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Title: Nitrogen Issues Speaker: Bill Pan online.wsu.edu

Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

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Page 1: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Title: Nitrogen Issues Speaker: Bill Pan

online.wsu.edu

Page 2: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Unit 2, Lesson 2:

Nitrogen, the Two-Edged Sword

Food production

Environmental ,

safety, health

issues

Page 3: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Learning Objectives

• The Dichotomy: Credited with saving millions of lives, ammonia synthesis was also created for war time purposes. Today it is also being linked to some of the most pressing environmental and safety problems.

Page 4: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Nutrient Management Issues

Nutrient

Management

Resource

Management

Crop Yield and

Quality

Enviro

nm

en

tal

Pro

tectio

n

So

il

Qu

ality

Page 5: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Carl Bosch (1874-1940)

The perfect catalyst, 1910

Large-scale production, 1913

Ammonia to nitrate, 1914

Nobel Prize in Chemistry, 1931

”chemical high pressure methods”

Fritz Haber (1868-1934) Began work on NH3, 1904

First patent, 1908

Commercial-scale test, 1909

Developed Cl2 gas production, 1914

Nobel Prize in Chemistry, 1918 ”for the synthesis of ammonia from its elements”

Smil, 2001

Page 6: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Industrial N Fertilizer

Production

Haber-Bosch

1200C, 500atm

3H + N 2NH 2 2 3

CO2, N2O (Greenhouse gases)

Natural gas

CH4

Page 7: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Inorganic N Fertilizer has been

largely responsible for

increased crop yields of the

Green Revolution

Page 8: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Haber-Bosch: Synthesis of Reactive N

0

1

2

3

4

5

6

7

1750 1800 1850 1900 1950 2000 2050

0

50

100

150

200

Humans Haber Bosch

Legumes/Rice NOx emissions

Galloway JN and Cowling EB. 2002; Galloway et al., 2002a

N-Discovered

N-Nutrient

BNF

Haber-Bosch

N2 + 3H2 2NH3

Hu

man

Po

pu

lati

on

, b

illi

on

s

Reactiv

e N

itrog

en

, Tg

DHumans = D Reactive N

Page 9: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Harvested Crop Acreage

Per Person in the World

0

0.05

0.1

0.15

0.2

0.25

Ye

ar

195

1

195

7

196

3

196

9

197

5

198

1

198

7

199

3

Page 10: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

A Plateau in Grain Production

World Grain Production

0

50

100

150

20019

60

1966

1972

1978

1984

1990

Year

Grai

n (m

illion

tons

)

Page 11: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Per Capita Grain Production

0

100

200

300

400

Ye

ar

195

1

195

7

196

3

196

9

197

5

198

1

198

7

199

3

Grain (kg/person)

Page 12: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Post World War II Adoption of

Commercial Fertilizers

Stonehenge

1960 1980 2000 2020Fe

rtili

ze

r N

utr

ien

t U

se

(m

illio

n to

ns)

0

10

20

30

40

50

60

70East Asia w/China)

N. Am., Europe

South Asia (w/India)

Latin America

Near East/North Africa

Subsaharan Africa

Source: FAO, World Agriculture: towards 2015/2030

~60% of nutrients are used on cereal crops,

predominantly wheat, rice, maize

Page 13: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Source: International Fertilizer Industry Association

Shifting Worldwide Distribution of Nitrogen Production

Current trends: http://www.fertilizer.org/ifa/statistics/pit_public/pit_public_statistics.asp

Page 14: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Global Competition is placing

increasing emphasis on crop quality

Page 15: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

M. Pidwirny. Physicalgeography.net. U. British Columbia

Page 16: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Changes in Spatial Relationships of

Trophic Pyramid (modified from Magdoff et al., 1997)

plants

animals

humans

soil

Industrial Agriculture Primitive agriculture

plants

animals

humans

soil

plants

animals

humans

soil

Urbanization

Page 17: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

N related environmental issue #1-

health concerns

• Nitrate contamination of groundwater

– methemoglobinemia (blue baby syndrome), cancer, diabetes

– EPA maximum limits: 10 ppm nitrate-N (10 mg/L) or 45 ppm nitrate, EU 0.1 mg nitrite-N/L

– BUT, meat preservative, antibacterial, lowers blood pressure

– Treatment systems are available but expensive

Page 18: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Nitrate in Drinking Water

in the Columbia Plateau

Page 19: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Fertilizer Use in the Columbia

Plateau

Page 20: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

China’s N Contamination Problem

Ground water nitrate above critical health standards:

•50% in northern China

•21% in Shaanxi Province

•30% in Guandong Province

Source: Yang et al., 2004, Agron. J. 1039-1049.

Atmospheric wet N deposition

~11 Tg N (12 kg N/ha/yr) –Xing, In Cowling et al., 2002.

Page 21: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Calculate-compare N intake from

• 1 liter of 10 ppm nitrate-N (NO3-N)

• ¼ lb preserved meat with 100 ppm nitrite-N

(NO2-N)

• 6 oz lettuce with 3500 ppm NO3 in the cell

sap…assume lettuce is 85% water.

• 5 g sensitive toothpaste with 5% KNO3 wet wt

Page 22: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

• Dead zone-algal

blooms and decay

cause oxygen

depletion of Gulf of

Mexico – see the

far-reaching

watershed of the

Mississippi River

N related environmental issue #2

Page 23: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Nitrate concentrations in the

lower Mississippi

Page 24: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Total N Flux Through the

Lower Mississippi

Page 25: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Worldwide Distribution of

Hypoxic Coastal Waters

These “dead zones” are associated with major population areas

or nutrient laden watersheds

Egypt

http://www.earth-policy.org/

Page 26: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Issue #3: Non-renewable resource

use • Reliance on natural

gas for Haber-Bosch process

• 3-4% of natural gas used for fertilizer production

• N price increases are driving farmers out of business

Page 27: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Issue #4 Safety in

transportation and handling

Page 28: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Issue #5: Soil Quality

How has the advent of inorganic N fertilizers affected soil

quality?

-more crop residues produced, builds soil organic matter

-Conversely, N fertilizers allow for less diverse crop rotations,

green manures not required.

-high levels of ammonium, nitrite can temporarily reduce

microbial activity.

Page 29: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Inorganic vs. Organic N

Sources • What are the pros and

cons?

• Use on farm resources

• Multiple benefits of organic sources on nutrient availability, soil quality

• Costs: storage, transportation, application

Page 30: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Issue #6: Public safety: Illegal Uses

of N fertilizers

• Anhydrous Ammonia Thefts and Releases Associated with Illicit Methamphetamine Production --- 16 States, January 2000--June 2004 http://www.cdc.gov/mmwr/preview/mmwrhtml/mm5414a4.htm

• Anhydrous ammonia, a colorless gas with a pungent, suffocating fumes, is used primarily as an agricultural fertilizer and industrial refrigerant (1). Anhydrous ammonia is also a key ingredient for illicit methamphetamine (meth) production in makeshift laboratories. Exposure to anhydrous ammonia can be immediately dangerous to life or health (1,2). Anhydrous ammonia generally is not available for sale to the public; states require a license for purchase. Because of this, many illicit meth producers (i.e., "cookers") resort to stealing anhydrous ammonia. If released into the environment, anhydrous ammonia can cause acute injuries to emergency responders, the public, and the cookers themselves. In addition, when handled improperly, anhydrous ammonia can be explosive and deadly. This report describes examples of anhydrous ammonia thefts associated with illicit meth production, summarizes ammonia theft events reported to the Agency for Toxic Substances and Disease Registry (ATSDR), and suggests injury prevention recommendations, such as installing valve locks or fencing on unattended tanks and donning appropriate personal protective equipment (PPE) when responding to releases.

• ATSDR maintains the Hazardous Substances Emergency Events Surveillance (HSEES) system to collect and analyze data about the public health consequences (i.e., morbidity, mortality, and evacuations) of hazardous substance--release events*. The information in this report is based on events reported to HSEES from 16 state health departments† during January 1, 2000--June 30, 2004§.

• Ammonium nitrate use in explosives-e.g. Sterling Hall, U WI, 1971; Oklahoma City, 1995

– Commercial ban as fertilizer due to heightened security concerns after 9/11

Page 31: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Issue #7: Air pollutants and

Greenhouse Gases: Ammonia and

N oxide emissions • Feedlot, manure storage, compost

pile

• Crop field emissions

• Water treatment by denitrification

–Food processing

–Manure lagoons

–Sewage treatment

Page 32: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Government Intervention:

Nutrient Management Plans • CAFO (confined animal feeding operations) in

WA http://agr.wa.gov/FoodAnimal/Livestock-Nutrient/CAFONutrientMgmtPlans.aspx

Page 33: Title: Nitrogen Issues Speaker: Bill Panapps.aoi.wsu.edu/onlineMedia/pdf_version/soils441_12_art(c123).pdfLarge-scale production, 1913 Ammonia to nitrate, 1914 Nobel Prize in Chemistry,

Stakeholders in the

Nutrient Management

• Farmers

• Public

• Fertilizer industry

• Government

• Universities