APPENDIX B

The method for determination of hydrate amount is based on Figure 6 and the assumptions of isotopic equilibrium between pore water and hydrate and 100% exclusion of Cl- during formation of hydrate.

First, values for the concentration of Cl- and 2H are assigned to the ascending brine and the transport equations (Appendix A) are used to generate flow-rate-independent curves (FRI-curves, see "Estimation of Hydrate Amount" section, this paper) using these values as boundary conditions (curves labeled 1, 2, and 3 in Fig. 6). The FRI-curves represent all possible combinations of in situ pore-water Cl- concentrations and 2H values ([Cl-]pw and 2Hpw) for the chosen boundary conditions.

Second, a vector V is constructed that starts from the FRI-curve ([Cl-]pw, 2Hpw) and projects into the [Cl-]-2H space with a slope given by

, (B1)

where is the isotope fractionation factor between hydrate and water.

This vector represents the change in [Cl-] and 2H that takes place when pore water with an initial composition given by the point ([Cl-]pw, 2Hpw) on the FRI-curve is diluted by hydrate meltwater. This is justified as follows.

Measured concentrations of Cl- and 2H ([Cl-]m, 2Hm) are volumetric averages of pore-water compositions ([Cl-]pw, 2Hpw) and hydrate meltwater compositions (0, 2HH),

and (B2)

, (B3)

where f is the volume fraction of hydrate meltwater. Because of the assumption of isotopic equilibrium, 2HH and 2Hpw are related through:

. (B4)

Following the example of Kvenvolden and Kastner (1990) the hydrogen isotope fractionation factor for the hydrate-water system is set equal to the fractionation factor for the ice-water system (1.021, Lehmann and Siegenthaler, 1991).

By evaluating

(B5)

from Equation B2, and

(B6)

from Equations B3 and B4, the slope of the vector may be derived from:

. (B7)

Third, the starting point of the vector V is moved along the FRI-curve until it intersects a measured pore water or hydrate sample composition (Fig. 6). This step is repeated until each measured point is represented by a vector.

Fourth, the vector V is decomposed into the vectors v1 and v2 (Fig. 6) which provides an estimate of the amount of hydrate based on the measured Cl- concentrations and 2H values respectively.