Predicting mobility of alkylimidazolium ionic liquids in soils

Background, aim, and scope  Ionic liquids (ILs) are a new class of alternative solvents that make ideal non-volatile media for a variety of industrial processes such as organic synthesis and biocatalysis, as alternative electrolytes, as phases and phase modifications in separation techniques, and as alternative lubricants. Once the large-scale implementation of ILs begins, the industrial application will follow. In view of their great stability, they could slip through classical treatment systems to become persistent components of the environment, where the long-term consequences of their presence are still unknown. Sorption on soils has a critical effect on the transport, reactivity, and bioavailability of organic compounds in the environment. So far, the IL sorption mechanism was investigated solely on the basis of batch experiments, which precluded any assessment of the dynamics of the process. An understanding of the mobility of ILs in soil columns is crucial for an accurate prediction of their fate in the soil. The aim of this study therefore was to investigate in detail the mobility of selected imidazolium ILs on three soil types. Moreover, it was decided to study these processes in soils from the coastal region (Gdańsk, Poland), which usually constitute a very important geochemical compartment, participating in the transport of contaminants on their way to the sea. Materials and methods  The mobility of alkylimidazolium ILs was investigated in columns containing soils from the coastal area. In addition, the sorption processes in all the soil systems studied were described isothermally and the equilibrium sorption coefficient was evaluated. The sorption capacities were determined according to OECD guidelines. Sorption dynamics was studied with use of polypropylene columns (diameter—10 mm, height—100 mm) packed with 10 g of soil. The ionic liquid solution was then injected into the soil column and left for 24 h to equilibrate. After this, a solution of 0.01 mM CaCl₂ was pumped through the column at a rate of 0.3 ml min^–1. Effluents were collected from the bottom of the column and analyzed by HPLC. Results  Sorption was strongest on the Miocene silt and the alluvial agricultural soil and weakest on the podsolic soil and Warthanian glacial till. The K _d value of long-chain ILs was far higher than that of the short-chain ones. Among the substances tested, hydroxylated ILs were usually more weakly sorbed. Desorption of ILs is inversely correlated with sorption intensity. The experimental results of the column tests correlate well with those from batch experiments. In the cases of weakly binding soils, ILs were detected almost immediately in the eluent. The elution profiles of long-chain ILs indicate that these compounds are very strongly sorbed onto most soils, although certain amounts were transported through the soil. ILs exhibit a certain mobility in soils: in particular, salts with short and/or hydroxylated side chains are extremely mobile. Discussion  The results indicate a stronger binding of ILs in the first sorption layer; once the first layer is saturated, there are no more active sites on the soil surface (no free charged groups); hence, there are no more strong electrostatic binding sites, and dispersive interaction becomes the dominant interaction potential. The influence of the structure of the ILs, especially the side-chain length was also confirmed: The K _d value of long-chain ILs was far higher than that of the short-chain ones. The long alkyl side chain facilitates dispersive interactions with soil organic matter and intermolecular binding, and the build-up of a second layer becomes possible. Among the substances tested, hydroxylated ILs were usually more weakly sorbed. The hydroxyl group in the side chain can alter the polarity of the compound so strongly that interaction with organic matter hardly occurs; these salts then remain in the aqueous phase. The experimental results from the column tests correlate well with those from batch tests. In the weakly binding soils (with low organic matter), the only binding to the soil surface must be via electrostatic interactions, although intermolecular van der Waals (ionic liquid–ionic liquid) interactions could also be taking place. The elution profile maxima for organic rich soils are far smaller than for the other soils. In the former, hydrogen bonding, dispersive and π…π interactions play a more important part than electrostatic interactions. The rapidly “disappearing” maxima of the elution peaks may indicate that, after elution of ILs from the second layer, it is difficult to extract further sorbed ILs. In the first layer, the ILs are bound by much stronger electrostatic interactions. To break these bonds, a greater energy is required than that sufficient to extract ILs from double sorption layers. Results indicate, moreover, that hydrophobic ILs will be sorbed in the first few centimeters of the soil; migration into the soil will therefore be almost negligible. Conclusions  Sorption of ILs was the strongest in soils with the highest cation exchange capacities and a high organic content. ILs were also more strongly bound to the first sorption layer. The sorption coefficients of long-chain ILs were far higher than those of short-chain ones; usually, hydroxylated derivatives were the least strongly sorbed. Results of soil column experiments to investigate the mobility of ILs in soils correlated well with those from batch tests, and the elution profiles were also well correlated with organic matter content. The observed rapidly disappearing elution peak maxima probably indicate that, after elution of the ILs from the second layer, it is difficult to extract further sorbed compounds. Recommendations and perspectives  Obtained results gave an interesting insight into mobility of ionic liquids in soil columns. However, several questions are now opened. It is therefore necessary to undertake further studies focused on total cycle of ionic liquids in the soil environment. This should include their evapotrasporation (lysimeter test), bioaccumulation by plants as well as degradation and transformation processes (chemical, biological, and physical) typically occurring in soils. Moreover, a further risk assessment of ILs is desirable since this study has indicated that these compounds, especially those with low lipophilicities, are generally mobile in the soil matrix. It is already known that short-chain ILs are characterized by low toxicities; should they enter the environment, they will probably migrate within the soil and pose a risk of contamination of surface and ground waters. This topic is relevant to the audience. Environmental threat of short-chain ionic liquids is currently unknown. From the predictive point of view, judging on known low acute toxic effects or high polarities of these compounds seems to be not enough to confirm their “environmental friendliness”. If we are to fully understand the potential environmental effects, one should also have an insight into long-term biological consequences of these ionic liquids, including chronic toxicity tests, bioaccumulation, and biotransformation rates as well as stability against natural elimination mechanisms.     

Correction to: Phenotypic and marker-assisted characterization of new apple genotypes with high resistance to fire blight

European Journal of Plant Pathology - A Correction to this paper has been published: https://doi.org/10.1007/s10658-021-02315-7     

Herbicidal activity of derivatives of 9-aminofluoren-9-ylphosphonic acid

A series of derivatives of 9-aminofluoren-9-ylphosphonic acid (phosphonic analogues of morphactins) were synthesized and screened for herbicidal activity against Lepidium sativum, Cucumis sativus and Lycopersicon esculentum. Ethyl 9-(N-alkylamino)fluoren-9-yl(phenyl)phosphinates appeared to be equipotent with glyphosate and thus may be recognized as new lead compounds for further structural modifications.     

Long-term estradiol-17β administration decreases the number of neurons in the caudal mesenteric ganglion innervating the ovary in sexually mature gilts

The effect of estradiol-17β (E(2)) on the number and distribution of neurons in the caudal mesenteric ganglion (CaMG) supplying the ovary of adult pigs was investigated. Also, the numbers of ovarian dopamine-β-hydroxylase (DβH-), neuropeptide Y (NPY-), somatostatin (SOM-), galanin (GAL-) and estrogen receptor (ER)-immunoreactive perikarya as well as the density of the intraganglionic nerve fibers containing DβH and/or NPY, SOM, GAL were determined. E(2) was administered i.m. from day 4 of the first studied estrous cycle to the expected day 20 of the second studied cycle. Injections of E(2) (1) increased the E(2) level in the peripheral blood approximately 4-5 fold, (2) decreased the number of small-sized Fast Blue-positive postganglionic neurons in the CaMG, (3) decreased the number of small perikarya in the ventral, dorsal and central regions of the CaMG, (4) decreased the number of large perikarya in the dorsal and central regions, (5) decreased the number of small and large perikarya in the CaMG that were DβH(+)/NPY(+), (6) decreased the number of small DβH(+) but NPY(-) perikarya, (7) decreased the number of small perikarya coded DβH(+)/SOM(+) and DβH(+)/SOM(-), (8) decreased the number of small DβH(+)/GAL(-) perikarya, (9) decreased the number of small and large perikarya expressing ER subtypes α and β and (10) decreased the total number of nerve fibers in the CaMG containing DβH and/or NPY and DβH and/or GAL. These results show that long-term E(2) treatment of adult gilts downregulates the populations of both noradrenergic and ERs expressing ovarian neurons in the CaMG. Our findings suggest also that elevated E(2) levels that occur during pathological states may regulate gonadal function(s) by affecting ovary supplying neurons.     

The tardigrade fauna of Tunisia,with an integrative description of Bryodelphax maculatus sp. nov. (Heterotardigrada: Echiniscidae)

The current knowledge of the diversity and distribution of tardigrade species in northern Africa is scarce and far from satisfactory. In this paper we review old and provide new faunistic records for various regions of Tunisia. Among the newly recorded taxa, we found a new heterotardigrade Bryodelphax maculatus sp. nov. The new species belongs to the weglarskae group, characterised by the presence of ventral plates, but differs from its congeners by a different arrangement of ventral plates and by conspicuous groups of cuticular tubercles on the ventral cuticle. The analysis of larval, juvenile and mature instars of the new species revealed, for the first time in heterotardigrades, ontogenetic variability in the development of ventral armature.

http://zoobank.org/urn:lsid:zoobank.org:pub:7EA21201-8C74-4BFD-8EAF-A131A78805F0     

BTH-mediated antioxidant system responses in apple leaf tissues

BTH (S-methylbenzo-1,2,3-thiadiazole-7-carbothiate), an active compound of the commercial preparation Bion, has been studied as an elicitor of resistance to fire blight (Erwinia amylovora) in apple. However, the biochemical mechanisms of its action are not fully elucidated. Our study indicated that BTH at the best time of its protection activity (2–14 days after application) induced changes in prooxidant–antioxidant balance in the leaves of apple trees, but in different ways in the enzymatic and nonenzymatic antioxidants. Glutathione as low molecular antioxidant as well as superoxide anion radical and lipid peroxides as oxidants exhibited changes at the early phase of BTH action. Glutathione-dependent enzymes were strongly affected by the elicitor used. On the 2nd day glutathione transferase (GST) and glutathione peroxidase (GSH-Px) activities increased by about 70% and 30% above the control, respectively. GST activity normalized about the 14th day but GSH-Px at the same time showed 27% of the control value. Among enzymes utilising hydrogen peroxide only catalase showed increase (37%) at the early phase of experiment. Compared with the control, BTH-treated plants did not show changes in ascorbate peroxidase and phenylalanine ammonia-lyase activities. Tocopherol (TOC) level diminished starting from the 7th day after BTH treatment and on the 14th day it was only 28% of the control. It is proposed that extinguishing of BTH-mediated signal resulted from TOC and glutathione action. The diminished ascorbate level at all examined times may play a crucial role in BTH-mediated cell growth regulation. The direct influence of BTH on lipid metabolism should be also taken into consideration.     

Effect of teleost pituitary gonadotropins on the in vitro maturation of carp oocytes

Studies were conducted on the effects of various kinds of teleost pituitary gonadotropins on the in vitro maturation of carp oocytes. It was ascertained that after 24 h of incubation with gonadotropins, the highest percentage of oocytes with the nucleus in the migrating or peripheral position, or of mature oocytes, was observed in the case of ciprinide gonadotropins.Centrifuged hypophysial homogenates of the pike, sea-trout and pike-perch displayed a considerably weaker activity. The results obtained are indicative of a specificity of teleost pituitary gonadotropins.     

Influence of lupin (Lupinus luteus L. cv. 4492 and Lupinus angustifolius L. var. zapaton) and fenugreek (Trigonella foenum-graecum L.) germination on microbial population and biogenic amines

Microbial population and bioactive amine profile and levels of two lupin species (Lupinus luteus L. cv. 4492 and Lupinus angustifolius L. var. zapaton) and fenugreek (Trigonella foenum-graecum L.) seeds as affected by germination were investigated. Microbial population increased considerably mainly in the first stage of germination (2 days), then small changes in bacterial numbers were observed up to 5 days to levels between 7.8 and 8.9 log colony-forming units/g. Microorganisms belonging to the Enterobacteriaceae family were dominant for the legumes tested. Ungerminated legume seeds contained putrescine, cadaverine, histamine, tyramine, spermidine, and spermine. Bioactive amine levels found in fenugreek seeds were between 3- and 4-fold higher than those found in lupin seeds. The highest total amine levels were found in fenugreek seeds [162 mg/kg of dry weight (dw)], followed by L. angustifolius var. zapaton seeds (84 mg/kg of dw) and, finally, L. luteus cv. 4492 (46 mg/kg of dw) seeds. The concentration of individual amines showed a gradual rising trend during the germination period in all tested sprouts, reaching levels >3 times higher than those found in ungerminated seeds. After 5 days of germination, the fenugreek sprouts contained the highest amount of total bioactive amines. Tyramine was the predominant amine in both lupin varieties, whereas cadaverine was the main bioactive amine detected in fenugreek. The results of this work thus indicated that microbial population and biogenic amine levels in the studied lupin and fenugreek sprouts are not a risk for healthy consumers or for individuals with restricted activity of detoxification enzymes.     

Association of the pine-infesting Pissodes species with ophiostomatoid fungi in Poland

Bark weevils are consistently associated with various fungi. They act as effective vectors for root-rot fungi, the rust pathogen and the ophiostomatoid fungi. In comparison with bark beetles, the interaction between ophiostomatoid fungi and bark weevils has been poorly studied in Europe. This study aims to clarify the ties among ophiostomatoid fungi and their weevil vectors in Pinus sylvestris. Samples associated with three bark weevils, including Pissodes castaneus, P. piniphilus and P. pini were collected from seven pine stands in Poland. Fungi were isolated from laboratory-reared and field-collected beetles, larvae and galleries of weevils. Isolates were identified based on morphology, DNA sequence comparison for two gene regions (ITS, ß-tubulin) and phylogenetic analyses. Fourteen morphological and phylogenetic ophiostomatoid species were identified among the 1,219 isolates. These 14 species included 11 novel associations between fungi and bark weevils. The most commonly encountered fungal associates of bark Pissodes species were Leptographium procerum, Ophiostoma quercus and O. minus. The spectrum of fungal associates was similar in three bark weevil species, despite some differences between species. Except for P. castaneus, all species of bark weevil were frequently associated with ophiostomatoid fungi. Pissodes castaneus does appear to be a consistent vector of L. procerum and Sporothrix inflata while O. minus, O. quercus and O. cf. rectangulosporium were often found in association with P. piniphilus and P. pini.