Groundwater Geochemistry

by Merkel, Broder J.; Planer-Friedrich, Britta; Nordstrom, Darrell Kirk

• ISBN13: 9783540241959
• ISBN10: 3540241957
• Edition: CD
• Format: Hardcover
• Copyright: 2005-04-15
• Publisher: Springer Verlag

Summary

The 2nd edition of "Groundwater Geochemistry a?? A practical guide to modeling of natural and contaminated aquatic systems" remains the comprehensive text book offering beginners and advanced modellers alike a minimum theoretical background and a strong focus on the practical solution of geochemical modeling with PHREEQC. The new edition covers the possibility to use PITZER equation and the CD music concept within the new version of PHREEQC. Examples for reactive transport use PHREEQCA's 1d features with multicomponent diffusion as well as PHAST with the graphical user interface GoPhast on 2d and 3d examples. Implementing uncertainties of thermodynamically data is addressed by means of the program Ljungskile. As in the 1st edition, detailed descriptions on how to solve each problem step by step guide the user from basic to more and more advanced hydrogeochemical modelling.

Author Biography

Broder J. Merkel was offered the chair of hydrogeology at the Technische Universitat Bergakademie Freiberg in 1993.

Table of Contents

Theoretical Background	1	(66)
Equilibrium reactions	1	(48)
Introduction	1	(3)
Thermodynamic fundamentals	4	(1)
Mass action law	4	(2)
Gibbs free energy	6	(1)
Gibbs phase rule	7	(1)
Activity	8	(1)
Ionic strength	8	(2)
Calculation of activity coefficient	10	(1)
Theory of ion dissociation	10	(2)
Theory of ion interaction	12	(2)
Theories of ion dissociation and ion interaction	14	(3)
Interactions at the liquid-gaseous phase boundary	17	(1)
Henry-Law	17	(1)
Interactions at the liquid-solid phase boundary	18	(1)
Dissolution and precipitation	18	(1)
Solubility product	18	(2)
Saturation index	20	(2)
Limiting mineral phases	22	(2)
Sorption	24	(1)
Hydrophobic /hydrophilic substances	24	(1)
Ion exchange	24	(6)
Mathematical description of the sorption	30	(4)
Interactions in the liquid phase	34	(1)
Complexation	34	(2)
Redox processes	36	(1)
Measurement of the redox potential	36	(1)
Calculation of the redox potential	37	(4)
Presentation in predominance diagrams	41	(4)
Redox buffer	45	(1)
Significance of redox reactions	46	(3)
Kinetics	49	(8)
Kinetics of various chemical processes	49	(1)
Half-life	49	(1)
Kinetics of mineral dissolution	50	(1)
Calculation of the reaction rate	51	(1)
Subsequent reactions	52	(1)
Parallel reactions	53	(1)
Controlling factors on the reaction rate	53	(2)
Empiric approaches for kinetically controlled reactions	55	(2)
Reactive mass transport	57	(10)
Introduction	57	(1)
Flow models	57	(1)
Transport models	57	(1)
Definition	57	(1)
Idealized transport conditions	58	(2)
Real transport conditions	60	(1)
Exchange within double-porosity aquifers	61	(2)
Numerical methods of transport modeling	63	(1)
Finite-difference / finite-element method	63	(2)
Coupled methods	65	(2)
Hydrogeochemical Modeling Programs	67	(44)
General	67	(17)
Geochemical algorithms	67	(2)
Programs based on minimizing free energy	69	(1)
Programs based on equilibrium constants	70	(1)
PHREEQC	70	(2)
EQ 3/6	72	(1)
Comparison PHREEQC - EQ 3/6	73	(3)
Thermodynamic data sets	76	(1)
General	76	(2)
Structure of thermodynamic data sets	78	(2)
Problems and sources of error in geochemical modeling	80	(4)
Use of PHREEQC	84	(27)
Structure of PHREEQC under the Windows surface	84	(1)
Input	85	(8)
Thermodynamic data	93	(1)
Output	94	(1)
Grid	95	(1)
Chart	95	(1)
Introductory Examples for PHREEQC Modeling	95	(1)
Equilibrium reactions	95	(1)
Example 1: Standard output -- seawater analysis	96	(2)
Example 2 equilibrium -- solution of gypsum	98	(1)
Introductory examples for kinetics	99	(1)
Defining reaction rates	100	(3)
Basic within PHREEQC	103	(3)
Introductory example for reactive mass transport	106	(5)
Exercises	111	(32)
Equilibrium reactions	112	(18)
Groundwater - Lithosphere	112	(1)
Standard-output well analysis	112	(1)
Equilibrium reaction - solubility of gypsum	113	(1)
Disequilibrium reaction - solubility of gypsum	113	(1)
Temperature dependency of gypsum solubility in well water	113	(1)
Temperature dependency of gypsum solubility in distilled water	113	(1)
Temperature and P(CO2) dependent calcite solubility	113	(1)
Calcite precipitation and dolomite dissolution	114	(1)
Calcite solubility in an open and a closed system	114	(1)
Pyrite weathering	114	(2)
Atmosphere -- Groundwater -- Lithosphere	116	(1)
Precipitation under the influence of soil CO2	116	(1)
Buffering systems in the soil	116	(1)
Mineral precipitates at hot sulfur springs	117	(1)
Formation of stalactites in karst caves	117	(1)
Evaporation	118	(1)
Groundwater	119	(1)
The pE-pH diagram for the system iron	119	(3)
The Fe pE-pH diagram considering carbon and sulfur	122	(1)
The pH dependency of uranium species	122	(1)
Origin of groundwater	123	(1)
Origin of spring water	124	(1)
Pumping of fossil groundwater in arid regions	125	(2)
Salt water / fresh water interface	127	(1)
Anthropogenic use of groundwater	127	(1)
Sampling: Ca titration with EDTA	127	(1)
Carbonic acid aggressiveness	128	(1)
Water treatment by aeration - well water	128	(1)
Water treatment by aeration - sulfur spring	128	(1)
Mixing of waters	129	(1)
Rehabilitation of groundwater	129	(1)
Reduction of nitrate with methanol	129	(1)
Fe(0) barriers	130	(1)
Increase in pH through a calcite barrier	130	(1)
Reaction kinetics	130	(7)
Pyrite weathering	130	(1)
Quartz-feldspar-dissolution	131	(1)
Degradation of organic matter within the aquifer on reduction of redox sensitive elements (Fe, As, U, Cu, Mn, S)	132	(1)
Degradation of tritium in the unsaturated zone	133	(4)
Reactive transport	137	(6)
Lysimeter	137	(1)
Karst spring discharge	137	(1)
Karstification (corrosion along a karst fracture)	138	(1)
The pH increase of an acid mine water	139	(1)
In-situ leaching	140	(3)
Solutions	143	(42)
Equilibrium reactions	143	(25)
Groundwater-Lithosphere	143	(1)
Standard-output well analysis	143	(2)
Equilibrium reaction-solubility of gypsum	145	(1)
Disequilibrium reaction -- solubility of gypsum	146	(1)
Temperature dependency of gypsumsolubility in well water	146	(1)
Temperature dependency of gypsum solubility in distilled water	146	(1)
Temperature and P(CO2) dependent calcite solubility	147	(1)
Calcite precipitation and dolomite dissolution	148	(1)
Comparison of the calcite solubility in an open and a closed system	149	(1)
Pyrite weathering	150	(2)
Atmosphere-Groundwater-Lithosphere	152	(1)
Precipitation under the influence of soil CO2	152	(1)
Buffering systems in the soil	152	(1)
Mineral precipitations at hot sulfur springs	152	(1)
Formation of stalactites in karst caves	153	(1)
Evaporation	154	(1)
Groundwater	155	(1)
The pE-pH diagram for the system iron	155	(1)
The Fe pE-pH diagram considering carbon and sulfur	156	(1)
The pH dependency of uranium species	157	(2)
Origin of groundwater	159	(1)
Origin of spring water	159	(1)
Pumping of fossil groundwater in arid regions	159	(1)
Salt water / fresh water interface	160	(1)
Anthropogenic use of groundwater	161	(1)
Sampling: Ca titration with EDTA	161	(1)
Carbonic acid aggressiveness	162	(1)
Water treatment by aeration - well water	162	(1)
Water treatment by aeration - sulfur spring	162	(2)
Mixing of waters	164	(1)
Rehabilitation of groundwater	165	(1)
Reduction of nitrate with methanol	165	(1)
Fe(0) barriers	166	(1)
Increase in pH through a calcite barrier	167	(1)
Reaction kinetics	168	(8)
Pyrite weathering	168	(3)
Quartz-feldspar-dissolution	171	(1)
Degradation of organic matter within the aquifer on reduction of redox sensitive elements (Fe, As, U, Cu, Mn, S)	172	(3)
Degradation of tritium in the unsaturated zone	175	(1)
Reactive transport	176	(9)
Lysimeter	176	(1)
Karst spring discharge	176	(2)
Karstification (corrosion along a karst fracture)	178	(1)
The pH increase of an acid mine water	179	(2)
In-situ leaching	181	(4)
References	185	(6)
Index	191