Estimating the hydraulic properties of the fracture network in a sandstone aquifer

The potential hydraulic behaviour of the fracture network in a major Triassic sandstone aquifer in the UK has been evaluated. The properties of the fracture network were determined using results from detailed scan line surveys at 10 sites, television and geophysical borehole logging, and packer testing. Six sets of discontinuities common to all sites were identified and statistically characterised (dip, strike, orientation, density, size, and estimated transmissivity). A discrete fracture network model was then used stochastically to investigate the properties of the network. In general, the network is poorly connected: it is estimated that 9% of the discontinuities intersecting boreholes are transmissive. The hydraulic behaviour of the network is generally dominated by one sub-horizontal bedding plane fracture set, although when present, a relatively infrequent north-south striking, sub-vertical set modifies the bulk flow properties significantly. Ignoring this latter set, the network's minimum representative volume is about 35 x 35 x 35 m. The upscaled permeability is anisotropic, being typically 23 times greater in the horizontal than in the vertical. Tortuosity in the north-south direction is around 1.6.     

Biotransformation of flumequine by the fungus Cunninghamella elegans

The metabolism of the antibacterial fluoroquinolone drug flumequine by Cunninghamella elegans was investigated using cultures grown in Sabouraud dextrose broth with 308microM flumequine. The cultures were extracted with ethyl acetate; metabolites were separated by high-performance liquid chromatography and identified by mass spectrometry and proton nuclear magnetic resonance spectroscopy. Flumequine was transformed to two diastereomers of 7-hydroxyflumequine (23 and 43% of the total chromatographic peak area at 280nm) and 7-oxoflumequine (11% of the total peak area). This is the first time that the two 7-hydroxy diastereomers have been characterized structurally; the hydroxyflumequines are known to have less antimicrobial activity than flumequine.     

Fractionation and Determination of Ah Receptor (AhR) Agonists in Organic Waste After Anaerobic Biodegradation and in Batch Experiments with PCB and decaBDE (8 pp)

Goals, Scope and Background

Anaerobic digestion of organic household waste can lead to an increase in dioxin-like content, as determined by dioxin-specific bioassays. This may be a result of bioactivation of Ah receptor (AhR) agonists into more potent congeners. Work towards identifying the contributing compound groups is important in order to understand the mechanisms and to assess the relevance behind this increase in dioxin-like toxicity, since the residue can be used as a soil fertilising agent. The aim with the present work was to identify compound groups with AhR agonistic properties that caused the previously reported increase in dioxin-like activity after anaerobic biodegradation

Methods

Firstly, chemical fractionation combined with dioxin bioassay testing was used to find bioactive classes of compounds. Secondly, batch digestion experiments with an externally added polychlorinated biphenyl (PCB) mixture (Clophen A50) and with decabrominated diphenyl ether (decaBDE), respectively, were studied as a possible process for transformation of precursors into more potent, dioxin-like compounds. Mesophilic (37ºC) and thermophilic (55ºC) anaerobic digestion were studied. Two different dioxin-specific bioassays were used to analyse AhR agonists in the biodegraded material, the CELCAD and the DR-CALUX.

Results and Discussion

AhR agonist activity was detected in both di- and polyaromatic fractions of digestate extracts, which indicated that a diverse mixture of compounds contributed to the bioassay responses. No quantifiable activities were induced by the monoaromatic fractions. Further fractionation based on planarity revealed higher concentrations of AhR agonists than what was detected after the first fractionation, probably due to non-additive biological interactions of compounds in the extract that were removed in the second fractionation. These results showed significant activity in the non-planar diaromatic fractions and in the co-planar fractions of both diaromates and polyaromates. In the batch experiment with externally added PCB, an increase in dioxin-like activity was seen after 21 days of digestion at mesophilic conditions. After completed digestion, the content of AhR agonists was equal to the start concentration. PCB analysis with GC-MS indicated that dehalogenation of PCBs occurred in the digestors. The batch experiment with decaBDE showed no significant changes in TEQ-concentrations over time.

Conclusions

The results show that the previously reported increase of AhR agonists during mesophilic anaerobic digestion is probably due to an accumulation of several different groups of AhR agonists, both diaromatic and polyaromatic, and both co-planar and non-planar. Batch experiments with externally added PCBs and decaBDE, respectively, did not result in any accumulation of AhR agonist activity after completed digestion, even though chemical analysis indicate a dechlorination of PCBs. Complex, unfractionated extracts were difficult to test using the bioassay approach. Removal of AhR antagonists or otherwise interacting compounds during fractionation may yield bio-TEQ values that are much higher than in the original extract.

Recommendations and Perspective

. Our results indicate that the environmental risk that AhR agonists may pose concerning large-scale anaerobic digestion of organic household waste probably depends on the efficiency of the digester and the sludge residence time. In order to obtain reliable results with the bioassays, an extensive cleanup and fractionation procedure is necessary. Without clean up and fractionation, there is a risk for false negatives and misleading conclusions. DR-CALUX and CELCAD were both suitable for these kinds of studies, provided that suitable fractionation methods are used.

     

Source apportionment of fine particulate matter in Phoenix, AZ, using positive matrix factorization

Speciated particulate matter (PM)2.5 data collected as part of the Interagency Monitoring of Protected Visual Environments (IMPROVE) program in Phoenix, AZ, from April 2001 through October 2003 were analyzed using the multivariate receptor model, positive matrix factorization (PMF). Over 250 samples and 24 species were used, including the organic carbon and elemental carbon analytical temperature fractions from the thermal optical reflectance method. A two-step approach was used. First, the species excluding the carbon fractions were used, and initially eight factors were identified; non-soil potassium was calculated and included to better refine the burning factor. Next, the mass associated with the burning factor was removed, and the data set rerun with the carbon fractions. Results were very similar (i.e., within a few percent), but this step enabled a separation of the mobile factor into gasoline and diesel vehicle emissions. The identified factors were burning (on average 2% of the mass), secondary transport (7%), regional power generation (13%), dust (25%), nitrate (9%), industrial As/Pb/Se (2%), Cu/Ni/V (7%), diesel (9%), and general mobile (26%). The overall contribution from mobile sources also increased, as some mass (OC and nitrate) from the nitrate and regional power generation factors were apportioned with the mobile factors. This approach allowed better apportionment of carbon as well as total mass. Additionally, the use of multiple supporting analyses, including air mass trajectories, activity trends, and emission inventory information, helped increase confidence in factor identification.     

Effects of Ageing and Microbial Component on Chemical Availability of 137Cs in a Long-term Experimental Site

A loamy soil contaminated with ¹³⁷CsCl 40 years ago was investigated by a sequential extraction technique to determine the effect of ageing on chemical availability of ¹³⁷Cs. The soil samples were sequentially extracted with H₂O, NH₄Ac, NH₂OH·HCl, H₂O₂, and HNO₃. Extractability of ¹³⁷Cs decreased in the order: HNO₃ > Residual > H₂O₂ > NH₄Ac > NH₂OH·HCl > H₂O. Only 0.94% in labile fractions (H₂O and NH₄Ac), while more than 96% was found in the strongly bound fraction (HNO₃ and residual). However, the activity percentage in labile fractions was increased to 1.34% after autoclaving treatment, while those in the other fractions did not significantly differ. This indicates that the microbial activity played a role in the ¹³⁷Cs retention. In the subsequent pot experiments with ryegrass and leek, specific activities in both plants were significantly higher in autoclaved soil than in non-autoclaved soil, and uptake of ¹³⁷Cs in the five cuts by ryegrass was 25% of the labile ¹³⁷Cs in the soil. In addition, a positive correlation was found between the amount of ¹³⁷Cs in labile fractions and that by plant uptake.     

Occurrence of diarrhetic shellfish poisoning (DSP) toxins in clams (Ruditapes decussatus) from Tunis north lagoon

The main diarrhetic shellfish toxins, okadaic acid (OA) and dinophysistoxin-1, 2 (DTX-2, 2) were detected by liquid chromatography-tandem mass spectrometry (LC-MS/MS) as pyrenacyl esters in clams (Ruditapes decussatus) collected in Tunis north lagoon from January 2007 to June 2008. Sample analyses by LC-MS/MS displayed OA and related congeners (DTX-2, 2) with a highest detected level of 21 μg OA eq/kg shellfish meat for the samples of January 2007. Nevertheless, all samples were MBA negative. During the study period, potentially toxic dinoflagellate Dinophysis sacculus was recorded all year, blooming at different times. Highest concentrations were recorded during January 2007 with 4.6?×?10(4) cells per liter and 4.10(4) cells per liter in the northern and southern districts, respectively. Results show that there is no significant correlation between D. sacculus densities in water column and diarrhetic shellfish poisoning (DSP) toxins concentrations unregistered in clams. These data reveal that DSP toxicity in clams of Tunis north lagoon is low according to European regulatory limit (160 μg OA eq/kg shellfish meat). However, a potential threat, in this area, is represented by DSP toxic species as D. sacculus and provides grounds for widen and reinforcing sanitary control of the phycotoxin measures in the region.     

Evaluation of usefulness of Microbial Assay for Risk Assessment (MARA) in the cyanobacterial toxicity estimation

The aim of the study was to elucidate the usefulness of the Microbial Assay for Risk Assessment (MARA) to evaluate toxicity in samples containing cyanobacterial products. Cyanobacterial extracts with different cyanotoxin contents and pure cyanotoxins—microcystin-LR, cylindrospermopsin and anatoxin-a—were tested. On the basis of the microbial reaction, MARA indicated only slight or no toxicity in the studied extracts. Similarly, no or low toxicity of pure toxins was detected at the concentrations used (up to 10 μg/ml). Weak relationships between the reactions of individual organisms exposed to cyanotoxin-containing extracts and to the same pure toxins were observed. On the other hand, inhibition of some organisms, such as Pichia anomalia, whose growth was not impacted by pure cyanotoxins, indicated the presence of other biologically active compounds in the studied extracts. In conclusion, MARA assay is not enough sensitive to be used as a good tool for cyanotoxin screening. It may, however, be applied in searching for antimicrobial/antifungal cyanobacteria-derived compounds.     

Chemical composition of ambient particulate matter and redox activity

Exposure to ambient particulate matter (PM) has been associated with a number of adverse health effects. Increasing studies have suggested that such adverse health effects may derive from oxidative stress, initiated by the formation of reactive oxygen species (ROS) within affected cells. The study aimed to assess physical characteristics and chemical compositions of PM and to correlate the results to their redox activity. PM_2.5 (mass aerodynamic diameter ≤2.5 μm) and ultrafine particles (UFPs, mass media aerodynamic diameter <0.1 μm) were collected in an urban area, which had heavy traffic and represented ambient air pollution associated with vehicle exhaust. Background samples were collected in a rural area, with low traffic flow. Organic carbon (OC), elemental carbon (EC), polycyclic aromatic hydrocarbons (PAHs), and metals were analyzed. The dithiothreitol activity assay was used to measure the redox activity of PM. Results showed that UFPs have higher concentrations of OC, EC, and PAHs than those of PM_2.5. Several metals, including Fe, Cu, Zn, Ti, Pb, and Mn, were detected. Among them, Cu had the highest concentrations, followed by Fe and Zn. Organic carbon constituted 22.8% to 59.7% of the content on the surface of PM_2.5 and UFPs. Our results showed higher redox activity on a per PM mass basis for UFPs as compared to PM_2.5. Linear multivariable regression analyses showed that redox activity highly correlated with PAH concentrations and organic compounds, and insignificantly correlated with EC and metals, except soluble Fe, which increased redox activity in particle suspension due to the presence of ROS.     

Factors regulating the coastal nutrient filter in the Baltic Sea

Ambio - The coastal zone of the Baltic Sea is diverse with strong regional differences in the physico-chemical setting. This diversity is also reflected in the importance of different...