In vitro pesticide degradation in turfgrass soil incubated under open and sealed conditions

Degradation of selected pesticides was conducted in a turfgrass soil from a golf course under open (i.e., allowing gas exchange with atmosphere) and sealed systems. The time required for 50% of the initial dose of fenitrothion (O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate), diazinon (O,O-dimethyl O-2-isopropyl-6-methylpyrimidin4-yl phosphorothioate), iprodione [3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxo-imidazolidine-1-carboxamide], mecoprop [(RS)-2-(4-chloro-otolyloxy)propionic acid], and asulam (4-aminophenylsulfonyl-carbamate) to dissipate (half-life, t 1/2) was less than 2 wk under both conditions. The t 1/2 values of dithiopyr (S,S'-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoro-methylpyridine-3,5-dicarbothioate) were 324 and 185 d under the open and sealed conditions, respectively. The t 1/2 values of isoprothiolane (di-isopropyl 1,3-dithiolan-2-ylidene-malonate), flutolanil (alpha,alpha,alpha-trifluoro-3'-isopropoxy-o-toluanilide), and benefin (N-butyl-N-ethyl-alpha,alpha,alpha-trifluoro-2,6-dinitro-p-toluidine) under the open conditions were 154, 336, and 47 d, respectively. The t 1/2 values of these pesticides increased slightly under the sealed conditions. The t 1/2 values of terbutol (2,6-di-tert-butyl-4-methylphenyl N-methycarbamate) and one of the major degradation products, N-demethyl-terbutol (2,6-di-tert-butyl-4-methylphenyl carbamate), were 182 and 291 d under the open conditions and increased by six- and threefold under the sealed conditions, respectively. The degradation system under the sealed conditions could characterize the persistence of terbutol and N-demethyl-terbutol, which were the most persistent in the field.     

Effect of nonylphenol surfactants on fungi following the application of sewage sludge on agricultural soils

The effect of nonylphenol on fungi following the application of contaminated sewage sludge on agricultural soil was studied in laboratory experiments. Nonylphenol bioavailability and adsorption were determined in the soil alone and soil-sludge mixtures. Mixing the soil with sludge made it possible to measure the nonylphenol concentration in the soil solution, which comprised between 6.6 x 10(-6) and 3.8 x 10(-7) M, according to the sludge. We then examined the dose-response relationship between nonylphenol concentration in the culture medium and both biomass production and germination rate of the spores from several strains of filamentous fungi. When applied in this range of concentration, nonylphenol was without noticeable short-term effect on these endpoints. Long-term exposure of fungi to nonylphenol was also assessed. The most intensive effect was a strong stimulation of spore production and germination in Fusarium oxysporum Schlechtendahl. Biomass production by the Fusarium strains also increased. Finally, nonylphenol was shown to induce laccase production in Trametes versicolor. We conclude that the potential of nonylphenol to adversely affect several soil fungi remains low.     

Impact of methylene chloride on microorganisms and phenanthrene mineralization in soil

This study investigated the effects of the quantity of methylene chloride, used as a carrier solvent for phenanthrene when added to soil, on phenanthrene mineralization kinetics, soil phospholipid fatty add profiles (PLFA), and phenanthrene distribution. Methylene chloride dosages of 25 microL/g soil or more resulted in an enrichment of saturated PLFAs, suggesting soil microorganisms had adjusted their cell membranes in response to the solvent. A greater fraction of phenanthrene mineralized when spiked in 5 microL/g than in 25 microL/g methylene chloride suggesting that the methylene chloride became toxic to phenanthrene-degrading organisms in soil. Phenanthrene was more equally distributed among 0.1 g soil subsamples if spiked in 25 than 5 or 1 microL methylene chloride per gram soil. Thus the amount of methylene chloride used to spike phenanthrene in soil strongly impacted the mineralization kinetics, phenanthrene distribution, and microbial community in soil. Because a variety of spiking methods are used in biodegradation research, scientists should consider the quantity of solvents used when comparing results among different studies.     

Thermal degradation kinetics and mechanisms of Posidonia Oceanica under inert and oxidative atmospheres

The thermal degradation characteristics of Posidonia Oceanica (PO), a marine biomass abundantly available on the coastal zone of the Mediterranean Basin, were investigated using thermogravimetric analysis under inert and oxidative atmospheres. The kinetic parameters of the both thermal degradations conditions were determined using n-reaction order model. Coats–Redfern and Phadnis–Deshpande methods were used to discuss the probable degradation mechanisms. Results showed that PO is an attractive alternative for energy production owing to its elevated heating value. Moreover, PO thermal degradation follows the usual shape of biomass decomposition. Hence, under inert atmosphere, its thermal degradation had two different stages after moisture release. The first stage corresponded to the volatiles release while the second stage corresponded to the char formation. The solid-state decomposition mechanisms followed by the devolatilization step of PO were two or three dimensional diffusion controlled reaction. However, the decomposition mechanism during PO char formation corresponded to a nucleation and growth mechanism. Under oxidative atmosphere, two stages were also observed corresponding to volatiles release and char combustion, respectively. The solid-state mechanism of volatiles release followed three dimensional diffusion controlled reaction while the char combustion mechanism corresponded to a contracting area phase boundary controlled reaction.     

Herbicides and herbicide degradation products in Upper Midwest agricultural streams during August base-flow conditions

Herbicide concentrations in streams of the U.S. Midwest have been shown to decrease through the growing season due to a variety of chemical and physical factors. The occurrence of herbicide degradation products at the end of the growing season is not well known. This study was conducted to document the occurrence of commonly used herbicides and their degradation products in Illinois, Iowa, and Minnesota streams during base-flow conditions in August 1997. Atrazine, the most frequently detected herbicide (94%), was present at relatively low concentrations (median 0.17 microg L(-1)). Metolachlor was detected in 59% and cyanazine in 37% of the samples. Seven of nine compounds detected in more than 50% of the samples were degradation products. The total concentration of the degradation products (median of 4.4 microg L(-1)) was significantly greater than the total concentration of parent compounds (median of 0.26 microg L(-1)). Atrazine compounds were present less frequently and in significantly smaller concentrations in streams draining watersheds with soils developed on less permeable tills than in watersheds with soils developed on more permeable loess. The detection and concentration of triazine compounds was negatively correlated with antecedent rainfall (April-July). In contrast, acetanalide compounds were positively correlated with antecedant rainfall in late spring and early summer that may transport the acetanalide degradates into ground water and subsequently into nearby streams. The distribution of atrazine degradation products suggests regional differences in atrazine degradation processes.     

Effects of suspended sediment on the biodegradation and mineralization of phenanthrene in river water

High suspended sediment (SPS) concentration commonly exists in many Asian rivers. Furthermore, climate change can cause high floods and lead to the resuspension of sediments and soil erosion, resulting in high SPS concentration in many natural waters. This research studied the impact of the presence of SPS and organic C composition of SPS on the biodegradation and mineralization of phenanthrene (PHE). Three sediments, including original sediment (OS), 375 degrees C (S375), and 600 degrees C (S600) combusted sediment, were studied. A flask-based 14C-respirometer system was applied to study the mineralization of [14C]PHE by Agrobacterium sp. The mineralization rate of PHE in the absence of SPS was significantly lower than that with the presence of OS and S600 but higher than that with S375, suggesting that the effect of the presence of sediment on PHE mineralization depended on its organic C composition. The residual levels of PHE in the S375 and OS systems were about 1.5 times that of the S600 system after incubation for 2 d. After 26-d incubation, the mineralization rates of PHE were 34.64, 29.40, and 14.00% in the OS, S600, and S375 systems, respectively. The first-order rate constants of the OS and S600 systems were about three times that of the S375 system. The net influence of SPS on the biodegradation and mineralization rates of PHE was dependent on its effects on compound bioavailability and bacteria population. This study suggested that black C played a key role in reducing the mineralization rates of PHE in sediments-even without aging.     

Ecotoxic effect of phenanthrene on nitrifying bacteria in soils of different properties

Information on ecotoxicity of organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), in terrestrial environment is needed for establishing soil quality criteria and for risk assessment purposes. An ecotoxic effect of a model PAH compound (phenanthrene) toward soils microorganisms (nitrifying bacteria) was evaluated in 50 different soils. The soil samples were collected from agricultural land in four regions of Poland with varying levels of industrialization (Slaskie, Dolnoslaskie, Podlaskie, and Lubelskie voievodeships). Soils were characterized for basic physicochemical properties (texture, organic matter content, pH(KCl), total nitrogen content, total sorption capacity) and the content of contaminants including PAHs (73-800 microg kg(-1)), Pb (6-720 mg kg(-1)), and Zn (9-667 mg kg(-1)). Ecotoxicity of phenanthrene (applied at 10, 100, 500, and 1000 mg kg(-1)) to soils microorganisms was evaluated in laboratory studies in control conditions (incubation of soils for 7 d at 20 +/- 2 degrees C). Nitrification potential was used as the ecotoxicity measurements end point. The EC50 values (146-1670 mg kg(-1)) calculated from the square root-X linear regression model differed significantly in various soils, although it was difficult to establish a causative relationship between soil physicochemical characteristic and phenanthrene toxicity. A significant factor in the assessment of soils vulnerability to the effect of phenanthrene was level of soil contamination, particularly with PAHs. Soils with previous contamination were more susceptible (mean EC50, 325 mg kg(-1)) than soils from uncontaminated, rural areas (mean EC50, 603 mg kg(-1)).     

Effect of environmental conditions on perceived psychological restorativeness of coastal parks

We investigated the hypothesis that perception of psychological restorativeness during visits to coastal parks is modified by objective and perceived environmental conditions. Visitors (n = 1153) to California beaches completed a survey on perceived weather, environmental quality, and perceived restorativeness. We used generalized ordinal logistic models to estimate the association between environmental parameters and odds of perceiving higher levels of restorativeness. Visitors perceived greater restorativeness at beaches when ambient temperatures were at or below mean monthly temperatures and during low tides. The odds of perceiving the environment as more psychologically restorative were three times greater when visiting on days defined by government policy as having good air quality (OR = 3.25; CI: 1.69–6.28). Visitors’ perception of air (OR = 1.56; CI: 1.14–2.18) and water quality (OR = 1.78; CI: 1.28–2.49) also affected perceived restorativeness; with perceived healthy days more restorative. Warmer temperatures with less space due to sea level rise and poor environmental quality will restrict restorative experiences in recreational facilities designed for urban populations.     

Microbial reduction of hexavalent chromium under vadose zone conditions

Hexavalent chromium [Cr(VI)] is a common contaminant associated with nuclear reactors and fuel processing. Improper disposal at facilities in and and semiarid regions has contaminated underlying vadose zones and aquifers. The objectives of this study were to assess the potential for immobilizing Cr(VI) using a native microbial community to reduce soluble Cr(VI) to insoluble Cr(III) under conditions similar to those in the vadose zone, and to evaluate the potential for enhancing biological Cr(VI) reduction through nutrient addition. Batch microcosm and unsaturated flow column experiments were performed. Native microbial communities in subsurface sediments with no prior Cr(VI) exposure were shown to be capable of Cr(VI) reduction. In both the batch and column experiments, Cr(VI) reduction and loss from the aqueous phase were enhanced by adding high levels of both nitrate (NO3-) and organic C (molasses). Nutrient amendments resulted in up to 87% reduction of the initial 67 mg L(-1) Cr(VI) in an unsaturated batch experiment. Molasses and nitrate additions to 15 cm long unsaturated flow columns receiving 65 mg L(-1) Cr(VI) resulted in microbially mediated reduction and immobilization of 10% of the Cr during a 45-d experiment. All of the immobilized Cr was in the form of Cr(III), as shown by XANES analysis. This suggests that biostimulation of microbial Cr(VI) reduction in vadose zones by nutrient amendment is a promising strategy, and that immobilization of close to 100% of Cr contamination could be achieved in a thick vadose zone with longer flow paths and longer contact times than in this experiment.     

Formation of pi-pi complexes between phenanthrene and model pi-acceptor humic subunits

Pi-pi interactions may play a role in association of aromatic compounds with natural organic substances. Complexation in aqueous solvents was studied between the pi donor, phenanthrene (PHEN), and model pi-acceptor species (quinones and N-heteroaromatic cations) that represent certain functional units of humic substances. Charge-transfer bands in the UV and ring-current shifts in the proton nuclear magnetic resonance (NMR) spectrum confirmed the face-to-face, pi-pi donor-acceptor nature of the bond. Complexation constants were obtained by the solubility enhancement method; solubility enhancements up to 2500 were found. Ruled out as predominant causes of solubility enhancement were monomer desolvation (i.e., "hydrophobic" effects), partitioning into micelles, pi-cation interactions, and pi-hydrogen bonding. Acceptor self-stacking and formation of higher-stoichiometry acceptor-donor complexes had to be considered in evaluating donor-acceptor equilibria in some cases. The affinity of acceptor for PHEN followed the order of increasing pi-acceptor strength and varied strongly with the degree of ring overlap with PHEN. Complexation between PHEN and the free solution faces of an acceptor was less favorable than intercalation of PHEN between two acceptor units in a stack. A positive hydrophobic effect on complexation was evident in water mixtures with acetone or methanol and found to correlate with the number of faces of PHEN requiring desolvation to form the complex. When hydrophobic effects are subtracted out, the pi-pi complex actually becomes favored as the solvent water content and polarity decline. The results suggest that phenanthrene, and by implication other donor aromatic compounds, are capable of forming pi-pi interactions with appropriate humic fragments.     

Effect of corn root exudates on the degradation of atrazine and its chlorinated metabolites in soils

DIMBOA (3,4-dihydro-2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), a major benzoxazinone of Poaceae plants, was isolated and purified from corn seedlings. The effect of isolated and purified DIMBOA on the degradation of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine], and its toxic breakdown products, desethylatrazine [2-chloro-4-amino-6-(isopropylamino)-s-triazine; DEA] and desisopropylatrazine [2-chloro-4-(ethylamino)-6-amino-s-triazine; DIA], was studied in the absence of plants using batch experiments, while the effect of corn root exudates on these compounds was determined in hydroponic experiments. Degradation experiments were performed in the presence and absence of 50 microM, 1 mM, or 5 mM DIMBOA resulting in ratios of DIMBOA to pesticide of 1:1, 20:1, and 100:1. We observed a 100% degradation of atrazine to hydroxyatrazine within 48 h at a ratio of DIMBOA to atrazine of 100:1. DIMBOA had the largest effect on atrazine, while it was about three times less effective on DEA and DIA. Corn (Zea mays L. cv. LG 2185) was exposed to 10 mg L(-1) of either atrazine, DEA, or DIA for 11 d in a growth chamber experiment. Up to 4.3 micromol L(-1) d(-1) of hydroxyatrazine were formed in the nutrient solutions by plants exposed to atrazine, while the formation of hydroxylated metabolites from plants exposed to DEA and DIA was smaller and also delayed. The formation of hydroxylated metabolites increased in the solution with plant age in all atrazine, DEA, and DIA treatments. HMBOA (3,4-dihydro-2-hydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), the lactam precursor of DIMBOA, and a tentatively identified derivative of MBOA (2,3-dihydro-6-methoxy-benzoxazol-2-one) were detected in the corn root exudates. Mass balance calculations revealed that up to 30% of the disappearance of atrazine and DEA, and up to 10% of DIA removal from the solution medium in our study could be explained by the formation of hydroxylated metabolites in the solution itself. Our results show that higher plants such as corn have the potential to promote the hydrolysis of triazine residues in soils by exudation of benzoxazinones.     

Aluminum effect on dissolution and precipitation under hyperalkaline conditions: II. Solid phase transformations

The high-level radioactive, Al-rich, concentrated alkaline and saline waste fluids stored in underground tanks have accidentally leaked into the vadose zone at the Hanford Site in Washington State. In addition to dissolution, precipitation is likely to occur when these waste fluids contact the sediments. The objective of this study was to investigate the solid phase transformations caused by dissolution and precipitation in the sediments treated with solutions similar to the waste fluids. Batch experiments at 323 K were conducted in metal- and glass-free systems under CO2 and O2 free conditions. Results from X-ray diffraction (XRD), quantitative X-ray diffraction (QXRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and energy dispersive X-ray fluorescence spectroscopy (EDXRF) indicated that significant solid phase transformations occurred in the sediments contacted with Al-rich, hyperalkaline, and saline solutions. The XRD and QXRD analyses confirmed that smectite and most likely biotite underwent dissolution. The SEM and the qualitative EDS analyses confirmed the formation of alumino-silicates in the groups of cancrinite and probably sodalite. The morphology of the alumino-silicates secondary phases changed in response to changes in the Si/Al aqueous molar ratio. The transformations in the sediments triggered by dissolution (weathering of soil minerals) and precipitation (formation of secondary phases with high specific surface area and probably high sorption capacities) may play a significant role in the immobilization and ultimate fate of radionuclides and contaminants such as Cs, Sr, and U in the Hanford vadose zone.     

Aluminum effect on dissolution and precipitation under hyperalkaline conditions: I. Liquid phase transformations

Substantial amounts of self-boiling, Al-rich, hyperalkaline, and saline high-level waste fluids (HLWF) were deposited to the vadose zone at the Hanford Site, in Washington State. The objective of this study was to investigate the effects of similar fluids on the extent of dissolution and precipitation in the sediments. Metal- and glass-free systems were used to conduct batch experiments at 323 K under CO2 and O2 free conditions. Base-induced dissolution of the soil minerals was rapid in the first 48 h as indicated by immediate releases of Si and Fe into the soil solution. Potassium release lagged behind and dissolution of K-bearing minerals (mica and K-feldspar) proceeded faster only after 2 to 3 d of the experiment. Silicon and Fe release exhibited high dependence on aqueous [Al] (rate orders <-1), because Al decreased free OH concentration in the contact solution and probably inhibited soil mineral dissolution. Initial K release exhibited low dependence on [Al] (fractional rate orders). Initial dissolution rates calculated based on Si release varied with aqueous [Al] from 29.47 to 4.35 x 10(-12) mol m(-2) s(-1). Aluminum participated in the formation of the secondary phases (precipitation rates of 10(-8) mol s(-1)) but the overall precipitation rate of alumino-silicate secondary phases was probably controlled by aqueous [Si] (rates of 10(-9), and rate constants between 0.0054 and 0.0084 h(-1)). The changes in the soil solution chemistry (release of K, Si, Fe, and other elements) may play a significant role in the fate of radionuclides and contaminants like Cs, Sr, Cr, and U in the Hanford sediments.     

Sampling silica and ferrihydrite colloids with fiberglass wicks under unsaturated conditions

The suitability of passive capillary samplers (PCAPS) for collection of representative colloid samples under partially saturated conditions was evaluated by investigating the transport of negatively and positively charged colloids in fiberglass wicks. A synthetic pore water solution was used to suspend silica microspheres (330 nm in diameter) and ferrihydrite (172 nm in diameter) for transport experiments on fiberglass wicks. Breakthrough curves were collected for three unsaturated flow rates with silica microspheres and one unsaturated flow rate with ferrihydrite colloids. A moisture characteristic curve, relating tensiometer measurements of matric potential to moisture content, was developed for the fiberglass wick. Results indicate that retention of the silica and the ferrihydrite on the wick occurred; that is, the wicks did not facilitate quantitative sampling of the colloids. For silica microspheres, 90% of the colloids were transmitted through the wicks. For ferrihydrite, 80 to 90% of the colloids were transmitted. The mechanisms responsible for the retention of the colloids on the fiberglass wicks appeared to be physicochemical attachment and not thin-film, triple-phase entrapment, or mechanical straining. Visualization of pathways by iron staining indicates that flow is preferential at the center of twisted bundles of filaments. Although axial preferential flow in PCAPS may enhance their hydraulic suitability for sampling mobile colloids, we conclude that without specific preparation to reduce attachment or retention, fiberglass wicks should only be used for qualitative sampling of pore water colloids.     

Pulverized coal stream ignition delay under conventional and oxy-fuel combustion conditions

The coal stream ignition process is critical to the performance of modern pulverized coal burners, particularly when operating under novel conditions such as experienced in oxy-fuel combustion. However, experimental studies of coal stream ignition are lacking, and recent modeling efforts have had to rely on comparisons with a single set of experiments in vitiated air. To begin to address this shortfall, we have conducted experiments on the ignition properties of two U.S. and two Chinese coals in a laminar entrained flow reactor. Most of the measurements focused on varying the coal feed rate for furnace temperatures of 1230–1320 K and for 12–20 vol.% O₂ in nitrogen. The influence of coal feed rate on ignition with a carbon dioxide diluent was also measured for 20 vol.% O₂ at 1280 K. A second set of measurements was performed for ignition of a fixed coal feed rate in N₂ and CO₂ environments at identical furnace temperatures of 1200 K, 1340 K, and 1670 K. A scientific CCD camera equipped with a 431 nm imaging filter was used to interrogate the ignition process. Under most conditions, the ignition delay decreased with increasing coal feed rate until a minimum was reached at a feed rate corresponding to a particle number density of approximately 4 × 10⁹ m^?3 in the coal feed pipe. This ignition minimum corresponds to a cold flow group number, G, of ～0.3. At higher coal feed rates the ignition delay increased. The ignition delay time was shown to be very sensitive to (a) the temperature of the hot coflow into which the coal stream is introduced, and (b) the coal particle size. The three high volatile bituminous coals showed nearly identical ignition delay as a function of coal feed rate, whereas the subbituminous coal showed slightly greater apparent ignition delay. Bath gas CO₂ content was found to have a minor impact on ignition delay.     

Predicting soil fumigant air concentrations under regional and diverse agronomic conditions

SOFEA (SOil Fumigant Exposure Assessment system; Dow AgroSciences, Indianapolis, IN) is a new stochastic numerical modeling tool for evaluating and managing human inhalation exposure potential associated with the use of soil fumigants. SOFEA calculates fumigant concentrations in air arising from volatility losses from treated fields for large agricultural regions using multiple transient source terms (treated fields), geographical information systems (GIS) information, agronomic specific variables, user-specified buffer zones, and field reentry intervals. A modified version of the USEPA Industrial Source Complex Short Term model (ISCST3) is used for air dispersion calculations. Weather information, field size, application date, application rate, application type, soil incorporation depth, pesticide degradation rates in air, tarp presence, field retreatment, and other sensitive parameters are varied stochastically using Monte Carlo techniques to mimic region and crop specific agronomic practices. Regional land cover, elevation, and population information can be used to refine source placement (treated fields), dispersion calculations, and risk assessments. This paper describes the technical algorithms of SOFEA and offers comparisons of simulation predictions for the soil fumigant 1,3-dichloropropene (1,3-D) to actual regional air monitoring measurements from Kern, California. Comparison of simulation results to daily air monitoring observations is remarkable over the entire concentration distribution (average percent deviation of 44% and model efficiency of 0.98), especially considering numerous inputs such as meteorological conditions for SOFEA were unavailable and approximated by neighboring regions. Both current and anticipated and/or forecasted fumigant scenarios can be simulated using SOFEA to provide risk managers and product stewards the necessary information to make sound regulatory decisions regarding the use of soil fumigants in agriculture.     

Impact of climatic and soil conditions on environmental fate of atrazine used under plantation forestry in Australia

We studied the leaching and dissipation of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-s-triazine) and its two principal metabolites (desethylatrazine and desisopropylatrazine) for more than two years through soil profiles at five forestry sites across Australia (representing subtropical, temperate and Mediterranean climatic conditions with rainfall ranging from 780 to 1536 mm yr^?1). Following atrazine applications at local label rates, soil cores were collected at regular intervals (up to depths of 90–150 cm), and the residues of the three compounds in soil were analysed in composite samples using liquid chromatography. Bromide was applied simultaneously with atrazine to follow the movement of the soil water. While bromide ion rapidly leached through the entire profile, in most cases the bulk of atrazine, desethylatrazine and desisopropylatrazine remained in the top 45 cm of the soil profile. However, a small fraction of residue moved deeper into the soil profile and at a subtropical site (Toolara) trace levels (ng L^?1) of atrazine and one of its metabolites (DEA) were detected in perched groundwater located at a depth of 1.8 m. Data on the total residues of atrazine in soil profiles from all sites except the Tasmanian site fitted a first-order decay model. The half-life of atrazine in surface soils at the subtropical sites (Toolara and Imbil) ranged from 11 to 21 days. Four separate applications of atrazine at Toolara resulted in a narrow range of half-lives (16 ± 3.6 days), confirming relatively rapid dissipation of atrazine under subtropical conditions (Queensland). In contrast, a prominent biphasic pattern of initial rapid loss followed by very slow phase of degradation of atrazine was observed under the colder temperate climate of Highclere (Tasmania). The data showed that while its 50% (DT₅₀) loss occurred relatively rapidly (36 days), more than 10% of herbicide residue was still detectable in the profile even a year after application (DT₉₀ = 375 days). The rate of dissipation of atrazine at warm subtropical Queensland sites (Imbil and Toolara) was 2–3 times faster than sites located in colder climate of Tasmania. The marked contrast in DT₅₀ values between subtropical and temperate sites suggest that climatic conditions (soil temperature) is one of the key factors affecting atrazine dissipation. At the Tasmanian site, the combination of leaching of the herbicide in subsoil and slower microbial activity at cooler temperatures would have caused a longer persistence of atrazine.     

Phosphorus sorption characteristics of estuarine sediments under different redox conditions

Phosphorus (P) plays a major role in eutrophication of aquatic systems. Estuarine sediments could function as sources or sinks for P to the overlying water column depending upon their physico-chemical characteristics. Understanding of P sorption phenomena in estuarine sediments is important in regulating the P availability in estuaries. Phosphorus sorption characteristics of sediments from the Indian River Lagoon, Florida, USA, were determined to examine the role of selected physico-chemical properties of the sediments on soluble reactive P status in estuary water. Mean equilibrium P concentrations (EPCo) of 0.75 mg L(-1) and mean P sorption maxima (Smax) of 32.2 mg kg(-1) were obtained under anaerobic conditions, compared with EPCo of 0.05 mg L(-1) and Smax of 132.7 mg kg(-1) under aerobic conditions. The higher EPCo values under anaerobic conditions and the greater Smax values under aerobic conditions were associated with amorphous and poorly crystalline iron. These results suggest that sediments enriched with amorphous and poorly crystalline forms of iron act as an excellent reservoir for P by adsorbing excessive P in aerobic sediment zones and releasing it upon burial under anaerobic conditions. This study also indicates that P compounds in sediments independently maintain equilibrium with P in solutions. Thus, heterogeneous systems like soil and sediment simply behave as a mixture of homogeneous surfaces as far as their P sorption characteristics are concerned, and hence can be successfully described by the Langmuir and Freundlich models.     

Photodegradation of selected herbicides in various natural waters and soils under environmental conditions

The photochemical degradation of herbicides belonging to different chemical groups has been investigated in different types of natural waters (ground, river, lake, marine) and distilled water as well as in soils with different texture and composition. Studied herbicides and chemical groups included atrazine, propazine, and prometryne (s-triazines); propachlor and propanil (acetanilides); and molinate (thiocarbamate). The degradation kinetics were monitored under natural conditions of sunlight and temperature. Photodegradation experiments were performed in May through July 1998 at low concentrations in water samples (2-10 mg/L) and soil samples (5-20 mg/kg), which are close to usual field dosage. The photodegradation rates of all studied herbicides in different natural waters followed a pseudo-first order kinetics. The half-lives of the selected herbicides varied from 26 to 73 calendar days in waters and from 12 to 40 d in soil surfaces, showing that the degradation process depends on the constitution of the irradiated media. The presence of humic substances in the lake, river, and marine water samples reduces degradation rates in comparison with the distilled and ground water. On the contrary, the degradation in soil is accelerated as the percentage of organic matter increases. Generally, the photodegradation process in soil is faster than in water. The major photodegradation products identified by using gas chromatography-mass spectrometry (GC-MS) techniques were the hydroxy and dealkylated derivatives for s-triazines, the dechlorinated and hydroxy derivative for the anilides, and the keto-derivative for the thiocarbamate, indicating a similar mode of degradation for each chemical category.     

Fate of pesticides in tropical soils of Brazil under field conditions

The potential of pesticides for nonpoint ground water pollution depends on their dissipation and leaching behavior in soils. We investigated the fate of 10 pesticides in two tropical soils of contrasting texture in the Brazilian Cerrado region near Cuiabá during an 80-d period, employing topsoil dissipation studies, soil core analyses, and lysimeter experiments. Dissipation of pesticides was rapid, with field half-lives ranging from 0.8 to 20 d in Ustox and 0.6 to 11.8 d in Psamments soils. Soil core analyses showed progressive leaching of polar pesticides in Psamments, whereas in Ustox pesticides were rapidly transported to 40 cm soil depth regardless of their sorption properties, suggesting that leaching was caused by preferential flow. In lysimeter experiments (35 cm soil depth), cumulative leaching was generally low, with < or = 0.02% and < or = 0.19% of the applied amounts leached in Ustox and Psamments, respectively. In both soils, all pesticides but the pyrethroids were detected in percolate at 35 cm soil depth within the first 6 d after application. Cumulative efflux and mean concentrations of pesticides in percolate were dosely correlated with their Groundwater Ubiquity Score (GUS). The presence of alachlor (2-chloro-2', 6'-diethyl-N-methoxymethylacetanilide), atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], simazine [2-chloro-4,6-bis(ethylamino)-1,3,5-triazine], and trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) throughout the soil profile and in percolate of wick lysimeters at 95 cm soil depth indicated that a nonpoint pollution of ground water resources in tropical Brazil cannot be ruled out for these substances.