Pump‐and‐Treat Groundwater Remediation Using Chlorine/Ultraviolet Advanced Oxidation Processes

Comparative studies of the use of chlorine/ultraviolet (Cl₂/UV) and hydrogen peroxide/ultraviolet (H₂O₂/UV) Advanced oxidation processes (AOPs) to remove trichloroethylene (TCE) from groundwater in a pump‐and‐treat application were conducted for the first time at the full‐scale operational level at two water treatment facilities in Northern California. In these studies, aqueous chlorine replaced hydrogen peroxide in the AOP treatment step, where the oxidant is exposed to UV light to produce highly reactive radical species that degrade groundwater contaminants. TCE removal rates as a function of initial chlorine dose and pH were then determined. At the site where the natural pH of the water was 7.1, TCE was removed (to a concentration of less than 0.5 µg/L) for nearly every chlorine dose point tested, and pH adjustment slightly enhanced the treatment process at this facility. The second site had a high natural pH of 7.7, and here, TCE was not completely removed for any chlorine dose up to 5.7 mg/L, although TCE removal did increase when the chlorine dose increased between 0.9 and 3.6 mg/L. Residual TCE remaining in the water post‐Cl₂/UV was readily removed using active carbon filtration, which is part of the overall treatment train at this facility. These studies also verified that Cl₂/UV AOP did not interfere with the photolysis of N‐nitrosodimethylamine or result in an effluent acutely toxic toward Ceriodaphnia dubia. Comparative economic analysis revealed that the chemical costs associated with Cl₂/UV AOP were 25 to 50% of the costs associated with in place H₂O₂/UV AOP treatment.     

Emission spectra of meteorites during thermoluminescence

The emission spectra of four ordinary chondrite meteorites of petrological type 5 have been recorded during thermoluminescence. Spectra from all four samples are similar. A very broad emission structure peaked near 470 nm and extending from 300 to at least 700 nm is found for the glow peaks from 150 to 250°C. The higher temperature peak, 300–500°C, exhibits a different character with a narrow emission band near 400 nm. A tentative model for a luminescence site is offered.The broad similarity between the four samples is particularly interesting as the samples include chondrites of different shock history.The importance of the changes in glow curve spectra with temperature are noted for kinetic analyses of conventional glow curves.     

Characteristics and quantitative of negative ion in salt aqueous solution by Raman spectroscopy at ?170°C

The results from Raman spectroscopy analysis of salt aqueous solutions at −170°C demonstrate that for those clearly sharp iron peaks whose Raman wavenumber is close to each other such as NO ₃ ⁻ and CO ₃ ²⁻ , their original shape could be restorable by the stripping technique, and that ice’s sharp characteristic peak 3090–3109 cm⁻¹) is steady, while the spectrum band of the complex compound (nCl⁻-[H⁺-OH⁻]_n) chlorine ion combined chemically with water molecule is 3401–3413 cm⁻¹. On the other hand, the research shows that the higher the negative iron concentration, the stronger its Raman characteristic peak intensity and the smaller the ice’s. Based on the number of data and theoretical work, the strong correlation of the molar concentration of negative ion with the S _i/S _{H 2}O band area ratio is built up. Moreover, the developed Raman method is successfully used in the component analysis of the field fluid inclusions from Silurian sandstone in Tarim basin.     

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.     

Retention of chloride in soil and cycling of organic matter‐bound chlorine

Chloride (Cl_inorg) is generally considered to be a hydrologically and chemically inert substance. Past research suggests that Cl_inorg participates in a complex biogeochemical cycle involving the formation of organically bound chlorine (Cl_org). The present study examines whether Cl_org cycling is sufficiently extensive as to influence the geochemical cycling of Cl_inorg. Undisturbed soil cores were collected in a coniferous forest soil in SE Sweden. The cores were stored in climate chambers for three months, irrigated with artificial rain, and the leachate was collected and analysed. The water balance of the lysimeters could be well described, and we found that 20–50% of the chlorine leached from the lysimeters was organically bound and that the amounts lost did not decrease with time. This strongly suggests that a substantial amount of Cl_org forms in topsoil, and that subsequent leaching to deeper layers causes a considerable withdrawal of Cl_inorg. The concentration of both organic carbon and Cl_org in the leachate was considerably higher than concentrations observed in the runoff in the actual catchment, suggesting that organic matter precipitates or is mineralized on its way through the soil. Copyright © 2005 John Wiley & Sons, Ltd.     

Zum Auftreten von leichtflüchtigen Halogenkohlenwasserstoffen im Badewasser

110 samples from two swimming-pools were gas-chromatographically investigated for halogenated hydrocarbons. In spite of varying chlorine concentrations between 0.1 and 2.5 mg/l Cl₂ the bacteriological results were unobjectionable. The total of the haloforms was between 1.2 and 182 μg/l, with the average value of 90 μg/l. Besides CHCl₃, CHBrCl₂, CHBr₂Cl and CCl₃NO₂ there were observed other, still unidentified compounds in the chlorinated bathing water which clearly are successive products of disinfection, too. The water treatment by flocculation and filtration does not bring about any elimination of trihalomethanes. Of special importance is the occurrence of trichloronitromethane in concentrations of 0.13 … 1.2 μg/l, whose LC₅₀ in the Daphnia test is 189 μg/l, at a threshold concentration of 160 μg/l. To limit the pollution of water and air to a minimum, specific conditions must be adhered to in the operation of indoor swimming-pools.     

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.     

Reactions of PAH with Chlorine and Chlorine Dioxide in Coal Tar Lined Pipes

In presence of disinfectants, PAH are remobilized from the coal tar lining of water distribution mains. Reactions of the PAH with chlorine and chlorine dioxide can lead to chlorinated PAH that might show higher mutagenic effects than the parent PAH. The application of the solid-phase microextraction as a sampling preparation method in combination with a gas chromatographic mass spectrometric device is a reliable and useful method to achieve detection limits in the lower nanogramme-per-liter level for PAH and chlorinated PAH. Thus, the reactions of four PAH (anthracene, fluoranthene, fluorene, and phenanthrene) with chlorine and chlorine dioxide under conditions prevalent in drinking water distribution systems could be investigated. In batch experiments with demineralized and drinking water at pH 7, the concentrations of fluoranthene, fluorene, and phenanthrene remained constant, whereas anthracene reacted quantitatively with both disinfectants. In these reactions, no chlorinated products could be detected, only mono-hydroxyanthracene and anthraquinone were formed. A reaction mechanism for both reaction products is proposed. The results suggest that oxidation is the major pathway of the reaction of PAH with disinfectants in the systems under investigation.     

芬兰海岸带水域蓝藻水华遥感监测

MODIS-Terra和MERIS数据被用于芬兰湾蓝藻水华的监测,并对两者的性能进行了比较.研究结果表明:MODIS-Terra 波段设置主要针对一类大洋水体,缺乏预警藻蓝素的有效波段;MERIS传感器设置了620nm和665nm波段,基本对应藻蓝素的吸收峰(630nm)和反射峰(650nm),具有蓝藻水华探测的潜力,但在藻华未成型之前,海岸带水体不同优势藻类具有相似的叶绿紊特征,较难辨别蓝藻水华.总的来说,MODlS和MERIS数据比较困难实现蓝藻水华初期预警,但可以有效监测已成型的蓝藻水华.这一方法可以用于中国太湖或者海岸带水体藻华探测和监测研究.     

Analysis of the spectral response of flourishing-withering vegetation changes based on ground spectral measurements

A structural mode was used to characterize vegetation composition at the plant leaf level and a flourishing-withering ratio was developed. The spectral responses of vegetation with different flourishing-withering ratios were analyzed, the change rates of the chlorophyll and moisture content indices of vegetation with different flourishing-withering ratios were compared, and correlations between the chlorophyll and moisture content indices were analyzed. The results reveal that leaves with an intermediate flourishing-withering ratio can increase the absorption signatures of vegetation and that band ranges of 570–700 nm and 1300–1540 nm can play a role in indicating changes in the flourishing-withering ratios of vegetation; NPQI, NPCI, R₆₉₅/R₄₂₀, R₆₉₅/R₇₆₀, R₇₅₀/R₇₀₀, the peak-value area of red selvedge, the red selvedge amplitude, the ratio between the red selvedge amplitude and the minimum amplitude, and the NDVI of vegetation change regularly with the change in flourishing-withering ratios, and these nine vegetation indices are highly related to the chlorophyll content. Vegetation indexes of NDWI and PRI are very sensitive to the flourishing-withering change in vegetation and are closely related to the moisture content, and the correlation coefficient is higher than 0.9. The derivative of the spectra is more effective in describing changes in the structural mode of vegetation with different flourishing-withering ratios, especially at band ranges of 552–628 nm and 630–686 nm, and it is more sensitive to the mixed flourishing-withering ratios of leaves rather than to the vegetation indices. The red selvedge position in the spectrum is highly related to the chlorophyll content and is not sensitive to changes in the structural mode of mixed flourishing-withering leaves. The red selvedge parameters are sensitive to changes in the flourishing-withering ratio at the peak-value area of the red selvedge amplitude and the ratio between the red selvedge amplitude and the minimum amplitude. The effect of a sand background on the spectrum of withering leaves is higher than that of flourishing leaves; the effect of a sand background increases with increasing proportions of withering leaves, the superposition effect of the sand background on mixed flourishing-withering leaves is about 7% at visible light bands of 400–700 nm and 1300–1540 nm, and is over 10% at the near infrared band range of 700–1300 nm.     

Chlorine in submarine glasses from the Lau Basin: seawater contamination and constraints on the composition of slab-derived fluids

Measurements of chlorine concentrations in matrix glasses from 18 primitive (>6 wt% MgO) and eight evolved lavas from active spreading centers in the Lau Basin back-arc system provide insight into the processes which control chlorine concentrations in subduction-related magmas, and can be used to investigate chlorine enrichment related to fluids derived from the underlying subducted slab. Chlorine contents of the glasses are highly variable (0.008-0.835 wt%) and generally high with respect to uncontaminated mid-ocean ridge basalt. Chlorine contents are highest in fractionated lavas from propagating ridge tips and lowest in more primitive basaltic lavas. Two different styles of enrichment in chlorine (relative to other incompatible elements) are recognized. Glasses from the Central Lau Spreading and Eastern Lau Spreading Center typically have low Ba/Nb ratios indicating minimal input of slab-derived components, and high to very high ratios of chlorine relative to K₂O, H₂O, and TiO₂. This style of chlorine enrichment is highest in the most fractionated samples and is consistent with crustal assimilation of chlorine-rich altered ocean crust material. Data from the literature suggest that contamination by chlorine-rich seawater-derived components also characterizes the Woodlark Basin and North Fiji Basin back-arc systems. The second style of chlorine enrichment reflects input from slab-derived fluid(s) to the mantle wedge from the adjacent Tonga subduction zone. Basaltic glasses from the Valu Fa Ridge and Mangatolu Triple Junction show correlations between ratios of chlorine and K₂O, H₂O, and TiO₂ and indices of slab-derived fluid input such as Ba/Nb, Ba/Th and U/Th, consistent with chlorine in these lavas originating from a saline fluid added to the mantle wedge. Within the Valu Fa Ridge the measured range of chlorine contents equates to a chlorine flux of 224-1120 kg/m/yr to the back-arc crust. Using a simple melting model and additional data from other back-arc and arc sample suites we conclude that chlorine is a major component within the slab fluids that contribute to many arc and back-arc melting systems, and probably plays an important role in regulating trace element transport by slab fluids in the mantle wedge. For the back-arc suites we have examined the estimated Cl/H₂O and Cl/K₂O ratios in the slab fluid component correlate with proximity to the arc front, suggesting that progressive dehydration of the slab and/or re-equilibration and transport within the mantle wedge may influence the overall degree of chlorine enrichment within the slab fluid component. The degree of chlorine enrichment observed in most back-arc lavas also appears too great to be explained solely by melting of amphibole, phlogopite or apatite within the mantle source and suggests that chlorine must be present in another phase, possibly a chlorine-rich fluid.     

RESPONSE SPECTRA FOR DIFFERENTIAL MOTION OF COLUMNS

The validity of the response spectrum concept for determining loads in structures excited by differential earthquake ground motion is examined. It is shown that the common definition of response spectrum for synchronous ground motion can be reconciled to remain valid in cases when the columns of extended structures experience different motions. Then, a relative displacement response spectrum for design of first-storey columns, SDC(T, δ, ζ, τ), is defined. In addition to natural period, T, and fraction of critical damping, ζ, this spectrum depends also on the ‘travel time’, τ (of the waves in the soil over distances about one half width, or length of the structure), and on a factor, δ, specifying the relative displacement of the first floor. It is shown how this spectrum can be determined using existing empirical scaling equations for relative displacement spectra SD(T, ζ) and for peak velocity and peak acceleration of strong ground motion. These new spectra are illustrated for a horizontal component of a record in the near field of the 1994 Northridge earthquake. The results show that differential motions are more important for short period (stiff) than for longer period (flexible) structures, and for structures founded on softer ground (small shear wave velocity). © 1997 by John Wiley & Sons, Ltd.     

Reconfiguration and closure of lobe flux by reconnection during northward IMF: possible evidence for signatures in cusp/cleft auroral emissions

Observations are presented of the response of the dayside cusp/cleft aurora to changes in both the clock and elevation angles of the interplanetary magnetic field (IMF) vector, as monitored by the WIND spacecraft. The auroral observations are made in 630 nm light at the winter solstice near magnetic noon, using an all-sky camera and a meridian-scanning photometer on the island of Spitsbergen. The dominant change was the response to a northward turning of the IMF which caused a poleward retreat of the dayside aurora. A second, higher-latitude band of aurora was seen to form following the northward turning, which is interpreted as the effect of lobe reconnection which reconfigures open flux. We suggest that this was made possible in the winter hemisphere, despite the effect of the Earth’s dipole tilt, by a relatively large negative X component of the IMF. A series of five events then formed in the poleward band and these propagated in a southwestward direction and faded at the equatorward edge of the lower-latitude band as it migrated poleward. It is shown that the auroral observations are consistent with overdraped lobe flux being generated by lobe reconnection in the winter hemisphere and subsequently being re-closed by lobe reconnection in the summer hemisphere. We propose that the balance between the reconnection rates at these two sites is modulated by the IMF elevation angle, such that when the IMF points more directly northward, the summer lobe reconnection site dominates, re-closing all overdraped lobe flux and eventually becoming disconnected from the Northern Hemisphere.     

Review of Abiotic Degradation of Chlorinated Solvents by Reactive Iron Minerals in Aquifers

Abiotic degradation of chlorinated solvents by reactive iron minerals such as iron sulfides, magnetite, green rust, and other Fe(II)‐containing minerals has been observed in both laboratory and field studies. These reactive iron minerals form under iron‐ and sulfate‐reducing conditions which are commonly found in permeable reactive barriers (PRBs), enhanced reductive dechlorination (ERD) treatment locations, landfills, and aquifers that are chemically reducing. The objective of this review is to synthesize current understanding of abiotic degradation of chlorinated solvents by reactive iron minerals, with special focus on how abiotic processes relate to groundwater remediation. Degradation of chlorinated solvents by reactive minerals can proceed through reductive elimination, hydrogenolysis, dehydrohalogenation, and hydrolysis reactions. Degradation products of abiotic reactions depend on degradation pathways and parent compounds. Some degradation products (e.g., acetylene) have the potential to serve as a signature product for demonstrating abiotic reactions. Laboratory and field studies show that various minerals have a range of reactivity toward chlorinated solvents. A general trend of mineral reactivity for degradation of chlorinated solvents can be approximated as follows: disordered FeS > FeS > Fe(0) > FeS₂ > sorbed Fe²⁺ > green rust = magnetite > biotite = vermiculite. Reaction kinetics are also influenced by factors such as pH, natural organic matter (NOM), coexisting metal ions, and sulfide concentration in the system. In practice, abiotic reactions can be engineered to stimulate reactive mineral formation for groundwater remediation. Under appropriate site geochemical conditions, abiotic reactions can occur naturally, and can be incorporated into remedial strategies such as monitored natural attenuation.     

乌梁素海沉水植物群落光谱特征及冠层水深影响分析

沉水植物对于改善富营养化水体和重建水生生态系统起着至关重要的作用.应用遥感技术可以实时、大面积监测沉水植物的分布和生长情况,而冠层水深直接影响沉水植物在湖泊、河流中的准确遥感解译.本研究基于实测光谱数据,分析了乌梁素海沉水植物光谱特征,并研究了冠层水深对乌梁素海沉水植物反射光谱的影响,建立了乌梁素海沉水植物冠层水深反演模型.结果表明:1)挺水植物在短波红外1662 nm和2223 nm附近分别有一个反射峰,这是挺水植物区别于沉水植物和漂浮藻类的重要波段; 0深度沉水植物(WDC=0)与漂浮藻类的光谱反射率非常接近,但是在绿波段(550～690 nm)有明显差异,因此,可以利用绿波段和短波红外波段的光谱特征来区分挺水植物、沉水植物和漂浮藻类.2)沉水植物群落的光谱反射率随冠层水深的增加而降低,在700～900 nm波段范围内变化最为明显,且在700～735 nm波段附近,沉水植物群落光谱反射率与冠层水深呈显著负相关.3)在建立的单波段/波段比沉水植物冠层水深反演模型中,波段比反演模型要优于单波段反演模型,波段比反演模型的决定系数R2 0.70,均方根误差13.70 cm,平均相对误差28%,反演精度较好,适用于10～60 cm沉水植物冠层水深的反演.4)利用波段响应函数,将实测光谱反射率积分到Landsat-8 OLI波段上,建立OLI了冠层水深反演模型,其中,波段比幂函数模型反演效果最好,R2为0.49,均方根误差为18.17 cm,平均相对误差40.05%.可用于精确大气校正后乌梁素海沉水植物冠层水深的反演.     

Using Chlorine Dioxide to Remove the Fouling of Ultrafiltration Membrane and Control Disinfection By‐Products

Ultrafiltration (UF) can remove natural organic matter (NOM) effectively. Moreover, chlorine dioxide (ClO₂) has been an alternative disinfectant as it forms fewer disinfection by‐products with NOM than chlorination does. Therefore, combining ClO₂ with UF may improve conventional purification processes. In this study, feed water containing humic acid with 4.07 mg/L total organic carbon (TOC) was dosed directly with various amounts of ClO₂ (0, 2, 5, 10, and 15 mg/L) before being filtered through a 5‐kDa UF membrane. With a low dose (2 mg/L ClO₂), UF removed humic acid effectively, as TOC was not detected in the permeate, and the permeate flux increased to about 80% of the initial permeate flux by cross flow. Moreover, the concentrations of ClO, ClO, and trihalomethanes in the permeate were below the United States Environmental Protection Agency guidelines.     

Association of iron oligomeric species with natural organic matter: a combined EELS and M?ssbauer investigation

The nature of the interaction between iron oxyhydroxide compounds and natural organic matter (NOM) may take various forms and is still a matter of debate. It is an important field to understand, especially for water treatment applications and for the knowledge of iron transport in the environment. The nature of association reached between iron oligomeric species and NOM is here investigated using M?ssbauer spectroscopy and electron energy-loss spectroscopy (EELS) at the Fe-L3 edge. Raw water NOM taken from Moselle River (France), natural humic substances extracted from the riverine suspended matter, and a synthesized humic-like substance, are coagulated with iron nitrate according to a jar-test procedure. The results from M?ssbauer spectroscopy indicate that Fe is present in an octahedral coordination environment, which is consistent with prior X-ray absorption spectroscopy reported in the literature. The areas beneath the peaks (Fe L3 edge) and the peak shapes of EELS spectra differ according to the origin of the organic matter, suggesting that various types of Fe populations can be distinguished using the EELS technique. Combining the selectivity of both M?ssbauer spectroscopy for identifying trace, poorly crystalline Fe solids, oxidation state and of EELS for being able to characterize the population of Fe based on L-edge spectra, appears promising for characterizing Fe in systems containing NOM.     

汶川地震强地面运动模拟

基于确定性震源模型的方法主要用于计算低频(11 Hz)地震动常用经验格林函数法或随机方法,对低频地震动模拟不够准确．本文在确定性震源模型方法基础上,尝试采用分解给定的震源模型的方法来模拟宽频带(0.1——10 Hz)强地面运动,即采用分级离散断层面和分解断层面破裂单元上升时间的方法,增加震源时间函数中的高频信号,从而避免了对地震记录丰富程度和准确性的依赖．文中模拟计算了汶川MS8.0地震在8个地震观测台的地震动,将模拟结果和观测记录进行了加速度时程曲线和傅里叶振幅谱的对比分析．对比结果显示,模拟估计的地震动峰值加速度和持续时间与观测记录的数据基本在plusmn;50%的精度范围内相同,傅里叶振幅谱显示模拟结果有得到10 Hz左右的高频成分. 四川盆地中的台站模拟结果高频衰减比观测记录要快,原因是模拟过程没有考虑场地效应.对强地震动模拟还是要综合考虑震源、传播路径和场地的影响．研究结果表明,此改变震源输入的确定性方法可应用于模拟近断层宽频强地面运动．      

Characteristics and quantitative of negative ion in salt aqueous solution by Raman spectroscopy at -170℃

The results from Raman spectroscopy analysis of salt aqueous solutions at -170℃ demonstrate that for those clearly sharp iron peaks whose Raman wavenumber is close to each other such as and , their original shape could be restorable by the stripping technique, and that ice's sharp characteristic peak (3090-3109 cm-1) is steady, while the spectrum band of the complex compound (nCl--[H+-OH-]n) chlorine ion combined chemically with water molecule is 3401-3413 cm-1. On the other hand, the research shows that the higher the negative iron concentration, the stronger its Raman characteristic peak intensity and the smaller the ice's. Based on the number of data and theoretical work, the strong correlation of the molar concentration of negative ion with the band area ratio is built up. Moreover, the developed Raman method is successfully used in the component analysis of the field fluid inclusions from Silurian sandstone in Tarim basin.