Optimization of a novel process for the ozonolysis of 2, 4‐dichlorophenol

An innovative process was studied for the destruction of 2,4‐dichlorophenol in water. The immiscible fluorinated solvent, inert and highly ozone soluble, was used as the solvent in the extraction‐ozonation system. Taguchi methods were applied in the design of experiments to identify the significant factors and establish the optimal combination of process parameters. The result indicate that this statistical technique can provide an extremely effective structured approach.     

Effects of the Ellagic acid on the N‐Acetyltransferase activity and Acetylation of 2‐aminofluorene in the rat

The effects of the ellagic acid on the in vitro and in vivo acetylation of 2‐aminofluorene were investigated in male Sprague‐Dawley rats. For in vitro examination, cytosols with or without ellagic acid co‐treatment showed different percentage of 2‐aminofluorene acetylation. For in vivo examination, pre‐treatment of male rats with ellagic acid (10 mg/kg) 24h prior to the administration of 2‐aminofluorene (50 mg/kg) resulted in a 26% and 29%, respectively, decrease in the urinary and fecal recovery of N‐acetyl‐2‐aminofluorene, and a 37% decrease in the metabolic clearance of 2‐aminofluorene to N‐acetyl‐2‐aminofluorene. This is the first demonstration that ellagic acid decrease the N‐acetylation of carcinogens in vitro and in vivo.     

Tessaria absinthioides: a possible bio‐monitor for Cd,Pb, and Cu,in the middle and lower basin of the loa river,North Chile

Some ecotoxic metals such as Cd, Pb, and Cu in Tessaria absinthioides were quantified to study its possible use as a bio‐indicator and/or bio‐monitor of these metals. This plant was chosen for its abundance in the area under study, along Chile and even in southern Latin America. For Cd, Pb, and Cu in all three parts of the plant (leaves, stems and roots) a different concentration pattern in each sampling areas was observed. In sampling areas Coya Sur and La Cascada copper and cadmium concentration decrease in order: leaves > roots > stems. In samples collected in Xalquincha the lowest concentrations of Cd and Pb were observed in stems. A maximum of cadmium concentration (9ug/gd.w. in leaves) was found in samples from La Cascada, a inflow to river Loa in Calama. High concentrations of lead were found in roots and leaves. Collected data demonstrate that the main pathway for cadmium is from ground water via roots into the plant. Some data obtained for lead and copper indicate that the influence of dust particles adsorbed on leaves and stems can be higher than uptake from ground water.     

Cytotoxic activity of spark‐decomposed sulfur hexafluoride and analysis of cytotoxic contributions of individual spark decomposition products†

Sulfur hexafluoride decomposed by electrical sparks has been found to by cytotoxic to hamster cells when tested in an in vitro cell survival assay, while SF₆ shows no cytotoxic activity. Chemical analysis of spark‐decomposed SF₆ has identified and quantified the following compounds: SOF₂, SO₂F₂, SF₄, SOF₄, SiF₄, SO₂ and HF. Each of these gases, at concentration ranges expected in spark‐decomposed SF₆, were tested for cytotoxic activity toward hamster cells. Of the gases showing cytotoxic activity, SO₂F₂ and SOF₄ were similar in activity, as were SOF₂ and SF₄, while the behavior of SiF₄ was different from the rest. None of these individual gases, at concentrations expected in spark‐decomposed SF₆, has sufficient cytotoxic activity to account for the cytotoxic effect of spark‐decomposed SF₆ observed in our assay system. A four‐component mixture of some of the gases enumerated above (at concentrations overestimating their abundance in spark‐decomposed SF₆) was much less cytotoxic than the spark‐decomposed SF₆ gas. A mathematical simulation of the cytotoxic activity of a mixture of gases at concentrations found in spark‐decomposed SF₆ was made, assuming independent cytotoxic effects from each component. The simulated cytotoxic effect thus computed was less than that seen in spark‐decomposed SF₆. Since individual components or mixtures of the major decomposition products do not account for the observed biological activity of spark‐decomposed SF₆, this suggests there may be one or more components, present in the spark‐decomposed gas at very low concentrations, which may have a very strong cytotoxic activity.     

Study of the levels of N‐methylcarbamate pesticides in waters of the river Huelva

A study on the levels of N‐methylcarbamate pesticides and some degradation products in waters of the river Huelva was carried out. This river constitutes the main water supply of the city of Seville at the south west of Spain with a population of almost one million inhabitants. N‐methylcarbamates were extracted from the water by using C‐18 solid phase cartridges. High performance liquid chromatography with UV detection was used to carry out the determinations. Residues of carbaryl, methiocarb sulphoxide and α‐naphthol were found in some of the analysed water samples.     

Concentrations of polychlorinated dibenzo‐p‐dioxins and dibenzofurans in outdoor air of North‐Rhine‐Westphalia,Germany

Measurements of polychlorinated dibenzo‐p‐dioxins (PCDD) and dibenzofurans (PCDF) in outdoor air of North‐Rhine‐Westphalia were carried out. Fifty‐six samples were taken at different sites in areas of different land use and emission structures. A special filter system allowed analysis of the gas and particle phases separately. It was found that higher chlorinated PCDD/PCDF (7 or 8 chlorine atoms) are collected on glass fiber filter and lower chlorinated PCDD/PCDF (tetra‐ and penta‐CDD/CDF) are absorbed on polyurethane foam. The following isomers were determined: OCDD, OCDF and 11 isomers with chlorine substitution in 2,3,7,8‐position as well as the sum of TCDD, PeCDD, HxCDD, HpCDD, TCDF, PeCDF, HxCDF, HpCDF and the sum of PCDD (4–8) and PCDF (4–8). No 2,3,7,8‐TCDD could be detected but 2,3,7,8‐TCDF was found at 15 sites. Mean concentration in the Rhine‐Ruhr‐District for the sum of PCDD (4–8) and PCDF (4–8) was 3.2pg/m³ and 5.5pg/m³ respectively. Detection limit for TCDD and PCDD/PCDF (5–8) was 0.1–0.2 pg/m³ and 0.005–0.015 pg/m³ respectively. There is no significant indication that 2,3,7,8‐chlorinated isomers of PCDD/PCDF are predominantly decomposed by photochemical reactions in outdoor air.     

Recovery efficiency of the hydrofluorocarbon (HFC‐134a) by activated carbons of different physicochemical properties

The adsorption characteristics of 1,1,1,2‐tetrafluoroethane (HFC‐134a) on activated carbon were investigated to evaluate the recovery efficiency of HFC‐134a by six activated carbons (two granular activated carbons (GAC1 and GAC2), one high‐surface area activated carbon (HAC), and three activated carbon fibers (ACF10, ACF15, and ACF20)). HFC‐134a adsorption on the activated carbons increased with increase in the specific surface area and pore volume of the activated carbon. The differential heat of the HFC‐134a adsorption decreased with increase in the percentage of the micropore volume to the total pore volume. The adsorption model of HFC‐134a on the activated carbon could be based on the Langmuir model. The constant a of the Langmuir plot of HAC and ACF20 is smaller than GAC1 or GAC2 and ACF10 or ACF15, respectively. The constant W_s of HAC has the largest value. The constant a was correlated to the heat of adsorption. It is concluded that the largest amount of HFC‐134a was adsorbed on HAC, and the least amount of interaction occurred between HFC‐134a and the HAC. The amount of HFC‐134a adsorbed on the activated carbons over time was applied to the Sameshima equation. The adsorption rate constant of HFC‐134a on HAC was the largest. The HAC could be suitable for the recovery of HFC‐134a.     

Preserving the maritime cultural heritage of the Mediterranean,a cradle of cultures,religions and civilizations—the holy land perspective

The article presents the main ancient marine sites of the Holy Land, points the endangered sites and the needed preservation activities. The ancient cultural heritage existing on the Mediterranean shores reflect important events in the history of humanity. It represents numerous important cultures, religions and traditions. This coastal and underwater heritage is rapidly eroded due to sea level rise, global changes and rapid coastal development. Actions taken by the state of Israel to rescue, protect and preserve the marine cultural heritage include: underwater rescue surveys, coastal erosion monitoring, risk assessment surveys and pilot projects for protecting and preserving the sea front of the antique sites at Akko, Apollonia and Ashkelon. Israel proposes that the Mediterranean and European countries will establish a collaborative project aimed at mapping the cultural recourses and establishing master plans for the protection and preservation of the marine and coastal cultural heritage of the Mediterranean.     

Mass spectral studies of 6‐n‐propyl‐2‐thiouracil,its oxygen,selenium and fluorinated congeners∗

The electron ionization mass spectra of the clinically used antithyroid agent 6‐n‐propyl‐2‐thiouracil (la), its minor metabolite, 6‐n‐propyluracil (lb) and their synthetic selenium and fluorinated analogs (1c and d) have been examined. The fragmentation pattern of these thiouracil and selenouracil studied bear strong similarities with those previously derived from a study of uracil analogs. Thus, the first step in the fragmentation is a retro Diel‐Alder decomposition with the loss of HCNX (X=O, S or Se) and the production of an ion radical which undergoes further fragmentation pathways which are discussed. 6‐n‐Propyl‐2‐selenouracil (1c) did show more complicated spectra due to the six natural isotopic abundance exhibited by the selenium atom. While the fluorinated analogs (1d) did substantiate the fact that the fragmentation pattern of these derivatives proceed through fragmentation between C₂ and N₃ bond since this produces the more resonance stabilized ion.     

Alkylation of metals and the activity of metal‐alkyls†

The biochemical basis for resistance to metal ion toxicity is emerging though it is complicated by the different resistance mechanisms. Several strategies for resistance to toxic metal ions have been identified:

1. The development of energy driven efflux pumps which keep toxic element levels low in the interior of the cell. Such mechanisms have been described for Cd(II) and As(V).

2. Oxidation (e.g. AsO^2‐ to AsO₄ ^3‐) or reduction (e.g. Hg²⁺ to Hg⁰) can enzymatically and intracellularly convert a more toxic form of an element to a less toxic form.

3. The biosynthesis of intracellular polymers which serve as traps for the removal of metal ions from solution such as traps have been described for cadmium, calcium, nickel and copper.

4. The binding of metal ions to cell surfaces.

5. The precipitation of insoluble metal complexes (e.g. metal sulfides and metal oxides) at cell surfaces.

6. Biomethylation and transport through cell‐membranes by diffusion controlled processes.

In this short review I shall discuss the implications of biomethylation as a detoxification mechanism for microorganisms as well as for certain higher organisms.     

Soxhlet extraction parameters’ influence on the recovery of polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) from a sediment,and artifact formation of PCDD

Soxhlet extraction of polychlorinated dibenzo‐p‐dioxins/dibenzofurans (PCDD/F) from sediment was studied using a designed experimental set‐up. Three variables were studied: three solvent combinations n‐hexane/methanol, dichloromethane/acetone and toluene/methanol; two extraction times, 8 and 16 h, and addition of bulk substances (sodium carbonate). The extraction efficiency was almost identical in all extractions, with the exception of extraction where toluene/ methanol was combined with sodium carbonate. In these samples a major effect was observed, due to formation of Hx‐, Hp‐ and OCDD isomers. Composition of formed PCDD was similar to PCDD isomers found in pentachlorophenol products.     

Characteristics of soil fauna community in the decomposition of Deyeuxia arundinacea litters北大核心CSCD

This study aimed to understand the soil fauna characteristics during the litter decomposition process of perennial herb Deyeuxia arundinacea. The litters were put in 6-, 30-, and 260-mesh litterbags to investigate their mass loss and the dynamics of soil faunal community during Aug. 2013 to Jul. 2014. Faster decomposition rate of Deyeuxia arundinacea in different meshes was found in the early period than in mid- and end-periods. Among different mesh sizes, 6-mesh had the fastest decomposition rate, followed by 30-mesh and 260-mesh. A total of 2218 individuals of soil fauna were obtained in different meshes, with 958, 737 and 523 individuals in 30-, 260- and 6-mesh respectively. Oribatida and Poduridae were the dominant groups, accounting for 73.22% of total individuals. The soil animal individual and group densities shared a very similar trend among the decomposition bags of three aperture sizes, all with obvious characteristics of seasonal dynamic distribution. During the 12 months of decomposition, the density of soil animal groups did not show significant difference between the 6 mesh and 260 mesh decomposition bags except for May. Correlation analysis showed that the group density was highly significantly correlated with average monthly temperature and rainfall, and the individual density significantly correlated with the average monthly temperature. The results indicated that the structure and diversity of soil fauna community of Deyeuxia arundinacea are influenced by hydrothermal conditions. The findings help in understanding the effect of soil fauna to perennial herb litter decomposition.     

Gas phase equilibria for dibenzo‐p‐dioxin,dibenzo‐p‐furan and biphenyl in the C‐H‐O system

The gas phase equilibrium calculation for the C‐H‐O system at atmospheric pressure and temperature from 773 to 1773 K at intervals of 250 K was performed to understand the generation and decomposition behavior of dibenzo‐p‐dioxin (DD), dibenzo‐p‐furan (DF) and biphenyl (BP) in relation to the existing oxygen potential. It is possible to categorize these results into three regions from the viewpoint of this potential: region (A), region (B) and region (C) are that of the higher, modest and lower oxygen potential, respectively. In region (A), the equilibrium amounts of DD, DF and BP are nearly zero. In region (B), they increase once and then decrease with rise in temperature. In the most characteristic region (C), they increase uniformly with rise in temperature.     

Synthesis of 2,5‐diaryl‐2,4‐pentadienenitriles and their spectral,fluorescence and mutagenic properties

The condensation of substituted cinnamaldehydes and arylacetonitriles using sodium ethoxide in ethanol at room temperature afforded 2,5‐diaryl‐2,4‐pentadienenitriles in good yield. The structure of the reaction products was established on the basis of their infrared, nuclear magnetic resonance and elemental analysis data. Two representative compounds were studied for their mutagenic activity. One of them showed a weak mutagenicity while the second showed a high mutagenic activity in TA97a Salmonella strain. Both were negative in TA100. Some of these pentadienenitriles showed fluorescence in solutions.     

Vigilance of mustached tamarins in single-species and mixed-species groups—the influence of group composition

Species that participate in mixed-species groups (MSG) may have complementary roles in antipredator strategies. We studied vigilance in mustached tamarins (Saguinus mystax), small arboreal primates that form stable mixed-species groups with saddleback tamarins (Saguinus fuscicollis), in order to examine how the direction of vigilance changes with different species group compositions and whether the division of labor between the two species can be confirmed. We did so by comparing quantitative and qualitative differences in vigilance behavior between same individuals in and out of association (case A); MSG and single-species groups of the same total group size from two different populations (case B); and MSG of the same group size but with a different ratio of conspecifics to heterospecifics (case C). We predicted that individuals would increase downward scanning when heterospecifics are absent or their percentage is low, but total vigilance would increase only in case A due to the group size effect. However, mustached tamarins increased total vigilance due to horizontal scanning in cases A and C, and the predictions were confirmed only in small-sized groups in case B. Thus, we found indications that associating tamarin species in MSG might complement each other in the direction of vigilance, but the division of labor alone does not satisfactorily explain all the findings. There appear to be other mechanisms at work that define how direction of vigilance changes with group size and species composition. Complementarity of species probably occurs due to species vertical stratification rather than differences in the direction of vigilance.     

Transport of butyltins at the water‐air interface and the adsorptive behavior of tributyltin in the surface microlayer

The transfer dynamics and enrichment phenomena of monobutyltin chloride(MBT), dibutyltin chloride(DBT) and tributyltin chloride(TBT) at the water‐surface microlayer (SM) interface were studied. The transport processes of the three compounds at the interface are very fast in the estuarine environment. The mass transfer coefficients are 1.54 m/h for MBT, 2.16 m/h for DBT, 1.56 m/h for TBT. The effect of various factors, including pH, salinity, suspended particulate and temperature, on the adsorptive behavior of TBT in the water's surface microlayer was also studied.     

Variations in the elemental compositions of plants,and computer‐aided sampling in ecosystems∗

To obtain comparable results of multi‐element analysis of plant materials by different laboratories, a harmonized sampling procedure for terrestrial and marine ecosystems is essential. The heterogeneous distribution of chemical elements in living organisms is influenced by different biological parameters. These parameters are mainly characterized by genetic predetermination, seasonal changes, edaphic and climatic conditions, and delocalization processes of chemical substances by metabolic activities.

The biological variations of the element content in plants were divided into 5 systematic levels, which are: 1. the plant species; 2. the population; 3. the stand (within an ecosystem); 4. the individual; and 5. the plant compartment. Each of these systematic levels can be related to: 1. genetic variabilities; 2. different climatic, edaphic and anthropogenic influences; 3. microclimatic or microedaphic conditions; 4. age of plants (stage of development), exposure to environmental influences (light, wind, pollution etc.), seasonal changes; and 5. transport and deposition of substances within the different plant compartments (organs, tissues, cells, organelles).

An expert system for random and systematic sampling for multi‐element analysis of environmental materials, such as plants, soils and precipitation is presented. After statistical division of the research area, the program provides advice for contamination‐free collection of environmental samples.     

The impact of a cement company’s CSR programmes on the lifestyles of a rural community: a case study in the Ring 1 area in Tuban,East Java,Indonesia

The studies about patterns and impacts of a company’s corporate social responsibility (CSR) programmes on the local communities have been conducted in a number of developed countries. The similar studies, however, were still rarely conducted in developing countries, particularly in Indonesia. This study aims at discussing the impact of the CSR programmes of a cement company on the lifestyles of a rural community in six villages in Tuban district of East Java Province in Indonesia. The study was conducted from January to September 2015, using qualitative data collection and analysis. This study found that the presence of the cement company has made both positive and negative impacts to the rural community. For the positive impacts, we can see the development of infrastructure that makes the villages become more representative; the emergence of new business opportunities, such as food stalls and boarding houses; and the improvement of the quality of human resources through free health care, education, and religious activities. The supports from the cement company, however, have not been distributed equally among the villagers. In addition, we can also see the following negative impacts: the increase of social tense among the villagers due to the tight competition to obtain work in the cement company; the uneasy relation between the local people and the immigrants who work in the cement company; the decrease in the number of people working in agricultural sectors, as most of them have moved or wish to move to the cement company.     

A theoretical‐methodological approach towards the evaluation of environmental pollutants

The recognition and analysis as well as a generally applicable ecotoxicological evaluation are parts of the strategy towards the determination of changes in the quality of environmental compartments and their effects on humans. The progress in the field of identification of qualitative effects calls for the creation of a theoretical basis for the empirical findings. With this task being the main concern, fundamental ideas on a theoretical‐methodological approach towards the ecotoxicological evaluation of environmental chemicals are discussed. The relationships between the molecular structure and the effect of the substances in abiotic and biotic environmental compartments are the basis of this approach.     

Synthesis and antithyroid activity of 6‐n‐propyl‐5‐arylazo‐2‐thiouracils †

The synthesis of several 6‐n‐propyl‐5‐arylazo‐2‐thiouracil derivatives was achieved. The antithyroid activity of these derivatives has been determined using iodine‐125‐thiocyanate discharge technique in rats, and 6‐n‐propyl‐2‐thiouracil (PTU) as a standard. None of the 5‐arylazo‐2‐thiouracil analogs showed antithyroid activity as compared to PTU. The structure‐activity relationships (SAR) of position 5 in the PTU molecule and the requirements for better binding to the proposed receptor are discussed.