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A grass soda technical lignin (PB1000) underwent a process combining solvent fractionation and treatment with an ionic liquid (IL), and a comprehensive investigation of the structural modifications was performed by using high-performance size-exclusion chromatography, P-31 NMR spectroscopy, thioacidolysis, and GC-MS. Three fractions with distinct reactivity were recovered from successive ethyl acetate (EA), butanone, and methanol extractions. In parallel, a fraction deprived of EA extractives was obtained. The samples were treated with methyl imidazolium bromide ([HMIM]Br) by using either conventional heating or microwave irradiation. The treatment allowed us to solubilize 28 % of the EA-insoluble fraction and yielded additional free phenols in all the fractions, as a consequence of depolymerization and demethylation. The gain of the combined process in terms of antioxidant properties was demonstrated through 2,2-diphenyl-1-picrylhydrazyl (DPPH.) radical-scavenging tests. Integrating further IL safety-related data and environmental considerations, this study paves the way for the sustainable production of phenolic oligomers competing with commercial antioxidants.

The development of the so-called bio-economy, replacing « black gold » by « green gold » towards industrial ecology as well as the promotion of the circular economy lead to consider wastes and biomass residues of different sources as new and valuable feedstocks. This global context requires a new paradigm in the way we should tackle the issue of material and process safety in advanced biorefineries. This was recently debated in a wokshop organized by DG Research [1] where safety consideration was pointed out as deserving dedicated research in this area. In addition, adequate safety management strategy implemented at early design stage was also perceived as a contributing factor of sustainability and societal acceptance of industry. Based on recently completed or on-going projects like Imidazolium or Evalbioraf (SAS Pivert), HUGS, ALFA-BIRD, ZELCOR, GREENLAND, FLEDGED (EU FP7 & H2020 programmes) or CORABIO (CR Picardy), the presentation will examplify key issues that needs to be considered towards proactive material hazard characterization or process safety in this sector. Final goal of the presentation is ultimately to explain the attendees how to move from conventional risk analysis and simple compliance to existing safety focused regulations towards advanced integration of safety management as a key and measurable sustainability aspect in the context of biorefining. Among material-focused safety issues, the cases of alternative solvents or green solvents like « ionic liquids » (Fig. 1a) [2] or deep eutectic solvents (Fig. 1b) or biofuels will be pointed out to show about ignored or underscored safety issues or on misleading data regarding their fire behaviour at large scale (fuel ethanol). The importance of revisiting self-heating behaviour (see Fig.2) and other safety related issues all along innovative value chains with biobased feedstock [3] will also be outlined with an insight on biobased residues like biomass materials issuing from phytoremediation of polluted soils. The emerging interest on furan derivatives since new biobased routes of productions were shown promising will also been commented in terms of new needs to dig in the relating safety issues. Even more rarely investigated in recent research [4/5], safety aspects mostly addressing the process side (preatreatment, conversion, downprocessing, emission abatement) will be the latter part of the presentation covering key aspects of biorefining as : a) biological conversion processes and « accidental » biological risks, b) upstream and downstream flexibility demand versus safety , c) process intensification and inherently safer design (ISD) potentially antagonistic aspects [6], d) safety issues pertaining to process water, thermal and carbon streams recycling or to process integration, e) hazards pertaining to zero waste and energy self-sufficient targets), f) Corrosive environment problems as compared to classical refineries. This latter issue at frontier of product and process safety will also be debated at light of existing new hazardous property « corrosive to metal » recently introduced in CLP Regulation 1272/2008/EC and findings from the ECORBIO project. Eventually, the interest to link the safety approach and the evaluation of the environmental impacts of biobased processes will be also discussed.

It is well known that process and economic constraints due to complexity of biomass conversion as well as low cost of fossil fuels context significantly affect the sustainability of biorefining. Ways to tackle such difficulties can be a) operating biorefineries with biomass from waste streams b) producing main or side streams of new molecules or materials with very high added values c) designing biorefinery systems with increased integration of processes, process streams, co-products and energy and material recycling d) in connection with point c) or not, making extensive use of local or global process intensification. The objective of the present work is to focus and outline the potential conflicts in terms of safety that may arise with the improvement of global sustainability target. Indeed, it is often considered that intensification is necessarily leading to inherently safer production systems. Through a review of literature on the concept of intensification, first promoted by Hendershot and coworkers in the early 80’s and Inherently Safer Design or Engineering (ISD by Keltz in 1978) a key way to consider safety in early stage of process design, the potential impacts on safety of the process is addressed in this work. Illustrations and discussions through examples of process intensification are provided, outlining the repercussion of intensification (like activating corrosion issues or triggering risks in effluent or emission treatment units or potential effects on downstream processes with relation to effluents).

The use of nanomaterials in various end products allows to achieve new and innovative properties which has resulted in their large scale deployment (Mitrano 2015; Piccinno 2012). Consequently, 300 000 to 400 000 european workers were potentially exposed to nanoparticles (NP) or their aggregate or agglomerate forms (NOAA) in 2012 (European Commission 2012). A important aspect of the measurement campaign presented in this work is the sampling duration of the exposure assessment. Indeed, long-term sampling is generally recommended to assess toxicology data. Thus, many studies only provide results as daily exposure values. But NP or NOAA exposure are believed to be usually a succession of several short-term exposures (Pietroiusti 2014). Furthermore, in the absence of reliable nanotoxicology data, European stakeholders e.g. trade union groups ask for a zero exposure during particulate exposure (van Broekhuizen 2012). In addition, short-term aerosol measurements permit the identification of nanoparticle release points, thus designing source control at workplace. In addition, to satisfy all these demands a relevant measurement strategy must be able to distinguish the NP or NOAA from the particulate background and to take into account the inhalable NOAA i.e. below 10 μm in size during a very short time of sampling. Therefore the assessment of exposure measurement should be able to deal with these issues and must be able to provide an adapted results analysis with practical recommendations of nanosafety to all stakeholders. Mini particle sampler is a new equipment making possible such an improvement (R'mili 2013). The objective of the present work is to propose a global approach to assess the nanoparticle exposure assessment at workplaces (see figure 1). The methodology and strategy of the global approach is to carry out the measurement campaigns using the Short Time Sampling coupled with exposure assessment, namely STS-EA merge the tiered approach (Consent Report 2011) and the INERIS-CEA-INRS (INERIS - CEA - INRS 2012) approach. To validate the method the STS-EA approach has been tested on five different nanomaterials as NPs of zirconium dioxide (ZrO2), titanium dioxide (TiO2) and silver (Ag); polyamide nanofibers; and multiwalled carbon nanotubes (MWCNT) used in 6 different process lines...

Nanomaterials are increasingly used in industrial products and cover a wide range of applications in cosmetics, functional materials, packaging and promising applications like the drug delivery which is still under investigation and development. The nanomaterials may exhibit interesting properties when compared to the same material in the micro scale. On the contrary their hazard potential may also be dramatically changed due to larger surface area and/or modified surface reactivity. Moreover, the nanomaterials due to their small size make the human beings more vulnerable to their exposure and can be transported deeper in the human body than microparticles. The production and handling of engineered nanomaterials in the work place may pose risks of exposure and hazards to workers. This may occur during the reception, storage, production and operations like cleaning of the work places and the equipment and also during the waste disposal. So, in an industrial context, particular attention has to be done on occupational safety issues related to nanomaterials. But, no consensual occupational exposure limits (OELs) are nowadays available for nanomaterials. In this context, a series of control banding approaches specific to nanomaterials were developed in the last decade to manage toxicological risks in workplaces involving nanomaterials. These CB methods for NMs focused on inhalation risks since it can considered to be most critical route of exposure than the ingestion and the dermal route. The present work concerns the project SANOWORK (7th European Framework Program, GA: 280716), whose main objective is to develop and implement design option based remediation strategies that will prevent workers exposure and/or potential hazards. The present contribution aims to present the work realized by INERIS to demonstrate the pertinence of qualitative and semi-quantitative approaches for the assessment of occupational risks. A series of pilot scale process lines were thus investigated by INERIS in the frame to evaluate the available tools in the assessment of occupational risks. The results showed that the application of existing CB tools to the SANOWORK process lines allowed to highlighting their capabilities and limitations for the design of safe industrial process lines involving nanomaterials.

Nanotechnology is often said to be the industry of the 21st century. Its growth and development may pose potential occupational health and safety issues. The “safety-by-design” approach may be a suitable solution to address these issues. It consists in taking into account the risks (exposure and hazards) and performances in the manufacturing of the future nanomaterial-based products to enhance their safety over their entire lifecycle. Synthesizing nanopowders is one of the techniques to elaborate nanoproducts. One of the major risks related to the powders is that of aerosolization. Indeed, particle release at the workplace (inhalation risk) is not to be underestimated and is therefore to be taken into account in the nanosafety-by-design approach. As a consequence, there is a need to develop experimental systems and protocols to assess dustiness of the powders. Among all the known techniques available to assess dustiness, the vortex shaker appears to be most promising for nano-dustiness [1, 2]. This system is based on the use of a “vortex” type mixer onto which a glass test tube containing the sample is mounted. The test tube is sealed with a stopper pierced with quarter-inch diameter stainless steel inlet and outlet tubes. Clean air is flowed in the glass test tube through the inlet. Air circulation within the glass tube combined with shaking makes the aerosolized fraction of the powder flow out through the outlet tube. Dustiness experiments have been carried out on ZrO2 powders produced by the PLASMACHEM company in the frame of the SANOWORK project (7th European Framework Program, GA: 280716). The studied materials included one original (unmodified) and three “modified-through-design” powders. The modified ZrO2 samples were synthesized with the aim to reduce aerosolization. The objective of these experiments was therefore to compare the dustiness of the original and modified powders. Several tests were performed on the powders and their aerosolized fractions. First, SEM observations were made to visualize the powders. The temporal evolution of the number concentration of the aerosolized fraction of the powder was monitored using particle counters whereas the aerosol composition and morphology was characterized by TEM analysis. The experimental results show significant reduction in the dustiness of some modified powders. These results make it clear that efforts made to modify powders in order to make them less emissive are worth implementing to reduce the inhalation risks. They also highlight dustiness tests as a simple and efficient tool to assist remediation strategies.