Removal mechanisms and fate of insecticides in constructed wetlands

Constructed wetlands (CWs), along with other vegetative systems, are increasingly being promoted as a mitigation practice to treat non-point source runoff to reduce contaminants such as pesticides. However, studies so far have mostly focused on demonstrating contaminant removal efficiency. In this study, using two operational CWs located in the Central Valley of California, we explored the mechanisms underlying the removal of pyrethroids and chlorpyrifos from agricultural runoff water, and further evaluated the likelihood for the retained pesticides to accumulate within the CWs over time.In the runoff water passing through the CWs, pyrethroids were associated overwhelmingly with suspended solids >0.7 μm, and the sorbed fraction accounted for 38-100% of the total concentrations. The derived K_d values for the suspended solids were in the order of 10⁴-10⁵, substantially greater than those reported for bulk soils and sediments. Distribution of pyrethroids in the wetland sediments was found to mimic organic carbon distribution, and was enriched in large particles that were partially decomposed plant materials, and clay-size particles (<2 μm). Retention of suspended particles, especially the very large particles (>250 μm) and the very fine particles, is thus essential in removing pyrethroids and chlorpyrifos in CWs. Under flooded and anaerobic conditions, most pyrethroids and chlorpyrifos showed moderate persistence, with DT₅₀ values between 106-353 d. However, the retained pyrethroids were very stable in dry and aerobic sediments between irrigation seasons, suggesting a possibility for accumulation over time. Therefore, the long-term ecological risks of CWs should be further understood before their wide adoption.     

Use of the electrical aerosol detector as an indicator of the surface area of fine particles deposited in the lung

Because of recent concerns about the health effects of ultrafine particles and the indication that particle toxicity is related to surface area, we have been examining techniques for measuring parameters related to the surface area of fine particles, especially in the 0.003- to 0.5-microm size range. In an earlier study, we suggested that the charge attached to particles, as measured by a prototype of the Electrical Aerosol Detector (EAD, TSI Inc., Model 3070), was related to the 1.16 power of the mobility diameter. An inspection of the pattern of particle deposition in the lung as a function of particle size suggested that the EAD measurement might be a useful indicator of the surface area of particles deposited in the lung. In this study, we calculate the particle surface area (micrometer squared) deposited in the lung per cubic centimeter of air inhaled as a function of particle size using atmospheric particle size distributions measured in Minneapolis, MN, and East St. Louis, IL. The correlations of powers of the mobility diameter, Dx, were highest for X = 1.1-1.6 for the deposited surface area and for X = 1.25 with the EAD signal. This overlap suggested a correspondence between the EAD signal and the deposited surface area. The correlation coefficients of the EAD signal and particle surface area deposited in the alveolar and tracheobronchial regions of the lung for three breathing patterns are in the range of Pearson's r = 0.91-0.95 (coefficient of determination, R2 = 0.82-0.90). These statistical relationships suggest that the EAD could serve as a useful indicator of particle surface area deposited in the lung in exposure and epidemiologic studies of the human health effects of atmospheric particles and as a measure of the potential surface area dose for the characterization of occupational environments.     

Toxicity of fipronil and its enantiomers to marine and freshwater non-targets

Fipronil is a phenylpyrazole insecticide used in agricultural and domestic settings for controlling various insect pests in crops, lawns, and residential structures. Fipronil is chiral; however, it is released into the environment as a racemic mixture of two enantiomers. In this study, the acute toxicity of the (S,+) and (R,-) enantiomers and the racemic mixture of fipronil were assessed using Simulium vittatum IS-7 (black fly), Xenopus laevis (African clawed frog), Procambarus clarkii (crayfish), Palaemonetes pugio (grass shrimp), Mercenaria mercenaria (hardshell clam), and Dunaliella tertiolecta (phytoplankton). Results showed that S. vittatum IS-7 was the most sensitive freshwater species to the racemic mixture of fipronil (LC50 = 0.65 microg/L) while P. pugio was the most sensitive marine species (LC50 = 0.32 microg/L). Procambarus clarkii were significantly more sensitive to the (S,+) enantiomer while larval P. pugio were significantly more sensitive to the (R,-) enantiomer. Enantioselective toxicity was not observed in the other organisms tested. Increased mortality and minimal recovery was observed in all species tested for recovery from fipronil exposure. These results indicate that the most toxic isomer of fipronil is organism-specific and that enantioselective toxicity may be more common in crustaceans than in other aquatic organisms.     

Natural and anthropogenic influences on a red-crowned crane habitat in the Yellow River Delta Natural Reserve, 1992–2008

This study aims to assess the relative importance of natural and anthropogenic variables on the change of the red-crowned crane habitat in the Yellow River Nature Reserve, East China using multitempopral remote sensing and geographic information system. Satellite images were used to detect the change in potential crane habitat, from which suitable crane habitat was determined by excluding fragmented habitat. In this study, a principal component analysis (PCA) with seven variables (channel flow, rainfall, temperature, sediment discharge, number of oil wells, total length of roads, and area of settlements) and linear regression analyses of potential and suitable habitat against the retained principal components were applied to explore the influences of natural and anthropogenic factors on the change of the red-crowned crane habitat. The experimental results indicate that suitable habitat decreased by 5,935 ha despite an increase of 1,409 ha in potential habitat from 1992 to 2008. The area of crane habitat changed caused by natural drivers such as progressive succession, retrogressive succession, and physical fragmentation is almost the same as that caused by anthropogenic forces such as land use change and behavioral fragmentation. The PCA and regression analyses revealed that natural factors (e.g., channel flow, rainfall, temperature, and sediment discharge) play an important role in the crane potential habitat change and human disturbances (e.g., oil wells, roads, and settlements) jointly explain 51.8 % of the variations in suitable habitat area, higher than 48.2 % contributed by natural factors. Thus, it is vital to reduce anthropogenic influences within the reserve in order to reverse the decline in the suitable crane habitat.     

Hg Vapor Emission from Broken Compact Fluorescent Lamps (CFLs) in an Acrylic Chamber

The United States Environmental Protection Agency/Environmental Response Team (US EPA/ERT), in collaboration with St. John's College, Dr. B. R. Ambedkar University, Agra, India, is conducting a study to determine Hg vapor emission rates resulting from broken compact fluorescent lamps (CFLs) in a residential setting. The overall objectives of the study are to determine Hg vapor emission data and provide homeowners with cleanup procedures and disposal options for broken CFLs. Most of the currently available CFLs in the US market are manufactured in China for US companies. Several different types of CFLs were purchased from local stores and their Hg content was determined. Based on previous studies, such as the 2011 study by Singhvi and colleagues, five popular spiral CFLs were selected for emission studies in an acrylic chamber. This study found that Hg vapor emissions from CFLs may be significantly greater than those from beads of liquid Hg with weights comparable to the Hg content of the CFLs. The average 24-hour Hg loss into the atmosphere from CFLs broken on a plastic surface ranged from 0.6% to 22% of the bulb content, while that for CFLs broken on carpet ranged from 2.6% to 28%. Projections for a 12 foot × 9.33 foot × 8 foot (25.4 m³) room based on the chamber measurements in this study indicate that CFL breakage in some household settings may produce 24-hour Hg concentrations above the 2000 Agency for Toxic Substances and Disease Registry (ATSDR) minimum risk level (MRL) of 0.2 μg/m³, for typical air exchange rates. This study also indicates that Hg emission may not be proportional to exposed surface area based on experiments using liquid Hg with different surface areas.     

Evaluation of Probes Used for Source Sampling of Hydrogen Fluoride

The body of information presented in this paper is directed to those individuals concerned with methods for the sampling and measurement of fluorides contained in stack gases produced during the manufacture of phosphate fertilizer or aluminum. An air stream containing gaseous hydrogen fluoride (HF), at concentrations of from 87 to 1700 µg F m^-3, was generated and passed through 193 to 198 cm lengths of Pyrex glass, type 316 stainless steel, TFE Teflon, and methyl methacrylate-coated aluminum probes at flow rates of 28 I min^-1. HF passing through the probes was collected in deionized water contained in a Greenburg-Smith impinger. The Teflon probe exhibited no loss of HF and no trend toward increased passage of HF with time. Significant amounts of fluoride were lost in 18 out of 20 tests with the methacrylate probe and in 4 out of 20 tests with the Pyrex and stainless steel probes. Trends toward increased passage of HF with time occurred with the latter three probe materials. The selective ion electrode and semiautomated methods gave equivalent results when samples were made alkaline to avoid sorption of fluoride by Tygon tubing used in the semiautomated method. These results demonstrated that a Teflon probe gave the most representative sample of gaseous HF. However, additional tests are needed before a final recommendation is made for a probe to sample fluorides in stack gases.     

Oxidation of bisphenol F (BPF) by manganese dioxide

Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO₂. At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 μM MnO₂ and 4.4 μM BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low (≤pH 5.5) and high pH (≥pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn²⁺ > Ca²⁺ > Mg²⁺ > Na⁺ and HPO₄²⁻ > Cl⁻ > NO₃⁻ ≈ SO₄²⁻, respectively. A total of 5 products were identified, from which a tentative pathway was proposed.     

Charismatic leadership and follower effects

On the basis of the current theories of charismatic leadership, several possible follower effects were identified. It is hypothesized that followers of charismatic leaders could be distinguished by their greater reverence, trust, and satisfaction with their leader and by a heightened sense of collective identity, perceived group task performance, and feelings of empowerment. Using the Conger–Kanungo charismatic leadership scale and measures of the hypothesized follower effects, an empirical study was conducted on a sample of 252 managers using structural equation modelling. The results show a strong relationship between follower reverence and charismatic leadership. Follower trust and satisfaction, however, are mediated through leader reverence. Followers' sense of collective identity and perceived group task performance are affected by charismatic leadership. Feelings of empowerment are mediated through the followers' sense of collective identity and perceived group task performance. Copyright © 2000 John Wiley & Sons, Ltd.     

Rotary drum soil blending for source zone remediation: Various application scenarios

Mechanical blending of contaminated soil with amendments has recently reemerged as an important treatment technology. From its original application using large‐diameter augers in the early 1990s to the current use of rotary drum blenders, soil blending is being used as an alternative to other remediation technologies like amendment injection and soil vapor and groundwater extraction. Shallow (approximately 10 m below ground surface [bgs] or less) soil blending also offers an alternative to excavation and disposal. Soil blending has been used to remediate a site with various contaminants including, but not limited to, chlorinated solvents, petroleum, and metals. The types of soils susceptible to soil blending vary from sands and gravels to silts and clays to fractured rock and combinations of all of these. The types of amendments blended include oxidants, reducing agents, biological enhancements, and stabilizing amendments. Soil blending systems deliver the power to the mixing head to adequately mix the soil and amendment to enhance remediation effectiveness. Since long‐term contamination is often a result of heterogeneously distributed residual contaminant in localized source zones that are difficult to access, the typical aim of soil blending is to homogenize the soil while effectively distributing amendment to these zones made accessible by blending. By effectively homogenizing the soil, however, soil blending will increase the void ratio and disrupt the shear strength and bearing capacity of the soil so an important component of a soil blending technology is proper recovery of these geotechnical parameters. This can be achieved by using well‐known soil improvement techniques such as amending all or a portion of the blended area with Portland cement or lime. Several case studies of soil blending treatments of different contaminants and amendments in various soil types are provided.