Hydroxyl, hydroperoxyl free radicals determination methods in atmosphere and troposphere

The hydroxyl radical (?OH) has a crucial function in the oxidation and removal of many atmospheric compounds that are harmful to health. Nevertheless, high reactivity, low atmospheric abundance, determination of hydroxyl, and hydroperoxyl radical's quantity is very difficult. In the atmosphere and troposphere, hydroperoxyl radicals (HO₂) are closely demanded in the chemical oxidation of the troposphere. But advances in technology have allowed researchers to improve the determination methods on the research of free radicals through some spectroscopic techniques. So far, several methods such as laser-induced fluorescence (LIF), high-performance liquid chromatography (HPLC), and chemical ionization mass spectroscopy have been identified and mostly used in determining the quantity of hydroxyl and hydroperoxyl radicals. In this systematic review, we have advised the use of scavenger as an advance for further researchers to circumvent some of these problems caused by free radicals. The primary goal of this review is to deepen our understanding of the functions of the most critical free radical (?OH, HO₂) and also understand the currently used methods to quantify them in the atmosphere and troposphere.     

Complex national sampling design for long-term monitoring of protected dry grasslands in Switzerland

We describe a probabilistic sampling design of circular permanent plots for the long-term monitoring of protected dry grasslands in Switzerland. The population under study is defined by the perimeter of a national inventory. The monitoring focus is on the species composition of the protected grassland vegetation and derived conservation values. Efficient trend estimations are required for the whole country and for some predefined target groups (six biogeographical regions and eleven vegetation types). The target groups are equally important regardless of their size. Consequently, intensified sampling of the less frequent groups is essential for sample efficiency. The prior information needed to draw a targeted sample is obtained from the sampling frame and external databases. The logistics and generalized delineation of the target population may pose further problems. Thus, investments in fieldwork and travel time should be well balanced by selecting a cluster sample. Second, any access problems in the field and non-target units in the sample should be compensated for by selecting reserve plots as they otherwise may considerably reduce the effective sample size. Finally, the design has to be flexible as the sampling frame may change over time and sampling intensity might have to be adjusted to redefined budgets or requirements. Likewise, the variables and biological items of interest may change. To fulfil all these constraints and to optimally use the available prior information, we propose a multi-stage self-weighted unequal probability sampling design. The design uses modern techniques such as: balanced sampling, spreading, stratified balancing, calibration, unequal probability sampling and power allocation. This sampling design meets the numerous requirements of this study and provides a very efficient estimator.     

Dairy manure as a potential source of crop nutrients and environmental contaminants

Although animal manure is applied to agricultural fields for its nutrient value, it may also contain potential contaminants. To determine the variability in such contaminants as well as in valuable nutrients, nine uncomposted manure samples from Idaho dairies collected during 2.5 years were analyzed for macro- and micro-nutrients, hormones, phytoestrogens, antibiotics, veterinary drugs, antibiotic resistance genes, and genetic elements involved in the spread of antibiotic resistance. Total N ranged from 6.8 to 30.7 (C:N of 10 to 21), P from 2.4 to 9.0, and K from 10.2 to 47.7 g/kg manure. Zn (103 – 348 mg/kg) was more abundant than Cu (56 – 127 mg/kg) in all samples. Phytoestrogens were the most prevalent contaminants detected, with concentrations fluctuating over time, reflecting animal diets. This is the first study to document the presence of flunixin, a non-steroidal anti-inflammatory drug, in solid stacked manure from regular dairy operations. Monensin was the most frequently detected antibiotic. Progesterones and sulfonamides were regularly detected. We also investigated the relative abundance of several types of plasmids involved in the spread of antibiotic resistance in clinical settings. Plasmids belonging to the IncI, IncP, and IncQ1 incompatibility groups were found in almost all manure samples. IncQ1 plasmids, class 1 integrons, and sulfonamide resistance genes were the most widespread and abundant genetic element surveyed, emphasizing their potential role in the spread of antibiotic resistance. The benefits associated with amending agricultural soils with dairy manure must be carefully weighed against the potential negative consequences of any manure contaminants.     

Development of a combined isotopic and mass-balance approach to determine dissolved organic carbon sources in eutrophic reservoirs

A combined mass-balance and stable isotope approach was set up to identify and quantify dissolved organic carbon (DOC) sources in a DOC-rich (9 mg L⁻¹) eutrophic reservoir located in Western France and used for drinking water supply (so-called Rophemel reservoir). The mass-balance approach consisted in measuring the flux of allochthonous DOC on a daily basis, and in comparing it with the effective (measured) DOC concentration of the reservoir. The isotopic approach consisted, for its part, in measuring the carbon isotope ratios (δ¹³C values) of both allochthonous and autochthonous DOC sources, and comparing these values with the δ¹³C values of the reservoir DOC. Results from both approaches were consistent pointing out for a DOC of 100% allochthonous origin. In particular, the δ¹³C values of the DOC recovered in the reservoir (−28.5 ± 0.2‰; n = 22) during the algal bloom season (May-September) showed no trace of an autochthonous contribution (δ¹³C in algae = −30.1 ± 0.3‰; n = 2) being indistinguishable from the δ¹³C values of allochthonous DOC from inflowing rivers (−28.6 ± 0.1‰; n = 8). These results demonstrate that eutrophication is not responsible for the high DOC concentrations observed in the Rophemel reservoir and that limiting eutrophication of this reservoir will not reduce the potential formation of disinfection by-products during water treatment. The methodology developed in this study based on a complementary isotopic and mass-balance approach provides a powerful tool, suitable to identify and quantify DOC sources in eutrophic, DOC-contaminated reservoirs.     

Study of the dispersion of VOCs emitted by a municipal solid waste landfill

The dispersion of VOCs emitted by a municipal solid waste landfill was studied for a period of over one year. Sixteen VOCs were monitored: linear alkanes from C₇ to C₁₁, BTEX, trimethylbenzene, trichlorethylene, tetrachlorethylene, α and β-pinenes, limonene. The analytical procedure was first comprised of static long-term sampling of about 2 months using radial diffusion Radiello tubes containing activated carbon, followed by extraction by solvent (i.e. CS₂) and GC/MS analysis. The results were initially analysed on the basis of the total concentration of the quantified VOCs, then by examining the concentrations of certain selected compounds. The influence of different parameters such as operating conditions, meteorological conditions and site morphology was highlighted on the basis of total VOC concentrations. In order to study the VOC's dispersion more closely, 5 compounds were chosen: toluene, benzene, limonene, and the sum trichlorethylene + tetrachlorethylene, as a “marker”, to verify the origin of the VOCs emitted. The results showed that the main source of VOCs is the open cell and lead to different hypotheses on interferences from neighbouring sources and to the proposal of solutions to limit the emission of VOCs and their dispersion. To our knowledge, this type of study has not been accomplished until this day.     

Trends in management plans and guides: 25 years of experience from Southern France

This study analysed 14 management plans and guidelines from a 25-year period to understand trends in conservation planning. A Rosetta Stone Analysis was used for the systematic comparison of plans and guidelines. Management plans incorporated management philosophies, management scenarios, opportunities for infrastructure, and plans for data collection by 2000. As of 2010, they incorporated ecosystem services, stakeholders’ objectives and methods for storing and analysing data. The results demonstrate the complex nature of management plans, with an important workload for site managers. Recommendations for future planning include adjustments in planning timeframes and a better identification of conservation targets from initial stages.