998 resultados para excess nitrogen
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We report synthesis, spectroscopic characterization, and thermal analysis of zinc acetylacetonate complex adducted by nitrogen donor ligands, such as pyridine, bipyridine, and phenanthroline. The pyridine adducted complex crystallizes to monoclinic crystal structure, whereas other two adducted complexes have orthorhombic structure. Addition of nitrogen donor ligands enhances the thermal property of these complexes as that with parent metal-organic complex. Zinc acetylacetonate adducted with pyridine shows much higher volatility (106 degrees C), decomposition temperature (202 degrees C) as that with zinc acetylacetonate (136 degrees C, 220 degrees C), and other adducted complexes. All the adducted complexes are thermally stable, highly volatile and are considered to be suitable precursors for metal organic chemical vapor deposition. The formation of these complexes is confirmed by powder X-ray diffraction, Fourier transform infrared spectroscopy, mass spectroscopy, and elemental analysis. The complexes are widely used as starting precursor materials for the synthesis of ZnO nanostructures by microwave irradiation assisted coating process. (c) 2015 Elsevier B.V. All rights reserved.
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Ultralight and macroporous three-dimensional reduced graphene oxide (rGO) foams are prepared by lyophilization (freeze-drying) technique to avoid a conventional template method. This method allows tailoring the porosity of the foams by varying the weight percentages of graphene oxide dispersions in water. Three different rGO foams of 0.2, 0.5 and 1.0 wt% are used for NO2 sensing. Sensing response from the tailored structure of rGO is found to be directly related to the density. A maximum of 20% sensing response is observed for a higher porosity of the structure, better than the known results so far on graphene foams in the literature. (C) 2015 Elsevier B.V. All rights reserved.
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Oxidative stress due to excessive accumulation of reactive oxygen or nitrogen species in the brain as seen in certain neurodegenerative diseases can have deleterious effects on neurons. Hydrogen peroxide, endogenously generated in neurons under normal physiological conditions, can produce an excess of hydroxyl radical via a Fenton mediated mechanism. This may induce acute oxidative injury if not scavenged or removed effectively by antioxidants. There are several biochemical assay methods to estimate oxidative injury in cells; however, they do not provide information on the biochemical changes as the cells get damaged progressively under oxidative stress. Raman microspectroscopy offers the possibility of real time monitoring of the chemical composition of live cells undergoing oxidative stress under physiological conditions. In the present study, a hippocampal neuron coculture was used to observe the acute impact of hydroxyl radicals generated by hydrogen peroxide in the presence of Fe2+ (Fenton reaction). Raman peaks related to nucleic acids (725, 782, 1092, 1320, 1340, 1420, and 1576 cm(-1)) showed time-dependent changes over the experimental period (60 mm), indicating the breakdown of the phosphodiester backbone as well as nuclear bases. Interestingly, ascorbic acid (a potent antioxidant) when cotreated with Fenton reactants showed protection of cells as inferred from the Raman spectra, presumably by scavenging hydroxyl radicals. Little or no change in the Raman spectra was observed for untreated control cells and for cells exposed to Fe2+ only, H2O2 only, and ascorbate only. A live dead assay study also supported the current observations. Hence, Raman microspectroscopy has the potential to be an excellent noninvasive tool for early detection of oxidative stress that is seen in neurodegenerative diseases.
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Electronically nonadiabatic decomposition pathways of guanidium triazolate are explored theoretically. Nonadiabatically coupled potential energy surfaces are explored at the complete active space self-consistent field (CASSCF) level of theory. For better estimation of energies complete active space second order perturbation theories (CASPT2 and CASMP2) are also employed. Density functional theory (DFT) with B3LYP functional and MP2 level of theory are used to explore subsequent ground state decomposition pathways. In comparison with all possible stable decomposition products (such as, N-2, NH3, HNC, HCN, NH2CN and CH3NC), only NH3 (with NH2CN) and N-2 are predicted to be energetically most accessible initial decomposition products. Furthermore, different conical intersections between the S-1 and S-0 surfaces, which are computed at the CASSCF(14,10)/6-31G(d) level of theory, are found to play an essential role in the excited state deactivation process of guanidium triazolate. This is the first report on the electronically nonadiabatic decomposition mechanisms of isolated guanidium triazolate salt. (C) 2015 Elsevier B.V. All rights reserved.
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We report a facile synthesis of three-dimensional (3D) nanodendrites of Pd nanoparticles (NPs) and nitrogen-doped carbon NPs (N-CNPs) by electroless deposition of Pd2+ ions. N-CNPs being an electron-enriched material act as a reducing agent. Moreover, the availability of a variety of nitrogen species in N-CNPs promotes the open arm structure as well as stabilizes the oriented 3D assembly of primary Pd NPs. The dendrites exhibit superior catalytic activity for methanol (0.5 M) oxidation in alkaline media (1 M NaOH) which is ascribed to the large electrochemical active surface area and the enhanced mass activity with repeated use. Further mass activity improvement has been realized after acid-treatment of dendrites which is attributed to the increment in the -OH group. The dendrites show higher mass activity (J(f) similar to 653 A g(-1)) in comparison with a commercial Pt-carbon/Pd-carbon (Pt-C/Pd-C) catalyst (J(f) similar to 46 and 163 A g(-1), respectively), better operational stability, superior CO tolerance with I-f/I-b (similar to 3.7) over a commercial Pt-C/Pd-C catalyst (I-f/I-b similar to 1.6 and 1.75, respectively) and may serve as a promising alternative to commercial Pt-C catalysts for anode application in alkaline fuel cells. To ensure the adaptability of our 3D-nanodendrites for other catalytic activities, we studied 4-nitrophenol reduction at room temperature. The 3D-nanodendrites show excellent catalytic activity toward 4-nitrophenol reduction, as well.
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We study an s-channel resonance R as a viable candidate to fit the diboson excess reported by ATLAS. We compute the contribution of the similar to 2 TeV resonance R to semileptonic and leptonic final states at the 13 TeV LHC. To explain the absence of an excess in the semileptonic channel, we explore the possibility where the particle R decays to additional light scalars X, X or X, Y. A modified analysis strategy has been proposed to study the three-particle final state of the resonance decay and to identify decay channels of X. Associated production of R with gauge bosons has been studied in detail to identify the production mechanism of R. We construct comprehensive categories for vector and scalar beyond-standard-model particles which may play the role of particles R, X, Y and find alternate channels to fix the new couplings and search for these particles.
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The behaviour of gaseous chlorine and alkali metals of three sorts of biomass (Danish straw, Swedish wood, and sewage sludge) in combustion or gasification is investigated by the chemical equilibrium calculating tool. The ranges of temperature, air-to-fuel ratio, and pressure are varied widely in the calculations (T=400-1800 K, gimel=0-1.8, and P=0.1-2.0 MPa). Results show that the air excess coefficient only has less significant influence on the release of gaseous chlorine and potassium or sodium during combustion. However, in biomass gasification, the influence of the air excess coefficient is very significant. Increasing air excess coefficient enhances the release of HCl(g), KOH(g), or NaOH(g) as well as it reduces the formation of KCl(g), NaCl(g), K(g), or Na(g). In biomass combustion or straw and sludge gasification, increasing pressure enhances the release of HCl(g) and reduces the amount of KCI(g), NaCl(g), KCI(g), or NaOH(g) at high temperatures. However, during wood gasification, the pressure enhances the formation of KOH(g) and KCI(g) and reduces the release of K(g) and HCl(g) at high temperatures. During wood and sewage sludge pyrolysis, nitrogen addition enhances the formation of KCN(g) and NaCN(g) and reduces the release of K(g) and Na(g). Kaolin addition in straw combustion may enhance the formation of potassium aluminosilicate in ash and significantly reduces the release of KCl(g) and KOH(g) and increases the formation of HCl(g).
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The majority of attempts to synthesize the theoretically predicted superhard phase β-C3N4 have been driven towards the use of techniques which maximize both the carbon sp3 levels and the amount of nitrogen incorporated within the film. However, as yet no attempt has been made to understand the mechanism behind the resultant chemical sputter process and its obvious effect upon film growth. In this work, however, the chemical sputtering process has been investigated through the use of an as-deposited tetrahedrally bonded amorphous carbon film with a high density nitrogen plasma produced using an rf-based electron cyclotron wave resonance source. The results obtained suggested the presence of two distinct ion energy dependent regimes. The first, below 100 eV, involves the chemical sputtering of carbon from the surface, whereas the second at ion energies in excess of 100 eV exhibits a drop in sputter rate associated with the subplantation of nitrogen within the carbon matrix. Furthermore, as the sample temperature is increased there is a concomitant decrease in sputter rate suggesting that the rate is controlled by the adsorption and desorption of additional precursor species rather than the thermal desorption of CN. A simple empirical model has been developed in order to elucidate some of the primary reactions involved in the sputter process. Through the incorporation of various previously determined experimental parameters including electron temperature, ion current density, and nitrogen partial pressure the results indicated that molecular nitrogen physisorbed at the ta-C surface was the dominant precursor involved in the chemical sputter process. However, as the physisorption enthalpy of molecular nitrogen is low this suggests that activation of this molecular species takes place only through ion impact at the surface. The obtained results therefore provide important information for the modeling and growth of high density carbon nitride. © 2001 American Institute of Physics.
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Structural changes induced by the incorporation of nitrogen into ta-C : H films have been studied by Electron Energy Loss Spectroscopy, X-Ray Photoelectron Spectroscopy, Fourier Transformed Infrared Spectroscopy and Ultraviolet-Visible Spectroscopy. ta-C:H films have been synthesised using a low pressure Electron Cyclotron Wave Resonance (ECWR) source which provides a plasma beam with a high degree of ionisation and dissociation. Nitrogen was incorporated by adding N2 to the C2H2 plasma used for the deposition of ta-C : H films. The N/C atomic ratio in the films rises rapidly until the N2/C2H2 gas ratio reaches three, and then increases more gradually, while the deposition rate decreases steeply. Chemical sputtering of the forming films and the formation of molecular nitrogen within the films limit the maximum nitrogen content to about N/C = 0.6. For low nitrogen content the films retain their diamond-like properties, however as N/C atomic ratio increases, a polymeric-like material is formed, with >C=N- structures and terminating C=N and NH groups that decrease the connectivity of the network.
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Wage stickiness is incorporated to a New-Keynesian model with variable capital to drive endogenous unemployment uctuations de ned as the log di¤erence between aggregate labor supply and aggregate labor demand. We estimated such model using Bayesian econometric techniques and quarterly U.S. data. The second-moment statistics of the unemployment rate in the model give a good t to those observed in U.S. data. Our results also show that wage-push shocks, demand shifts and monetary policy shocks are the three major determinants of unemployment fl uctuations. Compared to an estimated New-Keynesian model without unemployment (Smets and Wouters, 2007): wage stickiness is higher, labor supply elasticity is lower, the slope of the New-Keynesian Phillips curve is flatter, and the importance of technology innovations on output variability increases.
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Waterhyacinth (Eichhornia crassipes(Mart.) Solms), is a serious problem in the Sacramento Delta. Two weevil species (Neochetina bruchi Hustache and N. eichhorniae Warner) have been introduced as biological control agents. The purpose of this study was to test the hypothesis that nitrogen (N) in the tissue of waterhyacinth was not sufficient to support weevil growth and reproduction. Because it grows better on plants with high N content and because it has a greater impact on the growth of high N plants, N. bruchi may be a more effective biological control agent in the Sacramento Delta.
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In selecting an excess temperature at which to operate a power plant cooling system it has been customary to consider only thermal stresses and to use the ratio of the number of organisms killed to the number of organisms entrained. This frequently leads to the selection of a low excess temperature, AT, which, in turn, requires a large volume flow of cooling water. When mortalities due to physical and chemical stresses are included and the total number of entrained organisms killed is taken as the measure of the environmental damage, it becomes evident that the choice of a low excess temperature is seldom, if ever, best.
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Rice cultivation at any level in the Sacramento–San Joaquin Delta (existing or expanded) compels the need to quantify surface and subsurface loads of dissolved organic carbon (DOC), disinfection byproduct precursors (DBPPs) and nitrogen. This information can be used to develop Best Management Practices (BMPs) to reduce export of these constituents in order to improve drinking water quality. Although rice cultivation in the Delta is relatively limited, several factors outside of this research could contribute to increased rice acreage in the Delta: • Recently developed rice varieties seem more suitable for the Delta climate than earlier varieties which required warmer conditions; • Previous economic analyses (Appendix A.10) suggest rice is more profitable than corn, a dominant land use in the Delta; • Recent studies on wetlands at Twitchell Island suggest rice production can help mitigate oxidative subsidence (Miller et al. 2000); • The different oxidative states that result from flooding in rice as compared to those found in crops that require drained soils may help control crop specific weeds and nematodes when rice is incorporated into a crop rotation; and • Providing flooded conditions during a greater part of the year than other crops may benefit water birds. ... (PDF contains 249 pages)
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Executive Summary: The western National Coastal Assessment (NCA-West) program of EPA, in conjunction with the NOAA National Ocean Service (NOS), conducted an assessment of the status of ecological condition of soft sediment habitats and overlying waters along the western U.S. continental shelf, between the target depths of 30 and 120 m, during June 2003. NCA-West and NOAA/NOS partnered with the West Coast states (Washington (WA), Oregon (OR), and California (CA)), and the Southern California Coastal Water Research Project (SCCWRP) Bight ’03 program to conduct the survey. A total of 257 stations were sampled from Cape Flattery, WA to the Mexican border using standard methods and indicators applied in previous coastal NCA projects. A key study feature was the incorporation of a stratified-random sampling design with stations stratified by state and National Marine Sanctuary (NMS) status. Each of the three states was represented by at least 50 random stations. There also were a total of 84 random stations located within NOAA’s five NMSs along the West Coast including the Olympic Coast NMS (OCNMS), Cordell Bank NMS (CBNMS), Gulf of Farallones NMS (GFNMS), Monterey Bay NMS (MBNMS), and Channel Islands NMS (CINMS). Collection of flatfish via hook-and-line for fish-tissue contaminant analysis was successful at 50 EMAP/NCA-West stations. Through a collaboration developed with the FRAM Division of the Northwest Fisheries Science Center, fish from an additional 63 stations in the same region and depth range were also analyzed for fish-tissue contaminants. Bottom depth throughout the region ranged from 28 m to 125 m for most stations. Two slightly deeper stations from the Southern California Bight (SCB) (131, 134 m) were included in the data set. About 44% of the survey area had sediments composed of sands (< 20% silt-clay), about 47% was composed of intermediate muddy sands (20-80% silt-clay), and about 9% was composed of muds (> 80% silt-clay). The majority of the survey area (97%) had relatively low percent total organic carbon (TOC) levels of < 2%, while a small portion (< 1%) had high TOC levels (> 5%), in a range potentially harmful to benthic fauna. Salinity of surface waters for 92% of the survey area were > 31 psu, with most stations < 31 psu associated with the Columbia River plume. Bottom salinities ranged only between 31.6 and 34.4 psu. There was virtually no difference in mean bottom salinities among states or between NMS and non-NMS stations. Temperatures of surface water (range 8.5 -19.9 °C) and bottom water (range 5.8 -14.7 °C) averaged several degrees higher in CA in comparison to WA and OR. The Δσt index of watercolumn stratification indicated that about 31% of the survey area had strong vertical stratification of the water column. The index was greatest for waters off WA and lowest for CA waters. Only about 2.6 % of the survey area had surface dissolved oxygen (DO) concentrations ≤ 4.8 mg/L, and there were no values below the lower threshold (2.3 mg/L) considered harmful to the survival and growth of marine animals. Surface DO concentrations were higher in WA and OR waters than in CA, and higher in the OC NMS than in the CA sanctuaries. An estimated 94.3% of the area had bottom-water DO concentrations ≤ 4.8 mg/L and 6.6% had concentrations ≤ 2.3 mg/L. The high prevalence of DO from 2.3 to 4.8 mg/L (85% of survey area) is believed to be associated with the upwelling of naturally low DO water across the West Coast shelf. Mean TSS and transmissivity in surface waters (excluding OR due to sample problems) were slightly higher and lower, respectively, for stations in WA than for those in CA. There was little difference in mean TSS or transmissivity between NMS and non-NMS locations. Mean transmissivity in bottom waters, though higher in comparison to surface waters, showed little difference among geographic regions or between NMS and non-NMS locations. Concentrations of nitrate + nitrite, ammonium, total dissolved inorganic nitrogen (DIN) and orthophosphate (P) in surface waters tended to be highest in CA compared to WA and OR, and higher in the CA NMS stations compared to CA non-sanctuary stations. Measurements of silicate in surface waters were limited to WA and CA (exclusive of the SCB) and showed that concentrations were similar between the two states and approximately twice as high in CA sanctuaries compared to OCNMS or nonsanctuary locations in either state. The elevated nutrient concentrations observed at CA NMS stations are consistent with the presence of strong upwelling at these sites at the time of sampling. Approximately 93% of the area had DIN/P values ≤ 16, indicative of nitrogen limitation. Mean DIN/P ratios were similar among the three states, although the mean for the OCNMS was less than half that of the CA sanctuaries or nonsanctuary locations. Concentrations of chlorophyll a in surface waters ranged from 0 to 28 μg L-1, with 50% of the area having values < 3.9 μg L-1 and 10% having values > 14.5 μg L-1. The mean concentration of chlorophyll a for CA was less than half that of WA and OR locations, and concentrations were lowest in non-sanctuary sites in CA and highest at the OCNMS. Shelf sediments throughout the survey area were relatively uncontaminated with the exception of a group of stations within the SCB. Overall, about 99% of the total survey area was rated in good condition (<5 chemicals measured above corresponding effect range low (ERL) concentrations). Only the pesticides 4,4′-DDE and total DDT exceeded corresponding effect range-median (ERM) values, all at stations in CA near Los Angeles. Ten other contaminants including seven metals (As, Cd, Cr, Cu, Hg, Ag, Zn), 2-methylnaphthalene, low molecular weight PAHs, and total PCBs exceeded corresponding ERLs. The most prevalent in terms of area were chromium (31%), arsenic (8%), 2-methylnaphthalene (6%), cadmium (5%), and mercury (4%). The chromium contamination may be related to natural background sources common to the region. The 2-methylnaphthalene exceedances were conspicuously grouped around the CINMS. The mercury exceedances were all at non-sanctuary sites in CA, particularly in the Los Angeles area. Concentrations of cadmium in fish tissues exceeded the lower end of EPA’s non-cancer, human-health-risk range at nine of 50 EMAP/NCA-West and nine of 60 FRAM groundfish-survey stations, including a total of seven NMS stations in CA and two in the OCNMS. The human-health guidelines for all other contaminants were only exceeded for total PCBs at one station located in WA near the mouth of the Columbia River. Benthic species richness was relatively high in these offshore assemblages, ranging from 19 to 190 taxa per 0.1-m2 grab and averaging 79 taxa/grab. The high species richness was reflected over large areas of the shelf and was nearly three times greater than levels observed in estuarine samples along the West Coast (e.g NCA-West estuarine mean of 26 taxa/grab). Mean species richness was highest off CA (94 taxa/grab) and lower in OR and WA (55 and 56 taxa/grab, respectively). Mean species richness was very similar between sanctuary vs. non-sanctuary stations for both the CA and OR/WA regions. Mean diversity index H′ was highest in CA (5.36) and lowest in WA (4.27). There were no major differences in mean H′ between sanctuary vs. nonsanctuary stations for both the CA and OR/WA regions. A total of 1,482 taxa (1,108 to species) and 99,135 individuals were identified region-wide. Polychaetes, crustaceans and molluscs were the dominant taxa, both by percent abundance (59%, 17%, 12% respectively) and percent species (44%, 25%, 17%, respectively). There were no major differences in the percent composition of benthic communities among states or between NMSs and corresponding non-sanctuary sites. Densities averaged 3,788 m-2, about 30% of the average density for West Coast estuaries. Mean density of benthic fauna in the present offshore survey, averaged by state, was highest in CA (4,351 m-2) and lowest in OR (2,310 m-2). Mean densities were slightly higher at NMS stations vs. non-sanctuary stations for both the CA and OR/WA regions. The 10 most abundant taxa were the polychaetes Mediomastus spp., Magelona longicornis, Spiophanes berkeleyorum, Spiophanes bombyx, Spiophanes duplex, and Prionospio jubata; the bivalve Axinopsida serricata, the ophiuroid Amphiodia urtica, the decapod Pinnixa occidentalis, and the ostracod Euphilomedes carcharodonta. Mediomastus spp. and A. serricata were the two most abundant taxa overall. Although many of these taxa have broad geographic distributions throughout the region, the same species were not ranked among the 10 most abundant taxa consistently across states. The closest similarities among states were between OR and WA. At least half of the 10 most abundant taxa in NMSs were also dominant in corresponding nonsanctuary waters. Many of the abundant benthic species have wide latitudinal distributions along the West Coast shelf, with some species ranging from southern CA into the Gulf of Alaska or even the Aleutians. Of the 39 taxa on the list of 50 most abundant taxa that could be identified to species level, 85% have been reported at least once from estuaries of CA, OR, or WA exclusive of Puget Sound. Such broad latitudinal and estuarine distributions are suggestive of wide habitat tolerances. Thirteen (1.2%) of the 1,108 identified species are nonindigenous, with another 121 species classified as cryptogenic (of uncertain origin), and 208 species unclassified with respect to potential invasiveness. Despite uncertainties of classification, the number and densities of nonindigenous species appear to be much lower on the shelf than in the estuarine ecosystems of the Pacific Coast. Spionid polychaetes and the ampharetid polychaete Anobothrus gracilis were a major component of the nonindigenous species collected on the shelf. NOAA’s five NMSs along the West Coast of the U.S. appeared to be in good ecological condition, based on the measured indicators, with no evidence of major anthropogenic impacts or unusual environmental qualities compared to nearby nonsanctuary waters. Benthic communities in sanctuaries resembled those in corresponding non-sanctuary waters, with similarly high levels of species richness and diversity and low incidence of nonindigenous species. Most oceanographic features were also similar between sanctuary and non-sanctuary locations. Exceptions (e.g., higher concentrations of some nutrients in sanctuaries along the CA coast) appeared to be attributable to natural upwelling events in the area at the time of sampling. In addition, sediments within the sanctuaries were relatively uncontaminated, with none of the samples having any measured chemical in excess of ERM values. The ERL value for chromium was exceeded in sediments at the OCNMS, but at a much lower percentage of stations (four of 30) compared to WA and OR non-sanctuary areas (31 of 70 stations). ERL values were exceeded for arsenic, cadmium, chromium, 2- methylnaphthalene, low molecular weight PAHs, total DDT, and 4,4′-DDE at multiple sites within the CINMS. However, cases where total DDT, 4,4′-DDE, and chromium exceeded the ERL values were notably less prevalent at CINMS than in non-sanctuary waters of CA. In contrast, 2-methylnaphthalene above the ERL was much more prevalent in sediments at the CINMS compared to non-sanctuary waters off the coast of CA. While there are natural background sources of PAHs from oil seeps throughout the SCB, this does not explain the higher incidence of 2-methylnaphthalene contamination around CINMS. Two stations in CINMS also had levels of TOC (> 5%) potentially harmful to benthic fauna, though none of these sites exhibited symptoms of impaired benthic condition. This study showed no major evidence of extensive biological impacts linked to measured stressors. There were only two stations, both in CA, where low numbers of benthic species, diversity, or total faunal abundance co-occurred with high sediment contamination or low DO in bottom water. Such general lack of concordance suggests that these offshore waters are currently in good condition, with the lower-end values of the various biological attributes representing parts of a normal reference range controlled by natural factors. Results of multiple linear regression, performed using full model procedures to test for effects of combined abiotic environmental factors, suggested that latitude and depth had significant influences on benthic variables regionwide. Latitude had a significant inverse influence on all three of the above benthic variables, i.e. with values increasing as latitude decreased (p< 0.01), while depth had a significant direct influence on diversity (p < 0.001) and inverse effect on density (p <0.01). None of these variables varied significantly in relation to sediment % fines (at p< 0.1), although in general there was a tendency for muddier sediments (higher % fines) to have lower species richness and diversity and higher densities than coarser sediments. Alternatively, it is possible that for some of these sites the lower values of benthic variables reflect symptoms of disturbance induced by other unmeasured stressors. The indicators in this study included measures of stressors (e.g., chemical contaminants, eutrophication) that are often associated with adverse biological impacts in shallower estuarine and inland ecosystems. However, there may be other sources of humaninduced stress in these offshore systems (e.g., bottom trawling) that pose greater risks to ambient living resources and which have not been captured. Future monitoring efforts in these offshore areas should include indicators of such alternative sources of disturbance. (137pp.) (PDF contains 167 pages)