The Search for
What
and How Much ends with Spectronic® Spectrophotometers At the heart of qualitative and quantitative analysis are the questions WHAT and HOW MUCH. SpectronicfSpectrophotometers aid your search for answers to those questions. Each model in the Spectronic family was built to help meet the different needs of different labs at different times. Select the performance you need at a price that's right.
Select from an unsurpassed variety of s a m p l i n g capabilities. Eliminate cuvette m a t c h i n g with m i c r o flow-thru cell a n d process more than 300 S A M P L E S PER H O U R . Also get direct c o n c e n t r a t i o n readout plus best meter readability a n y w h e r e . (16 inches of linear absorbance).
C o n d u c t field analyses with this H A N D - H E L D unit that has a 20nm spectral slit w i d t h . Use all kinds of cuvettes. C o m p l e t e with r e c h a r g e a b l e battery.
Use up to 100mm path length for sensitive trace analysis.
+ Simple controls (no dark current adjust) Takes nearly any test tube or cell + 8nm spectral slit width -f- Automatic filter + Find out what m a d e S p e c t r o n i c 20 the M O S T P O P U L A R ever m a d e . M o r e than 100,000 have b e e n bought.
insertion
Spectronic 700
Expand selected segments of the standard curve with TWO CONCENTRATION MODES. Use modular quick-change sampling systems, including microflow-thru, to process more than 300 samples per hour. Inserts filters automatically. All this, plus built-in UV power supply.
BAUSCH & LOMB
Step into the UV region the solid state way and get the WIDEST WAVELENGTH RANGE (200-1000nm). Simple to use color-coded controls and digital readout. FOR QC: Push a button and verify instru ment setup, and check reagent quality and stand ard curve reproducibility.
Stability you need for LC MONITORING. Special push button to verify instru ment setup and check reagent quality and stand ard curve reproducibility. Don't overlook the highresolution 2nm spectral slit width.
Digital readout provides stable and accurate read ings of KINETIC REAC TIONS or small changes in concentration. Pick your own decimal position. Check out electronic calibration yourself.
Spectronic 100 AUTOMATE. Expand Spectronic Spectropho tometers to automated sys tems with data printer, sampler for unattended operations, diluter-pipetter for sample/reagent dis pensing. Lets you identify samples, consume less reagents, all automatically.
DOUBLE BEAM TOO. Five spectral slit widths to .25nm. Reflectance and high scanning speed modules. Couple to re corder for data display. Flow-thru accessories available.
For full details, write Bausch & Lomb, Analytical Systems Division, 820 Linden Avenue, Rochester, New York 14625.
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Table I. Significance of Metals (23,24) Metal I I (A) Li
Na Κ Rb
Cs
l(B) Cu
Ag
Au
Action
No k n o w n r e q u i r e m e n t ; reversible k i d n e y damage f r o m L i accumula t i o n of high L i doses or l o w Na doses Essential; required for nerve sig nal t r a n s p o r t f u n c t i o n s Essential; r e q u i r e d for nerve signal t r a n s p o r t f u n c t i o n s N o k n o w n r e q u i r e m e n t s ; can in terchange w i t h Κ in m e t a b o l i c processes; a c c u m u l a t i o n of Rb disrupts cell f u n c t i o n No k n o w n r e q u i r e m e n t s ; in s u f f i c i e n t k n o w l e d g e available
Toxicity
L D 5 0 (mouse) 1.06 g/kg
Metal
11(B) Zn
Cd
L D 5 0 (mouse) 1.21 g/kg
L D 5 0 (mouse) 1.20 g/kg Hg
Essential in trace a m o u n t s ; f o u n d in h e p a t o c u p r e i n , c y t o c h r o m e C oxidase, and c e r u l o p l a s m i n ; in volved in a n u m b e r of enzymes, e.g., phenol oxidases and c y t o c h r o m e oxidases; hemolysis f r o m high c o n c e n t r a t i o n s N o t essential; A g + salts absorb p o o r l y ; A g + remains impregnated in tissue as Ag 2 S (argyria) N o t essential; A u 3 + i n h i b i t s reversibly intralysosomal proteases by b i n d i n g s u l f h y d r a l groups; causes a g g l u t i n a t i o n , hemolysis, and i n h i b i t i o n of collagenases and elastases; used f o r t r e a t m e n t of rheumatoid arthritis
II 11 (A) Be T o x i c ; causes chemical p n e u m o nitis, acts as possible carcinogen in lungs and bones; damages skin and m u c o u s m e m b r a n e ; n o t ex creted f r o m m a m m a l i a n tissue; i n h i b i t s alkaline phosphatase, t h y m i d i n e ; t h y m i d y l a t e kinase, D N A polymerase; combines w i t h u n p h o s p h o r y l a t e d enzymes and competes w i t h Mg f o r enzymes; Be-enzyme c o m p l e x unable t o chelate w i t h A T P Mg Essential; high doses cause diarrhea ataxia, and d e a t h ; excess Mg de natures serum p r o t e i n s ; required for enzyme transport functions Sr Essential?; deposited in b o n e ; may be essential f o r c a l c i f i c a t i o n of bone and t e e t h ; evidence suggests l o w levels result in dental caries Ba No k n o w n r e q u i r e m e n t ; used as marker in digestive t r a c t ; similar t o Ca in its properties; h i g h l y t o x i c w h e n ingested; causes v o m i t i n g , diarrhea, affects central nervous s y s t e m ; causes convulsions-, causes s t o m a c h , intestines, and kidneys t o hemorrhage; causes p n e u m o coniosis; stimulates all muscles
L D 5 0 (mouse) 0.05 g/kg
L D 5 0 (rabbit) 0 . 0 0 8 g/kg N o data; con sidered t o x i c
III "11(A) AI
Ga
L D ! 0 (mouse) 0.5 m g / k g
In
Tl
LD50 30 m g / 1 0 0 ml of b l o o d L D 5 0 (mouse) 400 mg/kg
L D 5 0 (mouse) 70 m g / k g
644 A · ANALYTICAL CHEMISTRY, VOL. 48, NO. 8, JULY 1976
111(B) Sc
Action
Essential; c o n t a i n e d in a n u m b e r of m e t a l l o p r o t e i n s and enzymes; large a m o u n t s cause malaise, diz ziness, v o m i t i n g , diarrhea; re q u i r e d f o r skin repair Toxic-, depresses g r o w t h and re duces p r o t e i n and fat d i g e s t i o n ; causes h y p e r t e n s i o n and cardio vascular p r o b l e m s ; accumulates in k i d n e y , liver, and r e p r o d u c t i v e organs; replaces Zn and binds ir reversibly; causes p r o t e i n u r i a , gly cosuria, carcinomas, edematons, and p r o l i f e r a t i v e and fibrogenic effects o n lungs T o x i c ; H g + salts o x i d i z e d by tis sues and e r y t h r o c y t e s t o h i g h l y t o x i c H g 2 + ; Hg retained by liver, k i d n e y , b r a i n , heart, l u n g , and muscle tissues; c o m p l e x e s w i t h — S H groups; i n h i b i t s S-amino-leulinic acid dehydratase and c h l o r i n esterase a c t i v i t y ; Hg p r o t o p l a s m i c poison, damages central nervous system
No k n o w n r e q u i r e m e n t s ; p o o r l y absorbed since it f o r m s c o l l o i d a l AI ( O H ) , in vivo T o x i c ; causes t u b u l a r damage t o kidneys and a b n o r m a l damage t o bone m a r r o w ; d e p o s i t i o n in soft tissues results in a neuromuscular poison; linked to tumor formation and g r o w t h suppression N o t essential; l n C I 3 causes t o p i c a l c a l c i f i c a t i o n ; it accumulates in soft tissues, disrupts n o r m a l mech anisms of enzymes, and is related t o f o r m a t i o n of t u m o r s T o x i c and c u m u l a t i v e p o i s o n ; associated w i t h K; accumulates in e r y t h r o c y t e s , agglutinates, and lyses e r y t h r o c y t e s ; accumulates in k i d n e y , b o n e , and soft tissue
Toxicity
L D I 0 (rabbit) 2 . 0 g/kg
L D 5 0 (mouse) 0 . 0 2 7 g/kg
L D 5 0 (mouse) 0 . 0 2 7 g/kg
L D S 0 (rat) 4 . 3 g/kg L D 5 0 (rat) 0.05 g/kg
L D S 0 (rat) 0 . 0 0 3 g/kg
L D S 0 (rat) 0.026 g/kg
No k n o w n r e q u i r e m e n t s ; used as a L D S 0 (mouse) fecal marker t o m o n i t o r intestinal 4 . 0 g/kg a b s o r p t i o n ; involved w i t h g r o w t h depression and t u m o r p r o d u c t i o n , t o x i c i t y due t o r u p t u r e or b l o c k age of gastrointestinal tract L D , 0 (mouse) No k n o w n r e q u i r e m e n t s ; rare Rare 0.2 g/kg earths earths a c c u m u l a t e in soft tissues; no k n o w n i n v o l v e m e n t of rare earths in i n h i b i t i o n of specific enzymes
Matai
Action
Toxicity
Metal
IV
IV(A) Sn
Pb
Essential; lipid soluble; organo-tin compounds accumulate in central nervous system; no known involvement with specific enzyme systems Toxic; metabolism similar to Ca; accumulates in bones and soft tissues, particularly in the brain, resulting in reduced functioning; complexes with S—H groups, inhibits biosynthesis of heme, particularly in conversion of J amino levulinic acids to prophobilinogen, inhibits formation of heme from iron and protoporphyrin, decreases formation of 6-amino levulinic acid, decreases conversion of protoporphyrinogen into protoporphyrin IX; causes loss of amino acids, glucose, and phosphate in urine by structural damage to mitochondria of kidneys; has been linked to increased dental caries and is poorly excreted
LD 5 0 (dog) 0.16 g/kg
Essential?; various Ti salts therapeutic for skin disorders; Ti stimulates phagocytes, resulting in increased immunological activity No known requirements; accumulates in soft tissue and spleen; possesses anticarie activity in rats No known requirement; accumulates in liver; no information available on Hf activity
No data
LD 5 0 (rat) 0.15 g/kg
Nb
Ta
Zr
Hf
Sb
Bi
LD 5 0 (rat) 3.5 g/kg LD 5 0 (rat) 0.14 g/kg
Te
No known requirements; has been L D 5 0 (rat) of therapeutic value; accumulative 0.07 g/kg general system poison; causes dermatitis and bronchitis; carcinogenic in mouth, esophagus, larynx, and bladder; inhibits ATP synthesis by uncoupling oxidative phosphorylation and replacing stable phosphoryl group; inhibits thiodependent enzymes and binds to tissue proteins as keratin disulfides in hair, nails, and skin Inhibits thiol-containing enzymes; LD S 0 (mouse) no known value; has been of 0.6 g/kg therapeutic value No known requirements; causes L D 5 0 (rat) hepatitis and nephrotoxicity; pos- 0.7 g/kg sibly affects thio-containing enzymes Appears to be essential; mobilizes Fe to liver and Ca to bones; inhibits synthesis of cholesterol, phospholipids, and other lipids and
L D , 0 (rabbit) 0.2 g/kg
Essential; complexes with plasma proteins and is distributed to all tissues; replaces S in cystine, methionine; connected with increase in dental caries in children; irritates eyes, nose, throat, and respiratory tract; causes cancer of liver, pneumonia, degeneration of liver and kidney, and gastrointestinal disturbances; blocks some enzyme systems; found in mammary gland secretion No known requirements; reportedly not involved in enzyme systems; complexed by plasma proteins; causes renal and hepatic degeneration
VI(B) Cr Essential; CrVI more toxic than Crl 11 ; combines with /3-globulins; essential for normal metabolism of glucose; causes perforation of nasal septum, congestion, hyperemia, emphysema, tracheitis, bronchitis, pharyngitis, bronchopneumonia, cancer of respiratory tract, and dermatitis Essential; required by flavin deMo pendent metalloenzymes; retained in bone and soft tissue W No known requirements; retained in bone VII Mn
V(B) V
LD S 0 (rat) 3.0 g/kg LD S 0 (rat) 1.9 g/kg
VI(A) Se
V V(A) As
amino acids (theotic acid, uric acid); inhibits activities of following enzymes: tyrosinase, nathine reductase, xanthine, cystine, and nitriate reductase; has adverse bioeffects on tissue oxidation; inhibits sulfhydral activity, reduces blood lecithin content and precipitates serum proteins; inhibits excretion of corticosteroids, acetylcholine metabolism,liver acetylation process, activities of coenzymes A, Q, and 1, adenosine triphosphatases Accumulates in blood, bone marrow, and spleen; no known requirements No known requirements; accumulates in soft tissues
Toxicity
VI
IV(B) Ti
Action
Re
Affects central nervous system causing cramps, tremors, hallucinations; causes manganic pneumonia and renal degeneration No known requirements; considered biologically inert
LD 5 0 (rat) 0.003 g/kg
LD S 0 (rat) 0.002 g/kg
L D 5 0 (rat) 0.18 g/kg
LD 5 0 (rat) 0.19 g/kg LD S 0 (rat) 0.24 g/kg LD 5 0 (mouse) 0.21 g/kg
L D 5 0 (rat) 0.9 g/kg
ANALYTICAL CHEMISTRY, VOL. 48, NO. 8, JULY 1976 · 645 A
Metal VIII Fe
Co
Ni
Action
Essential; required f o r hemoglo bin requirements dependent on age and sex; F e l l not e x c r e t e d ; supposedly causes benign pneu moconiosis; has synergistic effects w i t h S 0 2 and carcinogens; inhibits glucose-6-phosphatase, succinic acid dehydrogenase, and other ox idative enzymes Essential; required f o r vitamin B 1 2 ; produces p o l y c y t h e m i a and affects normal g r o w t h of erythrocytes Essential; involved in e n z y m e ac t i v i t y , h o r m o n a l a c t i o n , structur al stability of biological macromolecules, and general m e t a b o lism; causes dermatitis, respiratory disorders, and cancer of respira t o r y system; reduces activities of c y t o c h r o m e oxidase, isocitrate de hydrogenase of liver, maleic de hydrogenase of kidney
animals is low, whereas absorption ef ficiency into the blood stream via the lungs can be quite high. Table II shows the relationship be tween the particulate loading in the atmosphere and the different sources of emissions. Diameters of particles range from 2 X 10~ 4 to 5 Χ ΙΟ2 μπι with the majority ranging from 1 X 1 0 - 2 to 10 Mm. Particulate material emissions are classified as either primary or secon dary. Primary emissions are produced by physical or chemical processes prior to injection into the atmosphere, and secondary emissions are produced by chemical reactions which occur in the atmosphere. Although primary and secondary particles are sometimes comparable in dimension, secondary particles generally tend to be some what smaller; subsequently, the con trol of secondary particle emission is difficult and often impossible. For the purposes of this discussion, we will ne glect secondary emissions since these particles seldom contain large amounts of trace metals. The first step in any study of the role of metals in the environment is to establish the form in which the metal exists. Normal analytical chemical techniques are not designed to mea sure oxidation states nor composition of the metal species required in envi ronmental studies of trace metals. Ad vanced analytical chemical techniques that enable such measurements are re quired. The source of the metal can general ly be used to determine the form of the metal ion. For example, the lead emitted from pre-1975 mobile sources
Toxicity
L D S 0 (rat) 0.9 g/kg
Action
Ru
N o k n o w n requirements; highly injurious t o lungs and eyes; re tained more in soft tissues N o k n o w n requirements; exhibits slight carcinogenic a c t i v i t y ; shows some c h e m o t h e r a p e u t i c activity against viral infections by inhibiting f o r m a t i o n of virus phospholipid N o k n o w n requirements; produces acute damage t o liver and kidney cells and hemolysis N o k n o w n requirements; a c c u m u lates in bone m a r r o w w h e r e it af fects m a t u r i t y of reticulocytes N o k n o w n requirements; used as nutritional and fecal m a r k e r ; in sufficient knowledge available N o k n o w n requirements; used in c h e m o t h e r a p y ; currently under going intense t o x i c i t y studies re lated to vehicle emission control
Rh
L D S 0 (rat) 0.5 g/kg
Pd
Os L D 5 0 (dog) 0.8 g/kg LD50 1—3 p p m
Ir
Pt
is in the following forms: unburnt tetraethyl lead, lead sulfate, various lead bromide complexes, and lead ox ides. In a particular situation, if it can be established that the sources of lead are mobile sources, then it is sufficient only to measure the lead concentra tion in airborne particles. Currently, only mobile sources of air pollution are strictly controlled by leg islation. Mobile sources contribute only about 35% of total metal loading in the atmosphere, whereas stationary sources, the major cause of airborne particulates, have yet to be effectively controlled. As a result of recent legis lative pressure, stationary sources are decreasing the size of the source ef fluent, often by the addition of man ganese and barium salts, to shift the optical properties of the smoke from the visible to the ultraviolet region of the spectrum, thereby concealing ob vious pollution but inadvertently in creasing potential health hazards. Sampling Techniques. The two types of samples normally obtained for analysis are either high volume or low volume (grab samples). High-volume samples are generally used if the concentrations of the met als are low. In determinations of nor mal daily levels of metal concentra tions in air, high-volume sampling techniques are routinely utilized. Low-volume samples require more specialized techniques, but could en hance the effectiveness of regulatory agencies to check polluters who exceed the maximum allowed level for a short period of time and still meet the daily allowed levels of emissions. Methods for collecting particulates
646 A « ANALYTICAL CHEMISTRY, VOL. 48, NO. 8, JULY 1976
Toxicity
Metal
L D 5 0 (rat) 0 . 3 6 g/kg L D 5 0 (rat) 0 . 2 8 g/kg
L D S 0 (rabbit) 0 . 0 2 g/kg L D 5 0 (dog) 400 mg/M3 vapor N o data
N o data
Table I I . Significant Sources of Man-Made Particulate Pollution in tr United States (2) Source
Emission millions ι tons/yi
Natural dusts: t o t a l , % Open burning: t o t a l , % Wildfire Controlled fire Slash b u r n i n g Accumulated titter Agricultural burning
63, 51.3 5 6 . 3 , 45
T r a n s p o r t a t i o n : total, % M o t o r vehicles Gasoline Diesel Aircraft Railroads Water transport N o n h i g h w a y use Agriculture Commercial Construction Other
1.2, 1.0
Incineration: total, % Municipal incineration On-site i n c i n e r a t i o n W i g w a m burners (ex cluding forest products disposal) Open d u m p
0.931, 0 0.0! 0.11
O t h e r m i n o r sources: total, % R u b b e r f r o m tires Cigarette smoke A e r o s o l s f r o m spray cans Ocean salt spray Grand total, %
1.284, 1
37 6 11 2.4
0.4: 0.2(
o.o: 0.2; 0.1!
o.o: o.o: 0.0(
o.o:
o.o: 0.6:
0.3· 0.2: 0.3! 0.3122.715
Table IV. Impurities in Various Filter Types (ng/cm 2 )
Glass fiber
from the atmosphere are of two cate gories: passing air collectors and fallen dust collectors. Passing air collectors are used to monitor suspended atmospheric par ticulates and can be further divided into the following types: • Cascade impacters that use the inertial size of the particles • Cyclones that use centrifugation, impaction, and filtration • Liquid impingers that use absorp tion • Electrostatic precipitators that use electrical potentials to charge the particles • Filters that depend upon particle size. Fallen dust collectors are similar to rainfall monitors and are routinely used for air monitoring of metals. Sampling times of at least one month are required to collect sufficient sam ple for analysis. During this extended period, interferences due to algae, fungi, insects, bird feces, and human factors make the sample questionable. The height above the ground at which the air is to be sampled is also signifi cant, since the particle loadings de crease with increase in height. Because air is heterogeneous, parti cles are usually collected from large volumes during a 24-h period. The use of such sampling periods reduces sam ple irregularities but precludes cycliTable I I I . Annual Metallic Emissions from Stationary and Mobile Sources (1970)(25) Stationary (mobile) sources. tons/yr
Metal Arsenic Barium Beryllium Cadmium Chromium Copper Lead Highway Off highway Manganese Magnesium Mercury Molybdenum Nickel Selenium Silver Titanium Vanadium Zinc Total
648 A ·
10 6 0 0 15 4 2 0 172
2 18 13 16 (197 (16 17 75
160 136 680 000 437) 563) 900 293
Emis sion, % 1.60 2.33 0.03 0.33 2.73 2.07 34.72
88 351 20 300 159 922
2.70 11.38 0.13 0.14 1.10 0.14 0.06 13.33 3.07 24.14
662 494
100
857 990
7 310 986 417
ANALYTICAL CHEMISTRY,
Silver membrane
Cellulose ester (MF-Millipore) 10
AI
(26-28)
Polystyrene (Microsorban) 20
Polycarbonate (Nuclepore) 6
0.03
0.1
Be
40
200
Cd
. ..
Ca
... . ..
260
300
6
Cr
80
60
14
2
3
Cu
20
20
40
320
3
Fe
4000
300
40
85
Pb
800
200
8
Mg Ni
7 X 10
Si Na
. ..
Ti
800
Zn
100
Nd(fod)3
Sm
Sm(thd)3, Sm(fod)3
Eu
Eu(thd)3, Eu(fod)3
Gd
Gd(thd)3, Gd(fod)3
Tb
Tb(thd)3, Tb(fod)3
Dy
Dy(thd)3, Dy(fod)3
Ho
Ho(thd),, Ho(fod)3
Er
Er(thd)3, Er(fod)3
Tm
Tm(thd),, Tm(fod)3
Yb
Yb(thd)3, Yb(fod),
Ln
Ln(thd)3, Ln(fod),
acac: 2 , 4 - p e n t a n e d i o n a t e , t f a : 1,1,1t r i f l u o r o - 2 , 4 - p e n t a n e d l o n a t e , f o d : 1,1,12,2,3,3-heptafluoro-7,7-d!methyl-4,6-octanedlonate, t h d : 2,2,6,6-tetramethyl-3,5heptanedionate.
digestion since lower-grade reagents may introduce metal concentrations that are higher than the sample. Ex tensive work has been reported (8) on solvent systems for biological diges tions that indicate chemical digestions are fast, efficient methods which mini mize the loss of metals by container surface adsorption or by volatilization. Other methods (9) for the removal of organic matrices generally require the use of low-temperature ashers or muffle furnaces. However, the longer time required for these processes is undesirable, and some metals are lost by volatilization. Normally, biological samples con tain high concentrations of potassium, sodium, and phosphorus which will usually interfere with subsequent chemical analysis. The use of masking agents or selective solvent extraction is required and commonly results in a partial loss of the metal ions of inter est. A number of studies ( 10) have been made into the relative merits of various procedures to remove these in terfering ions with limited success.
650 A · ANALYTICAL CHEMISTRY, VOL. 48, NO. 8, JULY 1976
10-'4g
Methods of Analysis
A list of current analytical tech niques which meet the constraint of ultratrace analysis is shown in Table V, and detection limits for some of these techniques are included in Ta bles VI-XII. Some of these techniques (NAA, XRF, EMP, ESCA, AES) are able to analyze biological and environmental samples directly, although the latter three techniques are surface tech niques requiring that the samples be very thin or homogeneous. The other techniques generally require that the sample be in solution, except for SSMS, which only requires the biolog ical samples to be ashed. A number of these techniques are not suitable for multielement analysis (NFAAS, ESCA, AES, ASV, DPP, and GC) lim iting their application. Tables V-XI show that not all these techniques are suitable for all metals. For example, NAA is not sensitive to lead or berylli um, and GC and CIMS are limited to metals which form thermally stable
Table X . Detection Limits fag) for X-ray Fluorescence Spectrometry Element* 3
Element"
(44-50)
Element"
Element"
Ag, 1.2
Cs,
0.15
N d , 0.30
Sr,
A I , 5.0
Cu, 0.00002
N i , 0.06
Tb, 159/ml
As, 0.11
E u , 0.66
Ρ,
T e , 0.12
Au,0.001 /cm2
Fe, 0 . 0 0 8 5
Pb, 0.0003
T h , 6.5 / m l
Ba, 0.12
Ga, 0.01
Rb, 0.0075
Ti,
Bi,
U (as U O 2 ) , 0 . 7 2
0.61
0.001
0.00007
0.001
Hg, 0.24
R h , 103 / m l
Ca, 0.100
In,
1.1
Sc, 0.38
U,
0.00002
C d , 0.40
K,
0.52
Se, 0 . 0 2 0 / c m 1
Y,
0.22
Ce, 0.17
L a , 0.12
Si,
Yb,6.8 /ml
C o , 0.05
M n , 0.00015
Sm,4.1 /ml
Z n , 0.00004
Cr, 0 . 0 0 0 0 6
M o , 0.072
Sn, 3.9 p p m
Zr,
170 p p m
0.00002
a
N o t available: Be, D y , Er, G d , Ge, H f , lr, L I , L u , Mg, Na, N b , N p , Os, Pa, Pd, Pr, Pu, Re, Sb, T a , T m , and w
volatile complexes. ESCA is the only ultratrace technique currently avail able for measurement of the oxidation state of the metal. The choice of the analytical technique is based on the requirement of the analysis and upon the personal preference of the analyti cal chemist. Metal Functions in Environmental and Biological Systems
This section reviews the significance of metals in environmental and biolog ical systems. Environmental Systems. The analysis of metals in air has currently generated two major concerns: deter mination of levels of toxic metals and establishment of the origin of the air borne particles. Determination of Levels of Toxic Metals. As mentioned previously in this report, only mercury and berylli um emissions are currently controlled by legislation, although cadmium and lead emissions are expected to be reg ulated soon. Regulatory monitoring of lead and mercury, which forms vola tile alkyl complexes, poses unique sampling and analysis problems. Tetraethyl lead, an additive to gaso line, may be emitted during manufac ture, dispensing at gasoline stations or operation of vehicles. Dimethyl mer cury is produced by various organisms from inorganic mercury salts. These two lipid soluble compounds are par ticularly environmentally significant since they can easily enter the body and cause potential health hazards. Although currently unregulated, the most toxic compound of nickel, nickel
carbonyl, has been established as an irritant and carcinogen. As gases or vapors, these compounds will readily enter the lungs where they may be ab sorbed into the blood stream. Normal collection of these com plexes by filtration is ineffective. The use of liquid impingers is the best method for collecting these com pounds, and the resulting solution can be analyzed directly by any technique sensitive to the metal of interest. Cur rently, the use of CIMS is being inves tigated in our laboratories as a method for analyzing air directly for these vol atile metal complexes. Nonvolatile forms of cadmium, be ryllium, and other potentially toxic metals are found in particulate matter easily collected by filtration. Although this collection procedure does not give any information on particle size with respect to metal concentration, it is sufficient for most monitoring studies. Filtration procedures allow high or low volumes of air to be monitored, al though the choice of filtering media is dependent on the volume sampled. Membrane filters which can be chemi cally cleaned to remove background contaminants should be chosen for low-volume samples, but should not be used for high-volume sampling be cause they are easily overloaded, which results in the degrading of their filtering characteristics. Glass fiber fil ters which have high background lev els of metals, but can collect large quantities of particulate matter, should be chosen. Probably the best method for sam pling particulate matter is the use of a
cascade impactor coupled with mem brane filters which allow particles greater than 1 μπι to be sized by im paction and particles smaller than 1 μτη to be collected by filtration. This sampling train allows particles which can enter the lungs (1 μπι) to be ana lyzed separately. However, ongoing studies in our laboratories have shown that some of the particles are not trapped on the surface of the mem brane filter, but are trapped in the in terstices with resulting difficulty in re moval by dissolution. To increase the overall accuracy, investigators should use analytical techniques which can analyze the filter directly. Using such techniques is mandatory if the partic ulate matter is not soluble in normal acid systems. If direct analysis of the filter is not possible, then the filter should be dissolved or ashed prior to analysis. The synergistic effect of metals on overall toxicity is an area of trace
Table X I . Detection Limits with Anodic Stripping Voltammetry and Differential Pulse Polarography
(51-67) Ele ment
Ag
ASV
DPP
0.25 ppb
Au
1.0 p p b
Bi
0.01 ng/ml
0.2 n g / m l
Cd
0.005 n g / m l
0 . 9 8 ng/ml
Co Cu
0.01 n g / m l 0.005 n g / m l
13.7 n g / m l
Eu
1.2 χ 1 0 - M
Fe
1 Mg/ml
Ga Hg
4.0 χ Ι Ο "
In
0.1 ng/ml
Κ
2 X ΙΟ-» Μ
0.4 ng/ml
1 χ 10"
5
9
Μ 8 X 10-' M
M 0.03 Mg/ml
Μη
Ni
0.1 g/ml
Pb
0.01 ng/ml
0.78 n g / m l 1.5 g / m l 5.0 χ Ι Ο " 8 g
Pd Pt
1 Χ ΙΟ-9 Μ
Rh
0.1 n g / m l
Sn
2.0 ng/ml
1 Χ ΙΟ"3 Μ
TI
0.01 ng/ml
4 χ 10_" M
U
0 . 1 8 Mg/ml
V Zn
0.08 Mg/ml 0.04 ng/ml
ANALYTICAL CHEMISTRY, VOL. 48, NO. 8, JULY 1976 · 651 A
Table X I I . Metal Chelates Separated by Gas Ch romatography (68)
Cr
acac, acac, acac, acac, acac,
Μη
tfa
Fe
Zn
tfa, hfa, f o d tfa, hfa, t h d hfa, t h d , f o d acac, tfa, hfa, f o d tfa, hfa, t h d
Ga
tfa
Zr
tfa, thd
Nb
hfa
Ru
tfa, hfa tfa, hfa
Be
metal analysis that has so far been ne glected. Such studies must be under taken before meaningful legislation to control metal emission can be pro posed. Furthermore, the emissions of only two metals from a wide field of possible toxic contributors are cur rently controlled by legislation. Envi ronmentalists and toxicologists must investigate the toxicity of all metals to provide the necessary evidence as to the hazards to our present society. Such toxicity studies should include direct toxicity and concertion between groups of metals to produce toxic re sults or synergistic effects which in crease in toxicity of organic pollu tants. Additionally, the relationship between the oxidation state of the metal and toxicity should be included. Establishment of Origin of Air borne Particles. The fingerprinting of emission sources is a potentially pow erful environmental monitoring tech nique determining the origin of air borne pollutants. Fingerprinting par ticulate emission requires the determi nation of relative concentrations of a series of metals preferably using a multielement technique. It is well es tablished that the emissions from sources are related to the fuels used and the products manufactured. How ever, source fingerprinting is currently being studied by regulatory agencies to police emitting sources. Source fin gerprinting also allows modeling the transport of particles in the atmo sphere to study nucleation, fallout, and the distance traveled by particles in such studies. Low-volume samples can be effectively employed to take grid samples from the air, thereby re ducing ground-level dust interference. Since size is not critical, membrane filters are normally used to collect samples for source fingerprinting. Interest in source fingerprinting to monitor metal emission is increasing, and effective utilization of such tech niques to monitor potentially hazard ous levels from a given source is antic ipated in the near future. Biological Systems. Toxicological Studies. Presently, two facets of metal toxicology exist, lethal dose studies (LD) and monitoring methods for de tection of unnatural states. LD studies are presently performed on a macrodosage scale. Metal content in the excreta and body fluids of test animals is monitored, and the metal distribution in sacrificed animals is determined. Monitoring such experi ments is time consuming, and animal autopsies are usually general in na
ture. Samples are usually taken from homogenized dissected organs and tissues. However, some ongoing re search (11) has attempted to obtain more detailed information from ab sorption site studies. Such studies are time consuming and generally yield little or no information of anabolic or catabolic pathways affected by the metal of interest. Several researchers (12-16) have combined toxicology with bacteriology to provide a larger number of avail able species, thereby obtaining more detailed information. The results ob tained concerning metallic effects on their metabolic pathways can now be related to those of mammals. Further more, mutagenic studies can be made very rapidly since bacteria reproduce rapidly. Finally, the administration of essential metals and metals of interest can be easily controlled by the use of defined synthetic growth media. To monitor effectively the levels of toxic metals in the body, prior knowledge of preferential storage locations is often required. Arsenic, for example, is stored in fingernails and in the hair. Metabolism and Transport Stud ies. The essential or nonessential na ture of trace metals in bodily func tions is determined by the following of transport and absorption processes in test animals in a manner similar to toxicological studies. In the past, it was common to analyze macrosamples of dissected tissues or organs. Recent trends (17, 18) include the analysis of single tissue layers and cells by using electron microscopy and electron mi croprobe analysis. Additionally, sever al current studies (19-22) reflect in creased interest in the effects of or ganic compounds on trace metal ab sorption. However, the oxidation and coordination state of the element of interest is rarely determined. Such a determination is important for all es sential and retained nonessential met als, except alkali or alkaline earth, be cause different chemical forms of such elements can affect their overall toxic ity. An ESCA method used to gather qualitative data concerning the envi ronment of the metal atom coupled with either a multielemental or single elemental method to determine the quantitative abundance could provide an effective analytical technique for relating metal oxidation states to tox icity. Conclusions Understanding the role of ultratrace metals in the environment and biolog ical systems is becoming increasingly
652 A · ANALYTICAL CHEMISTRY, VOL. 48, NO. 8, JULY 1976
AI Se V
Co Ni Cu
Rh
tfa, tfa, tfa, tfa tfa,
In
tfa
La
thd
Pr
fod,thd fod, t h d fod, t h d fod, thd fod, t h d fod, thd f o d , thd fod, thd fod, thd f o d , thd f o d , thd fod, thd
Nd Sm Eu Gd Tb Dy Ho Er Tm Yb La Hf
tfd
Ta
hfa
hfa, f o d hfa, f o d fod, thd hfa, f o d
important to the overall under standing of the potential hazards to our health and welfare. Investigations in the following areas should be vigor ously pursued by current and future scientists: • Determination of the oxidation state of metals' trace levels in the at mosphere and in biological systems • Determination of the synergistic effect of metals on the toxicity of other compounds • Determination of the relationship between particle size and metal con tent in atmospheric particulates • Use of bacterial systems to study the long-range effect of ultratrace metals on biological systems. An additional area which should re ceive extensive interest is the field of environmental toxicology. This study should consider the long-term effect of groups of relatively nontoxic material upon society.
Finally, t h e r e is still a need to establish baseline pollution levels of metals in t h e a t m o s p h e r e so t h a t any changes in t h e s e levels will be recorded.
Acknowledgment T h e a u t h o r s t h a n k Charles E. Figgins a n d F r a n k J. Maccioli for their help a n d suggestions.
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(64) W. Demerie, E. Temmerman, and F. Verbeck, Anal. Lett., 4, 247 (1971). (65) B. H. Vassos and R. A. Osteryoung, Chem. Instrum., 73-74, 257 (1974). (66) A. Lagrov and F. Verbeck, J. Electro anal. Chem., 19, 423 (1968). (67) P. Zuman, Proc Anal. Div. Chem. Soc, 12,199 (1975). (68) R. W. Moshier and R. E. Sievers, "Gas Chromatography of Metal Chelates", Pergamon Press, London, England, 1965; references cited therein. Part of this work was presented in the BenedettiPichler Award Symposium at the Second Nation al Meeting of the Federation of Analytical Chem istry and Spectroscopy Societies, Indianapolis, Ind., October 1975.
J o s e p h J . D u l k a (right) is a P h D can d i d a t e in chemistry a t t h e Pennsylva nia S t a t e University. H e graduated with a B S in chemistry from Miami University of Ohio in 1972. Currently, he is studying trace metal flow in bac terial systems. T e r e n c e H. R i s b y (left) is an assis t a n t professor of chemistry and a fac ulty m e m b e r of the Center for Air E n v i r o n m e n t Studies a t t h e Pennsylva nia S t a t e University. H e graduated with a P h D in chemistry from Imperi al College of Science and Technology, London University, in 1970. During the academic year 1970-71, he was t h e recipient of a E u r o p e a n fellowship from t h e Royal Society of L o n d o n a t t h e University of Madrid. His next po sition, as a research associate, was held a t t h e University of N o r t h Caro lina at Chapel Hill, and in 1972 he joined t h e Pennsylvania S t a t e Univer sity. Dr. Risby's research interests in clude t h e significance of metals in bio logical a n d environmental systems, electrical discharges, t h e r m o d y n a m i c s of gas liquid chromatography, a n d trace analysis by mass spectrometry.
ANALYTICAL CHEMISTRY, VOL. 48, NO. 8, JULY 1976 · 653 A
