Sybil P. Seitzinger

Transformation of the Nitrogen Cycle: Recent Trends, Questions, and Potential Solutions

Humans continue to transform the global nitrogen cycle at a record pace, reflecting an increased combustion of fossil fuels, growing demand for nitrogen in agriculture and industry, and pervasive inefficiencies in its use. Much anthropogenic nitrogen is lost to air, water, and land to cause a cascade of environmental and human health problems. Simultaneously, food production in some parts of the world is nitrogen-deficient, highlighting inequities in the distribution of nitrogen-containing fertilizers. Optimizing the need for a key human resource while minimizing its negative consequences requires an integrated interdisciplinary approach and the development of strategies to decrease nitrogen-containing waste.

The Nitrogen Cascade

Abstract Human production of food and energy is the dominant continental process that breaks the triple bond in molecular nitrogen (N2) and creates reactive nitrogen (Nr) species. Circulation of anthropogenic Nr in Earth’s atmosphere, hydrosphere, and biosphere has a wide variety of consequences, which are magnified with time as Nr moves along its biogeochemical pathway. The same atom of Nr can cause multiple effects in the atmosphere, in terrestrial ecosystems, in freshwater and marine systems, and on human health. We call this sequence of effects the nitrogen cascade. As the cascade progresses, the origin of Nr becomes unimportant. Reactive nitrogen does not cascade at the same rate through all environmental systems; some systems have the ability to accumulate Nr, which leads to lag times in the continuation of the cascade. These lags slow the cascade and result in Nr accumulation in certain reservoirs, which in turn can enhance the effects of Nr on that environment. The only way to eliminate Nr accumulation and stop the cascade is to convert Nr back to nonreactive N2.

Controlling Eutrophication: Nitrogen and Phosphorus

Improvements in the water quality of many freshwater and most coastal marine ecosystems requires reductions in both nitrogen and phosphorus inputs.

Closing the global N2O budget: nitrous oxide emissions through the agricultural nitrogen cycle

In 1995 a working group was assembled at the request of OECD/IPCC/IEA to revise the methodology for N2O from agriculture for the National Greenhouse Gas Inventories Methodology. The basics of the methodology developed to calculate annual country level nitrous oxide (N2O) emissions from agricultural soils is presented herein. Three sources of N2O are distinguished in the new methodology: (i) direct emissions from agricultural soils, (ii) emissions from animal production, and (iii) N2O emissions indirectly induced by agricultural activities. The methodology is a simple approach which requires only input data that are available from FAO databases. The methodology attempts to relate N2O emissions to the agricultural nitrogen (N) cycle and to systems into which N is transported once it leaves agricultural systems. These estimates are made with the realization that increased utilization of crop nutrients, including N, will be required to meet rapidly growing needs for food and fiber production in our immediate future. Anthropogenic N input into agricultural systems include N from synthetic fertilizer, animal wastes, increased biological N-fixation, cultivation of mineral and organic soils through enhanced organic matter mineralization, and mineralization of crop residue returned to the field. Nitrous oxide may be emitted directly to the atmosphere in agricultural fields, animal confinements or pastoral systems or be transported from agricultural systems into ground and surface waters through surface runoff. Nitrate leaching and runoff and food consumption by humans and introduction into sewage systems transport the N ultimately into surface water (rivers and oceans) where additional N2O is produced. Ammonia and oxides of N (NOx) are also emitted from agricultural systems and may be transported off-site and serve to fertilize other systems which leads to enhanced production of N2O. Eventually, all N that moves through the soil system will be either terminally sequestered in buried sediments or denitrified in aquatic systems. We estimated global N2O–N emissions for the year 1989, using midpoint emission factors from our methodology and the FAO data for 1989. Direct emissions from agricultural soils totaled 2.1 Tg N, direct emissions from animal production totaled 2.1 Tg N and indirect emissions resulting from agricultural N input into the atmosphere and aquatic systems totaled 2.1 Tg N2O–N for an annual total of 6.3 Tg N2O–N. The N2O input to the atmosphere from agricultural production as a whole has apparently been previously underestimated. These new estimates suggest that the missing N2O sources discussed in earlier IPCC reports is likely a biogenic (agricultural) one.

The fate of nitrogen and phosphorus at the land-sea margin of the North Atlantic Ocean

Five large rivers that discharge on the western North Atlantic continental shelf carry about 45% of the nitrogen (N) and 70% of the phosphorus (P) that others estimate to be the total flux of these elements from the entire North Atlantic watershed, including North, Central and South America, Europe, and Northwest Africa. We estimate that 61 · 109 moles y−1 of N and 20 · 109 moles y−1 of P from the large rivers are buried with sediments in their deltas, and that an equal amount of N and P from the large rivers is lost to the shelf through burial of river sediments that are deposited directly on the continental slope. The effective transport of active N and P from land to the shelf through the very large rivers is thus reduced to 292 · 109 moles y−1 of N and 13 · 109 moles y−1 of P.The remaining riverine fluxes from land must pass through estuaries. An analysis of annual total N and total P budgets for various estuaries around the North Atlantic revealed that the net fractional transport of these nutrients through estuaries to the continental shelf is inversely correlated with the log mean residence time of water in the system. This is consistent with numerous observations of nutrient retention and loss in temperate lakes. Denitrification is the major process responsible for removing N in most estuaries, and the fraction of total N input that is denitrified appears to be directly proportional to the log mean water residence time. In general, we estimate that estuarine processes retain and remove 30–65% of the total N and 10–55% of the total P that would otherwise pass into the coastal ocean. The resulting transport through estuaries to the shelf amounts to 172–335 · 109 moles y−1 of N and 11–19 · 109 moles y−1 of P. These values are similar to the effective contribution from the large rivers that discharge directly on the shelf.For the North Atlantic shelf as a whole, N fluxes from major rivers and estuaries exceed atmospheric deposition by a factor of 3.5–4.7, but this varies widely among regions of the shelf. For example, on the U.S. Atlantic shelf and on the northwest European shelf, atmospheric deposition of N may exceed estuarine exports. Denitrification in shelf sediments exceeds the combined N input from land and atmosphere by a factor of 1.4–2.2. This deficit must be met by a flux of N from the deeper ocean. Burial of organic matter fixed on the shelf removes only a small fraction of the total N and P input (2–12% of N from land and atmosphere; 1–17% of P), but it may be a significant loss for P in the North Sea and some other regions. The removal of N and P in fisheries landings is very small. The gross exchange of N and P between the shelf and the open ocean is much larger than inputs from land and, for the North Atlantic shelf as a whole, it may be much larger than the N and P removed through denitrification, burial, and fisheries. Overall, the North Atlantic continental shelf appears to remove some 700–950· 109 moles of N each year from the deep ocean and to transport somewhere between 18 and 30 · 109 moles of P to the open sea. If the N and P associated with riverine sediments deposited on the continental slope are included in the total balance, the net flux of N to the shelf is reduced by 60 · 109 moles y−1 and the P flux to the ocean is increased by 20 · 109 moles y−1. These conclusions are quite tentative, however, because of large uncertainties in our estimates of some important terms in the shelf mass balance.

Impacts of Atmospheric Anthropogenic Nitrogen on the Open Ocean

Increasing quantities of atmospheric anthropogenic fixed nitrogen entering the open ocean could account for up to about a third of the oceans external (nonrecycled) nitrogen supply and up to ∼3% of the annual new marine biological production, ∼0.3 petagram of carbon per year. This input could account for the production of up to ∼1.6 teragrams of nitrous oxide (N2O) per year. Although ∼10% of the oceans drawdown of atmospheric anthropogenic carbon dioxide may result from this atmospheric nitrogen fertilization, leading to a decrease in radiative forcing, up to about two-thirds of this amount may be offset by the increase in N2O emissions. The effects of increasing atmospheric nitrogen deposition are expected to continue to grow in the future.

Global distribution of nitrous oxide production and N inputs in freshwater and coastal marine ecosystems

This study examines N2O emissions from aquatic environments globally, particularly as they are affected by anthropogenic activity. The global distribution of N2O production in rivers and estuaries was modeled as a function of nitrification and denitrification rates, which were related to external nitrogen (N) inputs. N loading rates were estimated as a function of environmental parameters in the watersheds using two existing models that we adapted for global databases. Model estimated export of dissolved inorganic nitrogen (DIN) by world rivers to estuaries in 1990 is 20.8 Tg N yr−1; approximately 75% is estimated to be anthropogenic. DIN export to the Atlantic and Indian Oceans is similar (5.4 Tg N yr−1 and 4.6 Tg N yr−1, respectively); inputs to the Pacific are approximately 50% greater. China and southeast Asia account for over 50% of DIN export by world rivers. Globally, anthropogenic DIN export is predominately attributed to fertilizer N, followed by sewage and atmospheric deposition. About 8% of the total N inputs to the terrestrial environment can be accounted for as DIN export by rivers. Worldwide N2O emissions from rivers (55%), estuaries (11%), and continental shelves (33%) are calculated to be 1.9 Tg N yr−1. For rivers and estuaries, approximately 90% of N2O emissions are in the northern hemisphere in line with the regional distribution of DIN export by rivers. China and India account for about 50% of N2O emissions from rivers and estuaries. About 1% of the N input from fertilizers, atmospheric deposition, and sewage to watersheds is lost as N2O in rivers and estuaries. Globally, rivers and estuaries could account for approximately 20% of the current global anthropogenic N2O emissions and are similar in magnitude to a number of previously identified sources including direct emissions of N2O from soils induced by anthropogenic N inputs.

Nitrogen retention in rivers: model development and application to watersheds in the northeastern U.S.A.

A regression model (RivR-N) was developed that predicts the proportion of N removed from streams and reservoirs as an inverse function of the water displacement time of the water body (ratio of water body depth to water time of travel). When appliedto 16 drainage networks in the eastern U.S.,the RivR-N model predicted that 37% to 76%of N input to these rivers is removed duringtransport through the river networks.Approximately half of that is removed in1st through 4th order streams whichaccount for 90% of the total stream length. The other half is removed in 5th orderand higher rivers which account for only about10% of the total stream length. Most Nremoved in these higher orders is predicted tooriginate from watershed loading to small andintermediate sized streams. The proportion ofN removed from all streams in the watersheds(37–76%) is considerably higher than theproportion of N input to an individual reachthat is removed in that reach (generally<20%) because of the cumulative effect ofcontinued nitrogen removal along the entireflow path in downstream reaches. Thisgenerally has not been recognized in previousstudies, but is critical to an evaluation ofthe total amount of N removed within a rivernetwork. At the river network scale,reservoirs were predicted to have a minimaleffect on N removal. A fairly modest decrease(<10 percentage points) in the N removed atthe river network scale was predicted when athird of the direct watershed loading was tothe two highest orders compared to a uniformloading.

Global river nutrient export: A scenario analysis of past and future trends

[1] An integrated modeling approach was used to connect socioeconomic factors and nutrient management to river export of nitrogen, phosphorus, silica and carbon based on an updated Global NEWS model. Past trends (1970–2000) and four future scenarios were analyzed. Differences among the scenarios for nutrient management in agriculture were a key factor affecting the magnitude and direction of change of future DIN river export. In contrast, connectivity and level of sewage treatment and P detergent use were more important for differences in DIP river export. Global particulate nutrient export was calculated to decrease for all scenarios, in part due to increases in dams for hydropower. Small changes in dissolved silica and dissolved organics were calculated for all scenarios at the global scale. Population changes were an important underlying factor for river export of all nutrients in all scenarios. Substantial regional differences were calculated for all nutrient elements and forms. South Asia alone accounted for over half of the global increase in DIN and DIP river export between 1970 and 2000 and in the subsequent 30 years under the Global Orchestration scenario (globally connected with reactive approach to environmental problems); DIN river export decreased in the Adapting Mosaic (globally connected with proactive approach) scenario by 2030, although DIP continued to increase. Risks for coastal eutrophication will likely continue to increase in many world regions for the foreseeable future due to both increases in magnitude and changes in nutrient ratios in river export.

Sources of nitrate in rivers draining sixteen watersheds in the northeastern U.S.: Isotopic constraints

The feasibility of using nitrogen and oxygenisotope ratios of nitrate (NO3−) forelucidating sources and transformations ofriverine nitrate was evaluated in a comparativestudy of 16 watersheds in the northeastern U.S.A. Stream water was sampled repeatedly at theoutlets of the watersheds between January andDecember 1999 for determining concentrations,δ15N values, and δ18Ovalues of riverine nitrate.In conjunction with information about land useand nitrogen fluxes,δ15Nnitrate andδ18Onitrate values providedmainly information about sources of riverinenitrate. In predominantly forested watersheds,riverine nitrate had mean concentrations ofless than 0.4 mg NO3−-N L−1,δ15Nnitrate values of lessthan +5‰, and δ18Onitratevalues between +12 and +19‰. This indicatesthat riverine nitrate was almost exclusivelyderived from soil nitrification processes withpotentially minor nitrate contributions fromatmospheric deposition in some catchments. Inwatersheds with significant agricultural andurban land use, concentrations of riverinenitrate were as high as 2.6 mg NO3−-NL−1 with δ15Nnitratevalues between +5 and +8‰ andδ18Onitrate values generallybelow +15‰. Correlations between nitrateconcentrations, δ15Nnitratevalues, and N fluxes suggest that nitrate inwaste water constituted a major, and nitrate inmanure a minor additional source of riverinenitrate. Atmospheric nitrate deposition ornitrate-containing fertilizers were not asignificant source of riverine nitrate inwatersheds with significant agricultural andurban land use. Although complementary studiesindicate that in-stream denitrification wassignificant in all rivers, the isotopiccomposition of riverine nitrate sampled at theoutlet of the 16 watersheds did not provideevidence for denitrification in the form ofelevated δ15Nnitrate andδ18Onitrate values. Relativelylow isotopic enrichment factors for nitrogenand oxygen during in-stream denitrification andcontinuous admixture of nitrate from theabove-described sources are thought to beresponsible for this finding.