The influence of cosolvent and heat on the solubility and reactivity of organophosphorous pesticide DNAPL alkaline hydrolysis

The presented research concerned the compatibility of cosolvents with in situ alkaline hydrolysis (ISAH) for treatment of organophosphorous (OPP) pesticide contaminated sites. In addition, the influence of moderate temperature heat increments was studied as a possible enhancement method. A complex dense non-aqueous phase liquid (DNAPL) of primarily parathion (~50 %) and methyl parathion (~15 %) obtained from the Danish Groyne 42 site was used as a contaminant source, and ethanol and propan-2-ol (0, 25, and 50 v/v%) was used as cosolvents in tap water and 0.34 M NaOH. Both cosolvents showed OPP solubility enhancement at 50 v/v% cosolvent content, with slightly higher OPP concentrations reached with propan-2-ol. Data on hydrolysis products did not show a clear trend with respect to alkaline hydrolysis reactivity in the presence of cosolvents. Results indicated that the hydrolysis rate of methyl-parathion (MP3) decreased with addition of cosolvent, whereas the hydrolysis rate of ethyl-parathion (EP3) remained constant, and overall indications were that the hydrolysis reactions were limited by the rate of hydrolysis rather than NAPL dissolution. In addition to cosolvents, the influence of low-temperature heating on ISAH was studied. Increasing reaction temperature from 10 to 30 °C provided an average rate of hydrolysis enhancement by a factor of 1.4–4.8 dependent on the base of calculation. When combining 50 v/v% cosolvent addition and heating to 30 °C, EP3 solubility was significantly enhanced and results for O,O-diethyl-thiophosphoric acid (EP2 acid) showed a significant enhancement of hydrolysis as well. However, this could not be supported by para-nitrophenol (PNP) data indicating the instability of this product in the presence of cosolvent.

     

Ambient measurements of 2,2,4-trimethyl, 1,3-pentanediol monoisobutyrate in Southern California

2,2,4-trimethyl, 1,3-pentanediol monoisobutyrate (TPM) is a widely used solvent found in water-based coatings. Ambient measurements of TPM are reported here for the first time. Although this compound has been previously measured in indoor air, this study illustrates successful detection and quantification of TPM in ambient air at three locations in Southern California: Pico Rivera, Azusa, and Riverside. TPM was detected in every sample collected, with concentrations ranging from 0.7 to 49.5 parts per trillion (ppt). Collections took place during summer 2009, fall 2009, winter 2009/2010, and spring 2010, for 5-7 days during each season. The highest mean concentrations were observed during the summer months for each city, when coating activities are typically at their highest.     

Influence of flooding and metal immobilising soil amendments on availability of metals for willows and earthworms in calcareous dredged sediment-derived soils

Soil amendments previously shown to be effective in reducing metal bioavailability and/or mobility in calcareous metal-polluted soils were tested on a calcareous dredged sediment-derived soil with 26 mg Cd/kg dry soil, 2200 mg Cr/kg dry soil, 220 mg Pb/kg dry soil, and 3000 mg Zn/kg dry soil. The amendments were 5% modified aluminosilicate (AS), 10% w/w lignin, 1% w/w diammonium phosphate (DAP, (NH₄)₂HPO₄), 1% w/w MnO, and 5% w/w CaSO₄. In an additional treatment, the contaminated soil was submerged. Endpoints were metal uptake in Salix cinerea and Lumbricus terrestris, and effect on oxidation-reduction potential (ORP) in submerged soils. Results illustrated that the selected soil amendments were not effective in reducing ecological risk to vegetation or soil inhabiting invertebrates, as metal uptake in willows and earthworms did not significantly decrease following their application. Flooding the polluted soil resulted in metal uptake in S. cinerea comparable with concentrations for an uncontaminated soil.     

Characterizing the Relative Contributions of Large Vessels to Total Ocean Noise Fields: A Case Study Using the Gerry E. Studds Stellwagen Bank National Marine Sanctuary

In 2006, we used the U.S. Coast Guard’s Automatic Identification System (AIS) to describe patterns of large commercial ship traffic within a U.S. National Marine Sanctuary located off the coast of Massachusetts. We found that 541 large commercial vessels transited the greater sanctuary 3413 times during the year. Cargo ships, tankers, and tug/tows constituted 78% of the vessels and 82% of the total transits. Cargo ships, tankers, and cruise ships predominantly used the designated Boston Traffic Separation Scheme, while tug/tow traffic was concentrated in the western and northern portions of the sanctuary. We combined AIS data with low-frequency acoustic data from an array of nine autonomous recording units analyzed for 2 months in 2006. Analysis of received sound levels (10–1000 Hz, root-mean-square pressure re 1 μPa ± SE) averaged 119.5 ± 0.3 dB at high-traffic locations. High-traffic locations experienced double the acoustic power of less trafficked locations for the majority of the time period analyzed. Average source level estimates (71–141 Hz, root-mean-square pressure re 1 μPa ± SE) for individual vessels ranged from 158 ± 2 dB (research vessel) to 186 ± 2 dB (oil tanker). Tankers were estimated to contribute 2 times more acoustic power to the region than cargo ships, and more than 100 times more than research vessels. Our results indicate that noise produced by large commercial vessels was at levels and within frequencies that warrant concern among managers regarding the ability of endangered whales to maintain acoustic contact within greater sanctuary waters. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Incentives for low-input land-use types and their influence on the attractiveness of landscapes

Changes in agricultural policy have traceable effects on landscape aesthetics. For the catchment area of Lake Greifensee, an economic land-use model predicted land-use changes caused by agricultural policy. Three scenarios implementing different direct payment schemes show that land-use intensity will decrease by 2011 compared with the ‘reference status’ 2000.The output of the economic land-use model is explicit in space. It was assessed by the ‘naturalness’ perception factor of the method proposed by Hoisl et al. [1989. Landschaftsästhetik in der Flurbereinigung. Materialien zur Flurbereinigung—Heft 17. Bayerisches Staatsministerium für Ernährung, Landwirtschaft und Forsten, München] with regard to landscape aesthetics. Even though lower land-use intensity is generally predicted by 2011, the values of the ‘naturalness’ perception factor do not significantly improve if the payment scheme remains unchanged, or if the payment scheme is amended by incentives for specific location of the ecological compensation areas (ECAs). A significant reduction in the values of the ‘naturalness’ perception factor was found when subsidies for ECA's were cancelled. This leads us to the conclusion that in order to keep Swiss landscapes as attractive as they are at present, policy must sustain incentives for low-intensity land-use types.     

Biochar: a synthesis of its agronomic impact beyond carbon sequestration

Biochar has been heralded as an amendment to revitalize degraded soils, improve soil carbon sequestration, increase agronomic productivity, and enter into future carbon trading markets. However, scientific and economic technicalties may limit the ability of biochar to consistently deliver on these expectations. Past research has demonstrated that biochar is part of the black carbon continuum with variable properties due to the net result of production (e.g., feedstock and pyrolysis conditions) and postproduction factors (storage or activation). Therefore, biochar is not a single entity but rather spans a wide range of black carbon forms. Biochar is black carbon, but not all black carbon is biochar. Agronomic benefits arising from biochar additions to degraded soils have been emphasized, but negligible and negative agronomic effects have also been reported. Fifty percent of the reviewed studies reported yield increases after black carbon or biochar additions, with the remainder of the studies reporting alarming decreases to no significant differences. Hardwood biochar (black carbon) produced by traditional methods (kilns or soil pits) possessed the most consistent yield increases when added to soils. The universality of this conclusion requires further evaluation due to the highly skewed feedstock preferences within existing studies. With global population expanding while the amount of arable land remains limited, restoring soil quality to nonproductive soils could be key to meeting future global food production, food security, and energy supplies; biochar may play a role in this endeavor. Biochar economics are often marginally viable and are tightly tied to the assumed duration of agronomic benefits. Further research is needed to determine the conditions under which biochar can provide economic and agronomic benefits and to elucidate the fundamental mechanisms responsible for these benefits.     

Effects of uncertainty and variability on population declines and IUCN Red List classifications

The International Union for Conservation of Nature (IUCN) Red List Categories and Criteria is a quantitative framework for classifying species according to extinction risk. Population models may be used to estimate extinction risk or population declines. Uncertainty and variability arise in threat classifications through measurement and process error in empirical data and uncertainty in the models used to estimate extinction risk and population declines. Furthermore, species traits are known to affect extinction risk. We investigated the effects of measurement and process error, model type, population growth rate, and age at first reproduction on the reliability of risk classifications based on projected population declines on IUCN Red List classifications. We used an age‐structured population model to simulate true population trajectories with different growth rates, reproductive ages and levels of variation, and subjected them to measurement error. We evaluated the ability of scalar and matrix models parameterized with these simulated time series to accurately capture the IUCN Red List classification generated with true population declines. Under all levels of measurement error tested and low process error, classifications were reasonably accurate; scalar and matrix models yielded roughly the same rate of misclassifications, but the distribution of errors differed; matrix models led to greater overestimation of extinction risk than underestimations; process error tended to contribute to misclassifications to a greater extent than measurement error; and more misclassifications occurred for fast, rather than slow, life histories. These results indicate that classifications of highly threatened taxa (i.e., taxa with low growth rates) under criterion A are more likely to be reliable than for less threatened taxa when assessed with population models. Greater scrutiny needs to be placed on data used to parameterize population models for species with high growth rates, particularly when available evidence indicates a potential transition to higher risk categories.     

Carbon Monoxide Levels in Athletes during Exercise in an Urban Environment

ABSTRACT

Gas phase concentrations of individual polycyclic aromatic hydrocarbons (PAHs) were measured in real time in combustion products from a co-flow diffusion flame using laser photoionization (LP) time-of-flight mass spectrometry (TOF/MS). In particular, a naphthalene detection sensitivity of 4 parts per billion (ppb) was demonstrated. The use of calibration mixtures with argon indicated the feasibility of naphthalene detection at about 45 parts per trillion (ppt) at a signal-to-noise (S/N) ratio of 20. This suggests the possibility of low-ppt level detection at a S/N of 1. The novelty of the system is the use of a heated sampling probe and a continuously purged, heated-pulse valve that was positioned close to the ionization zone, thereby allowing the generation of photoions in the high-density region of the sample jet, where concentrations of PAH are high. Because the system developed allows for the real time detection of select species, it represents a useful tool in continuous emissions monitoring (CEM) for environmental compliance as well as direct process control.