Mineralization of soil-aged isoproturon and isoproturon metabolites by Sphingomonas sp. strain SRS2

The aim of the study was to determine the effect of aging of the herbicide isoproturon and its metabolites monodesmethyl-isoproturon and 4-isopropyl-aniline in agricultural soil on their availability to the degrading bacterium Sphingomonas sp. strain SRS2. The 14C-ring-labeled isoproturon, monodesmethyl-isoproturon, and 4-isopropyl-aniline were added to sterilized soil and stored for 1, 49, 71, or 131 d before inoculation with strain SRS2. The availability of the compounds was estimated from the initial mineralization and the amount of 14CO2 recovered after 120 d of incubation. Aging in soil for 131 d reduced the initial mineralization of isoproturon and monodesmethyl-isoproturon and, in the case of isoproturon, also reduced the recovery of 14CO2. Initial mineralization and recovery of 14CO2 from aged 4-isopropyl-aniline were slightly reduced, but less 14CO2 was generally produced than with isoproturon or monodesmethyl-isoproturon. Thus, recovery of 14CO2 from 14C-isoproturon and 14C-monodesmethyl-isoproturon was 50.7 to 64.4% of the initially added 14C, while recovery from 14C-4-isopropyl-aniline was only 11.7 to 17.0%. Sorption measurements revealed similar Freundlich constants (K(f)) for isoproturon and monodesmethyl-isoproturon, whereas K(f) for 4-isopropyl-aniline was more than fivefold greater. The findings imply that in soil, partial degradation of isoproturon to 4-isopropyl-aniline may lead to reduced mineralization of the herbicide due to sorption of the aniline moiety.     

Phosphorus flux from bottom sediments in Lake Eucha, Oklahoma

Phosphorus inputs into reservoirs include external sources from the watershed and internal sources from the reservoir bottom sediments. This study quantified sediment P flux in Lake Eucha, northeastern Oklahoma, USA, and evaluated the effectiveness of chemical treatment to reduce sediment P flux. Six intact sediment-water columns were collected from three sites in Lake Eucha near the reservoir channel at depths of 10 to 15 m. Three intact sediment and water columns from each site were incubated for 21 d at approximately 22 degrees C under aerobic conditions, and three were incubated under anaerobic conditions (N2 with 300 ppm CO2); sediment P flux was estimated over the 21 d for each core. The overlying water in the cores was bubbled with air for approximately 1 wk and then treated with aluminum sulfate (alum). The cores were incubated at approximately 22 degrees C for an additional 14 d under aerobic or anaerobic conditions, and sediment P flux after alum treatment was estimated for each core. Sediment P flux was approximately four times greater under anaerobic conditions compared with aerobic conditions. Alum treatment of the intact sediment-water columns reduced (8x) sediment P flux under anaerobic conditions. Internal P flux (1.03 and 4.40 mg m(-2) d(-1) under aerobic and anaerobic conditions, respectively) was greater than external P flux (0.13 mg m(-2) d(-1)). The internal P load (12 Mg yr(-1)) from reservoir bottom sediments was almost 25% of the external P load (approximately 48 Mg yr(-1)) estimated using a calibrated watershed model.     

Influence of aerobic and anaerobic conditions on survival of Escherichia coli O157:H7 and Salmonella enterica serovar Typhimurium in Luria-Bertani broth, farm-yard manure and slurry

The influence of aerobic and anaerobic conditions on the survival of the enteropathogens Escherichia coli O157:H7 and Salmonella serovar Typhimurium was investigated in microcosms with broth, cattle manure or slurry. These substrates were inoculated with a green fluorescent protein transformed strain of the enteropathogens at 10(7) cells g(-1) dry weight. Survival data was fitted to the Weibull model. The survival curves in aerobic conditions generally showed a concave curvature, while the curvature was convex in anaerobic conditions. The estimated survival times showed that E. coli O157:H7 survived significantly longer under anaerobic than under aerobic conditions. Survival ranged from approximately. 2 weeks for aerobic manure and slurry to more than six months for anaerobic manure at 16 °C. On average, in 56.3% of the samplings, the number of recovered E. coli O157:H7 cells by anaerobic incubation of Petri plates was significantly (p < 0.05) higher in comparison with aerobic incubation. Survival of Salmonella serovar Typhimurium was not different between aerobic and anaerobic storage of LB broth or manure as well as between aerobic and anaerobic incubation of Petri dishes. The importance of changes in microbial community and chemical composition of manure and slurry was distinguished for the survival of E. coli O157:H7 in different oxygen conditions.     

Effects of glyphosate and two herbicide mixtures on microbial communities in prairie wetland ecosystems: a mesocosm approach

A multitrophic outdoor mesocosm system was used to mimic a wetland ecosystem and to investigate the effects of glyphosate and two herbicide mixtures on wetland microbial communities. The glyphosate concentration used was 1000 times the environmentally relevant concentration (ERC). One herbicide mixture consisted of six auxin-type herbicides (2,4-D, MCPA, clopyralid, dicamba, dichlorprop, mecoprop), each at 1000 times the ERC. The second mixture was comprised of eight herbicides, including the six auxin-type herbicides as well as bromoxynil and glyphosate. For this mixture, a dose-response approach was used to treat mesocosms with the ERCs of each herbicide as the base concentration. Algal biomass and production and bacterial production and numbers for pelagic and attached communities were measured at different times over a 22-d period. The experimental results indicate that the eight-herbicide mixture, even at low concentrations, produced negative effects on microbial communities. Glyphosate on its own suppressed algal biomass and production for the duration of the study in pelagic and biofilm communities. Algal biomass and production, although initially depressed in the auxin-type herbicide treatment, were stimulated from Day 9 until experiment end. Due to their similar modes of action, the effects of this herbicide mixture appear to be a result of concentration addition. Such negative effects, however, were brief, and microbial communities recovered from herbicide exposure. Based on evidence presented in this study, it appears that glyphosate has a higher potential to inhibit primary production and chlorophyll content in pelagic and attached wetland algal communities than the auxin-type herbicide mixture.     

Influence of flooding on phosphorus mobility in manure-impacted soil

Agricultural lands are often used for constructing stormwater treatment areas (STAs) to abate nutrient loading to adjacent aquatic systems. Flooding agricultural lands to create STAs could stimulate a significant release of phosphorus (P) from soil to the water column. To assess the suitability of agricultural lands, specifically those impacted by animal operations, for the construction of STAs, soils from different components of the New Palm-Newcomer dairies (Nubbin Slough Basin, Okeechobee, Florida, USA) were collected by horizon and their P retention and release capacities estimated. In general, P released from A-horizon soil under flooded (anaerobic) conditions was greater than under drained (aerobic) conditions due to redox effect on iron (Fe) and consequent P releases. However, the P released from Bh-horizon soil was greater under aerobic conditions than under anaerobic conditions, possibly due to excessive aluminum (Al) content in the horizon. Double acid-extractable calcium (Ca), magnesium (Mg), Al, and P explained 87% of the variability in P release under aerobic conditions, and 80% of that under anaerobic conditions. The P release maxima indicated a high solubility of P in A-horizon soil from both active and abandoned dairies (13 and 8% of the total P, respectively), suggesting that these soils could function as potential sources of P to the overlying water column when used in STA construction. Preestablishment of vegetative communities or chemical amendment, however, could ameliorate high P flux from soil to the water column.     

Adsorption of pesticides onto quartz, calcite, kaolinite, and alpha-alumina

The fate of pesticides in aquifers is influenced by the small but not insignificant adsorption of pesticides to mineral surfaces. Batch experiments with five pesticides and four minerals were conducted to quantify the contributions to adsorption from different mineral surfaces and compare adsorption characteristics of selected pesticides. Investigated mineral phases included quartz, calcite, kaolinite, and alpha-alumina. Selected pesticides comprised atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea)], mecoprop [(RS)-2-(4-chloro-2-methylphenoxy)propionic acid], 2,4-D (2,4-dichlorophenoxyacetic acid), and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2-dioxide]. Specific surface area and mineral surface charge proved to be important for the adsorption of these pesticides. Detectable adsorption of the anionic pesticides (mecoprop, 2,4-D, and bentazone) was only measured when positive sites were present on the mineral surface. However, when CaCl2 was added as an electrolyte, a detectable adsorption of mecoprop and 2,4-D was also measured on kaolinite (which exhibits a negative surface charge), probably due to formation of Ca-pesticide--surface complexes. Adsorption of the uncharged pesticides (atrazine and isoproturon) was detected only on kaolinite. The lack of adsorption on alpha-alumina indicates that the uncharged pesticides have a greater affinity for the silanol surface sites (=SiOH) than for the aluminol surface sites (=AlOH) in kaolinite. No measurable effect of ionic strength was found for the uncharged pesticides. The results indicate that quartz and calcite play a smaller role than clay minerals.     

Atrazine, isoproturon, mecoprop, 2,4-D, and bentazone adsorption onto iron oxides

Iron oxides are important components influencing the adsorption of various inorganic and organic compounds in soils and sediments. In this study the adsorption on iron oxides of nonionic and ionic pesticides was determined as a function of solution pH, ionic strength, and pesticide concentration. The investigated iron oxides included two-line ferrihydrite, goethite, and lepidocrocite. Selected pesticides comprised atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea)], mecoprop [(RS)-2-(4-chloro-2-methylphenoxy)propionic acid], 2,4-D (2,4-dichlorophenoxyacetic acid), and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide]. The adsorption of the nonionic pesticides (atrazine and isoproturon) was insignificant, whereas the adsorption of the acidic pesticides (mecoprop, 2,4-D, and bentazone) was significant on all investigated iron oxides. The adsorption capacity increased with decreasing pH, with maximum adsorption reached close to the pKa values. The addition of CaCl2 in concentrations from 0.0025 to 0.01 M caused the adsorption capacity to diminish. The adsorption of bentazone was significantly lower than the adsorption of mecoprop and 2,4-D, illustrating the importance of a carboxyl group in the pesticide structure. The adsorption capacity on the iron oxides increased in the order: lepidocrocite < goethite < two-line ferrihydrite. The maximum adsorption capacities of meco-prop and 2,4-D on goethite were found to be equivalent to the site density of singly coordinated hydroxyl groups on the faces of the dominant (110) form, suggesting that singly coordinated hydroxyl groups are responsible for adsorption. Differences in adsorption capacities between iron oxides can be explained by differences in the surface site density of singly coordinated hydroxyl groups. The maximum measured adsorption capacity of mecoprop on two-line ferrihydrite was equivalent to 0.2 mol/mol Fe.     

Pyrene mineralization by Mycobacterium sp. strain KMS in a barley rhizosphere

To determine whether the soil Mycobacterium isolate KMS would mineralize pyrene under rhizosphere conditions, a microcosm system was established to collect radioactive carbon dioxide released from the labeled polycyclic aromatic hydrocarbon. Microcosms were designed as sealed, flow-through systems that allowed the growth of plants. Experiments were conducted to evaluate mineralization of 14C-labeled pyrene in a sand amended with the polycyclic aromatic hydrocarbons degrading Mycobacterium isolate KMS, barley plants, or barley plants with roots colonized by isolate KMS. Mineralization was quantified by collecting the 14CO2 produced from 14C-labeled pyrene at intervals during the 10-d incubation period. Roots and foliar tissues were examined for 14C incorporation. Mass balances for microcosms were determined through combustion of sand samples and collection and quantification of 14CO2 evolved from radiolabeled pyrene. No pyrene mineralization was observed in the sterile control systems. Greater release of 14CO2 was observed in the system with barley colonized by KMS than in microcosms containing just the bacterium inoculum or sterile barley plants. These findings suggest that phytostimulation of polycyclic aromatic hydrocarbons mineralization could be applied in remediation schemes.     

Anaerobic degradation of atrazine and metolachlor and metabolite formation in wetland soil and water microcosms

The half-lives, degradation rates, and metabolite formation patterns of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] were determined in an anaerobic wetland soil incubated at 24 degrees C for 112 d. At 0, 7, 14, 28, 42, 56, and 112 d, the soil and water were analyzed for atrazine and metolachlor, and their major metabolites. The soil oxidation-reduction potential reached -200 mV after 14 d. Degradation reaction rates were first-order for atrazine in anaerobic soil and for metolachlor in the aqueous phase. Zero-order reaction rates were best fit for atrazine in the aqueous phase and metolachlor in anaerobic soil. In anaerobic soil, the half-life was 38 d for atrazine and 62 d for metolachlor. In the aqueous phase above the soil, the half-life was 86 d for atrazine and 40 d for metolachlor. Metabolites detected in the anaerobic soil were hydroxyatrazine and deethylatrazine for atrazine, and relatively small amounts of ethanesulfonic acid and oxanilic acid for metolachlor. Metabolites detected in the aqueous phase above the soil were hydroxyatrazine, deethylatrazine, and deisopropylatrazine for atrazine, and ethanesulfonic acid and oxanilic acid for metolachlor. Concentrations of metabolites in the aqueous phase generally peaked within the first 25 d and then declined. Results indicate that atrazine and metolachlor can degrade under strongly reducing conditions found in wetland soils. Metolachlor metabolites, ethanesulfonic acid, and oxanilic acid are not significantly formed under anaerobic conditions.     

Bioavailability of organic phosphorus in a submerged aquatic vegetation-dominated treatment wetland

Enzymatic hydrolysis and mineralization of organic phosphorus (P) were determined in surface water samples collected from inflow and outflow of a submerged aquatic vegetation (SAV)-dominated treatment wetland of the Florida Everglades. Water samples were fractionated into three size fractions (> 0.4 micron, < 0.4 to > 0.05 micron, and < 0.05 micron) with a sequential flow filtration technique. The fractionated water samples were incubated to hydrolyze with alkaline phosphatase (APase) and phosphodiesterase (PDEase), and to mineralize at different redox and pH. Unlike APase, which hydrolyzed < or = 10% of organic P, PDEase hydrolyzed > or = 71% of organic P in unfiltered water from both inflow and outflow waters, suggesting the domination of bioavailable diester P in the water. Phosphodiesterase completely hydrolyzed organic P in the < 0.4- to > 0.05-micron and < 0.05-micron fractions, as compared with < or = 35% in the > 0.4-micron fraction. However, the P mineralization in inflow and outflow waters at different redox and pH showed that P associated with particulate > 0.4 micron had been mineralized the most. Phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy showed that surficial sediments from the inflow region contained a high proportion of polynucleotides, nucleoside monophosphates, and previously unreported glycerophosphoethanolamine and phosphoenolpyruvates. However, at the outflow, the relative proportion of polynucleotides and nucleoside monophosphates was reduced substantially. This suggests that the SAV wetland may sequester P via accretion of organic matter.     

Remediating RDX-contaminated ground water with permanganate: laboratory investigations for the Pantex perched aquifer

Ground water beneath the U.S. Department of Energy Pantex Plant is contaminated with the high explosive RDX (hexahydro-1,3,5-trinitro-1,3,5 triazine). The USDOE Innovative Treatment and Remediation Demonstration (ITRD) program identified in situ oxidation by permanganate as a technology fit for further investigation. We evaluated the efficacy of KMnO(4) to transform and mineralize RDX by determining degradation kinetics and carbon mass balances using (14)C-RDX. Aqueous RDX solutions (2-5 mg L(-1)) and RDX-contaminated slurries (50% solids, w/v) were treated with KMnO(4) at 1000, 2000, 4000, and 20000 mg L(-1). Treating an aqueous RDX solution of 2.8 mg L(-1) with 20000 mg KMnO(4) L(-1) decreased RDX to 0.1 mg L(-1) within 11 d while cumulative mineralization proceeded for 14 d until 87% of the labeled carbon was trapped as (14)CO(2). Similar cumulative mineralization was obtained when Pantex aquifer material was included in the solution matrix. Other experiments using 4000 mg KMnO(4) L(-1) showed that initial RDX concentrations (1.3-10.4 mg L(-1)) or initial pH (4-11) had little effect on reaction rates. Attempts to identify RDX degradates and reaction products showed that N(2)O was a product of permanganate oxidation and constituted 20 to 30% of the N balance. Time-course measurements of a (14)C-RDX solution treated with KMnO(4) revealed few (14)C-labeled degradates but through liquid chromatography-mass spectrometry (LC-MS) analysis, we present evidence that 4-nitro-2,4-diaza-butanol is formed. Aquifer microcosm studies confirmed that the transformation products not mineralized by KMnO(4) were much more biodegradable than parent RDX. These results indicate permanganate can effectively transform and mineralize RDX in the presence of aquifer material and support its use as an in situ chemical oxidation treatment for the Pantex perched aquifer.     

Effects of static vs. tidal hydrology on pollutant transformation in wetland sediments

This work addressed effects of hydrology on biogeochemical processes relevant to pollutant chemical transformation in wetland sediments. Microcosms were designed to impose three hydrologic conditions on salt marsh sediments: (i) drained-oxidized redox potenial (Eh); (ii) flooded-reduced Eh and, (iii) diurnal tide-oscillating Eh. The test chemicals were N- and/or S-heterocycles (NSHs) including quinoxaline (1,4-benzodiazine), 2-methylquinoxaline(2-methyl-1,4-benzodiazine), 2,3-dimethylquinoxalinen (2,3-dimethyl-1,4-benzodiazine), phenazine (2,3,5,6-dibenzo-1,4-diazine), acridine (2,3,5,6-dibenzopyridine), dibenzothiophene (2,3,5-dibenzothiophene), phenothiazine (dibenzo-1,4-thiazine), and phenanthridine (2,3-benzoisoquinoline). Biogeochemical processes reflected the hydrologic conditions in ways analogous to field settings, e.g., Eh characteristics were drastically different: static (flooded and drained) systems had reduced (mu = -428 mV +/- 57) and oxidized (mu = +73 mV +/- 32) values, respectively, with no evidence of periodic variation while the tidal systems exhibited regularly oscillating Eh (amplitudes 40-250 mV). Sediment trace gases also corresponded to the Eh, with the major species detected being CO2 and H2O (drained, tidal) vs. CO2 + H2O + sulfides + methane (flooded). The NSH transformation rates were different in each hydrologic regime and decreased as follows: tidal > or = drained > flooded. These results indicated that there were subtle differences in NSH processing in drained and tidal systems, but both of these systems transformed NSHs faster and to lower levels than flooded sediments. These data suggest that in situ remediation options that preserve wetland integrity and tidal hydrology can be as or more effective than static conditions that obtain in approaches such as impoundment and excavation-upland placement.     

偶氮染料的厌氧——好氧生物降解过程和影响因素

偶氮染料是总量最大、种类最多的合成染料,其降解处理通常采用厌氧-好氧技术。厌氧过程可实现偶氮染料的还原,好氧过程则完成还原产物芳香胺的去除。厌氧过程受偶氮染料结构和浓度、底物的种类和浓度、其他电子受体、氧化还原介体、温度和DO等环境因素以及水力停留时间的影响。好氧条件下芳香胺的降解过程受其自身的结构、浓度、外加碳源以及降解体系等影响,且自氧化过程影响了芳香胺的生物降解。在实际废水处理中应创造良好的条件提高偶氮染料的厌氧一好氧生物降解效率。     

Free-air carbon dioxide enrichment of soybean: influence of crop variety on residue decomposition

Elevated atmospheric CO2 can result in larger plants returning greater amounts of residue to the soil. However, the effects of elevated CO2 on carbon (C) and nitrogen (N) cycling for different soybean varieties have not been examined. Aboveground residue of eight soybean [Glycine max (L.) Merr.] varieties was collected from a field study where crops had been grown under two different atmospheric CO2 levels [370 micromol mol(-1) (ambient) and 550 micromol mol(-1) (free-air carbon dioxide enrichment, FACE)]. Senesced residue material was used in a 60-d laboratory incubation study to evaluate potential C and N mineralization. In addition to assessing the overall effects of CO2 level and variety, a few specific variety comparisons were also made. Across varieties, overall residue N concentration was increased by FACE, but residue C concentration was only slightly increased. Overall residue C to N ratio was lower under FACE and total mineralized N was increased by FACE, suggesting that increased N2 fixation impacted residue decomposition; total mineralized C was also slightly increased by FACE. Across CO2 levels, varietal differences were also observed with the oldest variety having the lowest residue N concentration and highest residue C to N ratio; mineralized N was lowest in the oldest variety, illustrating the influence of high residue C to N ratio. It appears (based on our few specific varietal comparisons) that the breeding selection process may have resulted in some varietal differences in residue quality which can result in increased N or C mineralization under elevated CO2 conditions. This limited number of varietal comparisons indicated that more work investigating varietal influences on soil C and N cycling under elevated CO2 conditions is required.     

Response of biogeochemical indicators to a drawdown and subsequent reflood

Temporal oscillations in hydrology are a common occurrence in wetlands and can result in alternating flooded and drained conditions in the surface soil. These oscillations in water levels can stimulate microbial activities and result in the mobilization and redistribution of significant amounts of carbon (C), nitrogen (N), and phosphorus (P). The goal of this study was to experimentally simulate a drawdown and reflood of marsh soil from a nutrient-enriched site and a reference site of a wetland (Blue Cypress Marsh Conservation Area, Florida). The goal was to better understand the changes in biogeochemistry and microbial activities present in these soils as a result of hydrological fluctuations. Measurements of dissolved reactive phosphorus (DRP), ammonia, and nitrate in the floodwater indicated significantly higher (alpha = 0.05) NH(4)(+) and DRP fluxes from the nutrient-enriched site; floodwaters in the cores from both sites contained significant NO(3)(-) concentrations (9.6 mg N L(-1)), which was rapidly consumed over the core incubation period (30 d). Water level drawdown and reflooding initially stimulated the soil microbial biomass, methanogenic rates, and extracellular enzyme activities (acid phosphatase and beta-glucosidase). The anaerobic microbial metabolic activities (CO(2)) where initially significantly (alpha = 0.05) enhanced by the reflood, resulting in roughly equivalent rates as the aerobic respiratory activities (CO(2)), presumably as a function of the high water column NO(3)(-) levels. This study illustrates that the reflood event in the hydrological cycles in a wetland can significantly stimulate the activities of hydrolytic enzymes and microbiological communities in these soils.     

Transformation of diphenylarsinic acid in agricultural soils

We investigated the transformation and fate of diphenylarsinic acid (DPAA) during incubation in two types of soils (Entisol and Andisol) under aerobic and anaerobic conditions. Under anaerobic conditions only, DPAA was transformed into methyldiphenylarsine oxide by methylation. Under both aerobic and anaerobic conditions, DPAA was degraded to phenylarsonic acid by dephenylation, and phenylarsonic acid was subsequently methylated to form methylphenylarsinic acid and dimethylphenylarsine oxide. The degradation of DPAA in the Andisol was less extensive than in the Entisol. In autoclaved soil under anaerobic conditions, DPAA underwent little degradation during the 24-wk incubation. In unautoclaved soils, the concentration of DPAA in soil clearly decreased after 24 wk of incubation, indicating that DPAA degradation was driven by microbial activity.     

Degradation of 14C-atrazine bound residues in brown soil and rendzina fractions

The remobilization and the fate of 14C-ring labeled atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) bound residues was examined in relation with the turnover of natural soil organic matter. Soil fractions of a brown soil and a rendzina were incubated under controled laboratory conditions. The mineralization of natural organic matter and atrazine-bound residues was respectively estimated by the amounts of CO2 and 14CO2 evolved during the incubation. The remobilization and distribution of 14C residues among the soil organic fractions were achieved after physical-chemical extractions of the samples. Comparisons of samples in abiotic and biotic conditions allowed us to assess the influence of microbial activity on the fate of atrazine-bound residues. The mineralization curves showed that natural organic matter and atrazine-bound residues had similar decomposition patterns. After 100 d of incubation, 0.8 to 3.6% of total organic C was evolved as CO2, while only 0.1% of the initial radioactivity was mineralized as CO2, and 7 to 15% was becoming extractable with water and methanol. Few differences were observed in the distribution of residues within organic compounds for both fractions of the rendzina, except a decrease of the 14C radioactivity of the 50- to 5000-microm fraction and a slight increase of that of humin. For the 0- to 5000-microm brown soil fraction, increased radioactivity in humin at the expense of humic (HA) and fulvic (FA) acids was detected after incubation, while for the 0- to 50-microm fraction more radioactivity was recovered with FA.     

Persistence of the sulfonylurea herbicides thifensulfuron-methyl, ethametsulfuron-methyl, and metsulfuron-methyl in farm dugouts (ponds)

Sulfonylurea herbicides are applied at relatively low rates (3 to 40 g ha(-1)) to control weeds in a variety of crops across the Canadian prairies. Because of their high phytotoxicity and the likelihood of their transport in surface runoff, there is concern about their possible impact to aquatic ecosystems. Little is known, however, about their persistence and behavior in aquatic ecosystems. To assess persistence in aquatic ecosystems, three prairie farm dugouts (ponds) were fortified with either thifensulfuron-methyl {methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylate}, ethametsulfuron-methyl {methyl 2-[[[[[4-ethoxy-6-(methylamino)-1,3,5-triazin-2-yl]amino]carbonyl]amino]sulfonyl]benzoate} or metsulfuron-methyl {methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazinyl)amino]carbonyl]amino]sulfonyl]benzoate}. The decreasing order of persistence of environmentally relevant concentrations (1 to 4.6 microg L(-1)) of these herbicides in dugout water over the June to October period was metsulfuron-methyl>ethametsulfuron-methyl>thifensulfuron-methyl. The corresponding dissipation half-lives (DT(50)) of 84, 30, and 16 d, respectively, are in the same relative order as the recropping intervals for these herbicides. Thifensulfuron-methyl showed a biphasic dissipation with slower dissipation during the winter months. In contrast, the dissipation of metsulfuron-methyl, the sulfonylurea herbicide with the longest DT(50), was somewhat enhanced under winter conditions. One of the major routes of sulfonylurea herbicide dissipation was removal from the water column when dugout water was lost during hydrological discharge. The relatively long persistence of these herbicides in water indicates that partitioning into sediments was minimal, the sulfonylurea and methyl ester linkages in these compounds were resistant to hydrolysis in weakly alkaline waters, and that microbial and photolytic degradation in dugout waters were slow.     

Herbicide and nutrient transport from an irrigation district into the South Saskatchewan River

Pesticides and nutrients can be transported from treated agricultural land in irrigation runoff and thus can affect the quality of receiving waters. A 3-yr study was carried out to assess possible detrimental effects on the downstream water quality of the South Saskatchewan River due to herbicide and plant nutrient inputs via drainage water from an irrigation district. Automated water samplers and flow monitors were used to intensively sample the drainage water and to monitor daily flows in two major drainage ditches, which drained approximately 40% of the flood-irrigated land within the irrigation district. Over three years, there were no detectable inputs of ethalfluralin into the river and those of trifluralin were less than 0.002% of the amount applied to flood-irrigated fields. Inputs of MCPA, bromoxynil, dicamba and mecoprop were 0.06% or less of the amounts applied, whereas that for clopyralid was 0.31%. The relatively higher input (1.4%) of 2,4-D to the river was probably due its presence in the irrigation water. Corresponding inputs of P (as total P) and N (as nitrate plus ammonia) were 2.2 and 1.9% of applied fertilizer, respectively. Due to dilution of the drainage water in the river, maximum daily herbicide (with the exception of 2,4-D) and nutrient loadings to the river would not have resulted in significant concentration increases in the river water. There was no consistent remedial effect on herbicides entering the river due to passage of the drainage water through a natural wetland. In contrast, a considerable portion of the nutrients entering the river originated from the wetland.     

Fate of arsenic in swine waste from concentrated animal feeding operations

Swine diets are often supplemented by organoarsenicals, such as 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) to treat animal diseases and promote growth. Recent work reported roxarsone degradation under anaerobic conditions in poultry litter, but no such data exist for swine wastes typically stored in lagoons nearby concentrated animal feeding operations (CAFOs). The objectives of this study were to: (i) characterize a suite of swine wastes collected from 19 randomly selected CAFOs for soluble arsenate [As(V)], arsenite [As(III)], dimethylarsenic acid (DMA), monomethylarsonic acid (MMA), 3-amino-4-hydroxyphenylarsonic acid (3-HPPA), p-arsanilic acid, and roxarsone, and (ii) determine the geochemical fate of roxarsone in storage lagoons nearby CAFOs. Swine waste suspensions were spiked with roxarsone and incubated under dark/light and aerobic/anaerobic conditions to monitor roxarsone degradation kinetics. Arsenic speciation analysis using liquid chromatography and inductively coupled plasma mass spectrometry (LC-ICPMS) illustrated the prevalence of As(V) in swine waste suspensions. Roxarsone underwent degradation to either organoarsenicals (3-HPPA) or As(V) and a number of unidentified metabolites. Roxarsone degradation occurred under anaerobic conditions for suspensions low in solids content, but suspensions higher in solids content facilitated roxarsone degradation under both anaerobic and aerobic conditions. Increased solids content enhanced roxarsone degradation kinetics under aerobic conditions. According to current waste storage and sampling practices, arsenic in swine wastes stored in lagoons has been overlooked as a possible environmental health issue.