Biochar affected by composting with farmyard manure.

Biochar applications to soils can improve soil fertility by increasing the soil's cation exchange capacity (CEC) and nutrient retention. Because biochar amendment may occur with the applications of organic fertilizers, we tested to which extent composting with farmyard manure increases CEC and nutrient content of charcoal and gasification coke. Both types of biochar absorbed leachate generated during the composting process. As a result, the moisture content of gasification coke increased from 0.02 to 0.94 g g, and that of charcoal increased from 0.03 to 0.52 g g. With the leachate, the chars absorbed organic matter and nutrients, increasing contents of water-extractable organic carbon (gasification coke: from 0.09 to 7.00 g kg; charcoal: from 0.03 to 3.52 g kg), total soluble nitrogen (gasification coke: from not detected to 705.5 mg kg; charcoal: from 3.2 to 377.2 mg kg), plant-available phosphorus (gasification coke: from 351 to 635 mg kg; charcoal: from 44 to 190 mg kg), and plant-available potassium (gasification coke: from 6.0 to 15.3 g kg; charcoal: from 0.6 to 8.5 g kg). The potential CEC increased from 22.4 to 88.6 mmol kg for the gasification coke and from 20.8 to 39.0 mmol kg for the charcoal. There were little if any changes in the contents and patterns of benzene polycarboxylic acids of the biochars, suggesting that degradation of black carbon during the composting process was negligible. The surface area of the biochars declined during the composting process due to the clogging of micropores by sorbed compost-derived materials. Interactions with composting substrate thus enhance the nutrient loads but alter the surface properties of biochars.

Effects of natural organic matter on the microporous sorption sites of black carbon in a Yangtze River sediment.

Black carbon (BC), characterized by high microporosity and high specific surface area (SSA), has been demonstrated to have substantial contributions to the sorption of hydrophobic organic chemicals in soils and sediments. Other naturally occurring organic matters provide soft and penetrable sorption domains while may cling to BC and affect its original surface properties. In this work, we studied the sorption sites of a Yangtze River sediment sample with organic carbon (OC) content of 3.3 % and the preheated sediment (combusted at 375 °C) with reduced OC content (defined as BC) of 0.4 % by gas and pyrene sorption. The SSA and microporosity of the pristine and preheated sediments were characterized by N2 and CO2 adsorption. The results suggest that the adsorption of N2 was hindered by amorphous organic carbon (AOC) in the pristine sediment but CO2 was not. Instead, the uptake of CO2 was higher in the presence of AOC, likely due to the partition of CO2 molecules into the organic matter. The pyrene adsorptions to BC in pristine and preheated sediments show a similar adsorption capacity at high concentration, suggesting that AOC of ca. 2.9 % in the pristine sediment does not reduce the accessibility to the sorption sites on BC for pyrene.

Sorption of a branched nonylphenol and perfluorooctanoic acid on Yangtze River sediments and their model components.

Many metabolites of organic surfactants such as nonylphenol (NP) and perfluorooctanoic acid (PFOA) are ubiquitously found in the environment and are toxic if not sorbed on soils and sediments. In this study, we quantified the sorption of the NP isomer with the highest endocrine activity, [4-(1-ethyl-1,3-dimethylpentyl) phenol] (NP111), and that of PFOA on Yangtze River sediments and its model components illite, goethite and natural organic matter. The sorption experiments were performed with (14)C-labeled NP111 and PFOA by batch or dialysis techniques. The results showed that the sorption isotherms of NP111 and PFOA on the sediments were fitted well by the linear adsorption model. The sorption of NP111 depended largely on the organic carbon content of the sediments. The K(OC) values of NP111 ranged from 6 × 10(3) to 1.1 × 10(4) L kg(-1) indicating that hydrophobic interaction between NP and organic carbon is the main mechanism of sorption. The sorption of NP111 on illite was poor. The sorption of PFOA on the sediments was significantly lower than that of NP111. The affinity of PFOA to adsorb on goethite was slightly higher than on the sediments, but was moderate on illite and negligible on a reference natural organic matter. Principal axis component analysis confirmed that various sediment parameters control the binding of PFOA. This analysis grouped the respective K(d) values to the contents of black carbon, iron oxides and clay, and, hence, to the specific surface area of the sediments.

Surface-associated metal catalyst enhances the sorption of perfluorooctanoic acid to multi-walled carbon nanotubes.

The perfluorooctanoic acid (PFOA) sorption behavior of two commercial multi-walled carbon nanotubes (MWCNTs) (C 150 P from Bayer MaterialScience: BA and C-MWNTs from NanoTechLabs Inc.: CP) was investigated from aqueous solution. The BA nanotubes contained Co/Mn/Mg/Al catalysts both on their outer surface and in the inner bore while CP contained Fe-based catalyst typically within the tubes. The adsorption isotherms of (14)C-radiolabeled PFOA were measured by batch experiments and fitted to the Freundlich model (r(2)>0.92). The adsorption affinity and capacity on BA were significantly higher than on CP. Increasing the pH reduced the adsorption of PFOA due to the electrostatic interaction between the pH-sensitive surface and the adsorbate. Increasing the NaCl concentration led to the aggregation of the MWCNTs reducing the available surface and thus the adsorption capacity. Removal of the catalyst from the outer surface of BA changed the electrophoretic mobility from a positive to a negative value and also decreased the adsorbed amount of PFOA. The surface charge of the surface-associated metal catalyst favors the electrostatic sorption of PFOA. Such surface modifications may be a promising way to improve the sorption capacity of MWCNTs for pollutants such as PFOA and to broaden their potential application in water purification.

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.

Pyrene and phenanthrene sorption to model and natural geosorbents in single- and binary-solute systems.

Sorption of pyrene and phenanthrene to model (illite and charcoal) and natural (Yangtze sediment) geosorbents were investigated by batch techniques using fluorescence spectroscopy. A higher adsorption of phenanthrene was observed with all sorbents, which is related to the better accessibility of smaller molecules to micropores in the molecular sieve sorbents. In addition, pyrene sorption in binary-solute systems with a constant initial concentration of phenanthrene (0.1 µmol L(-1) or 2 µmol L(-1)) was studied. A 0.1 µmol L(-1) concentration of phenanthrene causes no competitive effect on the pyrene sorption. A 2 µmol L(-1) concentration of phenanthrene significantly suppresses the sorption of pyrene, especially in the low concentration range; nonlinearity of the pyrene sorption isotherms thus decreases. The competitive effect of 2 µmol L(-1) phenanthrene on the pyrene sorption is overestimated by the ideal adsorbed solution theory (IAST) using the fitted single sorption results of both solutes. An adjustment of the IAST application by taking into account the molecular sieve effect is proposed, which notably improves the IAST prediction for the competitive effect.

Effect of organic carbon and mineral surface on the pyrene sorption and distribution in Yangtze River sediments.

The effect of organic carbon (OC) and mineral surface on the sorption of polycyclic aromatic hydrocarbon (PAH) pyrene molecule to four Yangtze River sediments was investigated by sorption batch techniques using fluorescence spectroscopy. Pyrene sorption to the mineral fraction was estimated with model sorbent illite, the main clay mineral in Yangtze sediment. The Freundlich model fitted sorption to illite and to sediments was normalized to the specific surface area (SSA). Comparison of the SSA-normalized sorption capacities of illite and sediments suggests a negligible contribution of the pyrene sorption to the mineral fraction. In addition, composite models, such as the linear Langmuir model (LLM) and the linear Polanyi-Dubinin-Manes model (LPDMM) were applied for fitting the sorption of pyrene to the pristine sediments. The application of composite models allows assessing the partition of pyrene into amorphous organic carbon (AOC) and the adsorption in the porous structure of black carbon (BC). The modelling results indicate that the pyrene adsorption to the minor BC components (<0.2%) is more effective than the partition to AOC (0.5-1.3%). Besides the pristine sediments, sediments preheated at 375 degrees C were also studied, in which the AOC fraction was removed during the preheating treatment. The modelling results with LPDMM and Polanyi-Dubinin-Manes model (PDMM) indicate a similar adsorption capacity of BC in pristine and preheated sediments, respectively. The low AOC concentrations in sediments do not diminish the BC micropore filling with pyrene. Simulation of pyrene distribution in the investigated Yangtze River sediments support the importance of the BC fraction in the PAH immobilization under environmental conditions.

Modeling the effects of Ca2+ and clay-associated organic carbon on the stability of colloids from topsoils.

The goals of the study were to investigate the effects of the soil-water phase ionic strength, mainly monitored by the calcium ion (Ca(2+)) concentration, on the stability behavior of easily dispersed topsoil colloidal clay-sized particles (<2 microm). The aggregation kinetics as a function of the Ca(2+) concentration was monitored by measuring the increase of the particle size over time with photon correlation spectroscopy. The critical coagulation concentrations (CCC) of Ca(2+) were measured. The Hamaker constants (A) characterizing the attractive chemical properties of the topsoil colloid surface were thus scaled according to the Derjaguin, Landau, Verwey, Overbeek (DLVO) theory by taking into account the electrokinetic behavior of the particles, measured by the zeta-potential. Effective values for the Hamaker constants of topsoil clay-sized colloids, clay minerals, and metal oxides were calculated by referring to reported values for crystalline silica or sand (quartz) particles. Potential-energy diagrams of interacting topsoil clay-sized colloids were calculated. The primary energy maximum and secondary energy minimum were used for modeling the aggregation kinetics along the Ca(2+) concentration by employing Marmur's model. Coagulation in the secondary energy minimum can only explain the aggregation efficiency of topsoil colloids at low Ca(2+) concentrations (<2 mM Ca(2+)) under unfavorable electrostatic conditions. The effect of surface-associated organic matter on the colloidal electrosteric stability was also investigated by comparing the topsoil colloid stability after the removal of organic matter.