Evaluation of diffusive gradients in thin film (DGT) samplers for measuring contaminants in the Antarctic marine environment

This work has been the first application of DGT samplers for measuring metals in water and sediment porewater in the Antarctic environment, and whilst DGT water sampling was restricted to quantification of Cd, Fe and Ni, preconcentration using Empore chelating disks provided results for an additional nine elements (Sn, Pb, Al, Cr, Mn, Co, Cu, Zn, As). Although higher concentrations were measured for some metals (Cd, Ni, Pb) using the Empore technique, most likely due to particulate-bound or colloidal species becoming entrapped in the Empore chelating disks, heavy metal concentrations in the impacted Brown Bay were found to be comparable with the non-impacted O'Brien Bay. Sediment porewater sampling using DGT also indicated little difference between Brown Bay and O'Brien Bay for many metals (Cd, Al, Cr, Co, Ni, Cu), however, greater amounts of Pb, Mn, Fe and As were accumulated in DGT probes deployed in Brown Bay compared with O'Brien Bay, and a higher accumulation of Sn was observed in Brown Bay inner than any of the other three sites sampled. Comparison of DGT derived porewater concentrations with actual porewater concentrations showed limited resupply of Cd, Pb, Al, Cr, Mn, Co, Ni, Cu, Zn and As from the solid phase to porewater, with these metals appearing to be strongly bound to the sediment, however, resupply of Fe and Sn was apparent. Based upon our observations here, we suggest that Sn, and to a lesser extent Pb, are critical contaminants.     

Storage mediums affect metal concentration in woodlice (Isopoda)

Terrestrial invertebrates are becoming widely established as tools to assess heavy metal pollution at contaminated sites. A practical and time saving method to sample terrestrial invertebrates consist of pitfall traps, often filled with a 4% formaldehyde solution and some detergent. The reliability of metal concentrations based on organisms captured and stored in this solution might however be questioned and we therefore tested the effect of formaldehyde on Zn, Cu, Cd and Pb concentration experimentally in three isopod species. Our results showed that in many cases, significant decreases in Cu concentrations compared to animals stored in a freezer were observed that could be as high as 40%, while Zn, Cd and Pb concentrations increased. A regression analysis of individual dry weight on individual size revealed that formaldehyde decreases the dry weight substantially and in that way causes increased measurements of Zn, Cd and Pb concentrations. We conclude that pitfall traps with formaldehyde should better not be used to collect animals in which concentrations of heavy metals or other toxic substances will be determined.     

Bioavailability and plant accumulation of heavy metals and phosphorus in agricultural soils amended by long-term application of sewage sludge

Amendment of agricultural soils with municipal sewage sludges provides a valuable source of plant nutrients and organic matter. Nevertheless, addition of heavy metals and risks of eutrophication continue to be of concern. Metal behaviour in soils and plant uptake are dependent on the nature of the metal, sludge/soil physico-chemical properties and plant species. A pot experiment was carried out to evaluate plant production and heavy metal uptake, soil heavy metal pools and bioavailability, and soil P pools and possible leaching losses, in agricultural soils amended with sewage sludge for at least 10 years (F20) compared to non-amended soils (control). Sewage sludge application increased soil pH, N, Olsen-extractable-P, DOC and exchangeable Ca, Mg and K concentrations. Total and EDTA-extractable soil concentrations of Cu and Zn were also significantly greater in F20, and soil metal (Cu, Mn and Zn) and P fractionation altered. Compared to the control, in F20 relative amounts of acid-extractable (Mn, Zn), reducible (Mn, Zn) and oxidisable (Cu, Zn) metal fractions were greater, and a dominance of inorganic P forms was observed. Analyses of F20 soil solutions highlighted risks of PO4 and Cu leaching. However, despite the observed increases in metal bioavailability sewage sludge applications did not lead to an increase in plant shoot concentrations (in wild plants or crop species). On the contrary, depending on the plant species, Mn and Zn tissue concentrations were within the deficiency level for most plants.     

DGT use in contaminated site characterization. The importance of heavy metal site specific behaviour

The objective of this study is to provide an insight into the techniques for measuring the lability of heavy metals in solid-phase pool of soils in order to assess the environmental risk arising from pollution. The technique of diffusive gradients in thin films (DGT) and a sequential extraction procedure were used to quantify the labile pools of Cu, Fe, Mn and Ni. These results were compared to metal concentrations in groundwater, measured directly using the in situ piezometers, and to the total concentration of metal in the soils. High concentrations of metal in the directly analysed soil solution compared to DGT measurement were attributed to the presence of colloidal metal. The use of DGT allowed only to calculate leaching parameters of the free ions and labile fractions of the metals. For this reason DGT technique needs preliminary investigation on metal speciation in soil solution before its application as a good tool in the characterization procedure of contaminated sites.     

Speciation of Cd and Zn in contaminated soils assessed by DGT-DIFS, and WHAM/Model VI in relation to uptake by spinach and ryegrass

A pot experiment was carried out to investigate the impact of Cd and Zn extractability in soil and speciation in pore water of industrial contaminated soils, on metal concentration in a metal sensitive species like spinach (Spinacia oleracea) and a more metal tolerant species like Italian ryegrass (Lolium multiflorum). For chemical speciation of Cd and Zn in pore water, WHAM/Model VI version 6.0 was used. The DGT technique was used to determine the effective concentration, C(E), of Cd and Zn in soils. The free ion activity in pore water correlated well with the contents in plants, and there was a linear relationship between the C(E) values and the concentration of Cd and Zn in both spinach and ryegrass in the non-toxic range. However, the C(E) values usually overestimated the plant contents when plants, particularly the spinach plants, were subjected to toxic concentration in the pore water. Metal uptake decreased in plants affected by toxicity, whereas metal binding to the Chelex resin did not. Thus, we found no linear relationship between the C(E) and metal contents in spinach, whereas a linear relationship was found between C(E)-Zn and the Zn concentration in ryegrass (r2=0.96, p<0.001). For Cd in ryegrass this relationship was weak (r2=0.53, p=0.18). This study indicates that the transport of metals from labile metal pools to the DGT-resin is linearly related to plant uptake only when plants are growing well, and that the applicability of DGT as an indicator for plant uptake seems species dependent.     

Metal accumulation in the greentail prawn, Metapenaeus bennettae, in Sydney and Port Hacking estuaries, Australia

Metal concentrations of the inshore greentail prawn, Metapenaeus bennettae, and surface sediments from locations within Sydney estuary and Port Hacking (Australia) were assessed for bioaccumulation and contamination. The current study aimed to assess metal concentrations in prawn tissue (tail muscle, exoskeleton, hepatopancreas and gills), relate whole body prawn tissue metal concentrations to sediment metal concentrations and animal size, as well as assess prawn consumption as a risk to human health. Metal concentrations were highest in sediment and prawns from contaminated locations (Iron Cove, Hen and Chicken Bay and Lane Cove) in Sydney estuary compared with the reference estuary (Port Hacking). Concentrations in sediments varied considerably between sites and between metals (As, Cd, Cr, Cu, Ni, Pb and Zn), and although concentrations exceeded Interim Sediment Quality Guideline-Low values, metals (As, Cd, Cr, Cu, Ni, Pb and Zn) were below Australian National Health and Medical Research Council human consumption guidelines in prawn tail muscle tissue. Metal concentrations in prawn tail muscle tissue were significantly different (p?≤?0.05) amongst locations for Pb, Zn and Cd, and metal concentrations were generally highest in gills tissue, followed by the hepatopancreas, exoskeleton and tail muscle. The exoskeleton contained the highest Sr concentration; the hepatopancreas contained the highest As, Cu and Mo concentrations; and the gills contained the highest Al, Cr, Fe and Pb concentrations. Concentrations of Pb, As and Sr were significantly different (p?≤?0.05) between size groups amongst locations.     

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.     

Distribution and accumulation of heavy metals in the sediments of Kaohsiung Harbor, Taiwan

The distribution, enrichment, and accumulation of heavy metals in the sediments, especially those at the vicinity of tributary estuaries of Kaohsiung Harbor, Taiwan were investigated. Sediment samples from six locations in the Kaohsiung Harbor were collected quarterly in the period from 2002 to 2005 and characterized for metal content (e.g., Hg, Pb, Cd, Cr, Cu, Zn and Al), water content, organic matter, total nitrogen, total phosphorous, total grease, and grain size. Results showed that metal concentrations varied from 0.58 mg kg(-1) for Cd to 596 mg kg(-1) for Zn. Metal concentrations at the vicinity of river mouths were higher than those at other locations. All heavy metals studied, except Cr, had relatively high enrichment factors and geo-accumulation indices in the estuaries. Moreover, metal concentrations correlated closely to the physical-chemical properties of the sediments, which strongly suggested the influence of industrial and municipal wastewaters discharged from the neighboring industrial parks and river basins. Results would help develop strategies for pollution control and sediment remediation of Kaohsiung Harbor.     

Sensitivity of Mediterranean woody seedlings to copper, nickel and zinc

The restoration of heavy metal contaminated areas requires information on the response of native plant species to these contaminants. The sensitivity of most Mediterranean woody species to heavy metals has not been established, and little is known about phytotoxic thresholds and environmental risks. We have evaluated the response of four plant species commonly used in ecological restoration, Pinus halepensis, Pistacia lentiscus, Juniperus oxycedrus, and Rhamnus alaternus, grown in nutrient solutions containing a range of copper, nickel and zinc concentrations. Seedlings of these species were exposed to 0.048, 1 and 4 microM of Cu; 0, 25 and 50 microM of Ni; and 0.073, 25 and 100 microM of Zn in a hydroponic silica sand culture for 12 weeks. For all four species, the heavy metal concentration increased in plants as the solution concentration increased and was always higher in roots than in shoots. Pinus halepensis and P. lentiscus showed a higher capacity to accumulate metals in roots than J. oxycedrus and R. alaternus, while the allocation to shoots was considerably higher in the latter two. Intermediate heavy-metal doses enhanced biomass accumulation, whereas the highest doses resulted in reductions in biomass. Decreases in shoot biomass occurred at internal concentrations ranging from 25 to 128 microg g-1 of Zn, and 1.7 to 4.1 microg g( -1) of Cu. Nickel phytoxicity could not be established within the range of doses used. Rhamnus alaternus and J. oxycedrus showed higher sensitivity to Cu and Zn than P. halepensis and, especially, P. lentiscus. Contrasted responses to heavy metals must be taken into account when using Mediterranean woody species for the restoration of heavy metal contaminated sites.     

Copper and Zn uptake by radish and pakchoi as affected by application of livestock and poultry manures

Environmental safety of agricultural utilization of livestock and poultry manures from intensive farming is attracting great attention because the manures often contain high concentrations of heavy metals and organic pollutants. Pot experiments, in which a pig manure (PM), a chicken manure (CM) and a commercial organic manure (OM) with different concentrations of Cu and Zn to simulate soil metal accumulation by manure application for different times were utilized in a garden soil at a rate of 2% (W/W), were conducted to study the effect of application of these livestock and poultry manures on growth of radish (Raphanus sativus L.) and pakchoi (Brassica chinensis L.) as well as their Cu and Zn uptake. The results exhibit that the manures except the PM improved the growth of radish and pakchoi. The difference of biomass among the same manure treatments containing different concentrations of Cu and Zn, however, was insignificant. In addition, application of the livestock and poultry manures significantly increased soil pHs and electric conductivities (EC) compared with the control, which is ascribed that these manures had high pH and contained large amounts of inorganic ions. The available soil Zn concentrations in the PM were higher than that in the CM and OM, and the extractable soil Cu concentrations in the three manures were almost the same after radish growth in the garden soil but were different after pakchoi growth. Zinc and Cu concentrations in the radish and pakchoi tissues increased when the soil Zn and Cu concentrations increased by manures application, but were still within a safe value. An except is the treatment PM4 in which the Zn concentration of the above-ground part of radish was 28.7 mg kg-1, exceeding the Chinese Food Hygiene Standard of 20 mg kg-1 based on fresh weight. Good correlation was obtained between the extractable soil Zn (or Cu) concentrations extracted by 1.0 mol l-1 NH4NO3 and the Zn (or Cu) concentrations in radish and pakchoi tissues, which was expected to be effective in forecasting Cu and Zn availability to radish and pakchoi in manure agronomic utilization.     

Effects of past sewage sludge additions on heavy metal availability in light textured soils: implications for crop yields and metal uptakes

The effect of heavy metal additions in past sewage sludge applications on soil metal availability and the growth and yield of crops was evaluated at two sites in the UK. At Gleadthorpe, sewage sludges enriched with salts of zinc (Zn), copper (Cu) and nickel (Ni) had been applied to a loamy sand in 1982 and additionally naturally contaminated Zn and Cu sludge cakes in 1986. At Rosemaund, sewage sludges naturally contaminated with Zn, Cu, Ni and chromium (Cr) had been applied in 1968-1971 to a sandy loam. From 1994 to 1997, the yields of both cereals and legumes at Gleadthorpe were up to 3 t/ha lower than the no-sludge control where total topsoil Zn and Cu concentrations exceeded 200 and 120 mg/kg, respectively, but only when topsoil ammonium nitrate extractable metal levels also exceeded 40 mg/kg Zn and 0.9 mg/kg Cu. At Rosemaund, yields were only decreased where total topsoil Cu concentrations exceeded 220 mg/kg or 0.7 mg/kg ammonium nitrate extractable Cu. These results demonstrate the importance of measuring extractable as well as total heavy metal concentrations in topsoils when assessing likely effects on plant yields and metal uptakes, and setting soil quality criteria.     

Diffusive gradients in thin films,Rhizon soil moisture samplers,and indicator plants to predict the bioavailabilities of potentially toxic elements in contaminated technosols

The phytoavailabilities and potential remobilization of potentially toxic elements (PTEs) such as Zn, Pb, Cd, As, and Sb were assessed in contaminated technosols from former mining and smelting sites. The PTE concentrations in soil pore water (SPW) and diffusive gradients in thin films (DGT)-measured concentration (C _DGT) methods were used to assess the bioavailabilities of PTE and their remobilization in this study. Together with classical Chelex-100 DGT probes to measure Zn, Cd, and Pb, novel ferrihydrite-backed DGT were used for As and Sb measurements alongside with Rhizon soil moisture sampler method for SPW sampling. To assess the phytoavailabilities of PTE, a germination test with dwarf beans as a plant indicator was used for this purpose. Dwarf bean primary leaves showed high Zn concentrations in contrast to Pb and Cd which showed low phytoavailabilities. Despite As and Sb are present in high concentrations in the mine tailings, their phytoavailabilities indicate very low bioavailabilities. The amounts of Zn, Pb, Cd, As, and Sb extracted with DGT devices correlated well with the total dissolved PTE concentrations in the SPW. The highest R values were observed for Zn, followed by Cd and Pb, indicating the ability of the soil to sustain SPW concentrations, which decreased in that order. Good correlations were also observed between each of dissolved PTE concentrations in SPW, DGT-measured PTE concentrations (C _DGT), and the accumulation of PTE in dwarf bean primary leaves. It could be concluded that the use of Rhizon soil moisture samplers and DGT methods may be considered to be a good methods to predict the PTE bioavailabilities in contaminated technosols.     

Ecological risk assessment of heavy metals in sediment and human health risk assessment of heavy metals in fishes in the middle and lower reaches of the Yangtze River basin

The concentrations of heavy metals (Cr, Cd, Hg, Cu, Zn, Pb and As) in the water, sediment, and fish were investigated in the middle and lower reaches of the Yangtze River, China. Potential ecological risk analysis of sediment heavy metal concentrations indicated that six sites in the middle reach, half of the sites in the lower reach, and two sites in lakes, posed moderate or considerable ecological risk. Health risk analysis of individual heavy metals in fish tissue indicated safe levels for the general population and for fisherman but, in combination, there was a possible risk in terms of total target hazard quotients. Correlation analysis and PCA found that heavy metals (Hg, Cd, Pb, Cr, Cu, and Zn) may be mainly derived from metal processing, electroplating industries, industrial wastewater, and domestic sewage. Hg may also originate from coal combustion. Significant positive correlations between TN and As were observed.     

Biomonitoring of trace metals in a mine-polluted estuarine system (Spain)

In this paper, we examine metal concentrations in the water and in the crustacean Balanus balanoides from the Huelva estuary, one of the most polluted estuaries in Europe. Metal levels in waters are very high, especially those of Zn, Fe and Cu. Zn presents the highest concentrations, with a mean value of 690 microg l-1 in 2001 and 301 microg l-1 in 2002. As the water flows down through the estuary toward the sea, the metal concentrations drop sharply and the pH rises. The metal concentrations in balanoides tissues are, in general, very high, undoubtedly due to the high metal pollution of the water where it lives. Metal concentrations in Balanus balanoides tissues behave similarly to those in the water, reaching maximums in the upper part of the estuary and diminishing as we approach the sea. The element that reaches the highest levels in Balanus balanoides is Zn, with a mean value of 54.6 g kg-1 in 2001 and 29.9 g kg-1 in 2002, followed by Cu and Fe. There is a significant correlation (p<0.01) for concentrations of Cd, Cu, Fe, Mn, Ni and Zn in Balanus balanoides relative to their concentration in waters. Barnacles showed a great capacity to accumulate metals, especially Zn, Cu and Fe. Based on the results obtained, we can conclude that Balanus balanoides is a good tool for monitoring trace metals in the Huelva estuary.     

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.     

Relationships between ambient geochemistry, watershed land-use and trace metal concentrations in aquatic invertebrates living in stormwater treatment ponds

Stormwater treatment ponds receive elevated levels of metals from urban runoff, but the effects of these pollutants on organisms residing in the ponds are unknown. We investigated the accumulation of Cu, Zn, and Pb by macroinvertebrates collected from stormwater treatment ponds in Maryland serving commercial, highway, residential and open-space watersheds, and determined whether watershed land-use classification influences metal concentrations in macroinvertebrates, sediments, and water. Three types of invertebrate samples were analyzed--molluscs, odonates, and composite. Zn concentrations in odonates from ponds draining watersheds with commercial development (mean = 113.82 micrograms g-1) were significantly higher than concentrations in the other land-use categories. Similarly, Cu levels in odonates from commercial ponds (mean = 27.12 micrograms g-1) were significantly higher than from highway (mean = 20.23 micrograms g-1) and open space (mean = 17.79 micrograms g-1) ponds. However, metal concentrations in sediments and water did not differ significantly among land-uses. The results suggest that despite the high variation in ambient metal concentrations within each land-use category, macroinvertebrates in ponds serving commercial watersheds accumulate higher levels of Cu and Zn. The levels of Cu, Zn, and Pb in invertebrates from all ponds were less than dietary concentrations considered toxic to fish.     

Characterization and spatial distribution of heavy metals in sediment from Cedar and Ortega rivers subbasin

The Cedar and Ortega rivers subbasin is a complex environment where both natural and anthropogenic processes influence the characteristics and distributions of sediments and contaminants, which in turn is of importance for maintenance, dredging and pollution control. This study investigated the characteristics and spatial distribution of heavy metals, including lead (Pb), copper (Cu), zinc (Zn) and cadmium (Cd), from sediments in the subbasin using field measurements and three-dimensional kriging estimates. Sediment samples collected from three sampling depth intervals (i.e., 0-0.10, 0.11-0.56 and 0.57-1.88 m) in 58 locations showed that concentrations of Pb ranged from 4.47 to 420.00 mg/kg dry weight, Cu from 2.30 to 107.00 mg/kg dry weight, Zn from 9.75 to 2,050.00 mg/kg dry weight and Cd from 0.07 to 3.83 mg/kg dry weight. Kriging estimates showed that Pb, Cu and Cd concentrations decreased significantly from the sediment depth of 0.10 to 1.5 m, whereas Zn concentrations were still enriched at 1.5 m. It further revealed that the Cedar River area was a potential source area since it was more contaminated than the rest of the subbasin. Comparison of aluminum (Al)-normalized metal concentrations indicated that most of the metals within the top two intervals (0-0.56 m) had concentrations exceeding the background levels by factors of 2-10. A three-dimensional view of the metal contamination plumes showed that all of the heavy metals, with concentrations exceeding the threshold effect level (TEL) that could pose a threat to the health of aquatic organisms, were primarily located above the sediment depth of 1.5 m.     

Heavy metal accumulation by Nicotiana glauca Graham in a solid waste disposal site

Nicotiana glauca Graham, is the only perennial shrub growing in a solid waste contaminated site in the Negev desert of Israel. The concentration of heavy metals (Cu, Fe, Mn, Zn, Ni, Cd and Pb) in the upper soil layer was significantly higher (p<0.01) than in non-contaminated desert soil. In root and shoot of N. glauca, growing in the site, the concentration of Cu, Zn and Fe was significantly higher (p<0.05) than in plants of a non-contaminated site. In a controlled experiment, the concentrations of Zn and Cu in root of plants grown, in a mixture of contaminated and non-contaminated soil (1:1) was 9.5 and 4.7 higher than that of plants grown in non-contaminated soil, respectively. While Zn was accumulated in shoot of plants grown in contaminated soil (531 mgkg(-1)) in significantly higher concentration than in plants grown in non-contaminated soil (56 mgkg(-1)), no significant differences were found in Cu accumulation. Growth of N. glauca was inhibited on contaminated soil, but no other obvious stress symptoms were apparent. Therefore, long term experiments under controlled conditions are planned to study the mechanism of heavy metal tolerance and accumulation in N. glauca.     

Impact of microbial activity on copper, lead and nickel mobilization during the bioremediation of soil PAHs

A fungal bioremediation method using P. frequentans removed up to 75% of phenanthrene with the addition of water and nutrients over a period of 30 d. During the bioremediation process, changes in metal behavior were monitored by an in situ technique (diffusive gradients in thin-films, DGT) and by soil solution chemistry. DGT provided absolute data on fluxes from the solid phase to the DGT device and relative trends of concentrations of the most labile metal species. DGT response indicated that bioremediation increases metal mobilization from the solid phase. Filtration provided data on the concentrations of solution phase (<0.45 microm) metal. In all case, metal fluxes and concentrations significantly increased after the bioremediation process began. Fluxes increased from <0.1 pg cm(-2)s(-1) before bioremediation to between 0.2 and 0.5 pg cm(-2)s(-1) after bioremediation. Metal concentrations in the soils solution (filtration at 0.45 microm) increased from 2 to 10 microg l(-1) (Cu), 1-4 microgl(-1) (Pb) and from 40 to 140 microg l(-1) (Ni) after bioremediation. Although over a short time period, these data strongly indicated that there was remobilization of metal from solid to solution (and thus to the DGT device) directly due to the bioremediation process. Although the mechanism was not unambiguously identified, it was shown not to be related to small changes in bulk pH over time and was attributed to the microbial action on the surface of the soil solid phase, releasing metal into solution. Additionally, differences in metal concentration and flux were observed in sterilized and non-sterilized soils and in the absence or presence of phenanthrene. The results indicated that the bioremediation of soil by P. frequentans increased the flux, lability and mobility of trace metal species and therefore the likely metal bioavailability to plants.