We and Nitrogen: Explosives to Eutrophication

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We and Nitrogen Explosives to Eutrophication
NOAA Central LibraryBrown Bag Seminar26 June
2008
Jawed Hameedi Center for Coastal Monitoring and
Assessment National Centers for Coastal Ocean
Science National Ocean Service, NOAA
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Four aspects

• Explosives and warfare
• Agriculture
• Nutrition
• Contemporary

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Stating the obvious!

• Nitrogen in the Earths atmosphere 78
• Nitrogen in the Earths crust 20 ppm
• P1,000 ppm
• Nitrogen in the human body 4th most abundant
  element

• Human Body (70 kg)
• Oxygen 43 kg
• Carbon 16 kg
• Hydrogen 7 kg
• Nitrogen 2 kg
• Calcium 1 kg
• Phosphorus
• Potassium
• Sulfur
• Sodium
• Chlorine

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Dr. Jekyll and Mr. Hyde split personality

• Building block for lifes essential molecules
  (nucleic acids, enzymes, pigments) deadly poison
  (cyanides, azides), anesthetic (nitrous oxide),
  key ingredient of nearly all antibiotics, and
  used in regulating heart function (nitric oxide,
  nitroprusside)
• Nearly all explosives are based on nitrogenous
  chemicals (e.g., TNT, nitroglycerine, nitrogen
  triiodide) nitrogen gas is used as a safeguard
  against certain liquid explosives.
• Hydrazine is used as a rocket fuel nitrogen gas
  is used to prevent fire in spacecraft chambers.
• Nitrous oxide is approved as a food additive
  (aerosol propellant whipped cream) alkyl
  nitrite (or poppers) taken with nitrous oxide
  causes hallucinations and surfing some alkyl
  nitrites were used as antidote for cyanide
  poisoning.

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I. Green Bamboo Fireworks

• First fireworks may have been caused by burning
  green bamboo shoots when dry wood ran out Han
  Dynasty (200 BC)
• Fast growing traps air pockets
• Various PAHs, alcohols and phenolic compounds
• Created sizzling sounds, little sparkles, and
  mini-explosions
• Nurtured a belief that the sounds and flames
  warded off the evil spirit Nian, which ate
  crops and people
• Exploding bamboos became a ritual during the
  Lunar New Year festivals, and then extended to
  weddings, births and other occasions

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Black Powder Explosions

• May have been discovered from accidental ignition
  of chemicals used to synthesize an elixir for
  life
• Initial ingredients in such experiments included
  chemicals of know medicinal value mercury,
  arsenic, honey, and salts of various kinds by
  mixing or cooking various combinations of them
• Many noblemen died after tasting different
  potions, and a few laboratories were destroyed
  during experiments until the fire chemical
  or huo yao was identified (500 to 900 AD)
• The fire chemical was potassium nitrate
  saltpeter or saltpetre or stone salt
• It was isolated and used in bamboo stems first
  to ward off evil spirits, then to scare off enemy
  soldiers.

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Ingredients for an explosive

• Fuel anything that would burn
• Charcoal, alcohol, fuel oil, honey, powdered
  aluminum
• An oxidant e.g., saltpeter, ammonium nitrate,
  perchlorate, etc.
• Reaction stabilizer or catalyst e.g., sulfur to
  help form potassium sulfide or potassium sulfate
• 10KNO3 3S 8C ? 2K2CO3 3K2SO4 6CO2 5N2
• 2KNO3 S 3C ? 3CO2 K2S N2

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Evolving pyrotechnology

• Add more saltpeter bigger and faster burn
• Concept of fuse
• Inventing fire arrows
• Paper firecrackers instead of bamboos
• When open at one end, escaping gas would propel
  the device a rocket was invented!
• Firework technology further evolved in Europe,
  notably Italy (1500-1700)

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Explosives in Europe

• Introduced by the Mongols, who brought the
  explosives technology from China by way of the
  Silk Road perhaps the Northern Route (13th
  Century)
• First pipe bomb black powder in bamboos
• Technology advancement by putting gunpowder in
  bronze metal bells (from cathedrals) ultimately
  inventing the cannon (14th and 15th Centuries)
  capable of hurling massive stones and destroying
  castle walls and enemy frontlines

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Quest for Saltpeter

• The ingredient of choice for weapons and wars but
  Europe had no minerals deposits of potassium
  nitrate
• only source being rotting organic matter, notably
  urine.
• Thus dung heaps became a resource creating
  artificial nitre beds to extract potassium
  nitrate crystals.
• In 1626, King Charles declared an edict for
  conserving and contributing wastes from humans
  and animals, and that edict was enforced by a
  police known as Petermen.
• The Golden Age of Guano Peru (1840-1880) more
  than 20 million tons was excavated from arid (no
  rain) islands off Peru largely under English
  monopoly
• The War of the Pacific (1879-83) was fought to
  control Chilean saltpeter (sodium nitrate) mines
  the worlds largest

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Haber-Bosch Process Nitrogen fixation

• Fritz Haber -- professor of physical chemistry
  and electrochemistry demonstrated (1909) a
  process of converting atmospheric nitrogen to
  liquid ammonia
• Carl Bosch a pioneer in high-pressure physics
  and manufacturing at BASF -- agreed to
  investigate large scale production

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Haber-Bosch Process

• Within years (1913), commercial production of
  ammonia was feasible, and Germany was producing
  60,000 tons of ammonia making it
  self-sufficient in the production nitrogen
  compounds (for example ammonium nitrate) for use
  in making bombs and explosives during World War I.

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II. Nitrogen Limitation in Agriculture

• Recognized in the earliest recorded times!
• Adaptations to this deficiency
• Enriching the farm with crop residues and animal
  manure
• Resting the soil between crops
• Importing plants, e.g., sorghum from Africa, that
  would fertilize the field

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The Age of Agricultural Revolution(8th to 13th
Centuries)

• Rashid, Umayyad, Abbasid, and Fatimid dynasties
• Introduced crop rotation system 4 different
  crops in a two-year cycle
• Planted fast-growing vegetables and grains in
  between the main crops
• Imported foreign crops citrus, sugarcane, rice,
  herbs, etc.
• Installed a pump-operated irrigation systems and
  canals
• Introduced a cash market for crops to assure
  supplies and pricing stability
• The Fertile Crescent became the most productive
  patch of land in the world.

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Four Crop Rotation England(18th Century)

• Wheat, barley, clover, and turnips assured food
  and fodder for livestock on a year-round basis
• Crop fertilization use of minerals

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Haber-Bosch Process

• The process is now producing nearly 100 million
  tons of nitrogen fertilizers each year (ammonium
  sulfate, ammonium phosphate, ammonium nitrate,
  and urea)
• 27 million tons used in China
• 11 million tons used in US
• 11 million tons used in India

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• There is no imminent shortage of nitrogen-based
  fertilizers
• The Haber-Bosch Process has been termed the
  Detonator of the Human Population Explosion
  implying that the current human population and
  its lifestyles could not have been supported by
  the naturally occurring nitrogen cycle.

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III. We need nitrogen!

• Nitrogen is essential to life it is needed for
  construction of lifes basic building blocks,
  i.e., DNA and RNA molecules, and is also required
  to make proteins and enzymes that are crucial to
  the functioning of our bodies

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There is no substitute for nitrogen intake!

• Our medical doctor friends tell us
• Nitrogen deficiency can result in growth
  retardation in children wasting of muscles,
  changes in skin pigmentation, reduced mental
  capacity, fatigue, and susceptibility to
  infections.

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Protein Paranoia

• The US recommended daily allowance is less than
  one-half of a quarter pounder each day (or
  roughly 50 lb per year)
• Americans consume the most roughly 275 lb per
  person each year
• Western European, Brazil, Argentina, New Zealand
  150-200 lb/year

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Other countries

• China meat consumption is on a rampant increase
  having steadily gone up
• 20 lb/year in the 1970s
• 120 lb/year in recent years
• Pakistan 27 lb/year
• India 12 lb/year
• These figures do not include seafood consumption,
  which in the US is about 16 lb/year

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Meat Production

• Because of this voracious (and increasing)
  appetite for meat
• We are sharing the Earths natural resources with
  more than a billion cows, about a billion pigs,
  nearly 2 billion sheep and goats, and 14 billion
  chickens
• Yearly meat production amounts to more than 200
  million tons
• China -- 60 million
• US 37 million
• Brazil 13 million
• France 6 million

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IV. So, whats the big problem?

• Only about 14 percent of nitrogen used as
  fertilizers results in crops and even lesser
  amount in human food. The remaining amount is
  lost
• during food production, including transportation
  and application of fertilizers, spoilage and
  waste
• seepage to groundwater and surface water streams
• as crop residue, animal waste
• via escape of gaseous chemicals to the
  atmosphere.
• Nitrate in particular does not bind well with
  soil it can be readily transported over long
  distances, typically ending up in large
  waterbodies

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Guess estimates of sources and amounts (million
metric tons, mt) of reactive nitrogen (1890)
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Guess estimates of sources and amounts (mt) of
reactive nitrogen (1890 and1990)
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Effects of nitrogen overload on land

• Nitrogen saturation of watersheds, i.e., more
  nitrogen is deposited than plants can use or
  bacteria can transform causing excessive algal
  growth even in the most remote alpine lakes
• Lakes, streams and soils are becoming acidic,
  resulting in fundamental changes in ecosystems
• Nitrogen in groundwater contaminates drinking
  water in some areas much above the criterion
  (400 vs. 10 mg NO3-N/L
• Nitrogen oxides promote formation of fine
  particulate matter in the air (respiratory
  problems)
• Nitrous oxide is an important greenhouse gas it
  has a global warming potential 329 times greater
  than that of carbon dioxide

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A Global Environmental Issue subject of
conferences, research initiatives and declarations

• The direct and indirect delivery of fertilizers
  (reactive nitrogen) into coastal bays and
  estuaries has increased tremendously in recent
  years, and there are indications that the problem
  will worsen globally
• In nearly all parts of the world, the effects of
  excessive nutrient enrichment in coastal waters
  are obvious
• Unwanted and excessive algal growth that cannot
  be utilized by animals
• Accumulation of large amounts of dead and
  decaying plant matter, and that sucks up
  dissolved oxygen in the water
• Dead zones have now been documented all over
  the world
• Coral reefs are surrounded by murky green, not
  azure blue, waters, with 40 of the worlds reefs
  in jeopardy of being lost.

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CAFOs animal meat producing factories

• In a book entitled This Steers Life, (Michael
  Pollan, NY Times March 31, 2002), it was noted
  that we have transformed what was once a
  solar-powered ruminant into the very last thing
  we need another fossil fuel machine.
• It has been estimated that annual production of
  cows in the US requires 158 million barrels of
  crude oil equivalents or more energy per cow
  than I use as gasoline each year!
• There is a general lack of management of manure
  from these operations the argument is that you
  will not be allowed to put untreated human waste
  from a town of 120,000 people on a farmland but
  you can do that if you had a CAFO farm with 4,000
  cows.

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Trends in national and utility-only NOX and SO2
emissions from 1985 to 2006 and projected to 2015

• Burning of fuel at high temperature (automobiles,
  power plants, electric utilities, other
  industries)
• Escape from fertilized fields

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Journey and fate of atmospheric nitrogen
deposition

• Would the transport of nitrogen from the
  watershed to rivers and streams be minimal if
  atmospheric deposition were less than 8
  kg/ha/year (as was shown in a northeast forest)?

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Relative contribution of nitrogen sources to
different estuaries on the US East Coast
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Maumee River watershed a poster child!

• Once a forested swampland now nearly all
  farmland and Toledo
• Tile drainage poor soil and water management
• Watershed loses millions of tons of soil to Lake
  Erie
• Approximately, 850,000 cubic yards 85,000 dump
  truck loads of sediment is dredged from Toledo
  Harbor each year
• Total phosphorus loading of about 100,000 kg/day
  Detroit River 2,250 kg/day

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Nitrogen and HABs

• Largely due to greatly increased inputs of
  reactive nitrogen to coastal bays and increased
  number of harmful algal bloom observations in
  recent years, nitrogen-related issues in coastal
  waters are stated or implied to include HABs.
• A direct relation between nitrogen
  over-enrichment, nearly always reported as
  concentration of dissolved inorganic nitrogen
  (DIN), and the onset and magnitude of HABs has
  remained difficult to quantify.

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Nitrogen control strategy

• Standards, criteria and strategy are required
  under Clean Water Act amendments (1977), and the
  Great Lakes Critical Programs Act (1990)
• EPA -- concept of ecoregions
• Adopt 25th percentile of historically reported
  nitrogen data
• Develop your own

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Delaware River Basin Commission

• None of the states accepted the Ecoregion
  criteria
• Delaware River flows through 5 aggregate
  ecoregions with N criteria of 0.54, 0.38, 0.31,
  0.69, and 0.71 mg/L (from upstream to downstream)
• Dischargers question no measureable change
  policy or capping nutrient discharge at some
  derived value of the dataset 17 year long for
  the bay effects?
• Nothing for the bay 1-2 mg/L very high ambient
  values

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No numerical criteria for nitrogen control

• None for coastal bays and estuaries
• Just a handful of states have approved ones
  for entire classes of rivers and streams
• No toxicological benchmarks for protection of
  coastal and estuarine organisms in Canada, an
  interim guideline exists (but not from impacts of
  eutrophication) 18 mg NO3/L
• National Estuaries Experts Workgroup (2006)
  report due?

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V. Take Home Messages -- I

• Excessive, unprecedented and increasing amounts
  of reactive nitrogen are entering the biosphere,
  almost entirely due to the Haber-Bosch process.
• Environmental concerns associated with nutrient
  enrichment are quite varied and potentially
  severe ranging from low or non-existent
  dissolved oxygen in waterbodies, to smog and
  greenhouse effects, to eutrophication and altered
  ecosystems, and jeopardy of coral reefs.
• There are no environmental or toxicological
  criteria for protection of coastal and estuarine
  organisms and ecosystems.

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Take Home Messages -- II

• Knowledge of nitrogenase
• Carbon sequestration on land
• Nitrogen fixation in the sea
• Effects of nitrogen deposition on the inorganic
  carbon cycle in the sea ocean acidification
• Increased release of carbon dioxide from peat
  bogs under increased nitrogen deposition

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• Thank You!
• Jawed.Hameedi_at_noaa.gov

Photographs Free downloads from the Internet,
NOAA, cited documents, and the author
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Nitrogenase

• The highly complex structure of the nitrogenase
  enzyme and its molybdenum-iron co-factor continue
  to surprise scientists
• Biosynthesis and catalytic roles also where and
  how the substrates bind (Smith, 2002)
• One implication is relative to the role of iron
  in oceanic nitrification.

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Carbon sequestration on land

• Many carbon sequestration scenarios for
  terrestrial ecosystems project hundreds of
  billion metric tons of carbon bound in trees and
  other plants where would thousands of million
  tons of nitrogen come from? (Gruber and Galloway,
  2008).

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Nitrogen fixation in the sea

• What really is the global distribution of
  nitrogen fixation in the sea?
• Recent data indicate that it is quite variable
  spatially, and the supply of iron may not be the
  primary limiting factor for marine nitrogen
  fixation (Deutsch, et al., 2007)
• The figure in my table 140 million metric tons
  is an often-repeated but still a crude estimate
  (Galloway and Cowling, 2002)

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Nitrogen deposition and ocean acidification

• The significance of 37 million tons of nitrogen
  deposition to the coastal and open ocean
  environments is yet to be determined,
  particularly in terms of ocean acidification and
  the inorganic carbon system
• Wet deposition of nitrate is acidic, and the dry
  deposition of ammonia is alkaline (Doney, et al.,
  2007)

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Nitrogen deposition on peat bogs

• High level of nitrogen input can make bogs such
  as peat bogs -- give off more carbon dioxide,
  thereby aggravating greenhouse effect.
• A huge amount of carbon is stored in peat layers,
  which consist of organic substances, such as
  polyphenols, that are difficult to break down.
• Bog mosses growing in nitrogen-enriched soils
  produce smaller amount of polyphenols also grass
  and sedge plants tend to proliferate this
  results in a net increase of carbon dioxide
  emissions (Uppsala University data).