====== Environmental Hydrology Notes ======
===== Topics =====
Please do research on one of the following topics:
* Alarm models in rivers, example from Rhine and rivers (e.g. Ukraine)
* Natural remediation - principles and applications
* Microbiological remediation of groundwater for oil spills
* Pump and treat of groundwater - focus on chlorinated hydrocarbons
* Artificial wetlands - principles and case studies
* Soil protection and remediation
* Phosphate recovery - Pilot Plant in Hamburg
===== PhreeqC scripts =====
TITLE Speciate seawater is replaced by fresh water
SOLUTION 0 Fresh terrestrial Water
units mmol/l
pH 7.0
Ca 1.0
Mg 0.1
Na 1.0
K 1.1
Alkalinity 2.0 as HCO3
S(6) 1.0
N(5) 0.1
Cl 0.2
SOLUTION 2-80 Fresh terrestrial Water
units mmol/l
pH 7.0
Ca 1.0
Mg 0.1
Na 1.0
K 1.1
Alkalinity 2.0 as HCO3
S(6) 1.0
N(5) 0.1
Cl 0.2
SOLUTION 1 SEAWATER FROM NORDSTROM AND OTHERS (1979)
units ppm
pH 8.22
# pe 8.451
density 1.023
temp 25.0
Ca 412.3 # mg/kg
Mg 1291.8
Na 10768.0
K 399.1
Alkalinity 141.682 as HCO3
S(6) 2712.0
N(5) 0.29 gfw 62.0
N(-3) 0.03 as NH4
Cl 19353.0
Fe 0.002
Mn 0.0002
Si 4.28
EXCHANGE 1-80
-equilibrate 1
X 0.1
TRANSPORT
-cells 80
-lengths 80*5.0
-shifts 80
-time_step 86400
-flow_direction forward
-dispersivities 80*4.0
-correct_disp true
-punch_cells 30
-punch_frequency 1
-print_cells 40
-print_frequency 40
SELECTED_OUTPUT
-file ex5.txt
-total Ca Mg Na K Cl
-molalities Ca+2 HCO3- Cl-
-si Calcite Gypsum
END
TITLE Seawater species
SOLUTION 0 Clean water for flushing
units mmol/kgw
pH 7.0
temp 10.0
Mg 5.0
Cd 1.0
Cl 12.0
SOLUTION 1 Pulse of polluted water with K-Alkalinity
units mmol/kgw
pH 7.0
temp 10.0
K 100
Cl 100
SOLUTION 2-50 Clean water in the soil (before pulse)
units mmol/kgw
pH 7.0
temp 10.0
Ca 100
Alkalinity 100
EXCHANGE 1-50
-equilibrate 2
X 0.0011
TRANSPORT # Make column temperature 0C, displace Cl
-cells 50
-shifts 50
-flow_direction forward
-boundary_conditions flux flux
-lengths 50*0.1 # m
-time_step 86400 # unit is second
-dispersivities 50*0.1 # dispersivity is given in m
-punch_cells 10 # 20 30 40 50
-punch_frequency 1
SELECTED_OUTPUT
-file EHP1.txt
-temperature
-step
-distance
-time
-totals Ca Mg K Cl Cd
-molalities CaX2 MgX2 CdX2
END
==== Sorption and Ion Exchange ====
You can include sorption by using the key - word exchange. The key word has an identifier (1-40). The exchange site is called X. The capacity is in this case 0.0011.
EXCHANGE 1-40
-equilibrate 1
X 0.0011
==== Surface Complexation ====
SURFACE 1
Hfo_sOH 5e-6 600. 0.09
Hfo_wOH 2e-4
Hfo_SOH or Hfo_wOH is the name of the surface binding site.
5e-6 or 2e-4 in this example is the total number of sites for this binding site, in moles; applies when -sites_units is absolute (default). Could also be given as site density, in sites per square nanometer when -sites_units is density.
600. in this example is th specific area of surface, in $m^2/g$ (square meter per gram). Default is 600 $m^2 /g$.
0.09 in this example is the mass of solid for calculation of surface area, g (gram); surface area is grams times specific_area_per_gram. Default is 0 g.
Only one parameter is realy needed, the first one. The other two are optional. Without any further information the default values of 600. and 0. are assumed otherwise.
TITLE Seawater species # Please use Minteq.v4 database
SOLUTION 0 Clean water for flushing
units mmol/kgw
pH 7.0
temp 10.0
Mg 5.0
Cd 1.0
Cl 15.0
As 1.0
SOLUTION 1 Pulse of polluted water with K-Alkalinity
units mmol/kgw
pH 7.0
temp 10.0
K 100
Cl 100
SOLUTION 2-50 Clean water in the soil (before pulse)
units mmol/kgw
pH 7.0
temp 10.0
Ca 100
Alkalinity 100
SURFACE 1-50
Hfo_sOH 5e-6 600. 0.09
Hfo_wOH 2e-4
TRANSPORT # Make column temperature 0C, displace Cl
-cells 50
-shifts 50
-flow_direction forward
-boundary_conditions flux flux
-lengths 50*0.1 # m
-time_step 86400 # unit is second
-dispersivities 50*0.1 # dispersivity is given in m
-punch_cells 10 # 20 30 40 50
-punch_frequency 1
SELECTED_OUTPUT
-file EHP1.txt
-temperature
-step
-distance
-time
-totals Ca Mg K Cl Cd As
END
==== Development of an Arsenic Filter ====
Modifications to the input file, 10.5.2017:
* Check and fix the charge balance error in solution 1
* add -molalities for As-species in SELECTED_OUTPUT.
* add molalities for species dissolved in water HAsO4-2 H2AsO4-
TITLE Seawater species # Please use Minteq.v4 database
SOLUTION 0 Clean water for flushing
units mmol/kgw
pH 7.0
temp 10.0
Mg 5.0
Na 1.0
Cl 8.0
As 1.0
SOLUTION 1 Pulse of polluted water with K-Alkalinity
units mmol/kgw
pH 7.0
temp 10.0
K 100
Cl 100
SOLUTION 2-50 Clean water in the soil (before pulse)
units mmol/kgw
pH 7.0
temp 10.0
Ca 100
Alkalinity 200
SURFACE 1-50
Hfo_sOH 5e-3 600. 0.5
Hfo_wOH 2e-3
TRANSPORT # Make column temperature 0C, displace Cl
-cells 50
-shifts 50
-flow_direction forward
-boundary_conditions flux flux
-lengths 50*0.1 # m
-time_step 86400 # unit is second
-dispersivities 50*0.1 # dispersivity is given in m
-punch_cells 10 # 20 30 40 50
-punch_frequency 1
SELECTED_OUTPUT
-file AsFilter.txt
-temperature
-step
-distance
-time
-totals Ca Mg K Cl As
-molalities HAsO4-2 H2AsO4- Hfo_sHAsO4-
END
==== Plotting ====
Dandi Shen has found and proposed a direct plotting from PhreeqC:
TITLE Seawater species
SOLUTION 0 Clean water for flushing
units mmol/kgw
pH 7.0
temp 10.0
Mg 5.0
Cd 1.0
Cl 12.0
SOLUTION 1 Pulse of polluted water with K-Alkalinity
units mmol/kgw
pH 7.0
temp 10.0
K 100
Cl 100
SOLUTION 2-50 Clean water in the soil (before pulse)
units mmol/kgw
pH 7.0
temp 10.0
Ca 100
Alkalinity 100
TRANSPORT # Make column temperature 0C, displace Cl
-cells 50
-shifts 50
-flow_direction forward
-boundary_conditions flux flux
-lengths 50*0.1 # m
-time_step 86400 # unit is second
-dispersivities 50*0.1 # dispersivity is given in m
-punch_cells 10 # 20 30 40 50
-punch_frequency 1
SELECTED_OUTPUT
-file EHP1.txt
-temperature
-step
-distance
-time
-totals Ca Mg K Cl Cd
USER_GRAPH total Ca with cells
-headings Ca Mg Cd
-axis_titles "Cell number" "Mg and Cd in mmol" "Ca in mmol"
-chart_title "Bla"
-axis_scale x_axis 0 46 10 1
-axis_scale y_axis 0 0.01 0.0005 0
-axis_scale sy_axis 0 0.1 0.005 0
-initial_solutions false
-connect_simulations true
-start
10 x = step_no
20 plot_xy x-4, tot("Ca"), color = Red, symbol = Square, symbol_size = 6, y-axis = 2
30 plot_xy x-4, tot("Mg"), color = Blue, symbol = Square, symbol_size = 6, y-axis = 1
40 plot_xy x-4, tot("Cd"), color = Green, symbol = Square, symbol_size = 6, y-axis = 1
-end
END
===== Adding organics to solution - pollution =====
REACTION 1
CH2O(NH3)0.07 1.0
1. 2. 3. 4. 8. 16. 32.0 64 125.00 250. 500. 1000. mmol
===== Assignment =====
==== Reactive Transport ====
The following problem is to be solved. In the city of Lübeck there is a polluted site 800 m from the river Trave. You should model the transport from the polluted site to the river and answer the questions:
- when does the pollutant reach the river?
- what is the concentration at the inflow to the river Trave?
The following analyses are available: Unpolluted infiltration water infiltrating at the site
TITLE Infiltrating water
SOLUTION 1 Infiltrate
units mg/l
pH 5.5
temp 10.0
Ca 2.5
Mg 0.215
Na 0.705
K 0.18
C(4) 7.5 as HCO3-
S(6) 5.0 as SO4
N(5) 1.18 as NO3
Cl 1.18
END
TITLE Groundwater upstream
SOLUTION 1 Groundwater
units mg/l
temp 10.0
pH 8.22
Ca 33.3
Mg 3.5
K 1.5
Na 7.5
C(4) 85.0 as HCO3-
S(6) 10.8 as SO4-2
Cl 11.8
N(5) 14.5 as NO3-
Fe 0.02
END
The exchanger X has a capacity of 0.005 mol. The exchanger is in equilibrium with the original unpolluted groundwater.
* __Group 1__: Model a pollution with 5 mg/L Cu in recharge water.
* __Group 2__: Model a pollution with 5 mg/L Cd in infiltration water.
* __Group 3__: Model a pollution with 5 mg/L Pb in infiltration water.
* __Group 4__: Model a pollution with 5 mg/L Cr in infiltration water.
== 4.2.1 Breakthrough Curves ==
When do the contaminants reach the river?
== 4.2.2 Concentration ==
Which concentrations do you observe?
== 4.2.3 Distribution ==
Which species are on the exchanger and at what concentration.
== 4.2.4 Surface complexation ==
What would surface complexation do?
==== Template for report ====
Please submit the report until 15. 09. 2018. Please prepare a 5 to 7 pages report for the assignment with introduction, problem statement, methodology and major results in a graph and/or table and conclusions.
Use can use this template: {{ :en:lectures:ehydrology:bsc-vorlage.docx |(Word)}}
===== Literature =====
- Appelo, C. Anthony J., and Dieke Postma. Geochemistry, groundwater and pollution. CRC press, 2004.
- Merkel, Broder J., and Britta Planer-Friedrich. Grundwasserchemie: praxisorientierter Leitfaden zur numerischen Modellierung von Beschaffenheit, Kontamination und Sanierung aquatischer Systeme. Springer-Verlag, 2008.
==== Links ====
* [[http://www.stoffdaten-stars.de/|Stoffdatenbank STARS]]
* Diagramme ([[http://www.lha.univ-avignon.fr/LHA-Logiciels.htm|Software]] zur Darstellung hydrochemischer Analysen)