Controls on dissolved organic carbon quantity and chemical character in temperate rivers of North America

Understanding the processes controlling the transfer and chemical composition of dissolved organic carbon (DOC) in freshwater systems is crucial to understanding the carbon cycle and the effects of DOC on water quality. Previous studies have identified watershed‐scale controls on bulk DOC flux and concentration among small basins but fewer studies have explored controls among large basins or simultaneously considered the chemical composition of DOC. Because the chemical character of DOC drives riverine biogeochemical processes such as metabolism and photodegradation, accounting for chemical character in watershed‐scale studies will improve the way bulk DOC variability in rivers is interpreted. We analyzed DOC quantity and chemical character near the mouths of 17 large North American rivers, primarily between 2008 and 2010, and identified watershed characteristics that controlled variability. We quantified DOC chemical character using both specific ultraviolet absorbance at 254 nm (SUVA254) and XAD‐resin fractionation. Mean DOC concentration ranged from 2.1 to 47 mg C L−1 and mean SUVA254 ranged from 1.3 to 4.7 L mg C−1 m−1. We found a significant positive correlation between basin wetland cover and both bulk DOC concentration (R2 = 0.78; p \u3c 0.0001) and SUVA254 (R2 = 0.91; p \u3c 0.0001), while other land use characteristics were not correlated. The strong wetland relationship with bulk DOC concentration is similar to that found by others in small headwater catchments. However, two watersheds with extremely long surface water residence times, the Colorado and St. Lawrence, diverged from this wetland relationship. These results suggest that the role of riverine processes in altering the terrestrial DOC signal at the annual scale was minimal except in river systems with long surface water residence times. However, synoptic DOC sampling of both quantity and character throughout river networks will be needed to more rigorously test this finding. The inclusion of DOC chemical character will be vital to achieving a more complete understanding of bulk DOC dynamics in large river systems

Abundance, Stable Isotopic Composition, and Export Fluxes of DOC, POC, and DIC From the Lower Mississippi River During 2006-2008

Sources, abundance, isotopic compositions, and export fluxes of dissolved inorganic carbon (DIC), dissolved and colloidal organic carbon (DOC and COC), and particulate organic carbon (POC), and their response to hydrologic regimes were examined through monthly sampling from the Lower Mississippi River during 2006–2008. DIC was the most abundant carbon species, followed by POC and DOC. Concentration and δ13C of DIC decreased with increasing river discharge, while those of DOC remained fairly stable. COC comprised 61 ± 3% of the bulk DOC with similar δ13C abundances but higher percentages of hydrophobic organic acids than DOC, suggesting its aromatic and diagenetically younger status. POC showed peak concentrations during medium flooding events and at the rising limb of large flooding events. While δ13C-POC increased, δ15N of particulate nitrogen decreased with increasing discharge. Overall, the differences in δ13C between DOC or DIC and POC show an inverse correlation with river discharge. The higher input of soil organic matter and respired CO2 during wet seasons was likely the main driver for the convergence of δ13C between DIC and DOC or POC, whereas enhanced in situ primary production and respiration during dry seasons might be responsible for their isotopic divergence. Carbon export fluxes from the Mississippi River were estimated to be 13.6 Tg C yr−1 for DIC, 1.88 Tg C yr−1 for DOC, and 2.30 Tg C yr−1 for POC during 2006–2008. The discharge-normalized DIC yield decreased during wet seasons, while those of POC and DOC increased and remained constant, respectively, implying variable responses in carbon export to the increasing discharge

Taking the pulse of snowmelt: in situ sensors reveal seasonal, event and diurnal patterns of nitrate and dissolved organic matter variability in an upland forest stream

Highly resolved time series data are useful to accurately identify the timing, rate, and magnitude of solute transport in streams during hydrologically dynamic periods such as snowmelt. We used in situ optical sensors for nitrate (NO3 −) and chromophoric dissolved organic matter fluorescence (FDOM) to measure surface water concentrations at 30 min intervals over the snowmelt period (March 21–May 13, 2009) at a 40.5 hectare forested watershed at Sleepers River, Vermont. We also collected discrete samples for laboratory absorbance and fluorescence as well as δ18O–NO3 − isotopes to help interpret the drivers of variable NO3 − and FDOM concentrations measured in situ. In situ data revealed seasonal, event and diurnal patterns associated with hydrological and biogeochemical processes regulating stream NO3 − and FDOM concentrations. An observed decrease in NO3 − concentrations after peak snowmelt runoff and muted response to spring rainfall was consistent with the flushing of a limited supply of NO3 − (mainly from nitrification) from source areas in surficial soils. Stream FDOM concentrations were coupled with flow throughout the study period, suggesting a strong hydrologic control on DOM concentrations in the stream. However, higher FDOM concentrations per unit streamflow after snowmelt likely reflected a greater hydraulic connectivity of the stream to leachable DOM sources in upland soils. We also observed diurnal NO3 − variability of 1–2 μmol l−1 after snowpack ablation, presumably due to in-stream uptake prior to leafout. A comparison of NO3 − and dissolved organic carbon yields (DOC, measured by FDOM proxy) calculated from weekly discrete samples and in situ data sub-sampled daily resulted in small to moderate differences over the entire study period (−4 to 1% for NO3 − and −3 to −14% for DOC), but resulted in much larger differences for daily yields (−66 to +27% for NO3 − and −88 to +47% for DOC, respectively). Despite challenges inherent in in situ sensor deployments in harsh seasonal conditions, these data provide important insights into processes controlling NO3 − and FDOM in streams, and will be critical for evaluating the effects of climate change on snowmelt delivery to downstream ecosystems

Diskless Image Management (DIM) for Cluster Administration

Large computing systems have large administration needs. But just as technologies have evolved to take advantage of certain parallelisms of large scale computing, administrating these technologies must evolve to take advantage of the associated operational efficiencies. Using a straightforward push technology, and scalable to thousands of blades, Diskless Image Management (DIM) allows system administrators to boot, patch, or modify one, several or all distributed images in minutes from a single management console. DIM was prototyped on the MareNostrum cluster with 2406 blades, but is scalable to 7000 blades. Using IBM JS20 blade technology MareNostrum consists of 172 BladeCenters

The effect of natural organic matter on mercury methylation by Desulfobulbus propionicus 1pr3

Methylation of tracer and ambient mercury (200Hg and 202Hg, respectively) equilibrated with four different natural organic matter (NOM) isolates was investigated in vivo using the Hg-methylating sulfate-reducing bacterium Desulfobulbus propionicus 1pr3. Desulfobulbus cultures grown fermentatively with environmentally representative concentrations of dissolved NOM isolates, Hg[II], and HS− were assayed for absolute methylmercury (MeHg) concentration and conversion of Hg(II) to MeHg relative to total unfiltered Hg(II). Results showed the 200Hg tracer was methylated more efficiently in the presence of hydrophobic NOM isolates than in the presence of transphilic NOM, or in the absence of NOM. Different NOM isolates were associated with variable methylation efficiencies for either the 202Hg tracer or ambient 200Hg. One hydrophobic NOM, F1 HpoA derived from dissolved organic matter from the Florida Everglades, was equilibrated for different times with Hg tracer, which resulted in different methylation rates. A 5 day equilibration with F1 HpoA resulted in more MeHg production than either the 4 h or 30 day equilibration periods, suggesting a time dependence for NOM-enhanced Hg bioavailability for methylation

Creating Virtual 3-D Outcrop

Because of the high precision of present-day GPS and reflectorless laser technology, geologic information and remotely sensed data (i.e., seismic and GPR grids, wells) can be positioned accurately in 3-D and reconstructed as a virtual image. Hence, we have developed the “virtual outcrop” for applications that require knowledge about the 3-D spatial arrangements of rock types

Development and validation of the ACE tool: Assessing medical trainees' competency in evidence based medicine

BACKGROUND: While a variety of instruments have been developed to assess knowledge and skills in evidence based medicine (EBM), few assess all aspects of EBM - including knowledge, skills attitudes and behaviour - or have been psychometrically evaluated. The aim of this study was to develop and validate an instrument that evaluates medical trainees’ competency in EBM across knowledge, skills and attitude. METHODS: The ‘Assessing Competency in EBM’ (ACE) tool was developed by the authors, with content and face validity assessed by expert opinion. A cross-sectional sample of 342 medical trainees representing ‘novice’, ‘intermediate’ and ‘advanced’ EBM trainees were recruited to complete the ACE tool. Construct validity, item difficulty, internal reliability and item discrimination were analysed. RESULTS: We recruited 98 EBM-novice, 108 EBM-intermediate and 136 EBM-advanced participants. A statistically significant difference in the total ACE score was observed and corresponded to the level of training: on a 0-15-point test, the mean ACE scores were 8.6 for EBM-novice; 9.5 for EBM-intermediate; and 10.4 for EBM-advanced (p < 0.0001). Individual item discrimination was excellent (Item Discrimination Index ranging from 0.37 to 0.84), with internal reliability consistent across all but three items (Item Total Correlations were all positive ranging from 0.14 to 0.20). CONCLUSION: The 15-item ACE tool is a reliable and valid instrument to assess medical trainees’ competency in EBM. The ACE tool provides a novel assessment that measures user performance across the four main steps of EBM. To provide a complete suite of instruments to assess EBM competency across various patient scenarios, future refinement of the ACE instrument should include further scenarios across harm, diagnosis and prognosis

Biomass offsets little or none of permafrost carbon release from soils, streams, and wildfire: an expert assessment

As the permafrost region warms, its large organic carbon pool will be increasingly vulnerable to decomposition, combustion, and hydrologic export. Models predict that some portion of this release will be offset by increased production of Arctic and boreal biomass; however, the lack of robust estimates of net carbon balance increases the risk of further overshooting international emissions targets. Precise empirical or model-based assessments of the critical factors driving carbon balance are unlikely in the near future, so to address this gap, we present estimates from 98 permafrost-region experts of the response of biomass, wildfire, and hydrologic carbon flux to climate change. Results suggest that contrary to model projections, total permafrost-region biomass could decrease due to water stress and disturbance, factors that are not adequately incorporated in current models. Assessments indicate that end-of-the-century organic carbon release from Arctic rivers and collapsing coastlines could increase by 75% while carbon loss via burning could increase four-fold. Experts identified water balance, shifts in vegetation community, and permafrost degradation as the key sources of uncertainty in predicting future system response. In combination with previous findings, results suggest the permafrost region will become a carbon source to the atmosphere by 2100 regardless of warming scenario but that 65%–85% of permafrost carbon release can still be avoided if human emissions are actively reduced

Context matters: combined influence of participation and intellectual stimulation on the promotion-focus/employee creativity relationship

In this paper, we examined the interactive effects of two contexts — participation and intellectual stimulation, and promotion focus on creativity. On the basis of a multi-organization sample of 213 employees, we tested and found that although promotion focus was positively related to creativity, the relationship between promotion focus and creativity was most positive when both participation and leader intellectual stimulation were high. We discuss the way contexts in combination influence employee creativity for promotion-oriented individuals, through increasing decision latitude as well as stimulating and promoting creativity