Punctual and continuous estimation of transit time from dissolved organic matter fluorescence properties in karst aquifers,application to groundwaters of ‘Fontaine de Vaucluse’ experimental basin (SE France)

For about 10 years, environmental tracing development using dissolved organic matter (DOM) has been the subject of several studies. Particularly, the use of characterization techniques, like fluorescence emission–excitation matrices has enabled the identification of DOM sources and monitoring them within mainland or marine hydrosystems. Moreover, hydrogeologists have shown the significance of total organic carbon content used as a fast seepage tracer in karstic aquifers. The aim of this study consists in using DOM fluorescence signals to develop a transit time semi-quantitative tracer in heterogeneous hydrosystems. The Low-Noise Underground Laboratory (Vaucluse, France) cuts the network of Fontaine de Vaucluse (FV) karstic vadose zone randomly, and offers a special access to different unstructured dripwaters, with different hydrodynamic behaviour, inside its galleries, i.e. not hierarchical as in natural caves. Previous long-term hydrodynamic and hydrochemical studies allowed the understanding of their hydrogeological behaviour and the estimation of mean transit times. That is why this site is adequate to develop new transit time tracers. After identification of the different DOM sources (i.e. lithic and rendzic leptosols), fluorescence intensities monitoring from soil leachates and dripwaters, for certain excitation–emission wavelength pairs, allowed the development of punctual transit time tracing, by spotting infiltration periods of fluorescent compounds, and monitoring their transfer within a hydrosystem. A fluorescence index (humification index) and the mean transit time of each gallery groundwater, stemmed from previous hydrodynamic and hydrochemical studies, allowed the calibration of a logarithmic relationship. This one allows the development of a continuous transit time tracing method that estimates transit times without long-term studies. It has been tested on two springs of FV catchment basin, providing transit time estimations for karstic hydrosystems that do not present a mixture between recent and pluriannual waters.     

Relationships between DOC concentration,molecular size and fluorescence properties of DOM in a stream

The patterns of dissolved organic matter (DOM) fluorescence properties were examined in a Precambrian shield stream over a seven-month field study. Unique spatial and temporal patterns of simultaneous changes were observed in dissolved organic carbon concentration (DOC), humic-like fluorescence intensity, maximum excitation and emission wavelengths and fluorescence index (the ratio of the emission intensity at a wavelength of 450 nm to that at 500 nm at an excitation wavelength of 370 nm). The spatial change indicates the alteration of DOM along the length of the stream, and temporal change corresponded to a drought event in August. In contrast to humic-like fluorescence, the protein-like fluorescence shows considerable variability, suggesting its ephemeral nature. There were strong relationships between humic-like fluorescence intensity, fluorescence index, maximum Ex/Em wavelengths, DOC concentration and molecular size of DOM. This study has significant implications to the understanding of the nature and biogeochemical cycling of DOM.     

Light scattering and extinction in a highly turbid coastal inlet

Multifactor regression analysis was used to test for relationships between chemical, physical and optical properties of the water column in the organically rich, highly turbid waters of Florida's Fort Pierce Inlet. Optical measurements were made at three visible light wavelengths (445 nm, 542 nm and 630 nm). Scattering by suspended particulate material was found to be the primary optical mechanism controlling downwelling irradiance at all three wavelengths. Larger particles showed constant scattering efficiencies of 2 when their diameters exceeded 3 to 5 microns, depending upon the wavelength used for observation. Selective absorption had a definite effect on the transmission of radiant energy in the 445 nm wavelength range. High correlation between extinction at 445 nm and the cross-sectional area of the suspended particulate material indicates particulate, rather than dissolved materials, are the major water column constituents that selectively absorb short wavelength radiant energy in this inlet. Spectral distribution of the downwelling radiant energy field was found to shift dramatically over a period of several months. These shifts in downwelling spectral irradiance were attributed to seasonal and/or event related shifts in concentrations of selectively absorbing compounds within the water column.     

Optimization of As(V) adsorption on Fe-RH-MCM-41-immobilized GAC using Box–Behnken Design: Effects of pH,loadings, and initial concentrations

This work focused on the removal from water of arsenate in the 100 to 500 μg/L range using Fe-RH-MCM-41 immobilized on GAC by a colloidal impregnation method. A Response Surface Method (RSM) based on the Box–Behnken Design (BBD) was used to evaluate the effects of pH, adsorbent loading, and initial arsenate concentrations. The thermal stability of Fe-RH-MCM-41/GAC was greater than 460 °C because Fe-RH-MCM-41 and epoxy resin covered the GAC, preventing GAC weight loss. The rate and capacity for arsenate adsorption on Fe-RH-MCM-41/GAC were higher than for GAC. The effects of pH, adsorbent loading, and initial arsenate concentration showed significant effects on efficiency, in terms of percent arsenate removal. Significant interaction occurred as positive effects between arsenate and arsenate concentrations, and pH and arsenate concentrations, and as negative effects between pH and pH, adsorbent loading and adsorbent loading, and adsorbent loading and arsenate concentrations.     

显微荧光光谱技术在油气成藏研究中的应用——以塔里木盆地巴什托上古生界油气藏为例

根据原油在紫外光的激发下产生荧光的特点,通过显微荧光光谱方法,对有机包裹体的荧光光谱进行定量化分析,利用其主峰波长与荧光强度、主峰波长与红/绿商的相关性,对塔里木盆地巴什托上古生界油气藏的成藏特征进行了初步研究。在研究区所采集的32块岩石样品中共获得64个荧光光谱数据。分析结果表明,巴什托上古生界油气藏存在3个油源,其主峰波长主要集中在439~443nm、469~472 nm和498~503 nm三个值段上,且为不同演化阶段的混源充注。前两者来自于寒武—奥陶系烃源岩,由下至上充注成藏;后一油源来自于石炭系巴楚组,随演化程度的变化同时向上、下两个方向充注。综合同期捕获不同主峰波长的有机包裹体,推测研究区至少存在4期油充注、1期天然气充注。     

An easy and fast IC-CL procedure for the monitoring of Cu(II) and Co(II) in environmental samples

A luminol chemiluminescence (CL) detection/flow injection analysis technique coupled with ion chromatography (IC) has been employed for the determination of low levels of Cu(II) and Co(II) in drinking water samples. The detection system was the CL of luminol/perborate or luminol/percarbonate in alkaline medium catalyzed by these transition metals. Oxalic acid in a solution of KOH and N(CH₃)₄OH was used as an eluent in the IC to improve the column selectivity (Dionex CS5A). Concentration and pH of the eluent affected simultaneously the CL intensity and the retention times (t _R). Under the elution conditions used here, the retention times of both metal ions were much greater when the concentration of oxalic acid was decreased. Thus, R _t(_Cu) = 2.15 min and t _R(_Co) = 4.50 min were measured at 80 mM oxalic acid concentration, while t _R raised to 4.12 and 18 min for Cu(II) and Co(II), respectively, using a 10-mM concentration, but on the other hand, the CL signals showed substantially higher values when the concentration of oxalic acid was lesser in the eluent. An optimum oxalic acid concentration of 20 mM and an eluent pH = 4.7 were selected in order to have reproducible signals with a total analysis time of 10 min. The optimum flow rate for the mobile phase was 1.5 mL min^?1. The concentration and pH of the postcolumn reagents also affected the CL signal, obtaining optimum concentrations of 5 mM for both oxidants (perborate or percarbonate) and luminol, this last dissolved in a 0.1-M borate buffer at pH 12. The optimum flow rate for the postcolumn reagents was 1 mL min^?1. Linear calibrations for both transition metal ions were established, with calculated detection limits of 0.15 ng mL^?1 for Co(II) and 0.20 μg mL^?1 for Cu(II). Others ions commonly present in natural waters showed little or no interference. The method was successfully applied to water samples spiked with Cu(II) and Co(II), obtaining recoveries in the range of 85–128%, depending on the metal concentrations.     

Molecular Weight Distribution of Dissolved Organic Matter in Lake Hongfeng Determined by High Performance Size Exclusion Chromatography （HPSEC） With On-Line UV-Vis Absorbance and Fluorescence Detection

1IntroductionDissolvedorganicmatter (DOM)isamixtureoforganicsubstancesconsistingmainlyofhighmolecularweightpolymericcompounds (KenandLee,1 974) .Itplaysanimportantroleincarboncyclingandbiogeochemicalmobilizationoftracemetalsandorganiccompoundsintheaquaticenvi ronment (BeffleandLeppard ,1 995) .InrecentyearsmanyresearchershavepaidattentiontothesecomplexesbasedontheMWDofDOM ,sincethefateandtransportoftracechemicalsareinfluencedbyitsmolecularsize (Chiouetal.,1 986) .Themolecularweightorfrac…     

雪冰中生物有机酸的测试分析方法研究

生物有机酸是构成酸雨的组分类别，对地表环境有着重要影响，由于其来源与生物界关系密切，因此，对其在雪冰中记录的研究是从历史的角度认识C，H，O等生源元素生物地球化学循环，认识过去生态和环境变化的途径之一，但是，由于其含量较低，易遭受污染等原因，雪冰中有机酸含量的定量测定一直是困扰研究人员的一个问题，在对目前有机酸测试分析现状，测试分析的难点和问题调研的基础上，文章提出了一种利用DX－300离子色谱测试山地冰川雪冰中生物有机酸含量的方法，该方法利用AS4A分析柱，AG4A保护柱，TAC－2样品富集柱和ATC－1阴离子捕集柱，以梯度淋洗方式，在14min内可分离检测出甲酸，乙酸，丙酮酸，甲烷磺酸，草酸等有机酸根离子及氟，氯，亚硝酸，硝酸，溴，磷酸和硫酸等常见无机阴离子，上述有机，无机离子的测试分析相对标准误差分别为：氟（2．0％），乙酸（4．5％），甲酸（2．0％），甲烷磺酸（16．9％），氯（3．1％），亚硝酸（3．9％），硝酸（2．2％），溴（4．9％）和硫酸（2．4％）。     

水体中溶解有机物的特性与测量

系统评述了水体中溶解有机物的特性及测量方法。介绍了水体中溶解有机物的研究概况,指出了开展水体中溶解有机物定量监测的必要性;详述了水体中溶解有机物的激光诱导荧光测量方法、对水体中有机物荧光光谱进行分析的特征光谱荧光标记技术和荧光强度归一化处理技术,以及利用激光诱导荧光方法测量水体中溶解有机物浓度的标定方法;综述了多种因素对利用激光诱导荧光方法测量的影响。     

Groundwater flow in the vicinity of two artificial recharge ponds in the Belgian coastal dunes

Since July 2002, tertiary treated wastewater has been artificially recharged through two infiltration ponds in the dunes of the Belgian western coastal plain. This has formed a lens of artificially recharged water in the dunes’ fresh water lens. Recharged water is recovered by extraction wells located around the ponds. Hydraulic aspects of the artificial recharge and extraction are described using field observations such as geophysical borehole loggings and a tracer test. Borehole logs indicate recharged water up to 20 m below surface, whereas the tracer test gives field data about the residence times of the recharged water. Furthermore, a detailed solute transport model was made of the area surrounding the ponds. Groundwater flow, capture zone, residence times and volume of recharged water in the aquifer are calculated. This shows that the residence time varies between 30 days and 5 years due to the complex flow pattern. The extracted water is a mix of waters with different residence times and natural groundwater, assuring a relatively stable water quality of the extracted water.     

Importance of heavy metal-organic matter interactions in natural waters

The role of organic ligands in metal complexing in natural waters has received little attention because of uncertainties regarding both the abundance and nature of dissolved organic carbon compounds. Recent data show that the bulk of dissolved organic matter in natural waters consists of highly oxidized and chemically and biologically stable polymeric compounds closely resembling soil humic substances. Average molar concentrations of these aquatic humics in major U.S. rivers range from 5 × 10^?6to 3 × 10^?5 moles 1^?1. Fractional elution of soil organic matter by meteoric waters may be considered to be the main process contributing to the presence of humic matter in rivers. The aquatic humic polymers participate in complex formation through ionizable functional groups with a range of differential acidities. The stabilities of metal-humic complexes in natural waters are higher than those of the corresponding inorganic metal complexes. Quantitative evaluation of the metal-organic interactions can be approached by applying variable equilibrium functions which take into account the differential physico-chemical characteristics of the active complexing sites on the polymer molecule. Assuming an average humic concentration of 10 mg 1^?1, complexation of trace metals can be significant even in the presence of excess concentrations of major cations.     

Characterisation of rapid infiltration flows and vulnerability in a karst aquifer using a decomposed fluorescence signal of dissolved organic matter

The fluorescent properties of dissolved organic matter (DOM) have been used as natural tracers in various water systems. However, only few studies have focused on groundwater systems, specifically, on karst systems. The aim of this study was to develop the use of the DOM fluorescence signal as a natural tracer, considering the multiple compartments of a karst system. This method was applied to the Lez hydrosystem, which supplies the city of Montpellier with drinking water. The hydrodynamics and hydrochemistry of the spring were monitored beginning March 2006. The DOM fluorescence was measured by the excitation–emission matrix spectroscopy technique. The analysis of the total fluorescence signal confirms the efficiency of this tool to trace rapid infiltration flows. Moreover, the decomposition of the signal into different fluorophores complements the information provided by the total signal. Indeed, the fluorescence emitted by the humic compounds seems to be the ideal tool for identifying rapid infiltration flows. Nevertheless, the fluorescence of protein-like compounds is better correlated with the inflow of faecal bacteria at the outlet. This decomposition of the fluorescence signal is an interesting way to provide information on both the rapid infiltration flow as well as the vulnerability of the karst aquifers.     

Metal pollution loading,Manzalah lagoon,Nile delta,Egypt: Implications for aquaculture

High cultural enrichment factors are found for Hg (13×), Pb (22.1×), and other potentially toxic metals (e.g., Sn, Zn, Cu, Ag) in the upper 20 cm of sediment cores from the southeastern Ginka subbasin of Manzalah lagoon, Nile delta, Egypt. Cores from other areas of the lagoon show little metal loading. Metal loading followed the closure of the Aswan High Dam, the availability of abundant cheap electricity, and the development of major power-based industries. Industrial wastes containing potentially toxic metals are dumped into the Nile delta drain system. The load carried by Bahr El-Baqar drain discharges into the Ginka subbasin, which acts as a sink and results in metal loading of the sediment deposited there. Further development of aquaculture in this subbasin, of food-stuff agriculture on recently reclaimed lagoon bottom, or where irrigation waters come from Bahr El-Baqar drain or its discharge should be halted or strictly limited until potentially toxic metals in the drain waters and sediment are removed and polluted input drastically reduced. This environmental assessment of heavy metals in aquaculture or agriculture development should extend to other waterbodies in the northern Nile delta, particularly Idku lagoon and lake Mariut, where industrial metal-bearing wastes discharge into the waterbodies.     

Evidence that polysaccharide and humic and fulvic acids are co-extracted during analysis but have different roles in the chemistry of natural waters

Reaction with periodic acid-Schiff reagent (PAS), a modified histochemical staining procedure, was used as an index of carbohydrate content of natural waters. Material derived from the standard method for extraction of soluble humic and fulvic acids (HFA) from natural waters, namely adsorption onto and subsequent elution from DEAE cellulose and XAD resin, showed 5–31% of its C content to be carbohydrate. On passage of pure polysaccharide through a DEAE column, 88% of the loading was retained and 50% was subsequently eluted into what would be classified as the HA fraction. Clearly DEAE extraction cannot be regarded as specific for HFA. Similarly, samples were analysed from 62 lentic (non-flowing) waters of varied chemistry and trophic status in NW England. 22%±5% (mean±S.D.) of dissolved organic C (DOC) was PAS+. The proportion of the DOC that reacted positively to the PAS test exceeded 30% of total DOC in sites where DOC concentration was low (<7 mg/l). There was no correlation in the concentrations of DOC and PAS+C suggesting the components of the former have independent sources. Aluminium and Si concentration correlated negatively with PAS+ concentration whilst exhibiting no correlation with DOC. Consequently, prediction of metal speciation in natural waters requires separate consideration of metal interaction with PAS+ and other components of DOC, such as HFA.     

Polycyclic aromatic hydrocarbons (PAHs) in lake sediments record historic fire events: Validation using HPLC-fluorescence detection

Understanding the natural mechanisms that control fire occurrence in terrigenous ecosystems requires long and continuous records of past fires. Proxies, such as sedimentary charcoal and tree-ring fire scars, have temporal or spatial limitations and do not directly detect fire intensity. We show in this study that polycyclic aromatic hydrocarbons (PAHs) produced during wildfires record local fire events and fire intensity. We demonstrate that high performance liquid chromatography with fluorescence detector (HPLC-FLD) is superior to gas chromatography–mass spectrometry (GC–MS) for detecting the low concentrations of sedimentary PAHs derived from natural fires. The HPLC-FLD is at least twice as sensitive as the GC–MS in selective ion monitoring (SIM) mode for parent PAHs and five times as sensitive for retene. The annual samples extracted from varved sediments from Swamp Lake in Yosemite National Park, California are compared with the observational fire history record and show that PAH fluxes record fires within 0.5 km of the lake. The low molecular weight (LMW) PAHs (e.g., fluoranthene, pyrene and benz[a]anthracene) are the best recorders of fire, whereas the high molecular weight (HMW) PAHs likely record fire intensity. PAHs appear to resolve some of the issues inherent to other fire proxies, such as secondary deposition of charcoal. This study advances our understanding of how PAHs can be used as markers for fire events and poses new questions regarding the distribution of these compounds in the environment.     

近岸沉积物再悬浮期间所释放溶解有机物的荧光特征

对采自厦门湾九龙江人海河口的4个沉积物样品进行了室内再悬浮模拟实验,利用荧光激发-发射矩阵光谱(EEMs)研究了再悬浮过程中从沉积物中释放出的有色溶解有机物(CDOM)的荧光特征,同时通过与相应站位沉积物间隙水和底层水的对比分析,探讨了河口近岸海域的沉积物再悬浮作用作为水体中溶解有机物来源之一的可能性.结果表明,对给定站位,CDOM相对荧光强度和溶解有机碳(DOC)含量分布变化非常一致,均为间隙水最高,再悬浮次之,底层水最低;站位之间,底层水和再悬浮水样中CDOM相对荧光强度随盐度的降低而增加,从海端向河端增加的趋势明显.EEMs分析表明,各样品中均存在类腐殖质荧光与类蛋白质荧光团,且模拟实验也表明再悬浮作用可释放类腐殖质与类蛋白质荧光物质到底层水中,表明底质再悬浮将是近岸水体中CDOM的一个重要来源.与相应的底层水相比,间隙水的荧光峰(如峰A/C)的位置发生红移.再悬浮样品中EEMs的荧光团同时表现出相应底层水和间隙水的特征,但是荧光峰(峰A和峰C)的最大激发和发射波长更接近底层水中相应荧光团,与间隙水相比,则发生谱峰位置的蓝移.近海端样品中荧光峰M明显,随着盐度的降低,底层水和再悬浮水样的γ(M/C)值逐渐降低,且海源的峰M由海端向河端逐渐消失,表明峰M属于海洋自生来源.本研究区域DOM的荧光指数在1.61～1.93之间,表明近海端样品DOM主要为生物来源,而近河端样品DOM主要为陆源输入,或者为陆源与生物活动共同作用的结果.     

Bromine and water quality – Selected aspects and future perspectives

Bromine is a microelement present in waters, both in inorganic and in a wide range of organic compounds, though at lower concentrations. Typically, concentrations of organobromine compounds in waters are several orders of magnitude lower than of bromides. Two issues are addressed in the paper: the influence of bromides on the quality of treated waters and organobromines as contaminants of natural waters. Bromide presence in treated water gives rise to formation of potentially mutagenic disinfection by-products (DBPs). Registered amounts of DBPs in potable waters, exceeding the admissible levels, and the published data on DBPs in waters used for leisure and recreation activities, clearly indicate the health risk. Major sources are identified and registered concentrations of EDB, DBCB, methyl bromide, bromacil and PBDEs in the aquatic environment are summarized. The effects of bromide on DBPs formation and numerous examples of organobromine contamination of the aquatic environment indicate that the presence of bromides and organobromine compounds in the aquatic environment will have to be given more consideration, for several reasons. Firstly, larger amounts of bromide are present in saline and contaminated waters and the proportion of such waters being handled is increasing. Similarly, the processes of water purification, treatment and disinfection are now playing a major role. Secondly, emissions from manufacturing of bromine-containing materials growing, due to, inter alia, intensive development of the electronic industry and the plastic manufacturing sector. Thirdly, bromine compounds are also used as medicine ingredients. There is now a growing awareness of the presence of pharmaceuticals in the aquatic environment. Fourth, low bromide concentrations in hypergene zones may be modified in the future, partly because of the climate changes, which may give rise to difficulties with water treatment systems.Water quality standards having relevance to water used for consumption are based only on the best-known (most widespread) DBPs. However new more restrictive legal regulations relating to the use of bromine compounds have been put in place prohibiting the use of certain bromine-based substances or restricting their amount in finished products. In the light of current legislation, the monitoring of water contamination with potentially toxic, mutagenic and endocrine-disrupting organobromine compounds is still unsatisfactory because newly discovered compounds are not included and certain factors governing the exposure to those substances are still left out.The effects of bromine (bromide and organobromine compounds) on water quality have been investigated by researchers from several fields of expertise. The water management authorities ought to make use of the available research data and identify the problems which need to be addressed directly and those which may emerge in the future.     

P350微色谱柱在线分离富集-火焰原子吸收光谱法测定矿石中痕量金

在王水介质条件下,用自行设计的微色谱柱在线分离富集系统分离富集矿石样品中的痕量金,采用火焰原子吸收光谱法进行测定。在原子吸收光谱仪吸喷溶液的流路上,用P350微色谱柱研究了金的分离富集条件,采用快速吸附和快速洗脱技术,以盐酸溶液为淋洗液,亚硫酸钠溶液为洗脱液,测定一个样品整个分离和测定过程仅需1 min,成功地克服了火焰原子吸收光谱法测定金灵敏度低的缺点。方法的相对标准偏差小于3.2%,检出限为0.078μg/g。与现行离线分离富集方法相比,建立的方法具有高效、快速、成本低廉的优点,经实际样品验证获得了较为满意的结果。     

Considerations on seismic microzonation in areas with two-dimensional hills

This paper presents the results of an extensive numerical parametric study on seismic behavior of 2D homogenous hills subjected to vertically propagating incident SV waves. It is shown that the amplification potential of these hills is strongly influenced by the wavelength, by the shape ratio, by the shape of the hill and in a less order of importance, by the Poisson ratio of the media. The 2D topography effect could be ignored, only if the hill has a shape ratio of less than 0.1 or if it is subjected to incident waves with predominant dimensionless periods of greater than 13 times the shape ratio. In incidence of waves with wavelengths longer than the width of the hill, the amplification curve usually finds its maximum at the crest and decreases towards the base of the hill. Else, some de-amplification zones would occur along the hill. Among hills with similar shape ratios, those with intermediate cross section areas show intermediate seismic behavior, too. Estimated seismic site coefficients for the crest of a 2D rocky hill depend on its shape ratio and could reach even 1.7, which encourages one to classify it according to standard site categorization procedures as soil profile types SC or SD instead of the conventional SB type.     

Dissolved organic carbon and volatile fatty acids in marine sediment pore waters

The results of a study of the contribution of microbial metabolic products to total dissolved organic carbon (DOC) levels in coastal sediments are presented. The data indicate that acidic volatile compounds make up a substantial fraction of pore water DOC's in both oxic and anoxic pore waters of coastal marine sediments. Formic, acetic and butyric acids are the principal volatile species identified at levels exceeding 10 μM. Acid concentrations are up to five times higher in anoxic pore waters than in oxic waters. Volatile organic acids show promise as indicators of diagenetic processes in marine sediments and of the ecological succession of microorganisms, in particular.