MABIe Be 1 .. N'42 rlc-. "5

Preliminary Analyses of Urban Wastes,

New York Metropolitan Region

M. Grant Gross

Research Oceanographer

Marine Sciences Research Center

State University of New York

Stony Brook, New York

March, 1970

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The Technical Report Series is pul:>lished l:>y the Marine Sciences Research Center, State University of New York, as a means of making preliminary technical data available to the scientific community and interested members of the community. Issuance of a technical report does not con­stitute formal publication as defined in the International Rules of Zoological and Botanical Nomenclature. Additional copies of a Technical Report may be obtained from the Marine Sciences Research Center, State University of New York, Stony Brook, New York 11790.

_________ I

CONTENTS

Abstract .......................................... e ............................................ 1

;J:ntroduction .•....••...•.....••.........•.•..•••.... 3

Sampling techniques and sample storage .....•....•... 6

Optical emission spectrochemical storage .•.•.•.....• 7

Application of spectrochemical analyses .•••..••..... 11

Carbon ana lyses ..•....•••••..•....•....•.•.•...••.•. 12

Discussion of data ..••.......•....•••.••••.•••••...• 15

Acknowledgments ...•••••.•.•..•••••••.•••.•....•••... 21

Bibliography .................................................... 0- .......................... 23

Appendix A. ~lants sampled and populations served ..• 24

Appendix B. Comparison of spectrochemical analyses

of standard rock samples ..••......•••••••.•.... 27

Appendix C. Spectrochemical analyses of replicate

samples from unmixed sludges .•••••••..•..•.•.•. 28

Appendix D. Spectrochemical analyses of duplicate

samples after grinding and mixing. Analyses

made at different times ..•.••••••••.•.••.•.•... 29

APpendix E. Spectrochemical analyses of sewage sludges,

New York Metropolitan Region .....•.•..•.......• 31

Appendix F. Some chemical properties of sewage sludges,

New York Metropolitan Region ...............•... 35

ABSTRACT

Preliminary analyses were made of 17 sewage sludge samples from sewage treatment plants serving 11.9 million persons in the New York Metropolitan Region. The sludges consist of about 55 per cent organic matter. This or­ganic matter accounts for about 55 per cent of the total oxygen demand of the sludges. About 45 per cent of the sludge is aluminosilicate material, chemically similar to shale. The sludge samples are enriched, compared to sedimentary rocks, soils and organisms, in the following elements: chromium, copper, lead and tin. These elements are common industrial materials, and are known to he highly toxic to marine organisms; some are carcinogenic. Further studies are required to determine the chemical form in which they occur in the sludges and whether they are re­leased to organisms or to sea water after dumping or de­position of the sludges.

These preliminary analyses indicate semi-quantitative spectrochemical analyses may be useful for determining order-of-magnitude concentrations of 24 elements commonly occurring in sewage sludges. Other techniques are re­quired to detect other possible pollutants, with usable precision. Loss on ignition, an ashing technique, is useful for use in analysis of organic matter in sewage sludges not containing large amounts of hydrous alumino­silicates.

INTRODUCTION

In August 1969 we began a study of the chemical compo­sition of waste solids from the New York Metropolitan Region that were dumped in the ocean. Specific attention was given to minor element concentration of these wastes which were likely to be toxic or carcinogenic to marine organisms, or to man if inadvertently introduced into the human food supply. Included in this project is the evaluation of existing ana­lytical techniques and commercial laboratories to determine their applicability for scientific studies of these materials and to regulatory agencies requiring information about the chemical composition of the wastes. Analytical techniques found to be satisfactory, could then be used to study the dispersion of wastes in the ocean, chemical speciation, and reactions among wastes, sea water, and marine organisms.

Sewage sludges were collected in August and September 1969 by Corps of Engineers personnel for 17 sewage treatment facilities (Appendix A) in the New York Metropolitan Region (Figure 1). These facilities serve a population of 11.9 million persons, about 75 per cent of the region's sewered popUlation (Interstate Sanitation Commission, 1969), and many industrial concerns (Federal Water Pollution Control Administration, 1965). Consequently, the samples analyzed provide a significant sample of the solids discharged by dumping of sewage sludges.

Initial emphasis has been on the development of samp1e­handling techniques and evaluation of screening techniques (Table 1) for later development of analytical procedures necessary to obtain a more complete characterization of these wastes. This has proven to be a formidable task be­cause the samples are heterogeneous in composition, unpleas­and to handle, and difficult to store, grind, and homogenize. Preliminary results presented here are the initial step in a larger study and will be used primarily in developing and evaluating other more precise techniques.

Island

() Primary treatment ..

• Secondary treatment

Figur~ 1. Location of se~age treatment plants from which

sludges were collected.

Table 1. Analytical Techniques Used.

Property Measured (quantity reported)

Minor element concentration (per cent by weight)

Total carbon (per cent by weight)

Carbonate-carbon (per cent by weight)

Oxidizable carbon (per cent by weight)

Reducing capacity (l1EQ/a)

Sulfide (MFQ/g)

Technique

Optical emission spectroscopy

Combustion in 02 at T:=:.1500°C, CO 2 analyzed

Acidification (E3

P04 ) CO 2 analyzed after heating sample

K2cr20~ in H3P0 4 , heated to 150 C analyzed

K2cr20~ in H3P0 4 , heated to 160 C, excess Cr

20

7 back titrated with ' Fe (NH) (S04)

Estimated Precision

Semi-quantitative, or order of magnitude

Quantitative, +2% of amount reported

Quantitative, +10% of amount reported

Quantitative, +5% of amount reported

Quantitative, + 5% of amount reported

Acidification (HCl) of Semi-quantitative ~10% sample with As-free Zn, of amount reported

, H2S precipitated in Zn ,acetate solution. Excess , iodine, and ,HCI added, back titrated with 'Na Theosulfate.

6

SAMPLING TECHNIQUES AND SAMPI,E STORAGE

Sludge samples were collected by Corps of Engineers personnel, placed in one-liter polye"thylene jars with screw caps, and delivered the same day to the Marine Sciences Research Center where they were frozen. Jar lids were loosened to permit gases to escape.

Stored frozen samples were removed from the deep-freeze unit and thawed by placing the containers in water in a fume hood. When thawed, each sample was poured into an aluminum­foil-lined shallow tray and placed under infrared heaters. The shallow sludge layer commonly dried within three hours forming a flaky, fibrous solid which was sealed in a plastic bag. The aluminum foil was discarded after each sample to avoid contamination.

'!'he samples were frozen in liquid nitrogen and ground (3-5 min) while frozen (Spex Industries Freezer Mill, model 6700). The powder was mixed and then placed in labelled plast:ic vials for storage. Attempts to grind sludges at room temperatures using conventional grinding apparatus were unsuccessful due to the large hair content and the tendency of the sample to char and coat the sides of the grinding chamber owing to heating during grinding. Both problems were avoided by use of the liquid-nitrogen grinding technique. 'rhis technique will also be useful for handling polluted sediment samples containing fibrous debris.

OPTICAL EMISSION SPECTROCHEMICAL ANALYSES

Preliminary chemical analyses on the samples were made using semi-quantitative spectrochemical analyses (Harvey, 1964, p. 1-8). This technique provides a semi-quantitative analysis for the concentration of 24 elemen't:s in sludges. The technique does not differentiate between those elements present in silicate minerals included in the sludges, or­ganic matter, or newly formed phases, such as sulfides. It does provide useful data for preliminary evaluation and es­tablishing the concentration range, permitting realistic selection of more precise analytical techniques for future analyses.

Prior to analysis the samples were ashed at approxi­mately 600(~10)OC and the weight loss recorded as loss on i~nition (Appendices C and D). In this step there is some possibility of loss of elements with a high vapor pressure such as mercury, tellurium, arsenic, and halides of bismuth, gallium, germanium. For most elements, loss during ignition is not a problem. The major function of ashing is to destroy organic matter and thereby increase the sensitivity of the analyses.

In spectrochemical analyses a 10 milligram sample of ashed sludge mixed with 10 milligram of high purity graphite is vaporized in a D. C. arc. Light is emitted at various wave lengths characteristic of the elements in the sample.

The intensity of each spectral line is a function of ' the concentration of that element in the sample. Intensities Of selected spectral lines, corrected for backgroum'il; are calculated as line-to-background ratios and multiplie'd by previously determined sensitivity factors for the spectral lines used. Sensitivity factors are determined by analysis of the spectrum of standard samples handled in the same manner.

Accuracy of the analytical results was checked by ana­lyzing standard rock samples for which the concentrations of both major and minor elements are known. These standard samples have been analyzed by several different techniques and the concentrations are known with sufficient precision to serve our purposes as checks on the quality of the data. Standard samples were submitted at the same time as the other materials and were handled in the same way. Ideally, one would use standard samples of nearly the same chemical and physical form as the unknowns being analyzed. Such standards were not available so the rock standards were;used as a SUbstitute.

7

Interpretation of the results must be made on the basis of whether the element,was a major constituent of the sample (concentration exceeding 1 per cent) or a minor constituent (concentration less than 1 per cent). For the major elements the analytical results agree within a factor of three (Ap­pend ices B, C). For minor elements, the agreement wasgener­ally within a factor of five, except for P where the data from the analyses were about ten times the preferred values in the literature.

Spectrochemical analyses are not completely insensi­tive to the chemical form of the element. Best agreement between analyses and literature values (Appendix B) was ob­tained with the sulfide-ore sample that corresponded most closely to the composition of the sludges. Less satisfactory agreement for the minor-element concentration was obtained with silicate rock samples (Syenite rock, Tonalite T~l).

Two possible sources of error involving sample ha!id.1~ng were investigated. These were: (1) sample heterogeneJt~/· causing different subsamples to differ significantlyAJ'l';" chemical composition; and (2) variation among analyses',per­formed at different times. The data (Appendix C) suggests that sample heterogeneity is a severe problem. Threedif'­f'erent subsamples were taken from a single sludge sample; each was separately ground and analyzed. These data'indi­cate that the variability in the results is especially severe for Ba, Cr, Cu, K, Ni, P, and Pb. For other elements, the variability is within the two-to-three-fold varia,bility expected of semi-quantitative analyses (Harvey, 1964).

Variation between analyses performed at different times (Appendix C) is usually within a factor of two times the amount reported. For example, a value reported as 0;1 per cent would normally lie between 0.05 and 0.2 per cent. These data are quite useful for screening purposes. Certain elements, including Co, Cr, K, Na, Ni, Mo, and Pb, exhibit 5-fold variation (values range from 5 to 1/5 times the amount reported). Both P and Sn exhibit large variations ("'-lOX) between analyses; more work is requ ired to deter­

mine if spectrochemical analyses for these elements are useful.

Although this technique of spectrochemical technique provides data (Appendix D) for 24 elements there are'severp.l potentially troublesome elements in sewage sludges thatcari not be detected by this technique, including As, Be, 'Bi, Cd, Ce, Ga, Hg, Sb, Th, Y, Yb (Table 2). Several of these elements are known to be toxic or carcinogenic (Fi~ure 2) to marine organisms (Bowen, 1966); their concentrations and chemical form in the sludges should be checked. This problem is currently under investigation, using other more sensitive techniques.

Figure 2. Elements in sewage sludges spectrochemical analyses. presented by BoWen, 1966

,

H

La

Ac

Biological effects

Highly Toxic

o Carcinogenic

Co Pr

Th Po

'"' \ I Probably Carcinogenic -

Nd Pm

U Np

that can be studied by semi-quantitative Biological effects are summarized from data

Sm

Pu -

He

o I FINe

s I CI I Ar

SelBrlKr

Te I Xe

Po I AI I Rn

Eu Gel Tb Oy Ho Er Tm Yb Lu .

Am Cm Bk Cf Es Fm Md No Lw ,

SpectrQchemical analyses

• Usable

C:J Marginal Utility

'"

10

Table 2. Reproducibility of spectrochemical analyses in ground, well-mixed sewage sludges.

Semi-QuantLtative

(±0.5times amount reported)

Si, re, Al, Ca,

Mg, Cu, Ba, P (?) ,

Mn(?), Ag, Zn, V,

Ni(?) , Sr, Zr

Qualitative Insufficient

(±5 times amount Sensitivity reported)

Mo, Na, Pb, Cr, Cd, Bi, As, Hg;,

K, Co, Sn Sb, Th, Be, Ga,'

Y, Yb, Ce

APPLICATION OF SPECTROCHEMICAL ANALYSES

Preliminary results from spectrochemical analyses sug­gest that they have substantial promise as a screening ana­lytical procedure, useful to obtain information about the order-of-magnitude concentrations for many common industrial pollutants. The technique is relatively simple, rapid, inexpensive, and useful for analysis of small samples of a wide variety of pollutants and polluted substances. The results are relatively insensitive to the chemical form of the element. Among the disadvantages are the fact that spectrochemical analyses do not provide information about the chemical form of the element in the substance analyzed. Consequently spectrochemical analyses provide little informa­tion about an element's probable behavior in the ocean'br its availability to marine organisms.

The decision whether to use spectrochemical analyses depends on the precision required. If the material to be analyzed varies widely in concentration, then spectrochemi­cal analyses can provide useful information.' On the other hand, if variations of a few per cent are significant' or'if information about chemical species is essential, then'spec­trochemical analyses have little utility.

Analysis of the data reveals that the minoreleinent concentrations tend to form two clusters. Those plants serving the highly industrialized metropolitan disuricts

·tend to the highest concentrations of typical industrial pollutants. New York City's Bowery Bay plant (Appendix E) had the highest Fe, Mg, Ti, Pb, Ni, Ag, Zn, Co, and Sr. Similar but slightly lower concentrations occurred in sludges from plants in Hunts Point, Bergen County, New, Jersey, and Yonkers, New York. The second group includes primarily residential areas such as Long Beach, Nassau' County, N. Y. and Newark Bay, N. J. It is interesting to note, however, that the highest Cu concentrations were found in sewage sludges from Glen Cove.

The next step in the data analysis will be to take the data reported here together with additional analyses and to analyze them with a factor-analysis program (Imbrie and Van Andel, 1941, Krumbein and Graybill, 1965). From this approach one can obtain a clearer picture of which elements tend to occur together and to select the best element"to use as a tracer for specific groups of industrial or municipal pollutants.

11

CARBON ANALYSES

Carbon, the most abundant element in sewage sludges, has received particular attention. We have attempted a charact­erization of carbonaceous compounds in sewage sludges because they are oxygen-demanding substances and because of their potential to marine organisms as a food source. Furthermore, common and relatively simple analytical procedures for deter­mining organic matter and carbon (Table 1) in sludges have been evaluated to determine their utility in routine analyses of sludges for monitoring or tracer experiments.

Carbon can occur in soils, sediments or sludqes in' different forms: (1) elemental carbon such as coal or graphite; (2) carbonate carbon, and (3) organic matter, All three forms are detected with accuracy and precision by a high-temperature dry-combustion technique. Carbon.,te' carbon is determined by collecting the C02 evolved after the sample is acidified. Results of these analyses (Appendix F) indicate that carbonate-carbon is not abundant in the sludge samples analyzed and can generally be ignored witllOut intro­ducing substantial error.

The simplest technique to, determine the abundance .of organic matter in sludges is the loss-on-ignition (LOl) procedure where a weighed sample is heated at 5500 C ,for several hours and the weight loss (in per cent) is used as a measure of the amount of organic matter, also known as volatile matter (American Public Health Association, 1965, p. 425). Loss on ignition was determined in conjunc,tipn with the spectrochemical analyses. These data are compared (Figure 3) to the total carbon content as determined'by dry combustion in C02-free oxygen at l5000 C in an induct,ion furnace with the C02 given off analyzed by gasometric techniques. Precision and accuracy of the total carbon (C-Total) analyses is about 3 per cent with a normal yield of about 95 per cent of the theoretical carbon content for simple sugars and carbohydrates (Gross, in press). Compar­ison of the LOl data and total carbon data indicates good agreement (±10 per cent). Total organic matter as deter­mined by LOl techniques indicates that it is about 1..9 x total carbon; this is in good agreement with the values of 1.8 reported by previous studies of the relationship between carbon content and organic matter in soils (Jackson, 1958) .

Oxidizable carbon was determined by wet combustion using 0.4 N K2cr207 in H3P04 heated to l600 C. Carbon diox­ide evolved was analyzed to determine the abundance of oxidizable carbon. These data (Appendix F) indicate that an average of about 65 per cent of the total carbon was decomposable by this technique. Oxidizable carbon' would presumably be most significant as an oxygen-demanding carbon species when present in water or possibly useful as a food source for organisms.

80 I I I , , , , ~ /' .

I- . / -'0 I· ~ LOI = 1.9 x CTOTAl - 70 j I- -~ - • oj l- I- --Z (!)

60 i- I -- • Z • •• / 0 -(j) /: (j) 50 - • 9 . -

. j .. • r- -

40 • I • , /, , , , , 10 20 30 40 50

TOTAL CARBON (%)

Figure 3. Loss-on-ignition (or volatile matter) in sludges as a function of the total carbon concentration as determined by high-temperature dry combustion.

13

Reducing capacity of the sludges was ascertained by back-titration (using ferrous ammonium sulfate) to determine excess K2Cr207 remaining after oxidation of organic carbon and other reducible species. This technique provides an estimate, similar to the standard technique (APRA, 1965) used to determine the total oxygen-demanding substances in sludges. The data (Appendix F) indicate that approximately 55 per cent of the total reducing capacity (or oxygen de­mand) of the sludges is due to oxidizable carbon compounds. Additional data are needed to determine the nature and .. abundance of other oxygen-demanding substances in.the. sludges.

The sulfide concentration in the sludges was deter­mined (Appendix F) in order to see if sulfide species might contribute significantly to the reducing capacity of the . sludges. Little sulfide was present in the samples when analyzed. None of the samples smelled of H2S when delivered.

These data suggest that total-carbon or loss-on­ignition analyses are useful techniques to estimate the amount of organic matter in sludges or sludge deposits. Total carbon analyses are more precise but require expen-.· sive equipment and a trained analyst. Loss-on-ignition analyses appears to provide useful data, accurate to ± 10 per cent, and can be done with simple equipment. The loss­on-ignition technique is most satisfactory in samples where hydrous components such as clay minerals are absent; loss­on-ignition results are often seriously in error for· clay­rich samples owing to the decomposition of clay minerals.

DISCUSSION OF DATA

Despite the limitations of the techniques used for these preliminary studies, the dat_a provide ~nteresting information about the general composition of sewage sludges. The loss­on-ignition data and organic contents calculated from total carbon analyses indicate that the sludges are about 55 per cent organic matter by weight. The available analytical data provide little information about the probable compo­sition of this organic matter except that about 65 per cent of the organic matter is oxidizable by K2Cr207 and consti­tutes about 55 per cent of the total oxygen demand of these materials (Appendix F).

Alumino-silicates, chemically analogous to shales (Pettijohn, 1957 p. 106), make up about 45 per cent of the sludges. Comparison of the chemical composition of these aluminosilicates and shales (Table 3) suggest that the sludges are enriched in Ti, Ca, and Na by a factor of about two (Figure 4) as compared to the materials normally found on the ocean bottom.

Because of their apparent similarities to sedimentary rocks and soil, I have compared the minor element compo­sition of the sludges to soils, shales, and sandstones (Figure 5). From these data it appears that several potentially toxic or carcinogenic elements are signifi­cantly enriched in the sludges: Ag l50x, Cr lOx, Cu SOx, Pb SOx, Sn 30x, and Zn 30x. (150x indicates an apparent enrichment of 150 times with respect to the concentration of the same element in shales). These elements are common industrial materials, and most have been widely recognized as waterborne pollutants in other areas (Bowen, 1966) . It is also interesting to note that these elements are known to be enriched in the organic (humus) parts of soils.

It is also instructive to compare the minor element concentration of sludges (Appendix E) with those of living organisms (Bowen, 1966). Despite their limitations the data are useful here to help identify potential problem areas and to pick useful tracers for identifying sewage materials in the marine environment.

The data (Figure 6) indicates that several minor elements are far more abundant in sludges than in organisms; the apparent enrichments are much larger than the uncertain-

15

Table 3. Abundance of major elements (as oxides) in typical sewage sludge and natural sediment deposits.

Average Carbon-free Sludge Sludgea b b Shale Sandstone

SiO? 21. 4% 63.6% 58.1% 78.3%

~·O ~l 2 0.4 1.2 0.65 0.25

1'-1 2°3 4.8 14.3 15.4 4.8

PeO 1.7 5.0 6.1 1.3

M.qO 1.0 3.0 2.4 1.2

CaO 2.1 6.2 3.1 5.5

Na 20 1.0 3.0 • 1.3 0.45

K 20 1.2 3.6 3.2 1.3

Organic c 56 0.80

P2

05 1.2 0.17 0.08

CO2 2.6 5 0

aChemical composition recalculated, and adjusted to 100% after subtracting carbon and phosphorus ~ontent.

bpettijohn, F. J. 1957. P. 107. Fe2

03

recalculated as PeO.

COrqanic matter calculated as total carbon xl.8.

~

0>

---~---

Si

Ti

AI

Fe

Mg

Co

No

K

C

P

+ I

+

I I

x I + ..

~ .. :t:

x .. I x + Shale • Soil

+ • x Sandstone i, x I Sludge

+ Median x -+-

.1 ..........---+ Range

.' x

+ x , •

x + • I

I II "I .1 . 1 I I I 01 I , , ,

Concentration (dry weight)

100%

I gig

Figure 4. Major elements in sewage sludges as compar",rI u;.t.h naturally occurring concentrations in soils, shales and sandstones (data from Bowen, 1966).

17

Ag.,[ --'--=.-~·~.+.~'··-'----r:·Sh::-"-·~ S!~l~~~-

j-'-------'-----'-:"'''- ,---~,""-.-,-, .... --,, -+- Sands10ne Me9lOIl + -.~ 8 ---+- 'J( .. S 'I '-,--'

,-•.• ---- ""ii}' .• ,----... ---..:.. '$ 01 RCHiqe

80 ,_._. __ 1:=-_-=-;. _. ____ '"_ ..

Co +

Cr + x··,,··,·· .. ··_, } .... __ ........ _ ... "-,, _~" .. v".' ,~~ .. , _' .. , "'~"."""." _'0" ___ '" _. '~) .-._ •• ' __ , • "'.~~.",~~ •• __ , ••• , _ ,·v.~~ ...... ~, .. ·,_~ ... •

Cu x -; .. '_ ... \ ......... _--, -+ _.-,."" ",,, .. ,' -" -1)-_ .•• "--'-­

""'-~~,-,.---,..-,---.-,--•. "..~, ..• '",''' .... ,-.~ ... -,.,-, ..... "~.'",.'" ..... -,...,.',~.<'."."-< .. "',,~.-. ... , •. -., ... - ... - ... ~, "" .• ~~- .--.,'-~-" " ~ ... ~,,~ ... ,,-,--...... ----,

Mo + eX 1-..... +-.. --__ .

Ni

Pb -=-.~=~.~~~~~ '~,,~.~~:.'~~~~~~:~~.,~~ .~:~=~:::::~-~~~~:~::~:~- "~.:." ... :.~=~.~:.: .. ~~~]

+ x_+___ I --~ .. ----.. ,,----.--.!--.. - .. -... ,.-.-,,-.. -... , ... , .. --.. --.. '.'. ' ........ _ ... ",,_._._-

Sn x -', .... -......... 1- .• ,._---~"~--,·,~ .. ,e··--· .. ~··-·~-"- .-.~~',-~ .... -.-... .. --,_. __ .. __ .-._ .. -.... _._ .... ,--_ ... _,.,. __ ......... ' ......... ,.

v

Zn l + x _ .... · .. , .. -1" .. · .... __ J.. ... J..,.,.1_LLU.lL, .. ..L .. LLl.J.J.,U, L._ J,_.l ... L!1.U1L, ... ,J_ .. ..!, .. U .. LU .. LL ... ,,,, .. L " .. 1., LU,L' .. :,.'

10,,6 10.4 10-3 10-2 10- 1 I 0/0

1O"! 10 10 2

10'7 " ICf,;:J

C " ")'''1 ,..', ,:;'l, , ,1, t'" ,,~ ,. \ ()" •• l,. ~;'., ... ',,~·\I!~ \"Ii'''.,j:

:'Jatura·I..l--"' oc(;uy-;i::t:-j C:"Y,'1.C'2ntr2tio)'ic, j~~l r:j:""J :\'-;, <~;\~."ll,. s ;-lfL! c-,dTV:;.;I::'OTi';;:';. r;':';::.l.ta (':rom ;.'-',O·,I';:::n \l~f.,{)J

Ag

B

Ba

Co

Cr

Cu

Mo

Ni

Pb

Sn

v Zn

A III!

&.

?

?III til.

III

10-1

10-7

' .... , ,

III!I I

8 II!!

A 8

"" Ll

8

A &. -l1li-

A

A 8

A iii!

&.

0 II1II""

A 8

A B 4

.1

10-6

.. " ' , '" "I Marine Land 8

PLANTS A A A ANIMALS 0 III --s--,--? "" . SLUDGES I

A

"" I

I

I

8 I

I

8 1

A I

I

I ,..j:)

... 1 ~ ..

.1 I , , .

10 1 102 103 104 ppm

10-5 10-4 10-3 10-2 gig

CONCENTRATION ,,~

Figure 6. Minor element concentrations in sewage sludges as compared to naturally occurring concentrations in marine and land plants and animals (Bowen, 1966).

19

20

ties in the analytical data. Elements occurring in the sludges with concentrations more than ten times greater than in marine plants are: Ba 20x, Co 50x, Cr 900x, Cu 600x, Mo 50x, Ni SOx, Pb 60x, Sn 300x, and V 20x. (20x indicates an enrichment of twentyfold with respect to marine plants) •

Considering that the sludges will serve, after deposi­tion, as substrates for organisms and as potential food sources, it seems reasonable to assume that the most troublesome elements will be those highly concentrated relative to both natural deposits and living organisms. Therefore, it appears that studies of Cr, Cu, Pb, and Sn should receive high priority; all four elements are known to be toxic, carcinogenic, or both. It must be kept in mind, however, that the chemical form of these elements will play an important, perhaps decisive role, in det.er­mining their biological effects. Thu~predictions of deleterious effects cannot be made reliably without more detailed information.

ACKNOWLEDGMENTS

Work reported here was supported financially by the State University of New York and the U. S. Army Corps of Engineers under contract DACW72-70-C-009. I thank Professor Roy A. Keller, State University College at Fredonia, Professor John A. Black, Suffolk County Community College, and Professors E. R. Baylor and P. K. Weyl of the Marine Sciences Research Center for their assistance and advice. Sample analyse~ handlin~ and carbon analyses were done by Mr. Y-J Liang, Marine Sciences Research Center.

- 21

BIBLIOGRAPHY

American Public Health Association. 1965. Standard Methods for the Examination of Water and Wastewater, Including Bottom Sediments and Sludges. Twelfth edition. New York. 769 pp.

Bowen, H. J. M. 1966. Trace Elements in Biochemistry. Academic Press, New York. 241 pp.

Federal Water Pollution Administration. 1965. Conference in the Matter of Pollution of the Interstate Waters of the Hudson River and its Tributaries - New York and New Jersey. Conference September 1965. 2 volumes.

Gross, M. G. In Press. Analysis of Carbonaceous Matter in Sediments and Sedimentary Rocks. Chapter 27. In R. E. Carver (editor) Techniques in Sedimentary Petrology. Wiley, New York.

Harvey, C. E. 1964. Semiquantitative Spectrochemistry. Applied Research Laboratories, Glendale Calif. 187 pp.

Imbrie, John and van Andel, of Heavy Mineral Data. 75: 1131-1156.

Tj. H. 1964. Vector Analysis Geol. Soc. America. Bull.

Interstate Sanitation Commission. 1969. 1968 Report of the Interstate Sanitation commission on the Water Pollution Control Activities and the Interstate Air Pollution Program. New York. 104 pp. plus Appendices.

Jackson, M. L. 1958. Soil Chemical Analysis. Prentice­Hall, Englewood Cliffs, New Jersey. 498 pp.

Krumbein, W. C. and Graybill, F. A. 1965. An Introduction to Statistical Models in Geology. New York, McGraw­Hill. 475 pp.

Pettijohn, F. J. 1957. Harper, New York.

Sedimentary Rocks. 718 pp.

Second edition.

23

Appendix A. Plants Sampled and Population Serveda

Sample number

690818001

690818002

690818003

690818004

690818005

6Q(1819001

Plant location

Ii/ards Island Plant

Hards Island, Manhattan

Runts Point Plant

Loster Street & Rya,.;a Avenue

Bronx, New York

Newtown Creek Plant

329 Greenpoint Avenue

Brooklyn, New York

Bowery Bay Plant

43-01 Berrian Boulevard

Astoria, Queens, New York

Tallmans Island Plant

127th Street & East River

College Point, Queens, New York

Port Richmond Plant

180 Richmond Terrace

Staten Island, New York

aInterstate Sanitation Comrnission, 1968.

Type of Treatment

Secondary

Secondary

Intermediate

Secondary

Secondary

Primary

Population Served (Thousand)

1,470

770

2,500

1,000

251

60

Sample number

6908190()3

690819004

690819005

690910001

690904001

Plant location

Rockaway Plant

106-21 Beach Channel Drive

Rockaway, Queens, New York

Jamaica Plant

150-20 134 Street

Jamaica, Queens, New York

26th I'lard Plant

Brooklyn, New York

West Co. Dept. of Public "lorks

Division of Sewars

Joint Treatment Plant

Ludlow Dock (South)

Type of Treatment

Secondary

Secondary

Secondary

Primary

Yonkers, Illestchester County, New York

Sewage Disposal Plant #2

Nassau County

Fast Rockaway, Long Island

Secondary

Population Served (Thousand)

90

415

385

415

600

N VI

Sample number

690904002

690904003

690925001

690925003

690925005

690925007

Plant location

Glen Cove Plant

.Morris Avenue

Glen Cove, Ne,·! York

Long Beach Plant

Pt. of National Boulevard & Bay

Long Beach, Nassau County, New York

Type of Treatment

Secondary

Secondary

Wilson Avenue Newark Bay Facility Primary

Newark, New Jersey

Joint ~leeting of Fssex & Union Primary

500 South 1st Street Counties

Elizabeth, (Vnion County), New Jersey

Bergen County Se,ver

Little Ferry, New Jersey

Middlesex County Sewage Auth.

Sayreville, New Jersey

Primary

Primary

Total Population Served

Population Served (Thousand)

25

29

2,899

465

5

500

11,939

>.)

0'

Appendix B. Comparison of spectrochemical analyses of standard rock samples with the preferred analytical data •

.

Sulfide Ore.

This preferred

1 2 Report Data

Syenite Rock

This Preferred

Reportl Data2

Tonali te Rock

This Preferred

Report l Data3

Si 15 16.2 13 27.8 17 29.3

Al 4.7 5.1 2.7 5.1 12 8.8

Fe 25 24 1.8 6.0 2.2 4.2

Ti 0.48 0.47 0.35 0.29 0.54 0.36

Mn 0.082 0.06 0.10 0.25 0.044 0.06

Ca 2.1 2.9 8.5 7.2 2.8 3.7

Mg 2.1 2.4 2.5 2.5 1.1 1.1

. Na 0.43 0.74 2.5 2.6 3.7 3.3

K 0.2 0.50 6.0 2.3 4.7 1.0 . P 0.5 0.04 0.5 0.09 0.5 0.06

Ba 0.05 0.02 0.05 0.03 0.05 0.068

B 0.002 0.002 0.003 0.01 0.002 0.001

Co 0.05 0.05 0.002 0.002 0.004 0.0013

Cr 0.03 0;036 0.01 0.005 0.006 0.0024

Cu 0.5 0.8 0.002 0.002 0.007 0.0047

Ni 1.1 1.3 0.06 0.004 0.001 0.0013

Pb 0.05 0.02 0.08 0.05 0.03 0.0037

Sr 0.01 0.01 0.01 0.03 0.02 0.041

V 0.004 0.02 0.004 0.009 0.007 0.0096

_Z_r ____ ~_.0_3_ .. __ 0_. 0_1 _____ 0_._0_9 ___ 0_"_3._-1..._0::..::.;' 0:..;2::..-_-.-;0:-,;.:-,;0.,.;;1:.;,7 __

1

2

3

Pacific Spectrochemical Laboratories, Inc. Sept. 29, 1969.

Webber, G. R. 1965. Second report of analytical data for CAAS syenite and sulphide standards. Geochemica et Cosmochimica Acta. 29:229-248.

\~. K. L. Thomas, 1963. Standard Geochemical sample T-l, Supplement 1. Part 1. Chemical analysis of T-l. Geological Survey Divis ion, ."linistry of Commerce and Industry, Government Printer, Dar Es Salaam.

27

28

Appendi~ C. Spectrochemical analyses of replicate samples from unmixed sludges.

6908-190031 6908-190032 6908-190033

Silicon 11. % Iron 1.8 Aluminum 5.0 Calcium 1.6 Magnesium 0.77 Copper 0.20 Barium ------Boron 0.0031 Phosphorus 0.52 Titanium 0.S5 Lead O.lS Manganese 0.039 Chromium 0.37 Nickel 0.061 Bismuth ------Molybdenum 0.00S7 Tin 0.056 Vanadium 0.014 Cadmium ND<0.006 Silver 0.0035 Sodium 2.1 Zinc 0.30 Zirconium 0.014 Cobalt 0.0080 Potassium 1.3 Strontium 0.012 Arsenic ND<0.06 Mercury ND<0.09 Antimony ND<O.OOS Thallium ND<O.lO Beryllium ND<0.0003 Gallium ND<0.003 yttrium ND<0.009 Ytterbium ND<0.004 Cerium ND<0.04 Other elements nil

Loss on 40.40% ignition (Sulfate ash)

Date of analyses: 1 Sept. 29, 1969

2 Dec. 10, 1969

12.% 1.8 4.1 3.0 0.99 0.23 0.046 0.0053 0.S4 0.51 0.17 0.027 0.21 0.039 ------0.00S4 0.035 0.0084 ------0.0020 1.1 0.3S 0.017 0.0049 0.69 0.0071 ------------------------------------------------------nil

3S.55%

2

ll. % 1.1 3.0 1.S 0.73 0.056 0.050 0.0020 0.37 0.29 0.016 0.0095 0.035 0.012

trace 0.024 0.0079

0.0015 1.6 0.12 0.010 0.0053 2.1 0.0095

nil

52.50%

Analyst: H. W. Johnson Pacific Spectrochemical Laboratory

ADPenc'ix D. Spectrochemical analyses of after grinding and mixing. different times.

6908-19001

1 2

Silicon 9.4% 11% Iron 1.4 1.9 Aluminum 4.6 4.1 Calcium 1.6 1.5 Magnesium 1.0 o . 8 Copper 0.19 0.15 Barium 0.068 0.066 Boron, 0.0030 0.0030 Phosphorus 0.37 0.51 Titanium 0.83 0.47 Lead 0.18 0.056 Manganese 0.019 0.025 Chromium 0.47 0.23 Nickel 0.048 0.048 Bismuth <0.002 ------

"Iolybdemum 0.0075 0.0037 Tin 0.056 0.031 Vanadium 0.013 0.013 Cadmium ------Silver 0.0031 0.0028 Sodium 2.6 1.7 Zinc 0.26 0.23 Zirconium 0.020 0.013 Cobalt 0.0094 0.0052 Pottassium 1.8 2.7 Strontium 0.013 0.014 Arsenic ------ ------

~ercury ------ ------

Antimony ------ ------

Thallium ------ ------

Beryllium ------ ------

Gallium ------ ------Yttrium ------ ------Ytterbium ------ -----~-

Cerium ------ ------

Loss on ignition 41. 6% 46.25% (sulfate ash)

duplicate samples Analyses made at

6908-19004

1 2

16.% 14% 2.3 1.8 3.0 3.0 2.4 2.4 0.72 0.83 0.16 0.11 0.076 0.065 0.0024 0.0025 1.0 0.11 0.49 0.39 0.084 0.065 0.047 0.047 0.14 0.071 0.043 0.025 ND<0.002 ------0.0083 trace 0.049 0.39 0.0073 0.0039 ------ ------

0.0025 0.0021 1.3 0.65 0.26 0.26 0.013 0.011 0.0083 0.0029 0.76 1.1 0.010 0.011 ------ ------------ ------------ ------------ ------------ ------

------ ------------ ------

------ ------

------ ------

36.8% 48.40%

ND - not c'etected, concentration less than value indicated. Analyses: Analyst: H. W. Johnson 1 September 29, 1969 Pacific Spectrochemical 2 969 Lahoratories December 10, 1

29

30

Appendix D cont.

6908-18002 6908-18005 --.----

1 2 1 2

Silicon 9.0% 8.9% 9.5% 10% Iron 2.0 2.6 1.8 1.5 Aluminum 4.3 2.5 4.8 2.7 Calcium 1.3 1.8 1.5 1.4 Magnesium 0.89 0.69 0.82 0.80 Copper 0.13 0.14 0.13 0.11 Barium 0.045 0.059 0.063 0.042 Boron 0.0038 0.0024 0.0036 0.0034 Phosphorus 1.3 0.91 0.63 0.70 Titanium 0.48 0.38 0.53 0.27 Lead 0.096 0.055 0.089 0.056 Manganese 0.024 0.017 0.030 0.040 Chromium 0.32 0.11 0.22 0.085 Nickel 0.023 0.19 0.046 0.033 Bismuth trace<0.002 _._---- ------ ------Molybdenum 0.0070 0.0016 0.0076 trace Tin 0.039 0.034 0.037 0.022 Vanadium 0.010 0.015 0.0082 0.0080 Cadmium ND<0.006 ------ ------ ------Silver 0.0022 0.0014 0.0027 0.0021 Sodium 1.8 1.2 1.4 1.1 Zinc 0.36 0.25 0.17 0.17 Zirconium 0.011 0.012 0.013 0.012 Cobalt 0.0089 0.0036 0.0055 0.0031 Potassium 0.83 2.7 0.83 1.8 Strontium 0.0014 0.0015 0.011 0.0075 Arsenic ND<0.06 -"----- ------ ------Mercury ND<0.09 ------ ------ ------Antimony ND<O.008 ------ ------ ------Thallium ND<O.10 ------ ------ ------Beryllium ND<0.0003 --_._-- ------ ------Gallium ND<0.003 ------ ------ ------Yttrium ND<0.009 ----.-- ------ ------Ytterbium ND<O.004 ------ ------ ------Cerium ND<0.04 ------ ------ ------

Loss on ignition 47.70% 53.75% 49.00% 55.40% (sulfate ash)

Appendix E. Spectrochemical analyses of sewage sludges, New York Metropolitan Region. a

S'ilicon­Iron· Aluminum­Ca Ie ium-Mn gn C'<:; lum­Copper·w

Sod itJm-Ti tanium· Chromium­Potnssium­Pho'phorus­Ba r iU!1l­

Boron­Lead-Nanganese ... Nickel· Molybdenum­Tin-Vanadi'Jf:\~ Bismuth· Silver· Z in_c'"

\.: arC's Island.

Punts !") • ,~

t Olr. ",.

Np~.·,' Yo,rk City

,(\ls ',..;tn\,.'n

C,.""k p'("~'I(> ry

Bay rI'a 111M:~I1S f.s-!dnd

7.0% 8.9% 11.% 10.% IO.~ 1.0 2.6 1,2 },b. 1.:, 1,7 2.5 2.5 2.7 2.7 1.2 1,8 3.7 1.6 1.(, 0.63 0.69 0. 59 Q~B!. O,BO 0.056 0.14 0.16 0.19 0.11 2.0 1.2 1.3 1. 7 L t -o~Ti 0.38 0.23 0.56 0.71 0.0:'0 0.11 0.080 jj5~;' 0.085 2.5 2.7 1.'/ 2.7 1.8 0.29 0.91 O. ('5 O. n 0.70

_q .• ,!!flQ 0.0:'9 0.10 0.011 0.042 0.00]6 O. OO?!,O:O[D4 D.0020 0.0034

trace \,0.00:, C.OoS 9212- Q ... l2.. 0.056 0.<)]1, 0.011 0.021. 0,029 0.01,0 0.0069 0.019 0.025 0.090 0.033 O.OOll 0.0016 0.0033 0-:-003'9 trac~ (0.002 0.021 0.034 0,028 0.048 0.022 0.0076 0.015 0.0059 O.Oll 0.0080

ND ,O.Oc)? _._ ... _--::C:-~7:-:__ trilcC'" 0.002 NO <0.002---------- .. ·----0.0015 0.0014 0.0016 Q.JlQJ .. J 0.0021 O--,QQ~ 0.25 0.2(, 0.29 0.17 0.0053 O.OIL 0.027 ~021 0.012 0.0015 0.0036 0.0039 0.0061 0.0031 0.0096 (\. OJ" 0.0097 O":lTIY' 0.0015 ND (0.06-· ... :'~:;';:-::":'''' •. - - -- - -- - ---- .- ..... - --- ==-~-;;;-- --- -- -... -........ NO ~ 0,09- -- -- ... -. -- .... -. - - ... --- -- - ..... -- --------.. - ---- ---- --.-ND < [). 008-··· .. • - ........ --- -- .. - --- - ... -- - ----"-' -- - ------------ ----NO (0.10-----·----·-------------------- .. ------------------- •. --­ND <.0.0003- -- .. - - ---- --- ----- - - --- --- --- --- -- --- --------- -- - - .. --­ND (0.003·--····-----------------------------------------------­NO (0.009- .. -----------------------------------------------------

Z 1. rcon i um" CobC11t­Stronti.um­Arsenic­Mercury­Anttmony .. Thorium­Bcryll ium­Ga llium­Yttrium­Ytterbium­Cerium· Other. elements-

~g ~8:8?,~:::::::::::::::::~::::::::::::::::::::::::::::::::::::: nil nil nil nil nil

t083 on ignition -, 64.55'. (9111fote a~h)

ND Not Datecte~

53.75%

MaxilDurn val,ue for )J.ement Mirlirnum value for ele~cnt

49.10"/, 47.90% S5.40%

a Analyst: P.W. Johnson. Pa~j.fic Spectrochnrnical Laboratories.

31

32

ADpendix E. Cont.

Silicon­Iron­Aluminum­Calcium­Magnes lum­Copper­Sodium­Titanium­Chromium­Potassium­Phosphorus­Barium­Boron­Lead­Manganese­Nickel­Molybdenum­Tin­Vanadium­Bismuth­Silver­Zinc­Zirconium­Coba 1 t­Strontium­Arsenic­Mercury­Antimony­Thorium­Beryllium­Gall iurn­Yttrium­Ytterbium-Cerium-

Port Richmond

New York ci ty

Rockaway Jamaica 26th ,':ard

11.% 11.% 14.% 9,5% 1.9 1.1 T.8 0.97 4.1 3.0 3.0 3.0 1.5 1.8 2.4 2.1 0.80 0.73 0.83 0.63 0.15 0.056 0.11 0.088 1.7 1.6 0.65 1.1 0.47 0.29 0.39 0.24 0.23 0.035 0.071 0.11 2.7 2.1 1.1 1.0 0.51 0.37 .Q..J-l. 0.30 0.066 0.050 0.065 0.048 0.0030 0.0020 0.0025 0.0017 0.056 0.016 0.065 0.023 0.025 0.0095 0.047 0.015 0.048 0.012 0.025 0.026 0.0037 l;r.1l..c.@.{0.002---------- 0.0021 0.031 0.024 0.039 0.029 0.013 0.0079 0.0039 0.0073 ND <0.002------~-- ----- trace {0.002 NO <0.002 0.0028 0.0015 0.0021 0.00092 0.23 0.12 0.26 0.16 0.013 0.010 0.011 0.0068 0.0052 0.0015 0.0029 0.0029 0.014 0.0095 0.011 0.0092 NO (0.06-----------------------------------------

. ND < 0.09- - - - --- - -- .. - - -- - ---- - - - --- - - ---- -- -- ----­NO (0.008---------------------------------------­NO <0.10----------------------------------------­NO ~0.0003--------------------------------------­NO <0.003---------------------------------------­NO (0.009---------------------------------------­NO<0.004-----------~---------------------------­NO (0.04-----------------------------------------

Other elements- nil nil nil nil

Loss on 19nit ion - • 46.25% 52.50% 48.40% 59.00%

1

Appendix E. Cont.

Silicon-Iron-Altlminum­Ca1cium-Magnesium­Copper­Sodium-Titanium-Chromium­Potass itlm­Phosphorus­Baritlm-Boron­Lead-Manganese­Nicke1-Mo1ybdenum­Tin-Vanadium­Bism:) th-Silver-Zinc-Zirconium­Coba 1 t-Strontium-Arsenic-Mercury­Antimony­Thorium- . Beryllium­Gallium-Yttrium­Ytterbium-

Nassau Nassau Cty #2

County, Glen Cove

N.Y. New Jersey Long Beach Newark Bav

8.0% 6.6% 8.3% 5.6% 1. 3 0.50 1. 3 0:-54 -1.9 1:8"- 1.3 2.0 1.4 0.81 -5.5- 0.52 0.52 0.36 0.55 0.22 0.13 0.34 0.047 0.038-0.62 0.25 0.6.4.' 0.-47-0.23 0.1'7- 0.24 0.25 0.17 0.064 0.020 0.15 0.69 0.36 0.4'7- 0.34 1.3 0.28 0.77 0.29 0.045 0.053 0.051 0.045 0.0038 0.0013 0.0020 0.0011 0.049 0.042 0.035 0.050-0.023 0.0078 0.Of1- 0.034 0.026 0.031-- 0.0085 0.019

t.!~c~ .. ~~.<2.0.3 0.0025 ND ,(0.002. 0.0050 0.033 0.064 -0.023-- 0.0068 0·.00073 0.0019 trace <0.002 0.0019 trace < 0.002- --- - - -- ----- --- - - -- -- ------- -- -- - - ---0.0016 0.0023 0.0011 0.00072 0.17 0.12 0.16 0.15 o . 0048 0.0084 .Q ,-OQ41 0.0081 0.0026 0.0015 0.0030 0.0059 0.0059 0.0042 0.0085 0.0045 ND (0.06----------------------------------------­ND < 0.09- - - - ------------------- --- ---- - -- --- - -- -­ND <0.008-------------------------------"-------­ND (0.10-----------------------------------------

ND (0.0003 ND '" 0.0003 trace (0.0003 ND <0.003 ND (0.003--------------------------- 0.0014 ND <0.009---------------------------------------­ND -( 0.004- - -- -- -- - -- -- --- ---- ----- ---- --- -- ------

Cerium- ND <0.04-----------------------------------------Other e1ements- nil nil nil nil

• Loss on ignition - 65.25%

(sulfa te ash) 75.15% 57.10% 77 .85%

33

34

1111111111111111111111111111111111111111111111111111111111111111

3 1794 02254684 1

Appendix E. Cont.

New J(~i:".s :: .• :_1_ .• _. ___ ._. _____ ._ ... __ NC'-\v, York .......... __ ._-_._-_.;.-._' ".~.--"-".'-"'-,---... - -... ,

Elizaheth Bergen ··~.iddl(~~')i;~X

Silicon-Iron-Alumlnum·-ea lcium­Nagl"'" tum­Copper­Sodium­Titanium­Chromium­Potass lum­Phosphorus­Barium­Boron­Lead­Manganese­Nickel­Molybdenum­Tin·· Vanad i um­Bismuth­Sil ver­Zinc-Z i rconium­Cob"lt·· Strontium­Ars'ertie·· Mercury­Ant imony­Thorium-Beryll ium­Ga 111 tll\1-

Yttr.i.um-Y t te. "tbium-

(-'0 un ty Coun t.:,

6.1% 10.% 5.3% 0.69 1.4 0.79 1.3 4.5 1.0 0.94 1.1 0.57 0.1,7 0.75 0.?5 0.059 0.081. (L (j1,4 0.75 0.39 0.15 0.26 1.2 0.72 0.14 0.81 0.021 0.78 '0-:81 0.18 0.56 2.1 :o.Ts-o . 041 !f;-069 0 ,'en 2 0.0020 0.0031 0.0038 0.023 0.06<j (l.03S--

. 0.019 O.O~~ 0.011 0.017 0.019 0.0044 0.0091 trace < 0.002 ND (0: oaf 0.028 -. 'O:Oi9' - . -- -- o:--o09i-0.0023 0.0034 0.0035 ND < 0.002.-------·---------------------0.0016 0.on1" Q .. ..QQO)~ 0.12 O.lJ O.OR? 0.0069 0.0031 0.0094 0,0034 0.001 0.0008? 0.00~1 0.0081 O.OO~1

1.9 1.9 2.0 0.86 (I. 1 ') O. t;)

0.063 1.7 0.92 0,01,6 0.0030 O.09? 0.050 o. 626~ 0.0080 0.032 0.0071

ttace < 0.002 0.0019 0.27 0.036 o.60i6 0.0091

NIl {Oo06· _ .... -. ~ __ "', ______ ....... _W"'_, .• ___ ... ___ · ___ ~_ ... ___ _

I:~D '( 0,. (;9·- - -.,..- ...... --- ... - -~-~,-- .. - -- - -- ..... -- _ ..... - _.- - -""_ ..

ND (0.008--------------------------------------­ND (0.10-----------------------------------------ND (0.0003----·-- .... -------·--- .. ------- trace ... 0_0003

ND (0 .. 00.) trace (0.003 ND (0.003 . trace < 0.003 ND < 0,009 .. -- - - .. -- - -- ------- .. ------ - -------- .. ---­NO (0.004------------------------- .. ----------- .. -

Cer i.Ule,-- ND <0.04-·· ...... - .. -- -- - •. - .... - --- - - -.," - --- - --- --'" _ .. -Other ('lc",e""ts- nn nil nIl nil

Loss on IgnJ tion (sulfate ash)

50.60% 79.13%

I