Diclofenac sodium aqueous systems at low concentrations: Interconnection between physicochemical properties and action on hydrobionts

Diclofenac sodium(DS) is a widely used nonsteroidal anti-inflammatory drug(NSAIDs).NSAIDs are poorly removed during standard wastewater treatment.The consequences of the presence of NSAIDs in rivers and lakes at 10~(-11)–10~(-8) mol/L are not yet established;therefore, ecotoxicologists have focused their efforts on studying the effect of lowconcentration NSAIDs on fish and hydrobionts, and also on predicting the potential risks to humans.Literature provides some information about the bioeffects of some NSAID solutions in low concentrations but there is no physicochemical explanation for these phenomena.Studying the physicochemical patterns of DS solutions in the low range of concentrations and establishing an interconnection between the solutions' physicochemical properties and bioeffects can provide a conceptually new and important source of information regarding the unknown effects of DS.The physicochemical properties and action of DS solutions on Ceriodaphnia affinis cladocerans,Paramecium caudatum infusoria, Chlorella vulgaris unicellular green algae, as well as on the growth of the roots of Triticum vulgare wheat seeds, were studied in the calculated concentration range of 1 × 10~(-3)–1 × 10~(-18) mol/L.The relationship between these phenomena was established using the certified procedures for monitoring the toxicity of natural water and wastewater.It was shown for the first time that water solutions of DS are dispersed systems in which the dispersed phase undergoes a rearrangement with dilution, accompanied by changes in its size and properties, which affects the nonmonotonic dependences of the system's physicochemical properties and could cause nonmonotonic changes in action on hydrobionts in the low concentration range.     

Anthropogenic threats to evolutionary heritage of angiosperms in the Netherlands through an increase in high-competition environments

Present biodiversity comprises the evolutionary heritage of Earth's epochs. Lineages from particular epochs are often found in particular habitats, but whether current habitat decline threatens the heritage from particular epochs is unknown. We hypothesized that within a given region, humans threaten specifically habitats that harbor lineages from a particular geological epoch. We expect so because humans threaten environments that dominated and lineages that diversified during these epochs. We devised a new approach to quantify, per habitat type, diversification of lineages from different epochs. For Netherlands, one of the floristically and ecologically best-studied regions, we quantified the decline of habitat types and species in the past century. We defined habitat types based on vegetation classification and used existing ranking of decline of vegetation classes and species. Currently, most declining habitat types and the group of red-listed species are characterized by increased diversification of lineages dating back to Paleogene, specifically to Paleocene-Eocene and Oligocene. Among vulnerable habitat types with large representation of lineages from these epochs were sublittoral and eulittoral zones of temperate seas and 2 types of nutrient-poor, open habitats. These losses of evolutionary heritage would go unnoticed with classical measures of evolutionary diversity. Loss of heritage from Paleocene-Eocene became unrelated to decline once low competition, shade tolerance, and low proportion of non-Apiaceae were accounted for, suggesting that these variables explain the loss of heritage from Paleocene-Eocene. Losses of heritage from Oligocene were partly explained by decline of habitat types occupied by weak competitors and shade-tolerant species. Our results suggest a so-far unappreciated human threat to evolutionary heritage: habitat decline threatens descendants from particular epochs. If the trends persist into the future uncontrolled, there may be no habitats within the region for many descendants of evolutionary ancient epochs, such as Paleogene.     

Sulfur organic compounds in bottom sediments of the eastern Gulf of Finland

Background, Aims and Scope Despite the large number of studies on the forms of sulfur in marine deposits, investigations on sulfur organic compounds are still rare. It is known that the processes leading to formation of intermediate and final sulfur compounds (including organic ones) in modern deposits are the results of microbiological transformation of sulfur containing proteins, as well as the microbiological reduction of sulfate ions. The latter are finally reduced by anaerobic sulfate-reducing bacteria to H₂S, HS⁻ and S²⁻; the total sum of these is referred to as ‘hydrogen sulfide’ in chemical oceanography. Further, the formation of reduced sulfur organic derivatives (sulfides and polysulfides) is the result of interaction of the organic substance destruction products with the sulfide ions. In such cases, the main source of organic substances, as well as sulfates for the sulfur reducing processes, is the pore water in the sediments. The choice of the target of our study is based on the fact that the eastern part of the Gulf of Finland water area receives the bulk of the anthropogenic load of the St. Petersburg region. Low vertical intermixing of the water thickness is observed there (thus creating a deficiency of oxygen near the bottom), and the bottom sea current transfers the polluted salty water of the Baltic Sea into the Neva Bay. The whole of the above are the preconditions for the formation of sulfur-bearing organic compounds. A great number of bottom sediment samples for analytical surveys were collected in the Eastern Gulf of Finland during research expeditions in the years of 1997 and 2001. These were screened for structures of sulfur organic microcontaminants, including organic forms of sulfur, using advanced instrumentation and experienced personnel in our two, cooperating laboratories. This work is a part of the research being carried out on organic micro-admixtures present in bottom sediments, and is the summary of our findings on previously unstudied sulfur organic substances there. Materials and Methods A number of sulfur organic compounds present in nineteen bottom sediment samples from the Eastern Gulf of Finland (EGF) were characterized by high performance gas chromatography connected to low and high resolution mass spectrometers (GC/LRMS and GC/HRMS). The structure screening was carried out as compared with literature and library mass spectra, and taking the GC retention times into account. In the cases of an absence of mass spectra not in the literature, interpretation of the most probable structures was performed with the help of high resolution mass-spectrometric data, fragmentation rules for sulfur-bearing organic substances and ICLU simulation of spectra. These data were registered to form a conclusive ‘fingerprint’ for identification and confirmation of the structure of each novel compound found, e.g. by later syntheses of authentic model compounds. The relative contents of sulfur organic compounds were determined from MS response ratios of each compound to 2-fluorine naphthalene (internal standard). Results This paper is a completion of work, which has been published in part as three papers in the European Journal of Mass Spectrometry. As the total study result, 43 sulfur-bearing compounds were characterized. The mass spectra of 20 of them were found in the literature. The most probable structures for the 23 compounds whose mass-spectra were not available in the literature data were proposed. All of those 23 compounds were detected in bottom sediments for the first time, and 5 of them were described as originating from plants or being generated by chemical synthesis products, while the remaining 18 substances were previously unknown. The structures of these were deduced to be most probably the following (in order of their GC retention): dichloromethyl thiylsulfenylchloride, chloromethyl dichloromethyl disulfide, 3,4-dithiacyclohexene, 1,2,4-trithiacycloheptane, 1,2,3-trithiacyclohexane, tetrathiacyclopentane, 3,4,5-trithiacyclohexene, 1,2,4-trithiacyclohexane, cyclopropylhydrotrisulfide, 1,2-dithiane-3-thiol, 1,3-dithiane-2-thiol, bis(trichloromethyl)-tri-sulfide, 1,2,4,5-tetrathiacyclohexane, 1,2,3,4-tetrathiacycloheptane, 1,2,3,4-tetrathiacycloheptane, 1,2,3,4-tetrathia-cyclo-hexane, pentathiacyclohexane, and 1,2,4,6-tetrathiacyclooctane. The highest amounts of sulfur organic compounds were found in the deepest, bottom areas in the open part of the sea, where the salinity was highest, and oxygen deficiency occurred as well. Also, some coastal places with a high solid matter deposition rate had elevated contents of sulfur organic compounds. Discussion From the 43 sulfur organic compounds found, the HRMS data provided the atomic composition of the molecular ions for 16 compounds with a high confidence (see Table 3). The LRMS spectra could be identified with catalogue or literature spectra in 29 cases. The MS information obtained was insufficient in two cases: 1) The obvious molecular ion (at m/z 110) of compound 1 was not visible in LRMS. 2) For compound 43, the HRMS measurement, due to the low intensity (2%) of the molecular ion (m/z 210), could not exclude the presence of 2 oxygen atoms (instead of one sulfur atom) in the molecule. Major fragments, however, of our 43, certainly contained no oxygen atoms according to HRMS. The limited LRMS data in the literature, for an isomer of 43, had m/z values of all fragments different from those of the compound found by us. The retention times (RT) formed one more evidence for identity between compounds in different samples. The use of different non-polar columns in GC and similar, but not identical, temperature programs produced eluted peaks of novel and known compounds in each sample (mixture) in GC/HRMS and GC/LRMS. These gave sets of RTs which were in a very significant linear correlation (measured example R = 0.999866, p = 1.85E-06, N = 5). Therefore, the RTs in the HRMS analysis systems could be converted to values comparable with those from the LRMS device. The RT values, HRMS m/z values, LRMS spectra, and ICLU simulation results for each organic sulfur compound form an identification ‘fingerprint’. The interpretation of these experimental data, with supporting use of fragmentation rules, allow the giving of a provisional name and structure to the ‘suspect’. In this study and in environmental surveys of micropollutants in general, the compounds suspected of anthropogenic or natural origin occur at low levels in complex mixtures. Therefore, no bulk amount of an authentic, pure model substance for the suspect is available quite often. The most probable name and structure from the fingerprint data are very useful in guiding the preparation of the model substance for a conclusive identification. Similarly, the unknown criminal can be identified in advance by forensic science and his fingerprint, DNA, etc. as registered before the arrest. The analogy can be found in the literature and CAS register of organic polysulfides, which in great part consists of the results of sensitive mixture analysis methods. Conclusions Sediment of the Eastern Gulf of Finland is over large areas anaerobic, as indicated by the existence of novel, non-oxygenated sulfur organic microcontaminants. These substances were most abundant in anoxic and saline, deep bottom regions, and, in addition, in one coastal area near industrial discharges. This occurrence, and also the limited information about sulfur organic compounds in scientific literature, is considered evidence for the dominantly natural processes in their formation. Recommendations and Perspectives The importance and necessity of investigating the sulfur organic compounds in the bottom sediments, result from the fact that their presence can be an indicator of stable anaerobic processes. Similarly, the oxygen disappearance (anoxia) in the marine water, due to a high concentration of the sulfate ions and relatively high content of organic matter, is practically always connected with the appearance of hydrogen sulfide and sulfides. The generation of sulfur organic compounds precedes the formation of the new, or expansion of the existing anaerobic (‘hydrogen sulfide’) zones, which lead to such environmental disasters as mass destruction of hydrobionts. Many organic compounds of sulfur, including sulfides and polysulfides, are toxic to the aquatic organisms. Therefore, in addition to the danger of mass wholesale deaths of marine fauna in the bottom sediments region, there exists a probability of secondary pollution of the water thickness as well, due to the entry of those substances from bottom sediments in the water when the environmental conditions are changed (stormy weather, floods, geological activity of the earth’s crust, etc.).     

Development and calibration of a portable radon sampling system for groundwater Rn activity concentration measurements

The assembling of a system for field sampling and activity concentration measurement of radon dissolved in groundwater is described. Special attention is given in presenting the calibration procedure to obtain the radon activity concentration in groundwater from the raw counting rate registered in a portable scintillation detector and in establishing the precision of the activity concentration measurements. A field procedure was established and the system tested during one year of monthly observations of ²²²Rn activity concentration in groundwater drawn from two wells drilled on metamorphic rocks exposed at Eastern São Paulo State, Brazil. The observed mean ²²²Rn activity concentrations are 374 Bq/dm³ in one well and about 1275 Bq/dm³ in the other one. In both wells the ²²²Rn activity concentrations showed a seasonal variation similar to variations previously reported in the literature for the same region.     

Occupational exposure to NDMA and NMor in the European rubber industry

Many nitrosamines are suspected of being human carcinogens, with the highest concentrations in the environment being measured in the rubber industry. Time trends of personal exposure to N-nitrosodimethylamine (NDMA) and to N-nitrosomorpholine (NMor) during the past two decades in the German rubber industry were analysed and compared with cross-sectional studies in the same period in the Netherlands, Poland, the UK and Sweden. In the majority of the surveyed departments exposures reduced over time, but considerable heterogeneity was present between departments and sectors. Significant reductions were primarily found in curing and post-treating departments and ranged from -3% year(-1) to -19% year(-1). In contrast, NDMA levels increased (+13% year(-1)) in maintenance and engineering in the tyres industry. Average NDMA-levels in general rubber goods (GRG) and NMor-levels in tyre production in Germany did not decrease significantly in the past two decades, whereas NDMA-levels in tyre production (-10% year(-1)) and NMor-levels in GRG (-7% year(-1)) declined significantly after the introduction of an exposure limit for total nitrosamines in Germany in 1988. Confidence intervals of average exposures in other studied countries largely overlap trends observed in Germany. Exposure to N-nitrosamines decreased on average two-to-five fold in the German rubber industry with comparable concentration levels in other European countries. Although average levels are well below the current limits exposure has not been eliminated, and incidental high exposures do still occur.     

Role of quantum dots nanoparticles in the chemical treatment of colored wastewater: Catalysts or additional pollutants

The objective of the study was to investigate the presence and the activity of quantum dots nanoparticles in colored wastewaters. The special interest is devoted to the investigation of their role in the typical treatment of water or wastewater, studying their influence on the effectiveness of applied treatments methods. The standard chemical processes for water treatment and disinfection (direct UV photolysis and direct ozonation) were applied for the degradation of colored organic pollutant, reactive azo dye, in the presence/absence of CdSe/ZnS core-shells quantum dots. The obtained results indicated that investigated nanoparticles inhibit the overall efficiency of applied processes, especially in the case of direct UV photolysis, although catalytic effect might be expected in part due to the semiconductor nature of quantum dots. Such results lead to a conclusion that CdSe/ZnS nanoparticles behave as additional pollutants in the system. They should be removed from the system prior the treatment, because their presence could decrease the efficiency, i.e., prolong the time of treatment and correspondingly increase the costs of the treatment process.     

Defining practical and robust study designs for interventions targeted at terrestrial mammalian predators

Conflicts between humans and mammalian predators are globally widespread and increasing, creating a long-lasting challenge for conservation and local livelihoods. Protection interventions, which are essential to conflict mitigation, should be based on solid evidence of effectiveness produced by robust study designs. Yet, it is unclear what study designs have been used in predator-targeted interventions and how they can be improved to provide best practices for replications. I examined how applications of five study designs (before-after, before-after-control-impact, control-impact, crossover [i.e., the same randomly assigned study units acting as treatments and controls during alternating trials], and randomized controlled trial) have changed over time and how these changes are related to authors, predator species, countries, and intervention types (aversion, husbandry, mixed interventions, invasive management, lethal control, and noninvasive management). I applied multinomial regression modeling to 434 cases (28 predator species and 45 countries) from 244 studies published from 1955 to 2020. Study design was related only to intervention type. Less reliable before-after and control-impact studies were the most common (47.7% and 38.2% of cases, respectively), and their use increased over years as did all interventions. The contribution of the most robust before-after-control-impact (7.4%), randomized controlled trial (5.3%), and crossover designs (1.4%) remained minor over time. Crossover is suitable for aversion, most husbandry techniques, and a few other interventions, but crossover interventions also have the most limitations in terms of applicability. Randomized controlled trial is generally applicable, but impractical or inappropriate for some interventions, and before-after-control-impact appears to be the most widely applicable study design for predator-targeted interventions.     

Use of fluff in a coking coal blend in a pilot scale

Journal of Material Cycles and Waste Management - Fluff is a shredder waste made up mostly of polymeric material generated in semi-integrated steel manufacturing plants, which is usually disposed...     

Resilience and lessons learned from COVID-19 emergency response

Environment Systems and Decisions -