Assessment of metal availability in smelter soil using earthworms and chemical extractions

Chemical immobilization is a relatively inexpensive in situ remediation method that reduces soil contaminant solubility, but the ability of this remediation treatment to reduce heavy metal bioavailability and ecotoxicity to soil invertebrates has not been evaluated. Our objectives were to (i) assess the ability of chemical immobilization amendments (municipal sewage sludge biosolids and rock phosphate) to reduce metal bioavailability and toxicity in a toxic metal-contaminated smelter soil and (ii) evaluate soil extraction methods using Ca(NO3)2 solution or ion-exchange membranes coated with diethylenetriaminepentaacetic acid (DTPA) as surrogate measures of metal bioavailability and ecotoxicity. We treated a soil contaminated by Zn and Pb milling and smelting operations and an uncontaminated control soil with lime-stabilized municipal biosolids (LSB), rock phosphate (RP), or anaerobically digested municipal biosolids (SS) and evaluated lethality of the remediated soils to earthworm (Eisenia fetida Savigny). Lime-stabilized municipal biosolids was the only remediation amendment to successfully immobilize lethal levels of Zn in the smelter soil (14-d cumulative mortality < or = 15%). Calcium nitrate-extractable Zn in the lethal Zn smelter soil-amendment combinations was 11.5 to 18.2 mmol/kg, compared with the nonlethal LSB amended soil (0.62 mmol/kg). The Ca(NO3)2-extractable Zn-based median lethal concentration (LC50) of 6.33 mmol/kg previously developed in Zn-spiked artificial soils was applicable in the remediated smelter soils despite a 14-fold difference in total Zn concentration. Chelating ion-exchange membrane uptake among the soils was highly variable (mean CV = 39%) compared with the Ca(NO3)2-extraction (mean CV = 1.9%) and not well related to earthworm toxicity.     

Immobilization of cesium-137 and uranium in contaminated sediments using soil amendments

Batch and dynamic leaching methods were used to evaluate the effectiveness of hydroxyapatite (HA), illite, and zeolite, alone and in combination, as soil additives for reducing the migration of cesium-137 (137Cs+) and uranium (U) from contaminated sediments. Amendment treatments ranging from 0 to 50 g kg(-1) were added to the sediment and equilibrated in 0.001 M CaCl2. After equilibration, the treatment supernatants were analyzed for 137Cs+, U, PO4, and other metals. The residual sediments were then extracted overnight using one of the following: 1.0 M NH4Cl, 0.5 M CaCl2, or the Toxicity Characteristic Leaching Procedure (TCLP) extractant. Cesium was strongly sorbed to the contaminated sediments, presumably due to interlayer fixation within native illitic clays. In fact, 137Cs+ was below detection limits in the initial equilibration solutions, the CaCl2 extract, and the TCLP solution, regardless of amendment. Extractants selective for interlayer cations (1.0 M NH4Cl) were necessary to extract measurable levels of 137Cs+. Addition of illitic clays further reduced Cs+ extractability, even when subjected to the aggressive extractants. Zeolite, however, was ineffective in reducing Cs+ mobility when subjected to the aggressive extractants. Hydroxyapatite was less effective than illite at reducing NH4+-extractable Cs+. Hydroxyapatite, and mixtures of HA with illite or zeolite, were highly effective in reducing U extractability in both batch and leaching tests. Uranium immobilization by HA was rapid with similar final U concentrations observed for equilibration times ranging from 1 h to 30 d. The current results demonstrate the effectiveness of soil amendments in reducing the mobility of U and Cs+, which makes in-place immobilization an effective remediation alternative.     

Endosulfan transport: I. Integrative assessment of airborne and waterborne pathways

To reduce endosulfan (C9H6O3Cl6S; 6,7,8,9,10,10-hexachloro-1,5, 5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin 3-oxide) contamination in rivers and waterways, it is important to know the relative significances of airborne transport pathways (including spray drift, vapor transport, and dust transport) and waterborne transport pathways (including overland and stream runoff). This work uses an integrated modeling approach to assess the absolute and relative contributions of these pathways to riverine endosulfan concentrations. The modeling framework involves two parts: a set of simple models for each transport pathway, and a model for the physical and chemical processes acting on endosulfan in river water. An averaging process is used to calculate the effects of transport pathways at the regional scale. The results show that spray drift, vapor transport, and runoff are all significant pathways. Dust transport is found to be insignificant. Spray drift and vapor transport both contribute low-level but nearly continuous inputs to the riverine endosulfan load during spraying season in a large cotton (Gossypium hirsutum L.)-growing area, whereas runoff provides occasional but higher inputs. These findings are supported by broad agreement between model predictions and observed typical riverine endosulfan concentrations in two rivers.     

Olfactory response to mushroom composting emissions as a function of chemical concentration

Odor pollution is a major problem facing mushroom [Agaricus bisporus (Lange) Imbach] compost production. Techniques for quantifying mushroom composting odors are needed to assess the effectiveness of odor control measures. Odor samples were obtained in nalophane bags from 11 mushroom composting sites. Samples were collected 0.2 m downwind from the pre-wetting heaps (aerated or unaerated) of raw composting ingredients (wheat straw, poultry and horse manures, and gypsum) and subsequent Phase I composting windrows or aerated tunnels. The odor concentrations (OCs) of the samples were assessed using serial dilution olfactometry and the chemical composition of the samples was determined using gas chromatography-mass spectrometry (GC-MS), both 24 h after sampling. Gas detector tubes were used for on-site measurement of gaseous compounds. Odorants that exceeded their published olfactory detection thresholds by the greatest order of magnitude, in decreasing order, were: H2S, dimethyl sulfide (DMS), butanoic acid, methanethiol, and trimethylamine. Concentrations of NH3 were not significantly correlated with OC, and they were not significantly affected by the use of aeration. Aeration reduced the OC and the combined H2S + DMS concentrations by 87 and 92%, respectively. There was a very close correlation (r = 0.948, P < 0.001) between the OC of bag samples and the combined H2S + DMS concentrations, measured on-site with detector tubes. This relationship was unaffected by the NH3 concentration or the type of compost: aerated or unaerated, pre-wet or Phase I, poultry manure-based or horse and poultry manure-based compost. Prediction of the OC will enable rapid and low-cost identification of odor sources on mushroom composting sites.     

Removal of herbicides from liquid media by fungi isolated from a contaminated soil

Fungi were isolated from soil samples corresponding to pesticide-contaminated soil (CS) and noncontaminated soil (NCS) in the Annaba vicinity (Algeria) and identified. The number of isolates obtained from CS and NCS were 263 and 288, respectively. The most frequent species (Aspergillus fumigatus, A. niger, A. terreus, Absidia corymbifera, and Rhizopus microsporus var microsporus) were not sensitive to the pesticides. The growth of the genus Trichoderma was inhibited by the pesticides, while genera Absidia and Fusarium were stimulated. The 53 species isolated were assayed for their ability to remove metribuzin from liquid medium. Only Botrytis cinerea from NCS and Sordaria superba and Absidia fusca from CS removed more than 50% of the compound after 5 d. Metamitron was very resistant. Among the 21 species tested, only Alternaria solani (from NCS), Drechslera australiensis (from CS and NCS), and Absidia fusca (from CS) reduced the concentration in the medium more than 10% (10-16%). Twelve species were grown with linuron, seven of them were inefficient in removing this compound. The two strains of Sordaria macrospora yielded 22 to 25% depletion, while Botrytis cinerea depleted linuron almost completely. Among the 31 species assayed for their ability to eliminate metobromuron, Botrytis cinerea (from CS and NCS) depleted almost completely the chemical from the medium. Rhizopus oryzae and Absidia fusca from CS removed 40 and 47% of the compound, respectively. No systematic relationships were observed between the soil contamination and herbicide elimination capacities of soil fungi. Absidia fusca and Botrytis cinerea were particularly interesting for bioremediation purposes because they were able to transform efficiently three of the four compounds assayed.     

Sorption of polycyclic aromatic compounds to humic and fulvic acid HPLC column materials

Two different humic acids (HA) and a fulvic acid (FA) were chemically immobilized to a high performance liquid chromatography (HPLC) silica column material. The immobilization was performed by binding amino groups in HA/FA to the free aldehyde group in glutardialdehyde attached to the silica gel. The HPLC column materials were compared with a blank column material made by applying the same procedure but without immobilizing HA or FA. Also, a column was made by binding carbonyl groups in HA to amino groups attached to the silica gel. The humic substances were selected to secure appropriate variation of their structural features. The retention factors of 45 polycyclic aromatic compounds (PAC) to the four columns were determined by HPLC. The advantage of the technique is a large number of compounds can easily be studied. The binding procedure does not appear to cause a drastic selection between the HA molecules. The k' values obtained for the two Aldrich HA columns agree in general reasonably. The retention or sorption of the compounds increased with the size of the PAC and the number of lipophilic substituents, but decreased when polar substituents were present. The PAC retention was much stronger to the two HA columns than to the FA and blank column, both for hydrophobic polycyclic aromatic hydrocarbons (PAH) and the polar PAC. Other factors impacting the PAC binding may be specific interactions with HA and the ionic strength of the aqueous phase. The technique has been applied to do direct determinations of Koc.     

The relationship between microbial carbon and the resource quality of soil carbon

The biological health of soil is an important aspect of soil quality because of the many critical functions performed by organisms in soil. Various indicators of soil quality have been proposed, but measurements of microbial biomass are most commonly used. During decomposition of plant residues in soil the relative intensities of the O-alkyl-C signal decreases and the alkyl-C signal increases in nuclear magnetic resonance (NMR) spectra. This leads to the suggestion that the alkyl-C to O-alkyl-C ratio of a soil may indicate the degree of decomposition. Consequently, the overall resource quality of soil C as a substrate for heterotrophic microorganisms may be inversely related to the alkyl-C to O-alkyl-C ratio. Our hypothesis is that a relationship exists between the size of the soil microbial community (microbial biomass) and the quality of soil carbon as a resource for microorganisms. New data have been combined with previously published data to show that there was a significant, negative correlation between the biomass C to total C (Cmic, to Corg) ratio and the alkyl-C to O-alkyl-C ratio (p < 0.01), which supports our hypothesis.     

Bioremediation of residual fertilizer nitrate: II. Soil redox potential and soluble iron as indicators of soil health during treatment

The prospect of using wastewater containing high loads of soluble organic matter (OM) for removing residual agricultural chemicals (fertilizer, pesticide, or herbicide) in farm soil, although promising, could have adverse effects on soil agricultural quality as a result of development of redoximorphic features in the soil profile. In this study, the effect of organic carbon supplement for bioremediation of residual fertilizer nitrate on soil properties, redox potential (Eh), pH, and metal ion mobilization was studied using sandy soils packed in columns. The study was included in a general project, described elsewhere (Ugwuegbu et al., 2000), undertaken to evaluate use of controlled water table management (WTM) systems to supply organic carbon for creating a reduced environment conducive to denitrification of residual fertilizer nitrate leaching from the farm to subsurface water. The columns were subjected to subirrigation with water containing soluble organic carbon in the form of glucose. The work was carried out in two experimental setups and the long-term effect of a range of glucose concentrations on the Eh, pH, and soluble levels of Fe and Mn was investigated. From the results obtained, it could be concluded that excessive organic carbon supplement to soil can have adverse effects on soil quality and that Eh and soluble Fe are the two most practical parameters for monitoring soil health during treatment of farm chemicals.     

Phytoremediation of aged petroleum sludge: effect of irrigation techniques and scheduling

The use of higher plants to accelerate the remediation of petroleum contaminants in soil is limited by, among other factors, rooting depth and the delivery of nutrients to the microsites at which remediation occurs. The objective of this study was to test methods of enhancing root growth and remediation in the subsurface of a contaminated petroleum sludge. The phytoremediation of highly contaminated petroleum sludge (total petroleum hydrocarbons >35 g kg(-1) was tested in the greenhouse as a function of the frequency and the depth of irrigation and fertilization. Water and dissolved plant nutrients were added to the soil surface or at a depth of 30 cm, either daily or weekly. Equivalent quantities of water and nutrients were added in all cases. Daily irrigation at a depth of 30 cm invoked greater root growth and enhanced contaminant degradation relative to all other treatments. In the absence of plants, residual concentrations of petroleum hydrocarbons after 7 mo were higher than with plants. The presence of plant roots clearly improved the physical structure of the soil and increased microbial populations. Thus, the plant roots in conjunction with daily additions of soluble N and P appeared to enhance oxygen transport to greater depths in the soil, stimulate petroleum-degrading microorganisms, and provide microbial access to soil micropores. Subsurface irrigation with frequent, small amounts of water and nutrients could significantly accelerate phytoremediation of field soils contaminated with petroleum hydrocarbons.     

Assessment of the risk of phosphorus loading due to resuspended sediment

Resuspension is a multiphase phenomenon where suspended solids encounter water layers differing in physico-chemical properties that affect the reactions of phosphorus (P). The role of resuspended sediment as a sink or source of dissolved P was determined in a laboratory study of P desorption-sorption equilibria. Gradual mixing was simulated using decreasing solid concentrations and varying environmental conditions (pH, redox, ionic strength). To describe the P exchange when the particles encounter dissimilar water layers, the extent of P sorption to or desorption from solids was expressed as a function of P concentration in the bath solutions. The equilibrium phosphorus concentration (EPC), at which there is no net P release from or retention to the particles, proved to be a suitable parameter for assessment of P load risk. Under oxic conditions at pH 7, commonly prevailing in lakes, the EPC values ranged from 11 to 27 microg P L(-1). The larger the water volume the suspended material was mixed with, the higher the P concentration, allowing desorption to occur. As for chemical factors affecting P mobilization, EPC followed the order: pH 7 < pH 7 anoxic < pH 9. A separate extraction experiment revealed that elevated pH enhanced P mobilization more as the concentration of solids decresed. The results demonstrate that high pH (a common characteristic in eutrophic lakes during summer), when linked with intensive resuspension, may markedly increase the internal P loading risk. As for the risk assessment, the quantification of the internal P loading would be improved by isotherm studies combined with field observations.