Using deuterated PAH amendments to validate chemical extraction methods to predict PAH bioavailability in soils

Validating chemical methods to predict bioavailable fractions of polycyclic aromatic hydrocarbons (PAHs) by comparison with accumulation bioassays is problematic. Concentrations accumulated in soil organisms not only depend on the bioavailable fraction but also on contaminant properties. A historically contaminated soil was freshly spiked with deuterated PAHs (dPAHs). dPAHs have a similar fate to their respective undeuterated analogues, so chemical methods that give good indications of bioavailability should extract the fresh more readily available dPAHs and historic more recalcitrant PAHs in similar proportions to those in which they are accumulated in the tissues of test organisms. Cyclodextrin and butanol extractions predicted the bioavailable fraction for earthworms (Eisenia fetida) and plants (Lolium multiflorum) better than the exhaustive extraction. The PAHs accumulated by earthworms had a larger dPAH:PAH ratio than that predicted by chemical methods. The isotope ratio method described here provides an effective way of evaluating other chemical methods to predict bioavailability.     

Emission reductions from woody biomass waste for energy as an alternative to open burning

Woody biomass waste is generated throughout California from forest management, hazardous fuel reduction, and agricultural operations. Open pile burning in the vicinity of generation is frequently the only economic disposal option. A framework is developed to quantify air emissions reductions for projects that alternatively utilize biomass waste as fuel for energy production. A demonstration project was conducted involving the grinding and 97-km one-way transport of 6096 bone-dry metric tons (BDT) of mixed conifer forest slash in the Sierra Nevada foothills for use as fuel in a biomass power cogeneration facility. Compared with the traditional open pile burning method of disposal for the forest harvest slash, utilization of the slash for fuel reduced particulate matter (PM) emissions by 98% (6 kg PM/BDT biomass), nitrogen oxides (NOx) by 54% (1.6 kg NOx/BDT), nonmethane volatile organics (NMOCs) by 99% (4.7 kg NMOCs/BDT), carbon monoxide (CO) by 97% (58 kg CO/BDT), and carbon dioxide equivalents (CO2e) by 17% (0.38 t CO2e/BDT). Emission contributions from biomass processing and transport operations are negligible. CO2e benefits are dependent on the emission characteristics of the displaced marginal electricity supply. Monetization of emissions reductions will assist with fuel sourcing activities and the conduct of biomass energy projects.     

Aquivalence revisited--new model formulation and application to assess environmental fate of ionic pharmaceuticals in Hamilton Harbour, Lake Ontario

A model formulation based on "aquivalence", as defined in terms of activity is presented to estimate the multimedia fate of ionizing chemicals. The aquivalence approach is analogous to fugacity but aquivalence is applicable to neutral and ionizing compounds, and has been applied previously to speciating chemicals, notably metals. The new aquivalence-based mass-balance model treats ionizing organic compounds that exist as interconverting neutral and ionic species which are subject to fate processes at differing rates. The model is illustrated by application to four ionizing pharmaceuticals in Hamilton Harbour, Lake Ontario. At the system pH of 7.9-8.5, ibuprofen, gemfibrozil, and naproxen are expected to be almost entirely ionic and triclosan split between ionic and neutral forms. Measured seasonal surface water concentrations, which were 2-10 times lower in the late summer and fall than during spring, were used to solve for unknown values of chemical half-life in the water column due to degradation (photo- and bio-) of the ionizing and neutral forms and secondarily, ionic sorption coefficients of the ionizing forms. Model estimates of half-lives in the habour's water ranged from 11 to 77, 11 to 147 and 10 to 37 for ionic ibuprofen, gemfibrozil, and naproxen, respectively; and 4-22 days and 2-9 days for ionic and neutral triclosan, respectively, with the shortest half-lives in spring and the longest in summer.     

Fish Migration, Dams, and Loss of Ecosystem Services in the Mekong Basin

The past decade has seen increased international recognition of the importance of the services provided by natural ecosystems. It is unclear however whether such international awareness will lead to improved environmental management in many regions. We explore this issue by examining the specific case of fish migration and dams on the Mekong river. We determine that dams on the Mekong mainstem and major tributaries will have a major impact on the basin’s fisheries and the people who depend upon them for food and income. We find no evidence that current moves towards dam construction will stop, and consider two scenarios for the future of the fisheries and other ecosystems of the basin. We conclude that major investment is required in innovative technology to reduce the loss of ecosystem services, and alternative livelihood strategies to cope with the losses that do occur.     

When does nitrate become a risk for humans?

Is nitrate harmful to humans? Are the current limits for nitrate concentration in drinking water justified by science? There is substantial disagreement among scientists over the interpretation of evidence on the issue. There are two main health issues: the linkage between nitrate and (i) infant methaemoglobinaemia, also known as blue baby syndrome, and (ii) cancers of the digestive tract. The evidence for nitrate as a cause of these serious diseases remains controversial. On one hand there is evidence that shows there is no clear association between nitrate in drinking water and the two main health issues with which it has been linked, and there is even evidence emerging of a possible benefit of nitrate in cardiovascular health. There is also evidence of nitrate intake giving protection against infections such as gastroenteritis. Some scientists suggest that there is sufficient evidence for increasing the permitted concentration of nitrate in drinking water without increasing risks to human health. However, subgroups within a population may be more susceptible than others to the adverse health effects of nitrate. Moreover, individuals with increased rates of endogenous formation of carcinogenic N-nitroso compounds are likely to be susceptible to the development of cancers in the digestive system. Given the lack of consensus, there is an urgent need for a comprehensive, independent study to determine whether the current nitrate limit for drinking water is scientifically justified or whether it could safely be raised.     

Changes in persistent contaminant concentration and CYP1A1 protein expression in biopsy samples from northern bottlenose whales, Hyperoodon ampullatus, following the onset of nearby oil and gas development

A small population of endangered northern bottlenose whales (Hyperoodon ampullatus) inhabits "The Gully" a Marine Protected Area on the Scotian Shelf, eastern Canada. Amid concerns regarding nearby oil and gas development, we took 36 skin and blubber biopsy samples in 1996-1997 (prior to major development) and 2002-2003 (five years after development began), and three samples from a population in the Davis Strait, Labrador in 2003. These were analysed for cytochrome P4501A1 (CYP1A1) protein expression (n=36), and for persistent contaminants (n=23). CYP1A1 showed generally low expression in whales from The Gully, but higher levels during 2003, potentially coincident with recorded oil spills, and higher levels in Davis Strait whales. A range of PCB congeners and organochlorine compounds were detected, with concentrations similar to other North Atlantic odontocetes. Concentrations were higher in whales from The Gully than from the Davis Strait, with significant increases in 4,4'-DDE and trans-nonachlor in 2002-2003 relative to 1996-1997.     

Seasonal and diurnal gas exchange differences in ozone-sensitive common milkweed (Asclepias syriaca L.) in relation to ozone uptake

Stomatal conductance and net photosynthesis of common milkweed (Asclepias syriaca L.) plants in two different soil moisture regimes were directly quantified and subsequently modeled over an entire growing season. Direct measurements captured the dynamic response of stomatal conductance to changing environmental conditions throughout the day, as well as declining gas exchange and carbon assimilation throughout the growth period beyond an early summer maximum. This phenomenon was observed in plants grown both with and without supplemental soil moisture, the latter of which should theoretically mitigate against harmful physiological effects caused by exposure to ozone. Seasonally declining rates of stomatal conductance were found to be substantial and incorporated into models, making them less susceptible to the overestimations of effective exposure that are an inherent source of error in ozone exposure indices. The species-specific evidence presented here supports the integration of dynamic physiological processes into flux-based modeling approaches for the prediction of ozone injury in vegetation.     

Patterns and sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in surficial sediments of Lakes Erie and Ontario

This study determines spatial trends and congener patterns of 2378-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in surficial sediments of Lakes Erie and Ontario. Sediments are enriched in 2378-PCDFs in Lake Ontario, and the PCDD/F concentrations increased from shallow near-shore sediments towards deep-water depositional zone sediments. In Lake Erie, sediments were dominated by octachlorodibenzo-p-dioxin, and the highest PCDD/F concentrations were observed in the western basin and the southern shoreline of the central basin with a decrease towards the eastern basin and the northern shoreline of the central basin. Principal components analysis revealed that chemical manufacture and disposal of chemical waste along the Niagara River has been a major PCDD/F source to Lake Ontario; while PCDD/Fs in Lake Erie are from multiple sources including industrial sources along the Detroit River, major tributaries along the southern shoreline of the lake, and atmospherically-derived material from the upper lakes and connecting channels.     

Managing Baltic Sea fisheries under contrasting production and predation regimes: ecosystem model analyses

Based on an earlier published ecosystem model, we have explored possible effects of different management scenarios for the Baltic Sea. The scenarios include an oligotrophication of the system, a drastic increase in the number of seals, and changes in the fishery management. From these simulations we conclude that fisheries, seals, and eutrophication all have strong and interacting impacts on the ecosystem. These interactions call for integrated management. The modeling highlights the potential for conflicts among management mandates such as flourishing fisheries, rebuilt seal populations, and substantially reduced eutrophication. The results also suggest that fisheries management reference points have to be adjusted in response to changes in the presence of natural predators or ecosystem productivity.