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The study focuses on the current state of curative mud deposits in Estonia as of 2022, examining changes over the past decade and providing essential information on curative mud quality. Total of 64 curative mud samples were collected in 2022, marking the first investigation into hazardous substances such as phenols, petroleum products, and pesticides. The study encompassed analyses of organic and mineral matter content, grain size, microbiology, and heavy metal concentrations, totalling 1649 measurements. Comparisons with previous data revealed stable organic matter concentrations in lake and marine sediments over the last decade. Microbiological contamination in curative mud samples was relatively low, indicating cleanliness. Petroleum product concentrations varied, with Haapsalu at 42 mg/kg, Värska at 118.6 mg/kg, and Käina below the limit of quantification. Phenol concentrations were generally below the limit of quantification, except for Värska. Pesticides were found in Värska samples, but in other sediments, levels were below the limit of quantification. Average heavy metal concentrations in curative mud decreased between 2013-2014 and 2022, remaining below the target value. The study's results are crucial for curative mud-related entrepreneurship in Estonia, facilitating compliance with the new regulatory standards. The comprehensive data obtained will contribute to the consistency and efficacy of curative mud-related practices in the country., (© 2024. The Author(s).)

Highly microporous adsorbents have been under considerable scrutiny for efficient adsorptive storage of H 2 . Of specific interest are sustainable, chemically activated, microporous carbon adsorbents, especially from renewable and organic precursor materials. In this article, six peat-derived microporous carbon materials were synthesized by chemical activation with ZnCl 2 . N 2 and CO 2 gas adsorption data were measured and simultaneously fitted with the 2D-NLDFT-HS model. Thus, based on the obtained results, the use of a low ratio of ZnCl 2 for chemical activation of peat-derived carbon yields highly ultramicroporous carbons which are able to adsorb up to 83% of the maximal adsorbed amount of adsorbed H 2 already at 1 bar at 77 K. This is accompanied by the high ratio of micropores, 99%, even at high specific surface area of 1260 m 2 g -1 , exhibited by the peat-derived carbon activated at 973 K using a 1:2 ZnCl 2 to peat mass ratio. These results show the potential of using low concentrations of ZnCl 2 as an activating agent to synthesize highly ultramicroporous carbon materials with suitable pore characteristics for the efficient low-pressure adsorption of H 2 .

This paper provides a methodological protocol for measuring diameter and other properties of mineral sand grains using an image analysis technique. The aeolian sand influx (ASI) from coastal bogs has been used to reconstruct changes in the past storminess. However, concentrations of sand grains in peat deposits, from which the ASI is calculated, tend to be low, and sieving and laser diffractometry cannot be applied. Manual counting of sands under microscope is time-consuming and less efficient because of possible human errors. This paper describes a protocol for an image analysis method used in our recent paper (Vandel et al. 2019) that overcomes those issues in sand grain measurements. After preliminary sample preparations, including loss-on-ignition and chemical pretreatments, this study uses ImageJ - a semi-automated image processing program - to analyze images captured under microscope. With proper sample size selection, pre-treatment, image capturing and image analysis settings in ImageJ described in this paper, the approach proved to be:•objective and efficient for analysing grain-size distribution even with low concentrations of sands in samples,•increasing reliability of the measurement and providing reproducible results by avoiding manual measuring processes, and•non-destructive and enabling further analyses on mineral composition and other properties of sand grains., (© 2020 The Authors. Published by Elsevier B.V.)

The abundance and properties of small standing water bodies (SSWB) is globally not well known for their ecological importance is undervalued and their detection suffers from technical limitations. In the current study, we used a combination of GIS-based methods (satellite, orthophoto, ground validation) to evaluate regional estimates of standing water body (SWB) inventories in two geographically different parts of Europe - France, and Estonia. In our study the SWBs surface area threshold limit was 0.00001 km 2 , exceeding the limits of previous studies (>0.002 km 2 ). The total number of SWBs in Estonia is 111 552 (2.5 per km 2 ) and in France 598 371 (1.1 per km 2 ). Our estimates show that the median size of SWBs in Estonia and France is 0.0003 km 2 and 0.0007 km 2 respectively, meaning that most of the SSWBs are not included in the global inventories, and their number is therefore underestimated. SSWBs (area below 0.01 km 2 ) form a significant share of the total shoreline length of SWBs, 70.3% in Estonia and 58.8% in France. As nearshore areas are often very productive with diverse habitats, the SSWBs hold a crucial role in maintaining biodiversity. Our results provide quantitative evidence that SSWBs are vital and abundant landscape elements, freshwater resources, and habitats that should not be ignored in global inventories., (© 2019 The Authors.)

A path to new synthons for application in crystal engineering is the replacement of a strong hydrogen-bond acceptor, like a C=O group, with a weaker acceptor, like a C=S group, in doubly or triply hydrogen-bonded synthons. For instance, if the C=O group at the 2-position of barbituric acid is changed into a C=S group, 2-thiobarbituric acid is obtained. Each of the compounds comprises two ADA hydrogen-bonding sites (D = donor and A = acceptor). We report the results of cocrystallization experiments of barbituric acid and 2-thiobarbituric acid, respectively, with 2,4-diaminopyrimidine, which contains a complementary DAD hydrogen-bonding site and is therefore capable of forming an ADA/DAD synthon with barbituric acid and 2-thiobarbituric acid. In addition, pure 2,4-diaminopyrimidine was crystallized in order to study its preferred hydrogen-bonding motifs. The experiments yielded one ansolvate of 2,4-diaminopyrimidine (pyrimidine-2,4-diamine, DAPY), C4H6N4, (I), three solvates of DAPY, namely 2,4-diaminopyrimidine-1,4-dioxane (2/1), 2C4H6N4·C4H8O2, (II), 2,4-diaminopyrimidine-N,N-dimethylacetamide (1/1), C4H6N4·C4H9NO, (III), and 2,4-diaminopyrimidine-1-methylpyrrolidin-2-one (1/1), C4H6N4·C5H9NO, (IV), one salt of barbituric acid, viz. 2,4-diaminopyrimidinium barbiturate (barbiturate is 2,4,6-trioxopyrimidin-5-ide), C4H7N4(+)·C4H3N2O3(-), (V), and two solvated salts of 2-thiobarbituric acid, viz. 2,4-diaminopyrimidinium 2-thiobarbiturate-N,N-dimethylformamide (1/2) (2-thiobarbiturate is 4,6-dioxo-2-sulfanylidenepyrimidin-5-ide), C4H7N4(+)·C4H3N2O2S(-)·2C3H7NO, (VI), and 2,4-diaminopyrimidinium 2-thiobarbiturate-N,N-dimethylacetamide (1/2), C4H7N4(+)·C4H3N2O2S(-)·2C4H9NO, (VII). The ADA/DAD synthon was succesfully formed in the salt of barbituric acid, i.e. (V), as well as in the salts of 2-thiobarbituric acid, i.e. (VI) and (VII). In the crystal structures of 2,4-diaminopyrimidine, i.e. (I)-(IV), R2(2)(8) N-H...N hydrogen-bond motifs are preferred and, in two structures, additional R3(2)(8) patterns were observed.

The understanding of intermolecular interactions is a key objective of crystal engineering in order to exploit the derived knowledge for the rational design of new molecular solids with tailored physical and chemical properties. The tools and theories of crystal engineering are indispensable for the rational design of (pharmaceutical) cocrystals. The results of cocrystallization experiments of the antithyroid drug 6-propyl-2-thiouracil (PTU) with 2,4-diaminopyrimidine (DAPY), and of 6-methoxymethyl-2-thiouracil (MOMTU) with DAPY and 2,4,6-triaminopyrimidine (TAPY), respectively, are reported. PTU and MOMTU show a high structural similarity and differ only in the replacement of a methylene group (-CH2-) with an O atom in the side chain, thus introducing an additional hydrogen-bond acceptor in MOMTU. Both molecules contain an ADA hydrogen-bonding site (A = acceptor and D = donor), while the coformers DAPY and TAPY both show complementary DAD sites and therefore should be capable of forming a mixed ADA/DAD synthon with each other, i.e. N-H...O, N-H...N and N-H...S hydrogen bonds. The experiments yielded one solvated cocrystal salt of PTU with DAPY, four different solvates of MOMTU, one ionic cocrystal of MOMTU with DAPY and one cocrystal salt of MOMTU with TAPY, namely 2,4-diaminopyrimidinium 6-propyl-2-thiouracilate-2,4-diaminopyrimidine-N,N-dimethylacetamide-water (1/1/1/1) (the systematic name for 6-propyl-2-thiouracilate is 6-oxo-4-propyl-2-sulfanylidene-1,2,3,6-tetrahydropyrimidin-1-ide), C4H7N4(+)·C7H9N2OS(-)·C4H6N4·C4H9NO·H2O, (I), 6-methoxymethyl-2-thiouracil-N,N-dimethylformamide (1/1), C6H8N2O2S·C3H7NO, (II), 6-methoxymethyl-2-thiouracil-N,N-dimethylacetamide (1/1), C6H8N2O2S·C4H9NO, (III), 6-methoxymethyl-2-thiouracil-dimethyl sulfoxide (1/1), C6H8N2O2S·C2H6OS, (IV), 6-methoxymethyl-2-thiouracil-1-methylpyrrolidin-2-one (1/1), C6H8N2O2S·C5H9NO, (V), 2,4-diaminopyrimidinium 6-methoxymethyl-2-thiouracilate (the systematic name for 6-methoxymethyl-2-thiouracilate is 4-methoxymethyl-6-oxo-2-sulfanylidene-1,2,3,6-tetrahydropyrimidin-1-ide), C4H7N4(+)·C6H7N2O2S(-), (VI), and 2,4,6-triaminopyrimidinium 6-methoxymethyl-2-thiouracilate-6-methoxymethyl-2-thiouracil (1/1), C4H8N5(+)·C6H7N2O2S(-)·C6H8N2O2S, (VII). Whereas in (I) only an AA/DD hydrogen-bonding interaction was formed, the structures of (VI) and (VII) both display the desired ADA/DAD synthon. Conformational studies on the side chains of PTU and MOMTU also revealed a significant deviation for cocrystals (VI) and (VII), leading to the desired enhancement of the hydrogen-bond pattern within the crystal.

In order to obtain complexes held together by hydrogen as well as halogen bonds, 6-chlorouracil [6-chloropyrimidin-2,4(1H,3H)-dione; 6CU] and its 3-methyl derivative [6-chloro-3-methylpyrimidin-2,4(1H,3H)-dione; M6CU] were cocrystallized with 2,4,6-triaminopyrimidine and the three triazine derivatives 2,4,6-triamino-1,3,5-triazine (melamine), 2,4-diamino-6-methyl-1,3,5-triazine and 2-chloro-4,6-diamino-1,3,5-triazine, which all offer complementary hydrogen-bonding sites. Three of these compounds form cocrystals with 6CU; however, melamine yielded only a new pseudopolymorph with 6CU, but formed a cocrystal with M6CU. All six cocrystals contain solvent molecules (N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidin-2-one), whose intermolecular interactions contribute significantly to the stabilization of the crystal packing. Each of these structures comprises chains, which are primarily formed by strong hydrogen bonds with a basic framework built by R2(2)(8) hydrogen bonds of either pure N-H...N or mixed patterns. Solvent molecules are aligned to the border of these chains via N-H...O hydrogen bonds. Two of the reported crystal structures containing 6CU show additional Cl...O halogen bonds, which connect the chains to two-dimensional layers, while one weak and one strong Cl...Cl interaction are observed in the two structures in which molecules of M6CU are present.

The results of seven cocrystallization experiments of the antithyroid drug 6-methyl-2-thiouracil (MTU), C(5)H(6)N(2)OS, with 2,4-diaminopyrimidine, 2,4,6-triaminopyrimidine and 6-amino-3H-isocytosine (viz. 2,6-diamino-3H-pyrimidin-4-one) are reported. MTU features an ADA (A = acceptor and D = donor) hydrogen-bonding site, while the three coformers show complementary DAD hydrogen-bonding sites and therefore should be capable of forming an ADA/DAD N-H...O/N-H...N/N-H...S synthon with MTU. The experiments yielded one cocrystal and six cocrystal solvates, namely 6-methyl-2-thiouracil-2,4-diaminopyrimidine-1-methylpyrrolidin-2-one (1/1/2), C(5)H(6)N(2)OS·C(4)H(6)N(4)·2C(5)H(9)NO, (I), 6-methyl-2-thiouracil-2,4-diaminopyrimidine (1/1), C(5)H(6)N(2)OS·C(4)H(6)N(4), (II), 6-methyl-2-thiouracil-2,4-diaminopyrimidine-N,N-dimethylacetamide (2/1/2), 2C(5)H(6)N(2)OS·C(4)H(6)N(4)·2C(4)H(9)NO, (III), 6-methyl-2-thiouracil-2,4-diaminopyrimidine-N,N-dimethylformamide (2/1/2), C(5)H(6)N(2)OS·0.5C(4)H(6)N(4)·C(3)H(7)NO, (IV), 2,4,6-triaminopyrimidinium 6-methyl-2-thiouracilate-6-methyl-2-thiouracil-N,N-dimethylformamide (1/1/2), C(4)H(8)N(5)(+)·C(5)H(5)N(2)OS(-)·C(5)H(6)N(2)OS·2C(3)H(7)NO, (V), 6-methyl-2-thiouracil-6-amino-3H-isocytosine-N,N-dimethylformamide (1/1/1), C(5)H(6)N(2)OS·C(4)H(6)N(4)O·C(3)H(7)NO, (VI), and 6-methyl-2-thiouracil-6-amino-3H-isocytosine-dimethyl sulfoxide (1/1/1), C(5)H(6)N(2)OS·C(4)H(6)N(4)O·C(2)H(6)OS, (VII). Whereas in cocrystal (I) an R(2)(2)(8) interaction similar to the Watson-Crick adenine/uracil base pair is formed and a two-dimensional hydrogen-bonding network is observed, the cocrystals (II)-(VII) contain the triply hydrogen-bonded ADA/DAD N-H...O/N-H...N/N-H...S synthon and show a one-dimensional hydrogen-bonding network. Although 2,4-diaminopyrimidine possesses only one DAD hydrogen-bonding site, it is, due to orientational disorder, triply connected to two MTU molecules in (III) and (IV).