Seasonal effect on ammonia nitrogen removal by constructed wetlands treating polluted river water in southern Taiwan

A pilot-scale constructed wetland (CW) system, combining a free water surface wetland and a subsurface wetland in series, was used to purify highly polluted river water. The concentrations of constituents varied seasonally. The effects of season-dependent parameters, such as temperature, mass loading rate and inflow salinity, on the removal of ammonia nitrogen (AN) in the wetland system were examined at a constant hydraulic loading rate, based on data from June 1998 to February 2000. AN removal of the CW varied cyclically with the seasons. The removal efficiency and the first-order volumetric removal rate constant (k(V)) increased exponentially with water temperature, yielding a high temperature coefficient (theta). However, the mass removal rate decreased exponentially as temperature increased. These contradictory results made the actual effect of temperature uncertain. The inhibition of high water salinity on AN removal was also unclear because k(V) (as well as k(V20)) and mass removal rate were inversely proportional to salinity. However, mass loading rate (MLR) predominantly affected both the removal efficiency and the mass removal rate of AN, both of which were factors that explicitly determined seasonality. A power equation, k(V20)' alpha MLR(-n), was proposed to correct the variation of the mass loading rate in estimating k(V) and thus in designing a constructed wetland.     

Riboflavin-photosensitized degradation of atrazine in a freshwater environment

The effect of the photosensitizer riboflavin (0, 10, 50, 100 microM) on the fate of atrazine (10 mg/l) in a freshwater environment was studied. It was found that at 100 microM riboflavin significantly enhanced the degradation of atrazine and more than 80% of atrazine in a natural water environment was depleted in 72 h. The relative contribution of microbial assemblages and the freshwater matrix to the degradation of atrazine and the degradation kinetics of atrazine were compared under different experimental conditions. The products and pathways of atrazine transformation were studied with GC-MS and HPLC with a photodiode array detector. The results show that dealkylation and alkyl chain oxidation are involved in the degradation of atrazine.     

Using polymer mats to biodegrade atrazine in groundwater: laboratory column experiments

Large-scale column experiments were undertaken to evaluate the potential of in situ polymer mats to deliver oxygen into groundwater to induce biodegradation of the pesticides atrazine, terbutryn and fenamiphos contaminating groundwater in Perth, Western Australia. The polymer mats, composed of woven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2-m-long flow-through soil columns. The polymer mats proved efficient in delivering dissolved oxygen to anaerobic groundwater. Dissolved oxygen concentrations increased from <0.2 mg l(-1) to approximately 4 mg l(-1). Degradation rates of atrazine in oxygenated groundwater were relatively high with a zero-order rate of 240-380 microg l(-1) or a first-order half-life of 0.35 days. Amendment with an additional carbon source showed no significant improvement in biodegradation rates, suggesting that organic carbon was not limiting biodegradation. Atrazine degradation rates estimated in the column experiments were similar to rates determined in laboratory culture experiments, using pure cultures of atrazine-mineralising bacteria. No significant degradation of terbutryn or fenamiphos was observed under the experimental conditions within the time frames of the study. Results from these experiments indicate that remediation of atrazine in a contaminated aquifer may be achievable by delivery of oxygen using an in situ polymer mat system.     

人工湿地处理含盐富营养化水的植物根际与非根际菌群分析

为了探究盐胁迫对于人工湿地植物根际与非根际微生态环境的影响,将垂直流人工湿地应用于含盐富营养化水体处理,考察了0.05%、0.50%和1.00%盐度水平下的脱氮效果,并采用高通量测序方法分析湿地植物千屈菜根际与非根际的菌群变化。结果表明：在0.50%和1.00%盐胁迫下,系统的硝化作用受到抑制;然而在各盐度水平下,${ {\rm{NO}}_{\rm{3}}^{\rm{ - }}}$-N的去除率均大于95%,盐度胁迫下反硝化菌更能适应环境。对人工湿地系统在0.05%、0.50%和1.00%盐度水平下千屈菜根际与非根际基质样品的OTU聚类情况分析可知,在盐胁迫下,千屈菜根系丰富了土壤中微生物的多样性,根际环境中的微生物多样性明显高于非根际环境。盐度胁迫抑制了硝化菌的生长,仅在0.05%盐度的非根际组和0.50%盐度的根际组检测到有硝化作用菌群的存在。与硝化菌相比,反硝化菌更耐盐冲击,0.05%、0.50%与1.00%盐度水平下,均检测到反硝化菌,在1.00%盐度水平下检测出耐盐反硝化菌黄杆菌属Flavobacterium。     

Methanotrophic activity in a diffusive methane/oxygen counter-gradient in an unsaturated porous medium

Microbial methane (CH4) oxidation is a main control on emissions of this important greenhouse gas from ecosystems such as contaminated aquifers or wetlands under aerobic onditions. Due to a lack of suitable model systems, we designed a laboratory column to study this process in diffusional CH4/O2 counter-gradients in unsaturated porous media. Analysis and simulations of the steady-state CH4, CO2 and O2 gas profiles showed that in a 15-cm-deep active zone, CH4 oxidation followed first-order kinetics with respect to CH4 with a high apparent first-order rate constant of approximately 30 h(-1). Total cell counts obtained using DAPI-staining suggested growth of methanotrophic bacteria, resulting in a high capacity for CH4 oxidation. This together with apparent tolerance to anoxic conditions enabled a rapid response of the methanotrophic community to changing substrate availability, which was induced by changes in O2 concentrations at the top of the column. Microbial oxidation was confirmed by a approximately 7 per thousand enrichment in CH4 stable carbon isotope ratios along profiles. Using a fractionation factor of 1.025+/-0.0005 for microbial oxidation estimated from this shift and the fractionation factor for diffusion, simulations of isotope profiles agreed well with measured data confirming large fractionation associated with microbial oxidation. The designed column should be valuable for investigating response of methanotrophic bacteria to environmental parameters in future studies.     

曝气条件下进水C/N对水平潜流型人工湿地脱氮效果和氮转化功能微生物丰度的影响

为提高潜流型人工湿地在低C/N条件下的污水处理效果,考察了在植物生长旺盛期曝气条件下不同C/N(0.9∶1、2∶1、4∶1)对污水的脱氮效率、微生物群落结构和功能微生物丰度的影响.结果表明:NO3-去除率为57.48％～83.19％且随C/N的增加而增加;当C/N为2和4时,可提高COD和TN的去除率,COD和TN去除...     

微波辅助光催化降解阿特拉津的表观动力学

以内分泌干扰物阿特拉津为目标物,建立循环流化床微波辅助光催化体系,研究其微波辅助光催化降解规律。表观动力学研究发现,当阿特拉津初始浓度较低时,其在微波辅助光催化体系中的降解符合表观一级反应动力学特征。降解反应速率常数与阿特拉津初始浓度呈负线性相关,与紫外光强呈正线性相关,与催化剂浓度呈抛物线性相关。表观反应速率常数kobs=3.95×10-4c-0.27030I1.2224W0.3283,该模型计算值与实验值吻合较好,平均相对偏差仅为0.5%,可用于预测微波辅助光催化降解低浓度有机污染物的反应规律。     

Monod kinetics rather than a first-order degradation model explains atrazine fate in soil mini-columns: Implications for pesticide fate modelling

Pesticide transport models commonly assume first-order pesticide degradation kinetics for describing reactive transport in soil. This assumption was assessed in mini-column studies with associated batch degradation tests. Soil mini-columns were irrigated with atrazine in two intermittent steps of about 30 days separated by 161 days application of artificial rain water. Atrazine concentration in the effluent peaked to that of the influent concentration after initial break-through but sharply decreased while influx was sustained, suggesting a degradation lag phase. The same pattern was displayed in the second step but peak height and percentage of atrazine recovered in the effluent were lower. A Monod model with biomass decay was successfully calibrated to this data. The model was successfully evaluated against batch degradation data and mini-column experiments at lower flow rate. The study suggested that first-order degradation models may underestimate risk of pesticide leaching if the pesticide degradation potential needs amplification during degradation.     

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.     

Biodegradation of nonylphenol in soil

We investigated the effects of various factors (brij 30, brij 35, yeast extract, hydrogen peroxide and compost) on the aerobic degradation of nonylphenol (NP) in soil and characterized the structure of the microbial community in that soil. Residues of NP were measured using gas chromatography-mass spectrometry (GC-MS) and a change of microbial communities was demonstrated using denaturing gradient gel electrophoresis (DGGE). The results showed that Taichung sandy clay loam had higher NP degradation rate than Kaoshiung silty clay. The addition of compost, yeast extract (0.5 mg/l), brij 30 (55 microM), or brij 35 (91 microM) enhanced NP degradation, while the addition of hydrogen peroxide (1.0 mg/l) inhibited its degradation. We also found that the addition of various substrates changed the microbial community in the soils. Cytophaga sp. and Ochrobactrum sp. were constantly dominant bacteria under various conditions in the soil.     

Biofiltration kinetics of a gaseous aldehyde mixture using a synthetic matrix

Although aldehydes contribute to ozone and particulate matter formation, there has been little research on the biofiltration of these volatile organic compounds (VOCs), especially as mixtures. Biofiltration degradation kinetics of an aldehyde mixture containing hexanal, 2-methylbutanal (2-MB), and 3-methylbutanal (3-MB) was investigated using a bench-scale, synthetic, media-based biofilter. The adsorption capacity of the synthetic media for a model VOC, 3-methylbutanal, was 10 times that of compost. Periodic residence time distribution analysis (over the course of 1 yr) via a tracer study (84-99% recovery), indicated plug flow without channeling in the synthetic media and lack of compaction in the reactor. Simple first-order and zero-order kinetic models both equally fit the experimental data, yet analysis of the measured rate constants versus fractional conversion suggested an overall first-order model was more appropriate. Kinetic analysis indicated that hexanal had a significantly higher reaction rate (k = 0.09 +/- 0.005 1/sec; 23 +/- 1.3 ppmv) compared with the branched aldehydes (k = 0.04 +/- 0.0036 1/sec; 31 +/- 1.6 ppmv for 2-MB and 0.03 +/- 0.0051 1/sec; 22 +/- 1.3 ppmv for 3-MB). After 3 months of operation, all three compounds reached 100% removal (50 sec residence time, 18-46 ppmv inlet). Media samples withdrawn from the biofilter and observed under scanning electron microscopy analysis indicated microbial growth, suggesting removal of the aldehydes could be attributed to biodegradation.     

Biodegradation of hydrocarbons vapors: Comparison of laboratory studies and field investigations in the vadose zone at the emplaced fuel source experiment, Airbase Vaerløse, Denmark

The natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone can only be predicted when information about microbial biodegradation rates and kinetics are known. This study aimed at determining first-order rate coefficients for the aerobic biodegradation of 13 volatile petroleum hydrocarbons which were artificially emplaced as a liquid mixture during a field experiment in an unsaturated sandy soil. Apparent first-order biodegradation rate coefficients were estimated by comparing the spatial evolution of the resulting vapor plumes to an analytical reactive transport model. Two independent reactive numerical model approaches have been used to simulate the diffusive migration of VOC vapors and to estimate degradation rate coefficients. Supplementary laboratory column and microcosm experiments were performed with the sandy soil at room temperature under aerobic conditions. First-order kinetics adequately matched the lab column profiles for most of the compounds. Consistent compound-specific apparent first-order rate coefficients were obtained by the three models and the lab column experiment, except for benzene. Laboratory microcosm experiments lacked of sensitivity for slowly degrading compounds and underestimated degradation rates by up to a factor of 5. Addition of NH3 vapor was shown to increase the degradation rates for some VOCs in the laboratory microcosms. All field models suggested a significantly higher degradation rate for benzene than the rates measured in the lab, suggesting that the field microbial community was superior in developing benzene degrading activity.     

Photolytic treatment of atrazine-contaminated water: products, kinetics, and reactor design.

This study investigates the products, kinetics, and reactor design of atrazine photolysis under 254-nm ultraviolet-C (UVC) irradiation. With an initial atrazine concentration of 60 microg/L (60 ppbm), only two products remain in detectable levels. Up to 77% of decomposed atrazine becomes hydroxyatrazine, the major product. Both atrazine and hydroxyatrazine photodecompose following the first-order rate equation, but the hydroxyatrazine photodecomposition rate is significantly slower than that of atrazine. For atrazine photodecomposition, the rate constant is proportional to the square of UVC output, but inversely proportional to the reactor volume. For a photochemical reactor design, a series of equations are proposed to calculate the needed UVC output power, water treatment capacity, and atrazine outlet concentration.     

处理高污染河水垂直流人工湿地微生物群落特性

为了研究处理高污染河水垂直流人工湿地基质和根际微生物群落特性,采用PCR-DGGE技术对其进行分析,使用通用引物（BAC 338F GC和BAC 805R）对16S rDNA V3~V5区基因片段进行扩增。结果表明,湿地系统中基质微生物群落多样性随基质深度的增加呈现先增大后减小,根际微生物群落多样性逐层递减,同一垂直深度根际微生物群落多样性均高于基质;根际微环境刺激了严格好氧菌Acinetobacter tjernbergiae（不动杆菌属的）出现,证明根系具有泌氧功能;聚类分析表明湿地系统中微生物群落相似度较高,并随深度增加依次递减;测序结果表明湿地系统中拟杆菌门和变形菌门在系统发育树中分别显示出高度序列同源性,湿地系统上、中层广泛分布着好氧菌Flavobacterium sp.（黄杆菌属）和Sporocytophaga sp.（生孢噬纤维菌属）,并出现了大量的脱硫功能菌。     

Rapid reductive dechlorination of atrazine by zero-valent iron under acidic conditions

The dechlorination of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) via reaction with metallic iron under low-oxygen conditions was studied using reaction mixture pH values of 2.0, 3.0, and 3.8. The pH control was achieved through addition of sulfuric acid throughout the duration of the reaction. The lower the pH of the reaction mixture, the faster the degradation of atrazine. The surface area of the sulfuric acid-treated iron particles was 0.31 (+/- 0.01) m2 g-1 and the surface area normalized initial pseudo-first order rate constants (kSA, where rate = kSA x (surface area/l) x [Atrazine]) at pH values of 2.0, 3.0, and 3.8 were equal to, respectively, 3.0 (+/- 0.4) x 10(-3) min-1 m-2 l, 5 (+/- 3) x 10(-4) min-1 m-2 l, and 1 (+/- 1) x 10(-4) min-1 m-2 l. The observed products of the degradation reaction were dechlorinated atrazine (2-ethylamino-4-isopropylamino-1,3,5-triazine) and possibly hydroxyatrazine (2-ethylamino-4-isopropylamino-6-hydroxy-s-triazine). Triazine ring protonation may account, at least in part, for the observed effect of pH on atrazine dechlorination via metallic iron.     

高效阿特拉津降解菌株DNSIO降解条件优化

从长期施用阿特拉津的寒地黑土耕层（0～10cm）土壤中筛选到一株能以除草剂阿特拉津为氮源生长的降解菌株,结合16SrRNA序列分析结果,将该菌株命名为Arthrobacter sp．DNSl0。在接种量为10。CFU／mL的条件下,菌株DNSl0在24h内对100mg／L阿特拉津的降解率为99．41％。单因子实验结果表明,菌株DNSl0适宜生长和降解的条件范围是：温度25～35＇12,pH值5．0～8．0,培养液盐度0．1％～2％,对阿特拉津最大耐受浓度可达1200mg／L。正交实验法进一步表明,该菌株保持较好生长及降解能力的最优方案是温度30℃,pH值7．5,培养液盐度0．5％。影响其降解能力的环境因素的主次顺序依次是：温度〉盐度〉pH值。     

Nitrogen limited biobarriers remove atrazine from contaminated water: laboratory studies

Atrazine is one of the most frequently used herbicides. This usage coupled with its mobility and recalcitrant nature in deeper soils and aquifers makes it a frequently encountered groundwater contaminant. We formed biobarriers in sand filled columns by coating the sand with soybean oil; after which, we inoculated the barriers with a consortium of atrazine-degrading microorganisms and evaluated the ability of the barriers to remove atrazine from a simulated groundwater containing 1 mg L(-1) atrazine. The soybean oil provided a carbon rich and nitrogen poor substrate to the microbial consortium. Under these nitrogen-limiting conditions it was hypothesized that bacteria capable of using atrazine as a source of nitrogen would remove atrazine from the flowing water. Our hypothesis proved correct and the biobarriers were effective at removing atrazine when the nitrogen content of the influent water was low. Levels of atrazine in the biobarrier effluents declined with time and by the 24th week of the study no detectable atrazine was present (limit of detection<0.005 mg L(-1)). Larger amounts of atrazine were also removed by the biobarriers; when biobarriers were fed 16.3 mg L(-1) atrazine 97% was degraded. When nitrate (5 mg L(-1) N), an alternate source of nitrogen, was added to the influent water the atrazine removal efficiency of the barriers was reduced by almost 60%. This result supports the hypothesis that atrazine was degraded as a source of nitrogen. Poisoning of the biobarriers with mercury chloride resulted in an immediate and large increase in the amount of atrazine in the barrier effluents confirming that biological activity and not abiotic factors were responsible for most of the atrazine degradation. The presence of hydroxyatrazine in the barrier effluents indicated that dehalogenation was one of the pathways of atrazine degradation. Permeable barriers might be formed in-situ by the injection of innocuous vegetable oil emulsions into an aquifer or sandy soil and used to remove atrazine from a contaminated groundwater or to protect groundwater from an atrazine spill.     

Constructed wetlands for mitigation of atrazine-associated agricultural runoff

Atrazine was amended into constructed wetlands (59-73x14x0.3 m) for the purpose of monitoring transport and fate of the pesticide to obtain information necessary to provide future design parameters for constructed wetlands mitigation of agricultural runoff. Following pesticide amendment, a simulated storm and runoff event equal to three volume additions was imposed on each wetland. Targeted atrazine concentrations were 0 microg/l (unamended control), 73 microg/l, and 147 microg/l. Water, sediment, and plant samples were collected weekly for 35 days from transects longitudinally distributed throughout each wetland and were analyzed for atrazine using gas chromatography. Between 17 and 42% of measured atrazine mass was within the first 30-36 m of wetlands. Atrazine was below detection limits (0.05 microg/kg) in all sediment and plant samples collected throughout the duration of this study. Aqueous half lives ranged from 16 to 48 days. According to these data, conservative buffer travel distances of 100-280 m would be necessary for effective runoff mitigation.     

Anaerobic treatment of atrazine bearing wastewater.

Performance of mixed microbial anaerobic culture in treating synthetic waste-water with high Chemical Oxygen Demand (COD) and varying atrazine concentration was studied. Performance of hybrid reactors with wood charcoal as adsorbent, with a dose of 10 g/l and 40 g/l, along with the microbial mass was also studied. All the reactors were operated in sequential mode with Hydraulic Retention Time (HRT) of 5 days. In all the cases, COD removal after 5 days was found to be above 81%. Initial COD was above 1,000 mg/l. From a hybrid reactor COD removal after 2 days was observed to be 90%. Atrazine reduction after 5 days by microbial mass alone was 43.8%, 40% and 33.2% with an initial concentration of 0.5, 1.0 and 2.0 mg/l respectively. MLSS on all the cases were almost same. Increasing MLSS concentration by about 2 fold did not increase the atrazine removal efficiency significantly. Maximum atrazine removal was observed to be 64% from the hybrid reactor with 10 g/l of wood charcoal and 69.4% from the reactor with 40 g/l of wood charcoal. Atrazine removal from the hybrid reactors after 15 days were observed to be 35.7% and 38.7%, which showed that the higher dose of wood charcoal in hybrid reactor did not improve the atrazine removal efficiency significantly. Specific methanogenic activity test showed no inhibitory effect of atrazine on methane producing bacteria. The performance of anaerobic microorganisms in removing atrazine with no external carbon source and inorganic nitrogen source was studied in batch mode. With an initial concentration of 1.0 mg/l, reduction of atrazine by the anaerobic microorganisms in absence of external carbon source after 35 days was observed to be 61.8% where as in absence of external carbon and inorganic nitrogen source the reduction was only 44.2% after 150 days. Volatilization loss of atrazine was observed to be insignificant.     

基于异构载体的海产品暂养水的协同处理

针对海产品暂养水盐度高、低温环境下靶向菌难驯化、难富集等问题,构建了微生物驯化富集装置,采用玉米芯作为异构载体与碳源,在低温条件下,通过检测水质与微生物群落结构等指标,探究了海产品暂养水对优势菌种演替的推动作用以及微生物群落结构与异构载体的相关性,并对污染物降解与水处理效果进行了分析评价。结果表明：在低温条件下,海产品暂养水对微生物的驯化富集效果较佳;以属水平为例,经过驯化富集培养的菌液主要以假单胞菌属(Pseudomonas)、拟杆菌属(Bacteroides)和气单胞菌属(Aeromonas)为主,同时异构碳源的构造也对微生物的生长起到一定的促进作用;挂膜后的异构碳源对高盐暂养水的处理效果较佳,脱氮率达到(73.46±0.55)%,除磷率为(40.03±0.55)%,除沫率为(82.14±0.23)%。该装置在投入靶向菌与异构碳源后,提高了对高盐暂养水的处理能力;同时,玉米芯作为碳源供给,其缓释效果能够克服能量的过释并减少能耗,保证微生物的存活与运行。研究探讨了微生物与异构载体协同处理高盐暂养水的效果及其耦合效应,为高盐暂养水处理技术的创新与农用废弃物的回收利用提供了参考。