Chloride and Organic Chlorine in Soil

Chloride is ubiquitous in soil, but the past years of research have revealed that organic matter also contains chlorine, in amounts similar to that of phosphorus. Hence, one of the major constituents of soil organic matter has previously been overlooked, and still very little is known about the turnover of organic chlorine in soil. In spite of the obvious connection between chloride and organic chlorine, organic chlorine rarely is considered when the biogeochemical cycling of chloride is in focus, and chloride rarely is taken into account when the occurrence and formation of natural organic chlorine compounds are in focus. The aim of the paper is to review ten years of research concerning the biogeochemical cycling of organic chlorine in soil, and to tie the biogeochemical cycling of organic chlorine to that of chloride.     

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.     

Zinc,lead, chlorine and FeOOH-bearing assemblages in the Apollo 16 sample 66095: Origin by impact of a comet or a carbonaceous chondrite?

Sample 66095, 89 collected from station 6 from the lunar Highlands in the Descartes Site shows evidence of mild to severe shock. These shock features are accompanied by an unusual enrichment in the volatile elements Cl, Zn and Pb and by the presence of FeOOH.FeOOH occurs in two distinct assemblages: (1) with metallic FeNi, (2) with troilite, sphalerite and two Cl bearing Zn, Fe sulfates. Lead is present exclusively in the second assemblage at the boundaries between troilite and goethite. Lead concentrations up to 0.4% were found. However, the nature of lead-bearing phase is unknown. X-ray fluorescence analyses of a 10 × 6 mm area of the thin section also yielded enhanced chlorine, sulfur and zinc contents.The formation of this unique assemblage and the introduction of the material rich in volatile elements is very probably genetically connected with an impact of a carbonaceous chondrite or a comet. The small range of the reaction between the volatile rich gases and metallic FeNi and troilite indicate a short-live-phenomenon and thus fumarolic activity is a very unlikely process.     

Balloon observations of organic and inorganic chlorine in the stratosphere: the role of HClO4 production on sulfate aerosols

Simultaneous observations of stratospheric organic and inorganic chlorine were made in September 1993 out of Fort Sumner, New Mexico, using JPL balloon-borne MkIV interferometer. Between 15 and 20 km, a significant fraction (20-60%) of the inorganic chlorine could not be accounted for by the sum of measured HCl, ClONO2, and HOCl. Laboratory measurements of the reaction of ClO radicals on sulfuric acid solutions have indicated that, along with HCl, small amounts of perchloric acid, HClO4, were formed. Very little is known about the fate of HClO4 in the stratosphere and we use a photochemical box model to determine the impact of this new species on the partitioning of inorganic chlorine in the stratosphere. Assuming that HClO4 is photochemically stable, it is shown that in the enhanced aerosol loading conditions resulting from Mt. Pinatubo's eruption, HClO4 could represent a significant reservoir of chlorine in the lower stratosphere, sequestering up to 0.2 ppbv (or 50%) of the total inorganic chlorine at 16 km. The occurrence of this new species could bring to closure the inorganic chlorine budget deficiency made apparent by recent ER-2 aircraft in situ measurements of HCl.     

小肠梗阻MSCT研究现状

小肠梗阻具有很高的发病率,早期准确诊断和全面病情评估是临床选择治疗方式的前提。多层螺旋CT (MSCT)在评价是否存在小肠梗阻、梗阻部位、严重程度及梗阻病因方面均具有很高的准确度,对继发性肠缺血也能提供有价值的影像学信息。本文对MSCT在小肠梗阻评价中的应用现状进行综述。      

Determination of chlorine concentrations in whole rock: Comparison between prompt-gamma activation and isotope-dilution AMS analysis

Accurate determination of chlorine concentrations in terrestrial rocks is of importance for the interpretation of terrestrial in-situ cosmogenic ³⁶Cl. Neutron capture by ³⁵Cl, together with production from Ca and K, is one of the three major production pathways of ³⁶Cl in rocks. Here, we present an inter-comparison of chlorine determinations by two procedures. The first approach is an independent Cl determination by prompt-gamma (neutron) activation analysis (PGAA). The second method is isotope-dilution based on isotopically enriched stable chlorine carrier added during chemical sample preparation for accelerator mass spectrometry (ID-AMS). Twenty-six (26) whole rock samples have been processed for PGAA and ID-AMS analysis. This study constitutes the first published inter-comparison for concentrations below 100 μgCl/g. Our results show no significant difference in Cl concentrations between methods. This agreement indicates good retention of chloride during the procedure we employ for whole rock sample dissolution. No significant loss of stable chlorine from either the spike or the sample occurs before isotopic equilibrium is reached, prior to AgCl precipitation. Uncertainties, which are <5% for both methods, affect the uncertainty of the total ³⁶Cl production rate less than 2% for our samples.The Cl concentration measured by PGAA can be used to calculate the amount of isotopically enriched spike for AMS-ID sample preparation with the aim to optimize ³⁶Cl analysis. Furthermore, PGAA offers an advance for the interpretation of ³⁶Cl measurements. It allows measurement of concentrations of major, minor and trace elements including the elements for ³⁶Cl production (Cl, K, Ca, Ti, and Fe), as well as of neutron absorbers and neutron moderators (H, B, Sm and Gd). These measurements are performed simultaneously and with a precision necessary for calculating the relative contributions to ³⁶Cl production from the different mechanisms.     

Ozone depletion in the plume of a solid-fueled rocket

The local effects of the emission of a solid-fueled rocket on the stratospheric ozone concentration have been investigated by photochemical model calculations. A one-dimensional horizontal model has been applied which calculates the trace gas composition at a single atmospheric altitude spatially resolved around the exhaust plume. Different cases were tested for the emissions of the Space Shuttle concerning the composition of the exhaust and the effects of heterogeneous reactions on atmospheric background aerosol.The strongest depletion of ozone is achieved when a high amount of the emitted chlorine is Cl₂. If it is purely HCl, the effect is smallest, though in this case the heterogeneous reactions show their largest influence. From the results it may be estimated whether ozone depletion caused by rocket launches can be detected by satellite instruments. It appears that the chance of coincidental detection of such an event is rather small.     

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.     

Chlorine Disinfection of Ground Water Obtained from 200M Deep Wells

The effect of chlorine concentration, ground water pH, and contact time on chlorine demand and the inactivation of coliform bacteria, Escherichia coli , was studied in the laboratory using a batch reactor under controlled environmental conditions. Ground water for this study was obtained from 200m deep wells in Bangkok, Thailand. The test results demonstrate that the kinetics of chlorine inactivation of coliforms in ground water consist of an initial rapid kill rate followed by a slower rate. Disinfection was more effective in acidic pH (5.5) than basic pH (8.5). Chlorine demand exerted by ground water increased with chlorine dose, contact time, and hydrogen ion concentration. Based on the applied chlorine dose, inactivation of E. coli by chlorine at neutral pH and room temperature was over two orders of magnitude less effective in ground water than in demand-free water. Because of the high chlorine demand exerted by this ground water, chlorine residuals leaving the treatment plant are likely to be unstable.     

Investigations on the Biodegradability of Chlorinated Fulvic Acids Untersuchungen zur mikrobiellen Verwertbarkeit gechlorter Fulvinsäuren

Microbial biodegradation of organic substances takes place during drinking water treatment, but also in the distribution net, if the drinking water still contains biodegradable organic substances. This phenomenon is called regrowth. The regrowth potential of a drinking water is high, when for instance ozonation is used as the last step of treatment. It was proved before, that ozonation increases the biodegradability of humic substances, which are the main fraction of organic carbon in drinking water. In this work the objective was to check, if chlorination has a similar effect on humic substances. Using the method developed by Werner of measuring the regrowth potential of a water it could be shown by dilution series with chlorinated and unchlorinated humic substances that the substrate quality of these organics is increased by chlorination. The better substrate quality is seen in the chlorinated solutions, which might contain also low molecular weight organic compounds, but also in the fulvic acid fraction after XAD-enrichment, which removes most of the low molecular weight organic compounds. The chlorination creates in the fulvic acid solutions a shift of molecular size to smaller molecules and higher polar substances, which might be the reasons for the better biodegradability. From these results it can be concluded, that chlorination produces substances, which are more easily biodegradable. But this will not produce regrowth problems as long as there is free chlorine present as a disinfectant. In contrast, when the chlorine demand is very high and no free chlorine is left, this might produce high colony counts in the distribution net.     

Possible effects of volcanic eruptions on stratospheric minor constituent chemistry

Although stratosphere penetrating volcanic eruptions have been infrequent during the last half century, periods have existed in the last several hundred years when such eruptions were significantly more frequent. Several mechanisms exist for these injections to affect stratospheric minor constitutent chemistry, both on the long-term average and for short-term perturbations. These mechanisms are reviewed and, because of the sensitivity of current models of stratospheric ozone to chlorine perturbations, quantitative estimates are made of chlorine injection rates. It is found that, if chlorine makes up as much as 0.5 to 1% of the gases released and if the total gases released are about the same magnitude as the fine ash, then a major stratosphere penetrating eruption could deplete the ozone column by several percent. The estimate for the Agung eruption of 1963 is just under 1% an amount not excluded by the ozone record but complicated by the peak in atmospheric nuclear explosions at about the same time. The long-term contribution to stratospheric CIX by volcanic eruptions is estimated as 0.1 ppbv for the period 1900–60 and 1 ppbv for the much more volcanically active period 1780–1840. All of the estimates are subject to large uncertainties, perhaps a factor of 2 or 3 on the high side and a factor of 10 or more on the low side.Paper presented at the IAGA/IAMAP Joint Assembly, Seattle, WA, U.S.A., August 1977.     

Using Chlorine Dioxide for Drinking Water Disinfection by the Application of the Chlorite/Chlorine Process

Chlorine dioxide stock solutions for the disinfection of drinking water are made by the application of chlorite/chlorine process in many waterworks. In such cases the stock solution is always characterised by a mixture of chlorine and chlorine dioxide. The disinfection of waters of different origin with a mixture of chlorine dioxide and chlorine showed the formation of odours of different intensity. The reasons are the re‐formation of chlorine dioxide and the formation of odorous disinfection by‐products. Applying the chlorine dioxide for disinfection, its re‐formation caused by the reaction of chlorite with chlorine is the dominant reason of odour formation. When chlorine is used, the formation of odorous by‐products becomes more relevant. In order to quantify the sensitivity of water concerning odour, the odour indicator coefficient OI was defined. The decreased demand of chlorine dioxide by applying chlorine and chlorine dioxide in combination is recognised to be the key in order to avoid the formation of odour after the disinfection of drinking water with chlorine dioxide.     

Ageing of Dissolved Halogenated Humic Substances and the Microbiological Influence on this Process

The distribution of halogens in various fractions of humic substances (HS), separated by their molecular weight, was found to be different for the different halogens. This was demonstrated for chlorine, bromine, and iodine in sewage and brown water samples by applying inductively coupled plasma mass spectrometry coupled with size‐exclusion chromatography. Quantification of the different fractions of iodinated humic substances was obtained by quadrupole mass spectrometry in connection with the isotope dilution technique using an ¹²⁹I‐enriched spike solution. Quantitative analysis was not possible for the corresponding chlorine and bromine species because of spectrometric interferences in the quadrupole instrument. The ageing of HS/halogen species was followed with respect to possible transformations of these species in a ground and sewage water sample up to eight weeks. Even if a distinct structural variation of the humic substance was observed with time by measuring the UV absorption, chlorine remained in the same molecular weight fraction and only a small change was found for the HS/bromine species after eight weeks. In contrast to these findings a substantial transformation of HS/iodine compounds took place, which demonstrated that the transfer probability of halogens from one to another HS fraction is increased with decreasing strength of the halogen bond to carbon. By comparing the results of an original sewage water sample with a filtered one and with another one which was enriched by microorganisms cultivated from the same original sample, a strong microbiological influence on the transformation of HS/iodine species was found. A quantitative balance of the corresponding HS/iodine fractions was calculated for an ageing period of eight weeks showing that iodine was preferably transferred to newly formed UV active HS substances of high molecular weight. In total, no iodine was released from the humic substances.     

Testing the use of OSL from quartz grains for dating debris flows in Miyun,northeast Beijing,China

Extreme seasonal summer rain storms are common in the mountains to the north east of Beijing and these often result in mass movement of sediment slurries transported for up to a few km. These debris flows can be deadly and are very destructive to infrastructure and agriculture. This project tests the application of luminescence dating to determining the return frequency of such extreme events. The high sediment concentration and the very short flow duration gives very little opportunity for daylight resetting during transport and only a small fraction of the total mass is likely to be reset before transport begins. Here we examine the quartz single-grain dose distribution from a recent known-age (<25 years) debris flow from a small (∼3.9 km²) catchment ∼140 km north of Beijing and compare it with those from three samples from a sedimentary sequence containing the evidence of multiple flow events.Multi-grain quartz OSL signals are dominated by the fast component and <1% of the 150–200 μm grains give a detectable test dose (4.5 Gy) response. Single-grain beta dose recovery gave a ratio of 0.97 ± 0.06 (n = 30) with an over-dispersion of 23 ± 8% (CAM). Both the recent known age and the palaeo-distributions are highly dispersed with over-dispersions greater than 50%. The average weighted doses range between ∼3 mGy and ∼6.5 Gy, indicating that all deposits are no more than a few thousand years. Minimum age modelling give an age estimate for the youngest sample consistent with the known age, and minimum ages for the older palaeo-deposits suggest that there have been at least 3 major debris flows in this small catchment in the last 1000 years.     

Rare-earth data on monzonoritic rocks related to anorthosites and their bearing on the nature of the parental magma of the anorthositic series

Major and trace elements have been determined in monzonoritic rocks (hypersthene-monzodiorite or jotunite) from two intrusions belonging to the South Rogaland anorthositic complex (Norway). The rare-earth abundance pattern reveals no Eu anomaly, or only a very small one. This fact together with field observations suggest that these rocks represent the parental magma of the anorthositic suite. High Ti and P abundances, low Si content, high Fe/Mg and K₂O/SiO₂ ratios are characteristics of the major element geochemistry. Absolute amounts of some trace elements abundances vary distinctly between the two intrusions. K/Rb ratios as high as 1700 are observed. Partial fusion of upper mantle kaersutite is proposed as a possible mechanism of magma generation. Partition coefficients between plagioclase phenocrysts and liquid are determined.     

On the behaviour of fluorine in volcanic processes

Volatile compunds play a very important role in both the evolution of magmas and the eruptive processes. Despite great interest in the knowledge of volatile distribution in magma chambers prior to eruptions, direct evidence of this kind is very difficult to obtain because a major quantity of gaseous species is released to the atmosphere during volcanic phenomena.Good estimates of volatile contents in magmas have been obtained by their distribution in coexisting mineral phases and microprobe analysis of glass inclusions; however, a sufficient set of data is not yet available to provide direct evidence of volatile concentrations in magma chambers before eruptive processes.Owing to their volatility, water, hydrogen, carbon dioxide, sulphur and chlorine compounds are largely concentrated in the explosive cloud. On the other hand, molecular species of fluorine, which are more soluble than water in magmatic melts, strongly partition into this latter phase rather than into the fluid. As a consequence, fluorine compounds are normally present in small concentrations in fumarolic gases and are not expected to degas appreciably from quenched volcanic products.With reference to the influence of weathering processes, recent research has shown that unaltered volcanic glasses have lost but a minor quantity of fluorine as a result of secondary reactions. Because of this, analytical data for fluorine in fresh igneous rocks would not differ significantly from the actual values pertaining to the magmatic stage.The distribution of fluorine in samples from Italy (Vesuvius, Vulcano, Lipari, Roccamonfina, Phlegraean Fields) and Greece (Santorini) appears to be correlated with the concentration of potassium, which is in accordance with theoretical assumptions and analytical results in other areas.According to experimental data, the presence of fluorine in magmas of silicate composition considerably enhances the solubility of water.Higher concentrations of water would mean a higher potential explosivity, and the possibility that the observed concentrations of fluorine can serve as a measure of different degrees of stored energy is considered.Contribution of C.N.R. Centro di Studio per la Mineralogia e la Geochimica dei Sedimenti.     

Compound‐Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis‐DCE compound‐specific isotope analysis of carbon and chlorine collected over a 16‐month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis‐DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ³⁷Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis‐DCE. Carbon isotopic values range between ?28.9 and ?20.7‰ VPDB for TCE, and ?26.5 and ?11.8‰ VPDB for cis‐DCE. In most wells, isotopic values remained steady over the 15‐month study. Isotopic enrichment from TCE to cis‐DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine‐carbon isotopic enrichment ratios (?_Cl/?_C) were 0.18 for TCE and 0.69 for cis‐DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume.     

Adjusting Chlorine Dosage and to Prevent Bio‐Growth and Minimize Trihalomethanes in Reverse Osmosis Filtrate in a Wastewater Reclamation Process

Feasibility of effluent reclamation for the Futian municipal WWTP in Taichung Taiwan was evaluated using an “SF‐UF‐RO” pilot plant. The optimal parameters of each unit were obtained during the pilot plant test. The pilot plant started the operation in late October 2008 and operated until January 2011. The reverse osmosis (RO) system produces 75 m³ water daily, and the produced water quality was comparable to the city water in Taichung. Chlorine dosed in the sand filtration (SF) inlet and ultrafiltration (UF) backwash had the most significant effect on the stability of system performance. When the chlorine was underdosed, biofilm clogged the bag filter (prefilter of UF) and led to the flow rate decay of the UF. The prefilter needed replacement every 1 or 2 weeks resulting in increased process cost. On the other hand, when the chlorine dosage was increased to mitigate the biofilm growth, the residual chlorine not only reacted with TOC and derived trihalomethanes (THMs) in the RO product water (more than 20 µg/L), but it also damaged the RO membrane. After trial and error, the chlorine concentration was optimized as 0.7 mg/L in SF inlet to prevent growth of biofilm as well as to control the residual chlorine in the RO inlet and THMs in the RO product water. It is suggested that cautiously adjusting chlorine dosage is essential for stably operating such a hybrid membrane system to reclaim the municipal wastewater.     

Nitrogen in fluids effecting retrogression of granulite facies gneisses: a debatable mantle connection

The abundance patterns of nitrogen, and chlorine in retrogressed granulite facies gneisses from southern East Greenland exhibit strong enrichment in the vicinity of small-scale shear zones. Sulfur in the shear zones occurs at the same concentration levels as in the adjacent country rock, but is depleted in the transition zone between shear zone and country rock. Within the shear zone sulfur occurs as sulfate, whereas in the country rock granulites it occurs as sulfide. Recrystallization of rock in the shear zone to scapolite-bearing, hornblende-absent assemblages, along with changes in the major element chemistry, demonstrates that these zones define migration pathways of chemically reactive fluids. Consideration of the computed fluid compositions, and of the mass ratios of chlorine/sulfur and nitrogen/sulfur demonstrate that the fluid equilibrated with continental crust prior to its passage through gneisses in the study area. Previous suggestions have been made that the mantle may act as a source region for nitrogen-rich fluids. However, equilibration of these S-, N- and Cl-rich fluids with crustal material precludes the use of element abundances to identify a mantle signature; the bulk of these fluid constituents must be considered crustal derived.