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.     

Liver and renal lesions in mercury-contaminated narwhals (Monodon monoceros) from North West Greenland

Narwhals (Monodon monoceros) from North West Greenland are known to bioaccumulate mercury (Hg) in tissues and internal organs. This is postulated to be a health concern and therefore studies were undertaken to conduct a screening study of Hg concentrations and histopathology of liver and renal tissues in a total of 12 specimens. The sample consisted of two sub-adults (one male, one female) and 10 adult (six males, four females) collected in Qaanaaq (Thule) 2010. In liver, Hg mean ± SD was 11.88 ± 10.47 μg/g ww (range: 0.39?31.8 μg/g ww) while the concentrations in kidneys were 1.85 ± 1.20 μg/g ww (range: 0.41?4.03 μg/g ww). There was no marked difference in Hg concentrations between males and females while sub-adults had significantly lower concentrations. The histological examinations of renal tissue showed glomerular capillary dilatation and basement membrane thickening, dilatation, and hyalinization of Bowman's space/capsule and tubular lesions with hyaline casts accompanied by interstitial fibrosis in the kidneys. In liver tissue, portal cell infiltrates and fibrosis, bile duct proliferation, lipid-filled Ito cells, and steatosis were found. There was no marked difference in histological prevalence between males and females and in Hg concentrations in individuals with or without lesions. Four of seven renal lesions and one liver lesion were found in the two sub-adult whales. Based upon these findings, as well as the nature of the lesions, evidence suggests that histopathological alterations were a result of age but that Hg might be an aggravating co-factor in development of renal lesions in particular.     

Speciation and carcinogenic classification—some limits of assessment and prevention procedures—the case of “nickel”

The speciation of nickel is of the highest importance for the definition of lists of substances for regulatory activity in terms of prevention, regarding possible cancer risk. A review is made of the different attitudes of outstanding administrations in front of nickel speciation. Some of them show a maximum of care in chemical definition, others reflect a lack of scientific rigor leading to generic classifications, more or less abusive. The great complexity of the chemistry and physicochemistry of nickel imposes the “two‐level speciation concept” (chemical and physicochemical), at least for compliance with the “Good Laboratory Practice” as far as experimental toxicology is concerned. Recommendations are exposed for the attention of toxicologists and regulators who have been for some years now extremely solicited for prevention aims.     

Elucidating the function of ejaculate expulsion and consumption after copulation by female Euxesta bilimeki

Postcopulatory processes can influence male reproductive success in several animal species. Females can use different mechanisms to bias male paternity after copulation. One of such mechanisms consists in expelling all or part of the ejaculate after copulation. Euxesta bilimeki is an Ulidiid fly whose females not only frequently expel ejaculates after mating but also consume the ejaculate after expulsion. In order to understand the significance of these behaviors we examined video recordings of courtship, copulatory, and postcopulatory behaviours. The presence of sperm in female storage organs was confirmed after mating with males of different sizes and was correlated with duration of courtship, copulation, and the period from the end of copulation to ejaculate expulsion. The effect of ejaculate consumption on female fitness (fecundity and longevity) was compared among females held under different dietary treatments: a rich diet consisting of protein, sugar and water, an intermediate diet composed of sugar and water, a poor diet of only water and females that were completely deprived of food and water. All of the observed females expelled ejaculates after mating. The probability of storing sperm in the two spermathecae and the ventral receptacle was correlated with interactions between the duration of all behaviours examined and male size. Except for starved females, who lived longer when allowed to consume ejaculates, ejaculate consumption had no effect on fitness. Results suggest that females can bias sperm storage according to male mating effort, while the consumed ejaculate had some nutritional value only evident when females were completely starved.     

The role of Greenland sharks (Somniosus microcephalus) in an Arctic ecosystem: assessed via stable isotopes and fatty acids

The Greenland shark (Somniosus microcephalus) is the only shark species known to inhabit ice-covered seas in the North Atlantic, but remains a missing component in most studies of Arctic food webs. In the present study, stable isotopes (SIs) of nitrogen (δ¹⁵N) and carbon (δ¹³C) and fatty acids (FAs) were analyzed to identify the role of Greenland sharks (sampled during June 2008–2009) in Kongsfjorden, a productive fjord on the west coast of Svalbard, Norway (~79ºN, 12–13ºE). The Greenland shark fed at a high trophic position (4.8) based on δ¹⁵N values, and δ¹³C confirmed that most (70 %) of their carbon was derived from phytoplankton-based food chains, which is consistent with a heavy reliance on pelagic teleosts and seals. Greenland sharks from Kongsfjorden had fatty acid profiles in both muscle and plasma (e.g., low 20:1n-9, high 22:5n-3) that suggested a low portion of Greenland halibut (Reinhardtius hippoglossoides) and high proportion of gadoids and seals in their diet compared to Greenland sharks sampled in Cumberland Sound, Canada, during April 2008, which were previously shown to derive much of their energy from Greenland halibut. The high proportions of seal fatty acids in both slow- (muscle) and fast- (plasma) turnover tissues indicate that trophic interactions between Greenland sharks and seals in Kongsfjorden are a common occurrence. Results from the present study suggest that Greenland sharks likely play a unique and significant role in Arctic marine food webs as a top predator of fishes and marine mammals.     

Vertical infiltration of fuel oil hydrocarbons in an agricultural soil

The influence of rainfall, air temperature and soil moisture on the vertical mobility in the soil of fuel oil hydrocarbons (HC) was investigated in a field experiment. A controlled spreading of fuel oil (nC10‐nC25) was performed at a rate of 5 L HCm^‐2 on an agricultural soil in summer and in winter. Concentration, chemical composition of HC and soil moisture were regularly determined at different soil depths between 0 and 140 cm, 1 h, 3, 8and 15 days (d) after the spreading of oil. Sorption of hydrocarbons onto the organo‐mineral matrix of the soil was studied in laboratory experiments. The results showed that in summer, with an air temperature of 24°C and without water leaching in the soil profile, 65% of the initial HC remained trapped in the 0–140 cm soil layer, about 20% of the HC volatilized and around 15% migrated deeper. A vertical selective migration of the lightest (nC10‐nC15) HC (naphthas) was shown lSd after the spreading of fuel oil. Naphthas progressively reached the 120–140 cm soil layers whereas the heavy fractions of oil (nC17‐nC25) migrated and concentrated in the 0–60 cm soil layers. In winter, when soil was regularly watered by rainfalls and at low air temperatures, only 47% of the initial HC remained in the 0–140 cm profile after 15 d. A fast vertical infiltration of naphthas occurred within the first 3 d. After 15 d, all HC were detected in the same relative amounts as in the initial oil in the whole profile. Volatilization was negligible in winter and an increase in the migration of total oil at depth in the soil profile was shown. As inferred from the laboratory experiments, the high soil moisture led to the decrease in HC sorption on the organo‐mineral matter of the soil.     

Determining patterns of variability in ecological communities: time lag analysis revisited

All ecological communities experience change over time. One method to quantify temporal variation in the patterns of relative abundance of communities is time lag analysis (TLA). It uses a distance-based approach to study temporal community dynamics by regressing community dissimilarity over increasing time lags (one-unit lags, two-unit lags, three-unit lags). Here, we suggest some modifications to the method and revaluate its potential for detecting patterns of community change. We apply Hellinger distance based TLA to artificial data simulating communities with different levels of directional and stochastic dynamics and analyse their effects on the slope and its statistical significance. We conclude that statistical significance of the TLA slope (obtained by a Monte Carlo permutation procedure) is a valid criterion to discriminate between (i) communities with directional change in species composition, regardless whether it is caused by directional abundance change of the species or by stochastic change according to a Markov process, and (ii) communities that are composed of species with population sizes oscillating around a constant mean or communities whose species abundances are governed by a white noise process. TLA slopes range between 0.02 and 0.25, depending on the proportions of species with different dynamics; higher proportions of species with constant means imply shallower slopes; and higher proportions of species with stochastic dynamics or directional change imply steeper slopes. These values are broadly in line with TLA slopes from real world data. Caution must be exercised when TLA is used for the comparison of community time series with different lengths since the slope depends on time series length and tends to decrease non-linearly with it.