scholarly journals Identifying degradation products responsible for increased toxicity of UV-degraded insensitive munitions

2021 ◽  
Author(s):  
Lee Moores ◽  
Alan Kennedy ◽  
Lauren May ◽  
Shinita Jordan ◽  
Anthony Bednar ◽  
...  

Degradation of insensitive munitions (IMs) by ultraviolet (UV) light has become a concern following observations that some UV-degradation products have increased toxicity relative to parent compounds in aquatic organisms. This investigation focused on the Army's IM formulation, IMX-101, composed of three IM constituents: 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and nitroguanidine (NQ). The IM constituents and IMX-101 were irradiated in a UV photo-reactor and then administered to Daphnia pulex in acute (48 h) exposures comparing toxicities relative to the parent materials. UV-degradation of DNAN had little effect on mortality whereas mortality for UV-degraded NTO and NQ increased by factors of 40.3 and 1240, making UV-degraded NQ the principle driver of toxicity when IMX-101 is UV-degraded. Toxicity investigations for specific products formed during UV-degradation of NQ, confirmed greater toxicity than the parent NQ for degradation products. Summation of the individual toxic units for the complete set of individually measured UV-degradation products identified for NQ only accounted for 25% of the overall toxicity measured in the exposures to the UV-degraded NQ product mixture. Given the underestimation of toxicity using the sum toxic units for the individually measured UV-degradation products of NQ, we conclude that: (1) other unidentified NQ degradation products contributed principally to toxicity and/or (2) synergistic toxicological interactions occurred among the NQ degradation product mixture that exacerbated toxicity.

2021 ◽  
Author(s):  
Sandrine Charles ◽  
Aude Ratier ◽  
Virgile Baudrot ◽  
Gauthier Multari ◽  
Aurélie Siberchicot ◽  
...  

Abstract In the European Union, more than 100,000 man-made chemical substances are awaiting an environmental risk assessment (ERA). Simultaneously, ERA of chemicals has now entered a new era. Indeed, recent recommendations from regulatory bodies underline a crucial need for the use of mechanistic effect models, allowing assessments that are not only ecologically relevant, but also more integrative, consistent and efficient. At the individual level, toxicokinetic-toxicodynamic (TKTD) models are particularly encouraged for the regulatory assessment of pesticide-related risks on aquatic organisms. In this paper, we first propose a brief review of classical dose-response models to put into light the on-line MOSAIC tool offering all necessary services in a turnkey web platform whatever the type of data to analyze. Then, we focus on the necessity to account for the time-dimension of the exposure by illustrating how MOSAIC can support a robust calculation of bioaccumulation factors. At last, we show how MOSAIC can be of valuable help to fully complete the EFSA workflow regarding the use of TKTD models, especially with GUTS models, providing a user-friendly interface for calibrating, validating and predicting survival over time under any time-variable exposure scenario of interest. Our conclusion proposes a few lines of thought for an even easier use of modelling in ERA.


2021 ◽  
Author(s):  
Florentina Laura Chiriac ◽  
Catalina Stoica ◽  
Iuiana Paun ◽  
Florinela Pirvu ◽  
Toma Galaon ◽  
...  

Abstract Organic UV-filters, including 4-hydroxybenzophenone (4-HBP) and 2,4-dihydroxybenzophenone (BP-1), are persistent emerging contaminants whose presence in the environment poses a threat to aquatic organisms due to their endocrine disruptor’s properties. For this reason, finding suitable technological processes for their safety and efficient removal from the environment represent a priority for the scientific community. To the author’s knowledge, until now, there are no studies reporting the biodegradation of 4-HBP and BP-1 by a single bacteria strain. In this paper, there were tested the 4-HBP and BP-1 biodegradation potential of two Gram-positive (Staphylococcus aureus and Enterococcus faecalis) and two Gram-negative (Salmonella typhimurium and Serratia rubidae). The 4-HPB biodegradation process was observed only in the presence of Gram-negative bacterial strains. Thus, the biodegradation rates of 4-HBP reached up to 12.7% after 24h of incubation in presence of Salmonella thyphimurium and up to 24.0% after 24h of incubation with Serratia rubidae. Staphylococcus aureus was able to biodegrade 26.7% of BP-1, while Salmonella thiphymurium was able to biodegrade 14.7% of BP-1 after 24h of incubation. Their biodegradation products generated during the 4-HBP biodegradation process by Serratia rubidae were analyzed through LC-MS/MS analysis. The (bio)degradation products were benzophenone and a multi-hydroxylated derivative of 4-HBP and the degradation pathways were proposed. The data obtained in this study gave important information regarding the 4-HBP and BP-1 potential biodegradation by single bacterial strains.


2021 ◽  
Author(s):  
Bijoli Mondal ◽  
Shib Sankar Basak ◽  
Arnab Das ◽  
Sananda Sarkar ◽  
Asok Adak

Abstract In the photochemical UV-H2O2 advanced oxidation process, H2O2 absorbs UV light and is decomposed to form hydroxyl radicals (OH·), which are highly excited and reactive for electron-rich organic compounds and hence can degrade organic compounds. In the present work, the UV-H2O2 process was investigated to degrade ciprofloxacin (CIP), one of India's widely used antibiotics, from aqueous solutions using a batch type UV reactor having photon flux = 1.9 (± 0.1) ×10-4 Einstein L-1 min-1. The effects of UV irradiation time on CIP degradation were investigated for both UV and UV-H2O2 processes. It was found that about 75% degradation of CIP was achieved within 60 s with initial CIP concentration and peroxide concentration of 10 mg L-1 and 1 mol H2O2/ mol CIP, respectively, at pH of 7(±0.1) and fluence dose of 113 mJ cm-2. The experimental data were analyzed by the first-order kinetics model to find out the time- and fluence-based degradation rate constants. Under optimized experimental conditions (initial CIP concentration, pH and H2O2 dose of 10 mg L-1, 7(±0.1) and 1.0 mol H2O2 / mol CIP, respectively), the fluence-based pseudo-first-order rate constant for the UV and UV-H2O2 processes were determined to be 1.28(±0.0) ×10-4 and 1.20(±0.04) ×10-2 cm2 mJ-1 respectively. The quantum yields at various pH under direct UV were calculated. The impacts of different process parameters such as H2O2 concentration, solution pH, initial CIP concentration, and wastewater matrix on CIP degradation were also investigated in detail. CIP degradation was favorable in acidic conditions. Six degradation products of CIP were identified. Results clearly showed the potentiality of the UV-H2O2 process for the degradation of antibiotics in wastewater.


1930 ◽  
Vol 7 (2) ◽  
pp. 109-131 ◽  
Author(s):  
G. L. CLARKE

1. A method is described for studying the responses of Daphnia to changes of light intensity with special attention to the behaviour of the individual and to the avoidance of "shock" effects. The types of apparatus used provide for rigid control of the temperature, for illumination from any direction, and for an adjustable rate of change of the light intensity by means of a chemical rheostat. 2. The great majority of Daphnia magna and Daphnia pulex were found to be primarily negatively phototropic and positively geotropic. That is, they always exhibited those tropistic signs under constant conditions of illumination. 3. A reduction of the light intensity causes a temporary reversal of the tropism signs. The secondary signs thus produced are positive phototropism and negative geotropism. 4. The presence of both phototropic and geotropic forces is proved by experiments in which illumination is (1) from one side, (2) from beneath, and (3) from two opposing sides or from above and below simultaneously. In these tests and in others in which very slow and very fast rates of dimming are used the phototropic and geotropic forces are resolved, antagonised, and neutralised in succession. The responses of the Daphnia indicate that there are two types of animals which exhibit exactly the same tropisms, but in one type phototropism is the stronger while in the other geotropism is the stronger. 5. In this material it was found that the temporary secondary tropistic signs persisted only a few minutes while the primary signs persisted for hours, although this effect was somewhat less marked in weak light or in darkness. 6. The difference between "time-change" and "place-change" of light in tensity is pointed out. Daphnia is stimulated by both types of change if the rate of change is sufficiently great. 7. That photosensitive animals are stimulated to respond to changes in the intensity of light only and are merely orientated by the direction of the light is shown in the work of previous, investigators as well as in this paper. The rigidity of this mechanism is indicated by experiments in which the light is graded in intensity at right angles to its direction and in which the light is rendered converging and diverging by a lens. 8. Evidence is given for believing that there is no "absolute optimum" light intensity for Daphnia but that a "relative optimum" exists which is the intensity to which the animals are adapted at the moment. 9. The interval between the inception of the reduction of the light intensity and the beginning of swimming movements in response is called the latent period. The faster the rate of dimming, the shorter is the duration of the latent period. A minimum, amount of intensity change is required to produce any response, at any speed, but beyond that the slower the rate of dimming, the greater is the amount of change required and hence the lower is the absolute intensity at which the response takes place. Ordinarily, the response is maximal in respect to both rate and magnitude. 10. Fatigue will interfere with experimentation unless guarded against. 11. Specimens of Daphinia with reversed primary signs gain temporary secondary signs following an increase of light intensity; otherwise they behave like the more usual forms. 12. The possibility that the processes of adaptation in Daphnia may account for the photic responses observed is discussed. Support for this theory is derived from the fact that it is possible to dim the light over a given range at such a slow rate that no response is produced.


1994 ◽  
Vol 8 (3) ◽  
pp. 591-597 ◽  
Author(s):  
John D. Nalewaja ◽  
Robert Matysiak ◽  
Edward Szelezniak

Experiments were conducted to determine the influence of spray carrier salts, UV light, and temperature on sethoxydim phytotoxicity to oat or yellow foxtail. Spray solution pH and ions present were both important to sethoxydim phytotoxicity to oat. Sodium and calcium salts were antagonistic to sethoxydim phytotoxicity only when the spray carrier pH exceeded 7. Ammonium salts and ammonium hydroxide were synergistic with sethoxydim, and the synergism was independent of spray solution pH. Ammonium sulfate, but not ammonium hydroxide, overcame sodium bicarbonate antagonism of sethoxydim. The antagonism of sethoxydim phytotoxicity by sodium bicarbonate was greatest in the presence of UV light and most pronounced when treated plants were exposed to mid-day sunlight. Sodium bicarbonate or low temperature may reduce the speed of sethoxydim absorption allowing for greater UV degradation of unabsorbed sethoxydim on the leaf surface.


Chemosphere ◽  
2020 ◽  
Vol 240 ◽  
pp. 124958 ◽  
Author(s):  
Lee C. Moores ◽  
Alan J. Kennedy ◽  
Lauren May ◽  
Shinita M. Jordan ◽  
Anthony J. Bednar ◽  
...  

2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Alvaro Lopez-Zaplana ◽  
Juan Nicolas-Espinosa ◽  
Micaela Carvajal ◽  
Gloria Bárzana

AbstractMelon (Cucumis melo L.) is a very important crop throughout the world and has great economic importance, in part due to its nutritional properties. It prefers well-drained soil with low acidity and has a strong demand for water during fruit set. Therefore, a correct water balance—involving aquaporins—is necessary to maintain the plants in optimal condition. This manuscript describes the identification and comparative analysis of the complete set of aquaporins in melon. 31 aquaporin genes were identified, classified and analysed according to the evolutionary relationship of melon with related plant species. The individual role of each aquaporin in the transport of water, ions and small molecules was discussed. Finally, qPCR revealed that almost all melon aquaporins in roots and leaves were constitutively expressed. However, the high variations in expression among them point to different roles in water and solute transport, providing important features as that CmPIP1;1 is the predominant isoform and CmTIP1;1 is revealed as the most important osmoregulator in the tonoplast under optimal conditions. The results of this work pointing to the physiological importance of each individual aquaporin of melon opening a field of knowledge that deserves to be investigated.


2007 ◽  
Vol 90 (6) ◽  
pp. 1547-1553 ◽  
Author(s):  
Alaa Khedr

Abstract The purpose of this work was to develop a sensitive, selective, and validated stability-indicating high-performance liquid chromatographic (LC) assay of atorvastatin (ATV) in bulk drug and tablet form. ATV was subjected to different stress conditions, including UV light, oxidation, acid-base hydrolysis, and temperature. ATV and its degradation products were analyzed on an Agilent Zorbax XDB C18 column using isocratic elution with acetonitrile0.02 M sodium acetate, pH 4.2 (45 + 55, v/v) for 25 min. The samples were monitored with fluorescence (FL) detection at 282 nm (excitation)/400 nm (emission). The response ratio of FL to UV detection (at 247 nm) for ATV was 1.66. The method showed good resolution of ATV from its decomposition products. The photodegradation products were separated by silica gel thin-layer chromatography using double development with ethyl acetaten-hexaneglacial acetic acidmethanol (40 + 55 + 0.5 + 4.5, v/v/v/v) followed by (39 + 55 + 0.5 + 5.5, v/v/v/v), and confirmed by LC-FL analysis. The FL response was linear over the investigated range for ATV. The linear range was 101200 ng/injection, and the limit of quantitation was 2.0 ng/injection.


2002 ◽  
Vol 85 (6) ◽  
pp. 1247-1252 ◽  
Author(s):  
Alejandro Álvarez-Lueje ◽  
Sara Pujol ◽  
Luis J Núñez-Vergara ◽  
Juan A Squella

Abstract Lercanidipine in ethanol–0.04M Britton-Robinson buffer (20 + 80) gives an irreversible anodic response on a glassy carbon electrode in a broad pH range (2–12) that depends on pH. This signal can be attributed to oxidation of the 1,4-dihydropyridine ring to give the corresponding pyridine derivative. For analytical purposes, differential pulse voltammetry at pH 4 was selected. Under these conditions, good values of both within- and interday reproducibility were obtained, with coefficient of variation (CV) values of 1.56 and 1.70%, respectively, for 10 successive runs. For quantitation, the calibration curve method was used for lercanidipine concentrations ranging from 1 × 10−5 to 1 × 10−4M. The detection and quantitation limits were 1.39 × 10−5 and 1.49 × 10−5, respectively. A liquid chromatographic method with electrochemical detection was used for comparison. The voltammetric method showed good selectivity with respect to both excipients and degradation products. The recovery study exhibited a CV of 0.94% and an average recovery of 98.3%, and it was not necessary to treat the sample before the analysis. The method was successfully applied to the individual tablet assay of lercanidipine in commercial tablets.


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