Nitro-PAH formation studied by interacting artificially PAH-coated soot aerosol with NO2 in the temperature range of 295–523 K

Diesel particulate matter poses a threat to human health, and in particular nitrated polycyclic aromatic hydrocarbons (NPAHs) found within and on the surface of these particles. Although diesel particulate filters (DPFs) have been designed and implemented to reduce these and other harmful diesel emissions, the particle loaded filters may act as a reaction chamber for the enhanced production of NPAHs from the nitration of PAHs with NO₂.Focus is on the investigation of the heterogeneous reactions that occur on soot particles by exposing laboratory produced pyrene- or benzo(a)pyrene-coated spark discharge soot particles to varying concentrations of NO₂ and temperatures while following the formation of products over time. The sole nitration product that was observed throughout the experiments with pyrene-coated soot was 1-nitropyrene (1-NPYR), which increased linearly with reaction time for all NO₂ concentrations chosen (0.11, 1.0, 2.0, 4.0 ppm, m m^?1). Resulting 1-NPYR formation rate increased exponentially with [NO₂]. Throughout the 3-h experiments less than 10% of pyrene has been converted to 1-NPYR and the partial reaction order with regard to [NO₂] was estimated to 1.52. Benzo(a)pyrene (BaP) was more reactive than pyrene. After 3 h reaction time almost 80% of the BaP has been converted to 6-NBaP.Highest 1-NPYR concentrations on particles were detected at 373 K, and at higher temperatures a considerable decrease in particulate 1-NPYR was observed. A similar trend was observed in a DPF simulation system (PM-Kat^®-like) with BaP-coated soot. In this case, highest 6-NBaP concentration on particles was detected at 423 K. Backed by corroborating results from separate gas/solid-phase partition experiments with 1-NPYR and 6-NBaP, it is likely that the newly formed 1-NPYR and 6-NBaP became transferred from particle to gas phase at higher temperatures. Results from this study confirm the presence of 1-NPYR and 6-NBaP in particulate and gas phase under conditions encountered in DPFs, especially when operated at low temperature situations of the aftertreatment system.     

Radium and radium-daughter nuclides in carbonates: a brief overview of strategies for determining chronologies

Radium isotopes have been used extensively to trace the movement of groundwater as well as oceanic water masses, but these radionuclides (and their daughters) are also useful chronometers for the determination of the time scales of other Earth and environmental processes. The purpose of this overview is to present the application of Ra and Ra daughters in the dating of carbonates. We show that the choice of dating method (decay of excess radionuclide or ingrowth of daughter) depends strongly on the parent/daughter activity ratios in the water in which the carbonate was precipitated. Thus freshly precipitated carbonates uniformly show excesses of ²²⁶Ra relative to its parent ²³⁰Th, and ²²⁶Ra decay can provide ages of carbonates over Holocene time scales. In contrast, carbonates are precipitated in waters of greatly varying ²¹⁰Pb/²²⁶Ra. Corals, deep-sea hydrothermal vent clams and the shelled cephalopod Nautilus live in waters with significant dissolved ²¹⁰Pb and all show excesses of ²¹⁰Pb in their carbonate. Bivalve molluscs from nearshore and coastal waters, and carbonates deposited from groundwater environments (e.g. travertines) in which ²¹⁰Pb is efficiently scavenged from solution, show deficiencies of ²¹⁰Pb relative to ²²⁶Ra. In contrast, fish otoliths strongly discriminate against ²¹⁰Pb regardless of the environment in which the fish lives. Deficiencies of ²²⁸Th relative to ²²⁸Ra are common in all carbonates. Useful time ranges for the ²¹⁰Pb/²²⁶Ra and ²²⁸Th/²²⁸Ra chronometers are ∼100 y and ∼10 y, respectively.     

Exposure to moderate concentrations of tropospheric ozone impairs tree stomatal response to carbon dioxide

With rising concentrations of both atmospheric carbon dioxide (CO₂) and tropospheric ozone (O₃), it is important to better understand the interacting effects of these two trace gases on plant physiology affecting land-atmosphere gas exchange. We investigated the effect of growth under elevated CO₂ and O₃, singly and in combination, on the primary short-term stomatal response to CO₂ concentration in paper birch at the Aspen FACE experiment. Leaves from trees grown in elevated CO₂ and/or O₃ exhibited weaker short-term responses of stomatal conductance to both an increase and a decrease in CO₂ concentration from current ambient level. The impairement of the stomatal CO₂ response by O₃ most likely developed progressively over the growing season as assessed by sap flux measurements. Our results suggest that expectations of plant water-savings and reduced stomatal air pollution uptake under rising atmospheric CO₂ may not hold for northern hardwood forests under concurrently rising tropospheric O₃.     

Vertical migration of radionuclides in undisturbed grassland soils

Literature data on numerical values obtained for the parameters of the two most popular models for simulating the migration of radionuclides in undisturbed soils have been compiled and evaluated statistically. Due to restrictions on the applicability of compartmental models, the convection–dispersion equation and its parameter values should be preferred. For radiocaesium, recommended values are derived for its effective convection velocity and dispersion coefficient. Data deficiencies still exist for radionuclides other than caesium and for soils of non-temperate environments.     

Liquid household hazardous wastes in the United States: Identification,disposal, and management plan

Present methods of disposal of today's hazardous household chemicals in the United States are frequently not acceptable because of pathways to groundwater, surface water, and the atmosphere. This report identifies potentially hazardous liquid waste in the household, notes current disposal practices, and recommends an improved management plan that utilizes consumer education, manufacturer cooperation, and governmental intervention. Laws requiring uniform disposal labeling on packaging are critical. Local, county, and state governments must be encouraged to coordinate the necessary infrastructure. Managing hazardous household wastes now will mitigate potential disposal problems.     

Simulating urban waste compost effects on carbon and nitrogen dynamics using a biochemical index

Composting has emerged as a valuable route for the disposal of urban waste, with the prospect of applying composts on arable fields as organic amendments. Proper management of urban waste composts (UWCs) requires a capacity to predict their effects on carbon and nitrogen dynamics in the field, an issue in which simulation models are expected to play a prominent role. However, the parameterization of soil organic amendments within such models generally requires laboratory incubation data. Here, we evaluated the benefit of using a biochemical index based on Van Soest organic matter fractions to parameterize a deterministic model of soil C and N dynamics, NCSOIL, as compared with a standard alternative based on laboratory incubation data. The data included C mineralization and inorganic N dynamics in samples of a silt loam soil (Typic Hapludalf) mixed with various types of UWC and farmyard manure. NCSOIL successfully predicted the various nitrogen mineralization-immobilization patterns observed, but underestimated CO(2) release by 10 to 30% with the less stable amendments. The parameterization based on the biochemical index achieved a prediction error significantly larger than the standard parameterization in only 10% of the tested cases, and provided an acceptable fit to experimental data. The decomposition rates and C to N ratios of compost organic matter varied chiefly according to the type of waste processed. However, 62 to 66% of their variance could be explained by the biochemical index. We thus suggest using the latter to parameterize organic amendments in C and N models as a substitute for time-consuming laboratory incubations.     

Preliminary ecotoxicological characterization of a new energetic substance, CL-20

A new energetic substance hexanitrohexaazaisowurtzitane (or CL-20) was tested for its toxicities to various ecological receptors. CL-20 (epsilon-polymorph) was amended to soil or deionized water to construct concentration gradients. Results of Microtox (15-min contact) and 96-h algae growth inhibition tests indicate that CL-20 showed no adverse effects on the bioluminescence of marine bacteria Vibrio fischeri and the cell density of freshwater green algae Selenastrum capricornutum respectively, up to its water solubility (ca. 3.6 mg l(-1)). CL-20 and its possible biotransformation products did not inhibit seed germination and early seedling (16-19 d) growth of alfalfa (Medicago sativa) and perennial ryegrass (Lolium perenne) up to 10,000 mg kg(-1) in a Sassafras sandy loam soil (SSL). Indigenous soil microorganisms in SSL and a garden soil were exposed to CL-20 for one or two weeks before dehydrogenase activity (DHA) or potential nitrification activity (PNA) were assayed. Results indicate that up to 10,000 mg kg(-1) soil of CL-20 had no statistically significant effects on microbial communities measured as DHA or on the ammonium oxidizing bacteria determined as PNA in both soils. Data indicates that CL-20 was not acutely toxic to the species or microbial communities tested and that further studies are required to address the potential long-term environmental impact of CL-20 and its possible degradation products.     

Importance of colloids in the transport within the dissolved phase (<450 nm) of artificial radionuclides from the Rhône river towards the Gulf of Lions (Mediterranean Sea)

The significance of colloidal fractions regarding the transport of artificial radionuclides in natural water systems is underlined by using sequential ultrafiltration both in the Rh?ne freshwater and the marine area under and outside the influence of the river outflow. Indeed, the Rhodanian aquatic system represents an interesting test site as various artificial radionuclides are released into the Rh?ne river by several nuclear installations. We focused our study on (137)Cs, (106)Ru, (60)Co, (238)Pu and (239+240)Pu. Our results show that Fe, Al and Organic carbon (OC) are the main components of colloidal matter. Colloids represent about 15% of dissolved (<450 nm) OC and 25% of dissolved Fe and Al exported towards the sea. Within the dissolved (< 450 nm) phase, these colloidal compounds are shown to account for the transport of 40% for both Co and Ru, 60% for (238)Pu and (239+240)Pu and have no significance on (137)Cs flux.     

New and versatile optical-immunoassay instrumentation for water monitoring

This article is a review of new and versatile optical-immunoassay instrumentation for water monitoring developed through two European Union projects, RIver ANAlyser (RIANA) and Automated Water Analyser Computer Supported System (AWACSS). Both projects utilise immunoassay techniques to isolate the analytes and Total Internal Reflection Fluorescence (TIRF) to quantify them. Completed in 1999, the RIANA project developed a sensitive and cost-effective analytical system capable of simultaneous detection of multiple-analytes in real-world water samples. The AWACSS project has been in progress since 2001 and is developing rugged-but-sensitive instrumentation that will detect up to 30 analytes simultaneously, will operate unattended, and will have networking capability.