Methods for synthesis of nonabromodiphenyl ethers and a chloro-nonabromodiphenyl ether

Polybrominated diphenyl ethers (PBDEs) have been used extensively as brominated flame retardants (BFRs) in textiles, upholstery and electronics. They are ubiquitous contaminants in wildlife and humans. A low concentration of nonabrominated diphenyl ethers (nonaBDEs) is present in commercial DecaBDE and they are also abiotic and biotic debromination products of decabromodiphenyl ether (BDE-209). The objective of the present work was to develop methods for synthesis of the three nonaBDEs, 2,2',3,3',4,4',5,5',6-nonabromodiphenyl ether (BDE-206), 2,2',3,3',4,4',5,6,6'-nonabromodiphenyl ether (BDE-207) and 2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (BDE-208), with the intention of making them available as authentic standards for analytical, toxicological and stability studies, as well as studies regarding physical-chemical properties. Two methods were developed, one based on perbromination of phenoxyanilines and the other via reductive debromination of BDE-209 by sodium borohydride followed by chromatographic separation of the three nonaBDE isomers formed. An additional nonabrominated compound, 4'-chloro-2,2',3,3',4,5,5',6,6'-nonabromodiphenyl ether (Cl-BDE-208), was also synthesized in the present work. Cl-BDE-208, prepared by the perbromination of 4-chlorodiphenyl ether, may be used as an internal standard in analysis of highly brominated diphenyl ethers. BDE-206, BDE-207, BDE-208 and Cl-BDE-208 were characterized by 1H NMR, 13C NMR, electron ionization mass spectra and by their melting points. The structures of all three nonaBDEs have been characterized previously by X-ray crystallography.     

Perfluorinated chemicals in relation to other persistent organic pollutants in human blood

In order to evaluate blood levels of some perfluorinated chemicals (PFCs) and compare them to current levels of classical persistent organic pollutants (POPs) whole blood samples from Sweden were analyzed with respect to 12 PFCs, 37 polychlorinated biphenyls (PCBs), p,p'-dichlorodiphenyl-dichloroethylene (DDE), hexachlorobenzene (HCB), six chlordanes and three polybrominated diphenyl ethers (PBDEs). The median concentration, on whole blood basis, of the sum of PFCs was 20-50 times higher compared to the sum of PCBs and p,p'-DDE, 300-450 times higher than HCB, sum of chlordanes and sum of PBDEs. Estimations of the total body amount of PFCs and lipophilic POPs point at similar body burdens. While levels of for example PCBs and PBDEs are normalized to the lipid content of blood, there is no such general procedure for PFCs in blood. The distributions of a number of perfluorinated compounds between whole blood and plasma were therefore studied. Plasma concentrations were higher than whole blood concentrations for four perfluoroalkylated acids with plasma/whole blood ratios between 1.1 and 1.4, whereas the ratio for perflurooctanesulfonamide (PFOSA) was considerably lower (0.2). This suggests that the comparison of levels of PFCs determined in plasma with levels determined in whole blood should be made with caution. We also conclude that Swedish residents are exposed to a large number of PFCs to the same extent as in USA, Japan, Colombia and the few other countries from which data is available today.     

Preliminary assessment of risk of ozone impacts to maize (Zea mays) in southern Africa

Surface ozone concentrations in southern Africa exceed air quality guidelines set to protect agricultural crops. This paper addresses a knowledge gap by performing a preliminary assessment of potential ozone impacts on vegetation in southern African. Maize (Zea mays L.) is the receptor of interest in the main maize producing countries, i.e. South Africa, Zambia and Zimbabwe. Surface ozone concentrations are estimated for the growing season (October to April) using photochemical modelling. Hourly mean modelled ozone concentrations ranged between 19.7 and 31.2 ppb, while maximums range between 28.9 and 61.9 ppb, and are near 30 ppb over South Africa and Zambia, while in Zimbabwe, they exceed 40 ppb and translate into monthly AOT40 values of over 3,000 ppb h in five of the seven months of the growing season. This study suggests that surface ozone may pose a threat to agricultural production in southern African, particularly in Zimbabwe.     

Toxicity of pesticides toward human immune cells U-937 and HL-60

Abstract

The industrialization of the agricultural sector has significantly increased the use of chemicals such as pesticides. Therefore, exposure to them is unavoidable, which makes it necessary to assess their safety for humans at actual exposure doses. This paper aims to determine toxicity of three types of pesticides toward human immune cells (HL-60 and U-937): glyphosate (GLY), deltamethrin (DEL), and chlorothalonil (CHL). Cell viability, membrane integrity, inflammation induction, and antioxidant activity were evaluated to determine differences in cellular response to the tested plant protection agents. In experimental models, all tested substances caused increased mortality of cells after only 24?h. Cell membrane damage was recorded under DEL and CHL influences. The largest disintegration of the cell membrane was due to the action of 100?μg/mL DEL for U-937 and CHL at 1?μg/mL for HL-60. GLY at a concentration of 3,600?μg/mL caused significant peroxidation of U-937 cells’ lipids. CHL-induced inflammation in both types of cells tested. DEL and GLY also induced antioxidant activity in cells. These results lead to the conclusion that the tested pesticides act cytotoxically to the cells of the human immune system in doses to which both farmers and consumers are exposed.     

Deriving heart rate variability indices from cardiac monitoring—An indicator of driver sleepiness

Objective: Driver fatigue is considered to be a major contributor to road traffic crashes. Cardiac monitoring and heart rate variability (HRV) analysis is a candidate method for early and accurate detection of driver sleepiness. This study has 2 objectives: to evaluate the (1) suitability of different preprocessing strategies for detecting and removing outlier heartbeats and spectral transformation of HRV signals and their impact of driver sleepiness assessment and (2) relation between common HRV indices and subjective sleepiness reported by a large number of drivers in real driving situations, for the first time.

Methods: The study analyzed >3,500 5-min driving epochs from 76 drivers on a public motorway in Sweden. The electrocardiograph (ECG) data were recorded in 3 studies designed to evaluate the physiological differences between awake and sleepy drivers. The drivers reported their perceived level of sleepiness according to the Karolinska Sleepiness Scale (KSS) every 5?min. Two standard methods were used for identifying outlier heartbeats: (1) percentage change (PC), where outliers were defined as interbeat intervals deviating >30% from the mean of the four previous intervals and (2) standard deviation (SD), where outliers were defined as interbeat interval deviating >4 SD from the mean interval duration in the current epoch. Three standard methods were used for spectral transformation, which is needed for deriving HRV indices in the frequency domain: (1) Fourier transform; (2) autoregressive model; and (3) Lomb-Scargle periodogram. Different preprocessing strategies were compared regarding their impact on derivation of common HRV indices and their relation to KSS data distribution, using box plots and statistical tests such as analysis of variance (ANOVA) and Student’s t test.

Results: The ability of HRV indices to discriminate between alert and sleepy drivers does not differ significantly depending on which outlier detection and spectral transformation methods are used. As expected, with increasing sleepiness, the heart rate decreased, whereas heart rate variability overall increased. Furthermore, HRV parameters representing the parasympathetic branch of the autonomous nervous system increased. An unexpected finding was that parameters representing the sympathetic branch of the autonomous nervous system also increased with increasing KSS level. We hypothesize that this increment was due to stress induced by trying to avoid an incident, because the drivers were in real driving situations.

Conclusions: The association of HRV indices to KSS did not depend on the preprocessing strategy. No preprocessing method showed superiority for HRV association to driver sleepiness. This was also true for combinations of methods for frequency domain HRV indices. The results prove clear relationships between HRV indices and perceived sleepiness. Thus, HRV analysis shows promise for driver sleepiness detection.     

Pigment composition and size distribution of phytoplankton in a confined Mediterranean salt marsh ecosystem

Pigment composition and size distribution of phytoplankton were analysed in a group of Mediterranean salt marshes, where hydrology is dominated by sudden inputs during sea storms, followed by long periods of confinement. These marshes are characterized by a low inorganic–organic nutrient ratio, and inorganic nitrogen is especially scarce due to denitrification. Nutrients were the main factor affecting phytoplankton biomass, while zooplankton grazing did not control either phytoplankton community composition, or their size distribution. The relative abundance of the different phytoplankton groups was analysed by correspondence analysis using the pigment composition measured by high-performance liquid chromatography (HPLC) and analysed with the CHEMTAX programme. In this analysis, phytoplankton pigment composition was correlated with two nutrient gradients. The first gradient was the ratio of nitrate–total nitrogen (TN), since the different phytoplankton groups were distributed according to their eco–physiological differences in nitrogen uptake. The second gradient was correlated with total nutrient loading. Biomass size distributions frequently showed a lack of intermediate sized nanophytoplankton (2.5–4 μm in diameter), and the importance of this lack of intermediate sizes correlated with dinoflagellate biomass. These results suggested that in confined environments, where nutrients are mainly in an organic form, dinoflagellates take advantage of their mixotrophy, by competing and grazing on smaller phytoplankters simultaneously.     

南非两个自然旅游经营项目中的当地社区受益体系

南非的两个自然旅游经营项目 - - 尼加拉私人狩猎保护区和洛克泰尔湾已经建立了完全不同 的当地社区受益体系 .一个是靠独立的外部捐款资助 , 另一个是通过分红利 .本文阐述了利益 管理机制以及每个体系对附近居民的影响 .居民的一些受益 ( 如就业、企业家机遇、资源利用 、对传统仪式的支持 ) 与正式的社区受益体系没有直接关系 .     

Encounters between Antarctic limpets, <Emphasis Type="Italic">Nacella concinna</Emphasis>, and predatory sea stars, <Emphasis Type="Italic">Lysasterias</Emphasis> sp., in laboratory and field experiments

Antarctic limpets, Nacella concinna, from the Admiralty Bay (King George Island, South Shetlands) for at least part of the year (austral winter) co-exist with predatory sea stars Lysasterias sp. Our laboratory and field experiments established that the presence of Lysasterias sp. or its odour had considerable influence upon their behaviour. Limpets’ responses, consisting of shell mushrooming, shell rotation and flight, were distinctly different from their reaction to other stimuli, such as food and conspecific odours, or mechanical stimulation. Moreover, a significant impact of sea star presence on limpets’ activity was observed, with limpets fleeing to a distance of 60 cm from the predator. Such reactions allow limpets to lower the incidence of sea star predation, but at the cost of presumptive disrupting of foraging and an additional energy expended for locomotion. A visible difference was noted between two limpet populations, with the rockpool limpets responding only after physical contact with being touched by a sea star, and the subtidal ones responding at a distance of up to 20 cm.