Author Institution: Department of Botany, The Ohio State Universit

Lawrey, James D.

Rudolph, Emanuel D.

The Ohio Journal of Science

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THE OHIO JOURNAL OF SCIENCEVol. 75 MAY, 1975 No. 3LICHEN ACCUMULATION OF SOME HEAVY METALS FROMACIDIC SURFACE SUBSTRATES OF COAL MINEECOSYSTEMS IN SOUTHEASTERN OHIO1JAMES D. LAWREY AND EMANUEL D. RUDOLPHDepartment of Botany, The Ohio State University, Columbus, Ohio 1+3210LAWREY, JAMES D. AND EMANUEL D.RUDOLPH. Lichen accumulation of someheavy metals from acidic surface sub-strates of coal mine ecosystems in South-eastern Ohio. Ohio J. Sci. 75(3): 113,1975.Surface coal mining results in the for-mation and release of sulfuric acid andthe mobilization of large quantities ofheavy metals. Terricolous lichens, par-ticularly those of the genus Cladonia, areimportant invaders on spoil material leftafter mining in Ohio, and are known tobe significant accumulators of variouselements. We analyzed lichen samplesand samples of the underlying substratefor P, K, Ca, Mg, Mn, Fe, Cu, Zn, Al,and Mo and found that lichens accumu-lated metals to many times the concentra-tions found in their substrates. Cla-donia cristatella samples washed withwater contained significantly less metals(Al, Fe, Mo) than the samples whichwere left untreated. Lichen material ex-tracted with acetone showed no sig-nificant drop in metal content comparedwith untreated lichens. The accumulat-ing nature of lichens in strip mine eco-systems makes them potential researchtools in mineral cycling studies.Surface coal mining involves the re-moval of the substrate overlying a coalseam which in the eastern U. S. is calledoverburden. It is usually high in sulfur-bearing pyritic compounds and sub-sequent weathering results in oxidationof the pyrites to sulfates. The resultantlow pH conditions contribute to in-1Manuscript received April 30, 1975, revisedJune 10, 1975 (75-25).creased solubility of numerous substrateelements, particularly metals (Grim andHill, 1974). The high concentrations ofheavy metals found in some strip minespoil materials are thought to be sig-nificant in limiting the successful re-establishment of vegetation, natural orintroduced, in these strip mine habitats(Barnhisel and Massey, 1969; Berg andVogel, 1973).Lichens appear to be among the moreimportant early invaders of some primarybare areas following surface mining.Huey (1973) sampled the lichen vegeta-tion which had colonized bituminous sur-face mines of various ages in Pennsyl-vania. She found that lichens, partic-ularly Cladonia spp., were an importantcomponent of the ground cover verysoon (as early as two years) after stripmines were abandoned and graded.Tuominen and Jaakkola (1973) reviewedmuch of the current literature regardinglichens as accumulators of minerals andradionuclides and indicated that theywere important accumulators of specificelements. In arctic ecosystems wherenutrients are frequently limiting, lichenshave been implicated as important trapsfor elements (Williams et al., 1975, inpress).The mechanism by which lichens ac-cumulate metals is an interesting prob-lem. One important role of lichens innature was considered to be rock weather-ing and soil formation. Lichens werethought to be significantly involved inbreaking down rock and contributing toprimary soil development and plant suc-cession. Whether or not this hypothesisis true, it stimulated research into themechanisms by which lichens are able to114 JAMES D. LAWREY AND EMANUEL D. RUDOLPH Vol. 75bind substrate elements. The lichencompounds, those chemical compoundswhich are uniquely characteristic oflichen species and used extensively inlichen systematics, were thought to beinvolved. These compounds often con-tain polar groups (such as -OH, -CHO,-COOH) which are capable of donatingelectrons. Two such groups when inortho positions favor chelation of cations(Iskandar and Syers, 1972; Williams andRudolph, 1974). The water solubility ofthe lichen compounds is also determinedby the number of these polar donorgroups. Iskandar and Syers (1971), in-dicated that the solubility of these com-pounds is very low in water but theybelieve that the water solubility of thesecompounds is sufficient to allow them toparticipate in rock weathering. Williamsand Rudolph (1974) showed that squa-matic acid from Cladonia squamosachelated iron, to a certain extent, fromsouthern Ohio sandstone. Fumarproto-cetraric acid from Parmelia conspersa,has been found to have a chelatingcapacity (Syers, 1969) and Iskandar andSyers (1972) showed that significantamounts of Ca, Mg, Fe and Al werecomplexed by lichen acid compounds.Syers and Iskandar (1973) recently re-viewed the current research on metalaccumulation by lichensSTUDY AREAWe collected lichens in NE sec 16,Clayton township, Perry Co., Ohio, aportion of a large (1782 ha.) reclamationarea presently owned by the State ofOhio. Extensive strip mining activiesfrom 1948 to 1960 have left a large por-tion of the area barren of all but scatteredand transient vegetation. In those sec-tions which have become secondarily re-forested, black locust (Robinia pseudo-acacia) is dominant over other less nu-merous deciduous tree species. In vari-ous places where original revegetation at-tempts were successful, red pine (Pinusresinosa) is now dominant. Blackberries(Rubus spp.) are the dominant shrubspecies in all places. Lindsay (1974) ex-amined the elemental content of numer-ous vascular plant species from this areato determine the suitability of strip minehabitats for wildlife. She found thatnumerous important forage species con-tained high amounts of metals. Al-though lichens, mosses and some her-baceous plants are commonly abundant,approximately 15% of the total surfacearea is primarily bare and devoid of allvegetation (Bookhout et al., 1967).Our study reports on the elementalcomposition of Cladonia spp. collected inan abandoned, severely disturbed acidsurface mine area in southeastern Ohio.The available amounts of heavy metalsin the subjacent substrates were analyzedand some preliminary evidence is pre-sented concerning the role of lichen acidsin binding metal cations by Cladoniacristatella.METHODSAVe collected samples of representative terri-colous lichens of the genus Cladonia, includingC. vertidllata (Hoffm.) Schaer., C. subcariosaNyl., C. capitata (Michx.) Spreng., C. cristatellaTuck., and C. sub tennis (Abb.) Evans. Thesewere handled with care to avoid contamination.Healthy podetia were clipped in the field, toremove them from their substrates, and werekept in paper envelopes. The substrate im-mediately subjacent to each lichen sampledwas collected to a depth of 1 cm and placed inpaper bags. Lichen material was oven dried24 h at 105° C and ground in a Wiley mill (20mesh screen). The concentrations of all ele-ments reported here were determined fromplant-ash solutions by spark-emission spectro-scopy by a method described by Jones andWarner (1969). The available concentrationsof Mn, Fe, Zn and Cu in the substrate sampleswere obtained by atomic absorption spectro-scopy.In order to determine the nature of the metal-accumulating mechanism of these strip minelichens, samples of the most numerous lichenfrom our study area, Cladonia cristatella, werecollected for laboratory treatment. The lichenacids characteristic of Cladonia cristatella(usnic, barbatic and didymic acids) are moresoluble in acetone than in water (Asahina andShibata, 1954). We extracted acetone-solubleand water-soluble substances, and then an-alyzed the washed lichen material that re-mained. All samples were air dried for 24 hat 25° C. One gram samples were then groundin a mortar and placed in 100 ml flasks. Halfthe flasks had 50 ml of acetone added, and tothe other half, 50 ml of double distilled waterwas added. The flasks were shaken con-tinuously for six h at 25° C. The lichen ma-terial was then filtered (Whatman #1 paper)and washed with 25 ml portions of eitheracetone or water. Then, all samples were ovendried for 24 h at 105° C, ground in a Wiley mill(20 mesh), and analyzed by emission spectro-scopy. Data obtained from the lichens washedwith acetone or water were then compared withNo. 3 STRIP MINE LICHENvS AND HEAVY METALS 115data from samples which had not been subjectedto an extraction treatment. Statistical evalua-tion by t test was done for the C. cristatelladata.RESULTS AND DISCUSSIONElemental analysis of five commonlyoccurring Cladonia spp. in the Perry Co.surface mine habitat (table 1) showedcomposition. The two lichen species col-lected under a Pinus resinosa canopy,Cladonia verticillata and C. subtenuis,contain lower amounts of Mo.Total amounts of metal elements inthe lichens were compared with availableamounts of the metals found in the sub-strate underlying each lichen collectedTABLE 1Total accumulated selected elements in Cladonia species from acidic surface coal minehabitats in Perry Co., Ohio.SpeciesOPEN HABITATCladonia cristatellaCladonia capitataCladonia subcariosaPINUS HABITATCladonia verticillataCladonia subtenuisP1600*1500150015001300K30003800300030003000Ca10001000100010001000Mg300300300300300Mn2727597640Fe152913153851085788Cu88187Zn2733373642Al16821829193613561293Mo5.2610.319.011.541.38"All data are expressed in ppm of oven dried weight.that concentrations of the macronutrientsP, K, Ca, Mg were extremely low. Thisis not surprising considering the smallamounts of these elements found in stripmine substrates (Plass and Vogel, 1973).The concentrations of trace metal cations,particularly Fe and Al, were high relativeto those observed for vascular plants inthe same area (Lindsay, 1974). Molyb-denum was also high in some species, afactor which may explain the low con-centration of Cu, to which Mo is prob-ably antagonistic. The species sampledshow a general similarity in elemental(Table 2). In all species sampled, thereare greater concentrations of each metalcation found in the lichen than availablein the subjacent substrate. This sug-gests that these lichen species accumu-lated Mn, Fe, Zn and Cu from the stripmine substrates. We were not able todetermine available Al for the substrates,but we would assume that the lichens alsoaccumulated Al to greater concentrationsthan are in available form in the sub-strate. The substrate pH data (table 2)indicate that these 15-25 year old surfacemine habitats are still being adverselyTABLE 2Total accumulated trace metal content and available substrate metal content forCladonia species and their substrates.MnSpeciestotallichenavail,substr.F e Zntotal avail,lichen substr.total avail,lichen substr.Cutotal avail,lichen substr.pHsubstrateOPEN HABITATCladonia cristaiella 27* 8 1529Cladonia capitata 27 10 1315Cladonia subcariosa 59 21 385P I N U S HABITATCladonia verticillata 76 14 1085Cladonia subtenuis 40 13 788183.33.43.53.73.6*A11 data are expressed as ppm of oven dried weight.116 JAMES D. LAWREY AND EMANUEL D. RUDOLPH Vol. 75affected by acid production. Thus, heavymetal mobilization is a continuing prob-lem. The pH levels of the substratesbeneath the Pinus resinosa canopy (forC. verticillata and C. subtenuis) areacidic, and unfavorably low for mostplants.These results indicate that Cladoniaspp. are locally important invaders andresidents in strip mine habitats withhighly acidic substrates. Lichens aresignificant heavy metal sinks capable ofaccumulating certain metal cations tomany times the concentrations found intheir associated substrates. Such lichensmay be important in trapping mobilizedmetals and removing them from surfacerun-off in disturbed ecosystems.The total amounts of metals in Cla-donia cristatella samples after washingand extracting with acetone or waterare shown in table 3. The untreatedThe pH of the lichen-water mixturesafter washing ranged from 4.7 to 6.0,but there was no correlation betweenthese pH levels and amounts of metalsextracted. Less metal was found in thematerial washed with water, suggestingthat the lichen acids are not contributingsignificantly to the accumulation of metalelements by Cladonia cristatella, but thatmetal cations are either adsorbed on thecell surfaces, or are loosely bound insidethe cells.There is contradictory evidence in therecent literature concerning the elutionof metals from lichen material with dis-tilled water. Subbotina and Tomoteeff-Ressovskii (1961) found that crustoselichens which had accumulated radio-active Fe and other metals releasedsignificant amounts of Fe in water solu-tions over a period of eight days. Thesedata support our findings. Brown andTABLE 3Total trace metal content of strip mine Cladonia cristatella samplesafter extraction with either acetone or water.Mn Fe Cu Zn Al MoCladonia cristatellauntreatedwashed six hourswith acetonewashed six hourswith water29 ± 6*20± 120±ll1226 ±4061140±378661 ±157***12±412±114±53710164± 9±21± 81498 ±1731529 ±1721078± 99**3.04±l2.32±0l . l l ± 0.69.61.15*A11 data expressed as ppm± standard deviation of oven dried weight (Sample Size N = 4).^Significantly less than untreated sample of 1% significance level.^Significantly less than untreated sample at 5% significance level.samples contain concentrations of metalscomparable to those found in the Cla-donia spp. from the original analyses(table 1). Those samples which werewashed with acetone do not contain sig-nificantly lower amounts of metal thanthe untreated samples. The sampleswashed with water exhibit concentrationsof Al, Fe and Mo which are signfiicantlylower than the untreated samples. Zincexhibited extreme variability from onethallus sample to another and appears toaccumulate unevenly. Zinc has been re-ported to have a wide range (up to 1000 X)of concentrations in lichens from thesame locality (Shimwell and Laurie,1972; Tuominen and Jaakkola, 1973).Slingsby (1972), however, found that dis-tilled water did not elute appreciableamounts of Pb or K from lichen ma-terial and Puckett et al. (1973) were un-able to elute significant amounts of metalions (Fe, Cu, Ni, Zn, Pb) from severallichen species, including Cladonia spp.They contended that ion exchange, ratherthan electrolyte sorption, was the mostimportant process involved in the accu-mulation of metals by lichens. Our datado not necessarily contradict their con-tention, but do indicate that under cer-tain circumstances, water does elute sig-nificant amounts of certain metals fromlichens.The fact that heavy metals may beNo. 3 STRIP MINE LICHENS AND HEAVY METALS 117removable by water is somewhat con-tradictory to our suggestion that lichensare metal accumulators in strip minehabitats. The natural situation, how-ever, is very different from our artificiallaboratory situation. In the strip minehabitat under low pH conditions, heavymetals become soluble. In this formthey are continually available for uptakeby lichens, especially during water move-ment. Under field conditions, the onlywater which participates in extraction isdue to natural precipitation. Rain wa-ter, particularly low pH rain water,probably removes small amounts of theheavy metals which were previously ac-cumulated by lichens. Lichen accumu-lation of heavy metals could occur con-comitantly with mobilization and re-lease of these metals during periods ofheavy precipitation. We suggest thatthe position lichens assume in the cyclingof minerals through these ecosystemsmakes them important components in theanalysis and modeling of such systems.Acknowledgments. We gratefully acknowl-edge the field and laboratory assistance ofPatricia Lawrey.LITERATURE CITEDAsahina, Y. and S. Shibata. 1954. Chemistryof lichen substances. Japan Soc. PromotionSci., Tokyo. [Engl trans]. 240 p.Barnhisel, R. I. and H. F. Massey. 1969.Chemical, mineralogical and physical prop-erties of eastern Kentucky acid-forming coalspoil materials. Soil Sci. 108: 367-372.Berg, W. A. and W. G. Vogel. 1973. Toxicityof acid-mine spoils to plants. Pages 57-68•in R. J. Hutnik and G. Davis, eds. Ecologyand Reclamation of Devastated Land. In-tern. Symp. on Ecology and Revegetation ofDrastically Disturbed Areas, Univ. Park,Pa.Bookhout, T. A., C. P. Stone, J. D. Bittner,R. A. Tubb, S. H. Taub, and R. E. Deis.1967. Potential of a strip-mined area for fishand wildlife reclamation. Report to U. S.Dept. Interior, Fish and Wildlife Service.The Ohio St. Univ. Res. Found. Proj. 2296.84 p.Brown, D. H. and D. R. Slingsby. 1972. Thecellular location of lead and potassium in thelichen Cladonia rangiferina (L.) Hoffm. NewPhytol. 71: 297-305.Grim, E. C. and R. D. Hill. 1974. Environ-mental protection in surface mining of coal.Nat. Environ. Res. Center. Office of R & D.U. S. E. P. A. Cincinnati, Ohio. Programelement No. 1BB040. 277 p.Huey, J. S. 1973. Lichen distribution andsuccession on selected sites of reclaimed bi-tuminous strip mines in Clearficld Co., Pa.Ph. D. thesis. The Ohio State Univ.,Columbus. 114 p.Iskandar, I. K. and J. K. Syers. 1971. Solu-bility of lichen compounds in water: pedo-genctic implications. Lichenologist 5: 45-50.and J. K. Syers. 1972. Metal complexformation by lichen compounds. J. Soil Sci.23:255-265.Jones, J. B. and M. H. Warner. 1969. An-alysis of plant-ash solutions by spark-emissionspectroscopy. Pages 152-160 in Develop-ments in applied spectroscopy. Vol. 7A.Plenum Press, N. Y.Lindsay, S. F. 1974. Nutritive values of veg-etation from strip mined areas in easternOhio. M. Sc. thesis. The Ohio State Univ.,Columbus. 107 p.Plass, W. T. and W. G. Vogel. 1973. Chemi-cal properties and particle-size distributionof 39 surface-mine spoils in southern WestVirginia. USDA Forest Serv. Res. Pap.NE-276. 8 p.Puckett, K. J., E. Nieboer, M. ]. Gorzynskiand D. H. S. Richardson. 1973. The uptakeof metal ions by lichens: a modified ion-exchange process. New Phytol. 72: 329-342.Subbotina, E. N. and N. V. Tomoteeff-Res-sovskii. 1961. The accumulation of somedispersed elements in water solutions bycrustose lichens. [In Russian, Eng. sum.].Bot. Zhurn. Kyyiv. 46: 212-221.Shimwell, D. W. and A. E. Laurie. 1972.Lead and zinc contamination of vegetationin the southern Pennines. Environ. Pollut.3: 291-301.Syers, J. K. 1969. Chelating ability offumarprotocetraric acid and Parmelia con-spersa. Plant Soil 31: 205-208.and I. K. Iskandar. 1973. Pedogeneticsignificance of lichens. Pages 225-244 in V.Ahmadjian and M. E. Hale, eds. TheLichens. Academic Press, N. Y.Tuominen, Y. and T. Jaakkola. 1973. Ab-sorption and accumulation of elements.Pages 185-223 in V. Ahmadjian and M. E.Hale, eds. The Lichens. Academic Press,N. Y.Williams, M. E. and E. D. Rudolph. 1974.The role of lichens and associated fungi in thechemical weathering of rock. Mycologia 66:648-660., E. D. Rudolph, E. A. Schofield andD. C. Prasher. 1975. The role of lichensin the structure, productivity and mineialcycling of the wet coastal tundra at Barrow,Alaska. The Bryologist (in press).

Lichen Accumulation of Some Heavy Metals from Acidic Surface Substrates of Coal Mine Ecosystems in Southeastern Ohio

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Lichen Accumulation of Some Heavy Metals from Acidic Surface Substrates of Coal Mine Ecosystems in Southeastern Ohio

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