Sorption Of Organic Matter Research Articles

Effect of Harsh or Mild Extraction of Soil on Pesticide Leaching to Groundwater

Assessment of leaching to groundwater is an important aspect of pesticide risk assessment. The first leaching tier usually consists of simulations with leaching scenarios based on pesticide-soil properties derived from laboratory studies. Because the extractability of pesticide residues in such studies decreases with time, the harshness of the extraction method influences these pesticide-soil properties. This study investigates the effect of using a mild or harsh extraction method on simulated leaching to groundwater with consideration of substances with a range of half-lives and organic matter sorption coefficient values for selected leaching scenarios. The model for linking the concentrations of the mild and the harsh systems was based on laboratory studies with two pesticides and a Dutch sandy soil and was tested against Canadian field studies with atrazine (6-chloro-2-ethyl-4-isopropyl-1,3,5-triazine-2,4-diamine). The degradation rate and the aged-sorption parameters of each "mild" soil-substance system were derived from a hypothetical laboratory incubation study using prescribed parameter values for the corresponding "harsh" soil-substance system. Simulations were performed for three European leaching scenarios (United Kingdom, France, Portugal). For the best-guess parameter set, the leaching concentrations of the harsh system were approximately equal to those of the mild system at leaching concentrations greater than 1 μg L and were at most approximately a factor of two higher than those of the mild systems at mild leaching concentrations between 0.01 and 0.1 μg L. However, an extreme parameter set led to harsh leaching concentrations that were at most approximately 10 times higher than the mild leaching concentrations at levels between 0.01 and 0.1 μg L.

The role of allophane nano-structure and Fe oxide speciation for hosting soil organic matter in an allophanic Andosol

We evaluated the impact of nano-structural characteristics of allophanic compounds and Fe oxide speciation on the efficiency of organo-mineral interactions in an allophanic Andosol derived from volcanic ash (Eifel mountains, Germany). The samples selected for our work represented a gradient from: (i) a pure synthetic allophane and (ii) model organo-mineral mixtures to (iii) particle size fractions of the natural Andosol. We thus aimed to link the processes operating at the individual molecular scale to the phenomena active at the aggregate scale. For a non-destructive characterization of the samples, we applied 129Xe NMR spectroscopy of adsorbed Xe atoms (to identify the mineral nano-structure and surface acid centres), ESEM (verifying the nano-spherical structure of allophane), 13C CPMAS NMR (for the nature of the soil organic matter (SOM)), 57Fe Mössbauer spectroscopy (Fe oxide speciation), and N2 adsorption (contribution of micro- and mesoporosity). By using the atomic probe Xe, we obtained evidence for a coupled mechanism of adsorption onto allophane requiring both the narrow pores (voids formed by the primary nano-spherules) and the acid centres located at the defect surfaces of the primary spherules. The validity of this coupled mechanism for the sorption of organic matter was confirmed by the concomitant blocking of acid centres (129Xe NMR data) and the decrease of the N2-available pore volumes (Vmicro and Vmeso) in the model samples DOM/- and NOM/allophane (DOM=dissolved OM, NOM=natural OM). In the Andosol, the high resistance of SOM against oxidation (OCresist=15–50%) was combined with preferential accumulation of certain organic compounds, e.g. potentially labile substrates such as carbohydrates, and the low molecular weight species such as amino acids. This feature was attributed to the peculiar microporous tortuous structure of allophane aggregates that likely impose certain criteria for the chemical nature and size of mineral-bound SOM. On the other hand, the revealed dominance of nanoparticulate Fe oxyhydroxides (57% ferrihydrite) and Fe-substituted allophane (supposedly formed due to co-precipitation of the Al, Si and Fe in the course of volcanic soil formation) may substantially contribute to the formation of highly resistant organo-mineral associations through the enhanced extent of reactive surface groups in nanoparticles, increased surface charge density and electron accepting properties of substituting Fe3+ species that supposedly enhance the proportion of oxidised organic components.

Thermal Stability of Goethite-Bound Natural Organic Matter Is Impacted by Carbon Loading.

Dissolved natural organic matter (NOM) sorption at mineral surfaces can significantly affect the persistence of organic carbon in soils and sediments. Consequently, determining the mechanisms that stabilize sorbed NOM is crucial for predicting the persistence of carbon in nature. This study determined the effects of loadings and pH on the thermal stability of NOM associated with synthetic goethite (α-FeOOH) particle surfaces, as a proxy for NOM-mineral interactions taking place in nature. NOM thermal stability was investigated using temperature-programmed desorption (TPD) in the 30-700 °C range to collect vibration spectra of thermally decomposing goethite-NOM assemblages, and to concomitantly analyze evolved gases using mass spectrometry. Results showed that NOM thermal stability, indicated by the range of temperatures in which CO2 evolved during thermal decomposition, was greatest in unbound NOM and lowest when NOM was bound to goethite. NOM thermal stability was also loading dependent. It decreased when loadings were in increased the 0.01 to 0.42 mg C m(-2) range, where the upper value corresponds to a Langmuirian adsorption maximum. Concomitant Fourier transform infrared (FTIR) spectroscopy measurement showed that these lowered stabilities could be ascribed to direct NOM-goethite interactions that dominated the NOM binding environment. Mineral surface interactions at larger loadings involved, on the contrary, a smaller fraction of the sorbed NOM, thus increasing thermal stability toward that of its unbound counterpart. This study thus identifies a sorption threshold below which NOM sorption to goethite decreases NOM thermal stability, and above which no strong effects are manifested. This should likely influence the fate of organic carbon exposed to thermal gradients in natural environments.

Sorption of paddy soil-derived dissolved organic matter on hydrous iron oxide–vermiculite mineral phases

Sorption of organic matter (OM) onto soil minerals affects OM dynamics, and is strongly controlled by mineral surface properties. Moreover, the degree and mechanism of interaction between different minerals may influence their surface reactivity. We therefore aimed to understand mineral surface modifications brought about by different Fe (hydr)oxide–vermiculite associations, and their influence on OM sorption. This could have important implications on OM dynamics in young hydromorphic soils where seasonal variations in redox conditions may affect mineral surfaces. Paddy soil-derived dissolved OM was used in sorption isotherms on mixed mineral phases obtained by precipitating different amounts of Fe (hydr)oxides on vermiculite. Results evidenced that the surface properties of vermiculite strongly drove Fe (hydr)oxide precipitation, and consequently OM sorption mechanisms. The change in surface charge with increasing Fe loading resulted in a higher retention of dissolved organic carbon. However, dissolved organic nitrogen adsorption isotherms and FTIR carboxyl vibrational shifts revealed the occurrence of two binding mechanisms, one driven by electrostatic attraction of N-containing compounds by the negatively charged vermiculite surface, and another involving ligand exchange of carboxylic compounds with the positive oxides, precipitated in localized nucleation sites. Moreover, the modification of both solution and solid properties during sorption, promoted the selective adsorption of aromatic molecules with increasing Fe coverage.

Contrasting effects of aged and fresh biochars on glucose-induced priming and microbial activities in paddy soil

The understanding of soil organic matter (SOM) decomposition to biochar (BC) addition in paddy soil remains limited. This study was to examine the glucose-induced priming effects of paddy soil as affected by aged and/or fresh BCs. Soil samples were collected from the paddy fields without and with BC applied 1 year before the laboratory incubation. The control without BC, the soil with BC applied in the field (aged BC), aged BC and the additional fresh BC applied (A/F-BC), and the soil with fresh BC (fresh BC), each with glucose (14C) addition or not were incubated under either moist or flooding conditions. Totally, 16 treatments were established. The aged-BC group treatments had greater carbon dioxide (CO2) efflux (averagely 26 %) compared to the control group, while CO2 efflux was reduced following fresh BC addition by 23 and 21 % in the A/F-BC and fresh-BC groups, respectively. In the presence of aged BC, microbial biomass and the potential activities of s-glucosidase, xylanase, cellobiohydrolase, and chitinase were increased under both moist and flooding conditions, but they were decreased in the fresh-BC group under flooding conditions. For the control group, positive priming of 58 and 102 μg C g−1 were observed after glucose addition under moist and flooding conditions, respectively. Positive priming was also observed in the fresh-BC group amounting to 34 and 19 μg C g−1 under moist and flooding conditions, respectively. However, negative priming was found in the soil samples with aged BC, especially under moist conditions, which was possibly due to the preferential use of glucose over the more recalcitrant organic C in both SOM and BC and SOC stabilization via either organic matter sorption on BC or the BC-induced organic-mineral interaction. BC effects on CO2 efflux and microbial activities depend strongly on its age. Aged BC improves soil microbial parameters and also contributes to C sequestration in soil by negative priming. In contrast, fresh BC addition depresses microbial activities but stimulates the mineralization of SOM and itself following glucose addition.

Properties and bioavailability of particulate and mineral‐associated organic matter in Arctic permafrost soils, Lower Kolyma Region, Russia

SummaryPermafrost degradation may cause strong feedbacks of arctic ecosystems to global warming, but this will depend on if, and to what extent, organic matter (OM) is protected against biodegradation by mechanisms other than freezing and anoxia. Here, we report on the amount, chemical composition and bioavailability of particulate (POM) and mineral‐associated OM (MOM) in permafrost soils of the East Siberian Arctic. The average total organic carbon (OC) stock across all soils was 24.0 ± 6.7 kg m−2 within 100 cm soil depth. Density fractionation (density cut‐off 1.6 g cm−3) revealed that 54 ± 16% of the total soil OC and 64 ± 18% of OC in subsoil horizons was bound to minerals. As well as sorption of OM to clay‐sized minerals (R2 = 0.80; P < 0.01), co‐precipitation of OM with hydrolyzable metals may also transfer carbon into the mineral‐bound fraction. Carbon:nitrogen ratios, stable carbon and nitrogen isotopes, 13C‐NMR and X‐ray photoelectron spectroscopy showed that OM is transformed in permafrost soils, which is a prerequisite for the formation of mineral‐organic associations. Mineral‐associated OM in deeper soil was enriched in 13C and 15N, and had narrow C:N and large alkyl C:(O‐/N‐alkyl C) ratios, indicating an advanced stage of decomposition. Despite being up to several thousands of years old, when incubated under favourable conditions (60% water‐holding capacity, 15°C, adequate nutrients, 90 days), only 1.5–5% of the mineral‐associated OC was released as CO2. In the topsoils, POM had the largest mineralization but was even less bioavailable than the MOM in subsoil horizons. Our results suggest that the formation of mineral‐organic associations acts as an important additional factor in the stabilization of OM in permafrost soils. Although the majority of MOM was not prone to decomposition under favourable conditions, mineral‐organic associations host a readily accessible carbon fraction, which may actively participate in ecosystem carbon exchange.

Factors influencing natural organic matter sorption onto commercial graphene oxides

Nanosized graphene materials are being considered as a class of new, high surface area sorbents suitable for water treatment applications. This study explored commercially available graphene powders of differing sizes, surface areas, and surface compositions for their ability to sorb dissolved natural organic matter (NOM) from water under varying solution conditions within batch reactors. The sorption kinetics of NOM on graphene powders were rapid and reached equilibrium within hours. Sorption isotherms for all graphenes and all NOM types were all best described with the Freundlich model. Sorption affinity improved with increasing graphene specific surface area, more graphene carbon content, greater NOM aromatic content, and lower solution pH. Graphene sorption behavior is compared to carbon nanotubes and granular activated carbon, and high surface area graphene may possess superior sorption rates and capacities, whereas low surface area graphene may be entirely ineffective. The high surface area graphene examined here also showed selectivity for the aromatic and high molecular weight NOM fractions within measurements of specific UV absorbance and size exclusion chromatography. The results suggest that aromatic interactions significantly participate in NOM binding, but that electrostatic interactions may also influence sorption capacity depending on solution pH and graphene surface charge.

Impact of Exotic Earthworms on Organic Carbon Sorption on Mineral Surfaces and Soil Carbon Inventories in a Northern Hardwood Forest

Exotic earthworms are invading forests in North America where native earthworms have been absent since the last glaciation. These earthworms bioturbate soils and may enhance physical interactions between minerals and organic matter (OM), thus affecting mineral sorption of carbon (C) which may affect C cycling. We quantitatively show how OM-mineral sorption and soil C inventories respond to exotic earthworms along an earthworm invasion chronosequence in a sugar maple forest in northern Minnesota. We hypothesized that mineral surface area in A horizons would increase as burrowing earthworms incorporated clay minerals from the B horizons and that enhanced contacts between OM and minerals would increase the OM sorption on mineral surfaces and mineral-associated C inventories in A horizons. Contrary to our hypotheses, mineral surface areas within A horizons were lowered because earthworm burrows only extended into the silt-rich loess that separated the A and clay-rich B horizons. Furthermore, where endogeic earthworms were present, a smaller fraction of mineral surface area was covered with OM. OM sorption on minerals in the A horizons shifted from a limitation of mineral surface availability to a limitation of OM availability within a decade after the arrival of endogeic earthworms. C-mineral sorption depends on earthworm consumption of OM as well as the composition and vertical distribution of minerals. This finding may thus explain the contradictory results reported in earlier investigations. Our results highlight the rapid and drastic effects of exotic earthworms on key ecosystem processes in deciduous forests in post-glacial settings.

Preferential sorption of some natural organic matter fractions to titanium dioxide nanoparticles: influence of pH and ionic strength.

Natural organic matter (NOM) sorption to nanoparticles (NPs) can influence their transport and bioavailability in the aquatic environment. The sorption affinity of NOM to surfaces including NPs is size dependent, and depending on environmental conditions, NOM may enhance or mitigate NPs toxicity. The aim of this study was to investigate the preferential sorption of different-sized fractions of NOM to titanium dioxide (TiO2) NPs. We specifically investigated the influence of pH, ionic strength, and NOM concentration on the extent of this preferential sorption using a constant sorbent concentration (400mg/L TiO2 NPs). Additionally, sorption of NOM to TiO2 NPs at varying pH was investigated. The nonsorbed NOM was separated from the sorbed, by 50nm polycarbonate membrane filters and ultracentrifugation. High-performance size exclusion chromatography (HPSEC) was used to determine the average molecular weights of NOM (MWw). Corroborative evidence of preferential sorption of different-sized molecular weight fractions of NOM was obtained from optical techniques such as absorbance and fluorescence spectrophotometry. The total organic carbon was measured by the Total Organic Carbon Analyzer-Shimadzu (TOC-VCPH). The results indicated that there is preferential sorption of larger sized fractions of NOM to TiO2 NPs irrespective of NOM concentration. It was observed that the sorption of larger sized fractions of NOM was much enhanced at lower pH and at higher ionic strength. Both absorbance and fluorescence spectrophotometric techniques gave credible corroborative evidence on the extent of preferential sorption of lager sized fractions of NOM with respect to pH and ionic strength. The sorption results demonstrated higher sorption at lower pH than at higher pH. Overall, the results of this study suggest that the environmental conditions are key factors that can contribute to NOM's fractional preferential sorption to NPs in the aquatic environment.

Biogeochemical Interface Formation: Wettability Affected by Organic Matter Sorption and Microbial Activity

Batch incubation and column percolation experiments with dissolved organic matter solution at different pH values were performed to investigate the effect of organic matter sorption and microbial activity on the wettability of clean quartz sand particles. Sodium azide was used as a biocide to control microbial activity. Changes in wettability were evaluated by contact angle measurements. Wettability of the quartz sand was found to significantly decrease after sorption of organic matter. An adsorbed C content of <0.1 g C kg−1 turned out to be effective in increasing the contact angle from initially 30 to >70°. Results of the percolation experiments revealed that the change in contact angle was depth dependent, with the greatest increase in the upper part of the columns. The low C/N ratio (<10) of the organic matter adsorbed in the upper part of the sand columns percolated without biocide addition suggested that the depth dependency was caused not only by sorption of organic matter but also was affected by microbial activity. This finding was supported by an increasing contact angle for sand columns percolated with a solution close to neutral pH (6.7), where more favorable living conditions for bacteria could be assumed. We also observed a trend of a linear inverse relationship between C/N ratio and contact angle, i.e., increasing contact angle with decreasing C/N ratio. Overall, the results indicated that the formation of biogeochemical interfaces can strongly change the original wetting properties of mineral particle surfaces.

The effects of organic matter–mineral interactions and organic matter chemistry on diuron sorption across a diverse range of soils

Sorption of non-ionic organic compounds to soil is usually expressed as the carbon-normalized partition coefficient (KOC), because it is assumed that the main factor that influences the amount sorbed is the organic carbon content of the soil. However, KOC can vary by a factor of at least ten across a range of soils. We investigated two potential causes of variation in diuron KOC – organic matter–mineral interactions and organic matter chemistry – for a diverse set of 34 soils from Sri Lanka, representing a wide range of soil types. Treatment with hydrofluoric acid (HF-treatment) was used to concentrate soil organic matter. HF-treatment increased KOC for the majority of soils (average factor 2.4). We attribute this increase to the blocking of organic matter sorption sites in the whole soils by minerals. There was no significant correlation between KOC for the whole soils and KOC for the HF-treated soils, indicating that the importance of organic matter–mineral interactions varied greatly amongst these soils. There was as much variation in KOC across the HF-treated soils as there was across the whole soils, indicating that the nature of soil organic matter is also an important contributor to KOC variability. Organic matter chemistry, determined by solid-state 13C nuclear magnetic resonance (NMR) spectroscopy, was correlated with KOC for the HF-treated soils. In particular, KOC increased with the aromatic C content (R=0.64, p=1×10−6), and decreased with O-alkyl C (R=−0.32, p=0.03) and alkyl C (R=−0.41, p=0.004) content.

Respiration and Sorption of Water-Extractable Organic Carbon as Affected by Addition of Ca2+, Isolated Clay or Clay-Rich Subsoil to Sand

Clay addition to light-textured soils is used to ameliorate water repellency and to increase nutrient retention. However, clay addition may also increase the potential to bind organic matter and thus C sequestration. Divalent calcium ions (Ca2+) play an important role in binding of organic matter to clay because they provide the bridge between the clay particles and organic matter which are both negatively charged. In the first experiment, quartz sand was mixed with clay isolated from a Vertosol at rates of 0, 50 and 300 g kg−1, finely ground mature wheat residues (20 g kg−1) and powdered CaSO4 at 0, 5 and 10 g kg−1. Soil respiration was measured over 28 d. Compared to the sand alone, addition of isolated clay at 300 g kg−1 increased cumulative respiration with a stronger increase than that at 50 g kg−1. Addition of CaSO4 increased electrical conductivity, decreased sodium adsorption ratio and reduced cumulative respiration. The latter can be explained by enhanced sorption of organic matter to clay via Ca2+ bridges. In a second experiment, isolated clay or subsoil of the Vertosol without or with powdered CaSO4 at 10 g kg−1 were used for a batch sorption with water-extractable organic C (WEOC) from wheat straw followed by desorption with water. Addition of 10 g kg−1 CaSO4 increased sorption and decreased desorption of WEOC in both subsoil and isolated clay. In the third experiment, subsoil of the Vertosol was used for a batch sorption in which WEOC was added repeatedly. Repeated addition of WEOC increased the concentration of sorbed C but decreased the sorbed proportion of the added WEOC. This indicates that sorption of WEOC may be underestimated if it is added only once in batch sorption experiments.

Impacts of biochar on bioavailability of the fungicide azoxystrobin: A comparison of the effect on biodegradation rate and toxicity to the fungal community

There is great interest in using biochar (BC) as a soil amendment to provide a long-term repository of carbon to mitigate climate change. BC can have major impacts on soil biogeochemical cycling processes, largely by the sorption and protection of organic matter from microbial turnover. Application of BC to agricultural soil could also affect the efficacy, fate and environmental impact of pesticides. In the current study we investigated the effect of BC on bioavailability of the fungicide azoxystrobin in soil. We found that application of BC had no effect on sorption or degradation of azoxystrobin, even at a rate of 2% w/w. While azoxystrobin reduced dehydrogenase activity, BC addition greatly increased dehydrogenase, although the inhibitory effect of azoxystrobin was still evident in BC amended soil. Using Terminal Restriction Fragment Length Polymorphism of fungal SSU rRNA gene ITS regions it was found that azoxystrobin altered the structure of the soil fungal community, although this effect was dampened by BC addition. BC application had minor effects on fungal community structure. We conclude that measurement of the effect of BC on pesticide bioavailability by analysis of biodegradation rate and non-target effects on fungal community structure gave contrasting conclusions.

Organic matter content and features related to associated mineral fractions in an acid, loamy soil

Sorption of soil organic matter on mineral surfaces is now recognized as a major organic carbon (C) stabilization process. To investigate the role of organo‐mineral interactions in carbon‐rich soils, we separated organo‐mineral associations by sequential density fractionation in the top‐ and subsoil of a forest Acrisol (umbrept) from southern France. Fractions were characterized by scanning electron microscopy, X‐ray diffraction, elemental analysis, 13C NMR and δ13C. For each horizon, we isolated five types of association: light organic matter non‐occluded, and occluded in aggregates (<1.9 g cm−3), and microaggregates formed by poorly crystallized mineral phases (1.9–2.2 g cm−3), by phyllosilicates (2.2–2.5 g cm−3) and by primary mineral particles weakly complexed with organic compounds (>2.5 g cm−3). Carbon accumulation in organo‐mineral fractions was correlated with a relative enrichment in hydrophobic compounds (alkyl C or aromatic C). In contrast, the content in nitrogen and carboxylic groups was more constant. Poorly crystalline mineral phases stabilized the largest amount of soil organic matter. We compiled data from previous studies carried out on soils with different mineralogies (n = 20) and found a significant correlation between the δ13C and the C:N ratio of sorbed organic compounds according to the C content of fractions. This general trend is in line with the conceptual model of a zonal structure of soil organic matter sorbed on mineral surfaces. Furthermore, we hypothesized that the accumulation of hydrophilic (O‐alkyl C) and hydrophobic (alkyl C and/or aromatic C) organic compounds on mineral surfaces is favoured by the structural organization of organo‐mineral associations. The same organo‐mineral associations were found in top‐ and subsoils, indicating similar stabilization processes in surface and deeper horizons.

The role of extracellular polymeric substances on the sorption of natural organic matter

In this study, the influence of extracellular polymeric substances (EPS) composition and quantity was explored for biosorption of natural organic matter (NOM), using variants of Pseudomonas aeruginosa and Pseudomonas putida. Model EPS (sodium alginate beads) were tested and sorption capacity for NOM was also elucidated. In the absence of divalent ions, minimal NOM biosorption was observed and differences among strains were negligible. Under presence of divalent ions, biosorption of NOM was proportional to the amount of EPS secreted by P. aeruginosa variants. For sorption tests with model EPS, divalent ions also promoted biosorption of tested NOM, and total biosorption was also proportional to alginate quantity. Carboxyl group content in both alginate EPS and NOM appeared to be linked to increased biosorption via bridging with divalent ions. The alginate overproducing strain possessed more potential NOM biosorption sites, while the wild-type and alginate deficient strains possessed fewer potential binding sites. In comparison, P. putida, secreting protein-based EPS, behaved differently for NOM biosorption, due to its hydrophobicity and the structural characteristics of proteins. Hydrophobic interactions appeared to enhance the biosorption of more hydrophobic Suwannee River humic acid by P. putida, whose biosorption of more hydrophilic NOM variants was similar to the alginate deficient strain. Mechanistically, the presence of a diffuse electrical double layer will present potential energy barriers limiting biosorption; however, divalent ion concentrations in the aquatic environment will promote biosorption processes, permitting functional group interactions between EPS and NOM. Bridging between hydrophilic carboxyl groups on alginate EPS and NOM appeared to be the dominant form of biosorption, while hydrophobic interactions enhanced biosorption for protein-based EPS.

Organic matter bound to mineral surfaces: Resistance to chemical and biological oxidation

Understanding the turnover of organic matter (OM) in soils necessitates information on biological stability and ecological functions. For easy characterization of slowly cycling OM, treatments using oxidants such as sodium hypochlorite (NaOCl) have been applied. The rationale for that approach is, however, questionable and concerns exist to which extent abiotic oxidation can mimic biological mineralization. Here we compare biological mineralization of mineral-bound OM to its resistance to chemical oxidation by 6 mass% NaOCl. Water-extractable OM, sorbed to goethite, vermiculite, and pyrophyllite at pH 4.0 and in different background electrolytes (CaCl 2, NaCl, NaCl–NaH 2PO 4) to favor or exclude certain binding mechanisms, was subsequently subjected to NaOCl treatment (pH 7, either for 18 or 6 × 6 h). Irrespective of mineral surface properties and mechanisms involved in OM sorption, NaOCl removed a constant portion of the sorbed OC. More OC survived when bound to goethite than to vermiculite, thus confirming previous results on the increase of oxidation-resistant OC with increasing Fe and Al (hydr)oxide contents in different soils. Mineralizable OC (within 90 days) was much smaller than the NaOCl-removable OC and both fractions were negatively correlated ( r 2 = 0.90 for the 18 h treatment; r 2 = 0.86 for the 6 × 6 h treatment), suggesting that chemically oxidizable OM does not represent the portion of sorbed OM available to biological consumption.

Evaluating pore structures of soil components with a combination of “conventional” and hyperpolarised 129Xe NMR studies

129Xe nuclear magnetic resonance (NMR) spectroscopic studies of xenon gas adsorbed on model systems representing soil porous components (Al (hyrd)oxides and charcoals) as well as natural soil materials (derived from a non-allophanic Andosol) were performed with the aim of characterising their micro- (< 2 nm) and mesopores (2–50 nm). Both conventional, i.e. thermally polarised (TP), and laser-polarised or hyperpolarised (HP) 129Xe NMR was applied. The latter technique significantly increased sensitivity of the measurements. Information on the pore size range was derived from the 129Xe resonance shifts, δ, monitored as function of Xe loading, whereas the temperature dependences of δ provided information on the nature of xenon–pore surface interactions in terms of effective adsorption enthalpies. Dissolved organic matter (DOM) sorption on the mesoporous Al 2O 3 was shown to proceed inhomogeneously indicative by the Xe adsorption enthalpies corresponding to the co-existing “empty” pores and pores coated with organic species. In AlOOH, an interconnected system of micro- and mesopores was tested. The enhanced sensitivity of HP 129Xe NMR allowed us detecting micropores in charcoals, where N 2 adsorption method underestimated porosity due to the restricted N 2 diffusion at 77 K. The interconnected pore structure of charcoals was attributed to the voids formed by both polyaromatic and aliphatic domains (evidenced by 13C NMR). The observed differences between the TP- and HP 129Xe NMR patterns were explained by the restricted xenon diffusion through charcoal particles caused by the constricted pore openings. Their suggested size is of the order of one or two diameters of the Xe atom. For the Andosol clay fractions, the large low-field 129Xe shifts (up to 175 ppm) increasing with Xe pressure indicated a developed porosity most obviously comprised by the interconnected micro- and mesopores. Such porous network may originate from the “multi-domain” structure of soil clay particles, i.e. particles formed by agglomerated nano-sized crystallites. The latter are assumed to be the polynuclear Al x (H 2O) y (OH) z clusters formed by hydrolysis reactions of Al 3+ species after the destroying of Al-humus complexes by the H 2O 2-oxidation.

Positive and negative carbon mineralization priming effects among a variety of biochar-amended soils

Abstract Pyrogenic carbon (biochar) amendment is increasingly discussed as a method to increase soil fertility while sequestering atmospheric carbon (C). However, both increased and decreased C mineralization has been observed following biochar additions to soils. In an effort to better understand the interaction of pyrogenic C and soil organic matter (OM), a range of Florida soils were incubated with a range of laboratory-produced biochars and CO 2 evolution was measured over more than one year. More C was released from biochar-amended than from non-amended soils and cumulative mineralized C generally increased with decreasing biomass combustion temperature and from hardwood to grass biochars, similar to the pattern of biochar lability previously determined from separate incubations of biochar alone. The interactive effects of biochar addition to soil on CO 2 evolution (priming) were evaluated by comparing the additive CO 2 release expected from separate incubations of soil and biochar with that actually measured from corresponding biochar and soil mixtures. Priming direction (positive or negative for C mineralization stimulation or suppression, respectively) and magnitude varied with soil and biochar type, ranging from −52 to 89% at the end of 1 year. In general, C mineralization was greater than expected (positive priming) for soils combined with biochars produced at low temperatures (250 and 400 °C) and from grasses, particularly during the early incubation stage (first 90 d) and in soils of lower organic C content. It contrast, C mineralization was generally less than expected (negative priming) for soils combined with biochars produced at high temperatures (525 and 650 °C) and from hard woods, particularly during the later incubation stage (250–500 d). Measurements of the stable isotopic signature of respired CO 2 indicated that, for grass biochars at least, it was predominantly pyrogenic C mineralization that was stimulated during early incubation and soil C mineralization that was suppressed during later incubation stages. It is hypothesized that the presence of soil OM stimulated the co-mineralization of the more labile components of biochar over the short term. The data strongly suggests, however, that over the long term, biochar–soil interaction will enhance soil C storage via the processes of OM sorption to biochar and physical protection.

Sorption of carbamazepine, 17α-ethinylestradiol, iopromide and trimethoprim to biomass involves interactions with exocellular polymeric substances

The sorption of carbamazepine (CBZ), iopromide (IOP), trimethoprim (TMP) and 17α-ethinylestradiol (EE2) was evaluated using four biomass types (pure ammonia oxidizing bacterial culture, two heterotrophic enrichment cultures with varying levels of oxygenase activity, and a full-scale nitrifying activated sludge (NAS) culture). CBZ and IOP did not sorb to the four biomass types. EE2 did not sorb to the pure culture but sorbed significantly to the heterotrophic cultures and NAS. TMP sorbed to the heterotrophic cultures and NAS, and was not evaluated for the pure culture. Three floc characteristics (hydrophobicity, median particle size, organic matter content) correlated moderately well with the EE2 organic matter sorption coefficient ( K OM,EE2). Zeta potential did not correlate well with K OM,EE2 but did with K OM,TMP, indicating that TMP sorption is more influenced by electrostatic factors than EE2. Once divalent cation-linked exocellular polymeric substances (EPS) were removed from flocs, EE2 and TMP sorption to the non-EPS (cellular) fraction decreased by approximately 50%. The correlation between K OM,EE2 for the non-EPS cellular fraction deteriorated while the correlation between K OM,TMP improved. EE2 seemed to sorb more strongly to EPS protein whereas TMP sorbed equally to polysaccharide and protein EPS. Attempts to develop predictive models were not successful. Pharmaceuticals that sorbed to biomass samples underwent biodegradation whereas those that did not sorb were not biodegraded, suggesting a relationship between sorption and pharmaceutical biotransformation.

Toluene and naphthalene sorption by iron oxide/clay composites

This study investigates the sorption of toluene and naphthalene by a sodium bentonite (BFN), an organoclay (WS35) and by their respective iron oxide hydrate composites Mag_BFN and Mag_S35. The organic matter content of WS35 and Mag_S35, determined by thermogravimetry, was used to obtain their organic matter sorption coefficients, which show that they are effective sorbents to remove organic contaminants from water, with a higher selectivity for naphthalene than for toluene sorption. The main iron oxide phase present in Mag_BFN and Mag_S35 is maghemite (γ-Fe2O3), which allows these sorbents to be separated from the effluent by a magnetic separation process after use.