Exam Module M.HEG.03 Hydrochemistry Friday 25.02.2011, 10.15 am 11.

45 am

Name: ..

Course: ...

Student Registration Number: ..

Calculators are OK, but no computers, no books, no written material allowed

Total marks = 42 (pass: 17) Answer any 2 parts!

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HEG Dr. T. Licha/ Dr. M. Lodemann

Module M.HEG.03 Hydrochemistry EXAM 2011

Part 1: Isotope Hydrology: in total 21 points to gain 1. Stable isotopes and radioisotopes (9 points):
a) How many protons (p) and neutrons (n) have the following isotopes:
1

(2.0)

H : O:

17 3 3

H : He: S: (2.0)

33

b) What are the common stable isotope ratios and their standards for : (for example: boron: 11B/10B, Standard NBS 951) hydrogen: oxygen: carbon: sulfur:

c)

H decays by ..... to ..... with a half-life of ... Standards (units) for mother/daughter:

(3.0)

14

C decays by ..... to .... with a half-life of ... Standards (units) for mother/daughter:

226

Ra decays by ..... to ....... Standards (units) for mother/daughter:

d) Write down the delta-notation formula for stable nitrogen isotopes.

(2.0)

2.

Global Meteoric Water Line (2 points):

The deuterium excess of ... (value) is due to...... and depends locally (for example EMWL) on ... (2.0)

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HEG Dr. T. Licha/ Dr. M. Lodemann 3.

Module M.HEG.03 Hydrochemistry EXAM 2011

Isotope Fractionation (5.5 points): (underline correct term where appropriate)

(1.5)

a) Write down the common formula for with respect to temperature effect and thermodynamical constants (temperature in Celsius or Kelvin ?):

b) Do isotope fractionation effects generally increase or decrease with increasing temperature ? (1.0) c) Evaporation (from ocean): kinetic or/and equilibrium process ? (0.5)

d) What means the fraction factor = 1.0075 between two phases (here between water and vapour at 50 oC) with respect to the enrichment factor [])? (1.0)

e) Write down the Rayleigh equation for 18O in the system vapour-rainout. What means R and f in this case ? (1.5)

4. Miscellaneous (4.5 points):

a) Are the 87Sr/86Sr ratios in carbonate aquifers in general higher or lower than in granites ? . Why ?: (2.0)

b) What means Dead carbon with respect to 14C dating of groundwaters ?

(1.5)

c) What happens during subrosion/weathering of evaporites with respect to the fractionation of sulfur isotopes ?

(1.0)

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HEG Dr. T. Licha/ Dr. M. Lodemann

Module M.HEG.03 Hydrochemistry EXAM 2011

Part 2: Organic Hydrochemistry: in total 21 points to gain 1)

CH3
m.p. 35 C , b.p. 240 C LD50: 1650 mg/kg 1.001 g/mL log Kow 3.87 m.p. -24 C , b.p. 172 C LD50: 500 mg/kg 1.3 g/mL log Kow 3.4 m.p. 186 C , b.p. >300 C LD50: > 375 mg/kg log Kow 0.04 pKa1 8.5, pKa2 10.3 m.p. -94 C , b.p. 72 C LD50: >5000 mg/kg 0.756 g/mL log Kow 1.5

Cl

2)
Cl

3)

HO

NH2

4)

OH Cl

5)
NO2

m.p. 106 C , b.p. >300 C LD50: 900 mg/kg log Kow 2.5 pKa 5.2

b.p. boiling point, m.p. melting point

a) How many isomers of methylated naphthalenes (1) exist? Draw the structures!

(3.0)

b) To which contaminant class do the compounds above belong to? 1. 2. 3. 4. 5. c) Which of the above substances (1-5) are liquids, solids and gases under standard temperature and pressure? Give reasons for your decision! Solids Liquids Gases

(2.5)

(2.5)

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HEG Dr. T. Licha/ Dr. M. Lodemann

d) Which are DNAPL and which are LNAPL?

Module M.HEG.03 Hydrochemistry EXAM 2011

(1.0)

e) Which of the compounds can form ions and what will their respective charge be at a typical groundwater pH of 7? (2.5)

f)

In which environmental compartment (soil, water, soil gas) is each compound predominantly distributed? Give reasons for your decision! 1. 2. 3. 4. 5.

(2.5)

g) Order the substances according to their expected retardation in an aquifer! Give reasons for your decision! (3.0)

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HEG Dr. T. Licha/ Dr. M. Lodemann

Module M.HEG.03 Hydrochemistry EXAM 2011

h) What is the apparent diffusion coefficient at 10 C in water for compound 2 with a concentration of 1 g/kg in a river sediment with the following properties: ds 2.3 kg/dm3, n 0.4, ne 0.2, fOM 0.02. Assume Henry sorption and total porosity to be the diffusion effective porosity. ( =1.306 cP) (4.0)

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HEG Dr. T. Licha/ Dr. M. Lodemann

Module M.HEG.03 Hydrochemistry EXAM 2011

Part 3: Inorganic Hydrochemistry: in total 21 points to gain

a) Explain and reason using examples what controls the abundance of ions in aquifers! (8.0)

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HEG Dr. T. Licha/ Dr. M. Lodemann

b) What is the pH of the following solutions ? 1) 0.1 M NaCl 2) 0.1 M NH4Cl

Module M.HEG.03 Hydrochemistry EXAM 2011

(4.0) 3) 0.1M Naac 4) 0.1M NH4ac

ac: acetate, pKa acetic acid 4.75, pKb ammonium 4.75

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HEG Dr. T. Licha/ Dr. M. Lodemann

Module M.HEG.03 Hydrochemistry EXAM 2011

c) What are the calcium and fluoride concentrations in mg/l at equilibrium of CaF2 (pKsp 10.4) in 0.02 M NaF solution ? (A = 0.5093 (l/mol)0.5). Write down the respective chemical equation. (9.0)

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HEG Dr. T. Licha/ Dr. M. Lodemann Supplement

Module M.HEG.03 Hydrochemistry EXAM 2011

1 n I = ci zi2 2 i=1
pH pH = 1 ( pK a log c0 ) 2

ai = fi ci

log fi = - Azi2(I)0.5 pH = pK a - log

1000 v sample

pOH

1 ( pK b log c0 ) 2

[HA] [ A ]

1 ( pK a (HY ) log c0 ) 2
n

c analyte = v T c T z TA fT Manalyte
o
+

c sa =

m+n

K SP mm nn

cs = K fr c w
R =1+

2.303 R T U eq = U ( H2/2H ) + lg a H + zF
log KOC = 0.74 log KOW + 0.15

K OA =

cO cA

b
ne

Kd

b = (1n )d s

fOM ~ 2 fOC
SI = log

Dw

3 . 595 10 -7 T = M 0.53
0,059V aOx lg a z Red

De = Dw n 2
Da = Dwne D = e (n + K d b ) f

[IAP ]
K SP

E E0 +

= 0.894, 1.002, 1.306 cP at 25C, 20C and 10C

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