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84 CHEMICAL PROBLEMS 2021 no. 2 (19) ISSN 2221-8688 @
UDC 543.3; 556.531
ASSESSMENT OF METAL POLLUTION IN WATER AND SURFACE SEDIMENTS OF
GORANCHAY RIVER
S.Sh. Mammadzada1, F.Y. Humbatov12, I.I. Mustafayev1
institute of Radiation Problems, National Academy of Sciences of Azerbaijan, H. JavidAve., 31 A, AZ 1143, Baku, Azerbaijan 2Azerbaijan University of Architecture and Construction A. Sultanova, 11, AZ 1073, Baku, Azerbaijan; e-mail: hfamil@mail.ru
Received 17.04.2021 Accepted 19.07.2021
Abstract: Concentration of metals in water and sediment samples from Goranchay River was examined to obtain information about metal pollution. Also, 6 surface sediments and water samples were collected from sampling points and analyzed for metals (Na, K, Mg, Ca, Al, Cr, Mn, Fe, Ni, Co, Cu, Zn, As, Cd, Sr, Ba, Pb) using Varian model Spectra AA 220 FS atomic absorption spectrometer. The average concentration of examined metals at the same sampling locations was in line with the order of
Ca>Fe>Mg>K>Na>Mn>V>Zn>Ni>Cr>Cu>Co>Pb in sediment samples. Single element pollution index values, including geo-accumulation index (Igeo), contamination factor (CF) and enrichment factor (EF), were used to evaluate contamination with metals in the examined sediment samples. Keywords: Goranchay river, water, sediment, metals, pollution DOI: 10.32 737/2221-8688-2021-2-84-93
Introduction
Heavy metals are considered to be serious pollutants of aquatic ecosystems due to their environmental persistence, toxicity, and ability to be incorporated into food chain [1].Heavy metal pollution in the natural environment is a worldwide problem because they are not removed from water due to the self-purification; however, they can get accumulated in reservoirs by means of biological and geochemical mechanisms and join the biological chain [2]. There are two main sources for lauding heavy metals into the environment: lithogenic and anthropogenic. Lithogenic is the natural process, such as weathering of rocks and volcanic activities that plays a noticeable role in enriching the water of reservoirs with heavy metals [3]. Anthropogenic sources arise from human activities, such as industry, agriculture, mining and construction of urban development that can transport pollutants to marine waters by rivers and outlets [4,5].
Goranchay is the North Caucasus River located in Azerbaijan. It flows through regions of Goygol and Goranboy and after joining with Kurakchay flows further to Kura. Length of the River is 81 km. It starts from a mountain area (height-3100 m) between Gamishdagh and Murovdagh. Goranchay is divided into two parts: Garachay and Goranchay near the village of Meshali in Goranboy region. Garachay and Goranchay flows parallel to each other up to Garachinar village. Main water sources of the Goranchay are snow, rains and underground waters. Water of the Goranchay is widely used as drinking water and for watering plantations in Goranboy region. Mean annual water usage of the river is 1.96 m3/s. During the period of intensive watering (July-August) 20% of the annual current is used. Spring flood of the river starts in March and continues till the end of July. Note that the River water is considered as moderately mineralized (300-500
CHEMICAL PROBLEMS 2021 no. 2 (19)
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mg/L) and known to have high amount of hydrocarbonates and calcium.
Materials and Methods
6 sampling points along Goranchay were estimated to examine heavy metal content in the study. Both water and sediment samples were collected from the same area. Note that pH, salinity, total dissolved solids, conductivity, temperature parameters of river water were measured at sampling points. Water samples were collected by means of a standard polyethylene water sampler which was rinsed a few times with river water from the sampling point before representative sampling from 15-30 cm below water surface. Two hundred millilitres of water was filtered through a 0.45 p,m membrane filter using a plastic filtration assembly without pump. A few drops of high-purity nitric acid were added to the filtrate to adjust to pH < 2. The sample was stored at 4 °C during transportations to the laboratory. Between each sampling, the water
Collected sediment samples air were dried in the laboratory, disaggregated with a mortar and pestle and passed through a 2 mm sieve. Particles with a bigger diameter than 2 mm were discarded. Dried, disaggregated and sieved particles (<2 mm) were mixed well and kept in labeled plastic containers for further analysis. To determine analytical and handling errors, two sub-samples were taken from each of these sediment samples, each undergoing an independent digestion procedure. Solutions were prepared using deionized water (from a Milli-Q apparatus (Millipore). Aliquots of
sampler was soaked with10% v/v nitric acid and rinsed with ultrapure water. All plastic-ware sample bottles, pipette tips, filtration unit and flasks were soaked in 10% v/v HNO3 for 24 h and rinsed with ultra pure water before being used. Ultra pure water collected from Milli-Q apparatus (resistivity 18.2 MQcm, pH (5.5-6.5)) was used throughout in all laboratory operations.Sediment samples from sampling points were collected by stainless-steel Van Veen grabs. Approximately 200 g of the sample was taken from the surface oxic layer of sediment at each station. Labeled samples stored in a frozen on the way back to the laboratory. Geographical locations of examined stations and measured water parameters(pH, conductivity (COND), total dissolved solids(TDS), salinity(SAL), dissolved oxygen(DO)) of Goranchay are given in Table 1.
approximately 0.5 g of sediment samples were weighed and added into the acid-cleaned TFM vessels and digested with a 9 ml of nitric and 3 ml of hydrochloric acid mixture in a microwave oven (Milestone Ethos 1 with HPR -1000/10S high pressure rotor). Samples transferred to 50 ml plastic vessels and diluted for analysis. Varian SpectrAA 220FS atomic absorption spectrometer system was used to determine heavy metal concentrations in samples to evaluate contamination levels in samples.
Table 1. GPS coordinates of sampling points and water parameters of Goranchay at the location
N/N Point description Coordinate pH COND TDS SAL DO DO
msm/cm mg/L % % mg/L
G1 YukhariAgcakand 40.406800° 46.522500° 7.12 146 85 0.01 86.8 8.89
G2 AshagiAgcakand 40.418596° 46.573495° 6.95 168 97 0.01 86.9 8.89
G3 Meshali 40.436619° 46.615070° 7.16 221 122 0.01 88.1 8.71
G4 Shafaq 40.453792° 46.641328° 7.52 331 191 0.02 89.4 8.68
G5 Shafibayli 40.483823° 46.713179° 7.71 404 233 0.02 91.1 8.45
G7 Goran 40.648798° 46.822691° 7.65 750 433 0.04 27.3 2.26
Results and discussion
The measured concentration of metals in water and sediment samples are given in Table 2 and Table 3 respectively. According to Table 2, concentrations of the analyzed elements in water samples of river Goranchay were as following: As: <0.5 mkg/L in all samples; Ba: ranged between 9-17 mkg/L; Cd: <0.1 mkg/L in all samples; Co: <0.7mkg/L in all samples; Cr: <0.5 mg/L in all samples; Cu: ranged between 0.60-2.26mkg/L; Fe: ranged between 6.64-33.05
Comparison between measured concentrations of investigated metal in water samples and limit values presented for the drinking water by World Health Organization (Table 2) shows that water of Goranchay is not polluted with metals and can be used for drinking purposes (with due regard for measured parameters in this study, further analysis is required for total evaluation). According to Table 3, measured parameters (examined metal concentrations) of sediment
mkg/L; Ni: ranged between 0.7-0.88mkg/L; Pb:<0.7 mkg/L in all samples; Mn: ranged between 0.357-4.257 mkg/L; Zn: ranged between 3.95-23.43mkg/L; Na: ranged between 3.78-18.59 mg/L; K: ranged between 0.49-1.49 mg/L; Mg: ranged between 2.98-13.35 mg/L, Ca ranged between 18.46-52.04 mg/L; Al: ranged between 11.15-29.85 mkg/L; Sr: ranged between 98-327.2 mg/L.
samples were as follows: Na: ranged between 543.52-3027.65 mg/kg, average concentration -1601,13 mg/kg; Ca: ranged between 27872.3484006.77 mg/kg, average concentration -56609.01 mg/kg; Zn:ranged between 54.92-89.33 mg/kg, average concentration -69.18 mg/kg; Mg: ranged between 15031.37-20263.06 mg/kg, average concentration -17523.41 mg/kg; K: ranged between 900.48-4483.56 mg/kg, average concentration -1857.87 mg/kg ; Mn: ranged
Table 2. Measured concentration of investigated metals in water samples
Element Unit G1 w G2 w G3 w G4 w G5 w WHO
Na mg/L 3.78 5.53 7.31 13.19 18.59 50
K mg/L 0.49 0.75 0.83 0.98 1.49 100
Mg mg/L 2.98 3.65 4.69 8.92 13.35 30
Ca mg/L 18.46 22.96 26.58 45.16 52.04 75
Al ug/L 26.27 29.85 16.56 11.15 12.90 200
Cr ug/L <0.5 <0.5 <0.5 <0.5 <0.5 50
Mn ug/L 0.637 4.257 0.503 0.357 0.512 100
Fe ug/L 20.69 33.05 9.26 8.83 6.64 300
Ni ug/L 0.700 0.810 0.720 0.840 0.880 70
Co ug/L <0.7 <0.7 <0.7 <0.7 <0.7 -
Cu ug/L 2.26 2.20 0.60 2.20 1.24 2000
Zn ug/L 13.79 22.76 3.95 9.09 23.43 5000
As ug/L <0.5 <0.5 <0.5 <0.5 <0.5 10
Cd ug/L <0.1 <0.1 <0.1 <0.1 <0.1 5
Sr ug/L 98.00 131.2 156.8 313.5 327.2 -
Ba ug/L 9.00 9.05 11.90 12.30 17.00 700
Pb ug/L <0.7 <0.7 <0.7 <0.7 <0.7 10
between 464.89-864.92 mg/kg, average concentration -695.04 mg/kg; Fe: ranged between 37714.38-61459.77 mg/kg, average concentration -43019.55 mg/kg; Co: ranged between 8.41-18.30 mg/kg, average concentration -14.02 mg/kg; Ni: ranged between 40.51-78.12 mg/kg, average concentration -57.06 mg/kg; Cu:
ranged between 23.97-46.05 mg/kg, average concentration -32.49 mg/kg; Pb: ranged between 2.89-7.31 mg/kg, average concentration -5.16 mg/kg; Cr: ranged between 28.52-112.27 mg/kg, average concentration -54.53 mg/kg ; V: ranged between 83.56-283.78 mg/kg, average concentration -140.71 mg/kg.
Table 3. Measured concentration of metals in sediment samples
G1 sed G2 sed G3 sed G4 sed G5 sed G7 sed
mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg
Na 3027.66 1302.80 1782.16 1349.16 1282.10 543.52
Ca 84006.77 57917.42 64287.16 42527.93 58860.16 27872.34
Zn 61.69 89.33 61.38 85.91 55.64 75.41
Mg 1878662 15031.37 16443.30 18436.59 17268.90 20263.06
K 1743.63 1133.55 1410.66 1961.17 900.48 4483.56
Mn 691.76 864.92 694.56 627.65 826.13 464.89
Fe 37731.18 61459.77 39896.80 43642.46 40305.39 40386.85
Co 14.21 18.30 13.46 12.91 17.48 13.35
Ni 40.51 43.10 58.42 78.02 71.91 58.03
Cu 31.51 46.05 29.88 32.56 23.97 29.30
Pb 6.04 7.31 4.64 4.67 2.89 4.67
Cr 28.52 34.83 38.41 59.36 112.27 67.39
V 129.51 283.78 134.25 132.18 97.76 83.56
Sediments are capable of recording the history and indicating the degree of pollution. To assess the degree of pollution of the heavy metal, it is necessary to compare the pollutant metal concentration with an unpolluted reference material (geochemical background)[6-13]. Absence of background values of metal concentrations in Azerbaijan estuarine systems made us to use the reference material. The reference material represents a benchmark to which the metal concentrations in the polluted samples are compared and measured. Many
authors used average shale values or average crustal abundance data as reference baselines [14]. In this work, average shale values are used as a reference material for background values [14]. Single element pollution indexes which give information of how an individual element is concentrated at a site of interest relative to the background were used to evaluate metal contamination. These include geo-accumulation index (Igeo), contamination factor (Cf) and enrichment factor (Ef).
Geo-Accumulation Index (Igeo)
A common criterion to evaluate the heavy metal pollution in sediments is the geo-accumulation index. The geo-accumulation index (Igeo) has been used since the late 1969s, and widely employed in European trace metal studies.
Geo-accumulation index was proposed by Muller [15] to determine metal contamination in sediments by comparing current concentrations with pre-industrial levels. It can be calculated using the following formula:
Igeo = l0g2[(Cn)/(1.5Bn)]
(1)
where Cn is the concentration of element "n," and Bn is the geochemical background value of the element n in average crust (average upper crustal concentration was given by Turekian K.K. Wedepohl, K.H) [14]. The factor 1.5 is incorporated in the relationship to account for possible variation in background data due to lithogenic effect. The geo-accumulation index (Igeo) scale consists of seven grades (0 - 6) ranging from unpolluted to highly polluted. Class 1 (uncontaminated to moderately contaminated): 0 <Igeo<1; Class 2 (moderately contaminated): 1<Igeo<2; Class 3 (moderately to heavily contaminated): 2<Igeo<3; Class 4 (heavily
contaminated): 3<Igeo<4; Class 5 (heavily to extremely contaminated): 4<Igeo<5; and Class 6 (extremely contaminated): 5>Igeo. Calculated Igeo values of metals are given in Table 4. As it can be seen from Table, Igeo values of Cr, Mn, Co, Zn and Pb are less than 0 in all sampling points. This indicates that investigated sediment samples can be categorized as practically unpolluted with mentioned heavy metals. Igeo values of V, Fe and Cu in sampling point 2, Ni in sampling points 4 and 5 are in the range of 0<Igeo<1 indicating uncontaminated to moderately contaminated level of pollution.
Table 4. Calculated Igeo values of metals in sediment samples
V Cr Mn Fe Co Ni Cu Zn Pb
-0.16797 -2.27445 -0.74888 -0.64006 -0.86839 -0.79931 -0.41465 -0.70408 -2.07762 G1 sed
0.963762 -1.98614 -0.42659 0.063826 -0.50372 -0.70998 0.132829 -0.17004 -1.80332 G2 sed
-0.11614 -1.84522 -0.74306 -0.55954 -0.94701 -0.2712 -0.4911 -0.71136 -2.4571 G3 sed
-0.13853 -1.21703 -0.88919 -0.43008 -1.0078 0.146161 -0.36747 -0.22636 -2.44953 G4 sed
-0.57377 -0.29771 -0.49279 -0.54484 -0.56976 0.028504 -0.80922 -0.8531 -3.14117 G5 sed
-0.80015 -1.03409 -1.32226 -0.54193 -0.9593 -0.2809 -0.51931 -0.41444 -2.45013 G7 sed
Contamination Factor
The level of metal contamination can be expressed by the contamination factor (CF). CF is the ratio between the metal content in the sediment and the background value of the metal. The contamination factor is used to determine the
where Cs and Cb: are the heavy metal contents in sample and background reference, respectively. According to Hakanson [17] CF<1 indicates low
contamination status of the sediment in the present study. Contamination factor is calculated according to the equation given by D. C. Thomilson, D. J. Wilson, C. R. Harris and D. W. Jeffrey [16].
(2),
contamination; 1<CF<3 indicates moderate contamination; 3<CF<6 indicates considerable degree of contamination; and CF>6 indicates very
high contamination. Calculated CF values of heavy metals in the analyzed samples are given in Table 5.Cf values of Cr in sampling points 1,2,3,4,7; Mn in sampling points 1,3,4,7; Fe in sampling point 1; Co in sampling points 1,3,4,7; Ni in sampling points 1 and 2; Cu in sampling point 5; Zn in sampling points 1,3,5; Pb in all sampling points are lower than 1 indicating low
contamination of sediments with mentioned heavy metals. CF values of V in sampling points 1-5; Cr in sampling point 5; Mn in sampling points 2 and 5; Fe in sampling points 2-7; Co in sampling points 2 and 5; Ni in sampling points 37; Cu in sampling points 1,2,3,4,7; Zn in sampling points 2,4,7 are in the range of 1<CF<3 which can be classified as moderately contaminated.
Table 5. CF values of metals in investigated samples
CF
V Cr Mn Fe Co Ni Cu Zn Pb
G1 sed 1.335139 0.310037 0.8926 0.96253 0.821638 0.861934 1.125302 0.92075 0.355359
G2 sed 2.925583 0.378621 1.116031 1.567851 1.057927 0.916991 1.644662 1.333228 0.42977
G3 sed 1.383976 0.417469 0.896206 1.017776 0.778061 1.242945 1.067222 0.916115 0.273168
G4 sed 1.362668 0.645251 0.809876 1.113328 0.745955 1.659931 1.162709 1.282185 0.274606
G5 sed 1.00779 1.22031 1.065973 1.028199 1.01059 1.529931 0.856033 0.83039 0.170022
G7 sed 0.861433 0.732487 0.599863 1.030277 0.771458 1.234619 1.04656 1.125466 0.274491
Enrichment Factor
The concept of enrichment factor (EF) was developed in the 1970s to evaluate the anthropogenic contribution. The enrichment factor (EF) is based on the standardization of a
tested element against a reference one. The obtained result is described as an enrichment factor (EF) given by the following equation [18].
(3),
where Cs and Cr are the content of the target element and reference element in the examined sediment, respectively and Csb and Crb are the content of the target element and reference element in the average shale. To identify anomalous metal concentration, geochemical normalization of the heavy metals data was used for the investigated element. The behavior of a given element in sediment established by comparing the concentration of certain heavy metal with the reference element. Because Al is one of the most abundant elements on the earth and usually has no pollution concerns, it is commonly used for normalization purpose [10,19,20]. In enrichment factor (EF) calculations, Fe is also widely used [21-23] as a reference element. In this study, we used Fe as a
reference element to differentiate natural and anthropogenic components. The world average shale and world average rock element concentrations are widely used as background concentrations in most of the studies [15]. EF<2 indicates that the source of a metal is crust materials or natural processes; whereas EF >2 indicates anthropogenic sources [24-26]. EF<2 indicates minimal enrichment, 2-5 indicates moderate enrichment, 5-20 indicates significant enrichment, 20-40 indicates very high enrichment and EF > 40 indicates extremely high enrichment. EF values of elements were calculated using Equation (3). Results are given in Table 6. Results shows that EF values of all heavy metals in all sampling points are less than 2. This means that
sources of the analyzed metals in sediment samples are crust materials or natural processes.
Table 6. EF values of metals in sediment samples
V Cr Mn Fe Co Ni Cu Zn Pb
1.387114 0.322107 0.927347 1 0.849268 0.895487 1.169108 0.956593 0.369192 G1 sed
1.865983 0.24149 0.711822 1 0.67132 0.584871 1.048991 0.850353 0.274114 G2 sed
1.359804 0.410178 0.880554 1 0.760572 1.221236 1.048583 0.900115 0.268397 G3sed
1.223959 0.57957 0.727437 1 0.666605 1.490963 1.044355 1.151669 0.246653 G4 sed
0.980151 1.186843 1.036738 1 0.97786 1.487972 0.832556 0.807616 0.165359 G5 sed
0.836118 0.710961 0.582235 1 0.744967 1.198337 1.015805 1.092391 0.266424 G7 sed
Conclusions
Metal concentrations (Na, K, Mg, Ca, Al, Cr, Mn, Fe, Ni, Co, Cu, Zn, As, Cd, Sr, Ba,Pb) of water samples and surface sediments from Goranchay River were measured. Comparison between measured concentration of heavy metal in water samples and limit values presented for the drinking water by World Health Organization (Table 2) shows that water of Goranchay is not polluted with heavy metals and can be used for drinking purposes (with due regard for measured parameters in this study, further analysis is needed for total evaluation).To investigate the contamination degree of heavy metals in sediments, geo-accumulation index
(Igeo),enrichment factor (EF) andcontamination factor (CF) were calculated. Calculated Igeo values of Cr, Mn, Co, Zn and Pb are less than 0 in all sampling points. This indicates that
investigated sediment samples can be categorized as practically unpolluted with mentioned heavy metals. Igeo values of V, Fe and Cu in sampling point 2, Ni in sampling points 4 and 5 are in the range of 0<Igeo<1 indicating uncontaminated to moderately contaminated level of pollution. CF values of heavy metals shows low or moderate contamination in all sediments from investigated sampling points. Calculation results showed that EF values of heavy metals in all sampling points are less than 2. This means that sources of the analyzed metals in sediment samples are crust materials or natural processes. According to the calculated single element pollution index values, it can be said that anthropogenic effect on sediments of Goranchay is considerably low and contamination level of sediments of the river is ranging from low to moderate.
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GORANQAYDAN GOTURULONSU VO DiB QOKUNTUSUNUMUNdLdRiNDd METALLARLA QiRKLONMONiN QiYMOTLdNDiRILMdSi
S.§. Msmmsdzads1, F.Y. Humbstov1'2, i.i. Mustafayev1
1AMEA-nin Radiasiya Problemlsri institutu AZ 1143, Baki, H. Cavidpr., 31 A, 2Memarliq vs tnqaat Universiteti AZ 1073 Baki, A.Sultanova kug., 11, e-mail: hfamil@mail.ru
Xulass: Gorangaydan goturulsn su vs dib gokuntusu numunslsrinds metallarla girklsnmsyls bagli informasiya toplamaq msqssdils metallarin konsentrasiyalari tsdqiq olunmuqdur. 6 ssth dib gokuntusu vs su numunssi numuns goturms noqtslsrindsn toplanmiq vs Varian SpectrAA 220FS atom absorbsiya spektrometri vasitssils metallara (Na, K, Mg, Ca, Al, Cr, Mn, Fe, Ni, Co, Cu, Zn, As, Cd, Sr, Ba, Pb) gors analiz olunmuqdur. Dib gokuntusu numunslsrinds eyni numuns goturms noqtssinds agir metallarin orta konsentrasiyalarinin azalma ardicilligi belsdir Fe>Mn>V>Zn>Ni>Cr>Cu>Co>Pb. Geo-akkumulyasiya indeksi, girklsnms faktoru, zsnginlsqms faktoru daxil olmaqla tsk elementli girklsnms indeksi qiymstlsrindsn dib gokuntusu numunslsrinds agir metallarla girklsnmsni qiymstlsndirmsk ugun istifads olunmuqdur. Agar sozlsr: Goran gayi, su, dib gokuntusu, agir metallar, girklsnms
ОЦЕНКА ЗАГРЯЗНЕНИЯ ВОДЫ И ПОВЕРХНОСТНЫХ ОТЛОЖЕНИЙ РЕКИ ГОРАНЧАЯ
МЕТАЛЛАМИ
С.Ш. Мамедзаде1, Ф.Ю. Гумбатов1'2, И.И. Мустафаев1
1 Институт Радиационных Проблем Национальной АН Азербайджана, AZ 1143, Баку, пр. Г.Джавида, 31 А, 2Университет архитектуры и строительства, AZ 1073, Баку, ул. А. Султановой, 11; e-mail: hfamil@mail.ru
Для получения информации о загрязнении металлами были определены концентрации металлов в воде и образцах донных отложений реки Горанчай. 6 проб отложений и воды были собраны в точках отбора проб и проанализированы на содержание металлов (Na, K, Mg, Ca, Al, Cr, Mn, Fe, Ni, Co, Cu, Zn, As, Cd, Sr, Ba, Pb) с помощью атомно-абсорбционного спектрометра Varian SpectrAA 220 FS. Средняя
концентрация исследованных металлов в тех же местах отбора проб следовала порядку Ca>Fe>Mg>K>Na>Mn>V>Zn>Ni>Cr>Cu>Co>Pb в пробах отложений. Значения индекса загрязнения одним элементом, включая индекс геоаккумуляции (Игео), коэффициент загрязнения (КЗ) и коэффициент обогащения (КО), использовались для оценки загрязнения тяжелыми металлами в исследованных пробах отложений.
Ключевые слова: Река Горанчай, вода, отложения, тяжелые металлы, загрязнение.
