Co-liquefaction of Macroalgae with Common Marine Plastic Pollutants

Macroalgal blooms are environmentally problematic and costly to remediate, but they also represent a vast untapped resource for the production of renewable chemicals and fuels. The responsible exploitation of such marine resources will become increasingly prominent in the transition away from the crude oil economy that currently dominates global productivity. However, crude oil-derived plastic pollution is now a ubiquitous presence in the marine environment, which hampers the effective conversion of marine feedstocks. If the full potential of macroalgae is to be realized, any large-scale industrial process will need to accommodate the presence of this plastic. This study, for the first time, aimed to assess the effect of several common marine plastic pollutants on the hydrothermal liquefaction (HTL) of four UK macroalgae species and determine the impact on the major HTL products and biocrude oil quality. Coliquefaction of polyethylene and polypropylene with L. digitata, U. lactuca, F. serratus, and S. muticum led to modest synergistic effects for plastic conversion. Under hydrothermal conditions, polyethylene underwent fragmentation to olefinic species, as well as oxidative depolymerization to form ketones. Modest synergistic effects on biocrude production were also observed for polypropylene, which depolymerized more readily in the presence of biomass to form gaseous propylene as well as oil-phase products. In both cases, the presence of plastics increased total biocrude carbon content, decreased nitrogen, and boosted higher heating value (HHV), constituting an overall improvement in biocrude fuel properties. Alternatively, nylon-6, typically originating from fisheries debris, depolymerized almost entirely under HTL conditions to form caprolactam, which partitioned mainly to the aqueous phase. While this is not favorable for biocrude production, the reclamation of marine nylon debris for hydrothermal processing to monomers may present a promising revenue stream in future biorefineries. The results demonstrate that plastic contaminants may well represent an opportunity, rather than a threat, to the successful development of an HTL macroalgal biorefinery

Assessing the Conversion of Various Nylon Polymers in the Hydrothermal Liquefaction of Macroalgae

Marine macroalgae offers a promising third generation feedstock for the production of fuels and chemicals, avoiding competition with conventional agriculture and potentially helping to improve eutrophication in seas and oceans. However, an increasing amount of plastic is distributed into the oceans, and as such contaminating macroalgal beds. One of the major plastic contaminants is nylon 6 derived from discarded fishing gear, though an increasing amount of alternative nylon polymers, derived from fabrics, are also observed. This study aimed to assess the effect of these nylon contaminants on the hydrothermal liquefaction of Fucus serratus. The hydrothermal liquefaction (HTL) of macroalgae was undertaken at 350 ◦C for 10 min, with a range of nylon polymers (nylon 6,nylon 6/6, nylon 12 and nylon 6/12), in the blend of 5, 20 and 50 wt.% nylon to biomass; 17 wt.% biocrude was achieved from a 50% blend of nylon 6 with F. serratus. In addition, nylon 6 completely broke down in the system producing the monomer caprolactam. The suitability of converting fishing gear was further demonstrated by conversion of actual fishing line (nylon 6) with the macroalgae, producing an array of products. The alternative nylon polymer blends were less reactive, with only 54% of the nylon 6/6 breaking down under the HTL conditions, forming cyclopentanone which distributed into the biocrude phase. Nylon 6/12 and nylon 12 were even less reactive, and only traces of the monomer cyclododecanone were observed in the biocrude phase. This study demonstrates that while nylon 6 derived from fishing gear can be effectively integrated into a macroalgal biorefinery, alternative nylon polymers from other sectors are too stable to be converted under these conditions and present a real challenge to a macroalgal biorefinery

Co-production of bio-oil and propylene through the hydrothermal liquefaction of polyhydroxybutyrate producing cyanobacteria

A polyhydroxybutyrate (PHB) producing cyanobacteria was converted through hydrothermal liquefaction (HTL) into propylene and a bio-oil suitable for advanced biofuel production. HTL of model compounds demonstrated that in contrast to proteins and carbohydrates, no synergistic effects were detected when converting PHB in the presence of algae. Subsequently, Synechocystis cf. salina, which had accumulated 7.5wt% PHB was converted via HTL (15% dry weight loading, 340°C). The reaction gave an overall propylene yield of 2.6%, higher than that obtained from the model compounds, in addition to a bio-oil with a low nitrogen content of 4.6%. No propylene was recovered from the alternative non-PHB producing cyanobacterial strains screened, suggesting that PHB is the source of propylene. PHB producing microorganisms could therefore be used as a feedstock for a biorefinery to produce polypropylene and advanced biofuels, with the level of propylene being proportional to the accumulated amount of PHB

Assessing hydrothermal liquefaction for the production of bio-oil and enhanced metal recovery from microalgae cultivated on acid mine drainage

The hydrothermal liquefaction (HTL) of algal biomass is a promising route to viable second generation biofuels. In this investigation HTL was assessed for the valorisation of algae used in the remediation of acid mine drainage (AMD). Initially the HTL process was evaluated using Arthrospira platensis (Spirulina) with additional metal sulphates to simulate metal remediation. Optimised conditions were then used to process a natural algal community (predominantly Chlamydomonas sp.) cultivated under two scenarios: high uptake and low uptake of metals from AMD. High metal concentrations appear to catalyse the conversion to bio-oil, and do not significantly affect the heteroatom content or higher heating value of the bio-oil produced. The associated metals were found to partition almost exclusively into the solid residue, favourable for potential metal recovery. High metal loadings also caused partitioning of phosphates from the aqueous phase to the solid phase, potentially compromising attempts to recycle process water as a growth supplement. HTL was therefore found to be a suitable method of processing algae used in AMD remediation, producing a crude oil suitable for upgrading into hydrocarbon fuels, an aqueous and gas stream suitable for supplementing the algal growth and the partitioning of most contaminant metals to the solid residue where they would be readily amenable for recovery and/or disposal

Towards a marine biorefinery through the hydrothermal liquefaction of macroalgae native to the United Kingdom

Hydrothermal liquefaction (HTL) is a promising biomass conversion method that can be incorporated into a biorefinery paradigm for simultaneous production of fuels, aqueous fertilisers and potential remediation of municipal or mariculture effluents. HTL of aquatic crops, such as marine macro- or microalgae, has significant potential for the UK owing to its extensive coastline. As such, macroalgae present a particularly promising feedstock for future UK biofuel production. This study aimed to bridge the gaps between previous accounts of macroalgal HTL by carrying out a more comprehensive screen of a number of species from all three major macroalgae classes, and examining the correlations between biomass biochemical composition and HTL reactivity. HTL was used to process thirteen South West UK macroalgae species from all three major classes (Chlorophyceae, Heterokontophyceae and Rhodophyceae) to produce bio-crude oil, a bio-char, gas and aqueous phase products. Chlorophyceae of the genus Ulva generated the highest bio-crude yields (up to 29.9% for U. lactuca). Aqueous phase phosphate concentrations of up to 236 mg L−1 were observed, obtained from the Rhodophyta, S. chordalis. Across the 13 samples, a correlation between increasing biomass lipids and increasing bio-crude yield was observed, as well as an increase in biomass nitrogen generally contributing to bio-crude nitrogen content. A broader range of macroalgae species has been examined than in any study previously and, by processing using identical conditions across all feedstocks, has enabled a more cohesive assessment of the effects of biochemical composition

Distinct Genetic Architectures for Male and Female Inflorescence Traits of Maize

We compared the genetic architecture of thirteen maize morphological traits in a large population of recombinant inbred lines. Four traits from the male inflorescence (tassel) and three traits from the female inflorescence (ear) were measured and studied using linkage and genome-wide association analyses and compared to three flowering and three leaf traits previously studied in the same population. Inflorescence loci have larger effects than flowering and leaf loci, and ear effects are larger than tassel effects. Ear trait models also have lower predictive ability than tassel, flowering, or leaf trait models. Pleiotropic loci were identified that control elongation of ear and tassel, consistent with their common developmental origin. For these pleiotropic loci, the ear effects are larger than tassel effects even though the same causal polymorphisms are likely involved. This implies that the observed differences in genetic architecture are not due to distinct features of the underlying polymorphisms. Our results support the hypothesis that genetic architecture is a function of trait stability over evolutionary time, since the traits that changed most during the relatively recent domestication of maize have the largest effects

Valorization, comparison and characterization of coconuts waste and cactus in a biorefinery context using NaClO2-C2H4O2 and sequential NaClO2-C2H4O2/autohydrolysis pretreatment

The search for new sources of lignocellulosic raw materials for the generation of energy and new compounds encourages the search for locations not well known and with a high potential for biomass availability as is the case of the Northeast Region of Brazil. Thus, the cactus (CAC), green coconut shell (GCS), mature coconut fibre and mature coconut shell were pretreated by NaClO2C2H4O2 and sequential NaClO2C2H4O2/autohydrolysis aiming at the obtention of high added-value compounds in the liquid fraction and solid phase. The yield of the solid phase was between 61.42 and 90.97% and the reduction up to 91.63% of lignin in the materials pretreated by NaClO2C2H4O2. After NaClO2C2H4O2/autohydrolysis pretreatment the obtained solids yield was between 43.57 and 52.08%, with a solubilization of the hemicellulose content up to 81.42%. For both pretreatments the cellulosic content remained almost unchanged. The pretreated solids were characterized by SEM, X-ray and crystallinity indexes showing significant modifications when submitted to pretreatments. These results were further confirmed by the enzymatic conversion yields of 81.6890.03 and 86.9790.36% of the LCMs pretreated by NaClO2C2H4O2 and pretreated by NaClO2C2H4O2/autohydrolysis, respectively. The resulting liquors had a total phenolic compounds content between 0.20 and 3.05 g/L, lignin recovered up to 7.40 g/L (absence of sulphur) and xylooligosaccharides between 16.13 and 20.37 g/L. Thus, these pretreatments showed an efficient fractionation of LCMs, especially in the GCS, being an important requirement for the generation of products and byproducts in the context of the biorefinery.The authors gratefully acknowledge the Brazilian research funding agencies CNPq and CAPES for financial support. Financial support from the Energy Sustainability Fund 2014-05 (CONACYT-SENER), Mexican Centre for Innovation in Bioenergy (CemieBio), Cluster of Bioalcohols (Ref. 249564) is gratefully acknowledged. We also gratefully acknowledge support for this research by the Mexican Science and Technology Council (CONACYT, Mexico) for the infrastructure project - INFR201601 (Ref. 269461) and CB-2015-01 (Ref. 254808).info:eu-repo/semantics/publishedVersio

Genome-Wide Identification of MicroRNAs in Response to Low Nitrate Availability in Maize Leaves and Roots

BACKGROUND: Nitrate is the major source of nitrogen available for many crop plants and is often the limiting factor for plant growth and agricultural productivity especially for maize. Many studies have been done identifying the transcriptome changes under low nitrate conditions. However, the microRNAs (miRNAs) varied under nitrate limiting conditions in maize has not been reported. MiRNAs play important roles in abiotic stress responses and nutrient deprivation. METHODOLOGY/PRINCIPAL FINDINGS: In this study, we used the SmartArray™ and GeneChip® microarray systems to perform a genome-wide search to detect miRNAs responding to the chronic and transient nitrate limiting conditions in maize. Nine miRNA families (miR164, miR169, miR172, miR397, miR398, miR399, miR408, miR528, and miR827) were identified in leaves, and nine miRNA families (miR160, miR167, miR168, miR169, miR319, miR395, miR399, miR408, and miR528) identified in roots. They were verified by real time stem loop RT-PCR, and some with additional time points of nitrate limitation. The miRNAs identified showed overlapping or unique responses to chronic and transient nitrate limitation, as well as tissue specificity. The potential target genes of these miRNAs in maize were identified. The expression of some of these was examined by qRT-PCR. The potential function of these miRNAs in responding to nitrate limitation is described. CONCLUSIONS/SIGNIFICANCE: Genome-wide miRNAs responding to nitrate limiting conditions in maize leaves and roots were identified. This provides an insight into the timing and tissue specificity of the transcriptional regulation to low nitrate availability in maize. The knowledge gained will help understand the important roles miRNAs play in maize responding to a nitrogen limiting environment and eventually develop strategies for the improvement of maize genetics