Original Research Bioavailability of Lead, Cadmium, and Nickel in Tatra Mountain National Park Soil

Transcription

1 Pol. J. Envion. Stud. Vol. 21, No. 2 (2012), Oiginal Reseach Bioavailability of Lead, Cadmium, and Nickel in Tata Mountain National Pak Soil Jezy Kwapuliński, Andzej Paukszto, Łukasz Papotny*, Renata Musielińska, Jolanta Kowol, Ewa Nogaj, Robet Rochel Depatment of Toxicology, Silesian Univesity of Medicine, Jagiellońska 4, Sosnowiec, Poland Received: 2 June 2011 Accepted: 15 Septembe 2011 Abstact Ou eseach investigated the bioavailability of Pb, Cd, and Ni in the soil of Tata Mountain National Pak (Chochołowska Valley, Kościeliska Valley, Małej Łąki Valley, and Stążyska Valley). The content of Pb, Cd, and Ni was estimated using the ASA method with accuacy of 0.1 µg/g. Rudd's methodology was applied to estimate diect and indiect bioavailability of the metals in question. Ions of Pb in pevailing amounts occu in indiectly bioavailable foms of cabonates and oganic compounds. Content of Pb and Ni as scace paticles is much highe in compaison to an aveage content of Cd in the soil. The amounts measued coesponding to 10 pecentile and geometic mean can be used as a efeence value in pospective eseach held in Tata Mountain National Pak o in othe potected aeas. Keywods: Tata Mountain National Pak, soil, metals, bioavailability, speciation analysis Intoduction Inceasing awaeness of the danges aising fom natual envionmental pollution makes it necessay to maintain egula checkups of the content of toxic elements and compounds in ai, soil, and food [1]. Fom among substances that have the most negative influence on the natual envionment, ions of metals of toxic chaacte have been in the cente of attention ecently. Thei toxicity consists in the ability to cumulate in living oganisms and thei chonic toxicity [2]. A natual souce of metals fo people and animals togethe with paticula matte absobed while beathing is plant mateial [12]. The main souce of contamination of plants with the metals in question on teitoy beyond the each of industial pollution, municipal waste, and that ceated by motoization is dust settled on leaves and on the soil itself, and the content of metals in it depends on the geochemical chaacteistics * lukasz.pap@wp.pl of the host ock and pedogenesis [3, 13, 14]. Compounds of most metals, especially the most toxic ones, ae easily soluble in soil solution and theefoe ae easily absobed by plants. Distibution of diffeent types of contamination in the natual envionment takes place between: atmospheic falls and soil onto which also fall dusts fom the ai. The migation of the metals in the soil is detemined by the soil s chemical, biological, and physical chaacteistics. In the pocesses of metal distibution in the system: atmospheic fall soil, the phenomenon of bioavailability in toxicological phase is of majo impotance. This phenomenon consists of the fom change of the xenobiotic, e.g. lead cabonate, which is less soluble, takes the fom of a chloide in consequence of the pocesses taking place in the suface laye, and theefoe is easily soluble. Anothe manifestation of this phenomenon is the diffeent chaacteistics of the way the chosen elements co-exist sepaately, e.g. in the dust suspended in the ai o in the total fall in compaison to soil solution. This leads to the fact that in

2 408 Kwapuliński J., et al. consequence of accumulation by subteanean pats of plants, a phenomenon of competition fo the ecepto, which might be a oot fo example, may occu [15-18]. Besides, in the teitoy of Tata Mountain National Pak long ange emission has been obseved, fequently with a souce located hundeds of kilometes away. The occuence of this phenomenon is poven by eseach on adium 226 distibution, namely on the glacie in Pod Chłopkiem Pass at Moskie Oko. The amount of this adioisotope, as a esult of pemanent emission is compaable to amounts occuing on the suoundings of Zabze [3]. Those dust pollutants mainly come fom the emission pocesses taking place while buning coal fo heating. Having taken into account contempoay publications, in ode to chaacteize the phenomenon of migation and accumulation of specific ions of metals it is necessay to become familia with thei chemical foms in which they occu in soil. In this context, with egad to specific eseach goals thee ae a few speciation methods available that concen soil. These fixed foms of occuence decide about ecotoxicological o physiological impotance of a paticula element in a tophic chain of plants, animals and humans [3-5, 19]. An illustation to that issue may be the outcome of eseach showing the content of those elements in a shinebone head among the inhabitants of Zakopane. The amounts wee as follows: Pb (12.92 µg /g), Ni (0.79 µg/g), and Cd (0.77 µg/g) [6]. Attention should be dawn to the fact that thee ae similaities between inhabitants of Zakopane and those living close to industial plants: µg/g as a esult of ca fume emissions as well as low emissions within the gounds of Zakopane. Speciation analysis is contempoaily consideed an appopiate method to specify the metal content in soil [6]. The synthetic emaks justify eseach, and as may be concluded fom publications, the fist of its kind dealing with bioavailability of Pb, Cd, and Ni in the soil of Tata Mountain National Pak. The infomation obtained makes a solid basis to estimate the eal ecotoxicological quality of soil in elation to specific popeties of thei accumulation by vaious plants. The point of ou eseach was to estimate the quantity of diectly and indiectly bioavailable Pb, Cd, and Ni in the soil fom the Pak. Reseach Methodology Pb, Cd, and Ni content was maked in 60 samples of soil taken in 2008 fom fou sites: Chochołowska Valley, Stążyska Valley, Kościeliska Valley, and Małej Łąki Valley. Specifying the chemical fom of the metals pesent in soil was done using Rudd s method (1988), consisting of a sequenced extaction using appopiate solutions at atio 1:40 at the mass of a 1g of soil with the following solutions: fo exchangeable fom: 1.0 M KNO 3 atio 1:40 fo adsobed fom: 0.5 M KF (ph=6.5) atio 1:40 fo oganic solution: 0.1 M Na 4 P 2 O 7 atio 1:40 fo cabonates: 0.1 M EDTA (ph=6.5) atio 1:40 fo sulphides: 6.0 M HNO 3 atio 1:40 fo esidues: 5 ml HNO 3 (twice) Soil sample was 10 cm 10 cm, taken in an open aea, without the undegowth fom a suface laye at a depth of 5 cm. Ai died, cushed, and sceened with a 1 mm sieve, soil was exposed to espective solutions fo 24 hous, then centifuged fo 10 minutes (4,000 pm), flushed with 25 cm 3 of edistilled wate, and centifuged fo 5 min (4,000 pm). The obtained extacts wee acidified with 1% HNO 3. The eagents used wee spectally pue made by Meck s (Supa Pue). Fo each seies of measues taken thee wee thee blank tests. The esults coming out of 6 samples wee coected with egad to values of blank tests. The content of heavy metals in the tested samples was maked using flame method ASA, with the use of a Philips Pye Unicam SP-9 spectophotomete at accuacy of 0.01 µg/g. Recovey fo the analytical pocedues applied was in-between % and contolled using patten solutions poduced by WZORMAT containing Pb, Cd, and Ni within the ange of concentation in soil. Results Content values found in ou eseach comply with nonpaametic distibution. Theefoe, to discuss the issue of bioavailability of the metals in question, geometical aveage was applied (Table 1). The esults pesented show vaiation with egad to the aea of occuence in espective chemical foms. Consideing the aveage values of metal content in the soil, the following may be pesented espectively to the place of occuence [µg/g]. Chochołowska Valley: exchangeable fom: Pb (5.78) > Cd (0.22) > Ni (0.02) adsobed fom: Pb (1.98) > Ni (1.97) > Cd (0.31) oganic solution: Pb (19.01) > Cd (1.47) > Ni (1.33) cabonates: Pb (34.05) > Ni (4.06) > Cd (1.07) sulphides: Pb (6.73) > Ni (4.12) > Cd (0.91) Kościeliska Valley: exchangeable fom: Pb (2.19) > Ni(1.01) > Cd (0.11) adsobed fom: Ni (1.89) > Pb (1.67) > Cd (0.35) oganic solution: Pb (18.48) > Ni (2.32) > Cd (2.26) cabonates: Pb (55.52) > Ni (5.91) > Cd (1.66) sulphides: Ni (10.80) > Pb (7.87) > Cd (0.98) Stążyska Valley: exchangeable fom: Pb (4.23) > Ni (0.21) > Cd () adsobed fom: Pb (1.77) > Ni (0.82) > Cd (0.23) oganic solution: Pb (17.76) > Cd(1.93) > Ni (0.85) cabonates: Pb (37.54) > Ni (3.07) > Cd (1.31) sulphides: Pb(5.16) > Ni(1.51) > Cd (0.98) Małej Łąki Valley: exchangeable fom: Pb (2.22) > Ni (0.74) > Cd (0.14) adsobed fom: Pb (1.80) > Ni (0.92) > Cd (0.45) oganic solution: Pb (21.81) > Cd (2.38) > Ni (1.81) cabonates: Pb (49.11) > Ni (5.63) > Cd (1.53) sulphides: Ni (9.53) > Pb (7.96) > Cd (1.10)

3 Bioavailability of Lead, Cadmium, and Nickel Table 1. Aveage metal content values at diffeent sites [µg/g]. Metal Chochołowska Valley Kościeliska Valley Exchangeable fom Stążyska Valley Małej Łąki Valley Pb Cd Ni Adsobed fom Pb Cd Ni Oganic solution Pb Cd Ni Cabonates Pb Cd Ni Sulphides Pb Cd Ni The aveage values of Pb, Cd, and Ni ae pesented in Table 1. They clealy indicate a paallel occuence of Pb in diffeent foms, while in Chochołowska Valley the top amount of diectly bioavailable foms is 7.76 µg/g, whee indiectly bioavailable foms each the value of µg/g. The amounts of Pb in exchangeable fom ae appoximately 25 times highe in compaison to amounts of Cd, and 280 times highe in compaison to the amount of Ni. In an adsobed fom the amounts of Pb and Ni ae compaable end equal to 2 µg/g, being six times highe when compaed to Cd. In an aea scope, the highest amounts of Pb wee found in diectly bioavailable fom in Stążyska Valley (6 µg/g) and the amounts of indiectly bioavailable compounds of Pb ae compaable to those fom Chochołowska Valley. Howeve, it must be stessed that indiectly bioavailable Pb in Małej Łąki Valley was 73 µg/g. Simila amounts in indiectly bioavailable foms wee found in soil fom Kościeliska Valley (73 µg/g). As may be concluded fom Table 1. the main poblem of Pb, Ni, and Cd migation is connected with potentially exploiting thei souces fom oganic amalgames o thei cabonate foms. The highest amounts of Cd in an adsobed fom wee found in the soil fom Małej Łąki Valley, and they ae about 0.15 µg/g highe in compaison to othe examined locations in the pak. Indiectly bioavailable amounts of Cd pove these emaks. Vey chaacteistic fo Ni is its significant occuence in the fom of cabonates in Kościeliska Valley (5.91 µg/g), in Małej Łąki Valley (5.61 µg/g), and mino amounts in Stążyska Valley (3.07 µg/g). While an aveage ange of occuence fo Pb is µg/g in the exchangeable fom and µg/g in the adsobed fom, the aveage level of occuence of Cd in both foms equals fom 0.3 µg/g to 0.45 µg/g. A bigge vaiation in Ni occuence in those foms was obseved in an aea scope. It is even moe visible in the example of Ni occuence in the fom of oganic solution and cabonates. The above statistical chaacteistics of element occuence illustates the values coesponding to 10 and 95 pecentile and geometical aveage fo all Tata Mountain National Pak aeas (Table 2) and vaiation factos. Table 2. Statistical chaacteistics of metal occuence in speciation foms in in Tata Mountain National Pak soil [µg/g]. Metal 10 pecentile Geometical aveage Exchangeable fom 95 pecentile Vaiation facto [%] Pb Cd Ni Adsobed fom Pb Cd Ni Oganic solution Pb Cd Ni Cabonates Pb Cd Ni Sulphides Pb Cd Ni Residues Pb Cd Ni

4 410 Kwapuliński J., et al. The content values of the elements contained in soil in thei speciation foms clealy indicate that content values of Pb, Cd, and Ni in diectly available fom can be efeence values as occuing in an aea anthopogenically unchanged. But indiectly bioavailable foms of Pb with thei values at 10 pecentile indicate the long-tem influence of ca touism that has been inceasing. In the past 15 yeas Pb tansfeed to a soil envionment mainly as a esult of using lead tetaethyl in petol. Compaing the content values of Pb in an intechangeable fom o the adsobed one, as well as in the fom of sulphides and so-called est, it may be assumed that these foms ae of geochemical oigin, while Pb compounds in the fom of oganic solution and cabonates ae the esult of ca and industial as well as household fume emissions. Futhemoe, it is poven by the fact that the vaiation facto is simila and equals fo Pb 47% fo oganic amalgames and fo cabonates 48%. The constant influence of pollutant emissions containing Pb, Cd, and Ni, which ae chaacteistic fo automobile emission, accoding to publications, take effect in less vaiability in occuence of these foms in compaison to diectly bioavailable foms. Fo example, vaiations in occuence of Pb in its intechangeable fom is thee times highe in compaison to oganic compounds and cabonates of that metal. Vaiation in occuence of Cd and Ni is much highe as well in both foms, intechangeable and adsobed and values, espectively (Cd 270% and 105%), in compaison to oganic amalgames 33% and cabonates 36%. Likewise, the vaiation of Ni in diectly bioavailable fom equals, espectively, 188% and 82%, and is much highe in compaison to diectly bioavailable foms. As chaacteistic content values fo the elements eseached in soil fom Tata Mountain National Pak, the following may be assumed: Pb in exchangeable fom (3.6 µg/g), in adsobed fom (1.50 µg/g), in oganic solution (19.3 µg/g), and in the fom of cabonates (4.0 µg/g). The amounts of Cd in espective foms each: 0.12 µg/g, 0.33 µg/g, 2.0 µg/g, and 1.4 µg/g. An aveage value of Ni content in exchangeable fom and the adsobed one equals 0.5 µg/g and 1.40 µg/g. In oganic solution and cabonates the values ae 1.58 µg/g and 4.67 µg/g. It must be stessed that fo the pupose of foecasts of ecological changes fo this aea o fo any othe potected aeas the content values coesponding to 95 pecentile ae of significant impotance, and it must be noted that they ae easonable at a level of contempoaily obseved local emissions and the intensity of taffic. As the soil is an element of the envionment chaacteized by emakable ability of bio-chemical changes taking place, fo example, in a plant oot zone, it might be expected that chemical phenomena chaacteistic by thei numbe will occu. Thei illustations ae not only aveage levels of occuence and thei vaiation, but the chaacte of cooccuence of Pb, Cd, Ni in a paticula speciation fom with othe metals in Tata Mountain National Pak (Figs. 1-6, Table 3). It tuned out that Pb content changes emakably, in a diectly popotional way in exchangeable fom, with Zn, whee the occuence of Ni is invesely popotional with C Fig. 1. Co-occuence of Pb, Cd, and Ni in exchangeable fom with othe metals in the soil in Tata Mountain National Pak fo 0.3 p < 0.05; 0.5 p < 0.01; 0.7 p < Fig. 2. Co-occuence of Pb, Cd, and Ni in adsobed fom with othe metals in the soil in Tata Mountain National Pak fo 0.3 p < 0.05; 0.5 p < 0.01; 0.7 p < Fig. 3. Co-occuence of Pb, Cd, and Ni in oganic solution with othe metals in the soil in Tata Mountain National Pak fo 0.3 p < 0.05; 0.5 p < 0.01; 0.7 p < Fig. 4. Co-occuence of Pb, Cd, and Ni in fom of cabonates with othe metals in the soil in Tata Mountain National Pak fo 0.3 p < 0.05; 0.5 p < 0.01; 0.7 p < 5.

5 Bioavailability of Lead, Cadmium, and Nickel Fig. 5. Co-occuence of Pb, Cd, and Ni in the fom of sulphides with othe metals in soil in Tata Mountain National Pak fo 0.3 p < 0.05; 0.5 p < 0.01; 0.7 p < 5. Fig. 6. Co-occuence of Pb, Cd, and Ni in est foms with othe metals in soil in Tata Mountain National Pak fo 0.3 p < 0.05; 0.5 p < 0.01; 0.7 p < 5. Amounts of exchangeable Cd foms change diectly popotionally with Mn and Zn. The numbe of significant inteactions with othe elements is geate in the case of adsobed foms. Adsobed foms of Pb, Cd, and Ni decide lagely about thei chemical inteactions. The geat elationship of Ni with Co and C and foms of oganic solution appeaed to be inteesting as well as in cases of Cd with Mn, Zn, and Pb. Pb showed high elation to changes in Zn and Cd content, which ae chaacteistic fo dusts poduced while bake pads ae ginding. The analysis of the chaacte of co-occuence of Pb, Cd, and Ni pesent in paticula speciation foms clealy suggests an ode that involves not only all the elements, but also the stenght of thei intedependence with cabonates of the metals in question. Vey stong intedependence of diectly popotional chaacte of Pb, Cd, and Ni concen Mn ( ) and Cu ( ). It must be stessed that the stongest elationships chaacteized by common coelation above 0.85 concened Cd with Pb and Ni with Pb and Cd (0.55-). Compaing the diagams pesented concening Ni, two popotional changes with cabonates Mn (0.67), Cu (0.64), Co (0.65), and Cd (0.6) of that element can be indicated. The smallest elation fom among the elements examined (Pb, Cd, and Ni) is to cabonate compounds of C. A supplement of the issue discussed ae the esults showing intedependence of Cd, Pb, and Ni with sulphides and so-called est. Two ae the most significant. Diectly popotional changes of Ni with C, Co, Cu, and Mn in the fom of sulphides, and to a lesse extent in the fom of socalled est. In a fom of est, two popotional changes stand out in the occuence of Pb with Cd and Zn, and to a lesse extent with Cu and Co. Attention must be paid to invesely popotional changes of Pb and Cd in the fom of sulphides. Discussion Reseach concening the occuence and co-occuence of Pb, Cd, and Ni in pak soil efes to contempoaily obseved eseach tends concening potected aeas, as well as to 12 theses included in the Euopean Soil Chat. Evey potected aea is influenced by a specific dust emission that diffes not only at thei dispesibility but also at thei pecentage of occuence of each of the elements mentioned, thei function, and aveage dust diamete. The aea of the pak is diffeentiated when it comes down to the content of Zn and C (57 µg/g). Additionally, these soils diffe in thei suface laye density that vaies fom 0.7 g/cm 3 fo the soil in Kuźnice and Myślenickie Tunie to 0.57 g/cm 3 fo the soil fom Świnicka Pass. Reseach conducted by Stobiński indicates the inceasing tendency in Zn and C content following the depth at which the samples wee taken. This vey fact, and the gowing automotive pesence in Zakopane Valley, diected inteest to Pb, Cd, and Ni as elements chaacteistic of automotive emissions. Zn and C content change, accoding to Stobiński s eseach, shall be connected with thei content in paent ock. What is moe, Pb, Cd, and Ni content values wee measued in elation to the species of tees pesent in a paticula aea, unlike in Kościeliska Valley, whee Pb content in diectly available foms was 2.5 times highe in compaison to Pb content in the same fom in Chochołowska Valley. The diffeentiating factos wee pedominant maples and sycamoes in Chochołowska Valley, while beeches dominated Kościeliska Valley. That obsevation also poved to be ight in the case of Stążyska Valley, whee soils fom the beech habitat also contained highe amounts of intechangeable foms of Pb, simila to Chochołowska Valley. Howeve, maple and sycamoe habitats wee affected, as it tuned out, in highe amounts of Pb and Ni in adsobed fom. Indiectly bioavailable content values of Pb in soil vaied fom µg/g, Cd: µg/g, and Ni: µg/g, and was getting homogenous as a esult of the pesence of thee species of sycamoe tees, beech, and spuce. That specific aveage may be obseved on the example of content values of Pb, Cd, and Ni in all foms of occuence (Table 1) in the soil fom Małej Łąki Valley. Physiogaphic chaacteistics of the fou valleys fom Tata Mountain National Pak clealy indicated the possibility of the penetation of the valleys by pollution in indiectly bioavailable foms. The valleys in question ae of closed chaacte and contempoay winds make them exposed to pevailing pollution fom ca emissions [7]. The poblem of heavy metals pesent in plants may also be connected with food poisoning. Contaminants and adulteants of medicinal plants can be phamacologically active

6 412 Kwapuliński J., et al. Table 3. Co-occuence of Pb, Cd, and Ni with othe metals in diffeent chemical foms. Metal Exchangeable fom Pb Cd Ni Adsobed fom Pb Cd Ni Oganic solution Pb Cd Ni Cabonates Pb Cd Ni Sulphides Pb Cd Ni Residues Pb Cd Ni and esponsible fo unexpected toxicity. Plants used in taditional medicine may be havested fom contaminated soils o cleaned impopely such that they may contain illness-poducing micooganisms. Ayuvedic medications, fo example, have been known to cause lead poisoning in childen because of thei contamination with this heavy metal and othes, such as asenic and mecuy, as has been signaled by Basha Saad et al. Contamination of cop and medicinal plant samples by oganic chemicals has become a pessing poblem in many Aab counties. This poblem, howeve, does not concen Tata Mountains National Pak and is quoted hee meely in ode to indicate potential isk involved while discussing the link between taditional medicine and heavy metals contamination. Most epots of toxic effects due to the use of hebal medicines and dietay supplements ae associated with hepatotoxicity (HT), although epots of othe toxic effects, including kidney, nevous system, blood, cadiovascula and dematologic effects, mutagenicity, and cacinogenicity, have also been published in medical liteatue. Hepatic impaiment esulting fom the use of conventional dugs is widely acknowledged, but thee is less awaeness of the potential HT of hebal pepaations and othe botanicals, many of which ae believed to be hamless and ae commonly used fo self-medication without supevision [8]. Wu et al. in thei pape pesent how Pseudomonas putida, a obust and vesatile antifungal hizosphee bacteium, is engineeed to poduce MBP-EC20, a metal-binding peptide that has high affinity fo cadmium. P. putida is also modestly cadmium esistant, due to the pesence of an efflux pump in the metalloegulatoy cad opeon. Poduction of MBP-EC20 in P. putida not only enables enhanced cadmium binding but also potects the engineeed stain and the colonized sunflowe plants against the toxic effects of cadmium. These esults demonstate that a combination of enhanced micobial biosoption and plantbacteium symbiosis is a pomising stategy fo heavymetal cleanup [9].

7 Bioavailability of Lead, Cadmium, and Nickel If othe plants wee to illustate the pesence of heavy metals in paticula pats, a tea plant would be a good example to show that pevailing metals ae accumulated in subteanean pats. Tea plants gown on un-contaminated soil showed simila As and Cd distibution. Concentations of As and Cd in feeding oots wee 2~50 times highe than those in stems o main oots, 5~100 times highe than those in old leaves, and 25~600 times highe than those in young shoots, suggesting that feeding oots wee the main accumulation ogan. The concentation of As and Cd in tea plants was in the ode: feeding oots > stems main oots > old leaves > young shoots [10]. Anothe plant that had been examined in ode to find a elationship between metals pesent in it was ice Genotypic and envionmental vaiation in Cd, C, As, Ni, and Pb concentations of gains, and the elationships between these heavy metals and Fe and Zn wee investigated in 2006 by Cheng et al. using 9 ice genotypes gown in 6 locations fo two successive yeas. Significant genotypic vaiation was detected in the five heavy metal concentations in gains, indicating the possibility of educing the concentation of these heavy metals in gains though beeding appoach. The envionmental effect vaied with metal, with Pb and Ni having geate vaiation than the othe thee metals. Thee was significant genotype-envionment (location) inteaction of the concentations of all five heavy metals in gains, suggesting the impotance of cultiva choice in poducing ice with low heavy metal concentations in gains fo a given location. Coelation analysis showed that Cd and As, C and Ni, and As and Pb concentations in ice gains wee closely associated, and that Ni concentation in gains is negatively coelated with Zn concentation [11]. Conclusions 1. Fo the need of estimating the tendency in changes of metals of anthopogenic oigin content in soil in Tata Mountain National Pak a statistical chaacteistics of occuence and co-occuence was established fo Pb, Cd, and Ni with othe metals. That chaacteistics may be applied to estimate the pollution level of potected aeas. 2. In potected aeas, on the example of Tata Mountain National Pak, indiectly bioavailable foms of metals will be pedominant ove the foms diectly bioavailable as a esult of a complex influence of local ca emission, heating emissions fom individual households and seconday foest dusting Pb. 3. Co-occuence of Pb and Cd was diffeentiated in tems of fom of occuence, the kind of metal and the sample site location as well as a tee habitat and species content of tees. Refeences 1. KOCJAN R., KOT A., PTASIŃSKI H. Chomium, zinc, coppe, nickel, cadmium and lead content in vegetables and fuits fom aeas of Stalowa Wola. Bomatol. Chem. Toksykol. 1, 31, SADY W. Factos limiting the nitate and heavy metals content in vegetables. Pzem. Fement. Owoc.-Wazyw. 5, 21, JAWOROWSKI Z. Ra-226 in the ice cap on the Chłopek Pass. Health Physics, 20, 675, GORLACH E., GAMBUŚ F. Potentially toxic tace elements in the soil (the excess, the hamfulness and the counteaction. Zesz. Pobl. Post. Nauk Roln. 472, 275, SINGH R. B., KABAŁA C. Distibution and Fom of Cadmium In Soils Nea a Coppe Smelte. Pol. J. Envion. Stud. 15, 90, BRODZIAK B., KWAPULIŃSKI J., RZEPKA J. Application of femu capitulum In estimation of the exposue to the selected heavy metals In inhabitants industial and eceations egions. Med. Śod. 7, (2), 105, KWAPULIŃSKI J., BEBEK M., MITKO K., FISCHER A., WIECHUŁA D. Analysis of the impact of fuel stations on the degee of soil contamination with heavy metals. Poblems of Ecology. Poblemy Ekologii, 11, 2, 101, SAAD B., AZAIZEH H., ABU-HIJLEH G., SAID O. Safety of Taditional Aab Hebal Medicine, Advance Access Publication. 3, (4), 433, WU H. C., WOOD K. T., MULCHANDANI A., CHEN. W. Engineeing Plant-Micobe Symbiosis fo Rhizoemediation of Heavy Metals. Depatment of Chemical and Envionmental Engineeing and Envionmental Toxicology Pogam, 72, (2), 1129, YUAN-ZHI SHI, JIAN-YUN RUAN, LI-FENG MA, WEN-YAN HAN, FANG WANG. Accumulation and distibution of asenic and cadmium by tea plants. J Zhejiang Univ. SCIENCE B, 9, (3), 265, CHENG WANG-DA, ZHANG GUO-PING, YAO HAI- GEN, WU WEI, XU MIN. Genotypic and envionmental vaiation in cadmium, chomium, asenic, nickel, and lead concentations in ice gains. J Zhejiang Univ. SCIENCE B, 7, (7), 565, STURSA J., MAZURSKI K. R. Coexistence individual heavy metals in Digitalis pupuea in the Giant Mountains in Beskidy Silesian egion. Poceedings Inten. Confe. Geological Poblems of the Giant Mountains Kakonosze National Pak. 1, 194, Some poblems of seconday emission fom polluted foest in Uppe Silesia Poland. Poceedings. Expetentagung Waldschadensfoschung in ostlichen Mitteleuopa und Bayen, GSF Beicht 29/ , The estimation of the level contamination of the ai nea foest shoe. Poceedings. Expetentagung Waldschadensfoschung in ostlichen Mitteleuopa und Bayen, GSF Beicht 29/91, , The compae of the investigation of an occuence of the metals in Taaxacum officinale. Web. in Southen Poland. Opea Concotica. 37, 225, Specific adioactivity of the given medicinal plants Kakonosze Mountains. Opea Concotica. 37, 363, Cationic equilibium of heavy metals in Utica dioica collected in Kakonosze and Beskidy Mountains. Opea Concotica. 37, 265, Occuence and coexistence of some metals in Utica dioica as esults of geochemical conditions Kakonosze. Opea Concotica. 37, 292, PAUKSZTO A., KOWOL J., KWAPULIŃSKI J., ROCHEL R., MIROSŁAWSKI J., BRODZIAK B., KROPCZYŃSKA A., ŚMIETANA B. Relationship Between Contents of Heavy Metals in the Nettle and Soil Case Study in Chochołowska Valley (the Tata Mountain National Pak), Pol. J. Envion. Stud. 15, (2A), 453, 2006.

8