Towards carbon neutrality of calcium carbide-based acetylene production with sustainable biomass resources

Acetylene is produced from the reaction between calcium carbide(CaC_(2))and water,while the production of CaC_(2) generates significant amount of carbon dioxide not only because it is an energy-intensive process but also the raw material for CaC_(2) synthesis is from coal.Here,a comprehensive biomass-to-acetylene process was constructed that integrated several units including biomass pyrolysis,oxygen-thermal CaC_(2) fabrication and calcium looping.For comparison,a coal-to-acetylene process was also established by using coal as feedstock.The carbon efficiency,energy efficiency and environmental impacts of the bio-based calcium carbide acetylene(BCCA)and coal-based calcium carbide acetylene(CCCA)processes were systematically analyzed.Moreover,the environmental impacts were further evaluated by applying thermal integration at system level and energy substitution in CaC_(2) furnace.Even though the BCCA process showed lower carbon efficiency and energy efficiency than that of the CCCA process,life cycle assessment demonstrated the BCCA(1.873 kgCO_(2eq) kg-prod^(-1))a lower carbon footprint process which is 0.366 kgCO_(2eq) kg-prod^(-1) lower compared to the CCCA process.With sustainable energy(biomass power)substitution in CaC_(2) furnace,an even lower GWP value of 1.377 kgCO_(2eq) kg-prod^(-1) can be achieved in BCCA process.This work performed a systematic analysis on integrating biomass into industrial acetylene production,and revealed the positive role of biomass as raw material(carbon)and energy supplier.

No effect of invasive tree species on aboveground biomass increments of oaks and pines in temperate forests

Prunus serotina and Robinia pseudoacacia are the most widespread invasive trees in Central Europe.In addition,according to climate models,decreased growth of many economically and ecologically important native trees will likely be observed in the future.We aimed to assess the impact of these two neophytes,which differ in the biomass range and nitrogen-fixing abilities observed in Central European conditions,on the relative aboveground biomass increments of native oaks Qucrcus robur and Q.petraea and Scots pine Pinus sylvestris.We aimed to increase our understanding of the relationship between facilitation and competition between woody alien species and overstory native trees.We established 72 circular plots(0.05 ha)in two different forest habitat types and stands varying in age in western Poland.We chose plots with different abundances of the studied neophytes to determine how effects scaled along the quantitative invasion gradient.Furthermore,we collected growth cores of the studied native species,and we calculated aboveground biomass increments at the tree and stand levels.Then,we used generalized linear mixed-effects models to assess the impact of invasive species abundances on relative aboveground biomass increments of native tree species.We did not find a biologically or statistically significant impact of invasive R.pseudoacacia or P.serotina on the relative aboveground,biomass increments of native oaks and pines along the quantitative gradient of invader biomass or on the proportion of total stand biomass accounted for by invaders.The neophytes did not act as native tree growth stimulators but also did not compete with them for resources,which would escalate the negative impact of climate change on pines and oaks.The neophytes should not significantly modify the carbon sequestration capacity of the native species.Our work combines elements of the per capita effect of invasion with research on mixed forest management.

Sustainable Furfural Biomass Feedstocks Electrooxidation toward Value-Added Furoic Acid with Energy-Saving H_(2) Fuel Production Using Pt-Decorated Co_(3)O_(4) Nanospheres

Here,furfural oxidation was performed to replace the kinetically sluggish O_(2)evolution reaction(OER).Pt-Co_(3)O_(4)nanospheres were developed via pulsed laser ablation in liquid(PLAL)in a single step for the paired electrocatalysis of an H_(2)evolution reaction(HER)and furfural oxidation reaction(FOR).The FOR afforded a high furfural conversion(44.2%)with a major product of 2-furoic acid after a 2-h electrolysis at 1.55 V versus reversible hydrogen electrode in a 1.0-M KOH/50-mM furfural electrolyte.The Pt-Co_(3)O_(4)electrode exhibited a small overpotential of 290 mV at 10 mA cm^(-2).As an anode and cathode in an electrolyzer system,the Pt-Co_(3)O_(4)electrocatalyst required only a small applied cell voltage of~1.83 V to deliver 10 mA cm^(-2),compared with that of the pure water electrolyzer(OER||HER,~1.99 V).This study simultaneously realized the integrated production of energy-saving H_(2)fuel at the cathode and 2-furoic acid at the anode.

The Use of Secondary Grape Biomass in Beef Cattle Nutrition on Carcass Characteristics, Quality and Shelf Life of Meat

We determined whether the inclusion of 100 g/kg dry matter of grape pomace silage (GPS) and grape pomace bran (GPB) as substitutes for other traditional fiber sources in the diet of steers (Charolais x Nellore) would improve carcass characteristics, meat quality and composition, and shelf life. Twenty-four animals (248 ± 19.32 kg of initial body weight) were fed a high concentrate diet for 121 days. Carcass characteristics were measured, and the longissimus dorsi muscle was analyzed for fatty acid (FA) profile and composition. The meat was sliced and stored in air-permeable packages for 10 days. On each sampling day (d 1, 3, 7, and 10), oxidative stability, bacterial load, lipid and protein oxidation, and staining were analyzed. The experimental diets influenced the pH of cold carcasses only. The GPS group had a higher pH than the control. The GPS and GPB groups showed improved oxidant status (i.e., lower lipid peroxidation and concentrations of reactive oxygen species were in the meat of both groups than in control). On the first day of storage, the antioxidant enzyme glutathione S-transferase activity was more significant in the meat of the GPS and GPB groups than in the control. The bacterial loads in the meat were attenuated by GPS inclusion;there were lower total coliform counts and a trend toward lower counts for enterobacteria in the control group. The diets altered the FA profile of the meat;i.e., the GPB diet allowed for a more significant amount of the n-6 omegas in the meat, while the GPS diet showed a tendency for a more significant amount of n-6 and 9 omegas. Both diets (GPS and GPB) increased the amounts of long-chain FAs. The GPS diet decreased saturated FA levels. We conclude that the dietary treatments GPS and GPB are a promising alternative to maintain meat quality standards throughout in real-world retail conditions. These treatments gave rise to an improvement in the nutritional value of the meat due to the more significant amounts of FAs that improve human health.

Species-specific and generalized allometric biomass models for eight Fagaceae species in the understory of evergreen broadleaved forests in subtropical China

Quantifying the biomass of saplings in the regeneration component is critical for understanding biogeochemical processes of forest ecosystems.However,accurate allometric equations have yet to be developed in sufficient detail.To develop species-specific and generalized allometric equations,154 saplings of eight Fagaceae tree species in subtropical China’s evergreen broadleaved forests were collected.Three dendrometric variables,root collar diameter(d),height(h),and crown area(ca)were applied in the model by the weighted nonlinear seemingly unrelated regression method.Using only d as an input variable,the species-specific and generalized allometric equations estimated the aboveground biomass reasonably,with R _(adj)^(2) values generally>0.85.Adding h and/or ca improved the fitting of some biomass components to a certain extent.Generalized equations showed a relatively large coefficient of variation but comparable bias to species-specific equations.Only in the absence of species-specific equations at a given location are generalized equations for mixed species recommended.The developed regression equations can be used to accurately calculate the aboveground biomass of understory Fagaceae regeneration trees in China’s subtropical evergreen broadleaved forests.

Renewable Biomass as a Platform for Preparing Green Chemistry

1 About the Special Issue Editor Qiaoguang Li is an associate professor and master’s supervisor in the Department of College of Chemistry and Chemical Engineering,Zhongkai University of Agriculture and Engineering.He received his PhD from Institute of Chemical Industry of Forestry Products,Chinese Academy of Forestry in 2018.He has been focusing his research on the chemical basis and application of natural resources.He has published nearly 30 international peer reviewed papers and applied for 10 patents.

Integrating remote sensing and 3-PG model to simulate the biomass and carbon stock of Larix olgensis plantation

Accurate estimations of biomass and its temporal dynamics are crucial for monitoring the carbon cycle in forest ecosystems and assessing forest carbon sequestration potentials.Recent studies have shown that integrating process-based models(PBMs)with remote sensing data can enhance simulations from stand to regional scales,significantly improving the ability to simulate forest growth and carbon stock dynamics.However,the utilization of PBMs for large-scale simulation of larch carbon storage distribution is still limited.In this study,we applied the parameterized 3-PG(Physiological Principles Predicting Growth)model across the Mengjiagang Forest Farm(MFF)to make broad-scale predictions of the biomass and carbon stocks of Larix olgensis plantation.The model was used to simulate average diameter at breast height(DBH)and total biomass,which were later validated with a wide range of observation data including sample plot data,forest management inventory data,and airborne laser scanning data.The results showed that the 3-PG model had relatively high accuracy for predicting both DBH and total biomass at stand and regional scale,with determination coefficients ranging from 0.78 to 0.88.Based on the estimation of total biomass,we successfully produced a carbon stock map of the Larix olgensis plantation in MFF with a spatial resolution of 20 m,which helps with relevant management advice.These findings indicate that the integration of 3-PG model and remote sensing data can well predict the biomass and carbon stock at regional and even larger scales.In addition,this integration facilitates the evaluation of forest carbon sequestration capacity and the development of forest management plans.

Biomass valorization via electrocatalytic carbon–carbon bond cleavage

Renewable electrocatalytic upgrading of biomass feedstocks into valuable chemicals is one of the promising strategies to relieve the pressure of traditional energy-based systems.Through electrocatalytic carbon–carbon bond cleavage of high selectivity,various functionalized molecules,such as organic acids,amides,esters,and nitriles,have great potential to be accessed from biomass.However,it has merely received finite concerns and interests in the biorefinery.This review first showcases the research progress on the electrocatalytic conversion of lipid/sugar-and lignin-derived molecules(e.g.,glycerol,mesoerythritol,xylose,glucose,1-phenylethanol,and cyclohexanol)into organic acids via specific carbon–carbon bond scission processes,with focus on disclosing reaction mechanisms,recognizing actual active species,and collecting feasible modification strategies.For the guidance of further extensive studies on biomass valorization,organic transformations via a variety of reactions,including decarboxylation,ring-opening,rearrangement,reductive hydrogenation,and carboxylation,are also disclosed for the construction of similar carbon skeletons/scaffolds.The remaining challenges,prospective applications,and future objectives in terms of biomass conversion are also proposed.This review is expected to provide references to develop renewed electrocatalytic carbon–carbon bond cleavage transformation paths/strategies for biomass upgrading.

Regulation of different light conditions for efficient biomass production and protein accumulation of Spirulina platensis

Light plays an important role in the photosynthesis and metabolic process of microalgae.However,how different light conditions regulate the biomass production and protein accumulation of microalgae is mostly unknown.In this study,the influence of different light conditions,including light colors,densities,and light:dark cycles on the cell growth and biochemical composition of Spirulina platensis was symmetrically characterized.Under different colored lights,S.platensis all shows an increase trend within the increased light intensity ranges;however,each showing different optimal light intensities.At the same light intensity,different colored lights show different growth rate of S.platensis following the sequence of red>white>green>yellow>blue.The maximum growth rate and protein accumulation were determined as 21.88 and 5.10 mg/(L·d)when illuminated under red LED.The energy efficiency of different light sources was calculated and ranked as red>white>blue≈green>yellow.Transcriptomic analysis suggests that red light can promote cell growth and protein accumulation by upregulating genes related to photosynthesis,carbon fixation,and C-N metabolism pathways.This study provides a conducive and efficient way to promote biomass production and protein accumulation of S.platensis by regulating light conditions.

Effect of Soil Fertility and Planting Density on the Partitioning of the Above-Ground Biomass of Eucalyptus in a Plantation (Pointe-Noire, Republic of Congo)

Afforestation and reforestation are useful approaches to improve carbon sequestration. With the advent of forest plantations, growing environment conditions have become increasingly restrictive for light, soil nutrients, and interactions between trees to acquire available resources. Tree biomass data are essential for understanding the forest carbon cycle and plant adaptations to the environment. The distribution of tree biomass depends on the sum of multiple stand conditions. The data are from a dedicated experiment with two very contrasting areas of fertility, and two planting densities, including a high density at planting in order to achieve thinning. The plant material consists of the high-performance clones of Eucalyptus urophylla × E. grandis and the reference clone E. PF1. We hypothesize that the distribution of biomass changes as the intensity of competition changes and that this is accelerated by the fertility of the sites in time. The results indicate that fertilization, planting density and clones have an impact on biomass partitioning.

Chemical looping reforming of the micromolecular component from biomass pyrolysis via Fe_(2)O_(3)@SBA-16

To solve the problems of low gasification efficiency and high tar content caused by solid–solid contact between biomass and oxygen carrier in traditional biomass chemical looping gasification process.The decoupling strategy was adopted to decouple the biomass gasification process,and the composite oxygen carrier was prepared by embedding Fe_(2)O_(3) in molecular sieve SBA-16 for the chemical looping reforming process of pyrolysis micromolecular model compound methane,which was expected to realize the directional reforming of pyrolysis volatiles to prepare hydrogen-rich syngas.Thermodynamic analysis of the reaction system was carried out based on the Gibbs free energy minimization method,and the reforming performance was evaluated by a fixed bed reactor,and the kinetic parameters were solved based on the gas–solid reaction model.Thermodynamic analysis verified the feasibility of the reaction and provided theoretical guidance for experimental design.The experimental results showed that the reaction performance of Fe_(2)O_(3)@SBA-16 was compared with that of pure Fe_(2)O_(3) and Fe_(2)O_(3)@SBA-15,and the syngas yield was increased by 55.3%and 20.7%respectively,and it had good cycle stability.Kinetic analysis showed that the kinetic model changed from three-dimensional diffusion to first-order reaction with the increase of temperature.The activation energy was 192.79 kJ/mol by fitting.This paper provides basic data for the directional preparation of hydrogen-rich syngas from biomass and the design of oxygen carriers for pyrolysis of all-component chemical looping reforming.

In Situ Mineralization of Biomass-Derived Hydrogels Boosts Capacitive Electrochemical Energy Storage in Free-Standing 3D Carbon Aerogels

Here,a novel fabrication method for making free-standing 3D hierarchical porous carbon aerogels from molecularly engineered biomass-derived hydrogels is presented.In situ formed flower-like CaCO_(3)molecularly embedded within the hydrogel network regulated the pore structure during in situ mineralization assisted one-step activation graphitization(iMAG),while the intrinsic structural integrity of the carbon aerogels was maintained.The homogenously distributed minerals simultaneously acted as a hard template,activating agent,and graphitization catalyst.The decomposition of the homogenously distributed CaCO_(3)during iMAG followed by the etching of residual CaO through a mild acid washing endowed a robust carbon aerogel with high porosity and excellent electrochemical performance.At 0.5 mA cm^(-2),the gravimetric capacitance increased from 0.01 F g^(-1)without mineralization to 322 F g^(-1)with iMAG,which exceeds values reported for any other free-standing or powder-based biomass-derived carbon electrodes.An outstanding cycling stability of~104%after 1000 cycles in 1 M HClO4 was demonstrated.The assembled symmetric supercapacitor device delivered a high specific capacitance of 376 F g^(-1)and a high energy density of 26 W h kg^(-1)at a power density of 4000 W kg^(-1),with excellent cycling performance(98.5%retention after 2000 cycles).In combination with the proposed 3D printed mold-assisted solution casting(3DMASC),iMAG allows for the generation of free-standing carbon aerogel architectures with arbitrary shapes.Furthermore,the novel method introduces flexibility in constructing free-standing carbon aerogels from any ionically cross-linkable biopolymer while maintaining the ability to tailor the design,dimensions,and pore size distribution for specific energy storage applications.

New Problems of Boiler Corrosion after Coupling Combustion of Coal and Biomass and Anti-Corrosion Technologies

This study explores the corrosion issues arising from the coupled combustion of coal and biomass and proposes potential solutions.Biomass,as a renewable energy source,offers advantages in energy-saving and carbon reduction.However,the corrosive effects of alkali metal compounds,sulfur(S)and chlorine(Cl)elements in the ash after combustion cannot be underestimated due to the high volatile content of biomass fuels.We investigate the corrosion mechanisms,as well as the transfer of Cl and alkali metal elements during this process.Comparative corrosion analyses are conducted among coal-fired boilers,pure biomass boilers and boilers with coupled combustion.Various biomass types in co-firing are studied to understand different corrosion outcomes.The main factors influencing corrosion include the physicochemical properties of biomass feedstock,furnace temperature and heating surface materials,with the chemical composition and ash content of biomass playing a dominant role.Currently,the methods used for anti-corrosion include water washing pretreatment of biomass feedstock,application of novel alloys and coatings and the development of additives to inhibit fouling,ash deposition and corrosion.Efficient inhibitors are economical and easy to produce.Additionally,biomass can be converted into biomass gasification gas,although challenges related to tar still need to be addressed.

Facile preparation of Fe/N-based biomass porous carbon composite towards enhancing the thermal decomposition of DAP-4

Fe/N-based biomass porous carbon composite(Fe/N-p Carbon) was prepared by a facile high-temperature carbonization method from biomass,and the effect of Fe/N-p Carbon on the thermal decomposition of energetic molecular perovskite-based material DAP-4 was studied.Biomass porous carbonaceous materials was considered as the micro/nano support layers for in situ deposition of Fe/N precursors.Fe/Np Carbon was prepared simply by the high-temperature carbonization method.It was found that it showed the inherent catalysis properties for thermal decomposition of DAP-4.The heat release of DAP-4/Fe/N-p Carbon by DSC curves tested had increased slightly,compared from DAP-4/Fe/N-p Carbon-0.The decomposition temperature peak of DAP-4 at the presence of Fe/N-p Carbon had reduced by 79°C from384.4°C(pure DAP-4) to 305.4°C(DAP-4/Fe/N-p Carbon-3).The apparent activation energy of DAP-4thermal decomposition also had decreased by 29.1 J/mol.The possible catalytic decomposition mechanism of DAP-4 with Fe/N-p Carbon was proposed.

Effect of temperature on suspension magnetization roasting of hematite using biomass waste as reductant:A perspective of gas evolution

The magnetization reduction of hematite using biomass waste can effectively utilize waste and reduce CO_(2) emission to achieve the goals of carbon peaking and carbon neutrality.The effects of temperatures on suspension magnetization roasting of hematite using biomass waste for evolved gases have been investigated using TG-FTIR,Py-GC/MS and gas composition analyzer.The mixture reduction process is divided into four stages.In the temperature range of 200-450℃ for mixture,the release of CO_(2),acids,and ketones is dominated in gases products.The yield and concentration of small molecules reducing gases increase when the temperature increases from 450 to 900℃.At 700℃,the volume concentrations of CO,H_(2) and CH_(4) peak at 8.91%,8.90% and 4.91%,respectively.During the suspension magnetization roasting process,an optimal iron concentrate with an iron grade of 70.86%,a recovery of 98.66% and a magnetic conversion of 45.70% is obtained at 700℃.Therefore,the magnetization reduction could react greatly in the temperature range of 600 to 700℃ owing to the suitable reducing gases.This study shows a detail gaseous evolution of roasting temperature and provides a new insight for studying the reduction process of hematite using biomass waste.

Effects of urbanization and forest type on species composition and diversity,forest characteristics,biomass carbon sink,and their associations in Changchun,Northeast China:implications for urban carbon stock improvement

Differences in forest attributes and carbon sequestration of each organ and layer between broadleaved and conifer forests of central and outer urban areas are not well-defined,hindering the precise management of urban forests and improvement of function.To clarify the effect of two forest types with different urbanization intensities,we determined differences in vegetation composition and diversity,structural traits,and carbon stocks of 152 plots(20 m×20 m)in urban park forests in Changchun,which had the largest green quantity and carbon density effectiveness.We found that 1.1-fold thicker and healthier trees,and 1.6-to 2.0-fold higher,healthier,denser,and more various shrubs but with sparser trees and herbs occurred in the central urban forests(p<0.05)than in the outer forests.The conifer forests exhibited 30–70%obviously higher tree aboveground carbon sequestration(including stem and leaf)and 20%bigger trees,especially in the outer forests(p<0.05).In contrast,1.1-to 1.5-fold higher branch stocks,healthier and more diverse trees were found in broadleaved forests of both the inner and outer forests(p<0.05).Plant size and dominant species had similarly important roles in carbon stock improvement,especially big-sized woody plants and Pinus tabuliformis.In addition,a higher number of deciduous or needle species positively affected the broadleaved forest of the central urban area and conifer forest of the outer urban area,respectively.These findings can be used to guide precise management and accelerate the improvement of urban carbon function in Northeast China in the future.

Unraveling the Rheology of Nanocellulose Aqueous Suspensions:A Comprehensive Study on Biomass-Derived Nanofibrillated Cellulose

The rheological properties of nanocellulose aqueous suspensions play a critical role in the development of nanocellulose-based bulk materials.High-crystalline,high-aspect ratio,and slender nanofibrillated cellulose(NFC)were extracted from four biomass resources.The cellulose nanofibrils and nanofibril bundles formed inter-connected networks in the NFC aqueous suspensions.The storage moduli of the suspensions with different concentrations were higher than their corresponding loss moduli.As the concentration increased,the storage and loss modulus of NFC dispersion increased.When the shear rate increased to a certain value,there were differences in the changing trend of the rheological behavior of NFC aqueous suspensions derived from different biomass resources and the suspensions with different solid concentrations.NFC dispersion’s storage and loss modulus increased when the temperature rose to nearly 80℃.We hope this study can deepen the understanding of the rheological properties of NFC colloids derived from different biomass resources.

Cross-upgrading of biomass hydrothermal carbonization and pyrolysis for high quality blast furnace injection fuel production:Physicochemical characteristics and gasification kinetics analysis

The paper proposes a biomass cross-upgrading process that combines hydrothermal carbonization and pyrolysis to produce high-quality blast furnace injection fuel.The results showed that after upgrading,the volatile content of biochar ranged from 16.19%to 45.35%,and the alkali metal content,ash content,and specific surface area were significantly reduced.The optimal route for biochar pro-duction is hydrothermal carbonization-pyrolysis(P-HC),resulting in biochar with a higher calorific value,C=C structure,and increased graphitization degree.The apparent activation energy(E)of the sample ranges from 199.1 to 324.8 kJ/mol,with P-HC having an E of 277.8 kJ/mol,lower than that of raw biomass,primary biochar,and anthracite.This makes P-HC more suitable for blast furnace injection fuel.Additionally,the paper proposes a path for P-HC injection in blast furnaces and calculates potential environmental benefits.P-HC of-fers the highest potential for carbon emission reduction,capable of reducing emissions by 96.04 kg/t when replacing 40wt%coal injec-tion.

Biomass-based production of trimellitic and trimesic acids

The production of industrial chemicals with renewable biomass feedstock holds potential to aid the world in pursuing a carbon-neutral society.Trimellitic and trimesic acids are important commodity chemicals in industry that are prepared by the oxidation of petroleum-derived trimethylbenzene.To reduce the dependence on the limited oil source,we develop a potential sustainable alternative towards trimellitic and trimesic acids using biomass-based 2-methyl-2,4-pentandiol(MPD),acrylate and crotonaldehyde as starting materials.The process for trimellitic acid includes dehydration/D-A reaction of MPD and acrylate,flow aromatization over Pd/C catalyst,hydrolysis and catalytic aerobic oxidation(60%overall yield).The challenging regioselectivity issue of D-A reaction is tackled by a matched combination of temperature and deep eutectic solvent ChCl/HCO_(2)H.Crotonaldehyde can also participate in the reaction,followed by Pd/C-catalyzed decarbonylation/dehydrogenation and oxidation to provide trimesic acid in 54%overall yield.Life cycle assessment implies that compared to conventional fossil process,our biomass-based routes present a potential in reducing carbon emissions.

The connection of phytoplankton biomass in the Marguerite Bay polynya of the western Antarctic Peninsula to the Southern Annular Mode

Antarctic coastal polynyas are biological hotspots in the Southern Ocean that support the abundance of hightrophic-level predators and are important for carbon cycling in the high-latitude oceans.In this study,we examined the interannual variation of summertime phytoplankton biomass in the Marguerite Bay polynya(MBP)in the western Antarctic Peninsula area,and linked such variability to the Southern Annular Mode(SAM)that dominated the southern hemisphere extratropical climate variability.Combining satellite data,atmosphere reanalysis products and numerical simulations,we found that the interannual variation of summer chlorophyll-a(Chl-a)concentration in the MBP is significantly and negatively correlated with the spring SAM index,and weakly correlated with the summer SAM index.The negative relation between summer Chl-a and spring SAM is due to weaker spring vertical mixing under a more positive SAM condition,which would inhibit the supply of iron from deep layers into the surface euphotic layer.The negative relation between spring mixing and spring SAM results from greater precipitation rate over the MBP region in positive SAM phase,which leads to lower salinity in the ocean surface layer.The coupled physical-biological mechanisms between SAM and phytoplankton biomass revealed in this study is important for us to predict the future variations of phytoplankton biomasses in Antarctic polynyas under climate change.