T. E. Graedel

A global model of natural volatile organic compound emissions

Numerical assessments of global air quality and potential changes in atmospheric chemical constituents require estimates of the surface fluxes of a variety of trace gas species. We have developed a global model to estimate emissions of volatile organic compounds from natural sources (NVOC). Methane is not considered here and has been reviewed in detail elsewhere. The model has a highly resolved spatial grid (0.5° × 0.5° latitude/longitude) and generates hourly average emission estimates. Chemical species are grouped into four categories: isoprene, monoterpenes, other reactive VOC (ORVOC), and other VOC (OVOC). NVOC emissions from oceans are estimated as a function of geophysical variables from a general circulation model and ocean color satellite data. Emissions from plant foliage are estimated from ecosystem specific biomass and emission factors and algorithms describing light and temperature dependence of NVOC emissions. Foliar density estimates are based on climatic variables and satellite data. Temporal variations in the model are driven by monthly estimates of biomass and temperature and hourly light estimates. The annual global VOC flux is estimated to be 1150 Tg C, composed of 44% isoprene, 11% monoterpenes, 22.5% other reactive VOC, and 22.5% other VOC. Large uncertainties exist for each of these estimates and particularly for compounds other than isoprene and monoterpenes. Tropical woodlands (rain forest, seasonal, drought-deciduous, and savanna) contribute about half of all global natural VOC emissions. Croplands, shrublands and other woodlands contribute 10–20% apiece. Isoprene emissions calculated for temperate regions are as much as a factor of 5 higher than previous estimates.

Global gridded inventories of anthropogenic emissions of sulfur and nitrogen

Two sets of global inventories of anthropogenic emissions of both oxides of sulfur and oxides of nitrogen for circa 1985 have been produced under the umbrella of the Global Emissions Inventory Activity (GEIA) of the International Global Atmospheric Chemistry Program. The two sets of inventories have different temporal, sectoral, and vertical resolution. Both were compiled using the same data sets; default data sets of global emissions have been refined via the use of more detailed regional data sets. This article reports on the compilation of the annual, one-vertical-level inventories, called version 1A; the inventory files are available to the scientific community via anonymous file transform protocol (FTP). Existing global inventories and regional inventories have been updated and combined on a 1° × 1° longitude/latitude grid. The resulting global anthropogenic emissions are 65 Tg S yr−1 and 21 Tg N yr−1; qualitative uncertainty estimates have been assigned on a regional basis. Emissions of both SOx and NOx are strongly localized in the highly populated and industrialized areas of eastern North America and across Europe; other smaller regions of large emissions are associated with densely populated areas with developed industries or in connection with exploitation of fuels or mineral reserves. The molar ratio of nitrogen to sulfur emissions reflects the overall character of sources; its value is generally between 0.33 and 10 for industrialized and heavily populated areas but varies over a wide range for other areas. We suggest that those requiring sulfur or nitrogen emission inventories standardize on the GEIA inventories, which we believe are authoritative and which are freely available to all users by anonymous FTP.

Metal stocks and sustainability

The relative proportions of metal residing in ore in the lithosphere, in use in products providing services, and in waste deposits measure our progress from exclusive use of virgin ore toward full dependence on sustained use of recycled metal. In the U.S. at present, the copper contents of these three repositories are roughly equivalent, but metal in service continues to increase. Providing todays developed-country level of services for copper worldwide (as well as for zinc and, perhaps, platinum) would appear to require conversion of essentially all of the ore in the lithosphere to stock-in-use plus near-complete recycling of the metals from that point forward.

Composite global emissions of reactive chlorine from anthropogenic and natural sources: Reactive Chlorine Emissions Inventory

Emission inventories for major reactive tropospheric CI species (particulate CI, HC1, C1NO2, CH3CI, CHCI3, CH3CCI3, C2C14, C2HC13, CH2C12, and CHCIF2) were integrated across source types (terrestrial biogenic and oceanic emissions, sea-salt production and dechlorination, biomass burning, industrial emissions, fossil-fuel combustion, and incinera- tion). Composite emissions were compared with known sinks to assess budget closure; relative contributions of natural and anthropogenic sources were differentiated. Model cal- culations suggest that conventional acid-displacement reactions involving Sov)+O3, S(Iv)+ H202, and H2SO4 and HNO3 scavenging account for minor fractions of sea-salt dechlorina- tion globally. Other important chemical pathways involving sea-salt aerosol apparently pro- duce most volatile chlorine in the troposphere. The combined emissions of CH3CI from known sources account for about half of the modeled sink, suggesting fluxes from known sources were unde:estimated, the OH sink was overestimated, or significant unidentified sources exist. Anthropogenic activities (primarily biomass burning) contribute about half the net CH3CI emitted from known sources. Anthropogenic emissions account for only about 10% of the modeled CHCl3 sink. Although poorly constrained, significant fractions of tropo- spheric CH2C12 (25%), C2HC13 (10%), and C2C14 (5%) are emitted from the surface ocean; the combined contributions of C2C14 and C2HC13 from all natural sources may be substan- tially higher than the estimated oceanic flux.

Challenges in Metal Recycling

Metals are infinitely recyclable in principle, but in practice, recycling is often inefficient or essentially nonexistent because of limits imposed by social behavior, product design, recycling technologies, and the thermodynamics of separation. We review these topics, distinguishing among common, specialty, and precious metals. The most beneficial actions that could improve recycling rates are increased collection rates of discarded products, improved design for recycling, and the enhanced deployment of modern recycling methodology. As a global society, we are currently far away from a closed-loop material system. Much improvement is possible, but limitations of many kinds—not all of them technological—will preclude complete closure of the materials cycle.

What Do We Know About Metal Recycling Rates

The recycling of metals is widely viewed as a fruitful sustainability strategy, but little information is available on the degree to which recycling is actually taking place. This article provides an overview on the current knowledge of recycling rates for 60 metals. We propose various recycling metrics, discuss relevant aspects of recycling processes, and present current estimates on global end‐of‐life recycling rates (EOL‐RR; i.e., the percentage of a metal in discards that is actually recycled), recycled content (RC), and old scrap ratios (OSRs; i.e., the share of old scrap in the total scrap flow). Because of increases in metal use over time and long metal in‐use lifetimes, many RC values are low and will remain so for the foreseeable future. Because of relatively low efficiencies in the collection and processing of most discarded products, inherent limitations in recycling processes, and the fact that primary material is often relatively abundant and low‐cost (which thereby keeps down the price of scrap), many EOL‐RRs are very low: Only for 18 metals (silver, aluminum, gold, cobalt, chromium, copper, iron, manganese, niobium, nickel, lead, palladium, platinum, rhenium, rhodium, tin, titanium, and zinc) is the EOL‐RR above 50% at present. Only for niobium, lead, and ruthenium is the RC above 50%, although 16 metals are in the 25% to 50% range. Thirteen metals have an OSR greater than 50%. These estimates may be used in considerations of whether recycling efficiencies can be improved; which metric could best encourage improved effectiveness in recycling; and an improved understanding of the dependence of recycling on economics, technology, and other factors.

Methodology of Metal Criticality Determination

A comprehensive methodology has been created to quantify the degree of criticality of the metals of the periodic table. In this paper, we present and discuss the methodology, which is comprised of three dimensions: supply risk, environmental implications, and vulnerability to supply restriction. Supply risk differs with the time scale (medium or long), and at its more complex involves several components, themselves composed of a number of distinct indicators drawn from readily available peer-reviewed indexes and public information. Vulnerability to supply restriction differs with the organizational level (i.e., global, national, and corporate). The criticality methodology, an enhancement of a United States National Research Council template, is designed to help corporate, national, and global stakeholders conduct risk evaluation and to inform resource utilization and strategic decision-making. Although we believe our methodological choices lead to the most robust results, the framework has been constructed to permit flexibility by the user. Specific indicators can be deleted or added as desired and weighted as the user deems appropriate. The value of each indicator will evolve over time, and our future research will focus on this evolution. The methodology has proven to be sufficiently robust as to make it applicable across the entire spectrum of metals and organizational levels and provides a structural approach that reflects the multifaceted factors influencing the availability of metals in the 21st century.

Tropospheric budget of reactive chlorine

Reactive chlorine in the lower atmosphere (as distinguished from chlorofluorocarbon-derived chlorine in the stratosphere) is important to considerations of precipitation acidity, corrosion, foliar damage, and chemistry of the marine boundary layer. Many of the chlorine-containing gases are difficult to measure, and natural sources appear to dominate anthropogenic sources for some chemical species. As a consequence, no satisfactory budget for reactive chlorine in the lower atmosphere is available. We have reviewed information on sources; source strengths; measurements in gas, aqueous, and aerosol phases; and chemical processes and from those data derive global budgets for nine reactive chlorine species and for reactive chlorine as a whole. The typical background abundance of reactive chlorine in the lower tropospheric is about 1.5 ppbv. The nine species, CH3 Cl, CH3 CCl3, HCl, CHClF2, Cl2* (thought to be HOCl and/or Cl2), CCl2 = CCl2, CH2 Cl2 , COCl2 , and CHCl3, each contribute at least a few percent to that total. The tropospheric reactive chlorine burden of approximately 8.3 Tg Cl is dominated by CH3 Cl (≈45 %) and CH3 CCl3 (≈25 %) and appears to be increasing by several percent per year. By far the most vigorous chlorine cycling appears to occur among seasalt aerosol, HCl, and Cl2*. The principal sources of reactive chlorine are volatilization from seasalt (enhanced by anthropogenically generated reactants), marine algae, volcanoes, and coal combustion (natural sources being thus quite important to the budget). It is anticipated that the concentrations of tropospheric reactive chlorine will continue to increase in the next several decades, particularly near urban areas in the rapidly developing countries.

Criticality of non-fuel minerals: a review of major approaches and analyses.

The criticality of nonfuel minerals is an emerging research subject that captures both the supply risks and the vulnerability of a system to a potential supply disruption. The significance of material criticality for the mass deployment of sustainable and other key technologies is currently obscured by diverse, often immature, and still evolving methodologies. This review explores why principal studies agree or disagree in designating the criticality of certain nonfuel minerals. We survey the literature and analyze several well documented studies in depth, demonstrating that the platinum group metals (e.g., essential for catalytic reduction of air pollutants), and the rare earth elements (e.g., essential for efficient electricity generation in wind turbines) are frequently singled out as critical, albeit by differing criteria. We also discuss the impacts of methodological choices on the designation of raw materials as critical. The treatment of substitutability, time horizons, and the aggregation level of criticality indicators are shown to be significant in this regard. We determine several important issues that have thus far been largely disregarded, especially the justification of methodological components, and policy responses to criticality designation.

Corrosion Mechanisms for Nickel Exposed to the Atmosphere

The physical and chemical phenomena responsible for the atmospheric corrosion of silver are presented. Corrosion layer formation, morphology, and chemical makeup are discussed in the context of silver-containing minerals and other crystalline structures that thermodynamics and kinetics suggest are likely to be present. The constituents that form during the corrosion process are then described, and the formation pathways of acanthite (Ag 2 S) and chlorargyrite (AgCl), the two minerals most often reported to be present in silver corrosion layers, are shown in schematic diagrams. The presence of these species and the essential absence of sulfate, nitrate, carbonate, or organic salts of silver are shown to be a natural consequence of the thin aqueous layer chemistry that obtains on silver in humid environments. The primary atmospheric agents responsible for the degradation are identified as H 2 S, COS, particulate chloride, and possibly HCl, all acting in the presence of moderate to high humidity. Gaseous hydrogen peroxide, which is sometimes present, strongly accelerates silver corrosion. Comprehensive kinetic simulations of the corrosion process are desirable, but await laboratory determinations of the rates of dissolution, and transformation of silver-containing chemical species.