Composting duck excreta enriched wood shavings: C and N transformations and bacterial pathogen reductions

Composting of agricultural and domestic wastes is used increasingly to reduce weight, volume, and odor; destroy animal and plant pathogens; and improve the quality of end-products to be used as soil amendments and growth substrates. The objective of this study was to investigate the transformation of C and N and the survival of bacterial populations and pathogenic bacteria during in-vessel composting of duck excreta enriched wood shavings. Two feedstocks, collected on different dates, were composted (C1 and C2) in an enclosed hall system equipped with an electromechanical turner. Temperature was continuously recorded, whereas moisture content and bacterial counts were determined twice a week. Data showed that, although the N content of C2 was only half of that of C1, both materials were fully biostabilized at the end of the composting period as indicated by extractable lipid ratios. In the compost with the low C/N ratio (C1), all bacterial populations were eliminated, whereas fecal streptococci, total coliforms, and gram-negative bacteria were still present in C2 at the end of the composting period. Our results emphasize that the composting of manures and other organic wastes needs to be properly managed to stabilize C and N and to eliminate or reduce bacterial populations.     

Aromatic hydrocarbon growth from indene

Aromatic hydrocarbon growth from indene (C9H8), which contains the five-membered ring cyclopentadienyl moiety, was investigated experimentally in a 4 s flow reactor over a temperature range 650-850 degrees C. Major products observed were three C18H12 isomers (chrysene, benz[a]anthracene and benzo[c]phenanthrene), two C17H12 isomers (benzo[a]fluorene and benzo[b]fluorene), and two C10H8 isomers (naphthalene and benzofulvene). Reaction pathways to these products are proposed. Indenyl radical addition to indene produces a resonance-stabilized radical intermediate which further reacts by one of two routes. Rearrangement by intramolecular addition produces a bridged structure that leads to the formation of C17H12 and C10H8 products. Alternatively, beta scission produces biindenyl, which leads to the formation of C18H12 products by a ring condensation mechanism analogous to that proposed for cyclopentadiene-to-naphthalene conversion. Temperature dependencies of both the partitioning between these two routes and the product isomer distributions are consistent with thermochemical modeling using semi-empirical molecular orbital methods. The results further illustrate the role of resonance-stabilized radical rearrangement in aromatic growth and condensation of systems with cyclopentadienyl moieties.     

Influence of diesel concentration on the fate of phenanthrene in soil

The aim of this study was to investigate the influence of diesel on the loss and bioavailability of soil-associated [14C]phenanthrene with time. In addition, the temporal development of phenanthrene catabolic activity and the impact of co-contaminant mixtures on the soil microflora were also assessed. With respect to compound fate, the results suggested that competitive effects between dissimilar co-contaminants did influence [14C]phenanthrene loss. Where diesel was present at a concentration of 0, 20, 200 and 2000 mg kg(-1), increased phenanthrene loss was observed with increasing diesel concentrations. In the 20,000 mg kg(-1) diesel treatment, however, a significantly higher amount of the initial [14C]activity remained after 225 days. Furthermore, initial degradation of phenanthrene in this treatment was retarded as a result of repressed phenanthrene catabolic activity. These results were complemented by a 4-fold increase in total culturable bacterial cell numbers in the 20,000 mg kg(-1) treatment when compared with the 2000 mg kg(-1) after 225 days of incubation time.     

Fate of nitrogen during composting of chicken litter

Chicken litter (a mixture of chicken manure, wood shavings, waste feed, and feathers) was composted in forced-aeration piles to understand the changes and losses of nitrogen (N) during composting. During the composting process, the chemical [different N fractions, organic matter (OM), organic carbon (C), and C:N ratio], physical, and microbial properties of the chicken litter were examined. Cumulative losses and mass balances of N and organic matter were also quantified to determine actual losses during composting. The changes in total N concentration of the chicken litter piles were essentially equal to those of the organic N. The inorganic N concentrations were low, and that organic N was the major nitrogenous constituent. The ammonium (NH(4)(+))-N concentration decreased dramatically during first 35 days of composting. However, the rapid decrease in NH(4)(+)-N during composting did not coincide with a rapid increase in (NO(3)(-)+NO(2)(-))-N concentration. The concentration of (NO(3)(-)+NO(2)(-))-N was very low (<0.5 g kg(-1)) at day 0, and this level remained unchanged during the first 35 days of composting suggesting that N was lost during composting. Losses of N in this composting process were governed mainly by volatilization of ammonia (NH(3)) as the pile temperatures were high and the pH values were above 7. The narrow C:N ratio (<20:1) have also contributed to losses of N in the chicken litter. The OM and total organic C mass decreased with composting time. About 42 kg of the organic C was converted to CO(2). On the other hand, 18 kg was lost during composting. This loss was more than half (59%) of the initial N mass of the piles. Such a finding demonstrates that composting reduced the value of the chicken litter as N fertilizer. However, the composted chicken contained a more humified (stabilized) OM compared with the uncomposted chicken litter, which would enhance its value as a soil conditioner.     

Dendroremediation of trinitrotoluene (TNT) Part 2: Fate of radio-labelled TNT in trees

BACKGROUND, AIM AND SCOPE: Problems of long-term existence of the environmental contaminant 2,4,6-trinitrotoluene (TNT) and necessities for the use of trees ('dendroremediation') in sustainable phytoremediation strategies for TNT are described in the first part of this paper. Aims of the second part are estimation of [14C]-TNT uptake, localisation of TNT-derived radioactivity in mature tree tissues, and the determination of the degree of TNT-degradation during dendroremediation processes. METHODS: Four-year-old trees of hybrid willow (Salix spec., clone EW-20) and of Norway spruce (Picea abies) were cultivated in sand or ammunition plant soil (AP-soil) in wick supplied growth vessels. Trees were exposed to a single pulse application with water solved [U-14C]-TNT reaching a calculated initial concentration of 5.2 mg TNT per kg dry soil. Two months after application overall radioactivity and extractability of 14C were determined in sand/soil, roots, stem-wood, stem-bark, branches, leaves, needles, and Picea May sprouts. Root extracts were analysed by radio TLC. RESULTS: 60 days after [14C]-TNT application, recovered 14C is accumulated in roots (70% for sand variants, 34% for AP-soil variant). 15-28% of 14C remained in sand and 61% in AP-soil. 3.3 to 14.4% of 14C were located in aboveground tree portions. Above-ground distribution of 14C differed considerably between the angiosperm Salix and the gymnosperm Picea. In Salix, nearly half of above-ground-14C was detected in bark-free wood, whereas in Picea older needles contained most of the above-ground-14C (54-69%). TNT was readily transformed in tree tissue. Approximately 80% of 14C was non-extractably bound in roots, stems, wood, and leaves or needles. Only quantitatively less important stem-bark of Salix and Picea and May shoots of Picea showed higher extraction yields (up to 56%). DISCUSSION: Pulse application of [14C]-TNT provided evidence for the first time that after TNT-exposure, in tree root extracts, no TNT and none of the known metabolites, mono-amino-dinitrotoluenes (ADNT), diaminonitrotoluenes (DANT), trinitrobenzene (TNB) and no dinitrotoluenes (DNTs) were present. Extractable portions of 14C were small and contained at least three unknown metabolites (or groups) for Salix. In Picea, four extractable metabolites (or groups) were detected, where only one metabolite (or group) seemed to be identical for Salix and Picea. All unknown extractables were of a very polar nature. CONCLUSIONS: Results of complete TNT-transformation in trees explain some of our previous findings with 'cold analytics', where no TNT and no ADNT-metabolites could be found in tissues of TNT-exposed Salix and Populus clones. It is concluded that 'cold' tissue analysis of tree organs is not suited for quantitative success control of phytoremediation in situ. RECOMMENDATIONS AND OUTLOOK: Both short rotation Salicaceae trees and conifer forests possess a dendroremediation potential for TNT polluted soils. The degradation capacity and the large biomass of adult forest trees with their woody compartments of roots and stems may be utilized for detoxification of soil xenobiotics.     

Using Radiocarbon to Apportion Sources of Polycyclic Aromatic Hydrocarbons in Household Soot

To determine whether polycyclic aromatic hydrocarbons (PAHs) in household soot were derived from the combustion of scrap wood or creosote that was impregnated in the wood (or some combination of both), the molecular composition and radiocarbon ( 14 C) content of the total carbon and several PAHs in the soot was investigated. The 5730-year half-life of 14 C makes it an ideal marker for identifying creosote-derived PAHs ( 14 C-free) versus those derived from the combustion of wood (contemporary 14 C). The 14 C abundance of phenanthrene, fluoranthene, pyrene, and retene was determined by accelerator mass spectrometry after solvent extraction and purification by preparative capillary gas chromatography. The molecular analysis (presence of retene and 1,7-dimethylphenanthrene) and bulk 14 C content (contemporary) of the soot indicated that wood combustion was a strong source of carbon to the soot. The 14 C of retene in two soot samples was also contemporary, indicating that it was derived from the combustion of the scrap wood. These results are consistent with previous work that has suggested that retene is an excellent marker of wood combustion. However, the 14 C content of phenanthrene, fluoranthene, and pyrene in one soot sample was much lower and revealed that these compounds had a mixed creosote and wood source. Using an isotopic mass balance approach, we estimate that 40 to 70% of phenanthrene, fluoranthene, and pyrene were derived from the combustion of the scrap wood. The results of this study show that molecular marker and bulk 14 C analysis can be potentially misleading in apportioning sources of every PAH, and that molecular-level 14 C analysis of PAHs can be a powerful tool for environmental forensics.     

Metabolism of aromatic hydrocarbons by the filamentous fungus Cyclothyrium sp

The metabolism of biphenyl, naphthalene, anthracene, phenanthrene, pyrene and benzo[a]pyrene by Cyclothyrium sp. CBS 109850, a coelomycete isolated for the first time in Brazil from industrially polluted estuarine sediment, was studied. The metabolites were extracted and separated by high performance liquid chromatography (HPLC) and characterized by UV spectral analyses and mass, and proton nuclear magnetic resonance ((1)H NMR) spectrometry. Cyclothyrium sp. transformed biphenyl to 4-hydroxybiphenyl and anthracene to anthracene trans-1,2-dihydrodiol. This isolate metabolized 90% of [9-(14)C]phenanthrene, producing phenanthrene trans-9,10-dihydrodiol as a major metabolite, phenanthrene trans-3,4-dihydrodiol, 1-hydroxyphenanthrene, 3-hydroxyphenanthrene, 4-hydroxyphenanthrene, and a novel metabolite, 2-hydroxy-7-methoxyphenanthrene. Circular dichroism spectra analyses indicated that the major enantiomers of phenanthrene trans-9, 10-dihydrodiol, phenanthrene trans-3,4-dihydrodiol and pyrene trans-4,5-dihydrodiol, a pyrene metabolite produced previously by Cyclothyrium sp. CBS 109850, were predominantly in the (R,R) configuration, revealing a high stereoselectivity for initial monooxygenation and enzymatic hydration of phenanthrene and pyrene by Cyclothyrium sp. CBS109850. The results also show a high regioselectivity since the K-regions of phenanthrene and pyrene were the major sites of metabolism.     

Degradation of CL-20 by white-rot fungi

In previous studies, we found that the emerging energetic chemical, CL-20 (C6H6N12O12, 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane), can be degraded following its initial denitration using both aerobic and anaerobic bacteria. The C and N mass balances were not determined due to the absence of labeled starting compounds. The present study describes the degradation of the emerging contaminant by Phanerochaete chrysosporium using ring-labeled [15N]-CL-20 and [14C]-CL-20. Ligninolytic cultures degraded CL-20 with the release of nitrous oxide (N2O) in amounts corresponding to 45% of the nitrogen content of CL-20. When ring-labeled [15N]-CL-20 was used, both 14N14NO and 15N14NO were observed, likely produced from -NO2 and N-NO2, respectively. The incubation of uniformly labeled [14C]-CL-20 with fungi led to the production of 14CO2 (> 80%). Another ligninolytic fungus, Irpex lacteus, was also able to degrade CL-20, but as for P. chrysosporium, no early intermediates were observed. When CL-20 was incubated with manganese peroxidase (MnP), we detected an intermediate with a [M-H]- mass ion at 345 Da (or 351 and 349 Da when using ring-labeled and nitro-labeled [15N]-CL-20, respectively) matching a molecular formula of C6H6N10O8. The intermediate was thus tentatively identified as a doubly denitrated CL-20 product. The concomitant release of nitrite ions (NO2-) with CL-20 degradation by MnP also supported the occurrence of an initial denitration prior to cleavage and decomposition.     

Tracing the transformation of labelled [1-13C]phenanthrene in a soil bioreactor

[1-(13)C]-labelled phenanthrene was incubated in a closed bioreactor to study the flux and biotransformation of polycyclic aromatic hydrocarbon (PAH) in contaminated soils on a bulk and molecular level. The degradation of extractable phenanthrene was observed by GC-MS measurements and the mineralisation was monitored by (13)CO(2) production. The transformation of the (13)C-label into non-extractable soil-bound residues was determined by carbon isotopic measurements. With these data we were able to calculate a carbon budget of the (13)C-label. Moreover, the chemical structure of non-extractable bound residues was characterised by applying selective chemical degradation reactions to cleave xenobiotic subunits from the macromolecular organic soil matrix. The obtained low molecular weight products yielded (13)C-labelled compounds which were identified using IRM (isotope ratio monitoring)-GC-MS and structurally characterised with GC-MS. Most of the (13)C-labelled products obtained by chemical degradation of non-extractable bound residues are well-known metabolites of phenanthrene. Thus, metabolites of [1-(13)C]phenanthrene formed during biodegradation appear to be reactive components which are subsequently involved in the bound residue formation. Hydrolysable amino acids of the soil residues were significantly labelled with (13)C as confirmed by IRM-GC-MS measurements. Therefore, phenanthrene-derived carbon was transformed by anabolic microbial processes into typical biologically derived compounds. These substances are likely to be incorporated into humic-like material after cell death.     

Biodegradation of phenanthrene in river sediment

The aerobic biodegradation potential of phenanthrene (a polycyclic aromatic hydrocarbon [PAH]) in river sediment was investigated in the laboratory. Biodegradation rate constants (k1) and half-lives (t1/2) for phenanthrene (5 microg/g) in sediment samples collected at five sites along the Keelung River in densely populated northern Taiwan ranged from 0.12 to 1.13 l/day and 0.61 to 5.78 day, respectively. Higher biodegradation rate constants were noted in the absence of sediment. Two of the sediment samples were capable of biodegrading phenanthrene at initial concentrations 5-100 microg/g; lower biodegradation rates occurred at higher concentrations. Optimal biodegradation conditions were determined as 30 degreesC and pH 7.0. Biodegradation was not significantly influenced by the addition of such carbon sources as acetate, pyruvate, and yeast extract, but was significantly influenced by the addition of ammonium, sulfate, and phosphate. Results show that anthracene, fluorene, and pyrene biodegradation was enhanced by the presence of phenanthrene, but that phenanthrene treatment did not induce benzo[a]pyrene biodegradation during a 12-day incubation period.     

Sorption behavior of metolachlor, isoproturon, and terbuthylazine in soils

The sorption-desorption of metolachlor [2-chloro-N-(ethyl-6-methyl phenyl)-N-(2-methoxy-1-methyl ethyl) acetamide], isoproturon [3-(4-isopropyl phenyl)-1,1-dimethyl urea] and terbuthylazine [N6-tert butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine] herbicides was studied in two German soils at 1:10 soil to water ratio by batch method. Equilibrium of herbicides between soil and water (0.01 M CaCl2) was attained in 2 h. Sorption data fitted very well to Freundlich equation, represented by very high correlation coefficient (r2 > 0.934). Comparison of Freundlich K values indicated that sorption of all the three herbicides was most pronounced in soil having higher organic carbon content. Koc values were as expected nearly identical for each herbicide in the two soils. The Freundlich constant (1/n) was about 1 for metolachlor and less than 1 for terbuthylazine and isoproturon indicating a L-type of sorption isotherms. Desorption of all the three herbicides showed hysteresis. Nearly equal amounts of metolachlor, isoproturon and terbuthylazine were desorbed from both soils. There was a good correlation between Koc and solubility.     

The effect of the corticosteroid hormone cortexolone on the metabolites produced during phenanthrene biotransformation in Cunninghamella elegans

The metabolism of phenanthrene and the mammalian corticosteroid hormone cortexolone by the fungus Cunninghamella elegans was studied. The amounts of the cortexolone transformation products, cortisol and epicortisol, were affected by the presence of phenanthrene. Approximately 40% more cortisol was produced by C. elegans in cultures with phenanthrene. In contrast, epicortisol formation decreased. C. elegans transformed phenanthrene to phenanthrene trans-1,2-,3,4-, and 9,10-dihydrodiols, phenols, diphenols (diols) and glucoside conjugates of 1-, 2-, 3-, 4-, and 9-phenanthrols. Almost all of the phenanthrene initially added was metabolized to ethyl acetate extractable metabolites. In the mycelia and culture medium extracts, phenanthrol glucosides represented 80% and 94% of the total metabolites, respectively. The major metabolite was the glucoside conjugate of 1-phenanthrol. The presence of cortexolone affected the biodegradation of phenanthrene by decreasing the amounts of phenanthrene metabolites compared to control cultures.     

Toxicity of various anions associated with methoxyethyl methyl imidazolium-based ionic liquids on Clostridium sp

We investigated the effects on the growth of the anaerobic bacterium, Clostridium sp., of the ionic liquid, 1-methoxyethyl-3-methyl imidazolium [MOEMIM]⁺, derived from imidazolium cation and paired with one of a variety of counter-ions, viz., tetrafluoroborate [BF₄]^-, hexafluorophosphate [PF₆]^-_, trifluoroacetate [CF₃COO]^-, bis(trifluoromethane)sulfonamide [Tf₂N]^-, methane sulfonate [OMS], and 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM][BF₄]. These anions, in association with [MOEMIM]⁺ lowered the growth rate of the bacterium, showing the following trend: [Tf₂N]^- ≧ [PF₆]^- > [BF₄]^- > [CF₃COO]^- > [OMS]⁻. Anions incorporating fluorine were more toxic than those without it, and their toxicity rose with an increase in the number of fluorine atoms. Also, [MOEMIM]⁺[BF₄]^- was less toxic than [BMIM]⁺[BF₄]^-, probably due to the presence of a methoxyethyl functional group integrated in the cation side chain.     

Polycyclic aromatic hydrocarbons and hydroxylated metabolites in the muscle tissue of Eurasian perch (Perca fluviatilis) through dietary exposure during a 56-day period

Eurasian perch (Perca fluviatilis) was exposed trophically to phenanthrene, pyrene and benzo[a]pyrene. Accumulation kinetics in the muscle tissue of parent PAHs and hydroxylated metabolites were established for 56 days at 3 levels of exposure (0, 100 and 500 μg/kg BW). Benzo[a]pyrene and 3-hydroxy-benzo[a]pyrene were not detected in the muscles. During exposure, there was an increase in phenanthrene, pyrene and their hydroxylated metabolites in the muscle tissue. Low transfer to muscle tissue was observed at equilibrium for phenanthrene (4.4 ± 0.6% and 2.7 ± 0.8%) and pyrene (1.0 ± 0.2% and 0.33 ± 0.09%), depending on the concentrations in the spiked feed.     

GC/MS analysis of polynuclear aromatic hydrocarbons in sediment samples from the Niger Delta region

Thirteen sediment samples from different locations in the Niger Delta region of Nigeria were analyzed for the presence of 16 polynuclear aromatic hydrocarbons (PAHs) via gas chromatography/mass spectrometry. The specific target compounds for this study included naphthalene, acenaphthylene, acenaphthene, flourene, phenanthrene, anthracene, flouranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]flouranthene, benzo[a]pyrene, benzo[ghi]perylene, dibenz[a,h]anthracene, and indeno[1,2,3-cd]pyrene. Four isotopically labeled polynuclear aromatic hydrocarbons (acanaphthene-d10, phenanthrene-d10, chrysene-d12 and perylene-d12) were used for internal standardization. All 16 PAHs were found in most of the thirteen samples with concentration ranging from 0.1 microg/kg to 28 microg/kg. It was also found that the 5 and 6-ring PAHs were present in higher concentrations than all the other compounds, indicating their high resistance to microbial degradation.     

Bioremediation of polycyclic aromatic hydrocarbon-contaminated saline-alkaline soils of the former Lake Texcoco

Polycyclic aromatic hydrocarbons (PAHs) such as phenanthrene, anthracene and Benzo[a]pyrene (BaP) are toxic for the environment. Removing these components from soil is difficult as they are resistant to degradation and more so in soils with high pH and large salt concentrations as in soil of the former lake Texcoco, but stimulating soil micro-organisms growth by adding nutrients might accelerate soil restoration. Soil of Texcoco and an agricultural Acolman soil, which served as a control, were spiked with phenanthrene, anthracene and BaP, added with or without biosolid or inorganic fertilizer (N, P), and dynamics of PAHs, N and P were monitored in a 112-day incubation. Concentrations of phenanthrene did not change significantly in sterilized Acolman soil, but decreased 2-times in unsterilized soil and >25-times in soil amended with biosolid and NP. The concentration of phenanthrene in unsterilized soil of Texcoco was 1.3-times lower compared to the sterilized soil, 1.7-times in soil amended with NP and 2.9-times in soil amended with biosolid. In unsterilized Acolman soil, degradation of BaP was faster in soil amended with biosolid than in unamended soil and soil amended with NP. In unsterilized soil of Texcoco, degradation of BaP was similar in soil amended with biosolid and NP but faster than in the unamended soil. It was found that application of biosolid and NP increased degradation of phenanthrene, anthracene and BaP, but to a different degree in alkaline-saline soil of Texcoco compared to an agricultural Acolman soil.     

In vitro EROD induction equivalency factors for the 10 PAHs generally monitored in risk assessment studies in The Netherlands

The ethoxy resorufin dealkylase (EROD) inducing potency of 10 polycyclic aromatic hydrocarbons (PAHs) is measured in the H4IIE in vitro bioassay and the results are compared to those reported in literature. The selected PAHs varied considerably in their potency to induce EROD activity. Anthracene (Ant) and phenanthrene (Phe) showed consistently no response. Naphthalene (Nap) showed no or a very weak response on EROD activity. Fluoranthene (Fla) and benzo[g,h,i]perylene (BghiP) showed weak responses at the highest doses. The other PAHs, including indeno[1,2,3-cd]pyrene (IP), benz[a]anthracene (BaA), benzo[a]pyrene (BaP), chrysene (Chr) and benzo[k]fluoranthene (BkF), showed full bell shaped dose-response curves. BaP EROD induction equivalency factors (BaP-1EF) were calculated and increased in the order Ant approximately Phe < Fla < Nap < BghiP < IP < BaA < BaP < Chr < BkF. Comparison of BaP-IEFs based on 50% effect concentration (EC50) or lowest effect concentration (LEC), yielded a significant relationship between both methods described by the equation log(BaPIEF(EC50) = 0.55 x log(BaPIEF(LEC)) + 0.07 (r2 = 0.913). BaP-IEFs as derived from our measurements and as reported in literature and measured in other in vitro assays deviated up to a factor of 17 among the different studies, but the potency rankings were comparable. For the PAH mixture as on average present in the human diet an overall tetrachlorodibenzo-p-dioxin (TCDD)-IEF of 1 x 10(-4) was estimated. The total PAH based TCDD induction equivalents (IEQ) intake then was calculated 300 pg/day, which is approximately 2 times higher then the PHAH based TCDD-EQ intake reported for humans.     

Use of spent mushroom compost to bioremediate PAH-contaminated samples

Spent mushroom compost (SMC) is a bulky waste byproduct of mushroom industry and produced abundantly. The SMC of Pleurotus pulmonarius immobilized laccase (0.88 mmoles min(-1) g(-1)) and manganese peroxidase (0.58 mmoles min(-1) g(-1)) of which the optimal temperatures were 45 and 75 degrees C, respectively. In laboratory test, complete degradative removal of individual naphthalene, phenanthrene, benzo[a]pyrene and benzo[g,h,i]perylene (200 mg PAH kg(-1) sandy-loam soil) by 5% SMC was obtained in two days under continuous shaking at 80 degrees C. The SMC-treated PAH samples had significantly reduced or removed their toxicities as revealed by the Microtox bioassay. These results were confirmed by gas chromatography-mass spectrometry analysis on the breakdown products. A phthalic derivative which is reported as a degradative product of PAHs by ozonation or ligninolysis was also detected in the SMC-treated samples. The results demonstrate the potential in employing SMC in ex situ bioremediation.     

Contributions to ecological chemistry CXII balance of conversion of buturon‐14C in wheat under outdoor conditions 1

Abstract

The urea herbicide buturon (N‐[p‐chlorophenyl] ‐N’ ‐methyl‐N’ ‐isobutinyl‐urea), ¹⁴C‐labeled, was sprayed on winter wheat as an aqueous formulation (2.98 kg/ha) under outdoor conditions. Upon harvest (three months after application), a total of 49. 2% of the applied radiocarbon was recovered: 2.0% in the plants, 46.9% in the soil, and 0.3% in the leaching water (depth > 50 cm); less than 0.1% was in the grains (0.464 ppm). Only about half of the radioactivity present in plants could be recovered under mild extraction conditions; about half of this was unchanged buturon. In straw and husk extracts, the following metabolites were identified by gaschromatography/mass spectrometry: N‐(p‐chlorophenyl)‐N‐methyl‐O‐methyl‐carbamate (metabolite I), N‐phenyl‐N’ ‐formyl‐urea (metabolite II), two unstable metabolites giving (p‐chlorophenyl)‐isocyanate upon purification (metabolites III and IV), N‐(p‐chlorophenyl)‐N’ ‐methyl‐N’ ‐isobutenylol‐urea (metabolite V), p‐chloroformanilide (metabolite VI) and biologically bound p‐chloroaniline (metabolite VII). In the root and basal stem extract, the following metabolites were identified by gas chromatography/mass spectrometry: N‐(p‐chlorophenyl)‐O‐methyl‐carbamate (metabolite VIII) and N‐(p‐chlorophenyl)‐N’ ‐methyl‐urea (metabolite IX).     

Portal absorption of 14C after ingestion of spiked milk with 14C-phenanthrene, 14C-benzo[a]pyrene or 14C-TCDD in growing pigs

Polycyclic aromatic hydrocarbons (PAHs) and dioxins are lipophilic organic pollutants occurring widely in the terrestrial environment. In order to study the PAHs and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) transfer in the food chain, pigs have been fed with milk mixed either with 14C-phenanthrene, with 14C-benzo[a]pyrene or with 14C-TCDD. The analysis of portal and arterial blood radioactivity showed that both PAHs and TCDD were absorbed with a maximum concentration at 4-6 h after milk ingestion. Then, the blood radioactivity decreased to reach background levels 24 h after milk ingestion. Furthermore, the portal and arterial blood radioactivities were higher for phenanthrene (even if the injected load was the lowest) than these of benzo[a]pyrene or these of TCDD, in agreement with their lipophilicity and water solubility difference. Main 14C absorption occurred during the 1-3 h time period after ingestion for 14C-phenanthrene and during the 3-6 h time period for 14C-benzo[a]pyrene and for 14C-TCDD. 14C portal absorption rate was high for 14C-phenanthrene (95%), it was close to 33% for 14C-benzo[a]pyrene and very low for 14C-TCDD (9%). These results indicate that the three studied molecules have a quite different behaviour during digestion and absorption. Phenanthrene is greatly absorbed and its absorption occurs via the blood system, whereas benzo[a]pyrene and TCDD are partly and weakly absorbed respectively. However these two molecules are mainly absorbed via the portal vein.