Biodegradation behavior of agricultural pesticides in anaerobic batch reactors

This study explored the biodegradation potential of two agricultural pesticides (2,4-D and isoproturon) as well as their effect on the performance of the anaerobic digestion process. Three 3.5 L batch reactors were used, having the same initial isoproturon concentration (25 mg/L) and different 2,4-D concentrations (i.e. 0, 100, or 300 mg/L, respectively). All systems were fed with equal amounts of primary sludge and digested sludge and operated at the low mesophilic range (32 +/- 2 degrees C). Following an acclimation period of approximately 30 days, complete 2,4-D removal was achieved, whereas isoproturon biodegradation was practically negligible. The presence of 2,4-D did not have a direct effect on acidogenesis since soluble organic carbon [expressed either as volatile fatty acids (VFAs) or as total organic carbon (TOC)] peaked within the first 10 days of operation in all bioreactors. Utilization of VFAs however appeared to follow two distinct patterns: one pattern was represented by acetate and butyrate (i.e. no acid accumulation) while the other was followed by propionate, isobuturate, valerate and isovalerate (i.e. acid accumulation, duration of which was related to the initial 2,4-D concentration). On the whole, all reactors exhibited a successful digestion performance demonstrated by complete VFAs utilization, considerable gas production (containing 45 to 65% methane by volume), substantial volatile suspended solids (VSS) reduction (42 to 50%), as well as pH and alkalinity recovery.     

The use of naturally generated volatile fatty acids for herbicide removal via denitrification

This research focuses on the removal of 2, 4-D via denitrification, with a particular emphasis on the effect of adding naturally generated volatile fatty acids (VFAs) as a carbon source. These VFAs had been produced from an acid-phase anaerobic digester (mean VFA concentration of 3153 ± 801 mg/L [as acetic acid]). The first step involved developing 2, 4-D degrading bacteria in a sequencing batch reactor (SBR) fed with both sewage and 2, 4-D (30–100 mg/L). Subsequent denitrification batch tests demonstrated that the specific denitrification rate increased from 0.0119 ± 0.0039 to 0.0192 ± 0.0079 g NO₃-N/g volatile suspended solids (VSS) per day, when using 2, 4-D alone versus 2, 4-D plus natural VFAs from the digester as a carbon source. Similarly, the specific 2, 4-D consumption rate increased from 0.0016 ± 0.0009 to 0.0055 ± 0.0021 g 2,4-D/g VSS per day, when using 2, 4-D alone as compared to using 2, 4-D plus natural VFAs. Finally, a parallel increase in the percent 2, 4-D removal was observed, rising from 28.33 ± 11.88 using 2, 4-D alone to 54.17 ± 21.89 using 2, 4-D plus natural VFAs.     

Degradation of 2,4-dichlorophenol by combining photo-assisted Fenton reaction and biological treatment.

The photo-Fenton reaction effect on the biodegradability improvement of 100 mg/L solution of 2,4-dichlorophenol (DCP) has been investigated. Biochemical oxygen demand (BOD) at 5 and 21 days, BODn/ chemical oxygen demand (COD) and BODn/total organic carbon (TOC) ratios, average oxidation state, and inhibition on activated sludge were monitored. For 50 mg/L hydrogen peroxide and 10 mg/L iron(II) initial concentrations and 40 minutes of reaction time in the photo-Fenton process, the biodegradability of the pretreated solution, measured as BOD5/COD ratio, was improved from 0 for the original DCP solution up to 0.18 (BOD21/COD = 0.24). At that point, all DCP was eliminated from the solution. To study the effect of the pretreatment step, the biological oxidation of pretreated solutions was tested in two semicontinuous stirred tank reactors, one operated with activated sludge and one with biomass acclimated to phenol. Results showed that more than 80% TOC removal could be obtained by codigestion of the pretreated solution with municipal wastewater. Total organic carbon removals of approximately 60% were also obtained when the sole carbon source for the aerobic reactors was the pretreated solution. The hydraulic retention times used in the bioreactors were of the same order of magnitude as those used at domestic wastewater treatment plants (i.e., between 12 and 24 hours). Kinetic studies based on pseudo-first-order kinetics have also been carried out. Constants were found to be in range 0.67 to 1.7 L x g total volatiles suspended solids(-1) x h(-1).     

温度对木质纤维素水解与挥发性脂肪酸累积的影响

木质纤维素厌氧消化过程产生的挥发性脂肪酸（VFAs）可作为外加碳源投加到人工湿地，解决人工湿地反硝化碳源不足的问题，但温度对木质纤维素厌氧消化生产VFAs过程的影响还有待深入探明。考察上述木质纤维素厌氧消化过程中有机碳源、糖与VFAs的变化规律，试图探明温度（10-55℃）对木质纤维素水解与VFAs累积的影响。研究结果表明，温度升高对木质纤维素的水解具有促进作用，对VFAs产量的影响显著。35℃时是生物质发酵产酸的最优条件，VFAs累积量不仅最早（第10天）达到最高值154mgCOD／g生物质，而且碳源的数量和品质均达到较高的水平。     

剩余污泥发酵产酸特征及基质释放规律研究

剩余污泥发酵既能实现污泥减量,又能获得污水生物脱氮除磷所需的挥发性脂肪酸VFAs等。采用序批式污泥发酵实验,在(30±1)℃的条件下,研究剩余污泥投配比对序批式污泥发酵系统污泥减量、产酸以及基质释放过程的影响,探索VFAs生成最大化的条件。实验结果表明:投加接种污泥不能明显提高序批式污泥发酵系统剩余污泥的减量效果,但可以改善污泥的产酸特性;当污泥投配比大于50%时,发酵过程中将出现2个VFAs浓度峰,且第二次峰浓度更大;较为理想的序批式污泥发酵投配比是60%~80%、发酵时间为5 d或25 d,前者VFAs表观转化率最大(约24%),后者发酵液中VFAs浓度最高(约600 mg/L);发酵过程中,NH4+-N总体呈上升趋势,磷浓度发酵5 d时达到最大值。     

利用气相色谱法测定剩余污泥厌氧消化产生的混合VFA

厌氧消化是剩余污泥处理的重要方法,消化过程中会产生大量的挥发性脂肪酸(VFA)。讨论了气相色谱在恒温条件下对剩余污泥厌氧消化过程中产生乙酸、丙酸、异丁酸、正丁酸、异戊酸、正戊酸测定的可行性。结果表明:各种酸出峰时间间隔清晰,易于识别;从数据平行测试的变异系数看,异戊酸的变异系数最大,也仅为3.23%,表明测试方法具有良好的可重复性;回收率实验表明,剩余污泥消化液中各种VFA组分的回收率在96%～105%之间,符合文献规定的测试要求。     

The anaerobic biodegradability of municipal sludge and fat, oil, and grease at mesophilic conditions.

The anaerobic biodegradability of municipal primary and secondary sludge with increasing levels of partially dewatered fat, oil, and grease (FOG) was assessed using a mixed methanogenic culture at 35 "C. Under batch conditions with an acclimated and enriched microbial population, the sludge loading was 3 kg volatile solids/m3 and the highest FOG loading tested was 1.5 kg volatile solids/m3, resulting in a methane yield of 245 mL methane/g sludge volatile solids added at 35 degrees C and 1010 mL methane/g FOG volatile solids added at 35 degrees C. Under semicontinuous feeding conditions, the sludge and sludge plus FOG loading tested were 3 and 3.75 kg volatile solids/m3-d, respectively. Within 23 days of operation, the volatile fatty acid concentrations were reduced below 200 mg chemical oxygen demand/L (187 mg/L as acetic acid). Enhancement of sludge digestion was observed in those reactors where codigestion of sludge and FOG took place, which was attributed to a higher level of microbial activity maintained in these reactors as a result of FOG degradation. The results of this study demonstrate that beneficial use of FOG through codigestion with municipal sludge is feasible.     

臭氧预处理—厌氧消化工艺促进剩余污泥减量化的研究

主要研究了臭氧氧化对剩余污泥的破解效果及污泥厌氧消化效率的影响.结果表明,随着臭氧投加量的增加,悬浮物(SS)、可挥发性悬浮物(VSS)逐步减少,而剩余污泥上清液中的溶解性COD(SCOD)、总有机碳(TOC)、蛋白质和多糖则明显增加.经臭氧预处理(臭氧投加量为0.050 g(以每克SS计))后,剩余污泥中温(35℃)厌氧消化效率明显提高,经65d稳定运行后,总挥发性固体(TVS)去除率为67.58％,与未经臭氧预处理的剩余污泥相比提高50.61％;甲烷平均产率为0.303 L(以每克TVS计),与未经臭氧预处理的剩余污泥相比提高54.59％.可见,臭氧预处理能有效促进污泥厌氧消化,从而达到污泥减量的目的.     

Effect of sludge-amendment or nutrient addition on the biodegradation of the herbicide isoproturon in soil

Adding sludge to agricultural soil results in added organic matter, nutrients and metallic and/or organic pollutants. These components may modify the behaviour of pesticides in the soil. We monitored possible changes in the degradation of the herbicide isoproturon (production of CO2 and degradation products) in soil amended with sludge, heavy metals or nitrogen and phosphorus. The treated and control soils were incubated under controlled conditions for 60 days. The nitrogen and phosphorus had the greatest effect on isoproturon degradation, independent of the presence of pollutants. Mineralisation of the herbicide to CO2 was slow and seemed to be linked to a fast degradation and to the accumulation of a complex degradation product that was neither catabolized nor adsorbed, 4,4'-diisopropylazobenzene. This degradation pathway also produced smaller amounts of non-extractable residues. Sewage sludge had no significant effect on isoproturon degradation, despite a large increase of organic matter mineralisation (factor 2).     

剩余污泥水解酸化液磷去除的影响因素研究

城市污水厂剩余污泥水解酸化后可产生高浓度挥发性有机酸(VFAs),其中的乙酸和丙酸是增强生物除磷(EBPR)工艺的有利基质.但水解酸化液中含有大量的磷,如不进行处理就作为碳源回用到污水处理工艺中,势必增加除磷负荷.利用鸟粪石沉淀法可以去除污水中的磷.对城市污水厂剩余污泥水解酸化液形成鸟粪石的影响因素进行了试验研究.结果表明,在最佳工艺条件下,正磷和总磷的去除率分别可达92.5%和83.8%.     

挥发性脂肪酸对厌氧干式发酵产甲烷的影响

为了提高中温干式厌氧间歇发酵效率,研究了发酵过程中间产物———挥发性脂肪酸对产甲烷的影响。实验分2批进行,第1批在牛粪发酵过程中分别添加乙酸、丙酸和丁酸,第2批发酵添加易产生挥发酸的厨余垃圾混合发酵。结果显示,添加单一挥发酸的发酵过程中,添加丙酸的产甲烷速度较慢,因为丙酸降解生成乙酸的速度较慢,减慢了甲烷的形成;混合发酵过程厨余垃圾产甲烷速度比牛粪快,发酵过程产生2个产气高峰;牛粪和厨余垃圾固体物质含量比在11∶1到5∶1范围内较好,比牛粪单独发酵产气多,产酸高但不酸败,产生的挥发酸主要是乙酸和丙酸,其中比例为7∶1混合发酵的产甲烷速率最大,为4.89 mL/(g VS·d)。实验表明,牛粪厌氧干式发酵过程添加一定量的厨余垃圾可加快挥发酸的产生并提高挥发酸产量,从而提高甲烷的产量,但是总挥发酸长时间超过10 000 mg/L,pH降到不适于产甲烷菌生长的范围时,将抑制甲烷的生成,挥发酸积累导致厌氧发酵酸败。     

好氧/缺氧消化降解污泥特征分析

为考察好氧/缺氧消化过程中污泥降解的特征，利用2个反应器进行对比试验，研究好氧/缺氧和好氧消化2个过程中VS的去除，pH和碱度变化，消化上清液中COD和氮元素变化等情况。试验结果表明:好氧/缺氧消化能够满足污泥稳定的要求，在常温条件下，消化16 d VS去除率即可达到38.2%，同时比好氧消化节约曝气能耗。好氧/缺氧消化对污泥中总氮的去除率高于传统的好氧消化，达到了36.4%，而且能够降低消化污泥上清液中的氨氮和硝态氮浓度。     

Laboratory evaluation of thermophilic-anaerobic digestion to produce Class A biosolids. 1. Stabilization performance of a continuous-flow reactor at low residence time.

There is increasing interest in the United States in producing biosolids from municipal wastewater treatment that meet the criteria for Class A designation established by the U.S. Environmental Protection Agency. Class A biosolids are intended to be free of pathogens and also must meet requirements for reduction of the vector-attraction potential associated with untreated sludge. High-temperature processes are considered to produce Class A biosolids if the combination of operating temperature and treatment time exceeds minimum criteria, but this option is not applicable to mixed, continuous-flow reactors. Such reactors, or any combination of reactors that does not meet the holding time requirement at a specific temperature, must be demonstrated to inactivate pathogens to levels consistent with the Class A criteria. This study was designed to evaluate pathogen inactivation by thermophilic anaerobic digestion in a mixed, continuous-flow reactor followed by batch or plug-flow treatment. In this first of a two-part series, we describe the performance of a continuous-flow laboratory reactor with respect to physical and chemical operating parameters; microbial inactivation in the combined continuous-flow and batch treatment system is described in the second part. Sludges from three different sources were treated at 53 degrees C, while sludge from one of the sources was also treated at 55 and 51 degrees C. Relatively short hydraulic retention times (four to six days) were used to represent a conservative operating condition with respect to pathogen inactivation. Treatment of a fermented primary sludge led to an average volatile-solids (VS) destruction efficiency of 45%, while VS destruction for the other two sources was near or below 38%, the Class A criterion for vector attraction reduction. Consistent with other studies on thermophilic anaerobic digestion of sludges at short residence times, effluent concentrations of volatile fatty acids (VFAs) were relatively high. Also consistent with other studies, the most abundant VFA in the effluent was propionate. Gas production ranged from 0.3 to 0.5 m3/kg VS fed and from 0.8 to 1.3 m3/kg VS destroyed.     

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.     

Influence of the organic loading rate on the performance and the granular sludge characteristics of an EGSB reactor used for treating traditional Chinese medicine wastewater

The effects of the organic loading rate (OLR) on the performance and the granular sludge characteristics of an expanded granular sludge bed (EGSB) reactor used for treating real traditional Chinese medicine (TCM) wastewater were investigated. Over 90 % of the COD removal by the EGSB reactor was observed at the OLRs of 4 to 13 kg COD/(m³ day). However, increasing the OLR to 20 kg COD/(m³ day) by reducing the hydraulic retention time (HRT 6 h) reduced the COD removal efficiency to 78 %. The volatile fatty acid (VFA) concentration was 512.22 mg/L, resulting in an accumulation of VFAs, and propionic acid was the main acidification product, accounting for 66.51 % of the total VFAs. When the OLR increased from 10 to 20 kg COD/(m³ day), the average size of the granule sludge decreased from 469 to 258 μm. There was an obvious reduction in the concentration of Ca²⁺ and Mg²⁺ in the granular sludge. The visible humic acid-like peak was identified in the three-dimensional excitation-emission matrix (EEM) fluorescence spectra of the soluble microbial products (SMPs). The fatty acid bond, amide II bond, amide III bond, and C–H bond bending were also observed in the Fourier transform infrared (FTIR) spectra of the SMPs. Methanobacterium formicicum, Methanococcus, and Bacteria populations exhibited significant shifts, and these changes were accompanied by an increase in VFA production. The results indicated that a short HRT and high OLR in the EGSB reactor caused the accumulation of polysaccharides, protein, and VFAs, thereby inhibiting the activity of methanogenic bacteria and causing granular sludge corruption.     

In-field variation in 2,4-D mineralization in relation to sorption and soil microbial communities

This study was undertaken to assess 2,4-D mineralization in an undulating cultivated field, along a sloping transect (458 m to 442 m above sea level), as a function of soil type, soil microbial communities and the sorption of 2,4-D to soil. The 2,4-D soil sorption coefficient (Kd) ranged from 1.81 to 4.28 L kg(-1), the 2,4-D first-order mineralization rate constant (k) ranged from 0.04 to 0.13 day(-1) and the total amount of 2,4-D mineralized at 130 days (M(130)) ranged from 24 to 39%. Both k and M(130) were significantly negatively associated (or correlated) with soil organic carbon content (SOC) and Kd. Both k and M(130) were significantly associated with two fatty-acid methyl esters (FAME), i17:1 and a18, but not with twenty-two other individual FAME. Imperfectly drained soils (Gleyed Dark Grey Chernozems) in lower-slopes showed significantly lesser 2,4-D mineralization relative to well-drained soils (Orthic Dark Grey Chernozems) in mid- and upper-slopes. Well-drained soils had a greater potential for 2,4-D mineralization because of greater abundance and diversity of the microbial community in these soils. However, the reduced 2,4-D mineralization in imperfectly drained soils was predominantly because of their greater SOC and increased 2,4-D sorption, limiting the bioavailability of 2,4-D for degradation. The wide range of 2,4-D sorption and mineralization in this undulating cultivated field is comparable in magnitude and extent to the variability of 2,4-D sorption and mineralization observed at a regional scale in Manitoba. As such, in-field variations in SOC and the abundance and diversity of microbial communities are determining factors that require greater attention in assessing the risk of movement of 2,4-D by runoff, eroded soil and leaching.     

The effect of Mg<Superscript>2+</Superscript> on digestion performance and microbial community structures in sludge digestion systems

The important criteria in anaerobic digestion is the rate-limiting step which decides the fate of value-added products especially from waste-activated sludge (WAS). Hence, the present study investigated the effect of magnesium (Mg²⁺) addition on anaerobic digestion of WAS. The lab-scale experiments were conducted at 25 °C with Mg²⁺ doses ranging from 0.01 to 0.2 mol/L. Maximum total volatile fatty acids (VFAs) production (372.78 mg COD/L) occurred at a Mg²⁺ dose of 0.2 mol/L, which was about eight times higher than the control tests. Further, Mg²⁺ addition facilitated sludge dewaterability and phosphorus removal. The mechanism of improved VFAs generation was analyzed from the view of both chemical and biological effects. Chemical effect significantly enhanced the release of calcium and iron in WAS, resulting in the disintegration of WAS, which benefited hydrolysis and acidification processes. Illumina MiSeq sequencing analysis revealed that enrichment of functional bacteria and the increase of bacterial diversity were obtained in the 0.2 mol Mg²⁺/L experiment, while the influence was negative on the reactor with 0.025 mol/L Mg²⁺. Meanwhile, methanogens were accordantly inhibited in the experiments with Mg²⁺ addition.     

碱预处理污泥产酸效果及其生物群落研究

为了提高污泥水解酸化过程中的挥发酸产量,获取污水脱氮除磷所需的内碳源,以深圳市罗芳污水厂的二沉池污泥为研究对象,采用不同的碱量对其进行预处理。通过测定碱预处理污泥水解酸化过程中的挥发酸浓度,并采用聚合酶链式反应-变性梯度凝胶电泳(polymerase chain reaction denature gradient gel electrophoresis,PCR-DGGE)技术对参与碱预处理污泥水解酸化产酸过程的主要微生物种群进行分析,结果表明,当碱投加量为0.20 g NaOH/g VSS时,初始溶出的蛋白浓度为1 780 mg/L;水解酸化15 d时,挥发酸总量达到3 473 mg/L;参与产酸的主要细菌属于Firmicutes、Proteobacteria、Bacteroidetes三个门类。     

Aerobic biodegradation of organotin compounds in activated sludge batch reactors

The biodegradation behavior of four organotin (OT) compounds, namely tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT) and triphenyltin (TPhT), was studied in lab-scale activated sludge batch reactors. The activated sludge was spiked with the OT compounds at a level of 100 microg l(-1) as Sn. Determination of the OT compounds by GC-FPD after ethylation in the dissolved and particulate phase revealed that 24 h after the start of the experiments, almost the total of OT compounds has been removed from the dissolved phase and is associated with the suspended solids. Calculation of mass balance in batch reactors showed that OT compounds biodegradation was performed via a sequential dealkylation process. Removals due to biodegradation were differentiated according to the parent compound. In experiments with non-acclimatized biomass, a percentage of 27.1, 8.3, 73.8 and 51.3 was still present as TBT, DBT, MBT and TPhT, respectively, at the end of the experiment (18th day). Half-lives (t1/2) of 10.2 and 5.1 days were calculated for TBT and DBT, respectively, whereas apparent t1/2 values could not be determined for MBT and TPhT (t1/2>18 days). The capacity of activated sludge to biodegrade OT compounds in the absence of supplemental substrate indicated that these compounds can be metabolized as single sources of carbon and energy in activated sludge systems. Excluding TBT, the presence of low concentrations of supplemental substrate did not affect the biodegradation potential of activated sludge. The acclimatization of biomass on OT compounds enhanced significantly biodegradation, resulting in significant decreases of half-lives of OT compounds. As a result in the presence of acclimatized biomass, half-lives of 1.4, 3.6, 9.8 and 5.0 days were calculated for TBT, DBT, MBT and TPhT, respectively.     

pH值对污泥发酵产酸的影响

利用剩余污泥厌氧发酵产生挥发性脂肪酸,可作为污水脱氮除磷的有机碳源,而pH值是发酵产酸过程中重要的控制参数.研究了不同pH值条件下剩余污泥厌氧发酵产酸过程中各参数变化规律,探索pH值对其过程的影响及其分析.结果表明,碱性条件有利于污泥发酵产酸过程,实验最佳条件是控制反应初始pH值为10.0,仅8d发酵挥发性脂肪酸浓度就达到8.90 mmol/L.此外,污泥在发酵过程中,酸性条件下NH4+-N和PO43--P的释放量均大于碱性条件.