Kinetic studies of reactions of the nitrate radical (NO3) with peroxy radicals (RO2): an indirect source of OH at night?

A discharge-flow system, coupled to cavity-enhanced absorption spectroscopy (CEAS) detection systems for NO3 at lambda = 662 nm and NO2 at lambda = 404 nm, was used to investigate the kinetics of the reactions of NO3 with eight peroxy radicals at P similar to 5 Torr and T similar to 295 K. Values of the rate constants obtained were (k/10(-12) cm(3) molecule(-1) s(-1)): CH3O2 (1.1 +/- 0.5), C2H5O2 (2.3 +/- 0.7), CH2FO2 (1.4 +/- 0.9), CH2ClO2 (3.8(-2.6)(+1.4)), c-C5H9O2 (1.2(-0.5)(+1.1)), c-C6H11O2 (1.9 +/- 0.7), CF3O2 (0.62 +/- 0.17) and CF3CFO2CF3 (0.24 +/- 0.13). We explore possible relationships between k and the orbital energies of the reactants. We also provide a brief discussion of the potential impact of the reactions of NO3 with RO2 on the chemistry of the night-time atmosphere.

Summer drought in northern midlatitudes in a time-dependent CO2 climate experiment

A time-dependent climate-change experiment with a coupled ocean–atmosphere general circulation model has been used to study changes in the occurrence of drought in summer in southern Europe and central North America. In both regions, precipitation and soil moisture are reduced in a climate of greater atmospheric carbon dioxide. A detailed investigation of the hydrology of the model shows that the drying of the soil comes about through an increase in evaporation in winter and spring, caused by higher temperatures and reduced snow cover, and a decrease in the net input of water in summer. Evaporation is reduced in summer because of the drier soil, but the reduction in precipitation is larger. Three extreme statistics are used to define drought, namely the frequency of low summer precipitation, the occurrence of long dry spells, and the probability of dry soil. The last of these is arguably of the greatest practical importance, but since it is based on soil moisture, of which there are very few observations, the authors’ simulation of it has the least confidence. Furthermore, long time series for daily observed precipitation are not readily available from a sufficient number of stations to enable a thorough evaluation of the model simulation, especially for the frequency of long dry spells, and this increases the systematic uncertainty of the model predictions. All three drought statistics show marked increases owing to the sensitivity of extreme statistics to changes in their distributions. However, the greater likelihood of long dry spells is caused by a tendency in the character of daily rainfall toward fewer events, rather than by the reduction in mean precipitation. The results should not be taken as firm predictions because extreme statistics for small regions cannot be calculated reliably from the output of the current generation of GCMs, but they point to the possibility of large increases in the severity of drought conditions as a consequence of climate change caused by increased CO2.

New evidence on the green building rent and price premium

This paper investigates the effect of voluntary eco-certification on the rental and sale prices of US commercial office properties. Hedonic and logistic regressions are used to test whether there are rental and sale price premiums for LEED and Energy Star certified buildings. The results of the hedonic analysis suggest that there is a rental premium of approximately 6% for LEED and Energy Star certification. A sale price premium of approximately 35% was found for 127 price observations involving LEED rated buildings and 31% for 662 buildings involving Energy Star rated buildings. When compared to samples of similar buildings identified by a binomial logistic regression for LEED-certified buildings, the existence of a rent and sales price premium is confirmed albeit with differences regarding the magnitude of the premium. Overall, the results of this study confirm that LEED and Energy Star buildings exhibit higher rental rates and sales prices per square foot controlling for a large number of location- and property-specific factors.

Periodic time series modeling of environmental proxy records with guaranteed positive growth rate estimation

Identifying a periodic time-series model from environmental records, without imposing the positivity of the growth rate, does not necessarily respect the time order of the data observations. Consequently, subsequent observations, sampled in the environmental archive, can be inversed on the time axis, resulting in a non-physical signal model. In this paper an optimization technique with linear constraints on the signal model parameters is proposed that prevents time inversions. The activation conditions for this constrained optimization are based upon the physical constraint of the growth rate, namely, that it cannot take values smaller than zero. The actual constraints are defined for polynomials and first-order splines as basis functions for the nonlinear contribution in the distance-time relationship. The method is compared with an existing method that eliminates the time inversions, and its noise sensitivity is tested by means of Monte Carlo simulations. Finally, the usefulness of the method is demonstrated on the measurements of the vessel density, in a mangrove tree, Rhizophora mucronata, and the measurement of Mg/Ca ratios, in a bivalve, Mytilus trossulus.

Comparing the UK Met Office climate prediction system DePreSys with idealized predictability in the HadCM3 model

The initial condition effect on climate prediction skill over a 2-year hindcast time-scale has been assessed from ensemble HadCM3 climate model runs using anomaly initialization over the period 1990–2001, and making comparisons with runs without initialization (equivalent to climatological conditions), and to anomaly persistence. It is shown that the assimilation improves the prediction skill in the first year globally, and in a number of limited areas out into the second year. Skill in hindcasting surface air temperature anomalies is most marked over ocean areas, and is coincident with areas of high sea surface temperature and ocean heat content skill. Skill improvement over land areas is much more limited but is still detectable in some cases. We found little difference in the skill of hindcasts using three different sets of ocean initial conditions, and we obtained the best results by combining these to form a grand ensemble hindcast set. Results are also compared with the idealized predictability studies of Collins (Clim. Dynam. 2002; 19: 671–692), which used the same model. The maximum lead time for which initialization gives enhanced skill over runs without initialization varies in different regions but is very similar to lead times found in the idealized studies, therefore strongly supporting the process representation in the model as well as its use for operational predictions. The limited 12-year period of the study, however, means that the regional details of model skill should probably be further assessed under a wider range of observational conditions.

New half-sandwich heterobimetallic CpMPt (M=Rh, Ir) dithiolato bridged complexes

Cationic heterobimetallic complexes 5–7 [(PPh3)2Pt(μ-edt)MClCp′)]BF4 (edt=−S(CH2)2S−; 5: M=Rh and Cp′=η5-C5H5; 6: M=Rh and Cp′=η5-C5Me5 and 7: M=Ir and Cp′=η5-C5Me5) were prepared by reaction of [Pt(edt)(PPh3)2] with [Cp′ClM(μ-Cl)2MClCp′] in THF in the presence of two equivalents of AgBF4. The crystalline structure of 5 was determined by X-ray diffraction methods. Cationic heterobimetallic complexes [(PPh3)2Pt(μ-S(CH2)2S)MClCp′)]BF4 (M=Rh, Ir) were prepared. The crystalline structure of [(PPh3)2Pt(μ-edt)RhClCp)]BF4 was determined by X-ray diffraction methods.

Optimal linearization trajectories for tangent linear models

We examine differential equations where nonlinearity is a result of the advection part of the total derivative or the use of quadratic algebraic constraints between state variables (such as the ideal gas law). We show that these types of nonlinearity can be accounted for in the tangent linear model by a suitable choice of the linearization trajectory. Using this optimal linearization trajectory, we show that the tangent linear model can be used to reproduce the exact nonlinear error growth of perturbations for more than 200 days in a quasi-geostrophic model and more than (the equivalent of) 150 days in the Lorenz 96 model. We introduce an iterative method, purely based on tangent linear integrations, that converges to this optimal linearization trajectory. The main conclusion from this article is that this iterative method can be used to account for nonlinearity in estimation problems without using the nonlinear model. We demonstrate this by performing forecast sensitivity experiments in the Lorenz 96 model and show that we are able to estimate analysis increments that improve the two-day forecast using only four backward integrations with the tangent linear model. Copyright © 2011 Royal Meteorological Society

Through Jewish eyes: polemical literature and the medieval papacy

Although the medieval papacy's stance towards the Jews is a well-established area of research, Jewish ideas about the papacy remain a surprisingly underdeveloped historical topic. This article explores such ideas through the genre of polemic and disputational literature. Jewish writers were keen to ensure the safety of their communities in western Europe and grateful for statements of papal protection. They fully acknowledged that popes had always played and would continue to play an important role in safeguarding their well-being and determining their future. Yet although contemporary and later writers often valued papal protection more highly than that of monarchs, emperors or clergy, they also knew that it had its carefully circumscribed limits. Furthermore, although they were respectful of the papacy's power, both spiritual and temporal, they were dismissive of the scriptural and theological formulations on which Christian claims for apostolic authority rested and highly critical of Christian beliefs about the papacy, in particular that of apostolic succession. Jewish ideas about both individual popes and the medieval papacy as an institution are therefore nuanced and complex; they deserve rigorous and wide-ranging investigation and it is hoped that this article will contribute to their better understanding.

A Gaussian-mixture ensemble transform filter

We generalize the popular ensemble Kalman filter to an ensemble transform filter, in which the prior distribution can take the form of a Gaussian mixture or a Gaussian kernel density estimator. The design of the filter is based on a continuous formulation of the Bayesian filter analysis step. We call the new filter algorithm the ensemble Gaussian-mixture filter (EGMF). The EGMF is implemented for three simple test problems (Brownian dynamics in one dimension, Langevin dynamics in two dimensions and the three-dimensional Lorenz-63 model). It is demonstrated that the EGMF is capable of tracking systems with non-Gaussian uni- and multimodal ensemble distributions. Copyright © 2011 Royal Meteorological Society

A scalable expressive ensemble learning using Random Prism: a MapReduce approach

The induction of classification rules from previously unseen examples is one of the most important data mining tasks in science as well as commercial applications. In order to reduce the influence of noise in the data, ensemble learners are often applied. However, most ensemble learners are based on decision tree classifiers which are affected by noise. The Random Prism classifier has recently been proposed as an alternative to the popular Random Forests classifier, which is based on decision trees. Random Prism is based on the Prism family of algorithms, which is more robust to noise. However, like most ensemble classification approaches, Random Prism also does not scale well on large training data. This paper presents a thorough discussion of Random Prism and a recently proposed parallel version of it called Parallel Random Prism. Parallel Random Prism is based on the MapReduce programming paradigm. The paper provides, for the first time, novel theoretical analysis of the proposed technique and in-depth experimental study that show that Parallel Random Prism scales well on a large number of training examples, a large number of data features and a large number of processors. Expressiveness of decision rules that our technique produces makes it a natural choice for Big Data applications where informed decision making increases the user’s trust in the system.

Seafood safety and quality: an analysis of the supply chain in the Sultanate of Oman

The globalization of trade in fish has created many challenges for the developing world specifically with regard to food safety and quality. International organisations have established a good basis for standards in international trade. Whilst these requirements are frequently embraced by the major importers (such as Japan, the EU and the USA), they often impose additional safety requirements and regularly identify batches which fail to meet their strict standards. Creating an effective national seafood control system which meets both the internal national needs as well the requirements for the export market can be challenging. Many countries adopt a dual system where seafood products for the major export markets are subject to tight control whilst the majority of the products (whether for the local market or for more regional trade) are less tightly controlled. With regional liberalization also occurring, deciding on appropriate controls is complex. In the Sultanate of Oman, fisheries production is one of the countries' chief sources of economic revenue after oil production and is a major source of the national food supply. In this paper the structure of the fish supply chain has been analysed and highlighted the different routes operating for the different markets. Although much of the fish are consumed within Oman, there is a major export trade to the local regional markets. Much smaller quantities meet the more stringent standards imposed by the major importing countries and exports to these are limited. The paper has considered the development of the Omani fish control system including the key legislative documents and the administrative structures that have been developed. Establishing modern controls which satisfy the demands of the major importers is possible but places additional costs on businesses. Enhanced controls such as HACCP and other management standards are required but can be difficult to justify when alternative markets do not specify these. These enhanced controls do however provide additional consumer protection and can bring benefits to local consumers. The Omani government is attempting to upgrade the system of controls and has made tremendous progress toward the implementation of HACCP and introducing enhanced management systems into its industrial sector. The existence of strengthened legislative and government support, including subsidies, has encouraged some businesses to implement HACCP. The current control systems have been reviewed and a SWOT analysis approach used to identify key factors for their future development. The study shows that seafood products in the supply chain are often exposed to lengthy handling and distribution process before reaching the consumers, a typical issue faced by many developing countries. As seafood products are often perishable, they safety is compromised if not adequately controlled. The enforcement of current food safety laws in the Sultanate of Oman is shared across various government agencies. Consequently, there is a need to harmonize all regulatory requirements, enhancing the domestic food protection and to continue to work towards a fully risk-based approach in order to compete successfully in the global market.

Children’s eye movements during reading

Children’s eye movements during reading. In this chapter, we evaluate the literature on children’s eye movements during reading to date. We describe the basic, developmental changes that occur in eye movement behaviour during reading, discuss age-related changes in the extent and time course of information extraction during fixations in reading, and compare the effects of visual and linguistic manipulations in the text on children’s eye movement behaviour in relation to skilled adult readers. We argue that future research will benefit from examining how eye movement behaviour during reading develops in relation to language and literacy skills, and use of computational modelling with children’s eye movement data may improve our understanding of the mechanisms that underlie the progression from beginning to skilled reader.

Older age of onset in child L2 acquisition can be facilitative: evidence from the acquisition of English passives by Spanish natives

We report a longitudinal comprehension study of (long) passive constructions in two native-Spanish child groups differing by age of initial exposure to L2 English (young group: 3;0-4;0 years; older group: 6;0-7;0 years); where amount of input, L2 exposure environment, and socio-economic status are controlled. Data from a forced-choice task show that both groups comprehend active sentences, not passives, initially (after 3.6 years of exposure). One year later, both groups improve, but only the older group reaches ceiling on both actives and passives. Two years from initial testing, the younger group catches up. Input alone cannot explain why the younger group takes 5 years to accomplish what the older group does in 4. We claim that some properties take longer to acquire at certain ages because language development is partially constrained by general cognitive and linguistic development (e.g. de Villiers, 2007; Long & Rothman, 2014; Paradis, 2008, 2010, 2011; Tsimpli, 2014).