Historical Overview

Historical Overview

Shakespeare (1564-1616) • Hamlet: How long will a man lie I' the earth ere he rot? • Gravedigger: I' faith, if he be not rotten before he die--as we have many pocky corses now-adays, that will scarce hole the laying in--he will last you some eight year or nine year; a tanner will last you nine year. • Hamlet: Why he more than another? • Gravedigger: Why, sir his hide is so tanned with his trade, that he will keep out water a great while; and you water is a sore decayer of your whoreson dead body."

AbioticBiotic • BIOGEOCHEMISTRY • Geology • Chemistry • Soils • OceanographyLimnology • Ecology • Microbiology • Animal and Plant Physiology

Journals • “Biogeochemistry” (1984) • “Global Biogeochemical Cycles” published by AGU

Other Major Journals Soils: Soil Science Soil Science Society of America Journal Journal of Environmental Quality Applied Soil Ecology Biology and Fertility of Soils Soil Biology and Biochemistry Geoderma

Other Major Journals Water: Limnology and Oceanography Water Research Hydrobiologia Water Resources Research Journal of Hydrology Hydrological Processes Geology: Geochimica Cosmochemica Acta Air: Atmospheric Chemistry

Other Major Journals Forestry: Canadian Journal of Forest Research Other: Ecology Ecological Applications Journal of Applied Ecology Bioscience Science Nature Water, Air and Soil Pollution

Societies that have important contributions to biogeochemistry Soil Science Society of America Ecological Society of America American Geophysical Union (Biogeochemistry Section) Society for Limnology and Oceanography

Meetings and workshops International Acid Rain Meetings BIOGEOMON Gordon Conference on the Hydrobiogeochemistry of Forested Catchments SCOPE meetings on nitrogen, carbon, sulfur and phosphorus Chapman Conferences (e.g., nitrogen) Northeastern Ecosystem Research Cooperative (NERC)

Historical Development of Biogeochemistry (Gorham) 1) Photosynthesis and respiration 2) Decomposition 3) Metabolism of nitrogen and sulfur 4) Mineral nutrition of plants 5) Weathering of rocks and soils.

Ancient History Plato (428-348 B.C.) accepted the ancient Greek (Empedocles of Agrigentum) theories about the primary elements of matter: air, water, earth and fire; he added a fifth element, which Aristotle (385-322 B.C.) subsequently explained as "heaven". There have been many advances in the understanding of chemistry (defined as the investigation and discussion of the properties of substances), geology (study of the rocks and minerals: description, origin and reactions) and biology (study of life).

Vernadsky and Suess Vernadsky (1863-1945) Biosphere term originated by the Austrian geologist Eduard Suess (1831-1914) in early 1900's and developed further by the Russian, Vladimir Vernadsky. Suess also coined the term hydrosphere and lithosphere to correspond with the term atmosphere which was already in usage. Vernadsky--Ukrainian geochemist, mineralogist, biogeochemist, crystallographer, holistic naturalist and the earliest proponent of the biosphere concept ; first to define many aspects of the biosphere including the role of man.

1600's and 1700's debate on how plants obtain matter for growth(E.J. Russell. 1927; Soil Conditions and Plant Growth) Palissy (1563) stated: "you will admit that when you bring dung into the field it is to return to the soil something that has been taken away . . . When a plant is burned it is reduced to a salty ash called alcaly by apothecaries and philosophers . . . Every sort of plant without exception contains some kind of salt. Have you not seen certain laborers when sowing a field with wheat for the second year in succession, burn the unused wheat straw which had been taken from the field? In the ashes will be found the salt that the straw took out of the soil; if this is put back the soil is improved. Being burnt on the ground it serves as manure because it returns to the soil those substances that had been taken away."

The search for the "principle: of vegetation” (1630-1750) Lord Bacon (philosopher and scientist) thought that water was the "principal nourishment" of plants.

For example the experiment by Van Helmont: “I took an earthen vessel in which I put 200 pounds of soil dried in an oven, then I moistened with rain water and pressed hard into it a shoot of willow weighing 5 pounds. After exactly five years the tree that had grown up weighed 169 pound and about three ounces. But the vessel had never received anything but rain water or distilled water to moisten the soil when this was necessary, and it remained full of soil, which was still tightly packed, and, lest any dust from the outside would get into the soil, it was covered with a sheet of iron coated with tin, but perforated with many holes. I did not take the weight of the leaves that fell in the autumn. In the end I dried the soil once more and got the same 200 pounds that I started with, less about two ounces. Therefore the 164 pounds of wood, bark and root, arose from the water alone” Of course the experiment overlooked the role of the 2 ounces lost and the importance of gases from the atmosphere.

Experiment showed: most of the water is transpired and some matter from the substrate is incorporated into the plant. Boerhaave (textbook ,1727) indicated that plants "absorb the juices of the earth and then work them up into food". Jethro Tell (introduced the horse hoe) stated that: "It is agreed that all the following materials contribute in some manner to the increase of plants, but it is disputed which of them is that very increase or food: (1) nitre, (2) water, (3) air, (4) fire, (5) earth."

Phlogiston theory • In the 17th century an important theory was the "Phlogiston theory“ • Explained that the burning of substances resulted in the release of "phlogiston". • Hypothesis accounted for a considerable number of observed phenomena. • For example, the reason that a burned candle in a jar went out was that the phlogiston could not escape. We know now that it is the absence of oxygen which causes the problem.

Joseph Priestley1733-1804England “I have discovered an air five or six times as good as common air” From William Jensen, University of Cincinnati

"The search for plant nutrients" Priestly (1771) experiments where critical in establishing that "that plants, instead of affecting the air in the same manner with animal respiration, reverse the effects of breathing, and tend to keep the atmosphere pure and wholesome, when it becomes noxious in consequences of animals either living, or breathing, or dying, and putrefying in it". He did not discover oxygen and in his later experiments did not know the importance of light in affecting these results. It could be argued that he never discovered oxygen but rather he isolated dephlogisticated air.

Ingen-Housz (1796) -- Dutch physician showed that purification goes on only in the presence of light and that only the green portion of the plant is involved with the purification. Also showed that plants respire and give carbon dioxide. The use of pot cultures and plant analyses were initiated to ascertain which materials cause plant growth. "Saltpetre, Epsom salt, vitriolated tartar (i.e., potassium sulphate) all lead to increased plant growth, yet they are three distinct salts. Olive oil is also useful." In many ways the advancement in understanding limited by methodology. How could these various substances be identified and quantified?

Theordore de Saussure (1804) 1) Developed the quantitative experimental method 2) Founder of agricultural chemistry (basis for later work by Boussingault, Liebig, Laws and Gilbert) 3) Grew plants in air and mixtures of air and carbon dioxide and measured the gas changes by eudiometric analyses (changes in volume of gas) and changes in the plant by "carbonisation". 4) Quantified how much oxygen plants give off and how much carbon dioxide they utilize. 5) Concluded that the soil contributed only a small part of the "plant food". His work suggested that the oxygen came from carbon dioxide and not from water: 6CO2 + 6H2O —> C6H12O6 +6O2

M. Bertholeet • (1748-1822) • French scientist • Experiments suggested that hydrogen in plant tissues came from water. • Grew plants in hydrogen free material and except for water and found that they still grew and indicating that the hydrogen came from the water. • Jean Senebier • (1742-1809) • Experiments which indicated the contrary to Saussure and suggested that the oxygen came from the carbon dioxide.

Dutch microbiologist C. B. Van Niel worked with purple sulfur bacteria (chemoautotrophs) which form S and not oxygen. • CO2 + 2H2S –> (CH2O)n + H2O + 2S • Assumed that the same progress is analogous in plant photosynthesis than you would substitute "O" for "S" and the oxygen would be derived from water. • Also found that if a plant is grown from seed in water there is no gain in ash: the amount of ash found in the plant after growth in water is the same as the amount of ash found in the seedling except for a small amount of ash input via dust (first references to the role of dry deposition?)

Justus Liebig1803-1873Germany Liebig reported in 1840 [disavowal of humus proponents]: "All explanations of chemists must remain without fruit, and useless, because, even to the great leaders in physiology, carbonic acid, ammonia, acids, and bases, are sounds without meaning, words without sense, terms of an unknown language, which awake no thoughts and no associations." The experiments quoted by the physiologists in support of their view are all "valueless for the decision of any questions". "These experiments are considered by them as convincing proofs, whilst they are fitted only to awake pity".

Liebig’s analytical laboratory (1840) (http://www.liebig-museum.de/home1.html)

The vehemence and tenor of Liebig's comments killed the "humus theory". Other scientists did much of the work, but Liebig was the most vocal in putting down the humus theory. Today that there is a renewed interest in "organic gardening.

Also this led to intensive studies on single elements and focuses on elemental interactions would come later. Russell in 1927 stated: “Only the boldest would have ventured after this to assert that plants derive their carbon from any source other than carbon dioxide, although it must be admitted that we have no proof that plants really do obtain all their carbon in this way.” Liebig latter added "by the deficiency or absence of one necessary constituent, all the others being present, the soil is rendered barren for all those crops to the life of which that one constituent is indispensable". [Currently known at Law of the Minimum] He also made mistakes [Do all scientists make mistakes?]and stated that "Plants will derive their ammonia from the atmosphere as they do carbonic acid". He also had developed his own chemical manure which would be sufficient for growth of crops, but his manure did not work well in practice. One problem “manure” did not contain nitrogen compounds and potassium and phosphate compounds were made insoluble by fusion with lime and calcium phosphate.

Rothamsted and Long-Term Research Joseph H. Gilbert and John B. Laws started in 1843 the famous field experiments at Rothamsted, England J.H. Gilbert J. B. Laws Long Term Research Plots Pictures from: http://www.mpcresearch.com/rothreview/

Not originally planned as a long term experiment, but rather was kept going initially by a controversy with Justus Liebig over the source of nitrogen for plants and what inputs were needed to maintain crop productivity. “I suspected that Laws and Gilbert needed to go on showing that they were right on all counts. And not only right, but right beyond all reasonable doubt. And so they kept the experiments going” (p. 33). [Demonstrating the importance of long term research] Currently archived samples are being used for trace metals and organics. Rothamsted Manor

There was considerable controversy on whether chemical fertilizers will ultimately exhaust the ground, and the Rothamsted plots showed that this was not a problem. Do you agree with this finding?

Soil Bacteriology Much of the early work revolved around the problem of where was nitrogen derived from. Even today the quantification of fixed N inputs is not an easy task and our understanding is far from being complete. Schloesing and Müntz (1877)which had sewage trickle down a column of sand and over time the ammonia was converted to nitrate after a delay of 20 days. Why was there a delay? It was shown that addition of small amounts of chloroform would stop the nitrification and if chloroform treatment was stopped nitrification would begin again. Nitrification was regulated by microorganisms or "organized ferments".

Pasteur Demonstrated the role of microorganisms in a variety of situations including causation of some diseases and for their role in decomposition. Hellriegel and Wilfarth (1888) Growth of non-leguminous plants (barley, oats, etc.) was directly proportional to nitrate supplied, while for leguminous plants there was no such relationship. Warington Nitrification was a two-step process with conversion of ammonia to nitrite and then nitrite to nitrate. Winogradsky (1890) isolated nitrifying bacteria.

There is great interest in nitrogen today. In the past, N generally considered a limiting nutrient and an important fertilizer. Due to high anthropogenic outputs of N (i.e., NOx from combustion, NH3 from livestock manures and inorganic N fertilizers), N may be in excess and cause problems relating to air quality, water acidification and water quality (eutrophication of coastal waters).

Major Advances in the early 1900's Biogeochemical cycles in lakes shown by Hoppe-Seyler (1895), Birge (1906), Birge and Juday (1911). Redox reactions between sediments and water studied by Einsele (1936) and Mortimer (1941, 1942). A major treatise was the book by Vernadsky (1924) on Geochemistry and another book "The Biosphere". The work of Redfield (1934) was important in the establishment that elemental ratios were predictable in marine systems and this was expanded to the total biosphere.

Major problems in following elemental dynamics because of both forward and backward reactions and the possibility of various reactants and products being involved. Advent of radioactive and stable isotopes allowed careful analysis of elemental pathways and cycles. What are differences between radioactive and stable isotopes?

Stable isotopes used to ascertain where oxygen produced from photosynthesis came from (CO2versus H2O) Team of scientists at U. of California in 1941 using O18 with the green alga Chlorella. Also, this isotope was used in analysis of elemental dynamics of aquaria and ponds. 6CO2 + 6 H2*O –> C6H12O6 + 6*O2 Later the use of stable isotopes became more important especially by Thode (Hamilton University, Canada) and Russians. Stable isotope work rapidly expanding including work on C, N and S cycling and mineral weathering.

1960's and the present In the latter 1960's environmental concerns became highlighted especially interests in pesticides and elements such as phosphorus which cause eutrophication of lakes. R. Carson's publication "Silent Spring" popularized concerns associated with pesticides especially chlorinated hydrocarbons. Roles of biotic interactions in affecting elements and the potential for accumulation of compounds along food chains shown. Her book followed the more formalized and scientific writings of Rudd. The EPA also and the popularization of ecology accelerated.

Eutrophication and Small Watershed Research Also in the latter 1960's and early 1970's shown that phosphate from detergent and agriculture was a major contributor to eutrophication of lakes. Much of this research focused on the region of the Great Lakes There is greater attention being played today on the role of agriculture, especially to N loadings to coastal and estuary waters.

Small watershed approach also became developed with notable work at Hubbard Brook (Likens and Bormann) and Coweeta (W.Swank) being notable examples. Initially started out for determining hydrological relationships since forest systems play an important role in flood control and biogeochemical analyses could be incorporated easily into such a format. Coweeta North Carolina Hubbard Brook New Hampshire

International Biological Program(latter 1960’s and early 1970’s) • Major goal the quantification of production in major ecosystems of the world stimulated work on ecosystem level and showed clearly the elemental dynamics were extremely important. • Various books were published including volumes such as Dynamic Properties of Forest Ecosystems (D. Reichle, ed; 1981) which included tabulation of ecosystem elemental contents and fluxes. • Ecological problems became to be tackled as "big science" using large multidisciplinary approaches. • Proposed National Ecological Observatory Network (NEON)

Ecosystem Manipulations There was also the beginning of experimental manipulations of both terrestrial and aquatic ecosystems. These have included chemical and biotic manipulations, both of which had major impacts on biogeochemistry and were helpful in understanding the role of biogeochemical processes (Carpenter et al., 1995).

Radionuclides • During this period it was proposed to use nuclear weapons to make a new Panama Canal. This was done under the general slogan of "Atoms for Peace". • Studies and concerns relating to the transport and fate of radionuclides associated with the testing of atomic weapons aided in analysis of elemental dynamics of ecosystems. • Work at Oak Ridge (Tenn.) on the cycling of cesium was notable. (Today we use “bomb-C to trace carbon cycle). • More recently the events at Chernobyl in the Ukraine had a major influence on environmental awareness related to nuclear reactors. The use of nuclear power has for the generation of electricity continues to be controversial.

SCOPE During the period (mid-1970's) there were also international efforts coordinated through SCOPE (Scientific Committee on Problems of the Environment) and sponsored through the United Nations. The efforts of this group continue today with a SCOPE group on nitrogen being active and recently finishing a synthesis on regional nitrogen budgets.

Green Revolution • Important in stimulating interest in developing countries with much of the emphasis on developing cultivars and use of fertilizer and pesticides. • Most recent concerns have focused on genetic engineering and concerns about how genetically engineered crops may interfere with non-target organisms (Bt crop threat to monarch butterfly). The use of genetically engineered crops has been more accepted in North America compared to Europe.

Gaia • Some parameters of the earth (temperature, composition of the ocean, atmospheric composition) have remained remarkably constant • Gaia Hypothesis --earth is a giant system composed of all organisms, atmosphere, seas and land surface and this gigantic system has the properties characteristic of an organism • Named Gaia after the Greek Earth goddess. • Proposed by Lovelock(chemical engineer, invented electron capture detector) • More recently Lovelock has championed “geophysiology” which views the biota and physical world as part of a global system capable of environmental regulation. Unlike the original Gaia hypothesis there are no teleological (organisms purposefully caused these conditions) demands placed on the biota. • This global system has also been termed the ecosphere.

Acid Rain • In the 1980's the major stimulus for biogeochemical research focused on "Acid Rain". Some of the major results have been summarized in NAPAP(National Acid Precipitation Assessment Program)documents. • Most recent international acid rain meeting was held in Japan (December 2000) with the next meeting to be held in Prague (2005). • Major attention with respect to acid rain and global pollution is shifting to the Far East, especially China with respect to increasing impacts. There is interest in North America and Europe on recovery of ecosystems from acid rain.

Historical Air Pollution • Pliny the Elder (23-79AD) mentioned saline rain damage to crops. • Hildegard von Bingen [1140AD] indicated that dust unhealthy for plants. • John Evelyn [1661] documented that SO2 damages plants. • Fabri [1670]indicated that volcanic acid rain damaged fruit. • Transport of air born pollutants --in Norway it was reported by Brand (1865) that “Britain’s suffocating coal dust is slowly descending over the country side, soiling all that is green, strangling all that strives to grow, creeping low and mixed with poison, stealing sun and light from the green valley . . . ”.

Historical Air Pollution Also records from Asia Hiroshige: Lime kilns at Hashiba Ferry, Sumida River One Hundred Famous Views of Edo; from Peter Brimblecombe

Historical Overview