Modeling the seasonal autochthonous sources of dissolved organic carbon and nitrogen in the upper Chesapeake Bay

In this paper we investigate the seasonal autochthonous sources of dissolved organic carbon (DOC) and nitrogen (DON) in the euphotic zone at a station in the upper Chesapeake Bay using a new mass-based ecosystem model. Important features of the model are: (1) carbon and nitrogen are incorporated by means of a set of fixed and varying C:N ratios; (2) dissolved organic matter (DOM) is separated into labile, semi-labile, and refractory pools for both C and N; (3) the production and consumption of DOM is treated in detail; and (4) seasonal observations of light, temperature, nutrients, and surface layer circulation are used to physically force the model. The model reasonably reproduces the mean observed seasonal concentrations of nutrients, DOM, plankton biomass, and chlorophyll a. The results suggest that estuarine DOM production is intricately tied to the biomass concentration, ratio, and productivity of phytoplankton, zooplankton, viruses, and bacteria. During peak spring productivity phytoplankton exudation and zooplankton sloppy feeding are the most important autochthonous sources of DOM. In the summer when productivity peaks again, autochthonous sources of DOM are more diverse and, in addition to phytoplankton exudation, important ones include viral lysis and the decay of detritus. The potential importance of viral decay as a source of bioavailable DOM from within the bulk DOM pool is also discussed. The results also highlight the importance of some poorly constrained processes and parameters. Some potential improvements and remedies are suggested. Sensitivity studies on selected parameters are also reported and discussed.     

淡水水体溶解有机氮对有毒藻种的生物有效性

溶解有机氮(Dissolved organic nitrogen,DON)是多数天然水体中溶解氮的主要组成部分。天然水体DON是许多微生命体包括有毒藻种的氮营养源,在供水安全以及水体富营养化等方面的生态环境效应不容忽视。文章系统地介绍了淡水水体DON含量与来源、生物有效性与估算方法,以及对有毒藻种生长的影响。DON的来源是影响水体中DON含量动态特征的关键因素。DON来源包括陆地径流,植物碎屑,土壤淋溶液,沉积物释放,大气沉降,藻类、大型植物、细菌与细胞死亡或自我分解,微型及大型浮游动物捕食和排泄、分泌物释放等。研究表明约有12%～72%的DON可迅速被生物所利用,具显著差异,究其原因可能是其来源组成、化学本质(分子质量与极性)、测试生物组成、是否有细菌作用等因素造成的。不同藻种具有不同氮源利用能力,DON对藻类生长具有直接或间接的作用,并可能影响藻类群落结构(有毒藻类成为优势种)。考虑到水环境保护与饮用水安全供水的重要性,未来研究应重视淡水水体DON生物有效性与其化学本质的揭示,尤其是对有毒藻种。     

淡水水体溶解有机氮对有毒藻种的生物有效性

溶解有机氮（Dissolved organic nitrogen,DON）是多数天然水体中溶解氮的主要组成部分。天然水体DON是许多微生命体包括有毒藻种的氮营养源,在供水安全以及水体富营养化等方面的生态环境效应不容忽视。文章系统地介绍了淡水水体DON含量与来源、生物有效性与估算方法,以及对有毒藻种生长的影响。DON的来源是影响水体中DON含量动态特征的关键因素。DON来源包括陆地径流,植物碎屑,土壤淋溶液,沉积物释放,大气沉降,藻类、大型植物、细菌与细胞死亡或自我分解,微型及大型浮游动物捕食和排泄、分泌物释放等。研究表明约有12％～72％的DON可迅速被生物所利用,具显著差异,究其原因可能是其来源组成、化学本质（分子质量与极性）、测试生物组成、是否有细菌作用等因素造成的。不同藻种具有不同氮源利用能力,DON对藻类生长具有直接或间接的作用,并可能影响藻类群落结构（有毒藻类成为优势种）。考虑到水环境保护与饮用水安全供水的重要性,未来研究应重视淡水水体DON生物有效性与其化学本质的揭示,尤其是对有毒藻种。     

Effect of environmental forcing on the fate of nutrients, dissolved organic matter and heavy metals released by a coastal wastewater pipeline

Discharges of nutrients, urea, dissolved organic matter and heavy metals by a sewage underwater pipeline are analysed in comparison to environmental conditions in a shallow coastal zone. Variable thermo-haline stratifications of the water column and currents in upper (2.62-34.97 cm s^-1) and deeper (0.83-10.91 cm s^-1) layers drive vertical diffusion and lateral transport of wastewaters. Loads of reactive phosphorus (0.13 tons d^-1) and ammonium (1.62 tons d^-1) by the pipeline are not negligible compared to the major river loads in the gulf. High concentrations of urea (≤11.51 μmol N dm^-3) were found in the area of wastewater release. Ammonium uptake (6.14-534 nmol N dm^-3 h^-1) strongly exceeded nitrate uptake (0.19-138 nmol N dm^-3 h^-1), indicating that discharges of ammonium by the pipeline are actively assimilated by plankton community even at low levels of light. Distribution of Zn (≤27.7 ppb), Cu (≤25.6 ppb), Cd (≤0.80 ppb) and Pb (≤13.5 ppb) in the water column and the measurement of their complex-forming capacity in seawater did not indicate a persistent perturbation of the pelagic environment due to heavy metals.     

洱海沉积物不同分子量溶解性有机氮空间分布及光谱特征

利用超滤技术对洱海沉积物溶解性有机氮(DON)进行分子量分级,探究了DON各组分空间分布特征,并运用紫外-可见吸收光谱和三维荧光光谱对其结构进行了表征.结果表明,洱海沉积物总DON含量ω(DON)为23.46—61.40 mg·kg-1,平均值为37.19 mg·kg-1,空间分布总体呈现南部>北部>中部的趋势;分子量大于1K Da的大分子组分ω(>1KDa)占ω(DON)的比例为79.1%—93.0%,即洱海沉积物DON是以大分子为主.沉积物DON各组分的芳香性及腐殖化程度较高,芳香环取代基中活性官能团种类较多,且南部芳香性及腐殖化程度最高,北部芳香环取代基种类最多;大分子组分DON含有类富里酸荧光物质,其来源于陆源输入和微生物降解共同作用.由此可见,洱海沉积物DON主要由大分子物质组成,其腐殖化程度较高且含类富里酸荧光物质,而此类DON对藻类的生物有效性较低,这可能是洱海沉积物氮含量较高而上覆水氮浓度较低的原因之一,即沉积物DON分子组成及其结构特征可在一定程度上作为湖泊营养水平的衡量指标.     

Dissolved nutrient dynamics along the southwest coastal waters of India during northeast monsoon: a case study

Dissolved nutrients, Chl-a and primary productivity were measured from seven transects along the coastal waters of the southeastern Arabian Sea during northeast monsoon. Ten major estuaries were chosen to study the influence of estuarine discharge on the nutrient dynamics in the coastal waters. The mean water discharge of the estuaries in the north (64.8?±?18?×?10⁵?m³?d^?1) was found to be higher than those in the south (30.6?±?21.4?×?10⁵?m³?d^?1), whereas the nutrient concentrations were found to be higher in the estuaries of the south. The results from the offshore waters were discussed in accordance with the depth contour classification, that is, shelf (depth?≤?30?m) and slope waters (depth?≥?30?m). Our results suggest that the estuarine discharge plays a major role in the nutrient distribution in near shore shelf waters, whereas in shelf and slope waters, it was mainly controlled by in situ biological processes. The inorganic form of N to P ratios were found to be higher than Redfield ratio in slope waters when compared with shelf waters, suggesting that PO₄^3? (<0.15?µmol?L^?1) is a limiting nutrient for primary production. The multivariate statistical analysis revealed that the nutrient dynamics in the coastal waters was controlled by both biological and physical processes.     

热带滨海区不同土地利用背景下土壤溶解性有机氮的组成与粒径分布特征

溶解态有机氮(DON)是土壤中活跃的氮库,其生态环境行为与它的化学组成和粒径分布密切相关。为评估热带滨海区不同土地利用方式对不同粒径中土壤溶解性有机氮组成特征的影响,从水稻田、橡胶园、菜园和果园采集土壤样品,通过一系列微滤和超滤(0.7,0.45,0.2,0.1μm,100,10,1 kDa)对土壤溶解性有机氮分级,并使用连续流动分析仪、三维荧光光谱和红外光谱研究了滤液中溶解态有机氮、无机氮的含量及荧光组分和有机官能团特征。结果表明,4种土地利用背景下土壤DON值的范围为5.25-10.88 mg·kg^-1,其大小顺序为水稻>菜园>果树>橡胶,且DON与溶解性总氮(DTN)的比值范围为26.08%-67.11%,其中橡胶土最高,水稻土最低;不同粒径下4种土地利用类型土壤DON主要集中在<100 kDa的粒径中,其值范围为4.85-9.48 mg·kg^-1,占全量的85.89%-92.41%。三维荧光光谱(3D-EEMs)及平行因子分析表明,4种土地利用背景下土壤DON含有两种类腐殖质组分及一种类蛋白质组分,且以类腐殖质组分为主,占比54.00%-77.67%;类蛋白组分对土地利用变化敏感,且随着粒径的减小,类蛋白组分占比增加,在<1 kDa组分中比例最高。红外光谱结果表明,4种土地利用背景下土壤DON主要在6个位置有相似的吸收峰,包含3410 cm^-1、1636 cm^-1、1402 cm^-1、1138-1035 cm^-1、673 cm^-1、602 cm^-1,不同土地利用背景下各吸收峰的透光度不同,强度最大的吸收来自游离的胺类N-H伸缩振动;水稻、菜园土壤DON芳香物质含量较高,结构较复杂。了解DON的组成与粒径分布对土地利用的响应,对进一步研究其生态环境行为具有重要意义。     

Geometry of Zn(II) complexes with dissolved organic matter: X-ray studies at variable pH

The structure of Zn(II) complexes with dissolved organic matter (DOM) is an important consideration in developing molecular-level models of Zn(II) speciation, but recent reports favoring the tetrahedral geometry differ from earlier findings that geometry was largely octahedral. In general, the presence of thiolate ligands favors the tetrahedral geometry, while O and N ligands favor the octahedral geometry. This work presents extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectroscopic results, indicating an octahedral geometry over the pH range of 5–9 for a freshwater DOM isolate. Changes in XANES derivatives as a function of pH can be explained in terms of ligand protonation and/or changing ligand groups. Tetrahedral Zn(II)–DOM geometry may be restricted to binding environments containing thiol groups.     

Comparison of different valent iron on anaerobic sludge digestion: Focusing on oxidation reduction potential,dissolved organic nitrogen and microbial community

• ORP value from −278.71 to −379.80 mV showed indiscernible effects on methane yield. • Fe(II) and Fe(III) promoted more degradation of proteins and amino acids than Fe⁰. • The highest enrichment of Geobacter was noted in samples added with Fe⁰. • Cysteine was accumulated during iron enhanced anaerobic sludge digestion. • Both iron content and valence were important for methane production. This study compared effects of three different valent iron (Fe⁰, Fe(II) and Fe(III)) on enhanced anaerobic sludge digestion, focusing on the changes of oxidation reduction potential (ORP), dissolved organic nitrogen (DON), and microbial community. Under the same iron dose in range of 0−160 mg/L after an incubation period of 30 days (d), the maximum methane production rate of sludge samples dosed with respective Fe⁰, Fe(II) and Fe(III) at the same concentration showed indiscernible differences at each iron dose, regardless of the different iron valence. Moreover, their behavior in changes of ORP, DON and microbial community was different: (1) the addition of Fe⁰ made the ORP of sludge more negative, and the addition of Fe(II) and Fe(III) made the ORP of sludge less negative. However, whether being more or less negative, the changes of ORP may show unobservable effects on methane yield when it ranged from −278.71 to −379.80 mV; (2) the degradation of dissolved organic nitrogen, particularly proteins, was less efficient in sludge samples dosed with Fe⁰ compared with those dosed with Fe(II) and Fe(III) after an incubation period of 30 d. At the same dose of 160 mg/L iron, more cysteine was noted in sludge samples dosed with Fe(II) (30.74 mg/L) and Fe(III) (27.92 mg/L) compared with that dosed with Fe⁰ (21.75 mg/L); (3) Fe⁰ particularly promoted the enrichment of Geobacter, and it was 6 times higher than those in sludge samples dosed with Fe(II) and Fe(III) at the same dose of 160 mg/L iron.     

长江重庆段溶解性有机物的荧光特性分析

利用三维荧光光谱(EEMs),并结合平行因子分析(PARAFAC)及主成分分析(PCA),研究了长江重庆段溶解有机物(DOM)的荧光组分特征及其污染来源,并探讨了荧光强度同溶解性有机碳(DOC)及溶解氧(DO)的相关性.结果表明,PARAFAC模型识别出长江重庆段DOM由2类6个荧光组分组成,即类腐殖质荧光组分C1(350/422 nm)、C4(245,305/395 nm)、C5(260,340/420 nm)、C6(260/480 nm)及类蛋白荧光组分C2(275/300 nm)、C3(227,278/329 nm).在DOM来源组成中,陆源的类腐殖质含量占62.56%,类蛋白物质含量占31.31%.类腐殖质组分的荧光强度同DOC的含量存在明显的线性正相关(r=0.73),类蛋白组分的荧光强度同DO的含量呈明显的线性负相关(r=0.80).EEMs-PARAFAC不仅可以表征长江重庆段DOM的光谱特征,示踪长江重庆段的有机污染程度,还可以为三峡库区水体保护提供依据.     

垃圾填埋场渗滤液溶解性有机质特性及其去除技术综述

垃圾填埋场渗滤液所含物质种类繁多,理化特性复杂,且随填埋时间等条件而变化.本文综合分析了垃圾渗滤液溶解性有机质的组成特征、结构特征及随年代变化特征.针对垃圾渗滤液难降解有机质的特性而研发的处理技术包括物化法、高级氧化法和微电解法等,并在实际工程中得到应用.随着越来越严格的渗滤液排放要求,溶解性有机质的去除应充分考虑投资的经济、运行的稳定性和可靠性.     

Research on polyhydroxyalkanoates and glycogen transformations: Key aspects to biologic nitrogen and phosphorus removal in low dissolved oxygen systems

In this paper, a study was conducted on the effect of polyhydroxyalkanoates (PHA) and glycogen transformations on biologic nitrogen and phosphorus removal in low dissolved oxygen (DO) systems. Two laboratory-scale sequencing batch reactors (SBR1 and SBR2) were operating with anaerobic/aerobic (low DO, 0.15–0.45 mg·L^-1) configurations, which cultured a propionic to acetic acid ratio (molar carbon ratio) of 1.0 and 2.0, respectively. Fewer poly-3-hydroxybutyrate (PHB), total PHA, and glycogen transformations were observed with the increase of propionic/acetic acid, along with more poly-3-hydroxyvalerate (PHV) and poly-3-hydroxy-2-methyvalerate (PH2MV) shifts. The total nitrogen (TN) removal efficiency was 68% and 82% in SBR1 and SBR2, respectively. In the two SBRs, the soluble ortho-phosphate (SOP) removal efficiency was 94% and 99%, and the average sludge polyphosphate (poly-P) content (g·g-MLVSS^-1) was 8.3% and 10.2%, respectively. Thus, the propionic to acetic acid ratio of the influent greatly influenced the PHA form and quantity, glycogen transformation, and poly-P contained in activated sludge and further determined TN and SOP removal efficiency. Moreover, significant correlations between the SOP removal rate and the (PHV+ PH2MV)/PHA ratio were observed (R²>0.99). Accordingly, PHA and glycogen transformations should be taken into account as key components for optimizing anaerobic/aerobic (low DO) biologic nitrogen and phosphorus removal systems.     

Three-dimensional fluorescence spectral characterization of soil dissolved organic matters in the fluctuating water-level zone of Kai County, Three Gorges Reservoir

Three-dimensional fluorescence spectroscopy was used to investigate the fluorescent properties of soil dissolved organic matter (DOM) in the water-level-fluctuation zone (WLFZ) of Kai County, Three Gorges Reservoir (TGR). Most of the soil DOM analyzed in this study was found to contain four fluorescence peaks. Peaks A and C represent humic-like fluorescence, whereas peaks B and D represent tryptophan-like fluorescence. Peaks E and F, which represent tyrosine-like fluorescence, only appeared in certain soils. Soil humus was the main source of DOM in soil, and higher concentration of soil DOM was found in the exposed soil than submerged soil. Compared to the peaks A and B, the fluorescence intensities of peaks C and D were strongly influenced by the fluctuating water level. Analysis of fluorescence intensities of different peaks in soil DOM showed that WLFZ soil was not contaminated significantly. Soil DOM contained at least two types of humic-like fluorescence groups and two types of protein-like fluorescence groups. The proportion of the content of peak A in soil organic matter was quite stable. The soil DOM in exposed soil had relatively high humification and aromaticity, and periodic submerging and exposure of soil had an impact on the humification of soil DOM.     

臭氧深度处理垃圾焚烧厂沥滤液时溶解性有机质（DOM）特性分析

采用荧光光谱、红外光谱和紫外-可见光谱技术分析了臭氧氧化深度处理沥滤液生化处理水过程中废水中DOM组成及结构变化.同步荧光光谱显示,反应过程中340—370 nm处的特征峰强度明显下降,小于270 nm的短波长范围内荧光强度有一个从高到低再升高的变化过程.三维荧光光谱表明,沥滤液生化处理水中含有两个类富里酸荧光峰（UV-FA：Ex/Em=250—255/410—450 nm;Vis-FA：Ex/Em=315—320/400—405 nm）,反应过程中荧光峰强度不断降低,其中UV-FA荧光峰的发射波长存在明显的蓝移现象,最大蓝移量40 nm.红外光谱表明,沥滤液生化处理水中含有多种芳香性特征峰,臭氧氧化过程中峰强度逐渐降低,部分特征峰消失,并有过氧化合物的CO伸缩振动峰生成.沥滤液生化处理水经臭氧氧化深度处理60 min后,其SUVA254值由3.01 L.mg-.1m-1降低到1.16 L.mg-.1m-1,A3/A4值由4.06上升到8.43.综合分析表明,臭氧氧化能够有效将沥滤液生化处理水中结构复杂的大分子芳香族化合物降解为芳构化程度较低、分子量较小的有机物.     

Excitation-emission matrix (EEM) fluorescence spectroscopy for characterization of organic matter in membrane bioreactors: Principles,methods and applications

• Principles and methods for fluorescence EEM are systematically outlined. • Fluorophore peak/region/component and energy information can be extracted from EEM. • EEM can fingerprint the physical/chemical/biological properties of DOM in MBRs. • EEM is useful for tracking pollutant transformation and membrane retention/fouling. • Improvements are still needed to overcome limitations for further studies. The membrane bioreactor (MBR) technology is a rising star for wastewater treatment. The pollutant elimination and membrane fouling performances of MBRs are essentially related to the dissolved organic matter (DOM) in the system. Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy, a powerful tool for the rapid and sensitive characterization of DOM, has been extensively applied in MBR studies; however, only a limited portion of the EEM fingerprinting information was utilized. This paper revisits the principles and methods of fluorescence EEM, and reviews the recent progress in applying EEM to characterize DOM in MBR studies. We systematically introduced the information extracted from EEM by considering the fluorescence peak location/intensity, wavelength regional distribution, and spectral deconvolution (giving fluorescent component loadings/scores), and discussed how to use the information to interpret the chemical compositions, physiochemical properties, biological activities, membrane retention/fouling behaviors, and migration/transformation fates of DOM in MBR systems. In addition to conventional EEM indicators, novel fluorescent parameters are summarized for potential use, including quantum yield, Stokes shift, excited energy state, and fluorescence lifetime. The current limitations of EEM-based DOM characterization are also discussed, with possible measures proposed to improve applications in MBR monitoring.     

Significant increase of assimilable organic carbon (AOC) levels in MBR effluents followed by coagulation,ozonation and combined treatments: Implications for biostability control of reclaimed water

• Annual AOCs in MBR effluents were stable with small increase in warmer seasons. • Significant increase in AOC levels of tertiary effluents were observed. • Coagulation in prior to ozonation can reduce AOC formation in tertiary treatment. • ∆UV₂₅₄ and SUVA can be surrogates to predict the AOC changes during ozonation. As water reuse development has increased, biological stability issues associated with reclaimed water have gained attention. This study evaluated assimilable organic carbon (AOC) in effluents from a full-scale membrane biological reactor (MBR) plant and found that they were generally stable over one year (125–216 µg/L), with slight increases in warmer seasons. After additional tertiary treatments, the largest increases in absolute and specific AOCs were detected during ozonation, followed by coagulation-ozonation and coagulation. Moreover, UV₂₅₄ absorbance is known to be an effective surrogate to predict the AOC changes during ozonation. Applying coagulation prior to ozonation of MBR effluents for removal of large molecules was found to reduce the AOC formation compared with ozonation treatment alone. Finally, the results revealed that attention should be paid to seasonal variations in influent and organic fraction changes during treatment to enable sustainable water reuse.