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# OAR Box 1131 Prepped by Ollie Stewart



### Document

Number: 

# 123)11-1-40 1 Docket Number: 

# A-83-2 2

Printed 4/21/2008 2:34:12 PM

Sheet 123 of 162P. 2



# V ^ 

# <^ P^ 0* ^ 

## ^ ORNL/NSF/EATC-3 0



## Impac t i fa Lea d Mining-Smeltin g Comple x

i n I k Me wLea i lil t legio n o

fSoofkas S Missour i

A . P . Watso n - R . I . Va n Hoo k - D . R . Jackso n - D . E . Reichl e 

# IM 

# im p HI ! r A Ri htr ? EP A AI R DOCKE T Environmenta l Science s Divisio n Publicatio n No . 88 1



### * •"""^yjrnr ^



# OA KRIDG E NATIONA L LABQRATO R OPERATE D B

YUNIO N CARBID E CORPORATIO N FOR TH E ENERGYRESEARC H AN D DEVELOPMEN TADMINISTRATE ^

""Yjr'iTwi TP. 3P. 4

ABSTRAC T
WATSON , Annett a P. , R . I . VA N HOOK , D . R . JACKSON , an dD . E . REICHLE . Impac t o f a lead mining-smeltin g comple xo nth e forest-floo r litte r arthropo d faun a inth e New Lea dBel t regio no f south eas t Missouri . ORNL/NSF/EATC-30 . Oa k Ridg e Nationa l Labora tory , Oa k Ridge , Tenn . 16 7 pp . Studie s o f biologica l activit y withi nth e litte r horizon s o f a watershe d contaminate d b y emission s fro

m a lead-or e processin g comple x focuse d o nth e litter-arthropo d foo d chai na s a mean s o f detectin g perturbation s i na heavy-meta l contaminate decosystem . Bot hpoin t
source s (smelte r stac k emissions ) an dfugitiv e source s (ore-handlin g processes , yar d dusts , and expose dconcentrat e piles ) contribute dt o th e Pb , Zn , Cu , and C

d level s inth e stud

y are a (Crooke dCree k Watershed , IronCounty , Missouri , 37°38 ' N Lat. , 91°07 ' Long.) . Characterizatio n o f arthropo d foo d bas e an d habita t wa s accomplishe db y critica l examina tio no f litte r mass , heav y meta l an

dmacronutrien t content , catio n exchang e capacity , an d pH . Arthropodtrophi c lj?ye l density , biomass , an d heav y meta l conten t wer e determine db y analysi s o f specimen s remove d fro m litte r b

y vo nTullgre nfunne l extraction , taxonomicall y classified , and segregate d int o th e trophi c categorie s o f detritivore , fungivore , littergrazer , omnivore , an d predator . Th e highes t concentratio no f litte r Pb , Zn , Cu , an dC doccurre di n 0 2 litter . Mea nvalue s o f 10300 0 pp m Pb , 491 0 pp

m Zn , 608 0 pp

m Cu , an d 17 9 pp m C d wer e found i nsample s collecte d0. 4 an d0. 8 k m fro m th e smelter . Thes e elevate d concentration s wer e strongl y correlate d(P<.01 ) wit hanaccumulatio no f undecompose d 0 2 material . Th e mea nannua l 0 2 mass/ m found 21. 0 k

m W o f th e smelte r (contro l area ) wa s 1030+12 6 (SE ) g/m 2 a s compare d t o 2198+20 1 (SE ) an d 1765+14 2 (SE ) g/m 2 fo r th e 6. 4 andP. 5

0. 8 k m sites , respectively . Th e mea nannua l mas s o f 0 1 materia l di dno t diffe r significantl y

throughou t th e study area , bu t varie dabou t a mea n
o f 433+2 9 (SE ) g/ m

(ranging fro

m 12 0 t o 48 0 g/m 2 ) . Mea nannua l 0 1 mas s
a t th e contro l are a wa s 471+3 4 (SE ) g/ m . Change s i nlitte r decompositio nwer e reflecte dinth e dynamic s o f th e litte r arthropo d community . Reduce dvalue s o f tota l arthropo d

2 2 densit y (no/ m ) an d biomas s (mg/ m

) occurre dsimultaneousl y wit helevate d concentration s o f Titte r heav y metals . Thi s reductio nintota l arthropo d biomas s and densit y

wa s governe d b

y a decreas e inbiomas s anddensit y o f th e predator , detritivor e an d fungivor e populations . I naddition , measurement s o f arthropo d richness , anestimat e o f maximu m diversity , reveale d tha t litte r arthropo d population s a t heavil y contaminate dsite s wer e les s ric hi ntaxa (family ) tha nwer e thos e locate delsewher e o nth e watershed . Food-chai ndilutio no f Pb , Zn , Cu , an d C d fro m litte r t o litte r consume r wa s occurring , a s indicate d b y th e mea nconcentratio nfactor s o f 0.07+0.0 2 (Pb) , 0.64+0.1 5 (Zn) , 0.38+0.1 0 (Cu) , an d0.34+0.0 5 (Cd) . Accumulatio no f Pbb y litte r consumer s wa s muc hles s tha ntha t foundfo r th e othe r thre e heav

y metals . T

ncontrast , predator y arthropod s on Crooke d Cree k Watershe d eithe r concentrate do r equilibrate dwit hrespec t t o Pb , Zn , and C

d fro m thei r prey , a s indicate db y mea ntota l predato r concentratio nfactor s o f 1.16+0.2 9 (Pb) , 1.27+0.1 4 (Zn) , an d1.27+0.0 2 (Cd) . O f al l fou r heav y metals , onl y

C u appeare dt o b e dilute db y food chai ntransfe r fro

m pre y t o predato r ( x= 0.67+0.10) . Measurement s o f fres hfoliag e an dlitte r macronutrien t concentra tion s an d litte r macronutrien t pool s indicate dtha t forest-nutrien t dynamic s onCrooke d Cree k Watershe d wer e seriousl y disturbed . Asigni- ^ f i can t Regressio n(P<.Q5 ) o f th e Ca , Mg , an dKconten t o f 0 1 an d0 2 v iP. 6

1 itte r occurre d relativ e t o th e rnntrn l withi nO. Rk m n f thf l star k Tw

o mechanism s wer e postulate d t o explai nthi s result : (1 ) Increase d leachin g o f cation s throug hth e litte r induce d b y a los s o f catio nexchang e capacity , a decreas e i npH , an d a decreas e i nmicrobia l immobilizatio no f macronutrients . (2 ) A decrease d uptak e o f macronutrient s du e t o roo t damag e produce d b

y heavy-meta l concentrations . Th e resul t woul d b e a reduce d annua l macronutrien t inpu t fro m litterfall .
A los s i nlitte r catio nexchang e capacit y andreductio ni nfresh-foliag e macronutrien t conten t wa s measure do nth e Crooke dCree k Watershed . A n accumulatio no f macronutrien t pool s i n0 2 litte r als o existe dbetwee n 1. 2 and 2. 0 k

m o f th e smelter .

v i 1P. 7

- • --t-^rTT T ' t'VWTTT T l

ORNL/NSF/EATC-3 0

Contrac t No . W-7405-eng-2 6

IMPAC T O F A

LEAD MINING-SMELTIN GCOMPLE XO N TH E FOREST-FLOO R LITTE RARTHROPO D FAUN A IN TH E NE W LEAD BEL T REGIO N O F SOUTHEAS T MISSOUR I
A . P . Watson , R . I . Va n Hook , D . R . Jackson , an d D . E . Reichl e ENVIRONMENTA L SCIENCE S DIVISIO N

Submitte db

y A . P . Watso na s a dissertatio nt o th e Graduat e Schoo l o f th e Universit y o f Kentucky inpartia l fulfillmen t o f th e requiremen t fo r th e degre e o f Docto r o f Philosophy Environmenta l Science s Divisio nPublicatio nNo . 88 1

Wor k supporte db

y th e Nationa l Scienc e Foundatio n- - RAN N Environmenta l Aspect s o f Trac e Contaminant s Program unde r NS F Interagenc y Agreemen t AE N 72-01243A0 3 wit hth e Energy Researc han

d Developmen t Administration .

JUL Y197 6

OAKRIDG E NATIONAL LABORATOR Y Oa k Ridge , Tennesse e 3783 0

operate db

y UNION CARBID E CORPORATIO N fo r th e ENERG YRESEARC H AN D DEVELOPMEN T ADMINISTRATIO NP. 8

ACKNOWLEDGMENT S
Thi s researc hwa s supporte db y th e Nationa l Scienc e Foundation RAN N Environmenta l Aspect s o f Trac e Contaminant s Program unde r NS F Interagenc y

Agreemen t AEN

72-10243A0 3 wit hth e Energy Researc han

d Developmen t Administration . Th e autho r performe dth e researc ha t th e Oa k Ridg e Nationa l Laborator y (ORNL , operate db

y Unio nCarbid e Corporatio nfo r th e Energ y Researc han

dDevelopmen t Administration ) whil e unde r appointmen t t o th e Laborator y Graduat e Participan t Program administere db

y Oa k Ridg e Associate dUniversities . Th e cooperatio no f th e AMAX-Homestak e Smeltin g Company personne l i s gratefull y

acknowledged . Specia l thank s i s du e Georg e Carr , environmenta l enginee r fo r th e smelte r operatio nnea r Bixby . Particula r recognitio ni s du e JohnWright , wh o cheerfull y supplie d invaluabl e fiel dassistanc e onCrooke dCree k Watershed . Ome r Phillip s provide dmuch-appreciate dtechnica l suppor t i nth e preparatio no f litte r sample s fo r heav y meta l analysis . Statistica l advic e an d counselin g o nexperimenta l desig nan danalytica l procedure s wer e capabl y furnishe db

y JohnBeauchamp , RonHiltunen , an dRo dStrando f th e Dat a Resource s Grou p(ORNL) . Nei l Griffit han dJerr y Raine , operator s o f th e Remot e Batch . Statio nFacilit y (ORNL) , provide dhelpfu l programmin g assistanc e an dra nth e numerou s job s submitted . W e als o wis ht o than k Dr . J . G . Rodriguez , Dr . B . C . Pass , Dr . P . H . Freytag , Dr . J . E . Leggett , Dr . J . A . Saye g (Universit y o f Kentucky) , andDr . W . F . Harri s (ORNL ) fo r critica l evaluatio n
o f th e manuscript .



### mTABL E O F CONTENT S T " "T»""T« f "' ' - "TtTfTf'"" "

Pag e P. 9

ACKNOWLEDGMENT S ABSTRAC T , LIS T O F TABLE S LIS T O F FIGURE S LIS T O F APPENDICE S . INTRODUCTIO N MATERIAL S AN D METHOD S Stud y Are a Samplin g Procedure s Locatio no f Stud y

Plot s Litte r Samplin g andInitia l Processin g . . Arthropo dSamplin g andInitia l Processin g Analytica l Procedure s Heavy Metal s Chemica l Characterizatio no f Litte r . . . Arthropo dDiversit y

Measuremen t Arthropo dPopulatio nDensit y andBiomas s . Statistica l Procedure s RESULT S AN D DISCUSSIO N Crooke dCree k Watershe dLitte r Litte r Mas s Litte r Heavy

Meta l Conten t Litte r Heavy

Meta l Poo l Chemica l Characterizatio no f Litte r . . , Arthropod s .... . Populatio nDensit y

andBiomas s , Heavy Metal s Concentratio nFactor s . Diversit y 

### m

x i
x v
x v i i 1 4 4 7 7 8 1 3 1 4 1 4 1 5 1 6 1 7 1 8 2 0 2 0 2 0 2 5 4 0 4 4 5 2 5 2 6 1 6 6 7 6

I XP.1 0

GENERAL DISCUSSION Heav y Meta l Effect s on Biot a Minera l Cyclin g SUMMAR YAND CONCLUSION S APPENDICE S Appendi xA Appendi xB Appendi xC Appendi xD REFERENCE S CITE D Pag e 8 1 8 1 8 6 8 9 9 3 9 4 10 1 12 9 13 8 15 1

•PBBIpgij,j..jjijUJJ iLIS T O F TABLE S

Tabl e 1 .
2 .



### 7 .

9 .

10 . Pag e 1 1

2 2

Watershe d 0 2 litte r mas s (g/ m , transforme d b

y Eqn . 3 ) ( n= 174 , F 2 3 15 0 = 3.838 , R 2 = 0.370) . Correlatio nmatri xresultin g fro m multipl e linea r regressio nanalysi s o f Crooke d Cree k Watershe d 0 2 litte r mas s (g/m 2 , transforme d b y Eqn . 3 ) ( n = 174 , F 2 3 15 0 = 3 ' 838 ' R = °- 3 7 °) - Multipl e linea r regressio nstatistic s fo r Crooke d Cree k Watershe d 0 2 litte r mas s (g/m 2 , transforme d b y Eqn . 3 ) an d independen t variable s selecte d b y th e backwar d eliminatio nprocedur e a t P = 0.2 5 ( n = 174 , F 1 4 15 9 = 6 ' 344 ' R 2 = °- 358 ) - Compariso no f Pb , Z n an d C d concentration s (ppm ) i n Walke r Branc hWatershe d and Crooke d Cree k Watershe d lea f litte r an

d soils . Septembe r mean s o f 0 1 heav y meta l pool s analyze d b y Duncan' s Ne w

Multipl e Rang e Test . Mean s followe d b y th e sam

e lette r ar e no t significantl y differen t a t th e 5 % level . Septembe r mean s o f 0 2 heav y meta l pool s analyze d b y Duncan' s New

Multipl e Rang e Test . Mean s followe d b y th e same lette r ar e no t significantl y differen t a t th e 5 % leve l (Duncan , 1951 ; Stee l an d Torrie , 1960) . 

### 23 Landscap e character s and dominan t vegetatio no f Crooke d Cree k Watershe d stud y sites . Seasona l mean s o f 0 1 litte r mas s analyze d b y Duncan' s New Multipl e Rang e Test . Mean s followe d b y the sam e lette r ar e no t significantl y differen t a t th e 5 % leve l (Duncan , 1951 ; Stee l an d Torrie , 1960) . Seasona l mean s o f 0 2 litte r mas s analyze d b y Duncan' s Ne w Multipl e Rang e Test . Mean s followe d b y th e same lette r ar e no t significantl y differen t a t th e 5% leve l (Duncan , 1951 ; Stee l and Torrie , 1960) . Seasona l mea nas hconten t {% dr y wt ) o f Crooke d Cree k Watershe d litter . On e standar d erro r in parenthese s (n=3) . Th e N

W transec t wa s chose na s representativ e o f th e watershed . Multipl e linea r regressio nstatistic s fo r Crooke d Cree k 3 6 

### 26

3 8

39

4 1

4 2

4 3

X I

!i«y»>J !P.1 2

Tabl e 

### 11 . 12 .
13 . 14 .
15 .
16 .

17 .

18 .

19 .

20 . Catio nexchang e capacit y an d p H o f 0 2 litte r o

n Crooke d Cree k Watershe d (N W transect) . Mea nmacronutrien t concentratio ni noa k leave s on Crooke d Cree k Watershe di nrelatio nt o distanc e fro m th e smelte r (n=6) . Macronutrien t pool s o f 0 2 litte r onCrooke dCree k Watershe d (N

W transect) . Seasona l mea narthropo dbiomas s (m g dry wt/m 2 ) in th e litte r 0 2 horizo no f Crooke d Cree k Watershed . On e standar d erro r inparenthese s (n=4) . Seasona l mea narthropo ddensit y (no./m 2 ) inth e litte r 0 2 horizo no f Crooke d Cree k Watershed . On e standar d erro r i nparenthese s (n=4) . Mea nannua l Crooke d Cree k Watershe d0 2 litte r arthropo d predator , detritivor e an d fungivor e biomas s (m g dr y wt/m 2 ) an

d densit y

(no./m 2 ) . Season s hav e bee npoole d a s replicates . Value s i nparenthese s ar e 1 standar d erro r (n=16) . Multipl e linea r regressio nstatistic s fo r Crooke d Cree k Watershe d 0 2 litte r arthropo dbiomas s (mg/m 2 , transforme d b

y Eqn . 3 ) ( n= 176 , F« - , c o = 6.931 , R 2 = 0.512) . 23 ' 15 2 Correlatio nmatri xresultin g fro m multipl e linea r regressio nanalysi s o f tota l arthropo dbiomas s (mg/nr , transforme d b

y Eqn . 3 ) found o

nCrooke d Cree k Watershe d ( n= 176 , F 2 3 15 2 = 6.931 , R 2 = 0.512) . Multipl e linea r regressio nstatistic s fo r Crooke d Cree k Watershe d 0 2 litte r arthropo dbiomas s (mg/m 2 , transforme d b

y Eqn . 3 ) and independen t variable s selecte d b

y th e backwar d eliminatio nprocedur e a t P = 0.2 5 ( n= 176 , F 1 4 ]6 1 = 10.178 , R 2 = 0.507) . Lea d concentration s (yg/ g dr y wt ) found associate d wit harthropo d trophi c level s onCrooke d Cree k Watershed . Specimen s fro m bot hlitte r horizons , al l seasons , and al l replicate s wer e poole dfo r chemica l analysi s (n=32) .



### xi i ""H'TT " '" ' T ""' r

Pag e 

### 4 7 4 8

5 1
5 3

5 4

5 5

5 8

5 9

60

6 3 

# 11 "T T T" r ""! , ""ff¥!" f "" ' P . 1 3

Tabl e 21 .



### 22 .

23 .

24 .
25 .
26 .
27 ,
28 . Zin c concentration s (yg/ g dr y wt ) found associate d wit harthropo d trophi c level s onCrooke d Cree k Watershed . Specimen s fro m bot hlitte r horizons , al l seasons , and al l replicate s wer e poole d fo r chemica l analysi s (n=32) . Coppe r concentration s (yg/ g dr y wt ) found associate d wit harthropo d trophi c level s o nCrooke d Cree k Watershed . Specimen s fro m bot hlitte r horizons , al l seasons , an

d al l replicate s wer e poole d fo r chemica l analysi s (n=32) . Cadmiu m concentration s (yg/ g dr y wt ) found associate d wit harthropo d trophi c level s onCrooke d Cree k Watershed . Specimen s fro m bot hlitte r horizons , al l seasons , an d al l replicate s wer e poole d fo r chemica l analysi s (n=32) . Weighte d concentratio nfactor s calculate d fo r P b transpor t i nth e Crooke d Cree k Watershe d litter arthropo d foo d chain . Weighte d concentratio nfactor s calculate d fo r Z n transpor t i nth e Crooke d Cree k Watershe d litter arthropo d food chain . Weighte d concentratio nfactor s calculate d fo r C u transpor t i nth e Crooke d Cree k Watershe d litter arthropo d foo d chain . Weighte d concentratio nfactor s calculate d fo r C d transpor t i nth e Crooke d Cree k Watershe d litter arthropo d foo d chain . Crooke d Cree k Watershe d litte r arthropo d diversit y indice s fo r eac hsite , horizo nan d season : a . Shannon-Weave r Index , H ' (calculate d b y Equatio n#1 ) b . Pielou' s evennes s index , J ' (calculate d b y Equatio n#2 ) c . Richnes s index , S (tota l numbe r o f families ) Pag e 6 4



### 6 5

6 7

6 9

7 0

7 1

7 2

7 7

x mP.1 4

LIS T O F FIGURE S Pag e Fig . 1 . Locatio no f Den t an d Iro nCountie s i nMissouri . 5 Crooke d Cree k Watershe d i s inIronCounty , 3 8 k m eas t o f Salem . Fig . 2 . Topography

an d vegetatio no f Crooke dCree k Watershed . 6 Stat e road s J , 32 , an dth e St . Louis-Sa nFrancisc o railwa y form th e W , N , an

d N E boundaries , respectively . Fig . 3 . Wind-ros e pattern s a t th e AMAX-Homestak e smelte r stac k 9

fo r Fal l an

d Winter , 197 0 an

dSprin g an

d Summer , 1971 . Dat a take nfro

m Wixson , ej

t al_. , 1972 . Fig . 4 . Samplin g gri d utilize d onCrooke d Cree k Watershe dfo r 1 0

collectio no f litte r an darthropod s i nth e presen t study . Crooke d Cree k Watershed , a 46 6 ha . portio n o f th e Clar k Nationa l Forest , i s locate d i nIron County , Missouri . Fig . 5 . Mea nlitte r mas s ( g dry wt/m" ) o f 0 1 an

d0 2 horizon s 2 1 o nCrooke d Cree k Watershe da s a functio no f distanc e an d directio nfro

m th e AMA Xsmelte r fo r th e September , 1974 , samplin g perio d ( x+

_1 SE , n=4) . Fig . 6 . Poole d mean s o f litte r mas s ( g dr y wt/ m ) o f 0 1 an

d0 2 2 4 horizon s onCrooke d Cree k Watershe da s a functio no f distanc e from

th e AMA Xsmelte r fo r eac hsamplin g period , 1974 . Value s fo r th e NE transec t wer e exclude dfro m computatio no f th e mean s ( x+ 1 SE , n=12) . Fig . 7 . Mean s o f litte r P bconten t (yg/ g dry wt ) i n0 1 an

d0 2 2 8 horizon s a s a functio no f distanc e an d directio nfro

m th e AMA Xsmelte r fo r th e September , 1974 , samplin g perio d ( x+

_1 SE , n=4) . Fig . 8 . Mean s o f litte r Z nconten t (yg/ g dry wt ) i n0 1 an

d0 2 2 9 horizon s a s a functio no f distanc e an d directio nfro

m th e AMAX_smelte r fo r th e September , 1974 , samplin g perio d ( x+

_ 1 SE , n=4) . Fig . 9 . Mean s o f litte r C u conten t (yg/ g dr y

wt ) in0 1 an

d0 2 3 0 horizon s a s a functio no f distanc e an d directio nfro

m th e AMA Xsmelte r fo r th e September , 1974 , samplin g perio d ( x+

_1 SE , n=4) . Fig . 10 . Mean s o f litte r C d conten t (yg/ g dry

wt ) in0 1 an

d0 2 3 1 horizon s a s a functio no f distanc e an ddirectio nfro

m th e AMA Xsmelte r fo r th e September , 1974 , samplin g perio d ( x+

_1 SE , n=4) . x

v

WgjBj | Wg^L^ l ^llt ll ^ l i'-'.-'tiV-'-W? T ^ °• > -m -T- T ^ * T'"PJ||,|I f P.1 5 "Tp j

Fig . 11 . Poole d mean s o f litte r Pb , Zn , Cu , an d C d concentration s (yg/ g dr y

wt ) a s a functio no f distanc e fro m th e AMA

X smelte r fo r September , 1974 . Value s fo r th e NE transec t wer e exclude d fro

m computatio no f thes e mean s ( x+ 1 SE , n=12) . Pag e 3 4

Fig . 12 . Mea nmacronutrien t concentration s o f Ca , Mg , K , an d P (+

_ 1 SE , n=12 ) in Crooke d Cree k Watershe dlitte r a s a functio no f distanc e fro m th e AMA Xsmelter . Dat a fro m Jackso nand Watson , 1976 . 

### 4 5

Fig . 13 . Mea nmacronutrien t poo l size s o f Ca , Mg , K , an d P (+

_1 SE , n=12 ) in Crooke d Cree k Watershe dlitte r a s a functio no f distanc e fro m the AMA Xsmelter . Dat a fro m Jackso nand Watson , 1976 . 

### 5 0

xv iP.1 6

LIS T O F APPENDICE S Appendi x Trophic-leve l assemblag e an dabundanc e o f arthropo d taxa (excludin g Acarina ) foundonCrooke dCree k Watershe d durin g th e study yea r (1974) . Listin g o f al l arthropo ddat a collecte dfro m Crooke d Cree k Watershe d litte r b y taxon , season , site , horizon , an

d lifestage . Trophi c leve l designation s wer e reference d i nAppendi xA . Seasona l mean s o f heav y meta l conten t (Pb , Zn , Cu , and Cd ) ranke d accordin g t o result s o f Duncan' s New Multipl e Rang e Test . Pooled , seasona l mean s o f litte r Pb , Zn , Cu , an d C d conten t (yg/ g dry

wt ) a s a functio no f distanc e fro m th e smelter . Value s fo r th e N E transec t wer e exclude d fro

m computatio n( x+ 1 SE , n=12) . Pag e 9 4

10 1



### 12 9

13 8

x v n

*"•^^TM ~ -pm

INTRODUCTIO N
Lea dpresentl y

occur s a s a globa l pollutan t (Committe e onBiologi c Effect s o f Atmospheri c Pollutants , 1972 ) bu t fe w reference s ar e availabl e documentin g th e effect s o f P bsource s onlitte r arthropods . Preliminar y

evidenc e exist s t o sugges t possibl e transfe r o f elementa l P bthroug hplant-herbivore-carnivor e foo dweb s fro m roadwa y "lin e sources " (Giles , e_

t al_. , 1973 ; Rolf e et ^ aj_. , 1974) . N o study ye t publishe dha s attempte dt o documen t suc hbiologica l transfe r withi na litte r system , althoug hi t ha s bee nshow ntha t litter-grazin g isopod s collecte dfrom

roadsid e ditchbank s contai nsignificantl y elevate d concentration s o f P brelativ e t o value s foundinpredaceou s spider s o r opilionid s (Williamso nan dEvans , 1972) . A s no heav y meta l analysi s o f th e decayin g vegetatio nwa s made , concentratio nfactor s coul dno t b e calculate dfro

m Williamso nan

dEvans ' data . Incontrast , no differ enc e coul db e detecte dindistributio no r abundanc e o f identica l taxa founda t site s rangin g intota l soil-lea dconten t fro m 7 0 pp m (roadwa y ditchbank ) t o 1900 0 pp m (overgrow

nlead-min e spoi l heaps ) (Williamso n andEvans , 1973) . However , neithe r tissue-lea dno r litter-substrat e leadanalyse s wer e performed . I t i s wel l know

ntha t th e seasona l uptak e o f nutrient s indecidu ou s forest s depend s upo nmineralizatio no f litte r b y saprovor e popula tion s (Ovington , 1960 ; Witkam pan dAusmus , 1975) . I t i s als o know n tha t litte r ca nserv e a s a heav y meta l reservoi r b

y chelatio no r catio n exchang e processe s (Ruhlin g an dTyler , 1973 ; Hirst , et . aj_. , 1961) . Becaus e disruptio no f decompositio nca naffec t th e fores t ecosyste m b y accelerate dnutrien t losse s an dreduce dmineralizatio nrate s (Tyler , 

### 1P.1 8

1972) , examinatio no f heavy-meta l effect s o nth e litte r communit y i s importan t i nfull y

understandin g basi c ecosystem processes . Inunperturbe decosystems , arthropod s o f th e litte r communit y ac t
a s "catalyst s o f microbia l metabolism " (Macfadyen , 1963 ) inth e decom positio nprocesses . Passag e o f litte r throug hth e arthropo dgu t pro duce s a substrat e favorabl e t o microbia l decompositio nvi a fragmentatio n
andchemica l alteratio n(Nicholson , e_ t aj_. , 1966 ; va nde r Drif t an d Witkamp , 1960 ; McBraye r andReichle , 1971) . Suc hsubstrat e modificatio n support s th e hypothesi s tha t thes e animal s ma y ac t a s decompositio n rat e regulator s (McBrayer , 1973) . Dispersa l andgrowt ho f microorganism s i s als o aide db y th e physica l presenc e o f arthropods . Inoculatio no f litte r substrat e can occu r fro

m spore s transporte do nspines , seta e an

dappendage s (Szabo , 1974 ; Witkamp , 1960 ) o r infeca l deposit s (Macfadyen , 1968) . Micro habitat s fo r bacteria l an dfunga l multiplicatio nar e produce db y arthropo dburrowin g activitie s (Szabo , 1974) . I nshort , litte r arthropod s an ddecompose r microorganism s ar e inseparabl y

linke dinth e breakdow no f non-livin g plan t material . An y perturbatio nuncouplin g th e clos e association s i nth e decompose r communit y

wil l hav e aneffec t onth e releas e o f nutrient s fro m litter . Th e primar y

objectiv e o f th e presen t study wa s t o determin e th e degre e t o whic hleadca nb e biologicall y transporte db

y th e principa l arthropo dfoodchain s presen t i na forest-floo r litte r communit y subjecte dt o heavy-meta l contamination . T o accomplis hthi s goal , i t
wa s als o necessar y

t o physicall y

an dchemicall y

characteriz e th e litte r habitat .P.1 9

Th e study

are a chose nwa s a southeaster nMissour i watershe dreceiv in g stac k emission s and fugitiv e sourc e dust s originatin g fro m an adjacen t primar y

lea d smelteropgrate d b v th e AMA Xan dHomestak e Smeltin g Companie s sinc e 1968 . Th e watershe di s uniqu e i ntha t th e woodlan d ecosyste m

i s largel y

intact , havin g sustaine dlittl e damag e du e t o th e extensiv e lumbering , burning , an dsoi l erosio ntha t characterize s many othe r smelte r site s (Jordan , 1971 , 1973 , 1975 ; Witkam pe_ t aJL , 1966) . I naddition , periodi c monitorin g o f smelte r emissions^i^ositeT^o nth e watershe d ha s bee nmad e sinc e 197 1 (Wixso ne_ t aj_. , 1972 ; Wixson , 1974) . Du e t o th e presenc e o f heav y metal s othe r tha nPbi nsourc e dusts , al l sample s wer e analyze d fo r Zn , Cu , andC da s wel l a s P bt o examin e fo r possibl e synergisti c o r additiv e effect s o nbiologica l transport .P.2 0

MATERIAL S AND METHOD S
Study Are a Th e stud y are a i s a 46 6 ha . watershe dlocate dinth e Clar k Nationa l Forest , IronCounty , Missour i (37°38 ' N Lat. , 91°07 ' Long. ) (Fig . 1) . Name dfo r it s mai ndrainage , Crooke dCree k Watershe d(CCW ) lie s onth e now

deepl y dissecte dremnant s o f th e Salem Plateau . Loca l topography

(Fig . 2 ) i s characterize db y hill s alternatin g wit hstee p valley s (Schwar z an

dSchwarz , 1959) . Th e second-growt hcanopy species , blac k oa k (Quercu s velutin a Lam.) , whit e oa k ((} . alb a L.) , norther n
redoa k (Q . borea l i s Michx.) , pos t oa k ((£ . stellat a Wang) , an dblack jac k oa k (C[ . marilandic a Muenchh) , provide d74+5 % (SE ) o f th e tota l canopy biomass . Shortlea f pin e (Pinu s echinat a Mill. ) provide d 16+6 % o f th e tota l canopy biomas s (Dixon , 1974) . Watershe dsoil s wer e thin , stony , limestone-residual , chert y sil t loams . Ridgetop s possesse da Lebano nsoi l typ e wit ha 5- 8 c m fragipan ; slop e soil s wer e dominate db y chert y sil t loam s o f th e Wildernes s (40% ) andClarksvill e (25% ) series . Valle y floor s wer e occupie db

y alluvia l Razor t an

dAshto nsoil s (Kickbush , 1975) . Soi l Conservatio nServic e dat a fro m neighborin g Den t Count y indicate da mea nannua l rainfal l o f 106. 7 c m wit h31 % o f th e precipi tatio nreceive di nth e sprin g (March-May) , 51 % i nth e summe r (June August ) an

dfal l (September-November) , an d18 % durin g th e winte r (December-February) . Mea ntemperature s inDen t Count y range dfro

m 0.6° C i nJanuar y

t o 25.5° C inJuly . Ther e wer e anaverag e o f 17 7 frost-fre e day s pe r yea r (Gilbert , 1971) .

# r iy>^".M'

. '•' * ' M * ' " » mm*mmnjmmmmmi**1*

ORNL-DW G 76-263 7
IRO N COUNTY DEN T COUNTY

Fig . 1 . Locatio no f Den t an d IronCountie s i n Missouri . Crooke dCree k Watershe di s i n IronCounty , 3 8 k m eas t o f Salem . e nT W = "x^-*TTT n

ORNL DW G75-1580 2

Fig . 2 . Topograph y

andvegetatio no f Crooke dCree k Watershed . Stat e road s J , 32 , andth e St . Louis-Sa nFrancisc o railwa y for m the W , N , andN E boundaries , respectively .P.2 3

Crooke dCree k Watershe dha s bee nsubjec t t o intermitten t grazin g b y cattle , sheep , an

d hog s bot hprio r to , an d following , purchas e b y th e U.S . Fores t Servic e fo r inclusio nin th e Nationa l Fores t Syste m i n th e 1930' s (Wright , 1974) . Althoug hth e origina l Fores t Servic e managemen t scheme calle dfo r multi-purpos e use , th e are a ha s become th e sit e o f lead/zin c mining , milling , an d smeltin g activit y

sinc e th e discover y o f ric hdeposit s nea r Viburnu m ( 8 k m N o f CCW ) in 1955 . Th e "Viburnu m Trend " i s no w

acknowledge dt o b e th e larges t an d riches t know

nlea d deposi t i n th e worl d(Missour i Divisio no f Geologica l Surve y an d Wate r Resources , 1971 , 1974) . A numberO_ f hea w mP^a ] gnnrrn< - rwir t n>ni
- ri-nnk-nr i Pi.nok^Ul a torche d AMA XLea dCo . o f Missouri , in cooperatio nwit hHomestak e Minin g Co. , ha s manage da primar y

lea dsmelte r a t th e ape xo f th e triangularly-shape d waTer*she

d Sinc e 1968~ ! A

mine-mil l comple xoperate db y COMINCO~HliieTica

n transport s Pb , Z n an d C u concentrat e alon g th e St . Louis-Sa nFrancisc o railwa y formin g th e northeaster nboundar y o f th e watershe d(Fig . 2) . Unti l 1974 , loade drailroa dcar s wer e no t covered , an d thei r dr y

content s
wer e readil y

blow nint o th e study

are a (Wright , 1974) . Expose dpile s o f C uconcentrat e adjacen t t o th e railwa y als o serv e a s sourc e areas . Thus , bot hpoin t source s (smelte r stac k emissions ) an d fugitiv e source s (ore-handling processes , yar ddusts , an d expose dconcentrat e piles ) contribute dt o th e heavy-meta l loadon th e watershed . Samplin g Procedure s Locatio no f Study Plot s Seasona l mean s o f wind-ros e pattern s wer e use dt o develo pa fiel d samplin g gri do n directiona l transect s originatin g fro m th e bas e o f th e8

smelte r stac k (Fig . 3) . Inaccordanc e wit hUnite dState s Fores t Servic e permanen t plo t inventor y procedures , 0.0 4 h

a (0. 1 A ) study

plot s (Fig . 4 )
wer e establishe d a t 0. 4 k m (0.2 5 mi ) interval s alon g eac htransec t (Clar k Nationa l Forest , 1972) . Th e on e exceptio nwa s th e placemen t o f th e thir d plo t onth e NE transec t 10 0 m fro m th e second . Th e locatio n
o f th e St . Louis-Sa nFrancisc o railwa y alon g th e easter nridgeto p boundar y prevente d th e locatio no f thi s sit e exactl y 1. 2 k m fro m th e stac k base . A gri d incorporatin g 3 2 site s o n7 transect s wa s employe ddurin g initia l samplin g i nSeptembe r an d December , 1973 . Result s fro m thes e samplin g period s indicate d tha t n o significan t difference s inheav y meta l conten t o r litte r mas s exis t betwee nno t onl y th e 1. 6 an

d2. 0 k m sites , bu t als o betwee nth e WNW-NW , NNW-N , an dNNE- N transects . A refine d gri d incorporatin g 1 5 site s o n4 transect s wa s use dfo r th e one yea r (1974 ) fiel d samplin g reporte d i nthi s stud y (Fig . 4) . A tree , conspicuousl y

marke d wit hflaggin g tap e anda naluminu m identificatio ntag , designate d th e cente r o f eac h0.0 4 h a study plot . Th e slop e and aspec t o f eac hplo t wer e measure dwit ha Hag a altimete r
and surveyor' s compass . Elevatio nmeasurement s wer e derive dfro m altimete r reading s correcte d fo r barometri c pressur e fluctuation s b y periodi c monitorin g a t severa l U.S.G.S . benchmark s i nth e area . A plo t
summar y o f landscap e characteristic s an ddominan t overstor y

specie s i s give ni nTabl e 1 .

Litte r Samplin g andInitia l Processin g Th e Soi l Scienc e Societ y o f Americ a recognize s tw o litte r horizons , 0 1 an d 02 . Plan t materia l o f th e 0 1 laye r ha s retaine dit s origina l



# mm 

# wmmm

# n

F »EQUENC V ( % j CAL- M 1 —

0 ? 1 ' . 0»p» t

• i *-T »-< 2 •)•• » •»-.? «

UMN O S»CC D .">o M

4 6 9 ' 0 ' ? 1 1 1 , 1 1 •0* C ' ••? )

• 4

- J «-«•', •

4 Jf 1

Wm o ftoso o r AMA X Sm.lrt r i n Sprin g S.OSO n 1971 .
*"> a R 0 , t o t iMa x Sm.lr. r l 0 , Summ. , ,97, .

W.n a Ro „ 0 , AMA X S»,l„ , ,„ , Fo „ s , „ o n 4 ,,, „ F i g

. 3

. Wind-ros e pattern s a t th e *'* 0 SPEE D ime m 0 * * « « ' 0 .1 „ Jt

*<" 0 Ro> t o r AMAX S mt)f „ f 0 f Winte r S«o»on , I97Q . 

# E S«j f S Kri ^ w ; fro m Wixson , e_

t aj_. , 1972

. Data take n

### 4 

## A

T O BOS S CROOKED ORNL-DW G 74-393 1 -T O BIXB Y

PRIVAT E ROA D

MAGMON T MIN E (COMINCO )

Fig

. 4

. TAILING S PON D

LOUIS-SA N FRANCISC O R R Samplin g gri dutilize do n Crooke d Cree k Watershe dfo r collec tio no f litte r and arthropod s i n th e presen t study . Crooke d Cree k Watershed , a 46 6 ha . portio no f th e Clar k Nationa l Forest , i s locate di n IronCounty , Missouri .

h o 0 )•-T 5 *T»r T w - • imnfTCTf " -v - 

### "T l



### 1 1 Tabl e 1 . Landscap e Character s an d Dominan t Vegetatio n o f Crooke d

Cree k Watershe d StudySites
.

Site * Slop e Aspec t Elevatio n (km ) (% ) (Q ) (m ) Dominan t Specie s
W 0. 4 12. 5 24 0 422. 7 Queraus stellata Wan g Q. marilandioa Mueunchh . W 0. 8 11. 5 12 6 418. 5 Q. alba L . Pinus echinata Mil l W 1. 2 5. 5 5 3 403. 5 Q. velutina Lam . Q. stellata Q. alba W 1. 6 10. 5 266 414. 8 Q. alba Q. stellata Q. velutina N W0. 4 7. 5 29 0 401. 7 Q. alba Q. aoacinea Q. velutina
v-- N

W 0. 8 11. 5 40 398. 9 Q. borealis Michx . Q. stellata Q. velutina 1. 2

N W2. 0 4 0 390. 1

382. 8 Q. stellata

Q. velutina Carya texana Buckl
. Q. stellata C. tomentosa (Poir. ) Crataegus spp . Juniperus virginiana Salix spp . 

### N
N N
N 0. 4
0. 8 1. 2
2. 0 1 8


### 9 2 4


### 7 29 0 29 0 6 5


### 27 0 423. 0

421. 5 392. 5
401. 7 Q. alba

Q. velutina Q. Velutina Q. alba Q. borealis Q. alba Q. stellata Q. velutina••rw r 'i*-vrrrw P.2 8
1 2

Site * (km ) N E 0. 4

N E 0. 8

N E 1. 2 Slop e



### 1 1 1 2 2 4 Aspec t 

# (° ) 31 0 27 0 6 5 W 10. 5 11. 5 18 5 (secondar ycontrol )

W 16. 4 8. 5 33 0 (secondarycontrol )

W 21. 0 (control ) 

### 9. 5 12 0 Elevatio n (m ) 413. 0
417. 9
392. 5 384. 7

424. 0

395. 6 Dominan t Specie s

Q. Q. Q. Q. Q. Q. Q. C. Q. C. alba velutina alba borealis alba marilandioa stellata velutina tomentosa alba velutina texana Q. stellata Q. velutina Carya ovalis (Wang. ) *Se e Fig

. 4,- T , , ,.-.,pr 1 3 conformation . Materia l o f th e 0 2 laye r i s fragmente d an d no longe r recognizabl e a s t o specie s o r origi n(Black , 1965) . Inthe presen t study , fou r replicat e sample s o f bot hlitte r horizon s wer e randoml y collecte d a t eac hwatershe d sit e an d a t on e contro l sit e 21. 0 k m wes t
o f th e smelte r are a durin g March , Jun e an d Septembe r o f 197 4 an d Januar y
o f 1975 . Eac hpai r o f sample s include d al l litte r withi na 0. 1 m area . T o reduc e edg e effec t an d facilitat e cuttin g throug hleave s an d stems , a circula r fram e o f stainles s stee l wit ha sharpene d edg e wa s use d (Medwicka-Kornas , 1971 ; McBraye r e t al. , 1974) . Additiona l collection s
wer e mad e a t 10. 5 an d 16. 4 k

m wes t o f th e smelte r are a i nSeptembe r 2 an d Januar y

t o establis ha measur e o f th e gradien t inlitte r mass/ m wit hdistance . Th e Septembe r sample s wer e collecte d prio r t o leaffall . I n1974 , leaffal l occurre d i nmid-Octobe r (Drobney , 1974) . Followin g transpor t t o th e laborator y an d extractio no f arthropods , th e litte r wa s hand-sorte d t o remov e rock , oven-drie d a t 100° C t o con stan t moisture , an

d weighe d t o th e neares t 0. 1 gm . Arthropo d Samplin g an d Initia l Processin g Field-collecte d litte r wa s place d int o polypropylen e bag s an d transporte d t o Oa k Ridg e Nationa l Laborator y instyrofoa

m cooler s packe d wit hic e t o maintai n5°C , a storag e temperatur e suitabl e fo r arthropo d surviva l (Edward s an d Fletcher , 1971) . Sample s wer e hel d
a t 5° C i ncontrolled-environmen t chamber s a t th e laborator y (7-1 0 da ) unti l arthropod s coul d b e remove d b y 72-hou r vo nTullgre nfunne l extrac tion . Arthropod s wer e collecte d inanaqueou s solutio no f 70 % ET0 H an d 5 % glycerin , identified , and store d i n70 % ET0 H fo r furthe r processin g (Macfadyen , 1955 , 1962) .P.3 0

1 4
Al l preserve darthropods , excep t Acarina , wer e classifie dt o famil y
an denumerate db

y taxo nandreplicat e pe r sit e fo r later analysis . A n adequat e measur e o f Acarin e populatio ndensit y an dbiomas s ina natura l system i s a projec t requirin g separat e stud y (McBraye r e_

t al_. , 1974) , an dwa s therefor e no t attempte dinth e presen t research . T o preven t difficultie s arisin g fro m attemptin g t o dr y

specimen s store dindilut e alcoho l containin g glycerine , specimen s wer e transferre dfro m th e von Tullgre nvial s t o holdin g vial s containin g 70 % ethano l only . Sample s
wer e the ndrie di nthes e latte r containers . Averag e dr y weight s o f
eac hlifestag e o f ever y taxo nfoundonCrooke dCree k Watershe dwer e calculate dfrom

individua l determination s o f 4-2 0 specimen s drie da t 70° C fo r 2 4 hour s andweighe dt o th e neares t 0.0000 1 g . Literatur e documentatio nwa s use dt o segregat e taxa int o th e trophi c categorie s detritivore , fungivore , littergrazer , omnivore , an dpredato r (se e Appendi xA) . Analytica l Procedure s Heav y Metal s Subsample s o f eac hlitter " replicat e wer e groun dt o #2 0 mes h finenes s i na Wile y

mil l andwet-digeste db y treatmen t wit h1: 1 HN0 3 / HC10 4 (Smith , 1953 ; Analytica l Method s Committee , 1960 ; Gorsuch , 1962) . Upo nattainin g complet e digestion , eac hsampl e wa s suspende din1 N_HC1 , heate da t 100° C fo r 1 0 minutes , filtere dthroug h#4 0 Whatma npaper , andanalyze db

y atomi c absorptio nspectrophotometr y fo r tota l Pb , Cd , Zn , an dC ucontent . Analytica l grad e reagent s wer e used . Al l prepara tio nmethod s andanalytica l procedure s wer e monitore dperiodicall y uti lizin g code dblank s an da NBS-SRM-157 1 standar d(orchar dleaves) .P.3 1

1 5 Analytica l result s fo r th e standard s wer e accurat e t o withi n on e standar d erro r o f th e mean . Drie d arthropod s o f individua l trophi c level s fro meac h o f tw o randoml yselecte d replicate s wer e poole d acros s seaso n an d horizon , an d dry-ashe d fo r 2 4 hour s a t 480° C - a temperatur e whic h prevent s lea d volatilizatio n (Gorsuch , 1962) . Th e remainin g as h wa s suspende d i n 0. 1 N ^ HN0 3 an d allowe d t o stan d undisturbe d fo r 2 4 hour s a t roo mtem
perature . Th e decan t wa s analyze d fo r tota l Pb , Cd , Zn , an d C u conten t b ygraphit e furnac e atomi c absorptio n spectrophotometry . Monitorin g o f preparatio n an d analytica l procedure s wa s performe d frequentl yusin g code d blank s an d NBS-SRM-157 7 standar d (bovin e liver ) a s previousl y discusse d fo r litte r samples .

Chemica l Characterizatio n o f Litte r Approximatel y1. 0 g sample s o f dried , groun d litte r collecte d fro m th e NW transec t wer e dry-ashe d overnigh t a t 550°C . Fiv e m l o f concen trate d HN0 3 wer e adde d t o th e as h and sample s wer e boile d t o dryness . Exactl y50. 0 m l o f 1. 0 N [ HC l wer e adde d t o th e residue , an d an yundis

solve d residu e wa s allowe d t o settl e t o th e botto mo f th e container
. An aliquo t o f eac h sampl e wa s analyze d b yatomi c absorptio n spectro
photometr yfo r tota l elementa l Ca , Mg , an d K . Phosphoru s wa s determine d b yth e automate d Technico n metho d (Lundgren , 1960) . Litte r catio n exchang e capacit y(Franci s and Grigal , 1971 ) wa s 8 5 determine d usin g 2 5 m l o f 1 NSrCl 2 i n a suspensio n o f 1. 0 g groun d litter
. Th e suspension s wer e shake n overnight , centrifuged , an d decanted . Th e litte r wa s the n sequentiall ywashe d wit h 2 5 m l eac h o f th e followin g solutions : distille d water , a 50:5 0 mixtur e o f ET0 H an d 

# 1-"•Tr-'TfrTn *



### 1 6 distille dwater , and2 washe s i n95 % ETOH . Th e washe dlitte r wa s O C 

### subsequentl y

radioassaye dfo r S r usin g anautomate dgamma spectro meter . Th e catio nexchang e capacit y wa s calculate db

y th e numbe r o f O C 

### S r equivalent s retaine d(adsorbed ) pe r gram o f litter . Litte r wa s prepare dfo r p H analysi s b

y suspendin g 1 g litte r in 1 0 m l distille dwate r followe db y anovernigh t equilibration . Determi nation s o f pH wer e mad e usin g a Cornin g Mode l 11 0 mete r wit ha combina tio nelectrod e (Jackso nandWatson , 1976) .

Arthropo dDiversit y

Measuremen t Communit y diversit y

i s generall y

though t t o b e directl y

correlate d wit hsystem

stabilit y

(Price , 1975 ; Odum , 1971) . T o gai nsome measur e o f stabilit y

i nCrooke dCree kWatershed , al l arthropo ddat a wa s sub jecte dt o diversit y

analysis . Diversit y o f anima l o r plan t tax a withi nanecosyste m i s a measur e o f it s heterogenity . A s such , i t i s compose do f tw o elements : th e richnes s o f taxa (tota l number ) andthei r equitabilit y (evennes s o f abundance ) (Peet , 1974 ; Price , 1975) . A commonl y use ddiversit y measur e i s th e Shannon-Weave r Inde x(H') wher e
s H ' - ^ P i 

### ln P i 

## ( D fo r p . th e proportio no f tota l individual s o f taxo nj_wit h£ th e tota l numbe r o f tax a (Shannon , 1948) . Evenness , J' , ca nb e estimate d fro m H ' H '

J ' = H ' ma x 

## TF T (2 ) fo r S equalin g th e tota l numbe r o f tax a presen t (Pielou , 1966 ; Price , 1975) .P.3 3

1 7 Arthropo d data , classifie d t o famil y (se e Appendi xB ) wer e use d t o calculat e H' , J' , an d richnes s fo r eac hsite . Th e standar ddeviatio n
o f H ' wa s estimate d b y Hutcheson' s approximatio nmetho d(Hutcheson , 1970) . Arthropo d Populatio nDensit y an d Biomas s Food-we binteraction s amon g litter-dwellin g arthropod s o f th e fores t floo r ar e intricate , andinvestigator s studyin g thi s communit y hav e mad e simplification s o f th e comple xprocesse s involve di nlitter system functio n(Szabo , 1974) . On e often-use dsimplificatio ni s th e segregatio no f organism s accordin g t o thei r feedin g habits , o r trophi c levels . I

na previou s study

o f arthropod s occupyin g th e mesi c deciduou s 13 7 fores t floor , Cs-tagge d litte r wa s successfull y use dt o delineat e fou r trophi c level s includin g littergrazers , fungivores , detritivores , an d predator s (McBraye r an d Reichle , 1971) . Thes e 4 categories , wit h th e additio no f anomnivor e level , wer e use di nsegregatin g Crooke d Cree k Watershe d arthropod s followin g taxonomi c classificatio nan d enumeratio n(Appendi xA an d B) . Omnivore s ar e scavenger s an dinclud e organism s tha t fee d upo nplan t an d anima l materia l tha t ha s no t ye t undergon e chemica l o r physica l chang e throug hdecompositio n(Hanson , 1962 ; Price , 1975) . Altere d organi c materia l (detritus ) serve s a s an energ y bas e fo r th e grou p classifie d a s detritivore s (Odum , 1971 ; McBraye r e_

t aj_. , 1974) . I

nth e presen t study , determinations o f foo d preferenc e withi neac hlif e stag e an dtaxo nwer e mad e b

y consultin g referenc e work s tha t incorporate d direc t observation , gu t analysis , an d radionuclid e trace r analysi s a s method s o f studyin g trophi c relation ships . Documentatio ninclude d Borro r an dD e Long , 1964 ; Borro r an d

### n

1 8 White , 1970 ; Cornstock , 1940 ; Chu , 1949 ; Hoff , 1949 , Jaques , 1951 ; Kaston , 1972 ; Lev i e_ t al_. , 1968 ; McBraye r an dReichle , 1971 ; McBraye r et

_aj_. , 1974 ; Peterson , 1956 ; Price , 1975 ; Ross , 1965 ; an dSzabo , 1974) . Tw o additiona l categorie s wer e create dt o organiz e group s fo r whic h
n o feedin g preferenc e coul d b e found i nth e literatur e ("unknown" ) o r
n o morphologica l developmen t occurre d onth e fores t floo r ("accidentals" ) Thi s latte r clas s wa s no t incorporate d int o any dat a analysi s procedure s
and include d insect s tha t wer e eithe r foliage , seed , stem , o r bol e feeder s fro

m th e canopy

o r roo t feeder s fro m th e soil . Th e occurrenc e
o f a fores t fir e in196 9 (Wright , 1974 ) disrupte dth e litte r arthropo d communit y

a t 2 site s o

nth e N transect , an

ddat a fro

m thi s transec t wer e delete d fro

m th e study . Statistica l Procedure s Litte r mass , heav

y meta l concentrations , an dheav y meta l pool s wer e analyze d a s a 4x3x4x 2 factoria l analysi s o f varianc e (ANOVA ) repli cate d 4 times . Experimenta l classe s include d4 seasons , 3 transects , 4 distances , an

d 2 horizons . Value s fro m th e NE transec t (se e Figs . 7 t o 10 ) wer e analyze d separatel y fro m th e mai r desig ndu e t o th e con foundin g treatmen t o f ore-concentrat e dust s blow nint o CC

W fro m th e railway . Al l mai neffect s an dinteraction s wer e teste dfo r signifi canc e (Snedeco r an

d Cochran , 1967) . Chemica l characterizatio ndat a gathere dfo r th e N W transec t wer e subjecte d t o a 4x5x 2 factoria l ANOV A desig nreplicate d3 times . Classe s fo r thi s analysi s wer e 4 seasons , 5 distance s (0.4 , 0.8 , 1.2 , 2.0 , an d 21. 0 km) , an

d 2 horizons . Again , al l mai neffect s an dinteraction s wer e teste d fo r significance .- ••m-rmrw- r *P" ' f '"FTTff r ~



### 1 9
Mea ncompariso ntestin g o f litte r standin g crop , ash , heav y meta l concentration s an

d heav y meta l pool s b

y seaso nan

d horizo nwa s performe d usin g Duncan' s Ne w

Multipl e Rang e Tes t (Duncan , 1951 ; Stee l an d Torrie , 1960) . Prio r t o regressio nanalysis , arthropo d biomas s an d densit y

an d litte r mas s dat a wer e transforme d b y th e followin g normalizatio nfunc tio n(Natrella , 1963) :
y = I n( x+ .5 ) 

### (3 )
Us e o f thi s functio nals o ha s a variance-stabilizin g effect , thu s allowin g applicatio no f linea r regressio nmodel s t o th e transforme d dat a (Natrella , 1963) . Significanc e testin g wa s accompanie d usin g standar d formula e (Drape r an d Smith , 1966 ; Stee l and Torrie , 1960) .RESULT S AND DISCUSSIO N

Crooke dCree k Watershe dLitte r Litte r Mas s Value s fo r 0 1 litte r mas s onCrooke dCree k Watershe drange dfro m 2 2 48 0 g/ m t o 12 0 g/ m

(Fig . 5 ) andwer e comparabl e t o th e annua l litte r 2 productio no f 34 9 g/ m /yr foundb

y Rochow (1974 ) ina centra l Missour i p oak-hickor y

forest , andth e Warm Temperat e Fores t mea no f 36 0 g/ m /yr derive db

y Bra y andGorham

(1964) . A s dat a fo r al l season s studie d in197 4 demonstrate dtrend s simila r t o thos e inFig . 5 , Septembe r wa s 2 chose nt o illustrat e litte r mass/ m followin g summe r decompositio nbu t prio r t o leaffall . Thus , dat a fro m th e autum

nsamplin g perio dshoul d demonstrat e conservativ e estimate s o f bot h0 1 an d0 2 litte r mass . N o significan t difference s in0 1 mas s amon g th e 1 5 watershe dsite s wer e detecte db

y Duncan' s Ne w

Multipl e Rang e Tes t (Tabl e 2) . A naccumulatio no f 0 2 litte r (fragmente dmateria l no longe r recog nizabl e a s t o specie s o r origin ) wa s eviden t a t site s nea r th e smelte r comple x( W

0. 4 km , N

W 0.4 , N 0.4 , N E 0.4 ) (Fig . 5 , Tabl e 3) . Maximu m 0 2 2 litte r mass/ m

fo r Septembe r occurre da t th e N an dNE 0. 4 sites , wit h value s o f 298 0 and259 0 g/m 2 , respectivel y (Tabl e 3) . Th e 0 2 litte r mas s fro m site s o nth e N E transec t wa s apparentl y no t affecte db

y the same distance-dependen t sourc e producin g accumulation s nea r th e smelter , becaus e 0 2 mas s a t N E 0. 8 and1. 2 ar e no t significantl y differen t fro

m tha t founda t th e 0. 4 k m site s onth e W , NW , an dN transect s (Tabl e 3) . Ingeneral , a declin e i n0 2 litte r mas s occurre da s distanc e fro m th e smelte r comple xincrease d(Fig . 6) . Althoug hthi s relationshi pwa s 

### 20ORN L DW G 76-339 9 (x10 2 ) 3 0 - 2 5

* 2 0 </ > 1 5 

## 1 ^ 0 - V FAL L 197 4 WES T TRANSEC T ° 2 ° 1
V

.

. - i i

. ——- 1 >——*-

0 4 0 . 8 1 2

DISTANC E (km ) 1.6-2. 0 21. 0 'V - (x10 2 )

3 0

<s i 2 5 * Q 2 0 % 1 5 <

5 0 i (»10 2 ) 3 5
3 0

<S J E 2 5 * o o . 2 0 (S, < 1 5 2 O < D 1 0 5
0 0 4 0. 8 1. 2 (.6-2. 0

DISTANC E (km ) 21. 0 

# 1 1 NORTHWES T TRANSEC T

i ~

^^** l

I
- . 1 i
r*"* *

•—i r V 

# L.:I^.

" I

A, 0.4 . 0. 8 1. 2

DISTANC E (km ) 1.6-2. 0 21. 0

NORTHEAS T TRANSEC T

. .1. . . 1 ... . 

# • K< |

i 1

- \ - • •

._. .

s \

. 1 , , V ' i r 1 . 1 - • -

.. __. _

0 4 0. 8 1 2

DISTANC E (km ) 21. 0 Fig
. 5 . Mea n litte r mas s ( g dr ywt/ m) o f 0 1 an d 0 2 horizon s o n Crooke d

Cree k Watershe d a s a functio n o f distanc e and directio n fro m th e AMAX smelte r fo r th e September , 1974 , samplin g perio d ( x ± 1 SE , n=4) . ro



### :iJM - Tabl e 2 . Seasona l mean s o f 0 1 litte r mas s analyze d b y Duncan' s Ne

w Multipl e followe d b

y th e same lette r ar e no t significantl y differen t a t th e Stee l and Torrie , 1960) . Rang e Test . Mean s 5 % leve l (Duncan , 1951 ;

Marc h Sit e (km ) N E 0. 4 N 0. 4 N W 2. 0 N W 1. 2 W 0 . 8 W 1. 2 W 1. 6 N 2. 0 W 21. 0 N W 0. 4 NW0. 8 N 1. 2 N E 1. 2 N E 0. 8 W 0. 4 N 0. 8 197 4 (g/m 2 )

Mea n ( x IO 2 ) 11. 8 7. 4 5. 4 5. 0 4. 7 4. 6 4. 5 4. 3 4. 2 4. 1 4. 0 3. 5 3. 4 3. 1 2. 5 2. 2 Dunca n

A A B A B A B A B A B A B A B A B A B A B A B A B B B B Jun e

Sit e (km ) N E 0. 4 W 0. 8 N 0. 4 N W 2. 0 W 1. 6 N W 1. 2 N E 1. 2 N E 0. 8 N W 0. 8 W 0. 4 NW0. 4 N 0. 8 N 2. 0 W 21. 0 W 1. 2 N 1. 2 197 4 (g/m 2 )

Mea n ( x IO 2 ) 11. 6 10. 5 9. 2 9. 0 7. 8 6. 8 5. 9 5. 6 5. 4 5. 4 5. 2 5. 1 4. 5 4. 4 3. 8 3. 1 Dunca n
A A A A A A A A A A A A A A A A September ,

Sit e (km ) W 1. 6 W 0. 8 W 0. 4 N W 1. 2 N 2. 0 N 0. 8 W 1. 2 W 21. 0 W 16. 3 N 0. 4 NW0. 4 N E 0. 4 NW0. 8 W 10. 4 N 1. 2 N E 0. 8 N E 1. 2 N W 2. 0 Mea n

( x IO 2 ) 4. 8 3. 9 3. 2 3. 1 2. 9 2. 8 2. 7 2. 7 2. 6 2. 5 2. 5 2. 1 2. 0 2. 0 1. 4 1. 4 1. 4 1. 2 197 4

Dunca n
A A A A A A A A A A A A A A A A A A January ,

Sit e (km ) W 0. 4 N E 0. 8 W 1. 2 N E 1. 2 W 10. 4 W 1. 6 N 0. 8 W 0. 8 N E 0. 4 W 16. 3 N 2. 0 N W 0. 8 W 21. 0 N 0. 4 N 1. 2 N W 1. 2 N W 0. 4 N W 2. 0 Mea n

( x IO 2 6. 5 5. 5 5. 2 5. 1 4. 8 4. 6 4. 5 4. 1 3. 8 3. 8 3. 7 3. 5 3. 5 3. 2 3. 2 3. 1 2. 7 2. 5 197 5 Duncan ) A A A A A A A A A A A A A A A A A A r o



## mTabl e 3 . Seasona l mean s o f 0 2 litte r mas s analyze d b y Duncan' s Ne w

Multipl e followe d b

y th e sam

e lette r ar e no t significantl y differen t a t th e Stee l and Torrie , 1960) . Rang e Test . Mean s 5 % leve l (Duncan , 1951 ;
Marc h Sit e (km ) N 0. 4 NE0. 4 NW0. 8 N E 0. 8 W 0. 8 N 0. 8 N E 1. 2 N 1. 2 W 1. 6 N W 0. 4 N W 1. 2 N 2. 0 N W 2. 0 W 1. 2 W 0. 4 W 21. 0 1974 (g /

Mean (x IO 2 ) 27. 1 25. 0 21. 4 20. 6 19. 9 19. 9 17. 5 17. 3 17. 2 16. 6 16. 0 14. 1 13. 6 13. 6 13. 3 9. 1 'm 2 ) Dunca n
A A B AB C AB C AB C AB C BC D BC D BC D BC D C D C D C D C D C D D Jun e

Sit e (km ) N E . 8 N E 1. 2 N 0. 4 N 1. 2 N 2. 0 N E 0. 4 N W 0. 8 W 1. 2 W 1. 6 N W 2. 0 W 0. 4 N W 1. 2 W 0. 8 NW0. 4 N 0. 8 W 21. 0 1974 (g/m 2 )

Mean (x IO 2 ) 30. 5 22. 8 22. 4 21. 6 20. 1 18. 7 18. 2 18. 1 16. 5 15. 6 14. 9 12. 6 11. 4 11. 1 8. 4 7. 2 Dunca n
A B B B B C BC D BC D BC D BCD E BCD E BCDE F CDE F DE F DE F E F E F September , Sit e (km ) N 0. 4 N E 0. 4 N E 1. 2 W 0. 4 N W 1. 2 N E 0. 8 N W 0. 4 N 2. 0 N 1. 2 NW0. 8 N 0. 8 N W 2. 0 W 0. 8 W 16. 3 W 21. 0 W 10. 4 W 1. 6 W 1. 2 Mean

(x IO 2 ) 29. 8 25. 9 22. 6 22. 2 21. 0 20. 7 20. 4 19. 4 18. 3 17. 9 17. 7 17. 5 13. 1 12. 3 12. 2 11. 8 10. 6 10. 6 197 4

Dunca n
A A B A B A B B C BC D BCD E BCDE F BCDEF G BCDEF G BCDEF G BCDEF G CDEFG H DEFG H EFG H FG H G H H January , 197 5 Sit e (km ) N E 0. 4 N E 0. 8 W 0. 4 N 0. 4 N E 1. 2 N 0. 8 NW0. 4 NW0. 8 N W 2. 0 N W 1. 2 W 1. 6 W 1. 2 N 2. 0 N 1. 2 W 0. 8 W 16. 3 W 21. 0 W 10. 4 Mea n

(x IO 2 ) 43. 2 34. 0 33. 0 28. 5 26. 6 26. 6 24. 4 21. 3 20. 8 20. 0 19. 6 19. 0 18. 5 18. 1 16. 0 12. 9 12. 5 12. 4 Dunca n

A B B B C BC D BC D CD E CDE F CDEF G DEF G DEF G DEF G DEF G EF G EFG H FG H FG H H r o

c o~"! T y»rl'*Wpi T

2 4 ORN L DWG . 74-11187 A

SP.iN C '9 T « 3 0 i ' 0 2 (N E "OANSEC T EiCLUDED I P.4 0

v t-^ .

, o - -

, i -..4^= 4

=f=^
0 6 1.

2 K-2. 0 DISTANC E (•* > ORN L DWG . 74-11186 A

0 8 1.

2 16-2. 0 DISTANC E (M l ORN L DWG . 7411189 R

— v , v
ran . i97 «

~ ~.'o 7 -Vr1 \ 

### s K

_ - T ^ •w~ ^ ~~*~f—-w-4—-IA —
5 1 j— • i *- f
0- 4 0. 6 1. 2 1.6-2. 0 OISMNC C (>• > 1 0 « 16 3 21. 0

3 " i ORN L DWG . 74-4349 A : '/ I f, V^~ 1 S. .INTE R t»r . 0 , IN C T.*NS£C

T E«CLUOC0

-

S i -H——•» - 

### ==1 r VV.-?-V>- ;

-i~Vr^fr-U^. -f t ft— 0 . O f I t I.-1. 0 10 . 4 I . S tl . 0 OltT.MC I (»• > Fig . 6 . Poole d mean s o f litte r mas s ( g dr y wt/ m ) o f 0 1 an

d 0 2 horizon s on Crooke d Cree k Watershe da s a functio no f distanc e fro m th e AMA Xsmelte r fo r eac hsamplin g period , 1974 . Value s fo r th e N E transec t wer e exclude d fro m computatio no f th e mean s ( x+ 1 SE , n=12) .2 5

mos t apparen t fo r th e Fal l an d Winte r samplin g periods , ther e wa s a consisten t and significan t accumulatio no nal l watershe dsite s (1818+
_ p 53 4 (SE ) g/ m

) whe ncompare d wit hth e primar y contro l site s (1208+32 8 (SE ) g/ m ) . No significan t difference s inmea n0 2 litte r mas s existe d betwee nth e primar y

an d secondar y

contro l plot s (Tabl e 3) . Thus , primar y contro l value s wer e assume d t o represen t th e unperturbe dconditio nfo r th e area . Fo r th e duratio no f th e study , watershe d 0 1 mass/ m (433+2 9 (SE ) 2 g/ m ) di d no t var y

significantl y

wit htime o r distanc e (Fig . 6) . In 2 contrast , contro l 0 1 litte r mass/ m fluctuate dabou t th e mea no f 350+3 5 2 (SE ) g/ m (Tabl e 2) , whic hcompare d favorabl y wit hliteratur e value s fo r th e fores t typ e unde r stud y (Rochow , 1974 ; Bra y an dGorham , 1964) . However , i t shoul d b e note d tha t th e mas s o f 0 1 litte r onCrooke dCree k Watershe d an

d th e contro l site s wer e no t foundt o b e significantl y differen t fro

m on e another . T o determin e i f litte r mas s determination s onthe watershe dhad bee nbiase d b

y depositio no f fugitiv e particulate s fro m th e stack , as h determination s wer e mad e fro m subsample s o f materia l collecte donth e N W transec t (Tabl e 4) . Duncan' s analysi s indicate dn o difference s i n litte r as hconten t exis t fo r eithe r litte r horizon . I naddition , th e rang e o f as hvalue s (5.3-19.1 % fo r 0 1 an d 20.8-62.5 % fo r 02 ) compare d favorabl y

wit hthos e o f othe r deciduou s fores t studie s (Reiner s an d Reiners , 1970 ; McBraye r e_ t aj_. , 1974 ; Henderson , 1971) . Litte r Heav

y Meta l Conten t Th e highes t concentration s o f al l fou r element s occurre din0 2 material , wher e heav y meta l value s ar e 1. 5 t o 2 time s greate r tha n

### 2 6

Tabl e 4 . Seasona l Mean as h conten t ( % dr ywt ) o f Crooke d Cree k Watershe d litter
. On e standard erro r i n parenthese s (n=3) . Th e N

W transec t wa s chose n a s representativ e o f th e watershed .

SPRIN G SUMME R FALL WINTE R

Sit e Horizo n (km ) Mea n As h Conten t Mea n

As h Conten t Mean

As h Conten t Mea n Ash Conten t

N W 0. 4 0 1

0 2 15. 6

58. 6 3.2 ) 4.8 ) 19. 1 43. 9 3.2 ] 4.5 : 14. 0 (3.9 ) 35. 7 (3.3 ) 9. 1

32. 0 0.7 ) 6.6 ) N W 0. 8 0 1

0 2 5. 6

36. 2 0.2 ) 3.0 ) 6. 6 31. 6 0.2 ! 4. 1 10. 3 (1.3 ) 31. 8 (3.7 ) 5. 6

42. 2 0.6 ) .11.6 ) N W 1. 2 0 1

0 2 7. 5

62. 5 0.3 ) 4.5 ) 7. 8 54. 0 0.4 ) 

### :i3.s : 10. 6 (0.7 )

49. 2 (1.1 ) 7. 3

40. 4 1.7 ) [14.6 ) 2. 0 0 1

0 2 18. 3

61. 4 

### ilO.O ) 5.7 ) 6. 8 20. 8 0.4 ] 1. 1 14. 6 (3.3 ) 36. 9 (4.5 ) 5. 3

39. 3 0.3 ) 8.4 ) W 21. 0 0 1 (control ) 0 2 5. 3 27. 5 0.2 ) 5.5 ) 6. 5 33. 9 0.5 ] 

### :io.7 : 7. 2

25. 7 (0.3 ) (4.6 ) 5. 2

27. 0 0.1 ) 2.2 )



# m

### 2 7

thos e foun d i n 0 1 litte r (Watson , 1976 ) (Figs
. 7-10) . Suc h accumula

tio n i n litte r and humu s i s though t t o b e governe d b ypassiv e exchang e betwee n heavymeta l ion s occurrin g i n precipitatio n an d foliag e leachat e
and th e macronutrien t ion s normall yboun d t o negativel ycharge d organi c group s (Ruhlin g an d Tyler , 1973 ; Tyler , 1972) . Exceptin g N E transec t results , Crooke d Cree k Watershe d lea d conten t o f 0 2 litte r ca n b e segre gate d accordin g t o distance : al l 0. 4 k mvalue s wer e no t differen t fro m
eac h othe r bu t wer e differen t fro mthos e foun d o n th e res t o f th e water
shed . Group s o f mean s fo r th e remainin g distance s grade d int o on e anothe r throug h th e controls . Contro l value s di d no t diffe r fro mth e 1. 2 k m o r watershe d boundar ysites
. Simila r distribution s occurre d fo r Zn , Cu , and Cd , althoug h equivalen t C d concentration s wer e disperse d
ove r a large r are a (Appendi x C) . A s dat a fo r al l samplin g period s illustrate d trend s simila r t o thos e i n Figs
. 7 t o 10 , Septembe r wa s chose n a s a representativ e seaso n t o demonstrat e conservativ e estimate s o f litte r lead , zinc , copper , an d cadmiu mcontent . O f th e 4 meta l contaminant s foun d i n Crooke d Cree k Watershe d litter , P b wa s th e mos t abundan t (Fig
. 7) . Zinc , th e secon d mos t abundan t heavymetal , wa s followe d b yC u an d C d (Figs
. 8-10) . Unde r
norma l operatin g conditions , particulat e stac k emission s fro mth e AMAX smelte r followe d th e sam e ran k order , i.e. , P b (1851 0 kg/yr ) > Z n (173 0 kg/yr ) > C u (83 0 kg/yr ) > C d (5 0 kg/yr ) (Purushothaman , 1974) . Ove r 99 % o f th e tota l heavy-meta l concentratio n foun d i n th e entir e litte r horizo n a t th e 0. 4 k m site s wa s du e t o Pb . Thi s percentag e decline d t o 93 % a t th e watershe d boundary, an d wa s furthe r reduce d to .2 8 • * TTT'T^ T -T'lrnw

ORN L DW

G 76-340 0 io 5

z o a :

z o u

z 10 "

2 - •
10 J I

J \ \ ; \ 1 > 1 ^ \ SEPT E

WEST \ ^ ! |

MBER.197 4 TR M

- - 0

—n NJSEC T 

### 1 

# \ X 

# Kl

X «k

' 

# \ 1 >>. .
CO N CO N .. .

1 i rRO L 0 , = 10 0 pp m TR0 L 0 2 =137pp m ^ * v S \ * ! \ . j > i ' | i i | i S 2

a i e a. ^10 5 z g I 5 U J u z o (- > z <

0. 4 0. 6

DISTANC E 1. 2

(km ) 1.6-2. 0

_10 5 $ a

z o

z o o

< U J 2 IO 4 —

— 1 1 

## i ' l v . l \ v i \ ^ 1 \ 1 > 1 1 1 1 T H TRANS E

^ v V

' i i s . • S 1 X

"x

. •

Fig

. 7

. 0. 4 0. 8 1. 2 DISTANC E (km ) 16-2. 0 4 1 ' i NORTHWPC TTCAwcrr T '

TV t \ \ \ \ \ !

i ! 1 i 

# V x — i

i N j

•i ^C S
,_. . . 0. 4 0. 8

DISTANC E 1.2 1.6-2. 0

(km ) 3
E 3 2 z o 

### i i i e z U J 

### 6 

### *

aMEANF5 !

| N0RTHE A I 

## i ! ^ ST TRANSEC T i \
\ \ \ N --

^> ' ' •

I 1

1

! 1 '< 1

0. 4 0. 8

DISTANC E 1. 2

(km ) Mean s o f litte r P bconten t (ug/ g dr y wt ) i n 0 1 an

d 0 2 horizon s a s a functio no f distanc e an d directio nfro

m th e AMA Xsmelte r fo r th e September , 1974 , sampling period ( x+ 1 SE , n=4) .

### 29 P.4 5 -i-InfT*'i"" , i 1 ' 1 ' " " "

a i E a a . Z o r - < a : i z U J o Z o
z < U J 2 1 0 J

2

3

5

• > SE P

WE S \ CO N \ CO N \ \ \ \ \ \ \ \ \

' TEMBER , 1 9

—o 2

—o , T TRANSE C 7 4

T TRO L 0) = 54. 5 pp m TRO L 0 2 =107. 9 pp m

i i X X X k *x^ . X / / •£ • 

### k^"--- *

s o

z o r - < C C r Z U J u z o

z < U J z 10 -

Fig

. 8

. a

z o r - < C C r Z U J u z o o 1 0

z < U J 2 5

2

3

5

• 5 0RNL-0W G 76-340 3

NORTHWES T TRANSEC T

« s N \ \ \ k \ \ \ \ \ \ \ \ \ \ \ \ •• > X i x > L ^ . I " -«Oi/t

_ i J^ 

### ^ ~" S \ 1 

### X

0. 4 0. 8 1. 2 1.6-2. 0 DISTANC E (km ) 0. 4 0. 8 1 2 1.6-2. 0 DISTANC E (km ) 1 i 1 NORT H TRANSEC T 1 i 

# 1

X " X

1 I

'-... . "**•» » ^
^^ ' v \ \ i s X ^ \ 

### 1 > 

## ! 1 1 a i e a a .
- 2 z o » - < c c r- , z io 3 U J u z o < J c N 5 z < U J 5 NORTHEAS I IHAN S

1

N X , < >

, !

i 1 1 EC T /

/ / / / / / f

0. 4 0. 8 DISTANC E 1. 2

(km ) 16-2. 0 0. 4 0. 8 DISTANC E 1.2

(km ) Mean s o f litte r Zn conten t (yg/ g dry wt ) in 0 1 an

d 0 2 horizon s a s a functio no f distanc e an d directio nfro

m th e AMA Xsmelte r fo r th e September , 1974 , samplin g perio d ( x+ 1 SE , n=4) .3 0

ORNL-DW G 76-340 1

Q

Z o < I c c r Z u i u z o 10 -

10 '

10 « 3 Q

< U J Z 2 ,0 3

10 ' Fig

. 9

. SEPTEMB E

WES T TR A I R, 197 4 | NSEC T 0 ? i
CONTRO L 0 , = 8 pp

m

s . V \ \ X v \

I I • I l 

## ^ i

i v 

### x i ^T*^ . J

- ^ r ^ 4 T 

### 1 1 5

z 10 J o H < I C C
u z o u < 3 2 z < U I , Z IO 2 

## 1 1 1 

### i NORTHWES TTRANSECT ; 

# K \ \ X ^ X N — f

~- \ f i \ \ \

X . \ \ \ X w I i .

0. 4 0. 8 1. 2 DISTANC E (km ) ] 1 ! ANSEC

T ! ! ! i i i 1 \ X f \ 

### 1 \ j \

i i

. ~ ^
' ^v .


### - x >-

, X
" \ X 

### X X

^ X ' 6-2. 0 0

10 " I 5 0. 4 0. 8 1. 2

DISTANC E (km )

z 2 o e - < c c 10 3 o z o

z <

10 < 0. 4 0. 8 DISTANC E 1. 2

(km ) 1.6-2. 0 0. 4 0. 8 DISTANC E 1. 2

(km ) 1.6-2. 0
1 1 1 I1 1 ! -"' ? 

## .>- ' J <

i J

.

Mean s o f litte r C

u conten t (yg/ g dr y

wt ) i n 0 1 an

d 0 2 horizon s a s a functio no f distanc e an d directio nfro

m th e AMA Xsmelte r fo r th e September , 1974 , sampling perio d ( x+ 1 SE , n=4) .3 1 ! 

### T> !

ORN L DW

G 76-340 2

s Q 10 < z o c c <_> z o u
z 4

10 1

3 o

- 1 0 z o 4 c c

z o o

z 4 U J 2

1 0 Fig

. 10

. SEP ' WE S

1

1 rEMBER,1 9

T TRANSEC "

—0 2
^ 1

^ CONTRO L 0, = 7 4

r

t \ CONTRO L 0 ? = i.ipp m \ " \ i s \ s 

## \ N i > L

i 1 ,

|

• v

^ v . ^

0. 4 0. 8 1. 2 DISTANC E (km )

?

5

2 •

1 1 NORT H TRANSEC T

' * X ! - ^ k

1 \

i ^
1 ^ k \ S \ i . a

— | 3 10 ' z o
4 C C
z o u
z 4 U J Z
I.6-2. 0 1 ° o

* o NORTHWES T TRANSEC T I

• s

. s : \ \ ' s \ s \ \ \ \ \ 1k -> -
T [ ^

10 '

4 C C r Z U J (- ) z o o • o u z 4 U J Z

10 1 0. 4 0. 8 1. 2 DISTANC E (km ) 1.6-2 0 0. 4 0. 8 1.2 DISTANC E (km ) 1.6-2. 0
1 NORTHEAS T TRANSEC T I * J \ \ \ \ \ ^ \ J*

,.• * +* \ \ ' \ V " \ ] \

• ! i 

## ! j 0. 4 0. 8 1 2 DISTANC E (km ) Means o f litte r C

d conten t (yg/ g dry

wt ) in 0 1 an

d 0 2 horizon s a s a functio no f distanc e an d directio nfro

m th e AMA Xsmelte r fo r th e September , 1974 , samplin g perio d ( x+ 1 SE , n=4) .

### 32

87.3 % a t th e 21. 0 k

m contro l sit e (Watson , 1975) . Th e concentratio no f deposite d Pbfollowe d th e distributio npredicte db y windros e pattern s (Fig . 3 ) i ntha t th e greates t concentration s wer e foundonth e N W an dN transect s (103,00 0 pp m an d 76,20 0 ppm , respectively) . Value s exceeding 90,00 0 pp

m wer e exhibite d fo r th e NE transec t (Fig . 7) , bu t wer e a resul t o f fugitiv e dus t depositio nfro m th e railwa y

lin e source . Wit hth e exceptio no f th e NE transect , a steady logarithmi c decreas e inconcentratio nwit hdistanc e fro m th e smelte r comple xwa s apparen t fo r al l metal s and compas s direction s (Figs . 7-10) . Thes e finding s wer e consisten t wit hthos e o f othe r samplin g program s measurin g heav y meta l depositio nwit hdistanc e fro m anare a sourc e (Roberts , e t al_. , 1974 ; Ruhlin g and Tyler , 1973) , and wer e a resul t o f th e particl e siz e distri butio no f particulat e stac k emission s (Bondiett i e_ t a]_. , 1975) . Storage , loadin g an

d transpor t o f Pb , Zn , an dC uconcentrat e fro

m th e C0MINC 0 millin g proces s hav e produce d larg e quantitie s o f metal-ric h dust s tha t ar e ofte nblow ndirectl y

int o th e watershed . Consideratio n o f thes e fugitiv e source s i s necessar y t o properl y

interpre t result s fo r th e N E transec t displaye d i nFigs . 7 t o 10 . Depositio nfro m secondar y source s wa s especiall y apparen t inth e cas e o f coppe r (Fig . 9) . A steady increas e i nC u conten t o f 0 2 litte r occurre dwit hincreasin g distanc e fro

m th e stack , and ca nbe attribute dt o th e storag e o f unecono mica l l y recoverabl e Cu concentrat e (4% ) i na nope nbi n2 0 yard s fro m th e N E 0. 8 k m study plot . A s a resul t o f th e confoundin g effec t o f secon dar y source s o nthes e data , thes e value s wer e no t include di nfigure s o f
seasona l poole d value s an d wer e analyze d separately . Whe ndistance-poole d mean s o f litte r Pb , Zn , Cu , an dC dconten t
ar e compared , difference s i nindividua l meta l concentration s o f th e—T.-K-7W — TMn"jy " • • --T»fTf 

### 3 3 P.4 9

two litte r horizon s a t eac hdistanc e incremen t ar e no t statisticall y differen t from

on e anothe r (Fig . 11 , Appendi xD) . Mean s o f tota l litte r (bot hhorizons ) heav

y metal s a t 0. 4 k

m differe dfro

m al l other s on th e watershe da t th e 0.1 % level ; th e 0. 8 k m value s differe dfro

m thos e a t 1. 2
an d1.6-2. 0 k

m a t th e 1 % level ; an d 1. 2 k m value s di d no t diffe r fro m thos e a t th e watershe dboundary . Thi s gradien t wa s commo nfo r al l 4 metals . Leas t square s multipl e linea r regressio nprocedure s wer e use dt o furthe r evaluat e th e relationshi pbetwee n0 2 litte r mas s an d litte r heav y meta l concentrations . Th e empiricall y derive dregressio nmode l include deffect s du e t o season , directio nan d distanc e fro

m th e AMA

X smelter , litte r heav

y meta l concentrations , an d al l interaction s du e t o multiplicativ e effects . Th e mode l wa s a s follows : I n( Y+ .5 ) = 6 Q + 0 1 x ] + B 2 x 2 + 63X 3 + 8 4 x 4 + 85X 5 + 6gX g + 6 7 X 7 + e 12 x l x 2 + B 13 x l x 3 + 6 23 X 2 X 3 + 6 11 X 1 X 1 + 3 22 X 2 X 2 + B 33 X 3 X 3 + 3 45 X 4 X 5 + 6 46 X 4 X 6 + e 47 x 4 x 7 +
6 56 X 5 X 6 + e 57 x 5 x 7 + e 67 x 6 X 7 + e 44 x 4 x 4 + B 55 X 5 X 5 + •
J 66 X 6 X 6 + 3 7 7 X 7 X 7 + e 

### (4 )

* 1 X o = X , =

XJ , = wher e x , = seaso n

directio n(transect ) distanc e P bconcentratio no f 0 2 litte r Z nconcentratio no f 0 2 litte r C uconcentratio no f 0 2 litte r C dconcentratio no f 0 2 litte r litte r mas s X- , = Y=3 4 TT- , '"-iTir" '

ORNL-OW

G 7J-999 g

IO 4

J I 9

E a 2 2 ORNL-OW C 79-1000 0

: n

CO N I N 1 1 \ % \ N * ' N E TRANSEC T 

### X

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# \ V

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# t \
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0. 4 0 9

DISTANC E (>• ) i.s-t. o

ORNL-OW G 79-999 7



### 1 I 1 v ^ 

### k J X

CONTRO L CONTRO L SEPTEMB E H , 197 4

- o , (N E TRANSEC T EXCLUOEO )

X\ f \ ^ X

0 t »6pp m 0 2 * 1!pp m 

# h ^ X . ^ .

O. S OISTANC I (»• > * a 

### i

.0 * 0 9 DISTANC E ('• )
ORNL-OWG 73-9,9 9

SEPTEMBER,197 4

\ (N E TRANSEC T

CONTR I \ \ \ \

L S \ ^ V » - 3 8 :XCLUOED I

••* - \ l

_i- ^

D L 0,-94. 9 p J L Oj.l07.9p i

gm (X ^ 1

o. t DISTANC E (»• ) Fig

. 11

. Poole d mean s o f litte r Pb , Zn , Cu , an d C d concentration s (yg/ g dr y wt ) a s a functio no f distanc e fro m th e AMA Xsmelte r fo r September , 1974 . Value s fo r th e N E transec t wer e exclude d fro m computatio no f thes e mean s ( x+ 1 SE , n=12) .

'.'Wi-llJ-JM'l'i.JL .P.5 1

3 5
Us e o f th e 23-variabl e mode l accounte dfo r 37.1 % o f th e variatio n observe d withi nth e data . Th e resultin g regressio nan dcorrelatio n statistic s ar e give ni nTable s 5 an d6 . Applicatio no f th e backwar d eliminatio nprocedur e a t P = 0.25 , th e significanc e leve l fo r entry , reduce dth e effectiv e variable s t o 10 ; whic haccounte d fo r 35.8 % o f th e tota l dat a variabilit y explaine db

y th e mode l (Drape r an

d Smith , 1966) . Th e resultin g regressio nstatistic s
ar e give ni nTabl e 7 . Significan t (P<.01) , positiv e correlatio ncoefficient s wer e obtaine d fo r th e first-orde r variable s o f season , litte r Zn , C uan dC d concentrations , an

d th e multiplicativ e interaction s o f litte r PbxCd , Z nxCu , and PbxC

u concentration s (Tabl e 6) . Thus , highlevel s o f heav y metal s i nth e 0 2 litte r occurre dsimultaneousl y wit hlarg e value s
o f litte r mass . Th e observe d effect s o f accumulate d0 2 litte r wer e no t du e t o any

singl e factor , bu t appeare dt o be interaction s amon g a comple x o f variables . Becaus e numerou s heav y meta l source s existe di nth e Ne w

LeadBel t
are a (fugitiv e sourc e dusts , othe r mine s andsmelters ) (Wixso ne t al. , 1972 ; Wixson , 1974) , th e validit y o f usin g selecte doff-watershe dsite s
a s control s wa s tested . Comparison s o f litte r an dA l soi l horizo nheav

y meta l value s wer e mad e betwee nCrooke d Cree k Watershe dan dWalke r Branc h Watershed , a relativel y undisturbe d deciduou s fores t study are a onth e Oa k Ridg e Nationa l Laborator y Reservation , Oa k Ridge , Tennessee . Ana lytica l procedure s simila r t o thos e use d i nth e presen t stud y hav e bee n use d t o deriv e Pb , Zn , an d C d conten t o f chestnu t oa k (Quercu s prinu s L. ) litte r and th e A

l soi l horizo n(Jackson , 1976 ; Va nHoo k e t al. , 1976 ) (se e Tabl e 8) . Whe nthes e determination s wer e compare dt o thos e

iMrJiiea.LjtJW8wwwwpw wP.5 2



### 3 6 Tabl e 5 . Multipl e linea r regressio nstatistic s fo r Crooke d Cree k

Watershe d 0 2 litte r mas s (transforme d b y Eqn . 3 ) ( n = 174, 23,15 0 = 3.838 , R 2 = .370 ) (g/m 2 )

Independen t Variabl e 6 n 8.02 1 0 0 0 407 723 33 5 

### + + + + + S E 0

. 0

. 0

. 1

. 379 16 4 91 7 21 8 Intercep t Seaso n Directio n Distanc e Litte r P bConcentratio n Litte r Z n Concentratio n Litte r Cu Concentratio n Litte r C

d Concentratio n Seaso nxDirectio nCrossproduct Seaso nxDistanc e Crossproduct Directio nxDistanc e Crossproduc t Seaso nxSeaso nCrossproduct Directio nxDirectio nCrossproduc t Distanc e xDistanc e Crossproduc t Litte r P bxZ n Concentratio n Crossproduc t Litte r P bxCu Concentratio n Crossproduc t Litte r P bxC

d Concentratio n Crossproduc t Litte r Z n xCu Concentratio n Crossproduc t Litte r Z n xC

d Concentratio n Crossproduc t Litte r Cu xC

d Concentratio n Crossproduct Litte r P bxPbConcentratio n Crossproduct Litte r Cu xCu Concentratio n Crossproduct -2.78xl0' 6 + 9.5xl0" 6 4.70xl0~ 4 + 4.46x10" 4 -3.51xl0" 4 + 3.42xlO" 4 -0.00 2 + 0.00 6 0.12 9 + 0.18 7 -0.08 9 + 0.21 0 

### 7.38 3 +6.70 6 0.09 9 + 0.031 9 -3.25 5 + 3.34 0 -4.07 9 + 3.62 1 -1.845xl0" 9 + 1.120xl0" 8 -3.468xl0" 9 + 2.635xl0" 9 1.800xl0" 7 + 1.400xl0" 7 -2.400xl0~ 7 + 3.800xl0" 7 -6.000X10* 8 + 5.8xl0" 6 1.190xl0' 6 + 4.220xl0" 6 -1.219xl0' 1 0 + 5.022xl0 -1 1 1.600x10" 7 + 1.4xl0" 7

## T\

Tabl e 5 (continued ) 

### 3 7

Independen t Variabl e g n+ S E Litte r C

d xC d Concentratio n Crossproduc t Litte r Z n xZ n Concentratio n Crossproduc t -3.794xl0' 5 + 5.901xl0" 5 9.000xl0" 8 + 2.900xl0" 7

### 3 8

Tabl e 6 . Correlatio n matri x resultin g frommultipl e linea r regressio n

analysi s o f Crooke d Cree k Watershe d 0 2 litte r mas s (g/m 2 , transforme d b

yEqn . 3 ) ( n = 174 , F23J5 0 = 3.838 , R 2 = .370) . Value s i n parenthese s ar e significanc e levels . ••" n



### X l * 2 X 4 

### * 5 Y

X l 

### x 2


### x 3 1 .19 6 .37 6

(.01 ) (.0001 ) 1 .00 2 (.979 ) 1 .31 8

(.0001 ) .00 5 (.949 ) .95 5 (.0001 ) 1 .22 2

(.0033 ) .00 2 (.978 ) .55 6 (.0001 ) .58 5 (.0001 ) .32 5 (.0001 ) -.01 1 (.882 ) .85 2 (.0001 ) .76 8 (.0001 ) .28 9

(.0001 ) .00 4 (.955 ) .84 7 (.0001 ) .72 7 (.0001 ) 1 .69 2 .39 4 (.0001 ) (.0001 ) 1 .89 3 (.0001 ) 

### 1 .35 2 (.0001 ) .03 3 (.669 ) .64 6 (.0001 ) .64 0 (.0001 ) .90 2 (.0001 ) .77 7 (.0001 ) .49 4 (.0001 ) 

### 1

### 3 9 Tabl e 7 . Multipl e linea r regressio nstatistic s fo r Crooke dCree k

Watershe d 0 2 litte r mas s (g/m 2 , transforme db y Eqn . 3 ) an d independen t variable s selecte d b y th e backwar d eliminatio nprocedur e a t P = 0.2 5 ( n = 174 , F, . , C Q = 6.344 , R 2 = 0.358) . ,4 ' 15 9 P.5 5 

## 1

Independen t Variabl e B n1 S E Intercep t Seaso n Litte r Z n Concentratio n Litte r Cu Concentratio n Litte r C

d Concentratio n Seaso nxSeaso nCrossproduc t Litte r P bxC

d Concentratio n Crossproduc t Litte r Z n xCu Concentratio n Crossproduc t Litte r PbxC

u Concentratio n Crossproduc t Litte r Cu xCu Concentratio n Crossproduc t Litte r P bxP bConcentratio n Crossproduc t 8.02 1 +0.37 9 -0.44 2 + 0.15 7 5.4xl0" 4 + 2.4xl0" 4 -3.0xl0' 4 + 2.2xl0' 4 -6.2xl0" 3 + 3.5xl0" 3 0.10 1 + 0.03 1 1.4xl0' 7 + 0.4xl0' 7
•1.5xl0" 7 + 0.7xl0' 7 •3.46xl0" 9 + 2.635xl0" 9 1.2xl0' 7 + 0.5xl0" 7
-1.219xl0" 1 0 + 5.022xl0 -1 14 0

o f th e CC

W controls , ther e wa s no significan t differenc e betwee nvalue s fo r C dan dZ ni neithe r litte r horizo n(Tabl e 8) . Apparently , particu late s responsibl e fo r th e Z nan dC dvalue s foundonCrooke dCree k Water she ddi dno t occu r i nsignifican t quantitie s a t 21. 0 k m wes t o f th e smelte r area . I

ncontrast , lea dvalue s a t Missour i contro l site s wer e 8 t o 1 7 time s greate r tha nth e Tennesse e values . Whe nsoi l comparison s
wer e made , th e Z nconten t o f Walke r Branc hWatershe dsoi l wa s greate r tha ntha t o f Crooke dCree k Watershe dsoi l b y a facto r o f 4 . Soi l C dan d ? bconten t di dno t diffe r significantl y betwee nth e tw

o study areas .
v,; ssour i control-sit e P bconcentration s ma y b e du e t o eithe r th e presenc e o f particulate s differen t fro m thos e responsibl e fo r Crooke d Cree k Watershe dP bo r th e occurrenc e o f a subterranea nP bmineralizatio n beneat hth e tre e roots . Metal s ar e know nt o accumulat e i ngroun dwate r
aroun dore-bearin g deposit s andca nb e detecte db y chemica l analysi s o f above-groun dvegetation . Goo dcorrelation s betwee nplan t an dsoi l P b conten t over

lea dmineralization s hav e bee nobtaine d(Cannon , 1960) .

Litte r Heav

y Meta l Poo l Th e availabl e heavy-meta l poo l inCrooke dCree k Watershe dlitte r wa s calculate db

y multiplyin g measure dvalue s o f Pb , Zn , Cu , an dC d 2 litte r conten t wit hth e correspondin g litte r mass/ m a t eac hsite . Mean s o f Septembe r litte r heav y meta l pool s analyze db y Duncan' s Ne w Multipl e Rang e Tes t ar e give ninTable s 9-10 . Seasona l variatio ni n amplitud e occurred , bu t trend s du e t o distanc e an ddirectio nwer e consisten t wit hthos e i nTable s 9-10 . Availabl e meta l pool s in0 1 litte r exhibite dth e same distributio n displaye db

y 0 1 litte r mas s fo r eac hsamplin g period , i.e. , no

### 4 1

Tabl e 8 . Compariso n o f Pb , Z n an d Cd concentration s (ppm ) i n Walke r Branc h Watershe d (WBW ) an d Crooke d Cree k Water
she d (CCW ) lea f litte r an d soils
. 

## T H

Sit e WBW 1

CCW 2 (21. 0 

### k m Horizo n 

### 0 1 0 2 A l 0 1 1 i tte r litte r soi l litte r site ) 0 2 litte r 

### A l soi l 

### P

b 

### 27 . 51 . 13 . 455 . 398 . 

### 13 . , 0

. 0

. 7

, 0

. 0

. 8 Z n 

### 42 . 110 . 

### 21 . 68 . Ill , 

### 5 . . 0

. 0

. 7

. 8

. 4

. 0 C d 

### .42 .8 1 .1 0 1.6 5 2.5 7 

### .2 3 

### 1 Dat a take n fromVa n Hoo k e t al_. , 197 6 (Fullerto n soi l o n WBW ) <n 11tter -72,n so11 -7T . 2 Dat a take n frompresen t dissertatio n (September ) an d Jackson , 197 6 (n 1itte r =16 , n SQi l =1) . 

### IP.5 8

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4 4 significan t chang e occurre d throughou t th e samplin g are a (Tabl e 9) . Despit e thi s lac k o f significance , i t ca nbe see ntha t pool-siz e wa s positivel y

relate d t o sourc e proximity . Th e distributio no f 0 2 litte r poo l value s parallele dthos e o f th e 0 2 litte r heavy-meta l concentration s (Appendi xC) , wit hsource-distanc e th e dominan t facto r i nestablishin g rank s o f mean s (Tabl e 10) . Th e ran k orde r o f metal-poo l size s als o follow s th e rankin g previousl y establishe d fo r th e concentratio ndata , i.e. , Pb>Zn>Cu>Cd . Ove r 95 % o f th e tota l meta l poo l a t th e 0. 4 k m site s wa s du e t o Pboccurrence , an ddecline d onl y slightl y

t o 93.2 % a t th e boundar y sites . Th e combinatio no f reduce d meta l depositio nan d 0 2 litte r mas s a t th e contro l sit e produce d
a Pbpoo l equallin g 60.5 % o f th e total . However , n o significan t differ ence s i npoo l siz e existe d betwee nth e contro l an dwatershe dboundar y sites . Chemica l Characterizatio no f Litte r Litte r Macronutrient s Al l macronutrien t catio nconcentration s wer e significantl y depresse d relativ e t o th e contro l inbot h0 1 an d0 2 litte r ou t t o 0. 8 k m fro m th e stac k sourc e (Fig . 12) . Tw o mechanism s ar e postulate dt o explai nthes e results : 1 ) increase d leachin g o f cation s throug hth e litte r cause db y a decreas e i nmicrobia l activit y and disruptio no f catio nexchang e processes , and 2 ) decrease d uptak e o f macronutrient s du e t o roo t damag e tha t resulte d i na reduce d annua l inpu t b y litterfall . Bot hhypothese s
wer e substantiate d b y litte r dat a collecte d fro m Crooke dCree k Watershed . Catio nexchang e processe s i n0 2 litte r wer e affecte db y a decreas e i nexchang e capacit y

an d a nincreas e i nacidit y (Tabl e 11) . Humus , th e4 5 P.6 1

*"

5 ( 0 | — z o OfiNL-OW O 75-10*5 0 ORNL-OW G 75-1095 2

LITTE R HORIZO N —

* 0 

# P^

0. 4 0. 8 1. 2 «. 6 •AH . 2. 0 " 2 t (CONTROL ) 0 1 STANC E FRO M SMELTE R (km ) 0. 4 0. 8 f. 2 1. 6 2. 0 2 1 (CONTROL ) DISTANC E FRO M SMELTE R (km )

ORNL-OW G 75-1095 4

2. 0 2 1 (CONTROL ) ORNL-OW G 75-1095 3 AAr- o

2. 0 2 1 (CONTRO U DISTANC E FRO M SMELTE R (km ) OISTANC E FRO M SMELTE R (km ) Fig . 12 . Mea nmacronutrien t concentration s o f Ca , Mg , K , an d P ( + 1 SE , n=12 ) i n Crooke d Cree k Watershe d litte r a s a functio no f distanc e fro

m th e AMA Xsmelter . Dat a fro m Jackso nand Watson , 1976 .

### 4 6 residu e o f decompositio nprocesses , act s a s a catio nexchange r andaid s inth e conservatio no f nutrien t cation s (Lut z an dChandler , 1946) . Humu s ma y

hav e a catio nexchang e capacit y a s higha s 11 0 meq/10 0 g an da buffere d p

H o f 4-5 . A s i t i s comprise do f a ric hmixtur e o f phenoli c
an d carboxyli c aci d groups , i t ca nreac t strongl y wit hheav

y metal s (Schnitze r and Khan , 1972) . Th e decreas e i nexchang e capacit y foundi n Crooke d Cree k Watershe d litte r (Tabl e 11 ) ma y hav e resulte dfro

m deple tiono f th e microbia l population s responsibl e fo r maintenanc e o f humi c reservoirs . Suc ha reductio ni nmicrobia l population s wa s als o indicate d b y a significan t declin e i nlitte r respiratio ndetecte dnea r th e smelte r (Ausmu s an

d Watson , 1975) . Increase d litte r acidit y (the additio no f mobil e anions ) i s als o know nt o encourag e catio nleachin g (McColl , 1972) . Th e acidi c litte r foundwithi n0. 8 k m o f th e AMA

Xstac k (Tabl e 11 ) ma y hav e resulte d fro

m S0 2 stac k emission s and/o r dissolutio no f meta l sulfid e particulates . Measurement s o f macronutrien t level s i nfres hsumme r leave s o f blac k and whit e oa k indicate d tha t canopy specie s o

nCrooke dCree k Watershe d ma y

b e experiencin g nutrien t depletio ndu e t o reduce duptak e (Tabl e 12) . Foliag e concentration s o f Ca , Kan dP wer e significantl y reduce d a t th e mos t heavil y contaminate d sit e (0. 4 km) . Thes e result s
ar e consisten t wit h0 1 litte r conten t o f macronutrients , wit hth e excep tiono f M

g (Fig . 12) . Th e reaso nfo r greate r uptak e o f M g wa s no t established . Analysi s o f macronutrien t pool s i n0 2 litte r fo r C a indicate da depressio nnea r th e smelte r (0. 4 an d 0. 8 km ) (Fig . 13) . Thi s declin e wa s produce d b

y th e extremel y

lo w C a concentratio n(Fig . 12 ) i nth e litte r a t thes e sites . N o significan t differenc e inmacronutrien t pool sP.6 3



### 47
Tabl e 11 . Catio nexchang e capacit y an d p H o f 0 2 litte r on Crooke d Cree k Watershe d (N W transect)' .

Distanc e (km ) CEC *

(meq/10 0 g ) 

### pH ' 0. 4 0. 8 1. 2 2. 0 2 1 (control ) 21.1 * 19.1 * 34. 9 33. 4 40. 3 4.0 * 4.1 * 5. 5 5. 2 5. 5 •Significantl y

differen t fro

m th e contro l a t P<.05 . 1 , 'Dat a fro

m Jackso nan

d Watson , 1976 . "Seasonall y

poole d value s (1974 , n=12) ,'«T'TIT'"H^" ' F^ 4 

### "T l
4 8

Tabl e 12 . Mea n macronutrien t concentratio n i n oa k leave s o n Crooke d

Creek,Watershe d i n relatio n t o distanc e fro m th e smelte r (n=6)l .

Distanc e (km )


### 0. 4 0. 8 1. 2 2. 0 21. 0 (co

n trol ) 

### C

a

7,615 * 9,517 * 11,56 9 10,35 0 13,01 6 

### M

g

1,60 9 1,44 8 1,66 3 1,76 7 1,50 4 

### K ug/ g 5,950 * 7,80 5 9,36 2 6,57 2 8,09 0 

### P

748 * 

### 93 1 1,17 3 

### 97 7 1,04 3
•Indicate s significantl ydifferen t fro m th e contro l a t th e 5 % leve l
Dat a fro m

Jackso n and Watson , 1976.

### 4 9 fo r M g and Kwa s found betwee nth e 0. 4 and0. 8 k m site s andth e control . Thi s apparen t parado xwa s explaine d b y a combinatio no f lo w macronutrien t concentration s (Fig . 12 ) an d hig hbiomas s accumulatio n(Tabl e 3 , Fig . 6 ) . Biomas s accumulatio nalon e accounte d fo r th e increas e i nal l macro nutrien t pool s betwee n1. 2 an d2. 0 k m (Fig . 13) . Th e P poo l i n0 2 litte r wa s no t depresse dfro m tha t o f th e contro l (Fig . 13) . However , a significan t depressio nexiste dfo r 0 1 litte r (Fig . 13) . Phosphoru s doe s no t behav e a s divalen t macronutrien t cations , fo r i t ma y

become bound i norgani c materia l an dmad e unavailabl e fo r
roo t uptake . Thi s bindin g coul daccoun t fo r th e accumulatio no f P i n0 2 litter . Wit hles s P availabl e fo r roo t uptake , incorporatio nint o ne w tissu e woul d b e decreased . Th e ne t resul t woul db e a substantia l dro p i n0 1 litte r P content . A declin e o f al l macronutrien t pool s in0 1 litte r wa s observe dt o 0. 8 k m fro m th e stac k (Tabl e 13) . Thi s depressio nwa s governe db y a decreas e i nmacronutrien t concentration s i nlitte r nea r th e smelter , and
no t b y litte r biomass . No significan t difference s o f macronutrien t poo l value s existe d betwee nth e 1. 2 an d 2. 0 k m site s whe ncompare dt o th e control . Thi s wa s evidenc e tha t macronutrien t uptak e ha dno t bee n significantl y

affecte d furthe r tha n0. 8 k m fro m th e smelte r stack . However , macronutrien t accumulatio ni n0 2 litte r pool s wa s indicativ e tha t uptak e ma y

b e affecte d i nth e future . Analysi s o f varianc e indi cate d a highl y

significan t interactio nbetwee nmacronutrien t pool s i n 0 1 and 0 2 litter . Th e significanc e o f thi s interactio ni s tha t th e compositio no f 0 2 litte r wa s drasticall y altere dfro

m norma l withi n0. 8 k m fro m th e stack . Du e t o incomplet e decomposition , th e bul k o f 0 2 biomas s wa s a heterogeneous mixtur e o f coarsel y t o finel y

fragmente d

# 1

30. 0

20. 0
E

10. 0 5 0
ORNL-OW

G 75-1095 * i r^ n T LITTE R HORIZO N

* I 

# -V-

1 0. 4 0. 8 1. 2 1. 6 2. 0 2 1 (CONTROL ) OISTANC E FRO M SMELTE R (km ) 2. 0 <

o '. 0 2

i - r ORNL-OW G 75-1095 8

LITTE R HORIZO N

0 1

- •%"*

0. 4 0.8 1. 2 1.6 2. 0 2 < (CONTROL

) DISTANC E FRO M SMELTE R (km ) ORNL-OW G 75-1095 5

0. 4 0. 8 1. 2 I. 6 2. 0 2 1 (CONTROL ) DISTANC E FRO M SMELTE R (km ) j = «. oLITTER(g/

z

_ l o 2 0.5 a .

0 1

1 

## I T

i

^,-i - » F ' ! 1 ORNL-OW G 73-1095 1 M .

LITTE R HORIZO N

_

- 0 2 ^

*£

% ""*
T

—

_ _o i ~ T7/--- E

1 ! •tr0. 4 0. 8 1. 2 1. 6 2. 0 2 1 (CONTROL ' OISTANC E FRO M SMELTE R (km ) Fig . 13 . Mea nmacronutrien t poo l size s o f Ca , Mg , K , an d P ( + 1 SE , n=12 ) i nCrooke dCree k Watershe dlitte r a s a functio no f distanc e fro m th e AMA Xsmelter . Dat a fro m Jackso nand Watson , 1976 .

nmpa»»

### 5 1 Tabl e 13 . Macronutrien t pool s o f 0 2 litte r onCrooke d Cree k

Watershe d (N

W transect)^ .

Ca pool ' (g/m 2 ) Mg pool '

(g/m 2 ) Kpool 2

(g/m 2 )

•Significantl y

differen t fro

m contro l a t P<.05 . Dat a fro m Jackso nan

d Watson , 1976 . P poo l (g/m 2 ) 6.5 * 10.9 * 22. 9 23. 5 18. 5 0.9 8

1.3 5 1.64 * 1.90 * 1.0 9 0.8 3

1.31 * 1.38 * 1.90 * 0.9 6 0.9 2

0.15 * 0.25 * 1.0 8 0.8 0 

# 1

'Seasonall y

poole d value s (1974 , n=12) .5 2

leave s an

d twig s wit ha smal l amoun t o f humu s mixe din . Thus , th e nutrien t conten t o f 0 2 litte r i nthi s are a wa s simila r t o tha t o f 0 1 Arthropod s Populatio nDensit y andBiomas s Regressio nanalysi s o f arthropo d densit y an dbiomas s dat a collecte d fro m th e 0 1 litte r horizo ndisclose d th e occurrenc e o f considerabl e variatio ntha t coul d no t b e explaine db y an y measure dvariable . Th e coefficien t o f variatio n(c.v.=10 0 xs/x ; Snedeco r an dCochran , 1967 ) exceede d 330% . I t seem s reasonabl e t o assume tha t physica l factors , suc ha s temperatur e o r relativ e humidity , woul dbe primar y controllin g agent s inth e arthropo d occupanc y o f th e 0 1 litte r horizon , fo r i t i s know ntha t temperatur e an d moistur e regime s ar e responsibl e fo r vertica l migratio nwithi nth e soil-litte r mediu m (Dowdy , 1944 , 1947 , an d1951) . Regardles s o f th e reason , n o measur e o f interaction s betwee narthropo d activit y an d litte r mas s o r heav y meta l conten t coul dbe discerne di n th e 0 1 horizo ndat a fro m thi s study . Therefore , onl y dat a fro

m th e 0 2 horizo nwer e analyze d (c.v . = 67.2%) . Th e effect s o f seaso no r winddirectio nwer e no t sufficien t t o explai nvariatio ni neithe r tota l arthropo dpopulatio nbiomas s and densit y o r populatio nbiomas s an d densitie s o f individua l trophi c levels . Distanc e fro m th e smelter , however , wa s a highl y significan t (P<.005 ) sourc e o f variatio nfo r predator , detritivore , fungivore , an d tota l arthropo d biomas s an ddensit y

inth e 0 2 litte r horizo n(se e Table s 14 , 1 5 and 16) . Replicat e effect s wer e insignifican t (P<.05 ) source s o f variatio n i nth e analysi s o f varianc e o f bot htota l an dtrophi c leve l densit y' TTTT
- " " TIT T 

# n l

5 3 Tabl e 14 . Seasona l mea n arthropo d biomas s (m g dr ywt/m 2 ) i n th e litte r horizo n o f Crooke d Cree k Watershed . On e standar d erro r i n parenthese s (n=4) . SPRIN G SUMME R FAL L WINTE R Sit e W 0, 4 W 0. 8 W 1. 2 W 1. 6 N W 0. 4 N W 0. 8 N W 1. 2 N W 2. 0 N E 0. 4 NE 0. 8 NE 1. 2 

### k

m k m k m k m k m k m k m k m k m k m k m W 21. 0 k

m (Control ) Mea n Biomas s

5.7 * ( 34.5 * ( 82. 9 ( 167. 1 ( 2.6 * 55. 6 66. 0 573. 0 11.3 * 23.9 * 110. 2 187. 8 4.0 )

11.4 ) 33.1 ) 70.9 ) 0.9 ) 30.3 )

r 14.2 ) (10.2 ) ( 5.7 ) ( 6.0 ) (60.1 ) (70.2 ) Mea n Biomas s

93. 5 ( 25. 4 ( 122. 8 ( 109. 5 ( 4.0 * 1 20.0 * 28. 9 195. 7 21. 3 15.5 * 56. 5 61. 5 54.4 )

4.4 ) 70.1 ) 48.8 ) 2.3 ) 1.9 ) [ 6.1 ) (20.9 ) ( 7.7 ) ( 5.0 ) (17.6 ) (22.1 ) Mea n Biomas s

11.6 * ( 20.7 * ( 54. 5 ( 190. 7 9.9 * 121. 6 88. 8 96. 9 4.7 * 73. 7 45. 1 137. 3 3.3 )

9 . 7 ) 17.6 ) 130.4 ) 4.2 )

' 65.1 ) ( 50.4 ) ( 61.3 ) 

### ( i.o ) ( 55.4 ) ( 22.2 ) ( 46.3 ) Mea n Biomas s

21. 3 30. 4 108. 0 19.4 * 3.2 * 26. 7 33. 8 140. 9 80. 6 25.0 * 29. 8 63. 9 (14.8 ) ( 10.2 ) (63.3 ) ( 6.7 ) ( 1.5 ) (13.8 ) ( 9.2 ) (54.3 ) (55.8 ) ( 6.8 ) (20.6 ) (17.6 )
•Significantl yreduce d fro mth e contro l (P<.10) .

### 5 4

Tabl e 15 . Seasona l mea n arthropo d densit y(no/m 2 ) i n th e litte r O 2

horizo n o f Crooke d Cree k Watershed . On e standar d erro r i n parenthese s (n=4) . P.7 0

SPRIN G SUMME R FAL L WINTE R Sit e Mea n Densit y Mea n Densit yMea n Densit yMea n Densit y 

## w w w w N W N W N W N W N E N E N E 0. 4 k

m 0. 8 k m 1. 2 k m 1. 6 k m 0. 4 k m 0. 8 k m 1. 2 k m 2. 0 k m 0. 4 k m 0. 8 k m 1. 2 k m W 21. 0 k

m (Control ) 55.0 * (

280.0 * ( 106. 0 1917. 5 ( 12.5 * 135. 0 452. 5 1137. 5 75.0 * 127.5 * 132.5 * 1217. 5 26.6 )

100.4 ) 558.1 ) 1175.1 ) 7.5 )

' 83.0 ) 196.0 )

' 599.5 ) 50.7 )

' 87.7 ) [ 88.5 ) ( 462.8 ) 165.0 * (

212. 5 ( 447. 5 257. 5 27. 5 130. 0 537. 5 1942. 5 127. 5 110. 0 252. 5 507. 5 129.4 )

70.9 ) 230.8 ) 121.5 ) 24.3 )

' 58.7 ) 207.0 ) 727.9 )

' 81.8 ) [ 52.3 ) [ 88.9 ) (317.9 ) 110. 0 (

123. 0 ( 198. 0 885. 0 75. 0 160. 0 263. 0 308. 0 43. 0 90. 0 70.0 * 358. 0 46.0 )

44.0 ) '104.0 ) '326.0 )

' 36.0 ) [ 77.0 )
r 145.0 ) [205.0 ) ( 24.0 ) ( 31.0 ) ( 32.0 ) (197.0 ) 50. 0 (

295. 0 ( 375. 0 ( 420. 0 ( 12.5 * 97. 5 270. 0 500. 0 512. 5 157. 5 177. 5 373. 0 21.2 )

138.8 ) 225.9 ) 176.1 ) 7.5 ) 47.1 ) 128.6 ) '250.3 )

r 479.0 )

' 67.9 )
r 138.8 ) (175.0 )

•Significantl yreduce d fro mth e contro l (POO) .P.7 1



### 5 5

Tabl e 16 . Mea

n annua l Crooke

d Cree k Watershe

d 0 2 litter arthropo

d predator , detritivor e an d fungivor e biomas s (m g dr ywt/m 2 ) an d densit y(no/m 2 ) . Seasons hav e bee n poole d a s replicates
. Value s i

n parenthese s ar e 1 standar d error (n=16) . Biomas s (mg/m 2 ) Densit y(no/m2 ) Sit e Predato r (km ) W 0. 4

W 0. 8

W 1. 2

W 1. 6

N W 0. 4

N W 0. 8
N W 1. 2

N W 2. 0

N E 0. 4

N E 0. 8

N E 1. 2

W 21. 0 (Control ) 6.1 ^

3.6 ) 12. 1 2.5 ) 15. 0 5.0 ) 11. 2 2.9 ) 2.1 ^ .4 ) 6.8 ^ 3.6 ) 14. 0 4.0 ) 87. 6 41.5 ) 5.7 ^ 2.4 ) 8.5 3 2.1 ) 17. 4 ' 8.4 ) 17. 3 ' 5.4 ) Detritivor e Fungivor e

22.1 * (13.9 ) ( 6.3 * (1.2 ) ( 33. 0 (13.6 ) ( 42. 4 (19.6 ) ( 2.3 * ( 2.1 ) 16.6 * ( 4.5 ) 12.6 * ( 2.9 ) 92. 6 (40.4 ) 18.5 * (15.4 ) 20. 4 (14.9 ) 27. 6 (17.7 ) 61. 1 (20.4 ) 1.2 *

0.3 ) 2.7 * 1.4 ) 15. 1 7.3 ) 13. 3 6.5 ) 0.8 * 0.3 ) 2.4 * 0.4 ) 5. 6 3.2 ) 16. 1 '12.0 ) 3.1 * 0.8 ) 1.1 * ' 0.3 ) 2.6 *
22. 1 (10.4 ) Predato r

19.0 * ( 5.5 ) 31.9 * ( 7.5 ) 76. 3 (22.0 ) 72. 5 (20.6 ) 10.6 * ( 1-9 ) 30.0 * ( 8.9 ) 71. 9 (38.9 ) 110. 6 (19.7 ) 21.9 * ( 2.8 ) 44.4 * ( 6.6 ) 45.6 * (17.3 ) 86. 9 (15.1 ) Detritivor e Fungivor e

36.9 * ( 15.4 ) ( 206. 9 ( 58.2 ) ( 240. 6 ( 93.0 ) 550. 6 (300.0 ) ( 6.3 * ( 3.8 ) ( 36.3 * ( 9.7 ) ( 143. 8 ( 75.7 ) 1001. 9 (429.3 ) ( 119. 4 ( 94.4 ) 79.4 * ( 27.6 ) 71.3 * ( 16.1 ) 294. 4 ( 69.4 ) 24.4 *

4.3 ) 41.3 * 16.1 ) 256. 3 164.3 ) 298. 1 145.5 ) 18.13 * 11.0 ) 60.0 * 13.7 ) 129. 4 77.4 ) 381. 3 261.0 ) 57.5 * 15.1 ) 20.0 * 7.1 ) 26.9 * ' 6.2 ) 511. 9 '243.4 )
•Significantlyreduce d fro mth e contro l valu

e (P<.10) .

### 5 6

andbiomass . Thus , i t wa s assume dtha t th e 4-replicat e desig nutilize d fo r arthropo dfield-samplin g o nCrooke dCree k Watershe di n197 4 wa s sufficien t t o adequatel y estimat e litte r arthropo dpopulations . Analysi s o f varianc e indicate dtha t neithe r season , distance , no r win ddirectio nhadsignifican t effect s onomnivor e o r littergraze r densit y andbiomass . Thi s resul t ma y b e du e t o th e variabilit y i n occurrenc e o f thes e trophi c group s onCrooke dCree k Watershe d- - omni vore s wer e foundi n75 % o f th e sample s andlittergrazer s occurre din onl y 53% . Member s o f th e othe r thre e trophi c level s wer e foundinove r 90 % o f th e samples . Leas t square s multipl e linea r regressio nprocedure s wer e usedt o evaluat e th e variatio nfoundinmeasurement s o f CC W tota l arthropo d biomas s anddensit y

(Table s 1 4 and15) . Th e empiricall y derive dregres sio nmode l include deffect s du e t o season , directio nanddistanc e fro m th e AMA Xsmelter , litte r heav y meta l concentration ; andal l interaction s du e t o multiplicativ e effects . Th e linea r mode l presente da s Equatio n# 4
wa s als o use dt o evaluat e th e dependen t variables , tota l arthropo dbio mas s anddensity . Us e o f th e 23-variabl e mode l accounte dfo r 51.2 % o f th e variatio nwithi nth e tota l arthropo dbiomass , bu t onl y 15.2 % o f th e tota l densit y

variation . Th e inabilit y

o f th e mode l t o adequatel y explai nvariabilit y

withi n th e arthropo ddensit y dat a ma y

b e du e t o severa l factors . First , i t i s highl y probabl e tha t th e relationship s betwee narthropo ddensit y an d th e measure dindependen t variable s ma y b e explaine db

y a non-linea r model . Onl y

multipl e linea r model s wer e evaluate dinth e presen t dat a analysis . Secondly , bot hhistorica l an dcurren t temperature-moistur e regime s ar e know

nt o b e importan t indeterminin g th e distributio no fP.7 3



### 5 7 arthropod s a t an

y on e poin t intime (Dowdy , 1944 , 1947 , 1951 ; Andre warth a 1961) . Thes e factors , fo r whic hn o record s wer e available , ma y be responsibl e fo r a larg e portio no f th e unexplaine dvariabilit y i nth e CC W arthropo d densit y

measurements . Examinatio no f regressio nstatistic s fro m analysi s o f arthropo d biomas s dat a reveale d tha t no t al l 2 3 variable s wer e necessar y t o accoun t fo r a majo r portio no f tota l variatio n(Table s 1 7 an d18) . Subsequen t analysi s b y stepwise , an

d forwar dan

dbackwar deliminatio n regressio nprocedure s (Drape r an d Smith , 1966 ) indicate dtha t th e latte r metho d provide d th e bes t evaluatio no f variabilit y withi nth e dat a a t P = 0.2 5 th e significanc e leve l fo r entry . Wit hth e numbe r o f effectiv e independen t variable s reduce dt o 9 , 50.7 % o f th e tota l variatio ncanb e accounte dfo r (Tabl e 19) . Signifi can t (P<.01 ) negativ e correlation , coefficient s wer e obtaine dfo r th e first-orde r variable s litte r Z nan d litte r C

dconcentration s an

dth e multiplicativ e interaction s o f litte r P bxZn , P bxCu , Z nxCu , Z nx C d an d C u xC d concentration s (Tabl e 18) . Th e second-orde r variable s
o f litte r Cu xCu an

d C d xC dwer e als o negativel y correlate d(P<.01 ) wit harthropo d biomas s (Tabl e 18) . Thus , highlevel s o f heav y metal s inth e litte r substrat e occurre dsimultaneousl y wit hsmal l arthropo dbio mas s values . Sinc e distanc e fro m th e AMA Xsmelte r wa s als o signifi cantl y correlate d wit hlitte r heav y meta l conten t (se e als o Figs . 7-10) , thi s heav

y meta l effec t onth e arthropo dbiomas s ma y be responsibl e fo r th e significan t distanc e effec t detecte db y previou s ANOV

A analysis . Interaction s betwee narthropo dbiomas s an dlitte r heav

y meta l conten t o nth e Crooke d Cree k Watershe dfores t floo r wer e no t simpl e one-to-on e relationships . Result s o f th e presen t regressio nanalysi s

### 5 8 • •T- S . » r T , - Tff ^ 1 T •

Tabl e 17 . Multipl e linea r regressio nstatistic s fo r Crooke dCree k

Watershe d 0 2 litte r arthropo dbiomas s (mg/m 2 , transforme d b y Eqn . 3 ) ( n = 176 , F 2 3 15 2 = 6.931 , R 2 = 0.512) . Independen t Variabl e Intercep t Seaso n Directio n Distanc e Litte r P bConcentratio n Litte r Z n Concentratio n Litte r Cu Concentratio n Litte r C

d Concentratio n Seaso nxDirectio nCrossproduc t Seaso nxDistanc e Crossproduc t Directio nxDistanc e Crossproduc t Seaso nxSeaso nCrossproduc t Directio nxDirectio nCrossproduc t B + S E p n- -0.05 9 + 0.69 4 0.24 0 + 0.35 7 4.08 6 + 1.99 2 -10.40 7 + 2.40 1 4.94xl0" 6 + 2.056xl0" 5 1.062xl0' 3 + 9.649xl0" 4 3.187xl0~ 4 + 7.262xl0" 4 -0.01 7 +0.01 3 -0.13 7 + 0.40 7 0.75 5 + 0.45 7 -18.29 6 + 14.53 6 -0.02 5 +0.06 9 9.54 8 + 7.21 2 

# - q

Distanc e xDistanc e Crossproduc t Litte r P bxZ n Concentratio n Crossproduc t Litte r P bxC

u Concentratio n Crossproduc t Litte r P bxC

d Concentratio n Crossproduc t Litte r Z n xC u Concentratio n Crossproduc t Litte r Z n xC

d Concentratio n Crossproduc t Litte r C

u xC d Concentratio n Crossproduc t Litte r P bxP bConcentratio n Crossproduc t Litte r C

u xC u Concentratio n Crossproduc t Litte r C

d xC d Concentratio n Crossproduc t Litte r Z n xZ n Concentratio n Crossproduc t 5.97 2 + 7.92 5 3.0xl0' 3 + 2.0xl0" 8 -4.0xl0" 8 + 2.0xl0" 8 -1.8xl0" 7 + 3.0xl0" 7 8.8xl0" 7 + 8.3xl0" 7 -1.718xl0' 5 + 1.257xl0" 5 8.87xl0" 6 + 8.96xl0" 6 -5.99xl0' 1 2 + 6.25xl0 -1 1 -4.1xl0" 7 + 3.0xl0" 7 2.002xl0' 4 + 1.293xl0" 4 -2.9xl0" 7 + 6.4xl0" 7

swwgmu'J i ^'J T•T
- 'i n WY^* ITTTTnTr"" " 

### T H

5 9 Tabl e 18 . Correlatio n matri x resultin g frommultipl e linea r

regressio n analysi s o f tota l arthropo d biomas s (mg/m 2 , transforme d b yEqn . 3 ) foun

d o n Crooke d Cree k Watershe d ( n = 176 , F 2 3 , „ = 6.931 , R 2 = 0.512) . Value s i n parenthese s ar e significanc e levels .

Y

X l Y 1 X l -.10 7 (.158 ) 1 

## x 2 -.38 0 (.0001 ) 0. 0 (1.0 ) X 3 -.45 9 (.0001 ) 0. 0 (1.0 ) X 4 X 5 X 6 -.51 4 -.31 7 -.20 5 (.0001 ) (.0001 ) (.006 ) .00 9 -.00 3 .01 1 (.906 ) (.965 ) (.885 ) X 7 -.47 6 (.0001 ) .04 2 (.577 ) .95 4 .55 1 .84 5 .84 2 .63 7 (.0001 ) (.0001 ) (.0001 ) (.0001 ) (.0001 ) 1 .57 7 .75 9 .72 0 .62 8 (.0001 ) (.0001 ) (.0001 ) (.0001 ) 1 .69 5 .39 8 .90 2 (.0001 ) (.0001 ) (.0001 ) 1 .89 4 .78 0 (.0001 ) (.0001 ) 

### 1 .49 8 (.0001 ) 

### 1

### 6 0

Tabl e 19 . Multipl e linea r regressio nstatistic s fo r Crooke dCree k

Watershe d0 2 litte r arthropo dbiomas s (mg/m 2 , transforme d b y Eqn . 3 ) an

d independen t variable s selecte db y th e back war deliminatio nprocedur e a t P = 0.2 5 ( n = 176 , F, . , c , = 10.178 , R 2 = 0.507) . 14 ' 16 1

Independen t Variabl e B + S E p n- P.7 6 

### T 

# 1

Intercep t 0 2 Litte r Z n Concentratio n 0 2 Litte r C

d Concentratio n 0 2 Litte r P bxZ n Concentratio n Crossproduc t 0 2 Litte r P bxC

u Concentratio n Crossproduc t 0 2 Litte r Z n xC u Concentratio n Crossproduc t 0 2 Litte r Z n xC

d Concentratio n Crossproduc t 0 2 Litte r Cu xC

d Concentratio n Crossproduc t 0 2 Litte r C u xC u Concentratio n Crossproduc t 0 2 Litte r C

d xC d Concentratio n Crossproduc t 

### -0.05 9 +0.69 4 0.00 1 + 0.000 6 -0.02 0 +0.01 0 l.OxlO' 8 + l.OxlO" 8 3.0xl0" 8 + l.OxlO" 8 4.4xl0' 7 + 1.5xl0" 7 18.6xl0' 6 + 6.0xl0" 6 10.3xl0" 6 + 5.5xl0~ 6 •2.5xl0" 7 + l.OxlO' 7 15.9xl0" 5 + 6.0xl0" 5P.7 7 T I I

6 1 indicate d tha t n o singl e facto r ca nb e isolate da s th e primar y sourc e o f variabilit y

i nwatershe d arthropo dbiomass . A comple xo f variable s mus t b e considered . However , i t wa s clearl y demonstrate dtha t th e heav y meta l conten t o f Crooke d Cree k Watershe dlitte r wa s no t onl y strongl y
an d negativel y

correlate d wit harthropo d biomass , bu t wa s als o respon sibl e fo r 50 % o f tota l dat a variation .
Heav y Metal s Field-collecte d arthropod s wer e poole d t o provid e sufficien t materia l fo r heav

y meta l analysi s o f eac htrophi c level . Specimen s categorize d b

y seaso nan

d replicate , variable s know nt o be insignifi can t i ncontrollin g populatio ndensit y and biomass , wer e combine d
acros s bot hlitte r horizons . Th e resultin g poole dsample s wer e com pose d o f 3 2 individua l sample s ( 4 season s x4 replicate s x2 horizons )
and wer e assaye d fo r Pb , Zn , Cu , an d C d content . ] Lead : Previou s documentatio no f arthropo d P bconcentration s associate d wit htrophi c classificatio nindicate dtha t th e mos t elevate d level s occurre d i nth e detritivore-fungivor e group s (Williamso nand Evans , 1972) . Isopod s feedin g i ndecayin g vegetatio nonYorkshir e roadside s containe d 68 2 pp m dr y wt Pb(Williamso nan dEvans , 1972) . Littergrazin g diplopod s andpredaceou s opilionid s andspider s wer e nex t i norde r o f decreasin g lea d content , wit hvalue s o f 82 , 45 , an d2 3 pp m respectively . Othe r publishe d value s fo r roadway-sourc e P bi narthro pod s wer e lowe r tha nthos e foundb y Williamso nan

dEvan s (Gile s e t al. , 1973 ; Institut e o f Envir . Studies , 1972) . Th e P bconten t o f isopod s collecte d o nYorkshir e ditchbank s i s comparabl e t o tha t o f Crooke dCree k Watershe dfungivores . Otherwise ,6 2

watershe dvalue s excee dal l previousl y publishe dinformatio nfo r comparabl e trophi c level s an dfo r th e same trophi c leve l a t the water she dcontro l sit e (Tabl e 20) . Elevate dquantitie s o f Pbwer e foun d associate dwit hpredaceou s arthropod s collecte dfro m heavil y Pb contaminate d site s nea r th e smelte r (c f Fig . 7 ) Zinc : Zin c i s know

nt o b e necessar y

t o a numbe r o f biologicall y importan t enzym e reaction s bot hb y actin g a s a nonspecifi c cofacto r incontrollin g th e rat e o f reactio nan da s a constituen t o f many metalloenzyme s (Orten , 1966) . Zin c i s als o necessar y fo r RN A an d DN A formatio n(Schroeder , 1974) . Thus , thi s elemen t i s a norma l componen t o f biologica l systems . However , du e t o th e complet e absenc e
o f comparabl e dat a i t i s no t know ni f th e quantitie s foun dassociate d wit hth e Crooke dCree k Watershe darthropo dpopulatio n(Tabl e 21 ) ar e differen t fro

m wha t woul db e expecte dina non-pollute dsystem . Copper : Coppe r i s containe dinth e arthropo dbloo dprotein , hemocyanin , an

di s a norma l constituen t o f al l arthropo dtissu e (Wieser , 1961 ; Wigglesworth , 1965) . However , sinc e trophi c leve l Cuconcentra tion s founda t th e 21. 0 k m contro l sit e wer e significantl y les s than an y o f thos e foundonth e watershed , th e elevate dlevel s o f C uasso ciate dwit hCrooke dCree k Watershe darthropod s ar e rea l (Tabl e 22) . Th e highes t level s o f Cufoundinth e spider , "othe r predator" , an domnivor e population s occurre da t thos e site s locate deithe r closes t t o th e smelte r o r alon g th e NE transect . Exposur e t o Cuconcentrat e onthi s transec t appeare dt o produc e elevate dCulevel s inlitte r arthro pod s comparabl e t o thos e produce db y exposur e t o stac k emissions . Cadmium : Previou s documentatio no f arthropo dC dconcentration s includ e value s fo r grasshopper s collecte da t varyin g distance s fro m1

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### 6 5
Tabl e 22 . Coppe r concentration s (pg/ g dr ywt ) foun d associate d wit h arthropo d trophi c level s o n Crooke d Cree k Watershed . Specimen s fro mbot h litte r horizon s an d al l season s an

d al l replicate s wer e poole d fo r chemica l analysi s (n=32) .

Sit e (km )
W 0. 4 W 0. 8 W 1. 2 W 1. 6 N W 0. 4 N W 0. 8 N W 1. 2 N W 2. 0 N E 0. 4 N E 0. 8 N E 1. 2 W 21. 0 (control ) Predator *

547. 8 138. 9 32. 5 28. 1 320. 5 37. 5 98. 0 59. 4 136. 2 83. 3 169. 1 48. 6 Spide r

197. 4 176. 6 174. 1 129. 8 242. 9 181. 5 72. 9 151. 9 448. 7 626. 0 480. 0 72. 9 TROPHI C Detriti

vor e 155. 9 204. 1 54. 9 13. 3 476. 2 79. 2 512. 8 50. 7 122. 0 163. 0 1189. 2 24. 1 LEVE L

Fungivor e
200. 0 555. 6 47. 6 75. 0 71. 7 220. 0 140. 2 172. 4 200. 0 137. 9 500. 0 149. 3 Litter

graze r 137. 1 86. 4 42. 5 200. 0 291. 3 72. 1 302. 2 101. 5 63. 8 275. 9 479. 5 109. 3 Omnivor e

156. 6 47. 3 43. 5 28. 8 84. 7 32. 8 27. 6 31. 8 263. 2 795. 5 768. 4 20. 4

*0the r tha n spider s6 6 10 9

a Z nsmelte r i nMontan a an d th e result s o f a C dtaggin g experimen t utilizin g a grass-cricke t (Pteronemobiu s sp.)-spide r (Lycos a sp. ) food chai n(Munshower , 1972 ; Va nHoo k an d Yates , 1975) . Grasshopper s feed in g oncontaminate d vegetatio ncontainin g 1. 8 an d1. 0 pp

m C d(2. 4 an

d 2 4 k m fro m th e smelte r source ) incorporate dwhole-body C dlevel s o f 7. 1
an d 1. 8 pp

m respectivel y

(Munshower , 1972) . Omnivorou s cricket s an d predaceou s spider s i na trace-contaminate d system (.06 9 pp

m Cdi n vegetation ) incorporate d muc hlowe r amount s o f C d(0.04 2 an

d0.03 0 ppm , respectivel y

(Va nHoo k an

d Yates , 1975) . Cadmiu m value s fo r Crooke dCree k Watershe darthropod s collecte da t th e contro l sit e wer e comparabl e t o thos e o f Munshower' s (1972 ) herbi vorou s grasshoppers , an d range d fro

m 1. 4 pp m fo r fungivore s t o 10. 2 pp m fo r omnivore s (Tabl e 23) . Th e averag e C d conten t o f bot hlitte r horizon s
a t th e CC

W contro l sit e wa s 5. 1 pp m (Appendi xC) . Cadmiu m i s commonl y foun d associate d wit hZningeologica l formation s (Schroeder , 1974) , an d i t i s expecte d tha t C d value s i nbiot a collecte dnea r a Znsmelte r woul d represen t a highl y

contaminate dcondition . Eve nthoug hdifferen t trophi c level s wer e studie d a t th e tw o site s i t wa s clea r tha t Crooke dCree k Watershe d arthropo d C d value s wer e eithe r comparabl e to , o r exceeded , thos e found nea r othe r C d source s (Tabl e 23) . Concentratio nFactor s Th e ecologica l consequence s o f heavy-meta l transpor t i nfoo d chain s canb e partiall y evaluate db

y a nanalysi s o f concentratio n facto r data . A

concentratio nfacto r (CF. ) i s define da s the "rati o o f elemen t leve l i nconsume r t o elementleye l i nfood-chai nbase " (Reichl e et_ al_. , 1970) . Element s ingeste d b y th e consume r ma y

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dilute d(C.F^ < 1.0) , concentrate d(CF . > 1.0) , o r underg o n o chang e (CF . = 1.0 ) relativ e t o th e level s foundi nth e foo dbase . Concen tratio nfactors , weighte db y th e proportio no f tota l biomas s provide d b y eac hlitte r horizo no r trophi c level , hav e bee nderive dfo r Pb , Zn , Cu , an dC di nth e CC W litter-arthropo d foo dchai n(Table s 24-27) . Concentratio nvalue s give ninTable s 20-2 3 wer e use di nth e calcula tions . A s anexampl e o f P bconcentratio nfacto r estimate s fo r th e litte r fauna:litte r foo dbas e a t th e W . 4 k m site , th e followin g calculatio nwa s performed : C F = P[ ) [Pb D ] + P F [Pb F ] + P Q [Pbg ] + p L [Pb L ]
p 0 1 [Pb 0 1 ] +p 0 2 [Pb 0 2 ] wher e P D= proportio no f tota l litte r faun a biomas s provide db y detritivore s = 0.67 1
p r = proportio no f tota l litte r faun a biomas s provide db y fungivore s = 0.04 5 p = proportio no f tota l litte r faun a biomas s provide db y " omnivore s = 0.27 7 p . = proportio no f tota l litte r faun a biomas s provide db y littergrazer s = 0.00 6 p m = proportio no f tota l litte r mas s provide db y 0 1 litte r = U l 0.18 0 p n 9 = proportio no f tota l litte r mas s provide db y 0 2 litte r = U6 0.82 0 [Pb D ] = concentratio no f Pb(yg/ g dr y wt ) foundassociate dwit h arthropo ddetritivore s = 1000. 0 [Pb F ] = concentratio no f Pb(ug/ g dry wt ) foundassociate dwit h arthropo dfungivore s = 388. 9 [P b] = concentratio no f P b(ug/ g dry wt ) foundassociate dwit h 0 arthropo domnivore s = 2857. 1. TM -. - ^ lrlrw ^^. mwnr -



### 6 9

Tabl e 24 . Weighte d concentratio nfactor s calculate d for P btranspor t i nthe Crooked Cree k watersne d litter-arthropod foo d chain .

if V i l* i

- Sit e 1

(km ) 

### W W W W N W N W N W N W N E N E N E 0. 4 0. 8 1. 2 1. 6 0. 4 0. 8 1. 2 2. 0 0. 4 0. 8 1. 2 W 21. 0 (control ) .itte r Fauna

Litte r 0.0 2 0.0 4 0.1 2 0.0 6 0.0 6 0.0 2 0.0 4 0.0 5 0.0 2 0.0 3 0.2 8 0.1 0 ^CENTRA "

Spider s Litte r Fauna 1.1 2 0.5 6 0.1 9 1.9 5 0.8 1 0.4 9 0.7 7 0.3 7 3.6 6 1.7 6 0.0 1 0.4 2 TIO

N FACTORS ^ Predators * Litte r Fauna 19.1 3 4.2 0 0.5 2 0.4 3 3.4 4 0.2 8 0.7 6 0.5 3 1.3 9 0.6 8 0.1 3 0.6 5
' |.i3 Al l Predator s

Litte r Fauna 10.6 7 2.4 9 0.4 2 1.1 7 2.7 5 0.3 1 0.7 6 0.5 1 2.3 9 1.2 3 0.1 0 0.6 0

*0the r thanspider s- • * r ~T>"H^r T " r «~rF»rif'' " P.8 6



### 7 0
Tabl e 25 . Weighte d concentratio n factor s calculate d fo r Z n transpor t

i n th e Crooke d Cree k Watershe d litter-arthropo d foo d chain
.

Sit e L (km )
W 0. 4 W 0. 8 W 1. 2 W 1. 6 N W 0. 4 N W 0. 8 N W 1. 2 N W 2. 0 N E 0. 4 N E 0. 8 N E 1. 2 W 21. 0 (control ) itte r Faun a Litte r 0.5 2 0.9 1 0.7 6 0.9 5 0.4 3 0.3 8 0.8 3 1.8 0 0.1 2 0.1 7 0.2 0 2.0 9 CONCENTRATIO NFACTOR S Spider s Litte r Fauna 0.7 1 1.5 5 1.9 9 1.8 3 0.9 8 2.1 5 1.1 8 0.8 0 2.9 0 2.0 2 1.5 1 2.5 7 Predators *

Litte r Faun

a 0.9 3 1.3 4 1.6 3 1.2 5 0.4 3 0.8 5 1.7 6 0.7 9 1.0 6 1.1 3 0.7 0 2.6 9 Al l Predator s

Litte r Faun

a 0.8 3 1.4 4 1.7 4 1.5 3 0.5 7 1.0 3 1.7 1 0.7 9 1.8 7 1.5 8 0.9 0 2.6 6

*0the r tha n spider s

### 7 1
Tabl e 26 . Weighte

d concentratio

n factor s calculate

d for C u transpor t i n th e Crooke d Cree k Watershe

d litter-arthropo

d foo d chain
. • *r"1

Sit e L 

### (km )
W 0. 4 W 0. 8 W 1. 2 W 1. 6 N W 0. 4 N W 0. 8 N W 1. 2 N W 2. 0 N E 0. 4 N E 0. 8 N E 1. 2 W 21. 0 (control ) .itte

r Faun a Litte r 0.1 7 0.9 2 0.3 4 0.2 8 0.2 3 0.1 5 1.1 0 0.6 1 0.0 9 0.0 8 0.2 2 2.0 6 CONCENTRATIO NFACTORS Spider s Litte r Faun

a 0.5 9 0.3 7 1.0 7 1.9 6 0.2 2 0.4 0 0.0 3 0.3 2 1.4 2 1.1 7 0.1 2 0.2 7 Predators *

Litte r Faun

a 1.8 4 0.3 2 0.4 7 0.4 4 0.8 3 0.5 1 0.4 6 0.7 2 0.5 5 0.1 5 0.1 3 0.6 8 Al l

Li t Predator s te r Faun a 1.2 5 0.3 4 0.6 5 1.1 8 0.6 7 0.4 9 0.4 2 0.6 6 0.9 3 0.6 7 0.1 3 0.5 9

*0the r tha

n spider sP.8 8 T l



### 7 2

Tabl e 27 . Weighte d concentratio nfactor s calculate dfo r C d transpor t inth e Crooke d Cree k Watershe d litter-arthropo d foodchain .

Sit e L (km )
W 0. 4 W 0. 8 W 1. 2 W 1. 6 N W 0. 4 N W 0. 8 N W 1. 2 N W 2. 0 N E 0. 4 N E 0. 8 N E 1. 2 W 21. 0 (control ) itte

r Faun a Litte r 0.6 5 0.2 2 0.5 1 0.3 9 0.3 8 0.3 3 0.2 6 0.5 0 0.1 0 0.1 0 0.3 4 0.6 4 CONCENTRATIO N FACTOR S Spider s Litter Faun

a 0.5 1 5.3 5 1.4 4 2.7 4 0.5 2 0.3 2 0.1 0 0.5 7 1.1 2 3.7 7 0.6 5 0.2 7 Predators *

Litter Faun

a 0.8 5 1.8 3 0.6 4 0.8 4 0.5 0 0.3 8 1.9 9 0.9 9 0.5 1 0.7 9 0.2 9 1.1 5 Al l Predator s

Litter Faun

a 0.6 9 3.4 8 0.8 8 1.7 7 0.5 1 0.3 7 1.8 2 0.9 3 0.7 8 2.3 1 0.3 8 0.9 7

*0the r tha nspider sP.8 9 

## "Ti l

7 3 [Pb, ] = concentratio no f Pb(ug/ g dr y wt ) foundassociate dwit h arthropo d littergrazer s = 485. 7 [Pb nl ] = concentratio no f P b(yg/ g dr y wt ) in0 1 litte r = U l 38.0x10 3 [Pb no ] = concentratio no f Pb(yg/ g dry wt ) in0 2 litte r = ^ 70.3xl0 3 C F . = 1482. 8 = .0 2 64486. 0

Lead: ) Th e concentratio no f Pbdecrease d fro m litte r t o litte r faun a o nCrooke d Cree k Watershe d (Tabl e 24) . A plo t o f th e log o f foo d bas e Pbconcentratio n(range : 43 0 t o 6877 0 ppm ) vs . correspondin g concentratio nfacto r value s fo r litter-feedin g faun a (range : 0.0 2 t o 0.28 ) illustrate d tha t a mea nconcentratio nfacto r o f 0.0 7 +

_0.0 2 (S.E. ) woul d b e anadequat e estimat e o f Pbtranspor t i nth e grazin g foo dchain . Arthropo d predator s appeare dt o be eithe r concentratin g o r i n equilibriu

m wit hth e P bconten t o f thei r litte r faun a prey . Wit hth e exceptio no f th e elevate d "othe r predator " concentratio nfacto r found
a t W 0. 4 km , th e predato r concentratio nfactor s range dbetwee n0.0 1 t o 4.20 . Th e correspondin g variatio ni npre y P bconcentratio nwa s fro m 4 3 t o 1151 6 ppm . A semilo g plo t o f pre y Pbconcentratio nvs . Pbconcentratio n factor s indicate d tha t a mea nconcentratio nfacto r woul db e anadequat e representatio no f Pbbiotransfe r fro m prey t o predator . Th e mean s are : t 0.2 9 (S.E. )

= 1.1 8 + 0.4 1 (S.E. ) C
- F -spiderPb = 1
- 0 1 ± 0
- 2 9 < S ' E
- > 

### CF . othe r predato r Pb C ' F 'tota l predato r P b= 1-1 6 + 0.2 9 (S.E. )
Thes e mean s ar e conservativ e intha t th e on e elevate dconcentratio n facto r a t th e W

0. 4 k m sit e ha s bee ndeleted .

### 7 4 P.9 0

Zinc : Zin c wa s bein g accumulate d inCrooke d Cree k Watershe d litte r faun a t o a muc hgreate r exten t tha nwa s Pb , althoug hconcentratio n (CF>1.0 ) doe s no t ye t appea r t o b e occurrin g (Tabl e 25) . Zin c i s require d b

y livin g system s (Orten , 1966 ; Schroeder , 1974) , an d th e concentratio nfactor s found fo r Crooke d Cree k Watershe d arthropod s ma y reflec t physiologica l requirements . Th e larges t litte r fauna:litte r concentratio nfactor s existe d wher e th e smalles t litter-Z nvalue s occurre d - W

1. 6 k m ([Zn,.. . ] = 10 0 ppm) . Litte r Znvarie d fro m 10 0 t o 389 4 pp

m whil e th e litte r faun a concentratio nfacto r estimation s varie d fro

m 0.1 2 t o 2.09 . Plottin g o f th e dat a a s previousl y discusse d indicate d tha t a mea no f 0.6 4 +

_0.1 5 (S.E. ) adequatel y represente d th e biologica l transfe r o f Z npresentl y occurrin g i nthi s foo d chain . I t i s no t clea r i f arthropo d predator s concentrate d o r equilibrate d Zninrelatio nt o thei r food base . A s predato r concentratio nfactor s varie d betwee n0. 4 and 2.7 , prey Z nvarie d betwee n206. 8 an d 909. 1 ppm . Mea nconcentratio nfactor s were :

C
F -sp,derZ n = 1
- 6 0 i°- 2 0 (S
E
- > "•othe r predato r *, - 1.0 8 ± 0.1 2 (S.E. ) "•tota l predato r Z B • 1.27 + 0.1 4 (S.E.) . Copper : Concentratio n(CF.>1.0 ) o f C u throug hth e litte r fauna : litte r foo d chai ndoe s no t appea r t o occu r onCrooke d Cree k Watershe d (Tabl e 26) . Coppe r wa s bein g accumulate d i nlitte r faun a t o a muc h greate r exten t tha nwa s Pb , bu t thi s phenomeno nma y b e a resul t o f copper' s presenc e i nth e arthropo d circulator y syste m a s hemocyani n (Wieser , 1961 ; Wigglesworth , 1965) . A s litte r coppe r concentration s varie d betwee n2 7 an

d 459 0 ppm , concentratio nfacto r value s varie d

### 7 5 P.9 1

betwee n 2 7 an d 459 0 ppm , concentratio n facto r value s varie d betwee n 0. 8
an d 2.06 . Th e mea n C u litte r faun a CF . wa s 0.3 8 +

_0.1 0 (S.E.) . Th e highes t litte r concentratio n facto r occurre d wher e th e smalles t litte r C u valu e existe d - - W 21. 0 km . I n contras t t o result s fo r P b an d Zn , C u appeare d t o b e dilute d b y food-chai n transfe r fro mpre yt o predato r o n Crooke d Cree k Watershed . Mea n concentratio n factor s were :

C

- F -spiderC u = 0

- 7 0 ±°- 1 9 ^ - E

- )
C

F 'othe r predato r C u = 0 ' 5 8 ±°- 1 4 < S ' E

- ) C ' F -tota l predato r C u = 0

- 6 7 ± 0

- 1 0 ^S.E. ) Cadmium : Concentratio n factor s fo r Crooke d Cree k Watershe d litte r faun a (Tabl e 27 ) were comparabl e t o thos e foun d fo r omnivorou s cricket s (Pteronemobiu s spp. , CF . = 0.6 ) fe d o n Cd-tagge d vegetatio n ([Cd ] = 0.06 9 ppm ) (Va n Hoo k and Yates , 1975) . Cadmiumwa s no t concentrate d i n th e Crooke d Cree k Watershe d litter-litte r faun a foo d chain , althoug h C d
wa s accumulate d t o a greate r degre e tha n P b (Tabl e 24) . Th e rang e o f predato r concentratio n factor s (0.1 0 t o 3.48 ) include d th e valu e calcu

late d fo r Lycosi d spider s preyin g upo n Cd-tagge d Pteronemobiu s (Va n Hoo k an d Yates , 1975) . Afte r 3 0 days ' feeding , Lycos a ha d accumulate d 70 % o f th e tota l C d availabl e i n th e pre ysubstrat e (i.e. , CF . = 0.7 ) (Va n Hoo k an d Yates , 1975) . Th e onl yothe r arthropo d food-chai n dat a availabl e dea l wit h herbivorou s grasshopper s tha t fe d o n Cd-contami

nate d vegetatio n nea r a Montan a Z n smelte r (Munshower , 1972) . Th e overal l grass-herbivor e concentratio n facto r wa s 1.3 . Concentratio n (CF.>1.0 ) o f Cd occurre d amon g th e predato r popula

tion s expose d t o pre ycontainin g <

_ 9 pp mC d ( W 0. 8 and 1. 6 km ; N W 1. 2 km ;- S UPf F>r*irrrvr

" T l

7 6
NE 0. 8 km ; an

d W 21. 0 km) . A t pre y

concentration s exceedin g 9 ppm , ai l predato r concentratio nfactor s < 1 . Diversit y
A nindicato r o f biologica l change s withi nth e Crooke dCree k Water she d fores t floo r communit y i s arthropo ddiversity . Us e o f Equation s 1
and 2 and dat a include d i n Appendi xB produce dth e diversity , evennes s
an d richnes s indice s give ni n Tabl e 28 . Significanc e testin g o f Pielou' s evennes s 'J ' an

d th e Shannon-Weave r Diversit y IndexH ' pointe dou t th e extrem e variabilit y

withi nth e data , an d no consisten t trend s coul db e observe d fo r thes e tw o parameter s (Hutcheson , 1970 ; O'Neil l e t al. , 1976) . However , richness , S , wa s show nt o b e a significan t indicato r o f heav y meta l effect s on Crooke dCree k Watershe darthropo ddiversit y (ANOVA) . Value s o f S (tota l numbe r o f taxa=families) , equivalen t t o H '
ma xan d necessar y

fo r th e computatio no f evennes s 'J * (Equatio n2) , varie d significantl y

wit hdistance , directio nan d distanc e xdirectio n interactio neffect s (P<.01) . Thus , th e richnes s componen t o f tota l arthropo d diversit y

wa s show

nt o b e mor e sensitiv e t o perturbation s on CC W tha neithe r th e evennes s o f abundanc e componen t o r tota l arthropo d diversity .""">" "W y » * T' ' 1M J Ml 1 ' T^ l

7 7 Tabl e 28
Crooke d Cree k Watershe d litte r arthropo d diversit y indice s fo r eac h site , horizo nan

d season . a . Shannon-Weave r Index , H ' (calculate d b y Equatio n#1) . b . Pielou' s evennes s inde xJ ' (calculate d b y Equatio n#2) . c . Richnes s inde xS (tota l numbe r o f families) ."y l


### 78 Shannon-Weave r Inde xH' . Sit e (km ) W 0. 4
W 0. 8
W 1. 2
W 1. 6
N W 0. 4
N W 0. 8
N W 1. 2
N W 2. 0
N E 0. 4
N E 0. 8
N E 1. 2
W 21. 0 (Control ) Ho r

0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 Marc h

197 4 0.69 3 2.08 3 2.47 9 1.70 8 1.90 6 1.76 9 1.35 9 1.38 2 2.94 6 1.55 7 2.15 1 1.88 7 2.21 2 1.99 5 1.55 5 1.37 8 1.09 9 1.12 6 2.02 0 2.596 * 2.09 5 2.518 * 2.17 6 1.62 5 Jun e

197 4 1.19 2 2.12 4 1.93 9 1.768 * 2.19 3 2.47 9 1.98 1 2.36 7 2.23 3 2.15 2 2.56 8 2.78 9 1.42 5 1.917 * 0.99 9 1.339 * 2.15 0 2.29 5 1.81 8 2.34 0 2.00 5 2.37 2 1.76 7 2.47 5 Sept

.

197 4 1.39 6 2.14 3 1.91 1 2.36 7 1.93 9 2.68 4 1.74 5 1.809 * 1.79 0 1.80 1 1.77 9 2.79 0 1.49 4 1.96 7 2.79 7 2.49 1 1.48 6 1.74 7 1.52 4 2.35 6 1.98 8 2.63 3 1.85 2 2.31 6 Jan

.

197 5 2.11 9 2.15 7 1.47 5 1.167 * 2.05 5 1.66 9 1.33 0 1.031 * 1.22 8 1.42 7 1.54 0 2.20 4 1.87 7 1.91 9 2.26 1 2.03 7 0.50 0 1.117 * .62 8 1.76 3 1.73 3 2.13 6 1.93 5 2.06 0 *Significantl y

differen t fro

m th e contro l a t P<.05 .—r> e •^rmryj'W'' • 

# m

b

. Evenness ' J 

### 7 9

Sit e (km ) W 0. 4
W 0. 8

W 1. 2

W 1. 6
N W 0. 4

N W 0. 8

N W 1. 2

N W 2. 0

N E 0. 4

N E 0. 8

N E 1. 2
W 21. 0 (Control ) 

### Ho

r
0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 Marc

h 197 4 1.00 0 .83 8 .87 5 .57 0 .74 3 .53 7 .84 5 .41 9 1.08 6 1.12 3 .81 5 .69 7 .76 5 .65 5 .51 1 .41 8 1.58 5 .82 9 1.03 8 .91 6 1.07 6 .79 2 .82 5 .49 9 Jun

e 197 4 .51 8 .72 2 .73 5 .59 0 .85 5 .77 0 .77 3 .74 5 .93 1 .98 0 .90 7 .94 7 .55 6 .67 7 .45 5 .39 0 1.10 5 .84 7 .79 0 .86 4 .87 1 .75 7 .62 4 .76 9 Sept . 197 4 .71 7 .81 2 .76 9 .83 5 .75 6 .88 2 .62 9 .57 7 .86 1 .72 5 .91 4 .89 0 .48 3 .66 8 1.06 0 .74 7 .76 4 .89 8 .85 1 .87 0 .95 6 .91 1 .77 2 .71 1 Jan .

197 5 .85 3 .89 9 1.06 4 .45 5 .89 3 .56 7 1.21 0 .35 0 1.11 7 .88 7 .95 7 .81 4 .90 3 .69 2 1.02 9 .65 9 .72 2 .41 3 .90 6 .61 0 .96 7 .73 9 1.08 0 .62 5

# 1 80 c . Richnes s Sit e (km ) W 0. 4

W 0. 8

W 1. 2

W 1. 6

N W 0. 4

N W 0. 8

N W 1. 2

N W 2. 0

N E 0. 4

N E 0. 8

N E 1. 2

W 21. 0 

### S .



### Ho r
0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 0 1 0 2 Marc

h 197 4 2 1 2 1 7 2 0 1 3 2 7 5 2 7 6 4 1 4 1 5 1 8 2 1 2 1 2 7 2 1 3 7 1 7 7 2 4 1 4 2 6 Jun

e 197 4 1 0 1 9 1 4 2 0 1 3 2 5 1 5 2 4 1 1 9 1 7 1 9 1 3 1 7 9 3 1 7 1 5 1 0 1 5 1 0 2 3 1 7 2 5 Sept . 197 4 7 1 4 1 2 1 7 1 3 2 1 1 6 2 3 8 1 2 7 2 3 2 2 1 9 1 4 2 8 7 7 6 1 5 8 1 8 1 1 2 6 Jan .

197 5 1 2 1 1 4 1 3 1 0 1 9 3 1 9 3 5 5 1 5 8 1 6 9 2 2 2 1 5 2 1 8 6 1 8 6 2 7GENERAL DISCUSSIO N
Heav y Meta l Effect s on Biot a Measure s o f biologica l activit y in Crooke dCree k Watershe dlitte r horizon s performe ddurin g th e presen t stud y include dlitte r mass ; tota l
andtrophi c leve l arthropo ddensit y an d biomass ; tota l arthropo ddiver sity , evennes s an

d richness ; an

d preliminar y

measurement s o f litte r respiration . Additiona l supportiv e dat a wer e collecte db y E . A . Bondiett i (1976 ) and includ e determination s o f litte r ureas e an d amin o sugar content . Trend s disclose db y analyse s o f thes e dat a indicate d tha t Crooke dCree k Watershe dforest-floo r biot a wer e undergoin g signi fican t change s a s a resul t o f exposur e t o th e heavv-meta i mnrpntratjop s foun d i n +h p "H+tfl r hnriynn v I t had bee ndemonstrate dtha t accumulationsjj f 0 2 litte r occu r a t Crooke dCree k Watershe dsite s tha t ha d receive dlarg e input s o f Pb , Zn , Cu , and Cd . Simila r accumulation s o f undecompose d organi c materia l hav e bee nfoundunde r appl e tree s subjecte dt o heav y application s o f Bordeau xmixtur e (CuSO. ) nea r Rothamsted , beneat hspruce-fi r forest s nea r heavy-meta l industria l activit y i n souther nSweden , an d i n th e oak-litte r horizo nwithi n1 k m o f a Pennsylvani a zincjsmelte r (Hirst , et_al_. , 1961 ; Tyler , 1972 ; Ruhlin g an d Tyler , 1973 ; Strojan , 1975) . Th e fungicida l activit y o f heavy-meta l ion s i s wel l documente d(Somers , 1961 ) and th e lac k o f litte r decompositio ni n th e appl e orchar dwa s directl y attribute dt o coppe r poisonin g o f litter-inhabitin g micro organism s (Hirs t et ^ al_. , 1961) . Decompositio nrate s o f spruc e litter , measure db

y C0 ~ evolution , wer e depresse db y Pb , Zn , Cu , an

d C d concen tration s simila r t o thos e foundon Crooke dCree k Watershe d(Ruhlin g and 8 18 2

Tyler , 1973) . A . simila r depressio no f CO p evolutio nwa s foundi n litte r sample s collecte d alon g on e transec t o f Crooke dCree k Watershe d(Ausmu s
an d Watson , 1975 ) and in Zn-contaminate d litte r collecte dwithi n6 k m o f th e sourc e (Strojan , 1975) . Thes e result s al l indicate da negativ e relationshi p t O exis t betwee n lit+p rHPf-nrnpn<Htin n .in H Titto ^ ho.-iv y meta l content , regardles s o f th e geographica l locatio no f th e study
area . Furthe r documentatio no f a heav y meta l effec t on litte r decomposi tio nwa s provide d b

y analysi s o f litte r amin o suga r an d ureas e conten t (Bondietti , 1976) . Amin o sugar s i n litte r primaril y exis t a s chitin , whic hi s resistan t t o degradatio nan d i s no t synthesize db y gree nplants . Thus , analysi s o f amin o sugar s i s a specifi c tes t fo r th e historica l presenc e o f decompose r organism s (fung i an d arthropods) . Th e result s o f thi s tes t o

n Crooke d Cree k Watershe d litte r indicate da marke ddecreas e i namin o sugar s occurre d t o a distanc e o f 0. 8 k m fro m th e stack . Ureas e enzyme activit y in litte r wa s measure dt o furthe r indicat e los s o f biologica l activit y o n th e watershed . Thi s tes t i s mor e sensi tiv e tha nth e amin o suga r assa y sinc e th e productio no f ureas e enzym e i s adversel y

influence d b

y heav y meta l contamination . Laborator y experi ment s on uncontaminate d litte r showe d tha t th e additio no f 10,00 0 pp m P b
o r 80 0 pp

m Z n cause d a 15 % reductio ni n ureas e enzym e activity . Bot h meta l concentration s and enzyme activit y i n thes e laborator y studie s wer e muc hhighe r tha nthos e foundo n th e watershed . Thus , i t wa s con clude d tha t th e greate r observe d los s o f enzyme activit y on th e watershe d
wa s no t simpl e inhibitio nbu t ma y b e partiall y

du e t o a depressio nin microbia l activity . A reductio no f enzyme activit y wa s foundt o occu r t o a distanc e o f 2. 0 k m fro m th e smelter , whic hwa s furthe r tha nth eP.9 9



### 83
observe deffec t o

namin o sugars . Thi s ma y indicat e tha t th e 2. 0 k m sit e i s presentl y

bein g slightl y

affecte db

y th e heav

y meta l emissions . Th e observe ddeclin e infunga l andbacteria l activit y woul db e reflecte dinarthropo dcommunit y dynamic s becaus e o f reduce dsubstrat e quality . A

depressio ni nth e funga l population s require dt o maintai n fungivore s andthei r predator s ca nb e expecte dt o resul t i na reductio n
o f densit y

an dbiomas s fo r thes e tw o arthropo dgroups . A paralle l declin e ma y

b e observe dincoprophagou s population s dependen t upo n microbia l enrichmen t o f thei r egeste dlitte r substrat e (McBrayer , 1973 ; Wieser , 1966) . Depresse dvalue s o f densit y an dbiomas s inpredator , detritivore , an

dfungivor e population s occurre da t heavil y contaminate d site s regardles s o f distanc e fro m th e smelte r (Table s 14-16) . Reduce d fungivor e an

ddetritivor e population s wer e probabl y du e t o lac k o f suitabl e substrat e - - few mycelia l mat s o r fruitin g bodie s wer e observe d durin g fiel dsamplin g a t th e affecte dplot s anddetritu s productio n appeare dt o b e negligible . A simila r reductio ni ndensit y

o f micro - an

d macroarthropod s o f litte r an dsoi l wa s observe da t study area s locate d1
and6 k m upwin dfro

m a Pennsylvani a zin c smelte r (Strojan , 1972) . Stroja nattribute dth e populatio ndeclin e t o th e presenc e o f heavy-meta l smelte r emission s (Zn , Cd , Cu , Pb , an dFe ) inforest-floo r organi c horizons . Sulfu r dioxid e emission s wer e discounte da s causativ e factor s du e t o th e neutralizin g influenc e o f ZnO (norma l litte r p H fo r thi s are a i s 4. 0 t o 5.0 , litte r a t th e 1 k m sit e wa s p

H 6.1 ) an

dth e efficienc y

o f th e smelter' s aci dplan t (Strojan , 1972) . Th e spars e predato r popula tion s observe da t heavil y contaminate dsite s o nCrooke dCree k Watershe d
ma y b e du e t o th e lac k o f suitabl e pre y o r th e result s o f toxicit y du ep. 1

8 4
t o biomagnification . Bot hhypothese s ar e supporte db y th e dat a (Table s 1 6 and24-27) . Th e occurrenc e o f measurabl e disruption s i npopulatio ndensit y an d biomas s suggeste dtha t a correspondin g disruptio ncoul db e occurring in arthropo dpopulatio ndiversity . I t wa s though t tha t suc ha measur e woul dgiv e some insigh t int o th e stabilit y o f th e Crooke dCree k Water she dlitte r system . Calculatio nan dsubsequen t statistica l testin g o f a Shannon-Weave r inde xapplie dt o eac hsit e indicate dlittl e chang e in arthropo ddiversit y

onCrooke dCree k Watershed , regardles s o f litte r heav y meta l loado r seaso n(Tabl e 28a ) (Shannon , 1948 ; Hutcheson , 1970) . Whe nsegregate dint o it s tw o component s o f richnes s an devennes s o f abundanc e (Pielou , 1966 ; Price , 1975) , diversit y o nth e watershe dwa s show nt o b e governe db

y aneve npopulatio ndistributio n(Tabl e 28b) . I n contrast , th e richnes s componen t wa s show nt o b e a sensitiv e indicato r
o f th e effect s du e t o distanc e anddirectio n(Tabl e 28c) . System para meter s o f 0 2 litte r mas s (Figs . 5 an d6 ) an dmacronutrien t pool s (Fig . 13 ) hav e already

demonstrate dtha t disruption s i necosystem integrit y ar e occurrin g onCrooke dCree k Watershed . Th e inabilit y o f th e Shannon Weave r inde xprocedur e t o detec t simila r disruption s onth e populatio n leve l reveale da seriou s lac k o f sensitivit y o f thi s metho dt o ecosystem leve l perturbations . Concentratio nfacto r dat a indicate dtha t neithe r Pb , Zn , Cu , o r C dar e presentl y

bein g concentrate dinth e litter-litte r feede r food chai nonCrooke dCree k Watershe d(Table s 24-27) . Althoug hleadwa s th e mos t abundan t heavy-meta l elemen t foun donth e watershed , i t wa s accumu late di nth e litte r faun a t o a muc hsmalle r exten t tha neithe r Zn , Cu ,P. 2



### 8 5
o r Cd . Thi s phenomeno nma y be du e t o difference s ininsec t physiolo gica l respons e t o eac helement . Coppe r i s a componen t o f th e arthropo dbloo dprotei nhemocyanin , whic hca nb e foundi nmos t insect s andisopod s an di nsome amphipo d anddecapo dspecie s (Wieser , 1961 , 1965 ; Wigglesworth , 1965) . Marin e arthropod s ar e bathe di ncopper-containin g medi a an dd o no t posses s well-develope dmechanism s fo r storag e an dmaintenanc e o f Cureserve s (Wieser , 1965) . I

ncontrast , terrestria l specie s mus t dependupo n thei r substrat e t o fulfil l thei r C urequirements . On e purpos e o f coprophag y

i nisopod s i s though t t o be maintenanc e o f a critica l Cu concentratio ni nthei r substrate , whic hhadbee npreviousl y though t t o consis t entirel y

o f Cu-poo r litte r (Wieser , 1966) . Th e greate r varia tio nan dlarge r value s o f C

uconcentratio nfactor s betwee nlitte r fauna : litte r foundo nCrooke dCree k Watershe drelativ e t o thos e fo r Pbma y be reflectin g th e variabilit y i nCurequirement s o f th e faun a (Tabl e 26) . Zin c i s require dbot ha s a mediato r an da s a constituen t o f enzym e reaction s (Orten , 1966) . Physiologica l requirement s fo r Z nb y th e Crooke dCree k Watershe dlitte r faun a appeare dt o be reflecte di nth e

m 

### litte r fauna:!itte r concentratio nfactors , particularl y whe ncompare d ;•• . t o th e muc hsmalle r value s calculate dfo r Pb(Table s 2 4 an d25) . Availabl e literatur e doe s no t documen t arthropo dphysiologica l require - '*-• ment s fo r Cd . Othe r tha ndisplayin g greate r accumulatio no f C drelativ e I t o Pb , th e significanc e o f C dconcentratio nfactor s fo r litte r fauna : litte r i nTabl e 2 7 i s no t known . Leadi s no t know nt o b e necessar y

fo r i plan t o r anima l growt han ddevelopment . t 

### Excep t fo r Cu , i t ha s no t bee npossibl e t o substantiat e a simila r

foo dchai ndilutio no f heav y metal s fro

m prey t o predato r onCrooke dP. 3

8 6
Cree k Watershed . Concentratio nfacto r dat a indicate dthat , inrelat i 

### o n t o thei r prey , arthropo dpredator s ma y b e eithe r concentratin g o r equi libratin g wit hrespec t t o Pb , Zn , andCd . Cadmiu m i s o f specia l inter est , fo r possibl e biomagnificatio noccurre donl y i nthos e predato r population s expose dt o pre y containin g £ 9 pp

m Cd . A t pre y

level s greate r tha n9 ppm , al l predato r concentratio nfactor s wer e les s tha n1 . Whil e cadmiu

m ca ndisplac e Z ni nenzym e reactions , i t i s no t physiolo gicall y require db

y arthropod s (Underwood , 1971) . I t i s possibl e tha t hig hlevel s o f pre y

C dma y b e toxi c t o thei r arthropo dpredators . I f th e letha l dos e t o spider s andothe r predator s i s greate r tha nth e
amoun t o f biologicall y availabl e C

di npre y

containin g 9 pp

m tota l Cd , the ndeat hwoul dresul t befor e biomagnificatio ncoul doccur . Minera l Cyclin g Remineralizatio no f nutrien t ion s inlitte r i s a norma l componen t
o f th e minera l cyclin g processe s o f deciduou s forest s (Ovington , 1960) . Earlie r discussio nha s pointe dou t th e rol e o f arthropod s indecomposi tion . I t ha s bee nsuggeste dtha t disruptio no f couple darthropo dand microorganis m

lif e cycle s b

y heav y meta l toxicit y

ma y completel y

dis rup t fores t minera l cyclin g (Tyler , 1972 ; Witkam pandAusmus , 1975 ; Ausmu s e_

t aj_. , 1975 ; Jackso nan dWatson , 1976) . Tyle r hypothesize s tha t suc htoxicit y

woul dfirs t resul t i na nincreas e i nth e amoun t o f incompletel y

decompose dlitte r materia l o nth e fores t floor . Reduce d decompositio nrate s woul dallow minera l nutrient s t o remai nboundi n a for m unavailabl e fo r plan t uptak e an dma y resul t ina neventua l pro ductivit y

decline .P. 4

8 7 Th e firs t stag e o f Tyler' s hypothesi s ha s bee nsubstantiate db y Crooke dCree k Watershe ddat a - - 0 2 litte r accumulation s hav e already occurre da t a numbe r o f site s (Figs . 5-6 , Appendi xC) . Th e subsequen t declin e i

nnutrien t availabilit y suggeste db

y Tyle r wa s corroborate db y preliminar y

measurement s o f fres hsumme r leave s collecte dfro m Crooke d Cree k Watershe dblac k an dwhit e oa k (Tabl e 12) . Foliag e concentration s
o f Ca , K , an

dP wer e significantl y reduce dwhe ncompared.t o th e contro l onl y a t th e sit e wit hth e greates t heav y meta l loa dandlitte r accumu lation . Thes e dat a sugges t a reductio ninroo t uptake . Durin g litte r sampling , i t wa s observe dtha t secondar y root s o f tree s di dno t occu r withi nan dbeneat hth e 0 2 litte r horizo na t site s
nea r th e smelter . A t th e contro l sites , considerabl e difficult y wa s involve di nseparatin g litte r materia l fro m th e thic k ma t o f fin e root s growin g throughou t th e 0 2 horizon . Greenhous e po t experiment s utilizin g health

y blac k oa k seedling s transplante dt o Crooke dCree k Watershe dsoi l verifie dth e field-observe deffect s onlatera l roo t growt h(Jackso nan

dWatson , 1976) . Furthe r indication s o f a disruptio ni nnutrien t cyclin g mechanism s
ar e th e change s i ncatio nexchang e capacit y an dp H fro m th e norma l stat e (Tabl e 11) . Th e declin e i ntota l litte r catio nexchang e capacit y onCrooke dCree k Watershed(coul d lead^t o a reduce dcapacit y o f litte r t o hol dnutrien t cations , resultin g i nleachin g losses . Thus , afte r initia l nutrien t bindin g du e t o reduce dremineralizatior r (cf . Tabl e 1 3 - Ca andM g pool s a t 1. 2 an

d2. 0 km , Kpoo l 0.8 , 1.2 , an d2. 0 km) , nutri ent s ma y b e los t entirel y

fro m th e system

(cf . Tabl e 1 3 - Ca poo l a t 0. 4 and0. 8 km) . Thi s effec t goe s beyondth e two-stag e hypothesi s o f Tyle r (1972) , wher e primar y production , limite db y th e lac k o f essentia l

JUJBMU "P. 5

8 8 nutrient s bound up i nundecomposin g litter , declines . Phosphoru s ma y

become tenaciousl y

bound inorgani c materia l an d thu s doe s no t behav e i nth e same manne r a s divalen t macronutrien t cations . Th e P poo l a t 0. 4 k m wa s no t differen t fro m tha t o f th e con tro l (Tabl e 13) , bu t th e P conten t o f fres hfoliag e a t th e same sit e
wa s significantl y

reduce d fro

m tha t o f th e control . Th e capacit y o f P t o bin d t o organi c materia l ma y be responsibl e fo r foliag e P depletion . Ingeneral , forest^nutrien t dynamic s o nCrooke dCree k Watershe dar e displayin g significan t sign s o f perturbatio n- excessiv e roo t mortality , depletedniiaTronutrien t concentration s i nfres hfoliage , a declin e i n catio nexchang e capacit y an d litte r Ca pool s nea r th e smelter , andan accumulatio no f litte r M g andKbetwee n0. 8 and2. 0 k m o f th e smelter . A majo r disruptio ni nnutrien t resourc e allocatio ndu e t o heav y meta l effect s onlitte r decompositio nwa s indicated . Eventually , i t canb e expecte d tha t productivit y wil l b e mos t depresse di ntree s whic har e no t toleran t o f heav

y metal s o r a reduce d suppl y o f availabl e nutrients . I t i s no t unrealisti c t o envisio nwidesprea d deforestatio no f non-toleran t specie s ove r anare a adjoinin g th e smelter , i f th e smelte r emission s continu e a t th e presen t leve l fo r a numbe r o f years . I t ca nb e furthe r hypothesize d tha t th e are a affecte db y th e smelte r ma y

b e increasin g insiz e du e t o th e continua l loadin g o f heav y meta l particulate s o nth e watershed . Th e are a 1. 2 - 2. 0 k m from th e stac k coul d eventuall y be affecte d t o th e sam e degre e a s th e exist ing are a withi n0. 8 k m fro m th e stack .^ TH ' • - *i ? P. 6

SUMMAR YAND CONCLUSION S

A numbe r o f measure s o f biologica l activit y withi nth e Crooke d Cree k Watershe dlitte r system hav e bee nmade . Studie s hav e focuse d
onth e litter-arthropo d foo dchai na s a mean s o f detectin g perturba tion s ina heavy-meta l contaminate dterrestria l ecosystem . T o ade quatel y characteriz e th e arthropo dfoodbas e an dhabitat , litte r mass , heav y meta l content , catio nexchang e capacity , pH , ureas e activity , andamin o suga r conten t wer e criticall y examined . Litte r horizon s on th e watershe dca nb e characterize d a s follows : 1 ) 0 1 litte r mas s ha s no t differe dthroughou t th e watershe d durin g th e perio do f study , bu t varie dabou t a mea no f 43 3 + 2 9 (SE ) g/m 2 . Mea nannua l 0 1 mas s a t .th e contro l sit e varie dabou t a mea no f 47 1 +

_3 4 (SE ) g/m 2 . 2 ) A naccumulatio no f undecompose d 0 2 litte r onCC W wa s positivel y

correlate dwit hlitte r heavy-meta l conten t (P<.01) . 3 ) Th e highes t concentration s o f litte r Pb , Zn , Cu , an dC d occurre di n0 2 litter . Th e mea nannua l rang e o f value s fo r heav y metal s (ppm ) onth e watershe dwer e 460 0 t o 103000 , 23 0 t o 4910 , 8 0 t o 6080 , an d1 4 t o 17 9 fo r Pb , Zn , Cu , an dCd , respectively . Althoug hlitte r graduall y became enriche di nZn , Cu , an dC drelativ e t o P ba s distanc e fro m th e smelte r increased , th e rank order o f concentra lion-parallele d tha t displaye db y stac k emissions , i.e. , Pb>Zn>Cu>Cd . 4 ) Measurement s o f 0 2 litte r ureas e activity , amin o sugar conten t (Bondietti , 19/b) , an dLO 2 evolutionreveale d a depressio no f norma l decompose r activit y i nIrtte r collecte dnea r heav

y meta l sources" !
Fro m thes e data , i t appeare dtha t annua l productio no f fres h litte r o nCrooke dCree k Watershed , a s estimate db y forest-floo r 0 1 litte r mass , hadno t ye t bee nadversel y affecte db

y exposur e t o smelte r emissions . Incontrast , significan t 0 2 litte r accumulation s hav e


### 8 9



## mmm

### 9 0 £7 ' "I T

occurreda s a resul t o f reduce ddecomposition . Bot hhistorica l an d
curren t microbia l activit y (measure db

y amin o suga r analysi s an dC0 2 evolution ) hav e bee ndepresse d a t site s locate dnea r th e AMA Xsmelter , th e primar y

heav y meta l sourc e o

nCCW . Sinc e litte r arthropod s ac t
a s "catalyst s o f microbia l metabolism" , i ndecompositio nprocesse s b y substrat e alteratio nan d inoculation , an

y gros s change s i nlitte r decompositio nshoul d b e reflecte d i nth e dynamic s o f th e arthropo d communit y

(Macfadyen , 1963) . Documente d effect s o nth e CC W litte r arthropo d population s wer e a s follows : 1 ) Whe ncompare d t o th e contro l site , reduce dvalue s ofLtota l
_ _ arthropo d biomas s (m g dry wt/m 2 ) an

ddensit y

(no./m 2 ) occurre d simultaneousl y

wit helevate d levels"O f Utte r heav y metals . 2 ) Thi s reductio ni ntota l arthropo d biomas s an ddensit y

wa s governe d b

y a decreas e i

nbiomas s an

ddensit y

o f th e predator , detritivor e an d fungivor e populations . 3 ) Measurement s o f arthropo d richness , anestimat e o f maximu m diversity , reveale d tha t litte r arthropo dpopulation s a t heavil y contaminate d site s wer e les s ric hintaxa (family ) tha nwer e thos e locate d elsewher e onth e watershed . Thes e effect s ma y

b e induce db

y change s i

nsubstrat e qualit y

o r actua l heav y meta l toxicity . Th e latte r hypothesi s wa s supporte db y analytica l result s o f heav

y meta l concentration s foundassociate dwit harthropo d trophi c levels . Food-chai ndilutio no f Pb , Zn , Cu , an d C dfro m litte r t o litte r consume r occurre d a s indicate d b y the mea nconcentratio no f 0. 7 +

_0.0 2 (SE ) (Pb) , 0.6 4 + 0.1 5 (SE ) (Zn) , 0.3 8 + 0.1 0 (SE ) (Cu) , an d0.3 4 + 0.0 5 (S E (Cd) . Biotransfe r o f P bt o litte r consumer s wa s muc hles s tha n tha t found fo r th e othe r thre e heav y metals . Incontrast , predator y arthropod s o nCrooke d Cree k Watershe dwer e eithe r concentratin g o r equilibratin g Pb , Zn , and Cd fro m thei r prey , a s indicate db y mea n.