substrate type and reaction condition, enabling the preparation of both (±)–stenine and (±)–neostenine from the same diene/dienophile combination. PMID:18396881

Drivers of Variability of Diel-Cycling and Episodic Hypoxia In ...

EPA Pesticide Factsheets

Eutrophication of coastal ecosystems is a longstanding environmental concern, exacerbated by population growth and associated nutrient pollution, and ultimately resulting in increased incidence of hypoxia. Shallow and highly productive estuaries and embayments are particularly susceptible to diel-cycling hypoxia, associated with day-night cycles of production and respiration, which can cause extreme excursions in dissolved oxygen (DO) concentrations from anoxia to super-saturation within a single day. Diel oxygen dynamics in these systems are complex, and may be influenced by wind forcing, vertical and horizontal mixing, variation in freshwater inflow, cloud cover, and temperature. To better understand the environmental drivers of periodic hypoxia, this study examined four northern Gulf of Mexico Estuaries (Weeks Bay, AL; Wolf Bay, AL; Fowl River, AL; and St. Louis Bay, MS). Dissolved oxygen varied strongly on a diel basis in all four systems, with periods of sustained low oxygen (>24 h) observed in both Weeks Bay and Wolf Bay. The duration and persistence of hypoxia further varied in response to changing salinity regimes and regional weather. These results underscore the dynamic nature of hypoxia in shallow estuarine systems, and highlight the importance of combining fixed site continuous monitoring data with spatial hydrographic surveys to accurately resolve DO dynamics. This abstract is submitted for presentation at the CERF conference held Nov 8-12 in Oregon

Diel variations in stream chemistry and isotopic composition of dissolved inorganic carbon, upper Clark Fork River, Montana, USA

USGS Publications Warehouse

Parker, Stephen R.; Gammons, Christopher H.; Poulson, Simon R.; DeGrandpre, Michael D.

2007-01-01

Many rivers undergo diel (24-h) concentration fluctuations of pH, dissolved gases, trace metals, nutrients, and other chemical species. A study conducted in 1994 documented such behavior in the upper Clark Fork River, Montana, a stream whose headwaters have been severely impacted by historic metal mining, milling, and smelting. The purpose of the present investigation was to expand on these earlier findings by conducting simultaneous diel samplings at two sites on the upper Clark Fork River separated by 2.5 h of stream travel time. By monitoring two stations, it was possible to more closely examine the processes that control temporal and spatial gradients in stream chemistry. Another objective was to examine diel changes in the δ13C composition of dissolved inorganic C (DIC) and their relationship to biological activity in the stream. The most important findings of this study include: (1) concentrations of dissolved and particulate heavy metals increased during the night and decreased during the day, in agreement with previous work; (2) these changes were positively correlated to diel changes in pH, dissolved O2, and water temperature; (3) dissolved concentrations increased during the night at the lower site, but showed the opposite behavior at the upper site; and (4) diel changes in δ13C-DIC were noted at both sites, although the timing and magnitudes of the cycles differed. Hypotheses to explain the first two observations include: cyclic co-precipitation of divalent metals with carbonate minerals; pH- and temperature-dependent sorption of metal cations onto the streambed and suspended particles; or photosynthetically enhanced oxidation and removal of Fe and Mn oxides at biofilm surfaces during the daytime. The latter model explains the majority of the field observations, including night-time increases in particulate forms of Fe and other elements.

Diel behavior of iron and other heavy metals in a mountain stream with acidic to neutral pH: Fisher Creek, Montana, USA

USGS Publications Warehouse

Gammons, C.H.; Nimick, D.A.; Parker, S.R.; Cleasby, T.E.; McCleskey, R. Blaine

2005-01-01

Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe2+ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters. Copyright ?? 2005 Elsevier Ltd.

Night sampling improves indices used for management of yellow perch in Lake Erie

USGS Publications Warehouse

Kocovsky, P.M.; Stapanian, M.A.; Knight, C.T.

2010-01-01

Catch rate (catch per hour) was examined for age-0 and age-1 yellow perch, Perca flavescens (Mitchill), captured in bottom trawls from 1991 to 2005 in western Lake Erie: (1) to examine variation of catch rate among years, seasons, diel periods and their interactions; and (2) to determine whether sampling during particular diel periods improved the management value of CPH data used in models to project abundance of age-2 yellow perch. Catch rate varied with year, season and the diel period during which sampling was conducted as well as by the interaction between year and season. Indices of abundance of age-0 and age-1 yellow perch estimated from night samples typically produced better fitting models and lower estimates of age-2 abundance than those using morning or afternoon samples, whereas indices using afternoon samples typically produced less precise and higher estimates of abundance. The diel period during which sampling is conducted will not affect observed population trends but may affect estimates of abundance of age-0 and age-1 yellow perch, which in turn affect recommended allowable harvest. A field experiment throughout western Lake Erie is recommended to examine potential benefits of night sampling to management of yellow perch. Published 2010. The article is a US Government work and is in the public domain in the USA.

Diel-scale temporal dynamics recorded for bacterial groups in Namib Desert soil

PubMed Central

Gunnigle, Eoin; Frossard, Aline; Ramond, Jean-Baptiste; Guerrero, Leandro; Seely, Mary; Cowan, Don A.

2017-01-01

Microbes in hot desert soil partake in core ecosystem processes e.g., biogeochemical cycling of carbon. Nevertheless, there is still a fundamental lack of insights regarding short-term (i.e., over a 24-hour [diel] cycle) microbial responses to highly fluctuating microenvironmental parameters like temperature and humidity. To address this, we employed T-RFLP fingerprinting and 454 pyrosequencing of 16S rRNA-derived cDNA to characterize potentially active bacteria in Namib Desert soil over multiple diel cycles. Strikingly, we found that significant shifts in active bacterial groups could occur over a single 24-hour period. For instance, members of the predominant Actinobacteria phyla exhibited a significant reduction in relative activity from morning to night, whereas many Proteobacterial groups displayed an opposite trend. Contrary to our leading hypothesis, environmental parameters could only account for 10.5% of the recorded total variation. Potential biotic associations shown through co-occurrence networks indicated that non-random inter- and intra-phyla associations were ‘time-of-day-dependent’ which may constitute a key feature of this system. Notably, many cyanobacterial groups were positioned outside and/or between highly interconnected bacterial associations (modules); possibly acting as inter-module ‘hubs’ orchestrating interactions between important functional consortia. Overall, these results provide empirical evidence that bacterial communities in hot desert soils exhibit complex and diel-dependent inter-community associations. PMID:28071697

Diel-scale temporal dynamics recorded for bacterial groups in Namib Desert soil

NASA Astrophysics Data System (ADS)

Gunnigle, Eoin; Frossard, Aline; Ramond, Jean-Baptiste; Guerrero, Leandro; Seely, Mary; Cowan, Don A.

2017-01-01

Microbes in hot desert soil partake in core ecosystem processes e.g., biogeochemical cycling of carbon. Nevertheless, there is still a fundamental lack of insights regarding short-term (i.e., over a 24-hour [diel] cycle) microbial responses to highly fluctuating microenvironmental parameters like temperature and humidity. To address this, we employed T-RFLP fingerprinting and 454 pyrosequencing of 16S rRNA-derived cDNA to characterize potentially active bacteria in Namib Desert soil over multiple diel cycles. Strikingly, we found that significant shifts in active bacterial groups could occur over a single 24-hour period. For instance, members of the predominant Actinobacteria phyla exhibited a significant reduction in relative activity from morning to night, whereas many Proteobacterial groups displayed an opposite trend. Contrary to our leading hypothesis, environmental parameters could only account for 10.5% of the recorded total variation. Potential biotic associations shown through co-occurrence networks indicated that non-random inter- and intra-phyla associations were ‘time-of-day-dependent’ which may constitute a key feature of this system. Notably, many cyanobacterial groups were positioned outside and/or between highly interconnected bacterial associations (modules); possibly acting as inter-module ‘hubs’ orchestrating interactions between important functional consortia. Overall, these results provide empirical evidence that bacterial communities in hot desert soils exhibit complex and diel-dependent inter-community associations.

The effects of constant and diel-fluctuating temperature acclimation on the thermal tolerance, swimming capacity, specific dynamic action and growth performance of juvenile Chinese bream.

PubMed

Peng, Jing; Cao, Zhen-Dong; Fu, Shi-Jian

2014-10-01

We investigated the effects of constant and diel-fluctuating temperature acclimation on the thermal tolerance, swimming capacity, specific dynamic action (SDA) and growth performance of juvenile Chinese bream (Parabramis pekinensis). The critical thermal maxima (CTmax), critical thermal minima (CTmin), lethal thermal maxima (LTmax), lethal thermal minima (LTmin), critical swimming speed (Ucrit) and fast-start escape response after 30 d acclimation to three constant temperatures (15, 20 and 25 °C) and one diel-fluctuating temperature (20±5 °C) were measured. In addition, feeding rate (FR), feeding efficiency (FE) and specific growth rate (SGR) were measured. The diel-fluctuating temperature group showed lower CTmin than the 20 °C group but a similar CTmax, indicating a wider thermal scope. SDA linearly increased with the temperature. Temperature variation between 20 and 25 °C had little effect on either swimming or growth performance. However, fish in the 15 °C group exhibited much poorer swimming and growth performance than those in the 20 °C group. Ucrit decreased slightly under low acclimation temperature due to the pronounced improvement in swimming efficiency under cold temperature. Fish in the diel-fluctuating temperature group fed more but exhibited similar SGR compared to 20 °C group, possibly due in part to an increase in energy expenditure to cope with the temperature fluctuation. The narrower thermal scope and lower CTmax of Chinese bream together with the conservation of CTmax with temperature acclimation, suggests that local water temperature elevations may have more profound effects on Chinese bream than on other fish species in the Three Gorges Reservoir. Copyright © 2014 Elsevier Inc. All rights reserved.

Demonstration of a diel trend in sensitivity of Gossypium to ozone: a step toward relating O3 injury to exposure or flux

PubMed Central

Grantz, D.A.

2013-01-01

Plant injury by ozone (O3) occurs in three stages, O3 entrance through stomata, overcoming defences, and attack on bioreceptors. Concentration, deposition, and uptake of O3 are accessible by observation and modelling, while injury can be assessed visually or through remote sensing. However, the relationship between O3 metrics and injury is confounded by variation in sensitivity to O3. Sensitivity weighting parameters have previously been assigned to different plant functional types and growth stages, or by differentially weighting O3 concentrations, but diel and seasonal variability have not been addressed. Here a plant sensitivity parameter (S) is introduced, relating injury to O3 dose (uptake) using three independent injury endpoints in the crop species, Pima cotton (Gossypium barbadense). The diel variability of S was determined by assessment at 2h intervals. Pulses of O3 (15min) were used to assess passive (constitutive) defence mechanisms and dose was used rather than concentration to avoid genetic or environmental effects on stomatal regulation. A clear diel trend in S was apparent, with maximal sensitivity in mid-afternoon, not closely related to gas exchange, whole leaf ascorbate, or total antioxidant capacity. This physiologically based sensitivity parameter provides a novel weighting factor to improve modelled relationships between either flux or exposure to O3, and O3 impacts. This represents a substantial improvement over concentration- or phenology-based weighting factors currently in use. Future research will be required to characterize the variability and metabolic drivers of diel changes in S, and the performance of this parameter in prediction of O3 injury. PMID:23404900

Environmental forcing does not induce diel or synoptic variation in the carbon isotope content of forest soil respiration

DOE PAGES

Bowling, D. R.; Egan, J. E.; Hall, S. J.; ...

2015-08-31

Recent studies have examined temporal fluctuations in the amount and carbon isotope content (δ 13C) of CO 2 produced by the respiration of roots and soil organisms. These changes have been correlated with diel cycles of environmental forcing (e.g., sunlight and soil temperature) and with synoptic-scale atmospheric motion (e.g., rain events and pressure-induced ventilation). We used an extensive suite of measurements to examine soil respiration over 2 months in a subalpine forest in Colorado, USA (the Niwot Ridge AmeriFlux forest). Observations included automated measurements of CO 2 and δ 13C of CO 2 in the soil efflux, the soil gasmore » profile, and forest air. There was strong diel variability in soil efflux but no diel change in the δ 13C of the soil efflux (δ R) or the CO 2 produced by biological activity in the soil (δ J). Following rain, soil efflux increased significantly, but δ R and δ J did not change. Temporal variation in the δ 13C of the soil efflux was unrelated to measured environmental variables, and we failed to find an explanation for this unexpected result. Measurements of the δ 13C of the soil efflux with chambers agreed closely with independent observations of the isotopic composition of soil CO 2 production derived from soil gas well measurements. Deeper in the soil profile and at the soil surface, results confirmed established theory regarding diffusive soil gas transport and isotopic fractionation. Deviation from best-fit diffusion model results at the shallower depths illuminated a pump-induced ventilation artifact that should be anticipated and avoided in future studies. There was no evidence of natural pressure-induced ventilation of the deep soil. However, higher variability in δ 13C of the soil efflux relative to δ 13C of production derived from soil profile measurements was likely caused by transient pressure-induced transport with small horizontal length scales.« less

Diel resource partitioning among juvenile Atlantic Salmon, Brown Trout, and Rainbow Trout during summer

USGS Publications Warehouse

Johnson, James H.; McKenna, James E.

2015-01-01

Interspecific partitioning of food and habitat resources has been widely studied in stream salmonids. Most studies have examined resource partitioning between two native species or between a native species and one that has been introduced. In this study we examine the diel feeding ecology and habitat use of three species of juvenile salmonids (i.e., Atlantic Salmon Salmo salar, Brown Trout Salmo trutta, and Rainbow Trout Oncorhynchus mykiss) in a tributary of Skaneateles Lake, New York. Subyearling Brown Trout and Rainbow Trout fed more heavily from the drift than the benthos, whereas subyearling Atlantic Salmon fed more from the benthos than either species of trout. Feeding activity of Atlantic Salmon and Rainbow Trout was similar, with both species increasing feeding at dusk, whereas Brown Trout had no discernable feeding peak or trough. Habitat availability was important in determining site-specific habitat use by juvenile salmonids. Habitat selection was greater during the day than at night. The intrastream, diel, intraspecific, and interspecific variation we observed in salmonid habitat use in Grout Brook illustrates the difficulty of acquiring habitat use information for widespread management applications.

Enzymatic catalysis of the Diels-Alder reaction in the biosynthesis of natural products.

PubMed

Oikawa, Hideaki; Tokiwano, Tetsuo

2004-06-01

Recent studies on enzymes catalyzing the Diels- Alder reaction. often named "Diels-Alderases", clearlydemonstrated the involvement of this synthetically useful reaction in the biosynthesis of natural products.This review covers natural Diels-Alder type cycloadducts. synthetic efforts on the chemical feasibility ofthe biosynthctic Diels - Alder reaction and a brief history of studies on Diels-Alderases. In addition,reaction mechanisms of artificial and natural Diels--Alderases are discussed.

DIEL VARIATIONS IN DISSOLVED METAL CONCENTRATIONS IN STREAMS: OCCURRENCE AND POSSIBLE CAUSES. (R829400E01)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Streamflow and water quality of the Grand Calumet River, Lake County, Indiana, and Cook County, Illinois, October 1984

USGS Publications Warehouse

Crawford, Charles G.; Wangsness, David J.

1987-01-01

A diel (24-hour) water-quality survey was done to investigate the sources of dry-weather waste inputs attributable to other than permitted point-source effluent and to evaluate the waste-load assimilative capacity of the Grand Calumet River, Lake County, Indiana, and Cook County, Illinois, in October 1984. Flow in the Grand Calumet River consists almost entirely of municipal and industrial effluents which comprised more than 90% of the 500 cu ft/sec flow observed at the confluence of the East Branch Grand Calumet River and the Indiana Harbor Ship Canal during the study. At the time of the study, virtually all of the flow in the West Branch Grand Calumet River was municipal effluent. Diel variations in streamflow of as much as 300 cu ft/sec were observed in the East Branch near the ship canal. The diel variation diminished at the upstream sampling sites in the East Branch. In the West Branch, the diel variation in flow was quite drastic; complete reversals of flow were observed at sampling stations near the ship canal. Average dissolved-oxygen concentrations at stations in the East Branch ranged from 5.7 to 8.2 mg/L and at stations in the West Branch from 0.8 to 6.6 mg/L. Concentrations of dissolved solids, suspended solids, biochemical-oxygen demand, ammonia, nitrite, nitrate, and phosphorus were substantially higher in the West Branch than in the East Branch. In the East Branch, only the Indiana Stream Pollution Control Board water-quality standards for total phosphorus and phenol were exceeded. In the West Branch, water-quality standards for total ammonia, chloride, cyanide, dissolved solids, fluoride, total phosphorus, mercury, and phenol were exceeded and dissolved oxygen was less than the minimum allowable. Three areas of significant differences between cumulative effluent and instream chemical-mass discharges were identified in the East Branch and one in the West Branch. The presence of unidentified waste inputs in the East Branch were indicated by differences in the chemical-mass discharges at three sites. Elevated suspended solids, biochemical-oxygen demand, and ammonia chemical-mass discharges at Columbia Avenue indicated the presence of a source of what may have been untreated sewage to the West Branch during the survey. (Author 's abstract)

The diel migrations and distributions within a Mesopelagic community in the North East Atlantic. 1. Introduction and sampling procedures

NASA Astrophysics Data System (ADS)

Roe, H. S. J.; Angel, M. V.; Badcock, J.; Domanski, P.; James, P. T.; Pugh, P. R.; Thurston, M. H.

(i) This paper is an introduction to a series of papers describing the diel migrations and interrelationships of a mesopelagic community in the northeast Atlantic. (ii) The biological and physical background to the sampling area is described. (iii) There was little physical structure in the water column to a depth of 1000 m. (iv) The influence of Mediterranean water was detectable at varying depths between 550 and 800 m during the sampling programme. The possibility of mesoscale activity at these depths is discussed. (v) The sampling programme is described. Using the I.O.S. rectangular midwater trawl, the RMT 1 + 8, one hour samples were taken at 4 depth horizons, 100, 250, 450 and 600 m. Each depth was fished continuously for 48 hr. (vi) Additional non-quantitative surface samples, and surface light measurements were made throughout the RMT 1 + 8 sampling period. (vii) 97 hauls were made and the data for fish, decapod Crustacea, mysids, euphausiids, amphipods, copepods, ostracods, siphonophores, medusae, cteniphores and chaetognaths analysed. (viii) General results in terms of total numbers and numbers of species taken by the RMT 1 and the RMT 8 are described. (ix) The populations at 100 and 250 m showed more diel variation than those at 450 and 600 m, but the proportions of individual species and groups changed continuously at all depths. (x) These changes are due to diel vertical migrations. The migrations of most species only involved a part of their populations.

An approach to quantify sources, seasonal change, and biogeochemical processes affecting metal loading in streams: Facilitating decisions for remediation of mine drainage

USGS Publications Warehouse

Kimball, B.A.; Runkel, R.L.; Walton-Day, K.

2010-01-01

Historical mining has left complex problems in catchments throughout the world. Land managers are faced with making cost-effective plans to remediate mine influences. Remediation plans are facilitated by spatial mass-loading profiles that indicate the locations of metal mass-loading, seasonal changes, and the extent of biogeochemical processes. Field-scale experiments during both low- and high-flow conditions and time-series data over diel cycles illustrate how this can be accomplished. A low-flow experiment provided spatially detailed loading profiles to indicate where loading occurred. For example, SO42 - was principally derived from sources upstream from the study reach, but three principal locations also were important for SO42 - loading within the reach. During high-flow conditions, Lagrangian sampling provided data to interpret seasonal changes and indicated locations where snowmelt runoff flushed metals to the stream. Comparison of metal concentrations between the low- and high-flow experiments indicated substantial increases in metal loading at high flow, but little change in metal concentrations, showing that toxicity at the most downstream sampling site was not substantially greater during snowmelt runoff. During high-flow conditions, a detailed temporal sampling at fixed sites indicated that Zn concentration more than doubled during the diel cycle. Monitoring programs must account for diel variation to provide meaningful results. Mass-loading studies during different flow conditions and detailed time-series over diel cycles provide useful scientific support for stream management decisions.

The effect of water table fluctuation on soil respiration in a lower coastal plain forested wetland in the southeastern U.S.

NASA Astrophysics Data System (ADS)

Miao, Guofang; Noormets, Asko; Domec, Jean-Christophe; Trettin, Carl C.; McNulty, Steve G.; Sun, Ge; King, John S.

2013-12-01

and environmental pressures on wetland hydrology may trigger changes in carbon (C) cycling, potentially exposing vast amounts of soil C to rapid decomposition. We measured soil CO2 efflux (Rs) continuously from 2009 to 2010 in a lower coastal plain forested wetland in North Carolina, U.S., to characterize its main environmental drivers. To understand and quantify the spatial variation due to microtopography and associated differences in hydrology, measurements were conducted at three microsites along a microtopographic gradient. The seasonal hysteresis in Rs differed by microtopographic location and was caused by the transitions between flooded and nonflooded conditions. Because flooded Rs was small, we reported Rs dynamics mainly during nonflooded periods. A nested model, modified from conventional Q10 (temperature sensitivity) model with dynamic parameters, provided a significantly better simulation on the observed variation of Rs. The model performed better with daily data, indicating that soil temperature (Ts) and water table depth (WTD) were the primary drivers for seasonal variation. The diel variation of Rs was high and independent of Ts and WTD, which both had small diel variations, suggesting the likely association with plant activity. Overall, the site-average soil CO2 efflux was approximately 960-1103 g C m-2 yr-1 in 2010, of which 93% was released during nonflooded periods. Our study indicates that Rs is highly linked to hydroperiod and microtopography in forested wetlands and droughts in wetlands will accelerate soil C loss.

1976 water-quality data in Bear Creek basin, Medford, Oregon

USGS Publications Warehouse

McKenzie, Stuart W.; Wittenberg, Loren A.

1977-01-01

The U.S. Geological Survey, in cooperation with the Rogue Valley Council of Governments, is studying surface-water-quality problems and their causes in the Bear Creek basin of southwestern Oregon. Two specific areas of investigation include: measurements of the quality and quantity of water in the irrigation canals and drainage system and the diel (during a 24-hour period) variation of water-quality parameters in the main stem of Bear Creek. The irrigation and drainage study involves 25 sites in canals and natural drainageways. One hundred thirty-three samples were collected for analysis, and discharge was determined at the time of collection. The diel study includes six sites on Bear Creek. On August 23-24, four parameters were monitored at all six sites during a 24-hour period.

Diel variation of larval fish abundance in the Amazon and Rio Negro.

PubMed

Araujo-Lima, C A; da Silva, V V; Petry, P; Oliveira, E C; Moura, S M

2001-08-01

Many streams and large rivers present higher ichthyoplankton densities at night. However, in some rivers this does not occur and larvae are equally abundant during the day. Larval drift diel variation is an important information for planning sampling programs for evaluating larval distribution and production. The aim of this study was to test whether the abundance of larval fish was different at either period. We tested it by comparing day and night densities of characiform, clupeiform and siluriform larvae during five years in the Amazon and one year in Rio Negro. We found that larvae of three species of characiform and larvae of siluriform were equally abundant during day and night in the Amazon. Conversely, the catch of Pellona spp. larvae was significantly higher during the day. In Rio Negro, however, larval abundance was higher during the night. These results imply that day samplings estimate adequately the abundance of these characiform and siluriform larvae in the Amazon, but not Pellona larvae. Evaluations of larved densities of Rio Negro will have to consider night sampling.

Population structure and genetic variation of the endangered species Elaeagnus mollis Diels (Elaeagnaceae).

PubMed

Zhang, J M; Zhang, F

2015-06-01

Elaeagnus mollis Diels is a group of shrubs and dwarf trees endemic to China and are endangered plants. However, the reason why these plants are endangered remains controversial. The current study aimed to explore the endangered status of E. mollis from a genetic perspective and to propose conservation strategies for this species. Using 16 polymorphic allozyme loci, the population genetic structure was investigated for three populations representing the taxa and variants. The variants exhibited relatively high levels of genetic variation compared to other woody shrubs with similar geographic distributions. The overall genetic diversity (HE = 0.352) was elevated compared to long-lived woody angiosperms. The average number of alleles per locus (A), percentage polymorphic loci (P), and observed heterozygosity (HO) were 2.0, 85.2, and 0.371, respectively. Furthermore, gene flow estimates within the population groups were also elevated. The life history and habitats of E. mollis play major roles in the levels of genetic diversity. The results of this study may help to device strategies for preserving the genetic diversity of E. mollis and for promoting planting.

Argon concentration time-series as a tool to study gas dynamics in the hyporheic zone.

PubMed

Mächler, Lars; Brennwald, Matthias S; Kipfer, Rolf

2013-07-02

The oxygen dynamics in the hyporheic zone of a peri-alpine river (Thur, Switzerland), were studied through recording and analyzing the concentration time-series of dissolved argon, oxygen, carbon dioxide, and temperature during low flow conditions, for a period of one week. The argon concentration time-series was used to investigate the physical gas dynamics in the hyporheic zone. Differences in the transport behavior of heat and gas were determined by comparing the diel temperature evolution of groundwater to the measured concentration of dissolved argon. These differences were most likely caused by vertical heat transport which influenced the local groundwater temperature. The argon concentration time-series were also used to estimate travel times by cross correlating argon concentrations in the groundwater with argon concentrations in the river. The information gained from quantifying the physical gas transport was used to estimate the oxygen turnover in groundwater after water recharge. The resulting oxygen turnover showed strong diel variations, which correlated with the water temperature during groundwater recharge. Hence, the variation in the consumption rate was most likely caused by the temperature dependence of microbial activity.

Diel resource partitioning among juvenile Atlantic Salmon, Brown Trout, and Rainbow Trout during summer

USGS Publications Warehouse

Johnson, James H.; McKenna, James E.

2015-01-01

Interspecific partitioning of food and habitat resources has been widely studied in stream salmonids. Most studies have examined resource partitioning between two native species or between a native species and one that has been introduced. In this study we examine the diel feeding ecology and habitat use of three species of juvenile salmonids (i.e., Atlantic Salmon Salmo salar, Brown Trout Salmo trutta, and Rainbow Trout Oncorhynchus mykiss) in a tributary of Skaneateles Lake, New York. Subyearling Brown Trout and Rainbow Trout fed more heavily from the drift than the benthos, whereas subyearling Atlantic Salmon fed more from the benthos than either species of trout. Feeding activity of Atlantic Salmon and Rainbow Trout was similar, with both species increasing feeding at dusk, whereas Brown Trout had no discernable feeding peak or trough. Habitat availability was important in determining site-specific habitat use by juvenile salmonids. Habitat selection was greater during the day than at night. The intrastream, diel, intraspecific, and interspecific variation we observed in salmonid habitat use in Grout Brook illustrates the difficulty of acquiring habitat use information for widespread management applications.

Primary and heterotrophic productivity relate to multikingdom diversity in a hypersaline mat

DOE PAGES

Bernstein, Hans C.; Brislawn, Colin J.; Dana, Karl; ...

2017-10-17

Benthic microbial ecosystems are widespread yet knowledge gaps still remain on the relationships between the diversity of species across kingdoms and productivity. Here, we ask two fundamental questions: (i) How does species diversity relate to the rates of primary and heterotrophic productivity? (ii) How do diel variations in light-energy inputs influence productivity and microbiome diversity? To answer these questions, microbial mats from a magnesium sulfate hypersaline lake were used to establish microcosms. Both the number and relatedness between bacterial and eukaryotic taxa in the microbiome were assayed via amplicon-based sequencing of 16S and 18S rRNA genes over two diel cycles.more » These results correlated with biomass productivity obtained from substrate-specific 13C stable isotope tracers that enabled comparisons between primary and heterotrophic productivity. Both bacterial and eukaryotic species richness and evenness were related only to the rates of 13C-labeled glucose and acetate biomass incorporation. Interestingly, measures of these heterotrophic relationships changed from positive and negative correlations depending on carbon derived from glucose or acetate, respectively. The bacterial and eukaryotic diversity of this ecosystem is also controlled, in part, from energy constraints imposed by changing irradiance over a diel cycle.« less

Primary and heterotrophic productivity relate to multikingdom diversity in a hypersaline mat

PubMed Central

Brislawn, Colin J.; Dana, Karl; Flores-Wentz, Tobias; Cory, Alexandra B.; Fansler, Sarah J.; Fredrickson, James K.; Moran, James J.

2017-01-01

Abstract Benthic microbial ecosystems are widespread yet knowledge gaps still remain on the relationships between the diversity of species across kingdoms and productivity. Here, we ask two fundamental questions: (i) How does species diversity relate to the rates of primary and heterotrophic productivity? (ii) How do diel variations in light-energy inputs influence productivity and microbiome diversity? To answer these questions, microbial mats from a magnesium sulfate hypersaline lake were used to establish microcosms. Both the number and relatedness between bacterial and eukaryotic taxa in the microbiome were assayed via amplicon-based sequencing of 16S and 18S rRNA genes over two diel cycles. These results correlated with biomass productivity obtained from substrate-specific 13C stable isotope tracers that enabled comparisons between primary and heterotrophic productivity. Both bacterial and eukaryotic species richness and evenness were related only to the rates of 13C-labeled glucose and acetate biomass incorporation. Interestingly, measures of these heterotrophic relationships changed from positive and negative correlations depending on carbon derived from glucose or acetate, respectively. The bacterial and eukaryotic diversity of this ecosystem is also controlled, in part, from energy constraints imposed by changing irradiance over a diel cycle. PMID:29045626

Behavioural Thermoregulatory Tactics in Lacustrine Brook Charr, Salvelinus fontinalis

PubMed Central

Bertolo, Andrea; Pépino, Marc; Adams, Julie; Magnan, Pierre

2011-01-01

The need to vary body temperature to optimize physiological processes can lead to thermoregulatory behaviours, particularly in ectotherms. Despite some evidence of within-population phenotypic variation in thermal behaviour, the occurrence of alternative tactics of this behaviour is rarely explicitly considered when studying natural populations. The main objective of this study was to determine whether different thermal tactics exist among individuals of the same population. We studied the behavioural thermoregulation of 33 adult brook charr in a stratified lake using thermo-sensitive radio transmitters that measured hourly individual temperature over one month. The observed behavioural thermoregulatory patterns were consistent between years and suggest the existence of four tactics: two “warm” tactics with both crepuscular and finer periodicities, with or without a diel periodicity, and two “cool” tactics, with or without a diel periodicity. Telemetry data support the above findings by showing that the different tactics are associated with different patterns of diel horizontal movements. Taken together, our results show a clear spatio-temporal segregation of individuals displaying different tactics, suggesting a reduction of niche overlap. To our knowledge, this is the first study showing the presence of behavioural thermoregulatory tactics in a vertebrate. PMID:21490935

Primary and heterotrophic productivity relate to multikingdom diversity in a hypersaline mat

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bernstein, Hans C.; Brislawn, Colin J.; Dana, Karl

Benthic microbial ecosystems are widespread yet knowledge gaps still remain on the relationships between the diversity of species across kingdoms and productivity. Here, we ask two fundamental questions: (i) How does species diversity relate to the rates of primary and heterotrophic productivity? (ii) How do diel variations in light-energy inputs influence productivity and microbiome diversity? To answer these questions, microbial mats from a magnesium sulfate hypersaline lake were used to establish microcosms. Both the number and relatedness between bacterial and eukaryotic taxa in the microbiome were assayed via amplicon-based sequencing of 16S and 18S rRNA genes over two diel cycles.more » These results correlated with biomass productivity obtained from substrate-specific 13C stable isotope tracers that enabled comparisons between primary and heterotrophic productivity. Both bacterial and eukaryotic species richness and evenness were related only to the rates of 13C-labeled glucose and acetate biomass incorporation. Interestingly, measures of these heterotrophic relationships changed from positive and negative correlations depending on carbon derived from glucose or acetate, respectively. The bacterial and eukaryotic diversity of this ecosystem is also controlled, in part, from energy constraints imposed by changing irradiance over a diel cycle.« less

Mechanisms of iron photoreduction in a metal-rich, acidic stream (St. Kevin Gulch, Colorado, U.S.A.)

USGS Publications Warehouse

Kimball, B.A.; McKnight, Diane M.; Wetherbee, G.A.; Harnish, R.A.

1992-01-01

Iron photoreduction in metal-rich, acidic streams affected by mine drainage accounts for some of the variability in metal chemistry of such streams, producing diel variations in Fe(II). Differentiation of the mechanisms of the Fe photoreduction reaction by a series of in-stream experiments at St. Kevin Gulch, Colorado, indicates that a homogeneous, solution-phase reaction can occur in the absence of suspended particulate Fe and bacteria, and the rate of reaction is increased by the presence of Fe colloids in the stream water. In-stream Fe photoreduction is limited during the diel cycle by the available Fe(III) in the water column and streambed. The quantum yield of Fe(II) was reproducible in diel measurements: the quantum yield, in mol E-1 (from 300 to 400 nm) was 1.4 ?? 10-3 in 1986, 0.8 ?? 10-3 in 1988 and 1.2 ?? 10-3 in 1989, at the same location and under similar streamflow and stream-chemistry conditions. In a photolysis control experiment, there was no detectable production of Fe(II) above background concentrations in stream-water samples that were experimentally excluded from sunlight. ?? 1992.

Diel Variation in Population Size and Ice Nucleation Activity of Pseudomonas syringae on Snap Bean Leaflets.

PubMed

Hirano, S S; Upper, C D

1989-03-01

The extent to which diel changes in the physical environment affect changes in population size and ice nucleation activity of Pseudomonas syringae on snap bean leaflets was determined under field conditions. To estimate bacterial population size and ice nucleation activity, bean leaflets were harvested at 2-h intervals during each of three 26-h periods. A tube nucleation test was used to assay individual leaflets for ice nuclei. Population sizes of P. syringae were determined by dilution plating of leaflet homogenates. The overall diel changes in P. syringae population sizes differed during each of the 26-h periods. In one 26-h period, there was a continuous increase in the logarithm of P. syringae population size despite intense solar radiation, absence of free moisture on leaf surfaces, and low relative humidity during the day. A mean doubling time of approximately 4.9 h was estimated for the 28-fold increase in P. syringae population size that occurred from 0900 to 0900 h during the 26-h period. However, doubling times of 3.3 and 1.9 h occurred briefly during this period from 1700 to 2300 h and from 0100 to 0700 h, respectively. Thus, growth rates of P. syringae in association with leaves in the field were of the same order of magnitude as optimal rates measured in the laboratory. The frequency with which leaflets bore ice nuclei active at -2.0, -2.2, and -2.5 degrees C varied greatly within each 26-h period. These large diel changes were inversely correlated primarily with the diel changes in air temperature and reflected changes in nucleation frequency rather than changes in population size of P. syringae. Thus, the response of bacterial ice nucleation activity to the physical environment was distinct from the changes in population size of ice nucleation-active P. syringae.

Ocean Acoustic Observatory Federation

DTIC Science & Technology

2001-09-30

range detection and localization of blue whale calls in the northeast Pacific Ocean ousing military hydrophone arrays, Jour. Acoust . Soc. Am., vol. 104...3616- 3624, 1998 . 5 Stafford , Kathleen M., Sharon L. Nieukirk, and Christopher G. Fox, Low-frequency whale sounds recorded on hydrophones... Stafford , Kathleen M., Blue Whale (Balaenoptera musculus) Vocalizations recorded in the North Pacific Ocean: Geographic, Seasonal, and Diel Variation,

On the Response of pH to Inorganic Nutrient Enrichment in Well-Mixed Coastal Marine Waters

EPA Science Inventory

Recent concerns about declining pH in the surface ocean in response to anthropogenic increases of CO2 in the atmosphere have raised the question of how this declining baseline of oceanic pH might interact with the much larger diel and seasonal variations of pH in coastal marine e...

Solution-phase parallel synthesis of hexahydro-1H-isoindolone libraries via tactical combination of Cu-catalyzed three-component coupling and Diels-Alder reactions.

PubMed

Zhang, Lei; Lushington, Gerald H; Neuenswander, Benjamin; Hershberger, John C; Malinakova, Helena C

2008-01-01

Parallel solution-phase synthesis of combinatorial libraries of hexahydro-1 H-isoindolones exploiting a novel "tactical combination" of Cu-catalyzed three-component coupling and Diels-Alder reactions was accomplished. Three distinct libraries consisting of 24 members (library I), 60 members (library II), and 32 members (library III) were constructed. Variation of three substituents on the isoindolone scaffold in library I was exclusively achieved by the choice of the building blocks. In the syntheses of libraries II and III, sublibraries of isoindolone scaffolds were prepared initially in a one-pot/two-step process and were further diversified via Pd-catalyzed Suzuki cross-coupling reaction with boronic acids at two different diversification points. The Lipinski profiles and calculated ADME properties of the compounds are also reported.

Origins of Stereoselectivity in the trans-Diels-Alder Paradigm

PubMed Central

Paton, Robert S.; Mackey, Joel L.; Kim, Woo Han; Lee, Jun Hee; Danishefsky, Samuel J.; Houk, K. N.

2010-01-01

The regioselectivity and stereoselectivity aspects of the Diels-Alder/radical hydrodenitration reaction sequence leading to trans-fused ring systems have been investigated with density functional calculations. A continuum of transition structures representing Diels-Alder and hetero-Diels-Alder cycloadditions as well as a sigmatropic rearrangement have been located, and they all lie very close in energy on the potential energy surface. All three pathways are found to be important in the formation of the Diels-Alder adduct. Reported regioselectivities are reproduced by the calculations. The stereoselectivity of radical hydrodenitration of the cis-Diels-Alder adduct is found to be related to the relative conformational stabilities of bicyclic radical intermediates. Overall, the computations provide understanding of the regioselectivities and stereoselectivities of the trans-Diels-Alder paradigm. PMID:20557046

Remote Acoustic Monitoring of North Atlantic Right Whales (Eubalaena glacialis) Reveals Seasonal and Diel Variations in Acoustic Behavior

PubMed Central

Matthews, Leanna P.; McCordic, Jessica A.; Parks, Susan E.

2014-01-01

Remote acoustic monitoring is a non-invasive tool that can be used to study the distribution, behavior, and habitat use of sound-producing species. The North Atlantic right whale (Eubalaena glacialis) is an endangered baleen whale species that produces a variety of stereotyped acoustic signals. One of these signals, the “gunshot” sound, has only been recorded from adult male North Atlantic right whales and is thought to function for reproduction, either as reproductive advertisement for females or as an agonistic signal toward other males. This study uses remote acoustic monitoring to analyze the presence of gunshots over a two-year period at two sites on the Scotian Shelf to determine if there is evidence that North Atlantic right whales may use these locations for breeding activities. Seasonal analyses at both locations indicate that gunshot sound production is highly seasonal, with an increase in the autumn. One site, Roseway West, had significantly more gunshot sounds overall and exhibited a clear diel trend in production of these signals at night. The other site, Emerald South, also showed a seasonal increase in gunshot production during the autumn, but did not show any significant diel trend. This difference in gunshot signal production at the two sites indicates variation either in the number or the behavior of whales at each location. The timing of the observed seasonal increase in gunshot sound production is consistent with the current understanding of the right whale breeding season, and our results demonstrate that detection of gunshots with remote acoustic monitoring can be a reliable way to track shifts in distribution and changes in acoustic behavior including possible mating activities. PMID:24646524

Remote acoustic monitoring of North Atlantic right whales (Eubalaena glacialis) reveals seasonal and diel variations in acoustic behavior.

PubMed

Matthews, Leanna P; McCordic, Jessica A; Parks, Susan E

2014-01-01

Remote acoustic monitoring is a non-invasive tool that can be used to study the distribution, behavior, and habitat use of sound-producing species. The North Atlantic right whale (Eubalaena glacialis) is an endangered baleen whale species that produces a variety of stereotyped acoustic signals. One of these signals, the "gunshot" sound, has only been recorded from adult male North Atlantic right whales and is thought to function for reproduction, either as reproductive advertisement for females or as an agonistic signal toward other males. This study uses remote acoustic monitoring to analyze the presence of gunshots over a two-year period at two sites on the Scotian Shelf to determine if there is evidence that North Atlantic right whales may use these locations for breeding activities. Seasonal analyses at both locations indicate that gunshot sound production is highly seasonal, with an increase in the autumn. One site, Roseway West, had significantly more gunshot sounds overall and exhibited a clear diel trend in production of these signals at night. The other site, Emerald South, also showed a seasonal increase in gunshot production during the autumn, but did not show any significant diel trend. This difference in gunshot signal production at the two sites indicates variation either in the number or the behavior of whales at each location. The timing of the observed seasonal increase in gunshot sound production is consistent with the current understanding of the right whale breeding season, and our results demonstrate that detection of gunshots with remote acoustic monitoring can be a reliable way to track shifts in distribution and changes in acoustic behavior including possible mating activities.

Diel variations in carbon isotopic composition and concentration of organic acids and their impact on plant dark respiration in different species.

PubMed

Lehmann, M M; Wegener, F; Werner, R A; Werner, C

2016-09-01

Leaf respiration in the dark and its C isotopic composition (δ(13) CR ) contain information about internal metabolic processes and respiratory substrates. δ(13) CR is known to be less negative compared to potential respiratory substrates, in particular shortly after darkening during light enhanced dark respiration (LEDR). This phenomenon might be driven by respiration of accumulated (13) C-enriched organic acids, however, studies simultaneously measuring δ(13) CR during LEDR and potential respiratory substrates are rare. We determined δ(13) CR and respiration rates (R) during LEDR, as well as δ(13) C and concentrations of potential respiratory substrates using compound-specific isotope analyses. The measurements were conducted throughout the diel cycle in several plant species under different environmental conditions. δ(13) CR and R patterns during LEDR were strongly species-specific and showed an initial peak, which was followed by a progressive decrease in both values. The species-specific differences in δ(13) CR and R during LEDR may be partially explained by the isotopic composition of organic acids (e.g., oxalate, isocitrate, quinate, shikimate, malate), which were (13) C-enriched compared to other respiratory substrates (e.g., sugars and amino acids). However, the diel variations in both δ(13) C and concentrations of the organic acids were generally low. Thus, additional factors such as the heterogeneous isotope distribution in organic acids and the relative contribution of the organic acids to respiration are required to explain the strong (13) C enrichment in leaf dark-respired CO2 . © 2016 German Botanical Society and The Royal Botanical Society of the Netherlands.

Seasonality of diel cycles of dissolved trace-metal concentrations in a Rocky Mountain stream

USGS Publications Warehouse

Nimick, D.A.; Cleasby, T.E.; McCleskey, R. Blaine

2005-01-01

Substantial diel (24-h) cycles in dissolved (0.1-??m filtration) metal concentrations were observed during summer low flow, winter low flow, and snowmelt runoff in Prickly Pear Creek, Montana. During seven diel sampling episodes lasting 34-61.5 h, dissolved Mn and Zn concentrations increased from afternoon minimum values to maximum values shortly after sunrise. Dissolved As concentrations exhibited the inverse timing. The magnitude of diel concentration increases varied in the range 17-152% for Mn and 70-500% for Zn. Diel increases of As concentrations (17-55%) were less variable. The timing of minimum and maximum values of diel streamflow cycles was inconsistent among sampling episodes and had little relation to the timing of metal concentration cycles, suggesting that geochemical rather than hydrological processes are the primary control of diel metal cycles. Diel cycles of dissolved metal concentrations should be assumed to occur at any time of year in any stream with dissolved metals and neutral to alkaline pH. ?? Springer-Verlag 2005.

Do predators influence the distribution of age-0 kokanee in a Colorado Reservoir?

USGS Publications Warehouse

Hardiman, J.M.; Johnson, B.M.; Martinez, P.J.

2004-01-01

Seasonal changes in reservoir conditions such as productivity, light, and temperature create spatiotemporal variation in habitat that may segregate or aggregate predators and prey, producing implications for the distribution, growth, and survival of fishes. We used hydroacoustics to document the diel vertical distribution of age-0 kokanee Oncorhynchus nerka relative to environmental gradients at Blue Mesa Reservoir, Colorado, during May-August of 2002. Temperature, light, and zooplankton density profiles were examined relative to foraging conditions for kokanee and their primary predator, lake trout Salvelinus namaycush. Age-0 kokanee displayed large diel vertical migrations in May despite the lack of an energetic advantage before reservoir stratification. Age-0 kokanee minimized near-surface foraging at this time, perhaps to avoid predation by visual predators, such as lake trout, in the well-lit surface waters. Strong reservoir stratification in midsummer appeared to provide a thermal refuge from lake trout that the kokanee exploited. By August vertical migrations were shallow and most kokanee remained in the epilimnion throughout the day. Although the energetic implications of the late-summer strategy are unclear, it appears that kokanee were responding to changes in their predator environment. A robust model for kokanee diel vertical migration across a range of systems should include a predator avoidance component.

Coupled Biogeochemical and Hydrodynamic Measurements over a Palauan Seagrass Bed: Can Seagrasses Mitigate Local Acidification Stress?

NASA Astrophysics Data System (ADS)

Hirsh, H.; Torres, W.; Shea, M.

2016-02-01

Interest in seagrass beds as a tool to locally mitigate ocean acidification is growing rapidly. Much of the interest in seagrasses is motivated by their root structure, which is able to sequester carbon over interannual and longer timescales. Far less is known about their biogeochemistry on shorter diel timescales, yet we know that diel cycle variation in CO2 chemistry on coral reefs can be quite substantial. Understanding short-term seagrass biogeochemistry is critical to evaluating if, and how, seagrasses may eventually be utilized to mitigate OA on coral reefs. We present the results of a high-resolution, 24-hour control volume experiment conducted in the Republic of Palau covering a 50m x 100m seagrass bed. Our dataset includes diel cycles of hydrodynamic (current profiles and turbulence), biogeochemical (pH, pCO2, TA, DIC, and O2), and environmental (temperature and salinity) parameters. We use these coupled hydrodynamic-biogeochemical measurements to estimate ecosystem metabolism and better quantify the capacity of seagrass to mitigate local acidification through the photosynthetic uptake of CO2. Combining our field observations with box model predictions allows us to gain better insight into the mechanisms that control seagrass metabolism and their ability to buffer CO2 for downstream corals.

Microwave-based reaction screening: tandem retro-Diels-Alder/Diels-Alder cycloadditions of o-quinol dimers.

PubMed

Dong, Suwei; Cahill, Katharine J; Kang, Moon-Il; Colburn, Nancy H; Henrich, Curtis J; Wilson, Jennifer A; Beutler, John A; Johnson, Richard P; Porco, John A

2011-11-04

We have accomplished a parallel screen of cycloaddition partners for o-quinols utilizing a plate-based microwave system. Microwave irradiation improves the efficiency of retro-Diels-Alder/Diels-Alder cascades of o-quinol dimers which generally proceed in a diastereoselective fashion. Computational studies indicate that asynchronous transition states are favored in Diels-Alder cycloadditions of o-quinols. Subsequent biological evaluation of a collection of cycloadducts has identified an inhibitor of activator protein-1 (AP-1), an oncogenic transcription factor.

The influence of sea ice, wind speed and marine mammals on Southern Ocean ambient sound.

PubMed

Menze, Sebastian; Zitterbart, Daniel P; van Opzeeland, Ilse; Boebel, Olaf

2017-01-01

This paper describes the natural variability of ambient sound in the Southern Ocean, an acoustically pristine marine mammal habitat. Over a 3-year period, two autonomous recorders were moored along the Greenwich meridian to collect underwater passive acoustic data. Ambient sound levels were strongly affected by the annual variation of the sea-ice cover, which decouples local wind speed and sound levels during austral winter. With increasing sea-ice concentration, area and thickness, sound levels decreased while the contribution of distant sources increased. Marine mammal sounds formed a substantial part of the overall acoustic environment, comprising calls produced by Antarctic blue whales ( Balaenoptera musculus intermedia ), fin whales ( Balaenoptera physalus ), Antarctic minke whales ( Balaenoptera bonaerensis ) and leopard seals ( Hydrurga leptonyx ). The combined sound energy of a group or population vocalizing during extended periods contributed species-specific peaks to the ambient sound spectra. The temporal and spatial variation in the contribution of marine mammals to ambient sound suggests annual patterns in migration and behaviour. The Antarctic blue and fin whale contributions were loudest in austral autumn, whereas the Antarctic minke whale contribution was loudest during austral winter and repeatedly showed a diel pattern that coincided with the diel vertical migration of zooplankton.

The influence of sea ice, wind speed and marine mammals on Southern Ocean ambient sound

NASA Astrophysics Data System (ADS)

Menze, Sebastian; Zitterbart, Daniel P.; van Opzeeland, Ilse; Boebel, Olaf

2017-01-01

This paper describes the natural variability of ambient sound in the Southern Ocean, an acoustically pristine marine mammal habitat. Over a 3-year period, two autonomous recorders were moored along the Greenwich meridian to collect underwater passive acoustic data. Ambient sound levels were strongly affected by the annual variation of the sea-ice cover, which decouples local wind speed and sound levels during austral winter. With increasing sea-ice concentration, area and thickness, sound levels decreased while the contribution of distant sources increased. Marine mammal sounds formed a substantial part of the overall acoustic environment, comprising calls produced by Antarctic blue whales (Balaenoptera musculus intermedia), fin whales (Balaenoptera physalus), Antarctic minke whales (Balaenoptera bonaerensis) and leopard seals (Hydrurga leptonyx). The combined sound energy of a group or population vocalizing during extended periods contributed species-specific peaks to the ambient sound spectra. The temporal and spatial variation in the contribution of marine mammals to ambient sound suggests annual patterns in migration and behaviour. The Antarctic blue and fin whale contributions were loudest in austral autumn, whereas the Antarctic minke whale contribution was loudest during austral winter and repeatedly showed a diel pattern that coincided with the diel vertical migration of zooplankton.

Photoreduction fuels biogeochemical cycling of iron in Spain's acid rivers

USGS Publications Warehouse

Gammons, C.H.; Nimick, D.A.; Parker, S.R.; Snyder, D.M.; McCleskey, R. Blaine; Amils, R.; Poulson, S.R.

2008-01-01

A number of investigations have shown that photoreduction of Fe(III) causes midday accumulations of dissolved Fe(II) in rivers and lakes, leading to large diel (24-h) fluctuations in the concentration and speciation of total dissolved iron. Less well appreciated is the importance of photoreduction in providing chemical energy for bacteria to thrive in low pH waters. Diel variations in water chemistry from the highly acidic (pH 2.3 to 3.1) Ri??o Tinto, Ri??o Odiel, and Ri??o Agrio of southwestern Spain (Iberian Pyrite Belt) resulted in daytime increases in Fe(II) concentration of 15 to 66????M at four diel sampling locations. Dissolved Fe(II) concentrations increased with solar radiation, and one of the stream sites showed an antithetic relationship between dissolved Fe(II) and Fe(III) concentrations; both results are consistent with photoreduction. The diel data were used to estimate rates of microbially catalyzed Fe(II) oxidation (1 to 3??nmol L- 1 s- 1) and maximum rates of Fe(III) photoreduction (1.7 to 4.3??nmol L- 1 s- 1). Bioenergetic calculations indicate that the latter rates are sufficient to build up a population of Fe-oxidizing bacteria to the levels observed in the Ri??o Tinto in about 30??days. We conclude that photoreduction plays an important role in the bioenergetics of the bacterial communities of these acidic rivers, which have previously been shown to be dominated by autotrophic Fe(II)-oxidizers such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans. Given the possibility of the previous existence of acidic, Fe(III)-rich water on Mars, photoreduction may be an important process on other planets, a fact that could have implications to astrobiological research. ?? 2008 Elsevier B.V. All rights reserved.

Microwave-Based Reaction Screening: Tandem Retro-Diels-Alder/Diels-Alder Cycloadditions of ortho-Quinol Dimers

PubMed Central

Dong, Suwei; Cahill, Kath arine J.; Kang, Moon -Il; Colburn, Nancy H.; Henrich, Curtis J.; Wilson, Jennifer A.; Beutler, John A.; Johnson, Richard P.; Porco, John A.

2011-01-01

We have accomplished a parallel screen of cycloaddition partners for ortho-quinols utilizing a plate-based microwave system. Microwave irradiation improves the efficiency of retro-Diels-Alder/Diels-Alder cascades of ortho-quinol dimers which generally proceed in a diastereoselective fashion. Computational studies indicate that asynchronous transition states are favored in Diels-Alder cycloadditions of ortho-quinols. Subsequent biological evaluation of a collection of cycloadducts has identified an inhibitor of activator protein-1 (AP-1), an oncogenic transcription factor. PMID:21942286

A Day in the Life of the Suwannee River: Lagrangian Sampling of Process Rates Along the River Continuum

NASA Astrophysics Data System (ADS)

Cohen, M. J.; Hensley, R. T.; Spangler, M.; Gooseff, M. N.

2017-12-01

A key organizing idea in stream ecology is the river continuum concept (RCC) which makes testable predictions about network-scale variation in metabolic and community attributes. Using high resolution (ca. 0.1 Hz) Lagrangian sampling of a wide suite of solutes - including nitrate, fDOM, dissolved oyxgen and specific conductance, we sampled the river continuum from headwaters to the sea in the Suwannee River (Florida, USA). We specifically sought to test two predictions that follow from the RCC: first, that changes in metabolism and hydraulics lead to progressive reduction in total N retention but greater diel variation with increasing stream order; and second, that variation in metabolic and nutrient processing rates is larger across stream orders than between low order streams. In addition to providing a novel test of theory, these measurements enabled new insights into the evolution of water quality through a complex landscape, in part because main-stem profiles were obtained for both high and historically low flow conditions. We observed strong evidence of metabolism and nutrient retention at low flow. Both the rate of uptake velocity and the mass retention per unit area declined with increasing stream order, and declined dramatically at high flow. Clear evidence for time varying retention (i.e., diel variation) was observed at low flow, but was masked or absent at high flow. In this geologically complex river - with alluvial, spring-fed, and blackwater headwater streams - variation across low-order streams was large, suggesting the presence of many river continuua across the network. This application of longitudinal sampling and inference underscores the utility of changing reference frames to draw new insights, but also highlights some of the challenges that need to be considered and, where possible, controlled.

Metatranscriptome sequence analysis reveals diel periodicity of microbial community gene expression in the ocean's interior

NASA Astrophysics Data System (ADS)

Vislova, A.; Aylward, F.; Sosa, O.; DeLong, E.

2016-02-01

Previous work has revealed diel periodicity of gene expression in key metabolic pathways in both autotrophic and heterotrophic microbes in the surface ocean. In this study, we investigated patterns of diel periodicity of gene expression in depth profiles (25, 75, 125 and 250 meters). We postulated that microbial diel transcriptional signals would be increasingly dampened with depth, and that the timing of peak expression of specific transcripts would be shifted in time between depths, in accordance with depth-dependent diel light variability. Bacterioplankton were sampled from four depths every four hours at station ALOHA (22° 45' N 158° W) over 2 days. RNA was extracted from cells preserved on filters, converted to cDNA, and sequenced on the Illumina platform. Surprisingly, harmonic regression analysis revealed an increasing proportion of genes with diel periodic expression patterns with increasing depth between 25- 125 meters. At 250 meters, the proportion of genes exhibiting diel expression patterns decreased an order of magnitude compared to the photic zone. Community composition, functional gene categories, and diel patterns of gene expression were significantly different between the photic zone and 250 meter samples. The signals driving diel periodic gene expression in microbes at 250 meters is under further investigation. These data are now beginning provide a better understanding of the tempo and mode of microbial dynamics among specific taxa, throughout the ocean's interior.

Diel variation in detection and vocalization rates of king (Rallus elegans) and clapper (Rallus crepitans) rails in intracoastal waterways

USGS Publications Warehouse

Stiffler, Lydia L.; Anderson, James T.; Welsh, Amy B.; Harding, Sergio R.; Costanzo, Gary R.; Katzner, Todd

2017-01-01

Surveys for secretive marsh birds could be improved with refinements to address regional and species-specific variation in detection probabilities and optimal times of day to survey. Diel variation in relation to naïve occupancy, detection rates, and vocalization rates of King (Rallus elegans) and Clapper (R. crepitans) rails were studied in intracoastal waterways in Virginia, USA. Autonomous acoustic devices recorded vocalizations of King and Clapper rails at 75 locations for 48-hr periods within a marsh complex. Naïve King and Clapper rail occupancy did not vary hourly at either the marsh or the study area level. Combined King and Clapper rail detections and vocalizations varied across marshes, decreased as the sampling season progressed, and, for detections, was greatest during low rising tides (P < 0.01). Hourly variation in vocalization and detection rates did not show a pattern but occurred between 7.8% of pairwise comparisons for detections and 10.5% of pairwise comparisons for vocalizations (P < 0.01). Higher rates of detections and vocalizations occurred during the hours of 00:00–00:59, 05:00–05:59, 14:00–15:59, and lower rates during the hours of 07:00–09:59. Although statistically significant, because there were no patterns in these hourly differences, they may not be biologically relevant and are of little use to management. In fact, these findings demonstrate that surveys for King and Clapper rails in Virginia intracoastal waterways may be effectively conducted throughout the day.

Hydrodynamic Controls on Acoustical and Optical Water Properties in Tropical Reefs

DTIC Science & Technology

2012-09-30

scattering, absorption, and backscattering , shows more complex variations, with a strong diel signal , but with a tidal influence reflecting asymmetry in...Relative acoustic backscatter (ABS) profiles were derived from individual ADCP beam echo intensity correcting for range and absorption using the sonar...REFERENCES Deines K. L., 1999, Backscatter estimation using Broadband acoustic Doppler current profilers. Proceedings of the IEEE Sixth Working

Diel variations of the bathymetric distribution of zooplankton groups and biomass in Cap-Ferret Canyon, France

NASA Astrophysics Data System (ADS)

Maycas, Encarna Ribera; Bourdillon, André; Macquart-Moulin, Claude; Passelaigue, Françoise; Patriti, Gilbert

1999-10-01

The bathymetric distribution, abundance and diel vertical migrations (DVM) of zooplankton were investigated along the axis of the Cap-Ferret Canyon (Bay of Biscay, French Atlantic coast) by a consecutive series of synchronous net hauls that sampled the whole water column (0-2000 m in depth) during a diel cycle. The distribution of appendicularians (maximum 189 individuals m -3), cladocerans (maximum 287 individuals m -3), copepods (copepods<4 mm, maximum 773 individuals m -3, copepods>4 mm, maximum 13 individuals m -3), ostracods (maximum 8 individuals m -3), siphonophores (maximum >2 individuals m -3) and peracarids (maximum >600 individuals 1000 m -3) were analysed and represented by isoline diagrams. The biomass of total zooplankton (maximum 18419 μg C m -3, 3780 μg N m -3) and large copepods (>4 mm maximum 2256 μg C m -3, 425 μg N m -3) also were determined. Vertical migration was absent or affected only the epipelagic zone for appendicularians, cladocerans, small copepods and siphonophores. Average amplitude of vertical migration was about 400-500 m for ostracods, some hyperiids and mysids, and large copepods, which were often present in the epipelagic, mesopelagic, and bathypelagic zones. Large copepods can constitute more than 80% of the biomass corresponding to total zooplankton. They may play an important role in the active vertical transfer of carbon and nitrogen.

Diel variation of ichthyoplankton recruitment in a wind-dominated temperate coastal lagoon (Argentina)

NASA Astrophysics Data System (ADS)

Bruno, Daniel O.; Delpiani, Sergio M.; Acha, Eduardo M.

2018-05-01

This study aimed to assess the diel changes of ichthyoplankton occurrence, during a known recruitment period, to a wind-dominated coastal lagoon (Argentina). We collected plankton samples at three sites of the lagoon's inlet area every 3 h during four 24 h cycles in mid austral summer. For each early-life history stage (eggs, yolk sac, preflexion larvae, postflexion larvae and early juveniles), the relationship between the abundance and possible combinations of the time of sampling, the wind effect, the wave period and the tidal state was evaluated by fitting generalized linear mix-effects models (GLMM). The wind effects depending on the time of sampling mainly affected fish abundance in all developmental stages. Overall, the highest abundances were collected at nocturnal hours when low-speed offshore winds blew. In addition, higher abundances of eggs, yolk sac and preflexion larvae were related to the incoming flood tide; whereas higher abundances of postflexion larvae and early juveniles were related to longer wave periods. We argued that the daily variation in the abundance of early-life history stages of fishes is related to the sea-land breeze cycle. Therefore, a conceptual framework of the recruitment process of eggs, larvae and early juveniles of fishes into this estuarine system considering the daily effect of winds is proposed.

The influence of sea ice, wind speed and marine mammals on Southern Ocean ambient sound

PubMed Central

van Opzeeland, Ilse; Boebel, Olaf

2017-01-01

This paper describes the natural variability of ambient sound in the Southern Ocean, an acoustically pristine marine mammal habitat. Over a 3-year period, two autonomous recorders were moored along the Greenwich meridian to collect underwater passive acoustic data. Ambient sound levels were strongly affected by the annual variation of the sea-ice cover, which decouples local wind speed and sound levels during austral winter. With increasing sea-ice concentration, area and thickness, sound levels decreased while the contribution of distant sources increased. Marine mammal sounds formed a substantial part of the overall acoustic environment, comprising calls produced by Antarctic blue whales (Balaenoptera musculus intermedia), fin whales (Balaenoptera physalus), Antarctic minke whales (Balaenoptera bonaerensis) and leopard seals (Hydrurga leptonyx). The combined sound energy of a group or population vocalizing during extended periods contributed species-specific peaks to the ambient sound spectra. The temporal and spatial variation in the contribution of marine mammals to ambient sound suggests annual patterns in migration and behaviour. The Antarctic blue and fin whale contributions were loudest in austral autumn, whereas the Antarctic minke whale contribution was loudest during austral winter and repeatedly showed a diel pattern that coincided with the diel vertical migration of zooplankton. PMID:28280544

A facile microwave-assisted Diels-Alder reaction of vinylboronates.

PubMed

Sarotti, Ariel M; Pisano, Pablo L; Pellegrinet, Silvina C

2010-11-21

The Diels-Alder reaction of vinylboronates can be easily performed using microwave irradiation giving excellent yields of the cycloadducts. Pinacol vinylboronate was the reagent of choice due to its stability towards hydrolysis, operational simplicity and yields of Diels-Alder products. To the best of our knowledge, this is the first example of microwave-assisted Diels-Alder reaction of boron-substituted dienophiles. Subsequent in situ oxidation of the cycloadducts with alkaline hydrogen peroxide afforded the alcohols efficiently.

Diel patterns and temporal trends in spawning activities of Robust Redhorse and River Redhorse in Georgia, assessed using passive acoustic monitoring

USGS Publications Warehouse

Straight, Carrie A.; Jackson, C. Rhett; Freeman, Byron J.; Freeman, Mary C.

2015-01-01

The conservation of imperiled species depends upon understanding threats to the species at each stage of its life history. In the case of many imperiled migratory fishes, understanding how timing and environmental influences affect reproductive behavior could provide managers with information critical for species conservation. We used passive acoustic recorders to document spawning activities for two large-bodied catostomids (Robust Redhorse Moxostoma robustum in the Savannah and Broad rivers, Georgia, and River Redhorse M. carinatum in the Coosawattee River, Georgia) in relation to time of day, water temperature, discharge variation, moonlight, and weather. Robust Redhorse spawning activities in the Savannah and Broad rivers were more frequent at night or in the early morning (0100–0400 hours and 0800–1000 hours, respectively) and less frequent near midday (1300 hours). Spawning attempts in the Savannah and Broad rivers increased over a 3–4-d period and then declined. River Redhorse spawning activities in the Coosawattee River peaked on the first day of recording and declined over four subsequent days; diel patterns were less discernible, although moon illumination was positively associated with spawning rates, which was also observed for Robust Redhorses in the Savannah River. Spawning activity in the Savannah and Broad rivers was negatively associated with water temperature, and spawning activity increased in association with cloud cover in the Savannah River. A large variation in discharge was only measured in the flow-regulated Savannah River and was not associated with spawning attempts. To our knowledge, this is the first study to show diel and multiday patterns in spawning activities for anyMoxostoma species. These patterns and relationships between the environment and spawning activities could provide important information for the management of these species downstream of hydropower facilities.

Lake Metabolism: Comparison of Lake Metabolic Rates Estimated from a Diel CO2- and the Common Diel O2-Technique.

PubMed

Peeters, Frank; Atamanchuk, Dariia; Tengberg, Anders; Encinas-Fernández, Jorge; Hofmann, Hilmar

2016-01-01

Lake metabolism is a key factor for the understanding of turnover of energy and of organic and inorganic matter in lake ecosystems. Long-term time series on metabolic rates are commonly estimated from diel changes in dissolved oxygen. Here we present long-term data on metabolic rates based on diel changes in total dissolved inorganic carbon (DIC) utilizing an open-water diel CO2-technique. Metabolic rates estimated with this technique and the traditional diel O2-technique agree well in alkaline Lake Illmensee (pH of ~8.5), although the diel changes in molar CO2 concentrations are much smaller than those of the molar O2 concentrations. The open-water diel CO2- and diel O2-techniques provide independent measures of lake metabolic rates that differ in their sensitivity to transport processes. Hence, the combination of both techniques can help to constrain uncertainties arising from assumptions on vertical fluxes due to gas exchange and turbulent diffusion. This is particularly important for estimates of lake respiration rates because these are much more sensitive to assumptions on gradients in vertical fluxes of O2 or DIC than estimates of lake gross primary production. Our data suggest that it can be advantageous to estimate respiration rates assuming negligible gradients in vertical fluxes rather than including gas exchange with the atmosphere but neglecting vertical mixing in the water column. During two months in summer the average lake net production was close to zero suggesting at most slightly autotrophic conditions. However, the lake emitted O2 and CO2 during the entire time period suggesting that O2 and CO2 emissions from lakes can be decoupled from the metabolism in the near surface layer.

Diel periodicity and chronology of upstream migration in yellow-phase American eels (Anguilla rostrata)

USGS Publications Warehouse

Aldinger, Joni L.; Welsh, Stuart A.

2017-01-01

Yellow-phase American eel (Anguilla rostrata) upstream migration is temporally punctuated, yet migration chronology within diel time periods is not well-understood. This study examined diel periodicity, chronology, and total length (TL) of six multi-day, high-count (285–1,868 eels) passage events of upstream migrant yellow-phase American eels at the Millville Dam eel ladder, lower Shenandoah River, West Virginia during 2011–2014. We categorized passage by diel periods (vespertine, nocturnal, matutinal, diurnal) and season (spring, summer, late summer/early fall, fall). We depicted passage counts as time-series histograms and used time-series spectral analysis (Fast Fourier Transformation) to identify cyclical patterns and diel periodicity of upstream migration. We created histograms to examine movement patterns within diel periods for each passage event and fit normal mixture models (2–9 mixtures) to describe multiple peaks of passage counts. Periodicity of movements for each passage event followed a 24-h activity cycle with mostly nocturnal movement. Multimodal models were supported by the data; most modes represented nocturnal movements, but modes at or near the transition between twilight and night were also common. We used mixed-model methodology to examine relationships among TL, diel period, and season. An additive-effects model of diel period + season was the best approximating model. A decreasing trend of mean TL occurred across diel movement periods, with the highest mean TL occurring during fall relative to similar mean values of TL for spring, summer, and late summer/early fall. This study increased our understanding of yellow-phase American eels by demonstrating the non-random nature of their upstream migration.

Lake Metabolism: Comparison of Lake Metabolic Rates Estimated from a Diel CO2- and the Common Diel O2-Technique

PubMed Central

Peeters, Frank; Atamanchuk, Dariia; Tengberg, Anders; Encinas-Fernández, Jorge; Hofmann, Hilmar

2016-01-01

Lake metabolism is a key factor for the understanding of turnover of energy and of organic and inorganic matter in lake ecosystems. Long-term time series on metabolic rates are commonly estimated from diel changes in dissolved oxygen. Here we present long-term data on metabolic rates based on diel changes in total dissolved inorganic carbon (DIC) utilizing an open-water diel CO2-technique. Metabolic rates estimated with this technique and the traditional diel O2-technique agree well in alkaline Lake Illmensee (pH of ~8.5), although the diel changes in molar CO2 concentrations are much smaller than those of the molar O2 concentrations. The open-water diel CO2- and diel O2-techniques provide independent measures of lake metabolic rates that differ in their sensitivity to transport processes. Hence, the combination of both techniques can help to constrain uncertainties arising from assumptions on vertical fluxes due to gas exchange and turbulent diffusion. This is particularly important for estimates of lake respiration rates because these are much more sensitive to assumptions on gradients in vertical fluxes of O2 or DIC than estimates of lake gross primary production. Our data suggest that it can be advantageous to estimate respiration rates assuming negligible gradients in vertical fluxes rather than including gas exchange with the atmosphere but neglecting vertical mixing in the water column. During two months in summer the average lake net production was close to zero suggesting at most slightly autotrophic conditions. However, the lake emitted O2 and CO2 during the entire time period suggesting that O2 and CO2 emissions from lakes can be decoupled from the metabolism in the near surface layer. PMID:28002477

Diel horizontal migration in streams: juvenile fish exploit spatial heterogeneity in thermal and trophic resources

USGS Publications Warehouse

Armstrong, Jonathan B.; Schindler, Daniel E.; Ruff, Casey P.; Brooks, Gabriel T.; Bentley, Kale E.; Torgersen, Christian E.

2013-01-01

Vertical heterogeneity in the physical characteristics of lakes and oceans is ecologically salient and exploited by a wide range of taxa through diel vertical migration to enhance their growth and survival. Whether analogous behaviors exploit horizontal habitat heterogeneity in streams is largely unknown. We investigated fish movement behavior at daily timescales to explore how individuals integrated across spatial variation in food abundance and water temperature. Juvenile coho salmon made feeding forays into cold habitats with abundant food, and then moved long distances (350–1300 m) to warmer habitats that accelerated their metabolism and increased their assimilative capacity. This behavioral thermoregulation enabled fish to mitigate trade-offs between trophic and thermal resources by exploiting thermal heterogeneity. Fish that exploited thermal heterogeneity grew at substantially faster rates than did individuals that assumed other behaviors. Our results provide empirical support for the importance of thermal diversity in lotic systems, and emphasize the importance of considering interactions between animal behavior and habitat heterogeneity when managing and restoring ecosystems.

Modeling Diel Oxygen Dynamics and Ecosystem Metabolism in Weeks Bay, Alabama.

EPA Science Inventory

Weeks Bay is a shallow eutrophic estuary that exhibits frequent summertime diel-cycling hypoxia and periods of dissolved oxygen (DO) oversaturation during the day. Diel DO dynamics in shallow estuaries like Weeks Bay are complex, and may be influenced by wind forcing, vertical an...

Modeling Diel Oxygen Dynamics and Ecosystem Metabolism in a Shallow, Eutrophic Estuary

EPA Science Inventory

Weeks Bay is a shallow eutrophic estuary that exhibits frequent summertime diel-cycling hypoxia and periods of dissolved oxygen (DO) oversaturation during the day. Diel DO dynamics in shallow estuaries like Weeks Bay are complex, and may be influenced by wind forcing, vertical an...

Temporal Links in Daily Activity Patterns between Coral Reef Predators and Their Prey

PubMed Central

Bosiger, Yoland J.; McCormick, Mark I.

2014-01-01

Few studies have documented the activity patterns of both predators and their common prey over 24 h diel cycles. This study documents the temporal periodicity of two common resident predators of juvenile reef fishes, Cephalopholis cyanostigma (rockcod) and Pseudochromis fuscus (dottyback) and compares these to the activity and foraging pattern of a common prey species, juvenile Pomacentrus moluccensis (lemon damselfish). Detailed observations of activity in the field and using 24 h infrared video in the laboratory revealed that the two predators had very different activity patterns. C. cyanostigma was active over the whole 24 h period, with a peak in feeding strikes at dusk and increased activity at both dawn and dusk, while P. fuscus was not active at night and had its highest strike rates at midday. The activity and foraging pattern of P. moluccensis directly opposes that of C. cyanostigma with individuals reducing strike rate and intraspecific aggression at both dawn and dusk, and reducing distance from shelter and boldness at dusk only. Juveniles examined were just outside the size-selection window of P. fuscus. We suggest that the relatively predictable diel behaviour of coral reef predators results from physiological factors such as visual sensory abilities, circadian rhythmicity, variation in hunting profitability, and predation risk at different times of the day. Our study suggests that the diel periodicity of P. moluccensis behaviour may represent a response to increased predation risk at times when both the ability to efficiently capture food and visually detect predators is reduced. PMID:25354096

Laboratory and field measurements of enantiomeric monoterpene emissions as a function of chemotype, light and temperature

NASA Astrophysics Data System (ADS)

Song, W.; Staudt, M.; Bourgeois, I.; Williams, J.

2013-10-01

Plants emit significant amounts of monoterpenes into the Earth's atmosphere where they react rapidly to form a multitude of gas phase species and particles. Many monoterpenes exist in mirror images forms or enantiomers. In this study the enantiomeric monoterpene profile for several representative plants (Quercus ilex L., Rosmarinus officinalis L., and Pinus halepensis Mill.) was investigated as a function of chemotype, light and temperature both in the laboratory and in the field. Analysis of enantiomeric monoterpenes from 19 Quercus ilex individuals from Southern France and Spain revealed four regiospecific chemotypes (genetically fixed emission patterns). In agreement with previous work, only Quercus ilex emissions increased strongly with light. However, for all three plant species no consistent enantiomeric variation was observed as a function of light, and the enantiomeric ratio of α-pinene was found vary by less than 20% from 100 and 1000 μmol m-2 s-1 PAR. The rate of monoterpene emission increased with temperature from all three plant species, but little variation in the enantiomeric distribution of α-pinene was observed with temperature. There was more enantiomeric variability between individuals of the same species than could be induced by either light or temperature. Field measurements of α-pinene enantiomer mixing ratios in the air taken at a Quercus ilex forest in Southern France, and several other previously reported field enantiomeric ratio diel cycle profiles are compared. All show smoothly varying diel cycles (some positive and some negative) even over changing wind directions. This is surprising in comparison with variations of enantiomeric emission patterns shown by individuals of the same species.

Diel variation in metabolism and ammonia excretion of Marphysa sanguinea (Polychaeta: Eunicidae)

NASA Astrophysics Data System (ADS)

Yang, Dazuo; Chen, Fudi; Zhou, Yibing; Xiu, Zhilong

2016-11-01

Polychaetes provide an excellent food resource for fish and represent the dominant zoobenthos in marine ecosystems. Diel variation in the rates of metabolism and ammonia-N excretion of Marphysa sanguinea were studied. The worms were grouped according to their wet body weight into small (S; 1.24±0.06 g), medium (M; 4.00±0.30 g), and large (L; 8.54±1.08 g) categories. Their weight-specific metabolic rates, based on aerobic respiration ( R), were measured at 16°C (±0.2°C) and classed as either routine ( R R) or standard ( R S) rates. Both respiration types decreased with increasing body weight. Respiration was described by R = a W b, where b was -0.400 9 and -0.532 0 for R R and R S, respectively. Diurnal changes in R S for each group was relatively flat, with a slightly increasing trend with time, but was relatively stable as a whole. R R of the diurnal variation of worms was higher than R S, but both had similar overall trends. The peak values of specific dynamic action (SDA) ( R SDA) in the S, M, and L groups were 2.704, 1.149, and 0.682 mg/(g•h), respectively. The durations of SDA were 13, 6, and 6 h, respectively and the energy expenditures of SDA were 377.98, 117.34, and 74.94 J/g, respectively. These data indicate that the metabolic rates were higher in smaller individuals, which is advantageous for their rapid growth.

Spatial and Temporal Variations in the Occurrence and Foraging Activity of Coastal Dolphins in Menai Bay, Zanzibar, Tanzania.

PubMed

Temple, Andrew J; Tregenza, Nick; Amir, Omar A; Jiddawi, Narriman; Berggren, Per

2016-01-01

Understanding temporal patterns in distribution, occurrence and behaviour is vital for the effective conservation of cetaceans. This study used cetacean click detectors (C-PODs) to investigate spatial and temporal variation in occurrence and foraging activity of the Indo-Pacific bottlenose (Tursiops aduncus) and Indian Ocean humpback (Sousa plumbea) dolphins resident in the Menai Bay Conservation Area (MBCA), Zanzibar, Tanzania. Occurrence was measured using detection positive minutes. Inter-click intervals were used to identify terminal buzz vocalisations, allowing for analysis of foraging activity. Data were analysed in relation to spatial (location) and temporal (monsoon season, diel phase and tidal phase) variables. Results showed significantly increased occurrence and foraging activity of dolphins in southern areas and during hours of darkness. Higher occurrence at night was not explained by diel variation in echolocation rate and so were considered representative of occurrence patterns. Both tidal phase and monsoon season influenced occurrence but results varied among sites, with no general patterns found. Foraging activity was greatest during hours of darkness, High water and Flood tidal phases. Comparisons of echolocation data among sites suggested differences in the broadband click spectra of MBCA dolphins, possibly indicative of species differences. These dolphin populations are threatened by unsustainable fisheries bycatch and tourism activities. The spatial and temporal patterns identified in this study have implications for future conservation and management actions with regards to these two threats. Further, the results indicate future potential for using passive acoustics to identify and monitor the occurrence of these two species in areas where they co-exist.

Diels-Alder Cycloadditions of Masked o-Benzoquinones with Alkenes.

PubMed

Georgopanou, Effie; Martini, Katerina-Irene; Pantazis, Panagiotis; Pelagias, Paulos; Voulgari, Penelope; Hadjiarapoglou, Lazaros P

2015-10-02

Diels-Alder cycloadditions of 3-oxobut-1-enyl substituted orthoquinone monoketals with olefinic dienophiles furnished functionalized ortho-endo bicyclo[2.2.2]octenone derivatives with high regio- and stereoselectivities. The competition between self-dimerization and Diels-Alder cycloaddition with an external dienophile usually exists, except in the case of 5-substituted orthoquinone monoketal.

Nature's Strategy for Catalyzing Diels-Alder Reaction.

PubMed

Oikawa, Hideaki

2016-04-21

The enzymes catalyzing a Diels-Alder-type reaction have been attractive targets for organic chemists for years. Recently, Zheng et al. (2016) reported the structure of a formal monofunctional Diels-Alderase PyrI4 complexed with the product and unveiled a detailed catalytic mechanism of a highly important enzyme. Copyright © 2016 Elsevier Ltd. All rights reserved.

Circadian Clock Gene Expression in the Coral Favia fragum over Diel and Lunar Reproductive Cycles

PubMed Central

Hoadley, Kenneth D.; Szmant, Alina M.; Pyott, Sonja J.

2011-01-01

Natural light cycles synchronize behavioral and physiological cycles over varying time periods in both plants and animals. Many scleractinian corals exhibit diel cycles of polyp expansion and contraction entrained by diel sunlight patterns, and monthly cycles of spawning or planulation that correspond to lunar moonlight cycles. The molecular mechanisms for regulating such cycles are poorly understood. In this study, we identified four molecular clock genes (cry1, cry2, clock and cycle) in the scleractinian coral, Favia fragum, and investigated patterns of gene expression hypothesized to be involved in the corals' diel polyp behavior and lunar reproductive cycles. Using quantitative PCR, we measured fluctuations in expression of these clock genes over both diel and monthly spawning timeframes. Additionally, we assayed gene expression and polyp expansion-contraction behavior in experimental corals in normal light:dark (control) or constant dark treatments. Well-defined and reproducible diel patterns in cry1, cry2, and clock expression were observed in both field-collected and the experimental colonies maintained under control light:dark conditions, but no pattern was observed for cycle. Colonies in the control light:dark treatment also displayed diel rhythms of tentacle expansion and contraction. Experimental colonies in the constant dark treatment lost diel patterns in cry1, cry2, and clock expression and displayed a diminished and less synchronous pattern of tentacle expansion and contraction. We observed no pattern in cry1, cry2, clock, or cycle expression correlated with monthly spawning events suggesting these genes are not involved in the entrainment of reproductive cycles to lunar light cycles in F. fragum. Our results suggest a molecular clock mechanism, potentially similar to that in described in fruit flies, exists within F. fragum. PMID:21573070

Do larval fishes exhibit diel drift patterns in a large, turbid river?

USGS Publications Warehouse

Reeves, K.S.; Galat, D.L.

2010-01-01

Previous research suggested larval fishes do not exhibit a diel drift cycle in turbid rivers (transparency <30 cm). We evaluated this hypothesis in the turbid, lower Missouri River, Missouri. We also reviewed diel patterns of larval drift over a range of transparencies in rivers worldwide. Larval fishes were collected from the Missouri River primary channel every 4 h per 24-h period during spring-summer 2002. Water transparency was measured during this period and summarized for previous years. Diel drift patterns were analyzed at the assemblage level and lower taxonomic levels for abundant groups. Day and night larval fish catch-per-unit-effort (CPUE) was compared for the entire May through August sampling period and spring (May - June) and summer (July - August) seasons separately. There were no significant differences between day and night CPUE at the assemblage level for the entire sampling period or for the spring and summer seasons. However, Hiodon alosoides, Carpiodes/Ictiobus spp. and Macrhybopsis spp. exhibited a diel cycle of abundance within the drift. This pattern was evident although mean Secchi depth (transparency) ranged from 4 to 25 cm during the study and was <30 cm from May through August over the previous nine years. Larval diel drift studies from 48 rivers excluding the Missouri River indicated the primary drift period for larval fishes was at night in 38 rivers and during the day for five, with the remaining rivers showing no pattern. Water transparency was reported for 10 rivers with six being <30 cm or 'low'. Two of these six turbid rivers exhibited significant diel drift patterns. The effect of water transparency on diel drift of larval fishes appears taxa-specific and patterns of abundant taxa could mask patterns of rare taxa when analyzed only at the assemblage level. ?? 2010 Blackwell Verlag, Berlin.

Diel cycling of zinc in a stream impacted by acid rock drainage: Initial results from a new in situ Zn analyzer

USGS Publications Warehouse

Chapin, T.P.; Nimick, D.A.; Gammons, C.H.; Wanty, R.B.

2007-01-01

Recent work has demonstrated that many trace metals undergo dramatic diel (24-h) cycles in near neutral pH streams with metal concentrations reproducibly changing up to 500% during the diel period (Nimick et al., 2003). To examine diel zinc cycles in streams affected by acid rock drainage, we have developed a novel instrument, the Zn-DigiScan, to continuously monitor in situ zinc concentrations in near real-time. Initial results from a 3-day deployment at Fisher Creek, Montana have demonstrated the ability of the Zn-DigiScan to record diel Zn cycling at levels below 100 ??g/l. Longer deployments of this instrument could be used to examine the effects of episodic events such as rainstorms and snowmelt pulses on zinc loading in streams affected by acid rock drainage. ?? Springer Science+Business Media B.V. 2006.

Computational design of an enzyme catalyst for a stereoselective bimolecular Diels-Alder reaction

PubMed Central

Siegel, Justin B.; Zanghellini, Alexandre; Lovick, Helena M.; Kiss, Gert; Lambert, Abigail R.; St.Clair, Jennifer L.; Gallaher, Jasmine L.; Hilvert, Donald; Gelb, Michael H.; Stoddard, Barry L.; Houk, Kendall N.; Michael, Forrest E.; Baker, David

2011-01-01

The Diels-Alder reaction is a cornerstone in organic synthesis, forming two carbon-carbon bonds and up to four new stereogenic centers in one step. No naturally occurring enzymes have been shown to catalyze bimolecular Diels-Alder reactions. We describe the de novo computational design and experimental characterization of enzymes catalyzing a bimolecular Diels-Alder reaction with high stereoselectivity and substrate specificity. X-ray crystallography confirms that the structure matches the design for the most active of the enzymes, and binding site substitutions reprogram the substrate specificity. Designed stereoselective catalysts for carbon-carbon bond forming reactions should be broadly useful in synthetic chemistry. PMID:20647463

Computational design of an enzyme catalyst for a stereoselective bimolecular Diels-Alder reaction.

PubMed

Siegel, Justin B; Zanghellini, Alexandre; Lovick, Helena M; Kiss, Gert; Lambert, Abigail R; St Clair, Jennifer L; Gallaher, Jasmine L; Hilvert, Donald; Gelb, Michael H; Stoddard, Barry L; Houk, Kendall N; Michael, Forrest E; Baker, David

2010-07-16

The Diels-Alder reaction is a cornerstone in organic synthesis, forming two carbon-carbon bonds and up to four new stereogenic centers in one step. No naturally occurring enzymes have been shown to catalyze bimolecular Diels-Alder reactions. We describe the de novo computational design and experimental characterization of enzymes catalyzing a bimolecular Diels-Alder reaction with high stereoselectivity and substrate specificity. X-ray crystallography confirms that the structure matches the design for the most active of the enzymes, and binding site substitutions reprogram the substrate specificity. Designed stereoselective catalysts for carbon-carbon bond-forming reactions should be broadly useful in synthetic chemistry.

Diel Variability of Total and Speciated Water-Soluble Inorganic Iodine in PM2.5 Aerosol at a Southern California Coastal Site

NASA Astrophysics Data System (ADS)

Pszenny, A.; Cotter, K.; Deegan, B.; Fischer, E.; Johnson, D.

2007-12-01

PM2.5 aerosol was sampled over nominal 3-hour intervals at the head of Zuma Beach in Malibu, California (USA) from 6 to 24 October 2006 by filtration at 1.13 m3 min-1 (STP) through 20 x 25 cm cellulose fiber (Whatman 41) filters that had been rinsed with deionized water (DIW). Exposed filters were removed from support cartridges as soon as possible after retrieval (usually within 2 hours), immediately sealed in clean polyethylene bags, and stored frozen until further processing. Following the field campaign one quarter of each filter was pressed into a pellet (2.0 cm diameter x 0.5 cm thick) and analyzed by neutron activation for total concentrations of I and several other trace elements. Our preliminary analyses indicate that sodium and iodine show a clear diel variation characterized by higher concentrations from late morning to early evening. We hypothesize that this diel variability is related to a persistent land/sea breeze circulation associated with the nearby coastal region. Other elements are indicative of variability in other aerosol sources such as soil dust (Al, Mn) and fossil fuel combustion (V). Second quarters are currently being extracted in DIW and analyzed in two ways: 1) for iodide by ion chromatography, and 2) for inorganic iodine in higher oxidation states (i.e., V to 0) by chemical reduction with ascorbic acid followed by determination of iodide by ion chromatography. Results of the trace element and speciated iodine analyses will be presented.

Phloem as Capacitor: Radial Transfer of Water into Xylem of Tree Stems Occurs via Symplastic Transport in Ray Parenchyma[OPEN

PubMed Central

Renard, Justine; Tjoelker, Mark G.; Salih, Anya

2015-01-01

The transfer of water from phloem into xylem is thought to mitigate increasing hydraulic tension in the vascular system of trees during the diel cycle of transpiration. Although a putative plant function, to date there is no direct evidence of such water transfer or the contributing pathways. Here, we trace the radial flow of water from the phloem into the xylem and investigate its diel variation. Introducing a fluorescent dye (0.1% [w/w] fluorescein) into the phloem water of the tree species Eucalyptus saligna allowed localization of the dye in phloem and xylem tissues using confocal laser scanning microscopy. Our results show that the majority of water transferred between the two tissues is facilitated via the symplast of horizontal ray parenchyma cells. The method also permitted assessment of the radial transfer of water during the diel cycle, where changes in water potential gradients between phloem and xylem determine the extent and direction of radial transfer. When injected during the morning, when xylem water potential rapidly declined, fluorescein was translocated, on average, farther into mature xylem (447 ± 188 µm) compared with nighttime, when xylem water potential was close to zero (155 ± 42 µm). These findings provide empirical evidence to support theoretical predictions of the role of phloem-xylem water transfer in the hydraulic functioning of plants. This method enables investigation of the role of phloem tissue as a dynamic capacitor for water storage and transfer and its contribution toward the maintenance of the functional integrity of xylem in trees. PMID:25588734

Genetic Selection for Improved Abzymes in E. Coli

DTIC Science & Technology

1994-08-03

immunoassay to scemen antibody phage libraries directly for catalysis of a bimolecular Diels - Alder reaction and have identified several active clones...sensitive growth selection assay in F coli for catalysts with chorismate mutase activity; and (3) we identified new abzymes for a Diels - Alder ...generated combinatorial antibody libraries from mRNA isolated from the spleens of mice hyperimmunized with transition state analogs for Diels - Alder and

An analysis of alternative conceptual models relating hyporheic exchange flow to diel fluctuations in discharge during baseflow recession

Treesearch

Steven M. Wondzell; Michael N. Gooseff; Brian L. McGlynn

2009-01-01

Diel fluctuations in streamflow during base flow have been observed in many streams and are typically attributed to water losses from evapotranspiration (ET). However, there is no widely transferable conceptual model that explains how ET results in diel fluctuations in streamflow at the watershed outlet. For fluctuations to occur, two factors must be present: (1) some...

Diel activity of Gulf of Mexico sturgeon in a northwest Florida bay

USGS Publications Warehouse

Wrege, B.M.; Duncan, M.S.; Isely, J.J.

2011-01-01

In this paper, we assess patterns in activity of Gulf of Mexico sturgeon Acipenser oxyrinchus desotoi over a 24-h period in the Pensacola bay system, Florida. Although seasonal migration of sturgeon is well documented, little information is available pertaining to daily variation in activity. We surgically implanted 58 Gulf sturgeon with acoustic transmitters in the Escambia (n=26), Yellow (n=8), Blackwater (n=12) and Choctawhatchee rivers (n=12) in June, July, September and October 2005. Gulf sturgeon location was monitored using an array of 56 fixed-station acoustic receivers. The relationship between frequency of Gulf sturgeon observations recorded on all acoustic receivers and time of day for all seasons combined indicated a strong diel activity pattern. Gulf sturgeon were frequently detected at night in all seasons with the exception of summer. Consecutive hourly observations indicated lateral movement of Gulf sturgeon between independent acoustic receivers on 15% of all observations of individuals. The use of an acoustic receiver array not only provides continuous data within a defined area, but also provides insight into nocturnal behavior of Gulf sturgeon not previously identified. ?? 2011 Blackwell Verlag, Berlin.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bernstein, Hans C.; Brislawn, Colin J.; Dana, Karl

Benthic microbial ecosystems are widespread yet knowledge gaps still remain on the relationships between the diversity of species across kingdoms and productivity. Here, we ask two fundamental questions: 1) How does species diversity relate to the rates of primary and heterotrophic productivity? 2) How do diel variations in light-energy inputs influence productivity and microbiome diversity? To answer these questions, microbial mats from a magnesium sulfate hypersaline Lake were used to establish microcosms. Both the number and relatedness between bacterial and eukaryotic taxa in the microbiome were assayed via amplicon based sequencing of 16S and 18S rRNA genes over two dielmore » cycles. These results correlated with biomass productivity obtained from substrate-specific 13C stable isotope incorporation that enabled comparisons between primary and heterotrophic productivity. Both bacterial and eukaryotic species richness and evenness were related only to the rates of 13C labeled glucose and acetate biomass incorporation. Interestingly, measures of these heterotrophic relationships changed from positive and negative correlations depending on carbon derived from glucose and acetate, respectively. Bacterial and eukaryotic diversity of this ecosystem is also controlled, in part, energy constraints imposed by changing irradiance over a diel cycle.« less

Laboratory and field measurements of enantiomeric monoterpene emissions as a function of chemotype, light and temperature

NASA Astrophysics Data System (ADS)

Song, W.; Staudt, M.; Bourgeois, I.; Williams, J.

2014-03-01

Plants emit significant amounts of monoterpenes into the earth's atmosphere, where they react rapidly to form a multitude of gas phase species and particles. Many monoterpenes exist in mirror-image forms or enantiomers. In this study the enantiomeric monoterpene profile for several representative plants (Quercus ilex L., Rosmarinus officinalis L., and Pinus halepensis Mill.) was investigated as a function of chemotype, light and temperature both in the laboratory and in the field. Analysis of enantiomeric monoterpenes from 19 Quercus ilex individuals from Southern France and Spain revealed four regiospecific chemotypes (genetically fixed emission patterns). In agreement with previous work, only Quercus ilex emissions increased strongly with light. However, for all three plant species no consistent enantiomeric variation was observed as a function of light, and the enantiomeric ratio of α-pinene was found to vary by less than 20% from 100 and 1000 μmol m-2 s-1 PAR (photosynthetically active radiation). The rate of monoterpene emission increased with temperature from all three plant species, but little variation in the enantiomeric distribution of α-pinene was observed with temperature. There was more enantiomeric variability between individuals of the same species than could be induced by either light or temperature. Field measurements of α-pinene enantiomer mixing ratios in the air, taken at a Quercus ilex forest in Southern France, and several other previously reported field enantiomeric ratio diel cycle profiles are compared. All show smoothly varying diel cycles (some positive and some negative) even over changing wind directions. This is surprising in comparison with variations of enantiomeric emission patterns shown by individuals of the same species.

[Thermal tolerance, diel variation of body temperature, and thermal dependence of locomotor performance of hatchling soft-shelled turtles, Trionyx sinensis].

PubMed

Sun, Pingyue; Xu, Xiaoyin; Chen, Huili; Ji, Xiang

2002-09-01

The thermal tolerance, body temperature, and influence of temperature on locomotor performance of hatchling soft-shelled turtles (Trionyx sinensis) were studied under dry and wet conditions, and the selected body temperature of hatchlings was 28.0 and 30.3 degrees C, respectively. Under wet condition, the critical thermal maximum and minimum averaged 40.9 and 7.8 degrees C, respectively. In the environments without thermal gradients, the diel variation of body temperature was highly consistent with the variation of both air and water temperatures, and the body temperature was more directly affected by water temperature than by air temperature, which implied that the physiological thermoregulation of hatchling T. sinensis was very weak. In the environments with thermal gradients, hatchling turtles could maintain relatively high and constant body temperatures, primarily through behavioral thermoregulation. The locomotor performance of hatchling turtles was highly dependent on their body temperature. Within a certain range, the locomotor performance increased with increasing body temperature. In our study, the optimal body temperature for locomotor performance was 31.5 degrees C, under which, the maximum continuous running distance, running distance per minute, and number of stops per minute averaged 1.87 m, 4.92 m.min-1, and 6.2 times.min-1, respectively. The correspondent values at 33.0 degrees C averaged 1.30 m, 4.28 m.min-1, and 7.7 times.min-1, respectively, which indicated that the locomotor performance of hatchling turtles was impaired at 33.0 degrees C. Therefore, extremely high body temperatures might have an adverse effect on locomotor performance of hatchling turtles.

Snapping shrimp sound production patterns on Caribbean coral reefs: relationships with celestial cycles and environmental variables

NASA Astrophysics Data System (ADS)

Lillis, Ashlee; Mooney, T. Aran

2018-06-01

The rich acoustic environment of coral reefs, including the sounds of a variety of fish and invertebrates, is a reflection of the structural complexity and biological diversity of these habitats. Emerging interest in applying passive acoustic monitoring and soundscape analysis to measure coral reef habitat characteristics and track ecological patterns is hindered by a poor understanding of the most common and abundant sound producers on reefs—the snapping shrimp. Here, we sought to address several basic biophysical drivers of reef sound by investigating acoustic activity patterns of snapping shrimp populations on two adjacent coral reefs using a detailed snap detection analysis routine to a high-resolution 2.5-month acoustic dataset from the US Virgin Islands. The reefs exhibited strong diel and lunar periodicity in snap rates and clear spatial differences in snapping levels. Snap rates peaked at dawn and dusk and were higher overall during daytime versus nighttime, a seldom-reported pattern in earlier descriptions of diel snapping shrimp acoustic activity. Small differences between the sites in snap rate rhythms were detected and illustrate how analyses of specific soundscape elements might reveal subtle between-reef variation. Snap rates were highly correlated with environmental variables, including water temperature and light, and were found to be sensitive to changes in oceanographic forcing. This study further establishes snapping shrimp as key players in the coral reef chorus and provides evidence that their acoustic output reflects a combination of environmental conditions, celestial influences, and spatial habitat variation. Effective application of passive acoustic monitoring in coral reef habitats using snap rates or snapping-influenced acoustic metrics will require a mechanistic understanding of the underlying spatial and temporal variation in snapping shrimp sound production across multiple scales.

Pulsed remineralisation in the northwestern Mediterranean Sea: a hypothesis

NASA Astrophysics Data System (ADS)

Denis, Michel; Martin, Valérie; Momzikoff, André; Gondry, Geneviève; Stemmann, Lars; Demers, Serge; Gorsky, Gaby; Andersen, Valérie

2003-02-01

A general study of biogeochemical processes (DYNAPROC cruise) was conducted in May 1995 at a time-series station in the open northwestern Mediterranean Sea where horizontal advection was weak. Short-term variations of the vertical distributions of pico- and nanophytoplankton were investigated over four 36-h cycles, along with parallel determinations of metabolic CO 2 production rates and amino acid-containing colloid (AACC) concentrations at the chlorophyll maximum depth. The vertical (0-1000-m depth) distributions of (i) AACC, (ii) suspended particles and (iii) metabolic CO 2 production rate were documented during the initial and final stages of these 36-h cycles. This study was concerned with diel vertical migration (DVM) of zooplankton, which provided periodic perturbations. Accordingly, the time scale of the experimental work varied from a few hours to a few days. Although all distributions exhibited a periodic behaviour, AACC distributions were generally not linked to diel vertical migrations. In the subsurface layer, Synechococcus made the most abundant population and large variations in concentration were observed both at day and at night. The corresponding integrated (over the upper 90 m) losses of Synechococcus during one night pointed to a potential source of exported organic matter amounting to 534 mg C m -2. This study stresses the potential importance of organic matter export from the euphotic zone through the daily grazing activity of vertically migrating organisms, which would not be accounted for by measurements at longer time scales. The metabolic CO 2 production exhibited a peak of activity below 500 m that was shifted downward, apparently in a recurrent way and independently of the vertical distributions of AACC or of suspended particulate material. To account for this phenomenon, a «sustained wave train» hypothesis is proposed that combines the effect of the diel superficial faecal pellet production by swarming migrators and the repackaging activity of the nonmigrating midwater populations. Our results confirm the recent finding that the particulate compartment is not the major source of the observed instantaneous remineralisation rate and shed a new light on the fate of organic matter in the aphotic zone.

Isotopic Responses to Processes Related to Oxygen Cycling During Diel Studies in the San Joaquin River, California

NASA Astrophysics Data System (ADS)

Silva, S. R.; Young, M. B.; Kendall, C.; Dahlgren, R. A.; Stringfellow, W. T.

2008-12-01

Episodic conditions of low dissolved oxygen (DO) occurring in the San Joaquin River deep water shipping channel (DWSC) at Stockton, California inhibit salmon migration during late summer and early fall. As part of a CALFED study to determine the sources of organic matter and nutrients related to the low DO problem, four diel studies were undertaken: two at the DWSC in 2006 and 2007 and two about 40 miles upstream at Crows Landing in 2005 and 2007. The purpose of the diel studies was to gain a better understanding of the transient processes controlling oxygen concentrations and to compare the range of diel variations of various isotopic measurements with those collected on a less frequent basis. The DWSC is dredged to about 40 feet deep and is tidally influenced. The river at Crows Landing is about 5 feet deep and well above tidal influence. Crows Landing was therefore used for comparison with the DWSC as a hydrologically less complicated portion of the river that has not been dredged. Samples were collected at two hour intervals from a one meter depth at Crows Landing. Values of d18O-DO, DO concentrations and pH showed a strong diel response linked to photosynthesis and the effects of bacterial respiration. The d13C of POM (composed mostly of algae) increased at night as expected while the C:N ratio of POM unexpectedly decreases, possibly due to an increased presence of zooplankton at night. Opposing trends of d15N and d18O of nitrate unrelated to a diurnal cycle suggest that source mixing was largely responsible for nitrate composition and concentration through much of the study. Samples were collected at two hour intervals from 1, 5, and 8 meter depths at Rough and Ready Island in the DWSC. Isotope and concentration data showed a distinct diurnal photosynthetic response at the 1 meter depth only. The 2007 DIC and POM isotopic data suggested that nitrification was significantly responsible for oxygen consumption through the duration of the study. The particularly low flow conditions in 2007 increased residence time and allowed water temperatures to rise accentuating the conditions for low DO concentrations. Compared to Crows Landing, where DO concentrations were near and above air saturation, DO concentrations at the DWSC were almost all below saturation reflecting the greater role of respiration and nitrification in the deeper, slower moving water where photosynthesis is restricted by light penetration and organic debris can accumulate. The diel studies illustrate that isotopes of DO, DIC, nitrate and POM provide unique information about the complex behavior of the DWSC. Furthermore, these data illustrate that sampling at a single depth or at a single time of day may not capture an accurate picture of conditions related to oxygen cycling.

Diversity-Oriented Approaches to Polycyclics and Bioinspired Molecules via the Diels-Alder Strategy: Green Chemistry, Synthetic Economy, and Beyond.

PubMed

Kotha, Sambasivarao; Chavan, Arjun S; Goyal, Deepti

2015-05-11

We describe diverse approaches to various dienes and their utilization in the Diels-Alder reaction to produce a variety of polycycles. The dienes covered here are prepared by simple alkylation reaction or via the Claisen rearrangement or by enyne metathesis of alkyne or enyne building blocks. Here, we have also included the Diels-Alder chemistry of dendralenes, a higher analog of cross-conjugated dienes. The present article is inclusive of o-xylylene derivatives that are generated in situ starting with benzosultine or benzosulfone derivatives. The Diels-Alder reaction of these dienes with various dienophiles gave diverse polycyclic systems and biologically important targets.

Habitat use by fishes of Lake Superior. II. Consequences of diel habitat use for habitat linkages and habitat coupling in nearshore and offshore waters

USGS Publications Warehouse

Gorman, Owen T.; Yule, Daniel L.; Stockwell, Jason D.

2012-01-01

Diel migration patterns of fishes in nearshore (15–80 m depth) and offshore (>80 m) waters of Lake Superior were examined to assess the potential for diel migration to link benthic and pelagic, and nearshore and offshore habitats. In our companion article, we described three types of diel migration: diel vertical migration (DVM), diel bank migration (DBM), and no diel migration. DVM was expressed by fishes migrating from benthopelagic to pelagic positions and DBM was expressed by fishes migrating horizontally from deep to shallow waters at night. Fishes not exhibiting diel migration typically showed increased activity by moving from benthic to benthopelagic positions within demersal habitat. The distribution and biomass of fishes in Lake Superior was characterized by examining 704 bottom trawl samples collected between 2001 and 2008 from four depth zones: ≤40, 41–80, 81–160, and >160 m. Diel migration behaviors of fishes described in our companion article were applied to estimates of areal biomass (kg ha−1) for each species by depth zone. The relative strength of diel migrations were assessed by applying lake area to areal biomass estimates for each species by depth zone to yield estimates of lake-wide biomass (metric tonnes). Overall, species expressing DVM accounted for 83%, DBM 6%, and non-migration 11% of the total lake-wide community biomass. In nearshore waters, species expressing DVM represented 74% of the biomass, DBM 25%, and non-migration 1%. In offshore waters, species expressing DVM represented 85%, DBM 1%, and non-migration 14% of the biomass. Of species expressing DVM, 83% of total biomass occurred in offshore waters. Similarly, 97% of biomass of non-migrators occurred in offshore waters while 83% of biomass of species expressing DBM occurred in nearshore waters. A high correlation (R2 = 0.996) between lake area and community biomass by depth zone resulted in 81% of the lake-wide biomass occurring in offshore waters. Accentuating this nearshore-offshore trend was one of increasing estimated total areal biomass of the fish community with depth zone, which ranged from 13.71 kg ha−1 at depths ≤40 m to 18.81 kg ha−1 at depths >160 m, emphasizing the importance of the offshore fish community to the lake ecosystem. The prevalence of diel migration expressed by Lake Superior fishes increases the potential of fish to link benthic and pelagic and shallow and deepwater habitats. These linkages enhance the potential for habitat coupling, a condition where habitats become interconnected and interdependent through transfers of energy and nutrients. Habitat coupling facilitates energy and nutrient flow through a lake ecosystem, thereby increasing productivity, especially in large lakes where benthic and pelagic, and nearshore and offshore habitats are often well separated. We propose that the application of biomass estimates to patterns of diel migration in fishes can serve as a useful metric for assessing the potential for habitat linkages and habitat coupling in lake ecosystems, and provide an important indicator of ecosystem health and function. The decline of native Lake Trout and ciscoes and recent declines in exotic Alewife and Rainbow Smelt populations in other Great Lakes have likely reduced the capacity for benthic-pelagic coupling in these systems compared to Lake Superior. We recommend comparing the levels and temporal changes in diel migration in other Great Lakes as a means to assess changes in the relative health and function of these ecosystems.

Using diel movement behavior to infer foraging strategies related to ecological and social factors in elephants.

PubMed

Polansky, Leo; Douglas-Hamilton, Iain; Wittemyer, George

2013-01-01

Adaptive movement behaviors allow individuals to respond to fluctuations in resource quality and distribution in order to maintain fitness. Classically, studies of the interaction between ecological conditions and movement behavior have focused on such metrics as travel distance, velocity, home range size or patch occupancy time as the salient metrics of behavior. Driven by the emergence of very regular high frequency data, more recently the importance of interpreting the autocorrelation structure of movement as a behavioral metric has become apparent. Studying movement of a free ranging African savannah elephant population, we evaluated how two movement metrics, diel displacement (DD) and movement predictability (MP - the degree of autocorrelated movement activity at diel time scales), changed in response to variation in resource availability as measured by the Normalized Difference Vegetation Index. We were able to capitalize on long term (multi-year) yet high resolution (hourly) global positioning system tracking datasets, the sample size of which allows robust analysis of complex models. We use optimal foraging theory predictions as a framework to interpret our results, in particular contrasting the behaviors across changes in social rank and resource availability to infer which movement behaviors at diel time scales may be optimal in this highly social species. Both DD and MP increased with increasing forage availability, irrespective of rank, reflecting increased energy expenditure and movement predictability during time periods of overall high resource availability. However, significant interactions between forage availability and social rank indicated a stronger response in DD, and a weaker response in MP, with increasing social status. Relative to high ranking individuals, low ranking individuals expended more energy and exhibited less behavioral movement autocorrelation during lower forage availability conditions, likely reflecting sub-optimal movement behavior. Beyond situations of contest competition, rank status appears to influence the extent to which individuals can modify their movement strategies across periods with differing forage availability. Large-scale spatiotemporal resource complexity not only impacts fine scale movement and optimal foraging strategies directly, but likely impacts rates of inter- and intra-specific interactions and competition resulting in socially based movement responses to ecological dynamics.

Physiological effects of environmentally relevant, multi-day thermal stress on wild juvenile Atlantic salmon (Salmo salar).

PubMed

Corey, Emily; Linnansaari, Tommi; Cunjak, Richard A; Currie, Suzanne

2017-01-01

The frequency of extreme thermal events in temperate freshwater systems is expected to increase alongside global surface temperature. The Miramichi River, located in eastern Canada, is a prominent Atlantic salmon ( Salmo salar ) river where water temperatures can exceed the proposed upper thermal limit for the species (~27°C). Current legislation closes the river to recreational angling when water temperatures exceed 20°C for two consecutive nights. We aimed to examine how natural thermal variation, representative of extreme high thermal events, affected the thermal tolerance and physiology of wild, juvenile Atlantic salmon. We acclimated fish to four thermal cycles, characteristic of real-world thermal conditions while varying daily thermal minima (16°C, 18°C, 20°C or 22°C) and diel thermal fluctuation (e.g. Δ5°C-Δ9°C). In each cycling condition, we assessed the role that thermal minima played on the acute thermal tolerance (critical thermal maximum, (CTMax)), physiological (e.g. heat shock protein 70 (HSP70), ubiquitin) and energetic (e.g. hepatic glycogen, blood glucose and lactate) status of juvenile Atlantic salmon throughout repeated thermal cycles. Exposure to 16-21°C significantly increased CTMax (+0.9°C) compared to a stable acclimation temperature (16°C), as did exposure to diel thermal fluctuations of 18-27°C, 20-27°C and 22-27°C, yet repeated exposure provided no further increases in acute thermal tolerance. In comparison to the reference condition (16-21°C), consecutive days of high temperature cycling with different thermal minima resulted in significant increases in HSP70 and ubiquitin, a significant decrease in liver glycogen, and no significant cumulative effect on either blood glucose or lactate. However, comparison between thermally taxed treatments suggested the diel thermal minima had little influence on the physiological or energetic response of juvenile salmon, despite the variable thermal cycling condition. Our results suggest that relatively cooler night temperatures in the summer months may play a limited role in mitigating physiological stress throughout warm diel cycle events.

Role of persistent low-level clouds in mitigating air quality impacts of wintertime cold pool conditions

NASA Astrophysics Data System (ADS)

VanReken, Timothy M.; Dhammapala, Ranil S.; Jobson, B. Thomas; Bottenus, Courtney L.; VanderSchelden, Graham S.; Kaspari, Susan D.; Gao, Zhongming; Zhu, Qiurui; Lamb, Brian K.; Liu, Heping; Johnston, Jeff

2017-04-01

The Yakima Air Wintertime Nitrate Study (YAWNS) was conducted in January 2013 to investigate the drivers of elevated levels of fine particulate matter (PM2.5) frequently present in the region during winter stagnation periods. An extended stagnation period occurred during the study. For the first four days of the event, skies were clear and the strong diel variation in air pollution patterns were consistent with the expected effects of strong low-level nighttime temperature inversions with moderate mixing during daylight hours. Later in the event a low-level cloud layer formed that persisted over the Yakima Valley for the next seven days while regional conditions remained stagnant. Coincident with the onset of cloud, the levels of all measured primary pollutants, including CO2, CO, NOx, particle number concentration, and black carbon, dropped dramatically and remained low with negligible diel variation for as long as the cloud layer was present. The observed patterns for these air pollutants are consistent with decreased stability and enhanced mixing associated with the cloud-topped boundary layer. Interestingly, levels of secondary pollutants, most notably particulate ammonium nitrate, did not exhibit the same decline. This difference may be due to shifts in the chemical production of secondary pollutants during cloudy conditions, or may merely reflect a further influence of mixing. The results imply that the best strategies for managing wintertime air quality during episodes of persistent cloud are likely different from those needed during clear-sky stagnation events.

Electron requirements for carbon incorporation along a diel light cycle in three marine diatom species.

PubMed

Morelle, Jérôme; Claquin, Pascal

2018-02-23

Diatoms account for about 40% of primary production in highly productive ecosystems. The development of a new generation of fluorometers has made it possible to improve estimation of the electron transport rate from photosystem II, which, when coupled with the carbon incorporation rate enables estimation of the electrons required for carbon fixation. The aim of this study was to investigate the daily dynamics of these electron requirements as a function of the diel light cycle in three relevant diatom species and to apprehend if the method of estimating the electron transport rate can lead to different pictures of the dynamics. The results confirmed the species-dependent capacity for photoacclimation under increasing light levels. Despite daily variations in the photosynthetic parameters, the results of this study underline the low daily variability of the electron requirements estimated using functional absorption of the photosystem II compared to an estimation based on a specific absorption cross section of chlorophyll a. The stability of the electron requirements throughout the day would suggest it is potentially possible to estimate high-frequency primary production by using autonomous variable fluorescence measurements from ships-of-opportunity or moorings, without taking potential daily variation in this parameter into consideration, but this result has to be confirmed on natural phytoplankton assemblages. The results obtained in this study confirm the low electron requirements of diatoms to perform photosynthesis, and suggest a potential additional source of energy for carbon fixation, as recently described in the literature for this class.

Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.

PubMed

Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo

2018-02-02

The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.

Diel movement and habitat use of the golden trout Oncorhynchus mykiss aguabonita in their native habitat on the Golden Trout Wilderness, California

Treesearch

K.R. Matthews

1996-01-01

Abstract.—I used radio transmitters to determine the diel habitat use and movement patterns of California golden trout Oncorhynchus mykiss aquabonita inside and outside cattle exclosures on the South Fork Kern River, Golden Trout Wilderness, California. Twenty-three golden trout were monitored from September 10 to 19, 1993, during 216 diel-tracking hours at four study...

Enhancing the Scope of the Diels-Alder Reaction through Isonitrile Chemistry: Emergence of a New Class of Acyl-Activated Dienophiles

PubMed Central

Townsend, Steven D.; Wu, Xiangyang; Danishefsky, Samuel J.

2012-01-01

α,β-Unsaturated imides, formylated at the nitrogen atom, comprise a new and valuable family of dienophiles for servicing Diels-Alder reactions. These systems are assembled through extension of recently discovered isonitrile chemistry to the domain of α,β-unsaturated acids. Cycloadditions are facilitated by Et2AlCl, presumably via chelation between the two carbonyl groups of the N-formyl amide. Applications of the isonitrile/Diels-Alder logic to the IMDA reaction, as well as methodologies to modify the N-formyl amide of the resultant cycloaddition product, are described. It is expected that this easily executed chemistry will provide a significant enhancement for application of Diels-Alder reactions to many synthetic targets. PMID:22708980

Diel growth dynamics in tree stems: linking anatomy and ecophysiology.

PubMed

Steppe, Kathy; Sterck, Frank; Deslauriers, Annie

2015-06-01

Impacts of climate on stem growth in trees are studied in anatomical, ecophysiological, and ecological disciplines, but an integrative framework to assess those impacts remains lacking. In this opinion article, we argue that three research efforts are required to provide that integration. First, we need to identify the missing links in diel patterns in stem diameter and stem growth and relate those patterns to the underlying mechanisms that control water and carbon balance. Second, we should focus on the understudied mechanisms responsible for seasonal impacts on such diel patterns. Third, information on stem anatomy and ecophysiology should be integrated in the same experiments and mechanistic plant growth models to capture both diel and seasonal scales. Copyright © 2015 Elsevier Ltd. All rights reserved.

Theoretical study of the Diels-Alder reaction between o-benzoquinone and norbornadiene

NASA Astrophysics Data System (ADS)

Quijano-Quiñones, Ramiro F.; Quesadas-Rojas, M.; Cuevas, Gabriel; Mena-Rejón, Gonzalo J.

2013-06-01

The reaction between norbornadiene and o-benzoquinone is an important step in polyalicyclic rigid structures synthesis. It has been considered that this reaction is an example of Diels-Alder (DA) and hetero-Diels-Alder (HDA) cycloadditions with o-benzoquinone acting as diene (forming C-C bonds) and heterodiene (forming O-C bonds). We have performed a Density Functional Theory study of this reaction, employing B3LYP, mPW1PW91, and B1B95 functionals and 6-31G(d,p) and 6-31+G(d,p) Gaussian type basis sets. The results indicate that Diels-Alder is a feasible mechanism for both reactions, but should not be the main route to the formation of products with C-C bonds.

Metabolism and antioxidant defense in the larval chironomid Tanytarsus minutipalpus: adjustments to diel variations in the extreme conditions of Lake Magadi

PubMed Central

Wood, Chris M.; Bergman, Harold L.; Johannsson, Ora E.; Laurent, Pierre; Chevalier, Claudine; Kisipan, Mosiany L.; Kavembe, Geraldine D.; Papah, Michael B.; Brix, Kevin V.; De Boeck, Gudrun; Maina, John N.; Ojoo, Rodi O.; Bianchini, Adalto

2017-01-01

ABSTRACT Insect larvae are reported to be a major component of the simple but highly productive trophic web found in Lake Magadi (Kenya, Africa), which is considered to be one of the most extreme aquatic environments on Earth. Previous studies show that fish must display biochemical and physiological adjustments to thrive under the extreme conditions of the lake. However, information for invertebrates is lacking. In the present study, the occurrence of the larval chironomid Tanytarsus minutipalpus is reported in Lake Magadi for the first time. Additionally, changes in larval metabolism and antioxidant defense correlated with diel variations in the extremely hostile environmental conditions of the lake are described. Wide variations in water temperature (20.2-29.3°C) and dissolved oxygen content (3.2-18.6 mg O2 l−1) were observed at different times of day, without significant change in water pH (10.0±0.03). Temperature and dissolved oxygen were higher at 13:00 h (29.3±0.4°C and 18.6±1.0 mg O2 l−1) and 19:00 h (29.3±0.8°C and 16.2±1.6 mg O2 l−1) and lower at 01:00 h (21.1±0.1°C and 10.7±0.03 mg O2 l−1) and 07:00 h (20.2±0.4°C and 3.2±0.7 mg O2 l−1). Significant and parallel increases in parameters related to metabolism (cholinesterase, glucose, cholesterol, urea, creatinine and hemoglobin) and the antioxidant system (SOD, GPx, GR, GSH and GSSG) were observed in larvae collected at 13:00 h. In contrast, no significant changes were observed in pro-oxidants (ROS and NO), TOSC and oxidative damage parameters (LPO and DNA damage). Therefore, the observed increases in temperature and dissolved O2 content in Lake Magadi were associated with changes in the antioxidant system of T. minutipalpus larvae. Adjustments performed by the chironomid larvae were efficient in maintaining body homeostasis, as well as protecting biomolecules against oxidative damage, so that oxidative stress did not occur. GSH-GSSG and GPx-GR systems appeared to play an essential role in the adjustments displayed by the chironomid larvae during the diel changes in the extreme conditions of Lake Magadi. PMID:27895051

Using Lagrangian sampling to study water quality during downstream transport in the San Luis Drain, California, USA

USGS Publications Warehouse

Volkmar, E.C.; Dahlgren, R.A.; Stringfellow, W.T.; Henson, S.S.; Borglin, S.E.; Kendall, C.; Van Nieuwenhuyse, E. E.

2011-01-01

To investigate the mechanism for diel (24h) changes commonly observed at fixed sampling locations and how these diel changes relate to downstream transport in hypereutrophic surface waters, we studied a parcel of agricultural drainage water as it traveled for 84h in a concrete-lined channel having no additional water inputs or outputs. Algal fluorescence, dissolved oxygen, temperature, pH, conductivity, and turbidity were measured every 30min. Grab samples were collected every 2h for water quality analyses, including nutrients, suspended sediment, and chlorophyll/pheophytin. Strong diel patterns were observed for dissolved oxygen, pH, and temperature within the parcel of water. In contrast, algal pigments and nitrate did not exhibit diel patterns within the parcel of water, but did exhibit strong diel patterns for samples collected at a fixed sampling location. The diel patterns observed at fixed sampling locations for these constituents can be attributed to algal growth during the day and downstream transport (washout) of algae at night. Algal pigments showed a rapid daytime increase during the first 48h followed by a general decrease for the remainder of the study, possibly due to sedimentation and photobleaching. Algal growth (primarily diatoms) was apparent each day during the study, as measured by increasing dissolved oxygen concentrations, despite low phosphate concentrations (<0.01mgL-1). ?? 2011 Elsevier B.V.

Winter diel habitat use and movement by subadult bull trout in the upper Flathead River, Montana

USGS Publications Warehouse

Muhlfeld, Clint C.; Glutting, Steve; Hunt, Rick; Daniels, Durae; Marotz, Brian

2003-01-01

We evaluated the diel habitat use and movement of subadult bull trout Salvelinus confluentus by use of radiotelemetry during winter in the upper Flathead River, Montana. Of the 13 monitored bull trout, 12 (92%) made at least one diel movement to other habitat locations during their respective day–night tracking surveys and moved an average of 73% of the time. The median distance moved from day to night locations by the mobile fish was 86 m (range, 27–594 m). Diel shifts in habitat use by nine of the tagged fish were related to light intensity; nocturnal emergence generally commenced immediately after the onset of night, and daytime concealment occurred at daybreak. When diel shifts in microhabitat use occurred, subadult bull trout moved from deep, midchannel areas during the day to shallow, low-velocity areas along the channel margins without overhead cover at night. Resource managers who wish to protect the overwintering habitat features preferred by subadult bull trout in the upper Flathead River should use natural flow management strategies that maximize and stabilize channel margin habitats at night.

Hysteresis responses of evapotranspiration to meteorological factors at a diel timescale: patterns and causes.

PubMed

Zheng, Han; Wang, Qiufeng; Zhu, Xianjin; Li, Yingnian; Yu, Guirui

2014-01-01

Evapotranspiration (ET) is an important component of the water cycle in terrestrial ecosystems. Understanding the ways in which ET changes with meteorological factors is central to a better understanding of ecological and hydrological processes. In this study, we used eddy covariance measurements of ET from a typical alpine shrubland meadow ecosystem in China to investigate the hysteresis response of ET to environmental variables including air temperature (Ta), vapor pressure deficit (VPD) and net radiation (Rn) at a diel timescale. Meanwhile, the simulated ET by Priestly-Taylor equation was used to interpret the measured ET under well-watered conditions. Pronounced hysteresis was observed in both Ta and VPD response curves of ET. At a similar Ta and VPD, ET was always significantly depressed in the afternoon compared with the morning. But the hysteresis response of ET to Rn was not evident. Similar hysteresis patterns were also observed in the Ta/VPD response curves of simulated ET. The magnitudes of the measured and simulated hysteresis loops showed similar seasonal variation, with relatively smaller values occurring from May to September, which agreed well with the lifetime of plants and the period of rainy season at this site. About 62% and 23% of changes in the strength of measured ET-Ta and ET-VPD loops could be explained by the changes in the strength of simulated loops, respectively. Thus, the time lag between Rn and Ta/VPD is the most important factor generating and modulating the ET-Ta/VPD hysteresis, but plants and water status also contribute to the hysteresis response of ET. Our research confirmed the different hysteresis in the responses of ET to meteorological factors and proved the vital role of Rn in driving the diel course of ET.

Diel predator activity drives a dynamic landscape of fear

USGS Publications Warehouse

Kohl, Michel T.; Stahler, Daniel R.; Metz, Matthew C.; Forester, James D.; Kauffman, Matthew J.; Varley, Nathan; White, P.J.; Smith, Douglas W.; MacNulty, Daniel R.

2017-01-01

A "landscape of fear" (LOF) is a map that describes continuous spatial variation in an animal's perception of predation risk. The relief on this map reflects, for example, places that an animal avoids to minimize risk. Although the LOF concept is a potential unifying theme in ecology that is often invoked to explain the ecological and conservation significance of fear, quantified examples of a LOF over large spatial scales are lacking as is knowledge about the daily dynamics of a LOF. Despite theory and data to the contrary, investigators often assume, implicitly or explicitly, that a LOF is a static consequence of a predator's mere presence. We tested the prediction that a LOF in a large-scale, free-living system is a highly-dynamic map with "peaks" and "valleys" that alternate across the diel (24-hour) cycle in response to daily lulls in predator activity. We did so with extensive data from the case study of Yellowstone elk (Cervus elaphus) and wolves (Canis lupus) that was the original basis for the LOF concept. We quantified the elk LOF, defined here as spatial allocation of time away from risky places and times, across nearly 1000-km2 of northern Yellowstone National Park and found that it fluctuated with the crepuscular activity pattern of wolves, enabling elk to use risky places during wolf downtimes. This may help explain evidence that wolf predation risk has no effect on elk stress levels, body condition, pregnancy, or herbivory. The ability of free-living animals to adaptively allocate habitat use across periods of high and low predator activity within the diel cycle is an underappreciated aspect of animal behavior that helps explain why strong antipredator responses may trigger weak ecological effects, and why a LOF may have less conceptual and practical importance than direct killing.

Say what? Coral reef sounds as indicators of community assemblages and reef conditions

NASA Astrophysics Data System (ADS)

Mooney, T. A.; Kaplan, M. B.

2016-02-01

Coral reefs host some of the highest diversity of life on the planet. Unfortunately, reef health and biodiversity is declining or is threatened as a result of climate change and human influences. Tracking these changes is necessary for effective resource management, yet estimating marine biodiversity and tracking trends in ecosystem health is a challenging and expensive task, especially in many pristine reefs which are remote and difficult to access. Many fishes, mammals and invertebrates make sound. These sounds are reflective of a number of vital biological processes and are a cue for settling reef larvae. Biological sounds may be a means to quantify ecosystem health and biodiversity, however the relationship between coral reef soundscapes and the actual taxa present remains largely unknown. This study presents a comparative evaluation of the soundscape of multiple reefs, naturally differing in benthic cover and fish diversity, in the U.S. Virgin Islands National Park. Using multiple recorders per reef we characterized spacio-temporal variation in biological sound production within and among reefs. Analyses of sounds recorded over 4 summer months indicated diel trends in both fish and snapping shrimp acoustic frequency bands with crepuscular peaks at all reefs. There were small but statistically significant acoustic differences among sites on a given reef raising the possibility of potentially localized acoustic habitats. The strength of diel trends in lower, fish-frequency bands were correlated with coral cover and fish density, yet no such relationship was found with shrimp sounds suggesting that fish sounds may be of higher relevance to tracking certain coral reef conditions. These findings indicate that, in spite of considerable variability within reef soundscapes, diel trends in low-frequency sound production reflect reef community assemblages. Further, monitoring soundscapes may be an efficient means of establishing and monitoring reef conditions.

Dual function catalysts. Dehydrogenation and asymmetric intramolecular Diels-Alder cycloaddition of N-hydroxy formate esters and hydroxamic acids: evidence for a ruthenium-acylnitroso intermediate.

PubMed

Chow, Chun P; Shea, Kenneth J

2005-03-23

The chiral ruthenium salen complex, 13b, functions as an efficient catalyst for the sequential oxidation and asymmetric Diels-Alder cycloaddition of hydroxamic acids and N-hydroxy formate esters. This result provides evidence for the formation of a ruthenium-nitroso formate (acyl nitroso) intermediate. The Diels-Alder precursors are prepared from simple building blocks, and the cycloadducts, bridged oxazinolactams, can serve as useful intermediates in organic synthesis.

Fine Scale Baleen Whale Behavior Observed via Tagging Over Daily Time Scales

DTIC Science & Technology

2012-09-30

right whales and sei whales) and the diel vertical migration behavior of their copepod prey. I hypothesize that (1) right whales track the diel...vertical migration of copepods by feeding near the bottom during the day and at the surface at night, and (2) sei whales are unable to feed on copepods at...depth during the day, and are therefore restricted to feeding on copepods at the surface only. Because copepod diel vertical migration is variable

Fine Scale Baleen Whale Behavior Observed via Tagging Over Daily Time Scales

DTIC Science & Technology

2013-09-30

sei whales) and the diel vertical migration behavior of their copepod prey. I hypothesize that (1) right whales track the diel vertical migration of... copepods by feeding near the bottom during the day and at the surface at night, and (2) sei whales are unable to feed on copepods at depth during the...day, and are therefore restricted to feeding on copepods at the surface only. Because copepod diel vertical migration is variable over time (days to

Natural Diels-Alderases: Elusive and Irresistable

PubMed Central

Klas, Kimberly; Tsukamoto, Sachiko; Sherman, David H.; Williams, Robert M.

2016-01-01

Eight examples of biosynthetic pathways wherein a natural enzyme has been identified and claimed to function as a catalyst for the [4+2] cycloaddition reaction, namely, Diels-Alderases, are briefly reviewed. These are discussed in the context of the mechanistic challenges associated with the technical difficulty of proving that the net formal [4+2] cycloaddition under study, indeed proceeds through a synchronous, mechanism and that the putative biosynthetic enzyme deploys the pericyclic transition state required for a Diels-Alder cycloaddition reaction. PMID:26495876

A Diels-Alder Route to Angularly Functionalized Bicyclic Structures

PubMed Central

Kim, Woo Han; Lee, Jun Hee; Aussedat, Baptiste; Danishefsky, Samuel J.

2010-01-01

A Diels-Alder based route to trans-fused angularly functionalized bicyclic structures has been developed. This transformation features the use of a tetrasubstituted dienophile in the cycloaddition step. PMID:20717474

[Chemistry and biosynthesis of prenylflavonoids].

PubMed

Nomura, T

2001-07-01

Many isoprenylated flavonoids have been isolated from mulberry trees and related plants (Moraceae). Among them, kuwanons G (13) and H (14) were the first isolated active substances exhibiting a hypotensive effect from the Japanese Morus root bark. These compounds are considered to be formed through an enzymatic Diels-Alder reaction of a chalcone (15) and dehydro-kuwanon C (16) or its equivalent. Since that time, about forty kinds of Diels-Alder type adducts structurally similar to that of 13 have been isolated from the moraceous plants. Some strains of Morus alba as well as M. bombycis callus tissues have a high productivity of mulberry Diels-Alder type adducts, such as chalcomoracin (26) and kuwanon J (28). The biosynthesis of the mulberry Diels-Alder type adducts has been studied with the aid of the cell strain. Chalcomoracin (26) and kuwanon J (28) were proved to be enzymatic Diels-Alder type reaction products by the administration experiment with O-methylchalcone derivatives. Furthermore, for the isoprenoid biosynthesis of prenylflavonoids in Morus alba callus tissues, a novel way through the junction of glycolysis and pentose-phosphate cycle was proposed. The crude enzyme fraction catalyzing the Morus Diels-Alder type reaction could be isolated. Studies of phenolic constituents of licorice (Glycyrrhiza species) were carried out. On the course of the structure determination of the phenolic constituents of licorice, two new NMR structure determination methods for prenylflavonoids were found. Furthermore, the prenylphenols isolated from licorice were summarized according to the origin of the materials.

Chemistry and biosynthesis of isoprenylated flavonoids from Japanese mulberry tree

PubMed Central

Nomura, Taro; Hano, Yoshio; Fukai, Toshio

2009-01-01

Many isoprenylated flavonoids have been isolated from Japanese mulberry tree (Moraceae). Among them, kuwanons G (1) and H (2) were the first isolated active substances exhibiting a hypotensive effect. These compounds are considered to be formed through an enzymatic Diels-Alder type reaction between an isoprenyl portion of an isoprenylphenol as the diene and an α, β-double bond of chalcone as the dienophile. The absolute configurations of these Diels-Alder type adducts were confirmed by three different methods. The stereochemistries of the adducts were consistent with those of ones in the Diels-Alder reaction involving exo- and endo-addition. Some strains of Morus alba callus tissues have a high productivity of mulberry Diels-Alder type adducts, such as chalcomoracin (3) and kuwanon J (4). The biosynthetic studies of the mulberry Diels-Alder type adducts have been carried out with the aid of the cell strain. Chalcomoracin (3) and kuwanon J (4) were proved to be enzymatic Diels-Alder type reaction products by the administration experiments with O-methylchalcone derivatives. Furthermore, for the isoprenoid biosynthesis of prenylflavonoids in Morus alba callus tissues by administration of [1,3-13C2]- and [2-13C]-glycerol, a novel way through the junction of glycolysis and pentose-phosphate cycle was proved. Two independent isoprenoid biosynthetic pathways, that for sterols and that for isoprenoidphenols, operate in the Morus alba cell cultures. The former is susceptible to compactin (ML-236) and the latter resists to compactin in the cell cultures, respectively. PMID:19907125

Diel and spatial patterns in the singing behavior of humpback whales off Oahu, Hawaii

NASA Astrophysics Data System (ADS)

Lammers, Marc O.; Stimpert, Alison K.; Au, Whitlow W. L.; Mooney, T. Aran

2005-09-01

The singing behavior of male humpback whales on the winter breeding grounds is still a poorly understood phenomenon. Previous work indicates that the chorusing levels of singing whales off west Maui are higher at night than during the day. However, the cause of this variation is not known. To investigate whether more whales sing at night or whether the same number simply move closer to near-shore recorders following sunset, the abundance and location of singing whales off Kaena Point, Oahu was examined. A bottom-moored recording system was used to establish that the same diel pattern observed off Maui also occurs off Oahu. The location of singing whales was determined by localizing singers along a preset transect track using a towed hydrophone array. More whales were found singing along the coastline examined at night than during the day. There was no indication of a shoreward migration. These results suggest that, at night, singing displays may be a more effective behavioral tactic than direct competition in a pod. Also, more singers were found along the northern part of the coastline, which is dominated by a shallow bank, indicating that singers were selective with respect to where they chose to sing.

Associations between benthic flora and diel changes in dissolved arsenic, phosphorus, and related physico-chemical parameters

USGS Publications Warehouse

Kuwabara, James S.

1992-01-01

Diel relationships between physical and chemical parameters and biomass were examined along a 57-km reach of Whitewood Creek, South Dakota, between 29 August and 2 September 1988. A time lag of ∼3-6 h for fluctuations in soluble reactive phosphorus (SRP) concentrations (ranging from 0.1 to 0.5 μM at the downstream sites) relative to dissolved arsenic (ranging from 0.3 to 1.2 μM as arsenate (pentavalent arsenic)) was consistent with our laboratory studies (reported elsewhere) showing preferential cell sorption of orthophosphate over arsenate by creek periphyton. The potential biological effects on SRP diel fluctuations contrasts with abiotic sorption controls for dissolved arsenate (a chemically similar anion). Cycles for pH, like water temperature cycles, lagged irradiance cycles by 1-3 h. Like pH, the amplitude of dissolved arsenic diel cycles was greatest at the site with most abundant biomass. Diel fluctuations in specific conductance (an indicator of groundwater inputs at elevated conductivity relative to the water column) were out of phase with both SRP and dissolved arsenic concentrations suggesting that groundwater was not the direct source of these solutes.

The effect of pressure on microwave-enhanced Diels-Alder reactions. A case study.

PubMed

Kaval, Nadya; Dehaen, Wim; Kappe, C Oliver; Van der Eycken, Erik

2004-01-21

It is demonstrated that microwave-assisted Diels-Alder reactions of substituted 2(1H)-pyrazinones with ethylene are significantly more effective utilizing pre-pressurized (up to 10 bar) reaction vessels.

Distribution of larval fishes related to potential navigation impacts on the upper Mississippi River, pool 7

USGS Publications Warehouse

Holland, L.E.; Sylvester, J.R.

1983-01-01

Ichthyoplankton samples were collected twice monthly during spring and summer 1981 from a variety of habitats in Navigation Pool 7 of the upper Mississippi River. Larval-fish distributions in the pool and variations in those distributions were analyzed relative to potential impacts of increased commercial navigation. Although as many as 66 species of adults have been found in the area (33 considered common), only 17 taxa were identified from our collections. In April and May, most larvae were collected in main-channel and main-channel-border areas next to major expanses of shallow backwaters. White bass Morone chrysops, yellow perch Perca flavescens, and crappies Pomoxis spp. were predominant. Numerous catostomids also were taken. In June and July, most larvae were taken in the lower pool. Freshwater drum Aplodinotus grunniens and gizzard shad Dorosoma cepedianum predominated in these samples, which also included many cyprinids and centrarchids. Diel patterns of abundance varied with species and sampling location. Freshwater drums were more abundant near the surface at midnight than during the day. Common carp Cyprinus carpio were most abundant in collections at dusk, whereas all other cyprinids were most abundant at dusk and dawn. Numbers of gizzard shad also increased slightly at dusk. Total numbers of larvae collected were greatest at dusk in main-channel and main-channel-border samples; backwater areas produced the greatest catches at midnight and dawn. Seasonal, spatial, diel, and species-specific variations in larval fish abundances significantly influenced the proportion of the community potentially vulnerable to increased boat traffic through Pool 7.

Synthesis of isochromene-type scaffolds via single-flask Diels-Alder-[4 + 2]-annulation sequence of a silyl-substituted diene with menadione.

PubMed

Lee, Jihoon; Panek, James S

2014-06-20

A sequential Diels-Alder reaction/silicon-directed [4 + 2]-annulation was developed to assemble hydroisochromene-type ring systems from menadione 2. In the first step, a Diels-Alder of the 1-silyl-substituted butadiene 1 with 2 furnished an intermediate cyclic allylsilane. Subsequently, TMSOTf promoted a [4 + 2]-annulation through trapping of an oxonium, generated by condensation between an aldehyde and the TBS protected alcohol resulted in the formation of a cis-fused hydroisochromene 13.

The influence of reaction conditions on the Diels-Alder cycloadditions of 2-thio-3-chloroacrylamides; investigation of thermal, catalytic and microwave conditions.

PubMed

Kissane, Marie; Lynch, Denis; Chopra, Jay; Lawrence, Simon E; Maguire, Anita R

2010-12-21

The Diels-Alder cycloadditions of cyclopentadiene and 2,3-dimethyl-1,3-butadiene to a range of 2-thio-3-chloroacrylamides under thermal, catalytic and microwave conditions is described. The influence of reaction conditions on the outcome of the cycloadditions, in particular the stereoselectivity and reaction efficiency, is discussed. While the cycloadditions have been attempted at the sulfide, sulfoxide and sulfone levels of oxidation, use of the sulfoxide derivatives is clearly beneficial for stereoselective construction of Diels-Alder cycloadducts.

Measurement and modeling of diel variability of polybrominated diphenyl ethers and chlordanes in air.

PubMed

Moeckel, Claudia; Macleod, Matthew; Hungerbühler, Konrad; Jones, Kevin C

2008-05-01

Short-term variability of concentrations of polybrominated diphenyl ethers (PBDEs) and chlordanes in air at a semirural site in England over a 5 day period is reported. Four-hour air samples were collected during a period dominated by a high pressure system that produced stable diel (24-h) patterns of meteorological conditions such as temperature and atmospheric boundary layer height. PBDE and chlordane concentrations showed clear diel variability with concentrations in the afternoon and evening being 1.9 - 2.7 times higher than in the early morning. The measurements are interpreted using a multimedia mass balance model parametrized with forcing functions representing local temperature, atmospheric boundary layer height, wind speed and hydroxyl radical concentrations. Model results indicate that reversible, temperature-controlled air-surface exchange is the primary driver of the diel concentration pattern observed for chlordanes and PBDE 28. For higher brominated PBDE congeners (47, 99 and 100), the effect of variable atmospheric mixing height in combination with irreversible deposition on aerosol particles is dominant and explains the diel patterns almost entirely. Higher concentrations of chlordanes and PBDEs in air observed at the end of the study period could be related to likely source areas using back trajectory analysis. This is the first study to clearly document diel variability in concentrations of PBDEs in air over a period of several days. Our model analysis indicates that high daytime and low nighttime concentrations of semivolatile organic chemicals can arise from different underlying driving processes, and are not necessarily evidence of reversible air-surface exchange on a 24-h time scale.

Predator avoidance during reproduction: diel movements by spawning sockeye salmon between stream and lake habitats.

PubMed

Bentley, Kale T; Schindler, Daniel E; Cline, Timothy J; Armstrong, Jonathan B; Macias, Daniel; Ciepiela, Lindsy R; Hilborn, Ray

2014-11-01

Daily movements of mobile organisms between habitats in response to changing trade-offs between predation risk and foraging gains are well established; however, less in known about whether similar tactics are used during reproduction, a time period when many organisms are particularly vulnerable to predators. We investigated the reproductive behaviour of adult sockeye salmon (Oncorhynchus nerka) and the activity of their principal predator, brown bears (Ursus arctos), on streams in south-western Alaska. Specifically, we continuously monitored movements of salmon between lake habitat, where salmon are invulnerable to bears, and three small streams, where salmon spawn and are highly vulnerable to bears. We conducted our study across 2 years that offered a distinct contrast in bear activity and predation rates. Diel movements by adult sockeye salmon between stream and lake habitat were observed in 51.3% ± 17.7% (mean ± SD) of individuals among years and sites. Fish that moved tended to hold in the lake for most of the day and then migrated into spawning streams during the night, coincident with when bear activity on streams tended to be lowest. Additionally, cyclic movements between lakes and spawning streams were concentrated earlier in the spawning season. Individuals that exhibited diel movements had longer average reproductive life spans than those who made only one directed movement into a stream. However, the relative effect was dependent on the timing of bear predation, which varied between years. When predation pressure primarily occurred early in the spawning run (i.e., during the height of the diel movements), movers lived 120-310% longer than non-movers. If predation pressure was concentrated later in the spawning run (i.e. when most movements had ceased), movers only lived 10-60% longer. Our results suggest a dynamic trade-off in reproductive strategies of sockeye salmon; adults must be in the stream to reproduce, but must also avoid predation long enough to spawn. Given the interannual variation in the timing and intensity of predation pressure, the advantages of a particular movement strategy will likely vary among years. Regardless, movements by salmon allowed individuals to exploit fine-scale habitat heterogeneity during reproduction, which appears to be a strategy to reduce predation risk on the spawning grounds. © 2014 The Authors. Journal of Animal Ecology © 2014 British Ecological Society.

Diel behavior of rare earth elements in a mountain stream with acidic to neutral pH

USGS Publications Warehouse

Gammons, C.H.; Wood, S.A.; Nimick, D.A.

2005-01-01

Diel (24-h) changes in concentrations of rare earth elements (REE) were investigated in Fisher Creek, a mountain stream in Montana that receives acid mine drainage in its headwaters. Three simultaneous 24-h samplings were conducted at an upstream station (pH = 3.3), an intermediate station (pH = 5.5), and a downstream station (pH = 6.8). The REE were found to behave conservatively at the two upstream stations. At the downstream station, REE partitioned into suspended particles to a degree that varied with the time of day, and concentrations of dissolved REE were 2.9- to 9.4-fold (190% to 830%) higher in the early morning vs. the late afternoon. The decrease in dissolved REE concentrations during the day coincided with a corresponding increase in the concentration of REE in suspended particles, such that diel changes in the total REE concentrations were relatively minor (27% to 55% increase at night). Across the lanthanide series, the heavy REE partitioned into the suspended solid phase to a greater extent than the light REE. Filtered samples from the downstream station showed a decrease in shale-normalized REE concentration across the lanthanide series, with positive anomalies at La and Gd, and a negative Eu anomaly. As the temperature of the creek increased in the afternoon, the slope of the REE profile steepened and the magnitude of the anomalies increased. The above observations are explained by cyclic adsorption of REE onto suspended particles of hydrous ferric and aluminum oxides (HFO, HAO). Conditional partition coefficients for each REE between the suspended solids and the aqueous phase reached a maximum at 1700 hours and a minimum at 0700 hours. This pattern is attributed to diel variations in stream temperature, possibly reinforced by kinetic factors (i.e., slower rates of reaction at night than during the day). Estimates of the enthalpy of adsorption of each REE onto suspended particles based on the field results averaged +82 kJ/mol and are similar in magnitude to estimates in the literature for adsorption of divalent metal cations onto clays and hydrous metal oxides. The results of this study have important implications to the use of REE as hydrogeochemical tracers in streams. Copyright ?? 2005 Elsevier Ltd.

Preliminary studies on haematological and plasmatic parameters in gilthead sea bream (Sparus aurata) held under day/night temperature variations.

PubMed

Matias, Ana C; Ribeiro, Laura; Araujo, Ravi L; Pousão-Ferreira, Pedro

2018-02-01

This study aimed to evaluate to what extent diel water temperature oscillations over a short period of time (41 h) affected haematologic and plasmatic parameters of gilthead sea bream. Sea bream juveniles (160 fish; 177.2 ± 20.9 g) were divided in two homogenous groups, experimental and control. The experimental group was exposed to water at 22.3 ± 0.6 °C between 5 a.m. and 5 p.m. and to colder water from 5 p.m. to 5 a.m. (temperature variation of 8.6 ± 0.3 °C) during 41h period, whereas for the control group, water temperature was maintained constant (22.4 ± 0.7 °C) for the same period. Fish were fed three times per day (10:30 a.m., 2 p.m., 4 p.m.). Blood was collected from fish caudal veins (n = 6) at different time points (10 a.m., 1 p.m., 5 p.m., 6:30 p.m., 8 p.m. and 10 a.m. of the following day) from each group, for haematologic (haematocrit and haemoglobin) and plasmatic (glucose, cortisol, triglycerides and total protein) determinations. All parameters studied tended to vary throughout the study period, both for experimental and control groups. Significant differences were observed between the two groups for all the studied parameters at different sampling points. These differences were observed near the influence of the cold-water period or during the cooling-water period. Results suggested that colder water temperature cycles depressed fish metabolic activity and affected the levels of the analysed blood-circulating metabolites. Overall, results suggested that stress response was similar for experimental and control groups and that gilthead sea bream were able to cope with diel water temperature variations.

Seismic Surveys Negatively Affect Humpback Whale Singing Activity off Northern Angola

PubMed Central

Cerchio, Salvatore; Strindberg, Samantha; Collins, Tim; Bennett, Chanda; Rosenbaum, Howard

2014-01-01

Passive acoustic monitoring was used to document the presence of singing humpback whales off the coast of Northern Angola, and opportunistically test for the effect of seismic survey activity in the vicinity on the number of singing whales. Two Marine Autonomous Recording Units (MARUs) were deployed between March and December 2008 in the offshore environment. Song was first heard in mid June and continued through the remaining duration of the study. Seismic survey activity was heard regularly during two separate periods, consistently throughout July and intermittently in mid-October/November. Numbers of singers were counted during the first ten minutes of every hour for the period from 24 May to 1 December, and Generalized Additive Mixed Models (GAMMs) were used to assess the effect of survey day (seasonality), hour (diel variation), moon phase and received levels of seismic survey pulses (measured from a single pulse during each ten-minute sampled period) on singer number. Application of GAMMs indicated significant seasonal variation, which was the most pronounced effect when assessing the full dataset across the entire season (p<0.001); however seasonality almost entirely dropped out of top-ranked models when applied to a reduced dataset during the July period of seismic survey activity. Diel variation was significant in both the full and reduced datasets (from p<0.01 to p<0.05) and often included in the top-ranked models. The number of singers significantly decreased with increasing received level of seismic survey pulses (from p<0.01 to p<0.05); this explanatory variable was included among the top ranked models for one MARU in the full dataset and both MARUs in the reduced dataset. This suggests that the breeding display of humpback whales is disrupted by seismic survey activity, and thus merits further attention and study, and potentially conservation action in the case of sensitive breeding populations. PMID:24618836

Seismic surveys negatively affect humpback whale singing activity off northern Angola.

PubMed

Cerchio, Salvatore; Strindberg, Samantha; Collins, Tim; Bennett, Chanda; Rosenbaum, Howard

2014-01-01

Passive acoustic monitoring was used to document the presence of singing humpback whales off the coast of Northern Angola, and opportunistically test for the effect of seismic survey activity in the vicinity on the number of singing whales. Two Marine Autonomous Recording Units (MARUs) were deployed between March and December 2008 in the offshore environment. Song was first heard in mid June and continued through the remaining duration of the study. Seismic survey activity was heard regularly during two separate periods, consistently throughout July and intermittently in mid-October/November. Numbers of singers were counted during the first ten minutes of every hour for the period from 24 May to 1 December, and Generalized Additive Mixed Models (GAMMs) were used to assess the effect of survey day (seasonality), hour (diel variation), moon phase and received levels of seismic survey pulses (measured from a single pulse during each ten-minute sampled period) on singer number. Application of GAMMs indicated significant seasonal variation, which was the most pronounced effect when assessing the full dataset across the entire season (p<0.001); however seasonality almost entirely dropped out of top-ranked models when applied to a reduced dataset during the July period of seismic survey activity. Diel variation was significant in both the full and reduced datasets (from p<0.01 to p<0.05) and often included in the top-ranked models. The number of singers significantly decreased with increasing received level of seismic survey pulses (from p<0.01 to p<0.05); this explanatory variable was included among the top ranked models for one MARU in the full dataset and both MARUs in the reduced dataset. This suggests that the breeding display of humpback whales is disrupted by seismic survey activity, and thus merits further attention and study, and potentially conservation action in the case of sensitive breeding populations.

Diel Vertical Migration Thresholds of Karenia brevis (Dinophyceae).

EPA Science Inventory

Light and nutrient availability change throughout dinoflagellate diel vertical migration (DVM) and/or with subpopulation location in the water column along the west Florida shelf. Typically, the vertical depth of the shelf is greater than the distance a subpopulation can vertical...

Synthesis of 3,4-dihydro-1,8-naphthyridin-2(1H)-ones via microwave-activated inverse electron-demand Diels-Alder reactions.

PubMed

Fadel, Salah; Hajbi, Youssef; Khouili, Mostafa; Lazar, Said; Suzenet, Franck; Guillaumet, Gérald

2014-01-01

Substituted 3,4-dihydro-1,8-naphthyridin-2(1H)-ones have been synthesized with the inverse electron-demand Diels-Alder reaction from 1,2,4-triazines bearing an acylamino group with a terminal alkyne side chain. Alkynes were first subjected to the Sonogashira cross-coupling reaction with aryl halides, the product of which then underwent an intramolecular inverse electron-demand Diels-Alder reaction to yield 5-aryl-3,4-dihydro-1,8-naphthyridin-2(1H)-ones by an efficient synthetic route.

The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry.

PubMed

Polgar, Lorenzo Massimo; van Duin, Martin; Picchioni, Francesco

2016-08-25

A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ethylene-propylene rubber, grafted with maleic anhydride, is thermo-reversibly cross-linked in two steps. The pending anhydride moieties are first modified with furfurylamine to graft furan groups to the rubber backbone. These pendant furan groups are then cross-linked with a bis-maleimide via a Diels-Alder coupling reaction. Both reactions can be performed under a broad range of experimental conditions and can easily be applied on a large scale. The material properties of the resulting Diels-Alder cross-linked rubbers are similar to a peroxide-cured ethylene/propylene/diene rubber (EPDM) reference. The cross-links break at elevated temperatures (> 150 °C) via the retro-Diels-Alder reaction and can be reformed by thermal annealing at lower temperatures (50-70 °C). Reversibility of the system was proven with infrared spectroscopy, solubility tests and mechanical properties. Recyclability of the material was also shown in a practical way, i.e., by cutting a cross-linked sample into small parts and compression molding them into new samples displaying comparable mechanical properties, which is not possible for conventionally cross-linked rubbers.

SPATIAL AND DIEL AVAILABILITY OF FLYING INSECTS AS POTENTIAL DUCKLING FOOD IN PRAIRIE WETLANDS.

EPA Science Inventory

The study examined spatial and diel availibility of flying insects that are a critical food resource to young duckings. Insects were sampled in three native prairie wetlands on the Woodworth Study Area of south-central North Dakota.

A recyclable fluorous organocatalyst for Diels-Alder reactions

PubMed Central

Chu, Qianli; Zhang, Wei; Curran, Dennis P.

2007-01-01

Chiral fluorous imidazolidinone catalyst 2 provides consistently high enantioselectivities in Diels-Alder reactions of dienes and α, β-unsaturated aldehydes. The catalyst can be readily separated from the reaction products by fluorous solid-phase extraction, and recovered in excellent purity for direct reuse. PMID:17710220

Temporal and Spatial Dynamics of Diel-Cycling Hypoxia in Four Northern Gulf of Mexico Estuaries

EPA Science Inventory

Eutrophication of coastal ecosystems has accelerated in recent decades due to population growth and associated nutrient pollution, resulting in increased incidence of hypoxia. Shallow and highly productive estuaries and embayments are particularly susceptible to diel-cycling hypo...

Diel distribution of age-0 largemouth bass, Micropterus salmoides, in B. E. Jordan Lake, North Carolina (USA) and its relation to cover

USGS Publications Warehouse

Irwin, E.R.; Noble, R.L.

2000-01-01

We used prepositioned area electrofishers (PAEs, 10X1.5 m) to assess diel differences in distribution of age-0 largemouth bass, Micropterus salmoides, in August 1992-1993 in a paired sampling design. PAEs were placed parallel to shore in an embayment of an unvegetated reservoir (B. E. Jordan Lake, North Carolina, USA). The catch per unit effort (CPUE=fish/PAE) was significantly higher at night than during the day in both years, indicating that age-0 largemouth bass exhibit nocturnal inshore movements. Age-0 largemouth bass captured inshore during day were smaller than those captured at night, indicating that movement patterns may change ontogenetically. Inshore-offshore movements of age-0 largemouth bass were significantly reduced in the presence of cover, suggesting that diel movements were influenced by specific habitat components. Diel movements likely were related to foraging, resting and predator avoidance behavior and could affect population dynamics and introduce bias in assessment programs.

A new approach to the synthesis of monomers and polymers incorporating furan/maleimide Diels-Alder adducts

NASA Astrophysics Data System (ADS)

Banella, Maria Barbara; Gioia, Claudio; Vannini, Micaela; Colonna, Martino; Celli, Annamaria; Gandini, Alessandro

2016-05-01

The Diels-Alder reaction between furan and maleimide moieties is a well-known and widely used strategy to build bio-based macromolecular structures with peculiar properties. The furan-maleimide adducts are thermally reversible because they can be broken above about 120°C and recombined at lower temperatures. At the moment only the monomers exhibiting the furan or the maleimide moieties on their extremity are used in order to get linear or cross-linked polymeric structures. The innovative idea described here consists in using a monomer bearing two carboxylic acidic groups on its extremities and a furan-maleimide Diels-Alder adduct within its structure. This monomer can give rise to classical polycondensation reactions leading to polymers. These polymers (which are polyesters in the present case) can be broken at high temperatures in correspondence of the furane-maleimide Diels-Alder adduct leading to segments exhibiting furan or maleimide moieties at their extremities, which at lower temperature recombine leading to random or block copolymers.

Regiocontrol by remote substituents. An enantioselective total synthesis of frenolicin B via a highly regioselective Diels-Alder reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kraus, G.A.; Li, J.; Gordon, M.S.

1993-06-30

The quinone subunit is contained in a broad range of biologically important natural products such as frenolicin B, which is a member of the pyranonaphthoquinone family. The diverse biological activity of quinones has led to the development of several new synthetic methods for quinones. Among the pathways featuring a cycloaddition reaction, one of the most general methods for the regiospecific synthesis of substituted quinones was pioneered by H.J. Rapoport and others. This method involves the Diels-Alder reaction of a substituted quinone. As part of a program to evaluate the directing effects of functional groups not directly attached to the atomsmore » undergoing Diels-Alder cycloaddition, we now report that remote substituents on a dienophile can confer excellent regioselectivity in Diels-Alder reactions. This work has led to an extremely direct synthesis of the pyranonaphthoquinone framework and to the first synthesis of frenolicin B (1). 19 refs., 1 fig.« less

Quantifying subtropical North Pacific gyre mixed layer primary productivity from Seaglider observations of diel oxygen cycles

NASA Astrophysics Data System (ADS)

Nicholson, David P.; Wilson, Samuel T.; Doney, Scott C.; Karl, David M.

2015-05-01

Using autonomous underwater gliders, we quantified diurnal periodicity in dissolved oxygen, chlorophyll, and temperature in the subtropical North Pacific near the Hawaii Ocean Time-series (HOT) Station ALOHA during summer 2012. Oxygen optodes provided sufficient stability and precision to quantify diel cycles of average amplitude of 0.6 µmol kg-1. A theoretical diel curve was fit to daily observations to infer an average mixed layer gross primary productivity (GPP) of 1.8 mmol O2 m-3 d-1. Cumulative net community production (NCP) over 110 days was 500 mmol O2 m-2 for the mixed layer, which averaged 57 m in depth. Both GPP and NCP estimates indicated a significant period of below-average productivity at Station ALOHA in 2012, an observation confirmed by 14C productivity incubations and O2/Ar ratios. Given our success in an oligotrophic gyre where biological signals are small, our diel GPP approach holds promise for remote characterization of productivity across the spectrum of marine environments.

Diel Variation of Biogenic Volatile Organic Compound Emissions- A field Study in the Sub, Low and High Arctic on the Effect of Temperature and Light

PubMed Central

Lindwall, Frida; Faubert, Patrick; Rinnan, Riikka

2015-01-01

Many hours of sunlight in the midnight sun period suggest that significant amounts of biogenic volatile organic compounds (BVOCs) may be released from arctic ecosystems during night-time. However, the emissions from these ecosystems are rarely studied and limited to point measurements during daytime. We measured BVOC emissions during 24-hour periods in the field using a push-pull chamber technique and collection of volatiles in adsorbent cartridges followed by analysis with gas chromatography- mass spectrometry. Five different arctic vegetation communities were examined: high arctic heaths dominated by Salix arctica and Cassiope tetragona, low arctic heaths dominated by Salix glauca and Betula nana and a subarctic peatland dominated by the moss Warnstorfia exannulata and the sedge Eriophorum russeolum. We also addressed how climate warming affects the 24-hour emission and how the daytime emissions respond to sudden darkness. The emissions from the high arctic sites were lowest and had a strong diel variation with almost no emissions during night-time. The low arctic sites as well as the subarctic site had a more stable release of BVOCs during the 24-hour period with night-time emissions in the same range as those during the day. These results warn against overlooking the night period when considering arctic emissions. During the day, the quantity of BVOCs and the number of different compounds emitted was higher under ambient light than in darkness. The monoterpenes α-fenchene, α -phellandrene, 3-carene and α-terpinene as well as isoprene were absent in dark measurements during the day. Warming by open top chambers increased the emission rates both in the high and low arctic sites, forewarning higher emissions in a future warmer climate in the Arctic. PMID:25897519

Food resource effects on diel movements and body size of cisco in north-temperate lakes.

PubMed

Ahrenstorff, Tyler D; Hrabik, Thomas R; Jacobson, Peter C; Pereira, Donald L

2013-12-01

The movement patterns and body size of fishes are influenced by a host of physical and biological conditions, including temperature and oxygen, prey densities and foraging potential, growth optimization, and predation risk. Our objectives were to (1) investigate variability in vertical movement patterns of cisco (Coregonus artedi) in a variety of inland lakes using hydroacoustics, (2) explore the causal mechanisms influencing movements through the use of temperature/oxygen, foraging, growth, and predation risk models, and (3) examine factors that may contribute to variations in cisco body size by considering all available information. Our results show that cisco vertical movements vary substantially, with different populations performing normal diel vertical migrations (DVM), no DVM, and reverse DVM in lakes throughout Minnesota and northern Wisconsin, USA. Cisco populations with the smallest body size were found in lakes with lower zooplankton densities. These smaller fish showed movements to areas of highest foraging or growth potential during the day and night, despite moving out of preferred temperature and oxygen conditions and into areas of highest predation risk. In lakes with higher zooplankton densities, cisco grew larger and had movements more consistent with behavioral thermoregulation and predator avoidance, while remaining in areas with less than maximum foraging and growth potential. Furthermore, the composition of potential prey items present in each lake was also important. Cisco that performed reverse DVM consumed mostly copepods and cladocerans, while cisco that exhibited normal DVM or no migration consumed proportionally more macro-zooplankton species. Overall, our results show previously undocumented variation in migration patterns of a fish species, the mechanisms underlying those movements, and the potential impact on their growth potential.

Algal productivity and nitrate assimilation in an effluent dominated concrete lined stream

USGS Publications Warehouse

Kent, Robert; Belitz, Kenneth; Burton, Carmen

2005-01-01

This study examined algal productivity and nitrate assimilation in a 2.85 km reach of Cucamonga Creek, California, a concrete lined channel receiving treated municipal wastewater. Stream nitrate concentrations observed at two stations indicated nearly continuous loss throughout the diel study. Nitrate loss in the reach was approximately 11 mg/L/d or 1.0 g/m2/d as N, most of which occurred during daylight. The peak rate of nitrate loss (1.13 mg/l/hr) occurred just prior to an afternoon total CO2 depletion. Gross primary productivity, as estimated by a model using the observed differences in dissolved oxygen between the two stations, was 228 mg/L/d, or 21 g/m2/d as O2. The observed diel variations in productivity, nitrate loss, pH, dissolved oxygen, and CO2indicate that nitrate loss was primarily due to algal assimilation. The observed levels of productivity and nitrate assimilation were exceptionally high on a mass per volume basis compared to studies on other streams; these rates occurred because of the shallow stream depth. This study suggests that concrete‐lined channels can provide an important environmental service: lowering of nitrate concentrations similar to rates observed in biological treatment systems.

Water color affects the stratification, surface temperature, heat content, and mean epilimnetic irradiance of small lakes

USGS Publications Warehouse

Houser, J.N.

2006-01-01

The effects of water color on lake stratification, mean epilimnetic irradiance, and lake temperature dynamics were examined in small, north-temperate lakes that differed widely in water color (1.5-19.8 m -1). Among these lakes, colored lakes differed from clear lakes in the following ways: (i) the epilimnia were shallower and colder, and mean epilimnetic irradiance was reduced; (ii) the diel temperature cycles were more pronounced; (iii) whole-lake heat accumulation during stratification was reduced. The depth of the epilimnion ranged from 2.5 m in the clearest lake to 0.75 m in the most colored lake, and 91% of the variation in epilimnetic depth was explained by water color. Summer mean morning epilimnetic temperature was ???2??C cooler in the most colored lake compared with the clearest lake. In clear lakes, the diel temperature range (1.4 ?? 0.7??C) was significantly (p = 0.01) less than that in the most colored lake (2.1 ?? 1.0??C). Change in whole-lake heat content was negatively correlated with water color. Increasing water color decreased light penetration more than thermocline depth, leading to reduced mean epilimnetic irradiance in the colored lakes. Thus, in these small lakes, water color significantly affected temperature, thermocline depth, and light climate. ?? 2006 NRC.

Site specific diel methane emission mechanisms in landfills: A field validated process based on vegetation and climate factors.

PubMed

Xin, Danhui; Hao, Yongxia; Shimaoka, Takayuki; Nakayama, Hirofumi; Chai, Xiaoli

2016-11-01

Diel methane emission fluxes from a landfill that was covered by vegetation were investigated to reveal the methane emission mechanisms based on the interaction of vegetation characteristics and climate factors. The methane emissions showed large variation between daytime and nighttime, and the trend of methane emissions exhibited clear bimodal patterns from both Setaria viridis- and Neyraudia reynaudiana-covered areas. Plants play an important role in methane transportation as well as methane oxidation. The notable decrease in methane emissions after plants were cut suggests that methane transportation via plants is the primary way of methane emissions in the vegetated areas of landfill. Within plants, the methane emission fluxes were enhanced due to a convection mechanism. Given that the methane emission flux is highly correlated with the solar radiation during daytime, the convection mechanism could be attributed to the increase in solar radiation. Whereas the methane emission flux is affected by a combined impact of the wind speed and pedosphere characteristics during nighttime. An improved understanding of the methane emission mechanisms in vegetated landfills is expected to develop a reliable model for landfill methane emissions and to attenuate greenhouse gas emissions from landfills. Copyright © 2016 Elsevier Ltd. All rights reserved.

A simple technique for continuous measurement of time-variable gas transfer in surface waters

USGS Publications Warehouse

Tobias, Craig R.; Bohlke, John Karl; Harvey, Judson W.; Busenberg, Eurybiades

2009-01-01

Mass balance models of dissolved gases in streams, lakes, and rivers serve as the basis for estimating wholeecosystem rates for various biogeochemical processes. Rates of gas exchange between water and the atmosphere are important and error-prone components of these models. Here we present a simple and efficient modification of the SF6 gas tracer approach that can be used concurrently while collecting other dissolved gas samples for dissolved gas mass balance studies in streams. It consists of continuously metering SF6-saturated water directly into the stream at a low rate of flow. This approach has advantages over pulse injection of aqueous solutions or bubbling large amounts of SF6 into the stream. By adding the SF6 as a saturated solution, we minimize the possibility that other dissolved gas measurements are affected by sparging and/or bubble injecta. Because the SF6 is added continuously we have a record of changing gas transfer velocity (GTV) that is contemporaneous with the sampling of other nonconservative ambient dissolved gases. Over a single diel period, a 30% variation in GTV was observed in a second-order stream (Sugar Creek, Indiana, USA). The changing GTV could be attributed in part to changes in temperature and windspeed that occurred on hourly to diel timescales.

Evaluating Aquatic Life Benefits of Reducing Nutrient Loading ...

EPA Pesticide Factsheets

Theoretical linkages between excess nutrient loading, nutrient-enhanced community metabolism (i.e., production and respiration), and hypoxia in estuaries are well-understood. In seasonally-stratified estuaries and coastal systems (e.g., Chesapeake Bay, northern Gulf of Mexico), hypoxia is predominantly seasonal, such that the spatial extent indicates potential aquatic life impacts. However, in relatively small and shallow Gulf of Mexico bays and bayous, hypoxia frequently occurs episodically or on a diel basis. This study utilized continuous DO monitoring and 3-D hydrodynamic (Environmental Fluid Dynamics Code) and water quality (Water Quality Analysis Simulation Program) models to examine physical and biological controls on DO dynamics and ecosystem metabolism in Weeks Bay, AL. Observed vertical DO gradients varied on a diel basis, with larger amplitude variations at depth relative to the surface, underscoring the importance of benthic production and respiration as a driver of ecosystem metabolism in shallow estuaries. Hydrodynamic and water quality models simulated seasonal and event-driven dynamics, but struggled to resolve the amplitude of daily DO fluctuations, particularly in bottom waters. Using these data in conjunction with the 10-year continuous O2 record from Weeks Bay, we applied empirical relationships and simple scaling relations to predict how reducing nutrient loading may affect the frequency, severity and duration of hypoxia. We further applied

Assembly of the Isoindolinone Core of Muironolide A by Asymmetric Intramolecular Diels-Alder Cycloaddition

PubMed Central

Flores, Beatris; Molinski, Tadeusz F.

2011-01-01

The hexahydro-1H-isoindolin-1-one core of muironolide A was prepared by asymmetric intramolecular Diels Alder cycloaddition using a variant of the MacMillan organocatalyst which sets the C4,C5 and C11 stereocenters. PMID:21751773

A microwave assisted intramolecular-furan-Diels-Alder approach to 4-substituted indoles.

PubMed

Petronijevic, Filip; Timmons, Cody; Cuzzupe, Anthony; Wipf, Peter

2009-01-07

The key steps of a versatile new protocol for the convergent synthesis of 3,4-disubstituted indoles are the addition of an alpha-lithiated alkylaminofuran to a carbonyl compound, a microwave-accelerated intramolecular Diels-Alder cycloaddition and an in situ double aromatization reaction.

Habitat use by fishes of Lake Superior. I. Diel patterns of habitat use in nearshore and offshore waters of the Apostle Islands region

USGS Publications Warehouse

Gorman, O.T.; Yule, D.L.; Stockwell, J.D.

2012-01-01

Diel patterns of distribution of fishes in nearshore (15–80 m depth) and offshore (>80 m) waters of the Apostle Islands region of Lake Superior were described using bottom trawls, mid-water trawls, and acoustic gear during day and night sampling. These data revealed three types of diel migration: diel vertical migration (DVM), diel bank migration (DBM), and no migration. DVM was expressed by fishes migrating from benthopelagic to pelagic strata and DBM was expressed by fishes migrating horizontally from deeper waters in the day to shallower waters at night while remaining within the benthopelagic stratum. Most fishes that did not exhibit diel migration showed increased nighttime densities as a result of increased activity and movement from benthic to benthopelagic strata. Rainbow Smelt (Osmerus mordax), Cisco (Coregonus artedi), Bloater (C. hoyi), Kiyi (C. kiyi), juvenile Trout-Perch (Percopsis omiscomaycus), and adult siscowet (Salvelinus namaycush siscowet) exhibited DVM. Lake Whitefish (C. clupeaformis), lean Lake Trout (Salvelinus namaycush namaycush), and juvenile siscowet exhibited DBM. Adult Trout-Perch and adult Pygmy Whitefish (Prosopium coulteri) exhibited a mixture of DBM and DVM. Burbot (Lota lota), Slimy Sculpin (Cottus cognatus), Spoonhead Sculpin (C. ricei), and Deepwater Sculpin (Myoxocephalus thompsonii) did not exhibit diel migration, but showed evidence of increased nocturnal activity. Ninespine Stickleback (Pungitius pungitius) exhibited a mixture of DVM and non-migration. Juvenile Pygmy Whitefish did not show a diel change in density or depth distribution. Species showing ontogenetic shifts in depth distribution with larger, adult life stages occupying deeper waters included, Rainbow Smelt, lean and siscowet Lake Trout, Lake Whitefish, Pygmy Whitefish, Ninespine Stickleback and Trout-Perch. Of these species, siscowet also showed an ontogenetic shift from primarily DBM as juveniles to primarily DVM as adults. Across all depths, fishes expressing DVM accounted for 73% of the total estimated community areal biomass (kg ha−1) while those expressing DBM accounted for 25% and non-migratory species represented 2% of the biomass. The proportion of total community biomass exhibiting DVM increased with depth, from 59% to 95% across ≤30 m to >90 m depth zones. Along the same depth gradient, the proportion of total community biomass exhibiting DBM declined from 40% to 1%, while non-migrators increased from 1% to 4%. These results indicate that DVM and DBM behaviors are pervasive in the Lake Superior fish community and potentially provide strong linkages that effect coupling of benthic and pelagic and nearshore and offshore habitats.

Diel variability of mercury phase and species distributions in the Florida Everglades

USGS Publications Warehouse

Krabbenhoft, D.P.; Hurley, J.P.; Olson, M.L.; Cleckner, L.B.

1998-01-01

Preliminary studies of mercury (Hg) cycling in the Everglades revealed that dissolved gaseous mercury (DGM), total mercury (Hg(T)), and reactive mercury (Hg(R)) show reproducible, diel trends. Peak water-column DGM concentrations were observed on or about noon, with a 3 to 7 fold increase over night-time concentrations. Production of DGM appears to cease during dark periods, with nearly constant water column concentrations that were at or near saturation with respect to the overlying air. A simple mass balance shows that the flux of Hg to the atmosphere from diel DGM production and evasion represents about 10% of the annual input from atmospheric deposition. Production of DGM is likely the result of an indirect photolysis reaction that involves the production of reductive species and/or reduction by electron transfer. Diel variability in Hg(T) and Hg(R) appears to be controlled by two factors: inputs from rainfall and photolytic sorption/desorption processes. A possible mechanism involves photolysis of chromophores on the surface of a solid substrate (e.g., the periphyton mat) giving rise to destabilization of sorbed mercury and net desorption during daylight. At night, the sorption reactions predominate and the water-column Hg(T) decreases. Methylmercury (MeHg) also showed diel trends in concentration but were not clearly linked to the solar cycle or rainfall at the study site.

Chromatographic and mass spectrometric fingerprinting analyses of angelica sinensis (Oliv.) diels dietary supplements

USDA-ARS?s Scientific Manuscript database

Angelica sinensis (Oliv.) Diels (“Danggui” in Chinese) is one of the most commonly used Traditional Chinese Medicines (TCMs). It has been used to invigorate blood circulation for the treatment of anemia, hypertension, chronic bronchitis, asthma, rheumatism and cardiovascular diseases. There are a lo...

DIEL FLUX OF DISSOLVED CARBOHYDRATE IN A SALT MARSH AND A SIMULATED ESTUARINE ECOSYSTEM

EPA Science Inventory

The concentrations of total dissolved carbohydrate (TCHO), monosaccharide (MCHO) and polysaccharide (PCHO) were followed over a total of ten diel cycles in a salt marsh and a 13 cu m seawater tank simulating an estuarine ecosystem. Their patterns are compared to those for total d...

The Diels-Alder cyclization of ketenimines.

PubMed

Erb, Jeremy; Strull, Jessica; Miller, David; He, Jean; Lectka, Thomas

2012-04-20

A Diels-Alder reaction between cyclopentadiene and a variety of ketenimines is reported. A copper(I)-bis(phosphine complex catalyzes the cycloaddition across the C═N bond of the ketenimine in a [4 + 2] reaction to give an enamine intermediate that is hydrolyzed upon purification to generate aminoketones. © 2012 American Chemical Society

Day-night and depth differences in haemolymph melatonin of the Norway lobster, Nephrops norvegicus (L.)

NASA Astrophysics Data System (ADS)

Aguzzi, J.; Sanchez-Pardo, J.; García, J. A.; Sardà, F.

2009-10-01

Few studies have been conducted to quantify and understand the role of melatonin in invertebrates, and particularly in crustaceans and in deep-sea animals. In this study, we examined day-night differences in haemolymph melatonin of the burrowing decapod crustacean Nephrops norvegicus (L.) during exposure to cycles of monochromatic blue light (480 nm) and darkness cycles of 10 and 0.1 lx. These differential intensity conditions simulate illumination at the depth of the shelf (80-100 m) and of the slope (300-400 m), where these lobster populations are chiefly found in the Western Mediterranean Sea. Our objectives were: (a) to verify the presence of melatonin in the haemolymph of this species using liquid chromatography/tandem mass spectrometry (LC-MS/MS) and fluorescence HPLC (HPLC); and (b) to study the relationship between diel variations in melatonin concentration and locomotor rhythms, in order to examine whether the former influences behaviour. Melatonin was identified in LC-MS/MS by Q1 and Q3 mass peaks at an elution time of 3.7 min, and it was also detected by HPLC. Melatonin concentration was found to be two orders of magnitude higher at 10 lx (4.8±5.3 ng ml -1) than at 0.1 lx (0.06±0.03 ng ml -1). Also, the increase at daytime in 10 lx was absent in 0.1 lx. When the locomotor rhythm of animals exposed to both photoperiod regimes was compared, the diel periodicity was found to be preserved, but the timing of activity shifted from night to day. Extrapolating these data to the field, we interpret our results to mean that locomotor activity preserves its diel character, but not its phase and amplitude, in a bathymetric range where haemolymph melatonin reduces its concentration and rhythmic fluctuation.

Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining

USGS Publications Warehouse

Borrok, D.M.; Nimick, D.A.; Wanty, R.B.; Ridley, W.I.

2008-01-01

Zinc and Cu play important roles in the biogeochemistry of natural systems, and it is likely that these interactions result in mass-dependent fractionations of their stable isotopes. In this study, we examine the relative abundances of dissolved Zn and Cu isotopes in a variety of stream waters draining six historical mining districts located in the United States and Europe. Our goals were to (1) determine whether streams from different geologic settings have unique or similar Zn and Cu isotopic signatures and (2) to determine whether Zn and Cu isotopic signatures change in response to changes in dissolved metal concentrations over well-defined diel (24-h) cycles. Average ??66Zn and ??65Cu values for streams varied from +0.02??? to +0.46??? and -0.7??? to +1.4???, respectively, demonstrating that Zn and Cu isotopes are heterogeneous among the measured streams. Zinc or Cu isotopic changes were not detected within the resolution of our measurements over diel cycles for most streams. However, diel changes in Zn isotopes were recorded in one stream where the fluctuations of dissolved Zn were the largest. We calculate an apparent separation factor of ???0.3??? (66/64Zn) between the dissolved and solid Zn reservoirs in this stream with the solid taking up the lighter Zn isotope. The preference of the lighter isotope in the solid reservoir may reflect metabolic uptake of Zn by microorganisms. Additional field investigations must evaluate the contributions of soils, rocks, minerals, and anthropogenic components to Cu and Zn isotopic fluxes in natural waters. Moreover, rigorous experimental work is necessary to quantify fractionation factors for the biogeochemical reactions that are likely to impact Cu and Zn isotopes in hydrologic systems. This initial investigation of Cu and Zn isotopes in stream waters suggests that these isotopes may be powerful tools for probing biogeochemical processes in surface waters on a variety of temporal and spatial scales.

A computational study of the Diels-Alder reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride

NASA Astrophysics Data System (ADS)

Rivero, Uxía; Meuwly, Markus; Willitsch, Stefan

2017-09-01

The neutral and cationic Diels-Alder-type reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride have been computationally explored as the first step of a combined experimental and theoretical study. Density functional theory calculations show that the neutral reaction is concerted while the cationic reaction can be either concerted or stepwise. Further isomerizations of the Diels-Alder products have been studied in order to predict possible fragmentation pathways in gas-phase experiments. Rice-Ramsperger-Kassel-Marcus (RRKM) calculations suggest that under single-collision experimental conditions the neutral product may reform the reactants and the cationic product will most likely eliminate CO2.

Nitropyrroles, Diels-Alder reactions assisted by microwave irradiation and solvent effect. An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Mancini, Pedro M. E.; Kneeteman, María N.; Cainelli, Mauro; Ormachea, Carla M.; Domingo, Luis R.

2017-11-01

The behaviors of N-tosylnitropyrroles acting as electrophilic dienophiles in polar Diels-Alder reactions joint to different dienes of increeased nucleophilicity are analyzed. The reactions were developed under microwave irradiation using toluene or protic ionic liquids (PILs) as solvents and in free solvent conditions. In all the cases explored we observed good yields in short reaction times. For these reactions, the free solvent condition and the use of protic ionic liquids as solvents offer similar results. However, the free solvent conditions favor environmental sustainability. The role of PILs in these polar Diels-Alder reactions has been theoretically studied within the Molecular Electron Density Theory.

Tandem enyne metathesis-Diels-Alder reaction for construction of natural product frameworks.

PubMed

Rosillo, Marta; Domínguez, Gema; Casarrubios, Luis; Amador, Ulises; Pérez-Castells, Javier

2004-03-19

Enynes connected through aromatic rings are used as substrates for metathesis reactions. The reactivity of three ruthenium carbene complexes is compared. The resulting 1,3-dienes are suitable precursors of polycyclic structures via a Diels-Alder process. Some domino RCM-Diels-Alder reactions are performed, suggesting a possible beneficial effect of the ruthenium catalyst in the cycloaddition process. Other examples require Lewis acid cocatalyst. When applied to aromatic ynamines or enamines, a new synthesis of vinylindoles is achieved. Monitorization of several metathesis reactions with NMR shows the different behavior for ruthenium catalysts. New carbenic species are detected in some reactions with an important dependence on the solvent used.

ADVANCED INTRAMOLECULAR DIELS-ALDER STUDY TOWARD THE SYNTHESIS OF (-)-MORPHINE: STRUCTURE CORRECTION OF A PREVIOUSLY REPORTED DIELS-ALDER PRODUCT. (R826113)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Interpreting diel hysteresis between soil respiration and temperature

Treesearch

C. Phillips; N. Nickerson; D. Risk; B.J. Bond

2011-01-01

Increasing use of automated soil respiration chambers in recent years has demonstrated complex diel relationships between soil respiration and temperature that are not apparent from less frequent measurements. Soil surface flux is often lagged from soil temperature by several hours, which results in semielliptical hysteresis loops when surface flux is plotted as a...

Seasonal and diel movements of white sturgeon in the lower columbia river

USGS Publications Warehouse

Parsley, M.J.; Popoff, N.D.; Van Der Leeuw, B. K.; Wright, C.D.

2008-01-01

Continuous monitoring of the movements and depths used by white sturgeon Acipenser transmontanus with acoustic telemetry technologies in the lower Columbia River provided information on diel and seasonal migrations, local movements, and site fidelity. White sturgeon moved to shallower water at night and showed greater activity, inferred from rates of movement, than during daytime. The extent of local movement within a season was variable among fish; some fish readily moved among habitats while the movements of others were more constrained. White sturgeon were absent from the study area (river kilometers 45-52) during winter and returned from upstream during the spring, confirming an upstream seasonal migration in the fall and downstream migration in spring. The return of individual fish and reoccupation of areas previously inhabited showed that some white sturgeon exhibit site fidelity. This work shows that studies seeking to characterize habitat for white sturgeon need to be cognizant of diel migrations and site fidelity. We urge caution in the use of limited fish location data to describe habitats if diel activities and fine-scale movements are not known.

Effects of smallmouth bass (Micropterus dolomeiu) on Atlantic salmon (Salmo salar) habitat use and diel movements in an artificial stream.

USGS Publications Warehouse

Zydlewski, Joseph D.; Coghlan, Stephen M.; Trial, Joan G.; Wathen, Gus

2012-01-01

Invasive smallmouth bass Micropterus dolomieu have been introduced to some of the last remaining watersheds that contain wild anadromous Atlantic salmon Salmo salar, yet little is known about the interactions between these species. We used an artificial stream equipped with passive integrated transponder tag antenna arrays to monitor habitat use and movements of age-0 Atlantic salmon and age-0 smallmouth bass in sympatry and allopatry. We used additive and substitutive designs to test for changes in habitat use, diel movements, and diel activity patterns of prior-resident Atlantic salmon or smallmouth bass resulting from the addition of conspecifics or heterospecifics. Atlantic salmon prior residents did not change their habitat use in the presence of conspecific or heterospecific invaders. However, Atlantic salmon invaders did lessen riffle habitat use by smallmouth bass prior residents during daytime. Atlantic salmon and smallmouth bass displayed different diel activity patterns of movement (Atlantic salmon were more nocturnal; smallmouth bass were more diurnal), which were affected by heterospecific introductions. Because the two species tended to favor different habitat types and displayed different diel activity patterns, we suggest that under the conditions tested, the level of interspecific competition for habitat was low. Age-0 Atlantic salmon and smallmouth bass may be able to avoid intense interspecific competition through spatial and temporal habitat partitioning. These data do not, however, predict the potential for competition under different seasonal or ontogenetic circumstances.

Metabolomic profiling in tomato reveals diel compositional changes in fruit affected by source–sink relationships

PubMed Central

Bénard, Camille; Bernillon, Stéphane; Biais, Benoît; Osorio, Sonia; Maucourt, Mickaël; Ballias, Patricia; Deborde, Catherine; Colombié, Sophie; Cabasson, Cécile; Jacob, Daniel; Vercambre, Gilles; Gautier, Hélène; Rolin, Dominique; Génard, Michel; Fernie, Alisdair R.; Gibon, Yves; Moing, Annick

2015-01-01

A detailed study of the diurnal compositional changes was performed in tomato (Solanum lycopersicum cv. Moneymaker) leaves and fruits. Plants were cultivated in a commercial greenhouse under two growth conditions: control and shaded. Expanding fruits and the closest mature leaves were harvested during two different day/night cycles (cloudy or sunny day). High-throughput robotized biochemical phenotyping of major compounds, as well as proton nuclear magnetic resonance and mass spectrometry metabolomic profiling, were used to measure the contents of about 70 metabolites in the leaves and 60 metabolites in the fruits, in parallel with ecophysiological measurements. Metabolite data were processed using multivariate, univariate, or clustering analyses and correlation networks. The shaded carbon-limited plants adjusted their leaf area, decreased their sink carbon demand and showed subtle compositional modifications. For source leaves, several metabolites varied along a diel cycle, including those directly linked to photosynthesis and photorespiration. These metabolites peaked at midday in both conditions and diel cycles as expected. However, transitory carbon storage was limited in tomato leaves. In fruits, fewer metabolites showed diel fluctuations, which were also of lower amplitude. Several organic acids were among the fluctuating metabolites. Diel patterns observed in leaves and especially in fruits differed between the cloudy and sunny days, and between the two conditions. Relationships between compositional changes in leaves and fruits are in agreement with the fact that several metabolic processes of the fruit appeared linked to its momentary supply of sucrose. PMID:25873655

Illustrating the Utility of X-Ray Crystallography for Structure Elucidation through a Tandem Aldol Condensation/Diels-Alder Reaction Sequence

ERIC Educational Resources Information Center

Hoang, Giang T.; Kubo, Tomohiro; Young, Victor G., Jr.; Kautzky, Jacob A.; Wissinger, Jane E.

2015-01-01

Two introductory organic chemistry laboratory experiments are described based on the Diels-Alder reaction of 2,3,4,5-tetraphenylcyclopentadienone, which is synthesized prior to or in a one-pot reaction, with styrene. Students are presented with three possible products, the "endo" and "exo" diastereomers and the decarbonylated…

Microwave-Enhanced Organic Syntheses for the Undergraduate Laboratory: Diels-Alder Cycloaddition, Wittig Reaction, and Williamson Ether Synthesis

ERIC Educational Resources Information Center

Baar, Marsha R.; Falcone, Danielle; Gordon, Christopher

2010-01-01

Microwave heating enhanced the rate of three reactions typically performed in our undergraduate organic chemistry laboratory: a Diels-Alder cycloaddition, a Wittig salt formation, and a Williamson ether synthesis. Ninety-minute refluxes were shortened to 10 min using a laboratory-grade microwave oven. In addition, yields improved for the Wittig…

Retro iminonitroso Diels-Alder reactions: interconversion of nitroso cycloadducts

PubMed Central

Yang, Baiyuan; Lin, Weimin; Krchnak, Viktor; Miller, Marvin J.

2009-01-01

Retro iminonitroso Diels-Alder reactions were investigated in both solution and solid phase. In thermal or Cu(I)-mediated reactions, interconversion of various nitroso cycloadducts occurred in the presence of separate dienes. Up to 99% of conversion was observed. Use of chiral ligands in the Cu(I)-medicated reactions gave new cycloadducts enantioselectively. PMID:20161032

A Computational Experiment of the Endo versus Exo Preference in a Diels-Alder Reaction

ERIC Educational Resources Information Center

Rowley, Christopher N.; Woo, Tom K.

2009-01-01

We have developed and tested a computational laboratory that investigates an endo versus exo Diels-Alder cycloaddition. This laboratory employed density functional theory (DFT) calculations to study the cycloaddition of N-phenylmaleimide to furan. The endo and exo stereoisomers of the product were distinguished by building the two isomers in a…

Sorocenols G and H, Anti-MRSA Oxygen Heterocyclic Diels-Alder-type Adducts from Sorocea muriculata Roots

USDA-ARS?s Scientific Manuscript database

Bioassay-guided fractionation of a root extract of Sorocea muriculata led to the isolation and identification of two new oxygen heterocyclic Diels-Alder-type adducts, sorocenols G (1) and H (2), along with lupeol-3-(3'R-hydroxytetradecanoate) and oxyresveratrol. The structures of 1 and 2 were eluci...

Diel flight behaviour and dispersal patterns of aquatic Coleoptera and Heteroptera species with special emphasis on the importance of seasons

NASA Astrophysics Data System (ADS)

Csabai, Zoltán; Kálmán, Zoltán; Szivák, Ildikó; Boda, Pál

2012-09-01

Dispersal flight is the most important and almost the only way for primary aquatic insects to find new water habitats. During a 30-week-long project, we monitored the flight dispersal behaviour of aquatic beetles and bugs with using highly and horizontally polarizing agricultural black plastic sheets laid onto the ground. Based on the flight data of more than 45,000 individuals and 92 species, we explored and described eight different diel flight activity patterns. We found that seven of eight dispersal patterns are consistent with the previous knowledge, while three conspicuous mass dispersal periods can be identified as in the mid morning and/or around noon and/or at nightfall. As an exception, we found a `daytime' pattern occurred exclusively in spring, in which mass dispersal can be seen from mid morning to late afternoon. In contrast to previous studies, we emphasize here that the seasonality has to be considered in evaluation of the diurnal flight activity. According to the seasons, a `three code sign' was proposed to indicate the diel dispersal flight behaviour of a species for a year. Most of the species utilize different diel activity patterns in different seasons. In spring, the daytime pattern was the preferred type, but in summer and autumn, the evening types were the most popular patterns. We stated that the seasonal change of air temperature has a crucial role in that a pattern could be manifested in a given season or not and brings a need to change the diel dispersal pattern among seasons.

Absence of consistent diel rhythmicity in mated honey bee queen behavior.

PubMed

Johnson, Jennifer N; Hardgrave, Emily; Gill, Curtis; Moore, Darrell

2010-07-01

Relatively little is known about the temporal control of behavior of honey bee queens under natural conditions. To determine if mated honey bee queens possess diel rhythmicity in behavior, we observed them in glass-sided observation hives, employing two focal studies involving continuous observations of individual queens as well as a scan-sampling study of multiple queens. In all cases, all behaviors were observed at all times of the day and night. In four of the five queens examined in focal studies, there were no consistent occurrences of diel periodicity for any of the individual behaviors. A more encompassing measure for periodicity, in which the behaviors were characterized as active (walking, inspecting, egg-laying, begging for food, feeding, and grooming self) or inactive (standing), also failed to reveal consistent diel rhythmicity. Furthermore, there were no consistent diel differences in the number of workers in the queen's retinue. Behavioral arrhythmicity persisted across seasons and despite daily changes in both light and temperature levels. Both day and night levels of behavioral activity were correlated with daytime, but not with nighttime, ambient temperatures. The behavior of the one exceptional queen was not consistent: diurnal activity patterns were present during two 24-h observation sessions but arrhythmicity during another. Based on the behavior observed by all but one of the queens examined in this work, the arrhythmic behavior by the mated honey bee queen inside the colony appears to be similar to that exhibited by worker bees before they approach the age of onset of foraging behavior. Copyright 2010 Elsevier Ltd. All rights reserved.

Quantitative structure-activation barrier relationship modeling for Diels-Alder ligations utilizing quantum chemical structural descriptors.

PubMed

Nandi, Sisir; Monesi, Alessandro; Drgan, Viktor; Merzel, Franci; Novič, Marjana

2013-10-30

In the present study, we show the correlation of quantum chemical structural descriptors with the activation barriers of the Diels-Alder ligations. A set of 72 non-catalysed Diels-Alder reactions were subjected to quantitative structure-activation barrier relationship (QSABR) under the framework of theoretical quantum chemical descriptors calculated solely from the structures of diene and dienophile reactants. Experimental activation barrier data were obtained from literature. Descriptors were computed using Hartree-Fock theory using 6-31G(d) basis set as implemented in Gaussian 09 software. Variable selection and model development were carried out by stepwise multiple linear regression methodology. Predictive performance of the quantitative structure-activation barrier relationship (QSABR) model was assessed by training and test set concept and by calculating leave-one-out cross-validated Q2 and predictive R2 values. The QSABR model can explain and predict 86.5% and 80% of the variances, respectively, in the activation energy barrier training data. Alternatively, a neural network model based on back propagation of errors was developed to assess the nonlinearity of the sought correlations between theoretical descriptors and experimental reaction barriers. A reasonable predictability for the activation barrier of the test set reactions was obtained, which enabled an exploration and interpretation of the significant variables responsible for Diels-Alder interaction between dienes and dienophiles. Thus, studies in the direction of QSABR modelling that provide efficient and fast prediction of activation barriers of the Diels-Alder reactions turn out to be a meaningful alternative to transition state theory based computation.

Diel rhythms in the volatile emission of apple and grape foliage.

PubMed

Giacomuzzi, Valentino; Cappellin, Luca; Nones, Stefano; Khomenko, Iuliia; Biasioli, Franco; Knight, Alan L; Angeli, Sergio

2017-06-01

This study investigated the diel emission of volatile organic compounds (VOCs) from intact apple (Malus x domestica Borkh., cv. Golden Delicious) and grape (Vitis vinifera L., cv. Pinot Noir) foliage. Volatiles were monitored continuously for 48 h by proton transfer reaction - time of flight - mass spectrometry (PTR-ToF-MS). In addition, volatiles were collected by closed-loop-stripping-analysis (CLSA) and characterized by gas chromatography-mass spectrometry (GC-MS) after 1 h and again 24 and 48 h later. Fourteen and ten volatiles were characterized by GC-MS in apple and grape, respectively. The majority of these were terpenes, followed by green leaf volatiles, and aromatic compounds. The PTR-ToF-MS identified 10 additional compounds and established their diel emission rhythms. The most abundant volatiles displaying a diel rhythm included methanol and dimethyl sulfide in both plants, acetone in grape, and mono-, homo- and sesquiterpenes in apple. The majority of volatiles were released from both plants during the photophase; whereas methanol, CO 2 , methyl-butenol and benzeneacetaldehyde were released at significantly higher levels during the scotophase. Acetaldehyde, ethanol, and some green leaf volatiles showed distinct emission bursts in both plants following the daily light switch-off. These new results obtained with a combined analytical approach broaden our understanding of the rhythms of constitutive volatile release from two important horticultural crops. In particular, diel emission of sulfur and nitrogen-containing volatiles are reported here for the first time in these two crops. Copyright © 2017. Published by Elsevier Ltd.

Diel rhythmicity of lipid-body formation in a coral- Symbiodinium endosymbiosis

NASA Astrophysics Data System (ADS)

Chen, W.-N. U.; Kang, H.-J.; Weis, V. M.; Mayfield, A. B.; Jiang, P.-L.; Fang, L.-S.; Chen, C.-S.

2012-06-01

The biogenesis of intracellular lipid bodies (LBs) is dependent upon the symbiotic status between host corals and their intracellular dinoflagellates (genus Symbiodinium), though aside from this observation, little is known about LB behavior and function in this globally important endosymbiosis. The present research aimed to understand how LB formation and density are regulated in the gastrodermal tissue layer of the reef-building coral Euphyllia glabrescens. After tissue fixation and labeling with osmium tetroxide, LB distribution and density were quantified by imaging analysis of serial cryo-sections, and a diel rhythmicity was observed; the onset of solar irradiation at sunrise initiated an increase in LB density and size, which peaked at sunset. Both LB density and size then decreased to basal levels at night. On a seasonal timescale, LB density was found to be significantly positively correlated with seasonal irradiation, with highest densities found in the summer and lowest in the fall. In terms of LB lipid composition, only the concentration of wax esters, and not triglycerides or sterols, exhibited diel variability. This suggests that the metabolism and accumulation of lipids in LBs is at least partially light dependent. Ultrastructural examinations revealed that the LB wax ester concentration correlated with the number of electron-transparent inclusion bodies. Finally, there was a directional redistribution of the LB population across the gastroderm over the diel cycle. Collectively, these data reveal that coral gastrodermal LBs vary in composition and intracellular location over diel cycles, features which may shed light on their function within this coral-dinoflagellate mutualism.

Time Lapse Electrical Resistivity to Connect Evapotranspiration and Groundwater Fluxes in the Critical Zone

NASA Astrophysics Data System (ADS)

Jarvis, S. K.; Harmon, R. E.; Barnard, H. R.; Randall, J.; Singha, K.

2017-12-01

The critical zone (CZ)—an open system extending from canopy top to the base of groundwater—is a highly dynamic and heterogeneous environment. In forested terrain, trees make up a large component of the CZ. This work aims to quantify the connection between vegetation and subsurface water storage at a hillslope scale within a forested watershed in the H.J. Andrews Experimental Forest, Oregon. To identify the mechanism(s) controlling the connection at the hillslope scale, we observe patterns in electrical conductivity using 2D-time lapse-DC resistivity. To compare inversions through time a representative error model was determined using L-curve criterion. Inverted data show high spatial variability in ground electrical conductivity and variation at both diel and seasonal timescales. These changes are most pronounced in areas corresponding to dense vegetation. The diel pattern in electrical conductivity is also observed in monitored sap flow sensors, water-level gauges, tensiometers, and sediment thermal probes. To quantify the temporal connection between these data over the course of the growing season a cross correlation analysis was conducted. Preliminary data show that over the course of the growing season transpiration becomes decoupled from both groundwater and soil moisture. Further decomposition of the inverted time lapse data will highlight spatial variability in electrical conductivity providing insight into the where, when, and how(s) of tree-modified subsurface storage.

Diel ontogenetic shift in parasitic activity in a gnathiid isopod on Caribbean coral reefs

NASA Astrophysics Data System (ADS)

Sikkel, P. C.; Ziemba, R. E.; Sears, W. T.; Wheeler, J. C.

2009-06-01

Ontogenetic niche shifts are characteristic of organisms with complex life cycles such as many marine invertebrates. Research has focused primarily on changes in habitat or diet. However, ontogenetic changes can also occur in the temporal pattern of foraging. Gnathiid isopods feed on fish blood throughout their larval stages and are the primary food item for cleaning organisms on coral reefs. At sites in Australia and the Caribbean, gnathiid larvae exhibit size-related differences in diel activity. However, it is unclear whether this is due to interspecific or intraspecific variation in behavior. Fish were deployed in cages near sunset on shallow reefs off St. John, U.S. Virgin Islands and allowed to be infected with larval gnathiids. Larvae collected from fish retrieved near midnight developed into adults, with most developing into females. In contrast, approximately 80% of gnathiids collected after first light developed into second or third stage larvae, and nearly all of the remaining, large, individuals developed into males. Comparison of ITS2 gene regions from individuals collected in emergence traps from the same reefs during the day versus during the night revealed no differences in this highly variable region. Thus, gnathiid larvae at this locality shift their time of activity as they develop, and larvae developing into males remain active over a longer time period than those developing into females.

Catchment scale controls the temporal connection of transpiration and diel fluctuations in streamflow

Treesearch

C.B. Graham; H.R. Barnard; K.L. Kavanagh; J.P. McNamara

2012-01-01

Diel fluctuations can comprise a significant portion of summer discharge in small to medium catchments. The source of these signals and the manner in which they are propagated to stream gauging sites is poorly understood. In this work, we analysed stream discharge from 15 subcatchments in Dry Creek, Idaho, Reynolds Creek, Idaho, and HJ Andrews, Oregon. We identified...

Bioenergetic evaluation of diel vertical migration by bull trout ( Salvelinus confluentus ) in a thermally stratified reservoir

Treesearch

Madeleine Eckmann; Jason Dunham; Edward J. Connor; Carmen A. Welch

2016-01-01

Many species living in deeper lentic ecosystems exhibit daily movements that cycle through the water column, generally referred to as diel vertical migration (DVM). In this study, we applied bioenergetics modelling to evaluate growth as a hypothesis to explain DVM by bull trout (Salvelinus confluentus) in a thermally stratified reservoir (Ross Lake...

Diterpenoid alkaloids from the roots of Aconitum brachypodum Diels.

PubMed

Yang, Li-Guo; Zhang, Ying-Jie; Xie, Jia-Ying; Xia, Wei-Jun; Zhang, Hai-Yuan; Tang, Meng-Yun; Mei, Shuang-Xi; Cui, Tao; Wang, Jing-Kun; Zhu, Zhao-Yun

2016-09-01

A new diterpenoid alkaloid, named bullatine H (1), along with 10 known diterpenoid alkaloids were isolated from the roots of Aconitum brachypodum Diels (Ranunculaceae). The structure of 1 was elucidated by analysis of its spectroscopic data. It should be noted that compound 1 is the first example with 11, 13-dioxygenated denudatine-type diterpenoid alkaloid isolated from Aconitum brachypodum.

The Synthesis of "N"-Benzyl-2-Azanorbornene via Aqueous Hetero Diels-Alder Reaction: An Undergraduate Project in Organic Synthesis and Structural Analysis

ERIC Educational Resources Information Center

Sauvage, Xavier; Delaude, Lionel

2008-01-01

The synthesis of "N"-benzyl-2-azanorbornene via aqueous hetero Diels-Alder reaction of cyclopentadiene and benzyliminium chloride formed in situ from benzylamine hydrochloride and formaldehyde is described. Characterization of the product was achieved by IR and NMR spectroscopies. The spectral data acquired are thoroughly discussed. Numerous…

Diel activity patterns of the Louisiana pine snakes (Pituophis ruthveni) in eastern Texas

Treesearch

Marc J. Ealy; Robert R. Fleet; D. Craig Rudolph

2004-01-01

This study examined the diel activity patterns of six Louisiana pine snakes in eastern Texas using radio-telemetry. snakes were monitored for 44 days on two study areas from May to October 1996. Louisana pine snakes were primarily diurnal with moderate crepuscular activity, spending the night within pocket gopher burrows or inactive on the surface. During daylight...

Nocturnality in synapsids predates the origin of mammals by over 100 million years

PubMed Central

Angielczyk, K. D.; Schmitz, L.

2014-01-01

Nocturnality is widespread among extant mammals and often considered the ancestral behavioural pattern for all mammals. However, mammals are nested within a larger clade, Synapsida, and non-mammalian synapsids comprise a rich phylogenetic, morphological and ecological diversity. Even though non-mammalian synapsids potentially could elucidate the early evolution of diel activity patterns and enrich the understanding of synapsid palaeobiology, data on their diel activity are currently unavailable. Using scleral ring and orbit dimensions, we demonstrate that nocturnal activity was not an innovation unique to mammals but a character that appeared much earlier in synapsid history, possibly several times independently. The 24 Carboniferous to Jurassic non-mammalian synapsid species in our sample featured eye morphologies consistent with all major diel activity patterns, with examples of nocturnality as old as the Late Carboniferous (ca 300 Ma). Carnivores such as Sphenacodon ferox and Dimetrodon milleri, but also the herbivorous cynodont Tritylodon longaevus were likely nocturnal, whereas most of the anomodont herbivores are reconstructed as diurnal. Recognizing the complexity of diel activity patterns in non-mammalian synapsids is an important step towards a more nuanced picture of the evolutionary history of behaviour in the synapsid clade. PMID:25186003

Scale-dependent temporal variations in stream water geochemistry.

PubMed

Nagorski, Sonia A; Moore, Iohnnie N; McKinnon, Temple E; Smith, David B

2003-03-01

A year-long study of four western Montana streams (two impacted by mining and two "pristine") evaluated surface water geochemical dynamics on various time scales (monthly, daily, and bi-hourly). Monthly changes were dominated by snowmelt and precipitation dynamics. On the daily scale, post-rain surges in some solute and particulate concentrations were similar to those of early spring runoff flushing characteristics on the monthly scale. On the bi-hourly scale, we observed diel (diurnal-nocturnal) cycling for pH, dissolved oxygen, water temperature, dissolved inorganic carbon, total suspended sediment, and some total recoverable metals at some or all sites. A comparison of the cumulative geochemical variability within each of the temporal groups reveals that for many water quality parameters there were large overlaps of concentration ranges among groups. We found that short-term (daily and bi-hourly) variations of some geochemical parameters covered large proportions of the variations found on a much longer term (monthly) time scale. These results show the importance of nesting short-term studies within long-term geochemical study designs to separate signals of environmental change from natural variability.

Scale-dependent temporal variations in stream water geochemistry

USGS Publications Warehouse

Nagorski, S.A.; Moore, J.N.; McKinnon, Temple E.; Smith, D.B.

2003-01-01

A year-long study of four western Montana streams (two impacted by mining and two "pristine") evaluated surface water geochemical dynamics on various time scales (monthly, daily, and bi-hourly). Monthly changes were dominated by snowmelt and precipitation dynamics. On the daily scale, post-rain surges in some solute and particulate concentrations were similar to those of early spring runoff flushing characteristics on the monthly scale. On the bi-hourly scale, we observed diel (diurnal-nocturnal) cycling for pH, dissolved oxygen, water temperature, dissolved inorganic carbon, total suspended sediment, and some total recoverable metals at some or all sites. A comparison of the cumulative geochemical variability within each of the temporal groups reveals that for many water quality parameters there were large overlaps of concentration ranges among groups. We found that short-term (daily and bi-hourly) variations of some geochemical parameters covered large proportions of the variations found on a much longer term (monthly) time scale. These results show the importance of nesting short-term studies within long-term geochemical study designs to separate signals of environmental change from natural variability.

Design and Synthesis of a Library of Tetracyclic Hydroazulenoisoindoles

PubMed Central

Brummond, Kay M.; Mao, Shuli; Shinde, Sunita N.; Johnston, Paul J.; Day, Billy W.

2009-01-01

Forty-four tetracyclic hydroazulenoisoindoles were synthesized via a tandem cyclopropanation/Cope rearrangement followed by a Diels-Alder sequence from easily available five-membered cyclic cross-conjugated trienones. These trienones were obtained from two different routes depending upon whether R1 and R2 are alkyl or amino acid derived functional groups, via a rhodium(I)-catalyzed cycloisomerization reaction. In order to increase diversity, four maleimides and two 1,2,4-triazoline-3,5-diones were used as dienophiles in the Diels-Alder step. Several Diels-Alder adducts were further reacted under palladium-catalyzed hydrogenation conditions, leading to a diastereoselective reduction of the trisubstituted double bond. This library has demonstrated rapid access to a variety of structurally complex natural product-like compounds via stereochemical diversity and building block diversity approaches. PMID:19366169

High Activity and Efficient Turnover by a Simple, Self-Assembled "Artificial Diels-Alderase".

PubMed

Martí-Centelles, Vicente; Lawrence, Andrew L; Lusby, Paul J

2018-02-28

The Diels-Alder (DA) reaction is a cornerstone of synthesis, yet Nature does not use catalysts for intermolecular [4+2] cycloadditions. Attempts to create artificial "Diels-Alderases" have also met with limited success, plagued by product inhibition. Using a simple Pd 2 L 4 capsule we now show DA catalysis that combines efficient turnover alongside enzyme-like hallmarks. This includes excellent activity (k cat /k uncat > 10 3 ), selective transition-state stabilization comparable to the most proficient DA catalytic antibodies, and control over regio- and chemoselectivity that would otherwise be difficult to achieve using small-molecule catalysts. Unlike other catalytic approaches that use synthetic capsules, this method is not defined by entropic effects; instead multiple H-bonding interactions modulate reactivity, reminiscent of enzymatic action.

Calibrating passive acoustic monitoring: correcting humpback whale call detections for site-specific and time-dependent environmental characteristics.

PubMed

Helble, Tyler A; D'Spain, Gerald L; Campbell, Greg S; Hildebrand, John A

2013-11-01

This paper demonstrates the importance of accounting for environmental effects on passive underwater acoustic monitoring results. The situation considered is the reduction in shipping off the California coast between 2008-2010 due to the recession and environmental legislation. The resulting variations in ocean noise change the probability of detecting marine mammal vocalizations. An acoustic model was used to calculate the time-varying probability of detecting humpback whale vocalizations under best-guess environmental conditions and varying noise. The uncorrected call counts suggest a diel pattern and an increase in calling over a two-year period; the corrected call counts show minimal evidence of these features.

Unified Total Syntheses of Fawcettimine Class Alkaloids: Fawcettimine, Fawcettidine, Lycoflexine, and Lycoposerramine B

PubMed Central

Pan, Guojun; Williams, Robert M.

2012-01-01

The total syntheses of the lycopodium alkaloids: fawcettimine, fawcettidine, lycoflexine, and lycoposerramine B have been accomplished through an efficient, unified, and stereocontrolled strategy, which relies on a Diels-Alder reaction to construct the cis-fused 6,5-carbocycles with one all-carbon quaternary center. Access to the enantioselective syntheses of both antipodes of those alkaloids can be achieved by kinetic resolution of the earliest intermediate via a Sharpless asymmetric dihydroxylation (Sharpless AD). Compared to existing approaches to these alkaloids, our synthetic route possesses superior stereocontrol over the C-4 and C-15 stereogenic centers as well as allowing for more functional variation on the 6-membered ring. PMID:22519642

Dissipation Rate of Turbulent Kinetic Energy in Diel Vertical Migrations: Comparison of ANSYS Fluent Model to Measurements

NASA Astrophysics Data System (ADS)

Dean, Cayla; Soloviev, Alexander; Hirons, Amy; Frank, Tamara; Wood, Jon

2015-04-01

Recent studies suggest that diel vertical migrations of zooplankton may have an impact on ocean mixing, though details are not completely clear. A strong sound scattering layer of zooplankton undergoing diel vertical migrations was observed in Saanich Inlet, British Colombia, Canada by Kunze et al. (2006). In this study, a shipboard 200-kHz echosounder was used to track vertical motion of the sound scattering layer, and microstructure profiles were collected to observe turbulence. An increase of dissipation rate of turbulent kinetic energy by four to five orders of magnitude was measured during diel vertical migrations of zooplankton in one case (but not observed during other cases). A strong sound scattering layer undergoing diel vertical migration was also observed in the Straits of Florida via a bottom mounted acoustic Doppler current profiler at 244 m isobath. A 3-D non-hydrostatic computational fluid dynamics model with Lagrangian particle injections (a proxy for migrating zooplankton) via a discrete phase model was used to simulate the effect of diel vertical migrations on the turbulence for both Saanich Inlet and the Straits of Florida. The model was initialized with idealized (but based on observation) density and velocity profiles. Particles, with buoyancy adjusted to serve as a proxy for vertically swimming zooplankton, were injected to simulate diel vertical migration cycles. Results of models run with extreme concentrations of particles showed an increase in dissipation rate of turbulent kinetic energy of approximately five orders of magnitude over background turbulence during migration of particles in both Saanich Inlet and the Straits of Florida cases (though direct relation of the turbulence produced by buoyant particles and swimming organisms isn't straightforward). This increase was quantitatively consistent, with turbulence measurements by Kunze et al. (2006). When 10 times fewer particles were injected into the model, the effect on dissipation rate of turbulent kinetic energy was an order of magnitude smaller than that from the extreme concentration. At a concentration of particles 100 times smaller than the extreme concentration, there was no longer an observable effect. In the Straits of Florida, direct turbulence measurements were not available to make a quantitative comparison. However, a small, but statistically significant decrease in northward current velocity profiles during migration times were observed after averaging these profiles over 11 months. A small decrease of current velocity connected to the vertical migrations of particles was reproduced in the Straits of Florida model case. The deviations in the velocity profiles can be explained by the increase in turbulent mixing during vertical migration periods.

Diel habitat partitioning by bull charr and cutthroat trout during fall and winter in Rocky Mountain streams

Treesearch

Michael J. Jakober; Thomas E. McMahon; Russell F. Thurow

2000-01-01

We used underwater observation to determine diel habitat partitioning between bull charr, Salvelinus confluentus, and cutthroat trout, Oncorhynchus clarki, during fall and winter (0.1-8.3°C) in two Rocky Mountain streams that differed in habitat availability. The majority (>70%) of both species emerged from concealment cover at night, though bull charr exhibited a...

Fourfold Diels-Alder reaction of tetraethynylsilane.

PubMed

Geyer, Florian L; Rode, Alexander; Bunz, Uwe H F

2014-12-08

A series of ethynylated silanes, including tetraethynylsilane, was treated with tetraphenylcyclopentadienone at 300 °C under microwave irradiation to give the aromatized Diels-Alder adducts as sterically encumbered mini-dendrimers with up to 20 benzene rings. The sterically most congested adducts display red-shifted emission through intramolecular π-π interactions in the excited state. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diels-Alder cycloadditions by microwave-assisted, continuous flow organic synthesis (MACOS): the role of metal films in the flow tube.

PubMed

Shore, Gjergji; Organ, Michael G

2008-02-21

Thin Pd films have been deposited on the inside of capillary-sized tubes through which compounds undergoing Diels-Alder reactions have been flowed while being heated with microwave irradiation; dramatic rate accelerations are observed in the presence of the film, which has been shown to play both a heating and catalytic role.

Indole synthesis by palladium-catalyzed tandem allylic isomerization - furan Diels-Alder reaction.

PubMed

Xu, Jie; Wipf, Peter

2017-08-30

A Pd(0)-catalyzed elimination of an allylic acetate generates a π-allyl complex that is postulated to initiate a novel intramolecular Diels-Alder cycloaddition to a tethered furan (IMDAF). Under the reaction conditions, this convergent, microwave-accelerated cascade process provides substituted indoles in moderate to good yields after Pd-hydride elimination, aromatization by dehydration, and in situ N-Boc cleavage.

Diels-Alder Cycloadditions: A MORE Experiment in the Organic Laboratory Including a Diene Identification Exercise Involving NMR Spectroscopy and Molecular Modeling

ERIC Educational Resources Information Center

Shaw, Roosevelt; Severin, Ashika; Balfour, Miguel; Nettles, Columbus

2005-01-01

Two Diels-Alder reactions are described that are suitable for a MORE (microwave-induced organic reaction enhanced) experiment in the organic chemistry laboratory course. A second experiment in which the splitting patterns of the vinyl protons in the nuclear magnetic resonance (NMR) spectra of two MORE adducts are used in conjunction with molecular…

Diels-Alder Synthesis of endo-cis-N-phenylbicyclo[2.2.2]oct-5-en-2,3-dicarboximide

ERIC Educational Resources Information Center

Baar, Marsha R.; Wustholz, Kristin

2005-01-01

A study investigated the Diels-Alder synthesis of endo-cis-N-phenylbicyclo [2.2.2]oct-5-en-2,3-dicarboximide. The amount of time taken by a reaction between the 1,3-cyclohexadiene and N-phenylmaleimide at room temperature and also whether the desired cycloadduct would precipitate directly from the reaction mixture was examined.

Origins of Stereoselectivity in Diels-Alder Cycloadditions Catalyzed by Chiral Imidazolidinones

PubMed Central

Gordillo, Ruth; Houk, K. N.

2011-01-01

B3LYP/6-31G(d) density functional theory has been used to study Diels-Alder reactions of cyclopentadiene with α,β-unsaturated aldehydes and ketones organocatalyzed by MacMillan’s chiral imidazolidinones. Preferred conformations of transition structures and reaction intermediates have been located. The dramatically different reactivities and enantioselectivities exhibited by two similar chiral imidazolidinones are rationalized. PMID:16536527

Diel changes in water chemistry in an arsenic-rich stream and treatment-pond system

USGS Publications Warehouse

Gammons, C.H.; Grant, T.M.; Nimick, D.A.; Parker, S.R.; DeGrandpre, M.D.

2007-01-01

Arsenic concentrations are elevated in surface waters of the Warm Springs Ponds Operable Unit (WSPOU), located at the head of the upper Clark Fork River Superfund site, Montana, USA. Arsenic is derived from historical deposition of smelter emissions (Mill and Willow Creeks) and historical mining and milling wastes (Silver Bow Creek). Although long-term monitoring has characterized the general seasonal and flow-related trends in As concentrations in these streams and the pond system used to treat Silver Bow Creek water, little is known about solubility controls and sorption processes that influence diel cycles in As concentrations. Diel (24-h) sampling was conducted in July 2004 and August 2005 at the outlet of the treatment ponds, at two locations along a nearby reconstructed stream channel that diverts tributary water around the ponds, and at Silver Bow Creek 2??km below the ponds. Dissolved As concentration increased up to 51% during the day at most of the stream sites, whereas little or no diel change was displayed at the treatment-pond outlet. The strong cycle in streams is explained by pH- and temperature-dependent sorption of As onto hydrous metal oxides or biofilms on the streambed. Concentrations of dissolved Ca2+ and HCO3- at the stream sites showed a diel temporal pattern opposite to that of As, and geochemical modeling supports the hypothesis that the concentrations of Ca2+ and HCO3- were controlled by precipitation of calcite during the warm afternoon hours when pH rose above 9.0. Nightly increases in dissolved Mn and Fe(II) concentrations were out of phase with concentrations of other divalent cations and are more likely explained by redox phenomena. ?? 2007 Elsevier B.V. All rights reserved.

Diel feeding periodicity of Ephemera simulans nymphs in summer and winter

USGS Publications Warehouse

Johnson, James H.; Ruggirello, Jack E.; Nack, Christopher C.

2012-01-01

We examined diel feeding periodicity of Ephemera simulans nymphs during summer and winter in a third-order stream in central New York. A total of 245 nymphs were collected at 4-h intervals over two 24 h periods and were immediately preserved in 80% ethanol. In the laboratory, we weighed each nymph and its digestive tract. The ratio of wet weight of the digestive tract to the total body weight at each 4-h interval was used to determine feeding periodicity. Diel feeding periodicity followed a similar pattern in summer and winter and was significantly higher at 08:00 hours. Feeding periodicity of E. simulans in Labrador Creek is asynchronous with the two most abundant fish species in the stream and may reflect predator avoidance behavior that has been shown for other mayfly species.

The behavioural ecology of two sympatric talitrid species, Talitrus saltator (Montagu) and Orchestia gammarellus (Pallas) on a Tyrrhenian sandy beach dune system

NASA Astrophysics Data System (ADS)

Colombini, Isabella; Fallaci, Mario; Gagnarli, Elena; Rossano, Claudia; Scapini, Felicita; Chelazzi, Lorenzo

2013-01-01

The behavioural ecology of a sub-population of Talitrus saltator living on the sandy shore of the Maremma Regional Park (Italy) was compared with that of Orchestia gammarellus inhabiting the retrodunal dune slack area. Monthly monitoring over a year determined the mean distribution patterns, their changes and whether these overlapped. Standard pitfall traps were placed along transects across the beach-dune-dune slack area. Experiments analysed the diel activity rhythms during spring and the activity patterns of the different age classes and the two sexes were compared within and between species. Local environmental conditions were registered with a microclimatic station. During May and September, plant hummocks were monitored to see whether surface movements of O. gammarellus could be restricted to certain periods of the year and to estimate densities within the vegetation. The plant biomass and moisture conditions within the hummocks were also recorded and substratum samples were collected at the base of the shrubs for laboratory analysis. To test for visual cues, orientation experiments with and without landscape view were carried out on the beach during morning and afternoon hours and contemporaneously for each species. Experiments to test the diel variation of scototaxis to a black shape were also performed over a 24 h period of time under controlled conditions. There was a spatial partitioning of the two species, with T. saltator moving along a sea-land axis according to diel and seasonal changes and with some individuals reaching the back of the dune in particular environmental conditions. No spatial overlap with the zonation patterns of O. gammarellus was observed, which was restricted to the dune slack area. Nocturnal surface activity was observed for both species with juveniles peaking at dawn and with O. gammarellus being strictly more nocturnal than T. saltator. Orientation experiments showed a higher ability of T. saltator to orient towards the shoreline using solar and local cues, whereas O. gammarellus seemed to have a stronger scototaxis. Differences in the behavioural responses are discussed in terms of the species ecological adaptations to their particular habitats.

Synthesis of a Self-Healing Polymer Based on Reversible Diels-Alder Reaction: An Advanced Undergraduate Laboratory at the Interface of Organic Chemistry and Materials Science

ERIC Educational Resources Information Center

Weizman, Haim; Nielsen, Christian; Weizman, Or S.; Nemat-Nasser, Sia

2011-01-01

This laboratory experiment exposes students to the chemistry of self-healing polymers based on a Diels-Alder reaction. Students accomplish a multistep synthesis of a monomer building block and then polymerize it to form a cross-linked polymer. The healing capability of the polymer is verified by differential scanning calorimetry (DSC) experiments.…

Syntheses of the hexahydroindene cores of indanomycin and stawamycin by combinations of iridium-catalyzed asymmetric allylic alkylations and intramolecular Diels-Alder reactions.

PubMed

Gärtner, Martin; Satyanarayana, Gedu; Förster, Sebastian; Helmchen, Günter

2013-01-02

Short and concise syntheses of the hexahydroindene cores of the antibiotics indanomycin (X-14547 A) and stawamycin are presented. Key methods used are an asymmetric iridium-catalyzed allylic alkylation, a modified Julia olefination, a Suzuki-Miyaura coupling, and an intramolecular Diels-Alder reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Processing Conjugated-Diene-Containing Polymers

NASA Technical Reports Server (NTRS)

Bell, Vernon L.; Havens, Stephen J.

1987-01-01

Diels-Alder reaction used to cross-linked thermoplastics. Process uses Diels-Alder reaction to cross-link and/or extend conjugated-diene-containing polymers by reacting them with bis-unsaturated dienophiles results in improved polymer properties. Quantities of diene groups required for cross-linking varies from very low to very high concentrations. Process also used to extend, or build up molecular weights of, low-molecular-weight linear polymers with terminal conjugated dienic groups.

Fast Hetero-Diels-Alder Reactions Using 4-Phenyl-1,2,4-Triazoline-3,5-Dione (PTAD) as the Dienophile

ERIC Educational Resources Information Center

Celius, Tevye C.

2010-01-01

A hetero-Diels-Alder reaction that proceeds rapidly and only requires a simple filtration to purify the product is presented. The dienophile, 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), is prepared by the heterogeneous oxidation of 4-phenylurazole by the bromenium ion, Br[superscript +], generated in situ by the oxidation of potassium bromide by…

Habitat utilization and diel behavior of juvenile bull trout (Salvelinus confluentus) at the onset of winter

Treesearch

R. F. Thurow

1997-01-01

Underwater observations were used to describe habitat use and diel behavior of juvenile bull trout (Salvelinus confluentus) at the onset of winter (0.8°C) in a second-order central Idaho stream. All fish observed during daytime counts were concealed beneath "home stones" (mean dimensions 32.3 by 21.9 cm) in primarily pool and run habitats. Focal point depths...

Multicatalytic asymmetric synthesis of complex tetrahydrocarbazoles via a Diels-Alder/benzoin reaction sequence.

PubMed

Liu, Yankai; Nappi, Manuel; Escudero-Adán, Eduardo C; Melchiorre, Paolo

2012-03-02

Expanding upon the recently developed aminocatalytic asymmetric indole-2,3-quinodimethane strategy, a straightforward synthesis of structurally and stereochemically complex tetrahydrocarbazoles has been devised. The chemistry's complexity-generating power was further harnessed by designing a multicatalytic, one-pot Diels-Alder/benzoin reaction sequence to stereoselectively access trans-fused tetracyclic indole-based compounds having four stereogenic centers with very high fidelity. © 2012 American Chemical Society

A year in the life of a thrombolite: comparative metatranscriptomics reveals dynamic metabolic changes over diel and seasonal cycles.

PubMed

Louyakis, Artemis S; Gourlé, Hadrien; Casaburi, Giorgio; Bonjawo, Rachelle M E; Duscher, Alexandrea A; Foster, Jamie S

2018-02-01

Microbialites are one of the oldest known ecosystems on Earth and the coordinated metabolisms and activities of these mineral-depositing communities have had a profound impact on the habitability of the planet. Despite efforts to understand the diversity and metabolic potential of these systems, there has not been a systematic molecular analysis of the transcriptional changes that occur within a living microbialite over time. In this study, we generated metatranscriptomic libraries from actively growing thrombolites, a type of microbialite, throughout diel and seasonal cycles and observed dynamic shifts in the population and metabolic transcriptional activity. The most transcribed genes in all seasons were associated with photosynthesis, but only transcripts associated with photosystem II exhibited diel cycling. Photosystem I transcripts were constitutively expressed at all time points including midnight and sunrise. Transcripts associated with nitrogen fixation, methanogenesis and dissimilatory sulfate reduction exhibited diel cycling, and variability between seasons. Networking analysis of the metatranscriptomes showed correlated expression patterns helping to elucidate how metabolic interactions are coordinated within the thrombolite community. These findings have identified distinctive temporal patterns within the thrombolites and will serve an important foundation to understand the mechanisms by which these communities form and respond to changes in their environment. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

Examining diel patterns of soil and xylem moisture using electrical resistivity imaging

NASA Astrophysics Data System (ADS)

Mares, Rachel; Barnard, Holly R.; Mao, Deqiang; Revil, André; Singha, Kamini

2016-05-01

The feedbacks among forest transpiration, soil moisture, and subsurface flowpaths are poorly understood. We investigate how soil moisture is affected by daily transpiration using time-lapse electrical resistivity imaging (ERI) on a highly instrumented ponderosa pine and the surrounding soil throughout the growing season. By comparing sap flow measurements to the ERI data, we find that periods of high sap flow within the diel cycle are aligned with decreases in ground electrical conductivity and soil moisture due to drying of the soil during moisture uptake. As sap flow decreases during the night, the ground conductivity increases as the soil moisture is replenished. The mean and variance of the ground conductivity decreases into the summer dry season, indicating drier soil and smaller diel fluctuations in soil moisture as the summer progresses. Sap flow did not significantly decrease through the summer suggesting use of a water source deeper than 60 cm to maintain transpiration during times of shallow soil moisture depletion. ERI captured spatiotemporal variability of soil moisture on daily and seasonal timescales. ERI data on the tree showed a diel cycle of conductivity, interpreted as changes in water content due to transpiration, but changes in sap flow throughout the season could not be interpreted from ERI inversions alone due to daily temperature changes.

Silica-promoted Diels-Alder reactions in carbon dioxide from gaseous to supercritical conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weinstein, R.D.; Renslo, A.R.; Danheiser, R.L.

1999-04-15

Amorphous fumed silica (SiO{sub 2}) was shown to increase yields and selectivities of several Diels-Alder reactions in gaseous and supercritical CO{sub 2}. Pressure effects on the Diels-Alder reaction were explored using methyl vinyl ketone and penta-1,3-diene at 80 C. The selectivity of the reaction was not affected by pressure/density. As pressure was increased, the yield decreased. At the reaction temperature, adsorption isotherms at various pressures were obtained for the reactants and the Diels-Alder adduct. As expected when pressure is increased, the ratio of the amount of reactants adsorbed to the amount of reactants in the fluid phase decreases, thus causingmore » the yield to decrease. The Langmuir adsorption model fit the adsorption data. The Langmuir equilibrium partitioning constants all decreased with increasing pressure. The effect of temperature on adsorption was experimentally determined and traditional heats of adsorption were calculated. However, since supercritical CO{sub 2} is a highly compressible fluid, it is logical to examine the effect of temperature at constant density. In this case, entropies of adsorption were obtained. The thermodynamic properties that influence the real enthalpy and entropy of adsorption were derived. Methods of doping the silica and improving yields and selectivities were also explored.« less

Nocturnality in synapsids predates the origin of mammals by over 100 million years.

PubMed

Angielczyk, K D; Schmitz, L

2014-10-22

Nocturnality is widespread among extant mammals and often considered the ancestral behavioural pattern for all mammals. However, mammals are nested within a larger clade, Synapsida, and non-mammalian synapsids comprise a rich phylogenetic, morphological and ecological diversity. Even though non-mammalian synapsids potentially could elucidate the early evolution of diel activity patterns and enrich the understanding of synapsid palaeobiology, data on their diel activity are currently unavailable. Using scleral ring and orbit dimensions, we demonstrate that nocturnal activity was not an innovation unique to mammals but a character that appeared much earlier in synapsid history, possibly several times independently. The 24 Carboniferous to Jurassic non-mammalian synapsid species in our sample featured eye morphologies consistent with all major diel activity patterns, with examples of nocturnality as old as the Late Carboniferous (ca 300 Ma). Carnivores such as Sphenacodon ferox and Dimetrodon milleri, but also the herbivorous cynodont Tritylodon longaevus were likely nocturnal, whereas most of the anomodont herbivores are reconstructed as diurnal. Recognizing the complexity of diel activity patterns in non-mammalian synapsids is an important step towards a more nuanced picture of the evolutionary history of behaviour in the synapsid clade. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

Enantioselective Diels-Alder reactions of unsaturated beta-ketoesters catalyzed by chiral ruthenium PNNP complexes.

PubMed

Schotes, Christoph; Mezzetti, Antonio

2011-01-01

We report here dicationic ruthenium PNNP complexes that promote the enantioselective Diels-Alder reaction of alpha-methylene beta-ketoesters with various dienes. Complex [Ru(OEt2)2(PNNP)](PF6)2, formed in situ from [RuCl2,(PNNP)] and (Et3O)PF6 (2 equiv.), catalyzes the Diels-Alder reaction of such unsaturated beta-ketoesters to give novel alkoxycarbonyltetrahydro-1-indanone derivatives (nine examples) with up to 93% ee. The crystal structure of the substrate-catalyst adduct shows that the lower face of the substrate is shielded by a phenyl ring of the PNNP ligand, which accounts for the high enantioselectivity. The attack of the diene from the open re enantioface of the unsaturated beta-ketoester is consistent with the absolute configuration of the product. A useful application of this method is the reaction with Dane's diene to give estrone derivatives with up to 99% ee and an ester-exo:endo ratio of up to 145:1 (after recrystallization). Besides the enantioselective formation of all-carbon quaternary centers, this methodology is notable because unsaturated beta-ketoesters have been rarely used in Diels-Alder reactions. Furthermore, enantiomerically pure estrone derivatives are interesting in view of their potential applications, including the treatment of breast cancer.

Diel shifts in the structure and function of nearshore estuarine fish communities.

PubMed

Yeoh, D E; Valesini, F J; Hallett, C S; Abdo, D A; Williams, J

2017-04-01

Day-night shifts in the nearshore fish fauna of a temperate microtidal estuary were assessed using a holistic suite of structural and functional community attributes. Mean fish species richness and diversity (taxonomic distinctness) were higher at night across all regions of the estuary and seasons, concurring with the findings of numerous comparable studies reviewed worldwide, while the diel period in which mean abundance was higher varied among seasons. Likewise, species and functional guild compositions (the latter based on feeding modes and habitat use) both differed significantly between day and night, with the extent of the diel shift again varying seasonally. Daytime fish communities were characterized by higher abundances of Atherinidae, Sillaginidae and Mugilidae, while Gobiidae were far more abundant at night. Marked shifts in size composition were also evident, with smaller fishes (<100 mm total length, L T ) being more prevalent during the day and larger fishes (≥200 mm L T ) proportionally more abundant at night. The above diel shifts were feasibly related to a range of predator-prey interactions and feeding-related movements, namely a nocturnal decrease in top-order avian piscivory coupled with an increase in invertebrate prey availability, resulting in changes in the presence and catchability of certain fish species in shallow estuarine waters. © 2016 The Fisheries Society of the British Isles.

OH radical "life expectancy" within and above the Amazon rainforest: vertical, diel and seasonal variations

NASA Astrophysics Data System (ADS)

Nölscher, A.; Yanez-Serrano, A. M.; Kesselmeier, J.; Artaxo, P. P.; Wolff, S.; Trebs, I.; Williams, J.

2013-12-01

The Amazon rainforest forest is the world's largest contiguous ecosystem. Being about 6 million km2 it is around two thirds the area of the United States. The Amazon forest plays an important part of the Earth's hydrological, energy and carbon cycles. Photosynthetic uptake of CO2 by the rainforest affects the global radiative budget and concomitant release of reactive biogenic volatile organic compounds (BVOCs) can directly impact the atmosphere's primary oxidant, the hydroxyl (OH) radical as well as aerosol production and growth. Direct measurement of the total atmospheric OH reactivity (or inverse OH lifetime), in parallel with the individual BVOC can reveal insights into the coupling between biogenic emissions, atmospheric oxidation processes, canopy transport, and the OH budget. In this study we present for the first time, vertical profiles of total OH reactivity and biogenic VOCs that were monitored simultaneously throughout dry season, wet season and transition periods, from a remote tropical rainforest site in the Amazon (Amazonian Tall Tower Observatory (ATTO), S 02°08'38.8'', W 58°59'59.5'', 120 m above sea level, 150 km NE of the city of Manaus, Brazil). The profiles consisted of sequential measurements at 0.05m, 0.5m, 4 m, 12m, 24m, 38m, 53m and 79m, a single profile taking 16 minutes to complete. The measurements were made using Proton Transfer Reaction Mass Spectrometry (PTR-MS), directly in the case of BVOC and using the Comparative Reactivity Method pre-reactor for total OH reactivity. The vertical, diel and seasonal variations in total OH reactivity will be discussed. Total OH reactivity and isoprene profiles were observed to vary strongly between the seasons. Biogenic emissions from the canopy impacted the measurements as well as photo-oxidation, turbulent mixing, and deposition. Tower in the Amazon rainforest for measurements of vertical profiles of BVOCs and total OH reactivity from the forest floor, through the canopy, up to 80m.

Optical characterization of the oceanic unicellular cyanobacterium Synechococcus grown under a day-night cycle in natural irradiance

NASA Technical Reports Server (NTRS)

Stramski, Dariusz; Shalapyonok, Alexi; Reynolds, Rick A.

1995-01-01

The optical properties of the ocenanic cyanobacterium Synechococcus (clone WH8103) were examined in a nutrient-replete laboratory culture grown under a day-night cycle in natural irradiance. Measurements of the spectral absorption and beam attenuation coefficients, the size distribution of cells in suspension, and microscopic analysis of samples were made at intervals of 2-4 hours for 2 days. These measurements were used to calculate the optical properties at the level of a single 'mean' cell representative of the acutal population, specifically, the optical cross sections for spectral absorption bar-(sigma(sub a)), scattering bar-sigma(sub b))(lambda), and attentuation bar-(sigma(sub c))(lambda). In addition, concurrent determinations of chlorophyll a and particulate organic carbon allowed calculation of the Chl a- and C-specific optical coefficients. The refractive index of cells was derived from the observed data using a theory of light absorption and scattering by homogeneous spheres. Low irradiance because of cloudy skies resulted in slow division rates of cells in the culture. The percentage of dividing cells was unusually high (greater than 30%) throughout the experiment. The optical cross sections varied greatly over a day-night cycle, with a minimum near dawn or midmorning and maximum near dusk. During daylight hours, bar-(sigma(sub b)) and bar-(sigma(sub c)) can increase more than twofold and bar-(sigma(sub a) by as much as 45%. The real part of the refractive index n increaed during the day; changes in n had equal or greater effect than the varying size distribution on changes in bar-(sigma(sub c)) and bar-(sigma(sub b)). The contribution of changes in n to the increase of bar-(sigma(sub c))(660) during daylight hours was 65.7% and 45.1% on day 1 and 2, respectively. During the dark period, when bar-(sigma(sub c))(660) decreased by a factor of 2.9, the effect of decreasing n was dominant (86.3%). With the exception of a few hours during the second light period, the imaginary part of the refractive index n' showed little variation over a day-night cycle, and bar-(sigma(sub a)) was largely controlled by variations in cell size. The real part of the refractive index at lambda = 660 nm was correlated with the intracellular C concentration and the imaginary part at lambda = 678 nm with the intracellular Chl a concentration. The C-specfic attenuation coefficient showed significant diel variability, which has implications for the estimation of oceanic primary production from measurements of diel variability in beam attenuation. This study provides strong evidence that diel variability is an important component of the optical characterization of marine phytoplankton.

A thermal dehydrogenative Diels-Alder reaction of styrenes for the concise synthesis of functionalized naphthalenes.

PubMed

Kocsis, Laura S; Benedetti, Erica; Brummond, Kay M

2012-09-07

Functionalized naphthalenes are valuable building blocks in many important areas. A microwave-assisted, intramolecular dehydrogenative Diels-Alder reaction of styrenyl derivatives to provide cyclopenta[b]naphthalene substructures not previously accessible using existing synthetic methods is described. The synthetic utility of these uniquely functionalized naphthalenes was demonstrated by a single-step conversion of one of these cycloadducts to a fluorophore bearing a structural resemblance to Prodan.

Structural basis for Diels-Alder ribozyme-catalyzed carbon-carbon bond formation

PubMed Central

Serganov, Alexander; Keiper, Sonja; Malinina, Lucy; Tereshko, Valentina; Skripkin, Eugene; Höbartner, Claudia; Polonskaia, Anna; Phan, Anh Tuân; Wombacher, Richard; Micura, Ronald; Dauter, Zbigniew; Jäschke, Andres; Patel, Dinshaw J

2015-01-01

The majority of structural efforts addressing RNA’s catalytic function have focused on natural ribozymes, which catalyze phosphodiester transfer reactions. By contrast, little is known about how RNA catalyzes other types of chemical reactions. We report here the crystal structures of a ribozyme that catalyzes enantioselective carbon-carbon bond formation by the Diels-Alder reaction in the unbound state and in complex with a reaction product. The RNA adopts a λ-shaped nested pseudoknot architecture whose preformed hydrophobic pocket is precisely complementary in shape to the reaction product. RNA folding and product binding are dictated by extensive stacking and hydrogen bonding, whereas stereoselection is governed by the shape of the catalytic pocket. Catalysis is apparently achieved by a combination of proximity, complementarity and electronic effects. We observe structural parallels in the independently evolved catalytic pocket architectures for ribozyme- and antibody-catalyzed Diels-Alder carbon-carbon bond-forming reactions. PMID:15723077

Enzymatic activity and partial purification of solanapyrone synthase: first enzyme catalyzing Diels-Alder reaction.

PubMed

Katayama, K; Kobayashi, T; Oikawa, H; Honma, M; Ichihara, A

1998-05-19

In cell-free extracts of Alternaria solani, an enzymatic activity converting prosolanapyrone II to solanapyrones A and D via oxidation and subsequent Diels-Alder reaction has been found. Chromatography with DEAE-Sepharose provided two active fractions, pools 1 and 2. The former fraction converted prosolanapyrone II to solanapyrones A and D in a ratio of 2.2:1 with optical purities of 99% and 45% ee, respectively. The latter fraction did so in a ratio of 7.6:1 with 99% and nearly 0% ee, respectively. The enzyme partially purified from pool 2 native molecular weight of 40-62 kD and a pl of 4.25. The high reactivity of prosolanapyrone III in aqueous solution and the chromatographic behavior of the enzyme in pool 2 suggest that a single enzyme catalyzes both the oxidation and Diels-Alder reaction.

"Clickable" Polymeric Nanofibers through Hydrophilic-Hydrophobic Balance: Fabrication of Robust Biomolecular Immobilization Platforms.

PubMed

Kalaoglu-Altan, Ozlem I; Sanyal, Rana; Sanyal, Amitav

2015-05-11

Fabrication of hydrophilic polymeric nanofibers that undergo facile and selective functionalization through metal catalyst-free Diels-Alder "click" reaction in aqueous environment is outlined. Electrospinning of copolymers containing an electron-rich furan moiety, hydrophobic methyl methacrylate units and hydrophilic poly(ethylene glycol)s as side chains provide specifically functionalizable yet antibiofouling fibers that remain stable in aqueous media due to appropriate hydrophobic hydrophilic balance. Efficient functionalization of these nanofibers is accomplished through the Diels-Alder reaction by exposing them to maleimide-containing molecules and ligands. Diels-Alder conjugation based functionalization is demonstrated through attachment of fluorescein-maleimide and a maleimide tethered biotin ligand. Biotinylated nanofibers were utilized to mediate immobilization of the protein streptavidin, as well as streptavidin coated quantum dots. Facile fabrication from readily available polymers and their effective functionalization under mild and reagent-free conditions in aqueous media make these "clickable" nanofibers attractive candidates as functionalizable scaffolds for various biomedical applications.

The hexadehydro-Diels-Alder reaction.

PubMed

Hoye, Thomas R; Baire, Beeraiah; Niu, Dawen; Willoughby, Patrick H; Woods, Brian P

2012-10-11

Arynes (aromatic systems containing, formally, a carbon-carbon triple bond) are among the most versatile of all reactive intermediates in organic chemistry. They can be 'trapped' to give products that are used as pharmaceuticals, agrochemicals, dyes, polymers and other fine chemicals. Here we explore a strategy that unites the de novo generation of benzynes-through a hexadehydro-Diels-Alder reaction-with their in situ elaboration into structurally complex benzenoid products. In the hexadehydro-Diels-Alder reaction, a 1,3-diyne is engaged in a [4+2] cycloisomerization with a 'diynophile' to produce the highly reactive benzyne intermediate. The reaction conditions for this simple, thermal transformation are notable for being free of metals and reagents. The subsequent and highly efficient trapping reactions increase the power of the overall process. Finally, we provide examples of how this de novo benzyne generation approach allows new modes of intrinsic reactivity to be revealed.

Polar Diels-Alder reactions using electrophilic nitrobenzothiophenes. A combined experimental and DFT study

NASA Astrophysics Data System (ADS)

Della Rosa, Claudia D.; Mancini, Pedro M. E.; Kneeteman, Maria N.; Lopez Baena, Anna F.; Suligoy, Melisa A.; Domingo, Luis R.

2015-01-01

The reactions between 2- and 3-nitrobenzothiophenes with three dienes of different nucleophilicity, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-1,3-butadiene and isoprene developed in anhydrous benzene and alternative under microwave irradiation with molecular solvents or in free solvent conditions, respectively, for produce dibenzothiophenes permit to conclude that both nitroheterocycles act as electrophile with the cited dienes. In the cases of the dienes 1-methoxy-3-trimethylsilyloxy-1,3-butadiene and 1-trimethylsilyloxy-1,3-butadiene which posses major nucleophilicity the observed product is the normal cycloaddition one. However when the diene is isoprene the product with both electrophiles follow the hetero Diels-Alder way. These reactions are considered polar cycloaddition reactions and the yields are reasonables. Moreover the polar Diels-Alder reactions of nitrobenzothiophenes with electron rich dienes 1-trimethylsilyloxy-1,3-butadiene have been theoretically studied using DFT methods.

Impact of diurnal temperature fluctuations on larval settlement and growth of the reef coral Pocillopora damicornis

NASA Astrophysics Data System (ADS)

Jiang, Lei; Sun, You-Fang; Zhang, Yu-Yang; Zhou, Guo-Wei; Li, Xiu-Bao; McCook, Laurence J.; Lian, Jian-Sheng; Lei, Xin-Ming; Liu, Sheng; Cai, Lin; Qian, Pei-Yuan; Huang, Hui

2017-12-01

Diurnal fluctuations in seawater temperature are ubiquitous on tropical reef flats. However, the effects of such dynamic temperature variations on the early stages of corals are poorly understood. In this study, we investigated the responses of larvae and new recruits of Pocillopora damicornis to two constant temperature treatments (29 and 31 °C) and two diurnally fluctuating treatments (28-31 and 30-33 °C with daily means of 29 and 31 °C, respectively) simulating the 3 °C diel oscillations at 3 m depth on the Luhuitou fringing reef (Sanya, China). Results showed that the thermal stress on settlement at 31 °C was almost negated by the fluctuating treatment. Further, neither elevated temperature nor temperature fluctuations caused bleaching responses in recruits, while the maximum excitation pressure over photosystem II (PSII) was reduced under fluctuating temperatures. Although early growth and development were highly stimulated at 31 °C, oscillations of 3 °C had little effects on budding and lateral growth at either mean temperature. Nevertheless, daytime encounters with the maximum temperature of 33 °C in fluctuating 31 °C elicited a notable reduction in calcification compared to constant 31 °C. These results underscore the complexity of the effects caused by diel temperature fluctuations on early stages of corals and suggest that ecologically relevant temperature variability could buffer warming stress on larval settlement and dampen the positive effects of increased temperatures on coral growth.

VARIATION IN THE ABUNDANCE OF SYNECHOCOCCUS SP. CC9311 NARB MRNA RELATIVE TO CHANGES IN LIGHT, NITROGEN GROWTH CONDITIONS AND NITRATE ASSIMILATION(1).

PubMed

Paerl, Ryan W; Tozzi, Sasha; Kolber, Zbigniew S; Zehr, Jonathan P

2012-08-01

Synechococcus- and Prochlorococcus-specific narB genes that encode for an assimilatory nitrate reductase are found in coastal to open-ocean waters. However, it remains uncertain if these picocyanobacteria assimilate nitrate in situ. This unknown can potentially be addressed by examining narB mRNA from the environment, but this requires a better understanding of the influence of environmental factors on narB gene transcription. In laboratory experiments with Synechococcus sp. CC9311 cultures exposed to diel light fluctuations and grown on nitrate or ammonium, there was periodic change in narB transcript abundance. This periodicity was broken in cultures subjected to a doubling of irradiance (40-80 μmol photons · m(-2)  · s(-1) ) during the mid-light period. Therefore, the irradiance level, not circadian rhythm, was the dominant factor controlling narB transcription. In nitrate-grown cultures, diel change in narB transcript abundance and nitrate assimilation rate did not correlate; suggesting narB mRNA levels better indicate nitrate assimilation activity than assimilation rate. Growth history also affected narB transcription, as changes in narB mRNA levels in nitrogen-deprived CC9311 cultures following nitrate amendment were distinct from cultures grown solely on nitrate. Environmental sampling for narB transcripts should consider time, irradiance, and the growth status of cells to ecologically interpret narB transcript abundances. © 2012 Phycological Society of America.

National Research Council Resident Research Associateship (NRC-RRA) program

DTIC Science & Technology

1988-08-01

Davis, C. J. Dymek, J. J. P. Stewart, H. P. Clark, W. J. Lauderdale, J. Am. Chem. Soc., 107, 5041-5046 (1985). 7. "Mechanism of the Diels - Alder ...Package" Dewar Research Group and J. J. P. Stewart, Quantum Chemistry Program Exchange, no. 506, nn, nnn, (1986) 16. "Mechanism of the Diels - Alder ...Kvisle, 0. Nirisen, M. Ystenes, and H. A. Oye, Proceedings of 1986 International Symposium on Transition Metals Catalyzed Polymerizations, Institute of

The unexpected product of Diels-Alder reaction between "indanocyclon" and maleimide

NASA Astrophysics Data System (ADS)

Dobrowolski, Michał A.; Roszkowski, Piotr; Struga, Marta; Szulczyk, Daniel

2017-02-01

A heterocyclic compound commonly known as "indanocyclon" undergoes an unexpected Diels-Alder addition with maleimide. The resulting product has been isolated and characterized in order to get an information about its structure and possible mechanism of the reaction. Extensive comparison of single crystal properties of 3-(2,8-dioxo-1,3-diphenyl-2,8-dihydrocyclopenta[a]inden-8a(1H)-yl)pyrrolidine-2,5-dione and favorable product of the reaction has been also performed.

Continuous-flow retro-Diels-Alder reaction: an efficient method for the preparation of pyrimidinone derivatives.

PubMed

Nekkaa, Imane; Palkó, Márta; Mándity, István M; Fülöp, Ferenc

2018-01-01

The syntheses of various pyrimidinones as potentially bioactive products by means of the highly controlled continuous-flow retro-Diels-Alder reaction of condensed pyrimidinone derivatives are presented. Noteworthy, the use of this approach allowed us to rapidly screen a selection of conditions and quickly confirm the viability of preparing the desired pyrimidinones in short reaction times. Yields typically higher than those published earlier using conventional batch or microwave processes were achieved.

Seasonal and Diel Activity Patterns of Eight Sympatric Mammals in Northern Japan Revealed by an Intensive Camera-Trap Survey.

PubMed

Ikeda, Takashi; Uchida, Kenta; Matsuura, Yukiko; Takahashi, Hiroshi; Yoshida, Tsuyoshi; Kaji, Koichi; Koizumi, Itsuro

2016-01-01

The activity patterns of mammals are generally categorized as nocturnal, diurnal, crepuscular (active at twilight), and cathemeral (active throughout the day). These patterns are highly variable across regions and seasons even within the same species. However, quantitative data is still lacking, particularly for sympatric species. We monitored the seasonal and diel activity patterns of terrestrial mammals in Hokkaido, Japan. Through an intensive camera-trap survey a total of 13,279 capture events were recorded from eight mammals over 20,344 camera-trap days, i.e., two years. Diel activity patterns were clearly divided into four categories: diurnal (Eurasian red squirrels), nocturnal (raccoon dogs and raccoons), crepuscular (sika deer and mountain hares), and cathemeral (Japanese martens, red foxes, and brown bears). Some crepuscular and cathemeral mammals shifted activity peaks across seasons. Particularly, sika deer changed peaks from twilight during spring-autumn to day-time in winter, possibly because of thermal constraints. Japanese martens were cathemeral during winter-summer, but nocturnal in autumn. We found no clear indication of predator-prey and competitive interactions, suggesting that animal densities are not very high or temporal niche partitioning is absent among the target species. This long-term camera-trap survey was highly cost-effective and provided one of the most detailed seasonal and diel activity patterns in multiple sympatric mammals under natural conditions.

Seasonal and Diel Vocalization Patterns of Antarctic Blue Whale (Balaenoptera musculus intermedia) in the Southern Indian Ocean: A Multi-Year and Multi-Site Study.

PubMed

Leroy, Emmanuelle C; Samaran, Flore; Bonnel, Julien; Royer, Jean-Yves

2016-01-01

Passive acoustic monitoring is an efficient way to provide insights on the ecology of large whales. This approach allows for long-term and species-specific monitoring over large areas. In this study, we examined six years (2010 to 2015) of continuous acoustic recordings at up to seven different locations in the Central and Southern Indian Basin to assess the peak periods of presence, seasonality and migration movements of Antarctic blue whales (Balaenoptera musculus intermedia). An automated method is used to detect the Antarctic blue whale stereotyped call, known as Z-call. Detection results are analyzed in terms of distribution, seasonal presence and diel pattern of emission at each site. Z-calls are detected year-round at each site, except for one located in the equatorial Indian Ocean, and display highly seasonal distribution. This seasonality is stable across years for every site, but varies between sites. Z-calls are mainly detected during autumn and spring at the subantarctic locations, suggesting that these sites are on the Antarctic blue whale migration routes, and mostly during winter at the subtropical sites. In addition to these seasonal trends, there is a significant diel pattern in Z-call emission, with more Z-calls in daytime than in nighttime. This diel pattern may be related to the blue whale feeding ecology.

Diel periodicity of pheromone release by females of Planococcus citri and Planococcus ficus and the temporal flight activity of their conspecific males

NASA Astrophysics Data System (ADS)

Levi-Zada, Anat; Fefer, Daniela; David, Maayan; Eliyahu, Miriam; Franco, José Carlos; Protasov, Alex; Dunkelblum, Ezra; Mendel, Zvi

2014-08-01

The diel periodicity of sex pheromone release was monitored in two mealybug species, Planococcus citri and Planococcus ficus (Hemiptera; Pseudococcidae), using sequential SPME/GCMS analysis. A maximal release of 2 ng/h pheromone by 9-12-day-old P. citri females occurred 1-2 h before the beginning of photophase. The highest release of pheromone by P. ficus females was 1-2 ng/2 h of 10-20-day-old females, approximately 2 h after the beginning of photophase. Mating resulted in termination of the pheromone release in both mealybug species. The temporal flight activity of the males was monitored in rearing chambers using pheromone baited delta traps. Males of both P. citri and P. ficus displayed the same flight pattern and began flying at 06:00 hours when the light was turned on, reaching a peak during the first and second hour of the photophase. Our results suggest that other biparental mealybug species display also diel periodicities of maximal pheromone release and response. Direct evaluation of the diel periodicity of the pheromone release by the automatic sequential analysis is convenient and will be very helpful in optimizing the airborne collection and identification of other unknown mealybug pheromones and to study the calling behavior of females. Considering this behavior pattern may help to develop more effective pheromone-based management strategies against mealybugs.

Assessing time-integrated dissolved concentrations and predicting toxicity of metals during diel cycling in streams

USGS Publications Warehouse

Balistrieri, Laurie S.; Nimick, David A.; Mebane, Christopher A.

2012-01-01

Evaluating water quality and the health of aquatic organisms is challenging in systems with systematic diel (24 hour) or less predictable runoff-induced changes in water composition. To advance our understanding of how to evaluate environmental health in these dynamic systems, field studies of diel cycling were conducted in two streams (Silver Bow Creek and High Ore Creek) affected by historical mining activities in southwestern Montana. A combination of sampling and modeling tools were used to assess the toxicity of metals in these systems. Diffusive Gradients in Thin Films (DGT) samplers were deployed at multiple time intervals during diel sampling to confirm that DGT integrates time-varying concentrations of dissolved metals. Thermodynamic speciation calculations using site specific water compositions, including time-integrated dissolved metal concentrations determined from DGT, and a competitive, multiple-metal biotic ligand model incorporated into the Windemere Humic Aqueous Model Version 6.0 (WHAM VI) were used to determine the chemical speciation of dissolved metals and biotic ligands. The model results were combined with previously collected toxicity data on cutthroat trout to derive a relationship that predicts the relative survivability of these fish at a given site. This integrative approach may prove useful for assessing water quality and toxicity of metals to aquatic organisms in dynamic systems and evaluating whether potential changes in environmental health of aquatic systems are due to anthropogenic activities or natural variability.

Light-mediated Zn uptake in photosynthetic biofilm

USGS Publications Warehouse

Morris, J.M.; Farag, A.M.; Nimick, D.A.; Meyer, J.S.

2006-01-01

Our experiments conducted under controlled laboratory conditions demonstrate diel uptake and release of zinc (Zn) in lab-cultured biofilm exposed to Zn concentrations that are present in some mining-impacted streams (1-2 mg Zn/l). Specifically, at constant pH, temperature, and aqueous Zn concentrations in the exposure water, biofilm accumulated Zn during the light periods of the photocycle and released Zn during the dark periods of the photocycle. The range of Zn uptake measured in biofilm during one light period in these laboratory experiments (0.6-8.3 mg Zn/g dw biofilm) encompassed the estimated Zn uptake (1.5-3.7 mg Zn/g dw biofilm) necessary to attribute aqueous diel Zn cycling in a mining-impacted stream in Montana (High Ore Creek) to uptake in biofilm. This is relevant to in situ studies of diel Zn cycling because we controlled three important parameters that naturally fluctuate daily in the field, thus demonstrating the potential for biofilm to remove large percentages of Zn from some mining-impacted streams. Researchers, modelers, regulators, and reclamation teams working in metals-contaminated streams should be aware of diel metal cycling, because the highest Zn concentrations (and therefore, perhaps the most toxic conditions) in the water column might occur at night, and the greatest exposure of grazers of phototrophs to dietborne Zn might occur during daylight hours. ?? Springer 2006.

Seasonal and Diel Vocalization Patterns of Antarctic Blue Whale (Balaenoptera musculus intermedia) in the Southern Indian Ocean: A Multi-Year and Multi-Site Study

PubMed Central

Leroy, Emmanuelle C.; Samaran, Flore; Bonnel, Julien; Royer, Jean-Yves

2016-01-01

Passive acoustic monitoring is an efficient way to provide insights on the ecology of large whales. This approach allows for long-term and species-specific monitoring over large areas. In this study, we examined six years (2010 to 2015) of continuous acoustic recordings at up to seven different locations in the Central and Southern Indian Basin to assess the peak periods of presence, seasonality and migration movements of Antarctic blue whales (Balaenoptera musculus intermedia). An automated method is used to detect the Antarctic blue whale stereotyped call, known as Z-call. Detection results are analyzed in terms of distribution, seasonal presence and diel pattern of emission at each site. Z-calls are detected year-round at each site, except for one located in the equatorial Indian Ocean, and display highly seasonal distribution. This seasonality is stable across years for every site, but varies between sites. Z-calls are mainly detected during autumn and spring at the subantarctic locations, suggesting that these sites are on the Antarctic blue whale migration routes, and mostly during winter at the subtropical sites. In addition to these seasonal trends, there is a significant diel pattern in Z-call emission, with more Z-calls in daytime than in nighttime. This diel pattern may be related to the blue whale feeding ecology. PMID:27828976

Out of the dark: 350 million years of conservatism and evolution in diel activity patterns in vertebrates.

PubMed

Anderson, Samantha R; Wiens, John J

2017-08-01

Many animals are active only during a particular time (e.g., day vs. night), a partitioning that may have important consequences for species coexistence. An open question is the extent to which this diel activity niche is evolutionarily conserved or labile. Here, we analyze diel activity data across a phylogeny of 1914 tetrapod species. We find strong phylogenetic signal, showing that closely related species tend to share similar activity patterns. Ancestral reconstructions show that nocturnality was the most likely ancestral diel activity pattern for tetrapods and many major clades within it (e.g., amphibians, mammals). Remarkably, nocturnal activity appears to have been maintained continuously in some lineages for ∼350 million years. Thus, we show that traits involved in local-scale resource partitioning can be conserved over strikingly deep evolutionary time scales. We also demonstrate a potentially important (but often overlooked) metric of niche conservatism. Finally, we show that diurnal lineages appear to have faster speciation and diversification rates than nocturnal lineages, which may explain why there are presently more diurnal tetrapod species even though diurnality appears to have evolved more recently. Overall, our results may have implications for studies of community ecology, species richness, and the evolution of diet and communication systems. © 2017 The Author(s). Evolution © 2017 The Society for the Study of Evolution.

Inferred fish behavior its implications for hydroacoustic surveys in nearshore habitats

USGS Publications Warehouse

DuFour, Mark R.; Mayer, Christine M.; Qian, Song S.; Vandergoot, Christopher; Kraus, Richard T.; Kocovsky, Patrick; Warner, David M.

2018-01-01

Population availability and vessel avoidance effects on hydroacoustic abundance estimates may be scale dependent; therefore, it is important to evaluate these biases across systems. We performed an inter-ship comparison survey to determine the effect of vessel size, day-night period, depth, and environmental gradients on walleye (Sander vitreus) density estimates in Lake Erie, an intermediate-scaled system. Consistent near-bottom depth distributions coupled with horizontal fish movements relative to vessel paths indicated avoidance behavior contributed to higher walleye densities from smaller vessels in shallow water (i.e., <15 m), although the difference decreased with increasing depth. Diel bank migrations in response to seasonally varying onshore-to-offshore environmental gradients likely contributed to day-night differences in densities between sampling locations and seasons. Spatial and unexplained variation accounted for a high proportion of total variation; however, increasing sampling intensity can mitigate effects on precision. Therefore, researchers should minimize systematic avoidance and availability related biases (i.e., vessel and day-night period) to improve population abundance estimates. Quantifying availability and avoidance behavior effects and partitioning sources of variation provides informed flexibility for designing future hydroacoustic surveys in shallow-water nearshore environments.

Six Month In Situ High-Resolution Carbonate Chemistry and Temperature Study on a Coral Reef Flat Reveals Asynchronous pH and Temperature Anomalies.

PubMed

Kline, David I; Teneva, Lida; Hauri, Claudine; Schneider, Kenneth; Miard, Thomas; Chai, Aaron; Marker, Malcolm; Dunbar, Rob; Caldeira, Ken; Lazar, Boaz; Rivlin, Tanya; Mitchell, Brian Gregory; Dove, Sophie; Hoegh-Guldberg, Ove

2015-01-01

Understanding the temporal dynamics of present thermal and pH exposure on coral reefs is crucial for elucidating reef response to future global change. Diel ranges in temperature and carbonate chemistry parameters coupled with seasonal changes in the mean conditions define periods during the year when a reef habitat is exposed to anomalous thermal and/or pH exposure. Anomalous conditions are defined as values that exceed an empirically estimated threshold for each variable. We present a 200-day time series from June through December 2010 of carbonate chemistry and environmental parameters measured on the Heron Island reef flat. These data reveal that aragonite saturation state, pH, and pCO2 were primarily modulated by biologically-driven changes in dissolved organic carbon (DIC) and total alkalinity (TA), rather than salinity and temperature. The largest diel temperature ranges occurred in austral spring, in October (1.5 - 6.6°C) and lowest diel ranges (0.9 - 3.2°C) were observed in July, at the peak of winter. We observed large diel total pH variability, with a maximum range of 7.7 - 8.5 total pH units, with minimum diel average pH values occurring during spring and maximum during fall. As with many other reefs, the nighttime pH minima on the reef flat were far lower than pH values predicted for the open ocean by 2100. DIC and TA both increased from June (end of Fall) to December (end of Spring). Using this high-resolution dataset, we developed exposure metrics of pH and temperature individually for intensity, duration, and severity of low pH and high temperature events, as well as a combined metric. Periods of anomalous temperature and pH exposure were asynchronous on the Heron Island reef flat, which underlines the importance of understanding the dynamics of co-occurrence of multiple stressors on coastal ecosystems.

Six Month In Situ High-Resolution Carbonate Chemistry and Temperature Study on a Coral Reef Flat Reveals Asynchronous pH and Temperature Anomalies

PubMed Central

Kline, David I.; Teneva, Lida; Hauri, Claudine; Schneider, Kenneth; Miard, Thomas; Chai, Aaron; Marker, Malcolm; Dunbar, Rob; Caldeira, Ken; Lazar, Boaz; Rivlin, Tanya; Mitchell, Brian Gregory; Dove, Sophie; Hoegh-Guldberg, Ove

2015-01-01

Understanding the temporal dynamics of present thermal and pH exposure on coral reefs is crucial for elucidating reef response to future global change. Diel ranges in temperature and carbonate chemistry parameters coupled with seasonal changes in the mean conditions define periods during the year when a reef habitat is exposed to anomalous thermal and/or pH exposure. Anomalous conditions are defined as values that exceed an empirically estimated threshold for each variable. We present a 200-day time series from June through December 2010 of carbonate chemistry and environmental parameters measured on the Heron Island reef flat. These data reveal that aragonite saturation state, pH, and pCO2 were primarily modulated by biologically-driven changes in dissolved organic carbon (DIC) and total alkalinity (TA), rather than salinity and temperature. The largest diel temperature ranges occurred in austral spring, in October (1.5 – 6.6°C) and lowest diel ranges (0.9 – 3.2°C) were observed in July, at the peak of winter. We observed large diel total pH variability, with a maximum range of 7.7 – 8.5 total pH units, with minimum diel average pH values occurring during spring and maximum during fall. As with many other reefs, the nighttime pH minima on the reef flat were far lower than pH values predicted for the open ocean by 2100. DIC and TA both increased from June (end of Fall) to December (end of Spring). Using this high-resolution dataset, we developed exposure metrics of pH and temperature individually for intensity, duration, and severity of low pH and high temperature events, as well as a combined metric. Periods of anomalous temperature and pH exposure were asynchronous on the Heron Island reef flat, which underlines the importance of understanding the dynamics of co-occurrence of multiple stressors on coastal ecosystems. PMID:26039687

Diel changes in metal concentrations in a geogenically acidic river: Rio Agrio, Argentina

NASA Astrophysics Data System (ADS)

Parker, Stephen R.; Gammons, Christopher H.; Pedrozo, Fernando L.; Wood, Scott A.

2008-12-01

Rio Agrio in Patagonia, Argentina is a geogenically acidic stream that derives its low-pH waters from condensation of acidic gases near its headwaters on the flanks of the active Copahue Volcano. This study reports the results of three diel (24-h) water samplings in three different pH regimes (3.2, 4.4 and 6.3) along the river. Changes in the concentration and speciation of Fe dominated the diel chemical changes at all three sites, although the timing and intensity of these cycles were different in each reach. At the two acidic sampling sites, total dissolved Fe and dissolved Fe(III) concentrations decreased during the day and increased at night, whereas dissolved Fe(II) showed the reverse pattern. These cycles are explained by Fe(III) photoreduction, as well as enhanced rates of precipitation of hydrous ferric oxide (HFO) during the warm afternoon hours. A strong correlation was observed between Fe(III) and As at the furthest upstream (pH 3.2) site, most likely due to co-precipitation of As with HFO. At the downstream (pH 6.3) location, Fe(II) concentrations increased at night, as did concentrations of rare earth elements and dissolved Al. Photoreduction does not appear to be an important process at pH 6.3, although it may be indirectly responsible for the observed diel cycle of Fe(II) due to advection of photochemically produced Fe(II) from acidic upstream waters. The results of this study of a naturally-acidic river are very similar to diel trends recently obtained from mining-impacted streams receiving acid rock drainage. The results are also used to explore the link between geochemistry and microbiology in acidic eco-systems. For example, Fe(III) photoreduction produces chemical potential energy (in the form of metastable Fe 2+) that helps support the bacterial community in this unique extreme environment.

Control of femtosecond laser driven retro-Diels-Alder-like reaction of dicyclopentadiene

PubMed Central

Das, Dipak Kumar; Goswami, Tapas; Goswami, Debabrata

2013-01-01

Using femtosecond time resolved degenerate pump-probe mass spectrometry coupled with simple linearly chirped frequency modulated pulse, we elucidate that the dynamics of retro-Diels-Alder-like reaction of diclopentadiene (DCPD) to cyclopentadiene (CPD) in supersonic molecular beam occurs in ultrafast time scale. Negatively chirped pulse enhances the ion yield of CPD, as compared to positively chirped pulse. This indicates that by changing the frequency (chirp) of the laser pulse we can control the ion yield of a chemical reaction. PMID:23814449

Excellent acceleration of the Diels-Alder reaction by microwave irradiation for the synthesis of new fluorine-substituted ligands of NMDA receptor.

PubMed

Sasaki, S; Ishibashi, N; Kuwamura, T; Sano, H; Matoba, M; Nisikawa, T; Maeda, M

1998-11-03

A series of 6,11-ethanobenzo[b]quinolizinium derivatives was synthesized through the Diels-Alder reaction between azoniaanthracne and the corresponding 1,1-disubstituted olefin. After a systematic investigation for achieving rapid synthesis, it was found that the reaction is accelerated in polar media such as H2O and trifluoroethanol. In particular, excellent acceleration was effected by microwave irradiation. The new fluorine-substituted ligands thus obtained exhibited potential affinity toward NMDA receptors.

Microwave-Assisted Organocatalytic Intramolecular Knoevenagel/Hetero Diels-Alder Reaction with O-(Arylpropynyloxy)-Salicylaldehydes: Synthesis of Polycyclic Embelin Derivatives.

PubMed

Martín-Acosta, Pedro; Feresin, Gabriela; Tapia, Alejandro; Estévez-Braun, Ana

2016-10-21

A highly efficient and regioselective approach to new polycyclic embelin derivatives through a domino Knoevenagel condensation/intramolecular hetero Diels-Alder reaction using O-(arylpropynyloxy)-salicylaldehydes in the presence of ethylenediamine diacetate (EDDA) is reported. This organocatalyzed protocol is compatible toward a wide range of aryl-substituted alkynyl ethers with electron-donating and electron-withdrawing groups. When other active methylene compounds were subjected to this domino reaction the corresponding adducts were obtained in high yield.

Diels-Alder reactions of 12-hydroxy-9(10®20)-5aH-abeo-abieta-1(10),8(9),12(13)-triene-11,14-dione.

PubMed

Majetich, George; Zhang, Yong; Tian, Xinrong; Zou, Ge; Li, Yang; Wang, Yangyang; Hu, Shougang; Huddleston, Eric

2013-06-14

12-Hydroxy-9(10-->20)-5aH-abeo-abieta-1(10),8(9),12(13)-triene-11,14-dione (quinone 2) served as the dienophile in numerous intermolecular Diels-Alder reactions. These cycloadditions were conducted either thermally (including microwave heating) or with Lewis acid activation. While most dienes reacted with quinone 2 in good chemical yield, others were incompatible under the experimental conditions used.

Stereoselective protecting group free synthesis of D,L-gulose ethyl glycoside via multicomponent enyne cross metathesis--hetero Diels-Alder reaction.

PubMed

Castagnolo, Daniele; Botta, Lorenzo; Botta, Maurizio

2009-07-27

An efficient and stereoselective synthesis of D,L-gulose was described. The key step of the synthetic route is represented by a multicomponent enyne cross metathesis-hetero Diels-Alder reaction which allows the formation of the pyran ring from cheap and commercially available substrates in a single synthetic step. The synthesis of D,L-gulose was accomplished without the use of protecting groups making this approach highly desirable also in terms of atom economy.

High-speed microwave-promoted hetero-Diels-Alder reactions of 2(1H)-pyrazinones in ionic liquid doped solvents.

PubMed

Van Der Eycken, Erik; Appukkuttan, Prasad; De Borggraeve, Wim; Dehaen, Wim; Dallinger, Doris; Kappe, C Oliver

2002-11-01

Inter- and intramolecular hetero-Diels-Alder reactions in a series of functionalized 2(1H)-pyrazinones were investigated under controlled microwave irradiation. The cycloaddition reactions were efficiently performed in sealed tubes, utilizing either a combination of 1,2-dichloroethane and a thermally stable ionic liquid, or 1,2-dichlorobenzene as reaction medium. In all cases, a significant rate-enhancement using microwave flash heating as compared to thermal heating was observed.

Studies toward the synthesis of palhinine lycopodium alkaloids: a Morita-Baylis-Hillman/intramolecular Diels-Alder approach.

PubMed

Sizemore, Nicholas; Rychnovsky, Scott D

2014-02-07

A synthetic route to the isotwistane core of palhinine lycopodium alkaloids is described. A Morita-Baylis-Hillman/intramolecular Diels-Alder (IMDA) strategy sets the vicinal all-carbon quaternary centers present in this family of natural products. The regioselectivity of the IMDA reaction is dictated by the conditions employed for silyl enol ether formation, with one set of conditions providing the core of cardionine and alternate conditions generating the desired isotwistane core of isopalhinine.

Determination of Trophic State Changes with Diel Dissolved Oxygen: A Case Study in a Shallow Lake.

PubMed

Xu, Zhen; Xu, Y Jun

2015-11-01

Current trophic state indices (TSI) have been reported to have limitations in assessing changes in eutrophication status of shallow waters. This study aimed to use intensive measurements on dissolved oxygen (DO) to improve the determination of tropic state changes. The authors deployed an environment monitoring buoy in a eutrophic shallow lake and recorded water temperature, DO, and chlorophyll-a concentrations at 15-minute intervals for two 1-year periods: from August 2008 to July 2009 and from August 2013 to July 2014. In addition, they recorded water levels over the same periods and collected water samples for nutrient analysis. The authors analyzed the high-time resolution DO records, compared the diel DO trends between the two 1-year periods, and proposed a new TSI using DO. They found that analyzing the change in diel DO ranges can improve commonly used methods for classifying trophic states and assessing the change of eutrophication status of waterbodies.

Diels-Alderase-free, bis-pericyclic, [4+2] dimerization in the biosynthesis of (±)-paracaseolide A

NASA Astrophysics Data System (ADS)

Wang, Tao; Hoye, Thomas R.

2015-08-01

The natural product paracaseolide A is a tetracyclic dilactone containing six adjacent stereocentres. Its skeleton occupies a unique structural space among the >200,000 characterized secondary metabolites. Six different research groups have reported a chemical synthesis of this compound, five of which used a thermal, net Diels-Alder [4+2] cycloaddition and dehydration at 110 °C to access the target by dimerization of a simple butenolide precursor. Here, we report that this dimerization proceeds under much milder conditions and with a different stereochemical outcome than previously recognized. This can be rationalized by invoking a bis-pericyclic transition state. Furthermore, we find that spontaneous epimerization, necessary to correct the configuration at one key stereocentre, is viable and that natural paracaseolide A is racemic. Together, these facts point to the absence of enzymatic catalysis (that is, Diels-Alderase activity) in the cycloaddition and strongly suggest that a non-enzyme-mediated dimerization is the actual event by which paracaseolide A is produced in nature.

An interpenetrating HA/G/CS biomimic hydrogel via Diels-Alder click chemistry for cartilage tissue engineering.

PubMed

Yu, Feng; Cao, Xiaodong; Zeng, Lei; Zhang, Qing; Chen, Xiaofeng

2013-08-14

In order to mimic the natural cartilage extracellular matrix, a novel biological degradable interpenetrating network hydrogel was synthesized from the gelatin (G), hyaluronic acid (HA) and chondroitin sulfate (CS) by Diels-Alder "click" chemistry. HA was modified with furylamine and G was modified with furancarboxylic acid respectively. (1)H NMR spectra and elemental analysis showed that the substitution degrees of HA-furan and G-furan were 71.5% and 44.5%. Then the hydrogels were finally synthesized by cross-linking furan-modified HA and G derivatives with dimaleimide poly(ethylene glycol) (MAL-PEG-MAL). The mechanical and degradation properties of the hydrogels could be tuned simply through varying the molar ratio between furan and maleimide. Rheological, mechanical and degradation studies demonstrated that the Diels-Alder "click" chemistry is an efficient method for preparing high performance biological interpenetrating hydrogels. This biomimic hydrogel with improved mechanical properties could have great potential applications in cartilage tissue engineering. Copyright © 2013 Elsevier Ltd. All rights reserved.

Nocturnal and diurnal activity of armored suckermouth catfish (Loricariidae: Pterygoplichthys) associated with wintering Florida manatees (Trichechus manatus latirostris)

USGS Publications Warehouse

Nico, Leo G.

2010-01-01

Several Pterygoplichthys species, members of the Neotropical catfish family Loricariidae, have been widely introduced outside their native ranges. In this paper, I present observations on the diel activity pattern of non-native Pterygoplichthys, tentatively identified as P. disjunctivus, with respect to their attachment and grazing on endangered Florida manatees, Trichechus manatus latirostris. The study was conducted in December 2009 at Volusia Blue Spring, an artesianal spring system in the St. Johns River basin, Florida (USA). Supplemented by information gathered during previous visits to the spring site, this study revealed that adult Pterygoplichthys are active throughout the diel period (day, twilight and night). However, juvenile Pterygoplichthys were largely nocturnal and only at night did they consistently join adults in attaching to manatees. The juveniles generally remain hidden during the day, probably responding to presence of diurnal predators, mainly birds. Differences in diel behaviors among different Pterygoplichthys size classes in Florida are consistent with published observations on loricariids inhabiting clearwater streams within their native ranges.

Correlation of molecular expression with diel rhythm of oviposition in Calliphora vicina (Robineau-Desvoidy) (Diptera: Calliphoridae) and implications for forensic entomology.

PubMed

George, Kelly A; Archer, Melanie S; Toop, Tes

2015-01-01

This study explored the molecular mechanisms potentially underlying blow fly nocturnal oviposition. A behavioral study revealed that Calliphora vicina (Robineau-Desvoidy) (Diptera: Calliphoridae) possesses a diel rhythm of oviposition in light under 12:12 light/dark conditions. Reversal to 12:12 dark/light resulted in oviposition behavior changing to align with the adjusted regime in most females, but four of 59 experimental females lacked a diel rhythm of oviposition (were arrhythmic). Real-time PCR was used to monitor the molecular expression levels of known circadian genes per and tim in C. vicina to determine whether gene expression and behavior correlated. As with behavior, reversing light/dark conditions changed rhythmic gene expression to align with an adjusted light regime. This suggests that although it is unlikely that C. vicina will colonize dead bodies at night, arrhythmic females and oviposition in the dark was demonstrated. © 2014 American Academy of Forensic Sciences.

Theoretical study of Diels-Alder cycloadditions of butadiene to C{sub 70}. An insight into the chemical reactivity of C{sub 70} as compared to C{sub 60}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mestres, J.; Duran, M.; Sola, M.

1996-05-02

The eight unique Diels-Alder cycloadditions of butadiene to C{sub 70} are analyzed theoretically and compared with the well-established, two possible Diels-Alder cycloadditions of butadiene to C{sub 60}. Full geometry optimizations of reactants, adducts, and transition states are performed using the AMI semiempirical method followed by single-point ab initio energy calculations. The results show that the cycloaddition of butadiene to the C{sub 70} fullerene in the gas phase is slightly more reactive than that to C{sub 60}. However, in toluene solution calculations yield that the different solvent effects on C{sub 60} and C{sub 70} cause a significant decrease of the energymore » barrier in the C{sub 60} cycloaddition, thus predicting a larger reactivity for C{sub 60} as compared to the C{sub 70} fullerene. 36 refs., 2 figs., 3 tabs.« less

Diel patterns in underwater sounds produced by beluga whales and Pacific white-sided dolphins at John G. Shedd Aquarium

NASA Astrophysics Data System (ADS)

Brickman, Jon; Tanchez, Erin; Thomas, Jeanette

2005-09-01

Diel patterns in underwater sounds from five beluga whales (Delphinapterus leucas) and five Pacific white-sided dolphins (Lagenorhynchus obliquidens) housed at John G. Shedd Aquarium in Chicago, IL were studied. Underwater sounds were sampled systematically over 24-h periods by using a battery-operated cassette recorder and an Ithaco 605C hydrophone controlled by a digital timer, which activated every hour and then shut off after 2.5 min. Belugas had 14 sounds and Pacific white-sided dolphins produced 5 sounds. For each species, the use of some sounds was correlated with other sounds. The diel pattern for both species was similar and mostly affected by the presence of humans. Sounds gradually increased after the staff and visitors arrived, peaked during the midday, gradually decreased as closing of the aquarium approached, and was minimal overnight. These data can help identify the best time of day to make recordings and perhaps could be used to examine social, reproductive, or health changes in these captive cetaceans.

Diel changes in the near-surface biomass of zooplankton and the carbon content of vertical migrants

NASA Astrophysics Data System (ADS)

Hays, Graeme C.; Harris, Roger P.; Head, Robert N.

Zooplankton biomass and the carbon content of vertical migrants were measured in the NE Atlantic (36.5°N, 19.2°W) between 11 and 18 July 1996 as part of the Plankton Reactivity in the Marine Environment (PRIME) programme. The increase in zooplankton biomass near the surface (0-100 m) at night compared to during the day suggested that diel vertical migration was an important feature at this site. For three species of vertically migrant copepods, Pleuromamma pisekii, P. gracilis and P. abdominalis, the carbon content of individuals collected at dusk was significantly less than for individuals collected at dawn, with this reduction being 6.2, 7.3 and 14.8%, respectively. This dawn-dusk reduction in carbon content is consistent with the diel pattern of feeding and fasting exhibited by vertical migrants and supports the suggestion that migrating zooplankton will cause an active export of carbon from the surface layers.

Diel timing and frequency of sugar feeding in the mosquito Anopheles gambiae, depending on sex, gonotrophic state and resource availability.

PubMed

Gary, R E; Foster, W A

2006-09-01

Little is known about the sugar-feeding behaviour of equatorial Africa's principal vector of malaria, Anopheles gambiae Giles (Diptera: Culicidae). It is suspected to feed on plant sugar infrequently, but possibly the timing depends on environmental circumstances, and males may differ markedly from females. These points of uncertainty were clarified in the laboratory, by monitoring both diel and longterm sugar-feeding activity in both sexes. Males fed on sugar in a nocturnal diel rhythm closely approximating non-specific flight activity. Female diel sugar-feeding patterns resembled published rhythms and cycles of host seeking. Males sugar fed nightly at an average frequency of about twice per night, sustained over 17 days. This was substantially higher than the sugar-feeding frequency of females that were allowed both blood and oviposition sites every night: they averaged about one sugar feed in every 4 nights. These females fed on sugar between gonotrophic cycles, after eggs were mature but before the next bloodmeal. They did not sugar feed during the 2 days after blood feeding, while blood was being digested and the eggs developed. A slight delay in the availability of either the oviposition site or blood led to an increase in female sugar-feeding frequency: they averaged more than once per night until the delayed resource was made available. These observations support the conclusion that sugar feeding is a normal part of the biology of both sexes of An. gambiae.

Questa baseline and pre-mining ground-water quality investigation. 20. Water chemistry of the Red River and selected seeps, tributaries, and precipitation, Taos County, New Mexico, 2000-2004

USGS Publications Warehouse

Verplanck, P.L.; McCleskey, R. Blaine; Nordstrom, D. Kirk

2006-01-01

As part of a multi-year project to infer the pre-mining ground-water quality at Molycorp's Questa mine site, surface-water samples of the Red River, some of its tributaries, seeps, and snow samples were collected for analysis of inorganic solutes and of water and sulfate stable isotopes in selected samples. The primary aim of this study was to document diel, storm event, and seasonal variations in water chemistry for the Red River and similar variations in water chemistry for Straight Creek, a natural analog site similar in topography, hydrology, and geology to the mine site for inferring pre-mining water-quality conditions. Red River water samples collected between 2000 and 2004 show that the largest variations in water chemistry occur during late summer rainstorms, often monsoonal in nature. Within hours, discharge of the Red River increased from 8 to 102 cubic feet per second and pH decreased from 7.80 to 4.83. The highest concentrations of metals (iron, aluminum, zinc, manganese) and sulfate also occur during such events. Low-pH and high-solute concentrations during rainstorm runoff are derived primarily from alteration 'scar' areas of naturally high mineralization combined with steep topography that exposes continually altered rock because erosion is too rapid for vegetative growth. The year 2002 was one of the driest on record, and Red River discharge reflected the low seasonal snow pack. No snowmelt peak appeared in the hydrograph record, and a late summer storm produced the highest flow for the year. Snowmelt was closer to normal during 2003 and demonstrated the dilution effect of snowmelt on water chemistry. Two diel sampling events were conducted for the Red River, one during low flow and the other during high flow, at two locations, at the Red River gaging station and just upstream from Molycorp's mill site. No discernible diel trends were observed except for dissolved zinc and manganese at the upstream site during low flow. Straight Creek drainage water was sampled periodically from 2001 to 2004 at the down stream end of surface drainage near the point at which it disappeared into the debris fan. This water has a minimal range in pH (2.7 to 3.2) but a substantial concentration range in many solutes; for example, sulfate concentrations varied from 525 to 2,660 mg/L. Many elements covary with sulfate suggesting that dilution is the primary control of the range in solute concentrations. A transect of water samples higher in the scar area were collected in October of 2003. They had a lower range in pH (2.44 to 3.05) and higher solute concentrations than those collected periodically from lower in the catchment. Water isotopes for the upper transect samples indicated slight evaporation, and in part, may account for the higher solute concentrations. Drainage waters also were collected from Hottentot, Junebug, Hansen, Little Hansen, and Goat Hill Gulch drainages. Most constituents from other scar drainage waters showed ranges of concentration similar to those of the Straight Creek waters. An exception was water collected from Goat Hill Gulch, which has some of the highest concentrations of any surface-water sample collected but also contained waste-rock leachates.

Plant-water relationships in the Great Basin Desert of North America derived from Pinus monophylla hourly dendrometer records.

PubMed

Biondi, Franco; Rossi, Sergio

2015-08-01

Water is the main limiting resource for natural and human systems, but the effect of hydroclimatic variability on woody species in water-limited environments at sub-monthly time scales is not fully understood. Plant-water relationships of single-leaf pinyon pine (Pinus monophylla) were investigated using hourly dendrometer and environmental data from May 2006 to October 2011 in the Great Basin Desert, one of the driest regions of North America. Average radial stem increments showed an annual range of variation below 1.0 mm, with a monotonic steep increase from May to July that yielded a stem enlargement of about 0.5 mm. Stem shrinkage up to 0.2 mm occurred in late summer, followed by an abrupt expansion of up to 0.5 mm in the fall, at the arrival of the new water year precipitation. Subsequent winter shrinkage and enlargement were less than 0.3 mm each. Based on 4 years with continuous data, diel cycles varied in both timing and amplitude between months and years. Phase shifts in circadian stem changes were observed between the growing season and the dormant one, with stem size being linked to precipitation more than to other water-related indices, such as relative humidity or soil moisture. During May-October, the amplitude of the phases of stem contraction, expansion, and increment was positively related to their duration in a nonlinear fashion. Changes in precipitation regime, which affected the diel phases especially when lasting more than 5-6 h, could substantially influence the dynamics of water depletion and replenishment in single-leaf pinyon pine.

Plant-water relationships in the Great Basin Desert of North America derived from Pinus monophylla hourly dendrometer records

NASA Astrophysics Data System (ADS)

Biondi, Franco; Rossi, Sergio

2015-08-01

Water is the main limiting resource for natural and human systems, but the effect of hydroclimatic variability on woody species in water-limited environments at sub-monthly time scales is not fully understood. Plant-water relationships of single-leaf pinyon pine ( Pinus monophylla) were investigated using hourly dendrometer and environmental data from May 2006 to October 2011 in the Great Basin Desert, one of the driest regions of North America. Average radial stem increments showed an annual range of variation below 1.0 mm, with a monotonic steep increase from May to July that yielded a stem enlargement of about 0.5 mm. Stem shrinkage up to 0.2 mm occurred in late summer, followed by an abrupt expansion of up to 0.5 mm in the fall, at the arrival of the new water year precipitation. Subsequent winter shrinkage and enlargement were less than 0.3 mm each. Based on 4 years with continuous data, diel cycles varied in both timing and amplitude between months and years. Phase shifts in circadian stem changes were observed between the growing season and the dormant one, with stem size being linked to precipitation more than to other water-related indices, such as relative humidity or soil moisture. During May-October, the amplitude of the phases of stem contraction, expansion, and increment was positively related to their duration in a nonlinear fashion. Changes in precipitation regime, which affected the diel phases especially when lasting more than 5-6 h, could substantially influence the dynamics of water depletion and replenishment in single-leaf pinyon pine.

Vertical distribution and diel migration of macrozooplankton in the St. Lawrence marine system (Canada) in relation with the cold intermediate layer thermal properties

NASA Astrophysics Data System (ADS)

Harvey, Michel; Galbraith, Peter S.; Descroix, Aurélie

2009-01-01

Vertical distribution of various species and stages of macrozooplankton (euphausiacea, chaetognatha, cnidaria, mysidacea, amphipoda) were determined for different times of the day and related to the physical environment. Stratified sampling with the BIONESS was carried out during seven cruises in spring and fall 1998, 2000, and 2001, and fall 1999, in two different habitats in the St. Lawrence marine system: the lower St. Lawrence Estuary and the NW Gulf of St. Lawrence. Our results indicate that the various macrozooplankton species were distributed throughout the whole water column including the surface layer, the cold intermediate layer (CIL), and the deep layer at different times of day and night in both areas during all periods. Moreover, three types of migrational patterns were observed within this zooplanktonic community: (1) nocturnal ascent by the whole population, (2) segregation into two groups; one which performed nocturnal accent and another which remained in the deep, and (3) no detectable migration. We also observed that the diel vertical migration (DVM) amplitude in most of the macrozooplankton species varied as a function of physical factors, in particular the spatio-temporal variations of the CIL thermal properties, including the upper and the lower limits of the CIL and the depth of the CIL core temperature. Finally, the different DVM patterns coupled with estuarine circulation patterns and bottom topography could place animals in different flow regimes by night and by day and contribute to their retention (aggregation) and/or dispersion in different areas, time of the day, and seasons.

Robust hierarchical state-space models reveal diel variation in travel rates of migrating leatherback turtles.

PubMed

Jonsen, Ian D; Myers, Ransom A; James, Michael C

2006-09-01

1. Biological and statistical complexity are features common to most ecological data that hinder our ability to extract meaningful patterns using conventional tools. Recent work on implementing modern statistical methods for analysis of such ecological data has focused primarily on population dynamics but other types of data, such as animal movement pathways obtained from satellite telemetry, can also benefit from the application of modern statistical tools. 2. We develop a robust hierarchical state-space approach for analysis of multiple satellite telemetry pathways obtained via the Argos system. State-space models are time-series methods that allow unobserved states and biological parameters to be estimated from data observed with error. We show that the approach can reveal important patterns in complex, noisy data where conventional methods cannot. 3. Using the largest Atlantic satellite telemetry data set for critically endangered leatherback turtles, we show that the diel pattern in travel rates of these turtles changes over different phases of their migratory cycle. While foraging in northern waters the turtles show similar travel rates during day and night, but on their southward migration to tropical waters travel rates are markedly faster during the day. These patterns are generally consistent with diving data, and may be related to changes in foraging behaviour. Interestingly, individuals that migrate southward to breed generally show higher daytime travel rates than individuals that migrate southward in a non-breeding year. 4. Our approach is extremely flexible and can be applied to many ecological analyses that use complex, sequential data.

The Fish Assemblage of a Newfoundland Estuary: Diel, Monthly and Annual Variation

NASA Astrophysics Data System (ADS)

Methven, D. A.; Haedrich, R. L.; Rose, G. A.

2001-06-01

Twice monthly sampling over two 16 month periods at a shallow site on Newfoundland's east coast showed the fish assemblage to be dominated by four taxa ( Gasterosteus aculeatus, G. wheatlandi, Osmerus mordax, Gadus spp.) that accounted for 96% of the individuals collected. Of the 16 479 fish measured, 65% were adults based on the estimated size of first spawning. The fish assemblage was dominated (86%) by species with demersal eggs, several of which spawn at the same shallow sites used by juveniles as nursery sites. Coastal spawning and demersal eggs maintain offspring in coastal nursery areas where survival is thought to be increased. Number of species and number of fish were both correlated with water temperature being highest from mid-summer to early autumn and lowest in winter. Temperature, time of spawning, and movements of juveniles and adults facilitated grouping species into five assemblages based on seasonal abundance: seasonal periodic species (summer and winter), regular species, regular species collected in all seasons except winter, and occasional (rare) species. At the diel scale, two consistent species groupings were observed: species that showed no significant difference between day and night and species caught primarily at night. Number of night species exceeded day species by a factor of two. No seine-caught species in shallow water exhibited significantly higher catches during the day. Observations by SCUBA divers indicated some species were more abundant during day time at slightly deeper depths. This observation in conjunction with day and night seining in shallower water, suggests these species aggregate in deeper water during day and move to shallow waters at night.

Responses of the picoprasinophyte Micromonas commoda to light and ultraviolet stress.

PubMed

Cuvelier, Marie L; Guo, Jian; Ortiz, Alejandra C; van Baren, Marijke J; Tariq, Muhammad Akram; Partensky, Frédéric; Worden, Alexandra Z

2017-01-01

Micromonas is a unicellular marine green alga that thrives from tropical to polar ecosystems. We investigated the growth and cellular characteristics of acclimated mid-exponential phase Micromonas commoda RCC299 over multiple light levels and over the diel cycle (14:10 hour light:dark). We also exposed the light:dark acclimated M. commoda to experimental shifts from moderate to high light (HL), and to HL plus ultraviolet radiation (HL+UV), 4.5 hours into the light period. Cellular responses of this prasinophyte were quantified by flow cytometry and changes in gene expression by qPCR and RNA-seq. While proxies for chlorophyll a content and cell size exhibited similar diel variations in HL and controls, with progressive increases during day and decreases at night, both parameters sharply decreased after the HL+UV shift. Two distinct transcriptional responses were observed among chloroplast genes in the light shift experiments: i) expression of transcription and translation-related genes decreased over the time course, and this transition occurred earlier in treatments than controls; ii) expression of several photosystem I and II genes increased in HL relative to controls, as did the growth rate within the same diel period. However, expression of these genes decreased in HL+UV, likely as a photoprotective mechanism. RNA-seq also revealed two genes in the chloroplast genome, ycf2-like and ycf1-like, that had not previously been reported. The latter encodes the second largest chloroplast protein in Micromonas and has weak homology to plant Ycf1, an essential component of the plant protein translocon. Analysis of several nuclear genes showed that the expression of LHCSR2, which is involved in non-photochemical quenching, and five light-harvesting-like genes, increased 30 to >50-fold in HL+UV, but was largely unchanged in HL and controls. Under HL alone, a gene encoding a novel nitrite reductase fusion protein (NIRFU) increased, possibly reflecting enhanced N-assimilation under the 625 μmol photons m-2 s-1 supplied in the HL treatment. NIRFU's domain structure suggests it may have more efficient electron transfer than plant NIR proteins. Our analyses indicate that Micromonas can readily respond to abrupt environmental changes, such that strong photoinhibition was provoked by combined exposure to HL and UV, but a ca. 6-fold increase in light was stimulatory.

Responses of the picoprasinophyte Micromonas commoda to light and ultraviolet stress

DOE PAGES

Cuvelier, Marie L.; Guo, Jian; Ortiz, Alejandra C.; ...

2017-03-09

Micromonas is a unicellular marine green alga that thrives from tropical to polar ecosystems. We investigated the growth and cellular characteristics of acclimated mid-exponential phase Micromonas commoda RCC299 over multiple light levels and over the diel cycle (14:10 hour light:dark). We also exposed the light:dark acclimated M. commoda to experimental shifts from moderate to high light (HL), and to HL plus ultraviolet radiation (HL+UV), 4.5 hours into the light period. Cellular responses of this prasinophyte were quantified by flow cytometry and changes in gene expression by qPCR and RNA-seq. While proxies for chlorophyll a content and cell size exhibited similarmore » diel variations in HL and controls, with progressive increases during day and decreases at night, both parameters sharply decreased after the HL+UV shift. Two distinct transcriptional responses were observed among chloroplast genes in the light shift experiments: i) expression of transcription and translation-related genes decreased over the time course, and this transition occurred earlier in treatments than controls; ii) expression of several photosystem I and II genes increased in HL relative to controls, as did the growth rate within the same diel period. However, expression of these genes decreased in HL+UV, likely as a photoprotective mechanism. RNA-seq also revealed two genes in the chloroplast genome, ycf2-like and ycf1-like, that had not previously been reported. The latter encodes the second largest chloroplast protein in Micromonas and has weak homology to plant Ycf1, an essential component of the plant protein translocon. Analysis of several nuclear genes showed that the expression of LHCSR2, which is involved in non-photochemical quenching, and five light-harvesting-like genes, increased 30 to >50-fold in HL+UV, but was largely unchanged in HL and controls. Under HL alone, a gene encoding a novel nitrite reductase fusion protein (NIRFU) increased, possibly reflecting enhanced N-assimilation under the 625 μmol photons m -2 s -1 supplied in the HL treatment. NIRFU's domain structure suggests it may have more efficient electron transfer than plant NIR proteins. Lastly, our analyses indicate that Micromonas can readily respond to abrupt environmental changes, such that strong photoinhibition was provoked by combined exposure to HL and UV, but a ca. 6-fold increase in light was stimulatory.« less

Responses of the picoprasinophyte Micromonas commoda to light and ultraviolet stress

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cuvelier, Marie L.; Guo, Jian; Ortiz, Alejandra C.

Micromonas is a unicellular marine green alga that thrives from tropical to polar ecosystems. We investigated the growth and cellular characteristics of acclimated mid-exponential phase Micromonas commoda RCC299 over multiple light levels and over the diel cycle (14:10 hour light:dark). We also exposed the light:dark acclimated M. commoda to experimental shifts from moderate to high light (HL), and to HL plus ultraviolet radiation (HL+UV), 4.5 hours into the light period. Cellular responses of this prasinophyte were quantified by flow cytometry and changes in gene expression by qPCR and RNA-seq. While proxies for chlorophyll a content and cell size exhibited similarmore » diel variations in HL and controls, with progressive increases during day and decreases at night, both parameters sharply decreased after the HL+UV shift. Two distinct transcriptional responses were observed among chloroplast genes in the light shift experiments: i) expression of transcription and translation-related genes decreased over the time course, and this transition occurred earlier in treatments than controls; ii) expression of several photosystem I and II genes increased in HL relative to controls, as did the growth rate within the same diel period. However, expression of these genes decreased in HL+UV, likely as a photoprotective mechanism. RNA-seq also revealed two genes in the chloroplast genome, ycf2-like and ycf1-like, that had not previously been reported. The latter encodes the second largest chloroplast protein in Micromonas and has weak homology to plant Ycf1, an essential component of the plant protein translocon. Analysis of several nuclear genes showed that the expression of LHCSR2, which is involved in non-photochemical quenching, and five light-harvesting-like genes, increased 30 to >50-fold in HL+UV, but was largely unchanged in HL and controls. Under HL alone, a gene encoding a novel nitrite reductase fusion protein (NIRFU) increased, possibly reflecting enhanced N-assimilation under the 625 μmol photons m -2 s -1 supplied in the HL treatment. NIRFU's domain structure suggests it may have more efficient electron transfer than plant NIR proteins. Lastly, our analyses indicate that Micromonas can readily respond to abrupt environmental changes, such that strong photoinhibition was provoked by combined exposure to HL and UV, but a ca. 6-fold increase in light was stimulatory.« less

Carbonate chemistry of an in-situ free-ocean CO2 enrichment experiment (antFOCE) in comparison to short term variation in Antarctic coastal waters.

PubMed

Stark, J S; Roden, N P; Johnstone, G J; Milnes, M; Black, J G; Whiteside, S; Kirkwood, W; Newbery, K; Stark, S; van Ooijen, E; Tilbrook, B; Peltzer, E T; Berry, K; Roberts, D

2018-02-12

Free-ocean CO 2 enrichment (FOCE) experiments have been deployed in marine ecosystems to manipulate carbonate system conditions to those predicted in future oceans. We investigated whether the pH/carbonate chemistry of extremely cold polar waters can be manipulated in an ecologically relevant way, to represent conditions under future atmospheric CO 2 levels, in an in-situ FOCE experiment in Antarctica. We examined spatial and temporal variation in local ambient carbonate chemistry at hourly intervals at two sites between December and February and compared these with experimental conditions. We successfully maintained a mean pH offset in acidified benthic chambers of -0.38 (±0.07) from ambient for approximately 8 weeks. Local diel and seasonal fluctuations in ambient pH were duplicated in the FOCE system. Large temporal variability in acidified chambers resulted from system stoppages. The mean pH, Ω arag and fCO 2 values in the acidified chambers were 7.688 ± 0.079, 0.62 ± 0.13 and 912 ± 150 µatm, respectively. Variation in ambient pH appeared to be mainly driven by salinity and biological production and ranged from 8.019 to 8.192 with significant spatio-temporal variation. This experiment demonstrates the utility of FOCE systems to create conditions expected in future oceans that represent ecologically relevant variation, even under polar conditions.

Exploiting the Electrophilic and Nucleophilic Dual Role of Nitrile Imines: One-Pot, Three-Component Synthesis of Furo[2,3-d]pyridazin-4(5H)-ones.

PubMed

Giustiniano, Mariateresa; Mercalli, Valentina; Amato, Jussara; Novellino, Ettore; Tron, Gian Cesare

2015-08-21

An expeditious multicomponent reaction to synthesize tetrasubstituted furo[2,3-d]pyridazin-4(5H)-ones is reported. In brief, hydrazonoyl chlorides react with isocyanoacetamides, in the presence of TEA, to give 1,3-oxazol-2-hydrazones which, without being isolated, can react with dimethylacetylene dicarboxylate to afford furo[2,3-d]pyridazin-4(5H)-ones with an unprecedented level of complexity in a triple domino Diels-Alder/retro-Diels-Alder/lactamization reaction sequence.

L-Pyroglutamic Sulphonamide as Hydrogen-Bonding Organocatalyst: Enantioselective Diels-Alder Cyclization to Construct Carbazolespirooxindoles.

PubMed

Ren, Ji-Wei; Wang, Jing; Xiao, Jun-An; Li, Jun; Xiang, Hao-Yue; Chen, Xiao-Qing; Yang, Hua

2017-06-16

Hydrogen-bonding organocatalysts L-pyroglutamic sulphonamides were readily synthesized for the first time by fully exploiting the potentials of L-pyroglutamic acid. The newly designed catalyst was successfully applied in catalyzing asymmetric Diels-Alder cyclization of methyleneindolinones with 2-vinyl-1H-indoles to efficiently assemble carbazolespirooxindoles in excellent stereoselectivity (up to 99% ee, >20:1 dr) and yields (up to 99%). Mechanistic studies disclosed that the well-designed hydrogen-bonding modes between L-pyroglutamic sulphonamide and substrates were crucial for stereocontrol in the cyclization.

Synthesis of Pyrrolo[1,2-a]pyrimidine Enantiomers via Domino Ring-Closure followed by Retro Diels-Alder Protocol.

PubMed

Fekete, Beáta; Palkó, Márta; Haukka, Matti; Fülöp, Ferenc

2017-04-13

From 2-aminonorbornene hydroxamic acids, a simple and efficient method for the preparation of pyrrolo[1,2- a ]pyrimidine enantiomers is reported. The synthesis is based on domino ring-closure followed by microwave-induced retro Diels-Alder (RDA) protocols, where the chirality of the desired products is transferred from norbornene derivatives. The stereochemistry of the synthesized compounds was proven by X-ray crystallography. The absolute configuration of the product is determined by the configuration of the starting amino hydroxamic acid.

Thermally cleavable surfactants

DOE Office of Scientific and Technical Information (OSTI.GOV)

McElhanon, James R; Simmons, Blake A; Zifer, Thomas

2009-11-24

Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments or the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.

Thermally cleavable surfactants

DOE Office of Scientific and Technical Information (OSTI.GOV)

McElhanon, James R; Simmons, Blake A; Zifer, Thomas

2009-09-29

Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments or the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.

Diels-Alder reactions of five-membered heterocycles containing one heteroatom

PubMed Central

Ding, Xiaoyuan; Nguyen, Son T.; Williams, John D.; Peet, Norton P.

2015-01-01

Diels-Alder reactions of five-membered heterocycles containing one heteroatom with an N-arylmaleimide were studied. Cycloaddition of 2,5-dimethylfuran (4) with 2-(4-methylphenyl)maleimide (3) in toluene at 60 °C gave bicyclic adduct 5. Cycloadditions of 3 with 2,5-dimethylthiophene (11) and 1,2,5-trimethylpyrrole (14) were also studied. Interestingly, the bicyclic compound 5 cleanly rearranged, with loss of water, when treated with p-toluenesulfonic acid in toluene at 80 °C to give 4,7-dimethyl-2-p-tolylisoindoline-1,3-dione (6). PMID:25838605

Diel distribution of zooplankton at the Mobil OTEC site (29/sup 0/N 88/sup 0/W) in the Northern Gulf of Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steen, Jr, J P; Gunter, G; Hartwig, E O

1982-01-01

In the study 128 copepod species and 43 other zooplankton taxa were identified from four depth strata (0 to 50 m, 50 to 100 m, 100 to 300 m and 300 to 500 m). Duplicate step-oblique tows at six hour intervals over 24 hours were taken at a site in the Gulf of Mexico. The distribution of zooplankton numbers and sizes, and species diversity, richness and evenness through a diel period are described.

Spectacular Rate Enhancement of the Diels-Alder Reaction at the Ionic Liquid/n-Hexane Interface.

PubMed

Beniwal, Vijay; Manna, Arpan; Kumar, Anil

2016-07-04

The use of the ionic liquid/n-hexane interface as a new class of reaction medium for the Diels-Alder reaction gives large rate enhancements of the order of 10(6) to 10(8) times and high stereoselectivity, as compared to homogeneous media. The rate enhancement is attributed to the H-bonding abilities and polarities of the ionic liquids, whereas the hydrophobicity of ionic liquids was considered to be the factor in controlling stereoselectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Tunable and Enantioselective Hetero-Diels-Alder Reaction Provides Access to Distinct Piperidinoyl Spirooxindoles.

PubMed

Jayakumar, Samydurai; Louven, Kathrin; Strohmann, Carsten; Kumar, Kamal

2017-12-11

The active complexes of chiral N,N'-dioxide ligands with dysprosium and magnesium salts catalyze the hetero-Diels-Alder reaction between 2-aza-3-silyloxy-butadienes and alkylidene oxindoles to selectively form 3,3'- and 3,4'-piperidinoyl spirooxindoles, respectively, in very high yields and with excellent enantioselectivities. The exo-selective asymmetric cycloaddition successfully regaled the construction of sp 3 -rich and highly substituted natural-product-based spirooxindoles supporting many chiral centers, including contiguous all-carbon quaternary centers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermally cleavable surfactants

DOEpatents

McElhanon, James R [Manteca, CA; Simmons, Blake A [San Francisco, CA; Zifer, Thomas [Manteca, CA; Jamison, Gregory M [Albuquerque, NM; Loy, Douglas A [Albuquerque, NM; Rahimian, Kamyar [Albuquerque, NM; Long, Timothy M [Urbana, IL; Wheeler, David R [Albuquerque, NM; Staiger, Chad L [Albuquerque, NM

2006-04-04

Two new surfactant molecules are reported which contain thermally labile Diels-Alder adducts connecting the polar and non-polar sections of each molecule. The two surfactants possess identical non-polar dodecyl tail segments but exhibit different polar headgroups. The surfactants become soluble in water when anionic salts are formed through the deprotonation of the surfactant headgroups by the addition of potassium hydroxide. When either surfactant is exposed to temperature above about 60.degree. C., the retro Diels-Alder reaction occurs, yielding hydrophilic and hydrophobic fragments and the aqueous solutions of the surfactants subsequently exhibit loss of all surface-active behavior.

Buoyancy differences among two deepwater ciscoes from the Great Lakes and their putative ancestor

USGS Publications Warehouse

Krause, A.E.; Eshenroder, R.L.; Begnoche, L.J.

2002-01-01

We analyzed buoyancy in two deepwater ciscoes, Coregonus hoyi and C. kiyi, and in C. artedi, their putative ancestor, and also analyzed how variations in fish weight, water content, and lipid content affected buoyancy. Buoyancy was significantly different among the three species (p < 0.0001). Estimates of percent buoyancy (neutral buoyancy = 0.0%) were: kiyi, 3.8%; hoyi, 4.7%; and artedi, 5.7%. Buoyancy did not change with fish weight alone (p = 0.38). Fish weight was negatively related to water content for all three species (p = 0.037). Lipid content was not significantly different between hoyi and kiyi, but artedi had significantly fewer lipids than hoyi and kiyi (p < 0.10). When artedi was removed from the analysis, fish weight and lipids accounted for 48% of the variation in buoyancy (p = 0.003), fatter hoyi were less dense than leaner hoyi, but fatter and leaner kiyi were no different in density. Our findings provide additional evidence that buoyancy regulation was a speciating mechanism in deepwater ciscoes and that kiyi is more specialized than hoyi for diel-vertical migration in deep water.

Phylogenetic, ecological, and allometric correlates of cranial shape in Malagasy lemuriforms.

PubMed

Baab, Karen L; Perry, Jonathan M G; Rohlf, F James; Jungers, William L

2014-05-01

Adaptive radiations provide important insights into many aspects of evolution, including the relationship between ecology and morphological diversification as well as between ecology and speciation. Many such radiations include divergence along a dietary axis, although other ecological variables may also drive diversification, including differences in diel activity patterns. This study examines the role of two key ecological variables, diet and activity patterns, in shaping the radiation of a diverse clade of primates, the Malagasy lemurs. When phylogeny was ignored, activity pattern and several dietary variables predicted a significant proportion of cranial shape variation. However, when phylogeny was taken into account, only typical diet accounted for a significant proportion of shape variation. One possible explanation for this discrepancy is that this radiation was characterized by a relatively small number of dietary shifts (and possibly changes in body size) that occurred in conjunction with the divergence of major clades. This pattern may be difficult to detect with the phylogenetic comparative methods used here, but may characterize not just lemurs but other mammals. © 2014 The Author(s). Evolution © 2014 The Society for the Study of Evolution.

Mercury speciation and exchanges at the air-water interface of a tropical artificial reservoir, French Guiana.

PubMed

Muresan, B; Cossa, D; Richard, S; Burban, B

2007-10-15

The distribution and speciation of mercury (Hg) in air, rain, and surface waters from the artificial tropical lake of Petit-Saut in French Guiana were investigated during the 2003/04 period. In the air, total gaseous mercury (TGM) at the dam station averaged 12+/-2 pmol m(-3) of which >98% was gaseous elemental mercury (GEM). GEM distribution depicted a day-night cycling with high concentrations (up to 15 pmol m(-3)) at dawn and low concentrations (down to 5 pmol m(-3)) at nightfall. Reactive gaseous mercury (RGM) represented <1% of the GEM with a mean concentration of 4+/-3 fmol m(-3). Diel RGM variations were negatively related to GEM. In the rain, the sum of all Hg species in the unfiltered (HgT(UNF)) averaged 16+/-12 pmol L(-1). Temporal distribution of HgT(UNF) exhibited a pattern of high concentrations during the late dry seasons (up to 57.5 pmol L(-1)) and low concentrations (down to 2.7 pmol L(-1)) in the course of the wet seasons. Unfiltered reactive (HgR(UNF)), dissolved gaseous (DGM) and monomethyl (MMHg(UNF)) Hg constituted 20, 5 and 5% of HgT(UNF), respectively. All measured Hg species were positively related and displayed negative relationships with the pH of the rain. In the reservoir surface waters, dissolved total mercury (HgT(D)) averaged 3.4+/-1.2 pmol L(-1) of which 10% consisted of DGM. DGM showed a trend of high concentrations during the dry seasons (480+/-270 fmol L(-1)) and lower (230+/-130 fmol L(-1)) in the course of the wet seasons. Diel variations included diurnal photo-induced DGM production (of about 60 fmol L(-1) h(-1)) coupled to minute to hour oxidation/reduction cycles (of >100 fmol L(-1) amplitude). Finally, calculated atmospheric Hg inputs to the Petit-Saut reservoir represented 14 mol yr(-1) whereas DGM evasion reached 23 mol yr(-1). Apportionment among forms of Hg deposition indicated that up to 75% of the total Hg invasive flux follows the rainfall pathway.

Decoupling the effects of primary production and residence time variation on nitrogen retention in a tidally-influenced spring run

NASA Astrophysics Data System (ADS)

Hensley, R. T.; Cohen, M. J.; Korhnak, L. V.

2013-12-01

Models of nitrogen (N) retention in river networks suggest biogeochemical as well as hydraulic properties exert considerable control on reach scale nutrient retention rates. Freshwater tidally influenced rivers provide a model system for decoupling metabolic vs. hydraulic controls on retention. The clear diurnal N retention signal in response to assimilatory uptake observed in other rivers becomes convoluted as the solar day moves in and out of phase with the semi-diurnal (~12.5 hr) tidal cycle. We used an upstream-downstream mass balance approach to estimate N retention at 15 minute intervals over an entire lunar month in Manatee Springs, a tidally varying, spring-fed stream in North Florida. Retention rates varied markedly with tidal forcing. Contrary to our expectations, higher retention rates and shorter uptake lengths were observed at low tide, corresponding to the shortest residence times, which varied between 22 and 71 minutes in this 350m reach. By profiling a continuously injected conservative tracer under both high and low tide conditions, we determined this was not the result of variation in lateral inflow (e.g., dilution from denitrified hyporheic porewater at lower channel stage). This increased retention at shorter residence times (and hence higher velocity) may be the result of greater turbulent mixing, which drives river water into the benthic reactive zone where the principal retention pathway, denitrification, occurs. After controlling for residence time effects, the residual retention signal exhibited a strong diel pattern. This assimilatory N retention was highly correlated with daily primary production (using the diel oxygen method), and estimated ecosystem molar C:N ratios (8.55×0.83:1) were comparable to observed tissue stoichiometry of the dominant autotrophs (9:1). N retention (blue) and residence time (red) calculated at 15 minute intervals. Note the inverse correlation; highest retention rates occur at the shortest residence times. N retention versus residence time separated into daytime (yellow) and nighttime (blue) data points. Note the daytime data points generally lie above the nighttime regression as a result of higher daytime retention due to assimilatory uptake.

Application of activity sensors for estimating behavioral patterns

USGS Publications Warehouse

Roberts, Caleb P.; Cain, James W.; Cox, Robert D.

2016-01-01

The increasing use of Global Positioning System (GPS) collars in habitat selection studies provides large numbers of precise location data points with reduced field effort. However, inclusion of activity sensors in many GPS collars also grants the potential to remotely estimate behavioral state. Thus, only using GPS collars to collect location data belies their full capabilities. Coupling behavioral state with location data would allow researchers and managers to refine habitat selection models by using diel behavioral state changes to partition fine-scale temporal shifts in habitat selection. We tested the capability of relatively unsophisticated GPS-collar activity sensors to estimate behavior throughout diel periods using free-ranging female elk (Cervus canadensis) in the Jemez Mountains of north-central New Mexico, USA, 2013–2014. Collars recorded cumulative number of movements (hits) per 15-min recording period immediately preceding GPS fixes at 0000, 0600, 1200, and 1800 hr. We measured diel behavioral patterns of focal elk, categorizing active (i.e., foraging, traveling, vigilant, grooming) and inactive (i.e., resting) states. Active behaviors (foraging, traveling) produced more average hits (0.87 ± 0.69 hits/min, 4.0 ± 2.2 hits/min, respectively; 95% CI) and inactive (resting) behavior fewer hits (−1.1 ± 0.61 95% CI). We differentiated active and inactive behavioral states with a bootstrapped threshold of 5.9 ± 3.9 hits/15-min recording period. Mean cumulative activity-sensor hits corresponded with observed diel behavioral patterns: hits increased during crepuscular (0600, 1800 hr) observations when elk were most active (0000–0600 hr: d = 0.19; 1200–1800 hr: d = 0.64) and decreased during midday and night (0000 hr, 1200 hr) when elk were least active (1800–0000 hr: d = −0.39; 0600–1200 hr: d = −0.43). Even using relatively unsophisticated GPS-collar activity sensors, managers can remotely estimate behavioral states, approximate diel behavioral patterns, and potentially complement location data in developing habitat selection models.

Abundance, biomass, vertical migration and estimated development rate of the copepod Calanus finmarchicus in the southern Gulf of Maine during late spring

NASA Astrophysics Data System (ADS)

Durbin, Edward G.; Gilman, Sharon L.; Campbell, Robert G.; Durbin, Ann G.

Abundance, biomass, diel vertical migration and estimated in situ development in the copepod Calanus finmarchicus were investigated during late spring in 1988 and 1989 in the southern Gulf of Maine. This region is an important feeding ground for the planktivorous right whale, Eubalaena glacialis. The 1988 study took place during the declining spring bloom, with phytoplankton biomass variable, but relatively high. The 1989 study occurred after seasonal stratification, and phytoplankton biomass was low. During the 1988 cruise the dominant stage in C. finmarchicus shifted from C1-C2 to C4-C5. Stage durations during 1988 (4.0 days for C3 and 6.6 days for C4), estimated from the temporal change in stage distribution, were similar to maximal values observed in the laboratory. In contrast, during 1989 stages C4 and C5 were dominant throughout the study period and development rate was slow (estimated C4 stage duration about 24 days). Diel vertical migration patterns changed, from an absence of migration at the first two 1988 stations where younger stages predominated (C1-C3), to a very strong diel vertical migration at the later 1988 stations where stages C3-C3 predominated. This was not a simple ontogenetic change in migratory behavior since all copepodite stages at each station showed similar patterns. During 1989 dense aggregations of C. finmarchicus remained in the surface layer both day and night, and no diel vertical migration was observed. A small, nonmigratory population of late-stage C. finmarchicus was found at depth. Individual body size of these copepods was considerably greater than those found at the surface. Differences in development rate between years reflect differences in the food environment, brought about by seasonal hydrographic changes and the development of more intense stratification. Diel vertical migration patterns, however, did not show a simple relation with food availability, and it is suggested that predation may play an important role in regulating the behavior of the copepods.

Long-term stability of tidal and diel-related patterns in mangrove creek fish assemblages in North Brazil

NASA Astrophysics Data System (ADS)

Castellanos-Galindo, G. A.; Krumme, U.

2014-08-01

Intertidal fish assemblages are thought to respond to tidal and diel rhythms although the assumption that these patterns are stable over long time scales (>1 year) is largely untested. Testing the validity of this assumption is necessary to assess whether short-term temporal patterns, once established, can be extrapolated over time and give a better understanding of the temporal dynamics of fish assemblages in coastal habitats. Here, we compare the fish assemblage structure from two intertidal mangrove creeks in North Brazil (Bragança Peninsula, Caeté estuary) sampled with the same sampling methodology (block nets), effort (two lunar cycles) and design (accounting for the combination of tidal and diel cycle) in the rainy seasons of 1999 and 2012 to evaluate the persistence, stability and recurrence of short-term patterns in the fish community organization. The interaction of tidal and diel cycles (inundations at spring tide-night, spring tide-day, neap tide-night, neap tide-day), found to be stable after 13 years, resulted in recurrent and stable intertidal mangrove fish assemblage compositions. The intertidal mangrove creek fish assemblage consisted of a persistent number of dominant species (seven). However, there were notable changes in fish catch mass, abundance and species dominance between 1999 and 2012. The most severe drought in North Brazil in 30 years, linked to lower precipitation and river runoff in the rainy season of 2012, may have resulted in (1) lower abundance of small juveniles of several dominant species in this assemblage (especially Ariidae - Cathorops agassizii and Sciades herzbergii) and (2) increased dominance of large-sized specimens of the tetraodontid Colomesus psittacus. Our findings highlight: (1) the overriding importance and stability of the interactive pulse of the tidal and diel cycles in determining short-term temporal patterns in intertidal mangrove fish assemblages in neotropical macrotidal estuaries despite the occurrence of extreme events (i.e. major decrease in rainfall) and (2) the large-scale influence that these extreme events can exert on recruitment processes in tropical estuarine fish assemblages.

Periodicity of sex pheromone biosynthesis, release and degradation in the lightbrown apple moth, Epiphyas postvittana (Walker).

PubMed

Foster, S P

2000-03-01

Pheromone titer in moths is a product of three processes occurring in or at the surface of the pheromone gland: biosynthesis, release, and intraglandular degradation, of pheromone. Changes in titers of sex pheromone, the fatty acyl pheromone analog (FAPA), and tetradecanoate, a pheromone biosynthetic intermediate, were studied in detail in the lightbrown apple moth, Epiphyas postvittana (Walker). Although changes in the pheromone titers in a day were relatively small, with the peak titer being 2-3 times greater than that at the trough, pheromone titer did show a distinct diel periodicity. Titer of the FAPA showed a similar, but less variable, diel pattern, but tetradecanoate titer showed little or no diel pattern. The pattern of pheromone titer suggested that females biosynthesize pheromone at two different rates during the photoperiod: a high rate during the latter half of the photophase and most of the scotophase, which is associated with a high pheromone titer, and a low rate throughout the first half of the photophase, which is associated with a low titer. Consistent with data on commencement of copulation, pheromone was released from the second hour of the scotophase through to the eighth hour. Pheromone release rate during this period appeared to be similar to the rate of pheromone biosynthesis. In contrast to the other two processes, pheromone degradation did not appear to have a diel pattern. Females decapitated at different times of the photoperiod showed a similar decline in pheromone titer, consistent with the reaction kinetics being first order in pheromone titer.

Regulation of nif gene expression and the energetics of N2 fixation over the diel cycle in a hot spring microbial mat.

PubMed

Steunou, Anne-Soisig; Jensen, Sheila I; Brecht, Eric; Becraft, Eric D; Bateson, Mary M; Kilian, Oliver; Bhaya, Devaki; Ward, David M; Peters, John W; Grossman, Arthur R; Kühl, Michael

2008-04-01

Nitrogen fixation, a prokaryotic, O2-inhibited process that reduces N2 gas to biomass, is of paramount importance in biogeochemical cycling of nitrogen. We analyzed the levels of nif transcripts of Synechococcus ecotypes, NifH subunit and nitrogenase activity over the diel cycle in the microbial mat of an alkaline hot spring in Yellowstone National Park. The results showed a rise in nif transcripts in the evening, with a subsequent decline over the course of the night. In contrast, immunological data demonstrated that the level of the NifH polypeptide remained stable during the night, and only declined when the mat became oxic in the morning. Nitrogenase activity was low throughout the night; however, it exhibited two peaks, a small one in the evening and a large one in the early morning, when light began to stimulate cyanobacterial photosynthetic activity, but O2 consumption by respiration still exceeded the rate of O2 evolution. Once the irradiance increased to the point at which the mat became oxic, the nitrogenase activity was strongly inhibited. Transcripts for proteins associated with energy-producing metabolisms in the cell also followed diel patterns, with fermentation-related transcripts accumulating at night, photosynthesis- and respiration-related transcripts accumulating during the day and late afternoon, respectively. These results are discussed with respect to the energetics and regulation of N2 fixation in hot spring mats and factors that can markedly influence the extent of N2 fixation over the diel cycle.

Aqueous catalysis: Methylrhenium trioxide (MTO) as a homogeneous catalyst for the Diels-Alder reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Z.; Espenson, J.H.

1997-04-16

The title compound proves to be an effective and efficient catalyst for the Diels-Alder reaction when the dienophile is an {alpha},{beta}-unsaturated ketone or aldehyde. It is especially effective in water. Equal amounts of any such dienophile and any of six representative dienes (isoprene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, cyclopentadiene, 1,2,3,4,5,-pentamethylcyclopentadiene, and 1,3-cyclohexadiene) were used, along with 1% MTO. The reactions gave usually > 90% isolated yield of the cycloaddition product except for the larger dienophiles. Nearly exclusively, there was formed one product isomer, the same one that usually predominates. The reactions were often run in chloroform (mostly) and in other organic solvents. Amore » select number were carried out in water, where the reactions gave a greater product yield in a considerably shorter time. Water, itself, is known to enhance the rates of Diels-Alder reactions, but MTO exerts an additional accelerating effect. Kinetics studies were carried out to show that the rate is proportional to the catalyst concentration. The products do not inhibit the reaction. The desirability of MTO as a Diels-Alder catalyst stems from a combination of favorable properties: the inertness to air/oxygen, the tolerance for many substrates, the use of an aqueous medium, and the absence of product inhibition. The initial step appears to be the (weak) coordination of the carbonyl oxygen to the electropositive rhenium center. Steric crowding around rhenium inhibits reactions of the larger dienophiles. 26 refs., 3 figs., 4 tabs.« less

Does biofilm contribute to diel cycling of Zn in High Ore Creek, Montana?

USGS Publications Warehouse

Morris, J.M.; Nimick, D.A.; Farag, A.M.; Meyer, J.S.

2005-01-01

Concentrations of metals cycle daily in the water column of some mining-impacted streams in the Rocky Mountains of the western USA. We hypothesized that biofilm in High Ore Creek, Montana, USA, sorbs and releases Zn on a diel cycle, and this uptake-and-release cycle controls the total and dissolved (0.45-??m filtered) Zn concentrations. We collected water samples from three sites (upstream, middle and downstream at 0, 350 and 650 m, respectively) along a 650-m reach of High Ore Creek during a 47-h period in August 2002 and from the upstream and downstream sites during a 24-h period in August 2003; we also collected biofilm samples at these sites. In 2002 and 2003, total and dissolved Zn concentrations did not exhibit a diel cycle at the upstream sampling site, which was ???30 m downstream from a settling pond through which the creek flows. However, total and dissolved Zn concentrations exhibited a diel cycle at the middle and downstream sampling sites, with the highest Zn concentrations occurring at dawn and the lowest Zn concentrations occurring during late afternoon (>2-fold range of concentrations at the downstream site). Based on (1) concentrations of Zn in biofilm at the three sites and (2) results of streamside experiments that demonstrated Zn uptake and release by nai??ve biofilm during the light and dark hours of a photocycle, respectively, we conclude that Zn uptake in photosynthetic biofilms could contribute a large percentage to the cycling of Zn concentrations in the water column in High Ore Creek. ?? Springer 2005.

Intra-population variation in activity ranges, diel patterns, movement rates, and habitat use of American alligators in a subtropical estuary

NASA Astrophysics Data System (ADS)

Rosenblatt, Adam E.; Heithaus, Michael R.; Mazzotti, Frank J.; Cherkiss, Michael; Jeffery, Brian M.

2013-12-01

Movement and habitat use patterns are fundamental components of the behaviors of mobile animals and help determine the scale and types of interactions they have with their environments. These behaviors are especially important to quantify for top predators because they can have strong effects on lower trophic levels as well as the wider ecosystem. Many studies of top predator movement and habitat use focus on general population level trends, which may overlook important intra-population variation in behaviors that now appear to be common. In an effort to better understand the prevalence of intra-population variation in top predator movement behaviors and the potential effects of such variation on ecosystem dynamics, we examined the movement and habitat use patterns of a population of adult American alligators (Alligator mississippiensis) in a subtropical estuary for nearly four years. We found that alligators exhibited divergent behaviors with respect to activity ranges, movement rates, and habitat use, and that individualized behaviors were stable over multiple years. We also found that the variations across the three behavioral metrics were correlated such that consistent behavioral types emerged, specifically more exploratory individuals and more sedentary individuals. Our study demonstrates that top predator populations can be characterized by high degrees of intra-population variation in terms of movement and habitat use behaviors that could lead to individuals filling different ecological roles in the same ecosystem. By extension, one-size-fits-all ecosystem and species-specific conservation and management strategies that do not account for potential intra-population variation in top predator behaviors may not produce the desired outcomes in all cases.

Intra-population variation in activity ranges, diel patterns, movement rates, and habitat use of American alligators in a subtropical estuary

USGS Publications Warehouse

Rosenblatt, Adam E.; Heithaus, Michael R.; Mazzotti, Frank M; Cherkiss, Michael S.; Jeffery, Brian M.

2013-01-01

Movement and habitat use patterns are fundamental components of the behaviors of mobile animals and help determine the scale and types of interactions they have with their environments. These behaviors are especially important to quantify for top predators because they can have strong effects on lower trophic levels as well as the wider ecosystem. Many studies of top predator movement and habitat use focus on general population level trends, which may overlook important intra-population variation in behaviors that now appear to be common. In an effort to better understand the prevalence of intrapopulation variation in top predator movement behaviors and the potential effects of such variation on ecosystem dynamics, we examined the movement and habitat use patterns of a population of adult American alligators (Alligator mississippiensis) in a subtropical estuary for nearly four years. We found that alligators exhibited divergent behaviors with respect to activity ranges, movement rates, and habitat use, and that individualized behaviors were stable over multiple years. We also found that the variations across the three behavioral metrics were correlated such that consistent behavioral types emerged, specifically more exploratory individuals and more sedentary individuals. Our study demonstrates that top predator populations can be characterized by high degrees of intra-population variation in terms of movement and habitat use behaviors that could lead to individuals filling different ecological roles in the same ecosystem. By extension, one-size-fits-all ecosystem and species-specific conservation and management strategies that do not account for potential intra-population variation in top predator behaviors may not produce the desired outcomes in all cases.

Biodegradable hyaluronic acid hydrogels to control release of dexamethasone through aqueous Diels-Alder chemistry for adipose tissue engineering.

PubMed

Fan, Ming; Ma, Ye; Zhang, Ziwei; Mao, Jiahui; Tan, Huaping; Hu, Xiaohong

2015-11-01

A robust synthetic strategy of biopolymer-based hydrogels has been developed where hyaluronic acid derivatives reacted through aqueous Diels-Alder chemistry without the involvement of chemical catalysts, allowing for control and sustain release of dexamethasone. To conjugate the hydrogel, furan and maleimide functionalized hyaluronic acid were synthesized, respectively, as well as furan functionalized dexamethasone, for the covalent immobilization. Chemical structure, gelation time, morphologies, swelling kinetics, weight loss, compressive modulus and dexamethasone release of the hydrogel system in PBS at 37°C were studied. The results demonstrated that the aqueous Diels-Alder chemistry provides an extremely selective reaction and proceeds with high efficiency for hydrogel conjugation and covalent immobilization of dexamethasone. Cell culture results showed that the dexamethasone immobilized hydrogel was noncytotoxic and preserved proliferation of entrapped human adipose-derived stem cells. This synthetic approach uniquely allows for the direct fabrication of biologically functionalized gel scaffolds with ideal structures for adipose tissue engineering, which provides a competitive alternative to conventional conjugation techniques such as copper mediated click chemistry. Copyright © 2015. Published by Elsevier B.V.

Total synthesis of the thiopeptide antibiotic amythiamicin D.

PubMed

Hughes, Rachael A; Thompson, Stewart P; Alcaraz, Lilian; Moody, Christopher J

2005-11-09

The thiopeptide (or thiostrepton) antibiotics are a class of sulfur containing highly modified cyclic peptides with interesting biological properties, including reported activity against MRSA and malaria. Described herein is the total synthesis of the thiopeptide natural product amythiamicin D, which utilizes a biosynthesis-inspired hetero-Diels-Alder route to the pyridine core of the antibiotic as a key step. Preliminary studies using a range of serine-derived 1-ethoxy-2-azadienes established that hetero-Diels-Alder reaction with N-acetylenamines proceeded efficiently under microwave irradiation to give 2,3,6-trisubstituted pyridines. The thiazole building blocks of the antibiotic were obtained by either classical Hantzsch reactions or by dirhodium(II)-catalyzed chemoselective carbene N-H insertion followed by thionation, and were combined to give the bis-thiazole that forms the left-hand fragment of the antibiotic. The key Diels-Alder reaction of a tris-thiazolyl azadiene with benzyl 2-(1-acetylaminoethenyl)thiazole-4-carboxylate gave the core tetrathiazolyl pyridine, which was elaborated into the natural product by successive incorporation of glycine and bis-thiazole fragments followed by macrocyclization.

Synthesis of tripeptide derivatized cyclopentadienyl complexes of technetium and rhenium as radiopharmaceutical probes.

PubMed

Nadeem, Qaisar; Can, Daniel; Shen, Yunjun; Felber, Michael; Mahmood, Zaid; Alberto, Roger

2014-03-28

We describe the syntheses of half-sandwich complexes of the type [(η(5)-Cp(CONH-R))M(CO)3] with M = Re or (99m)Tc. The R group represents different tri-peptides (tpe) which display high binding affinities for oligopeptide transporters PEPT2. The (99m)Tc complexes were prepared directly from [(99m)Tc(OH2)3(CO)3](+) and Diels-Alder dimerized, cyclopentadienyl derivatized peptides in water. This approach corroborates the feasibility of metal-mediated retro Diels-Alder reactions for the preparation of not only small molecules but also peptides carrying a [(η(5)-Cp)(99m)Tc(CO)3] tag. We synthesized the Diels-Alder product [(HCpCONH-tpe)2] from Thiele's acid [(η(5)-HCpCOOH)2] via double peptide coupling. The Re-complexes [(η(5)-CpCONH-tpe)Re(CO)3] were obtained by attaching [(Cp-COOH)Re(CO)3] directly to the N-terminus of peptides as received from SPPS. The authenticity of the (99m)Tc-complexes is confirmed by chromatographic comparison with the corresponding rhenium complexes, fully characterized by spectroscopic techniques.

Detection of transient radical cations in electron transfer-initiated Diels-Alder reactions by electrospray ionization mass spectrometry.

PubMed

Fürmeier, Sven; Metzger, Jürgen O

2004-11-10

The coupling of a simple microreactor to an atmospheric pressure ion source, such as electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI), allows the investigation of reactions in solution by mass spectrometry. The tris(p-bromophenyl)aminium hexachloroantimonate (1(*)(+)SbCl(6)(-))-initiated reactions of phenylvinylsulfide (2) and cyclopentadiene (3) and of trans-anethole (5) and isoprene (6) and the dimerization of 1,3-cyclohexadiene (8) to give the respective Diels-Alder products were studied. These preparatively interesting reactions proceed as radical cation chain reactions via the transient radical cations of the respective dienophiles and of the respective Diels-Alder addition products. These radical cations could be detected directly and characterized unambiguously in the reacting solution by ESI-MS-MS. The identity was confirmed by comparison with MS-MS spectra of the authentic radical cations obtained by APCI-MS and by CID experiments of the corresponding molecular ions generated by EI-MS. In addition, substrates and products could be monitored easily in the reacting solution by APCI-MS.

Vertical nitrogen flux from the oceanic photic zone by diel migrant zooplankton and nekton

NASA Astrophysics Data System (ADS)

Longhurst, Alan R.; Glen Harrison, W.

1988-06-01

Where the photic zone is a biological steady-state, the downward flux of organic material across the pycnocline to the interior of the ocean is thought to be balanced by upward turbulent flux of inorganic nitrogen across the nutricline. This model ignores a significant downward dissolved nitrogen flux caused by the diel vertical migration of interzonal zooplankton and nekton that feed in the photic zone at night and excrete nitrogenous compounds at depth by day. In the oligotrophic ocean this flux can be equivalent to the flux of particulate organic nitrogen from the photic zone in the form of faecal pellets and organic flocculates. Where nitrogen is the limiting plant nutrient, and the flux by diel migration of interzonal plankton is significant compared to other nitrogen exports from the photic zone, there must be an upward revision of previous estimates for the ratio of new to total primary production in the photic zone if a nutrient balance is to be maintained. This upward revision is of the order 5-100% depending on the oceanographic regime.

Synthesis of Polyheterocyclic Pyrrolo[3,4-b]pyridin-5-ones via a One-Pot (Ugi-3CR/aza Diels-Alder/N-acylation/aromatization/SN2) Process. A Suitable Alternative towards Novel Aza-Analogues of Falipamil.

PubMed

Zamudio-Medina, Angel; García-González, Ailyn N; Herrera-Carrillo, Genesis K; Zárate-Zárate, Daniel; Benavides-Macías, Adriana; Tamariz, Joaquín; Ibarra, Ilich A; Islas-Jácome, Alejandro; González-Zamora, Eduardo

2018-03-27

We describe the one-pot synthesis of twenty polyheterocyclic pyrrolo[3,4- b ]pyridin-5-ones via a cascade process (Ugi-3CR/aza Diels-Alder/ N -acylation/aromatization) in 20 to 95% overall yields, as well as four pharmacologically promising analogues via an improved cascade process (Ugi-3CR/aza Diels-Alder/ N -acylation/aromatization/S N 2): two piperazine-linked pyrrolo[3,4- b ]pyridin-5-ones in 33 and 34%, and a couple of Falipamil aza-analogues in 30 and 35% overall yields. It is worth highlighting the good substrate scope found, because final products are furnished with alkyl, aryl, and heterocyclic substituents. The use of chain-ring tautomerizable isocyanides (as key reagents for the Ugi-type three component reaction) allowed for a rapid and efficient assembly of the polysubstituted oxindoles, which were used in situ toward the complex products, conferring features like robustness, sustainability, and the one-pot approach to this synthetic methodology.

CCN activity and organic hygroscopicity of aerosols downwind of an urban region in central Amazonia: seasonal and diel variations and impact of anthropogenic emissions

NASA Astrophysics Data System (ADS)

Thalman, Ryan; de Sá, Suzane S.; Palm, Brett B.; Barbosa, Henrique M. J.; Pöhlker, Mira L.; Lizabeth Alexander, M.; Brito, Joel; Carbone, Samara; Castillo, Paulo; Day, Douglas A.; Kuang, Chongai; Manzi, Antonio; Ng, Nga Lee; Sedlacek, Arthur J., III; Souza, Rodrigo; Springston, Stephen; Watson, Thomas; Pöhlker, Christopher; Pöschl, Ulrich; Andreae, Meinrat O.; Artaxo, Paulo; Jimenez, Jose L.; Martin, Scot T.; Wang, Jian

2017-10-01

During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, size-resolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60 km downwind of the city of Manaus, Brazil, in central Amazonia for 1 year (12 March 2014 to 3 March 2015). Particle hygroscopicity (κCCN) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (κorg) was then calculated from κCCN and concurrent chemical composition measurements. The annual average κCCN increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely due to an increase in sulfate volume fraction. During both wet and dry seasons, κCCN, κorg, and particle composition under background conditions exhibited essentially no diel variations. The constant κorg of ˜ 0. 15 is consistent with the largely uniform and high O : C value (˜ 0. 8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of κorg and organic O : C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O : C, κorg, and κCCN increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into a deeper boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF (positive matrix factorization) analysis of AMS (aerosol mass spectrometry) spectra, were estimated through multivariable linear regression. For the SOA factors, the variation of the κ value with O : C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O : C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O : C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O : C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase in κorg with O : C, as observed during this and earlier field studies. This finding helps better understand and reconcile the differences in the relationships between κorg and O : C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.

CCN activity and organic hygroscopicity of aerosols downwind of an urban region in central Amazonia: Seasonal and diel variations and impact of anthropogenic emissions

DOE PAGES

Thalman, Ryan; de Sá, Suzane S.; Palm, Brett B.; ...

2017-10-05

During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, size-resolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60km downwind of the city of Manaus, Brazil, in central Amazonia for one year (12 March 2014 to 3 March 2015). Particle hygroscopicity (κCCN) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (κorg) was then calculated from κCCN and concurrent chemical composition measurements. The annual average κCCN increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely duemore » to an increase in sulfate volume fraction. Also, during both wet and dry seasons, κCCN, κorg, and particle composition under background conditions exhibited essentially no diel variations. The constant κorg of ~0.15 is consistent with the largely uniform and high O:C value (~0.8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of κorg and organic O:C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O:C, κorg, and κCCN increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into a deeper boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF analysis of AMS spectra, were estimated through multi-variable linear regression. For the SOA factors, the variation of the κ value with O:C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O:C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O:C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O:C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase of κorg with O:C, as observed during this and earlier field studies. Our finding helps better understand and reconcile the differences in the relationships between κorg and O:C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.« less

CCN activity and organic hygroscopicity of aerosols downwind of an urban region in central Amazonia: Seasonal and diel variations and impact of anthropogenic emissions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thalman, Ryan; de Sá, Suzane S.; Palm, Brett B.

During the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) campaign, size-resolved cloud condensation nuclei (CCN) spectra were characterized at a research site (T3) 60km downwind of the city of Manaus, Brazil, in central Amazonia for one year (12 March 2014 to 3 March 2015). Particle hygroscopicity (κCCN) and mixing state were derived from the size-resolved CCN spectra, and the hygroscopicity of the organic component of the aerosol (κorg) was then calculated from κCCN and concurrent chemical composition measurements. The annual average κCCN increased from 0.13 at 75 nm to 0.17 at 171 nm, and the increase was largely duemore » to an increase in sulfate volume fraction. Also, during both wet and dry seasons, κCCN, κorg, and particle composition under background conditions exhibited essentially no diel variations. The constant κorg of ~0.15 is consistent with the largely uniform and high O:C value (~0.8), indicating that the aerosols under background conditions are dominated by the aged regional aerosol particles consisting of highly oxygenated organic compounds. For air masses strongly influenced by urban pollution and/or local biomass burning, lower values of κorg and organic O:C atomic ratio were observed during night, due to accumulation of freshly emitted particles, dominated by primary organic aerosol (POA) with low hygroscopicity, within a shallow nocturnal boundary layer. The O:C, κorg, and κCCN increased from the early morning hours and peaked around noon, driven by the formation and aging of secondary organic aerosol (SOA) and dilution of POA emissions into a deeper boundary layer, while the development of the boundary layer, which leads to mixing with aged particles from the residual layer aloft, likely also contributed to the increases. The hygroscopicities associated with individual organic factors, derived from PMF analysis of AMS spectra, were estimated through multi-variable linear regression. For the SOA factors, the variation of the κ value with O:C agrees well with the linear relationship reported from earlier laboratory studies of SOA hygroscopicity. On the other hand, the variation in O:C of ambient aerosol organics is largely driven by the variation in the volume fractions of POA and SOA factors, which have very different O:C values. As POA factors have hygroscopicity values well below the linear relationship between SOA hygroscopicity and O:C, mixtures with different POA and SOA fractions exhibit a steeper slope for the increase of κorg with O:C, as observed during this and earlier field studies. Our finding helps better understand and reconcile the differences in the relationships between κorg and O:C observed in laboratory and field studies, therefore providing a basis for improved parameterization in global models, especially in a tropical context.« less

Diels-Alder and Stille Coupling Approach for the Short Protecting-Group-Free Synthesis of Mycophenolic Acid, Its Phenylsulfenyl and Phenylselenyl Analogues, and Reactive Oxygen Species (ROS) Probing Capacity in Water.

PubMed

Halle, Mahesh B; Yudhistira, Tesla; Lee, Woo-Hyun; Mulay, Sandip V; Churchill, David G

2018-06-15

A short, protecting-group-free synthesis is achieved. The synthesis is step-efficient and general. A Diels-Alder and Stille cross-coupling approach includes key transformations, allowing for a competitive synthesis which involves a rare halophenol Stille cross-coupling study. The phenylselenyl and phenylsulfenyl analogues were prepared as novel compounds in good overall yield. The applicability of one of the intermediates as a potential probe for reactive oxygen species (ROS) in water is investigated.

Diels-Alder reactions onto fluorinated and hydrogenated graphene

NASA Astrophysics Data System (ADS)

Denis, Pablo A.

2017-09-01

We studied Diels-Alder (DA) reactions onto functionalized graphene. When fluorine, hydrogen or oxygen functional groups are present on one side of the sheet, the DA cycloadditions become significantly more exergonic when performed on the opposite side. Hydrogen is more effective than fluorine and oxygen to promote these cycloadditions. In contrast with the results obtained for perfect graphene, the functionalization with H, F or O turns the DA reactions exergonic, with ΔG°298 = -127.2 kcal/mol. The reaction barriers are expected to be considerably lowered with respect to perfect graphene because the functional groups significantly reduce the distortion energy.

Phytochemical, cytotoxic and chemotaxonomic study on Ajuga forrestii Diels (Labiatae).

PubMed

Chen, Tong; Diao, Qing-Yan; Yu, Hai-Zhou; Jiao, Chun-Li; Ruan, Jian

2018-04-01

A phytochemical investigation of Ajuga forrestii Diels led to the isolation of 14 compounds, including eight neo-clerodane diterpenes (1-8), two phytoecdysteroids (9, 11), one stigmastane sterol (10) and three iridoid glycosides (12-14). The structures of these compounds were identified by spectroscopic methods and a comparison of their data with those reported in the literature. This is the first report of compounds 1-14 from A. forrestii. The cytotoxic activities of the aqueous extract of A. forrestii and several compounds have been studied and the chemotaxonomic significance of isolated compounds has also been summarised.

Diastereoselective Diels-Alder reactions of alpha-fluorinated alpha,beta-unsaturated carbonyl compounds: chemical consequences of fluorine substitution. 2.

PubMed

Essers, Michael; Mück-Lichtenfeld, Christian; Haufe, Günter

2002-07-12

Two alpha-fluoro alpha,beta-unsaturated carbonyl compounds, i.e., benzyl 2-fluoroacrylate (3) and 2-fluorooct-1-en-3-one (4), as well as the corresponding nonfluorinated parent compounds, were synthesized and subjected to Diels-Alder reactions with cyclopentadiene. The cycloadditions were conducted thermally, microwave-assisted, and Lewis acid-mediated (TiCl(4)). The fluorinated dienophiles exhibited a lower reactivity and exo diastereoselectivity, while the corresponding nonfluorinated parent compounds reacted endo selectively. DFT calculations suggest that kinetic effects of fluorine determine the stereoselectivity rather than higher thermodynamic stability of the exo products.

Diels-Alder cycloaddition in the synthesis of 1-azafagomine, analogs, and derivatives as glycosidase inhibitors.

PubMed

Salgueiro, Daniela A L; Sousa, Cristina E A; Fortes, A Gil; Alves, M José

2012-12-01

This comprehensive review deals with the synthesis of 1-azafagomine, analogs, and derivatives having the Diels-Alder cycloaddition as the key step. Most of the compounds referred are racemic or have been resolved by lipase transesterification. There are two asymmetric cycloadditions leading to 1-azafagomine or to an analog. In one case both enantiomers of 1-azafagomine were prepared together with a pair of derivatives. The study comprises glycosidase inhibition studies of the target compounds to a set of glycosidic enzymes, and evidenced molecular features that enhance or diminish their activity as glycosidase inhibitors.

Biogenetically inspired approach to the Strychnos alkaloids. Concise syntheses of (+/-)-akuammicine and (+/-)-strychnine.

PubMed

Ito, M; Clark, C W; Mortimore, M; Goh, J B; Martin, S F

2001-08-22

A linear synthesis of the indole alkaloid (+/-)-akuammicine (2) was completed by a novel sequence of reactions requiring only 10 steps from commercially available starting materials. The approach features a tandem vinylogous Mannich addition and an intramolecular hetero Diels-Alder reaction to rapidly assemble the pentacyclic heteroyohimboid derivative 8 from the readily available hydrocarboline 6. Oxidation of the E ring of 8 gave the lactone 9 that was converted into deformylgeissoschizine (11). The subsequent elaboration of 11 into 2 was effected by a biomimetically patterned transformation that involved sequential oxidation and base-induced skeletal reorganization. A variation of these tactics was then applied to the synthesis of the C(18) hydroxylated akuammicine derivative 36. Because 36 had previously been converted into strychnine (1) in four steps, its preparation constitutes a concise, formal synthesis of this complex alkaloid.

Insects in fluctuating thermal environments.

PubMed

Colinet, Hervé; Sinclair, Brent J; Vernon, Philippe; Renault, David

2015-01-07

All climate change scenarios predict an increase in both global temperature means and the magnitude of seasonal and diel temperature variation. The nonlinear relationship between temperature and biological processes means that fluctuating temperatures lead to physiological, life history, and ecological consequences for ectothermic insects that diverge from those predicted from constant temperatures. Fluctuating temperatures that remain within permissive temperature ranges generally improve performance. By contrast, those which extend to stressful temperatures may have either positive impacts, allowing repair of damage accrued during exposure to thermal extremes, or negative impacts from cumulative damage during successive exposures. We discuss the mechanisms underlying these differing effects. Fluctuating temperatures could be used to enhance or weaken insects in applied rearing programs, and any prediction of insect performance in the field-including models of climate change or population performance-must account for the effect of fluctuating temperatures.

Diel Metagenomics and Metatranscriptomics of Elkhorn Slough Hypersaline Microbial Mat

NASA Astrophysics Data System (ADS)

Lee, J.; Detweiler, A. M.; Everroad, R. C.; Bebout, L. E.; Weber, P. K.; Pett-Ridge, J.; Bebout, B.

2014-12-01

To understand the variation in gene expression associated with the daytime oxygenic phototrophic and nighttime fermentation regimes seen in hypersaline microbial mats, a contiguous mat piece was subjected to sampling at regular intervals over a 24-hour diel period. Additionally, to understand the impact of sulfate reduction on biohydrogen consumption, molybdate was added to a parallel experiment in the same run. 4 metagenome and 12 metatranscriptome Illumina HiSeq lanes were completed over day / night, and control / molybdate experiments. Preliminary comparative examination of noon and midnight metatranscriptomic samples mapped using bowtie2 to reference genomes has revealed several notable results about the dominant mat-building cyanobacterium Microcoleus chthonoplastes PCC 7420. Dominant cyanobacterium M. chthonoplastes PCC 7420 shows expression in several pathways for nitrogen scavenging, including nitrogen fixation. Reads mapped to M. chthonoplastes PCC 7420 shows expression of two starch storage and utilization pathways, one as a starch-trehalose-maltose-glucose pathway, another through UDP-glucose-cellulose-β-1,4 glucan-glucose pathway. The overall trend of gene expression was primarily light driven up-regulation followed by down-regulation in dark, while much of the remaining expression profile appears to be constitutive. Co-assembly of quality-controlled reads from 4 metagenomes was performed using Ray Meta with progressively smaller K-mer sizes, with bins identified and filtered using principal component analysis of coverages from all libraries and a %GC filter, followed by reassembly of the remaining co-assembly reads and binned reads. Despite having relatively similar abundance profiles in each metagenome, this binning approach was able to distinctly resolve bins from dominant taxa, but also sulfate reducing bacteria that are desired for understanding molybdate inhibition. Bins generated from this iterative assembly process will be used for downstream mapping of transcriptomic reads as well as isolation efforts for Cyanobacteria-associated bacteria.

Wave-induced mass transport affects daily Escherichia coli fluctuations in nearshore water.

PubMed

Ge, Zhongfu; Whitman, Richard L; Nevers, Meredith B; Phanikumar, Mantha S

2012-02-21

Characterization of diel variability of fecal indicator bacteria concentration in nearshore waters is of particular importance for development of water sampling standards and protection of public health. Significant nighttime increase in Escherichia coli (E. coli) concentration in beach water, previously observed at marine sites, has also been identified in summer 2000 from fixed locations in waist- and knee-deep waters at Chicago 63rd Street Beach, an embayed, tideless, freshwater beach with low currents at night (approximately 0.015 m s(-1)). A theoretical model using wave-induced mass transport velocity for advection was developed to assess the contribution of surface waves to the observed nighttime E. coli replenishment in the nearshore water. Using average wave conditions for the summer season of year 2000, the model predicted an amount of E. coli transported from water of intermediate depth, where sediment resuspension occurred intermittently, that would be sufficient to have elevated E. coli concentration in the surf and swash zones as observed. The nighttime replenishment of E. coli in the surf and swash zones revealed here is an important phase in the cycle of diel variations of E. coli concentration in nearshore water. According to previous findings in Ge et al. (Environ. Sci. Technol. 2010, 44, 6731-6737), enhanced current circulation in the embayment during the day tends to displace and deposit material offshore, which partially sets up the system by the early evening for a new period of nighttime onshore movement. This wave-induced mass transport effect, although facilitating a significant base supply of material shoreward, can be perturbed or significantly influenced by high currents (orders of magnitude larger than a typical wave-induced mass transport velocity), current-induced turbulence, and tidal forcing.

Simulation of Lake Victoria Circulation Patterns Using the Regional Ocean Modeling System (ROMS).

PubMed

Nyamweya, Chrispine; Desjardins, Christopher; Sigurdsson, Sven; Tomasson, Tumi; Taabu-Munyaho, Anthony; Sitoki, Lewis; Stefansson, Gunnar

2016-01-01

Lake Victoria provides important ecosystem services including transport, water for domestic and industrial uses and fisheries to about 33 million inhabitants in three East African countries. The lake plays an important role in modulating regional climate. Its thermodynamics and hydrodynamics are also influenced by prevailing climatic and weather conditions on diel, seasonal and annual scales. However, information on water temperature and circulation in the lake is limited in space and time. We use a Regional Oceanographic Model System (ROMS) to simulate these processes from 1st January 2000 to 31st December 2014. The model is based on real bathymetry, river runoff and atmospheric forcing data using the bulk flux algorithm. Simulations show that the water column exhibits annual cycles of thermo-stratification (September-May) and mixing (June-August). Surface water currents take different patterns ranging from a lake-wide northward flow to gyres that vary in size and number. An under flow exists that leads to the formation of upwelling and downwelling regions. Current velocities are highest at the center of the lake and on the western inshore waters indicating enhanced water circulation in those areas. However, there is little exchange of water between the major gulfs (especially Nyanza) and the open lake, a factor that could be responsible for the different water quality reported in those regions. Findings of the present study enhance understanding of the physical processes (temperature and currents) that have an effect on diel, seasonal, and annual variations in stratification, vertical mixing, inshore-offshore exchanges and fluxes of nutrients that ultimately influence the biotic distribution and trophic structure. For instance information on areas/timing of upwelling and vertical mixing obtained from this study will help predict locations/seasons of high primary production and ultimately fisheries productivity in Lake Victoria.

Wave-induced mass transport affects daily Escherichia coli fluctuations in nearshore water

USGS Publications Warehouse

Ge, Zhongfu; Whitman, Richard L.; Nevers, Meredith B.; Phanikumar, Mantha S.

2012-01-01

Characterization of diel variability of fecal indicator bacteria concentration in nearshore waters is of particular importance for development of water sampling standards and protection of public health. Significant nighttime increase in Escherichia coli (E. coli) concentration in beach water, previously observed at marine sites, has also been identified in summer 2000 from fixed locations in waist- and knee-deep waters at Chicago 63rd Street Beach, an embayed, tideless, freshwater beach with low currents at night (approximately 0.015 m s–1). A theoretical model using wave-induced mass transport velocity for advection was developed to assess the contribution of surface waves to the observed nighttime E. coli replenishment in the nearshore water. Using average wave conditions for the summer season of year 2000, the model predicted an amount of E. coli transported from water of intermediate depth, where sediment resuspension occurred intermittently, that would be sufficient to have elevated E. coli concentration in the surf and swash zones as observed. The nighttime replenishment of E. coli in the surf and swash zones revealed here is an important phase in the cycle of diel variations of E. coli concentration in nearshore water. According to previous findings in Ge et al. (Environ. Sci. Technol. 2010, 44, 6731–6737), enhanced current circulation in the embayment during the day tends to displace and deposit material offshore, which partially sets up the system by the early evening for a new period of nighttime onshore movement. This wave-induced mass transport effect, although facilitating a significant base supply of material shoreward, can be perturbed or significantly influenced by high currents (orders of magnitude larger than a typical wave-induced mass transport velocity), current-induced turbulence, and tidal forcing.

Production and carbonate dynamics of Halimeda incrassata (Ellis) Lamouroux altered by Thalassia testudinum Banks and Soland ex König

NASA Astrophysics Data System (ADS)

Barry, S.; Frazer, T.; Jacoby, C.

2013-05-01

Ocean acidification poses a serious threat to a broad suite of calcifying organisms. Scleractinian corals and calcareous algae that occupy shallow, tropical waters are vulnerable to global changes in ocean chemistry because they already are subject to stressful and variable carbon dynamics at the local scale. For example, net heterotrophy increases carbon dioxide concentrations, and pH varies with diurnal fluctuations in photosynthesis and respiration. Few researchers, however, have investigated the possibility that carbon dioxide consumption during photosynthesis by non-calcifying photoautotrophs, such as seagrasses, can ameliorate deleterious effects of ocean acidification on sympatric calcareous algae. Naturally occurring variations in the density of seagrasses and associated calcareous algae provide an ecologically relevant test of the hypothesis that diel fluctuations in water chemistry driven by cycles of photosynthesis and respiration within seagrass beds create microenvironments that enhance macroalgal calcification. In Grape Tree Bay off Little Cayman Island BWI, we quantified net production and characterized calcification for thalli of the calcareous green alga Halimeda incrassata growing within beds of Thalassia testudinum with varying shoot densities. Results indicated that individual H. incrassata thalli were ~6% more calcified in dense seagrass beds. On an areal basis, however, far more calcium carbonate was produced by H. incrassata in areas where seagrasses were less dense due to higher rates of production. In addition, diel pH regimes in vegetated and unvegetated areas within the lagoon were not significantly different, suggesting water exchange and mixing throughout the lagoon. These results suggest that, especially in well-mixed lagoons, carbonate production by calcareous algae may be more related to biotic interactions between seagrasses and calcareous algae than to seagrass-mediated changes in local water chemistry.

Direct measurement of NO3 radical reactivity in a boreal forest

NASA Astrophysics Data System (ADS)

Liebmann, Jonathan; Karu, Einar; Sobanski, Nicolas; Schuladen, Jan; Ehn, Mikael; Schallhart, Simon; Quéléver, Lauriane; Hellen, Heidi; Hakola, Hannele; Hoffmann, Thorsten; Williams, Jonathan; Fischer, Horst; Lelieveld, Jos; Crowley, John N.

2018-03-01

We present the first direct measurements of NO3 reactivity (or inverse lifetime, s-1) in the Finnish boreal forest. The data were obtained during the IBAIRN campaign (Influence of Biosphere-Atmosphere Interactions on the Reactive Nitrogen budget) which took place in Hyytiälä, Finland during the summer/autumn transition in September 2016. The NO3 reactivity was generally very high with a maximum value of 0.94 s-1 and displayed a strong diel variation with a campaign-averaged nighttime mean value of 0.11 s-1 compared to a daytime value of 0.04 s-1. The highest nighttime NO3 reactivity was accompanied by major depletion of canopy level ozone and was associated with strong temperature inversions and high levels of monoterpenes. The daytime reactivity was sufficiently large that reactions of NO3 with organic trace gases could compete with photolysis and reaction with NO. There was no significant reduction in the measured NO3 reactivity between the beginning and end of the campaign, indicating that any seasonal reduction in canopy emissions of reactive biogenic trace gases was offset by emissions from the forest floor. Observations of biogenic hydrocarbons (BVOCs) suggested a dominant role for monoterpenes in determining the NO3 reactivity. Reactivity not accounted for by in situ measurement of NO and BVOCs was variable across the diel cycle with, on average, ≈ 30 % missing during nighttime and ≈ 60 % missing during the day. Measurement of the NO3 reactivity at various heights (8.5 to 25 m) both above and below the canopy, revealed a strong nighttime, vertical gradient with maximum values closest to the ground. The gradient disappeared during the daytime due to efficient vertical mixing.

The diel rhythms of biosonar behavior in the Yangtze finless porpoise (Neophocaena asiaeorientalis asiaeorientalis) in the port of the Yangtze River: The correlation between prey availability and boat traffic.

PubMed

Wang, Zhitao; Akamatsu, Tomonari; Wang, Kexiong; Wang, Ding

2014-01-01

Information on the habitat use of the critically endangered Yangtze finless porpoise (Neophocaena asiaeorientalis asiaeorientalis) is critical for its conservation. The diel biosonar behavior of the porpoise in the port areas of the Yangtze River was examined along with simultaneous observations of fish density and boat traffic. Biosonar pulses from the porpoises were detected for 1233 min (5.77%) over a 21,380 min duration of effective observations. In total, 190 (5.63%) buzzes (an indication of prey capture attempts) were recorded among the 3372 identified click trains. Of the 168 echolocation encounters (bouts of click trains less than eight min apart), 150 (89.3%) involved single animals, indicating that solitary porpoises were frequently present and feeding in the port areas. Significant diel patterns were evident involving the biosonar behavior of the porpoises (including click trains and buzzes), fish density and boat traffic. The frequencies of the click trains and buzzes were significantly lower during the day than in the evening and at night, which suggests that porpoises in this region are primarily engaged in crepuscular and nocturnal foraging. The lack of a significant diel pattern in the echolocation encounters indicates the importance of the port in porpoise conservation. A forced feeding schedule may be associated with the lack of a significant correlation between porpoise acoustics and boat traffic. Overall, prey availability appears to be the primary factor that attracts porpoises. Additionally, porpoises tend to migrate or remain downstream in the morning and migrate or remain upstream in the evening, most likely to follow their prey. The findings of this study can be used to improve the conservation of the Yangtze finless porpoise.

The Diel Rhythms of Biosonar Behavior in the Yangtze Finless Porpoise (Neophocaena asiaeorientalis asiaeorientalis) in the Port of the Yangtze River: The Correlation between Prey Availability and Boat Traffic

PubMed Central

Wang, Zhitao; Akamatsu, Tomonari; Wang, Kexiong; Wang, Ding

2014-01-01

Information on the habitat use of the critically endangered Yangtze finless porpoise (Neophocaena asiaeorientalis asiaeorientalis) is critical for its conservation. The diel biosonar behavior of the porpoise in the port areas of the Yangtze River was examined along with simultaneous observations of fish density and boat traffic. Biosonar pulses from the porpoises were detected for 1233 min (5.77%) over a 21,380 min duration of effective observations. In total, 190 (5.63%) buzzes (an indication of prey capture attempts) were recorded among the 3372 identified click trains. Of the 168 echolocation encounters (bouts of click trains less than eight min apart), 150 (89.3%) involved single animals, indicating that solitary porpoises were frequently present and feeding in the port areas. Significant diel patterns were evident involving the biosonar behavior of the porpoises (including click trains and buzzes), fish density and boat traffic. The frequencies of the click trains and buzzes were significantly lower during the day than in the evening and at night, which suggests that porpoises in this region are primarily engaged in crepuscular and nocturnal foraging. The lack of a significant diel pattern in the echolocation encounters indicates the importance of the port in porpoise conservation. A forced feeding schedule may be associated with the lack of a significant correlation between porpoise acoustics and boat traffic. Overall, prey availability appears to be the primary factor that attracts porpoises. Additionally, porpoises tend to migrate or remain downstream in the morning and migrate or remain upstream in the evening, most likely to follow their prey. The findings of this study can be used to improve the conservation of the Yangtze finless porpoise. PMID:24823945

Large natural pH, CO2 and O2 fluctuations in a temperate tidal salt marsh on diel, seasonal, and interannual time scales

USGS Publications Warehouse

Baumann, Hannes; Wallace, Ryan; Tagliaferri, Tristen N.; Gobler, Christopher J.

2014-01-01

Coastal marine organisms experience dynamic pH and dissolved oxygen (DO) conditions in their natural habitats, which may impact their susceptibility to long-term anthropogenic changes. Robust characterizations of all temporal scales of natural pH and DO fluctuations in different marine habitats are needed; however, appropriate time series of pH and DO are still scarce. We used multiyear (2008–2012), high-frequency (6 min) monitoring data to quantify diel, seasonal, and interannual scales of pH and DO variability in a productive, temperate tidal salt marsh (Flax Pond, Long Island, US). pHNBS and DO showed strong and similar seasonal patterns, with average (minimum) conditions declining from 8.2 (8.1) and 12.5 (11.4) mg l−1 at the end of winter to 7.6 (7.2) and 6.3 (2.8) mg l−1 in late summer, respectively. Concomitantly, average diel fluctuations increased from 0.22 and 2.2 mg l−1 (February) to 0.74 and 6.5 mg l−1 (August), respectively. Diel patterns were modulated by tides and time of day, eliciting the most extreme minima when low tides aligned with the end of the night. Simultaneous in situ pCO2 measurements showed striking fluctuations between ∼330 and ∼1,200 (early May), ∼2,200 (mid June), and ∼4,000 μatm (end of July) within single tidal cycles. These patterns also indicate that the marsh’s strong net heterotrophy influences its adjacent estuary by ‘outwelling’ acidified and hypoxic water during ebb tides. Our analyses emphasize the coupled and fluctuating nature of pH and DO conditions in productive coastal and estuarine environments, which have yet to be adequately represented by experiments.

A Diel Flux Balance Model Captures Interactions between Light and Dark Metabolism during Day-Night Cycles in C3 and Crassulacean Acid Metabolism Leaves.

PubMed

Cheung, C Y Maurice; Poolman, Mark G; Fell, David A; Ratcliffe, R George; Sweetlove, Lee J

2014-06-01

Although leaves have to accommodate markedly different metabolic flux patterns in the light and the dark, models of leaf metabolism based on flux-balance analysis (FBA) have so far been confined to consideration of the network under continuous light. An FBA framework is presented that solves the two phases of the diel cycle as a single optimization problem and, thus, provides a more representative model of leaf metabolism. The requirement to support continued export of sugar and amino acids from the leaf during the night and to meet overnight cellular maintenance costs forces the model to set aside stores of both carbon and nitrogen during the day. With only minimal constraints, the model successfully captures many of the known features of C 3 leaf metabolism, including the recently discovered role of citrate synthesis and accumulation in the night as a precursor for the provision of carbon skeletons for amino acid synthesis during the day. The diel FBA model can be applied to other temporal separations, such as that which occurs in Crassulacean acid metabolism (CAM) photosynthesis, allowing a system-level analysis of the energetics of CAM. The diel model predicts that there is no overall energetic advantage to CAM, despite the potential for suppression of photorespiration through CO 2 concentration. Moreover, any savings in enzyme machinery costs through suppression of photorespiration are likely to be offset by the higher flux demand of the CAM cycle. It is concluded that energetic or nitrogen use considerations are unlikely to be evolutionary drivers for CAM photosynthesis. © 2014 American Society of Plant Biologists. All Rights Reserved.

A Diel Flux Balance Model Captures Interactions between Light and Dark Metabolism during Day-Night Cycles in C3 and Crassulacean Acid Metabolism Leaves1[C][W][OPEN

PubMed Central

Cheung, C.Y. Maurice; Poolman, Mark G.; Fell, David. A.; Ratcliffe, R. George; Sweetlove, Lee J.

2014-01-01

Although leaves have to accommodate markedly different metabolic flux patterns in the light and the dark, models of leaf metabolism based on flux-balance analysis (FBA) have so far been confined to consideration of the network under continuous light. An FBA framework is presented that solves the two phases of the diel cycle as a single optimization problem and, thus, provides a more representative model of leaf metabolism. The requirement to support continued export of sugar and amino acids from the leaf during the night and to meet overnight cellular maintenance costs forces the model to set aside stores of both carbon and nitrogen during the day. With only minimal constraints, the model successfully captures many of the known features of C3 leaf metabolism, including the recently discovered role of citrate synthesis and accumulation in the night as a precursor for the provision of carbon skeletons for amino acid synthesis during the day. The diel FBA model can be applied to other temporal separations, such as that which occurs in Crassulacean acid metabolism (CAM) photosynthesis, allowing a system-level analysis of the energetics of CAM. The diel model predicts that there is no overall energetic advantage to CAM, despite the potential for suppression of photorespiration through CO2 concentration. Moreover, any savings in enzyme machinery costs through suppression of photorespiration are likely to be offset by the higher flux demand of the CAM cycle. It is concluded that energetic or nitrogen use considerations are unlikely to be evolutionary drivers for CAM photosynthesis. PMID:24596328

A "Do-It-Yourself" phenotyping system: measuring growth and morphology throughout the diel cycle in rosette shaped plants.

PubMed

Dobrescu, Andrei; Scorza, Livia C T; Tsaftaris, Sotirios A; McCormick, Alistair J

2017-01-01

Improvements in high-throughput phenotyping technologies are rapidly expanding the scope and capacity of plant biology studies to measure growth traits. Nevertheless, the costs of commercial phenotyping equipment and infrastructure remain prohibitively expensive for wide-scale uptake, while academic solutions can require significant local expertise. Here we present a low-cost methodology for plant biologists to build their own phenotyping system for quantifying growth rates and phenotypic characteristics of Arabidopsis thaliana rosettes throughout the diel cycle. We constructed an image capture system consisting of a near infra-red (NIR, 940 nm) LED panel with a mounted Raspberry Pi NoIR camera and developed a MatLab-based software module (iDIEL Plant) to characterise rosette expansion. Our software was able to accurately segment and characterise multiple rosettes within an image, regardless of plant arrangement or genotype, and batch process image sets. To further validate our system, wild-type Arabidopsis plants (Col-0) and two mutant lines with reduced Rubisco contents, pale leaves and slow growth phenotypes ( 1a3b and 1a2b ) were grown on a single plant tray. Plants were imaged from 9 to 24 days after germination every 20 min throughout the 24 h light-dark growth cycle (i.e. the diel cycle). The resulting dataset provided a dynamic and uninterrupted characterisation of differences in rosette growth and expansion rates over time for the three lines tested. Our methodology offers a straightforward solution for setting up automated, scalable and low-cost phenotyping facilities in a wide range of lab environments that could greatly increase the processing power and scalability of Arabidopsis soil growth experiments.

Diel hysteresis between soil respiration and soil temperature in a biological soil crust covered desert ecosystem

PubMed Central

Li, Xinrong; Zhang, Peng; Chen, Yongle

2018-01-01

Soil respiration induced by biological soil crusts (BSCs) is an important process in the carbon (C) cycle in arid and semi-arid ecosystems, where vascular plants are restricted by the harsh environment, particularly the limited soil moisture. However, the interaction between temperature and soil respiration remains uncertain because of the number of factors that control soil respiration, including temperature and soil moisture, especially in BSC-dominated areas. In this study, the soil respiration in moss-dominated crusts and lichen-dominated crusts was continuously measured using an automated soil respiration system over a one-year period from November 2015 to October 2016 in the Shapotou region of the Tengger Desert, northern China. The results indicated that over daily cycles, the half-hourly soil respiration rates in both types of BSC-covered areas were commonly related to the soil temperature. The observed diel hysteresis between the half-hourly soil respiration rates and soil temperature in the BSC-covered areas was limited by nonlinearity loops with semielliptical shapes, and soil temperature often peaked later than the half-hourly soil respiration rates in the BSC-covered areas. The average lag times between the half-hourly soil respiration rates and soil temperature for both types of BSC-covered areas were two hours over the diel cycles, and they were negatively and linearly related to the volumetric soil water content. Our results highlight the diel hysteresis phenomenon that occurs between soil respiration rates and soil temperatures in BSC-covered areas and the negative response of this phenomenon to soil moisture, which may influence total C budget evaluations. Therefore, the interactive effects of soil temperature and moisture on soil respiration in BSC-covered areas should be considered in global carbon cycle models of desert ecosystems. PMID:29624606

Leaf carbohydrates influence transcriptional and post-transcriptional regulation of nocturnal carboxylation and starch degradation in the facultative CAM plant, Mesembryanthemum crystallinum.

PubMed

Taybi, Tahar; Cushman, John C; Borland, Anne M

2017-11-01

Nocturnal degradation of transitory starch is a limiting factor for the optimal function of crassulacean acid metabolism and must be coordinated with phosphoenolypyruvate carboxylase (PEPC)-mediated CO 2 uptake to optimise carbon gain over the diel cycle. The aim of this study was to test the hypothesis that nocturnal carboxylation is coordinated with starch degradation in CAM via a mechanism whereby the products of these pathways regulate diel transcript abundance and enzyme activities for both processes. To test this hypothesis, a starch and CAM-deficient mutant of Mesembryanthemum crystallinum was compared with wild type plants under well-watered and saline (CAM-inducing) conditions. Exposure to salinity increased the transcript abundance of genes required for nocturnal carboxylation, starch and sucrose degradation in both wild type and mutant, but the transcript abundance of several of these genes was not sustained over the dark period in the low-carbohydrate, CAM-deficient mutant. The diel pattern of transcript abundance for PEPC mirrored that of PEPC protein, as did the transcripts, protein, and activity of chloroplastic starch phosphorylase in both wild type and mutant, suggesting robust diel coordination of these metabolic processes. Activities of several amylase isoforms were low or lacking in the mutant, whilst the activity of a cytosolic isoform of starch phosphorylase was significantly elevated, indicating contrasting modes of metabolic regulation for the hydrolytic and phosphorylytic routes of starch degradation. Externally supplied sucrose resulted in an increase in nocturnal transcript abundance of genes required for nocturnal carboxylation and starch degradation. These results demonstrate that carbohydrates impact on transcriptional and post-transcriptional regulation of nocturnal carboxylation and starch degradation in CAM. Copyright © 2017 Elsevier GmbH. All rights reserved.

Effects of Co-Varying Diel-Cycling Hypoxia and pH on Growth in the Juvenile Eastern Oyster, Crassostrea virginica

PubMed Central

Keppel, Andrew G.; Breitburg, Denise L.; Burrell, Rebecca B.

2016-01-01

Shallow water provides important habitat for many species, but also exposes these organisms to daily fluctuations in dissolved oxygen (DO) and pH caused by cycles in the balance between photosynthesis and respiration that can contribute to repeated, brief periods of hypoxia and low pH (caused by elevated pCO2). The amplitude of these cycles, and the severity and duration of hypoxia and hypercapnia that result, can be increased by eutrophication, and are predicted to worsen with climate change. We conducted laboratory experiments to test the effects of both diel-cycling and constant low DO and pH (elevated pCO2) on growth of the juvenile eastern oyster (Crassostrea virginica), an economically and ecologically important estuarine species. Severe diel-cycling hypoxia (to 0.5 mg O2 L-1) reduced shell growth in juvenile oysters, as did constant hypoxia (1.2 and 2.0 mg O2 L-1), although effects varied among experiments, oyster ages, and exposure durations. Diel-cycling pH reduced growth only in experiments in which calcite saturation state cycled to ≤0.10 and only during the initial weeks of these experiments. In other cases, cycling pH sometimes led to increased growth rates. Comparisons of treatment effects across multiple weeks of exposure, and during a longer post-experiment field deployment, indicated that juvenile oysters can acclimate to, and in some cases compensate for initial reductions in growth. As a result, some ecosystem services dependent on juvenile oyster growth rates may be preserved even under severe cycling hypoxia and pH. PMID:27548256

Diel movement and habitat use by paddlefish in Navigation Pool 8 of the upper Mississippi River

USGS Publications Warehouse

Zigler, Steven J.; Dewey, Michael R.; Knights, Brent C.

1999-01-01

We studied diel movement and habitat use by paddlefish Polyodon spathula implanted with radio transmitters in Navigation Pool 8 of the upper Mississippi River. We radio-tracked five paddlefish during three randomly chosen 24-h periods each month in May, Aug, and Oct 1995. Paddlefish were located by boat one to three times every 3 h during each 24-h period. At each location, geographic coordinates were determined with a global positioning system receiver using the Precise Positioning Service, and depth was measured with a depth sounder. Location coordinates were plotted with ARC/INFO software on a Geographic Information System land–water coverage. Movement distances were calculated as the linear distance between sequential locations. Radio-tagged paddlefish usually remained in a secondary channel that had low current velocity during all seasons, whereas main channel, main channel border, tailwater, and backwater habitats were seldom used. Paddlefish strongly selected areas that were deep; about 62% of paddlefish locations were in areas with more than 6 m of depth, although this habitat constituted only 14.5% of the total study area. However, paddlefish used significantly shallower areas during the night than during the day. Paddlefish moved significantly larger distances at night than during the day in spring and fall, but differences in movement among diel periods during summer were not significant. Our research suggests that radiotelemetry studies that need to determine depth use or movement of paddlefish during small time scales may need to incorporate a diel component. However, study objectives to determine use of general habitat types by radio-marked paddlefish can be adequately met by tracking during the day.

Diazotrophic bacterioplankton in a coral reef lagoon: phylogeny, diel nitrogenase expression and response to phosphate enrichment.

PubMed

Hewson, Ian; Moisander, Pia H; Morrison, Amanda E; Zehr, Jonathan P

2007-05-01

We investigated diazotrophic bacterioplankton assemblage composition in the Heron Reef lagoon (Great Barrier Reef, Australia) using culture-independent techniques targeting the nifH fragment of the nitrogenase gene. Seawater was collected at 3 h intervals over a period of 72 h (i.e. over diel as well as tidal cycles). An incubation experiment was also conducted to assess the impact of phosphate (PO(4)3*) availability on nifH expression patterns. DNA-based nifH libraries contained primarily sequences that were most similar to nifH from sediment, microbial mat and surface-associated microorganisms, with a few sequences that clustered with typical open ocean phylotypes. In contrast to genomic DNA sequences, libraries prepared from gene transcripts (mRNA amplified by reverse transcription-polymerase chain reaction) were entirely cyanobacterial and contained phylotypes similar to those observed in open ocean plankton. The abundance of Trichodesmium and two uncultured cyanobacterial phylotypes from previous studies (group A and group B) were studied by quantitative-polymerase chain reaction in the lagoon samples. These were detected as transcripts, but were not detected in genomic DNA. The gene transcript abundance of these phylotypes demonstrated variability over several diel cycles. The PO(4)3* enrichment experiment had a clearer pattern of gene expression over diel cycles than the lagoon sampling, however PO(4)3* additions did not result in enhanced transcript abundance relative to control incubations. The results suggest that a number of diazotrophs in bacterioplankton of the reef lagoon may originate from sediment, coral or beachrock surfaces, sloughing into plankton with the flooding tide. The presence of typical open ocean phylotype transcripts in lagoon bacterioplankton may indicate that they are an important component of the N cycle of the coral reef.

Preliminary data used to assess the accuracy of estimating female white-tailed deer diel birthing-season home ranges using only daytime locations

USGS Publications Warehouse

Barber-Meyer, Shannon M.; Mech, L. David

2014-01-01

Because many white-tailed deer (Odocoileus virginianus) home-range and habitat-use studies rely only on daytime radio-tracking data, we were interested in whether diurnal data sufficiently represented diel home ranges. We analyzed home-range and core-use size and overlap of 8 adult-female Global-Positioning-System-collared deer during May and June 2001 and 2002 in the Superior National Forest, Minnesota, USA. We used 2 traditional means of analysis: minimum-convex polygons (MCP) and fixed kernels (95% FK, home range and 50% FK, core use) and two methods to partition day and night location data: (1) daytime = 0800-2000 h versus nighttime = 2000-0800 h and (2) sunup versus sundown. We found no statistical difference in size of home-range and core-use areas across day and night comparisons; however, in terms of spatial overlap, approximately 30% of night-range areas on average were not accounted for using daytime locations, with even greater differences between core-use areas (on average approximately 50%). We conclude that diurnal data do not adequately describe diel adult-female-deer, May-June home-ranges due to differences in spatial overlap (location). We suggest research to determine (1) if our findings hold in other circumstances (e.g., exclusive of the parturition period, other age classes, etc.), (2) if our conclusions generalize under other conditions (e.g., across deer range, varying seasons, etc.), (3) if habitat-use conclusions are affected by the incomplete overlap between diurnal and diel data, (4) how many nocturnal locations must be included to generate sufficient overlap, and (5) the influence of using other kernel sizes (e.g., 75%, 90%).

The nitrosocarbonyl hetero-Diels-Alder reaction as a useful tool for organic syntheses.

PubMed

Bodnar, Brian S; Miller, Marvin J

2011-06-14

Organic transformations that result in the formation of multiple covalent bonds within the same reaction are some of the most powerful tools in synthetic organic chemistry. Nitrosocarbonyl hetero-Diels-Alder (HDA) reactions allow for the simultaneous stereospecific introduction of carbon-nitrogen and carbon-oxygen bonds in one synthetic step, and provide direct access to 3,6-dihydro-1,2-oxazines. This Review describes the development of the nitrosocarbonyl HDA reaction and the utility of the resulting oxazine ring in the synthesis of a variety of important, biologically active molecules. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Landing periodicity of the mosquito Aedes aegypti in Trinidad in relation to the timing of insecticidal space-spraying.

PubMed

Chadee, D D

1988-04-01

Diel landing periodicity (biting cycle) of domestic Aedes aegypti (L.) in Trinidad, West Indies, was monitored using human bait during January-August 1980. The periodicity of females was predominantly diurnal (95.2% arriving during daylight or twilight) and bimodal, with consistent peaks at 06.00-07.00 and 17.00-18.00 hours. The diel periodicities at indoor and outdoor sites were virtually identical. Larger numbers of adults were collected outside than inside houses. It is recommended that the time of insecticidal ULV adulticiding should coincide with peaks in landing periodicity of the Ae.aegypti adults.

Microcontact Printing Patterning of an HOPG Surface by an Inverse Electron Demand Diels-Alder Reaction.

PubMed

Zhu, Jun; Hiltz, Jonathan; Tefashe, Ushula M; Mauzeroll, Janine; Lennox, R Bruce

2018-06-21

The chemical modification of an sp 2 hybridized carbon surface in a controllable manner is very challenging but also crucial for many applications. An inverse electron demand Diels-Alder (IEDDA) reaction using microcontact printing technique is introduced to spatially control the modification of a highly ordered pyrolytic graphite (HOPG) surface under ambient conditions. The covalent modification was characterized by Raman spectroscopy, XPS, and SECM. Tetrazine derivatives can effectively react with an HOPG surface and with microcontact printing methods resulting in spatially patterned surfaces being produced with micrometer-scale resolution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorogenic Behaviour of the Hetero-Diels-Alder Ligation of 5-Alkoxyoxazoles with Maleimides and their Applications.

PubMed

Renault, Kévin; Jouanno, Laurie-Anne; Lizzul-Jurse, Antoine; Renard, Pierre-Yves; Sabot, Cyrille

2016-12-19

Fluorogenic reactions are largely underrepresented in the toolbox of chemoselective ligations despite their tremendous potential, particularly in chemical biology and biochemistry. In this respect, we have investigated in full detail the fluorescence behaviour of the azaphthalamide, a scaffold which is generated through a hetero-Diels-Alder reaction of 5-alkoxyoxazole and maleimide derivatives under mild conditions that are compatible with, among others, peptide chemistry. The scope and limitations of such a fluorogenic labelling strategy were examined through four distinct applications, which target enzymatic activities or bioorthogonal reactions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microwave-promoted catalyst- and solvent-free aza-Diels-Alder reaction of aldimines with 6-[2-(dimethylamino)vinyl]-1,3-dimethyluracil.

PubMed

Sarma, Rupam; Sarmah, Manas M; Prajapati, Dipak

2012-02-17

A microwave-promoted aza-Diels-Alder reaction between 6-[2-(dimethylamino)vinyl]-1,3-dimethyluracil and aldimines has been developed for the construction of dihydropyrido[4,3-d]pyrimidines. Urea is effectively employed as an environmentally benign source of ammonia in the absence of any catalyst or solvent. The key step in the reaction is in situ generation and trapping of the reactive aldimine formed from urea and aldehyde by the diene system of the uracil. The reaction is clean, and excellent yields are obtained in a matter of a few minutes.

Ring-rearrangement metathesis of nitroso Diels-Alder cycloadducts.

PubMed

Vincent, Guillaume; Kouklovsky, Cyrille

2011-03-01

Strained nitroso Diels-Alder bicyclo[2.2.1] or [2.2.2] adducts functionalized with alkene side chains of diverse length undergo a ring-rearrangement metathesis process with external alkenes and Grubbs II or Hoveyda-Grubbs II ruthenium catalysts, under microwave irradiation or classical heating, to deliver cis-fused bicycles of various ring sizes, which contain a N-O bond. These scaffolds are of synthetic relevance for the generation of molecular diversity and to the total synthesis of alkaloids. The observation of unexpected reactions, such as epimerization or one-carbon homologation of the alkene side chain, is also reported. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heteropoly acid-catalyzed microwave-assisted three-component aza-Diels-Alder cyclizations: diastereoselective synthesis of potential drug candidates for Alzheimer's disease.

PubMed

Borkin, Dmitry; Morzhina, Elena; Datta, Silpi; Rudnitskaya, Aleksandra; Sood, Abha; Török, Marianna; Török, Béla

2011-03-07

A highly diastereoselective microwave-assisted three component synthesis of azabicyclo[2.2.2]octan-5-ones by a silicotungstic acid-catalyzed aza-Diels-Alder cyclization is described. The one-pot process involves the formation of the in situ generated Schiff base and its immediate cyclization with cyclohex-2-enone. The short reaction times, good yields and excellent diastereoselectivity make this annulation a practical and environmentally attractive method for the synthesis of the target compounds. Preliminary assays were carried out to determine the activity of the products in AChE as well as in amyloid β fibrillogenesis inhibition.

Computational Studies of Candida Antarctica Lipase B to Test its Capability as a Starting Point to Redesign New Diels-Alderases

PubMed Central

Świderek, Katarzyna; Moliner, Vicent

2015-01-01

The design of new biocatalysts is a target that is receiving increasing attention. One of the most popular reactions in this regard is the Diels-Alder cycloaddition due to its applications in organic synthesis and the absence of efficient natural enzymes that catalyze it. In this paper, the possibilities of using the highly promiscuous Candida Antarctica lipase B (CALB) as a protein scaffold to re-design a Diels-Alderase has been explored by means of theoretical quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations. Free energy surfaces have been computed for two reactions in the wild-type and in several mutants with hybrid AM1/MM potentials with corrections at M06-2X/MM level. The study of the counterpart reactions in solution has allowed performing comparative analysis that render interesting conclusion. Since the dienophile anchors very well in the oxyanion hole of all tested protein variants, the slight electronic changes from reactant complex to the transition state suggest that mutations should be focused in favoring the formation of reactive conformations of reactant complex that, in turn, would reduce the energy barrier. PMID:26624234

Covalently crosslinked diels-alder polymer networks.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bowman, Christopher; Adzima, Brian J.; Anderson, Benjamin John

2011-09-01

This project examines the utility of cycloaddition reactions for the synthesis of polymer networks. Cycloaddition reactions are desirable because they produce no unwanted side reactions or small molecules, allowing for the formation of high molecular weight species and glassy crosslinked networks. Both the Diels-Alder reaction and the copper-catalyzed azide-alkyne cycloaddition (CuAAC) were studied. Accomplishments include externally triggered healing of a thermoreversible covalent network via self-limited hysteresis heating, the creation of Diels-Alder based photoresists, and the successful photochemical catalysis of CuAAC as an alternative to the use of ascorbic acid for the generation of Cu(I) in click reactions. An analysis ofmore » the results reveals that these new methods offer the promise of efficiently creating robust, high molecular weight species and delicate three dimensional structures that incorporate chemical functionality in the patterned material. This work was performed under a Strategic Partnerships LDRD during FY10 and FY11 as part of a Sandia National Laboratories/University of Colorado-Boulder Excellence in Science and Engineering Fellowship awarded to Brian J. Adzima, a graduate student at UC-Boulder. Benjamin J. Anderson (Org. 1833) was the Sandia National Laboratories point-of-contact for this fellowship.« less

A comparison of diel nest temperature and nest site selection for two sympatric species of freshwater turtles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bodie, J.R.; Burke, V.J.; Smith, K.R.

1996-07-01

Diel nest temperature profiles were recorded form natural nests of eastern mud turtles (Kinosternon subrubrum) and Florida cooters (Pseudemys floridana) to determine whether nest microhabitat selection compensates for the effect of interspecific differences in nest depth on nest temperature. Kinosternon subrubrum nest depths were significantly shallower than those of P. floridana (t = 2.93, P < 0.01). We predicted that differences in nest depth would result in K. subrubrum nests being cooler at night and warmer during daylight than the deeper P. floridana nests. Diel temperature patterns agreed with out predictions at night, but P. floridana nest temperatures were notmore » lower than K. subrubrum nest temperatures during the day. Soil composition, slope and soil moisture were similar for the nest of both species. However, the amount of sunlight reaching the soil above K. subrubrum nest sites was substantially less than the amount above P. floridana nest sites. We suggest that these species select habitats for oviposition that differ in the amount and types of vegetative cover, which in turn affect exposure to sunlight and ultimately nest temperature. 27 refs., 2 figs.« less

Magnetic hyaluronic acid nanospheres via aqueous Diels-Alder chemistry to deliver dexamethasone for adipose tissue engineering.

PubMed

Jia, Yang; Fan, Ming; Chen, Huinan; Miao, Yuting; Xing, Lian; Jiang, Bohong; Cheng, Qifan; Liu, Dongwei; Bao, Weikang; Qian, Bin; Wang, Jionglu; Xing, Xiaodong; Tan, Huaping; Ling, Zhonghua; Chen, Yong

2015-11-15

Biopolymer-based nanospheres have great potential in the field of drug delivery and tissue regenerative medicine. In this work, we present a flexible way to conjugate a magnetic hyaluronic acid (HA) nanosphere system that are capable of vectoring delivery of adipogenic factor, e.g. dexamethasone, for adipose tissue engineering. Conjugation of nanospheres was established by aqueous Diels-Alder chemistry between furan and maleimide of HA derivatives. Simultaneously, a furan functionalized dexamethasone peptide, GQPGK, was synthesized and covalently immobilized into the nanospheres. The magnetic HA nanospheres were fabricated by encapsulating super-paramagnetic iron oxide nanoparticles, which exhibited quick magnetic sensitivity. The aqueous Diels-Alder chemistry made nanospheres high binding efficiency of dexamethasone, and the vectoring delivery of dexamethasone could be easily controlled by a external magnetic field. The potential application of the magnetic HA nanospheres on vectoring delivery of adipogenic factor was confirmed by co-culture of human adipose-derived stem cells (ASCs). In vitro cytotoxicity tests demonstrated that incorporation of dexamethasone into magnetic HA nanospheres showed high efficiency to promote ASCs viabilities, in particular under a magnetic field, which suggested a promising future for adipose regeneration applications. Copyright © 2015 Elsevier Inc. All rights reserved.

Enhancing Zeolite Performance by Catalyst Shaping in a Mesoscale Continuous-Flow Diels-Alder Process.

PubMed

Seghers, Sofie; Lefevere, Jasper; Mullens, Steven; De Vylder, Anton; Thybaut, Joris W; Stevens, Christian V

2018-03-26

In contrast to most lab-scale batch procedures, a continuous-flow implementation requires a thorough consideration of the solid catalyst design. In a previous study, irregular zeolite pellets were applied in a miniaturized continuous-flow reactor for the Diels-Alder reaction in the construction of norbornene scaffolds. After having faced the challenges of continuous operation, the aim of this study is to exploit catalyst structuring. To this end, microspheres with high uniformity and various sphere diameters were synthesized according to the vibrational droplet coagulation method. The influence of the use of these novel zeolite shapes in a mesoscale continuous-flow Diels-Alder process of cyclopentadiene and methyl acrylate is discussed. An impressive enhancement of catalyst lifetime is demonstrated, as even after a doubled process time of 14 h, the microspheres still exceeded the conversion after 7 h when using zeolite pellets by 30 %. A dual reason is found for this beneficial impact of catalyst shaping. The significant improvement in catalyst longevity can be attributed to the interplay of the chemical composition and the porosity structure of the microspheres. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Does Predation Influence the Seasonal and Diel Timing of Moose Calving in Central Ontario, Canada?

PubMed Central

Patterson, Brent R.; Mills, Kenneth J.; Middel, Kevin R.; Benson, John F.; Obbard, Martyn E.

2016-01-01

Birth synchrony is well documented among ungulates and is hypothesised to maximize neonate survival, either by minimizing the risk of predation through predator swamping or by synchronising birthing with increased seasonal food availability. We used encapsulated vaginal implant transmitters to locate and capture neonatal moose calves and document the seasonal and diel timing of parturition in two adjacent study areas with different predation pressure in central Ontario, Canada. We tested the hypothesis that predation promotes earlier and more synchronous birth of moose calves. Across both areas, proportionately more births occurred during the afternoon and fewer than expected occurred overnight. Mean date of calving averaged 1.5 days earlier and calving was also more synchronous in the study area with heavier predation pressure, despite average green-up date and peak Normalized Difference Vegetation Index date occurring 2 days later in this study area than in the area receiving lighter predation pressure. We encourage analysis of data on timing of parturition from additional study areas experiencing varying degrees of predation pressure to better clarify the influence of predation in driving seasonal and diel timing of parturition in temperate ungulates. PMID:27082234

Diel feeding ecology of Slimy Sculpin in a tributary to Skaneateles Lake, New York

USGS Publications Warehouse

Chalupnicki, Marc A.; Johnson, James H.

2016-01-01

Interactions among the benthic community are typically overlooked but play an important role in fish community dynamics. We examined the diel feeding ecology of Slimy Sculpin (Cottus cognatus) from Grout Brook, a tributary to Skaneateles Lake. Of the six time periods examined, Slimy Sculpin consumed the least during the nighttime (2400 h and 0400 h). Chironomids were the major prey consumed during all time periods except for 2400 h when ephemeropterans were the major prey consumed. There was a moderate preference by Slimy Sculpin for food from the benthos (0.59 ± 0.06) with Diptera (Chironomids), Ephemeroptera (Baetidae), and Trichoptera (Brachycentridae) representing the major taxa. Slimy Sculpin appear to be opportunistic feeders selecting what is most available in the brook. Index of fullness was variable and averaged 1.15% across the diel cycle. Daily ration was measured as a function of fish dry body weight and ranged from 0.12 to 0.22. Estimates of daily consumption ranged from 0.007% to 4.0% of body weight, which corresponds to reports for other species. These findings have application in gauging the relative importance of Slimy Sculpin in streams where highly valued salmonid species also occur.

When do predatory mites (Phytoseiidae) attack? Understanding their diel and seasonal predation patterns.

PubMed

Pérez-Sayas, Consuelo; Aguilar-Fenollosa, Ernestina; Hurtado, Mónica A; Jaques, Josep A; Pina, Tatiana

2017-06-16

Predatory mites of the Phytoseiidae family are considered one of the most important groups of natural enemies used in biological control. The behavioral patterns of arthropods can differ greatly daily and seasonally; however, there is a lack of literature related to Phytoseiidae diel and seasonal predation patterns. The predatory activity of three phytoseiid species (two Tetranychidae-specialists, Phytoseiulus persimilis and Neoseiulus californicus, and one omnivore, Euseius stipulatus) that occur naturally in Spanish citrus orchards was observed under laboratory conditions in winter and summer. The temperature and photoperiod of the climatic chamber where the mites were reared did not change during the experiment. Our study demonstrates that phytoseiids can exhibit diel and seasonal predatory patterns when feeding on Tetranychus urticae (Acari: Tetranychidae). Neoseiulus californicus was revealed to be a nocturnal predator in summer but diurnal in winter. In contrast, P. persimilis activity was maximal during the daytime, and E. stipulatus showed no clear daily predation patterns. The predatory patterns described in this study should be taken into account when designing laboratory studies and also in field samplings, especially when applying molecular techniques to unveil trophic relationships. © 2017 Institute of Zoology, Chinese Academy of Sciences.

Diel trends in plant sensitivity to ozone: Toward parameterization of the defense component of effective flux

NASA Astrophysics Data System (ADS)

Grantz, D. A.; Vu, H.; Heath, R. L.; Burkey, K.

2011-12-01

Ozone (O3) injury to vegetation can be conceptually divided into three stages: 1) O3 entrance into the leaf including fractionation of stomatal vs. non-stomatal deposition; 2) O3 overcoming initial metabolic defenses within individual leaves, and 3) oxidant attack by O3 or derivatives on bioreceptors to produce injury. Ozone deposition at canopy scale and uptake at leaf scale are routinely obtained by observational and modeling techniques (Massman and Grantz, 1995). Injury can be assessed experimentally. However, predictive association between ozone concentration or flux and injury is currently not well characterized. This is due to uncertainties in rates and capacities of ozone detoxification, the nature of plant defense mechanisms, and their temporal (diel and seasonal) variability (Heath et al., 2009; Massman et al., 2000). We have developed a plant sensitivity parameter (SO3) relating injury (I) to the sum of O3 flux and photon flux density (FO3 + PPFD) during exposure. By restricting leaf exposure to O3 to a brief (15 min) pulse, we assess passive defense mechanisms, assuming that the pulse duration provides insufficient time for induction of additional (active) defense capacity during exposure. Greenhouse grown Pima cotton was exposed in chambers to pulsed O3 at a range of concentrations, stomatal conductance was measured directly pre- and post-exposure, and injury was assessed 1 week later using several indicators. SO3, determined at 2 hour intervals, exhibited clear diel trends, with maximal sensitivity shortly after solar noon, and minimal sensitivity early and late in the photoperiod. This diel pattern of SO3 did not support suggestions that plant defense is correlated with instantaneous photosynthetic rate. There was only weak correlation between SO3 and whole leaf ascorbate, ascorbate redox poise, or total antioxidant capacity, though future measurements of apoplastic antioxidants may improve these relationships. The parameter, SO3, may be directly related to the weighting factor commonly used as a surrogate for plant defense in model relationships between injury and O3 flux (e.g. Massman et al. 2000). Diurnally varying SO3 incorporates the combined oxidative stresses of O3 and photochemistry, and can be combined with natural diel cycles of ozone concentration and models of stomatal conductance and photosynthesis, to yield integrated impacts of O3 on injury to vegetation.

[Benthic fauna associated to a Thalassia testudinum (Hydrocharitaceae) bed in Parque Nacional Morrocoy, Venezuela].

PubMed

Rodríguez, C; Villamizar, E

2000-12-01

The benthic fauna and diel variation in a shallow seagrass bed (Thalassia testudinum) were studied in Playa Mero, Venezuela. Samples of organisms and sediments were taken using PVC cylinders, 5cm in diameter, along a transect perpendicular to the coast. Seagrass cover, shoot density and biomass were estimated. The seagrass cover was homogeneous along the transect. The intermediate zone had the highest number of shoots and of above-ground and rhizome biomass. Composition and abundance of benthic organisms were related with seagrass and sediment characteristics. Sediment organic matter content and organism abundance were highest near the shore Molluscs, polychaetes, oligochaetes and nematodes were the most abundant groups. Species richness was higher in daytime (40 versus 28 at night). Gastropods were the most abundant organisms both at day and night while polychaetes and crustaceans increased during the day, and holoturids were more numerous at night.

Évolution nycthémérale des composantes biochimiques du phytoplancton de la retenue du barrage Idriss premier (Fès, Maroc)

NASA Astrophysics Data System (ADS)

Bahhou, J.; Alaoui Mhamdi, M.

1999-03-01

The diel changes of the biochemical composition of the phytoplankton were studied in the Idriss first reservoir (located on the Inaouen river at thirty Km from the city of Fes, Morrocco) during September 1994. Several biomass and metabolic indicators (proteins, carbohydrates, lipids, chlorophyll a and primary production) were assessed every fourth hour over tow days (7, 8 and 9 September). Since the Protein/Carbohydrates ratio (P/C) is largely recognised as a good integrator of the metabolic functions of the cells, we examined its distribution pattern concomitantly with aforementioned parameters. The results demonstrated enhanced P/C ratios clearly indicating that nutrients were sufficiently available for growth. In addition, this index showed a diel significant variation with levels higher in the night than in the day. Moreover, these results suggest that phytoplankton species during the night used the day-synthesised carbohydrates to insure the cell metabolic functioning. The P/C presents relatively high values in proposition to the ones that have been recorded in temperate regions, and seems to be related to azotic inputs of the Inaouen river. Dans le but de parfaire nos connaissances sur le fonctionnement du sous écosystème phytoplancton, nous nous sommes intéressés à étudier son cycle nycthéméral et son métabolisme cellulaire dans la retenue du barrage Idriss premier. Cette dernière, construite sur l'Oued Inaouène, est située à une trentaine de Km de la ville de Fès. Au cours de ce cycle, les prélèvements ont été effectués selon une séquence temporelle de 4 heures pendant 48 heures, les 7, 8 et 9 septembre 1994. L'étude de l'évolution des composantes biochimiques des cellules phytoplanctoniques à savoir les protéines, les glucides et les lipides a permis de mettre en évidence des variations nycthémérales importantes. Ces variations sont d'autant plus importantes que les variations spatiales observées entre les profondeurs. De plus, le rapport protéines/glucides (P/G), reconnu comme un bon indicateur de l'état physiologique des algues, présente des valeurs plus élevées la nuit que le jour au niveau du fond du lac. Ce résultat suggère que le phytoplancton utilise les produits de réserve synthétisés le jour pour assurer le fonctionnement métabolique des cellules. De plus, les valeurs de ce rapport sont relativement élevées par rapport à celle enregistrées dans les régions tempérés et semblent être liées aux ressources azotées du milieu en particulier les apports de l'Oued Inaouène.

Chlorotheolides A and B, Spiroketals Generated via Diels-Alder Reactions in the Endophytic Fungus Pestalotiopsis theae.

PubMed

Liu, Ling; Han, Yu; Xiao, Junhai; Li, Li; Guo, Liangdong; Jiang, Xuejun; Kong, Lingyi; Che, Yongsheng

2016-10-28

Chlorotheolides A (1) and B (2), two new spiroketals possessing the unique [4,7]methanochromene and dispiro-trione skeletons, respectively, and their putative biosynthetic precursors, 1-undecen-2,3-dicarboxylic acid (3) and maldoxin (4), were isolated from the solid substrate fermentation of the plant endophytic fungus Pestalotiopsis theae (N635). Their structures were elucidated based on NMR spectroscopic data and electronic circular dichroism calculations. Biogenetically, compounds 1 and 2 could be generated from the co-isolated 3 and 4 via Diels-Alder reactions. Chlorotheolide (2) showed an antiproliferative effect against the human tumor cell line HeLa and induced an autophagic process in the cells.

Classical Example of Total Kinetic and Thermodynamic Control: The Diels-Alder Reaction between DMAD and Bis-furyl Dienes.

PubMed

Borisova, Kseniya K; Kvyatkovskaya, Elizaveta A; Nikitina, Eugeniya V; Aysin, Rinat R; Novikov, Roman A; Zubkov, Fedor I

2018-04-20

A rare example of chemospecificity in the tandem Diels-Alder reaction of activated alkynes and bis-dienes has been revealed. The reaction between bis-furyl dienes and DMAD occurs at 25-80 °C and leads to kinetically controlled "pincer" adducts, 4a,8a-disubstituted 1,4:5,8-diepoxynaphthalenes. On the contrary, only thermodynamically controlled "domino" adducts (2,3-disubstituted 1,4:5,8-diepoxynaphthalenes) are formed in the same reaction at 140 °C. The "pincer" adducts can be transformed to the "domino" adducts at heating. The rate constants for reactions of both types were calculated using dynamic 1 H NMR spectroscopy.

The diel migrations and distributions within a mesopelagic community in the North East Atlantic. 7. Siphonophores

NASA Astrophysics Data System (ADS)

Pugh, P. R.

Siphonophores are by far the dominant macroplanktonic-micronektonic taxon of animals present in the 48 hr series of samples as a whole. A total of 35 species were identified, with four of these making up over 90% of the total numbers. Details of how the siphonophore population was estimated are discussed, but few species underwent clear cut diel vertical migration although there was considerable variability in their distributions over the sampling periods. The hydrography of the sampling area was investigated in relation to its possible effects on the faunal assemblages, and the important role of siphonophores as carnivores in the planktonic food chain was discussed.

The 2.5-diacyl-1,4-dimethylbenzenes: Examples of bisphotoenol equivalents

NASA Technical Reports Server (NTRS)

Meador, Michael A.

1987-01-01

The photochemistry of 2,5-dibenzoyl(DBX)-and 2,5-diacetyl-1,4-dimethylbenzene (DAX) has been investigated. Both compounds readily undergo photoenolization similar to 0-alkylphenyl ketones. However, unlike 0-alkylphenyl ketones DAX and DBX are each capable of undergoing two tandem photoenolizations. Photoenols derived from o-alkylphenyl ketones have been successfully trapped with Diels-Alder dienophiles to provide a convenient synthesis of substituted tetralins. Similarly, Diels-Alder trapping of DBX photoenils afforded substituted tetra- and octahydro anthracenes. Further mainpulation of these photadducts provided the corresponding anthracenes in good yield. The photochemistry of DAX and DBX will be discussed, in particular their use in the synthesis of substituted anthracenes.

Modelling the transport of common sole larvae in the southern North Sea: Influence of hydrodynamics and larval vertical movements

NASA Astrophysics Data System (ADS)

Savina, Marie; Lacroix, Geneviève; Ruddick, Kevin

2010-04-01

In the present work we used a particle-tracking model coupled to a 3D hydrodynamic model to study the combined effect of hydrodynamic variability and active vertical movements on the transport of sole larvae in the southern North Sea. Larval transport from the 6 main spawning grounds was simulated during 40 day periods starting on 2 plausible spawning dates, the 15/04 and the 01/05, during 2 years, 1995 and 1996. In addition to a "passive" behaviour, 3 types of active vertical movements inspired from previous studies have been tested: (1) Eggs and early larvae float in the surface waters, late larvae migrate toward the bottom and stay there until the end of the simulation; (2 and 3) Eggs float in the surface waters, early larvae perform diel vertical migrations in the surface waters, and (2) Late larvae perform diel vertical migrations in the bottom waters until the end of the simulation; or (3) Late larvae perform tidally synchronised vertical migrations in the bottom waters until the end of the simulation. These behaviours have been implemented in the model with vertical migration rates, positive or negative, which can account for buoyancy or real swimming activity. Variations in larval transport were analysed in terms of mean trajectories, final larvae distribution, larval retention above nurseries, and connectivity. Results suggest that the variations in larval retention above nurseries due to the varying hydrodynamic conditions are not consistent in space i.e. not the same for all the spawning sites. The effect of active vertical movements on larval transport is also not consistent in space: Effects of active vertical movements include decreased retention above nurseries, decreased transport and/or decreased horizontal dispersion of larvae through reduced vertical shear (depending on the zone). The variability in larval retention due to hydrodynamic variability is higher than variability due to differences in the behaviour of larvae. In terms of connectivity, exchanges of larvae between the 6 areas considered are moderate: 10 connections happened out of the 30 possible, and the amount of larvae exchanged is much lower than the amount of larvae retained except in a few cases. This is not incompatible with the possible existence of subpopulations of sole in the Eastern Channel and southern North Sea.

Grafting methyl acrylic onto carbon fiber via Diels-Alder reaction for excellent mechanical and tribological properties of phenolic composites

NASA Astrophysics Data System (ADS)

Fei, Jie; Duan, Xiao; Luo, Lan; Zhang, Chao; Qi, Ying; Li, Hejun; Feng, Yongqiang; Huang, Jianfeng

2018-03-01

Carbon fibers (CFs) were grafted with methyl acrylic via Diels-Alder reaction at the different oil bath temperature effectively creating a carboxyl functionalized surface. The effect of grafting temperature on the surface morphology and functional groups of carbon fibers were investigated by FTIR, Raman spectroscopy, XPS and SEM respectively. The results showed that the optimal grafting temperature was 80 °C, and the relative surface coverage by carboxylic acid groups increased from an initial 5.16% up to 19.30% significantly improved the chemical activity without damaging the skin and core region of the carbon fibers. Mechanical property tests indicated that the shear and tensile strength of the sample with the grafting temperature of 80 °C (CFRP-3) increased obviously by 90.3% and 78.7%, respectively, compared with the pristine carbon fibers reinforced composite. Further, the sample CFRP-3 exhibited higher and more stable friction coefficient and improved wear resistance, while the wear rate decreased 52.7%, from 10.8 × 10-6 to 5.1 × 10-6 mm3/N m. The present work shows that grafting methyl acrylic via Diels-Alder reaction could be a highly efficient and facile method to functionalize carbon fibers for advanced composites.

Diel spawning behavior of chum salmon in the Columbia River

USGS Publications Warehouse

Tiffan, K.F.; Rondorf, D.W.; Skalicky, J.J.

2005-01-01

We conducted a study during 2003 in a side channel of the Columbia River downstream of Bonneville Dam to describe the diel spawning behavior of wild chum salmon Oncorhynchus keta. We collected observational data on 14 pairs of chum salmon using a dual-frequency identification sonar. Spawners of both genders were observed chasing intruders during nighttime and daytime as nests were constructed. Regardless of diel period, females were engaged in digging to both construct nests and cover eggs, and courting males exhibited the prespawning behavior of tail-crossing. We observed a total of 13 spawning events, of which 9 occurred at night and 4 occurred during the day. Once chum salmon begin nest construction, visual cues are apparently not required for courtship, nest defense, and spawning. To enhance successful spawning, flows from Bonneville Dam during the spawning season were reduced during the day but were sometimes increased at night to pass water and meet power demand (i.e., reverse loading), the assumption being that chum salmon are inactive at night. Our findings show that this assumption was violated. Therefore, reverse loading may disrupt the complex prespawning behavior that occurs both during the day and at night, as well as attract spawners to areas that were dewatered during the day.

Characterizing multiple metal ion binding sites within a ribozyme by cadmium-induced EPR silencing

PubMed Central

Kisseleva, Natalia; Kraut, Stefanie; Jäschke, Andres; Schiemann, Olav

2007-01-01

In ribozyme catalysis, metal ions are generally known to make structural and∕or mechanistic contributions. The catalytic activity of a previously described Diels-Alderase ribozyme was found to depend on the concentration of divalent metal ions, and crystallographic data revealed multiple binding sites. Here, we elucidate the interactions of this ribozyme with divalent metal ions in solution using electron paramagnetic resonance (EPR) spectroscopy. Manganese ion titrations revealed five high-affinity Mn2+ binding sites with an upper Kd of 0.6±0.2 μM. In order to characterize each binding site individually, EPR-silent Cd2+ ions were used to saturate the other binding sites. This cadmium-induced EPR silencing showed that the Mn2+ binding sites possess different affinities. In addition, these binding sites could be assigned to three different types, including innersphere, outersphere, and a Mn2+ dimer. Based on simulations, the Mn2+-Mn2+ distance within the dimer was found to be ∼6 Å, which is in good agreement with crystallographic data. The EPR-spectroscopic characterization reveals no structural changes upon addition of a Diels-Alder product, supporting the concept of a preorganized catalytic pocket in the Diels-Alder ribozyme and the structural role of these ions. PMID:19404418

Domino Acylation/Diels-Alder Synthesis of N-Alkyl-octahydroisoquinolin-1-one-8-carboxylic Acids under Low-Solvent Conditions.

PubMed

Slauson, Stephen R; Pemberton, Ryan; Ghosh, Partha; Tantillo, Dean J; Aubé, Jeffrey

2015-05-15

The development of the domino reaction between an aminoethyl-substituted diene and maleic anhydride to afford an N-substituted octahydroisoquinolin-1-one is described. A typical procedure involves the treatment of a 1-aminoethyl-substituted butadiene with maleic anhydride at 0 °C to room temperature for 20 min under low-solvent conditions, which affords a series of isoquinolinone carboxylic acids in moderate to excellent yields. NMR monitoring suggested that the reaction proceeded via an initial acylation step followed by an intramolecular Diels-Alder reaction. For the latter step, a significant rate difference was observed depending on whether the amino group was substituted by a phenyl or an alkyl (usually benzyl) substituent, with the former noted by NMR to be substantially slower. The Diels-Alder step was studied by density functional theory (DFT) methods, leading to the conclusion that the degree of preorganization in the starting acylated intermediate had the largest effect on the reaction barriers. In addition, the effect of electronics on the aromatic ring in N-phenyl substrates was studied computationally and experimentally. Overall, this protocol proved considerably more amenable to scale up compared to earlier methods by eliminating the requirement of microwave batch chemistry for this reaction as well as significantly reducing the quantity of solvent.

Temporal and spatial transcriptomic and microRNA dynamics of CAM photosynthesis in pineapple.

PubMed

Wai, Ching M; VanBuren, Robert; Zhang, Jisen; Huang, Lixian; Miao, Wenjing; Edger, Patrick P; Yim, Won C; Priest, Henry D; Meyers, Blake C; Mockler, Todd; Smith, J Andrew C; Cushman, John C; Ming, Ray

2017-10-01

The altered carbon assimilation pathway of crassulacean acid metabolism (CAM) photosynthesis results in an up to 80% higher water-use efficiency than C 3 photosynthesis in plants making it a potentially useful pathway for engineering crop plants with improved drought tolerance. Here we surveyed detailed temporal (diel time course) and spatial (across a leaf gradient) gene and microRNA (miRNA) expression patterns in the obligate CAM plant pineapple [Ananas comosus (L.) Merr.]. The high-resolution transcriptome atlas allowed us to distinguish between CAM-related and non-CAM gene copies. A differential gene co-expression network across green and white leaf diel datasets identified genes with circadian oscillation, CAM-related functions, and source-sink relations. Gene co-expression clusters containing CAM pathway genes are enriched with clock-associated cis-elements, suggesting circadian regulation of CAM. About 20% of pineapple microRNAs have diel expression patterns, with several that target key CAM-related genes. Expression and physiology data provide a model for CAM-specific carbohydrate flux and long-distance hexose transport. Together these resources provide a list of candidate genes for targeted engineering of CAM into C 3 photosynthesis crop species. © 2017 The Authors The Plant Journal © 2017 John Wiley & Sons Ltd.

Diels-Alder functionalized carbon nanotubes for bone tissue engineering: in vitro/in vivo biocompatibility and biodegradability.

PubMed

Mata, D; Amaral, M; Fernandes, A J S; Colaço, B; Gama, A; Paiva, M C; Gomes, P S; Silva, R F; Fernandes, M H

2015-01-01

The risk-benefit balance for carbon nanotubes (CNTs) dictates their clinical fate. To take a step forward at this crossroad it is compulsory to modulate the CNT in vivo biocompatibility and biodegradability via e.g. chemical functionalization. CNT membranes were functionalised combining a Diels-Alder cycloaddition reaction to generate cyclohexene (-C6H10) followed by a mild oxidisation to yield carboxylic acid groups (-COOH). In vitro proliferation and osteogenic differentiation of human osteoblastic cells were maximized on functionalized CNT membranes (p,f-CNTs). The in vivo subcutaneously implanted materials showed a higher biological reactivity, thus inducing a slighter intense inflammatory response compared to non-functionalized CNT membranes (p-CNTs), but still showing a reduced cytotoxicity profile. Moreover, the in vivo biodegradation of CNTs was superior for p,f-CNT membranes, likely mediated by the oxidation-induced myeloperoxidase (MPO) in neutrophil and macrophage inflammatory milieus. This proves the biodegradability faculty of functionalized CNTs, which potentially avoids long-term tissue accumulation and triggering of acute toxicity. On the whole, the proposed Diels-Alder functionalization accounts for the improved CNT biological response in terms of the biocompatibility and biodegradability profiles. Therefore, CNTs can be considered for use in bone tissue engineering without notable toxicological threats.

Computational design of a Diels-Alderase from a thermophilic esterase: the importance of dynamics

NASA Astrophysics Data System (ADS)

Linder, Mats; Johansson, Adam Johannes; Olsson, Tjelvar S. G.; Liebeschuetz, John; Brinck, Tore

2012-09-01

A novel computational Diels-Alderase design, based on a relatively rare form of carboxylesterase from Geobacillus stearothermophilus, is presented and theoretically evaluated. The structure was found by mining the PDB for a suitable oxyanion hole-containing structure, followed by a combinatorial approach to find suitable substrates and rational mutations. Four lead designs were selected and thoroughly modeled to obtain realistic estimates of substrate binding and prearrangement. Molecular dynamics simulations and DFT calculations were used to optimize and estimate binding affinity and activation energies. A large quantum chemical model was used to capture the salient interactions in the crucial transition state (TS). Our quantitative estimation of kinetic parameters was validated against four experimentally characterized Diels-Alderases with good results. The final designs in this work are predicted to have rate enhancements of ≈103-106 and high predicted proficiencies. This work emphasizes the importance of considering protein dynamics in the design approach, and provides a quantitative estimate of the how the TS stabilization observed in most de novo and redesigned enzymes is decreased compared to a minimal, `ideal' model. The presented design is highly interesting for further optimization and applications since it is based on a thermophilic enzyme ( T opt = 70 °C).

The influence of hydrous Mn–Zn oxides on diel cycling of Zn in an alkaline stream draining abandoned mine lands

USGS Publications Warehouse

Shope, Christopher L.; Xie, Ying; Gammons, Christopher H.

2006-01-01

Many mining-impacted streams in western Montana with pH near or above neutrality display large (up to 500%) diel cycles in dissolved Zn concentrations. The streams in question typically contain boulders coated with a thin biofilm, as well as black mineral crusts composed of hydrous Mn–Zn oxides. Laboratory mesocosm experiments simulating diel behavior in High Ore Creek (one of the Montana streams with particularly high Zn concentrations) show that the Zn cycles are not caused by 24-h changes in streamflow or hyporheic exchange, but rather to reversible in-stream processes that are driven by the solar cycle and its attendant influence on pH and water temperature (T). Laboratory experiments using natural Mn–Zn precipitates from the creek show that the mobilities of Zn and Mn increase nearly an order of magnitude for each unit decrease in pH, and decrease 2.4-fold for an increase in T from 5 to 20 °C. The response of dissolved metal concentration to small changes in either pH or T was rapid and reversible, and dissolved Zn concentrations were roughly an order of magnitude higher than Mn. These observations are best explained by sorption of Zn2+ and Mn2+ onto the secondary Mn–Zn oxide surfaces. From the T-dependence of residual metal concentrations in solution, approximate adsorption enthalpies of +50 kJ/mol (Zn) and +46 kJ/mol (Mn) were obtained, which are within the range of enthalpy values reported in the literature for sorption of divalent metal cations onto hydrous metal oxides. Using the derived pH- and T-dependencies from the experiments, good agreement is shown between predicted and observed diel Zn cycles for several historical data sets collected from High Ore Creek.

Zooplankton diel vertical migration and contribution to deep active carbon flux in the NW Mediterranean

NASA Astrophysics Data System (ADS)

Isla, Alejandro; Scharek, Renate; Latasa, Mikel

2015-03-01

The diel vertical migration (DVM) of zooplankton contributes to the biological pump transporting material from surface to deep waters. We examined the DVM of the zooplankton community in different size fractions (53-200 μm, 200-500 μm, 500-1000 μm, 1000-2000 μm and > 2000 μm) during three cruises carried out in the open NW Mediterranean Sea. We assessed their metabolic rates from empirical published relationships and estimated the active fluxes of dissolved carbon to the mesopelagic zone driven by migrant zooplankton. Within the predominantly oligotrophic Mediterranean Sea, the NW region is one of the most productive ones, with a seasonal cycle characterized by a prominent spring bloom. The study area was visited at three different phases of the seasonal cycle: during the spring bloom, the post-bloom, and strongly stratified oligotrophic conditions. We found seasonal differences in DVM, less evident during the bloom. Changes in DVM intensity were related to the composition of the zooplanktonic assemblage, which also varied between cruises. Euphausiids appeared as the most active migrants in all seasons, and their life cycle conditioned the observed pattern. Immature stages, which are unable to perform large diel vertical movements, dominated during the bloom, in contrast to the higher relative importance of migrating adults in the other two sampling periods. The amount of dissolved carbon exported was determined by the migrant zooplankton biomass, being highest during the post-bloom (2.2 mmol C respired m- 2 d- 1, and up to 3.1 mmol C exported m- 2 d- 1 when DOC release estimations are added). The active transport by diel migrants represented a substantial contribution to total carbon export to deep waters, especially under stratified oligotrophic conditions, revealing the importance of zooplankton in the biological pump operating in the study area.

Genome-wide profiling of 24 hr diel rhythmicity in the water flea, Daphnia pulex: network analysis reveals rhythmic gene expression and enhances functional gene annotation.

PubMed

Rund, Samuel S C; Yoo, Boyoung; Alam, Camille; Green, Taryn; Stephens, Melissa T; Zeng, Erliang; George, Gary F; Sheppard, Aaron D; Duffield, Giles E; Milenković, Tijana; Pfrender, Michael E

2016-08-18

Marine and freshwater zooplankton exhibit daily rhythmic patterns of behavior and physiology which may be regulated directly by the light:dark (LD) cycle and/or a molecular circadian clock. One of the best-studied zooplankton taxa, the freshwater crustacean Daphnia, has a 24 h diel vertical migration (DVM) behavior whereby the organism travels up and down through the water column daily. DVM plays a critical role in resource tracking and the behavioral avoidance of predators and damaging ultraviolet radiation. However, there is little information at the transcriptional level linking the expression patterns of genes to the rhythmic physiology/behavior of Daphnia. Here we analyzed genome-wide temporal transcriptional patterns from Daphnia pulex collected over a 44 h time period under a 12:12 LD cycle (diel) conditions using a cosine-fitting algorithm. We used a comprehensive network modeling and analysis approach to identify novel co-regulated rhythmic genes that have similar network topological properties and functional annotations as rhythmic genes identified by the cosine-fitting analyses. Furthermore, we used the network approach to predict with high accuracy novel gene-function associations, thus enhancing current functional annotations available for genes in this ecologically relevant model species. Our results reveal that genes in many functional groupings exhibit 24 h rhythms in their expression patterns under diel conditions. We highlight the rhythmic expression of immunity, oxidative detoxification, and sensory process genes. We discuss differences in the chronobiology of D. pulex from other well-characterized terrestrial arthropods. This research adds to a growing body of literature suggesting the genetic mechanisms governing rhythmicity in crustaceans may be divergent from other arthropod lineages including insects. Lastly, these results highlight the power of using a network analysis approach to identify differential gene expression and provide novel functional annotation.

Metabolic Profiles and cDNA-AFLP Analysis of Salvia miltiorrhiza and Salvia castanea Diel f. tomentosa Stib

PubMed Central

Liang, Xiao; Liang, Zongsuo; Zhang, Meixiang; Shen, Shuang; Liu, Hongyun; Liu, Yan

2012-01-01

Plants of the genus Salvia produce various types of phenolic compounds and tanshinones which are effective for treatment of coronary heart disease. Salvia miltiorrhiza and S. castanea Diels f. tomentosa Stib are two important members of the genus. In this study, metabolic profiles and cDNA-AFLP analysis of four samples were employed to identify novel genes potentially involved in phenolic compounds and tanshinones biosynthesis, including the red roots from the two species and two tanshinone-free roots from S. miltiorrhiza. The results showed that the red roots of S. castanea Diels f. tomentosa Stib produced high contents of rosmarinic acid (21.77 mg/g) and tanshinone IIA (12.60 mg/g), but low content of salvianolic acid B (1.45 mg/g). The red roots of S. miltiorrhiza produced high content of salvianolic acid B (18.69 mg/g), while tanshinones accumulation in this sample was much less than that in S. castanea Diels f. tomentosa Stib. Tanshinones were not detected in the two tanshinone-free samples, which produced high contents of phenolic compounds. A cDNA-AFLP analysis with 128 primer pairs revealed that 2300 transcript derived fragments (TDFs) were differentially expressed among the four samples. About 323 TDFs were sequenced, of which 78 TDFs were annotated with known functions through BLASTX searching the Genbank database and 14 annotated TDFs were assigned into secondary metabolic pathways through searching the KEGGPATHWAY database. The quantitative real-time PCR analysis indicated that the expression of 9 TDFs was positively correlated with accumulation of phenolic compounds and tanshinones. These TDFs additionally showed coordinated transcriptional response with 6 previously-identified genes involved in biosynthesis of tanshinones and phenolic compounds in S. miltiorrhiza hairy roots treated with yeast extract. The sequence data in the present work not only provided us candidate genes involved in phenolic compounds and tanshinones biosynthesis but also gave us further insight into secondary metabolism in Salvia. PMID:22303439

Light quality modulates metabolic synchronization over the diel phases of crassulacean acid metabolism

PubMed Central

Ceusters, Johan; Borland, Anne M.; Taybi, Tahar; Frans, Mario; Godts, Christof; De Proft, Maurice P.

2014-01-01

Temporal compartmentation of carboxylation processes is a defining feature of crassulacean acid metabolism and involves circadian control of key metabolic and transport steps that regulate the supply and demand for carbon over a 24h cycle. Recent insights on the molecular workings of the circadian clock and its connection with environmental inputs raise new questions on the importance of light quality and, by analogy, certain photoreceptors for synchronizing the metabolic components of CAM. The present work tested the hypothesis that optimal coupling of stomatal conductance, net CO2 uptake, and the reciprocal turnover of carbohydrates and organic acids over the diel CAM cycle requires both blue and red light input signals. Contrasting monochromatic wavelengths of blue, green, and red light (i.e. 475, 530, 630nm) with low fluence rates (10 μmol m–2 s–1) were administered for 16 hours each diel cycle for a total treatment time of 48 hours to the obligate CAM bromeliad, Aechmea ‘Maya’. Of the light treatments imposed, low-fluence blue light was a key determinant in regulating stomatal responses, organic acid mobilization from the vacuole, and daytime decarboxylation. However, the reciprocal relationship between starch and organic acid turnover that is typical for CAM was uncoupled under low-fluence blue light. Under low-fluence red or green light, the diel turnover of storage carbohydrates was orchestrated in line with the requirements of CAM, but a consistent delay in acid consumption at dawn compared with plants under white or low-fluence blue light was noted. Consistent with the acknowledged influences of both red and blue light as input signals for the circadian clock, the data stress the importance of both red and blue-light signalling pathways for synchronizing the metabolic and physiological components of CAM over the day/night cycle. PMID:24803500

Specificity Responses of Grasshoppers in Temperate Grasslands to Diel Asymmetric Warming

PubMed Central

Wu, Tingjuan; Hao, Shuguang; Sun, Osbert Jianxin; Kang, Le

2012-01-01

Background Global warming is characterized by not only an increase in the daily mean temperature, but also a diel asymmetric pattern. However, most of the current studies on climate change have only concerned with the mean values of the warming trend. Although many studies have been conducted concerning the responses of insects to climate change, studies that address the issue of diel asymmetric warming under field conditions are not found in the literature. Methodology/Principal Findings We conducted a field climate manipulative experiment and investigated developmental and demographic responses to diel asymmetric warming in three grasshopper species (an early-season species Dasyhippus barbipes, a mid-season species Oedaleus asiaticus, and a late-season species Chorthippus fallax). It was found that warming generally advanced the development of eggs and nymphs, but had no apparent impacts on the hatching rate of eggs, the emergence rate of nymphs and the survival and fecundity of adults in all the three species. Nighttime warming was more effective in advancing egg development than the daytime warming. The emergence time of adults was differentially advanced by warming in the three species; it was advanced by 5.64 days in C. fallax, 3.55 days in O. asiaticus, and 1.96 days in D. barbipes. This phenological advancement was associated with increases in the effective GDDs accumulation. Conclusions/Significance Results in this study indicate that the responses of the three grasshopper species to warming are influenced by several factors, including species traits, developmental stage, and the thermal sensitivity of the species. Moreover, species with diapausing eggs are less responsive to changes in temperature regimes, suggesting that development of diapausing eggs is a protective mechanism in early-season grasshopper for avoiding the risk of pre-winter hatching. Our results highlight the need to consider the complex relationships between climate change and specificity responses of invertebrates. PMID:22848593

Role of hydrous iron oxide formation in attenuation and diel cycling of dissolved trace metals in a stream affected by acid rock drainage

USGS Publications Warehouse

Parker, S.R.; Gammons, C.H.; Jones, Clain A.; Nimick, D.A.

2007-01-01

Mining-impacted streams have been shown to undergo diel (24-h) fluctuations in concentrations of major and trace elements. Fisher Creek in south-central Montana, USA receives acid rock drainage (ARD) from natural and mining-related sources. A previous diel field study found substantial changes in dissolved metal concentrations at three sites with differing pH regimes during a 24-h period in August 2002. The current work discusses follow-up field sampling of Fisher Creek as well as field and laboratory experiments that examine in greater detail the underlying processes involved in the observed diel concentration changes. The field experiments employed in-stream chambers that were either transparent or opaque to light, filled with stream water and sediment (cobbles coated with hydrous Fe and Al oxides), and placed in the stream to maintain the same temperature. Three sets of laboratory experiments were performed: (1) equilibration of a Cu(II) and Zn(II) containing solution with Fisher Creek stream sediment at pH 6.9 and different temperatures; (2) titration of Fisher Creek water from pH 3.1 to 7 under four different isothermal conditions; and (3) analysis of the effects of temperature on the interaction of an Fe(II) containing solution with Fisher Creek stream sediment under non-oxidizing conditions. Results of these studies are consistent with a model in which Cu, Fe(II), and to a lesser extent Zn, are adsorbed or co-precipitated with hydrous Fe and Al oxides as the pH of Fisher Creek increases from 5.3 to 7.0. The extent of metal attenuation is strongly temperature-dependent, being more pronounced in warm vs. cold water. Furthermore, the sorption/co-precipitation process is shown to be irreversible; once the Cu, Zn, and Fe(II) are removed from solution in warm water, a decrease in temperature does not release the metals back to the water column. ?? 2006 Springer Science+Business Media B.V.

Spatial Dynamics and Expanded Vertical Niche of Blue Sharks in Oceanographic Fronts Reveal Habitat Targets for Conservation

PubMed Central

Queiroz, Nuno; Humphries, Nicolas E.; Noble, Leslie R.; Santos, António M.; Sims, David W.

2012-01-01

Dramatic population declines among species of pelagic shark as a result of overfishing have been reported, with some species now at a fraction of their historical biomass. Advanced telemetry techniques enable tracking of spatial dynamics and behaviour, providing fundamental information on habitat preferences of threatened species to aid conservation. We tracked movements of the highest pelagic fisheries by-catch species, the blue shark Prionace glauca, in the North-east Atlantic using pop-off satellite-linked archival tags to determine the degree of space use linked to habitat and to examine vertical niche. Overall, blue sharks moved south-west of tagging sites (English Channel; southern Portugal), exhibiting pronounced site fidelity correlated with localized productive frontal areas, with estimated space-use patterns being significantly different from that of random walks. Tracked female sharks displayed behavioural variability in diel depth preferences, both within and between individuals. Diel depth use ranged from normal DVM (nDVM; dawn descent, dusk ascent), to reverse DVM (rDVM; dawn ascent, dusk descent), to behavioural patterns where no diel differences were apparent. Results showed that blue sharks occupy some of the most productive marine zones for extended periods and structure diel activity patterns across multiple spatio-temporal scales in response to particular habitat types. In so doing, sharks occupied an extraordinarily broad vertical depth range for their size (1.0–2.0 m fork length), from the surface into the bathypelagic realm (max. dive depth, 1160 m). The space-use patterns of blue sharks indicated they spend much of the time in areas where pelagic longlining activities are often highest, and in depth zones where these fisheries particularly target other species, which could account for the rapid declines recently reported for blue sharks in many parts of the world's oceans. Our results provide habitat targets for blue shark conservation that may also be relevant to other pelagic species. PMID:22393403

The influence of warm-season precipitation on the diel cycle of the surface energy balance and carbon dioxide at a Colorado subalpine forest site

DOE PAGES

Burns, S. P.; Blanken, P. D.; Turnipseed, A. A.; ...

2015-12-15

Precipitation changes the physical and biological characteristics of an ecosystem. Using a precipitation-based conditional sampling technique and a 14 year data set from a 25 m micrometeorological tower in a high-elevation subalpine forest, we examined how warm-season precipitation affected the above-canopy diel cycle of wind and turbulence, net radiation R net, ecosystem eddy covariance fluxes (sensible heat H, latent heat LE, and CO 2 net ecosystem exchange NEE) and vertical profiles of scalars (air temperature T a, specific humidity q, and CO 2 dry mole fraction χ c). This analysis allowed us to examine how precipitation modified these variables frommore » hourly (i.e., the diel cycle) to multi-day time-scales (i.e., typical of a weather-system frontal passage). During mid-day we found the following: (i) even though precipitation caused mean changes on the order of 50–70 % to R net, H, and LE, the surface energy balance (SEB) was relatively insensitive to precipitation with mid-day closure values ranging between 90 and 110 %, and (ii) compared to a typical dry day, a day following a rainy day was characterized by increased ecosystem uptake of CO 2 (NEE increased by ≈ 10 %), enhanced evaporative cooling (mid-day LE increased by ≈ 30 W m –2), and a smaller amount of sensible heat transfer (mid-day H decreased by ≈ 70 W m –2). Based on the mean diel cycle, the evaporative contribution to total evapotranspiration was, on average, around 6 % in dry conditions and between 15 and 25 % in partially wet conditions. Furthermore, increased LE lasted at least 18 h following a rain event. At night, even though precipitation (and accompanying clouds) reduced the magnitude of R net, LE increased from ≈ 10 to over 20 W m –2 due to increased evaporation. Any effect of precipitation on the nocturnal SEB closure and NEE was overshadowed by atmospheric phenomena such as horizontal advection and decoupling that create measurement difficulties. Above-canopy mean χ c during wet conditions was found to be about 2–3 μmol mol –1 larger than χ c on dry days. This difference was fairly constant over the full diel cycle suggesting that it was due to synoptic weather patterns (different air masses and/or effects of barometric pressure). Lastly, the effect of clouds on the timing and magnitude of daytime ecosystem fluxes is described.« less

Chlorinated hydrocarbon contaminants in polar bears from eastern Russia, North America, Greenland, and Svalbard: Biomonitoring of Arctic pollution

USGS Publications Warehouse

Norstrom, R.J.; Belikov, Stanislav; Born, E.W.; Garner, G.W.; Malone, B.; Olpinski, S.; Ramsay, M.A.; Schliebe, S.; Stirling, I.; Sitshov, M.S.; Taylor, M.K.; Wiig, Øystein

1998-01-01

Adipose tissue samples from polar bears (Ursus maritimus) were obtained by necropsy or biopsy between the spring of 1989 to the spring of 1993 from Wrangel Island in Russia, most of the range of the bear in North America, eastern Greenland, and Svalbard. Samples were divided into 16 regions corresponding as much as possible to known stocks or management zones. Concentrations of dieldrin (DIEL), 4,4'-DDE (DDE), sum of 16 polychlorinated biphenyl congeners (sigma PCB), and sum of 11 chlordane-related compounds and metabolites (sigma CHL) were determined. In order to minimize the effect of age, only data for adults (320 bears age 5 years and older) was used to compare concentrations among regions. Concentrations of sigma PCB were 46% higher in adult males than females, and there was no significant trend with age. Concentrations of sigma CHL were 30% lower in adult males than females. Concentrations of sigma PCB, sigma CHL, and DDE in individual adult female bears were standardized to adult males using factors derived from the least-square means of each sex category, and geometric means of the standardized concentrations on a lipid weight basis were compared among regions. Median geometric mean standardized concentrations (lipid weight basis) and ranges among regions were as follows: sigma PCB, 5,942 (2,763-24,316) micrograms/kg; sigma CHL, 1,952 (727-4,632) micrograms/kg; DDE, 219 (52-560) micrograms/kg; DIEL, 157 (31-335) micrograms/kg. Geometric mean sigma PCB concentrations in bears from Svalbard, East Greenland, and the Arctic Ocean near Prince Patrick Island in Canada were similar (20,256-24,316 micrograms/kg) and significantly higher than most other areas. Atmospheric, oceanic, and ice transport, as well as ecological factors may contribute to these high concentrations of sigma PCB. sigma CHL was more uniformly distributed among regions than the other CHCs. Highest sigma CHL concentrations were found in southeastern Hudson Bay, which also had the highest DDE and DIEL concentrations. In general, concentrations of sigma CHL, DDE, and DIEL were higher in eastern than western regions, suggesting an influence of North American sources. Average sigma PCB concentrations in bears from the Canadian Arctic were similar to those in 1982-84, while average sigma CHL and DDE concentrations were 35-44% lower and DIEL was 90% lower. However, the significance of these temporal trends during the 1980s is not conclusive because of the problems of comparability of data.

Characterization of vanadium ion uptake in sulfonated diels alder poly(phenylene) membranes

DOE PAGES

Lawton, Jamie; Jones, Amanda; Tang, Zhijiang; ...

2015-11-28

Sulfonated diels alder poly(phenylene) (SDAPP), alternative aromatic hydrocarbon membranes for vanadium redox flow batteries (VRFBs) are characterized using electron paramagnetic resonance (EPR). Membranes soaked in sulfuric acid and vanadyl sulfate are analyzed to determine the membrane environment in which the vanadyl ion (VO 2+) diffuses in the membranes. These results are compared to Nafion 117 membranes. In contrast to Nafion, the VO 2+ in SDAPP membranes exists in two different environments. The results of analysis of rotational diffusion determined from fits the EPR spectral lineshapes in comparison with previously reported permeation studies and measurements of partitioning functions reported here suggestmore » that the diffusion pathways in SDAPP are very different than in Nafion.« less

Current Developments and Challenges in the Search for a Naturally Selected Diels-Alderase

PubMed Central

Kim, Hak Joong; Ruszczycky, Mark W.; Liu, Hung-wen

2012-01-01

Only a very few examples of enzymes known to catalyze pericyclic reactions have been reported, and presently no enzyme has been demonstrated unequivocally to catalyze a Diels-Alder reaction. Nevertheless, research into secondary metabolism has led to the discovery of numerous natural products exhibiting the structural hallmarks of [4+2] cycloadditions, prompting efforts to characterize the responsible enzymatic processes. These efforts have resulted in a growing collection of enzymes believed to catalyze pericyclic [4+2] cycloaddition reactions; however, in each case the complexity of the substrates and catalytic properties of these enzymes poses significant challenges in substantiating these hypotheses. Herein we consider the principles motivating these efforts and the enzymological systems currently under investigation. PMID:22260931

Diels-Alder addition to H2O@C60 an electronic and structural study

NASA Astrophysics Data System (ADS)

Reveles, J. Ulises; Govinda, K. C.; Baruah, Tunna; Zope, Rajendra R.

2017-10-01

Exohedral reactivity of endohedral fullerenes has aroused a significant interest because of its potential applications. The present letter examines the effect of an entrapped single water molecule on the reactivity of C60. We study the thermodynamics and kinetics of a Diels-Alder reaction occurring at all non-identical bonds of free C60 and H2O@C60. Our calculations show that encapsulation of water does not have a significant effect on H2O@C60 reactivity compared to C60, as attested by the investigation of the reaction under several orientations of H2O inside C60. Reaction and activation energies indicate that [6,6] bonds are the most reactive sites.

Metagenomic analysis of intertidal hypersaline microbial mats from Elkhorn Slough, California, grown with and without molybdate

DOE PAGES

D’haeseleer, Patrik; Lee, Jackson Z.; Prufert-Bebout, Leslie; ...

2017-11-15

Cyanobacterial mats are laminated microbial ecosystems which occur in highly diverse environments and which may provide a possible model for early life on Earth. Their ability to produce hydrogen also makes them of interest from a biotechnological and bioenergy perspective. Samples of an intertidal microbial mat from the Elkhorn Slough estuary in Monterey Bay, California, were transplanted to a greenhouse at NASA Ames Research Center to study a 24-h diel cycle, in the presence or absence of molybdate (which inhibits biohydrogen consumption by sulfate reducers). Here, we present metagenomic analyses of four samples that will be used as references formore » future metatranscriptomic analyses of this diel time series.« less

Metagenomic analysis of intertidal hypersaline microbial mats from Elkhorn Slough, California, grown with and without molybdate

DOE Office of Scientific and Technical Information (OSTI.GOV)

D’haeseleer, Patrik; Lee, Jackson Z.; Prufert-Bebout, Leslie

Cyanobacterial mats are laminated microbial ecosystems which occur in highly diverse environments and which may provide a possible model for early life on Earth. Their ability to produce hydrogen also makes them of interest from a biotechnological and bioenergy perspective. Samples of an intertidal microbial mat from the Elkhorn Slough estuary in Monterey Bay, California, were transplanted to a greenhouse at NASA Ames Research Center to study a 24-h diel cycle, in the presence or absence of molybdate (which inhibits biohydrogen consumption by sulfate reducers). Here, we present metagenomic analyses of four samples that will be used as references formore » future metatranscriptomic analyses of this diel time series.« less

Prediction of the chemo- and regioselectivity of Diels-Alder reactions of o-benzoquinone derivatives with thiophenes by means of DFT-based reactivity indices

NASA Astrophysics Data System (ADS)

Ghomri, Amina; Mekelleche, Sidi Mohamed

2014-03-01

Global and local reactivity indices derived from density functional theory were used to elucidate the regio- and chemoselectivity of Diels-Alder reactions of masked o-benzoquinones with thiophenes acting as dienophiles. The polarity of the studied reactions is evaluated in terms of the difference of electrophilicity powers between the diene and dienophile partners. Preferential cyclisation modes of these cycloadditions are predicted using Domingo's polar model based on the local electrophilicity index, ωk, of the electrophile and the local nucleophilicity index, Nuk, of the nucleophile. The theoretical calculations, carried out at the B3LYP/6-311G(d,p) level of theory, are in good agreement with experimental findings.

The [2 + 2] Cycloaddition-Retroelectrocyclization and [4 + 2] Hetero-Diels-Alder Reactions of 2-(Dicyanomethylene)indan-1,3-dione with Electron-Rich Alkynes: Influence of Lewis Acids on Reactivity.

PubMed

Donckele, Etienne J; Finke, Aaron D; Ruhlmann, Laurent; Boudon, Corinne; Trapp, Nils; Diederich, François

2015-07-17

The reaction of electrophilic 2-(dicyanomethylene)indan-1,3-dione (DCID) with substituted, electron-rich alkynes provides two classes of push-pull chromophores with interesting optoelectronic properties. The formal [2 + 2] cycloaddition-retroelectrocyclization reaction at the exocyclic double bond of DCID gives cyanobuta-1,3-dienes, and the formal [4 + 2] hetero-Diels-Alder (HDA) reaction at an enone moiety of DCID generates fused 4H-pyran heterocycles. Both products can be obtained in good yield and excellent selectivity by carefully tuning the reaction conditions; in particular, the use of Lewis acids dramatically enhances formation of the HDA adduct.

Vertical flux of respiratory carbon by oceanic diel migrant biota

NASA Astrophysics Data System (ADS)

Longhurst, A. R.; Bedo, A. W.; Harrison, W. G.; Head, E. J. H.; Sameoto, D. D.

1990-04-01

Interzonal diel migrant plankton and nekton obtain organic carbon by feeding at night above the main pycnoline of subtropical and tropical oceans, and respire part of it by day in the interior of the ocean below the pycnocline. Using data from seven oceanic stations, and conservative models to compute respiration at depth, we show that this flux of respiratory carbon ranged from 20 to 430 mg C m -2 d -1 or 13-58% of computed particulate sinking flux across the pycnocline. If this flux occurs consistently between 50°N and 50°S, it will add about 5-20% (depending on method of calculation) to current estimates of global sinking flux of organic carbon across the pycnocline.

Seasonal variation in the flux of euthecosomatous pteropods collected in a deep sediment trap in the Sargasso Sea

NASA Astrophysics Data System (ADS)

Almogi-Labin, A.; Hemleben, Ch.; Deuser, W. G.

1988-03-01

A 4-year series of sediment trap samples from a depth of 3.2 km in the Sargasso Sea (32°05'N, 64°15'W) has revealed seasonal variations in the flux of euthecosomatous pteropods. Total pteropod flux is related to seasonal variations of the total particulate and organic carbon flux with a lag of 1-1.5 months. High flux of pteropods (>200 specimens m -2 day -1) occurs in late winter to mid-summer. Shells of individual pteropod species arrive in deep water in a seasonal succession similar to that in the living assemblage. Peak fluxes of Styliola subula, Clio pyramidata and Limacina bulimoides were recorded from February to May. Limacina inflata, Limacina lesueuri and Cuvierina columnella entered the trap in maximum numbers from April to mid-August. Creseis virgula conica and C. acicula were most abundant from June to late August. The latter two are non-migrating, epipelagic pteropods and comprise <10% of the assemblage. Diel migrators dominate the pteropod assemblage (92%). During the summer months they appear to migrate at greater depth, without reaching the surface water. Although many young are produced, only a small fraction, about 4% in the case of L. inflata and L. bulimoides, survives and reaches maturity. Adult shell size of L. inflata and L. bulimoides varies seasonally, reaching maximum size during spring, probably in response to increasing food availability.

SAM-dependent enzyme-catalysed pericyclic reactions in natural product biosynthesis

NASA Astrophysics Data System (ADS)

Ohashi, Masao; Liu, Fang; Hai, Yang; Chen, Mengbin; Tang, Man-Cheng; Yang, Zhongyue; Sato, Michio; Watanabe, Kenji; Houk, K. N.; Tang, Yi

2017-09-01

Pericyclic reactions—which proceed in a concerted fashion through a cyclic transition state—are among the most powerful synthetic transformations used to make multiple regioselective and stereoselective carbon-carbon bonds. They have been widely applied to the synthesis of biologically active complex natural products containing contiguous stereogenic carbon centres. Despite the prominence of pericyclic reactions in total synthesis, only three naturally existing enzymatic examples (the intramolecular Diels-Alder reaction, and the Cope and the Claisen rearrangements) have been characterized. Here we report a versatile S-adenosyl-L-methionine (SAM)-dependent enzyme, LepI, that can catalyse stereoselective dehydration followed by three pericyclic transformations: intramolecular Diels-Alder and hetero-Diels-Alder reactions via a single ambimodal transition state, and a retro-Claisen rearrangement. Together, these transformations lead to the formation of the dihydropyran core of the fungal natural product, leporin. Combined in vitro enzymatic characterization and computational studies provide insight into how LepI regulates these bifurcating biosynthetic reaction pathways by using SAM as the cofactor. These pathways converge to the desired biosynthetic end product via the (SAM-dependent) retro-Claisen rearrangement catalysed by LepI. We expect that more pericyclic biosynthetic enzymatic transformations remain to be discovered in naturally occurring enzyme ‘toolboxes’. The new role of the versatile cofactor SAM is likely to be found in other examples of enzyme catalysis.

Passive Acoustic Monitoring the Diel, Lunar, Seasonal and Tidal Patterns in the Biosonar Activity of the Indo-Pacific Humpback Dolphins (Sousa chinensis) in the Pearl River Estuary, China.

PubMed

Wang, Zhi-Tao; Nachtigall, Paul E; Akamatsu, Tomonari; Wang, Ke-Xiong; Wu, Yu-Ping; Liu, Jian-Chang; Duan, Guo-Qin; Cao, Han-Jiang; Wang, Ding

2015-01-01

A growing demand for sustainable energy has led to an increase in construction of offshore windfarms. Guishan windmill farm will be constructed in the Pearl River Estuary, China, which sustains the world's largest known population of Indo-Pacific humpback dolphins (Sousa chinensis). Dolphin conservation is an urgent issue in this region. By using passive acoustic monitoring, a baseline distribution of data on this species in the Pearl River Estuary during pre-construction period had been collected. Dolphin biosonar detection and its diel, lunar, seasonal and tidal patterns were examined using a Generalized Linear Model. Significant higher echolocation detections at night than during the day, in winter-spring than in summer-autumn, at high tide than at flood tide were recognized. Significant higher echolocation detections during the new moon were recognized at night time. The diel, lunar and seasonal patterns for the echolocation encounter duration also significantly varied. These patterns could be due to the spatial-temporal variability of dolphin prey and illumination conditions. The baseline information will be useful for driving further effective action on the conservation of this species and in facilitating later assessments of the effects of the offshore windfarm on the dolphins by comparing the baseline to post construction and post mitigation efforts.

Influence of the late winter bloom on migrant zooplankton metabolism and its implications on export fluxes

NASA Astrophysics Data System (ADS)

Putzeys, S.; Yebra, L.; Almeida, C.; Bécognée, P.; Hernández-León, S.

2011-12-01

Studies on carbon active fluxes due to diel migrants are scarce and critical for carbon flux models and biogeochemical estimates. We studied the temporal variability and vertical distribution of biomass, indices of feeding and respiration of the zooplanktonic community north off the Canary Islands during the end of the late winter bloom, in order to assess vertical carbon fluxes in this area. Biomass distribution during the day presented two dense layers of organisms at 0-200 m and around 500 m, whereas at night, most of the biomass concentrated in the epipelagic layer. The gut pigment flux (0.05-0.18 mgC·m - 2 ·d - 1 ) represented 0.22% of the estimated passive export flux (POC flux) while potential ingestion represented 3.91% of the POC (1.24-3.40 mgC·m - 2 ·d - 1 ). The active respiratory flux (0.50-1.36 mgC·m - 2 ·d - 1 ) was only 1.57% of the POC flux. The total carbon flux mediated by diel migrants (respiration plus potential ingestion) ranged between 3.37 and 9.22% of the POC flux; which is three-fold higher than calculating ingestion fluxes from gut pigments. Our results suggest that the fluxes by diel migrants play a small role in the downward flux of carbon in the open ocean during the post-bloom period.

Dynamically Cross-linked Elastomer Hybrids with Light-Induced Rapid and Efficient Self-Healing Ability and Reprogrammable Shape Memory Behavior.

PubMed

Bai, Jing; Shi, Zixing

2017-08-16

Pristine carbon nanotubes (CNTs) were activated to exhibit Diels-Alder (DA) reactivity in a polymer matrix, which was modified with monomers containing furan groups. The DA-active polymer matrix was transferred into a dynamic reversible cross-linked inorganic-organic network via a Diels-Alder reaction with CNTs, where pristine CNTs were used as dienophile chemicals and furan-modified SBS acted as the macromolecular diene. In this system, the mechanical properties as well as resilience and solvent resistance were greatly improved even with the presence of only 1 wt % CNTs. Meanwhile, the hybrids retained recyclability and exhibited some smart behaviors, including self-healing and reprogrammable shape memory properties. Furthermore, due to the photothermal effect of CNTs, a retro-Diels-Alder (rDA) reaction was activated under laser irradiation, and healing of a crack on the hybrid surface was demonstrated in approximately 10 s with almost complete recovery of the mechanical properties. Such fast and efficient self-healing performance provides a new concept in designing self-healing nanocomposites with tunable structures and mechanical properties. Furthermore, the DA and rDA reactions could be combined to reprogram the shape memory behavior under laser irradiation or thermal treatment, wherein the temporary shape of the sample could be transferred to a permanent shape via the rDA reaction at high temperature.

Passive Acoustic Monitoring the Diel, Lunar, Seasonal and Tidal Patterns in the Biosonar Activity of the Indo-Pacific Humpback Dolphins (Sousa chinensis) in the Pearl River Estuary, China

PubMed Central

Wang, Zhi-Tao; Nachtigall, Paul E.; Akamatsu, Tomonari; Wang, Ke-Xiong; Wu, Yu-Ping; Liu, Jian-Chang; Duan, Guo-Qin; Cao, Han-Jiang; Wang, Ding

2015-01-01

A growing demand for sustainable energy has led to an increase in construction of offshore windfarms. Guishan windmill farm will be constructed in the Pearl River Estuary, China, which sustains the world’s largest known population of Indo-Pacific humpback dolphins (Sousa chinensis). Dolphin conservation is an urgent issue in this region. By using passive acoustic monitoring, a baseline distribution of data on this species in the Pearl River Estuary during pre-construction period had been collected. Dolphin biosonar detection and its diel, lunar, seasonal and tidal patterns were examined using a Generalized Linear Model. Significant higher echolocation detections at night than during the day, in winter-spring than in summer-autumn, at high tide than at flood tide were recognized. Significant higher echolocation detections during the new moon were recognized at night time. The diel, lunar and seasonal patterns for the echolocation encounter duration also significantly varied. These patterns could be due to the spatial-temporal variability of dolphin prey and illumination conditions. The baseline information will be useful for driving further effective action on the conservation of this species and in facilitating later assessments of the effects of the offshore windfarm on the dolphins by comparing the baseline to post construction and post mitigation efforts. PMID:26580966

Exploring the influence of Diels-Alder linker length on photothermal molecule release from gold nanorods.

PubMed

Vetterlein, Claudia; Vásquez, Rodrigo; Bolaños, Karen; Acosta, Gerardo A; Guzman, Fanny; Albericio, Fernando; Celis, Freddy; Campos, Marcelo; Kogan, Marcelo J; Araya, Eyleen

2018-06-01

We studied the photothermal release of carboxyfluorescein (CF) linked to the gold surface of gold nanorods (GNRs) by two Diels-Alder adducts of different lengths (n = 4 and n = 9). The functionalized GNRs were irradiated with infrared light to produce photothermal release of CF by a retro-Diels-Alder reaction. The adducts were chemisorbed on the GNRs and the functionalized nanoparticles were characterized by UV-vis, DLS, zeta potential and Raman and surface-enhanced Raman spectroscopy (SERS). On the basis of the degree of nanoparticle functionalization and the SERS results, we inferred the orientation of CF on the surface of the gold nanoparticle. Moreover, we determined the photothermal release profiles of CF from the gold surface by laser irradiation. The release was faster for the longer linker (n = 9). SERS revealed that, for the shorter linker (n = 4), molecules are oriented perpendicularly with respect to the gold surface, thereby maintaining the CF far from the surface. In contrast, the longer linker was observed to be tilted, thus maintaining CF close to the gold surface and therefore potentially favoring the photothermal transfer of energy. These results are relevant for the future development of the spatial and temporal controlled release of drugs by means of gold nanoparticles. Copyright © 2018 Elsevier B.V. All rights reserved.

FK-3000 isolated from Stephania delavayi Diels. inhibits MDA-MB-231 cell proliferation by decreasing NF-κB phosphorylation and COX-2 expression.

PubMed

Xu, Hong De; Cho, Soon-Chang; Bang, Mi-Ae; Bae, Chun-Sik; Choi, Yeonshik; Li, Yong-Chun; Lim, Seung-Kil; Shim, Jaegal; Park, Dae-Hun

2015-01-01

The World Health Organization (WHO) has reported that cancer is one of the most prevalent diseases and a leading cause of death worldwide. Many anticancer drug development studies have been pursued over the last few decades and several viable drugs have been discovered, such as paclitaxel, topotecan and irinotecan. Previously, our research group uncovered the cytocidal and cytostatic effects of the plant Stephania delavayi Diels. In this study, we determined the active chemical to be 6,7-di-O-acetylsinococuline (FK-3000). The FK-3000 half maximal inhibitory concentration (IC50) in MDA-MB-231 breast carcinoma cells at 48 h was 0.52 µg/ml and it induced apoptosis in a dose- and time-dependent manner. FK-3000 suppressed NF-κB nuclear translocation, decreased NF-κB phosphorylation, and decreased COX-2 protein expression. MDA-MB-231 xenografted mice were treated with FK-3000, Taxol, or their combination for 21 days. The tumor size was smallest in the co-treatment group, indicating that FK-3000 may have a synergistic effect with Taxol. FK-3000 treatment showed no adverse effects on blood cell counts, serum protein levels, or pathology. These studies demonstrate that FK-3000, isolated from S. delavayi Diels., is a promising, pathway-specific anticancer agent that exhibits low toxicity.

Behavioral responses of Atlantic cod to sea temperature changes.

PubMed

Freitas, Carla; Olsen, Esben Moland; Moland, Even; Ciannelli, Lorenzo; Knutsen, Halvor

2015-05-01

Understanding responses of marine species to temperature variability is essential to predict impacts of future climate change in the oceans. Most ectotherms are expected to adjust their behavior to avoid extreme temperatures and minimize acute changes in body temperature. However, measuring such behavioral plasticity in the wild is challenging. Combining 4 years of telemetry-derived behavioral data on juvenile and adult (30-80 cm) Atlantic cod (Gadus morhua), and in situ ocean temperature measurements, we found a significant effect of sea temperature on cod depth use and activity level in coastal Skagerrak. During summer, cod were found in deeper waters when sea surface temperature increased. Further, this effect of temperature was stronger on larger cod. Diel vertical migration, which consists in a nighttime rise to shallow feeding habitats, was stronger among smaller cod. As surface temperature increased beyond ∼15°C, their vertical migration was limited to deeper waters. In addition to larger diel vertical migrations, smaller cod were more active and travelled larger distances compared to larger specimens. Cold temperatures during winter tended, however, to reduce the magnitude of diel vertical migrations, as well as the activity level and distance moved by those smaller individuals. Our findings suggest that future and ongoing rises in sea surface temperature may increasingly deprive cod in this region from shallow feeding areas during summer, which may be detrimental for local populations of the species.

Air breathing in Magadi tilapia Alcolapia grahami, under normoxic and hyperoxic conditions, and the association with sunlight and reactive oxygen species.

PubMed

Johannsson, O E; Bergman, H L; Wood, C M; Laurent, P; Kavembe, D G; Bianchini, A; Maina, J N; Chevalier, C; Bianchini, L F; Papah, M B; Ojoo, R O

2014-03-01

Observations of the Magadi tilapia Alcolapia grahami in hot, highly alkaline Lake Magadi revealed that they air breathe not only during hypoxia, as described previously, but also during normoxia and hyperoxia. Air breathing under these latter conditions occurred within distinct groupings of fish (pods) and involved only a small proportion of the population. Air breathing properties (duration and frequency) were quantified from video footage. Air breathing within the population followed a diel pattern with the maximum extent of pod formation occurring in early afternoon. High levels of reactive oxygen species (ROS) in the water may be an irritant that encourages the air-breathing behaviour. The diel pattern of air breathing in the field and in experiments followed the diel pattern of ROS concentrations in the water which are amongst the highest reported in the literature (maximum daytime values of 2.53 – 8.10 μM H₂O₂). Interlamellar cell masses (ILCM) occurred between the gill lamellae of fish from the lagoon with highest ROS and highest oxygen levels, while fish from a normoxic lagoon with one third the ROS had little or no ILCM. This is the first record of air breathing in a facultative air-breathing fish in hyperoxic conditions and the first record of an ILCM in a cichlid species. © 2013 The Fisheries Society of the British Isles.

Extremely productive microbial communities in shallow saline pools respond immediately to changing meteorological conditions.

PubMed

Kirschner, A K T; Eiler, A; Zechmeister, T C; Velimirov, B; Herzig, A; Mach, R; Farnleitner, A H

2002-09-01

Diel changes in bacterial and cyanobacterial numbers, as well as heterotrophic bacterial production, were examined in two shallow alkaline pools, harbouring dense populations of cyanobacteria (up to 1100 x 109 cells l-1) and bacteria (up to 500 x 109 cells l-1). Together with the recorded bacterial production rates (925 micro gC l-1x h-1), these values are the highest reported for natural aquatic ecosystems. The investigations were performed during a fair-weather situation, and during a rapid change after a long-term fair-weather situation to thunderstorms and heavy rainfall. During fair weather, bacterial growth was significantly correlated to the diurnal light and temperature cycle. Prokaryotic abundances were fairly constant, and loss by grazing and viral lysis must have been of significant importance. During the invasion of rainy weather, the prokaryotic community showed a strong and immediate response. A significant enhancement of bacterial growth followed after rainfall, suggesting that the high salt concentrations had inhibited bacterial activity. Changes in bacterial and cyanobacterial numbers were consistent with this pattern. From comparison with the available literature, we conclude that diel changes of bacterioplankton are regulated by a complex combination of environmental factors specific for each investigated ecosystem. In the soda pools investigated, external abiotic factors were dominant on a diel scale. In larger ecosystems, such factors are much more buffered and internal biotic interactions may prevail.

Behavioral responses of Atlantic cod to sea temperature changes

PubMed Central

Freitas, Carla; Olsen, Esben Moland; Moland, Even; Ciannelli, Lorenzo; Knutsen, Halvor

2015-01-01

Understanding responses of marine species to temperature variability is essential to predict impacts of future climate change in the oceans. Most ectotherms are expected to adjust their behavior to avoid extreme temperatures and minimize acute changes in body temperature. However, measuring such behavioral plasticity in the wild is challenging. Combining 4 years of telemetry-derived behavioral data on juvenile and adult (30–80 cm) Atlantic cod (Gadus morhua), and in situ ocean temperature measurements, we found a significant effect of sea temperature on cod depth use and activity level in coastal Skagerrak. During summer, cod were found in deeper waters when sea surface temperature increased. Further, this effect of temperature was stronger on larger cod. Diel vertical migration, which consists in a nighttime rise to shallow feeding habitats, was stronger among smaller cod. As surface temperature increased beyond ∼15°C, their vertical migration was limited to deeper waters. In addition to larger diel vertical migrations, smaller cod were more active and travelled larger distances compared to larger specimens. Cold temperatures during winter tended, however, to reduce the magnitude of diel vertical migrations, as well as the activity level and distance moved by those smaller individuals. Our findings suggest that future and ongoing rises in sea surface temperature may increasingly deprive cod in this region from shallow feeding areas during summer, which may be detrimental for local populations of the species. PMID:26045957

Phytoplankton production in the Sargasso Sea as determined using optical mooring data

NASA Technical Reports Server (NTRS)

Waters, K. J.; Smith, R. C.; Marra, J.

1994-01-01

Optical measurements from an untended mooring provide high-frequency observations of in-water optical properties and permit the estimation of important biological parameters continuously as a function of time. A 9-month time series, composed of three separate deployments, of optical data from the BIOWATT 1987 deep-sea mooring located in the oligotrophic waters of the Sargasso Sea at 34 deg N, 70 deg W are presented. These data have been tested using several bio-optical models for the purpose of providing a continuous estimate of phytoplankton productivity. The data are discussed in the context of contemporaneous shipboard observations and for future ocean color satellite observations. We present a continuous estimation of phytoplankton productivity for the 9-month time series. Results from the first 70-day deployment are emphasized to demonstrate the utility of optical observations as proxy measures of biological parameters, to present preliminary analysis, and to compare our bio-optical observations with concurrent physical observations. The bio-optical features show variation in response to physical forcings including diel variations of incident solar irradiance, episodic changes corresponding to wind forcing, variability caused by advective mesoscale eddy events in the vicinity of the mooring, and seasonal variability corresponding to changes in solar radiation, shoaling of the mixed layer depth, and succession of phytoplankton populations.

Scales of variability of bio-optical properties as observed from near-surface drifters

NASA Technical Reports Server (NTRS)

Abbott, Mark R.; Brink, Kenneth H.; Booth, C. R.; Blasco, Dolors; Swenson, Mark S.; Davis, Curtiss O.; Codispoti, L. A.

1995-01-01

A drifter equipped with bio-optical sensors and an automated water sampler was deployed in the California Current as part of the coastal transition zone program to study the biological, chemical, and physical dynamics of the meandering filaments. During deployments in 1987 and 1988, measurements were made of fluorescence, downwelling irradiance, upwelling radiance, and beam attenuation using several bio-optical sensors. Samples were collected by an automated sampler for later analysis of nutrients and phytoplankton species compositon. Large-scale spatial and temporal changes in the bio-optical and biological properties of the region were driven by changes in phytoplankton species composition which, in turn, were associated with the meandering circulation. Variance spectra of the bio-optical paramenters revealed fluctuations on both diel and semidiurnal scales, perhaps associated with solar variations and internal tides, respectively. Offshore, inertial-scale fluctuations were apparent in the variance spectra of temperature, fluorescence, and beam attenuation. Although calibration samples can help remove some of these variations, these results suggest that the use of bio-optical data from unattended platforms such as moorings and drifters must be analyzed carefully. Characterization of the scaled of phytoplankton variability must account for the scales of variability in the algorithms used to convert bio-optical measurments into biological quantities.

Volatile organic compounds (VOCs) in photochemically aged air from the eastern and western Mediterranean

NASA Astrophysics Data System (ADS)

Derstroff, Bettina; Hüser, Imke; Bourtsoukidis, Efstratios; Crowley, John N.; Fischer, Horst; Gromov, Sergey; Harder, Hartwig; Janssen, Ruud H. H.; Kesselmeier, Jürgen; Lelieveld, Jos; Mallik, Chinmay; Martinez, Monica; Novelli, Anna; Parchatka, Uwe; Phillips, Gavin J.; Sander, Rolf; Sauvage, Carina; Schuladen, Jan; Stönner, Christof; Tomsche, Laura; Williams, Jonathan

2017-08-01

During the summertime CYPHEX campaign (CYprus PHotochemical EXperiment 2014) in the eastern Mediterranean, multiple volatile organic compounds (VOCs) were measured from a 650 m hilltop site in western Cyprus (34° 57' N/32° 23' E). Periodic shifts in the northerly Etesian winds resulted in the site being alternately impacted by photochemically processed emissions from western (Spain, France, Italy) and eastern (Turkey, Greece) Europe. Furthermore, the site was situated within the residual layer/free troposphere during some nights which were characterized by high ozone and low relative humidity levels. In this study we examine the temporal variation of VOCs at the site. The sparse Mediterranean scrub vegetation generated diel cycles in the reactive biogenic hydrocarbon isoprene, from very low values at night to a diurnal median level of 80-100 pptv. In contrast, the oxygenated volatile organic compounds (OVOCs) methanol and acetone exhibited weak diel cycles and were approximately an order of magnitude higher in mixing ratio (ca. 2.5-3 ppbv median level by day, range: ca. 1-8 ppbv) than the locally emitted isoprene and aromatic compounds such as benzene and toluene. Acetic acid was present at mixing ratios between 0.05 and 4 ppbv with a median level of ca. 1.2 ppbv during the daytime. When data points directly affected by the residual layer/free troposphere were excluded, the acid followed a pronounced diel cycle, which was influenced by various local effects including photochemical production and loss, direct emission, dry deposition and scavenging from advecting air in fog banks. The Lagrangian model FLEXPART was used to determine transport patterns and photochemical processing times (between 12 h and several days) of air masses originating from eastern and western Europe. Ozone and many OVOC levels were ˜ 20 and ˜ 30-60 % higher, respectively, in air arriving from the east. Using the FLEXPART calculated transport time, the contribution of photochemical processing, sea surface contact and dilution was estimated. Methanol and acetone decreased with residence time in the marine boundary layer (MBL) with loss rate constants of 0.74 and 0.53 day-1 from eastern Europe and 0.70 and 0.34 day-1 from western Europe, respectively. Simulations using the EMAC model underestimate these loss rates. The missing sink in the calculation is most probably an oceanic uptake enhanced by microbial consumption of methanol and acetone, although the temporal and spatial variability in the source strength on the continents might play a role as well. Correlations between acetone and methanol were weaker in western air masses (r2 = 0.68), but were stronger in air masses measured after the shorter transport time from the east (r2 = 0.73).

Revealing a circadian clock in captive arctic-breeding songbirds, lapland longspurs (Calcarius lapponicus), under constant illumination.

PubMed

Ashley, Noah T; Ubuka, Takayoshi; Schwabl, Ingrid; Goymann, Wolfgang; Salli, Brady M; Bentley, George E; Buck, C Loren

2014-12-01

Most organisms in temperate or tropic regions employ the light-dark (LD) cycle as the primary Zeitgeber to synchronize circadian rhythms. At higher latitudes (>66°33'), continuous illumination during the summer presents a significant time-keeping dilemma for polar-adapted species. Lapland longspurs (Calcarius lapponicus), arctic-breeding migratory songbirds, are one of the few recorded species maintaining an intact diel rhythm in activity and plasma melatonin titers during polar summer. However, it is unknown whether rhythms are endogenous and entrain to low-amplitude polar Zeitgeber signals, such as daily variations in light intensity and the spectral composition of the sun (as measured by color temperature). Wild-caught male and female longspurs were brought into captivity, and locomotor activity was assessed using infrared detection. To examine if rhythms were endogenous, birds were exposed to constant bright light (LL; 1300 lux) or constant darkness (DD; 0.1 lux). All birds exhibited free-running activity rhythms in LL and DD, suggesting the presence of a functional circadian clock. Mean periods in LL (22.86 h) were significantly shorter than those in DD (23.5 h), in accordance with Aschoff's rule. No birds entrained to diel changes in light intensity, color temperature, or both. To examine endogenous molecular clock function, the Per2 gene was partially cloned in longspurs (llPer2) and transcripts were measured in hypothalamic tissue punches, eye, and liver using competitive polymerase chain reaction. Ocular llPer2 gene expression was periodic in LL and elevated at ZT24 (CT24) for LD or constant conditions (LL and DD), but llPer2 rhythmicity was not detected in hypothalamus or liver. Plasma melatonin was significantly lower in LL compared with LD or DD. In conclusion, rhythmic ocular Per2 expression and melatonin secretion may maintain the circadian activity rhythm across the polar day. © 2014 The Author(s).

Role of Biotic and Abiotic Processes on Soil CO2 Dynamics in the McMurdo Dry Valleys, Antarctica

NASA Astrophysics Data System (ADS)

Risk, D. A.; Macintyre, C. M.; Lee, C.; Cary, C.; Shanhun, F.; Almond, P. C.

2016-12-01

In the harsh conditions of the Antarctic Dry Valleys, microbial activity has been recorded via measurements of soil carbon dioxide (CO2) concentration and surface efflux. However, high temporal resolution studies in the Dry Valleys have also shown that abiotic solubility-driven processes can strongly influence (and perhaps even dominate) the CO2 dynamics in these low flux environments and suggests that biological activity may be lower than previously thought. In this study, we aim to improve our understanding of CO2 dynamics (biotic and abiotic) in Antarctic Dry Valley soils using long-term automated measurements of soil CO2 surface flux and soil profile concentration at several sites, often at sub-diel frequency. We hypothesize that soil CO2 variations are driven primarily by environmental factors affecting CO2 solubility in soil solution, mainly temperature, and that these processes may even overprint biologic production in representative Dry Valley soils. Monitoring of all sites revealed only one likely biotic CO2 production event, lasting three weeks during the Austral summer and reaching fluxes of 0.4 µmol/m2/s. Under more typical low flux conditions (<0.10 µmol/m2/s) we observed a cyclical daily sink/source pattern consistent with CO2 solubility cycling that would not generally have been evident with normal synoptic afternoon sampling campaigns. Subsurface CO2 monitoring and a lab-controlled Antarctic soil simulation experiment confirmed that abiotic processes are capable of dominating soil CO2 variability. Diel temperature cycles crossing the freezing boundary revealed a dual abiotic cycle of solubility cycling and gas exclusion from ice formation observed only by high temporal frequency measurements (30 min). This work demonstrates a need for a numerical model to partition the dynamic abiotic processes underlying any biotic CO2 production in order to understand potential climate-change induced increases in microbial productivity in terrestrial Antarctica.

Recruitment of fish larvae and juveniles into two estuarine nursery areas with evidence of ebb tide use

NASA Astrophysics Data System (ADS)

Pattrick, Paula; Strydom, Nadine

2014-08-01

Recruitment of larvae and early juveniles, against the ebb tide in the shallower, slower-flowing marginal areas of two permanently open estuaries in the Eastern Cape, South Africa was observed. To determine tidal, diel and seasonal variations of larval and juvenile fish recruitment, fyke nets were used during a 24-hour cycle over two years from December 2010 to October 2012. On either side of each estuary bank, two fyke nets with mouth openings facing opposite directions (i.e. one net facing the incoming or outgoing tide and the other facing the opposing direction) were used to sample fishes. The aims of this study were to determine if 1) on the flood tide, were the nets facing the incoming tide collecting more larvae and early juveniles recruiting into the estuarine nursery area, than the nets facing the opposing direction and 2) on the ebb tide, were the nets facing the sea, and hence the opposing direction of the outgoing ebb tide, collecting more fishes recruiting into the nursery against the ebb tide, than the nets facing the outgoing ebb tide? Larval and juvenile fish CPUE, species diversity and richness varied seasonally between estuarine systems and between diel and tidal conditions. Highest catches were recorded on the flood tide, which coincided with sunrise in the Swartkops Estuary. Greatest catches of larvae and early juveniles were observed during the ebb tide at night in the Sundays Estuary. On the ebb tide, higher catches of several dominant species and several commercially important fishery species, occurred in the fyke nets which faced the sea, indicating the early developmental stages of these fish species are not necessarily being lost from the nursery. These larvae and juveniles are actively swimming against the ebb tide in the shallower, slower-flowing marginal areas facilitating recruitment against ebb flow.

Seasonal drift and feeding periodicity during summer of the amphipod, Gammarus psuedolimnaeus

USGS Publications Warehouse

Johnson, James H.

2014-01-01

Downstream drift of aquatic invertebrates is an important ecological process that varies temporally. Seasonal patterns of diel drift and diel feeding periodicity during summer of the amphipod Gammarus pseudolimnaeus were examined in a small stream in central New York. Seasonal trends in drift were similar with peak drift occurring from 2000 to 0400 h. Very little drift occurred during the day. Feeding intensity of G. pseudolimnaeus was greatest from 2000 to 0400 h and was significantly greater than at 0400 to 0800 h and 0800 to 1200 h. Previous research on feeding periodicity of this species found no evidence of periods of increased food consumption. Conflicting results between this study and earlier studies may be due to sampling drifting versus non-drifting amphipods.

ent-Kaurane-Based Regio- and Stereoselective Inverse Electron Demand Hetero-Diels-Alder Reactions: Synthesis of Dihydropyran-Fused Diterpenoids†

PubMed Central

Ding, Chunyong; Wang, Lili; Chen, Haijun; Wild, Christopher; Ye, Na; Ding, Ye; Wang, Tianzhi; White, Mark A.; Shen, Qiang; Zhou, Jia

2014-01-01

A mild and concise approach for the construction of 3,4-dihydro-2H-pyran ring integrated into the A-ring of the natural product oridonin using an optimized inverse electron demand hetero-Diels-Alder (IED HDA) reaction is reported herein. A self-dimerization of the exocyclic enone installed in the A-ring through a homo-HDA reaction was identified to exclusively give a dimeric ent-kaurane diterpenoid with the spirochroman core. Moreover, the efficient cross-HDA cycloadditions of this enone with various vinyl ethers or vinyl sulfides, instead of its own homo-HDA dimerization, were achieved in regio- and stereoselective manners, thus providing the access to novel dihydropyran-fused diterpenoids as potential anticancer agents to overcome chemoresistance. PMID:25225052

Intramolecular Aza-Diels-Alder Reactions of ortho-Quinone Methide Imines: Rapid, Catalytic, and Enantioselective Assembly of Benzannulated Quinolizidines.

PubMed

Kretzschmar, Martin; Hofmann, Fabian; Moock, Daniel; Schneider, Christoph

2018-04-16

Aza-Diels-Alder reactions (ADARs) are powerful processes that furnish N-heterocycles in a straightforward fashion. Intramolecular variants offer the additional possibility of generating bi- and polycyclic systems with high stereoselectivity. We report herein a novel Brønsted acid catalyzed process in which ortho-quinone methide imines tethered to the dienophile via the N substituent react in an intramolecular ADAR to form complex quinolizidines and oxazinoquinolines in a one-step process. The reactions proceed under very mild conditions, with very good yields and good to very good diastereo- and enantioselectivities. Furthermore, the process was extended to a domino reaction that efficiently combines substrate synthesis, ortho-quinone methide imine formation, and ADAR. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diel periodicity of drift of larval fishes in tributaries of Lake Ontario

USGS Publications Warehouse

Johnson, J. H.; McKenna, J.E.

2007-01-01

Diel patterns of downstream drift were examined during mid-June in three tributaries of Lake Ontario. Larval fishes were collected in drift nets that were set in each stream for 72 consecutive hours and emptied at 4-h intervals. Fantail darter (Ethostoma flabellare) and blacknose dace (Rhinichthys atractulus) were the two most abundant native stream fishes and were two of the three species collected in the ichthyoplankton drift. Fantail darter larvae comprised 100%, 98.9%, and 70.2% of the ichthyoplankton in the three streams. Most larval fishes (96%) drifted at night with peak catches occurring at 2400h in Orwell Brook and Trout Brook and 0400h in Little Sandy Creek. Based on stream temperatures, peak spawning and larval drift of blacknose dace probably occurred later in the season.

Keratinophilic fungi isolated from soils of long-term fold-grazed, degraded pastures in national parks of Slovakia.

PubMed

Javoreková, Soňa; Labuda, Roman; Maková, Jana; Novák, Ján; Medo, Juraj; Majerčíková, Kamila

2012-09-01

A total of 939 isolates of 11 genera representing 15 species of keratinophilic fungi were isolated and identified from the soils of three long-term fold-grazed pastures in national parks of Slovakia (Pod Ploskou, Strungový príslop, and Pod Kečkou) and one non-fold-grazed pasture in sierra Stolicke vrchy (Diel) using the hair-baiting technique. Keratinophilic fungi were present in all soil samples with a prevalence of Trichophyton ajelloi and Paecilomyces lilacinus. These fungi were more abundant in soil from fold-grazed pasture (Strungový príslop) compared to non-fold-grazed pasture (Diel). The occurrence of the other keratinophilic fungi was substantially lower, likely because of low pH in some soils.

Intramolecular inverse-electron-demand Diels-Alder reactions of imidazoles with 1,2,4-triazines: a new route to 1,2,3,4-tetrahydro-1,5-naphthyridines and related heterocycles.

PubMed

Lahue, Brian R; Lo, Sie-Mun; Wan, Zhao-Kui; Woo, Grace H C; Snyder, John K

2004-10-15

The intramolecular inverse-electron-demand Diels-Alder reaction between imidazoles and 1,2,4-triazines linked by a trimethylene tether from the imidazole N1 position to the triazine C3 proceed in excellent yields to produce 1,2,3,4-tetrahydro-1,5-naphthyridines. The reaction proceeds by a cycloaddition with subsequent loss of nitrogen, followed by a presumed stepwise loss of a nitrile. The analogous intramolecular cycloadditions employing a tetramethylene tether also proceeded to give 2,3,4,5-tetrahydro-1H-pyrido[3,2-b]azepines in acceptable yields. The reaction to produce the tetrahydro-1,5-naphthyridines can also be promoted with microwave irradiation.

NFLUX: a test of vertical nitrogen flux by diel migrant biota

NASA Astrophysics Data System (ADS)

Longhurst, A. R.; Bedo, A.; Harrison, W. G.; Head, E. J. H.; Horne, E. P.; Irwin, B.; Morales, C.

1989-11-01

At a station (NFLUX), occupied for 10 days in the northern Sargasso Sea, we assembled data to test the hypothesis that diel migrant biota in the open ocean induce a downward flux of dissolved inorganic nitrogen that is significant in relation to the passive flux under gravity of particulate organic nitrogen at the base on the photic zone. We founf taht NH 4+ excretion rates by day at depths below the photic zone were approximately 8% of particulate nitrogen flux obtained by a sediment trap array at the same depth. This figure is in the lower part of the range of values calculated previously for 10 published station data sets; we attribute this to the quite high rate of passive flux relative to primary production at the NFLUX station.

Intraday Water Quality Patterns in East Fork Poplar Creek with an Emphasis on Mercury and Monomethylmercury

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brooks, Scott C.; Lowe, Kenneth Alan

We conducted a diel sampling campaign at three locations along the Hg contaminated East Fork Poplar Creek (EFPC) in Oak Ridge, Tennessee to (i) quantify diel patterns of particulate and dissolved mercury (Hg) and monomethylmercury (MMHg) (HgD, HgP, MMHgD, and MMHgP, respectively) and associated water quality parameters along a longitudinal gradient of EFPC during the summer season, (ii) determine if diel patterns in Hg and/or MMHg are related to the daily photocycle or any other short term cycle, such as wastewater treatment plant discharge, (iii) determine if diel variability in turbidity and dissolved organic matter (DOM) composition correspond to particulatemore » HgP or MMHgP and dissolved organic carbon (DOC) or dissolved HgD or MMHgD. Samples were collected every two hours for a 30 hour period. The farthest upstream site was located at the boundary of Y-12 and the City of Oak Ridge (EFK 23.4) while two additional sites were located 7.2 kilometers (Wiltshire Drive, EFK 16.2) and 18 kilometers (Horizon Center, EFK 5.4) downstream of EFK 23.4).HgP and MMHgP concentrations increased overnight at EFK 16.2 and EFK 5.4 coincident with increases in turbidity and total suspended solids (TSS). These overnight increases were likely due to diel changes in the activity of macrobiota (re)suspending contaminated sediments in the creek. Both HgD and MMHgD were higher during the day at EFK 23.4 and EFK 5.4. The underlying causes for the patterns in HgD and MMHgD are less clear but correspond with similar patterns in DOC concentration and DOM composition. Photochemical reactions may also play a role in these HgD, MMHgD, DOC, and DOM patterns. Both Hg and MMHg loading increased with downstream distance. The greatest increase in loading occurred in the reach from EFK 23.4 to EFK 16.2 which encompasses areas where the Historic Release Deposits (HRD) have been identified. These results suggest that diffuse legacy sources of Hg, outside of Y-12, contribute Hg load to EFPC whereas MMHg is generated from instream processes.Intraday patterns in Hg and MMHg concentration and speciation have implications with respect to biotic exposure. Greater biotic activity and feeding during times of higher concentration would correspond to greater exposure than estimated from daily or longer term averages. Both Hg and MMHg responded rapidly to processes governing their concentration. This latter point is encouraging from the perspective of site remediation as it suggests that MMHg concentrations and flux in EFPC would respond rapidly to appropriate remedial actions.« less

Diels-Alder functionalized carbon nanotubes for bone tissue engineering: in vitro/in vivo biocompatibility and biodegradability

NASA Astrophysics Data System (ADS)

Mata, D.; Amaral, M.; Fernandes, A. J. S.; Colaço, B.; Gama, A.; Paiva, M. C.; Gomes, P. S.; Silva, R. F.; Fernandes, M. H.

2015-05-01

The risk-benefit balance for carbon nanotubes (CNTs) dictates their clinical fate. To take a step forward at this crossroad it is compulsory to modulate the CNT in vivo biocompatibility and biodegradability via e.g. chemical functionalization. CNT membranes were functionalised combining a Diels-Alder cycloaddition reaction to generate cyclohexene (-C6H10) followed by a mild oxidisation to yield carboxylic acid groups (-COOH). In vitro proliferation and osteogenic differentiation of human osteoblastic cells were maximized on functionalized CNT membranes (p,f-CNTs). The in vivo subcutaneously implanted materials showed a higher biological reactivity, thus inducing a slighter intense inflammatory response compared to non-functionalized CNT membranes (p-CNTs), but still showing a reduced cytotoxicity profile. Moreover, the in vivo biodegradation of CNTs was superior for p,f-CNT membranes, likely mediated by the oxidation-induced myeloperoxidase (MPO) in neutrophil and macrophage inflammatory milieus. This proves the biodegradability faculty of functionalized CNTs, which potentially avoids long-term tissue accumulation and triggering of acute toxicity. On the whole, the proposed Diels-Alder functionalization accounts for the improved CNT biological response in terms of the biocompatibility and biodegradability profiles. Therefore, CNTs can be considered for use in bone tissue engineering without notable toxicological threats.The risk-benefit balance for carbon nanotubes (CNTs) dictates their clinical fate. To take a step forward at this crossroad it is compulsory to modulate the CNT in vivo biocompatibility and biodegradability via e.g. chemical functionalization. CNT membranes were functionalised combining a Diels-Alder cycloaddition reaction to generate cyclohexene (-C6H10) followed by a mild oxidisation to yield carboxylic acid groups (-COOH). In vitro proliferation and osteogenic differentiation of human osteoblastic cells were maximized on functionalized CNT membranes (p,f-CNTs). The in vivo subcutaneously implanted materials showed a higher biological reactivity, thus inducing a slighter intense inflammatory response compared to non-functionalized CNT membranes (p-CNTs), but still showing a reduced cytotoxicity profile. Moreover, the in vivo biodegradation of CNTs was superior for p,f-CNT membranes, likely mediated by the oxidation-induced myeloperoxidase (MPO) in neutrophil and macrophage inflammatory milieus. This proves the biodegradability faculty of functionalized CNTs, which potentially avoids long-term tissue accumulation and triggering of acute toxicity. On the whole, the proposed Diels-Alder functionalization accounts for the improved CNT biological response in terms of the biocompatibility and biodegradability profiles. Therefore, CNTs can be considered for use in bone tissue engineering without notable toxicological threats. Electronic supplementary information (ESI) available: Experimental details on the preparation of HNO3 functionalized CNTs and supplementary analyses (μ-Raman, TG, EDS, acid-base titration, FTIR, roughness measurements, SEM and optical images) are shown. See DOI: 10.1039/c5nr01829c

Temporal network analysis identifies early physiological and transcriptomic indicators of mild drought in Brassica rapa

PubMed Central

Gehan, Malia A; Mockler, Todd C; Weinig, Cynthia; Ewers, Brent E

2017-01-01

The dynamics of local climates make development of agricultural strategies challenging. Yield improvement has progressed slowly, especially in drought-prone regions where annual crop production suffers from episodic aridity. Underlying drought responses are circadian and diel control of gene expression that regulate daily variations in metabolic and physiological pathways. To identify transcriptomic changes that occur in the crop Brassica rapa during initial perception of drought, we applied a co-expression network approach to associate rhythmic gene expression changes with physiological responses. Coupled analysis of transcriptome and physiological parameters over a two-day time course in control and drought-stressed plants provided temporal resolution necessary for correlation of network modules with dynamic changes in stomatal conductance, photosynthetic rate, and photosystem II efficiency. This approach enabled the identification of drought-responsive genes based on their differential rhythmic expression profiles in well-watered versus droughted networks and provided new insights into the dynamic physiological changes that occur during drought. PMID:28826479

Spatial and Temporal Patterns In Ecohydrological Separation

NASA Astrophysics Data System (ADS)

Jarvis, S. K.; Barnard, H. R.; Singha, K.; Harmon, R. E.; Szutu, D.

2017-12-01

The model of ecohydrological separation suggests that trees source water from a different subsurface pool than what is contributing to stream flow during dry periods, however diel fluctuations in stream flow and transpiration are tightly coupled. To better understand the mechanism of this coupling, this study examines spatiotemporal patterns in water isotopic relationships between tree, soil, and stream water. Preliminary analysis of data collected in 2015 show a trend in δ18O enrichment in xylem water, suggesting an increased reliance on enriched soil water not flowing to the stream as the growing season progresses, while xylem samples from 2016, a particularly wet year, do not have this trend. Variations in these temporal trends are explored with regard to distance from stream, aspect of hillslope, position in the watershed, size of the tree, and soil depth. Additionally, a near-stream site is examined at high resolution using water isotope data, sap flow, and electrical resistivity surveying to examine soil moisture and water use patterns across the riparian-hillslope transition.

Ontogenetic variation in food consumption of rusty crayfish (Orconectes rusticus) in a central New York stream

USGS Publications Warehouse

Johnson, J. H.; Nack, C.C.

2010-01-01

We examined feeding periodicity of three size groups of the rusty crayfish (Orconectes rusticus) at four-hour intervals over a 28-hour period during July in a headwater stream of the Susquehanna River drainage in central New York. Feeding activity was expressed as the ratio of stomach weight divided by the crayfish wet weight. The diel food consumption patterns of all three size groups of rusty crayfish (i.e., ??? 10 mm, 11-20 mm, and > 20 mm carapace length) were significantly different. Peak feeding of the smallest crayfish occurred during crepuscular periods. Food consumption of the intermediate size crayfish was highest at 2000 h, and feeding of large crayfish was consistently high from 1200 h to 0400 h. Feeding intensity of both small and intermediate size crayfish was highest when feeding intensity of large crayfsh was lowest. Ontogenetic differences in feeding periodicity may be associated with predation pressure from large rusty crayfish on smaller individuals.

Ontogenetic Variation in Food Consumption of Rusty Crayfish (Orconectes rusticus) in a Central New York Stream

USGS Publications Warehouse

Johnson, James H.; Nack, Christopher C.

2010-01-01

We examined feeding periodicity of three size groups of the rusty crayfish (Orconectes rusticus) at four-hour intervals over a 28-hour period during July in a headwater stream of the Susquehanna River drainage in central New York. Feeding activity was expressed as the ratio of stomach weight divided by the crayfish wet weight. The diel food consumption patterns of all three size groups of rusty crayfish (i.e., ≤ 10 mm, 11–20 mm, and > 20 mm carapace length) were significantly different. Peak feeding of the smallest crayfish occurred during crepuscular periods. Food consumption of the intermediate size crayfish was highest at 2000 h, and feeding of large crayfish was consistently high from 1200 h to 0400 h. Feeding intensity of both small and intermediate size crayfish was highest when feeding intensity of large crayfsh was lowest. Ontogenetic differences in feeding periodicity may be associated with predation pressure from large rusty crayfish on smaller individuals.

Increasing sensitivity of methane emission measurements in rice through deployment of ‘closed chambers’ at nighttime

PubMed Central

Wassmann, Reiner; Alberto, Ma. Carmelita; Tirol-Padre, Agnes; Hoang, Nghia Trong; Romasanta, Ryan; Centeno, Caesar Arloo; Sander, Bjoern Ole

2018-01-01

This study comprises field experiments on methane emissions from rice fields conducted with an Eddy-Covariance (EC) system as well as test runs for a modified closed chamber approach based on measurements at nighttime. The EC data set covers 4 cropping seasons with highly resolved emission rates (raw data in 10 Hz frequency have been aggregated to 30-min records). The diel patterns were very pronounced in the two dry seasons with peak emissions at early afternoon and low emissions at nighttime. These diel patterns were observed at all growing stages of the dry seasons. In the two wet seasons, the diel patterns were only visible during the vegetative stages while emission rates during reproductive and ripening stages remained within a fairly steady range and did not show any diel patterns. In totality, however, the data set revealed a very strong linear relationship between nocturnal emissions (12-h periods) and the full 24-h periods resulting in an R2-value of 0.8419 for all data points. In the second experiment, we conducted test runs for chamber measurements at nighttime with much longer deployment times (6 h) as compared to measurements at daylight (typically for 30 min). Conducting chamber measurements at nighttime excluded drastic changes of temperatures and CO2 concentrations. The data also shows that increases in CH4 concentrations remained on linear trajectory over a 6h period at night. While end CH4 concentrations were consistently >3.5 ppm, this long-term enclosure represents a very robust approach to quantify emissions as compared to assessing short-term concentration increases over time near the analytical detection limit. Finally, we have discussed the potential applications of this new approach that would allow emission measurements even when conventional (daytime) measurements will not be suitable. Nighttime chamber measurements offer an alternative to conventional (daytime) measurements if either (i) baseline emissions are at a very low level, (ii) differences of tested crop treatments or varieties are very small or (iii) the objective is to screen a large number of rice varieties for taking advantage of progress in genome sequencing. PMID:29390000

Dynamics of seawater carbonate chemistry, production, and calcification of a coral reef flat, Central Great Barrier Reef

NASA Astrophysics Data System (ADS)

Albright, R.; Langdon, C.; Anthony, K. R. N.

2013-05-01

Ocean acidification is projected to shift coral reefs from a state of net accretion to one of net dissolution this century. Presently, our ability to predict global-scale changes to coral reef calcification is limited by insufficient data relating seawater carbonate chemistry parameters to in situ rates of reef calcification. Here, we investigate natural trends in carbonate chemistry of the Davies Reef flat in the central Great Barrier Reef on diel and seasonal timescales and relate these trends to benthic carbon fluxes by quantifying net ecosystem calcification (nec) and net community production (ncp). Results show that seawater carbonate chemistry of the Davies Reef flat is highly variable over both diel and seasonal timescales. pH (total scale) ranged from 7.92 to 8.17, pCO2 ranged from 272 to 542 μatm, and aragonite saturation state (Ωarag) ranged from 2.9 to 4.1. Diel cycles in carbonate chemistry were primarily driven by ncp, and warming explained 35% and 47% of the seasonal shifts in pCO2 and pH, respectively. Daytime ncp averaged 36 ± 19 mmol C m-2 h-1 in summer and 33 ± 13 mmol C m-2 h-1 in winter; nighttime ncp averaged -22 ± 20 and -7 ± 6 mmol C m-2 h-1 in summer and winter, respectively. Daytime nec averaged 11 ± 4 mmol CaCO3 m-2 h-1 in summer and 8 ± 3 mmol CaCO3 m-2 h-1 in winter, whereas nighttime nec averaged 2 ± 4 mmol and -1 ± 3 mmol CaCO3 m-2 h-1 in summer and winter, respectively. Net ecosystem calcification was positively correlated with Ωarag for both seasons. Linear correlations of nec and Ωarag indicate that the Davies Reef flat may transition from a state of net calcification to net dissolution at Ωarag values of 3.4 in summer and 3.2 in winter. Diel trends in Ωarag indicate that the reef flat is currently below this calcification threshold 29.6% of the time in summer and 14.1% of the time in winter.

Structural Modification of Sol-Gel Materials through Retro Diels-Alder Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

SHALTOUT,RAAFAT M.; LOY,DOUGLAS A.; MCCLAIN,MARK D.

1999-12-08

Hydrolysis and condensation of organically bridged bis-triethoxysilanes, (EtO){sub 3}Si-R-Si(OEt){sub 3}, results in the formation of three dimensional organic/inorganic hybrid networks (Equation 1). Properties of these materials, including porosity, are dependent on the nature of the bridging group, R. Flexible groups (akylene-spacers longer than five carbons in length) polymerize under acidic conditions to give non-porous materials. Rigid groups (such as arylene-, alkynylene-, or alkenylene) form non-porous, microporous, and macroporous gels. In many cases the pore size distributions are quite narrow. One of the motivations for preparing hybrid organic-inorganic materials is to extend the range of properties available with sol-gel systems bymore » incorporating organic groups into the inorganic network. For example, organically modified silica gels arc either prepared by co-polymerizing an organoalkoxysilane with a silica precursor or surface silylating the inorganic gel. This can serve to increase hydrophobicity or to introduce some reactive organic functionality. However, the type and orientation of these organic functionalities is difficult to control. Furthermore, many organoalkoxysilanes can act to inhibitor even prevent gelation, limiting the final density of organic functionalities. We have devised a new route for preparing highly functionalized pores in hybrid materials using bridging groups that are thermally converted into the desired functionalities after the gel has been obtained. In this paper, we present the preparation and characterization of bridged polysilsesquioxanes with Diels-Alder adducts as the bridging groups from the sol-gel polymerization of monomers 2 and 4. The bridging groups are constructed such that the retro Diela-Alder reaction releases the dienes and leaves the dienophiles as integral parts of the network polymers. In the rigid architecture of a xerogel, this loss of organic functionality should liberate sufficient space to modify the overall porosity. Furthermore, the new porosity will be functionalized with the dienophilic olefin bridging group. We also demonstrate that by changing the type of Diels-Alder adduct used as the bridging group, we can change the temperature at which the retro-Diels-Alder reaction will occur.« less

Recyclable thermosetting thermal pad using silicone-based polyurethane crosslinked by Diels-Alder adduct

NASA Astrophysics Data System (ADS)

Kim, Jong-Woong; Lee, Da Hee; Jeon, Hee-Jeong; Jang, Sung Il; Cho, Hyun Min; Kim, Youngmin

2018-01-01

The recyclable silicone-based thermoset was successfully synthesized by making use of a Diels-Alder (DA) adduct as a cross-linker. The incorporation of the furan-tethered diol 1 into the polymer backbones realized the crosslinking of polymers via the DA reaction. The thermosetting polymer was dissolved in DMF after the retro DA reaction which was monitored by 1H NMR spectroscopy. Due to the retro DA reaction, polymer showed the mendable behavior when it was scratched followed by being heated. This polymer was mixed with alumina powders to fabricate the thermal pad. The thermal resistance of this pad was measured to be 0.48 K/W by a thermal transient test. The thermosetting composite was recycled via the retro DA reaction. The thermal resistance of the recycled one was similar to that of the original one.

Photochemistry of tricyclo[5.2.2.0(2,6)]undeca-4,10-dien-8-ones: an efficient general route to substituted linear triquinanes from 2-methoxyphenols. Total synthesis of (+/-)-Delta(9(12))-capnellene.

PubMed

Hsu, Day-Shin; Chou, Yu-Yu; Tung, Yen-Shih; Liao, Chun-Chen

2010-03-08

An efficient and short entry to polyfunctionalized linear triquinanes from 2-methoxyphenols is described by utilizing the following chemistry. The Diels-Alder reactions of masked o-benzoquinones, derived from 2-methoxyphenols, with cyclopentadiene afford tricyclo[5.2.2.0(2,6)]undeca-4,10-dien-8-ones. Photochemical oxa-di-pi-methane (ODPM) rearrangements and 1,3-acyl shifts of the Diels-Alder adducts are investigated. The ODPM-rearranged products are further converted to linear triquinanes by using an O-stannyl ketyl fragmentation. Application of this efficient strategy to the total synthesis of (+/-)-Delta(9(12))-capnellene was accomplished from 2-methoxy-4-methylphenol in nine steps with 20 % overall yield.

Solid-supported nitroso hetero Diels-Alder reactions. 1. Acylnitroso dienophiles: scope and limitations.

PubMed

Krchnák, Viktor; Moellmann, Ute; Dahse, Hans-Martin; Miller, Marvin J

2008-01-01

Polymer-supported acylnitroso dienophiles were prepared and used in hetero Diels-Alder (HDA) reactions with a variety of dienes. The transient acylnitroso dienophiles were prepared in situ from immobilized hydroxamates, which were attached to solid supports via several linkers each cleavable by different cleavage reagents, and served for the synthesis of both N-unsubstituted and N-derivatized HDA adducts. Model compounds were used to (i) optimize reaction conditions for solid-supported HDA reactions, (ii) evaluate the outcome of the reactions with various dienes, (iii) compare relative reactivities of dienes, and (iv) assess the stability of HDA adducts toward cleavage conditions typically used in solid-phase syntheses. Cleaved products were submitted to biological assays, and the results are reported. The accompanying paper, focused on complementary arylnitroso HDA reactions, includes a comparison of both HDA reactions.

P-chiral 1-phosphanorbornenes: from asymmetric phospha-Diels-Alder reactions towards ligand design and functionalisation.

PubMed

Möller, Tobias; Wonneberger, Peter; Sárosi, Menyhárt B; Coburger, Peter; Hey-Hawkins, Evamarie

2016-02-07

The principle of stereotopic face differentiation was successfully applied to 2H-phospholes which undergo a very efficient and highly stereoselective Diels-Alder reaction giving phosphorus-chiral 1-phosphanorbornenes with up to 87% yield. The observed reaction pathway has been supported by theoretical calculations showing that the cycloaddition reaction between 2H-phosphole 3a and the dienophile (5R)-(-)-menthyloxy-2(5H)-furanone (8) is of normal electron demand. Optically pure phosphanes were obtained by separation of the single diastereomers and subsequent desulfurisation of the sulfur-protected phosphorus atom. Finally, divergent ligand synthesis is feasible by reduction of the chiral auxiliary, subsequent stereospecific intramolecular Michael addition, and various functionalisations of the obtained key compound 13a. Furthermore, the unique structural properties of phospanorbornenes are presented and compared to those of phosphanorbornanes.

(125)I-Tetrazines and Inverse-Electron-Demand Diels-Alder Chemistry: A Convenient Radioiodination Strategy for Biomolecule Labeling, Screening, and Biodistribution Studies.

PubMed

Albu, Silvia A; Al-Karmi, Salma A; Vito, Alyssa; Dzandzi, James P K; Zlitni, Aimen; Beckford-Vera, Denis; Blacker, Megan; Janzen, Nancy; Patel, Ramesh M; Capretta, Alfredo; Valliant, John F

2016-01-20

A convenient method to prepare radioiodinated tetrazines was developed, such that a bioorthogonal inverse electron demand Diels-Alder reaction can be used to label biomolecules with iodine-125 for in vitro screening and in vivo biodistribution studies. The tetrazine was prepared by employing a high-yielding oxidative halo destannylation reaction that concomitantly oxidized the dihydrotetrazine precursor. The product reacts quickly and efficiently with trans-cyclooctene derivatives. Utility was demonstrated through antibody and hormone labeling experiments and by evaluating products using standard analytical methods, in vitro assays, and quantitative biodistribution studies where the latter was performed in direct comparison to Bolton-Hunter and direct iodination methods. The approach described provides a convenient and advantageous alternative to conventional protein iodination methods that can expedite preclinical development and evaluation of biotherapeutics.

Theoretical study of catalytic efficiency of a Diels-Alderase catalytic antibody: an indirect effect produced during the maturation process.

PubMed

Martí, Sergio; Andrés, Juan; Moliner, Vicent; Silla, Estanislao; Tuñón, Iñaki; Bertrán, Juan

2008-01-01

The Diels-Alder reaction is one of the most important and versatile transformations available to organic chemists for the construction of complex natural products, therapeutics agents, and synthetic materials. Given the lack of efficient enzymes capable of catalyzing this kind of reaction, it is of interest to ask whether a biological catalyst could be designed from an antibody-combining site. In the present work, a theoretical study of the different behavior of a germline catalytic antibody (CA) and its matured form, 39 A-11, that catalyze a Diels-Alder reaction has been carried out. A free-energy perturbation technique based on a hybrid quantum-mechanics/molecular-mechanics scheme, together with internal energy minimizations, has allowed free-energy profiles to be obtained for both CAs. The profiles show a smaller barrier for the matured form, which is in agreement with the experimental observation. Free-energy profiles were obtained with this methodology, thereby avoiding the much more demanding two-dimensional calculations of the energy surfaces that are normally required to study this kind of reaction. Structural analysis and energy evaluations of substrate-protein interactions have been performed from averaged structures, which allows understanding of how the single mutations carried out during the maturation process can be responsible for the observed fourfold enhancement of the catalytic rate constant. The conclusion is that the mutation effect in this studied germline CA produces a complex indirect effect through coupled movements of the backbone of the protein and the substrate.

Seasonal Changes in the Isotopic Compositions and Sinking Fluxes of Euthecosomatous Pteropod Shells in the Sargasso Sea

NASA Astrophysics Data System (ADS)

Fabry, V. J.; Deuser, W. G.

1992-04-01

Seasonal variations in the oxygen and carbon isotopic compositions and fluxes of five euthecosomatous pteropods were determined from a 14-month series of sediment trap deployments in the Sargasso Sea. Medium and large shell sizes of Styliola subula, Clio pyramidata, Limacina inflata, Creseis acicula, and Cuvierina columnella were collected throughout the sampling period. Comparisons of the δ18O of shell samples with the vertical and temporal variations in the calculated δ18O of aragonite in equilibrium with seawater suggest that these pteropods deposited the bulk of their shell mass at the following depths: S. subula and L. inflata at 50 m, C. pyramidata at 75 m, C. acicula in the upper 25 m, and C. columnella at 50-75 m. Although several of these species undergo diel vertical migration of several hundred meters in this region, the estimated depths of calcification match the upper parts of the species' vertical ranges, where the mean populations occur only at night. In all species, seasonal changes in the δ18O of shells were closely coupled to those of equilibrium δ18O for aragonite, suggesting that most of the shell mass of these individuals was formed within several months. Flux-weighted, mean δ18O values for the species reveal that seasonal variations in the sinking fluxes of shells would not affect the isotopic compositions of shell accumulations in Bermuda Rise sediments. Carbon and oxygen isotopes were positively correlated in all species except C. columnella, which suggests that temperature may influence the δ13C of the shells of these species.

Endogenous and exogenous control of ecosystem function: N cycling in headwater streams.

PubMed

Valett, H M; Thomas, S A; Mulholland, P J; Webster, J R; Dahm, C N; Fellows, C S; Crenshaw, C L; Peterson, C G

2008-12-01

Allochthonous inputs act as resource subsidies to many ecosystems, where they exert strong influences on metabolism and material cycling. At the same time, metabolic theory proposes endogenous thermal control independent of resource supply. To address the relative importance of exogenous and endogenous influences, we quantified spatial and temporal variation in ecosystem metabolism and nitrogen (N) uptake using seasonal releases of 15N as nitrate in six streams differing in riparian-stream interaction and metabolic character. Nitrate removal was quantified using a nutrient spiraling approach based on measurements of downstream decline in 15N flux. Respiration (R) and gross primary production (GPP) were measured with whole-stream diel oxygen budgets. Uptake and metabolism metrics were addressed as z scores relative to site means to assess temporal variation. In open-canopied streams, areal uptake (U; microg N x m(-2) x s(-1)) was closely related to GPP, metabolic rates increased with temperature, and R was accurately predicted by metabolic scaling relationships. In forested streams, N spiraling was not related to GPP; instead, uptake velocity (v(f); mm/s) was closely related to R. In contrast to open-canopied streams, N uptake and metabolic activity were negatively correlated to temperature and poorly described by scaling laws. We contend that streams differ along a gradient of exogenous and endogenous control that relates to the relative influences of resource subsidies and in-stream energetics as determinants of seasonal patterns of metabolism and N cycling. Our research suggests that temporal variation in the propagation of ecological influence between adjacent systems generates phases when ecosystems are alternatively characterized as endogenously and exogenously controlled.

High-resolution proxies for wood density variations in Terminalia superba

PubMed Central

De Ridder, Maaike; Van den Bulcke, Jan; Vansteenkiste, Dries; Van Loo, Denis; Dierick, Manuel; Masschaele, Bert; De Witte, Yoni; Mannes, David; Lehmann, Eberhard; Beeckman, Hans; Van Hoorebeke, Luc; Van Acker, Joris

2011-01-01

Background and Aims Density is a crucial variable in forest and wood science and is evaluated by a multitude of methods. Direct gravimetric methods are mostly destructive and time-consuming. Therefore, faster and semi- to non-destructive indirect methods have been developed. Methods Profiles of wood density variations with a resolution of approx. 50 µm were derived from one-dimensional resistance drillings, two-dimensional neutron scans, and three-dimensional neutron and X-ray scans. All methods were applied on Terminalia superba Engl. & Diels, an African pioneer species which sometimes exhibits a brown heart (limba noir). Key Results The use of X-ray tomography combined with a reference material permitted direct estimates of wood density. These X-ray-derived densities overestimated gravimetrically determined densities non-significantly and showed high correlation (linear regression, R2 = 0·995). When comparing X-ray densities with the attenuation coefficients of neutron scans and the amplitude of drilling resistance, a significant linear relation was found with the neutron attenuation coefficient (R2 = 0·986) yet a weak relation with drilling resistance (R2 = 0·243). When density patterns are compared, all three methods are capable of revealing the same trends. Differences are mainly due to the orientation of tree rings and the different characteristics of the indirect methods. Conclusions High-resolution X-ray computed tomography is a promising technique for research on wood cores and will be explored further on other temperate and tropical species. Further study on limba noir is necessary to reveal the causes of density variations and to determine how resistance drillings can be further refined. PMID:21131386

Variability of the carbonate chemistry in a shallow, seagrass-dominated ecosystem: implications for ocean acidification experiments

USGS Publications Warehouse

Challener, Roberta; Robbins, Lisa L.; Mcclintock, James B.

2016-01-01

Open ocean observations have shown that increasing levels of anthropogenically derived atmospheric CO2 are causing acidification of the world's oceans. Yet little is known about coastal acidification and studies are just beginning to characterise the carbonate chemistry of shallow, nearshore zones where many ecologically and economically important organisms occur. We characterised the carbonate chemistry of seawater within an area dominated by seagrass beds (Saint Joseph Bay, Florida) to determine the extent of variation in pH and pCO2 over monthly and daily timescales. Distinct diel and seasonal fluctuations were observed at daily and monthly timescales respectively, indicating the influence of photosynthetic and respiratory processes on the local carbonate chemistry. Over the course of a year, the range in monthly values of pH (7.36-8.28), aragonite saturation state (0.65-5.63), and calculated pCO2 (195-2537 μatm) were significant. When sampled on a daily basis the range in pH (7.70-8.06), aragonite saturation state (1.86-3.85), and calculated pCO2 (379-1019 μatm) also exhibited significant range and indicated variation between timescales. The results of this study have significant implications for the design of ocean acidification experiments where nearshore species are utilised and indicate that coastal species are experiencing far greater fluctuations in carbonate chemistry than previously thought.

Female turtles from hot nests: is it duration of incubation or proportion of development at high temperatures that matters?

PubMed

Georges, Arthur

1989-11-01

Mean daily temperature in natural nests of freshwater turtles with temperature-dependent sex determination is known to be a poor predictor of hatchling sex ratios when nest temperatures fluctuate. To account for this, a model was developed on the assumption that females will emerge from eggs when more than half of embryonic development occurs above the threshold temperature for sex determination rather than from eggs that spend more than half their time above the threshold. The model is consistent with previously published data and in particular explains the phenomenon whereby the mean temperature that best distinguishes between male and female nests decreases with increasing variability in nest temperature. The model, if verified by controlled experiments, has important implications for our understanding of temperature-dependent sex determination in natural nests. Both mean nest temperature and "hours spent above the threshold" will be poor predictors of hatchling sex ratios. Studies designed to investigate latitudinal trends and inter-specific differences in the threshold temperature will need to consider latitudinal and inter-specific variation in the magnitude of diel fluctuations in nest temperature, and variation in factors influencing the magnitude of those fluctuations, such as nest depth. Furthermore, any factor that modifies the relationship between developmental rate and temperature can be expected to influence hatchling sex ratios in natural nests, especially when nest temperatures are close to the threshold.

Asymmetric Oxidation of o-Alkylphenols with Chiral 2-(o-Iodoxyphenyl)-Oxazolines

PubMed Central

Boppisetti, Jagadish K.; Birman, Vladimir B.

2009-01-01

A new class of chiral iodine (V) derivatives has been prepared. These compounds have been found to transform ortho-alkylphenols into ortho-quinol Diels-Alder dimers with significant levels of asymmetric induction. PMID:19231848

A high-resolution time-depth view of dimethylsulphide cycling in the surface sea

PubMed Central

Royer, S.-J.; Galí, M.; Mahajan, A. S.; Ross, O. N.; Pérez, G. L.; Saltzman, E. S.; Simó, R.

2016-01-01

Emission of the trace gas dimethylsulphide (DMS) from the ocean influences the chemical and optical properties of the atmosphere, and the olfactory landscape for foraging marine birds, turtles and mammals. DMS concentration has been seen to vary across seasons and latitudes with plankton taxonomy and activity, and following the seascape of ocean’s physics. However, whether and how does it vary at the time scales of meteorology and day-night cycles is largely unknown. Here we used high-resolution measurements over time and depth within coherent water patches in the open sea to show that DMS concentration responded rapidly but resiliently to mesoscale meteorological perturbation. Further, it varied over diel cycles in conjunction with rhythmic photobiological indicators in phytoplankton. Combining data and modelling, we show that sunlight switches and tunes the balance between net biological production and abiotic losses. This is an outstanding example of how biological diel rhythms affect biogeochemical processes. PMID:27578300

Temperature-controlled cross-linking of silver nanoparticles with diels-alder reaction and its application on antibacterial property

NASA Astrophysics Data System (ADS)

Liu, Lian; Yang, Pengfei; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling

2017-05-01

Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV-vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.

Impact of scaffold rigidity on the design and evolution of an artificial Diels-Alderase

PubMed Central

Preiswerk, Nathalie; Beck, Tobias; Schulz, Jessica D.; Milovník, Peter; Mayer, Clemens; Siegel, Justin B.; Baker, David; Hilvert, Donald

2014-01-01

By combining targeted mutagenesis, computational refinement, and directed evolution, a modestly active, computationally designed Diels-Alderase was converted into the most proficient biocatalyst for [4+2] cycloadditions known. The high stereoselectivity and minimal product inhibition of the evolved enzyme enabled preparative scale synthesis of a single product diastereomer. X-ray crystallography of the enzyme–product complex shows that the molecular changes introduced over the course of optimization, including addition of a lid structure, gradually reshaped the pocket for more effective substrate preorganization and transition state stabilization. The good overall agreement between the experimental structure and the original design model with respect to the orientations of both the bound product and the catalytic side chains contrasts with other computationally designed enzymes. Because design accuracy appears to correlate with scaffold rigidity, improved control over backbone conformation will likely be the key to future efforts to design more efficient enzymes for diverse chemical reactions. PMID:24847076

Architecture of a Diels-Alderase ribozyme with a preformed catalytic pocket.

PubMed

Keiper, Sonja; Bebenroth, Dirk; Seelig, Burckhard; Westhof, Eric; Jäschke, Andres

2004-09-01

Artificial ribozymes catalyze a variety of chemical reactions. Their structures and reaction mechanisms are largely unknown. We have analyzed a ribozyme catalyzing Diels-Alder cycloaddition reactions by comprehensive mutation analysis and a variety of probing techniques. New tertiary interactions involving base pairs between nucleotides of the 5' terminus and a large internal loop forming a pseudoknot fold were identified. The probing data indicate a preformed tertiary structure that shows no major changes on substrate or product binding. Based on these observations, a molecular architecture featuring a Y-shaped arrangement is proposed. The tertiary structure is formed in a rather unusual way; that is, the opposite sides of the asymmetric internal loop are clamped by the four 5'-terminal nucleotides, forming two adjacent two base-pair helices. It is proposed that the catalytic pocket is formed by a wedge within one of these helices.

Iodine(III) Derivatives as Halogen Bonding Organocatalysts.

PubMed

Heinen, Flemming; Engelage, Elric; Dreger, Alexander; Weiss, Robert; Huber, Stefan M

2018-03-26

Hypervalent iodine(III) derivatives are known as versatile reagents in organic synthesis, but there is only one previous report on their use as Lewis acidic organocatalysts. Herein, we present first strong indications for the crucial role of halogen bonding in this kind of catalyses. To this end, the solvolysis of benzhydryl chloride and the Diels-Alder reaction of cyclopentadiene with methyl vinyl ketone served as benchmark reactions for halide abstraction and the activation of neutral compounds. Iodolium compounds (cyclic diaryl iodonium species) were used as activators or catalysts, and we were able to markedly reduce or completely switch off their activity by sterically blocking one or two of their electrophilic axes. Compared with previously established bidentate cationic halogen bond donors, the monodentate organoiodine derivatives used herein are at least similarly active (in the Diels-Alder reaction) or even decidedly more active (in benzhydryl chloride solvolysis). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Addition polymers from 1,4,5,8-tetrahydro-1,4;5,8-diepoxyanthracene and Bis-dienes. 2: Evidence for thermal dehydration occurring in the cure process

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Olshavsky, Michael A.; Meador, Michael A.; Ahn, Myong-Ku

1988-01-01

Diels-Alder cycloaddition copolymers from 1,4,5,8-tetrahydro-1,4;5,8-diepoxyanthracene and anthracene end-capped polyimide oligomers appear, by thermogravimetric analysis (TGA), to undergo dehydration at elevated temperatures. This would produce thermally stable pentiptycene units along the polymer backbone, and render the polymers incapable of unzipping through a retro-Diels-Alder pathway. High resolution solid 13C nuclear magnetic resonance (NMR) of one formulation of the polymer system before and after heating at elevated temperatures, shows this to indeed be the case. NMR spectra of solid samples of the polymer before and after heating correlated well with those of the parent pentiptycene model compound before and after acid-catalyzed dehydration. Isothermal gravimetric analyses and viscosities of the polymer before and after heat treatment support dehydration as a mechanism for the cure reaction.

From Biomass-Derived Furans to Aromatics with Ethanol over Zeolite.

PubMed

Teixeira, Ivo F; Lo, Benedict T W; Kostetskyy, Pavlo; Stamatakis, Michail; Ye, Lin; Tang, Chiu C; Mpourmpakis, Giannis; Tsang, Shik Chi Edman

2016-10-10

We report a novel catalytic conversion of biomass-derived furans and alcohols to aromatics over zeolite catalysts. Aromatics are formed via Diels-Alder cycloaddition with ethylene, which is produced in situ from ethanol dehydration. The use of liquid ethanol instead of gaseous ethylene, as the source of dienophile in this one-pot synthesis, makes the aromatics production much simpler and renewable, circumventing the use of ethylene at high pressure. More importantly, both our experiments and theoretical studies demonstrate that the use of ethanol instead of ethylene, results in significantly higher rates and higher selectivity to aromatics, due to lower activation barriers over the solid acid sites. Synchrotron-diffraction experiments and proton-affinity calculations clearly suggest that a preferred protonation of ethanol over the furan is a key step facilitating the Diels-Alder and dehydration reactions in the acid sites of the zeolite. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A high-resolution time-depth view of dimethylsulphide cycling in the surface sea

NASA Astrophysics Data System (ADS)

Royer, S.-J.; Galí, M.; Mahajan, A. S.; Ross, O. N.; Pérez, G. L.; Saltzman, E. S.; Simó, R.

2016-08-01

Emission of the trace gas dimethylsulphide (DMS) from the ocean influences the chemical and optical properties of the atmosphere, and the olfactory landscape for foraging marine birds, turtles and mammals. DMS concentration has been seen to vary across seasons and latitudes with plankton taxonomy and activity, and following the seascape of ocean’s physics. However, whether and how does it vary at the time scales of meteorology and day-night cycles is largely unknown. Here we used high-resolution measurements over time and depth within coherent water patches in the open sea to show that DMS concentration responded rapidly but resiliently to mesoscale meteorological perturbation. Further, it varied over diel cycles in conjunction with rhythmic photobiological indicators in phytoplankton. Combining data and modelling, we show that sunlight switches and tunes the balance between net biological production and abiotic losses. This is an outstanding example of how biological diel rhythms affect biogeochemical processes.

Diels-Alder active-template synthesis of rotaxanes and metal-ion-switchable molecular shuttles.

PubMed

Crowley, James D; Hänni, Kevin D; Leigh, David A; Slawin, Alexandra M Z

2010-04-14

A synthesis of [2]rotaxanes in which Zn(II) or Cu(II) Lewis acids catalyze a Diels-Alder cycloaddition to form the axle while simultaneously acting as the template for the assembly of the interlocked molecules is described. Coordination of the Lewis acid to a multidentate endotopic 2,6-di(methyleneoxymethyl)pyridyl- or bipyridine-containing macrocycle orients a chelated dienophile through the macrocycle cavity. Lewis acid activation of the double bond causes it to react with an incoming "stoppered" diene, affording the [2]rotaxane in up to 91% yield. Unusually for an active-template synthesis, the metal binding site "lives on" in these rotaxanes. This was exploited in the synthesis of a molecular shuttle containing two different ligating sites in which the position of the macrocycle could be switched by complexation with metal ions [Zn(II) and Pd(II)] with different preferred coordination geometries.

Poly(2-vinyl pyridine)-block-poly(ethylene oxide) featuring a furan group at the block junction-synthesis and functionalization.

PubMed

Rudolph, Tobias; Barthel, Markus J; Kretschmer, Florian; Mansfeld, Ulrich; Hoeppener, Stephanie; Hager, Martin D; Schubert, Ulrich S; Schacher, Felix H

2014-05-01

Furfuryl glycidyl ether (FGE) represents a highly versatile monomer for the preparation of reversibly cross-linkable nanostructured materials via Diels-Alder reactions. Here, the use of FGE for the mid-chain functionalization of a P2VP-b-PEO diblock copolymer is reported. The material features one furan moiety at the block junction, P2VP68 -FGE-b-PEO390 , which can be subsequently addressed in Diels-Alder reactions using maleimide-functionalized counterparts. The presence of the FGE moiety enables the introduction of dyes as model labels or the formation of hetero-grafted brushes as shell on hybrid Au@Polymer nanoparticles. This renders P2VP68 -FGE-b-PEO390 , a powerful tool for selective functionalization reactions, including the modification of surfaces. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Increased Diels-Alderase activity through backbone remodeling guided by Foldit players.

PubMed

Eiben, Christopher B; Siegel, Justin B; Bale, Jacob B; Cooper, Seth; Khatib, Firas; Shen, Betty W; Players, Foldit; Stoddard, Barry L; Popovic, Zoran; Baker, David

2012-01-22

Computational enzyme design holds promise for the production of renewable fuels, drugs and chemicals. De novo enzyme design has generated catalysts for several reactions, but with lower catalytic efficiencies than naturally occurring enzymes. Here we report the use of game-driven crowdsourcing to enhance the activity of a computationally designed enzyme through the functional remodeling of its structure. Players of the online game Foldit were challenged to remodel the backbone of a computationally designed bimolecular Diels-Alderase to enable additional interactions with substrates. Several iterations of design and characterization generated a 24-residue helix-turn-helix motif, including a 13-residue insertion, that increased enzyme activity >18-fold. X-ray crystallography showed that the large insertion adopts a helix-turn-helix structure positioned as in the Foldit model. These results demonstrate that human creativity can extend beyond the macroscopic challenges encountered in everyday life to molecular-scale design problems.

Biogeochemistry from Gliders at the Hawaii Ocean Times-Series

NASA Astrophysics Data System (ADS)

Nicholson, D. P.; Barone, B.; Karl, D. M.

2016-02-01

At the Hawaii Ocean Time-series (HOT) autonomous, underwater gliders equipped with biogeochemical sensors observe the oceans for months at a time, sampling spatiotemporal scales missed by the ship-based programs. Over the last decade, glider data augmented by a foundation of time-series observations have shed light on biogeochemical dynamics occuring spatially at meso- and submesoscales and temporally on scales from diel to annual. We present insights gained from the synergy between glider observations, time-series measurements and remote sensing in the subtropical North Pacific. We focus on diel variability observed in dissolved oxygen and bio-optics and approaches to autonomously quantify net community production and gross primary production (GPP) as developed during the 2012 Hawaii Ocean Experiment - DYnamics of Light And Nutrients (HOE-DYLAN). Glider-based GPP measurements were extended to explore the relationship between GPP and mesoscale context over multiple years of Seaglider deployments.

Critical Role of Diels-Adler Adducts to Realise Stretchable Transparent Electrodes Based on Silver Nanowires and Silicone Elastomer

NASA Astrophysics Data System (ADS)

Heo, Gaeun; Pyo, Kyoung-Hee; Lee, Da Hee; Kim, Youngmin; Kim, Jong-Woong

2016-05-01

This paper presents the successful fabrication of a transparent electrode comprising a sandwich structure of silicone/Ag nanowires (AgNWs)/silicone equipped with Diels-Alder (DA) adducts as crosslinkers to realise highly stable stretchability. Because of the reversible DA reaction, the crosslinked silicone successfully bonds with the silicone overcoat, which should completely seal the electrode. Thus, any surrounding liquid cannot leak through the interfaces among the constituents. Furthermore, the nanowires are protected by the silicone cover when they are stressed by mechanical loads such as bending, folding, and stretching. After delicate optimisation of the layered silicone/AgNW/silicone sandwich structure, a stretchable transparent electrode which can withstand 1000 cycles of 50% stretching-releasing with an exceptionally high stability and reversibility was fabricated. This structure can be used as a transparent strain sensor; it possesses a strong piezoresistivity with a gauge factor greater than 11.

Orthogonal Clickable Iron Oxide Nanoparticle Platform for Targeting, Imaging, and On-Demand Release.

PubMed

Guldris, Noelia; Gallo, Juan; García-Hevia, Lorena; Rivas, José; Bañobre-López, Manuel; Salonen, Laura M

2018-04-12

A versatile iron oxide nanoparticle platform is reported that can be orthogonally functionalized to obtain highly derivatized nanomaterials required for a wide variety of applications, such as drug delivery, targeted therapy, or imaging. Facile functionalization of the nanoparticles with two ligands containing isocyanate moieties allows for high coverage of the surface with maleimide and alkyne groups. As a proof-of-principle, the nanoparticles were subsequently functionalized with a fluorophore as a drug model and with biotin as a targeting ligand towards tumor cells through Diels-Alder and azide-alkyne cycloaddition reactions, respectively. The thermoreversibility of the Diels-Alder product was exploited to induce the on-demand release of the loaded molecules by magnetic hyperthermia. Additionally, the nanoparticles were shown to target cancer cells through in vitro experiments, as analyzed by magnetic resonance imaging. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bio-orthogonal Fluorescent Labelling of Biopolymers through Inverse-Electron-Demand Diels-Alder Reactions.

PubMed

Kozma, Eszter; Demeter, Orsolya; Kele, Péter

2017-03-16

Bio-orthogonal labelling schemes based on inverse-electron-demand Diels-Alder (IEDDA) cycloaddition have attracted much attention in chemical biology recently. The appealing features of this reaction, such as the fast reaction kinetics, fully bio-orthogonal nature and high selectivity, have helped chemical biologists gain deeper understanding of biochemical processes at the molecular level. Listing the components and discussing the possibilities and limitations of these reagents, we provide a recent snapshot of the field of IEDDA-based biomolecular manipulation with special focus on fluorescent modulation approaches through the use of bio-orthogonalized building blocks. At the end, we discuss challenges that need to be addressed for further developments in order to overcome recent limitations and to enable researchers to answer biomolecular questions in more detail. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

DOE PAGES

Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; ...

2015-11-14

In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not playmore » a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm 2.« less

Acidification and γ-aminobutyric acid independently alter kairomone-induced behaviour

PubMed Central

Cohen, Jonathan H.

2016-01-01

Exposure to high pCO2 or low pH alters sensation and behaviour in many marine animals. We show that crab larvae lose their ability to detect and/or process predator kairomones after exposure to low pH over a time scale relevant to diel pH cycles in coastal environments. Previous work suggests that acidification affects sensation and behaviour through altered neural function, specifically the action of γ-aminobutyric acid (GABA), because a GABA antagonist, gabazine, restores the original behaviour. Here, however, gabazine resulted in a loss of kairomone detection/processing, regardless of pH. Our results also suggest that GABAergic signalling is necessary for kairomone identification in these larvae. Hence, the mechanism for the observed pH effect varies from the original GABA hypothesis. Furthermore, we suggest that this pH effect is adaptive under diel-cycling pH. PMID:27703697

Movement, home range, and site fidelity of bluegills in a Great Plains Lake

USGS Publications Warehouse

Paukert, C.P.; Willis, D.W.; Bouchard, M.A.

2004-01-01

Little is known about the distribution, movement, and home ranges of bluegills Lepomis macrochirus in lentic environments. Therefore, the objectives of this study were to evaluate the seasonal and diel differences in movement rates, site fidelity, and home range of bluegills in a shallow, natural Great Plains lake. A total of 78 bluegills (200-273 mm total length) were implanted with radio transmitters in March and May 2000. Of these fish, 10 males and 10 females were randomly selected and located every 2 h during one 24-h period each month from April to September 2000. Bluegill movement peaked during midsummer: however, there was little difference in diel movements, suggesting relatively consistent movement throughout the 24-h period. Home range estimates (which included the 24-h tracking plus an additional six locations from the same fish located once per day for six consecutive days each month) ranged up to 172 ha, probably because only about half of the bluegills exhibited site fidelity during any month sampled. Bluegill movement did not appear to be strongly linked with water temperature, barometric pressure, or wind speed. These results suggest that bluegills move considerable distances and that many roam throughout this 332-ha shallow lake. However, diel patterns were not evident. Sampling bluegills in Great Plains lakes using passive gears (e.g., trap nets) may be most effective during the summer months, when fish are most active. Active sampling (e.g., electrofishing) may be more effective than the use of passive gears in spring and fall, when bluegills are less active.

A diels-alder modulated approach to control and sustain the release of dexamethasone and induce osteogenic differentiation of human mesenchymal stem cells

PubMed Central

Koehler, Kenneth C.; Alge, Daniel L.; Anseth, Kristi S.; Bowman, Christopher N.

2013-01-01

We report a new approach to controlled drug release based upon exploiting the dynamic equilibrium that exists between Diels-Alder reactants and products, demonstrating the release of a furan containing dexamethasone peptide (dex-KGPQG-furan) from a maleimide containing hydrogel. Using a reaction-diffusion model, the release kinetics were tuned to achieve sustained concentrations conducive to osteogenic differentiation of human mesenchymal stem cells (hMSCs). Efficacy was first demonstrated in a 2D culture model, in which dexamethasone release induced significant increases in alkaline phosphatase (ALP) activity and mineral deposition in hMSCs compared to a dexamethasone-free treatment. The results were similar to that observed with a soluble dexamethasone treatment. More dramatic differences were observed in 3D culture, where co-encapsulation of a dexamethasone releasing hydrogel depot within an hMSC-laden extracellular matrix mimetic poly(ethylene glycol) hydrogel resulted in a local and robust osteogenic differentiation. ALP activity reached levels that were up to six times higher than the dexamethasone free treatment. Interestingly, at 5 and 10 day time points, the ALP activity exceeded the dexamethasone positive control, suggesting a potential benefit of sustained release in 3D culture. After 21 days, substantial mineralization comparable to the positive control was also observed in the hydrogels. Collectively, these results demonstrate Diels-Alder modulated release as an effective and versatile new platform for controlled drug delivery that may prove especially beneficial for sustaining the release of low molecular weight molecules in hydrogel systems. PMID:23465826

Diel behavior of rearing fall Chinook salmon

USGS Publications Warehouse

Tiffan, Kenneth F.; Kock, Tobias J.; Skalicky, Joseph J.

2010-01-01

In fisheries science, habitat use is often inferred when fish are sampled or observed in a particular location. Physical habitat is typically measured where fish are found, and thus deemed important to habitat use. Although less common, a more informative approach is to measure or observe fish behavior within given habitats to more thoroughly assess their use of those locations. While this approach better reflects how fish use habitat, fish behavior can be difficult to quantify, particularly at night. For example, Tiffan and others (2002, 2006) were able to quantify habitat availability and characteristics that were important for rearing juvenile fall Chinook Salmon (Oncorhynchus tshawytscha) in the Hanford Reach of the Columbia River. The authors, however, could only speculate as to how juvenile salmon use habitat and respond to changes in water level fluctuations. Conversely, in this study we provide data on the diel activities of rearing juvenile wild fall Chinook Salmon which provides a better understanding of how fish “use” these rearing habitats. Diel behavior patterns are important because fish in the Hanford Reach are often stranded on shorelines when the water level rapidly recedes because of hydroelectric power generation at upriver dams (Nugent and others 2002; Anglin and others 2006). We hypothesize that juvenile salmon are at greater risk of stranding at night because they are less active and occupy habitat differently than during the day. We used underwater videography to collect behavioral information during the day and night to determine if juvenile fall Chinook Salmon are more susceptible to stranding when water level fluctuations occur at night.

Heat stress of two tropical seagrass species during low tides - impact on underwater net photosynthesis, dark respiration and diel in situ internal aeration.

PubMed

Pedersen, Ole; Colmer, Timothy D; Borum, Jens; Zavala-Perez, Andrea; Kendrick, Gary A

2016-06-01

Seagrasses grow submerged in aerated seawater but often in low O2 sediments. Elevated temperatures and low O2 are stress factors. Internal aeration was measured in two tropical seagrasses, Thalassia hemprichii and Enhalus acoroides, growing with extreme tides and diel temperature amplitudes. Temperature effects on net photosynthesis (PN ) and dark respiration (RD ) of leaves were evaluated. Daytime low tide was characterized by high pO2 (54 kPa), pH (8.8) and temperature (38°C) in shallow pools. As PN was maximum at 33°C (9.1 and 7.2 μmol O2  m(-2) s(-1) in T. hemprichii and E. acoroides, respectively), the high temperatures and reduced CO2 would have diminished PN , whereas RD increased (Q10 of 2.0-2.7) above that at 33°C (0.45 and 0.33 μmol O2  m(-2)  s(-1) , respectively). During night-time low tides, O2 declined resulting in shoot base anoxia in both species, but incoming water containing c. 20 kPa O2 relieved the anoxia. Shoots exposed to 40°C for 4 h showed recovery of PN and RD , whereas 45°C resulted in leaf damage. These seagrasses are 'living near the edge', tolerant of current diel O2 and temperature extremes, but if temperatures rise both species may be threatened in this habitat. © 2016 The Authors. New Phytologist © 2016 New Phytologist Trust.

Diel Patterns of Activity for Insect Pollinators of Two Oil Palm Species (Arecales : Arecaceae)

PubMed Central

Frérot, Brigitte; Poveda, Roberto; Louise, Claude; Beaudoin-Ollivier, Laurence

2017-01-01

The pollination of two oil palm species, Elaeis guineensis Jacquin and Elaeis oleifera Cortés (Arecales: Arecaceae), depends on a mutualistic relation with insects, which use male inflorescences as a brood site, and visits female inflorescences lured by the emitted odor, which is similar to that of males. Although the activity of visiting the inflorescences by these insects is critical for the adequate natural pollination of the host plant, their activity is poorly documented. In the present study, we determine the diel activity of two specialized pollinator weevils (Coleoptera: Curculionidae) on inflorescences of their respective host-palm: Elaeidobius kamerunicus Faust specialized on E. guineensis, and Grasidius hybridus O’Brien and Beserra specialized on E. oleifera. The average timing of activity was studied by using passive interception traps. Then the pattern and the duration were refined by using aspiration trapping within the active period for each insect species at the male and female inflorescences. All the experiments were conducted in an Ecuadorian oil palm plantation, located close to Amazonian forest. El. kamerunicus and G. hybridus were found to be the pollinators of E. guineensis and E. oleifera, respectively. The two species differed in their diel pattern of activity: E. kamerunicus was active in the morning and G. hybridus during a short period at dusk. For both palm species, insect visits were synchronous on both male and female inflorescences. The synchronicity is discussed as a strategy to maintain the relation mutualistic between partners. These findings increase our understanding of the oil palm pollination system. PMID:28365767

Synthesis of cyclopentadienyl capped polyethylene and subsequent block copolymer formation via hetero Diels-Alder (HDA) chemistry.

PubMed

Espinosa, Edgar; Glassner, Mathias; Boisson, Christophe; Barner-Kowollik, Christopher; D'Agosto, Franck

2011-09-15

In the current contribution it is demonstrated - for the first time - that poly(ethylene) (M(n) = 1,400 as well as 2,800 g  ·  mol(-1) , PDI = 1.2) can be readily equipped with highly reactive cyclopentadienyl (Cp) end groups. The Cp terminal poly(ethylene) can subsequently be reacted in an efficient hetero Diels-Alder (HDA) reaction with macromolecules (poly(isobornyl acrylate) (M(n) = 4,600 g  ·  mol(-1) , PDI = 1.10) and poly(styrene) (M(n) = 6,300 g  ·  mol(-1) , PDI = 1.13) featuring strongly electron withdrawing thiocarbonyl thio end groups, prepared via reversible addition fragmentation chain transfer (RAFT) polymerization employing benzylpyridin-2-yldithioformate (BPDF) as transfer agent. The resulting block copolymers have been analyzed via high-temperature size exclusion chromatography (SEC) as well as nuclear magnetic resonance (NMR) spectroscopy. The current system allows for the removal of the excess of the non-poly(ethylene) containing segment via filtration of the poly(ethylene)-containing block copolymer. However, the reaction temperatures need to be judiciously selected. Characterization of the generated block copolymers at elevated temperatures can lead - depending on the block copolymer type - to the occurrence of retro Diels-Alder processes. The present study thus demonstrates that RAFT-HDA ligation can be effectively employed for the generation of block copolymers containing poly(ethylene) segments. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diurnal Patterns of Heterotrophic and Autotrophic Soil Respiration in Maize and Switchgrass Bioenergy Cropping Systems

NASA Astrophysics Data System (ADS)

von Haden, A.; Marin-Spiotta, E.; Jackson, R. D.; Kucharik, C. J.

2016-12-01

A high proportion of carbon lost from terrestrial ecosystems occurs via soil CO2 respiration. Soil respiration is comprised of two contrasting sources: heterotrophic respiration (RH) from the decomposition of organic matter and autotrophic respiration (RA) from plant root metabolism. Since the two sources of soil respiration vary widely in their origin, the controls of each source are also likely to differ. However, the challenge of partitioning soil respiration sources in situ has limited our mechanistic understanding of RH and RA. Our objective was to evaluate the in situ diurnal controls of RH and RA in maize (Zea mays L.) and switchgrass (Panicum virgatum L.) bioenergy cropping systems. We hypothesized that both RH and RA would follow diurnal soil temperature trends, but that RA would also respond to diel patterns of photosynthetically active radiation (PAR). We also expected that diurnal soil respiration patterns would vary significantly within the growing season. We evaluated our hypothesis with six diurnal soil respiration campaigns during the 2015 and 2016 growing seasons at Arlington, WI, USA. RH showed clear oscillating diel trends, typically peaking in the mid-afternoon when near-surface soil temperatures were highest. Diurnal RA patterns were more nuanced than RH, but were generally highest in the late afternoon and showed the most pronounced diel trends during peak growing season in July. RA also tended to spike in concert with PAR, but this effect was much more prominent in maize than switchgrass. Continuing efforts will attempt to quantitatively separate the effects of soil temperature and PAR on RA.

Diel pattern of circadian clock and storage protein gene expression in leaves and during seed filling in cowpea (Vigna unguiculata).

PubMed

Weiss, Julia; Terry, Marta I; Martos-Fuentes, Marina; Letourneux, Lisa; Ruiz-Hernández, Victoria; Fernández, Juan A; Egea-Cortines, Marcos

2018-02-14

Cowpea (Vigna unguiculata) is an important source of protein supply for animal and human nutrition. The major storage globulins VICILIN and LEGUMIN (LEG) are synthesized from several genes including LEGA, LEGB, LEGJ and CVC (CONVICILIN). The current hypothesis is that the plant circadian core clock genes are conserved in a wide array of species and that primary metabolism is to a large extent controlled by the plant circadian clock. Our aim was to investigate a possible link between gene expression of storage proteins and the circadian clock. We identified cowpea orthologues of the core clock genes VunLHY, VunTOC1, VunGI and VunELF3, the protein storage genes VunLEG, VunLEGJ, and VunCVC as well as nine candidate reference genes used in RT-PCR. ELONGATION FACTOR 1-A (ELF1A) resulted the most suitable reference gene. The clock genes VunELF3, VunGI, VunTOC1 and VunLHY showed a rhythmic expression profile in leaves with a typical evening/night and morning/midday phased expression. The diel patterns were not completely robust and only VungGI and VungELF3 retained a rhythmic pattern under free running conditions of darkness. Under field conditions, rhythmicity and phasing apparently faded during early pod and seed development and was regained in ripening pods for VunTOC1 and VunLHY. Mature seeds showed a rhythmic expression of VunGI resembling leaf tissue under controlled growth chamber conditions. Comparing time windows during developmental stages we found that VunCVC and VunLEG were significantly down regulated during the night in mature pods as compared to intermediate ripe pods, while changes in seeds were non-significant due to high variance. The rhythmic expression under field conditions was lost under growth chamber conditions. The core clock gene network is conserved in cowpea leaves showing a robust diel expression pattern except VunELF3 under growth chamber conditions. There appears to be a clock transcriptional reprogramming in pods and seeds compared to leaves. Storage protein deposition may be circadian regulated under field conditions but the strong environmental signals are not met under artificial growth conditions. Diel expression pattern in field conditions may result in better usage of energy for protein storage.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burns, S. P.; Blanken, P. D.; Turnipseed, A. A.

Precipitation changes the physical and biological characteristics of an ecosystem. Using a precipitation-based conditional sampling technique and a 14 year data set from a 25 m micrometeorological tower in a high-elevation subalpine forest, we examined how warm-season precipitation affected the above-canopy diel cycle of wind and turbulence, net radiation R net, ecosystem eddy covariance fluxes (sensible heat H, latent heat LE, and CO 2 net ecosystem exchange NEE) and vertical profiles of scalars (air temperature T a, specific humidity q, and CO 2 dry mole fraction χ c). This analysis allowed us to examine how precipitation modified these variables frommore » hourly (i.e., the diel cycle) to multi-day time-scales (i.e., typical of a weather-system frontal passage). During mid-day we found the following: (i) even though precipitation caused mean changes on the order of 50–70 % to R net, H, and LE, the surface energy balance (SEB) was relatively insensitive to precipitation with mid-day closure values ranging between 90 and 110 %, and (ii) compared to a typical dry day, a day following a rainy day was characterized by increased ecosystem uptake of CO 2 (NEE increased by ≈ 10 %), enhanced evaporative cooling (mid-day LE increased by ≈ 30 W m –2), and a smaller amount of sensible heat transfer (mid-day H decreased by ≈ 70 W m –2). Based on the mean diel cycle, the evaporative contribution to total evapotranspiration was, on average, around 6 % in dry conditions and between 15 and 25 % in partially wet conditions. Furthermore, increased LE lasted at least 18 h following a rain event. At night, even though precipitation (and accompanying clouds) reduced the magnitude of R net, LE increased from ≈ 10 to over 20 W m –2 due to increased evaporation. Any effect of precipitation on the nocturnal SEB closure and NEE was overshadowed by atmospheric phenomena such as horizontal advection and decoupling that create measurement difficulties. Above-canopy mean χ c during wet conditions was found to be about 2–3 μmol mol –1 larger than χ c on dry days. This difference was fairly constant over the full diel cycle suggesting that it was due to synoptic weather patterns (different air masses and/or effects of barometric pressure). Lastly, the effect of clouds on the timing and magnitude of daytime ecosystem fluxes is described.« less

Passive Baited Sequential Fly Trap

USDA-ARS?s Scientific Manuscript database

Sampling fly populations associated with human populations is needed to understand diel behavior and to monitor population densities before and after control operations. Population control measures are dependent on the results of monitoring efforts as they may provide insight into the fly behavior ...

Stereocontrolled total syntheses of (±)-fawcettimine, (±)-lycoflexine, and (±)-lycoflexine N-oxide.

PubMed

Xu, Ke; Cheng, Bin; Li, Yun; Xu, Tingting; Yu, Cunming; Zhang, Jun; Ma, Zhiqiang; Zhai, Hongbin

2014-01-03

New stereocontrolled total syntheses of (±)-fawcettimine, (±)-lycoflexine, and (±)-lycoflexine N-oxide have been accomplished. The highlights include a one-pot annulation to construct the enedione and a microwave-promoted Diels-Alder reaction.

Contributive Research and Development

DTIC Science & Technology

1991-09-25

cyclopentadiene cracks down (evolves) at about 230 C by retro- Diels Alder reaction under ambient pressure, high pressure, or vacuum environments and the...block coagulation 3) lamination of extruded film 4) microwave drawing of extruded fiber. During processing of molecular composite solutions via wet

Hydrogen peroxide measurements in recreational marine bathing waters in Southern California, USA.

PubMed

Clark, Catherine D; De Bruyn, Warren J; Hirsch, Charlotte M; Jakubowski, Scott D

2010-04-01

Hydrogen peroxide (H(2)O(2)) was measured in the surf zone at 13 bathing beaches in Southern California, USA. Summer dry season concentrations averaged 122 +/- 38 nM with beaches with tide pools having lower levels (50-90 nM). No significant differences were observed for ebb waters at a salt marsh outlet vs. a beach (179 +/- 20 vs. 163 +/- 26 nM), and between ebb and flood tides at one site (171 +/- 24 vs. 146 +/- 42 nM). H(2)O(2) levels showed little annual variation. Diel cycling was followed over short (30 min; 24 h study) and long (d) time scales, with maximum afternoon concentration = 370 nM and estimated photochemical production rate of 44 nM h(-1). There was no correlation between the absorbance coefficient at 300 nm (used as a measure of chromophoric dissolved organic matter (CDOM) levels) and H(2)O(2). H(2)O(2) concentrations measured in this study are likely sufficient to inhibit fecal indicator bacteria in marine recreational waters through indirect photoinactivation. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Extreme diel dissolved oxygen and carbon cycles in shallow vegetated lakes.

PubMed

Andersen, Mikkel R; Kragh, Theis; Sand-Jensen, Kaj

2017-09-13

A common perception in limnology is that shallow lakes are homogeneously mixed owing to their small water volume. However, this perception is largely gained by downscaling knowledge from large lakes to their smaller counterparts. Here we show that shallow vegetated lakes (less than 0.6 m), in fact, undergo recurring daytime stratification and nocturnal mixing accompanied by extreme chemical variations during summer. Dense submerged vegetation effectively attenuates light and turbulence generating separation between warm surface waters and much colder bottom waters. Photosynthesis in surface waters produces oxygen accumulation and CO 2 depletion, whereas respiration in dark bottom waters causes anoxia and CO 2 accumulation. High daytime pH in surface waters promotes precipitation of CaCO 3 which is re-dissolved in bottom waters. Nocturnal convective mixing re-introduces oxygen into bottom waters for aerobic respiration and regenerated inorganic carbon into surface waters, which supports intense photosynthesis. Our results reconfigure the basic understanding of local environmental gradients in shallow lakes, one of the most abundant freshwater habitats globally. © 2017 The Author(s).

Diel and seasonal movement pattern of the dusky grouper Epinephelus marginatus inside a marine reserve.

PubMed

Koeck, Barbara; Pastor, Jérémy; Saragoni, Gilles; Dalias, Nicolas; Payrot, Jérôme; Lenfant, Philippe

2014-03-01

Temporal movement patterns and spawning behaviour of the dusky grouper Epinephelus marginatus were investigated using depth and temperature sensors combined to acoustic telemetry. Results showed that these fish are year-round resident, remaining inside the fully protected area of the marine reserve of Cerbère-Banyuls (65 ha) and display a diurnal activity pattern. Records from depth sensors revealed that groupers range inside small, distinct, and individual territories. Individual variations in habitat depth are only visible on a seasonal scale, i.e., between the spawning season and the rest of the year. In fact, during summer months when the seawater temperature exceeded 20 °C, tagged groupers made vertical spawning migrations of 4-8 m in amplitude. These vertical migrations are characteristic of the reproductive behaviour of dusky groupers, during which they release their gametes. The results are notable for the implementation of management rules in marine protected areas, such as reduced navigation speed, boating or attendance during spawning season. Copyright © 2013 Elsevier Ltd. All rights reserved.

Tropospheric OH and Cl levels deduced from non-methane hydrocarbon measurements in a marine site

NASA Astrophysics Data System (ADS)

Arsene, C.; Bougiatioti, A.; Kanakidou, M.; Bonsang, B.; Mihalopoulos, N.

2007-09-01

In situ continuous hourly measurements of C2-C8 non-methane hydrocarbons (NMHCS) have been performed from March to October 2006 at two coastal locations (natural and rural) on the island of Crete, in the Eastern Mediterranean. Well defined diel variations were observed for several short lived NMHCS (including ethene, propene, n-butane, n-pentane, n-hexane, 2-methyl-pentane). The daytime concentration of hydroxyl (OH) radicals estimated from these experimental data varied from 1.3×106 to ~4.0×106 radical cm-3, in good agreement with box-model simulations. In addition the relative variability of various hydrocarbon pairs (at least 7) was used to derive the tropospheric levels of Cl atoms. The Cl atom concentration has been estimated to range between 0.6×104 and 4.7×104 atom cm-3, in good agreement with gaseous hydrochloric acid (HCl) observations in the area. Such levels of Cl atoms can be of considerable importance for the oxidation capacity of the troposphere on a regional scale.

Thermal plasticity in young snakes: how will climate change affect the thermoregulatory tactics of ectotherms?

PubMed

Aubret, F; Shine, R

2010-01-15

Climate change will result in some areas becoming warmer and others cooler, and will amplify the magnitude of year-to-year thermal variation in many areas. How will such changes affect animals that rely on ambient thermal heterogeneity to behaviourally regulate their body temperatures? To explore this question, we raised 43 captive-born tiger snakes Notechis scutatus in enclosures that provided cold (19-22 degrees C), intermediate (19-26 degrees C) or hot (19-37 degrees C) thermal gradients. The snakes adjusted their diel timing of thermoregulatory behaviour so effectively that when tested 14 months later, body temperatures (mean and maximum), locomotor speeds and anti-predator behaviours did not differ among treatment groups. Thus, the young snakes modified their behaviour to compensate for restricted thermal opportunities. Then, we suddenly shifted ambient conditions to mimic year-to-year variation. In contrast to the earlier plasticity, snakes failed to adjust to this change, e.g. snakes raised at cooler treatments but then shifted to hot conditions showed a higher mean body temperature for at least two months after the onset of the new thermal regime. Hence, thermal conditions experienced early in life influenced subsequent thermoregulatory tactics; the mean selected temperature of a snake depended more upon its prior raising conditions than upon its current thermoregulatory opportunities. Behavioural plasticity thus allows snakes to adjust to suboptimal thermal conditions but this plasticity is limited. The major thermoregulatory challenge from global climate change may not be the shift in mean values (to which our young snakes adjusted) but the increased year-to-year variation (with which our snakes proved less able to deal).

Using air/water/sediment temperature contrasts to identify groundwater seepage locations in small streams

NASA Astrophysics Data System (ADS)

Karan, S.; Sebok, E.; Engesgaard, P. K.

2016-12-01

For identifying groundwater seepage locations in small streams within a headwater catchment, we present a method expanding on the linear regression of air and stream temperatures. Thus, by measuring the temperatures in dual-depth; in the stream column and at the streambed-water interface (SWI), we apply metrics from linear regression analysis of temperatures between air/stream and air/SWI (linear regression slope, intercept and coefficient of determination), and the daily mean temperatures (temperature variance and the average difference between the minimum and maximum daily temperatures). Our study show that using metrics from single-depth stream temperature measurements only are not sufficient to identify substantial groundwater seepage locations within a headwater stream. Conversely, comparing the metrics from dual-depth temperatures show significant differences so that at groundwater seepage locations, temperatures at the SWI, merely explain 43-75 % of the variation opposed to ≥91 % at the corresponding stream column temperatures. The figure showing a box-plot of the variation in daily mean temperature depict that at several locations there is great variation in the range the upper and lower loggers due to groundwater seepage. In general, the linear regression show that at these locations at the SWI, the slopes (<0.25) and intercepts (>6.5oC) are substantially lower and higher, while the mean diel amplitudes (<0.98oC) are decreased compared to remaining locations. The dual-depth approach was applied in a post-glacial fluvial setting, where metrics analyses overall corresponded to field measurements of groundwater fluxes deduced from vertical streambed temperatures and stream flow accretions. Thus, we propose a method reliably identifying groundwater seepage locations along streambed in such settings.

Identifying drivers of divergent methane fluxes from restored wetlands

NASA Astrophysics Data System (ADS)

Chamberlain, S.; Silver, W. L.; Anthony, T.; Hemes, K. S.; Oikawa, P.; Sturtevant, C.; Eichelmann, E.; Matthes, J. H.; Verfaillie, J. G.; Baldocchi, D. D.

2017-12-01

Restored wetlands in the Sacramento-San Joaquin Delta region of California are created, and actively managed, to reduce land subsidence and greenhouse gas (GHG) emissions from drained peatland agriculture. While these wetlands tend to be carbon sinks on a year-to-year basis, variation in methane (CH4) emissions determines whether sites are GHG sources or sinks. Two probable sources of CH4 flux variation across restored wetlands are soil carbon and iron content. These soil properties vary across the region and are a legacy of pre-drainage wetland geomorphology, where alluvium wetlands were mineral rich and carbon poor compared to adjacent peat accumulating sites. We explored drivers of CH4 flux variation from three restored wetlands using eddy covariance, data-driven analyses, and biogeochemical modeling to evaluate alternative hypotheses for observed flux differences. We observed significantly reduced annual CH4 fluxes from wetlands restored on alluvium soils compared to peat sites, and these differences were largest immediately following restoration and gradually reduced over the following three years. Model-based hypothesis testing demonstrates that long-term inhibition of methanogenesis by iron presence is the best explanation for these observations. Soil samplings conducted after four years of continuous inundation demonstrates significantly higher iron concentrations in the alluvium soils, of which 25-30% was in oxidized form capable of inhibiting CH4 production. Using information theory and wavelet analyses, we also demonstrate that CH4 fluxes from the alluvium wetland were decoupled from plant photosynthesis and transport at diel to multiday timescales, as expected when iron reduction inhibits rhizosphere methanogenesis. These findings demonstrate that iron presence is capable of attenuating ecosystem-scale wetland CH4 fluxes, and provide a basis for choosing future wetland restoration sites to minimize CH4 emissions.

Temporal and Spatial Comparisons of Underwater Sound Signatures of Different Reef Habitats in Moorea Island, French Polynesia.

PubMed

Bertucci, Frédéric; Parmentier, Eric; Berten, Laëtitia; Brooker, Rohan M; Lecchini, David

2015-01-01

As environmental sounds are used by larval fish and crustaceans to locate and orientate towards habitat during settlement, variations in the acoustic signature produced by habitats could provide valuable information about habitat quality, helping larvae to differentiate between potential settlement sites. However, very little is known about how acoustic signatures differ between proximate habitats. This study described within- and between-site differences in the sound spectra of five contiguous habitats at Moorea Island, French Polynesia: the inner reef crest, the barrier reef, the fringing reef, a pass and a coastal mangrove forest. Habitats with coral (inner, barrier and fringing reefs) were characterized by a similar sound spectrum with average intensities ranging from 70 to 78 dB re 1 μPa.Hz(-1). The mangrove forest had a lower sound intensity of 70 dB re 1 μPa.Hz(-1) while the pass was characterized by a higher sound level with an average intensity of 91 dB re 1 μPa.Hz(-1). Habitats showed significantly different intensities for most frequencies, and a decreasing intensity gradient was observed from the reef to the shore. While habitats close to the shore showed no significant diel variation in sound intensities, sound levels increased at the pass during the night and barrier reef during the day. These two habitats also appeared to be louder in the North than in the West. These findings suggest that daily variations in sound intensity and across-reef sound gradients could be a valuable source of information for settling larvae. They also provide further evidence that closely related habitats, separated by less than 1 km, can differ significantly in their spectral composition and that these signatures might be typical and conserved along the coast of Moorea.

Transpiration Driven Hydrologic Transport in vegetated shallow water environments: Implications on Diel and Seasonal Soil Biogeochemical Processes and System Management

NASA Astrophysics Data System (ADS)

Bachand, P.; Bachand, S. M.; Fleck, J.; Anderson, F.

2011-12-01

Hydrology arguably plays the most important role in biogeochemical cycling of mercury in wetlands and other shallow aquatic systems. CFSTR, PFR and non-ideal reactor models are oftentimes currently used to hydrologically assess these systems and to account for the fate, transport and cycling of constituents of concern (COC) with systems assumed to be non-leaky and with diffusion dominating soil transport. Yet a number of results in the literature imply transpiration drives soil transport: transpiration into the root zone is in the range of 50 - 75% of ET seasonally; gaseous emissions from aquatic systems show a diel pattern that tracks diel ET patterns; in long detention time aquatic systems ET is the largest sink for applied surface waters; and non-reactive tracers when applied to surface waters can find themselves in the root zone and within plants. All these findings strongly suggest transpiration driven infiltration into the root zone, is a significant hydrologic pathway for constituents and is an important transport mechanism. This paper examines the annual water budget for four shallow aquatic land uses in the Yolo Bypass, California: rice, wild rice, fallowed fields and wetlands. Results indicate that differences in hydrology between the fields, particularly the temporal nature of transpiration, play a significant role in mercury transformations and transport. During the irrigation period, fallowed fields discharged 6 cm of surface water (15% applied water), rice fields 31 - 43 cm (27 - 31% applied water), and wild rice fields 16 - 39 cm (15 - 31% applied water). Evapotranspiration rates were in the range of 120 - 130 cm/y for all land uses (i.e. rice, wild rice, fallowed fields and seasonal wetlands) except for the permanent wetland which was about 1/3 higher at about 170 cm/y. During the summer, approximately 50% of the applied surface water was drawn into the root zone to meet transpiration demands. Based upon results from our water budget and utilizing modified Peclet No. calculations, we quantified the relative importance of upward diffusion from the sediments and downward advection from transpiration as hydrologic transport mechanisms in the root zone. Transpiration driven infiltration moves water past the diffusive zone within 1 - 2 days in this system during the summer months. With the waning seasons, evapotranspiration diminishes until by winter diffusion dominates throughout the entire root zone. This model has great implications on the analyses of soil biogeochemical process in the root zone of shallow aquatic systems. Downward advection is a major transport mechanism into the root zone of shallow flooded aquatic systems and provides an important physical mechanism that drives variability in the seasonal and diel storage; release and cycling of COCs; and the creation of both a physical and chemical barrierd to upward diffusion of soil-borne COCs into the water column. Models that do not account for root zone interactions may not be able to capture diel and seasonal differences. Moreover, these interactions may lead to unanticipated environmental consequences as a result of cultural practices.

New Polybenzimidazole Architectures by Diels Alder Polymerization

DTIC Science & Technology

2012-02-14

stable organic polymers known.9 This class of polymers is aromatic with the heterocyclic benzimidazole group, a five membered imidazole ring...will allow benzimidazole ring systems to be prepared from the cycloaddition with an imidazole diene. The goals of the project included synthesis

MONITORING CYCLICAL AIR-WATER ELEMENTAL MERCURY EXCHANGE

EPA Science Inventory

Previous experimental work has demonstrated that elemental mercury evasion from natural water displays a diel cycle; evasion rates during the day can be two to three times evasion rates observed at night. A study with polychlorinated biphenyls (PCBS) found that diurnal PCB air/wa...

Catalytic asymmetric total synthesis of (+)-yohimbine.

PubMed

Mergott, Dustin J; Zuend, Stephan J; Jacobsen, Eric N

2008-03-06

The total synthesis of (+)-yohimbine was achieved in 11 steps and 14% overall yield. The absolute configuration was established through a highly enantioselective thiourea-catalyzed acyl-Pictet-Spengler reaction, and the remaining 4 stereocenters were set simultaneously in a substrate-controlled intramolecular Diels-Alder reaction.

Diel-Cycling Hypoxia in Northern Gulf of Mexico Estuaries: Impacts and Protection of Aquatic Life

EPA Science Inventory

Eutrophication of coastal ecosystems is a longstanding environmental concern, exacerbated by population growth and associated nutrient pollution, and ultimately resulting in increased incidence of hypoxia. Shallow and highly productive estuaries and embayments are particularly su...