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

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

e-

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Water H

O
105o

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, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

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, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

The Hydrological Cycle

The Oceans contain 97% of the global water inventory Less than 1% is available for drinking Density of Freshwater = 1.00x103 kg m-3 Density of Seawater = 1.03x103 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 (3.5% 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 = 32.4356 g kg-1

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

The Composition of Seawater: Its Elementary my dear Watson

All of the naturally occurring elements are present in Seawater Water 96.5% Everything Else 3.5%

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

The Composition of Seawater

Major constituents

H2O

Cl-

11 Major Ions make up 99.9% of dissolved

constituents by weight >1mg L-1 Concentration 21.9% Anions (Negatively Charged) 12.6% Cations (Positively Charged) Overall Salinity 34.482% (g kg-1 solvent)

Na+ SO42Mg2+ Ca2+

Minor constituents Trace constituents

F-

Sr2+

H2BO3-

Br-

HCO3-

K+

The Composition of Seawater

19000 10500 2700 1350 400 380

100000 10000 1000 100

140

65 10 8 4.6 1.2
Strontium Bromide Fluoride Borate

Chloride

Major Constituents (mg kg-1) 1st AQUALITY Symposium, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

Magnesium

Sodium

Sulfate

Bicarbonate

Potassium

Calcium

Water ~97%

Trace Constituents Minor Constituents

Chloride 54.995% Sodium 30.392%

Major Constituents

Fluoride 0.003% Strontium 0.023% Borate 0.013%

Sulfate 7.815%

Magnesium 4% Bromide 0.188% Calcium Bicarbonate Potassium 1.158% 1.100% 1st AQUALITY Symposium, April 2 0.405%

- 7, 2004, Oceanario de Lisboa, Portugal

The Composition of Seawater

Minor constituents
< 1 mg L-1 but >0.001 mg L-1 (= 1 ppb)

Trace constituents <0.001 mg L-1 Other Nitrogen, Silicon, Oxygen not included

Nitrogen is mostly present as a gas (N2) O, Si considered non-conservative (they vary considerably)

Dissolved Organic Carbon

Approximately 0.6mg L-1 in surface waters (Williams, Spotte)

Carbohydrates, phenols from algae, phytoplankton blooms

Higher in Aquarium Systems

Yellow water

The Composition of Seawater

0.18 0.16 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00
Manganese Vanadium Arsenic Titanium

Phosphorus

Rubidium

Minor Constituents (mg kg-1) 1st AQUALITY Symposium, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

Molybdemum

Lithium

Barium

Iodine

Aluminum

Uranium

Zinc

Nickel

Copper

Iron

Aluminum Nickel Uranium Copper 1.96% 1.37% 0.59% 0.59% Arsenic 0.59% Iron Molybdemum 1.96% 1.96% Zinc 1.96% Barium 5.87% Iodine 11.74% Phosphorus 14% Rubidium 23.48% Lithium 33.27%

Vanadium 0.39% Manganese 0.39% Titanium 0.20%

Water ~97%

Minor Constituents
Chloride 54.995% Sodium 30.392%

Major Constituents

Fluoride 0.003% Strontium 0.023% Borate 0.013%

Sulfate 7.815%

Magnesium 4% Bromide 0.188% Calcium Bicarbonate Potassium 1.158% 1.100% 1st AQUALITY Symposium, April 2 0.405%

- 7, 2004, Oceanario de Lisboa, Portugal

Hafnium Helium Cerium Scandium Indium Tantalum Dysprosium Praseodymium Gadolinium Erbium Ytterbium Samarium Thorium Holmium Ruthenium Beryllium Thulium Lutetium Protactinium Radium Radon
1.00E+00 1.00E-01 1.00E-02 1.00E-03 1.00E-04 1.00E-05 1.00E-06 1.00E-07 1.00E-08 1.00E-09 1.00E-10 1.00E-11 1.00E-12 1.00E-13 1.00E-14 1.00E-15 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-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00

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

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, Magnesium & other Alkali Earth Metals (Group II) Organically-Rich Marine Sediments (Copper, Uranium, Zinc)

Weathering of Igneous and Metamorphic Rock by rainfall and other mass movement of water on land

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

Sources of Constituents

Major Constituents
Most behave conservatively

SiO2 and Ca2+ are notable exceptions Bio-Unlimited Constituents (i.e. Sodium, Chloride) Bio-Intermediate Constituents
Depleted in surface waters, but never exhausted

Minor and Trace Constituents

Unlike Major constituents, 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, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

Sources of Constituents

Gases
Solubility of gases increases with decreasing temperature Nitrogen (N2) About 11 of the 11.5 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, bicarbonate, and carbonate -1 at 24oC as gas Only about 0.23 mg L Increasing atmospheric content during the last 60 years Other Gases Sulfur Dioxide (SO2) Air to Sea [acid rain, 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, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

A Comparison of Seawater to other waters (mg kg-1)

100000 10000 1000 100 10 1 0.1

SiO2

Br-

HCO3- SO42-

Cl-

Ca2+ Mg2+

K+

Na+

Na+ Seawater River Water Rainwater 10500 7 2

K+ 350 2 0.3

Mg2+ 1340 5 0.2

Ca2+ 420 15 0.15

Cl19000 9 4

SO422700 10 0.7

HCO3140 55 0.3

Br65 0 0

SiO2 1.2 11 0

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

pH of Seawater pH
Concentration of Hydrogen (Hydronium Ion) The p stands for Power
pH = - log10[H3O+] ExamplepH 8.2 8.2 = - log[H+] - 8.2 = log[H+] (flip the sign and take Antilog) [H+] = 10-8.2 mol L-1 [H+] = 6.3 x 10-9 mol L-1 pH ranges from 7.7 to 8.3 in surface waters

H3O+
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pH Scale is logarithmic
-

At pH 7, there is 10x more H3O+(aq) than at pH 8 Conversely, 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- e-

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

Alkalinity of Seawater
Formally, 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, so does the pH.
1st AQUALITY Symposium, April 2 - 7, 2004, Oceanario de Lisboa, 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

10

11

12

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

ORP of Seawater

Oxidation-Reduction Potential
OILRIG (Oxidation is Loss of electrons, 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, Reduced form Iron (II) Fe(OH)2 more soluble Therefore, for waters of High ORP:

Available Iron will be very low

This is true for Cobalt, Manganese Precipitated as hydroxides or hydrated oxides Biological significance where ORP varies dramatically
1st AQUALITY Symposium, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

ORP of seawater
Natural waters

ORP of Seawater

Very complex due to all of the redox couples present

In natural waters, redox reactions are usually quite different from

what would be predicted based on thermodynamics (Horne 1965, Stumm and Morgan 1981).
Surface waters are oxygen rich Oxidizing

Sediments, mangrove habitats, low oxygen, organics - 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 (Zobells or pH buffers with

Quinhydrone)

275 350mV is an acceptable safe range

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

Nutrients in Seawater

Nutrients
Polyatomic compounds containing Nitrogen, Phosphorus, Silicon

Nitrogen Ammonia (NH3+NH4+), Nitrite (NO2-), Nitrate (NO3-), N2 Nitrogen gas 11 mg L-1 [NH3+NH4+] + [NO2-] + [NO3-] = 0.5 mg L-1 Phosphorus

Phosphate (PO43- ) 0.06 mg L-1

The Magic Ratio Nitrogen:Phosphorus 15:1 molar ratio Same in both Tissue and Seawater Nutrients are depleted in surface waters, increase with depth Biologically limiting
1st AQUALITY Symposium, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

Nutrients in Aquarium Systems

- Ammonia (NH3+NH4+), 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, Mort, Aiken)

Algal turf scrubbing (Adey, et al) Electrochemical reduction Phosphorus Also can climb to undesirable levels, stimulating algal growth
1st AQUALITY Symposium, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

Chlorination and Ozonation

Increasing ORP: Add an oxidant

Sanitization or sterilization
Mammal, marine mammal, 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 - 7, 2004, Oceanario de Lisboa, Portugal

Chlorination and Ozonation

Inorganic Reaction Products of Chlorination

NaOCl + H2O<-> HOCl + Na+ + OH HOCl <-> OCl- + H+

hypochlorous acid - hypochlorite HOCl + Br -<-> HOBr + Cl HOBr <-> OBr- + H+ hypobromous acid - hypobromite HOCl + OCl- = Free Chlorine HOBr + OBr- = Active Bromine

Bromine (as bromide impurity) is sometimes restricted

when selecting salts for seawater formulation to prevent unwanted reactions

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

Chlorination and Ozonation

Inorganic Reaction Products of Ozonation

O3 + Cl- <-> O2 + OClO3 + Br - <-> O2 + OBr OCl- + Br - <-> OBr - + ClHOCl + Br -<-> HOBr + Cl HOBr <-> OBr- + H+

Monochloramines
NH3 + HOCl <-> NH2Cl + H2O Monobromamines prevail at NH4-N >0.8mg L-1 Bromine oxidation predominates in seawater so bromamines are favored

Mono and Dibromamines

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

Disinfection Byproducts
Nothing is Free. Unfortunately, Blue Water has a price Disinfection byproducts can and do form during Chlorination and

Ozonation

Dissolved organic substances Disinfection Byproducts THM trihalomethanes. Known mutagens and carcinogens! Humic and fulvic acids are precursors (cause yellow water) Chloroform, Bromoform, Bromochloromethane,

Dibromochloromethane

Packed column aeration for removal of volatile THM and NCl3

Bromate, Chlorate potential carcinogens Regulated DBP in drinking water Both species are stable and hard to get rid of, once formed
1st AQUALITY Symposium, April 2 - 7, 2004, Oceanario de Lisboa, Portugal

Disinfection Byproducts
- Bromate and Chlorate
O3 + Br - <-> O2 + OBr

O3 + OBr <-> 2O2 + Br

2O3 + OBr <-> 2O2 + BrO3

Sunlight induces conversion of up to 50% of OBr - to BrO3- in

chlorinated seawater (Macalady et al. 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, Medlar et al.)

Bromate to 10g L-1 Chlorite to 1000g L-1

USEPA D/DBP MCL in finished drinking water

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

Thank you, Enjoy the rest of the conference

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