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Physics and technology considerations for the deuterium–tritium fuel cycle and conditions for tritium fuel self sufficiency

The tritium aspects of the DT fuel cycle embody some of the most challenging feasibility and attractiveness issues in the development of fusion systems. The review and analyses in this paper provide important information to understand and quantify these challenges and to define the phase space of plasma physics and fusion technology parameters and features that must guide a serious R&D in the world fusion program. We focus in particular on components, issues and R&D necessary to satisfy three 'principal requirements': (1) achieving tritium self-sufficiency within the fusion system, (2) providing a tritium inventory for the initial start-up of a fusion facility, and (3) managing the safety and biological hazards of tritium. A primary conclusion is that the physics and technology state-of-the-art will not enable DEMO and future power plants to satisfy these principal requirements. We quantify goals and define specific areas and ideas for physics and technology R&D to meet these requirements. A powerful fuel cycle dynamics model was developed to calculate time-dependent tritium inventories and flow rates in all parts and components of the fuel cycle for different ranges of parameters and physics and technology conditions. Dynamics modeling analyses show that the key parameters affecting tritium inventories, tritium start-up inventory, and tritium self-sufficiency are the tritium burn fraction in the plasma (f b ), fueling efficiency (η f ), processing time of plasma exhaust in the inner fuel cycle (t p ), reactor availability factor (AF), reserve time (tr) which determines the reserve tritium inventory needed in the storage system in order to keep the plant operational for time t r in case of any malfunction of any part of the tritium processing system, and the doubling time (t d ). Results show that η f f b > 2% and processing time of 1–4 h are required to achieve tritium self-sufficiency with reasonable confidence. For η f f b = 2% and processing time of 4 h, the tritium start-up inventory required for a 3 GW fusion reactor is ~11 kg, while it is <5 kg if η f f b = 5% and the processing time is 1 h. To achieve these stringent requirements, a serious R&D program in physics and technology is necessary. The EU-DEMO direct internal recycling concept that carries fuel directly from the plasma exhaust gas to the fueling systems without going through the isotope separation system reduces the overall processing time and tritium inventories and has positive effects on the required tritium breeding ratio (TBR R ). A significant finding is the strong dependence of tritium self-sufficiency on the reactor availability factor. Simulations show that tritium self-sufficiency is: impossible if AF < 10% for any η f f b , possible if AF > 30% and 1% ≤ η f f b ≤ 2%, and achievable with reasonable confidence if AF > 50% and η f f b > 2%. These results are of particular concern in light of the low availability factor predicted for the near-term plasma-based experimental facilities (e.g. FNSF, VNS, CTF), and can have repercussions on tritium economy in DEMO reactors as well, unless significant advancements in RAMI are made. There is a linear dependency between the tritium start-up inventory and the fusion power. The required tritium start-up inventory for a fusion facility of 100 MW fusion power is as small as 1 kg. Since fusion power plants will have large powers for better economics, it is important to maintain a 'reserve' tritium inventory in the tritium storage system to continue to fuel the plasma and avoid plant shutdown in case of malfunctions of some parts of the tritium processing lines. But our results show that a reserve time as short as 24 h leads to unacceptable reserve and start-up inventory requirements. Therefore, high reliability and fast maintainability of all components in the fuel cycle are necessary in order to avoid the need for storing reserve tritium inventory sufficient for continued fusion facility operation for more than a few hours. The physics aspects of plasma fueling, tritium burn fraction, and particle and power exhaust are highly interrelated and complex, and predictions for DEMO and power reactors are highly uncertain because of lack of experiments with burning plasma. Fueling by pellet injection on the high field side of tokamak has evolved to be the preferred method to fuel a burning plasma. Extrapolation from the DIII-D penetration scaling shows fueling efficiency expected in DEMO to be <25%, but such extrapolations are highly uncertain. The fueling efficiency of gas in a reactor relevant regime is expected to be extremely poor and not very useful for getting tritium into the core plasma efficiently. Gas fueling will nonetheless be useful for feedback control of the divertor operating parameters. Extensive modeling has been carried out to predict burn fraction, fueling requirements, and fueling efficiency for ITER, DEMO, and beyond. The fueling rate required to operate Q = 10 ITER plasmas in order to provide the required core fueling, helium exhaust and radiative divertor plasma conditions for acceptable divertor power loads was calculated. If this fueling is performed with a 50–50 DT mix, the tritium burn fraction in ITER would be ~0.36%, which is too low to satisfy the self-sufficiency conditions derived from the dynamics modeling for fusion reactors. Extrapolation to DEMO using this approach would also yield similarly low burn fraction. Extensive analysis presented shows that specific features of edge neutral dynamics in ITER and fusion reactors, which are different from present experiments, open possibilities for optimization of tritium fueling and thus to improve the burn fraction. Using only tritium in pellet fueling of the plasma core, and only deuterium for edge density, divertor power load and ELM control results in significant increase of the burn fraction to 1.8–3.6%. These estimates are performed with physics models whose results cannot be fully validated for ITER and DEMO plasma conditions since these cannot be achieved in present tokamak experiments. Thus, several uncertainties remain regarding particle transport and scenario requirements in ITER and DEMO. The safety standard requirements for protection of the public and release guidelines for tritium have been reviewed. General safety approaches including minimizing tritium inventories, reducing tritium permeation through materials, and decontaminating material for waste disposal have been suggested.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NetFlow Dynamics

NetFlow Dynamics is a web-accessible analysis environment for simulating dynamic flows of materials on model networks. Performing a simulation requires both the NetFlow Dynamics application and a network model which is a description of the structure of the nodes and edges of a network including the flow capacity of each edge and the storage capacity of each node, and the sources and sinks of the material flowing on the network. NetFlow Dynamics consists of databases for storing network models, algorithms to calculate flows on networks, and a GIS-based graphical interface for performing simulations and viewing simulation results. Simulated flows are dynamic in the sense that flows on each edge of the network and inventories at each node change with time and can be out of equilibrium with boundary conditions. Any number of network models could be simulated using Net Flow Dynamics. To date, the models simulated have been models of petroleum infrastructure. The main model has been the National Transportation Fuels Model (NTFM), a network of U.S. oil fields, transmission pipelines, rail lines, refineries, tank farms, and distribution terminals. NetFlow Dynamics supports two different flow algorithms, the Gradient Flow algorithm and the Inventory Control algorithm, that were developed specifically for the NetFlow Dynamics application. The intent is to add additional algorithms in the future as needed. The ability to select from multiple algorithms is desirable because a single algorithm never covers all analysis needs. The current algorithms use a demand-driven capacity-constrained formulation which means that the algorithms strive to use all available capacity and stored inventory to meet desired flows to sinks, subject to the capacity constraints of each network component. The current flow algorithms are best suited for problems in which a material flows on a capacity-constrained network representing a supply chain in which the material supplied can be stored at each node of the network. In the petroleum models, the flowing materials are crude oil and refined products that can be stored at tank farms, refineries, or terminals (i.e. the nodes of the network). Examples of other network models that could be simulated are currency flowing in a financial network, agricultural products moving to market, or natural gas flowing on a pipeline network.

Corbet Jr., Thomas F↗

Closing the methane gap in US oil and natural gas production emissions inventories

Methane (CH 4 ) emissions from oil and natural gas (O&NG) systems are an important contributor to greenhouse gas emissions. In the United States, recent synthesis studies of field measurements of CH 4 emissions at different spatial scales are ~1.5–2× greater compared to official greenhouse gas inventory (GHGI) estimates, with the production-segment as the dominant contributor to this divergence. Based on an updated synthesis of measurements from component-level field studies, we develop a new inventory-based model for CH 4 emissions, for the production-segment only, that agrees within error with recent syntheses of site-level field studies and allows for isolation of equipment-level contributions. We find that unintentional emissions from liquid storage tanks and other equipment leaks are the largest contributors to divergence with the GHGI. If our proposed method were adopted in the United States and other jurisdictions, inventory estimates could better guide CH 4 mitigation policy priorities.

03 NATURAL GAS↗

A burnup credit approach irradiated fast-neutron reactor fuels/ nuclides of interest and fuel storage application - 14248

The concept of taking into account the reduction of the reactivity of nuclear used fuel due to their burnup is referred to as 'Burnup Credit' (BUC). Economic incentives offered by the implementation of a BUC methodology in criticality analyses of Light Water Reactor (LWR) used fuel facilities are nowadays well-demonstrated. The current prospect of reprocessing the fissile and fertile subassemblies of the PHENIX reactor in France, and the development of the 4.-Generation Fast-neutron Reactors (FR) enable research projects in relevant fuel cycle operations. Under these circumstances, the CEA and AREVA-NC have decided to study a burnup credit approach for irradiated fuels of the PHENIX reactor. This paper focuses on a preliminary investigation on the use of burnup credit for used FR fuel operations. The first step consists in analyzing and selecting the nuclides of interest for burnup calculation, on the basis of the 27 BUC nuclides (12 actinides and 15 fissions products) chosen for LWR-MOx fuels [1]. These nuclides are then involved in a criticality calculation (a used fuel pool) to highlight the interest of a BUC approach. This study highlights the interest of a burnup credit approach for FR fuels and shows that the highest contribution to reactivity loss is due to only one fission product: the {sup 149}Sm. The opportunity to take account of only one fission product is highly promising and will considerably simplify the way to determine a penalizing fuel inventory. Moreover, it is to notice that results for different configurations may differ from those obtained for a fuel storage application. Thus, specific analyses have to be carried out in order to study the applicability of the conclusions of this paper. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Mechanism of Nitrogenase H 2 Formation by Metal-Hydride Protonation Probed by Mediated Electrocatalysis and H/D Isotope Effects

Nitrogenase catalyzes the reduction of dinitrogen (N2) to ammonia (NH3) with obligatory reduction of protons (H+) to dihydrogen (H2) through a mechanism involving reductive elimination of two [Fe-H-Fe] bridging hydrides at its active site FeMo-cofactor. The overall rate-limiting step is associated with ATP-driven electron delivery from Fe protein, precluding isotope effect measurements on substrate reduction steps. Here, we use mediated bioelectrocatalysis to drive electron delivery to MoFe protein without Fe protein and ATP hydrolysis, thereby eliminating the normal rate-limiting step. The ratio of catalytic current in mixtures of H2O and D2O, the proton inventory, changes linearly with the D2O/H2O ratio, revealing that a single H/D is involved in the rate limiting step. Kinetic models, along with measurements that vary the electron/proton delivery rate and use different substrates, reveal that the rate-limiting step under these conditions is the H2 formation reaction. Altering the chemical environment around the active site FeMo-cofactor in the MoFe protein either by substituting nearby amino acids or transferring the isolated FeMo-cofactor into a different peptide matrix, changes the net isotope effect, but the proton inventory plot remains linear, consistent with an unchanging rate-limiting step. Density functional theory predicts a transition state for H2 formation where the proton from S-H+ moves to the hydride in Fe-H-, predicting the number and magnitude of the observed H/D isotope effect. This study not only reveals the mechanism of H2 formation, but also illustrates a strategy for mechanistic study that can be applied to other enzymes and to biomimetic complexes.

BINDING↗

Multiresource analysis and information system concepts for incorporating LANDSAT and GIS technology into large area forest surveys

A method of relating different classifications at each stage of a multistage, multiresource inventory using remotely sensed imagery is discussed. A class transformation matrix allowing the conversion of a set of proportions at one stage, to a set of proportions at the subsequent stage through use of a linear model, is described. The technique was tested by applying it to Kershaw County, South Carolina. Unsupervised LANDSAT spectral classifications were correlated with interpretations of land use aerial photography, the correlations employed to estimate land use classifications using the linear model, and the land use proportions used to stratify current annual increment (CAI) field plot data to obtain a total CAI for the county. The estimate differed by 1% from the published figure for land use. Potential sediment loss and a variety of land use classifications were also obtained.

Langley, P. G.↗

Derivation of a New Smoke Emissions Inventory using Remote Sensing, and Its Implications for Near Real-Time Air Quality Applications

A new emissions inventory of particulate matter (PM) is being derived mainly from remote sensing data using fire radiative power (FRP) and aerosol optical depth (AOD) retrievals from the Moderate Resolution Imaging Spectroradiometer (MODIS) instrument, as well as wind data from the Modern Era Retrospective-Analysis for Research and Applications (MERRA) reanalysis dataset, which spans the satellite era. This product is generated using a coefficient of emission, C(sub e), that has been produced on a 1x1 degree global grid such that, when it is multiplied with satellite measurements of FRP or its time-integrated equivalent fire radiative energy (FRE) retrieved over a given area and time period, the corresponding PM emissions are estimated. This methodology of using C(sub e) to derive PM emissions is relatively new and advantageous for near real-time air quality applications compared to current methods based on post-fire burned area that may not provide emissions in a timely manner. Furthermore, by using FRP to characterize a fire s output, it will represent better accuracy than the use of raw fire pixel counts, since fires in individual pixels can differ in size and strength by orders of magnitude, resulting in similar differences in emission rates. Here we will show examples of this effect and how this new emission inventory can properly account for the differing emission rates from fires of varying strengths. We also describe the characteristics of the new emissions inventory, and propose the process chain of incorporating it into models for air quality applications.

Ellison, Luke↗

Water inventories on Earth and Mars: Clues to atmosphere formation

Water is distributed differently on Earth and on Mars and the differences may have implications for the accretion of the two planets and the formation of their atmospheres. The Earth's mantle appears to contain at least several times the water content of the Martian mantle even accounting for differences in plate tectonics. One explanation is that the Earth's surface melted during accretion, as a result of development of a steam atmosphere, thereby allowing impact-devolitalized water at the surface to dissolve into the Earth's interior. In contrast, because of Mars' smaller size and greater distance from the Sun, the Martian surface may not have melted, so that the devolatilized water could not dissolve into the surface. A second possibility is suggested by the siderophile elements in the Earth's mantle, which indicates the Earth acquired a volatile-rich veneer after the core formed. Mars may have acquired a late volatile-rich veneer, but it did not get folded into the interior as with the Earth, but instead remained as a water rich veneer. This perception of Mars with a wet surface but dry interior is consistent with our knowledge of Mars' geologic history.

Carr, M. H.↗

A top-down assessment using OMI NO 2 suggests an underestimate in the NO x emissions inventory in Seoul, South Korea, during KORUS-AQ

Abstract. In this work, we investigate the NO x emissions inventory inSeoul, South Korea, using a regional ozone monitoring instrument (OMI) NO 2 product derived from the standard NASA product. We first develop a regional OMI NO 2 product by recalculating the air mass factors using a high-resolution (4 km × 4 km) WRF-Chem model simulation, which better captures the NO 2 profile shapes in urban regions. We then apply a model-derived spatial averaging kernel to further downscale the retrieval and account for the subpixel variability. These two modifications yield OMI NO 2 values in the regional product that are1.37 times larger in the Seoul metropolitan region and &gt;2 times larger near substantial point sources. These two modifications also yield an OMI NO 2 product that is in better agreement with the Pandora NO 2 spectrometer measurements acquired during the South Korea–United States Air Quality (KORUS-AQ) field campaign. NO x emissions are then derived for the Seoul metropolitan area during the KORUS-AQ field campaign using a top-down approach with the standard and regional NASA OMI NO 2 products. We first apply the top-down approach to a model simulation to ensure that the method is appropriate: the WRF-Chem simulation utilizing the bottom-up emissions inventory yields a NO x emissions rate of 227±94 kt yr –1 , while the bottom-up inventory itself within a 40 km radius of Seoul yields a NO x emissions rate of198 kt yr –1 . Using the top-down approach on the regional OMI NO 2 product, we derive the NO x emissions rate from Seoul to be 484±201 kt yr –1 , and a 353±146 kt yr –1 NO x emissions rate using the standard NASA OMI NO 2 product. This suggests an underestimate of 53 % and 36 % in the bottom-up inventory using the regional and standard NASA OMI NO 2 products respectively. To supplement this finding, we compare the NO 2 and NO y simulated by WRF-Chem to observations of the same quantity acquired by aircraft and find a model underestimate.When NO x emissions in the WRF-Chem model are increased by a factor of 2.13 in the Seoul metropolitan area, there is better agreement with KORUS-AQ aircraft observations and the recalculated OMI NO 2 tropospheric columns. Finally, we show that by using a WRF-Chem simulation with an updated emissions inventory to recalculate the air mass factor (AMF),there are small differences ( ~8 %) in OMI NO 2 compared tousing the original WRF-Chem simulation to derive the AMF. This suggests that changes in model resolution have a larger effect on the AMF calculation than modifications to the South Korean emissions inventory. Furthermore the current work is focused on South Korea using OMI, the methodology developed in this work can be applied to other world regions using TROPOMI and future satellite datasets (e.g., GEMS and TEMPO) to produce high-quality region-specific top-down NO x emissions estimates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

SCALE Modeling of the Fast Spectrum Heat Pipe Reactor

As part of the severe accident analysis collaboration with Sandia National Laboratories (SNL) and the Nuclear Regulatory Commission (NRC), SCALE models were developed for a fast-spectrum heat pipe reactor. These models were based on the Idaho National Laboratory (INL) Design A concept, which is an alternative design to the Los Alamos National Laboratory (LANL) Special Purpose Reactor (SPR), also known as the Megapower reactor. The model contains 1,134 heat pipes, surrounded by hexagonal fuel elements, with a potassium working fluid; the fuel is UO 2 with 19.75 wt% 235 U enrichment. The model contains axial beryllium oxide (BeO) reflectors above and below the active fuel region along with a radial alumina reflector containing 12 B 4 C control drums. The center of the core is left unfueled to make room for two shutdown control rods, one annular and one solid. The active region of the core was discretized into twenty axial and five radial zones to analyze spatial variations in power and burnup. Infinite lattice unit cell sensitivity studies were used to perform verification between the SCALE and INL models. The eigenvalue results agreed well with the reported results to within roughly 50 percent mille (pcm). Full-core model verification was performed by analyzing system eigenvalues with differing configurations of control drum and shutdown rod positions. These full core results all had eigenvalue differences less than 310 pcm. Control drum and shutdown rod worths were also compared, with differences of 3.2% or less. Using the verified model, the isotopic inventory and decay heat, as well as temperature feedback coefficients, were calculated and provided to SNL as input to the MELCOR severe accident code to analyze potential releases from this class of reactor. The results of the MELCOR analysis are provided in a different report.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Review of non destructive assay techniques utilised for decommissioning of plutonium facilities at AWE - 14418

Over the past fifteen years AWE has decommissioned and size reduced a large number of glove boxes that contained a wide spectrum of equipment that ranged from highly radiation attenuating structures, such as furnaces and lathes, to other less radiation attenuating apparatus, such as small discrete tools or simple work benches. In order to generate meaningful glove box residual fissile material inventory data, which can constructively inform the selection of measures needed to underwrite the criticality safety of size reduction and consignment to waste activities, several different types of Non Destructive Assay (NDA) measurement techniques are available at AWE. These are deployed for the estimate of the residual fissile material inventory prior to decommissioning activities and for the final NDA of waste containers, post decommissioning. The techniques range from the Decommissioning In-Situ Plutonium Inventory Monitor (DISPIM), through other Neutron Coincidence Counting (NCC) techniques (Neutron Panel monitoring) and gamma measurements to consideration of Thermo Luminescent Detector (TLD) data. This paper will present a comparison of the fissile material identified in the waste generated post decommissioning operations to the NDA estimate of the residual fissile material inventory for the glove boxes, as well as provide a direct comparison between the different NDA techniques available at AWE. The findings to date indicate that the glove box residual fissile material inventory used for criticality safety purposes bounds the decommissioning process, subject to the suitable deployment of the NDA technique and the inclusion of appropriate uncertainties. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Comparative evaluation of ERTS-A imagery for resource inventory in land use planning

There are no author-identified significant results in this report. Evaluation has begun on ERTS-1 imagery of Crook County for use in landform interpretation and geologic mapping and interpretation. Outside of Crook County the geology team has been impressed by the display of fault patterns in southeastern Oregon and has begun preliminary analyses of these. Using the color combiner a complete timber type map of (1) all the forest land within Crook County, and (2) all the Ochoco National Forest has been completed. The timber types consist of five density classes which are correlated with different species compositions as the first step in the multistage forest inventory. Using the ERTS magnetic tape data the computer center has produced a 12 by 25 mile strip printout of bands 5, 6, and 7. The computer printouts are to be analyzed for different timber types and possible insect damage. Other results are: (1) limited number of clearcuts in eastern Oregon and in Cascades evident; (2) positive transparencies of band 5 appear to be too dark for maximum information of forested areas; and (3) much more information in the computer printouts of bands 6 and 7, than 5, when analyzing forest conditions.

Simonson, G. H.↗

Comparative life cycle assessment of remote potable water supply for the Department of Defense

The Department of Defense (DOD) and other agencies, including relief organizations, require potable water for remote missions around the globe. As part of recent initiative by the U.S. Federal government through Executive Order 14057, the DOD has been instructed to investigate the sustainability of operations and practices within the context of climate change. One such practice that needs to be addressed is the procurement of potable water, an essential requirement of any remote mission or location. Currently, there are three primary means of procuring potable water at remote locations: bottled water, on-site purification, or tie-in to existing, local infrastructure. The first two operations are often considered the most secure options, but have sustainability concerns. The purpose of this study is to compare the environmental impacts of bottled water procurement versus on-site treatment via a mobile Reverse Osmosis Water Purification Unit (ROWPU), which uses multiple levels of filtration to make potable water from a local source. A cradle-to-gate assessment was developed for both systems to compare different options for potable water supply. An in person inventory was paired with data taken from the Ecoinvent 3.8 database to directly compare the two systems. The two systems are compared on a 5-year timeline to analyze the environmental impact of repeated bottled water transport versus diesel generator-fueled on-site treatment. Across all impact categories, the results indicate that high energy costs of the reverse osmosis process have significantly less impact on the environment than the repetitive transport and procurement of bottled water. The results of the study have important implications for advancing sustainable operations for remote communities or temporary settlements.

54 ENVIRONMENTAL SCIENCES↗

Opinion: Coordinated development of emission inventories for climate forcers and air pollutants

Emissions into the atmosphere of fine particulate matter, its precursors, and precursors to tropospheric ozone impact not only human health and ecosystems, but also the climate by altering Earth's radiative balance. Accurately quantifying these impacts across local to global scales historically and in future scenarios requires emission inventories that are accurate, transparent, complete, comparable, and consistent. In an effort to better quantify the emissions and impacts of these pollutants, also called short-lived climate forcers (SLCFs), the Intergovernmental Panel on Climate Change (IPCC) is developing a new SLCF emissions methodology report. This report would supplement existing IPCC reporting guidance on greenhouse gas (GHG) emission inventories, which are currently used by inventory compilers to fulfill national reporting requirements under the United Nations Framework Convention on Climate Change (UNFCCC) and new requirements of the Enhanced Transparency Framework (ETF) under the Paris Agreement starting in 2024. We review the relevant issues, including how air pollutant and GHG inventory activities have historically been structured, as well as potential benefits, challenges, and recommendations for coordinating GHG and air pollutant inventory efforts. We argue that, while there are potential benefits to increasing coordination between air pollutant and GHG inventory development efforts, we also caution that there are differences in appropriate methodologies and applications that must jointly be considered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Field operations with cesium clocks in HF navigation systems

Networks of HF phase comparison marine navigation stations employing cesium clocks are discussed. The largest permanent network is in the Gulf of Mexico where some fourteen base stations are continuously active and others are activated as needed. These HF phase comparison systems, which operate on a single transmission path, require a clock on the mobile unit as well. Inventory consists of upwards of 70 clocks from two different manufacturers. The maintenance of this network as an operating system requires a coordinated effort involving clock preparation, clock environment control, station performance monitoring and field service.

Christy, E. H.↗

The chemical composition of the pre-solar nebula

The chemical composition of comets may reflect an origin in the molecular cloud which subsequently formed the solar nebula. The chemistry of different types of interstellar clouds is contrasted, including an inventory of molecular species detected in Orion and in TMC 1. The first astronomical detections of the J = (1-0) transition of HCS(+) and the J = (16-15) transition of HC5N and the first detection of SO2 in a cold dust cloud are reported.

Irvine, W. M.↗

Carbon chemistry in dense molecular clouds: Theory and observational constraints

For the most part, gas phase models of the chemistry of dense molecular clouds predict the abundances of simple species rather well. However, for larger molecules and even for small systems rich in carbon these models often fail spectacularly. Researchers present a brief review of the basic assumptions and results of large scale modeling of the carbon chemistry in dense molecular clouds. Particular attention is to the influence of the gas phase C/O ratio in molecular clouds, and the likely role grains play in maintaining this ratio as clouds evolve from initially diffuse objects to denser cores with associated stellar and planetary formation. Recent spectral line surveys at centimeter and millimeter wavelengths along with selected observations in the submillimeter have now produced an accurate inventory of the gas phase carbon budget in several different types of molecular clouds, though gaps in our knowledge clearly remain. The constraints these observations place on theoretical models of interstellar chemistry can be used to gain insights into why the models fail, and show also which neglected processes must be included in more complete analyses. Looking toward the future, larger molecules are especially difficult to study both experimentally and theoretically in such dense, cold regions, and some new methods are therefore outlined which may ultimately push the detectability of small carbon chains and rings to much heavier species.

Blake, Geoffrey A.↗