Hydrogen and Methane Production, Energy Recovery, and Organic Matter Removal from Effluents in a Two-Stage Fermentative Process

This study evaluates the potential for using different effluents for simultaneous H-2 and CH4 production in a two-stage batch fermentation process with mixed microflora. An appreciable amount of H-2 was produced from parboiled rice wastewater (23.9 mL g(-1) chemical oxygen demand [COD]) and vinasse (20.8 mL g(-1) COD), while other effluents supported CH4 generation. The amount of CH4 produced was minimum for sewage (46.3 mL g(-1) COD), followed by parboiled rice wastewater (115.5 mL g(-1) COD) and glycerol (180.1 mL g(-1) COD). The maximum amount of CH4 was observed for vinasse (255.4 mL g(-1) COD). The total energy recovery from vinasse (10.4 kJ g(-1) COD) corresponded to the maximum COD reduction (74.7 %), followed by glycerol (70.38 %, 7.20 kJ g(-1) COD), parboiled rice wastewater (63.91 %, 4.92 kJ g(-1) COD), and sewage (51.11 %, 1.85 kJ g(-1) COD). The relatively high performance of vinasse in such comparisons could be attributed to the elevated concentrations of macronutrients contained in raw vinasse. The observations are based on kinetic parameters of H-2 and CH4 production and global energy recovery of the process. These observations collectively suggest that organic-rich effluents can be deployed for energy recovery with sequential generation of H-2 and CH4.

Mapping, organic matter mass and water volume of a peatland in Serra do Espinhaço Meridional

Peatlands form in areas where net primary of organic matter production exceeds losses due to the decomposition, leaching or disturbance. Due to their chemical and physical characteristics, bogs can influence water dynamics because they can store large volumes of water in the rainy season and gradually release this water during the other months of the year. In Diamantina, Minas Gerais, Brazil, a peatland in the environmental protection area of Pau-de-Fruta ensures the water supply of 40,000 inhabitants. The hypothesis of this study is that the peat bogs in Pau-de-Fruta act as an environment for carbon storage and a regulator of water flow in the Córrego das Pedras basin. The objective of this study was to estimate the water volume and organic matter mass in this peatland and to study the influence of this environment on the water flow in the Córrego das Pedras basin. The peatland was mapped using 57 transects, at intervals of 100 m. Along all transects, the depth of the peat bog, the Universal Transverse Mercator (UTM) coordinates and altitude were recorded every 20 m and used to calculate the area and volume of the peatland. The water volume was estimated, using a method developed in this study, and the mass of organic matter based on samples from 106 profiles. The peatland covered 81.7 hectares (ha), and stored 497,767 m³ of water, representing 83.7 % of the total volume of the peat bog. The total amount of organic matter (OM) was 45,148 t, corresponding to 552 t ha-1 of OM. The peat bog occupies 11.9 % of the area covered by the Córrego das Pedras basin and stores 77.6 % of the annual water surplus, thus controlling the water flow in the basin and consequently regulating the water course.

Development, characterization, and application of flowing atmospheric-pressure afterglow ionization for mass spectrometric analysis of ambient organic aerosols

Addressing current limitations of state-of-the-art instrumentation in aerosol research, the aim of this work was to explore and assess the applicability of a novel soft ionization technique, namely flowing atmospheric-pressure afterglow (FAPA), for the mass spectrometric analysis of airborne particulate organic matter. Among other soft ionization methods, the FAPA ionization technique was developed in the last decade during the advent of ambient desorption/ionization mass spectrometry (ADI–MS). Based on a helium glow discharge plasma at atmospheric-pressure, excited helium species and primary reagent ions are generated which exit the discharge region through a capillary electrode, forming the so-called afterglow region where desorption and ionization of the analytes occurs. Commonly, fragmentation of the analytes during ionization is reported to occur only to a minimum extent, predominantly resulting in the formation of quasimolecular ions, i.e. [M+H]+ and [M–H]– in the positive and the negative ion mode, respectively. Thus, identification and detection of signals and their corresponding compounds is facilitated in the acquired mass spectra. The focus of the first part of this study lies on the application, characterization and assessment of FAPA–MS in the offline mode, i.e. desorption and ionization of the analytes from surfaces. Experiments in both positive and negative ion mode revealed ionization patterns for a variety of compound classes comprising alkanes, alcohols, aldehydes, ketones, carboxylic acids, organic peroxides, and alkaloids. Besides the always emphasized detection of quasimolecular ions, a broad range of signals for adducts and losses was found. Additionally, the capabilities and limitations of the technique were studied in three proof-of-principle applications. In general, the method showed to be best suited for polar analytes with high volatilities and low molecular weights, ideally containing nitrogen- and/or oxygen functionalities. However, for compounds with low vapor pressures, containing long carbon chains and/or high molecular weights, desorption and ionization is in direct competition with oxidation of the analytes, leading to the formation of adducts and oxidation products which impede a clear signal assignment in the acquired mass spectra. Nonetheless, FAPA–MS showed to be capable of detecting and identifying common limonene oxidation products in secondary OA (SOA) particles on a filter sample and, thus, is considered a suitable method for offline analysis of OA particles. In the second as well as the subsequent parts, FAPA–MS was applied online, i.e. for real time analysis of OA particles suspended in air. Therefore, the acronym AeroFAPA–MS (i.e. Aerosol FAPA–MS) was chosen to refer to this method. After optimization and characterization, the method was used to measure a range of model compounds and to evaluate typical ionization patterns in the positive and the negative ion mode. In addition, results from laboratory studies as well as from a field campaign in Central Europe (F–BEACh 2014) are presented and discussed. During the F–BEACh campaign AeroFAPA–MS was used in combination with complementary MS techniques, giving a comprehensive characterization of the sampled OA particles. For example, several common SOA marker compounds were identified in real time by MSn experiments, indicating that photochemically aged SOA particles were present during the campaign period. Moreover, AeroFAPA–MS was capable of detecting highly oxidized sulfur-containing compounds in the particle phase, presenting the first real-time measurements of this compound class. Further comparisons with data from other aerosol and gas-phase measurements suggest that both particulate sulfate as well as highly oxidized peroxyradicals in the gas phase might play a role during formation of these species. Besides applying AeroFAPA–MS for the analysis of aerosol particles, desorption processes of particles in the afterglow region were investigated in order to gain a more detailed understanding of the method. While during the previous measurements aerosol particles were pre-evaporated prior to AeroFAPA–MS analysis, in this part no external heat source was applied. Particle size distribution measurements before and after the AeroFAPA source revealed that only an interfacial layer of OA particles is desorbed and, thus, chemically characterized. For particles with initial diameters of 112 nm, desorption radii of 2.5–36.6 nm were found at discharge currents of 15–55 mA from these measurements. In addition, the method was applied for the analysis of laboratory-generated core-shell particles in a proof-of-principle study. As expected, predominantly compounds residing in the shell of the particles were desorbed and ionized with increasing probing depths, suggesting that AeroFAPA–MS might represent a promising technique for depth profiling of OA particles in future studies.

Structural characterization of water-soluble atmospheric organic matter by ultrahigh-resolution mass spectrometry

Isolated water-soluble analytes extracted from fog water collected during a radiation fog event near Fresno, CA were analyzed using collision induced dissociation and ultrahigh-resolution mass spectrometry. Tandem mass analysis was performed on scan ranges between 100-400 u to characterize the structures of nitrogen and/or sulfur containing species. CHNO, CHOS, and CHNOS compounds were targeted specifically because of the high number of oxygen atoms contained in their molecular formulas. The presence of 22 neutral losses corresponding to fragment ions was evaluated for each of the 1308 precursors. Priority neutral losses represent specific polar functional groups (H2O, CO2, CH3OH, HNO3, SO3, etc., and several combinations of these). Additional neutral losses represent non-specific functional groups (CO, CH2O, C3H8, etc.) Five distinct monoterpene derived organonitrates, organosulfates, and nitroxy-organosulfates were observed in this study, including C10H16O7S, C10H17NO7S, C10H17 NO8S, C10H17NO9S, and C10H17NO10S. Nitrophenols and linear alkyl benzene sulfonates were present in high abundance. Liquid chromatography/mass spectrometery methodology was developed to isolate and quantify nitrophenols based on their fragmentation behavior.

Arsenic and selenium mobilisation from organic matter treated mine spoil with and without inorganic fertilisation

Organic matter amendments are applied to contaminated soil to provide a better habitat for re-vegetation and remediation, and olive mill waste compost (OMWC) has been described as a promising material for this aim. We report here the results of an incubation experiment carried out in flooded conditions to study its influence in As and metal solubility in a trace elements contaminated soil. NPK fertilisation and especially organic amendment application resulted in increased As, Se and Cu concentrations in pore water. Independent of the amendment, dimethylarsenic acid (DMA) was the most abundant As species in solution. The application of OMWC increased pore water dissolved organic-carbon (DOC) concentrations, which may explain the observed mobilisation of As, Cu and Se; phosphate added in NPK could also be in part responsible of the mobilisation caused in As. Therefore, the application of soil amendments in mine soils may be particularly problematic in flooded systems.

Optimized Demineralization Technique for the Measurement of Stable Isotope Ratios of Nonexchangeable H in Soil Organic Matter

To make use of the isotope ratio of nonexchangeable hydrogen (δ2Hn (nonexchangeable)) of bulk soil organic matter (SOM), the mineral matrix (containing structural water of clay minerals) must be separated from SOM and samples need to be analyzed after H isotope equilibration. We present a novel technique for demineralization of soil samples with HF and dilute HCl and recovery of the SOM fraction solubilized in the HF demineralization solution via solid-phase extraction. Compared with existing techniques, organic C (Corg) and organic N (Norg) recovery of demineralized SOM concentrates was significantly increased (Corg recovery using existing techniques vs new demineralization method: 58% vs 78%; Norg recovery: 60% vs 78%). Chemicals used for the demineralization treatment did not affect δ2Hn values as revealed by spiking with deuterated water. The new demineralization method minimized organic matter losses and thus artificial H isotope fractionation, opening up the opportunity to use δ2Hn analyses of SOM as a new tool in paleoclimatology or geospatial forensics.

Stabilisation of precipitates of pedogenic dissolved organic matter by multivalent cations

Purpose Precipitation of dissolved organic matter (DOM) by multivalent cations is important for biogeochemical cycling of organic carbon. We investigated to which extent cation bridges are involved in DOM precipitation and how cross-links by cations and water molecule bridges (WaMB) stabilise the matrix of precipitated DOM. Materials and methods DOM was precipitated from the aqueous extract of a forest floor layer adding solutions of Ca(NO3)2, Al(NO3)3 and Pb(NO3)2 with different initial metal cation/C (Me/C) ratios. Precipitates were investigated by differential scanning calorimetry before and after ageing to detect cation bridges, WaMB and restructuring of supramolecular structure. Results and discussion Twenty-five to sixty-seven per cent of the dissolved organic carbon was precipitated. The precipitation efficiency of cations increased in the order Ca < Al < Pb, while the cation content of precipitates increased in the order Pb < Ca < Al. The different order and the decrease in the WaMB transition temperature (T*) for Al/C > 3 is explained by additional formation of small AlOOH particles. Thermal analysis indicated WaMB and their disruption at T* of 53–65 °C. Like cation content, T* increased with increasing Me/C ratio and in the order Ca < Pb < Al for low Me/C. This supports the general assumption that cross-linking ability increases in the order Ca < Pb < Al. The low T* for high initial Me/C suggests less stable and less cross-linked precipitates than for low Me/C ratios. Conclusions Our results suggest a very similar thermal behaviour of OM bound in precipitates compared with soil organic matter and confirms the relevance of WaMB in stabilisation of the supramolecular structure of cation-DOM precipitates. Thus, stabilisation of the supramolecular structure of the DOM precipitates is subjected to dynamics in soils.