Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures

Immobilization of Burkholderia cepacia Lipase: Kinetic Resolution in Organic Solvents, Ionic Liquids and in Their Mixtures Biocatalysis opens the door to green and sustainable processes in synthetic chemistry allowing the preparation of single enantiomers, since the enzymes are chiral and accordingly able to catalyze chemical reactions under mild conditions. Immobilization of enzymes enhances process robustness, often stabilizes and activates the enzyme, and enables reuse of the same enzyme preparation in multiple cycles. Although hundreds of variations of immobilization methods exist, there is no universal method to yield the highly active, selective and stable enzyme catalysts. Therefore, new methods need to be developed to obtain suitable catalysts for different substrates and reaction environments. Lipases are the most widely used enzymes in synthetic organic chemistry. The literature part together with the experimental part of this thesis discusses of the effects of immobilization methods mostly used to enhance lipase activity, stability and enantioselectivity. Moreover, the use of lipases in the kinetic resolution of secondary alcohols in organic solvents and in ionic liquids is discussed. The experimental work consists of the studies of immobilization of Burkholderia cepacia lipase (lipase PS) using three different methods: encapsulation in sol-gels, cross-linked enzyme aggregates (CLEAs) and supported ionic liquids enzyme catalysts (SILEs). In addition, adsorption of lipase PS on celite was studied to compare the results obtained with sol-gels, CLEAs and SILEs. The effects of immobilization on enzyme activity, enantioselectivity and hydrolysis side reactions were studied in kinetic resolution of three secondary alcohols in organic solvents, in ionic liquids (ILs), and in their mixtures. Lipase PS sol-gels were shown to be active and stable catalysts in organic solvents and solvent:IL mixtures. CLEAs and SILEs were highly active and enantioselective in organic solvents. Sol-gels and SILEs were reusable in several cycles. Hydrolysis side reaction was suppressed in the presence of sol-gels and CLEAs.

Litter fall production and decomposition in a fragment of secondary Atlantic Forest of São Paulo, sp, southeastern Brazil

Litter fall consists of all organic material deposited on the forest floor, being of extremely important for the structure and maintenance of the ecosystem through nutrient cycling. This study aimed to evaluate the production and decomposition of litter fall in a secondary Atlantic forest fragment of secondary Atlantic Forest, at the Guarapiranga Ecological Park, in São Paulo, SP. The litter samples were taken monthly from May 2012 to May 2013. To assess the contribution of litter fall forty collectors were installed randomly within an area of 0.5 ha. The collected material was sent to the laboratory to be dried at 65 °C for 72 hours, being subsequently separated into fractions of leaves, twigs, reproductive parts and miscellaneous, and weighed to obtain the dry biomass. Litterbags were placed and tied close to the collectors to estimate the decomposition rate in order to evaluate the loss of dry biomass at 30, 60, 90, 120 and 150 days. After collection, the material was sent to the laboratory to be dried and weighed again. Total litter fall throughout the year reached 5.7 Mg.ha-1.yr-1 and the major amount of the material was collected from September till March. Leaves had the major contribution for total litter fall (72%), followed by twigs (14%), reproductive parts (11%) and miscellaneous (3%). Reproductive parts had a peak during the wet season. Positive correlation was observed between total litter and precipitation, temperature and radiation (r = 0.66, p<0.05; r = 0.76, p<0.05; r = 0.58, p<0.05, respectively). The multiple regression showed that precipitation and radiation contributed significantly to litter fall production. Decomposition rate was in the interval expected for secondary tropical forest and was correlated to rainfall. It was concluded that this fragment of secondary forest showed a seasonality effect driven mainly by precipitation and radiation, both important components of foliage renewal for the plant community and that decomposition was in an intermediate rate.

Hydrometallurgical recovery of valuable metals from secondary raw materials

Wastes and side streams in the mining industry and different anthropogenic wastes often contain valuable metals in such concentrations their recovery may be economically viable. These raw materials are collectively called secondary raw materials. The recovery of metals from these materials is also environmentally favorable, since many of the metals, for example heavy metals, are hazardous to the environment. This has been noticed in legislative bodies, and strict regulations for handling both mining and anthropogenic wastes have been developed, mainly in the last decade. In the mining and metallurgy industry, important secondary raw materials include, for example, steelmaking dusts (recoverable metals e.g. Zn and Mo), zinc plant residues (Ag, Au, Ga, Ge, In) and waste slurry from Bayer process alumina production (Ga, REE, Ti, V). From anthropogenic wastes, waste electrical and electronic equipment (WEEE), among them LCD screens and fluorescent lamps, are clearly the most important from a metals recovery point of view. Metals that are commonly recovered from WEEE include, for example, Ag, Au, Cu, Pd and Pt. In LCD screens indium, and in fluorescent lamps, REEs, are possible target metals. Hydrometallurgical processing routes are highly suitable for the treatment of complex and/or low grade raw materials, as secondary raw materials often are. These solid or liquid raw materials often contain large amounts of base metals, for example. Thus, in order to recover valuable metals, with small concentrations, highly selective separation methods, such as hydrometallurgical routes, are needed. In addition, hydrometallurgical processes are also seen as more environmental friendly, and they have lower energy consumption, when compared to pyrometallurgical processes. In this thesis, solvent extraction and ion exchange are the most important hydrometallurgical separation methods studied. Solvent extraction is a mainstream unit operation in the metallurgical industry for all kinds of metals, but for ion exchange, practical applications are not as widespread. However, ion exchange is known to be particularly suitable for dilute feed solutions and complex separation tasks, which makes it a viable option, especially for processing secondary raw materials. Recovering valuable metals was studied with five different raw materials, which included liquid and solid side streams from metallurgical industries and WEEE. Recovery of high purity (99.7%) In, from LCD screens, was achieved by leaching with H2SO4, extracting In and Sn to D2EHPA, and selectively stripping In to HCl. In was also concentrated in the solvent extraction stage from 44 mg/L to 6.5 g/L. Ge was recovered as a side product from two different base metal process liquors with Nmethylglucamine functional chelating ion exchange resin (IRA-743). Based on equilibrium and dynamic modeling, a mechanism for this moderately complex adsorption process was suggested. Eu and Y were leached with high yields (91 and 83%) by 2 M H2SO4 from a fluorescent lamp precipitate of waste treatment plant. The waste also contained significant amounts of other REEs such as Gd and Tb, but these were not leached with common mineral acids in ambient conditions. Zn was selectively leached over Fe from steelmaking dusts with a controlled acidic leaching method, in which the pH did not go below, but was held close as possible to, 3. Mo was also present in the other studied dust, and was leached with pure water more effectively than with the acidic methods. Good yield and selectivity in the solvent extraction of Zn was achieved by D2EHPA. However, Fe needs to be eliminated in advance, either by the controlled leaching method or, for example, by precipitation. 100% Pure Mo/Cr product was achieved with quaternary ammonium salt (Aliquat 336) directly from the water leachate, without pH adjustment (pH 13.7). A Mo/Cr mixture was also obtained from H2SO4 leachates with hydroxyoxime LIX 84-I and trioctylamine (TOA), but the purities were 70% at most. However with Aliquat 336, again an over 99% pure mixture was obtained. High selectivity for Mo over Cr was not achieved with any of the studied reagents. Ag-NaCl solution was purified from divalent impurity metals by aminomethylphosphonium functional Lewatit TP-260 ion exchange resin. A novel preconditioning method, named controlled partial neutralization, with conjugate bases of weak organic acids, was used to control the pH in the column to avoid capacity losses or precipitations. Counter-current SMB was shown to be a better process configuration than either batch column operation or the cross-current operation conventionally used in the metallurgical industry. The raw materials used in this thesis were also evaluated from an economic point of view, and the precipitate from a waste fluorescent lamp treatment process was clearly shown to be the most promising.

Decentralized management of organic household wastes in the Kathmandu Valley using small-scale composting reactors

The sustainable management of municipal solid waste in the Kathmandu Valley has always been a challenging task. Solid waste generation has gone rapidly high in the Kathmandu Valley over the last decade due to booming population and rapid urbaniza-tion. Finding appropriate landfill sites for the disposal of solid wastes generated from the households of the Kathmandu Valley has always been a major problem for Nepalese government. 65 % of total generated wastes from the households of Nepal consist of organic materials. As large fractions of generated household wastes are organic in na-ture, composting can be considered as one of the best sustainable ways to recycle organ-ic wastes generated from the households of Nepal. Model Community Society Development (MCDS), a non-governmental organization of Nepal carried out its small-scale project in five households of the Kathmandu Valley by installing composting reactors. This thesis is based on this small-scale project and has used secondary data provided by MCDS Nepal for carrying out the study. Proper man-agement of organic wastes can be done at household levels through the use of compost-ing reactors. The end product compost can be used as soil conditioners for agricultural purposes such as organic farming, roof-top farming and gardening. The overall average organic waste generation in the Kathmandu Valley is found to be 0,23 kg/person/day and the total amount of organic household wastes generated in the Kathmandu Valley is around 210 Gg/yr. Produced composts from five composting reac-tors contain high amount of moistures but have sufficient amount of nutrients required for the fertility of land and plant growth. Installation of five composting reactors in five households have prevented 2,74 Mg of organic wastes going into the landfills, thus re-ducing 107 kg of methane emissions which is equivalent to 2,7 Mg of carbondioxide.

Studies in selectivity of lipases in preparation of cyanohydrins, sugar conjugates and secondary alcohols

Biocatalysis can be applied in organic synthetic chemistry to counter challenges posed by increased demands towards chemo-, regio- and stereoselectivity, not forgetting the need for greener chemistry. During the last 30 years, biocatalysis with the use of enzymes as chiral catalysts has become more common in chemistry laboratories and industrial processes. In this thesis, the use of lipases as versatile biocatalysts in the acylation of alcohols is examined both in the light of literature examples and four original publications. In the first part of the work presented in this thesis lipases were utilized in two examples concerning secondary alcohols. First, the kinetic resolution of heterocyclic aromatic secondary alcohols through transesterification was thoroughly examined including the studies of competing hydrolysis and esterification reactions. In another example, lipases were utilized in the formation of a dynamic systemic resolution (DSR) process which in turn was used as a developmental tool in the optimization of the dynamic kinetic resolution (DKR) of five heterocyclic aromatic cyanohydrins in one pot for the preparation of cyanohydrin esters as single enantiomers. In the second part of the work, the regio- and stereoselectivity of lipases was used to form sugar conjugates of glyceric and β-amino acids. The primary hydroxyl groups of methyl α-D-galacto-, -gluco- and -mannopyranosides were now acylated trough lipasecatalyzed transesterification and enantioselective lipase-catalyzed ring-opening of β- lactams, respectively.

Microbial flora in organic honey samples of africanized honeybees from Parana river islands

The purpose of this study was to verify and compare the main contamination sources and the hygienic/sanitary conditions of organic honey samples of Apis mellifera from Parana River islands. Thirty-three (33) samples were analyzed between January 2005 and August 2006. Eleven (11) samples were collected by beekeepers and twenty-two (22) samples were collected and processed in accordance with ideal personal hygiene norms and good manufacturing practices. The samples underwent microbiological analysis in search of coliforms at 35 ºC and 45 ºC, as well as fungi enumeration analysis. As for fungi counting, the samples harvested by beekeepers showed values above the maximum established by Resolution nº 15/94 of Common Market Group - Mercosul. The results showed that secondary contamination sources are responsible for the reduction of organic honey quality.

Biotransformation of aromatic hydrocarbons and organic sulphides by fungi

Toluene is converted to benzyl alcohol by the fungi Mortierella isabellina and Helminthosporium species; in the latter case, the product is further metabolized. Toluene-a -d 1 , toluene-a,a-d2, and toluene-a,a,a-d 3 have been used with Mortierellaisabellina in a series of experiments to determine both primary and secondary deuterium kinetic isotope effects for the enzymic benzylic hydroxylation reaction. The values obtained, intermolecular primary kH/kD = intramolecular p rim a r y kH r kD = 1. 0 2 + O. 0 5, and sec 0 n dar y k H I kD = 1. 37 .:!. 0.05, suggest a mechanism for the reaction involving benzylic proton removal from a radical intermediate in a non-symmetrical transition state. 2H NMR (30.7 MHz) studies using ethylbenzene-l,1-d 2 , 3 -fluoroethylbenzene-l,1-d 2 , 4 -fluoroethylbenzene-l,1-d 2 , and toluene-dB as substrates with Mortierella isabellina suggest, based on the observable differences in rates of conversion between the substrates, that the hydroxylation of hydrocarbons at the benzylic position proceeds via a one electron abstraction from the aromatic ring, giving a radical cation. A series of 1,3-oxathiolanes (eight) were incubated with Mortierella isabellina , Helminthosporium , Rhizopus arrhizus , and Aspergillus niger . Sulphoxides were obtained from Mortierella isabellina and Rhizopus arrhizus using the substrates 2-phenyl-, 2-methyl-2-phenyl-, and 2-phenyl-2-tert. butyl-l,3-oxathiolane. The relative stereochemistry of 2-methyl-2-phenyl-l,3-oxathiolan-l-oxide was assigned based on lH decoupling, n.O.e, 1 and H NMR experiments. The lH NMR (200 MHz) of the methylene protons of 2-methyl-2-phenyl-l,3-oxathiolan-l-oxide was used as a diagnostic standard in assigning the relative stereochemistry of 2-phenyl-l,3-oxathiolan-l-oxide and 2-phenyl-2-tert. butyl-l,3-oxathiolan-l-oxide. The sulphoxides obtained were consistent with an oxidation occurring from the opposite side of the molecule to the phenyl substituent.

Organic inputs and farmers' management strategies in millet fields of western Niger

Research on soil fertility management in sub-Saharan Africa was criticized lately for largely ignoring farmers’ management strategies and the underlying principles. To fill this gap of knowledge, detailed interviews were conducted with 108 farm households about their rationale in managing the soil fertility of 307 individual fields in the agro-pastoral village territory of Chikal in western Niger. To amplify the farmers’ information on manuring and corralling practices, repeated measurements of applied amounts of manure were carried out within six 1-km^2 monitoring areas from February to October 1998. The interviews revealed that only 2% of the fields were completely fallowed for a period of 1–15 years, but 40% of the fields were at least partially fallowed. Mulching of crop residues was mainly practiced to fight wind erosion but was restricted to 36% of the surveyed fields given the alternative use of straw as livestock feed. Manure application and livestock corralling, as most effective tools to enhance soil fertility, were targeted to less than 30% of the surveyed fields. The application of complete fallow and manuring and corralling practices were strongly related to the households’ endowment with resources, especially with land and livestock. Within particular fields, measures were mainly applied to spots of poor soil fertility, while the restoration of the productivity of hard pans was of secondary importance. Given the limited spatial coverage of indigenous soil fertility measures and their strong dependence on farmers’ wealth, supplementary strategies to restrict the decline of soil fertility in the drought prone areas of Niger with their heavily weathered soils are needed.

The European organic food market - how to increase its transparency?

Der Europäische Markt für ökologische Lebensmittel ist seit den 1990er Jahren stark gewachsen. Begünstigt wurde dies durch die Einführung der EU-Richtlinie 2092/91 zur Zertifizierung ökologischer Produkte und durch die Zahlung von Subventionen an umstellungswillige Landwirte. Diese Maßnahmen führten am Ende der 1990er Jahre für einige ökologische Produkte zu einem Überangebot auf europäischer Ebene. Die Verbrauchernachfrage stieg nicht in gleichem Maße wie das Angebot, und die Notwendigkeit für eine Verbesserung des Marktgleichgewichts wurde offensichtlich. Dieser Bedarf wurde im Jahr 2004 von der Europäischen Kommission im ersten „Europäischen Aktionsplan für ökologisch erzeugte Lebensmittel und den ökologischen Landbau“ formuliert. Als Voraussetzung für ein gleichmäßigeres Marktwachstum wird in diesem Aktionsplan die Schaffung eines transparenteren Marktes durch die Erhebung statistischer Daten über Produktion und Verbrauch ökologischer Produkte gefordert. Die Umsetzung dieses Aktionsplans ist jedoch bislang nicht befriedigend, da es auf EU-Ebene noch immer keine einheitliche Datenerfassung für den Öko-Sektor gibt. Ziel dieser Studie ist es, angemessene Methoden für die Erhebung, Verarbeitung und Analyse von Öko-Marktdaten zu finden. Geeignete Datenquellen werden identifiziert und es wird untersucht, wie die erhobenen Daten auf Plausibilität untersucht werden können. Hierzu wird ein umfangreicher Datensatz zum Öko-Markt analysiert, der im Rahmen des EU-Forschungsprojektes „Organic Marketing Initiatives and Rural Development” (OMIaRD) erhoben wurde und alle EU-15-Länder sowie Tschechien, Slowenien, Norwegen und die Schweiz abdeckt. Daten für folgende Öko-Produktgruppen werden untersucht: Getreide, Kartoffeln, Gemüse, Obst, Milch, Rindfleisch, Schaf- und Ziegenfleisch, Schweinefleisch, Geflügelfleisch und Eier. Ein zentraler Ansatz dieser Studie ist das Aufstellen von Öko-Versorgungsbilanzen, die einen zusammenfassenden Überblick von Angebot und Nachfrage der jeweiligen Produktgruppen liefern. Folgende Schlüsselvariablen werden untersucht: Öko-Produktion, Öko-Verkäufe, Öko-Verbrauch, Öko-Außenhandel, Öko-Erzeugerpreise und Öko-Verbraucherpreise. Zudem werden die Öko-Marktdaten in Relation zu den entsprechenden Zahlen für den Gesamtmarkt (öko plus konventionell) gesetzt, um die Bedeutung des Öko-Sektors auf Produkt- und Länderebene beurteilen zu können. Für die Datenerhebung werden Primär- und Sekundärforschung eingesetzt. Als Sekundärquellen werden Publikationen von Marktforschungsinstituten, Öko-Erzeugerverbänden und wissenschaftlichen Instituten ausgewertet. Empirische Daten zum Öko-Markt werden im Rahmen von umfangreichen Interviews mit Marktexperten in allen beteiligten Ländern erhoben. Die Daten werden mit Korrelations- und Regressionsanalysen untersucht, und es werden Hypothesen über vermutete Zusammenhänge zwischen Schlüsselvariablen des Öko-Marktes getestet. Die Datenbasis dieser Studie bezieht sich auf ein einzelnes Jahr und stellt damit einen Schnappschuss der Öko-Marktsituation der EU dar. Um die Marktakteure in die Lage zu versetzen, zukünftige Markttrends voraussagen zu können, wird der Aufbau eines EU-weiten Öko-Marktdaten-Erfassungssystems gefordert. Hierzu wird eine harmonisierte Datenerfassung in allen EU-Ländern gemäß einheitlicher Standards benötigt. Die Zusammenstellung der Marktdaten für den Öko-Sektor sollte kompatibel sein mit den Methoden und Variablen der bereits existierenden Eurostat-Datenbank für den gesamten Agrarmarkt (öko plus konventionell). Eine jährlich aktualisierte Öko-Markt-Datenbank würde die Transparenz des Öko-Marktes erhöhen und die zukünftige Entwicklung des Öko-Sektors erleichtern. ---------------------------

Preparation of consistent soil data sets for modelling purposes: Secondary SOTER data for four case study areas

The common GIS-based approach to regional analyses of soil organic carbon (SOC) stocks and changes is to define geographic layers for which unique sets of driving variables are derived, which include land use, climate, and soils. These GIS layers, with their associated attribute data, can then be fed into a range of empirical and dynamic models. Common methodologies for collating and formatting regional data sets on land use, climate, and soils were adopted for the project Assessment of Soil Organic Carbon Stocks and Changes at National Scale (GEFSOC). This permitted the development of a uniform protocol for handling the various input for the dynamic GEFSOC Modelling System. Consistent soil data sets for Amazon-Brazil, the Indo-Gangetic Plains (IGP) of India, Jordan and Kenya, the case study areas considered in the GEFSOC project, were prepared using methodologies developed for the World Soils and Terrain Database (SOTER). The approach involved three main stages: (1) compiling new soil geographic and attribute data in SOTER format; (2) using expert estimates and common sense to fill selected gaps in the measured or primary data; (3) using a scheme of taxonomy-based pedotransfer rules and expert-rules to derive soil parameter estimates for similar soil units with missing soil analytical data. The most appropriate approach varied from country to country, depending largely on the overall accessibility and quality of the primary soil data available in the case study areas. The secondary SOTER data sets discussed here are appropriate for a wide range of environmental applications at national scale. These include agro-ecological zoning, land evaluation, modelling of soil C stocks and changes, and studies of soil vulnerability to pollution. Estimates of national-scale stocks of SOC, calculated using SOTER methods, are presented as a first example of database application. Independent estimates of SOC stocks are needed to evaluate the outcome of the GEFSOC Modelling System for current conditions of land use and climate. (C) 2007 Elsevier B.V. All rights reserved.

Self-assembly of peptide nanotubes in an organic solvent

The self-assembly of a modified fragment of the amyloid beta peptide, based on sequence A beta(16-20), KLVFF, extended to give AAKLVFF is studied in methanol. Self-assembly into peptide nanotubes is observed, as confirmed by electron microscopy and small-angle X-ray scattering. The secondary structure of the peptide is probed by FTIR and circular dichroism, and UV/visible spectroscopy provides evidence for the important role of aromatic interactions between phenylalanine residues in driving beta-sheet self-assembly. The beta-sheets wrap helically to form the nanotubes, the nanotube wall comprising four wrapped beta-sheets. At higher concentration, the peptide nanotubes form a nematic phase that exhibits spontaneous flow alignment as observed by small-angle neutron scattering.

Interaction of nitrogen dioxide (NO2) with a monolayer of oleic acid at the air–water interface – A simple proxy for atmospheric aerosol

The reactions between atmospheric oxidants and organic amphiphiles at the air water interface of an aerosol droplet may affect the size and critical supersaturation required for cloud droplet formation. We demonstrate that no reaction occurs between gaseous nitrogen dioxide (1000 ppm in air) and a monolayer of an insoluble amphiphile, oleic acid (cis-9-octadecenoic acid), at the air water interface which removes material from the air water interface. We present evidence that the NO2 isomerises the cis-9-octadecenoic (oleic) acid to trans-9-octadecenoic (elaidic) acid. The study presented here is important for future and previous studies of (1) the reaction between the nitrate radical, NO3, and thin organic films as NO2 is usually present in high concentrations in these experimental systems and (2) the effect of NO2 air pollution on the unsaturated fatty acids and lipids found at the air liquid surface of human lung lining fluid.

A novel satellite mission concept for upper air water vapour, aerosol and cloud observations using integrated path differential absorption LiDAR limb sounding

We propose a new satellite mission to deliver high quality measurements of upper air water vapour. The concept centres around a LiDAR in limb sounding by occultation geometry, designed to operate as a very long path system for differential absorption measurements. We present a preliminary performance analysis with a system sized to send 75 mJ pulses at 25 Hz at four wavelengths close to 935 nm, to up to 5 microsatellites in a counter-rotating orbit, carrying retroreflectors characterized by a reflected beam divergence of roughly twice the emitted laser beam divergence of 15 µrad. This provides water vapour profiles with a vertical sampling of 110 m; preliminary calculations suggest that the system could detect concentrations of less than 5 ppm. A secondary payload of a fairly conventional medium resolution multispectral radiometer allows wide-swath cloud and aerosol imaging. The total weight and power of the system are estimated at 3 tons and 2,700 W respectively. This novel concept presents significant challenges, including the performance of the lasers in space, the tracking between the main spacecraft and the retroreflectors, the refractive effects of turbulence, and the design of the telescopes to achieve a high signal-to-noise ratio for the high precision measurements. The mission concept was conceived at the Alpbach Summer School 2010.

Estimates of global multicomponent aerosol optical depth and direct radiative perturbation in the Laboratoire de Météorologie Dynamique general circulation model

The global cycle of multicomponent aerosols including sulfate, black carbon (BC),organic matter (OM), mineral dust, and sea salt is simulated in the Laboratoire de Me´te´orologie Dynamique general circulation model (LMDZT GCM). The seasonal open biomass burning emissions for simulation years 2000–2001 are scaled from climatological emissions in proportion to satellite detected fire counts. The emissions of dust and sea salt are parameterized online in the model. The comparison of model-predicted monthly mean aerosol optical depth (AOD) at 500 nm with Aerosol Robotic Network (AERONET) shows good agreement with a correlation coefficient of 0.57(N = 1324) and 76% of data points falling within a factor of 2 deviation. The correlation coefficient for daily mean values drops to 0.49 (N = 23,680). The absorption AOD (ta at 670 nm) estimated in the model is poorly correlated with measurements (r = 0.27, N = 349). It is biased low by 24% as compared to AERONET. The model reproduces the prominent features in the monthly mean AOD retrievals from Moderate Resolution Imaging Spectroradiometer (MODIS). The agreement between the model and MODIS is better over source and outflow regions (i.e., within a factor of 2).There is an underestimation of the model by up to a factor of 3 to 5 over some remote oceans. The largest contribution to global annual average AOD (0.12 at 550 nm) is from sulfate (0.043 or 35%), followed by sea salt (0.027 or 23%), dust (0.026 or 22%),OM (0.021 or 17%), and BC (0.004 or 3%). The atmospheric aerosol absorption is predominantly contributed by BC and is about 3% of the total AOD. The globally and annually averaged shortwave (SW) direct aerosol radiative perturbation (DARP) in clear-sky conditions is �2.17 Wm�2 and is about a factor of 2 larger than in all-sky conditions (�1.04 Wm�2). The net DARP (SW + LW) by all aerosols is �1.46 and �0.59 Wm�2 in clear- and all-sky conditions, respectively. Use of realistic, less absorbing in SW, optical properties for dust results in negative forcing over the dust-dominated regions.

A multimodel assessment of the influence of regional anthropogenic emission reductions on aerosol direct radiative forcing and the role of intercontinental transport

In this study, we assess changes of aerosol optical depth (AOD) and direct radiative forcing (DRF) in response to the reduction of anthropogenic emissions in four major pollution regions in the Northern Hemisphere by using results from nine global models in the framework of the Hemispheric Transport of Air Pollution (HTAP). DRF at top of atmosphere (TOA) and surface is estimated based on AOD results from the HTAP models and AOD-normalized DRF (NDRF) from a chemical transport model. The multimodel results show that, on average, a 20% reduction of anthropogenic emissions in North America, Europe, East Asia, and South Asia lowers the global mean AOD (all-sky TOA DRF) by 9.2% (9.0%), 3.5% (3.0%), and 9.4% (10.0%) for sulfate, particulate organic matter (POM), and black carbon (BC), respectively. Global annual average TOA all-sky forcing efficiency relative to particle or gaseous precursor emissions from the four regions (expressed as multimodel mean ± one standard deviation) is  ±3.5 ±0.8,  ±4.0 ±1.7, and 29.5 ±18.1mWm ±2 per Tg for sulfate (relative to SO2), POM, and BC, respectively. The impacts of the regional emission reductions on AOD and DRF extend well beyond the source regions because of intercontinental transport (ICT). On an annual basis, ICT accounts for 11 ±5% to 31 ±9% of AOD and DRF in a receptor region at continental or subcontinental scale, with domestic emissions accounting for the remainder, depending on regions and species. For sulfate AOD, the largest ICT contribution of 31 ±9% occurs in South Asia, which is dominated by the emissions from Europe. For BC AOD, the largest ICT contribution of 28 ±18% occurs in North America, which is dominated by the emissions from East Asia. The large spreads among models highlight the need to improve aerosol processes in models, and evaluate and constrain models with observations.