Formation of PFOA from 8:2 FTOH in closed-bottle experiments with brackish water

The formation of perfluorooctanoate (PFOA) from 1H,1H,2H,2H-perfluorodecanol (8:2 FTOH) was studied for the first time in laboratory experiments with brackish water. The water samples were collected from the Baltic Sea, which is one of the largest brackish water areas in the world and is polluted with PFOA and other perfluorinated compounds. The formation of PFOA was studied in closed-bottle experiments at different water temperatures. As a reference experiment, a modified OECD 310 test was conducted with sludge from a wastewater treatment plant and with brackish water. The PFOA and 8:2 FTOH were concentrated from water samples by solid-phase extraction (SPE) and were analysed using liquid chromatography–mass spectrometry. The effect of oxygen concentration on the formation of PFOA was studied using surface water samples with high and low oxygen contents. Other experiments were performed with oxygen-rich surface water and oxygen-deficient bottom water. The formation of PFOA was observed in all experiments; it was higher in the trial performed with brackish water than in the reference test carried out with sludge. Clear temperature dependence was observed in the formation of PFOA in brackish water tests; after a 30-day test period, a sixfold increase was observed in the amount of PFOA in surface water between the temperatures of 15 and 20 °C. Microbes were suggested as the major cause of the formation of PFOA, but other environmental characteristics, such as oxygen, could also affect the formation potential of PFOA.     

Molecular orbital studies on brominated diphenyl ethers. Part I--conformational properties

Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame retardants and quantities in the environment are on the rise. Because they are structurally related to polychlorinated biphenyls and also to thyroid hormones, there is serious concern that PBDEs may pose a danger to human health. Knowledge of their conformational properties is key to assessing their environmental fate and risk. The conformational properties of PBDEs were investigated by quantum chemical methods including semiempirical self-consistent field molecular orbital (SCF-MO), ab initio SCF-MO and density functional theory (DFT). Conformational analyses of model congeners 2,2',4,6'-tetrabromodiphenyl ether and 2,3,4,4',5,6-hexabromodiphenyl ether, based on energy maps calculated by semiempirical AM1 method, may indicate that all PBDE congeners except those with the tetra-ortho-bromination are conformationally flexible (or soft) due to low energy barriers for interconversion of stable conformers. The results of the conformational analyses are in conformity with recently published X-ray crystallographic data. For comparison with the results of the semiempirical method, higher level ab initio and DFT models were applied as well. The optimized geometries all lie well inside low energy regions on the maps and thus also ascertain the semiempirical calculations. According to computed geometric parameters and net atomic charges, the model B3LYP/3-21G* seemed to give better results than B3LYP/6-31G* and HF/6-31G*.     

Molecular orbital studies on brominated diphenyl ethers. Part II--reactivity and quantitative structure-activity (property) relationships

Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants and are increasingly turning up in the environment. Their structural similarities to polychlorinated biphenyls and thyroid hormones suggest they may be a risk to human health. The present study examines the reactivity of brominated diphenyl ethers (BDEs) on the basis of the electronic structures as calculated by semiempirical AM1 self-consistent field molecular orbital (SCF-MO) method. Frontier orbital energies were used to elucidate the reactivity of BDEs in electrophilic, nucleophilic and photolytic reactions. From an examination of the frontier electron densities, the regioselectivity, or orientation, of metabolic reactions of BDEs was predicted. Furthermore, satisfactory quantitative structure-activity (property) relationship (QSAR and QSPR) models were derived to calculate gas chromatographic and ultraviolet spectral properties and luciferase induction activities from the AM1-computed electronic parameters.     

联合基于野外的代谢组学和化学分析手段筛选优先关注新兴污染物：在五大湖流域的案例研究

由于毒性评估项目很难与日渐增长的需要测试的污染物保持同步,所以较难将关注点集中在影响水生生态系统的最为生物相关的污染物上。由于评估潜在毒性污染物所造成的生物影响已被证明是有效的,内生性代谢物的研究（代谢组学）对于剔除那些较低可能造成生物影响的污染物或许有一定帮助,从而找出生物重要性最高的污染物。本研究在北美五大湖流域的18个地点针对置于笼中的黑头软口鲦（Pimephales promelas）进行实验。我们测定了水体温度和水样中的污染物浓度（目标污染物132种,检出86种）,并使用1H-NMR谱测量了肝极性提取物中的内生性代谢物。利用偏最小二乘法回归来比对内生性代谢物的相对丰度与污染物浓度和环境温度。结果表明内生性极性代谢物的指标与最多49种污染物存在共同变化。因此我们认为至多52%的检出污染物与内生性代谢物变化的共同变化不显著,表明这些污染物很可能不会在这些地点造成可以检测到的影响。这是通过缩短对于实验地点有着潜在影响的污染物列表从而扫描出检出污染物生物相关性的第一步。类似的信息有助于风险评估者区分不同污染物的重要性并将重点毒性测试放在最为生物相关的污染物上。
精选自Nicol Janecko, Lucie Pokludova, Jana Blahova, Zdenka Svobodova, Ivan Literak. Linking field-based metabolomics and chemical analyses to prioritize contaminants of emerging concern in the Great Lakes basin. Environmental Toxicology and Chemistry: Volume 35, Issue 10, pages 2493–2502, October 2016. DOI: 10.1002/etc.3409
详情请见http://onlinelibrary.wiley.com/doi/10.1002/etc.3409/full
     

Friends and family vs. government: who does the public rely on more to prepare for natural disasters?

This paper examines what organizations and groups individuals rely on to help prepare for natural disasters and how reliance differs vis-à-vis demographic characteristics. Using data gathered from 2,008 individuals employed in the United States, the results revealed that individuals are significantly more likely to rely on friends and family than government organizations at the local, state, and federal level. The findings also suggest that this reliance varies across demographic groups. For example, data from the present study suggest that women and minority groups as well as individuals who are older and less educated are significantly more likely to rely on organizations to help prepare for natural disasters. This study contributes to the disaster management and risk communication literatures by offering key insights into the organizations and groups the American public in general, and certain demographic groups in particular, rely on when it comes to preparing for natural disasters. Knowledge about the organizations and groups that individuals rely on to help prepare for natural disasters can help policymakers and practitioners target those organizations as conduits to deliver critical preparedness information, as well as other information related to disaster mitigation, response, and recovery.     

Organic chlorine compounds in lake sediments. III. Chlorohydrocarbons, free and chemically bound chlorophenols

Chlorohydrocarbons and free and chemically bound chlorophenols, catechols and guaiacols were measured from lake sediments in Central Finland. Chlorohydrocarbons occurred at low backround levels except chlorocymenes from pulp mills and PCBs near the city of Äänekoski, where a local leakage occurrs. Free chlorophenols (hexane extractables) were found in all 18 areas studied, but the bound ones (extracted with strong alkali) only in the pulp mill reciepient lakes where they dominated. Preliminary analyses of chemically bound chlorophenols in high molecular fractions of spent bleach liquors and pulp mill effluents indicated that majority of chlorocatechols and guaiacols are bound already in the factory.     

Building a better baseline to estimate 160 years of avian population change and create historically informed conservation targets

Globally, anthropogenic land-cover change has been dramatic over the last few centuries and is frequently invoked as a major cause of wildlife population declines. Baseline data currently used to assess population trends, however, began well after major changes to the landscape. In the United States and Canada, breeding bird population trends are assessed by the North American Breeding Bird Survey, which began in the 1960s. Estimates of distribution and abundance prior to major habitat alteration would add historical perspective to contemporary trends and allow for historically based conservation targets. We used a hindcasting framework to estimate change in distribution and abundance of 7 bird species in the Willamette Valley, Oregon (United States). After reconciling classification schemes of current and 1850s reconstructed land cover, we used multiscale species distribution models and hierarchical distance sampling models to predict spatially explicit densities in the modern and historical landscapes. We estimated that since the 1850s, White-breasted Nuthatch (Sitta carolinensis) and Western Meadowlark (Sturnella neglecta) populations, 2 species sensitive to fragmentation of oak woodlands and grasslands, declined by 93% and 97%, respectively. Five other species we estimated nearly stable or increasing populations, despite steep regional declines since the 1960s. Based on these estimates, we developed historically based conservation targets for amount of habitat, population, and density for each species. Hindcasted reconstructions provide historical perspective for assessing contemporary trends and allow for historically based conservation targets that can inform current management.     

Quantifying anthropogenic threats to orchids using the IUCN Red List

Orchids are diverse, occur in a wide range of habitats and dominate threatened species lists, but which orchids are threatened, where and by what? Using the International Union for Conservation of Nature Red List, we assessed the range and diversity of threats to orchids globally including identifying four threat syndromes: (1) terrestrial orchids in forests that are endemic to a country and threatened by illegal collecting; (2) orchids threatened by climate change, pollution, transportation and disturbance/development for tourism, and recreation activities, often in East Asia; (3) epiphytic orchids in Sub-Saharan Africa including Madagascar with diverse threats; and (4) South and Southeast Asia orchids threatened by land clearing for shifting agriculture. Despite limitations in the Red List data, the results highlight how conservation efforts can focus on clusters of co-occurring threats in regions while remaining aware of the trifecta of broad threats from plant collecting, land clearing and climate change.     

Variations in public and private employees’ perceptions of organizational preparedness for natural disasters

Studies have demonstrated that public and private organizations differ in many respects (e.g. funding mechanisms and risk-taking capabilities). Based on this scholarship, we expect to see differences in their disaster preparedness levels. Hence, we propose the following research question: Are there variations in public and private employees’ perceptions of organizational preparedness for natural disasters? We answer this question by employing the theories of publicness and social identity. We define publicness through the core approach arguing that public and private organizations are uniquely different based on their legal status or ownership and social identity as an individual’s feeling of oneness or belongingness to a particular group or organization. Using data gathered in 2014 from a nationally representative sample of 1634 public and private employees in the United States, we posit that employees of private organizations will report higher preparedness levels in comparison to employees of public organizations. Our proposition is based on scholarship that found a negative relationship between publicness and organizational identification and a positive relationship between organizational identification and organizational performance. Contrary to our proposition, but in line with the disaster literature, the results showed that in general, employees of public organizations reported a higher preparedness level than employees of private organizations.