Passive sampling: partition coefficients for a silicone rubber reference phase

Silicone rubber sheeting can be used as a passive sampling device for hydrophobic organic contaminants in the environment to determine the available concentrations in water and sediments. Reliable sampler-water partition coefficients are required to determine the sampling rates and the dissolved contaminant concentrations in water and in sediment pore water. Log partition coefficients (logK(sr,w)) for silicone rubber-water have been estimated for 32 polycyclic aromatic hydrocarbons (PAHs), 2 deuterated PAH analogues and 32 chlorobiphenyls (CBs) using the cosolvent method, with methanol as cosolvent. Strong linear relationships were found with literature values for the corresponding log octanol-water partition coefficients (logK(ow)) for both CBs and PAHs, confirming that partitioning into the silicone rubber is strongly determined by the hydrophobicity of the compounds, which suggests logK(ow) is a good predictor of logK(sr,w) and that absorption is the main mechanism for accumulation of analytes into the silicone rubber polymer.     

Population dynamics and the economics of invasive species management: the greenhouse whitefly in California-grown strawberries

In agriculture, relatively few efficacious control measures may be available for an invasive pest. In the case of a new insect pest, insecticide use decisions are affected by regulations associated with its registration, insect population dynamics, and seasonal market price cycles. We assess the costs and benefits of environmental regulations designed to regulate insecticide applications on an invasive species. We construct a bioeconomic model, based on detailed scientific data, of management decisions for a specific invasion: greenhouse whiteflies in California-grown strawberries. The empirical model integrates whitefly population dynamics, the effect of whitefly feeding on strawberry yields, and weekly strawberry price. We use the model to assess the optimality of alternative treatment programs on a simulated greenhouse whitefly population. Our results show that regulations may lead growers to "under-spray" when placed in an economic context, and provide some general lessons about the design of optimal invasive species control policies.     

Surface geophysical exploration: developing noninvasive tools to monitor past leaks around Hanford’s tank farms

A characterization program has been developed at Hanford to image past leaks in and around the underground storage tank facilities. The program is based on electrical resistivity, a geophysical technique that maps the distribution of electrical properties of the subsurface. The method was shown to be immediately successful in open areas devoid of underground metallic infrastructure, due to the large contrast in material properties between the highly saline waste and the dry sandy host environment. The results in these areas, confirmed by a limited number of boreholes, demonstrate a tendency for the lateral extent of the underground waste plume to remain within the approximate footprint of the disposal facility. In infrastructure-rich areas, such as tank farms, the conventional application of electrical resistivity using small point-source surface electrodes initially presented a challenge for the resistivity method. The method was then adapted to directly use the buried infrastructure, specifically the steel-cased wells that surround the tanks, as “long” electrodes for both transmission of electrical current and measurements of voltage. Overcoming the drawbacks of the long electrode method has been the focus of our work over the past 7 years. The drawbacks include low vertical resolution and limited lateral coverage. The lateral coverage issue has been improved by supplementing the long electrodes with surface electrodes in areas devoid of infrastructure. The vertical resolution has been increased by developing borehole electrode arrays that can fit within the small-diameter drive casing of a direct push rig. The evolution of the program has led to some exceptional advances in the application of geophysical methods, including logistical deployment of the technology in hazardous areas, development of parallel processing resistivity inversion algorithms, and adapting the processing tools to accommodate electrodes of all shapes and locations. The program is accompanied by a full set of quality assurance procedures that cover the layout of sensors, measurement strategies, and software enhancements while insuring the integrity of stored data. The data have been shown to be useful in identifying previously unknown contaminant sources and defining the footprint of precipitation recharge barriers to retard the movement of existing contamination.     

How Do River Nitrate Concentrations Respond to Changes in Land-use? A Modelling Case Study of Headwaters in the River Derwent Catchment,North Yorkshire,UK

A combined semi-distributed hydrological model (CASCADE/QUESTOR) is used to evaluate the steady-state that may be achieved after changes in land-use or management and to explore what additional factors need to be considered in representing catchment processes. Two rural headwater catchments of the River Derwent (North Yorkshire, UK) were studied where significant change in land-use occurred in the 1990s and the early 2000s. Much larger increases in mean nitrate concentration (55%) were observed in the catchment with significant groundwater influence (Pickering Beck) compared with the surface water-dominated catchment (13% increase). The increases in Pickering Beck were considerably greater than could be explained by the model in terms of land-use change. Consequently, the study serves to focus attention on the long-term increases in nitrate concentration reported in major UK aquifers and the ongoing and chronic impact this trend is likely to be having on surface water concentrations. For river environments, where groundwater is a source, such trends will mask the impact of measures proposed to reduce the risk of nitrate leaching from agricultural land. Model estimates of within-channel losses account for 15–40% of nitrate entering rivers.     

The distribution and composition of hydrocarbons in sediments from the Fladen Ground, North Sea, an area of oil production

The distribution and composition of hydrocarbons in sediment from the Fladen Ground oilfield in the northern North Sea have been investigated. The total PAH concentrations (2- to 6-ring parent and alkylated PAHs, including the 16 US EPA PAHs) in sediments were relatively low (<100 microg kg(-1) dry weight). The PAH, the Forties crude and diesel oil equivalent concentrations were generally higher in sediment of fine grain size and higher organic carbon concentration. PAH distributions and concentration ratios indicated a predominantly pyrolytic input, being dominated by the heavier, more persistent, 5- and 6-ring compounds, and with a high proportion of parent PAHs. The n-alkane profiles of a number of the sediments contained small, high boiling point, UCMs, indicative of weathered oil arising from a limited petrogenic input. The geochemical biomarker profiles of the sediments that contained UCMs showed a small bisnorhopane peak and a high proportion of norhopane relative to hopane, indicating that there was contamination from both Middle Eastern and North Sea oils. Therefore contamination was not directly as a result of oil exploration activity in the area. The most likely source of petrogenic contamination was from general shipping activity.     

LogD: lipophilicity for ionisable compounds

The octanol/water partition coefficient (Kow) for organic compounds is widely used in predictive environmental studies. A significant proportion of contaminants of surface and ground water are ionisable (e.g. many pesticides, pharmaceuticals, metabolites). Such compounds may be partially ionised dependent on the pH. Since the neutral and ionic species exhibit different polarities, the Kow value of ionisable pesticides is pH dependent. It is therefore essential to determine Kow values over the full range of pH that occurs in the environment in order to get appropriate predictors. Numerous methods are available to measure lipophilicity but only a few are appropriate for ionisable pesticides (e.g. pH metric and filter probe methods). Parameters such as pH and ionic strength need to be carefully controlled when working with ionisable compounds. Variation of these factors probably explains why literature can yield Kow values that differ by more than one order of magnitude for some compounds. In this article, Kow values obtained for six acidic pesticides with three different methods are compared as well (data from the literature, measured by pH metric method and calculated with five computer programs). The values used in predictive regression equations needs to be either measured with a suitable method or selected from the literature with great care.