Jan Gilkrich Pahkiat

BSCE 1

Sulfur Reservoirs in Nature Reservoirs of sulfur:

The largest physical reservoir is the Earth's crust where sulfur is found in gypsum
(CaSO4) and pyrite (FeS2). The largest reservoir of biologically useful sulfur is found in
the ocean as sulfate anions (2.6 g/L), dissolved hydrogen sulfide gas, and elemental
sulfur.
•Other reservoirs include:
-Freshwater -contains sulfate, hydrogen sulfide and elemental sulfur

Land -contains sulfate -Atmosphere -contains sulfur oxide (SO2) and methane 2 sulfonic
acid (CH3SO3-); volcanic activity releases some hydrogen sulfide into the air.
Sulfur in Fossil Fuels

Human impact on the sulfur cycle is primarily in the production of sulfur dioxide
(SO2) from industry (e.g. burning coal) and the internal combustion engine. Sulfur dioxide
can precipitate onto surfaces where it can be oxidized to sulfate in the soil onto surfaces
where it can be oxidized to sulfate in the soil (it is also toxic to some plants), reduced to
sulfide in the atmosphere, or oxidized to sulfate in the atmosphere as sulfuric acid a
principal component of acid rain .
Igneous Rocks

Most igneous rocks crystallize from molten silicate (oxygen and silicon) magmas
and thus, the minerals in them are most often silicate or oxide minerals such as olivine,
pyroxene, feldspar, mica, amphibole, quartz, and iron-titanium oxides. There are two
subtypes of igneous rocks, those that crystallize below the surface of the Earth (called
intrusive) and those that are erupted and crystallize on or above the surface (called
volcanic). Those that crystallize below the surface cool slowly resulting in larger grains of
minerals whereas those that crystallize on or above the surface cool quickly resulting in
fine grain size or if quenched resulting in glass. There are different names for igneous
rocks based on whether it is intrusive or volcanic and its chemical composition which
determines the type of minerals in the rock.
Sedimentary Rocks

Most sedimentary rocks form from the products of weathering (by water, wind, and
ice) of other rocks at the surface of the Earth which are either solid minerals or solid
minerals that are dissolved into ions in water. There are two subtypes of sedimentary
rocks, those are dominantly composed of the solid weathering products (called clastic)
and those that form from the dissolved ions precipitating from water (precipitates). Those
clastic sedimentary rocks are made up of the clasts of minerals in the rock being
weathered that are not dissolved and new minerals formed from the breakdown of original
minerals during weathering. The precipitates are made up of minerals precipitated from
water (ocean or fresh). Loose sedimentary mineral grains become rock during burial
through processes termed lithification.
Metamorphic Rocks
 Metamorphic rocks form when a pre-existing rock is changed in response to
application of significant temperature and pressure (above those found at the surface of
the Earth) in the presence of water based fluids over long periods of time. The minerals
in a metamorphic rock depends on the original minerals in the pre-existing rock and the
new minerals that grow during metamorphism. The new minerals that grow during
metamorphism depend on the chemical components available in the rock being
metamorphosed and the temperature and pressure conditions and metamorphic rocks
are divided by the new metamorphic minerals and the texture of the rock. Metamorphic
temperatures and pressures range from those conditions found near the surface to hot
enough and deep enough that the pre-existing rock melts to become magma.
Cycling of Rocks

The rock cycle describes the progression of rocks that we see on the surface of
the Earth. The entire outer skin of the Earth was once all molten and as the Earth cooled
igneous rocks began to form from crystallization of magmas. The process of plate
tectonics cycled early formed rocks back into the Earth where they underwent
metamorphism and some of them melted to form magmas. As the atmosphere developed
weathering began and sedimentary rocks became part of the cycle.

Today the outer ring of the rock cycle is best described as igneous rocks forming from
crystallization of magmas and at the surface of the Earth these igneous rocks are
weathered to form the clastic and precipitates of sedimentary rocks. These sedimentary
rocks are progressively buried and undergo metamorphism and at high enough
temperature and pressure melt to form magmas and the cycle starts over again. The cycle
can be short cut too. Igneous rocks can undergo metamorphism skipping the weathering
step and metamorphic rocks rather than melting can be brought back up to the surface to
be weathered into sedimentary rocks.
Rocks of Intermediate Type

Rocks are not always easily placed into the categories, igneous, sedimentary, and
metamorphic. For example, there is no exact cutoff for when the temperature and
pressure is significant enough that a rock is said to be metamorphic. When a sand is
buried it becomes compressed and heated above surface air temperature and during this
process it becomes lithified into sandstone.
Phosphorus cycling in soils

The cycling of Pins oils has received much attention, in terms of both fertilization
and the natural development of ecosystems. Of the approximately 122,600 Tg P within
the soil/biota system on the continents, nearly 98% is held in soils in a variety of forms.
The exchange of P between biota and soils is relatively rapid, with an average residence
time of 13 years, whereas the average residence time of P in soils is 600 years

The most significant weathering source for phosphorus in soils are apatite
minerals. These minerals can be congruently weathered as a result of reaction with
dissolved carbon dioxide. In soils, P is released from mineral grains by several processes.
First, the reduced pH produced from respiration-related CO2 in the vicinity of both
degrading organic matter and root hairs dissolves P-bearing minerals (mainly apatites)
and releases P to root pore spaces. Second, organic acids released by plant roots also
can dissolve apatite minerals and release P to soil pore spaces (Jurinak et al., 1986).
Phosphorus is very immobile in most soils, and its slow rate of diffusion from dissolved
form in pore spaces strongly limits its supply to rootlet surfaces. Furthermore, much of
the available P in soils is in organic matter, which is not directly accessible for plant
nutrition. Plants have developed two specific tactics to increase the supply of P to roots.
Phosphatase, an enzyme that can release bioavailable inorganic P from organic matter,
is often excreted by plants and soil microbes, and the symbiotic fungi Mycorrhizae can
coat plant rootlets, excreting phosphatase and organic acids to release P and providing
an active uptake site for rapid diffusion of P from soil pore spaces to root surfaces (e.g.,
Schlesinger, 1997). Phosphorus in soils is present in a variety of forms, and the
distribution of P between these forms changes dramatically with time and soil
development. The forms of soil P can be grouped into refractory (not readily bioavailable)
and labile (readily bioavailable). The refractory forms include P in apatite minerals and P
co-precipitated with and/or adsorbed onto iron and manganese oxyhydroxides (termed
“occluded” P). The reducible oxyhydroxides have large binding capacities for phosphate,
due to their immense surface area and numerous delocalized positively charged sites
(e.g., Froelich, 1988). The labile forms include P in soil pore spaces (as dissolved
phosphate ion) and adsorbed onto soil particle surfaces (these forms are termed
“nonoccluded” P), as well as P incorporated in soil organic matter. On a newly-exposed
lithic surface, nearly all of the P is present as P in apatite. With time and soil development,
however, P is increasingly released from this form and incorporated in the others. Over
time, the total amount of of the sea are exceedingly low. Thus, much of the net P
physically eroded from continents is delivered relatively unaltered to the oceans, where it
is sedimented on continental margins and in the deep sea, until subduction or accretion
eventually returns P to be exposed on land again. Some of the particulate P is adsorbed
onto soil surfaces, held within soil oxide, and incorporated into particulate organic matter.
This P likely interacted with the biotic P cycle on land, and its fate upon transfer to the
ocean is poorly understood. For example, P adsorbed onto soil surfaces may be
effectively displaced by the high ionic strength of ocean water, providing an additional
source of P into the ocean. Furthermore, a small amount of the P incorporated into
terrestrial organic matter may be released in certain environments during bacterial
oxidation after sediment burial. Finally, some sedimentary environments along
continental margins are suboxic or even anoxic, conditions favorable for oxide dissolution
and release of the incorporated P. The net pre-human flux of dissolved P to the oceans
is 1 Tg P yr –1, with an additional 1–2 Tg P yr –1 of potentially
soluble P, bringing the total to about 2–3 Tg P yr –1. Thus, the residence time of
biologically available P on land is about 40–60 kyr with respect to export to the oceans.
That this residence time is of a glacial timescale may be no coincidence, and is likely tied
to variable inputs from continental weathering and output sinks driven by sea level
variations. However, the interaction between biologically available P on land and loss of
this P to the oceans is clearly relatively dynamic and suggests the relatively rapid cycling
of P on land.