Evaluation of the Chemcatcher and DGT passive samplers for monitoring metals with highly fluctuating water concentrations

Passive sampling devices accumulate chemicals continuously from water and can provide time weighted average (TWA) concentrations of pollutants over the exposure period. Hence, they offer a number of advantages over other conventional monitoring techniques such as spot or grab sampling. The diffusive gradient in thin film (DGT) and the Chemcatcher passive samplers can be used to provide TWA concentrations of labile metals, but the approaches to their calibration differ. DGT uses diffusion coefficients of metals in the hydrogel layer, whereas Chemcatcher uses metal specific uptake rates, with both sets of values obtained under controlled laboratory conditions with constant aqueous metal concentrations. However, little is known of how such samplers respond to fluctuating concentrations. We evaluated the responsiveness of these two passive sampling devices to rapidly changing concentrations of Cd, Cu, Ni, Pb and Zn in natural freshwater, over a relatively short deployment time. Maximum metal concentrations in water were varied between 70 and 140 microg L(-1). Experiments were carried out in a tank with a rotating carousel system and filled with Meuse river water, allowing a degree of control over experimental conditions while using natural river water. Fluctuating concentrations were obtained by stepwise addition of standard solutions of the metals. The reliability and accuracy of the TWA concentrations measured by the samplers were assessed by comparison with concentrations of the metals in spot samples of water taken regularly over the deployment period. The spot samples of water were either unfiltered (total), filtered (0.45 microm) or ultrafiltered (5 kDa). Predictive speciation modelling using the visual MINTEQ programme was also undertaken. There was reasonable agreement between the TWA concentrations of Cd and Ni obtained with Chemcatcher and DGT and the total Cd and Ni concentrations measured in repeated unfiltered spot samples. For elements (i.e. Cu, Pb, Zn) that associate to a significant degree with suspended solids, colloids or dissolved organic carbon, or form complexes with large organic ligands, optimum agreement was with the filtered or ultrafiltered fractions and with the predicted inorganic and inorganic-fulvic acid associated fractions. While Chemcatcher-based TWA concentration ranges for Cu and Zn were in best agreement with the total filtered fraction, there was lack of agreement for Pb. The combined use of DGT devices with open pore (OP) and restricted pore (RP) gels allowed the labile fraction of metal associated with large organic ligands or DOC to be differentiated and quantified, since this is available to DGT OP but unable to diffuse into the DGT RP. This evaluation of the two sampling devices clearly demonstrated their ability to react reliably to transient peaks in concentration of metal pollutants in water and indicated where future efforts are needed to improve calibration data. Such samplers may prove valuable in responding to the monitoring requirements of the European Union's Water Framework Directive.     

Comparison of in vivo and in vitro methodologies for the assessment of arsenic bioavailability in contaminated soils

An in vivo swine assay was utilised for the determination of arsenic (As) bioavailability in contaminated soils. Arsenic bioavailability was assessed using pharmacokinetic analysis encompassing area under the blood plasma-As concentration time curve following zero correction and dose normalisation. In contaminated soil studies, As uptake into systemic circulation was compared to an arsenate oral dose and expressed as relative As bioavailability. Arsenic bioavailability ranged from 6.9+/-5.0% to 74.7+/-11.2% in 12 contaminated soils collected from former railway corridors, dip sites, mine sites and naturally elevated gossan soils. Arsenic bioavailability was generally low in the gossan soils and highest in the railway soils, ranging from 12.1+/-8.5% to 16.4+/-9.1% and 11.2+/-4.7% to 74.7+/-11.2%, respectively. Comparison of in vivo and in vitro (Simplified Bioaccessibility Extraction Test [SBET]) data from the 12 contaminated soils and bioavailability data collected from an As spiked soil study demonstrated that As bioavailability and As bioaccessibility were linearly correlated (in vivo As bioavailability (mgkg(-1))=14.19+0.93.SBET As bioaccessibility (mgkg(-1)); r(2)=0.92). The correlation between the two methods indicates that As bioavailability (in vivo) may be estimated using the less expensive, rapid in vitro chemical extraction method (SBET) to predict As exposure in human health risk assessment.     

Geochemical Associations of Sellafield-Derived Radionuclides in Saltmarsh Deposits of the Solway Firth

This paper describes a study of the geochemical associations of Sellafield waste radionuclides in saltmarsh sediments from south-west s]Scotland. The contaminant radionuclides are transported to this environment in association with particulate material and ¹³⁷Cs was found to be predominantly (80-98%) non-extractable. In the case of ^239+240Pu there was a redistribution from the oxalate extractable oxide fraction to the pyrophosphate extractable organic fraction as a consequence of on-shore transfer of contaminated sediment. The relatively aggressive nature of the chemical extractants required to remove the radionuclides from the sediments suggests that they were in a form which was unlikely to result in their being released into the aquatic environment or taken up by plants. Plutonium had a greater potential mobility or bioavailability than Cs. Values of K^D for the desorption of ¹³⁷Cs from the sediment by freshwater, groundwater and seawater were all approximately 10⁵ L kg^-1, confirming its immobility in this environment. The desorption K_D values for stable ¹³³Cs were all approximately 10⁶ L kg^-1, so the stable Cs did not have a significant influence on the radiocaesium in this sediment.     

Gaps and opportunities for the World Heritage Convention to contribute to global wilderness conservation

Wilderness areas are ecologically intact landscapes predominantly free of human uses, especially industrial‐scale activities that result in substantial biophysical disturbance. This definition does not exclude land and resource use by local communities who depend on such areas for subsistence and bio‐cultural connections. Wilderness areas are important for biodiversity conservation and sustain key ecological processes and ecosystem services that underpin planetary life‐support systems. Despite these widely recognized benefits and values of wilderness, they are insufficiently protected and are consequently being rapidly eroded. There are increasing calls for multilateral environmental agreements to make a greater and more systematic contribution to wilderness conservation before it is too late. We created a global map of remaining terrestrial wilderness following the established last‐of‐the‐wild method, which identifies the 10% of areas with the lowest human pressure within each of Earth's 62 biogeographic realms and identifies the 10 largest contiguous areas and all contiguous areas >10,000 km². We used our map to assess wilderness coverage by the World Heritage Convention and to identify gaps in coverage. We then identified large nationally designated protected areas with good wilderness coverage within these gaps. One‐quarter of natural and mixed (i.e., sites of both natural and cultural value) World Heritage Sites (WHS) contained wilderness (total of 545,307 km²), which is approximately 1.8% of the world's wilderness extent. Many WHS had excellent wilderness coverage, for example, the Okavango Delta in Botswana (11,914 km²) and the Central Suriname Nature Reserve (16,029 km²). However, 22 (35%) of the world's terrestrial biorealms had no wilderness representation within WHS. We identified 840 protected areas of >500 km² that were predominantly wilderness (>50% of their area) and represented 18 of the 22 missing biorealms. These areas offer a starting point for assessing the potential for the designation of new WHSs that could help increase wilderness representation on the World Heritage list. We urge the World Heritage Convention to ensure that the ecological integrity and outstanding universal value of existing WHS with wilderness values are preserved.     

The interplay between incremental,transitional, and transformational adaptation: a case study of Canadian agriculture

Regional Environmental Change - We develop and apply a synthetic framework for understanding potential adaptations to climate change in the Canadian agriculture sector through a case study of...     

The Effects of Learner's Permit Requirements in Tennessee

Sixteen and 17 year-olds were surveyed at motor-vehicle offices in Tennessee after qualifying for their first driver's license. When the survey was conducted during October and November 1995, neither a learner's permit nor completion of a driver education course was required to obtain a license at age 16 or 17. The survey was repeated during December and January 1996–97, approximately one year after a requirement to hold a learner's permit for 90 days or complete a driver education course was implemented. Results from the 1991 drivers (ages 16 and 17) surveyed indicated Tennessee's licensing law change was associated with approximately 100 additional miles and 8 additional hours of practice driving prior to licensure for the typical 16 or 17 year-old, most often while supervised by a parent or guardian. Results are discussed in relation to the prelicense practice driving requirements of graduated licensing systems.     

Human Population Density and Prediction of Local Plant Extinction in Britain

Throughout the world, and particularly in densely populated countries like Britain, human activities exert a dominant influence on the abundance of both plants and animals. The commonness and rarity of plants in Britain has been plausibly linked to human land use. In Western Europe the identity of increasing and decreasing plants appears to depend on human population density, which is itself a crude measure of human impact on the landscape. The publication of new data on the changing distributions of scarce British plants allowed us to investigate the relationship between loss of scarce plants and human population density in Britain. Our results confirm that a direct effect of human population density on local plant extinctions can be detected at the regional scale in Britain. Although intensive agriculture is conventionally regarded as the greatest threat to British wildlife, our analysis suggests that urbanization may be at least as significant a danger.     

Comparison of nonideal sorption formulations in modeling the transport of phthalate esters through packed soil columns

Sorption of dimethyl phthalate (DMP), diethyl phthalate (DEP) and dipropyl phthalate (DPP) to two soil materials that vary in organic matter content was investigated using miscible displacement experiments under saturated flow conditions. Generated breakthrough curves (BTCs) were inversely simulated using linear, equilibrium sorption (LE), nonlinear, equilibrium sorption (NL), linear, first-order nonequilibrium sorption (LFO), linear, radial diffusion (LRD), and nonlinear, first-order nonequilibrium sorption (NFO) models. The Akaike information criterion was utilized to determine the preferred model. The LE model could not adequately describe phthalate ester (PE) BTCs in higher organic matter soil or for more hydrophobic PEs. The LFO and LRD models adequately described the BTCs but a slight improvement in curve-fitting was gained in some cases when the NFO model was used. However, none of the models could properly describe the desorptive tail of DPP for the high organic matter soil. Transport of DPP through this soil was adequately predicted when degradation or sorption hysteresis was considered. Using the optimized parameter values along with values reported by others it was shown that the organic carbon distribution coefficient (K(oc)) of PEs correlates well with the octanol/water partition coefficient (K(ow)). Also, a strong relationship was found between the first-order sorption rate coefficient normalized to injection pulse size and compound residence time. A similar trend of timescale dependence was found for the rate parameter in the radial diffusion model. Results also revealed that the fraction of instantaneous sorption sites is dependent on K(ow) and appears to decrease with the increase in the sorption rate parameter.     

Effect of soil ageing on in vivo arsenic bioavailability in two dissimilar soils

Arsenic (As) bioavailability in spiked soils aged for up to 12 months was assessed using in vitro and in vivo methodologies. Ageing (natural attenuation) of spiked soils resulted in a decline in in vivo As bioavailability (swine assay) of over 75% in soil A (Red Ferrosol) but had no significant effect on in vivo As bioavailability even after 12 months of ageing in soil B (Brown Chromosol). Sequential fractionation, however, indicated that there was repartitioning of As within the soil fractions extracted during the time course investigated. In soil A, the As fraction associated with the more weakly bound soil fractions decreased while the residual fraction increased from 12% to 35%. In contrast, little repartitioning of As was observed in soil B indicating that natural attenuation may be only applicable for As in soils containing specific mineralogical properties.     

Application of an in vivo swine model for the determination of arsenic bioavailability in contaminated vegetables

Considerable information is available in the literature regarding the uptake of arsenic (As) from contaminated soil and irrigation water by vegetables. However, few studies have investigated As speciation in these crops while a dearth of information is available on As bioavailability following their consumption. In this study, the concentration and speciation of As in chard, radish, lettuce and mung beans was determined following hydroponic growth of the vegetables using As-contaminated water. In addition, As bioavailability was assessed using an in vivo swine feeding assay. While As concentrations ranged from 3.0 to 84.2mg As kg(-1) (dry weight), only inorganic As (arsenite and arsenate) was detected in the edible portions of the vegetables. When As bioavailability was assessed through monitoring blood plasma As concentrations following swine consumption of As-contaminated vegetables, between 50% and 100% of the administered As dose was absorbed and entered systemic circulation. Arsenic bioavailability decreased in the order mung beans>radish>lettuce=chard.