Bottom-up approach for the reaction of xenobiotics and their metabolites with model substances for natural organic matter by electrochemistry-mass spectrometry (EC-MS)

Risk assessment of xenobiotics requires a comprehensive understanding of their transformation in the environment. As most of the transformation processes usually involve a redox reaction or a hydrolysis as the first steps of the transformation, we applied an approach that uses an electrochemical cell to investigate model “redox” reactions in aqueous solutions for environmental processes. We investigated the degradation of a variety of xenobiotics from polar to nonpolar and analyzed their degradation products by on-line coupling of electrochemistry with mass spectrometry (EC-MS). Furthermore, we evaluated possible binding reactions with regard to the generation of non-extractable residues with some model substances (catechol, phthalic acid, γ-l-Glutamyl-l-cysteinyl-glycine (GSH) and l-histidine) deduced from a natural organic matter (NOM) structure model and identified possible binding-sites.Whereas typically investigations in soil/water-systems have been applied, we used to our knowledge for the first time a bottom-up approach, starting from the chemicals of interest and different model substances for natural organic matter to evaluate chemical binding mechanisms (or processes) in the EC-MS under redox conditions. Under oxidative conditions, bindings of the xenobiotics with catechol, GSH and histidine were found, but no reactions with the model compound phthalic acid were observed. In general, no chemical binding has yet been found under reductive conditions. In some cases (i.e. benzo[a]anthracene) the oxidation product only underwent a binding reaction, whereas the xenobiotic itself did not undergo any reactions.EC-MS is a promising fast and simple screening method to investigate the environmental behavior of xenobiotics and to evaluate the potential risks of newly synthesized substances.     

Heavy Metals Fractionation in Ganga River Sediments, India

The Ganga River is the largest river in India which, originates in the Himalayas and along with the Brahmaputra River, another Himalayan river, transports enormous amounts of sediments from the Indian sub-continent to the Bay of Bengal. Because of the important role of river sediments in the biogeochemical cycling of elements, the Ganga river sediments, collected from its origin to the down stretches, were studied in the present context, to assess the heavy metals associated with different chemical fractions of sediments. The fractionation of metals were studied in the sediments using SM&T protocol for the extraction of heavy metals and geo-accumulation index (GAI) (Muller, Schwermetalle in den sedimenten des rheins – Veranderungen seit. Umschau, 79, 778–783, 1979) and Metal Enrichment Factor (MEF) in different fractions were calculated. As with many river systems, residual fractions constitute more than 60% of total metals, except Zn, Cu and Cr. However, the reducible and organic and sulfide components also act as major sinks for metals in the down stretches of the river, which is supported by the high GAI and MEF values. The GAI values range between 4 and 5 and MEF exceed more than 20 for almost all the locations in the downstream locations indicating to the addition of metals through urban and industrial effluents, as compared to the low metals concentrations with less GAI and MEF in the pristine river sediments from the rivers in Himalayas.     

用分级方法评估土壤对重金属的缓冲能力

研究了不同Cd,Zn,Cu和Pb负荷对5种土壤(油黄泥土、棕红壤、红壤、石砂土和紫砂土)中的重金属形态的影响,分析了不同土壤对重金属的缓冲作用及其影响因素.结果表明,未污染土壤中的重金属主要以残余态为主,占土壤重金属总量的51%以上.随着土壤重金属负荷的提高,土壤中交换态重金属的比例增大,残余态比例下降,有效性提高,对重金属的缓冲作用下降.由于Cd,Zn,Cu和Pb本身的特性不同,土壤中各组分与Cd,Zn,Cu和Pb的结合方式及程度不同.当外源重金属进入土壤后,土壤对重金属的缓冲性为:Pb>Cu>Zn Cd,酸性土壤和砂质土壤的缓冲能力较低.当重金属加入量较低时,重金属优先向氧化物结合态和有机质结合态转化;而当加入量较高时,向交换态和碳酸盐结合态转化的比例增加.土壤pH下降可使交换态Cd,Zn,Cu和Pb的比例递增,降低土壤对重金属的缓冲性,增加了重金属对环境影响的风险.      

Natural organic matter(NOM) removal from surface water by coagulation

IntroductionNaturalorganicmatter(NOM)inriversandlakesisacomplexmixtureofmoleculeswithvaryingmolecularweightandchemicalnatureandoriginatesfromavarietyofsources(degradationofterrestrialandaquaticorganisms,biologicalactivityinthewaterbody,humaninputsetc.).NO…     

引滦水中天然有机化合物的形态及紫外吸收特征

用改进的Leenheer法将引滦水中的天然有机化合物分离为悬浮态和溶解态两大类,后者又分离成憎水有机物、腐殖酸类、强阴离子化合物和其它亲水化合物4种。溶解态有机物含量在4—5mgC/L之间,其中半数左右为腐殖酸类,其紫外吸收强度远在其它形态之上。非极性憎水有机物在5％以下。     

Effects of Flooding on Lead and Cadmium Speciation in Sediments from a Drinking Water Reservoir

Římov water reservoir on the river Malše is the main source of drinking water for the town of České Budějovice and for the majority of inhabitants in the South Bohemian region, Czech Republic. Changes in cadmium and lead contents in bottom sediments before and after an extensive flood on the river Malše in August, 2002 were therefore determined. A five-step sequential extraction procedure was used in order to obtain more detailed information about the influence of the flood on heavy metal retention. In order to determine the mobility of lead and cadmium, the mobility factor (MF) for these heavy metals was calculated. The mobility factor of cadmium showed a significant decrease in the upper parts of the sediment profiles after the flood (e.g., from 59.4% to 49.1%) caused by a release of cadmium especially from the exchangeable fraction. There were no significant changes in the lead mobility factor after the flood, but a decrease of lead concentration in the exchangeable fraction was observed. Presented results show that the flood led to a leaching of the heavy metals present in bottom sediments into the environment.     

Fluorescence spectroscopic studies of the effect of granular activated carbon adsorption on structural properties of dissolved organic matter fractions

This work investigated the effect of granular activated carbon adsorption (GACA) on fluorescence characteristics of dissolved organic matter (DOM) in secondary effluent, by means of excitation–emission matrix (EEM) spectra, the fluorescence regional integration (FRI) method, synchronous spectra, the fluorescence index defined as the ratio of fluorescence emission intensity at wavelength 450 nm to that at 500 nm at excitation (λ_ex)=370 nm, and the wavelength that corresponds to the position of the normalized emission band at its half intensity (λ_0.5). DOM in the secondary effluent from the North Wastewater Treatment Plant (Shenyang, China) was fractionated using XAD resins into 5 fractions: hydrophobic acid (HPO–A), hydrophobic neutral (HPO–N), transphilic acid (TPI–A), transphilic neutral (TPI–N) and hydrophilic fraction (HPI). Results showed that fluorescent materials in HPO–N and TPI–N were less readily removed than those in the other fractions by GACA. The relative content of fluorescent materials in HPO–A, TPI–A and HPI decreased whereas that in HPO–N and TPI–N increased as a consequence of GACA. Polycyclic aromatics in all DOM fractions were preferentially absorbed by GACA, in comparison with bulk DOM expressed as DOC. On the other hand, the adsorption of aromatic amino acids and humic acid-like fluorophores exhibiting fluorescence peaks in synchronous spectra by GACA seemed to be dependent on the acid/neutral properties of DOM fractions. All five fractions had decreased fluorescence indices as a result of GACA. GACA led to a decreased λ_0.5 value for HPO–A, increased λ_0.5 values for HPO–N, TPI–A and HPI, and a consistent λ_0.5 value for TPI–N.     

Variations in δ13C of water–soluble leaf and phloem organic matter of Platycladus orientalis: influences of photosynthetic and post–photosynthetic fractionation

Analysis of variations in water–soluble organic matter (WSOM) δ¹³C of leaves and phloem can efficiently describe the δ¹³C distributions within plants and identify the temporal variation of δ¹³C. In this study, WSOM δ¹³C values of both leaves and phloem (twig, stem, and root) of Platycladus orientalis were measured during seven sunny days, including 2–hour interval measurements at three days for diel pattern analysis and 6–hour interval measurements at the remaining four days for day–to–day variation analysis. Analysis of WSOM δ¹³C in different plant organs showed that ¹³C was generally depleted from leaves to twigs, then enriched in stems and subsequently depleted in roots. Stems were significantly ¹³C–enriched compared to twigs (p?<?0.05), while δ¹³C differences between stems and other organs and among leaves, twigs and roots were not significant (p?>?0.05). No clear diel patterns in δ¹³C of leaves and phloem were found. Daily average δ¹³C values indicated that all plant organs had more positive values on sunny days during the dry season than during the wet season. Both photosynthetic and post–photosynthetic fractionation influence variations in WSOM δ¹³C. These results have implications for research on plant physiology and plant water use.     

Spatial variation of phosphorus fractionation in the coral reef sediments of Lakshadweep Archipelago,Indian Ocean

Surface sediments were collected from the shore and lagoons of Kavaratti, Kadamat and Agatti islands of Lakshadweep Archipelago during May 2015 and analysed for the spatial distribution of the micronutrient element, phosphorus. Phosphorus was separated by sequential extraction procedure into five fractions – exchangeable (Ex-P), iron bound, (Fe-P), calcium bound (Ca-P), organic and residual fractions (OP) and total phosphorus (TP). The average relative contribution of each P species to TP was: OP?>?Ca –P?>?Ex – P?>?Fe – P. The high concentration of organic and residual phosphorus (87–96%) compared to inorganic phosphorus is particularly evident at stations characterised by higher total phosphorus concentrations. Among the three forms of IP in the sediments, Ca-P was dominant at all stations. The OC/OP ratio ranged from 3 to 163 in the sediments, suggesting that the organic matter in sediments had been subjected to degradation. Hence, the major contribution towards organic and residual phosphorus form is from the residual fraction comprising biologically resistant or non-available phosphorus form composed of refractory materials. The concentration of phosphorus reported in the present study is higher than that of the earlier studies in Lakshadweep, indicating a terrestrial and anthropogenic in?uence on the sediment.     

水体冻结过程中卤乙酸前体物在水-冰体系中的分配研究

通过室内模拟试验,研究了水体冻结过程中,水体中溶解性有机物(DOM)和卤乙酸前体物在水-冰体系中的分配规律.按照DOM在XAD树脂上的吸附特性将其分为5个部分:疏水性有机酸(HPO-A),疏水性中性有机物(HPO-N),过渡亲水性有机酸(TPI-A),过渡亲水性中性有机物(TPI-N)和亲水性有机物(HPI).结果表明:在水体冻结过程中,5种DOM组分在水相中的DOC浓度均随冷冻时间的增长而增加,呈现冷冻浓缩效应.与溶解性有机碳(DOC)所表征的整体有机物相比,5种DOM组分中的卤乙酸(HAAs)前体物更倾向于停留在水相中浓缩.在5种DOM组分中,HPI是主要的HAAs前体物.5种DOM组分在未冻结水中的UV-254与HAAFP均表现出一定相关性,其中HPO-A, TPI-A和HPI的UV-254与HAAFP达到极显著水平.然而在融冰水中,这5种DOM组分的UV-254与HAAFP的相关性均不显著.