133 research outputs found
Laboratory Determination of the Infrared Band Strengths of Pyrene Frozen in Water Ice: Implications for the Composition of Interstellar Ices
Broad infrared emission features (e.g., at 3.3, 6.2, 7.7, 8.6, and 11.3
microns) from the gas phase interstellar medium have long been attributed to
polycyclic aromatic hydrocarbons (PAHs). A significant portion (10%-20%) of the
Milky Way's carbon reservoir is locked in PAH molecules, which makes their
characterization integral to our understanding of astrochemistry. In molecular
clouds and the dense envelopes and disks of young stellar objects (YSOs), PAHs
are expected to be frozen in the icy mantles of dust grains where they should
reveal themselves through infrared absorption. To facilitate the search for
frozen interstellar PAHs, laboratory experiments were conducted to determine
the positions and strengths of the bands of pyrene mixed with H2O and D2O ices.
The D2O mixtures are used to measure pyrene bands that are masked by the strong
bands of H2O, leading to the first laboratory determination of the band
strength for the CH stretching mode of pyrene in water ice near 3.25 microns.
Our infrared band strengths were normalized to experimentally determined
ultraviolet band strengths, and we find that they are generally ~50% larger
than those reported by Bouwman et al. based on theoretical strengths. These
improved band strengths were used to reexamine YSO spectra published by Boogert
et al. to estimate the contribution of frozen PAHs to absorption in the 5-8
micron spectral region, taking into account the strength of the 3.25 micron CH
stretching mode. It is found that frozen neutral PAHs contain 5%-9% of the
cosmic carbon budget, and account for 2%-9% of the unidentified absorption in
the 5-8 micron region.Comment: Accepted for publication in ApJ on 14 Feb 201
Turbulent mixing simulation using the Hierarchical Parcel-Swapping (HiPS) model
Turbulent mixing is an omnipresent phenomenon that permanently affects our everyday life. Mixing processes alsoplays an important role in many industrial applications. The full resolution of all relevant flow scales often poses a major challenge to the numerical simulation and requires a modeling of the small-scale effects. In transported Probability Density Function (PDF) methods, the simplified modeling of the molecular mixing is a known weak point. At this place, the Hierarchical Parcel-Swapping (HiPS) model developed by A.R. Kerstein [J. Stat. Phys. 153, 142-161 (2013)] represents a computationally efficient and novel turbulent mixing model. HiPS simulates the effects of turbulence on time-evolving, diffusive scalar fields. The interpretation of the diffusive scalar fields or a state space as a binary tree structure is an alternative approach compared to existing mixing models. The characteristic feature of HiPS is that every level of the tree corresponds to a specific length and time scale, which is based on turbulence inertial range scaling. The state variables only reside at the base of the tree and are understood as fluid parcels. The effects of turbulent advection are represented by stochastic swaps of sub-trees at rates determined by turbulent time scales associated with the sub-trees. The mixing of adjacent fluid parcels is done at rates consistent with the prevailing diffusion time scales. In this work, a standalone HiPS model formulation for the simulation of passive scalar mixing is detailed first. The generated scalar power spectra with forced turbulence shows the known scaling law of Kolmogorov turbulence. Furthermore, results for the PDF of the passive scalar, mean square displacement and scalar dissipation rate are shown and reveal a reasonable agreement with experimental findings. The described possibility to account for variable Schmidt number effects is an important next development step for the HiPS formulation. This enables the incorporation of differential diffusion, which represents an immense advantage compared to the established mixing models. Using a binary structure allows HiPS to satisfy a large number of criteria for a good mixing model. Considering the reduced order and associated computational efficiency, HiPS is an attractive mixing model, which can contribute to an improved representation of the molecular mixing in transported PDF methods
Vapor wall deposition in Teflon chambers
Teflon chambers are ubiquitous in studies of atmospheric chemistry. Secondary organic aerosol (SOA) formation can be underestimated, owing to deposition of SOA-forming vapors to the chamber wall. We present here an experimental protocol and a model framework to constrain the vapor–wall interactions in Teflon chambers. We measured the wall deposition rates of 25 oxidized organic compounds generated from the photooxidation of isoprene, toluene, α-pinene, and dodecane in two chambers that had been extensively used and in two new unused chambers. We found that the extent of prior use of the chamber did not significantly affect the sorption behavior of the Teflon films. Among the 25 compounds studied, the maximum wall deposition rate is exhibited by the most highly oxygenated and least volatile compounds. By optimizing the model output to the observed vapor decay profiles, we identified that the dominant parameter governing the extent of wall deposition of a compound is its wall accommodation coefficient (α_(wi)), which can be correlated through its volatility with the number of carbons and oxygens in the molecule. By doing so, the wall-induced deposition rate of intermediate/semi-volatile organic vapors can be reasonably predicted based on their molecular constituency. The extent to which vapor wall deposition impacts measured SOA yields depends on the competition between uptake of organic vapors by suspended particles and the chamber wall. The timescale associated with vapor wall deposition can vary from minutes to hours depending on the value of α_(w,i). For volatile and intermediate volatility organic compounds (small α_(w,i)), gas-particle partitioning will dominate wall deposition for typical particle number concentrations in chamber experiments. For compounds characterized by relatively large α_(w,i), vapor transport to particles is suppressed by competition with the chamber wall even with perfect particle accommodation
A comparative study of responses in planktonic food web structure and function in contrasting European coastal waters exposed to experimental nutrient addition
We quantify, compare, and generalize responses of experimental nutrient loadings (LN) on planktonic community structure and function in coastal waters. Data were derived from three mesocosm experiments undertaken in Baltic (BAL), Mediterranean (MED), and Norwegian (NOR) coastal waters. A planktonic model with seven functional compartments and 30-32 different carbon flows fit to all three experiments was used as a framework for flow-rate estimation and comparison. Flows were estimated on the basis of time series of measured biomass, some measured flows, and inverse modeling. Biomass and gross uptake rate of carbon of most groups increased linearly with increasing LN in the nutrient input range of 0-1 µmol N L-1 d-1 at all locations. The fate of the gross primary production (GPP) was similar in all systems. Autotrophic biomass varied by two orders of magnitude among locations, with the lowest biomass and response to nutrient addition in MED waters. The variation of GPP among sites was less than one order of magnitude. Mesozooplankton dominated by doliolids (Tunicata), but not those dominated by copepods, presumably exerted efficient control of the autotrophic biomass, thereby buffering responses of autotrophs to high nutrient input. Among the many factors that can modify the responses of autotrophs to nutrients, the time scale over which the enrichment is made and the precise mode of nutrient enrichment are important. We suggest a general concept that may contribute to a scientific basis for understanding and managing coastal eutrophicatio
Improved Normothermic Machine Perfusion After Short Oxygenated Hypothermic Machine Perfusion of Ischemically Injured Porcine Kidneys
Background: In an era where global kidney shortage has pushed the field of transplantation towards using more marginal donors, modified kidney preservation techniques are currently being reviewed. Some techniques require further optimization before implementation in full scale transplantation studies. Using a porcine donation after circulatory death kidney model, we investigated whether initial kidney hemodynamics improved during normothermic machine perfusion if this was preceded by a short period of oxygenated hypothermic machine perfusion (oxHMP) rather than static cold storage (SCS). Methods: Kidneys subjected to 75 minutes of warm ischemia were randomly assigned to either SCS (n = 4) or SCS + oxHMP (n = 4), with a total cold storage time of 240 minutes. Cold preservation was followed by 120 minutes of normothermic machine perfusion with continuous measurement of hemodynamic parameters and renal function. Results: oxHMP preserved kidneys maintained significantly lower renal resistance throughout the normothermic machine perfusion period compared to SCS kidneys (P < 0.001), reaching lowest levels at 60 minutes with means of 0.71 ± 0.35 mm Hg/mL/min/100 g (SCS) and 0.45 ± 0.15 mm Hg/mL/min/100 g (oxHMP). Accordingly, the oxHMP group had a higher mean renal blood flow versus SCS kidneys (P < 0.001). oxHMP kidneys had higher oxygen consumption during normothermic machine perfusion compared to SCS preserved kidneys (P < 0.001). Creatinine clearance remained similar between groups (P = 0.665). Conclusions: Preceding oxHMP significantly improved initial normothermic machine perfusion hemodynamics and increased total oxygen consumption. With the long period of warm ischemia, immediate kidney function was not observed, reflected by the findings of low creatinine clearance in both groups
Mesenchymal stromal cell treatment of donor kidneys during ex-vivo normothermic machine perfusion:A porcine renal autotransplantation study
Normothermic machine perfusion (NMP) of injured kidneys offers the opportunity for interventions to metabolically active organs prior to transplantation. Mesenchymal stromal cells (MSCs) can exert regenerative and anti-inflammatory effects in ischaemia-reperfusion injury. The aims of this study were to evaluate the safety and feasibility of MSC treatment of kidneys during NMP using a porcine auto-transplantation model, and examine potential MSC treatment-associated kidney improvements up to 14 days post transplantation. After 75 minutes of kidney warm ischaemia, four experimental groups of n=7 underwent 14 hours of oxygenated hypothermic machine perfusion. In three groups this was followed by 240 minutes of NMP with infusion of vehicle, ten million porcine or ten million human adipose derived MSCs. All kidneys were auto-transplanted after contralateral nephrectomy. MSC treatment did not affect perfusion haemodynamics during NMP or cause adverse effects at reperfusion, with 100% animal survival. MSCs did not affect plasma creatinine, glomerular filtration rate, neutrophil gelatinase-associated lipocalin concentrations or kidney damage assessed by histology during the 14 days, and MSCs retention was demonstrated in renal cortex. Infusing MSCs during ex vivo NMP of porcine kidneys was safe and feasible. Within the short post- transplant
Performance of the Redfield Ratio and a Family of Nutrient Limitation Indicators as Thresholds for Phytoplankton N vs. P Limitation
Nucleic Acid Content in Crustacean Zooplankton: Bridging Metabolic and Stoichiometric Predictions
Metabolic and stoichiometric theories of ecology have provided broad complementary principles to understand ecosystem processes across different levels of biological organization. We tested several of their cornerstone hypotheses by measuring the nucleic acid (NA) and phosphorus (P) content of crustacean zooplankton species in 22 high mountain lakes (Sierra Nevada and the Pyrenees mountains, Spain). The P-allocation hypothesis (PAH) proposes that the genome size is smaller in cladocerans than in copepods as a result of selection for fast growth towards P-allocation from DNA to RNA under P limitation. Consistent with the PAH, the RNA:DNA ratio was >8-fold higher in cladocerans than in copepods, although ‘fast-growth’ cladocerans did not always exhibit higher RNA and lower DNA contents in comparison to ‘slow-growth’ copepods. We also showed strong associations among growth rate, RNA, and total P content supporting the growth rate hypothesis, which predicts that fast-growing organisms have high P content because of the preferential allocation to P-rich ribosomal RNA. In addition, we found that ontogenetic variability in NA content of the copepod Mixodiaptomus laciniatus (intra- and interstage variability) was comparable to the interspecific variability across other zooplankton species. Further, according to the metabolic theory of ecology, temperature should enhance growth rate and hence RNA demands. RNA content in zooplankton was correlated with temperature, but the relationships were nutrient-dependent, with a positive correlation in nutrient-rich ecosystems and a negative one in those with scarce nutrients. Overall our results illustrate the mechanistic connections among organismal NA content, growth rate, nutrients and temperature, contributing to the conceptual unification of metabolic and stoichiometric theories.This research was supported by the Spanish Ministries of Science and Innovation (CGL2011-23681/BOS), and Environment, Rural and Marine Affairs (OAPN2009/067); ‘ConsejerÃa de Innovación, Ciencia y Empresa – Junta de AndalucÃa’ (Excelencia CVI-02598; P09-RNM-5376); The Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning (FORMAS) and Stockholm University’s strategic marine environmental research program ‘Baltic Ecosystem Adaptive Management’, and a Spanish government ‘Formación de Profesorado Universitario’ fellowship to F.J. Bullejos
Harmonization of human biomonitoring studies in Europe: characteristics of the HBM4EU-aligned studies participants
Human biomonitoring has become a pivotal tool for supporting chemicals' policies. It provides information on real-life human exposures and is increasingly used to prioritize chemicals of health concern and to evaluate the success of chemical policies. Europe has launched the ambitious REACH program in 2007 to improve the protection of human health and the environment. In October 2020 the EU commission published its new chemicals strategy for sustainability towards a toxic-free environment. The European Parliament called upon the commission to collect human biomonitoring data to support chemical's risk assessment and risk management. This manuscript describes the organization of the first HBM4EU-aligned studies that obtain comparable human biomonitoring (HBM) data of European citizens to monitor their internal exposure to environmental chemicals. The HBM4EU-aligned studies build on existing HBM capacity in Europe by aligning national or regional HBM studies. The HBM4EU-aligned studies focus on three age groups: children, teenagers, and adults. The participants are recruited between 2014 and 2021 in 11 to 12 primary sampling units that are geographically distributed across Europe. Urine samples are collected in all age groups, and blood samples are collected in children and teenagers. Auxiliary information on socio-demographics, lifestyle, health status, environment, and diet is collected using questionnaires. In total, biological samples from 3137 children aged 6-12 years are collected for the analysis of biomarkers for phthalates, HEXAMOLL((R)) DINCH, and flame retardants. Samples from 2950 teenagers aged 12-18 years are collected for the analysis of biomarkers for phthalates, Hexamoll((R)) DINCH, and per- and polyfluoroalkyl substances (PFASs), and samples from 3522 adults aged 20-39 years are collected for the analysis of cadmium, bisphenols, and metabolites of polyaromatic hydrocarbons (PAHs). The children's group consists of 50.4% boys and 49.5% girls, of which 44.1% live in cities, 29.0% live in towns/suburbs, and 26.8% live in rural areas. The teenagers' group includes 50.6% girls and 49.4% boys, with 37.7% of residents in cities, 31.2% in towns/suburbs, and 30.2% in rural areas. The adult group consists of 52.6% women and 47.4% men, 71.9% live in cities, 14.2% in towns/suburbs, and only 13.4% live in rural areas. The study population approaches the characteristics of the general European population based on age-matched EUROSTAT EU-28, 2017 data; however, individuals who obtained no to lower educational level (ISCED 0-2) are underrepresented. The data on internal human exposure to priority chemicals from this unique cohort will provide a baseline for Europe's strategy towards a non-toxic environment and challenges and recommendations to improve the sampling frame for future EU-wide HBM surveys are discussed
Interactive Effect of UVR and Phosphorus on the Coastal Phytoplankton Community of the Western Mediterranean Sea: Unravelling Eco- Physiological Mechanisms
Versión del editor4,411
- …