Chemical fractionation of heavy metals in urban soils of Guangzhou, China

Knowledge of the total concentration of heavy metals is not enough to fully assess the environmental impact of urban soils. For this reason, the determination of metal speciation is important to evaluate their environment and the mobilization capacity. Sequential extraction technique proposed by the former European Community Bureau of Reference (BCR) was used to speciate Cd, Cu, Fe, Mn, Ni, Pb, and Zn in urban soils from Guangzhou into four operationally defined fractions: HOAc extractable, reducible, oxidizable, and residual. The Cu, Fe, Ni, and Zn were predominately located in the residual fraction, Pb in the reducible fraction, and Cd and Mn within the HOAc extractable fraction. The order of Cd in each fraction was generally HOAc extractable > reducible > residual > oxidizable; Cu and Fe were residual > reducible > oxidizable > HOAc extractable; Mn was HOAc extractable > residual > reducible > oxidizable; Ni and Zn were residual > reducible > HOAc extractable > oxidizable; and Pb was reducible > residual > oxidizable > HOAc extractable. Cadmium was identified as being the most mobile of the elements, followed by Mn, Zn, Ni, Cu, Pb and Fe. Iron–Mn oxides can play an important role in binding Cd, Cu, Ni, Pb, and Zn and in decreasing their proportion associated with the residual fraction in the soils. With total concentrations of Cd, Cu, Ni, Pb, Zn, and Mn increase, these metals more easily release and may produce more negative effects on the urban environment.     

Trace metal speciation and contamination in an intertidal estuary

An analysis of the geochemical distribution of selected trace metals among various geochemical phases of the sediments in the Tees estuary was carried out using a sequential extraction technique and Differential Stripping Voltammetry. The sediments of the estuary are mainly organic rich clay silts and metal concentrations exceed those in the water column. Speciation results show that contamination of the estuary is mainly from anthropogenic sources. Pb and Zn are associated with the reducible, residual and oxidisable fractions. The speciation pattern of Cd was similar to those of lead and zinc. However there were also some exchangeable and bound to carbonate fractions although these were less significant. Cu is largely associated with the oxidisable and residual fractions, with insignificant bound to carbonate, exchangeable and reducible fractions. The most bioavailable forms of the metals are the free inorganic ions. Total metal concentrations in the estuary display a downward trend since the 1970s.     

Speciation and assessment of heavy metals in surface sediments of Jinjiang River tidal reach, southeast of China

The concentration and speciation of heavy metals (Cr, Ni, Cu, Zn, Cd, Pb) in surface sediments (??≤ 63 μm) of Jinjiang River tidal reach are determined to evaluate the metal behavior. A modified BCR three-step sequential extraction procedure is carried out, and the residual fraction is undertaken by microwave-assisted acid digestion. The index of geo-accumulation indicates that Cd appeared highest among all these heavy metals in surface sediments, Cr, Cu, Zn lower, and Ni, Pb the least. The percentage of Zn, Cd is comparatively higher in the acid soluble fraction, Pb and Cu higher in the reductive fraction, indicating larger potential danger to the environment. So it is essential for developing the future remediation plans and pollution control strategies.     

Total concentrations, fractionation and mobility of heavy metals in soils of urban area of Guwahati, India

This work describes the results of assessment of the heavy metals, Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn in urban soil of Guwahati City, India from 31 sites of five different land use types covering residential, commercial, industrial, public utilities, and roadside. Sequential extraction procedure was used to evaluate the relative distribution of the eight metals in exchangeable, carbonate, reducible (Fe?CMn oxide), organic and sulfide, and residual fractions. Of the eight metals, Cd and Co occur in lower concentrations (Cd <?< Co) in all types of land, and concentration variation from one type of land use to another is not much significant for both the metals. Ni presence is more than Co, and the concentrations show some variation depending on land use status. Average Cr and Cu concentrations are ??100?mg/kg, but Cr has a significantly higher presence in industrial land use. The results are similar in case of Pb. The two metals, Mn and Zn have domination over the other metals, and the values are ??300?mg/kg. Industrial and roadside soil contains much more Mn, while commercial soil is most enriched with Zn. Of the metals, Ni has the largest proportion (~42%) bound to the exchangeable fraction and Co, Cr, and Pb also have appreciable proportion bound to the same fraction. A significant amount of Co is associated with carbonates. The reducible fraction has bound considerable quantity of Mn and Zn, while most of Cu is associated with the organic and sulfide fraction. Both Cd and Pb are dominantly associated with the residual fraction. Computation of the mobility factor of the metals indicates Mn to be the most mobile metal present in the soil samples.     

Determination and speciation of heavy metals in sediments of the Juru River,Penang, Malaysia

The Juru River flows through largely urbanized areas and is grossly polluted by domestic wastes and discharges from pig farms. Other than carrying highly polluting organic materials, these wastes are also contaminated with heavy metals. To ascertain the extent of heavy metal pollution in the river, total and non-residual concentrations of Cu, Pb, Zn, Mn and Fe in sediment samples collected along the river were determined. The results indicate that both the total and non-residual metal concentrations in sediments can successfully be used to identify heavy metal pollution sources. The speciation of Zn, Mn and Fe in the sediment samples were investigated using a sequential leaching technique which identifies the elements among six operationally defined host fractions: (1) exchangeable, (2) carbonate and surface-associated, (3) easily reducible, (4) moderately reducible, (5) bound to organic matter and sulphides and (6) residual. The results indicate that Zn is mainly associated with the reducible fractions. Zn and Fe found in the moderately reducible fraction are significantly correlated, indicating that iron oxides is the preferred host phase by Zn.     

Comparison of leaching tests for the study of trace metals remobilisation in soils and sediments

Several leaching tests were applied and compared to study metal remobilisation on various unpolluted and contaminated soils and on several contaminated sediments. The trace elements considered were Cd, Cr, Cu, Ni, Pb and Zn, and leaching tests consisted of the application of reagents with contrasting characteristics and strengths in order to assess the information provided. An extraction with aqua regia permitted the estimation of the pseudo-total metal content in the sample. Mild extractants such as H2O, CaCl2 and NaNO3 showed low and similar leaching capacities. Acid (CH3COOH) and complexing (EDTA) agents were more effective in remobilising trace metals from soils and sediments. Cd and Zn showed similar extraction characteristics under both extractant solutions, whereas Cu and Pb were more sensitive to complexation, and Ni and Cr to acidification processes. Sequential chemical extractions provided additional information on the association of the trace elements with the different soil and sediment phases. Cd and Zn showed the highest mobility, Pb was associated to reducible solid phases, Cu and Ni to oxidisable phases, and Cr remained mostly in the residual fraction. The results obtained in this paper provided valuable information for choosing a leaching test, which is an instrument of environmental analysis for the estimation of trace metal mobility.     

Levels and speciation of heavy metals in soils of industrial Southern Nigeria

A knowledge of the total content of trace metals is not enoughto fully assess the environmental impact of polluted soils. Forthis reason, the determination of metal species in solution isimportant to evaluate their behaviour in the environment andtheir mobilization capacity. Sequential extraction procedure wasused to speciate five heavy metals (Cd, Pb, Cu, Ni and Zn) fromfour contaminated soils of Southern Nigeria into sixoperationally defined geochemical species: water soluble,enchangeable, carbonates, Fe-Mn oxide, organic and residual.Metal recoveries were within ± 10% of the independentlydetermined total Cd, Pb, Cu, Ni and Zn concentrations. The highest amount of Cd (avg. 30%) in the nonresidual fractionswas found in the exchangeable fraction, while Cu and Zn weresignificantly associated with the organic fraction. Thecarbonate fraction contained on average 14, 18.6, 12.6, 13 and11% and the residual fraction contained on average 47, 18, 33,50 and 25% of Cd, Pb, Cu, Ni and Zn respectively. Assuming thatmobility and bioavailability of these metals are related to thesolubility of the geochemical form of the metals, and that theydecrease in the order of extraction sequence, the apparentmobility and potential bioavailability for these five metals inthe soil were: Pb > Zn > Cu > Ni > Cd. The mobility indexes ofcopper and nickel correlated positively and significantly withthe total content of metals, while mobility indexes of cadmiumand zinc correlated negatively and significantly with the totalcontent of metals.     

Speciation and ecological risk of heavy metals in intertidal sediments of Quanzhou Bay, China

The chemical speciation of nine heavy metals in intertidal sediments from Quanzhou Bay was determined using a modified sequential extraction procedure, proposed by the Commission of the European Community Bureau of Reference. The results show that Mn presents the highest percentage in the acid-soluble fraction, and Pb and Cu present the highest percentages in the reducible fraction. The highest percentages of Fe, V, Cr, Ni, Zn, and Co were found in the residual fraction. The mobility order of the heavy metals studied on the basis of the nonresidual content of the elements is Mn > Pb > Cu > Co > Zn > Ni > Cr > V > Fe. The assessment on potential ecological risk indices of some heavy metals indicates that Zn, Ni, and Cr show moderate contamination, while Cu and Pb show slighter contamination. On the whole, the comprehensive potential ecological risk index of Cu, Zn, Ni, Cr, and Pb in the sediments presents moderate degree.     

Trace metals in the shells of blue mussels (Mytilus edulis) from the Poland coast of Baltic sea

The Odiel salt marshes (Marismas del Odiel) are an important nature area declared a Biosphere Reserve, but they are greatly affected by pollution from the Odiel River. Surface sediments from this area were analysed using the latest version of the BCR sequential extraction procedure to determine the fractionation of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn among four geochemical phases (acid-soluble, reducible, oxidisable and residual). The total content of each of the metals and As was also determined. The results showed high concentrations of As, Cd, Cu, Pb and Zn, with maximums of 791 mg kg⁻¹ of As, 8.5 mg kg⁻¹ of Cd, 2,740 mg kg⁻¹ of Cu, 1,580 mg kg⁻¹ of Pb and 3,920 mg kg⁻¹ of Zn. The concentrations of Cr, Mn and Ni were low since there are no sources of pollution by them in the area. A comparison of the metal and As levels with the sediment quality guidelines showed that the pollution is sufficient to produce noxious effects in aquatic organisms in most of the Odiel salt marshes. Based on the chemical distribution of the elements, it was found that Cd and Zn were the most mobile (i.e., elements that can pass easily into the water under changing environmental conditions). However, Cr, Fe, Ni and As were present in the greatest percentages in the residual fraction, which implies that these elements are strongly linked to the sediments.     

Associations of cadmium, zinc, and lead in soils from a lead and zinc mining area as studied by single and sequential extractions

An exploratory study of the area surrounding a historical Pb?CZn mining and smelting area in Zawar, India, detected significant contamination of the terrestrial environment by heavy metals. Soils (n?=?87) were analyzed for pH, EC, total organic matter (TOM), Pb, Zn, Mn, and Cd levels. The statistical analysis indicated that the frequency distribution of the analyzed parameters for these soils was not normal. The median concentrations of metals in surface soils were: Pb 420.21 ?? g/g, Zn 870.25 ?? g/g, Mn 696.70 ?? g/g, and Cd 2.09 ?? g/g. Zn concentrations were significantly correlated with Cd (r?=?0.867), indicating that levels of Cd are dependent on Zn. However, pH, electrical conductivity and total organic matter were not correlated significantly with Cd, Pb, Zn, and Mn. To assess the potential mobility of Cd, Pb, and Zn in soils, single (EDTA) as well as sequential extraction scheme (modified BCR) were applied to representative (n?=?23) soil samples. The amount of Cd, Pb, and Zn extracted by EDTA and their total concentrations showed linear positive correlation, which are statistically significant (r values for Cd, Pb, and Zn being 0.901, 0.971, and 0.795, respectively, and P values being <0.001). The correlation coefficients indicate a strong relation between EDTA-extractable metal and total metal. These results appear to justify the use of ??total?? metal contents as a useful preliminary indicator of areas where the risks of metal excess or deficiency are high. The EDTA extractability was maximum for Cd followed by Pb and Zn in soils from all the locations. As indicated by single extraction, the apparent mobility and potential bioavailability of metals in soils followed the order: Cd ?? Pb >?> Zn. Soil samples were sequentially extracted (modified BCR) so that solid pools of Cd, Zn, and Pb could be partitioned into four operationally defined fractions viz. acid-soluble, reducible, oxidizable, and residual. Cadmium was present appreciably (39.41%) in the acid-soluble fraction and zinc was predominantly associated (32.42%) with residual fraction. Pb (66.86%) and Zn (30.44%) were present mainly in the reducible fraction. Assuming that the mobility and bioavailability are related to solubility of geochemical forms of metals and decrease in the order of extraction, the apparent mobility and potential metal bioavailability for these contaminated soil samples is Cd > Zn > Pb.     

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.     

Heavy metals partitioning in sediments of the Kabini River in South India

Cu, Cr, Fe, Mn, Ni, Pb, and Zn in the sediments of the Kabini River, Karnataka, India was studied to determine the association of metal with various geochemical phases by sequential extraction. The variations of heavy metal concentration depend on the lithology of the river basin and partly on anthropogenic activities. The Kabini River sediments are dominated by Sargur supracrustals with amphibolites, gneisses, carbonates, and ultrabasic rocks weathering into gneissic and serpentine soils carrying a natural load of cationic heavy metals. The source of heavy metals in the Kabini riverbed sediments is normally envisaged as additional inputs from anthropogenic over and above natural and lithogenic sources. Geochemical study indicates the metals under study were present mostly in the least mobilizable fraction in the overlying water and it is concluded that heavy metals in these sediments are to a great extent derived from multisource anthropogenic inputs besides geochemical background contributions The results show that lead and chromium have higher potential for mobilization from the sediment due to higher concentration at the exchangeable ion and sulfide ion bounded, also Cu and Pb have the greatest percentage of carbonate fraction, it means that the study area received inputs from urban and industrial effluents. Association of the Fe with organic matter fraction can be explained by the high affinity of these elements for the humic substances. Further, Zn and Ni reveal a significant enrichment in sediment and it is due to release of industrial wastewater into the river. These trace metals are possible contaminants to enter into aquatic and food chain.     

Trace metals: Inputs, sedimentation and accumulation in San Vicente Bay, Chile

The present study deals with sediment dynamics affecting sediment-associated metal distributions in an embayment system experiencing pollution from coastal industries. Sedimentary metal content may originate from diagenetic processes of foundation rock on the bottom, allochthonous minerals from natural sources, and metals from industrial effluents along the coast. The study presents experimental estimations of quantities of metals entering the bay in industrial wastewater, measurements of metal content in particulate material captured in sediment traps, and metals distribution in surface sediments. Quantitative estimations of metals entering the system in industrial effluent showed the relation Pb Zn > Cu > Cr Ni > Cd. That of metals associated with particulate material from traps was Zn > Cr Cu > Pb > Ni > Cd and the abundance of metals in sediments was Zn > Cr > Cu > Pb > Ni > Cd. Finally, rates of bottom sediment accumulation are estimated in relation to the time of residence of water in the bay. The experimental data on sedimentation and sediment abundance were consistent with field observations on distribution and accumulation at sites of major sedimentation in this bay.     

Geochemical fractionation of trace elements in sediments of Hugli River (Ganges) and Sundarban wetland (West Bengal, India)

A sequential extraction procedure was carried out to determinate the concentrations of 11 elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) in different geochemical phases of sediments collected along the Hugli (Ganges) River Estuary and in the Sundarban mangrove wetland, eastern coastal part of India. The chemical speciation of elements was determined using the three-step sequential extraction procedure described by the European Community Bureau of Reference. Total metal concentration was determined using a microwave-assisted acid digestion procedure. Metal concentrations were near the background level except for As for which a moderate pollution can be hypothesized. The mobility order of the metals was: Cd?>?Mn?>?Cu?>?Zn?>?As?>?Co?>?Pb?>?Ni?>?Fe?>?Cr?>?Al. The highest percentage of Cd (>60%) was found in the most labile phase. Residual fraction was prevailing for Fe, Cr and Al, while Pb was mainly associated with the reducible fraction. Data were compared with Sediment Quality Guidelines to estimate the relationship between element concentrations and adverse biological effects on benthic community, finding the possibility of some toxic effects due to the presence of As in the entire studied area and Cd, only in Calcutta.     

Spatial, temporal, and speciation variations of heavy metals in sediments of Nan'ao Island, a representative mariculture base in Guangdong coast, China

Heavy metals in sediments from Baisha Bay, Nan'ao Island, one of Guangdong Province's largest mariculture bases in Southern China, were investigated. The results display that the concentrations of 6 heavy metals from surface sediments were 0.040-0.220 (Cd), 24.22-39.61 (Pb), 25.30-42.66 (Cr), 10.83-19.54 (Ni), 15.06-39.24 (Cu) and 55.12-141.73 mg kg(-1) (Zn), respectively. The highest concentrations and the greatest increasing rates of heavy metals were found in a sediment core in a fish cage culture area due to receiving sewage discharge, uneaten fish bait, and boat gasoline combustion. Cd was preferentially associated with the acid-soluble fraction and Pb mainly with the reducible fraction in surface sediments. Meanwhile, Cd and Pb displayed greatest labile fractions, indicating anthropogenic origin. A principal component analysis (PCA) revealed three groupings (Cd; Cr, Ni and Cu; Pb and Zn) that mainly result from different distributions of the metals in the various fractions. The ecological risk of the polluted sediments stemmed mainly from Cd, and from Pb and Cu to a lesser degree. It is suggested that the density of fish-stocking be controlled, periodic movement of rafts (cages) be introduced, and the total numbers of net-cages and human activities in the mariculture zones be restricted. in order to facilitate the recovery of the polluted sediment.     

Spatial distribution and potential ecologic risk assessment of heavy metals in the sediments of the Nansi Lake in China

The contamination levels and ecological risks of heavy metals in the sediments of the Nansi Lake were investigated. The contents of Cd, Cr, Cu, Pb, Zn, Ni, and Co in the surface sediments collected at 20 sites ranged from 0.08 to 1.12, 58.92 to 135.62, 38.09 to 78.65, 24.51 to 53.95, 110.51 to 235.36, 11.30 to 65.40, and 4.12 to 20.14 mg/kg, respectively. The results of partitioning analysis revealed that the proportions of soluble and exchangeable fraction were less than 1 %, the proportions of carbonate, amorphous oxides, organic matter, and crystalline oxides fraction were less than 10 %, and 10.52 % of Cd was associated with carbonate. The average proportions in the residual fraction ranged from 48.62 % for Cu to 73.76 % for Ni, indicating low mobility and bioavailability. The geoaccumulation index (I _geo), relative enrichment factor (REF), sediment pollution index (SPI), and potential effect concentration quotient (PECQ) values of the heavy metals in the sediments were not in agreement with each another. The average REF values of Cd and Zn were higher than those of other metals. However, the average PECQ values were higher for Cr and Ni than those of other metals, indicating that these two metals would cause higher adverse biological effects. Therefore, it is suggested that future management and pollution control might focus on Cd, Zn, Cr, and Ni in the sediments of the Nansi Lake.     

北方某水库表层沉积物重金属的赋存形态及其环境影响因子分析

为了解北方某水库重金属污染状况,采用BCR连续提取法对该水库表层沉积物中Cu、Pb、Zn、Cd的赋存形态进行了分析,对其含量及空间分布进行了研究,结合重金属总量讨论了各元素的潜在环境风险。结果表明,该水库表层沉积物中Cu、Pb、Zn、Cd的平均质量比分别为65.20 mg/kg、36.69 mg/kg、137.5 mg/kg、2.38 mg/kg,与该地区土壤元素背景值、该地区水系沉积物平均值及全国水系沉积物平均值相比,4种重金属元素均有一定程度的累积,其中Cd累积最为严重。形态分析结果表明,Cd主要以醋酸可提取态及可还原态存在,具有很高的环境风险;Pb主要以极高比例的可还原态存在,潜在风险较高;Zn和Cu存在较大比例的酸可提取态及可还原态,也具有一定程度的潜在风险。各元素生物有效性即可提取态含量排序为:Cd>Cu>Pb>Zn。     

Trace metal fractionation in the Pichavaram mangrove–estuarine sediments in southeast India after the tsunami of 2004

The geochemistry of coastal sediments of southern India was altered after the tsunami in 2004. A five-step sequential extraction procedure was applied to assess the effects of tsunami on mobility and redistribution of selected elements (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn). Ten surface sediments and three cores were analyzed for different metal fractions (exchangeable, carbonate, reduced, oxidized, and residual). Total metal concentrations increased in mangrove sediments after the tsunami, but their spatial distribution did not show significant variation (except Mn). The sediments were mixed by the tsunami, and there was lack of variation in metal concentrations in different fractions with depth (except Pb and Mn). High concentrations of Pb and Zn occurred in the oxide fractions, whereas Cu, Cr, Cd, and Ni were high in the organic and sulfide-rich fractions. Metals in the residual fraction (lattice bound) had the highest concentration suggesting their non-availability and limited biological uptake in the system. Most of the metals (except Mn) do not constitute a risk based on the different geochemical indices.     

Assessment of heavy metals in sediments from a typical catchment of the Yangtze River, China

An intensive investigation was conducted to study the accumulation, speciation, and distribution of various heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) in sediments from the Yangtze River catchment of Wuhan, China. The potential ecological risks posed by these heavy metals also were estimated. The median concentrations of most heavy metals (As, Cd, Cr, Cu, Ni, Pb, and Zn) were higher than the background values of soils in Wuhan and were beyond the threshold effect level (TEL), implying heavy metal contamination of the sediments. Carbonate-bound Cd and exchangeable Cd, both of which had high bioavailability, were 40.2% and 30.5% of the total for Cd, respectively, demonstrating that Cd poses a high ecological risk in the sediments. The coefficients of the relationship among Pb, Hg, and Cu were greater than 0.797 using correlation analysis, indicating the highly positive correlation among these three elements. Besides, total organic carbon content played an important role in determining the behaviors of heavy metals in sediments. Principal component analysis was used to study the distribution and potential origin of heavy metals. The result suggested three principal components controlling their variability in sediments, which accounted for 36.72% (factor 1: Hg, Cu, and Pb), 28.69% (factor 2: Cr, Zn, and Ni), and 19.45% (factor 3: As and Cd) of the total variance. Overall, 75% of the studied sediment samples afforded relatively low potential ecological risk despite the fact that generally higher concentrations of heavy metals relative to TEL were detected in the sediments.     

Assessment of heavy metal concentration in the Khoshk River water and sediment, Shiraz, Southwest Iran

Heavy metal contents and contamination characteristics of the water and sediment of the Khoshk River, Shiraz, Southwest Iran were investigated. The abundance of heavy metals decreases as Zn > Mn > Cr > Ni >Pb > Cu > Cd in water samples and Mn > Cr > Pb > Ni > Zn > Cu > Cd in sediments, respectively. Based on the enrichment factor and geoaccumulation index values, sediments were loaded with Cr, Zn, Pb, Cu, and Cd. Pearson correlation matrix as well as cluster and principal components analyses and analysis of variance were implemented on data from sampling sites. Based on the locations of sampling sites in clusters and variable concentrations at these stations, it was concluded that municipal, industrial, and domestic discharges in the Shiraz urban area strongly affected heavy metals concentrations in the Khoshk River water and sediment. Results obtained from principal components analysis of sediment samples showed that the high concentration of Ni was mainly from natural origin, related to the composition of parent rocks, while the elevated values of Cr, Zn, Pb, Cd, and Cu were due to anthropogenic activities.