Effects of temperature on sorption-desorption processes of imidacloprid in soils of Croatian coastal regions

Sorption-desorption behavior of imidacloprid in six soils collected from five coastal regions in Croatia at 20, 30 and 40°C was investigated using batch equilibrium technique. Isothermal data were applied to Freundlich, Langmuir and Temkin equations, and the thermodynamic parameters ΔH°, ΔG°, ΔS° were calculated. The sorption isotherm curves were non-linear and may be classified as L-type, suggesting a relatively high sorption capacity for imidacloprid. Our results showed that the K( sor ) ( F ) values decreased for all the tested soils as the temperature increased, indicating that the temperature strongly influences the sorption. Values of ΔG° were negative (-4.65 to -2.00 kJ/mol) indicating that at all experimental temperatures the interactions of imidacloprid with soils were spontaneous processes. The negative and small ΔH° values (-19.79 to -8.89 kJ/mol) were in the range of weak forces, such as H-bonds, consistent with interactions and partitioning of the imidacloprid molecules into soil organic matter. The ΔS° values followed the range of -57.12 to -14.51 J/molK, suggesting that imidacloprid molecules lose entropy during transition from the solution phase to soil surface. It was found that imidacloprid desorption from soil was concentration and temperature-dependent, i.e. at lower imidacloprid concentrations and temperature, lower desorption percentage occurred. Desorption studies revealed that hysteretic behavior under different temperature treatments existed, and it was more pronounced at 20°C in the soils with higher OC content. The study results emphasize the importance of thermodynamic parameters in controlling soil pesticide mobility in different geographical locations, seasons and greenhouse conditions.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Altered toxicity of organic pollutants in water originated from simultaneous exposure to UV photolysis and CdSe/ZnS quantum dots

The paper reports unforeseen results of increased toxicity of water, subsequent to interactions between CdSe/ZnS quantum dots (QDs), phenol and toluene under UV irradiation. The consistent pattern of changes in measured toxicity (TU) was observed and correlated with degradation of phenol and/or toluene. Spearman rank coefficients (SRCs) for data pairs sum-parameters vs. TU were calculated. The highest correlation between toxicity and degradation by-products was observed for hydroquinone (0.86) and catechol (0.89). The presence of QDs in tested concentration range in the absence of UV has shown low toxicity and no interactions with phenol and/or toluene. The leak of constituent core and shell metal ions was observed. The minor differences in physical characteristics of tested QDs of the same chemical composition led to rather different degradation patterns of phenol and toluene, and the amount of leak of the metal ions as well.     

Principal component analysis for soil contamination with organochlorine compounds

In order to investigate the distribution pattern of individual organochlorine compounds in soil samples collected from the sites (Canary Island – Spain, China, Germany, India, Romania, Russia, Serbia, Swiss, UK) affected by industrial activities to the more remote areas, principal component analysis was performed on the data taken from literature. Loading plots pointed out the strong correlation among the variables. Score plots revealed similar PCB- and OCP-soil patterns for majority of the investigated sites. Nevertheless, the temporal differences of PCB-soil loads have been identified: the late 1990s and early 2000s concentrations are similar to those of the early 1940s, and they are below the levels existed in 1980. The most pronounced PCB concentrations characterized the soil from 1966. For OCPs the influence of sites location on the detected concentration has been revealed: China and India were characterized by comparably higher loads of DDX (DDT and its metabolites) and of HCH-isomers, respectively.     

Choosing an appropriate soil-gas survey method

Three types of soil-gas surveys were performed over the same location at an industrial facility. The surveys performed were (1) a passive technique using buried collectors, (2) an active technique in which samples were collected in the field by pumping with subsequent analysis at a field laboratory, and (3) a screening technique that employed a hand-held survey instrument. Each of the surveys had desirable features, but there was considerable variability in the quality of data obtained, cost, and ease of performance. The passive and active surveys provided excellent detection limits, but the passive technique does not provide data in real time. The active survey was also time-consuming and required an analytical chemist in the field. Neither the active nor the passive survey were able to delineate the plume of contaminated groundwater. Consequently, the results from the rapid and inexpensive reconnaissance technique provided functionally equivalent data.Publication No. 3672, Environmental Sciences Division, ORNL.Operated by Martin Marietta Energy Systems, Inc. for the U.S. Department of Energy under Contract No. DE-AC05-840R21400.     

Policy relevance of three integrated assessment tools—A comparison with specific reference to agricultural policies

The Common Agricultural Policy (CAP), a system of market support instruments, direct income transfers, and rural development measures, has been put through an ongoing reform process in recent decades. This paper introduces three policy impact assessment tools (SIAT, SEAMLESS-IF, MEA-Scope tool) and analyses how these tools have responded to a number of challenges for integrated assessment modelling as reported in the international literature. Significant progress has been made with regard to modelling linkages whereas other challenges, particularly those related to issues of scale and uncertainty management, require further efforts. It is also analysed which CAP instruments are represented and what kinds of effects can be analysed at different scales. Market instruments and direct payments are comparatively well represented, while the ability to model rural development measures is mostly beyond the scope of these tools. Because each tool has found a different solution for coping with the common challenges of integrated assessment modelling, the choice of one of the tools for a particular application depends strongly on the policy questions being asked. The SIAT provides the big picture via its ability to represent broad changes in policy instruments with EU-wide cross-sector impacts. The most comprehensive analysis of agricultural policy instruments can be obtained with SEAMLESS-IF. The MEA-Scope tool complements the other two approaches with detailed regional profiles.     

Distribution and availability of potentially toxic metals in soil in central area of Belgrade,Serbia

Belgrade, capital city of Serbia, has over 1,600,000 inhabitants and over 400,000 vehicles trafficking every day on its streets. The investigation of soil pollution was performed by sequential extraction analysis to investigate the availability of potentially toxic metals (Zn, Cd, Pb, Co, Ni, Cu, Cr and Mn) under different oxidation and pH conditions. All investigated metals were mainly extracted from soils with neutral or acidic extractants. Serious pollution was observed along roads and streets with high traffic frequency, but Pb and Ni pollution was the highest since their concentrations exceed both soil Serbian standard and Canadian guidance values and is characteristic for all investigated sites. Cd, Cu, Cr and Zn concentrations are moderately high since they are between Canadian guideline and Serbian standard.     

Mycorrhizal benefit differs among the sexes in a gynodioecious species

Both plant sex and arbuscular mycorrhizal (AM) symbiosis influence resource acquisition and allocation in plants, but the interaction between these two components is not well established. As the different plant sexes differ in their resource needs and allocation patterns, it is logical to presume that they might differ in their relationship with AM as well. We investigate whether the association with AM symbiosis is different according to the host plant sex in the gynodioecious Geranium sylvaticum, of which, besides female and hermaphrodite plants, intermediate plants are also recognized. Specifically, we examine the effects of two different AM fungi in plant mass allocation and phosphorus acquisition using a factorial greenhouse/common garden experiment. Cloned G. sylvaticum material was grown in symbiosis with AM fungi or in non-mycorrhizal condition. We evaluated both the symbiotic plant benefit in terms of plant mass and plant P content and the fungal benefit in terms of AM colonization intensity in the plant roots and spore production. Our results suggest that G. sylvaticum plants benefit from the symbiosis with both AM fungal species tested but that the benefits gained from the symbiosis depend on the sex of the plant and on the trait investigated. Hermaphrodites suffered most from the lack of AM symbiosis as the proportion of flowering plants was dramatically reduced by the absence of AM fungi. However, females and intermediates benefited from the symbiosis relatively more than hermaphrodites in terms of higher P acquisition. The two AM fungal species differed in the amount of resources accumulated, and the fungal benefit was also dependent on the sex of the host plant. This study provides the first evidence of sex-specific benefits from mycorrhizal symbiosis in a gynodioecious plant species.     

U and Th in some brown coals of Serbia and Montenegro and their environmental impact

GOAL, SCOPE AND BACKGROUND: The objective of this paper is to determine and compare the concentrations of U and Th in soft to hard brown (lignite to sub-bituminous) coals of Serbia and Montenegro. It also presents comparison of the obtained data on U and Th concentrations with the published data on coals located in some other countries of the world. Almost the whole coal production of Serbia and Montenegro is used as feed coals for combustion in thermal power plants. METHODS: Channel samples from open pit and underground mines and core samples were collected for hard and soft brown coals. For the analysis the samples were decomposed using microwave technique. Obtained solutions containing U and Th were analyzed by inductively coupled plasma mass spectroscopy (ICP-MS) using NIST standards. RESULTS: Concentration of U from the investigated basins and the corresponding mine fields ranges within 0.60-70.10 mg/kg, 0.65-3.20 mg/kg, 0.95-6.59 mg/kg, 1.20-6.05 mg/kg, 0.80-6.66 mg/kg, 0.18-89.90 mg/kg, 0.19-4.14 mg/kg, and 0.28-3.52 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. Concentration of Th ranges within 0.20-2.60 mg/kg, 0.84-6.57 mg/kg, 1.48-6.48 mg/kg, 0.12-2.71 mg/kg, 0.13-4.95 mg/kg, 0.14-3.48 mg/kg, 0.29-3.56 mg/kg, and 0.17-1.89 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. DISCUSSION: Brown coal from Senje-Resavica, Kolubara, Kostolac and Pljevlja is characterized by low U concentration. Coals form the Krepoljin, Soko Banja and Sjenica basins have slightly higher U concentrations than the mentioned group. The highest concentration of U is characteristic for the coal from the Bogovina East field. Concentration of Th in coals from Serbia and Montenegro has proved to be low. Out of all investigated coal basins, only the coal from the Krepoljin and Kolubara basins has high concentration of Th. The hydrothermally altered rocks of the Timok dacite-andesite complex, representing the basement of the Bogovina basin, could be a potential source of U, especially at the bottom part of the Lower seam of the Bogovina East field. CONCLUSIONS: This study shows that brown coals in Serbia and Montenegro (soft to hard brown coals or lignite to sub-bituminous) contain low levels of U (5.30 mg/kg, average value and 2.10 mg/kg geometric mean value) and Th (1.80 mg/kg, average value and 1.12 mg/kg geometric mean value). There are some obvious differences in concentration of U and Th in coals from different basins in Serbia and Montenegro. The approximate value for U and Th release mainly from power plants was 644.33 t and 983.46 t, respectively within the period 1965-2000 for the studied mines in Serbia, and 23.76 t and 15.05 t for the Potrlica mine (Montenegro) within the period 1965-1997. RECOMMENDATIONS: The coals in Serbia and Montenegro show no identifiable unfavourable impact on the surrounding environment, due to low natural radioactive concentration of U and Th, but further investigations concerning human health should be performed. PERSPECTIVES: Preliminary research revealed that in some Serbian coals (and, particularly, parts of the coal seam) U and Th content are rather high. Such coals should be carefully studied, as well as U and Th concentrations in ash, fly ash, waste disposals, nearby soil and ground water. Further studies should include determination of the radioactivity of all these products, and estimation of possible health impact.