Acid-Catalyzed Liquefaction of Biomasses from Poplar Clones for Short Rotation Coppice Cultivations

Liquefaction of biomass delivers a liquid bio-oil with relevant chemical and energetic applications. In this study we coupled it with short rotation coppice (SRC) intensively managed poplar cultivations aimed at biomass production while safeguarding environmental principles of soil quality and biodiversity. We carried out acid-catalyzed liquefaction, at 160 °C and atmospheric pressure, with eight poplar clones from SRC cultivations. The bio-oil yields were high, ranging between 70.7 and 81.5%. Average gains of bio-oil, by comparison of raw biomasses, in elementary carbon and hydrogen and high heating, were 25.6, 67, and 74%, respectively. Loss of oxygen and O/C ratios averaged 38 and 51%, respectively. Amounts of elementary carbon, oxygen, and hydrogen in bio-oil were 65, 26, and 8.7%, and HHV averaged 30.5 MJkg−1. Correlation analysis showed the interrelation between elementary carbon with HHV in bio-oil or with oxygen loss. Overall, from 55 correlations, 21 significant and high correlations among a set of 11 variables were found. Among the most relevant ones, the percentage of elementary carbon presented five significant correlations with the percentage of O (−0.980), percentage of C gain (0.902), percentage of O loss (0.973), HHV gain (0.917), and O/C loss (0.943). The amount of carbon is directly correlated with the amount of oxygen, conversely, the decrease in oxygen content increases the elementary carbon and hydrogen concentration, which leads to an improvement in HHV. HHV gain showed a strong positive dependence on the percentage of C (0.917) and percentage of C gain (0.943), while the elementary oxygen (−0.885) and its percentage of O loss (0.978) adversely affect the HHV gain. Consequently, the O/C loss (0.970) increases the HHV positively. van Krevelen’s analysis indicated that bio-oils are chemically compatible with liquid fossil fuels. FTIR-ATR evidenced the presence of derivatives of depolymerization of lignin and cellulose in raw biomasses in bio-oil. TGA/DTG confirmed the bio-oil burning aptitude by the high average 53% mass loss of volatiles associated with lowered peaking decomposition temperatures by 100 °C than raw biomasses. Overall, this research shows the potential of bio-oil from liquefaction of SRC biomasses for the contribution of renewable energy and chemical deliverables, and thereby, to a greener global economy.

Redox-controlled chalcophile element geochemistry of the Polaris Alaskan-type mafic-ultramafic complex, British Columbia, Canada

ABSTRACT The Early Jurassic Polaris Alaskan-type intrusion in the Quesnel accreted arc terrane of the North American Cordillera is a zoned, mafic-ultramafic intrusive body that contains two main styles of magmatic mineralization of petrologic and potential economic significance: (1) chromitite-associated platinum group element (PGE) mineralization hosted by dunite (±wehrlite); and (2) sulfide-associated Cu-PGE-Au mineralization hosted by olivine (±magnetite) clinopyroxenite, hornblendite, and gabbro-diorite. Dunite-hosted PGE mineralization is spatially associated with thin discontinuous layers and schlieren of chromitite and chromitiferous dunite and is characterized by marked enrichments in iridium-subgroup PGE (IPGE) relative to palladium-subgroup PGE (PPGE). Discrete grains of platinum group minerals (PGM) are exceedingly rare, and the bulk of the PGE are inferred to reside in solid solution within chromite±olivine. The absence of Pt-Fe alloys in dunite of the Polaris intrusion is atypical, as Pt-enrichment of dunite-hosted chromitite is widely regarded as a characteristic feature of Alaskan-type intrusions. This discrepancy appears to be consistent with the strong positive dependence of Pt solubility on the oxidation state of sulfide-undersaturated magmas. Through comparison with experimentally determined PGE solubilities, we infer that the earliest (highest temperature) olivine-chromite cumulates of the Polaris intrusion crystallized from a strongly oxidized ultramafic parental magma with an estimated log f(O2) > FMQ+2. Parental magmas with oxygen fugacities more typical of volcanic arc settings [log f(O2) ∼ FMQ to ∼ FMQ+2] are, in turn, considered more favorable for co-precipitation of Pt-Fe alloys with olivine and chromite. More evolved clinopyroxene- and hornblende-rich cumulates of the Polaris intrusion contain low abundances of disseminated magmatic sulfides, consisting of pyrrhotite and chalcopyrite with minor pentlandite, pyrite, and rare bornite (≤12 wt.% total sulfides), which occur interstitially or as polyphase inclusions in silicates and oxides. The sulfide-bearing rocks are characterized by strong primitive mantle-normalized depletions in IPGE and enrichments in Cu-PPGE-Au, patterns that resemble those of other Alaskan-type intrusions and primitive arc lavas. The absolute abundances and sulfur-normalized whole-rock concentrations (Ci/S, serving as proxy for sulfide metal tenor) of chalcophile elements, including Cu/S, in sulfide-bearing rocks are highest in olivine clinopyroxenite. Sulfide saturation in the relatively evolved magmas of the Polaris intrusion, and Alaskan-type intrusions in general, appears to be intimately tied to the appearance of magnetite. Fractional crystallization of magnetite during the formation of olivine clinopyroxenite at Polaris resulted in reduction of the residual magma to log f(O2) ≤ FMQ+2, leading to segregation of an immiscible sulfide melt with high Cu/Fe and Cu/S, and high PGE and Au tenors. Continued fractionation resulted in sulfide melts that were progressively more depleted in precious and base chalcophile metals. The two styles of PGE mineralization in the Polaris Alaskan-type intrusion are interpreted to reflect the evolution of strongly oxidized, hydrous ultramafic parental magma(s) through intrinsic magmatic fractionation processes that potentially promote sulfide saturation in the absence of wallrock assimilation.

Sequential dependency for affective appraisal of food images

How we perceive the world is not solely determined by our experiences at a given moment in time, but also by what we have experienced in our immediate past. Here, we investigated whether such sequential effects influence the affective appraisal of food images. Participants from 16 different countries (N = 1278) watched a randomly presented sequence of 60 different food images and reported their affective appraisal of each image in terms of valence and arousal. For both measures, we conducted an inter-trial analysis, based on whether the rating on the preceding trial(s) was low or high. The analyses showed that valence and arousal ratings for a given food image are both assimilated towards the ratings on the previous trial (i.e., a positive serial dependence). For a given trial, the arousal rating depends on the arousal ratings up to three trials back. For valence, we observed a positive dependence for the immediately preceding trial only, while a negative (repulsive) dependence was present up to four trials back. These inter-trial effects were larger for males than for females, but independent of the participants’ BMI, age, and cultural background. The results of this exploratory study may be relevant for the design of websites of food delivery services and restaurant menus.

Equinoctial Asymmetry in Solar Quiet Fields along the 120° E Meridian Chain

Equinoctial asymmetry of the range of the solar quiet day variation (Sq) of the horizontal geomagnetic field (H) has been found in some low latitude geomagnetic observatories. This study conducted an investigation of its latitude distribution and the relationship with the solar cycle by using the H field measurements from six observatories along the 120° E meridian chain in the years 1957–2013. Results illustrate a significant equinoctial asymmetry of the SqH range at all observatories. Three main features were identified. First, the signature of the equinoctial asymmetry of the SqH range is opposite for observatories located at the northern and southern sides of the Northern Hemisphere Sq current focus. It shows larger values around spring than autumn equinox at southern observatories, and the converse is seen at northern observatories. Second, the asymmetry increases with the distance from the Sq current focus, suggesting the stronger sensitivity of the distant observatories than observatories around the focus. The result of linear fitting presents a positive dependence of the asymmetry coefficient on geographic latitude, with a reversal of the asymmetry occurring at 28.1° N near the focus of the average Sq current. Third, there is no obvious dependence of the equinoctial asymmetry of the SqH range on solar activity, suggesting a possible cause from some regional factors related to the ionospheric dynamo process.

Transient and Persistent Efficiency and Spatial Spillovers: Evidence from the Portuguese Wine Industry

This paper investigates the presence of spatial spillovers in firms’ productive (in)efficiency. For this purpose, a spatial stochastic frontier model is specified and estimated, accounting for spatial dependence and persistent and transient (in)efficiency. This approach is applied to a panel dataset from 2014 to 2019 of Portuguese wineries. Apart from the traditional input and output quantities used in the estimation of a production function, the novelty of this study is the inclusion of information on the firms’ exact location, which allows incorporating the neighboring dependence in the productive efficiency analysis. Empirical findings show that despite the Portuguese wineries’ technological positive dependence on spatial closeness for both inputs and outputs, the geographic closeness is not strong enough to provide overall productive efficiency gains.

Global variation in the fraction of leaf nitrogen allocated to photosynthesis

Plants invest a considerable amount of leaf nitrogen in the photosynthetic enzyme ribulose-1,5-bisphosphate carboxylase-oxygenase (RuBisCO), forming a strong coupling of nitrogen and photosynthetic capacity. Variability in the nitrogen-photosynthesis relationship indicates different nitrogen use strategies of plants (i.e., the fraction nitrogen allocated to RuBisCO; fLNR), however, the reason for this remains unclear as widely different nitrogen use strategies are adopted in photosynthesis models. Here, we use a comprehensive database of in situ observations, a remote sensing product of leaf chlorophyll and ancillary climate and soil data, to examine the global distribution in fLNR using a random forest model. We find global fLNR is 18.2 ± 6.2%, with its variation largely driven by negative dependence on leaf mass per area and positive dependence on leaf phosphorus. Some climate and soil factors (i.e., light, atmospheric dryness, soil pH, and sand) have considerable positive influences on fLNR regionally. This study provides insight into the nitrogen-photosynthesis relationship of plants globally and an improved understanding of the global distribution of photosynthetic potential.

The Sibling Distribution for Multivariate Life Time Data

A flexible class of multivariate distributions for continuous lifetimes is proposed. The distribution is defined in terms of the age-at-death of m siblings. The expression for the joint density is derived using classical results from mathematical demography. The parameters of the distribution are the age-specific birth and death rates, in addition to a vector of relative death times for the m siblings. For the case of constant birth and death rates we are able to derive an explicit expression for the bivariate sibling density, which is proven to be MTP2, and hence has positive dependence. Further, we show that a special case of the sibling distribution belongs to the Block-Basu class of multivariate distribution. In the general case, with age-dependent birth and death rates, evaluation of the density involves numerical integration, but is still feasible.

Morphometric Parameters of Lower Leg Tissues and Their Correlation with Laboratory Data in Patients with Post-Traumatic Osteomyelitis

Background. Knowledge about the pathological processes in the tissues of the limb is necessary for the targeted optimization of their course, the expectation of certain treatment results. The aim of the study was to determine the ratio of different severity cases and the correlation between individual clinical, laboratory and morphometric indicators of the tissues state in patients with trophic disorders in the extremity.Materials and Methods.The material was fragments of the lower leg tissues (bones, soft tissues, skin) of 38 patients with chronic post-traumatic osteomyelitis. Gradation morphometric indicators reflecting the tissues state in the lesion focuses were used. Frequency analysis of semiquantitative indicators and correlation analysis of the relationships between clinical, laboratory and morphometric indicators with the evaluation of the association coefficient were carried out. Results.Trophic disorders in the limb tissues (bones, soft tissues, muscles, skin), observed in patients with lower leg bones post-traumatic osteomyelitis, do not represent a group of well-defined pathological processes. They form a complex of dyscirculatory, ischemic, necrotic, dystrophic, atrophic, inflammatory, reparative and regenerative changes, which are combined in tissues in different proportions. This involves the use of a number of quantitative and semi-quantitative, gradation indicators: clinical, laboratory, and pathomorphological. Pathomorphological changes in the lesions in patients with chronic posttraumatic osteomyelitis of the lower leg bones with clinical signs of trophic disorders do not differ qualitatively from the changes usually detected in chronic post-traumatic osteomyelitis. In the bones, the most frequent are destructive focuses with a predominance of exudative and productive inflammation of high activity, sequestration and osteonecrosis. In paraossal soft tissues, more common are focuses, in which mature fibrous tissue and productive inflammation of low activity predominate. In the skin near the chronic post-traumatic osteomyelitis focuses, there is dermis fibrosis and productive inflammation of low activity.Conclusion. A number of correlations between clinical and laboratory parameters, on the one hand, and morphological parameters, on the other, have been established. The closest and most stable connections for different sites are the following indicators: blood leukocytes (negative dependence for affected bone, soft tissue and skin tissues), ESR (positive dependence for soft tissues), C-reactive protein (positive dependence for soft tissues and skin), agglutination with a polyvalent strain of Staphylococcus aureus (negative dependence for affected bones and skin).

On the Use of Entropy as a Measure of Dependence of Two Events

We define degree of dependence of two events A and B in a probability space by using Boltzmann-Shannon entropy function of an appropriate probability distribution produced by these events and depending on one parameter (the probability of intersection of A and B) varying within a closed interval I. The entropy function attains its global maximum when the events A and B are independent. The important particular case of discrete uniform probability space motivates this definition in the following way. The entropy function has a minimum at the left endpoint of I exactly when one of the events and the complement of the other are connected with the relation of inclusion (maximal negative dependence). It has a minimum at the right endpoint of I exactly when one of these events is included in the other (maximal positive dependence). Moreover, the deviation of the entropy from its maximum is equal to average information that carries one of the binary trials defined by A and B with respect to the other. As a consequence, the degree of dependence of A and B can be expressed in terms of information theory and is invariant with respect to the choice of unit of information. Using this formalism, we describe completely the screening tests and their reliability, measure efficacy of a vaccination, the impact of some events from the financial markets to other events, etc. A link is available for downloading an Excel program which calculates the degree of dependence of two events in a sample space with equally likely outcomes.

The emergence of a birth-dependent mutation rate in asexuals: causes and consequences

In unicellular organisms such as bacteria and in most viruses, mutations mainly occur during reproduction. Thus, genotypes with a high birth rate should have a higher mutation rate. However, standard models of asexual adaptation such as the 'replicator-mutator equation' often neglect this generation-time effect. In this study, we investigate the emergence of a positive dependence between the birth rate and the mutation rate in models of asexual adaptation and the consequences of this dependence. We show that it emerges naturally at the population scale, based on a large population limit of a stochastic time-continuous individual-based model with elementary assumptions. We derive a reaction-diffusion framework that describes the evolutionary trajectories and steady states in the presence of this dependence. When this model is coupled with a phenotype to fitness landscape with two optima, one for birth, the other one for survival, a new trade-off arises in the population. Compared to the standard approach with a constant mutation rate, the symmetry between birth and survival is broken. Our analytical results and numerical simulations show that the trajectories of mean phenotype, mean fitness and the stationary phenotype distribution are in sharp contrast with those displayed for the standard model. The reason for this is that the usual weak selection limit does not hold in a complex landscape with several optima associated with different values of the birth rate. Here, we obtain trajectories of adaptation where the mean phenotype of the population is initially attracted by the birth optimum, but eventually converges to the survival optimum, following a hook-shaped curve which illustrates the antagonistic effects of mutation on adaptation.