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.     

Sources,distribution, and acidity of sulfate–ammonium aerosol in the Arctic in winter–spring

We use GEOS-Chem chemical transport model simulations of sulfate–ammonium aerosol data from the NASA ARCTAS and NOAA ARCPAC aircraft campaigns in the North American Arctic in April 2008, together with longer-term data from surface sites, to better understand aerosol sources in the Arctic in winter–spring and the implications for aerosol acidity. Arctic pollution is dominated by transport from mid-latitudes, and we test the relevant ammonia and sulfur dioxide emission inventories in the model by comparison with wet deposition flux data over the source continents. We find that a complicated mix of natural and anthropogenic sources with different vertical signatures is responsible for sulfate concentrations in the Arctic. East Asian pollution influence is weak in winter but becomes important in spring through transport in the free troposphere. European influence is important at all altitudes but never dominant. West Asia (non-Arctic Russia and Kazakhstan) is the largest contributor to Arctic sulfate in surface air in winter, reflecting a southward extension of the Arctic front over that region. Ammonium in Arctic spring mostly originates from anthropogenic sources in East Asia and Europe, with added contribution from boreal fires, resulting in a more neutralized aerosol in the free troposphere than at the surface. The ARCTAS and ARCPAC data indicate a median aerosol neutralization fraction [NH₄⁺]/(2[SO₄^2?] + [NO₃^?]) of 0.5 mol mol^?1 below 2 km and 0.7 mol mol^?1 above. We find that East Asian and European aerosol transported to the Arctic is mostly neutralized, whereas West Asian and North American aerosol is highly acidic. Growth of sulfur emissions in West Asia may be responsible for the observed increase in aerosol acidity at Barrow over the past decade. As global sulfur emissions decline over the next decades, increasing aerosol neutralization in the Arctic is expected, potentially accelerating Arctic warming through indirect radiative forcing and feedbacks.     

High-impact conservation: invasive mammal eradications from the islands of western México

Islands harbor a disproportionate amount of the earth's biodiversity, but a significant portion has been lost due in large part to the impacts of invasive mammals. Fortunately, invasive mammals can be routinely removed from islands, providing a powerful tool to prevent extinctions and restore ecosystems. Given that invasive mammals are still present on more than 80% of the world's major islands groups and remain a premier threat to the earth's biodiversity, it is important to disseminate replicable, scaleable models to eradicate invasive mammals from islands. We report on a successful model from western México during the past decade. A collaborative effort between nongovernmental organizations, academic biologists, Mexican government agencies, and local individuals has resulted in major restoration efforts in three island archipelagos. Forty-two populations of invasive mammals have been eradicated from 26 islands. For a cost of USD 21,615 per colony and USD 49,370 per taxon, 201 seabird colonies and 88 endemic terrestrial taxa have been protected, respectively. These conservation successes are a result of an operational model with three main components: i) a tri-national collaboration that integrates research, prioritization, financing, public education, policy work, capacity building, conservation action, monitoring, and evaluation; ii) proactive and dedicated natural resource management agencies; and iii) effective partnerships with academic researchers in Mexico and the United States. What is now needed is a detailed plan to eradicate invasive mammals from the remaining islands in the region that integrates the needed additional financing, capacity, technical advances, and policy issues. Island conservation in western Mexico provides an effective approach that can be readily applied to other archipelagos where conservation efforts have been limited.     

Uphill permeation of Cr(VI) using Hostarex A327 as ionophore by membrane-solvent extraction processing

The transport of chromium by the emulsion pertraction technology (EPERT) using Hostarex A327 (tertiary amine) as a carrier has been investigated. The permeation of the metal is studied as a function of various experimental variables: hydrodynamic conditions, concentration of Cr(VI) and HCl in the source phase, carrier concentration and diluent in the organic phase, strippant concentration in the stripping phase and support characteristics of the membrane. The mass transfer coefficient and the thickness of the aqueous source boundary layer were estimated from the experimental data. Furthermore, the selectivity of the Hostarex A327-bases EPERT towards different metal ions and the behaviour of the system against other carriers are presented.     

Natural attenuation of diesel aliphatic hydrocarbons in contaminated agricultural soil

A diesel fuel spill at a concentration of 1 L m(-2) soil was simulated on a 12 m(2) plot of agricultural land, and natural attenuation of aliphatic hydrocarbons was monitored over a period of 400 days following the spill after which the aliphatic hydrocarbon concentrations were found to be below the legal contamination threshold for soil. The main fraction of these compounds (95%) remained at the surface layer (0-10 cm). Shortly after the spill (viz. between days 0 and 18), evaporation was the main origin of the dramatic decrease in pollutant concentrations in the soil. Thereafter, soil microorganisms used aliphatic hydrocarbons as sources of carbon and energy, as confirmed by the degradation ratios found. Soil quality indicators, soil microbial biomass and dehydrogenase activity, regained their original levels about 200 days after the spill.     

Screening the phytoremediation potential of desert broom (Baccharis sarothroides Gray) growing on mine tailings in Arizona, USA

The metal concentrations in a copper mine tailings and desert broom (Baccharis sarothroides Gray) plants were investigated. The metal concentrations in plants, soil cover, and tailings were determined using ICP-OES. The concentration of copper, lead, molybdenum, chromium, zinc, arsenic, nickel, and cobalt in tailings was 526.4, 207.4, 89.1, 84.5, 51.7, 49.6, 39.7, and 35.6mgkg(-1), respectively. The concentration of all elements in soil cover was 10-15% higher than that of the tailings, except for molybdenum. The concentration of copper, lead, molybdenum, chromium, zinc, arsenic, nickel, and cobalt in roots was 818.3, 151.9, 73.9, 57.1, 40.1, 44.6, 96.8, and 26.7mgkg(-1) and 1214.1, 107.3, 105.8, 105.5, 55.2, 36.9, 30.9, and 10.9mgkg(-1) for shoots, respectively. Considering the translocation factor, enrichment coefficient, and the accumulation factor, desert broom could be a potential hyperaccumulator of Cu, Pb, Cr, Zn, As, and Ni.     

Kinetic studies of endosulfan photochemical degradations by ultraviolet light irradiation in aqueous medium

Kinetic studies of endosulfan photochemical degradation in controlled aqueous systems were carried out by ultraviolet light irradiation at lambda = 254 nm. The photolysis of (alpha + beta: 2 + 1) endosulfan, alpha-endosulfan and beta-endosulfan were first-order kinetics. The observed rate constants obtained from linear least-squares analysis of the data were 1 x 10(-4) s(-1); 1 x 10(-4) s(-1); and 2 x 10(-5) s(-1), respectively, and the calculated quantum yields (phi) were 1, 1 and 1.6, respectively. Preliminary differential pulse polarographic (DPP) analysis allowed to observe the possible endosulfan photochemical degradation pathway. This degradation route involves the formation of the endosulfan diol, its transformation to endosulfan ether and finally the ether's complete degradation by observing the potential shifts.     

Using FTIR to corroborate the identity of functional groups involved in the binding of Cd and Cr to saltbush (Atriplex canescens) biomass

Fourier transform infrared (FTIR) studies were performed to confirm the chemical modification of saltbush (Atriplex canescens) biomass and to provide information about the identity and binding characteristics of the chemical groups responsible for the binding of Cd(II), Cr(III), and Cr(VI). In addition, studies were performed to determine the optimum time for the binding of the three ions by saltbush biomass, and to study the efficiency of HCl and sodium citrate as stripping agents. The metal quantification was performed using inductively coupled plasma optical emission spectroscopy (ICP-OES). The results showed that 10 min or less is enough to achieve the maximum metal binding, and that aqueous solutions of 0.1 mM HCl or sodium citrate were enough to strip more than 80% of the bound Cd. It was determined that more than 70% of the bound Cr(III) was stripped using 0.1 mM HCl. Chemical modification of carboxyl and ester groups on the biomass was performed. The FTIR results confirmed that the esterification of carboxyl groups and hydrolysis of ester groups in the native biomass had occurred. The direct effect of these modifications on the binding properties of the biomass provided strong evidence that the carboxyl functionality is the main group responsible for binding Cd and Cr(III). However, the IR data showed that for Cr(VI), a different type of functional group is involved.