Red Sea Water Chemistry
2017-05-31
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Red Sea Sea Water Chemistry Introduction and background knowledge before diving in The following pages provide more information on: • • • • • Background to Sea Water Composition of Sea Water Explanation of life support parameters Salinity (S.G.), pH Important elements in salt - Alkalinity, Calcium, Magnesium, others Undesirable nutrients - Phosphates, Nitrates Background to Sea Water Having a successful coral reef aquarium is dependent upon maintaining the physical and chemical water parameters of a natural reef environment. Therefore the choice of reef-salt formula is the most fundamental issue in the setup of any seawater aquarium. Sea water is not just a solution of sodium chloride (table salt) and water, but is a complex mixture of virtually every substance that can be found on earth. Latest studies have identified up to 80 elements in oceanic sea water, however the elemental composition around the thriving natural reefs vary slightly to the open ocean. While much is already known, the effect of many of these elements in the physiology of marine life is yet to be determined providing the basis for ongoing research. The correct level, in particular regarding trace elements can be critical. For example, very small amounts of copper, precisely those amounts normally found in natural sea water, are absolutely necessary for the correct functioning of the respiratory pigment in arthropods and mollusks. However, a slight increase in the amount of copper in the water surrounding the organisms will result in a similar increase in the internal cellular environment resulting in the denaturation of other cellular agents, killing these same organisms. Red Sea | Sea Water Chemistry Red Sea Red Sea | Sea Water Chemistry Bio-tech note: At the basic cellular level, all life is dependent upon the proper functioning of a complex series of coupled chemical reactions. These reactions are regulated and controlled by specific biological agents whose capabilities are determined by the properties of the internal cellular environment. In many marine creatures, the internal cellular environment is directly dependent upon the sea water medium that surrounds the organism. Changes in salinity, for example, are often directly responsible for changes in cellular metabolism. Additionally, chemicals dissolved in the sea water medium may directly affect the cellular functionality. This is particularly true of metal ions in sea water. In the proper amounts, various metal ions ensure that the biological agents are of the correct shape and have the appropriate function. When found in the wrong concentrations, however, many metal ions may interfere with, and change, the structures of the biological agents. These changes generally cause serious problems to the organism. Recommended parameters of artificial salt water Parameter Artificial salt water NSW 33-36 ppt Variable 8.2-8.4 8.0-8.3 2.5-4.5 meq./l 7-15dKH 2.5 meq/l 7 dKH 410 -460ppm 420 ppm 1250-1400ppm 1280 ppm Potassium * 380-410 ppm 390 ppm Phosphate < 0.1ppm 0.005ppm Ammonia < 0.1ppm Variable (typically < 0.1ppm) Nitrite < 0.2ppm Variable (typically < 0.0001ppm) Nitrate < 1 ppm Variable (typically < 0.1ppm) Silica < 2ppm < 0.06 – 2.7ppm Strontium 7-12ppm 8ppm 0.01-0.1ppm 0.000006ppm 0.05 – 0.07 ppm 0.06ppm total of all forms Salinity pH Alkalinity * Calcium * Magnesium * Iron Iodine * Dependant on Marine (fish only) or Coral Reef Aquarium. Due to the significant difference between the natural reef environment and the artificial reef system in the availability of elements some parameters must be maintained at levels different to those found in NSW Red Sea | Sea Water Chemistry Red Sea Red Sea | Sea Water Chemistry The composition of sea water Chemical elements in seawater are commonly grouped into three general categories: major, minor and trace. The distinction between the categories is arbitrary and different authors will use different concentrations for the dividing lines. Note: The following tables relate to an elemental analysis of seawater. This is not a formula of chemicals used to create a sea salt mix. Salt Water Major Minor Major elements >100ppm Trace 100ppm < Minor elements < 0.5ppm Chloride (Cl-)* 19353 Bromide (Br-)* Sodium (Na+)* 10781 Carbon Sulfate (SO4--)* 2712 Strontium (Sr+) Magnesium (Mg++)* 1284 Boron Calcium (Ca++) 419 Fluoride (F-)* Potassium (K+)* 390 Silicone 67 28 8.5 4.6 1.3 0.5 Trace elements: Element Symbol ppm Element Symbol ppm Element Symbol ppm LITHIUM Li 0.178 MANGANESE Mn 0.0003 RHENIUM Re 0.000004 RUBIDIUM Rb 0.12 ANTIMONY Sb 0.0002 THALLIUM Th 0.000002 IODINE I 0.06 COPPER Cu 0.0002 BERYLLIUM Be 0.000001 BARIUM Ba 0.05 URANIUM U 0.00015 DYSPROSIUM Dy 0.0000009 SELENIUM Se 0.004 CADIUM Cd 0.0001 ERBIUM Er 0.0000008 ARSENIC As 0.002 TUNGSTEN W 0.0001 YTTERBIUM Yb 0.0000008 CESIUM Cs 0.002 COBALT Co 0.00007 GADOLINIUM Gd 0.0000007 ZIRCONIUM Zr 0.0014 GERMANIUM Ge 0.00005 RUTHENIUM Ru 0.0000007 VANADIUM V 0.0012 SCANDIUM Sc 0.00004 PLATINUM Pt 0.0000006 ALUMINIUM Al 0.001 GOLD Au 0.00003 PRAESIDIUM Pr 0.0000006 MOLYBDENUM Mo 0.001 INDIUM In 0.00003 THULIUM Tm 0.0000002 NICKEL Ni 0.0007 TIN Sn 0.00003 BISMUTH Bi 0.0000001 IRON Fe 0.0005 SILVER Ag 0.00002 TERBIUM Tb 0.0000001 ZINC Zn 0.0005 YTTRIUM Y 0.000013 TITANIUM Ti 0.0000001 CERIUM Ce 0.0004 NIOBIUM Nb 0.00001 SAMARIUM Sm 0.00000005 CHROMIUM Cr 0.0004 HOLMIUM Ho 0.000008 EUROPIUM Eu 0.00000002 LEAD Pb 0.0004 HAFNIUM Hf 0.000007 RADIUM Ra 0000000001 GALLIUM Ga 0.0003 TANTALUM Ta 0.000007 LANTHANUM La 0.0003 MERCURY Hg 0.000005 Red Sea | Sea Water Chemistry Red Sea Red Sea | Sea Water Chemistry Life Support Parameters - Salinity The recommended salinity in a coral reef tank for optimal calcification: 33-36 ppt. The recommended salinity in a fish only tank: 30-38 ppt. Salinity must be monitored at least twice per week. The natural evaporation of the H2O from the sea water in an aquarium, unless replenished regularly will cause an increase in the salinity of the aquarium water. Salinity is critical to the health of marine organisms because of the process of osmoregulation that enables the organism to maintain the correct level of dissolved ions inside the body fluids. Salinity has a direct influence on marine organism’s metabolism and internal processes such as coral calcification. Bio-tech note: Osmoregulation is the active regulation of the osmotic pressure of an organism’s fluids to maintain the homeostasis of the organism’s water content; that is it keeps the organism’s fluids from becoming too dilute or too concentrated. Osmotic pressure is a measure of the tendency of water to move into one solution from another through a membrane by osmosis. The higher the osmotic pressure of a solution the more water wants to move into the solution. Pressure must be exerted on the “higher salinity” side of a selectivelypermeable membrane to prevent diffusion of water by osmosis from the “lower salinity” side. Organisms that are exposed to an environment with the incorrect salinity will be under stress as they will be expending a disproportionate amount of energy in maintaining their osmotic Definition and Measuring salinity Salinity is the summery of the mass of all of the dissolved salts in specified volume of water. It is expressed in terms of ppt (part per thousand) = g/L (gram per liter) = ‰ = psu, and can be measured with a refractometer or a Conductivity meters (mS). The more common method in the hobby is measuring the Specific Gravity or S.G. which is the ratio of the density of the salt water solution and the density of the same volume of pure water at 4°C. S.G. doesn’t have units and it is measured by hydrometer. The S.G. measurement is temperature dependant and therefore it is a meaningless number without knowing the actual temperature of the water sample. Note: A solution with a fixed salinity will have a lower S.G at a higher temperature. Red Sea | Sea Water Chemistry Red Sea Red Sea | Sea Water Chemistry Table showing the salinity from a known S.G, and temperature: Observed Reading 25.0 25.5 26 26.5 27 27.5 28 28.5 29 29.5 30 1.0210 30.2 30.3 30.6 30.7 30.9 31.1 31.3 31.5 31.7 32.0 32.1 1.0220 31.5 31.7 31.9 32.0 32.2 32.5 32.6 32.9 33.0 33.3 33.4 1.0230 32.8 33.0 33.2 33.4 33.5 33.8 33.9 34.2 34.5 34.6 34.8 1.0240 34.2 34.3 34.5 34.7 35.0 35.1 35.4 35.5 35.8 35.9 36.2 1.0250 35.5 35.6 35.9 36.0 36.3 36.4 36.7 36.8 37.1 37.2 37.5 1.0260 36.8 36.9 37.2 37.3 37.6 37.7 38.0 38.2 38.4 38.6 38.8 1.027 38.1 38.4 38.5 38.8 38.9 39.1 39.3 39.5 39.8 39.9 40.2 1.0280 39.4 39.7 39.8 40.1 40.2 40.5 40.7 40.8 14.1 41.2 41.5 1.0290 40.8 41.0 41.2 41.4 41.6 41.8 Professional conductivity meters will also measure temperature and will therefore give a reading that is adjusted for the temperature. The reading may already be translated into salinity (ppt) or may give the actual conductivity reading in millisiemens. The table below converts mS to salinity (S.G @ 25°C): mS to Salinity conversion (S.G. @ 25°C) Salinity ppt Conductivity mS S.G. Salinity ppt Conductivity mS S.G. 32.00 49.000 1.0210 36.44 55.000 1.0244 32.74 50.000 1.0216 37.19 56.000 1.0250 33.47 51.000 1.0221 37.94 57.000 1.0255 34.21 52.000 1.0227 38.69 58.000 1.0260 34.95 53.000 1.0233 39.45 59.000 1.0267 35.00 53.065 1.0235 40.21 60.000 1.0270 35.70 54.000 1.0238 Salinity of the world’s oceans. • The salinity of the natural coral reefs ranges from 33 to 40 ppt • The salinity of the Red Sea (the source of Red Sea’s salts) is 40 ppt Salinity (ppt) Red Sea | Sea Water Chemistry Red Sea Red Sea | Sea Water Chemistry Life Support Parameters - pH The recommended pH in a coral reef tank for optimal calcification: 8.2-8.4 The recommended pH in a fish only tank: 7.8 – 8.4 The pH should be monitored every other day A drop in pH can be fatal to marine organisms. pH drops are caused by: excessive CO2, decrease in Alkalinity, excessive nitrification & a build-up of organic matter. All biological processes occur in specific narrow range of pH, even the slightest changes in pH can affect fundamental processes in many marine organisms, such as calcification and the deposition of calcium carbonate skeletons. For example: • Optimal Calcification pH: 8.3 • Optimal ammonia removal from gills: 7.8-8.4 (marine fish). Chem-tech note: pH is a measure of how acidic/basic water is. The range goes from 0 - 14, with 7 being neutral. pH is really a measure of the relative amount of free hydrogen and hydroxyl ions in the water. Water that has more free hydrogen ions is acidic, whereas water that has more free hydroxyl ions is basic. pH is an important indicator of water that is changing chemically. Dissolved carbon dioxide (CO2) & alkalinity substances have a direct influence on pH levels in seawater due to the dynamic equilibrium that exists between molecules of carbonic acid, bicarbonate and carbonate CO2 + H2O <=> H2CO3 <=> H+ + HCO3- <=> 2H+ + CO32 (1%) (93%) (6%) - (equilibrium percentage in seawater) When the dissolved CO2 levels increase, the equation shifts to the right and more H+ ions are released to the water and the pH drops. When you have more alkalinity substances, such as CO32- The equation shifts to the left and the pH will climb. pH of the world’s oceans. • The pH of the natural coral reefs ranges from 8.05 – 8.12 Red Sea | Sea Water Chemistry Red Sea Red Sea | Sea Water Chemistry Important elements in salt: Alkalinity / Carbonate Hardness (dKH) The recommended Alkalinity (dKH) in a coral reef tank for optimal calcification: 3-4.5 (9-15 dKH) The recommended Alkalinity in a fish only tank: 2.2- 3 (6 - 8 dKH) Alkalinity ( also referred to as “pH Buffer” ) refers to the amount of acid required to lower the pH. It indicates the store of bicarbonate (HCO3-) and carbonate (CO3-) in the water which help to maintain a stable pH. Alkalinity is measured in milliequivalents/liter (meq/l) or carbonate hardness (dKH). 1 meq/l = 2.8 dKH The prevailing wisdom among marine biologists favors the notion that certain organisms calcify more quickly at a higher alkalinity than naturally occurs in seawater, therefore Red Sea recommends a higher alkalinity level (see spec for Coral Pro) for a Coral Reef Aquarium. Bio-tech note: Corals absorb bicarbonate as building blocks for their skeleton, by converting it to carbonate and then combine the carbonate with calcium to form calcium carbonate skeletons. Bicarbonate intake thus becomes a limiting factor in the calcification rate among many corals. This stems partially from the fact that both photosynthesis and calcification compete for bicarbonate, and the bicarbonate concentration starts out low. You should maintain alkalinity in the 3 -4.5 meq/L (9-15 dKH) range. Higher levels, although they do not adversely affect the coral, increase the likelihood of decreased calcium concentration. Calcium The recommended Calcium level in a coral reef tank for optimal calcification: 440 – 460 ppm The recommended Calcium level in a fish only tank: 380 - 460 ppm As mentioned above, corals primarily use calcium carbonate to form their skeletons. Most of the calcium comes from the surrounding water. Consequently, aquaria with growing coral, calcareous algae and giant clams (tridacnids), rapidly become depleted of calcium. Once the calcium level drops below 360ppm, corals can no longer absorb enough of it, and they stop growing. Calcium level should be maintained between 420-460ppm. Higher levels, although they do not adversely affect the coral, increase the likelihood of decreased alkalinity. Red Sea | Sea Water Chemistry Red Sea Red Sea | Sea Water Chemistry Magnesium The recommended Magnesium level in a coral reef tank for optimal calcification: 1250 – 1400 ppm The recommended Magnesium level in a fish only tank: 1100 – 1400 ppm Some corals and coralline algae deplete magnesium by absorbing it into their growing skeletons however Magnesium’s primary importance lies in its effect on the alkalinity/calcium balance in reef aquaria. Chem-tech note: Seawater and reef aquarium water ideally have calcium carbonate at super-saturation levels. This naturally causes calcium to precipitate out of solution, forming crystals that cannot re-dissolved at the natural pH of seawater. Magnesium binds to these crystals, effectively blocking their surface and preventing further precipitation that would otherwise pull more calcium out of the seawater. This helps keep calcium and alkalinity at natural levels and therefore Magnesium can be referred to as the buffer of the buffer. Potassium, Strontium, Iodine, Iron & Manganese All of these elements play an important role in the calcification process, the photosynthesis of the zooxanthellae and coloration of the corals. Therefore these elements and must be present in the correct levels Red Sea | Sea Water Chemistry Red Sea Red Sea | Sea Water Chemistry Undesirable nutrients in sea water or salt Coral reefs develop and flourish only in clear, unpolluted oligotrophic ocean areas i.e. areas with limited nutrients in the water. In the natural reef environment, the major nutrients nitrogen (ammonia, nitrites & nitrates), phosphorus (phosphates) and carbon are only available for the zooxanthellae (Coral symbiosis). In a reef aquarium nutrient levels above those required by the zooxanthellae will enhance the population of bacteria and algae which further reduces water quality Organics Pollution pathways: Reduce oxygen Increase bio-load Increase Nutrients Calcium Accessibility toxins Algea outbreak Damage to Toxins, compotition with Zoaxanthellee Phosphorus (Phosphates) The recommended maximum Phosphate level in a coral reef tank: 0.1 ppm The recommended maximum Phosphate level in a fish only tank: 1 ppm Inorganic orthophosphate occurs in aquaria in several chemical forms (PO4³, HPO32-) These phosphate forms enter the aquarium with through the decomposition of organic matter, fish waste, tap water, supp., salt mixes, live rocks, substrates and some methods of calcium and alkalinity supplementation. If allowed to accumulate above the recommended levels phosphates will cause the following problems: 1. Direct damage to corals by reducing available Ca ions for coral skeletogenesis. The formation of Calcium Phosphate Ca3(PO4)2 will inhibit the formation of Calcium Carbonate CaCO3 skeleton. 2. Increase zooxanthellae densities – reduce available nutrients to corals (bicarbonate) 3. Eutrophication – release of toxins to the water by algae. Red Sea | Sea Water Chemistry Red Sea | Sea Water Chemistry Red Sea Nitrogen (ammonia, nitrites & nitrates): Ammonia The recommended maximum Ammonia level in all marine tanks: 0.1 ppm Ammonia results from the decomposition of organic matter and from fish waste. It is highly toxic to marine life. In an established aquarium, the nitrifying bacteria rapidly convert ammonia to nitrite, nitrate and nitrogen gas, compounds with much less toxicity to fish than ammonia itself. Nitrite The recommended maximum Nitrite level in all marine tanks: 0.1 ppm As an intermediate product of ammonia oxidation, nitrite demands little or no attention from the reef aquarist. Nevertheless, tracking nitrite can prove instructive by demonstrating the biochemical processes at work in the aquarium. Nitrate The recommended maximum Nitrate level in a coral reef tank: 1.0 ppm The recommended maximum Nitrate level in a fish only tank: 10 ppm The nitrification process ends with the production of nitrate. Nitrate abundance usually results in the growth of algae and potential pests such as dinoflagellates, whose growth are spurred by nitrate. At the levels normally found in reef aquaria, nitrates carry no particular toxicity; in fact the zooxanthellae corals consume it as a nitrogen source. The negative effects of high nitrate levels are: Indirect damage to corals by increasing zooxanthellae densities: 1. Increase zooxanthellae densities – reduce available nutrients to corals (bicarbonate) 2. Intensive photosynthesis – high levels of oxygen radicals. 3. Eutrophication – release of toxins to the water by algae Red Sea | Sea Water Chemistry Red Sea The Red Sea The Red Sea is located between Asia and Africa and stretches over 1000 miles from the Gulf of Aquaba/Eilat in the north to join the Indian Ocean between Ethiopia and Yemen in the south. To anyone standing on its shore and gazing out across its heavenly waters, the Red Sea may seem to be a misnomer. Its blueness is eternal and anything less red cannot be imagined. The Red Sea, where the desert meets the ocean, is truly one of the planet’s most exotic and fascinating natural seascape environments. Beneath its crystal blue surface the Red Sea holds an oasis of living creatures, reefs, and coral formations. Red Sea | The Red Sea
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12:40:40+02:00, 2009:02:11 12:42:09+02:00, 2009:02:11 12:49:26+02:00, 2009:02:11 13:44:59+02:00, 2009:02:11 13:49+02:00, 2009:02:11 13:51:35+02:00, 2009:02:11 13:59:28+02:00, 2009:02:11 14:00:29+02:00, 2009:02:11 14:06:52+02:00, 2009:02:11 14:11:06+02:00, 2009:02:11 14:11:57+02:00, 2009:02:11 14:15:04+02:00, 2009:02:11 14:16:16+02:00, 2009:02:11 14:41:41+02:00, 2009:02:11 14:51:39+02:00, 2009:02:11 15:01:57+02:00, 2009:02:11 15:07:04+02:00, 2009:02:11 15:16:25+02:00, 2009:02:11 15:29:28+02:00, 2009:02:11 15:31:36+02:00, 2009:02:11 15:32:04+02:00, 2009:02:11 15:35:35+02:00, 2009:02:11 15:36:27+02:00, 2009:02:11 15:37:09+02:00, 2009:02:11 15:54:12+02:00, 2009:02:11 16:18:41+02:00, 2009:02:11 16:21:23+02:00, 2009:02:11 16:23:28+02:00, 2009:02:11 16:24:17+02:00, 2009:02:11 16:26:08+02:00, 2009:02:11 16:32:53+02:00, 2009:02:11 16:39:05+02:00, 2009:02:11 16:39:05+02:00, 2009:02:16 09:37:04+02:00, 2009:02:16 09:45:20+02:00, 2009:02:16 10:03:39+02:00, 2009:02:16 10:14:43+02:00, 2009:02:16 11:07:47+02:00, 2009:02:16 11:10:46+02:00, 2009:02:16 11:12:13+02:00, 2009:02:16 11:13:20+02:00, 2009:02:16 11:13:27+02:00, 2009:02:16 12:51:25+02:00, 2009:02:16 12:52:50+02:00, 2009:02:16 12:59:28+02:00, 2009:02:16 13:05:05+02:00, 2009:02:16 13:07:48+02:00, 2009:02:16 13:18:44+02:00, 2009:02:16 13:19:39+02:00, 2009:02:16 15:10:32+02:00, 2009:02:16 15:16:13+02:00, 2009:02:16 15:24:09+02:00, 2009:02:16 15:41:03+02:00, 2009:02:16 15:57:54+02:00, 2009:02:16 15:58:47+02:00, 2009:02:16 15:58:47+02:00, 2009:02:16 16:34:32+02:00, 2009:02:16 16:36:48+02:00, 2009:02:16 16:43:10+02:00, 2009:02:16 16:46:21+02:00, 2009:02:16 16:47:49+02:00, 2009:02:16 16:51:46+02:00, 2009:02:16 19:21:24+02:00, 2009:02:16 19:22:03+02:00, 2009:02:16 19:24:55+02:00, 2009:02:16 19:28:33+02:00, 2009:02:16 19:49:59+02:00, 2009:02:16 19:51:06+02:00, 2009:02:16 19:52:34+02:00, 2009:02:16 19:55:01+02:00, 2009:02:16 19:57:41+02:00, 2009:02:18 13:02:52+02:00, 2009:02:18 13:02:52+02:00, 2009:02:18 14:34:51+02:00, 2009:02:18 15:10:19+02:00, 2009:02:18 15:19:41+02:00, 2009:02:18 15:22:42+02:00, 2009:02:18 15:45:52+02:00, 2009:02:18 15:50:04+02:00, 2009:02:18 15:50:48+02:00, 2009:02:18 15:51:57+02:00, 2009:02:18 15:53:35+02:00, 2009:02:18 15:59:01+02:00, 2009:02:18 16:08:06+02:00, 2009:02:18 16:22:23+02:00, 2009:02:18 16:24:09+02:00, 2009:02:18 16:26:37+02:00, 2009:02:18 16:31:52+02:00, 2009:02:18 16:32:30+02:00, 2009:02:18 16:33:42+02:00, 2009:02:18 16:40:48+02:00, 2009:02:18 16:51:14+02:00, 2009:02:18 16:51:33+02:00, 2009:02:18 16:53:36+02:00, 2009:02:18 17:10:13+02:00, 2009:02:18 17:11:07+02:00, 2009:02:18 17:19:28+02:00, 2009:02:18 17:22:57+02:00, 2009:02:18 17:24:49+02:00, 2009:02:18 17:31:05+02:00, 2009:02:18 17:44:12+02:00, 2009:02:18 17:49:04+02:00, 2009:02:23 12:33:29+02:00, 2009:02:23 14:25:34+02:00, 2009:02:23 14:25:34+02:00, 2009:02:23 14:37:37+02:00, 2009:02:23 14:49:34+02:00, 2009:02:23 15:23:21+02:00, 2009:02:23 15:25:45+02:00, 2009:02:23 15:40:53+02:00, 2009:02:23 15:44:13+02:00, 2009:02:23 15:46:37+02:00, 2009:02:23 17:05:34+02:00, 2009:02:25 14:49:41+02:00, 2009:02:25 14:54:04+02:00, 2009:02:25 15:00:48+02:00, 2009:02:25 15:14:05+02:00, 2009:02:25 15:29:15+02:00, 2009:02:25 15:33:54+02:00, 2009:02:25 15:47:19+02:00, 2009:02:25 15:54:54+02:00, 2009:02:25 16:03:05+02:00, 2009:02:25 16:05:26+02:00, 2009:02:25 16:05:37+02:00, 2009:02:25 16:12:18+02:00, 2009:02:25 17:10:54+02:00, 2009:03:09 16:46:33+02:00, 2009:03:09 17:04:49+02:00, 2009:03:09 17:07:31+02:00, 2009:03:15 10:31:46+02:00, 2009:03:15 10:42:58+02:00, 2009:03:23 10:21:14+02:00, 2009:03:23 10:21:14+02:00, 2009:03:23 10:37:09+02:00, 2009:03:25 10:47:10+02:00, 2009:03:25 10:54:32+02:00, 2009:03:25 11:02:17+02:00, 2009:03:25 13:11:30+02:00, 2009:03:25 14:48:31+02:00, 2009:03:25 14:52:36+02:00, 2009:03:29 12:54:17+02:00, 2009:03:29 14:33:21+02:00, 2009:03:30 11:24:40+02:00, 2009:03:30 11:25:55+02:00, 2009:03:30 12:11:26+02:00, 2009:03:30 14:02:28+02:00, 2009:03:30 14:07:03+02:00, 2009:03:30 14:14:48+02:00, 2009:03:30 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17:07:07+03:00, 2009:04:22 16:20:37+03:00, 2009:04:22 16:20:37+03:00, 2009:04:22 16:30:09+03:00, 2009:04:22 16:36:04+03:00, 2009:05:11 15:00:44+03:00, 2009:05:11 15:00:44+03:00, 2009:05:11 15:16:53+03:00, 2009:05:11 15:22:15+03:00, 2009:05:11 15:33:12+03:00, 2009:05:11 15:34:52+03:00, 2009:05:11 16:42:26+03:00, 2009:05:11 16:43:14+03:00, 2009:05:11 16:48:05+03:00, 2009:05:11 17:31:13+03:00, 2009:05:11 17:32:03+03:00, 2009:05:11 17:38:12+03:00, 2009:05:11 17:46:01+03:00, 2009:05:11 17:47:36+03:00, 2009:05:11 17:49:31+03:00, 2009:05:12 07:57:17+03:00, 2009:05:12 10:42:29+03:00, 2009:05:12 10:43:23+03:00, 2009:05:12 11:01:03+03:00, 2009:05:12 11:06:15+03:00, 2009:05:12 11:06:48+03:00, 2009:05:12 11:07:42+03:00, 2009:05:12 11:22:33+03:00, 2009:05:12 11:27:24+03:00, 2009:05:12 11:43:24+03:00, 2009:05:12 11:45:20+03:00, 2009:05:13 09:07:11+03:00, 2009:05:13 09:08:28+03:00, 2009:05:20 09:12:34+03:00, 2009:05:20 09:12:34+03:00, 2009:05:20 11:54+03:00, 2009:05:20 12:08:26+03:00, 2009:05:20 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