Mineralization of CCl4 by the UVC-photolysis of hydrogen peroxide in the presence of methanol

A method for a photochemically induced mineralization of CCl4 is described in which use is made of reductive radicals. The UVC-photolysis (254 nm) of H2O2 added to aqueous solutions of CCl4 is leading to the homolysis of the oxidant yielding hydroxyl radicals (HO) that subsequently react with added methanol to generate hydroxymethyl radicals (CH2OH). The latter radicals initiate mineralization of CCl4 by reductive C-Cl bond splitting. CHCl3, C2Cl4 and C2Cl6 were found as reaction intermediates, but are quantitatively depleted in a parallel oxidative reaction manifold leading to mineralization. Carbon dioxide radical anion, CO2(-), an intermediate in the mineralization pathway of methanol, is also shown to initiate the mineralization of CCl4 by reductive dechlorination. A reaction mechanism is proposed and validated with computer simulations of all the experimental results.     

Evaluation of the best compromise between the urban air quality monitoring resolution by diffusive sampling and resource requirements

The need to collect data representative of overall urban pollution is all-important in order to monitor the population exposure. High spatial resolution monitoring using diffusive samplers allows studying of the urban pollutant distribution, thus enabling deeper investigation of their generation and diffusion mechanisms. Nevertheless, such a monitoring campaign has a certain cost. In this study we point out how to find the best compromise between the number of necessary measurements and the affordable costs for monitoring campaigns. We also describe an innovative method for the proper design of a fixed urban monitoring network by means of preliminary high spatial resolution campaigns using diffusive samplers. Four European capital cities (Dublin, Madrid, Paris and Rome) were monitored six times, each time for seven days. Benzene, toluene, ethylbenzene, xylenes (BTEX) and NO(2) concentrations were measured at 146 sites in Dublin, 293 in Madrid, 339 in Paris and 290 in Rome. Multiscale grids have been drawn which ranged in mesh size from 500 m to 2 km. The statistical processing of data produced a twofold result: the creation of isoconcentration maps with geostatistical procedures, and an algorithm aimed at locating the minimum number of sampling sites where the fixed monitoring stations should be placed. Average urban levels estimated on the basis of these selected sites differ by less than 8% from those calculated on the whole populations of the sampled points. The aim of this work is to investigate how far the resolution of a monitoring campaign of urban pollution by diffusive sampling can be reduced, thus making the monitoring less expensive in terms of human and financial resources, while preserving the same quality of the results that could be achieved with a higher resolution. We found that there is no significant loss of information when the resolution of the monitoring grid for BTEX is lowered to a mesh size of 1.85 km, that is a sampling site each 3.4 km(2), and that the minimum number of sampling sites to be used is N = 0.29 A, where A is the urban surface to be monitored (in km(2)). As the spatial distribution of NO(2) is less sensitive to the distance from the emission source than that of BTEX, this relationship could be retained as a valid lower limit for the mesh grid size also for NO(2) monitoring.     

Twenty-year inter-annual trends and seasonal variations in precipitation and stream water chemistry at the Bear Brook Watershed in Maine, USA

Mean annual concentration of ${\textrm{SO}}_{4}^{2-}$ in wet-only deposition has decreased between 1988 and 2006 at the paired watershed study at Bear Brook Watershed in Maine, USA (BBWM) due to substantially decreased emissions of SO₂. Emissions of NO_x have not changed substantially, but deposition has declined slightly at BBWM. Base cations, ${\textrm{NH}}_{4}^{+}$ , and Cl^??? concentrations were largely unchanged, with small irregular changes of <1 μeq L^???1 per year from 1988 to 2006. Precipitation chemistry, hydrology, vegetation, and temperature drive seasonal stream chemistry. Low flow periods were typical in June–October, with relatively greater contributions of deeper flow solutions with higher pH; higher concentrations of acid-neutralizing capacity, Si, and non-marine Na; and low concentrations of inorganic Al. High flow periods during November–May were typically dominated by solutions following shallow flow paths, which were characterized by lower pH and higher Al and DOC concentrations. Biological activity strongly controlled ${\textrm{NO}}_{3}^{-}$ and K^?+?. They were depressed during the growing season and elevated in the fall. Since 1987, East Bear Brook (EB), the reference stream, has been slowly responding to reduced but still elevated acid deposition. Calcium and Mg have declined fairly steadily and faster than ${\textrm{SO}}_{4}^{2-}$ , with consequent acidification (lower pH and higher inorganic Al). Eighteen years of experimental treatment with (NH₄)₂SO₄ enhanced acidification of West Bear Brook’s (WB) watershed. Despite the manipulation, ${\textrm{NH}}_{4}^{+}$ concentration remained below detection limits at WB, while leaching of ${\textrm{NO}}_{3}^{-}$ increased. The seasonal pattern for ${\textrm{NO}}_{3}^{-}$ concentrations in WB, however, remained similar to EB. Mean monthly concentrations of ${\textrm{SO}}_{4}^{2-}$ have increased in WB since 1989, initially only during periods of high flow, but gradually also during base flow. Increases in mean monthly concentrations of Ca^2?+?, Mg^2?+?, and K^?+? due to the manipulation occurred from 1989 until about 1995, during the depletion of base cations in shallow flow paths in WB. Progressive depletion of Ca and Mg at greater soil depth occurred, causing stream concentrations to decline to pre-manipulation values. Mean monthly Si concentrations did not change in EB or WB, suggesting that the manipulation had no effect on mineral weathering rates. DOC concentrations in both streams did not exhibit inter- or intra-annual trends.     

The evolution of the science of Bear Brook Watershed in Maine, USA

The Bear Brook Watershed in Maine (BBWM), USA is a paired watershed study with chemical manipulation of one watershed (West Bear = WB) while the other watershed (East Bear = EB) serves as a reference. Characterization of hydrology and chemical fluxes occurred in 1987–1989 and demonstrated the similarity of the ca. 10 ha adjacent forested watersheds. From 1989–2010, we have added 1,800 eq (NH₄)₂SO₄ ha^???1 y^???1 to WB. EB runoff has slowly acidified even as atmospheric deposition of SO $_{4}^{2-}$ has declined. EB acidification included decreasing pH, base cation concentrations, and alkalinity, and increasing inorganic Al concentration, as SO $_{4}^{2-}$ declined. Organic Al increased. WB has acidified more rapidly, including a 6-year period of increasing leaching of base cations, followed by a long-term decline of base cations, although still elevated over pretreatment values, as base saturation declined in the soils. Sulfate in WB has not increased to a new steady state because of increased anion adsorption accompanying soil acidification. Dissolved Al has increased dramatically in WB; increased export of particulate Al and P has accompanied the acidification in both watersheds, WB more than EB. Nitrogen retention in EB increased after 3 years of study, as did many watersheds in the northeastern USA. Nitrogen retention in WB still remains at over 80%, in spite of 20+ years of N addition. The 20-year chemical treatment with continuous measurements of critical variables in both watersheds has enabled the identification of decadal-scale processes, including ecosystem response to declining SO $_{4}^{-2}$ in ambient precipitation in EB and evolving mechanisms of treatment response in WB. The study has demonstrated soil mechanisms buffering pH, declines in soil base saturation, altered P biogeochemistry, unexpected mechanisms of storage of S, and continuous high retention of treatment N.     

Soil chemical and physical properties at the Bear Brook Watershed in Maine, USA

Acidic deposition leads to the acidification of waters and accelerated leaching and depletion of soil base cations. The Bear Brook Watershed in Maine has used whole-watershed chemical manipulations to study the effects of elevated N and S on forest ecosystem function on a decadal time scale. The objectives of this study were to define the chemical and physical characteristics of soils in both the reference and treated watersheds after 17 years of treatment and assess evidence of change in soil chemistry by comparing soil studies in 1998 and 2006. Results from 1998 confirmed depletion of soil base cation pools and decreased pH due to elevated N and S within the treated watershed. However, between 1998 and 2006, during a period of declining SO $_{4}^{\,\,2-}$ deposition and continued whole-watershed experimental acidification on the treated watershed, there was little evidence of continued soil exchangeable base cation concentration depletion or recovery. The addition of a pulse of litterfall and accelerating mineralization from a severe ice storm in 1998 may have had significant effects on forest floor nutrient pools and cycling between 1998 and 2006. Our findings suggest that mineralization of additional litter inputs from the ice storm may have obscured temporal trends in soil chemistry. The physical data presented also demonstrate the importance of coarse fragments in the architecture of these soils. This study underscores the importance of long-term, quantitative soil monitoring in determining the trajectories of change in forest soils and ecosystem processes over time.     

PAHs in the urban air of Sarajevo: levels,sources, day/night variation,and human inhalation risk

Polycyclic aromatic hydrocarbons (PAHs) are organic pollutants derived from pyrolysis and pyrosynthesis processes. Industrial activity, motor vehicle emission, and domestic combustion are the main sources of PAHs in the urban atmosphere. In this work, samples collected during the day and night in the urban area of Sarajevo are analyzed separately for gaseous and particle-bound PAHs; the possible origin of PAHs at the receptor site was suggested using different methods applied to the solid phase and to the total PAHs (gaseous + particulate phase). Finally, the risk level in Sarajevo associated to the carcinogenic character of the studied PAHs has been assessed. The result of this study suggests that (a) the total PAH concentrations were higher than those reported in other European cities; (b) the PAH daytime concentrations are higher than nocturnal concentrations: the sum of the PAH day/night ratios is 1.52 (gas) and 1.45 (particle phase); (c) stationary combustion and traffic were suggested to be the main sources of PAHs; (d) the average particle-bound benzo(a)pyrene (BaP) concentration (5.4 ng/m³) is higher than EU target annual value (1 ng/m³); and (e) PAH cancer risk exceeds the carcinogenic benchmark level recommended by the EPA mainly due to BaP during both the day and night periods.     

Measurement of mass exchange processes and coefficients in a simplified open-channel lateral cavity connected to a main stream

Lateral cavities are major storage zones in riverine environments for which the mass exchanges with the main stream strongly impact the characteristics of the habitat in these dead zones. An experimental work is presented here with a controlled main stream and a connected open-channel lateral cavity to assess the processes responsible for these exchanges and to quantify the exchange capacities. In a first step, the measurements of passive scalar transport allow us to identify the physical processes involved in the exchange of mass from the main stream and its spreading within the cavity. In a second step, the quantitative mass exchange coefficient, representative of the exchange capacity, is measured for 28 flow and cavity configurations. The sensibility analysis to the governing parameters proposed by the dimensional analysis then reveals that changing the geometric aspect ratio of the cavity does not affect the exchange coefficient while increasing the normalized water depth or decreasing the Reynolds number of the main stream tend to increase this coefficient. Indeed, these parameters modify both the growth rate of the mixing layer width at the interface and the amplitude of the alternating transverse velocity across the interface, thus affecting the exchange capacities from the main stream to the cavity.     

Real-world emissions of in-use off-road vehicles in Mexico

Off-road vehicles used in construction and agricultural activities can contribute substantially to emissions of gaseous pollutants and can be a major source of submicrometer carbonaceous particles in many parts of the world. However, there have been relatively few efforts in quantifying the emission factors (EFs) and for estimating the potential emission reduction benefits using emission control technologies for these vehicles. This study characterized the black carbon (BC) component of particulate matter and NOx, CO, and CO₂ EFs of selected diesel-powered off-road mobile sources in Mexico under real-world operating conditions using on-board portable emissions measurements systems (PEMS). The vehicles sampled included two backhoes, one tractor, a crane, an excavator, two front loaders, two bulldozers, an air compressor, and a power generator used in the construction and agricultural activities. For a selected number of these vehicles the emissions were further characterized with wall-flow diesel particle filters (DPFs) and partial-flow DPFs (p-DPFs) installed. Fuel-based EFs presented less variability than time-based emission rates, particularly for the BC. Average baseline EFs in working conditions for BC, NOx, and CO ranged from 0.04 to 5.7, from 12.6 to 81.8, and from 7.9 to 285.7 g/kg-fuel, respectively, and a high dependency by operation mode and by vehicle type was observed. Measurement-base frequency distributions of EFs by operation mode are proposed as an alternative method for characterizing the variability of off-road vehicles emissions under real-world conditions. Mass-based reductions for black carbon EFs were substantially large (above 99%) when DPFs were installed and the vehicles were idling, and the reductions were moderate (in the 20–60% range) for p-DPFs in working operating conditions. The observed high variability in measured EFs also indicates the need for detailed vehicle operation data for accurately estimating emissions from off-road vehicles in emissions inventories.

Implications: Measurements of off-road vehicles used in construction and agricultural activities in Mexico using on-board portable emissions measurements systems (PEMS) showed that these vehicles can be major sources of black carbon and NO_X. Emission factors varied significantly under real-world operating conditions, suggesting the need for detailed vehicle operation data for accurately estimating emissions inventories. Tests conducted in a selected number of sampled vehicles indicated that diesel particle filters (DPFs) are an effective technology for control of diesel particulate emissions and can provide potentially large emissions reduction in Mexico if widely implemented.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

Presence of carbamazepine,naproxen, and ibuprofen in wastewater from northern Tunisia

We investigated the occurrence of three pharmaceutical residues in four wastewater treatment plants (WWTPs) from northern Tunisia. The selected compounds were carbamazepine, naproxen, and ibuprofen; they are among the most commonly prescribed and widely used pharmaceutical agents worldwide. Samples (200?mL) were pre-concentrated using the solid phase extraction (SPE) enrichment procedure and the analysis of the pharmaceuticals was performed with high-performance liquid chromatography (HPLC-UV). The overall procedure provided limits of detection (LOD) lower than 0.5 µg.L^?1and recoveries of 78–97%. For the carbamazepine compound, the mean concentrations were 60.58, 93.19, and 132 µg.L^?1 for the Bizerte, Jendouba, and Tunis WWTPs, respectively. This pharmaceutical was not detected in the Beja WWTPs. Naproxen and ibuprofens were not detected in the Jendouba WWTP but were found in the three other WWTPs with concentrations ranging from 2.94 to 36.17 µg.L^?1 and from 8.02 to 43.22 µg.L^?1, respectively. From the obtained data, it seems that these WWTPs are not able to eliminate this kind of micro-pollutants.