Mobility control: How injected surfactants and biostimulants may be forced into low‐permeability units

Recovering dense nonaqueous‐phase liquid (DNAPL) remains one of the most difficult problems facing the remediation industry. Still, the most common method of recovering DNAPL is to physically remove the contaminants using common technologies such as total fluids recovery pumps, vacuum systems, and “pump‐and‐treat.” Increased DNAPL removal can be attained using surfactants to mobilize and/or solubilize the pollutants. However, very little is understood of the methods developed by petroleum engineers beginning in the 1960s to overcome by‐passed, low‐permeability zones in heterogeneous oil reservoirs. By injecting or causing the formation of viscous fluids in the subsurface, petroleum engineers caused increased in‐situ pressures that forced fluid flow into low permeability units as well as the higher permeability thief zones. Polymer flooding involves injecting a viscous aqueous polymer solution into the contaminated aquifer. Foam flooding involves injecting surfactant to decontaminate the high‐permeability zones and then periodic pulses of air to cause a temporary viscous foam to form in the high‐permeable zones after all DNAPL is removed. Later surfactant pulses are directed by the foam into unswept low‐permeable units. These methods have been applied to DNAPL removal using surfactants but they can also be applied to the injection of bio‐amendments into low‐permeability zones still requiring continued remediation. Here we discuss the principles of mobility control as practiced in an alluvial aquifer contaminated with chlorinated solvent and coal tar DNAPLs as well as some field results. © 2003 Wiley Periodicals, Inc.     

Improved source assessment of Si, Al and related mineral components to PM10 based on a daily sampling procedure

Samples obtained from an industrialized valley in the East Alpine region were collected daily for a half year and analyzed using X-ray fluorescence to examine the elements Si,Al,Fe,Ca,Mg,Na,K,Zn,P,S and Cl.Some factors affecting the changes of these elements were considered,including time,elemental correlations,weekday,weekend and seasonal changes.Diagnostic analysis provided an insight into a decoupling behavior that occursin siliceous and carbonates minerals.A decrease in Si and Al and an increase in carbonates,Na,K,Zn and P were observed during the cold season.However,a consistently high correlation of Si and Al was observed in all seasons.It was established that such high levels originated from street surface abrasion.The increase in variability and absolute levels of carbonates during the cold season was demonstrated by adding carbonates to the street surface as gritting material to increase the grip on snowy surfaces.A marked increase in Na and Cl was observed in winter which may have been caused by thaw salt that is widely used in winter in Austria.This was associated with a significant increase in K,Zn,and P in the cold season that was the result of domestic space heating with wood.PM10 levels in December were 12 μg/m3 and were higher than levels detected in July.It was established that such high levels originated from mineral oxides,wood smoke,and inorganic ionic material(s).     

U and Th in some brown coals of Serbia and Montenegro and their environmental impact

GOAL, SCOPE AND BACKGROUND: The objective of this paper is to determine and compare the concentrations of U and Th in soft to hard brown (lignite to sub-bituminous) coals of Serbia and Montenegro. It also presents comparison of the obtained data on U and Th concentrations with the published data on coals located in some other countries of the world. Almost the whole coal production of Serbia and Montenegro is used as feed coals for combustion in thermal power plants. METHODS: Channel samples from open pit and underground mines and core samples were collected for hard and soft brown coals. For the analysis the samples were decomposed using microwave technique. Obtained solutions containing U and Th were analyzed by inductively coupled plasma mass spectroscopy (ICP-MS) using NIST standards. RESULTS: Concentration of U from the investigated basins and the corresponding mine fields ranges within 0.60-70.10 mg/kg, 0.65-3.20 mg/kg, 0.95-6.59 mg/kg, 1.20-6.05 mg/kg, 0.80-6.66 mg/kg, 0.18-89.90 mg/kg, 0.19-4.14 mg/kg, and 0.28-3.52 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. Concentration of Th ranges within 0.20-2.60 mg/kg, 0.84-6.57 mg/kg, 1.48-6.48 mg/kg, 0.12-2.71 mg/kg, 0.13-4.95 mg/kg, 0.14-3.48 mg/kg, 0.29-3.56 mg/kg, and 0.17-1.89 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. DISCUSSION: Brown coal from Senje-Resavica, Kolubara, Kostolac and Pljevlja is characterized by low U concentration. Coals form the Krepoljin, Soko Banja and Sjenica basins have slightly higher U concentrations than the mentioned group. The highest concentration of U is characteristic for the coal from the Bogovina East field. Concentration of Th in coals from Serbia and Montenegro has proved to be low. Out of all investigated coal basins, only the coal from the Krepoljin and Kolubara basins has high concentration of Th. The hydrothermally altered rocks of the Timok dacite-andesite complex, representing the basement of the Bogovina basin, could be a potential source of U, especially at the bottom part of the Lower seam of the Bogovina East field. CONCLUSIONS: This study shows that brown coals in Serbia and Montenegro (soft to hard brown coals or lignite to sub-bituminous) contain low levels of U (5.30 mg/kg, average value and 2.10 mg/kg geometric mean value) and Th (1.80 mg/kg, average value and 1.12 mg/kg geometric mean value). There are some obvious differences in concentration of U and Th in coals from different basins in Serbia and Montenegro. The approximate value for U and Th release mainly from power plants was 644.33 t and 983.46 t, respectively within the period 1965-2000 for the studied mines in Serbia, and 23.76 t and 15.05 t for the Potrlica mine (Montenegro) within the period 1965-1997. RECOMMENDATIONS: The coals in Serbia and Montenegro show no identifiable unfavourable impact on the surrounding environment, due to low natural radioactive concentration of U and Th, but further investigations concerning human health should be performed. PERSPECTIVES: Preliminary research revealed that in some Serbian coals (and, particularly, parts of the coal seam) U and Th content are rather high. Such coals should be carefully studied, as well as U and Th concentrations in ash, fly ash, waste disposals, nearby soil and ground water. Further studies should include determination of the radioactivity of all these products, and estimation of possible health impact.     

Leaching of cyanogenic glucosides and cyanide from white clover green manure

Use of crops for green manure as a substitute for chemical fertilizers and pesticides is an important approach towards more sustainable agricultural practices. Green manure from white clover is rich in nitrogen but white clover also produces the cyanogenic glucosides (CGs) linamarin and lotaustralin; CGs release toxic hydrogen cyanide (HCN) upon hydrolysis which may be utilized for pest control. We demonstrate that applying CGs in the form of a liquid extract of white clover to large columns of intact agricultural soils can result in leaching of toxic cyanide species to a depth of at least 1m. Although degradation of the CGs during leaching proceeded with half lives in the interval 1.5-35 h depending on soil characteristics, a fraction of the applied CGs (0.9-3.2%) was recovered in the leachate as either CGs or toxic cyanide species. Detoxification of the HCN formed was rapid in soil and leachate from both sandy and loamy soil. However, 30% of the leachate samples exceeded the EU threshold value of 50 micrgl(-1) total cyanide for drinking water and 85% exceeded the US threshold of 5 micrgl(-1) for cyanide chronic ecotoxicity in fresh water. This study demonstrates that even easily degradable natural products present in crop plants as defense compounds pose a threat to the quality of groundwater and surface waters. This aspect needs consideration in assessment of the risk associated with use of crops as green manure to replace chemical fertilizers and pesticides as well as in genetic engineering approaches to design crops with improved pest resistance.     

Wood burning impact on PM10 in three Austrian regions

Anhydrosugars (levoglucosan, mannosan and galactosan) were investigated during one year in three Austrian regions at three types of sites (city-heavy traffic-impacted, city-residential and background) in order to assess the magnitude of the contribution of wood smoke to the particulate matter load and its organic fraction. The annually averaged concentrations of levoglucosan ranged from 0.12 to 0.48 μg m^?3. The levoglucosan concentration exhibited a strong annual cycle with higher concentrations in the cold season. The minor anhydrosugars had a similar annual trend, but their concentrations were lower by a factor of about 5 and about 25 in the cold season for mannosan and galactosan, respectively. Levoglucosan concentrations were higher at the inner-urban as compared to rural sites. The contribution of wood smoke to organic carbon and PM₁₀ levels was calculated using a constant ratio of levoglucosan and OC, respectively PM₁₀ as derived for fire wood typical for Alpine European regions [Schmidl, C., Marr, I.L., Caseiro, A.e, Kotianová, P., Berner, A., Bauer, H., Kasper-Giebl, A., Puxbaum, H., 2008a. Chemical characterisation of fine particle emissions from wood stove combustion of common woods growing in mid-European Alpine regions. Atmospheric Environment 42, 126–141]. The estimated contribution of wood smoke-OC to the OC of PM₁₀ ranged from one third to more than half in the cold season with higher contributions up to 70% in winter (December, January and February) in the smaller cities and the rural background. This indicates, that wood smoke is the predominant source of organic material at rural and small urban sites in central Europe. Consistently, wood smoke was an important contributor to PM₁₀ during the cold season, with contributions of around 10% in the Vienna larger region and around 20% at rural sites in the densely forested regions of Salzburg and Styria during the winter months. In those regions residential sites exhibited highest relative wood smoke contents in PM₁₀ during autumn (September till November), indicating the use of wood stoves for auxiliary heating in the transition of warm to cold season. Using the relationships between the different anhydrosugars the combustion of softwood was found to be dominant for the wood smoke occurrence in ambient air at the investigated sites. Potassium, a commonly used tracer for biomass burning, correlated well to levoglucosan, with a mass ratio of around 0.80 in the cold season.     

Sulfide assimilation by ectosymbionts of the sessile ciliate, <Emphasis Type="Italic">Zoothamnium niveum</Emphasis>

We investigated the constraints on sulfide uptake by bacterial ectosymbionts on the marine peritrich ciliate Zoothamnium niveum by a combination of experimental and numerical methods. Protists with symbionts were collected on large blocks of mangrove-peat. The blocks were placed in a flow cell with flow adjusted to in situ velocity. The water motion around the colonies was then characterized by particle tracking velocimetry. This shows that the feather-shaped colony of Z. niveum generates a unidirectional flow of seawater through the colony with no recirculation. The source of the feeding current was the free-flowing water although the size of the colonies suggests that they live partly submerged in the diffusive boundary layer. We showed that the filtered volume allows Z. niveum to assimilate sufficient sulfide to sustain the symbiosis at a few micromoles per liter in ambient concentration. Numerical modeling shows that sulfide oxidizing bacteria on the surfaces of Z. niveum can sustain 100-times higher sulfide uptake than bacteria on flat surfaces, such as microbial mats. The study demonstrates that the filter feeding zooids of Z. niveum are preadapted to be prime habitats for sulfide oxidizing bacteria due to Z. niveum’s habitat preference and due to the feeding current. Z. niveum is capable of exploiting low concentrations of sulfide in near norm-oxic seawater. This links its otherwise dissimilar habitats and makes it functionally similar to invertebrates with thiotrophic symbionts in filtering organs. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Uranium in stream and mineral water of the Federal Republic of Germany

The concentration of uranium was determined in 944 samples from stream water by the inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) method and represented on a color-shaded contour map. Uranium concentrations in surface water were determined to be between 0.007 μg/l and 43.7 μg/l with median of 0.33 μg/l. The regional distribution of uranium is influenced primarily by lithological and anthropogenic factors. In Mecklenburg, northern Brandenburg, and eastern Schleswig-Holstein, elevated uranium concentrations coincide with the extent of the last Weichselian ice sheet. The maximum concentrations are observed in the surface waters of the old mining districts in the western part of the Ore Mountains and in eastern Thuringia. Elevated concentrations are found in areas of agriculturally used loess soils. These concentrations correlate with the use of phosphate fertilizers. There is a zone of elevated concentrations up to 10.0 μg U/l in the Keuper Sandstone area south of the Thuringian Forest and from northwest of Stuttgart as far as Coburg. The distribution of elevated values in mineral water shows a clear correlation with the elevated values in surface water and the geology of those locations. Bunter and Keuper strata are the most important uranium source.     

Advanced REACH Tool (ART): calibration of the mechanistic model

The mechanistic model of the Advanced Reach Tool (ART) provides a relative ranking of exposure levels from different scenarios. The objectives of the calibration described in this paper are threefold: to study whether the mechanistic model scores are accurately ranked in relation to exposure measurements; to enable the mechanistic model to estimate actual exposure levels rather than relative scores; and to provide a method of quantifying model uncertainty. Stringent data quality guidelines were applied to the collated data. Linear mixed effects models were used to evaluate the association between relative ART model scores and measurements. A random scenario and company component of variance were introduced to reflect the model uncertainty. Stratified analyses were conducted for different forms of exposure (abrasive dust, dust, vapours and mists). In total more than 2000 good quality measurements were available for the calibration of the mechanistic model. The calibration showed that after calibration the mechanistic model of ART was able to estimate geometric mean (GM) exposure levels with 90% confidence for a given scenario to lie within a factor between two and six of the measured GM depending upon the form of exposure.