SQ10403

Water Composition and quality criteria

Composition of seawater, major and minor elements, dissolved elements in seawater Salinity, concepts, how to determined, salt balance. Residence time Composition of freshwater Dissolved gases Thermal and chemical stratifications Nutrients status: Eutrophy, oligotrophy and dystrophy

Composition of Seawater
Seawater is composed of a number of different components that can be divided into following phases: 1. Solids (materials that does not pass through a 0.45m filter): - Particulate organic matter (plant detritus) and - Particulate inorganic matter (minerals detritus) 2. Gases: - Conservative (N2, Ar, Xe) and - Non-conservatives (O2 and CO2) 3. Colloids (passes through a 0.45m filter, but is not dissolved): - Organic and - Inorganic 4. Dissolved solutes: - Inorganic solutes (1) Major (>1ppm) and (2) minor (<1ppm) and - Organic solutes.

Major constituents in seawater

Constituent Chloride (Cl-) Sodium (Na+) Sulfate (SO42-) Magnesium (Mg2+) Calcium (Ca2+) Potassium (K+) Bicarbonate(HCO3-) Bromide (Br-) Boric Acid (H3BO3) Strontium (Sr2+) Fluoride (F-) --------------------Total Concentration (ppt) 18.98 10.556 2.649 1.272 0.4 0.38 0.140 0.065 0.026 0.013 0.001 -----------------34.482 Ratio of constituent/total salts (%) 55.04 30.61 7.68 3.69 1.16 1.10 0.41 0.19 0.07 0.04 0.00 -------------------------------------99.99%

Table : Concentration of minor elements in Seawater

Element Symbol Si Li Rb P I N Ba Fe Zn Al Mo Cu As I Mn Concentration (mg/L) 3.0 0.17 0.12 0.07 0.06 0.05 0.03 0.01 0.01 0.01 0.01 0.003 0.003 0.002 0.002

The physical properties of pure water and seawater are remarkably similar with few exceptions. Some of those are as follows: Property Color -Small quantities - Large quantities Pure water Clear Blue-green because water molecules scattered blue and green wavelengths best Odorless Tasteless 7.0 (neutral) 1.00g/cm3 0oC 100oC Seawater Clear Same as pure water

Odor Taste pH Density at 4oC Freezing point Boiling point

Distinctly marine Salty 8.1 (slightly alkaline) 1.028g/cm3 -1.9oC 100.6oC

The table does not represent the last word in seawater compositions. Water flow across vegetation areas also dissolved various organic compounds and particulate organic matters both organic and inorganic. Mixing well in surface runoff and enriched river water. All those constituents finally deposited in to oceanic system and constitutes seawater as complex media.

Table: Average concentrations of the major ions in seawater (in parts per thousand)
Ions ClSO42HCO3BrH2BO3F by weight 18.980 2.649 0.140 0.065 0.026 0.001 Ions Na+ Mg2+ Ca2+ K+ Sr2+ by weight 10.556 1.272 0.400 0.380 0.013

Negative ions (anions) = 21.861

Positive ions (cations) = 12.621

Negative ions exceeds that of positive ions. Why does seawater not carry a net negative charge? What is the ratio of K+ concentration of the total salinity? What would be the potassium concentration if salinity rose from 34.482 to 36.

Seawater is electrically neutral because the proportions of total positive and total negative ions in molar terms are equal. To work out the molar concentration of an ion, simply divide the concentration in by the appropriate relative atomic or molecular mass. In case of Na+ and Cl- their ionic proportion (i.e. molar concentration) are much closer than their actual concentrations: 10.6 g/L Na+ = -------------23 g mol = 0.46mol/L 19.0 g/L Cl- = ------------------35.5 g/mol = 0.53 mol/L

Doing same for all other +ve and ve ions, and adding up totals, it will be more balanced.

From table the ratio is: Conc. K+ ----------------- = 0.380/34.482 = 0.011 Total salinity

If salinity rise to 36 Conc. of K+ ----------------36

= 0.011

So, Conc. of K+ = 0.011 x 36 = 0.396 (by weight)

The chloride ion in river originates mainly from the sea. It leaves the ocean as an aerosol and carried in the atmosphere to fall as rain and return to sea via rived. In sea water chloride is the most abundant, but in river water bio-carbonate is most abundant, chloride rank in 6th position.

Volcanoes produce large quantities of hydrogen chloride gas and the high level of volcanic activity early in the Earth history is probably the sources of majority of the chloride present in todays ocean.

Table: Approximate average percentages by weight of the ten most abundant elements in Earths crust

Element Silicon Aluminum Iron Calcium Sodium Potassium Magnesium Titanium Manganese Phosphorus

% by weight 28 8.2 5.6 4.2 2.4 2.4 2.0 0.6 0.1 0.1

Operation of hydrological cycle provides most of the dissolved constituents in seawater Another important process that contribute in seawater composition is: Hydrothermal vent circulation at the ocean ridge crusts Some of most abundant elements not appear at all in major ionic composition. The region lies in the degree of solubility and the chemical behavior of different elements when rocks are weathering and resulting products carried by surface run off through river to sea.

Many of the commonest elements in rocks, such as silicon, aluminium, and iron are not soluble. So, they transported and deposited mainly as solid particles of sand and clay. Sodium, calcium and potassium are relatively soluble and transported mainly in solution. Hydrothermal solution associated with sea floor spreading supply some elements to seawater solution (e.g. calcium, silicon, manganese) and remove others from it (e.g. magnesium, sulfur) However, the relative amounts of dissolved constitutes within ocean are controlled by complex and biological reactions in seawater

Definition: Salinity

Originally salinity was defined to the total amount of dissolved materials in grams in one kilogram of sea water. This is not useful because the dissolved materials is almost impossible to measure in practice. As volatile materials like gases difficult to measure. If seawater evaporate to dryness chlorides are lost in the last stages of drying

Concepts of salinity
Salinity is the total amount of dissolved material in grams in one kilogram of sea water. Thus salinity is a dimensionless quantity. The variability of dissolved salts is very small, so to define salinity it must be accurate and precise. But the range of salinity for most of the oceans is within 35. The average salinity of seawater is S = 35, which means that seawater is 3.5% salt and 96.5% H2O by weight

Classification of water based on salinity (Fast 1986):

- Freshwater less than 0.5

- Oligohaline 0.5 to 3.0 - Mesohaline 3.0 to 16.5 - Polyhaline 16.5 to 30 - Marine 30 to 40 - Brine or hyperhaline more than 40 Brackishwater is in the range of 0.5 to 30. In dry season some of the shrimp farm in Ecuador and Panama salinities are in the range of 40 to 60

Salinity based on Chlorinity Salinity is directly proportional to the amount of chlorine in sea water and chlorine can be measured accurately by a simple chemical analysis. Salinity was re-defined using chlorinity: S = 1.805 Cl + 0.03 As more and more accurate measurement were made the above equation become more inaccurate
Final equation is S = 1.80655 x Cl, Where, chlorinity (Cl) define as the concentration of chloride in SW.

Salinity based on Conductivity

Conductivity is a measure of the ability of water to conduct electricity. Conductivity is due to the dissolved ions, which are conductor. So, an increasing conductivity reading signifies the increasing concentration of dissolved ions. The unit is the micromho per centimeter. Distilled water 1-2 mhos/cm Freshwater 20-1500 mhos/cm Seawater more than 2000 mhos/cm Conductivity increases with the increase of salinity. Many instruments are design to read out both specific conductance and salinity

How is salinity determined?

1. Gravimetric methods: Evaporate to dryness. First precipitation is
CaCO3, follows by CaSO4, NaCl, K and Mg salts. Several problems exist and tedious process.

2. Analyze all major ions and sum. Problems: have to analyze 11 ions, some are difficult, cumulative errors are large. 3. Utilize the law of constant proportions chlorinity approach: Measure Cl% (which gives the sum of all halides: Cl- + F- + Br- + I-) by titration with AgNO3 to precipitate AgCl. The titration gives the g Cl equivalent in 1kg sea water. Ag+ + seawater = AgCl (s) + AgBr (s). The Cl can be converted to salinity using the equation: S = 1.80655 x Cl, where Cl chlorinity define as the concentration of chloride in SW. 4. Conductivity: Use the equation as before

5. Density: The measurement are normally made by passing water or sample through a vibrating tube encased in a constant temperature jacket. The density of the solution is proportional to the square of the period of the vibration. Use the following equation:
S = 1.3343 (p-po)103 + 2.155306 x 10-4 x [(p-po)103]2 1.171160 x 10-5 [(p-po)103]3

Where, (p-po) = B (t2 to2), t and to are respectively the periods of vibration for the solution and water. The system can be calibrated using N2 and H2O or standard seawater and H2O. The instrument constant (B) is determined from this calibration. 6. Sound speed: Measurement of sound speeds (U) relatives to pure water (Uo) the salinity can be determined as:
S = 0.91712 (U Uo) + 7.670097 x 10-4 x (U Uo)2 1.107557 x 10-5 (U Uo)3

7. Refractive index

Difficulties in dryness methods

The residue left after evaporation in gravimetric methods is mixture of complex salts, together with some water chemically bound to the solids, plus a small amount of organic material. The amount of water left behind can further be decreased by drying the residual salts at high temperature. This lead to other problems, such as: 1. Decomposition of some salts (loss of water and gaseous HCl from hydrous MgCl2) 2. Vaporization of decomposition organic matter 3. Expulsion of CO2 gases from carbonate salts.

Modern Salinometer are compact and rapid in operation, and can measures salinity to 0.001 or better. Conductivity sensors, have been incorporated into - in situ temperature-salinity instrument for use in shallow water, and - conductivity-temperature-depth (CTD) probes for use in the deep oceans. Because a salinity value determined by conductivity depends on the temperature and pressure at which the conductivity is measured. It is advisable to calibrate the system using weight-diluted seawater for better results

Precision in salinity determination by various methods

1. Evaporation to dryness 2. Composition studies of major components 3. Chlorinity 4. Conductivity 5. Density 6. Sound speed 7. Refractive index

0.01 0.01 0.002 0.001 0.004 0.03 0. 05

The Salt Balance: Addition and removal

The salts of the ocean come from the:
Land through river Chemical reaction of sea water with sediments Gases produced by volcanoes Spreading centers of the mid ocean ridge and rise system During volcanic eruptions sulfide and chloride gases are released, dissolved in rain water and carries to ocean as Cl- and SO42- ions. These Cl- and SO42- ions are acidic, grinded down and dissolved the rock over which it flows. It helps to liberate the other +ve ions such as, Na+, Ca2+ and Mg2+ from earth crust. When flowing through the fractured crust becomes heated. Heated reacted chemically with rock crust whereby copper, iron, manganese, zinc, potassium and calcium are dissolved in water

Salts are removed from sea water in a number of ways:

Sea spray from wave and action is blown a shore deposited a film of salt on the land Shallow arm of sea may becomes isolated the water evaporated and salt left behind to become land deposits Salt ions react with each other to form insoluble products that settled to ocean floor Biological process concentrated salt, which are removed with the harvest of organisms. Other biological process removes calcium by incorporating it into shells, silica is used to form hard parts of certain diatoms Adsorption is most important single process of ion removal.

Tiny clay mineral particles, weathered from rock are brought to ocean by he river or the winds, bind ions and molecules to their surface by a process known as adsorption The fecal pellets and skeleton left over of small organisms also act as adsorption surfaces. Calcium is removed rapidly from sea water, forming limestone and shells of marine organism. Na+ is moderately abundant in freshwater, but because it reacts slowly with other substances in sea water, it remains dissolved in ocean.

Residence time (RT)

The average time that the substances remains in solution in oceans is called its Residence time. Amount of substance in oceans RT = -------------------------------------------------------------------Rate at which substance is added to or removed from oceans The RT of substance in ocean depends on how reactive it is with the existing marine environment. Compounds that are less reactive have a longer residence time. The long residence time leads to the availability of higher concentrations of the dissolved substances. Calculations suggest that shallow surface water resides in ocean for period that average 100yrs, while deep water average between 1000 to 2000yrs.

Table: Approximate Residence Time of Ions in the Oceans Ions

Chloride Sodium Magnesium Potassium Sulfate Calcium Manganese Iron Aluminum

Time in years
100million infinite 260 million 22 million 11 million 11 million 1 million 0.0014 million (1400 yrs) 0.00014 million (140 yrs) 0.00010 million (100 yrs)

Source: The Worlds Oceans. Sverdrup, Duxbury and Duxbury,2005

Dissolved matter in inland waters

Most inland water is classed as freshwater: by definition means salinity lower than 3ppt. The concentration of solutes generally increases in river with distance from the source and can vary in response to discharge, while freshwater lake becomes more solutes enriched with time. The chemical composition of inland water is determined particularly by the catchments. Rain bringing some inputs, but the area with hard rock and thin soils adjacent to coast relatively unimportant. Many constituents of fresh water are, however at much higher concentrations then catchments weathering.

Table : Chemical constituents (mg/L) of rain water and river

Symbol ClNa+ SO4-2 Mg+2 Ca+2 K+ HCO3SiO2

Rainfall (continental) 0.2-2.0 0.2-1.0 1.0-3.0 0.05-0.5 0.2-4.0 0.1-0.5 0 0

Rainfall (marine & costal) 1.0-10.0 1.0-5.0 1.0-3.0 0.4-1.5 0.2-1.4 0.2-0.6 0 0

Rivers 3.4-7.0 3.2-7.0 3.5-15.1 1.4-5.2 5.3-24.2 1.0-1.6 26.7-80.1 6.8-16.3

The main differences is that HCO3- is the main anion in river and has a much higher concentration than ClCa2+ is the main cation in river water, followed by Na2+, Mg2+ and K+ The SiO2 is predominantly in the Unionized form Si(OH)4 in most river

The relative composition of rivers entering the oceans of various continents is shown as:

Dissolved Gases
The gases that composed the air is soluble in water, but solubility is not in it proportion. Solubility of various gases in surface of seawater at 0oC: Nitrogen Oxygen Carbon dioxide Argon 14.0mg/L 8.0mg/L 0.47mg/L 0.36mg/L

O2 and CO2 are important as they are non-conservative and depleted or produce with the depth. Oxygen is important in water, for respiration and carbon dioxide, for photosynthesis. Both originate mainly from the atmosphere, but diffusion mixes gases very slowly and physical mixing is required to ensure that they penetrate beyond the surface level.

Dissolved Oxygen
The major sources of oxygen in water are from air and also from photosynthetic activities. Solubility of oxygen depends on temperature, pressure salinity and so on depth. There exist inverse relationship of temperature and solubility of oxygen as shown below: Temperature (oC) 0 10 20 30 1 O2 solubility Temperature Solubility (mg/L) 8.0 6.3 5.2 4.3

Also with salinity solubility of O2 is inversely proportional Thus, seawater contains approximately 20% less oxygen than fresh water at an equivalent temperature and pressure. Dissolved oxygen concentration at saturation may be calculated as: Cm Saturation (%) = ----------- x 100 CS/ Cm is measured dissolved oxygen concentration in mg/L. TP CS/ = CS x ---------760 TP = BP + HP, where BP is the total pressure at given depth (mm Hg) and HP is the hydrostatic pressure (mm Hg) HP = (Z), where is the specific weight and Z is the depth.

Transfer of oxygen between air and water is reversible process. Transfer of oxygen from air to water occurs when water is unsaturated with dissolved oxygen and oxygen diffused from water to air when water supersaturated with dissolved oxygen. The driving forces causing net transfer of dissolved oxygen between air and water is the differences in oxygen tension. Although dissolved oxygen diffuses from air to water, but biological process are important than physical process to regulate oxygen concentration in water. Factors that control dissolved oxygen in natural water are: - Temperature - Light - Nutrients concentration - Species of plants/plankton - Abundance of plants/plankton -Turbulence or water mixing

Carbon dioxide

Carbon dioxide is subject to the same effect of temperature, pressure, salinity and depth as oxygen, but is considerably more soluble in water because it combines with alkali metals to form bicarbonates and carbonates according to the reactions

CO2 + H2O H2CO3 H+ + HCO3- 2H+ + CO32Therefore, very little carbon dioxide gas is present in water. Total dissolved carbon dioxide in oceans decreases with depth to about 100m and then is fairly constant to the bottom. This is because carbon uptake in the surface zone by biological activity (Photosynthesis and skeleton production) while, in deep water, lower rates of carbon uptake are balance by regeneration from decomposition of organic particles.

Thermal/chemical Stratification
Lakes share many physical characteristics with oceans, modified by their size and depth. All but the shallowest lakes undergo stratification similar to that in marine systems. Life in lakes and larger ponds experiences seasonal shifts. The heating and cooling of surface waters changes temperature and oxygen levels through out the basin.

With the onset of cooler weather, the temperature of epilimnion drops until it is the same as that of the hypolimnion. Then the water of the enter lake or begins circulating oxygen and nutrients. This circulation, which recharges oxygen and nutrients through the basin, is called the fall overturn. Stirred by wind, the overturn may last until ice forms.

Then comes winter, and the surface water cools to below 4oC. It becomes lighter again and remains on the surface. If winter is cold enough, surface water freezes, the process called winter stratification. In winter supply of oxygen is usually not greatly reduced because bacterial decomposition and respiration of organisms are not so great at low temperature. At low temperature water also holds more oxygen. But if ice form at the surface, it prevents photosynthesis, resulting in oxygen depletion for the enter lake and winter kill of the fish.

In spring the ice melts and water becomes warmer, it becomes heavier and sinks to the bottom.

Thus, when the surface temperature rises to 4oC, the lake takes another deep breath, as it were the spring overturn.

Nutrients Status
A close relationship exists between land and water ecosystems. Primarily through the hydrological cycle, one feeds on the other. The water carries it silt and nutrients in solution. Human activities, including road construction, logging, mining, construction and agricultural, add another heavy loaded silts and nutrients, especially nitrogen and phosphorus and organic matter. These inputs enrich aquatic systems, a process called eutrophication.

The term eutrophy (from the Greak eutrophos, well nourished) means a condition of being nutrient rich. The opposite is oligotrophy, the condition of being nutrient poor.

Eutrophic Systems
A typical lake has high surface to volume ratio; that is, the surface area is larger relative to depth. An abundance of nutrients, especially nitrogen and phosphorus, stimulates a heavy growth of algae and other aquatic plants. Increase photosynthesis production leads to an increases re-generation of nutrients and organic compounds, stimulating even further growth

Eutrophic condition Phytoplankton concentrations in the warm upper layer of the water, giving it a murky green cast. The turbidity reduces light penetration and restricts biological productivity to a narrow layer of surface water. Algae, inflowing organic debris and sediment, and remains of rooted plants drift to the bottom, adding to the highly organic sediments. Bacteria partially convert this dead organic matter into inorganic substances. The activities of these decomposers deplete the oxygen supply of the bottom sediments and deep water to the point at which this region of the lake cannot support aerobic life. The number of bottom species declines, although the biomass and number of organisms remain high.

Oligotrophic System
Oligotrophic lakes have a low surface to volume ratio. The water is clear and appears blue to blue-green in sunlight. The epilimnion is cool, the hyperlimnion is high in oxygen, and bottom sediments are largely inorganic. The nutrient content of the water, however, is low; and although nitrogen may be abundant, phosphorus is highly limited.

With the additions of increasing quantities of nutrients by human or natural way added to a lake or pond, it begins to change from oligotrophic to metatrophic to eutrophic

Oligotrophic condition
Low availability of nutrients causes low productivity of organic matter, particularly phytoplankton. Low organic matter production leaves little for decomposers, so oxygen concentration remains high in the hyperlimnion. The lack of decomposable organic matter means low bacterial populations and slow rates of microbial metabolism. Although the number of organisms in oligotriophic lakes and ponds may be low, species diversity is often high.

Dystrophic system
Water bodies that receive large amounts of organic matter from surrounding land, particularly in the form of humic materials that stain the water brown are called dystrophic (from dystrophs means ill nourished). Productivity of such water bodies is low, only low in phytoplankton production. Such types of water bodies generally have large productive littoral zone, particularly those developed bog flora. These zones are providing sources of both dissolved and particulate organic matter.

QUESTIONS?