Passive air sampling theory for semivolatile organic compounds

The mathematical modelling underlying passive air sampling theory can be based on mass transfer coefficients or rate constants. Generally, these models have not been inter-related. Starting with basic models, the exchange of chemicals between the gaseous phase and the sampler is developed using mass transfer coefficients and rate constants. Importantly, the inter-relationships between the approaches are demonstrated by relating uptake rate constants and loss rate constants to mass transfer coefficients when either sampler-side or air-side resistance is dominating chemical exchange. The influence of sampler area and sampler volume on chemical exchange is discussed in general terms and as they relate to frequently used parameters such as sampling rates and time to equilibrium. Where air-side or sampler-side resistance dominates, an increase in the surface area of the sampler will increase sampling rates. Sampling rates are not related to the sampler/air partition coefficient (K(SV)) when air-side resistance dominates and increase with K(SV) when sampler-side resistance dominates.     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

A framework for evaluating biodiversity mitigation metrics

Biodiversity mitigation is a cornerstone of applied conservation. Mitigation encompasses a suite of practices, ranging from planned avoidance of impacts to creation of new natural habitats. Accurate and appropriate metrics quantifying impacts to natural systems and the effectiveness of restoration are necessary to measure the success of different mitigation strategies. Because effective mitigation requires adequate metrics, we developed a Biodiversity Metrics Framework to assist practitioners and policy makers in assessing biodiversity mitigation metrics. Based on Noss’ Hierarchy of Biodiversity, the Scorecard highlights the mismatch between scientifically defined best practices and metrics required by policy. The Framework may serve a vital role in standardizing and validating mitigation projects into the future.

     

A queen pheromone induces workers to kill sexual larvae in colonies of the red imported fire ant (<Emphasis Type="Italic">Solenopsis invicta</Emphasis>)

We conducted five bioassays to study how queens control the execution of sexual larvae by workers in colonies of the red imported fire ant, Solenopsis invicta. In each assay, subset colonies were made from many large polygyne colonies, and the 20 sexual larvae they contained were monitored over time. Sexual larvae mostly survived in queenless colonies, but were mostly killed in colonies with a single dealated queen, regardless of whether or not the queen was fertilized. The larvae were also killed when fresh corpses of queens were added to queenless colonies. Whereas acetone extracts of queens did not produce a significant increase in killings, extracts in buffered saline induced workers to execute most sexual larvae, indicating successful extraction of an execution pheromone. We identified the probable storage location of the chemical as the poison sac, and found both fresh (1 day) and old (21 day) extracts of poison sacs to be equally effective in inducing executions. The pheromone is stable at room temperature, perhaps because venom alkaloids also present in the extracts keep the pheromone from degrading. It is apparently either proteinaceous or associated with a proteinaceous molecule, a novel finding, as no queen pheromone of a proteinaceous nature has been previously demonstrated in ants.     

Eight years of annual no-till cropping in Washington's winter wheat-summer fallow region

The tillage-based winter wheat (Triticum aestivum L.)-summer fallow (WW-SF) cropping system has dominated dryland farming in the Pacific Northwest USA for 125 years. We conducted a large-scale multidisciplinary 8-year study of annual (i.e., no summer fallow) no-till cropping systems as an alternative to WW-SF. Soft white and hard white classes of winter and spring wheat, spring barley (Hordeum vulgare L.), yellow mustard (Brassica hirta Moench), and safflower (Carthamus tinctorius L.) were grown in various rotation combinations. Annual precipitation was less than the long-term average of 301 mm in 7 out of 8 years. Rhizoctonia bare patch disease caused by the fungus Rhizoctonia solani AG-8 appeared in year 3 and continued through year 8 in all no-till plots. All crops were susceptible to rhizoctonia, but bare patch area in wheat was reduced, and grain yield increased, when wheat was grown in rotation with barley every other year. Remnant downy brome (Bromus tectorum L.) weed seeds remained dormant for 6 years and longer to heavily infest recrop winter wheat. There were few quantifiable changes in soil quality due to crop rotation, but soil organic carbon (SOC) increased in the surface 0–5 cm depth with no-till during the 8 years to approach that found in undisturbed native soil. Annual no-till crop rotations experienced lower average profitability and greater income variability compared to WW-SF. Yellow mustard and safflower were not economically viable. Continuous annual cropping using no-till provides excellent protection against wind erosion and shows potential to increase soil quality, but the practice involves high economic risk compared to WW-SF. This paper provides the first comprehensive multidisciplinary report of long-term alternative annual no-till cropping systems research in the low-precipitation region of the Pacific Northwest.     

Nitrogen fixation on a coral reef

Acetylene reduction was used to assess nitrogen fixation on all major substrates at all major areas over a period of 1 to 6 yr (1980–1986) at One Tree Reef (southern Great Barrier Reef). Experiments using ¹⁵N₂ gave a ratio of 3.45:1.0 for C₂H₂ reduced:N₂ fixed. Acetylene reduction was largely light-dependent, saturated at 0.15 ml C₂H₂ per ml seawater, and linear over 6 h. High fixation was associated with two emergent cyanophyte associations, Calothrix crustacea and Scytonema hofmannii, of limited distribution. Subtidally, the major contribution to nitrogen fixation came from well-grazed limestone substrates with an epilithic algal community in the reef flat and patch reefs (3 to 15 nmol C₂H₄ cm^-2 h^-1). Similar substrates from the outer reef slope showed lower rates. Nitrogen fixation on beach rock, intertidal coral rubble, reef crest and lagoon sand was relatively small (0.3 to 1.0 nmol C₂H₄ cm^-2 h^-1). Seasonal changes in light-saturated rates were small, with slight reduction only in winter. Rates are also reported for experimental coral blocks (13 to 39 nmol cm^-2 h^-1) and for branching coral inside and outside territories of gardening damselfish (3 to 28 nmol cm^-2 h^-1). This work supports the hypothesis that the high nitrogen fixation on the reef flat and patch reefs of the lagoon (34 to 68 kg N ha^-1 yr^-1) is because these subtidal areas support highly disturbed communities with the greatest abundance of nitrogen-fixing cyanophyte algae. It is calculated from a budget of all areas that One Tree Reef has an annual nitrogen fixation rate of 8 to 16 kg N ha^-1 yr^-1.     

Rapid enzyme immunoassays for the detection of carbaryl and methoprene in grains

In order for grain handlers and traders to reliably estimate residues of grain protectants in the field, antibody-based rapid tests were developed for carbaryl (1-naphthyl methylcarbamate) and methoprene [isopropyl (E,E)-(RS)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoate]. To complement the rapid analysis, a simple and rapid extraction technique was developed. In these tests, a pesticide-containing methanol extract of the grain sample and an enzyme-labeled component are added to precoated strips. After a brief incubation, the strips are washed and a substrate/chromogen for the enzyme is added. The color developed is stopped by acidification and the results are read either by eye or in a portable field photometer. The overall test time is under 20 minutes. For carbaryl, the test had a limit of detection of 4.5 ppb (1.1 ppm in grain), while the methoprene test had a limit of detection of 4 ppb (1 ppm in grain) based on the lower datum point, which is 15% inhibition, in the standard curves. Both assays can be used as a screening test for carbaryl and methoprene in animal feed grains.     

Bioindicators of enhanced nitrogen deposition

Increased deposition of atmospheric N largely from intensive agriculture is affecting biodiversity and the composition of natural and semi-natural vegetation in Europe. The value of species based bioindicators such as the Ellenberg N index and measurements of total tissue N and free amino acids in key plant species, is described with reference to a mixed woodland downwind of a livestock farm in the Scottish Borders, operated for over 20 years with a measured spatial gradient of ammonia concentration (29-1.5 microg m(-3)). All the indicators examined showed a relationship with N deposition and provided some indication of vegetation change. Total tissue N and arginine concentrations were most closely linked with ammonia concentrations and N deposition, with r(2) values of >0.97 and >0.78 respectively.     

Performance of anaerobic waste activated sludge digesters after microwave pretreatment.

Effects of microwave pretreatment on waste activated sludge (WAS) in mesophilic semicontinuous digesters with acclimatized inoculum at solids retention times (SRTs) of 5, 10, and 20 days are presented. Batch digesters determined optimum microwave temperature, intensity, WAS concentration, and percentage of WAS pretreated for highest WAS solubilization (soluble to total chemical oxygen demand ratio [SCOD:TCOD]) and biogas production. Pretreatment results indicated the potential to damage floc structure and release 4.2-, 4.5-, and 3.6-fold higher soluble proteins, sugars, and SCOD:TCODs compared with controls, with nucleic acid release. Pretreatment increased dewaterability and bioavailability of WAS with 20% higher biogas production compared with controls in batch digestion. In semicontinuous digesters, relative (to control) improvements in removals dramatically increased, as SRT was shortened from 20 to 10 to 5 days, with 23 and 26% higher volatile solids removals for WAS pretreated to 96 degrees C by microwave and conventional heating at a 5-day SRT.