Identification of sources of heavy metals in agricultural soils using multivariate analysis and GIS

Purpose

Heavy metals in agricultural soils readily enter the food chain when taken up by plants, but there have been few investigations of heavy metal pressure in farming areas with low background concentrations. This study was carried out in a cultivation area of Northeast China that has undergone decades of intensive farming, with the aim of identifying the sources of accumulated heavy metals in agricultural soils using multivariate analysis and geographic information system (GIS).

Materials and methods

In 2011, concentrations of total iron (Fe), manganese (Mn), copper (Cu), nickel (Ni), lead (Pb), zinc (Zn), cadmium (Cd), chromium (Cr) and cobalt (Co), as well as soil pH and organic matter, were measured at 149 sites in arable soils in the study area. The principal component analysis (PCA) was employed to extract hidden subsets from the raw dataset in order to detect possible sources. Metal contents in soils from various croplands were further investigated using analysis of variance. With the Kriging interpolation method, GIS was used to display the PCA results spatially to explore the influence of land use on heavy metal accumulation.

Results and discussion

Most of the studied metals in arable soils of the study area were shown to have low concentrations, except for Cd (0.241 mg?kg^?1). According to the results of the PCA analysis, Fe, Mn, Pb, Zn, Cd, and Co formed the first component (PC1) explaining 40.1 % of the total variance. The source of these metals was attributed to farming practices (“anthropogenic” factor). Cu, Ni, and Cr fell into the second component (PC2), heavy metals that derived from parent rock materials (“lithogetic” factor). This component describes 24.6 % of the total variance. Compared to paddy lands, soils in drylands had greater accumulations of all the metals in PC1, which can be explained by a higher rate of phosphorus fertilizer application and a longer farming history.

Conclusions

Owing to the natural low backgrounds, soils in the study area were safe from heavy metal pollution with a contamination risk of Cd the only exception. Multivariate analysis and GIS were effective means in helping to identify the sources of soil metals and addressing the land use influence on soil metals accumulation. This work can support the development of strategy and policies to aid in the prevention of widespread heavy metal contamination in area with characteristics similar to those of the study area.     

Mobilization of heavy metals from river sediments of Northern Greece by complexing agents

The influence of NTA, EDTA, STPP, Triton X100, PO _inf4 ^sup3 and NO _inf3 ^sup? on the mobilization of Pb, Cd, Cu, Cr and Mn from sediments of two rivers located in Northern Greece was studied. The release caused by all examined complexing agents was higher in deionized water than either Axios or Aliakmon river water due to the lack of competition of Ca and Mg cations with the heavy metals for the studied complexing agents, and the decrease of ionic strength. From all examined agents NTA and EDTA showed the greater mobilization ability. Copper showed the greater tendency for remobilization by all examined agents, (according to the order: EDTA?NTA, Triton X1004 PO _inf4 ^sup3? > NO _inf3 ^sup3? ?STPP) while Cr and Mn the smallest following the orders: NTA, PO _inf4 ^sup3? >> NO _inf3 ^sup? , Triton X1004 EDTA, STPP and STPP > EDTA > NTA > Triton X 100 ? PO _inf4 ^sup3? NO₃, respectively. An increase in mobilization was noticed with an increase of agent concentration and time of shaking.     

Origin,retention and release of trace metals from sediments of the river seine

Metallic contents (Fe, Mn, Pb, Cu, Cd, Zn, Cr) of sediments were measured in 14 sites in the River Seine (France) along 110 km; in three sites surrounding the sewage treatment plant at Achères, vertical profiles were established from cores and dialysis cells, and interface exchanges have been studied. Metal contamination increases downstream, except for Pb for which contamination is higher immediately downstream of stormdrains (up to 130 mg kg^?1); that confirms its urban origin. Upstream of Achères, metallic contamination increases with depth while downstream, contribution to sediments of suspended matter from the treatment plant, loaded with organic matter, alters the behaviour of metals within the first ten centimeters. A strong link between particulate organic carbon (POC), polycyclic aromatic hydrocarbons (PAH), polychlorobiphenyls (PCB) and metal contents has been established. The organic matter brought down by the treatment plant effluents induces a specific diagenesis downstream leading to metal release in summer as attested by a 30% metal contents decrease in sediments. Calculation of molecular diffusion fluxes shows that in september, the release phenomenon is ending.     

Distinguishing regional and local sources of pollution by trace metals and magnetic particles in fluvial sediments of the Morava River, Czech Republic

Purpose

Regional contamination of southern Moravia (SE part of the Czech Republic) by trace metals and magnetic particles during the twentieth century was quantified in fluvial sediments of the Morava River. The influence of local pollution sources on regional contamination of the river sediments and the effect of sampling site heterogeneity were studied in sediment profiles with different lithologies.

Materials and methods

Hundreds of sediment samples were obtained from regulated channel banks and naturally inundated floodplains and proxy elemental analyses were carried out by energy dispersive X-ray fluorescence spectroscopy (ED XRF) and further calibrated by inductively coupled plasma mass spectrometry (ICP MS). Magnetic susceptibility was determined as a proxy for industrial contamination. The age model for the floodplain sediments was established from ¹³⁷Cs and ²¹⁰Pb dating. Trace metal contamination was assessed by establishing the lithological background values from floodplain profiles and calculating enrichment factors (EF) of trace metals (i.e. Pb, Zn, Cu) and magnetic susceptibility for the entire study area.

Results and discussion

Channel sediments are unsuitable for the reconstruction of historical regional contamination due to their lithological heterogeneity and the “chaotic” influence of local sources of contamination, as well as the possibility of geochemical mobility of pollutants. On the other hand, sediments from regulated river banks qualitatively reflected the actual, local contamination of the river system.

Conclusions

This approach allowed us to distinguish the influence of local sources of contamination by comparison with more spatially averaged contamination signals from distal floodplain profiles. The studied area is weakly contaminated (EF ～1–2), while individual sediment strata from regulated channel banks reflect local sources of contamination and contain up to several times higher concentrations of trace metals.     

Spatial patterns and temporal changes of heavy metal distributions in river sediments in a region with multiple pollution sources

Purpose

The main purpose of this study was to evaluate temporal and regional variability of contamination by heavy metals (HMs) in river sediments using their enrichment factors (EFs) and benchmarking according to sediment quality guidelines (SQGs). The Zlin region in the Czech Republic (Morava and Drevnice River basins) represents a model area where several regionally specific ecological risk assessment studies have recently been conducted with a focus on organic pollution, eco-toxicity, geological, and geochemical characteristics.

Materials and methods

Four consecutive sediment sampling campaigns were undertaken in spring and autumn 2005–2006. Aqua-regia leachable content of Cd, Co, Cr, Cu, Ni, Pb, Sb, V, and Zn in surface sediments from 14 sites was analyzed using ICP-MS, and Hg content was analyzed using AMA-254 analyzer. EFs were calculated to identify the human impact on pollution in the area. Comparisons to SGQs were conducted to identify the areas and HMs of greatest risk.

Results and discussion

Calculation of EFs contributed to the effective clustering of HMs. Median EFs of Co, Ni, and V ranged from 0.9 to 1.4 at all sites indicating concentrations very close to natural geological background levels. There was greater enrichment at locally polluted sites, the highest in the cases of Cd, Sb, Hg, and Cr. Widespread influence of diffuse HM sources (traffic, agriculture, and urban wastes) was apparent from elevated concentrations of Pb, Cu, and Zn at all sites. EF values also helped to identify the greatest temporal changes and shifts in HMs contamination between adjacent sites caused by 50-year recurrence interval floods in early spring 2006. The impact was most apparent in downstream sites; namely directly below the confluence of the two major rivers.

Conclusions

The overall contamination of HMs in the region was classified as low-to-moderate with significantly contaminated sub-areas. The study showed relatively stable spatial distributions of HMs, indicating potential sources of pollution. Cu was identified as the HM of greatest risk. The study emphasizes the necessity of considering both environmental circumstances and background HM occurrence to prevent misinterpretation of the pollution situation. The use of EFs which include grain size proxy normalization and HM background levels, along with the comparison of the detected concentrations to SQGs, proved an efficient way to identify hazardous contamination from anthropogenic sources.     

Horizontal and vertical distribution of selected metals in the kubanni river,nigeria as determined by neutron activation analysis

Abstract

Neutron Activation Analysis (NAA) was used for the determination of metal concentrations of sediments sampled at specific locations of the Kubanni River in Nigeria. The sedimentation process was assessed by examining the variation of the concentrations of the metals in different cores with sediment depths. Fifteen metals: arsenic (As), cerium (Ce), europium (Eu), iron (Fe), gadolinium (Gd), hafnium (Hf), holmium (Ho), potassium (K), lanthanum (La), lutetium (Lu), samarium (Sm), scandium (Sc), thorium (Th), uranium (U), and ytterbium (Yb) were detected from the sediments in substantial concentrations; higher than the parts per million (μg g^‐1) value in some cases. Our results showed contamination of the surface sediments by U and Th, suggesting contributions from phosphate fertilizers used in farmlands around the basin as potential sources of these pollutants. Aeolian depositions emanating from the uranium‐rich region of Air (Niger) in the Saharan desert were considered to be other possibilities.     

砷-重金属复合污染土壤稳定化材料研究进展

我国土壤重金属污染现状十分严峻,多金属复合污染,尤其是砷-重金属复合污染普遍存在,治理难度大。土壤中累积的多金属污染物严重威胁土壤健康、农产品安全与人居环境安全。因此,多金属复合污染土壤修复是土壤污染治理和风险防控的重要命题。固化/稳定化技术是我国最为广泛使用的污染土壤修复技术,通过投加稳定化材料,降低多金属污染物在土壤中的可迁移性与生物有效性,从而实现多金属污染物暴露途径的有效阻断。对砷-重金属型复合污染土壤的稳定化作用机理进行了详细阐述并梳理了应对砷-重金属复合污染土壤的新型修复材料。砷与其它重金属的协同稳定化主要通过表面络合与沉淀作用实现。富含铁、钙元素的材料对这种类型土壤的稳定化具有优异的作用效果。砷-重金属协同稳定化材料的修复效果取决于稳定化材料的类型、复合污染物的种类、材料施用量、土壤条件（如pH,氧化还原电位、阳离子交换量等）,其中pH和土壤可溶性有机质含量对稳定化效果有显著的影响。本文发现,功能化生物质复合材料、工业固废基材料、改性复配天然矿物等绿色修复材料是近年来研究的热点。未来的研究亟须考虑砷与重金属污染物协同稳定剂的长效性,以及通过大田试验验证新型材料的应用潜能。     

Deposition of trace metals in stream sediments

Sediment samples have been collected downstream from a Pb smelter and analyzed for Cd, Cu, Fe, Pb, and Zn. The concentrations of these trace metals decrease with increased distance from the smelter. The decrease in trace metal contant has been utilized to provide an indication of how rapidly artificially high levels of trace metals are reduced to the carrying capacity of a natural water. Equilibrium calculations are utilized to predict the water's intrinsic trace metal carrying capacity.     

Effect of different forms and sources of arsenic on crop yield and arsenic concentration

Two greenhouse experiments were conducted to investigate the effects of different sources of As application on the yield of ryegrass (Lolium perenne L.) and barley (Hordeum vulgare L.) and the arsenic concentration in crop tissue. The soils used were a sand and a loam soil. In the first experiment (3 yr), As was applied either as sodium arsenite or as disodium hydrogen arsenate at the rate of 0, 2, 10, 50, and 250 mg As kg^?1 soil in year 1. In years 2 and 3, only the residual effect of As applied in year 1 was investigated. In the second experiment (5 yr), a NPK(16-7-12) fertilizer containing 10, 100 and 3000 mg As kg^?1 as sodium arsenite was applied at rates of 750 and 600 mg kg^?1 to ryegrass and barley, respectively, with lime and without lime. Arsenite had more inhibitory effect on crop yield than arsenate. Although the residual effect persisted up to year 3, it was found to be dependent on As application rate, soil type, and crop species. Only minor differences in As concentration in crops between arsenite and arsenate sources were observed. The yield reduction and the increase of As concentration in crops was highly related to As application rates. The As rates of 50 and 250 mg As kg^?1 resulted in significant yield reduction and marked increase of As concentration in both crops and these rates could be considered as critical for both crops. The application of As containing fertilizer had little or no effect on crop yield. The As concentration in both crops was little affected by the fertilizer containing up to 100 mg As kg^?1 but the concentration increased several folds when the fertilizer containing 3000 mg As kg^?1 was applied. The application of additional P to the treatment containing 3000 mg As kg^?1 fertilizer only slightly increased crop yields but it increased As concentration in ryegrass markedly. The repeated application of As containing fertilizer up to a period of 5 yr, even at 3000 mg As kg^?1 level, generally did not affect either the yields or the As concentration in both crops although a slight increase of As concentration in barley grain over the years was observed. In both experiments, the yield reduction and the increase in As concentration in crop tissue were lower in the loam soil than in the sand and barley straw cointained much higher As than barley grains, indicating that greater proportion of the As taken up by this crop was retained in the vegetative organs.     

Review of remediation technologies for sediments contaminated by heavy metals

Journal of Soils and Sediments - Contamination of sediments with heavy metals (HMs) is a worldwide environmental issue, due to the negative ecological effects of HMs. Sediments are an important...     

Control of geochemical mobility of arsenic by liming in materials subjected to acid mine drainage

Background  Acid mine drainage (AMD) results from the exposure of sulfide materials to atmospheric water and oxygen. In addition to AMD, oxidation of arsenopyrite and other As-bearing sulfides can release arsenic (As) into the environment. In view of the risk to living organisms due to contamination of ground and surface water sources with As, this work was carried out to evaluate the effectiveness of lime (CaCO₃) in controlling the dispersion of this metalloid in the environment. Methods  Partially oxidized samples of sulfide bearing materials from gold mines in Brazil were used to evaluate the arsenic mobilization by leaching tests. Columns containing ground samples, with and without liming treatments, were leached with distilled water every two weeks over a 156-day period. Results and Discussion  The acid-base accounting (ABA) static tests classified the samples as potential acid forming materials. In the treatments without liming, As, Fe and S concentrations in the leachates were higher than after treatment with carbonate. Nevertheless, the effectiveness of liming and As mobilization were lower in the sample containing goethite. A high correlation between Fe and As concentrations in the leachates (r=0.749) suggests that iron (hydr)oxides retained arsenic in the solid phase. Oxidation rates of As bearing sulfides were increased at low pH (2.0–3.9), probably due to the enhanced activity of bacteria (Acidithiobacillus) and decreased rate of Fe precipitation, thus reinforcing generation of acid water, and consequently releasing As. Conclusions and Perspectives  Our results corroborate the use of lime to control the dispersion of As in AMD-affected environments. However, the effectiveness of the liming treatment seems to be dependent on the presence of iron (hydr)oxides in the sample. These findings can be useful to remediate areas affected by acid mine drainage and arsenic mobilization in partially oxidized sulfide materials. ESS-Submission Editor: Chengrong Chen, PhD (c.chen@griffith.edu.au)     

Clay mineral composition of river sediments in the Amazon Basin

Clay minerals are important in evaluating the maturity of suspended sediments, weathering intensity and source area. However, there are processes that can change the mineral assemblage such as river transportation, deposition, remobilization and tributary inputs. In terms of water discharge and sediment yield, the Amazon is one of the largest rivers in the world. Most of the suspended sediments come from the Andes, crossing the lowlands before reaching the ocean. This study measures the spatial distribution of clay mineral assemblages over the entire Amazon basin. The results obtained show the main features of the Amazon River main stem and larger tributaries from their sources to their confluence. Clay mineral composition highlights the evolution of the Madeira and Marañón–Solimões River, which start in the Andes with high illite + chlorite content. Downstream, smectite contents increase. Moreover, all shield tributaries show high kaolinite content. The lower Amazon River is characterized by relative high smectite content, different from the Andean sources. The clay mineral results show that suspended sediments of the Amazon River have three main sources: 1) the Andes mountains; 2) the Amazon shields and 3) the Piedmont basins, especially the Pastaza alluvial megafan and the Fitzcarrald Arch basin. Lateral bank erosion plays also a significant role, by the introduction of more mature sediments into the river, enriched in smectite.     

Transport and distribution of heavy metals in Cauvery river

Heavy metal transport in Cauvery river chiefly takes place in the particulate form. Tributaries Hemevathi and Kabini draining highly mineralized areas contribute significantly to the heavy metal load of the Cauvery river. Particulate metal transport is influenced by the presence of major dams built across the river. Factor analysis of the elemental data identifies two major group of heavy metals, (a) Fe, Mn, Cr, V and Ti and (b) Cu, Pb and Zn in the suspended sediments of Cauvery river. Heavy metals in surface sediments show wide variations in their concentrations due to the non-uniform grain size distribution of the sediments. The elements Fe, Mn, Pb, Cu, Zn, Ni, Co and As are dominantly present in the <20 μm fraction of the river sediments. Speciation studies show that Fe-Mn oxide phase held the largest share of heavy metals in the sediments. The depth variation of heavy metals in the core sediments suggest their similar mobility during diagenesis. Geoaccumulation indices calculated suggest that Cd, Zn, Cr, Pb, Cu and Ni are enriched in sediments several times over background values.     

Retention and release of selected major and minor metals by the altamaha river marsh ecosystem

The retention and release of two major metals, K and Mg, and two minor metals, Zn and Mn, bySpartina alterniflora andSpartina cynosuroides salt marsh ecosystems along the terminal course of Altamaha river were investigated. The metal content in plant and soil samples collected from the two sites was measured periodically. A rectangular box-model of the ecosystem (1 m × 1 m × 0.5 m) was used to normalize the metal content of all materials in g m^?3. The net annual retention or release of the metals in the ecosystem was computed from the periodic changes in the metal content of the live plant, dead tissues and of the soil (HCI extractable). The system populated byS. alterniflora releases 1.53 g m^?3 of Mn while that covered byS. cynosuroides delivers 17.18 g m^?3 of Mn to the river. Zinc is retained at the annual rate of 0.17 g m^?3 by the former system and 1.21 g m^?3 by the latter. The annual retention rate of K and Mg byS. alterniflora system is 71.76 g m^?3 and 522.08 g m^?3 respectively, whileS. cynosuroides system retains annually 171.0 g m^?3 of K and 499.54 g m^?3 of Mg.     

An appraisal of microwave-assisted Tessier and BCR sequential extraction methods for the analysis of metals in sediments and soils

Purpose  

The purpose of this research was to assess the precision and accuracy of a BCR and Tessier microwave-assisted sequential extraction procedure, in comparison to the conventional versions for a range of metals using a soil, lake and estuarine certified reference material (CRM).     

An integrated geochemical and mineralogical approach for the evaluation of arsenic mobility in mining soils

Purpose  

The assessment of risk related to the presence of potentially toxic elements in soils is strictly related to the knowledge of their form and mobility. These relevant properties depend on the complex interactions of the elements of concern with the soil particles that generally cannot be addressed by a single technique. This study presents an integrated approach implementing geochemical and mineralogical investigation techniques on samples from a former mining area (Tolfa Mountains district, northern Latium, Italy), where exploiting activities occurred until the recent past. In particular, the As total concentration and the As distribution in solid phases is studied with the aim to evaluate the possibility of environmental pollution and consequent risks for the health of people living in the area and possibly affected in case of significant mobilization of this toxic element.     

Trace metals and lanthanides in a tropical river environment

The river Periyar in the State of Kerala, India is subjected to pollution from a number of industrial units such as zinc smelter, rare earth plant, phosphatic fertilizer unit etc. The levels of Zn and Cd in water and sediments in the river have in recent years increased ten fold as compared to a study conducted earlier during 1970. The levels of these trace metals in water increase at the backwater zone under high salinity in summer due to solubilisation from the sediments. Among the lanthanides Ce is the most predominant in water. Elements such as Ce, La, Sm, Gd and Y show a concentration factor of 10³ in sediments. The trace metals show maximum concentration at the top layer of sediment column extending up to 20 cm from the surface. Particle size analysis of river sediments in the industrial outfall area shows a mass median diameter of 11 μm with a geometric standard deviation of 2.4 for Zn and Cd.     

Microbial methylation of mercury in upper Wisconsin river sediments

The microbial methylation of Hg was studied in water and sediments from the Upper Wisconsin River by quantifying the methylation of radioactive Hg(II) (²⁰³Hg[NO₃]₂). Methylation activity was near detection limits in the water, highest in surface sediments (0 to 4 cm), and decreased with increasing sediment depth. Methylation had a temperature optimum of 35 °C. Organically enriched sediments exhibited higher methylation activity than less eutrophic sediments. Methylation activity in sediments was stimulated by the addition of peptone but not by glucose or starch. Oxygenation of sediments inhibited methylation activity. A summertime peak in methylation activity, observed in water, floc, and sediments, was related to factors other than temperature. More than 98% of the added ²⁰³Hg(II) was bound to sediments within 4 hr of inoculation, while more than 3% was methylated during a 10-day incubation. As much as 7% of the added ²⁰³Hg(II) was methylated in other experiments, suggesting that bound Hg is available for methylation. These data suggest that organic-rich surficial sediments in the Upper Wisconsin River have the potential to produce significant amounts of toxic methylmercury during late summer months.     

Butyltin and phenyltin compounds in river i bay sediments of Tokyo

The occurrence and current status of butyltin and phenyltin compounds were investigated in sediments collected from the Arakawa and Sumida Rivers and Tokyo Bay in 2000. A series of butyltin and phenyltin compounds, including monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monophenyltin (MPT), diphenyltin (DPT), and triphenyltin (TPT) was detected by gas chromatography-mass spectrometry (GC-MS). The total concentrations of the butyltin (MBT + DBT + TBT) and phenyltin (MPT + DPT + TPT) compounds ranged from 25.7 to 116 and from non-detectable levels to 22.4 ng g' (as Sn), respectively. The concentrations of the organotin (OT) compounds in sediments were relatively lower than those of the samples collected in 1984. OT compounds accounted for 124% (as Sn) of total Sn in the sediments. Among the OT compounds investigated, MBT was the most prevalent in the sediments.     

基于多元统计学和地统计学的土壤重金属源解析

The main objectives of this study were to introduce an integrated method for effectively identifying soil heavy metal pollution sources and apportioning their contributions, and apply it to a case study. The method combines the principal component analysis/absolute principal component scores (PCA/APCS) receptor model and geostatistics. The case study was conducted in an area of 31 km² in the urban-rural transition zone of Wuhan, a metropolis of central China. 124 topsoil samples were collected for measuring the concentrations of eight heavy metal elements (Mn, Cu, Zn, Pb, Cd, Cr, Ni and Co). PCA results revealed that three major factors were responsible for soil heavy metal pollution, which were initially identified as “steel production”, “agronomic input” and “coal consumption”. The APCS technique, combined with multiple linear regression analysis, was then applied for source apportionment. Steel production appeared to be the main source for Ni, Co, Cd, Zn and Mn, agronomic input for Cu, and coal consumption for Pb and Cr. Geostatistical interpolation using ordinary kriging was finally used to map the spatial distributions of the contributions of pollution sources and further confirm the result interpretations. The introduced method appears to be an effective tool in soil pollution source apportionment and identification, and might provide valuable reference information for pollution control and environmental management.