Influence of physiology and climate on δD of leaf wax n-alkanes from C3 and C4 grasses

We measured hydrogen isotope compositions (δD) of high-molecular-weight n-alkanes (C₂₇-C₃₃) from grasses grown in greenhouses and collected from the US Great Plains. In both cases, n-alkanes from C₄ grasses are enriched in D by more than 20‰ relative to those from C₃ grasses. The apparent enrichment factor (ε_C29-GW) between C₂₉n-alkane and greenhouse water is −165 ± 12‰ for C₃ grasses and −140 ± 15‰ for C₄ grasses. For samples from the Great Plains, δD values of C₂₉n-alkanes range from −280 to −136‰, with values for C₄ grasses ca. 21‰ more positive than those for C₃ grasses from the same site. Differences in C₃ and C₄ grass n-alkane δD values are consistent with the shorter interveinal distance in C₄ grass leaves, and greater back-diffusion of enriched water from stomata to veins, than in C₃ grass leaves. Great Plains’ grass n-alkane isotopic ratios largely reflect precipitation δD values. However, the offset or apparent fractionation between n-alkanes and precipitation is not uniform and varies with annual precipitation and relative humidity, suggesting climatic controls on lipid δD values. The dryer sites exhibit smaller absolute apparent fractionation indicative of D-enrichment of source waters through transpiration and/or soil evaporation. To explore the relationship between climate and n-alkane δD values, we develop three models. (1) The ‘direct analog’ model estimates δD_C29 values simply by applying the apparent enrichment factors, ε_C29-GW, observed in greenhouse grasses to precipitation δD values from the Great Plains. (2) The ‘leaf-water’ model uses a Craig-Gordon model to estimate transpirational D-enrichment for both greenhouse and field sites. The transpiration-corrected enrichment factors between C₂₉ and bulk leaf-water, ε_C29-GW, calculated from the greenhouse samples (−181‰ for C₃ and −157‰ for C₄) are applied to estimate δD_C29 values relative to modeled bulk leaf-water δD values. (3) The ‘soil- and leaf-water’ model estimates the combined effects of soil evaporation, modeled by analogy with a flow-through lake, and transpiration on δD_C29 values. Predictions improve with the addition of the explicit consideration of transpiration and soil evaporation, indicating that they are both important processes in determining plant lipid δD values. D-enrichment caused by these evaporative processes is controlled by relative humidity, suggesting that important climatic information is recorded in leaf wax n-alkane δD values. Calibration studies such as this one provide a baseline for future studies of plant-water-deuterium systematics and form the foundation for interpretation of plant wax hydrogen isotope ratios as a paleo-aridity proxy.     

δC of low-molecular-weight organic acids generated by the hydrous pyrolysis of oil-prone source rocks

Low-molecular-weight (LMW) aqueous organic acids were generated from six oil-prone source rocks under hydrous-pyrolysis conditions. Differences in total organic carbon-normalized acid generation are a function of the initial thermal maturity of the source rock and the oxygen content of the kerogen (OI). Carbon-isotope analyses were used to identify potential generation mechanisms and other chemical reactions that might influence the occurrence of LMW organic acids. The generated LMW acids display increasing ¹³C content as a function of decreasing molecular weight and increasing thermal maturity. The magnitudes of observed isotope fractionations are source-rock dependent. These data are consistent with δ¹³C values of organic acids presented in a field study of the San Joaquin Basin and likely reflect the contributions from alkyl-carbons and carboxyl-carbons with distinct δ¹³C values. The data do not support any particular organic acid generation mechanism. The isotopic trends observed as a function of molecular weight, thermal maturity, and rock type are not supported by either generation mechanisms or destructive decarboxylation. It is therefore proposed that organic acids experience isotopic fractionation during generation consistent with a primary kinetic isotope effect and subsequently undergo an exchange reaction between the carboxyl carbon and dissolved inorganic carbon that significantly influences the carbon isotope composition observed for the entire molecule. Although generation and decarboxylation may influence the δ¹³C values of organic acids, in the hydrous pyrolysis system described, the nondestructive, pH-dependent exchange of carboxyl carbon with inorganic carbon appears to be the most important reaction mechanism controlling the δ¹³C values of the organic acids.     

Depositional ice nucleation on NX illite and mixtures of NX illite with organic acids

Mineral dust particles are known to be efficient ice nuclei in the atmosphere. Previous work has probed heterogeneous ice nucleation on various laboratory dust samples including Arizona Test Dust, kaolinite, montmorillonite, and illite as atmospheric dust surrogates. However, it has recently been suggested that NX illite may be a better representation of atmospheric dust. Hiranuma et al. (2015) performed a laboratory comparison for immersion ice nucleation on NX illite, but here we focus on depositional ice nucleation because of its importance in low temperature cirrus cloud formation. A Raman microscope setup was used to examine the ice-nucleating efficiency of NX illite. Organic coatings on the NX illite particles were also investigated using a mixture of 5 dicarboxylic acids (M5). The ratio of NX illite to M5 was varied from 1:10 to 100:1. It was found that NX illite efficiently nucleates ice with S_ice = 1.07 ± 0.01 at ?47 °C, with S_ice slightly increasing at lower temperatures. In contrast, pure M5 is a poorer ice nucleus with S_ice = 1.30 ± 0.02 at ?40 °C, relatively independent of temperature. Further, it was found that M5 coatings on the order of several monolayers thick hindered the ice nucleating ability of NX illite. Optical images suggest that at colder temperatures (< ?50 °C) 1:1 NX illite:M5 particles and pure M5 particles nucleate ice depositionally, while at warmer temperatures (> ?50 °C) subsaturated immersion ice nucleation dominates. These experiments suggest that mineral dust particles may become less active towards ice nucleation as they age in the atmosphere.     

Climatic drivers of tree growth at tree line in Southwest Yukon change over time and vary between landscapes

Growth of trees at their altitudinal and latitudinal range limits is expected to increase as climate warms, but trees often exhibit unexplained spatial and temporal variation in climate-growth responses, particularly in alpine regions. Until this variability is explained, predictions of future tree growth are unlikely to be accurate. We sampled Picea glauca (white spruce) growing at forest and tree line on north and south aspects in two mountain ranges of southwest Yukon to determine how and why ring-width patterns vary between topographic settings, and over time. We used multivariate statistical analysis to characterize variation in ring-width patterns between topographic factors and time periods, and calculated correlations between ring-width indices and climate variables to explain this variation. Ring-width patterns varied more between mountain ranges than elevations or aspects, particularly in recent decades when ring-widths increased in one mountain range but not the other. Growth responses to summer temperature were notably weaker during warmer time periods, but growth was not positively correlated to summer precipitation, suggesting trees may not be suffering from temperature-induced drought stress. Rather, ring-width indices began responding positively to spring snow depth after 1976. We conclude that tree growth is unlikely to increase in synchrony with rising air temperatures across subarctic tree lines in southwest Yukon. Instead, they may decline in areas that are prone to thin snowpacks or rapid spring runoff due to the negative influence warming springs will have on snow depth and, consequently, early growing season soil moisture.     

Implications of simultaneously mitigating and adapting to climate change: initial experiments using GCAM

Most research on future climate change discusses mitigation and impacts/adaptation separately. However, mitigation will have implications for impacts and adaptation. Similarly, impacts and adaptation will affect mitigation. This paper begins to explore these two veins of research simultaneously using an integrated assessment model. We begin by discussing the types of interactions one might expect by impact sector. Then, we develop a numerical experiment in the agriculture sector to illustrate the importance of considering mitigation, impacts, and adaptation at the same time. In our experiment, we find that climate change can reduce crop yields, resulting in an expansion of cropland to feed a growing population and a reduction in bioenergy production. These two effects, in combination, result in an increase in the cost of mitigation.     

Biofouling confounds the uptake of trace organic contaminants by semi-permeable membrane devices (SPMDs)

The outer layers of layflat, low density polyethylene plastic tubing (the principal component of semi-permeable membrane devices, SPMDs) were biofouled at a clean site in Hong Kong coastal waters for periods of 1–4 weeks. Following pre-fouling, triolein was added to the SPMDs and, along with control (unfouled) devices, they were exposed to a range of organochlorine pesticides (-HCH, aldrin, p,p^′-DDT) and PAHs (anthracene, fluoranthene and benzo(a)pyrene) under laboratory conditions. Results showed that the uptake of contaminants by SPMDs was severely reduced by as much as 50% under fouling conditions in comparison to unfouled controls. The ultimate utility of SPMDs as passive monitors is thus reduced, although alternative measures, such as the use of permeability reference compounds may compensate, and allow for realistic evaluations of dissolved environmental concentrations in aquatic environments. However, due to the complexities involved in such procedures––especially as they need to be conducted on a case-by-case basis––the utility of SPMDs appears to be limited for estimates of bioavailability unless necessary calibrations are undertaken within each environment that the sampler is used.     

Trophic relationships of three sunfishes (Lepomis spp.) in an estuarine bayou

We examined ontogenetic, interspecific, and seasonal trophic patterns among sympatric sunfish species, redspotted sunfish,Lepomis miniatus; redear sunfish,Lepomis microlophus; and bluegill,Lepomis macrochirus, in an estuarine bayou. In particular we studied these feeding patterns in relation to relative abundances of prey from different benthic feeding habitats. All three sunfishes showed ontogenetic divergence in their trophic niches, reflecting different ecomorphological specializations. Small fishes depended on zooplankton, whereas larger fishes of all three species shifted their diets to benthic macrofauna. A potential for trophic resource partitioning was reflected by dietary differences among the three sunfish species. One impalied mechanism for resource partitioning was feeding habitat, as redear sunfish frequently used sediment-associated prey, while bluegill showed greater use of water-column-associated prey, and redspotted sunfish often used SAV-associated prey. However, all three sunfishes apparently used each feeding habitat to some degree; and, trophic differences were more clearly based on prey type than on feeding habitat. Redear sunfish, which can crush hard-shelled prey, exhibited the most distinctive diet. An apparent seasonal shift in feeding habitat occurred in autumn/winter, as indicated by increased overlap between diets and SAV. This shift was facilitated by changes in the relative abundances of several common prey types between benthic habitats. The relative abuandance and use of freshwater and estuarine-derived prey also varied seasonally, suggesting a possible trophic benefit of consistent prey availability in the estuarine bayou.