Co-planting of Salix interior and Trifolium pratense for phytoremediation of trace elements from wood preservative contaminated soil.

Phytoextraction potential of a co-planting system was evaluated using a shrub and an herbaceous species and compared with monocultures. A greenhouse experiment with Salix interior and Trifolium pratense grown in combination or alone was conducted for 120 days in soil either uncontaminated or contaminated with wood preservatives containing mixed chromated copper arsenate and pentachlorophenol (PCP). The results showed that the plant species produced similar amounts of dry biomass per pot in monoculture and co-planting, whether growing in contaminated or uncontaminated soil. Arsenic (As), chromium (Cr) and copper (Cu) concentrations in root tissue of S. interior increased 8.6%, 65.9% and 4.5%, respectively, in co-planting compared to its monoculture. T. pratense had superior concentration of As (14% higher) in root tissue when co-planted. However, the higher trace elements concentrations in the plant tissues did not translate into measurable differences in total trace element removal per pot, except for As. The bioconcentration factor for Cu and As was high in the belowground portions of the plants in co-planting. PCP levels in the soil decreased to values near the limit of detection in all treatments. These results suggest that co-planting S. interior with T. pratense could lead to higher phytoextraction potential than monoculture.

Phytoextraction of soil trace elements by willow during a phytoremediation trial in Southern Québec, Canada.

The phytoextraction of the trace elements (TEs) As, Cd, Cu, Ni, Pb, and Zn by willow cultivars (Fish Creek, SV1 and SX67) was measured during a 3-year field trial in a mildly contaminated soil. Biomass ranged from 2.8 to 4.4 Mg/ha/year at 30,000 plants/ha. Shoots (62%) were the main component followed by leaves (23%) and roots (15%). Biomass was positively linked to soluble soil dissolved organic carbon, K, and Mg, while TEs, not Cd and Zn, had a negative effect. The TE concentration ranking was: Zn > Cu > Cd > Ni, Pb > As, and distribution patterns were: (i) minima in shoots (As, Ni), (ii) maxima in leaves (Cd, Zn), or (iii) maxima in roots (Cu, Pb). Correlations between soil and plant TE were significant for the six TEs in roots. The amounts extracted were at a maximum for Zn, whereas Fish Creek and SV1 extracted more TE than SX67. More than 60% (91-94% for Cd and Zn) of the total TE was in the aboveground parts. Uptake increased with time because of higher biomass. Fertilization, the selection of cultivars, and the use of complementary plants are required to improve productivity and Cd and Zn uptake.

Soil trace element changes during a phytoremediation trial with willows in southern Québec, Canada.

This study determined the changes in trace elements (TE) (As, Cd, Cu, Ni, Pb, Zn) chemistry in the soils of a willow ("Fish Creek" - Salix purpurea, SV1 - Salix x dasyclados and SX67 - Salix miyabeana) plantation growing under a cold climate during a three-year trial. The soil HNO3-extractable and H2O-soluble TE concentrations and pools significantly decreased under most cultivars (Fish, SX67). Yet, TE changes showed inconsistent patterns and localized soil TE increases (Ni, Pb) were measured. Temporal changes in soil TE were also detected in control plots and sometimes exceeded changes in planted plots. Discrepancies existed between the amount of soil TE change and the amount of TE uptake by willows, except for Cd and Zn. Phytoremediation with willows could reduce soil Cd and Zn within a decadal timeframe indicating that they can be remediated by willows in moderately contaminated soils. However, the time needed to reduce soil As, Cu, Ni and Pb was too long to be efficient. We submit that soil leaching contributed to the TE decrease in controls and the TE discrepancies, and that the plantation could have secondary effects such as the accelerated leaching of soil TE.

Early rhizosphere microbiome composition is related to the growth and Zn uptake of willows introduced to a former landfill.

Although plants introduced for site restoration are pre-selected for specific traits (e.g. trace element bioaccumulation, rapid growth in poor soils), the in situ success of these plants likely depends on the recruitment of appropriate rhizosphere microorganisms from their new environment. We introduced three willow (Salix spp.) cultivars to a contaminated landfill, and performed soil chemical analyses, plant measurements, and Ion Torrent sequencing of rhizospheric fungal and bacterial communities at 4 and 16 months post-planting. The abundance of certain dominant fungi was linked to willow accumulation of Zn, the most abundant trace element at the site. Interestingly, total Zn accumulation was better explained by fungal community structure 4 months post-planting than 16 months post-planting, suggesting that initial microbial recruitment may be critical. In addition, when the putative ectomycorrhizal fungi Sphaerosporella brunnea and Inocybe sp. dominated the rhizosphere 4 months post-planting, Zn accumulation efficiency was negatively correlated with fungal diversity. Although field studies such as this rely on correlation, these results suggest that the soil microbiome may have the greatest impact on plant function during the early stages of growth, and that plant-fungus specificity may be essential.

Microbial activity and water-soluble trace element species in the rhizosphere of spring wheat (Triticum aestivum cv. USU-Perigee).

The influence of microbial activity on the concentration and speciation of trace elements (TEs) was assessed in a study on the bioavailability of TEs for edible plants. A growth chamber experiment with spring wheat (Triticum aestivum cv. USU-Perigee) was conducted and the bulk (Bk) and the rhizosphere (Rz) soil components were collected at maturity. A characterization of the microbial activity and population was made by measuring the microbial biomass, enzymes (acid phosphatase, arylsulfatase, dehydrogenase and urease) and 16S rDNA DGGE profiles. In soil water extracts, major solutes (H(+), Ca, Mg, Na, NH(4), K, Cl, NO(3), SO(4), total N, DON and DOC) and trace elements (Al, As, Cd, Ce, Cr, Cu, Fe, Pb, Tl, and Zn) including monomeric Al species, free Cu(2+) and labile Zn were determined. The partition of the variation indicated that 12.1% of the distribution of TEs in the Bk soil was significantly and exclusively explained by chemical properties while this value was less than 0.1% for the Rz soil. To the contrary, microbial properties contributed significantly to 12.3% of the distribution of TEs in the Rz soil whereas it explained less than 0.1% for the Bk soil. Detailed redundancy analyses identified several potential mechanisms (e.g. weathering of primary mineral, solubilisation of sesquioxides, bacterial effect on the redox status) explaining the fate of TEs in the Bk and Rz soils. This study revealed that microbial activity is strongly associated to the speciation of trace elements in the Rz of edible plants and points to some microbial processes influencing TE speciation.

Nutrient-assisted phytoremediation of wood preservative-contaminated technosols with co-planting of Salix interior and Festuca arundinacea.

The remediation of wood preservative-contaminated sites is an important issue due to the carcinogenic nature of some contaminants derived from wood preservatives (e.g., Cr+6, arsenate, and pentachlorophenol). This study evaluated the effects of fertilizer application on remediation potential of co-plantings of Salix interior Rowlee. (Salix) and Festuca arundinacea Schreb. (Festuca) in a wood preservative-spiked technosol while considering the potential contaminant and nutrient leaching. Two levels of nitrogen (N) and phosphorus (P) fertilizers, NaNO3 and NaH2PO4 (25 and 75 mg L-1), were applied to achieve three N:P ratios, i.e., 3:1 (75:25), 1:3 (25:75), and 1:1 (25:25), that were compared with a control treatment (0:0 N:P) in a mesocosm experiment. Roots of the plant supplied with 1:1 and 1:3 N:P had more than double arsenic (As) and copper (Cu) amounts (i.e., biomass × concentration) compared to the control ones. Highest As and Cu amounts in shoots were found for Salix stems and Festuca leaves in the 1:3 and 1:1 N:P treatments, respectively. Arsenic and P leaching was high in mesocosms supplied with 1:3 N:P. Contamination and nutrient leaching in the 1:1 N:P treatment did not differ from the control, except for Cu. In conclusion, 1:1 N:P treatment yielded the best results in terms of metal(loid) uptake and contaminant and nutrient leaching. In 1:1 N:P treatment, the maximum values of percent As, Cr, and Cu in Salix and Festuca aboveground were 0.18%, 0.024%, and 1.20% and 0.89%, 0.08%, and 1.78%, respectively.

The speciation of water-soluble Al and Zn in the rhizosphere of forest soils.

This study focuses on the relationships of dissolved Al and Zn speciation with microbial and chemical soil properties in the bulk and rhizosphere of forest soils. The soil components were sampled under Populus tremuloides Michx. at six sites located close to industrial facilities. Total water-soluble (Al(WS), Zn(WS)) and reactive (Al(R), Zn(R)) Al and Zn concentrations measured in soil water extracts, speciation data modeled by WHAM 6, chemical properties (pH, DOC, major cations and anions) and microbial properties (microbial biomass and enzyme activities) were measured on all soils. Enrichment in Al(R) and Zn(R) was observed in the rhizosphere compared to bulk soils. In a given soil material, the speciation of Al and Zn varied according to solution pH and Al-organic as well as Zn-organic complexes or Zn(2+) were generally the dominant species. The factors controlling the Al(WS), Zn(WS), Al(R) and Zn(R) concentrations differed between soil components, shifting from strictly chemical in the bulk (78%) to interactions among microbial and chemical variables in the rhizosphere (87%). Results further indicate that organic matter and pH were significantly linked to these response variables in the rhizosphere. Involvement of rhizospheric microorganisms occurred via pH changes induced by either the microbial assimilation of nitrogen or through the release of metals during the mineralization of roots. Our results therefore suggest that microbial activity is an important component of the biogeochemistry of Al and Zn in the rhizosphere. The study further provides key information to improve the assessment of ecological risk associated to Al and Zn in forest soils.

Labile zinc concentration and free copper ion activity in the rhizosphere of forest soils.

Water-soluble and acid-extractable Cu and Zn, water-soluble organic carbon (WSOC), pH, differential pulse anodic stripping voltammetry-labile Zn (ZnL), Zn2+ activity (Windemere humic aqueous model [WHAM]; http://chess.ensmp.fr/ chemsites.html), and Cu2+ activity with an ion-selective electrode were compared between the rhizosphere and the bulk components of nine acidic forest sites from southeastern Canada. At all sites, the WSOC contents were higher in the rhizosphere than in the bulk component. Acidity was also higher in the rhizosphere, although pH differences were significant at only five sites. The concentrations of Zn in water extracts and ZnL contents (at six sites) were higher in the rhizosphere, whereas acid-extractable Zn was only marginally increased in the rhizosphere. Calculations with WHAM indicated that free Zn2+ ion activities were higher in the rhizosphere than in the bulk soil but that the fraction of total dissolved Zn in water extracts that is present as free Zn2+ did not differ significantly between the two components. The concentration of Cu in the water extract was higher in the rhizosphere for all sites, but acid-extractable Cu levels did not differ. The fraction of water-soluble Cu present as Cu2+ was higher in the bulk soil, although Cu2+ activities did not significantly vary with proximity to roots. These results showed that the processes acting in the rhizosphere of forest soils strongly affected the concentrations of dissolved Zn and Cu and that this microenvironment should be considered when estimating the bioavailability and the ecological risks of metals in soils.

The sequestration of trace elements by willow (Salix purpurea)--which soil properties favor uptake and accumulation?

The effect of soil properties on trace element (TE) extraction by the Fish Creek willow cultivar was assessed in a 4-month greenhouse experiment with two contrasted soils and two mycorrhizal treatments (Rhizophagus irregularis and natives). Aboveground tissues represented more than 82 % of the willow biomass and were the major sink for TE. Cadmium and Zn were concentrated in leaves, while As, Cu, Ni, and Pb were mostly found in roots. Willow bioconcentration ratios were below 0.20 for As, Cu, Ni, and Pb and reached 10.0 for Cd and 1.97 for Zn. More significant differences in willow biomass, TE concentrations, and contents were recorded between soil types than between mycorrhizal treatments. A slight significant increase in Cu extraction by willow in symbiosis with Rhizophagus irregularis was observed and was linked to increased shoot biomass. Significant regression models between TE in willow and soil properties were found in leaves (As, Ni), shoots (As, Cd, Cu, Ni), and roots (As, Cu, Pb). Most of the explanation was shared between soil water-soluble TE and fertility variables, indicating that TE phytoextraction is related to soil properties. Managing interactions between TE and major nutrients in soil appeared as a key to improve TE phytoextraction by willows.

Trace elements in the pollen of Ambrosia artemisiifolia: what is the effect of soil concentrations?

Concentrations of nine trace elements (Ba, Cd, Cr, Cu, Mn, Ni, Pb, Tl and Zn) were measured in a plant bearing allergenic pollens (ragweed) and their transfers from soils to the roots and then to the pollens were investigated. The soil, roots and pollens collected from flowers were sampled at 26 urban sites. Soil pH, soil organic carbon and total-recoverable trace elements (TE) in soil, roots and pollens were measured. The three biogeochemical compartments are well discriminated according to their TE concentrations. The concentrations (in µg g(-1)) in pollens decreased as follow: Zn (59.5-205)>Mn (19.4-117)>Ba≈Cr≈Cu≈Ni≈Pb (0.54-27.7)>Cd (0.06-0.77)>>Tl (0.0015-0.0180). Mean elemental allocation within ragweed always favored roots over pollen but, at site level, inverse pattern is also observed mostly for Zn and slightly for Cu and Ni. Significant predictive models of TE concentrations in pollens were obtained using soil or root properties only for Cd, Ni and Pb. They all involved positive relationships between TE concentrations in pollens and in soil or roots. Estimates of short-term exposure of human to TE carried out by ragweed pollens indicate TE absorption of less than 50 ng, far below thresholds of air quality criteria. Investigating the TE chemistry of pollens is a required first step to validate the impact of TE in pollens on human health and on the prevalence and intensity of allergy symptoms and atopic diseases.

Speciation of zinc in contaminated soils.

The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn(2+), soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K(d)) for Zn ranged from 17 to 13,100 L kg(-1) soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn(2+) varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn(2+), dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils.

Comparing WHAM 6 and MINEQL+ 4.5 for the chemical speciation of Cu2+ in the rhizosphere of forest soils.

Metal speciation data calculated by modeling could give useful information regarding the fate of metals in the rhizospheric environment. However, no comparative study has evaluated the relative accuracy of speciation models in this microenvironment. Consequently, the present study evaluates the reliability of free Cu ion (Cu2+) activity modeled by WHAM 6 and MINEQL+ 4.5 for 18 bulk and 18 rhizospheric soil samples collected in two Canadian forested areas located near industrial facilities. The modeling of Cu speciation was performed on water extracts using pH, dissolved organic carbon (DOC), major ions, and total dissolved Al, Ca, Cu, Mg, and Zn concentrations as input data. Four scenarios representing the composition of dissolved organic substances using fulvic, humic, and acetic acids were derived from the literature and used in the modeling exercise. Different scenarios were used to contrast soil components (rhizosphere vs bulk) and soil pH levels (acidic vs neutral to alkaline). Reference Cu2+ activity values measured by an ion-selective electrode varied between 0.39 and 41 nM. The model MINEQL+ 4.5 provided good predictions of Cu2+ activities [root-mean-square residual (RMSR)= 0.37], while predictions from WHAM 6 were poor (RMSR = 1.74) because they overestimated Cu complexation with DOC. Modeling with WHAM 6 could be improved by adjusting the proportion of inert DOC and the composition of DOC (RMSR = 0.94), but it remained weaker than predictions with MINEQL+ 4.5. These results suggested that the discrepancies between speciation models were attributed to differences in the binding capacity of humic substances with Cu, where WHAM 6 appeared to be too aggressive. Therefore, we concluded that chemical interactions occurring between Cu and DOC were key factors for an accurate simulation of Cu speciation, especially in rhizospheric forest soils, where high variation of the DOC concentration and composition are observed.

Solid-solution partitioning of Cd, Cu, Ni, Pb, and Zn in the organic horizons of a forest soil.

We report the solid-liquid partitioning of Cd, Cu, Ni, Pb, and Zn in 60 organic horizon samples of forest soils from the Hermine Watershed (St-Hippolyte, PQ, Canada). The mean Kd values are respectively 1132, 966, 802, 3337 and 561. Comparison of those Kd coefficients to published compilation values show that the Kd values are lower in acidic organic soil horizons relative to the overall mean Kd values compiled for mineral soils. But, once normalized to a mean pH of 4.4, the Kd values in organic soil horizons demonstrate the high sorption affinity of organic matter, which is either as good as or up to 30 times higher than mineral soil materials for sorbing trace metals. Regression analysis shows that, within our data set, pH and total metal contents are not consistent predictors of metal partitioning. Indeed, metal sorption by the solid phase must be studied in relation to complexation by dissolved organic ligands, and both processes may sometime counteract one another.