The Properties and Composition of Seawater: An “Elemental” Overview

Dave Cohrs Water Quality Manager National Aquarium in Baltimore, US

The Properties and Composition of Seawater: An “Elemental” Overview
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Water and the Hydrological Cycle Elemental Trends – The Composition of Seawater Sources of Constituents pH, Alkalinity, ORP Nutrients: Natural vs. Artificial Environments Chlorination and Ozonation Disinfection byproducts

1st AQUALITY Symposium, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

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H2O Asymmetrical polar structure = permanent dipole Highest heat capacity of all solids and liquids (except ammonia) 4.184kJ/mol Highest surface tension of all liquids Dissolves more substances, in greater quantities than any other liquid – Seawater contains ~3.5% dissolved substances Highly transparent
1st AQUALITY Symposium, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

The Hydrological Cycle 1st AQUALITY Symposium.7. April 2 . 2004. Oceanario de Lisboa. Portugal .

April 2 . 2004.The Hydrological Cycle     (Water x 1015kg) – Rivers and Streams (1) – Soil Moisture and Seepage (70) – Salt Lakes and Inland Seas (104) – Freshwater Lakes (125) – Groundwater (8400) – Glaciers and Icecaps (29300) Total amount of Water on Land (38000) Total amount of Water in the Oceans (1322000) Total Water Supply (1360000) 1st AQUALITY Symposium. Portugal .7. Oceanario de Lisboa.

5% by weight) – Salinity is a function of density and temperature (oC) – The density of seawater normally increases with depth – Now measured as R = conductivity of seawater sample conductivity of standard KCl solution Where KCl solution = 32.The Hydrological Cycle      The Oceans contain 97% of the global water inventory Less than 1% is available for drinking Density of Freshwater = 1. April 2 . Oceanario de Lisboa. 2004.03x103 kg m-3 Salinity = Average Concentration of Dissolved Substances – Surface waters: salinities range from 33 to 37 mg kg-1 – Average: 35 mg kg-1 (3.00x103 kg m-3 Density of Seawater = 1.7. Portugal .4356 g kg-1 1st AQUALITY Symposium.

The Composition of Seawater: It’s Elementary my dear Watson    All of the naturally occurring elements are present in Seawater Water 96.5% Everything Else 3.5% H H O 1st AQUALITY Symposium. Oceanario de Lisboa.7. Portugal . 2004. April 2 .

9% of dissolved constituents by weight – >1mg L-1 Concentration – 21.482% (g kg-1 solvent) Na+ SO42Mg2+ Ca2+ Minor constituents  Trace constituents  F- Sr2+ H2BO3- Br- HCO3- K+ .The Composition of Seawater  Major constituents H2O Cl- – 11 Major Ions make up 99.9% Anions (Negatively Charged) – 12.6% Cations (Positively Charged) – Overall Salinity 34.

7.6 1. 2004. Oceanario de Lisboa.2 Strontium Bromide Fluoride Borate 1 Chloride Major Constituents (mg kg-1) 1st AQUALITY Symposium. April 2 .The Composition of Seawater 19000 10500 2700 1350 400 380 100000 10000 1000 100 140 65 10 8 4. Portugal Magnesium Sodium Sulfate Bicarbonate Potassium Calcium .

7.013% Sulfate 7.003% Strontium 0.815% Magnesium 4% Bromide 0.392% Major Constituents Fluoride 0. April 2 0. Portugal .100% 1st AQUALITY Symposium.158% 1. 2004. Oceanario de Lisboa.995% Sodium 30.405% .188% Calcium Bicarbonate Potassium 1.Water ~97% Trace Constituents Minor Constituents Chloride 54.023% Borate 0.

Spotte) –Carbohydrates.001 mg L-1 Other – Nitrogen. Si considered non-conservative (they vary considerably) – Dissolved Organic Carbon  Approximately 0.The Composition of Seawater  Minor constituents – < 1 mg L-1 but >0. Oxygen not included   Nitrogen is mostly present as a gas (N2) O.001 mg L-1 (= 1 ppb)   Trace constituents – <0. phytoplankton blooms  Higher in Aquarium Systems – Yellow water . Silicon. phenols from algae.6mg L-1 in surface waters (Williams.

12 0.00 Manganese Vanadium Arsenic Titanium Phosphorus Rubidium Minor Constituents (mg kg-1) 1st AQUALITY Symposium.7.16 0.14 0. April 2 .The Composition of Seawater 0. 2004.06 0. Portugal Molybdemum Lithium Barium Iodine Aluminum Uranium Zinc Nickel Copper Iron .08 0.10 0.04 0. Oceanario de Lisboa.18 0.02 0.

April 2 0.59% Iron Molybdemum 1.995% Sodium 30.003% Strontium 0.158% 1.59% Arsenic 0.74% Phosphorus 14% Rubidium 23. Oceanario de Lisboa.96% 1.405% .7.Aluminum Nickel Uranium Copper 1.392% Major Constituents Fluoride 0.188% Calcium Bicarbonate Potassium 1.023% Borate 0.96% Barium 5. 2004.48% Lithium 33.27% Vanadium 0. Portugal .37% 0.39% Titanium 0.100% 1st AQUALITY Symposium.39% Manganese 0.20% Water ~97% Minor Constituents Chloride 54.013% Sulfate 7.87% Iodine 11.815% Magnesium 4% Bromide 0.96% Zinc 1.96% 1.59% 0.

00E-12 1.00E-03 1. April 2 . 2004.00E-05 1.00E-15 1.00E-04 1.00E-13 1.00E-05 1.00E-09 1.Hafnium Helium Cerium Scandium Indium Tantalum Dysprosium Praseodymium Gadolinium Erbium Ytterbium Samarium Thorium Holmium Ruthenium Beryllium Thulium Lutetium Protactinium Radium Radon 1.00E-01 1.00E-02 1.00E-14 1.00E-16 Tin Cobalt Silver Cesium Antimony Mercury Krypton Cadmium Tungsten Neon Selenium Germanium Xenon Chromium Lead Gallium Zirconium Bismuth Lanthanum Yttrium Thallium Niobium Gold Neodymium Rhenium 1.00E-08 1.00E-10 1. Oceanario de Lisboa.00E-04 1.00E-07 1.00E-01 1.7.00E-06 1. Portugal .00E+00 1st AQUALITY Symposium.00E-11 1.00E-06 1.00E-03 1.00E+00 1.00E-02 1.

Oceanario de Lisboa. Zinc)  Weathering of Igneous and Metamorphic Rock by rainfall and other mass movement of water on land 1st AQUALITY Symposium. Portugal .7. 2004. Uranium. Magnesium & other Alkali Earth Metals (Group II) Organically-Rich Marine Sediments (Copper. April 2 .Sources of Constituents  Volcanic Activity/Atmospheric Interactions – Gaseous Emission    Chlorine (as Chloride) and other Halogens Sulfur Carbon Dioxide and Methane  Activity on the Sea Floor – – – Dissolution of minerals in rock of the oceanic crust from hydrothermal circulation Calcium.

most Minors and Traces:   Behave non-conservatively Concentrations are affected by biological or chemical processes – Depleted from or added to the water  Toxic above certain concentrations – (See AQUALITY discussion on heavy metals by Conklin) 1st AQUALITY Symposium. Sodium. 2004. April 2 .7. Portugal . Chloride) Bio-Intermediate Constituents – Depleted in surface waters.e. Oceanario de Lisboa.Sources of Constituents  Major Constituents – Most behave conservatively    SiO2 and Ca2+ are notable exceptions Bio-Unlimited Constituents (i. but never exhausted  Minor and Trace Constituents – Unlike Major constituents.

bicarbonate.Sources of Constituents  Gases – Solubility of gases increases with decreasing temperature – Nitrogen (N2)  About 11 of the 11.7. vulcanism]  Carbon Monoxide (CO) Sea to Air [microbial decomposition]  Nitrous Oxide (N2O) Sea to Air [microbial decomposition]  Methane (CH4) Sea to Air [anoxic conditions/microbial]  Methyl Iodide (CH3I) Sea to Air [Phytoplankton/Anoxic conditions]  Dimethyl Sulfide ((CH3)2S) Sea to Air [Phytoplankton/Anoxic conditions] 1st AQUALITY Symposium.5 mg L-1 total Nitrogen in seawater – Oxygen (O2)  Surface waters are consistently supersaturated due to liberation of oxygen by phytoplankton and wave activity driving gases into solution – Carbon Dioxide (CO2)  Present in seawater as carbonic acid. and carbonate -1 at 24oC as gas  Only about 0. April 2 . Oceanario de Lisboa. 2004. Portugal .23 mg L  Increasing atmospheric content during the last 60 years – Other Gases  Sulfur Dioxide (SO2) Air to Sea [acid rain.

2 11 0 1st AQUALITY Symposium.7 HCO3140 55 0. Oceanario de Lisboa. Portugal .1 SiO2 Br- HCO3.2 Ca2+ 420 15 0. 2004.SO42- Cl- Ca2+ Mg2+ K+ Na+ Na+ Seawater River Water Rainwater 10500 7 2 K+ 350 2 0.3 Mg2+ 1340 5 0. April 2 .A Comparison of Seawater to other waters (mg kg-1) 100000 10000 1000 100 10 1 0.15 Cl19000 9 4 SO422700 10 0.7.3 Br65 0 0 SiO2 1.

pH of Seawater • pH – Concentration of Hydrogen (Hydronium Ion) – The “p” stands for Power – pH = .2 = .3 in surface waters H3O+ ee- e.log10[H3O+] – Example…pH 8. April 2 .2 – 8. there is 10x more OH-(aq) at pH 8 than at pH 7 10-14 = [H+][OH-] 14 = pH + pOH 2H2O (l) = H3O+(aq) + OH-(aq) OH- e.2 mol L-1 – [H+] = 6.7. 2004. there is 10x more H3O+(aq) than at pH 8 Conversely. Portugal .7 to 8.e- e.log[H+] – .3 x 10-9 mol L-1 – pH ranges from 7. Oceanario de Lisboa.2 = log[H+] (flip the sign and take Antilog) – [H+] = 10-8.8.e- 1st AQUALITY Symposium.e-  pH Scale is logarithmic - - At pH 7.

April 2 . the net molar concentration of strong base cations in excess of the net molar concentration of strong acid ions (in terms of charge equivalents) – A = [Strong Base Cations] – [Strong Acid Anions] – A = ([Na+] + [K+] +2[Mg2+] + 2[Ca2+]) – ([Cl-] + [Br-] + 2[SO42-]) – Seawater is electrically neutral – This works out to about 2 mol m-3 – Therefore… – A = [HCO3-] + 2[CO32-] – A ≈ 2 mol m-3 throughout the oceans (A ≈ 140 mg kg-1) – K = [H3O+][HCO3-] [CO32-] – [H3O+] = K [HCO3-] [CO32-] Therefore the ratio of the concentration of bicarbonate and carbonate ions must control the hydronium concentration and pH! As the ratio increases. Portugal .Alkalinity of Seawater • Formally. Oceanario de Lisboa. 2004.7. so does the pH. 1st AQUALITY Symposium.

Portugal .pH & Alkalinity H2O + CO2 100 H2CO3 (carbonic acid) H2CO3 H+ + HCO3- 2H+ + CO32- CO32(carbonate ion) 50 average pH of seawater normal pH range of seawater HCO3(bicarbonate ion) 0 4 5 6 7 8 pH 9 10 11 12 1st AQUALITY Symposium. Oceanario de Lisboa.7. 2004. April 2 .

Reduction is Gain of electrons) – The oxidation state of elements with more than one valence state greatly affects their solubility suspended colloid – Oxidized form of Iron (III) Fe(OH)3 – very low solubility. for waters of High ORP: – Available Iron will be very low – This is true for Cobalt.ORP of Seawater  Oxidation-Reduction Potential – OILRIG (Oxidation is Loss of electrons. 2004. Manganese – Precipitated as hydroxides or hydrated oxides – Biological significance where ORP varies dramatically 1st AQUALITY Symposium. April 2 . – Reduced form Iron (II) Fe(OH)2 – more soluble – Therefore.7. Portugal . Oceanario de Lisboa.

low oxygen.7.Reducing – Aquarium systems – Generally considered to be a measure of the state of “cleanliness” – Use a platinum/combination electrode – Make sure the filling solution matches the ionic strength of the solution – Check against reference standards (Zobell’s or pH buffers with Quinhydrone) – 275 – 350mV is an acceptable “safe” range 1st AQUALITY Symposium. April 2 . – Surface waters are oxygen rich – Oxidizing – Sediments. redox reactions are usually quite different from what would be predicted based on thermodynamics (Horne 1965. Portugal . Oceanario de Lisboa. 2004. ORP of seawater – Natural waters ORP of Seawater – Very complex due to all of the redox couples present – In natural waters. mangrove habitats. Stumm and Morgan 1981). organics .

N2 – Nitrogen gas 11 mg L-1 – [NH3+NH4+] + [NO2-] + [NO3-] = ≤ 0. Oceanario de Lisboa. April 2 .) 0. 2004. Silicon – Nitrogen – Ammonia (NH3+NH4+). Phosphorus. Nitrate (NO3-). Portugal . Nitrite (NO2-).5 mg L-1 – Phosphorus – Phosphate (PO43. increase with depth – Biologically limiting 1st AQUALITY Symposium.06 mg L-1 – The Magic Ratio – Nitrogen:Phosphorus 15:1 molar ratio – Same in both Tissue and Seawater – Nutrients are depleted in surface waters.Nutrients in Seawater  Nutrients – Polyatomic compounds containing Nitrogen.7.

Nitrite (NO2-) – typically very low concentrations in stable systems where filtration is adequate. well maintained – Nitrate (NO3-) – Toxic in relatively low concentrations – Typically accumulates in fish or marine mammal systems – May be depleted in photosynthetically active systems (corals) – Biological effects at high concentration (much debate!) – Water exchanges – Denitrification systems (see Hignette.7. Aiken) – Algal turf scrubbing (Adey. stimulating algal growth 1st AQUALITY Symposium.Ammonia (NH3+NH4+). April 2 . Mort. Oceanario de Lisboa. et al) – Electrochemical reduction – Phosphorus – Also can climb to undesirable levels. 2004. Portugal .Nutrients in Aquarium Systems .

7. 2004. marine mammal. Portugal . or avian pools – Human/Animal interaction – Control of coliform and other bacteria – Improve clarity – Improve color  Consider Bromine and Chlorine in Seawater – Bromine (as Bromide) 65 mg L-1 – Chlorine (as Chloride) 19000 mg L-1  Both species react with Chlorine (typically NaClO) or Ozone (O3) to form weak acids – Strong oxidizing power – Increased ORP – Side Effects 1st AQUALITY Symposium. April 2 .Chlorination and Ozonation  Increasing ORP: Add an oxidant – Sanitization or sterilization – Mammal. Oceanario de Lisboa.

+ H+  hypobromous acid .hypobromite – HOCl + OCl.7.hypochlorite – HOCl + Br -<-> HOBr + Cl HOBr <-> OBr.= Free Chlorine – HOBr + OBr. Oceanario de Lisboa. 2004. Portugal . April 2 .Chlorination and Ozonation  Inorganic Reaction Products of Chlorination – NaOCl + H2O<-> HOCl + Na+ + OH– HOCl <-> OCl.= Active Bromine  – Bromine (as bromide impurity) is sometimes restricted when selecting salts for seawater formulation to prevent unwanted reactions 1st AQUALITY Symposium.+ H+ hypochlorous acid .

+ ClHOCl + Br -<-> HOBr + Cl HOBr <-> OBr.<-> OBr .<-> O2 + OClO3 + Br .+ H+  – Monochloramines NH3 + HOCl <-> NH2Cl + H2O Monobromamines prevail at NH4-N >0. 2004.+ Br . April 2 . Portugal .8mg L-1 Bromine oxidation predominates in seawater so bromamines are favored – Mono and Dibromamines   1st AQUALITY Symposium.<-> O2 + OBr OCl. Oceanario de Lisboa.Chlorination and Ozonation  Inorganic Reaction Products of Ozonation – – – – O3 + Cl.7.

April 2 . Unfortunately. Bromoform.7. Blue Water has a price… – Disinfection byproducts can and do form during Chlorination and Ozonation – Dissolved organic substances – Disinfection Byproducts –THM trihalomethanes. once formed 1st AQUALITY Symposium. Bromochloromethane. Portugal .Disinfection Byproducts – Nothing is Free. Known mutagens and carcinogens! – Humic and fulvic acids are precursors (cause yellow water) – Chloroform. Chlorate potential carcinogens – Regulated DBP in drinking water – Both species are stable and hard to get rid of. Oceanario de Lisboa. 2004. Dibromochloromethane – Packed column aeration for removal of volatile THM and NCl3 – Bromate.

Portugal .) – Bromate to 10µg L-1 – Chlorite to 1000µg L-1 – USEPA D/DBP MCL in finished drinking water 1st AQUALITY Symposium.Disinfection Byproducts .7. 2004.to BrO3. 1977) – Chlorate production favored in chlorinated natural seawater receiving strong sunlight (personal observation) – Bromate has been shown to be reduced to Br .by activated carbon (Marhaba.<-> O2 + OBr – – – – O3 + OBr – <-> 2O2 + Br – 2O3 + OBr – <-> 2O2 + BrO3 – Sunlight induces conversion of up to 50% of OBr . Medlar et al.in chlorinated seawater (Macalady et al.Bromate and Chlorate – O3 + Br . April 2 . Oceanario de Lisboa.

Enjoy the rest of the conference 1st AQUALITY Symposium. Portugal . Oceanario de Lisboa.7. April 2 .Thank you. 2004.