Anne E. Berns

Effect of heating time and temperature on the chemical characteristics of biochar from poultry manure.

Poultry manure (PM) chars were obtained at different temperatures and charring times. Chemical-physical characterization of the different PM chars was conducted by cross-polarization magic angle spinning (CPMAS) (13)C NMR spectroscopy and thermal analysis. CPMAS (13)C NMR spectra showed that the chemical composition of PM char is dependent on production temperature rather than on production duration. Aromatic and alkyl domains in the PM chars obtained at the lowest temperatures remained unchanged at all heating times applied for their production. The PM char obtained at the highest temperature consisted only of aromatic structures having chemical nature that also appeared invariant with heating time. Thermogravimetry revealed differences in the thermo-oxidative stability of the aromatic domains in the different PM chars. The PM char produced at the highest temperature appeared less stable than those produced at the lowest temperatures. This difference was explained by a protective effect of the alkyl groups, which are still present in chars formed at lower temperature. The analysis of the chemical and physicochemical character of poultry manure chars produced at different temperatures can increase understanding of the role of these materials in the properties and behavior of char-amended soils.

Fast field cycling NMR relaxometry characterization of biochars obtained from an industrial thermochemical process

PurposeBiochar has unique properties which make it a powerful tool to increase soil fertility and to contribute to the decrease of the amount of atmospheric carbon dioxide through the mechanisms of C sequestration in soils. Chemical and physical biochar characteristics depend upon the technique used for its production and the biomass nature. For this reason, biochar characterization is very important in order to address its use either for agricultural or environmental purposes.Materials and methodsThree different biochars obtained from an industrial gasification process were selected in order to establish their chemical and physical peculiarities for a possible use in agronomical practices. They were obtained by charring residues from the wine-making industry (marc) and from poplar and conifer forests. Routine analyses such as pH measurements, elemental composition, and ash and metal contents were performed together with the evaluation of the cross-polarization magic angle spinning (CPMAS) 13C NMR spectra of all the biochar samples. Finally, relaxometry properties of water-saturated biochars were retrieved in order to obtain information on pore size distribution.Results and discussionAll the biochars revealed basic pH values due to their large content of alkaline metals. The quality of CPMAS 13C NMR spectra, which showed the typical signal pattern for charred systems, was not affected by the presence of paramagnetic centers. Although paramagnetism was negligible for the acquisition of solid state spectra, it was effective in some of the relaxometry experiments. For this reason, no useful information could be retrieved about water dynamics in marc char. Conversely, both relaxograms and nuclear magnetic resonance dispersion profiles of poplar and conifer chars indicated that poplar char is richer in small-sized pores, while larger pores appear to be characteristic for the conifer char.ConclusionsThis study showed the potential of relaxometry in revealing chemical–physical information on industrially produced biochar. This knowledge is of paramount importance to properly direct biochar agronomical uses.

Chlordecone fate and mineralisation in a tropical soil (andosol) microcosm under aerobic conditions.

Chlordecone is a persistent organochlorine insecticide that, even decades after its ban, poses a threat to the environment and human health. Nevertheless, its environmental fate in soils has scarcely been investigated, and elementary data on its degradation and behaviour in soil are lacking. The mineralisation and sorption of chlordecone and the formation of possible metabolites were evaluated in a tropical agricultural andosol. Soil microcosms with two different soil horizons (S-A and S-B) were incubated for 215 days with 14C-chlordecone. At five different times (1, 33, 88, 150 and 215 days) the extractability of 14C-chlordecone was analysed. Mineralisation was monitored using 14CO2 traps of NaOH. The appearance of metabolites was studied using thin layer and gas chromatography techniques. At the end of the experiment, the water soluble 14C-activity was 2% of the remaining 14C-chlordecone for S-A and 8% for S-B. Only 12% of the remaining activity was non extractable and more than 80% remained extractable with organic solvents. For the first time to our knowledge, a significant mineralisation of chlordecone was measured in a microcosm under aerobic conditions (4.9% for S-A and 3.2% for S-B of the initial 14C-activity). The drastically lower emission of 14CO2 in sterilised microcosms indicated the biological origin of chlordecone mineralisation in the non-sterilised microcosms. No metabolites could be detected in the soil extracts. The mineralisation rate of chlordecone decreased by one order of magnitude throughout the incubation period. Thus, the chlordecone content in the soil remained large. This study confirms the existence of chlordecone degrading organisms in a tropical andosol. The reasons why their activity is restricted should be elucidated to allow the development of bioremediation approaches. Possible reasons are a heterogeneous distribution a chlordecone between sub-compartments with different microbial activities or a degradation of chlordecone by co-metabolic processes controlled by a limited supply of nutrients.

Effect of soil organic matter chemistry on sorption of trinitrotoluene and 2,4-dinitrotoluene

The sorption of organic contaminants in soil is mainly attributed to the soil organic matter (SOM) content. However, recent studies have highlighted the fact that it is not the total carbon content of the organic matter, but its chemical structure which have a profound effect on the sorption of organic contaminants. In the present study sorption of two nitroaromatic contaminants viz. trinitrotoluene (TNT) and 2,4-dinitrotoluene (2,4-DNT) was studied in different SOM fractions viz. a commercial humic acid, commercial lignin and humic acid and humin extracted from a compost. (13)C-DP/MAS NMR studies indicated that the structural composition of the organic carbon in different SOM fractions was different. The order of sorption of the nitroaromatics in the different sorbents was: humic acid-commercial>humic acid-compost>humin approximately lignin. Among the aliphatic and aromatic carbon fractions (representing bulk of SOM matrix), adsorption parameter K(f)(1/n) for nitroaromatics sorption correlated well with the aliphatic carbon (r=0.791 for TNT and 0.829 for 2,4-DNT) than the aromatic carbon (r=0.634 for TNT and r=0.616 for 2,4-DNT). However, among carbon containing functional groups, carbonyl carbon showed strong positive correlation with sorption of TNT (r=0.991) and 2,4-DNT (r=0.967) while O-alkyl carbon showed negative correlation (r=0.832 for TNT and r=0.828 for 2,4-DNT). The study indicates that aliphatic domains in the SOM significantly affect the non-specific sorption of both the nitroaromatic contaminants.

Biochar-Mediated [14C]Atrazine Mineralization in Atrazine-Adapted Soils from Belgium and Brazil

Biochar addition to soil has been reported to reduce the microbial degradation of pesticides due to sorption of the active compound. This study investigated whether the addition of hardwood biochar alters the mineralization of (14)C-labeled atrazine in two atrazine-adapted soils from Belgium and Brazil at different moisture regimens. Biochar addition resulted in an equally high or even in a significantly higher atrazine mineralization compared to the soils without biochar. Statistical analysis revealed that the extent of atrazine mineralization was more influenced by the specific soil than by the addition of biochar. It was concluded that biochar amendment up to 5% by weight does not negatively affect the mineralization of atrazine by an atrazine-adapted soil microflora.

Investigations on the binding mechanism of the herbicide simazine to dissolved organic matter in leachates of compost

14C-labelled simazine was composted together with biowaste on a pilot (m3) scale. The herbicide was quickly bound to the compost matrix. By aqueous extraction of 29 and 200 days old compost (equivalent to thermophilic and mesophilic phase of composting) only 4.2% and 3.1% respectively of the radioactivity in the compost samples could be extracted with water. Analysis of the extracts using high-performance size exclusion chromatography (HPSEC) revealed that the dissolved organic matter (DOM) had molecular weights ranging between 2 and 28 kDa. The amount of DOM-associated radioactivity increased from 53% (day 29) to 65% (day 200) of total extractable radioactivity. The type of binding of the 14C-labelled residues and the DOM was elucidated by silylation of humic matter and subsequent HPSEC. The data demonstrated that besides polar metabolites also intact simazine was bound to the DOM. A distinct shift from rather weak interactions to strong covalent linkages of simazine and its metabolites with increasing age of the compost was observed. The results showed that only low amounts of free simazine and its degradates can be extracted with water. We concluded that the shift towards stable covalent linkages is equivalent to a detoxification of the contaminant in aged compost. Consequently, the use of the analysed compost in its mature stage should not pose an environmental risk to the groundwater or the subsoil.

Effect of structural composition of humic acids on the sorption of a branched nonylphenol isomer

By using dialysis equilibrium experiments, the sorption of a branched nonylphenol isomer [4-(1-ethyl-1,3-dimethylpentyl)-phenol] (NP111) on various humic acids (HAs) isolated from river sediments and two reference HAs was studied. The HAs were characterized by solid-state (13)C direct polarization/magic angle spinning nuclear magnetic resonance ((13)C DP/MAS NMR) spectroscopy. Sorption isotherms of NP111 on HAs were described by a linear model. The organic carbon-normalized sorption coefficient (K(OC)) ranged from 2.3×10(3) to 1.5×10(4)Lkg(-1). Interestingly, a clear correlation between K(OC) value and alkyl C content was observed, indicating that the aliphaticity of HAs markedly dominates the sorption of NP111. These new mechanistic insights about the NP111 sorption indicate that the fate of nonylphenols in soil or sediment depends not only on the content of HA, but also on its structural composition.

Effect of RF Field Inhomogeneity and Sample Restriction on SpectralResolution of CP/MAS-13C NMR Spectra of Natural Organic Matter

It is well known that the induced B1 magnetic field in an NMR coil is inhomogeneously distributed. However, this issue has so far received little attention in the field of environmental NMR. As this research field often aims at quanti- tative results as well as relaxation phenomena, the repercussions of such inhomogeneity on peak integrals and relaxation times need to be taken into account. The objective of the present study was to test standard recording conditions on different sample positions in an NMR coil in order to determine the effect of the RF field inhomogeneity on the spectrum of a molecularly complex humic material and on some standard molecules of known structure and conformation. To this end, we measured the peak integral and signal half-height width of constant sample amounts at different heights in the rotor. In addition, the effect of sample posi- tion in the rotor on T1H and T2C relaxation times was determined. We showed that the response profiles of different chemical groups are not necessarily comparable to each other and that spectra of natural organic matter can change when confined to different regions of the coil. Furthermore, the relaxation measurements revealed that T1H and T2C relaxation times are position-dependent. Finally, the application of sample res- triction to the homogeneous region appeared very promising for enhancing the resolution of spectra of complex mixtures.

Interactive effects of MnO 2 , organic matter and pH on abiotic formation of N 2 O from hydroxylamine in artificial soil mixtures

Abiotic conversion of the reactive nitrification intermediate hydroxylamine (NH2OH) to nitrous oxide (N2O) is a possible mechanism of N2O formation during nitrification. Previous research has demonstrated that manganese dioxide (MnO2) and organic matter (OM) content of soil as well as soil pH are important control variables of N2O formation in the soil. But until now, their combined effect on abiotic N2O formation from NH2OH has not been quantified. Here, we present results from a full-factorial experiment with artificial soil mixtures at five different levels of pH, MnO2 and OM, respectively, and quantified the interactive effects of the three variables on the NH2OH-to-N2O conversion ratio (RNH2OH-to-N2O). Furthermore, the effect of OM quality on RNH2OH-to-N2O was determined by the addition of four different organic materials with different C/N ratios to the artificial soil mixtures. The experiments revealed a strong interactive effect of soil pH, MnO2 and OM on RNH2OH-to-N2O. In general, increasing MnO2 and decreasing pH increased RNH2OH-to-N2O, while increasing OM content was associated with a decrease in RNH2OH-to-N2O. Organic matter quality also affected RNH2OH-to-N2O. However, this effect was not a function of C/N ratio, but was rather related to differences in the dominating functional groups between the different organic materials.

Dynamics of benazolin under the influence of degrading maize straw in undisturbed soil columns

The effect of organic carbon amendment on the fate of benazolin was investigated in undisturbed soil columns. The soil columns were obtained from three different soil types located in three different regions with different crop production regimes. All soils were operated in a normal crop production regime, and one of the soils was additionally operated in low and high crop production regimes. Two experimental setups were conducted, one using [(14)C]maize straw and nonlabeled benazolin and one using nonlabeled maize straw and [(14)C]benazolin. The column experiments with [(14)C]maize straw showed that the residual crop residues remained mainly in the top layer. Benazolin and its metabolites showed a higher retention in columns that were amended with maize straw compared to column without amendment. The production regimes of the soils did not influence the behavior of benazolin. The effect of maize straw incorporation on the translocation and degradation of benazolin could well be caused by a change in the soil microbial activity, leading to an enhanced degradation of benazolin and producing metabolites exhibiting a sorption behavior different from the parent.