Microbial metabolism mediates interactions between dissolved organic matter and clay minerals in streamwater

Sorption of organic molecules to mineral surfaces is an important control upon the aquatic carbon (C) cycle. Organo-mineral interactions are known to regulate the transport and burial of C within inland waters, yet the mechanisms that underlie these processes are poorly constrained. Streamwater contains a complex and dynamic mix of dissolved organic compounds that coexists with a range of organic and inorganic particles and microorganisms. To test how microbial metabolism and organo-mineral complexation alter amino acid and organic carbon fluxes we experimented with 13C-labelled amino acids and two common clay minerals (kaolinite and montmorillonite). The addition of 13C-labelled amino acids stimulated increased microbial activity. Amino acids were preferentially mineralized by the microbial community, concomitant with the leaching of other (non-labelled) dissolved organic molecules that were removed from solution by clay-mediated processes. We propose that microbial processes mediate the formation of organo-mineral particles in streamwater, with potential implications for the biochemical composition of organic matter transported through and buried within fluvial environments.

Physico-geochemical and mineral composition of neem tree soils and relation to organic properties

The Neem tree, the oil of which has a long history of pesticide, fertilizer and medicinal use in India, has been studied extensively for its organic compounds. Here we present a physical, mineralogical and geochemical database resulting from the analyses of two Neem soil profiles (epipedons) in India. Neem tree derivatives are used in the manufacture of a variety of products, from anti-bacterial drugs and insecticides to fertilizers and animal feeds. A preliminary geochemical and mineralogical analysis of Neem soils is made to explore the potential for chemical links between Neem tree derivatives and soils. Physical soil characteristics, including colour, texture and clay mineralogy, suggest the two pedons formed under different hydrological regimes, and hence, are products of different leaching environments, one well-drained site, the other poorly drained. Geochemically, the two Neem soils exhibit similarities, with elevated concentrations of Th and rare earth elements. These elements are of interest because of their association with phosphates, especially monazite and apatite, and the potential link to fertilizer derivatives. Higher concentrations of trace elements in the soils may be linked to nutritional derivatives and to cell growth in the Neem tree.

Ultrasound-assisted electrochemical treatment of wastewaters containing organic pollutants by using novel Ti/Ta2O5-SnO2 electrodes

Advanced oxidation processes (AOPs) are modern methods using reactive hydroxyl radicals for the mineralization of organic pollutants into simple inorganic compounds, such as CO2 and H2O. Among AOPs electrochemical oxidation (EO) is a method suitable for coloured and turbid wastewaters. The degradation of pollutants occurs on electrocatalytic electrodes. The majority of electrodes contain in their structure either expensive materials (diamond and Pt-group metals) or are toxic for the environment compounds (Sb or Pb). One of the main disadvantages of electrochemical method is the polarization and contamination of electrodes due to the deposition of reaction products on their surface, which results in diminishing of the process efficiency. Ultrasound combined with the electrochemical degradation process eliminates electrode contamination because of the continuous mechanical cleaning effect produced by the formation and collapse of acoustic cavitation bubbles near to the electrode surface. Moreover, high frequency ultrasound generates hydroxyl radicals at water sonolysis. Ultrasound-assisted EO is a non-selective method for oxidation of different organic compounds with high degradation efficiencies. The aim of this research was to develop novel sustainable and cost-effective electrodes working as electrocatalysts and test their activity in electrocatalytic oxidation of organic compounds such as dyes and organic acids. Moreover, the goal of the research was to enhance the efficiency of electrocatalytic degradation processes by assisting it with ultrasound in order to eliminate the main drawbacks of a single electrochemical oxidation such as electrodes polarization and passivation. Novel Ti/Ta2O5-SnO2 electrodes were developed and found to be electrocatalytically active towards water (with 5% Ta content, 10 oxide film layers) and organic compounds oxidation (with 7.5% Ta content, 8 oxide film layers) and therefore these electrodes can be applicable in both environmental and energy fields. The synergetic effect of combined electrolysis and sonication was shown while conducting sonoelectrochemical (EO/US) degradation of methylene blue (MB) and formic acid (FA). Complete degradation of MB and FA was achieved after 45 and 120 min of EO/US process respectively in neutral media. Mineralization efficiency of FA over 95% was obtained after 2 h of degradation using high frequency ultrasound (381, 863, 1176 kHz) combined with 9.1 mA/cm2 current density. EO/US degradation of MB provided over 75% mineralization in 8 h. High degradation kinetic rates and mineralization efficiencies of model pollutants obtained in EO/US experiments provide the preconditions for further extrapolation of this treatment method to pilot scale studies with industrial wastewaters.

Modeling the Effect of Vapor Wall Deposition on the Formation of Secondary Organic Aerosol in Chamber Studies

Laboratory chamber experiments are used to investigate formation of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors under a variety of environmental conditions. Simulations of these experiments test our understanding of the prevailing chemistry of SOA formation as well as the dynamic processes occurring in the chamber itself. One dynamic process occurring in the chamber that was only recently recognized is the deposition of vapor species to the Teflon walls of the chamber. Low-volatility products formed from the oxidation of volatile organic compounds (VOCs) deposit on the walls rather than forming SOA, decreasing the amount of SOA formed (quantified as the SOA yield: mass of SOA formed per mass of VOC reacted). In this work, several modeling studies are presented that address the effect of vapor wall deposition on SOA formation in chambers.

A coupled vapor-particle dynamics model is used to examine the competition among the rates of gas-phase oxidation to low volatility products, wall deposition of these products, and mass transfer to the particle phase. The relative time scales of these rates control the amount of SOA formed by affecting the influence of vapor wall deposition. Simulations show that an effect on SOA yield of changing the vapor-particle mass transfer rate is only observed when SOA formation is kinetically limited. For systems with kinetically limited SOA formation, increasing the rate of vapor-particle mass transfer by increasing the concentration of seed particles is an effective way to minimize the effect of vapor wall deposition.

This coupled vapor-particle dynamics model is then applied to α-pinene ozonolysis SOA experiments. Experiments show that the SOA yield is affected when changing the oxidation rate but not when changing the rate of gas-particle mass transfer by changing the concentration of seed particles. Model simulations show that the absence of an effect of changing the seed particle concentration is consistent with SOA formation being governed by quasi-equilibrium growth, in which gas-particle equilibrium is established much faster than the rate of change of the gas-phase concentration. The observed effect of oxidation rate on SOA yield arises due to the presence of vapor wall deposition: gas-phase oxidation products are produced more quickly and condense preferentially onto seed particles before being lost to the walls. Therefore, for α-pinene ozonolysis, increasing the oxidation rate is the most effective way to mitigate the influence of vapor wall deposition.

Finally, the detailed model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to simulate α-pinene photooxidation SOA experiments. Unexpectedly, α-pinene OH oxidation experiments show no effect when changing either the oxidation rate or the vapor-particle mass transfer rate, whereas GECKO-A predicts that changing the oxidation rate should drastically affect the SOA yield. Sensitivity studies show that the assumed magnitude of the vapor wall deposition rate can greatly affect conclusions drawn from comparisons between simulations and experiments. If vapor wall loss in the Caltech chamber is of order 10^-5 s^-1, GECKO-A greatly overpredicts SOA during high UV experiments, likely due to an overprediction of second-generation products. However, if instead vapor wall loss in the Caltech chamber is of order 10^-3 s^-1, GECKO-A greatly underpredicts SOA during low UV experiments, possibly due to missing autoxidation pathways in the α-pinene mechanism.

Effect of gamma-irradiation on total organic carbon and trihalomethane formation potential

This research was conducted to study the use of radiation in water treatment as an alternative to chlorination which has caused health concerns due to the formation of harmful disinfection by-products. Groundwater solutions from the Biscayne aquifer were radiated with Cobalt-60 gamma radiation and studied for changes in dissolved organic carbon (DOC), UV absorbance at 254 nm (UV254), fluorescence and trihalomethane formation potential (THMFP). Molecular fractionations were conducted by ultrafiltration. Effect of the combination of radiation/peroxide was studied for DOC and UV254. Radiation showed significant removal in DOC and THMFP. Similar results were seen in the fluorescence and UV absorbance experiments. Radiation/peroxide did not improve the DOC removal. Radiation of the groundwater samples broke the larger molecular weight fractions in to smaller fractions.

Particle and gaseous emissions from compressed natural gas and ultralow sulphur diesel-fuelled buses at four steady engine loads

Exhaust emissions from thirteen compressed natural gas (CNG) and nine ultralow sulphur diesel in-service transport buses were monitored on a chassis dynamometer. Measurements were carried out at idle and at three steady engine loads of 25%, 50% and 100% of maximum power at a fixed speed of 60 kmph. Emission factors were estimated for particle mass and number, carbon dioxide and oxides of nitrogen for two types of CNG buses (Scania and MAN, compatible with Euro 2 and 3 emission standards, respectively) and two types of diesel buses (Volvo Pre-Euro/Euro1 and Mercedez OC500 Euro3). All emission factors increased with load. The median particle mass emission factor for the CNG buses was less than 1% of that from the diesel buses at all loads. However, the particle number emission factors did not show a statistically significant difference between buses operating on the two types of fuel. In this paper, for the very first time, particle number emission factors are presented at four steady state engine loads for CNG buses. Median values ranged from the order of 1012 particles min-1 at idle to 1015 particles km-1 at full power. Most of the particles observed in the CNG emissions were in the nanoparticle size range and likely to be composed of volatile organic compounds The CO2 emission factors were about 20% to 30% greater for the diesel buses over the CNG buses, while the oxides of nitrogen emission factors did not show any difference due to the large variation between buses.

Estimating indoor air quality using integrated 3D CAD building models

The indoor air quality (IAQ) in buildings is currently assessed by measurement of pollutants during building operation for comparison with air quality standards. Current practice at the design stage tries to minimise potential indoor air quality impacts of new building materials and contents by selecting low-emission materials. However low-emission materials are not always available, and even when used the aggregated pollutant concentrations from such materials are generally overlooked. This paper presents an innovative tool for estimating indoor air pollutant concentrations at the design stage, based on emissions over time from large area building materials, furniture and office equipment. The estimator considers volatile organic compounds, formaldehyde and airborne particles from indoor materials and office equipment and the contribution of outdoor urban air pollutants affected by urban location and ventilation system filtration. The estimated pollutants are for a single, fully mixed and ventilated zone in an office building with acceptable levels derived from Australian and international health-based standards. The model acquires its dimensional data for the indoor spaces from a 3D CAD model via IFC files and the emission data from a building products/contents emissions database. This paper describes the underlying approach to estimating indoor air quality and discusses the benefits of such an approach for designers and the occupants of buildings.

Vibrational spectroscopy of intercalated kaolinites. Part I

The industrial application of kaolinite is closely related to its reactivity and surface properties. The reactivity of kaolinite can be tested by intercalation, i.e. via the insertion of low molecular weight organic compounds between the kaolinite layers resulting in the formation of a nano-layered organo-complex. Although intercalation of kaolinite is an old and ongoing research topic, there is a limited knowledge available on the reactivity of different kaolinites, the mechanism of complex formation as well as on the structure of the complexes formed. Grafting and incorporation of exfoliated kaolinite in polymer matrices and other potential applications can open new horizons in the study of kaolinite intercalation. This paper attempts to summarize (without completion) the most recent achievements in the study of kaolinite organo-complexes obtained with the most common intercalating compounds like urea, potassium acetate, dimethyl sulphoxide, formamide and hydrazine using vibrational spectroscopy combined with X-ray powder diffraction and thermal analysis.

Patterns of substrate utilization during long-term incubations at different temperatures

Microorganisms play key roles in biogeochemical cycling by facilitating the release of nutrients from organic compounds. In doing so, microbial communities use different organic substrates that yield different amounts of energy for maintenance and growth of the community. Carbon utilization efficiency (CUE) is a measure of the efficiency with which substrate carbon is metabolized versus mineralized by the microbial biomass. In the face of global change, we wanted to know how temperature affected the efficiency by which the soil microbial community utilized an added labile substrate, and to determine the effect of labile soil carbon depletion (through increasing duration of incubation) on the community's ability to respond to an added substrate. Cellobiose was added to soil samples as a model compound at several times over the course of a long-term incubation experiment to measure the amount of carbon assimilated or lost as CO2 respiration. Results indicated that in all cases, the time required for the microbial community to take up the added substrate increased as incubation time prior to substrate addition increased. However, the CUE was not affected by incubation time. Increased temperature generally decreased CUE, thus the microbial community was more efficient at 15 degrees C than at 25 degrees C. These results indicate that at warmer temperatures microbial communities may release more CO2 per unit of assimilated carbon. Current climate-carbon models have a fixed CUE to predict how much CO2 will be released as soil organic matter is decomposed. Based on our findings, this assumption may be incorrect due to variation of CUE with changing temperature. (c) 2008 Elsevier Ltd. All rights reserved.

Advances in heterogeneous photocatalytic degradation of phenols and dyes in wastewater : a review

The heterogeneous photocatalytic water purification process has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible light spectrum. This paper aims to review and summarize the recently published works in the field of photocatalytic oxidation of toxic organic compounds such as phenols and dyes, predominant in waste water effluent. In this review, the effects of various operating parameters on the photocatalytic degradation of phenols and dyes are presented. Recent findings suggested that different parameters, such as type of photocatalyst and composition, light intensity, initial substrate concentration, amount of catalyst, pH of the reaction medium, ionic components in water, solvent types, oxidizing agents/electron acceptors, mode of catalyst application, and calcinations temperature can play an important role on the photocatlytic degradation of organic compounds in water environment. Extensive research has focused on the enhancement of photocatalysis by modification of TiO2 employing metal, non-metal and ion doping. Recent advances in TiO2 photocatalysis for the degradation of various phenols and dyes are also highlighted in this review.

Influence of parameters on the heterogeneous photocatalytic degradation of pesticides and phenolic contaminants in wastewater : a short review

In recent years, the application of heterogeneous photocatalytic water purification process has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible light spectrum. This paper aims to review and summarize the recently published works on the titanium dioxide (TiO2) photocatalytic oxidation of pesticides and phenolic compounds, predominant in storm and waste water effluents. The effect of various operating parameters on the photocatalytic degradation of pesticides and phenols are discussed. Results reported here suggested that the photocatalytic degradation of organic compounds depends on the type of photocatalyst and composition, light intensity, initial substrate concentration, amount of catalyst, pH of the reaction medium, ionic components in water, solvent types, oxidizing agents/electron acceptors, catalyst application mode, and calcinations temperature in water environment. A substantial amount of research has focused on the enhancement of TiO2 photocatalysis by modification with metal, non-metal and ion doping. Recent developments in TiO2 photocatalysis for the degradation of various pesticides and phenols are also highlighted in this review. It is evident from the literature survey that photocatalysis has shown good potential for the removal of various organic pollutants. However, still there is a need to find out the practical utility of this technique on commercial scale.