New light on a dark subject: comment

In their article, “New light on a dark subject: On the use of fluorescence data to deduce redox states of natural organic matter,” Macalady and Walton-Day (2009) subjected natural organic matter (NOM) samples to oxidation, reduction, and photochemical transformation. Fluorescence spectra were obtained on samples, which were diluted “to bring maximum uvvisible absorbance values below 1.0.” The spectra were fit to the Cory and McKnight (2005) parallel factor analysis (PARAFAC) model, and consistent variation in the redox state of quinone-like moieties was not detected. Based on these results they concluded that fitting fluorescence spectra to the Cory and McKnight (2005) PARAFAC model to obtain information about the redox state of quinone-like moieties in NOM is problematic. Recognizing that collection and correction of fluorescence spectra requires consideration of many factors, we investigated the potential for inner-filter effects to obscure the ability of fluorescence spectroscopy to quantify the redox state of quinone-like moieties. We collected fluorescence spectra on Pony Lake and Suwannee River fulvic acid standards that were diluted to cover a range of absorbance wavelengths, and fit these spectra to the Cory and McKnight (2005) PARAFAC model. Our results suggest that, in order for the commonly used inner-filter correction to effectively remove inner-filter effects, samples should be diluted such that the absorbance at 254 nm is less than 0.3 prior to the collection of fluorescence spectra. This finding indicates that inner-filter effects may have obscured changes in the redox signature of fluorescence spectra of the highly absorbing samples studied by Macalady and Walton-Day (2009).     

UV irradiation of natural organic matter (NOM): impact on organic carbon and bacteria

UV-induced transformation of dissolved organic matter (DOC) is often accompanied by reduction of molecular weight and aromaticity and an increase of low-molecular weight (LMW) matter that can be utilized as a substrate by heterotrophic bacteria. Moreover, the generation of reactive transients and mineralization of DOC occurs. For a better understanding of the modification that starts after irradiation and to distinguish between possible chemical and biological modifications, we selected different natural organic matter (NOM) from Norway and Germany. The aqueous solutions were treated by UV irradiation and divided into two aliquot samples. NaN₃ anti-bacterial treatment was applied to one sample, and high-pressure size-exclusion chromatography (HPSEC) analysis was used for both. In all samples, we found typical modifications of NOM after UV irradiation. Incubation (>7?days) of UV-irradiated NOM samples resulted in lower levels of LMW matter and increased aromaticity. Parallel to these changes of carbon fractions, an increase in bacterial cell numbers was observed. Addition of NaN₃ to NOM, however, inhibited the reduction of LMW matter, indicating that microbial activity accounted for the observed changes in NOM. Analysis of the bacterial community composition by denaturing gradient gel electrophoresis (DGGE) of the amplified 16S rRNA genes revealed that bacterial communities of non-irradiated and UV-irradiated NOM were different and that UV selected for specific members of ??-proteobacteria, ??-proteobacteria, and Bacteriodetes. Our results imply that after UV-irradiation of NOM, specific bacterial members are well adapted to low pH, high LMW DOC concentrations, and oxidative stress, and therefore thrive well on UV-irradiated humic matter.     

Spectroscopic investigation of humic substances in a tropical lake during a complete hydrological cycle

Fluorescence and UV‐VIS techniques were employed for the investigation of natural organic matter (NOM) of a tropical lake. The relationships of absorbance/dissolved organic carbon (A/DOC), fluorescence intensity/dissolved organic carbon (FI/DOC), fluorescence ratio (FR), and peak wavelength with the highest intensity (PW) were used to distinguish the pedogenic or aquagenic origin of NOM. The values of FR, PW and A₂₈₅/DOC of high waters (HW) or flooded period samples and of low waters (LW) period samples of the dry season, except for September 2002, confirm the predominance of pedogenic material. The spectra of water were similar to the standard fulvic acid (FA), and the spectra of FA from the lake were similar to the nearby soils, indicative of pedogenic predominance. The results confirm that the dissolved NOM of Patos Lagoon – MS (Brazil), in all sampling periods, predominantly consisted of humic substances (FA) of pedogenic origin.     

滇西试验场区的Q值及其随时间窗的变化

本文试用数字地震记录求取尾波Q值及其与频率的关系.在微机上处理触发数字地震仪记录的资料,原始记录经数字滤波器作窄带通滤波得到一组分频记录,经过时间序列分析的方法,可得到能量密度随时间衰减的曲线,该曲线比从可见记录求得的较为可靠.以散射模型的理论表达式进行曲线拟合,求得Q值及其与频率的关系.值得注意的是,这个结果对某一台站并非常数,尾波Q值是时间窗(即研究所用尾波的整个延续时间)的函数,其原因可能是由于不同到时的尾波采样区域和深度不同,以及多次散射的影响等.因此,当把Q值作为地震预报的一个参数时,延续时间是一个重要的可选择的因子.      

Molecular implications of hydrophobic organic partitioning theory

Recent normal phase silica followed by reverse phase XAD separation has led to the identification of several flavonoid and condensed tannin structures in Suwannee River Fulvic Acid (SFRA) (Leenheer, J. A., Rostad, C. (2004) Scientific Investigations Report 2004–5276, U.S. Geological Survey). We have used the molecular properties of one of these structures to define ideal behavior during partitioning of PAHs assuming that these structures function as an immiscible liquid solvent bound to finely dispersed mineral particles. Existing data for the partitioning of PAHs into NOM compared well to this ideal behavior under Raoult/Henry and Flory‐Huggins treatments, and activity coefficients of pyrene in the hypothetical NOM phase and the free energy of transfer were estimated. If experimental data on partitioning of PAHs into synthesized samples of these structures is similar to NOM uptake data, it will be attractive to assume that, a) much smaller components of the NOM complex than suggested by gross molecular weight may be important in environmental properties such as solubility enhancement, and b) the effective molar volumes within the NOM complex responsible for solubility enhancement may be solute, or solute class dependent.     

Metal Distribution in Different Size Fractions of Natural Organic Matter

In this paper, size‐exclusion chromatography (SEC) was used to determine the metal concentration in different size fractions of a bog lake water. Two methods were applied: (a) preparative SEC with off‐line metal concentration analysis and (b) direct coupling of an analytical SEC system on‐line with an inductively‐coupled plasma mass spectrometer (ICP‐MS). In the preparative SEC measurements, maximum concentrations were found for different metal ions in different size fractions of the natural organic matter (NOM). Normalization of metal concentrations to dissolved organic carbon concentration (DOC) yielded two maxima in the high and in the very low molecular‐weight fractions. Whereas good recoveries were found for Al, Fe, and Ni, only 40% were obtained for Pb. This indicates that Pb formed labile complexes with NOM, and hence could strongly interact with the column material. In the experiments with the analytical SEC‐ICP‐MS system, the same trends were observed, but with even lower recoveries than in the preparative system. Sample preconcentration and storage were also investigated with respect to decrease in metal concentration. During the ultrafiltration preconcentration step Al and Fe were removed only to a small extent, whereas about half of the initial Pb was lost. This indicates that Al and Fe were mainly bound to high molecular‐weight fractions of NOM. In contrast to that, Al and in particular Fe were removed from solution more than proportionally with respect to DOC because of aggregation of the NOM during storage, whereas Pb and Ni were concentrated relative to the DOC.     

Luminescence thermochronometry of feldspar minerals: Optimisation of measurement conditions for the derivation of thermal kinetic parameters using isothermal holding experiments

Luminescence thermochronometry is sensitive to very low temperatures (below ∼120 °C), and enables the resolution of thermal histories over sub-Quaternary timescales. Here we apply a multi-elevated-temperature post-infrared infrared-stimulated luminescence (MET-pIR-IRSL) measurement protocol to feldspar minerals to extract thermal histories. These thermal histories depend on the thermal stability of the MET signal, and are based on the thermal kinetic parameters extracted from isothermal decay experiments. However, the derived thermal kinetic parameters vary with experimental conditions, specifically with the isothermal holding temperatures (ITL) used. We analyse samples with independently known thermal histories, together with synthetic thermal history samples and samples with unknown thermal histories to test the validity of thermal kinetic parameters obtained from different combinations of isothermal holding data. This approach is tested on feldspars of different mineralogies and lithologies. We find that the temperatures inferred from inverting the data change, depending both on the number and on the highest ITL temperature used for thermal kinetic parameter derivation. Analysed samples validate the MET-pIR-IRSL protocol for extracting thermal histories, and we suggest that four isothermal holding temperatures between 190 and 250 °C are used for appropriate thermal kinetic parameter derivation.     

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.     

Acid Rain and Natural Organic Matter (NOM)

Twentyfive years of research on the effects of acid rain on rivers and lakes has, to a very small extent, documented changes in the nature and properties of natural organic matter (NOM). In Western Norway, a "whole-watershed-artificial-acidification-experiment" took place in the period 1988–1996. The goals of this long-term experiment were to study the role of NOM in acidification of surface water and the effects of acid precipitation on the quality and properties of NOM. In the HUMEX project (Humic Lake Acidification Experiment) one half of a lake and the corresponding catchment was artificially acidified with H₂SO₄ and NH₄NO₃ over a period of 5 years. The other half of the lake and catchment served as a control. In addition to monitoring of the general chemical composition of the water from the two lake halves, a number of other chemical and biological characteristics were studied. Here, we report the results related to changes in the nature and chemical properties of NOM. During the first few years of acidification, a significantly lower concentration of NOM was recorded in the acidified half of the catchment, compared with the control. However, statistical analyses of all data (covering a 2-years pre-treatment period and 5 years of treatment) related to the concentration of NOM (TOC, colour, and UV absorbance) did not suggest any significant effect on the quantity of NOM. This apparent discrepancy between the initial decrease in the concentration of NOM and no effect when the whole 5-years period is considered, may be due to the results of two different simultaneous processes. The results suggest that there first was a reduction of TOC and colour, as a consequence of the acidification, followed by an increase, perhaps owing to increased fertilisation (nitrogen) and in addition to a general temperature increase during the period. In addition, short-term studies of the aquatic surface microlayers, lipophilicity of the NOM, content of organic sulfur, and molecular size indicate differences in the quality of the NOM between the two lake halves, which could affect light absorption.     

Does Pumping Volume Affect the Concentration of Micropollutants in Groundwater Samples?

Information on concentrations of micropollutants (such as pharmaceuticals, pesticides, and industrial chemicals) in most highly dynamic riverbank filtration (RBF) systems is lacking, in contrast to data on standard chemical parameters. Sampling protocols have thus far been based on the stabilization of standard chemical parameters in relatively pristine environments. To determine whether groundwater samples for micropollutant analysis can be taken at a similar pumping volume as samples for testing standard chemical parameters in both environments, three groundwater monitoring wells in an RBF system were sampled at two points in time (after pumping of 3 well volumes and after pumping of 15 well volumes). Micropollutant concentrations were not significantly different between the two sampling points; therefore, appropriate samples can be drawn after pumping 3 well volumes. For a specific microbiological parameter (leucin incorporation), a statistically significant difference was found.     

基于小波分析和最小二乘支持向量机的中国大陆地震震级预测研究

利用小波分析方法分析百年来中国大陆地震资料, 得到了地震活动在不同时间尺度上的特征, 同时利用各种尺度的小波系数得出地震活动主要周期, 并把此周期值作为参数应用于最小二乘支持向量机预测中。 结果表明, 此方法报准率较高, 平均误差与均方差较小。     

STATISTICAL ANALYSIS OF AIRBORNE ELECTROMAGNETIC SIGNATURES OF DIFFERENT CONDUCTOR GROUPS IN TROPICAL TERRAIN OF KARNATAKA,INDIA*

AEM (airborne electromagnetic) anomalies caused by massive sulphide conductors and superficial conductors can be recognized with a statistical method, as shown by an analysis of Input AEM data from Karnataka State. The weathering in the survey area is of tropical type. Parameters, such as various amplitude ratios and time parameters (inverse of decay rate) for exponential and power-law decay were analyzed for sulphide bodies, conducting soil, superficial conductors, and cultural conductors. Time parameters τ₁ (exponential decay) is defined as ratio of time differences between the third and fourth channel to the logarithmic value of the relative amplitude of the two channels. Time parameter K₁ (power-law decay) is defined as ratio of the difference of the logarithmic values of the delay times of the third and fourth channels to the logarithmic value of the relative amplitude of the two channels. The two parameters have been useful in recognizing sulphide conductors. Also the first channel Input amplitude and logarithmic plot of the transients appear to be helpful in conductor identification. Channel ratios seem to be the least effective parameters of conductor identification. In the area studied both power-law and the conventional exponential decay were found equally suitable for approximating Input AEM transients.     

Estimation of time dependent virus inactivation rates by geostatistical and resampling techniques: application to virus transport in porous media

A methodology is developed for estimating temporally variable virus inactivation rate coefficients from experimental virus inactivation data. The methodology consists of a technique for slope estimation of normalized virus inactivation data in conjunction with a resampling parameter estimation procedure. The slope estimation technique is based on a relatively flexible geostatistical method known as universal kriging. Drift coefficients are obtained by nonlinear fitting of bootstrap samples and the corresponding confidence intervals are obtained by bootstrap percentiles. The proposed methodology yields more accurate time dependent virus inactivation rate coefficients than those estimated by fitting virus inactivation data to a first-order inactivation model. The methodology is successfully applied to a set of poliovirus batch inactivation data. Furthermore, the importance of accurate inactivation rate coefficient determination on virus transport in water saturated porous media is demonstrated with model simulations.     

AN APPROACH TO THE IDENTIFICATION OF FINE SEDIMENTS BY INDUCED POLARIZATION LABORATORY MEASUREMENTS*

Time-domain-induced polarization (IP) laboratory measurements were performed on about 200 fine sediment samples with varying water content. The results permitted an analysis of IP properties of clays, loams, silts, and sands. Particular emphasis has been given to the analysis of the chargeability m as a function of lithotype and the water content. By analyzing decay curves, a new parameter was identified. It is a statistically specific characteristic of the lithotype and is independent of the water content. Therefore, it provides a diagnostic parameter for lithotype identification. In association with the values of chargeability and electrical resistivity, this parameter permits a reliable evaluation of water content and yields useful information about the porosity and permeability of the lithotype.     

GC/MS Nontarget Analysis to Examine an Organic Groundwater Contamination. Part II: Graphical and Multivariate Methods for Searching Key Substances

GC/MS Nontarget Analysis to Examine an Organic Groundwater Contamination. Part II: Graphical and Multivariate Methods for Searching Key Substances In the nontarget analysis, a maximum of organic substances was extracted by a sequence which separates high polar, medium polar, and nonpolar compounds. This leads to the detection of 477 different organic substances in the example of the groundwater contamination investigated. To reduce the high expense for an exact identification of 477 compounds as a first step the individual compound is defined as a data set of retention time and the mass spectrum belonging to this retention time. The table of data contains now 477 individual compounds in groundwater samples collected at 10 different locations. The application of mathematical filters helps to reduce the size of the data set. Graphical methods enable large amounts of data to be visualized in a clear manner and enable to detect patterns in a data set. These patterns are the key to select typical compounds as indicator substances for the contamination source as well as the geogenic background. Similarities between the groundwater samples should not be changed by selection of the indicator compounds. Therefore, cluster analysis was applied as a controlling instrument for the final selection of the indicator compounds. The combination of graphical and multivariate data analysis is a useful tool to deduce indicator compounds for monitoring and control of complex environmental pollution states.     

A comparison of fluorescence and GC for the determination of petroleum hydrocarbons in mussels

The suitability of fluorescence spectroscopy for the determination of aromatic concentrations in mussel tissue was investigated. A mixture of aromatic compounds, with a total emission spectrum similar to those of the samples, was found to be the most suitable standard with measurement being made at the emission maximum. Significant correlations were found between aromatic hydrocarbon concentrations obtained by fluorescence spectroscopy and both aliphatic and aromatic hydrocarbon concentrations obtained by gas chromatographic analysis (GC). Results indicate that analysis of the aliphatic fraction by GC and fluorescence analysis of the aromatic fraction provides a suitable estimation of the relative degree of contamination of mussel tissues by petroleum hydrocarbons.     

Hydraulic properties of peat soils along a bulk density gradient—A meta study

Our understanding of hydraulic properties of peat soils is limited compared with that of mineral substrates. In this study, we aimed to deduce possible alterations of hydraulic properties of peat soils following degradation resulting from peat drainage and aeration. A data set of peat hydraulic properties (188 soil water retention curves [SWRCs], 71 unsaturated hydraulic conductivity curves [UHCs], and 256 saturated hydraulic conductivity [K_s] values) was assembled from the literature; the obtained data originated from peat samples with an organic matter (OM) content ranging from 23 to 97 wt% (weight percent; and according variation in bulk density) representing various degrees of peat degradation. The Mualem‐van Genuchten model was employed to describe the SWRCs and UHCs. The results show that the hydraulic parameters of peat soils vary over a wide range confirming the pronounced diversity of peat. Peat decomposition significantly modifies all hydraulic parameters. A bulk density of approximately 0.2 g cm^?3 was identified as a critical threshold point; above and below this value, macroporosity and hydraulic parameters follow different functions with bulk density. Pedotransfer functions based on physical peat properties (e.g., bulk density and soil depth) separately computed for bog and fen peat have significantly lower mean square errors than functions obtained from the complete data set, which indicates that not only the status of peat decomposition but also the peat‐forming plants have a large effect on hydraulic properties. The SWRCs of samples with a bulk density of less than 0.2 g cm^?3 could be grouped into two to five classes for each peat type (botanical composition). The remaining SWRCs originating from samples with a bulk density of larger than 0.2 g cm^?3 could be classified into one group. The Mualem‐van Genuchten parameter values of α can be used to estimate K_s if no K_s data are available. In conclusion, the derived pedotransfer functions provide a solid instrument to derive hydraulic parameter values from easily measurable quantities; however, additional research is required to reduce uncertainty.     

Hydrogen peroxide production rates in clean and polluted coastal marine waters of the Mediterranean, Red and Baltic Seas

The main aim of this study was to assess the hydrogen peroxide (HP) production rates (HPPR) related to anthropogenic pollution in coastal waters by laboratory and field experiments. HPPR's were assessed by simultaneous measurements of HP concentrations, cumulative solar UV irradiation and dissolved organic matter (DOM) fluorescence in the seawater samples at clean and polluted sites in the Mediterranean, Red and the Baltic Seas. The natural HP concentrations at all sites (8–100 nM) fall within the normal range recorded elsewhere, and follows a diurnal pattern. The polluted stations in the Mediterranean and Baltic Seas showed higher HPPR (3.2–16.6 nM m² W⁻¹ h⁻¹) than the clean stations, while in the Red Sea no significant differences were found because the station that was considered a priori polluted was actually rather clean (2–3 nM m² W⁻¹ h⁻¹). Laboratory experiments demonstrated that HPPR was positively linearly correlated to DOM fluorescence, however, this relationship was not found in the natural seawater samples examined in the field. The lack of relationship between HPPR and DOM in the field was attributed to enzymatic breakdown of HP as observed in dark decay experiments. HP dark decay rates were highest in polluted stations, probably due to larger bacterioplankton populations in these samples. Moreover, the HP dark decay rates were much lower in filtered than in non-filtered samples. Sun incubation of filtered (0.2 μm) seawater samples were performed to assess whether elimination of particles would yield higher HPPRs than in non-filtered samples. In the Baltic Sea (low UV irradiation) HPPR was higher in the filtered samples, while at sites with relatively high UV irradiation (Mediterranean and Red Seas), filtration of seawater did not stimulate HPPRs, probably due to UV-damage to planktonic microorganisms.     

Molar Masses and Radii of Humic Substances Measured by Light Scattering

A bulk aquatic natural organic material (NOM) was characterized by high-performance size exclusion chromatography (HPSEC) coupled with multi-angle laser light scattering (MALLS), UV-Vis, and refractive index detection. This technique was used to measure the molar mass and radius of the natural organic matter in solution. Results indicate that the NOM aggregates to a large extent at the concentrations used in this study (5... 15 mg mL^–1). The solution conditions of pH and ionic strength were also shown to affect the measured size of NOM. The number and type of HPSEC columns also influenced these measurements. The importance of using multiple detectors was illustrated by peaks that were not detected by all the detectors. While these data are preliminary and have large errors associated with them, it is nevertheless an indication that HPSEC-MALLS can be used to investigate the effects of solution conditions and aggregation on the size of humic substances in solution.     

Magnetostratigraphy of Cave Sediments: Application and Limits

The application of the magnetostratigraphy for dating of clastic and chemogenic cave sediments has been limited by the complex conditions underground and the lack of age constraints on these deposits for correlation with geomagnetic polarity timescale (GPTS). Without age constraints any correlation of obtained results cannot be explicit. Additionally, the dynamic character of cave infilling, exhumation and fossilisation expressed by unconformities within preserved sedimentary profiles can hide a substantial part of the geological time. The detailed internal division of deposits (breaks in deposition and related processes) and scarcity of fossils make the correlation of obtained magnetostratigraphic log with geomagnetic polarity timescales sometimes problematic. The analytical results confirmed that the complete step/field procedure offered by demagnetisation methods must be applied. The application of complete analysis only to pilot samples and shortened, selected field/step approach, to other samples did not offer sufficient data set for reliable interpretation.