Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs)

BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model.     

Management of microbial contamination in storm runoff from California coastal dairy pastures

A survey of storm runoff fecal coliform bacteria (FCB) from working farm and ranch pastures is presented in conjunction with a survey of FCB in manure management systems (MMS). The cross-sectional survey of pasture runoff was conducted on 34 pastures on five different dairies over 2 yr under varying conditions of precipitation, slope, manure management, and use of conservation practices such as vegetative filter strips. The MMS cross-sectional survey consisted of samples collected during 1 yr on nine different dairies from six loafing barns, nine primary lagoons, 12 secondary lagoons, and six irrigation sample points. Pasture runoff samples were additionally analyzed for Cryptosporidium sp. and Giardia duodenalis, whereby detectable concentrations occurred sporadically at higher FCB concentrations resulting in poor correlations with FCB. Prevalence of both parasites was lower relative to high-use areas studied simultaneously on these same farms. Application of manure to pastures more than 2 wk in advance of storm-associated runoff was related to a > or =80% reduction in FCB concentration and load compared to applications within 2 wk before a runoff event. For every 10 m of buffer length, a 24% reduction in FCB concentration was documented. A one-half (75%), one (90%), and two (99%) log10 reduction in manure FCB concentration was observed for manure holding times in MMS of approximately 20, 66, and 133 d, respectively. These results suggest that there are several management and conservation practices for working farms that may result in reduced FCB fluxes from agricultural operations.     

北京大气PM2.5中微量元素的浓度变化特征与来源

为了解北京大气细粒子中微量元素的污染水平和来源,在车公庄和清华园进行了连续1年、每周1次的PM2.5采样和全样品分析.微量元素浓度的周变化大,尤以冬季为甚,相邻2周最大相差达1.6倍;但除冬季的平均浓度较高之外,其季节变化并不显著.微量元素的富集因子在春季最低,反映了频繁发生的沙尘天气的影响.Se、Br和Pb的浓度比来自于北京A层土壤中的含量要高出约1000～8000倍,表明它们主要来自于人为污染.其中Se的富集度最高,反映了北京细粒子来自于燃煤污染的特征.Pb的年均浓度(0.31μg@m-3)虽然未超过WHO的年均标准,但与洛杉矶和布里斯班相比处于较高的水平;与Br、Se的比较分析表明,燃煤可能是Pb除机动车排放之外的另一个重要来源.     

Effects of some environmental parameters on catalase activity measured in the mussel (Mytilus galloprovincialis) exposed to lindane

Mussels (Mytilus galloprovincialis), collected from the Bizerta lagoon, were acclimated for four days to various conditions of temperature, salinity, photoperiod and food supply and then exposed to lindane at a concentration of 40 microg l(-1). Catalase activity, which is a biomarker of exposure to an oxidative stress, was measured in the whole soft tissues of control and assay groups. In control mussels, high temperature, high salinity and light duration significantly increased catalase activity whereas this activity decreased when food, composed of freeze-dried, algae was available. When mussels were treated with lindane, catalase activities were higher than in controls. This increase was significant with temperature, salinity and light duration. The food supply did not change catalase activity, which was always higher compared to controls. Oxidative stress was shown in mussels exposed to lindane. The results highlight the need of considering abiotic parameters in biomonitoring studies, and especially when using catalase as a biomarker.     

Peri-urban agro-ecosystems in the Mediterranean: diversity,dynamics, and drivers

Regional Environmental Change - To address sustainability challenges of agro-ecosystems located in Mediterranean urban regions, this paper focuses on the multidisciplinary subject of urban...     

Trying Not to Get Burned: Understanding Homeowners’ Wildfire Risk–Mitigation Behaviors

Three causes have been identified for the spiraling cost of wildfire suppression in the United States: climate change, fuel accumulation from past wildfire suppression, and development in fire-prone areas. Because little is likely to be performed to halt the effects of climate on wildfire risk, and because fuel-management budgets cannot keep pace with fuel accumulation let alone reverse it, changing the behaviors of existing and potential homeowners in fire-prone areas is the most promising approach to decreasing the cost of suppressing wildfires in the wildland–urban interface and increasing the odds of homes surviving wildfire events. Wildfire education efforts encourage homeowners to manage their property to decrease wildfire risk. Such programs may be more effective with a better understanding of the factors related to homeowners’ decisions to undertake wildfire risk–reduction actions. In this study, we measured whether homeowners had implemented 12 wildfire risk–mitigation measures in 2 Colorado Front Range counties. We found that wildfire information received from local volunteer fire departments and county wildfire specialists, as well as talking with neighbors about wildfire, were positively associated with higher levels of mitigation. Firsthand experience in the form of preparing for or undertaking an evacuation was also associated with a higher level of mitigation. Finally, homeowners who perceived higher levels of wildfire risk on their property had undertaken higher levels of wildfire-risk mitigation on their property.     

Government and voluntary policymaking for sustainability in mining towns: A longitudinal analysis of Itabira,Brazil

The socio‐economic fabric of single‐company mining towns needs to be carefully considered by both Government and companies in sustainability policymaking. Policy design and effectiveness in such towns are significantly impacted by the city's economic dependence on a single company. This paper explores the perceived effectiveness of government and voluntary private sector mining policies for pursuing sustainability in the historic mining town of Itabira, Brazil over a period of 20 years. Itabira serves as a worthwhile case study because it allows for an in‐depth and longitudinal analysis that can reveal valuable lessons to policymakers of different sectors and jurisdictions located elsewhere. Based on extensive face‐to‐face interviews and literature reviews, study results indicate that changes to the state environmental licensing policies in the 1990s led to significant socio‐environmental improvements in the area. The globalization of the mining company also contributed to an increase in the quantity and quality of voluntary industry policies. Recent technological improvements in the beneficiation processes of the mining company promises to extend the life of the mine to 2050. Although there are significant incremental socio‐environmental policies and programmes, sustainability remains an elusive vision in Itabira, with no clear objectives or monitoring and accountability mechanisms. The paper concludes by recommending a more formal integrated policymaking framework.     

Water security for northern peoples: review of threats to Arctic freshwater systems in Nunavut,Canada

Regional Environmental Change - Water is a fundamental component of the ecological integrity, economic development, and sustainability of northern regions, as well as the health and well-being of...