A note on non-parametric and semi-parametric modeling of wildfire hazard in Los Angeles County, California

This paper explores the use of, and problems that arise in, kernel smoothing and parametric estimation of the relationships between wildfire incidence and various meteorological variables. Such relationships may be treated as components in separable point process models for wildfire activity. The resulting models can be used for comparative purposes in order to assess the predictive performance of the Burning Index.

Silver nanoparticles: behaviour and effects in the aquatic environment

This review summarises and evaluates the present knowledge on the behaviour, the biological effects and the routes of uptake of silver nanoparticles (Ag NPs) to organisms, with considerations on the nanoparticle physicochemistry in the ecotoxicity testing systems used. Different types of Ag NP syntheses, characterisation techniques and predicted current and future concentrations in the environment are also outlined. Rapid progress in this area has been made over the last few years, but there is still a critical lack of understanding of the need for characterisation and synthesis in environmental and ecotoxicological studies. Concentration and form of nanomaterials in the environment are difficult to quantify and methodological progress is needed, although sophisticated exposure models show that predicted environmental concentrations (PECs) for Ag NPs in different environmental compartments are at the range of ng L(-1) to mg kg(-1). The ecotoxicological literature shows that concentrations of Ag NPs below the current and future PECs, as low as just a few ng L(-1), can affect prokaryotes, invertebrates and fish indicating a significant potential, though poorly characterised, risk to the environment. Mechanisms of toxicity are still poorly understood although it seems clear that in some cases nanoscale specific properties may cause biouptake and toxicity over and above that caused by the dissolved Ag ion. This review concludes with a set of recommendations for the advancement of understanding of the role of nanoscale silver in environmental and ecotoxicological research.     

Preliminary indications from atomic force microscopy of the presence of rapidly-formed nanoscale films on aquifer material surfaces

The objective of this study was to determine if there is a nanoscale surface film on aquifer-like materials exposed to deep groundwaters, as has previously been found on surfaces exposed to surface and soil waters. Such surface films will modify surface properties that are so important in determining the mobility of many groundwater pollutants. Muscovite mica was used because a) it is a good analogue for the main sorbing phases of many clastic aquifers and b) its cleavage planes are atomically flat allowing high resolution imaging. Freshly-cleaved muscovite plates were exposed to groundwater from a sandstone aquifer for 30 min, and surface properties (morphology, coverage, roughness and tip–substrate force interactions) were measured using atomic force microscopy (AFM). A patchy surface film of several nanometres in depth, incorporating larger separate particles, was found on the mica surface. This film was associated with significantly increased roughness values and AFM probe–sample interaction forces compared with pure water and inorganic (synthetic groundwater) solution controls. Although the results reported are preliminary in nature, if confirmed, such films are likely to affect sorption reactions, surface-facilitated redox interactions, non-aqueous phase liquid wetting angles, and colloid–pathogen–rock attachment, and will thus be of importance in understanding natural attenuation and migration of dissolved, non-aqueous and particulate phases in groundwaters.     

Long-term atmospheric deposition of current-use and banned pesticides in Atlantic Canada; 1980-2000

The occurrence of current-use and banned pesticides is reported in wet-precipitation collected from four sites across Atlantic Canada during the period 1980-2000. The most frequently detected compounds were alpha-HCH, gamma-HCH (lindane), chlorothalonil, pentachlorophenol, atrazine, and endosulfan. Median site concentrations varied between not-detected and 10.2 ng l(-1). Deposition of HCHs (hexachlorocyclohexane), chlorothalonil, and endosulfan at Kejimkujik (Keji) and Jackson, Nova Scotia, were generally similar. Significant spatial differences (p<0.05), however, were found for the HCH isomers and endosulfan at Keji and Gros Morne (Newfoundland and Labrador), areas geographically separated by the northern Gulf of St. Lawrence. Long-term deposition of alpha-HCH decreased (p<0.05) at both Keji (1980-2000) and Gros Morne (1994-2000), with half-lives of 5.9 and 4.5 y, respectively. A decreasing trend was also found for pentachlorophenol with a half-life of 4.9 y at Jackson. Significant negative trends (p<0.05) were observed for alpha-/gamma-HCH ratios during the study at Keji and Jackson, possibly reflecting changes in production and use patterns of technical HCH and lindane on a continental and perhaps hemispheric scale. Seasonal trends for alpha-HCH and gamma-HCH were found to vary over the 20-y study period at Keji, however, spatial trends were generally similar between sites. Seasonal trends were observed with peak deposition generally occurring during the growing period (spring-summer) for the HCHs, chlorothalonil, endosulfan, and atrazine. Bimodal seasonal trends were also observed for these compounds with the exception of endosulfan.     

Water Planning and Hydro-Climatic Change in the Murray-Darling Basin,Australia

More than a third of humanity lives in regions with less than 1 million liters of fresh water per person per year. Population growth will increase water demand while climate change in arid and semi-arid areas may reduce water availability. The Murray-Darling Basin in Australia is a region where water reform and planning have been used to reduce consumptive extraction to better sustain river ecosystems under climate variability. Using actual data and previously published models that account for climate variability and climate change, the trade-off between water extractions and water essential to the long-term ecological function of river systems is analysed. The findings indicate that better water planning and a more complete understanding of the effects of irrigation on regional climate evapotranspiration could: (1) increase the overall benefits of consumptive and non-consumptive water use; (2) improve riparian environments under climate variability; and (3) be achieved with only small effects on the profits and gross value of food and fiber production.     

Modelling the photooxidation of ULP,E5 and E10 in the CSIRO smog chamber

The photooxidation of fuel vapour was investigated in a smog chamber and simulated using three chemical mechanisms, the Master Chemical Mechanism (MCMv3.1), SAPRC-99 and the Carbon Bond chemical mechanism (CB05). Three varieties of fuel were used, unleaded petrol (ULP) and two ULP-ethanol blends which contained 5% and 10% ethanol (E5, E10). The fuel vapours were introduced into the chamber using two methods, by injecting the vapours from wholly evaporated fuel directly, and by injecting the headspace vapour from fuel equilibrated at 38 °C. The chamber experiments were simulated using the selected mechanisms and comparisons made with collected experimental data.The SAPRC-99 mechanism reproduced Δ(O₃–NO) more accurately for almost all fuel types and injection modes, with negligible model error for both injection modes. The average model error for MCM simulations was ?16% and for CB05 the average model error was ?34%. The predictions for the CB05 mechanism varied depending on injection mode, the Δ(O₃–NO) model error for wholly evaporated experiments was ?44%, compared to ?24% for headspace vapour experiments. The difference in aromatic content between experiments of different injection modes was likely to be the cause of the difference in model error for CB05. The model error for all headspace experiments was dependent upon the initial carbon monoxide concentrations.The results for Δ(O₃–NO) were matched by the prediction of other key products, with formaldehyde predicted to within 20% by both SAPRC and the MCM. The addition of ethanol to the base SAPRC mechanism altered the predictions of Δ(O₃–NO) by less than 2%. Changes observed in the concentrations of formaldehyde and acetaldehyde were consistent with the expected yields from ethanol oxidation.     

Kinetics and equilibrium properties of the biosorption of Cu2+ by algae

The purpose of this study was to examine the kinetics and equilibrium properties of freshwater algae with Cu²⁺. This was a model system to explore using algae as biosensors for water quality. Methods included making luminescence measurements (fluorescence) and copper ion-selective electrode (CuISE) measurements vs. time to obtain kinetic data. Results were analyzed using a pseudo-first-order model to calculate the rate constants of Cu²⁺ uptake by algae: k _p(Cu?Calgae)?=?0.0025?±?0.0006?s^?1 by CuISE and k _p(Cu?Calgae)?=?0.0034?±?0.0011?s^?1 by luminescence. The binding constant of Cu?Calgae, K _Cu?Calgae, was 1.62?±?0.07?×?10⁷?M^?1. Fluorescence results analyzed using the Stern?CVolmer relationship indicate that algae have two types of binding sites of which only one appears to affect quenching. The fluorescence-based method was found to be able to detect the reaction of algae with Cu²⁺ quickly and at a detection limit of 0.1?mg?L^?1.     

Phytotoxicity of silver nanoparticles to Lemna minor L

The use of silver nanoparticles (AgNPs) in commercial products has increased significantly in recent years. Although there has been some attempt to determine the toxic effects of AgNPs, there is little information on aquatic plants which have a vital role in ecosystems. This study reports the use of Lemna minor L. clone St to investigate the phytotoxicity of AgNPs under modified OECD test conditions. AgNPs were synthesised, characterised and subsequently presented to the L. minor. Results showed that inhibition of plant growth was evident after exposure to small (∼20 nm) and larger (∼100 nm) AgNPs at low concentrations (5 μg L⁻¹) and this effect became more acute with a longer exposure time. There was a linear dose-response relationship after 14 d exposure. Using predicted environmental concentrations for wastewaters it was found that AgNPs may pose a significant potential risk to the environment.     

Fluorescence characterization of cross flow ultrafiltration derived freshwater colloidal and dissolved organic matter

3-D fluorescence excitation-emission matrix (EEM) spectrophotometry was applied to investigate the fluorescence characterization of colloidal organic matter (COM) and truly dissolved organic matter (DOM) from an urban lake and a rural river fractionated by the cross flow ultrafiltration (CFUF) process with a 1kDa membrane. Relatively high tryptophan-like fluorescence intensity is found in the urban water, although the fluorescence of both water samples is mainly dominated by humic/fulvic-like fluorophores. During CFUF processing, the fluorescence intensities of humic/fulvic-like materials in the retentate increased rapidly, but a slight increase is also observed in the permeate fluorescence intensity. Very different ultrafiltration behaviour occurred with respect to the tryptophan-like fluorophore, where both permeate and retentate fluorescence intensities increase substantially at the beginning of the CFUF process, then tend to remain constant at high concentration factor (cf) values. Comparison with tryptophan standards demonstrates that freshwater tryptophan-like fluorescence is not dissolved and 'free', but is, in part, colloidal and related to the ultrafiltration behaviour of fulvic/humic-like matter. A good linear relationship between the retentate humic/fulvic-like fluorescence intensity and organic carbon concentration further reveals that fluorescent humic/fulvic-like substances are the dominant contributors to colloidal organic carbon, mainly in the colloidal fraction.     

Atmospheric Chemistry of Chlorinated Phenols

The quantum yields for the photodegradation of a series of chlorophenols have been used to estimate their rates of solar photodegradation In the atmosphere. The photochemical rates have been compared with the calculated rates of attack by atmospheric hydroxyl radicals. These two processes are complementary, with photolysis being faster for pentachlorophenol, and OH attack being faster for monochlorinated phenols. As a result, it is predicted that most chlorophenol congeners will have quite similar atmospheric half-lives.