Investigation of the ultraviolet photolysis method for the determination of organic nitrogen in aerosol samples

The research objective was to adapt the ultraviolet (UV)-photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2(2) factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 degrees C occurred at pH 2.0 with a 24-hr irradiance period at concentrations <33 microM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH4+), but urea released a near equimolar ratio of NH4+ and nitrate (NO3-). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM10 were 78.1 +/- 29.2 nmol-Nm(-3) and 8.3 +/- 4.9 nmol-Nm(-3), respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 +/- 5.7%, and the majority of the DON (79.1 +/- 18.2%) was found in the fine particulate matter (PM2.5) fraction. The average concentrations of DIN and DON in the PM2.5 fraction were 54.4 +/- 25.6 nmol-Nm(-3) and 6.5 +/- 4.4 nmol-Nm(-3), respectively.     

Investigation of the Ultraviolet Photolysis Method for the Determination of Organic Nitrogen in Aerosol Samples

Abstract

The research objective was to adapt the ultraviolet (UV)photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2² factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 °C occurred at pH 2.0 with a 24-hr irradiance period at concentrations < µM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH₄ ⁺), but urea released a near equimolar ratio of NH₄ ⁺ and nitrate (NO₃ ^?). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM₁₀ were 78.1 ± 29.2 nmol-Nm^?3and 8.3 ± 4.9 nmol-Nm^?3, respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 ± 5.7%, and the majority of the DON (79.1 ± 18.2%) was found in the fine particulate matter (PM_2.5) fraction. The average concentrations of DIN and DON in the PM_2.5 fraction were 54.4 ± 25.6 nmol-Nm^?3 and 6.5 ± 4.4 nmol-Nm^?3, respectively.     

Bioavailability of dissolved organic nitrogen in treated effluents.

The research objective was to assess dissolved organic nitrogen (DON) bioavailability in wastewater effluents from a pilot-scale nitrification plant and a laboratory-scale total nitrogen (TN) removal plant. The DON bioavailability was assessed using a 14-day bioassay protocol containing bacterial and algal inocula. Nitrogen species, dissolved organic carbon, chlorophyll a, and biomass (as total suspended solids and culturable cell counts) concentrations were measured to assess DON bioavailability. The results showed an increase in algal chlorophyll a concentration, with a concurrent increase in algal biomass over time; increased bacterial counts and a decrease in DON concentration over time; and increased carbon-to-nitrogen ratio at the end of the 14-day bioassay, indicating effluent DON bioavailability to algae and bacteria. Approximately 18 to 61% of the initial DON in low-total-nitrogen wastewater effluent (TN = 4 to 5 mg/L) sample was bioavailable. The results show that bacteria and algae uptake and release DON during their growth.     

Effects of land use and land cover, stream discharge, and interannual climate on the magnitude and timing of nitrogen, phosphorus, and organic carbon concentrations in three coastal plain watersheds.

In-stream nitrogen, phosphorus, organic carbon, and suspended sediment concentrations were measured in 18 subbasins over 2 annual cycles to assess how land use and land cover (LULC) and stream discharge regulate water quality variables. The LULC was a primary driver of in-stream constituent concentrations and nutrient speciation owing to differences in dominant sources and input pathways associated with agricultural, urban, and forested land uses. Stream discharge was shown to be a major factor that dictated not only the magnitude of constituent concentrations, but also the chemical form. In high discharge agricultural subbasins, where nitrate was the dominant nitrogen form, there was a negative correlation between discharge and nitrate concentration indicating groundwater inputs as the dominant pathway. In urban settings, however, nitrate was positively correlated with discharge, and, in forested subwatersheds, where dissolved organic nitrogen (DON) was the dominant nitrogen form, there was a positive correlation between discharge and DON, indicating washoff from the watershed as the dominant input pathway. Similarly, phosphorus concentrations were strongly regulated by LULC, discharge, and seasonality. This comparative study highlights that different mechanisms regulate different forms of nitrogen, phosphorus, and carbon, and thus field programs or water quality models used for regulatory purposes must assess these nutrient forms to accurately apply management plans for nutrient reductions.     

溶解氧对底泥扰动状态下水体中磷去除和固定的影响

以太湖梅梁湾底泥和上覆水为研究对象,通过实验室实验研究了底泥扰动状态下溶解氧水平（2～4mg／L、5～6mg／L、7～8mg／L）对上覆水中磷去除和固定的影响。结果表明,底泥扰动和溶解氧水平对上覆水中磷迁移有明显影响。扰动时间延长,溶解性磷酸盐（DIP）和溶解性总磷（DTP）均呈降低的趋势;但溶解氧水平提高,上覆水中DIP和DTP浓度有所增加。底泥扰动和溶解氧水平改变了悬浮物上不同形态磷的数量分布。随着溶解氧水平提高,NH4Cl-P（1～5d平均值）和Fe／Al—P（1～5d平均值）含量及其占总磷（Tot—P）的百分比均呈逐渐降低的趋势。另外,闭蓄态铁铝结合态磷（Fe／Al—P）占Fe／Al—P的比值从51．2％（2～4mg／L）增加至54．1％（7～8mg／L）。     

Simultaneous nitrification, denitrification, and phosphorus removal in single-tank low-dissolved-oxygen systems under cyclic aeration.

Simultaneous nitrification and denitrification (SND or SNdN) may occur at low dissolved oxygen concentrations. In this study, bench-scale (approximately 6 L) bioreactors treating a continuous feed of synthetic wastewater were used to evaluate the effects of solids retention time and low dissolved oxygen concentration, under cyclic aeration, on the removal of organics, nitrogen, and phosphorus. The cyclic aeration was carried out with repeated cycles of 1 hour at a higher dissolved oxygen concentration (HDO) and 30 minutes at a lower (or zero) dissolved oxygen concentration (LDO). Compared with aeration at constant dissolved oxygen concentrations, the cyclic aeration, when operated with proper combinations of HDO and LDO, produced better-settling sludge and more complete nitrogen and phosphorus removal. For nitrogen removal, the advantage resulted from the more readily available nitrate and nitrite (generated by nitrification during the HDO period) for denitrification (during the LDO period). For phosphorus removal, the advantage of cyclic aeration came from the development of a higher population of polyphosphate-accumulating organisms, as indicated by the higher phosphorus contents in the sludge solids of the cyclically aerated systems. Nitrite shunt was also observed to occur in the LDO systems. Higher ratios of nitrite to nitrate were found in the systems of lower HDO (and, to less dependency, higher LDO), suggesting that the nitrite shunt took place mainly because of the disrupted nitrification at lower HDO. The study results indicated that the HDO used should be kept reasonably high (approximately 0.8 mg/L) or the HDO period prolonged, to promote adequate nitrification, and the LDO kept low (< or =0.2 mg/L), to achieve more complete denitrification and higher phosphorus removal. The above findings in the laboratory systems find strong support from the results obtained in full-scale plant implementation. Two plant case studies using the cyclic low-dissolved-oxygen aeration for creating and maintaining SND are also presented.     

Phosphorus release in aerobic sludge digestion.

The objectives of this study are to examine the phosphorus release in aerobic sludge digestion and to better understand its governing mechanisms. In this study, phosphorus release was examined using the secondary sludge from both conventional and biological nutrient removal processes. The experiments were carried out at room temperature (22 +/- 2 degrees C), with or without automatic control of pH (4.5 to 7.8), and under three aeration schemes: fully aerobic (dissolved oxygen [DO] at 3 to 4 mg/L), low DO (0.2 to 0.8 mg/L), and cyclic (with alternate on/off aeration). The released phosphorus concentrations were 20 to 80 mg/L for the conventional sludge and 60 to 130 mg/L for the biophosphorus sludge. Higher phosphorus release also occurred at low pH (<6.0). As for the effect of DO, fully aerobic digestion caused higher phosphorus release than the low-DO and cyclic operations. For better understanding, the solid phosphorus in sludge was conceptually categorized into three forms: inorganic phosphorus precipitates, organic cellular phosphorus, and polyphosphate (poly-P) in polyphosphate-accumulating organisms. Dissolution of inorganic phosphorus precipitates is controlled by physical and chemical conditions, with pH being the most important in this study. Lowering the pH to 4 to 6 clearly promoted the release of inorganic phosphorus. Polyphosphate hydrolysis, on the other hand, was found to be regulated biologically (sensitive to occurrence of anaerobic conditions) and was insignificant in the glutaraldehyde-fixed sludge. Phosphorus release from organic phosphorus should correlate with the volatile solid (VS) digestion, which lyses the cells and frees the phosphorus covalently bonded with the organic matters. The amounts of phosphorus released per unit VS digested (deltaP/deltaVS) were therefore calculated for experiments with long periods of constant pH (to minimize interferences from dissolution/precipitation of inorganic phosphorus). The results suggested that some poly-P was hydrolyzed and released accompanying the aerobic VS digestion, but at rates far lower than those under anaerobic conditions.     

反硝化除磷的影响特性试验

采用SBR反应器(厌氧/缺氧/好氧工艺),分别研究了乙酸盐及硝酸盐浓度变化对反硝化除磷的影响特性。试验结果表明,当进水COD浓度>230mg/L时,乙酸盐浓度的变化对释磷、除磷速率等影响并不显著。在硝酸盐浓度<30mg/L时,硝酸盐浓度越高,缺氧段除磷速率也就越高。在C/P>23,C/N>5条件下,SBR系统对磷、氮去除率在90%以上。     

Effect of catchment land use and soil type on the concentration,quality, and bacterial degradation of riverine dissolved organic matter

We studied the effects of catchment characteristics (soil type and land use) on the concentration and quality of dissolved organic matter (DOM) in river water and on the bacterial degradation of terrestrial DOM. The share of organic soil was the strongest predictor of high concentrations of dissolved organic carbon, nitrogen, and phosphorus (DOC, DON, and DOP, respectively), and was linked to DOM quality. Soil type was more important than land use in determining the concentration and quality of riverine DOM. On average, 5–9 % of the DOC and 45 % of the DON were degraded by the bacterial communities within 2–3 months. Simultaneously, the proportion of humic-like compounds in the DOM pool increased. Bioavailable DON accounted for approximately one-third of the total bioavailable dissolved nitrogen, and thus, terrestrial DON can markedly contribute to the coastal plankton dynamics and support the heterotrophic food web.     

Water-soluble organic nitrogen in atmospheric aerosol: a comparison of UV and persulfate oxidation methods

Two well established methods that are widely applied in the determination of marine dissolved organic nitrogen (DON) have been investigated in their application to the determination of rainwater DON and the water-soluble organic nitrogen component of atmospheric aerosol. Empirical observation highlighted some difficulties in the analysis of DON in these non-marine matrices, so some practical suggestions for the extension of the oxidative methods to atmospheric samples are proposed.Ten rain samples, 20 aqueous aerosol extracts, and a suite of commercially obtained organic nitrogen compounds were both chemically oxidised by persulfate and oxidised by exposure to high-intensity ultraviolet light. The total dissolved nitrogen concentration of the rains in this study ranged from 4 to 35 μM nitrogen. The aerosol extracts were diluted to a pre-oxidation concentration range of 12–65 μM N for oxidation and analysis. Both UV and persulfate methods require the aqueous extract of the aerosol organic nitrogen to be diluted approximately to rainwater concentrations for optimal oxidation efficiency, since sub-optimal recoveries and high analytical variability arise at high concentration. Some potential causes of analytical interference at higher concentration are discussed.This study shows that total dissolved nitrogen results obtained by the two methods are linearly correlated (with an R² of 0.87 for 30 samples) over the full range of natural rainwater concentrations, but results obtained using the persulfate oxidation are about 30% lower than those obtained by photo-oxidation.     

Investigating phosphorus limitation in a fixed bed filter with phosphorus and nitrogen profile measurements

In 2000, the European Union adopted the European Water Framework Directive (WFD) (European Commission, 2000). The WFD focuses on increasingly stringent nutrient standards including ultra low nitrogen (< 2.2 mg N-total/L) and phosphorus concentrations (< 0.15 mg total phosphorus/L) in receiving surface waters and in relevant point sources like wastewater treatment plant (WWTP) effluent. Expansion of WWTPs with advanced post-treatment processes, like effluent filtration, is widely proposed to meet possible future effluent discharge standards. When combining biological nitrate-nitrogen and chemical phosphorus removal in one filter, phosphorus limitation in the denitrifying process may occur. This study investigated where in the filter bed and under which conditions phosphorus limitation occurs. Profile measurements for nitrate, nitrite, and orthophosphorus (PO4-P) combined with chemical oxygen demand (COD) and 02 were conducted. Results showed that the required PO4-P/NOx-N ratio is approximately 0.006 mg/mg after phosphorous precipitation and flocculation. Profile measurements have proven to be an applicable and useful tool. It showed how nitrate and orthophosphorus are removed through the filter bed based on the PO4-P/NOx-N ratio. When orthophosphorus is removed more rapidly and efficiently compared to nitrate, the PO4-P/NOx-N ratio decreases. When PO4-P/NOx-N ratio thresholds are approximately 0.006 mg/mg for a certain period of time and water temperatures varied significantly, orthophosphorus limitation may occur. Changing the filter-bed configuration or decreasing the coagulant dosage can prevent limitation of the denitrifying process because of a phosphorous shortage.     

水深对表面流人工湿地污染河水处理系统运行效果的影响

基于中试系统一年的连续运行监测,研究了水深对芦苇表面流人工湿地污染河水处理系统的影响。结果表明,水深对表面流人工湿地污染河水处理系统运行效果有很大影响,在进水COD、氨氮、总氮和总磷等分别为36±4.46、0.92±0.47、6.27±2.01和0.13±0.05 mg/L条件下,水深50 cm时处理效果最好,COD、氨氮、总氮和总磷去除率分别达到42.75%、58.42%、56.94%和43.24%。综合污染物去除效果和人工湿地建设工程量,芦苇表面流人工湿地的水深宜采用50 cm。人工湿地系统中植物光合生理和溶解氧等研究表明,水深主要通过影响植物生长和溶解氧等而影响人工湿地的水质净化效果。     

改进型A~2/O工艺处理城市生活污水的脱氮除磷效能研究

在分析传统A2/O工艺缺陷的基础上,提出了一种改进型A2/O工艺。为了防止回流污泥中的硝酸盐进入厌氧区,在传统A2/O工艺的厌氧区后面增加一个体积较小的缺氧选择池,回流污泥进入缺氧选择池,并进行反硝化消耗回流污泥中的硝酸盐;同时,在缺氧区通过反硝化除磷实现"一碳两用"。结果表明,改进型A2/O工艺有较好的脱氮除磷效果,在COD为298mg/L、TN为55mg/L左右、TP为7mg/L左右时,系统对COD、TN、TP的平均去除率分别为88.44%、77%、95%。     

沉水植被构建对上海辰山植物园景观湖水质的影响

以辰山植物园景观湖为研究对象,研究了景观湖建成初期沉水植物群落构建对水体水质因子的影响;并应用相关性分析(correlation analysis)和主成分分析(principal components analysis)对各水质和生态因子之间的相互关系进行了研究。结果表明,景观湖沉水植被建成1年后,水体水质处于Ⅲ类,其中叶绿素a含量5.48±1.930μg/L、总氮1.40±0.136mg/L、总磷0.080±0.015 mg/L、透明度108±20 cm、高锰酸盐指数5.50±1.26 mg/L;除高锰酸盐指数(CODMn)外,其他水质指标均较构建前有显著改善;并且景观湖水质显著优于外河道补充水源水质。相关性分析表明,景观湖水体叶绿素a含量与N、P营养盐呈显著正相关,但却与水温呈极显著负相关,这显示了草型景观湖水质的显著特征;主成分分析显示,第一主成分包含硝态氮、亚硝态氮、总磷、活性磷、叶绿素、水温、透明度和pH等变量,第二主成分包括高锰酸盐指数和氨氮等变量;第一主成分中的水质参数可作为辰山植物园景观湖后续水生态管理中的主要监测对象;此外,主成分分析还显示TP对水体叶绿素的增加具有很高正权重。     

The degradation of dissolved organic nitrogen associated with melanoidin using a UV/H2O2 AOP

The aim of this study was to examine the simultaneous degradation of dissolved organic nitrogen (DON) and associated colour from wastewater containing melanoidins by an advanced oxidation process (AOP). UV irradiation of H2O2 was used as the mechanism to create the hydroxyl radical for oxidation. Melanoidins are large nitrogenous organic compounds that are refractory during biological wastewater treatment processes. The simultaneous degradation of DON and colour, present as a result of these compounds, was investigated using an AOP. The oxidation process was much more capable of removing colour (99% degradation), dissolved organic carbon (DOC) (50% degradation) and DON (25% degradation) at the optimal applied dose of hydrogen peroxide for the system (3300 mg l(-1)). This indicated that colour and DON removal were decoupled problems for the purpose of treating melanoidin by an AOP and thus colour removal can not be used as an indication of DON removal Colour was caused by organic molecules with molecular weight greater than 10 kDa. Oxidation caused a partial reduction of the DON (41-15% of the total dissolved nitrogen) and DOC (29-14% of the DOC) associated with the large molecular weight fraction (>10 kDa) and almost complete colour removal (87-3% of the total colour). The degraded DON was mostly accounted for by the formation of ammonia (31% of the nitrogen removed from the large fraction) and small molecular weight compounds (66% of the nitrogen removed from the large fraction). The degraded DOC appeared to be mostly mineralised (to CO2) with only 20% of the degraded compounds appearing as small molecular weight DOC.     

污水生物除磷若干影响因素分析

在系统阐述污水生物除磷机理的基础上,深入分析了微生物群体平衡、城市污水水质、环境因子以及工艺运行参数和运行方式等方面对生物除磷效果的影响.分析结果表明:生物除磷系统的溶解氧浓度不宜太高,一般好氧区DO＜2 mg/L,厌氧区DO＜0.2 mg/L;厌氧段存在硝酸盐对生物释磷有负面影响,缺氧段存在一定浓度的硝酸盐有利于生物聚磷;碳源必须充分、易降解;TKN/COD＜0.1的城市污水有利于生物除磷;pH偏碱性可提高生物除磷效率;低温对生物除磷效果影响不明显.     

Internal ecosystem feedbacks enhance nitrogen-fixing cyanobacteria blooms and complicate management in the Baltic Sea

Eutrophication of the Baltic Sea has potentially increased the frequency and magnitude of cyanobacteria blooms. Eutrophication leads to increased sedimentation of organic material, increasing the extent of anoxic bottoms and subsequently increasing the internal phosphorus loading. In addition, the hypoxic water volume displays a negative relationship with the total dissolved inorganic nitrogen pool, suggesting greater overall nitrogen removal with increased hypoxia. Enhanced internal loading of phosphorus and the removal of dissolved inorganic nitrogen leads to lower nitrogen to phosphorus ratios, which are one of the main factors promoting nitrogenfixing cyanobacteria blooms. Because cyanobacteria blooms in the open waters of the Baltic Sea seem to be strongly regulated by internal processes, the effects of external nutrient reductions are scale-dependent. During longer time scales, reductions in external phosphorus load may reduce cyanobacteria blooms; however, on shorter time scales the internal phosphorus loading can counteract external phosphorus reductions. The coupled processes inducing internal loading, nitrogen removal, and the prevalence of nitrogen-fixing cyanobacteria can qualitatively be described as a potentially self-sustaining "vicious circle." To effectively reduce cyanobacteria blooms and overall signs of eutrophication, reductions in both nitrogen and phosphorus external loads appear essential.     

蜘蛛兰去除不同程度富营养水体中氮磷及抑藻效应简

研究了蜘蛛兰在不同程度富营养化水体中对氮、磷的去除和对藻类的抑制效应。结果表明,蜘蛛兰在3种不同程度富营养化水体中均能正常生长,且对富营养水体中的氮、磷和叶绿素a浓度均表现出良好的净化去除效果。在45 d的实验中,3种不同程度富营养水体的TN、NO₃^--N、NH₄⁺-N和TP浓度分别由初始的3.69~25.65、2.79~21.14、0.75~3.57和0.14~1.23mg/L降至1.25~18.99、1.08~16.03、0.18~1.39和0.06~0.77mg/L,在3种不同程度富营养水体中植物的平均生物量累积增长率分别为40.98% 、64.41% 和95.08%。实验各处理组富营养化水体中的叶绿素a浓度及荧光参数短期内都显著下降,而各对照组中则较稳定或略有下降。蜘蛛兰不仅可以净化富营养水体中营养元素,且对水体中藻类的生长有明显的抑制作用,其在水体生态修复工程中具有良好的应用前景。     

改良型Carrousel氧化沟工艺生物脱氮除磷效果研究

为了提高改良型Carrousel氧化沟工艺污水处理厂的脱氮除磷效果,结合某污水处理厂3年的运行实践,讨论了该工艺的处理效果,生物脱氮除磷原理及影响出水效果的因素.分析表明将DO控制在0.3～0.7 mg/L范围内,能够使出水中的TN浓度低于20 mg/L;在氧化沟中发生的同步硝化反硝化反应(SND)对总氮的去除的贡献占总系统脱氮的66%;该系统剩余污泥的含磷率为3.0%,生物细胞中平均含磷量可达细胞干重的4.2%;总磷去除率与污泥龄具有很好的线性关系,加大污泥排放量可以提高除磷效果.     

水葫芦对滇池底泥氮磷营养盐释放的影响

为了探讨水葫芦对富营养湖泊底泥氮磷营养盐释放的影响,通过原位采集滇池柱状底泥,以蒸馏水为上覆水,进行了25d的室内静态模拟实验。实验比较了水葫芦处理组和空白对照组底泥氨氮（NH4-N）、硝态氮（NO3^-N）、溶解性总氮（DTN）、正磷酸盐（PO4^3--P）等的释放特征。结果表明,与对照组相比,水葫芦处理组上覆水溶解氧、pH显著性降低,而PO4^3-P浓度显著性升高;在实验前2d,水葫芦处理组上覆水NH4^＋N和DTN浓度显著性高于对照组,而在5～25d时,其显著性低于对照组。根据上覆水营养盐浓度、水葫芦植株吸收营养盐总量,推算底泥氮磷营养盐释放的平均速率,表明水葫芦加速了滇池底泥氮、磷营养盐的释放速率,处理组氮、磷释放速率分别为对照组的5．3～170．2和1．5～21．6倍。