The placement of obstacles in front of doors is believed to be an effective strategy to increase the flow of pedestrians, hence improving the evacuation process. Since it was first suggested, this ...counterintuitive feature is considered a hallmark of pedestrian flows through bottlenecks. Indeed, despite the little experimental evidence, the placement of an obstacle has been hailed as the panacea for solving evacuation problems. In this work, we challenge this idea and experimentally demonstrate that the pedestrians flow rate is not necessarily altered by the presence of an obstacle. This result-which is at odds with recent demonstrations on its suitability for the cases of granular media, sheep and mice-differs from the outcomes of most of existing numerical models, and warns about the risks of carelessly extrapolating animal behaviour to humans. Our experimental findings also reveal an unnoticed phenomenon in relation with the crowd movement in front of the exit: in competitive evacuations, an obstacle attenuates the development of collective transversal rushes, which are hazardous as they might cause falls.
Biotic and abiotic emissions of molecular iodine and iodocarbons from the sea or the ice surface and the intertidal zone to the coastal/polar marine boundary layer lead to the formation of iodine ...oxides, which subsequently nucleate forming iodine oxide particles (IOPs). Although the link between coastal iodine emissions and ultrafine aerosol bursts is well established, the details of the nucleation mechanism have not yet been elucidated. In this paper, results of a theoretical study of a range of potentially relevant aggregation reactions of different iodine oxides, as well as complexation with water molecules, are reported. Thermochemical properties of these reactions are obtained from high level ab initio correlated calculations including spin-orbit corrections. The results show that the nucleation path most likely proceeds through dimerisation of I2O4. It is also shown that water can hinder gas-to-particle conversion to some extent, although complexation with key iodine oxides does not remove enough of these to stop IOP formation. A consistent picture of this process emerges from the theoretical study presented here and the findings of a new laboratory study reported in the accompanying paper (Gomez Martin et al., 2013).
With people trying to keep a safe distance from others due to the COVID-19 outbreak, the way in which pedestrians walk has completely changed since the pandemic broke out
. In this work, laboratory ...experiments demonstrate the effect of several variables-such as the pedestrian density, the walking speed and the prescribed safety distance-on the interpersonal distance established when people move within relatively dense crowds. Notably, we observe that the density should not be higher than 0.16 pedestrians per square meter (around 6 m
per pedestrian) in order to guarantee an interpersonal distance of 1 m. Although the extrapolation of our findings to other more realistic scenarios is not straightforward, they can be used as a first approach to establish density restrictions in urban and architectonic spaces based on scientific evidence.
When a sizable number of people evacuate a room, if the door is not large enough, an accumulation of pedestrians in front of the exit may take place. This is the cause of emerging collective ...phenomena where the density is believed to be the key variable determining the pedestrian dynamics. Here, we show that when sustained contact among the individuals exists, density is not enough to describe the evacuation, and propose that at least another variable -such as the kinetic stress- is required. We recorded evacuation drills with different degrees of competitiveness where the individuals are allowed to moderately push each other in their way out. We obtain the density, velocity and kinetic stress fields over time, showing that competitiveness strongly affects them and evidencing patterns which have been never observed in previous (low pressure) evacuation experiments. For the highest competitiveness scenario, we detect the development of sudden collective motions. These movements are related to a notable increase of the kinetic stress and a reduction of the velocity towards the door, but do not depend on the density.
Mercury is a contaminant of global concern. It is transported in the atmosphere primarily as gaseous elemental mercury, but its reactivity and deposition to the surface environment, through which it ...enters the aquatic food chain, is greatly enhanced following oxidation. Measurements and modelling studies of oxidised mercury in the polar to sub-tropical marine boundary layer (MBL) have suggested that photolytically produced bromine atoms are the primary oxidant of mercury. We report year-round measurements of elemental and oxidised mercury, along with ozone, halogen oxides (IO and BrO) and nitrogen oxides (NO2), in the MBL over the Galapagos Islands in the equatorial Pacific. Elemental mercury concentration remained low throughout the year, while higher than expected levels of oxidised mercury occurred around midday. Our results show that the production of oxidised mercury in the tropical MBL cannot be accounted for by bromine oxidation only, or by the inclusion of ozone and hydroxyl. As a two-step oxidation mechanism, where the HgBr intermediate is further oxidised to Hg(II), depends critically on the stability of HgBr, an additional oxidant is needed to react with HgBr to explain more than 50% of the observed oxidised mercury. Based on best available thermodynamic data, we show that atomic iodine, NO2, or HO2 could all play the potential role of the missing oxidant, though their relative importance cannot be determined explicitly at this time due to the uncertainties associated with mercury oxidation kinetics. We conclude that the key pathway that significantly enhances atmospheric mercury oxidation and deposition to the tropical oceans is missing from the current understanding of atmospheric mercury oxidation.
Despite the potential influence of iodine chemistry on the oxidizing capacity of the troposphere, reactive iodine distributions and their impact on tropospheric ozone remain almost unexplored aspects ...of the global atmosphere. Here we present a comprehensive global modelling experiment aimed at estimating lower and upper limits of the inorganic iodine burden and its impact on tropospheric ozone. Two sets of simulations without and with the photolysis of IxOy oxides (i.e. I2O2, I2O3 and I2O4) were conducted to define the range of inorganic iodine loading, partitioning and impact in the troposphere. Our results show that the most abundant daytime iodine species throughout the middle to upper troposphere is atomic iodine, with an annual average tropical abundance of (0.15–0.55) pptv. We propose the existence of a "tropical ring of atomic iodine" that peaks in the tropical upper troposphere (~11–14 km) at the equator and extends to the sub-tropics (30° N–30° S). Annual average daytime I / IO ratios larger than 3 are modelled within the tropics, reaching ratios up to ~20 during vigorous uplift events within strong convective regions. We calculate that the integrated contribution of catalytic iodine reactions to the total rate of tropospheric ozone loss (IOx Loss) is 2–5 times larger than the combined bromine and chlorine cycles. When IxOy photolysis is included, IOx Loss represents an upper limit of approximately 27, 14 and 27% of the tropical annual ozone loss for the marine boundary layer (MBL), free troposphere (FT) and upper troposphere (UT), respectively, while the lower limit throughout the tropical troposphere is ~9%. Our results indicate that iodine is the second strongest ozone-depleting family throughout the global marine UT and in the tropical MBL. We suggest that (i) iodine sources and its chemistry need to be included in global tropospheric chemistry models, (ii) experimental programs designed to quantify the iodine budget in the troposphere should include a strategy for the measurement of atomic I, and (iii) laboratory programs are needed to characterize the photochemistry of higher iodine oxides to determine their atmospheric fate since they can potentially dominate halogen-catalysed ozone destruction in the troposphere.
. We report a thorough analysis of the intermittent flow of pedestrians through a narrow door. The observations include five different sets of evacuation drills with which we have investigated the ...effect of door size and competitiveness on the flow dynamics. Although the outcomes are in general compatible with the existence of the faster-is-slower effect, the temporal evolution of the instantaneous flow rate provides evidence of new features. These stress the crucial role of the number of people performing the tests, which has an influence on the obtained results. Once the transients at the beginning and end of the evacuation are removed, we have found that the time lapses between the passage of two consecutive pedestrians display heavy-tailed distributions in all the scenarios studied. Meanwhile, the distribution of burst sizes decays exponentially; this can be linked to a constant probability of finding a long-lasting clog during the evacuation process. Based on these results, a discussion is presented on the caution that should be exercised when measuring or describing the intermittent flow of pedestrians through narrow doors.
The development of highly efficient and stable blue‐emitting dyes to overcome some of the most important shortcomings of available chromophores is of great technological importance for modern ...optical, analytical, electronic, and biological applications. Here, we report the design, synthesis and characterization of new tailor‐made BODIPY dyes with efficient absorption and emission in the blue spectral region. The major challenge is the effective management of the electron‐donor strength of the substitution pattern, in order to modulate the emission of these novel dyes over a wide spectral range (430–500 nm). A direct relationship between the electron‐donor character of the substituent and the extension of the spectral hypsochromic shift is seen through the energy increase of the LUMO state. However, when the electron‐donor character of the substituent is high enough, an intramolecular charge‐transfer process appears to decrease the fluorescence ability of these dyes, especially in polar media. Some of the reported novel BODIPY dyes provide very high fluorescence quantum yields, close to unity, and large Stokes shifts, leading to highly efficient tunable dye lasers in the blue part of the spectrum; this so far remains an unexploited region with BODIPYs. In fact, under demanding transversal pumping conditions, the new dyes lase with unexpectedly high lasing efficiencies of up to 63 %, and also show high photostabilities, outperforming the laser action of other dyes considered as benchmarks in the same spectral region. Considering the easy synthetic protocol and the wide variety of possible substituents, we are confident that this strategy could be successfully extended for the development of efficient blue‐edge emitting materials and devices, impelling biophotonic and optoelectronic applications.
So simple, so efficient, and so blue: 8‐Amino‐BODIPY dyes were prepared in a straightforward and efficient fashion (up to 95 % yield). They emit in the blue spectral region (see figure) with ϕ values up to 1.00, high laser efficiencies (up to 62 %), and good photostabilities. These results demonstrate that these new tailor‐made chromophores can overcome some of the shortcomings of commercial blue‐emitting dyes.
Reactive iodine compounds play a significant role in the atmospheric chemistry of the oceanic boundary layer by influencing the oxidising capacity through catalytically removing O3 and altering the ...HOx and NOx balance. The sea-to-air flux of iodine over the open ocean is therefore an important quantity in assessing these impacts on a global scale. This paper examines the effect of a number of relevant environmental parameters, including water temperature, salinity and organic compounds, on the magnitude of the HOI and I2 fluxes produced from the uptake of O3 and its reaction with iodide ions in aqueous solution. The results of these laboratory experiments and those reported previously (Carpenter et al., 2013), along with sea surface iodide concentrations measured or inferred from measurements of dissolved total iodine and iodate reported in the literature, were then used to produce parameterised expressions for the HOI and I2 fluxes as a function of wind speed, sea-surface temperature and O3. These expressions were used in the Tropospheric HAlogen chemistry MOdel (THAMO) to compare with MAX-DOAS measurements of iodine monoxide (IO) performed during the HaloCAST-P cruise in the eastern Pacific ocean (Mahajan et al., 2012). The modelled IO agrees reasonably with the field observations, although significant discrepancies are found during a period of low wind speeds (< 3 m s−1), when the model overpredicts IO by up to a factor of 3. The inorganic iodine flux contributions to IO are found to be comparable to, or even greater than, the contribution of organo-iodine compounds and therefore its inclusion in atmospheric models is important to improve predictions of the influence of halogen chemistry in the marine boundary layer.
The VELOUR study showed the benefit of FOLFIRI-Aflibercept (FA) versus FOLFIRI in patients with metastatic colorectal cancer (mCRC) in second-line treatment. However, only 36% of the included ...patients were ≥65 years. Thus, we seek to evaluate the efficacy and safety of FA in the elderly population in the context of routine practice.
We conducted an observational, retrospective, multicenter, observational study of patients ≥70 years with mCRC treated with FA after progression to oxaliplatin chemotherapy in routine clinical practice in 9 hospitals of the GITuD group.
Of 388 patients treated with FA between June 2013 and November 2018, 75 patients ≥70 years were included. The median number of cycles was 10 and the objective response (ORR) and disease control rates (DCR) were 33.8% and 72.0%, respectively. With a median follow-up of 27.1 months, median Progression-free survival (PFS) was 6.6 months and median Overall Survival (OS) was 15.1 months. One third fewer metastasectomies were performed in the ≥75 years' subgroup (24 vs. 52%, p = 0.024) and more initial FOLFIRI dose reductions (68 vs. 36%, p = 0.014). ORR (23.8% vs. 38.3%), DCR (42.8% vs. 85.1%), and PFS (4 vs. 7.8 months; p = 0.017) were significantly less, without difference in OS (9.9 vs. 17.1 months; p = 0.129). The presence of prior hypertension (HT) (PFS 7.9 vs. 5.7 months, p = 0.049) and HT ≥ grade 3 during treatment (PFS 7.6 vs. 6.6 months, p = 0.024) were associated with longer PFS. The most frequent grade 3/4 adverse events were: asthenia (21.3%), neutropenia (14.7%), and diarrhea (14.7%). 57.3% required FOLFIRI dose reduction; 34.7% of aflibercept, including discontinuation (5.3% and 18.7%, respectively).
FA combination is effective in patients ≥70 years. The occurrence of HT is predictive of efficacy. Close monitoring of toxicity and initial dose adjustment is recommended.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK