Dioxins, PCBs, and HCB in soil and peat profiles from a pristine boreal catchment

The aim of this study was to explore how atmospherically derived soil pollution is affected by environmental processes at two typical boreal catchment landscape type settings: wetlands and forested areas. Measurements of hydrophobic organic compounds (HOCs) in forest soil and peat from an oligotrophic mire at various depths were performed at a remote boreal catchment in northern Sweden. HOCs in peat were evenly distributed throughout the body of the mire while levels of HOCs in the forest soil increased with increased amount of organic matter. Evaluation of HOC composition by principal component analysis (PCA) showed distinct differences between surface soils and deeper soil and peat samples. This was attributed to vertical transport, degradation and/or shifting sources over time. The calculated net vertical transport differed between surface layers (0.3%) and deeper soils (8.0%), suggesting that vertical transport conditions and processes differ in the deeper layers compared to the surface layers.     

The influence of organic ligands on the retention of lead in soil

Organic acids are commonly produced and exuded by plant roots and soil microorganisms. Some of these organic compounds are effective chelating agents and have the potential to enhance metal mobility. The effect of citrate and salicylate on the leaching of lead in soil was investigated in a laboratory experiment. In short-term batch experiments, adsorption of lead to soil was slightly enhanced with increasing salicylate concentration (500-5000 microM) but decreased significantly in the presence of citrate. These observations suggested that citrate may enhance Pb leaching, but this was not observed in the column study. Soluble Pb in the presence and absence citrate or salicylate (up to 5000 microM) was added to soil columns at a moderate flow rate, but no Pb was observed to emerge from the soil in any of the soil columns. Rapid biodegradation of citrate in soil eliminated potential complexing ability. Breakthrough of Pb from soil was noted only when using small columns at high flow rates (>20 pore volumes per day). Under these conditions of physical and chemical non-equilibrium, citrate was not degraded and significantly enhanced Pb mobility. As in the batch adsorption experiments, the presence of salicylate reduced Pb leaching. Considering the extreme conditions required to induce Pb leaching, it is likely that Pb will remain relatively immobile in soil even in the presence of a strong complexing agent such as citrate.     

Development of a biobarrier for the remediation of PCE-contaminated aquifer

The industrial solvent tetrachloroethylene (PCE) is among the most ubiquitous chlorinated compounds found in groundwater contamination. The objective of this study was to develop a biobarrier system, which includes a peat layer to enhance the anaerobic reductive dechlorination of PCE in situ. Peat was used to supply primary substrate (electron donor) continuously. A laboratory-scale column experiment was conducted to evaluate the feasibility of this proposed system or PCE removal. This experiment was performed using a series of continuous-flow glass columns including a soil column, a peat column, followed by two consecutive soil columns. Anaerobic acclimated sludges were inoculated in all three soil columns to provide microbial consortia for PCE biodegradation. Simulated PCE-contaminated groundwater with a flow rate of 0.25 l/day was pumped into this system. Effluent samples from each column were analyzed for PCE and its degradation byproducts (trichloroethylene (TCE), cis-dichloroethylene (cis-DCE), vinyl chloride (VC), ethylene (ETH), and ethane). Results show that the decrease in PCE concentrations and production of PCE byproducts were observed over a 65-day operating period. Up to 98% of PCE removal efficiency was obtained in this passive system. Results indicate that the continuously released organics from peat column enhanced PCE biotransformation. Thus, the developed biobarrier treatment scheme has the potential to be developed into a cost-effective in situ PCE-remediation technology, and can be utilized as an interim step to aid in system scale-up.     

Attenuation of lead leachability in shooting range soils using poultry waste amendments in combination with indigenous plant species

Chemical immobilization technology utilizing poultry waste (PW) along with a native plant (Panicum maximum Jacq.) application was assessed for the attenuation of downward Pb dissolution and modification of Pb speciation in solid and liquid phases in the soil. A large column study with and without plant and PW applications was conducted using a Pb contaminated soil collected from a shooting range area. The PW application reduced water-extractable Pb by about 43% of that of the treatment without the PW and plant applications (Control). The cumulative Pb amount in column leachates over 100d was increased by the PW amendment (0.32mg) compared to Control (0.27mg), but was reduced to 0.23mg by the combined use of plant and PW amendment. Sequential extraction analysis revealed that the Pb fractions of PW-amended soils were shifted to less soluble phases as indicated by an increased residual fraction (20%) and decreased exchangeable and carbonate fractions (22%) than those in the Control soil. Thermodynamic equilibrium calculations demonstrated that predicted Pb(2+) activity was saturated with respect to cerussite in the Control soil and was supersaturated with respect to chloropyromorphite in the PW-amended soils. Our results suggest that the use of plant in combination with PW as a Pb immobilizing amendment attenuated downward Pb leaching and altered Pb species to more geochemically stable phases.     

Characteristics in oxidative degradation by ozone for saturated hydrocarbons in soil contaminated with diesel fuel

Although alkanes are relatively less reactive to chemical oxidation compared to alkenes, the chemical oxidation of alkanes has not been adequately explored in the context of environmental remediation efforts. Laboratory-scale column experiments were therefore conducted with soil artificially contaminated by diesel fuel as a surrogate for alkanes of environmental relevance. Particular attention was paid to saturated hydrocarbons refractory to volatilization. Reaction conditions involve 1485mgkg(-1) of the initial concentration of diesel range organics (DRO) and a constant ozone concentration of 119+/-6mgl(-1) at the flow rate of 50mlmin(-1). The observed removal of DRO reached 94% over 14h of continuous ozone injection. Ozone oxidation demonstrated effective removal of non-volatile DRO in the range of C(12)-C(24). Each alkane compound displayed comparable degradation kinetics, suggesting virtually no selectivity of ozone reactions with alkanes in soil. A pseudo-first order kinetic model closely simulated the removal kinetics, yielding a reaction rate constant of 0.213 (+/-0.021)h(-1) and a half-life of 3.3 (+/-0.3)h under the experimental conditions used in this study. An estimate of ozone demand was 32mg of O(3) (mgDRO)(-1).     

Evidence of the involvement of plant ligno-cellulosic structure in the sequestration of Pb: an X-ray spectroscopy-based analysis

European walnut (Juglans regia) plants were grown in pots, on peat soil contaminated with lead (Pb), for four years. European walnut was chosen because it grows in Mediterranean climates, it yields a high biomass, and a fine quality wood. In the above ground parts Pb concentration was 1000 times lower than in roots: in 50 g roots there was 450 mg of Pb. Microanalysis of roots found in periderm more than 50% of the total root Pb. Pb L(III) EXAFS spectroscopy was performed on: root powder from Pb-exposed plants, Pb-impregnated cellulose and lignin. Comparison of plant material with lignin and cellulose helped to envisage a plant disposal strategy for Pb. This may consist in establishing links with large organic molecules, which are abundant constituents of cell walls. EXAFS spectroscopy evidenced the presence of Pb-O bindings within the ligno-cellulosic structure in roots. Lead was scantly conveyed to the shoots, giving to walnut plants an added asset in Pb phytostabilization.     

Microbial cellulose decomposition in soils from a rifle range contaminated with heavy metals

The objective of this study was to assess the effects of heavy metals on microbial decomposition of cellulose in heavy metal-contaminated soils using a cotton strip assay. The assay is a measure of the potential of soil microorganisms to decompose the plant polymer, cellulose. Cellulolytic activity in soil was assessed by determining the reduction in tensile strength of the buried cotton strips over a 25- and 45-day period. Soils were obtained from a rifle range that contain high levels of lead, copper and zinc. The site has been used for approximately 50 years, resulting in metal levels of up to 30,000 mg/kg of lead, 4000 mg/kg of copper and 600 mg/kg of zinc in the most contaminated soils. All the metal-contaminated soils had lower degradation rates than the uncontaminated soils tested. Among the contaminated soils, however, the heavy metal concentration was not the major factor in determining the loss in tensile strength of the cotton strips, where cellulose decomposition was governed by other soil physicochemical properties. Soil with a higher cation exchange capacity, readily oxidisable material and volatile solids content had the greatest loss in tensile strength of cotton strips. Microbial adaptation to the presence of high concentrations of soil heavy metals and reduced bioavailability of metals is the likely explanation for this phenomenon.     

Biosurfactant technology for remediation of cadmium and lead contaminated soils

This research focuses on column experiments conducted to evaluate the potential of environmentally compatible rhamnolipid biosurfactant produced by Pseudomonas aeruginosa strain BS2 to remove heavy metals (Cd and Pb) from artificially contaminated soil. Results have shown that di-rhamnolipid removes not only the leachable or available fraction of Cd and Pb but also the bound metals as compared to tap water which removed the mobile fraction only. Washing of contaminated soil with tap water revealed that approximately 2.7% of Cd and 9.8% of Pb in contaminated soil was in freely available or weakly bound forms whereas washing with rhamnolipid removed 92% of Cd and 88% of Pb after 36 h of leaching. This indicated that di-rhamnolipid selectively favours mobilization of metals in the order of Cd>Pb. Biosurfactant specificity observed towards specific metal will help in preferential elution of specific contaminant using di-rhamnolipid. It was further observed that pH of the leachates collected from heavy metal contaminated soil column treated with di-rhamnolipid solution was low (6.60-6.78) as compared to that of leachates from heavy metal contaminated soil column treated with tap water (pH 6.90-7.25), which showed high dissolution of metal species from the contaminated soil and effective leaching of metals with treatment with biosurfactant. The microbial population of the contaminated soil was increased after removal of metals by biosurfactant indicating the decrease of toxicity of metals to soil microflora. This study shows that biosurfactant technology can be an effective and nondestructive method for bioremediation of cadmium and lead contaminated soil.     

Tracer diffusion from a horizontal fracture into the surrounding matrix: measurement by computed tomography

The vertical diffusion of NaI solution from a horizontal fracture into and within the surrounding matrix was tracked and quantified over time using an artificially fractured chalk core (30x5 cm) and a second-generation X-ray computed tomography (CT) scanner. The different tracer-penetration distances imaged in the matrix above and below the horizontal fracture are indicative of a greater tracer mass penetrating into the lower matrix. The enhanced transport in the matrix below the fracture was related to the Rayleigh-Darcy instability induced by the density differences between the heavier tracer solution in the fracture (1.038) and the distilled water that had initially resided in the matrix. Our observations suggest that below the fracture, the tracer is propagated by an advection-diffusion process that is characterized by both higher rates and higher concentrations relative to its propagation by diffusion above the fracture. The experimental results suggest that the prediction of contaminant migration in a rock intersected by both vertical and horizontal (e.g. along bedding planes) fractures is difficult because of density effects that result in different solute-penetration rates.     

Regional trends in soil acidification and exchangeable metal concentrations in relation to acid deposition rates

The deposition of high levels of reactive nitrogen (N) and sulphur (S), or the legacy of that deposition, remain among the world's most important environmental problems. Although regional impacts of acid deposition in aquatic ecosystems have been well documented, quantitative evidence of wide-scale impacts on terrestrial ecosystems is not common. In this study we analysed surface and subsoil chemistry of 68 acid grassland sites across the UK along a gradient of acid deposition, and statistically related the concentrations of exchangeable soil metals (1 M KCl extraction) to a range of potential drivers. The deposition of N, S or acid deposition was the primary correlate for 8 of 13 exchangeable metals measured in the topsoil and 5 of 14 exchangeable metals in the subsoil. In particular, exchangeable aluminium and lead both show increased levels above a soil pH threshold of about 4.5, strongly related to the deposition flux of acid compounds.     

Trend and concentrations of legacy lead (Pb) in highway runoff

This study presents the results of lead (Pb) concentrations from both highway runoff and contaminated soil along 32 and 23 highway sites, respectively. In general, the Pb concentration on topsoil (0-15 cm) along highways was much higher than the Pb concentration in subsurface soil (15-60 cm). The Pb deposited on soil appears to be anthropogenic and a strong correlation was found between the Pb concentration in surface soil and highway runoff in urban areas. The concentration of Pb measured during 1980s from highways runoff throughout the world was up to 11 times higher than the measured values in mid 1990 s and 2000s. The current Pb deposited on soil near highways appears to be a mixture of paint, tire weight balance and old leaded gasoline combustion. Overall, the Pb phase-out regulation reduced the Pb deposits in the environment and consequently lowered Pb loading into receiving waters.     

Isotopic characterisation of lead in contaminated soils from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria

Soil samples from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria contained very high concentrations of cadmium, lead and zinc (up to 140, 4900 and 5900 mg kg(-1), respectively). A roadside soil in a relatively uncontaminated area also contained high concentrations of the same metals (24, 1550 and 1870 mg kg(-1), respectively) indicating that the transport of ores could be a source of contamination. Even though the lead isotope ratios in all the samples fell within a very narrow range (for example, 1.186-1.195 for (206)Pb/(207)Pb), the samples could be differentiated into three distinct groups: ores ((206)Pb/(207)Pb and (208)Pb/(207)Pb ratios of 1.1874-1.1884 and 2.4755-2.4807, respectively), current deposition (1.1864 and 2.4704-2.4711, respectively) and local background (1.1927-1.1951 and 2.4772-2.4809, respectively). Although most of the current deposition has its origin in the ores used at the smelter, up to 12% could be from other sources such as petrol lead.     

Soil intervention as a strategy for lead exposure prevention: the New Orleans lead-safe childcare playground project

The feasibility of reducing children's exposure to lead (Pb) polluted soil in New Orleans is tested. Childcare centers (median = 48 children) are often located in former residences. The extent of soil Pb was determined by selecting centers in both the core and outlying areas. The initial 558 mg/kg median soil Pb (range 14-3692 mg/kg) decreased to median 4.1 mg/kg (range 2.2-26.1 mg/kg) after intervention with geotextile covered by 15 cm of river alluvium. Pb loading decreased from a median of 4887 μg/m(2) (454 μg/ft(2)) range 603-56650 μg/m(2) (56-5263 μg/ft(2)) to a median of 398 μg/m(2) (37 μg/ft(2)) range 86-980 μg/m(2) (8-91 μg/ft(2)). Multi-Response Permutation Procedures indicate similar (P-values = 0.160-0.231) soil Pb at childcare centers compared to soil Pb of nearby residential communities. At ～$100 per child, soil Pb and surface loading were reduced within hours, advancing an upstream intervention conceptualization about Pb exposure prevention.     

Thermal Immobilization of Lead Contaminants in Soils Treated in a Fixed- and Fluidized-Bed Incinerator at Moderate Temperatures

Abstract

Artificially lead-contaminated soils with different lead contents (200, 450, 600, and 900 ppm) were thermally immobilized in both fixed-bed and fluidized-bed modes at moderate treating temperatures (less than 500 °C) for various retention times. Cement powder and brick powder were added to the artificially contaminated soils to enhance lead immobilization. Results indicate that increasing treating temperature and time increases the extent of lead immobilization, as determined by the U.S. Environmental Protection Agency's (U.S. EPA) Toxicity Characteristics Leachability Procedure (TCLP). The percentage of lead leached from the soil/ cement mixtures was in the range of less than 0.251%, compared with the range between 13.6% and 40.7% for the corresponding soil/brick mixtures. As the amount of brick dust added to the Pb-doped soil was increased, the specific Pb immobilization effectiveness increased from 0.0675 to 0.149 mg Pb/g brick (for the 20- and 50-gram brick addition, respectively). An increase in air flow rate from 2 to 40 L/min caused a slight decrease in the Pb leaching percentage from 14.96% to 11.59%. Both the Freundlich and Langmuir isotherms give a satisfactory fit (r = 0.945 ~ 0.998) for the data derived from a TCLP test of the thermally-treated soil samples (105 °C and 500 °C) that contained lead contaminants. Sorption of lead contaminants in soil and sorbent matrices was the primary type of chemisorption. The kinetic results indicated that the Pb-doped soil system was too complicated to be described by a simple calculation.     

Soil lead levels in a small town environment: a case study from Mt Pleasant, Michigan

Few studies are made on the potential soil Pb burden for a small city in rural environment. Data obtained by atomic absorption spectrophotometry suggest a somewhat weak significant positive relationship (r=0.27) between increased traffic volume and roadside soil Pb content. Median soil Pb levels along the most heavily travelled roads are 320 microg g(-1) while background concentrations are 200 microg g(-1). No significant relationship is found between predominant wind direction and soil Pb content. Zones where cars idle have only slightly elevated Pb levels. Older homes have soil Pb values exceeding 1000 microg g(-1); a significant positive relationship (r=0.59) exists between increasing soil Pb and home age. Schools, which are mainly located away from heavily travelled roads and typically of brick construction, have soil Pb concentrations at background levels. In general, the small city Pb burden is lower than in major urban areas. However, soils around older homes and in special locales, such as salvage yards, have Pb levels comparable to major urban areas.     

Phytoextraction of lead from firing range soil by Vetiver grass

Phytoextraction techniques utilizing a sterile strain of Vetiver grass (Vetiveria zizanoides) along with soil amendments were evaluated for removing lead and other elements such as Zn, Cu, and Fe from the soil of a 50-year old active firing range at the Savannah River Site (SRS). Lead-contaminated soil (300-4500 ppm/kg) was collected, dried, placed in pots, fertilized, and used as a medium for growing transplanted Vetiver grass plants in a greenhouse. The uptake of metals by the plants was evaluated in response to various fertilization and pre-harvest treatment schemes. Baseline metal concentrations in the soil of all pots were measured prior to planting and when the plants were harvested. Plants grew better when fertilized with Osmocote fertilizer in comparison to plants fertilized with 10-10-10 (NPK) fertilizer. Application of a chelating agent, EDTA, one week prior to harvest significantly increased the amount of lead that was phytoextracted. Lead concentrations of up to 1390-1450 ppm/kg in tissue samples were detected. Maximum Pb levels were observed in root tissues. The addition of non-lethal doses of a slow-release herbicide in combination with EDTA did not appear to further enhance phytoextraction or the translocation of Pb into shoots. The study indicated that the use of Vetiver grass coupled with the use of chelating soil amendments has considerable potential for use as a remedial strategy for lead-contaminated soils such as those associated with firing ranges.     

Utilisation of chemically stabilized arsenic-contaminated soil in a landfill cover

The aim of the study was to determine if an As-contaminated soil, stabilized using zerovalent iron (Fe⁰) and its combination with gypsum waste, coal fly ash, peat, or sewage sludge, could be used as a construction material at the top layer of the landfill cover. A reproduction of 2 m thick protection/vegetation layer of a landfill cover using a column setup was used to determine the ability of the amendments to reduce As solubility and stimulate soil functionality along the soil profile. Soil amendment with Fe⁰ was highly efficient in reducing As in soil porewater reaching 99 % reduction, but only at the soil surface. In the deeper soil layers (below 0.5 m), the Fe treatment had a reverse effect, As solubility increased dramatically exceeding that of the untreated soil or any other treatment by one to two orders of magnitude. A slight bioluminescence inhibition of Vibrio fischeri was detected in the Fe⁰ treatment. Soil amendment with iron and peat showed no toxicity to bacteria and was the most efficient in reducing dissolved As in soil porewater throughout the 2 m soil profile followed by iron and gypsum treatment, most likely resulting from a low soil density and a good air diffusion to the soil. The least suitable combination of soil amendments for As immobilization was a mixture of iron with coal fly ash. An increase in all measured enzyme activities was observed in all treatments, particularly those receiving organic matter. For As to be stable in soil, a combination of amendments that can keep the soil porous and ensure the air diffusion through the entire soil layer of the landfill cover is required.     

Wetland influence on mercury fate and transport in a temperate forested watershed

The transport and fate of mercury (Hg) was studied in two forest wetlands; a riparian peatland and an abandoned beaver meadow. The proportion of total mercury (THg) that was methyl mercury (% MeHg) increased from 2% to 6% from the upland inlets to the outlet of the wetlands. During the growing season, MeHg concentrations were approximately three times higher (0.27ng/L) than values during the non-growing season (0.10ng/L). Transport of Hg species was facilitated by DOC production as indicated by significant positive relations with THg and MeHg. Elevated concentrations of MeHg and % MeHg (as high as 70%) were found in pore waters of the riparian and beaver meadow wetlands. Groundwater interaction with the stream was limited at the riparian peatland due to the low hydraulic conductivity of the peat. The annual fluxes of THg and MeHg at the outlet of the watershed were 2.3 and 0.092microg/m2-year respectively.     

Characteristics of nitrate horizontal transport in a paddy field of the Tai Lake region,China

The characteristics of nitrate horizontal transport in a major paddy soil, Wu Shan soil in the Tai Lake region, were studied. The concentration of nitrate during horizontal movement decreased with the increasing in distance from the tracer source, the change following a logarithmic function. The concentration of the nitrate was strongly correlated with the soil moisture content, as an exponential function. The horizontal transport velocity of nitrate was significantly correlated with the distance of the tracer source as power function. Therefore, the velocity of nitrate horizontal transport was controlled by the concentration gradient of nitrate, and soil water potential gradient from beginning to the 20 cm mark in the horizontal column. However, the velocity of nitrate horizontal was stable beyond 20 cm, where it was controlled by soil matric potential.     

Lead exposure of small herbivorous vertebrates from atmospheric pollution

Concentrations of Pb in livers of willow grouse (Lagopus lagopus), black grouse (Tetrao tetrix), and hare (Lepus timidus) were determined in samples collected during the period 1990-92 from 77 locations distributed across Norway. Our objective was to elucidate the impact of long-range atmospheric transport on the Pb exposure of the animals. The moss Hylocomium splendens was measured for atmospheric Pb deposition and Pb in soil at 60-cm depth was determined to reflect the natural geochemical background at the study locations. Strong positive relationships were found between Pb in liver and atmospheric deposition of Pb for all species and age groups studied. Results indicate that long-range atmospheric transport was the main source of Pb in the animals studied. This conclusion was supported by Pb analysis of typical food plants for the animals. Correlation between Pb in liver and Pb in soil mineral matter was observed only when considering sites with very low impact of atmospheric deposition. Even though the observed liver Pb concentrations may seem low (< or =12 microg g(-1) dw) they approach levels where sub-lethal effects cannot be ignored.