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At least 19 records

Constraining Bedrock Groundwater Residence Times in a Mountain System With Environmental Tracer Observations and Bayesian Uncertainty Quantification

Groundwater residence time distributions provide fundamental insights on the hydrological processes within watersheds. Yet, observations that can constrain groundwater residence times over broad timescales remain scarce in mountain catchment studies. We use environmental tracers (CFC-12, SF 6 , 3 H, and 4 He) to investigate groundwater residence times along a hillslope in the East River Watershed, Colorado, USA. We develop a Bayesian inference framework that applies a Markov-chain Monte Carlo (MCMC) approach to estimate noble gas recharge temperature, elevation, and excess-air parameters and the resulting environmental tracer concentrations. MCMC is then used to propagate the environmental tracer uncertainties to estimates of groundwater mean residence times inferred with lumped parameter models. All samples contain 3 H, CFC-12, and SF 6 in addition to terrigenic 4 He, suggesting a mixture of water characterized by modern and premodern residence times. 4He exponential mean residence times range from hundreds of years at the upslope well to thousands of years at the toe-slope well assuming average crustal production rates. We find that binary mixing residence time distributions with separate young and old mixing fractions are needed to predict the 4 He, CFC-12, SF 6 , and 3 H observations, supporting the importance of flow path mixing in this bedrock system. Our findings that the fractured bedrock hosts groundwater with a mixture of residence times ranging from decades to millennia suggest variable recharge dynamics and flow path mixing along the hillslope and highlight the importance of characterizing groundwater systems with observations that are sensitive to transport over a broad range of residence times.

54 ENVIRONMENTAL SCIENCES↗

New insights into the flow dynamics of a deep freshwater aquifer in the semi-arid and saline Cuvelai-Etosha Basin, Northern Namibia: Results of a multi-environmental tracer study

Study region A paleo-megafan system of the Cubango River in the northern parts of the semi-arid Cuvelai-Etosha Basin, shared by Angola and Namibia. It hosts a deep freshwater aquifer, the so-called Kalahari-Ohangwena 2 (KOH-2), with the potential to resolve the imminent regional water supply shortages. Study focus Hydrogeochemical and multi-environmental tracer studies incorporating the use of age tracers 14 C, 36 Cl, 81 Kr and 4 He to determine the age of groundwater and provide insights into the flow dynamics of the KOH-2. New hydrological insights for the region Stable water isotopes and noble gas thermometry show that in a period with higher rainfall and recharge, temperatures were at least 3 – 4 °C lower than today. Several arguments led to the conclusion that younger groundwater, possibly of an age of 35,000 years, is mixed with ancient saline pore water. These include: 1) the correlation of measured 36 Cl and 81 Kr ratios, as well as 4 He concentrations, using a binary mixing model, and 2) the substantial variation in 81 Kr ages, ranging from 40,000 to 170,000 years, over relatively short distances—a phenomenon challenging to explain by advective groundwater flow equations. Consequently, the ages derived from 81 Kr measurements serve as indicators of the extent of freshening and therefore describe mixing ages rather than absolute travel times.

54 ENVIRONMENTAL SCIENCES↗

Constraining Bedrock Groundwater Residence Times in a Mountain System with Environmental Tracer Observations and Bayesian Uncertainty Quantification: Modeling and Data Package

Groundwater residence times provide fundamental descriptions of hydrologic dynamics and mixing processes in mountainous watersheds. Yet, few observational datasets that can constrain groundwater residence times over broad timescales are available in high elevation mountain systems. Here we present field observations from May 2021 of dissolved noble gases (He, Ne, Ar, Kr, and Xe), Chloroflourcarbons (CFCs), Sulfurhexaflouride (SF6), and tritium (3H) sampled from the Pumphouse Lower Montane study site (wells PLM1, PLM6, and PLM7) within the East River Watershed, Colorado. The presented noble gas (PLM_noblegas_2021.csv) and environmental tracer (PLM_tracers_2021.csv) observation datasets, along with the associated modeling scripts, aide in quantifying groundwater residence times and recharge conditions in a high elevation mountain system. Furthermore, the modeling scripts quantify groundwater residence time and noble gas recharge condition uncertainties using a novel Markov-chain Monte Carlo approach. All data modeling scripts are written in the Python code.

54 ENVIRONMENTAL SCIENCES↗

Quantifying subsurface parameter and transport uncertainty using surrogate modelling and environmental tracers

Here, we combine physics-based groundwater reactive transport modelling with machine-learning techniques to quantify hydrogeological model and solute transport predictive uncertainties. We train an artificial neural network (ANN) on a dataset of groundwater hydraulic heads and 3 H concentrations generated using a high-fidelity groundwater reactive transport model. Using the trained ANN as a surrogate model to reproduce the input–output response of the high-fidelity reactive transport model, we quantify the posterior distributions of hydrogeological parameters and hydraulic forcing conditions using Markov chain Monte Carlo calibration against field observations of groundwater hydraulic heads and 3 H concentrations. We demonstrate the methodology with a model application that predicts Chlorofluorocarbon-12 (CFC-12) solute transport at a contaminated field site in Wyoming, United States. Our results show that including 3 H observations in the calibration dataset reduced the uncertainty in the estimated permeability field and infiltration rates, compared to calibration against hydraulic heads alone. However, predictive uncertainty quantification shows that CFC-12 transport predictions conditioned to the parameter posterior distributions cannot reproduce the field measurements. We found that calibrating the model to hydraulic head and 3 H observations results in groundwater mean ages that are too large to explain the observed CFC-12 concentrations. The coupling of the physics-based reactive transport model with the machine-learning surrogate model allows us to efficiently quantify model parameter and predictive uncertainties, which is typically computationally intractable using reactive transport models alone.

58 GEOSCIENCES↗

(Project 18-15502) Reducing Uncertainty in Radionuclide Transport Prediction Using Multiple Environmental Tracers (Final Report)

In order to successfully site and design a nuclear waste disposal facility, DOE scientists are required to show safe containment of the radioactive waste for up to 1 million years. A significant hurdle to accurately and convincingly demonstrating disposal safety is predicting the fate of radioactive elements once they enter the groundwater system surrounding the repository. These predictions are often made with computer models, which contain accurate physics of groundwater movement and chemical reactions that occur during groundwater flow. As computer power increases, the physics and chemistry of these computer simulators can become more and more realistic and the physically based error decreases. However, the ability of these computer models to provide accurate predictions in a specific place, over long time periods, requires the scientists and engineers to know the subsurface properties of the Earth that control groundwater movement. In particular, groundwater scientists and engineers need to know the groundwater fluid velocity, which can change over time and strongly vary with location within the groundwater system. Because the Earth’s subsurface cannot be directly seen, and can only be sampled at drilling locations, the properties of the groundwater system are never known completely, and computer models of groundwater transport will always have some amount of uncertainty. This project’s principal goal was to use chemicals and isotope “tracers”, which have been introduced to the groundwater system by natural processes over long time periods, to help inform computer models of the groundwater velocity and subsurface properties. The goal was to calculate how much better predictions of groundwater transport were when these “tracers” were used to inform the computer models.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Accuracy of environmental tracers and consequences for determining the Type Ia supernova magnitude step

Type Ia Supernovae (SNe Ia) are standardizable candles that allow us to measure the recent expansion rate of the Universe. Due to uncertainties in progenitor physics, potential astrophysical dependencies may bias cosmological measurements if not properly accounted for. The dependency of the intrinsic luminosity of SNe Ia with their host-galaxy environment is often used to standardize SNe Ia luminosity and is commonly parameterized as a step function. This functional form implicitly assumes two-populations of SNe Ia. In the literature, multiple environmental indicators have been considered, finding different, sometimes incompatible, step function amplitudes. We compare these indicators in the context of a two-populations model, based on their ability to distinguish the two populations. We show that local Hα-based specific star formation rate (lsSFR) and global stellar mass are better tracers than, for instance, host galaxy morphology. We show that tracer accuracy can explain the discrepancy between the observed SNe Ia step amplitudes found in the literature. Using lsSFR or global mass to identify the two populations can explain all other observations, though lsSFR is favoured. As lsSFR is strongly connected to age, our results favour a prompt and delayed population model. In any case, there exists two populations that differ in standardized magnitude by at least 0.121 ± 0.010 mag.

79 ASTRONOMY AND ASTROPHYSICS↗

Old-Aged groundwater contributes to mountain hillslope hydrologic dynamics

Understanding connectivity between the soil and deeper bedrock groundwater is needed to accurately predict a watershed’s response to perturbation, such as drought. Yet, the bedrock groundwater dynamics in mountainous environments are typically under-constrained and excluded from watershed hydrologic models. Here, we investigate the role of groundwater characterized with decadal and longer water ages on the hydrologic and mass-transport processes within a steep snow-dominated mountain hillslope in the Central Rocky Mountains (USA). We quantify subsurface and surface water mass-balance, groundwater flowpaths, and age distributions using the ParFlow-CLM integrated hydrologic and EcoSLIM particle tracking models, which are compared to hydrometric and environmental tracer observations. An ensemble of models with varied soil and hydrogeologic parameters reproduces observed groundwater levels and century-scale mean ages inferred from environmental tracers. The numerical models suggest soil water near the toe of the hillslope contains considerable (>60 % of the mass-flux) contributions from bedrock flowpaths characterized with water ages >10 years. Flowpath connectivity between the deeper bedrock and soil systems is present throughout the year, highlighting the potentially critical role of groundwater with old ages on processes such as evapotranspiration and streamflow generation. The coupled numerical model and groundwater age observations show the bedrock groundwater system influences the hillslope hydrodynamics and should be considered in mountain watershed conceptual and numerical models.

54 ENVIRONMENTAL SCIENCES↗

On the emergent scale of bedrock groundwater contribution to headwater mountain streams

We investigated the contribution of bedrock groundwater to streamflow as a function of catchment scale in a headwater stream. Synoptic surveys were conducted during hydrologically important periods of the year using multiple environmental tracers in stream water, soil water, and bedrock groundwater, along a first-order montane stream, in west-central Montana. Sampled analytes included 222 Rn, used to constrain total subsurface flux, and major and minor elements, used in end-member mixing analysis (EMMA) to identify the contributions of soil and bedrock groundwater to the stream. Partitioning between soil-derived and bedrock-derived groundwater was then analyzed as a function of the incremental and accumulated sub-catchment sizes. Radon results indicated that subsurface water contributions accounted for the majority of streamflow at all surveyed times. EMMA results revealed that the bedrock groundwater contribution to streamflow varied between 26% during peak snowmelt and 44% during late summer. Streamflow generation was dominated by soil groundwater contribution along the entire reach, but the bedrock groundwater contribution increased consistently with accumulated sub-catchment size. However, groundwater contributions were not well-correlated with incremental sub-catchment size. The scale at which increased bedrock groundwater discharge can be correlated with sub-catchment size appears to be >1 km 2 for our study. Our results are consistent with a conceptual model where streamflow is predominantly generated by a 3D subsurface nested flow system. Local subsurface heterogeneities control the stream source at local scales but begin to average out at scales >2 km 2 . Our study indicates that, while soil groundwater is the dominant source, bedrock groundwater remains an important and predictable contributor to streamflow throughout the year, even in a snow-dominated, mountainous headwater catchment.

environmental tracers↗

Impact of Advection Schemes on Tracer Interrelationships in Large-Eddy Simulations of Deep Convection

This study investigates the preservation of tracer interrelationships during advection in large-eddy simulations of an idealized deep convective cloud, which is particularly relevant to chemistry, aerosol, and cloud microphysics models. Employing the Cloud Model 1, advection is represented using third-, fifth-, and seventh-order weighted essentially non-oscillatory schemes. As a simplified analogy for cloud hydrometeors and aerosols, several inert passive tracers following linear and nonlinear relationships are initialized after the cloud reaches ~6-km depth. Numerical mixing in the simulated turbulent convective clouds leads to significant deviations from the initial nonlinear relationships between tracers. In these simulations, a considerable fraction of the grid points where the tracers’ nonlinear relationships are altered from advection are classified as unrealistic (e.g., ~13% for the environmental tracers on average), including errors from range-preserving unmixing and overshooting. Errors in the sum of three tracers are also relatively large, ranging between ~1% and 16% for 5% of the grid points in and near the cloud. The magnitude of unrealistic mixing and errors in the sum of three tracers generally increase with the order of accuracy of the advection scheme. These results are consistent across model grid spacings ranging from 50 to 200 m, and across three different flow realizations for each combination of grid spacing and advection scheme tested. Tests employing a previously proposed scalar normalization procedure show substantially reduced errors in the sum of three tracers with a relatively small negative impact on other tracer relationships. This analysis, therefore, suggests efficacy of the normalization procedure when applied to turbulent three-dimensional cloud simulations.

54 ENVIRONMENTAL SCIENCES↗

Matrix Diffusion Controls Mountain Hillslope Groundwater Ages and Inferred Storage Dynamics

Groundwater age distributions provide fundamental insights on coupled water and biogeochemical processes in mountain watersheds. Field-based studies have found mixtures of young and old-aged groundwater in mountain catchments underlain by bedrock; yet, the processes that dictate these groundwater age distributions are poorly understood. In this work, we use the coupled ParFlow-CLM integrated hydrologic and EcoSLIM particle tracking models to simulate groundwater age distributions on a lower montane hillslope in the East River Watershed, Colorado (USA). We develop a convolution-based approach to propagate fracture-matrix diffusion processes to the EcoSLIM advection-dominated age distributions. We compare observed 3 H and 4 He concentrations from two groundwater wells against model predictions that have varying advective transport times and matrix diffusion magnitudes. Based on a Monte Carlo analysis that considers uncertain matrix and fracture parameters, we find that matrix diffusion is needed to jointly predict 3 H and 4 He observations at both wells. The advection-dominated age distributions lack adequate mixing of young and old-aged water to capture the observed co-occurrence of 3 H and 4 He. The model scenario that best matches the 3 H, 4 He, and water level observations when considering both advective flowpath and matrix diffusion mixing processes has a dynamic bedrock groundwater reservoir that is susceptible to considerable storage losses during low-snow periods. This dynamic groundwater system amplifies the need to assimilate deeper bedrock groundwater into watershed hydro-biogeochemical predictions. This work further highlights the importance of considering matrix diffusion when interpreting environmental tracers in bedrock groundwater systems.

54 ENVIRONMENTAL SCIENCES↗

Dependence of Convective Cloud Microphysical Properties on Environmental Conditions during the TRACER and ESCAPE Field Campaigns: A Synergistic Approach of Observations, Machine Learning and Parcel Models

The sensitivity of convective clouds to aerosols and their interactions with environment, combined with limited observational constraints in parameterizations, introduces significant uncertainties in atmospheric models. Here, this study investigates the dependence of convective cloud microphysical properties on environmental conditions using a synergistic approach that combines unique observations from the TRACER and ESCAPE field campaigns, machine learning techniques, and parcel model simulations with a super-droplet microphysics scheme. A random forest algorithm identifies in-situ vertical velocity (w), temperature (T), and surface fine-mode aerosol mass concentration as the three most important environmental conditions influencing cloud properties including liquid water content (LWC), number concentration for particles with D max < 50 μm (N c ,<50), 50 μm ≤ D max ≤ 3000 μm (N c,50–3000 ), and droplet effective diameter (D e ). Results show that LWC, N c,<50 , and N c,50–3000 significantly increase with w in updrafts. Across w bins, as T decreases, LWC, D e , and N c,50–3000 increase, while N c,<50 decreases, which are closely linked to the distance above cloud bases. Warmer cloud bases yield higher LWC, greater N c,50–3000 , and smaller N c,<50 , while polluted environments produce greater N c,<50 . Parcel model simulations successfully replicate these observed dependencies. The simulation results indicate that warmer cloud bases enhance condensation generating larger droplets, and differences in droplet sizes are then amplified through collision-coalescence, resulting in a greater N c,50–3000 . Polluted conditions result in a greater N c,<50 primarily due to enhanced cloud condensation nuclei activation despite increased collision-coalescence rates compared to pristine conditions. This study provides observed quantitative patterns characterizing cloud microphysical properties as a function of key environmental parameters, offering valuable constraints for improving physics parameterizations and numerical models.

54 ENVIRONMENTAL SCIENCES↗

Challenges in studying water fluxes within the soil-plant-atmosphere continuum: A tracer-based perspective on pathways to progress

Tracing and quantifying water fluxes in the hydrological cycle is crucial for understanding the current state of ecohydrological systems and their vulnerability to environmental change. Especially the interface between ecosystems and the atmosphere that is strongly mediated by plants is important to meaningfully describe ecohydrological system functioning. Many of the dynamic interactions generated by water fluxes between soil, plant and the atmosphere are not well understood, which is partly due to a lack of interdisciplinary research. This opinion paper reflects the outcome of a discussion among hydrologists, plant ecophysiologists and soil scientists on open questions and new opportunities for collaborative research on the topic "water fluxes in the soil-plant-atmosphere continuum" especially focusing on environmental and artificial tracers. We emphasize the need for a multi-scale experimental approach, where a hypothesis is tested at multiple spatial scales and under diverse environmental conditions to better describe the small-scale processes (i.e., causes) that lead to large-scale patterns of ecosystem functioning (i.e., consequences). Novel in-situ, high-frequency measurement techniques offer the opportunity to sample data at a high spatial and temporal resolution needed to understand the underlying processes. Here we advocate for a combination of long-term natural abundance measurements and event-based approaches. Multiple environmental and artificial tracers, such as stable isotopes, and a suite of experimental and analytical approaches should be combined to complement information gained by different methods. Virtual experiments using process-based models should be used to inform sampling campaigns and field experiments, e.g., to improve experimental designs and to simulate experimental outcomes. On the other hand, experimental data are a pre-requisite to improve our currently incomplete models. Interdisciplinary collaboration will help to overcome research gaps that overlap across different earth system science fields and help to generate a more holistic view of water fluxes between soil, plant and atmosphere in diverse ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Evaluating E3SM Global Storm‐Resolving Model Simulations of Deep Convection: Insights From DP‐SCREAM During TRACER

Global Storm-Resolving Models (GSRMs) are becoming increasingly vital for advancing climate modeling and improving the prediction of extreme weather events. Houston, a coastal region frequently affected by deep convective storms, offers an ideal setting to evaluate the ability of GSRMs to simulate deep convection. This study assesses the performance of the Doubly Periodic Simple Cloud-Resolving E3SM (Energy Exascale Earth System Model) Atmosphere Model (DP-SCREAM) using observations from the TRacking Aerosol Convection interactions ExpeRiment (TRACER) campaign. DP-SCREAM effectively reproduces the diurnal cycles of clouds and precipitation, demonstrating much greater skill than the E3SM single column model. The DP-SCREAM is demonstrated to be applicable to coastal regions, partially due to the forcing data sets already capturing the influence of breezes. DP-SCREAM also replicates biases persistent in the global version of SCREAM: the underrepresentation of boundary layer shallow clouds, a lack of mid-level congestus clouds, and the popcorn convection, characterized by small and disorganized convective cells generating the strongest precipitation. To investigate these issues, two sensitivity experiments were conducted: increasing the mixing length and scaling up the buoyancy flux within the Simplified Higher Order Closure scheme. Increasing the mixing length improved mid-level congestus representation and reduced unrealistic early morning fog occurrence. Enhancing buoyancy flux only marginally improved the bias of underproduced big convective cells. In conclusion, an additional resolution sensitivity test at 0.5 km grid spacing demonstrated that a refined horizontal resolution alone is insufficient to resolve these biases.

54 ENVIRONMENTAL SCIENCES↗

Agile Allocation in the Tundra: A Single Growing Season of Warming Increases Nutrient Availability While Decreasing Fine-Root Length

The majority of plant biomass is located belowground in Arctic ecosystems and plant roots are responsible for the uptake of the nutrients that constrain plant growth in these infertile ecosystems. Despite performing a crucial role connecting primary producers to the soil, roots are relatively understudied in the Arctic and their functional response to a rapidly warming and increasingly variable climate is unknown. Here, we assessed whether one growing season with elevated temperatures would have an impact on nutrient uptake and allocation by applying a warming technique that increased daily air temperatures by 3.2 °C. Destructive sampling was performed at the peak of the growing season to quantify biomass pools of carbon (C) and nitrogen (N), root traits, and uptake of a 15 N tracer ( 15 NH 4 + ) for the dominant plant species, Arctagrostis latifolia. We found that soil nutrient availability increased with short-term warming, but A. latifolia NH 4 + uptake remained unchanged. Fine-root length density and root biomass within the soil profile, however, were both reduced by warming. N allocation patterns across plant tissues were also altered by warming. NH 4 + uptake was best fit with a logistic model that captured the spatial relationship between roots and soil (NH 4 + uptake expressed per length fine root and NH 4 + availability expressed per unit soil volume) rather than a traditional Michaelis–Menten model. Our results indicate that short-term experimental warming can shift plant–soil interactions, suggesting that the tundra’s belowground response to elevated temperatures may be more dynamic than previously recognized.

15N tracer↗

Linking Synoptic Patterns to Cloud Properties and Local Circulations Over Southeastern Texas

This report classifies meteorological regimes in the southeastern Texas region to identify environmental conditions that favor sea-breeze induced convection. The classification is accomplished using a Self-Organizing Map (SOM) approach. We applied SOM to 10 years of 700-hPa geopotential height anomalies during the summer months from reanalysis data to distinguish three dominant synoptic regimes, with a continuum of transitional states between those. The primary regimes include: (a) a pre-trough regime associated with a synoptic trough, (b) a post-trough regime with upper-level northerly flow, and (c) an anticyclonic regime within the westward extent of the Bermuda High. We project the data from the Geostationary Operational Environmental Satellite and the Next Generation Weather Radar system onto each SOM node to investigate the characteristics of cloud and precipitation properties in different regimes. When southeastern Texas is positioned to the southwest quadrant of a maritime high pressure system, an increased cloud frequency is observed over the region during the afternoon hours due to significant moisture advection. A confluence of synoptic southerly flow and sea-breeze circulation commonly occurs in this regime. When a high pressure system is over southeastern Texas, the area is dominated by large-scale subsidence with weak pressure gradients and moderate precipitable water vapor. This weak synoptic forcing is favorable for the formation of a sea-breeze circulation. This is confirmed by an enhanced onshore flow and a decreased temperature at the surface in the early afternoon, as well as a sharp increase in radar echo top height.

54 ENVIRONMENTAL SCIENCES↗

Stereo Camera Deployment in Support of TRACER (Field Campaign Report)

An improved understanding of the salient environmental controls on cloud formation, evolution, and eventual dissipation is critical to address ongoing challenges with cloud process and parameterization representations in global climate and Earth system models. One goal for the recent U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility’s Tracking Aerosol Convection Interactions Experiment (TRACER) campaign was to collect a comprehensive data set that enabled such convective cloud process studies and key demonstrations for those controls that influenced cloud life cycle (i.e., aerosols, thermodynamics) in the Houston, Texas region. To help accomplish this, ARM instrumentation during TRACER was tasked with tracking a large number of individual, isolated convective cells – and to follow the evolution of these cells at high spatiotemporal resolution to characterize changes in cloud dynamic and microphysical properties. Since Houston experiences a range of convective clouds, it was known that the standard ARM Mobile Facility (AMF) instruments may not be sufficient to completely document initiating, transient, or dissipating low- or shallow-cloud behaviors that were also expected during this campaign (in terms of sensitivity, resolution, and/or operational availability). As one partial solution, a supplemental stereo camera deployment (this sub-campaign) was requested to augment the ARM AMF instrumentation to better address shallow and shallow-to-deep transitional types of cloud process drivers during TRACER (ARM stereo cameras for clouds [STEREOCAM]; Romps and Öktem 2018). The primary scientific focus was the relationships between cloud properties and the ambient conditions, which points to several key TRACER science questions including: ‘What is the relationship between cloud size or updraft intensity to the environmental wind shear and/or humidity?’ Overall, the ARM TRACER stereo camera deployment demonstrated unique effectiveness in observing a wide range of critical shallow, congestus, and transitioning or time-evolving cloud characteristics. The data sets from these cameras include information on the clouds' horizontal dimensions, elevations, and depths, while also enabling potential products for cloud initiation and dissipation rates, and vertical velocities. Stereo cameras simultaneously inform on cloud life cycle stage and spatial properties such as cloud fractional coverage, which should provide complementary information for ARM users when combined with TRACER cloud radars, lidar, and/or other profiling sensors. Moreover, camera products offer large-eddy simulation (LES),-scale-appropriate cloud coverage, depth, and spatial variability estimates, while opening additional avenues to challenge difficult process questions on cloud updrafts/entrainment and their covariability with environmental controls such as wind shear and humidity.

47 OTHER INSTRUMENTATION↗

Boron isotopic analysis in bulk silicate materials using the Neoma MS/MS MC-ICP-MS

Boron (B) isotopes are a valuable tracer with applications ranging from geological, environmental, and nuclear studies because B isotopic fractionation is highly sensitive to chemical processes yielding distinct isotopic trends in natural and anthropogenic systems. Despite this wide applicability, there remain relatively few measurements on well-described reference materials and in some cases, poor agreement between various methods. We report a method for boron isotope ratio measurement in solution on the Neoma MS/MS MC-ICP-MS specifically targeting bulk silicates. We evaluate the performance of the method and instrument as it relates to the measurement of the absolute boron isotope ratio ( 10 B/ 11 B). The results indicate that the method produces data in agreement with literature values and that the sample–standard bracketing technique is appropriate for the Neoma MS/MS MC-ICP-MS which has been in use for decades on previous generation instruments. Careful tuning of the MS/MS lenses is required to obtain precision comparable to non MS/MS equipped MC-ICP-MS. With careful tuning, internal and external precisions of ∼0.3‰ were achieved. However, when the MS/MS is not properly tuned external precisions exceed 3‰. Nevertheless, our results for IAEA B-6, BCR-2, BHVO-2 and W-2a reference materials overlap the 1σ range of previously reported 10 B/ 11 B. Data are reported for total boron quantities down to a few tens of nanograms. Our procedure yielded blanks as low as 3 ng but up to 29 ng, making blank corrections important for small samples sizes in the few 10s of nanogram range. We report B isotope ratios for AGV-2G, SL-1G, GSC-2G, GSD-2G, GSE-2G, RLS-132, RLS-140, NKT-1G, and T1-G glass reference materials that have not been previously reported in the literature.

Scott, Sean R. [Pacific Northwest National Laborat↗