Hydrolysis of chlorpyrifos in natural waters of the Chesapeake Bay

Chlorpyrifos is the most widely used insecticide in the Chesapeake Bay region. Recent studies show that this organophospate chemical is consistently present in the air, rain and surface waters of the Chesapeake Bay region, suggesting a long environmental half-life. Hydrolytic degradation of chlorpyrifos is likely a dominant removal process, but existing hydrolysis data do not reflect conditions in the Chesapeake Bay. In this project, hydrolysis rates of chlorpyrifos were measured in sterilized, ambient water from the mouth of four Chesapeake Bay tributaries ranging in salinity from 0 to 17 ppt. The measured hydrolysis half-lives varied from 24 d in the Patuxent River to 126 d in the Susquehanna River. These results indicate that pH alone cannot be used as a single parameter to predict hydrolysis under field conditions. The influence of copper concentration, and other water constituents, need to be further evaluated as they may emerge as independent predictors to assess the fate of pesticides in natural systems.     

Formation of PCDDs and PCDFs during the combustion of polyvinylidene chloride

In laboratory-scale combustion of polyvinylidene chloride (PVDC) with a quartz tubular furnace designed and fabricated to provide the desired combustion temperature and mixing state of combustion gas with air, it was found that at 800 degrees C or higher the level of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans [corrected] (PCDDs/PCDFs) resulting from PVDC combustion was no higher than that from heating air alone, and thus far below the levels which resulted from PVDC combustion at 750 degrees C or lower. The results provide the first laboratory confirmation of the relation between PVDC incineration temperature and PCDD/PCDF formation, and of the primary importance of high temperature, turbulence for mixing between air and combustion gas, and sufficient residence time, as governing factors for the minimization of PCDD/PCDF formation in municipal solid waste incinerators.     

A reproducible approach to the reporting of organochlorine compounds in epidemiologic studies

A growing body of research indicates that the most biologically active PCB congeners and organochlorines are not the most abundant components in human and wildlife samples. As researchers attempt measurement on a wider pool of less abundant compounds, they inevitably face quantification problems. To address this problem and enhance comparability across studies, we propose a standardized approach to report organochlorines that is based on a reproducible method to determine the limit of quantification (LQ). Two statistical methods are incorporated into our approach, one by Gibbons termed the Alternative Minimum Level (AML), and one based on determining a region of stable relativestandard deviation in instrument response (RSD). We illustrate our approach using historical samples collected during the 1960s from a cohort of pregnant women enrolled in the Child Health and Development Study. The results are applicable to determining the LQ of any method, and are of utmost importance to environmental scientists conducting trace organic analyses of complex mixtures. Our results demonstrate that: (1) precision as measured by RSD is the most important criterion in determining LQ; (2) the AML routinely isolates a region of constant RSD; and (3) the precision of the instrument detector response as measured with pure standards locates the LQ applicable for real samples - that is, the true limits of quantification reside in the detector, not the matrix effects or analyte recoveries associated with real samples. A corollary of these findings is that bias due to matrix effects and analyte recoveries can be assessed separately from precision and LQdetermination. Previous approaches involved spiking matrix blanks to determine LQ, a problematic strategy for real world, complex matrices. We have now validated the use of pure standards in LQ determination, an approach that is practical and accessible to most analysts.     

Chemical kinetic modeling of de novo synthesis of PCDD/F in municipal waste incinerators

A kinetic model is developed for de novo synthesis of PCDD/F from carbon in incinerator fly ash. The main mechanistic steps considered in the model are carbon gasification, PCDD/F formation, desorption and degradation. Rate equations are derived which can relate PCDD/F formation with process variables including carbon concentration of fly ash, partial pressure of oxygen, reaction temperature and time. The kinetic model has been verified using laboratory de novo synthesis data reported in the literature. When the model is applied to industrial incinerator conditions, PCDD/F formation levels of 0.1-0.5 microg/N m3 in the gas phase and 0.1-1.2 microg/g in the solid phase are calculated, and both are in good agreement with incinerator measurements.     

Hydroxyl radical scavenging role of chloride and bicarbonate ions in the H2O2/UV process

Simultaneous effect of inorganic anions, such as chloride and bicarbonate ions, on the scavenging of hydroxyl radicals (HO*) in the H2O2/UV process is the focus of this paper. The model compound of n-chlorobutane (BuCl) was used as the probe of HO*. By changing the pH conditions (2-9) and the concentrations of NaCl (0.25-2500 mM) and NaHCO3 (25 mM), the variation of HO* concentrations and the rate of H2O2 decomposition were compared. In general, the BuCl and H2O2 follow closely the first-order reaction within the first 10 and 40 min, respectively. In the presence of chloride alone at the pH range of 2-6, the HO* concentration in the reaction mixture increases with the increase of pH, and the HO* concentration at pH = 6 is 100 times of that at pH = 2. Including bicarbonate species in the solution, the peak HO* concentration was found at a certain pH, which shifts from 4, 5, to 5-7, as the molar ratios of chloride/bicarbonate species increase from 1 to 100. In addition, without bicarbonate species HO* concentration decreases significantly with increasing chloride concentration but remained rather unchanged beyond 1250 mM. In contrast, the HO* scavenging in the presence of bicarbonate species became relatively significant only when the chloride concentration reached beyond 250 mM. Throughout all experiments of different water quality conditions, the H2O2 decomposition rate remains rather unchanged.     

Changes of foraging patch selection and utilization by a giant panda after bamboo flowering

Environmental Science and Pollution Research - The bamboo flowering leads to the habitat fragmentation and food quality decline of a giant panda. Few empirical research has been conducted about the...     

Anti-oviposition activities of used sock media against a dengue vector: prospects of eco-friendly control and solutions to pollution

Yearly, huge amounts of sock refuse are discarded into the environment. Socks contain many molecules, and worn ones, which are rich in smell-causing bacteria, have a strong influence on animals’ behaviors. But the impacts of sock odor on the oviposition behavior of dengue vectors are unknown. We assessed whether Aedes albopictus changes its oviposition activity in response to the presence of used socks extract (USEx) in potential breeding grounds, using choice and no-choice bioassays (NCB). When furnished even chances to oviposit in two sites holding USEx and two others containing water (control), Ae. albopictus deposited significantly less eggs in USEx than in water sites. A similar pattern of oviposition preference was also observed when there were more oviposition options in water. When there were greater oviposition opportunities in USEx sites, Ae. albopictus oviposited preferentially in water. Females laid significantly more eggs during the NCB involving water than USEx. Also, significantly more mature eggs were retained by females in the NCB with USEx than in that with water. These observations strongly suggest the presence of molecules with either repellent or deterrent activities against Ae. albopictus females and provide an impetus to advocate the integration of used socks in dengue control programs. Such applications could be a realistic end-of-life recourse to reroute this waste from landfills.

     

Development and evaluation of a continuous coarse (PM10-PM2.5) particle monitor

In this paper, we describe the development and laboratory and field evaluation of a continuous coarse (2.5-10 microm) particle mass (PM) monitor that can provide reliable measurements of the coarse mass (CM) concentrations in time intervals as short as 5-10 min. The operating principle of the monitor is based on enriching CM concentrations by a factor of approximately 25 by means of a 2.5-microm cut point round nozzle virtual impactor while maintaining fine mass (FM)--that is, the mass of PM2.5 at ambient concentrations. The aerosol mixture is subsequently drawn through a standard tapered element oscillating microbalance (TEOM), the response of which is dominated by the contributions of the CM, due to concentration enrichment. Findings from the field study ascertain that a TEOM coupled with a PM10 inlet followed by a 2.5-microm cut point round nozzle virtual impactor can be used successfully for continuous CM concentration measurements. The average concentration-enriched CM concentrations measured by the TEOM were 26-27 times higher than those measured by the time-integrated PM10 samplers [the micro-orifice uniform deposit impactor (MOUDI) and the Partisol] and were highly correlated. CM concentrations measured by the concentration-enriched TEOM were independent of the ambient FM-to-CM concentration ratio, due to the decrease in ambient coarse particle mass median diameter with an increasing FM-to-CM concentration ratio. Finally, our results illustrate one of the main problems associated with the use of real impactors to sample particles at relative humidity (RH) values less than 40%. While PM10 concentrations obtained by means of the MOUDI and Partisol were in excellent agreement, CM concentrations measured by the MOUDI were low by 20%, and FM concentrations were high by a factor of 5, together suggesting particle bounce at low RH.     

Genotoxic damage in free-living Algerian mouse (Mus spretus) after the Coto Doñana ecological disaster

The Do?ana National Park (Spain), one of the most important wildlife sites in the West of Europe, was affected (25 April 1998) by the spill of acidic waste rich in toxic metals (mainly zinc, lead, copper, etc.), arsenic and aromatic amines from the Aznalcollar mine accident. Micronuclei test with May Grunwald-Giemsa and with CREST-antikinetocore staining using DAPI as counter-staining were performed on peripheral blood erythrocytes from Algerian mice to evaluate genotoxic damage. Animals were collected in four locations each differently affected by the disaster. Higher frequencies of micronuclei and CREST-positive micronuclei were observed in the sites, which were reached by toxic sludge and contaminated water in comparison with those located within the park. The results obtained applying the two methods indicate that DAPI staining is more sensitive in detecting micronuclei. Genotoxic biomonitoring should be further carried out in the area to control the mutagenetic level in natural populations.