Fluorescence as a Tool for Tracing the Organic Contamination from Pulp Mill Effluents in Surface Waters

Three‐dimensional fluorescence spectra of water samples from an eucalyptus bleached kraft pulp mill and from a river, upstream and downstream of the discharge of the effluent, revealed the existence of a peak at δ_exc = 280 nm and δ_em = 340 nm Δδ = 60 nm), characteristic of effluentπs organic matter. Humic substances were isolated from the effluent by sequential adsorption onto resins XAD‐8 and XAD‐4 in series. Their synchronous fluorescence spectra with Δδ = 60 nm do also exhibit an intense signal at δ_exc = 280 nm (≈ 300 nm in the humic acid fraction). The peak is absent in the spectra of humic substances isolated from a non‐polluted site of the river, but it is clearly seen in the spectra of the humic substances from a site downstream of the discharge of the effluent. Synchronous fluorescence spectra (Δδ = 60 nm) of water samples from the river and its lagoon were recorded and revealed to be an easy and fast way of tracing the organic contamination from the effluent.     

The Geochemical Effects of Microbial Humic Substances Reduction

As part of a study on microbial redox alteration of humic substances we investigated the potential effect of this metabolism on the fate of heavy metals and hydrocarbons as a result of conformational alteration of the humic molecular structure due to microbial reduction. Our studies indicate that the microbial reduction of humic acids (HA) results in significant morphological and geochemical alterations. X‐ray microscopy analysis indicate that the conformational structure of the humic colloids is altered as a result of the redox change. In the reduced state, the HA appeared as small dense particles, on reoxidation, large loose aggregates were formed. In addition, spectrofluorometric studies indicated that the binding capacity of the HA for naphthalene was decreased by 10% when the HA was reduced. Similarly, the reduced HA yielded higher surface tension values at all concentrations tested which is indicative of a more hydrophilic and less hydrophobic solute. On reoxidation, the surface tension values reverted back to values similar to those obtained for the untreated oxidized HA. These data indicate that the hydrophobicity of the HA is altered on biological reduction of the HA and that this alteration is reversible. In contrast the reduced HA demonstrated a 15% higher affinity for heavy metals such as divalent cobalt than the oxidized HA. In addition to increasing the binding capacity of HA for heavy metals, the reduction of the HA also decreased the bioavailability and toxicity of bound heavy metals such as chromium. When incubated in the presence of Cr(III) and HA, cells of Escherichia coli grew much more rapidly in the presence of the reduced HA suggesting that the higher metal binding capacity of the reduced humic substances resulted in a removal of the Cr(III) from solution and hence reduced its bioavailability and toxicity. These studies demonstrate that HA redox state and reduction of humic acids by microorganisms can have a significant effect on the molecular morphology and binding constants of HA for heavy metals and hydrocarbons and also directly affects the bioavailability of these compounds in the environment.     

Influence of IHSS Standard and Reference Materials on Copper and Mercury Toxicity to Vibrio fischeri

The reduction in light emission of the marine bacterium Vibrio fischeri used in the standard Microtox^® bioassay was measured for the metals copper and mercury. The concentration at which the light emission was reduced by 50% (EC₅₀) was determined to be (3.43 ± 0.83) μmol/L for Cu²⁺ and (0.66 ± 0.01) μmol/L for Hg²⁺. The reduction of the toxicity of these metals by humic and fulvic acids were studied using IHSS Standard and Reference Materials. Copper toxicity was reduced 17...20% by the soil and peat fulvic acids and 9...20% by the aquatic fulvic acids. While there appeared to be little difference in the reduction of Cu toxicity by fulvic acids from soils, peats, or aquatic systems, Hg toxicity was reduced 3.6...7.3% by the soils and peats, while aquatic fulvic acids reduced Hg toxicity 14...16%. Soil fulvic acids appear to have significantly less capacity to reduce Hg toxicity than Cu toxicity. Humic acids had much higher reductions of Cu toxicity (44...124%) compared to the fulvic acids, with little difference between aquatic and soil or peat humic acids, 44...124% and 67...100%, respectively. However, humic and fulvic acids, regardless of origin, had approximately the same effect on Hg toxicity with 3.5...16% reduction by fulvic acids and 8...20% reduction by humic acids. Unlike the fulvic acids, no clear trend was observed relative to origin of the humic acids. There was no correlation between percent reduction of Cu or Hg toxicity by the organic compounds and copper binding capacity (CuBC), C/N ratio, or carboxyl content of the materials. Examination of natural organic matter (NOM) isolated by reverse osmosis techniques from three water sources had reductions of both Cu and Hg toxicity that were most similar to the Suwannee River and Nordic fulvic acids.     

Differences between Humic Substances from Riverine,Estuarine, and Marine Environments Observed by Fluorescence Spectroscopy

Sixteen samples of fulvic acids and XAD‐4 fractions of riverine, estuarine, coastal, and open ocean origin have been studied by emission and synchronous molecular fluorescence spectroscopy. Certain features of the molecular fluorescence are related to the nature, the content, and the origin of those aquatic humic substances (HS). Riverine HS appear several times richer in fluorophores than marine HS, which can be well observed by emission fluorescence spectroscopy. Synchronous‐scan spectra of fulvic acids and of XAD‐4 fractions from the aquatic environments studied, emphasized the quality differences of their fluorophores. These features are useful as tracers of humic substances related with their natural environment source or even with their anthropogenic origin.     

Spectroscopic Characterization of Fulvic Acid Fractions of a Contaminated Groundwater

Two fulvic acid (FA) samples taken from a former gas production facility in the Southwest of Germany were characterized using advanced fluorescence techniques. Steady-state fluorescence (fluorescence excitation, synchronous fluorescence) as well as time-resolved fluorescence were applied. Distinct differences between the sample B22 FA taken within the contamination plume and the sample B53 FA taken downstream were found. Comparison with a model compound for metabolites and humic substances revealed that due to the downstream passage the characteristics of the dissolved organic matter became more humic-like. The assignment of single classes of compounds in the sample B22 FA is discussed in terms of their synchronous fluorescence spectra and fluorescence decay time distribution.     

Degradation and Transformation of Aquatic Humic Substances by Laccase-producing Fungi Cladosporium cladosporioides and Polyporus versicolor

A phenoloxidase-producing fungus – Cladosporium cladosporioides – was isolated from water of a bog lake. At high concentrations of carbon (333 mM) and nitrogen (12 mM), the fungus demonstrated the formation of a laccase and a high ligninolytic activity. After addition of riverine or groundwater humic substances into culture media (ca. 1 mg mL^–1), the fungus showed the ability of degrading (utilizing) of about 60% of these substances. However, the exact quantification of the degree of degradation was difficult because of adsorption of humic matter on fungal mycelium. Reisolated humic substances were lower in aromatic and higher in aliphatic structures. A crude enzyme from the C. cladosporioides culture showed only low activity in decolorizing humic substances, whereas decolorization up to 50% was observed when using a laccase preparation from Polyporus versicolor, and especially in the presence of a redox mediator.     

Spectroscopic Characterization of Organic Structures and Organic‐Inorganic Interactions in Paper Mill Sludge

The organic composition and organic‐inorganic interaction in paper mill sludge (PS) solvent extracts (hexane, ethyl acetate, acetone and ethanol) and humic fractions, humic acid (HA) and humin (HU) were studied by electron paramagnetic resonance spectroscopy (EPR), proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H NMR; ¹³C NMR), Fourier‐transformed infrared spectroscopy (FTIR), and ultraviolet‐visible spectroscopy (UV‐vis). The strategy of fractionating the PS, sequentially, with organic solvents of increasing polarity is a reliable analytical procedure for humic substance sample separation because it results in more purified fractions. FTIR, ¹H NMR and ¹³C NMR results showed that hexane extract consisted mainly of aliphatic hydrocarbon structures. Their contents in the extracts decreased as the polarity of the extracting solvent increased and the content of oxygen functional groups increased. Carboxylic and carboxylate functional groups were found in the acetone extract, and ester and ether functions were predominantly found in the ethanol extract. EPR spectra revealed some Fe³⁺ complexes with rhombic structure (g₁ = 4.3; g₂ = 9.0) in the humic fractions and in all solvent extracts, except hexane. Quasi‐octahedral Fe³⁺ complexes (g = 2.3; ΔH_pp ≤ 400 G) were found in the HU fraction and in the acetone extract. The organic free radical content in the HA fraction was higher than the non‐fractionated PS sample and HU fraction.     

Adsorbed and Bound Residues in Fulvic Acid Fractions of a Contaminated Groundwater – Isolation:, Chromatographic and Spectroscopic Characterization

Humic substances (HS) were isolated from two contaminated groundwater samples (B22 and B53) from a site of a former gas facility. The isolation yielded almost only the fulvic acid fractions (FA). For characterization spectroscopic (UV, fluorescence) and chromatographic techniques (hydrophobic interaction chromatography – HIC as well as size-exclusion chromatography – SEC) were applied. The sample designated B22 FA was collected from the contamination plume whereas the sample B53 FA was collected downstream. Distinct differences were exhibited by these samples. The UV and fluorescence spectra as well as the HIC and SEC chromatograms of the B53 FA sample resemble those of the FA fraction obtained from natural water (groundwater, bog). The HIC and SEC chromatograms reveal the presence of organic compounds in B22 FA which can be derived from coal tar contaminants or their metabolites. Some of the compounds can be extracted from the FA fraction with non-polar organic solvents indicating adsorptive forces between the contaminants and the FA fraction.     

Combined Effects of Molecular Size and Electroendosmotic Flow on the Capillary Electrophoretic Behaviour of Humic Substances

The electroendosmotic flow (EOF), generated by the migration of solvated ions near the charged capillary surface, is an important factor in determining the capillary electrophoretic behaviour of humic substances (HS). We investigated the electrophoretic mobilities of HS fractions of reduced molecular-weight polydispersity extracted from peat and from a spodosol either in the presence or after suppression of the EOF. When the EOF was not suppressed, HS migrated to the cathode in spite of their negative charge. Fractionation of HS according to molecular size was achieved in polyacrylamide-coated capillaries filled with 0.05 M tris-phosphate buffer. In uncoated capillaries filled with the same buffer, all fractions had very close mobilities. Addition of polyethylene glycol MW 4000 at concentrations above its entanglement threshold caused the migration times of larger molecules to increase more than those of smaller molecules. The separation was a linear function of molecular size up to 75000 g mol^–1 for peat HS and to 50000 g mol^–1 for HS extracted from the spodosol.     

Alkaline Degradation of Dissolved Organic Matter

The degradation of dissolved organic matter (DOM) was studied in alkaline solution. The products were characterised using UV/vis spectroscopy, size‐exclusion chromatography (SEC), and by the analysis of low‐molecular‐weight organic acids (LMWOA). The degradation experiments were performed with water from a brown water lake or its isolated fulvic acid fraction and sodium hydroxide at different reaction times and temperatures. Depending on the wavelength and the reaction time, the UV/vis absorbance between 230 nm and 600 nm increased or decreased. The behaviour of model compounds during reactions in alkaline media was compared to the UV/vis spectroscopic behaviour of DOM. The release of LMWOA was described by kinetic data and compared to the data of model reactions. Evidence was given for the carboxylic esters playing a significant role in the release of LMWOA only during the beginning of the alkaline degradation. The results gained by SEC with on‐line UV and DOC detection showed that the average size of DOM was decreasing, and that a major part of the degradation products consisted of low‐molecular‐weight mono‐ and dicarboxylic acids.     

Approaches to the Immunochemical Analysis of Non-extractable Triazine Residues in Refractory Organic Substances (ROS) and Characterization of ROS

The tendency of several pesticides to form non-extractable residues requires simple and fast screening methods. Immunochemical methods can meet this demand. They are based on selective and highly sensitive antibody binding to pesticide residues exposed on refractory organic substances (ROS). s-Triazines were used as an example to show the feasibility of this approach. It was proven that under laboratory conditions atrazine was bound to ROS. Antibody recognition pointed to the availability of free ethyl and isopropyl groups exposed at the non-extractable s-triazine residue. Therefore, it is suggested on the basis of antibody selectivities that binding of atrazine to ROS may take place by substitution of the chlorine residue. In the next step, aquatic ROS isolated from surface waters located in an agricultural area were examined for non-extractable s-triazines. ROS from a lake were found to contain bound residues, whereas none were detected in the creek samples. As an outlook the feasibility of serological characterization of ROS is discussed. The novel concept of serotyping is based on the fractionation of ROS by electrophoretic techniques followed by an immunoreaction with polyclonal antibodies directed against different ROS. When immunoelectrophoresis is used, precipitation lines can be compared and checked for identity and cross-reactivity. This approach can form the basis for classifying ROS and determine similarities with unknown ROS.     

太湖五里湖区表层沉积物中酸挥发性硫化物和同步提取金属

湖泊底泥中的酸溶硫化物易与二价金属生成难溶金属硫化物,从而制约沉积物中二价有毒金属的化学活性以及生物有效性,进而影响沉积物的环境质量.对沉积物中的酸溶硫化物(AVS)和同步提取金属(SEM)进行测定,依据SEM/AVS的比值可以判定重金属生物有效性.通过对太湖五里湖、梅梁湾表层沉积物夏季和秋季AVS与SEM的采样分析,结果表明:研究区域内AVS的含量夏季高于秋季,SEM受季节影响很小,SEM/AVS大于1,且秋季高于夏季,初步判断该湖区沉积物中重金属具有潜在的生物毒性.     

Changes of Acute Toxicity of Organic Chemicals to Daphnia magna in the Presence of Dissolved Humic Material (DHM)

With a series of substituted anilines, a series of substituted phenols as well as diazinon and tetrabromobisphenol-A alterations of short-term acute toxicity to the waterflea Daphnia magna have been studied in the presence of dissolved humic material (DHM). The results may be categorised as follows: No alteration in acute toxicity occurred with: tetrabromobisphenol-A, o-toluidine, 3,4-dichloroaniline, and pentachlorophenol. Toxicity decreases significantly with: diazinon, 4-chloroaniline, and 4-nitrophenol. Significant toxicity increases were observed with 2,4-dichlorophenol and 2,4,5-trichlorophenol. As demonstrated for diazinon, our study reveals that in the presence of DHM and light the chemical speciation of this chemical is altered and daughter products are produced most likely via photoactive species of DHM. Most probably the toxicity of both the parent and daughter compounds is changed as well. Alterations in acute toxicity of organic chemicals may thus be attributed to the adsorption to DHM as well as to the photoactive species mediated production of daughter products with toxicity different from that of the parent compounds.     

Clustering Analysis of Spatial Distribution of Seismicity in the Yellow Sea and Bohai Sea

According to tie records of seismic station networks of China's continent and Korea Peninsula and the historical data,the complete seismicity pattern was obtained for the first time.The seismic zoning was conducted by means of the cluster analysis method.The map's spatial distribution of seismicity from 1960 to 1994 shows that there are three strong seismic zones:the first one strikes in the NE direction,from the Jiangsu plain in China to the central Korean Peninsula; the second strikes in the NW direction,from the Bohai Sea,China to the southern Korean Peninsula; the third strikes in the NW direction,from the western Liaoning Province to Pyongyang.Most of earthquakes are located along these three zones,the seismic intensity is lower than that in the mainland,and exhibited the feature of fractured crust of a marginal sea basin.     

Distribution and Chemical Forms of Heavy Metals in the Flood 1997 Sediments of the Upper and Middle Odra River and its Tributarie:, Poland

At the beginning of August 1997, 72 samples of flood sediments were taken along the Upper and Middle Odra river and its tributaries. The concentrations of Zn, Pb, Cu, Cd, Co, Ni, Cr, Mn, and Fe in the bulk samples and in the <20 μm fraction were determined by AAS method. The contents of metals vary in wide ranges and are significantly higher in the <20 μm fraction of sediments. The range concentrations vary as following: Zn 274...3 656 mg/kg, Pb 79...1 773 mg/kg, Cd 1.7...11.8 mg/kg, Cu 38...2 244 mg/kg, Cr 14...384 mg/kg, Co 4...73 mg/kg, Hg 0.2...3.9 mg/kg, Mn 214...6 972 mg/kg, and Fe 1.5...16.3 %. The highest amount of the metals was found in the Wrocław and Głogów regions. The mobile (exchangeable and carbonatic fractions) portions of metals reached up to 50 % of Zn, 40 % of Pb and Cu and 60 % of Mn.     

新疆艾比湖主要入湖河流同位素及水化学特征的季节变化

通过野外调查取样和室内测试分析,利用水文化学以及氢氧稳定同位素技术,分析艾比湖主要入湖河流氢氧同位素及水化学的组成特征,并探讨其季节性变化.结果表明：地表水水质指标高值多出现于博乐市、温泉市和精河县及艾比湖湿地附近,主要污染为水体富营养化、工矿业污染以及有机质污染,其污染程度夏、秋季高于春、冬季.河水的δ¹⁸O与δ²H存在明显的线性关系,其相关指数为夏季（R²=0.99） > 春季（R²=0.98） > 秋季（R²=0.96） > 冬季（R²=0.90）,均沿当地大气降水线分布,受西北干旱区强烈的蒸发作用影响,各季节河流斜率均小于8,氘过量参数值多为正值.博尔塔拉河与精河地表水体δ¹⁸O值整体上表现为沿流程逐渐偏正的趋势,博尔塔拉河水体氢氧同位素与高程相关指数表现为春季（R²=0.70） > 冬季（R²=0.57） > 夏季（R²=0.45） > 秋季（R²=0.30）,精河因其海拔差异不大,流程简短,与高程相关性低.博尔塔拉河和精河氢氧同位素与氯化物、硫酸盐、五日生物需氧量等指标间存在相关性,且在夏、秋季最大,相关系数R>0.75,与总磷、Cu²⁺、色度、浊度等指标基本都不显著相关,相关系数R<0.25.     

黄海和渤海海域地震空间分布的集群分析

本文依据中国大陆地震台网和朝鲜半岛地震台网记录及历史资料，获得了黄海和涝海海域的地震空间分布图像，采用集群分析法进行了地震分带，对１９６０～１９８４年地震资料的分析显示，存在３个大的地震带，第一条是北东走向，从中国苏北平原到朝鲜半岛中部；第二条是北西走向，从中国渤海到朝鲜半岛南部；第三条是北西向，从中国辽宁省西部到朝鲜平壤附近。大部分地震都落了这３个带中，地震强度低于大陆，显示出破碎的边缘盆地地壳     

春秋两季鄱阳湖浮游动物的编目、数量分布与变动

分析鉴定了1999年春、秋两季,在鄱阳湖区8个断面24个采样站采得的水样．共观察到各类浮游动物共150种．其中轮虫动物物种最为丰富,为96种,占总种数的64．0％,且单位体积的数量亦呈明显优势,说明轮虫动物是该湖区浮游动物的优势类群;其次为原生动物．24个采样站中,原生动物、轮虫动物、枝角类、桡足类这四类浮游动物个体数量分布的差异极大,其中第10、12、13和23号站中的个体数量较高,超过100ind／L最大数量出现在13号站,个体数量高达1101．60ind／L鄱阳湖浮游动物的数量有明显的季节变动,尤属轮虫的变动最大．本次调查中轮虫和枝角类的数量春季大于秋季,而原生动物和桡足类则秋季大于春季．     

云南程海和阳宗海季节性分层及其消退对冬季水华的潜在影响

基于2014年10月2016年7月在云南程海和阳宗海开展了4个季度(秋季,10月;冬季,1月;春季,4月;夏季,7月)的调查,研究了两个湖泊的水体分层特征,探讨了热力分层及其变化与其他环境因子对浮游植物生物量的潜在影响,结果显示:程海和阳宗海水体分层的特征均为冬季混合、春季形成分层、夏秋季分层稳定,两湖均属暖单次混合型湖泊;程海分层期温跃层的平均深度(顶界)、厚度和强度分别为17.70±3.89 m、5.54±4.44 m和0.67±0.43℃/m,阳宗海的分别为12.53±3.35 m、8.25±4.85 m和0.53±0.43℃/m.在热力分层稳定期,两湖底层达到缺氧甚至厌氧状态,底层的电导率总体较表层高.调查期间,两个湖泊水柱表层浮游植物生物量(以叶绿素a浓度表征)均在冬季出现峰值,程海和阳宗海的分别为19.22±11.08和45.82±9.41μg/L;进一步分析发现,热力分层的消退可能是导致水体表层无机营养盐升高(底层供给)的重要原因,加之适宜的光热条件可诱导两湖冬季水华的发生;在其他季节转化期间,浮游植物生物量变化的主要影响因子亦具有一定的共性及湖泊与季节异质性.