The RCP greenhouse gas concentrations and their extensions from 1765 to 2300

We present the greenhouse gas concentrations for the Representative Concentration Pathways (RCPs) and their extensions beyond 2100, the Extended Concentration Pathways (ECPs). These projections include all major anthropogenic greenhouse gases and are a result of a multi-year effort to produce new scenarios for climate change research. We combine a suite of atmospheric concentration observations and emissions estimates for greenhouse gases (GHGs) through the historical period (1750?C2005) with harmonized emissions projected by four different Integrated Assessment Models for 2005?C2100. As concentrations are somewhat dependent on the future climate itself (due to climate feedbacks in the carbon and other gas cycles), we emulate median response characteristics of models assessed in the IPCC Fourth Assessment Report using the reduced-complexity carbon cycle climate model MAGICC6. Projected ??best-estimate?? global-mean surface temperature increases (using inter alia a climate sensitivity of 3°C) range from 1.5°C by 2100 for the lowest of the four RCPs, called both RCP3-PD and RCP2.6, to 4.5°C for the highest one, RCP8.5, relative to pre-industrial levels. Beyond 2100, we present the ECPs that are simple extensions of the RCPs, based on the assumption of either smoothly stabilizing concentrations or constant emissions: For example, the lower RCP2.6 pathway represents a strong mitigation scenario and is extended by assuming constant emissions after 2100 (including net negative CO₂ emissions), leading to CO₂ concentrations returning to 360 ppm by 2300. We also present the GHG concentrations for one supplementary extension, which illustrates the stringent emissions implications of attempting to go back to ECP4.5 concentration levels by 2250 after emissions during the 21^st century followed the higher RCP6 scenario. Corresponding radiative forcing values are presented for the RCP and ECPs.     

Efficacy of Hollow‐Fiber Ultrafiltration for Microbial Sampling in Groundwater

The goal of this study was to test hollow‐fiber ultrafiltration as a method for concentrating in situ bacteria and viruses in groundwater samples. Water samples from nine wells tapping a shallow sandy aquifer in a densely populated village in Bangladesh were reduced in volume approximately 400‐fold using ultrafiltration. Culture‐based assays for total coliforms and Escherichia coli, as well as molecular‐based assays for E. coli, Bacteroides, and adenovirus, were used as microbial markers before and after ultrafiltration to evaluate performance. Ultrafiltration increased the concentration of the microbial markers in 99% of cases. However, concentration factors (CF = post‐filtration concentration/pre‐filtration concentration) for each marker calculated from geometric means ranged from 52 to 1018 compared to the expected value of 400. The efficiency was difficult to quantify because concentrations of some of the markers, especially E. coli and total coliforms, in the well water (WW) collected before ultrafiltration varied by several orders of magnitude during the period of sampling. The potential influence of colloidal iron oxide precipitates in the groundwater was tested by adding EDTA to the pre‐filtration water in half of the samples to prevent the formation of precipitates. The use of EDTA had no significant effect on the measurement of culturable or molecular markers across the 0.5 to 10 mg/L range of dissolved Fe²⁺ concentrations observed in the groundwater, indicating that colloidal iron did not hinder or enhance recovery or detection of the microbial markers. Ultrafiltration appears to be effective for concentrating microorganisms in environmental water samples, but additional research is needed to quantify losses during filtration.     

Assessment of sacrificial anode impact by aluminum accumulation in mussel Mytilus edulis: a large-scale laboratory test

Since the early 1960s, the application of aluminum alloy sacrificial anodes to mitigate marine corrosion has been well known. The aim of this work was to study aluminum bioconcentration in Mytilus edulis by an in vitro test performed in two tanks: the first containing non-contaminated water (NCW) and the second containing aluminum-contaminated water (CW) (530 μg L⁻¹) released by sacrificial anode. The mussels were collected and examined over a period of 8 weeks. A comparison between the aluminum concentrations in the digestive glands of mussels from the CW and NCW tanks shows that the highest value (1700 mg/kg d.w.) was found in the CW mussels collected after 13 days. In NCW, the mean aluminum concentration in digestive glands during the test was 281 mg/kg d.w. The rapid concentration decrease in digestive glands is probably due to the inhibition of filtering activity due to valve closure at the high concentration as well as the induction of the detoxification response.     

Development and application of a physically based landscape water balance in the SWAT model

Watershed scale hydrological and biogeochemical models rely on the correct spatial‐temporal prediction of processes governing water and contaminant movement. The Soil and Water Assessment Tool (SWAT) model, one of the most commonly used watershed scale models, uses the popular curve number (CN) method to determine the respective amounts of infiltration and surface runoff. Although appropriate for flood forecasting in temperate climates, the CN method has been shown to be less than ideal in many situations (e.g. monsoonal climates and areas dominated by variable source area hydrology). The CN model is based on the assumption that there is a unique relationship between the average moisture content and the CN for all hydrologic response units (HRUs), and that the moisture content distribution is similar for each runoff event, which is not the case in many regions. Presented here is a physically based water balance that was coded in the SWAT model to replace the CN method of runoff generation. To compare this new water balance SWAT (SWAT‐WB) to the original CN‐based SWAT (SWAT‐CN), two watersheds were initialized; one in the headwaters of the Blue Nile in Ethiopia and one in the Catskill Mountains of New York. In the Ethiopian watershed, streamflow predictions were better using SWAT‐WB than SWAT‐CN [Nash–Sutcliffe efficiencies (NSE) of 0·79 and 0·67, respectively]. In the temperate Catskills, SWAT‐WB and SWAT‐CN predictions were approximately equivalent (NSE > 0·70). The spatial distribution of runoff‐generating areas differed greatly between the two models, with SWAT‐WB reflecting the topographical controls imposed on the model. Results show that a water balance provides results equal to or better than the CN, but with a more physically based approach. Copyright © 2010 John Wiley & Sons, Ltd.     

Uncertainties in determining microbial biomass C using the chloroform fumigation–extraction method

We tested the accuracy of the chloroform fumigation–extraction method, which is commonly used to determine soil biomass C concentrations. Accurate and precise determination of total microbial biomass is important in order to characterize soil properties and to develop predictive metal transport models for soils. Two natural soils, and individual soil components, including silica sand, montmorillonite, kaolinite, a humic acid, and Bacillus subtilis bacterial cells, were fumigated for 24 h. Following the fumigation, C from fumigated and unfumigated samples was extracted using a 0.5 M K₂SO₄ solution. The difference between the C content in the fumigated and unfumigated samples ideally represents C due to biomass because the fumigation procedure should lyse cells and release biomass C. We observed increased C release upon fumigation for bacteria-only samples, confirming the ability of fumigation to lyse cells. There was no difference in extracted C concentration between fumigated and unfumigated samples of silica sand and of humic acid, confirming that the fumigation process does not introduce additional organic C to samples of these soil components. However, the fumigated clay samples both showed increased C release relative to the unfumigated controls, indicating that significant concentrations of the fumigant, chloroform, adsorbed onto the clay minerals studied here. Additionally, we found significant chloroform remaining in the extracts from two fumigated natural soils. Attempts to remove the chloroform from the soils or soil components prior to extraction by increasing the evacuation time, or to remove chloroform in the extracts by sparging them vigorously with nitrogen gas, both failed. This research reveals that chloroform gas may adsorb significantly to clays and the clay fraction of natural soils. Thus, the fumigation–extraction method must be corrected to account for the added chloroform C and accurately assess the concentration of biomass C in soils that contain significant concentrations of clays.     

Timescales and mechanisms of REE and Hf uptake in fossil bones

Rare earth element (REE) patterns of fossil bones and teeth are widely used as proxies for provenance, taphonomy, and palaeoenvironment. In order to investigate if fossil bones behave as closed systems over geologic time, REE profiles were analysed by LA-ICPMS along cross sections of 54 bones from various well-characterised and well-dated settings. These include terrestrial and marine diagenetic environments, covering Early Triassic to Holocene ages. In general, all fossil bones exhibit the highest REE concentrations at the outer rim, gradually decreasing by up to four orders of magnitude toward the inner bone cortex. Intra-bone REE concentration gradients decrease significantly from Quaternary via Tertiary to Mesozoic specimens, suggesting long term REE uptake and open system behaviour of fossil bone. This view is further corroborated by ¹⁷⁶Lu-¹⁷⁶Hf dating of selected samples, all yielding significantly younger ages than the known chronostratigraphic ages. Hence, there is clear evidence for long term open system behaviour of fossil bones with respect to REE, which is in marked contrast to currently accepted models suggesting that REE uptake is only early diagenetic. Although unexpected, statistically significant four to seven point isochrons are observed for four fossil dinosaur bone samples and one Upper Triassic Mastodonsaurus tooth with MSWDs ranging from 0.083 to 4.5. Notably, mobility of Lu alone cannot account for the observed age patterns. Assuming constant Lu uptake rates over time, the radiometric ages should only be as low as half of the chronostratigraphic age. However, a six-point isochron defined by subsamples of a single Upper Triassic Mastodonsaurus tooth yields an age of 65.2 ± 1.1 Ma (MSWD = 0.68), much younger than half of the stratigraphic age (ca. 234 Ma). Hence, Hf must also undergo late diagenetic exchange. Likely mechanisms to account for the presence of statistically meaningful isochrons as well as for the late diagenetic exchange of both REE and Hf are diffusion, adsorption, and dissolution-reprecipitation processes.     

Whole-watershed mercury balance at Sagehen Creek, Sierra Nevada, CA

Few data are available on mercury (Hg) dynamics at high-elevation mountain sites. In this project, a whole-watershed approach was used to quantify major fluxes and pools of Hg in Sagehen basin, a closed basin in the Sierra Nevada mountains in California. Over a period spanning 9 months (January-September 2009), we estimated wet deposition inputs to the watershed at 3.8 μg m⁻². Dry deposition added additional Hg in the range of 0.30-2.45 μg m⁻² during this time period, and was the dominant deposition process during summer time. Seasonal snowpack accounted for only half of the Hg deposited by wet deposition. We suggest that photo-induced reduction of Hg(II) in snow and subsequent volatilization was responsible for this loss. Thus, snowpacks in the Sierra Nevada mountains likely reduce the effective atmospheric mercury flux via wet deposition due to significant emission fluxes prior to snowmelt. As such, wet Hg deposition could be of lesser importance as a Hg source in snow-dominated systems. Finally, stream runoff collected at the outlet of the watershed could account for only 4% of total Hg wet deposition suggesting that a large fraction of mercury deposition was sequestered in the ecosystem, specifically in the soils.     

Defining an absolute reference frame for ‘clumped’ isotope studies of CO2

We present a revised approach for standardizing and reporting analyses of multiply substituted isotopologues of CO₂ (i.e., ‘clumped’ isotopic species, especially the mass-47 isotopologues). Our approach standardizes such data to an absolute reference frame based on theoretical predictions of the abundances of multiply-substituted isotopologues in gaseous CO₂ at thermodynamic equilibrium. This reference frame is preferred over an inter-laboratory calibration of carbonates because it enables all laboratories measuring mass 47 CO₂ to use a common scale that is tied directly to theoretical predictions of clumping in CO₂, regardless of the laboratory’s primary research field (carbonate thermometry or CO₂ biogeochemistry); it explicitly accounts for mass spectrometric artifacts rather than convolving (and potentially confusing) them with chemical fractionations associated with sample preparation; and it is based on a thermodynamic equilibrium that can be experimentally established in any suitably equipped laboratory using commonly available materials.By analyzing CO₂ gases that have been subjected to established laboratory procedures known to promote isotopic equilibrium (i.e., heated gases and water-equilibrated CO₂), and by reference to thermodynamic predictions of equilibrium isotopic distributions, it is possible to construct an empirical transfer function that is applicable to data with unknown clumped isotope signatures. This transfer function empirically accounts for the fragmentation and recombination reactions that occur in electron impact ionization sources and other mass spectrometric artifacts. We describe the protocol necessary to construct such a reference frame, the method for converting gases with unknown clumped isotope compositions to this reference frame, and suggest a protocol for ensuring that all reported isotopic compositions (e.g., Δ₄₇ values; [Eiler and Schauble, 2004] and [Eiler, 2007]) can be compared among different laboratories and instruments, independent of laboratory-specific analytical or methodological differences. We then discuss the use of intra-laboratory secondary reference frames (e.g., based on carbonate standards) that can be more easily used to track the evolution of each laboratory’s empirical transfer function. Finally, we show inter-laboratory reproducibility on the order of ±0.010 (1σ) for four carbonate standards, and present revised paleotemperature scales that should be used to convert carbonate clumped isotope signatures to temperature when using the absolute reference frame described here. Even when using the reference frame, small discrepancies remain between two previously published synthetic carbonate calibrations. We discuss possible reasons for these discrepancies, and highlight the need for additional low temperature (<15 °C) synthetic carbonate experiments.     

Mercury in the Southern Ocean

We present here the first mercury speciation study in the water column of the Southern Ocean, using a high-resolution south-to-north section (27 stations from 65.50°S to 44.00°S) with up to 15 depths (0-4440 m) between Antarctica and Tasmania (Australia) along the 140°E meridian. In addition, in order to explore the role of sea ice in Hg cycling, a study of mercury speciation in the “snow-sea ice-seawater” continuum was conducted at a coastal site, near the Australian Casey station (66.40°S; 101.14°E). In the open ocean waters, total Hg (Hg_T) concentrations varied from 0.63 to 2.76 pmol L⁻¹ with “transient-type” vertical profiles and a latitudinal distribution suggesting an atmospheric mercury source south of the Southern Polar Front (SPF) and a surface removal north of the Subantartic Front (SAF). Slightly higher mean Hg_T concentrations (1.35 ± 0.39 pmol L⁻¹) were measured in Antarctic Bottom Water (AABW) compared to Antarctic Intermediate water (AAIW) (1.15 ± 0.22 pmol L⁻¹). Labile Hg (Hg_R) concentrations varied from 0.01 to 2.28 pmol L⁻¹, with a distribution showing that the Hg_T enrichment south of the SPF consisted mainly of Hg_R (67 ± 23%), whereas, in contrast, the percentage was half that in surface waters north of PFZ (33 ± 23%). Methylated mercury species (MeHg_T) concentrations ranged from 0.02 to 0.86 pmol L⁻¹. All vertical MeHg_T profiles exhibited roughly the same pattern, with low concentrations observed in the surface layer and increasing concentrations with depth up to an intermediate depth maximum. As for Hg_T, low mean MeHg_T concentrations were associated with AAIW, and higher ones with AABW. The maximum of MeHg_T concentration at each station was systematically observed within the oxygen minimum zone, with a statistically significant MeHg_Tvs Apparent Oxygen Utilization (AOU) relationship (p < 0.001). The proportion of Hg_T as methylated species was lower than 5% in the surface waters, around 50% in deep waters below 1000 m, reaching a maximum of 78% south of the SPF. At Casey coastal station Hg_T and Hg_R concentrations found in the “snow-sea ice-seawater” continuum were one order of magnitude higher than those measured in open ocean waters. The distribution of Hg_T there suggests an atmospheric Hg deposition with snow and a fractionation process during sea ice formation, which excludes Hg from the ice with a parallel Hg enrichment of brine, probably concurring with the Hg enrichment of AABW observed in the open ocean waters. Contrastingly, MeHg_T concentrations in the sea ice environment were in the same range as in the open ocean waters, remaining below 0.45 pmol L⁻¹. The MeHg_T vertical profile through the continuum suggests different sources, including atmosphere, seawater and methylation in basal ice. Whereas Hg_T concentrations in the water samples collected between the Antarctic continent and Tasmania are comparable to recent measurements made in the other parts of the World Ocean (e.g., Soerensen et al., 2010), the Hg species distribution suggests distinct features in the Southern Ocean Hg cycle: (i) a net atmospheric Hg deposition on surface water near the ice edge, (ii) the Hg enrichment in brine during sea ice formation, and (iii) a net methylation of Hg south of the SPF.