Effects of long-term irrigation with treated wastewater. Part II: Role of organic carbon on Cu,Pb and Cr behaviour

The long-term impact of irrigation on a Mediterranean sandy soil irrigated with treated wastewater (TWW) since 1980 was evaluated. The main soil properties (CEC, pH, size distribution, exchangeable cations and chloride, hydraulic conductivity) as well as the organic matter and Cu, Cr and Pb speciation in an irrigated soil and a non-irrigated control soil at various soil depths were monitored and compared during a 2 year experiment. In this second part, we focused on Cu, Cr and Pb behaviour in relation with soil organic carbon (SOC). Soil samples were collected every 3 months during 2 years at the depths 0–20, 20–40 and 40–60 cm and were analysed for exchangeable and total metals, organic carbon content, metal sequential extraction and humic substances – Humic Acids (HA), Fulvic Acids (FA) and Non-Humified Fraction (NHF). Long-term irrigation with a domestic treated wastewater (TWW) may be considered safe with regard to trace metal accumulation in soil. Irrigation lowered the HA and NHF fractions of SOC and made the FA fraction more mobile. Cu bound preferentially to the SOC fraction, Cr was found mainly in the reducible fraction and Pb was bound to all fractions indiscriminately. Cu exhibited a high affinity for the HA fraction, while Pb and Cr had a high affinity for the FA fraction, which indicates a greater mobility of the organically-bound Pb and Cr than of the organically-bound Cu. Evaluation of the potential metal mobility has to take into account not only the usual speciation between labile, reducible and oxidisable fractions, but also the nature of the SOC responsible for the oxidisable fraction.     

Mobility and ecological risk assessment of heavy metals in surface sediments of Xiamen Bay and its adjacent areas,China

Xiamen Bay (XMB) has received substantial loadings of pollutants from industrial and municipal wastewater discharged since the 1980s. To assess ecological risks and the current spatial changes of metal contaminants in bottom surface sediments, 12 samples were collected. Samples were subjected to a total digestion technique and analyzed by ICP–OES for Cu, Pb, Zn, Cr, and Cd, and by AFS for Hg and As. Among these metals, Zn had the highest values (68–268 mg kg⁻¹), followed by Pb (27–71 mg kg⁻¹), and lower concentrations were found for Cd (42–1,913 μg kg⁻¹) and Hg (0–442 μg kg⁻¹). In comparison with the average crustal abundance values, the results indicated that nearly half of the sediment samples of XMB and its adjacent areas were contaminated by Cd, Pb, Zn, and As. Furthermore, based on the modified BCR sequential extraction procedure, the chemical speciation of heavy metals (Cd, Cr, Cu, Pb, Zn, Hg, and As) in selected sediment samples were evaluated in this study. Data from BCR sequential extractions indicated that Cd posed a medium ecological risk, whereas, Cr posed low risk since its exchangeable and carbonate fractions were below 4%, and the mobility of heavy metals in XMB decreased in the order Cd > Pb > Cu > Zn > Hg > As > Cr. By applying mean effects range median quotients (mERMQ), the results showed that Yuandang Lagoon with mERMQ value >0.5 would be expected to have the greatest potential toxic risk in amphipod within XMB and its adjacent areas.     

The effect of traffic on levels,distribution and chemical partitioning of harmful metals in the street dust and surface soil from urban areas of Tehran,Iran

Due to the explosive industrialization and rapid expansion of the population in many parts of the world, heavy metals are released into the environment continuously and pose a great risk on human health. Street dust and surface soil samples from very heavy, heavy, medium and low traffic areas and a natural site in Tehran, Iran, were analyzed for some physicochemical features, total and chemical fractionating of selected metals (Zn, Al, Sr, Pb, Cu, Cr, Cd, Co, Ni and V) to investigate the influence of traffic on their mobility and accumulation in the environment. The pH, electrical conductivity (EC), carbonates and organic carbon contents were similar in soil and dust samples from the areas with same traffic. The traffic increases EC contents in dust/soil matrixes, but has no effect on concentrations of metals in soil samples. Rises in metal levels with traffic were found in dust samples. Moreover, the traffic increases the percentage of both acid-soluble and reducible fractions, which are related to Pb and Zn. The mobilization of Cu, Zn, Pb, Cr in dust samples was easier than in soil. The speciation of metals except Cd is mainly affected by physicochemical features in soil, though total metals affected the speciation in dust samples (except chromium and nickel).     

Speciation of trace metals in sediments of a tropical estuary

Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.     

Partitioning of transition metals in oxidised and reduced zones of sulphide-bearing fine-grained sediments

Distribution and forms of transition metals (Ti, Zn, Ni, Co, Mn, Fe, Cu, V and Cr) were investigated in oxidised, partly oxidised and reduced zones of sulphide-bearing fine-grained sediments located in the coastal areas of western Finland. Samples for the analysis and study of vertical distribution of elements were taken from each vertical 10 cm section in pits ranging in depth between 2 and 3 metres, while bulk samples for characterisation of species and forms of metals were taken from 3 zones in each pit: the acid sulphate soil (characterised by acid and oxidising conditions), transition zone (characterised by a steep pH gradient and partly oxidising conditions) and the reduced zone (pH >6). The former samples were digested in aqua regia (3:1:2 HCl:HNO₃:H₂O), while the latter were digested in aqua regia and hot concentrated acids (HClO₄–HNO₃–HCl–HF) and were subjected to extractions with acid ammonium acetate, H₂O₂ and acid ammonium oxalate. Each leachate was analysed for metals with ICP–AES.The vertical variation in the concentrations of Ti were small at all the studied sites indicating that the sediments are homogeneous and that the total losses of other elements from the soil profiles (acid sulphate soil+transition zone) are not extensive. Field observations, extractions with ammonium oxalate, and concentration–variation patterns indicated that Fe-oxide is largely precipitated and retained also in these acid soils. There are, however, indications of redistribution of Fe within the soil profiles. The results also demonstrated that Mn, Ni, Zn, Co and Cu have been lost in considerable amounts from the acid sulphate soils. However, whereas Mn in general has been lost throughout the soil profile, part of the Zn, Ni and Co released in the acid sulphate soils have migrated downward and been reimmobilised in the transition zone immediately above the reduced zone. Also Cu has been lost from the acid sulphate soil, but generally in smaller proportions than Mn, Zn, Ni and Co. Dissolved metal sulphides seem to be major sources of the mobilised metal fractions. A main part of the V and Cr in the sediments are associated with weathering-resistant minerals. These metals are therefore, like Ti, only to a limited extent mobilised by the oxidation of the sulphide-bearing sediments.     

Impact of historical metalworks on the concentrations of major and trace elements in sediments: a case study in Finland

The concentrations of major and trace elements were determined (aqua regia leach and ICP-AES analyses) in stream, lake and dredged sediments downstream of the historical Antskog iron- and copperworks, S.Finland. The levels of Ag, Cd, Cu, Pb and Zn are highly elevated in all studied sediment types: roughly half of the studied lake-sediment samples contain >5 ppm Ag, >15 ppm Cd, >0.1% Cu, >0.1% Pb and >0.3% Zn. In the dredged sediment material located onshore, the concentrations of Ag, Cu and Pb are comparable to those in the polluted lake-sediment samples, while in stream sediments elevated metal concentrations are found especially in samples characterised by high concentrations of organic material. The source of the elevated metal concentrations is the historical metalworks at Antskog, mainly the copperworks of the 19th century. Compared to the limit values for contaminated soils in Finland, the concentrations of Cu, Pb and Zn are on average elevated by factors >10 in the polluted horizons of lake sediments, >5 in the dredged sediment located onshore and >2 at the most heavily contaminated site in the stream. Since the surface waters in the area are used for agricultural purposes and for various leisure activities, it is necessary to make further detailed investigations into the extent of the metal pollution and to determine species, mobility and bioavailability of the metals.     

Characteristics of distribution and chemical speciation of heavy metals in environmental mediums around Jinchang mining city,Northwest China

Heavy metal contamination was the main environmental problem around the Jinchang Ni–Cu mine area of Gansu, Northwest China. The concentration of heavy metals (Cr, Cu, Ni, Pb, and Zn) in various environmental mediums around the Jinchang Ni–Cu mine area were analyzed using atomic absorption spectrometry (AAS). The different chemical speciation of heavy metals was extracted using BCR (European Community Bureau of Reference) sequential extraction procedure, and the concentration of chemical speciation of each heavy metal was measured by inductively coupled plasma-atomic emission spectrometry. The results showed that Cu and Ni were the most important heavy metal pollutants in various mediums including cultivated soils, dust on slagheap surfaces, tailings, and sediments in waste water drains. In the tailings and sediments, the concentrations of Ni were obviously higher than those of Cu, whereas, in the soil and dust, the concentrations of Cu were higher than those of Ni. Analysis of chemical speciation indicated that Cr and Zn were mainly in residual fraction; Cu was mainly in oxidizable fraction; Ni was mainly in reducible fraction and acid soluble fraction; and Pb was mainly in reducible fraction and residual fraction. The extent of contamination of various environmental mediums was different because the heavy metals were derived from different sources. Furthermore, the mobility of various heavy metals was different because of the different distribution of chemical speciation.     

pH对长江下游沉积物中重金属元素Cd、Pb 释放行为的影响

河流沉积物中的重金属元素对水生生物和人类具有潜在的危害性,主要是由于环境条件的变化会使沉积物中的重金属元素释放到水体中。因此,研究影响沉积物中重金属元素释放的因素是十分重要的。研究了长江下游沉积物在不同pH条件下重金属元素Cd、Pb的释放能力和释放前后Cd、Pb形态的变化。结果表明,Cd、Pb在沉积物中的释放主要是在酸性条件下发生的,并且释放率随pH的升高而迅速降低,pH＞7.0后,释放率都非常低。释放能力Cd明显大于Pb。形态分析的4个典型沉积物样品中,Cd在南京位点样品中主要存在于残渣态中,其余3个位点样品主要存在于弱酸态和可还原态中,Pb在4个典型沉积物样品中主要存在于可还原态中。pH的变化使沉积物中Cd的各形态都不同程度地发生了释放,弱酸态和可还原态释放的程度最大,而Pb的各个形态释放都不明显。     

贵阳城市土壤重金属元素形态分析

选取贵阳市62个代表性的表层土壤样品,分析了其重金属元素的含量和存在形态.结果表明,贵阳城市土壤中5种重金属元素(Cr、Cu、Pb、Zn和Cd)的含量较高,且变化较大.表层土壤中Cr、Cu、Zn主要以残渣态形式存在,Pb主要以可氧化态形式存在.Cd可还原态含量高达47.5%,残渣态含量最低,说明Cd较活泼,具有潜在的环境影响能力.     

The effect of mineralogy on the mobility of heavy metals in mine tailings: a case study in the Samsanjeil mine,Korea

This study examined the chemical speciation and mobility of As and heavy metals in a tailings impoundment in Samsanjeil mine located in Gosung, Korea, as well as the factors affecting them. XRD, SEM, and 5-step sequential extraction were used to examine the samples at two sampling sites (NN and SN sites). The pH of the tailings decreased with increasing depth at the NN site (from 7.2 to 2.8), whereas no significant differences were observed at the SN site (8.1–8.8). The samples at the SN site showed a larger amount of calcite than those at the NN site, indicating that calcite plays an important role buffering the pH in the study sites. Jarosite was found only at the lower part of the NN site, where calcite was not found. The mineralogical observation of jarosite and calcite was also confirmed by SEM. The concentrations of As and heavy metals in the tailings were as follows: Cu > As > Zn > > Pb > Co > Cr > Ni > Cd. The total concentrations of Ni, Zn, Co, and Cd were higher at the SN site than those at the NN site. On the other hand, the concentrations of As and Cr existing as oxyanions were higher at the NN site, which can be explained by the mobility changes of those elements affected by pH variations. At the NN site, the fractions of heavy metals bound to the Fe/Mn oxides, except for As and Cr, decreased, and Cu, Zn, and Co showed an increasing fraction of exchangeable metals with increasing depth. This suggests that the pH and resulting surface charge of minerals, such as goethite and jarosite, are the dominant factors controlling the chemical speciation of metals. These results highlight the importance of mineralogy in controlling the mobility and possible bioavailability of heavy metals in tailings.     

Soil and groundwater pollution of an urban catchment by trace metals: case study of the Addis Ababa region, central Ethiopia

Analysis of the total heavy metal (Cr, Cd, Pb, As, Cu, Ni, Zn, Co) concentration was performed on 33 soil samples taken from different profiles and soil types in a highly urbanized and industrial sector of Addis Ababa, central Ethiopia. They were analyzed using aqua regia extraction coupled with a four-stage sequential extraction (SE) procedure. The objectives of the analysis were to investigate the degree of soil heavy metal contamination, its binding forms, mobility and the implications for the groundwater resource. The results show a relatively high content of the analyzed trace metals in the soil attributed to anthropogenic and geogenic sources. Although most of the trace metals are found in the upper few centimeters of the residual soils, because of churning processes within the black cotton soils, vertical distribution of the trace metals is complex. According to the heavy metal SE analysis, the major heavy metal contribution is from the residual followed by the hydroxide phases. Groundwater heavy metal contamination is present with more than 90 and 50% of the analyzed groundwater samples exceeding WHO guidelines for Cr and Cd, respectively. Since the degree of soil heavy metal contamination has apparently not surpassed the soil’s buffering capacity, it appears that the transport path of these toxic metals to the groundwater is through fractures, joints, and related preferential flow paths.     

Heavy metals pollution in the soils of suburban areas in big cities: a case study

Soil pollution in agricultural areas surrounding big cities is a major environmental problem. Tabriz is the largest city in the northwest of Iran and the fourth largest city in the country. Soil samples were taken from 46 sites in the suburbs of the Tabriz city, and separate samples were taken from control site and analyzed. The results indicated that the mean pH value of the soil samples was 9.29, while the mean EC value was 354.33 μs/cm and the amount of TOC and TOM was 0.99 and 1.7 %, respectively. The mean concentrations of Cd, Pb, Cu, Cr, Ni, and Zn in the soil were determined to be 1.61, 10.56, 101.25, 87.40, 38.73, and 98.27 mg/kg, respectively (dry weight). The concentrations of heavy metals (Cd, Pb, Cu, Cr, and Zn), with the exception of Ni, were higher than the concentrations of the same heavy metals at the control site. Despite these elevated concentrations, the concentrations of heavy metals were lower than the toxicity threshold limit of agricultural soils. The values of the pollution index revealed that the metal pollution level was Pb > Cr > Cu > Zn > Cd > Ni, and the mean value of the integrated pollution index was determined to be 1.81, indicating moderate pollution. Nevertheless, there were some sites that were severely polluted by Cr (maximum values of 1,364 mg/kg). It was concluded that city probably has affected the surrounding agricultural area. Application of wastewater (municipal and industrial) as irrigation water, using of sludge as soil fertilizer, and atmospheric perceptions have been considered as main reasons of increased heavy metals concentrations found in the studied area.     

Distribution and chemical speciation of heavy metals in the surficial sediments of the Bak?r?ay and Gediz Rivers, Eastern Aegean

The pollution of aquatic ecosystem by heavy metals has assumed serious proportions due to their toxicity and accumulative behaviour. The toxicity and fate of the water borne metal is dependent on its chemical form and therefore quantification of the different forms of metal is more meaningful than the estimation of its total metal concentrations. A five-step sequential extraction procedure was applied for the determination of the distribution of seven elements (Pb, Cr, Cu, Mn, Zn, Ni, Fe) in sediment samples collected from Bakır?ay and Gediz Rivers. According to this study, the results of metals are mostly retained in the residual, oxidizable and reducible fractions. Based on the chemical distribution of metals, we found that Cr, Zn, Cu and Ni are the most non-mobile metals. Pb is the metal that showed the highest percentages in the residual and reducible fractions. Mn is present in the higher percentages in the reducible and carbonate fractions. However, Fe is present in the greatest percentages in the residual fraction, which implies that these metals are strongly linked to the sediments. The risk assessment code as applied to the present study shows that about 12.3–26.9 and 15.7–33.5% of manganese at most of the sites exist in carbonate fraction in the Bakır?ay and Gediz Rivers, respectively. Therefore, Mn comes under the medium risk category in the Bakır?ay and high-risk category in the Gediz River. Speciation pattern of Cu, Zn, Pb, Cr, Ni, Fe shows low to medium risk to aquatic environment health in both rivers.     

Interactions between Cd,Cu, Pb,and Zn and four different mine soils

The chemical associations of Cd, Cu, Pb, and Zn in four mine soil samples from the Amizour-Bejaia Pb/Zn mine (Algeria) have been investigated by a five-step sequential extraction procedure. Although Cd preferentially binds to carbonates, Cu, Pb, and Zn are mainly associated with the organic and reducible fractions. Batch adsorption experiments with either mono- or multi-metallic solutions are described with the Freundlich isotherm model. Whatever the nature of the soil sample, the sorption behavior for each given metal except Pb is very similar, indicating that the binding sites at the soil surface are progressively occupied by the metal from the solution. On each soil sample, the decreasing order of sorption can be established as Pb >> Cu > Cd > Zn. When the four metals are simultaneously applied to each soil sample, their specific behavior is strongly affected by their interactions and/or competition for the available surface sites: we generally observed isotherm curves with a slight maximum before the plateau at higher solution concentration. Although Cu is only slightly affected by the other metals, in the case of Pb, Cd, and Zn, the sorbed amounts strongly decreased.     

Removal of heavy metals from a contaminated soil using organic chelating acids

Changes in heavy metal speciation and uptake by maize in a soil before and after washing with chelating organic acids, citric acid, tartaric acid and ethylenediaminetetraacetic acid were assessed. A sandy loam was collected from the vicinity of the Benue industrial layout, Makurdi, Nigeria and spiked with a quinternary mixture of nickel, copper, zinc, cadmium and lead nitrates to achieve higher levels of contamination. Batch soil washing experiments performed on 1.0 g portions of the spiked soil using 0.05 M chelating agents at a solid:liquid ratio of 1:25 showed that washing efficiencies varied in the order: ethylenediaminetetraacetic acid> citric acid> tartaric acid with metal extraction yields typically following the sequence, copper> nickel> zinc> cadmium> lead. Sequential extractions proposed by the European Communities Bureau of Reference method used to assess the redistribution of heavy metal forms in the soil showed that apparent metal mobilities were reduced upon soil washing. Citric acid removed most of the metals hitherto associated with the exchangeable and reducible fractions; tartaric acid, the exchangeable metal pools; and ethylenediaminetetraacetic acid, the non-residual metal pools. Heavy metal assay of harvested biomass of maize grown on unwashed and washed soil samples indicated that metal transfer coefficients, decreased in the order of treatment: ethylenediaminetetraacetic acid <citric acid <tartaric acid <unwashed soil. Ethylenediaminetetraacetic acid and citric acid appeared to offer greater potentials as chelating agents to use in remediating the high permeability soil. Tartaric acid, however, is recommended in events of moderate contamination.     

Distribution of heavy metals in urban soils – a case study of Danang-Hoian Area (Vietnam)

 This work is part of a research study which is intended to study the degree of anthropogenic influences of the trace metal distribution of soils from Danang-Hoian area (Vietnam). Cu, Ni, Zn and Zr show significant effects in most of the cultivated soil categories, especially in the industrial soils. Extremely high levels of Pb (up to 742 μg/g) are observed in the industrial soil category, which shows an enrichment factor 114 as compared to rural soils. Cd shows only a relative local enrichment with the maximum level of 4.6 μg/g in urban soils. Sequential extraction was performed in selected samples to evaluate the geochemical trace metals. The result indicates that Zn and Cr are mainly found in the crystal and amorphous Fe oxide bounded forms. The contents of Cr in these fractions comprise more than 94% of total extractable Cr. In the case of Zn, 85% of total extractable Zn is in fractions F_V and F_VI. Cu is mainly found in the organic fraction at an average of 39.3% of total extractable content. On the other hand, heavy metal contents show an increasing tendency in the fine fraction (silt and clay). Received: 4 February 1998 · Accepted: 26 November 1998     

Spatial trends and losses of major and trace elements in agricultural acid sulphate soils distributed in the artificially drained Rintala area,W. Finland

Acid sulphate soils, common in the coastal areas of Finland, contribute strongly to high acid, S and metal loadings on adjacent surface waters. This, in turn, is causing significant harm to the aquatic ecology. There is, however, limited knowledge on the total amounts of acidity and chemical elements leached from these soils. The overall objective of this study was to determine geochemical patterns in acid sulphate soils and their parent sediments and, based on the identified patterns assess the extent, mechanisms and present state of leaching of major and trace elements from these soils. The distribution of pH, aqua regia extractable concentrations of P and metals (Al, Ba, Ca, Co, Cr, Cu, Fe, K, La, Mg, Mn, Na, Ni, Sr, Th, Ti, V, Zn) and total concentrations of S and C were determined in 30 vertical profiles collected in the 23 km² large Rintala agricultural area (mid-western Finland) underlain largely with S-rich sediments. It was found that approximately 70% of the area consists of acid sulphate soils with a minimum pH<4.0, an average depth of 1.8 m, and S concentrations in the parent sediments varying from 0.24 to 1.04%. Acid sulphate soils have not developed where the S concentrations in the sediments are ⩽0.10% or where the concentrations of organic C in the soil zones are >4%. Four different methods were used to estimate the losses of chemical elements from the acid sulphate soils: (1) the concentrations in the soil were compared with those in the parent sediments, (2) due to indicated heterogeneities in several profiles, the vertical changes of the immobile Ti was used to re-calculate element losses, (3) element depletions in the acid sulphate soils (as compared to those in the parent sediments) were compared to the corresponding depletions in the non acid sulphate soils, (4) element concentrations in drainage waters were compared with those in the parent sediments. Based on these calculations, it was assessed that the percentual leaching of the aqua regia extractable fraction (total for S) has been as follows: S (40–50%), Na (30–50%), Mn (25–35%), Sr (15–20%), Ca–Ni–Co (approximately 10%), Mg–K–Zn (5–10%), Th–La–Cu–Al–P–Ti–Fe (<5%), and Ba–Cr–V (<1%). While it was possible to quite accurately estimate the percentages and thus the amounts of elements lost, it was not possible to estimate the rate of leaching as there is no available detailed information on dates when ditching activities and thus oxidation-acidification processes started. Other calculations indicated that the mobile S reservoir is still some 15 ton/hectare, which is huge but still smaller than the losses that have occurred since the area was drained (23–28 ton/hectare).     

金昌市铜镍矿区周围土壤中重金属的迁移特征

对金昌矿区不同区域土壤5~20 cm层中重金属各化学形态及活性态的迁移行为进行了研究,结果表明：土壤中重金属不同化学形态迁移率不同,弱酸提取态、可还原态、可氧化态和残渣态平均迁移率分别为0.13、0.51、0.30和0.54。重金属总量和活性态（包括弱酸提取态、可还原态、可氧化态）迁移率也表现出很大差异,尾矿区土壤Cr总量迁移率较高为0.65,而其活性态迁移率较低为0.26,Ni与Cr迁移特征完全相反,总量迁移率为0.26,而活性态迁移率为0.67;农田土壤中Pb总量迁移率低而活性态迁移率高,Ni与Zn特征相似,总量迁移率高而活性态迁移率相对较低;大棚地土壤中重金属迁移率均较低,Cu和Ni活性态几乎未发生向下迁移。可见,重金属的迁移与其化学形态分布关系密切,与重金属总量的迁移率相比,活性态迁移率能够更有效地反映出土壤中重金属的迁移特征和潜在危害性。