Safer management of process changes in chemical reactors

Nowadays many chemical industries are SMEs where multi-purpose batch or semi-batch reactors are commonly used. Vent sizing for realistic runaway scenario is not an easy task for such enterprises since they have usually few resources and use multi-purpose reactors with fast process turnovers. As a consequence these batch and semi-batch reactors are usually equipped with emergency relief systems sized once forever when the reactor is designed. This can lead to a large underestimation of the vent area in case of runaway reactions occurring when processes different from the ones considered for originally sizing the vent are carried out.The approach proposed in this work aims to identify the maximum reactor load leading to safe conditions even in case of runaway phenomena to be handled with the emergency relief system already installed (or even with a smaller vent area). This approach allows avoiding the change of the emergency relief system with a larger vent area (as required every time a new more hazardous process has to be carried out on existing reactors) at the price of lower plant productivity.     

The toxicity of sulfamethazine to Daphnia magna and its additivity to other veterinary sulfonamides and trimethoprim

Sulfonamides (SAs), the oldest chemotherapeutic agents used for antimicrobial therapy, still play an important role in veterinary mass treatments. Consequently, traces of these compounds, alone or in combinations, have been repeatedly detected in the environment. Sulfamethazine (SMZ) deserves particular attention not only because it is the most used veterinary SA, but also due to its proven effects on fertility in mice and on thyroid hormone homeostasis in rats. In this study, after evaluating the acute toxicity to Daphnia magna of six veterinary SAs and trimethoprim (TMP), the additivity of SMZ to each other compound was tested using the isobologram method. Two reproduction tests on the same biological model were also performed in order to derive LOEC and NOEC of SMZ. The acute EC₅₀ was in the range 131–270 mg L⁻¹ for all the compounds tested with the exception of sulfaguanidine (EC₅₀ = 3.86 mg L⁻¹). In acute binary tests SMZ showed a complex interaction with sulfaquinoxaline (superadditivity, additivity or subadditivity) at the three different combination ratios tested, simple additivity to TMP and less than additive interaction when paired to the other SAs. LOEC and NOEC of SMZ obtained from reproduction tests were 3.125 and 1.563 mg L⁻¹, respectively. In conclusion, SMZ should not harm the crustacean population at environmentally realistic concentrations. Its toxicity is comparable to that of other systemic SAs, and their binary interactions are less than additive. The same can not be entirely said for enteric SAs, and considering that these compounds are administered at high doses and mostly excreted in unmetabolised form, further evaluation of their impact to the aquatic environment seems advisable.     

Pesticide removal from waste spray-tank water by organoclay adsorption after field application: an approach for a formulation of cyprodinil containing antifoaming/defoaming agents

Purpose  

Many reports on purification of water containing pesticides are based on studies using unformulated active ingredients. However, most commercial formulations contain additives/adjuvants or are manufactured using microencapsulation which may influence the purification process. Therefore, the main objective of this work was to develop and test a pilot scheme for decontaminating water containing pesticides formulated with antifoaming/defoaming agents.     

A study of climate change and anthropogenic impacts in West Africa

BACKGROUND, AIM AND SCOPE: During the last decades ecological conditions in West Africa have dramatically changed. Very evident is the climate change, which has resulted in a southward shift of the climate zones, e.g. a spread of the desert (Sahara) into the Sahelian zone. After the drought period of the early 1970s and 1980s, livestock density increased resulting in an intensification of grazing pressure. This anthropogenous phenomenon leads to similar landscape changes as those caused by the climate. Only very few investigations exist on vegetation dynamics, climate changes and land use changes for the Sudanian zone. The paper presents data on changes of precipitation, of land use, of the geographical range of species, and of the composition of the flora, which have to be regarded as proofs of the sahelisation of large areas of the Sudanian zone. MATERIALS AND METHODS: Area of investigation: Burkina Faso. Precipitation data analysis: precipitation data from 67 stations; time series analysis and geo-statistical spatial interpolation. Analysis of land use change: Landsat satellite MSS and ETM+ data, acquired for two different dates between 1972 and 2001 analyzed by the software ERDAS/IMAGINE version 8.6 and ArcView 3.2 with the Spatial Analyst extension. Intensive ground truthing (160 training areas). Inventory of the flora: based on the data of the Herbarium Senckenbergianum (FR) in Frankfurt, Germany, and of the herbarium of the university of Ouagadougou (OUA), Burkina Faso, as well as on various investigations on the vegetation of Burkina Faso carried out in the years 1990 to 2005 by the team of the senior author. Life form analysis of the flora: based on the inventory of permanent plots. RESULTS AND DISCUSSION: Precipitation: Remarkable latitudinal shift of isohyets towards the South translates to a general reduction of average rainfall in great parts of the country. The last decade (1990-1999) shows some improvement, however, the more humid conditions of the 1950's and 1960's are not yet established again. Landcover change: In the study region the extent of arable fields and young fallows increased during the last 30 years from 580 km(2) in 1972 to 2870 km(2) in 2001. This means an average land cover conversion rate of 0.9% per year for the 6 departments considered. Change of the distribution of Sahelian and Sudanian species: Several species, mentioned in older literature as strictly Sahelian, today also occur in the Sudanian zone. Parallel to the spread of former strictly Sahelian species into the Sudanian zone, some former Sahelo-Sudanian species have withdrawn from the Sahel. Changes of the life form spectra of the flora: Considering their life form spectra, the flora of heavily grazed and of protected areas in the Sudanian zone show great differences. On areas intensively grazed the percentage of therophytes is evidently higher than on protected areas. Just the opposite is true for the phanerophytes. Their percentage is higher on the protected area than on the grazed zones. At the first glance, it is obvious to link the changes in flora and vegetation with the climate changes that have occurred during the last five decades (decrease of annual precipitation). However, not only climatic conditions have changed, but also population has increased, the percentage of land intensively used for agriculture and pasturing has increased and the time for soil regeneration today is much shorter than it was some decades ago. Thus, the landscape of the Sudanian zone has become a more Sahelian character. A comparison of the flora of an intensively used area of the Sudanian zone with that of a protected area shows a remarkable change in the life form spectra. The spectrum of the intensively used area is almost identical with that of the typical Sahelian flora. This comparison shows that the anthropogenic influence plays a greater role in the sahelisation of the Sudanian zone than the climate change. CONCLUSION: Climate change and anthropogenic influence both, lead to a sahelisation of landscape and flora. Thus in many parts of the Sudanian zone of West Africa sahelisation phenomena will remain and even increase independently from the reestablishment of the more humid climate conditions of the 1950ies. RECOMMENDATIONS AND PERSPECTIVES: In order to maintain some parts of the characteristic Sudanian landscape with its characteristic flora and vegetation, the number and size of protected areas should be augmented. For all protected areas it has to be ensured, that protection is reality, i.e. respected an understood by local people, not only fiction. As long as the enlargement of intensively used areas continues the sahelisation of flora, vegetation and landscape will continue too.     

Challenges in quantifying biosphere-atmosphere exchange of nitrogen species

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N(2) fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N(2)O, NO and bi-directional NH(3) exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols.     

Probability distributions of arsenic in soil from brownfield sites in Beijing (China): statistical characterization of the background populations and implications for site assessment studies

A probabilistic analysis was performed on soil arsenic concentration data from 4 brownfield sites at Beijing (Chaoyang and Haidian Districts), involved in environmental assessment studies. The available data sets were processed to provide a statistical characterization of the background populations and differentiate “anomalous data” from the natural range of variation of arsenic concentrations in soil. The site-specific background distributions and the existing wide-scale background values defined for the Beijing area were compared, discussing related implications for the definition of metal contamination soil screening levels (SSLs) in site assessment studies. The statistical analysis of As data sets discriminated site-specific background populations, encompassing 88% to 94% of the sample data, from outliers values, associated with either subsoil natural enrichments or possible anthropogenic releases. Upper Baseline Concentration (UBC) limits (+ 2σ level), including most of the site-specific metal background variability, were derived based on the statistical characterization of the background populations. Sites in the Chaoyang South District area had UBC values in the range 10.4–12.6 mg·kg^-1. These ranges provide meaningful SSL values to be adopted for As in local site assessment studies. Using the wide-scale background value for the Beijing area would have erroneously classified most of the areas in the subject sites as potentially contaminated.     

Secondary sexual characters signal fighting ability and determine social rank in Alpine ibex (Capra ibex)

Social dominance is a fundamental aspect of male evolutionary ecology in polygynous mammals because it determines access to estrous females. As it is rarely possible to monitor marked individuals of known morphology, little is known about the determinants of male dominance. We studied the social structure of Alpine ibex males in Gran Paradiso National Park, Italy in 2003, 2006, and 2007. Dominance interactions produced a linear social hierarchy. In ibex males, body mass and horn length are key traits in male-male combat, and both increase with age. We explored the links between age, body mass, horn length, and social rank. Ibex males showed much age-independent phenotypic heterogeneity and rapidly growing males reached high rank at a younger age than slow-growing males. Because there is no trade-off between horn growth and longevity, fast-growing males may face weak potential costs of rapid growth and high fitness benefit of achieving high rank. Violent interactions were more likely to occur between males similar in both mass and horn length, independently of age. We suggest that only high-quality individuals can afford a strategy of rapid growth for both secondary sexual characters, and likely reap substantial fitness benefits.     

The three-dimensionality of obstructed shear flows

Obstructed shear flows (i.e. those over permeable media) are common in the environment. An archetypal example, flow over a submerged vegetation canopy, is investigated here. Like any flow through complex geometry, canopy flows are characterised by strong spatial gradients. The focus of this experimental study is the three-dimensionality of aquatic canopy flow, in particular that of the coherent interfacial vortices that govern mixing into and out of the canopy. It is shown here that the vortices have a finite lateral scale that is comparable to their vertical scale; both are of the order of the drag length scale of the canopy, (C _D a)⁻¹, where a is the frontal area density and C _D is a bulk drag coefficient. The finite lateral extent of the vortices generates strong lateral hydrodynamic gradients, both instantaneously and in the long-term. The instantaneous gradients, which can contribute greatly to the dispersion of dissolved and particulate species, are far more pronounced. Finally, the potential for canopies to generate differential roughness secondary circulation is examined. In the consideration of vertical scalar transport, this circulation can be of the same order as turbulent diffusion.     

How humans shape wolf behavior in Banff and Kootenay National Parks, Canada

This paper describes the conceptualization and implementation of an agent-based model to investigate how varying levels of human presence could affect elements of wolf behavior, including highway crossings; use of areas in proximity to roads and trails; size of home ranges; activities, such as hunting, patrolling, resting, and feeding pups; and survival of individuals in Banff and Kootenay National Parks, Canada. The model consists of a wolf module as the primary component with five packs represented as cognitive agents, and grizzly bear, elk, and human modules that represent dynamic components of the environment. A set of environmental data layers was used to develop a friction model that serves as a base map representing the landscape over which wolves moved. A decision model was built to simulate the sequence of wolf activities. The model was implemented in a Java Programming Language using RePast, an agent-based modeling library. Six months of wolf activities were simulated from April 16 to October 15 (i.e., a season coherent with regard to known wolf behaviors), and calibrated with GPS data from wolf radiocollars (n = 15) deployed from 2002 to 2004. Results showed that the simulated trajectories of wolf movements were correlated with the observed trajectories (Spearman's rho 0.566, P < 0.001); other critical behaviors, such as time spent at the den and not traveling were also correlated. The simulations revealed that wolf movements and behaviors were noticeably affected by the intensity of human presence. The packs’ home ranges shrank and wolves crossed highways less frequently with increased human presence. In an extreme example, a wolf pack whose home range is traversed by a high-traffic-volume highway was extirpated due to inability to hunt successfully under a scenario wherein human presence levels were increased 10-fold. The modeling prototype developed in this study may serve as a tool to test hypotheses about human effects on wolves and on other mammals, and guide decision-makers in designing management strategies that minimize impacts on wolves and on other species functionally related to wolves in the ecosystem.     

Transcending scale dependence in identifying habitat with resource selection functions

Multi-scale resource selection modeling is used to identify factors that limit species distributions across scales of space and time. This multi-scale nature of habitat suitability complicates the translation of inferences to single, spatial depictions of habitat required for conservation of species. We estimated resource selection functions (RSFs) across three scales for a threatened ungulate, woodland caribou (Rangifer tarandus caribou), with two objectives: (1) to infer the relative effects of two forms of anthropogenic disturbance (forestry and linear features) on woodland caribou distributions at multiple scales and (2) to estimate scale-integrated resource selection functions (SRSFs) that synthesize results across scales for management-oriented habitat suitability mapping. We found a previously undocumented scale-specific switch in woodland caribou response to two forms of anthropogenic disturbance. Caribou avoided forestry cut-blocks at broad scales according to first- and second-order RSFs and avoided linear features at fine scales according to third-order RSFs, corroborating predictions developed according to predator-mediated effects of each disturbance type. Additionally, a single SRSF validated as well as each of three single-scale RSFs when estimating habitat suitability across three different spatial scales of prediction. We demonstrate that a single SRSF can be applied to predict relative habitat suitability at both local and landscape scales in support of critical habitat identification and species recovery.