Instrumental Methods of Analysis 1. Introduction

Instrumental Methods of Analysis1. Introduction

1. Writing Intensive1. Rewrites are Required2. Large Amount of Excel Data Management

2. Work1. Individual

1. Work Log2. Own Sample3. Exams4. Lab Book pages

2. Group1. Division and Attribution of Labor (Accountability)2. Reports3. Calibration Curves

3. Single Analyte (Skill Development and Cross Comparison Methods)1. Overlapping Themes

1. Statistics/Sampling2. Solution Chemistry3. EDTA4. Isotopes5. Phase Separations

1. Writing Intensive2. Work3. Single Analyte4. Problem Based

• What is best method for lead analysis?• What is best method for This particular sample?

5. Ethics and Service Learning1. How do we know?2. Critical Thinking

Instrumental Methods of Analysis1. Introduction

Electronics, Spectroscopy, Electrochemistry, Chromatography

Confusion Confusion

“Too much from instructor” information

IodideElectrolysis

Chromium &permanganate

UV-Vis

FluorideIon Selective

Electrode

Quinine Fluorescence

Cu GraphiteFurnaceAtomic

Absorption

DMSO Infrared

Spectroscopy

Methanol GasChromatography

7 different analytes7 different methods

How do we selectOr compare methods/Instruments?

Figures of Merit Theme Knowledge

Pb AnodicStripping

Voltammetry

Pb DithizoneUV-Vis

Tetraethyl 207Pb MS

Pb Ion Selective Electrode

Pb EDTA InfraredSpectroscopy

EDTA Pb HPLC

207Pb in EDTA by proton NMR

Pb Atomic Absorption

Calcein BluePb Fluorescence

Quenching

Choose Method: Cross Compare/measure LOD

Role of solution pH important

Pb Limit of detection?Pb Linear range?Pb Selectivity?Pb Signal/Noise?

Week Topic “Lab” Concept Stat Chem Isotope

Ethics

1 Pb & Society; Statistics and Ethics Pototo populations x x

2 Signals & Noise; LOD Analog & Digital filters x

3 Relevant Chemistry; Exam I ISE & Pb(OH)2 x

4 Intro Spectroscopy IR & UV-Vis x

5 Molecular Spectroscopy IR & UV-Vis x

6 Fluorescence and AA Fluorescence and FAA x x

7 AA and Vibrational, Exam II Fluorescence and FAA x x

8 Break, NMR Break

9 NMR, Off campus sampling NMR, ASV x x x

10 MS, NMR, ASV x x x

11 Intro Electrochem., Select Method sample prep x x x

12 Potentiometry, sample analysis x x

13 ASV, Take home exam III ICP-MS, GC x x

14 Separations ICP-MS, GC x x

15 Separations How do we know? Ethics x x

Why Lead?

Health

Same size,Shape, chemistryDifferentOrbitals,Different total Number of electrons

Warren et al, TIBS, 1998, 23, 217

Current measurementsno longer rely on zincprotoporphyrinas PbB effectson fetal developmentcan be detectedat values of PbB<5 ug/dL

ALAD dehydratase with lead binding site

An estimated 40% of lead in blood plasma bound to ALAD

Wetmur, 1994

Enhanced ALA concentration leadsto tautomers which easily formradicals which may attack the cellwall - leading to early cell death. Heme dies about 20% earlier

Hammond and Dietrich, 1990

Because lead affected ALADresulting in overproduction of ALAALA may also affect the functionof GABA but a close similarityin molecular structure

GABA controls leaf tip growth, and brain development. Functionchanges with time, so growing tips and infants differentially affected from adults

Herlenius and Lagercrantz, 2001Ben-Ari1, 2001

Certain portions of the brain more greatly affected: prefrontal cortex: problem solvinghippocampus (memory)cerebellum (motor coordination, body movement, posture and balance)

Why Lead?

Everywhere

Lead as anore in the earthrelatively benign

Human activitydistributeslead into theenvironment

Modern major uses

1. Pigments2. Leaded Gasoline3. Munitions

Eliminating Childhood Lead Poisoning:A Federal Strategy Targeting Lead Pain Hazards, Feb. 2000

Decade ThousandTonswhite lead

ThousandTons red lead(litharge)

MillionsOccupiedUnits

White leadper unit(pounds)

Remainingleadthousandstons

1914-23 1340 0 24.35 110 413

1920-29 1307 356 29.91 87 184

1930-39 737 421 34.86 42 104

1940-49 476 1189 42.83 22 72

1950-59 196 816 43.02 7 37

1960-69 82 781 63.45 3 20

1970-79 29 625 80.39 1 841

Cement block

ash

Sewagesludge

landfill

incinerate

Mine

reclaim

fertilizer

groundwater

Depositlocally

Bottom sludge

Depositelsewhere

Fishing sinkers& shot

Plant uptake

Flow to groundwater

To air

Other Ecosytem Impacts of Lead

2009 Class Project

Loyola Chem Sr.

S. 1994Growing Scientists20 5th graders map park soil lead

F 1994Northwest IncineratorAustin homes: Yard Soil Lead

F 1995Northwest IncineratorGrid map

House DustUptown 5th graders sample and tourlabs

F 1996

F 1997House DustLittle village Boys and Girls Club(failed) F 1998Northwest Incinerator

Tight grid and isotopes

F. 1999Bethel New Life: BrownfieldSoil sampling

F 2000Orozco School: House Dust

F 2001Pullman: White Lead Factory

House DustWest Pullman White Lead factory

F 2002

Alanah Fitch [email protected]

S 2008Lead in ToysEvanston Childcare

NationalAward forThe Class

ACSMtgposter

Homes Municipal Waste Incinerator

Incinerator 1994, 1995, 1998

Lead Elimination Action DriveWest-side Alliance for a Safe Environment (WASTE)Center for Neighborhood TechnologyAustin Neighborhood Council

Pb?

Wind

BackgroundSoil lead “Shadow” depends on

Stack heightLargest depositionIs here

Decreasing amts

Incinerator 1994, 1995, 1998

Incinerator 1994, 1995, 1998

Students meet withelderly ladies who letthem sample soils.The ladies discuss theirconcerns.

sampling

Control

4915 W. Kamerling

440

1040

2311431

4822 W. Potomac

187

150 250

1850 1385

4833 W. Crystal

garage

372

1800

Incinerator 1994, 1995, 1998

Front

Back

Soil Lead in parts per million (ppm)

439

2620

3067

700

2808

BRICK

2900

1133

6613 N. Ashland

1538

FRAME

6729 N. Ashland

Incinerator 1994, 1995, 1998

Comparison homes, 17 mile away

Second year: Resample with respect tothe wind; also allowing for up and down windcomparisons. Wins a National Award.

Luke later goes to CroatiaOn UN project onLead dispersion bygasoline

Incinerator 1994, 1995, 1998

North

Chicago

Washington

Demolished lot

Wind Pattern

Cic

ero

2312

8982

32

1231210546346

15

320

42

0

101

Pul

aski 644 mO

rr H

igh

Sch

ool

Incinerator 1994, 1995, 1998

This data presentedTo Mayor’s advisorycouncil

Class final: enterBusch National Env.Award competition –Place third

0

2

4

6

8

10

12

14

PPM Soil Lead

Fre

qu

ency

< 0.5 mile from incinerator

> 0.5 mile from incinerator

Incinerator 1994, 1995, 1998

Wind

BackgroundSoil lead “Shadow” depends on

Stack height Largest depositionIs here

Decreasing amts

Incinerator 1994, 1995, 1998

0

1530

4661

-61

-46

-30

-15

0

15

30

46

61

NNNE

NE

ENE

E

SE

Incinerator 1994, 1995, 1998

Last time: we finally set up an experiment worthy of an An air pollution expert

Across1 the system of pipes and other apparatus for conveying water,

liquid wastes, etc., as in a building3. the fluid that circulates and carries oxygen throughout the human

body4. being placed at risk8 the quality of degree of being toxic or harmful to plants or animal

life9. the introduction of harmful substances or products into the

environment10. a mixture of pigment and liquid12. food, eating healthy14. a pain located in the head15. the age group affected most by lead poisoning17. President on the $20 bill18. a transparent, odorless, tasteless liquid, a compound of hydrogen

and oxygen, H20, that constitutes rain, oceans, lakes, rivers, etc.19. . to take ill through eating

Down2. a heavy, comparatively soft, malleable, bluish‑gray metal. A

toxic metal, that has been widely used in paints, plumbing and fixtures, and in some water supply service lines

3. composer thought to have had lead poisoning5. the portion of the earth's surface consisting of dirt6. the air, water, minerals, organisms, and all other external factors

surrounding and affecting a given organism at any time7. dry particle of earth10. a table illustrating the periodic system, in which the chemical

elements are shown in related groups11. . the process of preparing the samples by breaking down the baby

wipes into a substance suitable testing13. a silver‑white divalent metal found in limestone, chalk, milk16. the science that deals with the composition and properties of

substances and various elementary forms of matter

2009 – Brainstorm on Projects

Short list by next week

Health Effects of Lead

Inhalation depends uponthe particle size.

This data is for humans

Dissolution of lead carbonate particles insimulated gastric juices as a function of particle size

For birds, the uptake will depend upon the pH and grinding action in the gizzard. For ruminants, the uptake will depend upon the lifetime in the digestive organs

94-99% of lead attached toexternal surfaces of erythrocytes

1-6% lead in plasma,of which 99% attached toproteins

~0.1 to 0.6 % of lead isas the free cation

Ca BaActive uptake ofcalcium,apparentlyto lesser extent other divalent similarsized cations,including lead.

Recognition will be similar for various species

Calcium uptake is controlled by Vitamin D and growth regulators parathyroid hormone (PTH)

Calcium is stored to the endoplasmic reticulum, lead will alsogo there

Basophilic Stippling of Dog Blood caused by nucleation ofribonucleoproteins in presence of lead

High lead causes deformation of blood cells and shorter lifetime ofthe red blood cell.Double whammy - production is also affected

Current measurementsno longer rely on zincprotoporphyrinas PbB effectson fetal developmentcan be detectedat values of PbB<5 ug/dL

Renal biopsy of a 28 year old shipwrecker. Dense intranuclear inclusion body is characterized by a fibrillary outer margin; Cramer, Goyer et al. Brit. J. Indust. Med., 1984

1 hour after exposurelead isfoundwithin the kidneys,becausekidneysare monitoringbloodcalciumlevels viathe glomerular filtration rate

Renal biopsy of a 28 year old shipwrecker. Interstitial fibrosis with atrophy of some tubular lining cells; Cramer, Goyer et al. Brit. J. Indust. Med., 1984

Damage to kidney results in hypertension gout

Thomas Rowlandson’s The King’s Bath

Cruikshank’s gout

Calcium is closely monitored by kidney because it plays a largerole in various signalling processes

Calcium bound to calmodulinC. Yang, G. S. Jas, K. Kuczera, J. Biomolecular Structural Dynamics,2001, 19,257-271

Lead double whammy1. Low lead turns on triggers2. Hi lead turns off triggers

Calcium serves as a trigger for musclecontractions: troponin C

Colic is a form of muscle spasmingSo are the “shakes”

Lead, like calcium, is deposited to the hard tissuesImplications for the Trophic level of lead in the environment

Osteocalcin (bone Gla protein (BGP)) controls calcium depositionand is affected by lead: weaker bones for affected individuals

Longitudinal Section & Cross Section of Bone

TrabecularBone

Compact Bone

Seizures can result from lead due to Ca triggers of the synapses

Other Irrelevant Information thatIs mildly amusing/interesting on Lead

886oC

-0.2oC (Au)230oC (Ag)

Purity of Pb: 99.9% achieved

~5,000 years ago Cuppellation Begins