Partitioning of Zn,Cd, Pb,and Cu in organic-rich soil profiles in the vicinity of a zinc smelter

Abstract

A five-step sequential extraction procedure was applied to organic-rich soil samples from five soil profiles situated 1–8 km from a zinc smelter. The partitioning of Zn, Cd, Pb, and Cu into five operationally defined fractions (exchangeable, “carbonate’’-bound, reducible, oxidizable, and residual) was studied at different soil depths down to 35cm. In the surface soil (0–1 cm) a major part of Pb and Cu was extracted in the oxidizable fraction, whereas for Zn and Cd slightly more was extracted in the ‘‘carbonate”-fraction than in the other four fractions. Extracted metal proportions in the oxidizable fraction were respectively of the order of 30%, 20%, 50%, and 80% for Zn, Cd, Pb, and Cu in the surface soil for all sites, but these proportions decreased with soil depth. In the surface soil less than 20% of all the elements were extracted in the residual fraction, but the proportions associated with this fraction generally increased with soil depth. In the C-horizon, differences in extracted proportions of Pb and Cu in the residual fraction were probably due to geochemical factors, whereas for Zn the low extracted proportion at a highly contaminated site (20%) may be due to Zn migration to the C-horizon at this site. For Cd the extracted proportions in the C-horizon were lower than for the other elements, generally below 20%, presumably because Cd is weaker in terms of its adsorption to the soil than the other elements studied. Total concentrations of the metals decreased strongly with increasing distance from the smelter, but less systematic differences were observed for their distributions among fractions. Potentially bioavailable metal proportions (exchangeable + “carbonate”-bound fraction) in the surface soil were about 50%, 60%, 20%, and 10% for Zn, Cd, Pb, and Cu, respectively. In C-horizon soil the mobility sequence Cd>Zn>Pb = Cu was generally observed. The present results indicate that the concentrations and chemical fractionation of Zn, Pb, and Cd in these soils represent a considerable risk to natural terrestrial food chains.     

Characterization of Heavy Metal Fractions in Agricultural Soils by Sequential Extraction Procedure: The Relationship Between Soil Properties and Heavy Metal Fractions

The present research was conducted to determine heavy metals in agricultural soils from Çanakkale, Turkey, using a sequential extraction procedure (acid soluble, reducible, oxidizable, and residual) as proposed by the Community Bureau of Reference (BCR) of the European Commission. Soil samples were taken from 12 different cultivated sites and analyzed for Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn concentrations. The results revealed an order of Mn > Cd > Pb > Co > Ni > Cu > Zn > Cr for the heavy metals based on the sum of the first three fractions (acid soluble + reducible + oxidizable). The relationships between soil properties and each metal fraction were identified through Pearsons's correlation analysis. Hierarchical cluster analysis was performed to determine the behaviors and similarities of metals in each fraction. While Mn, Pb, and Zn exhibited subjective behaviors in the acid-soluble fraction, Cd, Co, Cu, Cr, and Ni exhibited similar behaviors with each other.     

Trace Metal Fractionation by the Sequential Extraction Method in Sediments from the Lis River (Portugal)

The extractable contents of Zn, Pb, Cu, Cr, Mn, Ni, Fe and Al were evaluated in sediments from the Lis River (Portugal) using the three-step sequential extraction procedure described by Community Bureau of Reference (BCR, now the Standards, Measurement and Testing Programme) of the European Union. The distribution of trace metals among the exchangeable, water and acid soluble, reducible, oxidizable and residual fractions was determined. The highest metal concentrations were observed in samples collected at the most polluted river sites (animal husbandry, domestic, industrial and agricultural wastes). Pb, Cu, Cr, Ni, Fe and Al were found mainly associated with the residual and organic fractions. High concentrations of Zn and Mn were found in the exchangeable/acid soluble fraction.     

Heavy Metals (Cd,Cu, Ni,Pb, and Zn) Fractionation in River Sediments,Hamedan, Western Iran

Five heavy metals (Cd, Cu, Ni, Pb, and Zn) in river sediments from Abshineh River, Hamedan, western Iran, were fractionated by a sequential extraction procedure. Cu, Ni, Pb, and Zn existed in sediments mainly in residual fraction (mean 92%, 86%, 77%, and 65%, respectively), whereas Cd occurred mostly as organic matter (mean 41%) and exchangeable (mean 25%) fractions. The mean percent of mobile fraction of Cd, Cu, Ni, Pb, and Zn in contaminated sediments was 25, 13, 4, 24, and 10, respectively, which suggests that the mobility and bioavailability of the five metals in sediments probably decline in the following order: Cd = Pb > Cu > Zn > Ni. The metal levels were also evaluated according to the contamination factor, which revealed significant anthropogenic pollution of Cd and Pb.     

铜锈环棱螺对沉积物中重金属的生物积累及其与重金属赋存形态的关系

以铜锈环棱螺（Bellamya aeruginosa）为测试生物,采用28 d沉积物生物积累试验研究铜锈环棱螺对污染河流沉积物中重金属的生物积累,并探讨其与重金属赋存形态的关系.结果表明：铜锈环棱螺肝胰脏对Cd、Pb、Cu、Cr、Zn和Mn均具有较强的积累作用.不同重金属的积累量存在较大差别,Zn的积累量最多,占重金属总积累量的84.32%±4.36%,其次为Cu,占7.67%±2.84%;Pb、Cr和Mn的比例相对较少,分别为3.62%±1.84%、2.22%±1.03%和1.33%±0.15%;Cd所占比例最少,为0.83%±0.53%.肝胰脏中重金属元素之间的相关性均不显著.肝胰脏金属污染指数与沉积物污染综合指数具有显著的正相关关系,铜锈环棱螺可以作为沉积物重金属污染的监测生物.不同沉积物Cd、Cr、Zn和Mn的生物-沉积物积累因子（BSAF）具有较大的差异,Cu和Pb的BSAF比较稳定.Cd的生物积累与沉积物中Cd的可交换的与酸可溶态及可氧化态显著相关;Pb的生物积累与Pb的可还原态显著相关;Cu的生物积累与Cu的可氧化态显著相关;Mn的生物积累与Mn的可交换的与酸可溶态和可还原态显著相关;Cr和Mn的生物积累与其不同形态和总量均不相关.BSAF不宜作为衡量铜锈环棱螺对沉积物中重金属生物积累能力的指标.     

The Concentration and Partitioning of Heavy Metals in Surface Sediments of the Maharlu Lake,SW Iran

In this study, an assessment is made of the environmental impacts of heavy metal concentration and fractionation in bed sediments of the saline Maharlu Lake, SW Iran. Total elemental analysis indicated that sediments were highly enriched in Pb and Cd. Sequential extraction analysis revealed that salt of the lake is probably highly contaminated with Cd, Pb, and Co. Due to the oxidizing conditions of the lake, the organic matter fraction of the elements was not significant. In all sediments, Cd, Pb, Co, Mn, and Zn were strongly associated with exchangeable plus carbonate fractions, with mean percentage of 76.4%, 65.3%, 56%, 40.9%, and 34.3%, respectively. On average, the percentage of Ni associated with the sum of the exchangeable and carbonate fractions was 19.8%. Cr, Fe, and Cu fractionation indicated that these metals are environmentally inert and immobile. Statistical relationships among metal fractions and sediment properties showed that Cd, Pb, Zn, Ni, Co, and Mn were mainly from recent anthropogenic sources, while such sources were less important for Cr, Cu, and Fe. The latter metals represented natural geochemical levels.     

Heavy Metal Partitioning in Bottom Sediments of the Matanza-Riachuelo River and Main Tributary Streams

This study provides geochemical partitioning, potential bioavailability, and enrichment of Cd, Cu, Pb, and Zn in bottom sediments collected from the Matanza-Riachuelo River and its main tributary streams. A modified Tessier sequential extraction procedure, complemented with acid volatile sulfide (AVS) and simultaneous extracted metals (SEM) measurements, was applied to determine the partitioning of metals into four fractions (metals bound to amorphous sulfide, carbonate, and exchangeable), bound to Fe/Mn oxides (reducible), bound to organic matter/sulfide (oxidizable) and residual. Spatial and vertical distributions of metals were studied. The core sediments show a decreasing concentration of metals with depth. In top sediments, non-residual Cu was mainly associated with oxidizable phase, whereas Pb, Cd, and Zn were mainly associated with amorphous sulfide. Pb exhibited the highest enrichment in all sites. The ratio AVS/SEM was greater than one at sediment sections close to the water column, indicating that metals extracted with hydrochloric acid were mainly associated with the amorphous sulfide. The strong influence of amorphous sulfide in the retention of Cd, Pb, and Zn in anoxic sediments of Matanza-Riachuelo river system suggests that dredging and aeration could lead to the remobilization of metals from sediments to the water column, hence making the metals more available to the biota.     

Sequential extraction and speciation of Ba,Cu, Ni,Pb and Zn in soil contaminated with automotive industry waste

Abstract

Sequential extraction or fractionation of heavy metals in the solid phase and their speciation in soil solution are important tools for assessing changes resulting from land use and/or pollution. The distribution of the various forms of Ba, Cu, Ni, Pb and Zn was evaluated in soil samples taken from a polluted area, and the speciation of cations and anions in a soil solution contaminated with automotive industry waste. We evaluated the sequential extraction and speciation of Ba, Cu, Ni, Pb and Zn in a Leptosol associated with a Cambisol and contaminated with automotive industry waste. Soil samples were collected at 0-0.2 m (a mix of soil and waste); 0.2-0.4 m (waste only), and 0.4-0.6 m (soil only) both in the polluted area and in two contiguous unpolluted areas: a sugarcane plantation and a forest fragment. Total concentrations of metals in the polluted area were above limits for intervention established by European Community regulations. Cu was mostly distributed in the residual and in the oxide-bonded fractions, except for the waste-only sample, in which the carbonate-bonded fraction was significant. Zn was concentrated in the residual and carbonate-bonded fractions, while Ba, Ni and Pb predominated in the residual fraction of the contaminated samples. Metals in the soil solution were predominantly in the hydroxyl forms, except for Ba, which was mostly in the ionic form (Ba²⁺).     

Distribution,bioavailability, and potential risk assessment of the metals in tributary sediments of Three Gorges Reservoir: The impact of water impoundment

To investigate the impact of water impoundment on the metal contamination in sediments cores from the three tributaries of Three Gorges Reservoir (TGR), the concentrations, distribution, bioavailability, and potential risk of eight trace metals between summer and winter were analyzed using sequential analysis. The mean contents of all studied metals were higher than the geochemical background value, and were higher in summer than in winter. The results of the partitioning study indicated that Cr and Ni prevailed in the residual fraction, while a small proportion was found in the easily soluble fractions. Cu and Zn were distributed mainly in the residual and reducible fraction, while Cd and Pb were predominantly associated with non-residual fractions. These observations suggested that the most easily mobilized metals in the study area were Cd and Pb. The mean enrichment factors (EF) of Cu, Zn, Cd and Hg were higher than 1.5, revealing the potential anthropogenic inputs, whilst the EF of other metals remained within the range of natural variability. The positive correlation between non-residual Cu, Zn and Cd and their EF values further indicated that anthropogenic inputs were the potentially major contributor for the enrichment of Cu, Zn and Cd in TGR sediments. The results evaluated by both potential ecological risk index and modified risk assessment code (mRAC) of all sampling sites demonstrated the relatively high potential risk of sediment contamination effect in TGR.     

Total concentrations and fractionation of heavy metals in road-deposited sediments collected from different land use zones in a large city (Nanjing), China

Abstract

In order to investigate heavy metal contamination in an urban environment during urbanization and economic development, 35 road-deposited sediment samples were collected from seven different land-use zones (commercial, residential, traffic, scenic park, educational, industrial and peri-urban) in Nanjing, a large city in P.R. China. The ranges of total metal concentrations found were: 28.7–272 mg kg^?1 for Cu; 24.8–268 mg kg^?1 for Ni; 37.3–204 mg kg^?1 for Pb; 140–798 mg kg^?1 for Zn; 0.44–2.19mg kg^?1 for Cd; and 60.6–250 mg kg^?1 for Cr. Metal fractionation was carried out using a modified three-step European Bureau of References (BCR) sequential extraction procedure. Cadmium and Zn were found predominantly associated with the acid extractable fractions; Ni and Cr were dominant in the residual fraction; Pb was predominantly associated with the residual and reducible fractions; Cu was dominant in the oxidizable and residual metal fractions. Based on the sum of the acid-extractable, reducible, and oxidizable fractions, Cd, Zn and Pb are potentially the most toxic metals in the road-deposited sediment in Nanjing. No significant differences, except for Zn, were found in the metal fractionation pattern for Cu, Ni, Pb, Cd, and Cr in different land use zones.     

强还原过程对设施菜地土壤重金属形态转化的影响

设施菜地由于污水灌溉、粪肥施用等导致重金属污染.本文通过土柱淹水同时添加玉米秸秆培养和后期通水淋洗,研究强还原法对设施土壤重金属(Cd、Cu、Pb和Zn)形态转化的影响.结果表明: 强还原处理使土壤pH显著降低,玉米秸秆处理变化更显著;土壤氧化还原电位(Eh)迅速下降至-280 mV左右.玉米秸秆处理可以促进土壤中Cd、Cu、Pb和Zn活化,第9天土壤中有机物及硫化物结合态和残渣态Cd、Cu、Pb和Zn含量比重下降;至15 d培养结束,土壤中4种重金属含量较对照分别减少18.1%、19.0%、16.1%和15.7%.玉米秸秆处理可以增加土壤中Cd和Zn的溶出量,但是Cu的溶出量减少;胶体结合态Cd和Pb含量较对照增加、Cu较对照显著减少、Zn没有显著变化.强还原可以引起设施土壤重金属活化,提高蔬菜积累重金属的风险,而且其随土壤水分的运移可能导致水体的污染.     

Bioavailability and mobility of heavy metals in soil in vicinity of a coal mine from Huaibei,China

This study investigated the concentrations of Co, Cr, Cu, Mn, Ni, Pb and Zn in surface soil and corn cob samples collected from agricultural fields near a coal mine from Huaibei, China. Meanwhile, the mobility and availability of heavy metals in soil samples were evaluated by a modified three-step The European Community Bureau of Reference (BCR) sequential extraction procedure. The total concentrations of metals in soil pose no ecological threats to the local plants. Transfer factors of essential metals, Cu and Zn, as well as those of non-essential metal Pb, were higher than those of the remained metals. The results of BCR fractionation analysis revealed that the acid soluble, reducible and oxidizable fractions of the Mn, Pb and Zn were higher than those of the residual fraction, suggesting that these elements may be more bioavailable. The pH and organic matter contents of soil were significant parameters affecting speciation of metals in soil samples. Hierarchical cluster analysis indicated significant correlations between metal levels in corn grains and more available (acid soluble and reducible) fractions in soil, indicating that heavy metals in the first two fractions were more available for corn crops. The elevated mobility and bioavailability of Pb in soil are of great concern in the study area.     

贵州兴仁煤矿区农田土壤重金属化学形态及风险评估

为了解煤矿区周边农田土壤重金属污染状况,采集了贵州省兴仁县某典型煤矿区农田土壤样品64份,测定了土样中重金属(As、Cr、Pb、Zn、Cd、Hg、Cu、Ni)总量及各形态含量,采用单因子指数法、潜在生态风险指数法(Hkanson法)和风险评估编码法(RAC)对研究区主要土壤利用类型(水稻土、薏米地、植烟土和菜园土)中重金属进行潜在生态风险评估和环境风险评价.结果表明： 不同利用类型土壤中重金属含量除Zn外,其他元素均明显超过贵州省背景值.单因子指数法评价结果表明,As、Pb、Hg和Cu污染较为严重,均属重度污染.形态分析表明,土壤中重金属形态构成差异明显,酸可提取态As、酸可提取态Cd所占比例较高;Cr、Zn、Cu、Ni主要以残渣态为主;Pb主要以可还原态和残渣态为主;而Hg的酸可提取态、可还原态、可氧化态均占有相当比例,三者之和大于55%.重金属可利用度大小顺序为:As(63.6%)>Hg(57.3%)>Cd(56.4%)>Pb(52.5%)>Cu(45.7%)>Zn(32.8%)>Ni(26.2%)>Cr(13.2%).潜在生态风险指数表明,各类型土壤潜在生态风险(RI)〖JP2〗为:菜园土(505.19)>薏米地(486.06)>植烟土(475.33)>水稻土(446.86),均处于较高风险.风险评估编码法结果显示,As在水稻土、薏米地及植烟土中均处于高风险,在菜园土中处于中等风险;Cd、Hg均处于中等风险,Cr、Pb、Zn、Cu和Ni均处于低风险.因此,对该区域农田土壤进行管控时应重点考虑As、Cd和Hg污染.     

Heavy metals in water,sediments, fish and plants of river Hindon,U.P., India

We analysed the concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn in the water, sediments, fish and plants of the River Hindon, U.P., India, at seven sampling stations, in the year 1982. Considerable variation in concentration between water, sediments, fish and plants were noted. The concentration in the water was in the order Fe > Zn > Cr > Mn > Cu > Pb > Ni > Co > Cd, in the sediments, Fe > Mn > Zn > Ni > Cr > - Co > Cu > Pb > Cd; in a fish (Heteropnuestes fossilis) Fe > Zn > Mn > Pb > Ni > Co > Cu > Cd > Cr, and in a plant (Eicchornia crassipes) Fe > Mn > Zn > Ni > Cu > Cr > Pb > Co > Cd.     

Trace element concentrations of oligochaetes and relations to sediment characteristics in the reservoir at Altenwörth/Austria

Summary The sediments of the River Danube in the Reservoir at Altenwörth/Lower Austria, are moderately polluted with Zn, Pb, and Cd, whereas concentrations of As, Co, Cr, Cu and Ni are typical of background values. Deposit-feeding oligochaetes living in these sediments were analyzed for their trace element concentrations (As, Cd, Cu, Pb, Zn) to study pathways of recycling of sediment bound amounts to the food web. Compared with background values of benthic deposit feeders from the literature, Cu and As are low, whereas some samples were enhanced in Pb, Cd and Zn. Within the rather narrow concentration ranges, relations of tissue concentrations with chemical and mineralogical compositions of the sediment were hardly found. Increase of clay mineral contents went in parallel with increasing Cd, Zn, and Cu in the tissues, and As in the tissues with total As content. Pb in the tissues was closely related to Pb-concentrations in the pore water. By means of sequential leaching, some further relations between trace element contents in the tissues and solid phases were found. The organic detrital phase positively correlates with As-uptake, whereas hydroxylamine-reducible Mn/Fe-oxyhydroxides influence the Pb-level, and dithionite-reducible Fe/Mn influence the Cu-level. Exchangeable and weak-acid-mobile fractions of the respective metals, however, did not correlate with tissue-levels, nor did the oxalate-extractable Fe-hydroxide coatings, which carry a major part of the heavy metals at fine grain sizes in the Danube sediments investigated. Zn in the tissues was largely independent from all investigated parameters.     

Solid-Phase Chemical Fractionation of Selected Trace Metals in Some Northern Kentucky Soils

The fractionation and distribution with depth of Cd, Cr, Cu, Ni, Pb, and Zn in 26 soils of Northern Kentucky were determined through a sequential extraction procedure in response to environmental concerns about increasing anthropogenic inputs in a fast-paced, urbanizing area. The selected sites have not received any biosolid- or industrial-waste applications. Average total concentrations per metal in soil profiles derived from alluvial, glacial till, and residual materials ranged from 0.43 to 56.00 mg kg^?1 in the sequence Zn > Ni > Pb > Cr > Cu > Cd, suggesting relatively small anthropogenic inputs. The distribution of Cu, Cr, Ni, and Zn increased with soil depth, whereas Cd and Pb remained stable, indicating a strong geological or pedogenic influence. Residual forms were most important for the retention of Cu, Zn, and Ni. Cadmium and Pb exhibited a strong affinity for the Fe-Mn oxide fraction, while Cr showed the strongest association with the organic fraction. In terms of metal mobility and toxicity potential inferred from metal concentrations in labile fractions, Cd posed the greatest risk, followed by Cr ～ Pb > Ni > Zn > Cu. Soil pH, OM, and clay content were the most important parameters explaining the partitioning of metals in labile and residual fractions, emphasizing the importance of metal fractionation in soil management decisions. Alluvial soils generally contained the highest total and labile metal concentrations, suggesting potential metal enrichment through anthropogenic additions and depositional processes. These environments exhibit the highest risk for metal mobilization due to drastic changes in redox conditions, which can destabilize existing metal retention pools.     

Bioavailability and Concentration of Heavy Metals in the Sediments and Leaves of Grey Mangrove, <Emphasis Type="BoldItalic">Avicennia marina</Emphasis> (Forsk.) Vierh,in Sirik Azini Creek,Iran

The concentration and bioavailability of Ni, Cu, Cd, Zn, and Pb in the sediments and leaves of grey mangrove, Avicennia marina, were studied throughout Sirik Azini creek (Iran) with a view to determine heavy metals bioavailability, and two methods were used. Results show that Zn and Ni had the highest concentrations in the sediments, while Cd and Cu were found to have the lowest concentrations in the sediments. Compared to the mean concentrations of heavy metals in sedimentary rock (shales), Zn and Cu showed lower concentration, possibly indicating that the origin of these heavy metals is natural. A geo-accumulation index (I _geo) was used to determine the degree of contamination in the sediments. I _geo values for Zn, Cu, Pb, and Ni showed that there is no pollution from these metals in the study area. As heavy metal concentrations in leaves were higher than the bioavailable fraction of metals in sediments, it follows that bioconcentration factors (leaf/bioavailable sediment) for some metals were higher than 1.     

Heavy metals in water,sediments and invertebrates from a metal-contaminated river free of organic pollution

A study was made of water, sediments and invertebrates in the R. Derwent, North-East England, at one site above and three sites below a stream bringing in high concentrations of Zn, Cd and Pb derived from an active fluorspar mine. The mean concentrations of these metals in filtrable water at the unpolluted site were 0.020, <0.0003, 0.005 mg l^-1, respectively, while those at the first polluted site were 0.29, 0.0006, 0.016 mg l^-1. The benthic macroinvertebrate fauna was dominated by insects; all taxa present at the unpolluted site were represented at one or more of the polluted sites. In almost all cases the elevated concentrations of metals in water and sediments at polluted sites were paralleled by higher concentrations in animals. Significant positive correlations were demonstrated between metal concentrations in certain taxa and those in their environment e.g. Ecdyonurus venosus and aqueous Pb. Mayflies tended to concentrate Zn, Cd and Pb to higher levels than other groups. Comparison of carnivorous species with other taxa revealed no indication of increased metal concentrations at higher trophic levels.     

Concentration and ecological risk of heavy metal in street dusts of Eslamshahr,Iran

This study was done to evaluate heavy metal concentrations in street dust samples, to compare measured concentrations in samples to background concentrations in order to make evaluations for pollution indices, and to describe the quality of street dust in the studied area in relation to pollution. A total of 30 cumulative samples were collected from the streets of Eslamshahr City. Concentrations of heavy metals were determined using an Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES). Results determined mean concentrations (mg/kg) of the heavy metals Cd, Cr, Cu, Ni, Pb, and Zn, in collected samples of street dust as 0.34, 35.1, 239, 42.4, 71.3, and 573, respectively. I_geo values for Cd and Cr, Cu, Ni, Pb, and Zn showed level of moderately polluted, unpolluted, moderately to strongly polluted, unpolluted, moderately polluted and moderately to strongly polluted, respectively. The pattern of total metal concentrations in the studied area was ranked as follows: Zn and Cu>Pb>Cd>Ni>Cr. The highest values for the monomial potential ecological risk (E_r) were observed for Cd (114). The mean level of RI for the studied soil samples was 192 (91.3–244), which is classed as presenting a strong potential ecological risk.     

Effects of Amendments and Water Conditions on the Chemical Speciation of Cd and Pb in Contaminated Paddy Soil in a Mining Area

Lime, sepiolite and peat were used as amendments to study their effects on the chemical speciation of Cd and Pb in a polluted paddy soil under moist and water-logged conditions. The results showed that application of amendments reduced acid-extractable Cd (up to 12.56% and 5.07%) and Pb (up to 6.69% and 2.68%) in moist and water-logged soils, respectively. The reducible Cd and residual Cd was increased while the oxidizable Cd was decreased after adding amendments. However, the oxidizable Pb was increased while the residual Pb was decreased in amended soil, and the reducible Pb presented a different changing trend under moist and water-logged conditions. The soil pH was significantly correlated with different fractions of Cd and Pb in soil, which indicated a distinct influence of soil pH on the redistribution process of Cd and Pb fractions in amended soil.