Instrumental Methods of Analysis 1. Introduction. Writing Intensive Rewrites are Required Large Amount of Excel Data Management Work Individual Work Log Own Sample Exams Lab Book pages Group Division and Attribution of Labor (Accountability) Reports Calibration Curves - PowerPoint PPT Presentation
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Instrumental Methods of Analysis 1. Introduction 1. Writing Intensive 1. Rewrites are Required 2. Large Amount of Excel Data Management 2. Work 1. Individual 1. Work Log 2. Own Sample 3. Exams 4. Lab Book pages 2. Group 1. Division and Attribution of Labor (Accountability) 2. Reports 3. Calibration Curves 3. Single Analyte (Skill Development and Cross Comparison Methods) 1. Overlapping Themes 1. Statistics/Sampling 2. Solution Chemistry 3. EDTA 4. Isotopes 5. Phase Separations
Transcript
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
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
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
