Llus Fontbot, Fluids, September 2012, p.

201209

!!

Reminder: three types of ore-bearing uids!

!! !! !!

Surface uids (meteoric, marine)! Hydrothermal uids! Magmas!

FLUID

CONSTITUANTS (S, LIGANDS, METALS)

TRANSPORT

PRECIPITATION

US FOC

This chapter: ! ! ! ! ! Sources and types of hydrothermal uids! Sources of constituents! Fluid transport! Constituents: transport and precipitation mechanisms!

Llus Fontbot, Fluids, September 2012, p. 2

Meteoric

Seawater

Connate

?
Metamorphic

Magmatic

Juvenile (mantle)

?
Bodnar (kluweronline)

60

50 Salinity(wt % NaCl equivalent "Secundary" magmatic fluid

40

30

Basinal brines

20

a M
10

at gm

m ic-

m ric o e et

n ixi

Metamorphic fluids

"Primary" magmatic fluid

Secondary magmatic fluid

100

200

300

400

500

600

800

900

Temperature (C)

Llus Fontbot, Fluids, September 2012, p. 3

(metals)

(Hedenquist)

(directly segregated from a magma)

Pettke, Heinrich

Llus Fontbot, Fluids, September 2012, p. 4

unr.edu/homepage/arehart/Courses/471-671/ Lecture_09._Isotopes_handout.pdf!

Hedenquist & Richards, 1998

Llus Fontbot, Fluids, September 2012, p. 5

!! When hydrothermal uids of magmatic origin arrive close to the surface tend to be acidic and oxidizing.! !! However, by water-rock interaction the uids will tend! !! to neutralize (reaction with carbonates, feldpars.)! !! to reduce (reaction with Fe2+ abundant in most rocks, organic C)! !! On the other side, saline uids that originally were not acidic, by interaction with rocks during their migration path, may become acidic. For example, Na+ can be xed by plagioclases and Cl- may form the acid ClH. !

Llus Fontbot, Fluids, September 2012, p. 6

Modern solutions
Element Seawater 1 Salton Sea 2 Cheleken 3 oil field Mississ. Black smoker

Ancient solutions (fluid inclusions)

4 (MVT) 5 (MVT) 6 (Bingham) 7 Bajo la Alumbrera

Cl Na Ca K Sr Ba Li Rb Cs Mg B Br I F NH4 HCO3H2 S SO42Fe Mn Zn Pb Cu

18,890 10,556 400 380 8

155,000 50,400 28,000 17,500 400 235 215 135 14 54 390 120 18 15 409 >150 16b 5 2,290 1,400 540 102 8

157,000 76,140 19,708 409 636 ---a 7.9 1.0 0 3,080 --526,50 31.7 ----31.9 0 309 14.0 46,5 3.0 9.2 1.4

158,200 59,500 36,400 538 1,110 61 ------1,730 --870 ----39 ----310 298 --300 80 ---

87,000 40,400 8,600 3,500 ----------5,600 <100 ------------1,200 --450 10,900 --9,100

46,500 19,700 7,500 3,700 ----------570 185 ------------1,600 --690 1,330 --140

295,000 152,000 4,400 67,000 --------------------------11,000 8,000 ---------

160,000 125,000 85 95 750

1272 65

140 2649

85,000 150,000 14,000 4,500 7,600

a Not determined. b Sulfide present; all S reported as H2S.

Llus Fontbot, Fluids, September 2012, p. 7

Cold calcium-rich vent fluid mixes turbulently with cold, sulfate- and calcium-rich seawater, resulting in precipitation of a ring of calcium sulfate (anhydrite). Metal sulfides and oxides carried in the hot fluid also precipitate rapidly during the mixing process, forming a plume of dark particles above the vent.

http://www.whoi.edu/oceanus/viewArticle.do?id=2400

Llus Fontbot, Fluids, September 2012, p. 8

World annual mine production: 13600000 t (2002) 132 m ! Every 1.5 year a new Bingham = 8.75 cm

~20600000 t of copper

Llus Fontbot, Fluids, September 2012, p. 9

Topics !
Sources and types of hydrothermal uids! Constituants - sources ! Fluid transport! Constituants: transport and precipitation mechanisms!

! ! ! !

Llus Fontbot, Fluids, September 2012, p. 10

SO4= or S= ?!
a uid there is SO4= and S= * ! !! in order to form sulfates, SO4= must be dominant (=> oxidizing conditions)! !! in order to form suldes, S= must be dominant (=> reducing conditions)! !! SO4= reduction !
!! in ! bacterial reduction (low T, up to ~ 80C)! ! by hydrocarbons (TSR)! ! other reductants (Fe2+, C4+)!

* and other S species like HSO4-, HS-, ...!

Llus Fontbot, Fluids, September 2012, p. 11

Topics !
Sources and types of hydrothermal uids! Constituent sources ! Fluid transport! Constituents: transport and precipitation mechanisms!

! ! ! !

Llus Fontbot, Fluids, September 2012, p. 12

A.! B.! C.! D.!

Thermal anomalies of magmatic origin : 80% of crustal uid ow ! Thermal anomalies caused by crustal thinning ! Gravitational movement! Others: "buoyancy"= ascension by density differences (controlled by salinity or temperature), sediment compression !

Llus Fontbot, Fluids, September 2012, p. 13

Duration of hydrothermal systems !

Topics !
Sources and types of hydrothermal uids! Constituant sources ! Fluid transport! Constituants: transport and precipitation mechanisms!

! ! ! !

Llus Fontbot, Fluids, September 2012, p. 14

At high T, metal solubilities are high.! At T < 400C metal solubility is in most cases controlled by following complexes:!

Chloride complexes!
Only effective complexes for virtually all base metals! in part also for gold!! !MeCl2(aq) + H2S(aq) = MeS(s) + 2H+ + 2Cl- ! ! ! ! !! examples: ! ZnCl2(aq) + H2S(aq) = ZnS(s) + 2H+ + 2Cl- !! ! !AuCl2-(aq) + 1/2H2O = Au(s) + 2Cl- + H+ + 1/4O2!

Pb, Zn, Cu! Au!

Sulde complexes!
Me(HS)3-(aq) + H+ = MeS(s) + 2H2S(aq)! example: Au(HS)2-(aq) + 1/2 H2 = Au(s) + H2S + HS-!

very important for Au, only effective complex below 250C! no base metals!

Llus Fontbot, Fluids, September 2012, p. 15

Saline uids may transport Pb, Zn, Cu, Ag, and Au*.! !! At T < 250C Au is best (~only) transported by sulde complexes! !! U can be transported by carbonate complexes and W by OH- complexes.! !! In general, non saline uids can transport Au, Ag, U, REE, but CAN NOT transport base metals. !
!!

* Below 250C, Au transport as chloride complex is ineffective!

Llus Fontbot, Fluids, September 2012, p. 16

According to the environment different mechanisms to precipitate Au.! High suldation (acidic and oxidizing conditions).....! Low suldation (close to neutrality, reducing conditions)...! Orogenic gold... !

Llus Fontbot, Fluids, September 2012, p. 17

Corbett & Leach 1997! Au transported as chloride! Au transported as bi-sulde! favors precipitation ! increases solubility!

T decrease or pH increase !

Mixing with low pH uids!

Corbett and Leach, 1997"

Llus Fontbot, Fluids, September 2012, p. 18

.. one of the possibilities is to destabilize the bi-sulde complex by forming suldes in the host rock!

Haeberlin (2002)

La Lima vein, Pataz, Peru!

Llus Fontbot, Fluids, September 2012, p. 19

Silica: Below 350C - precipitation largely controlled by decreasing T! Above 350C- also inuenced by decreasing salinity (A) and ! pressure (C, e.g. porphyry stockwork veins!)!

Calcite: precipitation largely controlled by increasing T,! also by decreasing P (=> increasing pH!)!

Llus Fontbot, Fluids, September 2012, p. 20

Madjarovo, vein nr. 2, Bulgaria!

L. Fontbot (2003)

Madjarovo, vein nr. 2, Bulgaria!

L. Fontbot (2003)

Llus Fontbot, Fluids, September 2012, p. 21

Madan, Bulgaria!

L. Fontbot (2003)

(Redrawn from Blount and Dickson, 1969)

(Redrawn from Blount 1977, in Corbett & Leach 1997)