Evidence for biodegradation and volatilisation of dissolved petroleum hydrocarbons during in situ air sparging in large laboratory columns

Laboratory column experiments run for up to 13 days compared air sparging of groundwater contaminated by dissolved petroleum hydrocarbons in sterile and non-sterile aquifer sediments as well as uncontaminated sediments and groundwater. Loss of dissolved BTEX compounds in the contaminated columns was very rapid, occurring through volatilisation. The majority of the dissolved total organic carbon (TOC) persisted for much longer periods however. A direct comparison between losses from sterile and non-sterile columns suggested a negligible contribution of biodegradation to the removal of TOC. This was difficult to confirm through examination of O₂ utilisation because oxidation of a small amount of reduced sulphur in the aquifer materials was the dominant sink for O₂. Despite this, it was possible to conclude that less than 22% of the removal of TOC was through biodegradation during the first three days of air sparging.     

Application of tracer ratio and inverse dispersion methods with boat-based plume measurements to estimate ammonia emissions from seabird colonies

Ammonia emissions from two contrasting seabird colonies in Scotland were measured, based on the determination of atmospheric concentrations downwind of the colonies. Atmospheric concentrations of ammonia (NH₃) across the downwind plume were compared with the inverse application of a Gaussian dispersion model (ID) to calculate the modelled NH₃ emission that would generate the measured cross-wind-integrated plume concentration. In parallel, a tracer gas (sulphur hexafluoride, SF₆) was released from the colonies with air samples taken to allow determination of SF₆ concentrations. On the basis of the known emission rate of SF₆, the magnitude of ammonia emissions was estimated by the cross-wind-integrated tracer ratio (TR) of NH₃/SF₆ concentrations. Coupled with data on annual bird attendance, the measurements indicate annual emissions from the Isle of May and the Bass Rock of 18 and 132 tonnes NH₃-N year^–1, respectively. The measured NH₃ emissions were compared with estimates of seabird nitrogen excretion to estimate the proportion of excreted N that is volatilised as NH₃ (F_Nr). The emission estimates of the two methods compared favourably, giving 4 and 6 kg NH₃-N h^–1 (F_Nr = 15%) for the Isle of May for the ID and TR methods, respectively, and 21 and 25 kg NH₃-N h^–1 (F_Nr = 50%) for the Bass Rock for the ID and TR methods, respectively. The results provide the first measurement-based estimates to allow regional up scaling of ammonia emissions from seabirds.     

Bromine in waste incineration partitioning and influence on metal volatilisation

INTENTION, GOAL, SCOPE, BACKGROUND: The halogen bromine is far less abundant than chlorine, but it can be found at high concentrations in special materials like flame retarded plastics. The fate and effects of Br in waste incineration are not well understood. It may have similar implications like Cl for the volatilisation of heavy metals and the formation of low volatile organic compounds. Due to its lower oxidation potential, there is a risk of formation of elementary Br2 in the offgas. OBJECTIVE: Co-combustion tests of different types of Br containing plastic waste materials (up to 22%) and MSW in the TAMARA pilot plant for waste incineration were conducted to investigate the Br partitioning and the influence of Br on metal volatilisation. METHODS: The Br inventory of the fuel mix was elevated to approx. 1 wt-%. All input and output mass flows of the furnace have been sampled and the partitioning of Cl, Br, S, and a number of heavy metals, has been calculated on the basis of closed mass balances. RESULTS AND DISCUSSION: Organically-bound Br was typically released to more than 90% into the raw gas. Elementary Br2 was detected at high Br levels. Its presence was always analysed when all SO2 in the raw gas was oxidised to SO3. Br enhances the volatilisation of metals like K, Zn, Cd, Sn, Sb, and Pb out of the fuel bed principally in the same way as Cl. The tests gave strong indication that the promoting influence of the halogens on metal volatilisation is more pronounced than that of the fuel bed temperature. The volatilised metals are condensated on the fly ashes and are discharged along with the filter ashes. CONCLUSIONS: As long as a surplus of SO2 is present in the raw gas no Br2 is formed. Although the halogen induced transfer out of the fuel bed causes high concentrations of volatile metals in the filter ashes, a recovery is not economically feasible for the time being. The volatilisation gives no rise to metal emission problems as long as efficient dedusting is achieved. RECOMMENDATION AND OUTLOOK: If there is a risk of Br2 formation, in wet scrubbing a reducing agent has to be added to the neutral scrubber for efficient abatement. Filter ashes should be disposed of in a way that enables access for recovery in the future. The exact volatilisation characteristics of the various metals have to be studied in future using specifically tailored experiments.     

Meteorological and pedological influence on the PCBs distribution in mountain soils

Polychlorinated biphenyls (PCBs) are a threat to environmental and human health due to their persistence and toxicological effects. In this paper, we analyse some meteorological and organic-matter-related effects on their distribution in the soils of an Alpine environment that is not subject to direct contamination. We collected samples and measured the contamination of 12 selected congeners from three soil layers (O, A1 and A2) and from North-, plain- and South-facing slopes on six different dates spanning the entire snowless portion of the year. We recorded the hourly air and soil temperatures, humidity and rainfall in the study period. We found evidence that PCBs contamination in soils varies significantly, depending on sampling date, layer and aspect. The observed seasonal trend shows an early summer peak and a rapid decrease during June. The layer effect demonstrates higher dry-weight-based concentrations in the O layer, whereas the differences are much smaller for SOM-based concentrations. Different factors caused significantly higher concentrations in northern soils, with a N/S enrichment factor ranging from 1.8 to 1.5 during the season. The southern site has significantly more rapid early-summer re-volatilisation kinetics (half-time of 16 d for South, 25 d for North).     

Preferential retention of POPs on the northern aspect of mountains

Soils are the main reservoirs of POPs in mountain ecosystems, but the great variability of the concentrations, also at small scale, leaves some uncertainties in the evaluation of environmental burdens and exposure. The role of the aspect of the mountain side and the seasonal variation in the contamination levels was analysed by means of several soil samples taken from central Italian Alps. A greater contamination content was present in northern soils with a mean ratio between the north vs. south normalised concentration of around a factor of 2 (North-South Enrichment Factor). Experimental factors agreed with theoretical calculations based on temperature-specific calculated K_sa values. From May to November consistent differences in normalised concentrations up to 5-fold were observed. A dynamic picture of the POP contamination in high altitudinal soils is derived from the data in this work, with spring-summer half-lives between 60 and 120 days for most of the compounds.