GEOL 463 Oilfield Water Notes (Temporary version: to be replaced) Oilfield waters are routinely analysed for major

ions and some trace elements. The main ions analysed are Na+, Ca2+, Mg2+, K+, Cl-, SO42-, HCO3-, CO32-. Also commonly analysed are Br, Li, Fe, and SiO2. Isotopic analyses (O, C, Sr) are sometimes analysed for fluid tracing and provenance studies. Ion concentrations are variably expressed as ppm, mg l-1, meq l-1, and mmol l-1. mg l-1 = ppm / fluid density For dilute solutions, therefore, where water density is nearly 1.0, ppm is almost the same as mg l-1. For saline solutions, the dissolved salts increase the density of the fluid, so the values are not the same. It is useful to convert the fluid concentrations to milliequivalents, to test the validity of the analysis: meq l-1 = mg l-1 x valence / molecular weight The sum of the cations expressed in meq l-1 should be the same as the sum of the anions. For fresh waters, the difference in this balance should be < 5%. For saline waters, the difference should be < 10%. If the balance is poor, then there is probably either analytical error or important ions have not been analysed. Saline waters are commonly expressed as mg kg-1 or mmol kg-1 because their fluid density can be much greater than 1.0. Subsurface waters can be classified as free or irreducible. Free waters are normal waters that pass, or have passed through the pore system of the rock. They included waters recently in circulation (meteoric) waters, and connate waters, which are no longer in circulation and may have remained immobile in pores for millions of years. Meteoric waters may be fresh of saline; connate waters are normally brines. Formation waters (oilfield brines) are the fluids that were in the formation before drilling. They are mostly connate, or connate water mixed with meteoric water. Meteoric waters generally contain < 10 g l-1 total dissolved salts (TDS). They may be oxidizing or reducing, but do not generally increase in salinity with depth. Connate waters have salinities of 20 to > 300 g l-1 TDS (for comparison, seawater salinity is 35 g l-1 TDS). The salinity of connate waters generally increases with depth. Most subsurface waters are dominated by Na+ and Cl-. Compared to seawater they show a major decrease in SO42- and HCO3-, a reversal of the Mg:Ca ratio (i.e. connate brines are relatively enriched in Ca2+), and a major increase in ionic concentration. The increasing salinity with depth is poorly understood, but probably involves:

Dissolution of buried evaporites Filtering of ions in shale-sandstone units (ions concentrate in sandstones) Slow sinking of brines and upward displacement of less dense fluids

Water analyses can help in both exploration and production. In exploration, variations in fluid composition can help to delimit reservoir boundaries and reveal connectivity of different strata. Saline waters are generally more favorable for locating petroleum reservoirs. If the trapped fluid is saline, then there is less chance that any associated petroleum has been degraded by contact with meteoric water, or flushed from the reservoir.