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Topic Name: Large Source of Nitrate has Found in Near-Surface Desert Soils as Water Evaporates on Dry Lake Beds

Category: Environmental engineering

Research persons: Robert Graham

Location: University of California, Riverside, United States

Details

A University of California - Riverside -led study in the Mojave Desert, Calif., has found that soils under “desert pavement” have an unusually high concentration of nitrate, a type of salt, close to the surface. Vulnerable to erosion by rain and wind if the desert pavement is disrupted, this vast source of nitrate could contaminate surface and groundwaters, posing an environmental risk.

Study results appear in the March issue of Geology.

Desert pavement is a naturally occurring, single layer of closely fitted rock fragments. A common land surface feature in arid regions, it has been estimated to cover nearly half of North America’s desert landscapes.

Nitrate, a water soluble nitrogen compound, is a nutrient essential to life. It is also, however, a contaminant. When present in excess in aquatic systems, it results in algal blooms. High levels of nitrate in drinking water have been associated with serious health issues, including methaemoglobinaemia (blue baby disease, marked by a reduction in the oxygen-carrying capacity of blood), miscarriages and non-Hodgkin’s lymphoma.

Salts, including nitrate, are formed in deserts as water evaporates on dry lake beds. These salts then get blown on to the desert pavement by winds. Other contributors of nitrate to desert pavement soils are atmospheric deposition (the gradual deposition of nutrient-rich particulate matter from the air), and soil bacteria, which convert atmospheric nitrogen into nitrate that is usable by plants and other organisms.

Ordinarily, in moist soils, plants and microbes readily take up nitrate, and water flushing through the soils leaches the soils of excess nitrate.

But desert pavement, formed over thousands of years, impedes the infiltration of water in desert soil, restricting plant development and resulting in desert pavement soils becoming nitrate-rich (and saltier) with time.

“After water, nitrogen is the most limiting factor in deserts, affecting net productivity in desert ecosystems,” said Robert Graham, a professor of soil mineralogy in the Department of Environmental Sciences and the lead author of the research paper. “The nitrate stored in soils under desert pavement is a previously unrecognized vast pool of nitrogen that is particularly susceptible to climate change and human disturbance. Moister climates, increased irrigation, wastewater disposal, or flooding may transport high nitrate levels to groundwater or surface waters, which is detrimental to water quality.”

In their study, Graham and his colleagues sampled three widely separated locations with well-developed desert pavement in the Mojave Desert. The locations were selected to represent a variety of landforms commonly found in the desert. The researchers found that the nitrate they observed in association with desert pavement was consistent across the landforms.

“Deserts account for about one-third of Earth’s land area,” Graham said. “If our findings in the Mojave can be extrapolated to deserts worldwide, the amount of nitrate – and nitrogen – stored in near-surface soils of warm deserts would need to be re-estimated.”

Graham and his team of researchers found that nitrate concentration in soils under desert pavement in the Mojave reached a maximum (up to 12,750 kilograms per hectare) within 0.1 to 0.6 meter depth. In contrast, at each location they studied, the soils without desert pavement had relatively low nitrate concentrations (80 to 1500 kilograms per hectare) throughout the upper meter. “In these nonpavement locations, water was able to infiltrate the soil and transport the nitrate to deeper within the soil,” Graham explained.

The researchers note in the paper that desert land use – road construction, off-road vehicle use, and military training – often disrupts fragile land surfaces, increasing surface erosion by rain and wind. According to them, nitrogen-laden dust transported by wind from disturbed desert pavement soils may impact distant nitrogen-limited ecosystems, such as alpine lakes.

Furthermore, the researchers note that increased soil moisture resulting from climate change increases the potential for “denitrification” – a naturally-occurring process in soil, where bacteria break down nitrates to return nitrogen gas to the atmosphere. “Denitrification also produces nitrous oxide, a major greenhouse gas,” Graham said.

Next in their research, Graham and his colleagues will examine the spatial distribution of desert pavement throughout the Mojave Desert to explore how different levels of nitrate are associated with different kinds of desert pavement. Together with UCR’s David Parker, a professor of soil chemistry, they will look in the desert also for perchlorate, which may be associated with nitrate.

Note for Nitrate
In inorganic chemistry, a nitrate is a salt of nitric acid with an ion composed of one nitrogen and three oxygen atoms (NO3−). In organic chemistry the esters of nitric acid and various alcohols are called nitrates. Nitrate from food, especially vegetables, is converted in the human digestive tract to nitrite which reacts with amines to form carcinogenic nitrosamines.
The nitrate ion is a polyatomic ion with the empirical formula NO3− and a molecular mass of 62.0049. It is the conjugate base of nitric acid, consisting of one central nitrogen atom surrounded by three identical oxygen atoms in a trigonal planar arrangement. The nitrate ion carries a formal charge of negative one, where each oxygen carries a −2/3 charge while the nitrogen carries a +1 charge, and is commonly used as an example of resonance.
Almost all inorganic nitrate salts are soluble in water at standard temperature and pressure.
In organic chemistry a nitrate is a functional group with general chemical formula RONO2 where R stands for any organic residue. They are the esters of nitric acid and alcohols formed by nitroxylation. Examples are methyl nitrate formed by reaction of methanol and nitric acid, the nitrate of tartaric acid, and the inappropriately named nitroglycerin.
In freshwater or estuarine systems close to land, nitrate can reach high levels that can potentially cause the death of fish. While nitrate is much less toxic than ammonia or nitrite, levels over 30 ppm of nitrate can inhibit growth, impair the immune system and cause stress in some aquatic species. However, in light of inherent problems with past protocols on acute nitrate toxicity experiments, the extent of nitrate toxicity has been the subject of recent debate.
In most cases of excess nitrate concentrations, the principle pathway of entering aquatic systems is through surface runoff from agricultural or landscaped areas which have received excess nitrate fertilizer. These levels of nitrate can also lead to algae blooms, and when nutrients become limiting (such as potassium, phosphate or nitrate) then eutrophication can occur. As well as leading to water anoxia, these blooms may cause other changes to ecosystem function, favouring some groups of organisms over others. Consequently, as nitrates form a component of total dissolved solids, they are widely used as an indicator of water quality.
Nitrates are also a by-product of septic systems. Specifically, they are a naturally occurring chemical that is left after the break down or decomposition of animal or human waste. Water quality may also be affected through ground water resources that have a high number of septic systems in a watershed. Septics leach down into ground water resources or aquifers and supply near by bodies of water. Lakes that rely on ground water are often affected by nitrification through this process.

Note for Methemoglobinemia
Methemoglobinemia, also known as met-Hb, is a disorder characterized by the presence of a higher than normal level of methemoglobin in the blood. Methemoglobin is a form of hemoglobin that does not bind oxygen. When its concentration is elevated in red blood cells, anemia and tissue hypoxia can occur.
Normally, methemoglobin (methaemoglobin) levels are <1%, as measured by the co-oximetry test. Elevated levels of methemoglobin in the blood are caused when the mechanisms that defend against oxidative stress within the red blood cell are overwhelmed and the oxygen carrying ferrous ion (Fe2+) of the heme group of the hemoglobin (haemoglobin) molecule is oxidized to the ferric state (Fe3+). This converts hemoglobin to methemoglobin, a non-oxygen binding form of hemoglobin that binds a water molecule instead of oxygen. Spontaneous formation of methemoglobin is normally counteracted by protective enzyme systems: NADH methemoglobin reductase (cytochrome-b5 reductase) (major pathway), NADPH methemoglobin reductase (minor pathway) and to a lesser extent the ascorbic acid and glutathione enzyme systems.
Methemoglobinemia can be treated with supplemental oxygen and methylene blue 1% solution (10mg/ml) 1-2mg/kg administered intravenously slowly over five minutes followed by IV flush with normal saline. Methylene blue restores the iron in hemoglobin to its normal (reduced) oxygen-carrying state. This is achieved through the enzyme inducing effect of methylene blue on levels of diaphorase II (NADPH methemoglobin reductase). Diaphorase II normally contributes only a small percentage of the red blood cells reducing capacity but is pharmacologically activated by exogenous cofactors, such as methylene blue, to 5 times its normal level of activity. Genetically induced chronic low-level methemoglobinemia may be treated with oral methylene blue daily. Also, vitamin C can occasionally reduce cyanosis associated with chronic methemoglobinemia but has no role in treatment of acute acquired methemoglobinemia.
Signs and symptoms of methemoglobinemia (methemoglobin >1%) include shortness of breath, cyanosis, mental status changes, headache, fatigue, exercise intolerance, dizziness and loss of consciousness. Arterial blood with elevated methemoglobin levels has a characteristic chocolate-brown color as compared to normal bright red oxygen containing arterial blood.
Severe methemoglobinemia (methemoglobin >50%) patients have dysrhythmias, seizures, coma and death. Healthy people may not have many symptoms with methemoglobin levels < 15%, however patients with co-morbidities such as anemia, cardiovascular disease, lung disease, sepsis, or presence of other abnormal hemoglobin species (e.g. carboxyhemoglobin, sulfehemoglobin or sickle hemoglobin) may experience moderate to severe symptoms at much lower levels (as low as 5-8%).

Note for Greenhouse Gas
Greenhouse gases are components of the atmosphere that contribute to the greenhouse effect. Without the greenhouse effect the Earth would be uninhabitable; in its absence, the mean temperature of the earth would be about −19 °C (−2 °F, 254 K) rather than the present mean temperature of about 15 °C (59 °F, 288 K). Greenhouse gases include in the order of relative abundance water vapour, carbon dioxide, methane, nitrous oxide, and ozone. Greenhouse gases come from natural sources and human activity.
When sunlight reaches the surface of the Earth, some of it is absorbed and warms the surface. Because the Earth's surface is much cooler than the sun, it radiates energy at much longer wavelengths than the sun does, peaking in the infrared at about 10µm. The atmosphere absorbs these longer wavelengths more effectively than it does the shorter wavelengths from the sun. The absorption of this longwave radiant energy warms the atmosphere; the atmosphere also is warmed by transfer of sensible and latent heat from the surface. Greenhouse gases also emit longwave radiation both upward to space and downward to the surface. The downward part of this longwave radiation emitted by the atmosphere is the "greenhouse effect." The term is a misnomer, as this process is not the mechanism that warms greenhouses.
The major greenhouse gases are water vapor, which causes about 36–70% of the greenhouse effect on Earth (not including clouds); carbon dioxide, which causes 9–26%; methane, which causes 4–9%, and ozone, which causes 3–7%. It is not possible to state that a certain gas causes a certain percentage of the greenhouse effect, because the influences of the various gases are not additive. (The higher ends of the ranges quoted are for the gas alone; the lower ends, for the gas counting overlaps.) Other greenhouse gases include, but are not limited to, nitrous oxide, sulfur hexafluoride, hydrofluorocarbons, perfluorocarbons and chlorofluorocarbons .
The major atmospheric constituents (nitrogen, N2 and oxygen, O2) are not greenhouse gases. This is because homonuclear diatomic molecules such as N2 and O2 neither absorb nor emit infrared radiation, as there is no net change in the dipole moment of these molecules when they vibrate. Molecular vibrations occur at energies that are of the same magnitude as the energy of the photons on infrared light. Heteronuclear diatomics such as CO or HCl absorb IR; however, these molecules are short-lived in the atmosphere owing to their reactivity and solubility. As a consequence they do not contribute significantly to the greenhouse effect.
Late 19th century scientists experimentally discovered that N2 and O2 did not absorb infrared radiation (called, at that time, "dark radiation") and that CO2 and many other gases did absorb such radiation. It was recognized in the early 20th century that the known major greenhouse gases in the atmosphere caused the earth's temperature to be higher than it would have been without the greenhouse gases.

Graham was joined in the study by Daniel Hirmas, a doctoral candidate in the Department of Environmental Sciences at UCR; Christopher Amrhein, a professor of soil chemistry at UCR; and Yvonne Wood of the University of California Cooperative Extension, Inyo-Mono Counties, Bishop, Calif. The research was funded by the University of California Kearney Foundation of Soil Science.