Analysis of the Codorus Creek

Quantitative Analytical Chem.

Fall 2002

Agenda

• Background– Purpose of study– Sampling scheme– Major Polluters– Clean-up Acts

• Chloride Analysis

• Sulfates

Agenda Continued

• Sulfites

• Calcium and Magnesium

• Nitrates

• Various Metals (silver, mercury, and lead)

Codorus Creek Study

• Purpose of Study– Use various analytical techniques from

previous methods• Titrimetric, gravimetric, and UV-Vis

– Determine amounts of analyte in East and West Branches and Main Branch of Codorus Creek

Where Our Water Comes From

• http://www.yorkwater.com/

Sampling Scheme

• Sampled above and below PH Glatfelter (West Branch)– 616 Bridge

• Sampled above and below Indian Rock Dam (East Branch)– Ridge View Rd.– Reynolds Mill Rd.

• Sampled from the South Branch• Sampled from Waterway Bar and Grill, Philadelphia

St.• Sampled from Indian Rock Campground

Sampling Scheme Continued

• Make standard curves

• Test samples

• Compared values with the spec. (Hach kit)

• Spiked samples to determine % recovery

Major Industries That Pollute

• Brunner Island

• PH Glatfelter

• Baker Refractories

• Lehigh Portland Cement

Other Pollution

• Farmland– Nitrates

• Urban/Storm Runoff

• Industrial Waste

• Municipal Waste– Source:

Cleanup Acts

• Codorus Creek Cleanup June 2002– Source: www.pawatersheds.org

Analysis of Chloride

Testing performed by Kim and Jamie

Chloride Analysis

• Method from Quantitative Chemical Analysis by Daniel C. Harris

• Used in Class previously

• Found on page 859-860 of text

• Acceptable levels of Chloride are 0.01 ppm– www.epa.gov

Method

• Standard Curve– 0.03 g Dextrin to 50 mL of known conc. Plus 5

drops of dichlorofluorescein• 1ppm, 0.8 ppm, 0.6 ppm, 0.2 ppm, 0.05 ppm, and

0.01 ppm of chloride

– Titrated with 4 g of AgNO3 dissolved in 200 mL DI water

– Titrated until pink endpoint

Standard Curve of Chloride

0

10

20

30

40

50

60

70

80

0 0.2 0.4 0.6 0.8 1 1.2

ppm

mL A

gNO3

Samples

• 50 mL of sample put into Erlenmeyer Flask with 0.03 g Dextrin

• Added 5 drops of dichlorofluorescein• Titrated with AgNO3 to a pink endpoint

Location PPM By Spect

PPM By Spect

Philadelphia St.

0.227 mg/L

0.23 mg/L

0.041 mg/L

0.07 mg/L

Indian Rock Dam

0.066 mg/L

0.07 mg/L

0.022 mg/L

0.02 mg/L

West Branch (Below P.H. Glatfeder)

0.222 mg/L

0.24 mg/L

0.223 mg/L

0.25 mg/L

East Branch Above

0.010 mg/L

0.05 mg/L

0.028 mg/L

0.03 mg/L

East Branch Below

0.120 mg/L

0.13 mg/L

0.222 mg/L

0.21 mg/L

South Branch

0.01 mg/L

0.02 mg/L

0.036 mg/L

0.04 mg/L

Titration and Spec. Data

Location PPM (by spec)

Recovered amount

Percent Recovery

Philadelphia St.

0.07 mg/L Not enough sample

Indian Rock Dam

0.02 mg/L 0.988 96.7 %

West Branch (Below P.H. Glatfeder)

0.25 mg/L 1.211 96.8 %

East Branch Above

0.03 mg/L 0.986 95.7 %

East Branch Below

0.21 mg/L 1.194 98 %

South Branch 0.04 mg/L 0.987 94.9 %

Spikes

Results

• Different levels of chloride at different points along the Codorus Creek

• Highest levels 0.227 ppm– Philadelphia St.

– Stagnant water

– Shopping cart

• Lowest levels– South Branch and East Branch above Glatfelter

• 0.01 ppm---acceptable limits

Results….

• Spike Recovery– Average= 96.42% – 1 ppm spikes

Error

• Color of endpoint– Pinks hard to determine– Dull vs. bright

• Samples– Occasionally 1st sample turned right away– Other 3 trials were okay

Error…

• Water collection– After periods of rain

• Dilution errors– Pipetting

• Titration errors– Color of endpoint

• Hints of green when it turned pink– When poured down the drain

Sulfates

Testing performed by Rob and Howie

Primary Source of Sulfates

Worst Case Offenders - 1999

• Brunner Island – 71,188 tons

• PH Glatfelter – 6,521 tons

• Baker Refractories – 3,609 tons

• Lehigh Portland Cement – 1,368 tons

Sulfate Wet Deposition

Hazards of Sulfates In Water

• Below 250 ppm no direct harm to people

• Causes acidification– Kills fish– Decreases biodiversity– Causes chronic stress– At pH 5.0 most fish eggs can’t hatch

Effects of pH

Long-Term Trend in Stream Chemistry

Sulfate Analysis: Baseline

• 90 mL distilled water

• 10 mL BaCl2

• Take 20 mL off top

• 3 drops calmagite

• Titrate with EDTA

• Get Standard Zero

Sampling Procedure

• 90 mL Sample

• 10 mL BaCl2

• Allow to precipitate overnight

• Pull 20 mL off top

• 3 drops calmagite

• Titrate with EDTA

• Average Titrations

Formulas

• Standard Zero – Average Titration

• Divide by 1000

• Multiply by .0434 M EDTA

• Multiply by mw SO4 (96)

• Divide by .09 L (Amount of water sample)

• Get ppm

Spikes

• 3 different distilled water samples (.1 L)

• Added sodium sulfate (mw = 142.04 g)– #1 - .0087 g = 58.8 ppm Got 48.2 ppm– #2 - .0493 g = 333.4 ppm Got 315.7 ppm– #3 - .1194 g = 807.5 ppm Got 733.6 ppm

Results Trial 1

Location Test Kit (ppm) Titration Results (ppm)

Below PHG 80 26.39 / 51.0

Below Dam   37.03

Indian River   9.26

Above Spring Grove

11 6.02

Philadelphia St   10.65

Results Trial 2

Location Test Kit (ppm) Titration Results (ppm)

South Branch 6 18.5

Below Dam 7 6.02

Indian River 19 18.5

Above Dam 6 9.3

Sources of Error

• Determination of titration endpoint

• Titration errors

• Precipitation time

• Measurements

• Quantity of original sample

• Testing performed by John

Sulfitesin the

CODORUS!

KI-KIO3 volumetric method

Performed by John

What are sulfites used for?

• Used to sanitize and preserve foods

• Used in the wine industry as an antioxidant and antimicrobial

• Dehydration of fruits and vegetables

• Wood pulping and paper making

Effects of sulfites

• Causes allergic reactions in asthmatics

• FDA and ATF have mandated that sulfites in foods at levels of 10 ppm or higher be reported on labels

Procedure

• Standard potassium iodide-iodate titrant(diluted 100 times from procedure found in Standard Methods for Water and Wastewater)

• Starch indicator

KI-KIO3

• ~.4400 g anhydrous KIO3

• 4.35 g KI

• .0310 g sodium bicarbonate

• Place in 1000 ml volumetric flask and fill to the mark

Starch indicator

• Boil 100 ml water

• Weigh out 1 g of starch and place in 10 ml of water

• Pour paste into boiling water

• Boil until clear

• Must be made before every class

Put it all together!

• In 250 ml flask

• 1 ml sulfuric acid

• .1 g sulfamic acid

• 50 ml water sample

• 1 ml starch indicator

• Titrate with KI- KIO3 until blue

Calculation of Sulfites

• Used known amounts of sodium sulfite to create calibration curve

• Calculated amount of sulfites from equation by plugging in the amount of titrant used

Data

• Minimum detectable limits 2 mg/L = 2 ppm

• All data came out negative except Philadelphia street from both days and the east branch from day two

• Most data below minimum detectable limits

Day 1Trial g sulfamic ml KI-KIO3 ppm

Philadelphia 1 0.1014 10.3 0.962 0.1006 10.6 1.923 0.1004 11 3.2

Day 2Trial g sulfamic ml KI-KIO3 ppm

Philadelphia 1 0.1017 10.1 0.322 0.1014 10.3 0.963 0.1004 9.9 NA

East BranchAbove Dam 1 0.1007 10.7 2.24

2 0.1007 10.4 1.283 0.1009 9.9 NA

East Branchbelow dam 1 0.1004 9.8 NA

2 0.1005 10.1 0.323 0.1024 10.3 0.96

Data

Results

• Day 1– Philadelphia Street

• .96 ppm

• 1.92 ppm

• 3.20 ppm

• Day 2– East Branch below

• .32 ppm• .96 ppm

– Philadelphia Street• .32 ppm• .96 ppm

– East Branch above dam• 2.24 ppm• 1.28 ppm

Spikes

• Added a 2.508 x 10-7 M solution of sodium sulfite

• About doubled the level of sulfites in the water

• Made all of the samples above the detectable limit

Conclusions

• The levels of sulfites in the water is below detectable levels

• Error– Calibration curve– Detecting endpoint

Ca2+ and Mg2+ Concentrations

By

Jennie Waughtel

And

George Collins

Points of Interest

There are no minimum or maximum standards set by the EPA

Raw Water Data from The York Water Company

Ca concentration (ppm):

Mg Concentration (ppm):

Method of Analysis• EDTA Titration

– Reagents Needed

– EDTA Solution• 0.6 g Na2H2EDTAdihydrate dissolved in 500ml distilled H20

– Calmagite indicator– 0.5 M NaOH

• 5 g NaOH dissolved in 250 ml distilled H20

– Buffer (pH 10)

• 142 ml of 28% aqueous NH3 to 17.5 g of NH4Cl• Dilute with distilled H2O to 250 ml• Adjust pH using 1M HCL• Target pH 10: Actual pH 10.03

Method of Analysis

• Procedure for total Ca2+ and Mg2+ ppm

– Pipet 50ml of sample into 250ml flask

– Add 3ml by pipet of Buffer Reagent

– Add 6 drops of Calmagite indicator

– Titrate with EDTA solution until the wine red color changes to blue

Method of Analysis

• Procedure for total Ca2+ ppm

– Pipet 50ml of sample into 250ml flask

– Add 30 drops (1.1ml) of NaOH Reagent and wait 2 min to precipitate Mg(OH)2

– Add 6 drops of Calmagite indicator

– Titrate with EDTA solution until the wine red color changes to blue

Results of Analysis• Ca2+ Concentrations

– East Branch above Lake Redman : 28.485 ppm– East Branch below dam : 41.289 ppm– West Branch above Spring Grove : 43.881 ppm– West Branch below Glatfelter : 88.141 ppm– Indian Rock Dam : 55.705 ppm– Philadelphia Street : 48.655 ppm– South Branch : 32.816 ppm

– Overall average : 48.402 ppm

Ca2+ Concentrations (ppm)

28.485

41.28943.881

88.141

55.705

48.655

32.816

48.402

28.00030.00032.00034.00036.00038.00040.00042.00044.00046.00048.00050.00052.00054.00056.00058.00060.00062.00064.00066.00068.00070.00072.00074.00076.00078.00080.00082.00084.00086.00088.000

East Branch aboveLake RedmanEast Branch belowDamWest Branch aboveSpring GroveWest Branch belowGlatfelterMain Creek at IndianRock DamMain Creek atPhiladelphia StreetSouth Branch

Overall Average

Results of Analysis• Mg2+ Concentrations

– East Branch above Lake Redman : 15.786 ppm– East Branch below dam : 15.689 ppm– West Branch above Spring Grove : 8.738 ppm– West Branch below Glatfelter : 48.210 ppm– Indian Rock Dam : 24.850 ppm– Philadelphia Street : 28.423 ppm– South Branch : 18.579 ppm

– Overall average : 22.727 ppm

Mg2+ Concentrations (ppm)

15.78615.689

8.738

48.210

24.850

28.423

18.579

22.727

7.0009.000

11.00013.00015.00017.00019.00021.00023.00025.00027.00029.00031.00033.00035.00037.00039.00041.00043.00045.00047.00049.000

East Branch aboveLake RedmanEast Branch belowDamWest Branch aboveSpring GroveWest Branch belowGlatfelterMain Creek at IndianRock DamMain Creek atPhiladelphia StreetSouth Branch

Overall Average

Background

EPA Standards

Monitoring water ways

Health effects

Previous Studies

Iowa study

Studies on Lower Susquehanna Basin

EPA study

Procedure • Pipet 10ml. of sample into an Erlenmeyer flask

• Add 2ml. of 30% salt solution, which was previously prepared using 300g. NaCl and diluted in 1L of water

• Cool the sample in an ice bath for approximately 5 minutes

• Once cool, pipet 10ml. of 13N (6.5M) Sulfuric acid solution into the flask

• The Sulfuric acid solution prepared by diluting 180.55ml of 18M Sulfuric acid to 500ml. of water

• Add 0.5ml Brucine reagent, which is prepared by dissolving 1g. brucine sulfate and 0.1g. sulfanilic acid in 70ml. of water

• Place clear mixture into a water bath and boil for approximately 25-35 minutes

• After heating, the mixture should exude a noticeable pale yellow color (which is a sign of nitrate present in solution)

• Using UV-VIS instrument test samples for absorbance

Qualitative Analysis

UV-VIS Spectrophotometer was used to measure absorbance . Matter can capture electromagnetic radiation and convert the energy of a photon to internal energy. This process is called absorption. Energy is transferred from the radiation field to the absorbing species. We describe the energy change of the absorber as a transition or an excitation from a lower energy level to a higher energy level. Since the energy levels of matter are quantized, only light of energy that can cause transitions from one level to another will be absorbed.So by measuring absorbance at specific wavelength we can determine Nitrate concentration in our sample.

Qualitative Analysis

After blanking the instrument with distilled water sample we ran a 722ppm Nitrate standard. We observed that at 352nm absorbance was higher than that at 410nm. After running a series of standards ranging from low concentration to high concentration we constructed a calibration curve. Calibration curve showed that absorbance at 410 is more stable and therefore has a better correlation of absorbance vs. concentration.

Calibration Curve

Next step was to create a calibration curve. We ran several standards and then plotted absorbance vs. concentration of nitrate in our samples.

Calibration Curve

y = 0.0005x + 0.0083

R2 = 0.9802

0.00E+00

5.00E-02

1.00E-01

1.50E-01

2.00E-01

2.50E-01

0 100 200 300 400

Concentration of Nitrate (ppm)

Abs

orba

nce

Quantitative Analysis

Sample ppm AbsorbanceS. Branch A 13.20 1.49E-02S. Branch B 10.00 1.33E-02S. Branch C 12.00 1.43E-02S. Branch Avg. 11.73Spike A 166.00 9.13E-02Spike B 161.80 8.92E-02Spike C 160.20 8.84E-02Spike Avg. 162.67

Spike ppm Added: 160.44% Recovery: 94.07%

Below PHG 230.7 ppmAbove S.G. 52.0 ppmPhilladelphia St. 10.0 ppmBelow Dam N/DIndian R.Dam N/DE.B. Above Redman 72.8 ppm

Sources of Error

• Brucine reagent very unstable (to be stored at 5 F at all times)

• Errors in preparation of brucine-sulfanilic acid reagent, specifically when measuring precisely 0.1 g of sulfanilic acid

• Errors in calculations

• The fact that the water samples were not always fresh samples

• Procedures were done over a period of different days

Conclusion

Heavy Metal Analysis

Lead, Mercury, and Silver

Performed by Ben

Health Hazards

• Mercury– From industrial and agricultural sources– .002 ppm EPA level– elemental mercury damages brain and kidneys– methylmercury- formed in water, most toxic

• bioaccumulative• very small levels cause severe neurological damage

and death• most severe in infants and children

Health Hazards

• Lead– from industrial and agricultural sources– .015 ppm EPA level– delay mental and physical development in

infants and children– affects the heart liver, and nervous system and

causes kidney problems and high blood pressure in adults

Health hazards

• Silver– from industrial and agricultural sources– low toxicity to humans– no EPA level found

Gravimetric Analysis

• Metal ions precipitated out as insoluble chlorides with HCl

• Then the precipitates were separated• PbCl2

– dissolves in boiling water, others won’t– remaining precipitates filtered out– acetic acid and K2CrO4 added to filtrate to

obtain PbCrO4

Gravimetric Analysis continued

• Hg2CL2– Remaining precipitate added to 6 M NH4OH – AgCl dissolves– Hg2Cl2 reacts with NH4OH to form

HgNH2CL, a black to gray precipitate– filtered and dried

Gravimetric Analysis continued

• AgCl– 6 M HNO3 added to filtrate– A white AgCl precipitate forms in an acidic

environment– filtered and dried

Water Sample results

mercury lead silver

East branch above the dam

Below detectable limits

Below detectable limits

Below detectable limits

East branch below the dam

Below detectable limits

Below detectable limits

Below detectable limits

West branch above P.H.G.

Below detectable limits

Below detectable limits

Below detectable limits

West Branch below P.H.G.

Below detectable limits

Below detectable limits

Below detectable limits

South Branch Below detectable limits

Below detectable limits

Below detectable limits

Codorus Creek Indian Rock

Below detectable limits

Below detectable limits

Below detectable limits

Codorus Creek Philadelphia St

Below detectable limits

Below detectable limits

Below detectable limits

Detectable limits

• Using chloride forms of metals, the lowest concentration able to form precipitate was 50 ppm

• Also, the lowest detectable limit using the current balances is 1.7 ppm

Errors

• Gravimetric analysis may not be best method due to minute levels to be measured

• Also, measuring for elemental forms of the metal, which in water may be present in other forms, such as methylmercury or lead sulfides