Detection of methylquinoline transformation products in microcosm experiments and in tar oil contaminated groundwater using LC-NMR

N-heterocyclic compounds are known pollutants at tar oil contaminated sites. Here we report the degradation of methyl-, and hydroxy-methyl-substituted quinolines under nitrate-, sulfate- and iron-reducing conditions in microcosms with aquifer material of a former coke manufacturing site. Comparison of degradation potential and rate under different redox conditions revealed highest degradation activities under sulfate-reducing conditions, the prevailing conditions in the field. Metabolites of methylquinolines, with the exception of 2-methylquinolines, were formed in high amounts in the microcosms and could be identified by ¹H NMR spectroscopy as 2(1H)-quinolinone analogues. 4-Methyl-, 6-methyl-, and 7-methyl-3,4-dihydro-2(1H)-quinolinone, the hydrogenated metabolites in the degradation of quinoline compounds, were identified by high resolution LC-MS. Metabolites of methylquinolines showed persistence, although for the first time a transformation of 4-methylquinoline and its metabolite 4-methyl-2(1H)-quinolinone is described. The relevance of the identified metabolites is supported by the detection of a broad spectrum of them in groundwater of the field site using LC-NMR technique. LC-NMR allowed the differentiation of isomers and identification without reference compounds. A variety of methylated 2(1H)-quinolinones, as well as methyl-3,4-dihydro-2(1H)-quinolinone isomers were not identified before in groundwater.     

Characterization of slow pyrolysis biochars: effects of feedstocks and pyrolysis temperature on biochar properties

Biochars are increasingly used as soil amendment and for C sequestration in soils. The influence of feedstock differences and pyrolysis temperature on biochar characteristics has been widely studied. However, there is a lack of knowledge about the formation of potentially toxic compounds that remain in the biochars after pyrolysis. We investigated biochars from three feedstocks (wheat straw, poplar wood, and spruce wood) that were slowly pyrolyzed at 400, 460, and 525°C for 5 h (straw) and 10 h (woodchips), respectively. We characterized the biochars' pH, electrical conductivity, elemental composition (by dry combustion and X-ray fluorescence), surface area (by N adsorption), water-extractable major elements, and cation exchange capacity (CEC). We further conducted differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffractometry to obtain information on the biochars' molecular characteristics and mineralogical composition. We investigated trace metal content, total polycyclic aromatic hydrocarbon (PAH) content, and PAH composition in the biochars. The highest salt (4.92 mS cm) and ash (12.7%) contents were found in straw-derived biochars. The H/C ratios of biochars with highest treatment temperature (HTT) 525°C were 0.46 to 0.40. Surface areas were low but increased (1.8-56 m g) with increasing HTT, whereas CEC decreased (162-52 mmol kg) with increasing HTT. The results of DSC and FTIR suggested a loss of labile, aliphatic compounds during pyrolysis and the formation of more recalcitrant, aromatic constituents. X-ray diffractometry patterns indicated a mineralogical restructuring of biochars with increasing HTT. Water-extractable major and trace elements varied considerably with feedstock composition, with trace elements also affected by HTT. Total PAH contents (sum of EPA 16 PAHs) were highly variable with values up to 33.7 mg kg; irrespective of feedstock type, the composition of PAHs showed increasing dominance of naphthalene with increasing HTT. The results demonstrate that biochars are highly heterogeneous materials that, depending on feedstock and HTT, may be suitable for soil application by contributing to the nutrient status and adding recalcitrant C to the soil but also potentially pose ecotoxicological challenges.     

Molecular structures and associations of humic substances in the terrestrial environment

Here we show, for the first time, evidence of the primary molecular structures in humic substances (HS), the most abundant naturally occurring organic molecules on Earth, and their associations as mixtures in terrestrial systems. Multi-dimensional nuclear magnetic resonance (NMR) experiments show us that the major molecular structural components in the mixtures operationally defined as HS are aliphatic acids, ethers, esters and alcohols; aromatic lignin derived fragments; polysaccharides and polypeptides. By means of diffusion ordered spectroscopy, distinct diffusion coefficients consistent with relatively low molecular weight molecules were observed for all the components in the mixtures, and saccharides were the largest single class of component present. Liquid chromatography NMR confirmed that HS components can be easily separated and nuclear Overhauser effect (NOE) enhancements support the finding that the components are of relatively low molecular weight <~2,000 Da. The widely recognized properties of HS, i.e., characteristics indicative of crosslinked, macromolecular networks, can now be explained as aggregation of mixtures, most likely instigated by complexation with metal cations.     

Validating a Safety Climate Model in Metal Processing Industries: A Replication Study

This paper attempts to replicate a safety climate model originally tested in Australia to assess its applicability in a different context: namely, across production workers in 22 medium-sized metal processing organizations in Austria. The model postulates that safety knowledge and safety motivation mediate the relation between safety climate on the one hand and safety compliance and participation on the other. Self-report data from 1075 employees were analyzed using structural equation modeling (SEM). The results of the replication study largely confirmed the original safety climate model. However, in addition to indirect effects, direct links between safety climate and actual safety behavior were found.     

Pulverized coal stream ignition delay under conventional and oxy-fuel combustion conditions

The coal stream ignition process is critical to the performance of modern pulverized coal burners, particularly when operating under novel conditions such as experienced in oxy-fuel combustion. However, experimental studies of coal stream ignition are lacking, and recent modeling efforts have had to rely on comparisons with a single set of experiments in vitiated air. To begin to address this shortfall, we have conducted experiments on the ignition properties of two U.S. and two Chinese coals in a laminar entrained flow reactor. Most of the measurements focused on varying the coal feed rate for furnace temperatures of 1230–1320 K and for 12–20 vol.% O₂ in nitrogen. The influence of coal feed rate on ignition with a carbon dioxide diluent was also measured for 20 vol.% O₂ at 1280 K. A second set of measurements was performed for ignition of a fixed coal feed rate in N₂ and CO₂ environments at identical furnace temperatures of 1200 K, 1340 K, and 1670 K. A scientific CCD camera equipped with a 431 nm imaging filter was used to interrogate the ignition process. Under most conditions, the ignition delay decreased with increasing coal feed rate until a minimum was reached at a feed rate corresponding to a particle number density of approximately 4 × 10⁹ m^?3 in the coal feed pipe. This ignition minimum corresponds to a cold flow group number, G, of ～0.3. At higher coal feed rates the ignition delay increased. The ignition delay time was shown to be very sensitive to (a) the temperature of the hot coflow into which the coal stream is introduced, and (b) the coal particle size. The three high volatile bituminous coals showed nearly identical ignition delay as a function of coal feed rate, whereas the subbituminous coal showed slightly greater apparent ignition delay. Bath gas CO₂ content was found to have a minor impact on ignition delay.     

Kin discriminators in the eusocial sweat bee <Emphasis Type="Italic">Lasioglossum malachurum</Emphasis>: the reliability of cuticular and Dufour’s gland odours

The ability to discriminate degrees of relatedness may be expected to evolve if it allows unreciprocated altruism to be preferentially directed towards kin (Hamilton in J Theor Biol 7:1–16, 1964). We explored the possibility of kin recognition in the primitively eusocial halictid bee Lasioglossum malachurum by investigating the reliability of worker odour cues that can be perceived by workers to act as indicators of either nest membership or kinship. Cuticular and Dufour’s gland compounds varied significantly among colonies of L. malachurum, providing the potential for nestmate discrimination. A significant, though weak, negative correlation between chemical distance and genetic relatedness (r = −0.055, p < 0.001) suggests a genetic component to variation in cuticular bouquet, but odour cues were not informative enough to discriminate between different degrees of relatedness within nests. This pattern of variation was similar for Dufour’s gland bouquets. The presence of unrelated individuals within nests that are not chemically different from their nestmates suggests that the discrimination system of L. malachurum is prone to acceptance errors. Compounds produced by colony members are likely combined to generate a gestalt colony chemical signature such that all nestmates have a similar smell. The correlation between odour cues and nest membership was greater for perceived compounds than for non-perceived compounds, suggesting that variability in perceived compounds is a result of positive selection for nestmate recognition despite potentially stabilising selection to reduce variability in odour differences and thereby to reduce costs derived from excessive intracolony nepotistic behaviour.     

Habitat use of a multispecific seagrass meadow by green turtles Chelonia mydas at Mayotte Island

We investigated the habitat use in green turtles exploiting a 13-ha multispecific seagrass meadow at Mayotte Island, south-western Indian Ocean. A phyto-ecological survey shows the occurrence of eight seagrass species, dominated by Halodule uninervis and Syringodium isoetifolium, distributed according to four distinct seagrass communities along the depth gradient. Direct underwater censuses show that green turtles occurred all over the meadow. Yet when community relative surface area was taken into account green turtles preferentially frequented the most seaward, biomass-richer S. isoetifolium-dominated community, suggesting that green turtles compensate for their intrinsically nutrient-poor herbivorous diet. Additionally, smaller (<80 cm standard curved carapace length, SCCL) individuals also preferentially occurred in the most shoreward H. univervis-dominated community where no larger (>80 cm SCCL) individuals were sighted, suggesting habitat use is indicative of diet selection and may reflect size-specific food requirements and physiology.     

Environmental impact of historical harbour city Zadar (Croatia) on the composition of marine sediments and soils

Large amounts of oyster shells are produced as a by-product of shellfish farming in coastal regions without beneficial use options. Accordingly, this study was conducted to evaluate the potential for the use of waste oyster shells (WOS) containing a high amount of CaCO₃ to improve soil quality and to stabilize heavy metals in soil. To accomplish this, an incubation experiment was conducted to evaluate the ability of the addition of 1–5 wt% WOS to stabilize the Pb (total 1,246 mg/kg) and Cd (total 17 mg/kg) in a contaminated soil. The effectiveness of the WOS treatments was evaluated using various single extraction techniques. Soil amended with WOS was cured for 30 days complied with the Korean Standard Test method (0.1 M·HCl extraction). The Pb and Cd concentrations were less than the Korean warning and countermeasure standards following treatment with 5 wt% WOS. Moreover, the concentrations of Cd were greatly reduced in response to WOS treatment following extraction using 0.01 M·CaCl₂, which is strongly associated with phytoavailability. Furthermore, the soil pH and exchangeable Ca increased significantly in response to WOS treatment. Taken together, the results of this study indicated that WOS amendments improved soil quality and stabilized Pb and Cd in contaminated soil. However, extraction with 0.43 M·CH₃COOH revealed that remobilization of heavy metals can occur when the soil reaches an acidic condition.     

Variation in sex pheromone emission does not reflect immunocompetence but affects attractiveness of male burying beetles—a combination of laboratory and field experiments

Life history theory predicts a trade-off between male sexual trait expression and immunocompetence. Using burying beetles, Nicrophorus vespilloides, as a model, we investigated the relationship between male immune function, sex pheromone emission, and attractiveness under field conditions. In the first experiment, we tested whether there is a positive correlation between immune capacity, sex pheromone characteristics (quantity, relative composition, and time invested in pheromone emission), and male attractiveness. As a measurement of immune capacity, we used an individual’s encapsulation ability against a novel antigen. In the second experiment, we specifically examined whether a trade-off between chemical trait expression and immune function existed. To this end, we challenged the immune system and measured the subsequent investment in sex pheromone emission and the attractiveness of the male under field conditions. We found that a male’s immunocompetence was neither related to the emission of the male’s sex pheromone nor to its attractiveness in the field. Furthermore, none of the immune-challenge treatments affected the subsequent investment in pheromone emission or number of females attracted. However, we showed that the same males that emitted a high quantity of their sex pheromone in the laboratory were able to attract more females in the field. Our data suggest that the chemical signal is not a reliable predictor of a male’s immunocompetence but rather is a general important fitness-related trait, with a higher emission of the sex pheromone measured in the laboratory directly affecting the attractiveness of a male under field conditions.