Susan Tandy

Remediation of metal polluted mine soil with compost: co-composting versus incorporation.

Trace element contamination of post-industrial sites represents a major environmental problem and sustainable management options for remediating them are required. This study compared two strategies for immobilizing trace elements (Cu, Pb, Zn, and As) in mine spoil: (1) co-composting contaminated soil with organic wastes and (2) conventional incorporation of mature compost into contaminated soil. Sequential chemical extraction of the soil was performed to determine temporal changes in trace element fractionation and bioavailability during composting and plant growth. We show that mine spoil can be co-composted successfully and this action causes significant shifts in metal availability. However, co-composting did not lead to significant differences in metal partitioning in soil or in plant metal uptake compared with simply mixing mine spoil with mature compost. Both treatments promoted plant growth and reduced metal accumulation in plants. We conclude that co-composting provides little additional benefit for remediating trace-element-polluted soil compared with incorporation of compost.

The use of DGT for prediction of plant available copper, zinc and phosphorus in agricultural soils

Soil chemical extractions are widely used to predict the nutritional status of soils. However, the correlation between extracted elements and plant uptake is often poor, especially if compared over a range of soil types. The aim of this study was to examine a new method called Diffusive Gradients in Thin films (DGT), which measures the diffusive supply of elements, thereby mimicking a plant root. The ability of DGT to assess plant-available P, Zn and Cu was tested in a wide range of typical Scandinavian agricultural soils along with conventional methods (EDTA and DTPA for Cu and Zn; NaHCO3 for P and soil solution concentrations). Extracted soil concentrations were compared to that of the element in the youngest fully developed leaf of barley (Hordeum vulgare L.) grown in pots. For Zn and P, only DGT could predict plant uptake while conventional extraction methods and soil solution analyses performed poorly. All soil tests could predict Cu concentration in leaves, but the DGT technique proved to be most accurate followed by the soil solution concentration of Cu. We conclude that DGT is much more accurate at predicting plant-available P, Zn and Cu than commonly used methods for analysing plant-available nutrients in soil.

Heavy metal fractionation during the co-composting of biosolids, deinking paper fibre and green waste.

Due to the introduction of the European Union Landfill Directive, composting has become a potentially viable disposal route for some organic wastes. As waste-derived compost is frequently added to soil to improve soil quality, it is important to quantify the environmental risk posed by potentially toxic elements contained within it. Here we used a sequential chemical extraction procedure to investigate the temporal dynamics of heavy metals (Cu, Zn, Pb and Ni) during the co-composting of biosolids, deinking paper fibre and green waste. Overall, composting over 26 weeks reduced the availability of Ni, had no effect on Pb and slightly increased the availability of Cu and Zn. We conclude that although the total Cu and Ni concentrations in the compost exceed legislative guidelines for land application, due to their recalcitrant nature within the compost, this compost posed very little threat to soil or plant quality if used in agriculture or land restoration.

FT-IR as an alternative method for measuring chemical properties during composting.

Chemical properties have been used as a way of following the composting process and compost maturity, however, their analysis is very time consuming as each must be separately determined. By developing a more rapid method to predict these properties, time and cost would be saved. This study investigates the use of Fourier Transform mid-Infrared Spectroscopy (FT-IR) for this purpose. FT-IR spectra and measured values of several chemical properties from a variety of compost mixtures were used to produce calibrated models using partial least-squares regression analysis which predicted the known chemical properties. These models displayed a range of accuracies that for most properties was more than sufficient to follow at least broad dynamic changes associated with maturation. The best calibrations were achieved for total C, total N, LOI, lignin, and cellulose with r(2) values within the range 56-77%. Some degree of calibration was achieved for available-P and NH(4)(+)-N, with r(2) values of between 40% and 57%. No useful calibration could be achieved for NO(3)(-) or pH.

Release of antimony from contaminated soil induced by redox changes

Soil contamination by toxic antimony (Sb) released from corroding ammunition has become an issue of public concern in various countries. Many of these soils are at least occasionally subject to waterlogging; yet mechanisms controlling Sb mobility under anaerobic conditions are still poorly understood. We investigated Sb concentration and speciation dynamics in a calcareous shooting range soil in terms of changing redox conditions using microcosm experiments. The transition to reducing conditions invoked by indigenous microbial activity at first led to the immobilization of Sb, as Sb(V) was converted to Sb(III), which binds more extensively to iron (hydr)oxides. When reducing conditions continued, the previously sorbed Sb(III) was gradually released into solution due to reductive dissolution of the iron (hydr)oxides. Speciation measurements in the solid phase by Sb K-edge XANES spectroscopy and in the soil solution by liquid chromatography ICP-MS provided the first evidence that Sb(III) predominated at low redox conditions (Eh <0.05 V) in both phases. The results show that Sb(V) is less stable in reducing environments than commonly assumed. Given that Sb(III) is generally more toxic than Sb(V), the mobilization of Sb(III) under Fe-reducing conditions may significantly increase (eco)toxicological risks arising from Sb-contaminated soils that are prone to flooding or waterlogging.

Availability of Zinc and the Ligands Citrate and Histidine to Wheat: Does Uptake of Entire Complexes Play a Role?

Organic ligands in soils affect the availability of trace metals such as Zn to plants. This study investigated the effects of two of these ligands, citrate and histidine, on Zn uptake by wheat under hydroponic conditions. Uptake of (65)Zn in the presence of these ligands was compared to uptake in the presence of EDTA at the same free Zn concentration (Zn(2+) ~ 50 nM). In the presence of citrate Zn root uptake was enhanced ~3.5 times and in the presence of histidine, by a factor of ~9, compared to the EDTA treatments. Citrate uptake was slightly reduced in the treatment containing ligands and Zn compared to the treatment containing the same ligand concentration but no Zn. In addition, a higher uptake of Zn than of citrate was observed. This suggests that the enhanced Zn uptake was primarily due to increased supply of Zn(2+) by diffusion and dissociation of Zn-citrate complexes at the root surface. Histidine uptake was much higher than citrate uptake and not influenced by the presence of Zn. As histidine forms stronger complexes with Zn than citrate, the results suggest that the enhancement of Zn uptake in the presence of histidine was in part due to the uptake of undissociated Zn-histidine complexes.

Comparison of different microbial bioassays to assess metal‐contaminated soils

These experiments compared the sensitivity of four different types of bioassay over time after five metals were added to a wide range of soils at the maximum concentrations in the European Union Sewage Sludge Directive. Three were chronic assays (most probable number of Rhizobium leguminosarum, soil microbial C and Biolog substrate utilization). The fourth bioassay, an acute biosensor, employed a lux-marked luminescent bacterium (Escherichia coli) in the soil pore water. Five metals were added to 23 different soils as a mixture at Zn = 300, Cd = 3, Pb = 300, Cu = 135, and Ni = 75 mg/kg as nitrate salts and compared with unamended controls. Zinc and Cu were the metals most likely to be toxic at the concentrations used here. In the case of Rhizobium, the number of cells in soil was not affected after 11 d; however, by 818 d the numbers had decreased by four orders of magnitude with increasing concentrations of Zn and Cu in soil solution. Microbial biomass also was not affected after 11 d, but significantly decreased with increased Zn (p < 0.001) and Cu (p < 0.01) in soil solution after 818 d. Toxicity to the soil microbial biomass increased with time, whereas the toxicity to the biosensor remained the same. Biolog substrate utilization profiles were not responsive to the concentrations used here.

Antimony retention and release from drained and waterlogged shooting range soil under field conditions

Many soils polluted by antimony (Sb) are subject to fluctuating waterlogging conditions; yet, little is known about how these affect the mobility of this toxic element under field conditions. Here, we compared Sb leaching from a calcareous shooting range soil under drained and waterlogged conditions using four large outdoor lysimeters. After monitoring the leachate samples taken at bi-weekly intervals for >1.5 years under drained conditions, two of the lysimeters were subjected to waterlogging with a water table fluctuating according to natural rainfall water infiltration. Antimony leachate concentrations under drained conditions showed a strong seasonal fluctuation between 110 μg L(-1) in summer and <40 μg L(-1) in winter, which closely correlated with fluctuations in dissolved organic carbon (DOC) concentrations. With the development of anaerobic conditions upon waterlogging, Sb in leachate decreased to 2-5 μg L(-1) Sb and remained stable at this level. Antimony speciation measurements in soil solution indicated that this decrease in Sb(V) concentrations was attributable to the reduction of Sb(V) to Sb(III) and the stronger sorption affinity of the latter to iron (Fe) (hydr)oxide phases. Our results demonstrate the importance of considering seasonal and waterlogging effects in the assessment of the risks from Sb-contaminated sites.

Internal Zn allocation influences Zn deficiency tolerance and grain Zn loading in rice (Oryza sativa L.)

One of the important factors that influences Zn deficiency tolerance and grain Zn loading in crops is the within-plant allocation of Zn. Three independent experiments were carried out to understand the internal Zn distribution patterns in rice genotypes grown in Zn-sufficient and Zn-deficient agar nutrient solution (ANS). In one of the experiments, two rice genotypes (IR55179 and KP) contrasting in Zn deficiency tolerance were leaf-labeled with 65Zn. In the other two experiments, two Zn biofortification breeding lines (IR69428 and SWHOO) were either root- or leaf-labeled with 65Zn. Rice genotype IR55179 showed significantly higher Zn deficiency tolerance than KP at 21 and 42 days after planting. When KP was Zn-deficient, it failed to translocate 65Zn from the labeled leaf to newly emerging leaves. Similarly, the root-to-shoot translocation of unlabeled Zn was lower in KP than in IR55179. These results suggest that some Zn-efficient rice genotypes have greater ability to translocate Zn from older to actively growing tissues than genotypes sensitive to Zn deficiency. Among the two Zn biofortication breeding lines that were leaf-labeled with 65Zn at 10 days before panicle initiation stage, 65Zn distribution in the grains at maturity was similar between both genotypes in Zn-sufficient conditions. However, under Zn-deficient conditions, SWHOO accumulated significantly higher 65Zn in grains than IR69428, indicating that SWHOO is a better remobilizer than IR69428. When the roots of these two Zn biofortication breeding lines were exposed to 65Zn solution at 10 days after flowering, IR69428 showed higher root uptake of 65Zn than SWHOO in Zn-sufficient conditions, but 65Zn allocation in the aerial parts of the plant was similar between both genotypes.

Contaminated land clean-up using composted wastes and impacts of VOCs on land.

This paper describes experiments that demonstrate the effects and potential for remediation of a former steelworks site in Wales polluted with polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Under field conditions, PAH-contaminated soil was composted in-vessel, with or without organic feedstocks, receiving forced aeration for 80 days followed by 4 months maturation. Treatments compared PAH removal in contaminated soil to contaminated soil mixed with three different organic waste mixes after composting and after composts were spread to land. After composting, PAH concentrations declined in all treatments, by up to 38%. Sixteen months after the composts were landspread and vegetation was established, only those containing contaminated soil with organic additions exhibited further PAH removal, by up to 29%. Composting resulted in a decline in the relative concentration of small PAHs, whereas the landspreading-vegetation phase saw a decline in the relative concentration of medium PAHs in two of the three composts exhibiting PAH removal. Under controlled glasshouse conditions, vegetated soil columns of differing depths were exposed to VOCs from beneath. VOC vapour affected both shoot and root growth and soil microbial activity; effects varied with distance from the VOC source. This work demonstrated that on-site remediation of aged PAH-contaminated land can be successfully initiated by in-vessel co-composting followed by land spreading and vegetation, within a practical timeframe.