Estuaries

Environmental Geochemistry DM Sherman, University of Bristol

Significance of Estuaries
Estuaries are major habitats for wildlife.

Many estuaries are greatly impacted by urban and agricultural runoff.

Significance of Estuaries (UK)

Geochemical Significance of Estuaries

Interface between Rivers and Seawaters: determines flux of chemical species into the ocean. Riverine pollutants react with seawater and may be accumulated in estuarine sediments. Chemical Processes: Mixing between River water and Seawater Change in ionic strength Change in pH Colloid flocculation

Rivers vs Seawater
Concentration in Average River (mmol/ kg) Seawater Concentration (mmol/kg) (M/Cl)sw (M/Cl)riv

pH ClNa+ Mg+2 SO4 K+ HCO3 BrH4SiO4

-2

5-7 0.16 0.224 0.138 0.068 0.334 0.033 0.852 -0.173

8.3 54.6 48.0 5.4 2.9 1.0 1.0 0.211 0.087 0.10 0.002 1 0.62 0.11 0.12 0.009 0.09 0.0007

Ca+2

Colloids
Colloids are very small particles that remain suspended in aqueous solutions. Much of the chemical flux in rivers in in the colloidal form. Primary colloidal phases in Rivers are: Clay minerals (kaolinite, montmorillonite) Iron (hydr)oxides (goethite, hematite, ferrihydrite). Humic/Fulvic acids associated with FeOOH.

Colloidal, particulate and dissolved

In practice, everything that passes through a 0.2 m filter is classed as dissolved. However, this includes much of the colloidal fraction.

Surface Charge of Colloids

+1/2 -1/2 -1/2

Surface charge is a function of pH, reflecting the variable protonation of surface oxygens. At the pHpzc, the surface charge is zero.

Sorption of Metals on Colloids

Sorption of Cu+2, Ni+2 on Goethite

Recall that sorption onto FeOOH minerals is a major control on the dissolved concentrations of metals.

Colloid Flocculation
Colloids will flocculate when their surface charge = 0. This will occur at the pHpzc and with increasing ionic strength.

Flocculation of colloids in estuaries will incorporate them (and their sorbed metals) into estuarine sediments.

Behavior during mixing River and Seawater

Mechanisms for Removal from Solution

Increased sorption of cations with increasing pH Flocculation of < 0.2 m colloid particles to decrease apparent dissolved concentration of Fe

Mechanisms for Adding to Solution

Complexation by Cl or HCO3from seawater causes desorption from colloidal FeOOH. But increasing pH (with salinity) causes readsorption.

Estuarine Sediments

Anoxic Conditions in Estuarine Sediments

As organic matter is consumed by respiration, O2 is depleted and new electron acceptors are used.
Anoxic mud

Marine Evaporite Basins

Restricted circulation and evaporation leads to increased salinity. Evaporite mineral sequence reflects relative solubility of CaCO3 (calcite), Gypsum (CaSO4.2H2O) and Halite (NaCl) Thermodynamic modelling of evaporite sequences is complicated by the highly non-ideal activities of ions at high ionic strength.

Pollution of Estuaries

Case Study: Hg pollution in California

Hg was used to extract gold during the California gold rush. Hg deposits are found in the Coast Ranges.

Erosion of mine tailings has led to Hg pollution of San Francisco Bay

The Wheal Jane Spill (Falmouth)..

In 1993 a major spill of mine waste released serious amounts of acid mine waste and heavy metals into Falmouth Bay.

Tamar Estuary (Pb)

Tamar Valley/Buttspiill Mine

10

Depth (cm)

30 50 70 90 2 4 6 8 pH 10 0 2 4 6 Porewater Pb (ppm) 0 1000 2000 Tot. Pb (ppm)

10

Tamar Estuary (Zn)

10

Depth (cm)

30 50 70 90 0 20 40 60 Porewater Zn (ppm)

Tot. Zn (ppm)

Summary
Much of the chemistry of estuaries is controlled by the flocculation of colloids which may remove some dissolved ions from solution. Some sorbed species (anions) should be released by increase in pH. Sorption at increased pH may incorporate trace heavy metals into estuarine sediments.

1000

400

600

200

800

6 8 pH

10

11