Determination of vapor pressure-temperature relationships of current-use pesticides and transformation products

Sub-cooled liquid vapor pressures (P(L)(0)) of current-use organochlorine and organophosphate pesticides (chlorothalonil, chlorpyrifos methyl, diazinon, fipronil) and selected transformation products (chlorpyrifos oxon, heptachlor epoxide, oxychlordane, 3,5,6-trichloro-2-pyridinol) were determined at multiple temperatures using the gas chromatography retention time technique. Results were utilized to determine vapor pressure-temperature relationships and to calculate enthalpies of vaporization (DeltaH(vap)). While results for chlorothalonil and diazinon were comparable with published values, the measured value for fipronil (1.82 x 10(-6) Pa) is almost an order of magnitude higher than the reported literature value (3.7 x 10(-7) Pa). The availability of vapor pressure temperature relationships for these chemicals will aid in pesticide risk assessment development and improve the effectiveness of mitigation and remediation efforts.     

Development of cleaner-burning brick kilns in Ciudad Juarez, Chihuahua, Mexico

The following results provide a comparison between net airborne contamination produced by the traditional form of kiln used in Northern Mexico and by those modified according to a design by Dr. Robert Marquez. What has become known as the MK style kiln was intended to significantly reduce contaminant emissions. The concept involves covering the kiln with a dome and channeling the output of an active kiln through a second, identical loaded kiln for its additional filtration of the effluents. Kilns of a pair are connected via clay brick channels. The roles are reversed after the initial kiln is refilled. Significant reductions in the particulate and gaseous emissions were achieved in the prototype system, but a connectional problem with recent kiln pairs has also limited the degree of operational success. The problem did not mask the potential of the MK kiln, as will be shown. Additional anticipated benefits to the owners of MK kilns, such as reduced operating cycles and decreased quantities of fuel, also have been verified. Key measurements made during all of the burns were of aerosol densities and buoyancies in the flues, kiln temperatures, and, on a number of occasions, chemical analyses of both aerosol and gaseous effluents. Continuous time histories of aerosol densities for most burns (of a total of -40) provide a basis for examining features and the effects of differing styles of operation with respect to burn efficiency and net contaminant masses. Covering the active kiln with a dome produces a net reduction in dry aerosol effluent mass of a factor between 5 and 10, whereas the addition of a filter kiln produces a net reduction of about a factor of 2. The use of used motor oil as a fuel further reduced aerosol contamination by -1 order of magnitude.     

Comparison of topological,empirical and optimization-based approaches for locating quality detection points in water distribution networks

Environmental Science and Pollution Research - The positioning of quality detection points as well as the frequency of sampling is a crucial aspect for the implementation of Water Safety Plans...     

Assessing the effectiveness of green synthetized silver nanoparticles with Cryptocarya alba extracts for remotion of the organic pollutant methylene blue dye

Environmental Science and Pollution Research - In the present work, silver nanoparticles (AgNPs) synthetized with Cryptocarya alba (Peumo) leaf extract were studied. The fabrication method was...     

Structural confirmation of the sea ice biomarker IP25 found in Arctic marine sediments

IP₂₅ is a highly branched isoprenoid and an organic geochemical biomarker that is produced by some Arctic sea ice diatoms. IP₂₅ has previously been used in Arctic palaeo sea ice reconstruction studies and as a tracer for studying Arctic food webs. Here, the molecular structure of IP₂₅ has been confirmed by ¹H and ¹³C NMR spectroscopy following large-scale extraction from marine sediments obtained from the Canadian Arctic and purification using a combination of open-column and HPLC chromatographic methods. The structure of IP₂₅ was consistent between the three different sampling locations and was identical to that found previously for this biomarker following synthesis from a closely related highly branched isoprenoid diene. Since this study represents the first structural characterisation of IP₂₅ in sediments, future analysis of sedimentary IP₂₅ for palaeo Arctic sea ice reconstructions can be carried out with much greater confidence.     

A compilation of field surveys on gaseous elemental mercury (GEM) from contrasting environmental settings in Europe,South America,South Africa and China: separating fads from facts

Mercury is transported globally in the atmosphere mostly in gaseous elemental form (GEM, \( {\text{Hg}}_{\text{gas}}^{0} \) ), but still few worldwide studies taking into account different and contrasted environmental settings are available in a single publication. This work presents and discusses data from Argentina, Bolivia, Bosnia and Herzegovina, Brazil, Chile, China, Croatia, Finland, Italy, Russia, South Africa, Spain, Slovenia and Venezuela. We classified the information in four groups: (1) mining districts where this contaminant poses or has posed a risk for human populations and/or ecosystems; (2) cities, where the concentration of atmospheric mercury could be higher than normal due to the burning of fossil fuels and industrial activities; (3) areas with natural emissions from volcanoes; and (4) pristine areas where no anthropogenic influence was apparent. All the surveys were performed using portable LUMEX RA-915 series atomic absorption spectrometers. The results for cities fall within a low GEM concentration range that rarely exceeds 30 ng m^?3, that is, 6.6 times lower than the restrictive ATSDR threshold (200 ng m^?3) for chronic exposure to this pollutant. We also observed this behavior in the former mercury mining districts, where few data were above 200 ng m^?3. We noted that high concentrations of GEM are localized phenomena that fade away in short distances. However, this does not imply that they do not pose a risk for those working in close proximity to the source. This is the case of the artisanal gold miners that heat the Au–Hg amalgam to vaporize mercury. In this respect, while GEM can be truly regarded as a hazard, because of possible physical–chemical transformations into other species, it is only under these localized conditions, implying exposure to high GEM concentrations, which it becomes a direct risk for humans.     

Atmospheric deposition of pesticides to an agricultural watershed of the Chesapeake Bay

The Choptank River watershed, located on the Delmarva Peninsula of the Chesapeake Bay, is dominated by agricultural land use, which makes it vulnerable to runoff and atmospheric deposition of pesticides. Agricultural and wildlife areas are in close proximity and off-site losses of pesticides may contribute to toxic effects on sensitive species of plants and animals. High-volume air samples (n = 31) and event-based rain samples (n = 71) were collected from a single location in the watershed representing regional background conditions. Surface water samples were collected from eight stations in the tidal portion of the river on five occasions during 2000. Chlorothalonil, metolachlor, atrazine, simazine, endosulfan, and chlorpyrifos were frequently detected in the air and rain, with maximal concentrations during the period when local or regional crops were planted. The wet deposition load to the watershed was estimated at 150 +/- 16, 61 +/- 7, and 51 +/- 6 kg yr(-1) for chlorothalonil, metolachlor, and atrazine, respectively. The high wet deposition load compared with the estimated annual usage for chlorothalonil (13%) and endosulfan (14-90%) suggests an atmospheric source from outside the watershed. Net air-water gas exchange fluxes for metolachlor varied from -44 +/- 19 to 9.3 +/- 4.1 ng m(-2) d(-1) with negative values indicating net deposition. Wet deposition accounted for 3 to 20% of the total metolachlor mass in the Choptank River and was a more important source to the river than gas exchange. Estimates of herbicide flux presented here are probably a low estimate and actual rates may be significantly higher in areas closer to pesticide application.     

CUMULATIVE EFFECTIVE STREAM POWER AND BANK EROSION ON THE SACRAMENTO RIVER,CALIFORNIA, USA1

ABSTRACT: Bank erosion along a river channel determines the pattern of channel migration. Lateral channel migration in large alluvial rivers creates new floodplain land that is essential for riparian vegetation to get established. Migration also erodes existing riparian, agricultural, and urban lands, sometimes damaging human infrastructure (e.g., scouring bridge foundations and endangering pumping facilities) in the process. Understanding what controls the rate of bank erosion and associated point bar deposition is necessary to manage large alluvial rivers effectively. In this study, bank erosion was proportionally related to the magnitude of stream power. Linear regressions were used to correlate the cumulative stream power, above a lower flow threshold, with rates of bank erosion at 13 sites on the middle Sacramento River in California. Two forms of data were used: aerial photography and field data. Each analysis showed that bank erosion and cumulative effective stream power were significantly correlated and that a lower flow threshold improves the statistical relationship in this system. These correlations demonstrate that land managers and others can relate rates of bank erosion to the daily flow rates of a river. Such relationships can provide information concerning ecological restoration of floodplains related to channel migration rates as well as planning that requires knowledge of the relationship between flow rates and bank erosion rates.     

Toxicity attenuation of olive mill wastewater in soil slurries

Olive mill wastewaters are toxic for plants and microbes due to their high polyphenol content. We studied the effect of agricultural soil as a natural catalyst to promote polyphenol oxidation and polymerization, and in turn detoxify olive mill wastewaters. We show that model polyphenols are fully converted in soil slurries. Their products show no toxicity to the growth of a typical soil bacterium, Bacillus cereus, and reduced phytotoxicity in germination tests with English cress seeds. Those findings are promising for the sustainable treatment of olive wastewater in aerated soil slurries.     

Association of metals (mercury, cadmium and zinc) with metallothionein-like proteins in storage organs of stranded dolphins from the Mediterranean sea (Southern Italy)

Selected toxic and essential metals (mercury, Hg; cadmium, Cd; and zinc, Zn) were determined in the liver and in the kidney collected from 13 dolphins (Stenella coeruleoalba and Tursiops truncatus) stranded along the southern coasts of Italy from 1991 to 1999. Liver samples were also analysed for their methyl mercury (MeHg) and selenium (Se) contents. For subcellular fractionation, liver and kidney samples were homogenized in Tris-HCl buffer; after centrifugation, the supernatant (cytosol) was separated from pellets (insoluble fraction), heated at 80 degrees C for 10 min and centrifuged in order to separate the precipitate containing the thermolabile high molecular weight proteins. The cytosol heat-stable fraction, including metallothionein-like proteins (MTLPs), was then purified by gel filtration chromatography on Sephadex G-75 column. The three subcellular fractions collected (insoluble fraction, thermolabile fraction and purified heat-stable fraction) were analysed for their Hg, Cd and Zn contents. The analytical results confirm previous similar studies on toothed whales in showing that: (1) in the liver, as well as in the kidney, Hg was mainly found in the insoluble fraction, therefore, metallothioneins seem to have no role in the Hg detoxification; (2) in the liver, the molar ratio between Se and inorganic Hg was very close to 1; this suggests that the final compound of MeHg detoxification could be HgSe (tiemannite); (3) in almost all the samples, Cd and Zn were detected in the purified heat-stable fraction (including MTLPs). The mechanism of Cd detoxification and Zn homeostasis is also discussed.