MD a ; Marine Perrier
email: marine.perrier7@orange.fr

MD PhD Brigitte Delemer

MD Sophie Deguelte

MD e ; Vincent Legros

MD a ; Hedia Brixi

MD PhD Reza Kianmanesh

MD PhD Guillaume Cadiot

Total gastrectomy for severe proton pump inhibitor-induced hypomagnesemia in a MEN1/Zollinger Ellison syndrome patient

Keywords: proton pump inhibitor, hypomagnesemia, gastrinoma, Zollinger-Ellison syndrome, Multiple Endocrine Neoplasia type 1 syndrome, total gastrectomy

niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

Introduction

Gastrinomas are functional neuroendocrine tumors (NETs) whose incidence is 0.5-2/million population /year, preferentially located in the pancreas or duodenum [START_REF] Jensen | ENETS Consensus Guidelines for the management of patients with digestive neuroendocrine neoplasms: functional pancreatic endocrine tumor syndromes[END_REF]. These NETs are characterized by a hormonal hypersecretion of gastrin, leading to a clinical syndrome known as the Zollinger-Ellison syndrome (ZES). Patients with ZES experience acid-related peptic complications (peptic ulcer disease, gastroesophageal reflux disease) and volumogenic diarrhea, related to gastric acid hypersecretion. ZES is part of the Multiple Endocrine Neoplasia type 1 (MEN1) autosomal-dominant syndrome in 20-30% of cases [START_REF] Jensen | ENETS Consensus Guidelines for the management of patients with digestive neuroendocrine neoplasms: functional pancreatic endocrine tumor syndromes[END_REF]. MEN1/ZES patients usually have an unpredictable course and frequently present with multiple duodenal gastrinomas in up to 80% of cases, with other pancreatic NETs (functional or non-functional) and the prognosis is negatively affected by lymph node and liver metastases [START_REF] Ruszniewski | Clinical, anatomical, and evolutive features of patients with the Zollinger-Ellison syndrome combined with type I multiple endocrine neoplasia[END_REF].

Consequently, local resection or enucleation rarely leads to long-term cure in patients with MEN1-associated gastrinomas. Surgery other than pancreaticoduodenectomy is associated with a high recurrence rate (>90%) [START_REF] Jensen | ENETS Consensus Guidelines for the management of patients with digestive neuroendocrine neoplasms: functional pancreatic endocrine tumor syndromes[END_REF][START_REF] Shao | Surgical management of Zollinger-Ellison syndrome: Classical considerations and current controversies[END_REF].

Medical treatment of gastric acid hypersecretion with proton pump inhibitors (PPIs) is the standard in ZES [START_REF] Jensen | ENETS Consensus Guidelines for the management of patients with digestive neuroendocrine neoplasms: functional pancreatic endocrine tumor syndromes[END_REF] in order to prevent peptic complications [START_REF] Poitras | The Zollinger-Ellison syndrome: dangers and consequences of interrupting antisecretory treatment[END_REF]. All available PPIs are effective in this indication. Besides, oral or intravenous histamine H2-receptor antagonists (H2RA) are also effective [START_REF] Jensen | ENETS Consensus Guidelines for the management of patients with digestive neuroendocrine neoplasms: functional pancreatic endocrine tumor syndromes[END_REF], but many ZES patients need high doses and frequent dosing with a non-homogeneous tolerance profile [START_REF] Mccarthy | H2-Histamine receptor blocking agents in the Zollinger-Ellison syndrome. Experience in seven cases and implications for long-term therapy[END_REF][START_REF] Osefo | Gastric acid hypersecretory states: recent insights and advances[END_REF][START_REF] Ito | Diagnosis of Zollinger-Ellison syndrome: increasingly difficult[END_REF]. Optimal and definitive control of acid hypersecretion using high-dose PPI therapy is required in cases of MEN1-associated multiple gastrinomas.

However, a growing literature suggests that life-long PPI use is not innocuous [START_REF] Lee | Insights into Effects/Risks of Chronic Hypergastrinemia and Lifelong PPI Treatment in Man Based on Studies of Patients with Zollinger-Ellison Syndrome[END_REF]. Long-term PPI intake has been associated with calcium and vitamin B12 malabsorption, risk of bone fractures, Clostridium difficile infection, community-acquired pneumonia, dementia or chronic kidney disease [START_REF] Lehault | Review of the Long-Term Effects of Proton Pump Inhibitors[END_REF][START_REF] Nehra | Proton Pump Inhibitors: Review of Emerging Concerns[END_REF]. Several recent studies have also reported PPI-induced hypomagnesemia [START_REF] Epstein | Proton-pump inhibitors and hypomagnesemic hypoparathyroidism[END_REF][START_REF] Cundy | Proton pump inhibitors and severe hypomagnesaemia[END_REF][START_REF] Park | The Association between the Use of Proton Pump Inhibitors and the Risk of Hypomagnesemia: A Systematic Review and Meta-Analysis[END_REF][START_REF] Kieboom | Proton pump inhibitors and hypomagnesemia in the general population: a population-based cohort study[END_REF][START_REF] Liao | Does the use of proton pump inhibitors increase the risk of hypomagnesemia: An updated systematic review and meta-analysis[END_REF] resulting in serious complications, such as paresthesia, seizures, muscle spasms, tremors, agitation, nausea or arrhythmia. In 2011, the U.S. Food and Drug Administration (FDA) alerted about risks of hypomagnesemia during prolonged PPI therapies (longer than one year) and communicated advice on the management of these situations [START_REF] Research | FDA Drug Safety Communication: Low magnesium levels can be associated with long-term use of Proton Pump Inhibitor drugs (PPIs)[END_REF].

Only two case reports relating PPI-induced hypomagnesemia in ZES patients have been described in the literature [START_REF] Eyal | From hypomagnesaemia to Zollinger-Ellison syndrome: an adverse effect of a proton pump inhibitor[END_REF][START_REF] Ströker | Severe symptomatic hypomagnesaemia induced by the chronic use of proton pump inhibitors: a case report of a patient with Zollinger-Ellison syndrome[END_REF]. We report here the first case of life-threatening PPI-induced hypomagnesemia in a MEN1/ZES patient, and discuss about acid hypersecretion control and complex surgical management in MEN1/ZES patients.

Case report

A 56-year-old man was referred to our institution in August 2015 for a suspicion of ZES, as he presented with typical reflux symptoms, fluid diarrhea and vomiting over a period of ten years, regressing quickly when taking esomeprazole (80 mg per day). The upper gastrointestinal endoscopy showed a 12-mm well-differentiated G1 NET in the posterior wall of the duodenal bulb (Ki67 1%). The former results, associated with high serum gastrin level (1317 pg/ml ; normal <125 pg/ml), enabled the diagnosis of ZES to be made [START_REF] Metz | Diagnosis of Zollinger-Ellison syndrome in the era of PPIs, faulty gastrin assays, sensitive imaging and limited access to acid secretory testing[END_REF]. No other lesions were seen during endoscopic ultrasound (EUS). Meanwhile, MEN1 syndrome was suspected because of the elevation of plasma calcium level (2.70 mmol/L ; normal 2.15 -2.50 mmol/L) associated with high plasma level of parathyroid hormone (188 pg/ml ; normal 14 -87 pg/ml). The complete endocrine assessment confirmed the primary hyperparathyroidism and showed a prolactin-secreting pituitary macroadenoma, a left adrenal adenoma and a 7-cm thymic tumor. Genetic screening of MEN1 gene identified a mosaicism at exon 5 (c.784-9G>A). Prolactin hypersecretion was treated by cabergoline. Primary hyperparathyroidism with serum hypercalcemia was treated by cinacalcet because parathyroid surgery was delayed as a thymic tumor was diagnosed. A thymectomy was performed in 2017: the histological analysis revealed a G2 NET (Ki67 15%). The patient was closely monitored by endocrinologists and gastroenterologists in our institution and continued long-term PPI therapy in order to control symptoms of the ZES (esomeprazole 120 mg per day).

On June 1, 2018, the patient presented with recurrent episodes of vomiting approximately 10 times per 24 hours over the previous 3 days, and a 6-kg weight loss over 1 month. The patient was hospitalized in the intensive care unit (ICU) for metabolic alkalosis and severe ionic disorders. Clinical examination showed multidirectional nystagmus, vertigo and gait instability. No otological or neurological causes were found. A severe hypomagnesemia was diagnosed (undetectable serum magnesium level <0.10 mmol/L ; normal 0.7 -1.1 mmol/L). Intravenous rehydration and correction of electrolyte disturbances were successfully performed. Esomeprazole had to be continued (120 mg per day) in order to control symptoms of the ZES. On June 19, 2018, uncontrollable vomiting recurred and the upper gastrointestinal endoscopy showed an ulcerated esophagitis leading to an increase in PPI doses (esomeprazole 240 mg per day). In July 2018, the patient was readmitted to the ICU for severe vomiting, convulsive seizures and loss of consciousness. The Glasgow Coma Scale score was 6 on ICU admission. Clinical examination showed extracellular dehydration and a cerebellar syndrome (severe truncal ataxia, multidirectional nystagmus and dysarthria). Blood tests showed impaired renal function, hypokalemia, undetectable serum magnesium level (<0.21 mmol/L ; normal 0.7 -11 mmol/L), normal blood glucose level and normal serum calcium level. This severe symptomatic hypomagnesemia was proved to be due to gastrointestinal loss, as urinary fractional excretion of magnesium was low (<0.56 mmol/L). First, intravenous magnesium supplementation and rehydration, with temporary discontinuation of PPIs were initiated. A substitution with ranitidine, a H2RA, was done (600 mg per day). After 36 hours stopping PPIs, the patient reported acute abdominal pain associated with abundant melena.

The gastrointestinal endoscopy showed an erosive duodenitis. High-dose PPIs were urgently resumed. Cerebellar syndrome partially regressed after intravenous magnesium supplementation, but ataxia persisted. Oral magnesium supplementation was tried, but hypomagnesemia and diarrhea recurred, requiring daily intravenous infusions (13.5 g of magnesium sulfate per day). Somatostatin receptor scintigraphy showed a lesion near the 2nd duodenum, with no other abnormality. However, EUS showed two infracentimetric hypervascular tumors in the pancreatic head.

Finally, further to repeated hospital admissions to the ICU, as the patient was presenting with sequella cerebellar syndrome, severe hypomagnesemia requiring daily intravenous infusions, and early gastrointestinal bleeding secondary to discontinuation of PPIs, a surgical management of the MEN1 gastrinomas was considered in order to definitely stop PPIs. Different surgical possibilities were discussed at expert multidisciplinary meetings: local resection plus lymphadenectomy, pancreaticoduodenectomy (PD) and total gastrectomy (TG). The patient's personal history was marked by non-insulin-dependent diabetes, active smoking, dyslipidemia, ischemic heart disease with active stents, recent pulmonary embolism and restrictive ventilatory disorder. Due to the MEN1 syndrome, the curative resection of all NETs would have required a PD. Risks and rewards were assessed for each of the 3 surgical options as presented in Table 1. According to the comorbidities (ECOG performance status 3), the MEN1 syndrome, the poor prognosis of the resected thymic NET [START_REF] Gibril | Prospective study of thymic carcinoids in patients with multiple endocrine neoplasia type 1[END_REF][START_REF] Ito | Causes of death and prognostic factors in multiple endocrine neoplasia type 1: a prospective study: comparison of 106 MEN1/Zollinger-Ellison syndrome patients with 1613 literature MEN1 patients with or without pancreatic endocrine tumors[END_REF], and the imperative need to definitely preclude the use of PPIs, it was decided to perform a TG. TG was associated with lower postoperative morbimortality than PD and allowed the permanent cessation of PPIs by suppressing acid hypersecretion. A TG done through roux-en-y esophago-jejunostomy and jejunojejunostomy, and implementation of a feeding jejunostomy were performed in January 2019. Histopathological examination of the resected stomach showed hypertrophic gastropathy of the body and fundus secondary to ZES (Figure 1). The postoperative course was affected by a fistula at the esophago-jejunal anastomosis, requiring surgical reintervention. In April 2019, the patient complained of dysphagia due to a severe anastomotic stenosis, which required regular balloon dilations. In August 2019, the feeding jejunostomy was removed and the patient resumed sufficient oral nutrition. After one year of postoperative follow-up, PPIS were never resumed, gait instability partially regressed, serum magnesium levels were normal, and no recurrent or metastatic disease was identified.

Discussion

PPI-induced hypomagnesemia has been described since 2006 in the literature [START_REF] Epstein | Proton-pump inhibitors and hypomagnesemic hypoparathyroidism[END_REF]. Considering all the adverse effects reported to the FDA while taking PPIs, 1% of them were related to hypomagnesemia [START_REF] Luk | Proton pump inhibitor-associated hypomagnesemia: what do FDA data tell us?[END_REF]; this risk being increased by concomitant use of loop diuretics and prolonged PPI therapy [START_REF] Kieboom | Proton pump inhibitors and hypomagnesemia in the general population: a population-based cohort study[END_REF]. Recent studies have clarified potential mechanisms, but the pathophysiology is imperfectly known [START_REF] William | Proton-pump inhibitor-induced hypomagnesemia: Current research and proposed mechanisms[END_REF]. PPI-induced hypomagnesemia is due to an alteration of active intestinal absorption, the passive pathway not being impaired. The main mechanism appears to be a pH-dependent regulation of the TRPM6 transporter in the colonic enterocyte [START_REF] William | Proton-pump inhibitor-induced hypomagnesemia: Current research and proposed mechanisms[END_REF], but individual epigenetic polymorphisms could explain why hypomagnesemia is not uniformly seen among PPI users [START_REF] Hess | Common single nucleotide polymorphisms in transient receptor potential melastatin type 6 increase the risk for proton pump inhibitor-induced hypomagnesemia: a case-control study[END_REF]. Besides, no dosedependent effect [START_REF] Chowdhry | Proton pump inhibitors not associated with hypomagnesemia, regardless of dose or concomitant diuretic use[END_REF] of PPIs has been described in the general population. Therefore, there are currently no guidelines regarding prevention and monitoring of drug-induced hypomagnesemia [START_REF] Atsmon | Drug-induced hypomagnesaemia : scope and management[END_REF]. We could recommend vigilance when prescribing prolonged PPI therapy (longer than one year) or when combining with predisposing factors known to increase the risk of hypomagnesemia (i.e. medications such as loop diuretics, malabsorption, extensive bowel resections, chronic alcoholism, or hereditary tubulopathies). Moreover, the case of this patient emphasizes the need for systematic screening and careful monitoring of serum magnesium level in all ZES patients receiving life-long PPI therapy. No preventive treatment is necessary, but low serum magnesium levels require therapeutic measures ranging from high-dose magnesium supplementation to surgical management of the ZES.

The place of surgery in MEN1-associated gastrinomas remains controversial [START_REF] Norton | Resolved and Unresolved Controversies in the Surgical Management of Patients With Zollinger-Ellison Syndrome[END_REF][START_REF] Norton | Gastrinomas: Medical or Surgical Treatment[END_REF]. MEN1/ZES patients usually have multiple duodenal gastrinomas, other pancreatic NETs and lymph node metastases. Consequently, complete cure is very difficult to achieve in this situation (<10% when PD is not performed), and it is often recommended that surgery should be restricted to patients with tumors > 2 cm to prevent metastatic dissemination [START_REF] Jensen | ENETS Consensus Guidelines for the management of patients with digestive neuroendocrine neoplasms: functional pancreatic endocrine tumor syndromes[END_REF]. Hence, surgical management of MEN1-associated gastrinomas was deferred in the initial patient's course according to the prognostic impact of the MEN1 syndrome. However, recent publications support aggressive surgery for both long-term biochemical cure and prolongation of survival by preventing liver metastases [START_REF] Shao | Surgical management of Zollinger-Ellison syndrome: Classical considerations and current controversies[END_REF][START_REF] Bartsch | Outcome of duodenopancreatic resections in patients with multiple endocrine neoplasia type 1[END_REF][START_REF] Lopez | Long-term results of surgery for pancreatic neuroendocrine neoplasms in patients with MEN1[END_REF][START_REF] Imamura | Biochemically curative surgery for gastrinoma in multiple endocrine neoplasia type 1 patients[END_REF].

Tonelli et al reported 77% of curability after pancreatic surgery for MEN1-associated gastrinomas [START_REF] Tonelli | Pancreatectomy in multiple endocrine neoplasia type 1-related gastrinomas and pancreatic endocrine neoplasias[END_REF]. However, the overall in-hospital mortality after PD for pancreatic NETs has been reported at 6%, while morbidity is mainly affected by pancreatic fistula occurrence in up to 14% [START_REF] Jilesen | Postoperative Complications, In-Hospital Mortality and 5-Year Survival After Surgical Resection for Patients with a Pancreatic Neuroendocrine Tumor: A Systematic Review[END_REF]. PD with tumor-free margins and lymphadenectomy appears to be the best choice for lesions of the pancreatic head, in an attempt to completely remove all NETs.

Conversely, partial duodenectomy or pancreas-preserving total duodenectomy have been associated with risk of recurrence and persistent postoperative hypergastrinemia [START_REF] Imamura | Biochemically curative surgery for gastrinoma in multiple endocrine neoplasia type 1 patients[END_REF][START_REF] Lopez | Partial pancreaticoduodenectomy can provide cure for duodenal gastrinoma associated with multiple endocrine neoplasia type 1[END_REF]. In this patient, considering the preoperative assessment, the MEN1 syndrome and the imperative need for a definitive withdrawal of PPIs, the probability that biochemical cure could not be obtained by surgery alone was high. Moreover, gastric acid hypersecretion can persist long-term even after a curative resection in up to 60% of patients (despite normogastrinemia), requiring antisecretory drugs [START_REF] Pisegna | Effects of curative gastrinoma resection on gastric secretory function and antisecretory drug requirement in the Zollinger-Ellison syndrome[END_REF][START_REF] Ojeaburu | Mechanism of acid hypersecretion post curative gastrinoma resection[END_REF]. Somatostatin analogues could also have been considered as their antigastrin properties have been described since 1988 in ZES patients [START_REF] Ruszniewski | Long-acting somatostatin (SMS 201-995) in the management of Zollinger-Ellison syndrome: evidence for sustained efficacy[END_REF][START_REF] Gomes-Porras | Somatostatin Analogs in Clinical Practice: A Review[END_REF], but the risk of long-term recurrence of hypergastrinemia and, therefore, the need for PPIs cannot be completely removed. Hence, considering the associated comorbidities that would have increased the morbi-mortality of PD, the multidisciplinary staff decided to perform a TG, the only way to definitely preclude the use of PPIs by suppressing gastric acid hypersecretion [START_REF] Franz | Is total gastrectomy still a viable option in the management of patients with the Zollinger-Ellison syndrome?[END_REF] with an acceptable morbimortality [START_REF] Rattner | Insulinomas and other tumours[END_REF] (Table 1).

In conclusion, this is the first case reporting a life-threatening PPI-induced hypomagnesemia in a MEN1/ZES patient. In the rare cases of persistent and life-threatening PPI-induced hypomagnesemia in patients with ZES, surgery should be considered early in order to obtain definitive and tight control of gastric acid secretion.

Complete tumor removal is recommended in sporadic gastrinomas, whereas aggressive curative surgery (i.e. PD when possible) is necessary in MEN1/ZES patients. TG could be proposed in frailty patients who are not eligible for curative pancreatoduodenal resection.

1 Table 1 : Surgical management of duodeno-pancreatic gastrinomas in MEN1/ZES patients [START_REF] Norton | Resolved and Unresolved Controversies in the Surgical Management of Patients With Zollinger-Ellison Syndrome[END_REF][START_REF] Ojeaburu | Mechanism of acid hypersecretion post curative gastrinoma resection[END_REF][START_REF] Ruszniewski | Long-acting somatostatin (SMS 201-995) in the management of Zollinger-Ellison syndrome: evidence for sustained efficacy[END_REF][START_REF] Gomes-Porras | Somatostatin Analogs in Clinical Practice: A Review[END_REF][START_REF] Franz | Is total gastrectomy still a viable option in the management of patients with the Zollinger-Ellison syndrome?[END_REF]. a Gastric acid hypersecretion can persist long term even after a curative resection in up to 60% of patients (despite normogastrinemia), requiring antisecretory drugs. b The 90-day mortality after pancreaticoduodenectomy for cancer is double the 30-day mortality

Surgical options

grant from any funding agency in the public, commercial or not-for-profit sector.


* Brassard

S Godbout

Framework for consequential life cycle assessment of pyrolysis biorefineries: A case study for the conversion of primary forestry residues

Keywords: Pyrolysis, Biochar, Bio-oil, Consequential LCA, Primary forestry residues, Biofungicide

In an endeavor towards GHG neutrality, alternatives to fossil carbon resources are explored, such as the use of biomass carbon. Pyrolysis, a thermochemical process that can convert residual biomasses into liquid (bio-oil), solid (biochar) and gaseous (non-condensable gases) products is gaining increased attention, as it both supplies alternatives to fossil carbon while potentially inducing socalled negative emissions through the biochar. Yet, the pyrolysis technical and environmental performance is heavily dependent upon process operational parameters and biomass types. In the perspective of national strategic bioeconomy planning, this study presents an easily replicable consequential life cycle assessment (LCA) framework to quantify the environmental performance of a pyrolysis biorefinery where process conditions are documented, and boundaries expanded to consider the current use of the residual biomass. Results obtained from this method are intended to provide insights for evidence-based decision making towards investments in the low fossil carbon future. The proposed LCA framework was applied to a national case study for the use of primary forestry residues (PFR). Results showed that as compared to the reference scenario in which PFR are left on soil to decay, pyrolysing PFR to biocrude oil, wood vinegar, biochar and gas presents tradeoffs in six out of the 16 impact categories studied. These results highlighted that the biomass feedstock supply, the pyrolysis technology, the co-products yields, properties and uses, as well as the choice of marginal technologies have an influence on the environmental performance of pyrolysis biorefineries.

Highlights

• A consequential LCA framework for pyrolysis biorefineries was developed • A case-study for the use of primary forest residues (PFR) was presented • Life cycle inventory data for pyrolysis were compiled and presented • The environmental performance was assessed for 16 impact categories • Pyrolysis of PFR is climate-efficient as 80% of biochar's carbon is sequestered

Introduction

Bioeconomy development for the conversion of residual biomass into bio-based products, food, feed and bioenergy is needed to accelerate the transition towards low fossil carbon use. A study by Hamelin et al. [START_REF] Hamelin | A spatial approach to bioeconomy: Quantifying the residual biomass potential in the EU-27[END_REF] revealed the importance of residual biomass as a feedstock for the European bioeconomy, where a theoretical potential of 8500 PJ year -1 was estimated. Among the biomass sources, primary forestry residues (PFR) which include logging residues, stumps, roots and dead or damaged trees represented 3200 PJ year -1 . In France alone, it is estimated that at least 2.7 Million Mg DM year -1 (~ 42 PJ) of logging residues (branches, treetops, leaves, needles and bark) could be harvested without reducing soil fertility [START_REF] Colin | Disponibilités Forestières Pour L'Énergie et les Matériaux à L'horizon[END_REF]. Moreover, recent work indicates a theoretical potential (i.e. without considering environmental or economic constraints) of 8.4 Million Mg DM year -1 (4.4 -13.9 Million Mg DM year -1 ) in the country [START_REF] Karan | Towards local bioeconomy: A stepwise framework for highresolution spatial quantification of forestry residues[END_REF]. Currently, most of logging residues are left on soil. This contributes to increasing soil's organic carbon and minerals (Ca, Mg, K, P, and N) stocks, to maintaining biodiversity and to avoiding soil compaction [START_REF] Landmann | Recommandations pour une récolte durable de biomasse forestière pour l'énergie -Focus sur les menus bois et les souches[END_REF], among others. Removal of logging residues can alter soil productivity under some site and stand conditions [START_REF] Thiffault | Effects of forest biomass harvesting on soil productivity in boreal and temperate forests -A review[END_REF][START_REF] Rocha | Forest residue removal decreases soil quality and affects wood productivity even with high rates of fertilizer application[END_REF] and negatively affect biodiversity [START_REF] Ranius | The effects of logging residue extraction for energy on ecosystem services and biodiversity: A synthesis[END_REF]. On the other hand, harvesting PFR can provide advantages such as reducing risk of pest infestation [START_REF] Schroeder | Insect Pests And Forest Biomass For Energy BT -Sustainable Use of Forest Biomass for Energy: A Synthesis with Focus on the Baltic and Nordic Region[END_REF], reducing the risk of forest fires and facilitating reforestation work [START_REF] Maier | Life cycle assessment of forest-based biomass for bioenergy: A case study in British Columbia, Canada[END_REF]. The implementation of harvest and management guidelines based on the specific local conditions are often promoted as a measure to limit the negative impacts of forestry residues removal [START_REF] Giuntoli | Domestic heating from forest logging residues: environmental risks and benefits[END_REF].

Biological and thermochemical processes are two alternatives for biomass feedstock conversion to produce bio-based products and bioenergy. Thermochemical conversion processes use heat to convert lignocellulosic biomasses such as forestry residues, agricultural crop residues and perennial crops. Among the thermochemical conversion processes, pyrolysis is used to convert dry biomass (generally < 10% water content [START_REF] Bridgwater | An Overview of Fast Pyrolysis of Biomass[END_REF]) at elevated temperature (350-700°C) in limited oxygen environment, into a solid biochar, a liquid bio-oil and non-condensable gases (NCGs). Pyrolysis products yields and properties highly depend on biomass characteristics as well as process operational parameters. In a pyrolysis biorefinery, bio-based products (e.g. biochar and wood vinegar) and renewable energy (bio-oil and NCGs) combinations can be produced from biomass by controlling the operational parameters of the plant [START_REF] Bridgwater | Renewable fuels and chemicals by thermal processing of biomass[END_REF]. Until now, fast pyrolysis plants have been used essentially to supply renewable fuels for heating purposes. Bio-oil produced from pyrolysis as a source of energy can be stored and transported easily as compared to raw biomass feedstock. However, some issues may arise from bio-crude oil combustion in heating appliances due to the high content of reactive oxygen-containing compounds [START_REF] Ren | Thermogravimetric investigation on the degradation properties and combustion performance of bio-oils[END_REF]. High-quality bio-oil with low water content, low oxygen content and low acidity can be produced from biomasses with high content of cellulose and low ash content [START_REF] Tews | Biomass direct liquefaction options: technoeconomic and life cycle assessment[END_REF], by selecting appropriate pyrolysis parameters. Besides the use of bio-crude oil for combustion purposes, the production of terrestrial transport fuels and even jet fuels by upgrading bio-crude oil is maturing [START_REF] Perkins | Process development status of fast pyrolysis technologies for the manufacture of renewable transport fuels from biomass[END_REF].

The global environmental impact of a pyrolysis plant depends on many factors, both linked to the upstream biomass supply chain, and the downstream activities such as the pyrolysis technology itself or the way the generated co-products are used. Life cycle assessment (LCA) is a widely used and normalized [START_REF] Finkbeiner | The New International Standards for Life Cycle Assessment: ISO 14040 and ISO 14044[END_REF] environmental assessment methodology to quantify the environmental performance of products and services. In the context of climate emergency, such tools for evidence-based decision making are key for ensuring the environmental performance of future investments in low fossil carbon economy. Only a few LCA studies on pyrolysis systems have been published so far. Albeit valuable, these suffer from short-comings. Notably, they all use allocation techniques where the overall environmental impact is randomly partitioned between the product studied (typically bio-oil) and its co-products (e.g. non-condensable gases, biochars), whether according to the market value of these at a certain point in time, or their dry/wet mass, etc. In other words, the exact use of the coproducts is completely disregarded in most studies, which influences the environmental performance of the pyrolysis system. In LCA, this particular way of handling multi-functionality of products is typically referred to as attributional LCA (A-LCA), while a full inclusion of the co-products along with an understanding of their fate and what they replace on the market is often referred to as consequential LCA (C-LCA) [START_REF] Brandão | Consequential Life Cycle Assessment: What, How, and Why?[END_REF]. In other words, a consequential LCA model includes all the activities that are expected to change as a consequence of a change in demand for the functional unit [START_REF] Ekvall | Attributional and consequential LCA in the ILCD handbook[END_REF]. Sharifzadeh et al. [START_REF] Sharifzadeh | The multi-scale challenges of biomass fast pyrolysis and bio-oil upgrading: Review of the state of art and future research directions[END_REF] reported that there is a critical knowledge gap regarding C-LCA evaluation of fast pyrolysis. Examples of A-LCA studies evaluating the environmental performance of pyrolysis of forestry biomass are shown in Table 1. Other limitations of the current published studies include a lack of transparency about life cycle inventory data, the exclusion of capital goods in the analysis and the evaluation of a narrow set of environmental impact categories.

The aim of this study is to provide a generic consequential LCA framework for the quantification of the environmental performance of pyrolysis biorefineries, along with a transparent and detailed life cycle inventory of the pyrolysis process itself. The objective is to supply the analytical tools needed in order to figure out if it is environmentally viable to use residual biomass as an input in a pyrolysis biorefinery to produce bio-based products, biochar and bioenergy. To illustrate the proposed framework, a case study for the use of PFR in an auger pyrolysis reactor is presented. Producing renewable jet fuel.

Circulating fluidized bed reactor, 500°C. Bio-oil is converted to a mixture of hydrocarbons by hydrodeoxygenation (H2).

Poplar, willow, corn stover and forestry residues.

MJ of fuel

Well-to-wake, from feedstock cultivation to products end use.

GWP100

[24] Ecoinvent v.2.2

Gasoline and diesel produced from fast pyrolysis and hydroprocessing for use of the fuel in a vehicle.

Fast pyrolysis: circulating fluidized bed.

Forestry residues 1 km traveled by a lightduty passenger vehicle.

Well-to-wheel Climate change, Net energy value.

[25]

Literature sources, Ensyn/UOP (for pyrolysis)

Pyrolysis oil combustion for power generation.

Fast pyrolysis integration with power plant.

Woodchips 1 kWh electricity generated

Cradle-to-Grave GWP100

Methodology 2.1 Overall consequential LCA framework

The LCA methodology follows the ISO international standards: ISO 14040 [START_REF]ISO 14040: Environmental management -Life Cycle Assessment -Principles and Framework[END_REF] and 14044 [START_REF]ISO 14044: Environmental Management -Life Cycle Assessment -Requirements and Guidelines[END_REF]. The consequential LCA approach was selected over the attributional method since it is recognised as the most suitable to support decision-making [START_REF] Roos | Consequential life cycle assessment of bioenergy systems -A literature review[END_REF].

Background life cycle inventory (LCI) data were retrieved from Ecoinvent v.3 [START_REF] Moreno-Ruiz | Documentation of changes implemented in ecoinvent v3[END_REF] and Agri-footprint [START_REF] Durlinger | Agri-footprint 4.0 -Part 1: Methodology and basic principles[END_REF][START_REF] Durlinger | Agri-footprint 4.0 -Part 2: Description of data[END_REF] databases, while foreground data were taken from literature, pyrolysis experiments and characterisation of co-products. Conformingly with the consequential LCA rationale, marginal processes were used, which can be defined as the technologies installed due to expected long-term changes in demand [START_REF] Weidema | Marginal production technologies for life cycle inventories[END_REF]. The life cycle impact assessment (LCIA) is carried out to translate all flows into 16 characterized impact category metrics using the Environmental Footprint (EF) Method 2.0 as implemented in the Simapro LCA software, version 9.0 (PRé Consultants B.V., The Netherlands). The EF method was selected since it is in accordance with the recommendations of the European Commission [START_REF] Commission | Commission recommendation on the use of common methods to measure and communicate the life cycle environmental performance of products and organisations[END_REF][START_REF]Product Environmental Footprint Category Rules Guidance. PEFCR Guid Doc -Guid[END_REF]. Data quality was evaluated for all flows of the model (Table S19), conforming with ISO standards 14040 and 14044 [START_REF]ISO 14040: Environmental management -Life Cycle Assessment -Principles and Framework[END_REF][START_REF]ISO 14044: Environmental Management -Life Cycle Assessment -Requirements and Guidelines[END_REF]. Moreover, the importance of data for each flow in the 16 impact categories was qualitatively assessed (Tables S20 andS21 in the supporting document).

Goal and scope definition

Besides the production of a framework for pyrolysis LCA, the goal of this illustrative case study is to quantify the environmental performance of pyrolysis biorefineries fed with PFR, where the pyrolysis process is driven by the production of bio-crude oil. The vision is to compare this environmental performance with the current system in which PFR are left on soil to decay (reference case, also referred to as counterfactual case). It will allow determining whether it is environmentally viable or not to harvest PFR for conversion by pyrolysis to produce bioenergy, biochar and bio-based products (herein biopesticide). As the results of the LCA to be performed are intended for strategic investment decisions, it is the longer-term temporal scope (30 years) that is considered herein to select the marginal technologies. The time horizon for the impact assessment is 100 years. The geographical scope of interest is metropolitan France.

The functional unit, i.e. the unit to which input and output flows are related, corresponds to the management of 1000 kg of dry biomass. This is selected in the perspective of using the framework essentially with residual biomass, but also for future comparison with other bioeconomic uses for this feedstock.

Scenario description and system boundaries

The system boundary (Figure 1) includes the biomass supply chain (harvest, chipping, transport), the conditioning of biomass (e.g. storage, grinding, drying), the pyrolysis plant construction and operation (including the fractional condensation of pyrolysis gases) and the use of the pyrolysis coproducts. The system boundaries are expanded to include what is affected by the use of PFR for pyrolysis and the use of the biorefinery co-products.

A mass balance (Table S1 andS2) was established considering the harvest of 1000 kg of dry PFR (conifer species) from forests of France. The quality and partition between the different co-product of pyrolysis are highly dependent upon process conditions, among other the temperature, the residence time of biomass in the reactor and the flowrate and type of carrier gas [START_REF] Demirbas | Effects of temperature and particle size on bio-char yield from pyrolysis of agricultural residues[END_REF][START_REF] Brassard | Pyrolysis in auger reactors for biochar and bio-oil production: A review[END_REF]. The quantity and properties of each pyrolysis co-product (bio-crude oil, wood vinegar, non-condensable gases and biochar) were determined based on published and on-going experimental data, as further described by Brassard et al. [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF]. Accordingly, the auger reactor technology was selected for the pyrolysis process.

Substitution of products and related services

As illustrated in Figure 1, harvesting PFR avoids its counterfactual management, which is the decay on soil. Here, the vision is to produce bio-crude oil to be used in small-scale oil boilers in areas without access to the gas grid. Other uses of the bio-crude oil could of course be considered, for instance as a feedstock for bio-based aviation fuels following hydro-processing and hydro-cracking [START_REF] Liu | Process design and evaluations for producing pyrolytic jet fuel[END_REF]. Here, the purpose was to illustrate that the selected use of the bio-crude oil conditions the whole system boundary for the LCA. In the short-term, bio-crude oil would likely substitute fossil fuel oil. For instance, fuel oil represents 12.8% of energy sources used for building heating systems in France [START_REF] Fontan | Agir en cohérence avec les ambitions -Rapport annuel neutralité carbone[END_REF]. In the longer-term, it may rather prevent the deployment of biomass boilers [START_REF] Wenzel | Carbon footprint of bioenergy pathways for the future Danish energy system[END_REF], which is considered herein.

Biochar is applied to soil as amendment and it is considered that no additional process is avoided by this, as no soil amendment would have been added otherwise. The wood vinegar is used as a biofungicide and chemical fungicides production is therefore avoided.

It is considered that non-condensable gases are burned in a natural gas industrial furnace (> 100 kW) for district heat production. The equivalent amount of heat is considered avoided from the combustion of natural gas in the same industrial furnace. The vision is that the heat could be used at the pyrolysis plant which is nearby a city where natural gas grid is accessible. Similarly, the heat produced by district cogeneration (CHP) is considered to substitute the heat produced by the combustion of natural gas.

The marginal electricity mix used in all processes (high and medium voltages) is taken from Ecoinvent 3.5 for consequential modeling. Accordingly, the power sources for France are wind (84%), wood (13.2%), geothermal and hydroelectricity.

Scenario modelling and life cycle inventory 2.5.1 Biomass supply chain

The PFR feedstock can be defined as the by-products of wood harvesting. In this study, it is considered that only logging residues (treetops and small branches less than 7 cm; stumps are excluded) are harvested for pyrolysis. The biomass supply chain considered herein includes the harvest of PFR in forest by forwarder, transport to the roadside, chipping to 10-100 mm using a mobile chipper consuming diesel and transport to the biomass depot by van. This corresponds to the most widespread supply chain for logging residues after final fellings in Europe, including France [START_REF] Díaz-Yáñez | Forest chips for energy in Europe: Current procurement methods and potentials[END_REF]. The operation time of forwarder and chipper for processing 1 Mg of dry biomass was calculated [START_REF] Eriksson | Energy efficient storage of biomass at Vattenfall heat and power plants[END_REF][START_REF] Jirousek | Productivity and costs of the mechanised cut-to-length wood harvesting system in clear-felling operations[END_REF] as detailed in the supporting document (Table S3 andS4). Meta-analyses of field studies did not report significant reduction of soil organic carbon (SOC) following removal of forestry residues [START_REF] Giuntoli | Domestic heating from forest logging residues: environmental risks and benefits[END_REF]. Therefore, changes in forest carbon stocks due to forestry residues removal are assumed to be negligible [START_REF] Tews | Biomass direct liquefaction options: technoeconomic and life cycle assessment[END_REF].

The chemical composition of PFR at harvesting (Table 2) was determined based on a compilation of literature data. The moisture content of wood residues collected in the forest is variable and depends on many parameters. Typical moisture content for fresh forestry residues is near 50% [START_REF] Whittaker | Dry Matter Losses and Methane Emissions During Wood Chip Storage: the Impact on Full Life Cycle Greenhouse Gas Savings of Short Rotation Coppice Willow for Heat[END_REF], and can vary from 48 to 57% [START_REF] Hofmann | Drying effects and dry matter losses during seasonal storage of spruce wood chips under practical conditions[END_REF]. In a study by Pettersson and Nordfjell [START_REF] Pettersson | Fuel quality changes during seasonal storage of compacted logging residues and young trees[END_REF], moisture content of logging residues stored in small piles at the felling site dropped from approximatively 50% to 28.6% in 3 weeks in June. According to Thörnqvist [START_REF] Thörnqvist | Drying and storage of forest residues for energy production[END_REF], the biomass can reach 25% moisture content by the end of summer when they remain in the logging area. Routa et al. [START_REF] Routa | Precision measurement of forest harvesting residue moisture change and dry matter losses by constant weight monitoring[END_REF] reported that logging residues can dry by up to 30% in the forest during a 6-week period if weather conditions are favorable. Accordingly, it is here considered that fresh PFR at 50% moisture content are left on soil in dry weather conditions for passive drying during at least a six weeks period to reach 29.9% moisture content before harvesting. This reliance on passive drying implies that PFR are harvested only between May and October.

Biomass storage and conditioning

The surface area of the building needed to store the biomass was calculated based on considerations detailed in the supporting document. Storage of wet biomass can cause microbial decomposition and chemical reactions at high temperatures [START_REF] Jirousek | Productivity and costs of the mechanised cut-to-length wood harvesting system in clear-felling operations[END_REF][START_REF] Whittaker | Dry Matter Losses and Methane Emissions During Wood Chip Storage: the Impact on Full Life Cycle Greenhouse Gas Savings of Short Rotation Coppice Willow for Heat[END_REF], which increases the dry matter loss (and therefore emissions to air) besides causing a decline in fuel quality. The dry matter loss can be associated with methane (CH4) emissions from the chips pile [START_REF] Whittaker | Dry Matter Losses and Methane Emissions During Wood Chip Storage: the Impact on Full Life Cycle Greenhouse Gas Savings of Short Rotation Coppice Willow for Heat[END_REF]. According to the review performed by Hofmann et al. [START_REF] Hofmann | Drying effects and dry matter losses during seasonal storage of spruce wood chips under practical conditions[END_REF], the maximum moisture content for storage stability is between 15 and 30 %. Drying in forest to less then 30% water content prior to chipping and storage therefore allows stable storage conditions with few losses of dry matter [START_REF] Routa | Precision measurement of forest harvesting residue moisture change and dry matter losses by constant weight monitoring[END_REF]. A 2% dry matter loss during storage was selected in the present case study [START_REF] Eriksson | Energy efficient storage of biomass at Vattenfall heat and power plants[END_REF]. It is assumed that only CH4 and CO2 were emitted due to the degradation of dry matter, based on Tonini et al. [START_REF] Tonini | Bioenergy Production from Perennial Energy Crops: A Consequential LCA of 12 Bioenergy Scenarios including Land Use Changes[END_REF] (see calculation in the supporting document, Table S6).

Auger pyrolysis reactors, as considered in this study, require biomass with small particle size to favor the heat transfer and to ensure complete reaction [START_REF] Tews | Biomass direct liquefaction options: technoeconomic and life cycle assessment[END_REF]. A range of particle size of 1-3 mm is typically recommended for pyrolysis [START_REF] Steele | Life-Cycle Assessment of Pyrolysis Bio-Oil Production[END_REF][START_REF] Zhong | Life-cycle assessment of flash pyrolysis of wood waste[END_REF][START_REF] Thiffault | management as pre-treatment practices in Canadian forest biomass supply chains[END_REF]. In the study by Brassard et al. [START_REF] Brassard | The Production of Engineered Biochars in a Vertical Auger Pyrolysis Reactor for Carbon Sequestration[END_REF], wood particle size between 1 and 3.8 mm was used for pyrolysis in an auger reactor. The pyrolysis scenario studied here considers that wood chips are grinded using a stationary electric chipper (Table S7). The mass loss into dust following grinding was estimated to 1% of total mass at the inlet of the grinder. This dust is here burned for heat and power co-generation (Table S9).

Biomass physicochemical properties will influence both the pyrolysis process and the various properties of co-products. More specifically, the moisture content of biomass has high importance as it influences the physicochemical properties of bio-oil [START_REF] Hognon | Comparison of pyrolysis and hydrothermal liquefaction of Chlamydomonas reinhardtii. Growth studies on the recovered hydrothermal aqueous phase[END_REF]. Bridgwater et al. [START_REF] Bridgwater | An Overview of Fast Pyrolysis of Biomass[END_REF] recommend a water content below 10 wt% prior to feeding the pyrolyzer in order to produce a bio-oil with a water content below 30 wt%. Therefore, it is here considered that PFR are further dried to 10 wt% moisture prior to pyrolysis [START_REF] Ayer | Supplying renewable energy for Canadian cement production: Life cycle assessment of bioenergy from forest harvest residues using mobile fast pyrolysis units[END_REF][START_REF] Steele | Life-Cycle Assessment of Pyrolysis Bio-Oil Production[END_REF] with a rotary dryer [START_REF] Del Giudice | Wood Chip Drying through the Using of a Mobile Rotary Dryer[END_REF]. The temperature generally employed is around 200°C but should not be above 250°C in order to prevent degradation of dry matter [START_REF] Haque | Techno-Economic and Environmental Evaluation of Biomass Dryer[END_REF]. In these conditions and with a biomass water content < 30 wt% prior to drying, degradation of dry matter and consequently gas emissions are considered to be negligible [START_REF] Milota | Emissions from Biomass in a Rotary Dryer[END_REF] at the drying stage. The energy needed to evaporate 1 kg of water from biomass was estimated to 4 MJ kg -1 water, according to literature [START_REF] Li | Evaluation of a biomass drying process using waste heat from process industries: A case study[END_REF][START_REF] Roberts | Life Cycle Assessment of Biochar Systems: Estimating the Energetic, Economic, and Climate Change Potential[END_REF]. Therefore, the total heat needed was calculated based on the quantity of water to evaporate (Table S8). It is considered that the energy source to heat the rotary dryer is natural gas burned in an industrial furnace.

Pyrolysis and condensation

Mass balance of the pyrolysis biorefinery (Table S2) was established based on experiments carried out with a semi-pilot scale auger reactor of 1 kg biomass per hour capacity [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF]. These experiments were performed using pyrolysis parameters (temperature, residence time and nitrogen flowrate) that were determined using the response surface methodology approach to produce the highest yield of bio-oil [START_REF] Brassard | The Production of Engineered Biochars in a Vertical Auger Pyrolysis Reactor for Carbon Sequestration[END_REF]. Nitrogen is used as a carrier gas to prevent the injection of oxygen in the pyrolysis system. The residence time represents the duration that biomass stays in the reactor.

Further pyrolysis experiments on the set-up described by Brassard et al. [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF] were carried out by Álvarez-Chávez [START_REF] Álvarez-Chávez | Bio-oil yield and quality enhancement through fast pyrolysis and fractional condensation concepts[END_REF] to study the fractional condensation of bio-oil in order to obtain a bio-crude oil with lower water content and an aqueous fraction. The condensation system consists in two double shell stainless tubes in which water/glycol (50:50 mixture in the first condenser and 100:0 in the second condenser) circulates counter flow to pyrolysis gases. The heavy phase (bio-crude oil) is obtained in the first condenser in which the cooling fluid is set at high temperature and the light phase (wood vinegar) is obtained in the second condenser at a lower temperature. The pyrolysis and condensation operational parameters and product yields considered in this case study are presented in Table 3. Electricity supply to the pyrolysis and condensation units was calculated (Table S10 and S11) based on the energy consumption of the semi-pilot pyrolysis unit described by Brassard et al. [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF]. A few industrial scale pyrolysis units were developed in the last few years. Perkens et al. [START_REF] Perkins | Process development status of fast pyrolysis technologies for the manufacture of renewable transport fuels from biomass[END_REF] listed twenty pyrolysis plants around the world operating at feed rates of 1 to 274 Mg per day. Industrial auger pyrolyzers with capacities up to 50 Mg day -1 are available on the market [START_REF] Perkins | Process development status of fast pyrolysis technologies for the manufacture of renewable transport fuels from biomass[END_REF][START_REF] Campuzano | Auger reactors for pyrolysis of biomass and wastes[END_REF].

On this basis, the full-scale pyrolysis plant modelled in this study is expected to process 20 Mg of biomass (10% w.c.) per day and 4800 Mg per year. It is considered that products yields and properties will be similar to the results obtained in the semi-pilot reactor described above [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF] (Table 3). The construction of the pyrolysis plant was modeled using the infrastructure process "Synthetic gas factory" from Ecoinvent 3.5 (see the details in the supporting document, Table S10). This process includes buildings and facilities (including dismantling) of a typical biomass gasifier as well as land use. Its lifetime is assumed to be 50 years.

Combustion of bio-crude oil and avoided combustion of wood chips

The produced bio-crude oil has a water content of 18.8 wt% and an energy content of 18.3 MJ kg -1 [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF]. The heat produced by bio-oil burning (5725 MJ, which considers 80% conversion efficiency for the oil burner) is considered to replace the equivalent heat provided by the combustion of softwood chips in a central or small-scale furnace (50 kW).

Transport distance from pyrolysis plant to the burner is conservatively estimated to 200 km. In general, the emissions from bio-oil combustion are between those of light (fossil) oil and heavy oil, but particulate emissions can be higher and SOx emissions are very low [START_REF] Lehto | Review of fuel oil quality and combustion of fast pyrolysis bio-oils from lignocellulosic biomass[END_REF]. Similarly, Hou et al. [START_REF] Hou | Co-Firing of Fast Pyrolysis Bio-Oil and Heavy Fuel Oil in a 300-kWth Furnace[END_REF] experimented the combustion of a blend of 2.5% bio-oil / 97.5% heavy fuel oil and found that emissions were not different as compared to the combustion of pure heavy fuel oil. Ren et al. [START_REF] Ren | Thermogravimetric investigation on the degradation properties and combustion performance of bio-oils[END_REF] also reported that raw bio-oil had comparable combustion performance to fuel oil. Accordingly, the partition of C, N and S compounds in the gaseous emissions from bio-crude combustion was modeled using the partition of gases provided by the process "Heat, central or small-scale, other than natural gas {Europe without Switzerland} | heat production, light fuel, at boiler 100 kW, non-modulating | Conseq, U" retrieved from Ecoinvent database version 3.5 (Table S12).

Combustion of non-condensable gases and avoided combustion of natural gas

The non-condensable gases (NCGs) composition considered herein is based on the sampling and characterization work described by Brassard et al. [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF]. In this study, hydrogen (H2) has not been analyzed and was therefore added to all other compounds reported. The volumetric concentration (%vol.) of H2 was fixed at 5.2%vol. based on simulations made from the equilibrium reactions presented by Ferreira et al. [START_REF] Ferreira | A Holistic Review on Biomass Gasification Modified Equilibrium Models[END_REF] and the remaining volumetric composition was adjusted on the basis of the results reported by Brassard et al. [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF]. The resulting composition and lower heating value (LHV) of the pyrolysis NCGs is presented in Table 4.

It is considered that NCGs are burned in a natural gas industrial furnace (> 100 kW) for district heat production. This results in 858.7 MJ of heat produced, which was calculated from the calorific value of gases (Table 4) and the heat conversion efficiency of syngas estimated at 75% by Roberts et al. [START_REF] Roberts | Life Cycle Assessment of Biochar Systems: Estimating the Energetic, Economic, and Climate Change Potential[END_REF]. The equivalent amount of heat is considered avoided from the combustion of natural gas in the same industrial furnace, but with an efficiency of 85%.

The partition of C, N and S compounds in the gaseous emissions from non-condensable gases combustion was modeled using the partition of gases provided by the process "Heat, district or industrial, natural gas {Europe without Switzerland} | heat production, natural gas, at industrial furnace > 100 kW, | Conseq, U" retrieved from Ecoinvent database version 3.5 (Table S14).

Biochar as a soil amendment

The biochar elementary composition (Table 5) was determined based on pyrolysis experiments with woody biomass [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF] and adjusted according to the chemical composition of the PFR considered herein (Table 2). It is considered that biochar is transported on a 100 km distance from the pyrolysis plant to a farm with a freight lorry, mixed with manure, and applied with a conventional manure spreader (see detailed process in Table S15).

Biochar applied to soil increases soil C stocks, resulting in net CO2 removals from the atmosphere. A large fraction of C in biochar is retained in soil over several decades, but the time it remains will vary depending on the type of biochar and soil conditions [START_REF] Paustian | Climate-smart soils[END_REF]. According to 12 studies published after 2010, the C sequestration potentiel by 2050 ranges between 0.03 and 6.6 Gt CO2e yr -1 [START_REF]IPCC Special Report on Climate Change, Desertification, Land Degradation, Sustainable Land Management, Food Security, and Greenhouse gas fluxes in Terrestrial Ecosystems[END_REF]. Schmidt et al. [START_REF] Schmidt | Pyrogenic carbon capture and storage[END_REF] demonstrated that pyrolytic carbon capture and storage can attain carbon sequestration efficiency (CSE) of more than 70% when C in biochar and bio-oil are sequestered, CSE being defined as the percentage of the feedstock C being captured [START_REF] Werner | Biogeochemical potential of biomass pyrolysis systems for limiting global warming to 1.5 °C[END_REF]. According to Budai et al. [START_REF] Budai | Biochar Carbon Stability Test Method : An assessment of methods to determine biochar carbon stability[END_REF], a biochar H/Corg molar ratio in the range 0.4 -0.7 would indicate that the fraction of biochar C remaining after 100 years (Fperm) is equal to 50%. The IPCC [START_REF]Appendix 4. Method for Estimating the Change in Mineral Soil Organic Carbon Stocks from Biochar Amendments: Basis for Future Methodological Development[END_REF] indicated that the Fperm is 80% ( ± 11%) for biochar produced at medium temperature (450-600 °C). In a LCA of large-scale biochar production, Azzi et al. [START_REF] Azzi | Prospective Life Cycle Assessment of Large-Scale Biochar Production and Use for Negative Emissions in Stockholm[END_REF] have set the carbon stability of biochar to 80%, but also considered lower and higher values of 70 and 90% in a sensitivity analysis. Therefore, Fperm was set to 80% in the present case study.

Wood vinegar used as a biofungicide

The composition of the aqueous fraction of bio-oil (wood vinegar) was derived from unpublished data produced from fractional condensation experiments with the pyrolysis set-up described by Brassard et al. [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF]. Accordingly, it has a water content of 53.1 wt%, it contains sugars (5.7 wt%), phenolic compounds (8.2 wt%) and acetic acid (11.4 wt%). Some studies reported that phenolic compounds in the wood vinegar have an antifungal potential [START_REF] Pizzolitto | Inhibitory Effect of Natural Phenolic Compounds on Aspergillus parasiticus[END_REF][START_REF] Zabka | Antifungal efficacy of some natural phenolic compounds against significant pathogenic and toxinogenic filamentous fungi[END_REF][START_REF] Hwang | Antimicrobial effect of the wood vinegar from Cryptomeria japonica sapwood on plant pathogenic microorganisms[END_REF][START_REF] Hossain | Insecticidal and anti-microbial activity of bio-oil derived from fast pyrolysis of lignin, cellulose, and hemicellulose[END_REF][START_REF] Baimark | Study on wood vinegars for use as coagulating and antifungal agents on the production of natural rubber sheets[END_REF]. According to Jung [START_REF] Jung | Growth inhibition effect of pyroligneous acid on pathogenic fungus,Alternaria mali, the agent of Alternaria blotch of apple[END_REF], phenols in combination with methanol and carboxylic acid are the major anti-fungal compounds found in bio-oil. Using the aqueous fraction of bio-oil as a bio-fungicide is consistent with the increase of the global biopesticide market that was valued at 3 Billion USD in 2017 [START_REF] Damalas | Current Status and Recent Developments in Biopesticide Use[END_REF] and 4.4 Billion USD in 2019 [START_REF]Fortune Business Insights. Biopesticides Market Size, Share & COVID-19 impact Analysis, By Type (Bioinsecticide, Biofungicide, Bionematicide, and Others), Source (Microbials and Biochemicals), Mode of Application (Foliar Application, Seed Treatment, Soil Treatment, and Others)[END_REF]. Among all biopesticides, biofungicides hold the largest market share [START_REF]Fortune Business Insights. Biopesticides Market Size, Share & COVID-19 impact Analysis, By Type (Bioinsecticide, Biofungicide, Bionematicide, and Others), Source (Microbials and Biochemicals), Mode of Application (Foliar Application, Seed Treatment, Soil Treatment, and Others)[END_REF].

In this case study, wood vinegar is expected to replace a typical fungicide on the market. Generic fungicide LCI data were taken from Agri-Footprint database (2017; Table S17) but the process was modified by integrating the marginal sources of energy considered herein. In that process, the application rate of fungicide is 0.292 kg a.i. ha -1 by mixing 1 kg of fungicide to 370 kg of water. The same total volume but with a different proportion of wood vinegar (16.3 kg) and water (354 kg) is applied in the pyrolysis scenario. In this solution, the acetic acid concentration is limited to 0.5% in order to avoid damage to the plants [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF].

Counterfactual fate of PFR

It is considered that the counterfactual fate of PFR is the decay on soil, i.e. the PFR are left on-site and never harvested. All the C from biomass decay on soil is considered to be released as CO2 because forest soils are generally aerobic [START_REF] Giuntoli | Domestic heating from forest logging residues: environmental risks and benefits[END_REF]. The decomposition rate of PFR within 100 years was estimated at 91% based on a study by Repo et al. [START_REF] Repo | Indirect carbon dioxide emissions from producing bioenergy from forest harvest residues[END_REF]. The authors developed a model simulating the decomposition of forestry residues and reported that 2-16% of the initial branch (Norway spruce species) remains after 100 years. Accordingly, the decay of 1 Mg of PFR on soil would emit 1715 kg CO2e and would sequester 169.6 kg CO2e.

Uncertainty analysis

The sources of uncertainty in LCA are numerous and are related to data (parameter uncertainty), choices made in the construction of scenarios and impact assessment modelling choice [START_REF] Bamber | Comparing sources and analysis of uncertainty in consequential and attributional life cycle assessment: review of current practice and recommendations[END_REF]. In this study, uncertainty is assessed using sensibility analysis for the potentially sensitive parameters identified after a contribution analysis. The parameters selected for a sensitivity analysis are the one that are uncertain and for which a change can cause a different conclusion in the impact assessment for a given impact category.

Results and Discussions 3.1 Impact assessment 3.1.1 Climate change impact

The pyrolysis scenario shows a reduction of 906.4 kg CO2e Mg -1 dry PFR as compared to the reference (or counterfactual) scenario in the climate change impact category (Figure 2). The modeled pyrolysis plant processing 4800 Mg of biomass (10% w.c.) per year would therefore contribute to a reduction of 4264 Mg CO2e year -1 . This corresponds to ca. 645 average passenger cars (a mix of car sizes and fossil fuel use) travelling 20,000 km, based on the Ecoinvent process " Transport, passenger car, EURO 4 | Conseq, U".

The difference between both scenarios is mainly due to the sequestration of ~142 kg Cbiochar Mg -1 dry PFR in the pyrolysis scenario, considering that 80% of the biochar-C remains in soils for more than 100 years. The CO2 emissions from the combustion of bio-crude oil (674 kg CO2e) is the biggest contributor to the climate change category as its importance was defined as crucial (Table S20). It is followed by the emissions from PFR storage and pretreatment (295 kg CO2e) which includes 206 kg CO2e from wood chips storage (88.2% from CH4 and 11.6% from CO2), and 87 kg CO2e from drying using heat from natural gas combustion. The contributions of the PFR supply chain processes (harvest and transport) and of the pyrolysis & condensation processes are relatively small.

Considering the objective of limiting the increase in the global average temperature to well below 2°C above pre-industrial levels [80], PFR are thus clearly better managed as a feedstock to pyrolysis for bio-oil and biochar production than left unharvested to decay in forests (reference). However, Giuntoli et al. [START_REF] Giuntoli | Domestic heating from forest logging residues: environmental risks and benefits[END_REF] demonstrated that the climate mitigation efficiency of bioenergy production from forest logging residues depends on the decay rate of biomass left on soil. The result obtained for the case study presented herein is based on the hypothesis that 91% of the forest residues left on soil will decompose and emit CO2 within 100 years [START_REF] Repo | Indirect carbon dioxide emissions from producing bioenergy from forest harvest residues[END_REF].

The reduction of 906.4 kg CO2e Mg -1 dry PFR stands in the range of 0.4 -1.2 Mg CO2e Mg -1 (dry feedstock) reported in other studies on the life cycle climate change impact of biochar systems [START_REF] Cowie | Biochar, carbon accounting and climate change[END_REF].

In the present study, only the C sequestration potential of biochar was considered as a GHG emission mitigation effect. However, Azzi et al. [START_REF] Azzi | Prospective Life Cycle Assessment of Large-Scale Biochar Production and Use for Negative Emissions in Stockholm[END_REF] reported that considering cascading effects of biochar could double the benefits provided by biochar in terms of CO2 emissions mitigation. This additional effect can be obtained when biochar is used to feed cows to reduce enteric CH4 emissions, mixed with manure to reduce emissions from manure storage and applied to soil to reduce N2O emissions from nitrogen fertilization. A meta-analysis [START_REF] Borchard | Biochar, soil and land-use interactions that reduce nitrate leaching and N2O emissions: A meta-analysis[END_REF] revealed that biochar overall reduces N2O emissions by 38% (compared to situations without biochar application), but that reductions are greater immediately after application. Biochar can provide additional benefits when added to soil and have positive effect on soil physical, chemical and biological properties, which can increase plant growth [START_REF] Brassard | 4 -Biochar for soil amendment[END_REF]. However, these effects are specific to biochar type, manure and soil properties and environmental conditions. Figure 2. Contribution analysis for climate change impact category (kg CO2e Mg -1 dry PFR). PFR: primary forestry residues; NCG: Non-condensable gases; CHP: Combined heat and power.

Trade-offs

Trade-offs were observed for six impacts, i.e. impacts for which the reference scenario presents a higher performance than for the pyrolysis case. These are "cancer human health effects", "freshwater eutrophication", "resource use (minerals & metals)", "ozone depletion", "Acidification, terrestrial and freshwater", and "water scarcity" (Figure 3). The pyrolysis and condensation process is the highest contributor in the first three impact categories mentioned above. Most of the contribution (82 to 85%) of this process is from the use of electricity as a source of energy in the pyrolysis process. In the consequential electricity mix used (France), 84% of electricity is produced from wind turbines.

The main substance contributing to "Cancer human health effects" is chromium, emitted to water and air from the steel production for the construction of wind turbines. Similarly, the main substance contributing to "Freshwater eutrophication" is phosphate, which is emitted by the copper production used for the construction of wind turbines. The contributions to "Resource use, mineral and metals" essentially stem from three processes: pyrolysis (metals used in the construction of wind turbines for electricity production), storage of biomass (metals used in the construction of the building hall), and combustion of bio-crude oil (chromium and cooper used for the boiler and storage tanks).

Though it was unimportant for climate change, electricity consumption of the pyrolysis process is thus a critical spot for these impacts. The consumption of the pyrolysis reactor (781 kWh Mg -1 biomass) measured in experiments with a semi-pilot scale reactor could be slightly overestimated for a full-scale pyrolysis plant. For instance, Tews et al. [START_REF] Tews | Biomass direct liquefaction options: technoeconomic and life cycle assessment[END_REF] established the energy balance of a fast pyrolysis plant with a capacity of 3000 Mg of dry biomass per day, modeled based on a compilation of experimental data. Authors indicated that the need in heat and power of the pyrolysis unit is ca. 12% of energy content of biomass input, which would be equivalent to 564 kWh Mg -1 biomass in the present scenario. The trade-off (i.e. delta between the pyrolysis and reference scenario) in the impact category "Acidification terrestrial and freshwater" is only 0.018 mol H + eq Mg -1 PFR. The main contributing substances to this impact in the pyrolysis scenario are nitrogen oxides (NOx, 60.9%) and Sulfur dioxide (SO2, 30.8%). About 45% of these substances are emitted from the combustion of bio-crude oil. In the reference scenario, 64.7% of the contribution to this impact comes from NOx emissions from wood chips combustion.

The contribution to ozone depletion is, in the pyrolysis scenario, mainly due to the harvest of forestry residues (PFR supply chain) and the drying of wood (PFR storage/pretreatment). Methane (bromochlorodifluoro-, Halon 1211) emitted from the transport through pipeline of natural gas used as an energy source to dry the wood to 10% w.c. contributes for 40.3% of the total emissions in this category. Similarly, in the reference scenario, combustion of natural gas (marginal energy replacing the energy produced by dust and NCGs combustion) contributes to the "ozone depletion" potential mainly because of the emission of Halon 1211. Finally, about 25% of the total CFC111 eq. of the pyrolysis scenario is due to methane (bromotrifluoro-, Halon 1301) emitted from the diesel production used by the forwarder for PFR harvest and by the lorry for the transport of the wood chips.

The process consuming the highest amount of water is, in both scenarios, the application of pesticides (37 m 3 for biofungicides in the pyrolysis scenario and 49.5 m 3 for fungicides in the reference scenario). However, the use of water is higher in the pyrolysis scenario (+5.7 m 3 because 13.6 m 3 of water is needed for condensation).

Remaining impact categories

In the nine additional impact categories (Figure 4), the environmental performance of the pyrolysis scenario is better (lower impact) than in the reference scenario. The combustion of wood chips is the major contributor in the reference scenario for many impact categories. In the impact categories "photochemical ozone formation (HH)", "eutrophication marine" and "eutrophication terrestrial", the main contributing substance is nitrogen oxides (NOx), which is mainly emitted from the combustion of wood chips (reference scenario), and bio-crude oil and NCGs (pyrolysis scenarios). NOx emissions from the combustion of softwood chips at a furnace (50 kW; marginal heat in areas without access to the gas grid) is relatively high (0.143 g MJ -1 ) as compared to the emission of NOx calculated for the combustion of bio-crude oil (0.07 g MJ -1 ) in a small-scale boiler (100 kW). The quality of this data (i.e. NOx emission for these combustion processes) is acceptable (Table S19) but could be improved by experimental measurement of emissions from the combustion of bio-crude oil. Moreover, NOx emissions from combustion can be reduced by adopting different types of measures like energy efficiency improvements or specific mitigation technologies [START_REF]Guidance document on control techniques for emissions of sulphur, NOx[END_REF]. However, such technologies like selective catalytic reduction, which can reduce NOx emissions by 80-95%, are applied only on large combustion plants (> 100 MW) as it would not be cost-effective on smaller combustion units.

0.E+00 The combustion of wood chips also contributes highly to the "ecotoxicity freshwater" and "noncancer human health effects" impact categories. The main contributor substance is zinc accumulated in soil in ashes and emitted to air.

According to the model, particulate matter (< 2.5 µm) emissions from the combustion of woodchips are higher than from combustion of bio-crude oil for the same amount of heat produced. This is why the number of disease increase is higher in the reference scenario for the "respiratory inorganics" impact category (Figure 4).

The production of wood chips used for combustion contributes to the higher "land use" impact in the reference scenario, due to occupation of forest land (intensive). In the Ecoinvent process, it is considered that 27577 m 2 x year are occupied and 674 m 2 are transformed per tonne of wood chips. Indirect land use changes are not even included. Pyrolysis also contributes to land use impact due to the considered electricity mix, produced partly from wood.

Carbon-14 emitted to air during the fabrication of fungicide is the main contributor to the ionizing radiation impact category in the reference scenario. In the pyrolysis scenario, the biomass supply chain contributes mostly to the ionizing radiation. Emissions of Carbon-14 come from diesel production, which is used as an energy source for harvest and transport of residues.

Finally, the "Resource use, energy carriers" impact is higher in the reference scenario because the fabrication of fungicides consumes a lot of energy, mostly from natural gas, uranium, oil and coal. Combustion of natural gas and wood chips also contribute to the high energy consumption of the reference scenario. In the pyrolysis scenario, biomass drying is the most energy consuming process (natural gas).

Sensitivity analysis

The potential for C sequestration by biochar is a key parameter for the impact category climate change (Fig. 2). Therefore, based on literature data, a sensitivity analysis for C sequestration values (Fperm) of 70, 80 (baseline) and 90% (over 100 years) was performed (Figure 5). It shows that even with a lower C sequestration potential (70%), the pyrolysis scenario still presents a lower GHG impact than the reference scenario. Considering a C sequestration potential of 90%, the GHG savings reaches 1.06 Mg CO2e per Mg of dry PFR harvested. ). PFR: primary forestry residues; NCG: Noncondensable gases.

The process "pyrolysis and condensation" is the major contributor to "Cancer human health effects" and "eutrophication freshwater" impact categories, contributing to the trade-off for the pyrolysis scenario. A decrease of the overall impact from this process could contribute to reduce or avoid a trade-off. The electricity consumption of the pyrolysis reactor, which contributes mostly to this process, could have been overestimated due to a lower efficiency of the semi-pilot scale reactor as compared to an industrial scale reactor. Therefore, a sensitivity analysis considering a reduction of 15% and 30% of electricity consumption of the pyrolysis reactor was performed. Even with the reduction of the electricity consumption of up to 30%, the pyrolysis scenario presents a trade-off of 12% for the cancer human health effect (Figure S1) and 24.9% for the eutrophication freshwater (Figure S2). The trade-off in the impact category "acidification terrestrial, freshwater" is very low in the baseline case (1.8%) and is therefore avoided with reductions of 15% and 30% of electricity consumption (Figure S3).

Fungicides production is the process contributing the most to the environmental impact of the reference scenario in the following impact categories: "Eutrophication freshwater" (69.2%), "ionizing radiation" (90.9%), "water scarcity" (85.1%) and "resources use, energy carriers" (52.9%). Moreover, fungicides have a non-negligible contribution in the "acidification terrestrial, freshwater" impact category in which a small trade-off is observed. However, the dose of wood vinegar that could be applied in the field to replace fungicides is still uncertain, as literature data are not available at large scale. A 0.5% acetic acid concentration in the biofungicide solution was selected for the baseline scenario, which could be sufficient to observe a fungicide effect, according to an experiment described in [START_REF] Brassard | Bio-based products from woody biomass pyrolysis for a sustainable bioeconomy[END_REF]. As this experiment was carried out in incubation conditions, the required concentration in the field could be higher. Therefore, a sensitivity analysis considering 0.5% (baseline), 0.75% (sensibility 1 -S1) and 1% (sensibility 2 -S2) concentrations of acetic acid was performed for the impact categories mentioned above. Increasing the concentration of acetic acid means that the amount of wood vinegar produced in the pyrolysis scenario (240.2 kg) will be spread on a reduced surface area. Consequently, less fungicide will be substituted (14.7 kg, 9.8 kg and 7.4 kg for the baseline, S1 and S2, respectively). Results of the sensitivity analysis show that an increased dose of wood vinegar (reduced quantity of fungicides avoided) increases the trade-off in the impact category "Eutrophication freshwater" and "acidification terrestrial, freshwater" (Figure S4 and S5). In the "ionizing radiation" impact category, the reduction of the emission of kBq U-235 eq. in the pyrolysis scenario as compared to the reference scenario is decreased from 14.33 in the baseline to 5.73 for S2 (Figure S6). Regarding the "resources use, energy carriers" impact category, the pyrolysis scenario presents a better environmental performance in the baseline and for S1 (Figure S7). However, S2 results in a trade-off, as the energy use is 186 MJ lower in the reference scenario. It means that the energy use for fungicide production is a key parameter in this impact category. This sensitivity analysis was also done in the "water scarcity" impact category (Figure S8), as an increased dose of wood vinegar will reduce the use of water for dilution in the pyrolysis and reference scenarios. The trade-off was increased from 5.67 m 3 (baseline) to 11.35 m 3 (S2).

Conclusion

A consequential LCA framework for the evaluation of the environmental performance of a pyrolysis biorefinery was developed and applied to a case study in which primary forestry residues are used. The method presented requires extending the system boundaries in order to consider the counterfactual use of biomass. It also requires to consider marginal technologies (i.e. technologies avoided in the pyrolysis scenario). In ten out of sixteen impact categories, the pyrolysis scenario presented a better environmental performance than the reference scenario in which forestry residues are left on soil to decay. Among others, pyrolysis of PFR was shown as climate-efficient, in particular based on the consideration that 80% of biochar's carbon is sequestered in soils for at least 100 years. The results highlighted that the environmental performance of pyrolysis can vary according to many factors, including the biomass feedstock supply, the pyrolysis technology, the coproducts yields, properties and uses and the identification of marginal technologies. Assumptions such as the C sequestration potential of biochar, the energy consumption of the pyrolysis reactor and the efficient dose of wood vinegar to substitute fungicide have an impact on the results. Therefore, foreground data from pyrolysis, combustion and agronomic experiments are needed to refine LCA models. Finally, techno-economic studies considering all the processes and products included in the LCA system boundary are needed to validate the economic feasibility of pyrolysis.

Figure 1 .

 1 Figure 1. Process flow diagram of the pyrolysis scenario studied. Dotted lines represent avoided processes (reference scenario). Processes without flow indicate no losses. PFR: Primary forest residues; NCG: Non-condensable gas; CHP: Combined heat and power.

Figure 3 .

 3 Figure 3. Contribution analysis (per Mg dry PFR) for six impact categories presenting a trade-off for pyrolysis scenario. PFR: primary forestry residues; NCG: Non-condensable gases.

Figure 5 .

 5 Photochemical ozone formation, HH

Table 1 .

 1 Non-exhaustive list of publications about life cycle assessment of pyrolysis systems using forestry biomass as feedstock

	Ref.	Background data 1	Goal and aim of pyrolysis	Pyrolysis technology	Biomass	Functional unit	System Boundaries	LCIA method and Impact categories studied (2-10)
	[20]	Ecoinvent 3.3 database	Producing bio-oil and biochar for the displacement of fossil fuels (heat) in cement manufacturing.	50 Mg per day mobile plant using steel-shot fluidized bed technology and feedstock drying process at the front-end.	Dry wood chips (2% w.c.)	300000 Mg of cement	From feedstock acquisition to the use products for energy generation.	TRACI (v.2.1) method. ACD, EUT, GWP, ODP, SMOG, RESP. CED method 1.08.
	[21]	Aspen modeling software (pyrolysis) / USA LCI database.	Substituting fossil fuels by bio-oil for heat production.	Fluidized bed pyrolysis feed. 2000 Mg (dry biomass) per day.	Wood chips /pine, 7% w.c., <3 mm particle.	1 MJ of energy (bio-oil)	Cradle-to-grave: From collection of forestry residues combustion. to bio-oil	TRACI (v.3) method. GWP, ACD, aquatic EUT, SMOG, ODP, RESP.
	[22]	Database in Simapro	Converting biomass from waste wood (residential, institutional, commercial and municipal) to bio-oil.	Flash pyrolysis (500°C). 1783 kg of bio-oil per hour.	Waste wood 3mm particle. municipal), < commercial, institutional, (residential,	kgbio-oil h -1 of 1783 Production	bio-oil. combustion of center to management From waste	EDIP 200X method.
		GREET model
		(GREET.nt
	[23]	vq.3.0.12844),
		database
		version 12384.

GWP, ODP, ACD, EUT, SMOG, ecotoxicity (water, chronic or acute, soil chronic), human toxicity (air, water, soil), waste (bulk, hazardous, radioactive).

Table 2 .

 2 Elemental composition of primary forestry residues at harvest

	Element	Unit	Value
	Carbon (C)	% (d.b)	51.5
	Oxygen (O)	% (d.b)	40.5
	Hydrogen (H)	% (d.b)	6.0
	Nitrogen (N)	% (d.b)	0.44
	Sulfur (S)	% (d.b)	0.01
	Ashes	% (d.b)	1.5
	Water content	% (w.b)	29.9

Table 3 .

 3 Parameters and product yields considered for the pyrolysis of PFR (as soft wood residues)

	Pyrolysis parameters
	Temperature	°C	559
	Biomass residence time	s	61
	N2 flow rate	L min -1	3
	1 st condenser temperature	°C	120
	2 nd condenser temperature	°C	4
	Product yields
	Bio-crude oil	wt%	36.1
	Wood vinegar	wt%	22.2
	Biochar	wt%	26.5
	Non-condensable gases	wt%	15.2

Table 4

 4

	. Characterization of pyrolysis non-condensable gases
	Composition	Unit	Value
	CO	%vol.	43.2
	CO2	%vol.	42.9
	CH4	%vol.	7.34
	C2H4	%vol.	0.58
	C2H6	%vol.	0.74
	H2	%vol.	5.2
	Lower heating value	MJ kg -1	7.0

Table 5

 5

	. Characterization of biochar (% d.b.)
	Parameter	Value
	Carbon (C)	70.8
	Nitrogen (N)	0.44
	Hydrogen (H)	4.27
	Oxygen (O)	19.4
	Sulfur (S)	0.008
	Ashes	5.09

Ensyn/UOP : http://www.ensyn.com/honeywell-uop.html;

LCIA: Life cycle impact assessment;

ACD: Acidification potential;

EUT: Eutrophication potential;

GWP: Global warming potential;

GWP100: Global warming potential on a 100 years time horizon;

ODP: Ozone depletion potential;

SMOG: Photochemical oxidant formation;

RESP: Respiratory effects;

CED: Cumulative energy demand.

VOCs, dust (including PM10, PM2.5 and black carbon) from stationary sources. 2012.

Acknowledgments

This work was carried out within the framework of the research project Cambioscop (https://cambioscop.cnrs.fr), partly financed by the French National Research Agency, Programme Investissement d'Avenir (ANR-17-MGPA-0006) and Region Occitanie (18015981). Additional funding was supplied by the Fonds de recherche du Québec -Nature et technologie (FQRNT) (Excellence postdoctoral grant). The authors further acknowledge Étienne Le Roux, Brenda Judith Alvarez-Chavez, Vijaya Raghavan and Joahnn H. Palacios for their contribution to the several experimental studies used to establish the foreground system of our analysis. Concetta Lodato (DTU) is also acknowledged for performing the simulations on the H2 content of NCGs.