EnvironmentAsia AvailableAvailable online online at www.tshe.org/EA at www.tshe.org/EA The international journal published by the Thai Society of Higher Education Institutes on Environment EnvironmentAsiaEnvironmentAsia 8(1) 2 (2009)(2015) 133-14350-54
Genotoxicity Assessment of Mercuric Chloride in the Marine Fish Therapon jaruba Distribution of Selected Heavy Metals in Sediment of the River Basin of Coastal Area of Nagarajan Nagarani,Chanthaburi Arumugam Kuppusamy Province, Kumaraguru, Gulf of Thailand Velmurugan Janaki Devi and Chandrasekaran Archana Devi Jakkapan Potipat a, b, Nongnutch Tangkrock-olan c and Herbert F. Helander d Center for Marine and Coastal Studies, School of Energy, Environment and Natural Resources, a Graduate School,Madurai Faculty Kamaraj of Science, University, Burapha Madurai-625021, University, Chonburi, India 20131 Thailand b Department of Environmental Science, Faculty of Science and Technology, Rambhai Barni Rajabhat University, Chantaburi, 22000 Thailand Abstract c Department of Aquatic Science, Faculty of Science, Burapha University, Chonburi, 20131 Thailand d Department of Gastroresearch, Sahlgren Academy, Göteborg University, Sweden The aim of the present study was to standardize and to assess the predictive value of the cytogenetic analysis byAbstract Micronucleus (MN) test in fish erythrocytes as a biomarker for marine environmental contamination. Micronucleus frequency baseline in erythrocytes was evaluated in and genotoxic potential of a common chemical was determined in fishThe experimentally sediment samples exposed from in 24 aquarium stations inunder coastal controlled area of Chanthaburiconditions. Fish Province (Therapon were collected jaruba) wereduring exposed March for2012 96 to hrsMarch to a 2013 single and heavy analyzed metal for (mercuric heavy metal chloride). contents Chromosomal (Pb, Cd, Cr, Fe,damage Cu and was Zn), determined pH, organic as mattersmicronuclei and grain frequency sizes. Thein fishcorrelation erythrocytes. analyses Significant showed that increase heavy metalin MN concentrations frequency was were observed affected in by erythrocytes the content ofof fishorganic exposed matter to and mercuric the size chloride.of clay particles. Concentration The evaluation of 0.25 ppm of the induced quality the of highest sediment MN was frequency carried out (2.95 using micronucleated the geoaccumulation cells/1000 index cells ( Icomparedgeo) and the toenrichment 1 MNcell/1000 factor (EF) cells as in well control as the animals).comparison The with study those revealed in the Thailand’s that micronucleus sediment quality test, as guideline an index (SQG) of cumulative values. The exposure,results of the appears geoaccumulation to be a sensitive index andmodel the enrichmentto evaluate factorgenotoxic values compounds of the heavy in metals fish under content controlled in the sediments conditions. revealed that the study area was unpolluted and not enriched, respectively. The relationship between the heavy metals concentration Keywords:and the organic genotoxicity; matter, and mercuric the clay chloride;particle was micronucleus proposed by using the multiple regression equations.
Keywords: heavy metals; geoaccumulation index (Igeo); enrichment factor (EF); Chanthaburi Province
1. Introduction laboratory and field conditions. In 2006 Soumendra 1. Introduction etenvironment al., made an in attempt many toparts detect of geneticthe world biomarkers (Naji and In India, about 200 tons of mercury and its inIsmail, two fish2011; species, Yap and Labeo Wong, bata 2011; and BanerjeeOreochromis et al., compounds Heavy metalare introduced pollution isinto a serious the environment and widely mossambica,2012; Ong et al.,by 2013). MN and binucleate (BN) annuallyenvironmental as effluents problem from due industries to the (Saffi,persistent 1981). and erythrocytes The coastal in thearea gill of Chanthburiand kidney Province erythrocytes on the Mercuricnon-biodegradable chloride has properties been used of in the agriculture contaminants. as a exposedGulf of Thailand to thermal has a totalpower coastline plant of discharge approximately at fungicide,Sediments arein ultimatemedicine sink as anda topical storage antiseptic of heavy metals and Titagarh120 kilometers. Thermal It covers Power around Plant, 1,722 Kolkata, square India. kilometer disinfectant,accumulated and in coastalin chemistry areas as carried an intermediate by particles in of theThe three present river studybasin namely:was conducted the Wang-Ta-Nord, to determine the thethat production have been of transported other mercury as a compounds.result of erosion The theChanthaburi acute genotoxicity and the Welu. of the The heavy largest metal mangrove compound area contaminationand advection fromof aquatic original ecosystems sites in the by terrestrial heavy HgClin the2 eastern in static part systems. of Thailand Mercuric with high chloride abundance is toxic, and metalsenvironment and pesticides (Förstner, has 1978). gained increasing attention solvablebiodiversity in water of flora hence and itfauna can penetratewas located the in aquatic the Welu in recentThe distribution decades. Chronicof heavy exposuremetals level to inand the animals.river basin Mutagenic (Aksornkoae, studies 1975). with This native region fish is species notable accumulationsediments are of often these analyzed chemicals based in aquatic on the biota total representfor various an kinds important of anthropogenic effort in activities determining including: the canmetal result content in tissue(Yap and burdens Wong, that 2011) produce as well adverse as some potentialagriculture, effects fisheries, of toxic gemstone agents. mining,This study tourism, was effectsgeochemical not only indices in the directly to help exposed and support organisms, the carriedrecreation out activitiesto evaluate and the urban use ofcommunities the micronucleus (Raine, butinvestigation also in human of heavy beings. metal pollution in the study test1994). (MN) for the estimation of aquatic pollution area.Fish The provides degree aof suitable heavy modelmetals for loading monitoring in the using The marine aim edible of this fish study under is lab to conditions. investigate the aquaticsediment genotoxicitycan be harmful toand the environmentwastewater depending quality concentration and the distribution of heavy metals in becauseon the geochemical of its ability condition to metabolize existing xenobiotics in the sediments. and 2.the Materials surface sediments and methods from 24 stations of the river basin accumulatedPeng et al. (2009) pollutants. reported A that micronucleus the data of pH,assay organic has of coastal area of Chanthaburi Province and to classify beenmatter used and successfully grain size which in several temporally species and (De spatially Flora, 2.1.the qualitySample assessment Collection of surface sediments by using et al., 1993, Al-Sabti and Metcalfe, 1995). The varied amongst collected sediment samples are main the geoaccumulation index (Igeo) and the enrichment micronucleusinfluence on heavy (MN) metals test mobilizationhas been indeveloped sediments. factorThe (EF). fish speciesThe determination selected for onthe the present relationship study together The studies with usingDNA-unwinding the geoaccumulation assays index as wasbetween collected the heavy from metal Pudhumadam concentrations coast and of Gulfsediment of perspective methods for mass monitoring of Mannar, Southeast Coast of India. Therapon (Igeo) and the enrichment factor (EF) to study on characteristics (pH, organic matter and grain size ) and clastogenicitythe distribution and of genotoxicityheavy metals in in fish the andsediments mussels as jarbuathe evaluation belongs on theto thedistribution order Perciformes of heavy metals of usingthe (Dailianiswell as to evaluateet al., 2003). and to assess the degree of heavy familyPCA (Principal Theraponidae. Component The Analysis)fish species, and theTherapon multiple metalsThe contamination MN tests have of been polltuion successfully in the usedland-sea as jarbuaregression(6-6.3 anlysis cm inhave length been and included. 4-4.25 g in weight) a measure of genotoxic stress in fish, under both was selected for the detection of genotoxic effect J. Potipat et al. / EnvironmentAsia 8(1) (2015) 133-143
2. Materials and Methods 2.3. Statistical analysis
2.1. Sediment sampling station All statistical analyses were performed by using Statistical Package for Social Science (SPSS) Version The surface sediments were collected from 24 18 (Serial No.5083337). The correlation coefficient stations along the study sites which were divided between the heavy metal concentrations, the organic into 3 zones symbolically: A, B and C representing matter, the grain size and the pH in the surface sediment industrial (near Map Ta Phut industrial estate), urban showed differences of these relationships. The Principal community and agriculture or conservative land use Component Analysis (PCA) and the multiple regression areas, respectively (Fig. 1). At each station, the composite technique were used to summarize of the distribution sediments of 3 subsamples were collected by using the of heavy metals in the study area. Ekman grab during March 2012 to March 2013. The surface sediment samples from each station were placed 3. Results and Discussion in the polyethylene plastic bags and kept in an ice box during the transportation to the laboratory at Rambhai 3.1. The concentration of heavy metals and sediment Barni Rajabhat University to be stored at -20oC in a characteristics freezer for further analysis The average variation of heavy metal concentra- 2.2. Heavy metals analysis tions in the sediments of the river basin of coastal area of Chanthaburi Province from 24 stations were 1.818 The heavy metals determined included Pb, Cd, Cr, ± 0.525 μg/g for Pb, 0.018 ± 0.005 μg/g for Cd, 8.644 Fe, Cu and Zn. The sediment samples were microwave ± 1.648 μg/g for Cr, 17,860 ± 3,385 μg/g for Fe, 7.414 digested using a mixture of aqua regia (HNO3: HCl, ± 1.952 μg/g for Cu and 18.122 ± 3.367 μg/g for Zn 1:3 v/v) and hydrofluoric acid (HF) (Thongra-aret al., (means ± SD) as shown in Table 2. The highest average 2008). The instrumental analysis was carried out by concentrations of Pb, Cd, Cr, Fe and Zn in the sediment using the graphite furnace atomic absorption spectro- were observed in the Chanthaburi river basin (B), while photometer Model SpectrAA-640 Varian (Pb, Cd, Cr) the highest average concentration of Cu was found in the and the flame atomic absorption spectrophotometer Welu river basin (C). All the heavy metals concentrations Model Spectrometer 3110, Perkin-Elmer (Fe, Cu, Zn). observed were lower than those from the sediment The selected sediment characteristics were quality guideline (SQG) for Thailand (PCD, 2006) as determined as follows: the pH in surface sediments well as the world average sediment (Sparks, 2003). were measured in a 1: 2.5 (sediment: water) suspension The correlation coefficient analysis between (Madejón et al., 2002), organic matter (OM) by using the heavy metal concentrations and the sediment the weight loss on ignition technique (Combs and characteristics with correlation coefficient values were Nathan, 1998) and particle size the distribution by shown in Table 3 displaying positive correlation with using the sieve analysis technique (American Society the sediment organic matter (OM) in silt and clay for Testing Materials, 2007). particles, whereas Pb, Fe and Zn showed negative The precision and accuracy of the analytical correlation with pH and sand particle. The result of techniques were assessed by comparing with those of this study indicated that the OM and clay particle the Marine Sediment Reference Material (MESS-3) were relatively more statistically significant than pH, from the National Research Council of Canada and this silt and sand particles in controlling the distribution of was found to be close to the certified values (Table 1). Pb, Cd, Cr, Fe, Cu and Zn in the sediments of high r
Table 1. The content analysis and recovery percentage of the certified reference material (Marine Sediment Reference Materials: MESS-3) from the National Research Council, Canada
Element Certified value Present study (n=5) % Recovery Coefficient of variation Pb 21.1 ± 0.7 18.8 ± 0.7 89.0 3.7 Cd 0.24 ± 0.01 0.20 ± 0.02 84.2 10 Cr 105 ± 4 93 ± 5 88.8 5.3 Fe 43,400 ± 1,100 38,870 ± 850 89.6 2.2 Cu 33.9 ± 1.6 37.5 ± 1.6 110.6 4.3 Zn 159 ± 8 168 ± 7 105.7 4.2
134 J. Potipat et al. / EnvironmentAsia 8(1) (2015) 133-143
100 0 100
Kilometers
Wang-Ta-Nord river
Chanthaburi river N Namtokphlio ' National Park 30 A
12° B Welu river
N GULF OF THAILAND
12°22'
C
101°56' E 102°02' E 102°08' E 102°14' E
A1 C7 C1 B1 A2101°52' E B5 B4 A3 B2 C2 A4 B3 C6 C3 A5 A6 B6 B9 C4 B7 C5 A7 B8 B10
(A) Wang-Ta-Nord (B) Chanthaburi (C) Welu Figure 1. The three river basins of Chanthaburi coastal area and sampling stations Figure 1. The three river basins of Chanthaburi coastal area and sampling stations
135 J. Potipat et al. / EnvironmentAsia 8(1) (2015) 133-143 2.9 19.5 20.1 25.2 16.8 20.6 13.9 24.3 16.3 16.9 18.9 Clay % 2.3 41.6 40.8 43.7 41.7 45.2 39.3 45.6 37.0 39.2 41.4 Silt % Particle Size Distribution 2.8 38.9 39.1 42.8 41.5 45.3 37.5 42.3 33.8 35.6 39.7 Sand % 2.7 3.1 4.2 2.4 3.3 1.9 3.6 1.9 2.5 2.7 0.6 OM % pH 8.11 7.77 7.49 8.06 7.66 7.26 8.23 7.23 7.04 7.66 0.37 95 Zn 121 3.367 11.644 19.199 16.774 22.675 17.930 21.392 13.322 21.941 14.272 18.122 33 Cu 31.6 6.653 8.372 5.938 7.542 7.414 9.800 5.831 8.998 3.692 1.952 10.832 - Fe 3,385 19,615 16,526 20,767 10,059 16,689 17,860 41,000 20,492 10,733 22,671 16,981 Cr 72 81 9.322 8.127 4.948 8.192 8.644 6.327 7.740 1.648 11.308 10.763 10.731 Cd 0.09 0.17 0.99 0.020 0.028 0.016 0.027 0.016 0.018 0.024 0.010 0.017 0.005 Concentration of heavy metals (μg/g) 19 Pb 35.8 2.511 2.209 3.039 1.542 2.075 1.084 1.536 1.818 1.045 1.577 0.525 Mean Max Mean Max Min Mean Mean Max Min Min SD B C A Welu Location Chathaburi (7 stations) (7 stations) (10 stations) Wang-Ta-Nord Sediments of the coastal area Chanthaburi (24 stations) average sediment World Sparks (2003) Proposed sediment quality guidelines (SQG) Thailand by PCD (2006)* for Table 2. The concentration of heavy metals (μg/g) and characteristics in sediments the three river basin coastal area Chanthaburi Province 2. Table * Equilibrium Partitioning Approach (EqP) Method * Equilibrium Partitioning
136 3. Results and Discussion
3.1. The concentration of heavy metals and sediment characteristics
The average variation of heavy metalJ. Potipat concentrations et al. / EnvironmentAsia in the sediments 8(1) (2015) of 133-143the river basin of coastal area of Chanthaburi Province from 24 stations were 1.818 ± 0.525 μg/g for Pb, 0.018Table ± 0.005 3. The μg/g correlation for Cd, 8.644coefficient ± 1.648 between μg/g forheavy Cr, metals,17,860 pH, ± 3,385organic μ g/gmatter for and Fe, grain7.414 size ± (n=24) 1.952 μg/g for Cu and 18.122 ± 3.367 μg/g for Zn (means ± SD) as shown in Table 2. The highest average concentrationsPb Cd of Pb, Cd,Cr Cr, FeFe and Zn inCu the sedimentZn werepH observedOM in the Sand Silt Clay ChanthaburiPb river basin1.000 (B), while the highest average concentration of Cu was found in the Welu riverCd basin (C).0.687** All the1.000 heavy metals concentrations observed were lower than those from the sediment quality guideline (SQG) for Thailand (PCD, 2006) as well as the world average sedimentCr (Sparks,0.484* 0.636**2003). 1.000 TheFe correlation0.409* coefficient0.553** analysis0.638** between1.000 the heavy metal concentrations and the sediment characteristicsCu -0.009 with0.339 correlation0.249 coeffici0.122ent values1.000 were shown in Table 3 displaying positive correlationZn 0.331 with the0.682** sediment0.608** organic0.645** matter (OM)0.312 in silt and1.000 clay particles, whereas Pb, Fe and Zn showed negative correlation with pH and sand particle. The result of this study indicated thatpH the OM0.033 and clay0.234 particle0.327 were re-0.697**latively more0.308 statistically-0.619** significant1.000 than pH, silt and sandOM particles0.556** in controlling0.613** the0.422* distribution0.443* of Pb,0.408* Cd, Cr,0.558** Fe, Cu and-0.462* Zn in the1.000 sediments Sandof high -0.103r values. Chen0.105 et al0.072. (2007) demonstrated-0.160 0.254 that the0.144 OM and0.131 clay were-0.486* more 1.000 important Siltfactor in0.099 affecting0.063 the heavy0.253 metals distribution0.066 0.268 than other0.164 characteristics0.157 in-0.327 the -0.384 1.000 studied sediment of high correlation coefficient values. An organic compound in the sediment Clay 0.602** 0.553** 0.412* 0.473* 0.562** 0.575** -0.246 0.740** -0.688** 0.405* 1.000 plays an important role in heavy metals distribution because heavy metals are generally *, **: Correlation is significant at the 0.05 and 0.01 level, respectively bounded in largest fraction to the OM (Peng et al., 2009). The grain size is the one of the most investigated supported indicative of heavy metals distribution when the grain size decreasesvalues. and the Chen metal et contents al. (2007) increases. demonstrated that the OM the heavy metals in all the river basin of Chanthaburi and clay were more important factor in affecting the coastline. Fe and Zn are highest Igeo values and Table 3. Theheavy correlation metals coefficient distribution between than otherheavy characteristics metals, pH, organic in matterconcentration and grain sizein sediment (n=24) as shown in Fig. 2. Glasby the studied sediment of high correlation coefficient et al. (2004) indicating that the crustal weathering may Pb Cd Cr Fe Cu Zn pH OM Sand Silt Clay Pb 1.000values. An organic compound in the sediment plays be the main source of Fe and Zn in the sediment which Cd 0.687** 1.000 an important role in heavy metals distribution because major element in the earth’s crust have highest Igeo Cr 0.484* 0.636** 1.000 Fe 0.409*heavy metals 0.553** are 0.638**generally 1.000 bounded in largest fraction values. It is known that floods enhance the transportation Cu -0.009to the OM0.339 (Peng et 0.249 al., 2009). 0.122 The grain 1.000 size is the one of natural and anthropogenic sediment into the river Zn 0.331 0.682** 0.608** 0.645** 0.312 1.000 pH 0.033of the most 0.234 investigated 0.327 supported -0.697** indicative0.308 -0.619** of heavy 1.000and subsequently deposit in the environment of the OM 0.556**metals distribution 0.613** 0.422* when the 0.443* grain size 0.408* decreases 0.558** and -0.462*river 1.000mouth. Chanthaburi Province was classified as a Sand -0.103the metal0.105 contents 0.072 increases. -0.160 0.254 0.144 0.131high -0.486*risk area 1.000of landslide, water flow and flood due Silt 0.099 0.063 0.253 0.066 0.268 0.164 0.157 -0.327 -0.384 1.000 Clay 0.602** 0.553** 0.412* 0.473* 0.562** 0.575** -0.246to the 0.740** landslide -0.688** disaster 0.405* of Kitchakood 1.000 Mountain in *, **: Correlation is significant at the 0.05 and 0.01 level, respectively 3.2. Geoaccumulation index (Igeo) 2000 and flooding crisis in 2006 (Anecksamphant, 2004). Furthermore, Fe and Zn are micronutrients in a geo 3.2. Geoaccumulation The geoaccumulation index (I ) index (Igeo) was used to define fertilizer and an addition to the ingredient of the degree of anthropogenic pollution in the sediment supplementary food in shrimp farms whereas in 2003 The(Förstner geoaccumulation et al., 1993). index The geoaccumulation(Igeo) was used to indexdefine can the degreethe shrimp of anthropogenic farm land, urban land and agriculture pollution bein thecalculated sediment using (Förstner the following et al., 1993). equation: The geoaccumulationdeveloping index can area be calculated are continuously increasing in using the following equation: Chanthaburi Province up to these days (Runping and C n Kheoruenromne, 2003). Igeo = log2 1.5 Bn Table 4. The geoaccumulation index classification (Förstner where C is the measured concentration of the sediment for heavy metal (n), B is the n et al., 1993) n geochemical backgroundwhere Cn is concentration the measured of concentrationthe heavy metal of (n) the and 1.5 is the correction factor for variationsediment in the backgroundfor heavy metal values (n), due B nto is lithogenic the geochemical effects. In the present study, the average crustbackground concentrations concentration were used of as the the heavybackground metal values (n) of: 12.5Sediment μg/g for Pb, 0.2 μg/g for Cd,and 100 1.5 μ isg/g the for correction Cr, 56,300 factor μg/g forfor Fe, variation 55 μg/g in for the Cu, andAccumulation 70 μg/g for Zn I(Taylor,geoClass Pollution Intensity Index (I ) 1964). background values due to lithogenic effects. In the geo present study, the average crust concentrations were >5 6 Very Strong Pollution used as the background values of: 12.5 μg/g for Pb, 0.2 >4-5 5 Strong to Very Strong μg/g for Cd, 100 μg/g for Cr, 56,300 μg/g for Fe, 55 >3-4 4 Strongly Polluted μg/g for Cu, and 70 μg/g for Zn (Taylor, 1964). >2-3 3 Moderately to Strongly The classification and results of I values of geo >1-2 2 Moderately to Polluted the study area are shown in Table 4 and in Table 5, >0-1 1 Unpolluted to Moderate respectively. Whereas, Table 5 show the negative <0 0 Practically Unpolluted values (Igeo<0) indicated that there was no pollution from
137 The classification and results of Igeo values of the study area are shown in Table 4 and in Table 5, respectively. Whereas, Table 5 show the negative values (Igeo<0) indicated that there was no pollution from the heavy metals in all the river basin of Chanthaburi coastline. Fe and Zn are highest Igeo values and concentration in sediment as shown in Fig. 2. Glasby et al. (2004) indicating that the crustal weathering may be the main source of Fe and Zn in the sediment which major element in the earth’s crust have highest Igeo values. It is known that floods enhance the transportation of natural and anthropogenic sediment into the river and subsequently deposit in the environment of the river mouth. Chanthaburi Province was classified as a high risk area of landslide, water flow and flood due to the landslide disaster of Kitchakood Mountain in 2000 and flooding crisis in 2006 (Anecksamphant, 2004). Furthermore, Fe and Zn are micronutrients in a fertilizer and an addition to the ingredient of supplementary food in shrimp farms whereas in 2003 the shrimp farm land, urban land and agriculture developing area are continuously increasing in Chanthaburi Province up to these days (Runping and Kheoruenromne, 2003).
Table 4. The geoaccumulation index classification (Förstner et al., 1993)
Sediment Accumulation Index IgeoClass Pollution Intensity (Igeo) >5 6 Very Strong Pollution >4-5 5 Strong to Very Strong >3-4 4 Strongly Polluted >2-3 3 Moderately to Strongly >1-2 2 Moderately to Polluted >0-1 1 Unpolluted to Moderate <0 0 Practically Unpolluted J. Potipat et al. / EnvironmentAsia 8(1) (2015) 133-143
Figure 2. The plot of heavy metal concentrations and Igeo index FigureFigure 2. 3. The The plot plot of of heavy heavy metal metal concentrations concentrations and and I geoenrichment index factor (EF) 3.3. Enrichment Factor (EF) that of the Non Essential Elements (Pb and Cd except 3.4. PCA (Principal Component Analysis)Cr). Hem (1985) reported that Cr was the 17th most The Enrichment Factor is a tool to differentiate abundant metal in the earth’s crust and it was found that
3.3. Enrichmentthe Factorsources (EF) of heavy metalsThe between results of lithogenic the PCA studyand onthe the amount sedim inent sedimentary of the three rocksampling was higher sites point than outthose that the tendency of the heavy metals distribution was distinctly located which revealed an naturally occurring Iron (Fe) whereas it has been of Pb and Cd. In addition, Cr is a major component of obvious separation in the first principal score axis as shown in Fig. 4. The first group The Enrichmentused successfully Factor byis aseveral tool to researchesdifferentiate to the normalize sources of steelheavy alloys metals furnitures between (10-26%) and it is used in many lithogenic andthe naturally heavy metalsoccurring containingdistribution Iron (Fe) the whereain sample rivers itand from has estuarine beenthe Welu used riversuccessfullyproducts basin in (C) dailyby could several life be more distinguished than Pb and in the Cd lower (Bielicka right researches to sedimentsnormalize (Rule,the heavy 1986;of themetals Herut plot. distribution Theand Sandler,second in group 2006;river areand Naji mostly estuarine et althe., sediments sample2005). from (Rule, the Wang-Ta-Nord river basin (A) 1986; Herut andand Sandler,Ismail, 2011;2006; isBanerjeeNaji located and Ismail,etin althe., upper 2012).2011; right BanerjeeThe ofEF the foret plot. al ., 2012).TheZn th irdisThe a group natural EF for of element Fe- samples of from highest the enrichment Chanthaburi factor river normalizationFe-normalization is defined by: isbasin defined (B) wasby: found in the left of the firstand principal high concentration score axis. found in the sediment in the river This PCA indicated the differences in the heavy metals concentration observed in the basin is a result of derivation and accelerated erosion sediment samples from the three river basin of coastal area of Chanthaburi Province. The MX /FeX sample on land (Baptista Neto et al., 2000). Furthermore, the EF distribution= of heavy metals depends on their concentration in the sediment as well as the Heavy metals widespread of urbanization, the use of fertilizers and physicochemicalMC/FeC characteristicsshale of both sediment and seawater (de Vallejuelo et al., 2014). pesticides in agricultural activities are minor sources However, there are several sources of heavy metals in the sediment from the Chanthanburi where Mx is the concentration of heavy metals in of Zn (Ghrefat and Yusuf, 2006). where Mx is the concentrationcoastline of andheavy from me thetals different in the examined of land usesample, in th eFe boundaryx is the of each river basin. In the past the examined sample, Fex is the concentration of Fe concentration of Fe in the examined(1991), sample, land useMc inis the concentrationcoastal zone of of Ch heavyanthaburi metals Province in was dominated by prawn in the examined sample, Mc is the concentration of 3.4. PCA (Principal Component Analysis) average shale or undisturbed sedimentaquaculture and Fe developmentsc is the concentration (45.3% of of the Fe landin average portion shale of the or study area). The major terrestrial undisturbed sediments.heavy metals As inthere averageland were uses shale no reportewithin or undisturbed thed data coastline available, sediment are riceth e averagepaddies shale(24.5%), values fruit orchards (14.2%), mangrove used in this studyand Fewerec is those the concentration byforests Turekian (6.1%), and of WedepohlFerubber in average plantations (1961) shale of (4.9%) background andThe upland results levels forests ofheavy the PCA(3.5%) study (Raine, on the 1994). sediment Moreover, of the metals. The undisturbedor undisturbed sediment sediments.the values widespread As utilized there encroaching were:were no20 reportedμ urbanization,g/g for Pb,three 0.3 tour μ samplingg/gism for and Cd, sites recreation 90 point outactivities that the are tendency continuously of the μg/g for Cr, 45data μg/g available, for Cu, andtheincreasing 95average μg/g forshale in Zn.both values upland used and in coastline this heavy area of metals Chanthaburi distribution Province, was distinctly especially located along which the The EFstudy results were from those the byChanthaburi present Turekian investigation and river. Wedepohl were (1961) shown of in Tablerevealed 5 and an the obvious separation in the first principal classification backgroundof EF values levelswas shown heavy in metals.Table 6. TheThe EFundisturbed values of allscore heavy axis metals as shown at all in Fig. 4. The first group containing stations were sedimentfound to valuesbe less utilizedthan 1 (EF<1) were: 20 which μg/g indicatedfor Pb, 0.3 that μg/g there the was sample no heavy from metals the Welu river basin (C) could be enrichment detectedfor Cd, in90 the μg/g study for areaCr, 45(Fig. μg/g 3). for Cu, and 95 μg/g distinguished in the lower right of the plot. The second The resultsfor Zn. of an analysis of the Igeo and EF values (Figs. 2 andgroup 3) showed are mostly that the the sample from the Wang-Ta-Nord distribution of theThe Essential EF results Elements from the(Fe, present Cu and investigation Zn) were higher were thanriver that basin of the (A) Non is located in the upper right of the plot. Essential Elementsshown (Pb in Table and Cd5 and except the classification Cr). Hem (1985) of EF reported values wasthat CrThe was third the group 17th most of samples from the Chanthaburi river abundant metalshown in the in earth’sTable 6. crust The andEF valuesit was foundof all heavy that the metals amount at inbasin sedimentary (B) was rock found was in the left of the first principal higher than thoseall stations of Pb and were Cd. found In addition, to be less Cr than is a 1major (EF<1) component which ofscore steel axis. alloys furnitures (10-26%) andindicated it is used that in many there products was no heavyin daily metals life more enrichment than Pb and CdThis (Bielicka PCA indicatedet al., the differences in the heavy 2005). detected in the study area (Fig. 3). metals concentration observed in the sediment samples Zn is a natural element of highest enrichment factor and high concentration found in The results of an analysis of the Igeo and EF from the three river basin of coastal area of Chanthaburi the sediment valuesin the river(Figs. basin 2 and is a3) result showed of derivationthat the distribution and accelerated of Province.erosion on The land distribution of heavy metals depends (Baptista Netothe et Essential al., 2000). Elements Furthermore, (Fe, Cu the and widespread Zn) were higher of urbanization, than on their the use concentration of fertilizers in the sediment as well as the and pesticides in agricultural activities are minor sources of Zn (Ghrefat and Yusuf, 2006).
Table 6. The classification of enrichment factor (Naji and Ismail, 2011) 138 EF range Assessment Category Comment < 1 I no enrichment 1 - 2.9 II minor enrichment 3 - 4.9 III moderate enrichment 5 - 9.9 IV moderately severe enrichment 10 - 24.9 V severe enrichment 25 - 49.9 VI very severe enrichment > 50 VII extremely severe enrichment
J. Potipat et al. / EnvironmentAsia 8(1) (2015) 133-143
Table 5. Heavy metals enrichment factor (EF) and geoaccumulation index (Igeo) values in the three river basin of coastal area of Chanthaburi Province
Pb Cd Cr Fe Cu Zn Station EF Igeo EF Igeo EF Igeo EF Igeo EF Igeo EF Igeo A1 0.28 -3.88 0.15 -4.92 0.36 -4.35 - -2.98 0.68 -3.57 0.69 -2.83 A2 0.35 -2.90 0.22 -3.64 0.22 -4.41 - -2.31 0.61 -3.07 0.51 -2.59 A3 0.21 -3.56 0.15 -4.13 0.26 -4.08 - -2.24 0.34 -3.81 0.60 -2.29 A4 0.17 -4.16 0.18 -4.13 0.29 -4.18 - -2.51 0.44 -3.74 0.64 -2.46 A5 0.20 -3.41 0.15 -3.99 0.27 -3.80 - -2.04 0.46 -3.20 0.48 -2.42 A6 0.20 -3.86 0.13 -4.54 0.30 -4.08 - -2.44 0.48 -3.54 0.43 -2.98 A7 0.15 3.88 0.12 -4.32 0.16 -4.57 - -2.05 0.41 -3.37 0.48 -2.41 B1 0.38 -2.63 0.18 -3.84 0.32 -3.74 - -2.17 0.34 -3.78 0.46 -2.60 B2 0.31 -3.06 0.26 -3.43 0.28 -4.04 - -2.31 0.44 -3.54 0.61 -2.34 B3 0.19 -3.57 0.13 -4.13 0.27 -3.90 - -2.08 0.47 -3.20 0.43 -2.59 B4 0.26 -3.01 0.13 -4.13 0.22 -4.08 - -2.02 0.29 -3.88 0.48 -2.40 B5 0.30 -2.90 0.17 -3.78 0.26 -3.94 - -2.08 0.42 -3.37 0.51 -2.37 B6 0.27 -3.02 0.14 -4.06 0.23 -4.08 - -2.06 0.19 -4.47 0.35 -2.88 B7 0.18 -3.41 0.14 -3.90 0.21 -4.06 - -1.90 0.18 -4.38 0.48 -2.27 B8 0.26 -3.04 0.18 -3.64 0.25 -3.92 - -2.02 0.29 -3.84 0.50 -2.33 B9 0.25 -3.22 0.17 -3.84 0.21 -4.27 - -2.15 0.50 -3.20 0.46 -2.58 B10 0.28 -3.20 0.17 -4.06 0.27 -4.13 - -2.31 0.51 -3.31 0.64 -2.26 C1 0.38 -3.56 0.17 -4.76 0.26 -4.92 - -3.07 0.62 -3.80 0.58 -3.17 C2 0.24 -4.11 0.13 -5.06 0.28 -4.72 - -2.98 0.59 -3.78 0.54 -3.17 C3 0.15 -4.01 0.08 -5.06 0.19 -4.47 - -2.20 0.37 -3.66 0.34 -3.04 C4 0.18 -3.76 0.16 -4.06 0.25 -4.08 - -2.22 0.51 -3.24 0.49 -2.56 C5 0.19 -3.56 0.14 -4.06 0.26 -3.90 - -2.06 0.56 -2.93 0.56 -2.21 C6 0.28 -3.17 0.22 -3.64 0.30 -3.92 - -2.28 0.59 -3.08 0.57 -2.40 C7 0.22 -3.31 0.20 -3.47 0.27 -3.80 - -2.02 0.54 -2.93 0.50 -2.33 Max 0.38 -2.63 0.26 -3.43 0.36 -3.74 - -1.90 0.68 -2.93 0.69 -2.21 Min 0.15 -4.16 0.08 -8.67 0.16 -4.92 - -3.07 0.18 -4.47 0.34 -3.17 Mean 0.24 -3.42 0.16 -4.29 0.26 -4.14 - -2.27 0.45 -3.53 0.51 -2.56 SD 0.07 0.42 0.04 1.04 0.04 0.30 - 0.32 0.13 0.41 0.09 0.29 Average crust a 12.5 0.2 100 56,300 55 70 (μg/g) Average shale b 20 0.3 90 47,200 45 95 (μg/g) (A-Wang-Ta-Nord, B-Chanthaburi and C-Welu) a Taylor (1964) b Turekian and Wedenphol (1961)
Table 6. The classification of enrichment factor (Naji and Ismail, 2011)
EF range Assessment Category Comment < 1 I no enrichment 1 - 2.9 II minor enrichment 3 - 4.9 III moderate enrichment 5 - 9.9 IV moderately severe enrichment 10 - 24.9 V severe enrichment 25 - 49.9 VI very severe enrichment > 50 VII extremely severe enrichment
139 J. Potipat et al. / EnvironmentAsia 8(1) (2015) 133-143
Figure 3. The plot ofFigure heavy 3. metal The plotconcentrations of heavy metal and enrichmentconcentrations factor and (EF) enrichment factor (EF) physicochemical 3.4.characteristics PCA (Principal of bothComponent sediment Analysis) (4.9%) and upland forests (3.5%) (Raine, 1994). and seawater (de Vallejuelo et al., 2014). However, there Moreover, the widespread encroaching urbanization, are several sources of heavyThe metalsresults inof the PCAsediment study ontourism the sedim andent recreation of the three activities sampling are sites continuously point out from the Chanthanburithat thecoastline tendency and of from the theheavy different metals distribuincreasingtion was in distinctlyboth upland located and which coastline revealed area an of of land use in the boundaryobvious separation of each river in the basin. first Inprincipal the Chanthaburi score axis as Province, shown in especially Fig. 4. The along first the group Chanthaburi past (1991), land usecontaining in the coastal the sample zone of from Chanthaburi the Welu riverriver. basin (C) could be distinguished in the lower right Province was dominatedof the plot. byThe prawn second aquaculture group are mostly the sample from the Wang-Ta-Nord river basin (A) developments (45.3%is located of thein the land upper portion right of of the the plot. 3.5. The Multiple third group regression of samples analysis from the Chanthaburi river basin (B) was found in the left of the first principal score axis. study area). The major terrestrial land uses within the This PCA indicated the differences in the heavy metals concentration observed in the coastline are rice paddies (24.5%), fruit orchards The relationship between the heavy metals sediment samples from the three river basin of coastal area of Chanthaburi Province. The (14.2%), mangrove forests (6.1%), rubber plantations concentration and the sediment characteristics could distribution of heavy metals depends on their concentration in the sediment as well as the physicochemical characteristics of both sediment and seawater (de Vallejuelo et al., 2014). However, there are several sources of heavy metals in the sediment from the Chanthanburi coastline and from the different of land use in the boundary of each river basin. In the past (1991), land use in the coastal zone of Chanthaburi Province was dominated by prawn aquaculture developments (45.3% of the land portion of the study area). The major terrestrial land uses within the coastline are rice paddies (24.5%), fruit orchards (14.2%), mangrove forests (6.1%), rubber plantations (4.9%) and upland forests (3.5%) (Raine, 1994). Moreover, the widespread encroaching urbanization, tourism and recreation activities are continuously increasing in both upland and coastline area of Chanthaburi Province, especially along the Chanthaburi river.
Figure 4. Principal componentFigure 4. Principal analysis ofcomponent heavy metal analysis concentrations of heavy me in talsediments concentrations of the three in sediments river basin of theof coastal three river area of Chanthaburi Provincebasin of coastal area of Chanthaburi Province
3.5. Multiple regression analysis
The relationship between the140 heavy metals concentration and the sediment characteristics could be explained by the multiple regression equations as displayed in Table 7. The results of statistical analysis revealed that all heavy metals had significantly positive relationship with the organic matter (OM) and the clay particle size whereas Fe and Zn had also significantly negative relationship with the pH. This finding was in accordance with that of Buajan and Pumijumnong (2010) which demonstrated major affect and high relationship of OM to heavy metals in the sediment. The organic matter in the sediment is very important in controlling the heavy metals mobility and leaching in the sediment. The heavy metals forming complexes with OM can be carry to be deposited whereas the forms are enhanced or retained depending on the physicochemical characteristics of the sediments (Toribio and Romanyà, 2006). Haque and Subramanian (1982) reported that metal adsorption capacity increased with decreased grain size (sand J. Potipat et al. / EnvironmentAsia 8(1) (2015) 133-143 Table 7. Multiple regression equation of heavy metals concentration in sediments of coastal area of Chanthaburi Province Heavy metals (μg/g) Multiple regression equation R2 Significance of regression Pb YPb = 1.630 + 0.634(OM; %) + 0.101(Clay; %) 0.657 0.000 Cd YCd = 0.022 + 0.005(OM; %) + 0.001(Clay; %) 0.699 0.000 Cr YCr = 11.584 + 0.047(OM; %) + 0.149(Clay; %) 0.618 0.002 Fe LogYFe = 3.397 + 0.038(OM; %) + 0.012(Clay; %) – 0.095(pH) 0.412 0.030 Cu YCu = 13.038 + 1.415(OM; %) + 0.094(Clay; %) 0.541 0.023 Zn YZn = 9.817 + 1.729(OM; %) + 0.002(Clay; %) – 1.696(pH) 0.433 0.032 be explained by the multiple regression equations as mechanism of the distribution of all heavy metals was displayed in Table 7. The results of statistical analysis controlled by the organic matter (OM) and the clay revealed that all heavy metals had significantly positive particle size. The geoaccumulation index (Igeo) and relationship with the organic matter (OM) and the clay the enrichment factor (EF) showed that the low particle size whereas Fe and Zn had also significantly contamination of heavy metals was found at all stations negative relationship with the pH. This finding was which indicated that the heavy metals pollution in in accordance with that of Buajan and Pumijumnong sediment of the river basin of coastal area of (2010) which demonstrated major affect and high Chanthaburi was not a serious threat to the local relationship of OM to heavy metals in the sediment. ecosystem in study area. However, the investigation The organic matter in the sediment is very important in and monitoring should be continuously performance controlling the heavy metals mobility and leaching in to assess the long term effect of heavy metals in the sediment. The heavy metals forming complexes with Chanthaburi coastline. OM can be carry to be deposited whereas the forms are enhanced or retained depending on the physicochemical Acknowledgements characteristics of the sediments (Toribio and Romanyà, 2006). Haque and Subramanian (1982) reported that This research work is a sub-theme of the Ph.D. metal adsorption capacity increased with decreased dissertation entitled “Distribution, Bioconcentration and Depuration of Selected Heavy Metals in the River Basin of grain size (sand 141 J. Potipat et al. / EnvironmentAsia 8(1) (2015) 133-143 Baptista Neto JA, Smith BJ, McAllister JJ. Heavy metal Naji A, Ismail A. 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