Analytical model for site-specific isotope fractionation in 13C during sorption: determination by isotopic 13C NMR spectrometry with vanillin as model compound

The aim of this study was to conceive a reactive transport model capable of providing quantitative site-specific enrichment factors for fractionation in ¹³C isotopic content during sorption. As test compound the model treats vanillin, for which the ¹³C isotopic content at natural abundance at each of the 8 carbon positions can be measured by quantitative ¹³C nuclear magnetic resonance spectrometry. This technique determines the isotope ratios with a resolution better than ±1‰ (0.1%) at each carbon position. Site-specific isotope fractionations were recorded in chromatography column experiments with silica RP-18 as stationary phase. The one dimensional reactive transport model accounted for the sorption/desorption behavior of 8 individual ¹³C-isotopomers and one ¹²C-isotopomer of vanillin and reproduced satisfactorily the bulk (average over the whole compound) fractionation observed during elution. After model calibration, the enrichment factors were fitted for each carbon site where a significant fractionation was recorded. To show the interest of such a transport model for environmental studies, the model, extended to three dimensions, was exploited to simulate reactive transport in an aquifer. These results show that significant ¹³C isotope fractionation is expected for 4 out of 8 ¹³C-isotopomers in vanillin, and illustrate that bulk isotope ratios measured by conventional compound specific isotope analysis and mass spectrometry would hardly document significant isotope fractionations in vanillin. It is concluded that modeling of site-specific isotope ratios in molecules is a priori feasible and may help to quantify unknown processes in the environment.     

Environmental evaluation of transfer and treatment of excess pig slurry by life cycle assessment

Slurry management is a central topic in the agronomic and environmental analysis of intensive livestock production systems. The objective of this study is to compare the environmental performance of two scenarios of collective slurry management for the disposal of excess nitrogen from animal manure. The scenarios are the transfer of slurry and its injection to crop land, and the treatment of slurry in a collective biological treatment station. The study is based on a real case in the West of France, where a group of farmers is developing a collective plan for the disposal of almost 7000 m(3) of excess pig slurry. The evaluation is carried out by Life Cycle Assessment, where emissions and resource consumption are quantified and aggregated into four environmental impact categories: eutrophication, acidification, climate change, and non-renewable energy use. Ammonia emitted is the most important contributor to acidification and eutrophication, while methane contributes most to climate change. Both ammonia and methane are mostly emitted during the storage of slurry and, in the case of the treatment scenario, also during composting the solid fraction of the slurry. The two management strategies are similar with respect to climate change, whereas eutrophication and acidification are twice as large for treatment relative to transfer. Electricity needed for the treatment process is the main contributor to non-renewable energy use for the treatment scenario, while the transfer scenario represents a net energy saving, as energy saved by the reduction of mineral fertiliser use more than compensates for the energy needed for transport and injection of slurry. The overall environmental performance of transfer is better than that of treatment, as it involves less acidification, eutrophication and non-renewable energy use. The method employed and the results obtained in this study can provide elements for a transparent discussion of the advantages and disadvantages of contrasting excess slurry management scenarios as well as the identification of the main aspects determining their environmental performance.     

Declining levels of PCB, HCB and p,p′-DDE in adipose tissue from food producing bovines and swine in Sweden 1991–2004

The official control programme for organochlorine (OC) contaminants in food producing animals in Sweden was used to study temporal and spatial trends of the polychlorinated biphenyl CB 153, hexachlorobenzene (HCB) and p,p′-DDE in adipose tissue from bovines and swine 1991–2004. Our results show that efforts to decrease OC contamination of animal feed and the environment have had a positive impact on the contamination of the animal production. OC concentrations declined significantly in almost all studied regions of Sweden. OC temporal trends were slower in bovines (6–8% per year) than in swine (10–12%). Power analyses showed that data from more than 10 years of sampling were needed for a detection of an annual OC level change of 5% in both species in the control programme, due to large within- and between-year variation in OC levels. CB 153 and p,p′-DDE levels were higher in southern than in northern Sweden. Levels decreased with age in milk cows, but not in young nulliparous cows (heifers) and bulls. Moreover, milk cows and bulls had significantly lower OC levels than heifers. Levels were not age-dependent among swine, but castrated male swine (barrows) had significantly lower OC levels than young female swine (gilts). Levels of the studied OCs are now in many cases below the LOQ of the analytical method used. Future time trend studies of these OCs thus depend on lowered LOQs in the control programme.     

Information seeking in documents by pilots: Assessment of the reliability problems caused by the transition from paper to electronic

Information seeking is completely ignored in research on aviation psychology and more generally in issues of air transport safety. But information seeking occupies a central place in the pilots’ work. And this activity is undergoing an important development: the transition from paper to electronic documents. A contribution to the assessment of this transition is presented here. The assessment is focused on deterioration of information access, understanding and exploitation, and their possible negative consequences in terms of reliability. The exploitation of the documentation by pilots, and particularly the information seeking activity, are described and linked to their contexts (i.e. the main tasks of flying that require information seeking). Then an users test is presented where some information-seeking tasks are evaluated in terms of cost and errors, by comparing electronic and paper documents. The results show that electronic documents provide new functions that seem useful but also that too many new functions generate difficulties. Then it seems that pilots need some time to learn how to use these new documents. Reducing attention needed to perform a task such as calculation is risky. Some aspects of information seeking by the pilots should be better analysed and evaluated.     

Bringing the outside in: Can “external” workers experience insider status?

The current study examines the possibility that agency workers can experience perceived insider status despite their assumed “outsider” category. One hundred ninety‐one agency workers from Canadian financial firms completed surveys assessing agency worker perceptions regarding the level of support from both their supervisors and the client firms' permanent workers, as well as the agency workers' level of perceived insider status and affective commitment toward the client firm. Agency worker supervisors (within the client firm) assessed the agency workers' level of interpersonal facilitation. Results indicate that: (1) Agency workers can experience perceived insider status, regardless of their objective classification as outsiders; (2) perceived support from supervisors and the client firms' permanent workers contribute to agency worker perceptions of insider status; and (3) perceptions of insider status are associated with higher levels of both affective commitment and interpersonal facilitation, even in workers that are considered marginally tied to the organization. Copyright © 2009 John Wiley & Sons, Ltd.     

Passaic river sediment interstitial water phase I toxicity identification evaluation

A suite of tests was conducted to evaluate and identify the cause or causes of toxicity in Passaic River sediments. Sediment toxicity was measured with three types of bioassays: a whole sediment bioassay with the marine amphipod, Ampelisca abdita, and interstitial water bioassays with A. abdita and the bioluminescent bacterium Vibrio fisheri (Microtox((R))). In addition, a Phase I Toxicity Identification Evaluation (TIE) was conducted to elucidate the cause of observed toxicity. Analytical concentrations of selected residues in whole sediment and interstitial water from the five sampling stations were considered in conjunction with the conclusions drawn from the toxicity tests and Phase I TIE results. Finally, a toxic units approach was used to evaluate the predicted toxicity of measured interstitial water residue concentrations. There was a lack of toxic response in the short-term interstitial water bioassays, indicating that oxidants, soluble forms of metals, and dissolved phase neutral organics were not likely toxicants. However, there was significant toxicity indicated by the whole sediment A. abidita bioassays. After 10 days, there was complete or near complete mortality in amphipods exposed to all of the sediment samples tested. Removal of interstitial water toxicity by filtration was common to all four stations that exhibited measurable initial toxicity. The observed toxicity characteristics are consistent with particle associated neutral organics. This conclusion is supported by toxicity removal via filtration, lack of toxicity in the Microtox((R)) assays, and the fact that whole sediments were more toxic than was interstitial water.     

Coupling occurs before breakdown during biotransformation of Acid Blue 62 by white rot fungi

Only few data exist on the metabolites produced during the biotransformation of anthraquinonic dyes by white rot fungi (WRF). During the biotransformation of an anthraquinonic dye Acid Blue 62 (ABu62) using Pycnoporus sanguineus MUCL 41582 strain, it was previously demonstrated that the blue colour of the medium turned to red before complete dye decolourisation. To better understand the phenomenon, this study carried out ABu62 biotransformation with five different WRF strains (Coriolopsis polyzona MUCL 38443, Perenniporia ochroleuca MUCL 41114, Perenniporia tephropora MUCL 41562, P. sanguineus MUCL 38531 and Trametes versicolor MUCL 38412) and compared with P. sanguineus MUCL 41582 previously described. A multi-methodological approach (using capillary electrophoresis, mass spectrometry, HPLC, UV, NMR and IR spectroscopies) was developed to characterise the metabolites involved and monitor their apparition. Seven metabolites were commonly found with all strains, suggesting a common metabolic pathway for ABu62 biotransformation. During the first days, dimer and oligomers of the initial ABu62 molecule were observed: the main one absorbed in the 500nm region, explaining the red colour appearance of the medium. This main metabolite was made up of two molecules of ABu62 linked by an azo bond, minus a cyclohexyl moiety. After a longer incubation time, breakdown products were observed. Based on these products characterizations, a bioconversion pathway was proposed.     

A long-term monitoring study of chlorophyll,microbial contaminants,and pesticides in a coastal residential stormwater pond and its adjacent tidal creek

Stormwater ponds are commonly used in residential and commercial areas to control flooding. The accumulation of urban contaminants in stormwater ponds can lead to water-quality problems including nutrient enrichment, chemical contamination, and bacterial contamination. This study presents 5 years of monitoring data assessing water quality of a residential subdivision pond and adjacent tidal creek in coastal South Carolina, USA. The stormwater pond is eutrophic, as described by elevated concentrations of chlorophyll and phosphorus, and experiences periodic cyanobacterial blooms. A maximum monthly average chlorophyll concentration of 318.75 μg/L was measured in the stormwater pond and 227.63 μg/L in the tidal creek. Fecal coliform bacteria (FCB) levels were measured in both the pond and the tidal creek that exceeded health and safety standards for safe recreational use. A maximum monthly average FCB level of 1,247 CFU/100 mL was measured in the stormwater pond and 12,850 CFU/100 mL in the tidal creek. In addition, the presence of antibiotic resistant bacteria and pathogenic bacteria were detected. Low concentrations of herbicides (atrazine and 2,4-D), a fungicide (chlorothalonil), and insecticides (pyrethroids and imidacloprid) were measured. Seasonal trends were identified, with the winter months having the lowest concentrations of chlorophyll and FCB. Statistical differences between the stormwater pond and the tidal creek were also noted within seasons. The tidal creek had higher FCB levels than the stormwater pond in the spring and summer, whereas the stormwater pond had higher chlorophyll levels than the tidal creek in the summer and fall seasons. Chlorophyll and FCB levels in the stormwater pond were significantly correlated with monthly average temperature and total rainfall. Pesticide concentrations were also significantly correlated with temperature and rainfall. Pesticide concentrations in the stormwater pond were significantly correlated with pesticide concentrations in the adjacent tidal creek. Chlorophyll and FCB levels in the tidal creek, however, were not significantly correlated with levels in the pond. While stormwater ponds are beneficial in controlling flooding, they may pose environmental and human health risks due to biological and chemical contamination. Management to reduce residential runoff may improve water quality in coastal stormwater ponds and their adjacent estuarine ecosystems.     

Singular Spectrum Analytic (SSA) Decomposition and Reconstruction of Flowering: Signatures of Climatic Impacts

An empirical approach for the decomposition and reconstruction of long-term flowering records of eight eucalypt species is presented. Results from singular spectrum analysis (SSA) allow for characterisation of the dynamic and complex flowering patterns in response to temperature and rainfall throughout the year. SSA identified trend, annual, biennial and other sub-components of flowering. The ability to discriminate flowering and climate relationships is demonstrated based on SSA (cross-)correlation analysis. SSA also identified the cyclical influence of temperature and rainfall on peak flowering. For each species, there is, on average, 6 months of the annual cycle when temperature positively influences flowering and 6 months when the influence of temperature is negative. For all species, rainfall exerts a negative influence when temperature is positive. Investigation of short-term and long-term lags of climate on flowering provided best-case climatic scenarios for each species’ flowering; e.g. more intense peak flowering is likely in Eucalyptus leucoxylon when cool, wet conditions coincide with peak flowering and is further enhanced if the preceding autumn and winter were warm and dry, and the previous spring and summer cool and wet. Three clear species groupings, according to similar SSA (cross-)correlation signatures, were identified: (1) E. leucoxylon and E. tricarpa; (2) E. camaldulensis, E. melliodora and E. polyanthemos and (3) E. goniocalyx, E. microcarpa and E. macrorhyncha. Lastly, change point years for flowering based on SSA sub-components in four of the species seem to align with years of major shift in global ENSO signal (1951/1957/1958) as indicated by the extended multivariate ENSO index.