Can increasing carbon dioxide cause climate change?

The realistic physical functioning of the greenhouse effect is reviewed, and the role of dynamic transport and water vapor is identified. Model errors and uncertainties are quantitatively compared with the forcing due to doubling CO2, and they are shown to be too large for reliable model evaluations of climate sensitivities. The possibility of directly measuring climate sensitivity is reviewed. A direct approach using satellite data to relate changes in globally averaged radiative flux changes at the top of the atmosphere to naturally occurring changes in global mean temperature is described. Indirect approaches to evaluating climate sensitivity involving the response to volcanic eruptions and Eocene climate change are also described. Finally, it is explained how, in principle, a climate that is insensitive to gross radiative forcing as produced by doubling CO2 might still be able to undergo major changes of the sort associated with ice ages and equable climates.

Variability of the ocean heat content during the last millennium - an assessment with the ECHO-g Model

Studies addressing climate variability during the last millennium generally focus on variables with a direct influence on climate variability, like the fast thermal response to varying radiative forcing, or the large-scale changes in atmospheric dynamics (e. g. North Atlantic Oscillation). The ocean responds to these variations by slowly integrating in depth the upper heat flux changes, thus producing a delayed influence on ocean heat content (OHC) that can later impact low frequency SST (sea surface temperature) variability through reemergence processes. In this study, both the externally and internally driven variations of the OHC during the last millennium are investigated using a set of fully coupled simulations with the ECHO-G (coupled climate model ECHAMA4 and ocean model HOPE-G) atmosphere-ocean general circulation model (AOGCM). When compared to observations for the last 55 yr, the model tends to overestimate the global trends and underestimate the decadal OHC variability. Extending the analysis back to the last one thousand years, the main impact of the radiative forcing is an OHC increase at high latitudes, explained to some extent by a reduction in cloud cover and the subsequent increase of short-wave radiation at the surface. This OHC response is dominated by the effect of volcanism in the preindustrial era, and by the fast increase of GHGs during the last 150 yr. Likewise, salient impacts from internal climate variability are observed at regional scales. For instance, upper temperature in the equatorial Pacific is controlled by ENSO (El Nino Southern Oscillation) variability from interannual to multidecadal timescales. Also, both the Pacific Decadal Oscillation (PDO) and the Atlantic Multidecadal Oscillation (AMO) modulate intermittently the interdecadal OHC variability in the North Pacific and Mid Atlantic, respectively. The NAO, through its influence on North Atlantic surface heat fluxes and convection, also plays an important role on the OHC at multiple timescales, leading first to a cooling in the Labrador and Irminger seas, and later on to a North Atlantic warming, associated with a delayed impact on the AMO.

Temperatures at the last interglacial simulated by a coupled ocean-atmosphere climate model

The last interglacial (Eemian, 125,000 years ago) has generally been considered the warmest time period in the last 200,000 years and thus sometimes been used as a reference for greenhouse projections. Herein we report results from a coupled ocean-atmosphere climate model of the surface temperature response to changes in the radiative forcing at the last interglacial. Although the model generates the expected summer warming in the northern hemisphere, winter cooling of a comparable magnitude occurs over North Africa and tropical Asia. The global annual mean temperature for the Eemian run is 0.3 degrees C cooler than the control run. Validation of simulated sea surface temperatures (SSTs) against reconstructed SSTs supports this conclusion and also the assumption that the flux correction, fitted for the present state, operates satisfactorily for modest perturbations. Our results imply that contrary to conventional expectations, Eemian global temperatures may already have been reached by the mid 20th century.

Geochemistry of Globigerinoides ruber from ODP Hole 130-806B

A sea surface temperature (SST) record based on planktonic foraminiferal magnesium/calcium ratios from a site in the western equatorial Pacific warm pool reveals that glacial-interglacial oscillations in SST shifted from a period of 41,000 to 100,000 years at the mid-Pleistocene transition, 950,000 years before the present. SST changes at both periodicities were synchronous with eastern Pacific cold-tongue SSTs but preceded changes in continental ice volume. The timing and nature of tropical Pacific SST changes over the mid-Pleistocene transition implicate a shift in the periodicity of radiative forcing by atmospheric carbon dioxide as the cause of the switch in climate periodicities at this time.

Effects of Simulated Drought on the Carbon Balance of Everglades Short-Hydroperiod Marsh

Hydrology drives the carbon balance of wetlands by controlling the uptake and release of CO2 and CH4. Longer dry periods in between heavier precipitation events predicted for the Everglades region, may alter the stability of large carbon pools in this wetland's ecosystems. To determine the effects of drought on CO2 fluxes and CH4 emissions, we simulated changes in hydroperiod with three scenarios that differed in the onset rate of drought (gradual, intermediate, and rapid transition into drought) on 18 freshwater wetland monoliths collected from an Everglades short-hydroperiod marsh. Simulated drought, regardless of the onset rate, resulted in higher net CO2 losses net ecosystem exchange (NEE) over the 22-week manipulation. Drought caused extensive vegetation dieback, increased ecosystem respiration (Reco), and reduced carbon uptake gross ecosystem exchange (GEE). Photosynthetic potential measured by reflective indices (photochemical reflectance index, water index, normalized phaeophytinization index, and the normalized difference vegetation index) indicated that water stress limited GEE and inhibited Reco. As a result of drought-induced dieback, NEE did not offset methane production during periods of inundation. The average ratio of net CH4 to NEE over the study period was 0.06, surpassing the 100-year greenhouse warming compensation point for CH4 (0.04). Drought-induced diebacks of sawgrass (C3) led to the establishment of the invasive species torpedograss (C4) when water was resupplied. These changes in the structure and function indicate that freshwater marsh ecosystems can become a net source of CO2 and CH4 to the atmosphere, even following an extended drought. Future changes in precipitation patterns and drought occurrence/duration can change the carbon storage capacity of freshwater marshes from sinks to sources of carbon to the atmosphere. Therefore, climate change will impact the carbon storage capacity of freshwater marshes by influencing water availability and the potential for positive feedbacks on radiative forcing.

Present-day Pattern Variations in the Central and Eastern Pacific El Nino

El Niño and the Southern Oscillation (ENSO) is a cycle that is initiated in the equatorial Pacific Ocean and is recognized on interannual timescales by oscillating patterns in tropical Pacific sea surface temperatures (SST) and atmospheric circulations. Using correlation and regression analysis of datasets that include SST’s and other interdependent variables including precipitation, surface winds, sea level pressure, this research seeks to quantify recent changes in ENSO behavior. Specifically, the amplitude, frequency of occurrence, and spatial characteristics (i.e. events with maximum amplitude in the Central Pacific versus the Eastern Pacific) are investigated. The research is based on the question; “Are the statistics of ENSO changing due to increasing greenhouse gas concentrations?” Our hypothesis is that the present-day changes in amplitude, frequency, and spatial characteristics of ENSO are determined by the natural variability of the ocean-atmosphere climate system, not the observed changes in the radiative forcing due to change in the concentrations of greenhouse gases. Statistical analysis, including correlation and regression analysis, is performed on observational ocean and atmospheric datasets available from the National Oceanographic and Atmospheric Administration (NOAA), National Center for Atmospheric Research (NCAR) and coupled model simulations from the Coupled Model Inter-comparison Project (phase 5, CMIP5). Datasets are analyzed with a particular focus on ENSO over the last thirty years. Understanding the observed changes in the ENSO phenomenon over recent decades has a worldwide significance. ENSO is the largest climate signal on timescales of 2 - 7 years and affects billions of people via atmospheric teleconnections that originate in the tropical Pacific. These teleconnections explain why changes in ENSO can lead to climate variations in areas including North and South America, Asia, and Australia. For the United States, El Niño events are linked to decreased number of hurricanes in the Atlantic basin, reduction in precipitation in the Pacific Northwest, and increased precipitation throughout the southern United Stated during winter months. Understanding variability in the amplitude, frequency, and spatial characteristics of ENSO is crucial for decision makers who must adapt where regional ecology and agriculture are affected by ENSO.

Present-day Pattern Variations in the Central and Eastern Pacific El Nino

El Niño and the Southern Oscillation (ENSO) is a cycle that is initiated in the equatorial Pacific Ocean and is recognized on interannual timescales by oscillating patterns in tropical Pacific sea surface temperatures (SST) and atmospheric circulations. Using correlation and regression analysis of datasets that include SST’s and other interdependent variables including precipitation, surface winds, sea level pressure, this research seeks to quantify recent changes in ENSO behavior. Specifically, the amplitude, frequency of occurrence, and spatial characteristics (i.e. events with maximum amplitude in the Central Pacific versus the Eastern Pacific) are investigated. The research is based on the question; “Are the statistics of ENSO changing due to increasing greenhouse gas concentrations?” Our hypothesis is that the present-day changes in amplitude, frequency, and spatial characteristics of ENSO are determined by the natural variability of the ocean-atmosphere climate system, not the observed changes in the radiative forcing due to change in the concentrations of greenhouse gases. Statistical analysis, including correlation and regression analysis, is performed on observational ocean and atmospheric datasets available from the National Oceanographic and Atmospheric Administration (NOAA), National Center for Atmospheric Research (NCAR) and coupled model simulations from the Coupled Model Inter-comparison Project (phase 5, CMIP5). Datasets are analyzed with a particular focus on ENSO over the last thirty years. Understanding the observed changes in the ENSO phenomenon over recent decades has a worldwide significance. ENSO is the largest climate signal on timescales of 2 - 7 years and affects billions of people via atmospheric teleconnections that originate in the tropical Pacific. These teleconnections explain why changes in ENSO can lead to climate variations in areas including North and South America, Asia, and Australia. For the United States, El Niño events are linked to decreased number of hurricanes in the Atlantic basin, reduction in precipitation in the Pacific Northwest, and increased precipitation throughout the southern United Stated during winter months. Understanding variability in the amplitude, frequency, and spatial characteristics of ENSO is crucial for decision makers who must adapt where regional ecology and agriculture are affected by ENSO.

Single particle characterization using the soot particle aerosol mass spectrometer (SP-AMS)

Understanding the impact of atmospheric black carbon (BC) containing particles on human health and radiative forcing requires knowledge of the mixing state of BC, including the characteristics of the materials with which it is internally mixed. In this study, we demonstrate for the first time the capabilities of the Aerodyne Soot-Particle Aerosol Mass Spectrometer equipped with a light scattering module (LS-SP-AMS) to examine the mixing state of refractory BC (rBC) and other aerosol components in an urban environment (downtown Toronto). K-means clustering analysis was used to classify single particle mass spectra into chemically distinct groups. One resultant cluster is dominated by rBC mass spectral signals (C+1 to C+5) while the organic signals fall into a few major clusters, identified as hydrocarbon-like organic aerosol (HOA), oxygenated organic aerosol (OOA), and cooking emission organic aerosol (COA). A nearly external mixing is observed with small BC particles only thinly coated by HOA ( 28% by mass on average), while over 90% of the HOA-rich particles did not contain detectable amounts of rBC. Most of the particles classified into other inorganic and organic clusters were not significantly associated with BC. The single particle results also suggest that HOA and COA emitted from anthropogenic sources were likely major contributors to organic-rich particles with low to mid-range aerodynamic diameter (dva). The similar temporal profiles and mass spectral features of the organic clusters and the factors from a positive matrix factorization (PMF) analysis of the ensemble aerosol dataset validate the conventional interpretation of the PMF results.

The Effects of Organic Matter Amendments and Migratory Waterfowl on Greenhouse Gas and Nutrient Dynamics in Managed Coastal Plain Wetlands

Wetland ecosystems provide many valuable ecosystem services, including carbon (C) storage and improvement of water quality. Yet, restored and managed wetlands are not frequently evaluated for their capacity to function in order to deliver on these values. Specific restoration or management practices designed to meet one set of criteria may yield unrecognized biogeochemical costs or co-benefits. The goal of this dissertation is to improve scientific understanding of how wetland restoration practices and waterfowl habitat management affect critical wetland biogeochemical processes related to greenhouse gas emissions and nutrient cycling. I met this goal through field and laboratory research experiments in which I tested for relationships between management factors and the biogeochemical responses of wetland soil, water, plants and trace gas emissions. Specifically, I quantified: (1) the effect of organic matter amendments on the carbon balance of a restored wetland; (2) the effectiveness of two static chamber designs in measuring methane (CH4) emissions from wetlands; (3) the impact of waterfowl herbivory on the oxygen-sensitive processes of methane emission and coupled nitrification-denitrification; and (4) nitrogen (N) exports caused by prescribed draw down of a waterfowl impoundment.

The potency of CH4 emissions from wetlands raises the concern that widespread restoration and/or creation of freshwater wetlands may present a radiative forcing hazard. Yet data on greenhouse gas emissions from restored wetlands are sparse and there has been little investigation into the greenhouse gas effects of amending wetland soils with organic matter, a recent practice used to improve function of mitigation wetlands in the Eastern United States. I measured trace gas emissions across an organic matter gradient at a restored wetland in the coastal plain of Virginia to test the hypothesis that added C substrate would increase the emission of CH4. I found soils heavily loaded with organic matter emitted significantly more carbon dioxide than those that have received little or no organic matter. CH4 emissions from the wetland were low compared to reference wetlands and contrary to my hypothesis, showed no relationship with the loading rate of added organic matter or total soil C. The addition of moderate amounts of organic matter (< 11.2 kg m-2) to the wetland did not greatly increase greenhouse gas emissions, while the addition of high amounts produced additional carbon dioxide, but not CH4.

I found that the static chambers I used for sampling CH4 in wetlands were highly sensitive to soil disturbance. Temporary compression around chambers during sampling inflated the initial chamber CH4 headspace concentration and/or lead to generation of nonlinear, unreliable flux estimates that had to be discarded. I tested an often-used rubber-gasket sealed static chamber against a water-filled-gutter seal chamber I designed that could be set up and sampled from a distance of 2 m with a remote rod sampling system to reduce soil disturbance. Compared to the conventional design, the remotely-sampled static chambers reduced the chance of detecting inflated initial CH4 concentrations from 66 to 6%, and nearly doubled the proportion of robust linear regressions from 45 to 86%. The new system I developed allows for more accurate and reliable CH4 sampling without costly boardwalk construction.

I explored the relationship between CH4 emissions and aquatic herbivores, which are recognized for imposing top-down control on the structure of wetland ecosystems. The biogeochemical consequences of herbivore-driven disruption of plant growth, and in turn, mediated oxygen transport into wetland sediments, were not previously known. Two growing seasons of herbivore exclusion experiments in a major waterfowl overwintering wetland in the Southeastern U.S. demonstrate that waterfowl herbivory had a strong impact on the oxygen-sensitive processes of CH4 emission and nitrification. Denudation by herbivorous birds increased cumulative CH4 flux by 233% (a mean of 63 g CH4 m-2 y-1) and inhibited coupled nitrification-denitrification, as indicated by nitrate availability and emissions of nitrous oxide. The recognition that large populations of aquatic herbivores may influence the capacity for wetlands to emit greenhouse gases and cycle nitrogen is particularly salient in the context of climate change and nutrient pollution mitigation goals. For example, our results suggest that annual emissions of 23 Gg of CH4 y-1 from ~55,000 ha of publicly owned waterfowl impoundments in the Southeastern U.S. could be tripled by overgrazing.

Hydrologically controlled moist-soil impoundment wetlands provide critical habitat for high densities of migratory bird populations, thus their potential to export nitrogen (N) to downstream waters may contribute to the eutrophication of aquatic ecosystems. To investigate the relative importance of N export from these built and managed habitats, I conducted a field study at an impoundment wetland that drains into hypereutrophic Lake Mattamuskeet. I found that prescribed hydrologic drawdowns of the impoundment exported roughly the same amount of N (14 to 22 kg ha-1) as adjacent fertilized agricultural fields (16 to 31 kg ha-1), and contributed approximately one-fifth of total N load (~45 Mg N y-1) to Lake Mattamuskeet. Ironically, the prescribed drawdown regime, designed to maximize waterfowl production in impoundments, may be exacerbating the degradation of habitat quality in the downstream lake. Few studies of wetland N dynamics have targeted impoundments managed to provide wildlife habitat, but a similar phenomenon may occur in some of the 36,000 ha of similarly-managed moist-soil impoundments on National Wildlife Refuges in the southeastern U.S. I suggest early drawdown as a potential method to mitigate impoundment N pollution and estimate it could reduce N export from our study impoundment by more than 70%.

In this dissertation research I found direct relationships between wetland restoration and impoundment management practices, and biogeochemical responses of greenhouse gas emission and nutrient cycling. Elevated soil C at a restored wetland increased CO2 losses even ten years after the organic matter was originally added and intensive herbivory impact on emergent aquatic vegetation resulted in a ~230% increase in CH4 emissions and impaired N cycling and removal. These findings have important implications for the basic understanding of the biogeochemical functioning of wetlands and practical importance for wetland restoration and impoundment management in the face of pressure to mitigate the environmental challenges of global warming and aquatic eutrophication.

Elucidating the Space-Time Structure of Low Level Warm Season Precipitation Processes in the Southern Appalachian Mountains Using Models and Observations

Light rainfall is the baseline input to the annual water budget in mountainous landscapes through the tropics and at mid-latitudes. In the Southern Appalachians, the contribution from light rainfall ranges from 50-60% during wet years to 80-90% during dry years, with convective activity and tropical cyclone input providing most of the interannual variability. The Southern Appalachians is a region characterized by rich biodiversity that is vulnerable to land use/land cover changes due to its proximity to a rapidly growing population. Persistent near surface moisture and associated microclimates observed in this region has been well documented since the colonization of the area in terms of species health, fire frequency, and overall biodiversity. The overarching objective of this research is to elucidate the microphysics of light rainfall and the dynamics of low level moisture in the inner region of the Southern Appalachians during the warm season, with a focus on orographically mediated processes. The overarching research hypothesis is that physical processes leading to and governing the life cycle of orographic fog, low level clouds, and precipitation, and their interactions, are strongly tied to landform, land cover, and the diurnal cycles of flow patterns, radiative forcing, and surface fluxes at the ridge-valley scale. The following science questions will be addressed specifically: 1) How do orographic clouds and fog affect the hydrometeorological regime from event to annual scale and as a function of terrain characteristics and land cover?; 2) What are the source areas, governing processes, and relevant time-scales of near surface moisture convergence patterns in the region?; and 3) What are the four dimensional microphysical and dynamical characteristics, including variability and controlling factors and processes, of fog and light rainfall? The research was conducted with two major components: 1) ground-based high-quality observations using multi-sensor platforms and 2) interpretive numerical modeling guided by the analysis of the in situ data collection. Findings illuminate a high level of spatial – down to the ridge scale - and temporal – from event to annual scale - heterogeneity in observations, and a significant impact on the hydrological regime as a result of seeder-feeder interactions among fog, low level clouds, and stratiform rainfall that enhance coalescence efficiency and lead to significantly higher rainfall rates at the land surface. Specifically, results show that enhancement of an event up to one order of magnitude in short-term accumulation can occur as a result of concurrent fog presence. Results also show that events are modulated strongly by terrain characteristics including elevation, slope, geometry, and land cover. These factors produce interactions between highly localized flows and gradients of temperature and moisture with larger scale circulations. Resulting observations of DSD and rainfall patterns are stratified by region and altitude and exhibit clear diurnal and seasonal cycles.

Delta 44/40 Ca, Mg/Ca and Sr/Ca record of Globigerinoides sacculifer and calculated temperatures and salinity changes of ODP Hole 165-999A

The delta18O values of planktonic foraminifera increased in the Caribbean by about 0.5? relative to the equatorial East Pacific values between 4.6 and 4.2 Ma as a consequence of the closure of the Central American Gateway (CAG). This increase in delta18O can be interpreted either as an increase in Caribbean sea surface (mixed layer) salinity (SSS) or as a decrease in sea surface temperatures (SST). This problem represents an ideal situation to apply the recently developed paleotemperature proxy delta44/40Ca together with Mg/Ca and d18O on the planktic foraminifer Globigerinoides sacculifer from ODP Site 999. Although differences in absolute temperature calibration of delta44/40Ca and Mg/Ca exist, the general pattern is similar indicating a SST decrease of about 2-3 8C between 4.4 and 4.3 Ma followed by an increase in the same order of magnitude between 4.3 and 4.0 Ma. Correcting the delta18O record for this temperature change and assuming that changes in global ice volume are negligible, the salinity-induced planktonic delta18O signal decreased by about 0.4? between 4.4 and 4.3 Ma and increased by about 0.9? between 4.3 and 4.0 Ma in the Caribbean. The observed temperature and salinity trends are interpreted to reflect the restricted exchange of surface water between the Caribbean and the Pacific in response to the shoaling of the Panamanian Seaway, possibly accompanied by a southward shift of the Intertropical Convergence Zone (ITCZ) between 4.4 and 4.3 Ma. Differences in Mg/Ca- and delta44/40Ca-derived temperatures can be reconciled by corrections for secular variations of the marine Mg/Ca[sw] and delta44/40Ca, a salinity effect on the Mg/Ca ratio and a constant temperature offset of ~2.5 °C between both SST proxy calibrations.

Modeling long-term variability and change of soil moisture and groundwater level - from catchment to global scale

The water stored in and flowing through the subsurface is fundamental for sustaining human activities and needs, feeding water and its constituents to surface water bodies and supporting the functioning of their ecosystems. Quantifying the changes that affect the subsurface water is crucial for our understanding of its dynamics and changes driven by climate change and other changes in the landscape, such as in land-use and water-use. It is inherently difficult to directly measure soil moisture and groundwater levels over large spatial scales and long times. Models are therefore needed to capture the soil moisture and groundwater level dynamics over such large spatiotemporal scales. This thesis develops a modeling framework that allows for long-term catchment-scale screening of soil moisture and groundwater level changes. The novelty in this development resides in an explicit link drawn between catchment-scale hydroclimatic and soil hydraulics conditions, using observed runoff data as an approximation of soil water flux and accounting for the effects of snow storage-melting dynamics on that flux. Both past and future relative changes can be assessed by use of this modeling framework, with future change projections based on common climate model outputs. By direct model-observation comparison, the thesis shows that the developed modeling framework can reproduce the temporal variability of large-scale changes in soil water storage, as obtained from the GRACE satellite product, for most of 25 large study catchments around the world. Also compared with locally measured soil water content and groundwater level in 10 U.S. catchments, the modeling approach can reasonably well reproduce relative seasonal fluctuations around long-term average values. The developed modeling framework is further used to project soil moisture changes due to expected future climate change for 81 catchments around the world. The future soil moisture changes depend on the considered radiative forcing scenario (RCP) but are overall large for the occurrence frequency of dry and wet events and the inter-annual variability of seasonal soil moisture. These changes tend to be higher for the dry events and the dry season, respectively, than for the corresponding wet quantities, indicating increased drought risk for some parts of the world.

Measurements of small ice crystals in arctic cirrus: observations from the Indirect and Semi-Direct Aerosol Campaign (ISDAC)

In-situ observations on the size and shape of particles in arctic cirrus are less common than those in mid-latitude and tropical cirrus with considerable uncertainty about the contributions of small ice crystals (maximum dimension D<50 µm) to the mass and radiative properties that impact radiative forcing. In situ measurements of small ice crystals in arctic cirrus were made during the Indirect and Semi-Direct Aerosol Campaign (ISDAC) in April 2008 during transits of the National Research Council of Canada Convair-580 between Fairbanks and Barrow, Alaska and during Mixed Phase Arctic Cloud Experiment (MPACE) in October 2004 with the University of North Dakota (UND) Citation over Barrow, Alaska. Concentrations of small ice crystals with D < 50 μm from a Cloud and Aerosol Spectrometer (CAS), a Cloud Droplet Probe (CDP), a Forward Scattering Spectrometer Probe (FSSP), and a two-dimensional stereo probe (2DS) were compared as functions of the concentrations of crystals with D > 100 μm measured by a Cloud Imaging Probe (CIP) and two-dimensional stereo probe (2DS) in order to assess whether the shattering of large ice crystals on protruding components of different probes artificially amplified measurements of small ice crystal concentrations. The dependence of the probe comparison on other variables as CIP N>100 (number concentrations greater than diameter D>100 μm),temperature, relative humidity respect to ice (RHice), dominant habit from the Cloud Particle Imager (CPI), aircraft roll, pitch, true air speed and angle of attack was examined to understand potential causes of discrepancies between probe concentrations. Data collected by these probes were also compared against the data collected by a CAS, CDP and CIP during the Tropical Warm Pool-International Cloud Experiment (TWP-ICE) and by a CAS and 2DS during the Tropical Composition, Cloud and Climate Coupling (TC4) missions. During ISDAC, the CAS and FSSP both overestimated measurements of small ice crystals compared to both the CDP and 2DS by 1-2 orders of magnitude. Further, the amount of overestimation increased with the concentrations from the CIP2 (N>100 > 0.1 L-1). There was an unexplained discrepancy in concentrations of small crystals between the CDP and 2DS during ISDAC. In addition, there was a strong dependence on RHice of the average ratios of the N3-50, CAS/N3-50,CDP, N3-50, FSSP096/N3-50,CDP, N3-50, CAS/N3-50,FSSP096, N10-50, CDP/N3-50,2DS, N10-50, FSSP096/N10-50,2DS. Continued studies are needed to understand the discrepancy of these probes.