Rates Of Nitrogen-Excretion By Species Of Mytilus (Bivalvia - Mollusca)

The results of experiments recorded by Bayne & Scullard (1977) confirmed earlier studies (Bayne, 1973) in describing a decline in the rate of oxygen uptake (Vo2) by Mytilus edulis during starvation, eventually reaching a steady-state value, called the standard rate of oxygen consumption. Earlier experiments had also shown that if such starved mussels were fed, oxygen uptake increased rapidly to a high level called the active rate of oxygen consumption (Thompson & Bayne, 1972; Bayne, Thompson & Widdows, 1973). Some of this increase in metabolic rate is undoubtedly due to an increased filtration rate that is stimulated by the presence of food (the ‘mechanical cost of feeding’ discussed by Bayne et al. 1976), and part is due to the ‘physiological costs of feeding’, which includes energy utilized in digestion and assimilation of the food, and energy that is lost during deamination and other catabolic processes that accompany digestion (Warren & Davis, 1967). Increases in metabolic rate associated with feeding have been called the specific dynamic action (SDA) of the ration (see Harper, 1971, for a discussion) or the apparent SDA (Beamish, 1974)5 and they have been related to aspects of protein metabolism (Krebs, 1964). This paper describes the results of some experiments designed to examine the relationships between SDA and ammonia excretion in Mytilus edulis L.

Apparent Specific Dynamic Action In Mytilus-Edulis L

The results of experiments recorded by Bayne & Scullard (1977) confirmed earlier studies (Bayne, 1973) in describing a decline in the rate of oxygen uptake (Vo2) by Mytilus edulis during starvation, eventually reaching a steady-state value, called the standard rate of oxygen consumption. Earlier experiments had also shown that if such starved mussels were fed, oxygen uptake increased rapidly to a high level called the active rate of oxygen consumption (Thompson & Bayne, 1972; Bayne, Thompson & Widdows, 1973). Some of this increase in metabolic rate is undoubtedly due to an increased filtration rate that is stimulated by the presence of food (the ‘mechanical cost of feeding’ discussed by Bayne et al. 1976), and part is due to the ‘physiological costs of feeding’, which includes energy utilized in digestion and assimilation of the food, and energy that is lost during deamination and other catabolic processes that accompany digestion (Warren & Davis, 1967). Increases in metabolic rate associated with feeding have been called the specific dynamic action (SDA) of the ration (see Harper, 1971, for a discussion) or the apparent SDA (Beamish, 1974)5 and they have been related to aspects of protein metabolism (Krebs, 1964). This paper describes the results of some experiments designed to examine the relationships between SDA and ammonia excretion in Mytilus edulis L.

Ocean-atmosphere trace gas exchange

The oceans contribute significantly to the global emissions of a number of atmospherically important volatile gases, notably those containing sulfur, nitrogen and halogens. Such gases play critical roles not only in global biogeochemical cycling but also in a wide range of atmospheric processes including marine aerosol formation and modification, tropospheric ozone formation and destruction, photooxidant cycling and stratospheric ozone loss. A number of marine emissions are greenhouse gases, others influence the Earth's radiative budget indirectly through aerosol formation and/or by modifying oxidant levels and thus changing the atmospheric lifetime of gases such as methane. In this article we review current literature concerning the physical, chemical and biological controls on the sea-air emissions of a wide range of gases including dimethyl sulphide (DMS), halocarbons, nitrogen-containing gases including ammonia (NH3), amines (including dimethylamine, DMA, and diethylamine, DEA), alkyl nitrates (RONO2) and nitrous oxide (N2O), non-methane hydrocarbons (NMHC) including isoprene and oxygenated (O)VOCs, methane (CH4) and carbon monoxide (CO). Where possible we review the current global emission budgets of these gases as well as known mechanisms for their formation and loss in the surface ocean.

Response of an Arctic Sediment Nitrogen Cycling Community to Increased CO2

Ocean acidification influences sediment/water nitrogen fluxes, possibly by impacting on the microbial process of ammonia oxidation. To investigate this further, undisturbed sediment cores collected from Ny Alesund harbour (Svalbard) were incubated with seawater adjusted to CO2 concentrations of 380, 540, 760, 1,120 and 3,000 μatm. DNA and RNA were extracted from the sediment surface after 14 days' exposure and the abundance of bacterial and archaeal ammonia oxidising (amoA) genes and transcripts quantified using quantitative polymerase chain reaction. While there was no change to the abundance of bacterial amoA genes, an increase to 760 μatm pCO2 reduced the abundance of bacterial amoA transcripts by 65 %, and this was accompanied by a shift in the composition of the active community. In contrast, archaeal amoA gene and transcript abundance both doubled at 3,000 μatm, with an increase in species richness also apparent. This suggests that ammonia oxidising bacteria and archaea in marine sediments have different pH optima, and the impact of elevated CO2 on N cycling may be dependent on the relative abundances of these two major microbial groups. Further evidence of a shift in the balance of key N cycling groups was also evident: the abundance of nirS-type denitrifier transcripts decreased alongside bacterial amoA transcripts, indicating that NO3 − produced by bacterial nitrification fuelled denitrification. An increase in the abundance of Planctomycete-specific 16S rRNA, the vastmajority of which grouped with known anammox bacteria, was also apparent at 3,000 μatm pCO2. This could indicate a possible shift from coupled nitrification–denitrification to anammox activity at elevated CO2.

Impacts of bioturbation on temporal variation in bacterial and archaeal nitrogen-cycling gene abundance in coastal sediments

In marine environments, macrofauna living in or on the sediment surface may alter the structure, diversity and function of benthic microbial communities. In particular, microbial nitrogen (N)-cycling processes may be enhanced by the activity of large bioturbating organisms. Here, we study the effect of the burrowing mud shrimp Upogebia deltaura upon temporal variation in the abundance of genes representing key N-cycling functional guilds. The abundance of bacterial genes representing different N-cycling guilds displayed different temporal patterns in burrow sediments in comparison with surface sediments, suggesting that the burrow provides a unique environment where bacterial gene abundances are influenced directly by macrofaunal activity. In contrast, the abundances of archaeal ammonia oxidizers varied temporally but were not affected by bioturbation, indicating differential responses between bacterial and archaeal ammonia oxidizers to environmental physicochemical controls. This study highlights the importance of bioturbation as a control over the temporal variation in nitrogen-cycling microbial community dynamics within coastal sediments.

Environmental hypoxia but not minor shell damage affects scope for growth and body condition in the blue mussel Mytilus edulis (L.)

The effects of short-term (7 d) exposure to environmental hypoxia (2.11 mg O-2 L-1; control: 6.96 mg O-2 L-1) and varying degrees of shell damage (1 or 2, 1 mm diameter holes; control: no holes) on respiration rate, clearance rate, ammonia excretion rate, scope for growth (SFG) and body condition index were investigated in adult blue mussels (Mytilus edulis). There was a significant hypoxia-related reduction in SFG (>6.70 to 0.92J g(-1) h(-1)) primarily due to a reduction in energy acquisition as a result of reduced clearance rates during hypoxia. Shell damage had no significant affect on any of the physiological processes measured or the SFG calculated. Body condition was unaffected by hypoxia or shell damage. In conclusion, minor physical damage to mussels had no effect on physiological energetics but environmental hypoxia compromised growth, respiration and energy acquisition presumably by reducing feeding rates.

Decadal reanalysis of biogeochemical indicators and fluxes in the North West European shelf-sea ecosystem

In this paper we present the first decadal reanalysis simulation of the biogeochemistry of the North West European shelf, along with a full evaluation of its skill and value. An error-characterized satellite product for chlorophyll was assimilated into a physical-biogeochemical model of the North East Atlantic, applying a localized Ensemble Kalman filter. The results showed that the reanalysis improved the model predictions of assimilated chlorophyll in 60% of the study region. Model validation metrics showed that the reanalysis had skill in matching a large dataset of in situ observations for ten ecosystem variables. Spearman rank correlations were significant and higher than 0.7 for physical-chemical variables (temperature, salinity, oxygen), ∼0.6 for chlorophyll and nutrients (phosphate, nitrate, silicate), and significant, though lower in value, for partial pressure of dissolved carbon dioxide (∼0.4). The reanalysis captured the magnitude of pH and ammonia observations, but not their variability. The value of the reanalysis for assessing environmental status and variability has been exemplified in two case studies. The first shows that between 340,000-380,000 km2 of shelf bottom waters were oxygen deficient potentially threatening bottom fishes and benthos. The second application confirmed that the shelf is a net sink of atmospheric carbon dioxide, but the total amount of uptake varies between 36-46 Tg C yr−1 at a 90% confidence level. These results indicate that the reanalysis output dataset can inform the management of the North West European shelf ecosystem, in relation to eutrophication, fishery, and variability of the carbon cycle.

Insight into the key aspects of the regeneration process in the NOx storage reduction (NSR) reaction probed using fast transient kinetics coupled with isotopically labelled (NO)-N-15 over Pt and Rh-containing Ba/Al2O3 catalysts

For the first time, the coupling of fast transient kinetic switching and the use of an isotopically labelled reactant (15NO) has allowed detailed analysis of the evolution of all the products and reactants involved in the regeneration of a NOx storage reduction (NSR) material. Using realistic regeneration times (ca. 1 s) for Pt, Rh and Pt/Rh-containing Ba/Al2O3 catalysts we have revealed an unexpected double peak in the evolution of nitrogen. The first peak occurred immediately on switching from lean to rich conditions, while the second peak started at the point at which the gases switched from rich to lean. The first evolution of nitrogen occurs as a result of the fast reaction between H2 and/or CO and NO on reduced Rh and/or Pt sites. The second N2 peak which occurs upon removal of the rich phase can be explained by reaction of stored ammonia with stored NOx, gas phase NOx or O2. The ammonia can be formed either by hydrolysis of isocyanates or by direct reaction of NO and H2.

The study highlights the importance of the relative rates of regeneration and storage in determining the overall performance of the catalysts. The performance of the monometallic 1.1%Rh/Ba/Al2O3 catalyst at 250 and 350 °C was found to be dependent on the rate of NOx storage, since the rate of regeneration was sufficient to remove the NOx stored in the lean phase. In contrast, for the monometallic 1.6%Pt/Ba/Al2O3 catalyst at 250 °C, the rate of regeneration was the determining factor with the result that the amount of NOx stored on the catalyst deteriorated from cycle to cycle until the amount of NOx stored in the lean phase matched the NOx reduced in the rich phase. On the basis of the ratio of exposed metal surface atoms to total Ba content, the monometallic 1.6%Pt/Ba/Al2O3 catalyst outperformed the Rh-containing catalysts at 250 and 350 °C even when CO was used as a reductant.

Insight into association reactions on metal surfaces: Density-functional theory studies of hydrogenation reactions on Rh(111)

Hydrogenation reaction, as one of the simplest association reactions on surfaces, is of great importance both scientifically and technologically. They are essential steps in many industrial processes in heterogeneous catalysis, such as ammonia synthesis (N-2+3H(2)-->2NH(3)). Many issues in hydrogenation reactions remain largely elusive. In this work, the NHx (x=0,1,2) hydrogenation reactions (N+H-->NH, NH+H-->NH2 and NH2+H-->NH3) on Rh(111) are used as a model system to study the hydrogenation reactions on metal surfaces in general using density-functional theory. In addition, C and O hydrogenation (C+H-->CH and O+H-->OH) and several oxygenation reactions, i.e., C+O, N+O, O+O reactions, are also calculated in order to provide a further understanding of the barrier of association reactions. The reaction pathways and the barriers of all these reactions are determined and reported. For the C, N, NH, and O hydrogenation reactions, it is found that there is a linear relationship between the barrier and the valency of R (R=C, N, NH, and O). Detailed analyses are carried out to rationalize the barriers of the reactions, which shows that: (i) The interaction energy between two reactants in the transition state plays an important role in determining the trend in the barriers; (ii) there are two major components in the interaction energy: The bonding competition and the direct Pauli repulsion; and (iii) the Pauli repulsion effect is responsible for the linear valency-barrier trend in the C, N, NH, and O hydrogenation reactions. For the NH2+H reaction, which is different from other hydrogenation reactions studied, the energy cost of the NH2 activation from the IS to the TS is the main part of the barrier. The potential energy surface of the NH2 on metal surfaces is thus crucial to the barrier of NH2+H reaction. Three important factors that can affect the barrier of association reactions are generalized: (i) The bonding competition effect; (ii) the local charge densities of the reactants along the reaction direction; and (iii) the potential energy surface of the reactants on the surface. The lowest energy pathway for a surface association reaction should correspond to the one with the best compromise of these three factors. (C) 2003 American Institute of Physics.

Formation of NH4[Hg-3(NH)(2)](NO3)(3) and transformation to [Hg2N](NO3)

NH4[Hg-3(NH)(2)](NO3)(3) (1) and [Hg2N](NO3) (2) are obtained from cone. aqueous ammonia solutions of Hg(NO3)(2) at ambient temperature and under hydrothermal conditions at 180 degreesC, respectively, as colourless and dark yellow to light brown single crystals. The crystal structures {NH4[Hg-3(NH)(2)](NO3)(3): cubic, P4(I)32, a = 1030.4(2) pm, Z = 4, R-all = 0.028; [Hg2N](NO3): tetragonal, P4(3)2(1)2, a = 1540.4(1), c = 909.8(1) pm, Z = 4, R-all = 0.054} have been determined from single crystal data. Both exhibit network type structures in which [HNHg3] and [NHg4] tetrahedra of the partial structures of 1 and 2 are connected via three and four vertices, respectively. 1 transforms at about 270 degreesC in a straightforward reaction to 2 whereby the decomposition products of NH4NO3 are set free. 2 decomposes at about 380 degreesC forming yellow HgO. Most certainly, I is identical with a mineral previously analyzed as

[Ag(NH3)(2)]ClO4: Crystal structures, phase transition, and vibrational spectra

[Ag(NH3)(2)](ClO4) is obtained from a solution of AgClO4 in cone. ammonia as colourless single crystals (orthorhombic, Pnmn, Z = 4, a = 795.2(1) pm, b 617.7(1) pm, c = 1298.2(2) pm, R-all = 0.0494). The structure consists of linearly coordinated cations, [Ag(NH3)(2)](+), stacked in a staggered conformation and of tetrahedral (ClO4)(-) anions. A first order phase transition was observed between 210 and 200 K and the crystal structure of the low-temperature modification (monoclinic. P2/m, Z = 4, a = 789.9(5) pm, b = 604.1(5) pm, c = 1290.4(5) pm, beta = 97.436(5)degrees, at 170 K, R-all = 0.0636) has also been solved. Spectroscopic investigations (IR/Raman) have been carried out and the assignment of the spectra is discussed.

Self-potential signatures associated with an injection experiment at an in situ biological permeable reactive barrier

Strategies available to evaluate the performance of in situ permeable reactive barriers are currently not well developed and often rely on fluid and media sampling directly from the permeable reactive barrier (PRB). Here, we investigate the utility of the self-potential (SP) method as a technique to monitor in situ PRB performance. Our field study was conducted at in situ biological PRB in Portadown, Northern Ireland, UK, which was emplaced to assist in the remediation of groundwater contamination (e.g., hydrocarbons, ammonia) that resulted from the operations and waste disposal practices of a former gasworks. Borehole SP measurements were collected during the injection of contaminant groundwater slugs in an attempt to monitor/detect the response of the microbial activity associated with the breakdown of the added contaminants into the PRB. In addition, an uncontaminated groundwater slug was injected into a different portion of the PRB as a ‘control’ and SP measurements were collected for comparison to the SP response of the contaminant slugs. The results of the SP signals due to the contaminant injections show that the magnitude of the response was relatively small (<10 mV) yet showed a consistent decrease during both contaminant injections. The net decrease in SP recorded during the contaminant injections slowly rebounded to near background values through ~44 hours post-injection. The SP response during the uncontaminated injection showed a slight, albeit negligible (within the margin of error), 1 mV increase in the measured SP signals, in contrast to the contaminant injections. The results of the SP signals recorded from the uncontaminated groundwater injection also persisted through a period of ~47 hours after injection but show a net increase in SP relative to pre-injection values. Based on the difference in SP response between the contaminated and uncontaminated injections, we suggest that the responses are likely to be the result of differences in the chemistry of the injection types (contaminated versus uncontaminated) and in situ groundwater. We argue that the SP signals associated with the contaminated injections are dominated by diffusion (electrochemical) potential, possibly enhanced by a microbial effect. While the results of our investigation show a consistent SP response associated with the contaminant injections that is dominated by diffusional effects, further studies are required in order to better understand the effect of microbial activity on SP signals and the potential utility for the SP method to detect/monitor changes that may be indicative of biological PRB performance.

Synthesis of the alkaloids hopromine, hoprominol and hopromalinol, using transamidation methods.

Synthesis of the unsym. Homalium alkaloids hopromine (I, R = H, R1 = pentyl), hoprominol (I, R = OH, R1 = pentyl) and hopramalinol (I, R = OH, R1 = Ph), in diastereoisomeric mixt. form, is reported. The component eight-membered azalactams are first prepd. N-(3-halogenopropyl)-4-pentyl- and 4-heptylazetidin-2-ones are aminated and ring expanded in liq. ammonia to give, after reductive methylation, the corresponding 4-alkyl-5-methyl-1,5-diazacyclooctan-2-ones. Synthesis of the 4-(2-hydroxyheptyl)-5-methyl-1,5-diazacyclooctan-2-one required for hoprominol and hopromalinol is carried out via 4-allyl ?-lactam ring expansion to the eight-membered 4-allylazalactam, followed by methylation, epoxidn. and epoxide opening with lithium dibutylcuprate. A similar epoxidn.-cuprate sequence was carried out on the epoxypropyl ?-lactam, as its N-tert-butyldimethylsilyl deriv., and led to a convenient copper-catalyzed N- to O-migration of the protection; this migration is examd. Alkylation gave O-tert-butyldimethylsilyl-protected N-(3-chloropropyl)-4-(2-hydroxyheptyl)azetidin-2-one which could be aminated and transamidated in excellent yield, to give, after methylation, a superior sequence to the required eight-membered hydroxy azalactam. Although satisfactory for attachment of the first azalactam unit, a dibromobutane coupling system proved unreactive for the second. Couplings with unmethylated, methylated, and benzyloxycabronyl-protected azalactams were examd. using (E)-1,4-dibromobutene and (Z)-1,4-dichlorobutene as the bridging unit. Employing the latter, coupling the first N-methylated azalactam with potassium bis(trimethylsilyl)amide as the base, and then the second with bis(trimethylsilyl)amide-sodium hydride as the base system, provided a satisfactory synthetic outcome. Hydrogenation under acidic conditions gave the unsym. structures hopromine, hoprominol and hopromalinol, as well as the more simple and sym. alkaloid, homaline.

Use of microtechnologies for intensifying industrial processes

The use of new technologies based on microstructured reactors in industrial processes, including the obtainment of hydrogen peroxide, the catalytic oxidation of ammonia, the utilization of rocket fuels, fine organic synthesis, polymerization, and phase transfer catalysis, were considered. The transition to microtechnologies considerably increases the performance of the process; at the same time, the product yield increases as compared with periodically operating reactors, which allows for a reduction of costs at the separation stage of the reaction mixture and the extraction of the reaction products.

A survey of molecular line emission towards ultracompact HII regions

We have used the JCMT to survey molecular line emission towards 14 ultracompact HII regions (G5.89, G9.62, G10.30, G10.47, G12.21, G13.87, G29.96, G31.41, G34.26, G43.89, G45.12, G45.45, G45.47, and G75.78). For each source, we observed up to ten 1 GHz bands between 200 and 350 GHz, covering lines of more than 30 species including multiple transitions of CO isotopes, CH3OH, CH3CCH, CH3CN and HCOOCH3, and sulphuretted molecules. The number of transitions detected varied by a factor of 20 between sources; which were chosen following observations of high-excitation ammonia (Cesaroni et al. 1994a) and methyl cyanide (Olmi et al. 1993). In half our sample (the line-poor sources), only (CO)-O-17: (CO)-O-18, SO, (CS)-S-34 and CH3OH were detected. In the line-rich sources, we detected over 150 lines, including high excitation lines of CH3CN, HCOOCH3; C2H5CN, CH3OH, and CH3CCH. We have calculated the physical conditions of the molecular gas. To reproduce the emission from the line-rich sources requires both a hot, dense compact core and an ambient cloud consisting of less dense, cooler gas. The hot cores, which are less than 0.1 pc in size; reach densities of at least 10(8) cm(-3) and temperatures of more than 80 K. The line-poor sources can be modelled without a hot core by a 20-30 K, 10(5) cm(-3) cloud. We find no correlation between the size of the HII region and the current physical conditions in the molecular environment. A comparison with chemical models (Millar et al. 1997) confirms that grain surface chemistry is important in hot cores.