project their influence · data analysis and interpretation: 1, discussion of results and data...

PROJECT NO. 23

GEOCHEMISTRY AND HYDROGEOLOCY O f AGRICULTUBE WATERSHED NO. 10, llND THEIR INFLUENCE ON THE CHEMICAL COMPOSITION

OF WATER llND SEDIMENTS

bY Eric Veska

Department of Geological Sciences Brock University

St. Catharines , Ontario

August I!lll

AUGUST 1977

Dr. P. A. Peach of t h e Department of Geological Sciences a t Brock Un ive r s i ty has r ep laced D r . J. A. C. Fortescue as p r o j e c t l eade r on the Watershed No. 10. Study.

Mr. E. Veska, a s s o c i a t e i n v e s t i g a t o r of P r o j e c t No. 23. , has performed all t he ana lyses and sample c o l l e c t i o n f o r t he North Creek Watershed Study, i nc lud ing t h e p repa ra t ion of t h i s r e p o r t .

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The study discussed in this document was carried out as part of the efforts of the Pollution from Land Use Activities Reference Group, an or- ganization of the International Joint Commission, established under the Canada-U.S. Great Lakes Water Quality Agreement of 1972. Funding was provided through the Ontario Ministry of Agriculture and Food. Findings and conclusions are those of the author and do not necessarily reflect the views of the Reference Group or its recommendations to the Commission. Certain data files employed in this report were generously made available by the University of Windsor (Department of Geography) and the Ontario Ministy of the Environment. The writer gratefully acknowledges the collaboration of Dr. J . A . C . Fortescue and Dr. P.A. Peach and of useful comments from pro- fessors at Brock University and the University of Waterloo. The Department of Geological Sciences at Brock University made space available to house the project. Grateful acknowledgement is expressed to Ms. B. Foster and and also to Miss K. O'Hearn for typing this report.

PAGE NO.

LIST OF TABLES

LIST OF FIGURES

SUMMARY

INTRODUCTION: 1. Study Objectives 2 . Study Approach

DATA COLLECTION NETHODS : 1. Description of Field Methods 2. Description of Laboratory Methods

EXPERIMENTAL RESULTS

DATA ANALYSIS AND INTERPRETATION: 1, Discussion of Results and Data Interpretation 2 . Conclusions and Degree to Which Project Objectives

Were Met

RELATIONSHIP OF PROJECT RESULTS TO PLUARG OBJECTIVES:

Pollutants Contributed To Surface and Ground Waters?

2. What Is The Extent Of Pollutant Contributions and What Are The Unit Area Loadings By Seasons From The Anomalous Site To Surface and Ground Waters?

Sources To Boundary Waters?

1. From What Sources and From What Causes Are

3 . To What Degree Are Poilutants Transmitted From

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B I BLIOGRAPIFY

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APPENDICES:

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103 1.

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Geochemical Concentrations In Bottom Sediments, Suspended Sediments, Stream Waters and Well Waters In The Anomalous North Central Sector Of The North Creek Watershed Additional Chemical and Textural Parameters On The Bottom Stream Sediments In The Study Area Comparison Of Till Underlying The Anomaly With The Nearby Halton Till Composition Geochemic a1 Concentrations In Sediment Core N1 Additional Chemical and Textural Parameters On Sediments From Core N 1 (i) Total Discharge Data For the

Months of 1976 In The North Creek Water shed

(ii) Daily Discharge Data For Days Of Sample Collection In 1976

(i) Monthly and Annual Precipitation Values For The North Creek Watershed In 1976

Days Of Sample Collection In 1976 (ii) Daily Precipitation Data For

Atmospheric Loading Data For The North Creek Watershed

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TABLE

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Precision Test On Soil Standard

Precision Test on Waters

Surface Water Analyses From The Anomalous Study Area

Cation - Anion Balance On The Surface Water Analyses

Eh - pH Relationships

Comparitive Table On The Geochemical Composition Of The Local S o i l and Bedrock With The Anomalous Geochemical Values

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FIGURE

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Index Maps for the Study Area: a) Location, b) Topography, c) Bedrock Contour, d) Bedrock Geology

Detailed Study on the North Central Sector

Performance Test of Analytical Methods

Comparative Analyses between Emission and Atomic Absorption

Trace Element Distribution from Bottom Stream Sediments in the North Creek Watershed

Na

K

Sr

si

As

Pb

Zn

Cd

Ni

Ti

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Distribution Map

Distribution Map

Distribution Map

Distribution Map

Distribution Map

Distribution Map

Di s t r ibu t ion Map

Distribution Map

Distribution Map

Distribution Map

Distribution Map

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FIGURE

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Sn

Mo

Be

Fe

A 1

Mn

cu

Cr

P

Y

Distribution Map

Distribution Map

Distribution Map

Distribution Map

Distribution Map

Distribution Map

Distribution Map

Distribution Map

Distribution Map

Distribution Map

Geochemical Comparison Amongst Four Measured Parameters In The Anomalous North Creek Waters:

Sr

Na

Ca

K

Zn

Cd

Pb

As

Ti

Ni

Scan Sheet

Scan Sheet

Scan Sheet

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Scan Sheet

Scan Sheet

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FIGURE

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cu

Ag

C r

Sn

S i

Be

Fe

A1

Mn

P

Scan Sheet

Scan Sheet

Scan Sheet

Scan Sheet

Scan Sheet

Scan Shee t

Scan Sheet

Scan Sheet

Scan Sheet

Scan Sheet

AdLit ional Chemica, and Tex tu ra l Parameters On The Bottom Sediments I n The Study Area

Water Chemistry O f The Anomalous S i t e As Represented by V e r t i c a l Bar Graphs

Cross S e c t i o n a l View of The North Creek Water shed

Geological Desc r ip t ion Of The Cross Sec t ion A t The Anomaly S i t e

Geochemical Core InvesL iga t i an Adjacent To The Anomalous North Creek Waters For Elements Zn, Pb, A s , Cd, Ag, C r , Xi, Mo, Cu

Geochemical Core I n v e s t i g a t i o n Adjacent To The Anomalous North Creek Waters F o r Elements m, Nd, Ca, K, k'

Geochemical Core I n v e s t t i g a t i o n Adjacent To The Anomalous North Creek Waters For Elements T i , S r , F P , Al, Be, Si

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Additional Chemical and Textural Parameters on Sediments from Core N1

Comparison Amongst the Geochemical, Chemical, and Textural Parameters on the Sediments from Well Core N1

Textural Comparison between Bottom Stream Sediments of the Study Area and Sediments from Core N1

Mineral Stability in the Anomalous North Creek Waters

Activity Diagram for the System HC1 - H20 - CaO - C02 - MgO in the Anomalous North Creek Waters at OOC

Predominance Diagram f o r the Stability of Calcium and Magnesium Carbonates in the Anomalous North Creek Waters

Water Well Traverses

Water Well Profiles in the North Creek Watershed

Mineral Stability in the Anomalous North Creek Waters

Eh-pH Diagrams for the Anomalous North Creek Waters for Elements S, Ni, Fey Mn

Eh-pH 'Diagrams for the Anomalous North Creek Waters for Elements Cd, A s , Zn, Pb

Eludication of the Origin and Cause for the Anomalous Site in Reference to Traverse "C"

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Thermodynamic eva lua t ion of t he ion s p e c i a t i o n of the major chemical c o n s t i t u e n t s from t h e anomalous s p r i n g and su r face wa te r s showed gypsum t o be supe r sa tu ra t ed i n these anomalous s p r i n g waters . Downstream from the sp r ing , t h e l o s s of t he sp r ings carbon dioxide i n a t t a i n i n g equ i l ib r ium wi th the atmospheric carbon dioxide, r e s u l t e d i n the su r face waters being supe r sa tu ra t ed wi th r e s p e c t t o the carbonate minerals, such as c a l c i t e , a r agon i t e , magnesite and dolomite, Therefore, the mixing of the c h a r a c t e r i s t i c CaJcMg*HCO3*SO4 groundwater from the underlying bedrock, appeared t o be the p r i n c i p a l e f f e c t upon the sp r ing water con- taminat ion of the major c o n s t i t u e n t s i n the North Creek wa te r s ,

Downstream from the sp r ing , t he minor c o n s t i t u e n t s such as, t he heavy me ta l s , a r e co -p rec ip i t a t ed wi th CaC03, complexed with the s u l - phate r a d i c a l and o t h e r i no rgan ic l i gands and form aquo metal complexes. I n r e l a t i o n t o t ime, t he r e l a t i v e heavy metal concen t r a t ions i n these anomalous su r face wa te r s showed d i r e c t r e l a t i o n s h i p s with r e s p e c t t o p r e c i p i t a t i o n and the su r face water discharge of the North Creek waters .

Th i s b r i e f l y summarized the o r i g i n and the geochemical h i s t o r y of the abnormality of t he high metal values . me ta l s are der ived n a t u r a l l y from the d i s s o l u t i o n of the bedrock mineral d e p o s i t s , t hus contaminating the groundwater discharge i n the North Creek waters. The c o n t r i b u t i o n of man's a c t i v i t i e s as a source of heavy metal contamination i n these n a t u r a l waters appeared t o be neg l igab le , s ince the imp l i ca t ion of atmospheric p o l l u t i o n was proven t o be r e l a t i v e l y minute

The source of t hese high heavy

The North Creek watershed Study (AG-10) w a s one of the eleven a g r i - c u l t u r a l watersheds s e l e c t e d f u r the d e t a i l e d s t u d i e s programme of the A g r i c u l t u r a l Watershed S tud ie s (Task C- I n t e r n a t i o n a l Reference Group on Great Lakes P o l l u t i o n from Land Use A c t i v i t i e s (PLUARG)). The study w a s b a s i c a l l y concerned wi th the element d i s t r i b u t i o n and the i d e n t i f i c a t i o n of any contaminant sources of the Twenty Mile Creek Tr ibu ta ry .

The o b j e c t i v e s of the North Creek Watershed Study (AG-10) i n i t i a t e d Apr i l , 1976 were:

1. To determine the d i s t r i b u t i o n , amount and o r i g i n of twenty macro- n u t r i e n t s , m i c r o n u t r i e n t s , and t r a c e elements i n the North Creek Branch Watershed (AG-10) i n terms of n a t u r a l weathering during the Holocene per iod and any a c c e l e r a t e d t ransformations r e s u l t i n g from man's a c t i v i t i e s during the l a s t two hundred yea r s .

2 . To examine and i n t e r p r e t d i s t r i b u t i o n p a t t e r n s f o r the twenty elements i n stream sediments, s o i l s , s u b s o i l s and stream water i n Watershed No. 10 i n terms of the geochemical h i s t o r y of the a r e a , p a t t e r n s r e - s u l t i n g from man's a c t i v i t i e s and the o r i g i n and flow paths of the stream water leaving the watershed,

These s tudy o b j e c t i v e s h e l p i n i d e n t i f y i n g the source of some of t he contaminants i n the North Creek Watershed, and i n so doing, h e l p i n d e t e r - mining t h e e f f e c t on the n a t u r a l waters . The t r a n s p o r t a t i o n mechanism of the contaminants from the source t o the mouth of the t r i b u t a r y bas in of the North Creek, thence by Twenty Mile Creek t o Lake Ontar io , w i l l be es t imated by a prepared model based upon the four s tud ied parameters: 1) bottom stream sediments, 2 ) suspended sediments, 3 ) stream wa te r s and 4 ) well waters .

3

f l STUDY llPPROllCH U

A. STUDY LOCATION

The l o c a t i o n of the North Creek Watershed i s shown i n Figure 1.a . It i s p a r t of the Twenty Mile Creek Drainage System on t o p of the Niagara Escarpment. The watershed i s h a l f a mile south of the v i l l a g e of Smith- v i l l e and w i t h i n the boundary l i m i t s of West Lincoln and Grimbsy Town- s h i p s . The gene ra l topography of the study a r e a i s shown i n Figure 1.b.

A contour map of t h e S i l u r i a n bedrock underlying the watershed i s shown i n Figure 1.c. The Lockport Formation forms the c r e s t of the Niagara Escarpment; and c o n s i s t s of t h ree Members, 1) the medium c r y s t a l l i n e c r i n o i d a l Gasport I.,imestone a s the b a s a l beds, 2) the che r ty , f i n e l y c r y s t a l l i n e Goat I s l a n d Dolostone, and 3) the dark brown a p h a n i t i c t o sugary Eramosa Dolostone a s the upper u n i t . The l a s t Member may be f u r t h e r sub-divided i n t o a lower dolostone s e c t i o n with b l ack , bituminous sha ly p a r t i n g s , the so c a l l e d "Vinemount Shale", and an upper s e c t i o n of a dark grey, dense dolostone. The Guelph Formation o v e r l i e s t he Lockport Formation towards the south and i s a dark brown, a p h a n i t i c t o medium c r y s t a l l i n e , porous dolostone. The Lockport-Guelph Contact zone (1) l i e s j u s t n o r t h of the North Creek Watershed as shown i n the bedrock geology map i n Figure 1.d. It should be noted t h a t the Eramosa Member i s bituminous and f o r the most p a r t magnesian throughout the s e c t i o n and c o n t a i n s f i n e specimens ( 2 ) of s e l e n i t e , c e l e s t i t e , dolomite, s p h a l e r i t e and galena.

Overlying the bedrack, i s t i w i fL+ l ton tCl1, covered i n t u r n by Lake Warren g l a c i o l a c u s t r i n e s i l t and c l a y d e p o s i t s , The Ontar io S o i l Survey has c l a s s i f i e d one-third o f the watershed as O r t h i c Huniic Gleysols and two-thirds as O r t h i c Gray B r o w n Luvi sols,

The e n t i r e watershed i s c l a s s i f i c d a s r u r a l , wi th va r ious l i v e s t o c k ope ra t ions , such as d a i r y , b e e € , p i g s > pou l t ry , and horses . Much of the land i s under p a s t u r e , f o r e s t and cash c rops , such a s corn, soybeans and small g r a i n .

..-. -: <--

.I . , - . a. -.,

EXPLINATlON

FIG. 1 .d BEDROCK GEOLOGY ( Modified from Liberty (1975)Cbased upon OMOE well records)

Guelph Formaticn (Dolostone)

Eramosa Member (Dotostone) E2

shale) 8

LE GENO

B. STUDY DESIGN

The geochemical analyses of bottom stream sediments i n Watershed AG-10 was f i r s t approached on a reconnaissance b a s i s . of t h e bottom sediments were c o l l e c t e d , each being taken f i f t y f e e t up- stream from a road br idge l o c a t i o n during the month of May, 1976. Analyses of t hese i n d i c a t e d areas of high va lues of heavy elements w i t h i n t h e watershed, e s p e c i a l l y i n the n o r t h c e n t r a l s e c t o r .

F i f t y grab samples

To account c a r e f u l l y f o r the s p a t i a l d i s t r i b u t i o n of the chemical elements i n the North Creek Watershed, t oge the r w i th t h e i d e n t i f i c a t i o n of a l l poss ib l e po in t sources of contaminants, a more d e t a i l e d study was undertaken. This was based on 250 sample s i t e s w i th samples being taken t o a depth of t e n cen t ime te r s during the months of June and J u l y , 1976. A l l bottom sediments were analyzed f o r twenty elements and the r e l a t i v e concen t r a t ion of each was p l o t t e d on prepared base maps. Chemical a n a l y s i s of t h e bottom sediments de l inea ted an a r e a of high metal con- c e n t r a t i o n s i n t h e n o r t h c e n t r a l s e c t o r of the twenty square mile watershed. Thus, t he d e t a i l e d study confirmed the conclusions der ived e a r l i e r during t h e prel iminary study.

A f u r t h e r and more d e t a i l e d survey was e s t a b l i s h e d i n o rde r t o d i s - cover t h e o r i g i n of t he anomalous values i n t h e n o r t h central s e c t o r of t h e North Creek Watershed. chemical a n a l y s i s of bottom stream sediments, suspended sediments, s t ream waters and w e l l wa te r s ; t e x t u r a l a n a l y s i s of t he bottom stream sed i - ments; and a complete water a n a l y s i s . This included c a t i o n and anion d i s - t r i b u t i o n i n the anomalous s u r f a c e waters .

This survey was implemented by performing

A d e t a i l e d s tudy, both chemically and t e x t u r a l l y of the l i t h o l o g y of cored sediments and bedrock i n w e l l s d r i l l e d ad jacen t t o the anomalous a r e a , was made t o determine the o r i g i n of t h e anomalously high heavy me ta l s .

OESCRIPTION OF FIELD METHODS Q The anomalous n o r t h c e n t r a l s e c t o r of t he watershed was v i s i t e d

twice weekly between September 1 / 7 6 t o November 26/76, c o l l e c t i n g bottom sediments, suspended sediments and stream waters a t f i f t e e n sampling s i t e s ( s i t e s A-0 on Figure 2 ) . I n a d d i t i o n , we l l waters were c o l l e c t e d from the t h r e e piezometer d r i l l ho le s ( N I , N 2 , N3 l oca t ed on Figure 2 ) . The r e s u l t s of t he a n a l y s i s on the samples c o l l e c t e d , were designed t o show p o s s i b l e r e l a t i o n s h i p s amongst the chemical concen t r a t ions of t he fou r types o f m a t e r i a l s c o l l e c t e d i n the anomalous a r e a ,

A l l bottom stream sediments were sampled from the same l o c a t i o n s each time us ing a hand-held p l a s t i c c o r i n g apparatus ( 3 ) ; two samples being taken t o a depth of about 10 cm. a t each l o c a t i o n , These samples were then s t o r e d i n l a b e l l e d , man i l l a bags f o r l abora to ry s tudy,

Representat ive stream water and suspended sediment samples were ob- t a ined by use of a U . S , D.H. - 48 water sampler i n which the t e f l o n i n t a k e valve avoided any poss ib l e metal contamination. A t each sample l o c a t i o n , a U.S. D.H. - 48 sampler was used t o take depth i n t e g r a t e d water samples from t h r e e p o i n t s along a t r a v e r s e ac ross the stream. Water samples were then poured i n t o two, prewashed one l i t e r polyethylene b o t t l e s and l a t e r c e n t r i f u g e d i n the l abora to ry , The a d d i t i o n of two m l . concentrated n i t r i c acid as a p rese rva t ive Lo one of the one liter b o t t l e s prevented p r e c i p i t a t i o n of m e t a l l i c i o n s t o avoid spurious r e s u l t s during metal determinat ion. The o t h e r b o t t l e was not a c i d i f i e d so t h a t a determinat ion could be made of t h e so lub le elements.

Three h o l e s werta d s i l l l . t i on the >,( cc -ill b !uk <it the a n t w c ~ l o u s s i t u t o o b t a i n r e p r e s e n t a t i v e groundwater s&,pLes ds a medii5 of comparison with t h e adjacent su r face wa te r s i n the stream. I n add i t ion , samples of s o i l and bedrock from the d r i l l cdre wc1-c' an:ily:ied f o r a geochemical d i s t r i b u t i o n w i t h d e p t h from thc day1rg ; t r~ I i r f a , . ~ 112 lie underlying bedrock. The s o i l s w e r v a l s o analysed i c i t y , percentage ca rbona te s , perccntagc organic II r . 1 I i . t x . u, c . Siibs:mples were taken a t 10 cui. i i i t e r v a l s from c3 'J i r m . i i t t c rva l s from core N 2 . 'I'Iiesc iwssured parameters c o u l d i? d t o d l Cine the composition of the qua^ e r n a r y d e p o s i t s arid J i rock . The core d r i l l i n g w a s c a r r i e d out using

FIG. 2. DETAILED STUDY ON THE NORTH CENTRAL SECTOR OF THE NORTH CREEK WATERSHED

a t r u c k mounted d r i l l (CME Model 55) equipped wi th hollow stem augers from the Un ive r s i ty of Waterloo, The augers a r e 16.8 cm. i n o u t s i d e diameter w i th a hollow annulus of 8 . 3 cm. spoon sample tubes, wrapped i n p l a s t i c bags and l a t e r s t o r e d a t a tem- pe ra tu re of 4OC f o r f u t u r e l a b o r a t o r y study. A diamond d r i l l was used t o o b t a i n samples of bedrock t o depths ranging from two t o f i v e f e e t from the bedrock su r face . A t each t e s t hole s i t e , an observat ion well was i n s t a l l e d a t t h e sediment-bedrock i n t e r f a c e , c o n s i s t i n g of a P.V.C.

p l a s t i c pipe of 2.5 cm. i n s i d e diameter. were drawn up by use of a battery-powered e l e c t r i c a l water pump. l imina ry precaut ions were f i r s t taken t o ensure r e p r e s e n t a t i v e water samples. These included, t h e f l u s h i n g of t h e water pump hoses wi th double deionized water c a r r i e d t o the s i t e i n t h e one l i t e r polyethylene b o t t l e s . The pump then drew water from t h e w e l l s , r i n s i n g out i t s hoses wi th w e l l water be fo re the f i n a l sample was taken, Only one of t he two c o l l e c t e d w e l l water samples w a s a c i d i f i e d from each s i t e ,

These couple toge the r i n 1 . 7 m, l e n g t h s ,

D r i l l i n g samples a r e c o l l e c t e d through the auger annulus using s p l i t -

From these w e l l s , water samples Pre-

Geochemical environments a r e u s u a l l y expressed q u a n t i t a t i v e l y i n terms of ox ida t ion p o t e n t i a l c H as we l l as pH; these environments a r e the r e s u l t of an o v e r a l l chemical balance of t he t o t a l c o n t e n t , During the s tudy per iod of September 1/76 t o November 26/76, t h e pH measurements of t h e wa te r s were no t performed i n t h e f i e l d bu t i n t h e l abora to ry because of c l i m a t i c c o n d i t i o n s . When the pH-eH measurements on the wa te r s were performed on May 10/77 a t t h e anomalous n o r t h c e n t r a l s e c t o r of the watershed, a more accu ra t e pH measurement was made, Because temperature compensation i s necessary f o r accu ra t e pH measurement, t he temperature of t he water was d i r e c t l y read wi th a mercury thermometer. For c a l i b r a t i o n , a b o t t l e of temperature c o n t r o l l e d pH 7.41 b u f f e r was brought i n t o tem- p e r a t u r e equ i l ib r ium with the stream wa te r s f o r 15 minutes, Afterwards, the temperature compensator of the I .B.C. pH Trophy meter w a s c a l i b r a t e d according t o t h e s t reams temperature and t h e pH measured by p l ac ing the g l a s s e l e c t r o d e i n t o the pH-controlled b u f f e r s o l u t i o n while s t i l l i n temperature cqu i l i b r i , li ,) 1 _ I t I . I L ~ . A . I ~ .

For determining the eH a i the strcaui water , the eH e l e c t r o d e used w a s a Corning manufactuicd r,'nti.uum UJectrode, with a calomel r e fe rence e l e c t r o d e , Platinum ( 4 ) LS t h c rimst s u i t a b l e e l e c t r o d e m a t e r i a l f o r eH measurements; being cheiilr(.nlly i i re r t , i t does n o t p a r t i c i p a t e i n t h e ox ida t ion - reduc t ion reaction e x ~ . ~ ' p ~ a s a conductor of e l e c t r o n s . The I .B.C. pH Trophy Meter w a s u s e d t o measure the p o t e n t i a l s of the e l e c t r o d e s . The f i n a l EMF reading w a s r e c ~ r c l u d a f t e r an e q u i l i b r a t i o n time of approximately a h a l f an hour ,

The s e l f p o t e n t i a l of the stream sediment w a s a l s o measured i n a

similar fash ion , w i th the except ion t h a t the platinum e l e c t r o d e was placed f i r m l y i n t o the mud, while the r e fe rence e l e c t r o d e was s i t u a t e d near the sur face of the water as a precaut ion a g a i n s t i n t e r f e r e n c e from the clay- charged p a r t i c l e s .

The measured vo l t age of the i n e r t e l e c t r o d e r e fe rence p a i r is added a l g e b r a i c a l l y t o the p o t e n t i a l of the r e fe rence e l e c t r o d e t o der ive a t a c o r r e c t i v e eH (5) of the h a l f c e l l r e a c t i o n occuring a t the platinum e l e c t r o d e . I n a d d i t i o n , the s a t u r a t e d calomel e l e c t r o d e (sce) must be c o r r e c t e d f o r temperature (T) according t o the equation (6) :

E o ( s c ~ ) = 0.2415 - 0.00076 (T - 25)

12

9 OESCRIPTION OF LllBORllTORY METHODS

A. CHEMICAL ANALYSIS

Systemic measurement of the pH of the stream and w e l l wa te r s w a s conducted i n the l abora to ry by t h e use of a I . B , C , pH Trophy meter which w a s first s tandardized wi th b u f f e r s pH 4 and pH 8 before a c t u a l measurements were made. a t room temperature (about 2 1 C ) , S i m i l a r i l y , samples from the d r i l l c o r e s and bottom sediments were measured f o r pH by d i s p e r s i n g the sediment ( log.) i n CaC12 s o l u t i o n ( 7 ) .

Laboratory pH measurements were measured d i r e c t l y 0

Analysis f o r t r a c e elements i n the d r i l l core samples, bottom sed i - ments, suspended sediments, stream and we l l waters were determined by the A.R.L. D i rec t Reading Mul t i e l enen t Emission Spectrograph (Plasma Source) Q . A . 137. The sample p repa ra t ion of t he bottom sediments and d r i l l core samples f o r Q.A. 137 a n a l y s i s c o n s i s t e d of oven drying t h e sediment samples a t a temperature of 105OC f o r 24 hours; manually g r ind ing t h e sediments t o a powder i n a mortar ; s c reen ing the powder through an e i g h t y mesh Fcreen; weighing a 500 mg, a l i q u o t of the minus e i g h t y mesh material on a d i g i t a l Cahn Electro-balance and p l ac ing i t i n t e s t tubes; adding 10 m l . of cold 12% V.V. hydrochlor ic a c i d t o each of the samples; shaking the mixture f o r a period of e i g h t hours; c e n t r i - fuging the samples f o r t e n minutes a t 2000 r ,p .m,; decant ing the e x t r a c t and n e b u l i s i n g i t i n t o the argon stream of t h e plasma of t he emission spectrograph .

This method of cold hydrochlor ic ac id e x t r a c t i o n of m e t a l l i c e l e - ments from s o i l s and bottom stream sediments has been used ex tens ive ly i n environmental geochemistry, Although t h i s method does no t e x t r a c t the e n t i r e metal con ten t from the sediments and rock matr ix , i t does b r i n g i n t o s o l u t i o n the non-residual me ta l s which have been absorbed from the aqueous medium. This p a r t i a l e x t r a c t i o n technique (8) shows no as- s o c i a t i o n wi th the typc of rock forming the sediment and g ive r e s u l t s only f o r the weakly he ld me ta l s , which include those o r i g i n a t i n g from po l lu t ed w a t e r s , Using t h i s method, a measure can be found of t he complexed, absorbed and p r e c i p i t a t e d me ta l s i n t h ~ sediments of the North Creek Water- shed, The applications i n using the partial extraction technique for

13

ana lyses of non-residual elements has proven t o be q u i t e success fu l i n the pas t (9, 10, 11).

Suspended sediment ana lyses were performed by c e n t r i f u g i n g the sampled stream water i n t e s t tubes taken from the two b o t t l e s a t each s p e c i f i c l o c a l i t y , The suspended ma t t e r was c o l l e c t e d wi th a t e f l o n s p a t u l a from the t e s t tube,placed on a watch g l a s s and then oven d r i e d a t a temperature of 60 C , Dried suspended sediment was weighed, placed i n t o a t e s t tube and then e x t r a c t e d with 10 m l . 12% V . V . hydrochlor ic a c i d ; using t h e same e x t r a c t i o n procedure as o u t l i n e d f o r t he bottom sediment a n a l y s i s .

0

Stream and w e l l water samples were cen t r i fuged and the r e s u l t i n g decant d i r e c t l y passed i n t o the n e b u l i s e r of t he emission spectrograph.

PRECISION CHECK

Throughout the a n a l y s i s of the emission spectrograph, a continuous check on the p r e c i s i o n of t h e analyses of the sediment samples f o r poss ib l e instrument d r i f t was maintained by checking the l i n e a r working range of s tandard sediment concen t r a t ions . A sediment s tandard was made by adding approximately a gram of bottom sediments from each of the sampled watershed s i t e s t o a con ta ine r and placing t h i s on a shaker f o r e i g h t hours u n t i l a homogenized mixture was thought t o have been reached. S i m i l a r i l y , t he wa te r s were checked f o r poss ib l e instrument d r i f t by n o t i n g t h e l i n e a r i t y of ana lyses of a s tandard water made by adding 2 m l . concentrated n i t r i c ac id t o a l i t e r of deionized wa te r ,

PERFORMANCE TEST ON REPRODUCIBILITY OF RESULTS

A r e p r o d u c i b i l i t y t e s t of a n a l y t i c a l r e s u l t s and e x t r a c t i o n pro- cedures f o r the sediments w a s c a r r i e d out by weighing ten 500 mg, a l i - quots of t he prepared sediment s tandard and e x t r a c t i n g the samples each wi th an equal amount of 12% V.V. hydrochlor ic a c i d . The r e s u l t s wh ich i n d i c a t e b a s i c a l l y the a b i l i t y of the e x t r a c t i o n with cold hydroch1c.r i

ac id and the emission spectrograph t o reproduce s i m i l a r numbers from the s i n g l e composite s tandard of the type of m a t e r i a l t o be t e s t e d a re shown i n Table 1. I n a d d i t i o n , a comparative t e s t f o r the elements, Cu, N i , P b , Zn, w a s conducted t o compare the a n a l y t i c a l r e s u l t s obtained w i t h the emission spectrograph (Q.A. 137) and the atomic absorpt ion spectrometer ( A . A . S . Perkin-Elmer Model 403) . This showed t h a t the c o e f f i c i e n t o f v a r i a t i o n f o r the emission spectrograph i s l e s s than t h a t f o r atomic absorpt ion. For example, the c o e f f i c i e n t s o f v a r i a t i o n f o r lead werc

1.4

TABLE I - PRECISION TEST ON SOIL STANDARD

(i, e. 10 duplicates)

(Note: All Samples Performed on Q,A.137; exception(*)on A.A.S.)

ELEMENT STANDARD DEVIATION

(l%/g)

COEFFICIENT OF VARIATION

(%) ~ ~~

260-280

860-900

250-266

2060- 2280

249-263

8-8.6

38.2-39 -13

270 10.54 3.9

K 878 11.35 1.29

Sr

si

258.4 4.79 1.85

2158 71.46 3.31

254 6 As 4.60 1.81

Cd

Cr

8.56 .21 2.41

39.14 .55 1.41

co

Mo

Ti

CU

* cu Ni

JX Ni

Pb

JX Pb

If,- 14

20-26

38.2-42.6

12.0-13.8

12- 12

12- 12

20. I!<

56- 60

3 0 - 3 6

14

23.4

40.16

13.38

12

12

12.4

57.8

33

0

1.90

1.42

.41

0

0

1.27

1.14

2.36

0

8.11

3.54

3.1

0

0

10.2

1.96

7.2

1.25

1.84

1.95

2.43

1.96% by emission spectrograph and 7.2% by atomic absorpt ion (Note however, t h a t t h e r e s p e c t i v e mean Pb va lues f o r the two instruments vary s i g n i f i c a n t l y i n concen t r a t ion ) . Thus, the emission spectrograph seems t o be more p rec i se than t h e atomic abso rp t ion f o r most of t he elements s t u d i e d .

Analyses of water were a l s o subjected t o a similar t e s t f o r r e - p l i c a t i o n of t he r e s u l t s . a s i n g l e s i t e were analysed and the mean and v a r i a t i o n s c a l c u l a t e d . showed a low c o e f f i c i e n t of v a r i a t i o n as i n d i c a t e d i n Table 2 , y e t no t as low as t h a t achieved i n the sediments r e p r o d u c i b i l i t y t e s t i n Table 1,

Five samples of a s i n g l e batch of water from These

O v e r a l l , Barr inger (12) had found t h a t t he emission spectrograph has comparable l i m i t s of d e t e c t i o n and p r e c i s i o n t o the atomic absorpt ion spectrometry and t h a t i t has a g r e a t e r s e n s i t i v i t y i n the case of some elements ,

PERFORMANCE TEST ON ANALYTICAL METHODS

This t e s t r e q u i r e s t h a t the sediment s tandard be weighed i n dup l i - c a t e s ranging from 0 . 1 gram t o 1 .0 gram i n c l u s i v e l y a t 0 .1 gram i n c r e - ments. Both sets were e x t r a c t e d with 12% V.V. hydrochlor ic a c i d , To one s e t , a f i x e d concen t r a t ion of an element known t o be present i s added (The sample i s sp iked) , This "method of a d d i t i o n s t e s t " , i f p l o t t e d wi th o r i g i n a l sample weight ve r sus element concen t r a t ion should t h e o r e t i c a l l y have two p a r a l l e l l i n e s , t h e lower l i n e passing through the o r i g i n which i f so would suggest t h a t the a n a l y t i c a l a n a l y s i s f o r t h a t element i s f r e e from b i a s , Also, t he two p a r a l l e l l i n e s should be sepa ra t ed by the amount of known spike add i t ion . The accuracy of t he analyses i s i n d i c a t e d by the c loseness t o the t h e o r e t i c a l . Figure 3 i n d i c a t e s t h a t the analyses by the emission spectrograph f o r the elemeiiLs Sr, Zn, and Cu a r e accu ra t e and f r e e from b i a s . There i s some p o s i t i v e b i a s f o r Pb. The atomic absorpt ion ana lyses correspond i n general t o t hose of t he emission spectrograph i n accuracy, although the elements ZII, Cu and Pb a l l have p o s i t i v e b i a s as shown i n Figure 3 . Nickel, when determined showed an e x t r a c t i o n de f i c i ency i n the upper weights from 0.6 grams t o 1 .0 grams and a l s o a corresponding b i a s i n each of t he a n a l y s i s . Although the abso lu te n i c k e l values may be erroneous, the va lues a r e u s e f u l i n t h a t comparisons may be made wi th m a t e r i a l t r e a t e d i n the same way during r e g i o n a l reconnaissance,

The amounts of Zn, Cu, Pb and N i determined from the performance t e s t s made on the emission spectrograph were p l o t t e d a g a i n s t those from the t e s t s on the atomic absorpt ion spectrograph and the r e s u l t s a r e shown i n

16

ELEMENT

Na

K

Sr

si

As

N i

Pb

Zn

PRECISION TEST ON WATERS

(i.e. 5 duplicates)

NOTE: A l l Samples Performed on Q.A. 137

11.3-11.7 11.5 .187

11.3- 12.4 11.52 .492

.539-. 555 .545 ,007

4.00-4.94 4 .52 .396

2.33-2.58 2.402 ,102

,145-. 194 .16 ,020

1.06- 1.21 1.098 ,065

,357- ,394 .367 .016

COEF’FICI ENT OF VARIATION

(%I

1.63

4 .27

1 .20

8 .75

4 .25

12.56

5.92

4 .38

L

W

KZ

O

Y

Lo

m

- W

a,

fi

I '

:

FIG. 4.

COMPARATIVE ANALYSES BETWEEN EMISSION AND ATOMIC ABSORPTION

P ’E b c a, U

a

0

Parts per million determined by ATOMIC ABSORPTION

Parts per million determined by ATOMIC ABSORPTION

20

f o r a per iod of e i g h t hours , spectrometry a n a l y s i s

The r e s idue was then c o l l e c t e d f o r mass

C . 'L'ESTURAI ANALY S I S

p a r t i c l e s i z e a n a l y s i s was chosen t o provide informat ion about t he s i z e f r a c t i o n i n t h e s t ream sediments and i n the core N I sediments, where t , a ( t i i t ?-.I[ ioi i , L j f anomalous t r a c e elements occur , I n a d d i t i o n , the t e x t u r e g ives informat ion concerning the c l a s s i f i c a t i o n of t he Quaternary d e p o s i t s , Grain s i z e a n a l y s i s was performed by the p i p e t t e method ( 1 5 ) .

The r e s u l t s from t h e d e t a i l e d geochemical s tudy on bottom stream sediments from Watershed AG-10 a re shown i n F igures 5-25 i n c l u s i v e l y , i n which t h e r e l a t i v e concen t r a t ion of each element i s p l o t t e d a t the r e s p e c t i v e loca t ion . The anomalous n o r t h c e n t r a l s e c t o r of the watershed i s i n d i c a t e d by h igh concen t r a t ions of N a , K , S r , S i , As, Pb, Zn, Cd, N i , T i , Ag, Sn and Mo shown i n F igu res 5-17; low concen t r a t ions of Be and Fe i n F igu res 18 and 19 and random concen t r a t ions of A l , Mn, Cu, C r and P i n F igu res 20-24 i n c l u s i v e . Overa l l , t he re i s a f a i r l y uniform d i s t r i b u t i o n of Y a s shown i n F igure 25 d i spe r sed throughout the e n t i r e watershed, What fo l lows i s a geochemical hypothes is t o exp la in the o r i g i n of t he anomalous s i t e i n the n o r t h c e n t r a l s e c t o r of t h e North Creek Watershed.

The anomalous a r e a w a s e x a i i n e d f o r poss ib l e r e l a t i o n s h i p s e x i s t i n g between t h e bottom sediments, suspended sediments, s t ream waters and w e l l wa te r s ; i n o t h e r words, t he four parameters s tud ied . Samples of these fou r types of m a t e r i a l were taken biweekly f o r a t o t a l of fou r t een weeks, The concen t r a t ions of each of the twenty elements were measured f o r each sample and t h e r e s u l t s shown i n F igures 26-45 i n c l u s i v e l y ,

A s a means of demonstrat ing the va lues obta ined f o r ana lyses of t h e fou r types of m a t e r i a l (F igures 26-45 i n c l u s i v e ) i n t h e anomalous a r e a of the nor th c e n t r a l s e c t o r , the botLom sed imen t s a r e grouped i n t o t h r e e c a t e g o r i e s , The f i r s t group i s the geochemicai i nc rease i n coi,ccnt x-dt- iot i w i t h t h e time dur ing the sample c o l l e c t i o n period f o r e lements Na, K , %n, Pb, Cd, N i , C r , and Sn; t he second group a s the s t a b i l i t y of t he chemical concent ra t ions w i i 11 > I,

and t h 6 t h i r d , t l l c nic. l i coIIL(;iitl I I L O ~ . ; w i i t i i i n i u t x r e ~ ~ I Tor a decru;ise j n i ) c T L ~ # ~ - o l e x i i t s Ca, S I , Ag, and A s ,

I ’ / L111d C I l . L’ :

The s t i i dy f o r t h ( s i i b p t > t t t ; ~ ‘ c l sediint~iits i s d iv ided i n t o th ree c a t e g o r i e s , Thost: elenients increasit l i , ’ i i r I i enti.iL-il)ns wi th time a re K , P , C d , T i and Sn; the elements S i P’I M i l , !%e, Cu, Cr, N i , Cd, and A s which S I i g h t l y increase t h c i r <‘c)nc CI; 1 L II:, wi th t ime; and l a s t l y , those e l e - ments t h a t slightly i n c r c i:,c t 1 ~ ~ 1 1 r coric-Lnt-raLions wi th t ime, wi th the ex- c e p t i o n €o r a decrcsaso L : L t : b , , . L I I of October a re elements Ca, Na, S r , Z n , Ph , arid Ag.

FIG. 5. TRACE ELEMENT DISTRIBUTION FROM BOTTOM STREAM SEDIMENTS IN THE NORTH CREEK WATERSHED

r- \

I

I I I

I I I n

W I

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k2

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I Propct NO 23

,

8/16/76

5 21 -\

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__- - - _ _ _ _

FIG. 15. TRACE ELEMENT DISTRIBUTION FROM BOTTOM STREAM SEDIMENTS IN THE NORTH CREEK WATERSHED

c3 W

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Prcpored by ERIC VESKC Brock Un YeT%!)-

Drott-d by R ASNEW 8 E J E S U I FIG. 19. TRACE ELEMENT DISTRIBUTION FROM BOTTOM STREAM SEDIMENTS IN THE NORTH CREEK WATERSHED

j

i'

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i.' M

LEGEND -__

e 0 0 8 0 0

_____ __

Prepwed by ERIC Brock V E S U b UnlvCrllty FIG. 22. TRACE ELEMENT DISTRIBUTION FROM BOTTOM STREAM SEDIMENTS IN THE NORTH CREEK WATERSHED

O 5-11 0 + 5

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t- 3

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t- CK

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t- z UJ k- 6

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A PiePotea by ERIC V E S K I FIG. 25. em<" Y" *e'lliy 1 TRACE ELEMENT DISTRIBUTION FROM BOTTOM STREAM SEDIMENTS IN THE NORTH CREEK WATERSHED ciotted by a ASNEA 6 i VESKA

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GEOCHEMICAL

FIG. 3 6 .

FIG. 3 7 .

COMPARISON AMONGST FOUR MEASURED PARAMETERS IN THE ANOMALOUS NORTH CREEK WATERS

cu OCT 13 / 76

A . c o I I o n , 1 * I Y M 0

BITE LOCATIONS

OCT. 26/76 NOV. 12 / 76

. I

NOV. 26/76

!=

- bttan Sediments ___ Surpnded Sediments ...... f)r.anWmt- . WI Water

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I- 8 .n . OD h UI

CR c. . c!J H

Fr

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The stream wa te r s may be divided i n t o fou r groups. The f i r s t group c o n s i s t e d of elements whose concen t r a t ion does no t vary wi th time, such a s Ha, K, S r , Cu, C r , S i and Be. The second group P, Zn, Pb, Cd, A s , N i and Sn a r e those i n which the chemical concen t r a t ion inc reased ab rup t ly from September 28/76 t o October 13/76. chemical concen t r a t ions f o r Fe, A l , Mn and T i , decreased wi th t ime, The l a s t group c o n s i s t e d only of calcium, the chemical concen t r a t ion of which does n o t f l u c t u a t e g r e a t l y w i t h time, except f o r a sudden decrease on October 13/76.

During the same per iod, t he

Extreme anomalous cond i t ions a r e w e l l def ined f o r s i t e "1-I" i n F igu res 26-45 i n c l u s i v e and i n Appendix 1 f o r the November 26/76 c o l l e c t e d samples. A gene ra l obse rva t ion of s i t e rrHf' i n d i c a t e d t h a t N a and Sr a r e the only elements which show a p o s i t i v e c o r r e l a t i o n i n the geochemical d i s t r i b u t i o n p a t t e r n s of t he f o u r s tud ied m a t e r i a l s , bottom stream sediments, suspended sediments, stream wa te r s and wel l wa te r s , A p o s i t i v e c o r r e l a t i o n i n the geochemical p a t t e r n s e x i s t e d betwcen the w e l l wa te r s and s t ream wa te r s f o r most of the elements s t u d i e d . I n a d d i t i o n , t he elements Cay Mn, Zn, Pb, Cd, Ag, N i , and C r a t s i t e "H" have s p a t i a l l y a d i r e c t r e - l a t i o n s h i p amongst t h e suspended sediments, stream and we l l wa te r s y e t an i n d i r e c t r e l a t i o n s h i p wi th the bottom sediments, Elements t h a t a r e high only i n scspended sediments a r e K , S i , Fe, A l , Be, A s , T i and Cu,

S i t e "L" w a s f a i r l y anomalous r e l a t i v e t o s i t e "H" i n t he geochemical d i s t r i b u t i o n p a t t e r n s f o r both the bottom and suspended sediments, as shown f o r Zn, Ag, Sr and C a i n Figures 30, 3 7 , 26 and 28 r e s p e c t i v e l y ,

I n o rde r t o discover the reason f o r the l ack of s i m i l a r i t y between the a n a l y t i c a l r e s u l t s f o r t he bottom stream sediments and the o t h e r t h ree types of m a t e r i a l (suspended sediment, stream waters and wel l .nsaters:, a program of more d e t a i l e d measurement was embarked upon. t e x t u r a l ana lyses , mass spectrometry, c a t i o n exchange capac i ty and l o s s on i g n i t i o n f o r t he bottom sediments. Mass spectrometry n x m l y ~ c ~ nrude on the bottom sediments showed m i d l 1 cliaincd l r y d ~ c v ~ k~rl>on:; Lc t 1'1

i n a l l of t h e f i f t e e n sampled s i t e s ; Iiowevcr, oiily s i t c s "k1" m u "Pi" contained elemental s u l f u r . Cai-ion exchauge c a p a c i t i e s were fourid t o in- c r e a s e f o r s i t e s "H" a t 44.7 iiieq/100 g. and I'M" a t 44.7 rueq/100 g . a s shown i n Figure 46. S i m i l a r i l y , the organic ma t t e r c o n t e n t , shown i n Figure 4 6 , i nc reased i n r e l a t i v e percent a t sLlres "H" (9.89%) and "M" (9 .70%). I n c o n t r a s t , t he r e l a t i v e per n l u ) t o L a 1 ccxhonates (Figure 4 6 ) decreased a t s i t e s "H" (15.5%) and "p;?' (J4,$L), y e t i nc reased a t s i t e s "1" (19 .4%) , "IC1' (19.9%) and "L" ( 2 1 , 8 % ) ~ ~ i i c i : e v i d e n t l y corresponds wi t11 the pH in- c rease f o r t he l a t t e r s i t e s 111 Pigarc 4 6 , Gcain s i z e anaLTrst's (Figure 46) on the bottom stream sediments revealed t h a t t he s i z e O F sLtiid Lrnct ion

This included

a

cn w

I

I- z E

W

CL a

Li z 0

I- t- 0

w

m

$E X

P n

a

z

d P

i

- .~

S

31VN

O8tiV

3 1

ViO

i %

i nc reased downstream corresponding t o a decrease i n t h e mean s i z e of the c l a y s i z e f r a c t i o n , f a i r l y cons t an t i n s ize , s t ream sediments are summarized i n Appendix 2.

With t h i s , t h e s i l t s i z e f r a c t i o n however remained The d e t a i l e d t e x t u r a l analyses f o r t he bottom

Surface water ana lyses performed by t h e Min i s t ry of t h e Environment on t h e November 26/76 water samples a r e shown i n Table 3, f o r t h e cat ion-anion balance f o r t hese n a t u r a l wa te r s , The anomalous s i t e llH1l contained h igh concen t r a t ions of Na, Ca, Mg, SO +, NOj, a l k a l i n i t y and low concen t r a t ions of K, C 1 and NH3 i n t h e wa te r s , n ad i t i o n , the waters a t s i t e "HI1 showed i n c r e a s e s i n s p e c i f i c conduc t iv i ty up t o 2500 pmho/cm,; c a l c u l a t e d t o t a l d i s so lved s o l i d s up t o 2047 mg/l; and i o n i c s t r e n g t h up t o 0.06, These s u r f a c e water analyses a r e diagrammatically shown i n Figure 47,

Table 4 accounted

The geochemical d a t a have o u t l i n e d the gene ra l anomalous n o r t h c e n t r a l s e c t o r w i th r e fe rence t o s i t e "H1' e s p e c i a l l y , and s i t e s "L" and l'M1l i n F igu res 26-45, underground s p r i n g o r f i c e on the south c reek bank a t s i t e "H". presence of bubbles emanating from t h e o r f i c e and the occurrence of ye l - lowish and reddish-brown r e s i d u e s , were e s p e c i a l l y ev iden t i n the sp r ing , The s p r i n g water: were much c o l d e r (8OC) than t h e average su r face water temperatures (18 C) as i n d i c a t e d from Table 5, It should be noted t h a t s i t e s "L" and ' W 1 a l s o have low water temperatures a t about 15 C and 14 C r e s p e c t i v e l y , Study of t h e eH-pH r e l a t i o n s h i p s i n the anomalous a r e a , as shown i n Table 5, i n d i c a t e s t h a t t h e su r face and s p r i n g wa te r s show the e x i s t e n c e of an o x i d i z i n g environment. Observation of Table 5 in - d i c a t e s t h a t t r a n s p o r t a t i o n of s p r i n g water from the s p r i n g ' s o r f i c e t o s i t e "H",increases t h e eH from +,154 v o l t s t o +.240 v o l t s and s i m i l a r i l y for t h e pH, as from 7.2 to 8 . 5 . The eH-pH r e l a t i o n s h i p i n t h e sediment- water i n t e r f a c e are similar t o those of the eH-pH of the anomalous sur- f a c e waters . For example, Table 5 r e l a t e s t he d i f f e r e n c e from the s p r i n g s i t e bank t o anomalous s i t e llH1' as an i n c r e a s e i n pH from 7.1 t o 7.3 and eH from +.005 t o +,140 v o l t s ,

Closer i n v e s t i g a t i o n l e d t o the discovery of an The

0 0

A drawing of t h e logs of t he we l l c o r e s from t h e anomaly s i t e showing t h e c o r r e l a t i o n between t h e m a t e r i a l s encountered i n each co re i s shown i n Figure 48. Wells N3, N 1 and N2 were d r i l l e d r e s p e c t i v e l y ad jacen t t o s i t e s "B" , "H" and "L" , A geo log ica l d e s c r i p t i o n of t h i s c r o s s s e c t i o n shown i n Figure 49 inc lude t h e Lockport and Guelph Dolostone Formations; t h e Halton till where Appendix 3 matches the c o r e ' s till d e s c r i p t i o n wi th the l o c a l till composition found nearby; and the Lake Warren g l ac io l acus - t r i n e s i l t s and c l a y s which i s i d e n t i f i e d from the s t r a t i f i c a t i o n of varves

57

TABLE 3 - SURFACE WATER mALYSIS FROM THE ANOMALOUS STUDY AREA

(waters sampled on Nov. 26/76)

LOCATION

CONCENTRATION UNITS

Fe Ca

Q3 Na K

xLKASIf?IPY C f SO4 N03( as N) NO2( as h7)

si02

MI3 ( as N) SOLIJBLE P

TOTAL DISSOLVED SOLIDS

I O N I C STREWGTH SPECIFTC CONDUCTANCE

(rnirsomhos @ 25'C) pH @ 2O0C

PCO? L.

A

(%/I) 5.31 092

94,O '

44 1 7 10.5 162.2 %-LO 175 518

.043

. 9 2 1 ,021 5 i ,

,014 * . 9

7.5 -: "29

B

(mg/l) 1.41 ,092 124 64 17.5 50 209.7 195 240 .270 ,128 .219 ,023 794

.020 1320

7.4 -1.82

F

( m d l ) 4.23 .138 76 29.5 9.5 14 74.4 61 170 ,217 '.020 ,061 .060 397

.OlO 640.

7.8 -1.76

H

(mg/l) 1.41 ,092 145 2 60 87.5 11 241.4 28 1387 9.30 .220 ,143 .018 2047

.060 2 500

8.2 -2 A 1

J

(mg/l) 2.12 ,184 103 92 45 10 318,2 75 380 .027 .013 .061 ,025 862

.022 1330

8.3 -2.42

L

(mg/l) 4.95 .046 117 66.5 35 10.5 274.3 70 330 ,239 .020 .143 .026 7 64

.018 1150

8.1 -3.22

I" a lo I 8 km

M

(mg/l) 0.71 .138 61 49.5 28 10.5 182.9 55 170 2.466 ,076 .219 .026 466

.012 7 60

8.1 -1.54

( m d l ) 1.41 092

71 49 34.5 30.5 267 70 170

,131 2.125 .082 557

,011 880

7.7 -1.32

.28a

TABLE 4 CATION - ANION BALANCE ON THE SURFACE WATER ANALYSES (waters collected on N o v . 26/76)

.*- I to Lbkm

C a 4.691 6.188 3.792 7.236 5.140 5.838 3.044 3.543

Mg 3.619 5.265 2.427 21.39 7.568 5.47 4.072 4.031

1.501 1,218 Na .74 .761 .413 3.806 1.96 1.523

K .269 1.279 .358 .281 .2 56 .269 .269 .780

lJl TOTAL CATIONS 9.325 13.502 6.996 - ' 32.733 14.9313 13.109 9.608 9.861

ALKALINITY 2.658 3.437 1.219 3,957 5.216 4.496 2.997 4.376

rD

c1

so4

NO3

TOTAL ANIONS

PERCENT DIFFERENCE (%) BETIWEN CATIONS & ANIONS

Ca/Mg

3.103 5.501 1 . 721

3.644 4.997 3.539

,00837 .00439 .003 5

9.414 13.941 6.484 .

,952 3.253 7.89

1 . 3 1 .2 1 .6

1.975 1.552 ,790 2 . 116 1.975

28.877 7.912 6.871 3.539 3.539

,150 .OW29 .003S5 ,0398 .00487

9.896 8.131 38.787 15.246 13.347

3.221 2.11 1.816 5.87 .359

.34 .68 1 . 1 .75 .88

nco3/so4 ,729 .688 ,344 ,137 ,659 .654 .847 1.237

FIG. 47. WATER

35

c.

t c .- - L

25

Y

z t- 4 LL

0

k 15 w 0 z 0 c)

IO

5

0

CHEMISTRY OF THE ANOMALOUS SITE AS REPRESENTED BY VERTICAL BAR GRAPHS

LEGEND

F

H

J t

0 .3 I .7 2.2 2.'9 3:s 3:7 DISTANCE (miled DOWNSTREAM FROM SITE 'A" -

0

4 -4

TABLE 5 - Eh - pH RELATIONSHIPS - (measured May 10/77)

WATERS

SEDIMENT -WATER INTERFACE

LOCATION

TEMPERATURE ('C) (AIR TEMP. (3 17.c)

PH

eH (volts)

PE

PH

eH (volts)

PE

L M 0 - J - H SPRING - . F - B - A - SITE

20 19 19 8 14 17 15 14 17

7.7 7.4 7.9 7.2 8.5 8.0 8.5 8.4 8.0

+.365 +.385 +.350 +.154 +.240 +.411 +.304 +.385 +.375

+6.29 +6.65 +6.05 . +2.77 +4.22 +7.15 +5.33 6 . 7 7 +6.52

6.9 7.0 7.0 7.1 7.3 7.0 7.5 7.0 * 6.8

+.195 +.220 +.191 +.005 +.140 +.185 +.149 +.190 +.193

+3.36 +3.80. +3.30 + .09 +2.46 +3.22 +2.59 +3.34 +?.36

G. 48.

E

5

CROSS SECTIONALVIEW OF WELL CORES AT THE ANOMALY SITE OF THE NORTH CREEK WATERSHED

3 = ~ E q . L 7 1 - WELL N3 - - - . - - -.- - - - - - .V C a f l - m

LEGEND

\

Water T i b l e (August 3 : ' ; - ' \ \

Dolos tone \ \

Vugs c o n t a i n i n g c e l c i - r - y s t a l s s ? ' na -e r l t e and g a l e r c - , I 7 r a l s

LOCAT ION -

FIG. 49.

GEOLOGICAL DESCRIPTION OF THE CROSS-SECTION AT THE ANOMALY SITE

I -5-

I co I I co I

Soi l Horizon

rb

AB

Lake Warren Glocidoarhinr Cs Silts md clays

CO

Halton Till C t

SOIL PROFILE LEGEND

Description

Organic matter accumulation

Gley zone, # i l t y clay

Gleyed zone undergoing per iodic reduct ion, dominantly a clay texture

S i l t y sand layer

S i l t y clay horizon; evidence of varves near the Co/Ct interface

Silty clay till

The m a t e r i a l s found i n co res N 1 and N2 were examined i n order t o de t e r - mine the geochemical c i r c u l a t i o n of the major and minor c o n s t i t u e n t s towards the anomalous s i t e s "H", "L" and W"M' through i n t e r a c t i o n by spr ings and seeps , N 1 and N2 r e s u l t e d i n a few c h a r a c t e r i s t i c p a t t e r n s , increased i n concent ra t ion j u s t above the water t a b l e (measured August 31/76) and very s l i g h t l y i n t h e till l aye r f o r both co res were heavy metals such as Zn, Pb, A s , Cd, Ag, C r , N i , Mo, Cu as shown i n Figure 50; those elements t h a t increased i n concent ra t ion j u s t above the water t a b l e and i n the till l a y e r were t h e elements having so luble salts Ca, N a , K, as shown i n F igure 51; elements t h a t were d e f i c i e n t i n concent ra t ion a t the water t a b l e and a l s o i n the till l a y e r were Fe, Al, Be, S i , S r , T i , shown i n Figure 52; and f i n a l l y , those elements wi th a random d i s t r i b u t i o n were Mn and P shown i n Figure 51.

A geochemical d i s t r i b u t i o n wi th depth on core sediments from we l l s Those elements t h a t

Chemical c h a r a c t e r i s t i c s toge ther wi th t e x t u r a l analyses were s tud ied w i t h depth on core N 1 which seemed t o be the most anomalous i n terms of e lemental concent ra t ions as shown i n Appendix 4 and Figures 50, 51 and 52. Appendix 5 and Figure 53 show t h a t pH va lues f o r the core sediments are the h ighes t (pH 8.2) when measured j u s t above the water t a b l e (recorded August 31/76), S i m i l a r i l y , the c a t i o n exchange capac i ty , percent organic mat te r and percent t o t a l carbonate va lues inc rease i n the upper s e c t i o n of N 1 3 j u s t above the water t a b l e as 29.3 meq/lOOg., 4.9% and 25.2% respec t ive ly i n F igure 53. of Figure 53. It i s noted t h a t the lower s e c t i o n of N 1 3 j u s t below the water t a b l e con ta ins the h ighes t sand percentage a t 31.8%.

Textura l a n a l y s i s on core N 1 l ed t o the c h a r a c t e r i s t i c p a t t e r n s

FIG. 50. GEOCHEMICAL CORE INVESTlGATlON ADJACENT TO THE ANOMALOUS NORTH CREEK WATERS l m R S - UTUST Y m l

LE- 8 a t r Td* l4Y. I9761 BJra--run. .-ca* m.h B M tr. * I * rs

As Cr

FIG. 51. GEOCHEMICAL CORE INVESTIGATION ADJACENT TO THE ANOMALOUS MORTH CREEK WATERS (CORES [Y)ILLED AUGUST 3J9761

LEGEND mWta Table (Aug31.1976) gl ~ ~ d r o d c - Dobeme HSeUImnI Cue Analysts OWock Cue Anolysrs

K

FIG. 52. GEOCHEMICAL CORE INVESTIGATION ADJACENT TO THE ANOMALOUS NORTH CREEK WATERS (CCfES ORLLLED W T 3lJ9m)

LEGEN) @ W d W Toble (AW 3,1976) Becdroc* - Dmrtm

n&drock C a e r\naiyws %dhnmt CWC Analysis

I- P

68

OISCUSSION OF THE RESULTS AND DATA INTERPRETATION II The compilation of geochemical patterns from cores N1 and N2, led to

the conclusion that the upper N13 section is anomalous with respect to its surrounding horizons. Heavy metals, such as zinc, have a concentration in the sediments of the N13 layer above the level of the water table (measured August 31/76) four times greater than that of the sediments in the adjacent core at N23 also above the water table level (measured August 31/76). This is shown in Figure 50. Similarily to sections N13 and N23 adjacent to stream sites "H" and "L" respectively, the concentration of zinc in bottom sediments at site "H" is greater than that at site "I," by ten fold (Figure 11). Therefore it was decided to study the lithology and geochemistry of the core N1 sediments to determine if other correlations exist between the N13 section and that of the adjacent stream site "H".

Figure 54 illustrates the close association in geochemical distribution patterns for the high concentrations Sr, Ca, Na, K, Zn, Pb, As and Ni 'with chemical patterns for increasing amounts of pH, cation exchange capacity, percent organic matter and percent carbonates above the water table (measured August 31/76) in the sediments in the upper section of N13. Below and at the water table level in the lower section of N13, the Fe, Al, Si, Be and Ti chemical concentrations tend to decrease in this sandy horizon, The deficiency of the Fey Al, Si and Be concentrations is explained by the lack of clay (ie. Figure 5 4 ) ; while titanium's apparent deficiency at the water table is explained by its immobilization in the stable 4+ oxidation state in an oxidizing environment,

Note that the cation exchange capacity and percent organic carbon is very high in both the bottom sediments at site "H" 44.7 meq/100g, and 9.9% respectively and the sediments in the upper N13 layer 29.8 meqI100g. and 4.9% respectively.

Figure 55 shows that the lower section of N 1 3 (sediment sample No. 15

69

FIG. 54. COMPARISON AMONGST THE GEOCHEMICAL, CHEMICAL. AND TEXTURAL PARAMETERS ON THE SEDIMENTS FROM WELL CORE N"f

FIG. 55.

TEXTURAL COMPARISON BETWEEN BOTTOM STREAM SEDIMENTS OF THE STUDY AREA

AND SEDIMENTS FROM CORE 'IN I"

POSITION DOWNSTREAM-(le A - 0 iw1ustve)-

n. ... I ,a1.

71

l oca t ion wi th depth) , b e s t f i t t e d the t e x t u r a l dimensions of the bottom sediments a t s i t e "H" r a t h e r than the upper N 1 3 s e c t i o n (sediment sample No. 13 l o c a t i o n wi th depth) , In add i t ion , t h e heavy metal concent ra t ions , such a s 500 ppm f o r Zn i n the bottom sediments a t s i t e "H" corresponded b e s t t o the 500 ppm f o r Zn concent ra t ion i n the sediments of the lower s e c t i o n of N 1 3 r a t h e r than the 2000 p p Zn concent ra t ion i n the sediments of the upper N 1 3 s ec t ion . charging towards the su r face , may move l a t e r a l l y through the sandy sedi - ments of the lower N13 l aye r towards the day l igh t sur face a t s i t e "H", while sediments of the upper N13 l aye r c o l l e c t the bulk of the major and minor d isso lved c o n s t i t u e n t s i n the organic f r a c t i o n ,

Therefore , i t appeared t h a t groundwater d i s -

This suggested t h a t i t may be poss ib le t o c o r r e l a t e the water q u a l i t y d a t a , e s p e c i a l l y the d isso lved elements with the underlying bedrock com- p o s i t i o n and na ture . Surface water da t a , concerning the concent ra t ions

of major c a t i o n s , C a Mg , K , H , and anions C 1 , SO4 HCO3

OH , S i 0 2 , were ca l cu la t ed t o l i s t ion spec ia t ion by a WATFIV computer program (16). This mixing c a l c u l a t i o n i s dependent upon the t o t a l concent ra t ions of the major element spec ie s , temperature and pH, which then d i s t r i b u t e d the

ions i n t o ion p a i r s such as:

CaS04 , CaHC03

- -- tt ff + + -

- 0

0 + 0 + 0 + H2CO3 , MgOH , MgS04 MgHCO3 , MgC03 , CaOH - - 0 + 0 0 0 0 -

CaC03 , NaS04 , Na2S04 , NaC03 , Na2C03 , NaCI , KS04 , 0 0 0 --

K C I O , HSO4-, H2SO4 , H C I , HqSi04 , H3Si04-, and H2Si.04 , and then l i s t s

them i n t o the r e spec t ive p a r t s per mi l l i on , mo la l i t y and a c t i v i t y u n i t s . N o t e t h a t the t o t a l concent ra t ions f o r each element a re def ined by similar

r e l a t i o n s h i p s t o t h a t f o r magnesium i e ,

MgS04 t MgHC03 -6 MgC03 . 1.n L idd i t ion , t he computer program ca lcu la t ed

++ + =Mg + M @ H + Mgt 0 t a 1

0 + 0

the p a r t i a l p ressures of caxt.)on dioxide and the s a t u r a t i o n i n d i c e s (S .T . ) f o r minera ls der ived from the above ion spec ia t ion p rocess . For example, cons ider ing each of t h e mineral's s o l u b i l i t y product (Ksp) a t a s p e c i f i e d temperature near 0 C ( t h i s was the approximate temperature a t which the waters were srinipl*:cl nil NoveLnbt'r 26 /76) and i t s r e spec t ive i o n i z a t i o n product (KIP). d aolit(.lorl LJI I1 be thermodynamically over- s a tu ra t ed with r e spec t t < \ T( r e i , i i i q nincral, i f the l a t t e r (KIP) exceeds the former ( ~ s p ) , L i t t lus way i t may be poss ib le t o i d e n t i f y concent ra t ions of unusual cons t i t u c n t s i n groundwater and sur f ace water

0

a t the anomalous s i t e , and thus provide a n a t u r a 1 , t r a c e r by which the bedrock source of the water can be i d e n t i f i e d (17). For example, the ind iv idua l mineral s a t u r a t i o n i n d i c e s w i l l i n d i c a t e whether d i s s o l u t i o n o r p r e c i p i t a t i o n processes occur a t a c e r t a i n s i t e i n these n a t u r a l waters .

Reference t o Figure 56, i n d i c a t e s t h a t minera ls such as b r u c i t e , hydromagnesite, nesquehoni te , and h u n t i t e were a l l undersaturated i n the sur face waters , whereas minera ls l i k e a ragon i t e , magnesite, c a l c i t e and dolomite were a l l s a tu ra t ed o r even supersa tura ted i n the anomalous sur- f ace waters ( e s p e c i a l l y s i t e s "H", "1" and "L"). Note t h a t the n a t u r a l waters a t s i t e s "I" and "L" i n Figure 56 a r e both supersa tura ted f o r the l a t t e r s e t of carbonates , while the waters a t s i t e "H" a re only a t the s a t u r a t i o n point f o r those minera ls . This corresponded wi th t h e i r abundance of carbonates i n the bottom sediments a t s i t e s "H", "I" and "L". Furthermore, a c t i v i t y and predominance diagrams a r e convenient ly provided so as t o r ep resen t a graphic summary of the mineral sequences i f equi l ibr ium were a t t a i n e d . The a c t i v i t y diagram (18) i n Figure 57, where the log a c t i v i t y r a t i o of Mg:€? versus the log a c t i v i t y r a t i o of Ca:H , show t h a t the sur face waters throughout the anomalous North Creek sec t ion a r e more s t a b l e i n the dolomit ic phase r a t h e r than the magnesite of c a l c i t e phases. The predominance diagram (19) i n Figure 58 provided add i t iona l information, t h a t the anomalous sur face waters a re i n s l i g h t equi l ibr ium between the a rgon i t e and h u n t i t e metastable phases y e t completely e q u i l i b r a t e d i n the dolomi t ic s t a b l e phase. Therefore , the sur face waters along the anomalous s e c t i o n seem t o have some con t r ibu t ion of carbonate c o n s t i t u e n t s from the Lockport and Guelph Dolostone Formations through groundwater i n t e r a c t i o n s .

2

The r a t i o of Ca:Mg i s use fu l in s tudying waters der ived from car - bonate rocks. The Ca:Mg r a t i o i n waters from a dolomit ic source , tends t o r e f l e c t the 1:l composition (20) of those ions i n the rock, so long as the s o l u t i o n i s no t subjected t o too many inf luences t h a t may cause CaCO3 p r e c i p i t a t i o n . Table 4 i n d i c a t e s t h a t the Ca:Mg r a t i o i s low a t the extreme anomalous s i t e "H" ( l o c a t i o n adjacent t o the sp r ing s i t e ) at a value of 0 . 3 4 which normally corresponds with the hydrolyzaie t y p e s ( 2 1 ) . Reference t o Traverse "Att on the wel l l i t h o l o g i e s ( 2 2 ) i n Figures59 and 60, i nd ica t ed a sha le u n i t (wel l No 31) west of the anomalous s i t e This sha le u n i t i s probably the "Vinemount Shale" ( s t r a t i g r a p h i c a l l y known as the Lower Eramosa Dolomitic-Shale Bed), which i s present i n Hamilton, y e t i s known t o pinch out somewhere towards the e a s t . The Ca:Mg r a t i o may however be misleading here because the re may be mixing of the waters der ived from the Lower Eramosa Dolomitic-Shale Beds wi th the dolomit ic waters of the Upper Eramosa Beds and the Guelph Formation. A l t e rna t ive ly , the l o w Ca:Mg r a t i o can be accounted €or by the incongruent d i s s o l u t i o n of the

"H".

73

v) a

w z d a w I

a 0

f

74

FIG. 57. OyaLOUS N-s AT 76'76 ACTIVITY D I A G W . FOR THE SYSTW HCl-i$O-CaO-C%-MnO I N THE AN

.

FIG. 58.

Y

3 8.000 1o.OoO 1 2 . m 1Y.000 1 LOG F I [ C R + t I / R ( H + ) P

( Helgenson e t . a l . , 1969 )

IW

PREDOMINANCE DIAGRAM FOR THE STABILITY OF CALCIUM AND MAGNESIUM CARBONATES I N THE ANaMALOUS NORTH CREEK WATERS ON NOV.26176

b W wJ3h

-12 -ll -la -9 -8 -7 -5 -5 -4 -3 -2 -1 0 log pcq-

FIG. IO.i8. Reizclonr among a lc ivm and magnaium carbonates at 25 T and i atmosphere c o d pressure. as a lunctim d?- (in atmos- pheres) and [Cat *]fiMg* '1. Solid lirer show equilibrium +elations bemcen ruble phases: dashed lines show equilibrium rclations between mcwuble phases, and betwcea meuruble and stable phases. [From a flgure by A. 6. Grpenter. in khmit t (ed.). op. cit.. P. 26: by permission.] ( Garrels and Christ, 1965 )

n

W I

v) e

W

l- a 3

Y

W

W

tx 0

I

I- e 0

Z

Wc

l

I

t-$

ZF

W

> a

cn W

2 8 a -J .J

W 3

0: I- w

s 0

0

u3

c3 H

Frc

'0

W

E 0

4

77

dolostone formations, r e s u l t i n g i n CaC03 p r e c i p i t a t i o n (evidence of c a l c i t e c r y s t a l s i n bedrock Note t h a t the Vinemount Shale conta ins up t o 50% c l a y minera ls and f i s s u r e s of carbonaceous m a t e r i a l (personal communication, Mostaghel, 1977). I n add i t ion , the compilat ion of geochemical d a t a (23) of g l a c i o l a c u s t r i n e s i l t s and c l ays , till and underlying bedrock u n i t s from the s tudy a rea (Table 6), suggests t h a t elements such as Zn, Pb, Fe, Mn, a r e der ived mainly from the Lower Eramosa Dolomitic-Shale Beds. This dolomit ic-shale bed c a r r i e s vugs conta in ing s p h a l e r i t e , galena, c a l c i t e , dolomite, gypsum, c e l e s t i t e and many o the r mineral g ra ins , and i t i s probable t h a t the d i s s o l u t i o n of these minera ls c o n t r i b u t e s towards the c i r c u l a t i n g groundwaters, Elements such as N i , C r and Cu, may be der ived from assoc ia t ion wi th the s u l f i d e s as t r a c e elements i n the bedrock o r even from the d i s s o l u t i o n of the heavy minera ls incorporated i n t o the l o c a l till mat r ix , from which d isso lved c o n s t i t u e n t s a r e cont r ibu ted t o the o v e r a l l composition of the groundwater,

vugs of core N 1 as shown i n Figure 4 8 ) .

Returning t o the mineral s t a b i l i t e s i n these anomalous sur face waters , dolomite f o r example i s supersa tura ted , and thus favourable t o p r e c i p i t a t e thermodynamically; y e t i t w i l l n o t form as the r e s u l t of the involvement of k i n e t i c p r inc ip l e s . The nuc lea t ion of highly ordered s t r u c t u r e s (24) such as dolomite i s a slow process a t low temperatures

and when i n competi t ion f o r Gaff and Cog t o c a l c i t e , dolomit ic p r e c i p i t a t i o n i s prevented, The same p r inc ip l e a p p l i e s t o o the r carbonates , i n t h a t nuc lea t ion i s needed f o r p r e c i p i t a t i o n t o occur , The r a t e of nuc lea t ion ( 2 5 ) i s dependent upon the i n t e r f a c i a l energy, supe r sa tu ra t ion , temperature and the c o l l i s i o n frequency e f f i c i e n c y f a c t o r s , d i t i o n s a r e met, high pH; low carbon dioxide p a r t i a l p ressure , super- s a t u r a t i o n ; high r a t e of nucleation; common ion effect; minimal solid s o l u t i o n wi th o the r metal ions ; and f i n a l l y minimal sh i e ld ing a c t i o n of the e l e c t r o l y t e s , Generally then, i f the thermodynamic and k i n e t i c f a c t o r s a r e s a t i s f i e d , p r e c i p i t a t i o n w i l l r e s u l t . Another complicated example of a given s o l u b i l i t y r e l a t i o n a t t h d anomaly s i t e , i s t h a t of magnesite, which e x i s t s with one O F the :;t&le hydrates e i t h c r nesquehonite o r hydromagnesite. Magnesite (26) i s formed e i t h e r by high temperature o r by slow a l t e r a t i o n of these s t a b l e hydrated carbonates . The l a t t e r is probably what happened i n the anomalous s i t e f o r t he s a t u r a t i o n of magnesite i n the North Creek waters , as ind ica t ed by the s a t u r a t i o n l e v e l diagrams i n Figure 56. For example, the nesquehonite and hydromagnesite phases a re under- s a t u r a t e d i n t h e i r metastable st act’s, while magnesite i s s l i g h t l y over- s a t u r a t e d ,

-- i ons i n a s o l u t i o n wi th r e spec t

Thus c a l c i t e , f o r example w i l l p r e c i p i t a t e i f the following con-

78

TP5LE 6 - COMPARATIVE TABLE ON THE GEOCHEMICAL COMPOSITION OF THE LOCAL SOIL AXD BEDROCK WITH THE ANOMALOUS CgOCHEMICAL VALUES

GLACIOLACUSTRINE SILTS AND CLAYS:

Background range for bottom strew sediments in the Watershed

&omaloue

homalous sediment value from core N1 (section N 13)

scream sediment value from study area

HALTON TILL:

Underlying Haltoo Till at anomaly (core N1)

Clalton Till, 3 mi. N.E. of anomaly (Peonstra, 1977)

Halton Till, 4 mi. N.W. of anomaly (Barnett , 1975)

\D

BEDROCK; - Underlying dolostone at anomaly site (core N1)

EKamOSa Iblostone Member (Warren & Devault ,1961)

Upper Eramosa Dolostone Member (Moetage1,1977)

Lower Eramosa Dolomitic - Shale Member (Mostagel,l977) Goat Island Dolostone Member (Mostagel, 1977)

Casport himestone Member (Mostagel, 1977)

25 - 50 25 - 50 9,000 - 9,500 400 - 800 8 - 12 20 25 10 - 15 250

439 la4 5,920 886 184 43.7 42.3 1

2,000 245 2,000 800 40 42 43 1

416.8 215.4 5 , 000 700 24.9

22 - 36 - - 77 - 147 19 - 65 40 - - 575

338 104.32 5,513.33 257.78 22.21

- - - 325 61

636.06 773.77 7,277.05 896.72 - 1,037 S O 912.50 11,575.00 1,975.00 - 273.07 855.76 6,811.54 1,290.38 - 307.93 806.34 7,279.36 1,007.94 -

TYPE OF EXTRACTTON USED

Present Study - Cold 12 Y. V.V. hydrochloric acid nnrnett. 1975 - Hydrofluoric and perchloric acid mixture Feenstra. 1977 - I'crchloric acid Wostagel, 1977 - Fusion with mixture of lithium carbonate Wirren 6 Devault, 1961 - Aquia regia and boric acid

23 .a

60 - 77 55

20.513

-

9.8

36 - 57 45

3.4

8

-

9

4

61

8

52

63

It should be noted a t t h i s po in t , t h a t the waters contained low pC02 ( i e Table 3) a t the anomalous s i t e , Lower equi l ibr ium Co2 pressures (27) usua l ly r e s u l t i n a high degree of s a t u r a t i o n f o r a given flow r a t e , and thus s i m i l a r i l y , would have a s i g n i f i c a n t con t ro l on the s t a t e of s a t u r a t i o n of the sp r ing waters a t s i t e ItHrq, Therefore, the l o s s of carbon dioxide i s the probable cause of the s a t u r a t e d su r face waters .

'In the anomalous a rea , minera ls such as sodium carbonates and sodium s u l f a t e s were undersa tura ted i n the sur face waters , a s shown by the s a t u r a t i o n l e v e l s i n Figure 61. Minerals l i k e anhydri te were under- s a t u r a t e d i n the waters while gypsum was found t o be supersa tura ted i n the waters a t the anomalous s i t e "H" ( i e Figure 61). The formation of gypsum (28) o f t e n takes place under non-equilibrium condi t ions and k i n e t i c f a c t o r s , while anhydri te should be favoured a t higher temperatures, Note t h a t t he high s u l f a t e conten t may have been der ived e i t h e r from the d t s - s o l u t i o n of gypsum c r y s t a l s from the underlying bedrock o r by r e p e t i t i v e ox ida t ion of s u l f i d e minera ls .

From the surface water da t a i n Table 3 on the abundance of major

+ + 33 -!-I- c a t i o n c o n s t i t u e n t s ( i e Na , K , C a , Mg ) a t the anomalous s i t e "HI'

( i e which r e f l e c t s a s i g n i f i c a n t groundwater con t r ibu t ion t o the North

+ Creek Waters), K was n o t considered as one of the predominant c a t i o n s i n the groundwater. i t b e s t f u l f i l l s the c rys ta l lochemica l cand i t ion (29) requi red f o r the s t a b i l i t y of c e r t a i n c l a y s , Thus, because of the p r e f e r e n t i a l absorpt ion and incorpora t ion i n t o the s i l icate s t r u c t u r e of c l a y s , potassium i s much l e s s abundant i n s o l u t i o n of the hydrosphere than sodium.

Potassium i n water does n o t become hydrated, y e t

The a l k a l i n e e a r t h ions , i e Ca and Mg, a r e roughly considered by most water chemists t o be two ions wi th similar behaviour i n t h e hydrosphere. However, the geochemical behaviour of magnesium (30) i s sub- s t a n t i a l l y d i f f e r e n t from t h a i of calcium, Magnesium ions a re smaller than sodium o r calcium ions , and the re fo re , have a s t ronger charge dens i ty and a g r e a t e r a t t r a c t i o n f o r water molecules. This may a l s o expla in the low Ca:Mg r a t i o i n the anomalous waters i n t h a t magnesium w i l l tend t o form so lub le hydrated complexes, while calcium forms p r e c i p i t a t e s ( i e c a l c i t e ) a t low temperature.

F igures 26 and 27 i n d i c a t e t h a t the chemical concent ra t ions of Sr and Na predominate i n a l l of the f o u r measured parameters and a s such, have a g r e a t a f f i n i t y f o r absorpt ion i n t o sediments a t s i t e "H". This , however does

not mean t h a t Sr and Na have a g r e a t e r exchangeable ca t ion s t a t u s than the t f 4-

v)

w a

@ 0 I

I- a 0

z

in a L

in

81

+t + o the r c a t i o n s s ince ions l i k e Ca and K may be incorporated i n t o c l ay minera ls i n t h e i r hydraul ic movement from the bedrock t o the day l igh t sur- f ace . Calcium has been known t o be the most connnon exchangeable c a t i o n i n s o i l s , as no t i ced a t s i t e “H”. chemical p a t t e r n s i n F igures , 30, 31, 32, 37, 38, 44 f o r elements Zn, Cd, Pb, Ag, C r , Mn, r e spec t ive ly , a r e somewhat i d e n t i c a l wi th the geochemical p a t t e r n s f o r calcium (Figure 28) i n almost a l l of the four s tud ied parameters a long the stream.

I n t e r e s t i n g i s t h a t the heavy metal geo-

The o the r i n t e r e s t i n g aspect: from Figures 26-45 i nc lus ive , i s t h a t elements such as Fey A l , S i , Be, K , As, Cu, T i , only increased i n the suspended sediments r a t h e r than i n the o the r th ree s tud ied parameters, reason i s t h a t , some of these elements w i l l tend t o form s t a b l e hydro- l y s a t e s ( i e Fe(OH)3, A1(OH)3, Be (OH)*, Ti(0H) ) as a r e s u l t of the

The

4

ox id iz ing stream water environment and eventua l ly p r e c i p i t a t e a t the o r f i c e and f u r t h e r downstream depending upon the res idence time i n these su r face waters , probably hemat i te , g o e t h i t e , o r f e r r i c hydroxide, on the bank of the spr ing o r f i c e .

The f e r r i c i r o n was seen a s a reddish-brown p r e c i p i t a t e ,

Observations of the anions i n the surface waters a t the anomalous s i t e “H” i n Table 3 , showed low concent ra t ions of ch lor ide and ammonia, y e t high concent ra t ions of n i t r a t e , su lpha te and a l k a l i n i t y . The com- b i n a t i o n of the l e s s e r ch lo r ide conten t wi th a higher n i t r a t e content may be the r e s u l t of the ch lo r ide so rp t ion i n t o c l ays (31) o r incorpora t ion i n t o organic mat te r i n the subsurface horizons ( i e upper sec t ion of N13) i n the anomalous a rea . S i m i l a r i l y , the low ammonia concent ra t ion a t the anomalous s i t e w a s probably caused by i t s absorpt ion i n t o clays; most

l i k e l y i n the NH4 +

s t a t e ( 3 2 ) .

The h i g h su lpha te content rcsu l t s from the oxida t ion of sulphide minera ls ( e i t h e r cliemicdl Jy o r by b a c l e r i a l ac t ion ) and the d i s s o l u t i o n of gypsum. The h i g h a l k a l i n i t y was der ived from the mixing of the carbonate groundwaters wi th the sur face waters . The bicarbonate ion predominates over the carbonate ion s ince these waters a re i n the pH range of 7 - 1 1 ( 3 3 ) .

After the spr ing water , with i t s high a l k a l i n i t y and sulphate content e n t e r s the sur face waters , the formation and p r e c i p i t a t i o n of hydroxides, carbonates and su lpha te s of the a l k a l i s , ( i e N a 2 C 0 3 ) , a l k a l i e a r t h s ( i e

CaS04. 2H20) and heavy metals ( i e ZnCO mation of these metal spec ies depend g r e a t l y upon k i n e t i c s , supe r sa tu ra t ion

PbS04) occured. The r a t e of fo r - 3 ’

pH, p r e c i p i t a t i o n , discharge e t c . The concept of co -p rec ip i t a t ion (34) of heavy meta ls wi th hydroxides, carbonates and su lpha tes , i s a very impor- t a n t means i n c o n t r o l l i n g the metal concent ra t ion i n an aqua t i c environment,

P r e c i p i t a t i o n and discharge should be noted as only p a r t of the c o n t r i b u t i n g f a c t o r s i n c o n t r o l l i n g p r e c i p i t a t i o n . o f mineral spec ies i n n a t u r a l waters . For example, discharge increased (Appendix 6) i n the month of October, 1976 while p r e c i p i t a t i o n decreased s t e a d i l y from September, 1976 t o November, 1976 (Appendix 7 ) . A s noted e a r l i e r , the chemical concen- t r a t i o n s of Na, K , Zn, Cd, Pb, Ni,Sr and C r increased i n bottom sediments wi th time. This may be explained by the subsequent decrease i n prec ip i - t a t i o n which would lower the t r a n s p o r t a t i o n r a t e of these elements and cause t h e i r subsequent f a l l o u t i n t o the sediments, The o the r group c l a s s i f i e d f o r the bottom sediments, w a s the s t a b i l i t y p a t t e r n of chemical concen- t r a t i o n s with time except f o r a decrease i n concent ra t ion i n the month of October f o r elements Ca , S r , Ag, and A s . This can be explained by the increased d ischarge r a t e i n the month of October. This explanat ion can a l s o be appl ied to one of the mentioned suspended sediment groups, which c l a s s i f i e d elements as moderately inc reas ing t h e i r concent ra t ions wi th time except f o r a decrease i n the month of October namely Ca, N a , S r , Ag, Zn, and Pb. As f o r the s t ream waters , the increased runoff f o r the month of October caused the abrupt change i n chemical concent ra t ions . During t h i s per iod, the chemical concent ra t ions of Fe, A l , Mn and T i decreased. Therefore, i t appeared t h a t i on exchange along wi th the p r e c i p i t a t i o n and discharge, seem t o be the dominant f a c t o r s i n con- t r o l l i n g the chemical concent ra t ions i n these anomalous waters .

Eh-pH d a t a f o r the sp r ing waters were p lo t t ed f o r the systems S - S O 4 , Fe, N i , Mn i n Figure 6 2 ( 3 5 ) and Cd, A s , Zn and Pb i n Figure 6 3 ( 3 6 ) . O b -

s e r v a t i o n of these eH-pH diagrams showed t h a t SO4 , N i , Mn , Cd , Zn ,

H A S ~ ~

-- + + u i + *

-- -- , Fe203(S04 ) and PbS04 were the predominant ions i n the s p r i n g

waters . It must be considered t h a t these eH-pH diagrams a re f o r s p e c i f i c environmental condi t ions and r e s u l t s could d i f f e r due t o sampling con- d i t i o n s . Nevertheless , the given eH-pH diagrams show a f i r s t approximation as t o i o n ( s ) expected i n the anomalous waters , The spr ing waters appeared t o be i n a f a i r l y low ox id iz ing environment, which i s r e f l e c t e d by the l o w ox id i z ing environment i n the bottom scdiments (Table 5 ) .

83

FIG. 62. Eh-pH DIAGRAMS FOR THE ANOMALOUS NORTH CREEK WATERS

(measured May 10/77)

(Carrels and C h r i s t , 1965)

0 Spring Waters

LOCATION OF SPRINGJ

n (Garrels . ind C h r i s t , 1965)

FIG. 63.

Eh-pH DIAGRAMS FOR THE ANOMALOUS NORTH CREEK WATERS (measured May 10/77)

$&Anomalous Surface Waters

0 Spring Waters

.I. '

1 . t .

..I

. ..

... E.

. .I

...

Pb (Carrels and Christ, 1965)

FIG. 6 4 .

ELUWCATION OF THE (>RIGIN AND CAUSE FOR THE ANOMALOUS SITE IN REFERENCE TO TRAVERSE "C"

< GROUNDWATER FLOW MODEL

C. GEOCHEMICAL PROCESSES €

CUNClUSlONS AND DEGREE TO WHICH PROJECT 22 OBJECTIVES WERE MET

The ob jec t ive of t h i s s tudy was t o determine the source of the anomalously high metal va lues de tec ted during rou t ine monitor ing, A groundwater s p r i n g wi th high d isso lved metal con ten t s was loca ted i n the n o r t h c e n t r a l s e c t o r of the watershed. A geochemical model f o r the anomalous s i t e was developed, u t i l i z i n g the d a t a from Traverse "A" of F igures 59 and 60 along wi th the rock types of the three we l l s ec t ions . The c r o s s s e c t i o n of Traverse "C" loca ted i n Figure 64a, summarized the o r i g i n and geochemical h i s t o r y of the abnormality, which i s caused n a t u r a l l y and no t by man's a c t i v i t i e s .

The geologica l a spec t i s shown i n Figure 64b. The source of heavy me ta l s w a s a topographic low where bedrock i s c lose t o the sur face . Sup- plemented by the l i t h o l o g i c a l d e s c r i p t i o n i n Figures 59 and 60 and the bedrock contour map i n Figure l .c . , groundwater flow w a s assumed t o migra te from the northwest end of the watershed towards the southeas t . A t t he northwest end, groundwater received i t s water supply mainly from sur face waters which passes through the overlying s o i l horizons, picking up carbon dioxide from the s o i l a i r (geochemical s t e p 1 i n Figure 64d). C a l c i t e o r dolomite minera ls present i n the s o i l a r e d isso lved i n the r e s u l t a n t carbonic ac id . Groundwater s a tu ra t ed wi th mineral c o n s t i t u e n t s from the till (geochemical s t e p 2 i n Figure 64d) flowed downslope a t the b e d r o c k / t i l l i n t e r f a c e of the Lockport and Guelph Formations. the bedrock, the groundwater i s probably d i f f u s e , r e s u l t i n g i n a l a rge number of small sp r ings and seeps. Larger spr ings may e x i s t because of s t r a t i g r a p h i c of s t r u c t u r a l f e a t u r e s (37). This was the case a t the anomalous s i t e , where groundwater was emi t ted l a t e r a l l y as spr ings a t the two s t r a t i g r a p h i c con tac t s Lower Eramosa Dolomitic-Shale/Upper Eramosa Dolostone I n t e r f a c e and a t the Goat I s l a n d Dolostone/Lower Eramosa Dolo- mit ic-Shale I n t e r f a c e . The former con tac t may be seen i n Figure ld(38) as "windows" i n the bedrock formations. It should be noted t h a t the anomalous t r a c e metal concent ra t ions shown i n F igures 5-25 i n c l u s i v e l y , d i r e c t l y correspond t o the "window" l o c a t i o n s of Figure Id. This suggested t h a t groundwater migra t ing through the f r a c t u r e s and bedding planes of the Guelph and Lockport Formations d isso lved some c a l c i t e and dolomite (geochemical s t e p 3 i n Figure 64d), and moving through the Upper Lockport Formation, i t encountered minera ls (39) such as s p h a l e r i t e , galena,

wi th in

a7

c e l e s t i t e and gypsum and d isso lved m e t a l l i c c a t i o n s and su lpha te , s o l u t i o n of gypsum and s l i g h t ox ida t ion of sulphide minera ls (geochemical s t e p 4 i n Figure 64d) provided the high su lpha te content i n the waters a t the anomalous s i t e .

The d i s -

It is bel ieved t h a t t he dolomit ic-shale beds (see Figure 64b) from which the groundwater chemistry w a s der ived, were about 800 m. e a s t of the anomaly s i t e . c h a r a c t e r i s t i c of hydro lysa tes conta in ing organic s i l i c e o u s sha le . I n add i t ion , the heavy metal concent ra t ions of Zn and Pb i n the spr ing waters a r e der ived from r e p e t i t i v e oxida t ion of s p h a l e r i t e and galena minerals (40) incorporated i n the sulphide r i c h Lower Eramosa Dolomitic-Shale Beds ( l e . r e f e r t o Table 6 as a comparit ive means f o r suggest ing t h a t the high Zn and Pb concent ra t ions o r i g i n a t e from the Lower Eramosa).

The low Ca/Mg and HCO3/SO4 r a t i o s i n the spr ing waters were

As su lpha te ions a r e r e l eased i n t o s o l u t i o n from gypsum weathering, c a l c i t e i s p r e c i p i t a t e d i n the dolostones and can be seen i n vugs i n the bedrock d r i l l core N 1 as the r e s u l t of the incongruent d i s s o l u t i o n of dolomite, With p r e c i p i t a t i o n of the c a l c i t e , t he re would be a decrease i n the supe r sa tu ra t ion of dolomit ic waters as well as a low Ca/Mg r a t i o (geochemical s t e p 5 i n Figure 64d). The c a t i o n exchange would be a very important process a f f e c t i n g the water chemistry of the groundwater migra t ing through t h i s dolomit ic-shale bed because of the order of a b s o r b i l i t y of major c a t i o n s (Ca>Mg>Na) i n c l a y minerals . (One Ca w i l l r ep l ace one Mg o r two Na and so on. As t h i s b i a s i n c a t i o n exchange f o r calcium cont inues, r e l eased Mg are de tec ted i n the spr ing waters a t h igher concent ra t ions than Cay g iv ing r i s e t o the low Ca/Mg r a t i o ) .

The low HC03/S04 ratio at the anomaly i s an i n d i c a t i o n of increased su lpha te wi th low bicarbonate concent ra t ions , thus upse t t i ng the carbonate e q u i l i b r i a . For example, i n the r eac t ion :

-.. ft Ca + so4 + 2H20 CaS04.2H20

equi l ibr ium s h i f t s t o the r i g h t when groundwaters a r e enriched i n su lpha te . Therefore , gypsum w i l l be supersa tura ted , poss ib ly p r e c i p i t a t i n g in the sp r ing waters because the sulphate c o n t r o l s the chemical r e a c t i o n s .

The groundwaters ca r ry ing the major c o n s t i t u e n t s , charac te r ized by low Ca/Mg and HCO3/SO4 r a t i o s , passes from the s t r a t i g r a p h i c bedrock contac t between the Lower Eramosa and the Upper Eramosa, upward along a sandy permeable l e n s i d e n t i f i e d a s t h e sediments from the lower N13 s e c t i o n of core N 1 , t o be f i n a l l y discharged a s an a r t e s i a n sp r ing on the stream bank a t s i t e "HI' ( see Fig. 64 c ) . The movement of minor c o n s t i t u e n t s , such as heavy meta ls (41, 42, 43, 44, 45) i n groundwater i s similar t o the major c o n s t i t u e n t s . For example

chemical and phys ica l processes appear t o be pr imar i ly c o n t r o l l i n g the s p r i n g ' s water chemistry f o r the heavy meta ls ; emphases pr imar i ly placed upon the conplexation of heavy meta ls with the su lpha te ions , che la t ion wi th o the r inorganic o r organic l igands and scavenging of heavy metals by hydro lysa tes (geochemical s t e p 6 i n Figure 64d).

It i s now poss ib l e t o d i scuss the cha rac t e r of the contaminated groundwater leav ing the aqu i f e r on November 26/76. minera ls i n the anomalous sp r ing water i n F igures 56 and 61, shows t h a t the n a t u r a l waters a r e s a t u r a t e d wi th r e spec t t o c a l c i t e , a ragoni te , magnesite, and dolomite, and supersa tura ted wi th r e spec t t o gypsum (geochemical s t e p 7 i n Figure 64d). The s a t u r a t i o n of these carbonate minera ls i s the r e s u l t of carbon dioxide being l o s t t o t he atmosphere, "degassing". creases the mine ra l ' s s a t u r a t i o n i n d i c e s of the r e spec t ive minera ls q u i t e ab rup t ly toge ther wi th a s l i g h t increase i n pH.

The s t a b i l i t y of s eve ra l

This in -

Downstream from the anomaly, t h e c reek waters c o l l e c t e d on November 26/76 appear t o have the r eve r se s i t u a t i o n , i n t h a t c a l c i t e , a ragoni te , magnesite and dolomite a r e a l l supersa tura ted , whereas gypsum i s under- s a t u r a t e d (geochemical s t e p 8 i n Figure 64d). b r i a seems s o l e l y t o be the c o n t r o l l i n g mechanism downstream from the anomaly due t o the degassing of carbon dioxide from the spring-derived waters i n a t t a i n i n g equi l ibr ium with the atmosphere. It i s noted from the chemical concent ra t ions i n bottom sediments, suspended sediments, s t ream waters and w e l l waters a t the anomalous s i t e , t h a t q u a l i t a t i v e l y , the d a i l y discharge c o n t r o l s the r a t e of mineral e q u i l i b r i a i n these n a t u r a l waters .

Thus, t he carbonate e q u i l i -

The pH of the c reek waters i nc reases downstream pH 7.2-pH8.5 along wi th the temperature 8 C - 15OC, from the s p r i n g ' s o r f i c e . the carbon dioxide p a r t i a l p ressure i n the water drops from log Pco2 = -2.41 a t m . near the sp r ing s i t e t o -3.22 atm. a t s i t e "L" 100 m , downstream. A t s i t e "M" 200 m. downstream from s i t e "L", the log Pc02 inc reases t o -1.54 a t m . I nc iden t ly , the log P i n the atmosphere i s approximately -3.5 atm, (46) . supersa tura ted carbonate s o l u t i o n a t some poin t downstream from the spr ing . The supe r sa tu ra t ion te rmina t ing a t s i t e "L" i s because equi l ibr ium has been reached wi th the atmospheric carbon dioxide. Thus pH can be a s i g n i f i c a n t determinat ive f a c t o r i n the chemistry of n a t u r a l waters .

0 A s a r e s u l t ,

A s mentioned beforeyC?4e l o s s of carbon dioxide would r e s u l t i n a

The chemical concent ra t ions of Zn, Pb, Ca and S r i n the bottom sed i - ments (Figures 30, 32, 28, 26 r e spec t ive ly ) a r e con t ro l l ed by p r e c i p i t a t i o n , d i scharge and CaC03. A s the CaC03 i s p r e c i p i t a t e d from the supersa tura ted s o l u t i o n downstream of the sp r ing discharge, the sp r ing der ived meta ls a r e

89

a l s o co -p rec ip i t a t ed (47, 48) and occur at higher than background l e v e l s i n the m a t e r i a l analyzed f o r the bottom sediments, Higher metal values may have been de tec ted i n the suspended sediments from the anomaly s i t e , depending upon the res idence time of t he p a r t i c u l a r ma t t e r , The heavy metals and major c o n s t i t u e n t s are high i n the stream waters at the

anomaly because of the che la t ion wi th anions ( i e SO4 , HC03 , C03 or simply the formation of aquo metal i ons .

-- - -- - , OH )

The ob jec t ive of the North Creek Study have been f u l f i l l e d by the discovery of a source of bedrock-derived heavy elements i n the anomalous n o r t h c e n t r a l s e c t o r of the watershed t o account f o r the p lo t t ed geochemical d i s t r i b u t i o n maps i n Figures 5-25 i nc lus ive ly . t h e anomalous high meta l values was found wi th in the bedrock i n the n o r t h c e n t r a l sector and a geochemical model t o expla in the observed phenomena was developed. Po l lu t ion from atmospheric sources , der ived from major c i t i e s nearby d id no t con t r ibu te s i g n i f i c a n t l y t o the anomalously h igh l e v e l s of heavy meta ls as the concent ra t ions i n p r e c i p i t a t i o n samples (Appendix 8) were much lower than those i n the North Creek waters , Thus, the imp l i ca t ion t h a t man's pas t o r present a c t i v i t i e s may have been respons ib le f o r the h igh heavy metal conten ts of t he stream water was n o t supported by the geochemical evidence.

The o r i g i n of

FROM WHllT SOURCES AND FROMWHllT CAUSES ARE POLLUTAWTS CONTRIBUTED TO SURFACE AND GROUND WllTERS ?

Q The multi-element geochemical approach, by use of the Di rec t

Reading Emission Spectrograph Q,A, 137, has succeeded i n de r iv ing a s o l u t i o n t o the problem of the source of t he abnormality i n the no r th c e n t r a l s e c t o r of the watershed.

From the combination of d a t a der ived from the geochemical s tudy, as we l l as the chemical, e lectrochemical and t e x t u r a l determinat ions used i n t h i s anomalous a rea , i t w a s concluded t h a t the anomaly i s i n f a c t caused by n a t u r a l sources r a t h e r than by man's a c t i v i t i e s . i nd ica t ed a r t e s i a n spr ings t o be the source of t he anomalously high chemical elements which are emanating a t s t r a t i g r a p h i c con tac t s between the Lower Eramosa Dolomitic-Shale/Upper Eramosa Dolostone I n t e r f a c e and the Goat I s l a n d Dol,ostone/Lower Eramosa Dolomitic Shale I n t e r f a c e .

The r e s u l t s have

The sp r ing waters contained high va lues of t o t a l d i sso lved s o l i d s ; s p e c i f i c conductance; i o n i c s t r eng th , t he anions, S O 4 , HC03, NO3 together wi th minute amounts of NH3 and C 1 ; so luble c a t i o n s , C a y Mg, N a y together wi th minute amounts of K; and heavy metals, Zn, Cd, Pb, N i , Ag, C r , t u - ge ther wi th low concent ra t ions of Fe and Be, waters revea led t h a t t h i s secondary environment i s s l i g h t l y oxid iz ing . The cause of these anomalous waters can be explained by the d i s s o l u t i o n of gypsum and carbonate minera ls of the Lockport Formation i n conjunct ion with the ox ida t ion of the disseminated su lphides such as s p h a l e r i t e and galena which are normal components of the dolomit ic-shale beds of the Lower Era- mosa. The groundwater becomes s a t u r a t e d wi th these minera ls , which emanate a t the sp r ing t o become p a r t of the North Creek waters . predominate anion i n c o n t r o l l i n g the s p r i n g ' s water chemistry by com- p lexa t ion wi th the so lub le s and heavy metals . Gypsum thermodynamically p r e c i p i t a t e s a t the o r f i c e of the l a r g e s t sp r ing , Downstream from the spr ing s i t e , the changes i n the s a t u r a t i o n of the carbonate minera ls are the r e s u l t of t he saturated-bedrock mineral waters l o s i n g carbon dioxide on moving towards equi l ibr ium wi th the atmosphere, r e s u l t i n g i n a super-

The eH-pH d a t a f o r the spr ing

Sulphate i s the

saturated solution of c a l c i t e , aragonite, magnesite and dolomite, Thus, carbonate equi l ibr ia is more important i n the North Creek waters downdip from the spring s i t e rather than sulphate chemistry,

WHAT IS THE fWTENT OF POLLUTANT CONTRIBUTIONS MAT IRE THE UNIT AREA LOADINGS BY SEASONS FROM THE ANOMALOUS SITE TO SURFACE AND 6ROUND WATERS?

The ex ten t of p o l l u t a n t con t r ibu t ions is pr imar i ly dependent upon the p r e c i p i t a t i o n and discharge levels of t he stream waters a t the time of sampling. water wi th carbon d ioxide ; as sur face water seeps through the s o i l zone and i n c r e a s e s the recharge a r e a northwest of the anomaly wi th oxygen-bearing ground waters, approaching equi l ibr ium wi th r e spec t t o the wal l rock ( f o r example, the r a t e of d i s s o l u t i o n and ox ida t ion processes w i l l c o n t r o l the amount of bedrock c o n s t i t u e n t s r e l eased t o the c i r c u l a t i n g groundwaters) and the time of t he spr ing discharge i n t o the North Creek waters a f t e r the i n i t i a l i n f i l t r a t i o n of sur face water i n the S i l u r i a n bedrock. The geochemical model s tudy, based upon the bottom stream sediments, suspended sediments, stream waters and we l l waters c o l l e c t e d biweekly from September 1/76 t o November 26/76 showed t h a t the increased runoff f o r t he month of October in f luenced the r e l a t i v e chemical concent ra t ions . As a conclusion, p r e c i p i t a t i o n and d ischarge , a long wi th ion exchange, d i f f u s i o n r a t e s through the carbonate bedrock and o the r r e l a t e d f a c t o r s , c o n t r o l the r e l a t i v e chemical concent ra t ions as repor ted i n the anomalous waters of the n o r t h c e n t r a l s e c t o r of the watershed.

P r e c i p i t a t i o n plays a dominant r o l e i n supplying the ground-

Discharge e f f e c t s the res idence t i m e of the groundwaters

A followup study, concerning the water q u a l i t y v a r i a b l e s i n major and minor constituents with respect to the daily spring water discharge and the d a i l y s t ream water discharge would g ive the u n i t a r e a loadings per element by seasons leav ing the bedrock aqu i f e r and the watershed r e spec t ive ly .

TO WHAT DE6REE ARE POLLUTANTS TRANSMITTED FROM 8 SOURCES TO BOUNDARY WAT€RS ?

During t r a n s p o r t downstream from the spr ing , the t r a n s p o r t a t i o n mechanism f o r the heavy me ta l s , Zn and Pb, seem t o have co -p rec ip i t a t ed wi th the carbonates t o f i n a l l y accumulate i n the bottom stream sediments, I n the suspended sediments, heavy metals a r e complexed e i t h e r with or - ganic ma t t e r o r w i th the i r o n and manganese oxides , The complexation of heavy meta ls with inorganic l igands predominate i n the North Creek stream wa te r s ,

Quan t i t a t ive ly , the approximate percentage reduct ion f o r the amounts of heavy meta ls are ca l cu la t ed f o r t h e i r t r anspor t through a given s e c t i o n of the anomalous stream ( i e from s i t e "HI' t o s i t e "0" l oca t ed i n Figure 2). The stream waters i nd ica t ed a percentage r e - duc t ion of 56% Zn, 3% Pb, 81% Ni and 60% C r . I n comparison t o the suspended sediments, the percent reduct ions were 83% Zn, 86% Pb, 96% N i and 81% C r . Thus, the heavy meta ls assoc ia ted with suspended sediments have a s h o r t e r res idence time than i n the d isso lved s t a t e i n the North Creek su r face waters ,

To account i n f u l l f o r t he degree by which the North Creek pol- l u t a n t s a r e t ransmi t ted t o the boundary waters of Lake Ontar io , would r e q u i r e a f u r t h e r study on the t o t a l con t r ibu t ion of these n a t u r a l pollutants t o the Twenty Mile Creek flowing into Lake Ontario.

1. Liberty, B.A., "Paleozoic Geology of the NiagaraArea, Southern Ontario", Ontario Division of Mines, Map 2344 - 1975.

2. Guillet, G.R., "Notes on Zinc-Lead Mineralization in Silurian Dolomite of the Niagara Escarpment and Bruce Peninsula, Ontario", Ontario Department of Mines, MP. 8 . 1967.

3. Sutton, R.G., "An Inexpensive Hana-Operated Sediment Corer", J. Sed. Petrol Vol. 44 (3). pp, 928-930 . 1974. -' '

4. Zobell, C.E., "Studies on Redox Potential of Marine Sediments," - Bull. her. Assoc. Petrol. Geo l . , Vol. 30 (4). pp. 477-513, 1946.

5, Garrels, R.M., Mineral Equilibria at Low Temperature and Pressure, Harper and Brothers Publishers, New York, N. Y, 1960.

6. Glasstone, S , , An Introduction to Electrochemistry, D. VanNostrand Co., Princeton, N . J . , p. 232. 1942.

7. Peech, M., Methods of S o i l Analysis Part 2 , C.A. Blacked., pp. 914-26. 1965.

8 . Agemain, H. and Chaw, A.S.Y., "Evaluation of Extraction Techniques for the Determination of Metals in Aquatic Sediments", The Analyst, Vol. 101, NO. 1207, pp. 761-7. 1976.

9. Fortescue, J.A.C., "A Preliminary Study of the Use of Stream Sediment Geochemistry to Detect the Effects of Man's Activities on the Environ- ment around St, Catharines, Ontario," Brock University, Dept. of Geological Sciences, St. Catharines, Res. Rept. Ser. No, 2, 22 p, 1971.

10. Gawron, E,, "The Effect of Collecting Time and Grain Size on the Sampling of Stream Sediments for Geochemical Mapping in the St. Catharines Area, Ontario", Brock University, Dept. of Geological Sciences, St. Catharines, Res. Rept. Ser. No. 3., 33p. 1973.

97

11.

12.

13 . 14.

15 . 16.

17 .

18.

19.

20 .

21 0

22.

Bradshaw, P.M.D., e t . al., "Exploration Geochemistry", Canadian Mining Journa l , Vol. 93, No. 5, pp. 53-85. 1972.

Bradshaw, P.M.D., "Data from Barr inger Research", Barr inger Research Paper. 1974.

Chapman, H.D., Methods of S o i l Analysis, Pa r t 2, C.A. Black ed., pp. 891-901. 1965.

Atkinson, H.J. e t . al . , "Chemical Methods of S o i l Analysis", Chem. Div. Sci . Serv., CDA, Contrib. No. 169 (Revised). 1958.

McKeague, J.A., Manual on S o i l Sampling and Methods of Analysis, S o i l Research I n s t i t u t e . 1976.

Truesde l l , A.H. and Jones, B.F., "WATEQ, a Computer Program f o r Calcu- l a t i n g Chemical E q u i l i b r i a i n Natural Waters". J. Res. U.S. Geol. -* Surv , No. 2., pp. 233-48. 1974.

Langmuir, D., "The Geochemistry of Some Carbonate Ground Waters i n Cent ra l Pennsylvania", Geochim. Cosmochim. Acta, Vol. 35, pp. 1023-45. 1971.

Helgenson, H.C.,et. al . , Handbook of Theore t ica l Ac t iv i ty Diagrams Depicting Chemical E q u i l i b r i a i n Geological Systems Involving an Aqueous Phase a t One Atm. and O°C t o 3OO0C, Freeman, Cooper & Co., San Francisco, 253p. 1969.

Garre l s , A.M. and C h r i s t , C.L., So lu t ions , Minerals and Equ i l ib r i a , Freeman, Cooper & Co., San Fransico, 450 p., 1965.

Hem, J.D., "Study and I n t e r p r e t a t i o n of the Chemical C h a r a c t e r i s t i c s of Natura l Waters," U.S. Geol. Survey, Water - Supply Paper No. 1473, 363p, 1970.

Hem, J.D. 1970.

Ontar io Minis t ry of the Environment, Water Well Data i n the Srni thvi l le Loca l i ty , Unpublished Report , Toronto Off ice , 1976.

L i s t ed References i n Table 6:

Barne t t , P., " T i l l Matrix C h a r a c t e r i s t i c s of the Upper and Lower T i l l s

98

of the Niagara Peninsula , Ont.", Unpublished MSc. Thesis , Univers i ty of Waterloo, Waterloo, Ont. 1975.

Feens t ra , B.H., Personal C m u n i c a t i o n on some Geochemical Concentra- t i o n from the Halton T i l l i n the Smi thvi l le Area, Ont. Dept. of Mines, Toronto, 1977,

Mostaghel, M . , Personal Communication on some Geochemical Concentrat ions from Local Bedrock near the Study Area, Brock Univers i ty , S t . Cathar ines , 1977.

Warren, H.V. and Delavaul t , R.E. , "The Lead, Copper, Zinc and Molybdenum Content of some Limestones and Related Rocks i n Southern Ontario", =. - Geol. Vol. 56, pp. 1265-72, 1961,

24. Bla t t , H., Or ig in of Sedimentary Rocks, Prent ice Hall I n c . , New Jersey , 634 p. 1972,

25. S t m , W. and Morgan, J .F . , Aquatic Chemistry, John Wiley & Sons, Inc . , Toronto, 683 p, 1970.

26. Krauskopf, K.B., In t roduc t ion t o Geochemistry, McGraw-Hi11 Co., Toronto, 721 p. 1967,

27, Basse t t , J . , "Hydrology and Geochemistry of the Upper Lost River Drain- age Basin, Indiana", Na t ' l . Speleol . SOC. Bul l . , Vol. 38 ( 4 ) , pp. 79- 87. 1976.

28. Bla t t , H . 1972.

29. M i l l o t , G., Geology of Clays: Weathering, Sedimentology, Geochemistry, Springer Verlag, New York, 429p. 1970.

30. Hem, J.D. 1970.

31. Feth , J . H . , "Sources of Mineral Cons t i tuents i n Water from Granitic Rocks, S i e r r a Nevada", U.S. Geol. Survey Water Supply Paper, No, 1535- I, 70 p , 1964.

32. Hem, J. D. 1970.

33. Hem, J. D. 1970.

99

3 4 .

35.

36.

37

38

39

40.

41.

42.

43.

Forstner, U,, "Forms and Sediment Associations of Nutrients, Pesticides and Metals", in Proceedings of a Workshop on the Fluvial Transport of Sediment-Associated Nutrients and Contaminants, I.J.C. Research Advisory Board, Kitchener, Ont. p.219. 1976.

Listed References in Figure 62:

Garrels, R.M. and Christ, C.L. 1965. Hem, J.D. 1970.

Listed References in Figure 63:

Ferguson, J.F. and Gavis, J . , "A Review of the Arsenic Cycle in Natural Waters", Water Research, Vol. 6. pp. 1259-74, 1972,

Garrels, R.M. and Christ, C.L. 1965.

Hem, J.D., "Chemistry and Occurrence of Cadmium and Zinc in Surface Water and Groundwater", Water Resources Research, Vol. 8 ( 3 ) , pp. 660- 79. 1972.

Shuster, E.T. and White, W.B., "Seasonal Fluctuations in the Chemistry of Limestone Springs: A possible Means for Characterizing Carbonate Aquifers", Journal of Hydrology, Vol. 14. pp. 93-128, 1971.

Liberty, B, A . 1975,

Hewitt, D.F., Rocks and Minerals of Ontario, Ontario Department of Mines Publication, Toronto, Canada, 108 p . 1965.

Boyle, R.W. , "Geology, Geochemistry, and Origin of the Lead-%irrc-: , i .Lver Deposits of the Keno Hill - Galena Hill Area, Yukon Territory", Geol, Surv. Can., Bulletin 111, 302 p. 1965,

-

Lee, G . F . and Hoadley, A.W., "Eiologir,ol A c t i v i t y in li: I . ~ L I ~ t o rtie Chemic a1 Equi 1 i br i um Compo s i t. i 011 (3 f Na t LIZ' a 1 Ida t e r s , i ~i Eq u i 1 i b r i mi Concepts in Natural Water Systems, Advances in Chemical Series, No, 67., American Chemical Society, Washington, D . C . , pp. 319-37. 1967.

Rubin, A, J, , Aqueous - Environmental Cheiiii stry of Metals, Ann Arbor Science Publishers Inc., Ann A r b o r , Michigan, pp. 1-77. 1974.

Reuter, J.H. and P e r d u e , E , M . "importance of Heavy Metal - Organic Matter Interactions in Natural Waters", Geochim, Cosmochim. Acta,VoL. 41. pp. 325-34. 1977.

44. Baas Becking, L.G.M., et. al., "Limits of the Natural Environment in Terms of pH and Oxidation - Reduction Potentials", Journ. of Geol., Vol. 68 (3). pp, 243-80. 1960.

45. Fairbridge, R.W., The Encyclopedia of Geochemistry and Environmental Studies, Van Nostrand Reinhold Co., Toronto, Canada, p.1150. 1972.

46. Garrels, R.M. and Christ, C.L. 1965.

47. Lee, G.F. and Hoadley, A.W. 1967.

48. Boyle, R.W. 1965.

101

APPENDIX I

GEOCHEMICAL CONCENTRATIONS I N BOTTOM SEDIMENTS, SUSPENDED SEDIMENTS, STREAM WATERS AND WELL WATERS I N THE ANOMALOUS NORTH CENTRAL SECTOR OF THE NORTH

CREEK WATERSHED - sampled on Nov. 26/76

POSITION DOWNSTREAM -( ie. A - 0 inclusive)---

105

GEOCHEXCCAL CONCMTRATIONS I N BOTTOM SEDIMeWTS

SAMPLE SITE

A B C D E F c

I J K L M N 0

-

n

SAMPLE SITZ

A B C D E F G H I J X L M N 0

-

SAMPLE SITE -

A B C D E F C H I J K L M N 0

Sr w 25.7 26.6 24.8 21.0 20.6 26.4 49.5 106 99.7 45.5 51.8 io8 52.3 37.3 81.5

za u& 82.1 98.3 89.5 69.4 70.9 96.8 380 I19 43 9 113 393 277 106 84.6 150

Fa (udg)

19200 19200 20000 14800 13900 20000 14800 19200 13 LOO 14800 11300 13100 21500 13900 14800

&!EL& 360 351 ' 254 272 360 452 500 727

514 650 553 692 525 452

846

K &E!&

888

a43

932

843 755

999 1690 1240 3170 1150 2620 2620 1330 977 2350

C. Iralrt! 5700 5210 4720 5700 4970 5700

43800 lZ000

9120 66800 73600 16900 6920

55500

88700

GEOCI@XICAL CONCENTRATIONS IN BOTTOM SEDIMENTS

Cd u 9.71 7.34 9.48 7.58 7.11 9.71 10.9 10.4 12.8 9.48 10.4 10.9 12.3 7.58 10.9

Pb LE&

68.9 80.0

79.4

62.3 61.2 84.4 143 99.9 184 94.4 156 157 115 76.7 133

AB

lreLHT 134 101 111 91.6 90.3 160 187 178 214 159

176 175 106 171

iao

GEOCHEMICAL CONCENTRATIONS M BOTTOM SEDMENTS

A 1 ( U d d

6390 5730 6140 6050 4940 5420 4860 5380 4730 5760 4550 4240 4850 5160 5000

Mn (ne/€!)

559 1129 255 205 381 886 459

851 667 513 842 6 14 598 795

486

Be ( J J d g )

.846

. 7 4 3 1910 . 7 6 9 ,660 ,851 ,639 ,758 ,486 . 7 74 ,515 .463

.543

.598

. i a i

A6 Cr u && ,738 30.7 .738 39.2 .738 33.4 .738 24.0 .738 25.0 .738 32.2 1.23 42.3 .984 31.7 2.46 35.1 .984 39.9 1.72 34.6 1.72 36.5 .984 34.6 .738 24.0 1.23 31.2

Ni (UP/ 8 )

19.0 31.1 21.9 15.2 15.4 20.5 43.7 23.3 37.7 29.8 37.2 35.3 23.8 18.5 31.0

SI (us lg )

2500 2540 2350 2390 2210 2280 2690 2450 3120 2770 2920 2750 2270 2370 2640

Ti L l ! u

44.7 44.0 51.7 50.6

39.0 43.4 47.4 57.8 42.5 35.1

48.7 51.6

. 63.7

33.4,

48.8

cu ( v g l g )

11.1 9.61 1 5 . 6 16.3 10.6 12 . o 20.2 13.0 16.8 :2.0 ' 16.3 13.5 12.5 13.0 17.3

SAMPLE SITE - Sr

rn U. m ,103 ,112

A

.128 624

C. (mg/tL

,539 4.31 - - ,776 536

1.05 9.80 1.32 ,477

Ag M

.N.D.

.0053 - -

.OOfZ 0005

.N.D.

.0034

.0005 to002

Cr id11

,005 ,010 - - ,029 .008 .002 ,062 ,009 ,006

A B C D E F G H I J K L M N 0

.0051

.006S

- I 130 ,049 ,073 ,732 ,152 .063 - - ,070 ,057 130

- .003a ,0014 .0057 ,0239 ,0107 ,0043 - - .0057 .0037 .OW3

,556 ,168 .OS3 1.212 ,229 a105 - ,666 * 788 ,189

- ' ,614

.658 , a99

- ,0001 .0009 .0002

- .002 * 002 ,008

C E O C m C A L CONCENTRATIONS IN SUSPENDED SEDIMENTS

SAEipLE SITE

A B C D E

c H I J K L M N 0

-

,. 2

N f ( m e l l ~

006 .006

Ti (ms/l)

,026 ,054

,0013 ,0050 - - * 0081 .0022 .0008 ,0205 .0034 ,0014

,018 .029 - - ,045 ,017 .008 .142 ,026 ,015 -

,029 .079

.016

.064 - -

.070

.023 ,006 .173 ,026 * 002

- .054 ,046 .008 ,196 .037 .025 -

- .121 .035 I012 .26S .041 .02a -

.007 * 008 ,005 .054 * 008 .006 - - - -

,0007 .007 * 011 ,0008 .007 .a12 .0017 a 020 .041

.006

.006 ,029

-002 .003 * 002

.006 a008 .034

GE-CAL CONC~TRATIONS IN S U S m E D SEDIIGSTS

A1 A3dJ.L 1.01 3.41

Mn m ,016 ,920

Be A!!&& ,000059 .000177

si

,950 2.96

cu

.003 ,004 - - ,006 .004 .001 ' .020 .004 ,002 - 7

,0007 ,0007. .005

SAMpLe SITE

A B C D E I G H I J K L M N 0

- Fa &!&La.

1.90 7.46 - - 8.44 3.52 4.81 24,05 4.03 2.64 - - .695 .672 .932

- 4.30 1.77 ,234 12 * 12 1.57 1.05 - - .283 ,299 ,403

- .185 .023 .005 .276 .037 .023

- .000349 ,000097 .0000237 .0007 ,0001 * 00007 1

- 4.07 1.50 ,288 10.76 1.54 1.12

- ,009 ,009 .034

,0000225 .0000218 .000082

,271 ,312 ,920

107

OBDCReMICAL CONCENTRATIONS IN STREAM WATERS

SAYPLE SITE

A B C D E F G H I

- Sr (mell)

,433 .896

N. Jmg/l)

10.1 10.6

Co

123 123 - - 111 123 132 146 130 123

123 84.4 123 123

C r ( m u l l )

.074

.099 7.91 18.1 -

,545 .321 1.08 4.54 1.28 1.05

11.3 9.04 9.04 11.6 9.04 9.04

.012 ,012 8 012 ,014 a012 ,012

,074 .074 .074 .I86 . I24 .124

.074

.074 ,074 ,074

-

8.97 7.96 13.0 38.0 19.9 19.5

16.5 15.9 16.8 19.5

- 1.11 ,891 ,870 .707

,012 .012 ,012 .012

11.3 9.04 11.3 11.3

G E O C B W L C A L CONCENTFATIONS IN STREAM WATERS

SAMPLE SITE - Pb

(mgll) AS

(mg/l)

2.00 2.60 - - 2.93 2.88 2.41 2.93 2.76 2.85

,279 .377 -

* 800 1.00 _. - 1.00 .911 ,911 1.40 ,956 1.09

,198 ,307 - - * 210 .549 .I49 2 998 .210 ,452

,331 ,186 ,259 ,186

-

N. D. N.D. - - N.D. N .D. N.D. N.D. N.D. N.D.

.303

.254

.303 ,660 ,377 ,353

.328 ,279 .353 ,291

I

.080

.Ob7 ,067 ,092 , os0 a080

,092 ,067 .092 ,080

1.36 1.18 1.47 1.36

3.74 3.86 4.13 3.99

N.D. N.D. N.D. N.D.

GEOCHEKlCAL CONCEXTPATIONS IN STREAM WATERS

SAYEE SITE

A B C D E F G H

- Fc lme/l)

,092 .092 - - X * D . . I38 ,046 ,092 ,092 . I84

S i (mai?)

.i !?.

:, '. I-- - N.D. N.D. N.D. N.D. X . D . N.D.

N.D. N.D. N.D. X.D.

-

-^-- - i . i a 1.4L ,235 .471 ,471. .706

1.65 2:s

1.14 ,411

-

'I. - _

.013 ,013 N . D . .013 N.D. , 013

,013 X.D. ,013 ,013

- .Ob6 .135 ,092 $092

GEOCHEMICAL CONCENTRATIONS IN WELL WATERS

ELEMENT

.S25 1.04 . 697 Zn

Cd

Pb

A s

N i

T i

sr

Na

K

Ca

.092

1.71

.168

2.38

,130

1.89

4.09 6.97 4.05

.174 .707 ,210

N.D.

1 .2

N.D. N.D.

12.8 5.5

23.6 28.2 72.1

33.9 22.6 29.4

103 140 110

As

cr

Fe

A1

Mn

Be

si

cu

.012 .025 .012

.149 .248 .149

. 046

.193

N.D.

. 242

.184

,193

,043 ,150 ,016

N . D . N.D. N.D.

5.55 7 . 0 6 7.06

"013 .013 .013

,

APPENDIX 2

SlYiPLE x SAND Z SILT x CLAY pa X C03 X ORGANIC CEC SITE CARBON ( ~ S / 1 o O s )

A 0 C D E F G H I J K L M N 0

46.39 24.25 15.32 18-79 7.55

11.55 38 . 59 32 . 13 56.77 16.85 62.36 36.24 33.73 50.50 47.86

29.64 43 . 3s 47.23 38 67 47.5s 51 18 34.60 42.42 26.70 48.71 23.99 38.51 42.60 32.58 32.95

23.97 32.40 37.45 42.54 44-90 37.27 26.81 25.45 16.53 34.44 13 . 65 25.26 23.67 16.92 19.19

6.4 7 .O 5.0 5.2 6.6 6.4 7 .O 7.4 8.1 7-7 7 .7 8.3 7.2 7.2 7.0

12.29 6.59 23.42 23.42 8.20 6.49

10.20 7.40 26.00 23 -42 11.18 7:20

7.56 5.35 18 52 23 -42 9 .oo 6.69

12.72 8.90 34.06 15.53 9.89 64.70 19.38 2.71 17.66

* 19.16 9.15 5.60 19.88 2.33 19.80 21.76 5.56 16.82 14.03 9.70 44.70 9.10 7.12 .29.80 17.04 5.83 18.74

APPENDIX 3

CWARXSON OF TILL UNDERLYING THE ANOMALY WITH THE

NEARBY HALTON TIU COMPOSITION

Hal ton T i l l Composition T i l l Composition a t Anomaly Si te 4 Miles N.W. of .

Anomaly (Barnett, 1975)

(3 samples) (1 sample)

X Sand

X Total Carbonate

X Dolomite

X Calcite

Calcite/ Dolomite Ratio

21.83 % 27 %

57.59 %

20.58 %

28.0%

50 %

23 %

23.2 %

10 x

1.32

113

APPENDIX 4 - GEOCHEMICAL CONCENTRATIONS IN SEDIMENT' CORE N 1 .

1 ' -

aAmw za a l c e l

a 52.7 1 18.6

3 51.1 4 68.9 5 111 6 95.4 7 3 14 8 895

10 1m 11 1730 13 1990 14 581 16 306 11 186 I8 9 9

20 191 21 199 22 168 23 81.8 24 80.1 2s 145 16 133 2 1 143 28 149 29 371 30 b21 31 421 II 424 I3 441

19 a23

1 6.53

1 3.52 b 4.02 5 6.78 6 J.53 7 4.02 8 15.3

a 4.02

10 30.7 11 34.7 13 34.7 14 35.7 16 21.1 11 22.1 I8 23.5 19 25.8 20 22 .8 21 26.8 21 22.8

24 20.6 25 33.6

2J az.3

26 21.3 27 27,s

23.1 34.1

28 29 30 38.6 31 62.5 32 33.6 33 35.9

SmPLL si - 1M. &@!L 1 1770 2 1740 3 1770 4 2040 5 2140 6 2140 1 24 10 8 2680 10 IC60 I 1 3310 11 3410 14 I990 1b i 7 8 0 11 29YO 18 2900 19 2740 20 2790 2 1 1-80 22 2313 21 2910 24 3oso 25 IOJO 26 3210 21 3160 28 1120 29 1820 30 1750 31 1860 32 2310 13 2220

n u As 4 I r d l p r c l l e p c r 50.9 8#19 102 A95 35.0 7.20 92.6 ,148 34.0 1.10 102 * 2U 5J.6 15.1 191 .495 62.7 19.1 222 1.49 12.8 12.r 163 . b95 12.8 8.19 101 . w 5 91.J 12.7 165 .991 180 19.6 2.35 1.98 191 21.6 259 2 . U 233 24.1 281 2.w 161 1b.9 236 2.11 135 11.5 118 2.m 108 10.7 114 1.78 111 10.7 118 1.16 121 10.1 111 1.78 116 10.2 183 1.11 ia8 10.7 19s 1.78 113 10.1 150 1.78 99.9 10.7 10 1.78 1M 11.1 1b1 1.78 110 11.7 116 1.02 114 11.5 180 1.78 109 11.5 116 1.18 125 11.1 167 2.02 206 ia .6 214 2.71 208 11.1 aaJ 2.75 a i 3 11.1 a25 2.15 2J3 13.2 a i 6 2.15 191 12.2 227 2.75

coI(GQInArI0UI In S C D M m C W Y 1

cu Ti sr ?* lpel leel uel lpez 9.32 36.8 31.0 0620 6.11 35.3 27.4 8410 4.31 31.0 24.0 9370 4.62 17.1 14.3 9110 8.58 27.8 74.4 9310 6.11 28.0 49.2 9310 12.1 26.2 76.3 7980 15.3 22.8 96.1 1990 31.8 45.a 102 9370 34.3 44.7 118 9370 49.2 30.1 120 9370 21.5 26.8 97.1 4260 17.3 66.8 111 6170 16.8 81.3 134 1650 15.8 85.1 la6 1290 15.1 70.6 123 6540 14.0 74.1 1J2 6790 15.8 U.6 121 6563 18.8 79.7 iaa 6640 11.8 95.6 22s 8270 15.6 102 186 9190 15.8 73.1 1U 6080 16.8 86.2 169 8560 16.3 1P 175 8790

9.22 30.5 89.1 3190 10.7 31.2 90.0 4340 8.14 35.3 93.6 4360 9.46 41.3 101 JO10 11.4 35.4 106 1980

:5.J 88.6 168 1290

o~ocgwclrt C ~ ~ ~ T L ~ T L O N S m s m m ~ corn ni

xn N. C. X &!el leprl

50J zoa 1,380 758

258 31.9 1,380 572 298 61.8 :.210 804 2080 9 1 , s J,290 1130 6&0 86.U 9.580 851 201 101 10,620 804 118 !45 2S.JOO 1480 874 191 31,000 2990 1200 208 119.000 3h00 908 2.73 18J.000 1540 824 165 156,000 4050 1130 454 98,SOO 1630

461 439 92.230 3290

520 447 96.700 3340 J10 414 91, roo 3490 474 316 85, so0 1090 so7 139 82,600 1240 I07 35s 99,800 1240 163 *08 121.000 3130 556 416 111.200 1340 512 a16 92.400 34LO 591 424 96.000 3 130 714 16’3 152,000 so10

556 188 1,100 665

466 424 88,400 3290

J6! 431 95,200 1140

701 581 170,000 5090 668 563 240,000 5020 668 573 2LO ,000 5010 5lJ a2 240,000 SO20

h

lea 16.2 13.0 11.2

31.2 26.J 17.7 21.2 28.2 30.0 35.9 24.1 21.2 20.9 20.9 19.5 20.9 2l.l 21.1 20.9 21.9 22.9 21,7 21.1

22.7 23 , l 24.4 24.1 24.6

31.2

a ~ , 6

Al leeL bI60 4170 4340 5460 6710 J380 5660 6090 4910 5240 5880 1910 3710 L630 4440 3710 3900 3720 3110 4820 5210 hi30 5030 5210 4190 1620 1510 1750

2100 a320

P .LE& 6 4 3 70 J75 1120 LO10 869 552 507 179 688 801 507 314 364 364 114 134 134 180 395 39s 364 195 425 380 213 a i 1 213 218

ui

lea 11.9 10.5 1.09 10.5 19.8 13.7 11.6 25.9 33.0 35.7 36.9 28.6 20.0 20.1 20.7

20.1 11.5 21.5 22.0 23.5 11.4 23.1 u.1 24.1 23.1 23.7 23.7 2J.0 28.7

20.1

. 510 , 6 9 1 .a59 ,704 ,569 .601 .412 .457 .JJO .245 . l l J .186 .160 ,337 ,330 .31J .337 .462 .472 ,374 .461 ,487 .ua .239 .242 .237

, 2 4 9 .a61

5.4 6.3 5.9 7 b - i

7 3 8.0 7.9 7.9

8.2 7 9

m.2

6 9 I , ~ .+ 8.1 7.2 7.9 8.3 ?. i 8.0 8.0 8.0 7.9 3 . 1 !.9 8.0 1.9 7.9 8.0 8.3

1 1 6

ADDITIONAL CHEMICAL AND TEXTURAL PARAMETERS

ON SEDIMENTS FROM CORE " N l "

SAMPLE % Sand PH G! 20° c

'Z Silt % Clay % Cog % ORGANIC

CARBON - - 6.4 6.25 6.4 7.4 7.65 7.8 8.0 7.9 8.0 7.9 8.2 8.2 8.2 7.9 8.0 6.9 7.4 7.9 8.0 8.0 8.0 7,9 8.0 7.9 7.9 8.0

1 15.33 2 _I_

3 6.82

63.84 20 84

31.76

36.57

40.13

- - -

- - 5.22

6.09 5.23

4.78

- - - - 3.46 3.15 4.89

.27.68 ,

27.68

20.22

- -

- 6.98

~ ~~

61.42

51.03

43.73

50.68

- - -

5 13.04 6 7 16.14 8 9 18.23 10 11 19.53 12 13 29.26 14 - 15 31.82 16 17 5.97 20 9.32 21 8.84 24 25 9,99 26 29 21.30 30 31 23.98 33 16.46

- 7

- -

- - - -

8.89 7.31

9.89 -

25.54 19.38 19.58 19.38 20.64 29,82 11.08

31.09

30.02 50.45

49.86

45.88

48. SI 57.78 56.45

47.09

- - ____T1

-

21.49 21.75 25,22

23 54

14.90 16.14 13.63

- -

20.88

22.31.

45.53 32.90 34.71

- - .- 2.41

18.10 2.57 2.58 1.98

20.64

20.22 - 42.92

25.06 - 19.43

16.02 - 2.30

53.64 - 2.33 17.66

54.66 21.35 33.48 1.59 64.48 19.08 36.70 3 . 1 3 23 "43.

I '

APPQIDU 6 - TOTAT. DISCHAXI28 DATA (cubic f r a t por recond) FOR TIU MO”U8 OF 1976 IN TEE NOBTR cREtI[ WATERSHED

(data r r c r iv rd from the Rlnirtxy of Erivirornnrnt (1977))

JAN. FEB. UAX. APR. WAY JUN8 JULY AVC. SEPT. OCT, NOV. DE.. ANNUAL

430.08 2038.6 1401.4 678.49 433.79 24.63 51.6 16.21 15.85 30.19 16.77 28.36 5165.97

M f L Y DISCHARGK DAZA (oubic f r a t par recond) pOa DAYS OF SAMpLg COLLECTION I N 1976 (data rrcaivod f ron tho Mtnirtry of Pnviroouant (1977))

SEPT. 1 SEPT. 14 SEPT. 2% OCT. 13 OCT. 26 uov. 12 mV. 26

,211 .34 1.3 1.4 .82 .a .43

- APPENDIX 7

~ m x ~ y AND mN, PUCIYITATION VALUES (rmn.) FOR THE NORTH CREEK WATERSHED IN 1976 (data received from Dr. M. Sanderson (1977))

JAN. FEB. MAR. APR. MAY JUNE JULY WG. SEPT. OCT. NOV. DEC. ANNUAL

49 53 134 82 94 95 69 31 74 55 12 31 779

DAILY PRECIPITATION DATA (m.) FOR DAYS OF SAMPLE COLLECTION I N 1976 (data received from Dr. M. Sanderron (1977))

SEPT. 1 SEPT. 14 SEPT. 28 OCT. 13 OCT. 26 NOV. 1.2 * NOV. 26

0 0 0 4 0 0 6

A’MoSpI(ERIC LOADING DATA FOR THE NORTH CR88K WATERSHED (data received from Dr. W. Sanderron (1977))

Data of Sample Pr rc ip1t r t ion Specific so4 . c1 Ms cn N. I( Collection i n 1976 QuAntity Conductance (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l)

(=.I ()rmho)

nay 15-Junr 12

June 12-July 13

July 13-Aug. 8

Aup. 8-Sept. 9.

Sept. 9-Oct. 1

Oct. 1-Nov. 3

NOV. 3-Dee. 4

2.9

112

68

32

97

55

I;‘

ZU

(PPb)

72

72.6 11 2.37 ---- 2.65 2.58 0.70

55.5 7.0 0.97 3.5 1.25 0.90

152.3 7.0 4.2 2.45 3.5 17 0.90

53.4 16.5 1.29 1.55 3.35 1.28 0.36

I Z . 8 6.0 0.81 1.55 2.4 0.66 0.25

‘ 4 8 . 6.3 -..*. 2.25 3.0 2.15 2.35

project their influence · data analysis and interpretation: 1, discussion of results and data...

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