Review of generic scenario environmental release and occupational exposure models used in chemical risk assessment.

Under the Toxic Substances Control Act (TSCA), the United States Environmental Protection Agency (USEPA) is required to determine whether a new chemical substance poses an unreasonable risk to human health or the environment before the chemical is manufactured in or imported into the United States. This manuscript provides a review of the process used to evaluate the risk associated with a chemical based on the scenarios and models used in the evaluation. Specifically, the Generic Scenarios and Emission Scenario Documents developed by the USEPA were reviewed, along with background documentation prepared by USEPA to identify the core elements of the environmental release and occupational exposure scenarios used to assess the risk of the chemical being evaluated. Additionally, this contribution provides an overview of methods used to model occupational exposures and environmental releases as part of the chemical evaluation process used in other jurisdictions, along with work being performed to improve these models. Finally, the alternative methods to evaluate occupational exposures and environmental releases that may be used as part of the decision-making process regarding a chemical are identified. The contribution provides a path forward for reducing the time required and improving the chemical evaluation of the unreasonable risk determination regarding the manufacture or import of a chemical.

Application of read-across methods as a framework for the estimation of emissions from chemical processes.

The read-across method is a popular data gap filling technique with developed application for multiple purposes, including regulatory. Within the US Environmental Protection Agency's (US EPA) New Chemicals Program under Toxic Substances Control Act (TSCA), read-across has been widely used, as well as within technical guidance published by the Organization for Economic Co-operation and Development, the European Chemicals Agency, and the European Center for Ecotoxicology and Toxicology of Chemicals for filling chemical toxicity data gaps. Under the TSCA New Chemicals Review Program, US EPA is tasked with reviewing proposed new chemical applications prior to commencing commercial manufacturing within or importing into the United States. The primary goal of this review is to identify any unreasonable human health and environmental risks, arising from environmental releases/emissions during manufacturing and the resulting exposure from these environmental releases. The authors propose the application of read-across techniques for the development and use of a framework for estimating the emissions arising during the chemical manufacturing process. This methodology is to utilize available emissions data from a structurally similar analogue chemical or a group of structurally similar chemicals in a chemical family taking into consideration their physicochemical properties under specified chemical process unit operations and conditions. This framework is also designed to apply existing knowledge of read-across principles previously utilized in toxicity estimation for an analogue or category of chemicals and introduced and extended with a concurrent case study.

Recycling of Plastics in the United States: Plastic Material Flows and Polyethylene Terephthalate (PET) Recycling Processes.

As efforts are made toward establishing a circular economy that engages in activities that maintain resources at their highest values for as long as possible, an important aspect is understanding the systems which allow recycling to occur. In this article a common plastic, polyethylene terephthalate, i.e., PET or plastic #1, has been studied because it is recycled at relatively high rates in the U.S. as compared to other plastics. A material flow analysis is described for PET resin showing materials collected, reclaimed for flake, and converted into items with recycled content. Imports/exports, reclaimer residue, and disposal with mismanaged waste are all shown for U.S. flows of PET. Barriers to recycling PET exist in the collecting, sorting, reclaiming, and converting steps, and this article describes them, offers some solutions, and suggests some research that chemists and engineers could focus on to improve the systems. This effort also models sorting at material recovery facilities (MRF) and reclaimers, with detailed descriptions of the material streams involved, to characterize the resource use and emissions from these operations that are key processes in the recycling system. Example results include greenhouse gas intensities of 8.58 kg CO2 equiv per ton of MRF feed and 103.7 kg CO2 equiv per ton of reclaimer PET bale feed. The results can be used in system analyses for various scenarios and as inputs in economic input-output and life cycle assessments.

Linking Molecular Structure via Functional Group to Chemical Literature for Establishing a Reaction Lineage for Application to Alternatives Assessment.

The evaluation of potential alternatives for chemicals of concern (CoC) requires an understanding of their potential human health and environmental impacts during the manufacture, use, recycle and disposal life stages. During the manufacturing phase, the processes used to produce a desired chemical are defined based on the sequence of chemical reactions and unit operations required to produce the molecule and separate it from other materials used or produced during its manufacture. This paper introduces and demonstrates a tool that links a chemical's structure to information about its synthesis route and the manufacturing process for that chemical. The structure of the chemical is entered using either a SMILES string or the molecule MOL file, and the molecule is searched to identify functional groups present. Based on those functional groups present, the respective named reactions that can be used in its synthesis routes are identified. This information can be used to identify input and output materials for each named reaction, along with reaction conditions, solvents, and catalysts that participate in the reaction. Additionally, the reaction database contains links to internet references and appropriate reaction-specific keywords, further increasing its comprehensiveness. The tool is designed to facilitate the cataloging and use of the chemical literature in a way that allows user to identify and evaluate information about the reactions, such as alternative solvents, catalysts, reaction conditions and other reaction products which enable the comparison of various reaction pathways for the manufacture of the subject chemical. The chemical manufacturing processing steps can be linked to a chemical process ontology to estimate releases and exposures occurring during the manufacturing phase of a chemical.

Framework towards more Sustainable Chemical Synthesis Design - A Case Study of Organophosphates.

In recent years, the advancement of sustainable chemistry concepts and approaches along with their demonstrated application has become a central part of the design, synthesis, and manufacture of a chemical. Sustainable chemistry not only utilizes the principles of green chemistry, but also expands to incorporate economic, societal, and environmental aspects. This is further elucidated by the incorporation of life cycle assessment/thinking to include the raw material production, manufacture, processing, and use and disposal stages, allowing for a comprehensive evaluation of the environmental and human health impacts attributed to a chemical. This contribution outlines an approach for the development of a preliminary framework for the sustainable synthesis of a chemical that is identified as an alternative for an existing chemical of concern. The framework is introduced concurrently with a case study for organophosphates that are selected as potential replacements for brominated flame retardants (BFRs). This framework is designed to apply existing knowledge of green chemistry to the synthesis of alternatives, along with its integration into Life Cycle Assessment culminating in the development of a more overall sustainable chemical entity when compared to its predecessor.

The current and emerging sources of technical lignins and their applications.

Technical lignins are bulk feedstocks. They are generated as byproducts from pulping or cellulosic ethanol production. Since lignin undergoes significant structural changes in the chemical and physical treatments, all technical lignins are unique in terms of chemical structure, molecular weight, polydispersity, and impurity profile. Kraft lignin is potentially the largest source of technical lignin as new isolation technologies have been implemented on industrial scale in recent years. Lignosulfonate has been an integral product in sulfite pulping biorefinery. It has a well-established market in construction industry. Organosolv-like lignin production is increasing as cellulosic ethanol has been promoted as the substitute of fossil fuel. It may have unique applications because it has low molecule weight and is free from sulfur. Technical lignin application is expected to expand as the characteristics are improved with fractionation or chemical modification. The application of technical lignin has been focusing on developing products equivalent to those made by petroleum chemicals. The recent development in technical lignin supply should increase its market share as additives in polyurethanes and as the substitute of phenol-formaldehyde adhesives. Quality improvement of technical lignin may also encourage the study of lignin as an alternative feedstock for carbon fiber. In addition, technical lignin depolymerization has been extensively explored to provide renewable aromatic chemicals. Starting from controlled pyrolysis and thermal liquefaction as the baseline technologies, many different chemical depolymerization have been invented with a wide range of underlying chemical principles.

An Overview of Biorefinery Derived Platform Chemicals from a Cellulose and Hemicellulose Biorefinery.

Until recently, most of energy and industrially produced chemicals were derived from fossil fuel-based resources. This along with the continued depletion of finite fossil resources and their attributed adverse environmental impacts, alternatively sourced and more sustainable resources are being pursued as feedstock replacements. Thus, biomass has been identified as an alternate renewable and more sustainable resource as a means to reduce this sector's dependence on fossil fuel-based resources and to alleviate their environmental impacts. As such, lignocellulosic biomass has been further identified and demonstrated as an abundant renewable resource for the production of biofuels, platform chemicals, and their respective value-added products. This review article provides an overview of the techniques developed for the valorization of biomass in the production of platform chemicals within a biorefinery, and the status for commercialization.

Synthesis of aminomethyl- and bis-aminomethyl-fluorescein energy transfer terminators.

Synthesis of aminomethyl and bis-aminomethylfluorescein derived energy transfer terminators is described.