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Nitrate & Nitrite Levels in Water & Food: Human Exposure & Health Risks, Study Guides, Projects, Research of Nutrition

The concentrations of nitrate and nitrite in water and food, their sources, and the potential health risks associated with human exposure. It also mentions the factors affecting nitrate transport from land to water, the impact of atmospheric deposition, and the policies implemented to reduce nitrogen emissions. data on nitrate and nitrite levels in various water systems and foodstuffs, as well as human intake and population exposure.

What you will learn

  • What are the potential health risks associated with human exposure to nitrate and nitrite?
  • What are the sources of nitrate and nitrite in water and food?
  • Which populations are at higher risk of exposure to nitrate and nitrite?
  • What policies have been implemented to reduce nitrogen emissions and mitigate nitrate contamination?
  • How does atmospheric deposition affect nitrate concentrations in water systems?

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177 NITRATE AND NITRITE
6. POTENTIAL FOR HUMAN EXPOSURE
6.1 OVERVIEW
Nitrate and nitrite are ubiquitous in the environment. Specific salts have occasionally been identified in
hazardous waste sites. Ammonium nitrate, sodium nitrate, and sodium nitrite were identified in 7, 3, and
2, of the 1,832 hazardous waste sites, respectively that have been proposed for inclusion on the EPA
National Priorities List (NPL) (ATSDR 2015). However, the number of sites evaluated for these
substances is not known. The frequency of these sites can be seen in Figures 6-1, 6-2, and 6-3.
Nitrate may enter the environment via natural and anthropogenic sources. Nitrate and nitrite occur
naturally in the environments as a part of the earth’s nitrogen cycle. A major source of anthropogenic
nitrate and nitrite is artificial fertilizers, and various industrial processes also produce nitrate in their waste
streams (Environment Canada 2012; WHO 1978). Inorganic fertilizer and nitrification of animal waste
are the principal sources of nitrate in the environment (Environment Canada 2012; Nolan et al. 1997).
However, contributions from human waste must be taken into account as well. Point and non-point
anthropogenic sources that contribute include industrial waste water, mining (explosives) waste water,
agricultural and urban runoff, feedlot discharges, septic system and landfill leachate, lawn fertilizers,
storm sewer overflow, and nitric oxide and nitrogen dioxide from vehicle exhaust (Environment Canada
2012). Additionally, organic forms of nitrogen in the environment from various sources may undergo
ammonification to form inorganic ammonia and ammonium, and nitrification to form nitrate, and have the
potential to be released into surface waters (Environment Canada 2012). Inorganic nitrate and nitrite in
soil and water can be taken up by plants used for human consumption (ATSDR 2013a).
Exposure from drinking water of private wells is a source of concern as elevated concentrations have been
reported in some wells, yet these water sources are not routinely tested, monitored, or regulated since they
are not covered by the Safe Drinking Water Act (SDWA). About 15% of Americans use private wells as
a source of drinking water and an important percentage of them may have a septic system serving their
homes. Additionally, nitrate and nitrite exposure can occur from the ingestion of foods containing high
levels of these chemicals (ATSDR 2013a).
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6. POTENTIAL FOR HUMAN EXPOSURE

6.1 OVERVIEW

Nitrate and nitrite are ubiquitous in the environment. Specific salts have occasionally been identified in

hazardous waste sites. Ammonium nitrate, sodium nitrate, and sodium nitrite were identified in 7, 3, and

2, of the 1,832 hazardous waste sites, respectively that have been proposed for inclusion on the EPA

National Priorities List (NPL) (ATSDR 2015). However, the number of sites evaluated for these

substances is not known. The frequency of these sites can be seen in Figures 6-1, 6-2, and 6-3.

Nitrate may enter the environment via natural and anthropogenic sources. Nitrate and nitrite occur

naturally in the environments as a part of the earth’s nitrogen cycle. A major source of anthropogenic

nitrate and nitrite is artificial fertilizers, and various industrial processes also produce nitrate in their waste

streams (Environment Canada 2012; WHO 1978). Inorganic fertilizer and nitrification of animal waste

are the principal sources of nitrate in the environment (Environment Canada 2012; Nolan et al. 1997).

However, contributions from human waste must be taken into account as well. Point and non-point

anthropogenic sources that contribute include industrial waste water, mining (explosives) waste water,

agricultural and urban runoff, feedlot discharges, septic system and landfill leachate, lawn fertilizers,

storm sewer overflow, and nitric oxide and nitrogen dioxide from vehicle exhaust (Environment Canada

2012). Additionally, organic forms of nitrogen in the environment from various sources may undergo

ammonification to form inorganic ammonia and ammonium, and nitrification to form nitrate, and have the

potential to be released into surface waters (Environment Canada 2012). Inorganic nitrate and nitrite in

soil and water can be taken up by plants used for human consumption (ATSDR 2013a).

Exposure from drinking water of private wells is a source of concern as elevated concentrations have been

reported in some wells, yet these water sources are not routinely tested, monitored, or regulated since they

are not covered by the Safe Drinking Water Act (SDWA). About 15% of Americans use private wells as

a source of drinking water and an important percentage of them may have a septic system serving their

homes. Additionally, nitrate and nitrite exposure can occur from the ingestion of foods containing high

levels of these chemicals (ATSDR 2013a).

  1. POTENTIAL FOR HUMAN EXPOSURE

Figure 6-1. Frequency of NPL Sites with Ammonium Nitrate Contamination

  1. POTENTIAL FOR HUMAN EXPOSURE

Figure 6-3. Frequency of NPL Sites with Sodium Nitrite Contamination

  1. POTENTIAL FOR HUMAN EXPOSURE

6.2 RELEASES TO THE ENVIRONMENT

The Toxics Release Inventory (TRI) data should be used with caution because only certain types of

facilities are required to report (EPA 2005). This is not an exhaustive list. Manufacturing and processing

facilities are required to report information to the TRI only if they employ 10 or more full-time

employees; if their facility is included in Standard Industrial Classification (SIC) Codes 10 (except 1011,

1081, and 1094), 12 (except 1241), 20–39, 4911 (limited to facilities that combust coal and/or oil for the

purpose of generating electricity for distribution in commerce), 4931 (limited to facilities that combust

coal and/or oil for the purpose of generating electricity for distribution in commerce), 4939 (limited to

facilities that combust coal and/or oil for the purpose of generating electricity for distribution in

commerce), 4953 (limited to facilities regulated under RCRA Subtitle C, 42 U.S.C. section 6921 et seq.),

5169, 5171, and 7389 (limited S.C. section 6921 et seq.), 5169, 5171, and 7389 (limited to facilities

primarily engaged in solvents recovery services on a contract or fee basis); and if their facility produces,

imports, or processes ≥25,000 pounds of any TRI chemical or otherwise uses >10,000 pounds of a TRI

chemical in a calendar year (EPA 2005).

Nitrate is released into the environment through both natural and anthropogenic sources. Naturally

occurring nitrate and nitrite are part of the earth’s nitrogen cycle. Anthropogenic sources, including

animal and human organic wastes as well as nitrogen-containing fertilizers, increase the concentrations of

nitrate in the environment. Nitrate and nitrite are present in the environment, in soils and water, and to a

lesser extent, in air, plant materials, and meat products. Concentrations of nitrite in plants and water are

low relative to nitrate concentration due to the fact that nitrite is easily oxidized to nitrate (WHO 1978).

Nitrate is the ion detected in the majority of groundwater and surface water samples because the nitrite

ion is easily oxidized to nitrate in the environment; the nitrate ion is stable and is chemically unreactive

under most environmental conditions (IARC 2010; WHO 2011b).

6.2.1 Air

Estimated releases of 301,654 pounds (~137 metric tons) of nitrate compounds to the atmosphere from

2,110 domestic manufacturing and processing facilities in 2013, accounted for about 0.1% of the

estimated total environmental releases from facilities required to report to the TRI (TRI13 2014). These

releases are summarized in Table 6-1. Estimated releases of 65,201 (~30 metric tons) pounds of sodium

nitrite were released to the atmosphere from 363 domestic manufacturing and

  1. POTENTIAL FOR HUMAN EXPOSURE

Table 6-1. Releases to the Environment from Facilities that Produce, Process, or

Use Nitrate Compoundsa

Reported amounts released in pounds per yearb

Total release

On- and off-

Statec^ RF d^ Air e^ Water f^ UIg^ Land h^ Other i^ On-sitej^ Off-sitek^ site

PA 67 9,139 7,212,765 0 66,541 2,428 7,224,885 65,988 7,290,
PR 7 0 0 1,465 120 34 1,465 154 1,
RI 6 0 121 0 0 20,098 121 20,098 20,
SC 43 3,001 2,346,088 0 178,745 458 2,376,696 151,596 2,528,
SD 8 0 2,995,074 2,000 338,782 6 3,280,324 55,538 3,335,
TN 45 270 2,748,175 470,956 125,258 1,678 2,772,445 573,892 3,346,
TX 131 788 14,234,564 7,762,004 876,395 7,165 21,822,716 1,058,200 22,880,
UT 37 329 97,000 0 1,282,016 29 714,559 664,815 1,379,
VA 42 3,558 10,978,189 0 4,587 1 10,981,823 4,511 10,986,
VT 6 0 124,890 0 57,395 0 124,890 57,395 182,
WA 46 8,770 1,190,505 0 981,730 0 1,631,774 549,231 2,181,
WI 127 591 2,162,376 0 2,339,390 31,174 3,734,315 799,216 4,533,
WV 18 18,000 2,140,714 0 2,138 0 2,160,673 179 2,160,

WY 5 0 633 6,569,900 249 0 6,570,782 No data 6,570, Total 2,110 301,654 188,570,641 40,832,332 22,848,913 985,811 242,566,590 10,972,761 253,539, aThe TRI data should be used with caution since only certain types of facilities are required to report. This is not an exhaustive list. Data are rounded to nearest whole number. bData in TRI are maximum amounts released by each facility. cPost office state abbreviations are used. dNumber of reporting facilities. eThe sum of fugitive and point source releases are included in releases to air by a given facility. fSurface water discharges, waste water treatment-(metals only), and publicly owned treatment works (POTWs) (metal and metal compounds). gClass I wells, Class II-V wells, and underground injection. hResource Conservation and Recovery Act (RCRA) subtitle C landfills; other onsite landfills, land treatment, surface impoundments, other land disposal, other landfills. iStorage only, solidification/stabilization (metals only), other off-site management, transfers to waste broker for disposal, unknown jThe sum of all releases of the chemical to air, land, water, and underground injection wells. kTotal amount of chemical transferred off-site, including to POTWs. RF = reporting facilities; UI = underground injection Source: TRI13 2014 (Data are from 2013)

  1. POTENTIAL FOR HUMAN EXPOSURE

processing facilities in 2013, accounted for about 0.8% of the estimated total environmental releases from

facilities required to report to the TRI (TRI13 2014). These releases are summarized in Table 6-2.

Estimated releases of 125,680,001 pounds (~57,007 metric tons) of ammonia were released to the

atmosphere from 2,292 domestic manufacturing and processing facilities in 2013, accounted for about

77% of the estimated total environmental releases from facilities required to report to the TRI (TRI

2014). These releases are summarized in Table 6-3.

6.2.2 Water

Estimated releases of 188,570,641 pounds (~85,534 metric tons) of nitrate compounds to surface water

from 2,110 domestic manufacturing and processing facilities in 2013, accounted for about 74% of the

estimated total environmental releases from facilities required to report to the TRI (TRI13 2014). These

releases are summarized in Table 6-1. Estimated releases of 2,472,668 pounds (~1,122 metric tons) of

sodium nitrite compounds to surface water from 363 domestic manufacturing and processing facilities in

2013, accounted for about 30% of the estimated total environmental releases from facilities required to

report to the TRI (TRI13 2014). These releases are summarized in Table 6-2. Estimated releases of

4,221,440 pounds (~1,914 metric tons) of ammonia to surface water from 2,292 domestic manufacturing

and processing facilities in 2013, accounted for about 2.6% of the estimated total environmental releases

from facilities required to report to the TRI (TRI13 2014). These releases are summarized in Table 6-3.

EPA (2009d) reported that the Mississippi River drains >40% of the area of the contiguous 48 states and

carries roughly 15 times more nitrate than any other river in the country. EPA (2009d) noted that the

nitrate load in the Mississippi rose from 200,000 to 500,000 tons per year in the 1950s and 1960s to an

average of approximately 1,000,000 tons per year during the 1980s and 1990s; the data indicate that the

nitrate load decreased slightly in the early 2000s.

Nitrate is commonly detected in various surface waters and groundwaters such as shallow, rural domestic

wells. Contamination of water systems is a consequence of inorganic fertilizer use, animal manures,

septic systems, and waste water treatment (ATSDR 2013a; Nolan 1999; WHO 2011b). Ammonium ions

in sludge from waste water treatment plants, as well as effluents from those plants and septic systems, are

rapidly converted to nitrate (WHO 1978). Various industrial process produce nitrate in their waste

streams. For example, potassium nitrate, calcium nitrate,

  1. POTENTIAL FOR HUMAN EXPOSURE

Table 6-2. Releases to the Environment from Facilities that Produce, Process, or

Use Sodium Nitritea

Reported amounts released in pounds per yearb

Total release

On- and

Statec^ RF d^ Air e^ Water f^ UIg^ Land h^ Other i^ On-sitej^ Off-sitek^ off-site

WI 13 10,231 28 0 69,018 0 10,259 69,018 79,
WV 4 165 44,552 0 3 0 44,717 3 44,

Total 363 65,201 2,472,668 1,698,994 4,027,823 50,760 4,469,774 3,845,673 8,315, aThe TRI data should be used with caution since only certain types of facilities are required to report. This is not an exhaustive list. Data are rounded to nearest whole number. bData in TRI are maximum amounts released by each facility. cPost office state abbreviations are used. dNumber of reporting facilities. eThe sum of fugitive and point source releases are included in releases to air by a given facility. fSurface water discharges, waste water treatment-(metals only), and publicly owned treatment works (POTWs) (metal and metal compounds). gClass I wells, Class II-V wells, and underground injection. hResource Conservation and Recovery Act (RCRA) subtitle C landfills; other onsite landfills, land treatment, surface impoundments, other land disposal, other landfills. iStorage only, solidification/stabilization (metals only), other off-site management, transfers to waste broker for disposal, unknown jThe sum of all releases of the chemical to air, land, water, and underground injection wells. kTotal amount of chemical transferred off-site, including to POTWs. RF = reporting facilities; UI = underground injection Source: TRI13 2014 (Data are from 2013)

6. POTENTIAL FOR HUMAN EXPOSURE

Table 6-3. Releases to the Environment from Facilities that Produce, Process, or Use Ammoniaa

Reported amounts released in pounds per yearb

Total release On- and off-

  • AK 2 0 310,000 0 1,730,003 0 2,040,003 No data 2,040, Statec RF d Air e Water f UIg Land h Other i On-sitej Off-sitek site
  • AL 56 5 10,970,520 5,000 589,240 1,003 11,012,324 553,444 11,565,
  • AR 26 0 3,776,021 0 14,399 4,217 3,790,167 4,470 3,794,
  • AZ 32 3,295 0 0 39,894 78 43,189 78 43,
  • CA 139 7,172 1,967,150 20,684 956,477 65,682 2,831,868 185,297 3,017,
  • CO 39 1 1,850,266 0 54,944 50 1,904,854 407 1,905,
  • CT 26 58,098 202,953 0 698 54,000 261,051 54,698 315,
  • DC 4 0 0 0 0 0 0 No data
  • DE 6 0 2,850,359 0 0 0 2,850,359 No data 2,850,
  • FL 36 479 850,888 23,373,722 264,705 0 24,261,115 228,680 24,489,
  • GA 57 511 12,284,962 0 352,756 196,086 12,573,225 261,090 12,834,
  • GU 1 0 181,244 0 196 0 181,440 No data 181,
  • HI 7 0 439,915 0 0 0 439,915 No data 439,
  • IA 46 23,005 6,737,465 0 133,387 28 6,886,605 7,280 6,893,
  • ID 25 53 2,462,856 0 1,590,643 0 4,021,989 31,564 4,053,
  • IL 108 28,202 6,428,670 14,007 454,232 2,346 6,875,892 51,565 6,927,
  • IN 62 439 19,965,218 0 3,287,114 12,527 19,965,662 3,299,636 23,265,
  • KS 27 38,262 108,068 340,905 98,569 21 585,186 639 585,
  • KY 44 990 5,031,265 0 313,935 532 5,305,617 41,104 5,346,
  • LA 48 4,502 10,169,890 1,576,528 55,015 0 11,753,676 52,259 11,805,
  • MA 42 10 115 25,928 27,091 217,377 145 270,376 270,
  • MD 21 0 739,290 0 84,199 35 739,687 83,837 823,
  • ME 12 1,209 2,854,965 0 63 0 2,856,209 28 2,856,
  • MI 103 10,021 1,714,827 0 228,050 33,121 1,732,091 253,928 1,986,
  • MN 53 1,076 1,471,856 0 78,276 250 1,536,094 15,364 1,551,
  • MO 37 2,852 1,752,877 0 241,834 5,100 1,977,139 25,524 2,002,
  • MS 28 372 6,495,644 0 329 0 6,496,345 No data 6,496,
  • MT 10 0 234,169 0 43,891 0 272,860 5,200 278,
  • NC 41 1 6,563,023 0 236,361 236,692 6,793,505 242,572 7,036,
  • ND 10 0 113,400 0 15,640 0 129,040 No data 129,
  • NE 25 187 11,785,649 0 243,650 40 12,022,108 7,418 12,029,
  • NH
  • NJ 40 0 5,313,118 0 41,966 376 5,354,858 602 5,355,
  • NM 14 55,000 42,240 0 662,620 0 406,331 353,529 759,
  • NV 27 6 2,800 0 3,947,279 2 3,729,262 220,825 3,950,
  • NY 73 5,337 5,797,905 0 437,314 28,473 5,804,333 464,696 6,269,
  • OH 111 1,987 6,081,057 134,614 182,994 64,665 6,219,720 245,598 6,465,
  • OK 37 13,010 4,246,811 534,620 180,969 0 4,970,061 5,349 4,975,
  • OR 40 1,000 542,093 0 6,833 0 545,071 4,855 549,
  • AL Statec RF d Air e Water f UIg Land h Other i On-sitej Off-sitek off-site
  • AR 7 0 254 0 0 0 254 No data
  • AZ 3 0 0 0 9,117 0 9,117 No data 9,
  • CA
  • CO 2 255 0 0 0 0 255 No data
  • FL 1 0 0 0 0 0 0 No data
  • GA 11 98 648,256 0 101,148 68 749,502 68 749,
  • IA 3 0 2,517 0 0 0 2,517 No data 2,
  • ID 1 0 0 0 0 0 0 No data
  • IL 32 1,637 18,600 0 90,065 15 20,237 90,080 110,
  • IN 20 1 1,130,853 0 3,312,017 4,896 1,130,854 3,316,913 4,447,
  • KS 2 0 0 0 0 0 0 No data
  • KY 10 1,016 0 0 41,435 36,320 27,291 51,480 78,
  • LA 9 0 48,000 1,500,000 107 0 1,548,000 107 1,548,
  • MA 5 0 0 0 0 0 0 No data
  • MD
  • MI 42 12,992 4 0 181,207 2,490 18,745 177,948 196,
  • MN 6 0 194,173 0 0 0 194,173 No data 194,
  • MO 13 2,871 0 0 412 3,685 2,871 4,097 6,
  • MS 6 8,489 7,895 0 26,296 3 16,384 26,299 42,
  • NC 4 0 4,455 0 0 0 4,455 No data 4,
  • NE 4 0 21,200 0 1,182 1,637 21,467 2,552 24,
  • NJ 9 200 68,032 0 2,898 0 68,290 2,840 71,
  • NM 1 0 0 0 0 0 0 No data
  • NV 1 2 0 0 33,641 0 33,642 No data 33,
  • NY 8 11,807 4,925 0 2,800 220 16,732 3,020 19,
  • OH 35 13,067 731 0 77,303 1,134 13,798 78,437 92,
  • OK 3 289 9,010 0 17,405 0 9,299 17,405 26,
  • OR
  • PA
  • RI 1 0 0 0 0 0 0 No data
  • SC 19 1,530 69,403 0 787 190 70,933 977 71,
  • SD 3 6 121 25 5,500 0 5,652 0 5,
  • TN
  • TX 38 34 199,659 198,969 54,487 0 449,818 3,331 453,
  • VA UT 1 No data No data No data No data No data No data No data No data
  • AK 6 23,099 7,012 136 24,075 0 54,323 No data 54, Statec RF d Air e Water f UIg Land h Other i On-sitej Off-sitek site
  • AL 70 4,060,001 209,278 9,343 43,646 294 4,287,915 34,647 4,322,
  • AR 47 1,837,750 114,277 0 5,499 511 1,956,076 1,961 1,958,
  • AS 1 20 0 0 0 0 20 No data
  • AZ 20 336,273 0 0 722 0 336,989 6 336,
  • CA 118 2,801,456 26,830 2,870 165,409 369 2,978,123 18,811 2,996,
  • CO 19 269,063 17,833 0 101,218 2,430 385,942 4,602 390,
  • CT 15 74,775 155 0 0 0 74,930 No data 74,
  • DC 2 165 0 0 0 0 165 No data
  • DE 7 58,659 6,071 0 23 0 64,730 23 64,
  • FL 63 5,607,959 244,014 464,183 960,078 0 6,343,579 932,655 7,276,
  • GA 81 12,615,696 268,976 0 166,494 153 12,967,436 83,883 13,051,
  • HI 9 100,496 1,000 1,200 0 0 102,696 No data 102,
  • IA 79 7,333,058 108,999 0 210,562 6,621 7,545,358 113,882 7,659,
  • ID 19 2,844,444 27,824 0 167,548 0 3,023,068 16,749 3,039,
  • IL 112 3,081,028 110,035 0 69,293 4,620 3,246,667 18,309 3,264,
  • IN 64 1,600,854 45,833 707,485 77,195 0 2,423,117 8,250 2,431,
  • KS 37 3,056,601 6,490 38,214 49,185 15,483 3,130,592 35,381 3,165,
  • KY 47 971,022 55,064 0 48,663 1,845 1,036,520 40,073 1,076,
  • LA 72 13,461,749 585,745 4,582,747 326,520 0 18,630,317 326,444 18,956,
  • MA 30 178,727 41 0 1,622 0 178,768 1,622 180,
  • MD 16 523,890 48,675 0 2 0 572,565 2 572,
  • ME 10 753,203 89,718 0 0 0 842,921 No data 842,
  • MI 70 1,681,959 36,582 9,790 7,181 7,875 1,731,377 12,010 1,743,
  • MN 61 1,870,843 49,112 0 35,092 2,270 1,938,690 18,627 1,957,
  • MO 46 422,032 228,193 0 44,490 251 654,800 40,166 694,
  • MS 34 4,700,259 188,194 0 2,181 0 4,889,803 830 4,890,
  • MT 10 449,711 5,420 0 264,118 0 719,205 44 719,
  • NC 86 2,661,108 85,427 0 73,410 110 2,781,752 38,302 2,820,
  • ND 13 16,199,585 4,476 11,500 474,130 0 16,689,625 66 16,689,
  • NE 44 974,508 26,655 0 162,935 4,643 1,021,771 146,970 1,168,
  • NH 9 127,211 447 0 0 2 127,658 2 127,
  • NJ 43 527,774 9,790 0 24,984 74 537,605 25,017 562,
  • NM 6 98,819 0 2,300 11,561 0 112,680 No data 112,
  • NV 12 132,670 560 0 228,759 1 361,989 1 361,
  • NY 50 687,039 50,197 0 974 274 737,570 915 738,
  • OH 115 6,430,630 100,258 1,715,361 76,575 2,560 8,244,156 81,229 8,325,
  • OK 24 5,433,575 18,832 696,880 137,282 0 6,282,692 3,877 6,286,
  • OR 31 1,156,034 35,599 0 9,980 0 1,192,997 8,616 1,201,
  1. POTENTIAL FOR HUMAN EXPOSURE

silver nitrate, and sodium nitrate used in several industrial applications have waste waters with high-

nitrate concentrations (Environment Canada 2012). Discharges of these waste streams increase the

concentrations of nitrate and nitrite in surface waters. Treatment of these waste streams may only remove

a portion of nitrogen. Factors such as nitrogen loading, population density, soil drainage characteristics,

and woodland to cropland ratios, affect the transport of nitrogen from land to water (Nolan et al. 1997;

Zhang et al. 1998). Increased levels of nitrite in drinking water may also be a consequence of

contamination by boiler fluid additives (ATSDR 2013a). High risk waters for nitrate contamination

include areas having soils with high permeability, high-nitrogen input, and low woodland to cropland

ratios (Nolan et al. 1997; Zhang et al. 1998).

Natural sources of nitrate and nitrite include wet and dry deposition of atmospheric nitric acid and nitrate

ion. These are formed in the atmosphere as a result of nitrogen cycling. Atmospheric deposition is a

factor for nitrate concentrations in water systems (Momen et al. 1999). Atmospheric nitrogen (NO 3 - ,

NO 2 - , and NH 4 +), mainly from natural sources but a result of anthropogenic sources as well, have been

estimated to contribute 182 kilotons of inorganic nitrogen per year to Canadian surface waters via wet and

dry deposition (Environment Canada 2012). In the United States, deposition contributes an estimated

3.2 million tons (3,200 kilotons) of nitrogen per year to watersheds (Momen et al. 1999; Nolan 1999;

Nolan et al. 1997). Owens et al. (1994) reported that nitrogen input to a grass pasture from precipitation

was equivalent to 10% of the nitrogen fertilizer applied during a 5-year period. The concentration of

nitrate-nitrogen in the precipitation during 1975–1980 was reported as 1.1 mg/L (ppm), which correlated

to an input of 12.0 kg nitrate-nitrogen/hectare. A 10-year average was also evaluated for the years 1980–

1990, which resulted in an input of 8.9 kg nitrate-nitrogen/hectare (Owens et al. 1994).

Stagnation of nitrate-containing and oxygen-poor drinking water in galvanized steel pipes and

chlorination disinfectant residues can lead to conditions where nitrite is formed via chemical reactions in

the distribution pipes by Nitrosomonas bacteria (WHO 2011b).

A U.S. Geological Survey (USGS) study across the United States showed that 7% of 2,388 domestic

wells and about 3% of 384 public-supply wells were contaminated with nitrate levels above the EPA

drinking water standard of 10 mg/L (10 ppm) (ATSDR 2013a). Between 1994 and 1996, 24 lakes in the

Adirondack Park, United States, were studied to assess the contribution of in-lake processes, atmospheric

deposition, and watershed cover on the lakes’ nitrate concentrations (Momen et al. 1999). Weighted

means for nitrate concentrations as a result of precipitation near the lakes were reported for all seasons

during the study period and ranged from 13.86 to 35.52 μeq/L. Nitrogen concentrations throughout the

  1. POTENTIAL FOR HUMAN EXPOSURE

study period ranged from 2.1 to 22 μmol/L. Both atmospheric deposition and average lake depth were

considered strong factors in concentrations of nitrate in lakes. It was concluded that the average lake

depth was the most important factor; greater average depths correlated to higher nitrate concentrations.

This was attributed to decreased contact time with lake sediment, decreasing the potential for removal

processes (Momen et al. 1999).

Concentrations of nitrate in freshwater downstream from an open-pit coal mining operation have been

reported to exceed 44 mg nitrate/L (Nordin and Pommen 1986). This is attributed to high nitrate levels in

waste streams due to explosive residues. Monitoring studies conducted by the USGS indicate that nitrate

and nitrite levels are several times greater in streams and groundwater in areas classified as agricultural

use rather than as urban use, mixed use, or undeveloped land (USGS 2010a, 2010b).

Policies implemented by the European Union (EU) to reduce nitrogen emissions from agricultural point

sources were reviewed by Velthof et al. (2014). The Nitrates Directive (ND) was implemented to protect

water quality across Europe by inhibiting nitrates released by agricultural sources from leaching into

groundwater and surface waters through the use of good farming practices. Although regional differences

in emissions were large throughout the entire EU, nitrate leaching into groundwater and surface waters

was estimated to decrease by 16% in nitrate leaching vulnerable zones over the period of 2000–2008,

primarily as a result of lower nitrogen emissions from fertilizers and manures (Velthof et al. 2014).

Seawater nitrate concentrations that occur naturally due to nitrification processes can be as high as 2.4 mg

nitrate/L (Environment Canada 2012). Assimilation into biological systems can deplete nitrate

concentrations in marine environments, causing seasonal variations in nitrate concentrations. Winter

concentrations off the Canadian Atlantic coast were reported to be 0.54 mg nitrate/L, a magnitude higher

than summer concentrations of <0.03 mg nitrate/L (Environment Canada 2012).

6.2.3 Soil

Estimated releases of 22,848,913 pounds (~10,364 metric tons) of nitrate compounds to soils from

2,110 domestic manufacturing and processing facilities in 2013, accounted for about 9% of the estimated

total environmental releases from facilities required to report to the TRI (TRI13 2014). An additional

40,832,332 pounds (~18,521 metric tons), constituting about 16% of the total environmental emissions,

were released via underground injection (TRI13 2014). These releases are summarized in Table 6-1. An

estimated release of 4,027,823 pounds (~1,826 metric tons) of sodium nitrite were emitted to soils from

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decomposes to yield water and dinitrogen trioxide or nitric acid, nitric oxide, and water (WHO 1978;

WHO 2011b).

6.3.1 Transport and Partitioning

Nitrate and nitrite are inorganic water-soluble salts with the potential for rapid migration through soils to

surface water and groundwater (Nolan 1999; Taylor 2004; EPA 2009a). Sorption of anions such as

nitrate is insignificant in most soils; therefore, leaching of excess soil nitrate into oceans, lakes, streams,

and groundwater is an important consideration (Taylor 2004). Drainage characteristics of soils are

strongly related to nitrate levels in shallow wells near agricultural areas (Nolan et al. 1997; Zhang et al.

1998). Other factors affecting leaching potential include the texture of the soil, pH, precipitation rates,

tillage, and the types of crops or vegetation that may be planted in the soils.

The mobility of nitrate in a mid-European semi-natural grassland ecosystem as a function of plant

diversity was investigated (Scherer-Lorenzen et al. 2003). The greatest leaching was observed in bare

ground plots as well as plots planted only with legumes. Experiments with plots containing a wider

variety of plant species indicated that total nitrate plant uptake increased and leaching losses decreased

with increasing plant diversity due to greater root biomass within the soils. The leaching of nitrate

decreased in the following order: bare plots > pure legumes > legumes + grasses > legumes + grasses +

herbs (Scherer-Lorenzen et al. 2003). Annual nitrate leaching in an apple orchard was 4.4–5.6 times

greater in plots treated with conventional farming practices (calcium nitrate fertilizer) as compared to

plots treated by organic farming practices, in which nitrogen application was accomplished by loadings of

chicken manure and alfalfa meal (Kramer et al. 2006). Reduced leaching was accompanied by increased

denitrification in the organic treatment areas. Kitchen et al. (2015) investigated groundwater nitrate as a

result of leaching due to agriculture cropping systems over time (1994–2004) and found the greatest

decreases in groundwater nitrate concentration occurred as groundwater moved through an in-field tree

line or through a riparian zone.

Nitrate leaching from croplands with high fertilizer use is a major source of groundwater nitrate

concentrations. In Nebraska, groundwater concentrations of nitrate have been correlated with nitrogen-

containing fertilizer application rates and residual nitrogen in surface soils (Schepers et al. 1991). The

reduction of nitrate concentrations in groundwater through agricultural management practices was

assessed in Nebraska’s central Platte River valley (Exner et al. 2010). Groundwater nitrate concentration

reports were studied from 1986 to 2003. Peak levels, during 1988, in the primary aquifers were

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26.8 mg nitrate-nitrogen/L. A gradual decline was observed with the implementation of fertilizer

management regulations. In 2003, nitrate-nitrogen levels in the aquifer averaged 22.0 mg/L.

Nitrate in soils and surface water are susceptible to denitrification resulting in gaseous losses to the

atmosphere (Taylor 2004). Nitrate in the atmosphere, emitted by denitrification, industrial processes, and

vehicle exhaust, is deposited on land and water in precipitation, gases, and dry particles (Nolan 1999;

Taylor 2004). Atmospheric deposition is a factor for nitrate concentrations in water systems (Momen et

al. 1999; Nolan 1999; Nolan et al. 1997).

6.3.2 Transformation and Degradation

Nitrate and nitrite has the potential to move into various environmental compartments and are subject to

abiotic and biotic degradation processes. Transformation and degradation processes include

denitrification to atmospheric nitrogen and plant uptake (Newton 2005; Nolan 1999). Conversion is

achieved via biotic process carried out by auto- and heterotrophic bacteria (Hammerl and Klapotke 2006).

Under aerobic conditions in aquatic systems, ammonia and nitrite are converted to nitrate via nitrification.

Conversion is achieved through a biotic process carried out by autotrophic nitrifying bacteria. Under

anaerobic conditions in aquatic systems, bacteria convert nitrate to nitrite, which is further reduced to the

gaseous compounds nitric oxide (NO), nitrous oxide (N 2 O), and N 2 (nitrogen). These compounds are

subsequently released to the atmosphere. Results from a study of denitrification in riverbed sediments

found that potential rates for denitrification are limited by environmental conditions such as available

organic carbon and temperature, rather than concentration of nitrate itself (Pfenning and McMahon1997).

Higher rates were demonstrated in experiments with added carbon sources. Additionally, higher rates of

denitrification were measured at 22°C compared to those at 4°C (Pfenning and McMahon1997).

6.3.2.1 Air

Nitrogen compounds are formed in the air by natural phenomena such as lightning (Hord et al. 2011), or

may be discharged into air from industrial processes, motor vehicles, agricultural practices, or emitted by

denitrification processes. Nitrate is present in air primarily as nitric acid and inorganic aerosols, as well

as nitrate radicals and organic gases or aerosols (WHO 2011b). Nitrate in the atmosphere is subject to

wet and dry deposition and are deposited on land via precipitation, gases, and dry particles (Nolan 1999;

Taylor 2004).

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calcium nitrate fertilizer and chicken manure. Nitrogen emissions were higher in the organically treated

plots, as compared to the conventional and integrated plots. Nitrate leaching was much greater (4.4–

5.6 times higher) in the conventional plots as compared to the organically treated plots.

6.4 LEVELS MONITORED OR ESTIMATED IN THE ENVIRONMENT

Reliable evaluation of the potential for human exposure to nitrate and nitrite depends in part on the

reliability of supporting analytical data from environmental samples and biological specimens.

Concentrations of nitrate and nitrite in unpolluted atmospheres and in pristine surface waters are often so

low as to be near the limits of current analytical methods. In reviewing data on nitrate and nitrite levels

monitored or estimated in the environment, it should also be noted that the amount of chemical identified

analytically is not necessarily equivalent to the amount that is bioavailable. The analytical methods

available for monitoring nitrate and nitrite in a variety of environmental media are detailed in Chapter 7.

Nitrate occurs naturally in the environments as a part of the earth’s nitrogen cycle. Elevated levels may

be present due to anthropogenic sources such as fertilizers, and human or animal wastes. High levels of

nitrate in drinking water pose a health risk to infants, children, and pregnant or nursing women (EPA

2009a).

6.4.1 Air

Anthropogenic emissions of nitrogen oxides (NOx) are now of the same order of magnitude as natural

emissions (Hammerl and Klapotke 2006). Air pollution is considered a minor source of exposure to

nitrate (WHO 2011b). Nitrate in the atmosphere is generally a result of nitrogen oxides released into the

atmosphere that are oxidized to nitric acid, in turn forming nitrate particles (Matsumoto and Tanaka

1996). Atmospheric levels of particulate nitrate are highly dependent on temperature and the chemical

composition of aerosol and gases in the atmosphere, especially particulate ammonium nitrate and gaseous

nitric acid (Matsumoto and Tanaka 1996). Reported atmospheric nitrate concentrations range from low

concentrations of 0.1–0.4 μg/m^3 up to higher-level concentrations ranging from 1 to 40 μg/m^3 (WHO

1978, 2011b). Concentrations in Netherland air samples have been reported to range from 1 to 14 μg/m^3.

Indoor nitrate aerosol concentrations of 1.1–5.6 μg/m^3 appear to be related to outdoor concentrations

(WHO 2011b). Zhuang et al. (1999) evaluated the concentrations of fine and coarse particle nitrate in the

atmosphere over Hong Kong. The average daily concentrations for fine and coarse particle nitrate were

found to be 0.583 and 1.663 μg/m^3 , respectively.

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6.4.2 Water

Nitrate and nitrite concentrations in water are typically expressed as either mg nitrate/L (ppm nitrate) and

mg nitrite/L (ppm nitrite), or mg nitrate as nitrogen (nitrate-nitrogen/L) and mg nitrite as nitrogen (nitrite

nitrogen/L) (IARC 2010). The federal drinking-water standard maximum contaminant level (MCL) for

nitrate is 10 mg nitrate-nitrogen/L and the MCL for nitrite is 1 mg nitrite-nitrogen/L (EPA 2009c; USGS

2010a; WHO 2011b). Inorganic nitrate and nitrite are very soluble in water and occur naturally in

groundwater and surface water as a result of the earth’s nitrogen cycle. Naturally occurring background

levels of nitrate (concentrations expected if there were no effects of human development and

anthropogenic sources) have been estimated as 1.0 and 0.24 mg nitrate-nitrogen/L for groundwater and

streams, respectively, in the United States (USGS 2010a).

A comprehensive report analyzed nutrient levels in 5,101 wells from 51 different study areas (Burow et

al. 2010; USGS 2010a). Monitoring data from 1993 to 2003 indicated that nitrate levels in groundwater

varied widely across the nation, with some of the highest levels observed in the Northeast (particularly

southern Pennsylvania), the Midwest, the state of California, and select regions of the Northwest

(Washington state and Idaho). The report concluded that nitrate levels in deep aquifers were likely to

continue to increase as shallow groundwater with high levels of nitrate gravitate downward (USGS

2010a). The highest levels of nitrate were observed in oxic groundwater (water containing >0.5 ppm DO)

as opposed to anoxic groundwaters and shallow wells in agricultural areas, which tended to have greater

levels than in urban areas (USGS 2010a). Burow et al. (2010) analyzed these data and reported that

nitrate concentrations exceeded the MCL (10 mg nitrate-nitrogen/L) in 437 wells (8%). Levels exceeded

the MCL in 20% of wells classified as agricultural land-use setting, and 3% were above the MCL in wells

classified as urban use. In monitoring data from bank and in-stream wells in the San Joaquin River in

California, collected between 2006 and 2008, the concentration of nitrate exceeded the detection limit

(0.01 mg/L) in 5% of the groundwater samples and the concentrations in surface waters ranged from 1 to

3 mg/L. It was reported that 17 of the 26 nested monitoring wells, along the river bed and river bank, had

no detectable concentrations of nitrate during the monitoring period (USGS 2013a).

Monitoring data obtained from 1991 to 1995 in shallow groundwater of coastal plains in the Albemarle-

Pamlico Drainage Unit, in North Carolina and Virginia, have indicated the presence of increased nitrate

concentrations as a result of agriculture and anthropogenic sources. Shallow groundwater concentrations

are higher at inner coastal sites with well-drained soils compared with outer coastal sites. Areas with

anthropogenic nitrogen sources, such as fertilizer and manure, had aquifer concentrations >3 mg nitrate