Ammonia in Groundwater, Runoff, and Streams
Written by Mr. Brian Oram, PG
Nitrogen - Ammonia in Water
Ammonium Ion (NH4+)
Nitrogen is an essential nutrient that is required by all plants and animals for the formation of amino acids. In its molecular form, nitrogen cannot be used by most aquatic plants, therefore it must be converted to another form.
One such form is ammonia (NH3). Ammonia may be taken up by plants or oxidized by bacteria into nitrate (NO3-) or nitrite (NO2).
Ammonia (NH3+) is a colorless gas with a strong pungent odor. Ammonia will react with water to form a weak base. The term ammonia refers to two chemical species which are in equilibrium in water (NH3, un-ionized and NH4+, ionized). Tests for ammonia usually measure total ammonia (NH3 plus NH4+). The toxicity to ammonia is primarily attributable to the un-ionized form (NH3), as opposed to the ionized form (NH4+). In general, more NH3 and greater toxicity exist at higher pH.
When dissolved in water, normal ammonia (NH3) reacts to form an ionized species called ammonium (NH4+)
NH3 + H2O NH4+ + OH-
This is a shorthand way of saying that one molecule of ammonia reacts with one molecule of water to form one ammonium ion and a hydroxyl ion. From the doubled headed arrow, we can tell that the reaction can go either way and hydroxyl ions and ammonium ions could combine to form ammonia and water. This is precisely what happens as the pH of water increases; that is the water becomes more alkaline. You may recall that alkalinity is caused by an increase in hydroxyl ions. An increase in hydroxyl ions (or alkalinity) pushes the equilibrium to the left and more unionized ammonia is formed.
At any given time, there will be both ammonia molecules and ammonium ions present. The quantity of each species is dependent on both pH and temperature.
Ammonia exists in two forms in the water:
NH3 ( this is called unionized ammonia )
NH4+ ( this is called ionized ammonia )
Together, these two forms of ammonia are called TAN which means total ammonia nitrogen
NH3 is the principal form of toxic ammonia. It has been reported toxic to freshwater organisms at concentrations ranging from 0.53 to 22.8 mg/L. Toxic levels are both pH and temperature dependent. Toxicity increases as pH increases and as temperature increases. Plants are more tolerant of ammonia than animals, and invertebrates are more tolerant than fish. Hatching and growth rates of fishes may be affected. In the structural development, changes in tissues of gills, liver, and kidneys may also occur. Toxic concentrations of ammonia in humans may cause loss of equilibrium, convulsions, coma, and death.
Ammonia levels in excess of the recommended limits may harm aquatic life. Ammonia toxicity is thought to be one of the main causes of unexplained losses in fish hatcheries. Although the ammonia molecule is a nutrient required for life, excess ammonia may accumulate in the organism and cause alteration of metabolism or increases in body pH. Different species of fish can tolerate different levels of ammonia but in any event, less is better. Rainbow trout fry can tolerate up to about 0.2 mg/l while hybrid striped bass can handle 1.2 mg/l.
Fish may suffer a loss of equilibrium, hyperexcitability, increased respiratory activity and oxygen uptake, and increased heart rate. At extreme ammonia levels, fish may experience convulsions, coma, and death. Experiments have shown that the lethal concentration for a variety of fish species ranges from 0.2 to 2.0 mg/l. Trout appear to be most susceptible of these fish and carp the least susceptible.
At higher levels (>0.1 mg/liter NH3) even relatively short exposures can lead to skin, eye, and gills damage. Slightly elevated ammonia levels falling within the acceptable range may adversely impact aquatic life. Fish may experience a reduction in hatching success; reduction in growth rate and morphological development; and injury to gill tissue (i.e., hyperplasia), liver, and kidneys. Hyperplasia-the gill filaments are swollen and clumped together, reducing the fish's ability to 'breath'.
Elevated levels can also lead to ammonia poisoning by suppressing normal ammonia excrement from the gills. If fish are unable to excrete this metabolic waste product there is a rise in blood-ammonia levels resulting in damage to internal organs. The fish response to toxic levels would be lethargy, loss of appetite, laying on the pond bottom with clamped fins, or gasping at the water surface if the gills have been affected. Because this response is similar to the response to poor water quality, parasite infestations, and other diseases.
Experiments have shown that exposure to un-ionized ammonia concentrations as low as 0.002 mg/l for six weeks causes hyperplasia of gill lining in salmon fingerlings and may lead to bacterial gill disease.
Sources of Ammonia
Agricultural: The primary agricultural sources include accidental releases of ammonia-rich fertilizer during transport (because of vehicle accident, faulty hose connections, and human error); and livestock waste (from barnyards, feedlots, pastures, and rangeland).
Residential and Urban: Household use of ammonia-containing cleaning products, on-lot septic systems, and improper disposal of ammonia products may contribute to nonpoint pollution.
Atmospheric Deposition - Available data suggests nitrogen (directly and via rainfall) constitutes a large portion of total nitrogenous inputs to estuarine and marine systems and a somewhat lesser portion of total N inputs to freshwater systems (12). Ammonia in the atmosphere is derived from combustion processes such as domestic heating, burning of municipal waste, and internal-combustion engines.
Point sources: The following industrial processes produce ammonia emissions and effluent: conversion of coal to coke in coke plants, metallurgic operations, ceramic production, strip mining, chemical synthesis (nitric acid, synthetic monomers, and plastics), waste gas treatment, sewage treatment plants, ammonium nitrate explosive production, production of refrigeration equipment, production of household cleaners, oil refineries, and food processing.
Nice Reference - Farmers Guide to Ammonia (pdf)
Surface Water Quality- Chemical Parameters
Ammonia Screening Tests
EPA Technical Fact Sheet on Ammonia (Science and Technology Site)
1999 Update of Ambient Water
Quality Criteria for Ammonia
Well Water Testing Kit
Wetland Education and Training
Inland Restoration; Wetland Delineation (Basics)
Stream Restoration Training - 6 classes
Drinking Water Treatment
Stormwater Management and Groundwater Basics
Water Well Design
Note: Thank you to Randi in PA for finding a typo !
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