The potential of willow for remediation of heavy metal polluted calcareous urban soils

Growth performance and heavy metal uptake by willow (Salix viminalis) from strongly and moderately polluted calcareous soils were investigated in field and growth chamber trials to assess the suitability of willow for phytoremediation. Field uptakes were 2-10 times higher than growth chamber uptakes. Despite high concentrations of cadmium (≥80 mg/kg) and zinc (≥3000 mg/kg) in leaves of willow grown on strongly polluted soil with up to 18 mg Cd/kg, 1400 mg Cu/kg, 500 mg Pb/kg and 3300 mg Zn/kg, it is unsuited on strongly polluted soils because of poor growth. However, willow proved promising on moderately polluted soils (2.5 mg Cd/kg and 400 mg Zn/kg), where it extracted 0.13% of total Cd and 0.29% of the total Zn per year probably representing the most mobile fraction. Cu and Pb are strongly fixed in calcareous soils.     

Copper bioavailability in the rhizosphere of maize (Zea mays L.) grown in two Italian soils

In this study, potentially bioavailable copper was estimated in two soils (a fungicide polluted and a natural soil) using a passive sampling technique, DGT. As plants can alter copper mobility and bioavailability in the soil, the rhizosphere properties of Zea mays L. were investigated using rhizoboxes.

Compared to the total concentration, the soluble and the potentially bioavailable copper concentration in the bulk soils were generally low (less than 0.20% and 0.06% respectively), with a sixfold increase in the rhizosphere of the polluted soil. Our results suggest that maize cultivation in a polluted vineyard soil could increase the potentially available fraction of copper. DGTs showed a good sensitivity to soil properties and to root-induced changes in the rhizosphere, but the potentially bioavailable copper could not be related to the copper concentration in the above ground parts of maize. The results suggest that DGT may be used to predict some effects of the cultivation of polluted soils, for example, metal mobility and increased availability, but they cannot mimic the uptake of a tolerant plant.

For both soils, dissolved organic carbon (DOC) concentrations were threefold higher in the rhizosphere than in the bulk soil, whilst bioaccumulation in leaves and roots was not significant. DOC production, usually effective in ion mobilization and assimilation, may help also in the reduction of Cu uptake at toxic concentrations. The sequestration of available Cu in soil and soil solution by DOC seems to contribute to maize tolerance.     

Influences of thermal decontamination on mercury removal, soil properties, and repartitioning of coexisting heavy metals

Thermal treatment is a useful tool to remove Hg from contaminated soils. However, thermal treatment may greatly alter the soil properties and cause the coexisting contaminants, especially trace metals, to transform and repartition. The metal repartitioning may increase the difficulty in the subsequent process of a treatment train approach. In this study, three Hg-contaminated soils were thermally treated to evaluate the effects of treating temperature and duration on Hg removal. Thermogravimetric analysis was performed to project the suitable heating parameters for subsequent bench-scale fixed-bed operation. Results showed that thermal decontamination at temperature >400 °C successfully lowered the Hg content to <20 mg kg⁻¹. The organic carbon content decreased by 0.06-0.11% and the change in soil particle size was less significant, even when the soils were thermally treated to 550 °C. Soil clay minerals such as kaolinite were shown to be decomposed. Aggregates were observed on the surface of soil particles after the treatment. The heavy metals tended to transform into acid-extractable, organic-matter bound, and residual forms from the Fe/Mn oxide bound form. These results suggest that thermal treatment may markedly influence the effectiveness of subsequent decontamination methods, such as acid washing or solvent extraction.     

Changes in pH,dissolved organic matter and Cd species in the rhizosphere soils of Cd phytostabilizer Athyrium wardii (Hook.) Makino involved in Cd tolerance and accumulation

Phytostabilization has great practical significance and flexibility in the ecological restoration of mining tailings and remediation of heavy metals polluted soils. However, potential use of metallophytes in phytostabilization is limited by a lack of knowledge of many basic plant processes. A mining ecotype (ME) Athyrium wardii, Pb/Cd phytostabilizer, and a non-mining ecotype (NME) A. wardii were grown in a pot experiment to investigate the chemical characteristics of the rhizosphere when exposed to the Cd polluted soils. Rhizobags were used to collect rhizosphere and bulk soils, separately. The results indicated that the ME A. wardii was more efficient in Cd accumulation in the root than NME after growing in Cd polluted soils for 50 days in a green house. Soil solution pH and dissolved organic carbon (DOC) concentration in the rhizosphere of ME A. wardii were higher than in the bulk soil and initial values (before planting), whereas the increment in the ME A. wardii were greater than NME. Owing to the increasing of rhizosphere soil pH, exchangeable Cd significantly decreased, whereas the other Cd species were increased with increasing soil DOC values. It is assumed that the ME A. wardii was effective in stabilizing Cd from the mobile fraction to non-mobile fractions. Results from this study suggest that rhizosphere alkalinization and the exudation of high amounts of dissolved organic matter (DOM) to reduce heavy metal mobility might be the two important mechanisms involved in the metal tolerance/accumulation of ME A. wardii.     

Characterization of mercury species in brown and white rice (Oryza sativa L.) grown in water-saving paddies

In China, total Hg (Hg_T) and methylmercury (MeHg) were quantified in rice grain grown in three sites using water-saving rice cultivation methods, and in one Hg-contaminated site, where rice was grown under flooded conditions. Polished white rice concentrations of Hg_T (water-saving: 3.3 ± 1.6 ng/g; flooded: 110 ± 9.2 ng/g) and MeHg (water-saving 1.3 ± 0.56 ng/g; flooded: 12 ± 2.4 ng/g) were positively correlated with root-soil Hg_T and MeHg contents (Hg_T: r² = 0.97, MeHg: r² = 0.87, p < 0.05 for both), which suggested a portion of Hg species in rice grain was derived from the soil, and translocation of Hg species from soil to rice grain was independent of irrigation practices and Hg levels, although other factors may be important. Concentrations of Hg_T and other trace elements were significantly higher in unmilled brown rice (p < 0.05), while MeHg content was similar (p > 0.20), indicating MeHg infiltrated the endosperm (i.e., white rice) more efficiently than inorganic Hg(II).     

Effects of municipal solid waste compost and mineral fertilizer amendments on soil properties and heavy metals distribution in maize plants (Zea mays L.)

Soil amendments based on crop nutrient requirements are considered a beneficial management practice. A greenhouse experiment with maize seeds (Zea mays L.) was conducted to assess the inputs of metals to agricultural land from soil amendments. Maize seeds were exposed to a municipal solid waste (MSW) compost (50 Mg ha⁻¹) and NPK fertilizer (33 g plant⁻¹) amendments considering N plant requirement until the harvesting stage with the following objectives: (1) determine the accumulation of total and available metals in soil and (2) know the uptake and ability of translocation of metals from roots to different plant parts, and their effect on biomass production. The results showed that MSW compost increased Cu, Pb and Zn in soil, while NPK fertilizer increased Cd and Ni, but decreased Hg concentration in soil. The root system acted as a barrier for Cr, Ni, Pb and Hg, so metal uptake and translocation were lower in aerial plant parts. Biomass production was significantly enhanced in both MSW and NPK fertilizer-amended soils (17%), but also provoked slight increases of metals and their bioavailability in soil. The highest metal concentrations were observed in roots, but there were no significant differences between plants growing in amended soil and the control soil. Important differences were found for aerial plant parts as regards metal accumulation, whereas metal levels in grains were negligible in all the treatments.     

Green manure plants for remediation of soils polluted by metals and metalloids: Ecotoxicity and human bioavailability assessment

Borage, white mustard and phacelia, green manure plants currently used in agriculture to improve soil properties were cultivated for 10 wk on various polluted soils with metal(loid) concentrations representative of urban brownfields or polluted kitchen gardens. Metal(loid) bioavailability and ecotoxicity were measured in relation to soil characteristics before and after treatment. All the plants efficiently grow on the various polluted soils. But borage and mustard only are able to modify the soil characteristics and metal(loid) impact: soil respiration increased while ecotoxicity, bioaccessible lead and total metal(loid) quantities in soils can be decreased respectively by phytostabilization and phytoextraction mechanisms. These two plants could therefore be used for urban polluted soil refunctionalization. However, plant efficiency to improve soil quality strongly depends on soil characteristics.     

Assessment of bacterial communities and characterization of lead-resistant bacteria in the rhizosphere soils of metal-tolerant Chenopodium ambrosioides grown on lead-zinc mine tailings

Bacterial communities in the rhizosphere soils of metal tolerant and accumulating Chenopodium ambrosioides grown in highly and moderately lead-zinc mine tailings contaminated-soils as well as the adjacent soils with low metal contamination were characterized by using cultivation-independent and cultivation techniques. A total of 69, 73, and 83 bacterial operational taxonomic units (OTUs) having 84.8-100% similarity with the closest match in the database were detected among high, moderate, and low-contamination soil clone libraries, respectively. These OTUs had a Shannon diversity index value in the range of 4.06-4.30. There were 9, 10, and 14 bacterial genera specific to high, moderate, and low metal-contaminated soil clone libraries, respectively. Phylogenetic analysis showed that the Pb-resistant isolates belonged to 8 genera. Pseudomonas and Arthrobacter were predominant among the isolates. Most of the isolates (82-86%) produced indole acetic acid and siderophores. More strains from the highly metal-contaminated soil produced 1-aminocyclopropane-1-carboxylate deaminase than the strains from the moderately and lowly metal-contaminated soils. In experiments involving canola grown in quartz sand containing 200 mg kg⁻¹ of Pb, inoculation with the isolated Paenibacillusjamilae HTb8 and Pseudomonas sp. GTa5 was found to significantly increase the above-ground tissues dry weight (ranging from 19% to 36%) and Pb uptake (ranging from 30% to 40%) compared to the uninoculated control. These results show that C. ambrosioides harbor different metal-resistant bacterial communities in their rhizosphere soils and the isolates expressing plant growth promoting traits may be exploited for improving the phytoextraction efficiency of Pb-polluted environment.     

Critical Limits for Hg(II) in soils, derived from chronic toxicity data

Published chronic toxicity data for Hg(II) added to soils were assembled and evaluated to produce a data set comprising 52 chronic end-points, five each for plants and invertebrates and 42 for microbes. With end-points expressed in terms of added soil Hg(II) contents, Critical Limits were derived from the 5th percentiles of species sensitivity distributions, values of 0.13 μg (g soil)⁻¹ and 3.3 μg (g soil organic matter)⁻¹ being obtained. The latter value exceeds the currently recommended Critical Limit, used to determine Hg(II) Critical Loads in Europe, of 0.5 μg (g soil organic matter)⁻¹. We also applied the WHAM/Model VI chemical speciation model to estimate concentrations of Hg²⁺ in soil solution, and derived an approximate Critical Limit Function (CLF) that includes pH; log [Hg²⁺]_crit = −2.15 pH −17.10. Because they take soil properties into account, the soil organic matter-based limit and the CLF provide the best assessment of toxic threat for different soils. For differing representative soils, each predicts a range of up to 100-fold in the dry weight-based content of mercury that corresponds to the Critical Limit.     

Mercury, cadmium and lead concentrations in different ecophysiological groups of earthworms in forest soils

Bioaccumulation of Hg, Cd and Pb by eight ecophysiologically distinct earthworm species was studied in 27 polluted and uncontaminated forest soils. Lowest tissue concentrations of Hg and Cd occurred in epigeic Lumbricus rubellus and highest in endogeic Octolasion cyaneum. Soils dominated by Dendrodrilus rubidus possess a high potential of risk of Pb biomagnification for secondary predators. Bioconcentration factors (soil-earthworm) followed the sequence ranked Cd > Hg > Pb. Ordination plots of redundancy analysis were used to compare HM concentrations in earthworm tissues with soil, leaf litter and root concentrations and with soil pH and CEC. Different ecological categories of earthworms are exposed to Hg, Cd and Pb in the topsoil by atmospheric deposition and accumulate them in their bodies. Species differences in HM concentrations largely reflect differences in food selectivity and niche separation.     

Responses to ozone pollution of alfalfa exposed to increasing salinity levels

Stomatal closure and biosynthesis of antioxidant molecules are two fundamental components of the physiological machinery that lead to stress adaptation during plant's exposure to salinity. Since high stomatal resistance may also contribute in counteracting O₃ damages, we hypothesized that soil salinization may increase O₃ tolerance of crops. An experiment was performed with alfalfa grown in filtered (AOT40 = 0 in both years) and non-filtered (AOT40 = 9.7 in 2005 and 6.9 ppm h in 2006) open-top chambers. Alfalfa yield was reduced by O₃ (−33%) only in plants irrigated with salt-free water, while the increasing levels of soil salinity until 1.06 dS m⁻¹ reduced both stomatal conductance and plant O₃ uptake, thus linearly reducing O₃ effects on yield. Therefore a reliable flux-based model for assessing the effects of O₃ on crop yield should take into account soil salinity.     

Reducing plant uptake of PAHs by cationic surfactant-enhanced soil retention

Reducing the transfer of contaminants from soils to plants is a promising approach to produce safe agricultural products grown on contaminated soils. In this study, 0-400 mg/kg cetyltrimethylammonium bromide (CTMAB) and dodecylpyridinium bromide (DDPB) were separately utilized to enhance the sorption of PAHs onto soils, thereby reducing the transfer of PAHs from soil to soil solution and subsequently to plants. Concentrations of phenanthrene and pyrene in vegetables grown in contaminated soils treated with the cationic surfactants were lower than those grown in the surfactant-free control. The maximum reductions of phenanthrene and pyrene were 66% and 51% for chrysanthemum (Chrysanthemum coronarium L.), 62% and 71% for cabbage (Brassica campestris L.), and 34% and 53% for lettuce (Lactuca sativa L.), respectively. Considering the impacts of cationic surfactants on plant growth and soil microbial activity, CTMAB was more appropriate to employ, and the most effective dose was 100-200 mg/kg.     

Hexabromocyclododecanes in limnic and marine organisms and terrestrial plants from Tianjin,China: Diastereomer- and enantiomer-specific profiles,biomagnification, and human exposure

To interpret the distribution of hexabromocyclododecanes (HBCDs) in various organisms, we measured the concentrations and diastereomer and enantiomer profiles of HBCDs in 21 different species of limnic and marine cohorts from Tianjin, China. The concentration ranges of HBCDs in limnic and marine organisms were 64.3–1111 ng g⁻¹ lw and 85.5–989 ng g⁻¹ lw, respectively. Living habitat and feeding habits had important impacts on HBCD diastereomer distribution. Most of the species appeared to preferentially select (+)-α-, (−)-β- and (−)-γ-HBCD. There is a tendency that the total and α-HBCDs were magnified as trophic level increased with trophic magnification factors (TMFs) around 2. The concentrations of HBCDs in the limnic and marine fishes were highest in the liver, followed by the gill, skin, and muscle. In terrestrial plants, the highest concentrations of HBCDs were observed in the leaf, followed by the root and the rhizosphere soil. Plants showed enantioselectivity for HBCD enantiomers, which varied with plant species and organs (leaf vs. root) of the same plant. Higher estimated daily intakes (EDIs) of HBCDs were observed from fish than from wheat.     

Accumulation of phenanthrene and pyrene in rhizosphere soil

A study was conducted to determine PAH concentrations in the rhizosphere of plants grown in soil containing phenanthrene or pyrene. The rhizosphere of tall fescue and wheat grown in sterile soil contained 4-5-fold higher pyrene concentrations than unplanted soil. The rhizosphere of several plant species grown in non-sterile soil temporarily contained appreciably more phenanthrene or pyrene than unplanted soil, but those PAHs were degraded with time. The data suggest that plants accumulate such hydrophobic compounds in the rhizosphere after facilitating their transport toward the roots.     

Growth response and phytoextraction of copper at different levels in soils by Elsholtzia splendens

Phytoremediation is a promising approach for cleaning up soils contaminated with heavy metals. Information is needed to understand growth response and uptake mechanisms of heavy metals by some plant species with exceptional capability in absorbing and superaccumulating metals from soils. Greenhouse study, field trial, and old mined area survey were conducted to evaluate growth response and Cu phytoextraction of Elsholtzia splendens in contaminated soils, which has been recently identified to be tolerant to high Cu concentration and have great potential in remediating contaminated soils. The results from this study indicate that the plant exhibited high tolerance to Cu toxicity in the soils, and normal growth was attained up to 80 mg kg(-1) available soil Cu (the NH4OAc extractable Cu) or 1000 mg kg(-1) total Cu. Under the field conditions, a biomass yield of 9 ton ha(-1) was recorded at the soil available Cu level of 77 mg kg(-1), as estimated by the NH4OAc extraction method. Concentration-dependent uptake of Cu by the plant occurred mainly at the early growth stage, and at the late stage, there is no difference in shoot Cu concentrations grown at different extractable soil Cu levels. The extractability of Cu from the highly polluted soil is much greater by the roots than that by the shoots. The NH4OAc extractable Cu level in the polluted soil was reduced from 78 to 55 mg kg(-1) in the soil after phytoextraction and removal of Cu by the plant species for one growth season. The depletion of extractable Cu level in the rhizosphere was noted grown in the mined area, even at high Cu levels, the NH4OAc extractable Cu in the rhizosphere was 30% lower than that in the bulk soil. These results indicate that phytoextraction of E. splendens can effectively reduce the plant-available Cu level in the polluted soils.     

Gaseous mercury emissions from unsterilized and sterilized soils: The effect of temperature and UV radiation

Mercury (Hg) emissions from the soils taken from two different sites (deciduous and coniferous forests) in the Adirondacks were measured in outdoor and laboratory experiments. Some of the soil samples were irradiated to eliminate biological activity. The result from the outdoor measurements with different soils suggests the Hg emission from the soils is partly limited by fallen leaves covering the soils which helps maintain relatively high soil moisture and limits the amount of heat and solar radiation reaching the soil surface. In laboratory experiments exposure to UV-A (365 nm) had no significant effect on the Hg emissions while the Hg emissions increased dramatically during exposure to UV-B (302 nm) light suggesting UV-B directly reduced soil-associated Hg. Overall these results indicate that for these soils biotic processes have a relatively constant and smaller influence on the Hg emission from the soil than the more variable abiotic processes.     

The sea–air exchange of mercury (Hg) in the marine boundary layer of the Augusta basin (southern Italy): Concentrations and evasion flux

The first attempt to systematically investigate the atmospheric mercury (Hg) in the MBL of the Augusta basin (SE Sicily, Italy) has been undertaken. In the past the basin was the receptor for Hg from an intense industrial activity which contaminated the bottom sediments of the Bay, making this area a potential source of pollution for the surrounding Mediterranean. Three oceanographic cruises have been thus performed in the basin during the winter and summer 2011/2012, where we estimated averaged Hg_atm concentrations of about 1.5 ± 0.4 (range 0.9–3.1) and 2.1 ± 0.98 (range 1.1–3.1) ng m⁻³ for the two seasons, respectively. These data are somewhat higher than the background Hg_atm value measured over the land (range 1.1 ± 0.3 ng m⁻³) at downtown Augusta, while are similar to those detected in other polluted regions elsewhere. Hg evasion fluxes estimated at the sea/air interface over the Bay range from 3.6 ± 0.3 (unpolluted site) to 72 ± 0.1 (polluted site of the basin) ng m⁻² h⁻¹. By extending these measurements to the entire area of the Augusta basin (∼23.5 km²), we calculated a total sea–air Hg evasion flux of about 9.7 ± 0.1 g d⁻¹ (∼0.004 t yr⁻¹), accounting for ∼0.0002% of the global Hg oceanic evasion (2000 t yr⁻¹). The new proposed data set offers a unique and original study on the potential outflow of Hg from the sea–air interface at the basin, and it represents an important step for a better comprehension of the processes occurring in the marine biogeochemical cycle of this element.     

Effect of octylphenol on physiologic features during growth in Arabidopsis thaliana

Alkylphenol ethoxylates are widely used as detergents, emulsifiers, solubilizers, wetting agents and dispersants. Octylphenol (OP) ethoxylates, one of alkylphenol ethoxylates, represent 15–20% of the market, and their metabolic residues may be discharged to surface waters, sediments and soils as a persistent and ubiquitous pollutant. We tested the response of Arabidopsis thaliana to different concentrations of OP. OP affected the germination percentage and mean germination period. 10 d treatment with OP, especially high concentration (10 and 50 mg L⁻¹), decreased shoot and root biomass and root length of 30 d-old A. thaliana. Content of chlorophyll was decreased but that of proline was increased in leaves with OP treatment. OP caused oxidative stress in leaves; malondialdehyde content was increased, and the activities of ascorbate peroxidase, catalase and superoxide dismutase were induced. OP affects the physiologic and morphologic features of A. thaliana during growth. Because plants might be exposed to OP for a long time in the surroundings, more attention needs to be paid to the effect of OP on plants.     

In situ fixation of metals in soils using bauxite residue: biological effects

Soils polluted with heavy metals can cause phytotoxicity and exhibit impared microbial activities. In this paper we evaluate the responses of different biological endpoints to in situ remediation processes. Three soil amendments (red mud, beringite and lime) were applied to two soils polluted by heavy metals. Oilseed rape, wheat, pea and lettuce were grown successively in pots on the untreated and amended soils and their yield and metal uptake were determined. A suite of microbial tests (lux-marked biosensors, Biolog and soil microbial biomass) were performed to determine the effect of the soil amendments on the functionality and size of the soil microbial community. In both soils all three amendments reduced phytotoxicity of heavy metals, enhanced plant yields and decreased the metal concentrations in plants. The red mud treatment also increased soil microbial biomass significantly. The microbial biosensors responded positively to the remediation treatments in the industrially-contaminated soil used in the experiment. Red mud applied at 2% of soil weight was as effective as beringite applied at 5%. The results also showed that since the biological systems tested respond differently to the alleviation of metal toxicity, a suite of biological assays should be used to assess soil remediation processes.