Comparative study of degradation of toluene and methyl isobutyl ketone (MIBK) in aqueous solution by pulsed corona discharge plasma

Effectiveness of pulsed power plasma for the degradation of two toxic volatile organic compounds (VOCs), toluene and methyl isobutyl ketone (MIBK), in aqueous solution was evaluated. The plasma degradation of MIBK has been studied for the first time. The influence of initial concentration of target compound, solution pH and scavengers on percentage degradation was evaluated. 100% removal of 200 mg/L of toluene and MIBK was achieved both in liquid and gaseous phases after 12 and 16 min of plasma treatment, respectively. The first order rate constant of toluene and MIBK degradation (for 200 mg/L each) was 0.421 and 0.319 min^?1 respectively when they were treated individually, and these values decreased slightly during degradation of their mixture. MIBK degradation was slower than toluene and it might be due to semi volatile and hydrophilic nature of MIBK. The effect of initial concentration of toluene and MIBK showed different degradation patterns. Highest degradation of both the compounds was obtained in neutral pH and in absence of scavengers. ?OH radical was the major reactive species involved in their degradation. Their degradation in real environmental matrices showed that removal reduced significantly in secondary effluent due to scavenging of reactive species by various ions and organic matter. The total number of degradation intermediates identified in case of toluene and MIBK was 11 and 14 respectively and formate was the one recalcitrant byproduct generated. The degradation pathway of toluene and MIBK involving reactions of reactive oxygen and nitrogen species and reductive species is proposed.     

Carbon, nitrogen balances and greenhouse gas emission during cattle feedlot manure composting

Carbon and N losses reduce the agronomic value of compost and contribute to greenhouse gas (GHG) emissions. This study investigated GHG emissions during composting of straw-bedded manure (SBM) and wood chip-bedded manure (WBM). For SBM, dry matter (DM) loss was 301 kg Mg(-1), total carbon (TC) loss was 174 kg Mg(-1), and total nitrogen (TN) loss was 8.3 kg Mg(-1). These correspond to 30.1% of initial DM, 52.8% of initial TC, and 41.6% of initial TN. For WBM, DM loss was 268 kg Mg(-1), TC loss was 154 kg Mg(-1), and TN loss was 1.40 kg Mg(-1), corresponding to 26.5, 34.5, and 11.8% of initial amounts. Most C was lost as CO2 with CH4 accounting for <6%. However, the net contribution to greenhouse gas emissions was greater for CH4 since it is 21 times more effective at trapping heat than CO2. Nitrous oxide (N2O) emissions were 0.077 kg N Mg(-1) for SBM and 0.084 kg N Mg(-1) for WBM, accounting for 1 to 6% of total N loss. Total GHG emissions as CO2-C equivalent were not significantly different between SBM (368.4 +/- 18.5 kg Mg(-1)) and WBM (349.2 +/- 24.3 kg Mg(-1)). However, emission of 368.4 kg C Mg(-1) (CO2-C equivalent) was greater than the initial TC content (330.5 kg Mg(-1)) of SBM, raising the question of the net benefits of composting on C sequestration. Further study is needed to evaluate the impact of composting on overall GHG emissions and C sequestration and to fully investigate livestock manure management options.     

Study of individual reactions of the sour compression process for the purification of oxyfuel-derived CO2

Following the feasibility study of sour compression process as a novel purification method of producing NO_x-free, SO₂-free oxyfuel-derived CO₂ using actual fluegas, in this paper, we present the study of the individual reactions taking place in the process in a controlled environment. We have previously showed that an increase of NO/NO₂ concentration in the inlet stream is beneficial for SO₂ removal as NO₂ promotes SO₂ oxidation and the further removal as liquid acid. In this study we show that the reaction SO₂ + NO₂ → SO₃ + NO does not take place significantly in the absence of liquid water at a range of conditions relevant to the sour compression process. When liquid water is present, SO₂ is oxidised by NO₂ regenerating NO with the rate of conversion of SO₂ being dependent on the acid concentration in the liquid. The formation of small liquid droplets where very low levels of pH (?0) can be reached is shown to be of great importance to the SO₂ + NO₂ conversion process.     

Woody biomass phytoremediation of contaminated brownfield land

Economic and environmental regeneration of post-industrial landscapes frequently involves some element of re-afforestation or tree planting. We report field trials that evaluate whether woody biomass production is compatible with managing residual trace element contamination in brownfield soils. Large-scale mapping of contamination showed a heterogenous dispersion of metals and arsenic, and highly localised within-site hotspots. Yields of Salix, Populus and Alnus were economically viable, showing that short-rotation coppice has a potentially valuable role in community forestry. Mass balance modelling demonstrated that phytoextraction potentially could reduce contamination hotspots of more mobile elements (Cd and Zn) within a 25-30-year life cycle of the crops. Cd and Zn in stems and foliage of Salix were 4-13 times higher than EDTA-extractable soil concentrations. Lability of other trace elements (As, Pb, Cu, Ni) was not increased 3 years after planting the coppice; woody biomass may provide an effective reduction of exposure (phyto-stabilization) to these less mobile contaminants.     

Adsorption and desorption characteristics of hydrophobic pesticide endosulfan in four Indian soils

Adsorption and desorption characteristics of endosulfan in four Indian soils were studied extensively. The soils used were clayey soil (CL--lean clay with sand), red soil (GM--silty gravel with sand), sandy soil (SM--silty sand with gravel) and composted soil (PT--peat) as per ASTM (American Society for Testing and Materials) standards. Adsorption and desorption rates were calculated from kinetic studies. These values varied for alpha and beta endosulfan depending on the soil type. Maximum specific adsorption capacities (qmax) for different soils were calculated by Langmuir model. The values varied from 0.1 to 0.45 mg g(-1) for alpha endosulfan and 0.0942-0.2722 mg g(-1) for beta endosulfan. Maximum adsorption took place in clay soil followed by composted soil and red soil. Adsorptions of alpha and beta endosulfan were negligible in sand. The binding characteristics of various functional groups were calculated using Scatchard plot. Effect of functional groups was more predominant in clayey soil. Organic matter also played a significant role in adsorption and desorption of endosulfan. Endosulfan adsorption decreased drastically in clay soil when the pH was reduced. Desorption was higher at both acidic and alkaline pH ranges compared to neutral pH. Results indicated that alpha endosulfan is more mobile compared to beta endosulfan and mobility of endosulfan is maximum in sandy soil followed by red soil. It can be inferred that crystal lattice of the clay soil plays a significant role in endosulfan adsorption and desorption. Immobilization of endosulfan is more advisable in clay soil whereas biological and or chemical process can be applied effectively for the remediation of other soil types.     

Inbreeding Depression in the Speke's Gazelle Captive Breeding Program

Abstract: The Speke's gazelle ( Gazella spekei ) captive breeding program has been presented as one of the few examples of selection reducing the genetic load of a population and as a potential model for the captive breeding of endangered species founded from a small number of individuals. In this breeding program, three generations of mate selection apparently increased the viability of inbred individuals. We reanalyzed the Speke's gazelle studbook and examined potential causes for the reduction of inbreeding depression. Our analysis indicates that the decrease in inbreeding depression is not consistent with any model of genetic improvement in the herd. Instead, we found that the effect of inbreeding decreased from severe to moderate during the first generation of inbreeding, and that this change is responsible for almost all of the decline in inbreeding depression observed during the breeding program. This eliminates selection as a potential explanation for the decrease in inbreeding depression and suggests that inbreeding depression may be more sensitive to environmental influences than is usually thought.     

Determination of commonly used polar herbicides in agricultural drainage waters in Australia by HPLC

The present study describes the application of different extraction techniques for the preconcentration of ten commonly found acidic and non-acidic polar herbicides (2,4-D, atrazine, bensulfuron-methyl, clomazone, dicamba, diuron, MCPA, metolachlor, simazine and triclopyr) in the aqueous environment. Liquid-liquid extraction (LLE) with dichloromethane, solid-phase extraction (SPE) using Oasis HLB cartridges or SBD-XC Empore disks were compared for extraction efficiency of these herbicides in different matrices, especially water samples from contaminated agricultural drainage water containing high concentrations of particulate matter. Herbicides were separated and quantified by high performance liquid chromatography (HPLC) with an ultraviolet detector. SPE using SDB-XC Empore disks was applied to determine target herbicides in the Murrumbidgee Irrigation Area (NSW, Australia) during a two-week survey from October 2005 to November 2005. The daily aqueous concentrations of herbicides from 24-h composite samples detected at two sites increased after run-off from a storm event and were in the range of: 0.1-17.8 microg l(-1), < 0.1-0.9 microg l(-1) and 0.2-17.8 microg l(-1) at site 1; < 0.1-3.5 microg l(-1), < 0.1-0.2 microg l(-1) and < 0.2-3.2 microg l(-1) at site 2 for simazine, atrazine and diuron, respectively.     

Using spatially explicit,time-dependent analysis to understand how social factors influence conservation outcomes

Conservation across human-dominated landscapes requires an understanding of the social and ecological factors driving outcomes. Studies that link conservation outcomes to social and ecological factors have examined temporally static patterns. However, there may be different social and ecological processes driving increases and decreases in conservation outcomes that can only be revealed through temporal analyses. Through a case study of the invasion of Falcataria moluccana in Hawaii, we examined the association of social factors with increases and decreases in invader distributions over time and space. Over 7 years, rates of invader decrease varied substantially (66–100%) relative to social factors, such as building value, whether land was privately or publically owned, and primary residence by a homeowner, whereas rates of increase varied only slightly (<0.1–3.6%) relative to such factors. These findings suggest that links between social factors and invasion in the study system may be driven more by landowners controlling existing invasive species, rather than by landowners preventing the spread of invasive species. We suggest that spatially explicit, time-dependent analyses provide a more nuanced understanding of the way social factors influence conservation outcomes. Such an understanding can help managers develop outreach programs and policies targeted at different types of landowners in human-dominated landscapes.     

Borehole‐scale testing of matrix diffusion for contaminated‐rock aquifers

A new method was developed to assess the effect of matrix diffusion on contaminant transport and remediation of groundwater in fractured rock. This method utilizes monitoring wells constructed of open boreholes in the fractured rock to conduct backward diffusion experiments on chlorinated volatile organic compounds (CVOCs) in groundwater. The experiments are performed on relatively unfractured zones (called test zones) of the open boreholes over short intervals (approximately 1 meter) by physical isolation using straddle packers. The test zones were identified with a combination of borehole geophysical logging and chemical profiling of CVOCs with passive samplers in the open boreholes. To confirm the test zones are within inactive flow zones, they are subjected to a series of hydraulic tests. Afterward, the test zones are air sparged with argon to volatilize the CVOCs from aqueous to air phase. Backward diffusion is then measured by periodic passive‐sampling of water in the test zone to identify rebound. The passive (nonhydraulically stressed) sampling negates the need to extract water and potentially dewater the test zone. The authors also monitor active flowing zones of the borehole to assess trends in concentrations in other parts of the fractured rock by purge and passive sampling methods. The testing was performed at the former Pease Air Force Base (PAFB) in Portsmouth, New Hampshire. Bedrock at the former PAFB consists of fractured metasedimentary rocks where the authors investigated back diffusion of cis‐1,2‐dichloroethylene (cis‐1,2‐DCE), a CVOC. Postsparging concentrations of cis‐1,2‐DCE showed initial rebounding followed by declines, excluding an episodic spike in concentrations from a groundwater recharge event. The authors theorize that there are three processes that controlled concentration responses in the test zones postsparging. First, the limited back diffusion of CVOCs from a halo or thin zone of rock around the borehole contributes to the initial rebounding. Second, aerobic degradation of cis‐1,2‐DCE occurred causing declines in concentrations in the test zone. Third, microflow from microfractures contributed to the episodic spike in concentrations following the groundwater recharge event. In active flow zones, the latter two processes are not measurable due to equilibration from groundwater transport between the borehole and active flowing fractures.