Ramdani et al. World Journal of Pharmaceutical Research
HEAVY METALS ACCUMULATION IN SPECIES FROM MINE
KARZET YOUCEF (ALGERIA)
Takia Lograda, Zahra Harkati, Katia Adel and Messaoud Ramdani*
Laboratory of Natural Resource Valorisation, SNV Faculty, Ferhat Abbas University Setif-1, 19000 Setif, Algeria.
ABSTRACT
Levels of six trace metals were assessed in five species (Marrubium vulgare, Hertia cheirifolia, Gladiolus italicus, Triticum turgidum and
Juncus maritimus) and their association with the bio-accumulation was
investigated. Samples were collected at 2 sites. The species studied, have high contents of ETM, with average metal concentrations; Pb (1,97 ± 5,33); Zn (5,41 ± 5,55); Cu (0,45 ± 0,18); Fe (42, 54 ± 62, 58); Mn (8,81 ± 6,35) and Cd (0,42 ± 0,42). The sampled of plants of the mine Kharzet youcef show very high concentrations of Mn, Zn and Cd, by against, the concentrations of these elements in plant samples of Mehdia site are very low. The concentrations of Fe in species M.
vulgare and H. cheirifolia sampled from the site Kharzet Youcef, are
very high. The Pb rate is very high in H. cheirifolia, sampled from the mine site (1525 mg / kg), concentrations in the other species, are low; generally below standard. These species studied are recognized plants tolerant to the high levels of Cu, Zn, Mn and Cd, and can be used as bio-accumulator and bio-indicator of pollution by these heavy metals.
KEYWORDS: heavy metals, bioaccumulation, bioindication, plants, Mine, Algeria.
INTRODUCTION
The notion of "Trace Elements Metal" (ETM) is poorly defined, it be substituted for that of heavy metals.[1] The trace elements include 80 chemical elements constituents of the crust, who’s the ETM.[2]
This generic term of ETM refers to toxic metals and whose average content in soils is less than 1g/kg.[3] The most commonly used classification of ETM by biologists is based on the affinity of ETM with ligands, oxygenated ligands (Class A) (Pb, Zn, Fe and Mn), nitrogenous or sulphidic ligands (Class B) (Cd, Cu), or for the 2 types of
Volume 5, Issue 11, 250-260. Research Article ISSN 2277– 7105
*Corresponding Author
Dr. Messaoud Ramdani
Laboratory of Natural
Resource Valorisation,
SNV Faculty, Ferhat Abbas
University Setif-1, 19000
Setif, Algeria. Article Received on 09 Sept. 2016,
Revised on 29 Sept. 2016, Accepted on 19 Oct. 2016
ligands (intermediate class).[4] All soils naturally contain the Trace Elements Metal. Thus, their presence is not indicative of pollution.[2] The rates of ETM depend on the original rock forming the soil.[5] Heavy metal pollution is a serious environmental problem especially in developing countries.[6] The contamination of the soils and plants by the ETM has been widely reported.[7-9] Heavy metal contamination of the environment may result from natural processes.[10]
Plants, which are at the base of the food chain, can take up the ETM from the soil solution. This absorption occurs through non- specific pathways. These plants of remediation, they absorb the ETM, generally by bioaccumulation or biosorption. Both processes normally occur in plants, depending on type of species and the heavy metals.[11] The hyper accumulating plants are able to accumulate high levels of heavy metals in their aerial parts at concentrations 10 to 100 times higher than those tolerated by most plants.[12,13]
The concentrations of ETM, causing a toxic effect on the food chain are lower than those producing the phytotoxicity. In the majority of cases, plants can contain too much trace elements for consumption, while also not show any symptoms.[14] However, the biological effects of a contaminant or her bioaccumulation by an organism are not systematically related to the total concentration of the contaminant in the soil.[15-17] The plants have levy capabilities of different trace elements, so it is unclear whether this levy is low, normal or high. Certain authors have attempted to give the metal concentration values of a normal plant, with which to compare samples of a given species.[18,19]
The aim of this work is to study the potential for bioaccumulation of five plant species, of Cd, Fe, Pb, Mn, Cu and Zn, collected on the soil of a zinc mine, in the context of their use in bioindication and phytoremediation.
MATERIALS AND METHODS 1- Study area
1.1. Selection of plant species
The selection of plant species is focused on the dominant plants in the site of mine of Kherzet Youssef; the same species were sampled from the site of Mahdia (Table 1). The sampling of the aerial parts was performed by hand pulling. The samples were placed in paper bags and transported to the laboratory.
2- Samples Preparation 2.1- Cleaning and grinding
It consists to eliminate any atmospheric deposition. After fresh weight measurement, 400g plant samples were dried at 80°C for 48 h and the dry weight was then measured. Then ground and sieved through a nylon sieve to obtain a fine powder.
2.2- Minéralisation
The method of Tauzin and Just20 was used. It consists in calcining 1 to 2g (stems, leaves and roots crushed) in a muffle furnace at 450°C for four hours. The ash thus obtained are mineralized by aqua regia (25% HNO3 and 75% HCl) then reduced to dry until discoloration
of the mineral deposit occurs, on a sand bath. The residue is redissolved in 10ml HCl 5%, and then filtered on Whatman paper with 0,45μm of diameter, completed to 20 ml with HCl 5%. Heavy metals were assayed by Atomic Absorption Spectrophotometer with Flame (AASF) in the laboratory of Valorisation of Natural Biological Resources, Setif University
2.3- Analytical procedures for ETM concentrations
The concentrations of the following elements Cr, Cu, Ni, Cd, Fe and Pb were determined by Atomic Absorption Spectrophotometry with Flame (AASF). There are no established standards of trace elements concentration in pplants. To interpret the results of each element studied, we use as standard reference values, the unit's concentration ranges.The obtained results in (g/l) are transformed in mg/kg using the following relationship: [T(mg/kg)=C(V/S)] Where T = element concentration in mg/Kg
C = concentration of the element in mg/l determined by the calibration curve S = sample weight in grams
V = extraction volume in ml
3- Statistical analysis
between the presence of these elements and the vehicle circulations. Cluster analysis, Unweighted pair group method with arithmetic mean (UPGMA), was carried out on the original variables and on the Manhattan distance matrix to seek for hierarchical associations among the elements and stations. The statistical analyses were carried out using STATISTICA 10 software.
RESULTS
After selecting the probable sites; of each site five species were collected and subjected to analysis of heavy metals by AAF. This analysis revealed the presence of high rates of ETM in the studied plants (Table 2)
The concentrations Mn, Zn and Cd, in the studied plants, are highly variable. The samples of Kharzet youcef (pushing on the floor of the mine) reveal a presence of high levels of these elements, far exceeding international standards. While samples from the region of Mehdia show a very low rate, sub standard, except for Gladiolus italicus of Mehdia region that contains high levels of Mn (Fig. 2). The rate accumulated by Juncus maritimus, indicates that this species can be considered super-accumulator of Mn.
The Cd concentrations of the samples from Kharzet youcef reveal a presence of a high rate, exceeding the standard; while samples from the region of Setif show a very low rate (cadmium values are multiplied by 10, order to have a homogeneous graph). Our results show that the soil of the mine Kharzet Youcef (Zinc Mine) is rich in Zn and Cd, while that of Setif is poor in these elements. The species used in this study are bio-accumulator of zinc, and can be used as bio-indicators of pollution Zinc.
The concentration of Pb in Hertia cheirifolia, sampled from the mine site, is very high; the rate recorded is in the order 1525 mg/kg (Fig. 3). The other species studied, from both sites show low levels of Pb, usually these rates are below standard. These results show that the Kharzet Youcef station is rich in Pb, while the site of Mehdia is weakly low in Pb. The species Hertia cheirifolia, can be considered as accumulatrice and can be used in bio-indication pollution Pb.
Hertia cheirifolia, can be considered bio-accumulators of Fe, so they are bio-indicators of soil pollution by Fe.
The Cu concentrations are highly variable, our samples have a high rate, exceeding the standard, it is noted that the samples of Kharzet Youcef accumulate more the Cu than samples Mahdia (Fig. 4). All species are bio-accumulator of Cu.
Comparing accumulation rates show a significant difference in total concentrations of ETM. To compare profiles ETM we considered each element as a quantitative dependent variable. The three-dimensional spatial projection of species based on three main axes from the ACP (Fig. 5) shows that our species are divided into four groups. The species harvested from the Mahdia region find themselves sets (MVS, HCS, TTS, JMS and GIS) (M. vulgar, H. cheirifolia, T. turgidum, J. maritimus and G. italicus), characterized by very low rates variables (Zn, Cu, Fe, Mn and Cd).
The second assembly includes three species collected from the mine Kharzet Youcef (TTM, GIM and JMM) (T. turdidum, G. italicus and J. maritimus) with average rates of ETM, exceeding the AFNOR standards. Both species (MVM and HCM) (M. vulgar and H.
cheirifolia) sampled from the mine were separated from the rest of the species with very high
rates of ETM. L’analyse des clusters UPGMA (fig. 6), basée sur la distance du linkage, confirme la séparation des espèces en trois clades bien distincts.
The first clustration separates species M. vulgar and H. cheirifolia sampled from Mine Kharzet Youce, with a rate of accumulation of ETM very important. The second clustration is divided into two branches; the first part includes the species collected in the Setif region, with a low rate of ETM, and the second branch brings together the species collected from the mine Kharzet Youcef with greater ETM accumulation rates, than in Setif species, but remains low
Table 1: The species sampled
Species Family Biological type
Gladiolus italicus Mill. Iridaceae
Geophytes
Juncus maritimus Lam. Juncaceae
Hertia cheirifolia (L.) Kuntze Asteraceae
Hemicryptophytes
Marrubium vulgare L. Lamiaceae
Triticum turgidum L.
Table 2: The rates of accumulation of heavy metals (mg/kg)
Species Sampling sites* Code Fe Pb Cu Mn Zn Cd
Marrubium vulgar M MVM 17410,71 3,57 78,57 1214,29 1060,71 85,71
S MVS 83,04 117,86 40,18 135,71 22,32 1,79
Hertia cheirifolia M HCM 10267,86 1525 47,32 1119,64 959,82 75
S HCS 1116,07 10,71 41,07 236,61 26,79 1,79
Triticum turgidum M TTM 1678,57 9,82 31,25 1112,50 1005,36 51,79
S TTS 1144,64 0 23,21 147,32 19,64 8,93
Juncus maritimus M JMM 2598,21 71,43 51,79 1646,43 923,21 77,68
S JMS 1157,14 0 32,14 131,25 18,75 1,79
Gladiolus italicus M GIM 1396,43 19,64 30,36 1196,43 792,86 67,86
S GIS 1125,89 0 26,79 924,11 0 1,79
Standards 150 1 10 200 50 0,05
* M= mine of Karzet Youcef (Ain Azel); S= Mahdia (Setif)
Figure 1: Sampled sites
MVM MVS HCM HCS TTM TTS JMM JMS GIM GIS Standards
Species -200
0 200 400 600 800 1000 1200 1400 1600 1800
E
T
M
c
o
n
ce
n
tr
at
io
n
(
m
g
/
k
g
)
Zn Mn Cd*10
MVM MVS
HCM HCS
T T M T T S
[image:7.595.179.420.76.239.2]JMM JMS GIM GIS Standards Species -2000 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 P b a n d F E c o n ce n tr a tio n s (m g /k g ) Fe Pb
Figure 3: Concentration of Pb and Fe of the samples studied
MVM MVS
HCM HCS
T T M T T S
[image:7.595.178.420.286.442.2]JMM JMS GIM GIS Standard Species 0 10 20 30 40 50 60 70 80 90 C u c o n ce n tr a tio n ( m g /k g )
Figure 4: Cu concentration in the samples
TTSJMS MVS HCS GIS TTM GIM JMM HCM M VM -4 -3 -2 - 1 0 1 2 3
Fact 1 : 65,29
% -1,5 -1,0 -0,5 0,0 0,5 1,0 1,5
Fac t 2: 15,62%
- 2 , 0 - 1 , 5 - 1 , 0 - 0 , 5 0 , 0 0 , 5 1 , 0
1 , 5 2 , 0
Fact 3: 14 ,58% TTSJMS MVS HCS GIS TTM GIM JMM HCM M VM
Figure 5: Spatial projection of species on the first 3 axes from the ACP
[image:7.595.201.395.487.592.2] [image:7.595.161.434.637.742.2]DISCUSSION
The plants analyzed showed of ETM accumulation variable in their aerial parts, especially for (Cu, Zn, Mn, Cd). In general the concentrations are too high in plant samples from the mine site Kharzet Youcef, this contamination has many origins including, among others, the mining activity that can transmit this contamination in the food chain.[21]
The concentrations of elements (Pb, Cu, Zn, Mn, Cd, Fe) are very high in most samples of plants of the mine and exceed international standards (Cheng, 2003). The species Marrubium vulgar, Hertia cheirifolia, Triticum turgidum, Juncus maritimus et Gladiolus italicus are hyperaccumulating of Pb, Cu, Zn, Mn, Cd, Fe, because the rate of these is high relative to the mass of dry matter.[21] These species can be used in the "phytoextraction" based on the use of potential hyperaccumulation to extract the contaminants from the soil and transfer them to the aerial parts of these higher plants.[22-24]
Concerning phytoremediation of soils contaminated by heavy metals, the species studied are good examples because they represent the high accumulation of metals properties. The chemical composition of wild plants was the subject of several research.[25-27] These authors stated that wild species most often present very high tolerance to heavy metals.
CONCLUSION
This research aimed to identify bio-indicator plants and bio-accumulative ETM in two sites, one polluted by discharges of mine Kharzet youcef and the other is considered less polluted control site. Analyses have shown that we can qualify the studied plants (Triticum turgidum, Juncus maritimus et Gladiolus italicus) as a bioaccumulator and to a lesser extent plants
(Marrubium vulgar, Hertia cheirifolia),
ACKNOWLEDGEMENTS
The work was supported by VRBN laboratory, Ferhat Abbas University (Sétif 1), Algeria
REFERENCES
1. Miquel G. Rapport d’information. Office parlementaire d'évaluation des choix scientifiques, Tech, 2001; 261: 346-344.
2. Baize D. Teneurs totales en métaux lourds dans les sols français premiers résultats du programme ASPITET. Courrier de l'Environnement de l'INRA, 2000; 39: 37-46.
3. Conelly NG Damhus T, Hartshorn RM and Hutton AT. Nomenclature of inorganic chemistry. Published for the International Union of Pure and Applied Chemistry (IUPAC). The Royal Society of Chemistry, 2005; 12: 373-377.
4. Nieboer E and Richardson DHS. The replacement of the nondescript term “heavy metals” by a biologically and chemically significant classification of metal ions., Environmental Pollution Series B, Chemical and Physical, 1980; 1: 3-26.
5. Robert M et Juste C. Dynamique des éléments traces de l’écosystème sol. In Club CRIN Environnement. 2nd ed. Spéciation des métaux dans le sol. CRIN, Paris : 1999.
6. Duffus JH. Heavy metals-a meaningless term. Chem. Int., 2001; 23: 163-167.
7. Simmons RW, Pongsakul P, Chaney R, Saiyasitpanich D, Klinphoklap S, Nobuntou W. The relative exclusion of zinc and iron from rice grain in relation to rice grain cadmium as compared to soybean: implications for human health. Plant Soil, 2003; 257: 163-170. 8. Tossapol Limcharoensuk, Najjapak Sooksawat, Anchana Sumarnrote, Thiranun Awutpet,
Maleeya Kruatrachue, Prayad Pokethitiyook, Choowong Auesukaree. Bioaccumulation and biosorption of Cd2+ and Zn2+ by bacteria isolated from a zinc mine in Thailand, Ecotoxicology and Environmental Safety, 2015; 122: 322-330.
9. Berrow ML & Burridge JC. Uptake, Distribution, and Effects of Metal Compounds on plants, in Metals and their Compounds in the Environment", Merrian, E. ed., VCH Verlags gesellshaft, Weinhiem: 1991; pp. 399-410.
10.Robards K, Worsfold P. Cadmium: toxicology and analysis. A review. Analyst, 1991; 116: 549-568.
11.Ledin M. Accumulation of metals by microorganisms-processes and importance for soil systems. Earth Sci. Rev., 2000; 51: 1-31.
13.Krämer U and Chardonnens AN. The use of transgenic plants in the bioremediation of soils contaminated with trace element. Microbiol Biotechnol, 2001; 55: 661-672.
14.William G and Hopkin G. Physiologie végétale, 1ère Ed. De Boek, Paris: 2003.
15.Lanno R, Wells J, Conder J, Bradham K, Basta N. The bioavailability of chemicals in soil for earthworms. Ecotox Env. Safety, 2004; 57: 39-47.
16.Van Gestel, CAM. Physico-chemical and biological parameters determine metal bioavailability in soils. Science of the Total Environment, 2008; 406: 385-395.
17.Pauget B, Gimbert F, Scheifler R, Coeurdassier M, de Vaufleury A. 2012. Soil parameters are key factors to predict metal bioavailability to snails based on chemical extractant data. Science of the Total Environment, 2012; 431: 413-425.
18.Markert B. Establishing of “reference plant” for inorganic characterization of different plant species by chemical fingerprinting. Water Air Soil Pollut, 1992; 64: 533-538. 19.Islam E, Yang XE, He ZL and Mahmood Q. Assessing potential dietary toxicity of heavy
metals in selected vegetables and food crops. Journal of Zhejiang University Sci. B, 2007; 8(1): 1-13.
20.Tauzin C et Juste C. Effet de l’application à long terme de diverses matières fertilisantes sur l’enrichissement en métaux lourds des parcelles. Rapport du contrat 4084/93. Ministère de l’environnement, France: 1986.
21.Ben Ghaya A, Hamrouni L, Mastouri Y, Hanana M and Charles G. Impacts of toxic metals on vegetation of the Djebel Hallouf mine in the area of Sidi Bouaouane in Bou Salem, Northwestern Tunisia, Geo-Eco-Trop, 2013; 37(2): 243-254
22.Kambhampati MS, Begonia GB, Begonia MFT and Bufford Y. Phytoremediation of a lead-contaminated soil using Morning Glory (Ipomoea lacunosa L.): effects of a synthetic chelate, Bulletin of Environmental Contamination and Toxicology, 2003; 71(2): 379-386. 23.Mnasri M, Ghabriche R, Fourati E, Zaier H, Sabally K, Barrington S, Lutts S, Abdelly C
and Ghnaya T. Cd and Ni transport and accumulation in the halophyte Sesuvium portulacastrum: implication of organic acids in these processes. Front. Plant Sci., 2015; 6(156): 1-9.
24.Gardea-Torresdey JL, Peralta-Videab JR, de la Rosa G, Parsons JG. Phytoremediation of heavy metals and study of the metal coordination by X-ray absorption spectroscopy. Coord. Chem. Rev., 2005; 249: 1797-1810.
26.Tomašević M, Rajšić S, Đorđević D, Tasić M, Krstić J, Novaković V. Heavy metals accumulation in tree leaves from urban areas, Environmental Chemistry Letters, 2004; 2(3): 151-154.