Enhanced stability of hydrogen peroxide in the presence of subsurface solids

The stabilization of hydrogen peroxide was investigated as a basis for enhancing its downgradient transport and contact with contaminants during catalyzed H(2)O(2) propagations (CHP) in situ chemical oxidation (ISCO). Stabilization of hydrogen peroxide was investigated in slurries containing four characterized subsurface solids using phytate, citrate, and malonate as stabilizing agents after screening ten potential stabilizers. The extent of hydrogen peroxide stabilization and the most effective stabilizer were solid-specific; however, phytate was usually the most effective stabilizer, increasing the hydrogen peroxide half-life to as much as 50 times. The degree of stabilization was nearly as effective at 10 mM concentrations as at 250 mM or 1 M concentrations. The effect of stabilization on relative rates of hydroxyl radical activity varied between the subsurface solids, but citrate and malonate generally had a greater positive effect than phytate. The effect of phytate, citrate, and malonate on the relative rates of superoxide generation was minimal to somewhat negative, depending on the solid. The results of this research demonstrate that the stabilizers phytate, citrate, and malonate can significantly increase the half-life of hydrogen peroxide in the presence of subsurface solids during CHP reactions while maintaining a significant portion of the reactive oxygen species activity. Use of these stabilizers in the field will likely improve the delivery of hydrogen peroxide and downgradient treatment during CHP ISCO.     

Transport of Sr2+ and SrEDTA2- in partially-saturated and heterogeneous sediments

Strontium-90 has migrated deep into the unsaturated subsurface beneath leaking storage tanks in the Waste Management Areas (WMA) at the U.S. Department of Energy's (DOE) Hanford Reservation. Faster than expected transport of contaminants in the vadose zone is typically attributed to either physical hydrologic processes such as development of preferential flow pathways, or to geochemical processes such as the formation of stable, anionic complexes with organic chelates, e.g., ethylenediaminetetraacetic acid (EDTA). The goal of this paper is to determine whether hydrological processes in the Hanford sediments can influence the geochemistry of the system and hence control transport of Sr(2+) and SrEDTA(2-). The study used batch isotherms, saturated packed column experiments, and an unsaturated transport experiment in an undisturbed core. Isotherms and repacked column experiments suggested that the SrEDTA(2-) complex was unstable in the presence of Hanford sediments, resulting in dissociation and transport of Sr(2+) as a divalent cation. A decrease in sorption with increasing solid:solution ratio for Sr(2+) and SrEDTA(2-) suggested mineral dissolution resulted in competition for sorption sites and the formation of stable aqueous complexes. This was confirmed by detection of MgEDTA(2-), MnEDTA(2-), PbEDTA(2-), and unidentified Sr and Ca complexes. Displacement of Sr(2+) through a partially-saturated undisturbed core resulted in less retardation and more irreversible sorption than was observed in the saturated repacked columns, and model results suggested a significant reservoir (49%) of immobile water was present during transport through the heterogeneous layered sediments. The undisturbed core was subsequently disassembled along distinct bedding planes and subjected to sequential extractions. Strontium was unequally distributed between carbonates (49%), ion exchange sites (37%), and the oxide (14%) fraction. An inverse relationship between mass wetness and Sr suggested that sandy sediments of low water content constituted the immobile flow regime. Our results suggested that the sequestration of Sr(2+) in partially-saturated, heterogeneous sediments was most likely due to the formation of immobile water in drier regions having low hydraulic conductivities.     

Sulfidation treatment of molten incineration fly ashes with Na2S for zinc, lead and copper resource recovery

The present study focuses on the conversion of heavy metals involved in molten incineration fly ashes to metal sulfides which could be thereafter separated by flotation. The sulfidation treatment was carried out for five molten incineration fly ashes (Fly ash-A to Fly ash-E) by contacting each fly ash with Na(2)S solution for a period of 10 min to 6h. The initial molar ratio of S(2-) to Me(2+) was adjusted to 1.20. The conversion of heavy metals to metal sulfides was evaluated by measuring the S(2-) residual concentrations using an ion selective electrode. The formation of metal sulfides was studied by XRD and SEM-EDS analyses. In the case of Fly ash-A to Fly ash-D, more than 79% of heavy metals of zinc, lead and copper was converted to metal sulfides within the contacting period of 0.5h owing to a fast conversion of metal chlorides to metal sulfides. By contrast, the conversion of about 35% was achieved for Fly ash-E within the same contacting period, which was attributed to a high content of metal oxides. Further, the S(2-) to Me(2+) molar ratio was reduced to 1.00 to minimize Na(2)S consumption and the conversions obtained within the contacting period of 0.5h varied from 76% for Fly ash-D to 91% for Fly ash-C. Finally, soluble salts such as NaCl and KCl were removed during the sulfidation treatment, which brought about a significant enrichment in metals content by a factor varying from 1.5 for Fly ash-D to 4.9 for Fly ash-A.     

Bacteria transport and deposition under unsaturated conditions: the role of the matrix grain size and the bacteria surface protein

Unsaturated (80% water saturated) packed column experiments were conducted to investigate the influence of grain size distribution and bacteria surface macromolecules on bacteria (Rhodococcus rhodochrous) transport and deposition mechanisms. Three sizes of silica sands were used in these transport experiments, and their median grain sizes were 607, 567, and 330 microm. The amount of retained bacteria increased with decreasing sand size, and most of the deposited bacteria were found adjacent to the column inlet. The deposition profiles were not consistent with predictions based on classical filtration theory. The experimental data could be accurately characterized using a mathematical model that accounted for first-order attachment, detachment, and time and depth-dependent straining processes. Visual observations of the bacteria deposition as well as mathematical modelling indicated that straining was the dominant mechanism of deposition in these sands (78-99.6% of the deposited bacteria), which may have been enhanced due to the tendency of this bacterium to form aggregates. An additional unsaturated experiment was conducted to better deduce the role of bacteria surface macromolecules on attachment and straining processes. In this case, the bacteria surface was treated using a proteolitic enzyme. This technique was assessed by examining the Fourier-transform infrared spectrum and hydrophobicity of untreated and enzyme treated cells. Both of these analytical procedures demonstrated that this enzymatic treatment removed the surface proteins and/or associated macromolecules. Transport and modelling studies conducted with the enzyme treated bacteria, revealed a decrease in attachment, but that straining was not significantly affected by this treatment.     

Ozone pre-treatment as improver of PAH removal during anaerobic digestion of urban sludge

Polycyclic aromatic hydrocarbons are ubiquitous persistent pollutants. They may accumulate in sludge during wastewater treatment because of their low biodegradability and their hydrophobic characteristics. Combination of ozonation and anaerobic digestion may be efficient to remove PAHs naturally present in sludge. The objective of this study was to investigate the impact of ozone pre-treatment, with and without surfactant addition, on the anaerobic degradation of 12 PAHs (from low to high molecular weight). Under anaerobic digestion without ozonation pre-treatment, the highest removals were obtained for the lightest PAHs (3-aromatic rings). Ozonation pre-treatment of sludge allowed to increase biodegradability or bioavailability of each PAH, and the PAH removals were well correlated to the PAH solubility. Finally, addition of tyloxapol before sludge ozone pre-treatment had antagonist effects on PAH removal during anaerobic digestion: negative impact on anaerobic ecosystem activity and improvement of PAH bioaccessibility (particularly the PAHs with the highest octanol water partition coefficients).     

Future climate scenarios and rainfall--runoff modelling in the Upper Gallego catchment (Spain)

Global climate change may have large impacts on water supplies, drought or flood frequencies and magnitudes in local and regional hydrologic systems. Water authorities therefore rely on computer models for quantitative impact prediction. In this study we present kernel-based learning machine river flow models for the Upper Gallego catchment of the Ebro basin. Different learning machines were calibrated using daily gauge data. The models posed two major challenges: (1) estimation of the rainfall-runoff transfer function from the available time series is complicated by anthropogenic regulation and mountainous terrain and (2) the river flow model is weak when only climate data are used, but additional antecedent flow data seemed to lead to delayed peak flow estimation. These types of models, together with the presented downscaled climate scenarios, can be used for climate change impact assessment in the Gallego, which is important for the future management of the system.     

The influence of EDDS and EDTA on the uptake of heavy metals of Cd and Cu from soil with tobacco Nicotiana tabacum

Phytoextraction, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. In order to enhance phytoextraction the use of chelating agents has been proposed. This study aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposed, as an alternative to ethylene diamine tetraacetate (EDTA). EDDS revealed a higher toxicity to tobacco (Nicotiana tabacum) in comparison to EDTA, but no toxicity to microorganisms. The uptake of Cu was increased by the addition of EDTA and EDDS, while no increase was observed in the uptake of Cd. Both chelating agents showed a very low root to shoot translocation capability and the translocation factor was lower than the one of the control. Heavy metals where significantly more phytoavailable than in the control, even after harvesting, resulting in a high heavy metal leaching possibility, probably owing to a low biodegradation rate of EDDS. New seedlings which were transplanted into the EDDS treated pots 7d after the phytoextraction experiment, showed signs of necrosis and chlorosis, which resulted in a significantly lower biomass in comparison to the control. The seedlings on the EDTA treated pots showed no toxicity signs. Contrary to previous opinions the results of this study revealed the chelating agents EDTA and EDDS as unsuitable for enhanced phytoextraction using tobacco.     

A study of climate change and anthropogenic impacts in West Africa

BACKGROUND, AIM AND SCOPE: During the last decades ecological conditions in West Africa have dramatically changed. Very evident is the climate change, which has resulted in a southward shift of the climate zones, e.g. a spread of the desert (Sahara) into the Sahelian zone. After the drought period of the early 1970s and 1980s, livestock density increased resulting in an intensification of grazing pressure. This anthropogenous phenomenon leads to similar landscape changes as those caused by the climate. Only very few investigations exist on vegetation dynamics, climate changes and land use changes for the Sudanian zone. The paper presents data on changes of precipitation, of land use, of the geographical range of species, and of the composition of the flora, which have to be regarded as proofs of the sahelisation of large areas of the Sudanian zone. MATERIALS AND METHODS: Area of investigation: Burkina Faso. Precipitation data analysis: precipitation data from 67 stations; time series analysis and geo-statistical spatial interpolation. Analysis of land use change: Landsat satellite MSS and ETM+ data, acquired for two different dates between 1972 and 2001 analyzed by the software ERDAS/IMAGINE version 8.6 and ArcView 3.2 with the Spatial Analyst extension. Intensive ground truthing (160 training areas). Inventory of the flora: based on the data of the Herbarium Senckenbergianum (FR) in Frankfurt, Germany, and of the herbarium of the university of Ouagadougou (OUA), Burkina Faso, as well as on various investigations on the vegetation of Burkina Faso carried out in the years 1990 to 2005 by the team of the senior author. Life form analysis of the flora: based on the inventory of permanent plots. RESULTS AND DISCUSSION: Precipitation: Remarkable latitudinal shift of isohyets towards the South translates to a general reduction of average rainfall in great parts of the country. The last decade (1990-1999) shows some improvement, however, the more humid conditions of the 1950's and 1960's are not yet established again. Landcover change: In the study region the extent of arable fields and young fallows increased during the last 30 years from 580 km(2) in 1972 to 2870 km(2) in 2001. This means an average land cover conversion rate of 0.9% per year for the 6 departments considered. Change of the distribution of Sahelian and Sudanian species: Several species, mentioned in older literature as strictly Sahelian, today also occur in the Sudanian zone. Parallel to the spread of former strictly Sahelian species into the Sudanian zone, some former Sahelo-Sudanian species have withdrawn from the Sahel. Changes of the life form spectra of the flora: Considering their life form spectra, the flora of heavily grazed and of protected areas in the Sudanian zone show great differences. On areas intensively grazed the percentage of therophytes is evidently higher than on protected areas. Just the opposite is true for the phanerophytes. Their percentage is higher on the protected area than on the grazed zones. At the first glance, it is obvious to link the changes in flora and vegetation with the climate changes that have occurred during the last five decades (decrease of annual precipitation). However, not only climatic conditions have changed, but also population has increased, the percentage of land intensively used for agriculture and pasturing has increased and the time for soil regeneration today is much shorter than it was some decades ago. Thus, the landscape of the Sudanian zone has become a more Sahelian character. A comparison of the flora of an intensively used area of the Sudanian zone with that of a protected area shows a remarkable change in the life form spectra. The spectrum of the intensively used area is almost identical with that of the typical Sahelian flora. This comparison shows that the anthropogenic influence plays a greater role in the sahelisation of the Sudanian zone than the climate change. CONCLUSION: Climate change and anthropogenic influence both, lead to a sahelisation of landscape and flora. Thus in many parts of the Sudanian zone of West Africa sahelisation phenomena will remain and even increase independently from the reestablishment of the more humid climate conditions of the 1950ies. RECOMMENDATIONS AND PERSPECTIVES: In order to maintain some parts of the characteristic Sudanian landscape with its characteristic flora and vegetation, the number and size of protected areas should be augmented. For all protected areas it has to be ensured, that protection is reality, i.e. respected an understood by local people, not only fiction. As long as the enlargement of intensively used areas continues the sahelisation of flora, vegetation and landscape will continue too.     

Application of activated sludge model no. 3 for the modeling of organic matter biodegradation at thermophilic temperatures.

The primary aim of our research was to investigate the applicability of activated sludge models (ASM) for aerobic thermophilic processes, especially autothermal thermophilic aerobic digestion (ATAD). The ASM3 model (Gujer et al., 1999) theoretically seems to be the most suitable, because storage plays an important role in a batch-feed cycle system like ATAD. The ASM3 model was extended with an activation step of the thermophilic organisms. This model was calibrated and verified by independent test results, demonstrating its ability to describe the process. The growth (microH = 26.04 day(-1)), storage (k(STO) = 20.39 day(-1)), hydrolysis (kH = 11.15 day(-1)) and decay rates (b 9H,O2) = 1.28 day(-1), b(STO,O2 = 1.10 day-1)) obtained from calibration are significantly higher at 55 degrees C than at mesophilic temperatures, justifying the faster metabolism at higher temperatures. An inert fraction of the biomass (characterized by the model parameter f(i) = 0.4) was found to be significantly greater than in the mesophilic case. This can be attributed to the lower diversity of the thermophilic species and thus to their narrower substrate spectra.     

Refinery evaluation of optical imaging to locate fugitive emissions

Fugitive emissions account for approximately 50% of total hydrocarbon emissions from process plants. Federal and state regulations aiming at controlling these emissions require refineries and petrochemical plants in the United States to implement a Leak Detection and Repair Program (LDAR). The current regulatory work practice, U.S. Environment Protection Agency Method 21, requires designated components to be monitored individually at regular intervals. The annual costs of these LDAR programs in a typical refinery can exceed US$1,000,000. Previous studies have shown that a majority of controllable fugitive emissions come from a very small fraction of components. The Smart LDAR program aims to find cost-effective methods to monitor and reduce emissions from these large leakers. Optical gas imaging has been identified as one such technology that can help achieve this objective. This paper discusses a refinery evaluation of an instrument based on backscatter absorption gas imaging technology. This portable camera allows an operator to scan components more quickly and image gas leaks in real time. During the evaluation, the instrument was able to identify leaking components that were the source of 97% of the total mass emissions from leaks detected. More than 27,000 components were monitored. This was achieved in far less time than it would have taken using Method 21. In addition, the instrument was able to find leaks from components that are not required to be monitored by the current LDAR regulations. The technology principles and the parameters that affect instrument performance are also discussed in the paper.