EART20302 Reservoir and Production Chemistry

Practical 3. Diagenetic Cementation Reactions

Along with the physical process of compaction, the formation of mineral cements can drastically alter the porosity and permeability of source and reservoir rocks. In this practical we will 1) model the formation of dolomite cement in the Gippsland basin, a major offshore Australian petroleum province, and then 2) model the precipitation of dolomite together with anhydrite to explain the diagenetic cements in parts of the Lyons sandstone, a petroleum reservoir in the Denver basin of the western USA. I. Gippsland Basin Oil is in the Latrobe group, a fluvial sandstone rich in quartz, K-feldspar, and illite (which can be modelled by muscovite). Porosities can be over 25%, and permeability can be greater than 2 darcys. However, in parts dolomite cement can make up 40% of the volume, plus kaolinite and quartz cement equal to several more percent of the volume. Here, K-feldspar is leached and pyrite is corroded. The proposed explanation is that fresh meteoric water recharges the Latrobe group where it outcrops on land and this mixes with more saline formation waters offshore. To test this idea, we will mix these two fluids in contact with the solid phases known to be present, and see whether mineral cements are produced. A) Create a fresh water in REACT and equilibrate it with the rock. swap Maximum Microcline for Al+++ swap Quartz for SiO2(aq) swap Muscovite for K+ T = 60 TDS = 8530 pH = 6.95 Ca++ = 32 mg/l Mg++ = 9 mg/l Na+ = 2943 mg/l HCO3- = 1135 mg/l
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SO4-- = 1461 mg/l Cl- = 2953 mg/l 1 free cm3 Muscovite 1 free cm3 Quartz 1 free cm3 Maximum Microcline go

B) Turn the resulting fluid into a reactant with excess amounts to titrate into the saline water. We need to keep the result, so we pick it up. We also need to make a lot of it so we can go further than a 1:1 mix. pickup reactants = fluid reactants times 100

C) Prepare the saline fluid in equilibrium with the correct mineral assemblage, and then react it with the previous fluid. swap Maximum Microcline for Al+++ swap Quartz for SiO2(aq) swap Muscovite for K+ swap Dolomite-ord for HCO3T = 60 TDS = 32320 pH = 5.55 Ca++ = 220 mg/l Mg++ = 1000 mg/l Na+ = 11000 mg/l
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SO4-- = 900 mg/l Cl- = 19000 mg/l 10 free cm3 Muscovite 10 free cm3 Quartz 10 free cm3 Maximum Microcline 10 free cm3 Dolomite-ord go

1) Write the important precipitation reaction(s). SiO2(aq) -> Quartz Ca++ + Mg++ + 2 HCO3- -> Dolomite-ord + 2 H+ 6 H2O + K+ + 3 Al+++ + 3SiO2(aq) -> Muscovite + 10 H+ 2) Write the important dissolution reaction(s). Maximum microcline + 4 H+ = 2 H2O + K+ + Al+++ + 3 SiO2(aq) 3) Explain how acidity is generated and/or neutralized. See dissolution and precipitation reactions above. Dissolution outpaces precipitation to buffer and finally neutralize the acidity in the system. 4) Make a plot of mineral volume changes as a function of fresh water mass reacted.

5) Explain in detail what happens to the volume of K-feldspar in the system. What controls this reaction pathway?

Early on, as the K+ activity coefficient rises, the K+ activity is increased and this drive the dissolution reaction to the left (precipitation). As the activity coefficients reach steady state and as the fluids mix, this effect no longer control the feldspar chemistry and it dissolves.

II. Lyons Sandstone This is a quartz sandstone that has: i) a red facies with abundant iron oxides plus quartz and calcite cement overgrowths, ii) a gray facies with no iron oxides or calcite. The gray facies is deep, has residual bitumen, and is a petroleum reservoir. This facies is cemented with anhydrite and dolomite which occupy up to 25% and 15% of the rocks pre-cement volume, respectively. This facies is of special interest due to the petroleum presence. Geochemical evidence constrains the formation of this gray facies to be due to diagenesis and not due to original deposition or very early alteration. The idea is that a less permeable underlying formation, the Fountain formation which is separated from the Lyons by an aquitard, at points contributed fluids with a different chemistry into the Lyons formation. Dispersive mixing within the gray facies produced a unique mineralogical reaction pathway. A summary diagram is below.

A) Create a Lyons groundwater, using data from a current borehole and keeping it in equilibrium with calcite and quartz, also raise the temperature from 51 oC to 100 oC. We need to save this as a reactant fluid. swap Calcite for H+ swap Quartz for SiO2(aq) Na+ = 108 mg/kg Ca++ = 40 mg/kg Mg++ = 1 mg/kg Cl- = 9 mg/kg

SO4-- = 36 mg/kg HCO3- = 340 mg/kg balance on HCO31 free cm3 Calcite 1 free cm3 Quartz T initial = 51, final = 100 go pickup fluid save Lyons_100 This saves the result as a reactant for use later B) We cant directly measure the Fountain fluid, so we assume that it is in equilibrium with the evaporite minerals we know are present, including dolomite, anhydrite, magnesite, and quartz, plus a high concentraion of Na+ and Cl- due to halite dissolution. We infer pH from carbonate partial pressure. By assuming dolomite and magnesite saturation, we have indirectly fixed the calcite degree of saturation. Using these constraints we can calculate an inferred fluid composition and then make it a reactant for titration into the Lyon fluid as we did in the Gippsland example. reset swap CO2(g) for H+ swap Magnesite for Mg++ swap Anhydrite for SO4 swap Dolomite-ord for Ca++ swap Quartz for SiO2(aq) Na+ = 3 molal Cl- = 3 molal f CO2(g) = 60

1 free mole Magnesite 1 free mole Anhydrite 1 free mole Dolomite-ord 1 free mole Quartz balance on HCO3T = 100 go

C) Now, we mix the two and see how the fluid evolves. pickup reactants = fluid reactants times 15 read Lyons_100 (do not reset configuration when prompted) swap Quartz for SiO2(aq) swap Calcite for HCO3100 free mol Quartz 100 free mol Calcite balance on Clgo 1) Plot volume change of minerals as a function of Fountain brine reacted.

2) Write the overall reaction that controls the formation of cement. 2 Calcite + Mg++ + SO4-- -> Dolomite + Anhydrite 3) Discuss the assumptions that have gone into this model and what changes you would make to improve your predictive capability in this case. There are many. Two key ones involve the omission of any redox active couples and that calcite buffers HCO3-.