Kinetics of the alkaline hydrolysis of important nitroaromatic co-contaminants of 2,4,6-trinitrotoluene in highly contaminated soils

Until this day, large amounts of TNT and related nitroaromatic compounds are found in soils. To obtain basic data for alkaline hydrolysis of these compounds as a novel remediation technology for contaminated soils, we investigated two soils (HTNT2, ELBP2) from two former ammunition plants in Germany. Hydrolysis was performed at pH 11 and pH 12 by addition of Ca(OH)2. During treatment at pH 12 the TNT content dropped to almost zero, and the content of the aminodinitrotoluenes (2A-4,6DNT, 4A-2,6DNT) and the 2,4-dinitrotoluene (2,4-DNT) decreased by about 75% (only HTNT2) and 63%, respectively. The experimental data were described using a pseudo-first-order kinetic. Furthermore, an increase of 2,6-DNT and trinitrobenzene (TNB) as well as in one case also of TNT was initially noted in addition to hydrolysis, leading temporarily to an increase of their total amounts of up to 147%, 986%, and 122%, respectively. The results demonstrate that alkaline hydrolysis is difficult when nitroaromatics except TNT represent the major contaminants. However, regarding 2,6-DNT and TNB higher reduction rates than calculated were actually achieved by alkaline hydrolysis. In the case that TNT is the only contaminant or if it is accompanied by certain lower concentrated nitroaromatics alkaline hydrolysis is a valuable remediation technology, especially for soils that are highly contaminated.     

N-15 NMR study of the immobilization of 2,4- and 2,6-dinitrotoluene in aerobic compost

Large-scale aerobic windrow composting has been used to bioremediate washout lagoon soils contaminated with the explosives TNT (2,4,6-trinitrotoluene) and RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) at several sites within the United States. We previously used 15N NMR to investigate the reduction and binding of T15NT in aerobic bench-scale reactors simulating the conditions of windrow composting. These studies have been extended to 2,4-dinitrotoluene (2,4DNT) and 2,6-dinitrotoluene (2,6DNT), which, as impurities in TNT, are usually presentwherever soils have been contaminated with TNT. Liquid-state 15N NMR analyses of laboratory reactions between 4-methyl-3-nitroaniline-15N, the major monoamine reduction product of 2,4DNT, and the Elliot soil humic acid, both in the presence and absence of horseradish peroxidase, indicated that the amine underwent covalent binding with quinone and other carbonyl groups in the soil humic acid to form both heterocyclic and non-heterocyclic condensation products. Liquid-state 15N NMR analyses of the methanol extracts of 20 day aerobic bench-scale composts of 2,4-di-15N-nitrotoluene and 2,6-di-15N-nitrotoluene revealed the presence of nitrite and monoamine, but not diamine, reduction products, indicating the occurrence of both dioxygenase enzyme and reductive degradation pathways. Solid-state CP/MAS 15N NMR analyses of the whole composts, however, suggested that reduction to monoamines followed by covalent binding of the amines to organic matter was the predominant pathway.     

Optimization for biodegradation of 2,4,6-trinitrotoluene (TNT) by Pseudomonas putida

In this study, a strain of Pseudomonas putida KP-T202, isolated from the soil in a contaminated site, degraded 2,4,6-trinitrotoluene (TNT). In order to make this biodegradation process commercially feasible and reduce biodegradation time, optimal environmental factors are determined. At an initial concentration of 100 mg/l, TNT was totally degraded within 15 h under aerobic conditions. The optimal conditions for the biodegradation of TNT were found to be 30 degrees C, pH 7, 1% corn steep liquor (CSL), 0.025% NH,CI and 0.1% Tween 80; the reaction rate constant was 0.348 h(-1) These environmental conditions can be used to improve the efficiency of large-scale reactors for the treatment of TNT-contaminated wastewater and soil. In addition, the intermediates were identified as 2-amino-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene, 2,4-dinitrotoluene and 2,6-dinitrotoluene.     

Geochemical modulation of bioavailability and toxicity of nitroaromatic compounds to aquatic plants

Nitroaromatic compounds (NACs) are prominent soil and sediment contaminants that are strongly adsorbed by smectites at extents that depend on hydration properties of the exchangeable cation. Potassium smectites adsorb nitroaromatics much more strongly than calcium smectites, so that adjustment of K+ versus Ca2+ occupation on cation exchange sites in smectites can be used to modulate the retention and release of nitroaromatics. We suggest that this modulation can be used to advantageously manage the bioavailability and toxicity of NACs during bioremedation. We have measured the toxicity of 2,4-dinitrotoluene (2,4-DNT) to duckweed grown in smectite suspensions and utilized Ca2+/K+ exchange to retain or release 2,4-DNT. Retention by potassium smectite reduced bioavailability and hence toxicity to duckweed. Addition of Ca2+ to replace K+ by ion exchange released adsorbed 2,4-DNT, which is toxic to duckweed. So smectites can be used to sequester or release 2,4-DNT predictably and provide means to control bioavailability and environmental toxicity.     

Detoxification of 2,4-dinitrotoluene by transgenic tobacco plants expressing a bacterial flavodoxin

Significant effort has been directed in recent times to the use of plants to extract and detoxify nitroaromatics from polluted industrial facilities. We have explored the possibility of overcoming the phytotoxicity of the highly toxic and recalcitrant nitroderivative 2,4-dinitrotoluene (2,4-DNT) by expressing a cyanobacterial flavodoxin (Fld) in tobacco plants. We demonstrate here that transformants accumulating Fld in plastids display a remarkable increase in the ability to tolerate, take up, and transform 2,4-DNT, as compared to their wild-type siblings. We also show that Fld mediates one-electron reduction of 2,4-DNT in the presence of oxygen and especially in anaerobiosis. Moreover, Fld-loaded chloroplasts are able to convert 2,4-DNT into its aminoderivatives in the presence of light. The results suggest that expression of Fld in landscape plants could facilitate effective cleanup of sites contaminated with this class of pollutants.     

Volatilization and biodegradation of naphthalene in the vadose zone impacted by phytoremediation

The combined remediation mechanisms of volatilization and biodegradation in the vadose zone were investigated for naphthalene remediation at a creosote-contaminated site where a poplar tree-based phytoremediation system has been installed. Concurrent field and laboratory experiments were conducted to study the transport and biodegradation of naphthalene in the vadose zone. Soil gas sampling showed that more than 90% of the naphthalene vapors were biodegraded aerobically within 5-10 cm above the water table during the summer months. Peak naphthalene soil gas concentrations were observed in the late summer, corresponding with peak naphthalene aqueous concentrations and the minimum saturated zone thickness. An analytical solution was developed for vapor transport where the diffusion coefficient and first-order biodegradation rate vary vertically in two discrete zones. First-order aerobic biodegradation rates in laboratory columns using unsaturated site soil ranged from 5 to 28 days(-1) with a mean rate of 11 days(-1). The observed naphthalene mass flux at the source (3.3-22 microg cm(-2) d(-1)) was enhanced by aerobic biodegradation and was greater than the mean observed flux in the abiotic control column and the maximum theoretical mass flux by factors of 7 and 28, respectively.     

Field-deployable sniffer for 2,4-dinitrotoluene detection

A field-deployable instrument has been developed to detect low-level 2,4-dinitrotoluene (2,4-DNT) vapors. The system is based on previously developed artificial nose technology and employs an array of sensory materials attached to the distal tips of an optical fiber bundle. Both semiselective and nonspecific, cross-reactive sensors were employed. Each sensor within the array responds differentially to vapor exposure so the array's fluorescence response patterns are unique for each analyte. The instrument is computationally "trained" to discriminate target response patterns from nontarget and background environments. This detection system has been applied to detect 2,4-DNT, an analyte commonly detected on the soil surface above buried 2,4,6-trinitrotoluene (TNT) land mines, in spiked soil and aqueous and ground samples. The system has been characterized and demonstrated the ability to detect 120 ppb 2,4-DNT vapor in blind (unknown) humidified samples during a supervised field test.     

15N NMR investigation of the covalent binding of reduced TNT amines to soil humic acid,model compounds,and lignocellulose

The five major reductive degradation products of TNT-4ADNT (4-amino-2,6-dinitrotoluene), 2ADNT (2-amino-4,6-dinitrotoluene), 2,4DANT (2,4-diamino-6-nitrotoluene), 2,6DANT (2,6-diamino-4-nitrotoluene), and TAT (2,4,6-triaminotoluene)-labeled with 15N in the amine positions, were reacted with the IHSS soil humic acid and analyzed by 15N NMR spectrometry. In the absence of catalysts, all five amines underwent nucleophilic addition reactions with quinone and other carbonyl groups in the soil humic acid to form both heterocyclic and nonheterocyclic condensation products. Imine formation via 1,2-addition of the amines to quinone groups in the soil humic acid was significant with the diamines and TAT but not the monoamines. Horseradish peroxidase (HRP) catalyzed an increase in the incorporation of all five amines into the humic acid. In the case of the diamines and TAT, HRP also shifted the binding away from heterocyclic condensation product toward imine formation. A comparison of quantitative liquid phase with solid-state CP/MAS 15N NMR indicated that the CP experiment underestimated imine and heterocyclic nitrogens in humic acid, even with contact times optimal for observation of these nitrogens. Covalent binding of the mono- and diamines to 4-methylcatechol, the HRP catalyzed condensation of 4ADNT and 2,4DANT to coniferyl alcohol, and the binding of 2,4DANT to lignocellulose with and without birnessite were also examined.     

Mechanisms affecting the infiltration and distribution of ethanol-blended gasoline in the vadose zone

One- and two-dimensional experiments were conducted to examine differences in the behavior of gasoline and gasohol (10% ethanol by volume) as they infiltrate through the unsaturated zone and spread at the capillary fringe. Ethanol in the spilled gasohol quickly partitions into the residual water in the vadose zone and is retained there as the gasoline continues to infiltrate. Under the conditions tested, over 99% of the ethanol was initially retained in the vadose zone. Depending on the volume of gasoline spilled and the depth to the water table, this causes an increase in the aqueous-phase saturation and relative permeability, thus allowing the ethanol-laden water to drain into the gasoline pool. Under the conditions tested, the presence of ethanol does not have a significant impact on the overall size or shape of the resulting gasoline pool at the capillary fringe. Residual gasoline saturations in the vadose zone were significantly reduced however because of reduced surface and interfacial tensions associated with high ethanol concentrations. The flux of ethanol in the effluent of the column ranged from 1.4 x 10(-4) to 4.5 x 10(-7) g/(cm2 min) with the LNAPL and from 6 x 10(-3) to 3.0 x 10(-4) g/(cm2 min) after water was introduced to simulate rain infiltration. The experimental results presented here illustrate that the dynamic effects of ethanol partitioning into the aqueous phase in the vadose zone create an initial condition that is significantly different than previously understood.     

Persistence and biodegradation of monoethanolamine and 2-propanolamine at an abandoned industrial site

Soil and groundwater samples were collected at the site of a former chemical processing plant in areas impacted by accidental releases of MEA (monoethanolamine) and IPA (2-propanolamine or isopropanolamine). Although their use had ceased ca. 10 years before sample collection, soils collected at contamination sites had MEA concentrations ranging from ca. 400 to 3000 mg/kg and IPA concentrations from ca. 30 to 120 mg/kg. Even though alkanolamines are miscible in water, transport to groundwater was slow, apparently because they are present in soil as bound cations. Only one groundwater sample (near the most highly contaminated soil)from wells directly adjacentto and down-gradient from the contaminated soils had detectable MEA, and none had detectable IPA. However, ammonia was found in the soil samples collected in the MEA-contaminated areas (ca. 500-1400 mg/kg) and the groundwater (80-120 mg/L), as would be consistent with bacterial degradation of MEA to ammonia, followed by transport of ammonia into the groundwater. Counts for bacteria capable of using MEA or IPA as a sole carbon source were ca. 5 x 106 and 1 x 106 (respectively) per gram in uncontaminated site soil, but no such organisms were found in highly contaminated soils. Similarly, bacterial degradation of MEA in slurries of highly contaminated soils was slow, with ca. 8-20 days required for half of the initial concentrations of MEA to be degraded at 20 degrees C and 30-60 days at 10 degrees C. In contrast, bacterial degradation studies using uncontaminated site soils spiked with ca. 1300 mg/L either MEA or IPA showed very rapid degradation of both compounds,with more than 99% degradation occurring in less than 3 days with quantitative conversion to ammonia, followed by slower conversion to nitrite and nitrate. The results obtained in the site soils, the groundwater samples, and from the biodegradation studies demonstrate that MEA and IPA can persist for decades on soil at high (hundreds of mg/kg) concentrations without significant migration into groundwater, despite the fact that they are miscible in water. Since MEA and IPA exist primarily as cations at the pH of site soils, their persistence apparently results from strong binding to soil, as well as inhibition of natural bioremediation in highly contaminated field soils.     

Arsenate adsorption structures on aluminum oxide and phyllosilicate mineral surfaces in smelter-impacted soils

A clearer understanding of arsenic (As) retention and transport in forest soils impacted by copper smelter emissions may reduce risks to human health and provide insight into As behavior in the vadose zone. On Vashon-Maury Island in Puget Sound, As is predominantly associated with the fine (< 63 microm) fraction of surficial soils. X-ray diffraction of oriented samples from the < 2 microm size fraction indicate that clinochlore isthe dominant phyllosilicate. X-ray absorption spectroscopy (XAS) was employed to examine As oxidation state and local coordination environment in impacted soil samples. Arsenic is present as As(V) in tetrahedral coordination with oxygen, associated with aluminum (Al) octahedra in bidentate binuclear (bridging) structures with As-Al distances of 3.15 - 3.16 angstroms. Including multiple scattering (MS) paths derived from the arsenate tetrahedron in esperanzaite significantly improved the match between XAS fine structure (EXAFS) data and models generated from theoretical phase and amplitude functions. The data are interpreted to indicate arsenate adsorption onto poorly crystalline aluminum oxyhydroxides and/or the edges of clinochlore interlayer hydroxyl sheets with constrained geometries causing MS to be important This implies that As initially released from the smelter as particulate As(III) and As(V) oxides was oxidized, dissolved, and adsorbed onto soil minerals and colloids; no evidence for relic arsenic oxide was observed. Physical transport of arsenic oxide particles and As adsorbed on soil colloids may account for limited downward migration of As within the soil column. The oxidizing and mildly acidic pH conditions in the upper vadose zone promote stable sorption complexes; barring substantial changes in soil chemistry, As is not expected to experience significant mobilization.     

Structure-reactivity of naphthenic acids in the ozonation process

Large volumes of oil sands process-affected water (OSPW) are produced in northern Alberta by the surface mining oil sands industry. Naphthenic acids (NAs) are a complex mixture of persistent organic acids that are believed to contribute to the toxicity of OSPW. In situ microbial biodegradation strategies are slow and not effective at eliminating chronic aquatic toxicity, thus there is a need to examine alternative remediation techniques. NAs with multiple rings and alkyl branching are most recalcitrant to microbial biodegradation, but here we hypothesized that these same structural features may lead to preferential degradation in the ozonation process. Total NA degradation increased with increasing pH for commercial NA solutions, suggesting a hydroxyl radical mechanism and that naturally alkaline OSPW would unlikely require pH adjustment prior to treatment. For commercial NAs and OSPW, NAs with more rings and more carbon (and more H atoms) were depleted most rapidly in the process. Relative rate measurements with binary mixtures of model NA compounds not only confirmed this structure reactivity but also indicated that alkyl branching patterns were an additional factor determining NA reactivity. The results demonstrate that ozonation is complementary to microbial biodegradation, and the process remains a promising water reclamation strategy for the oil sands industry.     

Hydrolytic stability of toluene diisocyanate and polymeric methylenediphenyl diisocyanate based polyureas under environmental conditions

Polyureas were prepared by reacting toluene diisocyanate (TDI) or polymeric methylenediphenyl diisocyanate (PMDI) with water under prolonged vigorous mixing at room temperature. Hydrolytic degradation of these (powdered) TDI- and PMDI-based polyureas was studied by measuring the rates of formation of free toluenediamine (TDA) or methylenedianiline (MDA) in water as a function of time by utilizing HPLC. The heterogeneous hydrolysis reactions were carried out in glass reaction tubes under nitrogen with initial polyurea loadings of 2 g/L in deionized water or buffer solution. In the case of TDI-polyurea, concentrations of free 2,4- and 2,6-toluenediamine in water were measured after hydrolysis at 120, 140, and 160 degrees C. The hydrolysis of PMDI-polyurea was carried out at 150, 160, and 170 degrees C, and concentrations of 2,4'-methylenedianiline (2,4'-MDA), 4,4'-methylenedianiline (4,4'-MDA), and 2,4-bis(p-aminobenzyl)aniline were measured. In both cases the rate of formation of diamine was well represented by both a pseudo-first-order reaction and a zero-order reaction. The temperature dependence of rate constants fit Arrhenius behavior. The half-time for hydrolysis of TDI-polyurea at 25 degrees C was calculated to range from about 18,000 to 300,000 years and that of PMDI-polyurea was estimated to range from about 110,000 to 12 million years, depending on the kinetic assumptions made. The half-times for hydrolysis at buffered pH levels of 4, 7, and 9 were within a factor of 2 of those in deionized water. These results are of importance in understanding the fate of polyureas formed in the event of a release of TDI or PMDI into the environment.     

Dynamics of the functional gene copy number and overall bacterial community during microcystin-LR degradation by a biological treatment facility in a drinking water treatment plant

Information is limited on the potential for microcystins (MCs) degradation by carrier-attached biofilms obtained in winter that were not exposed to detectable levels of MCs in the preceding months. Under controlled laboratory conditions, we confirmed that microcystin-LR (MCLR) was effectively biodegraded within 5.5 days in cultures of the biofilm sampled in winter. Quantitative polymerase chain reaction (qPCR) assays revealed that seasonal variations in the MCLR-degradation potential of the biofilm were closely related to the initial MCLR-degrader population in the biofilm. Indigenous MCLR-degraders in the biofilm could accumulate by exposure to natural MCLR in the water column, accelerating MCLR-degradation. The qPCR assay suggested that MCLR may be a primary substrate for the degraders in the presence of another labile organic carbon associated with the biofilm under the present study conditions. qPCR and PCR-denaturing gradient gel electrophoresis (DGGE) for 16S rDNA demonstrated that the overall bacterial population from the winter biofilm rapidly increased with the MCLR-degrader population and remained stable after day 3.5, while the overall bacterial community structure shifted throughout the entire biodegradation period. This study is important to the in-depth understanding of microbial degradation of MCs and could facilitate the bioremediation of MCs in polluted habitats.     

Development of engineered natural organic sorbents for environmental applications. 4. Effects on biodegradation and distribution of pyrene in soils

The effects of engineered natural organic amendments on the biodegradation and distribution of pyrene in soils were assessed. Pyrene was aged for 105 days in soils amended with either raw or superheated water (SHW)-processed MI peat or soybean stalks, and then subjected to biodegradation with specifically selected microorganisms for 130 days. Initial rates of pyrene mineralization in the soils were increased by addition of raw MI peat, but markedly decreased by additions of SHW-processed MI peat and both processed and raw soybean stalks. Pyrene sorbed by the processed organic sorbents was, however, slowly but steadily degraded by microorganisms over a greater than 4-month test period. Pyrene distributions in the soils were examined by sequential extractions of samples before and after biodegradation. Fractions of pyrene extracted readilywith water or water/methanol mixtures were decreased substantially in both soils bythe addition of processed amendments, while the nonextractable fractions associated with humic and fulvic acids and humin were increased markedly. The results demonstrate that SHW-processed amendments effectively reduce the ecological and human availability and aqueous phase extractability of organic contaminants while facilitating their steady microbial degradation and eventually complete remediation.     

Compositional evolution of the emplaced fuel source in the vadose zone field experiment at Airbase Verløse, Denmark

A field experiment was performed in a sandy vadose zone, studying the fate of an emplaced fuel-NAPL source, composed of 13 hydrocarbons and a tracer. The UNIFAC model was used to testthe nonideal behavior of the source, and the numerical model MIN3P was used for assessing the effect of biodegradation on source evolution. The diffusive loss to the surrounding vadose zone and the atmosphere created temporary gradients in mole fractions of the individual compounds within the source NAPL. The evolution of the source composition corresponded in general with expectations based on Raoult's Law, with the exception thatthe mole fractions of aromatic compounds in the source NAPL decreased faster than fractions of aliphatic compounds of similar volatility. Calculation of activity coefficients (y) using the UNIFAC model implied nonideal conditions, with composition-dependent gammas different from 1. Positive deviations were calculated for the aromatic compounds. The effect of biodegradation on source depletion, evaluated by numerical modeling, was greater for the aromatic as compared to the aliphatic compounds. Hence, the faster depletion of the aromatic relative to aliphatic compounds of similar volatility is both a result of the nonideality of the mixture and a result of partitioning and biodegradation in the pore-water. Vapor concentrations of the compounds in the source were in reasonable agreement with predictions based on the modified Raoult's Law with the UNIFAC predicted gammas and the NAPL composition for the most volatile compounds. For the less volatile compounds, the measured vapor concentrations were lower than predicted with the largest deviations for the least volatile compounds. This field experiment illustrated that nonideal behavior and bioenhanced source depletion need to be considered at multicomponent NAPL spill sites.     

Identification of UV photoproducts and hydrolysis products of butachlor by mass spectrometry

The photoproducts and hydrolysis products of butachlor in water were identified by gas chromatography/mass spectrometry. When exposed to UV light, butachlor in aqueous solution was rapidly degraded, giving at least 11 photoproducts as a result of dechlorination with subsequent hydroxylation or cyclization processes. The chemical structures of nine degradation compounds were identified on the basis of mass spectrum interpretation and literature data. Major photoproducts are identified as 8-ethyl-1-butoxymethyl-4-methyl-2-oxo-1,2,3,4-tetrahydro-quinoline, 2-hydroxy-2',6'-diethyl-N-(butoxymethyl) acetanilide, and a compound related to butachlor. Minor photoproducts are identified as 2,6-diethylaniline; 1-acetyl-7-ethylindole; N-(2,6-diethylphenyl)-N-(butoxymethyl)acetamide; 2-oxo-N-(2,6-diethyl-phenyl)-N-(butoxymethyl)acetamide; 1-hydroxyacetyl-2-butoxyl-3-methyl-7-ethylindole; 1-acetyl-2-butoxyl-3-methyl-7-ethylindole; and two compounds with the chemical structure unknown. The half-lives of butachlor UV photolysis were 7.54, 10.56, and 12.22 min in deionized water, river water, and paddy water, respectively. The half-lives of butachlor hydrolysis at pH 4, 7, and 10 were 630, 1155, and 1155 days at 25 +/- 1 degrees C, respectively. A hydrolysis product at pH 4 was identified by GC/MS to be 2-hydroxy-2',6'-diethyl-N-(butoxymethyl) acetanilide.     

Aerobic biodegradation of hopanes and other biomarkers by crude oil-degrading enrichment cultures

The degradation of petroleum biomarkers was examined using mixed cultures of microorganisms enriched from surface soils at four different hydrocarbon-contaminated sites. These cultures degraded C30 17alpha(H),21beta(H)-hopane and the C31-C34 extended hopanes in Bonny Light crude oil after 21 days of incubation at 30 degrees C. The C35 extended hopanes were conserved, and no 25-norhopanes were detected during the incubation. Denaturing gradient gel electrophoresis (DGGE) analysis of the enrichment cultures demonstrated distinct microbial community profiles. Additional studies with the LC culture demonstrated a consistent biomarker degradation pattern after growth on three crude oils: a Nigerian Bonny Light crude, a Venezuelan crude oil, and Alaskan North Slope 521. The onset of biomarker degradation was observed between days 14 and 21 but only at 30 degrees C and at oil concentrations below 6 mg/mL. The biomarker profiles following degradation by these enrichment cultures are similar to numerous field observations and may represent the dominant biodegradation pattern found in many hydrocarbon-contaminated aerobic surface environments.     

Degradation of carbendazim and 2,4-dichlorophenoxyacetic acid by immobilized consortium on loofa sponge

A fungicide, carbendazim (methyl-2-benzimidazole carbamate; MBC), and a herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), could be simultaneously degraded by a microbial consortium obtained from several soil samples in Japanese paddy fields with enrichment continuous culture. The degradation ability of the consortium was increased by immobilization on loofa (Luffa cylindrica) sponge in comparison with that of free-living consortium. MBC and 2,4-D were completely degraded within 5.5 d and 1.5 d, respectively. The toxicity of these pesticides in culture medium to Daphnia magna was reduced by treatment with the consortium corresponding to their degradation. The degradation ability of the immobilized consortium at pHs in the range from 6 to 9, at temperatures from 15 degrees C to 37 degrees C, and at low NH(4)(+)-N concentrations (1-10 mg/l) was not very different from that under the basal condition (pH 7, 30 degrees C, 424 mg/l NH(4)(+)-N and 472 mg/l PO(4)(3)(-)-P). At low pHs 4 and 5, the ability was significantly lower than that of the basal condition. Moreover, incubation at low PO(4)(3)(-)-P concentrations (1-10 mg/l) caused a decrease in pH at which the degradation ability also became lower. However, the ability in this culture completely recovered when pH was adjusted to 7 or the phosphate concentration was increased to the basal level. Analysis by denaturing gradient gel electrophoresis (DGGE) showed the whole population of the consortium became faint at low pH or low phosphate concentrations but became distinct again as much as those under the basal conditions, indicating that the decrease in the degradation ability caused by low pH was due to that whole population of the consortium underwent serious damage but could survive and recover. These results suggest the immobilized consortium on loofa sponge is a promising material for bioremediation of polluted water with these pesticides in paddy fields.     

Use of potassium formate in road winter deicing can reduce groundwater deterioration

We present here an aquifer scale study on the fate of potassium formate, an alternative, weakly corrosive deicing agent in soil and subsurfaces. Potassium formate was used to deice a stretch of a highway in Finland. The fate of the formate was examined by monitoring the groundwater chemistry in the underlying aquifer of which a conceptual model was constructed. In addition, we determined aerobic and anaerobic biodegradation rates of formate at low temperatures (-2 to +6 degrees C) in soil microcosms. Our results show that the formate did not enter the saturated zone through the thin vadose zone; thus, no undesirable changes in the groundwater chemistry were observed. Furthermore, the conceptual model explained the distribution of chloride in the aquifer used in deicing for the past 30 years. We recorded mineralization potential up to 97% and up to 17% within 24 h under aerobic and anaerobic conditions, respectively, in the soil and subsurface samples obtained from the site. This demonstrates that biodegradation in the topsoil layers was responsible for the removal of the formate. We conclude that the use of potassium formate can potentially help diminish the negative impacts of road winter deicing on groundwater without jeopardizing traffic safety.