(Benjamin, 1.1 & 1.4)

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1 Updated: 23 January 2018 Print version Lecture #1 Intro: Course Administration, Scope and Chemistry Review (Stumm & Morgan, Chapt. 1) (pp.1-4) (Benjamin, 1.1 & 1.4) David Reckhow CEE 680 #1 1

2 Course Administration Course Syllabus Textbook: Benjamin, Water Chemistry, 2 nd Edition, Waveland Press, 2015 must read, not all topics may be covered Detailed Course Outline Homework policy most graded; Projects MINEQL, review of literature Web site David Reckhow CEE 680 #1 2

3 Other References 1. Pankow, Aquatic Chemistry Concepts. Lewis Publ., Chelsea, MI, Stumm & Morgan, Aquatic Chemistry. 3rd Ed., John Wiley & Sons., 1995 Extra copy on shelf in 3 rd floor Elab II office UM Science GB855.S Jensen, A problem Solving Approach to Aquatic Chemistry, Wiley, UM Science GB855.J Sawyer, McCarty & Parkin, Chemistry for Environmental Engineering, McGraw Hill, Extra copy of 3 rd edition on shelf in 3 rd floor Elab II office 5. Eby, Principles of Environmental Geochemistry, Cengage Learning, Langmiur, Aqueous Environmental Geochemistry, Prentice-Hall, Brezonik & Arnold, Water Chemistry, Oxford Univ Press, 2011 FC On line: GB855.B eb 8. Snoeyink & Jenkins, Water Chemistry, John Wiley & Sons., UM Science QD169.W3 S66 David Reckhow CEE 680 #1 3

4 General Questions for Water, Soil & Geochemists What is the chemical composition of natural waters? Will it change with time, location? What happens to chemical species when they enter new aquatic or non-aquatic environments? How does transport affect the chemistry? What types of reactions occur in managed natural systems? What do we need to do to make it work better? David Reckhow CEE 680 #1 4

5 Examples for Water Treatment How can we use chemistry to stop corrosion and dissolution of lead? What with the ph, alkalinity and hardness be after mixing two different types of water e.g., groundwater and surface water How do we get the best performance from chemical precipitation processes e.g., coagulation, softening What can we do to optimize oxidation treatments e.g., removal of Mn, trace organic constituents David Reckhow CEE 680 #1 5

6 Example 1: Lead and Water Lead is a neural toxin Especially serious in children EPA: Pb & Cur Rule Published in 1991 The treatment technique for the rule requires systems to monitor drinking water at customer taps. If lead concentrations exceed an action level of 15 ppb or copper concentrations exceed an action level of 1.3 ppm in more than 10% of customer taps sampled (i.e., 90%ile), the system must undertake a number of additional actions to control corrosion. David Reckhow CEE 680 #1 6

7 Flint Michigan Crisis Timeline April 2014: the city stopped getting its water from Detroit as a cost-saving measure and began instead drawing water from the Flint River. High blood lead levels noted in children Water led levels were above standard Oct 16, 2015: Flint switches back to Detroit Water Sources EPA website: VPI website: 12/22/2015 Rachel Maddow video: David Reckhow CEE 680 #1 7

8 Flint Water Quality - Edwards Parameter Before 4/2014 After 4/2014 ph units Hardness mg-caco3/l Alkalinity mg-caco3/l Chloride mg/l Sulfate mg/l CSMR Inhibitor 0.35 None mg-p/l Larson Ratio WQ data From MOR and 2014 WQR CSMR chloride to sulfate mass ratio Larson Ratio ([Cl - ] + 2[SO 4-2 ])/[HCO 3- ] David Reckhow CEE 680 #1 8

9 Edwards slide David Reckhow CEE 680 #1 9

10 Daily Hampshire Gazette: 22 Jan 2016 das David Reckhow CEE 680 #1 10

11 Daily Hampshire Gazette: 22 Jan 2016 Environmental Justice issue David Reckhow CEE 680 #1 11

12 Example 2: differing water quality Many, perhaps most, drinking water utilities have multiple sources Often those sources have contrasting water quality Especially common for regional supplies, like Tampa Bay David Reckhow CEE 680 #1 12

13 Groundwater and surface water Tampa Bay area and regional supply Groundwater River water Ocean water: desal David Reckhow CEE 680 #1 13

14 Pinellas County Water Calcium Iron Standard WQ Analyte List (103 total) 1,1-Dichloro-2- propanone Bromochloroacetonitrile 1,1,1-Trichloroethane 1,4-Dichlorobenzene cis-1,3- Dichloropropene 1,1,2,2-2,2-Dichloropropane Dibromochloromethane Tetrachloroethane n-propylbenzene ortho-xylene Dichloroacetic acid Total Haloacetic Acids (HAA5) Magnesium 1,1,2-Trichloroethane 2-Chlorotoluene Dibromomethane sec-butylbenzene Chloropicrin Trichloroacetic acid Arsenic 1,1-Dichloroethane 4-Chlorotoluene Styrene Decafluorobiphenyl Alkalinity as CaCO3 Copper 1,1-Dichloroethylene 4-Isopropyltoluene Ethylbenzene tert-butylbenzene Dibromoacetonitrile Total Hardness Lead 1,1-Dichloropropene Benzene Fluorobenzene Tetrachloroethylene Dichloroacetonitrile Bromide Chloride Nitrate as N Dichlorodifluoromethane 1,2,3- Trichlorobenzene 1,2,4- Trichlorobenzene 1,2,4- Trimethylbenzene Bromobenzene Hexachlorobutadiene Toluene Bromochloromethane Isopropylbenzene meta/para-xylene Nitrite as N 1,2-Dichlorobenzene Bromoform Methyl bromide Bromodichloromethane Total Trihalomethanes trans-1,2- Dichloroethylene trans-1,3- Dichloropropylene Orthophosphate as P 1,2-Dichloroethane Carbon tetrachloride Methyl chloride Trichloroethene Orthophosphate as PO4, calculated Sulfate Phosphorus, Total (as P) 1,2-Dichloropropane Chlorobenzene 1,2,3- Trichloropropane 2-Bromopropionic Acid 1,3,5- Trimethylbenzene Chloroethane Methylene chloride Methyl tert-butyl ether Trichlorofluorometha ne Total Haloacetonitriles Trichloroacetonitrile Chloral hydrate Total Dissolved Solids Ammonia as N Decafluorobiphenyl UV 254 Free Ammonia as N Total Organic Carbon Heterotrophic Plate Count 1,1,1,2- David Reckhow 1,3-Dichloropropane cis-1,2-1,1,1-trichloro-2- CEE n-butylbenzene 680 #1 Dibromoacetic acid 14 Tetrachloroethane Dichloroethylene propanone E. coli Vinyl chloride Bromoacetic acid Total Coliforms 1,3-Dichlorobenzene Chloroform Naphthalene Xylene (total) Chloroacetic acid

15 Keller 2 Groundwater source: Eldridge Wilde Wellfield 40 MGD WQ Challenge ppm H2S, VOCs Water Treatment Air Stripping with CO2 Chlorination Ammoniation Polyphosphate Air treatment Water scrubbing with caustic & chlorine David Reckhow CEE 680 #1 15

16 Majors mostly inorganics Keller Plant 2 Sample Station: Aug 9, 2010 Parameter Value Units Parameter Value Units Calcium 77.7 mg/l Sulfate 4 mg/l Iron mg/l Phosphorus, Total (as P) 0.23 mg/l Magnesium 5.08 mg/l Alkalinity as CaCO3 209 mg/l Arsenic mg/l Total Hardness 215 mg/l Copper mg/l Total Dissolved Solids 316 mg/l Lead mg/l Ammonia as N 0.84 mg/l Bromide 0.05 mg/l Free Ammonia as N 0.16 mg/l Chloride 22 mg/l Total Organic Carbon 3.7 mg/l Nitrate as N 0.04 mg/l UV cm - 1 Nitrite as N 0.02 mg/l Heterotrophic Plate Count 3 CFU/ml Orthophosphate as P 0.12 mg/l E. coli 1 MPN/100ml Orthophosphate as PO mg/l Total Coliforms 1 MPN/100ml David Reckhow CEE 680 #1 16

17 Trace Organics above MDL Keller Plant 2 Sample Station: Aug 9, 2010 Parameter Value Units Parameter Value Units Bromodichloromethane 8.3 ug/l Dibromoacetonitrile 0.77 ug/l Chloroform 45 ug/l Dichloroacetonitrile 10.7 ug/l Dibromochloromethane 0.9 ug/l Total Haloacetonitriles 13.3 ug/l Total Trihalomethanes 54.2 ug/l Trichloroacetonitrile 0.12 ug/l 1,1,1-Trichloro-2-propanone 3.47 ug/l Chloral hydrate 5.45 ug/l 1,1-Dichloro-2-propanone 1.36 ug/l Dichloroacetic acid 12.6 ug/l Bromochloroacetonitrile 1.73 ug/l Total Haloacetic Acids (HAA5) 31.8 ug/l Chloropicrin 0.21 ug/l Trichloroacetic acid 19 ug/l David Reckhow CEE 680 #1 17

18 Pinellas Questions What does the detailed analysis tell you? Does it make sense? Expressions of concentration? Principle of electroneutrality? TDS, TH, Alk, TOC, UV what do these mean David Reckhow CEE 680 #1 18

19 Pinellas calculations 1 conc (mg/l) GFW mm charge/m meq/l pos neg Calcium 77.7 mg/l Iron mg/l Magnesium 5.08 mg/l Arsenic mg/l Copper mg/l Lead mg/l Bromide 0.05 mg/l Chloride 22 mg/l Nitrate as N 0.04 mg/l Nitrite as N 0.02 mg/l Orthophosphate as P 0.12 mg/l Orthophosphate as PO4, calculated 0.37 mg/l Sulfate 4 mg/l Phosphorus, Total (as P) 0.23 mg/l Alkalinity as CaCO3 209 mg/l Total Hardness 215 mg/l Total Dissolved Solids 316 mg/l Ammonia as N 0.84 mg/l Free Ammonia as N 0.16 mg/l Total Organic Carbon 3.7 mg/l UV cm - 1 Heterotrophic Plate Count 3 CFU/ml E. coli 1 MPN/100ml Total Coliforms 1 MPN/100ml Total add sum exclude TDS, TH diff % 12.0% David Reckhow CEE 680 #1 19

20 Pinellas calcs 2 mass of E. coli 0.5 um diameter 2 um long cylinder volume um E-10 mm E-13 cm3 density 1 g/cm3 mass/cell 3.93E-13 g 3.93E-10 mg E.coli example conc 1 in 100 ml mass concentra tion 3.93E-09 mg/l 3.93E-06 ug/l 3.93E-03 ng/l HPC example conc 3 in 1 ml mass concentra tion 1.18E-06 mg/l 1.18E-03 ug/l 1.18E+00 ng/l David Reckhow CEE 680 #1 20

21 Pinellas Discussion Missing Na, K 13.5 mg/l Na would close the balance David Reckhow CEE 680 #1 21

22 Stoichiometry: Lake Example Basic limnology tells us that phosphorus stimulates algal growth, they produce O 2, and bacteria consume O 2 when the algae die If we add 1 mg P to a small lake How much algal biomass is produced? How much O 2 is produced? How much O 2 is later consumed? Elemental analysis of algae: empirical formula C 106 H 263 O 110 N 16 P David Reckhow CEE 680 #2 22

23 Solution Balance equation 106 CO NO 3- + HPO H 2 O + 18 H + C 106 H 263 O 110 N 16 P O 2 Use stoichiometric coefficients Biomass: O 2 production: O 2 consumption: 1mmole P 3551mg a lg ae 1mmole a lg ae 1mg P 31mg P 1mmole a lg ae 1mmole P 115mg a lg ae 1mmole P 32mg O 2 138mmole O 1mg P 31mg P 1mmole O 2 1mmole P 142mg O 2 2 David Reckhow CEE 680 #2 23

PFOA Perfluorooctanoic acid (PFOA), also known as C8 and perfluorooctanoate, is a synthetic compound.

It has been used in the manufacture of such prominent consumer goods as polytetrafluoroethylene (commercially known as Teflon).

PFOA has been detected in the blood of more than 98% of the general US population in the low and sub-ppb range, and levels are higher in chemical plant employees

24 PFOA Perfluorooctanoic acid (PFOA), also known as C8 and perfluorooctanoate, is a synthetic compound. One industrial application is as a surfactant in the production of fluoropolymers. It has been used in the manufacture of such prominent consumer goods as polytetrafluoroethylene (commercially known as Teflon). PFOA has been manufactured since the 1940s in industrial quantities. PFOA persists indefinitely in the environment. It is an animan carcinogen. PFOA has been detected in the blood of more than 98% of the general US population in the low and sub-ppb range, and levels are higher in chemical plant employees and surrounding subpopulations. How general populations are exposed to PFOA is not completely understood. PFOA has been detected in industrial waste, stain resistant carpets, carpet cleaning liquids, home dust, microwave popcorn bags, water, food, some cookware and PTFE such as Teflon. Daily Hampshire Gazette, 27 January 2016 David Reckhow CEE 680 #4 24

25 Relation with Environmental Engineering Math Biology Environmental Engineering Physics Chemistry David Reckhow CEE 680 #1 25

Relation with Classic Chemistry Disciplines Physical Chemistry Inorganic Chemistry 680 Thermodynamics Analytical Chemistry Organic Chemistry 697z 684 Kinetics CEE 680 Water Chemistry

26 Relation with Classic Chemistry Disciplines Physical Chemistry Inorganic Chemistry 680 Thermodynamics Analytical Chemistry Organic Chemistry 697z 684 Kinetics CEE 680 Water Chemistry CEE 572 & 772 Chemical Analysis CEE 684 Chemical Kinetics CEE 697z Organics in water CEE 680 is very similar to Geo-Sci 519 (Aqueous Environmental Geochemistry David Reckhow CEE 680 #1 26

27 Interdisciplinary sub-fields From Brezonik & Arnold, 2011 David Reckhow CEE 680 #1 27

28 Natural Water Environment Chemistry of: Water column Sediments Soil Groundwater Atmosphere S&M: Fig. 1.1; Pg. 2 David Reckhow CEE 680 #4 28

29 Model Complexity: Phases Single Phase to multi-phase Gas Gas Aqueous Solution Aqueous Solution Aqueous Solution Solid Phase Aqueous Solution Solid Phase Solid α Aqueous Solution Solid β Solid γ Solid α Gas Aqueous Solution Solid β Solid γ After S&M: Fig. 1.2 Pg. 4 David Reckhow CEE 680 #4 29

30 Review Units Mass based Molarity Molality Normality Mole fraction Atmospheres Chemical Stoichiometry mass balance balancing equations Thermodynamics law of mass action types of equilibria David Reckhow CEE 680 #1 30

Factor Prefix Symbol 10 1 deka da 10 2 hecto d 10 3 kilo k 10 6 mega M

31 SI Unit prefixes Factor Prefix Symbol 10-1 deci d 10-2 centi c 10-3 milli m 10-6 micro µ 10-9 nano n pico p femto f atto a Factor Prefix Symbol 10 1 deka da 10 2 hecto d 10 3 kilo k 10 6 mega M 10 9 giga G tera T peta P exa E David Reckhow CEE 680 #1 31

32 Mass Based Concentration Units Solid samples 17.5mg Pb 1kg soil x10 g Pb 3 1x10 g soil 17.5g Pb 10 6 g soil 17.5 ppm m Pbin soil 1mg / kg 1µ g / kg 1ppm 1ppb m m David Reckhow CEE 680 #1 32

33 Liquid samples 0.35mg Fe 1L water x 3 1L water 10 g water Density of Water at 5ºC 0.35mg Fe 3 10 g water x10 g Fe 3 10 g water 0.35g Fe 10 6 g water 0.35 ppm m Fe in water David Reckhow CEE 680 #1 33

34 Mass/Volume Units Mass/Mass Units Typical Applications g/l (grams/liter) (parts per thousand) Stock solutions mg/l (milligrams/liter) 10-3 g/l ppm (parts per million) Conventional pollutants (DO, nitrate, chloride) µg/l (micrograms/liter) ppb (parts per billion) Trihalomethanes, Phenols. 10-6g/L ng/l (nanograms/liter) ppt (parts per trillion) PCBs, Dioxins 10-9g/L pg/l (picograms/liter) 10-12g/L Pheromones David Reckhow CEE 680 #1 34

35 Gas samples (compressible) 0.056mg Ozone 3 1m air Could be converted to a ppm m basis But this would change as we compress the air sample Could also be converted to a ppm v basis Independent of degree of compression But now we need to convert mass of ozone to volume of ozone David Reckhow CEE 680 #1 35

36 Ideal Gas Law By definition: mass( g) n GFW An ideal gas Will occupy a certain fixed volume as determined by: PV V nrt RT P mass( g) GFW regardless of the nature of the gas Where: Ppressure Vvolume nnumber of moles Ttemp Runiversal gas constant L-atm/mole-ºK GFWgram formula weight n RT P 22.4 L at 1 atm, ºK David Reckhow CEE 680 #1 36

37 Convert mass to moles Now we know that ozone s formula is O 3 Which means it contains 3 oxygen atoms Therefore the GFW 3x atomic weight of oxygen in grams or 48 g/mole 0.056mg Ozone 3 1m air nmass(g)/gfw n0.056x10-3 g/(48g/mole) n x10-3 moles x10 1m 3 3 moles air Ozone David Reckhow CEE 680 #1 37

38 ppm v Now determine ppm v volume volume ozone air x10 moles x22.4l 3 1m air x10 L Ozone 3 1x10 L air ppm O in air 26 ppb v O 3 v 3 in air / mole David Reckhow CEE 680 #1 38

39 Mole & volume fractions Based on the ideal gas law: The volume fraction (ratio of a component gas volume to the total volume) is the same as the mole fraction of that component n Therefore: Defined as: Volume fraction V V i total And since the fraction of the total is one-millionth of the number of ppm: 6 Vi ni 10 ppm v V n David Reckhow CEE 680 #1 39 n i total total total V V i total n n i RT P RT P total Defined as: mole fraction

40 Partial pressures Based on the ideal gas law: PV And defining the partial pressure (P i ) as the pressure a component gas (i) would exert if all of the other component gases were removed. P nrt n V RT We can write: P i n V i total RT and P total n V total total RT Which leads to: And: P i P total P n n P i total i total n n P i total total10 6 ppm v David Reckhow CEE 680 #1 40

41 Earth s Atmosphere Divide by 100 and you get the partial pressure for a total pressure of 1 atm. David Reckhow CEE 680 #1 41

42 To next lecture David Reckhow CEE 680 #1 42

Course Administration

Updated: 2 January 2018 Print version Lecture #1 Intro: Course Administration, Scope and Chemistry Review (Stumm & Morgan, Chapt. 1) (pp.1 4) (Benjamin, 1.1 & 1.4) David Reckhow CEE 680 #1 1 Course Administration