Carbon-isotopic analysis of individual pollen grains from C3 and C4 grasses using a spooling-wire microcombustion interface

Pollen grains from grasses using the C₃ and C₄ photosynthetic pathways have distinct ranges of δ¹³C values that may be used to estimate their relative abundance in paleorecords. We evaluated a spooling-wire microcombustion device interfaced with an isotope-ratio mass spectrometer (SWiM-IRMS) for δ¹³C analysis of individual grass-pollen grains. Pollen from four C₃ and four C₄ grass species was isolated through micromanipulation and analyzed as single grains suspended in water. A carbon yield greater than the 2σ range of the carbon content of blanks containing only water was used to distinguish samples containing pollen (“pollen present”) from those not containing pollen. This criterion resulted in the exclusion of ∼45% of the 946 samples applied to the wire. The average δ¹³C values (±1σ) of the remaining samples were −26.9‰ (±6.3‰) and −11.5‰ (±9.6‰) for C₃ grasses and C₄ grasses, respectively, after blank-correcting the δ¹³C data. These results suggest that the SWiM-IRMS system can be used to distinguish C₃ from C₄ grass pollen. The high variability in measured δ¹³C values is likely caused by a combination of factors. These include natural isotopic variability among individual pollen grains; the relatively poor precision that can be obtained when determining δ¹³C values of such small samples; and the uncertainty in the magnitude, isotopic composition, and stability of the analytical blank. Nonetheless, high percentages of individual pollen grains were correctly classified as being of either C₃ or C₄ origin. On average, 90% (range = 78-100%) of pollen grains from C₃ grasses had δ¹³C values more negative than the cutoff threshold of −19.2‰; while 84% (range = 77-90%) of pollen grains from C₄ grasses had δ¹³C values more positive than −19.2‰. Compared with analysis using an elemental analyzer interfaced with an IRMS (EA-IRMS), the number of pollen grains required for δ¹³C-based evaluation of C₃/C₄ grass composition is many times lower with the SWiM-IRMS. Additionally, δ¹³C data from the SWiM-IRMS does not need to be incorporated into a mixing model to derive estimates of the abundance of C₃ and C₄ grass pollen. Carbon-isotopic analysis of individual grass-pollen grains using the SWiM-IRMS system may help improve our understanding of the evolutionary and ecological significance of grass taxa in the paleorecord.     

NanoSIMS isotopic analysis of small presolar grains: Search for Si3N4 grains from AGB stars and Al and Ti isotopic compositions of rare presolar SiC grains

We report isotopic ratio measurements of small SiC and Si₃N₄ grains, with special emphasis on presolar SiC grains of type Z, and new nucleosynthesis models for ²⁶Al/²⁷Al and the Ti isotopic ratios in asymptotic giant branch (AGB) stars. With the NanoSIMS we analyzed 310 SiC grains from Murchison (carbonaceous CM2 chondrite) separate KJB (diameters 0.25-0.45 μm) and 153 SiC grains from KJG (diameters 1.8-3.7 μm), 154 SiC and 23 Si₃N₄ grains from Indarch (enstatite EH4 chondrite) separate IH6 (diameters 0.25-0.65 μm) for their C and N isotopic compositions, 549 SiC and 142 Si₃N₄ grains from IH6 for their C and Si isotopic compositions, 13 SiC grains from Murchison and 66 from Indarch for their Al-Mg compositions, and eight SiC grains from Murchison and 10 from Indarch for their Ti isotopic compositions. One of the original objectives of this effort was to compare isotopic analyses with the NanoSIMS with analyses previously obtained with the Cameca IMS 3f ion microprobe. Many of the Si₃N₄ grains from Indarch have isotopic anomalies but most of these apparently originate from adjacent SiC grains. Only one Si₃N₄ grain, with ¹³C and ¹⁴N excesses, has a likely AGB origin. The C, N, and Si isotopic data show that the percentage of SiC grains of type Y and Z increase with decreasing grain size (from ∼1% for grains >2 μm to ∼5-7% for grains of 0.5 μm), providing an opportunity for isotopic analyses in these rare grains. Our measurements expand the number of Al-Mg analyses on SiC Z grains from 4 to 23 and the number of Ti analyses on Z grains from 2 to 11. Inferred²⁶Al/²⁷Al ratios of Z grains are in the range found in mainstream and Y grains and do not exceed those predicted by models of AGB nucleosynthesis. Cool bottom processing (CBP) has been invoked to explain the low ¹²C/¹³C ratios of Z grains, but this process apparently does not lead to increased ²⁶Al production in the parent stars of these grains. This finding is in contrast to presolar oxide grains where CBP is needed to explain their high ²⁶Al/²⁷Al ratios. The low ^46,47,49Ti/⁴⁸Ti ratios found in Z grains and their correlation with low ²⁹Si/²⁸Si ratios extend the trend seen in mainstream grains and confirm an origin in low-metallicity AGB stars. The relatively large excesses in ³⁰Si and ⁵⁰Ti in Z grains are predicted by our models to be the result of increased production of these isotopes by neutron-capture nucleosynthesis in low-metallicity AGB stars. However, the predicted excesses in ⁵⁰Ti (and ⁴⁹Ti) are much larger than those found. Even lowering the strength of the ¹³C pocket cannot solve this discrepancy in a consistent way.     

Comparison of benthic invertebrate assemblages at Spartina alterniflora marshes reestablished after an oil spill and existing marshes in the Arthur Kill (NY/NJ)

In January 1990, an oil spill damaged salt marshes along the banks of the Arthur Kill (New York and New Jersey, USA). In the years following the spill, Spartina alterniflora seedlings were planted at a number of the oil damaged sites and successfully reestablished at these sites. In 1996, the National Marine Fisheries Service began a study to compare the benthic invertebrate assemblages at the reestablished S. alterniflora marshes to those at nearby existing marshes in the Arthur Kill. Oligochaetes, nematodes, and the small tube-building polychaete, Manayunkia aestuarina were the dominant taxa in the study. Significant differences were found in the abundances of all invertebrate individuals, oligochaetes, and nematodes between the September and May sampling times but not between reestablished and existing marshes. Although benthic invertebrate community structure was similar at reestablished and existing marshes three to four years after planting, the functional similarity of these marshes was not assessed in this study.     

Assessment of carbon in woody plants and soil across a vineyard-woodland landscape

Background

Quantification of ecosystem services, such as carbon (C) storage, can demonstrate the benefits of managing for both production and habitat conservation in agricultural landscapes. In this study, we evaluated C stocks and woody plant diversity across vineyard blocks and adjoining woodland ecosystems (wildlands) for an organic vineyard in northern California. Carbon was measured in soil from 44 one m deep pits, and in aboveground woody biomass from 93 vegetation plots. These data were combined with physical landscape variables to model C stocks using a geographic information system and multivariate linear regression.

Results

Field data showed wildlands to be heterogeneous in both C stocks and woody tree diversity, reflecting the mosaic of several different vegetation types, and storing on average 36.8 Mg C/ha in aboveground woody biomass and 89.3 Mg C/ha in soil. Not surprisingly, vineyard blocks showed less variation in above- and belowground C, with an average of 3.0 and 84.1 Mg C/ha, respectively.

Conclusions

This research demonstrates that vineyards managed with practices that conserve some fraction of adjoining wildlands yield benefits for increasing overall C stocks and species and habitat diversity in integrated agricultural landscapes. For such complex landscapes, high resolution spatial modeling is challenging and requires accurate characterization of the landscape by vegetation type, physical structure, sufficient sampling, and allometric equations that relate tree species to each landscape. Geographic information systems and remote sensing techniques are useful for integrating the above variables into an analysis platform to estimate C stocks in these working landscapes, thereby helping land managers qualify for greenhouse gas mitigation credits. Carbon policy in California, however, shows a lack of focus on C stocks compared to emissions, and on agriculture compared to other sectors. Correcting these policy shortcomings could create incentives for ecosystem service provision, including C storage, as well as encourage better farm stewardship and habitat conservation.

     

Tidal boundary conditions in SEAWAT

SEAWAT, a U.S. Geological Survey groundwater flow and transport code, is increasingly used to model the effects of tidal motion on coastal aquifers. Different options are available to simulate tidal boundaries but no guidelines exist nor have comparisons been made to identify the most effective approach. We test seven methods to simulate a sloping beach and a tidal flat. The ocean is represented in one of the three ways: directly using a high hydraulic conductivity (high-K) zone and indirect simulation via specified head boundaries using either the General Head Boundary (GHB) or the new Periodic Boundary Condition (PBC) package. All beach models simulate similar water fluxes across the upland boundary and across the sediment-water interface although the ratio of intertidal to subtidal flow is different at low tide. Simulating a seepage face results in larger intertidal fluxes and influences near-shore heads and salinity. Major differences in flow occur in the tidal flat simulations. Because SEAWAT does not simulate unsaturated flow the water table only rises via flow through the saturated zone. This results in delayed propagation of the rising tidal signal inland. Inundation of the tidal flat is delayed as is flow into the aquifer across the flat. This is severe in the high-K and PBC models but mild in the GHB models. Results indicate that any of the tidal boundary options are fine if the ocean-aquifer interface is steep. However, as the slope of that interface decreases, the high-K and PBC approaches perform poorly and the GHB boundary is preferable.     

Anaerobic precipitation of manganese and co-existing metals in mine impacted water treated with crab shell-associated minerals

The chemical and physical treatment mechanisms by which crab shell removes metals from mine impacted water (MIW) were evaluated under anaerobic and biologically limited conditions in closed systems and kinetic tests. Raw (R-SC20) and deproteinized (DP-SC20) crab shell were tested and compared to limestone to quantify the contribution of chitin-associated minerals and proteins to alkalinity generation and metal precipitation. Single-metal closed systems (initial Mn and Fe = 0.18 mM and Al = 0.34 mM) containing 5 g/L of either R- or DP-SC20, yielded an increase in pH from 3 to 9.2-10.2, generation of 0.83-1.87 mM of alkalinity, and resulted in ?95% removal of metals within 72 h. In contrast, 5-125 g limestone/L only raised the pH to 7.8-8.3, produced lower alkalinity (0.56-0.63 mM), and resulted in less metal removal (?85%). In kinetic tests with 5 g-DP-SC20/L, removal of ?95% of the initial metal load was achieved after 0.5, 6, and 48 h for Al, Fe, and Mn, respectively. Geochemical calculations (PHREEQC) indicate that limestone-treated systems were close to equilibrium with calcite (CaCO₃), whereas octacalcium phosphate (Ca₄H(PO₄)₃) appears to be a controlling phase in systems treated with R- and DP-SC20. The probable mechanisms for Mn removal are the precipitation of rhodochrosite (MnCO₃) and/or sorption. In the case of Al and Fe, geochemical calculations point to the precipitation of hydroxides; however, visual observations in Fe systems suggest the formation of green rust, a precursor of other, more stable phases like goethite or lepidocrocite. Several factors may account for the faster changes observed with R- and DP-SC20 compared to limestone: increased dissolution and degree of supersaturation, the presence of phosphates, the release of organic compounds, and a significantly larger surface area. These results are the first to verify and quantify the capacity of crab shell-associated minerals to treat MIW under biologically limited conditions.     

Control of deep convection by sub-cloud lifting processes: the ALP closure in the LMDZ5B general circulation model

Recently, a new conceptual framework for deep convection scheme triggering and closure has been developed and implemented in the LMDZ5B general circulation model, based on the idea that deep convection is controlled by sub-cloud lifting processes. Such processes include boundary-layer thermals and evaporatively-driven cold pools (wakes), which provide an available lifting energy that is compared to the convective inhibition to trigger deep convection, and an available lifting power (ALP) at cloud base, which is used to compute the convective mass flux assuming the updraft vertical velocity at the level of free convection. While the ALP closure was shown to delay the local hour of maximum precipitation over land in better agreement with observations, it results in an underestimation of the convection intensity over the tropical ocean both in the 1D and 3D configurations of the model. The specification of the updraft vertical velocity at the level of free convection appears to be a key aspect of the closure formulation, as it is weaker over tropical ocean than over land and weaker in moist mid-latitudes than semi-arid regions. We propose a formulation making this velocity increase with the level of free convection, so that the ALP closure is adapted to various environments. Cloud-resolving model simulations of observed oceanic and continental case studies are used to evaluate the representation of lifting processes and test the assumptions at the basis of the ALP closure formulation. Results favor closures based on the lifting power of sub-grid sub-cloud processes rather than those involving quasi-equilibrium with the large-scale environment. The new version of the model including boundary-layer thermals and cold pools coupled together with the deep convection scheme via the ALP closure significantly improves the representation of various observed case studies in 1D mode. It also substantially modifies precipitation patterns in the full 3D version of the model, including seasonal means, diurnal cycle and intraseasonal variability.