Dealing with disjunct concentration measurements in eddy covariance applications: A comparison of available approaches

Using proton transfer reaction mass spectrometry equipped with a quadrupol mass analyser to quantify the biosphere-atmosphere exchange of volatile organic compounds (VOC), concentrations of different VOC are measured sequentially. Depending on how many VOC species are targeted and their respective integration times, each VOC is measured at repeat rates on the order of a few seconds. This represents an order of magnitude longer sample interval compared to the standard eddy covariance (EC) method (5–20 Hz sampling rates). Here we simulate the effect of disjunct sampling on EC flux estimates by decreasing the time resolution of CO₂ and H₂O concentrations measured at 20 Hz above a temperate mountain grassland in the Austrian Alps. Fluxes for one month are calculated with the standard EC method and compared to fluxes calculated based on the disjunct data (1, 3 and 5 s sampling rates) using the following approaches: i) imputation of missing concentrations based on the nearest neighbouring samples (iDEC_nn), ii) imputation by linear interpolation (iDEC_li), and iii) virtual disjunct EC (vDEC), i.e. flux calculation based solely on the disjunct concentrations. It is shown that the two imputation methods result in additional low-pass filtering, longer lag times (as determined with the maximum cross-correlation method) and a flux loss of 3–30% as compared to the standard EC method. A novel procedure, based on a transfer function approach, which specifically corrects for the effect of data treatment, was developed, resulting in improved correspondence (to within 2%). The vDEC method yields fluxes which approximate the true (20 Hz) fluxes to within 3–7% and it is this approach we recommend because it involves no additional empirical corrections. The only drawback of the vDEC method is the noisy nature of the cross-correlations, which poses problems with lag determination – practical approaches to overcome this limitation are discussed.     

Urban tracer dispersion experiments during the second DAPPLE field campaign in London 2004

As part of the DAPPLE programme two large scale urban tracer experiments using multiple simultaneous releases of cyclic perfluoroalkanes from fixed location point sources was performed. The receptor concentrations along with relevant meteorological parameters measured are compared with a three screening dispersion models in order to best predict the decay of pollution sources with respect to distance. It is shown here that the simple dispersion models tested here can provide a reasonable upper bound estimate of the maximum concentrations measured with an empirical model derived from field observations and wind tunnel studies providing the best estimate. An indoor receptor was also used to assess indoor concentrations and their pertinence to commonly used evacuation procedures.     

Verification of diffusive and pumped samplers for volatile organic compounds using a controlled atmosphere test facility

There is a requirement to verify the performance of sorbent-based passive or active samplers and to extend their use, where possible, to monitor volatile organic compounds (VOCs) that are known to be photochemical ozone pre-cursors or are relevant to the activities of the petrochemical industry. We report measurements of the 14-day diffusive uptake rates for the VOCs: i-butane (2-methyl propane), n-butane, i-pentane (2-methyl butane), n-pentane, n-hexane, benzene, toluene, and m-xylene (at environmental level concentrations) for industry standard axial samplers (Perkin–Elmer-type samplers) containing the sorbents Carbopack-X, -Z, -B or Tenax-TA. We also present data on back-diffusion, blank levels, and storage for the above sorbents, and describe the simultaneous use of the sorbent Carbopack-X for pumped sampling of certain VOCs. The results were obtained by dosing samplers in a controlled atmosphere test facility (CATFAC) operating under well-defined conditions of concentration, nominal temperature of 20 °C, wind speed of 0.5 m s^?1, and relative humidities of 0% and 80%. Field measurements were also obtained to provide supplementary data to support the laboratory study. Results are compared to existing published data, where these are available.     

Contribution of transition metals in the reactive oxygen species activity of PM emissions from retrofitted heavy-duty vehicles

We assessed the contribution of water-soluble transition metals to the reactive oxygen species (ROS) activity of diesel exhaust particles (DEPs) from four heavy-duty vehicles in five retrofitted configurations (V-SCRT, Z-SCRT, DPX, hybrid, and school bus). A heavy-duty truck without any control device served as the baseline vehicle. Particles were collected from all vehicle-configurations on a chassis dynamometer under three driving conditions: cruise (80 km h^?1), transient UDDS, and idle. A sensitive macrophage-based in vitro assay was used to determine the ROS activity of collected particles. The contribution of water-soluble transition metals in the measured activity was quantified by their removal using a Chelex^® complexation method. The study demonstrates that despite an increase in the intrinsic ROS activity (per mass basis) of exhaust PM with use of most control technologies, the overall ROS activity (expressed per km or per h) was substantially reduced for retrofitted configurations compared to the baseline vehicle. Chelex treatment of DEPs water extracts removed a substantial (≥70%) and fairly consistent fraction of the ROS activity, which ascertains the dominant role of water-soluble metals in PM-induced cellular oxidative stress. However, relatively lower removal of the activity in few vehicle-configurations (V-SCRT, DPX and school bus idle), despite a large aggregate metals removal, indicated that not all species were associated with the measured activity. A univariate regression analysis identified several transition metals (Fe, Cr, Co and Mn) as significantly correlated (R > 0.60; p < 0.05) with the ROS activity. Multivariate linear regression model incorporating Fe, Cr and Co explained 90% of variability in ROS levels, with Fe accounting for the highest (84%) fraction of the variance.     

Analysis of 3-year observations of CFC-11, CFC-12 and CFC-113 from a semi-rural site in China

In-situ measurements of atmospheric chlorofluorocarbons (CFCs) can be used to the assess their global and regional emissions and to check for compliance with phase-out schedules under Montreal protocol and its amendments. The atmospheric mixing ratios of CFC-11 (CCl₃F), CFC-12 (CCl₂F₂) and CFC-113 (CCl₂F–CClF₂) have been measured by an automated in-situ GC-ECDs system at the regional Chinese Global Atmosphere Watch (GAW) station Shangdianzi (SDZ), from November 2006 to October 2009. The time series for these three principal CFCs showed large episodic events and background conditions occurred for approximately 30% (CFC-11), 52% (CFC-12) and 56% (CFC-113) of the measurements. The mean background mixing ratios for CFC-11, CFC-12 and CFC-113 were 244.8 ppt (parts per trillion, 10^?12, molar) 539.6 ppt and 76.8 ppt, respectively, for 2006–2009. The enhanced CFC mixing ratios compared to AGAGE sites such as Trinidad Head (THD), US and Mace Head (MHD), Ireland suggest regional influences even during background conditions at SDZ, which is much closer to highly-populated areas. Between 2006 and 2009 background CFCs exhibited downward trends at rates of ?2.0 ppt yr^?1 for CFC-11, ?2.5 ppt yr^?1 for CFC-12 and ?0.7 ppt yr^?1 for CFC-113. De-trended 3-year average background seasonal cycles displayed small fluctuations with peak-to-trough amplitudes of 1.0 ± 0.02 ppt (0.4%) for background CFC-11, 1.3 ± 2.1 ppt (0.3%) for CFC-12 and 0.2 ± 0.4 ppt (0.3%) for CFC-113. On the other hand, during pollution periods these CFCs showed much larger seasonal cycles of 11.2 ± 10.7 ppt (5%) for CFC-11, 7.5 ± 6.5 ppt (2%) for CFC-12 and 1.0 ± 1.2 ppt (1.2%) for CFC-113, with apparent winter minima and early summer maxima. This enhancement was attributed to prevailing wind directions from urban regions in summer and to enhanced anthropogenic sources during the warm season. In general, horizontal winds from northeast showed negative contribution to atmospheric CFCs loading, whereas South Western advection (urban sector: Beijing) had positive contributions.     

Experimental exposure of juvenile savannah monitors (Varanus exanthematicus) to an environmentally relevant mixture of three contaminants: effects and accumulation in tissues

Using varanids as indicators of pollution in African continental wetlands was previously proposed. The present study aimed at understanding experimentally how monitors absorb and accumulate pollutants and how they are affected. The relevance of non-destructive sampling was also evaluated. Savannah monitors (Varanus exanthematicus) were orally exposed during 6 months to a mixture of lead, 4,4′-dichlorodiphenyltrichloroethane (4,4′-DDT) and chlorpyrifos-ethyl (CPF) or to the vehicle only. Proportionally to their mass, exposed monitors received the same dose: 20 then 10 mg lead?kg^?1, 2 then 0.5 mg CPF?kg^?1 and 4 mg 4,4′-DDT?kg^?1. Individuals surviving contamination were euthanized after 4 or 6 months of experiment. Tissues were analysed for lead by atomic absorption spectrophotometry and for DDT and CPF by gas chromatography. Exposed monitors absorbed all three pollutants but only lead (essentially in bone, tail tips and phalanxes) and 4,4′-DDT plus its main metabolites (essentially in fat and liver) accumulated. CPF killed ten individuals. Clear correlations occurred between the total quantity of lead or 4,4′-DDT administered and concentrations in tissues. Tail tips and skin samples are recommended non-destructive indicators for lead and organochlorine pesticides contamination, respectively. This work confirms that monitors can be used as relevant indicators of environmental pollution by lead and organochlorine pesticides. Although varanids withstand heavy lead and DDT contamination, our results suggest that CPF can be lethal at very low doses to the herpetofauna and emphasize the importance of considering all taxa in impact assessment studies, including reptiles.     

Compositional changes of crude oil SARA fractions due to biodegradation and adsorption on colloidal support such as clays using Iatroscan

The compositional changes of saturates, aromatics, resins and asphaltenes (SARA) fractions in aqueous clay/oil microcosm experiments with a hydrocarbon-degrading microorganism community were analysed using Iatroscan. The clay mineral samples used in this study were organomontmorillonite, acid-activated montmorillonite and K, Ca, Zn and Cr montmorillonites produced by modifying the original montmorillonite sample. The evaluation and quantification of biodegradation and adsorption were carried out using a combination of the Iatroscan and gravimetric analysis. The SARA compositions in the presence of organomontmorillonite and acid-activated montmorillonite after incubation follow the same pattern in which the aromatic fraction is higher than the other fractions unlike in the presence of unmodified, K, Ca and Zn montmorillonites, where the saturates fraction is higher than the other fractions. Changes in SARA fractions due to biodegradation seemed to occur most in the presence of unmodified and calcium montmorillonites; hence, the removal of SARA fractions due to biodegradation was significant and enhanced in the presence of these two clay samples. However, biodegradation in the presence of organomontmorillonite and acid-activated and Cr montmorillonites was hindered. The study indicated that Cr montmorillonite adsorbed resins most, whereas Zn and K montmorillonites adsorbed aromatics most after incubation.     

Sexual difference in PCB congener distributions of burbot (Lota lota) from Lake Erie

Concentrations of 86 congeners of polychlorinated biphenyls (PCBs) were determined for 25 adult female and 25 adult male burbot (Lota lota) from Lake Erie. Significant differences in mean proportions of total PCB concentration between males and females ages 14–17 were found for 26 congeners. Males generally had higher mean proportions of hexachloro congeners, whereas females had higher mean proportions of more highly chlorinated congeners. In contrast, only four congeners exhibited differences between males and females ages 6–13 in mean proportions of total PCB. Therefore, the sexual difference in PCB congener distribution widened for older burbot. Males ages 14–17 also had higher proportions of certain hexachloro congeners than the other three demographic groups (males ages 6–13, females ages 6–13, and females ages 14–17) we examined. The reverse was true for more highly chlorinated congeners. The results supported a previous hypothesis that older male burbot spent a substantial amount of time feeding in the vicinity of mouths of rivers with sediment contaminated with PCBs. However, additional studies are needed to clarify and corroborate this apparent “hot spot” effect, such as seasonal movements, spatial distributions, and diet of burbot; and PCB congener distributions of various species of prey fishes captured at various locations throughout the eastern basin of Lake Erie and at different locations in the contaminated rivers.     

Modifications to an H2S Tape Sampler for Increasing Sensitivity and Accuracy in H2S Sampling

The tape samplers using lead acetate impregnated paper tapes for continuous hydrogen sulfide sampling are subject to a number of errors which can throw considerable doubt on the accuracy of H₂S concentrations being measured. Some of the errors have been minimized with a change in the humidification system and a reduction of the lamp intensity in the optical system.     

Fine Paniculate Removal and S02 Absorption with a Two Stage Wet Scrubber

This paper includes results from pilot plant studies and early field demonstration units and a discussion of the application of the limestone wet scrubbing process to a low sulfur syb-butuminous coal. This latter application required the development of a hybrid two stage scrubber to enable collection of the fine particulate matter as well as removal of a significant amount of the sulfur dioxide.