Metal accumulation in earthworms inhabiting floodplain soils

The main factors contributing to variation in metal concentrations in earthworms inhabiting floodplain soils were investigated in three floodplains differing in inundation frequency and vegetation type. Metal concentrations in epigeic earthworms showed larger seasonal variations than endogeic earthworms. Variation in internal levels between sampling intervals were largest in earthworms from floodplain sites frequently inundated. High and low frequency flooding did not result in consistent changes in internal metal concentrations. Vegetation types of the floodplains did not affect metal levels in Lumbricus rubellus, except for internal Cd levels, which were positively related to the presence of organic litter. Internal levels of most essential metals were higher in spring. In general, no clear patterns in metal uptake were found and repetition of the sampling campaign will probably yield different results.     

Effects of mercury on visible/near-infrared reflectance spectra of mustard spinach plants (Brassica rapa P.)

Mustard spinach plants were grown in mercury-spiked and contaminated soils collected in the field under controlled laboratory conditions over a full growth cycle to test if vegetation grown in these soils has discernible characteristics in visible/near-infrared (VNIR) spectra. Foliar Hg concentrations (0.174-3.993ppm) of the Mustard spinach plants were positively correlated with Hg concentration of soils and varied throughout the growing season. Equations relating foliar Hg concentration to spectral reflectance, its first derivative, and selected vegetation indices were generated using stepwise multiple linear regression. Significant correlations are found for limited wavelengths for specific treatments and dates. Ratio Vegetation Index (RVI) and Red Edge Position (REP) values of plants in Hg-spiked and field-contaminated soils are significantly lower relative to control plants during the early and middle portions of the growth cycle which may be related to lower chlorophyll abundance or functioning in Hg-contaminated plants.     

Determining metal origins and availability in fluvial deposits by analysis of geochemical baselines and solid-solution partitioning measurements and modelling

Metals in floodplain soils and sediments (deposits) can originate from lithogenic and anthropogenic sources, and their availability for uptake in biota is hypothesized to depend on both origin and local sediment conditions. In criteria-based environmental risk assessments, these issues are often neglected, implying local risks to be often over-estimated. Current problem definitions in river basin management tend to require a refined, site-specific focus, resulting in a need to address both aspects. This paper focuses on the determination of local environmental availabilities of metals in fluvial deposits by addressing both the origins of the metals and their partitioning over the solid and solution phases. The environmental availability of metals is assumed to be a key force influencing exposure levels in field soils and sediments. Anthropogenic enrichments of Cu, Zn and Pb in top layers could be distinguished from lithogenic background concentrations and described using an aluminium-proxy. Cd in top layers was attributed to anthropogenic enrichment almost fully. Anthropogenic enrichments for Cu and Zn appeared further to be also represented by cold 2 M HNO₃ extraction of site samples. For Pb the extractions over-estimated the enrichments. Metal partitioning was measured, and measurements were compared to predictions generated by an empirical regression model and by a mechanistic-kinetic model. The partitioning models predicted metal partitioning in floodplain deposits within about one order of magnitude, though a large inter-sample variability was found for Pb.     

Metals and arsenic in soils and corresponding vegetation at Central Elbe river floodplains (Germany)

Floodplain soils at the Elbe river are frequently polluted with metals and arsenic. High contents of these pollutants were detected down to subsoil layers. NH4NO3-extractable (phytoavailable) Cd, Ni, and Zn were elevated in horizons with high acidity. Among five common floodplain plant species, Artemisia vulgaris showed highest concentrations of Cd, Cu, and Hg, Alopecurus pratensis of As and Phalaris arundinacea of Ni, Pb, and Zn. Relationships were weak between metal concentrations in plants and phytoavailable stocks in soil. As and Hg uptake seems to be enhanced on long submerged soils. Enrichments of Cd and Hg are linked to a special plant community composition. Grassland herbage sampled in July/August revealed higher concentrations of As (+122%), Hg (+124%), and Pb (+3723%) than in May. To limit harmful transfers into the food chain, low-lying terraces and flood channels revealing highest contaminations or phytoavailabilities should be excluded from mowing and grazing.     

Difference of lead,copper and zinc concentrations between interiors and exteriors of peds in some contaminated soils

Solute transport of elements in soils depends on the soil structural and hydraulic properties, and it is controlled by sorption and diffusion, which both limit the mobility and distribution of elements in soils. This study was conducted to compare lead (Pb), copper (Cu) and zinc (Zn) concentrations between ped exteriors and interiors of some contaminated soils. The results show that the differences of the heavy metals between exteriors and interiors decreased in the order clayey soil, clayey loam soil, loam soil. For same soils, the differences decreased from Pb to Cu to Zn. The differences in readily extractable concentrations of the three metals between ped exteriors and interiors were much larger than the differences in their total metals, this may indicate that extractable metals were more recently deposited. The higher Pb and Cu concentrations in the ped exteriors than interiors may additionally be explained by anthropogenic input, movement and downward through preferential flow.     

Linking biosensor responses to Cd, Cu and Zn partitioning in soils

Soils bind heavy metals according to fundamental physico-chemical parameters. Bioassays, using bacterial biosensors, were performed in pore waters extracted from 19 contrasting soils individually amended with Cd, Cu and Zn concentrations related to the EU Sewage Sludge Directive. The biosensors were responsive to pore waters extracted from Zn amended soils but less so to those of Cu and showed no toxicity to pore water Cd at these environmentally relevant amended concentrations. Across the range of soils, the solid-solution heavy metal partitioning coefficient (K(d)) decreased (p<0.01) with increasing amendments of Cu and Zn; Cu exhibited the highest K(d) values. Gompertz functions of Cu and Zn, K(d) values against luminescence explained the relationship between heavy metals and biosensors. Consequently, biosensors provide a link between biologically defined hazard assessments of metals and standard soil-metal physico-chemical parameters for determining critical metal loadings in soils.     

Behaviour of alpha-, beta-, gamma-, and delta-hexachlorocyclohexane in the soil-plant system of a contaminated site

The behaviour of the organochlorine pesticide hexachlorocyclohexane (HCH) is investigated. The concentrations of alpha-, beta-, gamma-, and delta-HCH isomers were measured in soils, rhizosphere and vegetation in a contaminated area in Galicia (NW Spain). The total concentration of HCH in soils reached values close to 20,000 mgkg(-1). The plants analysed (Avena sativa L., Chenopodium spp., Solanum nigrum L., Cytisus striatus (Hill) Roth, and Vicia sativa L.) accumulated HCH, especially the beta-HCH isomer, in their tissues. The most likely mechanisms of HCH accumulation in plants were sorption of soil HCH on roots and sorption of volatilized HCH on aerial plant tissues. The concentrations of HCH obtained from the bulk and rhizosphere soils of selected plant species suggest that roots tend to reduce levels of the HCH isomers in the rhizosphere. The results reflect the importance of vegetation in the distribution of organochlorine compounds in the soil-plant system.     

Heavy metal concentrations in soil and earthworms in a floodplain grassland

We determined accumulated heavy metal concentrations (Cd, Pb, Cu, Zn) of earthworms in moderately contaminated floodplain soils. Both soil and mature earthworms were sampled before and after flooding and earthworm species were identified to understand species specific differences in bioconcentration. Accumulated metal concentrations in floodplain earthworms differed before and after flooding. Differences in uptake and elimination mechanisms, in food choice and living habitat of the different earthworm species and changes in speciation of the heavy metals are possible causes for this observation. Regression equations taken from literature, that relate metal accumulation by earthworms in floodplains as a function of metal concentration in soil, performed well when all species specific data were combined in an average accumulation, but did not address differences in accumulation between earthworm species.     

Influence of organic acids on the transport of heavy metals in soil

Vegetation historically has been an important part of reclamation of sites contaminated with metals, whether the objective was to stabilize the metals or remove them through phytoremediation. Understanding the impact of organic acids typically found in the rhizosphere would contribute to our knowledge of the impact of plants in contaminated environments. Heavy metal transport in soils in the presence of simple organic acids was assessed in two laboratory studies. In the first study, thin layer chromatography (TLC) was used to investigate Zn, Cd, and Pb movement in a sandy loam soil as affected by soluble organic acids in the rhizosphere. Many of these organic acids enhanced heavy metal movement. For organic acid concentrations of 10mM, citric acid had the highest R(f) values (frontal distance moved by metal divided by frontal distance moved by the solution) for Zn, followed by malic, tartaric, fumaric, and glutaric acids. Citric acid also has the highest R(f) value for Cd movement followed by fumaric acid. Citric acid and tartaric acid enhanced Pb transport to the greatest degree. For most organic acids studied, R(f) values followed the trend Zn>Cd>Pb. Citric acid (10mM) increased R(f) values of Zn and Cd by approximately three times relative to water. In the second study, small soil columns were used to test the impact of simple organic acids on Zn, Cd, and Pb leaching in soils. Citric acid greatly enhanced Zn and Cd movement in soils but had little influence on Pb movement. The Zn and Cd in the effluents from columns treated with 10mM citric acid attained influent metal concentrations by the end of the experiment, but effluent metal concentrations were much less than influent concentrations for citrate <10mM. Exchangeable Zn in the soil columns was about 40% of total Zn, and approximately 80% total Cd was in exchangeable form. Nearly all of the Pb retained by the soil columns was exchangeable.     

Risk assessment of heavy metal pollution for detritivores in floodplain soils in the Biesbosch, The Netherlands, taking bioavailability into account

Floodplains of the European rivers Rhine and Meuse are heavily polluted. We investigated the risk of heavy metal pollution (Cd, Cu, Pb, Zn) for detritivores living in a floodplain area, the Biesbosch, the Netherlands, affected by these rivers. Total soil, pore water and 0.01 M CaCl(2) extractable concentrations and concentrations in plant leaves, earthworms, isopods and millipedes were measured in two sites and compared with literature data to assess possible risks. Based on total metal concentrations in soil, serious effects on detritivores were expected. However, 0.01 M CaCl(2) extractable, pore water and plant leaf concentrations were similar to metal concentrations found in unpolluted areas. Concentrations of Cu and Cd in earthworms and Cu in millipedes were higher in the Biesbosch than in animals from reference areas. All other measured concentrations of heavy metals in earthworms, isopods and millipedes were similar to the ones found in reference areas. Despite high total soil concentrations, effects of Zn, Cu, Pb and Cd pollution on isopods are therefore not expected, while millipedes may only be affected by Cu. Since Cu and Cd levels in earthworms were increased compared to animals in unpolluted soils, this faunal group seems to be most at risk. Given the engineering role of earthworms in ecosystems, effects on the ecological functioning of floodplain soils therefore cannot be excluded.     

Determination and evaluation of cadmium, lead and nickel in greenhouse soils of Almería (Spain)

This study determines total levels of three (Cd, Pb and Ni) potentially toxic trace elements in western Almería (Spain) greenhouse surface soil horizons using microwave digestion; it establishes the geochemical baseline concentration, and it investigates possible relationships between soil properties and elemental concentrations. The results show that the soil concentration of these heavy metals is lower than mentioned in the European and Spanish normative, but they are higher than those reported by other authors working on agricultural soils. The obtained geochemical baseline concentrations (mg kg(-1)) were: Cd 0.4-0.8, Pb 2.5-89.9 and Ni 16.1-30.7. Using the upper baseline criterion, 88% of greenhouse soils have relatively higher content of heavy metals because of their Cd, Pb and Ni concentration. Moreover, soil properties are related to heavy metals contents suggesting that among Cd, Pb and Ni have a similar origin and those total metal concentrations are controlled primarily by soil compositions.     

Lead and cadmium in indoor air and the urban environment

The present study was conducted to find potential terrestrial biomonitors for heavy metals in indoor air in an urban environment. TSP, PM(10), and PM(2.5) were collected in three retirement facilities in the urban area of Vienna. In addition, particulate matter and soil, vegetation, and isopods (Porcellio scaber L.) were collected in the adjacent garden areas. Aerosols were sampled with a low-volume air sampler. The sampled materials were wet ashed and total lead and cadmium contents were determined. Water-soluble heavy metal concentrations were measured in aqueous extracts from air exposed filters, soil, and vegetation. Lead and cadmium were analyzed by graphite furnace AAS. Lead contents in the vegetation were inferred from water-soluble lead in soils. Lead in isopods generally reflected the contents in vegetation. Cadmium in plants probably derived from soil solutions as well as from atmospheric input. Isopods reflected the total cadmium contents in soils. Particulate matter was dominated by PM(2.5), both with respect to mass concentrations and to heavy metal contents. The indoor aerosol was found to be influenced by human activity, indoor sources, and outdoor particles. Relationships between indoor airborne heavy metals and the contents in vegetation (lead and cadmium: positive) and isopods (lead: negative) were identified to have the potential for biomonitoring indoor air quality.     

Effect of submergence-emergence sequence and organic matter or aluminosilicate amendment on metal uptake by woody wetland plant species from contaminated sediments

Site-specific hydrological conditions affect the availability of trace metals for vegetation. In a greenhouse experiment, the effect of submersion on the metal uptake by the wetland plant species Salix cinerea and Populus nigra grown on a contaminated dredged sediment-derived soil and on an uncontaminated soil was evaluated. An upland hydrological regime for the polluted sediment caused elevated Cd concentrations in leaves and cuttings for both species. Emergence and soil oxidation after initial submersion of a polluted sediment resulted in comparable foliar Cd and Zn concentrations for S. cinerea as for the constant upland treatment. The foliar Cd and Zn concentrations were clearly higher than for submerged soils after initial upland conditions. These results point at the importance of submergence-emergence sequence for plant metal availability. The addition of foliar-based organic matter or aluminosilicates to the polluted sediment-derived soil in upland conditions did not decrease Cd and Zn uptake by S. cinerea.     

The solid-solution partitioning of heavy metals (Cu,Zn, Cd,Pb) in upland soils of England and Wales

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.     

Chemical and plant tests to assess the viability of amendments to reduce metal availability in mine soils and tailings

The goal of this research was to assess the potential of several industrial wastes to immobilise metals in two polluted soils deriving from an old Pb/Zn mine. Two different approaches were used to assess the performance of different amendments: a chemical one, using extraction by ethylenediaminetetraacetic acid (EDTA), and a biological one, using Lupinus albus as a bio-indicator. Four amendments were used: inorganic sugar production waste (named ‘sugar foam’, SF), sludge from a drinking water treatment sludge (DWS), organic waste from olive mill waste (OMW) and paper mill sludge (PMS). Amendment to soil ratios ranged from 0.1 to 0.3 (w/w). All the amendments were capable of significantly decreasing (p?<?0.05) EDTA-extractable Pb, Zn and Cu concentrations in the two soils used, with decreases in ranges 21–100, 25–100 and 2–100 % for Pb, Zn and Cu, respectively. The amendments tested were also effective in reducing the bioavailability of Pb and Zn for L. albus, which gave rise to a decrease in shoot metal accumulation by the lupine plants compared to that found in the control soil. That decrease reached up to 5.6 and 2.8 times for Pb and Zn, respectively, being statistically significant in most cases. Moreover, application of the OMW, DWS and SF amendments led to higher average values of plant biomass (up to 71 %) than those obtained in the control soil. The results obtained showed the technology put forward to be a viable means of remediating mine soils as it led to a decrease in the availability and toxicity of metals and, thus, facilitated the growth of a vegetation layer.     

Evaluation of plant availability of soil trace metals by chemical fractionation and multiple regression analysis

Soil samples with a range of chemical and physical properties were collected from 10 different rural regions of China. Trace metals (Ni, Co, Cu, and Pb) in the soils were partitioned by a sequential extraction procedure into Mg(NO(3))(2) extractable (F1), CH(3)COONa extractable (F2), NH(2)OH.HCl extractable (F3), HNO(3)?H(2)O(2) extractable (F4), and residual (F5) fractions. Chemical fractionation showed that F1 fraction of the metals was less than 1% and residue was the dominant form for Cu and Ni in all samples, and for Co in most of the samples. Significant interrelationships of the fractions varied considerably with the different metals. Winter wheat (Triticum aestivum L.) and alfalfa (Medicago sativa L.) had been grown on the soils in a pot-culture experiment under greenhouse conditions for 40 days. Metal availability to the plants was evaluated by simple and multiple regression analysis. The Mg(NO(3))(2) extractable Co (F1) was significantly correlated with Co concentrations in different parts of wheat and in the whole of alfalfa. For the other metals, the independent variables of the multiple regression models, chosen by stepwise selection, were given as: F1 and F2 + F3 + F4 for Ni; F1, F2 + F3 and F4 for Cu; and F3 + F4 for Pb. The results of this study demonstrate that the sequential extraction procedure, in conjunction with multiple regression models using a combination of correlated fractions as an independent variable, may be useful for the prediction of plant absorption of trace metals in soils.     

Sorption of phenanthrene by soils contaminated with heavy metals

The fate of polycyclic aromatic hydrocarbons (PAHs) in soils with co-contaminants of heavy metals has yet to be elucidated. This study examined sorption of phenanthrene as a representative of PAHs by three soils contaminated with Pb, Zn or Cu. Phenanthrene sorption was clearly higher after the addition of heavy metals. The distribution coefficient (K(d)) and the organic carbon-normalized distribution coefficient (K(oc)) for phenanthrene sorption by soils spiked with Pb, Zn or Cu (0-1000 mg kg(-1)) were approximately 24% larger than those by unspiked ones, and the higher contents of heavy metals added into soils resulted in the larger K(d) and K(oc) values. The enhanced sorption of phenanthrene in the case of heavy metal-contaminated soils could be ascribed to the decreased dissolved organic matter (DOM) in solution and increased soil organic matter (SOM) as a consequence of DOM sorption onto soil solids. Concentrations of DOM in equilibrium solution for phenanthrene sorption were lower in the case of the heavy metal-spiked than unspiked soils. However, the decreased DOM in solution contributed little to the enhanced sorption of phenanthrene in the presence of metals. On the other hand, the sorbed DOM on soil solids after the addition of heavy metals in soils was found to be much more reactive and have far stronger capacity of phenanthrene uptake than the inherent SOM. The distribution coefficients of phenanthrene between water and the sorbed DOM on soil solids (K(ph/soc)) were about 2-3 magnitude larger than K(d) between water and inherent SOM, which may be the dominant mechanism of the enhanced sorption of phenanthrene by soils with the addition of heavy metals.     

Bioaccumulation of heavy metals in the earthworms Lumbricus rubellus and Aporrectodea caliginosa in relation to total and available metal concentrations in field soils

The aim of this study was to determine important metal pools for bioaccumulation by the earthworms Lumbricus rubellus and Aporrectodea caliginosa in soils with high binding capacity. Cd, Cu and Zn concentrations in soil, pore water and CaCl(2) extracts of soil, in leaves of the plant species Urtica dioica and in earthworms were determined at 15 field sites constituting a gradient in metal pollution. Variations in the Cu and Cd concentrations in L. rubellus and Cu concentrations in A. caliginosa were best explained by total soil concentrations, while variation in Cd concentration in A. caliginosa was best explained by pore water concentrations. Zn concentrations in L. rubellus and A. caliginosa were not significantly correlated to any determined variable. It is concluded that despite low availability, earthworms in floodplain soils contain elevated concentrations of Cu and Cd, suggesting that uptake takes place not only from the soluble metal concentrations.     

Spatial distribution and internal metal concentrations of terrestrial arthropods in a moderately contaminated lowland floodplain along the Rhine River

Soil metal concentrations, inundation characteristics and abundances of 14 arthropod taxa were investigated in a moderately contaminated lowland floodplain along the Rhine River and compared to the hinterland. Internal metal concentrations were determined for the orders of Coleoptera (beetles) and Araneida (spiders) and were related to soil concentrations. The floodplain was characterized by larger arthropod abundance than the hinterland, in spite of recurrent inundations and higher soil metal concentrations. Most arthropod taxa showed increasing abundance with decreasing distance to the river channel and increasing average inundation duration. For Cd, Cu, Pb and Zn, significant relations were found between arthropod concentrations and concentrations in soil. Significant relations were few but positive, indicating that increasing soil concentrations result in increasing body burdens in arthropods. For arthropod-eating vertebrates, these results might imply that larger prey availability in the floodplain coincides with higher metal concentrations in prey, possibly leading to increased exposure to metal contamination.     

Arsenic and mercury concentrations in major landscape components of an intensively cultivated watershed

To provide an understanding of arsenic (As) and mercury (Hg) concentrations in soil, sediment, water, and fish tissues, samples were collected from a Mississippi River alluvial floodplain located in northwest Mississippi. As concentrations increased approximately an order of magnitude from water (5.12 micrograms/l) to fish tissues (36.99 micrograms/kg) and an additional two orders of magnitude in soils, lake sediments, and wetland sediments (5728, 5614, and 6746 micrograms/kg), respectively. Average Hg concentrations in water, soils, lake sediments, and fish were 2.16 micrograms/l, 55.1, 14.5 and 125 micrograms/kg, respectively. As and Hg concentrations were within published ranges for uncontaminated soil, water, and sediments. As concentrations represented a low risk. Hg concentrations were also low but showed a greater tendency to concentrate in fish tissue. The dominant mode of entry of these materials into aquatic systems is through storm-generated runoff. Since both metals accompany sediments, agricultural conservation practices such as reduced tillage, buffer riparian strips, and bordering sediment ponds or drainage wetlands will minimize watershed input to aquatic systems.