Nitrate is a polyatomic ion with the chemical formula . Salts containing this ion are called nitrates. Nitrates are common components of fertilizers and explosives. Almost all inorganic nitrates are solubility in water. An example of an insoluble nitrate is bismuth oxynitrate.
giving:
Dividing by 0.0118 and rearranging gives the equilibrium relation:
However, in reality, nitrogen, oxygen, and water do not combine directly to form nitrate. Rather, a reductant such as hydrogen reacts with nitrogen to produce "fixed nitrogen" such as ammonia, which is then oxidized, eventually becoming nitrate. Nitrate does not accumulate to high levels in nature because it reacts with reductants in the process called denitrification (see Nitrogen cycle).
Nitrate is used as a powerful terminal electron acceptor by denitrifying bacteria to deliver the energy they need to thrive. Under anaerobic conditions, nitrate is the strongest electron acceptor used by prokaryote (bacteria and archaea) to respirate. The redox couple / is at the top of the Redox gradient for the anaerobic respiration, just below the couple oxygen (/), but above the couples Mn(IV)/Mn(II), Fe(III)/Fe(II), /, /. In natural waters, inevitably contaminated by microorganisms, nitrate is a quite unstable and labile dissolved chemical species because it is metabolism by denitrifying bacteria. Water samples for nitrate/nitrite analyses need to be kept at 4 °C in a refrigerated room and analysed as quick as possible to limit the loss of nitrate.
In the first step of the denitrification process, dissolved nitrate () is Catalysis Redox into nitrite () by the Enzyme catalysis of bacteria. In aqueous solution, dissolved nitrite, N(III), is a more powerful oxidizer that nitrate, N(V), because it has to accept less and its Redox is less kinetically hindered than that of nitrate.
During the biological denitrification process, further nitrite reduction also gives rise to another powerful oxidizing agent: nitric oxide (NO). NO can fix on myoglobin, accentuating its red coloration. NO is an important biological Cell signaling and intervenes in the vasodilation process. Still, it can also produce free radicals in biological tissues, accelerating their degradation and aging process. The reactive oxygen species (ROS) generated by NO contribute to the oxidative stress, a condition involved in vascular dysfunction and Atherosclerosis.
Previously, nitrate determination relied on spectrophotometric and colorimetric measurements after a specific reagent is added to the solution to reveal a characteristic color (often red because it absorbs visible light in the blue). Because of interferences with the brown color of dissolved organic matter (DOM: Humic substance and Humic substance) often present in soil pore water, artefacts can easily affect the absorbance values. In case of weak interference, a blank measurement with only a naturally brown-colored water sample can be sufficient to subtract the undesired background from the measured sample absorbance. If the DOM brown color is too intense, the water samples must be pretreated, and inorganic nitrogen species must be separated before measurement. Meanwhile, for clear water samples, colorimetric instruments retain the advantage of being less expensive and sometimes portable, making them an affordable option for fast routine controls or field measurements.
Colorimetric methods for the specific detection of nitrate () often rely on its conversion to nitrite () followed by nitrite-specific tests. The Redox of nitrate to nitrite can be effected by a copper-cadmium alloy, metallic zinc, or hydrazine. The most popular of these assays is the Griess test, whereby nitrite is converted to a deeply red colored azo dye suited for UV–vis spectrophotometry analysis. The method exploits the reactivity of nitrous acid () derived from the acidification of nitrite. Nitrous acid selectively reacts with aromatic amines to give diazonium salts, which in turn couple with a second reagent to give the azo dye. The detection limit is 0.02 to 2 μM. Such methods have been highly adapted to biological samples and soil samples.
In the dimethylphenol method, 1 mL of concentrated sulfuric acid () is added to 200 μL of the solution being tested for nitrate. Under strongly acidic conditions, nitrate ions react with 2,6-dimethylphenol, forming a yellow compound, Nitrophenol. This occurs through electrophilic aromatic substitution where the intermediate nitronium () ions attack the aromatic ring of dimethylphenol. The resulting product (Nitrophenol) is analyzed using UV-vis spectrophotometry at 345 nm according to the Lambert-Beer law..
Another colorimetric method based on the chromotropic acid (dihydroxynaphthalene-disulfonic acid) was also developed by West and Lyles in 1960 for the direct spectrophotometric determination of nitrate Ion.
If formic acid is added to a mixture of brucine (an alkaloid related to strychnine) and potassium nitrate (), its color instantly turns red. This reaction has been used for the direct colorimetric detection of nitrates.
For direct online chemical analysis using a flow-through system, the water sample is introduced by a peristaltic pump in a flow injection analyzer, and the nitrate or resulting nitrite-containing effluent is then combined with a reagent for its colorimetric detection.
Nitrates are produced by a number of species of nitrifying bacteria in the natural environment using ammonia or urea as a source of nitrogen and source of free energy. Nitrate compounds for gunpowder were historically produced, in the absence of mineral nitrate sources, by means of various fermentation processes using urine and dung.
Lightning strikes in earth's nitrogen- and oxygen-rich atmosphere produce a mixture of oxides of nitrogen, which form Nitrous acid ions and nitrate ions, which are washed from the atmosphere by rain or in occult deposition.
Nitrates are produced industrially from nitric acid.
Nitrates are used as in agriculture because of their high solubility and biodegradability. The main nitrate fertilizers are Ammonium nitrate, Sodium nitrate, potassium, Calcium nitrate, and magnesium salts. Several billion kilograms are produced annually for this purpose. The significance of nitrate extends beyond its role as a nutrient since it acts as a signaling molecule in plants, regulating processes such as root growth, flowering, and leaf development.
While nitrate is beneficial for agriculture since it enhances soil fertility and crop yields, its excessive use can lead to nutrient runoff, water pollution, and the proliferation of aquatic dead zones.
In fact, nitrates (), often present at too high concentration in drinkwater, are only the precursor chemical species of (), the real culprits of methemoglobinemia. Nitrites produced by the Denitrification (directly in the drinkwater, or after ingestion by the infant’s digestive system) are more powerful Oxidizing agent than nitrates and are the chemical agent really responsible for the Redox of Fe2+ into Fe3+ in the tetrapyrrole heme of hemoglobin. Indeed, nitrate anions are too weak oxidizers in aqueous solution to be able to directly, or at least sufficiently rapidly, oxidize Fe2+ into Fe3+, because of kinetics limitations.
Infants younger than 4 months are at greater risk given that they drink more water per body weight, they have a lower NADH-cytochrome b5 reductase activity, and they have a higher level of fetal hemoglobin which converts more easily to methemoglobin. Additionally, infants are at an increased risk after an episode of gastroenteritis due to the production of by bacteria.
However, other causes than nitrates can also affect infants and pregnant women. Indeed, the blue baby syndrome can also be caused by a number of other factors such as the cyanotic heart disease, a congenital heart defect resulting in low levels of oxygen in the blood, or by gastric upset, such as diarrheal infection, protein intolerance, heavy metal toxicity, etc.
An acceptable daily intake (ADI) for nitrate ions was established in the range of 0–3.7 mg (kg body weight)−1 day−1 by the Joint FAO/WHO Expert Committee on Food Additives (JEFCA).
In most cases of excess nitrate concentrations in aquatic systems, the primary sources are wastewater discharges, as well as surface runoff from agricultural or areas that have received excess nitrate fertilizer. The resulting eutrophication and algae blooms result in anoxia and dead zones. As a consequence, as nitrate forms a component of total dissolved solids, they are widely used as an indicator of water quality.
The impact of increased nitrate deposition extends beyond plant communities to affect soil microbial populations. The change in soil chemistry and nutrient dynamics can disrupt the natural processes of nitrogen fixation, nitrification, and denitrification, leading to altered microbial community structures and functions. This disruption can further impact the Nutrient cycle and overall ecosystem health.
Nitrate ingestion rapidly increases the Blood plasma nitrate concentration by a factor of 2 to 3, and this elevated nitrate concentration can be maintained for more than 2 weeks. Increased plasma nitrate enhances the production of nitric oxide, NO. Nitric oxide is a physiological signaling molecule which intervenes in, among other things, regulation of muscle blood flow and mitochondrial respiration.
Many meat processors claim their meats (e.g. bacon) is "uncured" – which is a marketing claim with no factual basis: there is no such thing as "uncured" bacon (as that would be, essentially, raw sliced pork belly). "Uncured" meat is in fact actually cured with nitrites with virtually no distinction in process – the only difference being the USDA labeling requirement between nitrite of vegetable origin (such as from celery) vs. "synthetic" sodium nitrite. An analogy would be purified "sea salt" vs. sodium chloride – both being exactly the same chemical with the only essential difference being the origin.
Anti-hypertensive diets, such as the DASH diet, typically contain high levels of nitrates, which are first reduced to nitrite in the saliva, as detected in saliva testing, prior to forming nitric oxide (NO).
The values above are on a dry (moisture-free) basis.
Uses
Agriculture
Firearms
Industrial
Photographic film
Medicinal and pharmaceutical use
Toxicity and safety
Methemoglobinemia
Drinking water standards
Aquatic toxicity
Human impacts on ecosystems through nitrate deposition
Dietary nitrate
Cured meats
Domestic animal feed
Generally safe for beef cattle and sheep Caution: some subclinical symptoms may appear in pregnant horses, sheep and beef cattle High nitrate problems: death losses and abortions can occur in beef cattle and sheep Maximum safe level for horses. Do not feed high nitrate forages to pregnant mares
Salts and covalent derivatives
See also
External links
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