Microbial formation and degradation of oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) in soil during short-term incubation

We tested whether OPAHs were formed during 19-wk incubation of a fertile soil at optimum moisture in the dark. The soil had initial mean (±s.e., n = 3) concentrations of 22 ± 1.7 (Σ28PAHs) and 4.2 ± 0.34 μg g−1 (Σ14OPAHs). After 19 wk, individual PAH and OPAH concentrations had decreased by up to 14 and 37%, respectively. Decreases in % of initial concentrations were positively correlated with their KOW values for PAHs (r = 0.48, p = 0.022) and 9 OPAHs (r = 0.78, p = 0.013) but negatively, albeit not significantly, for 5 OPAHs (r = −0.75, p = 0.145) suggesting net formation of some OPAHs. The latter was supported by significantly increasing 1-indanone/fluorene ratios while the other OPAH to parent-PAH ratios remained constant or tended to increase. We conclude that OPAHs are formed in soils during microbial turnover of PAHs in a short time.

Oxygen Isotopic and Soluble Ionic Composition of a Shallow Firn Core, Inilchek Glacier, Central Tien Shan

Oxygen isotopic and soluble ionic measurements made on snow-pit (2 in depth) and firn-core (12.4 m depth samples recovered from the accumulation zone 5100 m) of Inilchek glacier 43degrees N, 79degrees E) provide information on recent (1992-98) climatic and environmental conditions in the central Tien Shan region of central Asia. The combined 14.4 m snow-pit/firn-core profile lies within the firn zone, arid contains only one observed melt feature (10 m temperature = - 12 degreesC), Although some post-depositional attenuation of the sub-seasonal delta(18)O record is possible, annual cycles are apparent throughout the isotope profile. We therefore use the preserved delta(18)O record to establish a depth/age scale for the core. Mean delta(18)O values for the entire core and for summer periods are consistent with delta(18)O/temperature observations, and suggest the delta(18)O record provides a means to reconstruct past changes in summer surface temperature at the site. Major-ion (Na(+), K(+), Mg(2+), Ca(2+), NH(4)(+), Cl(-), NO(3)(-), SO(4)(2-)) data from the core demonstrate the dominant influence of dust deposition on the soluble chemistry at the site, arid indicate significant interannual variability in atmospheric-dust loading during the 1900s. Anthropogenic impacts oil NH(4)(+) concentrations are observed at the site, and suggest a summer increase in atmospheric NH(4)(+) that may be related to regional agricultural (nitrogen-rich fertilizer use activities.

Occurrence, gas/particle partitioning and carcinogenic risk of polycyclic aromatic hydrocarbons and their oxygen and nitrogen containing derivatives in Xi'an, central China

29 parent- and alkyl-polycyclic aromatic hydrocarbons (PAHs), 15 oxygenated-PAHs (OPAHs), 11 nitrated-PAHs (NPAHs) and 4 azaarenes (AZAs) in both the gaseous and particulate phases, as well as the particulate-bound carbon fractions (organic carbon, elemental carbon, char, and soot) in ambient air sampled in March and September 2012 from an urban site in Xi'an, central China were extracted and analyzed. The average concentrations (gaseous+particulate) of 29PAHs, 15OPAHs, 11NPAHs and 4AZAs were 1267.0±307.5, 113.8±46.1, 11.8±4.8 and 26.5±11.8ngm(-3) in March and 784.7±165.1, 67.2±9.8, 9.0±1.5 and 21.6±5.1ngm(-3) in September, respectively. Concentrations of 29PAHs, 15OPAHs and 11NPAHs in particulates were significantly correlated with those of the carbon fractions (OC, EC, char and soot). Both absorption into organic matter in particles and adsorption onto the surface of particles were important for PAHs and OPAHs in both sampling periods, with more absorption occurring in September, while absorption was always the most important process for NPAHs. The total carcinogenic risk of PAHs plus the NPAHs was higher in March. Gaseous compounds, which were not considered in most previous studies, contributed 29 to 44% of the total health risk in March and September, respectively.

A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee, Switzerland

In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in Central Switzerland. Comparisons between calculated equilibrium isotope values, using the fractionation equation of Friedman and O’Neil, (1977) and measured oxygen isotope ratios of calcite in the sediment-traps reveal that oxygen isotopic values of autochthonous calcite (δ18O) are in isotopic equilibrium with ambient water during most of the spring and summer, when the majority of the calcite precipitates. In contrast, small amounts of calcite precipitated in early-spring and again in late-autumn are isotopically depleted in 18O relative to the calculated equilibrium values, by as much as 0.8‰. This seasonally occurring apparent isotopic nonequilibrium is associated with times of high phosphorous concentrations, elevated pH (∼8.6) and increased [CO32−] (∼50 μmol/l) in the surface waters. The resulting weighted average δ18O value for the studied period is −9.6‰, compared with a calculated equilibrium δ18O value of −9.4‰. These data convincingly demonstrate that δ18O of calcite are, for the most part, a very reliable proxy for temperature and δ18O of the water.

Oxygen Supplementing, Biocompatible Outer Membranes for Enhanced Performance of Implantable Glucose Sensors

Lack of linearity and sensitivity, oxygen dependence, biofouling and tissue inflammation hinder the development of implantable biosensors for continuous monitoring of glucose. Herein, we report the development of stacked outer membranes based on LBL/PVA hydrogels that improve sensor sensitivity, linearity, oxygen independence and counter biofouling and inflammation. While the inner LBL membrane affords tunable diffusivity, the outer PVA is capable of releasing anti-inflammatory drugs/tissue response modifying agents to counter acute and chronic inflammation, and to induce neo-angiogenesis at the implant site. Sensors were fabricated by immobilizing GOx enzyme on top of 50 μm platinum wires, followed by deposition of stacked LBL/PVA hydrogel membranes. The response of the sensors at 0.7V to various glucose concentrations was studied. Michelis-Menten analysis was performed to quantify sensor performance in terms of linearity and oxygen dependence. The interplay between sensor performance and inward glucose diffusivity was elucidated using (i) various LBL membranes and (ii) various freeze-thaw (FT) cycles of PVA. Incorporation of LBL/PVA stacked membranes resulted in an 8 fold increase in sensor linearity and a 9 fold decrease in oxygen dependence compared to controls. The enhancement in the sensor performance is attributed to (i) the oxygen storing capability of PVA hydrogel due to the formation of hydrophobic domains during its freezing/ thawing employed for its physical crosslinking and (ii) regulation of glucose flux by the inner LBL membrane. Such membranes offer significant advantages over presently available outer membranes in lieu of (i) their ability to control inflammation, (ii) their modulus that closely matches that of subcutaneous human tissue, (iii) non-necessity of reactive chemical crosslinking agents, (iv) tunable sensitivity and (v) supplemental storage of oxygen.

Dinoflagellate cyst assemblages, oxygen isotope records of foraminifera, and alkenone and Mg/Ca-based SST estimates for the time interval 3.40-3.18 Ma (Late Pliocene) from five North Atlantic and Caribbean sediment cores

The early Late Pliocene (3.6 to ~3.0 million years ago) is the last extended interval in Earth's history when atmospheric CO2 concentrations were comparable to today's and global climate was warmer. Yet a severe global glaciation during marine isotope stage (MIS) M2 interrupted this phase of global warmth ~3.30 million years ago, and is seen as a premature attempt of the climate system to establish an ice-age world. Our geochemical and palynological records from five marine sediment cores along a Caribbean to eastern North Atlantic transect show that increased Pacific-to-Atlantic flow via the Central American Seaway weakened the North Atlantic Current (NAC) and attendant northward heat transport prior to MIS M2. The consequent cooling of the northern high latitude oceans permitted expansion of the Greenland ice sheet during MIS M2, despite near-modern atmospheric CO2 concentrations. Before and after MIS M2, heat transport via the NAC was crucial in maintaining warm climates comparable to those predicted for the end of this century.

Manganese concentrations and flux data of sediments from Broken and Ninetyeast Ridge

Decomposition of organic matter combined with density stratification generate a pronounced intermediate water oxygen minimum zone (OMZ) in the northwest Indian Ocean. This zone currently lies between water depths of 200 and 2000 m and extends approximately 5000 km southeast from the Arabian coast. Based upon benthic foraminiferal assemblage changes, it has been suggested that this OMZ was even more extensive during the late Miocene-early Pliocene (6.5-3.0 Ma), with a maximum volume and/or intensity at approximately 5.0 Ma. While this inference may contribute to an understanding of the history of northwest Indian Ocean upwelling, corroborating geochemical evidence for this interpretation has heretofore been lacking. Ocean Drilling Program (ODP) sites 752, 754, and 757 on Broken and Ninetyeast ridges are located within central Indian Ocean intermediate water depths (1086-1650 m) but outside the present lateral dimensions of the Indian Ocean OMZ. High-resolution chemical analyses of sediment from these sites indicate significant reductions in the flux of Mn and normalized Mn concentrations between 6.5 and 3.0 Ma that are most pronounced at approximately 5.0 Ma. Because late Miocene-Pliocene paleodepths for these sites were essentially the same as at present and because extremely low sedimentation rates (0.3-1.3 cm/ky) most likely precluded sedimentary metal oxide diagenesis, we suggest that the observed Mn depletions reflect diminished deposition of reducible Mn oxyhydroxide phases within O2 deficient intermediate waters and that this effect was most intense at approximately 5.0 Ma. This interpretation implies that waters with less than 2.0 mL/L O2 extended at least 1500 km beyond their present limits and is consistent with changes in benthic foraminifera assemblages. We further suggest this expanded Indian Ocean OMZ is related to regionally and/or globally increased biological productivity.

Benthic carbon turnover, sediment pigment concentrations and sinking fluxes of POC in the southeastern Beaufort Sea during CCGS Amundsen cruise 2008

The effects of changing ice and atmospheric conditions on the upwelling of deep nutrient-laden waters and biological productivity in the coastal Beaufort Sea were quantified using a unique combination of in situ and remote-sensing approaches. Repeated instances of ice ablation and upwelling during fall 2007 and summer 2008 multiplied the production of ice algae, phytoplankton, zooplankton and benthos by 2 to 6 fold. Strong wind forcing failed to induce upward shifts in the biological productivity of stratified waters off the shelf.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, Ross Sea

Dissolved and particulate organic matter was measured during six cruises to the southern Ross Sea. The cruises were conducted during late austral winter to autumn from 1994 to 1997 and included coverage of various stages of the seasonal phytoplankton bloom. The data from the various years are compiled into a representative seasonal cycle in order to assess general patterns of dissolved organic matter (DOM) and particulate organic matter (POM) dynamics in the southern Ross Sea. Dissolved organic carbon (DOC) and particulate organic carbon (POC) were at background concentrations of approximately 42 and 3 µM C, respectively, during the late winter conditions in October. As the spring phytoplankton bloom progressed, organic matter increased, and by January DOC and POC reached as high as 30 and 107 µM C, respectively, in excess of initial wintertime conditions. Stocks and concentrations of DOC and POC returned to near background values by autumn (April). Approximately 90% of the accumulated organic matter was partitioned into POM, with modest net accumulation of DOM stocks despite large net organic matter production and the dominance of Phaeocystis antarctica. Changes in NO3 concentration from wintertime values were used to calculate the equivalent biological drawdown of dissolved inorganic carbon (DICequiv). The fraction of DICequiv drawdown resulting in net DOC production was relatively constant (ca. 11%), despite large temporal and spatial variability in DICequiv drawdown. The C : N (molar ratio) of the seasonally produced DOM had a geometric mean of 6.2 and was nitrogen-rich compared to background DOM. The DOM stocks that accumulate in excess of deep refractory background stocks are often referred to as "semi-labile" DOM. The "semi-labile" pool in the Ross Sea turns over on timescales of about 6 months. As a result of the modest net DOM production and its lability, the role DOM plays in export to the deep sea is small in this region.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, Arabian Sea

Concentrations of total organic carbon (TOC) were determined on samples collected during six cruises in the northern Arabian Sea during the 1995 US JGOFS Arabian Sea Process Study. Total organic carbon concentrations and integrated stocks in the upper ocean varied both spatially and seasonally. Highest mixed-layer TOC concentrations (80-100 µM C) were observed near the coast when upwelling was not active, while upwelling tended to reduce local concentrations. In the open ocean, highest mixed-layer TOC concentrations (80-95 µM C) developed in winter (period of the NE Monsoon) and remained through mid summer (early to mid-SW Monsoon). Lowest open ocean mixed-layer concentrations (65-75 µM C) occurred late in the summer (late SW Monsoon) and during the Fall Intermonsoon period. The changes in TOC concentrations resulted in seasonal variations in mean TOC stocks (upper 150 m) of 1.5-2 mole C/m**2, with the lowest stocks found late in the summer during the SW Monsoon-Fall Intermonsoon transition. The seasonal accumulation of TOC north of 15°N was 31-41 x 10**12 g C, mostly taking place over the period of the NE Monsoon, and equivalent to 6-8% of annual primary production estimated for that region in the mid-1970s. A net TOC production rate of 12 mmole C/m**2/d over the period of the NE Monsoon represented ~80% of net community production. Net TOC production was nil during the SW Monsoon, so vertical export would have dominated the export terms over that period. Total organic carbon concentrations varied in vertical profiles with the vertical layering of the water masses, with the Persian Gulf Water TOC concentrations showing a clear signal. Deep water (>2000 m) TOC concentrations were uniform across the basin and over the period of the cruises, averaging 42.3±1.4 µM C.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, Pacific Ocean

Total organic carbon (TOC) was analyzed on four transects along 140°W in 1992 using a high temperature combustion/discrete injection (HTC/DI) analyzer. For two of the transects, the analyses were conducted on-board ship. Mixed-layer concentrations of organic carbon varied from about 80 µM C at either end of the transect (12°N and 12°S) to about 60 µM C at the equator. Total organic carbon concentrations decreased rapidly below the mixed-layer to about 38-40 µM C at 1000 m across the transect. Little variation was observed below this depth; deep water concentrations below 2000 m were virtually monotonic at about 36 µM C. Repeat measurements made on subsequent cruises consistently found the same concentrations at 1000 m or deeper, but substantial variations were observed in the mixed-layer and the upper water column above 400 m depth. Linear mixing models of total organic carbon versus sigmaT exhibited zones of organic carbon formation and consumption. TOC was found to be inversely correlated with apparent oxygen utilization (AOU) in the region between the mixed-layer and the oxygen minimum. In the mixed-layer, TOC concentrations varied seasonally. Part of the variations in TOC at the equator was driven by changes in the upwelling rate in response to variations in physical forcing related to an El Niño and to the passage of tropical instability waves. TOC export fluxes, calculated from simple box models, averaged 8±4 mmol C/m**2/day at the equator and also varied seasonally. These export fluxes account for 50-75% of the total carbon deficit and are consistent with other estimates and model predictions.

Part of the global DOC versus AOU (dissolved organic carbon/apparent oxygen utilization) data compilation, BATS

The contributions of total organic carbon and nitrogen to elemental cycling in the surface layer of the Sargasso Sea are evaluated using a 5-yr time-series data set (1994-1998). Surface-layer total organic carbon (TOC) and total organic nitrogen (TON) concentrations ranged from 60 to 70 µM C and 4 to 5.5 µM N seasonally, resulting in a mean C : N molar ratio of 14.4±2.2. The highest surface concentrations varied little during individual summer periods, indicating that net TOC production ceased during the highly oligotrophic summer season. Winter overturn and mixing of the water column were both the cause of concentration reductions and the trigger for net TOC production each year following nutrient entrainment and subsequent new production. The net production of TOC varied with the maximum in the winter mixed-layer depth (MLD), with greater mixing supporting the greatest net production of TOC. In winter 1995, the TOC stock increased by 1.4 mol C/m**2 in response to maximum mixing depths of 260 m. In subsequent years experiencing shallower maxima in MLD (<220 m), TOC stocks increased <0.7 mol C/m**2. Overturn of the water column served to export TOC to depth (>100 m), with the amount exported dependent on the depth of mixing (total export ranged from 0.4 to 1.4 mol C/m**2/yr). The exported TOC was comprised both of material resident in the surface layer during late summer (resident TOC) and material newly produced during the spring bloom period (fresh TOC). Export of resident TOC ranged from 0.5 to 0.8 mol C/m**2/yr, covarying with the maximum winter MLD. Export of fresh TOC varied from nil to 0.8 mol C/m**2/yr. Fresh TOC was exported only after a threshold maximum winter MLD of ~200 m was reached. In years with shallower mixing, fresh TOC export and net TOC production in the surface layer were greatly reduced. The decay rates of the exported TOC also covaried with maximum MLD. The year with deepest mixing resulted in the highest export and the highest decay rate (0.003 1/d) while shallow and low export resulted in low decay rates (0.0002 1/d), likely a consequence of the quality of material exported. The exported TOC supported oxygen utilization at dC : dO2 molar ratios ranging from 0.17 when TOC export was low to 0.47 when it was high. We estimate that exported TOC drove 15-41% of the annual oxygen utilization rates in the 100-400 m depth range. Finally, there was a lack of variability in the surface-layer TON signal during summer. The lack of a summer signal for net TON production suggests a small role for N2 fixation at the site. We hypothesize that if N2 fixation is responsible for elevated N : P ratios in the main thermocline of the Sargasso Sea, then the process must take place south of Bermuda and the signal transported north with the Gulf Stream system.