Spatial and temporal trace metal distribution of a Peruvian basin: recognizing trace metal sources and assessing the potential risk

Recent efforts have been made to determine the environmental impact of mining over the past 11 years in the Jequetepeque River basin, in northern Peru. We have now analyzed data from two studies to elucidate the spatial and temporal trace metal distributions and to assess the sources of contamination. These two studies were carried out from 2003 to 2008 by a Peruvian government administration and from 2008 to 2010 by us. We analyzed 249 samples by principal component analysis, measuring: pH, electrical conductivity, total dissolved solids, total suspended solids, chloride, weak-acid-dissociable cyanide, total cyanide, nitrite and nitrate, ammonium, sulfate, and trace metals and metalloids (Al, As, Ca, Cd, Cu, Cr, Fe, Mg, Mn, Ni, Pb, and Zn). Within the spatial distribution of the basin, the highest Al, As, Cu, Fe, Ni, and Pb concentrations were found at the closest point to the mine sites for both periods of time, with the higher peaks measured during the first years of the sampling data. Temporal trends showed higher concentrations of Cu and Fe in samples taken before 2005, at which point the two mines were closed. Risk assessment was quantified by the hazard quotient as related to water ingestion. The risk for human health posed by the concentrations of several trace metals and metalloids was found to be highly adverse (As and Cr), significant (Al, Cd, Cu, Fe, and Pb), or minimal (Ni and Zn).     

Dissolved and particulate metals in water from Sonora Coast: a pristine zone of Gulf of California

The purpose of this study was to investigate the distribution of metals (Cd, Pb, Hg, Cu, Fe, Mn, and Zn) in dissolved and particulate fractions in seawater from Bacochibampo Bay, Northern part of Mexico. Water samples were collected from November 2004 to October 2005. Metal analysis was done by graphite furnace atomic absorption spectroscopy. Results indicated highest concentrations of dissolved Cd and Zn in the sites localized at the mouth and center of the bay. During summer and spring, the highest levels of Cd, Mn, and Fe were detected, Zn in fall, and Pb and Cu in winter and spring. Mercury was the only metal that was not found in this fraction. In particulate fraction, Fe, Hg, and Mn were the most abundant elements in all the sampling sites, followed by Zn, Cu, Pb, and Cd. The highest levels of the majority of the metals were observed in the coastline, suggesting a continental and/or urban source for these chemicals. The highest level of Cd was detected during the summer and the rest of the metals in the fall. Statistically significant correlations were observed between dissolved and particulate forms of Pb:Mn, Cu:Fe, and Cu:Mn. The mean partition coefficient values were as follows: Fe>Mn>Cu>Pb>Cd>Zn. All dissolved metal concentrations found, except Pb, were lower than EPA-recommended water quality values. The levels of dissolved metals in this study reveal low bioavailability and toxic potential. However, further toxicological and sediment chemistry studies in this area are needed for a full risk assessment.     

Spatial distribution of trace metals (Cd, Pb, Hg, Cu, Zn, Fe and Mn) and oligo-elements (Mg, Ca, Na and K) in surface sediments of the Gulf of Tunis (Northern Tunisia)

The purpose of this paper is to evaluate the levels and spatial distribution of trace metals (Cd, Pb, Cu, Hg, Zn, Fe, and Mn), oligo-elements (Mg, Ca, Na and K), total organic carbon (TOC), and total nitrogen (TN) in the fine fraction of surface sediments collected from 38 stations in Gulf of Tunis (Mediterranean Sea, Northern Tunisia) between 2004 and 2005. The results showed that metals, oligo-elements, TOC, and TN concentrations in the sediments of the Gulf of Tunis are generally low compared to those found in other similar coastal marine areas. The spatial distribution of metals showed areas of major accumulation of Pb, Cd, Cu, Fe, and Zn in the central area of the Gulf and near the Mejerda River. The marine currents are influencing factors on metal accumulation in sediments. The principal component analysis applied to our elemental analytical results showed that there is a positive correlation between Fe, Zn, Cu, and Pb. These metals have a stronger affinity with site connection in the sediments than Ca and Mn.     

Dynamics and quantification of dissolved heavy metals in the Mahanadi river estuarine system,India

Dynamics of heavy metals such as Fe, Mn, Zn, Cr, Cu, Co, Ni, Pb, and Cd in surface water of Mahanadi River estuarine systems were studied taking 31 different stations and three different seasons. This study demonstrates that the elemental concentrations are extremely variable and most of them are higher than the World river average. Among the heavy metals, iron is present at highest concentration while cadmium is at the least. The spatial pattern of heavy metals suggests that their anthropogenic sources are possibly from two major fertilizer plants and municipal sewage from three major towns as well as agricultural runoff. The temporal variations for metals like Fe, Cu, and Pb exhibit higher values during the monsoon season, which are related to agricultural runoff. Concentrations of Ni, Pb, and Cd exceed the maximum permissible limits of surface water quality in some polluted stations and pose health risks. Dissolved heavy metals like Fe, Mn, Cr, Ni, and Pb exhibit a non-conservative behavior during estuarine mixing, while Zn, Cu, and Co distribution is conservative. Distribution of cadmium in the estuarine region indicates some mobilization which may be due to desorption. The enrichment ratio data suggest that various industrial wastes and municipal wastes contribute most of the dissolved metals in the Mahanadi River. The Mahanadi River transports 18.216 × 10³ t of total heavy metals into the Bay of Bengal and the calculated rate of erosion in the basin is 128.645 kg km^− 2 year^− 1.     

Distribution and solid-phase speciation of toxic heavy metals of bed sediments of Bharali tributary of Brahmaputra River

Heavy metal (Fe, Mn, Zn, Cu, Ni, Pb, and Cd) concentrations and their chemical speciations were investigated for the first time in bed sediments of Bharali River, a major tributary of the Brahmaputra River of the Eastern Himalayas. Levels of Fe, Mn, Pb, and Cd in the bed sediments were much below the average Indian rivers; however, Cu and Zn exhibit levels on the higher side. Enrichment factors (EF) of all metals was greater than 1 and a higher trend of EF was seen in the abandoned channel for most metals. Pb showed maximum EF of 32 at site near an urban center. The geoaccumulation indices indicate that Bharali river is moderately polluted. The metals speciations, done by a sequential extraction regime, show that Cd, Cu, and Pb exhibit considerable presence in the exchangeable and carbonate fraction, thereby showing higher mobility and bioavailability. On the other hand, Ni, Mn, and Fe exhibit greater presence in the residual fraction and Zn was dominant in the Fe?CMn oxide phase. Inter-species correlations at three sites did not show similar trends for metal pairs indicating potential variations in the contributing sources.     

Chemometric study on the trace metal accumulation in the sediments of the Cochin Estuary―Southwest coast of India

The distribution and accumulation of trace metals in the sediments of the Cochin estuary during the pre-monsoon, monsoon and post-monsoon periods were investigated. Sediment samples from 14 locations were collected and analysed for the metal contents (Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb), organic carbon, total nitrogen, total sulphur and grain size. The data were processed using statistical tools like correlation, factor and cluster analysis. The study revealed an enrichment of Cd and Zn in the study area particularly at station 2, which is confirmed by enrichment factor, contamination factor and geoaccumulation index. The factor analysis revealed that the source of Cd and Zn may be same. The study indicated that the spatial variation for the metals like Mg, Cr, Fe, Co, Ni, Cu, Zn, Cd and Pb were predominant unlike Mn which shows a temporal variation. The strong association of trace metals with Fe and Mn hydroxides and oxides are prominent along the Cochin estuary. The anthropogenic inputs of industrial effluents mainly control the trace metals enrichment in the Cochin estuary.     

Heavy metals in cooler waters in Riyadh, Saudi Arabia

Water samples were collected from 400 coolers in Riyadh area. From each cooler, one feed and one cooled water samples were collected. These samples were analyzed for trace metals like Al, Cr, Cu, Fe, Mn, Ni, Pb, and Zn by Inductively Coupled Plasma (ICP) Spectrophotometer equipped with ultrasonic nebulizer. Out of 400 coolers, water from 382 (95.50%) were found to meet World Health Organization (WHO), Saudi Arabian Standards Organization (SASO), and United States Environmental Protection Agency (USEPA) drinking water standards whereas water from 18 coolers (4.50%) were found to have elevated levels of Fe, Pb, and Ni metals. In one cooler, water was allowed to stand for 12 h and a 1 L sample collected every 2 h. All the metals mentioned above with the exception of Pb were found to increase due to standing time.     

花垣河锰污染及其成因分析

对花垣河河水中8个监测断面（S1-S8）水样和堆积在河岸附近MnSO4废渣及其浸出液中Mn、Cd、Pb、Cu和Zn等5种重金属元素的总量进行了分析。结果表明，花垣河河水中Mn和Cd质量浓度超过《地表水环境质量标准》（GB3838—2002）V类水体标准；MnSO4废渣浸出液中Cd超过《危险废物鉴别标准》（GB5058．3—1996）规定值。将花垣河河水中Mn、Cd、Pb、Cu和Zn的含量与MnSO4废渣浸出液中相应的元素含量进行相关性分析，r=0．957（P〈0．01），表明堆积在花垣河河岸附近MnSO4废渣是可能造成花垣河污染的主要来源。     

Water quality trends in Polyphytos reservoir, Aliakmon River, Greece

A water quality monitoring program was undertaken from June 2004 to May 2005, on a monthly basis, in Polyphytos Reservoir of Aliakmon River. Depth, water temperature, dissolved oxygen, conductivity, pH and transparency (Secchi disk) were measured in situ, while collected water samples were analyzed in the laboratory for the determination of BOD, COD, total phosphorus (TP), ortho-phosphate (OP), chlorophyll-a (Chl-a), ammonium, nitrite and nitrate, total Kappajeldahl nitrogen (TKN) and heavy metals (Fe, Mn, Cu, Cr, Pb, Ni and Cd). Measured concentrations were compared to those from two previous studies conducted in July 1987 to June 1988 and January 1991 to February 1993. The following conclusions are drawn: the effect of the watershed on the lake environment, mostly through Aliakmon River, is significant, and it accelerates the eutrophication of the lake. The anoxic zones, which were defined in the lake, reinforce this conclusion. Nitrate, nitrite and ammonia were measured at lower concentrations compared to previous studies, while total phosphorus and chlorophyll-a were found at increased concentrations. The current trophic state of Polyphytos reservoir is eutrophic, based on the OECD method and Carlson's Trophic State Indices (TSI). The concentration of BOD and COD ranged at low levels. Furthermore, the mean concentrations of metals Fe, Mn, Cu, Cr, Pb, and Cd were below the potable water standards set by WHO and EU. During most part of the study period the ratio N/P for Polyphytos reservoir was higher than 7.2:1, and therefore, phosphorus is the limiting nutrient for algal growth.     

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.     

Assessment of background levels of trace metals in water and soil from a remote region of Himalaya

Selected trace metals were estimated by atomic absorption spectrometry in the water and soil samples collected from the remote region of Himalaya. The soil samples were analysed for soluble and acid extractable fraction of trace metals. In water samples, Ca, Na, Mg and K emerged as dominant contributors, whereas, Ca, Na, K, Mg, Fe and Pb were estimated at comparatively higher levels in the water extract of the soil. In case of acid extract of the soil samples, Ca, K, Fe, Mg, Mn and Na were found at elevated concentrations. Based on mean levels of the metals, following decreasing concentration order was observed in water samples: Ca > Na > Mg > K > Pb > Co > Cu > Zn > Mn > Cr > Fe > Cd > Li, however, in the acid extract of the soil, following order was noted: Ca > K > Fe > Mg > Mn > Na > Pb > Zn > Cr > Li > Cu > Co > Cd. The correlation study revealed appreciably diverse mutual relationships of trace metals in the water and soil samples. The multivariate cluster analyses exhibited divergent apportionment of trace metals in water and soil samples. Among the trace metals, Cd, Pb, Li, Zn, Cr, Cu, Mn and Co exhibited extreme to significant anthropogenic enrichment in the soil samples, while the rest of the metals were mostly contributed by the natural processes.     

Metal concentrations in the soils and native plants surrounding the old flotation tailings pond of the copper mining and smelting complex Bor (Serbia)

In this study concentrations of metals in the native plants and soils surrounding the old flotation tailings pond of the copper mine were determined. It has been established that the soil is heavily contaminated with copper, iron and arsenic, the mean concentrations being 1585.6, 29,462.5 and 171.7 mg kg(-1) respectively. All the plants, except manganese, accumulated metallic elements in concentrations which were either in the range of critical and phytotoxic values (Pb and As) or higher (Zn), and even much higher (Cu and Fe) than these values. Otherwise, the accumulation of Mn, Pb and As was considerably lower than that of Cu, Fe and Zn. In most plants the accumulation of target metals was highest in the root. Several plant species showed high bioaccumulation and translocation factor values, which classify them into species for potential use in phytoextraction. The BCF and TF values determined in Prunus persica were 1.20 and 3.95 for Cu, 1.5 and 6.0 for Zn and 1.96 and 5.44 for Pb. In Saponaria officinalis these values were 2.53 and 1.27 for Zn, and in Juglans regia L. they were 8.76 and 17.75 for Zn. The translocation factor in most plants, for most metals, was higher than one, whereas the highest value was determined in Populus nigra for Zn, amounting to 17.8. Among several tolerant species, the most suitable ones for phytostabilization proved to be Robinia pseudoacacia L. for Zn and Verbascum phlomoides L., Saponaria officinalis and Centaurea jacea L. for Mn, Pb and As.     

Determination of trace heavy metals in harvested rainwater used for drinking in Hebron (south West Bank,Palestine) by ICP-MS

Rainwater samples harvested for drinking from the west part of Hebron (south of West Bank in Palestine), the largest city in the West Bank, were analyzed for the content of different trace heavy metals (Cr, Mn, Co, Ni, Cu, Zn, Mo, Ag, Cd, Bi, and Pb) by inductively coupled plasma mass spectrometry (ICP-MS). This study was conducted to determine the water quality of harvested rainwater used for drinking of south West Bank (case study, Hebron area). A total of 44 water samples were collected in November 2012 from 44 house cisterns used to collect rainwater from the roofs of houses. The samples were analyzed for their pH, temperature, electrical conductivity, total dissolved solids, and different heavy metal contents. The pH of all water samples was within the US Environmental Protection Agency limits (6.5–8.5), while some water samples were found to exceed the allowed WHO limit for total dissolved solids (TDSs) in drinking water. Results showed that concentrations of the heavy metals vary significantly between the 44 samples. Results also showed that the concentration of five heavy metals (Cr, Mn, Ni, Ag, and Pb) is higher than the WHO limits for these heavy metals in drinking water. Overall, our findings revealed that harvested rainwater used for drinking of this part of south West Bank is contaminated with heavy metals that might affect human health.     

Determination of trace metals in drinking water in Irbid City-Northern Jordan

Drinking water samples from Irbid, the second populated city in Jordan were analyzed for trace metals (As, Ba, Cd, Pb, Cr, Cu, Fe, Zn, Mn, Ni, and Se) content. The study was undertaken to determine if the metal concentrations were within the national and international guidelines. A total of 90 drinking water samples were collected from Al-Yarmouk University area. The samples were collected from three different water types: tap water (TW), home-purified water (HPW), and plant-purified water (PPW). All the samples were analyzed for trace metals using an inductively coupled plasma-optical emission spectrometry. All the samples analyzed were within the United States Environmental Protection Agency admissible pH limit (6.5–8.5). The results showed that concentrations of the trace metals vary significantly between the three drinking water types. The results showed that HPW samples have the lowest level of trace metals and the concentrations of some essential trace metals in these samples are less than the recommended amounts. Slight differences in the metal contents were found between HPW samples, little differences between PPW samples; however, significant differences were found between TW samples. Although some TW samples showed high levels of trace metals, however, the mean level of most elements determined in the samples were well within the Jordanian standards as well as the World Health Organization standards for drinking water.     

Trace element concentration in groundwater of Pesarlanka Island, Krishna Delta, India

There is a growing concern over the potential accumulation of trace element concentration in groundwater of coastal aquifer owing seawater encroachment in the last several decades. A total of 29 groundwater samples collected from Pesarlanka Island, Krishna delta, Andhra Pradesh, India were analyzed for 13 trace elements (B, V, Mn, Fe, Ni, Co, Cu, Zn, As, Sr, Cd, Ba, and Pb) using inductively coupled plasma mass spectrometry. The results reveal that B, Fe, Ni, As, Sr, and Pb vary from 11.22 to 710.2, 1.25 to 684.6, 0.02 to 37.33, 27.8 to 282.3, 164.1 to 7,009, and 1.97 to 164.4 μg/l, respectively. Ba, Cd, Co, Cu, Ni, V, and Zn are almost within permissible limits for drinking water, but As, Fe, Mn, Pb, B, and Sr are above the permissible limit. The toxic element Pb is 1.64 times more than the maximum permissible limits of drinking water. The minimum value of As is also 2.78 times more, whereas the maximum is 28.2 times the permissible limit. The spatial distributions of alkaline earths (Sr, Ba), transition metals (V, Co, Ni, Fe), metallic elements (Cu, Pb), and (As) were found in considerable variation in the entire Island. Good cross-correlations were found between As, B, Co, and Sr with total dissolved solids and among other trace elements such as B, As, Co, and Sr. The variability observed within the groundwater samples is closely connected to the sea spray input; hence, it is primarily a consequence of geographical and meteorological factors, such as distance from the ocean and time of year. The trace element levels, in particular those of heavy metals, are very low, suggesting an origin from natural sources rather than from anthropogenic contamination. A few trace elements (Sr and B) are found as sensitive parameters responding to changes in fresh to saline groundwater environment. The highly elevated trace elements in this area which may be attributed to marine sediments or death and decay of plants are presented in this paper.     

Contamination by lead in sediments at Toledo River,hydrographic basin of PARANÁ III

Due to intense agricultural and industrial activities, the environment has been affected by increasing amounts of pollutants, such as lead, a toxic heavy metal. When introduced to the environment, toxic metals are distributed and incorporated into the liquid medium, sediments, and aquatic biota; bioaccumulating. This research aimed to identify and quantify the levels of toxic metals present in the waters and sediments of Toledo River, compare the obtained results with legislation and other studies, as well as to evaluate the possible pollutant sources of the water body. Six water and sediment samples were taken at seven strategic sites. The concentrations of Cu, Zn, Fe, Mn, Cd, Pb, and Cr in water were compared to the maximum limits established by Brazilian legislation IN CONAMA No. 357/05, for class II fresh waters. The sediment samples were submitted to nitroperchloric digestion, and then the total concentrations of the metals were determined by flame atomic absorption spectrometry (FAAS). The toxicological quality of the Toledo River has been considerably affected by the activities carried out in its surroundings, such as extensive areas of agriculture, pig farming and industrial areas, causing concentrations of Cd, Fe, and mainly Pb, which is observed at concentrations higher than value allowed by the legislation.     

Metal Pollution Assessment of Sediment and Water in the River Hindon, India

The metal pollution in water and sediment of the River Hindon in western Uttar Pradesh (India) was assessed for Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn. The metal concentrations in water showed wide temporal variation compared with bed sediment because of variability in water discharge and variations in suspended solid loadings. Metal concentrations in bed sediments provided a better evaluation of the degree and the extent of contamination in the aquatic environment, Santagarh and Atali being the most polluted sites of the river. The ratio of heavy metals to conservative elements (Fe, Al, etc.) may reveal the geochemical imbalances due to the elevated metal concentrations normally attributed to anthropogenic sources. Metal/Al ratios for the bed sediments of the river Hindon were used to determine the relative mobility and general trend of relative mobility occurred Fe > Mn > Zn > Cr > Ni > Pb > Cu > Cd.     

Macro- and microelement distribution in organs of Glyceria maxima and biomonitoring applications

The content of nutrients (N, P, K, Ca and Mg) and of trace metals (Fe, Cu, Mn, Zn, Pb, Cd, Co and Ni) in water, bottom sediments and various organs of Glyceria maxima from 19 study sites selected in the Jeziorka River was determined. In general, the concentrations of nutrients recorded in the plant material decreased in the following order: leaf>root>rhizome>stem, while the concentrations of the trace elements showed the following accumulation scheme: root>rhizome>leaf>stem. The bioaccumulation and transfer factors for nutrients were significantly higher than for trace metals. G. maxima from agricultural fields was characterised by the highest P and K concentrations in leaves, and plants from forested land contained high Zn and Ni amounts. However, the manna grass from small localities showed high accumulation of Ca, Mg and Mn. Positive significant correlations between Fe, Cu, Zn, Cd, Co and Ni concentrations in water or sediments and their concentrations in plant indicate that G. maxima may be employed as a biomonitor of trace element contamination. Moreover, a high degree of similarity was noted between self-organizing feature map (SOFM)-grouped sites of comparable quantities of elements in the water and sediments and sites where G. maxima had a corresponding content of the same elements in its leaves. Therefore, SOFM could be recommended in analysing ecological conditions of the environment from the perspective of nutrients and trace element content in different plant species and their surroundings.     

贵州煤矿区表层水-沉积物重金属分布特征及来源分析——以新寨河为例

为探索贵州煤矿区表层水-沉积物中重金属的分布特征及来源,科学制定环境保护与污染治理措施,以新寨河为研究对象,在11个样点共采集66个表层水体和沉积物样品,通过对Cd、Pb、Cr、Zn、Cu、As、Hg、Fe、Mn等9种重金属元素进行分析,揭示其在新寨河的空间分布特征。同时,利用多指数法开展了有毒重金属元素污染状况评价,通过相关性分析和主成分分析解析了重金属的来源。结果表明,新寨河流域表层水体中,Fe、Mn点位超标率达100%。表层水中重金属元素的平均含量排序为Fe＞Mn＞Zn＞Cu＞Cr＞As＞Cd＞Pb＞Hg,而沉积物中重金属元素的平均含量排序则是Fe＞Mn＞Zn＞Cr＞Cu＞As＞Pb＞Cd＞Hg,表明新寨河表层水体和沉积物中重金属元素的空间分布存在一定差异。各重金属元素的内梅罗综合污染指数介于0.59~1.13之间,表明新寨河表层水体中重金属的污染程度达到轻微污染水平。单种重金属元素的潜在生态危害系数计算结果显示,90.91%和9.09%的沉积物样点分别被归类为轻微风险和中等风险。所有样点沉积物的潜在生态危害指数介于14.57~120.55之间(均值为72.08),表明新寨河沉积物的潜在生态风险较低。Cu、As在多个样点存在污染现象,需予以重点监控管理。新寨河流域重金属的来源可分为三大类:Cd、Pb、Cr、Zn、Cu为第一类,对应地表径流源;As、Fe、Mn为第二类,对应煤矿开采源;Hg为第三类,对应复合源。     

Assessment of elemental distribution and trace element contamination in surficial wetland sediments, Southern Tibetan Plateau

In order to analyze and evaluate different trace metals on surface water of the Changjiang River, concentrations of dissolved trace metals (Cu, Ni, Fe, Co, Sc, Al, Zn, Pb, Cd, Se, As, Cr, and Hg), major elements(Ca and Mg), and nutrient(NO $_{3}^{-})$ were measured. Samples were taken at 76 positions along Changjiang River in flood and dry seasons during 2007?C2008. Spatial distributions identified two main large zones mainly influenced by mineral erosion (sites 1?C22) and anthropogenic action (sites 23?C76), respectively. Principal component analysis (PCA) and hierarchical cluster analysis were used to identify the variance distinguishing the origin of water. Four significant components were extracted by PCA, explaining 74.91% of total variable. Cu, Ni, Fe, Co, Sc, Al, Ca, and Mg were mainly associated with the weathering and erosion of various rocks and minerals, while an anthropogenic source was identified for Cd and As. Although erosion was one source of Pb and Zn, they were also input by atmospheric deposition and industrial pollutions. NO $_{3}^{-}$ and Se were mainly associated with agriculture activities. However, Hg and Cr showed different sources. CA confirmed and completed the results obtained by PCA, classifying the data into two large groups representing different areas. Group 1 referred to the upper reaches which represented samples mainly corresponding to natural background areas. Group 2 referred to the middle and lower reaches including samples under anthropogenic influence. Meanwhile, group 2 was subdivided into three new groups, representing agricultural, industrial, and various artificial pollution sources, respectively.