Executive Summary Integrated Science Assessment Oxides of Nitrogen and Sulfur Ecological Criteria December 2008 ¦ EPA/600/R-08/082F U.S. Environmental Protection Agency | Office of Research and Development | National Center for Environmental Assessment http://cfpub.epa.gov/ncea/cfm/recordisplay.cfm?deid=201485 Introduction his Integrated Science Assessment (ISA) is a synthesis and evaluation of M the most policy-relevant science that forms the scientific foundation for the review of the secondary (welfare-based) national ambient air quality standards (NAAGS) for oxides of nitrogen (NOx) and oxides of sulfur (SOx). The Clean Air Act defi- nition of welfare effects includes, but is not limited to, effects on soils, water, wildlife, vegetation, visibility, weather, and climate, as well as effects on man-made materials, economic values, and personal comfort and well-being. The current secondary NAAQS for SOx, set in 1973, is a 3-hour aver- age of 0.5 ppm1 sulfur dioxide (SO2), not to be exceeded more than once per year. The secondary NAAQS for NOx is identi- cal to the pri- mary standard set in 19711 an annual average not to exceed 0.053 ppm nitrogen dioxide (NO2). The current secon- dary NAAQS were set to protect against di- rect damage to vegetation by exposure to gas-phase SOx or NOx. Scope 7 his ISA is focused on ecological effects resulting from current deposi- tion of compounds containing nitro- gen (N) and sulfur (S). Acidification, N nutri- ent enrichment and effects of sulfate (SO42 on methylation of mercury (Hg) are high- lighted in the document. The following fig- ure illustrates the scope of the document. 1 ppm= 1000 ppb Atmospheric cycle of N oxides See figure 2-16 Ambient Air Concentration Sunlight Dissolution 2H+ +SO42- ~ H++N03 Atmospheric cycle of S compounds See figure 2-18 Oxidation S02 H2SO4 NO* ~HNOa Wet Deposition H*. NH4+, NO3-, S042 t/li VOC [ Foliar and nutrient effects Dry deposition NOx, NHX, SOx Deposition C and N cycle in terrestrial ecosystem See figure 3-36 Acidification of water + Eutrophication Hg cycle in aquatic ecosystem See figure 3-59 Ecological Effect C, N and P cycle in aquatic ecosystem See figure 3-40 ------- ISA for Oxides of Nitrogen arid Sulfur Executive Summary Both N and S contribute to acidification of ecosystems. This ISA considers several chemical forms that contribute to acidifying deposition, including gases and particles derived from SOx, NOx, and reduced nitro- gen (NHx). Deposition of N contributes to N-nutrient en- richment and eutrophication. An assess- ment of the complex ecological effects of atmospheric N deposition requires consid- eration of many different chemical forms of reactive N (Nr). For this reason, the ISA in- cludes evaluation of data on the most common reduced inorganic forms of N, ammonia (NHa) and ammonium (NH/); on oxidized inorganic forms including nitric ox- ide (NO) and N02> nitrate (N03~), nitric acid (HNO3), and nitrous oxide (N2O); and on or- ganic N compounds including peroxyacetyl nitrate (PAN). Other welfare effects addressed in the ISA include effects of SO42" deposition on Hg methylation, along with evidence related to direct exposure to gas-phase NOx and SOx. The key conclusions of the ISA follow. ------- ISA for Oxides of Nitrogen arid Sulfur Executive Summary Current concentrations and deposition mbient annual NOx and SOx con- centrations as reported in the routine national networks have decreased substantially owing to controls enacted since the 1970s. NOx decreased -35% in the period 1990-2005, to current an- nual average concentrations of -15 ppb. Emissions of SOx have been substantially re- duced in recent years: annual average ambient SOx concentrations have de- creased -50% in the period 1990-2005 and now stand at -4 ppb for both aggregate annual and 24-hour average concentra- tions nation-wide. Emitted NOx, SOx, NHx and other pollutants can be transported vertically by convection into the upper part of the mixed layer on one day, then transported overnight in a layer of high concentrations. Once pollut- ants are lofted to the middle and upper tro- posphere, they typically have a much longer lifetime and, with the generally stronger winds at these altitudes, can be transported long distances from their source regions. The length scale of this transport is highly variable owing to differing chemical and meteorological conditions encoun- tered along the transport path. ------- ISA for Oxides of Nitrogen anci Ann. Numerical chemical-transport models (CTMs) are the prime tools for computing emissions and interactions among pollutants like NOx, SOx, and NHx, their transport and transformation including production of sec- ondary aerosols like ammonium nitrate and ammonium sulfate, the evolution of particle size distributions, the resulting atmospheric concentrations and the deposition of these pollutants to the surface. CTMs are driven by calculated emissions for primary species such as NOx, SOx, NH3, and primary particu- late matter, and by the meteorological fields produced by other numerical predic- tion models. As such, CTMs are the chief means of relating emitted pollutants with deposited ones. The emitted, transported, and transformed pollutants reach the surface where they can have ecological effects largely through deposition. Direct and indirect wet and dry deposition to specific locations like water- sheds depend on air pollutant emissions and concentrations in the airshed above the wa- tershed, but the shape and areal extent of the airshed is quite different from that of the watershed owing to the transport and trans- formation of emitted pollutants described above. Deposition is spatially heterogeneous across the U.S. In the years 2004-2006, routine na- tional monitoring networks reported mean S deposition in the U.S. highest east of the Mis- sissippi River with the highest reported depo- sition, 21 kg S/ha/yr, in the Ohio River Valley where most recording stations reported three-year averages for this period of more than 10 kg S/ha/yr. Numerous other stations in the eastern U.S. reported S deposition greater than 5 kg S/ha/yr. Data are sparse for the central U.S. between the 100th me- ridian and the Mississippi River; but, where available, deposition values there were lower than in most of the eastern U.S., rang- ing from 4 to over 5 kg S/ha/yr. Total S depo- sition in the U.S. west of the 100th meridian is lower than in the East or upper Midwest, ow- ing to lower densities of high-emitting sources in the West. In the years 2004-2006, all routine recording stations in the West re- ported less than 2 kg S/ha/yr and many re- ported less than 1 kg S/ha/yr. S was primarily deposited in the form of wet SO42-, followed by a smaller proportion of dry SO2, and a much smaller proportion of dry SO42-. Expanding urbanization, agricultural intensi- fication, and industrial production during the previous 100 years have produced a nearly 10-fold increase in total N deposited from the atmosphere compared to pre-industrial levels. NOx, chiefly from fossil fuel combus- tion, often dominates total N pollution in the U.S. and comprises from 50 to 75% of current 4 ------- ISA for Oxides of Nitrogen anci Ann. total N atmospheric deposition. This wet and dry atmospheric N deposition is spatially heterogeneous, too, owing to the influence of meteorology, transport, precipitation pat- terns and land use. For 2004-2006, routine national monitoring networks reported the highest mean N deposition totals in the U.S. in the Ohio River Valley, specifically in the states of Indiana and Ohio, with values greater than 9 kg N/ha/yr. N deposition was lower in other parts of the East, including the Southeast and in northern New England. In the central U.S., the highest N annual average deposi- tion totals were on the order of 6 to 7 kg N/ha/yr. Measured concentrations and in- ferred deposition totals were dominated by wet NOs" and NH/ species, followed by dry HNO3, dry NH/, and dry N03~. NH3 is not yet measured routinely in any national net- works; however, smaller-scale intensive monitoring and numerical air quality model- ing both indicate that it may account for more than 80% of the dry reduced N deposi- tion total. The thin coverage of monitoring sites in many locations, especially in the rural West, means that limited data exist on deposition totals in a large number of potentially sensi- tive places. Numerical modeling experi- ments can help fill in these data gaps and suggest that local and even regional areas of high ambient concentration and deposi- tion exist where measured data are un- available. Model-predicted values for N deposition in some regions of the Adiron- dacks in New York are greater than 20 kg N/ha/yr; other model estimates as high as 32 kg N/ha/yr have been made for a region of southern California, where more than half of that total was predicted to come from NO and NO2. The ISA concludes that the national-scale networks routinely monitoring N deposition are inadequate to characterize both the full range of reduced and oxidized forms of N deposition and the substantial regional het- erogeneity across the landscape of the U.S. Although S and N deposition in most areas of the U.S. occurred as wet deposition, there were some exceptions, including parts of California where N deposition was primar- ily dry. 5 ------- ISA for Oxides of Nitrogen and Sulfur Executive Summary Ecological effects of acidification ~~ W he effects of acidifying deposition m on ecosystems have been well § studied over the past several dec- ades and vulnerable areas have been iden- tified in the U.S. The wealth of data has led to the development of widely used ecologi- cal models for predicting soil and surface water acidification. Regional and ecosys- tem vulnerability to acidification results from inherent sensitivity and exposure to acidify- ing deposition. Sensitivity of terrestrial and aquatic ecosys- tems to acidification from S and N deposi- tion is regional and predominantly governed by surficial geology. Other factors contribut- ing to the sensitivity of soils and surface wa- ters to acidifying deposition include topog- raphy, vegetation, soil chemistry, land use, and hydrologic flowpath. most sensitive to terrestrial effects from acidi- fying deposition include forests in the Adi- rondack Mountains of New York, the Green Mountains of Vermont, the White Mountains of New Hampshire, the Allegheny Plateau of Pennsylvania, and high-elevation forest ecosystems in the central and southern Ap- palachians. While studies show some recov- ery of surface waters, there are widespread areas of ongoing depletion of exchange- able base cations in forest soils in the north- eastern U.S., despite recent decreases in acidifying deposition. In aquatic systems, consistent and coherent evidence from multiple studies of many species shows that acidification can cause the loss of acid-sensitive species, and that more species are lost with greater acidifica- tion. These effects are linked to changes in Soil acidification is a natural process, but is often accelerated by acidifying deposition, which can decrease con- centrations of exchangeable base cations in soils. Biological effects of acidification on terrestrial ecosystems are generally attributable to Al toxic- ity and decreased ability of plant roots to take up base cations. Areas The evidence is sufficient to infer a causal relationship between acidifying deposition and effects on: (1) biogeochemistry related to terrestrial and aquatic ecosystems; (2) biota in terrestrial and aquatic ecosystems. 6 ------- ISA for Oxides of Nitrogen and Sulfur Executive Summary surface water chemistry, including concen- trations of SO42", NOs", inorganic Al, and cal- cium (Ca2+), surface water pH, sum of base cations, acid neutralizing capacity (ANC), vertebrates, and fish species richness. These effects on species richness may also affect ecosystem services, such as biodiversity and cultural services such as fishing and tourism. Although both N and S deposition can cause terrestrial and aquatic acidification, S deposition is generally the primary cause of chronic acidification, with secondary con- tributions from N deposition. Following de- creases in S deposition in the 1980s and 1990s, one quarter to one third of the chronically acidic lakes and streams in the U.S. were no longer acidic during baseflow in the year 2000. A number of lakes and streams, however, remain acidic even though wet SO42- deposition has decreased by as much as 30% since 1989. N deposition, which has also decreased in the years since 1990 in most places in the U.S. with routine monitoring, is the primary cause of episodic acidification which, despite its short duration, has been shown to cause long-term bio- logical effects. Many of the surface waters most sensitive to acidification in the U.S. are found in the Examples of biogeochemical indicators of effects from acidifying deposition on ecosystems Ecosystem Biogeochemical Indicator Terrestrial • Soil base saturation • Inorganic Aluminum concentration in soil water • Soil carbon-to-nitrogen ratio Aquatic • Sulfate • Nitrate • Base cations • Acid neutralizing capacity • Surface water inorganic Aluminum • pH Examples of biological indicators of effects from acidifying deposition on ecosystems Indicator Measure Terrestrial Ecosystems Red Spruce Sugar Maple • Percent dieback of canopy trees • Dead basal area, crown vigor index, fine twig die- back Aquatic Ecosystems Fishes, zoo- • Presence/absence plankton, crus- • Fish condition factor taceans, rotifers • Biodiversity and base cation surplus. These effects are also influenced by historical inputs to these systems. Decreases in ANC and pH and in- creases in inorganic Al concentration con- tribute to declines in zooplankton, macroin- 7 ------- ISA for Oxides of Nitrogen arid Sulfur Executive Summary —i 1 1 1 \ 1— -200 -100 0 100 200 300 400 500 ANC(|ieq/L) Number of fish species per lake vs. acidity status, expressed as acid neutralizing capacity (ANC), for Adirondack lakes. Source: Suliivcin et nL 9006b Adirondack Mountains. Northeast, the Southeast, and the moun- tainous West. In the West, acidic surface waters are rare and the extent of chronic surface water acidification that has oc- curred to date has been limited. However, episodic acidification does occur. In both the mountainous West and the Northeast, the most severe acidification of surface wa- ters generally occurs during spring snowmelt. The ISA highlights evidence from two well- studied areas to provide more detail on how acidification affects ecosystems: The Adirondacks (NY) and Shenandoah Na- tional Park (VA). In the Adirondacks, the cur- rent rates of N and S deposition exceed the amount that would allow recovery of the most acid sensitive lakes. In the Shenan- doah, past SO# has accumulated in the soil and is slowly released from the soil into stream water where it causes acidification, making parts of this region sensitive to even the current lower deposition loadings. Numerical models spe- cifically calibrated to these locations and conditions suggest that the number of acidic streams will increase even under current deposition loads. Regions of the northern and eastern U.S. that contain appreciable numbers of lakes and streams sensitive to deleterious effects from acidifying deposition. Source: Stoddard et ai., 2003 8 ------- ISA for Oxides of Nitrogen and Sulfur Executive Summary Ecological effects of nitrogen rhere are many well-studied effects of N deposition on ecosystems and some vulnerable areas have been identified in the U.S. However, the full extent of ecosystem vulnerability is still unknown. Substantial empirical information from spe- cific ecosystems and for specific endpoints is available, but given the complexity of the N cycle, a broadly applicable and well- tested predictive model of the ecological effects of N deposition is not yet available. Though the sensitivity of ecosystems to N deposition deposition across the U.S. varies, a large body of evidence clearly demonstrates a relationship between N deposition and a broad range of ecological effects. The contribution of N deposition to total N load varies among ecosystems. Atmos- pheric N deposition is the main source of new N to most headwater streams, high elevation lakes, and low-order streams. At- mospheric N deposition contributes to the total N load in terrestrial, wetland, freshwa- ter, and estuarine ecosystems that receive N through multiple pathways (i.e. biological N- fixation, agricultural land runoff and waste water effluent). There are multiple biogeo- chemical indicators of N deposition effects. Examples of biogeochemical indicators of effects from reactive N deposition on ecosystems Ecosystem Biogeochemical Indicator • NO3 leaching • Nitrification • Denitrification Terrestrial • N2O emissions and • CH4 emissions Wetland • Soil C:N ratio • Foliar / plant tissue [N], C:N, N:magnesium, N:phosphorus • Soil water [NO3 ] and [NH4 ] • Chlorophyll a Freshwater • Water [NOs ] and • Dissolved inorganic N Estuarine • Dissolved oxygen • N:P The evidence is sufficient to infer a causal rela- tionship between N deposition, to which NOx and NHx contribute, and the alteration of the following: (1) biogeochemical cycling of N and carbon (C) in terrestrial, wetland, freshwater aquatic, and coastal marine ecosystems; (2) biogenic flux of methane (CH4), and N2O in terrestrial and wetland ecosystems; (3) species richness, species composition, and biodiversity in terrestrial, wetland, freshwater aquatic and coastal marine ecosystems. 9 ------- ISA for Oxides of Nitrogen and Sulfur Executive Summary In terrestrial ecosystems, the onset of NC>3~ leaching is one of the best documented biogeochemical indicators that an ecosys- tem receives more N than it uses and is able to retain. N removal by ecosystems is a valuable ecosystem service regulating wa- ter quality. When atmospheric deposition of N impairs the ability of terrestrial and aquatic ecosystems to retain and remove N, NOs" leaching occurs and the degrada- tion of water quality can occur. The onset of leaching was calculated to occur with deposition levels between 5.5 and 10 kg N/ha/yr for sensitive eastern forests. In the mixed conifer forests of the Sierra Nevada and San Bernardino mountains, the onset of increased NC>3~ leaching was calculated to be 17 kg N/ha/yr. Several studies in the Rocky Mountains indicate that the capacity of alpine catchments to retain N was ex- ceeded at levels greater than 5-10 kg N/ha/yr. N deposition alters the biogenic sources and sinks of two greenhouse gases (GHGs), ChU and N2O, in terrestrial and wetland ecosys- tems, resulting in increased emissions to the atmosphere. Non-flooded upland soil is the largest biological sink and takes up about 6% of atmospheric CH4. N addition de- creases CH4 uptake in coniferous and de- ciduous forests, and N addition increases CH4 production in wetlands. Soil is the larg- est source of N2O, accounting for 60% of global emissions. N deposition increases the biogenic emission of N2O in coniferous for- est, deciduous forests, grasslands, and wet- lands. Although N addition can cause a general stimulation of biogenic CH4 and N2O emissions from soils, it is difficult to gen- eralize a dose-response relationship be- tween the amount of N addition and the changes in GHG flux on a large heteroge- neous landscape. This is because GHG pro- duction is influenced by multiple environ- mental factors (e.g., soil, vegetation and climate), which vary greatly over small spa- tial and temporal scales. N is often the most limiting nutrient to growth in ecosystems. N deposition thus often in- creases primary productivity, thereby alter- ing the biogeochemical cycling of C. N Examples of biological indicators of effects from N deposition on ecosystems Ecosystem Biological Indicators Terrestrial and • Altered community composi- Wetlands tion, biodiversity and/or popu- lation decline. Taxa affected include: diatoms, lichen, my- corrhizae, moss, grasses and other herbaceous plants • Plant root: shoot ratio • Terrestrial plant bio- mass/production Freshwater • Phytoplankton bio- and Estuarine mass/production • Toxic or nuisance algae blooms • Submerged aquatic vegetation • Fauna from higher trophic lev- els 10 ------- ISA for Oxides of Nitrogen arid Sulfur Executive Summary deposition can cause changes in ecosys- tem C budgets. However, whether N depo- sition increases or decreases ecosystem C- sequestration remains unclear. A limited number of studies suggest that N deposition may increase C-sequestration in some for- ests, but has no apparent effect on C- sequestration in non-forest ecosystems. In terrestrial ecosystems, N deposition can accelerate plant growth and change C al- location patterns (e.g. shoot:roof ratio), which can increase susceptibility to severe fires, drought, and wind damage. These ef- fects have been shown in studies con- ducted in the western U.S. and Europe. The alteration of primary productivity can also alter competitive interactions among plant species. The increase in growth is greater for some species than others, leading to possi- ble shifts in population dynamics, species composition, community structure, and in few instances, ecosystem type. There are numerous sensitive terrestrial biota and ecosystems that are affected by N deposition. Acidophytic lichens are among the most sensitive terrestrial taxa to N depo- sition, with adverse effects occurring with exposures as low as 3 kg N/ha/yr in the Pacific Northwest and southern California. The onset of declining biodiversity in grass- lands has been estimated to be 5 kg N/ha/yr in Minnesota and the European Un- ion. Altered community composition of al- pine ecosystems in the Rocky Mountains and forest encroachment into temperate grasslands in Southern Canada is estimated to be 10 kg N/ha/yr. The productivity of many freshwater ecosys- tems is N-limited. N deposition can alter species assemblages and cause eutropni- cation of aquatic ecosystems to the extent that N is the growth-limiting nutrient. In the Rocky Mountains, deposition loads of ap- proximately 1.5-2 kg N/ha/yr are reported to alter species composition in the diatom communities in some freshwater lakes, an indicator of impaired water quality. 11 ------- ISA for Oxides of Nitrogen and Sulfur Executive Summary In estuarine ecosystems, N from atmospheric and non-atmospheric sources contributes to increased phytoplankton and algal produc- tivity, leading to eutrophication. Estuary eu- trophication is an ecological problem indi- cated by water quality deterioration, resulting in numerous adverse effects includ- ing hypoxic zones, species mortality, and harmful algal blooms. The calculated con- tribution of atmospheric deposition to total N loads can be as high as 72% in estuaries. The Chesapeake Bay is an example of a large, well-studied, and severely eutrophic estuary that is calculated to receive as much as 30% of its total N load from the at- mosphere. Examples of quantified relationships between deposition levels and ecological effects Kg N/ha/yr Ecological effect Altered diatom communities in high elevation freshwater lakes ~1.5 and elevated N in tree leaf tissue high elevation forests in the west- ern U.S. 3.1 Decline of some lichen species in the western U.S. Altered growth and coverage of alpine plant species in the western U.S. Onset of decline of species rich- ness in grasslands of the U.S. and U.K. Onset of nitrate leaching in Eastern forests of the U.S. Multiple effects in tundra, bogs and freshwater lakes in Europe Multiple effects in arctic, alpine, 5-15 subalpine and scrub habitats in Europe 5.5 - 10 5-10 Other welfare effects: Mercury methylation Hg is highly neurotoxic and once methy- lated, principally by S-reducing bacteria, it can be taken up by microorganisms, zoo- plankton and macroinvertebrates, and concentrated in higher trophic levels, in- cluding fish eaten by humans. In 2006, 3,080 fish consumption advisories were issued be- cause of methylmercury (MeHg), and as of July 2007, 23 states had issued statewide advisories. The production of meaningful amounts of MeHg requires the presence of S042- and Hg, and where Hg is present, in- creased availability of SCU2- results in in- creased production of MeHg. The amount of MeHg produced varies with oxygen content, temperature, pH, and sup- ply of labile organic C. Watersheds with conditions known to be conducive to Hg methylation can be found in the northeast- ern U.S. and southeastern Canada, but bi- otic Hg accumulation has been widely ob- served in other regions that have not been studied as extensively, and where a different set of conditions may exist. The evidence is sufficient to infer a causal relationship be- tween S deposition and in- creased Hg methylation in wetlands and aquatic envi- ronments. 12 ------- ISA for Oxides of Nitrogen and Sulfur Executive Summary Other welfare effects: Direct phytotoxic Acute and chronic exposures to SO2 have phytotoxic effects on vegetation which in- clude foliar injury, decreased photosynthe- sis, and decreased growth. Acute exposures to NO2, NO, PAN, and HNO3 cause plant foliar injury and decreased growth. How- ever, the majority of studies have been per- formed at concentrations of these gas- phase species above current ambient con- ditions observed in the U.S. Consequently, there is little evidence that current concen- Conclusion The main effects of N and S pollution assessed in the ISA are acidification, N en- richment, and Hg methylation. Acidification of ecosystems is driven primarily by deposition resulting from SOx, NOx, and NHx pollution. Acidification from the deposition resulting from current emission levels causes a cascade of effects that harm susceptible aquatic and terrestrial ecosystems, including slower growth and injury to forests and localized extinction of fishes and other aquatic species. In addition to acidification, atmospheric deposition of reactive N re- sulting from current NOx and NHx emissions along with other non-atmospheric sources (e.g., fertilizers and wastewater), causes a suite of ecological changes within sensitive ecosystems. These include increased primary productivity in most N-limited ecosystems, biodiversity losses, changes in C cycling, and eutro- phication and harmful algal blooms in freshwater, estuarine, and ocean eco- systems. In some watersheds, additional SO42" from atmospheric deposition in- creases Hg methylation rates by increasing both the number and activity of S- reducing bacteria. Methylmercury is a powerful toxin that can bioaccumulate to toxic amounts in food webs at higher trophic levels (e.g. bass, perch, otters, or kingfishers). 13 trations of gas-phase S or N oxides are high enough to cause phytotoxic effects. One excep- tion is that some studies indicate that cur- rent HNO3 concentrations may be contributing to the decline in lichen species in the Los Angeles basin. The evidence is sufficient to infer a causal relationship between exposure to SO2, NO, NO2, PAN, and HNOs and injury to vegetation. ------- |