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RATIONALE: For most of the last two decades, a considerable effort has been made towards improving time-of-flight mass spectrometry (TOF MS), which has become an irreplaceable instrumental platform for the purposes of performing analytical measurements in life sciences, such as molecular biology, proteomics, medicine, etc. This can primarily be attributed to the ability of TOF MS to rapidly detect and identify nearly any targeted chemical trace with both high precision and accuracy. However, multi-span TOF MS experiments are limited due to aberrations arising from multiple reflection; our proposed scheme will minimize these aberrations. METHODS: The inhomogeneous accelerating field is generated without using meshes by changing the potentials on the electrodes of the mirror. The ions are extracted from the ion source by short impulse activation of the accelerating electric field. Since the ions are extracted from various points of the source, even ions with identical masses acquire different velocities during acceleration. RESULTS: We have shown that the "rear" ions of the packet catch up with the "front" ions, and packets of ions with identical masses are compressed in the direction of their movement. It is concluded that, by placing the detector in a plane with the greatest compression of ion packets, an enhanced performance of a time-of-flight mass spectrometer is achieved. CONCLUSIONS: We have shown that effective spatial-temporal focusing allows a small mass spectrometer to achieve high resolution and sensitivity. We also propose and numerically evaluate a new platform for designing multi-stage and multi-reflective time-of-flight analyzers with wedge-shaped mirrors. We applied the simulation results to the modernization of old equipment and showed that by simply replacing the electrostatic mirror with an optimized one, a significant increase in the analyzing power can be achieved.
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BACKGROUND: This paper is based on the studies of the biogeochemical structure of the water column in the anoxic Fjord Hunnbunn (south-eastern Norway) performed in 2009, 2011 and 2012. This Fjord is an enclosed basin of brackish water separated by a narrow and shallow outlet to the sea with a permanently anoxic layer. We show how an oxygenated intrusion could lead to both positive and negative effects on the ecosystem state in Hunnbunn due to a change in the biogeochemical structure. RESULTS: During the stratified periods in 2009 and 2012 the anoxic layer amounted to approximately 10% of the total water volume in the Fjord, while dissolved oxygen (DO) was present in 80-90% of the water. In the autumn of 2011 the water chemistry structure observed in Fjord Hunnbunn was clearly affected by a recent oxygenated intrusion defined by abnormal salinity patterns. This led to a shift of the DO boundary position to shallower depths, resulting in a thicker anoxic layer comprising approximately 40% of the total water volume, with DO present only in approximately 60% of the water. The oxygenated water intrusions led to a twofold decrease of the concentrations of hydrogen sulphide, ammonia, phosphate and silicate in the deep layers with a simultaneous increase of these nutrients and a decrease of the pH level in the surface layers. The concentrations of manganese, iron, and mercury species changed dramatically and in particular revealed a significant supply of iron and methylmercury to the water column. CONCLUSIONS: Oxic water intrusions into anoxic fjords could lead not only to the flushing of the bottom anoxia, but to a dispersal of sulphidic and low oxygen conditions to the larger bottom area. The elevation of the hydrogen sulphide to the shallower layers (that can be rapidly oxidized) is accompanied by the appearance in the subsurface water of methylmercury, which is easily accumulated by organisms and can be transported to the surrounding waters, affecting the ecosystem over a larger area.
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The Black Sea is the largest euxinic basin on the Earth. The anoxic zone consists of the upper part water mass stratified by density, and the lower water mass homogenized relative to density (depth >1750 m), named the Bottom Convective Layer. To assess homogeneity and possible exchange of matter across the upper and lower boundaries of the Bottom Convective Layer, new data on stable isotope composition of S, O and H were obtained. Samples were collected in August 2008 and March 2009 from two stations located in the eastern central part of the Black Sea. Distribution of δ(18)O and δD values of water for the entire water column did not vary seasonally. Appreciable differences were marked for δD value variation in the picnocline area (water depth 200-400 m) and in the BCL 5 m above the bottom that might be caused by penetration of intrusions with elevated portion of shelf modified Mediterranean Water. Observed linear relationship between δ(18)O (or δD) and salinity indicates that mixing water and salt occurs at the same time, and the deep water of the Black Sea has two end members: the high-salinity Mediterranean seawater and freshwater input. In the Bottom Convective Layer, the average δ(34)S (H2S) was -40.6 ± 0.5 and did not vary seasonally. At the bottom (depth > 2000 m), (34)S depletion down to -41.0 was observed. Our δ(34)S (SO4) data are by 2-3 higher than those measured previously for the Bottom Convective Layer. Sulfate from the aerobic zone with δ(34)S (SO4) = +21 corresponds to ocean water sulfate and that has not been subjected to sulfate reduction. Average δ(34)S (SO4) values for depths > 1250 m were found to be +23.0 ± 0.2 (1σ). Sulfur isotope composition of sulfate does not change in the Bottom Convective Layer and on its upper and lower boundaries, and does not depend on the season of observation.
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The Caspian Sea, the world's largest enclosed water body, experiences significant transformations in its physico-chemical properties and a decline in bioresources due to extensive anthropogenic activities. These activities include the discharge of diverse pollutants and bio-physical alterations such as over-fishing, hunting, and physical alterations to rivers. While acute manifestations such as a fall in the Caspian water levels and wetland desiccation are more overt, the pervasive impact of human activities contributes to a likely irreversible decline in environmental quality that we aim to spotlight in this discussion in order to facilitate its restoration.
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Monitoramento Ambiental , Oceanos e Mares , Conservação dos Recursos Naturais , Áreas AlagadasRESUMO
This study presents new data on concentration of dissolved trace elements (DTE) in the Lena River-Laptev Sea mixing zone. Mean concentrations of some dissolved heavy metals in the mixing zone of fresh waters of the Lena River and sea waters of the Laptev Sea on the middle shelf and on the outer shelves are: 0.7± 0.05 µÐ and 0.5 ± 0.04 µÐ for Fe, 0.06 ± 0.01 µÐ and 0.07 ± 0.01 µÐ for Ni, 0.01 ± 0.003 µÐ and 0.003 ± 0.002 µÐ for Zn, 59.2 ± 7.4 nÐ and 73.4 ± 12.8 nÐ for Cu, respectively. Two major groups of DTE distribution were revealed according to their spatial behavior. The Li, V, As, Rb, Sr, Mo, U concentrations increase towards the outer shelf with increasing salinity. In contrast, mean concentrations of Al, Ti, Mn, Fe, Co decrease with increasing distance from the coast. The identified transport of freshwaters to a distance of 400 km is reflected in the distribution of DTE, which suggests that these elements are able to reach to the Central Arctic Ocean.
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Monitoramento Ambiental , Rios , Água do Mar , Oligoelementos , Poluentes Químicos da Água , Oligoelementos/análise , Poluentes Químicos da Água/análise , Rios/química , Água do Mar/química , Metais Pesados/análise , Oceanos e MaresRESUMO
Microplastic pollution was studied in surface waters of Isfjorden, Svalbard in July 2021 as a part of an international regional harmonisation exercise. Surface microplastics (0.5-5 mm) were sampled with a neuston net in triplicate per study site in several branches of Isfjorden, covering populated and unpopulated fjords. High spatial variability of microplastic abundance (0-32,700 items/km2) was observed within a single fjord resulting from the hydrodynamic pattern formed through the interaction of surface currents, freshwater runoff, and wind conditions. Maximum microplastic abundance was not correlated with the distance from the local source and was instead defined by local small-scale hydrodynamics. Future recommendations for correct assessment of surface microplastics concentration in estuarine environments are presented.
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Arctic rivers are receiving increased attention for their contributing of mercury (Hg) to the Arctic Ocean. Despite this, the knowledge on both the terrestrial release sources and the levels of Hg in the rivers are limited. Within the Arctic, the Barents region has a high industrial development, including multiple potential Hg release sources. This study presents the first overview of potential Hg release sources on Norwegian and Russian mainland draining to the Barents Sea. Source categories cover mining and metallurgy industry; historical pulp and paper production; municipal and industrial solid waste handling; fossil fuel combustion; and past military activities. Available data on Hg in freshwater bodies near the identified potential release sources are reviewed. Levels of Hg were occasionally exceeding the national pollution control limits, thereby posing concern to the local human population and wildlife. However, the studies were sparse and often unsystematic. Finally, we present new data of Hg measured in five Barents rivers. These data reveal strong seasonality in the Hg levels, with a total annual flux constituting 2% of the panarctic total. With this new insight we aspire to contribute to the international efforts of reducing Hg pollution, such as through the effective implementation of the Minamata Convention. Future studies documenting Hg in exposed Barents freshwater bodies are warranted.
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Mercúrio , Humanos , Mercúrio/análise , Rios , Monitoramento Ambiental , Resíduos Industriais , Regiões ÁrticasRESUMO
Comparative investigations of microplastic (MP) occurrence in the global ocean are often hampered by the application of different methods. In this study, the same sampling and analytical approach was applied during five different cruises to investigate MP covering a route from the East-Siberian Sea in the Arctic, through the Atlantic, and into the Antarctic Peninsula. A total of 121 subsurface water samples were collected using underway pump-through system on two different vessels. This approach allowed subsurface MP (100 µm-5 mm) to be evaluated in five regions of the World Ocean (Antarctic, Central Atlantic, North Atlantic, Barents Sea and Siberian Arctic) and to assess regional differences in MP characteristics. The average abundance of MP for whole studied area was 0.7 ± 0.6 items/m3 (ranging from 0 to 2.6 items/m3), with an equal average abundance for both fragments and fibers (0.34 items/m3). Although no statistical difference was found for MP abundance between the studied regions. Differences were found between the size, morphology, polymer types and weight concentrations. The Central Atlantic and Barents Sea appeared to have more MP in terms of weight concentration (7-7.5 µg/m3) than the North Atlantic and Siberian Arctic (0.6 µg/m3). A comparison of MP characteristics between the two Hemispheres appears to indicate that MP in the Northern Hemisphere mostly originate from terrestrial input, while offshore industries play an important role as a source of MP in the Southern Hemisphere. The waters of the Northern Hemisphere were found to be more polluted by fibers than those of the Southern Hemisphere. The results presented here suggest that fibers can be transported by air and water over long distances from the source, while distribution of fragments is limited mainly to the water mass where the source is located.
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Microplásticos , Poluentes Químicos da Água , Regiões Antárticas , Regiões Árticas , Monitoramento Ambiental , Plásticos , Água , Poluentes Químicos da Água/análiseRESUMO
Northern Dvina River is one of the largest rivers in the European Arctic flowing into the White Sea through the populated regions with developed industry. Floating plastics include microplastics (0.5-5 mm) and mesoplastics (5-25 mm) were observed on seasonal variations in the Northern Dvina River mouth. The samples were collected every month from September to November 2019 and from May to October 2020 with a Neuston net that was togged 3 nautical miles in the Korbel'nyy Branch of the River delta. Chemical composition of the plastic particles was determined using a Fourier transmission infrared spectrometer. The majority of the microplastics were identified as polyethylene 52.6%, followed by polypropylene 36.8%. After estimating the export fluxes of microplastics from the Northern Dvina River to the Arctic, there is no significant seasonal variation of the river export of microplastics. The microplastics export rate during the spring flood period in May turned out to be maximum, 58 items/s, while the minimum discharge was in September with a value of 9 items/s. The average weight concentration of microplastics was 18.5 µg/m3, which is higher than it was found in the Barents Sea - 12.5 µg/m3 and several times higher than in the Eurasian Arctic on average - 3.7 µg/m3. These results indicate that the Northern Dvina River is being one of the main sources of microplastic pollution of the White and the Barents Seas.
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Microplásticos , Rios , Estações do Ano , Poluentes Químicos da Água , Regiões Árticas , Monitoramento Ambiental/métodos , Microplásticos/análise , Oceanos e Mares , Rios/química , Poluentes Químicos da Água/análiseRESUMO
Submarine tailing disposal (STD) in fjords from land-based mines is common practice in Norway and takes place in other regions worldwide. We synthesize the results of a multidisciplinary programme on environmental impacts of STDs in Norwegian fjords, providing new knowledge that can be applied to assess and mitigate impact of tailing disposal globally, both for submarine and deep-sea activities. Detailed geological seafloor mapping provided data on natural sedimentation to monitor depositional processes on the seafloor. Modelling and analytical techniques were used to assess the behaviour of tailing particles and process-chemicals in the environment, providing novel tools for monitoring. Toxicity tests showed biological impacts on test species due to particulate and chemical exposure. Hypersedimentation mesocosm and field experiments showed a varying response on the benthos, allowing to determine the transition zone in the STD impact area. Recolonisation studies indicate that full community recovery and normalisation of metal leakage rates may take several decades due to bioturbation and slow burial of sulfidic tailings. The results are synthesised to provide guidelines for the development of best available techniques for STDs.
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Estuários , Metais , Meio Ambiente , Monitoramento Ambiental , NoruegaRESUMO
The main objectives of this work were the acquisition of new data on floating marine macro litter (FMML) and natural floating objects in the Arctic seas, an initial assessment of the level of pollution by FMML and an analysis of potential sources. The results of this study present the first data on FMML distribution in Russian Arctic shelf seas in relation to oceanographic conditions (i.e. position of water masses of different origin as described by temperature, salinity, dissolved oxygen and pH). The main finding of this study is that FMML was found only in the water of Atlantic origin, inflowing from the Barents Sea, where FMML average density on the observed transects was 0.92 items/ km2. Eastern parts of the study, Kara Sea, Laptev Sea and East Siberian Sea were practically free from FMML. No input from rivers was detected, at least in autumn, when the observations were performed.
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Monitoramento Ambiental , Oceanografia , Regiões Árticas , Oceanos e Mares , Plásticos , Federação RussaRESUMO
It is a great challenge to sample seawater across interfaces, for example the halocline or the redoxcline, to investigate trace metal distribution. With the use of 10l sampling bottles mounted to a wire or a CTD-Rosette it is possible to obtain a maximum vertical resolution of 5m. For the detection of small vertical structures in the vertical distribution of trace metals across the redoxcline, the CTD-Bottle-Rosette is not sufficient. Therefore, a PUMP-CTD-System was developed, which enables water sampling with high resolution (1m maximum) along a vertical profile. To investigate the suitability and possible contamination sources of this device two experiments were carried out in the Gotland Basin. The first experiment consisted of two separate profiles. The first profile was obtained with the CTD-Bottle-Rosette and the second with the PUMP-CTD-System. Both were taken from the bottom to the surface water layer. The second experiment was a combined profile obtained from the surface to the bottom with the PUMP-CTD-System attached to the CTD-Bottle-Rosette. Concentrations of dissolved Pb, Cd, Cu, Zn, Fe, Mn, Co and Ni from the "Niskin Bottles" and from the PUMP were measured and compared for each investigation. We demonstrate that it is useful to perform vertical sampling from lower to higher concentrations, e.g. surface to bottom in this environment, and that a longer flushing is required for sampling seawater in the anoxic bottom water. A comparison of the two systems for oxygen and hydrogen sulphide measurements showed an improvement of the precision and the quality of the sampling when using the PUMP. Thus, metal speciation at the oxic-anoxic gradient zone and on a high vertical resolution will be accessible. As concentrations of dissolved Pb, Cd, Cu, Zn, Co, Ni, Fe and Mn in seawater sampled with both devices were in the same range, we conclude that the PUMP-CTD-System is well suited to sample seawater for trace metal analyses.
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Água do Mar/análise , Oligoelementos/análise , Poluentes Químicos da Água/análise , Monitoramento Ambiental/instrumentação , Monitoramento Ambiental/métodos , Oceanos e Mares , Purificação da Água/instrumentação , Purificação da Água/métodosRESUMO
The long-term variability of the physical and biochemical structure of oxic and suboxic layers in the Black Sea was studied using a one-dimensional coupled hydrophysical and biogeochemical model. The focus was on the correlation between atmospheric forcing (2 m air temperature and dew point temperature, surface level pressure, surface wind) affected by the North Atlantic Oscillation in and the regional responses. The quality of model performance was demonstrated using observed vertical and temporal distribution of biogeochemical variables. It was shown that during 1960-2000, the long-term variability of simulated winter-mean SST in the Black Sea correlated reasonably well with the variability of 2 m air temperature. Furthermore, the thermal state of the upper ocean impacted largely on the variability of biogeochemical variables, such as oxygen, nitrate and phytoplankton concentration. The tele-connection between North Atlantic Oscillation and Black Sea biogeochemistry was manifested in a different way for the specific time-interval 1960-2000; the corresponding regime shifts were thus associated with the large scale forcing. One such extreme event occurred in 1976 leading to a pronounced shift in the oxygen and hydrogen sulfide state.
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Clima , Monitoramento Ambiental/estatística & dados numéricos , Modelos Teóricos , Fitoplâncton/fisiologia , Água do Mar/química , Temperatura , Mar Negro , Monitoramento Ambiental/métodos , Sulfeto de Hidrogênio/análise , Nitratos/análise , Oxigênio/análise , Dinâmica PopulacionalRESUMO
After the discovery of ANaerobic AMMonium OXidation (anammox) in the environment, the role of heterotrophic denitrification as the main marine pathway for fixed N loss has been questioned. A 3 part, 15 month time series investigating nitrite reductase (nirS) mRNA transcripts at a single location in the Black Sea was conducted in order to better understand the activity of anammox and denitrifying bacteria. Here we show that both of these groups were active, as well as being concurrent in the lower suboxic zone over this time span. Their distributions, however, differed in that only expression of denitrification-type nirS was seen in the upper suboxic zone, where geochemistry was variable. Depth profiles covering the suboxic zone showed that the four groups of anammox-type sequences were expressed consistently in the lower suboxic zone, and were consistent with anammox 16 S rDNA gene profiles. By contrast, denitrifier-type nirS sequence groups were mixed; some groups exhibited consistent expression in the lower suboxic zone, while others appeared less consistent. Co-occurrence of both anammox and denitrifier expression was common and ongoing. Both types of transcripts were also found in samples with low concentrations of sulfide (>2 µM). Six major groups of denitrifier-type nirS transcripts were identified, and several groups of denitrifier-type nirS transcripts were closely related to sequences from the Baltic Sea. An increase in denitrifier-type nirS transcript diversity and depth range in October 2007 corresponded to a small increase in mixed layer net community productivity (NCP) as measured by O(2)/Ar gas ratios, as well as to an increase in N(2) concentrations in the suboxic zone. Taken together, the variations in expression patterns between anammox and denitrification provide one possible explanation as to how near instantaneous rate measurements, such as isotope spike experiments, may regularly detect anammox activity but underreport denitrification.
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Computational formulae for the coefficients of the third-order spherical aberration and the second-order axial chromatic aberration are presented for an axially symmetric electrostatic electron mirror. A technique for eliminating the high-order derivatives of the potential axial distribution in mirror systems from the integrands is described. Conditions for elimination of spherical and axial chromatic aberrations, either separately or simultaneously, are found for a three-electrode axially symmetric mirror composed of coaxial cylinders of the same diameter. A principal scheme of the transmission electron microscope, where an electrostatic electron mirror serves as its objective, is presented.