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Anoxic waters

Anoxic waters are areas of sea water or fresh water that are depleted of dissolved oxygen. This condition is generally found in areas that have restricted water exchange. In most cases, oxygen is prevented from reaching the deeper levels by a physical barrier (silt) as well as by a pronounced density stratification, in which, for instance, heavier hypersaline waters rest at the bottom of a basin. Anoxic conditions will occur if the rate of oxidation of organic matter by bacteria is greater than the supply of dissolved oxygen. Anoxic waters are a natural phenomenon,[1] and have occurred throghout geological history. Anoxic basins exist at present, for example, in the Baltic Sea,[2] and elsewhere (see below). Recently, there have been some indications that eutrophication has increased the extent of the anoxic areas in areas including the Baltic Sea, and the Gulf of Mexico.[3]

Causes and effects


Anoxic conditions result from several factors; for example, stagnation conditions, [4] density stratification, inputs of organic material, and strong thermoclines. The bacterial production of sulfide starts in the sediments, where the bacteria find suitable substrates, and then expands into the water column.

When oxygen is depleted in a basin, bacteria first turn to the second-best electron acceptor, which in sea water is nitrate. Denitrification occurs, and the nitrate will be consumed rather rapidly. After reducing some other minor elements, the bacteria will turn to reducing sulfate. If anoxic sea water becomes reoxygenized, sulfides will be oxidized to sulfate according to the chemical equation: HS + 2 O2 HSO4 In the Baltic Sea the slowed rate of decomposition under anoxic conditions has left remarkably preserved fossils retaining impressions of soft body parts, in Lagersttten.

Anoxic event

As early as 1911, major oceanic currents were well mapped and understood, albeit without today's understanding of how they affect regional and global climatological conditions.

This world perspective on oceanic currents demonstrates the interdependencies of transnational regions on circulating currents. Oceanic anoxic events or anoxic events occur when the Earth's oceans become completely depleted of oxygen (O2) below the surface levels. Although anoxic events have not happened for millions of years, the geological record shows that they happened many times in the past. Anoxic events may have caused mass extinctions.[citation needed] These mass extinctions were so characteristic they include some of those which geobiologists employ to serve as a time marker in biostratigraphic dating. It is believed[by whom?] oceanic anoxic events are strongly linked to lapses in key oceanic current circulations, to climate warming and greenhouse gases.

Occurrence
Oceanic anoxic events most commonly occurred during periods of very warm climate characterized by high levels of carbon dioxide (CO2) and mean surface temperatures probably in excess of 25 C (77 F). The Quaternary levels, our current period, are just 13 C (55 F) in comparison. Such rises in carbon dioxide may have been in response to a great outgassing of the highly flammable natural gas (methane) some have christened an "oceanic burp".[2][4] Vast quantities of methane are normally locked into the Earth's crust on the continental plateaus in one of the many deposits consisting of compounds of methane hydrate, a solid precipitated combination of methane and water much like ice. Because the methane hydrates are unstable, save at cool temperatures and high (deep) pressures, scientists have observed smaller "burps" due to tectonic events. Studies suggest the huge release of natural gas[4] could be a major climatological trigger, methane itself being a greenhouse gas many times more powerful than carbon dioxide. However, anoxia was also rife during the Hirnantian (late Ordovician) ice age. Oceanic anoxic events have been recognized primarily from the already warm Cretaceous and Jurassic Periods, when numerous examples have been documented,[6][7] but earlier examples have been suggested to have occurred in the late Triassic, Permian, Devonian (Kellwasser event/s), Ordovician and Cambrian. The PaleoceneEocene Thermal Maximum (PETM), which was characterized by a global rise in temperature and deposition of organic-rich shales in some shelf seas, shows many similarities to oceanic anoxic events. Typically, oceanic anoxic events last for under half a million years, before a full recovery.

Consequences
Oceanic anoxic events have had many important consequences. It is believed that they have been responsible for mass extinctions of marine organisms both in the Paleozoic and Mesozoic.[8] The early Toarcian and Cenomanian-Turonian anoxic events correlate with the Toarcian and Cenomanian-Turonian extinction events of mostly marine life forms. Apart from possible atmospheric effects, many deeperdwelling marine organisms could not adapt to an ocean where oxygen penetrated only the surface layers. Another, economically significant consequence of oceanic anoxic events is the fact that the prevailing conditions in so many Mesozoic oceans has helped produce most of the world's petroleum and natural gas reserves. During an oceanic anoxic event, the accumulation and preservation of organic matter was much greater than normal, allowing the generation of potential petroleum source rocks in many environments across the globe. Consequently some 70 percent of oil source rocks are Mesozoic in age, and another 15 percent date from the warm Paleogene: only rarely in colder periods were conditions favorable for the production of source rocks on anything other than a local scale.

Major oceanic anoxic events

Jurassic and Cretaceous The timeline data of the Jurassic and Cretaceous The concept of the oceanic anoxic event (OAE) was first proposed in 1976 by Seymour Schlanger (19271990) and geologist Hugh Jenkyns[9] and arose from discoveries made by the Deep Sea Drilling Project (DSDP) in the Pacific Ocean. It was the finding of black carbon-rich shales in Cretaceous sediments that had accumulated on submarine volcanic plateaus (Shatsky Rise, Manihiki Plateau), coupled with the fact that they were identical in age with similar deposits cored from the Atlantic Ocean and known from outcrops in Europe - particularly in the geological record of the otherwise limestone-dominated Apennines[9] chain in Italy - that led to the realization that these widespread intervals of similar strata recorded highly unusual oxygen-depleted conditions in the world ocean during several distinct discrete periods of geological time. Sedimentological investigations of these organic-rich sediments, which have continued to this day, typically reveal the presence of fine laminations undisturbed by bottom-dwelling fauna, indicating anoxic conditions on the sea floor, believed to be coincident with a low lying poisonous layer of hydrogen sulfide.[1] Furthermore, detailed organic geochemical studies have recently revealed the presence of molecules (so-called biomarkers) that derive from both purple sulfur bacteria[1] and green sulfur bacteria: organisms that required both light and free hydrogen sulfide (H2S), illustrating that anoxic conditions extended high into the illuminated upper water column. Such sulfidic (or euxinic) conditions, which exist today in many water bodies from ponds to various land-surrounded mediterranean seas[10] such as the Black Sea of today, were particularly prevalent in the Cretaceous Atlantic but also characterized other parts of the world ocean. In an ice-free sea of these supposed super-greenhouse worlds, oceanic waters were as much as 200 meters higher, in some eras. During the time spans in question, the continental plates are believed to have been well separated, and the mountains we know today were (mostly)

future tectonic eventsmeaning the overall landscapes were generally much lower and even the half super-greenhouse climates would have been eras of highly expedited water erosion[1] carrying massive amounts of nutrients into the world oceans fueling an overall explosive population of microorganisms and their predator species in the oxygenated upper layers. Detailed stratigraphic studies of Cretaceous black shales from many parts of the world have indicated that two oceanic anoxic events were particularly significant in terms of their impact on the chemistry of the oceans, one in the early Aptian (~120 Ma), sometimes called the Selli Event (or OAE 1a) after the Italian geologist, Raimondo Selli (19161983), and another at the CenomanianTuronian boundary (~93 Ma), sometimes called the Bonarelli Event (or OAE 2) after the Italian geologist, Guido Bonarelli (18711951). Insofar as the Cretaceous OAEs can be represented by type localities, it is the striking outcrops of laminated black shales within the vari-colored claystones and pink and white limestones near the town of Gubbio in the Italian Apennines that are the best candidates. The 1-meter thick black shale at the CenomanianTuronian boundary that crops out near Gubbio is termed the Livello Bonarelli after the man who first described it in 1891. More minor oceanic anoxic events have been proposed for other intervals in the Cretaceous (in the Valanginian, Hauterivian, Albian and ConiacianSantonian stages), but their sedimentary record, as represented by organic-rich black shales, appears more parochial, being dominantly represented in the Atlantic and neighboring areas, and some researchers relate them to particular local conditions rather than being forced by global change. The only oceanic anoxic event documented from the Jurassic took place during the early Toarcian (~183 Ma).[6][7] Because no DSDP or ODP (Ocean Drilling Program) cores have recovered black shales of this age there being little or no Toarcian ocean crust remaining in the world ocean the samples of black shale primarily come from outcrops on land. These outcrops, together with material from some commercial oil wells, are found on all major continents and this event seems similar in kind to the two major Cretaceous examples.

Atmospheric effects
A model put forward by Lee Kump, Alexander Pavlov and Michael Arthur in 2005 suggests that oceanic anoxic events may have been characterized by upwelling of water rich in highly toxic hydrogen sulfide gas which was then injected into the atmosphere. This phenomenon would likely have poisoned plants and animals and caused mass extinctions. Furthermore, it has been proposed that the hydrogen sulfide rose to the upper atmosphere and attacked the ozone layer, which normally

blocks the deadly ultraviolet radiation of the Sun. The increased UV radiation caused by this ozone depletion would have amplified the destruction of plant and animal life. Fossil spores from strata recording the Permian extinction show deformities consistent with UV radiation. This evidence, combined with fossil biomarkers of green sulfur bacteria, indicates that this process could have played a role in that mass extinction event, and possibly other extinction events. The trigger for these mass extinctions appears to be a warming of the ocean caused by a rise of carbon dioxide levels to about 1000 parts per million.[15]

Hypoxia (environmental)
Hypoxia, or oxygen depletion, is a phenomenon that occurs in aquatic environments as dissolved oxygen (DO; molecular oxygen dissolved in the water) becomes reduced in concentration to a point where it becomes detrimental to aquatic organisms living in the system. Dissolved oxygen is typically expressed as a percentage of the oxygen that would dissolve in the water at the prevailing temperature and salinity (both of which affect the solubility of oxygen in water; see oxygen saturation and underwater). An aquatic system lacking dissolved oxygen (0% saturation) is termed anaerobic, reducing, or anoxic; a system with low concentrationin the range between 1 and 30% saturationis called hypoxic or dysoxic. Most fish cannot live below 30% saturation. A "healthy" aquatic environment should seldom experience less than 80%. The exaerobic zone is found at the boundary of anoxic and hypoxic

Where hypoxia occurs

Hypoxia can occur throughout the water column and also at high altitudes as well as near sediments on the bottom. It usually extends throughout 20-50% of the water column, but depending on the water depth and location of pycnoclines

(rapid changes in water density with depth)[1] it can occur in 10-80% of the water column. For example, in a 10-meter water column, it can reach up to 2 meters below the surface. In a 20-meter water column, it can extend up to 8 meters below the surface.[2] Hypoxia can also occur outside of an aquatic environment, in conditions where the oxygen content of the air is reduced. This is common, for example, in the sealed burrows of some subterranean animals, such as blesmols.[3]

Causes of hypoxia

Decline of oxygen saturation to anoxia, measured during the night in Kiel Fjord, Germany. Depth = 5 m Oxygen depletion can result from a number of natural factors, but is most often a concern as a consequence of pollution and eutrophication in which plant nutrients enter a river, lake, or ocean, and phytoplankton blooms are encouraged. While phytoplankton, through photosynthesis, will raise DO saturation during daylight hours, the dense population of a bloom reduces DO saturation during the night by respiration. When phytoplankton cells die, they sink towards the bottom and are decomposed by bacteria, a process that further reduces DO in the water column. If oxygen depletion progresses to hypoxia, fish kills can occur and invertebrates like worms and clams on the bottom may be killed as well.

Still frame from an underwater video of the sea floor. The floor is covered with crabs, fish, and clams apparently dead or dying from oxygen depletion. Hypoxia may also occur in the absence of pollutants. In estuaries, for example, because freshwater flowing from a river into the sea is less dense than salt water, stratification in the water column can result. Vertical mixing between the water bodies is therefore reduced, restricting the supply of oxygen from the surface waters to the more saline bottom waters. The oxygen concentration in the bottom layer may then become low enough for hypoxia to occur. Areas particularly prone to this include shallow waters of semi-enclosed water bodies such as the Waddenzee or the Gulf of Mexico, where land run-off is substantial. In these areas a so-called "dead zone" can be created. The World Resources Institute has identified 375 hypoxic coastal zones around the world, concentrated in coastal areas in Western Europe, the Eastern and Southern coasts of the US, and East Asia, particularly in Japan.[4]

Jubilee photo from Mobile Bay Hypoxia may also be the explanation for periodic phenomena such as the Mobile Bay jubilee, where aquatic life suddenly rushes to the shallows, perhaps trying to escape oxygen-depleted water. Recent widespread shellfish kills near the coasts of Oregon and Washington are also blamed on cyclic dead zone ecology.[5]

Solutions
To combat hypoxia, it is essential to reduce the amount of land-derived nutrients reaching rivers in runoff. Defensively this can be done by improving sewage treatment and by reducing the amount of fertilizers leaching into the rivers. Offensively this can be done by restoring natural environments along a river; marshes are particularly effective in reducing the amount of phosphorus and nitrogen (nutrients) in water. Technological solutions are also possible, such as that used in the redeveloped Salford Docks area of the Manchester Ship Canal in England, where years of runoff from sewers and roads had accumulated in the slow running waters. In 2001 a compressed air injection system was introduced, which raised the oxygen levels in the water by up to 300%. The resulting improvement in water quality led to an increase in the number of invertebrate species, such as freshwater shrimp, to more than 30. Spawning and growth rates of fish species such as roach and perch also increased to such an extent that they are now amongst the highest in England.
[6]

Graphs of oxygen and salinity levels at Kiel Fjord in September 1998. In a very short time the oxygen saturation can drop to zero when offshore blowing winds drive surface water out and anoxic depthwater rises up. At the same time a decline in temperature and a rise in salinity is observed (from the longterm ecological observatory in the seas at Kiel Fjord, Germany). New approaches of long-term monitoring of oxygen regime in the ocean observe online the behavior of fish and zooplankton, which changes drastically under reduced oxygen saturations (ecoSCOPE) and already at very low levels of water pollution.

Bog chemistry
In certain northern European sphagnum acidic bogs, a condition of hypoxia arises that prevents tissue decay by impeding micro-organisms in the soil and groundwater. Remarkable preservation of human mummies has occurred in some cases such as the discovery of Haraldskr Woman and Tollund Man in Jutland, Denmark and Lindow man in Cheshire, England. Ocean deoxygenation Ocean deoxygenation is a term that has been suggested to describe the expansion of oxygen minimum zones in the world's oceans as a consequence of anthropogenic emissions of carbon dioxide [1]. Oceanographers and others have discussed what phrase best describes the phenomenon to non-specialists. Among the options considered have been 'ocean suffocation' (which was used in a news report from May 2008 [2]), 'ocean oxygen

deprivation' [3], 'decline in ocean oxygen', 'marine deoxygenation', 'ocean oxygen depletion' and 'ocean hypoxia'

Dead zone (ecology) .

Red circles show the location and size of many dead zones. Black dots show dead zones of unknown size. The size and number of marine dead zonesareas where the deep water is so low in dissolved oxygen that sea creatures cant survivehave grown explosively in the past half-century. NASA Earth Observatory[1] Dead zones are hypoxic (low-oxygen) areas in the world's oceans, the observed incidences of which have been increasing since oceanographers began noting them in the 1970s. These occur near inhabited coastlines, where aquatic life is most concentrated. (The vast middle portions of the oceans which naturally have little life are not considered "dead zones".) The term can also be applied to the identical phenomenon in large lakes. In March 2004, when the recently established UN Environment Programme published its first Global Environment Outlook Year Book (GEO Year Book 2003) it reported 146 dead zones in the world's oceans where marine life could not be supported due to depleted oxygen levels. Some of these were as small as a square kilometre (0.4 mi), but the largest dead zone covered 70,000 square kilometres (27,000 mi). A 2008 study counted 405 dead zones worldwide.[2][3]

Causes

Dead zones are often caused by the decay of algae during algal blooms, like this one off the coast of La Jolla, San Diego, California.

Climate has a significant impact on the growth and decline of ecological dead zones. During Spring months, as rainfall increases, more nutrient rich water flows down the mouth of the Mississippi River. At the same time, as sunlight increases during the Spring, algal growth in the dead zones increases dramatically. In Fall months, tropical storms begin to enter the Gulf of Mexico and break up the dead zones and the cycle repeats again in the spring. Aquatic and marine dead zones can be caused by an increase in chemical nutrients (particularly nitrogen and phosphorus) in the water, known as eutrophication. These chemicals are the fundamental building blocks of single-celled, plant-like organisms that live in the water column, and whose growth is limited in part by the availability of these materials. Eutrophication can lead to rapid increases in the density of certain types of these phytoplankton, a phenomenon known as an algal bloom. Although these algae produce oxygen in the daytime via photosynthesis, during the night hours they continue to undergo cellular respiration and can therefore deplete the water column of available oxygen.[citation needed] In addition, when algal blooms die off, oxygen is used up further during bacterial decomposition of the dead algal cells. Both of these processes can result in a

significant depletion of dissolved oxygen in the water, creating hypoxic conditions. Dead zones can be caused by natural and by anthropogenic factors. Use of chemical fertilizers is considered the major human-related cause of dead zones around the world. Natural causes include coastal upwelling and changes in wind and water circulation patterns. Runoff from sewage, urban land use, and fertilizers can also contribute to eutrophication.[4] Notable dead zones in the United States include the northern Gulf of Mexico region, surrounding the outfall of the Mississippi River, and the coastal regions of the Pacific Northwest, and the Elizabeth River in Virginia Beach, all of which have been shown to be recurring events over the last several years. Additionally, natural oceanographic phenomena can cause deoxygenation of parts of the water column. For example, enclosed bodies of water such as fjords or the Black Sea have shallow sills at their entrances causing water to be stagnant there for a long time. The eastern tropical Pacific Ocean and Northern Indian Ocean have lowered oxygen concentrations which are thought to be in regions where there is minimal circulation to replace the oxygen that is consumed (e.g. Pickard & Emery 1982, p 47).[5] These areas are also known as Oxygen Minimum Zones (OMZ). In many cases OMZ's are permanent or semi-permanent areas. Remains of organisms found within sediment layers near the mouth of the Mississippi River indicate four hypoxic events before the advent of artificial fertilizer. In these sediment layers, anoxia-tolerant species are the most prevalent remains found. The periods indicated by the sediment record correspond to historic records of high river flow recorded by instruments at Vicksburg, Mississippi.

Effects

Underwater video frame of the sea floor in the Western Baltic covered with dead or dying crabs, fish and clams killed by oxygen depletion Low oxygen levels recorded along the Gulf Coast of North America have led to reproductive problems in fish involving decreased size of reproductive organs, low egg counts and lack of spawning. In a study of the Gulf killifish by the Southeastern Louisiana University done in three bays along the Gulf Coast, fish living in bays where the oxygen levels in the water dropped to 1 to 2 parts per million (ppm) for 3 or more hours per day were found to have smaller reproductive organs. The male gonads were 34% to 50% as large as males of similar size in bays where the oxygen levels were normal (6 to 8 ppm). Females were found to have ovaries that were half as large as those in normal oxygen levels. The number of eggs in females living in hypoxic waters were only one-seventh the number of eggs in fish living in normal oxygen levels. (Landry, et al., 2004) Fish raised in laboratory-created hypoxic conditions showed extremely low sexhormone concentrations and increased elevation of activity in two genes triggered by the hypoxia-inductile factor (HIF) protein. Under hypoxic conditions, HIF pairs with another protein, ARNT. The two then bind to DNA in cells, activating genes in those cells. Under normal oxygen conditions, ARNT combines with estrogen to activate genes. Hypoxic cells in a test tube didn't react to estrogen placed in the tube. HIF appears to render ARNT unavailable to interact with estrogen, providing a mechanism by which hypoxic conditions alter reproduction in fish. (Johanning, et al., 2004) It might be expected that fish would flee this potential suffocation, but they are often quickly rendered unconscious and doomed. Slow moving bottom-dwelling creatures like clams, lobsters and oysters are unable to escape. All colonial animals are extinguished. The normal re-mineralization and recycling that occurs among benthic life-forms is stifled.

Locations

DRAINAGE SYSTEM OF ANOXIC WATER

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