Exam Module B6 Hydrochemistry Thursday 11.04.

2008, 10am 1pm

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HEG Dr. T. Licha

Module B6 Hydrochemistry EXAM 2007/08

Answer 2 out of 3 Question Blocks!

Question 1 Sampling a) Describe sampling processes of surface water as compared to groundwater sampling, what are the differences? What considerations are there? b) Describe giving your reasons which parameters need to be analysed directly on site. c) What other parameters must be documented when measuring conductivity, Eh and Ph d) Describe giving reasons the procedure for calibrating pH electrodes e) How is the m-value defined? How and were is it deduced? How do samples need to be prepared for its measurement? f) In field measurement a 100ml sample was titrated with 3ml 0,2N salt solution, before colour change of Methylorange (pH 4,2) was noted. How high was the hydrogen-carbonate concentration in the sample in mmol/l and mg/l g) To which water type does the following waters belong too? (values are in mg/l) pH:7,23 Eh:53m/V Conductivity:875 uS/cm Na:27,90 Ca:113,00 Mg:10,20 K:9,10 SO4-2 :74,0 HCO3:5,6 Cl-:102,0 NO3-:29,0 Check the groundwater composition is it plausible? With which reading could there be an error?

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HEG Dr. T. Licha Question 2 Chemical Equlibria

Module B6 Hydrochemistry EXAM 2007/08

a) write the reaction equation for the following minerals in water and calculate the solubility product at 250C using the thermodynamic constants given CaF2 and CaSO4*2H2O Thermodynamic constant (G0f) in [KJ/mol] at 250C Ca2+(aq) -553.54 F-(aq) -278.8 H2O(l) -228.6 CaF2(s) -277.7[Kcal/mol] SO42-(aq) -744.6 CaSO4*2H2O(s) -1797.2 b) By what factor do the solubilitys of calcit (CaCO3), anhydrit (CaSO4) and flussspat (CaF2) differ in water at 250C ? Use tabulated solubility products! c) Calculate the solubility of schwerspat (BaSO4) in distilled water and estimate it in sea water (29g/l NaCl)! Explain the difference! d) Calculate the following pH values of aqueous solutions at 250C Hcl 400mmol/l, NaOH 20g/l, vinigar 1 mol/l, sodium acetate 8.2 g/l e) Give examples for natural buffering systems in the soil/groundwater environment. Comment on how a buffer functions using your examples! f) What percentage of phenol is dissociated at pH6, pH9 at pKs and at pH 11? (pKs Phenol 9.9) g) How high is the theoretical redox potential at 250C and how high is pe of the solution dominated by a iron redox system with following concentrations Fe2+: 53mg/l Fe3+:10mg/l pH=1,5 h) what are the differences and similarities between absorption and ion exchange

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HEG Dr. T. Licha

Module B6 Hydrochemistry EXAM 2007/08

Question 3 Distribution Equilibria PART I a) Explain using the properties of a member of the contaminant classes BTEX, VOC and PAH respectively their environmental behaviour. Explain their respective transport characteristics in groundwater and in the unsaturated zone. PART II b) How high is the solubility of a hydrophobic organic substance with (log Kow = 4) in a natural groundwater with a DOC of (10 mg/l)? If the solubility of this substance in clean water is (5mg/l), how large is the effect of DOC in %? log K DOC = 0.937 log K OW 0.46 c) A crude oil with a mean molar mass of 241.8 g/mol contains 1 % by weight Benzothiophene with a molar mass of (134.2 g/mol). How high is the saturation concentration of Benzothiophene in water from crude oil? Assume ideal phase behaviour. cwsat =1.6 mmol/l (subcooled liquid solubility). Part III d) A groundwater has a Dichloromethane (DCM) concentration of 20 mg/l. Do you expect to detect (DCM) in the vadoze zone by air sampling if your analytical methods to detect DCM in air has a limit of detection of 50ppm ? (Henry constant of DCM = 0.11 and the density of air is 1.3 g/l) e) A lab ran a batch absorption analysis with natural sediment to characterise the absorption behaviour of a)Phenol b)Anilin at pH 7. Find the best isotherm fit and associated parameters from the following data:
Phenol cw ug/l 1 5 10 50 100 500 1000 cs ug/kg 12.1 46.5 85.6 331 601 2360 4240 Anilin cw ug/l 0.1 0.2 0.5 1 2 10 50 cs ug/kg 395 724 1420 2100 2750 3670 3930

Estimate the retardation coefficient for phenol for the concentration range 1-5 ug/l using the data given with an effective porosity of 0.2 and for a quartz dominated sand with a fOM of 0.002 and an effective porosity of 0.2. Estimate the fOM of the sediment used for the analysis above and rate the labs results.

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