Effect of two major N-nitroso hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) metabolites on earthworm reproductive success

Soil and topical tests were employed to investigate the effect of two N-nitroso metabolites of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) on earthworm reproduction. The lowest observed effect concentration (LOEC) for cocoon production and hatching was 50mg/kg for both hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX) and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX) in soil. MNX and TNX also significantly affected cocoon hatching in soil (p<0.001) and in topical tests (p=0.001). The LOECs for cocoon hatching were 1 and 10mg/kg for MNX and TNX in soil, respectively, and 10mg/L in the topical test. Greater than 100mg/kg MNX and TNX completely inhibited cocoon hatching. In soil, the EC20 values for MNX were 8.7 and 8.8mg/kg for cocoon and juvenile production, respectively, compared to 9.2 and 9.1mg/kg for TNX, respectively. The EC20 values for the total number of cocoon hatchlings were 3.1 and 4.7mg/kg for MNX and TNX, respectively, in soil and 4.5 and 3.1mg/L in the topical test. Both MNX and TNX inhibited cocoon production and hatching, suggesting that they may have a negative affect on soil ecosystems at contaminated sites.     

Prediction of Pb speciation in concentrated and dilute nutrient solutions

Despite the presence of numerous studies in the literature examining the phytotoxicity of Pb, there is a lack of precise quantitative data on limiting concentrations of Pb for plant growth. Using the PhreeqcI chemical equilibrium model, simulations were conducted to examine the speciation of Pb in concentrated and dilute nutrient solutions. Due to the higher P concentration of Hoagland's solution (1000microM), precipitation of chloropyromorphite (Pb5(PO4)3Cl) was predicted to occur at lower pH values, and at lower Pb concentrations, than for a dilute nutrient solution (2microM P). Although nutrient solutions prepared in the glasshouse were supersaturated (and Pb concentrations were substantially higher than predicted by modeling), they confirmed the importance of the P concentration in influencing the precipitation of Pb. Given the low solubility of Pb-phosphates, nutrient solutions with low P concentrations should be utilized, and plant growth should be related to measured Pb concentrations rather than to the quantity of Pb initially added.     

A directional passive air sampler for monitoring polycyclic aromatic hydrocarbons (PAHs) in air mass

A passive air sampler was developed for collecting polycyclic aromatic hydrocarbons (PAHs) in air mass from various directions. The airflow velocity within the sampler was assessed for its responses to ambient wind speed and direction. The sampler was examined for trapped particles, evaluated quantitatively for influence of airflow velocity and temperature on PAH uptake, examined for PAH uptake kinetics, calibrated against active sampling, and finally tested in the field. The airflow volume passing the sampler was linearly proportional to ambient wind speed and sensitive to wind direction. The uptake rate for an individual PAH was a function of airflow velocity, temperature and the octanol-air partitioning coefficient of the PAH. For all PAHs with more than two rings, the passive sampler operated in a linear uptake phase for three weeks. Different PAH concentrations were obtained in air masses from different directions in the field test.     

U and Th in some brown coals of Serbia and Montenegro and their environmental impact

GOAL, SCOPE AND BACKGROUND: The objective of this paper is to determine and compare the concentrations of U and Th in soft to hard brown (lignite to sub-bituminous) coals of Serbia and Montenegro. It also presents comparison of the obtained data on U and Th concentrations with the published data on coals located in some other countries of the world. Almost the whole coal production of Serbia and Montenegro is used as feed coals for combustion in thermal power plants. METHODS: Channel samples from open pit and underground mines and core samples were collected for hard and soft brown coals. For the analysis the samples were decomposed using microwave technique. Obtained solutions containing U and Th were analyzed by inductively coupled plasma mass spectroscopy (ICP-MS) using NIST standards. RESULTS: Concentration of U from the investigated basins and the corresponding mine fields ranges within 0.60-70.10 mg/kg, 0.65-3.20 mg/kg, 0.95-6.59 mg/kg, 1.20-6.05 mg/kg, 0.80-6.66 mg/kg, 0.18-89.90 mg/kg, 0.19-4.14 mg/kg, and 0.28-3.52 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. Concentration of Th ranges within 0.20-2.60 mg/kg, 0.84-6.57 mg/kg, 1.48-6.48 mg/kg, 0.12-2.71 mg/kg, 0.13-4.95 mg/kg, 0.14-3.48 mg/kg, 0.29-3.56 mg/kg, and 0.17-1.89 mg/kg for the Kostolac, Kolubara, Krepoljin, Sjenica, Soko Banja, Bogovina East field, Senje-Resavica and Pljevlja basins, respectively. DISCUSSION: Brown coal from Senje-Resavica, Kolubara, Kostolac and Pljevlja is characterized by low U concentration. Coals form the Krepoljin, Soko Banja and Sjenica basins have slightly higher U concentrations than the mentioned group. The highest concentration of U is characteristic for the coal from the Bogovina East field. Concentration of Th in coals from Serbia and Montenegro has proved to be low. Out of all investigated coal basins, only the coal from the Krepoljin and Kolubara basins has high concentration of Th. The hydrothermally altered rocks of the Timok dacite-andesite complex, representing the basement of the Bogovina basin, could be a potential source of U, especially at the bottom part of the Lower seam of the Bogovina East field. CONCLUSIONS: This study shows that brown coals in Serbia and Montenegro (soft to hard brown coals or lignite to sub-bituminous) contain low levels of U (5.30 mg/kg, average value and 2.10 mg/kg geometric mean value) and Th (1.80 mg/kg, average value and 1.12 mg/kg geometric mean value). There are some obvious differences in concentration of U and Th in coals from different basins in Serbia and Montenegro. The approximate value for U and Th release mainly from power plants was 644.33 t and 983.46 t, respectively within the period 1965-2000 for the studied mines in Serbia, and 23.76 t and 15.05 t for the Potrlica mine (Montenegro) within the period 1965-1997. RECOMMENDATIONS: The coals in Serbia and Montenegro show no identifiable unfavourable impact on the surrounding environment, due to low natural radioactive concentration of U and Th, but further investigations concerning human health should be performed. PERSPECTIVES: Preliminary research revealed that in some Serbian coals (and, particularly, parts of the coal seam) U and Th content are rather high. Such coals should be carefully studied, as well as U and Th concentrations in ash, fly ash, waste disposals, nearby soil and ground water. Further studies should include determination of the radioactivity of all these products, and estimation of possible health impact.     

Effect of herbicides on glutathione S-transferases in the earthworm, <Emphasis Type="Italic">Eisenia fetida</Emphasis>

AIM AND BACKGROUND: Earthworms have been studied as a readily available, easily maintainable and cheap test species for assessing chemical pollution, and may be an alternative to in vivo rodent bioassays. The current investigation aims to characterize detoxification enzymes in Eisenia fetida and stress response against two herbicides with different modes of action, namely, fenoxaprop and metolachlor. METHODS: Herbicides were applied to soil containing earthworms. Animals were then collected, sacrificed and shock-frozen. Extracted protein was analyzed for glutathione S-transferase (GST) activity using CDNB (1-chloro-2,4-dinitrobenzene), DCNB (1,2-dichloro-4-nitrobenzene), pNBC (p-nitrobenzylchloride), PNOBC (p-nitrobenz-o-ylchloride) and selected herbicides. GST isoenzymes were partially purified by affinity chromatography and molecular weights were estimated by SDS-PAGE. RESULTS: In E. fetida protein extracts, GST activity towards model compounds ranked as CDNB>DCNB>PNBOC>PNBC. Fluorodifen was not conjugated at all, but fenoxaprop and metolachlor were conjugated at low rates. Furthermore, the GST isoenzyme pattern changed during the incubation with herbicides, either due to stress or as a defense reaction. After incubation with monochlorobimane, a strong fluorescence of the intestinal tract and the intersegments was observed, indicating organ-specific GST induction. DISCUSSION: According to the author's knowledge, here, for the first time, evidence is presented that E. fetida GST are also capable of conjugating a wider range of xenobiotic substrates. Different forms of GST were observed and changes in GST isoforms due to the herbicide treatment were also noticed. GST conjugation rates varied between different herbicides used in this experiment. It might be assumed that herbicides may well be detoxified by earthworms, to a certain extent, but that they are also potent stress factors influencing the detoxification system of the animal. High doses or long exposure might lead to deleterious effects on earthworms and limit their survival rate. The use of the animals as bioindicators for herbicides and herbicide residues seems very promising, but is surely influenced by the lack of detoxification for some compounds. CONCLUSIONS: Conjugation of several xenobiotics with model substances and herbicides is proven in the earthworm E. fetida. However, E. fetida has only limited capabilities of detoxifying herbicidal compounds. Different isoforms of GST were involved and altered in their activity after treatment. RECOMMENDATIONS AND PERSPECTIVES: The accumulation of GS-conjugates and their determination via fluorescence microscopy is a quick and secure, additional marker for exposure that should be further developed to complement existing biotests. The described methods and endpoints might help to understand the complex reaction of earthworms towards herbicides and lead to an adapted test methodology.     

Comparison of surface emissions and subsurface distribution of cis- and trans-1,3-dichloropropene and chloropicrin in sandy field beds covered with four different plastic films

The purpose of this study was to conduct a field study at a Florida field site on surface emissions and subsurface distribution of cis-and trans-1,3-dichloropropene (1,3-D) and chloropicrin (CP) in raised beds injected with Telone C35 with four replications. A total of 16 beds were applied with Telone C35 by chisel injection and covered with four different plastic films, 4 beds for each film. Each bed was installed with five 20-cm long soil pore air probes and a surface air collection pan at arbitrarily locations along the length of each bed for sampling soil pore air and surface air, respectively, for analysis of the three biologically active compounds, cis- and trans-1,3-D and CP. We found that average concentrations of the three compounds at 20-cm depth among the beds covered with four different plastic films generally were not statistically different. Among the four beds covered with the same plastic film, average concentrations of the three compounds were statistically different only in the four metallic PE covered beds at 5 and 24 hours after injection. Volatilization rates of the three compounds among the beds covered with four different plastic films, with the exception of CP at 48 hours after injection, were not statistically different. It appeared that initial upward diffusion and volatilization flux were influenced by solar radiation. Initial subsurface concentrations of the three compounds and volatilization flux, especially cis-1,3-D, were greater in the beds on the east side of the field than that in the beds on the west side of the field. Whether or not difference in initial subsurface concentrations of the compounds between east side beds and west side beds may influence fumigant efficacy remains to be determined.     

Humic substances

GOAL, SCOPE AND BACKGROUND: Freshwater bodies which chemistry is dominated by dissolved humic substances (HS) seem to be the major type on Earth, due to huge non-calcareous geological formations in the Northern Hemisphere and in the tropics. Based on the paradigm of the inertness of being organic, direct interactions of dissolved HS with freshwater organisms are mostly neglected. However, dissolved organic carbon, the majority of which being HS, are natural environmental chemicals and should therefore directly interact with organisms. Major results that widened our perspective on humic substance ecology come from experiments with the compost nematode, Caenorhabditis elegans, which behaved contradictorily to textbook knowledge and provoked an in-depth re-consideration of some paradigms. APPROACH: To overcome old paradigms on HS and their potential interactions with organisms, we reviewed recent international literature, as well as 'grey' literature. We also include results from own ongoing studies. RESULTS: This review focuses on direct interactions of dissolved HS with freshwater organisms and disregards indirect effects, such as under-water light quenching. Instead we show with some macrophyte and algal species that HS adversely interfere with photosynthesis and growth, whereby closely related algal species show different response patterns. In addition to this, HS suppress cyanobacteria more than eukaryotic algae. Quinones in the HS appear to be the effective structure. Furthermore, HS can modulate the offspring numbers in the nematode C. elegans and cause feminization of fish and amphibians--they possess hormone-like properties. The ecological consequences of this potential remain obscure at present. HS also have the potential to act as chemical attractants as shown with C. elegans and exert a mild chemical stress upon aquatic organisms in many ways: induction of molecular chaperons (stress proteins), induction and modulation of biotransformation and anti-oxidant enzymes. Furthermore, they produce an oxidative stress with lipidperoxidation as one clear symptom or even stress defense strategy. Stronger chemical stresses by HS may even lead to teratogenic effects as shown with fish embryos; all physiological responses to HS-mediated stress require energy, which were compensated on the expense of yolk as shown with zebra fish embryos. One Finnish field survey supports the view of a strong chemical stress, as the weight yield in fish species decreases with increasing HS content in the lakes. DISCUSSION: HS exert a variety of stress symptoms in aquatic and compost organisms. According to current paradigms of ecotoxicology, these symptoms have to be considered adverse, because their compensation consumes energy which is deducted from the main metabolism. However, the nematode C. elegans looks actively for such stressful environments, and this behavior is only understandable in the light of new paradigms of aging mechanisms, particularly the Green Theory of Aging. In this respect, we discuss the mild HS-mediated stress to aquatic and compost organisms. New empirical findings with HS themselves and HS building blocks appear to be consistent with this emerging paradigm and show that the individual lifespan may be expanded. At present the ecological consequences of these findings remain obscure. However, a multiple-stress resistance may be acquired which improves the individual fitness in a fluctuating environment. CONCLUSIONS: It appears that dissolved HS have to be considered abiotic ecological driving forces, somewhat less obvious than temperature, nutrients, or light. PERSPECTIVES: The understanding of the ecological control by dissolved humic substances is still fragmentary and needs to be studied in more details.     

Sensitivity of two dispersion models (AERMOD and ISCST3) to input parameters for a rural ground-level area source

As of December 2006, the American Meteorological Society/U.S. Environmental Protection Agency (EPA) Regulatory Model with Plume Rise Model Enhancements (AERMOD-PRIME; hereafter AERMOD) replaced the Industrial Source Complex Short Term Version 3 (ISCST3) as the EPA-preferred regulatory model. The change from ISCST3 to AERMOD will affect Prevention of Significant Deterioration (PSD) increment consumption as well as permit compliance in states where regulatory agencies limit property line concentrations using modeling analysis. Because of differences in model formulation and the treatment of terrain features, one cannot predict a priori whether ISCST3 or AERMOD will predict higher or lower pollutant concentrations downwind of a source. The objectives of this paper were to determine the sensitivity of AERMOD to various inputs and compare the highest downwind concentrations from a ground-level area source (GLAS) predicted by AERMOD to those predicted by ISCST3. Concentrations predicted using ISCST3 were sensitive to changes in wind speed, temperature, solar radiation (as it affects stability class), and mixing heights below 160 m. Surface roughness also affected downwind concentrations predicted by ISCST3. AERMOD was sensitive to changes in albedo, surface roughness, wind speed, temperature, and cloud cover. Bowen ratio did not affect the results from AERMOD. These results demonstrate AERMOD's sensitivity to small changes in wind speed and surface roughness. When AERMOD is used to determine property line concentrations, small changes in these variables may affect the distance within which concentration limits are exceeded by several hundred meters.     

Characterizing ammonia emissions from swine farms in eastern North Carolina: part 1--conventional lagoon and spray technology for waste treatment

Ammonia (NH3) fluxes from waste treatment lagoons and barns at two conventional swine farms in eastern North Carolina were measured. The waste treatment lagoon data were analyzed to elucidate the temporal (seasonal and diurnal) variability and to derive regression relationships between NH3 flux and lagoon temperature, pH and ammonium content of the lagoon, and the most relevant meteorological parameters. NH3 fluxes were measured at various sampling locations on the lagoons by a flowthrough dynamic chamber system interfaced to an environmentally controlled mobile laboratory. Two sets of open-path Fourier transform infrared (FTIR) spectrometers were also used to measure NH3 concentrations for estimating NH3 emissions from the animal housing units (barns) at the lagoon and spray technology (LST) sites. Two different types of ventilation systems were used at the two farms. Moore farm used fan ventilation, and Stokes farm used natural ventilation. The early fall and winter season intensive measurement campaigns were conducted during September 9 to October 11, 2002 (lagoon temperature ranged from 21.2 to 33.6 degrees C) and January 6 to February 2, 2003 (lagoon temperature ranged from 1.7 to 12 degrees C), respectively. Significant differences in seasonal NH3 fluxes from the waste treatment lagoons were found at both farms. Typical diurnal variation of NH3 flux with its maximum value in the afternoon was observed during both experimental periods. Exponentially increasing flux with increasing surface lagoon temperature was observed, and a linear regression relationship between logarithm of NH3 flux and lagoon surface temperature (T1) was obtained. Correlations between lagoon NH3 flux and chemical parameters, such as pH, total Kjeldahl nitrogen (TKN), and total ammoniacal nitrogen (TAN) were found to be statistically insignificant or weak. In addition to lagoon surface temperature, the difference (D) between air temperature and the lagoon surface temperature was also found to influence the NH3 flux, especially when D > 0 (i.e., air hotter than lagoon). This hot-air effect is included in the statistical-observational model obtained in this study, which was used further in the companion study (Part II), to compare the emissions from potential environmental superior technologies to evaluate the effectiveness of each technology.     

Trends in snowpack chemistry and comparison to National Atmospheric Deposition Program results for the Rocky Mountains, US, 1993–2004

Seasonal snowpack chemistry data from the Rocky Mountain region of the US was examined to identify long-term trends in concentration and chemical deposition in snow and in snow-water equivalent. For the period 1993–2004, comparisons of trends were made between 54 Rocky Mountain Snowpack sites and 16 National Atmospheric Deposition Program wetfall sites located nearby in the region. The region was divided into three subregions: Northern, Central, and Southern. A non-parametric correlation method known as the Regional Kendall Test was used. This technique collectively computed the slope, direction, and probability of trend for several sites at once in each of the Northern, Central, and Southern Rockies subregions. Seasonal Kendall tests were used to evaluate trends at individual sites.Significant trends occurred during the period in wetfall and snowpack concentrations and deposition, and in precipitation. For the comparison, trends in concentrations of ammonium, nitrate, and sulfate for the two networks were in fair agreement. In several cases, increases in ammonium and nitrate concentrations, and decreases in sulfate concentrations for both wetfall and snowpack were consistent in the three subregions. However, deposition patterns between wetfall and snowpack more often were opposite, particularly for ammonium and nitrate. Decreases in ammonium and nitrate deposition in wetfall in the central and southern rockies subregions mostly were moderately significant (p<0.11) in constrast to highly significant increases in snowpack (p<0.02). These opposite trends likely are explained by different rates of declining precipitation during the recent drought (1999–2004) and increasing concentration. Furthermore, dry deposition was an important factor in total deposition of nitrogen in the region. Sulfate deposition decreased with moderate to high significance in all three subregions in both wetfall and snowpack. Precipitation trends consistently were downward and significant for wetfall, snowpack, and snow-telemetry data for the central and southern rockies subregions (p<0.03), while no trends were noted for the Northern Rockies subregion.