Open Collections

UBC Theses and Dissertations

UBC Theses Logo

UBC Theses and Dissertations

Arsenic in plants important to two Yukon First Nations : impacts of gold mining and reclamation practices Nicholson, Heather Christine 2002

Your browser doesn't seem to have a PDF viewer, please download the PDF to view this item.

Item Metadata

Download

Media
831-ubc_2003-0065.pdf [ 17.27MB ]
Metadata
JSON: 831-1.0090884.json
JSON-LD: 831-1.0090884-ld.json
RDF/XML (Pretty): 831-1.0090884-rdf.xml
RDF/JSON: 831-1.0090884-rdf.json
Turtle: 831-1.0090884-turtle.txt
N-Triples: 831-1.0090884-rdf-ntriples.txt
Original Record: 831-1.0090884-source.json
Full Text
831-1.0090884-fulltext.txt
Citation
831-1.0090884.ris

Full Text

Arsenic in Plants Important to Two Yukon First Nations: Impacts of Gold Mining and Reclamation Practices by Heather Christ ine N icho lson B . S c , Queen 's University, 1999 A T H E S I S S U B M I T T E D IN P A R T I A L F U L F I L L M E N T O F T H E R E Q U I R E M E N T S F O R T H E D E G R E E O F M A S T E R O F S C I E N C E in T H E F A C U L T Y O F G R A D U A T E S T U D I E S (Department of Geography) W e accept this thesis as conforming to the required standard T H E U N I V E R S I T Y O F BRITISH C O L U M B I A December 2002 © Heather Christ ine Nicho lson, 2002 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, 1 agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of GeO&tZf\ The University of British Columbia Vancouver, Canada Date bee . Iff 'OZ DE-6 (2788) II Abstract This project examines arsenic in plants growing near closed or reclaimed gold mines located in the traditional territories of two Yukon First Nations. A total of 238 soil and plant samples (comprising 9 different species) were collected from Mt. Nansen, Arctic Gold and Silver, and Venus Mine tailing properties. At each property, samples were collected near the suspected point source of contamination, approximately 1 -3 km away, and from background sites. Species were chosen for their ethnobotanical significance to the Little Salmon/Carmacks and the Carcross/Tagish First Nations, based on interviews with Elders and other knowledgeable people. Total and inorganic arsenic concentrations were determined using ICP-MS and AAS instrumentation, and organic arsenic concentrations were calculated from the difference. Uptake of arsenic by plants was low compared to soil arsenic concentrations. In both plants and soil, the arsenic form was predominantly inorganic. Concentrations in berries at all three sites were low or undetectable, and are therefore considered safe to eat under Health Canada tolerable daily intake guidelines for inorganic arsenic. At Mt. Nansen, the lichen "caribou moss" (Cetraria/Cladina spp.), Bolete mushrooms (Leccinum spp.), and the medicinal shrubs willow (Salix spp.) and Labrador tea (Ledum groenlandicum/L. decumbens spp.) had high mean arsenic concentrations around point sources or at sites up to 1.5 km away. These localized high concentrations will not likely affect foraging animals, given their constant movement. However, Carmacks residents could avoid gathering all species with elevated arsenic around the Mt. Nansen mining property until reclamation is complete. Table of Contents Page Abstract ii T a b l e of Contents iii List of F igures v List of T a b l e s vi List of Append i ces vii Acknowledgements viii Dedicat ion ix Chap te r 1: Introduction and Resea rch Object ives 1 1.1 Introduction 1 1.2 R e s e a r c h Object ives 2 Chapter 2: Literature Rev iew 3 2.1 A rsen i c 3 2.1.1 Introduction 3 2.1.2 A rsen i c in Soi l 4 2.1.3 A r s e n i c Uptake in Plants 7 2.1.4 Phys io log ica l and Biochemical Effects of A rsen i c in P lants 8 2.1.5 Plant Mechan i sms to R e d u c e Toxicity 10 2.1.6 T h e Uptake of A rsen ic by Humans 12 2.1.7 T h e Movement of A rsen ic in the Body 13 2.1.8 Effects of A rsen ic in Humans 14 2.1.9 A rsen i c Gu ide l ines 14 2.2 Stud ies of A rsen ic in Northern Plants 16 2.2.1 Point Source Studies 16 2.2.2 Stud ies Determining Base l ine Concentrat ions 19 2.3 Introduction to Ethnobotany and Tradit ional Knowledge 21 Chap te r 3: Si te Descr ipt ions and Methods 22 3.1 Study Si tes 22 3.1.1 Mt. N a n s e n Property 22 iv Page 3.1.2 V e n u s Mine Property 26 3.1.3 Arct ic Go ld and Si lver Mine Property 30 3.2 Sampl ing Methodology 32 3.3 Laboratory Ana lys is 36 3.4 Stat ist ical Ana lys is 37 Chapte r 4: Resu l ts 38 4.1 Mt. N a n s e n Mine Site 45 4.2 V e n u s Mine Tai l ings Site 48 4 .3 Arct ic Go ld and Si lver Mine Tai l ings Site 50 Chapte r 5: D iscuss ion 50 5.1 Compar i sons Wi th Other Yukon Data 50 5.2 Tempora l T rends 51 5.3 Interpretation of Resul ts 55 5.3.1 Mt. N a n s e n Mine Site 55 5.3.2 V e n u s Mine Tai l ings Site 56 5.3.3 Arct ic Go ld and Si lver Mine Tai l ings Site 58 5.4 Ethnobotany 58 5.4.1 D iscuss ion of Plants Sampled in this Study 58 5.4.2 Preparat ion of Plant Medic ine 66 5.5 To lerab le Daily Intake Calculat ions 67 5.5.1 Mt. Nansen Mine Site 68 5.5.2 V e n u s Mine Tai l ings Site 68 5.5.3 Arct ic G o l d and Si lver Mine Tai l ings Site 69 Chapter 6: Recommendat ions 69 6.1.1 Mt. Nansen Mine Site 69 6.1.2 V e n u s Mine Tai l ings Site 70 6.1.3 Arct ic Go ld and Si lver Mine Tai l ings Site 71 Chapte r 7: Limitations 71 Chapte r 8: Conc lus ions 72 Re fe rences 73 A p p e n d i c e s 85 V List of F igures Page 1. Locat ion of the study sites within the traditional territories of the Little 2 Sa lmon /Ca rmacks First Nation, and the Carc ross /Tag ish First Nat ion 2. Mt. N a n s e n aer ial photograph showing the tail ing ponds, B r o w n - M c D a d e 2 5 open pit, and Dome Creek in 1990 3. Aer ia l photograph of V e n u s tail ings pond showing its proximity to W i n d y 28 A rm of Tag i sh Lake and Montana Mountain in A ) 1975, and B) 1990 4. Aer ia l photograph of the Arct ic Go ld and Si lver property showing the 32 mill, tai l ings pond, and Tank Creek in 1995 5. Sampl ing locat ions at the Mt. Nansen study site, including background 33 and point source locations 6. Sampl ing locat ions for the Arct ic Go ld and Silver, and the V e n u s Mine 34 tail ing si tes 7. M e a n total arsen ic concentrat ion in plants col lected at e a c h mine site 39 8. M e a n total arsen ic concentrat ion in soi ls col lected at e a c h mine site 40 9. M e a n arsen ic concentrat ion in soi ls col lected at each mine site 40 10. M e a n arsen ic concentrat ion in plants col lected at each mine site 41 11. M e a n organic a rsen ic concentrat ion in plants col lected at e a c h mine site 42 12. M e a n organic a rsen ic concentrat ion in soi ls col lected at e a c h mine site 43 13. B io log ica l Absorpt ion Coeff icient (BAC) for spec ies at different locat ions 44 within the three mine study sites 14. M e a n inorganic a rsen ic concentrat ion in plants co l lec ted at e a c h mine 46 site 15. M e a n inorganic arsen ic concentrat ion in soi ls col lected at e a c h mine site 49 16. Total a rsen ic concentrat ions in soil samples col lected from Mt. N a n s e n 52 in 1984 and 2001 17. Total a rsen ic concentrat ions in raspberry samples col lected throughout 53 the Y u k o n in different years 18. Total a rsen ic concentrat ions in soi l samples co l lected from the V e n u s 54 Mine tai l ings site in 1984 and 2001 19. B io log ica l Absorpt ion Coefficient (BAC) plotted against total soi l a rsen ic 57 vi List of Tab les Page 1. C o m m o n arsen ica ls and their historical uses 5 2. G loba l a rsen ic inputs to soil from human activit ies 6 3. Strategies by plants to avoid heavy metal stress 10 4. Est imated average daily intake of inorganic a rsen ic by the C a n a d i a n 13 genera l populat ion 5. Cr i ter ia for a rsen ic contamination in soi l in ug/kg (ppm) dry weight 15 6. M e a n arsen ic concentrat ions in vegetation col lected throughout the 20 Y u k o n 7. Breakdown of samples ana lysed for arsenic content at e a c h mine 35 site vii Append ices Page A 1 . Nutrit ional table for important plant foods and medic ines used in the 86 Y u k o n . A 2 . Latin, (Northern) Tutchone, Tag ish , Tlingit, and common names of 88 some Y u k o n plant spec ies . A 3 a . A N O V A results for testing dif ferences between the m e a n s 89 (Wi lcoxon Rank S u m test for independent groups at a = 0.05) for locat ion (1, 2, or 3). Data sets include total arsenic, inorganic arsenic , and organic arsenic. A 3 b . Resu l ts of normality and significant means tests done after 90 A N O V A s were performed. A 3 c . Resu l ts of equal var iance, and model testing to determine effects of 92 geology on arsen ic concentrat ions at each mine site locat ion ( 1 , 2 , or 3). A 3 d . Resu l ts of statistical tests compar ing wil low s tems versus wi l low 94 leaves. A 4 . Compar i son of mean total arsenic concentrat ions in data co l lec ted 95 from previous studies and in this study. A 5 . To le rab le Dai ly Intake (TDI) calculat ions b a s e d on the mean, 99 maximum, and minimum (dry and wet) inorganic a rsen ic concentrat ions (shown in bold) in different plant samp les . T a b l e s are differentiated by spec ies and location (1, 2, or 3). A 6 a . G lossa ry of common plant compounds. 102 A 6 b . G lossa ry of se lected terms used in or related to this dissertat ion. 102 Vlll Acknowledgements Th is study would never have been done in the first p lace if my superv isor G r e g Henry hadn't pointed out the Northern Contaminants Program websi te . Pat R o a c h , my unofficial second superv isor up north and the Yukon Contaminants Commit tee Chai r , sugges ted ideas for the eventual project. Both were an integral part of it ever s ince. The i r gu idance, and the suggest ions offered by Les Lavkul ich a n d Br ian Compton are greatly apprec iated. My 2001 Yukon field season ran smoothly partly because I had such fantast ic f ield ass is tants, and partly because of logistical support by the fol lowing amaz ing individuals: Bever ley Brown, Dawn Char l ie , Dan Cresswe l l , Haro ld Ga tensby , Pat R o a c h , Dan Sprague, and Rob Stroshein. Thanks to my superstar f ield ass is tants (Jenni fer J o e and Ernest R ichards in Carc ross , and C indy Char l ie , V a n e s s a Char l ie , and J a s o n Fai rc lough in Carmacks) for braving mosqui toes and those odd rainy days to get all the sampl ing f in ished. Y o u guys are awesome! Equal ly as important were the people who provided technical support: spec ia l recognit ion goes to A l Doherty, J e a n Beckerton, C indy D ickson, J o a n Earner, Ruth Hal l , Brett Har tshome, Norma Kass i , W a y n e Kettley, Murray Lundberg, Wi l l i am Mann , Doris M c L e a n , G o r d Mitchel l , S u e Moody, Ron Pearson , Karen Pel let ier, Dan Sprague, Dick Sti l lwell , Bob van Dijken, Jody Walker , and Gerry Whit ley. I am indebted to Mary Gamberg for providing her a rsen ic data from previous years with which to compare my own, and to Sandy Lapsky , the Geography Department 's f inancial wizard. I wou ld particularly like to express gratitude to part icipating E lders from the Little S a l m o n / C a r m a c k s First Nation and the Carc ross /Tag ish First Nat ion. Y o u r knowledge of local plants was incredible, and I really enjoyed learning from you. To my lab-mates Sandra Rolph, Dave Bean , Becky Za la tan and Kar in Clark: thanks for the laughs, help with statistics and computers, and the chats about the north. Y o u kept things sane ; S a n , W e d n e s d a y yoga and sushi nights will be m issed ! Thanks a lso to the phys ics crowd and the geography girls for the entertaining movie nights, socce r games , surpr ise dinners, hiking trips, and suggest ions that peas shou ld be a d d e d to spaghett i sauce . I am extremely grateful to Mom, Dad, Lynn, Dav id , and G r a n d m a for their express ion of love and interest; to the Weste rn N icho lsons for making hol idays feel as if I were at home; and to Tom Davis, for his cont inuous support and principal role in making Vancouve r so enjoyable. Thanks and love to you al l . Acknowledgement is gratefully given to the fol lowing organizat ions that awarded grants to G r e g Henry and/or Heather Nicho lson: Northern Contaminants Program (DIAND), Min ing Environment Resea rch Group (Yukon Government) , A I N A Grant- in-Aid Program (Arctic Institute of North Amer ica) , Natural S c i e n c e s and Engineer ing R e s e a r c h Counc i l of C a n a d a , and the Northern Scient i f ic Tra in ing Program (DIAND). Dedicated to the memory of Howard Morton Brown June 16, 1904 - December 28, 2000 Loving Grandfather, Mentor, and Environmentalist Chapter 1: Introduction and Research Objectives 1 1.1 Introduction Th is study examines arsenic in plants signif icant to Yukon ' s Little S a l m o n / C a r m a c k s First Nation ( L S C F N ) and the Carc ross /Tag ish First Nat ion ( C T F N ) , at three gold mine sites found within their respect ive traditional territories (Figure 1). Loca l residents who gather plant foods and medic ines in the vicinity of the mines were concerned about arsen ic exposure from direct consumpt ion or from the foraging an imals they hunt and trap. A rsen i c is commonly assoc ia ted with gold-bear ing ore. Pr ior to a completed mine reclamat ion program, arsenic can be re leased to the surrounding environment through windblown tail ings, or through hydrologic pathways such as groundwater s e e p a g e and over land flow. The element can then enter plants by the root sys tem or by foliar absorpt ion. Health r isks assoc ia ted with ingesting plants contain ing arsen ic depend on the concentrat ion and the form of arsen ic present; inorganic a rsen ic is more toxic than organic forms. It is, therefore, of interest to determine the forms taken up by different plants compared to surrounding soi ls, and in what concentrat ions. A round the Mt. Nansen mining property, the L S C F N "pick blueberr ies, cranberr ies, b lackberr ies, stone berr ies and arct ic raspberr ies p lus Labrador tea, car ibou horn moss and other assorted medicinal plants. Mushrooms are a lso harvested in s e a s o n " (Noble, 2000, 3). One component of the study was to determine if plants traditionally gathered near Mount Nansen by the L S C F N are safe to consume. Min ing has intermittently taken p lace here s ince the 1920's. T h e most recent operat ion ( B Y G Natural R e s o u r c e s Inc: Oct '96 - Feb '99) c losed due to environmental infractions. The site w a s left with an improperly des igned tail ings pond and an open pit as potential contaminat ion sources. The Department of Indian Affairs and Northern Development (DIAND, a lso known as INAC) operate a wastewater treatment program that will l ikely cont inue until the mine is rehabil itated (P. Roach , pers. comm., 2002) . T h e C T F N gathered berries near two abandoned mines south of Carc ross , Y u k o n , prior to warnings being raised about their high arsen ic content. T h e tail ings from the V e n u s and the Arct ic Go ld and Si lver propert ies are now c a p p e d , and the sites are cons idered "contained" (B. Hartshorne, pers. comm., 2002). By us ing previously collected data from the tailing sites as well as collections made in 2 0 0 1 , pre- and post-reclamation arsenic concentrations could be compared, and health risks determined for the current levels of arsenic in the fruit. BEAUFORT SEA A L A S K A Carcross/Tagish First Nation BRITISH C O L U M B I A IOO a t 200 st-SCALE W KILOMSTEDS Figure 1. Location of the study sites within the traditional territories of the Little Salmon/Carmacks First Nation, and the Carcross/Tagish First Nation. 1.2 Research Objectives There were four primary objectives in this project: • To determine if plants gathered in the vicinity of the three tailing sites are safe for consumption; 3 • T o examine temporal and spatial trends of arsenic in soi l and plants at three mine s i tes in varying s tages of reclamation; • To determine the form of arsenic preferentially taken up by different plant spec ies ; • To investigate the ethnobotanical s igni f icance of common local plants to the First Nat ions. T h e object ives of this study were initially identified by the Little S a l m o n / C a r m a c k s First Nat ion in a proposal submitted in 2000 to the Y u k o n Loca l Contaminant Conce rns ( L C C ) committee of the Northern Contaminants Program. T h e L C C Cha i r (Pat Roach) sugges ted that a compar ison of reclaimed mine sites would be usefu l , and so the project was broadened to the Carc ross region. It is recogn ized that the original L S C F N proposal e n c o m p a s s e d object ives other than testing for contaminat ion in local vegetat ion: W e would like to do more extensive testing and studies of plants, water and an imals in that particular a rea to ensure the berries, plants and game [are] safe to cont inue to harvest... we are quite concerned with the effects on our health shou ld we cont inue to harvest from the land in the a rea as we have done for thousands of years (Noble, 2000, 3). Conc lud ing statements from this study about the health of the land surrounding the Mount N a n s e n mine should be taken in context of the object ives, s ince an analys is of wildlife and water was beyond the scope of this dissertat ion. Chapter 2: Literature Review 2.1 A r s e n i c 2.1.1 Introduction A rsen i c is found naturally in water, air, soi l , and biota, a n d is the 2 0 t h most abundant element in the earth's crust with a concentrat ion of ~1.5 to 2 ppm (National R e s e a r c h Counc i l , 1977). It is assoc ia ted with z inc, lead, gold, copper, and particularly su lph ide ores, and can be re leased through natural eros ion and mining pract ices. A r s e n i c is itself mined and used for d iverse agricultural and industrial appl icat ions. Its compounds have been used as insect ic ides, and for bronzing and medic ina l purposes for mi l lennia; bronze al loys have been dated back to 3000 B . C . (Nr iagu and A z c u e , 4 1990). A l leged ly d iscovered by Albertus Magnus c i rca. 1250 A . D . as he mixed soap with orpiment, a rsen ic ("arsenicum" L. or "arsenikon" Gr. for yel low orpiment) ga ined notoriety in the Middle A g e s as a murder and suic ide po ison. Fo r the past two centur ies, however, arsenic has been predominantly used for w e e d and insect control and as a wood preservat ive. High purity forms of the element have recent ly found roles in the manufactur ing of lasers, ammunit ion, and pyrotechnics (Bhumbla and Keefer, 1994). Tab le 1 d isp lays a list of some common arsen ic compounds and their common industrial uses . Often inc luded in studies of heavy meta ls 1 because of its densi ty of 5.72 g / c m 3 and toxic propert ies, arsen ic is neither a metal nor non-metal as it d isp lays propert ies of both. It is therefore commonly referred to as a semi-metal or metal loid. A r s e n i c occurs naturally in four oxidation states: A s + S (arsenate), A s + 3 (arsenite), A s " 3 (arsine), and A s 0 (elemental arsenic) . A long with environmental condit ions (e.g. pH and soi l type), the oxidat ion state determines the arsenic fraction that is mobi le and ava i lab le to biota. The toxicity of this element a lso depends on its form; inorganic a rsen ic is more phytotoxic than organoarsen ica ls (C -As structures). For example, the order of dec reas ing toxicity is: A s " 3 > A s + 3 > A s + 5 > monomethylarsonic ac id (MMA) > dimethylars in ic ac id (DMA) (Pantsar -Kal l io and Manninen, 1997). Because of the differing toxicit ies ( leading to different health r isks), and likely due to improved analyt ical techn iques, there has been an increas ing shift away from analyz ing total arsen ic over the past few decades . 2.1.2 A rsen i c in Soi l A r s e n i c in so i ls comes from the weather ing of rocks. T h e element is a component of more than 200 minerals, including arsen ides and su lph ides of silver, n ickel and cobalt, plus oxides arsenates, and arseni tes (Smedley and Kinniburgh, 2002) . S o m e examples of minerals with arsen ic are: adamite, annaberg i te , apatite, arsenopyr i te (the most common), cobaltite, erythrite, g laucodot, mimetite, nickel ine, ol ivenite, orpiment, proustite, realgar, scorodite, and skutterudite (Mottana etal., 1977). A r s e n i c in so i ls a lso comes from human inputs such as sewage , min ing waste rock, insect ic ides, ferti l izers, and atmospher ic fallout of smelters and fossi l fuel combust ion. r 1 This term is defined by the rather arbitrary physical property of density; elements exceeding 5 g/cm3 are called heavy metals. Classifications based on biochemical properties would be more suitable. 5 Tab le 1. C o m m o n arsenica ls and their historical uses (from Nr iagu and A z c u e , 1990, and supp lemented by National Resea rch Counc i l , 1977; Lederer and Fensterhe im, 1983; K o c h , 1998). Dates indicate the first known use of the chemica l . Names and Abbreviations Inorganic Compounds Chemical Formula Uses and other notes Arsenic metal, elemental arsenic: A s 0 As Alloy, solder, electrophotography High-purity arsenic (99.9999%) e.g. Gallium arsenide GaAs and other Group 3A and Group V A compounds Photoemissive surfaces, optoelectric devices, solar cells, semiconductors Arsenic acid (arsenate): As 5 or As (V) AsO(OH) 3 1955: wood preservative salts, feed additive, cotton desiccant, defoliant Arsenic sulphide Pyrotechnics, depilatory (leather industry) Arsenic trisulphide (orpiment) A s 2 S 3 Pigment Arsenic trioxide (white arsenic) A s 2 0 3 Poison, soil sterilant, herbicide, medicine or virility compound in some past cultures Arsenopyrite (mispickel) FeAsS Common sulphide mineral Arsenous acid (arsenite): A s + 3 or As (III) As(OH) 3 Arsine (arsenic hydride) As" 3 or As (-III) A s H 3 Gas Calcium arsenate C a 3 ( A s 0 4 ) 2 1906: insecticide (cotton crops) London purple mixture of A s 2 0 3 , C a C 0 3 , Fe and Al oxides, dye etc. -1870-1960: insecticide (fruit crops) Chromated copper arsenate (CCA) Mixture of C r A s 0 4 & Cu 3 (AsO 4 ) 2 *4H 2 0 1938: wood preservative Copper arsenite (Scheele's green) Cu(As0 2 ) 2 Pigment Lead arsenate Pb 3 (As0 4 ) 2 1892: insecticide (esp. for gypsy moths) Sodium arsenite N a A s 0 2 1890: soil sterilant, weed control, cattle/sheep dip, potato defoliant, tree debarker Tetraarsenic tetrasulphide (realgar) A s 4 S 4 Pigment; treatment of ulcers Organic Compounds Arsanilic acid C 6 H 4 N H 2 A s O ( O H ) 2 Animal feed additive Arsenobetaine: (AB) (CH3)3As + C H 2 c o c r Arsenocholine: (AC) (CH3)3As + C H 2 C H 2 O H Arsenosugars: (X-XIII) Composition varies depending on type of sugar Copper acetoarsenite (Paris green) Cu(CH 3 COO) 2 *3Cu(As0 2 ) 2 1868-1957: pigment, insecticide Dimethylarsinic/cacodylic acid: (DMA) (CH 3 ) 2 AsO(OH) Post WWII: defoliant (cotton fields) Disodium methylarsonate: (DSMA) (CH 3 )AsO(ONa) 2 • Post WWII: pesticide, herbicide Lewisite (2-chlorovinyldichloroarsine) CICH=CHAsCI 2 WWI: Chemical warfare (gas) Methylarsine (MeAsH 2 ) CHsAsHz Monomethylarsonic acid: (MMA) CH3AsO(OH) 2 Post WWII: defoliant, herbicide Salvarsan (arsphenamine) Complicated Treatment of syphilis & sleeping sickness 6 Tab le 2 quanti f ies the major anthropogenic sources of soi l arsenic : emiss ions from waste commerc ia l products (e.g. insect icides) and coal ash dominate. Tab le 2. G loba l a rsen ic inputs to soil from human activit ies (from Nr iagu and A z c u e , 1990). SOURCE As (x10e)(kg/yr) Median Range Agricul tural and food wastes 3 0-6.0 An ima l was tes 2.8 1.2-4.4 Logging and other wood wastes 1.65 0-3 Urban refuse 0.4 0.09-0.7 Munic ipa l sewage s ludge 0.13 0.01-0.24 M isce l l aneous organic wastes 0.13 0-0.25 So l id wastes , metal manufacturing 0.11 0.01-0.21 C o a l fly ash and bottom ash 21.9 6.7-37 Fert i l izer 0.01 0-0.02 Peat (agricultural and fuel uses) 0.27 0.04-0.5 W a s t a g e of commerc ia l products 38.5 36-41 A tmospher ic fallout 13.2 8.4-18 Total input soils 82 52-112 Mine tai l ings 9.1 7.2-11 Smel ter s lags and wastes 6.8 4.5-9.0 Total discharge on land 98 64-132 T h e type of arsenic found naturally in soi ls is usual ly inorganic: typically arsenate, in its stable forms such a s H A S O 4 2 and H2ASO4" (Wauchope , 1981; Bur lo ef al., 1999). Arseni te , as As (OH)3 , prevai ls under reducing condi t ions (Mar in etal., 1993) or if the soi l is contaminated from smelt ing p rocesses or mining activit ies prior to ox id iz ing back into arsenate (Porter and Peterson, 1977). Bacter ia and fungi methylate both types of inorganic spec ies into M M A and DMA, two organoarsen ica ls commonly found in soi ls . T h e availabi l i ty of soi l a rsen ic to biota is determined by its concentrat ion and chemica l form, and by environmental condit ions such as soi l composi t ion, soi l pH and cl imate. Natural arsenic levels vary according to soil type but typical background concentrat ions range from <1 to 95 ppm: the range in soi l type is represented by a mean of 4.4 ppm for podzols and a mean of 9.3 for h istosols (Kaba ta -Pend ias and Pend ias , 2001). A literature review of studies that examined phytotoxic levels of soil a rsen ic showed arsen ic concentrat ions were five t imes more phytotoxic in sands and loams, compared to clay soi ls (Sheppard, 1992). Soi l type not only indicates the 7 minerals present as potential binding sites, but a lso the relative c lay and humus contents, which provide large surface areas with great capac i t ies for cat ion exchange. A rsena te ions are f ixed by many soil constituents such as clay, humus, and calc ium (Kaba ta -Pend ias and Pend ias , 2001), but are most strongly bound to hydrous iron and a luminum ions that coat soi l particles (Woo lson , 1981). T h e result ing insoluble compounds are not easi ly leached out of the system by precipitation or irrigation. Due to its strong retention to surfaces, arsenic is not as mobi le as other e lements. In turn, these compounds may be re-oxidized, or further reduced into g a s e o u s methyl a rs ines (Woo lson , 1981). The composi t ion of the parent rock mater ial is a factor for the type of a rsen ic in soi l . For example, soi ls formed from arsenopyr i te rock can produce phytoavai lable arsenic that is predominantly arseni te (Bech ef al., 1997). If external arsen ic concentrat ions increase, more a rsen ic is made avai lab le to plants (Pal iour is and Hutchinson, 1991; Mar in et al., 1993). L ike t race metals, a rsen ic concentrat ions can increase if the soil pH is lowered: ac id ic condi t ions enhance cat ion exchange and solubility, thereby mobil izing metals and metal loids. Th is was demonstrated with Oryza sativa (rice), when Mar in et al. (1993) found that lowering the pH increased the amount of soluble arsenic avai lable for uptake. Similar ly, Meha rg and Macna i r (1991) found that as the pH increased, the rate of arsenate uptake dec reased in Holcus lanatus (velvet grass). Bech et al. (1997) performed a c a s e study of arsen ic .in vegetat ion growing around a Peruv ian copper mine. Resu l ts showed how low clay content and acidi f ied soil increased arsenic availabil ity, the latter due to increased solubil i ty of the iron and aluminum oxide binding compounds. B ioava i lab le a rsen ic can a lso increase when the pH is increased however, as sorpt ion to iron ox ides and part iculate matter becomes weaker. Fo r instance, when the p H is ra ised to >8.5 in semi-ar id or arid environments, arsenic in sediments can exper ience high dissolut ion rates (Smedley and Kinniburgh, 2002). 2.1.3 A r s e n i c Uptake in Plants Uptake of a rsen ic through the leaves can occur, particularly when herb ic ides and pest ic ides are sprayed directly on the plants. However, uptake is typical ly through the root-soil interface, driven by the water potential gradient between the air and the root system. Ions, including soluble arsenic spec ies , move apoplast ica l ly with the influx of 8 water through the root hairs to the cortex. The ions are barr icaded from enter ing the stele and are instead "forced" into the protoplasm, where they are transferred to vesse ls v ia the per icyc le (Punz and Sieghardt, 1993). O n c e in the vesse l s , they can be transported throughout the shoot. To overcome the p lasma membrane barrier, speci f ic protein carr iers are responsib le for shuttling ions across and into the ce l l . A rsena te sha res a carr ier with its chemical analogue, phosphate. A r s e n i c uptake is general ly low, and studies demonstrate that most plants have far lower total a rsen ic va lues than the medium in which they are growing (Milton and Johnson , 1999; Pitten ef al., 1999). Pitten ef al. (1999) looked at an o ld military site where even though certain 'hot spots ' y ie lded 250 g of a rsen ic in 1 kg soi l (250 000 ppm), ana lys is of on-site Holcus lanatus showed its highest concentrat ion w a s 26 mg/kg (ppm), and the median value was 0.7 mg/kg (ppm). A rsen i c loads in terrestrial plants growing on uncontaminated sites typically do not exceed 0.2 ppm (Cul len and Reimer, 1989). In terms of a rsen ic speciat ion, Tamak i and Frankenberger (1992) found that arsenate was three to four t imes more likely to be absorbed by most terrestrial plants compared to arsenite. The type of plant, and mobility of the individual a rsen ic spec ies are factors inf luencing where the arsenic is stored and how much can be absorbed . A s roots are the primary entry pathways, their a rsen ic concentrat ions are often higher than in other parts of the plant such as the stems, leaves, or fruits (Pal iour is and Hutch inson, 1991; Mar in ef al., 1993; Dushenko ef a/., 1995; Pitten ef al., 1999). However , t race elements, including arsenic, often accumulate in the extremities of a plant such as in twig ends, outer bark, and the tops of trees (Dunn, 1995). 2.1.4 Phys io log ica l and Biochemical Effects of A rsen ic in Plants T h e primary impact of arsenic toxicity on plants is a reduct ion in growth (Kabata-P e n d i a s and Pend ias , 2001). Th is response was noted with soi l a rsen ic concentrat ions >2 ppm (Pitten ef al., 1999). Other responses include ch loros is , d iscolourat ion, necros is , dehydrat ion, and reduced availabil i ty of essent ia l e lements (National R e s e a r c h Counc i l , 1977; Dushenko ef al., 1995). T h e latter study found that at high a rsen ic concentrat ions, the freshwater emergent plant Typha latifolia (cattails) showed leaf tip necros is , reduced stand height, and dec reased levels of copper , manganese and z i nc in the root. 9 T h e thorough review by Punz and Sieghardt (1993) out l ined the fol lowing important responses of plant roots to heavy metals, which can be app l ied to arsenic : • changes in root b iomass - typically a reduction in weight; • changes in the root system architecture - increased lateral root growth leading to a compacted system; • changes in growth rate; • inhibit ion of root elongat ion - largely due to a disruption of cel l d iv is ion and mitosis. They a lso noted other important morphological changes , including root d iscolourat ion, dec reased root hair density, vesse l diameter, and vesse l number, and structural changes to hypodermis, endodermis, and per icycle. Further physio logical r esponses include damage to root cel l membrane, dec reased water permeabi l i ty of the p lasmalemma, dec reased turgor or p lasmolysis, reduced root respirat ion, reduced water uptake, and increased water f low resistance (Punz and Seighardt , 1993). Due to their chemica l similarity, arsenate can rep lace phosphate in cel lular p rocesses such as transport, and enzyme react ions (e.g. arsenate inhibits pyruvate dehydrogenase , the enzyme involved in respiration). A rsena te uncoup les oxidative phosphory lat ion by replacing stable phosphate esters used in creat ing A T P with unstable arsenate esters, thereby reducing the availabil i ty of phosphate for A T P product ion (Tamas and Wysock i , 2001). A rsena te can reduce to arsenite, which then attacks protein sul fhydryls (Ul lr ich-Eber ius ef al., 1989); reacting with thiol groups on the act ive site of enzymes , thereby inhibiting enzyme activity (Burlo et al., 1999; T a m a s and W y s o c k i , 2001) . Arsen i te a lso disrupts root funct ions, inhibits leaves from taking up other e lements, and at high enough concentrat ions, will inhibit seed germination (Carbonel l ef al., 1998). Roots become increasing stunted and browned as concentrat ions are ra ised (Marcus -Wyner and Ra ins , 1982). Arseni te a lso inhibits pyruvate dehydrogenase (Koch , 1998) and can initiate lipid peroxidat ion (Snel ler et al., 2000). R i ce plants, wh ich predominant ly take up the more toxic arsenite spec ies due to the reducing condi t ions of their f looded habitats, exhibit "rice blight" or straighthead d isease , which deforms pan ic les and florets, and affects sterility (Marin ef al., 1992). The two organic arsenica ls M M A and D M A may affect protein synthes is and water relat ions. Appl icat ions of D M A to cotton grass, r ice, and tomato plants revealed severa l or all of the fol lowing condit ions: root p lasmolys is , leaf wilt ing, d iscolourat ion, 10 cur led leaf margins, and necros is of leaf tips and margins (Marcus -Wyner and Ra ins , 1982; Mar in et al., 1992; Burlo ef al., 1999). Absorpt ion of other e lements is a lso impacted: increased organic arsenic treatments on a wet land g rass showed high sod ium, and low potassium and magnes ium concentrat ions in the root, and high ca lc ium in the leaves (Carbonel l ef al., 1998). 2.1.5 Plant Mechan i sms to R e d u c e Toxicity P lants util ize different avo idance and tolerance strategies to reduce arsen ic toxicity. T h e s e strategies involve restricting the movement of the e lement into the plant, or by us ing a number of internal p rocesses to detoxify the compound . Tab le 3 summar izes these strategies as descr ibed by P u n z and Sieghardt (1993). Tab le 3. Strategies by plants to avoid metal stress (from P u n z and Sieghardt , 1993). Resistance Strategy Classification of Response Exc lus ion of metal ions A v o i d a n c e B iochemica l /enzymat ic changes on the root surface A v o i d a n c e Extracel lular deposit ion A v o i d a n c e Binding (fixation) to cel l wall components A v o i d a n c e Binding to pept ides (metallothioneins) To le rance Binding to peptides (phytochelatins) To le rance Compartmental izat ion in the vacuo le To le rance Excret ion A v o i d a n c e Shedd ing of plant parts or whole organs avo idance/ to lerance Plants appear to be select ively tolerant to different a rsen ic spec ies . S ince arseni te disturbs enzymes by reacting with thiols, more plants have evo lved to lerance capabi l i t ies to arsenate. Arsenate tolerance is not limited to vascu la r plants however, and has been found in fungi and bacteria, as well as mosses , and l ichens (Meharg and Macna i r , 1990). Intolerant plants indiscriminately take up phosphate and arsenate together (Pal iour is and Hutchinson, 1991), while "tolerant" 2 plants show reduced arsenate (Meharg and Macnair , 1990). Genera l responses emp loyed by arsenate-resistant plants to high concentrat ions include downregulat ion of phosphate /arsenate 2 Terminology as used in the literature; it is recognized that reduced arsenate uptake in "tolerant" plants is in fact, an avoidance mechanism. 11 transport carr iers leading to reduced uptake (Meharg and Macnai r , 1990; Sharp ies et al., 2000) , phytochelat ion, convers ion of arsenate into less toxic methylated spec ies (Benson et al., 1981; Meharg and Macnair , 1991), and the uninhibited extraction of soil a rsen ic by hyperaccumulators. Phytochelat ins are metal binding polypept ides that act as metal and semi-metal regulators, sequester ing agents, and detoxifiers in plants (and some fungi), which funct ion ana logous ly to metal lothioneins found in fungi, invertebrates, mammals and insects. A r sen i c (both arsenate and arsenite forms) is one of the e lements that will induce synthes is of phytochelat ins (but not necessar i ly metal lothioneins) (Gril l ef al., 1987). Induction was observed in vivo and in vitro for Rauvolfia serpentina (snakeroot), Arabidopsis (thale cress) , and S/'/ene vulgaris (Schmdger ef al., 2000) . Stef fens (1990) sugges ts that phytochelat ins may be part of a c y t o p l a s m - w a c u o l e shuttle system. The role of vacuo le storage for phytochelat in-bound metals appears to be a relatively new subject of study and no information speci f ic to arsen ica ls was found. Hyperaccumulators are a specia l c lass of plants that tolerate high concentrat ions of metals normally toxic to "regular plants". Recent ly, Pteris vittata (brake fern) was d iscovered to be an accumulator of arsenic, containing 125 t imes the amount found in the soi l , and convert ing much of the arsenate into arsenite as it t ranslocated from the roots to the fronds (Ma ef al., 2001). This is the first known arsen ic hyperaccumulator , and its potential use for c leaning up contaminated sites in sui table habitats is enormous. A r s e n i c appears to accumulate in older t issues of some plants (Bech et al., 1997), espec ia l l y older leaves (Porter and Peterson, 1975; Wyt tenbach ef al., 1996). T h e s e s inks al low the ions to be removed from sites where more d a m a g e could occur, and/or permit shedd ing to occur. Certainly litter exhibits accumulat ion (Milton and Johnson , 1999), though the authors recognize this cou ld be due to surface contaminat ion, binding by humus complexes, metabol ism and subsequent excret ion by bacter ia, or as a plant detoxification mechanism such as leaf absc i ss ion . Marcus -W y n e r and Ra ins (1982) observed a decrease in cotton leaf a rsen ic over 7 weeks from the day when the plants were sprayed with DMA. They sugges ted this w a s because the damaged leaves fell off, or the element was not being t rans located into healthier t issues, or there was a dilution-effect as plant growth cont inued but the total arsen ic content remained unchanged. Leaf absc iss ion as a detoxif ication mechan ism was more clear ly demonstrated by a study of arsenic in different need le age c l asses of 12 Norway spruce (Wyttenbach ef al., 1996). The resulting posit ive relat ionship between age and arsen ic concentrat ion was thought to be a result of the binding of the A s 3 " anion to mercapto groups of structural proteins in the leaf, and subsequent inability to t ranslocate to younger needles. Other recent data have shown that concentrat ions in leaves of dec iduous trees are simi lar to or exceed concentrat ions in twigs, while coni ferous need le concentrat ions tend to be lower (Dunn, 1995). Th is response was not observed with another conifer spec ies ; a rsen ic concentrat ions in Pseudotsuga menziesii (Douglas fir) were less in older need les , and highest in stem t issue (Warren ef al., 1968). 2.1.6 T h e Uptake of A rsen ic by Humans A rsen i c enters the human body on a daily bas is from var ious environmental med ia . T h e major pathways are v ia food and water ingest ion, and inhalat ion (e.g. by smokers , or workers util izing the element). Absorpt ion through the sk in can a lso occur, though this is uncommon. Sea food , mushrooms and other foods general ly contain organic arsenic , while water usual ly contains inorganic arsenic . Not all the arsen ic in foods is biological ly avai lable. Accord ing to the C a n a d i a n Counc i l of Min is ters of the Environment ( C C M E ) most arsenic in f ish is tied up in complex organic forms (e.g. arsenobeta ine) that are not broken down in the human body, whi le the remainder are largely s imple structures (e.g. trimethyl arsine) that are rapidly excreted ( C C M E , 2001). Tab le 4 shows the average amount of inorganic a rsen ic taken in by Canad ians , broken down by age groups and arsenic source. T h e s e are est imates only, based on data in previous studies, and assuming character ist ics about a part icular age group. For example , on a daily bas is adults are assumed to breathe 23 m 3 of air, drink 1.5 L of water, and ingest 20 mg of soi l , and smoking is based on the assumpt ion of smoking 20 cigarettes per day with 40-120 ng of arsenic each ( C C M E , 1995). T h e A g e n c y for Tox ic Subs tances and D isease Registry est imates that people who smoke two packs of cigarettes a day are inhaling 12 mg of a rsen ic per day ( A T S D R , 1993). For a 70 kg adult, this is 85 times the va lue prov ided by Health C a n a d a as a tolerable daily level of arsenic (section 2.1.9), exc lud ing contr ibut ions from other sources shown in Tab le 4. 13 Tab le 4. Est imated average daily intake of inorganic a rsen ic by the C a n a d i a n general populat ion (from C C M E , 1995; adapted from Hughes etal., 1994). Age Assumed Body Weight (kg) Estimated Daily Intake (ug/kg bw/day) Water Food A i r Soi l /Dirt Total Cigaret te smoking 0 to <6 months 7 0.5 0.2 0.0003 0.029 0.729 6 months to <5 years 13 0.3 0.3 0.0004 0.062 0.662 5 to <12 years 27 0.2 0.2 0.0004 0.007 0.407 12 to <20 years 57 0.1 0.1 0.0004 0.004 0.204 0.01-0.04 20 - 70 years 70 0.1 0.08 0.0003 0.003 0.183 0.01-0.03 2.1.7 T h e Movement of A rsen ic in the Body From the digest ive tract or lungs, arsenic is rapidly abso rbed into the bloodstream. D isso lved arsenic is more efficiently absorbed than low solubil i ty compounds such as lead arsenate and gall ium arsenide (National R e s e a r c h Counc i l , 1999). A r sen i c is bound to sulfhydryl-containing proteins or other compounds in the blood such as haemoglobin, glutathione, and cysteine, and then rapidly transported to organs such as the liver, sp leen, kidney, lungs, and skin (Wickst roem, 1972). Due to the strong binding of arsenite to sulfhydryl groups (section 2.1.4), this form is more likely to accumula te in t issues compared to arsenate or organic arsenic , wh ich are absorbed and then tend to be excreted (Bertolero et al., 1987). A s with plants, o rgan ic a rsen ic is cons idered much less toxic than inorganic arsenic. Accord ing to the Federa l -Prov inc ia l Subcommit tee on Drinking Wa te r ( F P S D W ) , a rsen ic is most often stored in the skin, bone, and musc le ( F P S D W , 1996). However, a rsen ic res idence time is highest in the hair, nai ls, sk in, and lungs, l ikely due to their strong p resence of keratin (cysteine) or proteins (sulfhydryl groups) as binding sites (National R e s e a r c h Counc i l , 1999). T h e body uses two major ways to remove inorganic arsenic : methylat ion, and direct urinary excret ion of the unaltered compound. In the former, the body can detoxify - 4 0 - 8 0 % of ingested arsenite and arsenate by convert ing these inorganic forms into methylated organic forms, which are then largely excreted through urine, or to a lesser extent, e l iminated through hair, nails, skin, breast milk, sweat, and f aeces ( F P S D W , 1996; Nat ional R e s e a r c h Counc i l , 1999). 14 2.1.8 Effects of A rsen i c in Humans A rsen i c was one of the 44 chemica ls registered on C a n a d a ' s first Priority Subs tances List in 1989, and a s s e s s e d by 1994 under the C a n a d i a n Environmental Protect ion Act. A rsen ic is cons idered a group 1 ("carcinogenic to humans") subs tance by Heal th C a n a d a . Due to its carc inogenic propert ies, many arsenic-conta in ing products have now been banned, including the insect ic ides that were so prevalent in past agricultural programs. Organ systems affected by inorganic arsen ic include the sk in , respiratory, card iovascular , immune, genitourinary, reproductive, gastrointest inal, and the nervous sys tem. S o m e non-carc inogenic effects assoc ia ted with arsen ic exposure from drinking water inc lude diabetes, sk in thickening, tingling or numbness in l imbs, hear ing impairment, hypertension, anaemia, peripheral vascu lar (blackfoot) d i sease , and chronic coughing (National Resea rch Counc i l , 1999). C a n c e r of the lung, kidney, liver, and bladder have been obse rved in countr ies 20-30 years ,a f ter known arsenic exposure v ia drinking wel ls. T h e majority of c a s e s document ing human effects from arsenic pollution deal with contaminated drinking water, often from mining dra inage. 3 The worst ep isode to-date is taking p lace in Bang ladesh , where one quarter of the populat ion (120 mill ion) is affected by wel ls contaminated with arsen ic re leased by natural condit ions (Nordstrom, 2002) . Drinking water contaminat ion has been or is a lso occurr ing at a smal ler sca le in India, Argent ina, V ie tnam, Inner Mongo l ia , Chi le , and Mexico (Nordstrom, 2002). Exposure from air and water is correlated with skin les ions and inc reased skin, lung, and internal cancers , yet the element does not typical ly c a u s e tumours in laboratory exper iments (Clewel l ef a/., 1999). Th is observat ion has created a controversia l debate over the presence of a threshold concentrat ion, beyond which carc inogen ic effects are observed (Clewel l ef a/., 1999). 2.1.9 A r s e n i c Gu ide l ines 3 Other important sources contributing arsenic in groundwater include organic rich or black shales, Holocene alluvial sediments (with slow flushing rates), mineralized or volcanogenic areas, and thermal springs (Nordstrom, 2002). 15 Federa l l y accepted thresholds for identifying a rsen ic contaminat ion in vegetat ion have not yet been establ ished; too little is known about the e lement 's toxicity in individual spec ies . Researchers instead a s s e s s an a rea b a s e d on known and determined background levels. They can then ass ign health r isks b a s e d on tolerable dai ly intake (TDI) guidel ines and knowledge of diet. Heal th C a n a d a and the Wor ld Heal th Organizat ion publ ish TDI guidel ines, which indicate the amount of a subs tance that is safe to consume on a daily basis. The TDI for inorganic a rsen ic is currently set at 2 ug/kg body weight/day, although Health C a n a d a is currently reviewing data to r e a s s e s s this va lue (M.T. Lo, pers. comm., 2002). No TDI is ava i lab le for organic arsenic , l ikely g iven its low toxicity and consequent low priority. Contaminat ion thresholds have been set for soi l by var ious agenc ies . T h e Y u k o n Contaminated Si tes Regulat ion ( C S R ) was passed in 1996 with the purpose of providing guidel ines to identify, manage, and c lean up contaminated s i tes in the Yukon (Department of Renewab le Resources , 1996). Standards are provided for agricultural, park land, resident ial , commercia l , and industrial sites. T h e C a n a d i a n Counc i l of Ministers of the Environment created environmental quality gu ide l ines for water, soi l , sediment, air, and marine food in four land use categor ies: agricultural, resident ia l /park land, commercia l , and industrial. The 1997 soi l quality guidel ine for inorganic a rsen ic was updated in 2001 ( C C M E , 2001). For both the C S R and C C M E , the industrial land use category is most sui table for this study. A military guidel ine based on initial investigations of the Distant Ear ly Warn ing ( D E W ) L ine radar sites prompted the development of the D E W Line C leanup Cri ter ia ( D C C ) in 1991 (Envi ronmental S c i e n c e s Group, 1995). Tab le 5 compares these three common environmental criterions consul ted by northern researchers for a rsen ic contaminat ion. Tab le 5. Cri ter ia for arsenic contamination in soil in pg/g (ppm) dry weight (from Environmental S c i e n c e s Group, 1995; Department of Renewab le R e s o u r c e s , 1996; C a n a d i a n Counc i l of Ministers of the Environment ( C C M E ) , 2001). Yukon Contaminated Sites Regulation (CSR) (Industrial) Plants1 CCME Guideline Inorganic As CCME SQG E* Inorganic As DEW Line Cleanup Criteria (DCC) Tier I3 Tier II4 150 12 50 - 30 1 Toxici ty to plants and soi invertebrates 2 So i l quality guidel ine for the environment (as compared to human health) 3 T i e r l-contaminated soi l may be p laced in an on-site landfill 4 T i e r I l-contaminated soil must be entirely removed from the site 16 T h e mine sites examined in this study are on federal ly control led land and therefore not cons idered under C S R guidel ines; the D IAND W a s t e Program uses C C M E va lues instead (B. Hartshorne, pers. comm., 2002). However , it is my opinion that the Y u k o n C S R guidel ine is the most appropriate for. this study: the C C M E and D C C guidel ines are general values, and are not representat ive of soi l containing anomalous arsen ic concentrat ions. They are of less use in mining reg ions where gold ore is naturally assoc ia ted with bedrock containing arsenic. A l though the 150 ppm C S R guidel ine is a lso a general value, it has taken arsenic- r ich soi l samp les into cons iderat ion prior to calculat ing the final va lue for industrial si tes. 2.2 Stud ies of A rsen i c in Northern Plants Recen t studies have been done on trace metal accumula t ions in northern vegetat ion, including studies of arsenic in plants. R e s e a r c h tends to focus on three categor ies: 1) contributions from local point sources, 2) identifying natural 'basel ine ' concentrat ions, and 3) contributions from diffuse sources distr ibuted to northern latitudes v ia air and water circulation systems. T h e s e categor ies can be difficult to dist inguish though, part icularly the latter two, s ince a rsen ic is so ubiquitous. Identifying the speci f ic source of the e lement would require a thorough survey that uses 'fingerprinting' techniques: compar ing chemica l composi t ions of local soi l , water, and vegetat ion samples to known industrial sources , and attempting to pinpoint the geographical location of the source. Th is w a s done in a recent study of lead in northern vegetation (France and Bla is , 1998). Diffuse sources include arsenic re leased by vo lcan ic activity and pollution, which can migrate north. However, the general lack of mobility of this element, due to its strong sorpt ion by soi l constituents such as c lays, hydroxides, and organ ic material (Kaba ta -Pend ias and Pend ias , 2001), suggests that most a rsen ic in Y u k o n soi ls and plants represents local sources or reflects basel ine concentrat ions. 2.2.1 Point Source Stud ies Point sources include mining properties, smelters, and military s i tes. A rsen ic results from studies taking p lace at such locations will be rev iewed for purposes of 17 compar ison with this study. The mine sites include Mt. Nansen , Arct ic G o l d and Si lver, and V e n u s M ines in the Yukon , and G ian t /Con Mine in Yel lowkni fe, NT, and the smelter is one located in north-western Russ ia . The relevant military si tes inc lude Yukon ' s A ish ih ik airstrip, and radar stations in northern C a n a d a . Many studies show increased arsen ic in plants located near mines (Godin and Osier , 1985; Dunn, 1995; Bech et al., 1997; Ash ley , 1999; Davey, 1999). Wh i l e this may be due to uptake from naturally enr iched soi ls, it a lso indicates the importance of cons ider ing airborne sources. One project looked at total a rsen ic in berr ies gathered near act ive mines (Con and Giant), and abandoned mines (Salmita and Burwash) in the Ye l lowkn ives Dene traditional territory. Resul ts showed that 21 of 51 berry samp les exceeded the contaminat ion threshold of 0.1 ug/g (ppm) (Davey, 1999). Th is limit was the Heal th C a n a d a guidel ine for arsenic in fruit ju ices, used by the author who recogn ized that no guidel ine exists for fruit. The highest (wet weight) concentrat ions found in individual spec ies were the fol lowing: raspberry (1.91 ppm Giant Mine), blueberry (0.16 ppm Salmita), cranberry (0.64 ppm C o n Mine), gooseber ry (0.20 ppm Giant Mine), rose hip (0.86 ppm C o n Mine), and cloudberry (0.32 ppm Salmita) (Dene Nat ion, 1998). Concentrat ions in berries from mine si tes were signif icantly higher than those from control si tes, and the authors suggest that the mines do have an effect on a rsen ic levels in berr ies. A final recommendat ion was to avo id picking berr ies in certain locat ions and w a s h them thoroughly in other areas. Other researchers studying arsenic in soil and vegetat ion around Y u k o n gold mines a lso came to these conclus ions. The V e n u s Mine had been mined for c lose to a century and in 1995, its tail ings underwent a cap and barrier wal l construct ion project. T h e total a rsen ic content of raspberr ies was examined prior to, and after this project. In 1983, raspberr ies were picked from two sites at the V e n u s tai l ings site and on a whim, sent to be b io -assayed (J. Cruikshank, pers. comm., 2001). T h e results from the f resh berr ies showed 4.7 and 15 ppm arsenic content, whi le a samp le of preserved jam p icked 1.5 km away had <0.20 ppm (referred to in G o d i n and Os ie r (1985)). Further testing of vegetat ion, water, and sediments by Envi ronment C a n a d a ' s Envi ronmenta l Protect ion Serv ice revealed one of f ive s i tes with consistent contaminat ion (2.3 to 40 ppm); sand was visible on all samp les with e levated arsen ic (Godin and Osier , 1985). S igns were erected to warn berry p ickers away from the area due to high arsen ic concentrat ions, and cl inics were set up to test hair and f ingernai ls 18 for a rsen ic exposure in local residents - the results of which were negat ive (God in and Osier , 1985). In 1984, a thorough study of the vegetat ion, water, and soi l in the vicinity of the V e n u s tai l ings was undertaken, and for compar ison, sampl ing at the Mt. Nansen mining a rea was a lso performed (Godin and Osier , 1985). T h e results of the vegetat ion survey indicated ev idence of windborne contamination by sand and dust at the V e n u s site. Non- r insed raspberr ies had significantly greater concentrat ions than r insed raspberr ies at the two sample sites around the tail ings pond (36.6 ve rsus 9.6 ppm, and 93.3 versus 33.3 ppm for the V e n u s and Mt Nansen sites, respect ively). R o s e h i p s and gooseber r ies col lected at these same sites a lso had e levated concentrat ions, as did the leaves of raspberry, rosehip, and gooseberr ies shrubs. There w a s little ev idence of a rsen ic contaminat ion at the Mt. Nansen site as f i reweed leaves, and juniper berries, b lueberr ies, and mossberr ies had arsen ic concentrat ions <1 ppm. Subsequen t raspberry sampl ing at the V e n u s tai l ings showed a dec rease in concentrat ions after the cap was installed. Repl icate samp les co l lected in 1995 had a mean of 134.5 ppm wet weight (Roach , 1995), while a 2001 sample w a s 0.1 ppm (P. R o a c h , pers. comm., 2002). A sample col lect ion in 1999 was predominantly carr ied out at the Arct ic Go ld and Si lver M ine survey (Roach and Cunn ingham, 2000). S a m p l e s co l lected in the dra inage a rea in between the tai l ings and a beaver pond y ie lded high total a rsen ic concentrat ions in wi l low (43.9 ppm) and sedges (4.3 ppm), while bearberry w a s only 0.6 ppm. S a m p l e s co l lected nearby (off-site a long Tank Creek) had less var ied total a rsen ic results: wi l low (1.95 ppm), sedge (4.56 ppm), bearberry (0.3 ppm), a lder (2.5 ppm), and raspberry (4.6 ppm). S ince the arsen ic w a s predominant ly inorganic, it w a s recommended that local residents avoid picking raspberr ies. T h e Arct ic G o l d and Si lver tai l ings were capped in 2000 ( E B A Engineer ing Consul tants Ltd., 2001). Ba rcan ef al. (1998) examined concentrat ions of metals a n d metal lo ids in berr ies and mushrooms col lected around a n ickel -copper smelter at Monchegorsk , Ko la Pen insu la , R u s s i a . Relevant spec ies include lowbush cranberr ies, b lueberr ies, and Bolete mushrooms. The researchers found that arsen ic concentrat ions did not exceed health s tandards: maximum dry weight sample concentrat ions for the relevant spec ies inc luded 0.37 ppm (Vaccinium vitis-idaea), 0.25 ppm {V. myrtillus), 1.3 ppm (Leccinum aurantiacum), and 0.16 ppm ( L scabrum). However, the berr ies and mushrooms were 19 inedib le within a 3000 k m 2 a rea surrounding the smelter complex due to dust emiss ions caus ing e levated nickel (and in one area, strontium) concentrat ions. A n environmental study of Yukon 's Aish ih ik Airstr ip w a s carr ied out in 1994 (Environmental S c i e n c e s Group, 1995). P C B and inorganic element ( including arsenic) concentrat ions were determined in soi l , water, and plants co l lec ted on-si te, and from background areas . Seventeen samples of shrubs (predominantly wil low) and g rasses were ana lysed for arsenic; for some samples, the roots and shoots were separa ted and individually ana lysed . The study def ined plants as being contaminated when their concentrat ions exceeded twice the background levels, which was determined from 3 wil low samp les to be <0.2 ppm. On-si te, the majority of samp les were <0.2 ppm also, with a high range of 0.8 ppm (willow shoots) and 2.6 ppm (willow roots). So i l from the Aish ih ik Airstr ip site was a lso evaluated using the C C M E resident ia l /park land criteria, and no samp les were found to exceed the 30 ppm threshold (range 1.9 to 15.7 ppm). T h e background levels of arsenic in soil showed a mean of 6.9 ppm (Environmental S c i e n c e s Group , 1995). Dushenko et al. (1996) examined 960 plants for P C B and inorganic element concentrat ions (including arsenic) at 43 sites in the C a n a d i a n Arct ic. T h e s e included 707 plants co l lec ted from military radar s i tes (abandoned or former D E W Line, Po le Vault , or P ine G a p stations), 162 background plants col lected up to 10 km away from the military si tes, and 91 samples from 6 remote background s i tes >20 km away from any human presence. Samp les compr ised leaves, s tems, and root t issue, al though some samp les were subdiv ided as at the Aishih ik site. Fo r the remote background samp les (predominantly willow), 29 had detectable arsenic, with a mean of 0.59 ppm, and a high of 8 ppm. For the site background samples , 29 had detectable arsenic , with a mean of 0.69 ppm, and a high of 46.5 ppm. 2.2.2 Stud ies Determining Base l ine Concentrat ions A large inventory of traditional diet information w a s col lected from Northwest Territory Dene and Metis groups by Berti ef al. (1998). The only a rsen ic concentrat ions in plants pub l ished in the article were for blueberr ies (2.5 ppm) and cranberr ies (2.8-3.0 ppm), wh ich are low enough not to be of concern using Heal th C a n a d a TDI criteria. 20 F lork iewicz et al. (1995) col lected 110 plant samp les from Y u k o n ' s R o s s River a n d W a t s o n Lake communit ies in 1993. They found no unusual ly high arsen ic concentrat ions in a pilot study that was intending to capture base l ine levels of e lements in country foods, including plants used a s traditional foods a n d medic ine. A n expanded study (1993-1995) examined samples co l lected in the communit ies of W a t s o n Lake, Tes l in , Whi tehorse, Ha ines Junct ion, R o s s River, and Dawson (Gamberg , 2000). A s with mammal and bird t issues, no e levated arsen ic concentrat ions were found in 107 plant samples. Resu l ts are shown in T a b l e 6. Tab le 6. M e a n arsen ic concentrat ions in vegetat ion col lected throughout the Y u k o n (from Gamberg , 2000). Data are grouped to show relative a rsen ic concentrat ions in different plant parts and plant types. Plant part n Arsenic Concentration (mg/kg dry weight) Bark 1 <0.01 Berry 46 <0.01 F lowers 9 0.11 Forbs 9 0.29 Everg reens 4 0.07 Mushroom 4 0.8 A s part of the dietary benefit/risk assessment of >70 spec ies of tradit ional plant and animal foods consumed by Yukon First Nat ions, a rsen ic w a s ana lysed in 20 samp les of berr ies col lected from Yukon communit ies. T h e researchers found that a rsen ic levels were low in all 171 traditional food samples , including plant foods. Al l berr ies had undetectable arsen ic concentrat ions except for o n e lowbush cranberry sample co l lected from the Carc ross community with 1.3 ppm (Receveur et al., 1998). K o c h et al. (2000) examined the forms of arsen ic avai lab le to plants col lected around Yel lowkni fe, Northwest Territories. G iven the high natural a rsen ic concentrat ions in the area, basel ine concentrat ions should exceed that of other regions with different geology. O n average, Koch et al. (2000) found that m o s s e s had higher total a rsen ic than grasses/shrubs (825 ppm versus 53 ppm dry weight, respect ively), and of this total, inorganic forms were dominant over organic forms. Mo re than 5 0 % of this e lement cou ld not be extracted by analyt ical techniques and its form remains unknown. W h a t organic forms that could be extracted and identif ied include 21 a rsendsugars and methylated spec ies . Thei r percentage of total a rsen ic ranged from 0-11 % ( A s + 3 ) versus 8-88% ( A s + 5 ) for the 14 plant spec ies ana lyzed . 2.3 Introduction to Ethnobotany and Tradit ional Knowledge First Nat ion people are strongly connected to the land, and they have great understanding of biotic and abiot ic systems through their histor ic l i festyle and culture. Th is traditional knowledge has been passed through generat ions v ia an oral history. The work ing definit ion of traditional knowledge used by the Northern Contaminants Program is the fol lowing: A n exist ing Abor ig inal knowledge system of lands, waters, c l imates, s e a s o n s and related animal behaviours in an Abor ig inal territory, based on ancestra l exper iences , oral history, subs is tence harvest ing and tradit ional use of plants and animals, as well as the use of historical waterways, trails and other nomad ic travel paths (Counci l of Yukon First Nat ions, 2000). Tradit ional and western-based scientif ic knowledge can be used together to research ethnobotany: the study of plants important to people, wh ich incorporates knowledge of cultural and historic roles, l inguistic and botanical c lassi f icat ions, and ecology. Plants have been gathered as food and medic ines by First Nat ions for mi l lennia. Contemporary nutritive and chemical analys is of traditional plants al lows an understanding of why these plants remain effective cho ices . In spite of known contaminat ion in northern ecosystems from pollution sources located in industr ial ized regions further south (persistent organic pollutants, heavy metals, etc.), the benefi ts of consuming traditional foods (versus those purchased from the market) outweigh the r isks (We in , 1994; J e n s o n ef. al, 1997). P lants are used daily by northerners throughout the c i rcum-arct ic region (Arctic Moni tor ing a n d A s s e s s m e n t Programme, 1997). Wi th reference to Y u k o n First Nat ion diets, typical edible plants include arctic dock (Rumex arcticus), f i reweed (Epilobium angustifolium), wi ld on ions/ch ives (Allium schoenoprasum), dande l ion leaves (Taraxacum officinale), wild rhubarb (Polygonum alaskanum), bear root (Hedysarum alpinum), Labrador tea leaves (Ledum spp.), Bolete mushrooms (Leccinum spp.), puff bal ls (Lycoperdon spp.), morels (Morchella spp.), shaggy mane mushrooms (Coprinus comatus), blueberry (Vaccinium spp.), crowberry (Empetrum nigrum), low-bush cranberry (V. vitis-idaea), h ighbush cranberry (Viburnum edule), soapber ry (Shepherdia 22 canadensis), strawberry (Fragaria spp.), c loudberry (Rubus chamaemorus), rosehips (Rosa acicularis), currants and gooseberry (Ribes spp.), and Saska toon berry (Amelanchier alnifolia) (Nardell i and W e i n , 1996; Receveu r et al., 1998; D. Char l ie , pers. comm., 2001). Plants are often important sources of vi tamin C , vitamin A, ca lc ium, fibre, fo lacin, thiamine, and fibre (Medical Serv ices Branch , 1994). S o m e nutrient composi t ion va lues for se lected berries, plant greens, roots, and others are l isted in Append ix 1. R e c e v e u r et al. (1998) completed a territory-wide study of dietary benefi ts and r isks assoc ia ted with the consumpt ion of traditional foods by Y u k o n First Nat ion people. They had the fol lowing observat ions: 1) traditional foods are consumed 5 7 % of the year (80% in summer, and 4 0 % in winter), 2) 5 8 % of the househo lds surveyed col lect plants, 3) plant foods are consumed in summer and to a lesser extent, winter, 4) berr ies are c o n s u m e d by the most number of people compared to other plants; in descend ing order of the top 10 spec ies by summer use (blueberries, wi ld raspberr ies, low bush cranberr ies, wi ld strawberries, high bush cranberr ies, soapberr ies , crowberr ies, Labrador tea, mushrooms, ba lsam fir), 5) the youngest generat ion (20-40) consumes more market food than older generat ions, including fewer berr ies, mushrooms, and wild rhubarb (Receveur et al., 1998). Chapter 3: Site Descriptions and Methods 3.1 Study S i tes A genera l site map showing the locations of the mines and the traditional territories of the two Y u k o n First Nat ions is found in F igure 1. 3.1.1 Mt. N a n s e n Property Phys ica l Geography Th is site is located - 6 0 km west of Carmacks , Y T (62° 05 ' N, 137° 05 ' W ) , at an elevat ion between 945 and 1525 m (tailings pond at ~1133 m) (K lohn-Cr ippen, 1995). Important waterways include Pony Creek and Dome Creek that drain west into Victor ia Creek , which in turn drains south into Nisl ing River. A n archaeo log ica l site used as an 23 educat ional camp by the L S C F N is situated severa l ki lometres from the mine near Vic tor ia Lake, a "once favoured f ishing spot [that] has been s p u m e d for years now s ince no one is sure whether the f ish are safe to eat or not" (Noble, 2000, 3). T h e a rea exper iences a sub-Arct ic continental cl imate, with long co ld winters, short mild summers, and low to moderate precipitation (Atmospher ic Environment Serv ice , 1993; J a c k s o n , 2000). In a region of d iscont inuous permafrost, the so i l orders found here include G leyso ls , Organics , Regoso ls , Turb ic Cryoso ls , and Eutr ic Bruniso ls (Tarnocai , 1987). The area was not glaciated during the M c C o n n e l l g laciat ion (which ended ~11,000 years ago) and weathering of bedrock has subsequent ly occur red in a reas to depths of <75 m, while leaching and oxidation of su lph ides and other compounds have taken p lace in mineral ized zones (Mel l ing, 1994). In the immediate a rea of the tai l ings pond, surficial materials of moss, peat, and organic silts and sands over l ie g lac ia l till and sands , which in turn cover bedrock (T.W. H iggs Assoc ia tes , 1994; K lohn-Cr ippen , 1995). Broad vegetat ion types here are coniferous forest on lower s lopes and alpine tundra on upper s lopes and ridgetops. Local wildlife spec ies include wood bison, wood land car ibou, moose, wolf, fox, squirrel, ground squirrel , g roundhogs, ptarmigan, grouse, waterfowl, swans, grizzly and black bears (T .W. H iggs Assoc ia tes , 1994; L S C F N , 1998). F ish are not found in Dome Creek (which directly rece ives mine d ischarge) or Victor ia Creek, but whitefish and grayl ing occupy the Nis l ing River ( L S C F N , 1998). During the 2001 field season , moose tracks were observed in the tai l ings. Ungulate densi t ies around the Mt. Nansen property itself are general ly low: moose densi t ies are fewer than 100 per 1000 k m 2 (Department of Renewab le Resou rces , 2000), and the wood bison herd has estab l ished itself in the Nis l ing River a rea ~10-15 km southwest of the mine (T.W. Higgs Assoc ia tes , 1994). T h e mine is located in the south-eastern limit of the woodland car ibou (K laza herd) range. However, moose and car ibou continue to be hunted in this region. A n elder from the L S C F N ment ions "the mine site is in the middle of a migration corr idor that the car ibou use traditionally to get to their wintering grounds" ( J .G . Moore & Assoc ia tes , Ltd, 1998, 14). T h e bedrock geology of the Mount Nansen mine envi rons is complex; rock c l a s s e s include ultramafics, metamorphics, and vo lcanics . S a m p l e s in this study were largely taken from the P P A regional unit, which is compr ised of sch is ts , amphibol i te, gne iss , phyllite, quartzite, and ultramafics (Tempelman-Klui t , 1984). S o m e background 24 samp les were located in the D M g P W regional unit that is compr ised of amphibol i te, schist , and phyll ite (Tempelman-Klui t , 1984). The region of the B r o w n - M c D a d e open pit where the ore was extracted contains andesite, dacite, brecc ia, tuffs, rhyolite, porphyry, p lugs and others of vo lcanic origin (Tempelman-Kluit , 1984). Bedrock is exposed and shattered on ridge tops and upper s lopes of the val leys where there is little or no tree cover (K lohn-Cr ippen, 1995). Min ing History T h e Mt. Nansen property consists of four separate gold and si lver deposi ts : B rown -McDade Zone , F lex Zone , W e b b e r Zone , and Huest is Ve in . Underground mining has taken p lace at Mt. Nansen s ince 1947, though p lacer activity has occurred s ince 1899 (Mineral Resou rces Branch, 2000). The mill was constructed for a 1967 to 1969 product ion per iod, used again during 1975-1976, between Oc tober 1996 and February 1999 when B Y G Resources Ltd. was in operat ion, and is used currently for treating water (Mineral Resou rces Branch, 2000). Pr ior tb the B Y G activity, mine work ings were smal l underground gold and si lver operat ions. Ore w a s brought to the mill and p rocessed using flotation, and tail ings were deposi ted in two smal l ponds. A n aer ial photograph of the property taken in 1990 shows the posit ion of the tai l ings ponds in relation to Dome Creek, as well as exploration t renches for the B r o w n - M c D a d e open pit (Figure 2). M ine waste from this period is est imated as the fol lowing: 25 ,000 tonnes sulphide-r ich tai l ings and 41,000 tonnes of stockpi led ore near the mill p lus an ore dump at P o n y C reek (Brodie, 1998; Mountjoy and Ramsay , 2000). T h e B Y G set-up was both an underground and open pit extraction of ore. The mill w a s retrofitted to accommodate a carbon- in- leach p rocess for producing gold and si lver (T.W. Higgs Assoc ia tes , 1995). A new tail ings pond was constructed on the Dome C reek val ley floor ~1.5 km downstream from the mill us ing local fill material for the impoundment, and the creek itself was diverted (Mountjoy and Ramsay , 2000). Infrastructure difficulties arose from placing the pond over permafrost. T h a w problems led to dam eros ion and instability concerns, as the material has the ability to liquefy and "pipe" when thawed (Mountjoy and Ramsay , 2000). F rom the reported 788,000 tonnes of rock excavated by the B Y G operat ion by the end of 1998, an est imated 513,000 tonnes of waste rock was p roduced (Hureau, 1999). It cons is ted of clay-altered granodiorite and fe ls ic porphyry rock types, and was 2 5 located adjacent to the Brown-McDade adit to the northeast and to the west. A n est imated 258,174 m3 of tail ings was also produced and p laced in the 294 ,000 m3 capaci ty pond (Mountjoy and Ramsay , 2000). F igure 2. Mt. N a n s e n aerial photograph showing the tai l ing ponds, B rown-McDade open pit, and Dome C reek in 1990 (Geographic Data, 1990a). T h e sca le is - 1 :20 ,000 . Wa te r R e s o u r c e s , a div is ion within D IAND, se i zed the property in 1999 after B Y G violated their water l icense condit ions. The company w a s f ined the maximum amount of $100 ,000 per charge for not meeting effluent quali ty s tandards, exceeding the a l lowable cyan ide concentrat ion in the tail ings pond, and for not fi l ing a required 26 chemical analysis report (Steele, 1999). The fourth violation of mining past the oxide zone into the lower sulphide zone (which induces metal leaching), did not go before the Yukon Territorial Court (van Dijken, pers. comm., 2001). BYG's environmental legacies include a structurally unstable dam, metal leaching in the Brown-McDade pit walls and floor, and in the tailings dam where the sulphide-rich tailings were deposited along with oxide tailings, and high cyanide, copper, zinc, and arsenic levels in the pond. Reclamation Activities BYG went into receivership in March 1999, but the receiver (D. Manning and Associates Inc.) gave up property responsibilities in July 1999. The federal government contracted general site cleanup duties to Ketza Construction Ltd. A larger seepage collection dam and pump-back system was installed to reclaim and treat water, as part of the ongoing wastewater treatment program initiated by BYG in fall 1997. Cleanup and reclamation is expected to cost $8-10 million at the cost of DIAND, who has already spent $1.7 million (including BYG's $455,000 water license security) as of November 2000 (P.H. Beaubier, pers. comm., 2000). Reclamation will not occur until the current operator (Water Resources) abandons the site such that the Contaminants and Waste Management Division can step in, and when sufficient funds are available (P. Roach, pers. comm., 2002). 3.1.2 Venus Mine Property Physical Geography The Venus Mine tailings site (60° 02' N, 134° 37' W) is 22 km south of Carcross, YT at an elevation of 670 m. It is located on a narrow strip of land bordered by the Klondike Highway #2 to the east, and Windy Arm of Tagish Lake to the west. The abandoned mine site is 2 km further south on the west side of the highway at an elevation of 670-960 m (Environmental Services, 1997). As with Mt. Nansen, this area experiences a sub-Arctic continental climate though the temperatures are more moderate and precipitation is less here (Atmospheric Environment Service, 1982). Permafrost is very discontinuous in this region. Local soils are predominantly Dystric Brunisols, with Cryosols existing over permafrost. A typical soil profile would be a silty clay layer overlying a permeable sand and gravel 27 layer (Westermann and Nahir, 1999). Vegetat ion is dominated by coni ferous forest and alp ine tundra. Loca l wildlife includes Dal l 's sheep, moose, wolf, porcupine, gr izzly and b lack bear, grouse, ptarmigan, peregrine fa lcon, go lden eag le , and waterfowl birds such as mergansers (Environmental Serv ices , 1999). T h e tai l ings site is located in the Nak ina Format ion of the C a c h e C r e e k Group. T h e bedrock c lass here is volcanic, with the main rock type largely greenstone/metabasi te, with hornblende diorite, chert, and carbonate. T h e geology in the region of the mine is the Montana Mountain Vo lcan ics , compr ised of regions with either rhyolite, or andesi te and dacite. The ore itself is predominant ly arsenopyr i te, and has been est imated at 10% arsenopyrite, 8% iron pyrite, and quartz (Jack, 1981). Min ing History T h e V e n u s vein is a gold/si lver/ lead/zinc quartz vein, and all four of the metals have been excavated. Underground mining activity has taken p lace here s ince the turn of the century. In 1966, V e n u s Mines Ltd. began explorat ion and by 1970, a 272 tonne/day capaci ty mill had been built just north of the current tai l ings about 2 km north of the mine (Environmental Serv ices, 1997). Th is mill only operated from September 1970 to J u n e 1971, and tail ings were deposi ted in a natural depress ion with perimeter d ikes constructed using the area 's natural c lay and silt soi l layer (Jack, 1981; K lohn-Cr ippen , 1995). A decant pipe was installed to drain water from the pond. Aer ia l photographs of the tail ings pond are shown in F igures 3 A and 3B . Uni ted Keno Hill M ines Ltd. (UKHM) opt ioned the V e n u s c la ims from 1978, and in 1979, they dec ided to re-open the mine (Environmental Se rv i ces , 1997). U K H M began construct ion on a new V e n u s mill and tail ings impoundment in B C , 33.6 km from C a r c r o s s and less than 10 km south of the mine. The new mill w a s built with the expectat ion that the old tail ings would be transferred from their exist ing site, and rep rocessed . By 1981, mine c losure occurred due to overest imates of ore reserves, fal l ing metal pr ices, and environmental problems. P rocess ing of ore had not yet occurred, and the 197fj's tai l ings remained in their current locat ion (with the except ion of 360 tonnes that were excavated in 1981 (K lohn-Cr ippen, 1995)). Est imated tonnage of tai l ings based on production reports from this period ranges from 51,700 - 54,400 tonnes (K lohn-Cr ippen, 1995). Calcu lat ions based on auger samp les co l lec ted prior to Figure 3. Aerial photographs of the Venus tailings pond showing its proximity to Windy Arm of Tagish Lake and Montana Mountain as shown in A) 1975, scale -1:4000 (Geographic Data, 1975) and B) 1990, scale -1:20,000 (Geographic Data, 1990b). Reclamation Activities In 1993, under the auspices of DIAND's Arctic Environmental Strategy - Action on Waste program, the environmental impact of 49 abandoned mining properties was assessed, and recommendations for remediation were suggested. The Venus Mine tailings site was not the focus of the Venus Mine property report, but was identified as having potential environmental concerns. Wind and water erosion of the tailings were 29 causing health, water quality, and aesthetic concerns about this highly public site along a major tourist route. A number of water quality tests on tailings pond water, Venus Mine adit drainage, Windy Arm lake water, sediments, fish and invertebrates have been performed since 1975 (Robson and Weagle, 1978; Jack, 1981, Godin and Osier, 1985, Environmental Services, 1997). Water quality results were generally poor, but the studies showed that high arsenic concentrations released from the tailing site and adits had no or little impact on lake organisms. High arsenic and metals are naturally present in Montana Mountain soils and sediments, and arsenic found in Windy Arm is attributed to a number of sources, of which Venus Mine is only one (Mann, 1998). However, the arsenic found in surrounding vegetation was attributed to the tailings (as discussed in section 2.3.1). Further assessment led to the decision to consolidate, impound and cap the eroding tailings (the mill had already been removed because of the 1993 assessment). The site underwent rehabilitation work between August 11 and October 20, 1995 when the following components were installed at the cost of $1.2 million: a Waterloo Barrier sheet pile wall; a multi-layered cap comprised of a geotextile, silty clay, and drain rock on top; a plug to a decant pipe outlet; and a drainage discharge system (Vallerand, 1995; Westermann and Nahir, 1999). In addition to containing the pond area tailings with a barrier wall, 3656 m 3 of windblown tailings were excavated and placed in the pond area (Vallerand, 1995). After the cap was constructed, the land surrounding the tailings site was transferred to the C T F N as part of their land claim (MINFILE, 1998). In 1997, a sand and gravel buttress to support a potentially unstable section of the wall was constructed, and additional material was placed on areas of the cap that were settling or where water was ponding on the surface. Drain rock was again added in 1999 for aesthetic purposes, and to make certain further ponding would not occur (Westermann and Nahir, 1999). Acid rock drainage (ARD) was an early concern that has now been diminished by using the aforementioned multi-layered cap design. ARD forms when four factors are present: exposed sulphide minerals (e.g. pyrite), oxygen, water, and the bacteria Thacillus ferrooxidans. Though the bacteria are present at this site, and the metal-rich tailings are acid-generating, the neutralization potential of the ore is currently high enough that the acid is neutralized (pH tests of the decant water are consistently 30 alkal ine) (Davidge, 1984; Poush insky Consul t ing Ltd., 1994). T h e cap des ign further reduces A R D potential by using multiple layers that submerge the tai l ings in groundwater that is draining through the cap, thereby reducing the oxygen concentrat ion. After a rsen ic levels in berries were tested in the ear ly 1980's , the Ca rc ross community heeded attention to the s igns and avoided the a rea , in spite of the site being a traditional harvest ing site by the Carc ross /Tag ish First Nat ion (H. Ga tensby , pers. comm., 2001) . S ince the 1995 capping, subsequent tests on the berr ies have increasingly pointed to this site as a p lace to pick berr ies once aga in . 3.1.3 Arct ic Go ld and Si lver Mine Property Phys ica l Geography Th is abandoned mill and tailing si te, is located 4 km S W of C a r c r o s s (60° 05 ' N, 134° 4 1 ' W ) at approximately 1000 m. T h e majority of physiographic detai ls provided for the V e n u s site apply to A G S . T h e cl imate would be slightly modified due to the higher e levat ion of the tai l ings site, as wel l a s other factors such as s lope and aspect. The local vegetat ion is of the subalp ine type, with white spruce, alpine fir, white birch, and alder in c leared a reas (Environmental Serv i ces , 1998). T h e bedrock geology of the immediate region is c lass i f ied as C a r c r o s s granite, within the Nis l ing R a n g e Plutonic suite. The main rock types include quartz monzonite, granite, alaski te, and granodiorite (Hart and Radloff, 1990). The ore p rocessed at the mill came from mines further up Montana Mountain, which are in a region of (altered) Mon tana Mounta in Pluton granite from the Mt. Mclntyre Plutonic Sui te (Mann, 1998). Min ing History T h e mining c la ims assoc ia ted with the Arct ic G o l d and S i lver tai l ings site include Arct ic Car ibou , B ig Thing, Peer less , and Pr ide of Yukon . Al l were underground gold and si lver deposi ts and were located approximately 4 km further south at an elevat ion of 1500-1700 m (Arctic Car ibou) and 1600-1700 m (Big Thing). T h e s e c la ims were staked as ear ly as 1905, and worked between 1910 and 1922 and aga in dur ing 1966 to 1969 by Arct ic Min ing & Explorat ion Ltd (whose name changed to Arct ic G o l d and Si lver 31 Min ing Ltd. in 1968) (DIAND Technica l Serv ices , 1993b). In J u n e 1967, construct ion began on a 272 tonne/day capacity mill and concentrator that operated during May -December 1968 and March-October 1969 (DIAND Techn ica l Serv i ces , 1993b). The mines were not very profitable however, as the mill c losed down having only p rocessed a total of 50,751 tonnes of ore after these two s e a s o n s (Environmental Se rv i ces , 1998). T h e ore w a s separated using flotation. During this time, the mill d ischarged 3 2 approximately 27 ,000 m tail ings into the 24,700 m (190 m x 130 m) pond area (Environmental Serv ices , 1998; E B A Engineer ing Consul tants Ltd., 2001) . Rec lamat ion Activi t ies T h e mill and tail ings impoundment site was not l isted among the 49 mining propert ies a s s e s s e d by DIAND in 1993, though the mines that fed the mill were inc luded. Due to concerns about environmental quality ra ised by the Ca rc ross /Tag i sh First Nat ion, government and other interested parties, the site w a s a s s e s s e d in 1997. A s s e s s m e n t s revealed windblown tail ings a long the northeast edge of the impoundment, as wel l as tail ings spil l ing into an unnamed pond 80 m to the west v ia a decant pipe. The pond was originally a marsh from which T a n k C reek f lowed, d ischarg ing to Bennett Lake. At an a c c e s s road at the north end of the marsh, the c reek w a s diverted into a 1 m culvert. Beavers built a dam over this culvert to create a pond. T h e tai l ings site is shown in a 1995 aerial photograph (Figure 4). Wa te r quality studies provided ev idence that the tai l ings were acid-generat ing (Environmental Serv ices , 1998), and elevated arsenic, iron, and su lphate levels in Tank C reek had been recorded as early as 1976 (Weag le et al., 1976). T h e s e studies did not show that aquat ic biota was impacted (Weag le et al., 1976; R o a c h , 1997). However, there was ev idence of contamination in the surrounding terrestrial vegetat ion (as d i scussed in sect ion 2.3.1). After another environmental assessment , the dec is ion was made to re-col lect the e roded tai l ings and to p lace them into a capped impoundment. The mill had already been taken out, but the recommendat ion to remove its concrete foundat ion w a s a lso made (Environmental Serv ices , 1998). W h e n the tai l ings were re-col lected in the summer of 1999, the dam was destroyed and the a rea turned back into a marsh. Between Ju ly 1999 and September 2000, the tai l ings were covered with a low permeabil i ty cap des igned to prevent A R D production by el iminating the factors of water 32 and oxygen. The cap compr ised a layer of local sand , gravel and cobb les , which was over la in by a layer of c layey silt ( E B A Engineer ing Consu l tants Ltd., 2001) . F igure 4. Aer ia l photograph of the Arct ic Go ld and Si lver property showing the mill, tai l ings pond, and Tank Creek in 1995 (Geographic Data, 1995). S c a l e is - 1 : 2 0 , 0 0 0 . 3.2 Sampl ing Methodology T h e field s e a s o n (comprising of site assessment , interviews, and sampl ing) took p lace between Ju ly 11 and A u g 29, 2001. Important local plants were initially d i scussed with members of the Little Sa lmon/Carmacks First Nat ion, and the C a r c r o s s / T a g i s h First Nat ion. E lders provided their perspect ives on local vegetat ion: food and medic inal uses , cultural importance, and general ecological knowledge. Seve ra l knowledgeable younger people provided input as well. The intent of the interviews w a s to determine 33 which spec ies were most important to study, g iven that not every spec ies would be found at all the mine site locations. Consequent ly , al though berr ies compr ised the majority of spec ies that were eventually sampled, the importance of yarrow, birch, rose hips, and spruce pitch a rose during d iscuss ions with the E lders . The eight interview participants had grown up in the region of the mine sites and/or were well acquainted with plant medicine. Many conversat ions inc luded a "show and tell" component - trips to a garden or habitat near the community, or bringing medic ine out from storage, such that a visual descr ipt ion of the s p e c i e s being d i scussed could be provided. For instance, W . Atlin (pers. comm., 2001) pointed out roseh ips in her Ca rc ross garden and mentioned that eating three roasted roseh ips per day would prevent getting a co ld . A thapaskan (Tutchone and Tagish) and Tlingit (Inland Tlingit) traditional names of these common local plants were obta ined through the consul tat ions, and with the use of language and historical books (Appendix 2). Sampl ing at e a c h mine site fol lowed a transect des ign such that plants and soil were col lected from three locations: adjacent to the tai l ings or other point source of contaminat ion, 1-3 km away, and background samp les co l lec ted up to 20 km away. Gene ra l sampl ing locat ions for Mt. Nansen are shown in F igure 5. F igure 6 shows the sampl ing locat ions for the Arct ic Go ld and Si lver and the V e n u s M ine tai l ing si tes. F igure 5. Sampl ing locations at the Mt. Nansen study site, inc luding background and point source locat ions. Geo logy , dominant wind direction, and historical land use were condit ions cons idered when choos ing sample areas. In order to compare temporal trends, attempts were made to collect spec ies that had been samp led in prev ious studies (e.g. raspberr ies at V e n u s , and mossberr ies at Mt. Nansen) . However , this w a s occas iona l ly not poss ib le due to the absence of ripe fruit (e.g. raspberr ies at Arc t ic G o l d and Silver). 34 >':iv.:::::::*:':::*' -S-xi-^ i>:':v:-''''''-' •"'' • ' '*:"* - : :: :: :>* :' :: :*-Xv: ::^: ;>:w.y.....: ..>—-:v:::::v:::::::::;::::;::::>v^ >:.::v::-:-:.s':V:::::y:':-:::\';: N Site A3 .SiteV3 111 . • . - • • v Site A2i I : Y U K 0 N jjs'^ Site A2 Old mill site ..mi mm :4Zm mmm 1111; P L A T E A U Arctic Gold and Silver capped tailings Sample Location Legend % : , ©Point source of As • VI or A1: around tailings pond " ® V2 or A2: 1-3 km away V3 or A3: background Big Thing (Arctic Caribou) claim sites <9 Old mill site f ;.; Site VU Venus capped tailings L J kilometres V e n u s M i n e * ' F igure 6. Sampl ing locat ions for the Arct ic Go ld and Si lver, and the V e n u s Mine tailing si tes. T h e majority of plants sampled were berries, which are predominant ly used for food and have historic ceremonial and cultural s igni f icance (Thornton, 1999); other 35 spec ies are foods of foraging animals harvested by the First Nat ions (e.g. car ibou, moose , squirrels, ptarmigan, and grouse). A l l plants col lected in this study have medic inal uses . Tab le 7 shows the plants that were samp led and ana l ysed for arsen ic content at e a c h of the three mine sites. Tab le 7. Breakdown of samples ana lysed for arsen ic content at e a c h mine site. Species Tissue Sites Total Type Mt. Nansen AG&S Venus Blueberr ies (Vaccinium spp.) berry 22 0 0 22 Lowbush cranberr ies (V. vitis-idaea) berry 23 0 0 23 Labrador tea (Ledum groenlandicum and L. decumbens) shoot 21 0 0 21 Bolete mushroom (Leccinum spp.) stem 21 0 0 21 Car ibou moss (Cladina mitis and Cetraria nivalis) thallus 21 0 0 21 Wi l low (Salix spp.) stem 22 0 0 22 Wi l low (Salix spp.) leaves 22 0 0 22 Crowberr ies (Empetrum nigrum) berry 22 0 0 22 Soapber r ies (Shepherdia canadensis) berry 0 . 10 0 10 Raspber r ies (Rubus acaulis) berry 0 0 12 12 Soi l N/A 23 10 9 42 Total 197 20 21 238 At least three samples of a plant spec ies were co l lected from e a c h location. S p e c i e s were identified using plant guidebooks, and sample locat ions were recorded us ing a hand-he ld G P S unit (Garmin 12XL) . S a m p l e s were photographed in situ, prepared, and stored f rozen. Preparat ion included creat ing voucher spec imens, separat ing wil low leaves and stems, removing the mushroom cap from the stalk, c lean ing l ichen of leaf matter, and rinsing mushroom stems, wi l low leaves and Labrador tea shoots twice in de- ion ized water. At least three samples of soil were a lso col lected at e a c h locat ion (0-10 cm depth) us ing plast ic scoops and Whi r lpak™ bags to minimize external contaminat ion. S a m p l e s were sh ipped frozen to either U B C or Enviro-test Laborator ies. The col lect ion of 424 samples was prioritized in fall 2001 , during which time the budget was f ina l ized. A total of 238 plant and soil samples were se lec ted for inorganic and organic 36 arsen ic analys is : 197 from Mt. Nansen , 20 from the V e n u s tai l ings, and 21 from the Arc t ic G o l d and Si lver site (Table 7). A l l other samp les remain in f rozen s torage at U B C . Emphas i s was p laced on col lect ing and analys ing plants from Mt. N a n s e n b e c a u s e this site has not yet been c leaned up unlike the other two s i tes, a n d a rsen ic data from plants has not been col lected from here s ince 1984. S p e c i e s c h o s e n for ana lys is were those repeatedly mentioned by community residents, and a lso sufficiently abundant in the vicinity of the mine. For example, puffballs and c loudberr ies are important local plants to the Little Sa lmon /Carmacks First Nat ion, but were not found growing at each of the three locations around a particular mine, and therefore were exc luded from the final list of samples to be ana lysed. Other spec ies were exc luded b e c a u s e of their apparent lesser s igni f icance to First Nat ion members (for example, a l though rosehips, Labrador tea, willow, and goose-berr ies were present around the V e n u s Mine , raspberr ies were the spec ies most often p icked there by local residents). 3.3 Laboratory Ana lys is Enviro-test Laborator ies in Edmonton, A B was chosen to ana l yse the samp les in this 2001 study because the company had previously ana lysed organ ic and inorganic a rsen ic concentrat ions in plant t issues from the V e n u s and the Arct ic G o l d and Si lver si tes. Thei r analyt ical technique was deve loped for a prev ious study, and is not common in the literature. Most commercial and university labs can only ana lyze for total arsenic , whi le a few university labs are capab le of speciat ion techn iques that al low the concentrat ion of speci f ic compounds to be determined (e.g. A s 3 + , A s 5 + , or a rsenosugars) . The preparation and analys is procedure fo l lowed by Enviro-test (H. Z h a o , pers. comm., 2002) is descr ibed here: samples se lec ted for ana lys is were f reeze-dr ied (plant t issue) or oven-dr ied (soils), ground, and then separa ted into two parts. O n e part was wet-ashed, digested, and ana lysed for total a rsen ic us ing an Inductively Coup led P l a s m a M a s s Spectrometer that had a detect ion limit of 0.05 mg/kg for plant t issue and 0.1 mg/kg for soi ls. The other part was used to obtain inorganic a rsen ic va lues by first extracting arsenic from the sample with 2 0 % HCI ( E P A procedure 1632), mixing part of the extraction with HBr-Hydraz ine sulphate, and then using hydr ide generat ion Atomic Absorpt ion Spect roscopy. Organ ic a rsen ic was then 37 ca lcu la ted from the difference between total and inorganic va lues. Resu l ts were reported in both (as-received) wet weight and dry weight, us ing moisture content to convert the former. Qual i ty Control (QC) data confirm that analys is methods were recover ing and account ing for all the arsenic present, and ensured that instruments were properly cal ibrated. Repor ted and internal laboratory Q C checks used by Enviro-test inc luded the use of s tandard certif ied reference materials ( C R M ' s ) , sample matrix sp ikes, system and method blanks, sample dupl icates, continuing cal ibrat ion verif ication s tandards, and alternate source standards. C R M ' s are avai lable for total a rsen ic tests (using NIST 2709 S O I L and NIST 1575 P INE N E E D L E S ) ; however there are currently no C R M ' s ava i lab le for inorganic arsenic. A Q C report for total arsenic was sent on June 17, 2002, a long with Q C for the 19 re -checked samples , fol lowed on June 18, 2002 by a rev ised spreadsheet of the final results due to two incorrectly entered results. Al l Q C data from both the total and inorganic a rsen ic ana lyses were acceptable, using default limits recommended by the U S E P A . 3.4 Stat ist ical Ana lys is Statist ical analys is was performed using J M P - I N vers ion 4.0.3 ( S A S Institute Inc., 2000). Pr ior to using the J M P - I N program, the inorganic and organ ic a rsen ic concentrat ions provided by Enviro-test were added together to obtain total arsenic. Undetectab le concentrat ions were ass igned a 0.001 ppm va lue in order to be able to statistically ana lyse these data. The distribution of all a rsen ic data sets (total, inorganic, and organic) for each spec ies was then examined. The Shap i ro -Wi lk goodness-of- f i t (or W statistic) test was used to check for normality, and outlier and quanti le box plots identif ied outl iers. A nonparametr ic analys is of var iance ( A N O V A ) was performed using the Wi lcoxon /Kruska l -Wa l l i s Rank Sum test (a = 0.05). A N O V A s were carr ied out using the Fit Y by X function where Y = arsenic (dry weight; either total, inorganic, or organic arsenic) and X = Location). If the data were not normally distributed (the situation for 11 of 13 spec ies for all arsenic data sets), six common transformations were attempted: \og(x + l), *Jx + 0.5, log\0(x + i), arcsin(V*), log(x), and ^/x+^[x + l. In 4 5 % of all cases where transformations were attempted, the data could be transformed to normality. 38 S p e c i e s data that were normally distributed were then tested parametr ical ly. Tes ts for equal var iance, e.g. O'Br ien 's test, ( S A S Institute Inc., 2000) were used to indicate whether heteroskedastici ty was present. In data sets where unequa l var iance occur red, the var iance-weighted W e l c h F test (Welch 's approximate f) w a s used . The var iances were cons idered unequal if the p value for either F test was smal l (<0.05). G i ven the nature of the data, Tukey-Kramer 's H S D was deemed most sui table as a post -hoc test for di f ferences among means (Zar, 1984). The underly ing geo logy of the sample locat ions was then tested as a nested variable in the A N O V A s . T h e remaining spec ies that were not initially distributed normal ly were tested nonparametr ical ly. Dunn 's test, as provided in Zar (1984), was used to determine di f ferences among means, similar to the Tukey-Kramer 's H S D test for normally distr ibuted data. The spec ies data were then ranked such that the new data cou ld be treated parametr ical ly and checked for normality, signif icant means , and equa l var iance. T h e rank transformation method is straightforward, easy to use , and acceptab le for multi-factor ana lyses (Conover and Iman, 1981; Potvin and Roff, 1993; Johnstone, 1995). Geo logy was then examined as an explanatory var iable. Deta i led statistical analys is results for the data sets are d isp layed in Append ix 3. Chapter 4: Results Resu l ts support other studies that found plant uptake was low compared to soi l concentrat ions. M e a n total arsenic concentrat ions in plants at all mining propert ies ranged from undetectable to 31.1 ppm (Figure 7), whi le mean total soi l concentrat ions ranged from 9.087 to 11373 pg/g (ppm) (Figure 8). Berry spec ies had little or undetectable mean total arsenic (< 1.3 ppm), and medic inal shrubs (Labrador tea, wi l low leaves, and wil low stems) had <16.7 ppm mean total arsenic . Higher a rsen ic concentrat ions were found in plant and soi l samples co l lec ted around the point source(s) of contaminat ion, and concentrat ions dec reased with increas ing d is tance (F igures 7 and 8, respectively). This was the trend general ly observed at all the tail ing s i tes (mushrooms were the only significant except ion at the Mt. N a n s e n site). II 3 tQ o ° c Arsenic concentration (mg/kg) 0 .3 01 Q. o CO O C CD -v| O CD O »-»-9L ^ CO K> CO CD o' 8 8 i-co TT 3 CO cu OJ m 0) *<! o <-< CQ CD 3 CO C 2 S 5 ' TJ CO 3 r-* CU CO CD S 8 | . | rf CD IT CL CD Q) co "T" Q) CD 3 CB 1 & £ CD § 3 CD » s ? cq 3 T3 TJ CD — O 3 CD<Q W o c3 I as a ? CD co 13 . ro ro oo o o» o * A cn O Ol o 40 Figure 8. M e a n total arsen ic concentration (±SE; dry weight) in so i ls co l lected at each mine site. Sampl ing classi f icat ion as 1 (around point source) , 2 (ca. 1-3 km away), or 3 (background). M e a n s with the same letter within a site are not different (p=0.05). T h e dominant form of arsenic was inorganic, both in soi l (F igure 9) and plants (Figure 10). Of the samples with detectable arsenic, the organ ic form w a s absent in blueberry and cranberry (Figure 11). 100000 E c o s CD o a o o o CD < 10000 .2 1000 100 10 N1 (8) | N2 (9) | N3 (6) Mt. Nansen M Organic Arsenic M Inorganic Arsenic V1 (3) | V2(3) | V3 (3) Venus A1 (4) | A2 (3) | A3 (3) AG&S Figure 9. M e a n arsen ic concentrat ion (dry weight) in soi ls co l lec ted at e a c h mine site. Sampl ing c lassi f icat ion as 1 (around point source) , 2 (ca. 1-3 km away), or 3 (background). Samp le s ize is shown in brackets. S tandard error bars are shown for total a rsen ic concentrat ions. 0) TJ T l CO 2 . CD* CD 2 . c 3 0 _», 1 p 13 CO =*. cu cu ° - 5 C O ? rn 8 | 8 o cu —i CO o ' CU C i SH CQ < 3 i i f TJ 5-• S ss. 8 N = CD CD » § . § .8 . Q CD | CD _. 0) cr J 3 3 5- 2 5 ^ ' CD CO ' 55" co =3 cu | i CD (Q —i 3 2-cr co CD CO £ 8 CD o (fi 3 O °> 3 S 3 o c PI g . CT C CD 3 cu CO CT CO O o 53 3 CU S 53 Q. O 3 o CO CO CT CD I 3 c CO 3 I CD 5 Q) = c6 9 co § CD = co € Arsenic concentration (mg/kg) o i o c n o o i o o i o o i o I 53 CO TJ cr CD co O CO TJ cr CD CJ) CO CJ) 3 S 3 w 3 ± 3 W 3 § O) co ro 3 co 3 5 D—i CO i3 CO 3 M 3 Ko o CO 3 6 O) CO S 5 i ^ N> *S CO 3 £ 3 to 3 & • 3 O c3 0) 3 o' > CQ 0) 3 > -3 CO CO CD CD 3 3 . O o CO 3 CO CD 13 < CD C co > O Co CO I* ro C f l ) Tl O fl) CD c . O Q) <fl ° O CQ CD o 53 CD 5 o' r o CO o l i 3 fl) ef z s •< o o f f CO £ CT " * Q) Q. £ ^ <Q $ o 5 C CQ 5" CD Q) I (fl cfl | 8 = CD IT O CD CD w Q-0) Q) 3 ~* fD © _ 0) a s -? 3 | S =r w 3 Q) P Cfl CD A) Q. 3 CD "D (fl — 3><Q CD o O cfl i i P I s Arsen ic concentrat ion (mg/kg) _ k . _ j . _ i . __ __. NJ O M J > c r ) C o o r « O J > . c r ) O o o 43 Organ ic a rsen ic may not have been present in all soi l samp les , but the mean concentrat ion in soi ls for any particular location shows that a rsen ic was detectable (Figure 12). 10000 N1 N2 | N3 Mt. Nansen Figure 12. M e a n organic arsenic concentration (±SE; dry weight) in so i ls co l lected at each mine site. Sampl ing classif icat ion as 1 (around point source) , 2 (ca. 1-3 km away), or 3 (background). M e a n s with the same letter within a site are not different (p=0.05). A Bio logical Absorpt ion Coefficient (BAC) indicates the ratio of an element concentrat ion in a plant to the same element concentrat ion in the surrounding soil (Kovalevsky, 1969; Kaba ta -Pend ias and Pend ias , 2001). M e a n a rsen ic ratios were general ly low (<2.5) for all locations (Figure 13); va lues greater than one reflect high a rsen ic va lues in plants growing in soil with low concentrat ions for some individual soil and plant pairs. T h e B A C values for berries did not exceed 0.015, and ranged from 0.02 (N1) to 0.11 (N2) for mushrooms. The highest B A C va lues were found in car ibou moss and the medic inal shrubs: caribou moss ranged from 0.1 (N3) to 2.5 (N2), Labrador tea had less than 1.8, and wil low did not exceed 0.62. The re was no apparent trend in the locat ions yielding the highest B A C va lues, as both N1 and N2 had equal contr ibutions. T h e B A C values are likely underest imates b e c a u s e of ass ign ing 0.001 ppm to samp les less than the detection limit. 00 J l > { Q ' CO <l> Biological Absorption Coefficient co CD 3 — CD S-CQ i s ' CD — CJ > 1 - f 0) O 1 1 Q . 3 CO O o o — CD S B 5L CD o) 3 CO - 3 ; CD CD 3 > O O 11 Q co 2- CD-S' w => 0) CO * * ^-v Q . 3 i CQ CD £ 3 CQ 3 Q - ~ I f CQ 3 cr CD 3 CD CO CO CD CO CT c CD CT CD CD CO _ o 3 Q) o — CO CT CO O 0) CT CD —i CD' CO 0) CT —1 Q> Q. O —i •—* CD 0) CO CO CT CD CD CO CO ZT —l O o 3 S i i | cn < co $ 1 i 0) CO T3 CT CD —i —i CD CO CO o 01 X> CT CD -l CD CO O b 2 < < < co > to > CO o Ol b CO b 45 4.1 Mt. N a n s e n Mine Site B lueberr ies (Vaccinium spp.) B lueberr ies had less than detectable arsenic for 19 of 22 samp les . T h e highest detectable arsen ic concentrat ion was 0.5 ppm, from an N2 sample co l lec ted - 4 0 m west of the upper old tail ings pond and near the edge of Dome Cr . T h e other two detectable samp les (0.3 ppm) came from a site ~5 m west of a N-S or iented a c c e s s road running paral lel to the Brown-McDade open pit, and from a site ~500 m down Dome C reek from the tail ings pond on the north s ide. Non-parametr ic A N O V A showed no signif icant di f ferences between the means of N1 , N2, and N3 for all three arsen ic data sets (Figures 7, 11, and 14). Ca r i bou moss (CladinafCetraria spp.) Car ibou moss (lichen) y ie lded the highest a rsen ic concentrat ions of all plant spec ies . A rsen i c was detectable in all samples , ranging from 0.2 ppm (background samp le from a north facing s lope of a hill north of R o u n d Lake) to 96 .5 ppm (N1 sample co l lected - 0 . 7 5 m from the south edge of the tai l ings pond). There w a s signif icant variat ion among the three locations ( A N O V A p<0.05), and Tu key-Kramer 's H S D test showed that the means for locations N1 and N3 were signif icantly different for all a rsen ic forms. N2 and N3 were a lso significantly different for total and inorganic a rsen ic (F igures 7 and 14). Cranber r ies (Vaccinium vitis-idaea) Of the 23 cranberry samples , 19 had less than the 0.05 ppm detect ion limit. The highest a rsen ic concentrat ion was 0.5 ppm, from two samp les co l lected from N2 sites. T h e first was samp led ~1 km west of the tail ings pond and ~150 south of Dome C reek on the edge of an old road. The second was col lected - 2 0 m west of the lower old tai l ings pond and - 4 0 m N E of Dome Creek. The remaining samp le with detectable a rsen ic (0.3 ppm) came from a site located directly be low the upper o ld tai l ings pond. Non-parametr ic A N O V A on the total, organic, and inorganic data revea led no signif icant di f ferences between the means of N1 , N2, and N3 , (F igures 7, 11, and 14). O fl) CD £ S 32 CD O Q) 3' = #—)-CO 3 o o fl) o' hO 0) to CD ZJ o' 8 0) 0) >" o Q - m cu - • o 9-CQ "< i i 3 CQ Q . ZT 1+ 5 = CD 12-0) 0) 3 3 CO CO I I —> CD CO Q_ I s CD CD =- 0) £ _ T ? 3 £ 3 § CD =T. CO 3 iK Q) CD •§ CO CD 0) Q. 3 CD T3 (O — 0) 3 =; CQ CD o i * CD*8 1 1 g N1 CT c CD CT CD O S a c/> o o fl) CT CD CD § " a, » o 3 c 00 zr —^  o o _3_ CO S CD = CO $ CO to TJ CT CD to O 0) T3 CT CD Arsen ic concentrat ion (mg/kg) Ol o Ol o N2 ^ N3 N1 N2 N3~ N1 N2 N3 N1 N2  N3 § N1 CT CD N2 N3 N2 _ ^ N1 CD $ s I N3 N1 V1 V2 V3 A1 A2 A) 0) fl) D o fl) 0) fl) N1 bfl) s= N2 I or N2 bB-N3 ' cr o 0) 0) 0) o 3 A3 cr o D o ) CT CT O 0) 0) 0) H fl) ~* CT H 0) 0) CT 0) HQ) 47 Labrador T e a (Ledum groenlandicum/L decumbens spp.) T h e var iance of Labrador tea arsen ic data was high: samp les ranged from an undetectable background sample col lected on the east s ide of Back C r e e k (several hundred meters from the Pony Creek conf luence) to an 87.8 ppm samp le co l lec ted 1.5 m from the south-east edge of the tail ings pond. The next highest samp le w a s 5.8 ppm from a site on the south edge of Pony Creek, west of the waste rock pile near the adit. There was signif icant variation among the sites ( A N O V A p<0.05) for all forms of arsen ic . T h e Tukey-Kramer H S D test on the transformed total a n d inorganic a rsen ic data showed signif icant dif ferences between N1-N3 , and N 2 - N 3 (F igures 7 and 14). For organ ic arsenic, Dunn's test of the original data did not show any signif icant d i f ferences between locations. However, Tukey-Kramer 's H S D test on the ranked organic data showed that N1 and N3 were signif icantly different (Figure 11). Mossber r i es (Empetrum nigrum) Of the 22 crowberry samples, 19 had less than detectable arsen ic . T h e two highest total a rsen ic concentrat ions (0.7 ppm and 0.5 ppm) were found near the Brown-M c D a d e open pit: the first is a sample col lected from a west- fac ing s lope ~30 m east of the pit, and the other col lected 10 m from Pony Creek and west of the adit located there. It is interesting to note that a 0.4 ppm sample, unusual ly all o rgan ic arsenic , was co l lec ted from the east- facing s lope above the road north of R o u n d Lake . There were no signif icant di f ferences between the means in the A N O V A s (F igures 7, 11, and 14). Bolete Mushrooms (Leccinum spp.) Twe lve of twenty-one mushroom stem samples had undetectable arsenic, including some col lected around point sources. The highest concentrat ion (34.8 ppm) was found in a sample col lected beside an E - W oriented a c c e s s road - 1 . 5 km north east of the tai l ings pond, and <1 km west of the open pit and waste rock pile. T h e next highest sample w a s 2.6 ppm from a location - 5 0 m east of the lower o ld tai l ings pond and bes ide a stream (-1 km northwest of the new tai l ings pond). Non-parametr ic A N O V A w a s signif icant for total and inorganic a rsen ic data. Both the non-parametr ic Dunn 's test (original data) and Tukey-Kramer 's H S D test ( ranked data) revealed signif icant di f ferences in the means between locations N2 and N3 for total and inorganic a rsen ic (F igures 7 and 14). 48 Wi l low S tems (Salix spp.) Wi l l ow stems ranged from undetectable to 28.6 ppm (on a hill east of the pit). T h e next highest concentrat ion was 2.2 ppm (east of the adit near Pony Creek) . Wi l low stem data responded to a log transformation except for organic a rsen ic data, which required be ing ranked in order to run parametr ic tests. The re was signif icant variation among the locat ions ( A N O V A p<0.05) for the total and inorganic a rsen ic data. At p<0.10, A N O V A was signif icant for o rgan ic a rsen ic data. For all a rsen ic forms, the Tukey-Kramer H S D test showed signif icant di f ferences between the means of N1 and N3 (Figures 7, 11, and 14). W i l l ow L e a v e s (Salix spp.) Concentra t ions ranged from undetectable to 22.1 ppm (on the hill east of the pit). The s e c o n d highest concentrat ion was 2.2 ppm (east of the adit). A l l three original data sets were not normally distributed. Non-parametr ic A N O V A showed there were di f ferences among the locations. Both the non-parametr ic Dunn 's (original data) and the Tukey -Kramer H S D test (ranked data) showed signif icant d i f ferences between means for N 1 - N 2 and N1 -N3 for both total and inorganic a rsen ic (F igures 7 and 14). T h e Tukey-Kramer 's H S D test a lso showed N2 and N3 were signif icantly different for inorganic a rsen ic (Figure 14). In a separate analys is of a rsen ic found in s tems versus leaves, mean concentrat ions were not significantly different from one another between locat ions (Appendix 3). So i l So i l data ranged from 0.8 ppm (N2) to 3083 ppm (N1). Two samp les exceeded Y u k o n C S R guidel ine, the second va lue be ing 2320 ppm (N1). So i l samp le means between the locat ions were not significantly different for total, organic, and inorganic a rsen ic (F igures 8, 12, and 15). 4.2 V e n u s Mine Site Raspber r ies (Rubus acaulis) Of the twelve raspberry samples col lected from the vicinity of the tai l ings pond, the gravel pit, and a longs ide the highway near Carc ross , the only samp les with 49 100000 "Si E c o ••o CO c CD o § o o 'c 11 10000 1000 100 N1 | N2 | N3 Mt. Nansen A2 AG&S Figure 15. M e a n inorganic arsenic concentration (±SE; dry weight) in soi ls co l lected at e a c h mine site. Sampl ing classi f icat ion as 1 (around point source) , 2 (ca. 1-3 km away), or 3 (background). M e a n s with the same letter within a site are not different (p=0.05). detectable arsen ic were those found around the capped tai l ings pond. Tota l arsenic concentrat ions of these four samples ranged from 0.4 ppm to 2.9 ppm, with an average of 1.25 ppm (Figure 7). Inorganic arsenic content ranged from 0.4 ppm to 1.2 ppm, with a mean of 0.775 ppm (Figure 14). A N O V A was signif icant for total and inorganic a rsen ic data. Dunn 's test (original data) and the Tukey-Kramer ' s H S D test (on ranked data) showed that locat ions V 1 - V 2 and V 1 - V 3 were signif icantly different for both of these forms of a rsen ic (Figures 7 and 14). So i l So i l a rsen ic concentrat ions at the V e n u s tai l ings site ranged from 11.5 ppm (V3) to 23 ,970 ppm (V1), and three of the nine samples exceeded the Y u k o n C S R . T h e two highest soi l a rsen ic concentrat ions were col lected from the s a m e genera l a reas where the two highest raspberry concentrat ions were samp led : the h ighest found ~2 m from a stream located at the south end of the cap, and the second highest (9040 ppm) was col lected a long the N E edge of the cap. The third V1 sample w a s 1109 ppm. A N O V A showed that there were dif ferences among the locat ions samp led . U s i n g Tukey-Kramer 's H S D test, V1 was different from both V 2 and V 3 (Figure 8, 12, and 15). 50 4.3 Arct ic Go ld and Si lver Mine Site Soapber r ies (Shepherdia canadensis) Al l nine soapberry samples had undetectable arsen ic levels. So i l So i l concentrat ions from the Arct ic Go ld and Si lver site ranged from 4.9 (A3) to 83.2 ppm (an A1 sample site located on a vegetated mound in the east centre of the capped tail ings). The mean total arsenic concentrat ion for A1 samp les co l lec ted around the tai l ings (50.5 ppm) did not exceed the 150 ppm Y u k o n C S R standard, and these concentrat ions were quite consistent. A N O V A was signif icant for inorganic a rsen ic but subsequent parametr ic tests showed no significant di f ferences among the means . Chapter 5: Discussion The results indicate that for some spec ies there is a spatial trend of lower a rsen ic concentrat ions further away from point sources. W h e n compared to data from previous studies, other spat ial and temporal trends become apparent as wel l . T h e s e results can be interpreted in terms of individual spec ies response, poss ib le explanatory factors, spec i f ic plant uses (as conveyed by First Nat ion interview part icipants), and guidel ine compar isons . For spec ies with detectable inorganic arsenic , a ca lcu lat ion of To lerab le Dai ly Intakes was warranted for the Carmacks and Ca rc ross res idents interested in gather ing at the mine sites. These issues will be examined in the fol lowing chapter. 5.1 Compar i sons Wi th Other Yukon Data T h e overal l lack of detectable arsenic in the berr ies co l lected from Mt. Nansen , Arct ic G o l d and Si lver, and background locations for the V e n u s Mine tai l ings property is comparab le to a rsen ic concentrat ions in the same berr ies samp led at other Y u k o n sites such as the communit ies of Dawson City, Ha ines Junct ion, R o s s River, Tes l i n , W a t s o n Lake, and Whi tehorse (Gamberg, 2000). Refer to Append ix 4 for spec i f ic results. For Mt. Nansen spec ies with consistently detectable a rsen ic such as car ibou moss and wil low twigs, the low concentrat ions found in the background samp les (N3) 51 were representat ive of the data col lected by Gamberg (2000) in Dawson City, R o s s River, and W a t s o n L a k e 4 (Appendix 4). Th is similarity w a s observed with the mushroom data as wel l , al though it is noted that only one sample (from Whi tehorse) w a s identif ied as a Bolete mushroom (Appendix 4). Its compar ison is cha l lenged by the di f ference in parts ana lysed (thallus compr ised of cap and stem versus stem), part icularly if mushrooms store arsenic in different a reas as other spec ies do. 5.2 Tempora l T rends A r s e n i c content in the 2001 Mt. Nansen berries was a lso comparab le to the 1984 Mt. N a n s e n results found by God in and Os ie r (1985). Attempts were made to sample in the s a m e vicinity as their 1984 study (location N4 in Figure 5; ana lysed as locat ion N2). Dur ing the 1984 study by God in and Os ie r (1995), Mt. N a n s e n sur face and depth soi l samp les were col lected from locations around the old tail ing ponds. Depth samp les (up to 0.5 m) general ly had low total arsenic concentrat ions that ranged between 10 and 180 ppm. O n e except ion was a 28,000 ppm sample col lected from the embankment separat ing the two ponds, at approximately 40 cm depth. T h e 1984 sur face samp les ranged from <5 ppm to 300 ppm. Excluding 1984 data from locat ions not repl icated in s the 2001 study (location N4), and excluding samples col lected in 1984 at depths greater than 10 cm (the maximum 2001 depth), a compar ison of total a rsen ic data from the two studies shows similar results: 1984 concentrat ions in sur face samp les range from 70 to 150 ppm; 1984 concentrat ions in 10 cm depth samples range from 30 to 60 ppm; and 2001 concentrat ions range from 4.1 to 112 ppm (Figure 16). T h e temporal pattern of arsenic concentrat ions in raspberr ies co l lec ted near the V e n u s tai l ings shows a distinct decrease s ince the cap was constructed in 1995 (Figure 17). So i l a rsen ic concentrat ions here are a lso lower than the data co l lec ted in an earl ier study (Figure 18). In 1984, total arsenic concentrat ions from sur face samp les ranged from 45,000 to 83,000, and depth samples (approximately 10 cm) ranged from 800 to 70 ,000 ppm; there was a distinct decrease in depth for all locat ions around the tai l ings pond (Godin and Osier , 1985). 4 Small sample size (typically n=1) in previous studies affected the ability to determine significant differences and standard error calculations. I f CO §-. w 3 ?r CQ 3 g-co H % O Z 1 CO CQ CD C CD CD 0) 0) 3 (Q O TJ Z, O z 3 CO co cr cr o CO CQ CD 3 CD 2 T3 C CD 3 CQ Q-CD ^ £ c o CD 3 cr Q) o o CO CO CD c TJ "2 * CD pt XJ -l O CO CJ 3 Q . CD o ? 2. co Q TJ 5 CD » % 3 ^ Q- O CD , n CO <£ CO 00 «-•-O CO TJ 2 CO > CD o* o. co_ 3 Er o CO Q E T § Q. CD 3 ~ 3 CO CO o l l CD H* CO CO N'JT1 2.CL CO , 3 o a 1 ^ 2T=> 0) CO 1 ° 2- CO CO CD ' 3 COTJ 9> CD 3 co "2. o 3 ' 2 CQ CD o a 0) CD ^ 3 co 3 3 "2. CD (D QJ _ - • O 3 o-CD 3 O ' ' 3. CO CD — tf) Q .  CD 3 T 0) 3 3 CD 3 Q. CO 3 co co I I o S 3 O CO c <» 2-CD 9> W O CD C 3 c i s -TJ -»• O CD 3 0 0 CO ^ 2 CD 5= o O 2. 3 C ~ CD 2 3 ro Q . to c CO ^~ O N> (D QJ 1\5 TJ w =T O f o Q w 3 to c o po CD CT f o to c O N> CD O l o ^ o A rsen ic concentrat ion (mg/kg) io CD CXJ o ro J*. o o o o o o o o o o o o o o to 2 CD 2 CO CO 2 CO 2 CO 2 -3 2 35 2 39 CO o c a CD CO CD 00 O o o , 0 NJ O O —k Q. 0) ST Co" CA 0) so. =r c o Q_ q ~ O o Q. 3' fl) 3 Q. O CO. CD CD 00 CD CD cn o. DO 3" O 3 O 0) o CD CD O l CD CD CD Q. 0) 3 3 7J O 0) o 3-0) 3 Q. O c 3 3 u' CQ z r fl) 3 O Q QT 31 5 ' c 0) o CO CO CQ CO ro io cn CD fl) O 3 ^ Q- . eg | co 2-c 5 g o co CQ 3 c 3 Q. CO 0) 3 •o CD CO 3 o' 8 3 2 3 —l 0) o' 3 CO CO | CO _. 3"CQ S 3 3 —. — 3 => -CT fl) 75 CO fl) "O " c r CD CD & _ o. o =* CD o 3 Q. S"' I CQ' 3" i =0 C Cr c CO Q> s-c Co' 0) <S -v - 3 •>J II TJ CD CO Wi $ TT =; 3 3 3 «Q O » a- 2? ~ < fl) (O 3 - 5 , o o CD O CD Q. O 3 8 o J CD 2, CL cf 3 C CO 3 CD Arsen ic concentrat ion (mg/kg) o c n o c n o c n o c n o c n o < x 3 ro o o ro o o ro < ro co co 4-< ro co co CD < ro ro o o < CO ro o o 4^ -v 2 sr > CO CD o* eg cr 7TTJ ^ 3 ? CD CO O s § Er CD l o ? ro 2 Q ho -»> -J 3 3 3? Q. C0_ ct T ° Q S 6T co = CD =j 2 ^ 3 § 3 a m < • to to S II SS, cr cF 0) - i o O CQ CD £ CD 3 00 CL • O H C0_ O CD CD —i — DJ CO CO 00 CD 01 3 aT o ' RS Arsen ic concentrat ion (mg/kg) co3 oo T3. CD to to 2 o — o CO = Q) CD ?! o =* S 5 S"- ° O 3 3 Q. CD CD 2. $ a. 55 CD *< a s TJ • O 3 -vl ° - cn 3 CD at 3 & co' o & w c ^ CL H-:< co • m CO Q. CD 2-3 *< •2. £ CD CD CO CQ CD C5 CO' 5' « to 0 2. 1 «» 3 Q) 3 ' 3 Cr-CL s ^ cT8 CD a CD Q. 3 3 , CD Q) o co 2 CD CD O =r C 3 <-CQ CD «» to r -O s 1 1 O z* go CD < « Cf < i 5T 3 = CD CQ D? CO =r. « ,3 ?*CQ CD to '<% ro CD n -CQ ^ ?j CO < oo CD jfl k ro CO jv cn CD 00 CO o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o V9 55 5:3 Interpretation of Resul ts 5.3.1 Mt. N a n s e n Mine Site Low or undetectable concentrat ions in berry samp les suggest that if the plant is taking up arsenic , it is not being stored in the fruit. Indeed concentrat ions are higher in the shoots of other shrubs (Labrador tea and willow). In the so le c a s e where plant parts cou ld be compared , there were no significant di f ferences between a rsen ic stored in the older woody t issue of the wil low stems and the arsen ic found in the leaves. Th is result w a s unl ike the data descr ibed in Dunn (1995) where there are c lear di f ferences in a rsen ic concentrat ions between the stems and twigs versus the roots and outer bark ( lodgepole pine), the inner and outer bark (red spruce and paper birch). However, as shown earl ier, spec ies have individual responses to a rsen ic in the environment and cannot be readi ly compared. It was difficult to determine whether contamination in Mt. N a n s e n vegetat ion was due to mineral extraction or natural sources. Lower concentrat ions in plants at greater d is tances from point sources suggest mining activity (predominantly wind-eroded tai l ings and exposed soil) is a factor, modified by any toxici ty-reducing mechan isms used by a spec ies . Wi th background levels being similar to concentrat ions found in other Y u k o n plants growing on var ied substrates (Appendix 4), bedrock geology appears not to be a strong influence in determining uptake. However , ore is extracted from a reas with naturally greater arsenic concentrat ions, and some A N O V A models indicated that the variation in concentrat ions could be exp la ined by bedrock geology type (Appendix 3). However, the surficial geology was largely consis tent throughout the study site, and bel ieved to be more of a factor for arsen ic uptake than bedrock geology. T h e results of two spec ies suggest different conc lus ions as to the origin of the a rsen ic caus ing higher concentrat ions. The B A C for car ibou moss sugges ts these l ichens take up arsen ic more efficiently than other spec ies . Though l ichens contain rh izome-l ike structures that can absorb elements from their substrate, the genera l lack of a root sys tem suggests absorpt ion is primarily from airborne sources . G i v e n the lack of exposed rock sur faces in the Nansen region, this points to mining activi t ies such as the p resence of t renches, tail ings, the open pit, and a waste rock pi le a s be ing primary . s o u r c e s of aeo l ian arsenic. For Bolete mushrooms, the mean for locat ion N2 was 56 skewed by one sample with an arsenic concentrat ion >10 t imes that of the next highest concentrat ion. Th is is attributed to natural uptake from the surrounding so i l , though it is a lso poss ib le that soi l part icles remained on the stalk after r insing. A l though some Mt. Nansen soil samples (from N1 , N2, and N3) e x c e e d e d the C C M E guidel ine of 50 ppm and some N1 samples exceeded the Y u k o n C S R guidel ine of 150 ppm, naturally high arsenic content in the soi l is suspec ted to be the major explanat ion. It has been suggested that there is a relat ionship between high Bio logical Absorp t ion Coeff icient va lues and essent ia l e lements (Timperley et al., 1973; Kova levsky , 1995a). Plotted on a l inear sca le , the B A C for essent ia l e lements (e.g. copper and z inc) dec reases as soil concentrat ions increase, whi le non-essent ia l e lements (e.g. nickel) show a low yet similar concentrat ion regard less of the soi l concentrat ion (Kovalevsky, 1995a). The shape of the logarithmic plot c reated from the 2001 data i l lustrates the lack of essential i ty for arsen ic by plants, as do the low B A C va lues observed during this study (Figure 19). Kova levsky (1995b) writes that e lements in plant a s h have B A C va lues on the order of 300,000, 3000, and 1.0 for plant-gas, plant-water, and plant-soil relat ionships, respectively. The B A C va lues for the spec ies in this study are general ly lower than the plant-soil ratio. 5.3.2 V e n u s Mine Site A r s e n i c concentrat ions in raspberry samples have dec reased sharp ly s ince the tai l ings pond was capped in 1995. Th is indicates that the dust problem prior to capp ing has been min imized. T h e dec rease in total soil arsenic concentrat ions between 1984 and 2001 appears to be a result of the 1995 cap construction when (access ib le) windblown tai l ings found in the surrounding landscape were consol idated into the exist ing pond. T h e a rsen ic in these impounded tail ings is bel ieved to be immobile, therefore would not be the source of the high concentrat ions still found in soi l samp les co l lec ted around the V e n u s tai l ings. A s the levels exceed what would be expected from an arsenic-r ich geo log ica l substrate, my interpretation is that hot spots exist. T h e dominant wind direct ion at the V e n u s site is from the south; high soil concentrat ions potential ly reflect windblown tai l ings not col lected during the capping project. Biological Absorpt ion Coeff icient o o m m o o CD O O m m o Ol 2 o m i o CO o o m m o o CO o co CD 3 o-O o 3 O CD 3 I o' 3 B CQ^  CQ O O O O O o o o o + I V • • r X o o o m m m + + + o o o o ** • X I H I * • X •It • • 3 2 CO CD i f i 5 0) CO TJ cr CD CD CO I CO o Q> "O cr CD CD $ CO OT I 5 . co 0 2T 1 & i s CO w i 3 o CO co % CD" CD =5 3 co-co co 58 5.3.3 Arct ic Go ld and Si lver Mine Site Wh i l e other berries (bearberry and raspberry) had detectable inorganic a rsen ic in the 1999 study at the Arct ic Go ld and Si lver property (Roach and Cunn ingham, 2000), no pre-reclamat ion soapberry data exists, so spec ies cannot be compared as such . (Readers are reminded that the 2001 col lect ion was based on berr ies that were ripe and abundant throughout the entire study site.) The occur rence of w indborne tai l ings is no longer an issue as it may have been during the 1999 study, suggest ing that if there was an impact from dust on local soapberr ies, it has now been min imized. A rsen i c concentrat ions in soil from the Arct ic Go ld and S i lver property are of low concern . A l though the mean concentrat ion of samples co l lected around the tai l ings exceeds the territorial background concentrat ion, Montana Mounta in bedrock is arsen ic -rich, which leads to e levated soil arsenic levels. 5.4 Ethnobotany Interview comments about the spec ies chosen for ana lys is in this study are prov ided in the fol lowing sect ion, supplemented by other literature sources . T h e medic inal propert ies of a particular plant are often assoc ia ted with chemica ls found within the leaves, roots, stems, or fruit. For this reason, the descr ipt ion for e a c h spec ies inc ludes compounds found within the plant, uses of individual plant parts, general habitat, and any advisor ies about the plant. A g lossary of chemica l compounds is located in Append ix 6a . A g lossary of se lected terms used throughout this dissertat ion is found in Append ix 6b. 5.4.1 D iscuss ion of P lants Samp led in Th is Study B l u e b e r r y - food, medic ine The berr ies contain vitamin C . Blueberry leaves contain tannins, f lavonoids, a lka lo ids, and ir idoids (Maries etal., 2000). S p e c i e s of blueberr ies found in the Yukon include the abundant Vaccinium uliginosum (bog blue/bilberry), and V. caespitosum (dwarf blue/bi lberry) and V. ovalifolium (oval- leaf blue/huckleberry) which are found only in the south. V. uliginosum / 59 is typical ly 20-60 cm tall, and grows in wet ac id ic a reas such as swamps and muskegs, as wel l as in wood lands, heath, and on alpine s lopes (Cody, 2000). V. caespitosum grows to - 2 0 cm, and is found in alpine and subalp ine a reas whi le V. ovalifolium is 20 -100 cm high, and grows on subalp ine s lopes (Cody, 2000). L ike most berries, blueberr ies are eaten as raw fruit or "candy", canned , or cooked in muffins or cook ies (female elder, pers. comm., 2001). Eat ing berr ies improves acne, while consuming syrup can treat vomit ing (Mar ies et al., 2000). Leaves and roots are both boi led and drunk to treat d iarrhea: leaf tea (and dr ied berries) are a lso taken for urinary tract infections, and the tea is used by some diabet ics to moderate sugar levels (Kershaw, 2000). S tems are boi led and drunk to help prevent pregnancy (Maries ef al., 2000) whi le stems and leaf tea is drunk to improve co lds (Andre and Fehr, 2001). Root tea is gargled for sore throats, or used to treat sores (Kershaw, 2000). Bolete mushroom - food, medic ine Leccinum insigne (aspen scaber stalk), L. aurantiacum (orange birch bolete/red-capped scabe r stalk), and L. scabrum (birch bolete/common scabe r stalk) are three members of the Bolete family of mushrooms found in the Y u k o n . A l l three can be misidenti f ied due to their similar appearance: L. insigne has a reddish to orange-brown cap and grows under aspen or mixed aspen and birch stands, L. aurantiacum has an orange-red cap and grows under coniferous and dec iduous trees, and L. scabrum has a brown cap and is found under birch trees (Lincoff, 1981). A l l have b lack sca les on white stalks, and under the caps are spongy pores rather than gil ls (Parker, 1994). Nutrition information speci f ic to this family was not avai lab le, but Kuhnle in and Turner (1991) write that mushrooms general ly have high moisture content, few vitamins, and minor levels of carbohydrates, fibre, protein, and lipids. O n e can get d iarrhea from eat ing too many Bolete mushrooms (K. Char l ie , pers. comm., 2001). Bolete s tems are typically eaten and the cap d iscarded, though the latter is consumed if no maggots are present. Mushrooms are p icked whenever it rains. They are then cut up and p laced in the f reezer or dried - a de l icacy for e lders . A d d e d to f ish soup, f ish chowder, or frying onions (female elder, pers. comm., 2001) , mushrooms are eaten raw, roasted, or fr ied. They can a lso be rolled in the campf i re to b lacken; the b lack part is removed and the remainder eaten (V. Johnn ie and B .P . Johnn ie , pers. 60 comm., 2001). T h e s e "orange tops" have been used to make mushroom soup to ent ice anorex ics to eat (female elder, pers. comm., 2001). They are a lso eaten by moose (K. Char l ie , pers. comm., 2001) and bears (D. Char l ie , pers. comm., 2001). Caribou moss (lichen) - animal fodder, medicine, soup th ickener L ichen spec ies compris ing "caribou moss" are found in wet and dry coni ferous forests (such as Yukon ' s ubiquitous spruce stands), as well as peat lands. They are frut icose l ichens that form c lumped mats, often in late snow-melt regions (Andre and Fehr, 2001). S p e c i e s most commonly identified as reindeer l ichen inc lude Cladina mitis (yellow), and Cladina rangiferina (grey/green), though numerous other Cladonia and Cetraria have the character ist ic branchlets of car ibou moss (Vitt ef al., 1988). T h e s e l ichens contain polysacchar ides, proteins, and ac ids that may cause s tomach upsets if not cooked well (Kuhnlein and Turner, 1991). S o m e peop le are sensi t ive to usn ic ac id , which may result in red, itchy skin (Kershaw, 2000) . Part ial ly d igested l ichens from the car ibou rumen were mixed with a variety of other plants and eaten (Kuhnlein and Turner, 1991). Car ibou moss is regularly consumed by grouse, ptarmigan, gopher, car ibou, porcupine, and buffalo (M. Roberts and E. Billy, pers. comm., 2001). These l ichens are a lso eaten by bears , birds, mice, and dogs (female elder, pers. comm., 2001). The Tutchone name comes from the "gew" sound made when you walk on dry moss (M. Rober ts and E. Bil ly, pers. comm., 2001). T h e thal lus is boi led and the fluid drunk for medicinal purposes - any bad disease can be cured (female elder, pers. comm., 2001). Drinking either the tea or dr ied and powdered l ichen soaked in water can help treat intestinal worms (Mar ies ef al., 2000). T h e tea a lso rel ieves s tomach and chest pains, and is drunk to maintain energy, while l ichen itself can be eaten fried, after being boi led twice and strained, or dr ied and added to soup as a th ickener (Andre and Fehr, 2001). T e a made from grey re indeer l ichen (Cladina rangiferina as opposed to green reindeer l ichen, C. mitis) is taken for fevers, d iarrhea, jaundice, tuberculosis, and convuls ions (Kershaw, 2000). Cranberry - food, medic ine Vaccinium vitis-idaea ( lowbush cranberry) is a shrub that resembles Arctostaphylos uva-ursi (bearberry/stoneberry/kinnikinnick). They can be differentiated 61 by the smal l b lack spots located on the underside of the cranberry leaves (B. Brown, pers. comm., 2001), and by opening up a berry to s e e if has a s e e d and the character is t ic whit ish f lesh of a bearberry (Hargrave, 1997). Growing in bogs and other open ac id ic areas, the shrubs are usual ly only 5 - 2 0 cm tall (Cody, 2000) . Lowbush cranberry leaves and berries contain arbutin, a subs tance that prevents certain bacter ia from sticking to bladder and urinary tract wal ls such that an infection is c a u s e d (Kershaw, 2000; Mar ies et al., 2000). The berr ies a lso conta in benzo ic ac id therefore keep well in storage (Wil lard, 1992). Diarrhea can ar ise by consuming large amounts of berr ies (Kershaw, 2000). Ea ten raw, the berries are best p icked in autumn after the first frost. Cranberry jam is somet imes made: berries are added to flour and sugar and then boi led (K. Char l ie , pers. comm., 2001). Berr ies are boi led and the juice is saved (M. Rober ts and E. Bil ly, pers. comm., 2001). Cranberry juice is used for kidney problems, colds, st imulating the appetite, reducing heartburn, and as a dye (Wil lard, 1992; Andre and Fehr, 2001) . A c rushed or boi led cranberry mash can be used as a poult ice (e.g. for meas les rash), and the berr ies are eaten to improve nausea , sore throats, c ramps, childbirth pains, and convu ls ions (Kershaw, 2000; Viereck, 1987). Cranberry leaf tea is a genera l tonic (Viereck, 1987). Oi ly skin and hair can be treated using a r inse (Wi l lard, 1992). A tea made from boi led roots and stems is used for b ladder problems (Mar ies ef al., 2000). Crowberry - food, medic ine Empetrum nigrum (crowberry/mossberry/blackberry) grows in moist, mossy regions on the forest floor, in swamps, heathlands, and on tundra (Cody, 2000). The plants are general ly less than 15 cm (Andre and Fehr, 2001). T h e s e black berries are eaten raw, used for jam (W. At l in, pers. comm., 2001), or fr ied with g rease and p laced in a jar with bannock (K. Char l ie , pers. comm., 2001). Thei r f lavour is improved if berr ies are picked after the first frost and by adding other ingredients such as lemon and sugar (Wil lard, 1992). O n e can get const ipated if too many are eaten (M. Rober ts and E. Billy, pers. comm., 2001). Crowberry shoots are boi led and drunk to al leviate d iarrhea, co lds , kidney problems, and tuberculosis, while the roots or berries can be boi led and used to treat sore eyes (Viereck, 1987; Wi l lard, 1992). A tea from berries, s tems, and roots treats 62 s tomach-aches (Andre and Fehr, 2001). Shoots can be chewed or app l ied to sk in to treat fevers (Mar ies ef al., 2000). Labrador tea - medic ine Ledum groenlandicum (common Labrador tea, a lso known as L. palustre spp. groenlandicum) and L. palustre (northern/marsh Labrador tea, a l so known a s L. palustre spp. decumbens) are the two types of Labrador tea found in the Y u k o n . L. palustre is found in dwarf shrub and moss- l ichen heaths, and grows to 50 cm, whi le L. groenlandicum is common in peat lands, bogs, and meadow with a typical growth of 30-60 cm (Cody, 2000). Both spec ies have green leaves with fuzzy orange unders ides. Labrador tea contains toxins (ledol), and narcot ic compounds (Kershaw, 2000). L e a v e s contain tannins, f lavonoids, volati le oils, and smal l amounts of po isonous andromedotoxin (Maries et al., 2000). It is suggested that this spec ies is not dr ied in an enc losed space , as high concentrat ions of volati le oi ls may affect the heart (Hutchens, 1991). The re are a number of reactions that can occur from consuming large doses of this spec ies . They include headaches , vomiting, inc reased d rows iness and urination, c ramps, del ir ium, heart palpitations, temporary paralysis, and death (Kershaw, 2000; Mar ies et al., 2000). For this reason, Kuhnlein and Turner (1991) recommend that the plant be consumed infrequently, and in dilute tea form. There is confl ict ing information about whether or not to boil the shoots for long periods; a lka lo ids may be dest royed, but ledol is re leased (Kershaw, 2000). Labrador tea is drunk daily as a tonic, and has many more medic inal uses than ment ioned below. Shoots are boi led, stored in a jar in the fr idge, and drunk as a tea served hot or co ld (K. Char l ie , pers. comm., 2001). The liquid is good for heart attacks and the s tomach (V. Johnn ie and B .P . Johnnie, pers. comm., 2001) , chest pain, bad co lds, and for a face wash (to improve acne) (female elder, pers. comm., 2001) . Mar ies et al. (2000) mentions that leaves have been put on wounds, chewed to treat flu, d iarrhea, and bad breath, and powdered to treat burns. Despi te treating diarrhea, Labrador tea is a slight laxative (Viereck, 1987). A female elder (pers. comm., 2001) sa id it makes one relax when one is depressed , and ca l led it a "s leep ing pil l, though the f lowers are no good; just the leaves are used" . The tea can a l so treat a lcohol ism: shrubs are p icked, boi led for 1 hour, put in a jar, and drunk tea four to f ive t imes per day 63 - "no a lcohol from then on" (V. Johnnie and B .P . Johnn ie , pers. comm. , 2001). Labrador tea can wash out lice, treat insect bites, and repel insects (Wi l lard, 1992). Raspberry - food, medic ine Rubus arcticus ssp. acaulis (dwarf raspberry/nagoonberry) and Rubus idaeus (wild red raspberry/tal l raspberry) are common in the Y u k o n . T h e former is a low-growing shrub (< 15 cm) that is found in shaded wooded regions surrounding lakes (Andre and Fehr, 2001). R. idaeus is found in disturbed si tes such as a longs ide roads, and open wood land c lear ings - they are usual ly less than 1.5 m high (Cody, 2000). Raspber ry leaves contain fragarine, which acts to both relax and st imulate the uterus wal l musc les (Kershaw, 2000). L e a v e s a lso conta in tannins, f lavonoids and vitamin C (Mar ies et al., 2000). The berries are mildly laxative (Wi l lard, 1992). Berr ies are eaten raw, and used for making raspberry jams and jel l ies. F lowers can be added to sa lads, and peeled shoots are a lso consumed (Wil lard, 1992). Berr ies are good for nerves, while roots can be powdered to make into a tea for arthritis (I. Ca lmegane , pers. comm., 2001). Leaves and stalks are used for treating burns (K. Char l ie , pers. comm., 2001). Raspberry stems and roots are boi led and drunk to treat d iarrhea and fevers, gargled for sore throats, or used as an astr ingent /wash for wounds (Viereck, 1987; Mar ies et al., 2000). Raspber ry leaf tea is a lso given to pregnant women for nausea and menstruating women who have c ramps or high f lows (Wi l lard, 1992; Kershaw, 2000). Soapberry - food, medic ine, soap Shepherdia canadensis (soapberry/soopolal l ie) is a shrub with bright red berr ies dotted with gold. It usual ly grows 1-2 m in the south (60 cm further north), and is found in open dry spruce stands, a long rivers, and on alpine s lopes (Cody, 2000 ; Andre and Fehr, 2001). Ke rshaw (2000) mentions the berries are a source of vi tamin C and iron, a l though this is not indicated in nutrient tables l isted in either Kuhn le in and Turner (1991) or Med ica l Serv ices Branch (1994). The berr ies a lso conta in sapon in ; consuming too many berries can cause diarrhea, vomit ing, and c ramps as this detergent- l ike subs tance irritates the s tomach (Kershaw, 2000; Mar ies et al., 2000). 64 The i r bitter f lavour is improved if berr ies are p icked after the first frost (Wil lard, 1992) and by adding other ingredients. W h e n combined with sugar and water and wh ipped, a frothy " ice cream" dessert is created. W . Atl in (pers. comm., 2001) ment ions a typical ratio might be a "heaping tablespoon of berr ies, 4 tab lespoons of water, and 1 tab lespoon of sugar", and warns that the "mixture will not r ise if there is any butter or oil on the beater or bowl". In Tlingit culture, soapberr ies were the most ce lebra ted type of berr ies produced at a feast, and the whipped dessert was served last (Thornton, 1999). Soapber r ies are most popular eaten as ice cream (K. Char l ie , pers. comm., 2001 ; female elder, pers. comm., 2001). They are a lso eaten with bannock (female elder, pers. comm., 2001), and by mixing with grease and sa lmon eggs (V. Johnn ie and B P . Johnn ie , pers. comm., 2001 ; female elder, pers. comm., 2001). Bo i led juice is good for ulcers (M. Roberts and E. Billy, pers. comm. , 2001 ; K. Char l ie , pers. comm., 2001 ; female elder, pers. comm., 2001) , for wash ing out the s tomach (M. Rober ts and E. Billy, pers. comm., 2001), and for const ipat ion (Kershaw, 2000). A mixture of soapberry juice, sugar and water is used for acne , boi ls, digest ion problems, and gal ls tones (Turner, 1997). S tems are boi led and drunk for a laxative (Kershaw, 2000). The tea a lso can help prevent miscarr iages, treat tuberculos is and venerea l d i sease , or be used as a wash for cuts and swel l ings (Mar ies et al., 2000). Bark tea a ids problems with eyes (Kershaw, 2000). A tea made from s tems and roots is sa id to rel ieve s tomach pains and diarrhea, whi le raw berr ies or berry tea is recommended for co lds or sore throats (Andre and Fehr, 2001). Berr ies c a n improve flu and indigest ion condit ions; crushed or boi led, the raw berr ies can a lso be used as soap (Kershaw, 2000). The berries were mentioned as a good medic ine; a d iabet ic woman ate them and her blood sugar was level for a week (W. Atl in, pers. comm. , 2001). Willow - medic ine, tools, animal fodder, and fuel Salix spec ies are common in Yukon 's wet muskeg a reas , on f loodpla ins and a longs ide creeks, and in wel l-drained open birch, aspen , and spruce s tands (Cody, 2000). They range from prostrate growth to up to 7 m tall (Andre and Fehr , 2001). There are 34 known spec ies of Salix in the Yukon ; the most abundant of wh ich include S. arbusculoides, S. arctica (dwarf willow), S. glauca (b lue-green wil low), S. myrtillifolia, S. planifolia, and S. reticulata (net-veined willow) (Cody, 2000). 65 Wi l low bark contains f lavonoids, tannins, a ldehydes, and sa l icy la tes such as sal ic in (Mar ies ef al., 2000). S o m e parts of wil low have high asco rb i c ac id content (Kuhnle in and Turner, 1991). Y o u n g shoots of this shrub are food for moose, car ibou, a n d s o m e horses (female elder, pers. comm., 2001). Grouse , ptarmigan and moose eat the soft parts of wi l low (M. Rober ts and E. Billy, pers. comm., 2001), whi le bears eat pussy wi l lows and beavers eat the bark (W. Atl in, pers. comm., 2001). M o o s e eat twigs in wintertime (K. Char l ie , pers. comm., 2001). Wi l l ow branches and roots provide shelter, fuel, and multiple tools. Wi l l ow is used for making baskets, dream catchers, picture f rames, c rad les for babies, and f rames for bab ies ' faces so they are not smothered while s leep ing ; the f rames are a lso p laced over the mouth to avoid mosqui toes or germs (female elder, pers. comm. , 2001). Other wi l low uses include snowshoes, smokehouses , sweat lodge f rames, canoes , nets, rope, and mats (Maries ef al., 2000; Andre and Fehr, 2001). W i l l ow is used for medicinal purposes (I. Ca lmegane , pers. comm. , 2001) and is co l lected in spr ing and fall (female elder, pers. comm., 2001). U s e d as a substitute for aspir in, wi l low is a pain remedy for headaches (female elder, pers. comm., 2001 ; I. C a l m e g a n e , pers. comm., 2001), and is a lso good for os teoporos is , a n d arthritis (female elder, pers. comm., 2001). The bark is pee led off, boi led, and the l iquid drunk, though the stem can a lso be cut off and sucked (female elder, pers. comm., 2001) . Wi l low can help bee st ings: leaves are chewed, bal led up and p laced on stung a rea (V. Johnn ie and B .P . Johnn ie , pers. comm., 2001). Wi l l ow leaf tea can be used as a wash for skin infections and wi l low bark tea is drunk to rel ieve diarrhea, digest ion, rheumatism, and urinary tract infections (Kershaw, 2000). C rushed leaves or pee led roots can treat rashes, cuts, u lcers, and toothaches (Mar ies ef al., 2000 ; And re and Fehr, 2001). Ke rshaw (2000) ment ions these condi t ions (along with ulcers, corns, and cancers) that are improved us ing bark tea or bark strips. A poult ice of powdered bark in cream can be appl ied externally to treat gangrene (Hutchens, 1991). T e a made from the root he lps treat internal b leed ing, throat constr ict ion, and venereal d i sease (Wil lard, 1992). 66 5.4.2 Preparat ion of Plant Medic ine First Nat ion people (usually older women) fol low speci f ic s teps for harvest ing med ic ines that have been passed down through generat ions. T h e s teps have spiritual connect ions, as shown below in the list of suggest ions ment ioned by Ida C a l m e g a n e (pers. comm., 2001). • It is important to a lways give a gift - my grandma sa id it doesn' t matter what, as long as it is important to you. Beads and silk and tobacco are examples . T o b a c c o is mostly still used . • S a y prayers before you ever pick medic ines. If you're picking medic ine for someone e lse , you say who you are picking medic ine for, and ask the spirits to help you and ask b less ings. • A lways pick from plenty - never pick from any p lace that doesn' t have many. Leave some behind. • Have a little on hand. Never stockpi le it. It's good to pick it f resh. • Most of plants can be picked just about anytime. Plants growing on the ground - I l ike to get in summer months. Pick ing usual ly based on someone need ing it. • Fo r women, it's really important that you're not on moon time [menstruation] when picking medic ines, as women have ability to give life and at that time, you're very strong. Med ic ines picked at that time goes into you and are not patient. [This is] taboo to do in our culture. [This isn't an issue when you] become an e lder and no longer have moon times. C lear ly harvest ing dates for berries and other seasona l plant parts co inc ide with the time of year when the plant is ripe and at its peak. Th is differs accord ing to shifts in seasona l cl imate and micro-site condit ions, but the fol lowing t imeframe suits the southern Y u k o n : currents and strawberries appear in early summer (late June) , b lueberr ies, raspberr ies, and Saska toon berries are usual ly p icked mid to late summer, and cranberr ies, mossberr ies, and rose hips tend to be harvested after the first frost in Sep tember (Hargrave, 1997). Carefu l s teps are a lso fol lowed when preparing medic ine. Th is is revea led in the fol lowing descr ipt ion by I. Ca lmegane (pers. comm., 2001) for prepar ing tea from the bark of a medic inal tree spec ies such as red alder, ba lsam fir, or J a c k P ine . 67 Pick bark from the north s ide of the plant because the sun is too hot on the morning s ide (east). Take a sharp knife and peel 2-3 s l i ces off tree (18" x 2" wide) - then you know you don't kill the tree and that it is there for you to use aga in some other time. Put them in an enamel or Pyrex pot. Put a gal lon and a half of water in. O n c e it comes to full boil, turn the heat down and boil gently for 25-35 min (no longer). Strain as soon as it coo ls off. T a k e all of the water out and store it co ld. [The medicine is ready to be drunk. If the receiver of the medic ine is still s ick after one week], next week, put 1 branch [slice] in. Lay under bush when [the medicine is no longer needed] and say prayers. Or use a good burning barrel. Never put it in garbage and destroy it like that. W . Atl in had this adv ice for knowing when to take and when to stop taking medic ine: take a teaspoon first to see if [the medicine] agrees with you . If you take it against your wil l , it's not going to help you. . . your body c raves it and when it doesn' t c rave it anymore, that's when it's enough. S h e a lso pointed out the importance of p ick ing and prepar ing medic ine wel l : if you don't treat medic ine right, it g o e s away and doesn' t grow there anymore. . . medic ines have to be nice and c lean - no dirt... use the s a m e pot (W. At l in, pers. comm., 2001). Fami ly members and local Elders taught many of those interviewed about medic ines at an early age. Some continue to prepare only the med ic ines p a s s e d down to them; whi le others communicate with knowledgeable people in other communi t ies to exchange ideas, and occasional ly consult publ ished literature. 5.5 To lerab le Dai ly Intake Calculat ions To lerab le dai ly intake (TDI) va lues were calculated from inorganic a rsen ic data taken from each of the three locations at the V e n u s and Mt. N a n s e n mining propert ies, for all spec ies with detectable arsenic (Appendix 5). G i ven the var iance in the data, TDI 's have been provided for the mean concentrat ion found at a part icular locat ion, and for the samp les with the highest and lowest concentrat ions. TDI 's are separa ted by age group us ing Heal th C a n a d a age and body weight s tandards, and are reported in grams/day in terms of wet weight (as berries would be p icked and eaten raw) as wel l as dry weight (useful for comparat ive purposes a s moisture content is no longer a factor). T h e s e are sugges ted va lues only, based on the s ize of the sample populat ion col lected at e a c h location (n=3 to 9). 68 S i n c e consumpt ion patterns change annual ly b a s e d on the product ion s u c c e s s of e a c h s e a s o n , residents can individually determine how much they are consuming of a part icular food, and dec ide berry and mushroom picking locat ions accordingly. 5.5.1 Mt. N a n s e n Mine Site The high variabil ity in concentrat ions of mushrooms (and consequent T D l calculat ions) suggests residents pick from the Mt. N a n s e n region with caut ion. There was no apparent spatial pattern with this spec ies , but samp les apparent ly had less a rsen ic when col lected from areas where the ground was not d isturbed. R isk to foragers is likely low as Bolete mushrooms are not the primary food source for any wildlife spec ies . The health risk from Labrador tea is difficult to determine s ince the shoots are boi led for tea, rather than directly ingested. The T D l grams/day va lues are conservat ive est imates as they are based on the assumpt ion that the entire shoot is consumed . It is unknown how much arsen ic is re leased from the plant during boi l ing. T h e TDI 's for wil low leaves are a lso conservat ive est imates, g iven that the leaves are chewed but not ingested when used medicinal ly. M o o s e and other wildlife consume wi l low shoots but insufficient information is avai lable about the foraging habits of these an imals in order to a s s e s s the health risk of consuming wil low s tems by foragers at Mt. N a n s e n . L ikewise, insufficient information was avai lable in order to ca lcu la te a r isk-based assessmen t of the l ichen-car ibou-human food chain. Th is may be a low priority s ince car ibou tend to stay in val leys west of Mt. Nansen and likely do not ingest any apprec iab le amount of arsenic-r ich l ichen. The concentrat ion of arsen ic in berries fell wel l be low any n e e d to calculate a T D l . Cranberr ies , mossberr ies, and blueberr ies should be cons idered safe to eat by C a r m a c k s residents, according to the results from all a reas samp led in 2001 . 5.5.2 V e n u s Mine Site T h e TDI 's for raspberr ies at the V e n u s Mine tai l ings site (V1) a re encourag ing, g iven the history of high arsenic contamination here. Adul ts can safe ly consume 811.6 69 g/d, whi le young babies can safely eat 81.2 g/d (Appendix 5). S i n c e a rsen ic is still detectable in raspberr ies, it is suggested that residents cons ider p ick ing berr ies here, but to use the TDI 's with the knowledge that the mean is based on only four samp les co l lected around the capped tail ings. 5.5.3 Arc t ic G o l d and Si lver M ine Site TDI 's cou ld not be calculated for soapberr ies at the Arct ic G o l d and Si lver property s ince they had undetectable arsenic. Chapter 6: Recommendations B a s e d on the results of this study, severa l s i te-speci f ic recommendat ions can be made (beyond those suggested earl ier with regards to the cho ice of gathering locat ions). 6.1.1 Mt. N a n s e n Mine Site The first recommendat ion is to monitor water at Pony C reek downst ream of waste rock as "exist ing ore dump from previous mining of the su lph ide ore from the B rown -McDade zone which is located in the Pony Creek dra inage. . . is currently a source of contaminat ion to Pony Creek" (T.W. Higgs Assoc ia tes , 1995, p. 51). Th is ore dump w a s to have been either re-processed or t ransported to the tai l ings pond by B . Y . G . R e s o u r c e s Inc, prior to their mine reclamation. Accord ing to T . W . Higgs A s s o c i a t e s (1995), this should be a priority activity. Thoroughly r insing shrubs that are used medicinal ly prior to use is a lso recommended , a s windborne dust is suspected to have been the r eason for samp les with the highest a rsen ic concentrat ions in wil low and Labrador tea. However , residents will not l ikely gather from the Mt. Nansen property itself until mine reclamat ion has been completed, and certainly berries and shrubs col lected in this study are ava i lab le in other areas . A dust monitoring program examining arsen ic in wet and dry particulate deposi t ion would be useful for determining the source of this element. 70 If pond water is low and the tail ings exposed, it may be prudent to erect a temporary fence around the perimeter for col lect ing windborne tai l ings, and to prevent foragers from wading through or drinking the water. Th is is l ikely not poss ib le around^ other structures (e.g. B rown-McDade open pit), though a reclamat ion program should re -seed bare ground to prevent erosion. T h e suggest ion to construct a fence around the pond and to p lace a net over it to d iscourage waterfowl was given to DIAND in 2000, which responded with the fol lowing comments: I think there are measures which are more pract ical, effective and less costly. To build a fence, the posts would have to be p laced in permafrost or unconsol idated material and would not remain upright. A n electr ic fence on surface tr ipods would be ineffective in keeping large mammals out of the tai l ings a rea and would pose a risk to the DIAND-contracted work force. G i ven the substant ial ly reduced cyanide levels now in the tai l ings pond, there is little danger to wildlife. With the onset of winter, the pond and saturated tai l ings are f rozen, so there is almost no possibil i ty of mammals being t rapped in soft material. T h e waterfowl is gone for the year. Even during the summer there are people moving around the site constantly, so large mammals do not frequent the site. D IAND's approach of reducing the cyan ide concentrat ions in the pond and the water levels as much as poss ib le is the best and most cost effective solut ion to the concerns of contamination of the tai l ings pond water (P .H . Beaubier , pers. comm., 2000). B a s e d on the higher arsenic concentrat ions in car ibou moss, C a r m a c k s residents may cons ider monitoring the movement of car ibou in the region, part icularly around the tai l ings pond, and study their arsenic concentrat ions if necessary . T h e last recommendat ion for this property is to maintain sampl ing of vegetat ion so as to monitor temporal trends. Spec ies that were col lected but not ana lysed in the 2001 study include red moss (Sphagnum spp.), puffball mushrooms (Lycoperdon spp.), c loudberry (Rubus chamaemorus), red bearberry (Arctostaphylos rubra), car ibou horn (Cornicularia aculeata), and grey car ibou moss (Cladina rangiferina). Most are not full col lect ions (between 1 and 25 samples) , but they remain in f rozen storage at U B C and are ava i lab le for analys is should the need ar ise, and shou ld funds become avai lable. 6.1.2 V e n u s Mine Site B a s e d on the arsenic found in the sole plant spec ies (raspberr ies) ana lysed at this site, high soi l concentrat ions do not appear to be a concern . Loca l residents can 71 cons ider picking berries here once again. However, it is sugges ted that raspberr ies and other plants are periodical ly sampled to ensure that a rsen ic concentrat ions remain low. Wi l low, soapberr ies , gooseberr ies, and black currents were a lso co l lec ted from the s a m e locat ions during the 2001 field season and are in storage at U B C shou ld further ana lys is be required. 6.1.3 Arct ic Go ld and Si lver Mine Site Undetectable arsen ic concentrat ions in soapberr ies co l lected dur ing the 2001 f ield s e a s o n indicate that these berries are safe to eat, and residents can return to this berry-picking site. No conc lus ions could be made about other spec ies at this mining property, al though a full col lect ion of mossberr ies, Labrador tea, and wi l low leaves and s tems were a lso sampled during 2001 and are avai lable for ana lys is if requested. Chapter 7: Limitations Severa l procedural details may explain the p resence of unusual data. In order to mimic consumpt ion habits by wildlife and humans, the forage plants of wi l low twigs and car ibou moss were deliberately not r insed with water during sample preparat ion, unl ike the medicinal spec ies of Labrador tea and wi l low leaves. It is noted that the car ibou moss may have contained dust part icles or smal l amounts of debr is not removed during the c leaning process. Insufficient r insing of mushroom stalks may have a l lowed soi l part ic les to remain. A s wil low leaves and twigs were prepared differently, the ability to directly compare wil low parts is affected. . Organ ic a rsen ic concentrat ions in some samples (mostly soi ls) in this study were unusual ly high, even exceed ing the inorganic concentrat ion in certain c a s e s . Organ ic a rsen ic is not common, except in mushrooms, some plants, f ish, a lgae, shel l f ish, and worms (W. Cu l len , pers. comm., 2002). The most p lausib le explanat ion is the laboratory technique of subtracting HCI extractable (inorganic) results from the total concentrat ion to determine organic concentrat ion (L. C h a n , pers. comm. , 2002; W . Cu l len , pers. comm., 2002). W h e n inorganic arsen ic is bound in a compl icated soi l matrix (e.g. to organic l igands), it is not easi ly extracted; consequent ly the value reported as inorganic arsen ic will be lower than the true concentrat ion, and the organic 72 concentrat ion will be falsely elevated (L. C h a n , pers. comm., 2002) . Another source was crit ical of this technique, stating that "crude separat ions into so -ca l led 'organic ' and > ' inorganic ' fractions have been based on methods that have been shown to be app l icab le to some food, such as f ish, but the value of those separat ions when appl ied to other foods, such as meat and grain, is moot" (National R e s e a r c h Counc i l , 1999, 67). Laboratory procedures did not include s ieving soil samp les prior to ana lys is . Due to a potential inclusion of humus material, organic matter content was determined in soil samp les with detectable organic arsenic using the LOI method. Unfortunately, there was little correlat ion, suggest ing that the inorganic arsen ic was bound to compounds other than organic matter (such as the iron and aluminum ox ides descr ibed earl ier). Chapter 8: Conclusions Arsen i c is a common element found in var ious environmental media , and is particularly prevalent in certain areas of the Yukon containing arsenic- r ich bedrock. Low arsen ic concentrat ions were found in vegetat ion col lected around the Mt. Nansen , V e n u s , and Arct ic Go ld and Si lver mining properties, and the 2001 data were typical of other Y u k o n data for the same spec ies . Higher concentrat ions were found in select samp les of car ibou moss, willow, and Labrador tea co l lected from Mt. Nansen . Windborne dust from historic and recent mining activity may be a c a u s e , but natural uptake of soi l a rsen ic is a lso likely. Most spec ies revealed decreas ing concentrat ions at locat ions further away from probable point sources of contaminat ion. T h e majority of this detectable arsen ic was inorganic. At si tes where data were ava i lab le in previous years , temporal trends indicate either a decrease in a rsen ic (after the V e n u s tai l ings were capped) or a continuation of non-detectable results (Mt. Nansen) . Berr ies had consistent ly low or undetectable arsenic concentrat ions at all three mine si tes. To lerab le Dai ly Intake data are provided for local residents to make informed cho ices about where to pick popular plant foods and medic ines. More information is required about the uptake of arsenic from vegetat ion not directly c o n s u m e d by humans, such as food eaten by animals, or medicinal spec ies . 73 References A g e n c y for Tox ic Subs tances and D isease Registry ( A T S D R ) . 1993. Toxicological profile for arsenic (update). TP-92 /02 . At lanta, Georg ia : A T S D R . Andre , A . , and A . Fehr. 2001 . Gwich'in ethnobotany: plants used by the Gwich'in for food, medicine, shelter and tools. Inuvik, Northwest Terri tories: Gwich ' in Soc ia l and Cul tural Institute and Aurora Resea rch Institute. Arct ic Monitor ing and Assessmen t Programme. 1997. Arctic pollution issues: a state of the arctic environment report. Os lo : Arct ic Monitor ing and A s s e s s m e n t Programme. Ash ley , P . M . , and B . G . Lottermoser. 1999. A rsen ic contaminat ion at the Mo le River mine, northern New South W a l e s . Australian Journal of Earth Sciences, 46: 8 6 1 -874. A tmospher ic Environment Serv ice. 1982. Canadian climate normals: temperature and precipitation, 1951-1980. Vol. 2: The North - Yukon and Northwest Territories. Ottawa: Environment C a n a d a . A tmospher ic Environment Serv ice. 1993. Canadian climate normals, 1961-1990. Vol. 3: Yukon and Northwest Territories. Downsview, Ontario: Envi ronment C a n a d a . Ba rcan , V . S . , E .F . Kovnatsky, and M.S. Smetannikova. 1998. Absorp t ion of heavy metals in wild berr ies and edible mushrooms in an a rea affected by smelter emiss ions . Water, Air, and Soil Pollution, 103: 175-195. B e c h , J . , C . Poschenr ieder , M. Llugany, J . Barce lo , P. Tume, F . J . Tob ias , J .L . Bar ranzue la , and E.R. V a s q u e z . 1997. A rsen ic and heavy metal contaminat ion of soi l and vegetat ion around a copper mine in Northern Peru . Science of the Total Environment, 203: 83-91. B e n s o n , A .A . , R.V. Cooney , and J . M . Herrera-Lasso. 1981. A r s e n i c metabol ism in a lgae and higher plants. Journal of Plant Nutrition, 3: 285-292 . Berti, P .R. , O. Receveur , H.M. C h a n , and H.V. Kuhnle in. 1998. Dietary exposure to chemica l contaminants from traditional food among adult Dene /Met i s in the western Northwest Territories, C a n a d a . Environmental Research Section A, 76: 131-142. Bertolero, F., G . P o z z i , E. Sabbion i , and E. Saffiotti. 1987. Ce l lu la r uptake and metabol ic reduction of pentavalent to trivalent arsen ic as determinants of cytotoxicity and morphological transformation. Carcinogenesis, 8: 803-808. Bhumbla , D.K., and R.F . Keefer. 1994. A rsen ic mobil izat ion and bioavai labi l i ty in soi ls. In Arsenic and the Environment. Parti. Cycling and Characterization. J . O . Nr iagu (ed.). N e w York: Wi ley, pp. 51-82. 74 Bowman, B., and D. Baker. 1998. Mine reclamation planning in the Canadian north. Yel lowkni fe: Canad ian Arct ic Resou rces Committee, Northern Minera ls Program Work ing Pape r No. 1. Brodie, M .J . 1998. Report on: Mt. Nansen mine closure cost assessment. W e s t Vancouver : Brodie Consul t ing Ltd. Bur lo, F.<, I. Guijarro, A .A . Carbonel l -Barrach ina, D. Va lero , and F .Mar t i nez -Sanchez . 1999. A rsen i c spec ies : effects on and accumulat ion by tomato plants. Journal of Agricultural and Food Chemistry, 47: 1247-1253. C a n a d i a n Counc i l of Ministers of the Environment ( C C M E ) . 1995. Canadian soil quality guidelines for contaminated sites. Human health effects: inorganic arsenic. Final report. Ottawa: National Contaminated Si tes Remedia t ion Program, Environment C a n a d a . C a n a d i a n Counc i l of Ministers of the Environment ( C C M E ) . 2001 . Canadian soil quality guidelines for the protection of environmental and human health: arsenic (inorganic) (1997). Updated in Canadian environmental quality guidelines, 1999. W inn ipeg : C a n a d i a n Counc i l of Ministers of the Environment. Carbone l l , A .A . , M.A. Aarab i , R.D. DeLaune, R .P . Gambre l l , and W . H . Patr ick Jr. 1998. A rsen i c in wet land vegetat ion: availability, phytotoxicity, uptake and effects on plant growth and nutrition. Science of the Total Environment, 217: 189-199. C lewel l , H.J . , P .R. Gentry, H.A. Barton, A . M . Shipp, J . W . Yager , and M.E . Anderson . 1999. Requi rements for a biological ly realistic cancer risk assessmen t for inorganic arsenic . International Journal of Toxicology, 18: 131 -147. Cody , W . J . 2000. Flora of the Yukon Territory. Second Edition. Ottawa: Nat ional R e s e a r c h Counc i l P ress . Conover , W . J . , and R.L. Iman. 1981. Rank transformations a s a br idge between parametr ic and nonparametr ic statistics. American Statistician, 35: 124-129. Counc i l of Y u k o n First Nat ions. 2000. Traditional knowledge research guidelines: a guide for researchers in the Yukon. Whi tehorse: Counc i l of Y u k o n First Nat ions. Cu l len , W . R . , and K .J . Reimer. 1989. A rsen ic speciat ion in the environment. Chemical Reviews, 89: 713-764. Davey, E. 1999. A rsen ic levels in berries and soi ls from the Ye l lowkn ives Dene First Nat ion Tradit ional Territory. In Synopsis of Research Conducted under the 1998/99 Northern Contaminants Program. S. Kalhok (ed.). Ottawa: Department of Indian Affairs and Northern Development, pp. 81-85. Dav idge, D. 1984. Oxidation of Yukon mine tailings. Envi ronment C a n a d a , Envi ronmental Protect ion Serv ice, Regional Program Report 84-15. 75 Dene Nat ion. 1998. Arsenic levels in berries and soils from the Weledeh Yellowknives Dene First Nation traditional territory. Yel lowkni fe: D e n e Nat ion Lands and Environment Department. Department of Renewab le Resources . 1996. Contaminated sites regulations. Whi tehorse : Department of Renewab le Resources , Government of Y u k o n . Department of Renewab le Resources . 2000. Yukon state of the environment report, 1999. Whi tehorse: Department of Renewab le Resou rces , Government of Yukon . D IAND Techn ica l Serv ices . 1993a. Abandoned mines assessment report 105D-02-1: Venus. Whi tehorse: Department of Indian Affairs and Northern Development . D IAND Techn ica l Serv ices . 1993b. Abandoned mines assessment report 105D-02-2: Big Thing. Whi tehorse: Department of Indian Affairs and Northern Development . Dunn, C E . 1995. A field guide to b iogeochemical prospect ing. In Biological systems in mineral exploration and processing. Brooks, R.R. , C E . Dunn, and G . E . M . Hal l (eds.). New York: El l is Horwood Limited, pp. 345-369. Dushenko , W.T . , D.A. Bright, and K .J . Reimer. 1995. A rsen i c b ioaccumulat ion and toxicity in aquat ic macrophytes exposed to gold-mine effluent: re lat ionships with environmental partitioning, metal uptake and nutrients. Aquatic Botany, 50: 141-158. Dushenko , W.T . , S .L . Grundy, and K .J . Reimer. 1996. V a s c u l a r plants as sensi t ive indicators of lead and P C B transport from local sources in the C a n a d i a n Arct ic. Science of the Total Environment, 188: 29-38. E B A Engineer ing Consul tants Ltd. 2001. Research of low permeability cover performance at the Arctic Gold and Silver Mine site, Carcross, Yukon. Whi tehorse: Min ing Environment Resea rch Group, report 2001-1 . Envi ronmental S c i e n c e s Group: Roya l Roads Military Co l lege , V ic tor ia . 1995. An environmental study of the Aishihik Airstrip, Yukon Territory. Wh i tehorse : Indian and Northern Affairs C a n a d a . Envi ronmenta l Serv ices . 1997. Phase II Environmental assessment of the Venus abandoned mine site. Edmonton: Publ ic Works and Government Se rv i ces C a n a d a . Envi ronmental Serv ices . 1998. Phase III environmental assessment of the Arctic Gold and Silver mill and tailings impoundment. Edmonton: Pub l i c W o r k s and Government Serv ices C a n a d a . Envi ronmental Serv ices . 1999. Phase III environmental assessment: Venus abandoned mine site final report. Edmonton: Pub l ic W o r k s and Government Se rv i ces C a n a d a . 76 Federa l -Prov inc ia l Subcommit tee on Drinking Wate r ( F P S D W ) . 1996. Gu ide l ines for C a n a d i a n drinking water quality. Ottawa: Minister of Supp ly and Se rv i ces C a n a d a . Fe rgusson , J . E . 1990. The heavy elements: chemistry, environmental impact and health effects. Oxford: Pergamon Press . F lork iewicz, R., L.L. A l len , and M. Gamberg . 1995. Contaminants in plants used as traditional food and medicine by Kaska First Nations in the Yukon. P resen ted at a workshop hosted by tl ie Yukon Contaminants Commit tee on January 30, 1994, rev ised Augus t 3, 1995. Whi tehorse: Department of Renewab le Resou rces , Government of Yukon . F rance , R.L. and J . M . Bla is . 1998. Lead concentrat ions and stable isotopic ev idence for t ranspolar contamination of plants in the Canad ian High Arct ic. Ambio, 27(7): 506-508. Gamberg , M. 2000. Contaminants in Yukon country foods. Wh i tehorse : Department of Indian Affairs and Northern Development, Northern Contaminants Program. Geog raph i c Data. 1975. A24.214: 33 [1:4000]. Government of Y u k o n Department of Infrastructure, Transportat ion Branch, Whi tehorse, Y T . Geog raph i c Data. 1990a. A27668 : 150 [1:20,000]. Government of Y u k o n Department of Infrastructure, Transportat ion Branch, Whi tehorse, Y T . Geog raph i c Data. 1990b. A27666 : 82 [1:20 000]: Government of Y u k o n Department of Infrastructure, Transportat ion Branch, Whi tehorse, Y T . Geog raph i c Data. 1995. A24240 : 138 [1:20,000] September 18. Indian and Northern Affairs C a n a d a Departmental Library (Yukon Region) , Whi tehorse , Y T . God in , B., a n d T . R . Osier . 1985. A survey and comparison of arsenic concentrations in water, soils, and vegetation between the Venus Mine property and the Mount Nansen property, Yukon. Environment C a n a d a , Environment Protect ion Serv ice . Gri l l , E., E.L. Winnacker , and M.H. Zenk. 1987. Phytochelat ins, a c l ass of heavy-metal b inding pept ides from plants, are functionally ana logous to metal lothioneins. Proceedings of the National Academy of Sciences of the United States of America, 84: 439-443 . Hargrave, A . 1997. S o , do you know where there's any good berry patches. In Great northern lost moose catalogue. Whi tehorse: Lost M o o s e Pub l ish ing, pp. 64-65. Hart, C . J . R., and J . K. Radloff. 1990. Geo logy of Whi tehorse, Al l igator Lake , Fenwick Creek , Carc ross , and part of Rob inson Map A r e a s (105D/11, 6, 3, 2 & 7). (1:50,000). Explorat ion and Geo log ica l Serv ices Div is ion, Y u k o n , Indian and Northern Affairs C a n a d a , Open Fi le 1990-4. In Yukon digital geology. S . P . Gordey and A . J . M a k e p e a c e (eds.). Geo log ica l Survey of C a n a d a O p e n F i le D3826 and 77 Explorat ion and Geo log ica l Serv ices Div is ion, Yukon , Indian and Northern Affairs C a n a d a , O p e n F i le 1999-1 (D). Heal th C a n a d a . 1996. Health-based tolerable daily intakes/concentrations and tumorigenic doses/concentrations for priority substances. Ottawa: Envi ronmental Heal th Directorate, Health Protection Branch, Health C a n a d a . Hol land, B., A . A . W e l c h , I.D. Unwin, D.H. Buss , A . A . Pau l , and D.A.T. Southgate. 1991. McCance and Widdowson's The composition of foods. 5th edit ion. Cambr idge : Roya l Soc ie ty of Chemistry and Ministry of Agriculture, F isher ies and F o o d . Hughes , K., M .E . Meek, and R. Burnett. 1994. Inorganic arsenic : evaluat ion of r isks to health from environmental exposure in C a n a d a . Environmental Carcinogenesis and Ecotoxicology Reviews (Journal of Environmental Science and Health) C12(2) : 145-159. Hureau, S .A . 1999. 1998 Annual report. Water license QZ94-004: Mount Nansen mine. Submit ted to the Yukon Territory Wate r Board . Wh i tehorse : B . Y . G . Natural R e s o u r c e s Inc. Hutchens, A . R . 1991. Indian herbalogy of North America. Bos ton : Shambha la Publ icat ions, Inc. J . G . Moore & Assoc ia tes , Ltd. 1998. Public interest hearing on water licence QZ9-004 B.Y.G. Natural Resources. Vol.1. Held on March 11, 1998. Wh i tehorse : Y u k o n Territory Wate r Board. Jack , M .E . 1981. Baseline study of the watershed near Venus Mine, Yukon and Venus Mill, British Columbia. Environment C a n a d a , Environmental Protect ion Serv ice , Reg iona l Program Report 81-18. J a c k s o n , L .E . 2000. Quaternary geology of the Carmacks map area, Yukon Territory. Ottawa: Geo log ica l Survey of C a n a d a . J e n s o n , J . , K. Adare , and R. Shearer (eds.). 1997. Canadian Arctic contaminants assessment report. Ottawa: Department of Indian Affairs and Northern Development , Northern Contaminants Program. Johns tone , J . F . 1995. Responses of Cassiope tetraaona. a high arctic evergreen dwarf shrub, to variations in growing season temperature and growing season length at Alexandra Fiord, Ellesmere Island. M.Sc . thesis. Vancouver : Universi ty of Brit ish Co lumbia . Kaba ta -Pend ias , A. and H. Pend ias . 2001. Trace elements in soils and plants. 3 r d edit ion. B o c a Raton, Flor ida: C R C Press . Kershaw, L. 2000. Edible and medicinal plants of the Rockies. Edmonton: Lone P ine Publ ish ing. 78 K lohn-Cr ippen . 1995. B.Y.G. Natural Resources Inc. Mt. Nansen gold project: Tailings impoundment final design report. Calgary : K lohn-Cr ippen Consu l tants Ltd. K o c h , I. 1998. Arsenic and antimony species in the terrestrial environment. Ph .D . thesis, Vancouver : University of British Co lumbia . Koch , I., L. W a n g , C A . Ol lson, W . R . Cu l len , and K . J . Reimer . 2000. The predominance of inorganic arsenic spec ies in plants from Yel lowkni fe , Northwest Terr i tor ies, C a n a d a . Environmental Science and Technology, 34: 22-26 . Kova levsky , A . L . 1969. B iogeochemica l parameters and some spec ia l s tudies on them (in Russ ian ) . Trud. Buriat. Inst. Yestven. Nauk #2. 6-28. C i ted in: Kova levsky , A . L . 1995. The b iogeochemica l parameters of mineral prospect ing. In Biological systems in«mineral exploration and processing. Brooks, R.R. , C E . Dunn, and G . E . M . Hal l (eds.). N e w York: El l is Horwood Limited, pp. 267 -281 . Kova levsky , A . L . 1995a. The b iogeochemical parameters of mineral prospect ing. In Biological systems in mineral exploration and processing. Brooks , R .R . , C E . Dunn, and G . E . M . Hal l (eds.). New York: El l is Horwood Limited, pp. 267 -281 . Kova levsky , A . L . 1995b. Barrier-free b iogeochemica l prospect ing. In Biological systems in mineral exploration and processing. Brooks, R.R. , C E . Dunn, and G . E . M . Hal l (eds.). New York: El l is Horwood Limited, pp. 283-299. Kuhnle in , H.V., and N.J . Turner. 1991. Traditional plant foods of Canadian indigenous peoples: nutrition, botany, and use. Phi ladelphia: Go rdon and B reach Sc ience Pub l ishers . Lederer , W . H . , and R . J . Fensterheim (eds.). 1983. Arsenic: industrial, biomedical, environmental perspectives. New York: V a n Nostrand Re inho ld Pub l ish ing. Lincoff, G . H. 1981. National Audubon Society: field guide to North American mushrooms. New York: Al fred A. Knopf. Little Sa lmon Ca rmacks First Nation ( L S C F N ) . 1998. Little Sa lmon C a r m a c k s First Nat ion comments for Yukon Water Board hearing March 1 1 , 1 9 9 8 . In Public interest hearing re: licence QZ94-004. Sections 7 and 8. Whi tehorse : Y u k o n Territory Wa te r Board . Little Sa lmon Ca rmacks First Nation ( L S C F N ) . 1999. Dan Yoonji K'ok: A noun dictionary of Northern Tutchone, Carmacks Dialects. Ca rmacks , Y u k o n Territory: Little Sa lmon Carmacks First Nation. M a , L.Q., K .M . Komar, C. Tu , W . Zhang , Y . C a i , and E.D. Kennel ley . 2001 . A fern that hyperaccumulates arsenic. Nature, 409: 579. M a n n , W . D . 1998. Montana Mountain mining review and acid rock drainage potential. Environmental Serv ices , Publ ic Works and Government Se rv i ces C a n a d a . 79 Marcus -Wyner , L , and D.W. Ra ins . 1982. Uptake, accumulat ion, and translocat ion of arsen ica l compounds by cotton. Journal of Environmental Quality, 11(4): 715-719. Mar in , A . R . , P . H . Massche leyn , and W . H . Patr ick Jr. 1992. T h e inf luence of chemica l form and concentrat ion of arsenic on rice growth and t issue a rsen ic concentrat ion. Plant and Soil, 139: 175-183. Mar in , A . R . , P . H . Massche leyn , and W . H . Patr ick Jr. 1993. So i l redox-pH stability of a rsen ic spec ies and its inf luence on arsen ic uptake by r ice. Plant and Soil, 152: 245-253 . Mar ies , R . J . , C . C lave l le , L. Monteleone, N. Tays , and D. Burns. 2000. Aboriginal plant use in Canada's northwest boreal forest. Vancouver , U B C P r e s s . M c C l e l l a n , C . 2001 . My old people say: an ethnographic survey of southern Yukon Territory. Vol. 1. Hul l , Quebec : Canad ian Museum of Civ i l izat ion. Med ica l Se rv i ces Branch. 1994. Native foods and nutrition: an illustrated reference manual. Heal th C a n a d a . Meharg , A .A . , and M.R. Macnair . 1990. A n altered phosphate uptake system in arsenate-tolerant Holcus lanatus L. New Phytologist, 116: 29-35 . Meha rg , A . A . , and M.R. Macnair . 1991. Uptake, accumulat ion and translocat ion of arsenate in arsenate-tolerant and non-tolerant Holcus lanatus L. New Phytologist, 117: 225-231 . Mel l ing, D. 1994. M e m o to J im Smith ( B . Y . G . Natural Resources ) regarding waste rock sampl ing program. Referred in: T .W. Higgs Assoc ia tes . 1994. Initial environmental evaluation Mt. Nansen Development. Vol. 1. Wh i tehorse : B . Y . G . Natural R e s o u r c e s Inc. Mi l ton, A . , and M. Johnson . 1999. A rsen ic in the food cha ins of a revegetated metal l i ferous mine tail ings pond. Chemosphere, 39(5): 765-779. Minera l R e s o u r c e s Branch. 2000. Mount Nansen Property. In Yukon Mineral Property Update, January 2000. Department of Economic Development , Government of Y u k o n , pp. 45-47. M INF ILE . 1998. Minfile 105D-005 Summary Report. Whi tehorse : Y u k o n Geo logy Program. Mottana, A . , R. C resp i , and G . Liborio. 1977. Simon and Schuster's guide to rocks and minerals. Translat ion of Mineral! e rocce. M. Pr inz, G . Har low, J . Peters (eds.). N e w York: S imon & Schuster Inc. 80 Mountjoy, K . J . , and S. Ramsay . 2000. Final report vers ion 1 - historical review, site assessmen t and field sampl ing program of the Mount N a n s e n mine site, Yukon . Vancouver , Cono r Paci f ic Environmental Techno log ies Inc. Nardel l i , V . M . and E .E . W e i n . 1996. The healthy eating handbook for Yukon First Nations. Edmonton: Canad ian Circumpolar Institute. Nat ional R e s e a r c h Counc i l . 1977. Arsenic. Wash ing ton , D.C. : Nat ional A c a d e m y of S c i e n c e s . Nat ional R e s e a r c h Counc i l : subcommittee on A rsen i c in Drinking Water . 1999. Arsenic in drinking water. Wash ington, D.C.: Nat ional A c a d e m y of S c i e n c e s . Nob le , C . 2000. Little Salmon/Carmacks First Nation Northern Contaminants Program Proposal 2000. Submitted to the Yukon Local Contaminant C o n c e r n s committee of the Northern Contaminants Program. Carmacks : Little Sa lmon C a r m a c k s First Nat ion. Nordstrom, D.K. 2002. Wor ldwide occurrences of a rsen ic in groundwater. Science, 2 9 6 : 2 1 4 3 - 2 1 4 6 . Nr iagu, J . O . , and J . M . Azcue . 1990. Food contaminat ion with a rsen ic in the environment. In Food contamination from environmental sources. J . O . Nr iagu and M.S . S immons (eds.). New York: Wi ley, pp. 121-143. Pal iour is , G . , and T . C . Hutchinson. 1991. Arsen ic , cobalt and nickel to lerances in two populat ions of S/7ene vulgaris (Moench) Garcke from Ontar io, C a n a d a . New Phytologist, 117: 449-459. Pantsar -Ka l l io , M. , and P . K . G . Manninen. 1997. Spec ia t ion of mobi le a rsen ic in soi l samp les as a function of pH . Science of the Total Environment. 204: 193-200. Parker , H. 1994. Alaska's mushrooms:. a practical guide. Ancho rage , A l a s k a : A l a s k a Northwest Books . Pitten, F.A., G . Muller, P. Kbnig, D. Schmidt, K. Thurow, and A . Kramer. 1999. R isk assessmen t of a former military base contaminated with o rganoarsen ic -based warfare agents: uptake of arsenic by terrestrial plants. Science of the Total Environment, 226: 237-245. Porter, E.K., and P . J . Peterson. 1975. A rsen ic accumulat ion by plants on mine waste (United Kingdom). Science of the Total Environment, 4: 365-371 . Porter, E.K., and P . J . Peterson. 1977. A rsen ic to lerance in g rasses growing on mine waste. Environmental Pollution, 14: 255-265. Potv in, C , and D.A. Roff. 1993. Distribution-free and robust statist ical methods: v iable alternatives to parametr ic stat ist ics? Ecology, 74: 1617-1628. 81 Poush insky Consul t ing Ltd. 1994. Venus Mine tailings: study of remedial options. Klohn-Cr ippen . P u n z , W . F . , and H. Sieghardt. 1993. The response of roots of he rbaceous plant spec ies to heavy metals. Environmental and Experimental Botany, 33 : 85-98. Receveur , O., N. K a s s i , H. M. C h a n , P. Berti, and H.V. Kuhnle in . 1998. Yukon First Nations' assessment of dietary benefit/risk. Macdona ld C a m p u s of McGi l l University, S te -Anne-de-Be l levue, Q C : Centre for Indigenous Peop les ' Nutrition and Environment. Rip ley, E.A., R .E . Redmann , and A .A . Crowder. 1996. Environmental effects of mining. Delray Beach , Flor ida: St. Lucie Press . R o a c h , P. 1995. V e n u s Mine tail ings study. In Northern Water Resources studies. Arctic Environmental Strategy: summary of recent aquatic ecosystem studies. J . Chou inard and D. Milburn (eds.). Ottawa: Indian Affairs and Northern Development , Northern Affairs Program, pp. 145-147. R o a c h , P. 1997. Arctic Gold and Silver mine tailings pond discharge evaluation for the Carcross Tagish First Nation. A Water Contaminants evaluation under the Walk in Project File 9590-2-11. Whi tehorse: Wate r Affairs Div is ion, Northern Affairs Program. R o a c h , P. and E. Cunn ingham. 2000. Arctic Gold and Silver Mine arsenic contamination. Whi tehorse: Department of Indian Affairs and Northern Development . R o b s o n , W. , and K. Weag le . 1978. The effect of the abandoned Venus Mines tailing pond on the aquatic environment of Windy Arm, Tagish Lake, Yukon Territory. Fisher ies and O c e a n s C a n a d a , Environmental Protect ion Serv ice , Reg iona l Program Report 78-13. S A S Institute Inc. 2000. J M P - I N statistical d iscovery software. Ve rs ion 4.0.3. Paci f ic Grove , Cal i fornia: Duxbury Press . Schmoger , M.E.V . , M. Oven , and E. Gri l l . 2000. Detoxif icat ion of a rsen ic by phytochelat ins in plants. Plant Physiology, 122: 793-801. Sharp ies , J . M . , A . A . Meharg , S . M . Chambers , and J . W . G . Ca i rney . 2000 . Symbiot ic solut ion to a rsen ic contamination. Nature, 404: 951-952. Sheppa rd , S . C . 1992. Summary of phytotoxic levels of soi l arsenic . Water, Air, and Soil Pollution, 64: 539-550. Srhedley, P.L. , and D .G. Kinniburgh. 2002. A review of the source , behaviour, and distribution of arsen ic in natural waters. Applied Geochemistry, 17: 517-568. 82 Snel ler , F .E . , L .M van Heerwaarden, H. Schat , and J . A . C . Verklei j . 2000 . Toxicity, metal uptake, and accumulat ion of phytochelat ins in S/7ene vulgaris exposed to mixtures of cadmium and arsenate. Environmental Toxicology and Chemistry, 19(12): 2982-2986. Stef fens, J . C . 1990. The heavy metal-binding pept ides of plants. Annual Review of Plant Physiology and Plant Molecular Biology, 41 : 553-575. S tee le , A . 1999. Judge suggests changes to water act. Yukon News, M a y 21 , p. 6. Streit, B. and W . Stumm. 1993. Chemica l propert ies of metals. In Plants as biomonitors. Indicators for heavy metals in the terrestrial environment. B. Marker ! (ed.). We inhe im, Germany: V C H , pp. 31-62. T. W . Higgs Assoc ia tes . 1994. Initial environmental evaluation: Mt. Nansen Development. Vol. 1. Whi tehorse: B . Y . G . Natural R e s o u r c e s Inc. T. W . H iggs Assoc ia tes . 1995. Mt. Nansen Water License Application. Whi tehorse: B . Y . G . Natural Resou rces Inc. Tamak i , S . , and W.T . Frankenberger. 1992. Environmental b iochemistry of arsenic. Reviews of Environmental Contamination and Toxicology, 124: 79-110. T a m a s , M.J . , and R. Wysock i . 2001. Mechan isms involved in metal loid transport and to lerance acquisi t ion. Current Genetics, 40: 2-12. Tarnoca i , C . 1987. Quaternary soi ls. In Research in Yukon. Xllth International Quaternary Association (INQUA) Congress Field Excursions A20a and A20b. S .R . Mor ison and C . A . S . Smith (eds.). Ottawa: National R e s e a r c h Counc i l , pp. 16-21. Tempelman-Klu i t , D. J . 1984. Geo logy , Laberge (105E) and C a r m a c k s (1151), Yukon Territory. (1:250,000). Geo log ica l Survey of C a n a d a , O p e n F i le 1101. In Yukon digital geology. S . P . Gordey and A . J . M a k e p e a c e (eds.). Geo log i ca l Survey of C a n a d a O p e n Fi le D3826 and Explorat ion and Geo log ica l Se rv i ces Div is ion, Y u k o n , Indian and Northern Affairs C a n a d a , Open Fi le 1999-1 (D). Thornton, T .F . 1999. Tle ikw aani , the "berried" landscape: the structure of Tlingit edib le fruit resources at G lac ie r Bay, A l a s k a . Journal of Ethnobiology, 19: 27-48. Timper ley, M.H. , R.R. Brooks, and P . J . Peterson. 1973. The s ign i f icance of essent ia l and non-essent ia l trace elements in plants in relation to b iogeochemica l prospect ing. Journal of Applied Ecology, 7: 429-439. Turner, N.J . 1997. Food plants of interior first peoples. Vancouver : U B C P r e s s , and Victor ia: Roya l Brit ish Co lumbia Museum. Ul l r ich-Eber ius, C.I., A . Sanz , and A . J . Novacky. 1989. Eva luate of a rsenate- and vanadate -assoc ia ted changes of electrical membrane potential and phosphate transport in Lemna gibba G 1 . Journal of Experimental Botany, 40 : 119-128. 83 Va l le rand , P. 1995. Venus Mine tailings: site rehabilitation construction management report. Edmonton: Publ ic Works and Government Serv ices C a n a d a . V iereck , E . G . 1987. Alaska's wilderness medicines: healthful plants of the far north. Anchorage : A l a s k a Northwest Books. Vitt, D.H. , J . E . Marsh , and R.B. Bovey. 1988. Mosses and lichens and ferns of Northwest North America. Edmonton, Alberta: Lone P ine Pub l ish ing. War ren , H.V., R . E . Delavault, and J . Barakso. 1968. The a rsen ic content of Doug las Fir as a guide to some gold, si lver and base metal deposi ts . Canadian Mining and Metallurgical Bulletin, 61 : 860-867. W a u c h o p e , R.D. 1981. Uptake, translocation and phytotoxicity of a rsen ic in plants. In Arsenic. W . H . Lederer and R .J . Fensterheim (eds.). N e w York: V a n Nostrand Re inho ld Company , pp. 348-375. W e a g l e , K., W . R o b s o n , and K. Gul len . 1976. Water quality and biological survey at Arctic Gold and Silver Mines Ltd., Yukon Territory, Summer 1975. Whi tehorse : Envi ronmental Protect ion Serv ice, Report Number E P S 5 - P R - 7 6 - 1 0 . W e i n , E . E . 1994. The traditional food supply of native Canad ians . Canadian Home Economics Journal, 44(2): 74-77. Wes te rmann , H., and M. Nahir. 1999. C a s e study: rehabil i tation of mine tai l ings at the V e n u s Mine mill site near Carc ross , Yukon Territories. Edmonton: A s s e s s m e n t and Remedia t ion of Contaminated Si tes in Arct ic and C o l d C l imates ( A R C S A C C ) Proceed ings , May 3-4. Sess ion 3: Mining contamination and c lean-up. pp. 67-74. Wicks t roem, G . 1972. A rsen ic in the ecosystem of man. Work-Environment-Health, 9: 2. Wi l la rd , T. 1992. Edible and medicinal plants of the Rocky Mountains and neighbouring Territories. Calgary: Wi ld R o s e Co l lege of Natural Hea l ing . Witt ig, R. 1993. Genera l aspects of biomonitoring heavy metals by plants. In Plants as biomonitors. Indicators for heavy metals in the terrestrial environment. B. Markert (ed.). We inhe im , Germany: V C H , pp. 3-27. W o o l s o n , E.A. 1981. Man 's perturbation of the arsen ic cyc le . In Arsenic. W . H . Lederer and R . J . Fensterheim (eds.). New York: V a n Nost rand Re inho ld Company , pp. 393-407. Wyt tenbach, A. , S . Bajo, and L. Tobler. 1996. A rsen ic concentrat ions in success i ve need le age c l asses of Norway spruce (Picea abies [L.] Karst.). Fresenius Journal of Analytical Chemistry, 1996: 668-671. Zar, J . H . 1984. Biostatistical analysis. Second edition. Eng lewood Cliff, N e w Jersey: Prent ice Hal l . Persona l Communicat ions At l in, W inn ie . Persona l communicat ion. 2001 August 20. Beaubier , P . H . Letter to S. Johnnie. 2000 November 22. Bil ly, E v a . Pe rsona l communicat ion. 2001 Ju ly 23 . Brown, Bever ley. Persona l communicat ion. 2001 July 21 . C a l m e g a n e , Ida. Persona l communicat ion. 2001 August 19. C h a n , Laur ie. Persona l communicat ion. 2002 June 24, July 5. Char l ie , Dawn. Pe rsona l communicat ion. 2001 Apr i l 17, A u g . 22 . Char l ie , Kitty. Persona l communicat ion. 2001 July 25. Cru ikshank, Jul ie. Persona l communicat ion. 2001 June 20. Cu l len , Wi l l iam. Persona l communicat ion. 2002 March 11, 12. Ga tensby , Harold. Persona l communicat ion. 2001 July 17. Hartshorne, Brett. Persona l communicat ion. 2002 August 8. Johnn ie , Violet. Persona l communicat ion. 2001 July 24. Johnn ie , Bil ly Peter. Persona l communicat ion. 2001 July 24. Lo, Me i -Te in . 2002. Persona l communicat ion. 2002 Apri l 10. R o a c h , Patr ick. Persona l communicat ion. 2002 August 8, 12. Rober ts , May. Persona l communicat ion. 2001 July 23. S a m , Kathy. Pe rsona l communicat ion. 2001 August 26. van Dijken, B. Persona l communicat ion. 2001 August 10. Zhao , Henry. Persona l communicat ion. 2002 March 7. Appendices 85 A 1 . Nutrit ional table for important plant foods and medic ines used in the Y u k o n . A 2 . Latin, (Northern) Tutchone, Tag ish , Tlingit, and common names of some Y u k o n plant spec ies . A 3 a . A N O V A results for testing differences between the means (Wi lcoxon Rank S u m test for independent groups at a = 0.05) for location (1, 2, or 3). Data sets include total arsenic, inorganic arsenic, and organic arsenic . A 3 b . Resu l ts of normality and significant means tests done after A N O V A s were performed. A 3 c . Resu l ts of equal var iance, and model testing to determine effects of geo logy on a rsen ic concentrat ions at each mine site location (1, 2, or 3). A 3 d . Resu l ts of statistical tests compar ing wil low stems versus wi l low leaves. A 4 . Compar i son of mean total arsenic concentrat ions in data co l lected from previous studies and this study. A 5 . To lerab le Dai ly Intake (TDl) calculat ions based on the mean, maximum, and minimum (dry and wet) inorganic arsenic concentrat ions (shown in bold) in different plant samples. Tab les are differentiated by spec ies and locat ion (1, 2, or 3). A 6 a . G lossa ry of common plant compounds. A 6 b . G lossa ry of se lec ted terms used in or related to this dissertat ion. 86 CD o < o 5 CD TS - 3 o o € co O c CD o 0_ t— © ro TD o o i 1 0) CD TJ TO TO TO TO — OJ 2 CD TJ CD CO •c CD CL CD E ro c c o E E o O a> E ro c g < c CD O CO i i i CD CN CD CD , CO LO CN CD O N CO CD CD CD T— CN CN i i i CN , LO ^ ™ °° fr; ' Z- T - co co 1 0 CN CD i — co co CO CO CO CD ci I I I I o CO CO "3" LO CO CD CO LO i i CO CN CN LO 1 CD h- 1 CD 'IT-1 1 CO CD 1 t i • • $ CD , T— T— CM CM CD CO r- co CO i co ' CD CD 1 CN ' 1 "~ | T— CO T— CO 1 1 CO ' CO CO CD CM CD ' 1 1 1 o LO CM 0 0 O CO ^ 00 £2 CN CN CO ^ CN LO CD CM ^ # ' § CO •<- CN <D ^ LO i r- in m T -i t LO CO s oo <° ^ * ' ? CM LO LO cn co ^ T - m co CO CO CO o CN CM r-CM CO CO CD I— , °^  00 LO CD .CD CO ' £ CM CD CO ' CD ^ ^ ^ Ri CD CD CD T ^ CD CO ^  a, CM ' ' CD ? £ CD CO LO '. CD CM LO CD , r-- r*-d d czi ci CM i O CD CD 00 T - CD CO CO N CO O O T - r- O CM O O O i i i , N-CN-tCDOOr-CNOO ( ^ O) (O CD N N O ' C D C D CO LO CD T - CD Ci T - Ci Ci LO f I - ^ LO °P CO LO LO CN CD CD ™ 00 CM CO 00 , CM (N S , N CD O) T - . CD CO CD LO CD . CD CN LO CD , LO , , CD CD 00 CD CO -3- CD CD CD 00 00 00 CO N N 00 00 00 CD 00 OO h~ CD LO , CN , , , . LO CM . O CD LO N- CN , CO t— • LO CD CD CD CD CO LO CD LO LO LO CO i t i i i i CD Xl CD TJ 0) CD XI ro CD -=! CO TO > O O H T3 i i CO co £ .® r fc o £ £ l o CD xi CD _3 xi t ro TJ XI C CD o X co 3 1 5 S = CO "O CD c CD > c e 8 S 3 O W TJ O $ $ X> 5 XI Xl ro TO a. x: £ Xl CD a. 'c 3 ; o "3 S S .5 .5 P P o o CO (0 e CO §• CD s e 3 c 8 .8 T J c JO c .to CO C; g g co TJ o -s cu .co . ,^ ~~ ~ - U - j c o c o c o L u c o O : CO 3 .to 55 c co g 1 1 CL ?> " 2 C CD 2 -5 s- 8-1 <o .5 JC 3 CO o S CD CO CO <D E O co JC o co co w 3 3 3 -Q -Q -Q 3 3 3 CC CC CC CO _ 3 CD fl) Q. ro co iO 3 § 3 «0 co co .ro § § § tc -q: u. •S 3 JC -2 CO CO CD CD or 6: CO o f .CO S ^ 43 CO 3 X Q S ° co 2 2 a CO o CD o 3 D. TJ CO (D 8 I Xl ii= S .3 I O tc 5 oi > M to .2 <o .co Q. <o oa g -S 42 5 5 S -3 IP § 8. to co § 0> -H ~" CD CD fi CC <t <T Ct LU 87 c 8 CO O < o 5 CD T J 3 o i 1 E O) E 3 o>| o n i CD O 0) 2 T J >, XT CO LL c CD 2 o. © CO "O o o CD 0)1 o> — CD 2 CD T J CD 10 r CO CL CD E CO c c o E E o o CD E CO c o c CD O CO i i i • O CN CO O i • CO ' CM CM t- to CO CO ' i 1 CD ' 1 S CN O CM CO i n i i i i i i CD CM CM O O -3" i i g> C>| i i i i JO , T - CN CO CO CD h~ 1 i 1 1 1 1 -r-I co CO , T - CO CO ^ CD O) O m o 0 0 0 c o c o CO co CO ui S C O O J C O C O S C O O O C M - ' T T - ^ T - C M C M C O T -o oi r o in co J?: LO TJ" O) 00 f N CM O O 1^ CO CM CM i n CO cn co CD X l CO CD ro c c JSC CO C T ? _ _ m CO CO CO £ X ! X ! XI CD c £ £ S I CO CO (0 C C <D CD CD x: o C-> ~ x: t t o CO CO .£ * £ X l T J T J CO C o 'c 10 CD > o T J 2 8 CD CD CQ CO S ro 2 co ,C •§ ^ c S is § o> cB co CD CD OQ rt 5 2 I CO & c ro co 2 Q . -5 I S co c \ © ro C L Q - as C L U) c^  OC E T J CO X) 0 als em rcti XI i s CO c o ro > c § T J 1 E o o \— _c CO E o E CT> CD ro 2> i- CD « !§ $ I CO sp co eo 8- 9-Q - CL -32 co .c CO £ co § $ 5 § 2 0? ^ * CO CD O CD C L co £ CO co 1 CO CD T J c ro o x E o c ro c o >-c o E E o o Oi c 1 0 ro XI ro CO > ro o c ro ro T J CO ro o © co CD E ro c c o E E o o c ro o CO g l E o o = o 2 I C L E co J9 O >- CO CD ro 0 xi © T J fi "2 • — — C C J ) r= St C X_ O g m —1 m CO CO O E o ro XI C O i  XJ O 5 CO CO O > 3 (0  Q . T J CO ro o 0 C L co CO o, 8 a: 5 .c •5 O E CO co c o 0 ! (A 0 E (0 c c o E E o o £ c LU o c c c i-e, CO . ro - Q ,8! CD u. co" co O E i i 8 , ro • Q "o c o CO CD TJ C L CO i f CD ro C L O I'll o CO x ^ CO P E 0 ) CO © m ro L U g) CO * * , c CJ> o ro1 II ro" S CD .2 t . CO O " L -TJ CD 2 H Jo i— CD TJ C _ CO. E -3> o Q -o o •= CD X Q J e S *8 j c CD i_ 3 O o ro lo £ o o ro X l CD C o E ro CO >i CD c TJ i (tl CD X t CD cl| ro CD XI CD CO o o E CD" i a o ro C L -g O CO CO St § ro co O co CO o E TJ 0 co" CO o E ro ro, Q J , ro i f . ro ro i o x: CO o CD XI c 2 o c 'ro c 3 O E 0 XI c ro t_ o X CO 3 X I X g> x LU o - © > 3 CT 5 LU CO 0 X >, LU < "co CO 5 3 CO •ro J C ro C T C T 0 3 O) c CO c "5> •c , o JQ < c o LU TT QC TT LU UU "c CO TJ LU LU © "o ro ro |TJ ro c ro c 0 'I c E © '1 c JUL IS? TJ C ? CO o CD CO "CO X CJ) ©• JC o O) C cf II 0 TJ 'CO X E >© JC co •© c =ro o >. x: CD IS 1=3 CO p C L C L CO .ro 8 0)1 •8 I' C L C L CO E 3 C 8 0 - j C L C L co s I —J C L C L CO C o © C L CO O 0 CO eg ct: .CO 55 c * ro c CO O CO "S 0 JC & JC CO E 3 I & I CO s . 3 .5 8 5 co ro IS CO E . 3 .5 8 |3 0 E 3 S 3 s ou 990 0 ||OS ou 99C0 AjjaqdsBJ snusA ou S090 |IOS ou 000'l- AjjaqdBOS IAISOV ou Z960 |IOS ou W O O SIU8}S MO|||M OU 3600 S8AB8| MO||IM OU 9ZS0 LUOOJLjSnUJ OU fr93'0 AjjaqMOJO saA owo 68} JOpBjqB"| ou 000" I AjjaquBJO ssA 9000 ssoLU noquBO ou 000'1- Aj jaqaniq U8SUBN }|AJ iluBOj^urjjs UOI}BOO| s a p a d s iinsay oiN3syv oiNvoyo saA LZOO ||OS saA 900 0 AjjaqdsBJ snusA saA geoo ||OS OU 000' V Aj jaqdBos IAISOV ou WZ"0 |IOS saA l-OO'O SW8}S MO | | |M saA KJO'O S8AB8| MO||jM saA fr30'0 woojusniu ou 901-0 AjjaqMOjo saA 3000 68} JOpBjqB- ] ou H 3 0 AjjaquBJO saA l-OO'O SSOUJ n o q u e o OU ZLVO Aj jsqsn iq U8SU6N }|AJ ilUBO!;!u6js U0J1B00| s s p a d s 91!S l i n s a y OIN3SUV 0INV9HONI saA Z30 0 |jOS saA 900 0 AjjaqdsBJ snusA ou 3900 ||OS ou 000' I A j j s q d B o s IAISOV ou 9Z30 ||OS saA OOO'O SUJ8}S MO|||M saA l-OO'O S8AB8| MO||jM saA ttO'O ujoojLjsnuj ou VPZ'O AjjaqMOJO saA 3000 68} j o p e j q e n ou H 3 0 Aj jaquejo saA l-OO'O ssow noqjJBO ou ZLVO Aj jaqsniq U8SUBN }|AI £}ueoy!u6js UOj}BOO| s a p a d s 81!S }|nsa>j OIN3SMVIVIOI ojuesje O | U B 6 J O pue 'ojuasjB O J U B 6 J O U ! 'OJU.9S.JB IBJOI gpnpin sjgs B I B O .(goo = D I B sdnoj6 luepuedepuj JOJ. is9i. wns ^UBy UOXOOIJAA) 9}\S L J 0 B 9 \B (£ JO 'Z '0 SUOJlBOO| 6U0LUB S90U9J9.JJ,!P 61N1S91. JOJ . sjinsej VAONV B£V 6 8 90 0 | o_ Q . CO o c 00 CD x: CO CO " O LO o o V Q . -6 "£ CP ro o 8 T3 C C .9P — 00 CD ^ .ti o CO c .E co E c_ CD jS" £ ro —• "o CO ^ C CO o c I 'L? •- S-« "S C 8 ci o " w * 00 * cu -0 CO - j co O CO TO 1 | o E a - £ E £ o o) ^ c o X, p i c? o j2 C "D * II 8 L £ c co a CO CO o T J CO g ° 0 c5 II C CM C 8.8 § § V -C CO g LO Q O c CO CD c c 3 Q 8 q> 8 5. co CO Z o o d A 8 co c CD (0 CO c <D (0 O Z a> . D - ±L CO S CO CD 51 i X ) CO CO o E CO CM CO CM CO CD I1 CO o CO CD •a* a ro ro o X J CO o cn CD II CM CO ^J-" O . CO C CM g II C CO <= LO § P Q O So c 45 3 CO <D c c 3 Q Q co a: CD S I I i 5 .s Q_ (0 o z < o oc O £ 8 CO CM o o ro cu w CO c CD (0 O Z CD . CL — CO S CO CM LO CO CM IS CO z I CM z I CO I CM z co" Z CO z I CM z co" co Z i CM CO z 1 CM Z co" I CO I CM 0 0 z I CM O CO CO '5? O O CO o o o CO CO o be •2 J CD 5 5 8 ro I &} i— o si xi CO mi XI co x CO CO O TJ E E 91 C 8 x> CO < 8 L>— "c o z < o z a ro ro o XJ cp o cS | CN ro c - 2 C CO g l b Q O * CO *: c § Q Q co a: tD S .2 t CN .8 I •c CO o o d A 5T 8 ro c CD » tD CO O Z a> . o. ~ co S CO CN CO CD ft to o CO 2 (A CD to a ro ro o XJ CD O CD "5 T CN 8 ro ^ . - - i ro g> a . co -c CN fi g n C CO § p Q O c s 2 8 CO tD C c Q Q co a: tD s CO z o CN I co o o d A § ro < O OC O c CD CO CO c tD (0 O Z tD . C L ± ; co S s CO I co IS • i ^— z c "co |CN CO > CO I CO I c :8 CO > 00 z CO z CO z 8 2 CD 3 | CO t i l o o o 8 o o o o CN LO CO CN d CO CO o E li 8 CO o XJ ro ro CO CD > ro fi o 0 5 ro o (0 CO ro 92 o CO CO ro CO c g 15 8 c o o o "S g CO c J= CD co _g> § CO -o o c§ Q-•5 ff & CD o J ; 2 o c c ° CO * ! CD C II y= co =, CD 0> = <» ° «i r - r - OT ~ • - CO E XJ CD B CO" a> 5 "Jo "O CD "O 0 " D c ~ =J 16 D) O C .S .E g> co CO k CD -Jr; 3 +-> CD •S s 2 o c E Q co "O . II CO « * CD" o 3 C CM TJ " ~o CO 2 > c E •coB£ CD O CO o ffl X CD CO j « co "5 CD = to c o CD E II or *= * oCO < CO o o V QJ x: o CD It CD CO 3 •«-» CO 0) 8 c CD CD > ro Si CD CN z c g s _ o CD — XI o >s CD o -S 9 o CD o I is CO CD ro •S 8 CO •JD u, 5 c CD CO CO C CD CO O Z CD . C L ±1 CO S LO s CD CD I1 ro o CO CD C L , to^  CD 5 cl TJ CD E Ic ro I c O l CD mi o LO o d v QJ J C o CD CM > CM LO o d v O - Z *= a. c o CD CD £ O c D) 'co Q) XI CD ~~ CO >> CD o -S o c © CD o > CD | - 3 O 2 § J — cF CO CD « 8 CO 18 o O z < o o z CD (0 CO C CD CO o Z CD . C L £ CO S I s-CN o CD CD m •3-o o o to cn 8 CO CM 00 CM 8 o d CO o o o d V I s-CM o o CO CO CM o CD I co o d oo co d CD CO o d o d 3 d CD 3 CD > O c I CO I CM CM O I s-o 3 o d "co CO o E 3 8 co £ o PQ CO X) CD E o o 1 _c CO 3 E 93 CO » : CO CO E L_ o c o I'D i CD E CO c CO I c o . ro 1 o E o c i v QJ 'ii CD LO o 0 V 0-1 —-c O. CO CD £ °' c O) CO Q) X t CO 5! CM z > < T— Z CD TJ O ^ < 0 >» CD o -£ co O c ro CO O > 9 o CD ro I § 8 EQ ^ QJ 0 0) Q j CD ctr 42 8 LL CO < o c CD (0 co c CD CO O Z CD . C L — co S 3 CD s CD CD CD CD CO o CO CD £ | 5T co 2 a" CM ro s « ± 8 8 CD TJ O >» CD cn •§« 51! SI o CD O CD ^ — 8 90 co O £ 05 CD CO L O o 0 V Q J Co ro 42 g LL I eo o O Z < o a: o c CD CO CO C CD CO O Z CD . C L £ CO S CO CD CD CD m CO CD o c i CO CM CO in I o l o 0 Is-CN o o CO CD o d CM CO Is-o d CM o d E o 2 J C CO 3 E 94 c o o o CO < m o ci v ° - Z CL £ o F? ro £ o c CD 'to ro J Q CD ' L _ CD > 5! CN z > < z c CO o CD CD O CD CO o O d CD O CD T J O ?> CD o •§ ro CD O > o CD O CD OQ io = O £ g to CD Co" o d V Q . w 42 J C LL o •c CD o CD CO to 0) ro. o CO c 42 to LL CD > 5C i» "co o 3 c r CD c CD to CO C CD CO O Z CD . C L £ co S CO CD S1 CD O CO CD CM > C D C O CN T— I S- oo r— IS- CO L O CD i— CO CO •*r C D T — C O O t o 00 < C O oo o o 00 C N d d d d d d d z > oo C O CO C O OO oo t o C D CD t o CM o o 1 1 o i i T - IS- CO o o <  o i t— I S- o o L O o d d d d d v' d Z d V data C L « ^ IPN1 c g to 1 1 1 s o i i C O C D 0792 2703 8148 0441 6207 irmal fican Geo o o d d d d d d d no gni i— o to z c CO oo co T— CO CM CD o CM o o T J I CO i i CO CO CM o C O CD -Cl — L - 8 i C N i oo c o o O o E CO o o d d d d d d d 45 CO var Ge c CO c co ^ _ CD L O x — CD CO g •sr L O t— ^ — o C O o CD i • o i i CM t o C O o o C N • o i o r - o o oo c o d d d d d d d w CD T J O c to >, CD O 00 CD C O • q - 00 >< CD CD CM o o t o t o o I S-.„.„ r> • i ! oo t o o o o ode eolc arial Gee i •r-d i C D d d d o d o d C O d E O > 0 c j Q T — CO -a- CM .CD CO I S- oo C D CD o c O o o C O T — o OQ CO o CM C O o o o test re Q . Q. CO d d d d d CO *-» o CO d T J T J r- 0 0202 <D 0 0 0 0 0 CD oo IS-V C L test 0 j * itioi alu 0202 alu alu alu alu alu alu It: test c CO oca > 0202 > > > > > > C D JC LL oca o d o o o o o o d o L . — c c c c c c c CD ch o £ CD CO 1 med. 3 CO to c 42 to ro >—J o CO o CO CM CO L O CO CM arianc CO _g o o o L O T C O C O arianc 42 LL "53 r— ocat q 0.01 o T — 0.03 0.27 0.39 0.08 0.04 0.98 > E 1 1 15 O nor 3 C T a: c CD o NIC to nsen rry** j moss* t lor tea** t 0 I E o leaves** stems** GA oecie Na ebe iboi nbe u CO 1— /-> ssb shrc ow ow « QC oecie . *» 3 rn CO Lac o — — "Q o C O 2 JQ 8 b Lac E E 5 CO CN d m Is-CM d ro CO i l IS-CD CO O O O o o CO o d co i n o CN o , ro t CD O CO , ro % 0 95 >» .c = o » CO -S o .8 cn a. " Q- Q co c ^ I 2 tO >, w TJ x : rs —•. w II to O | c f to Q) TJ - « — ' to to =3 O > CD Q . E o i 4— TJ CD O CD ro TJ c to c o ' ro JD to O TJ C ro c TJ O O II OQ o" O O CM O O CD CD E ro O to CD O c CD O c o o o 'c Q) TJ O CO to 1 ro ro o c ro CD E 4— o c o to " l _ CO Q . E o O CO ro TJ ro TJ CD o o o E ro sz CO c 'c c 13 o TJ c ro X T o CO o CM O O CM E E c o CO o CD —I to _ j CD CL o ro o a: LU CO LO T J O J c - r -w cu 'o CD CL CO co tu >-CO Ol| 0) j/> 5 < < < < < < m o o o < < < < o o o < < < < < < o i i i CO CO to O O O •S -S -S .8) .O) ,g) "3 "3 "3 I I .5 .5 8 cj . £ £ £ I I CO CO o o .CD .CJ) C L C L co I .5 c i G C L CJ CO 1 .5 G CJ s | 2 CD c CO C L C L CO S , 3 .5 CJ o C L C L CO .1 .5 8 s C L C L CO C L C L CO C L CO C L CO co co to to .c .c .c .c T j T j T j CO CO CO JO o o o o .to c fo CD CD o o co , C TJ co O co .c T j CO _ o o CO CD -g to to CD Oj Tj Tj CO CO CD <D •S 45 T3 Tj Co CO CO .CO ,CO s . 3 8 s s 3 . 3 .3 .3 G G cj o s . 3 .3 G o co to CD CD 45 45 Tj T J V T oo .to •s =1 11 .5 .3 8 8 to JO CO co to to to to - » . - - , . - > . • - » . - > . CD CD CD J D X I X J o o o o CD CD CD CD CD CD X I X I X I X I X I X I CO CO CO CO CO o o O CD O T- i - o O , 0 0 0 0 0 0 d o o d o d o S co n . CD CN £ CO CD CD CD X I X I X I o o o o CD CD CD CD X I X I X ) X I o o o O O O CM CO T— CO CD CO CO CO CM to CD CD CM CO "~ CO CO in LO LO T T— ^_ CO CO "* CO CO LO LO LO cn CD Oi CD CD 00 o o o CD CD CD CD o o o CD CD CD CD CD CD CD Oi CD CD CD o o o O) CD CD CD o o o CD CD CD CD Oi CM CM CM T— CM CM CM o o T— CM 00 LO T -CD O O CM CD > it to to o ct CD CO o to CD to _J c o to CO CO c o CD tM CM c CD to c CO c CD to sr. CO CO CM CO • i 5 I c o to CO Q \ tu L -CD 1 CD > > > k. to to to to to CO o o o Cd CH Ct & CD CD CO c CO > i t CO CO o ct CD CO —I c o w "co CD co _ i c o CO CO CJ c 3 —> to CD c 'to X CD .E o to m CD 2i c CD to cz CO ^ O l - O • O T J T J X J T J T J O O T J T -V V V V V V Q Q V o o T- TJ V LO m CM r - - o o _ _ — — — — •* O O C D T J T J T J T J T J T J O od d v v v v v v d ^ cr cf ^ cr ^ c T c ? c r c ? ^ c ? c ? & ^ CD X ) CD 3 CD X I CD 3 CD X I CD 3 CD X I CD 3 CD XI CD 3 CD X I CD 3 CD X I CD 3 CD XI CD 3 O Q O Q C Q C Q C Q C Q C Q C Q C Q CO to CO CO to to CO CO to CO CO to CO CO o o o o o o o 3 3 3 3 3 3 3 O O o o o o o X I X I n X ) X I X I n l _ ' C s '< 'CC ' l _ \ CO CO ro CO CO CO ro o o O O O O O CD X I c CO CO 3 X I o CD X I c co to 3 X ) o CD X I c co CO 3 X I o CD X I c CO CD X I CO CJ O CO 3 X I o CD X I c co CO 3 X I o CD X I c co CO 3 X I o < 96 W .92 u «, CO TO « ui CO §1 t l 2 « 5 < <= o o T * < o o < < < < < < c o m o o o < < o o o < < < o o o c o m CO CO T j TJ E E S S 2 2 2 2 . O ) . O ) . O ) .CJ) £ c c c £ £ S £ 2 2 2 2 H3 H3 -+3 CD QJ OJ QJ Q . Q . Q . Q . ,£ ,£ ,S £ Uj UJ LU LU S S E 2 2 2 .O) .O) .Ol £ £ c S E E 2 2 2 CD CD CD 3- 9- 8-.E ,E ,£ LU LU UJ E E S 2 5 2 , D ) . O ) . O ) £ £ £ E S E 2 2 2 H3 H5 «C CD CD CD S- S- S-,E ,6 ,S LU UJ UJ s i £ -2 r- C I .O TJ c: CO CD CD - Q - Q CO J O C E CJ 5 CD I CD CD i, I i i T j T j CD CD •8 -S ? ? E S 3 . 3 .Ci .Ci •5 T J c c J O J O c c CD CD O O E t O) O) co c CD - Q T3 E .2> 3 s= 3 O .Ci CZ •5 c J O c CD co £ E 3 . C CJ O CD O-C L CO I .c G cj CD . -J C L C L CO i CJ o CD C L Q . CO I . C 8 CD TJ CD 1=. CD TJ O cz T J CD C CD T J o cz I & I t— & s CD J D CD JZ1 CD X ) CD xi CD X I CD xi CD X I CD X I CD X ) CD CD X I X I CD 2 xi — i - ~ i — i J = J = J = O O O c c c CO CO CO o cz 2 w w xi xi X I CO CO CO _ZJ _3 zz E E E "co To "ro CD CD OJ J = to CO "to •.—• X I X I r— O o o o o o I s - o o q O 1 o 1 1 1 q q o o O o o d d d d d d d d d d d cn co CO •>- T" m CO CO CD co CM CM co CO U") m l O i n T— T_ CO co o o CD CD CD CD CD CD 00 00 o o o CD CD o o CD CD CD CD CD CD CD CD o o o CD CD CM CM CM CM CM "*"" IO m CM ^ I s -o o o CD Tl" O CM CM O d d co CD co T— Is- 00 CO T— _^ _^ in in un ,_ co CO o o o CD CD CD o o o oo 00 o o o CD CD CD o o o CD CD CM CM CM CM CM CM *~ CM CO* z Z c o CZ cz 'XJ CD CD co CO CO o CZ c o CO CO -1 z z 5 CD > Ct co CO o Ct CD CO CZ o CO c o o c ZJ CM CM f^j J Z CO CO CD CO CO c £ £ I CD r- 5 2 = ° <o "S CD ii; c CD CO CZ CO cz CD CO CZ CO w CD c > CD rt g <o 3 8 z ct CD J ^ CO _ l c o CO CM CO CD to cz CD CO tz CO cz CD CO tz CO CD o J C CD CD to CD rr CM co z, z z ^ i 5 t-' 5 5 5 £ £ £ i§ zS ^ c CD CO cz CO c CD CO tz CO to zs c CD > CO 3 c CD > un o — — — — — m T - O T J T J T J T J T J T J O 0 0 v v v v v v 0 - . Is- o Is- I s-CO o in Is- o CD CD o TJ q q TJ TJ CO CM q o m o V d d d V V to d d d d d iri d o o o Is-& cr-CD XI CZ CO \ o to 3 X ) 5 o CD X ) c CO CD X I o CD X I o CD X l o CD X ) 5 o CD X I o CD X I o CD X l 5 o CD X I o CD X I 5 o O O O O O O O O O O O CO co CO CO CO CD CD CD CD CD 1— H 1- h- H < \ < \ o o o o o TJ TJ TJ TJ TJ CO CO CO CO f s l_ \ \ X I X I X i J D J D CO CO co CO CO —I 1 — i _ l _ l E E E E E E o o o o o o o o o o o o L . L . ! L . t _ J Z sz J Z J Z J Z J Z to to CO to to to 3 3 3 3 3 3 5 5 5 5 5 5 £ cr-! U _ CD CD X I X ) C L C L co co co co Ct Ct 97 CO 0) G Q. CO ro ro LU CO « 5 1 r- t to o o TJ-< m m a o w m L L O O < < < < < L L L L . < < < < o o o < < < TJ TJ CD CU tz cz CD CD TJ TJ O O C C TJ SJ, i jz CD TJ CD CD TJ TJ CD CD TJ TJ CD C CD T J O c CO CO CO CO CO CO CO 3 3 3 3 3 3 CD CO CO CO CO CO CO CD CD CD CD CD CD .2 T) TJ TJ TJ TJ TJ TJ CO CO CO CO CO CO CO 3 3 3 3 3 3 3 -Q •Q •Q •Q -Q •Q •O 3 3 3 3 3 3 3 CC cc cc CC CC cc CC TJ CD a> TJ O c .co 53 c co c CO o co "§ CD J C Q. CD • C CO 53 c •§ CD C CO o CO "5 CD •a CD - C CO 55 c TJ CO c s CO 1 a CD co CO 53 C CO c CO o co "§ CD J C 8-• C _ co co 55 c •§ CD C 8 .ro "§ CD •a CD - C & 55 C TJ CO c CO o CO "5 <D & 53 c co c CO o .ro "5 <D §" JC co CO 3 CJ CO 3 •e co 3 CL CL CL CL co co co co ft CO CO c o CD CO CD ja CM CD Jd L . 1 L _ & i cf CD £1 CD £1 CD ja QJ J3 CD CD ja CD ja CD J3 CD CD ja CD ja CD J3 CD CD CD n £* ja CD ja CD jQ CD ja CD CD CO CO CO 0 ) 0 ) 0 ) 'M CM o 00 O o o o o OO L O L O i O 1 o o 1 o 1 1 1 1 1 1 1 1 o cb L O d d d d d d CO CM CO T l - T " Tj- T— T - T - - t— CO m CN •sf CJ) t— co CO L O L O in Oi CJ) co CO L O in 00 CJ) O O oo CJ) o o O) CJ) O) CJ) O) CJ) CJ) CJ) O) CJ) O) C D CJ) o O CJ) O) o o CJ) CJ) CJ) O) CJ) o O) CJ) CJ) CJ) CJ) T— CN CN T— T— CM CN T— T - *~ *~ T— ^~ *~ o o o o o o o d d o o o CM O d d d T J - co co m m T J -CM CO o o o o o o T— CM CO < < <L CJ) O) CJ) O) CJ) o T-T-T-T-T - C N C M C N C O > £ ^ > £ £ £ > £ l O t O l O l O l O l O l O C O u ) C C C C C C Z C C c C D C D C D C D C D C D C D C D c D > > > > > > > > > CD > Lc CO CO o OC CD CO c o CO c o o CO CD c 'co I CD SO CD > CD > CO CD CO CO o8 08 CD > CC CD CO I c o CO o t j - J CO CD CD o J= CD CD > CD > CO CO o3 o3 CD > CO »3 CD CO c o CO CD CO = T J T J C O W ^ § 2 2 S i 2 i 3 ™ > o o S c o c > o o o r o « « g O O a g c o > O O C ) § § § o o X o o CD CO CD CO CO CJ) T I -CO oo o O CN T— TJ T f d d V CM TJ TJ TJ V V V < < _ _ _ _ o o — — — — T J T J T J T J C O C M T J T J T J T J v v v v ^ : 0 - v v v v o o o < < < — — — — CO CO TJ TJ TJ TJ CM O v v v v 0 - ^ CD CD ja ja C L to co CD ja a. co to C D C D C D C D C D C D C D C D C D C D j a j a j a j a j a j a j a j a j a j a CL CL CL to C L C L to CO CO CO t o c o c o c o c o c o t o t o CL to co CL CL CL CD CD CD CD ja ja ja ja O . O . O . Q . to CO CO CO CO CO co co co to CD co CD CD ja JO CL co o CD JD C L CL CO CO o o CD CD § 5 5 ja ja ° ° ° a a = = = § g § ^ £ 98 CO o ro, Q-l (0 co cp CO CO oil ro ,« cu J5 L L L u O O O O O O m L t 1 C Q C D O O O C D 0 3 C Q C Q O O O O O O TJ 73 co co c c co co T J T J C L C L C L Q . C L C L C L C L C L C L C L C L CO CO CO to CO CO CO CO CO CQ CO CO CO O) CO to to to CO CO CO CO CO m O) O) O) O) O) > 1 1 1 1 1 oo CO i - o d d i - T- Is- CJ> CD CJ) CJ) CJ) CJ) CJ) CJ) T - CM < < CO CO > > o o o o o o CM CM CM CO CO CO CO CO co > > > CO CO CO 0) Q) _CD CJ) O) T t O ) o o CM d d r» CJ) CO o o o o o o CM CM CM TO •«J-eo LO ^ CD CM CM CM CM CJ) 00 CD CM CM CM CM CO CO CO T t CO CO T t T t T t • t T t T t T t T t 00 00 00 00 0 O O 00 00 00 00 0 0 O O O O CJ) CD CJ) CJ) 0 O O CJ) O) CJ) CJ) 0 0 O O O O T— T— CM CM CM T— T— T— T— CM CM CM CM CM CM co 55 cz c T J T J CO m CO CO T J T J O O _ _ O O _ ^ ^ .9 O 2 2 2 T5 CJ i— L -< < c CO co c CO CM CO o ~ £ CO 3 Z « "= 9 cu fe. CO c c CO CO _ CD £ o C L JS CD t T J 3 _ CO CM CM z z g c ro 51 - 7 CO C L CD T J CM" CM C CD CO C CO c CO co tz CO 2 2 co o 3 CO CO 3 c CD > C L CO T J CO 3 C CD > co o CO C L CO T J CM CO CO C CD > cz CO > CO 3 C CD £ CO 3 C CO > CO CO 3 CZ CO > CD > CO > co > to to (0 08 03 S T J O O 08 T J O 0 T t O) CO CJ) LO 00 0 CJ) O CO IS-0 CM LO d d T t d d 0 0 0 0 CO q 0 0 0 q q Is- 00 d d d d co T t CM 00 CO Is- CO T t Is- CM O 0 0 0 q O 0 0 q d q d d co 0 d 0 0 Is-0 0 0 0 co m 00 CO 0 T— T t 00 Is- T— co 0 co co oq T— 0 co LO CM CM CM Is- T— CO CM 0 0 0 0 0 0 < < < IS-o CJ) O O O O O O O 0 = = = = = = = = = = = = = = = = = = = = = = = = = 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 l i i i i i i i w w w w w w w w w w w w w w w o : > w 99 A 5 . To lerab le Dai ly Intake (TDl) calculat ions based on the mean, maximum, and minimum (dry weight and wet weight) inorganic arsen ic concentrat ions (shown in bold) in different plant samples. Tab les are differentiated by spec ies and locat ion (1, 2, or 3); a b s e n c e of a location indicates concentrat ions were undetectable (age and body weight c l a s s e s from Health C a n a d a (1996)). Mt. Nansen property: Labrador T e a : Locat ion 1 Body T D l (g/d) A g e weight Max. Min . Min . (kg) M e a n (wet) M e a n (dry) Max. (wet) (dry) (wet) (dry) 2.097 7.033 9.78 32.1 0.1 0.4 0 to <6 months 7 6.7 2.0 1.4 0.4 140.0 35.0 6 months to <5 13 years 12.4 3.7 2.7 0.8 260 .0 65.0 5 to <12 years 27 25.8 7.7 5.5 1.7 540.0 135.0 12 to <20 years 57 54.4 16.2 11.7 3.6 1140.0 285.0 20+ years 70 66.8 19.9 14.3 4.4 1400.0 350.0 Labrador T e a : Locat ion 2 Body T D l (g/d) A g e weight Max. Min . Min. (kg) M e a n (wet) M e a n (dry) Max. (wet) (dry) (wet) (dry) 0.160 0.500 0.42 1.2 0.06 0.2 0 to <6 months 7 87.5 28.0 33.3 11.7 1458.3 140.0 6 months to <5 13 years 162.5 52.0 61.9 21.7 2708.3 260.0 5 to <12 years 27 337.5 108.0 128.6 45.0 5625.0 540.0 12 to <20 years 57 712.5 228.0 271.4 95.0 11875.0 1140.0 20+ years 70 875.0 280.0 333.3 116.7 14583.3 1400.0 Labrador tea: Locat ion 3 Body T D l (g/d) A g e weight Max. Min . Min. (kg) Mean (wet) M e a n (dry) Max. (wet) (dry) (wet) (dry) 0.037 0.101 0.15 0.4 < DL <DL 0 to <6 months 7 375.0 139.1 93.3 35.0 N/A N/A 6 months to <5 13 years 696.4 258.3 173.3 65.0 N/A N/A 5 to <12 years 27 1446.4 536.4 360.0 135.0 N/A N/A 12 to <20 years 57 3053.6 1132.5 760.0 285.0 N/A N/A 20+ years 70 3750.0 1390.7 933.3 350.0 N/A N/A 100 Wi l low leaves: Locat ion 1 Body TDI (g/d) A g e weight Max. M in . Min. (kg) M e a n (wet) M e a n (dry) Max. (wet) (dry) (wet) (dry) 0.987 4.043 5.26 22.1 0.12 0.4 0 to <6 months 7 14.2 3.5 2.7 0.6 116.7 35.0 6 months to <5 13 years 26.3 6.4 4.9 1.2 216.7 65.0 5 to <12 years 27 54.7 13.4 10.3 2.4 450.0 135.0 12 to <20 years 57 115.5 28.2 21.7 5.2 950.0 285.0 20+ years 70 141.8 34.6 26.6 6.3 1166.7 350.0 Wi l low leaves: Locat ion 2 Body TDI (g/d) A g e weight Max. Min . Min. (kg) M e a n (wet) Mean (dry) Max. (wet) (dry) (wet) (dry) 0.071 0.3 0.14 0.7 < DL <DL 0 to <6 months 7 197.2 46.7 100.0 20.0 N/A N/A 6 months to <5 13 years 366.2 86.7 185.7 37.1 N/A N/A 5 to <12 years 27 760.6 180.0 385.7 77.1 N/A N/A 12 to <20 years 57 1605.6 380.0 814.3 162.9 N/A N/A 20+ years 70 1971.8 466.7 1000.0 200.0 N/A N/A Wi l low leaves: vocation 3 Body TDI (g/d) A g e weight Max. M in . Min. (kg) M e a n (wet) Mean (dry) Max. (wet) (dry) (wet). (dry) 0.011 0.034 0.06 0.2 < D L <DL 0 to <6 months 7 1272.7 411.8 233.3 70.0 N/A N/A 6 months to <5 13 years 2363.6 764.7 433.3 130.0 N/A N/A 5 to <12 years 27 4909.1 1588.2 900.0 270.0 N/A N/A 12 to <20 years 57 10363.6 3352.9 1900.0 570.0 N/A N/A 20+ years 70 12727.3 4117.6 2333.3 700.0 N/A N/A 101 Mushroom: Locat ion 1. A g e Body weight (kg) M e a n (wet) 0.055 M e a n (dry) 0.458 TDI (g/d) Max. (wet) 0.19 Max. (dry) 1.4 Min . (wet) < D L Min. (dry) <DL 0 to <6 months 7 254.5 30.6 73.7 10.0 N/A N/A 6 months to <5 years 13 472.7 56.8 136.8 18.6 N/A N/A 5 to <12 years 27 981.8 117.9 284.2 38.6 N/A N/A 12 to <20 years 57 2072.7 248.9 600.0 81.4 N/A N/A 20+ years 70 2545.5 305.7 736.8 100.0 N/A N/A Mushroom: Locat ion 2. A g e Body weight (kg) M e a n (wet) 0.532 Mean (dry) 5.125 TDI (g/d) Max. (wet) 3.69 Max. (dry) 34.8 Min . (wet) < D L Min. (dry) <DL 0 to <6 months 7 26.3 2.7 3.8 0.4 N/A N/A 6 months to <5 years 13 48.9 5.1 7.0 0.7 N/A N/A 5 to <12 years 27 101.5 10.5 14.6 1.6 N/A N/A 12 to <20 years 57 214.3 22.2 30.9 3.3 N/A N/A 20+ years 70 263.2 27.3 37.9 4.0 N/A N/A Venus Mine tailings site: Raspber r ies : Locat ion 1 Body TDI (g/d) A g e weight M e a n M e a n Max. Max. M in . Min. (kg) (wet) (dry) (wet) (dry) (wet) (dry) 0.17 0.775 0.25 1.2 0.11 0.4 0 to <6 months 7 81.2 18.1 56.0 11.7 127.3 35.0 6 months to <5 years 13 150.7 33.5 104.0 21.7 236.4 65.0 5 to <12 years 27 313.0 69.7 216.0 45.0 490 .9 135.0 12 to <20 years 57 660.9 147.1 456.0 95.0 1036.4 285.0 20+ years 70 811.6 180.6 560.0 116.7 1272.7 350.0 102 A 6 a . G lossa ry of common plant compounds (from Mar ies et a l . (2000)) alkaloid - bitter tasting compounds produced naturally by plants and used for herbivore de fense (affects their nervous system) flavonoid- important antioxidant iridoid - deters herbivores and helps prevent bacterial infections salicylate - type of compound from which acety lesal icyc l ic ac id ( A S A or aspir in) was original ly synthes ized. Re l ieves pain, reduces fever, and acts as an anti-inflammatory. saponin - chemica l that acts like detergent, which froths if shaken in water. tannin - acts as an astringent (causing t issue to shrink and f luids to be retained); is effective at stopping bleeding and preventing infection when app l ied topical ly to cuts and sores. Ingesting large doses (e.g. strong tea) is damaging to the throat l ining. volatile/essential oil - aromatic oils with medic inal , industrial, and cosmet ic u s e s (e.g. components of c leaning suppl ies and aromatherapy). They evaporate easi ly . A 6 b . G lossa ry of se lec ted terms used in or related to this dissertat ion bioaccumulation - ability of living organisms to accumulate e lements in concentrat ions higher than the median for the spec ies in an unpol luted environment (Wittig, 1993) cation exchange capacity (CEC) - the ability of a soi l to hold and exchange ions; organ ic matter and c lays are good ion exchangers as negat ive charges on soil co l lo ids attract cat ions (Fergusson, 1990) contaminant - a substance whose presence causes a deviat ion from the normal composi t ion of the environment (Environmental Sc i ences Group , 1995) ligand - a subs tance that binds with another, such as an organic molecu le with a metal (Rip ley etal., 1996) metalloids/semi-metal - elements that exhibit only a partial metal l ic character or they occur in metal l ic as well as non-metal l ic form (Streit and Stumm, 1993) phytotoxicity - toxic to plants (Ripley et al., 1996) pollutant - a subs tance that has a detrimental effect on the environment (Environmental S c i e n c e s Group, 1995) reclamation - an approximation of pre-disturbance condi t ions with an emphas is on the re-establ ishment of native spec ies . Genera l ly inc ludes any treatment that is not restoration, where pre-mining condit ions need not be restored but rather where a different condit ion is establ ished that is appropriate to surrounding land uses and condi t ions (Bowman and Baker, 1998) rehabilitation - the return of a disturbed site to a stable and permanent use or condit ion that is directed by a pre-mine plan. The use or condit ion must not contribute to environmental deterioration and be consistent with surrounding aesthet ic va lues (Bowman and Baker, 1998) restoration - affected landscapes are restored to condit ions that ex isted prior to the disturbance in quest ion. This includes recreating the original topography and re-establ ish ing the previous land use or land condit ion, as wel l as groundwater patterns and plant and animal communit ies (Bowman and Baker , 1998) tailings - component of washed or milled ore that is too poor to be treated further; as dist inguished from the concentrates - the "materials of value" (Rip ley ef al., 1996) 

Cite

Citation Scheme:

        

Citations by CSL (citeproc-js)

Usage Statistics

Share

Embed

Customize your widget with the following options, then copy and paste the code below into the HTML of your page to embed this item in your website.
                        
                            <div id="ubcOpenCollectionsWidgetDisplay">
                            <script id="ubcOpenCollectionsWidget"
                            src="{[{embed.src}]}"
                            data-item="{[{embed.item}]}"
                            data-collection="{[{embed.collection}]}"
                            data-metadata="{[{embed.showMetadata}]}"
                            data-width="{[{embed.width}]}"
                            async >
                            </script>
                            </div>
                        
                    
IIIF logo Our image viewer uses the IIIF 2.0 standard. To load this item in other compatible viewers, use this url:
http://iiif.library.ubc.ca/presentation/dsp.831.1-0090884/manifest

Comment

Related Items