Quantifying interactions between propranolol and dissolved organic matter (DOM) from different sources using fluorescence spectroscopy

Beta blockers are widely used pharmaceuticals that have been detected in the environment. Interactions between beta blockers and dissolved organic matter (DOM) may mutually alter their environmental behaviors. To assess this potential, propranolol (PRO) was used as a model beta blocker to quantify the complexation with DOM from different sources using the fluorescence quenching titration method. The sources of studied DOM samples were identified by excitation–emission matrix spectroscopy (EEMs) combined with fluorescence regional integration analysis. The results show that PRO intrinsic fluorescence was statically quenched by DOM addition. The resulting binding constants (log K _oc) ranged from 3.90 to 5.20, with the surface-water-filtered DOM samples claiming the lower log K _oc and HA having the highest log K _oc. Log K _oc is negatively correlated with the fluorescence index, biological index, and the percent fluorescence response (P _i,n) of protein-like region (P _I,n) and the P _i,n of microbial byproduct-like region (P _II,n) of DOM EEMs, while it is correlated positively with humification index and the P _i,n of UVC humic-like region (P _III,n). These results indicate that DOM samples from allochthonous materials rich in aromatic and humic-like components would strongly bind PRO in aquatic systems, and autochthonous DOM containing high protein-like components would bind PRO more weakly.     

Relating dissolved organic matter fluorescence and functional properties

The fluorescence excitation–emission matrix properties of 25 dissolved organic matter samples from three rivers and one lake are analysed. All sites are sampled in duplicate, and the 25 samples include ten taken from the lake site, and nine from one of the rivers, to cover variations in dissolved organic matter composition due to season and river flow. Fluorescence properties are compared to the functional properties of the dissolved organic matter; the functional assays provide quantitative information on photochemical fading, buffering capacity, copper binding, benzo[a]pyrene binding, hydrophilicity and adsorption to alumina. Optical (absorbance and fluorescence) characterization of the dissolved organic matter samples demonstrates that (1) peak C (excitation 300–350 nm; emission 400–460 nm) fluorescence emission wavelength; (2) the ratio of peak T (excitation 220–235 nm; emission 330–370 nm) to peak C fluorescence intensity; and (3) the peak C fluorescence intensity: absorbance at 340 nm ratio have strong correlations with many of the functional assays. Strongest correlations are with benzo[a]pyrene binding, alumina adsorption, hydrophilicity and buffering capacity, and in many cases linear regression equations with a correlation coefficient >0.8 are obtained. These optical properties are independent of freshwater dissolved organic carbon concentration (for concentrations <10 mg L⁻¹) and therefore hold the potential for laboratory, field and on-line monitoring and prediction of organic matter functional properties.     

Relating dissolved organic matter fluorescence and functional properties

The fluorescence excitation–emission matrix properties of 25 dissolved organic matter samples from three rivers and one lake are analysed. All sites are sampled in duplicate, and the 25 samples include ten taken from the lake site, and nine from one of the rivers, to cover variations in dissolved organic matter composition due to season and river flow. Fluorescence properties are compared to the functional properties of the dissolved organic matter; the functional assays provide quantitative information on photochemical fading, buffering capacity, copper binding, benzo[a]pyrene binding, hydrophilicity and adsorption to alumina. Optical (absorbance and fluorescence) characterization of the dissolved organic matter samples demonstrates that (1) peak C (excitation 300–350 nm; emission 400–460 nm) fluorescence emission wavelength; (2) the ratio of peak T (excitation 220–235 nm; emission 330–370 nm) to peak C fluorescence intensity; and (3) the peak C fluorescence intensity: absorbance at 340 nm ratio have strong correlations with many of the functional assays. Strongest correlations are with benzo[a]pyrene binding, alumina adsorption, hydrophilicity and buffering capacity, and in many cases linear regression equations with a correlation coefficient >0.8 are obtained. These optical properties are independent of freshwater dissolved organic carbon concentration (for concentrations <10 mg L⁻¹) and therefore hold the potential for laboratory, field and on-line monitoring and prediction of organic matter functional properties.     

Characterization of binding site heterogeneity for copper within dissolved organic matter fractions using two-dimensional correlation fluorescence spectroscopy

The heterogeneity of copper binding characteristics for dissolved organic matter (DOM) fractions was investigated based on the fluorescence quenching of the synchronous fluorescence spectra upon the addition of copper and two-dimensional correlation spectroscopy (2D-COS). Hydrophobic acid (HoA) and hydrophilic (Hi) fractions of two different DOM (algal and leaf litter DOM) were used for this study. For both DOM, fluorescence quenching occurred at a wider range of wavelengths for the HoA fractions compared to the Hi fractions. The combined information of the synchronous and asynchronous maps derived from 2D-COS provided a clear picture of the heterogeneous distribution of the copper binding sites within each DOM fraction, which was not readily recognized by a simple comparison of the changes in the synchronous fluorescence spectra upon the addition of copper. For the algal DOM, higher stability constants were exhibited for the HoA versus the Hi fractions. The logarithms of the stability constants ranged from 4.8 to 6.1 and from 4.5 to 5.0 for the HoA and the Hi fractions of the algal DOM, respectively, depending on the associated wavelength and the fitted models. In contrast, no distinctive difference in the binding characteristics was found between the two fractions of the leaf litter DOM. This suggests that influences of the structural and chemical properties of DOM on copper binding may differ for DOM from different sources. The relative difference of the calculated stability constants within the DOM fractions were consistent with the sequential orders interpreted from the asynchronous 2D-COS. It is expected that 2D-COS will be widely applied to other DOM studies requiring detailed information on the heterogeneous nature and subsequent effects under a range of environmental conditions.     

Distinguishing sources of groundwater nitrate by 1H NMR of dissolved organic matter

Dissolved organic matter (DOM) originating from a certain source usually carries characteristic marks in its molecular structures that can be recognized by spectroscopic analysis. Sources of water-borne contaminants, such as nitrate, can be identified by recognition of the characteristics of DOM entrained in the water. In this study, DOM in groundwaters sampled from a dairy/crop production area (Chino Basin, CA) was analyzed by 1H nuclear magnetic resonance (1H NMR). Results showed that DOM derived from natural soil organic matter has a characteristic resonance at a chemical shift region of 4.0-4.3 ppm, while DOM derived from dairy wastes has a characteristic resonance at a lower chemical shift region of 3.2-3.6 ppm. These signature resonances were then used to distinguish the origins of nitrate in the groundwater. It was found that disposal of dairy wastes on croplands is the primary source of nitrate contamination in groundwater underlying the Chino Basin dairy area.     

改良型AO法组合工艺中有机物的三维荧光分析

采用三维荧光(EEM)光谱技术,对上海竹园第二污水处理厂改良型AO法组合工艺运行过程中的各种溶解性有机物(DOM)进行分析,并对比研究传统好氧活性污泥法曝气池出水和A/O脱氮工艺硝化池出水DOM的EEM光谱的迁移变化特性.结果表明,各种DOM中主要的荧光物质有类蛋白质(荧光峰A和B)及类腐殖质(荧光峰C),经改良型AO法组合工艺处理后,荧光峰的强度降低了14％～60％,同时类蛋白质和腐殖质的结构也发生了变化;腐殖酸溯源表明DOM中的腐殖酸以微生物代谢产生的带有荧光基团的腐殖酸类为主.     

三维荧光区域积分评估城市污水中溶解性有机物去除

以三维荧光技术为手段,结合荧光区域积分和聚类分析,考察某城市污水厂污水处理过程中溶解性有机物的去除状况。研究结果表明,采用三维荧光区域积分可以表征城市污水中易降解、可降解和难降解有机物相对含量的变化趋势,能够有效识别污水中溶解性有机物的指纹特征。城市污水中类蛋白等易降解物质含量约占总荧光物质的50%,在污水厂曝气池缺氧段,易降解基质被大量去除。曝气池顺水流方向约225 m处,溶解性有机物的去除已基本完成。三维荧光光谱中区域II和III的积分标准体积与TOC的皮尔森相关指数分别为0.964和0.970。和其他荧光指数相比,这2个区域的积分标准体积与TOC的相关度更高。     

垃圾渗滤液处理工艺中有机污染物的三维荧光光谱

利用荧光发射和三维荧光光谱研究了三峡库区某垃圾堆场的渗滤液及其处理工艺出水溶解性有机质(DOM)的荧光光谱特性。堆场渗滤液的DOM含有类酪氨酸、色氨酸及紫外区类富里酸,特征荧光峰中心位于E_x/E_m=275 nm/305 nm,为高激发波长类酪氨酸,与前人的研究结果并不一致,这可能与垃圾的堆放期有关。渗滤液和各处理工艺出水的荧光指数f_450/500均大于1.9,表明腐殖质主要为微生物源。渗滤液在处理前后荧光峰特征和强度均发生明显改变,类蛋白荧光强度与DOC值变化趋势基本一致。生化处理工艺中,类蛋白荧光强度降低了66.4%～95.5%,紫外区类富里酸荧光强度只降低了28.8%,显示类蛋白质具有良好的可生化性,而类富里酸相对较难生化降解。三维荧光光谱能反映渗滤液处理过程中污染物的种类、性质和数量等变化信息,能快速地进行定性分析、定量评价。     

垃圾渗滤液中溶解性有机物对土壤中重金属迁移的影响

垃圾渗滤液主要组分中含有重金属和大量的溶解性有机物(DOM).实验选用北方最具代表性的褐土为供试样品,通过室内土柱淋滤实验研究了垃圾渗滤液溶解性有机物对重金属Cu、Cd、Pb和Zn在土壤中的迁移行为的影响.结果显示,DOM对土壤中Cd、Zn的垂直迁移起着促进作用,而对Cu、Pb迁移起着一定的抑制作用;不同浓度的垃圾淋洗...     

Impact of aquaculture on distribution of dissolved organic matter in coastal Jeju Island,Korea, based on absorption and fluorescence spectroscopy

Environmental Science and Pollution Research - In Jeju Island, multiple land-based aquafarms were fully operational along most coastal region. However, the effect of effluent on distribution and...     

基于三维荧光光谱-平行因子分析及紫外-可见吸收光谱对制药污水不同处理工艺单元溶解性有机物特征分析

利用三维荧光光谱-平行因子分析法和紫外-可见吸收光谱2种技术方法对某制药园区污水处理厂处理过程中污水溶解性有机物种类、分子量、腐殖化程度等进行表征,同时对解析出的溶解性有机物组分和水质指标进行相关性分析。三维荧光光谱-平行因子分析法解析出5类大分子溶解性有机物,组分C1是制药污水中特征污染物,组分C2和C3属于类腐殖质物质,组分C4和C5为类蛋白质物质。紫外-可见吸收光谱表明,处理过程中溶解性有机物分子量逐渐降低,腐殖化程度呈现先上升后下降的趋势。相关性分析表明,组分C4和SUVA₂₅₄数值可以快速推断污水处理过程中氮含量变化情况,组分C2和C3可以推断污水溶解性有机碳变化情况。本研究技术方法和结果可以为监测污水处理厂运行情况和日后改进污水处理工艺提供支持。     

Tracing the sources of refractory dissolved organic matter in a large artificial lake using multiple analytical tools

Structural and chemical characteristics of refractory dissolved organic matter (RDOM) from seven different sources (algae, leaf litter, reed, compost, field soil, paddy water, treated sewage) were examined using multiple analytical tools, and they were compared with those of RDOM in a large artificial lake (Lake Paldang, Korea). Treated sewage, paddy water, and field soil were distinguished from the other sources investigated by their relatively low specific UV absorbance (SUVA) values and more pronounced fulvic-like versus humic-like fluorescence of the RDOM samples. Microbial derived RDOM from algae and treated sewage showed relatively low apparent molecular weight and a higher fraction of hydrophilic bases relative to the total hydrophilic fraction. For the biopolymer types, the presence of polyhydroxy aromatics with the high abundance of proteins was observed only for vascular plant-based RDOM (i.e., leaf litter and reed). Molecular weight values exhibited positive correlations with the SUVA and the hydrophobic content among the different RDOM, suggesting that hydrophobic and condensed aromatic structures may be the main components of high molecular weight RDOM. Principal component analysis revealed that approximately 77% of the variance in the RDOM characteristics might be explained by the source difference (i.e., terrestrial and microbial derived) and a tendency of further microbial transformation. Combined results demonstrated that the properties of the lake RDOM were largely affected by the upstream sources of field soil, paddy water, and treated sewage, which are characterized by low molecular weight UV-absorbing and non-aromatic structures with relatively high resistance to further degradation.     

台特玛湖流域水体溶解性有机质的光谱特征与来源解析

为探究台特玛湖水体水质超标原因,结合流域自然条件,以水中溶解性有机质(DOM)为研究对象,分析DOM的光谱特征和来源,通过平行因子分析(PARAFAC)和荧光区域积分分析(FRI)对台特玛湖流域水体DOM进行定性与定量分析。结果表明：PARAFAC识别出台特玛湖流域DOM中 4种主要荧光组分,分别为腐殖酸、类色氨酸、类酪氨酸(B峰和D峰),水体DOM主要组分为色氨酸类蛋白质和酪氨酸类蛋白质,占总体比例为66.57%,说明DOM来源主要以内源输入为主,腐殖化程度低;台特玛湖流域水体水质超标主要是因为尾闾湖的封闭性、面积大、高蒸发量且为浅水湖泊,导致个别水质指标不断富集;水体DOM各组分与TN和COD呈显著正相关,氟化物与矿化度之间呈显著正相关。本研究为台特玛湖水质超标提出的原因分析及建议措施可为台特玛湖流域水环境保护提供依据。     

基于三维荧光光谱特征峰的水体有机污染物综合指标检测

对来源不同一的32个水样进行三维荧光光谱的测定,并用5种典型有机物的荧光特征峰A(腐殖酸类)、C(腐殖酸类)、B(络氨酸类)、T1(色氨酸类)、T2(色氨酸类)进行了单一和组合式建模,发现对于来源不同一的水体的总有机含碳量(TOC)、化学耗氧量(COD)的检测采用这种提取特征峰建模的效果并不理想.该研究说明,依据典型特...     

工业园区污水厂处理过程中溶解性有机物的三维荧光特征分析

随着工业园区的不断发展,工业园区污水处理越来越引起人们关注。污水中溶解性有机物(dissolved organic matter, DOM)的组分特征对污水处理效果有显著影响。因此,通过三维荧光光谱(excitation-emission-matrix spectra, 3D-EEMs)结合平行因子(parallel factor, PARAFAC)分析,考察了江西5家工业园区污水厂的DOM组分沿程变化特征及其来源特征。结果表明：工业园区污水厂进水COD/DOC在3.74~8.05,进水中有机物芳香化程度比一般城市污水厂的进水高;各工业园区污水厂处理过程中全部水样的荧光物质均呈现类蛋白质>类腐殖质、腐殖化程度较低的特征,DOM来源主要受到生物源的影响;污水厂对类色氨酸芳香蛋白和类腐殖质有机物的削减效果相对较好(21%~43%),对类SMP有机物的削减效果较弱(0%~3%);类色氨酸芳香蛋白(Ex/Em=235 nm/335 nm;Ex/Em=235 nm/340 nm)和类SMP物质(Ex/Em=285 nm/315 nm;Ex/Em=290 nm/320 nm)为江西五家工业园区污水厂出水中持续存在的DOM。本研究结果可为进一步了解工业园区污水厂的DOM沿程变化特征提供科学参考。     

Chemical and biological characterization of dissolved organic matter from silver fir and beech forest soils

Despite a growing attention to the dissolved organic matter (DOM) in terrestrial ecosystems and evidence of the fact that vegetation affects the quality of both undissolved and dissolved organic matter in soil, the role of DOM as a biological indicator is still poorly understood. In this work, the fertility of 59 sites, divided into eight key alliances of the order Fagetalia sylvaticae Pawl., was studied considering chemical and biological parameters such as soil DOM, hormone-like activity, low-molecular-weight (LMW) aliphatic and phenolic acids, and floristic data. Both non-parametric tests and principal component analysis (PCA) revealed differences between silver fir and beech forests and within each type of forest. There were also differences between neutrophilous and acidophilous types. What's more, PCA reveals the dominance of the auxin (IAA)-like activity, and of some phenolic acids in distinguishing the acidophilous beeches (ACI) form the other types, whereas the gibberellin (GA)-like activity is more relevant in neutrophilous conditions such as thermophilous (THE) and mesophilous (MESO) beeches and montane (MO), high montane (HMA), high montane (HMC) silver fir forests. The GA-like activity is also related to the succinic, fumaric, malonic, and l-malic acids in the MO, HMA and HMC silver fir forests. Moreover, the role of LMW aliphatic acids in mobilizing the hormone-like activity, which improves forest growth, is stressed. The growth of seedlings of Picea abies was influenced by the phenolic acid content. At concentrations between 1 and 100 microM, phenylacetic and protocatechuic acids inhibited root growth to the same extent as indoleacetic acid, while p-hydroxybenzoic acid had a stimulating effect comparable to that of gibberellic acid. The aliphatic and phenolic acids appear to be related to plant strategies that influence soil fertility affecting plant growth through rhizodeposition. The role of LMW aliphatic and phenolic acids as molecular markers of ecosystem function is noted.     

Relationships between colored dissolved organic matter and dissolved organic carbon in different coastal gradients of the Baltic Sea

Due to high terrestrial runoff, the Baltic Sea is rich in dissolved organic carbon (DOC), the light-absorbing fraction of which is referred to as colored dissolved organic matter (CDOM). Inputs of DOC and CDOM are predicted to increase with climate change, affecting coastal ecosystems. We found that the relationships between DOC, CDOM, salinity, and Secchi depth all differed between the two coastal areas studied; the W Gulf of Bothnia with high terrestrial input and the NW Baltic Proper with relatively little terrestrial input. The CDOM:DOC ratio was higher in the Gulf of Bothnia, where CDOM had a greater influence on the Secchi depth, which is used as an indicator of eutrophication and hence important for Baltic Sea management. Based on the results of this study, we recommend regular CDOM measurements in monitoring programmes, to increase the value of concurrent Secchi depth measurements.     

Chemical characteristics of chromophoric dissolved organic matter in rainwater

Proton nuclear magnetic resonance (¹H-NMR), UV absorbance and excitation-emission matrix (EEM) fluorescence spectroscopy were used to define the chemical characteristics of chromophoric dissolved organic matter (CDOM) in whole and C₁₈ extracted rainwater. The average total recovery of fluorescence determined from the sum of extract and filtrate fractions relative to the whole was 86% suggesting that 14% of fluorescent CDOM in rainwater is comprised of very hydrophobic material that cannot be eluted from the column. Half the fluorescence of rainwater was recovered in the filtrate fraction which is important because it suggests that 50% of the chromophoric material present in precipitation is relatively hydrophilic. The average spectral slope coefficient was smaller in extracted samples (16.3 ± 9.0 μm^?1) relative to whole samples (18.9 ± 2.8 μm^?1) suggesting that the extracted material contains larger molecular weight material. Approximately one-third of the total dissolved organic carbon (DOC) in rainwater exists in the extract fraction suggesting that a large percentage of the uncharacterized DOC in rainwater can be accounted for by these hydrophobic macromolecular species. The fluorescence of extracted samples is strongly correlated with total NMR integration and is most sensitive to aromatic protons suggesting that molecules in this region are the most important in controlling the optical properties of rainwater. The lower removal efficiency of CDOM in rainwater relative to surface waters or the water-soluble fraction of aerosols during solid phase extraction (SPE) suggests that rainwater contains significantly more hydrophilic chromophoric compounds which are compositionally different than found in these other aquatic matrices.     

Impact of dissolved organic matter on bioavailability of chlorotoluron to wheat

Chlorotoluron (Chl) is a phenylurea herbicide and is widely used for controlling weeds. While it has brought great benefits to crop production, it has also resulted in contamination to ecosystem. In this study, we investigated accumulation of chlorotoluron (Chl) and biological responses of wheat plants as affected by dissolved organic matter (DOM). Wheat seedlings grown under 10 mg kg⁻¹ Chl for 4 d showed a low level of chlorophyll accumulation and damage to plasma membrane. The growth was inhibited by exposure of chlorotoluron. Treatment with 50 mg DOC kg⁻¹ DOM derived either from sludge (DOM-SL) or straw (DOM-ST) attenuated the chlorotoluron toxicity to plants. Both DOMs decreased activities of catalase, peroxidase and superoxide dismutase in Chl-treated seedlings. However, an increased glutathione S-transferases activity was observed under the same condition. Wheat plants treated with Chl in the presence of DOM accumulated less Chl than those treated with Chl alone. Moreover, in the presence of DOM, bioconcentration factor (BCF) decreased whereas translocation factors increased. Analyses with FT-IR spectra confirmed the regulatory role of DOMs in reducing Chl accumulation in wheat.