Abstract: In a small, open and resource-poor economy, import and export dependency have an ever-growing impact on local policy decisions, which makes local (environmental) policy-makers increasingly depend on global data. This increases the interest in models that link local production and consumption data to global production, trade and environmental data. The recent increase in availability of global environmentally extended multi-regional input-output tables (EE-MRIO tables) provides an opportunity to link them with existing local environmentally extended input-output tables (EE-RIO tables). These combined tables make it possible (1) to analyse the links between local and global production and consumption and (2) to study global value chains, material use and environmental impacts simultaneously. However, estimations using input-output (I-O) analyses contain errors due to imperfect databases. In this article the magnitude of specification, aggregation and time errors are estimated and compared. The results show the need to combine local datasets with multi-regional ones and show that highest detailed (country and sector levels) as well as time series of I-O tables are the way forward for using I-O analyses in local policy-making. The paper provides guidance on trading off investments in model adoption and/or extension and the reliability of estimation results.

Abstract: The ID21 beamline (European Synchrotron Radiation facility, France) is a multi micro-analytical platform combining X-ray and infrared micro-probes, for characterization of elements, species, molecular groups and crystalline structures in complex materials. Applications are mainly in the fields of cultural heritage, life science, environmental and earth sciences, materials sciences. Here, we first present the status of instruments: (i) the scanning micro-spectroscopy end-station, operating from 2.0 to 9.2 keV, under vacuum and offering cryo conditions, for the acquisition of 2D micro X-ray fluorescence (mu XRF) maps, single point micro X-ray Absorption Near Edge Structure (mu XANES) spectra and speciation maps with sub-micrometric resolution; (ii) the XANES full-field end-station, operating in the same vacuum and energy conditions, for the acquisition of hyper-spectral radiographs of thin concentrated samples, resulting in speciation maps with micrometric resolution and millimetric field of view; (iii) the scanning micro-X-ray diffraction (mu XRD)/mu XRF end-station, operating at 8.5 keV, in air, for the acquisition of 2D crystalline phase maps, with micrometric resolution; and (iv) the scanning infrared microscope, operating in the mid-infrared range for the acquisition of molecular maps and some structural maps with micrometric resolution. Recent hardware and software developments are presented, as well as new protocols for improved sample preparation of thin sections. Secondly, a review of recent applications for the study of cultural heritage is presented, illustrated by various examples: determination of the origin of the color in blue Chinese porcelains and in brown Sevres porcelains; detection of lead in ink on Herculaneum papyri; identification and degradation of modeling materials used by Auguste Rodin and of chrome yellow pigments used by Vincent van Gogh. Cryo capabilities are illustrated by the analysis of plants exposed to chromate solutions. These examples show the variety of materials analyzed, of questions tackled, and particularly the multiple advantages of the ID21 analytical platform for the analysis of ancient and artistic materials.

Abstract: The ability of urban wastewater systems to adapt and transform as a response to change is an integral part of sustainable development. This requires technology and infrastructure that can be adapted to new operational challenges. In this study the adaptive capacity of urban wastewater systems is evaluated by assessing the interdependencies between system components. In interdependent and therefore tightly coupled systems, changes to one systems component will require alteration elsewhere in the system, therefore impairing the capacity of these systems to be changed. The aim of this paper is to develop a methodology to evaluate the adaptive capacity of urban wastewater systems by assessing how change drivers and innovation affect existing wastewater technology and infrastructure. The methodology comprises 7 steps and applies a change impact table and a design structure matrix that are completed by experts during workshops. Change impact tables quantify where change drivers, such as energy neutrality and resource recovery, require innovation in a system. The design structure matrix is a tool to quantify emerging changes that are a result of the innovation. The method is applied for the change driver of energy neutrality and shown for two innovations: a decentralised upflow anaerobic sludge blanket reactor followed by an anammox process and a conventional activated sludge treatment with enhanced chemical precipitation and high temperature-high pressure hydrolysis. The results show that the energy neutrality of wastewater systems can be address by either innovation in the decentralised or centralised treatment. The quantification of the emerging changes for both innovations indicates that the decentralised treatment is more disruptive, or in other words, the system needs to undergo more adaptation. It is concluded that the change impact and change propagation method can be used to characterise and quantify the technological or infrastructural transformations. In addition, it provides insight into the stakeholders affected by change.

Abstract: A quasi 3D modelling approach was developed by integrating a crop growth (LINGRA-N) and a hydrological model (Hydrus-1D) to simulate and visualize water flow, soil-water storage, water stress and crop yield over a heterogeneous sandy field. We assessed computational efficiency and uncertainty with low to high-spatial resolution input factors (soil-hydraulic properties, soil-layer thickness and groundwater level) and evaluated four irrigation scenarios (no, current, optimized and triggered) to find the optimal and cost-effective irrigation scheduling. Numerical results showed that the simulation uncertainty was reduced when using the high-resolution information while a fast performance was maintained. The approach accurately determined the field scale irrigation requirements, taking into account spatial variations of input information. Optimal irrigation scheduling is obtained by triggered-irrigation resulting in saving up to similar to 300% water as compared to the current-irrigation, while yield increased similar to 1%. Overall, the approach can be useful to help decision makers and applicants in precision farming. (C) 2017 Published by Elsevier Ltd.

Abstract: Several HNO3-based leaching approaches were tested and optimized to selectively recover Pb and other minor metals (Cu, Ni, Zn) from secondary lead smelter residues (i.e., slag and matte). Firstly, the leaching behaviors of Pb and the matrix element Fe were studied at atmospheric pressure in the temperature range 25-70 degrees C. These elements were present in both materials studied as sulfide and oxide phases. For the sulfur-rich matte residue, the Pb leaching increased from 63% to 69% upon increasing the HNO3 concentration from 0.2 M to 0.5 M. However, by adding Fe(III) as an oxidation agent, Pb leaching from the matte amounted to 90% at 25 degrees C. At a higher temperature, Pb leaching was reduced due to PbSO4 precipitation. In this process, Cu, Zn and Ni leaching was insignificant. For the slag residue, HNO3 could not leach Pb (0.03% Pb leached), while Fe leaching was 19.8% due to a galvanic effect. However, Pb leaching of the slag was 82% in the presence of additional Fe(III). Secondly, to enhance leaching of the other base metals (Cu, Zn and Ni) from the matte, roasting followed by water leaching and (microwave assisted or autoclave) pressurized leaching in 0.5 M HNO3 were applied. During roasting, the FeS phase converted to Fe2O3 above 500 degrees C, and PbS and Pb phases were transformed into insoluble PbSO4 above 400 degrees C. Cu, Ni and Zn leaching was drastically enhanced by a roasting step at 600 degrees C followed by leaching with 0.5 M HNO3 at 50 degrees C, or by pressurized HNO3 leaching above 130 degrees C, whereby Pb leaching almost ceased due to PbSO4 precipitation. During the roasting above 600 degrees C, or microwave assisted extraction (MAE) at 160 degrees C for 15 min, FeS was completely converted to iron oxides that can be used as raw material for pig iron production. Based on the results, the methods investigated can be combined as process steps of two possible routes for the selective recovery of valuable metals and the production of a clean source of Fe oxides from the secondary lead smelting residues studied. (C) 2017 Elsevier B.V. All rights reserved.

Abstract: A combined Raman and electrochemical study of natural orpiment (As2S3), an arsenic sulfide pigment, was used to assess the quick formation of oxidized species such as arsenic oxide (As2O3) upon exposing the pigment to 405 nm or 532 nm monochromatic light while simultaneously recording the Raman spectra of the exposed sample. During this process, a distortion of the main band at 355 cm−1, associated with the stretching of the AsS3/2 pyramids of natural orpiment, was observed as well as an increased intensity of the 359 cm−1 band, corresponding to covalent AsAs bonds in natural orpiment. The distortion was accompanied by an overall decrease of the global Raman signal for natural orpiment, which could be explained by a loss in the crystal structure. The same phenomena were recorded in reference natural orpiment model paint samples stored for a long time together with verdigris (Cu(OH)2·(CH3COO)2·5H2O) and minium (Pb3O4) paints, the latter two appearing darkened on their sides closest to the orpiment sample as well as in several historical samples containing natural orpiment mixed with various blue pigments. By SEM-EDX and XRPD analysis, respectively on loose material and cast thin-sections of model paint samples, the darkening was identified as dark sulfide species such as chalcocite (Cu2S) and galena (PbS), suggesting the release of volatile sulfide or related species by the natural orpiment paint. XANES analyses of paint samples presenting AsAs bond increase indicated the presence of sulfur species most likely identified as organosulfur compounds formed upon the AsAs bond formation and explained the darkening of the Cu- and Pb-based pigments. To the best of our knowledge, this article reports for the first time the light-induced formation of AsAs bonds in natural orpiment used as an artists' pigment and objectively demonstrates the incompatibility between orpiment and (arsenic) sulfide-sensitive pigments.

Abstract: Enzyme-based electrochemical biosensors are an inspiration for the development of (bio)analytical techniques. However, the instability and reproducibility of the reactivity of enzymes, combined with the need for chemical reagents for sensing remain challenges for the construction of useful devices. Here we present a sensing strategy inspired by the advantages of enzymes and photoelectrochemical sensing, namely the integration of aerobic photocatalysis and electrochemical analysis. The photosensitizer, a bioinspired perfluorinated Zn phthalocyanine, generates singlet-oxygen from air under visible light illumination and oxidizes analytes, yielding electrochemically-detectable products while resisting the oxidizing species it produces. Compared with enzymatic detection methods, the proposed strategy uses air instead of internally added reactive reagents, features intrinsic baseline correction via on/off light switching and shows C-F bonds-type enhanced stability. It also affords selectivity imparted by the catalytic process and nano-level detection, such as 20 nM amoxicillin in μl sample volumes.

Abstract: We introduce LPMLE3, a new 1-D approach to quantify vertical water flow components at streambeds using temperature data collected in different depths. LPMLE3 solves the partial differential equation for coupled water flow and heat transport in the frequency domain. Unlike other 1-D approaches it does not assume a semi-infinite halfspace with the location of the lower boundary condition approaching infinity. Instead, it uses local upper and lower boundary conditions. As such, the streambed can be divided into finite subdomains bound at the top and bottom by a temperature-time series. Information from a third temperature sensor within each subdomain is then used for parameter estimation. LPMLE3 applies a low order local polynomial to separate periodic and transient parts (including the noise contributions) of a temperature-time series and calculates the frequency response of each subdomain to a known temperature input at the streambed top. A maximum-likelihood estimator is used to estimate the vertical component of water flow, thermal diffusivity, and their uncertainties for each streambed subdomain and provides information regarding model quality. We tested the method on synthetic temperature data generated with the numerical model STRIVE and demonstrate how the vertical flow component can be quantified for field data collected in a Belgian stream. We show that by using the results in additional analyses, nonvertical flow components could be identified and by making certain assumptions they could be quantified for each subdomain. LPMLE3 performed well on both simulated and field data and can be considered a valuable addition to the existing 1-D methods.

Abstract: The combination of several micro-XRF analysis modes is presented for the investigation of an illuminated parchment manuscript. With a commercial instrument, conventional micro-XRF spot analysis (0D) and mapping (2D) are performed, yielding detailed lateral elemental information. Depth resolution becomes accessible by mounting an additional polycapillary lens in front of an SDD detector. Quantitative confocal depth profiles (1D) are presented as well as the full separation of the front and the backside decorations with the help of fast 3D mappings of specific areas. Only through the use of these multidimensional modes can elemental information be assigned both to lateral and depth positions, making the analysis of such heterogeneous samples feasible.

Abstract: Antibiotics such as sulfamethoxazole (SFX) are environmentally hazardous after being released into the aquatic environment and challenges remain in the development of engineered prevention strategies. In this work, a mathematical model was developed to describe and evaluate cometabolic biotransformation of SFX and its transformation products (TPs) in an enriched ammonia oxidizing bacteria (AOB) culture. The growth-linked cometabolic biodegradation by AOB, non-growth transformation by AOB and nongrowth transformation by heterotrophs were considered in the model framework. The production of major TPs comprising 4-Nitro-SFX, Desamino-SFX and N-4-Acetyl-SFX was also specifically modelled. The validity of the model was demonstrated through testing against literature reported data from extensive batch tests, as well as from long-term experiments in a partial nitritation sequencing batch reactor (SBR) and in a combined SBR + membrane aerated biofilm reactor performing nitrification/denitrification. Modelling results revealed that the removal efficiency of SFX increased with the increase of influent ammonium concentration, whereas the influent organic matter, hydraulic retention time and solid retention time exerted a limited effect on SFX biodegradation with the removal efficiencies varying in a narrow range. The variation of influent SFX concentration had no impact on SFX removal efficiency. The established model framework enables interpretation of a range of experimental observations on SFX biodegradation and helps to identify the optimal conditions for efficient removal. (C) 2017 Elsevier Ltd. All rights reserved.

Abstract: A plasma-enhanced atomic layer deposition (ALD) process using the Ag(fod)(PEt3) precursor [(triethylphosphine)(6,6,7,7,8,8,8-heptafluoro-2,2-dimethy1-3,5-octanedionate)silver(I)] in combination with NH3-plasma is reported. The steady growth rate of the reported process (0.24 +/- 0.03 nm/cycle) was found to be 6 times larger than that of the previously reported Ag ALD process based on the same precursor in combination with H-2-plasma (0.04 +/- 0.02 nm/cycle). The ALD characteristics of the H-2-plasma and NH3-plasma processes were verified. The deposited Ag films were polycrystalline face-centered cubic Ag for both processes. The film morphology was investigated by ex situ scanning electron microscopy and grazing-incidence small-angle X-ray scattering, and it was found that films grown with the NH3-plasma process exhibit a much higher particle areal density and smaller particle sizes on oxide substrates compared to those deposited using the H-2-plasma process. This control over morphology of the deposited Ag is important for applications in catalysis and plasmonics. While films grown with the H-2-plasma process had oxygen impurities (similar to 9 atom %) in the bulk, the main impurity for the NH3-plasma process was nitrogen (similar to 7 atom %). In situ Fourier transform infrared spectroscopy experiments suggest that these nitrogen impurities are derived from NH surface groups generated during the NH3-plasma, which interact with the precursor molecules during the precursor pulse. We propose that the reaction of these surface groups with the precursor leads to additional deposition of Ag atoms during the precursor pulse compared to the H-2-plasma process, which explains the enhanced growth rate of the NH3-plasma process.

Abstract: Organic municipal solid waste (OMSW) as a feedstock for energy recovery and material recycling offers the potential to reduce environmental impacts from energy production while displacing emission intensive waste management strategies such as landfills. This paper quantifies the environmental impact of anaerobic digestion of local, residual biomass. A life-cycle assessment was jointly performed for two scenarios for the biological treatment of local organic municipal solid waste and pig manure in the Netherlands. Scenario 1 was a separate treatment using anaerobic digestion, and Scenario 2 was a bio-refinery system that integrates anaerobic digestion of organic, municipal solid waste, and co digestion of pig manure and other organic co-substrates \. For both scenarios, electricity and heat are generated using a combined heat and power engine. The bio-refinery system (Scenario 2) contribution to climate change resulted in 0.16 Mt CO2 eq./yr, which is lower than the 0.17 Mt CO2 eq./yr of Scenario 1. Both scenarios are found to be beneficial with regard to resource depletion and human toxicity. The integration of organic waste and manure anaerobic digestion has no effect on acidification and terrestrial eutrophication impact categories, resulting in 43.59 AE eq. and 86.33 AE eq. for Scenario 1 and 43.58 AE eq. and 86.30 AE eq. for Scenario 2. Moreover, Scenario 2 yields 18% lower emissions than those from natural gas derived electricity in the Netherlands. The biorefinery system represents an opportunity to improve organic waste-management strategies, at the same time as reducing the environmental impact from energy production and the costs for surplus manure disposal by producing high-quality commodities that can be traded on the market. (C) 2017 Elsevier Ltd. All rights reserved.