Biodegradability and ecotoxicity of amine oxide based surfactants

The aerobic and anaerobic biodegradability as well as the aquatic toxicity of two fatty amine oxides and one fatty amido amine oxide were investigated. Aerobic biodegradation was evaluated using the CO(2) headspace test (ISO 14593) and biodegradation under anaerobic conditions was assessed employing a standardised batch test. The three amine oxide based surfactants tested were readily biodegradable under aerobic conditions but only the alkyl amido amine oxide was found to be easily biodegradable under anaerobic conditions. Toxicity to Photobacterium phosphoreum and Daphnia magna was evaluated. Bacteria (EC(50) from 0.11 to 11 mg l(-1)) proved to be more sensitive to the toxic effects of the amine oxide based surfactants than crustacea (IC(50) from 6.8 to 45 mg l(-1)). The fatty amido amine oxide showed the lowest aquatic toxicity.     

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.     

Risk assessment of linear alkylbenzene sulphonates, LAS, in agricultural soil revisited: robust chronic toxicity tests for Folsomia candida (Collembola), Aporrectodea caliginosa (Oligochaeta) and Enchytraeus crypticus (Enchytraeidae)

To obtain robust data on the toxicity of LAS, tests with the collembolan Folsomia candida L., the oligochaetes Aporrectodea caliginosa Savigny (earthworm) and Enchytraeus crypticus Westheide and Graefe (enchytraeid) were performed in a sandy loam soil. Additionally limited tests with LAS spiked to sewage sludge, and subsequently mixed into soil, were performed. For the endpoint of interest, reproduction in soil, we found an EC10 of 205 mg LAS kg(-1) soil [8.6-401] [95% confidence limits] for F. candida and an EC10 of 46 mg LAS kg(-1) soil [13-80] for A. caliginosa after 28 days. E. crypticus was not affected by concentrations up to 120 mg LAS kg(-1) soil. When adding (low contaminated) non-spiked sludge to soil, high stimulation of reproduction was observed for E. crypticus and A. caliginosa but not for F. candida. We argue that this difference in stimulative response between the tested species is related to the difference in feeding behaviour. Sludge spiked with LAS did not significantly affect the reproduction of F. candida (fertility: number of juvenile offspring) and A. caliginosa (fecundity: number of cocoons) (dose equivalent to 181 g and 91 g LAS kg(-1) sludge, respectively). Significantly reduced reproduction was observed for E. crypticus (at 120 mg LAS kg(-1) soil+sludge corresponding to 72 g LAS kg(-1) sludge) compared to non-spiked sludge. The reproduction by E. crypticus was, however, comparable to the reproduction observed in the control soil without sludge. Compared to LAS directly spiked to soil, the reproductive output of organisms exposed to spiked sludge was either not significantly different (F. candida, E. crypticus) or significantly improved (A. caliginosa). More studies are needed in order to make firm conclusions on the potential effect of artificially contaminated sludge in soil systems.     

Mechanism of decolorization and degradation of CI Direct Red 23 by ozonation combined with sonolysis

The decolorization and degradation of CI Direct Red 23, which is suspected to be carcinogenic, were investigated using ozonation combined with sonolysis. The results showed that the combination of ozonation and sonolysis was a highly effective way to remove color from waste water. The operational parameters, namely concentration of the dye, pH, ozone dose and ultrasonic density, were investigated during the process. The decolorization of the dye followed pseudo-first-order kinetics. Increasing the initial concentration of Direct Red 23 led to a decreasing rate constant. The optimum pH for the reaction was 8.0, and both lower and higher pH decreased the removal rate. The effect of the ozone dose on the dye decolorization was much greater than that of the sonolysis density. Intermediates such as naphthalene-2-sulfonic acid, 1-naphthol, urea and acetamide were detected by gas chromatography coupled with mass spectrometry in the absence of pH buffer, while nitrate and sulfate ions and formic, acetic and oxalic acids were detected by ion chromatography. A tentative degradation pathway was proposed without any further quantitative analyses. During the degradation, all nitrogen atoms and phenyl groups of Direct Red 23 were degraded into urea, nitrate ion, nitrogen and formic, acetic and oxalic acids, etc.     

Effect of soil moisture dynamics on dense nonaqueous phase liquid (DNAPL) spill zone architecture in heterogeneous porous media

The amount, location, and form of NAPL in contaminated vadose zones are controlled by the spatial distribution of water saturation and soil permeability, the NAPL spill scenario, water infiltration events, and vapor transport. To evaluate the effects of these processes, we used the three-phase flow simulator STOMP, which includes a new permeability-liquid saturation-capillary pressure (k-S-P) constitutive model. This new constitutive model considers three NAPL forms: free, residual, and trapped. A 2-D vertical cross-section with five stratigraphic layers was assumed, and simulations were performed for seven cases. The conceptual model of the soil heterogeneity was based upon the stratigraphy at the Hanford carbon tetrachloride (CT) spill site. Some cases considered co-disposal of NAPL with large volumes of wastewater, as also occurred at the Hanford CT site. In these cases, the form and location of NAPL were most strongly influenced by high water discharge rates and NAPL evaporation to the atmosphere. In order to investigate the impact of heterogeneity, the hydraulic conductivity within the lower permeability layer was modeled as a realization of a random field having three different classes. For six extreme cases of 100 realizations, the CT mass that reached the water table varied by a factor of two, and was primarily controlled by the degree of lateral connectivity of the low conductivity class within the lowest permeability layer. The grid size at the top boundary had a dramatic impact on NAPL diffusive flux just after the spill event when the NAPL was present near the ground surface. NAPL evaporation with a fine grid spacing at the top boundary decreased CT mass that reached the water table by 74%, compared to the case with a coarse grid spacing, while barometric pumping had a marginal effect for the case of a continuous NAPL spill scenario considered in this work. For low water infiltration rate scenarios, the distribution of water content prior to a NAPL spill event decreased CT mass that reached the water table by 98% and had a significant impact on the formation of trapped NAPL. For all cases simulated, use of the new constitutive model that allows the formation of residual NAPL increased the amount of NAPL retained in the vadose zone. Density-driven advective gas flow from the ground surface controlled vapor migration in strongly anisotropic layers, causing NAPL mass flux to the lower layer to be reduced. These simulations indicate that consideration of the formation of residual and trapped NAPLs and dynamic boundary conditions (e.g., areas, rates, and periods of different NAPL and water discharge and fluctuations of atmospheric pressure) in the context of full three-phase flow are needed, especially for NAPL spill events at the ground surface. In addition, NAPL evaporation, density-driven gas advection, and NAPL vertical movement enhanced by water flow must be considered in order to predict NAPL distribution and migration in the vadose zone.     

Comparison of calculated and measured foliar O3 flux in crop and forest species

We designed a new gas exchange system that concurrently measures foliar H2O, O3, and CO2 flux (HOC flux system) while delivering known O3 concentrations. Stomatal responses of three species were tested: snapbean, and seedlings of California black oak (deciduous broadleaf) and blue oak (evergreen broadleaf). Acute O3 exposure (120-250 ppb over an hour) was applied under moderate light and low vapor pressure deficits during near steady state conditions. The rate of stomatal closure was measured when the whole plant was placed in the dark. An adjacent leaf on each plant was also concurrently measured in an O3-free cuvette. Under some conditions, direct measurements and calculated foliar O3 flux were within the same order of magnitude; however, endogenously low gs or O3 exposure-induced depression of gs resulted in an overestimation of calculated O3 fluxes compared with measured O3 fluxes. Sluggish stomata in response to light extinction with concurrent O3 exposure, and incomplete stomatal closure likewise underestimated measured O3 flux.     

Toxic fluoride and arsenic contaminated groundwater in the Lahore and Kasur districts, Punjab, Pakistan and possible contaminant sources

The present study is the first attempt to put forward possible sources of As, F- and SO4(2-) contaminated groundwater in the Kalalanwala area, Punjab, Pakistan. Five rainwater and 24 groundwater samples from three different depths were analyzed. Shallow groundwater from 24 to 27 m depth contained high F- (2.47-21.1mg/L), while the groundwater samples from the deeper depth were free from fluoride contamination. All groundwater samples contained high As (32-1900 microg/L), in excess of WHO drinking water standards. The SO4(2-) ranges from 110 to 1550 mg/L. Delta34S data indicate three sources for SO4(2-) air pollutants (5.5-5.7 per thousand), fertilizers (4.8 per thousand), and household waste (7.0 per thousand). Our important finding is the presence of SO4(2-), As and F- in rainwater, indicating the contribution of these elements from air pollution. We propose that pollutants originate, in part, from coal combusted at brick factories and were mobilized promotionally by the alkaline nature of the local groundwater.     

Gravitational infusion of ethylenediurea (EDU) into trunks protected adult European ash trees (Fraxinus excelsior L.) from foliar ozone injury

Adult ash trees (Fraxinus excelsior L.), known to be sensitive or insensitive to ozone, determined by presence or absence of foliar symptoms in previous years, were treated with ethylenediurea (EDU) at 450 ppm by gravitational trunk infusion on six occasions at 21-day intervals in summer 2005 at Turin, Italy. At the end of the season, foliar ozone injury on EDU-treated trees was not complete, but was greatly and significantly reduced when compared to results from trees infused with water. Significant symptom reduction occurred at any crown level in the treated trees suggesting that EDU protected whole crowns. Gravitational infusion of EDU resulted in protection from ozone injury for ozone-sensitive ash trees. The amount of EDU needed to provide protection is assumed to be in the range 13-26 mg m(-2) leaf.     

Lichen and moss bags as monitoring devices in urban areas. Part II: trace element content in living and dead biomonitors and comparison with synthetic materials

Lobes of the lichen Pseudevernia furfuracea (L.) Zopf and shoots of the moss Hypnum cupressiforme Hedw. were subjected to different treatments (water washing, oven drying, HNO3 washing, NH4-oxalate extraction) to assess the influence of vitality on accumulation efficiency, during a 6-week exposure in bags in two Italian cities, Trieste and Naples. No trend emerged between treatments, in terms of accumulation ability, for major and trace elements. Only water-washed lichens showed an increased C and N content after exposure in both cities. Element concentrations generally reached higher values in mosses than in lichens, especially for Al, Fe, and Zn (both cities), and for Cu, Mg and Na (Naples). Surface development strongly influenced accumulation capacity of the biomonitors. Quartzose and cation exchange filters revealed, on a weight basis, a poor performance. In urban environments, surface interception of atmospheric particulate seems to play a major role in accumulation, irrespective of organism vitality.     

A biomimetic absorbent for removal of trace level persistent organic pollutants from water

A novel biomimetic absorbent containing the lipid triolein was developed for removing persistent organic pollutants (POPs) from water. The structural characteristics of the absorbent were obtained by SEM and a photoluminescence method. Under optimum preparation conditions, triolein was perfectly embedded in the cellulose acetate (CA) spheres, the absorbent was stable and no triolein leaked into the water. Dieldrin, endrin, aldrin and heptachlor epoxide were effectively removed by the CA--triolein absorbent in laboratory batch experiments. This suggests that CA-triolein absorbent may serve as a good absorbent for those selected POPs. Triolein in the absorbent significantly increased the absorption capacity, and lower residual concentrations of POPs were achieved when compared to the use of cellulose acetate absorbent. The absorption rate for lipophilic pollutants was very fast and exhibited some relationship with the octanol--water partition coefficient of the analyte. The absorption mechanism is discussed in detail.