Occurrence, polarity and bioavailability of dissolved organic matter in the Huangpu River, China

Dissolved organic matter （DOM） plays an important role in biogeochemical cycles in aquatic ecosystem. To investigate the characteristics of DOM in Huangpu River {the last tributary of the Yangtze River）, surface water samples were collected along the river from December 2011 to June, 2013. The concentrations of dissolved organic carbon （DOC）, the absorbance and fluorescence spectrum of DOM in water samples were measured. Fluorescent DOM in the Huangpu River was decomposed into four components by the parallel factor analysis （PARAFAC）, including one humic-like substance and three protein-like substances. It showed that high spatial variability of DOC concentration was observed in the upstream water compared to the downstream water, and so did the absorbance coefficients of chromophoric dissolved organic matter and the total fluorescence intensities of different PARAFAC components of DOM. Furthermore, there was a large difference between the polarity and bioavailability of DOM in the Huangpu River. Polar compounds dominated tyrosine-like component of fluorescent DOM in all seasons. Tryptophan-like and humic-like substances had more polar fraction in summer and autumn than those in winter, while aromatic protein-like materials had the highest polar fraction in winter. Almost all of fluorescent DOM components were refractory in spring, while less than 20% of fluorescent DOM in average were biodegradable within 4 weeks in other seasons. We concluded that the spatial variation in the abundance of DOM in the Huangpu River is mainly affected by the water discharges from the Hangjiahu Plain and the seasonal difference in polarity and bioavailability of DOM is largely determined by its origins.     

Changes of DOM and its correlation with internal nutrient release during cyanobacterial growth and decline in Lake Chaohu, China

The seasonal changes in dissolved organic matter (DOM), and its correlation with the release of internal nutrients during the annual cycle of cyanobacteria in the eutrophic Lake Chaohu, China, were investigated from four sampling periods between November 2020 and July 2021. The DOM fluorescence components were identified as protein-like C1, microbial humic-like C2, and terrestrial humic-like C3. The highest total fluorescence intensity (F_T) of DOM in sediments during the incubation stage is due to the decomposition and degradation of cyanobacteria remains. The lowest humification of DOM and the highest proportion of C1 in waters during the initial cyanobacterial growth indicate that fresh algae are the main source. The highest molecular weight of DOM and F_T of the C2 in sediments during cyanobacterial outbreaks indicate the concurrent deposition of undegraded cyanobacterial remains and microbial degradation. The components of DOM are affected mainly by the dissolved total phosphorus in waters, while the temperature drives the annual cycle of cyanobacteria. The decreasing C1 in sediments and increasing nutrients in waters from the cyanobacterial incubation to outbreak indicate that mineralization of algal organic matter contributes importantly to the release of internal nutrients, with the strongest release of phosphorus observed during the early growth of cyanobacteria. The humic-like C2 and C3 components could also affect the dynamics of internal phosphorus through the formation of organic colloids and organic–inorganic ligands. The results show that the degradation of DOM leads to nutrients release and thus supports the continuous growth of cyanobacteria in eutrophic Lake Chaohu.     

Effect of photo-biodegradation and biodegradation on the biogeochemical cycling of dissolved organic matter across diverse surface water bodies

The objective of this research was to quantify the temporal variation of dissolved organic matter(DOM) in five distinct waterbodies in watersheds with diverse types of land use and land cover in the presence and absence of sunlight. The water bodies were an agricultural pond, a lake in a forested watershed, a man-made reservoir, an estuary, and a bay. Two sets of samples were prepared by dispensing unfiltered samples into filtered samples in 1:10 ratio(V/V). The first set was exposed to sunlight(10 hr per day for 30 days) for examining the combined effect of photo-biodegradation, while the second set was stored in dark for examining biodegradation alone. Spectroscopic measurements in tandem with multivariate statistics were used to interpret DOM lability and composition. The results suggest that the agricultural pond behaved differently compared to other study locations during degradation experiments due to the presence of higher amount of microbial humic-like and protein-like components derived from microbial/anthropogenic sources. For all samples, a larger decrease in dissolved organic carbon(DOC) concentration(10.12% ±9.81% for photo-biodegradation and 6.65% ± 2.83% for biodegradation) and rapid transformation of DOM components(i.e., terrestrial humic-like components into microbial humic and protein-like components) were observed during photo-biodegradation experiments.Results suggest that sunlight facilitated DOM biodegradation, resulting in simpler recalcitrant molecules regardless of original composition. Overall, it was found that combined effects of light and bacteria are more efficient than bacterial effects alone in remineralizing and altering DOM, which highlights the crucial importance of sunlight in transforming aquatic DOM.     

Identifying the major fluorescent components responsible for ultrafiltration membrane fouling in different water sources

Three-dimensional fluorescence excitation–emission matrix(EEM) coupled with parallel factor analysis(PARAFAC) was performed for a total of 18 water samples taken from three water sources(two lakes and one wastewater treatment plant(WWTP) secondary effluent),with the purpose of identifying the major ultrafiltration(UF) membrane foulants in different water sources. Three fluorescent components(C1, C2 and C3) were identified,which represented terrestrially derived humic-like substances(C1), microbially derived humic-like substances(C2), and protein-like substances(C3). The correlations between the different fluorescent components and UF membrane fouling were analyzed. It was shown that for the WWTP secondary effluent, all three components(C1, C2 and C3) made a considerable contribution to the irreversible and total fouling of the UF membrane.However, for the two lakes, only the C3 exhibited a strong correlation with membrane fouling, indicating that the protein-like substances were the major membrane foulants in the lake waters. Significant attachment of C1, C2 and C3 to the UF membrane was also confirmed by mass balance analyses for the WWTP secondary effluent; while the attachment of C1 and C2 was shown to be negligible for the two lakes. The results may provide basic formation for developing suitable fouling control strategies for sustainable UF processes.     

Photo-production of dissolved inorganic carbon from dissolved organic matter in contrasting coastal waters in the southwestern Taiwan Strait, China

Photo-production of dissolved inorganic carbon (DIC) from chromophoric dissolved organic matter (CDOM) is an important transformation process in marine carbon cycle, but little is known about this process in Chinese coastal systems. This study investigated an estuarine water sample and a coastal seawater sample from the subtropical waters in southeast of China. Water samples were exposed to natural sunlight and the absorption and fluorescence of CDOM as well as the DIC concentration were measured in the summer of 2009. The estuarine water had higher CDOM level, molecular weight and proportion of humic-like fluorescent components than the seawater that exhibited abundant tryptophan-like fluorescent component. After a 3-day irradiation, the CDOM level decreased by 45% in the estuarine water and 20% in the seawater, accompanied with a decrease in the molecular weight and aromaticity of DOM which was inferred from an increase in the absorption spectral slope parameter. The photo-degradation rates of all the five fluorescent components were also notable, in particular two humic-like components (C4 and C5) were removed by 78% and 69% in the estuarine water and by 69% and 56% in the seawater. The estuarine water had a higher photo-production rate of DIC than the seawater (4.4 vs. 2.5 μupmol/(L.day)), in part due to its higher CDOM abundance. The differences in CDOM compositions between the two types of waters might be responsible for the higher susceptibility of the estuarine water to photo-degradation and hence could also affect the photo-production process of DIC.     

Simulated photo-degradation of dissolved organic matter in lakes revealed by three-dimensional excitation-emission matrix with regional integration and parallel factor analysis

Simulated photo-degradation of fluorescent dissolved organic matter(FDOM) in Lake Baihua(BH) and Lake Hongfeng(HF) was investigated with three-dimensional excitationemission matrix(3 DEEM) fluorescence combined with the fluorescence regional integration(FRI),parallel factor(PARAFAC) analysis,and multi-order kinetic models.In the FRI analysis,fulvic-like and humic-like materials were the main constituents for both BH-FDOM and HF-FDOM.Four individual components were identified by use of PARAFAC analysis as humic-like components(C1),fulvic-like components(C2),protein-like components(C3) and unidentified components(C4).The maximum 3 DEEM fluorescence intensity of PARAFAC components C1-C3 decreased by about 60%,70% and 90%,respectively after photo-degradation.The multi-order kinetic model was acceptable to represent the photo-degradation of FDOM with correlation coefficient(R_(adj)~2)(0.963-0.998).The photo-degradation rate constants(k_n) showed differences of three orders of magnitude,from 1.09 x 10~(-6) to 4.02 x 10~(-4) min-1,and half-life of multi-order model(T_(1/2)~n)ranged from 5.26 to 64.01 min.The decreased values of fluorescence index(FI) and biogenic index(BI),the fact that of percent fluorescence response parameter of Region I(P_(Ⅰ,n)) showed the greatest change ratio,followed by percent fluorescence response parameter of Region II(P_(Ⅱ,n),while the largest decrease ratio was found for C3 components,and the lowest T_(1/2)~n was observed for C3,indicated preferential degradation of protein-like materials/components derived from biological sources during photodegradation.This research on the degradation of FDOM by 3 DEEM/FRI-PARAFAC would be beneficial to understanding the photo-degradation of FD OM in natural environments and accurately predicting the environmental behaviors of contaminants in the presence of FDOM.     

Seasonal variability in CDOM absorption and fluorescence properties in the Barataria Basin, Louisiana, USA

Absorption and fluorescence properties of chromophoric dissolved organic matter(CDOM) along a 124 km transect in the Barataria Basin,a large estuary located in Louisiana,USA,were investigated during high and low flow periods of the Mississippi River in the spring and winter of 2008-2009. Mean CDOM absorption at 355 nm from the marine to the freshwater end member stations ranged from(3.25 ± 0.56) to(20.76 ± 2.43) m-1 for the three month high flow period whereas it varied from(1.48 ± 1.08) to(25.45 ± 7.03) m-1 for the same stations during low flow period. Corresponding salinity values at these stations indicated the influence of river and shelf exchanges in the lower basin and precipitation and runofl in the upper basin. An inverse relationship of CDOM absorbance and fluorescence with salinity observed in the basin could be a useful indicator of salinity. CDOM fluorescence also varied over a large range showing an approximately 8 to 12-fold increase between the marine and freshwater end members for the two flow seasons. Excitation-emission matrix spectral plots indicated the presence of various fluorescence components with highest being the A-peak,lowest the T-peak,and the C and M-peaks showing similar trends along the transect. During low flow season the A/C ratio were well correlated with station locations indicating increased terrestrial influence towards the upper basin. CDOM absorption and fluorescence at 355 nm were highly correlated and independent of CDOM sources suggesting that fluorescence could be used to characterize CDOM in the basin.     

Characterization of dissolved organic matter as N-nitrosamine precursors based on hydrophobicity, molecular weight and fluorescence

It is very important to identify the dominant precursors for N-nitrosamine formation from bulk organic matter, to enhance the understanding of N-nitrosamine formation pathways in water treatment plants and allow the development of practical treatment technologies. In this study, dissolved organic matter (DOM) from two source waters was fractionated with XAD resins and ultra- filtration membranes. The N-nitrosamine formation potential (FP) (ng of N-nitrosamines formed per mg of dissolved organic carbon (DOC)) from raw water and each fraction were measured and correlated with the fluorescence excitation-emission matrix (EEM), molecular weight (MW) and other assays. The results showed that the hydrophilic fraction had N-nitrosamine FP 1.3 to 3.5 times higher than the hydrophobic fraction from both source waters. The DOM fraction with low MW was the dominant fraction in these two source waters and contributed more precursors for N-nitrosamine formation than the larger MW fraction. The EEM spectra indicated there were notable amounts of soluble microbial products (SMPs) and aromatic proteins in the two studied rivers, which probably originated from wastewater discharge. The SMPs tended to be more closely correlated with N-nitrosodimethylamine formation potential than the other DOM components. Higher N-nitrosamine FP were also related to fractions with lower DOC/DON ratios and lower SUVA 254 values.     

Extraction and characterization of bound extracellular polymeric substances from cultured pure cyanobacterium (Microcystis wesenbergii)

Preliminary characterization of bound extracellular polymeric substances（bEPS） of cyanobacteria is crucial to obtain a better understanding of the formation mechanism of cyanobacterial bloom. However,the characterization of bEPS can be affected by extraction methods. Five sets（including the control） of bEPS from Microcystis extracted by different methods were characterized using three-dimensional excitation and emission matrix（3DEEM） fluorescence spectroscopy combined chemical spectrophotometry; and the characterization results of bEPS samples were further compared. The agents used for extraction were NaOH,pure water and phosphate buffered saline（PBS） containing cationic exchange resins,and hot water. Extraction methods affected the fluorescence signals and intensities in the bEPS. Five fluorescence peaks were observed in the excitation and emission matrix fluorescence spectra of bEPS samples. Two peaks（peaks T1 and T2） present in all extractions were identified as protein-like fluorophores,two（peaks A and C） as humic-like fluorophores,and one（peak E） as a fulvic-like substance.Among these substances,the humic-like and fulvic-like fluorescences were only seen in the bEPS extracted with hot water. Also,NaOH solution extraction could result in strong fluorescence intensities compared to the other extraction methods. It was suggested that NaOH at pH 10.0 was the most appropriate method to extract bEPS from Microcystis. In addition,dialysis could affect the yields and characteristics of extracted bEPS during the determination process. These results will help us to explore the issues of cyanobacterial blooms.     

Characteristics of dissolved organic matter （DOM） in leachate with different landfill ages

The main objective of the study was to investigate the characteristics of dissolved organic matter (DOM) in leachate with different landfill ages through the chemical, spectroscopic, and elemental analysis. Humic acid (HA), fulvic acid (FA), and hydrophilic (HyI) fractions were isolated and purified by the XAD-8 resin combined with the cation exchange resin method. The analytical results of fluorescence excitation-emission matrix spectroscopy (EEMs) revealed that the fluorescence peaks were protein-like fluorescence for young landfill leachate, while the fluorescence peaks for medium and old landfill leachate were humic-like and fulvic-like fluorescence, respectively. Elemental analysis showed that carbon, hydrogen, and nitrogen content decreased with landfill age, while the oxygen content increased. Moreover, the nitrogen content in these isolated fractions followed HA ＞ HyI ＞ FA. The results of elemental analysis, FT-IR, and fluorescence EEMs also confirmed that aromatic carbons and portions of aliphatic functional groups were more abundant in leachate samples with increasing landfill age.     

Degradation and detoxification of microcystin-LR in drinking water by sequential use of UV and ozone

Microcystins (MCs) produced by cyanobacteria are strong hepatotoxins and classified as possible carcinogens.MCs pose a considerable threat to human health through tainted drinking and surface waters.Herein filtrated water from a waterworks in Harbin,China,was spiked with microcystin-LR (MC-LR) extracted from a toxic scum of microcystis aeruginosa,and the spiked sample waters were treated using UV irradiation with consequent ozonation process (UV/O3),compared with ozonation at a dose range commonly applied in water treatment plants,UV irradiation at 254 nm and UV irradiation combined with ozonation (UV+O3),respectively.The remaining of toxins were analyzed using high-performance liquid chromatography and also determined using a protein phosphatase type 2A inhibition assay,which was utilized to evaluate the reduction in toxicity.Results indicated that in comparison to other three processes (O3,UV,and UV+O3),UV/O 3 process could effectively decrease both the concentration and toxicity of MC-LR at 100 μg/L level after 5 min UV irradiation with consequent 5 min ozonation at 0.2 mg/L (below 1 μg/L),while 0.5 mg/L ozone dose was required for the level below 0.1 μg/L.The addition of an UV treatment step to the existing treatment train may induce significant transformation of micropollutants and breaks down the natural organic matters into moieties unfavorable for ozone decomposition,stabilizing the ozone residual.These findings suggested that sequential use of UV and ozone may be a suitable method for the removal of these potentially hazardous microcystins from drinking water.     

太湖水中微囊藻毒素的测定及其分布特征

为了调查太湖水体中微囊藻毒素的污染程度,运用固相萃取-高效液相色谱技术测定了微囊藻毒素(MC-RR,MC-LR)的含量水平。该方法线性范围0.2～5 mg/L,相关系数大于0.99,2种藻毒素的最低检测限分别为0.05μg/L(MC-RR)和0.048μg/L(MC-LR)。结果表明,夏季太湖水体中MCs总体含量高于冬季;微囊藻毒素MC-LR的含量大于MC-RR。总体上看来,太湖北部(梅梁湾)水域中藻毒素的污染比其它区域水体严重。     

臭氧-紫外预处理对高有机物原水混凝效果的影响

以腐殖酸为模型污染物,分别考察了臭氧氧化、紫外照射及臭氧-紫外联合预处理过程对高有机物原水混凝性能的影响.结果表明,3种预处理方式均对原水中的溶解性腐殖酸具有明显的矿化作用.紫外及臭氧-紫外联合预处理还对后续的混凝过程具有强化作用.随着臭氧投量的增加和紫外照射时间的延长,混凝过滤出水的TOC和浊度呈明显下降趋势.当臭氧浓度(O3/C)达到9.0 mg/mg时,预处理对腐殖酸的去除率可以达到47%,过滤出水TOC含量为3.5 mg/L,浊度为2.6 NTU;紫外光照射3 h可去除原水中52%的溶解性有机物,其出水TOC为2.0 mg/L,浊度低于1.0 NTU.臭氧-紫外联合预处理后的混凝效果要明显优于二者单独作用的系统.在联合预处理系统中,当预臭氧浓度(O3/C)为1.0 mg/mg紫外照射时间为1 h时,过滤出水TOC为2.6 mg/L,且浊度低于1.0 NTU.不同预处理条件下的矿化作用主要是通过.OH实现的,同时.OH还对溶解性腐殖酸的团聚结构产生破坏作用,使其稳定性降低,从而促进了混凝过程对有机物的去除.     

微囊藻毒素-LR多克隆抗体的制备

通过对新西兰大白兔免疫自制的微囊藻毒素-LR(Microcystin-LR,MC-LR)完全抗原BSA-MC-LR,获得了质量较好的抗MC-LR的多克隆抗体,间接ELISA表明抗体的效价能达到1.5×10⁵;固定包被抗原OVA-MC-LR,采用间接竞争ELISA测定水体中的微囊藻毒素,标准曲线表明对水样中MC-LR的检测下限为10ng/L,线性区间为30ng/L·3μg/L,能满足对饮用水和地表水中MC-LR的检测要求.     

预臭氧与后臭氧-生物活性炭联用工艺研究

利用静态批量和动态连续试验初步研究了预臭氧及预臭氧与后臭氧-BAC组合工艺对南方某含溴离子水库水的处理效果和相应的处理条件.静态实验结果表明,预臭氧反应量在0.5～1.0mg/L范围内,在有效去除消毒副产物(DBPFP,主要包括THMFP和HAAFP)的同时,臭氧副产物溴酸可以控制在10μg/L以下,而继续增加臭氧反应量则会导致DBPFP的增加.当水中溴离子浓度达到96μg/L时,使用臭氧必须采取溴酸控制措施.连续动态实验结果表明,预臭氧与臭氧-生物活性炭组合工艺对于2μm以上颗粒物、COD_Mn、TOC等的去除均有明显的效果,可以进一步抑制DBPs的形成.     

Effects of advanced oxidation pretreatment on residual aluminum control in high humic acid water purification

Due to the formation of disinfection by-products and high concentrations of Al residue in drinking water purification, humic substances are a major component of organic matter in natural waters and have therefore received a great deal of attention in recent years. We investigated the effects of advanced oxidation pretreatment methods usually applied for removing dissolved organic matters on residual Al control. Results showed that the presence of humic acid increased residual Al concentration notably. With 15 mg/L of humic acid in raw water, the concentrations of soluble aluminum and total aluminum in the treated water were close to the quantity of Al addition. After increasing coagulant dosage from 12 to 120 mg/L, the total-Al in the treated water was controlled to below 0.2 mg/L. Purification systems with ozonation, chlorination, or potassium permanganate oxidation pretreatment units had little effects on residual Al control; while UV radiation decreased Al concentration notably. Combined with ozonation, the effects of UV radiation were enhanced. Optimal dosages were 0.5 mg O3/mg C and 3 hr for raw water with 15 mg/L of humic acid. Under UV light radiation, the combined forces or bonds that existed among humic acid molecules were destroyed; adsorption sites increased positively with radiation time, which promoted adsorption of humic acid onto polymeric aluminum and Al(OH)3(s). This work provides a new solution for humic acid coagulation and residual Al control for raw water with humic acid purification.     

γ-Al2O3催化臭氧氧化水中嗅味物质机理探讨

以γ-Al₂O₃粉末为催化剂,研究催化臭氧氧化去除水体中典型嗅味物质2-甲基异茨醇（MIB）的效能与机理.结果表明,γ-Al₂O₃能够明显促进臭氧氧化去除MIB,表现出很好的催化活性,叔丁醇对γ-Al₂O₃催化氧化去除MIB过程具有明显的抑制作用.在催化臭氧氧化去除MIB过程中,γ-Al₂O₃表面电荷状态及表面羟基的带电性质与溶液的pH值有关.当溶液pH值与γ-Al₂O₃ 的pH_zpc接近时,γ-Al₂O₃的催化作用最为明显.γ-Al₂O₃催化臭氧氧化过程中自由基的相对量值R_ct比单独臭氧氧化过程高出近1个数量级,这进一步表明γ-Al₂O₃能明显促进臭氧分解产生更多的羟基自由基.最后还考察了不同摩尔比例的臭氧分解促进剂与抑制剂对γ-Al₂O₃催化臭氧分解的影响.     

电催化臭氧技术降解啶虫脒

研究了臭氧氧化、紫外/臭氧(UV/O₃)和电催化臭氧(electro-peroxone, EP)3种技术降解啶虫脒的机制,比较了3种技术降解地下水和地表水中啶虫脒的效率和能耗(使用E_EO指标表征)。发现啶虫脒为臭氧难氧化物质,与臭氧(O₃)和羟基自由基(·OH)的二级反应速率常数分别为(0.05±0.01) mol/(L·s)、(2.8±0.2)×109 mol/(L·s)。经6 min臭氧氧化后,地下水和地表水中的啶虫脒去除率仅为26%和64%。与之相比,UV/O₃和EP技术可以完全去除地下水和地表水中的啶虫脒。臭氧氧化、UV/O₃和EP技术降解啶虫脒的能耗分别为0.11~0.27,1.22~1.24,0.12~0.24 kW·h/m3。结果表明,EP技术是一种去除饮用水中啶虫脒的高效低耗技术。     

紫外光在臭氧降解不同有机物过程中的协同作用

利用O3／UV分别对与臭氧有不同反应活性的对氯苯酚、硝基苯、乙酸和草酸进行了降解试验，结果表明，UV与臭氧化降解的协同作用与目标有机物本身的性质有很大关系，在本实验条件下，UV与臭氧的联用反而降低了对氯苯酚的臭氧化降解效率，30min后体系的TOC去除率仅有59％，而单独臭氧化TOC的去除率达到了66％；对硝基苯和草酸而言，UV均明显地提高了臭氧的降解效率，40min时两者TOC的去除率分别为44％和90％，比单独臭氧化处理分别高出了6％和33％；但是，O3／UV对乙酸几乎无降解活性．在这4种有机物的单独臭氧化降解过程中，除对氯苯酚外，水中均可检测到溶解臭氧．以上的实验结果表明，目标有机物对紫外光的吸收及单独臭氧化过程水中溶解臭氧的存在是O3／UV降解效率提高的必要条件．除UV对目标有机物的活化作用外，降解过程的中间产物H2O2也是O3／UV降解效率提高的一个重要因素，UV分解溶解臭氧在此过程可能仅起了辅助作用。     

O3/H2O2氧化工艺去除水中硝基苯的研究

以硝基苯为代表性有机污染物 ,对比了臭氧化和O3/H2 O2 高级氧化工艺对水中硝基苯的去除效果 .发现与臭氧化相比 ,O3/H2 O2 高级氧化工艺可以显著地提高水中硝基苯的去除效率 .无论在臭氧化还是在O3/H2 O2 高级氧化工艺中 ,水中硝基苯的降解都主要是由OH·完成的 .通过考察O3/H2 O2 高级氧化工艺去除水中硝基苯的影响因素发现 ,在O3和过H2 O2 投量相同的条件下 ,多次投加O3和催化剂H2 O2 对水中硝基苯的处理效果明显优于一次性投加 ;在本次试验条件下 ,O3/H2 O2 高级氧化工艺降解蒸馏水和自来水中硝基苯的最优H2 O2 与O3摩尔比均为 0 5 ,HCO- 3碱度水平 (以CaCO3计 )在低于 1 0 0mg/L范围内对去除硝基苯无显著影响