Denitrification is a critical process regulating the removal of bioavailable nitrogen (N) from natural and human-altered systems. While it has been extensively studied in terrestrial, freshwater, and marine systems, there has been limited communication among denitrification scientists working in these individual systems. Here, we compare rates of denitrification and controlling factors across a range of ecosystem types. We suggest that terrestrial, freshwater, and marine systems in which denitrification occurs can be organized along a continuum ranging from (1) those in which nitrification and denitrification are tightly coupled in space and time to (2) those in which nitrate production and denitrification are relatively decoupled. In aquatic ecosystems, N inputs influence denitrification rates whereas hydrology and geomorphology influence the proportion of N inputs that are denitrified. Relationships between denitrification and water residence time and N load are remarkably similar across lakes, river reaches, estuaries, and continental shelves. Spatially distributed global models of denitrification suggest that continental shelf sediments account for the largest portion (44%) of total global denitrification, followed by terrestrial soils (22%) and oceanic oxygen minimum zones (OMZs; 14%). Freshwater systems (groundwater, lakes, rivers) account for about 20% and estuaries 1% of total global denitrification. Denitrification of land-based N sources is distributed somewhat differently. Within watersheds, the amount of land-based N denitrified is generally highest in terrestrial soils, with progressively smaller amounts denitrified in groundwater, rivers, lakes and reservoirs, and estuaries. A number of regional exceptions to this general trend of decreasing denitrification in a downstream direction exist, including significant denitrification in continental shelves of N from terrestrial sources. Though terrestrial soils and groundwater are responsible for much denitrification at the watershed scale, per-area denitrification rates in soils and groundwater (kg Nkm � 2 � yr � 1 ) are, on average, approximately one-tenth the per-area rates of denitrification in lakes, rivers, estuaries, continental shelves, or OMZs. A number of potential approaches to increase denitrification on the landscape, and thus decrease N export to sensitive coastal systems exist. However, these have not generally been widely tested for their effectiveness at scales required to significantly reduce N export at the whole watershed scale.

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Denitrification across landscapes and waterscapes: a synthesis.

Nitrate attenuation in groundwater: a review of biogeochemical controlling processes.

Nature’s photosynthesis uses the sun’s energy with chlorophyll in plants as a catalyst to recycle carbon dioxide and water into new plant life. Only given sufficient geological time, millions of years, can new fossil fuels be formed naturally. The burning of our diminishing fossil fuel reserves is accompanied by large anthropogenic CO2 release, which is outpacing nature’s CO2 recycling capability, causing significant environmental harm. To supplement the natural carbon cycle, we have proposed and developed a feasible anthropogenic chemical recycling of carbon dioxide. Carbon dioxide is captured by absorption technologies from any natural or industrial source, from human activities, or even from the air itself. It can then be converted by feasible chemical transformations into fuels such as methanol, dimethyl ether, and varied products including synthetic hydrocarbons and even proteins for animal feed, thus supplementing our food chain. This concept of broad scope and framework is the basis of what we call...

Anthropogenic Chemical Carbon Cycle for a Sustainable Future

Denitrification, the reduction of the nitrogen (N) oxides, nitrate (NO3-) and nitrite (NO2-), to the gases nitric oxide (NO), nitrous oxide (N2O), and dinitrogen (N2), is important to primary production, water quality, and the chemistry and physics of the atmosphere at ecosystem, landscape, regional, and global scales. Unfortunately, this process is very difficult to measure, and existing methods are problematic for different reasons in different places at different times. In this paper, we review the major approaches that have been taken to measure denitrification in terrestrial and aquatic environments and discuss the strengths, weaknesses, and future prospects for the different methods. Methodological approaches covered include (1) acetylene-based methods, (2) 15N tracers, (3) direct N2 quantification, (4) N2:Ar ratio quantification, (5) mass balance approaches, (6) stoichiometric approaches, (7) methods based on stable isotopes, (8) in situ gradients with atmospheric environmental tracers, and (9) molecular approaches. Our review makes it clear that the prospects for improved quantification of denitrification vary greatly in different environments and at different scales. While current methodology allows for the production of accurate estimates of denitrification at scales relevant to water and air quality and ecosystem fertility questions in some systems (e.g., aquatic sediments, well-defined aquifers), methodology for other systems, especially upland terrestrial areas, still needs development. Comparison of mass balance and stoichiometric approaches that constrain estimates of denitrification at large scales with point measurements (made using multiple methods), in multiple systems, is likely to propel more improvement in denitrification methods over the next few years.

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Methods for measuring denitrification: diverse approaches to a difficult problem

Carbon dioxide disposal in carbonate minerals

The sudden, catastrophic release of gas from Lake Nyos on 21 August 1986 caused the deaths of at least 1700 people in the northwest area of Cameroon, West Africa. Chemical, isotopic, geologic, and medical evidence support the hypotheses that (i) the bulk of gas released was carbon dioxide that had been stored in the lake's hypolimnion, (ii) the victims exposed to the gas cloud died of carbon dioxide asphyxiation, (iii) the carbon dioxide was derived from magmatic sources, and (iv) there was no significant, direct volcanic activity involved. The limnological nature of the gas release suggests that hazardous lakes may be identified and monitored and that the danger of future incidents can be reduced.

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The 1986 Lake Nyos Gas Disaster in Cameroon, West Africa

[1] Recharge rates of nitrate (NO3−) to groundwater beneath agricultural land commonly are greater than discharge rates of NO3− in nearby streams, but local controls of NO3− distribution in the subsurface generally are poorly known. Groundwater dating (CFC, 3H) was combined with chemical (ions and gases) and stable isotope (N, S, and C) analyses to resolve the effects of land use changes, flow patterns, and water-aquifer reactions on the distributions of O2, NO3−, SO4=, and other constituents in a two-dimensional vertical section leading from upland cultivated fields to a riparian wetland and stream in a glacial outwash sand aquifer near Princeton, Minnesota. Within this section a “plume” of oxic NO3−-rich groundwater was present at shallow depths beneath the fields and part of the wetland but terminated before reaching the stream or the wetland surface. Groundwater dating and hydraulic measurements indicate travel times in the local flow system of 0 to >40 years, with stratified recharge beneath the fields, downward diversion of the shallow NO3−-bearing plume by semiconfining organic-rich valley-filling sediments under the wetland and upward discharge across the valley and stream bottom. The concentrations and δ15N values of NO3− and N2 indicate that the NO3− plume section was bounded in three directions by a curvilinear zone of active denitrification that limited its progress; however, when recalculated to remove the effects of denitrification, the data also indicate changes in both the concentrations and δ15N values of NO3− that was recharged in the past. Isotope data and mass balance calculations indicate that FeS2 and other ferrous Fe phases were the major electron donors for denitrification in at least two settings: (1) within the glacial-fluvial aquifer sediments beneath the recharge and discharge areas and (2) along the bottom of the valley-filling sediments in the discharge area. Combined results indicate that the shape and progress of the oxic NO3− plume termination were controlled by a combination of (1) historical and spatial variations in land use practices, (2) contrast in groundwater flow patterns between the agricultural recharge area and riparian wetland discharge area, and (3) distribution and abundance of electron donors in both the sand aquifer and valley-filling sediments. The data are consistent with slow migration of redox zones through the aquifer in response to recharging oxic groundwater during Holocene time, then an order-of-magnitude increase in the flux of electron acceptors as a result of agricultural NO3− contamination in the late twentieth century, to which the redox zone configuration still may be adjusting. The importance of denitrification for NO3− movement through formerly glaciated terrains should depend on the source areas and depositional environments of the glacial sediments, as well as geomorphology and recent stream-valley sediment history.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2001WR000663

Denitrification in the recharge area and discharge area of a transient agricultural nitrate plume in a glacial outwash sand aquifer, Minnesota

Magnetization and geochemistry of greigite-bearing Cretaceous strata, North Slope basin, Alaska

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

Leachate from municipal landfills can create groundwater contaminant plumes that may last for decades to centuries. The fate of reactive contaminants in leachate-affected aquifers depends on the sustainability of biogeochemical processes affecting contaminant transport. Temporal variations in the configuration of redox zones downgradient from the Norman Landfill were studied for more than a decade. The leachate plume contained elevated concentrations of nonvolatile dissolved organic carbon (NVDOC) (up to 300 mg/L), methane (16 mg/L), ammonium (650 mg/L as N), iron (23 mg/L), chloride (1030 mg/L), and bicarbonate (4270 mg/L). Chemical and isotopic investigations along a 2D plume transect revealed consumption of solid and aqueous electron acceptors in the aquifer, depleting the natural attenuation capacity. Despite the relative recalcitrance of NVDOC to biodegradation, the center of the plume was depleted in sulfate, which reduces the long-term oxidation capacity of the leachate-affected aquifer. Ammonium and methane were attenuated in the aquifer relative to chloride by different processes: ammonium transport was retarded mainly by physical interaction with aquifer solids, whereas the methane plume was truncated largely by oxidation. Studies near plume boundaries revealed temporal variability in constituent concentrations related in part to hydrologic changes at various time scales. The upper boundary of the plume was a particularly active location where redox reactions responded to recharge events and seasonal water-table fluctuations. Accurately describing the biogeochemical processes that affect the transport of contaminants in this landfill-leachate-affected aquifer required understanding the aquifer's geologic and hydrodynamic framework.

Michele L.W. Tuttle

Papers

The 1986 Lake Nyos Gas Disaster in Cameroon, West Africa

Denitrification in the recharge area and discharge area of a transient agricultural nitrate plume in a glacial outwash sand aquifer, Minnesota

Magnetization and geochemistry of greigite-bearing Cretaceous strata, North Slope basin, Alaska

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

Biogeochemical Evolution of a Landfill Leachate Plume, Norman, Oklahoma