Biodegradation of pentaerythritol tetranitrate (PETN) by anaerobic consortia from a contaminated site

This study examined the role of denitrifying and sulfate-reducing bacteria in biodegradation of pentaerythritol tetranitrate (PETN). Microbial inocula were obtained from a PETN-contaminated soil. PETN degradation was evaluated using nitrate and/or sulfate as electron acceptors and acetate as a carbon source. Results showed that under different electron acceptor conditions tested, PETN was sequentially reduced to pentaerythritol via the intermediary formation of tri-, di- and mononitrate pentaerythritol (PETriN, PEDN and PEMN). The addition of nitrate enhanced the degradation rate of PETN by stimulating greater microbial activity and growth of nitrite reducing bacteria that were responsible for degrading PETN. However, a high concentration of nitrite (350 mg L⁻¹) accumulated from nitrate reduction, consequently caused self-inhibition and temporarily delayed PETN biodegradation. In contrast, PETN degraded at very similar rates in the presence and absence of sulfate, while PETN inhibited sulfate reduction. It is apparent that denitrifying bacteria possessing nitrite reductase were capable of using PETN and its intermediates as terminal electron acceptors in a preferential utilization sequence of PETN, PETriN, PEDN and PEMN, while sulfate-reducing bacteria were not involved in PETN biodegradation. This study demonstrated that under anaerobic conditions and with sufficient carbon source, PETN can be effectively biotransformed by indigenous denitrifying bacteria, providing a viable means of treatment for PETN-containing wastewaters and PETN-contaminated soils.     

Direct and indirect photolysis of two quinolinecarboxylic herbicides in aqueous systems

The photodegradation of two quinolinecarboxylic herbicides, 7-chloro-3-methylquinoline-8-carboxylic acid (QMe) and 3,7-dichloroquinoline-8-carboxylic acid (QCl), was studied in aqueous solution at different irradiation wavelengths. The effect of sunlight irradiation was investigated also in the presence of titanium dioxide (TiO₂). UV irradiation degraded rapidly QMe affording 7-chloro-3-methylquinoline (MeQ) through a decarboxylation reaction. The reaction rate was lower in the presence of dissolved organic carbon (DOC) because of the adsorption of the herbicide on the organic components. Instead, QCl was stable under both UV light and sunlight irradiation. The irradiation of QMe or QCl solutions with simulated sunlight in the presence of TiO₂ produced the complete mineralization of the two herbicides.     

Respiration induced by substrate and bacteria diversity after application of diuron,hexazinone, and sulfometuron-methyl alone and in mixture

Abstract

After application, herbicides often reach the soil and affect non-target soil microorganisms, decreasing their population, diversity or affecting metabolic activity. Therefore, laboratory studies were performed to evaluate the effects of diuron, hexazinone and sulfometuron-methyl alone and mixed upon carbon transformation by soil microorganisms in clayey and sandy soils and the effect on bacterial diversity and structure. Control treatment without herbicide application was also performed. Sub-samples from the control and herbicide treatments (10?g – in triplicate) were collected before herbicide application and 7, 14, 28 and 42?days after treatment (DAT), then 1?mL of ¹⁴C-glucose solution was applied. The released ¹⁴CO₂ was trapped in 2?M NaOH solution and the radioactivity was analyzed by liquid scintillation counting (LSC), 12?h after glucose application. The effect of herbicides on bacterial diversity was evaluated by T-RFLP. The experiment was conducted in a complete randomized design. Hexazinone did not affect ¹⁴CO₂ evolution. Diuron showed a greater ¹⁴CO₂ evolution in sandy and clayey soil, while sulfometuron-methyl led to an increase in sandy soil, at 42 DAT. A greater evolution of carbon was observed in the treatment with herbicide mixture in sandy soil, compared with the same treatment in clayey soil or control. However, the herbicide mixture application did not affect the soil biological activity measured by the respiration rate induced by substrate. On the other hand, the herbicide mixtures affected the bacterial diversity in both soils, being the strongest effect to diuron and sulfometuron-methyl in clayey soil and hexazinone in sandy soil.     

Impact of carbon source on nitrous oxide emission from anoxic/oxic biological nitrogen removal process and identification of its emission sources

Wastewater treatment is an important source of nitrous oxide (N₂O), which is a strong greenhouse gas and dominate ozone-depleting substance. The purpose of this study was to evaluate the effect of carbon source on N₂O emission from anoxic/oxic biological nitrogen removal process. The mechanisms of N₂O emission were also studied. Long-term experiments were operated to evaluate the effect of three different carbon sources (i.e., glucose, sodium acetate, and soluble starch) on N₂O emission characteristics. And batch experiments, in the presence or absence of specific inhibitors, were carried out to identify the sources of N₂O emission. The ammonia-oxidizing bacteria (AOB) and denitrifiers community compositions under different circumstances were also analyzed based on which the underlying mechanisms of N₂O emission were elucidated. The conversion ratios of N₂O in reactors with glucose, sodium acetate, and soluble starch were 5.3 %, 8.8 %, and 2.8 %, respectively. The primary process responsible for N₂O emission was nitrifier denitrification by Nitrosomonas-like AOB, while denitrification by heterotrophic denitrifiers acted as the sink. Reactor with sodium acetate showed the highest N₂O emission, together with the highest nitrogen and phosphate removal ratios. Carbon source has a significant impact on N₂O emission quantity and relatively minor effect on its production mechanism.     

Theoretical aspects and experimental evidence of the capacity of humic substances to bind herbicides by charge-transfer mechanisms (electron donor-acceptor processes)

Theoretical aspects of the possible occurrence of electron donor-acceptor processes involving free radical intermediates and leading to stable charge-transfer complexes between electron donor herbicides and acceptor quinone-like units of humic acids have been discussed on the basis of similar mechanisms occurring on biological scale in the chloroplasts. Experimental evidence of the former hypotheses was given by the analyses of infrared and electron spin resonance data obtained from interaction complexes of a number of s-triazines and substituted ureas (photosynthesis inhibitor herbicides) with soil humic acids. In the case of s-triazines it was shown that with decrease of the capacity of humic molecules to form ionic and hydrogen bonds, the tendency to act as electron acceptor increased, as shown by the higher free radical generation observed after the interaction process. The existence of correlations between the bioactivity of substituted ureas - expressed as inhibitory potency in the Hill reaction (pI₅₀ indexes) - and free radical concentrations in the humic acid - herbicide complexes was also demonstrated.     

Effects of the herbicide molinate on the metabolic activities of a degradative Streptomyces griseus strain

Abstract

Cometabolic degradation of the herbicide molinate was tested using two microorganisms, Arthrobacter sp., strain M3 and Streptomyces griseus strain M2; the latter classified on the basis of the presence of the enzymatic cofactor SF‐420. The strains M3 and M2, inoculated in a basic salts medium with glucose as carbon source and added with 100 mg L^‐1 of molinate, degraded respectively 35 and 51% of the herbicide in 36 days.

Increasing concentrations of molinate, ranging from 50 to 200 mg L^‐1 in glucose medium, did not affect the final ATP yield of the strain M2, but decreased the final growth yield and the ATP synthesis rate. Moreover, the onset of coenzyme SF‐420 synthesis was progressively delayed.

In contrast, surprisingly, SF‐420 final yield and production rate were increased by progressive increasing concentrations of molinate in the mineral medium.     

Strategies to evaluate biodegradability: application to chlorinated herbicides

The biodegradability of nitrochlorinated (diuron and atrazine) and chlorophenoxy herbicides (2,4-D and MCPA) has been studied through several bioassays using different testing times and biomass/substrate ratios. A fast biodegradability test using unacclimated activated sludge yielded no biodegradation of the herbicides in 24 h. The inherent biodegradability test gave degradation percentages of around 20–30 % for the nitrochlorinated herbicides and almost complete removal of the chlorophenoxy compounds. Long-term biodegradability assays were performed using sequencing batch reactor (SBR) and sequencing batch membrane bioreactor (SB-MBR). Fixed concentrations of each herbicide below the corresponding EC₅₀ value for activated sludge were used (30 mg L^?1 for diuron and atrazine and 50 mg L^?1 for 2,4-D and MCPA). No signs of herbicide degradation appeared before 35 days in the case of diuron and atrazine and 21 days for 2,4-D, whereas MCPA was partially degraded since the early stages. Around 25–36 % degradation of the nitrochlorinated herbicides and 53–77 % of the chlorophenoxy ones was achieved after 180 and 135 days, respectively, in SBR, whereas complete disappearance of 2,4-D was reached after 80 days in SB-MBR.     

Studies on the origin of the methylsulfonyl‐containing metabolites from propachlor

Abstract

Metabolites in which the chlorine from propachlor has been replaced by a cysteine group or a methylsulfonyl group [‐S(O₂) CH₃] are present in the urine of rats dosed orally with propachlor. In the present study, urine from rats given single oral doses of ³⁵S‐labeled cysteine conjugate of propachlor contained metabolites having the methylsulfonyl groups labeled with S. No metabolites containing ¹⁴C‐labeled methylsulfonyl groups were isolated from urine of rats given single oral doses of the cysteine conjugate of propachlor in which the cysteine group was uniformly labeled with ¹⁴C. These findings show that the cysteine conjugate of propachlor is the source of sulfur in the methylsulfonyl‐containing metabolites. Therefore, we suggest that a C‐S lyase present in the animal cleaves the cysteine conjugate of propachlor and thus allows further metabolism of the sulfur to a methylsulfonyl moiety.     

Sorption and desorption kinetics of diuron,fluometuron, prometryn and pyrithiobac sodium in soils

Abstract

The sorption and desorption characteristics of four herbicides (diuron, fluometuron, prometryn and pyrithiobac‐sodium) in three different cotton growing soils of Australia was investigated. Kinetics and equilibrium sorption and desorption isotherms were determined using the batch equilibrium technique. Sorption was rapid (> 80% in 2 h) and sorption equilibrium was achieved within a short period of time (ca 4 h) for all herbicides. Sorption isotherms of the four herbicides were described by Freundlich equation with an r² value > 0.98. The herbicide sorption as measured by the distribution coefficient (K_d) values ranged from 3.24 to 5.71 L/kg for diuron, 0.44 to 1.13 L/kg for fluometuron, 1.78 to 6.04 L/kg for prometryn and 0.22 to 0.59 L/kg for pyrithiobac‐sodium. Sorption of herbicides was higher in the Moree soil than in Narrabri and Wee Waa soils. When the K_d values were normalised to organic carbon content of the soils (K_oC), it suggested that the affinity of the herbicides to the organic carbon increased in the order: pyrithiobac‐sodium < fluometuron < prometryn < diuron. The desorption isotherms were also adequately described by the Freundlich equation. For desorption, all herbicides exhibited hysteresis and the hysteresis was stronger for highly sorbed herbicides (diuron and prometryn) than the weakly sorbed herbicides (fluometuron and pyrithiobac‐sodium). Hysteresis was also quantified as the percentage of sorbed herbicides which is not released during the desorption step ω = [n_ad / n_de ‐1] x 100). Soil type and initial concentration had significant effect on ω. The effect of sorption and desorption properties of these four herbicides on the off‐site transport to contaminate surface and groundwater are also discussed in this paper.     

Degradation of telone II in contaminated and noncontaminated soils

Abstract

Degradation of the nematicide Telone II (cis‐ and trans‐1,3‐dichloropropene comprise the active ingredients) in soil was studied using ¹⁴C‐l,3‐dichloropropene (DCP) along with soil samples collected from a field test site near Quincy, Florida. A mixed bacterial culture isolated from the soil in the presence of a second carbon source, glucose or yeast extract, completely degraded ¹⁴C‐DCP to ¹⁴CO₂, water‐soluble products, and microbial mass. ¹⁴C‐DCP in soil was also degraded to ¹⁴CO₂. After 28 days of incubation, the labeled chemical was completely degraded to ¹⁴CO₂, water‐soluble metabolites, bound‐residues, and possibly some microbial mass. Little or no difference was observed in the degradation of ¹⁴C‐DCP in soil samples collected one week prior to field application of Telone II, or two weeks and two years after application.     

Trace level determination of selected sulfonylurea herbicides in wetland sediment by liquid chromatography electrospray tandem mass spectrometry

Sulfonylurea herbicides are widely used in crop production on the Canadian prairies and a portion of these herbicides applied to cropland are inevitably lost to surrounding aquatic ecosystems. Little is known regarding the presence of sulfonylurea herbicides in wetlands located amongst cropland. This paper describes a new analytical method for the extraction and the determination of seven sulfonylurea herbicides (thifensulfuron-methyl, tribenuron-methyl, ethametsulfuron-methyl, metsulfuron-methyl, rimsulfuron, nicosulfuron and sulfosulfuron) in wetland sediment. The method provided > 85% analyte recovery from fortified sediment for six of the seven sulfonylurea herbicides with a limit of quantification (LOQ) of 1.0 μ g kg^{? 1}. Tribenuron-methyl had significantly lower recovery compared to the other six sulfonylurea herbicides (LOQ = 2 μ g kg^{? 1}). Mean recovery standard deviations were < 10%. This methodology was used to quantify sulfonylurea herbicide residues in sediment samples collected from prairie wetlands situated within the agricultural landscape of Saskatchewan and Manitoba, Canada. This is the first-known detection of sulfonylurea herbicide residues in prairie wetland sediments. Ethametsulfuron-methyl, sulfosulfuron and metsulfuron-methyl, the three most environmentally persistent of the seven sulfonylurea herbicides monitored in the surveillance component of this study, were most frequently detected in wetland sediment with mean concentrations ranging from 1.2 to 10 μ g kg^{? 1}.     

碳源类型及进水量分配对CMICAO工艺脱氮除磷的影响

研究了分别以葡萄糖和乙酸钠为碳源时多点交替进水阶式A2/O(CMICAO)工艺氮磷的去除效果,以及在不同进水C/N比时各进水量分配对脱氮除磷效果的影响.结果表明,在相同的进水COD浓度下,乙酸钠比葡萄糖更适合作为碳源,更能提高脱氮除磷效率.以葡萄糖为碳源时,COD为200 mg/L、C/N比为5、缺氧池与厌氧池进水配比为1∶2时,出水COD、TN、氨氮和TP浓度分别为28.5、10.8、2.1和0.5 mg/L,均达到国家一级A排放标准.若采用葡萄糖作为碳源,投加量以使进水C/N比为5～7.5为宜,外加碳源时缺氧池与厌氧池进水分配比可统一采用1∶1.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.     

Combined effect of diuron and simazine on photosystem II photochemistry in a sandy soil and soil amended with solid olive-mill waste

Diuron (3-(3,4-dichlorophenyl)- = 1,1-dimethylurea) and simazine (6-chloro-N ², N ⁴-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the effect of these herbicides on Photosystem II photochemistry of Olea europaea L., and whether the amendment of soil with an organic waste (OW) from olive oil production industry modifies this effect. For this purpose, herbicide soil adsorption studies, with unamended and OW-amended soil, and chlorophyll fluorescence measurements in adult olive leaves, after one, two and three weeks of soil herbicide treatment and/or OW amendment, were performed. Soil application of these herbicides reduced the efficiency of Photosystem II photochemistry of olive trees due to chronic photoinhibition, and this effect is counterbalanced by the addition of OW to the soil. OW reduces herbicide uptake by the plant due to an increase in herbicide adsorption.     

Sorption of atrazine and metolachlor by earthworm surface castings and soil

Abstract

Atrazine and metolachlor were more strongly retained on earthworm (Lumbricus terrestris L.) castings than on soil, suggesting that earthworm castings at the surface or at depth can reduce herbicide movement in soil. Herbicide sorption by castings was related to the food source available to the earthworms. Both atrazine and metolachlor sorption increased with increasing organic carbon (C) content in castings, and Freundlich constants (K_f values) generally decreased in the order: soybean‐fed > corn‐fed > not‐fed‐earthworm‐castings. The amount of atrazine or metolachlor sorbed per unit organic carbon (K_oc values) was significantly greater for corn‐castings compared with other castings, or soil, suggesting that the composition of organic matter in castings is also an important factor in determining the retention of herbicides in soils. Herbicide desorption was dependent on both the initial herbicide concentration, and the type of absorbent. At small equilibrium herbicide concentrations, atrazine desorption was significantly greater from soil than from any of the three casting treatments. At large equilibrium herbicide concentrations, however, the greater organic C content in castings had no significant effect on atrazine desorption, relative to soil. For metolachlor, regardless of the equilibrium herbicide concentration, desorption from soybean‐ and corn‐castings treatments was always less than desorption from soil and not‐fed earthworm castings treatments. The results of this study indicate that, under field conditions, the extent of herbicide retention on earthworm castings will tend to be related to crop and crop residue management practices.     

Ferric iron amendment increases Fe(III)-reducing microbial diversity and carbon oxidation in on-site wastewater systems

Onsite wastewater systems, or septic tanks, serve approximately 25% of the United States population; they are therefore a critical component of the total carbon balance for natural water bodies. Septic tanks operate under strictly anaerobic conditions, and fermentation is the dominant process driving carbon transformation. Nitrate, Fe(III), and sulfate reduction may be operating to a limited extent in any given septic tank. Electron acceptor amendments will increase carbon oxidation, but nitrate is toxic and sulfate generates corrosive sulfides, which may damage septic system infrastructure. Fe(III) reducing microorganisms transform all major classes of organic carbon that are dominant in septic wastewater: low molecular weight organic acids, carbohydrate monomers and polymers, and lipids. Fe(III) is not toxic, and the reduction product Fe(II) is minimally disruptive if the starting Fe(III) is added at 50–150 mg L^?1. We used ¹⁴C radiolabeled acetate, lactate, propionate, butyrate, glucose, starch, and oleic acid to demonstrate that short and long-term carbon oxidation is increased when different forms of Fe(III) are amended to septic wastewater. The rates of carbon mineralization to ¹⁴CO₂ increased 2–5 times (relative to unamended systems) in the presence of Fe(III). The extent of mineralization reached 90% for some carbon compounds when Fe(III) was present, compared to levels of 50–60% in the absence of Fe(III). ¹⁴CH₄ was not generated when Fe(III) was added, demonstrating that this strategy can limit methane emissions from septic systems. Amplified 16S rDNA restriction analysis indicated that unique Fe(III)-reducing microbial communities increased significantly in Fe(III)-amended incubations, with Fe(III)-reducers becoming the dominant microbial community in several incubations. The form of Fe(III) added had a significant impact on the rate and extent of mineralization; ferrihydrite and lepidocrocite were favored as solid phase Fe(III) and chelated Fe(III) (with nitrilotriacetic acid or EDTA) as soluble Fe(III) forms.     

Effects of soil attributes and straw accumulation on the sorption of hexazinone and tebuthiuron in tropical soils cultivated with sugarcane

Brazil is the largest sugarcane producer in the world in which hexazinone (3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4-dione) and tebuthiuron (1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea) are heavily used. Sugarcane harvesting is changing from the manual system with previous straw burning to the mechanized system without straw burning. The lack of burning results in soil organic carbon accumulation mainly in clayey soils, which should affect herbicides availability and fate. Therefore, we evaluated sorption of these herbicides in soil samples with and without straw burning. Both herbicides presented low apparent sorption coefficients (mean K_d,app= 0.6 and 2.4 L kg^?1 for hexazinone and tebuthiuron, respectively), suggesting that they may leach to groundwater. Moreover, their sorption correlated primarily with soil organic carbon (SOC), but iron oxide contents extracted with ammonium oxalate (Fe₂O₃^AOX) also affected it (K_d,app = ?0.228 + 0.0397 SOC + 0.117 Fe₂O₃^AOX for hexazinone and K_d,app = ?1.407 + 0.201 SOC + 0.348 Fe₂O₃^AOX for tebuthiuron). Soil organic carbon accumulation due to straw maintenance in the field positively affected sorption of both herbicides, but its effects were not enough to classify them as “non-leachers.”     

不同污泥源条件下ANAMMOX启动及其与反硝化协同脱氮对比

采用城市生活污水配水同时启动两组ASBR,R1接种好氧硝化污泥,R2按2∶1混合接种短程硝化和厌氧氨氧化污泥,研究2个ANAMMOX反应器启动的可行性及其差异。实验结果表明,R1和R2均可成功启动ANAMMOX,R1需130 d,R2仅需73 d;稳定期R1和R2反应器NH4+-N、NO2--N和TN去除率分别达95.30%、91.30%、76.28%和96.2%、98.3%、90.1%,且周期内NH4+-N、NO2--N和NO3--N降解规律相似;R1和R2反应器发生的主要反应为厌氧氨氧化,但同时存在反硝化作用;2组反应器稳定运行后污泥颜色、形态及微生物组成相似,经SEM观察多为球状菌。     

Oxidative dealkylation of five phenylurea herbicides by the fungus CunninghamellaechinulataThaxter

Microorganisms isolated from soil degrade phenylurea herbicides via two major pathways: (i) direct hydrolysis by an amidase leading to N,O-dimethylhydroxylamine, CO₂ and aniline¹ and (ii) N-dealkylation, which has been described as the first step in urea herbicide degradation by a variety of organisms including mammals, plants and microbial systems (for a review see reference 2).Until now no attempts have been made to investigate the mechanism of N-demethylation of substituted ureas in soil microorganisms, due to the instability of the N-hydroxymethyl intermediates. This reaction mechanism has only been described in detail in green plants^3–5. As among soil fungi Phycomycetes are known to demethylate phenylurea herbicides^6,7 this study has been made to identify intermediate hydroxymethyl compounds from urea herbicides, when incubated with the fungus $\text{Cunninghamella echinulata Thaxter}$.