The impacts of trace metals on grass communities along the floodplains of Soda Butte Creek, Montana and Wyoming by Julie Ann Stoughton A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Earth Sciences Montana State University © Copyright by Julie Ann Stoughton (1995) Abstract: Existing research documents that high levels of copper and other, trace metals can be toxic to plants, but little has been written about the spatial extent of ecosystem disturbance due to trace metal deposition. Outside of Yellowstone National Park, in Montana and Wyoming, tailings from an old mine have been deposited downstream by large flood events. Elevated levels of trace metals from the displaced tailings have been identified 25 km downstream (Meyer, 1993). This study evaluates whether grass species diversity, density, and biomass: (1) decrease as trace metal concentrations increase; and (2) decrease as soil pH decreases. In order to assess the role of environmental variables unrelated to mine tailings, the study also evaluated whether grass species diversity, density, and biomass: (1) vary with soil clay content and salinity; (2) vary as a function of distance from the stream channel or elevation above the. channel; or (3) change in the downstream direction. Trace metal levels frequently exceed Maximum Acceptable Concentrations for agricultural soils (Kabata-Pendias and Pendias, 1992) at points within all four meadows sampled along Soda Butte Creek. pH levels in the four sites mark the presence of strongly acid and moderately acid soils, with values as low as pH 3.4. Results from four meadow sites along Soda Butte Creek indicate that vegetation diversity, density, and biomass decrease at threshold levels of trace metals and soil pH. CuSum plots of diversity in relation to trace metal levels show a decrease in mean diversity at 3I5ppm copper, 22ppm arsenic, 4.2% iron, 65ppm lead, and 17Oppm zinc. Densities of Phleum pratense and Poa pratensis were significantly lower (p<=0.001) on plots with more than 25Oppm copper. Above-ground biomass of Phleum pratense was also significantly lower on plots with copper levels above 250ppm. Decreased mean grass density was found on plots with pH<6.4, but the only statistically significant difference was for Juncus balticus. which had increased density on plots with pH<6.4. In contrast to the clear impacts of trace metals and pH on vegetation, factors such as soil salinity, soil clay content, site elevation above stream and distance from stream did not alter vegetation patterns. THE IMPACTS OF TRACE METALS ON GRASS COMMUNITIES ALONG THE FLOODPLAINS OF SODA BUTTE CREEK, MONTANA AND WYOMING by Julie A nn S to u g h to n A thesis su b m itte d in p a rtia l fu lfillm en t o f th e re q u ire m e n ts fo r th e degree of M aster o f Science in E arth Sciences MONTANA STATE UNIVERSITY Bozeman, M o n tan a D ecem ber 1995 ii APPROVAL of a thesis su b m itted by Julie A nn S toughton This thesis h as been re a d by each m em b er o f th e thesis co m m ittee a n d h as b een fo u n d to be satisfacto ry re g a rd in g c o n ten t, English usage, f o r m a t, citations, b ib lio g rap h ic style, a n d consistency, a n d is re a d y fo r subm ission to the College of G raduate Studies. / Date 0 . C h airp erso n , G rad u ate Com m ittee A pproved fo r th e M ajor D ep artm en t r- Date z - W M Head, M ajor D ep artm en t A pproved fo r the College of G raduate Dean tu d ies iii STATEMENT OF PERMISSION TO USE In p re s e n tin g th is th esis in p a rtia l fu lfillm en t o f th e re q u ire m e n ts fo r a m a ste r's d eg ree a t M o n tan a S tate U niversity, I ag ree th a t th e L ibrary sh all m ake it available to b o rro w ers u n d e r ru le s o f th e Library. If I h a v e in d ic a te d m y in te n tio n to co p y rig h t th is th esis b y in clu d in g a c o p y rig h t n o tic e p a g e, c o p y in g is allo w ab le o n ly fo r sc h o la rly p u rp o se s, c o n siste n t w ith "fair use" as p re s c rib e d in th e U.S. C o p y rig h t Law. R equests fo r p e rm issio n fo r e x te n d e d q u o ta tio n fro m o r re p ro d u c tio n o f this thesis in w hole o r in p a rts m ay b e g ra n te d o n ly b y th e co p y rig h t h o ld e r. Signature Date /nXtX '3 r •( Wff-y---- ---------- V /ffO ___________ ACKNOWLEDGEMENTS I o ffe r h e a r tfe lt th a n k s to m y a d v iso r. D r. A n d rew M arcus, w ho h a s b e e n a m e n to r in th e fu lle s t sense. I w ill re m e m b e r h im fo r his lo v e o f g e o g ra p h y , h is c o m m itm e n t to h e lp in g m e le a rn a n d g ro w th ro u g h o u t m y m a ste r's p ro ject, his p ro fessio n al skills a n d w isdom , a n d th e jo y a n d h u m o r h e b ro u g h t to all situations. I am also in d e b te d to m y o th e r com m ittee m e m b e rs, in c lu d in g D r. K athy H ansen, w ho firs t w elcom ed m e in to th e D e p a rtm e n t of E arth Sciences a n d in s p ire d m e to becom e a g eo g rap h er; D r. R obin Patten, fo r h e r ad v ice in th e field a n d ecological in sig h ts; a n d Dr. Bill Q uim by, fo r h is statistical assistance a n d su p p o rt. S e v e ra l o rg a n iz a tio n s p r o v id e d fin a n c ia l s u p p o rt fo r th is p ro je c t, in c lu d in g th e M o u n tain R esearch C en ter a t M o n tan a S ta te U n iv ersity , th e C in n a b ar F o u n d atio n , Yellow stone Ecosystem Studies, a n d th e D e p a rtm e n t o f E arth Sciences. I a p p re c ia te th e ir in v e stm e n t in this im p o rta n t research . In th e s p irit o f in te rd is c ip lin a ry re s e a rc h , I s o u g h t th e w isd o m o f n u m e ro u s facu lty a n d g ra d u a te stu d en ts. I w ould p a rtic u la rly like to th a n k Dr. R obin T iern ey , D r. Steve C herry, Dr. Jo n W raith, D r. Bill Inskeep, Dr. M att Lavin, Clain Jones, C had M oore, a n d Ian Godwin. Scott Ladd, W endi Urie, D enise C ulver, a n d G ary M ilner o ffe re d in v a lu a b le assistan ce in th e field a n d th e classroom , n o t to m e n tio n comic relief. I also ,am th an k fu l fo r th e h elp o f m y field a n d la b crew, in clu d in g Joe, Pam, C indy, M elinda, Erin, Jo n ath o n , Amy, Chris, M ark, Leslie, a n d Sam. . Finally, I o ffe r a sp ecial th a n k y o u to D an K ind, K aren A llen, Jo h n M cConnell, a n d C arol K uester fo r believing in m e, a n d to m y fam ily fo r th e ir lifetim e love a n d su p p o rt. vi TABLE OF CONTENTS Page I. RESEARCH OBJECTIVES AND SIGNIFICANCE..........................................................I R esearch Q u e stio n s............................... L ite ra tu re R eview ................................. B ioavailability o f T race m etals pH a n d Redox Potential..... Clay M in e ra ls ...................... O rganic M a tte r.................... P lant U ptake o f Trace M etals.... H eavy M etal Toxicity in Plants Toxicity o f Specific E lem e n ts........... ........................................................10 C opper................................................ 11 L ead....................................................................................... 11 Z in c ........................................................................... 12 I r o n .............................................................. 13 A rs e n ic ..:................................................................................................13 G rass Species C haracteristics a n d Responses to Trace M etals.....................................................................................14 R elated Studies in th e Cooke City A re a ................................................... 14 2. FIELD AREA AND METHODS................................... ................................... ,.............. 17 Field A re a .................................................................................................................. 17 H abitat T ypes.................................................................................................. 17 Study S ites.................................... ................................................................ 21 G eneral Clim ate C h ara c te ristic s.......................... 24 H istoric M ining Practices............................................................................ 26 C hm ate Events arid Tailings T ra n sp o rt.................................................. 27 M ethods...................................................................................................................... 28 F ie ld w o rk ........................................................................................................29 Soil A n aly sis...................................................................................................32 3. DATA................................................................................................................................. 34 Soil S am ples.................................................................................. 34 Study S ites................................................................................................................. 35 Fish M eadow ...;...............................................................................................35 v ii TABLE OF CONTENTS - Continued Hollywood M eadow ....................................................................................... 38 Icebox M eadow ............................................................. ;.............................. .38 R ound P rairie.................................................................................................. 39 4. DATA ANALYSIS.............................................................................. '........................... 40 R elationship o f T race M etals a n d V e g e ta tio n .............................................. 41 D iversity........................................................................................................... 42 D ensity.............................................................................................................. 45 B iom ass........................................ 49 R elationship o f Soil C haracteristics a n d V eg etatio n ................. 50 pH ............................... 50 D iversity.......................................................... 50 D ensity.......... ..........................;..............................................................50 B iom ass...................................................................................................55 S a lin ity ........................ 55 P ercent Clays...................................................................................................57 M u ltiv ariate A n a ly sis..................................................................................... .....58 D istance fro m a n d Elevation above S tre a m ...................................................59 D ow nstream V a ria tio n s........................... 64 5. SUMMARY AND CONCLUSIONS........................................................................ 66 S u m m a ry ................................................................................................................... 66 D iscu ssio n ................................................................................................................. 68 F u tu re R e s e a rc h ..................................................................................................... 71 R e c o m m e n d a tio n s..................................................................................................73 REFERENCES........................ 75 APPENDIX................................... 84 Key to Colum n H eadings..................................................... 85 Key to Colum n N u m b ers................................ 86 D ata T able.................................................................................................................. 88 v iii LIST OF TABLES Table P ag e 1. N o rth e a st E ntrance Station: T e m p e ra tu re a n d p re c ip ita tio n fo r Ju n e, July, a n d A ugust...................................................................................26 2. C om parison of m eans, s ta n d a rd deviations, a n d ran g es a t O-IOcm a n d 10-20cm d e p th s o f tra c e m etals in fo u r m eadow s along Soda Butte C re e k ......................................................................................... 34 3. M ean, s ta n d a rd d eviation, a n d ra n g e o f vegetation, soil (O-IOcm), a n d m e tal v ariab les in Fish Meadow, Hollywood M eadow, Icebox M eadow, a n d R ound Prairie along Soda Butte Creek, MT a n d WY..................................................................................................37 4. T race m etal c o n cen tratio n s along Soda Butte Creek, MT a n d WY in re la tio n to suggested m axim um tra c e m etal lev els............................... 41 5. K ruskal W allis co m p ariso n of m e an species d en sity on plots w ith hig h (Cu>250ppm ) a n d low (Cu<250ppm) levels o f copper, fo r all grasses a n d fo rb s in c lu d e d in th e M argalef D iversity I n d e x ....................................................................................................... 46 6. K ruskal W allis com parison o f m e an species d en sity o n plots w ith h ig h (pH>6.4) a n d low (pH<6.4) pH levels, fo r all grasses a n d fo rbs in c lu d e d in th e M argalef D iversity Index....,............................ 54 7. R esults of logistic re g re ssio n an aly sis fo r fo u r grass species 59 ix LIST OF FIGURES F ig u re P ag e 1. M ap o f stu d y a re a a n d Yellowstone re g io n ................................................... 18 2. M ap o f m eadow stu d y sites along Soda Butte Creek, MT a n d WY............. 19 3. Photo of Fish M eadow ............................................................................................22 4. Photo o f H ollywood M eadow ................................................................................22 5. Photo of Icebox M eadow ........................................................................................23 6. Photo of R ound P rairie........................................................................................... 23 7. N o rth e a st e n tra n c e sta tio n c lim o g ra p h ......................................................... 25 8. V ariatio n in m e an d e n sity levels o f P h leu m n ra te n s e along a sam ple tra n se c t............................................................ 9. Box plots o f As, Cu, Fe, Pb, a n d Zn a t stu d y sites along Soda Butte Creek, MT a n d WY........................................................................................ 36 10. S catter p lo t o f DMg (M argalef s D iversity Index) a n d c o p p er levels w ith a n o v erlay of sm o o th ed d a ta p o in ts a n d CuSum p lo t o f cum ulative d ev iatio n fro m m ean d iv e rsity (DMg) in re la tio n to c o p p er levels along Soda Butte C reek..................................................................................................... 43 11. CuSum plots o f th e cum ulative d ev iatio n from m ean d iv ersity (DMg) in re la tio n to arsenic, iro n , lead, a n d zinc levels as calculated fo r Fish M eadow, Hollywood Meadow, a n d Icebox M eadow .............................................................. ;............................... 44 12. S catter p lo t of co p p er levels in re la tio n to d en sity o f P h leu m p ra te n se a n d Poa n ra te n sis along Soda Butte C re e k .................................. 47 13. CuSum plots o f cum ulative deviations fro m th e m ean d en sity in re la tio n to c o p p er levels fo r P h le u m p ra te n s e a n d Poa p r a te n s is ............................. ....................................................................48 14. S catter p lo t o f ab o v e-g ro u n d biom ass of P hleum p ra te n s e in re la tio n to c o p p er levels along Soda Butte C reek..................................49 J X LIST OF FIGURES - C ontinued 15. S catter p lo t o f M arg alefs D iversity Index (DMg) a n d pH levels, w ith a n overlay o f sm o o th ed diversity d a ta a n d CuSum p lo t of th e cum ulative d ev iatio n from m ean d iv ersity (DMg) h i re la tio n to soil pH fo r th e com bined d a ta from Fish^ Hollywood, a n d Icebox M eadow s........................................ 5V 16. S catter p lo t o f pH in re la tio n to d e n sity o f Poa p ra te n sis along Soda Butte Creek................................. :.................................................................. 52 17. CuSum p lots o f cum ulative d ev iatio n s fro m m ean d e n sity in re la tio n to pH levels fo r two grass sp ecies................................................... 53 18. S catter p lo t o f a b o v e-g ro u n d biom ass o f P hleum n ra te n s e in re la tio n to pH levels along Soda Butte Creek...........................................55 19. CuSum p lo t o f th e cum ulative d ev iatio n s fro m m ean d iv ersity (DMg) h i re la tio n to salinity, a n d scatter p lo t o f P h le u m n ra te n s e d e n sity in re la tio n to s a lin ity ........................................ 56 20. CuSum p lo t o f th e cum ulative d ev iatio n s fro m m ean d iv ersity (DMg) in re la tio n to p e rc e n t c la y ............... :................................. 57 21. S catter p lo t o f P h leu m p ra te n s e d e n sity in re la tio n to p e rc e n t clays............................................................................................................. 58 22. O verlay of changes in c o p p er levels relativ e to ch an g es in d iv e rsity (DMg) along tra n sec ts in th re e m eadow s.....................................61 23. S catter p lots o f M arg alefs D iversity Index (DMg) in re la tio n to d istan ce fro m stre am c h an n e l a n d elev atio n o f sam ple . p o in t above stre a m C h an n el.............................................................................. 62 24. C o n cen tratio n o f c o p p er in re la tio n to d istan ce fro m stre am c h an n e l a n d e lev a tio n of sam ple p o in t above stre am c h a n n e l............ 63 25. Box p lo t o f M arg alefs D iversity Index (DMg) fo r Fish, Hollywood, a n d Icebox M eadow s........................................................................65 xi ABSTRACT Existing re s e a rc h d o c u m en ts th a t h ig h levels o f c o p p e r a n d other, tra c e m etals can b e toxic to p lan ts, b u t little h a s b e e n w ritten a b o u t th e spatial e x te n t of ecosystem d istu rb a n c e d u e to trace m e ta l deposition. O utside o f Yellowstone N ational Park, in M o n tan a a n d W yom ing, tailings fro m a n o ld m in e hav e b e e n d e p o site d d o w n stre am b y la rg e flo o d ev en ts. Elevated levels o f tra c e m e ta ls fro m th e d isp la ce d tailings h a v e b e en id e n tifie d 25 km d o w n stream (M ey er, 1993). T his s tu d y e v a lu a te s w h e th e r g ra ss sp ecies d iv e rs ity , d e n sity , a n d biom ass: (I) d ecrea se as tra c e m etal c o n ce n tra tio n s in crease; a n d (2) d ecrease as soil pH d ecreases. In o rd e r to assess th e ro le o f e n v iro n m e n ta l v a ria b le s u n re la te d to m in e tailin g s, th e s tu d y also e v a lu a te d w h e th e r g rass sp ec ie s diversity, d ensity, a n d biom ass: (I) v a ry w ith soil clay c o n te n t a n d salinity; (2) v a ry as a fu n c tio n o f d istan ce fro m th e stre a m c h an n e l o r elev atio n above t h e . chan n el; o r (3) ch an g e in th e d o w n stream d irectio n . T race m etal levels fre q u e n tly exceed M axim um A cceptable C o n cen tratio n s fo r a g ric u ltu ra l soils (K abata-P endias a n d Pendias, 1992) a t p o in ts w ith in all fo u r m eadow s sam pled along Soda Butte Creek. pH levels in th e fo u r sites m a rk th e p re sen c e o f stro n g ly a cid a n d m o d e ra te ly acid soils, w ith values as low as pH 3.4. R esults fro m fo u r m ead o w sites along Soda B utte C reek in d ic a te th a t v e g eta tio n diversity, d ensity, a n d biom ass d ecrease a t th re s h o ld levels o f tra c e m etals a n d soil pH. CuSum plots o f d iv e rsity in re la tio n to tra c e m etal levels show a d ecrea se in m e an d iv e rsity a t 3 IS p p m co p p er, 2 2 p p m arsen ic, 4.2% iro n , 65p p m le ad , a n d 17Oppm zinc. D ensities o f P h le u m p r a te n s e a n d P o a n ra te n sis w ere significantly low er (p<=0.001) o n plots w ith m o re th a n 25Oppm c o p p er. A b o v e -g ro u n d b io m ass o f P h le u m p r a te n s e w as a lso sig n ific a n tly low er o n plots w ith c o p p er levels above 250ppm . D ecreased m e a n grass d e n sity was fo u n d on plots w ith pH<6.4, b u t th e o n ly statistically sig n ifican t d ifferen ce was fo r Tuncus b a ltic u s. w hich h a d in c re a se d d en sity o n p lo ts w ith pH<6.4. In c o n tra st to th e clear im pacts o f tra c e m etals a n d pH o n v eg etatio n , facto rs su ch as soil salinity, soil clay co n ten t, site elev atio n above stre a m a n d distance fro m stre am d id n o t a lte r veg etatio n p a tte rn s. I CHAPTER I RESEARCH OBJECTIVES AND SIGNIFICANCE R esearch Q uestions Existing re se a rc h d o cu m en ts th a t h ig h levels of c o p p e r a n d o th e r m etals can be toxic to p la n ts (K abata-Pendias a n d P endias, 1992). In th e m o u n tain o u s West, w here histo ric a n d active m ines d o t th e landscape, tra c e m etals released b y m in in g a c tiv ity c an p o se to x icity h a z a rd s to v e g e ta tio n . O u tsid e th e n o r th e a s t c o rn e r o f Y ellow stone N atio n al Park, ta ilin g s fro m th e in a c tiv e M cLaren o p e n p it m in e h a v e b e e n a so u rc e o f su ch tra c e m etals. Before co rrectiv e actions w ere reco m m en d ed fo r th is tailings d e p o sit in 1989 (B ureau of R eclam ation, 1994), th e tailings im p o u n d m e n t d am fa ile d d u rin g a la rg e flo o d e v e n t in 1950 a n d Soda B utte C reek c a rrie d tailin g s a n d tra c e m etals dow nstream . Elevated levels o f trace m etals in floodplain sedim ents have b een id e n tifie d as fa r as 25km dow nstream (M eyer, 1993). Little is know n a b o u t th e sp a tia l d is trib u tio n o f th e tr a n s p o r te d tra c e m etals a n d th e ir im p a c t o n d o w n stre am v eg etatio n . This re s e a rc h focuses on assessing th e im p acts o f th e d isp laced m in e tailin g s o n g ra ssla n d v e g e ta tio n along Soda B utte C reek w ith in Y ellow stone N a tio n a l P ark. S p ecifically , th e s tu d y e v a lu a te s w h e th e r g rass sp ec ie s d iv e rsity , d e n sity , a n d biom ass: (I ) d e c re a se as tra c e m e ta l c o n c e n tra tio n s increase; a n d (2) decrease as soil pH d ecreases. These k ey issues w ere ch o sen o n th e basis o f re se a rc h in o th e r areas w h ere h ig h tra c e m e ta l levels a n d low 2 pH levels led to d ecrea se d v egetatio n diversity, d ensity, a n d biom ass (M acnicol a n d Beckett, 1985; K abata Pendias a n d Pendias, 1992; Levy e t aL, 1992). In o rd e r to assess th e ro le o f en v iro n m e n ta l v ariab les u n re la te d to m in e tailings, I also e v alu ated w h e th e r grass species diversity, d en sity , an d biom ass: (I) v a ry w ith soil clay c o n te n t a n d salinity; (2) v a ry as a fu n c tio n o f d istan ce fro m th e stre am c h an n e l o r elevatio n ab o v e th e channel; o r (3) change in th e d o w n stre a m d ire c tio n . Each o f th e se e n v iro n m e n ta l v a ria b le s can a ffe ct v eg etatio n p a tte rn s. For exam ple, h ig h clay co n ten ts can d ecrease trace m etal a v a ila b ility a n d th u s re d u c e im p acts o f tra c e m etals (Allbw ay, 1995); h ig h sa lin ity can re d u c e p la n t yields (Brady, 1990); site lo c atio n in re la tio n to a w a te r so u rc e c an in flu e n c e m o istu re levels, w h ich th e n a ffe c t p la n t g row th (B arbour e t al., 1987); a n d th e do w n stream lo catio n o f a site is tie d to changes in e lev a tio n a n d h a b ita t ty p e (D espain, 1990). This s tu d y w ill a d d to o u r know ledge of th e te m p o ra l a n d sp atial im p acts o f m in e tailin g s in h ig h la n d e n v iro n m e n ts . T his re s e a rc h w ill n o t o n ly p ro v id e in fo rm a tio n o n im p acts o f p a s t m ining activity, b u t m a y also p ro v e u sefu l in assessing th e p o te n tia l im p acts o f a n e a rb y p ro p o se d m ine. Crown B utte Mines, Inc., a su b sid ia ry of N o ran d a M inerals C orp., h a s su b m itte d exten siv e p ro p o sa ls fo r a n u n d e rg ro u n d gold m in e a d ja c e n t to th e o ld M cLaren o p e n p it m in es (G re a te r Y ellow stone C oalition, 1992). T he m ining o p e ra tio n as p ro p o se d w ould n o t d irectly affect Soda B utte Creek, because p re lim in a ry p lan s fo r th e m ine suggest p lacem en t of th e tailin g s p ile in th e a d ja c e n t F isher C reek d ra in a g e (C row n B utte M ines, Inc., 1992). H ow ever, th e p re lim in a ry E n v iro n m en tal Im p a c t S tatem en t lists sites in th e Soda B utte C reek d ra in a g e as a lte rn a tiv e ta ilin g s im p o u n d m e n t locations (USES a n d DSL, 1995). R esearch o n th e ex ten t a n d im pacts o f tra c e 3 m e ta l d istrib u tio n in th e Soda B utte C reek a re a will p ro v e u sefu l in p lan n in g m itig a tio n m e a s u re s , a sse ssin g th e p o te n tia l h a z a rd s o f th e re m a in in g M cLaren tailings, a n d estim atin g p o te n tia l im p acts o f th e p ro p o se d m in e o n o th e r stre a m d rain ag es. L ite ra tu re Review As scientists c o n tin u e to assess th e im plications of h u m a n reso u rce use, a com plex p ic tu re o f th e links b etw een m in e ra l e x tra c tio n a n d im p acts o n p la n ts a n d soils h a s e m e rg e d . W h en m in in g a c tiv ity in c re a s e d in th e n in e te e n th a n d e a rly tw e n tie th c e n tu ry , m in e rs h a d littie know ledge o f th e im pacts o f th e w aste p ro d u c ts o f th e ir tra d e , i.e. m ine tailings containing m an y h eav y m etals. Today, th ese h isto ric d ep o sits o f m ine tailings p o se a significant h a z a rd in term s o f m etal co n tam in atio n in soils a t th e m in e site a n d in alluvial soils d o w n stream (M arcus, 1989, 1991). W ithout rem ed iatio n , th e h eav y m etal c o n ta m in a tio n o f soils g e n e ra lly will la s t fo r d ecad es to c e n tu rie s, as soils serve as h eav y m etals sinks (Franzle, 1993). T he lite ra tu re speaks to several asp ects o f th is com plex e n v iro n m e n ta l issu e. W ork b y p la n t a n d soil sc ie n tists ex p lain s th e soil fa c to rs w h ich in flu en c e b io av ailab ility a n d tra n s p o rt o f tra c e m etals in to p la n t tissues, th e effects of toxicity o f specific tra c e m etals o n v eg etatio n , a n d ch arac te ristic s a n d to le ra n c e levels o f in d iv id u a l p la n t species (K abata P endias a n d P en d ias, 1992). M any stu d ie s focus on site-specific im p acts o f a b a n d o n e d m ines a n d m in e tailings, a n d a few exam ine th e d o w n stre am im p acts o f d isp laced m in e tailings (C ham bers e t al., 1987; Levy et al., 1992; Erickson a n d N orton, 1994). 4 E ioavailabilitv o f T race M etals C e rta in tra c e m e ta ls a re c o n sid e re d e sse n tia l fo r p la n t g ro w th a n d re p ro d u c tio n . A t h ig h levels, how ever, th e se sam e tra c e m e ta ls can le a d to m ild o r sev ere d ecreases in y ie ld (M acnicol a n d Beckett, 1985). The fa c to rs w hich c o n tro l p la n t u p ta k e o f tra c e m e ta ls in clu d e: ( I ) c o n c e n tra tio n a n d sp eciatio n o f th e m e ta l in th e soil a n d w a te r solution; (2) m o v em en t o f th e m e ta l fro m th e b u lk soil to th e ro o t surface; (3) tra n s p o rt o f m etal fro m th e ro o t su rface in to th e root; a n d (4) tra n slo ca tio n from th e ro o t to th e shoot. Of th e se facto rs, m e ta l c o n c e n tra tio n a n d sp eciatio n in th e soil a re th e p rim a ry influence on p la n t u p ta k e o f m etals (Alloway, 1995). T race m e ta l sp ec ia tio n re fe rs to th e p h ases (solid, liq u id o r gas) a n d chem ical fo rm o f each elem en t, w hich c an ra n g e fro m in so lu b le a n d h e n c e n o n -b io a v a ila b le solids, to p o te n tia lly b io a v a ila b le o rg a n ic a n d in o rg a n ic c o m p lex es, to b io a v a ila b le a n io n s a n d c a tio n s in th e a tm o s p h e re . soil s o lu tio n o r Specific soil c o n d itio n s e x e rt m a jo r c o n tro ls o n tra c e m e ta l so lu b ility (sp e cia tio n ) a n d b io a v ailab ility . Soil p ro cesses w hich can a ffe ct tra c e m e ta l so lu b ility in c lu d e d isso lu tio n , so rp tio n , com p lex atio n , m ig ratio n , p re c ip ita tio n , occlusion, diffusion, b in d in g b y organic su b stan ces, a b so rp tio n a n d s o rp tio n by m ic ro b io ta , a n d v o la tiliz a tio n (K abata-P endias a n d P en d ias, 1992). T hese soil processes, in tu rn , a re co n tro lled b y soil p ro p e rtie s su ch as soil pH , re d o x p o te n tia l, a n d c a tio n e x ch an g e c ap a c ity (CEC) a n d b y th e carb o n ate, Fe a n d Mn h y d ro u s oxide, a n d clay m ineral c o n te n t o f th e soil. Soil p ro p e rtie s a n d c o m p o sitio n c a n serv e as a n in d ic a to r o f th e b io av ailab ility o f tra c e m etals in soils a n d are easier to m e asu re th a n specific soil processes. P lant a n d soil scientists g en erally agree th a t soil pH an d red o x p o te n tia l e x ert th e g re a te st in flu en c e o n tra c e m etal b io av ailab ility (A driano, 5 1986; B arbour, e t al., 1987; K abata-Pendias a n d Pendias, 1992; Alloway, 1995). Clay m in e ra ls a n d o rg an ic m a tte r a re th e soil p ro p e rtie s w hich a re th e m o st im p o rta n t con tro ls o n th e so rp tio n o f tra c e m etals (Horowitz, 1991). These key soil processes a n d c o n tro ls a re exam in e d fu r th e r in th e follow ing subsections. pH a n d Redox P o te n tia l: Soil o x id a tio n -red u c tio n sta tu s in flu en ces th e s o lu b ility a n d to x ic ity o f tra c e m e ta ls a n d c o n tro ls n u tr i e n t a v a ila b ility (Alloway, 1995). As soil oxygen is d e p le te d d u e to w aterlogging o r com paction, a n a e ro b ic m ic ro o rg a n ism s p re d o m in a te a n d c e rta in tra c e m e tals u n d e rg o re d u ctio n . The c o n se q u e n t low red o x p o te n tia l o f a w aterlogged soil can le ad to re d u c ed p h o to sy n th esis (K ludze a n d DeLaune, 1995) an d d ecreased live biom ass (Koch a n d M endelssohn, 1989). In g en eral, low er red o x p o te n tia ls co in cid e w ith th e m ost m obile io n fractions (Brady, 1990). Acid soils (pH < 6.5) lead to leaching o f various elem ents, including zinc, copper, a n d iro n . A driano (1986) re p o rts th a t in soils w ith a pH betw een 4.2 a n d 6.6, zinc is m obile, arsenic is m o d e ra tely m obile, a n d c o p p e r an d lead a re slowly, m obile. Soil acid ificatio n stro n g ly im p a c ted tra c e m e ta l m o b ility in a s tu d y b y K abata-P endias a n d W iacek (1 9 8 6 ). Total m etal c o n c e n tra tio n (th e sum of iro n , m anganese, zinc, lead, copper, a n d cadm ium ) was 9080 n g /l fo r an acidified soil solution versus 17 n-g/l in th e sam e soil type w ith a n e u tra l pH. A review o f lite ra tu re o n m etal fluxes in fo re st soils co n clu d ed th a t b o th soil ty p e a n d v e g e ta tio n ty p e affect th e ra te o f soil a cid ificatio n a n d m etal leach in g (B ergkvist e t al., 1 9 8 9 ). O verall, in c re a s in g pH re d u c e s h e a v y m e ta l b io a v ailab ility a n d d ecreasin g pH in c re ase s m o b ility o f h e a v y m etal catio n s (B arbour e t al, 1987; Brady, 1990). pH levels also in flu en c e o th e r soil re a ctio n s. For exam ple, h y d ro ly sis a n d organic com plexing a re th e m ost p re v a le n t reactio n s in soil solutions, a n d ) 6 b o th a re pH sen sitiv e (K abata-P endias a n d Pendias, 19 9 2 ). In solid p h a se re a c tio n s, soil colloids dev elo p n e g ativ ely c h arg ed su rfaces a t h ig h pH a n d a d so rb cations (heavy m etals). C hanges in pH c an c re a te o b serv ab le changes in v e g e ta tio n p a tte rn s . W indblow n su lfu r d u s t fro m a p la n t in A lb erta c reated ex trem ely acid soils (pH I to 2) w ithin 200m o f th e p la n t, a n d m oss p lan ts in th e a re a w ere m ostly d ead . F u rth e r dow nw ind soil pH in c re ase d to 3.6 a n d th e m oss was d e ad o r dy in g (N yborg a n d M alhi, 1 9 9 1 ). Sm all re g io n s o f th e K lam ath M o u n tain s in C alifornia h a v e ex trem ely acidic soils (pH <4.5) w here a re a s w ith o u t conifers a re s u rro u n d e d b y n o rm a l co n ifero u s fo rests (D ahlgren, 1 9 9 4 ). V eg etatio n ty p e s o n a d ja c e n t p e a t m o u n d s in M in n eso ta e x h ib it stro n g lin k s b etw een d iv ersity a n d pH (G laser e t al., 1990). pH levels can also ch an g e rad ically o v er sh o rt d istan ces (K ershaw a n d Looney, 1985). A stu d y o f th e m ic ro d istrib u tio n o f T rifo liu m re p e n s rev ealed a pH g ra d ie n t w hich v aried b y a facto r o f 3 in a 60 cm d istance (Snaydon, 1962). I Clav M in erals: T he larg e surface a re a a n d p e rm a n e n t surface n eg ativ e c h arg e o f clay m in e ra ls in flu en ce tra c e m e ta l b io av ailab ility b y th e ir affin ity fo r catio n s (H orow itz, 1991). H igher clay co n ten ts g en erally in d icate a h ig h e r catio n exchange cap acity (CEC) (A driano, 1986) an d h en ce h ig h ad so rp tio n a n d b u fferin g c ap a c itie s (K abata-P endias a n d Pendias, 1992). C o n seq u en tly , th e p re sen c e o f clays can re d u c e th e b io av ailab ility of h e av y m etals. Blume a n d B nim m er (1987) d escrib e clay a d so rp tio n levels o f several tra c e m etals below th e pH level w h ere m etals fo rm stro n g oxides o r hydroxo-com plexes. Clays h av e m e d iu m a d so rp tio n of zinc below pH 5.5, m ed iu m a d so rp tio n o f c o p p e r below pH 4.5, h ig h a d so rp tio n o f lead below pH 4.0, a n d v ery h ig h ad so rp tio n of iron(III) below pH 3.5. A dsorption does v a ry according to th e type o f clay, fo r 7 exam ple, k a o lin ite a d s o rb e d 3.4 m eq /lO O g Zn2+ w h e rea s m o n tm o rillo n ite adsorbed 88 to 108 m eq/lO O g Zn2+ (Stuanes, 1976). O rg an ic M a tte r: O rganic m a tte r h a s h ig h a b so rp tiv e c ap acities fo r cations a t pH levels > 5 (Alloway, 1995). T race m etals can fo rm com plexes w ith so lu b le o rg a n ic lig a n d s o r c h e la te co m p lex es w ith h u m ic acid s (L inehan, 1985). In c o n tra st to th e com plexes o f hu m ic acids a n d m etal ions, com plexes o f m etals a n d fulvic acids te n d to be m o re b io av ailab le (C o tten ie e t ah, 1979; H orth, 1988). Blume a n d B riim m er (1987) state th a t organic m a tte r can fix iro n a n d le a d v e ry strongly, a n d zinc slightly. A driano (1986) lists copper, lead, an d zinc as h av in g a h ig h a ffin ity fo r o rg an ic m a tte r. A lth o u g h org an ic m a tte r can co n tro l tra c e m e ta l bioavailability, in m o st soils organic m a tte r com prises o nly 2% o f to tal soil w eight (K abata-Pendias a n d P endias, 1992). Plant U ptake of Trace M etals P la n ts p o sse ss a n a m azin g a b ility to a d a p t to n e w o r c h em ica lly im b a la n c e d e n v iro n m e n ts. For m o st p la n ts, how ever, th e ir a b ility to a d a p t re a ch e s lim its w h en tra c e m e ta l levels d ro p below o r rise above a ra n g e o f acceptable levels (Beckett a n d Davis, 1977). A lth o u g h o th e r p la n t tissues can a b so rb tra c e m etals, th e m a jo rity o f . a b so rp tio n occurs in p la n t roots. D uring passive u p tak e, tra c e m etals diffuse in to th e ro o t, w hereas active u p ta k e b rin g s trace m etals in to th e p la n t a g ain st a c o n c e n tra tio n g ra d ie n t (i.e. tra c e m e ta l c o n ce n tra tio n s in sid e th e p la n t a re h ig h e r th a n tra c e m e ta l c o n c e n tra tio n s o u ts id e th e p la n t) (R orison a n d R obinson, 1986; A llow ay, 1995). S cien tists d isag ree a b o u t specific u p ta k e m echanism s fo r in d iv id u al elem ents, b u t th e ra te of trace m etal u p tak e shows a 8 p o sitiv e c o rre la tio n w ith th e p o o l o f b io av ailab le m etals a t th e ro o t su rface (K abata-Pendias a n d Pendias, 1992). Plants a re m o st likely to a b so rb tra c e m etals w hich a re p re se n t in soil so lu tio n s in a n io n ic o r a c h e la te d a n d com plexed fo rm , a lth o u g h o rg an ic com p o u n d s p ro d u c e d b y ro o ts can release tra c e m etals fixed to clay m in erals. In o n e s tu d y (O lsen e t al., 1981) su n flo w er p la n ts u n d e r stress d u e to iro n deficiency p ro d u c e d ro o t exudates w hich low ered th e soil pH. T he low ered pH th e n so lubilized th e iro n , in creasin g its bioavailability. T ra n s fe r co efficien ts o ffer a fra m e o f re fe re n c e fo r co m p arin g p la n t u p ta k e o f d iffe re n t tra c e m etals. T he tra n s fe r coefficient is th e ra tio betw een th e m e ta l c o n c e n tra tio n in above g ro u n d p la n t tissu e a n d th e to ta l m e ta l c o n c e n tra tio n in th e soil. T ran sfer coefficients Usted b y Kloke e t al. (1994) fo r trace m etals c o n sid ered in th is stu d y include: c o p p er 0.1-10, lead 0.01-0.1, zinc 1-10, a n d arsenic 0.01-0.1. A tm ospheric d ep o sitio n o f h e av y m etals can also le a d to p la n t u p tak e. Fine p a rtic u la te m a tte r associated w ith m etal co n tam in an ts can a d h ere d ire c tly to p la n t leaves fo r fo liar u p ta k e a n d m o v em en t w ith in th e p la n t. In a d d itio n , ra in sp lash o f c o n ta m in a te d soil p articles o n to a p la n t le a f re p re se n ts a n o th e r tr a n s p o r t m e c h a n ism in a re a s w h ere c o n ta m in a n ts a re p re s e n t a t th e soil surface (H aygarth a n d Jones, 1992). In m in e d a re a s sim ila r to th o se o f Soda B utte C reek, tailin g s h a v e im p a c te d soils a n d p la n ts in m o u n ta in m eadow s (Levy, 1992). H ydraulically tra n s p o rte d m in e tailin g s fro m m in in g n e a r Leadville, C o lo rad o in th e e a rly 1900's a re resp o n sib le fo r h ig h soil m etal levels a n d acidic soils (pHs less th a n 5.6). T race m e ta l c o n c e n tra tio n s in p la n ts w ere sig n ifican tly c o rre la te d w ith to tal soil m etal levels fo r lead a n d Iuncus so ., lead a n d Poa so ., a n d zinc a n d Poa 9 sp. F or m a n y m e ta ls p la n t m e ta l c o n c e n tra tio n s ex ceed "norm al" fo liag e concentrations of 3 to 20 p p m copper, 0.10 to 1.0 p p m cadm ium , 2 to 5 p p m lead, an d 15 to 150 p p m zinc. T he Sum m itville, C olorado m in e d is a s te r also re s u lte d in d o w n stream d is tu rb a n c e d u e to tr a n s p o r t of acid ic, m e ta l-b e a rin g s u rfa c e w a te r a n d sed im en t (King, 1995). Soils along th e A lam osa River 25 to 5 0 k m .d o w n stream fro m Sum m itville ra n g e from 38 to g re a te r th a n 75p p m co p p er. C opper levels in a lfa lfa a n d b a rle y irrig a te d w ith m e ta l-e n ric h e d w a te r a re h ig h e r th a n levels in c o n tro l fields, b u t sim ilar to levels re p o rte d fo r o th e r areas in th e W estern U.S. S tudies o f w etlan d s in th e v alley show h ig h e r m etal levels in a q u a tic p la n ts re c eiv in g w a te r fro m th e m in e d a re a th a n in p la n ts w ith a d iffe re n t w a ter source. Heavy M etal Toxicitv in Plants A fin e lin e exists betw een re q u ire d co n ce n tra tio n s o f tra c e m etals a n d levels w hich p ro v e h a rm fu l to p la n t m etab o lism . D istin g u ish in g "excessive" q u a n titie s c an b e difficu lt. As tra c e m e ta l c o n c e n tra tio n s in c re ase to h ig h levels, p la n ts show o n e o f th re e b e h av io ral resp o n ses: ( I ) n o change, d u e to to leran ce m echanism s; (2) d ev elo p m en t o f b eh av io ral to leran ce; o r (3) dam age a n d d e ath , d u e to lack of tolerance (K abata-Pendias a n d Pendias, 1992). M u ltilp le p la n t sp ec ie s g ro w in g o n m in e ra l d e p o s its h a v e b e e n id e n tifie d as m e ta l to le ra n t, in c lu d in g c o p p e r to le ra n t G v o sp h H a p a tr in i, P o lv c a r p e a s p i r o s t v l i s . A c r o c e o h a lu s r o b e r t i . a n d M e r c e v a la tifo lia : iro n to le ra n t B etula sp . a n d C lusia rosea: lead to le ra n t E rian th u s g iganteus: a n d zinc to le ra n t Viola c alam in eria (C annon, 1960). M cGrath et al. (1993) tested T h laso i c a e ru le s c e n s . a species a d a p te d to m e ta l-ric h le a d /z in c soils in Europe, a n d fo u n d zinc accum ulations 150 tim es th a t o f a n o n -accu m u lato r species. 10 Som e p la n t p o p u la tio n s c o lo n iz in g m in e sp o ils h a v e d e v e lo p e d b e h a v io ra l to le ra n c e s o v e r tim e, d e m o n s tra te d b y lo w er s h o o t tissu e m e ta l c o n ce n tra tio n s in to le ra n t popu latio n s. A re n a ria douglasii. B rom us m ollis, a n d V u ln ia m ic ro s ta c h y a p la n ts grow ing o n c o p p e r m in e spoils a ccu m u lated less c o p p e r in s h o o t tissu e th a n p la n ts o f th e sam e species fro m c o n tro l sites (K ruckeberg a n d W u, 1992). P lan t a d a p ta tio n to in c re a se d m etal levels c an o ccu r ra p id ly , som etim es w ith in a few y e a rs o f th e d is tu rb a n c e (T yler e t al., 1989). S ensitivity o f in d iv id u a l species c an v a ry greatly, a lth o u g h m o st grasses , a re m o re to le ra n t o f excessive tra c e m etals (A driano, 1986). A stu d y o f p la n t re sp o n se to h ig h levels of tra c e m etals in sewage sludge fo u n d ch ard , le ttu c e, beets, a n d carro ts w ere in to le ra n t, w h ereas th e grasses Poa p ra te n s is . F e stu c a sp .. A vena sp.. D actvlis s lo m e ra ta w ere to le ra n t a n d B rom us in e rm is was v e ry to le ra n t (Logan a n d C haney, 1983). T ra c e m e ta l a c c u m u la tio n s in p la n ts d iffe r b e tw e e n p la n t p a r ts . G enerally, c o n c e n tra tio n s in v e g eta tiv e tissu e a re h ig h e r th a n in seeds. In c o m , fo r exam ple, m etal co n ce n tra tio n s d ecrease fro m le a f to stem to h u sk to kern el. Trees show a d ecrease in m e tal co n cen tratio n s fro m ro o ts to foliage to b ra n c h to tru n k . o f a p la n t. T race m etal levels can also change o v er th e grow ing season Fescue leaves (F e s tu c a s p .) sh o w ed a d e c re a se in cad m iu m , c h ro m iu m , c o p p e r, m a n g a n e s e , le a d and zin c as th e grow ing s e a s o n p ro g ressed (A driano, 1986). Toxicitv o f Specific Elem ents T he tra c e m etals o f in te re s t in this s tu d y in clu d e co p p er, lead, zinc, iro n , a n d a rsen ic . e lem en t. Specific im pacts' of tra c e m e ta l toxicity v a ry fro m e le m e n t to 11 C o p p e r: Toxic c o n ce n tra tio n s o f c o p p e r can cau se tissu e d am ag e a n d elo n g atio n o f ro o t cells, a lte ra tio n o f m e m b ra n e p erm eab ility , p e ro x id a tio n o f c h lo ro p la s t m e m b ra n e lip id s a n d in h ib itio n o f p h o to s y n th e tic e le c tro n tra n s p o rt, a n d im m o b ilizatio n of c o p p e r in cell walls, in cell vacuoles a n d in n o n -d iffu sib le c o p p e r p ro te in com plexes (K abata-Pendias a n d P en d ias, 1992). Alloway (1995) lists c o p p er as am ong th e m o st toxic tra c e m etals w hen p re s e n t a t excessive levels. S ym ptom s o f c o p p e r to x ic ity in c lu d e re d u c e d g ro w th vigor, p o o rly d e v elo p e d a n d d isco lo red ro o ts, a n d le a f chlorosis (A driano, 1986). Roots, w hich a re th e m a in site o f c o p p e r a b so rp tio n , also serve as th e lo catio n fo r d e p o sitio n o f excess c o p p e r (Linder, 1991). A lthough c o p p e r is essen tial fo r p la n ts , o n ly a n a rro w ra n g e o f c o p p e r c o n c e n tra tio n s p ro v e a cc e p tab le fo r p la n t g ro w th (B arber, 1995). For ex am p le, P e tte rso n (1 9 7 6 ) d o c u m e n te d d e p re ssed p la n t grow th w ith a solution o f lO nm ol/L copper. B oth soil pH a n d in te ra c tio n w ith o th e r tra c e m e ta ls affect c o p p e r bioavailability (A driano, 1986; Linder, 1991; K abata-Pendias a n d Pendias, 1992; A llow ay, 1995; B arber, 1995). C opper av ailab ility in creases below pH 6, a n d peaks below pH 5. As pH levels in crease above pH 6.5, c o p p e r com plexes form . O rganically com plexed c o p p er increases above pH 7. C opper ab so rp tio n can be in h ib ite d by zinc, b ecause b o th a re a b so rb e d b y th e sam e m ech an ism (Linder, 1991). L ead: Lead can also in te rfe re w ith essen tial p la n t p ro cesses su ch as p h o to s y n th e sis , g ro w th , a n d m itosis w h e n p re s e n t in h ig h c o n c e n tra tio n s (K abata-Pendias a n d Pendias, 1992). For exam ple, le ad 's a b ility to m im ic th e b eh av io r of calcium can in h ib it p la n t enzym es. Sym ptom s o f le a d toxicity in 12 p la n ts a re n o t well know n, a lth o u g h th e y in c lu d e d a rk g reen leaves, w ilting o f o ld e r leaves, stu n te d foliage, a n d brow n sh o rt ro o ts (Foy e t al„ 1978). As w ith co p p er, p la n ts a b so rb le a d th ro u g h th e ir ro o ts, a n d store excess le a d in th e roots. O rganic m a tte r is co n sid e re d th e p rim a ry soil sink o f excess lead. High soil pH also serves to d ecrease le a d u p tak e b ecau se th e lead form s in so lu b le com plexes. im m obilizing th e lead . For exam ple, le a d c an com plex w ith p h o sp h ate s, th u s In ad d itio n , zinc can re d u c e th e tra n slo c a tio n o f le a d from p la n t ro o ts to tops (A driano, 1986; K abata-Pendias a n d Pendias, 1992). In g en eral, a lth o u g h le a d is c o n sid e re d to p o te n tia lly b e o n e o f th e m o st toxic tra c e m etals, le a d so lu b ility , m obility, a n d th u s b io av ailab ility are g e n erally low over a w ide ra n g e o f pH levels (AUoway, 1995). Z inc: Sym ptom s o f zinc toxicity in clu d e chlorotic a n d n ecro tic leaf tips, re ta rd e d p la n t grow th, a n d "b arb ed wire" ro o ts (Cannon, 1960). As w ith c o p p er a n d lead, p la n t ro o ts te n d to co n tain m o re zinc th a n p la n t tops. M any p la n ts c an to le ra te h ig h levels o f zinc, w h ich is n o t c o n sid e re d h ig h ly p h y to to x ic (K abata-Pendias a n d Pendias, 1992); how ever, zinc is co n sid e re d highly m obile a n d bioavailable (Alloway, 1995). Zinc u p ta k e a n d bioavailability re la te m o st closely to pH, h y d ro u s oxides a n d clay m in e ra ls (Alloway, 1995). S olubility of zinc in c re ase s u n d e r acidic conditions, b u t zinc can also form com plexes w ith soluble org an ic m aterials in soils w ith pH levels g re a te r th a n 6.5 (B arber, 1995). S everal tra c e m etals, in clu d in g co p p er, iro n , a n d arsenic, h a v e an tag o n istic in te ra c tio n s w ith zinc, in w hich th e u p ta k e of one elem en t can b e com petitively lim ited b y th e o th e r (K abata-Pendias a n d Pendias, 1992). 13 Iro n : Signs o f iro n to x icity v a ry w idely am ong p la n t g en o ty p es a n d ' species, a lth o u g h sym ptom s can in clu d e d a rk g reen foliage a n d s tu n te d ro o ts a n d to p s (Foy, 1983). P lants can tak e u p larg e q u a n titie s o f iro n w h en in soluble form . It h a s b een re p o rte d th a t fo rb s ab so rb m o re iro n th a n grasses. T he level o f iro n bio av ailab ility re la te s closely to soil pH a n d ra tio s o f iro n w ith o th e r h e a v y m etals such as m an g an ese a n d c o p p e r (K abata-Pendias a n d P e n d ia s, 1992). D ecreasing soil pH in creases iro n so lu b ility , a n d toxic effects also te n d to co rre la te w ith salin ity a n d low soil p h o sp h o ro u s (Foy e t al., 1978). In c o n tra st, w h en iro n c h elate co m p o u n d s form , th e y a re m o re stab le th a n c o m p o u n d s w ith o th e r tra c e elem en ts, u n less h ig h c o n ce n tra tio n s o f th e o th e r ions cause m ass action d isp lacem en t (Barber, 1995). A rs e n ic : G row th re d u c tio n is th e m o st com m on sy m p to m o f a rsen ic toxicity, in a d d itio n to le a f w ilting a n d v io le t c o lo ra tio n (A driano, 1 9 8 6 ). S p e c ific ally , excess a rs e n ic re d u c e s w a te r m o b ility a n d h in d e rs se e d g e rm in atio n (Alloway, 1995). Plants in th e rice, bean, a n d legum e fam ilies a re co n sid e re d sensitive to excess levels of arsen ic. As w ith th e o th e r trace m etals discussed, p la n ts te n d to c o n ce n tra te excess arsenic in ro o t tissue. T he soil p ro p e rtie s w hich in flu en c e a rsen ic so lu b ility in c lu d e p e rc e n t clays, organic m a tte r, hydroxides, a n d pH (W oolsen e t al., 1973). Sandy soils fa c ilita te h ig h e r a rse n ic m o b ility a n d p h y to to x ic ity th a n clay ey soils. For exam ple, san d y soils h av e a toxicity th re sh o ld o f 40m g /k g v ersu s 2 0 0 m g/kg fo r clay ey soils (S h ep p a rd , 1992). A rsenic im p a c ts v a ry in th a t toxicity o f th e e lem en t in creases a t pHs less th a n 5, y e t h ig h e r pH soils m a y in crease p la n t arsen ic u p ta k e. 14 G rass Species C h aracteristics a n d R esponses to T race m etals: The v ast m a jo rity o f s tu d ie s o n p la n t re s p o n s e to tra c e m e ta l to x ic ity fo cu s o n a g ric u ltu ra l p la n ts . M any o f th e se stu d ie s grow p la n ts u n d e r la b o ra to ry c o n d itio n s a n d d o n o t s tu d y tra c e m e ta l to x icity u n d e r n a tu ra l c o n d itio n s. M acnicol a n d Beckett (1985) list critical co n cen tratio n s o f tra c e m etals in p la n t tissues (p p m d ry w eight) o f cro p p la n ts a n d species u sed as te st p lan ts fo r 10% yield losses. The critical levels w ere 1-20 p p m arsenic, 10-30 p p m copper, an d I 100-500 p p m zinc. K abata-Pendias a n d Pendias (1992) r e p o r t sim ilar critical c o n c e n tra tio n s fo r g row th d e p re ssio n in sen sitiv e p la n t species, in clu d in g 1520 p p m copper a n d 150-200 p p m zinc. O ne o f th e grasses in c lu d e d in th is stu d y , D e s c h a m n s ia c e s p ito s a . is know n to colonize d istu rb e d sites a n d displays h ig h to leran ce fo r acid soils a n d h ig h c o n c e n tra tio n s o f so lu b le m etals (Brow n e t al., 1 9 8 8 ). to le ra n ce v aries w ith local p o p u la tio n . D e s c h a m n s ia D e sc h am n sia c e s n ito s a from a c o p p e r m ill ta ilin g s p ile n e a r A naconda, MT fo r exam ple, w ere sig n ific a n tly m o re to le ra n t o f c o p p e r a n d zinc th a n a com m ercial p o p u la tio n o f th e sam e species (S urbrugg, 1982). D ow nstream fro m a fo rm er m ining reg io n in Spain, b o th Tuncus effu su s a n d B ra ch v th e c iu m riv u la re co n tain ed e lev ated trace m etal levels, th a t ra n g e d fro m 290 to 11800 p p m zinc a n d 4 to 1690 p p m lead (Sanchez et al., 1994). A lthough Sanchez e t al.'s stu d y fo u n d n o co rrelatio n betw een m etal levels in J. effu su s a n d valley sedim ents, th e a u th o rs re p o rt Tuncus s p p . growing in m in e tailings a n d m in e w a ter p o n d s in o th e r a re as a ro u n d th e w orld. R elated Studies in th e Cooke City A rea S everal re s e a rc h e rs h a v e s tu d ie d th e M cLaren m in e site o r m in in g re la te d im p a c ts o n th e S oda B utte C reek flo o d p lain . C ham bers e t al. (1 9 8 7 ) , 15 stu d ie d on site im p acts of. th e M cLaren o p e n p it m ine, exa m in in g trace m etal levels, soil c h arac te ristic s, a n d v eg etatio n resp o n se. T he m in e spoil m aterial, fro m th e sam e so u rce as th e m in e tailin g s, h a s low o rg an ic m a tte r, low pH, h ig h b u lk d e n sity a n d in c re ase d m etal solubility. T he p re se n c e o f this spoil m a te ria l h a s h a d im p acts o n soil m icrobiota, m esobiota, m acro b io ta, a n d p la n t species com p o sitio n . P lants w hich h av e n a tu ra lly re c o lo n ize d th e a re a grow p rim a rily in places w ith am en a b le soil c h arac te ristic s (e.g., soil pHs g re a te r th a n 7.0). H ow ever, th e se n a tu ra lly re v e g e ta te d areas still h a d sig n ifican tly low er v eg etativ e c o v er a n d biom ass th a n n e a rb y re fe re n c e a re a s w hich h a d n o t b e e n d is tu rb e d . A vailab ility o f iro n , m a n g an ese, a lu m in u m a n d zinc in creased in sites w ith pHs below 6.5. Efforts b y Brown e t al. (1984) to re e sta b lish v e g eta tio n o n th e M cLaren a lp in e m in e site fo c u se d on th e ro le o f fe rtiliz e rs in d ev elo p in g p ro te c tiv e p la n t cover. D espite re p e a te d applicatio n s o f fertilizer over a fo u r y e ar p erio d , th e re s e a rc h e rs fo u n d th a t species d iv e r s ity . o n th e m in e -im p a c te d sites re m a in e d low. T he re se a rc h e rs sta te d th a t in creases in species d iv ersity m ay on ly o ccu r over a long tim e p erio d , a n d a re in flu en ced b y clim atic v ariatio n . A n o th e r s tu d y by C ham bers e t al. (1991) ta rg e te d D aisy Creek, , in th e S tillw ater River d ra in a g e below th e M cLaren m ine. The re se a rc h e rs ex am ined s m a ll sc a le s p a tia l d is tu r b a n c e by m e a s u rin g v e g e ta tio n and so il ch aracteristics a t 500m in tervals along th e creek, u p stre a m a n d dow nstream o f a n acid m ine d ra in a g e source. C o n cen tratio n s of alu m in u m , c o p p er a n d iro n te n d e d to d e crea se in a d o w n stream d ire c tio n a n d w ere g e n erally in v e rsely re la te d to pH levels. T he h ig h e st pH levels o c c u rre d u p s tre a m of th e acid d ra in a g e a n d a t th e p o in t fu r th e r fro m th e acid d rain ag e. tra c e m e ta l le v e ls in p la n ts w ere p o o r ly c o r r e la te d R esults of tests o n w ith soil m e ta l 16 c o n cen tratio n s; how ever, th e re sea rc h ers suggested this co u ld be a fu n c tio n o f h ig h ly organic soils a n d re d u c e d p la n t u p ta k e, o r th e to le ra n c e o f th e C arex n a y s o n is th e y stu d ie d . C opper levels in C arex leaves d id exceed su g g ested m axim a fo r p la n ts a n d livestock forages. B a rb a ra E rickson, o f th e U.S. G eologic Survey, h a s c o lle cte d p la n t sam ples from seven sites along Soda Butte Creek from th e m in e tailings to a site n e a r th e co n flu en ce o f Soda B utte C reek a n d th e Lam ar R iver (Erickson a n d N orton, 1994). She collected grasses, h o rsetails (E quisetum s p .). Iodgepole p in e (P in u s c o n to r ta ) . E ngelm ann sp ru ce (P icea e n e e lm a n n ii). a n d willow sh o o ts (Salix sp .) in th e fall of 1992 a n d 1993. Results of trace m etal analysis o n th e p la n t sam ples show d o w n stre am d e crea se s in c o p p e r lev els fo r willow a n d grass, a n d decreases in zinc levels fo r grass. Lead a n d iro n levels v a ry in th e d o w n stre a m d ire c tio n . T he h ig h e s t c o p p e r, le ad , a n d zinc levels w ere id e n tifie d in p la n ts collected fro m th e tailin g s site. These re su lts suggest th a t p la n t m e ta l u p ta k e along Soda B utte C reek m ay co rre la te w ith th e p resen ce of m in e ta ilin g s. F u r th e r sam p lin g w o u ld b e u sefu l to c o lle c t p la n ts fro m a d ja c e n t d ra in a g es w ith o u t m in e tailin g s to estim ate b a ck g ro u n d p la n t m e ta l levels, c o m p a re m e ta l levels in p la n ts co llected a t d iffe re n t p o in ts in th e grow ing season, a n d an aly ze th e re la tio n s h ip betw een soil m etal levels a n d p la n t m e tal c o n ce n tra tio n s. 17 CHAPTER 2 FIELD AREA AND METHODS Field A rea T he Soda B utte C reek flo o d p lain s w ere u se d to ex am in e th e im pacts o f d isp la ce d M cLaren m in e tailings. Soda B utte C reek o rig in a te s e a st o f Cooke City, M ontana, th e n flows p a st m ine tailings fro m th e M cLaren o p en p it m in es a n d in to Y ellowstone N ational Park (Figure I). The stream also flows p a st a n d actively e ro d e s th e RepubUc sm elter site a t th e so u th w est e n d o f Cooke C ity (Kirk, 1992). Soda B utte Creek re a ch e s th e Lam ar R iver 30 km d o w n stre am from Cooke City. T he m e a d o w /g rasslan d s along th e creek a re c h a ra c te riz e d b y a v a r i e t y . o f g ra sse s in c lu d in g P h le u m p r a t e n s e , B ro m u s e n e r m i s . A g r o p v r o n s p .. D e s c h a m p s ia c e s p ito s a . a n d Poa s p .. fo rb s, willows (Salix s p .). a n d c o n ife rs (D espain, 1990). The tailings sed im en ts in th e m e ad o w /g rasslan d s flo o d p lain a p p e a r as a d iscrete oxidized la y e r ran g in g in thickness fro m 35cm to 5cm o r less, a n d a re u n e v en ly d istrib u te d (M eyer, 1993). H abitat Types E n g e lm a n n sp ru c e (P ic e a e n g e l m a n n i i ) a n d s u b a lp in e fir (A b ie s la sio c a rp a ) forests, along w ith s c a tte re d m eadow s a n d w illow thickets b o rd e r th e u p p e r re a ch e s o f Soda Butte Creek. Below Icebox C anyon (Figure 2), Soda B utte C reek e n te rs b ro a d v a lle y g ra ssla n d s o f g rasses, sed g es, sa g e b ru s h B ozem an Yellowstone Region Livingston Utah R ed L o d g e Colorado Cooke City _Montan_a W yom in g Yellowstone /' V ./x \d o h o National Yellowstone Lake Figure I. Map of stu d y area a n d Y ellowstone region. C o o k e Cityi Soda Butte Creek Study Sites FISH MEADOW/ McLaren Tailings Pile Shoshone I___ Nat[onaJ_Forest____ Yellowstone National Parkx , N \ ^Icebox Canyon 5km rTjQ r/5 Figure 2. Map of m eadow study sites along Soda Butte Creek, MT an d YVY. 20 (A rte m e sia sp .), ra b b itb ru s h (C hrvsotham m us sp .). a n d w ildflow ers (E v ersm an , 1992). T he m e ad o w /g rasslan d s fo u n d alongside Soda B utte C reek a re classified in to sev eral h a b ita t ty p es (D espain, 1 9 9 0 ).. T u fted h a irg ra s s ID e s c h a m o s ia c e s p i t o s a ) / sed g e (C a re x sp..) a n d T u fte d h a irg ra s s /I d a h o fescu e (F e s tu c a id a h o e n s is ) h a b ita ts o c cu r alo n g s tre a m sid e s. T y p ically th is h a b ita t ty p e occurs in a re a s w h ere su fficien t g ro u n d w a te r accu m u lates. The soils d e riv e fro m alluvial m a te ria l a n d a re h ig h in clay, silt, a n d org an ic m a tte r. A v a rie ty o f o th e r sedges (e.g. C arex a th ro s ta c h v a a n d C arex a lb o n ig ra ) a n d fo rb s (e.g. P o ly g o n u m b is to rto id e s . A n te n n a ria c o rv m b o sa . a n d P o te n tilla g ra c ilis) o ccu r in th e tu fte d h a irg ra ss h a b ita t types. In m o re m e sic site s, th e p r e d o m in a n t h a b ita t ty p e s a r e Id a h o fe s c u e /b e a rd e d w h e a tg ra ss (A g ro o v ro n s c rib n e ri) ab o v e 2 2 70m a n d Id a h o fe s c u e /b lu e b u n c h w heatgrass. (A g ro o v ro n so ic a tu m ) fro m 1670m to 1970m . T he Id a h o fe scu e h a b ita ts in m o is te r a re a s fe a tu re a stic k y g e ra n iu m (G e r a n iu m v is c o s is s im u m ) p h a se r a th e r th a n b e a rd e d w h e atg rass. O th e r co m m o n sp ec ie s in c lu d e P o te n tilla g r a c ilis . B ro m u s c a r i n a t u s , S o lid a g o m isso u rien sis a n d C arex ra v n o ld sii (D espain, 1990). Soils in b o th h a b ita t types are d e riv e d fro m an d esitic volcanics. T he m e a d o w /g ra ssla n d h a b ita ts alo n g Soda Butte C reek also c o n tain a n u m b e r o f in tro d u c e d species, such as com m on tim o th y (P h leu m p ra te n s e ) (R um ely a n d Lavin, 1993). In tro d u c e d species often p ro v e m o re re silie n t to clim ate ch an g e a n d e n v iro n m e n ta l d is tu rb a n c e th a n n a tiv e species (Rom m e, 1992). 21 Study Sites Four m e ad o w /g rasslan d stu d y sites along Soda Butte C reek w ere selected to re p re s e n t v a rie d elev a tio n s a n d d o w n stre a m d ista n ce s fro m th e ta ilin g s so u rce a n d b ecau se o f th e ir a cc e ssib ility (Figure 2). B ased o n soil p ro b e surveys, all th e m eadow s selected h a d a n oxidized o ran g e soil la y e r th a t w ere m in e tailings, b a se d o n d escrip tio n s b y M eyer (1993), as well as areas w ith o u t e v id e n c e o f ta ilin g s. T h e m ead o w s s e le c te d a lso c o m m u n itie s w ith s im ila r sp ecies c o m p o sitio n . r e p r e s e n t v e g e ta tio n A lth o u g h se v e ra l o f th e m eadow s ex ten d upslo p e across old flo o d p lain terraces (M eyer, 1993), th e stu d y sites w ere lim ited to th e m o d e rn floodplain. Fish m eadow (elevation 2175m ) is lo c ated 9km d o w n stre am from Cooke City along U.S. R oute 212 (Figure 2). This sm all m ead o w is betw een two 9 0 ° b e n d s in Soda Butte Creek, on th e n o rth side o f th e creek. D ense fo rest hem s in th e m ead o w o n th e n o rth a n d east, th e so u th edge ru n s along th e creek, a n d the w est side is a steep slope up to th e ro a d b e d (Figure 3). W ithin th e m eadow , a few willows a re sca tte re d am ongst th e grasses an d forbs. Tuncus b a lticu s was p re v a le n t in th is m eadow , w hich was a w e tte r site th a n th e m e ad o w site s d o w n stream . H ollyw ood M eadow sits o n th e e a s t side o f Soda B utte C reek a t a n elevation o f 2130m , 15.5km from Cooke City (Figure 2). I selected a section o f th e m eadow lo cated betw een Soda Butte C reek a n d a d e p re ssio n b e h in d a tre e islan d fo r sam pling. This sam ple a re a in clu d es a relativ ely b a re p atch o f m ine tailings exposed a t th e surface. Hollyw ood m eadow co n tain s a diverse a rra y o f grasses a n d forbs, w ith s c a tte re d sag e b ru sh o n old flo o d p lain te rra c es fu r th e r I fro m th e creek (Figure 4). 22 Figure 3. Fish M eadow (top) a n d Figure 4. Hollywood M eadow (bottom ) 23 Figure 5. Icebox M eadow (top) an d Figure 6. Round Prairie (bottom ) 24 Icebox M eadow occupies a n a rro w strip betw een th e highw ay a n d th e creek, 17.8km d o w n stream from Cooke City (Figure 2). This m ead o w a t 2 1 00m h a s E ngelm ann sp ru c e a n d willow, in a d d itio n to g rasses a n d forbs. As in H ollyw ood m ead o w , s c a tte re d sa g e b ru sh o c cu r f u r th e r fro m th e c re ek o n e lev ated flo o d p lain te rra c e s (Figure 5). A fter S oda B utte C reek p asses th ro u g h Icebox C an y o n , it !lows in to R ound P rairie a t 2055m . R ound P rairie covers a m u ch la rg e r a re a th a n th e u p stre a m m eadow s, b u t th e stu d y site was lim ited to a series o f sm all "islands" b e tw ee n in te rm itte n t c h an n e ls a t th e so u th e n d o f th e p ra irie , 22.4km fro m Cooke C ity (Figure 6). T hese "islands" w ere e q u iv alen t in size to th e o th e r stu d y sites. G eneral C lim ate C haracteristics A ir m asses fro m th e Pacific O cean, th e A rctic, a n d th e Gulf o f M exico a ffe c t th e c lim a te o f th e n o r th e r n Y ellow stone a re a . As th e je t s tre a m m ig rate s so u th in th e w in ter, storm s b rin g m o istu re fro m th e Pacific. From D ecem b er u n til F eb ru ary , Y ellow stone also receives cold, d ry c o n tin e n ta l a ir m asses fro m th e w estern G reat Plains. In co n trast, su m m er storm s arise m o re o ften from locahzed convection th a n fro m fro n ta l system s (D espain, 1990). W inter is th e lo n g est season in th e stu d y area, lastin g fro m m id to la te O cto b er u n til la te M arch o r e a rly A pril, w ith p e rm a n e n t sn o w c o v er a n d b elo w -freezin g a v e ra g e d a ily te m p e ra tu re s ra n g in g fro m 0 ° to -10°C. T he su m m er season in. July a n d A ugust is c h a ra c te riz e d b y w a rm e r days ( IO0C to 13°C), occasional n ig h t te m p e ra tu re s b elow 0°C a n d fre q u e n t th u n d e rsto rm s. Freezing ev en in g co n d itio n s o ccu r ag ain in S ep tem b er (D espain, 1990). T he N o rth e a st E n tran ce S tation SNOTEL site is a d jac e n t to Soda Butte Creek a t th e n o r th e a s t b o r d e r o f Y ellow stone N a tio n a l P ark a n d p ro v id e s s e a s o n a l 25 p re c ip ita tio n a n d te m p e ra tu re d a ta (Figure 7) (SCS,1994). T he snow pack lasts a p p ro x im a te ly 200 d ay s o f th e y ear, w ith a p eak snow w a ter eq u iv alen ce o f ap p ro x im ately 25cm , usually occurrin g n e a r April I (D espain, 1990). A verage a n n u a l p re c ip ita tio n a t th e N o rth e a st E n tran c e sta tio n (2 1 6 2 m ) is < 70cm (Despain, 1990). 80 “ I Q 40 m 5 20 £> 0 I -20 g Month of the Year Figure 7. Y ellow stone N ational Park N o rth e a st E n tran ce S tatio n C lim ograph (Despain, 1990). Table I lists average m axim um a n d m inim um re c o rd ed te m p e ratu res a n d a v e ra g e p re c ip ita tio n a m o u n ts b a se d o n SNOTEL d a ta fro m th e N o rth e a st Entrance Station d u rin g th e growing season. D uring th e 1993 field season, th e clim ate was w etter th a n th e p reviou s ten y e a r average by a t least 2.4cm e a c h m o n th , a n d co o ler th a n th e ten y e a r m axim um te m p e ra tu re s a n d a v e ra g e te m p e ra tu re s by v ary in g a m o u n ts (T able I). The significance to v eg etatio n sam p lin g o f th e cool 1993 su m m e r is d iscu ssed la te r in th e sectio n o n field w o rk . 26 T able I. Y ellow stone N atio n al Park N o rth e a st E n tran ce S tation: T e m p e ra tu re a n d P recip itatio n fo r June, July, a n d A ugust.__________________________________ Tmax (0C) AVG 1993 1994 JUNE 29 Tmin (0C) AVG 1993 1994 Tavg (0C) AVG 1993 1994 Prec (cm) AVG 1993 1994 16.1 20.1 - 4 .5 0.6 1.2 8 .8 8.4 10.7 7 9.5 7.7 JULY 2 8 .4 17.7 23.7 - I 1.9 2.9 11 9.8 13.3 7 .1 9.5 6.0 AUG 19.7 24.9 - 2 .5 2.2 3.6 1 1 .5 10.9 14.3 3 .6 6.2 3.7 2 9 .2 AVG tem perature d a ta from 1 9 8 4 ,1 9 8 6 ,1988, 1990, 1992 SNOTEL (SCS, 1994) AVG precipitation d a ta from 1984, 1986, 1988, 1990, 1992 prec (SCS, 1994) 1993 an d 1994 d a ta from U.S. D epartm ent o f Commerce (1993, 1994) H istoric M ining P ractices Cooke City, lo cated below th e h ead w aters of Soda B utte Creek (Figure I), cam e in to ex isten c e as a m in in g tow n. Crow In d ia n s m a n a g e d to k e ep fu rtra p p e rs a n d m in e rs a t b a y fo r n e a rly 50 y ears from th e tim e Jo h n C olter first saw th e a re a in 1808. Two groups o f p ro sp ecto rs re tu rn e d to th e a re a in 1864 a n d w ere, follow ed b y a n influ x o f m in ers a n d m in in g claim s. In th e 1870's 80 tons o f silver-lead o re fro m M iller M ountain a n d R epublic M ountain w ere sm elted b y th e E astern M ontan a M ining a n d Sm elting C om pany (Crow n Butte Mines, Inc., 1994). / Jay Cooke, Jr. a rriv e d from th e East in 1880, b o u g h t th e R epublic M ine p ro p e rty , a n d p ro m ised to bring a ra ilro a d to th e area, so th e resid en ts d ecid ed to n a m e th e tow n Cooke City (G yan-G orski, 1977). A ro a d was b u ilt into Cooke City b y Jack A llen in s u b se q u e n t y ears, b u t th e ra ilro a d n e v e r m aterialized . The p o p u la tio n o f th e a re a ra n g e d fro m 10 p eo p le to 1,000 p eo p le as m in es o p e n ed a n d closed a n d ru m o rs a b o u t th e ra ilro a d circulated (H ansen, 1962). M ajor G eorge Eaton in v ested in th e R epublic M ining C om pany in 1883, d eveloping m ines a n d a sm elter on th e so u th side of Soda B utte Creek a t th e so u th east e n d of Cooke City. In 1885, th e Republic sm elter p ro d u c e d 440 tons o f 27 s ilv e r-le a d b u llio n fro m R epublic M o u n tain o re a n d M ille r M o u n tain o re (C row n B utte M ines, Inc., 1994). W hen th e R epublic m in e a n d sm elter s h u t dow n in 1886, m ining c o n tin u e d th ro u g h th e 1890's o n H en d erso n M ountain a t th e H om estake m ine, th e D aisy m ine, a n d th e Alice E. m in e. The H om estake m in e a n d th e D aisy m in e g e n e ra te d 4 2 0 to n s o f o re b e fo re th e H o m e s ta k e p r o p e r ty w as a b a n d o n e d . A ctiv ity o n th e D aisy c laim th e n in c re a s e d , follow ing a n in itial sh ip m e n t o f 390 to n s o f ore, u n til th e D aisy m ine closed in 1894. A cyanide m ill processed 2500 to n s o f o re fro m th e Alice E. m ine in 1893, b u t m ining o p e ra tio n s ceased b y 1895 (Crown Butte Mines, Inc., 1994). M ine p ro d u c tio n e n te re d a lull in th e e a rly 190 0 's b u t re tu rn e d w ith th re e o p e n p it m in es in the. 1930's. T he G len g arry C o m p an y a t Lulu Pass o p e ra te d th e Como Pit fro m th e m id -1 9 4 0 's u n til 1955. In th e la te 1940's, th e H om estake g ro u p o f m in es w ere also re o p e n e d . The M cLaren G old M ines C om pany b e g an o p e n p it o p e ra tio n s o n th e w est side o f F ish er M o u n tain in 1933, a n d c o n tin u e d u n til 1953. The co m p an y p u rc h a se d th e sm elter b u ilt b y M ajor G eorge Eaton on Soda Butte Creek, a n d tra n sfo rm e d it in to a mill. O ver th e course o f its o p eratio n s, th e M cLaren m in e p ro d u c e d 60,000 ounces o f gold, 88,000 o u n ces o f silver, a n d 2000 to n s o f c o p p e r (Crow n B utte M ines, Inc., 1994). Tailings fro m th e M cLaren m in e w ere sto re d a t th e m ill site (Figures I a n d 2) in th e h e ad w a te rs of Soda Butte Creek, a n d a re th e p ro b a b le so u rce o f th e m ine tailings d eposits now fo u n d along th e floodplains o f Soda Butte C reek (M eyer, 1993). A t p re s e n t large-scale m in in g has ceased a n d Cooke City a n d Silver G ate re ly on to u rism a n d re c re a tio n fo r th e ir econom ic base. Clim ate Events a n d Tailings T ran sp o rt Cooke City re sid e n ts, in te rv ie w ed b y R alph G lidden, re c a lle d a tailin g s im p o u n d m e n t d a m fa ilu re in th e su m m er o f 1950 follow ing a series o f h e a v y 28 ra in sto rm s a n d flash floods in th e u p p e r b asin (M eyer, 1993). A tailings p o n d on M iller C reek m ig h t h a v e fa ile d a s w ell. The Y e llo w sto n e P a rk S u p e rin te n d a n t's r e p o r t fo r Ju n e, 1950 ex p resses c o n ce rn a b o u t a fa ilu re o f th e M cLaren tailings d a m (YNP, 1950): Large q u a n titie s o f m in e tailin g s flow ed in to Soda B utte C reek th ro u g h a b re a k in th e e a r th w all o f t h e ' settlin g p o n d s o f th e M cLaren m in e s w hich a re lo c a te d a b o u t five m iles a b o v e th e n o rth -e a s t e n tra n c e o f th e p a rk ...th e w all was b e in g r e p a i r e d w h en a n in sp e c tio n was m a d e o n Ju n e 28 b u t th e m ass o f th e a cc u m u la te d m in e refu se con tin u es to be a serious th r e a t to p a rk w a te r s .. D aily a n d h o u rly p re c ip ita tio n re c o rd s show a ra in s to rm o n Ju n e 24, 1950 d ro p p e d 4.83cm of ra in betw een 1300 a n d 1400 local tim e, a n d a to tal o f 5.15cm fo r th e d a y (USDC, 1950). T he h o u rly re c o rd s co n flict w ith th e d a ily re c o rd s, w hich list 2.2cm o f p re c ip ita tio n fo r Ju n e 24, 1950. However, if th e h o u rly re c o rd s a re c o rrect, th e s u d d e n in flu x o f ra in co u ld p ro d u c e a flo o d e v e n t a n d tailings failu re. In a d d itio n , 2.53cm o f p re c ip ita tio n fell Ju n e 22, 1950, w hich m ay have s a tu ra te d th e g ro u n d p rio r to th e ra in sto rm on Ju n e 24, 1950 (USDC, 1950). P relim in ary stu d ies along th e flo o d p lain s o f Soda B utte C reek b y M eyer (1993) in d ic a te th a t th e larg e flood e v en t tra n sp o rte d m in e tailings as fa r as 25 km dow nstream . E lem ent levels in th e tailings im p o u n d m e n t a n d in flo o d p lain sed im en ts exceed b ack g ro u n d levels b y several o rd e rs o f m a g n itu d e a n d m etal levels decline in c o n ce n tra tio n dow nstream , as w ould b e ex p ected w ith d ilu tio n d u rin g d o w n stream tra n s p o rt (M eyer, 1993). M ethods I co llected d a ta on v eg etatio n , soil a n d site c h arac te ristic s in o rd e r to s tu d y p o ssib le re la tio n s b etw een h e a v y m e ta l levels a n d g rass co m m u n ities 29 alo n g th e flo o d p la in . I sam p led tra c e m e ta l c o n c e n tra tio n s , soil pH , soil electrical c o n d u ctiv ity (EC), a n d p e rc e n t clays a t two soil d e p th s fo r 45 to 100 p o in ts in each stu d y site. V egetation d a ta a t the sam e sam p le p o in ts in c lu d e d d e n sity o f fo u r g rass species, p e rc e n t co v er, ab o v e g ro u n d biom ass o f o n e grass species, a n d species d iv e rsity a n d a b u n d a n c e . I also m e a s u re d th e e le v a tio n o f e ac h sam ple, p o in t a b o v e th e activ e s tre a m c h a n n e l a n d its d istan ce to th e stre am channel. Fieldw ork In each m eadow , I d o c u m en ted th e d istan ce to th e stre a m c h an n e l a n d elev atio n above th e stre am fo r each sam ple p o in t b y surveying transects. This d a ta was u sed to d e te rm in e w h e th e r th e tailings c o n c e n tra te d in a sy stem atic s p a tia l p a tte r n , w ith in a c e rta in d is ta n c e fro m th e s tre a m c h a n n e l o r a t specific elev atio n s ab o v e th e ch an n el. In ad d itio n , th e se d a ta allow ed m e to te s t if d is ta n c e fro m th e s tre a m a n d e le v a tio n ab o v e th e c h a n n e l a f f e c te d v e g e ta tio n p a tte rn s . T he tra n se c ts r a n p e rp e n d ic u la r to th e d ire c tio n o f stre a m flow a n d began a t eq u ally sp aced in terv als along th e stream bank. T he tra n se c t sp acin g along th e stre a m b a n k v a rie d accord in g to th e le n g th a n d w id th o f each site. T he d ista n ce betw een tra n se c ts was IOm in Fish M eadow, 15m in H ollyw ood M eadow, 30m in Icebox M eadow a n d 15m in R ound P rairie. T he tr a n s e c ts e x te n d e d in to th e m eadow s vary in g d istan ces, d e p en d in g o n th e w idth o f th e active flo o d p lain . My objective, b a se d o n p re lim in a ry d a ta p lo ttin g species d e n sity vs. n u m b e r o f q u a d ra ts, was to p la ce en o u g h tra n s e c ts to ach iev e a m in im u m sam ple size o f 30 q u a d ra ts in each m ead o w (C hapm an, 1986). m a rk e d th e e n d p o in ts o f each tra n se c t w ith flagging fo r fu tu re referen ce. I 30 In each o f th e fo u r m e a d o w /g ra s s la n d s s e le c te d fo r stu d y , I u sed system atic sam pling w ith m ultiple ra n d o m starts along th re e to six tran sects to locate sam p le p o in ts (Brown, 1983). A ra n d o m n u m b e r ta b le p ro v id e d th e location o f th e first q u a d ra t on each tra n se c t w ithin 200cm o f the stream edge. S u b se q u en t q u a d ra ts w ere spaced a t two m e te r in te rv a ls alo n g th e tra n se c t from th e first q u a d ra t. D ata from a sam ple tra n sec t show ed th a t th e v a ria tio n in m ean d en sity levels d a m p ed at this two m e te r in terv al along a 30m tra n sec t (Figure 8). I u sed c irc u la r q u a d ra ts to m in im ize sam p lin g e rro r a sso c iate d w ith hig h b o u n d a ry lengthcarea ratio s (C hapm an, 1986). T he q u a d ra t size of SOOcrn2 was w ith in th e suggested size ra n g e fo r sam pling grasses a n d fo rb s (Bonham, 1989). mean density Number of quadrats along transect Figure 8. V ariation in m ean d en sity levels o f P hleum p ra te n s e along a sam ple tra n s e c t. Four p e re n n ia l grass species w ere selected d u e to th e ir p resen ce in m y stu d y a re a a n d ease o f identification, inclu d in g D escham psia cesp ito sa. B rom us s p . A g ro p v ro n s p .. a n d P h Ieu m p r a te n s e (W hipple, 1993). In each c irc u lar q u a d ra t I re c o rd e d grass species d en sity , visually estim ated th e p e rc e n t co v er o f m oss, h erb s, grasses, a n d b a re ground; a n d collected ab o v e-g ro u n d grow th 31 o f P h le u m p ra te n s e d u rin g th e sum m er o f 1993. T he b io d iv e rsity m e asu re s I c o n d u cte d in 1994 (d escrib ed below) a d d e d d en sity d a ta fo r all grass a n d fo rb species in Fish M eadow, Hollywood M eadow, a n d Icebox M eadow. I collected soil sam ples fro m O-IOcm w ithin 269 q u a d ra ts a n d fro m 1020cm fo r 125 q u a d ra ts (m an y q u a d ra ts lack ed sufficient d e p th fo r a 10 -2Ocm sam ple). I also re c o rd e d soil color a n d te x tu re a n d n o te d th e d e p th o f th e soil la y er. D ividing th e soil p ro file in to two d e p th s allow ed fo r a m o re fo cu sed p ic tu re of th e d is trib u tio n o f tra c e m etals in th e flo o d p lain a n d acco u n ts fo r v e g eta tio n w ith d iffe re n t ro o t lengths. All soil sam ples w ere sto re d in ziploc bags in a fre e z e r u n til I b eg an analysis. D uring th e first w eek o f A ugust in 1994, I re tu rn e d to m y stu d y sites to collect d a ta fo r a b io d iv e rsity index. I re lo c a te d th e tra n sec ts in Fish M eadow, H ollywood M eadow a n d Icebox M eadow a n d u sed th e sam e q u a d ra t spacing a n d lo catio n s. W ithin e ac h q u a d ra t I c o u n te d th e n u m b e r o f d is tin c t species (d iv e rsity ) a n d th e n u m b e r o f in d iv id u a ls o f e ac h s p e c ie s (M agurran, 1988). (a b u n d a n c e ) O verall, th e su m m er o f 1994 was w a rm e r a n d d rie r th a n sum m er 1993 (USDC, 1994). In 1994, average daily tem p eratu res fo r the m o n th s of May, June, July a n d A ugust w ere I to 7°F h ig h e r th a n in 1993 (Table I). The a v erag e m in im u m d a ily te m p e ra tu re s w ere n o m o re th a n 4°F h ig h e r w hile av erag e m axim um d a ily te m p e ra tu re s w ere u p to IO0F w a rm e r in 1994. The clim ate s ta tio n re c o rd e d 3.3 m o re in c h es o f p re c ip ita tio n b etw een May a n d A ugust o f 1993 th a n th e sam e m o n th s in 1994 (USDC, 1994). These differences in clim ate re s u lte d in e a rlie r p la n t m a tu ra tio n in 1994. As a co n seq u en ce, species id e n tific a tio n w as e a s ie r a n d p e rh a p s m o re a c c u ra te in 1994. A co m p ariso n of th e n u m b e r o f q u a d ra ts co n tain in g B rom us s p . a n d A g ro p y rp n so . shows a slight in crease in 1994. In 1993, A g ro p y ro n sp . o ccu rred in 6% o f 32 th e q u a d ra ts v ersu s 8% in 1994, a n d B ro m u s sp . o c cu rred in 9% o f th e 1993 q u ad rats a n d 14% o f th e 1994 quadrats. Soil A nalysis T he soil sam ples w ere first oven d rie d o v ern ig h t in a fo rced a ir o v en a t 3 5 °C. Each sam ple was sieved fo r 3.5 m in u te s using a m e ch an ical siev er to rem o v e th e c o arse fra c tio n (>2m m ) (Klute, 1986). G enerally, soil fra g m e n ts la rg e r th a n 2m m (pebbles a n d cobbles) h a v e only a m in o r ro le in soil fu n c tio n (B arbour, 1987). T he soil analysis p ro c e d u re s I u sed re q u ire d soil size <2m m (M ontague, 1984; Klute, 1986). T he sieving tim e was selected b ased o n th e sm all size o f th e sam ples (<75g) (Tyler, 1993) a n d because I o n ly d id one size split using th e sieve (less th a n a n d g re a te r th a n 2m m ). A pproxim ately 3g o f each sam ple was sen t to C hem ex Labs in Butte, MT fo r a 32 e le m e n t in d u c tiv e ly co u p led p la sm a (ICP) analysis. Chem ex u ses a n a q u a re g ia d ig e stio n , w hich disso lv es o rg a n ic m a tte r a n d sulfide m in e ra ls. D e te c tio n lim its v a ry fro m o n e e le m e n t to a n o th e r . ICP m e a s u re m e n t p recision varies fro m + /- 100% a t d etectio n lim its to + /- 10% a t values 100 tim es h ig h e r th a n d e tec tio n lim its (Chemex, 1991). To select th e elem ents w hich w ould b e co n sid ered in d a ta analysis, th re e c rite ria serv ed to elim in ate u n n e e d e d tra c e m etals: (I) th e tra c e elem en t level o fte n fell below d e te c tio n lim its; (2) th e re was n o sig n ifican t v a ria tio n in th e tra c e e le m e n t lev el th ro u g h o u t th e s tu d y reg io n ; o r (3) a cco rd in g to th e lite ra tu re , th e tra c e e le m e n t d id n o t exceed toxic levels (K abata-P endias a n d P e n d ia s, 1992). I e lim in a te d 27 o f th e 32 re p o rte d tra c e elem en ts, re ta in in g arsenic, copper, iro n , lead , a n d zinc fo r fu r th e r analysis. In o rd e r to assess th e level o f p re c isio n of th e tra c e e lem en t re su lts, I sen t a n a d d itio n a l 27 d u p licate soil sam ples to th e la b o ra to ry . For each o f th e 33 five elem en ts u sed in m y stu d y I c alcu lated th e av erag e p e rc e n t d ifferen ce in re su lts b e tw ee n th e d u p lic a te s a n d th e o rig in al. T he a v e ra g e d iffe re n c e s ra n g e d fro m 6% fo r iro n , 7% fo r zinc, 8% fo r copper, a n d 14% fo r lead, to 36% fo r a rsen ic . pH a n d EC analysis w ere co n d u cted o n a 1:2 so il/w a ter solution following p ro c e d u res o u tlin ed b y M ontagne (1984). I p laced Sg of each soil sam ple in to a te st tu b e a n d a d d e d IOml o f d eio n ized w ater. A Beckm an pH m e te r a n d ATC (te m p e ra tu re p ro b e ) p ro v id e d pH values. The sam ples th e n sa t o v e rn ig h t to allow p a rtic u la te m a tte r to settle, a f te r w hich EC w as m e a s u re d w ith a p re c a lib ra te d cell. P e rc e n t clays p re s e n t in e ac h soil sam p le w ere d e te rm in e d using a h y d ro m e te r. Following th e m eth o d o u tlin e d b y Klute (1986), I vyeighed 40.0g of each sam ple in to a b eak er, a d d e d deio n ized w ater an d IOOmL o f HMP (Sodiumh ex am e ta p h o sp h a te ) so lution to d isp erse aggregates. A fter soaking o v ern ig h t, th e sam ples w ere m ixed fo r 5 m in u tes in a n electric m ixer, th e n tra n sfe rre d to a se d im e n ta tio n c y lin d e r w ith e n o u g h d e io n iz ed w ater to b rin g th e so lu tio n volum e to I lite r. Following a th o ro u g h m ixing w ith a p lu n g e r, I low ered th e h y d ro m e te r in to th e su sp e n sio n a n d re c o rd e d re a d in g s a t 30 seco n d s, 60 seconds, 1.5 h o u rs, a n d 24 h o u rs to calcu late th e p e rc e n t clay fractio n in each sam ple. 34 CHAPTER 3 DATA Each o f th e fo u r stu d y sites v a rie d slightly in e lev a tio n , m o rp h o lo g y , soil ch arac te ristic s a n d v eg etatio n . The follow ing d iscu ssio n com pares th e 0- IOcm a n d IO-ZOcm soil sam ples a t all sites, th e n h ig h lig h ts th e n a tu r e o f vegetation, soils, a n d trace m etals w ith in each m eadow . Copies o f the com plete d a ta set a re available fro m Dr. A ndrew M arcus, D e p artm en t o f E arth Sciences, M ontana State U niversity, Bozeman, MT 59717. Soil Sam ples Each soil sam ple was divided in to a O-IOcm sam ple a n d a IO-ZOcm sam ple. For each o f th e five trace m etals, a W ilcoxon Signed Ranks T est show ed th a t th e m e an levels w ere significantly h ig h e r (p= 0.000) in the 10 - ZOcm subsam ples (Table Z). Table Z. C om parison o f m eans, s ta n d a rd deviations a n d ra n g e s of trace m etals a t O-IOcm a n d IO-ZOcm d ep th s in fo u r m eadow s along Soda Butte Creek.________ TRACE METAL ■ ARSENIC ppm COPPER ppm IRON % LEAD ppm ZINC ppm n MEAN O-IOcm 13.77 152.35 • 3.79 42.73 104.83 269 STDDEV O-IOcm 13.45 107.44 1.10 26.93 44.77 269 RANGE O-IOcm 2 -7 2 ' 25-668 2.4-9.2 14-190 50-432 269 MEAN 10-2 0cm 18.8 203.48 4.24 54.4 133.22 125 STD DEV 10-2 0cm 2 1 .0 4 183.70 1.37 43.72 • 88.87 125 RANGE• 10-2 0cm 2-118 31-1143 2.6-9.3 8-270 5 0 -5 9 8 125 35 A P earso n C orrelation, how ever, show s th e trace m e ta l levels a t th e two d e p th s h a d c o rre la tio n coefficients ran g in g fro m r=0.73 to r= 0.76, in d icatin g a close association betw een m etal co n ce n tra tio n s a t d iffe re n t d e p th s. Due to this close asso ciatio n , th e fa c t th a t IO-ZOcm sam ples w ere n o t av ailab le fo r o v e r h a lf th e q u a d ra ts b e ca u se o f shallow soil p ro files, a n d th e a ssu m p tio n b y vario u s a u th o rs th a t th e top IOcm o f soil c o n tain 65% o f th e to tal ro o t biom ass (B artos a n d Sim s, 1974; M ilchunas a n d L a u e n ro th , 1989), I u sed th e soil c h a r a c te ris tic s fro m th e O-IOcm la y e r f o r th e m a jo r ity o f s ta tis tic a l com parisons in th e follow ing ch ap ters. Box p lo ts of arsenic, copper, iron, le ad , a n d zinc levels a t th e fo u r m eadow sites illu s tra te th e ra n g e o f trace m etal levels w ithin each site fo r th e O-IOcm soil sam ples (Figure 9). Study Sites Fish M eadow T he v e g eta tio n in Fish M eadow (Figures 2 a n d 3) is c h a ra c te riz e d b y species w hich flo u rish in w e tte r h a b ita ts. Mosses, Tuncus b a ltic u s. C arex s p ., a n d E q u ise tu m v a r ie g a tu m w ere th e first, second, fo u rth , a n d sev en th m o st fre q u e n t species, as d e te rm in e d b y th e p e rc en ta g e o f p lo ts w ith each sp ecies. The o th e r six m o st fre q u e n t species in d escen d in g o rd e r w ere A ster h e sp e ris. T r if o liu m r e n e n s . P h le u m n r a t e n s e . A n te n n a r ia a n a p h a l o i d e s . T r if o liu m lo n g ip es. a n d Poa p ra te n s is . Fish M eadow is th e only site w h ere I d id n o t fin d A g ro n v ro n so . The n u m b e r o f d iffe re n t species in in d iv id u a l q u a d ra ts ra n g e d fro m th re e to tw elve (Table 3). T h e ra n g e o f e le c tric a l c o n d u c tiv ity v a lu es fa ll w ith in a n o rm a l s p e c tru m fo r n o n -s a lin e soils (B rady, 1990), a n d th e p e rc e n t clay v a lu es Cl 30- S 20- Figure 9. 300 200 - Box plots of As, Cu, Fe, Pb, and Zn at study sites along Soda Butte Creek. Center line is median, center square is mean, top and bottom edges of box are 25th and 75th quartiles, ends of whiskers are 10th and 90th quartiles. meadow, H-Hollywood Meadow, I-Icebox Meadow, R-Round Prairie. F-Fish Table 3.. M ean, sta n d a rd deviation, a n d ran g e of vegetation, soil (0-1 Ocm), a n d m etal variables in Fish Meadow (FISH), Hollywood M eadow (HLYWD), Icebox M eadow (ICEBOX), an d Round Prairie (RNDPR), along Soda Butte Creek, MT a n d WY V A R IA B L E Poa so. Densityd' FISH 1.87 M EAN HLYWD ICEBOX RNDPR NA 8.02 4.56 STA N D A R D DEVIATION FISH HLYWD ICEBOX RNDPR NA 3 .4 8 7.70 4.15 FISH 0-17 RA N G E HLYWD ICEBOX 0-30 0-18 RNDPR NA Bromus so. Density Asroovron so. Density Phleum oratense Density .11 .45 .35 .23 .53 1.40 2 .3 8 .92 0-3 0-9 0-19 0-7 O .47 .15 .02 0 1.47 .71 .14 0 0-9 0-5 0-1 .8 9 2.51 3.46 3.81 1.64 2 .8 9 3 .4 2 3.97 0-5 0-12 0-16 0-27 Biomass (gK #Species/plot (S) Diversity Index .170 .46 .84 NA 1.14 NA 0-5.39 . NA 8 .3 7 1.71 7.26 1.72 3.10 0 .8 2 2.48 0.61 NA NA 2-12 0.312 .8 6 NA NA (DMs)O % Clay 0 -1 .2 7 8 3-12 0.443.06 0-4.31 NA NA .3 3 6 2.32 0.57 .70 7.47 1.71 18.88 14 20.51 14.5 8.54 8 .7 3 10.23 7.10 pH 9 6.46 5.89 7.22 6.40 4.44 .59 7.58 .5.8855.58 4.5-7.74 Salinity (dS/m) 1.6947.78 3.757 ,9 6 .48-3.21 2 -7 2 2 .3 8 41.44 6.757.58 .47-1.85 2-24 59-668 2^869,18 20-190 66-432 25-483 2.45- 6.96 14-116 52-214 Arsenic (Ppmlfi Copper (ppm) Iron (%) 1.16 15 .9 8 18 2.9 21 1.00 5 .2 6 12 .53 16 1.40 12 .25 5 5.8149.75 5.647.16 .73-1.94 2-54 234 4.38 209 4.27 149 3 .8 8 73 3.08 113 .99 101 1.27 102 1.18 30 .30 50-535 2.69-7.3 Lead (ppm) Zinc (ppm) 49 126.0 53 121 55 119 23 72 20 45 35 53 24 6 16 4.94 ■ 38 - 18-116 66-272 0-13 0-3.49 ' .22-6.03 ■2-48 32-206 2.43-4.1 14-52 50-134 65 . 76 76 101 46 101 . n (# of quadrats) 46 65 46 76 65 101 o' Density - Number of culms per quadrat J5 Above-ground biomass of Phleum pratense O Margalefs Diversity Index (Magurran, 1988) DMg=(S-I)Zln N where S=#species/plot and N=total # of individuals of all species/plot 5 pH values converted from mean and standard deviation of proton activity levels si All trace element levels are total metal concentrations 38 a p p ro x im a te th e p e rc e n t clay values fo u n d in th e o th e r m ead o w sites. T he pH levels in Fish M eadow in d icate th e p resen ce o f m o d e ra tely acid soils. T race m etal levels in Fish M eadow exceed b a c k g ro u n d levels in Soda Butte Creek floodplains (M eyer, 1993) and. M axim um A cceptable C o n cen tratio n s (MAC) fo r a g ric u ltu ra l soils (K abata-Pendias a n d Pendias, 1992). This m ead o w h a d th e h ig h e st m e a n co n ce n tra tio n s o f co p p er, iro n , a n d zinc, alth o u g h p eak c o n ce n tra tio n s fo r th ese elem ents o c cu rred in Hollywood M eadow (Table 3). Hollywood M eadow T he p la n t species in Hollywood M eadow (Figures 2 a n d 4) are sim ilar to th o se in Fish M eadow , a lth o u g h th e fre q u e n c y ra n k s d iffer. The te n m o st fre q u e n t species in H ollyw ood M eadow (fro m h ig h e r to lo w er freq u en cies) in c lu d e P oa n ra te n s is . m osses, T rifo liu m re p e n s . A ster h e s o e riu s . A n te n n a ria a n a p h a lo id e s . Tuncus b a ltic u s . T rifo liu m lo n e ip e s. F r a e a ria v e sc a . C arex s p .. a n d A goseris e la u c a . The soils in Hollywood M eadow in clu d e som e stro n g ly acid soils, w ith pH values as low as 3.75 (Brady, 1990). All o f th e q u a d ra ts h a v e n o n -salin e soils. The ra n g e o f clay values is sim ilar to th e o th e r m eadow sites (Table 3). T race m etal levels in H ollyw ood M eadow in c lu d e a m o re ex ten siv e ra n g e th a n th e o th e r sites, in c lu d in g th e h ig h e st c o n ce n tra tio n s of each tra c e m e ta l fo u n d an y w h ere in th e stu d y sites. Icebox M eadow Icebox M eadow (Figures 2 a n d 5) co n tain s species th a t a re also fo u n d in Fish M eadow a n d H ollyw ood M eadow . T he te n m o st fr e q u e n t species in d e sc e n d in g o r d e r w ere T r ifo liu m r e p e n s . P o a n r a t e n s i s . Tuncus b a l t i c u s . 39 A n te n n a ria a n a p h a lo id e s . F ra s a ria vesca. P h leu m e r a te n se . C arex so ., m o sses, A ster h e sp e riu s. a n d E guisetum v a rie s a tu m . Icebox M eadow soils d iffe r fro m th e o th e r m e a d o w sites in th e ir re la tiv e ly h ig h salin ity levels (T able 3). T he m e an EC is still n o n -salin e, b u t several q u a d ra ts h a v e EC values above 4.0 d S /m , th e in d ic a to r value fo r saline soils (M ontagne, 1984). P ercent clay valu es p arallel th e ra n g e o f values fo u n d in th e o th e r m eadow sites. pH levels ra n g e fro m 4.45 to 7.74, in d icatin g th e p resen ce o f strongly acid, m o d e ra tely acid, a n d n e u tra l soils (Brady, 1990). Icebox M eadow h a d th e h ig h est m e an co n cen tratio n s o f le ad a n d a rse n ic am ong th e fo u r m eadow s a n d som e q u a d ra ts h a d trace m etal levels reach in g o r exceeding MAC (K abata-P endias a n d Pendias, 1992). M ean tra c e m etal levels exceed b a c k g ro u n d tra c e m e ta l levels in th e Soda B utte C reek flo o d p la in (M eyer, 1994). R ound P rairie D ue to tim e c o n strain ts on th e field season, I d id n o t com pile a com plete species list fo r R ound P rairie (Figures 2 a n d 6). The v e g eta tio n d a ta th a t was collected fo r th is site in d ic a te s th a t P h le u m p r a te n s e was p re s e n t in g re a te r densities th a n a t th e o th e r sites (Table 3). Soil c h arac te ristic s in R ound P rairie re fle c t a "norm al" ra n g e o f values. P e rc e n t clay levels v a ry like th e o th e r m ead o w sites, pH le v e ls in d ic a te p re d o m in a n tly n e u tra l soils, a n d EC values a re all no n -salin e (Table 3). In term s o f tra c e m e ta l levels, m e a n c o p p e r a n d le a d levels ex ceed b a c k g ro u n d levels, as d o som e o f th e p e a k arsen ic a n d zinc levels (M eyer, 1994). A rsenic, c o p p e r, le ad , a n d zinc levels also fall w ith in c o n se rv a tiv e estim ates o f MAC (K abata-Pendias a n d Pendias, 1992). 40 CHAPTER 4 DATA ANALYSIS This s tu d y e v a lu a te s w h e th e r g ra ss sp ecies d iv e rs ity , d e n sity , a n d biom ass: (I) d ecrease as tra c e m etal co n ce n tra tio n s in crease; a n d (2) d ecrease as soil pH d e creases. In o rd e r to assess th e ro le o f e n v iro n m e n ta l v a ria b les u n re la te d to m in e tailings, I also e v a lu a te d w h e th e r grass species d iv e rsity , d e n sity a n d biom ass: (I) v a ry w ith soil clay c o n ten t a n d salinity; (2) v a ry as a fu n c tio n o f d ista n ce fro m th e stre am c h a n n e l o r elev atio n ab o v e th e ch an n el; o r (3) ch an g e in th e d o w n stream d ire c tio n . This c h a p te r p re se n ts a n an aly sis of th e d a ta to answ er these questions. T he v ariab les exam ined in this stu d y d o n o t h av e n o rm a l d istrib u tio n s, w ith th e ex ce p tio n o f d is ta n c e fro m s tre a m c h a n n e l a n d e le v a tio n a b o v e stre a m c h a n n e l. T he soil a n d tra c e m e ta l v a ria b le s in p a rtic u la r te n d to in c lu d e o u tliers. In a d d itio n , th e p a tc h y d istrib u tio n o f m in e tailings im p lie s th a t s p a tia l a u to c o r r e la tio n co llin e arity . statistics. ex ists a n d so m e o f th e v a ria b le s d is p la y T he d a ta th u s v io late m a n y o f th e a ssu m p tio n s o f p a ra m e tric Given th e n a tu re o f th e d a ta co llected fo r th is stu d y , m uch o f th e a n aly se s th e re fo re u tilize d e sc rip tiv e statistics a n d d ire c t g ra d ie n t a n aly sis (Gauch, 1982) o r n o n p a ra m etric tests (Daniel, 1990). S catterplots w ere u sed to d e m o n stra te th e re la tio n betw een in d e p e n d e n t v a ria b le s a n d v e g eta tio n . Specific sc a tte r p lo ts w ere sm o o th e d u sin g S u p er Sm ooth to h e lp w ith d a ta in te rp re ta tio n (V enable a n d Ripley, 1994). In o rd e r 41 to m o re p re c ise ly id e n tify th e th re s h o ld p o in t w h ere d iv e rsity , d e n sity , o r b io m a ss d e c lin e d , I u s e d p lo ts o f c u m u la tiv e d e v ia tio n s fro m th e m e a n d e p e n d e n t v a ria b le . T h resh o ld s o n th e se p lo ts a re show n b y shifts in th e cum ulative d eviations th a t a re consisten tly below o r above th e overall m ean. A CuSum p lo t is c o n stru cte d b y so rtin g th e p a ire d x (e.g. p p m co p p er) a n d y (e.g., m e a n grass d ensity) v alu es fro m low to h ig h x, su b tra ctin g th e m e a n y v alu e fro m all y values, th e n co m p u tin g a n d p lo ttin g th e cu m u lativ e sum o f all th e d ev iatio n s fro m th e m e a n y, as x in creases fro m (Borkowski, 1995). x m in to Xm a x If th e re is n o th re s h o ld re la tio n sh ip , th e CuSum p lo t will v a cillate a ro u n d zero (th e p o in t w h ere a y v alu e e q u als th e m ean y). If a th re s h o ld re la tio n sh ip does exist, th e p lo t will show a n u p w a rd o r d ow nw ard tre n d in re la tio n to th e m e an y, follow ed b y a rev erse o r p la te a u of th a t tre n d . R elationship o f Trace M etals a n d V egetation T he tra c e m e ta l c o n c e n tra tio n s fro m all fo u r m e ad o w sites (T able 4) fre q u e n tly exceed M axim um A cceptable C o n cen tratio n s fo r a g ric u ltu ra l soils (K abata-P endias a n d Pendias, 1992). This suggests th a t tra c e m etals m ay affect v e g eta tio n div ersity , d en sity , a n d biom ass, as h y p o th e siz e d .. S catterp lo ts a n d cum ulative d eviation plots a re u sed h e re to d eterm in e if im p acts do occur. Table 4. T race m etal concen tratio n s along Soda Butte Creek, MT a n d WY in re la tio n to suggested m axim um trace m e tal levels.________________________ TRACE METAL BACKGROUND LEVELS* MCLAREN TAILINGS PILE* FLOODPLAIN SOILS (0-2 0cm) MAC in Ag • Soils§ Arsenic (ppm) <10 37-97 2-118 2-50 Copper (ppm) 29-37 20-140 841-12,600 25-1143 NA Iron (%) 4.8-5.0 11.7-26.1 2.4-9.3 Lead (ppm) 11-13 71-672 20-500 8-270 Zinc (ppm) 70-400 63-69 120 50-598 * Trace metal levels of historic floodplain terraces and McLaren tailings (Meyer, 1993) § Maximum Acceptable Concentration (MAC) in agricultural soils as given by various authors in Trace Elements in Soils and Plants (Kabata-Pendias and Pendias, 1992) 42 D iv ersity T he re la tio n s h ip betw een b io d iv e rsity a n d tra c e m etals offers in sig h ts a b o u t th e im pacts o f trace m etals on th e v egetation co m m u n ity as a whole. The M argalef D iversity Index (DMg) m easu res d iv ersity w ith a ra tio o f th e n u m b e r o f d iffe re n t species a n d th e a b u n d an c e o f all species in a plot: DMg = S -l/ln N w here S=total n u m b e r o f species p e r p lo t a n d N=total n u m b e r o f in d iv id u als of all species p e r p lo t (M agurran, 1988). ) Plots o f DMg a n d tra c e m e ta l lev els in d ic a te th a t th e tra c e m etals d o affect d iv ersity . A sc a tte r p lo t o f DMg in re la tio n to c o p p e r levels rev eals a w ide ra n g e of d iversities up to SOOppm co p p er, a t w hich p o in t th e v a ria tio n in d iv ersity a p p e a rs to decline (Figure 10). A lthough th e sc a tte r p lo t alo n e d o e s n o t re v e al clear tre n d s, th e o v erlay o f sm o o th ed d a ta p o in ts shows a n o v erall d eclin e o f d iv e rsity in re la tio n to in c re a sin g c o p p er levels. The s m o o th in g ro u tin e u sed looks fo r overall tre n d s in th e d ata, b u t is flexible enough to pick u p a b ru p t changes in th e d a ta (V enable a n d R ip ley ,. 1994). D iversity le v e ls v a ry slig h tly b etw een 120 a n d SOOppm c o p p er, b u t d e c lin e stea d ily a b o v e S lS p p m c o p p er (Figure 10). A CuSum p lo t o f DMg in re la tio n to c o p p er levels shows th e sam e p a tte rn as th e sm o o th ed d a ta . The cum ulative tre n d s rev eal th a t d iv e rsity levels a re above th e m ean o r vacillating a ro u n d th e m e an u n til th e cu m u lativ e d ro p in d iv e rsity above S lS p p m c o p p er (Figure 10). D iversity also a p p e a rs to d eclin e above 2 2ppm arsenic, 4.2% iron, 65p p m lead, an d 17Oppm zinc (Figure 11). 43 3 .5 - ----------B-----□ 3 n I a n □ I T SrO 3 rV □ % =P 3 . n l QQ r*□ @ - C □ □ — a = Smooth ■ * * * • • □ □ □ □ 5 □ n cP • LI □ =Bn DMg a =Jnr^ a ***** — 3 D □ ] □ = = --------C------- C D D □ □ □ D C% t II — I D D n S 1 □ B [ 35 II . Oc; — Q I 3 a O □ ----------- rB---- 0- O 100 200 300 400 500 600 TOO Fish, Hollywood, and Icebox Meadows - Copper (ppm) 12.00 O) Z % Q ? 5 5 6e 5 IO -F 10.00 ■ 8 .0 0 -H- / 6 .0 0 - C 0 1 II 4.00- 2.00 3E O * * -F rtr I DMg S t* 4- -F -------iF--------- 9 * * + * -F -F -F 0.00 100 200 300 400 600 700 Fish, Hollywood, and Icebox Meadows - Copper (ppm) Figure 10. S catter p lo t o f DMg (M arg alefs D iversity Index) a n d c o p p er levels w ith a n o v e rla y o f s m o o th e d d a ta p o in ts a n d CuSum p lo t o f c u m u la tiv e d e v iatio n from m e an d iv e rsity (DMg) in re la tio n to c o p p er levels along S o d a Butte Creek. Cumulative Deviation from Mean Diversii £■14.00 gI 12.00 1 10.00 5 E 8.00 S 6.00 C § •2 4.00 Sa, 2.00 I 0.00 I -2.00 2.00 3.00 4.00 5.00 6.00 7.00 8,00 9.00 10.00 Cumulative Deviation from Mean Diversity Iron (%) £ . 10. 0 0 - I 5 3 8 . 00 - C 8 5 6.0 0 - I DMg Sm |§ c M n j - _B___ B D c 4.00- 0 ! S 2.°0 1a D D □ D 0.00- 3 E 3 ° D 3 D r-C U I - 2.00 0 50 100 150 200 250 300 350 400 450 Zinc (ppm) Figure 11. CuSum plots of the cumulative deviation from the mean diversity (DMg) as calculated for Fish Meadow, Hollywood Meadow, and Icebox Meadow. 45 D ensity D ensities w ere n o te d fo r 33 species o f grasses a n d fo rb s in th e m ead o w sites (Table 5). P h le u m p ra te n s e a n d P oa p ra te n s is p ro v id e a good p o rtr a it o f ov erall grass re sp o n se to tra c e m e tals b e ca u se b o th o ccu r fre q u e n tly in th e stu d y sites along Soda Butte Creek. C opper was u sed to exam ine re la tio n sh ip s betw een d e n sity a n d tra c e m etals b ecau se it is a clear in d ic a to r o f th e m in e tailings (M eyer, 1993), a n d c o p p e r levels c o rre la te well w ith th e o th e r tra c e m etal levels. S catter p lo ts o f P h le u m p r a te n s e a n d Poa p ra te n s is d en sities in re la tio n to c o p p er levels show w ide v a ria tio n in d e n sity levels u p to 2 5 Oppm c o p p er, a t w hich p o in t a th re s h o ld is p a sse d a n d m e a n d e n sitie s d e c re a se (Figure 12). S c a tte r p lo ts fo r th e d e n sity o f th e o th e r grasses in re la tio n to c o p p er levels show a sim ilar p a tte rn . Using CuSum p lo ts to look fo r a th re sh o ld p o in t in c o p p e r levels reveals a d istin c t d ro p below th e m e an a t 2 IG ppm co p p er fo r P h leu m p ra te n se d e n sity a n d a t 2 3 Gppm c o p p e r fo r Poa p ra te n s is d en sity (Figure 13). CuSum p lo ts of P h le u m p r a te n s e d e n sity in re la tio n to th e o th e r fo u r tra c e m etals show a sim ilar th re s h o ld p a tte rn . S catter p lo ts o f all 33 species in d ic a te th a t, o n average, species ex h ib it a th re sh o ld to le ra n c e fo r c o p p er n e a r 2 50ppm . W hen th e d e n sity d a ta fo r each species is d iv id e d in to d e n sities ab o v e a n d below 2 5 Oppm a K ruskal W allis m ean s te st in d icates th e species w hich show re d u c e d d en sity . The d a ta violate th e K ruskal-W allis a ssu m p tio n o f in d e p e n d e n t o b s e rv a tio n s a n d id e n tic a l p o p u la tio n s (D aniel, 1990), th erefo re, o n ly v e ry sm all P v alu es (p<=0.001) will be co n sid e re d significant. Based on this d a ta sep aratio n , P h leu m p ra te n se . Poa p ra te n s is a n d Tuncus b a ltic u s d e n sity a re significantly d iffe re n t (Table 5). 46 T able 5. K ruskal Wallis com parison o f m e an species d en sity o n plots w ith h ig h (C u>250ppm ) a n d low (C u<250ppm ) levels of copper, fo r all grasses a n d forbs in c lu d e d in th e M argalef D iversity Index. T h ere w ere 4 9 p lo ts w here c o p p e r levels e x ce e d ed 2 5Oppm a n d 114 p lo ts w h e re c o p p e r levels w ere less th a n 250ppm. Species List A c h ille a s p p . A g o se ris glau ca A g ro p yro n spp. A n g e lic a s p p . A n te n n a ria a n a p h a lo id e s A s te r h e s p e r iu s A stra g a lu s sp p . B ro m u s s p p . C arex s p p . C era stic u m sp p . C irsiu m sc a rio su m D e sc h a m p sia c e s p ito s a E p ilo b iu m a n g u stifo h u m E q u isetu m v a rie g a tu m F ragaria v e sc a G en tia n a d e to n s a Ju n cu s b a ltic u s M u h le n b e rg ia filifo r m is P e d ic u la ris s p p . P h leu m p r a te n s e Poa ju n c ifo lia Poa p r a te n s is P o te n tilla sp p . Saxifraga s p p . I S axifraga s p p .2 S e n e c io cra ssu lu s S m ilacin a sp p . T araxacum s p p . T rifo liu m lo n g ip e s T rifo liu m r e p e n s T rigloch in m a r itim u m V ero n ica s p p . V iola s p p . AVERAGE DENSITY DENSITY p values DENSITY Cu > 2 5 Oppm Cu < 2 5 Oppm 0.14 0.00 0.19 0.058 0.10 0.012 0.48 0.65 0.20 0.00 0.011 0.2-8 0.14 0.25 0.123 0.49 4.45 .3,84 4.72 0.373 1.72 0.092 1.35 1.88 0.487 0.40 0.10 0.53 0.36 0.20 0.43 0.961 1.54 1.37 1,61 0.759 0.04 0.02 0.615 0.05 . 0.050 0.11 0.02 0.15 0.512 0.01 0.00 0.01 0.470 0.15 0.08 0.18 14.87 0.045 11.73 4.43 0.095 1.11 0.98 0.69 0.07 0.02 0.09 0.348 31.24 11.28 0.000 17.28 0.22 0.281 0.25 0.33 0.10 0.18 0.15 0.628 1.42 3.49 0.000 1.79 0.14 0.20 0.138 0.00 0.001 2.80 6.35 5.28 0.04 0.353 0.00 0.03 0.127 0.04 0.00 0.01 0.02 0.02 0.901 0.02 0.221 0.47 0.58 0.55 0.04 0.353 0.03 0.00 0.087 0.02 0.12 0.09 3.18 0.603 2.95 2.43 0.348 13.22 11.96 13.76 0.02 0.04 0.01 0.531 0.127 0.02 0.00 0.01 0.02 0.512 0.01 0.00 Density (Phleum pratem 47 A .-V a'-MA, A A i AAi /XfvAlV ' AR. VvAA AAA AKA.. \A A A A A AZA AA , AAAAAA AAAAAA A AA A A A .-./'yWA' A A A /A A AA A A Density (Poagrgjtensjs) Soda Butte Creek - Copper (ppm) OO 0 0 # " » OO- O- O O OOOO OO J S W U -rv OU -SO C- -O—O- :: : i c:HM # Soda Butte Creek - Copper (ppm) Figure 12. S c a tte r p lo t o f c o p p e r levels in re la tio n to d e n sity of P h le u m p ra te n se an d Poa p ra te n sis along Soda Butte Creek. 48 L I6 I ^I _ll I : 1 I tr 100 " £ \ O _________ % cu & £ C S Z P h le u m p r a t e n s e I 40 O 0 O O V O 0 > O O 0 3 E ° -20- I O 100 200 300 400 500 600 700 Soda Butte Creek - Copper (ppm) 160-1 I SI § I4U I 120 Il y # # 100 I I I I B I > O 3 ‘f 80 «=- % O P o a p ra te n s is % L % * « - 40 20 * 0 3 U » OO * . -4 0 - 0 e 100 200 300 400 500 600 700 Soda Butte Creek - Copper (ppm) Figure 13. CuSum p lo ts o f cum ulativ e d e v iatio n s fro m th e m ean d e n sity in re la tio n to c o p p er levels fo r P hleum p ra te n s e an d Poa p ra te n s is . 49 Both Phleum p ra te n se a n d Poa p ra te n sis h a d lower den sities on th e plots w ith c o p p er levels above 25Oppm, a n d Tuncus b a lticu s h a d h ig h e r d e n sity on th e high c o p p e r p lots. A lthough th e o th e r species d id n o t show significant differences in d en sity a t the 0.001 level, a to tal of 26 of th e 33 species listed h a d low er m e an d e n sitie s o n th e h ig h c o p p e r plots. T he c o m b in a tio n o f th e sm aller n u m b e r o f plots w ith high c o p p e r levels, th e re la tiv e ra rity of m an y species o n th e list, a n d th e rig o ro u s statistical c rite ria m ay p ro v id e a p a rtia l ex p lan a tio n for th e lack o f significant d ifferen ces. Biomass I collected th e a b o v e -g ro u n d bio m ass o f P h le u m p r a te n s e from Fish, H ollywood, a n d Icebox M eadows. S catter p lo ts of biom ass in re la tio n to trace m etals show th re sh o ld relatio n sh ip s w ith c o p p er (Figure 14). S catter p lo ts fo r biom ass a n d th e o th e r trace m etals w ere sim ilar. In a d d itio n , using a th re sh o ld v alu e o f 2 5 Oppm to d iv id e th e d a ta , th e K ruskal W allis c o m p a ris o n of m eans in d ic a te d th a t n o n - p a r a m e tr ic P h l e u m p r a t e n s e b io m a s s w as significantly d ifferen t above a n d below th e co p p er th re sh o ld (p<=0.001). 6 □ c O , 4 □ Biomass □ □ □ 3 ^ v» O E O □ Si q 3 I5 . „ □ C d d E 3 0) □ C 2 I ' ^ Dr ^ D , Dg ^ D ? lD [ ^ n ____________________________________________________ .C Q- 0 -' 0 liux-j u i u h u i - i ^ 100 200 ----------------- 300 — rT n, rnr a rn^— a□ I, 400 o -------------------,----------------a— I 500 600 700 Fish, Hollywood, and Icebox Meadows - Copper (ppm) Figure 14. S catter plo t of Phleum p ra te n se biom ass in re la tio n to co p p er levels. 50 RelationshiD o f Soil C h aracteristics a n d V egetation SR pH levels along Soda B utte C reek a re as low as pH 3.4, m ark in g th e p re sen c e o f stro n g ly acid a n d m o d e ra te ly acid soils. T hese low pH levels also c o rre sp o n d som ew hat w ith d e c re a se d grass d iv ersity , a n d m o re c learly w ith d en sity a n d biom ass. D iv e rs ity : As w ith th e s c a tte r p lo t o f d iv e rsity in re la tio n to c o p p e r levels, th e s c a tte r p lo t o f d iv e rsity in re la tio n to pH d o e s n o t p ro v id e a n im m ed iate p ic tu re o f tre n d s in th e d a ta (Figure 15). H ow ever, th e o v erlay o f sm o o th e d d iv e rsity d a ta show s a n o v erall in c re ase in d iv e rsity as pH levels increase. The exception to this tre n d is a d ecrease in d iv e rsity betw een pH 6.4 an d pH 6.6. T he CuSum co m p ariso n o f d iv ersity (DMg) a n d pH shows d iv ersity levels slightly above th e m e an a t pH 4.0 (Figure 15). However, th e overall tre n d fro m pH 4.0 to pH 6.2 shows diversity levels below- th e m ean. From pH 6.2 to pH 6.5, d iv e rsity levels in c re ase above th e m ean , as seen in th e o v e rla y o f sm o o th ed d iv ersity d a ta. D iversity levels fall below th e m ean d iv ersity level fro m pH 6,5 to pH 7.0. Above pH 7.0, d iversity levels in crease steadily. D e n s i t y : A s c a tte r p lo t o f P o a p r a t e n s i s d e n sity in re la tio n to pH illu stra te s th e th re sh o ld p a tte rn , w ith m e a n d en sity in creasin g betw een pH 6.0 a n d pH 6.5 (Figure 16). A cum ulativ e su m o f d ev iatio n s p lo t shows d e n sity levels below th e m e an fro m pH 3.5 to pH 7.15 arid in creasin g above th e m e an fro m pH 7.15 to pH 8.0 fo r P h le u m p r a te n s e . D ensity levels o f Poa p ra te n s is also fall below th e m e a n d en sity level fro m pH 3.5 to pH 7.1, th e n c o n tin u ally in crease above th e m ean(F igure 17). 51 3 .5 - o> Q □ □ □ 3 □ □ 3 n ' n n SC 1 □ d [3 0 5 S : D ^ □ O Z n =O □Q] c *□ □ □ * • B □ LI ff- □ □ n □ 100 □ □ □ SD ----------- S---- 0 • □ D CP O Smooth □ □ =T=L B B I1 D ] • □ □ % 3 H J 15J _____i? U $ §> hr d □ - I O DMg O'",--- r— 200 300 400 500 600 TOO Fish, Hollywood, and Icebox Meadows - Copper (ppm) 12.00 oi 5 f; #-*■ io .oo 44- . c 8.00 ________ g 5 I £% -H6.00 I 5 S E* 4- 4* * 1 * O 0 1 \ DMg •P I * 4 'r o 2.00 E 3 O 0.00 0 4- ** J♦ 44* 4- * 4-------T-------4- 4- 4* 4- 4100 200 300 400 500 600 700 Fish, Hollywood, and Icebox Meadows - Copper (ppm) Figure 15. S catter plo t of M arg alefs D iversity Index (D m 8) a n d pH levels, w ith a n o v e rla y o f s m o o th e d d iv e rsity d a ta a n d CuSum p lo t o f th e c u m u lativ e d ev iatio n from m ean d iv e rsity (DMg) in re la tio n to soil pH fo r th e co m b in ed d a ta from Fish, Hollywood, an d Icebox Meadows. 52 Figure 16. S catter plo t of pH in relatio n to d en sity of Poa p ra te n sis along Soda Butte Creek. W hen a pH th re sh o ld of pH 6.4 was u sed to gro u p th e d ata, eighty-tw o p e rc e n t o f th e p lo ts w ith low pH levels w ere also in th e h ig h c o p p er su b set. T he o n ly species w ith a sig nifican t d ifferen c e (p<=0.001) in d en sity using a Kruskal-W allis co m p ariso n of m eans was Tuncus balticus (Table 6). As w ith th e c o p p e r co m p ariso n , Tuncus b a ltic u s d e n sity was h ig h e r o n th e low pH p lo ts th a n on th e h ig h e r pH plots. A lthough o n ly o ne species show ed a significant differen ce in d en sity , 22 o f th e 33 grasses a n d forbs h a d h ig h e r m ean d e n sity on th e h ig h e r pH plots. The lack of sig n ifican t d ifferen ces in v eg etatio n m ay relate to th e small sam ple size of th e pH<6.4 group (n=28 v ersu s n=135), o th e r e n v iro n m e n ta l factors, a n d th e rigo ro u s statistical c rite ria used. Cumulative Deviation from Mean Density (Phleum pr 53 O P h le u m p r a t e n s e Cumulative Deviation from Mean Density (Poa pratensis) Soda Butte Creek - pH O P o a p ra te n s is Soda Butte Creek - pH Figure 17. CuSum plots of cum ulative d ev iatio n s from m ean d en sity in relatio n to pH levels for P hleum p ra te n se an d Poa p ra te n sis . 54 Table 6. K ruskal W allis co m p ariso n o f m e an species d e n sity o n plots w ith low (pH<6.4) a n d h ig h (pH>6.4) pH levels, fo r all grasses a n d fo rb s in clu d ed in th e M argalef D iversity Index. T here w ere 28 p lo ts w ith pH <6.4 a n d 135 plots w ith pH>6.4. Species List Achillea, spp. Agoseris glauca A gropyron spp. Angelica spp. A ntennaria anaphaloid.es A ste rh e sp e riu s Astragalus spp. Brom us spp. Carex spp. Cerasticum spp. Cirsium scariosum D escham psia cespitosa Epilobium angustifolium E quisetum variegatum Fragaria vesca G entiana detonsa Juncus baltieus M uhlenbergia filiform is Pedicularis spp. Phleum pra ten se Poa juncifolia Poa pratensis Potentilla spp. Saxifraga spp. I Saxifraga spp.2 Senecio crassulus Sm ilacina spp. Taraxacum spp. Trifolium longipes Trifoliitm rep en s Triglochin m a ritim u m Veronica spp. Viola spp. AVERAGE DENSITY DENSITY p values DENSITY pH < 6.4 pH >= 6.4 0.14 0.00 0.16 0.188 0.04 0.48 0.58 0.060 . 0.20 0.00 0.24 0.076 0.54 0.25 0.482 0.19 4.45 5.46 4.24 ' 0.252 1.72 1.46 1.77 0.979 0.07 0.40 . 0.47 0.401 0.36 0.18 0.40 0.782 1.54 1.39 1.56 0.885 0.04 0.04 0.04 0.871 0.11 0.07 0.12 . 0.321 0.01 0.00 0.01 0.648 0.07 0.17 0.532 0.15 11.73 4.25 13.28 ' 0.107 1.04 . 0.98 0.720 0.98 0.07 0.00 0.08 0.220 29.89 14.67 0.001 17.28 0.07 0.25 0.196 0.29 0.15 0.04 0.18 0.216 2.27 1.79 ■ 3.03 0.391 0.14 0.00 0.17 0.303 5.28 2.46 5.87 0.018 0.04 0.03 0.00 0.519 0.01 0.00 0.01 0.648 0.02 0.04 0.01 0.455 0.57 0.54 0.55 0.315 0.04 0.03 0.00 0.519 0.987 0.09 0.11 0.09 2.95 3.61 2.81 0.224 13.22 12.24 17.96 0.053 0.02 0.02 0.00 0.519 0.04 0.01 0.00 0.028 0.01 0.00 0.01 0.648 55 B iom ass: S catter plots o f a b o v e-g ro u n d biom ass o f P h le u m p ra te n s e in re la tio n to pH show a th re s h o ld p a tte rn w hich m a tch es th e tre n d s seen in density, w ith decreased biom ass below pH 6.5 (Figure 18). O □ S 5 □ Biomass □ o A 4 □ O V* C q J a. 2 I □ □ E A n nD Dn E ' 3 (LI Z £ I 1 o I—I Q 3.5 rrhJ 4 n 4.5 1— 1 5 f—i f—I m 5.5 r n r~i rrniiiBL 6 6.5 im i i i S i 7 lQ D 7.5 8 Fish, Hollywood, and Icebox Meadows - pH Figure 18. S catter plo t of Phleum p ra te n se biom ass in re la tio n to pH Salinity (EC) D iversity does n o t a p p e a r to v ary co n sisten tly as a fu n ctio n o f salinity. The c u m u lativ e d e v iatio n s from m ean d iv e rsity (DMg) in re la tio n to salin ity fluctuate above a n d below the m ean DMg, w ithout any co n sisten t tren d s (Figure 19). D iversity levels flu c tu a te abo v e a n d below th e m e an u p to 2.3 d S /m salinity. At 2.3 d S /m , d iv e rsity levels d ro p below th e m e an , th e n in c re ase again a t 3.0 dS /m . T he in crease in d iv ersity above 3.0 d S /m m ay in d icate th e p resen ce of salt-to le ra n t species (Brady, 1990). S alinity a n d d e n sity e x h ib it a w eak th re sh o ld re la tio n sh ip . A s c a tte r plo t o f P h leu m p ra te n s e d e n sity in re la tio n to salinity shows a slight d ecrease in av erag e d e n sity above 2.75 d S /m (Figure 19). resu lts in a sim ilar plot. Relating biom ass to salin ity 56 Cumulative Deviation from Mean Dlversl v DMg Density (Phleum pratense) Fish, Hollywood, and Icebox Meadows - Salinity (dS/m) Figure 19. CuSum plo t of th e cum ulative d ev iatio n s from m ean d iv ersity (DMg) in re la tio n to salinity, a n d sca tte r p lo t o f P h leu m p ra te n s e d e n sity in re la tio n to salinity. 57 P ercen t Clavs High c lay levels c an d e c re a se th e b io a v a ila b ility (K abata-P endias a n d Pendias, 1992). o f tra c e m e ta ls However, th e re is n o c lea r re la tio n sh ip betw een p e rc e n t clay a n d v eg etatio n c h arac te ristic s in th is study. A CuSum plo t o f d iv ersity a n d p e rc e n t clays shows D m 8 levels above a n d below th e m ean DMg from 0% to 20% clay (Figure 20). At 20% clay, DMg tre n d s above th e m ean as far as 23% clay, th e n vacillates above a n d below th e m ean. O) 5Q_ i 5 5 C § s E S O 0 1 V DMg I3 E 3 O - 10.00 Fish, Hollywood, and Icebox Meadows - Percent Clay Figure 20. CuSum p lo t of th e cum ulative deviations from m ean diversity (DMg) in re la tio n to p e rc e n t clay. Likewise, s tu d y re su lts in d ic a te d e c re a se d d e n sity a t high clay levels (F igure 21). T he e x p la n a tio n fo r th e se fin d in g s m ay re la te m o re to p la n t grow th re q u ire m e n ts th a n to tra c e m etal availability. 58 30-. A A Phleum pratense 5 20 I A iD 15< lu AA ^ in A A A A A “ AA A ZA A A A AAA A Li AIAAA A-ZKVw A A AAA A A AAZ A A "A&,m~ ZA zzzf CL A A AA Aa AAAZAA Z A j W , / \ A A A A AAAA A , A , A A V V Y W i YY Al 1k/V\AAAZAAA VZA , ICA A A ZA A A TyA AA/tifcA- ^A1 AZ,/ |A; ■' A AAQA*; I 5 o 0 10 20 A A 30 O A 50 60 Soda Butte Creek - Percent Clays Figure 21. S catter p lo t of Phleum p ra te n se d en sity in re la tio n to p ercen t clays. M ultiv ariate A nalysis B ecau se s e v e ra l of th e c o n tr o l v a r ia b le s d is p la y c o llin e a r ity (p a rtic u la rly pH a n d trace m etals), it is difficult to allocate "responsibility" fo r v ariatio n s in an y one resp o n se v ariab le to o n e control v ariab le. I used logistic reg ressio n to assess th e p o te n tia l im p o rtan ce o f the d iffe re n t co n tro l v a ria b les (i.e. tra c e m e ta l c o n c e n tra tio n s , soil p a ra m e te rs ) in d riv in g v a ria tio n s in grasslan d com position. Logistic reg ressio n uses p re se n c e /a b se n c e d a ta fo r the d e p e n d e n t v a ria b le a n d ev alu a te s th e im p o rta n c e of v a rio u s in d e p e n d e n t v ariables (Hintze, 1992). I tested th e in flu en ce o f p e rc e n t clays, pH, salin ity , co p p er, iro n , a n d zinc on th e p re sen c e an d ab sen ce o f th e fo u r grasses w ith h ig h e st d en sities, in c lu d in g P h le u m p r a t e n s e . Poa p r a te n s is . A e ro o v ro n s p . a n d B ro m u s s p .. 59 T able 7 p re s e n ts re su lts fro m th is e x p lo ra to ry use o f logistic reg ressio n . ta b le show s th e p e r c e n t o f sp ecies p re s e n c e /a b s e n c e re s u lts The c o r r e c tly p re d ic te d b y th e logistic m o d el a n d th e in d e p e n d e n t v a ria b les w here p<=0.10 fo r each species. In g en eral, th e logistic re g re ssio n m o d e ls w ere b e tte r a t p re d ic tin g p re se n c e fo r th e m o re com m o n species (P h leu m p ra te n s e a n d P oa p ra te n s is ) a n d b e tte r a t p re d ic tin g ab sen ce fo r th e ra re species (B ro m u s s p . a n d A g ro p y rp n sp .). As w ith o th e r analyses, b o th pH levels a n d tra c e m e ta l levels a p p e a r to be significant. The c o m b in ed d a ta suggest th a t th e tailings, w ith th e ir low pHs a n d h ig h tra c e m etals, a re larg ely re sp o n sib le fo r re d u c e d d iv ersity , d e n sity , a n d biom ass o f grass species along Soda B utte Creek. Table 7. Results o f Logistic R egression A nalysis fo r fo u r grass species MODEL PREDICTIONS CONTROL VARIABLES, - P VALUES % Clay pH EC Cu Fe Zn PRESENT % correct ABSENT % correct Phleum oratense NS 0.0011 NS 0.0003 0.0011 NS' 94.62% 25.32% Poa oratensis 0.0565 0.0554 NS 0.0033 0 .0 3 6 8 NS 89.32% 38.98% AsroDvron spp. 0.0945 0.0683 NS NS NS 0 .0 9 3 9 11.11% 99.60% NS 0.0056 NS NS NS NS 0.00% 100.00% DEPENDENT VARIABLES Bromus SEE- D istance from a n d Elevation above Stream E n v iro n m en tal ch arac te ristic s such as th e lo catio n o f a site in r e la tio n to a w a te r so u rce can a ffect tra c e m e ta l m o b ility a n d in flu e n c e v e g e ta tio n diversity. For th e m o st p a r t trace m etals w ere p atch ily d is trib u te d w ith in each site. T he follow ing d iscu ssio n h ig h lig h ts th e re su lts fo r c o p p er, w h ich a re p o sitiv ely c o rre la te d w ith th e re su lts fo r th e o th e r tra c e m etals. G rap h s o f 60 sam p le tra n s e c ts in Fish M eadow , H ollyw ood M eadow, a n d Icebox M eadow illu stra te th e v a rie d n a tu re o f c o p p er levels a n d diversify, (DMg) in re la tio n to d ista n ce fro m stre a m c h a n n e l (Figure 22). Both c o p p e r levels a n d d iv e rsity rise a n d fall a t sev e ra l p o in ts along e a c h tra n s e c t r a th e r th a n follow ing a p a tte rn d efin e d by th e d istance of th e sam ple p o in t fro m th e stream . D iversity a n d c o p p e r levels a re in v e rsely re la te d in som e cases. At sev eral p oints along th e tra n s e c ts d iv e rs ity d e c re a se s w h en c o p p e r levels ris e a b o v e SOOppm; h o w ev er, a t o th e r p o in ts d iv e rs ity re m a in s h ig h w h e n c o p p e r levels ris e above SOOppm. The overall th re sh o ld p a tte rn s discussed e a rlie r offer a c lea re r ex p lan atio n o f th e re la tio n sh ip b etw een tra c e m etals a n d diversity. S c a tte r p lo ts o f d iv e rsity (DMg) in re la tio n to d ista n c e d o n o t show a re la tio n s h ip betw een v e g eta tio n a n d lo c atio n as fa r as 34m fro m th e s tre a m (Figure 23). T he low er d iv e rsity levels b e y o n d 34m m ay re la te m o re to site c o n d itio n s such as m o istu re stre ss th a n tailin g s, since th e h ig h e r c o p p e r levels a re fo u n d w ith in 35 to 45m o f th e stre am (Figure 24). Elevation ab o v e th e stre a m c h an n e l a n d d iv ersity a re n o t c o rre la ted (Figure 23). S c a tte r p lo ts o f c o p p e r levels in re la tio n to d is ta n c e o f th e sam p le q u a d ra t fro m th e stre am edge show th e h ig h e st m etal levels w ith in 35 m, a n d d e c re a sin g m e ta l levels b e y o n d 4 5 m (F igure 24). This suggests th a t th e m a jo rity o f th e m in e tailings a t m y s tu d y sites w ere d e p o site d in flo o d p la in a re as w ith in 4 5 m o f th e c u rre n t stre a m c h an n e l. No a p p a r e n t re la tio n sh ip exists b e tw e e n th e tra c e m etal levels a n d th e e le v a tio n ab o v e th e s tre a m c h a n n e l o f each sam ple q u a d ra t (Figure 24). 61 a 300 S- 200 0 5 10 15 20 25 - 2 .5 5 - 1 .5 •< - 0 .5 JF 30 Fish Meadow Transect B- Distance from stream (m) 700 600 Copper (ppm) 500 400 300 200 100 0 0 I I I 5 10 15 ' I I 20 25 30 Hollywood Meadow Transect F - Distance from stream (m) Copper (ppm) 2 a I Index (I 2 S Icebox Meadow Transect C - Distance from stream (m) Figure 22. O verlay o f changes in c o p p er levels relativ e to changes in d iv ersity (DMg) along tran sects in th re e m eadow s. 62 3 .5 - — * ------------------------------------------------------------------------------------------------------------------------------------------------ * * i - Z J. u * * Q o . o> ZL O S * : * * ****** * ^ * . * ' * . * * * * * * ,Z ,* * * * * * _____ _____________ * * _______________________________________________________ * * 15 ' I * DMg * * * * *** ^ * * f I ^ * . * * * * I * * • : • * 4 * * . * * * • * * * * t * ★ II ★ A W ^ * * * * ------1 1 * * 1 - — I I ■ I 10 1 ' * I 20 ' I 30 * i 40 60 50 Distance from stream (m) 3.5 X 3 X X X DMg O) Q ^ Z .O I C V “ * *% „ 2 ** x x x a kX & x* x V ^ t * X x * cX _____________________ x & _____________________________________________ X ^ X KI 0) S Q " I.O I S - - _____________________________ 'I O O) B 5 I 1 ; „ _____________________________ X X XX 0.5 x X 0 I -C.4 I X _________ * I I l I - I- - -0.2 0 0.2 0.4 0.6 • I I 0.8 I I ' 1.2 I .4 Elevation above stream (m) Figure 23. S catter p lots o f d iv ersity (DMg) in relatio n to d istan ce from s tre a m c h an n e l a n d elevation o f sam ple p o in t above stream ch an n el. 63 700■ 600 Copper ■ , ■■ " : - ‘ i I 0 10 • i V : /C :'-:' 0-i V . ■. ■. : V ■ r . : . * ■ ■■ yIOO I Copper (ppm) 500 C- : . ' ' - - ‘ ’■ "■: ^ ' I 2 ' ' 0 I 3 •••*"■ ! ! ' I 0 0 I 5 0 I 6 0 . I 7 0 8 0 Distance from stream (m) Copper (ppm) Copper -0.5 0 0.5 I 1.5 2 Elevation above stream (m) Figure 24. C o n cen tratio n o f c o p p er (ppm ) in relatio n to d ista n ce from stre am c h an n el a n d elev atio n of sam ple p o in t ab o v e stream ch an n el. 64 The sca tte r p lo ts o f c o p p er in re la tio n to d istan ce a n d elev atio n fo r Soda B utte C reek closely resem b le th e co rre sp o n d in g plots fo r in d iv id u a l m ead o w s. T he la c k o f a c le a r sp a tia l p a tte r n su g g ests th a t th e v a ria tio n s in t h e s e g ra ssla n d c o m m u n ities in th e a re as s tu d ie d a re o n ly w eakly co n tro lled , if a t all, b y h y d ra u lic fa c to rs su ch as g ro u n d w a te r levels o r in c re a s e d m o istu re levels in d ep ressio n s close to th e stre am channel. D ow nstream V ariations D ata analysis in d icates th a t a do w n stream spatial p a tte rn exists fo r som e v ariab les a n d n o t fo r others. I co m p ared d a ta from th e fo u r m eadow stu d y sites to d e te rm in e if collective d o w n stre am ch an g es in e n v iro n m e n t w ere d riv in g v a ria tio n s in v e g e ta tio n ch arac te ristic s b etw een sites. I also u sed d a ta fro m th e in d iv id u a l sites to assess do w n stream d ifferences in tra c e m etal levels. D ow nstream differences in v e g eta tio n d iv ersity can b e visualized w ith a box p lo t (Figure 25). sites. T he m e an M argalef D iversity In d ex is 1.7 fo r all th re e T hus v e g e ta tio n d iv e rsity re m a in s fa irly c o n sta n t b e tw ee n th e th re e u p p e r m e a d o w site s. R o u n d P ra irie w as n o t in c lu d e d in th e d iv e rs ity m easu rem en ts d u e to tim e co n strain ts d u rin g th e field season. The sim ilarities in m e an d iv ersity fro m m eadow to m ead o w suggest th a t th e o v e ra ll e n v iro n m e n ta l c o n tro ls o n v e g e ta tio n (e.g., c lim ate, e le v a tio n , w a te r a v a ila b ility , so il c h a ra c te ris tic s ) d o n o t v a ry s ig n ific a n tly in th e d o w n stream directio n . It a p p ea rs th a t w ith in m eadow v a ria tio n s in trace m e ta l levels a n d soil c h a r a c te ris tic s serv e as th e p rim a ry fa c to rs in flu e n c in g d iffe re n c e s in v e g e ta tio n r a th e r th a n th e d o w n stre a m m eadow s. p o s itio n s o f th e 65 2 .5 O) Z s _c 5"O K J Q SO P O 5 Fish Hollywood Icebox Figure 25. Box p lo t of M argalefs D iversity Index (DMg) for Fish, Hollywood, a n d Icebox M eadows. C enter line is m edian, c e n te r square is m ean, top an d b o tto m edges of box a re 2 5 th a n d 7 5th qu artiles, e n d s of w hiskers a re IOth a n d 9 0 th q u a rtile s . Som e o f th e tra c e m etal levels show a n o v e ra ll d o w n stre a m d e c lin e (Figure 9). Because th e sam ple design o f this stu d y d id n o t a tte m p t to sam ple e v ery site co m pletely, th e d o w n stre am v a ria tio n s sh o u ld be in te rp re te d as g en eral tre n d s. d ire c tio n . M edian a n d m ean c o p p er a n d iro n d eclin e in a d o w n stream The zinc m ean d eclines slightly, w hile the m e d ia n flu ctu ates th e n declines in R ound P rairie (Figure 9). D eclining trace e le m e n t c o n ce n tra tio n s d o w n stre a m m ay be a ttrib u ta b le to d ilu tio n of th e ta ilin g s sed im en t w ith u n c o n ta m in a te d se d im e n t d u rin g tra n s p o rt (Lewin, 1977; M arcus, 1987). In c o n tra st, m ean a n d m ed ian arsenic a n d lead levels in crease do w n stream from Fish M eadow to Icebox Meadow, th en decline in Round P rairie (Figure 9). 66 CHAPTER 5 SUMMARY AND CONCLUSIONS S u m m ary ' This re s e a rc h ex am in ed th e d is trib u tio n o f tra c e m e tals a n d im pacts o f th e se m etals o n m eadow v eg etatio n along th e floodplains o f Soda Butte Creek, M o n tan a a n d W yom ing in Y ellowstone N atio n al Park. T he tra c e m etals w ere tr a n s p o r te d d u rin g a la rg e flo o d e v e n t in 1950, w h ic h c a r r ie d d o w n stre a m fro m th e M cL aren m in e im p o u n d m e n t o u ts id e ta ilin g s Cooke C ity, M ontana. The d a ta collected fo r this stu d y in clu d e grass a n d fo rb densities, soil pH, soil clay co n ten t, soil salinity a n d soil m etal content, a n d site elevation a n d d istan ce from th e stre am in 281 circu lar q u a d ra ts in fo u r m eadow s. The tra c e m etals stu d ie d in clu d e arsenic, copper, iro n , lead, an d zinc. V egetation d a ta was collected in 1993 a n d 1994. Q u ad rats w ere in th e sam e locations d u rin g b o th field seasons. The w arm er, d rie r w e ath e r d u rin g th e 1994 season re s u lte d in e a rlie r p la n t m a tu ra tio n . It is possible th a t th e d iffe re n c e s in su m m e r w e a th e r a lte re d v e g e ta tio n p a tte rn s d u rin g th e two seasons, th e re fo re , to m a in ta in consistency, th e d a ta an aly ses of d iv ersity a n d d en sity d id h o t com bine d a ta from th e two seasons. T he p rim a ry fin d in g o f th is p ro je c t w as th e th re s h o ld re la tio n s h ip b e tw e e n v e g e ta tio n a n d tra c e m e ta ls fro m th e tailin g s in th e flo o d p lain . V egetation d iv e rsity , d en sity , a n d bio m ass all v a rie d w id ely u p to a c e rta in tra c e m etal level, a t w hich p o in t m e an d iv ersity , d e n sity a n d biom ass d ro p p e d 67 sig n ific a n tly (F igures 10, 12, 14). T his re la tio n s h ip w as p a rtic u la rly w ell illu stra te d w ith CuSum p lo ts o f th e tra c e m etals a n d v e g eta tio n ch aracteristics (Figures 10, 11, 13). V egetation d iv e rsity d eclin ed above a th re sh o ld p o in t of 3 IS p p m co p p er, 22p p m arsen ic, 4.2% iro n , 65p p m lead , a n d 17Oppm zin c (Figures 10 a n d 11). Not all species show ed statistically sig n ifican t d e crea se s in d e n sity , a lth o u g h 26 o f 33 species h a d low er m e an d e n sity on p lo ts w ith c o p p e r levels above 2 5 Oppm (Table 5). Iu n c u s b a ltic u s was th e exception to th is finding, w ith a significant in crease in d e n sity o n th e h ig h e r c o p p er plots. V e g etatio n c h a ra c te ris tic s also v a rie d w ith soil pH. pH levels in th e stu d y a re a w ere closely c o rre la te d w ith h ig h tra c e m etal levels, w hich reflects th e low pH o f th e tailings source m a te ria l. pH h a d a th re s h o ld re la tio n sh ip w ith v e g e ta tio n sim ila r to th a t o f th e m etals (Figures 15, 16, 18). At soil pH levels below 6.5, m e an v eg etatio n d e n sity a n d biom ass d e c re a se d (Figure 17). Tw o-thirds o f th e species h a d low er m e an d e n sity o n p lo ts w ith pH<6.5 (T able 6). H ow ever, v e ry few species shoy/ed sta tistic a lly sig n ific a n t d e crea se s in d e n sity on plots w ith pH<6.5, w hich m ay reflect th e sm all n u m b e r of plots w ith low pH values. The re la tio n sh ip betw een pH a n d v eg etatio n d iv ersity w a s.n o t as stro n g as th e links betw een pH a n d d e n sity o r b io m ass. The s m o o th e d o v erlay o n th e sc a tte r p lo t of v eg etatio n d iv ersity in re la tio n to pH shows a n o verall in c re a se in d iv e rsity as pH levels in crease (Figure 15). The ex cep tio n to this tre n d was a slight d ro p in d iv e rsity fro m pH 6 A to pH 6.6, w hich n iay re la te to o th e r e n v iro n m e n ta l factors. Soil sa lin ity a n d clay c o n te n t d id n o t a lte r v e g e ta tio n p a tte rn s in a co n sisten t m a n n e r to th e sam e ex ten t as trace m etals a n d pH levels (Figures 19, 20, a n d 21). Likewise, th e distan ce of each p lo t fro m th e stre am was n o t a key in flu en c e o n v e g e ta tio n p a tte rn s, w ith th e ex cep tio n o f p lo ts m o re th a n 35m 68 fro m th e stream , w here d iv e rsity d e crea se d (Figure 23). T he elevation o f each sam ple p lo t d id n o t affect diversity, d en sity o r biom ass. V ariations in th e d iv e rsity a n d d e n sity o f grasses re la te d m o re to local changes in tra c e m etals a n d pH asso ciated w ith d isp ersio n o f th e tailings th a n to d o w n s tre a m c h a n g e s in e n v iro n m e n ta l c o n tro ls . T h is fin d in g w as s u p p o rte d b y box p lo ts o f d iv e rs ity fo r th re e m ead o w sites, w h ere m e a n d iv ersity d id n o t v a ry betw een m eadow s (Figure 25). D iscussion W hile th is s tu d y fo c u se d p rim a rily o n th e e m p iric a l re la tio n s h ip s betw een vegetatio n p a ra m ete rs, trace m etals, a n d pH levels, th e stu d y o utcom es c an o ffe r in s ig h ts as to th e e c o lo g ic a l m e c h a n is m s w h ic h in flu e n c e c o m m u n ity stru c tu re . T he stu d y resu lts show a n in te re stin g d isp a rity b etw een th re sh o ld tra c e m etal levels fo r changes in d iv ersity a n d changes in d en sity . CuSum p lo ts fo r th e d e n sity o f two grass species show d e c re a se d d en sity ab o v e 216ppm c o p p er fo r P h le u m n ra te n s e a n d above 236 p p m Copper fo r Poa p ra te n s is (Figure 13). In c o n tra st, th e th re s h o ld lev el fo r d e c re a se d d iv e rsity o ccu rs a t 3 IS p p m c o p p er (Figure 10). The d iv e rsity in d ex in clu d es d en sity d a ta fo r th e m ajo rity of p la n t species in th e stu d y sites, w hich p ro v id es a n o v erall p o rtra it of p la n t c o m m u n ity re sp o n se to tra c e m etals a n d pH levels. H ow ever, th e fa c t th a t d e n sity d e crea se s a t low er tra c e m etal levels suggests th a t p la n t d e n sity is a m o re sen sitiv e m e a s u re o f v e g e ta tio n th re s h o ld levels th a n d iv e rsity . A h ig h e r th re s h o ld level fo r d ro p s in d iv e rsity m ean s th a t in d iv id u a l species w ith low er tra c e m e ta l th re sh o ld s h a v e a lre a d y b e en a ffe cted . In, a d d itio n , in d iv id u a l species can v a ry d ra m a tic a lly in th e ir re sp o n se to e n v iro n m e n ta l 69 p a ra m e te rs. For exam ple, d e n sity o f Tuncus b a ltic u s was sig n ifican tly h ig h e r on th e p lo ts w ith c o p p e r levels ab o v e 2 5 0 p p m , a n d five o th e r species h a d h ig h e r m e an d en sity o n hig h co p p er p lo ts (Table 5). The d e n sity d a ta fo r th e se m etal to le ra n t species was in clu d ed w ith d a ta fo r th e 26 o th e r m etal in to le ra n t species in calculating th e d iv e rsity index. D iversity th re sh o ld s a n d d e n sity th re sh o ld s fo r pH levels ex h ib it m o re sim ila r b e h a v io r th a n th e tra c e m e ta l re s u lts. D iv e rs ity le v els in c re a s e consistently above pH 7.0 (Figure 15) a n d d en sity levels in crease above pH 7.15 fo r P h le u m p r a te n s e a n d pH 7.1 fo r P oa p ra te n s is (Figure 17). N evertheless, th e d iv e rsity in d ex in cludes d a ta a b o u t species w ith h ig h e r m e an d en sities o n plots w ith pH levels, below 6.4 a n d species w ith low er m e an d en sities on low pH plots (Table 6). C learly, n o t all species ex h ib it th e sam e re sp o n se to changes in tra c e m etal levels o r pH levels. T he to le ra n ce o f a n in d iv id u a l species to ex trem e c o n d itio n s ,can a ffect its co m p etitiv e a b ility in a p la n t co m m u n ity . P lants w hich d o m in a te h a b ita ts w ith sev ere c o n d itio n s a re so m etim es re s tric te d to th e se h a b ita ts b e c a u se th e y a re p o o r c o m p e tito rs o n less e x tre m e site s (B arbour e t al., 1987). For exam ple, s e rp e n tin e e n v iro n m e n ts ty p ic a lly a re h ig h in toxic tra c e m etals, w ith v e ry acidic o r basic pH level's. S e rp e n tin e e n d em ics fre q u e n tly grow fa s te r o n n o n s e rp e n tin e soils, b u t o n ly in th e a b se n c e o f in te rsp e c ific co m p etitio n . T olerance, o f s e rp e n tin e soils can be c o n sid ered a m ech an ism fo r avoiding com petition. A s tu d y o f d is trib u tio n g ra d ie n ts fo r several grass species along a pH g ra d ie n t fro m pH 3.5 to pH 8.0 show ed th a t each species h a d a unique resp o n se to v a rie d pH levels, a n d th e a b u n d a n c e levels o f d iffe re n t species o v e rla p p e d c o n sid e ra b ly (G rim e a n d Lloyd, 1973). T he re la tiv e ly low d iv e rsity levels 70 b etw een pH 6.5 a n d pH 7.0 in th is stu d y (Figure. 15) c o m p ared to h ig h e r a n d low er pH levels co u ld re la te n o t o n ly to d ifferin g re s p o n se s o f in d iv id u a l species to changes in pH, b u t also to ch an g es in co m p etitio n . T ilm an (1990) suggests th a t species d iffe r in th e ir a b ility to co m p ete fo r a lim iting soil re so u rc e , w hich th e n in flu en c es th e ir a b ility to colonize sites w ith n u trie n t p o o r substrates. In th e case o f d iffe re n t th re s h o ld levels fo r d iv e rs ity a n d d e n sity in re la tio n to tra c e m e ta ls, b o th to le ra n c e a n d c o m p e titio n m a y ex p lain th e v a ria tio n in re sp o n se to h igh tra c e m etal levels. The d is tu rb a n c e c au sed b y th e d e p o s itio n o f m in e ta ilin g s p ro v id e d a m e c h a n is m fo r in c re a s in g p o p u la tio n s o f m e ta l to le ra n t species in th e se areas. D iversity a n d d e n sity in a re a s w ith lo w er tra c e m e ta l levels m o s t lik ely re la te to c o m p e titio n fo r n u trie n ts a n d e n v iro n m e n ta l h e te ro g e n e ity (Begon e t al., 1986). As sta te d b y W h ittak er (1965), th e "loosely o rd e re d com plexity" o f la n d p la n t com m unities e m p h asizes th e n e e d fo r b o th g e n e ra l a n d specific o b se rv a tio n s to o b ta in a b a la n c e d p e rs p e c tiv e on v e g e ta tio n p a tte rn s . In th e case o f th is stu d y , as discu ssed prev io u sly , changes in d e n sity o f in d iv id u a l species m ay p ro v id e a b e tte r e stim a te o f p la n t h e a lth , w hile d iv e rsity m e a su re s illu s tra te b r o a d p a tte rn s . D ue to th e e n v iro n m e n ta l h e te ro g e n e ity o f th e s tu d y sites a n d n ic h e d iffe re n tia tio n b etw een species, h ig h tra c e m e ta l levels a n d low pH levels im p act in d iv id u a l species m o re th a n th e co m m u n ity d iv e rsity . N evertheless, th e d is p la c e d m in e ta ilin g s c a n h a v e c o n tin u e d im p a c ts o n th e p la n t c o m m u n ity as a w hole fa r in to th e fu tu re . Once excess tra c e m etals e n te r a system , th e y re m a in b o u n d to soil co m p o n en ts, in c o rp o ra te d in to p la n t tissues, o r can b e in g e ste d b y anim als o v er a n ex ten siv e tim e p e rio d . E stim ates o f 71 re sid en c e tim e in soils fo r tra c e m etals in te m p e ra te clim ates ra n g e fro m 1000 to 3000 y e ars fo r co p p er, lead , a n d zinc (K abata-Pendias a n d P en d ias, 1992). T he sp a tia l d is trib u tio n o f im p acts w ill m o st lik ely re m a in co n fin ed to th e m eadow s along Soda B utte Creek w h ere th e tailings w ere o rig in ally d ep o sited . As th e tailings a re in c o rp o ra te d in to a re a soils, fu rth e r tra n s p o rt o n th e scale o f th e 1950 flood e v en t is unlikely. F u tu re R esearch This stu d y e sta b lish e d b ro a d asso ciatio n s betw een m e ad o w v e g eta tio n along Soda Butte Creek, tra c e m etals, a n d soil pH. T hese associations suggest m a n y av en u es fo r fu tu re re sea rc h . First, th e sp atial e x te n t a n d to tal accu m u la tio n o f tailin g s along S oda Butte C reek n eed s to be d o cu m en ted in o rd e r to evaluate th e p o ten tial ex ten t of tailings re la te d im pacts. The d a ta fro m m y re se a rc h p ro je c t could be u sed to stu d y th e sp atial a u to c o rre la tio n o f v a ria b le s a n d p re d ic t th e d istrib u tio n of ta ilin g s d e p o sits u sin g k rieg in g c o u p le d w ith f u r th e r sam p lin g . A glo b al p o s itio n in g sy ste m (GPS) u n it w o u ld p ro v e u sefu l fo r m a p p in g d e p o sits, p e rh a p s b y sy stem atically collecting a n d an alyzing soil sam p les fro m k n o w n g eo g rap h ic lo cations. In o rd e r to p re d ic t w hich tra c e m etals a re av ailab le fo r p la n t u p ta k e, fu tu re re s e a rc h sh o u ld q u a n tify the b io av ailab le frac tio n o f each of th e tra c e m etals. D iscussions o f tra c e m etal c h e m istry in th e lite ra tu re suggest th a t tra c e m e ta l e x tra ctio n s can p ro v id e a b e tte r e stim ate o f b io a v ailab le m e tals th a n to ta l m etal c o n c e n tra tio n s (K abata-P endias a n d P e n d ia s, 1992). F u tu re w ork co u ld estab lish th e p artitio n in g o f tra c e m etals am ong soil fractio n s such 72 as organic m a tte r, clays,, a n d h y d ra te d m e ta l oxides, in O rder to e stim ate th e bioavailable pool o f tra c e m etals. As a p a rt o f biogeochem ical cycles, tra c e m etals can accu m u late in soils, p la n ts, a n d o th e r organism s. B arb ara E rickson's v e g eta tio n stu d y along Soda B utte C reek (1994) p ro v id e s th e first step in assessing tra c e m etal u p ta k e b y p la n ts. F u rth e r v e g eta tio n studies co u ld in c lu d e a co m p ariso n of m etal lev els in d iffe re n t p la n t p a rts (roots, shoots, seeds), testing p la n ts a t d ifferen t p o in ts in th e grow ing sea so n , a n d e x p a n d in g th e c o lle c tio n a r e a b e y o n d th e stream b an k s a n d in to th e m eadow s. T he tailings d a m b re a k o c c u rre d o v er fo rty y ears ago, a n d som e p la n t species m ay h a v e d e v elo p e d to le ra n c e m ech an ism s in re sp o n se to h ig h tra c e m etal levels. Tuncus b a ltic u s . fo r exam ple, h a d significantly h ig h e r d e n sity o n th e h ig h c o p p e r a n d low pH plots. F u rth e r re s e a rc h co u ld ex am in e w h e th e r th is species utilizes to le ra n c e m ech an ism s. In a d d itio n , im p acts d u e to th e tailings m ay cause changes in p la n t assem blages. The sam pling schem e o f th is s tu d y w as d e sig n e d fo r co m m o n g rass sp ecies, b u t a d iff e r e n t sam p lin g p ro c e e d u re m ig h t a d d re ss th e ex ten t o f im pacts on ra re o r th re a te n e d species. A lthough th e p re sen c e o f h ig h levels o f h eav y m e tals can affect p la n ts d ire c tly , o th e r c o m p o n en ts o f th e eco sy stem also face p o te n tia l risks. For exam ple, soil m ic ro -o rg a n ism a ctiv ity d e crea se s in th e p re s e n c e o f c e rta in h e av y m etals, w hich in te rfe re s w ith n o rm a l biom ass a ctiv ity (Alloway, 1995). A stu d y o f fo rm e r m ining a re as in th e O iartzu n riv e r v alley , Spain, re p o rte d h ig h d o w n stream c o n ce n tra tio n s o f h e av y m etals in sed im en ts, moss, a n d fish tissues (Sanchez e t al., 1994). A nim als can in ta k e h eav y m etals b y consum ing p la n ts w ith trace m e ta ls o n th e p la n t surface o r w ith in th e p la n t tissues, o r b y in g estin g soil (A driano, 73 1986; H aygarth a n d Jones, 1992). D ow nstream accu m u latio n o f trace m etals in soils a n d p la n ts h e a r Leadville, C olorado, c au sed a d v e rse h e a lth effects in grazing livestock (Levy, 1992). Sheep a re co n sid e re d p a rtic u la rly sensitive to copper, toxicity, a n d o th e r anim als can accu m u late c o p p er in th e liv er (G ouch e t ah, 1979). Some re se a rc h e rs have th e o riz e d th a t s o il/p la n t system s serve to m inim ize tra c e m e ta l toxicity, in th a t p la n t grow th will Slow o r cease b e fo re tra c e m e ta ls a c c u m u la te to levels h a rm fu l fo r a n im a ls (A llow ay, 1 9 9 5 ). H ow ever, th is th e o ry neglects th e fa c t th a t an im als c an in g e st c o n ta m in a te d soils, a n d th a t p la n ts can dev elo p to le ra n c e s a n d acc u m u la te h ig h levels o f h e av y m etals. R egardless, th e c lea r asso ciatio n betw een m etals a n d p la n ts in m e a d o w s a lo n g S oda B utte C reek in d ic a te s th a t f u tu r e re se a rc h on b io accu m u latio n o f tra c e m etals in w ildlife in Yellowstone N ational Park m a y be a p p ro p ria te . R eco m m en d atio n s T he re s u lts o f th is stu d y h a v e im p licatio n s fo r re s o u rc e m a n a g e rs in Y ellow stone N a tio n al P ark a n d fo r th e c o rp o ra tio n re s p o n s ib le fo r th e M cLaren tailings pile o u tsid e Cooke City, M ontana. Park m a n ag e rs n e ed to b e a w are o f p o te n tia l th re a ts to Y ellow stone flo ra a n d fa u n a . A lth o u g h th e d isp la c e d M cLaren tailings a re n o t d ecim atin g v e g eta tio n along Soda B utte Creek, th e tailin g s h a v e h a d a n im pact. locations o f all th e tailings d eposits. At p re sen t, n o o n e h a s m a p p e d th e A re c o n n aisa n ce o f th e m eadow s alo n g Soda B utte C reek w ould be useful fo r re m e d iatio n a n d m o n ito rin g . Because th e ta ilin g s a re p a tc h ily d is tr ib u te d im possible to rem ove. th e y w o u ld b e d iff ic u lt a n d p e r h a p s However, p a rk m a n ag e rs m ay w an t to in v estig ate th e fe a s ib ility o f re v e g e ta tin g sites w h e re b a r e p a tc h e s o f m in e ta ilin g s a re 74 exposed a t th e soil surface. In a d d itio n , p a rk m an ag ers m ay w an t to c o n s id e r th e use o f soil a m e n d m e n ts such as lim in g o r fertilizers to m itig ate tailings im pacts. T h e re m a in in g m in e tailin g s p o se a p o te n tia l th r e a t to Y ellow stone Park, p a rtic u la rly if th e im p o u n d m e n t is h o t secured. In 1990, u n d e r d irectio n o f th e E nvironm ental P rotection Agency, K ennecott C opper C om pany fin a n c e d site re m e d ia tio n to stab ilize th e tailin g s. p re p a re d by th e B u re au A 1994 re s p o n s e a c tio n r e p o r t o f R e c la m a tio n c o n firm s t h a t th e ta ilin g s im p o u n d m e n t co n tin u es to d isch arg e m etal-rich efflu en t d ire c tly to Soda Butte C reek (B ureau of R eclam ation, 1994). Soda B utte C reek also ero d es exposed p o rtio n s o f th e tailings im p o u n d m en t. A n o th e r large flo o d e v e n t could c a rry m o re ta ilin g s d o w n stre a m . F u rth e r site re m e d ia tio n c o u ld a v e rt f u t u r e e n v iro n m e n ta l im pacts fro m th e tailings. T he o th e r im p licatio n of this stu d y re la tes to th e p ro p o s e d New W orld D istrict gold m in e in th e F isher C reek d ra in a g e . D ep en d in g o n th e ty p e o f processing, th e tailings fro m th e p ro p o se d m in e m ay also c o n ta in high levels o f acid -g en eratin g w aste rock. Clearly, th e location a n d fu tu re stab ility o f th e tailings im p o u n d m e n t is k ey to avo id in g d o w n stre am im p acts. A lthough th e M cLaren ta ilin g s w e re im p o u n d e d less th a n fifty y e a rs ago, th e d isp la c e d tailings m a y c o n tin u e to d e g ra d e th e la n d sc a p e fo r d e c a d e s to com e. The p ro p o se d New W orld M ine could hav e sim ilar, b u t m u ch la rg e r scale im pacts, u n less we le a rn fro m th e p a s t b y giving c arefu l c o n sid e ra tio n to th e lo n g ­ te rm im pacts of re so u rce extraction on d o w n stream ecosystem s. REFERENCES 76 REFERENCES VzA d rian o , D.C. 1986. 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Q u a d rat n u m b e r DIST D istance o f q u a d ra t fro m stre am c h an n el in m e te rs ELEV Elevation of q u a d ra t above stre am c h an n e l in m eters As Total arsenic c o n te n t o f O-IOcm soil sam ple in p p m Cu T otal c o p p er c o n te n t o f O-IOcm soil sam ple in p p m Fe T otal iro n c o n ten t o f O-IOcm soil sam ple in p e rc e n t Pb Total lead co n ten t of O-IOcm soil sam ple in p p m Zn T otal zinc c o n ten t o f O-IOcm soil sam ple in p p m As2 T otal arsenic c o n te n t o f 10-2 Ocm soil sam ple in p p m Cu2 T otal c o p p er c o n ten t o f 10-20cm soil sam ple in p p m Fe2 T otal iro n c o n te n t o f 10-20cm soil sam ple in p e rc e n t Pb 2 Total le ad c o n ten t o f 10-20cm soil sam ple in p p m Zn2 Total zinc c o n ten t o f 10-2 0cm soil sam ple in p p m %CL1 P ercen t clay c o n te n t o f O-IOcm soil sam ple %CL2 P ercent clay c o n te n t of 10-20cm soil sam ple pH I pH level o f O-IOcm soil sam ple pH2 pH level o f 10-20cm soil sam ple ECl Electrical C onductivity o f O-IOcm soil sam ple in (xmhos 86 Key to Colum n H eadings - C ontinued Colum n H eading D e sc rip tio n EC2 Electrical C onductivity o f IO-ZOcm soil sam ple in ^m hos SALl Soil salinity o f O-IOcm soil sam ple in d S /m BIOM A bove-ground biom ass o f P hleum p ra te n se in gram s DIV N um ber of d istin c t species w ith in th e q u a d ra t DMg M arg ale fs D iversity Index fo r th e q u a d ra t Key to Colum n N um bers* * Colum n n u m b e rs re fe r to p la n t species. R eported values in d ic a te n u m b e r o f ind iv id u als of th a t p la n t w ithin th e q u a d ra t, un less otherw ise n o ted . Colum n N u m b er P lan t Name I A chillea spp. 2 A g oseris glauca 3 A g ro p y ro n spp. 4 A ngelica spp. 5 A n te n n a ris a n a p h a lo id es 6 A s te r h e sp e riu s 7 ' A stragalus spp. 8 B rom us spp. 9 Carex spp. 10 . C erasticum spp. 11 C ircium scariosum 12 D eschkm psia cespitosa 13 E pilobium a n g u stifo liu m 87 Key to Column N u m b ers-Con tin n e d Colum n N u m b er P la n t Name 14 E quisetum variegatum 15 Fragaria vesca 16 G entiana detonsa 17 Ju n cu s balticus 18 M u h le n b e rg ia filifo rm is 19 Pedicularis spp. 20 . P hleum p r a te n se 21 Poa jtm c ifo lia 22 Poa p ra te n sis 23 P otentilla spp. 24 Saxifraga spp. I 25 Saxifraga spp. 2 26 Senecio erassulus 27 Sm ilacina spp. 28 Taraxacum spp. 29 T rifolium lo n g ip es 30 T rifo liu m re p e n s 31 T riglochin m a ritim u m 32 Veronica spp. 33 Viola spp. 34 M oss spp. ( I indicates p resen ce, 0 indicates absence) Cu Fe Q DIST ELEV As Fa I 0.96 0.16 Fa 2 2.96 0.42 Fa 3 4.96 Fa 4 6.96 Fa 5 8.96 0.4 Fa 6 10.96 0.41 Fa 7 12.96 0.41 6 144 3.87 Fa 8 14,96 T Pb Zn A s2 Cu2 Fe2 Pb2 Zn2 %CL1 %CL2 pH I pH2 50 3.25 18 66 2 116 3.50 32 80 34.38 23.06 6.55 6.16 34 86 6 165 3.93 34 84 20.06 10.06 6.53 6.55 0.45 6 134 3.23 16 174 4.14 36 0.41 2 155 3 .8 2 2 . 6.76 266.88 1.07 6.49 309.90 1.24 8 156 3.76 5.81 6.52 322.61 1.29 4 145 3.58 36 84 7.63 6.49 272.75 1.09 38 90 5.81 6.5 292.30 1.17 42 106 13.5 6.51 338.25 1.35 9 16.96 18.96 0.34 Fa 11 20.96 0.335 Fa 12 22.96 0.34 24.96 0.34 26.96 0.34 1.19 5.88 10 13 1.17 10.63 Fa 14 292.30 424.28 298.17 145.66 92 Fa Fa EC2 SALI 36 . 88 94 36 0.46 18 152 3.66 4 123 3.32 0.48 Fa ECI 42 92 6 171 .3.95 32 84 7.63 -2 107 3.09 28 82 -2 85 3.29 26 80 18,31 6 95 3.13 28 82 2 91 3.00 54 2.69 28 76 18 66 6 138 3.46 38 96 -2 11.81 192 4.20 30 94 14.19 257 5.92 36 98 17.47 6.7 6.54 115.36 222.89 1.23 1.00 236.58 6.6 6.51 21.25 307.94 251.24 6.67 11.19 11.81 12 6.67 6.56 12.94 4 6.68 0.95 1 7 9 .8 8 0.89 207.25 0.83 6.71 346.07 201.38 310.87 1.38 Fa 15 28.96 0.35 8 154 4.11 34 88 21.25 Fa 16 30.96 0.39 6 126 3.79 36 96 23.26 Fb I 0.71 0.62 12 174 4.09 34 106 Fb 2 2.71 36 102 44 110 12 237 4.75 46 114 8 2 8 2 4.78 48 120 17.63 6.45 369.42 1.48 0.625 22 244 4.50 0.63 18 330 5.02 46 19.77 6.33 363.58 1.45 0.65 2 6 305 5.27 0.685 3 6 433 6.54 62 Fb 3 4.71 0.66 12 187 4.26 0.63 16 227 4.49 Fb 4 6.71 0.62 Fb _ 5 Fb 6 8.71 10.71 Fb 7 12.71 Fb 8 14.71 6.44 305.01 305.01 1.22 247.90 282.90 296.51 345.11 0.99 222.62 0.89 439 6.35 84 190 17.15' 13 6.53 6.05 419 7.17 102 170 17.68 10.63 6.4 5.77 864 9.33 138 366 118 17.47 6.5 15.38 6.55 6.22 2 6 6 .3 7 349.97 1.19 1.07 56 138 54 887 9.30 144 354 20.17 12.38 6.33 245.95 447.19 0.98 146 66 809 8.32 142 360 17.11 18.38 6.18 222.62 0.89 23.1 5.93 416.08 1.66 20.75 5.78 425.80 1.70 389.14 1.56 5.99 20.71 8 0 170 70 156 84 148 22.71 0.73 14 303 5.31 62 156 21.84 49.75 5.64 6.48 334.23 1.34 24.71 0.72 20 303 4.81 58 162 43.56 6.78 266.81 1.07 9 16.71 Fb 18.71 Fb 10 11 Fb 12 13 6.51 20.13 66 1.24 14.19 0.68 24 439 6.72 0.7 38 444 7.30 Fb Fb 0.63 36 48 6.5 T DIST ELEV As Cu Fe Pb Zn A s2 Fb Q 14 26.71 0.75 24 270 4.89 68 194 Fb 15 28.71 0.75 48 122 Fe I 1.4 18 255 4.73 0.5 -2 111 3.44 Fe 2 3.4 0.625 8 135 3.64 Fe 3 5.4 0.595 Fe 4 7.4 Fe 5 Fe 28 Cu2 Fe2 Pb2 Zn2 497 ,6.14 68 198 %CL1 %CL2 pH I pH 2 ECI 31.07 20.75 6.78 6.55 3 2 2 .6 7 23.13 6.89 . EC2 SALI 2 4 7 .5 4 1.29 147.37 0.73 0.95 261.99 1.05 28 86 4 234 4.14 38 104 18.38 20.13 7,16 7.19 183.01 38 94 26 320 4.46 56 158 18.38 18.88 7.03 6.97 237.91 12 198 3.70 38 108 20 297 4.70 64 140 24.29 19.95 7.03 7.01 90 224 86 917 8.79 168 390 68 180 15.16 . 14.69 15.34 6.69 9.4 0.535 42 535 6.05 0.515 30 358 5.22 195.53 260.07 216.72 230.21 6.68 326.53 1.31 '6 11.4 0.495 26 350 4.90 76 194 19-24 6.33 322.67 1.29 Fe 7 13.4 0.5 54 265 4-80 116 272 14.29 6.91 371.80 1.49 Fe 8 15.4 0.58 18 355 4.59 66 214 22.8 6.77 291.85 1.17 Fe 9 17.4 0.61 154 22.37 6.86 235.02 0.94 Fe 10 19.4 50 138 27.86 6.96 221.54 0.89 Fe 11 21.4 0.61 16 269 4.55 0.62 12 203 4.08 58 164 21.25 7.07 200.35 0.80 Fe 12 23.4 0.64 28 415 5.48 70 172 15.88 6.79 485.46 1.94 Fe 13 25.4 0.67 14 266 4.38 48 126 15.92 6.91 288.96 1.16 Fe 14 27.4 0,7 .14 290 4.52 42 124 12.14 7.07 183.97 Fe 15 29.4 0.73 14 282 4.34 38 112 Flc I' 1.22 0.03 He 2 3.22 0.085 He 3 5.22 0.11 He 4 7.22 0.075 He 5 9.22 0.03 He 6 11.22 -0.01 He 7 13.22 -0.05 He 8 15.22 -0.09 He 9 17.22 -0.13 He 10 19.22 -0.06 -2 75 .3.27 22 72 7.75 168.77 0.68 He 11 21.22 0.02 2 69 3.41 22 82 -2 49 2.64 22 68 9.38 8.25 7.9 135.43 0.54 12 23.22 0.1 2 75 3.31 22 84 2 60 2.65 18 68 10 7.06 7:96 He 22 305 4.31 62 8 185 4.06 36 96 14.51 9.44 8.81 7.08 7.26 7.88 299.56 119.81 1.04 0.92 0.74 1 6 7 .6 0 61.47 1.20 0.48 T Q DIST He 13 25.22 Pb Zn A s2 Cu2 86 3.52 22 88 6 156 5.70 98 3.71 26 92 8 107 3.31 30 0.34 14 212 4.15 44 144 28 144 3.95 80 194 ELEV As 0.175 -2 0.255 4 Cu Fe Fe2 Pb2 Zn2 %CL1 %CL2 pH I pH 2 ECI 9.38 21.25 7.72 7.76 126.06 87.51 0.50 88 20.06 15.38 7.79 7.76 148.98 102.10 0.60 78 166 11.75 5.25 7.22 7.63 167.73 110.43 0.67 122.93 89.59 184.40 142.72 0.49 46 142 EC2 SALl He 14 27.22 He 15 29.22 He 16 31.22 0.42 16 216 4.10 42 128 30 149 3.69 5.76 3.5 7.31 7.61 He 17 33.22 40 130 32 208 4.11 86 194 5.24 6.44 6.56 7.44 292 5.36 6.45 4.63 7.31 7.42 167.73 150.02 0.67 262 4.67. 2 4 6 414 58 122 5.25 7.56 7.29 7.46 157.31 132.31 0.63 He 18 35.22 0.5 18 231 4.16 0.585 26 279 4.84 186 92 He 19 37.22 0.64 2 4 256 4.27 54 156 22 He 20 39.22 0.62 60 346 4.92 168 432 He 21 41.22 0.6 46 2 6 7 4.76 122 276 He 22 43.22 0.58 48 283 4.98 He 45.22 0.56 14 181 23 6 161 12 171 66 7.27 9.95 68 173 4.44 164 332 8.51 106 182 118 280 5.20 270 452 150.02 7.25 7.58 273.99 130.23 1.10 12.74 17.62 7.2 7.24 202.58 111.62 0.81 21.24 23.06 7.33 7.45 195.34 95.09 0.78 159.17 139.53 148.83 112.66 0.60 14 125 3.53 36 102 3.57 30 96 14 168 3.71 30 86 7.06 4.13 7.36 7.61 3.86 36 108 2 170 3.83 28 84 8.25 5.88 7.39 7.49 He 24 47.22 0.58 He 25 49.22 0.58 He 26 51.22 0.58 6 140 3.76 24 84 10 176 4.24 36 90 24.25 15.38 7.42 7.39 He 27 53.22 0.58 6 126 3.39 28 82 6 149 3.93 34 88 12.38 7.69 7.39 7.6 2 170 3.74 10 157 3.73 28 34 84 2 225 4.16 36 98 13.63 13 7.52 90 10 241 4.47 36 102 14.19 11.25 30 104 14 212 4.20 34 100 20.63 38 102 8 48 114 30 Hd. I 1.31 0.175 Hd 2 3.31 0.475 Hd 3 5.31 0.67 Hd 4 7.31 -2 184 3.99 0.62 12 230 4.15 Hd 5 9.31 0.59 10 224 4.04 Hd 6 11.31 0.59 Hd 7 13.31 Hd 8 Hd 0.60 8.75 32 106 3.77 0.74 0.64 164.34 160.20 160.20 130.23 0.66 7.74 183.61 148.54 0.73 7.3 7.61 254.79 127.91 1.02 14.19 7.39 7.62 14.75 17.75 7.36 7.59 0.81 48 120 17.75 14.25 7.15 7.66 265.10 125.85 165.04 204.24 156.79 0.64 1.06 98 18 2 3 8 4.35 203 3.91 10 236 4.13 42 122 22 192 3.57 62 154 28.16 26.13 7.43 7.68 239.31 136.16 0.96 0.575 10 232 4.12 42 106 6 145 3.30 40 100 25.44 16.06 7.41 7.71 15.31 0.55 10 225 3.75 38 104 18.19 7.51 286.76 126.88 210.43 0.84 9 17.31 0.575 4 240 4.12 108 20.5 7.03 529.17 2.12 Hd 10 19.31 0.475 24 321 5.04 46 156 19.56 6.46 402.29 1.61 Hd Hd 11 21.31 64 162 19.38 5.51 504.41 2.02 12 23.31 0.413 30 390 5.98 0.213 52 452 9.18 112 182 23.33 3.75 836.57 3.21 Hd 13 25.31 0.2 58 346 5.85 144 114 18.88 4.12 289.86 1.16 Hd 30 27.31 18 171 4.18 42 104 17.69 7.23 281.61 1.13 0.275 42 203.21 0.82 1.15 Pb Zn As2 ECI EC2 SALI 3.08 20 72 13.63 7.21 193.93 0.78 8 143 3.56 24 88 14.75 7.34 289.86 1.16 0 10 149 3.62 36 98 32 167 4.09 94 182 11.67 10.63 7.5 7.66 173.30 128.18 0,69 36 96 18 183 3.95 42 110 11.81 33.75 7.51 7.53 182.53 108.70 0.73 0.925 20 158 3.59 42 104 16 238 4.46 48 106 26.63 20.13 7.24 7.29 189.71 135.36 0.76 0.885 14 180 3.82 42 104 20 185 3.98 46 108 1.69 2.25 7.22 7.3 159.97 110.75 0.64 0.863 14 204 4.10 48 116 28 170 3.74 64 158 4 13.56 7.3 7.58 223.55 142.54 0.89 54 110 28 138 3.36 . 74 166 14.13 12.07 0.83 20 214 4.08 0.813 6 202 3.89 54 122 44 134 3.50 100 234 7.37 4.63 7.36 7.52 181.51 126.13 0.73 8 14.07 0.788 12 179 3.74 46 114 26 111 3.15 72 182 11.75 13 7.35 7.65 168.87 136.12 0.68 He 9 16.07 0.763 22 167 3.38 50 118 4 92 3.19 40 104 21.88 13 7.62 7.82 175.01 146.35 0.70 He 10 18.07 52 124 10.43 6.43 7.52 7.6 163.75 142.26 0.66 He 11 20.07 0.74 20 143 3.21 6 59 2.87 0.713 He 12 22.07 0.638 28 133 2.98 62 178 He 13 24.07 0.488 32 278 5.75 78 132 He 14 26.07 0.55 58 316 7.35 He 15 28.07 100 124 He 16 30.07 0.638 48 338 4.80 0.613 24 315 5.39 He 17 32.07 0.5 18 187 3.88 44 100 He 18 34.07 0.513 14 160 3.45 38 94 Hf I 0.91 0.725 8 146 3.46 32 82 18 154 4.07 34 106 7.06 8.81 Hf 2 2.91 0.738 12 180 3.96 40 100 30 108 3.62 82 214 6.44 9.44 Hf 3 4.91 3.71 54 140 14.69 7.46 Hf 4 6.91 0.6 24 178 3.86 50 114 15.81 7.17 Hf 5 8.91 Hf 6 7 10.91 12.91 98 2.86 0.568 10 176 3.57 0.338 14 240 4.58 T Q DIST ELEV As Hd 31 29.31 0.35 Hd 32 31.31 -0.05 He I ' 0.07 He 2 2.07 0.963 He 3 4.07 He 4 6.07 He 5 8.07 He 6 10.07 He 7 He Hf Cu 2 101 10 137 3.44 0.68 20 161 0.6 Fe 2 26 128 Cu2 Fe2 Pb2 Zn2 66 - 88 66 116 %CL1 %CL2 pH I 7.33 181.15 0.72 6.17 7.05 383.80 1.54 6.09 4.36 541.41 2.17 5.81 3.83 329.55 1.32 4.08 26 1143 5.44 70 256 2.31 316.25 1.26 12 50 110 6.94 1.06 6.65 7.19 286.57 131.00 1.15 10.56 4.69 7.12 7.41 231.30 177.06 191.39 0.93 7.55 7.68 168.21 0.67 7.34 7.61 181 3.79 6.44 7.37 144 3.49 50 134 7.06 7.63 7.22 8 30 104 33.83 25 6.96 48 20 150 3.43 195 4.01 46 120 33.23 11.25 7.08 8 14.91 0.413 18 229 4.44 50 130 Hf 9 16.91 0.455 20 329 5.19 58 152 0.80 7.16 16 Hf 200.99 5.31 30 86 42 106 128 pH2 - 47.78 6.85 34.24 5.86 105.01 146.80 120.30 . 173.31 0.77 0.59 0.69 196.76 0.79 134.57 107.04 177.39 112.14 7.36 ■ 165.42 204.47 195.22 0.54 0.71 7.05 7.02 246.59 0.66 0.78 0.99 T ELEV As Cu Fe Pb Zn A s2 Cu2 Fe2 Pb2 Zn2 %CL1 %CL2 Q DIST Hf 10 18.91 0.468 72 280 8.86 190 128 660.67 2.64 Hf 11 20.91 . 0.588 36 343 8.15 94 108 76 212 7.61 186 118 14.5 8.52 4.04 3.36 509.63 401.74 2.04 Hf 12 22.91 0.65 36 668 5.68 90 214 52 436 3.96 112 598 5.09 7 5.19 6.62 229.13 128.43 0.92 Hf 4 3 24.91 0.24 14 8 97 2.99 8.25 8.25 7.01 7.31 240.43 166.45 0.96 Hf 14 26.91 0.4 8 130 3 .7 2 42 104 Hf 15 28.91 0.48 36 Ia I 1.06 0.25 8 120 3.41 2 40 3.59 Ia 2 3.06 0.468 Ia 3 5.06 Ia 4 7.06 Ia 5 9.06 Ia 6 Ia 82 3.24 28 88 19.5 32 86 pH I pH 2 3.88 ECI EC2 SALI 10.01 7.43 304.13 1.22 98 12.9 7.25 482.91 1.93 16 66 5.88 7.5 493.94 1.98 58 3.43 26 76 2 107 4.01 26 78 10.63 10.63 6.9 375.72 1.50 0.44 12 113 3.60 0.425 14 117 3.44 28 86 14 184 3.83 34 92 36.75 26.63 6.78 34 96 31.3 6.31 8 107 3.10 40 96 16.5 6.93 851.63 3.25 11.06 . ' 0.4 18 177 3.77 42 110 . 20.69 6.71 885.69 3.36 7 13.06 40 98 26.4 6.38 1608.07 5.52 Ia 8 15.06 0.34 14 88 3.03 54 128 35.47 7.08 9 7 6 .8 7 3.63 Ia 9 17.06 0.32 20 58 2 .7 6 54 124 29.01 6.51 1217.33 4.35 Ia 10 19.06 0.29 20 52 140 21.35 6.49 1530.92 5.29 Ia 11 21.06 0.29 18 66 2.85 47 2.87 52 142 23.16 6.41 1545.95 Ia 12 23.06 0.29 28 54 126 Ib I 0.45 0.025 95 2.85 6 128 3.89 Ib 2 2.45 0.168 28 329 4.85 56 144 27.13 6.53 Ib 3 4.45 0.13 26 262 4.37 64 144 42.82 6.51 1255.00 4.47 Ib 4 6.45 74 170 32.5 6.34 1330.00 4.69 Ib 5 8.45 0.113 28 156 3.83 0.113 34 79 3.01 66 146 35.64 7.13 5.52 Ib 6 10.45 0.113 3 4 66 68 4.77 Ib 7 12.45 0-113 28 Ib 8 14.45 Ib 9 16.45 0.9 26 0.075 24 39 2.63 33 2.45 Ib 10 18.45 0.08 32 Ib 11 20.45 0.08 _28 0.42 0.375 4 18 109 3.26 31 2.77 2.47 56 2.61 37 2.57 36 94 - 7.3 706.35 31 6.60 1776.39 6.89 8 211 4.54 32 96 20 27.13 6.22 2.82 6.03 5,34 0.70 7 1230.00 243.00 6.93 1220.00 303.00 4.39 4.36 315,00 473.00 1.26 150.00 219.00 0.60 156 42.72 7 76 192 34.82 7.01 570.00 2.28 60 168 36.96 201.00 0.80 168 19.65 6.89 6.42 1260.00 4.48 70 164 22.93 23.44 7.05 212.00 0.85 6.52 '982.00 3.65 64 70 168 Fe Pb Zn A s2 12 112 4.51 . 28 84 14 143 5.14 32 34 98 14 233 4.75 40 T Q DIST Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Id Id Id Id Id Id Id Id Id Id Id Id Id Id I 1.3 ELEV As 0.35 2 3.3 0.605 3 5.3 0.588 4 7.3 0.568 5 9.3 0.525 2 2 6 11.3 7 Cu 8 151 3.81 Cu2 18 236 4.83 46 120 4.43 52 160 34 _ 631 0.475 36 285 6.96 90 64 13.3 0.413 40 317 6 .2 4 96 112 8 15.3 0.4 44 303 6.27 9 17.3 0.388 32 10 19.3 0.33 2 6 11 21.3 0.3 48 273 6.56 12 23.3 13 331 Fe2 PbZ Zn 2 %CL1 %CL2 pH I 88 15.94 17.75 6.78 98 19.75 15.94 6.96 16.63 7.31 ECI EC2 SALI 663.27 2.65 616.18 331.63 2.46 6.55 786.50 3.06 96 190 24.75 18.47 6.37 . 979.87 3.64 82 20.69 17.75 4.5 282.54 1.13 3 1 .7 8 6.06 801.53 3.10 96 118 19.5 5.85 881.68 3.35 150 25.31 6.43 1578.01 5.43 80 1 7 0 28.2 6.4 1277.44 4.53 90 23.3 5.77 636.22 2.54 0.225 36 278 4.92 96 112 55.58 5.27 25.3 0.225 44 305 6.85 116 132 17.69 4:55 14 27.3 0.225 3 6 68 2.81 86 192 28.93 6.76 ' 15 29.3 0.225 3 6 50 2.94 90 214 21.16 6.57 I 0.12 2 2.12 0.998 2 2 3 4.12 4 121 2.96 127 3.44 68 100 86 5.89 pH2 315 8.95 120 82 26 237 5.42 215 4.36 52 120 40 284 5.56 42 112 17.63 6.12 0.97 16 170 3.74 0.955 2 2 160 3.88 72 114 5 8.12 0.888 18 136 3.61 64 102 ' 6 10.12 0.775 .12 142 3.51 56 7 12.12 0.69 12 124 3.22 32 8 14.12 9 0.4 4 104 3.70 30 98 22.44 19.44 6.77 6.89 100 138 21.19 16.5 7.17 7.89 66 349.00 1.40 1164.97 4.19 1285.90 4.56 551.52 404.05 667.53 336.22 2.21 7.41 373.58 1.49 12.88 7.17 619.35 2.48 12.88 7.2 781.56 3.04 98 10.5 6.5 1250.50 4.45 84 9.94 6.78 879.87 3.34 22 166 3.74 54 116 11.63 6.68 1000.80 3.70 16.12 0.59 20 208 3.97 58 126 12.28 6.69 1007.68 3.72 10 18.12 62 136 13 12 20.12 22.12 16.64 11.75 6.85 11 0.53 28 255 4 .2 6 0.49 40 483 5.95 0.47 12 206 3.04 7.63 3.5 13 24.12 14 26.12 0 ,6 6 8 80 168 54 40 106 56 529 6.65 540 6.92 114 290 124 274 6.6 7.48 6.92 7 2.67 764.85 2.99 2.49 3.06 1.87 0.425 2 38 2.70 18 62 8.75 6.84 622.30 385.38 453.21 202.52 7 8 6 .4 8 0.425 6 28 2.63 14 52 7 6.87 467.96 1.81 T DIST ELEV As Cu Fe Pb Zn As2 38 90 Cu2 Fe2 Pb2 Zn2 %CL1 %CL2 pH I pH2 ECI 22 . 233 5.56 50 94 9.94 9.94 6.95 7.25 597.73 195.64 2.39 222 6.68 78 80 10.5 9.94 7.15 6.88 592.81 470.91 2.37 EC2 SALI Ie Q I 0.75 0.325 Ie 2 2.75 1.225 22 214 5.22 58 106 Ie 3 4.75 1.338 36 286 6.70 88 104 11.06 7.08 569.22 2,28 Ie 4 6.75 84 168 10.5 7.74 319.51 1.28 Ie 5 8.75 1-3 36 255 5.38 1.288 22 232 4.54 60 148 9.31 7,69 347.03 1.39 Ie 6 10.75 1.268 20 213 4.60 58 120 13.56 7.15 700.95 2.80 Ie 7 12.75 1.888 24 257 4.88 70 168 14.69 7.3 639.02 2.56 Ie 8 14.75 4 82 3.30 34 94 2 70 3.79 28 82 17.63 11.19 6.54 7.5 9 16.75 6 36 3.08 16 58 -2 18 . 60 14.19 9.5 7.09 7.51 Ie 10 18.75 1,25 4 35 3.10 16 64 -2 36 3.20 32 3.02 780.58 328.36 526.94 314.59 3.04 Ie 1.238 1.268 16 58 15.94 11.75 7.02 7.37 11 20.75 1.35 2 31 3.23 18 64 8 31 12 62 14.13 12.94 6.72 6.99 426.67 311.64 150.55 151.53 1.71 Ie 0.60 Ie 12 1.35 6 28 2.96 42 64 13.56 6.18 124.15 0.50 Ie 13 22.75 24.75 1.35 • 6 25 3.26 18 68 8.88 6.05 55.72 0.22 8 130 4.03 36 3.16 Ra I 1.81 0.3 6 117 3.49 26 84 14 154 3.93 30 88 Ra 2 3.81 0.7 6 91 3.20 22 76 8 146 3.80 26 86 Ra 3 5.81 0.72 4 99 3.39 26 80 Ra 4 7.81 0.62 -2 70 2.97 18 66 -2 118 3.61 26 Ra 5 9.81 0.42 Rb I 1.28 0.18 8 77 3.08 20 76 12 152 3.70 38 108 Rb 2 3.28 0.28 8 84 3.13 22 78 6 140 3.81 Rb 3 5.28 0.23 2 89 3.24 24 76 6 145 .3.73 121 Rb 4 7.28 0.03 2 58 2.92 16 64 Rb 5 9.28 -0.3 6 50 2.68 18 60 8 Re I 0.14 Re 2 2.14 Re 3 4 4.14 0.4 6.14 0.73 Re 11.25 7.34 7.47 183.97 115.58 0.74 14.63 7.35 7.45 220.57 0.88 18.19 4 0.6 24 125 3.90 14.75 82 ,15.25 2.11 7.32 124.25 188.79 0.76 20.56 7.09 7.21 201.31 125.22 0.81 12.88 12.88 7.48 7.42 1.01 36 100 16.38 16.38 7.4 7.4 251.40 133.89 223,46 169.52 0.89 26 94 24.75 18.97 7.33 7.31 219.61 153.17 0.88 3.61 26 82 11.88 15.38 7.38 7.27 174.33 118.91 0.70 77 2.72 20 68 9.5 11.25 6.97 6.75 357.73 473.62 1.43 183.40 0.73 52 134 8.88 7.02 0.41 Re 5 ' 8.14 0.87 Re 6 10.14 0.87 18 90 3.21 22 < 76 12 94 3.38 24 76 13.56 11.75 7.19 7.12 263.01 8 74 3.07 20 74 4 55 2.86 18 64 12.02 7.13 7.15 6.89 221.69 8 121 28 92 16 204 4.05 36 108 20.07 8.88 7.27 7.11 3.65 185.42 1.05 121.93 270.06 114.88 0.89 1.08 Fe2 PbZ Zn2 %CL1 %CL2 pH I PH2 50 3.09 24 68 22.38 22.38 7.16 7.25 390.99 188.44 1.56 35 2.99 14 54 18.18 16.5 7.16 7.27 192 4.22 52 140 14.13 13 7.46 7.41 320.45 H 70.30 232.00 134.00 0.93 8 106 3.69 32 92 16.62 12.44 7.27 7.3 50 130 32 99 3.50 70 196 12.94 13.56 7.44 7.43 312.00 158.00 202.00 132.00 0.81 3.31 28 96 12 115 3.58 48 134 14.69 13 7.36 7.43 94 3.35 28 86 30 227 4.60 56 152 15.88 15.94 7.2 7.15 252.00 143.00 239.00 139.00 0.96 2 100 3.25 22 80 4 96 3.03 22 82 11.81 10.06 6.77 6.41 267.00 281.00 1.07 6 101 3.47 -2 86 2.96 24 82 10 194 3.84 34 94 7.56 6.44 6.75 350.00 1.40 22 70 4 111 3.55 28 80 7 6.44 7.02 6.74 6 82 3.20 20 74 8 145 3.52 30 92 10.5 6.44 7.28 7.02 371.00 248.00 310.41 15,2.71' 1.24 0.85 4 96 3.39 26 80 14 195 4.25 34 102 11.06 12.88 7.18 6.65 0.038 2 38 2.86 14 60 0.23 -2 45 2.99 18 64 -2 40 2.84 14 60 8.25 5.31 7.16 4.09 0.313 6 18 60 4 46 3.03 20 66 10.63 10.63 7.35 4 6.09 0.525 -2 45 2.89 54 2.79 20 60 5.75 7.2 266.07 1.06 5 8.09 0.613 2 3.01 22 66 3.38 7.35 162.48 0.65 Re 6 10.09 0.605 -2 53 3.03 22 66 6.38 7.28 228.49 0.91 Re 7 12.09 0.59 -2 45 2.95 18 62 5.19 7.29 186.86 0.75 Re 8 14.09 0.58 2 59 3.08 20 68 Re .9 16.09 0.513 2 52 2.92 20 64 Re 10 18.09 0.455 -2 Re 20.09 0.4 22.09 0.668 51 3.05 -2 78 3.17 4 110 3.37 18 24 Re 11 12 Re 13 24.09 0.755 2 104 3.29 0.755 18 180 4.01 T Q DIST Re 7 Re 8 Rd Pb Zn As2 58 3.05 20 70 10 32 2.66 14 50 2 6 90 3.44 26 82 18 8 82 3.12 22 74 ELEV As Cu 12.14 0.94 4 14.14 0.94 -2 I 1'.7 0.92 Rd 2 3.7 1.02 Rd 3 5.7 1.1 Rd 4 7.7 1.05 6 Rd 5 •9.7 0.89 14 Rd 6 11.7 0.6 Rd 7 13.7 0.4 Rd 8 15.7 0.41 Rd 9 17.7 0.43 Rd 10 19.7 0.67 Rd 11 21.7 0.85 Rd 12 23.7 0.85 Rd 13 25.7 Re I 0.09 Re 2 2.09 Re 3 Re Re Re 14 26.09 Fe 18 135 3.63 91 61 Cu2 2.38 61 3.29 18 70 4.56 1.28 1.25 1.01 1.48 0.80 290.44 169.59 7.46 . 212.24 168.58 0.85 6.73 7.19 1.39 1.16 272.16 1.09 7.17 230.52 211.23 236.62 0.92 7.33 7.2 11.31 7.18 7.3 230.52 230.52 290.78 145.39 5.75 7.33 17.19 5.75 66 EC2 SALl 348.33 234.55 199.04 7.32 8.13 2 ECl 7.13 4 87 3.21 24 74 24 76 84 12 132 3.46 28 88 27.81 15.94 28 82 16 204 4.27 40 106 17.19 8.94 7.15 7.08 38 102 14 210 4.16 38 102 12.44 6 7.17 7.2 308.95 203.95 200.92 115.10 0.95 0.92 1.16 1.24 0.80 T Re Q 15 DIST 28.09 ELEV As 0.71 Cu Fe 6 113 3.43 Pb Zn A s2 Cu2 28 82 252 4.72 20 Fe2 Pb2 Zn2 %CL1 %CL2 pH I pH 2 46 122 27.5 29.63 7.19 6.79 90 6.95 7.14 ECI 0.74 7.22 7.21 260.49 109.04 1.04 7.25 307.94 109.04 Re 16 30.09 0.655 6 67 3.01 20 70 6 129 3.70 28 33.75 32.56 Re 17 32.09 0 .7 1 3 -2 77 3.13 22 72 6 61 2.91 16 62 32.56 28.5 Re 18 34.09 0.75 -2 67 2.93 18 66 2 40 2.78 8 52 21.25 7.07 Re 19 36.09 0.75 -2 74 3.09 22 76 11.75 7.26 247.36 Re 20 38.09 -2 60 2.88 20 66 11.75 7.2 295.83 Re 21 40.09 0.745 0.72 6 69 3.07 24 74 13.74 6.97 439.19 Re 22 42.09 0.67 6 77 3.21 30 90 16 94 3.35 42 110 Re 23 44.09 0.638 12 70 3.10 34 96 2 46 2.95 18 Re 24. 46.09 0.61 6 57 2.88 18 62 28 Re 25 48.09 0.613 8 68 2.96 36 100 22 107 3.56 116 3.74 165 4.17 Re 26 Re. 27 - 1.18 1.76 7.05 7.18 324.10 206.98 1.30 10.3 10.63 7.14 6.95 236.26 156.49 0.95 76 186 . 11.78 21.25 7.12 7.34 264.53 146.73 1.06 76 196 13 12.38 7.26 7.37 272.49 134.15 1.09 88 194 8.81 7.63 7.25 139.39 0.95 5.88 7.23 7.13 7.14 237.91 6.18 241.05 143.58 0.96 18.47 13.56 7.25 7.12 235.81 159.30 0.94 74 8 88 3.25 20 24 76 0.625 82 16 165 4.03 68 172 8 73 3.04 20 72 2 109 3.65 36 66 3.05 1.23 0.99 13.56 52.09 0.62 12 1.49 12.94 24 50.09 EC2 SALI 184.76 247.36 373.57 128.22 80 Re 28 54.09 0.638 Re 29 56.09 0.668 24 135 3.57 42 120 14.75 7.13 266.20 1.06 12 119 3.50 22 84 11.75 7.09 244.19 0.98 6 206 4.10 36 102 41.44 7:02 274.59 1.10 24 24 84 219.04 229.52 243.15 0.88 116.68 0.47 Re 30 58.09 0.625 Re 31 60.09 0.588 0.54 10 122 3.49 0.375 12 91 3.30 Re 32 62.09 Re 33 64.09 Rf I 0.42 Rf 2 Rf 10 397 5.26 54 136 86 31.79 23 4 35 2.75 18 54 2.42 3 4.42 0.43 2 39 2.57 14 52 13 7.55 142.72 0.57 Rf 4 6.42 0.4 2 45 2.87 20 60 18.31 7.46 193.77 0.78 Rf 5 8.42 0.5 Rf 6 10.42 0.575 2 54 2.81 18 62 22.33 7.4 300.03 1.20 Rf 7 12.42 0.613 2 20. 64 16.5 0.69 8 14.42 0.538 2 26 68 20 7.48 7.47 171.89 Rf 69 3.06 62 3.05 231.28 0.93 Rf 9 16.42 0.55 2 56 2.95 24 64 18.88 7.57 226.07 0.90 10 .18.42 0.55 2 52 3.00 20 64 5.88 7.41 260.45 1.04 Rf 50 0.97 0 .3 0.475 -2 12 6.76 7 17.13 35 2.71 7.13 11.81 15.38 7.52 7.49 111.47 FeZ PbZ ZnZ %CL1 Zn AsZ 59 3.06 22 70 10.5 60 3.18 70 9.38 59 3.08 28 24 70 2 55 2.77 20 0.775 2 53 2.69 30.42 0 .7 3 8 2 17 32.42 0.675 Rf 18 34.42 Rf 19 Rf Q DIST Rf 11 20.42 0.575 2 Rf 12 22.42 0.613 2 Rf 13 24.42 0.66 2 Rf 14 26.42 0.7 Rf 15 28.42 Rf 16 Rf ELEV As Cu Fe Cu2 Pb T %CL2 pH I pH 2 ECI ECZ SALI 7.33 339.62 1.36 7.35 254.20 1.02 10.5 7.34 253.15 1.01 60 7 7.37 252.11 1.01 22 58 5.88 7.58 197.94 0.79 58 2.82 20 62 5.25 7.26 264.61 1.06 2 60 3.10 28 70 9.38 7.44 234.07 0.94 0.68 4 51 2.78 22 60 11.19 7.45 180.30 36.42 0.538 2 43 2.80 22 58 20 38.42 0.568 2 41 2.81 16 56 7.69 7.44 188.73 Rf 21 40.42 0.59 2 45 3.00 24 62 11.19 7.39 2 0 2 .4 4 Rf 22 42.42 0.675 4 16 23 44.42 0.75 2 18 60 62 -2 Rf 46 2.98 52 3.00 Rf 24 46.42 0.82 2 66 2.83 20 60 -2 Rf 25 48.42 0.825 4 53 2.76 18 56 18.31 7.33 203.49 0.81 Rf 26 50.42 0.83 2 55 2.87 22 58 18.31 7.19 221.42 0.89 Rf 27 52.42 0.82 2 50 2.79 20 58 18.88 7.23 207.71 0.83 Rf 28 54.42 4 51 2.61 20 52 20.06 7.28 288.90 1.16 Rf 29 56.42 0 .7 6 8 0.725 Rf 30 58.42 0.825 4 49 2.67 20 52 18.25 7.16 357.43 1.43 58 20.06 7.28 303.49 1.21 18.25 7.31 225.78 4 52 3.30 55 3.19 ZO 16 66 68 11.19 9.44 10.06 11.75 11.75 89 3.21 30 70 20.06 7.49 7.44 7.36 7.26 0.72 128.63 0.86 0.75 0.81 7.48 210.87 139.18 7.58 2 4 5 .6 7 233.02 142.34 7.37 18.88 215.09 0.84 0.98 0.93 Rf 31 60.42 0.788 14 57 2.74 24 Rf 32 62.42 0.74 2 61 2.84 22 66 Rf 33 64.42 0.768 2 72 3.10 24 74 32 163 4.13 98 220 19.08 17.63 7.25 7.3 295.09 140.72 1.18 Rf 34 66.42 0.738 4 72 3.03 24 68 -2 194 4.07 42 J 08 20.01 18.25 7.27 7.08 463.11 353.90 1.85 Rf 35 68.42 0.538 69 3.10 20 66 6 3.57 40 108 25.44 6.94 6.86 Rf 36 37 70.42 0.45 8 2 80 3.01 24 74 0.413 4 39 2.43 16 52 Rf 72.42 161 24.19 18.94 7.1 744 0.90 2 7 9 .3 4 206.88 135.47 0.83 0.54 DMg I 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Fa Q BIOM DIV I 0.00 8 1.47 0 0 0 0 0 6 0 0 0 0 0 0 0 96 0 I 0 0 0 Fa 2 0.00 9 1.59 0 0 0 0 0 0 0 0 I 0 0 0 0 128 0 3 0 0 0 Fa 3 0.00 6 0.98 0 0 0 0 8 4 0 0 0 0 0 0 137 Q 0 0 0 2 Fa 4 0.00 8 1.44 0 0 0 0 4 I 0 0 2 0 0 0 0 0 115 0 0 0 0 0 Fa 5 0.13 8 1.54 0 0 0 0 3 5 0 0 0 0 ,0 0 0 67 0 3 0 0 0 Fa 6 0.00 9 1.73 0 0 0 0 I 3 0 0 0 0 0 0 0 75 0 0 0 0 0 Fa 7 0.00 11 2.09 0 0 0 0 6 I 0 0 3 0 0 0 ■0 74 0 0 18 I 0 Fa 8 0.44 9 1.71 0 0 0 0 0 2 0 0 0 0 0 0 2 89 0 0 4 0 I Fa 9 0.00 9 1.62 0 0 0 0 8 10 0 0 0 0 0 0 0 95 I 0 14 0 0 Fa 10 0.00 8 1.80 0 0 0 0 0 0 0 0 4 0 0 0 0 31 0 0 3 0 0 Fa 11 0.00 8 1.80 0 0 0 0 0 I 0 0 3 0 0 0 0 21 0 I 0 I 0 Fa 12 0.00 7 1.33 0 0 0. 0 0 0 0 .0 4 0 0 0 0 72 0 0 4 0 0 Fa 13 0.00 7 1.57 0 0 0 0 0 0 0 0 I 0 0 0 0 . 31 0 0 0 0 0 Fa 14 0.00 6 1.13 0 0 0 0 0 3 0 0 2 0 0 0 0 0 0 0 0 Fa 15 0.62 8 1.55 0 0 0 0 0 4 0 0 3 0 0 0 0 3 68 75 0 0 0 I 0 Fa 16 0.26 10 2.06 0 0 . 0 0 0 11 0 0 0 3 0 10 8 0 0.00 8 1.64 0 ■0 0 9 0 .0 0 0 0 0 0 32 32 0 I 0 0 0 Fb 0 .. 0 0 0 0 2 0 Fb 2 0.33 12 2.50 0 0 0 3 9 7 0 0 0 0 0 0 0 19 4 0 9 4 0 Fb 3 0.95 9 1.87 0 0 0 0 9 3 0 0 0 0 0 0 0 0 0 0 36 2 yO Fb 4 0.74 10 2.04 0 0 0 0 6 5 0 0 I 0 0 0 0 0 0 0 48 0 0 Fb 5 0.00 12 2.38 0 0 0 0 10 5 0 0 3 0 0 0 0 6 I 0 58 0 0 Fb 6 0.93 9 1.70 0 0 . 0 16 2 0 0 I 0 0 0 0 11 0 0 •63 0 0 Fb 7 0.62 8 1.57 0 .o 0 ' 0 0 11 4 0 0 0 0 0 0 . 0 18 0 0 0 0 Fb 8 0.00 12 2.35 0 0 0 9 10 I 0 0 3 0 0 0 0 0 0 0 62 63 2 Fb 9 0.00 10 2.24 0 0 0 2 8 3 0 7 0 0 0 0 0 0 0 0 0 10 0.27 0 0 0 2 9 5 0 0 0 O 0 0 0 0 0 0 0 Fb 11 0.00 •12 1.89 2.56 15 37 0 Fb 0 I 0 0 0 2 7 0 0 0 2 0 0 0 0 0 0 0 25 0 I Fb 12 0,00 12 2.89 0 0 0 I 4 I 0 I I 0 0 0 0 0 0 0 24 0 0 Fb 13 0.00 10 2.11 0 0 0 3 2 5 0 2 6 0 0 0 0 0 0 0 48 I 0 T 9 . I 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Fb 14 0.15 5 1.18 0 O 0 0 0 I 0 0 3 0 0 0 0 0 0 0 16 0 0 T Q BIOM DIV DMg Fb 15 0.00 11 3.06 0 0 0 0 4 2 0 I 0 0 0 0 0 0 0 0 5 I 0 Fe I 0.00 8 1.99 0 O 0 0 0 5 0 0 2 O 0 0 0 0 0 0 10 0 0 Fe 2 0.00 11 2.11 0 O 0 0 0 5 0 0 2 . 0 0 0 0 50 0 0 34 0 0 Fe 3 1.28 6 1.17 O 0 0 0 0 0 0 0 2 • O 0 0 0 10 0 ■ 0 52 0 0 Fe 4 0.00 4 0.65 0 0 0 0 0 0 0 0 5 0 0 0 0 12 0 0 81 0 0 Fe 5 0.00 3 0.45 0 0 0 0 0 0 0 O 2 0 O 0 0 0 O 0 83 0 0 Fe 6 0.00 3 0.44 0 O 0 0 0 O 0 0 0 0 0 0 0 0 0 0 95 0 0 Fe 7 0.00 6 1.28 0 0 0 0 0 0 0 0 I 0 0 0 0 0 O 0 44 0 0 Fe 8 0.00 10 1.98 0 0 0 0 0 4 0 0 3 0 O 0 O 55 0 0 18 3 0 Fe 9 0.00 1.79 0 0 0 O 3 I 0 O 2 0 O O 0 42 0 0 31 2 2 9 Fe 10 0.00 8 1.72 0 O O 3 0 ,1 0 O 0 0 0 0 0 0 37 4 I Fe 11 1.10 8 1.50 0 0 0 0 2 O 0 O I O 3 0 O O 7 O 0 0 88 4 0 Fe 12 0.00 4 0.74 0 O 0 0 0 O O O I 0 O 0 0 0 0 0 53 3 0 Fe 13 0.00 8 1.58 O 0 0 0 I O 0 0 0 O 0 0 2 0 0 0 55 0 0 Fe 14 0.00 10 2.32 0 0 0 0 I - 3 0 I I 0 0 0 0 0 0 I 12 0 0 Fe 15 0.00 1.46 O 0 0 0 7 3 O 0 0 O 0 0 0 0 0 0 41 0 0 7 He I 0.00 7 1.66 O 0 0 0 0 O O 0 0 O 0 0 8 0 O 0 O 0 0 He 0.00 5 1.19 O 0 0 0 0 O 0 0 O O 0 0 0 0 O 0 0 0 0 He 2 3 0.00 5 1.24 0 O O O 0 0 0 O 0 0 O 0 0 0 0 0 0 I 0 He 4 0.14 8 1.76 0 O 0 0 0 O 0 0 O 0 I 0 2 0 0 0 0 7 0 0 0 0 0 0 O 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 10 8 0 0 0 6 0 0 0 O 0 2 0 0 0 0 2 0 I 52 O 0 7 0 0 0 0 12 0 0 I 0 He 5 1.29 2 0.48 0 0 0 He 6 0.00 3 0.63 0 0 0 He 7 0.00 7 2.50 0 0 0 0 0 0 0 0 He 8 0.00 8 1.64 O . 0 0 0 0 0 0 O 0 O He 9 0.00 1.95 O O 0 0 0 O 0 0 0 0 10 0.21 2.46 O O 0 0 0 0 0 O 9 0 3 0 I 29 O I O 0 0 4 He 8 11 0 I 2.65 0 O 0 0 2 I 0 0 0 ' 0 0 0 0 5 0 0 0 0 0 2.39 0 0 2 0 0 4 0 0 0 0 0 0 0 0 2 I 0 0 2 He 11 He 12 0.11 10 1.07 10 I I 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 13 1.00 10 2.55 0 0 0 0 0 4 0 I 0 0 I 0 0 0 2 0 4 0 0 He 14 0.10 9 2.61 0 0 0 I 0 4 0 0 I 0 0 0 0 0 0 0 0 0 I He 15 0.72 4 1.00 0 0 0 0 11 5 0 0 0 0 I 0 0 0 0 .0 0 0 0 He 16 1.43 6 1.70 5 I 0 0 0 0 0 0 0 0 I 0 0 I 0 0 0 0 He 17 0.00 2 0.29 0 2 0 0 0 0 P 0 0 0 0 0 . o 0 0 , 0 0 0 0 0 He 18 0.28 3 0.53 0 0 0 . 0 0 0 0 0 0 0 0 0 0 0 0 0 32 0 ■ 0 He 19 0.16 5 1.08 0 0 ■0 0 0 0 0 0 . 0 0 0 0 0 0 2 0 28 0 0 He 20 0.00 4 0.94 0 0 0 0 0 0 0 0 0 0 0 0 0 ■0 0 0 7 0 0 He 21 0.00 . 4 0.83 0 0 0 0 0 I 0 0 0 0 . 0 0 0 0 I 0 25 0 0 He 22 0.28 9 2.43 0 4 0 0 0 0 0 0 0 0 I 0 0 0 I 0 I 0 0 He 23 0.03 3 0.80 0 0 3 0 0 0 0 0 0 0 0 0 0 __ 0 3 0 0 0 0 He 24 0.00 2 0.35 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 He 25 1.49 I 0.00 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 0 0 0 0 0 0 He 26 0.75 4 1,11 0 0 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 He 27 0.46 4 0.90 0 0 0 0 0 0 9 0 0 0 0 0 0 0 0 0 6 0 0 0 I 0 T Q BIOM DIV • - Hd I 1.17 10 2.56 0 3 0 0 4 0 . 0 I 0 0 0 0 0 0 3 0 Hd 2 0.98 13 3.49 0 I • 0 0 4 I 3 .1 0 I 0 0 0 0 0 0 0 0 Hd 3 0.94 10 2.40 0 4 0 0 11 2 3 0 0 I 0 2 0 0 0 0 0 0 0 0 Hd 4 0.09 11 • 2,72 0 0 0 0 5 8 I I 3 0 ■ 0 0 0 0 0 0 0 0 0 Hd 5 0.00 9 , 1.89 0 0 0 0 13 0 0 0 9 0 0 0 0 0 0 ■0 11 0 0 Hd 6 1.29 12 3.10 0 6 I 0 0 3 0 2 0 0 0 0 0 0 2 0 10 Hd 7 0.52 7 1.73 -0 2 0 0 5 2 0 0 0 0 0 0 2 0 0 0 2 0 0 0 0 Hd 8 0.00 7 0 3 0 0 0 4 0 0 0 0 0 0 0 0 I 0 0 0 0 Hd 9 0.07 10 1.76 2.20 0 2 0 0 3 3 0 0 7 0 0 0 0 0 4 0 36 0 0 Hd 10 0.00 8 1.83 0 9 I 0 0 5 0 0 0 0 0 0 0 14 0 0 11 0.00 7 1.55 0 0 0 0 Hd 0 0 0 2 0 0 0 3 0 0 0 0 0 0 24 0 0 Hd 12 0.33 11 2.73 0 0 0 0 0 0 0 I 0 0 0 .0 0 0 0 I 0 9 0 0 Hd 13 0.12 3 0.42 0 0 0 2.60 0 0 0 0 9 0 0 0 0 0 0 0 I 0 0 0 0 0 0 0 0 0 105 0 0 0 0 0 30 2.10 12 0 0 0 Hd 0 0 14 4 100 DMg He T Q BIOM DIV Hd 31 1 .2 8 11 Hd 32 0.60 12 DMg I 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 2.35 0 0 0 0 15 5' 0 0 0 0 0 0 0 17 2 0 14 0 I 2.89 0 ' I 0 0 3 I 0 0 3 • 0 I 0 0 0 3 0 3 0 0 He I 0 .0 0 8 2.02 0 0 7 0 2 I 0 I 7 0 0 0 0 0 0 0 0 He 2 4.31 10 2.68 0 2 3 0 5 3 0 I 3 0 . 0 0 0 0 0 0 0 0 0 0 0 He 3 0.00 2.28 0 0 0 0 3 2 0 I 0 0 0 0 0 0 0 0 13 0 0 He 4 0.24 9 11 2.52 0 5 0 0 8 4 0 2 2 0 0 0 0 0 0 0 9 0 0 He 5 0.30 12 2.79 0 3 I 0 6 I 0 0 0 0 0 0 0 2 0 3 0 0 He 6 0.25 8 1.89 0 2 I 0 I 0 0 0 0 . 0 0 0 0 0 0 0 0 7 0 0 He 7 0.52 10 2.42 0 8 I 0 0 0 0 0 0 0 0 0 0 0 5 0 0 0 0 He 8 0.15 12 3.06 0 3 3 P I 0 0 0 0 0 I 0 0 0 I 0 0 0 0 He 9 1.28 6 1.42 0 I I 0 0 3 0 0 0 0 0 0 0 0 5 0 0 0 0 He 0.58 5 0.00 10 1.13 2 0 0 0 0 0 0 4 0 0 0 0 0 0 I 0 0 0 0 He 10 11 2.07 0 18 0 0 0 2 23 .0 0 0 0 0 0 0 3 0 0 0 0 He 12 0.11 10 2 3 0 0 0 0 0 5 0 0 0 0 0 0 2 0 0 0 0 He 13 0.28 9 2 .3 3 2.11 0 0 0 0 I 2 0 0 0 0 0 0 0 31 0 0 14 0.00 7 1.37 0 0 0 0 0 3 0 0 I o 0 0 He 0 . 0 0 0 0 0 0 66 0 0 He 15 0.00 0 0 0 0 0 0 0 0 0 0 0 .0 0 0 0 0 0 0 0 He 16 0 0 .0 0 2.32 10 2.41 0 0 0 0 ■ 0 4 0 0 I 0 0 0 ' 0 3 0 0 0 0 I He 17 0.00 7 1.49 0 0 0 0 10 0 0 6 0 0 0 0 0 12 0 0 0 0 I He 18 0.51 9 2.40 0 0 0 0 5 0 I 0 0 I 0 0 0 0 0 0 0 0 4 Hf I 1.57 8 1.95 0 0 0 0 4 5 11 0 0 0 0 ■ 0 0 0 2 0 0 0 0 Hf 2 0.15 8 1.99 0 0 0 0 0 5 0 0 0 0 I 0 0 0 5 0 0 0 0 Hf 3 1.24 10 2.54 0 I I 0 0 3 2 0 4 0 0 0 0 0 4 0 0 0 0 Hf 4 0.56 6 1.30 0 0 0 0 23 0 0 4 0 0 0 0 0 0 0 0 13 0 0 Hf 5 0.00 8 1.76 0 0 0 0 17 0 0 I 0 0 0 2 0 25 0 0 6 0.27 6 0 0 0 0 11 0 5 0 0 0 0 6 0 0 0 7 0.00 3 0 0 0 0 0 0 5 0 0 0 0 0 0 0 0 Hf 8 0.00 4 0.70 0 0 ■ 6 2 0 I 0 0 0 0 0 0 0 0 0 . Hf 9 0.00 4 0.69 0 0 0 . 0 . 0 0 28 88 0 Hf 1.20 0.44 0 I 0 Hf 3 0 6 0 0 2 0 0 0 0 0 0 0 0 0 0 ■ 0 0 0 0 r 64 58 18 19 T Q BIOM DIV DMg I 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Hf 10 0.32 8 1.63 0 0 0 0 6 I 0 0 6 0 0 0 0 0 0 0 55 0 0 Hf 11 0.00 7 1.78 0 0 0 0 0 0 0 . 0 0 0 0 0 0 0 6 0 0 0 0 Hf 12 0.00 5 1.23 0 0 0 0 0 5 0 O 0 0 0 0 0 4 0 0 0 0 0 Hf 13 0.00 4 0.79 0 0 0 0 0 0 0 0 26 0 0 0 0 4 0 0 0 0 0 Hf 14 0.20 5 0.93 0 0 0 0 26 0 0 0 0 3 0 0 0 42 0 0 0 0 0 Hf 15 0.88 8 1.66 0 0 0 0 8 0 0 0 2 0 0 0 0 37 0 0 0 I 0 Ia I 0.00 9 1.90 0 0 0 0 0 6 0 2 0 I 0 2 43 0 0 0 0 I Ia 2 1.32 8 1.95 0 0 0 0 2 6 0 . 0 0 2 0 I 0 0 0 0 0 0 0 0 Ia 3 0.33 10 2.11 0 0 0 0 11 3 0 0 4 0 0 0 0 35 0 0 0 0 0 Ia 4 0.00 11 2.19 0 0 0 0 16 I 0 0 2 0 0 0 0 46 I 0 20 0 0 Ia 5 0.50 6 1.15 0 0 0 0 10 0 0 0 4 0 0 0 0 0 I 0 54 0 0 Ia 0.21 9 2.14 0 0 0 0 8 0 I 0 0 0 0 11 0 0 0 7 1.58 0 0 0 0 11 0 0 4 0 0 0 0 0 0 0 0 21 0 0.31 0 2 8 Ia 6 7 0 0 Ia 8 0.00 10 2.59 0 0 0 0 2 4 0 0 0 0 0 0 0 3 3 0 5 0 0 Ia 9 0.30 12 2.86 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