Ordered mesoporous materials in catalysis

Evidence is accumulating that sorption of organic chemicals to soils and sediments can be described by “dual-mode sorption”:  absorption in amorphous organic matter (AOM) and adsorption to carbonaceous materials such as black carbon (BC), coal, and kerogen, collectively termed “carbonaceous geosorbents” (CG). Median BC contents as a fraction of total organic carbon are 9% for sediments (number of sediments, n ≈ 300) and 4% for soils (n = 90). Adsorption of organic compounds to CG is nonlinear and generally exceeds absorption in AOM by a factor of 10−100. Sorption to CG is particularly extensive for organic compounds that can attain a more planar molecular configuration. The CG adsorption domain probably consists of surface sites and nanopores. In this review it is shown that nonlinear sorption to CG can completely dominate total sorption at low aqueous concentrations (<10-6 of maximum solid solubility). Therefore, the presence of CG can explain (i) sorption to soils and sediments being up to 2 orders of m...

Extensive sorption of organic compounds to black carbon, coal, and kerogen in sediments and soils: mechanisms and consequences for distribution, bioaccumulation, and biodegradation

BACKGROUND The invention of the Haber-Bosch (H-B) process in the early 1900s to produce ammonia industrially from nitrogen and hydrogen revolutionized the manufacture of fertilizer and led to fundamental changes in the way food is produced. Its impact is underscored by the fact that about 50% of the nitrogen atoms in humans today originate from this single industrial process. In the century after the H-B process was invented, the chemistry of carbon moved to center stage, resulting in remarkable discoveries and a vast array of products including plastics and pharmaceuticals. In contrast, little has changed in industrial nitrogen chemistry. This scenario reflects both the inherent efficiency of the H-B process and the particular challenge of breaking the strong dinitrogen bond. Nonetheless, the reliance of the H-B process on fossil fuels and its associated high CO 2 emissions have spurred recent interest in finding more sustainable and environmentally benign alternatives. Nitrogen in its more oxidized forms is also industrially, biologically, and environmentally important, and synergies in new combinations of oxidative and reductive transformations across the nitrogen cycle could lead to improved efficiencies. ADVANCES Major effort has been devoted to developing alternative and environmentally friendly processes that would allow NH 3 production at distributed sources under more benign conditions, rather than through the large-scale centralized H-B process. Hydrocarbons (particularly methane) and water are the only two sources of hydrogen atoms that can sustain long-term, large-scale NH 3 production. The use of water as the hydrogen source for NH 3 production requires substantially more energy than using methane, but it is also more environmentally benign, does not contribute to the accumulation of greenhouse gases, and does not compete for valuable and limited hydrocarbon resources. Microbes living in all major ecosystems are able to reduce N 2 to NH 3 by using the enzyme nitrogenase. A deeper understanding of this enzyme could lead to more efficient catalysts for nitrogen reduction under ambient conditions. Model molecular catalysts have been designed that mimic some of the functions of the active site of nitrogenase. Some modest success has also been achieved in designing electrocatalysts for dinitrogen reduction. Electrochemistry avoids the expense and environmental damage of steam reforming of methane (which accounts for most of the cost of the H-B process), and it may provide a means for distributed production of ammonia. On the oxidative side, nitric acid is the principal commodity chemical containing oxidized nitrogen. Nearly all nitric acid is manufactured by oxidation of NH 3 through the Ostwald process, but a more direct reaction of N 2 with O 2 might be practically feasible through further development of nonthermal plasma technology. Heterogeneous NH 3 oxidation with O 2 is at the heart of the Ostwald process and is practiced in a variety of environmental protection applications as well. Precious metals remain the workhorse catalysts, and opportunities therefore exist to develop lower-cost materials with equivalent or better activity and selectivity. Nitrogen oxides are also environmentally hazardous pollutants generated by industrial and transportation activities, and extensive research has gone into developing and applying reduction catalysts. Three-way catalytic converters are operating on hundreds of millions of vehicles worldwide. However, increasingly stringent emissions regulations, coupled with the low exhaust temperatures of high-efficiency engines, present challenges for future combustion emissions control. Bacterial denitrification is the natural analog of this chemistry and another source of study and inspiration for catalyst design. OUTLOOK Demands for greater energy efficiency, smaller-scale and more flexible processes, and environmental protection provide growing impetus for expanding the scope of nitrogen chemistry. Nitrogenase, as well as nitrifying and denitrifying enzymes, will eventually be understood in sufficient detail that robust molecular catalytic mimics will emerge. Electrochemical and photochemical methods also demand more study. Other intriguing areas of research that have provided tantalizing results include chemical looping and plasma-driven processes. The grand challenge in the field of nitrogen chemistry is the development of catalysts and processes that provide simple, low-energy routes to the manipulation of the redox states of nitrogen.

http://science.sciencemag.org/content/sci/360/6391/eaar6611.full.pdf

Beyond fossil fuel-driven nitrogen transformations.

Chars originating from the burning or pyrolysis of vegetation may significantly sorb neutral organic contaminants (NOCs). To evaluate the relationship between the char composition and NOC sorption,...

Compositions and sorptive properties of crop residue-derived chars.

Biochar application to soils is being considered as a means to sequester carbon (C) while concurrently improving soil functions. The main focus of this report is providing a critical scientific review of the current state of knowledge regarding the effects of biochar application to soils on soil properties and functions. Wider issues, including atmospheric emissions and occupational health and safety associated to biochar production and handling, are put into context. The aim of this review is to provide a sound scientific basis for policy development, to identify gaps in current knowledge, and to recommend further research relating to biochar application to soils. See Table 1 for an overview of the key findings from this report. Biochar research is in its relative infancy and as such substantially more data are required before robust predictions can be made regarding the effects of biochar application to soils, across a range of soil, climatic and land management factors. Definition In this report, biochar is defined as: “charcoal (biomass that has been pyrolysed in a zero or low oxygen environment) for which, owing to its inherent properties, scientific consensus exists that application to soil at a specific site is expected to sustainably sequester carbon and concurrently improve soil functions (under current and future management), while avoiding shortand long-term detrimental effects to the wider environment as well as human and animal health." Biochar as a material is defined as: "charcoal for application to soils". It should be noted that the term 'biochar' is generally associated with other co-produced end products of pyrolysis such as 'syngas'. However, these are not usually applied to soil and as such are only discussed in brief in the report. Biochar properties Biochar is an organic material produced via the pyrolysis of C-based feedstocks (biomass) and is best described as a ‘soil conditioner’. Despite many different materials having been proposed as biomass feedstock for biochar (including wood, crop residues and manures), the suitability of each feedstock for such an application is dependent on a number of chemical, physical, environmental, as well as economic and logistical factors. Evidence suggests that components of the carbon in biochar are highly recalcitrant in soils, with reported residence times for wood biochar being in the range of 100s to 1,000s of years, i.e. approximately 101,000 times longer than residence times of most soil organic matter. Therefore, biochar addition to soil can provide a potential sink for C. It is important to note, however, that there is a paucity of data concerning biochar produced from feedstocks other than wood, but the information that is available is discussed in the report. Owing to the current interest in climate change mitigation, and the irreversibility of biochar application to soil, an effective evaluation of biochar stability in the environment and its effects on soil processes and functioning is paramount. The current state of knowledge concerning these factors is discussed throughout this report.

Biochar Application to Soils - A Critical Scientific Review of Effects on Soil Properties, Processes and Functions

Isotopic evidence (δ13C, δ37Cl, δ2H) for distinct transformation mechanisms of chloroform: Catalyzed H2-water system vs. zero-valent iron (ZVI)

1 TU Darmstadt, Institute for Applied Geosciences, Darmstadt, Germany 2 Federal Institute for Geosciences and Natural Resources – BGR, Hannover, Germany 3 Gesellschaft fur Internationale Zusammenarbeit International Services – GIZ IS, Riyadh, Kingdom of Saudi Arabia 4 Helmholtz-Centre for Environmental Research – UFZ, Halle, Germany 5 Ministry of Water & Electricity, Riyadh, Kingdom of Saudi Arabia

http://www.bgr.bund.de/EN/Themen/Wasser/Veranstaltungen/hydroarid_2012/download/Poster_Reshid.pdf?__blob=publicationFile&v=2

Identification of Multiple Nitrate Sources in Selected Saudi Arabian Aquifers Using a Multi-Isotope Approach

The coastal and carbonate Mean Sea Level Aquifer (MSLA) of Malta is characterised by high anisotropy and heterogeneity, which together make evaluating the aquifer system parameters a challenging task. In this paper, we present an approach for the determination of the hydrogeological parameters of this coastal aquifer based on tidal-induced groundwater fluctuations that can be applied in other similar contexts. This work presents an analysis of data undertaken on monitoring boreholes located in the Malta MSLA exhibiting tidal-induced groundwater fluctuations. This allowed us to determine the values of three main hydrogeological parameters: hydraulic diffusivity, transmissivity and hydraulic conductivity. These will subsequently be used as an input for groundwater flow and reactive transport modelling purposes. In this study, a methodology based on the fast Fourier transform (FFT) is proposed to improve the applicability of the Jacob–Ferris method to the observed groundwater level and sea level fluctuations. The FFT reproduced signals allowed us to isolate the component induced by sea tides, thus eliminating short- and long-term variations of the water table induced by other disruptive factors. Results showed high variability of hydrogeological parameters within a short distance, reflecting the high anisotropy and heterogeneity of the aquifer system. The transmissivity values derived from the Jacob–Ferris method are complemented with results derived from the pumping tests with the aim of estimating the spatial distribution of the aquifer transmissivity for the study area. The spatial variability of transmissivity values is analysed by means of geostatistics tools for estimating uncertainty, correlation and variation in space through the use of semi-variograms.

/pdf/determining-aquifer-hydrogeological-parameters-in-coastal-2le4hdse.pdf

Determining Aquifer Hydrogeological Parameters in Coastal Aquifers from Tidal Attenuation Analysis, Case Study: The Malta Mean Sea Level Aquifer System

Trichloroethylene (TCE) was degraded aerobically with the strain Burkholderia cepacia G4. The degradation leveled out after similar to 40 hours, while the removal efficiency depended on the optical cell density (OD540) During the experiment at an OD540 of 0.8, TCE was degraded up to 59.3%, with an isotopic difference between initial and remaining substrate of 12.3 parts per thousand. At a lower OD540 of 0.5 the amount of TCE degraded was only 40.5% and the delta(13)C(TCE) difference between initial and remaining substrate was 10.5 parts per thousand

Changes of the carbon isotopic composition of trichloroethylene during aerobic biodegradation: : a new tool to estimate removal efficiencies

Water phase as well as gas phase catalysis using noble metals is a promising technology for water treatment However, catalytic reactions are in general hampered by catalyst deactivation due to complex water chemistry, especially the presence of reduced sulfur species In a mobile pilot scale treatment unit (Treatment Train) techniques were developed to, (i) optimize reaction rates and, (ii) to increase the stability of the catalysts against deactivation Examples are presented for both, water phase catalysis and gas phase catalysis Approaches for the water phase rely on tailored support materials for catalyst protection while in the gas phase pretreatment of the poisonous compounds is favored

/pdf/groundwater-remediation-methods-based-on-noble-metal-4j1aikxjrf.pdf

Christoph Schüth

Papers

Isotopic evidence (δ13C, δ37Cl, δ2H) for distinct transformation mechanisms of chloroform: Catalyzed H2-water system vs. zero-valent iron (ZVI)

Identification of Multiple Nitrate Sources in Selected Saudi Arabian Aquifers Using a Multi-Isotope Approach

Determining Aquifer Hydrogeological Parameters in Coastal Aquifers from Tidal Attenuation Analysis, Case Study: The Malta Mean Sea Level Aquifer System

Changes of the carbon isotopic composition of trichloroethylene during aerobic biodegradation: : a new tool to estimate removal efficiencies

Groundwater remediation methods based on noble metal catalysts – results from the pilot unit Treatment Train