Chapter Seventeen: Semi-Micro Qualitative Analysis and Metal Ions

 

 

Chemicals:

 

The solutions are dispensed in 250 mL dropping bottles, except the conc. (15M) HNO3. Dry salts are dispensed in a small bottle. We push a micro-spatula through a cork for each dry salt. We use 3 sets of reagents for each room (except the 15 M HNO3).

 

1. 3 M ammonium acetate

231.2 grams per liter

 

2. 6 M ammonium chloride

320 grams per liter (sat.)

 

3.                  1 M ammonium thiocyanate

76 grams per liter

 

4. 0.2 M dimethylglyoxime

12 grams per liter ethanol (95%)

 

5. 3% hydrogen peroxide

Dilute purchased 30%

6. 0.2 M lead acetate

76 grams per liter

7. 0.5 M potassium chromate

97.1 grams per liter

8. 0.2 M potassium ferrocyanide

84.5 grams K4Fe(CN)6 3H2O per liter

9. 0.2 M stannous chloride

Dissolve 45.0 g SnCl2 2H2O in 170 mL conc. HCl

Dilute to 1 liter with water

Add solid tin to preserve

 

10. 5% thioacetamide

50 grams per liter

11. Conc. HCl

12. Conc. HNO3

13. Conc. NH3

14. 6 M acetic acid

345 mL glacial per liter

15. 6 M HCl

500 mL conc. per liter

 

16. 6 M HNO3

390 mL conc. per liter

 

17. 6 M NH3

405 mL conc. per liter

 

18. 6 M NaOH

240 grams per liter

 

19. KNOWN SOLUTION

To make 1 liter of solution:

(10 mg ion conc. per mL)

 

15.8 grams AgNO3

14.0 grams Hg2(NO3)2 2H2O + 11 mL conc. HNO3

16.0 grams Pb(NO3)2

16.7 grams Hg(NO3)2 1/2H2O

37.5 grams Cu(NO3)2 3 H2O

27.5 grams Cd(NO3)2 4H2O

77.0 grams Cr(NO3)3 9H2O

72.5 grams Fe(NO3)3 9H2O + 2 mL conc. HNO3

50.0 grams Ni(NO3)2 6H2O

46.0 grams Zn(NO3)2 6H2O

42.4 mL Mn(NO3)2 50% solution

 

Dissolve the above 11 salts all together in one solution.

 

20. Make a Group III only solution also

To make 1 L of solution use:

 

77.0 grams Cr(NO3)3 9H2O

72.5 grams Fe(NO3)3 9H2O + 2 mL conc. HNO3

50.0 grams Ni(NO3)2 6H2O

46.0 grams Zn(NO3)2 6H2O

42.4 mL Mn (NO3)2 50% solution

Dissolve the above 5 salts together in one solution.

21. Individual solutions for unknowns

These solutions are used to make the unknown samples (30 mg ion per mL) To make 500 mL solution:

a. AgNO3; 24 grams

 

b. HgNO3 H2O; 21 grams + 6 mL conc. HNO3

 

c. Pb(NO3)2; 24 grams

 

d. Hg(NO3)2 H2O; 25.5 grams

 

e. Cu(NO3) 3H2O; 57 grams

 

f. Cd(NO3)2 4H2O; 41.2 grams

 

g. Cr(NO3)3 9H2O; 117 grams

 

h. Fe(NO3)3 9H2O; 108 grams + 2mL conc HNO3

 

i. Ni(NO3)3 6H2O; 75 grams

 

j. Zn(NO3)2 6H2O; 69 grams

 

k. Mn(NO3)2; 63 mL (50%)

 

22. Dry Salts

(NH4)2SO4, ammonium sulfate

NaBiO3, sodium bismuthate

Na2S2O4, sodium dithionite

 

23. Litmus paper

Cut in small pieces

 

24. Dithizone paper

Whatman 3 mm chromatography paper (Chap. 15)

Dip strips in a solution of 0.1 g dithizone in 100 mL acetone

Allow to dry, cut into pieces

Store in a tightly closed bottle (brown). It will keep 6 months or more.

 

 

Per Room:

 

1. Labels

 

2. Matches

 

3. #2 corks

4. Centrifuges

 

5. Extra test tubes

 

6. 2 microburners per hood

 

7. Box of 9 inch disposable (glass) Pasteur pipets

 

8. Waste jars

 

 

Per Student:

 

1 - #0 casserole with cork handle

 

1 - Each ring stand, ring, wire gauge, burner, matches

 

1 - 1/2" test tube brush

 

1 - Test tube rack

 

4 - Test tube clamps

 

12 - Test tubes (12 x 75 mm or size to fit centrifuges)

 

1 - 250 mL beaker

 

2 - 4 inch stirring rods (4mm)

 

1 - 2 inch watch glass

 

1 - 2 mL rubber bulb

 

1 - 10 mL graduated cylinder

 

2 - Thin-stem pipets

 

1 - Waste cup

 

1 - Wash bottle

 

Unknowns (1 per student):

Three cations per unknown. 10 - 12 drops of each cation will give the student enough unknown for 3 trials.

 

The following pages contain the case studies and references that we use with the unknown samples. We randomly number the case studies and then make unknown samples to match. The unknowns contain three cations chosen from the list of possibilities. The student is given the opportunity to choose a case study and is then given the corresponding unknown sample to analyze. Each of the 11 cations must be accounted for, as being either present or absent in the unknown. When the analysis has been finished, a report form is turned in to the instructor. The instructor grades the report, and then gives the reference, including the actual contents of the sample, to the student. The case study and the reference are to be included in the student's laboratory report. You may make copies as needed or rewrite.

 

Cation concentration is recommended to be 10 mg cation per mL. The solutions are therefore made at 30 mg/mL to allow for dilution when mixed together in the unknown sample. Following are the possible cations. Use any combination of three cations to prepare the unknown sample.

 

1. Ni2+, Zn2+, Pb2+, Ag+, Fe3+, Mn2+, Cr3+, Cd2+

 

2. Cu2+, Cd2+, Hg2+, Pb2+, Ni2+, Zn2+, Ag+, Cr3+

 

3.                  Cu2+, Cr3+, Cd2+, Pb2+, Hg22+

 

4. Fe3+, Ni2+, Zn2+, Mn2+, Cr3+, Pb2+, Cu2+

 

5. Ag+, Pb2+, Hg2+, Cr3+, Fe3+, Cu2+, Hg22+, Ni2+, Zn2+

 

6. Zn2+, Ni2+, Cr3+, Fe3+, Ag+

 

7. Ni2+, Mn2+, Fe3+, Cu2+, Zn2+

 

8. Pb2+, Zn2+, Cr3+, Hg2+

 

9. Ag+, Cr3+, Cd2+, Fe3+, Ni2+, Pb2+, Zn2+

 

10. Zn2+, Fe3+, Cr3+

 

11. Ni2+, Cr3+, Fe3+

 

12. Fe3+, Cu2+, Cd2+

 

13. Fe3+, Zn2+, Hg22+, Hg2+

 

14. Cu2+, Cd2+, Hg2+

 

15. Zn2+, Pb2+, Cu2+, Ni2+

 

16. Cr3+, Cu2+, Fe3+, Cd2+

 

17. Fe3+, Zn2+, Mn2+

 

18. Pb2+, Cd2+, Ni2+, Zn2+, Hg2+

 

19. Zn2+, Cu2+, Fe3+, Ni2+, Mn2+

 

20. Pb2+, Ag+, Cu2+, Cd2+, Zn2+, Hg2+

 

21. Zn2+, Cd2+, Pb2+, Hg2+

 

22. Pb2+, Fe3+, Zn2+

 

23. Pb2+, Ag+, Zn2+, Cd2+

 

24. Pb2+, Ni2+, Cd2+, Zn2+, Fe3+

 

25. Pb2+, Cd2+, Fe3+, Hg2+

 

26. Pb2+, Cd2+, Cu2+, Zn2+, Hg2+

 

27. Pb2+, Cu2+, Ag+, Hg2+

 

28. Ag+, Pb2+, Cu2+, Ni2+, Zn2+

 

29. Zn2+, Cu2+, Fe3+ Ni2+, Mn2+

 

30. Pb2+, Cd2+, Zn2+, Mn2+, Fe3+, Hg2+

 

31. Ni2+, Mn2+, Fe3+, Cu2+, Zn2+, Pb2+, Ag+

 

32. Cu2+, Zn2+, Fe3+, Pb2+, Ni2+, Cr3+

 

33. Fe3+, Zn2+, Cr3+, Pb2+, Cd2+

 

34. Pb2+, Zn2+, Cd2+, Mn2+, Ni2+, Cr3+, Cu2+, Fe3+

 

35. Fe3+, Zn2+, Cr3+, Pb2+

 

36. Ag+, Pb2+, Zn2+, Cr3+, Cu2+, Fe3+, Mn2+, Ni 2+

 

37. Ag+, Zn2+, Ni2+, Hg2+, Pb2+, Fe3+, Cr3+

 

38. Fe3+, Mn2+, Ni2+, Zn2+

 

39. Cu2+, Zn2+, Mn2+

 

40. Zn2+, Ni2+, Mn2+, Cr3+, Fe3+, Ag+, Cu2+, Pb2+, Hg2+, Cd2+

 

41. Zn2+, Fe3+, Cr3+, Cu2+, Ni2+, Mn2+

 

42. Zn2+, Cu2+, Fe3+, Ni2+, Mn2+, Pb2+, Ag+, Cd2+, Hg2+

 

43. Ag+, Pb2+, Mn2+, Ni2+

 

44. Mn2+, Fe3+, Cr3+, Zn2+

 

45. Cu2+, Mn2+, Zn2+, Cd2+

 

46. Hg2+, Mn2+, Zn2+

 

47. Fe3+, Mn2+, Cu2+, Cr3+

 

CASE NUMBER 1

 

With the aim of revitalizing Britain's failing oyster production industry, a new oyster hatchery was established at Conway, North Wales in 1966. Using a tested scheme for hatching and larval production, the unit was set up under controlled commercial conditions using filtered estuary water for the tanks containing adult breeding stock, and filtered water in separate tanks for larvae released by the breeding stock. After rearing for about 8 weeks, the larvae settle as spat and are transferred to growing trays in the shallow estuary. A continuous water flow is maintained in the breeding and growing tanks by pumping from an intake at the narrow river end of the tidal region. Since the operating and growing conditions had been proved before the unit was established, a "settling" rate of spat of about 60% was expected as normal. Yet, in a curious and at first unexplained way, the unit suffered cyclic failures in which larval mortality was sometimes close to 100%. Three years of careful water analysis on this type of sample pointed up the problem.

 

REFERENCE: (i) The Toxic Metals, A. Tucker, Ballantine Books, N.Y., N.Y., 1972, p. 151.

(ii) H. Elderfield, L. Thornton, J. S. Webb, "Heavy Metals and Oyster Culture in Wales", Marine Pollution Bulletin, 2, 3, 1971.

 

CASE NUMBER 2

 

Ornithologists estimate that in the single massive "kill" of seabirds in the Irish sea in the autumn of 1969, between 50,000 and 100,000 seabirds died. Most of them were Guillemots, although razorbills and puffins were also among the 17,347 birds recorded after being washed up on the shores of Britain. In spite of comprehensive investigation no specific cause emerged. Indeed it was concluded that the deaths were the result of a combination of factors; the time of year, with the birds weakened after moult; a period of unusually stormy weather for August and September, which had made feeding difficult; the direct effects of starvation on the ability to survive; and the mobilization of various accumulated poisons through loss of flesh. Among these poisons were high concentrations of polychlorinated biphenyls (widely used industrial solvents). This finding was itself disturbing and quite unexpected by ornithologists. No less unexpected, and perhaps more sinister, was the indication of high levels of contamination by a whole range of toxic metals. There was no uniform distribution, but simply a scatter of findings, which showed that from time to time during their lives these birds had been feeding on marine organisms severely contaminated by the types of substances in this sample.

 

REFERENCE: The Seabird Wreck of 1969 in the Irish Sea, edited by M. W. Holdgate, Natural Environment Research Council.

 

CASE NUMBER 3

 

"Another group of chronic disorders may arise from accumulation of one or more non-essential or abnormal trace elements, which man in his infinite wisdom has mined from the earth and spread over its surface. Exposures to them are new, not more than 5,000 years old, but in the last century they have become much wider and heavier, especially during the last 50 years. If homeostatic mechanisms for these elements had not developed during the last half million years because of very low human exposures (ie., lack of need) or were poorly developed because of fairly low exposures, it is unlikely that modern man has evolved them. If not adapted, some of these trace elements, absorbed and accumulating in the tissues with age, may cause biochemical abnormalities leading to disease. They can enter food in amounts larger than "normal" from processing, packages and cases, be dissolved by soft water from pipes, be inspired from air polluted by industrial wastes and automobile exhausts." Your sample contains some of these materials.

 

REFERENCE: H. A. Schroeder, "Some Prospects for Research on Biologically Active Trace Elements",Trace Substances in Environmental Health, I (Proceedings of University of Missouri's 1st Annual Conference on Trace Substances in Environmental Health), 1967, p. 21.

 

CASE NUMBER 4

 

"In studying the biological role of trace elements, we should naturally like to know which of them are essential and which of them are merely accidental inclusions in the tissues of the body. Our success in answering this straight forward question depends on the extent to which we can improve the sensitivity of chemical analysis. Unless we can detect an element and measure its distribution among the tissues of the body, it is unlikely that we shall ever be able to say anything meaningful about its biological purpose. Trace element studies also illuminate and extend the humanist tradition on which modern science is based, for they remind us emphatically of the importance of man in relation to his environment and of the importance of observation (rather than tradition and superstition) as the basis of speculation which leads to scientific advance." Your sample contains some of the biologically important trace elements now under study.

 

REFERENCE: J. M. A. Lenihan, "Technology and Humanity", Trace Substances in Environmental Health, I (Proceedings of University of Missouri's 1st Annual Conference on Trace Substances in Environmental Health), 1967, p. 141.

 

CASE NUMBER 5

 

The following is a quote from a recent book, "The Toxic Metals", by A. Tucker (Ballantine Books 1972). "Further, it is very noticeable that the toxicities of metals (and other environmental contaminants) seem always to be considered singly, a hangover from the laboratory necessity to produce unambiguous figures for lethality in experimental biological systems. Such an assessment has no relevance to the real environmental situation. Contaminants never occur singly, are often additive or even synergistic in their effects and present a gross insult of great complexity and perhaps of enormously enlarged potential for damage. While it is true that all living systems, through their ability to break down poisonous substances into reusable chemical building blocks, have great power of detoxification, provided that the system does not become overloaded. The toxic metals cannot be broken down this way. They do not degrade." Your sample contains a mixture of metal cations typical of those found in a polluted river.

 

REFERENCE: The Toxic Metals, A. Tucker, Ballantine Books, N.Y., N.Y., 1972, p. 209.

 

CASE NUMBER 6

 

Much recent research in trace elements studies has been directed towards elucidating which specific trace elements are essential to life. Smith noted recently that conventional methods of animal experimentation may not produce deficiencies of trace elements required in nanogram (10-9 g) levels, since the animal obtains adequate quantities from non-dietary sources. Such contaminating sources are: cages, food, cups, litter, water bottles, and atmospheric dust. A controlled environment system was developed to prevent such contamination using modified isolators and techniques originally developed from germ free studies. The system provides a barrier against airborne contamination. This was accomplished using thin film plastic isolators supplied with filtered air. The supporting equipment including cages, water bottles, food cups and weighing device were completely plastic minimizing contamination from these sources. Your sample contains materials that certainly would be contaminant arising from a normal animal cage environment.

 

REFERENCE: J. C. Smith, Trace Substances in Environmental Health, II (Proceedings of University of Missouri's 2 nd Annual Conference on Trace Substances in Environmental Health), 1968, p.223.

 

CASE NUMBER 7

 

Recently, in a paper entitled (The Role of Trace Metals in Chemical Carcinogenesis - Asbestos Cancers", D. B. Lowe et al, proposed the following interesting hypothesis concerning asbestos and lung cancer. Asbestos per se plays a passive role in carcinogenesis; the active role is taken by the trace metals with which it is associated. Benzpyrene, or related polycyclic aromatic hydrocarbons, derived from external environmental sources (eg., packing) or from asbestos itself is the carcinogen. Whether cancer develops depends on the residence time of the unmetabolized benzpyrene in the host and the inherent susceptibility of the host. Trace metals commonly associated with lung cancer should inhibit the metabolism of benzpyrene, thus increasing the residence time. Trace metals naturally occurring in the host should accelerate the metabolism, thus ridding the lung of the carcinogen. Your sample contains the metal ions suggested (in the paper by Lowe) as playing a role.

 

REFERENCE: J. R. Dixon, D. B. Lowe, D. E. Richards, H. E. Stokinger, Trace Substances in Environmental Health, II (Proceedings of University of Missouri's 2nd Annual Conference on Trace Substances in Environmental Health), 1968, p. 141.

 

CASE NUMBER 8

 

Metal-binding compounds are being used with increasing frequency for the treatment of many diseases, even though the basis for their use does not always involve the complexing ability of the compound. Even when used for intentional binding of certain metals in vivo, treatment is not always successful. Of the large number of chelating (binding) compounds developed during the past few years, most have had very limited use in biologic applications but a few (eg., BAL - 2, 3-dimercaptopropanol, EDTA - ethylene diamine tetraacetic acid, penicillamine - b, b-dimethylcysteine) have been found to be beneficial in eliminating excessive accumulations of toxic metals from the body. Your sample contains a mixture of types of metals (cations) that have yielded to chelation therapy.

 

REFERENCE: J. T. McCall, K. G. McLennan, N. P. Goldstein, R. V. Randall, Trace Substances in Environmental Health, II (Proceedings of University of Missouri's 2nd Annual Conference on Trace Substances in Environmental Health), 1968, p. 127.

 

CASE NUMBER 9

 

The U. S. Geological Survey is collaborating with the Environmental Health Center of the University of Missouri to provide a description of the natural trace element environment of Missouri for use in their epidemiological studies. The success of such a study will depend to some extent, on the recognition of unnatural or artificial geochemical effects. Because sampling of much of the bedrock geology must of necessity take place in road cuts where bedrock is best exposed, the influence of highway environment on the trace element content of the roadside landscape needs evaluation. Unusual accumulations of Pb in soils and vegetation along highways have been demonstrated in many studies (eg., studies by Cannon and Bowles in Colorado and Maryland demonstrated noticeable increases in Pb contents of plants adjacent to thorough-fares). Such accumulation of Pb in soils and plants adjacent to roadways is generally ascribed to contamination by combustion products of leaded gasoline. Little work has been undertaken however, with regard to possible changes of metal abundance in general in roadside materials. A recent paper by Connor et al analyzed roadside samples for the cations present in your sample.

 

REFERENCE: J. J. Conner, J. A. Erdman, J. D. Sims, R. J. Ebens, Trace Substances in Environmental Health, IV (Proceedings of University of Missouri's 4th Annual Conference on Trace Substances in Environmental Health), 1970, p. 26.

 

CASE NUMBER 10

 

The relationship between the environment and human health and disease, notably between iodine levels and goiter incidence and between water fluoride levels and the prevalence of dental caries and mottled enamel, are highly convincing and are supported by abundant experimental evidence. Numerous other links between the environment and disease of a more serious nature have been proposed. Differential mortality from cancer of the stomach in different parts of England and Holland has been correlated with soil type, and the highest prevalence of total cancer and stomach cancer has been related to particular types of soil in New Zealand. More recently a high inverse correlation has been demonstrated between the selenium status of several states of the USA, as indicated by the average selenium content of different forage crops, and the age and sex-adjusted death rates of the population of those states. It should be emphasized that these associations rest heavily upon correlation rather than causation. This problem has been examined with great thoroughness and conviction by Hill who maintains that an association needs to be studied from nine different viewpoints. These are strength, consistency, specificity, temporality, biological gradient, plausibility, coherence, experiment and analogy. Your sample liquid contains cations which have also been suggested as being connected (in trace amounts) to human and animal health.

 

REFERENCE: E. J. Underwood, Trace Substances in Environmental Health, IV(Proceedings of University of Missouri's 4th Annual Conference on Trace Substances in Environmental Health), 1970, p. 9.

 

CASE NUMBER 11

 

There is now abundant evidence that the growth, health and well-being of man and his domesticated animals are determined, among other things, by the amounts and proportions of the various trace elements to which they are exposed. Intakes of these elements come from ingestion with the food and drinking water and from inhalation of the environmental air. In most circumstances the food provides an overwhelming proportion of total exposure. This does not mean that the water supply and the atmosphere cannot be significant sources of these elements in some areas, or that these sources should not be critically considered in any overall assessment of geographical and geochemical factors affecting health and disease. Indeed, high natural levels of fluoride in the water supplies in many parts of the world have been incriminated as the cause of endemic fluorosis in man and animals and controlled artificial fluoridation of the water supplies has been exploited widely as a means of reducing the incidence of another tissue in man, dental caries. Some of the other trace elements that are important to man and animals are present in your unknown sample.

 

REFERENCE: E. J. Underwood, Trace Substances in Environmental Health, IV (Proceedings of University of Missouri's 4th Annual Conference on Trace Substances in Environmental Health), 1970, p. 3.

 

CASE NUMBER 12

 

The metal cations present in this sample were recently analyzed for by means of a laser used as a sampling device. In 1962 the laser was proposed as a sampling tool for use in conjunction with emission spectrography by Brech et al. They pointed out that the laser could be used to vaporize a small, precisely defined region of a biological surface, such as teeth, and thereby prepare it for further excitation required for emission spectrography. In 1963 Rosan used this technique to seek metals in dried sections of brain and pancreas. They reported that as little as 10-10 moles of some biologically active cations could be detected, and they emphasized the heterogeneity of biological target areas. Wilson has reported a case of calcinosis cutis in which the laser microprobe was used to sample the skin lesion.

 

REFERENCE: A. Yunice, E. F. Perry, H. M. Perry, Jr., Trace Substances in Environmental Health, II (Proceedings of University of Missouri's 2nd Annual Conference on Trace Substances in Environmental Health) 1968.

 

CASE NUMBER 13

 

Widespread anger developed in Kyushu, Japan during the Minamata affair and, when it became known that the Minamata chemical plant was involved in the release of the wastes, those deprived of a living by the fishing ban and those whose families had suffered casualties several times attacked the factory. Neither the local nor central governments would pay the compensation that was demanded, and at no time have the factory authorities admitted that they were in any way responsible. In Nov. 1959 about 3000 fishermen and other peasant workers stormed the factory, but were eventually beaten off by police. Those identified as leaders of the attack were brought to trial and punished. Finally, local politicians intervened and after negotiations (by its own experiments the company then knew its effluents were to blame) the company agreed to pay token damages. Relatives of adult victims received the equivalent of $250, and those of infant victims $75. In exchange the company denied liability in any way and further demanded that those receiving compensation should sign a document which precluded all action for further compensation even if "at some future time the Minamata disease is proven to be the result of waste water from the plant". The waste liquid analyzed like the type of liquid you have.

 

REFERENCE: The Toxic Metals, A. Tucker, Ballantine Books, N.Y., N.Y., 1972, p. 44.

 

CASE NUMBER 14

 

Recently a U. S. Geological Survey Study was made of elements in soils and other surficial materials taken at a depth of approximately 8 inches at locations about 50 miles apart throughout the conterminous U. S. The samples were analyzed for 30 chemical elements by spectrographic and chemical methods. The analysis of the 863 samples provide for the first time estimates of average abundances of the elements in the United States soils. The chemical data were plotted on maps to show the variation in soil compositions. The most striking feature of the variation map patterns is the sharp contrast between the chemistry of soils of the Eastern and Western states. Another notable feature displayed by the patterns is the paucity of most elements in soils from the Atlantic and Gulf Coastal Plains. Smaller scale features of possible significance can also be observed, but the low sampling density makes interpretation difficult. Your sample contains some of the main elements the survey chemists were interested in.

 

REFERENCE: H. T. Shacklette, Trace Substances in Environmental Health, IV (Proceedings of University of Missouri's 4th Annual Conference on Trace Substances in Environmental Health), 1970, p. 69.

 

CASE NUMBER 15

 

The increased interest in outdoor recreation within recent years has focused much attention on the quality of the nation's rivers and streams. This situation has been especially true in several areas of Idaho because of pollution by one of Idaho's oldest industries, mining. Due to the complex pollution problem, a broad based study program supported primarily by the Idaho Bureau of Mines and Geology was established to collect, analyze and interpret water quality information from one of Idaho's major rivers which has received mining waste for over 80 years. The Coeur d'Alene River system of northern Idaho is divided into 3 components: the North Fork which supports a healthy aquatic community, the South Fork which has received mining wastes and has been devoid of aquatic life, and the Main Stem which has been affected by the condition of the South Fork. Samples collected from the Coeur d'Alene River over a 16 month period indicate that some metals are above the toxic limits for fish survival. The recent research has also shown that raw sewage discharged into the South Fork throughout its reach is the source of a complex pollution problem. Your liquid sample contains some of the metals discovered to be in high concentrations in the South Fork.

 

REFERENCE: L. L. Mink, R. E. Williams, A. T. Wallace, Trace Substances in Environmental Health, IV (Proceedings of University of Missouri's 4th Annual Conference on Trace Substances in Environmental Health), 1970, p. 69.

 

CASE NUMBER 16

 

In a recent study planned and evaluated by the staff of the Consumer and Food Economics Research Division, the Division of Agricultural Research Service USDA, in the autumn of 1966, 6,000 lunches were collected from 300 schools in 19 states. The lunches were then analyzed for vitamin and trace element content. Schools and states were selected to represent the United States as a whole and the five geographic regions of the National School Lunch Program. During 1964-65 schools in the Southeast served 50 million more lunches than were served in the Midwest, the region with the next highest number. Each day when the lunches were collected any inedible material present, such as chicken bones, was removed from the food. The total edible portion was carefully transferred to containers and frozen for subsequent shipment in the frozen state to the laboratory for analysis. At the lab the lunches were weighed, transferred to a large stainless steel blender and homogenized. One composite was made of all 20 lunches from each school. All composites were kept in frozen storage until analyzed. It was found that the contents of certain trace metals were low, in comparison with current estimates of dietary needs or usual intake as found in other research. Your liquid sample contains some of the trace (here in large quantity) metals that the USDA study was concerned about.

 

REFERENCE: E W. Murphy, B. K. Watt, L. Page, Trace Substances in Environmental Health IV (Proceedings of University of Missouri's 4th Annual Conference on Trace Substances in Environmental Health), 1970, p. 194.

CASE NUMBER 17

 

Secondary metabolites consist of an enormous diversity of natural products, narrowly restricted in taxonomic distribution, without known function in growth of the producer cells, and which are formed for a short period of time by microbial cells that have recently stopped dividing. Of the many thousands of secondary metabolites that have been characterized chemically, those of most interest are compounds toxic either to various microbial species (ie., antibiotics) or to cells and tissues of plants, animals or man (ie., toxine, hallucinogens, etc.). The range of concentrations of trace metals and phosphate, as well as of pH values, temperature and oxygen tension is considerably narrower for efficient production of secondary metabolites than is the range tolerated for growth of the producer microorganisms. Certain trace metal concentrations are especially important in both natural and laboratory environment for secondary metabolism of species of Bacillus, other bacterial genera and also species of yeasts and molds. Trace metals are critical for the production of the bacterial toxins of Pseudonomas, tetanus, diphtheria, staphylococcal food poisoning and dysentary. Trace metal concentrations also control the synthesis of such fungal products as aflatoxin, malformin, fusarial wilt, lysergic acid and ergotamine. The probable site of action of the metals involves transcription or translation of the toxin synthetases. Your liquid sample contains some of the metal cations which are thought to be important in toxigenesis (the production of toxins).

 

REFERENCE: E. D. Weinberg, Trace Substances in Environmental Health IV (Proceedings of University of Missouri's 4th Annual Conference on Trace Substances in Environmental Health), 1970, p. 233.

 

 

CASE NUMBER 18

 

The major concern of air pollution control and research has been and still is primarily with the so-called "major" pollutants such as sulfur oxides, particulate matter, ozone and related oxidants and carbon monoxide. Interest has been rising, however, about the health hazards of trace substances and a number of research projects are now under way. Although the National Air Sampling Network has been routinely monitoring some 15 trace elements for over a decade, the results have been inconsistent and little attention has been paid to them or use made of them for studies of health effects. A number of potentially toxic elements have been identified in occasional samples of air, but next to nothing is known about their concentrations or chemical form. A major problem in evaluation of the role of airborne elements is that very little is known about ecological cycles from air to food chains and water supplies. In order to adequately plan epidemiologic studies of health effects and in order to intelligently institute standards for control such information is urgently needed. Your liquid sample contains metals that could possibly be transferred from the air environment to the water environment.

 

REFERENCE: R. E. Carroll, Trace Substances in Environmental Health III (Proceedings of University of Missouri's 3rd Annual Conference on Trace Substances in Environmental Health), 1969, p. 227.

 

CASE NUMBER 19

 

The extreme biological consequences of even small changes in the concentrations of the trace elements as well as the very small amounts which are required suggests that their action can only be that of vital links in enzyme systems. The patterns of trace element interaction vary considerably. One element may enhance the function or utilization of another. The interactions may be direct with one element substituting for another, forming compounds with properties disadvantageous to the animal. An element may change the micro-environment, perhaps a change in ion concentration, with resulting attention in the metabolic pathways of a second element. The possibility of interaction becomes almost infinitely complex when elements are integral parts of the same system with both being essential! A deficiency of one element blocks the functioning of the system and the second element is unable to complete the necessary metabolic reaction. One of the many remaining unsolved problems of the metabolism of trace elements in animals concerns the fact that in deficiency conditions, clinical evidence, often severe manifestations, may be exhibited while the level of the trace elements within individual tissues of the animal remain at significant levels. Your liquid sample contains metal cations thought to interact strongly in biological systems.

 

REFERENCE: G. K. Davies, Trace Substances in Environmental Health III (Proceedings of University of Missouri's 3rd Annual Conference on Trace Substances in Environmental Health), 1969, p. 135.

 

CASE NUMBER 20

 

The following passage was taken from "Water Wasteland" (a Nader Report): "But outfall measurements by themselves may not detect all the pollutants going into a stream, ... in fact outfall measurements without plant inspections are still grossly inefficient. As one Federal investigator pointed out to the Task Force:

 

Most industries run all their wastes from many different processes together into a single stream sometimes before the discharge point. If you can get into the plant, you can analyze the wastes from different processes to find out their content. But if you can only measure at the effluent outfall, you have to separate out the different constituents. For example, GM (General Motors) has combined wastes in their discharge point. Knowing that plating wastes contain, say cyanide, etc., we would run chemical tests for these elements. But if we could get in the plant and discover that they don't have that particular process, or they run those wastes out somewhere else, we could eliminate that test. That would cut your analysis by more than half in most cases." Your liquid sample contains the cations that would be typical of those in an outfall from a large metal fabrication factory.

 

REFERENCE: Water Wasteland, A Nader Report, 1971, p. 242.

 

CASE NUMBER 21

 

"The Kumanoto investigators got down to their work with commendable speed. Giving first priority to a two-pronged attack aimed at plotting the distribution of the disease and identifying its cause, the scientists set about eliminating one by one the naturally occurring diseases and the compounds whose poisonous symptoms, although in some ways similar, did not fully tie in with those of the Minamata victims. By this time, September - October 1956, events along the coast were giving a decisive lead. Not only cats, but other domestic animals began to go mad and die, the fish in Minamata Bay began to be washed up dying on the shores, and the wild birds which ate them, particularly carrion crows, began to stagger, convulse and die in large numbers. The "disease" was spreading fast. By November, having eliminated contagious encephalitis and other naturally occurring diseases, the study group turned to the possibility of some kind of heavy metal poisoning. The distribution of the disease revealed it to be concentrated primarily along the coast and, with the fish dying, it took no great leap of imagination to suggest a connection between the two. The field of search, although it went on properly to include an examination of drinking water, and of the sewage system, began to narrow down." You can narrow it down much further by analyzing your liquid sample which contains trace metals which could have been responsible for the disease!

 

REFERENCE: The Toxic Metals, A. Tucker, Ballantine Books, N.Y., N.Y., 1972, p. 21.

 

CASE NUMBER 22

 

REINHART v. LANCASTER AREA REFUSE AUTHORITY WELLS (Water Pollution). 201 Pa Super 614, 1931 2d 670-676

 

This action arose as a result of filling operations on land owned by defendant McFalls and leased by him to the other defendant, Lancaster, for the purpose of dumping refuse thereon. Plaintiffs are appealing the grant of a judgment now for the defendants following verdicts for money damages in plaintiff's favor in 2 actions of trespass brought for contamination of wells located on their respective properties. The court here reversed the judgment and held that the defendants, in bringing polluted material, particularly items such as garbage, red paint, etc., which might permeate the earth and resist filtration, failed to use due care in handling such material when they placed it in close proximately to plaintiff's land and wells, of which they were aware, and into excavations they had made below the surface of the land, and then compressing it into the ground by running trucks over it. Since they had received general warnings about the results of this operation, the effect on the percolating waters was reasonably foreseeable. The well water might analyze like your liquid sample! Produce evidence for the plaintiff.

 

REFERENCE: Selected Water Resources Abstracts 2, #3, W69-00845.

 

CASE NUMBER 23

 

Rapid development of uranium mining in the Elliot Lake area, Ontario, caused widespread radiological and sewage pollution of the Serpent River system. The widely used acid leaching process of uranium ore treatment produces large amounts of waste, both solid and liquid. For each ton of ore, nearly one ton of tailings and at least two tons, and as much as five tons, of water, acids, trace metals and neutralizers are produced. Not all the uranium and none of the radium-226 is extracted from the ore, so the tailings piles contribute some radioactivity to water passing through them. Some lakes and streams contain more than the safe amount of radium. Leaks in the refining systems also contribute to pollution. All sewage is treated but lake and stream pollution by increased oxygen demand and an increase of nutrients is common and has made one former swimming area obnoxious. No fish can live in Angel and Home Lakes, and algae are present in excessive amounts. Your liquid sample contains the type of cations to be expected in waste liquors from acid ore extraction.

 

REFERENCE: Selected Water Resources Abstracts, W69-01165.

 

CASE NUMBER 24

 

"Just as in the marine environment there are certain organisms which, because they are highly efficient at concentrating metals, can be used as pollution indicator species, so do some plants rapidly concentrate metals from the atmosphere. Indeed some kinds of moss are much more efficient at this than anything man has yet devised. Their unique properties as a kind of exchange resin capable of concentrating at very high efficiency all metallic elements were first exploited as a means of assessing contamination by scientists in Sweden who, alerted by the mercury problem, decided to survey the whole country for airborne contaminants. Such a task might seem virtually impossible, but the value of indigenous natural "sniffers", continually concentrating airborne metals, meant that long-averaged samples of metallic exposure could be obtained simply by analyzing judiciously selected samples on one common species of moss. Air contamination gradients discovered by this method in Sweden showed that, in all probability, the major sources of airborne metallic contamination lay outside the country's own borders, thus raising a controversy about Europe's high industrial chimney philosophy that will not be easily or cheaply resolved." Your liquid sample contains metals (as cations) that are thought to arise as air pollutants and finish up, via fallout, in aquatic systems."

 

REFERENCE: (i) The Toxic Metals, A. Tucker, Ballantine Books, N.Y., N.Y., 1972, p. 167.

(ii) A. Ruhling, G. Tyler, J. of Applied Ecology 8, 497, 1971.

 

CASE NUMBER 25

 

Scientifically and historically, the lack of adequate estuarial studies has arisen because estuary conditions fall into neither of the established areas of aquatic study - freshwater and marine. Dynamically and ecologically, estuaries differ widely, but they share the common fate of being used as open sewers for the disposal of all manner of untreated effluent. And they are dying. Even vast and biologically rich brackish areas like Chesapeake Bay (which might seem large enough to digest any insult), are seriously threatened. But any meaningful evaluation of the situation, whether designed to define present environmental conditions and hazards or to delineate safe latitudes for industrial development, requires a very expensive investment of skilled manpower. Marine biologists cannot work alone in these regions where land and freshwater meet the sea and tidal action. They need the support of fresh water biologists, chemists and biochemists, hydrographers, sedimentologists and geochemists. Industry cannot or will not mount such operations and it is only just dawning on governments that for survival, they are essential. Your liquid sample contains metal ions that have been recently studied in order to elucidate their action on estuarial environments.

 

REFERENCE: The Toxic Metals, A. Tucker, Ballantine Books, N.Y., N.Y., 1972, p. 155.

 

CASE NUMBER 26

 

The following quote was taken from the Nader Report called "Vanishing Air".

"Air pollution (and its fallout on soil and water) is a form of domestic chemical and biological warfare. The efflux from motor vehicles, plants, and incinerators of sulfur oxides, hydrocarbons, carbon monoxide, nitrogen oxides, particulates and trace metal contaminants amounts to compulsory consumption of violence by most Americans. There is no full escape from such violent ingestions, for breathing is required. This damage, perpetuated increasingly in direct violation of local, state and federal law, shatters people's health and safety but still escapes inclusion in the crime statistic. "Smogging" a city or town has taken on the proportions of a massive crime wave yet federal and state statistical compilations of crime pay attention to muggers and ignore "smoggers". As a nation which purports to apply law for preserving health, safety and property, there is a curious permissiveness toward passing and enforcing laws against the primary polluters who harm our society's most valued rights." Your liquid sample contains metal cation fallout that arose from industrial atmospheric contamination.

 

REFERENCE: Vanishing Air, (A Nader Report), 1971.

 

CASE NUMBER 27

 

The calendar of the Limbourgs and indeed their entire cycle in the Tres Riches Heures has become in our time one of the most famous of all works of art, even though, until recently, nearly everyone has known it only in reproductions that blur its subtle light and color or its perfect detail. Such wide popularity is absolutely exceptional for an illuminated manuscript that is closed in a library rather than, like other forms of painting, displayed in a public place. So familiar are the miniatures of the Limbourgs that we may be surprised to learn that they disappeared for 3 centuries, without apparently leaving, during the time, any record of appreciation whatsoever. We know that the Duc de Berry and the painters of the day greatly prized the miniatures. The appraisers of the Duke's estate fixed a relatively high price for the manuscript, which had been only half completed at his death in 1416; and still in the early sixteenth century Flemish illuminators paid tribute to the calendar pictures by imitating figures and entire compositions. Thereafter, like medieval art in general, the manuscript disappeared from history. In 1856 the perceptive founder of the museum at Chantilly bought it from an Italian family. The beautiful colors used in Tres Riches Heures were made from a variety of natural sources, eg., rocks, plants. Your liquid sample contains metal cations, derivatives of which were used by the illuminator of Tres Riches Heures, Paul Limbourg.

 

REFERENCE: Tres Riches Heures, Original Reproductions (1968).

 

CASE NUMBER 28

 

Acid mine drainage, almost all of it from coal mines, pollutes an estimated 10,000 miles of streams in the U. S. An estimated 60 to 70% of the drainage comes from abandoned mines, and about 85% of that amount comes from exhausted underground mines. Mine drainage can be alkaline as well as acidic, but acid drainage is the more serious problem. The formation of acid mine water involves initially the oxidation of pyrite to form in a series of chemical reactions, sulfates, sulfuric acid, iron oxides and probably other compounds. Water that enters the mine dissolves oxidation products, and the resulting acidic solution, which may now contain compounds of several different metals, runs eventually into surface waters. Three forms of oxidation are believed to be involved: chemical, electrochemical, and bacterially catalyzed. The key to the overall rate of oxidation is the reaction of exposed pyrites with moist air. One means of dealing with acid mine water is to prevent or minimize its formation at the source, and this is being practiced by industry. Measures that can be used include flooding or sealing, to prevent air from entering the mine and oxidizing the pyrite. Your liquid sample contains metal ions that might be found in water drainage from an old mine.

 

REFERENCE: Cleaning Our Environment: The Chemical Basis for Action, American Chemical Society, Washington, D.C., USA, 1969.

 

CASE NUMBER 29

 

A great deal remains to be learned about trace element function and toxicity in animals and plants. There are yawning gaps in present knowledge of trace element-water-soil-plant-animal interrelationships. Even when considering a single soil type, local water, a single plant species, one trace element and one species of animal, the complexities are enormous. A host of variables, including the availability of major nutrients, climate and soil acidity, the state of maturity of both plant and animal, the availability of all other trace elements and the form of other elements such as sulfur, have to be included in the picture. In practice the situation is even more daunting for seldom, if ever, are relationships confined to single species. While deficiency disease and symptoms of poisoning tend to show up fairly rapidly in animals such as sheep and cattle which are confined to specific areas, enormous variations of trace element uptake can be produced by commonplace activities, such as fertilizer treatment of soil, for fertilizers may be rich in a potentially toxic trace element, and in any case may lead to major changes in the pattern of plant growth. Different plants have different trace element uptake. Quite apart from leading to marked variations in the availability of trace elements to a feeding animal, plants may also contain other biologically active compounds which block the utilization of important trace elements within the animal. Your liquid sample contains some of the cations which have been found to be important in animal nutrition.

 

REFERENCE: The Toxic Metals, A. Tucker, Ballantine Books, N.Y., N.Y., 1972, p. 143.

 

CASE NUMBER 30

 

The term trace-element comprises some 25-30 elements which were, because of the coarseness of analytical techniques, detected in amounts so small that they were described simply as "traces" in early analysis of living tissues. With advances in technique and in the understanding of the biological roles of some metals, there has been a tendency in the English-speaking countries to refer to the essential metals as micronutrients, thus splitting off a small and as yet incomplete group from the others which are either benign or poisonous. This sounds tidy but may be misleading for, in nature, things tend to be much too complicated to be compressed into simplistic categories. Cross interferences, such as blocking or potentiating ability, can in differing circumstances transfer a metal from one category to another. The micronutrient may be capable of poisoning the system, and the toxic element may be better tolerated in some circumstances than in others. One at least, arsenic, although traditionally regarded as the most potent of metallic poisons, is of relatively low mammalian toxicity when compared to some of the other trace elements. Your liquid sample contains several metal cations that are now regarded as being extremely important in biological systems.

 

REFERENCE: The Toxic Metals, A. Tucker, Ballantine Books, N.Y., N.Y., 1972, p. 140.

 

CASE NUMBER 31

 

Certain trace elements which are strongly associated with air pollution sources in the Lake Michigan basin may be contributing significantly to lake water pollution by an atmospheric fallout route. A partial inventory of air pollution emissions for 30 trace elements has been made for the Chicago, Milwaukee, and northwest Indiana metropolitan areas, based on available published information, and compared with natural and pollution stream trace element inputs. Evidence indicates that the atmosphere may be the major source of several trace metals in Lake Michigan. Moreover, the evidence suggests that air pollution probably exceeds expected unpolluted stream inputs for many additional elements in Lake Michigan, highlighting the need for more comprehensive chemical data to quantify the evaluation. Your liquid sample contains several of the cations that appear to constitute fallout into aquatic systems from the atmosphere.

 

REFERENCE: J. W. Winchester, G. D. Nifong, "Water Pollution in Lake Michigan by Trace Elements from Pollution Aerosol Fallout", Michigan University, Ann Arbor. (from Selected Water Resources Abstracts, W71-08764).

 

CASE NUMBER 32

 

At present some 86 fossil fuel plants are discharging their thermal effluents into the waters abounding the east coast. By 1980 power needs will require 200 billion gallons of water per day or approx. one sixth of our annual nationwide runoff and nearly 32% of all power stations will be adjacent to various estuaries. By the year 2000, utility companies will be utilizing almost twice the national fresh water runoff and a lifetime supple of either 10 million tons of uranium or 100,000 million tons of coal. Advanced nuclear reactors, highly more efficient, will be needed to ensure the safety of our waterways. Fossil-fueled plants are approx. 40% efficient, whereas nuclear fueled plants tend to be less efficient, at 33%. A 1000 mw nuclear fueled plant will utilize nearly 1.3 billion gallons of water per day. Though one plant may raise the temperature only a few degrees within a limited area from the discharge canal, an accumulation of heated effluent from multiple units could prove disastrous for many miles, especially during critical periods of the year. Your liquid sample contains cations that probably would constitute waste effluent (besides thermal pollution) from a power plant.

 

REFERENCE: Selected Water Resources Abstracts, W71-00255.

 

CASE NUMBER 33

 

One of the greatest earthquakes of all time struck south-central Alaska on March 27, 1964. In some coastal areas, local subsidence was superimposed on regional tectonic subsidence to heighten the flooding damage. Ground and surface waters were measurably affected by the earthquake, not only in Alaska but throughout the world. Much new and corroborative basic geologic and hydrologic information was accumulated in the course of the earthquake studies, and many new or improved investigative techniques were developed. Chief among these were the recognition that lakes can be used as giant tiltmeters, the refinement of methods for measuring land-level changes by observing displacement of barnacles and other sessile organisms, and the relating of hydrology to seismology by world-wide study of hydroseisms in surface water bodies and in wells. Your liquid sample contains cations which increased in concentration in lakes as a result of earthquake activity.

 

REFERENCE: E. B. Eckel, "The Alaskan Earthquake, March 27, 1964, Lessons and Conclusions", Geological Survey, Washington, D. C. (from Selected Water Resources Abstracts W71-03706).

 

CASE NUMBER 34

 

In 1968 the Canada Center for Inland waters undertook a systematic monitoring of Lakes Ontario, Eric, Huron and Superior in a study of the major and trace elements. The data gathered on major elements during the period July to November, 1968, were examined and the results compared on a lake-wide basis with earlier compilations to appraise recent trends and changes in the composition of these waters. Because the concentrations of all major ions for which data are available in Lake Superior have not changed for the last 70-80 years, their levels are apparently controlled by the runoff from the drainage basin and that lost through St. Mary's River. Chloride and sulfate have increased in Lake Michigan and Lake Huron. This increase is most likely caused by human activities. In Lakes Erie and Ontario all the major ions except bicarbonate and magnesium have shown a dramatic increase since 1910. Previous to that the lakes were essentially unaffected by human activities. The median values of minor elements are generally below 10 micrograms/liter in the Great Lakes. Sorption by oxides of manganese, etc., and by suspended organic and inorganic material seems a plausible mechanism for the removal of minor elements from the lakes. Your liquid sample contains some of the cations that were monitored in this particular study.

 

REFERENCE: Selected Water Resources Abstracts W71-05883.

 

CASE NUMBER 35

 

Soil erosion and sediment deposition in urban areas are as much an environmental blight as badly paved and littered streets, dilapidated buildings, billboard clutter, inept land use, and air, water and noise pollution. In addition, sediment has many direct and indirect effects on streams that may be either part of or very remote from the urban environment. Sediment, for example, is widely recognized as a pollutant of streams and other water bodies. Much of the disturbed soil in urban construction areas erodes and becomes sediment in streams; the sediment damages water control works and aquatic habitat, degrades water quality, increases flood damages, and lowers the environmental attractiveness. During the process of stabilization of an area after construction, streams tend to erode their beds and banks as a result of increased runoff. Documentation of erosion sources and amounts, of sediment concentration in runoff, of stream channel changes, and of the location and amounts of deposition together with an economic analysis of sediment damages and a pertinent research program provides the knowledge needed to find the best solutions to a wide variety of existing and future urban sediment problems. Your liquid sample contains metal ions thought to be of paramount importance in water pollution arising from urban erosion.

 

REFERENCE: H. P. Guy, "Geological Survey Circular", 601-E, 1970, (from Selected Water Resources Abstracts W71-00393).

 

CASE NUMBER 36

 

Spend liquor (steel industry pickling waste) is an aqueous solution containing from about 0.5 to 10% acid, perhaps 12% iron and several other metals. Either undissolved or in solution, if discharged untreated to a waterway it is a three fold menace, first for its acid content, second for its iron content, and third for its content of other metals. Depending on the chemical and physical form of the metals, the liquor may turn the waste muddy brown, deposit slime, and exert a strong oxygen demand. Huge amounts of pickling acid, 35 to 40 lbs. for every ton of steel, are used in the finishing operations. It is estimated that 8 to 15 gallons of spend liquor are produced per ton of steel pickled. Since 50,000,000 tons of steel are pickled each year, spend liquors are produced at a rate of half a billion gallons per year. They are essentially six types of approaches that can be taken for the disposal of spend pickle liquor: (1) discharge to a waterway, (2) deep well disposal, (3) neutralization, (4) hauling by contractor, (5) recovery processes, (6) regeneration processes. The fact that a few of the available recovery and regeneration methods are in actual use in the steel industries seems to be a reflection not so much on the technical uncertainties of these methods but of the fact that much simpler if less effective ways of disposal are still open, consistent to whatever local regulations are in effect. Your liquid sample constitutes the type of waste water (spend liquor) a typical steel pickling plant might put out.

 

REFERENCE: Environmental Science and Technology, 4, 5, 1970.

 

CASE NUMBER 37

 

The "New Lead Belt" of southeast Missouri, predicted to be one of the largest lead deposits in the world, extends from just west of Ellington on a due north line to Vibinnum. At present this area is one of sparse population and relative wilderness, with rugged hills and swift, crystal-clear streams. It was anticipated that the lead mining activity would stimulate a sharp increase in industrial activity in this area. Here then was a potential "before-after" study in pollution. It was presumed that this intense mining activity could cause significant contamination in the stream waters by heavy metals, notably primary ore metals. Analytical methods for such metals have been developed using atomic absorption spectroscopy. The data obtained from these analyses have been arranged in histograms and critically analyzed. The background concentrations were established to 4-6 ppb (parts per billion) for several of the metals. Both short and long term contamination was identified by using data distributions. Your liquid sample contains metal ions of importance in this particular "New Lead Belt" pollution study.

 

REFERENCE: N. H. Tibbs, "The Background Concentrations of Metals in Streams on the New Lead Belt, Missouri", Missouri University. (from Selected Water Resource Abstracts W71-04182).

 

CASE NUMBER 38

 

The quantity and quality of drainage waters were significantly altered following deforestation of a northern hardwood's watershed ecosystem. Annual water runoff exceeded the expected value (based on undisturbed watershed) by 39% during the first water year after deforestation and by 28% during the second. Deforestation resulted in large increases in concentrations of all major ions except ammonium, sulfate, and carbonic acid. Sulfate was the only major ion that decreased after deforestation. In undisturbed watershed, stream water has a pH of about 5.1 from sulfuric acid, whereas after deforestation it became a nitric acid solution of pH 4.3 enriched in metallic ions and dissolved silica. The increase in nitrate concentration in precipitation may somewhat increase air pollution. Greatly increased export of dissolved nutrients from deforested ecosystems was due to an alteration of the ecosystem nitrogen cycle. Increased availability of nitrate and hydrogen ions resulted from nitrification. Total new export of dissolved inorganic substances was 14-15 times greater than from natural ecosystems. The deforestation experiment resulted in significant pollution of the drainage stream with nitrate concentration exceeding the maximum recommended for drinking water. A bloom of algae appeared each summer. This liquid sample contains material (in cation form) found in runoff from a deforested watershed.

 

REFERENCE: Selected Water Resources Abstracts, W71-01489.

 

CASE NUMBER 39

 

Of all the dams built by rich nations for poor nations hoping to grow richer that way, the one built by Soviet Russia for Egypt is in a class of its own. The High Dam at Aswan is the biggest and most expensive in the world. It made the late President Nasser's political fortune, but spread such ecological havoc that his country may never get over it. The dam, built without sluices, traps approx. an annual 100 million tons of Nile sediment "containing volcanic materials which produce the most fertile soil on earth". Since practically all cultivated soil in Egypt was formed and nourished by the sediment, for which no adequate man-made substitute has been devised, the lack of it strikes at the heart of Egyptian agriculture. Without the Nile sediment, much of Egypt's six million cultivated acres need chemical fertilizer already. In fact, agriculture is now absorbing 2,350,000 tons of artificial fertilizer so far. Two-thirds of it, according to Egyptian and World Bank calculations, is the amount needed to make up for lost fertility and mineral content once supplied by the silt. The cost of just this much comes to upwards of a hundred million dollars a year, cutting about a fifth of the average income from the yield per acre, quite a cut for a farmer earning perhaps $75 a year. This is a recurrent, annual expense for eternity. Your liquid sample contains cations important in the Nile Delta agriculture.

 

REFERENCE: Our Chemical Environment, J. C. Giddings, M. B. Monroe, Canfield Press (Harper and Row), San Francisco, 1972.

 

CASE NUMBER 40

 

Earth is a metal rich planet in a metal poor universe. The core of our planet, by all evidence is mainly metal. The crust of the earth is nearly one quarter metal. This metal-laden spaceship is a mere speck, all but lost in a vast universe composed principally of the non-metals hydrogen and helium. Metals may not dominate outer space but they dominate the chemical space of the periodic table. Of 105 known elements, 83 are metals. Many of the heavy metals have a voracious chemical appetite for sulfur. They are largely combined with sulfur in the earth's natural ore bodies and when they inadvertently enter a living organism they relentlessly seek out the sulfur of that organism's enzymes. The crucial catalyst-regulators of life chemistry are dotted with sulfur atoms, and they become the natural targets of heavy metals. The subsequent chemical bonding between enzyme, sulfur, and the heavy-metal intruders destroys enzyme function and then sickens and kills. For us the rich metal environment of earth is a two-edged sword. The positive side has long been recognized. Only recently have we been made aware of the negative side: some metals, when released widely to the environment, can be dangerous and ecologically disrupting. Your liquid contains biologically important cations.

 

REFERENCE: Our Chemical Environment, J. C. Giddings, M. B. Monroe, Canfield Press (Harper and Row), San Francisco, 1972.

 

CASE NUMBER 41

 

Present programs for controlling potential threats to health from new substances and technological innovations are doomed to failure because we lack the scientific knowledge to provide a sound basis for control. Current testing techniques have been developed almost exclusively for the study of acute, direct toxic effects. In contrast most untoward effects of the technological environment are delayed and indirect...yet little is being done in schools of medicine and public health or in research institutes or government laboratories to develop the kind of knowledge that is needed for evaluating long-range effects on man of modern ways of life. There is no need to belabor the obvious truth that while modern science has been highly productive of isolated fragments of knowledge, it has been far less successful in dealing with the complexity of natural phenomena, especially those involving life. In order to deal with problems of organized complexity it is therefore essential to investigate situations in which several interrelated systems function in an integrated manner. Multifactorial investigations will naturally demand entirely new conceptual and experimental methods very different from those involving only one variable which have been the stock in trade of experimental science during the past 30 years and to which there is an increasing tendency to limit biological research. Your liquid sample contains cations that are known to exhibit interrelated functions in biological systems.

 

REFERENCE: R. Dubos, Medical Tribine, Oct 28, 1964.

 

CASE NUMBER 42

 

Recent research in the solid-waste area has focused on developing methods that may alleviate serious water pollution problems for the nearly 20,000 metal-plating and coating facilities across the nation. Electroplating and metal finishing wastes are significant stream pollutants - either directly, owing to their content of toxic and corrosive materials such as cyanide, acids and metals, or indirectly, owing to the deleterious effect of these components on sewage treatment systems. Bureau of Mines researchers have shown that reducing an organic-cyanide electroplating waste with formaldehyde (HCHO) will cause certain metals to coprecipitate while destroying all of the poisonous cyanides. Another method which is even more promising employs two plating waste solutions to recover metals. Processes have also been developed for recovering expensive metals from cuttings and grindings left over when "super-alloy" jet engine parts are machined. Such scrap containing a variety of metals has a metal content worth nearly $1000 per ton. It is regularly sold to overseas markets for far less because of the high cost of separating and recovering the metals by methods now available in the U. S. Your liquid sample contains metal ions typical of those generated in the electroplating industry and which normally finish up in aquatic systems.

 

REFERENCE: C. B. Kenahan, Environmental Science and Technology, 5, 594, 1971.

 

CASE NUMBER 43

 

The Bureau of Mines has recently been active in researching methods for reclaiming valuable materials from mining, metallurgical, chemical, and industrial processing operations. This work not only includes salvage and reuse, but also stabilizing nonusable mineral waste. A large scale effort has been made to stabilize the waste tailing piles from mining operations that have no utilization values. These wastes are often air, water and land pollution sources. Successful chemical and vegetative techniques have been demonstrated on uranium mill tailing piles. Thirty four acres of uranium leach plant residues, located on the Navajo Indian Reservation in Arizona have been effectively stabilized against wind erosion using a low cost chemical method developed by Bureau scientists. In Durango, Co., another 13 acre plot of waste uranium tailings was stabilized under vegetative cover. West Virginia University developed a process for producing rock wool insulation from coal ash slag, a waste product from coal-fired central power plants. Commercially competitive structural concrete blocks have also been fabricated. Stanford University researchers (under a Bureau grant) demonstrated the technical and economic feasibility of producing stream cured calcium silicate bricks from California gold mine waste. Your liquid sample contains metal ions that are common in waste liquid effluents from mining and metallurgical operations.

 

REFERENCE: C. B. Kenahan, Environmental Science and Technology, 5, 594, 1971.

 

CASE NUMBER 44

 

About 3.6 million tons of solid wastes are generated each year in the U. S. Agricultural wastes constitute nearly two-thirds of the total, and mineral wastes account for most of the rest. Mineral wastes, not including the large amounts of overburden removed in surface mining but including those wastes generated by mining, processing and utilization of all minerals and fossil fuels amount to about 30% of the total wastes. Fuels account for only 125 million tons, or about 3% of all solid wastes generated. The last complete survey of mining operations in the U. S. indicated that in 1964 about 3.2 million acres of land had been disturbed by surface mining. Of this total about 41% resulted from coal production. As yet only a few tenths of 1% of the total land area of the U. S. has been disturbed by surface mining. The effects of such mining on the environment, however, vary widely and depend upon such factors as the type of mining, characteristics of overburden, steepness of terrain, amount of rainfall and temperature. Where land reclamation is not practiced water pollution from acid mine drainage and silt damage occur. It is possible, however, to prevent much of this damage through proper land reclamation, adequate drainage and planting to achieve soil stabilization. In the principal coal mining areas the average costs of completely reclaiming coals land range from $169 to $362 per acre, an average cost of 4 to 8 cents per ton. Your liquid sample contains metal ions leached from mine tailings in a coal mining area.

 

REFERENCE: A. Mills, H. R. Johnson, H. Perry, Environmental Science and Technology, 5, 30, 1971.

 

CASE NUMBER 45

The presence of trace elements in public water supplies has long been of interest to physicians, public health chemists, biologists and others alike. For some, this interest has been due to the beneficial effects exhibited by certain trace elements. For others, interest is related to the threats to human health posed by the presence of minute amounts of toxic elements. The list of those elements already recognized as important water quality parameters lengthens as research into the basic character of water quality progresses. Through the use of highly sophisticated instrumentation such as emission spectroscopy, activation analysis and more recently, atomic absorption spectrophotometry, it is now possible to determine accurately smaller and smaller concentrations of these trace elements. This painstaking research is of the utmost practical significance because it provides the essential information that enables health authorities to establish realistic limits or tolerable concentrations of the various elements in drinking water. The physiological significance of each trace element found in water must be evaluated in terms of the total human environment. The amount tolerable in water is often dictated both by the intrinsic potency of the substance as well as by its possible occurrence in other areas such as the atmosphere and in foods. Your sample contains cations for which the USPHS recently revised water quality standards.

 

REFERENCE: J. F. Kopp, Trace Substances in Environmental Health III (Proceedings of University of Missouri's 3rd Annual Conference on Trace Substances in Environmental Health), 1969, p. 59.

 

CASE NUMBER 46

 

The coastal margin -- the ribbon of land and water where people and oceans meet and are profoundly influenced by each other -- has only recently come to be recognized and treated as a valuable and perishable resource. It is actually a complex of unique physical resources: estuaries and lagoons, marshes, beaches and cliffs, bays and harbors, islands and spits and peninsulas. In the year 2000 half of the estimated 312 million population of the U. S. will live on 5% of the land area in three coastal urban belts: the megalopolises of the Atlantic, the Pacific and the Great Lakes. Along with the people will come an intensification of competing demands for the limited resources of the narrow fragile, coastal zone. To make matters worse, the coastal resource is shrinking under the pressure of natural forces (hurricanes have caused $5 billion in damage to the U. S. economy in the past 15 years) and human exploitation and neglect. More than a tenth of the 10.7 million square miles of shellfish-producing waters bordering the U. S. is now unusable because of pollution. Dredging, drainage projects and even chemical mosquito control programs are having devastating effects on fish and other aquatic life. The amount of industrial waste reaching the oceans will increase sevenfold within a decade. Your liquid sample contains cations that have recently been detected in large amounts in waste water pouring into the Savannah River.

 

REFERENCE: E. Wenk Jr., Scientific American, September, 1969., p. 83.

 

CASE NUMBER 47

 

Areas of anomalous metal content in soils and plants have been shown to be associated with several kinds of geologic environment. The following table shows excesses and deficiencies to be expected in areas marked by geochemical differentiation.

 

Unique Geologic Possible Deficiencies Possible Excess in

Environments in Geologic Unit Geologic Unit

____________________________________________________________________________

 

a) Limestones Mo, Sr, Ca, Mg P, K

 

b) Drift (Glaciated) Zn, Sr, Mo, Co, B, Mg Ti, Fe, Cr, Ni, Zn, Pb

P, I

 

c) Peat bogs Cu (unavailable) Zn, Cu, Pb, Cd

 

d) Serpentine N, P, Ca, Mo, Mn Ni, Cr, Mg, Fe

 

e) Uranium deposits

Colorado Plateau U, V, Se, Mo

____________________________________________________________________________

Your liquid sample contains metal ions thought to be deficiencies in coastal plain sands.

 

REFERENCE: H. L. Cannon, Trace Substances in Environmental Health, III (Proceedings of University of Missouri's 3rd Annual Conference on Trace Substances in Environmental Health), 1969, p.21.

 

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