[Determination of six halogenated solvent residues in olive oil by headspace gas chromatography].

The residual amount of halogenated solvents in olive oil is an important indicator of its quality. The National Olive Oil Quality Standard GB/T 23347-2021 states that the residual amount of individual halogenated solvents in olive oil should be ≤0.1 mg/kg and that the total residual amount of halogenated solvents should be ≤0.2 mg/kg. COI/T.20/Doc. No. 8-1990, which was published by the International Olive Council, describes the standard method used for the determination of halogenated solvents in olive oil. Unfortunately, this method is cumbersome, has poor repeatability and low automation, and is unsuitable for the detection and analysis of residual halogenated solvents in large quantities of olive oil. At present, no national standard method for determining residual halogenated solvents in olive oil is available in China. Thus, developing simple, efficient, accurate, and stable methods for the determination of residual halogenated solvents in olive oil is imperative. In this paper, a method based on automatic headspace gas chromatography was established for the determination of residual halogenated solvents, namely, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, dibromochloromethane, tetrachloroethylene, and bromoform, in olive oil. The samples were processed as follows. After mixing, 2.00 g (accurate to 0.01 g) of the olive oil sample was added into a 20 mL headspace injection bottle and immediately sealed for headspace gas chromatography analysis. Blank virgin olive oil was used to prepare a standard working solution and the external standard method for quantification. The solvents used in the preparation of halogenated solvent standard intermediates were investigated and methanol was selected as a replacement for N,N-dimethylacetamide to prepare a halogenated solvent standard intermediate owing to its safety. The effects of different injection times (1, 2, 3, 4, 5, 6 s), equilibration temperatures (60, 70, 80, 90, 100, 110, 120 ℃), and equilibration times (4, 5, 8, 10, 20, 30, 40 min) of the headspace sampler on the detection of the residual amounts of the six halogenated solvents were investigated. The optimal injection time and equilibration temperature were 3 s and 90 ℃, respectively. The method demonstrated good analytical performance for the six halogenated solvents when the equilibration time was 30 min. A methodological study was conducted on the optimized method, and the results showed that the six halogenated solvents exhibited good linear relationships in the range of 0.002-0.200 mg/kg, with correlation coefficients of ≥0.9991. The limits of detection (LODs) and quantification (LOQs) of 1,1,1-trichloroethane and bromoform were 0.0006 and 0.002 mg/kg, respectively. The LODs and LOQs of chloroform, carbon tetrachloride, dibromochloromethane, and tetrachloroethylene were 0.0003 and 0.001 mg/kg, respectively. The average recoveries under different spiked levels were 85.53%-115.93%, and the relative standard deviations (n=6) were 1.11%-8.48%. The established method was used to analyze 13 olive oil samples available in the market. Although no halogenated solvents were detected in these samples, a limited number of samples does not represent all olive oils. Hence, monitoring residual halogenated solvents in olive oil remains necessary for its safe consumption. The LOQs of the method for the six halogenated solvents were significantly lower than that of the COI/T.20/Doc. No. 8-1990 standard method (0.02 mg/kg). In addition, the developed method can be conducted under short operation times with high precision and degree of automation as well as good accuracy. Thus, the proposed method is suitable for the determination and analysis of the residues of the six halogenated solvents in large batches of olive oil samples.

[Transformation mechanism of carbon tetrachloride and the associated micro-ecology in landfill cover, a typical functional layer zone].

Landfill is one of the important sources of carbon tetrachloride (CT) pollution, and it is important to understand the degradation mechanism of CT in landfill cover for better control. In this study, a simulated landfill cover system was set up, and the biotransformation mechanism of CT and the associated micro-ecology were investigated. The results showed that three stable functional zones along the depth, i.e., aerobic zone (0-15 cm), anoxic zone (15-45 cm) and anaerobic zone (> 45 cm), were generated because of long-term biological oxidation in landfill cover. There were significant differences in redox condition and microbial community structure in each zone, which provided microbial resources and favorable conditions for CT degradation. The results of biodegradation indicated that dechlorination of CT produced chloroform (CF), dichloromethane (DCM) and Cl- in anaerobic and anoxic zones. The highest concentration of dechlorination products occurred at 30 cm, which were degraded rapidly in aerobic zone. In addition, CT degradation rate was 13.2-103.6 µg/(m2·d), which decreased with the increase of landfill gas flux. The analysis of diversity sequencing revealed that Mesorhizobium, Thiobacillus and Intrasporangium were potential CT-degraders in aerobic, anaerobic and anoxic zone, respectively. Moreover, six species of dechlorination bacteria and eighteen species of methanotrophs were also responsible for anaerobic transformation of CT and aerobic degradation of CF and DCM, respectively. Interestingly, anaerobic dechlorination and aerobic transformation occurred simultaneously in the anoxic zone in landfill cover. Furthermore, analysis of degradation mechanism suggested that generation of stable anaerobic-anoxic-aerobic zone by regulation was very important for the harmless removal of full halogenated hydrocarbon in vadose zone, and the increase of anoxic zone scale enhanced their removal. These results provide theoretical guidance for the removal of chlorinated pollutants in landfills.

Death is in the air: Confirmation of decomposition without a corpse.

This case report summarises the investigation of a death scene in the trunk of a car. Air sampling, laser-induced breakdown spectroscopy, and gas chromatography/mass spectrometry on samples of carpet and tyre well scrapings from the vehicle's trunk were utilised to confirm the presence of a human decompositional event even though no human remains were discovered in the vehicle. Air sampling has been used in numerous industries for many decades, but only recently has been applied to forensic investigations although it has been at the centre of controversy over the use of this technique in such cases. This report also describes the value of such investigative tools and points to the discovery of evidence, which, without the use of these techniques, would not have been identified.

Fabrication of bimetallic Ag/Fe immobilized on modified biochar for removal of carbon tetrachloride.

As an effective conventional absorbent, biochar exhibited limited adsorption ability toward small hydrophobic molecules. To enhance the adsorption capacity, a novel adsorbent was prepared by immobilizing nanoscale zero-valent iron onto modified biochar (MB) and then the elemental silver was attached to the surface of iron (Ag/Fe/MB). It's noted that spherical Ag/Fe nanoparticles with diameter of 51nm were highly dispersed on the surface of MB. As the typical hydrophobic contaminant, carbon tetrachloride was selected for examining the removal efficiency of the adsorbent. The removal efficiencies of carbon tetrachloride by original biochar (OB), Ag/Fe, Ag/Fe/OB and Ag/Fe/MB were fully investigated. It's found that Ag/Fe/MB showed higher carbon tetrachloride removal efficiency, which is about 5.5 times higher than that of the OB sample due to utilizing the merits of high adsorption and reduction. Thermodynamic parameters revealed that the removal of carbon tetrachloride by Ag/Fe/MB was a spontaneous and exothermic process, which was affected by solution pH, initial carbon tetrachloride concentration and temperature. The novel Ag/Fe/MB composites provided a promising material for carbon tetrachloride removal from effluent.

Emissions estimates of carbon tetrachloride for 1992-2014 in China.

Discrepancies in emission estimates of carbon tetrachloride (CCl4, CTC), between bottom-up and top-down methods, have been shown since the 1990s at both the global and regional scale. This study estimates the emissions of China from 1992 to 2014 based on emission functions and aggregated activity information given reasonable uncertainties. The results show that emissions increase from 7.3 Gg/yr (5.6-9.1 Gg/yr at 95% confidential interval) to 14.0 (9.1-19.5) Gg/yr with a growth rate of 6.7 (1.9-11.4) %/yr during 1992-2002 and then decrease to a minimum of 4.3 (1.9-8.0) Gg/yr in 2011. More than 54% of the emissions during 1992-2009 are from the process agents sector. The estimates are comparable with those of other studies and those in this study based on observations during 2011-2014 using the interspecies correlation method. China's contribution to global emissions increases from 7.5% to 19.5% during 1992-2009, but the contribution is reduced to 9.9% and 8.0% in 2010 and 2011, respectively, indicating the effectiveness of compliance with the Montreal Protocol and its subsequent Amendments and Adjustments, whereby CTC emissions are phased-out. The results of this study are beneficial for narrowing the gap between bottom-up estimates and top-down emission calculations of CTC in China.

Atmospheric carbon tetrachloride in rural background and industry surrounded urban areas in Northern Iberian Peninsula: Mixing ratios, trends, and potential sources.

Latest investigations on atmospheric carbon tetrachloride (CTC) are focused on its ozone depleting potential, adverse effects on the human health, and radiative efficiency and Global Warming Potential as a greenhouse gas. CTC mixing ratios have been thoroughly studied since its restriction under the Montreal Protocol, mostly in remote areas with the aim of reporting long-term trends after its banning. The observed decrease of the CTC background mixing ratio, however, was not as strong as expected. In order to explain this behavior CTC lifetime should be adjusted by estimating the relative significance of its sinks and by identifying ongoing potential sources. Looking for possible sources, CTC was measured with high-time resolution in two sites in Northern Spain, using auto-GC systems and specifically developed acquisition and processing methodologies. The first site, Bilbao, is an urban area influenced by the surrounding industry, where measurements were performed with GC-MSD for a one-year period (2007-2008). The second site, at Valderejo Natural Park (VNP), is a rural background area where measurements were carried out with GC-FID and covering CTC data a nonsuccessive five-year period (2003-2005, 2010-2011, and 2014-2015years). Median yearly CTC mixing ratios were slightly higher in the urban area (120pptv) than in VNP (80-100pptv). CTC was reported to be well mixed in the atmosphere and no sources were noticed to impact the rural site. The observed long-term trend in VNP was in agreement with the estimated global CTC emissions. In the urban site, apart from industrial and commercial CTC sources, chlorine-bleach products used as cleaning agents were reported as promotors of indoor sources.

[Evaluation on the capability of testing carbon tetrachloride, benzene, methylbenzene, dimethylbenzene, p' p-DDT of the provincial centers for disease control and prevention].

OBJECTIVE: To evaluate the Centers of Disease Control and Prevention's (CDC) provincial divisions' capabilities of detectingconcentrations of organic parameters such as carbon tetrachloride, benzene, methylbenzene, dimethylbenzene and pesticide parameter of p' p-DDT in drinking water, by adopting a quality control assessment methodology of interlaboratory comparison. METHODS: All laboratories had been divided into 2 groups, each of which contained aboutl6 laboratories. Organic concentrations and pesticide concentrations were assigned to 2 sample groups. Testing capabilities of the laboratories were evaluated through the use of robust statistical methods. RESULTS: Thirty CDC provincial divisions, including municipalities under the central government and in autonomous regions, participated in this interlaboratory comparison. Twenty laboratories obtained positive results in all parameters, accounting for 66.7%. Eight laboratories' results were suspicious, accounting for 26.7%. Finally, 2 laboratories produced outliers, accounting for 6.7%. CONCLUSIONS: The majority of provincial CDC participants in this interlaboratory comparison are capable of testing the concentrations of organic parameterssuch as carbon tetrachloride, benzene, and methylbenzene, dimethyl benzene, and pesticide concentrations of p' p-DDT in drinking water.

Seasonal and diurnal variations of atmospheric peroxyacetyl nitrate, peroxypropionyl nitrate, and carbon tetrachloride in Beijing.

Atmospheric peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), and carbon tetrachloride (CCl4) were measured from September 2010 to August 2011 in Beijing. PAN exhibited low values from mid-autumn to early spring (October to March) with monthly average concentrations ranging from 0.28 to 0.73 ppbV, and increased from early spring to summer (March to August), ranging from 1.37-3.79 ppbV. The monthly variation of PPN was similar to PAN, with low values (below detection limit to 0.18 ppbV) from mid-autumn to early spring, and a monthly maximum in September (1.14 ppbV). The monthly variation of CCl4 was tightly related to the variation of temperature, exhibiting a minimum in winter (69.3 pptV) and a maximum of 180.6 pptV in summer. Due to weak solar intensity and short duration, PAN and O3 showed no distinct diurnal patterns from morning to night during winter, whereas for other seasons, they both exhibited maximal values in the late afternoon (ca. 15:00 to 16:00 local time) and minimal values during early morning and midnight. Good linear correlations between PAN and PPN were found in autumn (R = 0.91), spring (R = 0.94), and summer (R = 0.81), with slopes of 0.130, 0.222, and 0.133, respectively, suggesting that anthropogenic hydrocarbons dominated the photochemical formation of PANs in Beijing. Positive correlation between PAN and O3 in summer with the low slopes (deltaO3/deltaPAN) ranging from 9.92 to 18.0 indicated serious air pollution in Beijing, and strong negative correlation in winter reflected strong O3 consumption by NO titration and less thermal decompositin of PAN.

Enhanced dechlorination of carbon tetrachloride by Geobacter sulfurreducens in the presence of naturally occurring quinones and ferrihydrite.

The effect of naturally occurring quinones including lawsone (LQ), ubiquinone (UQ), juglone (JQ), and 1,4-naphthoquinone (NQ) on the biotransformation of carbon tetrachloride (CT) in the presence of Geobacter sulfurreducens and ferrihydrite was investigated. AQDS was used as the model compound for comparison. The reductive dissolution of ferrihydrite by G. sulfurreducens was enhanced by AQDS, NQ, and LQ. However, addition of UQ and JQ had little enhancement effect on Fe(II) production. The bioreduction efficiency and rate of ferrihydrite was highly dependent on the natural property and concentration of quinone compounds and the addition of low concentrations of LQ and NQ significantly accelerated the biotransformation rate of CT. The pseudo-first-order rate constants for CT dechlorination (kobsCT) in AQDS-, LQ- and NQ-amended batches were 5.4-5.8, 4.6-7.4 and 2.4-5.8 times, respectively, higher than those in the absence of quinone. A good relationship between kobsCT for CT dechlorination and bioreduction ratio of ferrihydrite was observed, indicating the important role of biogenic Fe(II) in dechlorination of CT under iron-reducing conditions. Spectroscopic analysis showed that AQDS and NQ could be reduced to semiquinones and hydroquinones, while only hydroquinones were generated in LQ-amended batches.

Chip-scale Mid-Infrared chemical sensors using air-clad pedestal silicon waveguides.

Towards a future lab-on-a-chip spectrometer, we demonstrate a compact chip-scale air-clad silicon pedestal waveguide as a Mid-Infrared (Mid-IR) sensor capable of in situ monitoring of organic solvents. The sensor is a planar crystalline silicon waveguide, which is highly transparent, between λ = 1.3 and 6.5 µm, so that its operational spectral range covers most characteristic chemical absorption bands due to bonds such as C-H, N-H, O-H, C-C, N-O, C=O, and C≡N, as opposed to conventional UV, Vis, Near-IR sensors, which use weaker overtones of these fundamental bands. To extend light transmission beyond λ = 3.7 µm, a spectral region where a typical silicon dioxide under-clad is absorbing, we fabricate a unique air-clad silicon pedestal waveguide. The sensing mechanism of our Mid-IR waveguide sensor is based on evanescent wave absorption by functional groups of the surrounding chemical molecules, which selectively absorb specific wavelengths in the mid-IR, depending on the nature of their chemical bonds. From a measurement of the waveguide mode intensities, we demonstrate in situ identification of chemical compositions and concentrations of organic solvents. For instance, we show that when testing at λ = 3.55 µm, the Mid-IR sensor can distinguish hexane from the rest of the tested analytes (methanol, toluene, carbon tetrachloride, ethanol and acetone), since hexane has a strong absorption from the aliphatic C-H stretch at λ = 3.55 µm. Analogously, applying the same technique at λ = 3.3 µm, the Mid-IR sensor is able to determine the concentration of toluene dissolved in carbon tetrachloride, because toluene has a strong absorption at λ = 3.3 µm from the aromatic C-H stretch. With our demonstration of an air-clad silicon pedestal waveguide sensor, we move closer towards the ultimate goal of an ultra-compact portable spectrometer-on-a-chip.

Subsoil heterogeneities controlling porewater contaminant mass and microbial diversity at a site with a complex pollution history.

This study seeks to improve our understanding of the conceptual model of pollutant transport and fate in cases of DNAPL contamination at sites with a complex contamination history. The study was carried out in an unconfined aquifer of alluvial fans in the Tarragona Petrochemical Complex (Spain). Two boreholes were drilled and continuous cores were recovered in order to carry out a detailed core description at centimeter scale and a comprehensive sampling of borehole cores. The biogeochemical heterogeneity at these sites is controlled by the conjunction of lithological, hydrochemical and microbiological heterogeneities. Biodegradation processes of contaminant compounds take place not only at the level of the dissolved fraction in the aquifer but also at the level of the fraction retained in the fine, less conductive materials as shown by the biodegradation haloes of parent and metabolite compounds. Sampling the low-conductivity levels also allowed us to identify compounds, e.g. BTEX, that are the remaining traces of the passage of old contaminant plumes whose sources no longer exist. This enabled us to describe past biogeochemical processes and to partially account for the processes occurring today. Transition zones, characterized by numerous textural changes, constitute ecotones whose biostimulation could be effective in promoting the acceleration of the remediation of the multiple pollution at these sites.

Direct and simultaneous determination of trace-level carbon tetrachloride, peroxyacetyl nitrate, and peroxypropionyl nitrate using gas chromatography-electron capture detection.

Gas chromatography equipped with electron capture detector (GC-ECD) has been widely used for detecting atmospheric peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN). However, to the best of our knowledge, only a few capillary columns have been adopted for separation to achieve the direct and simultaneous analysis of the two atmospheric pollutants. This paper demonstrates a novel method for directly and simultaneously measuring atmospheric carbon tetrachloride (CCl(4)), PAN, and PPN using GC-ECD with a DB-1 separation column. The responses of the GC-ECD to PAN, PPN, and CCl(4) were individually calibrated by using gas mixtures prepared via volatilization of synthesized solutions of PAN and PPN or high-purity CCl(4) reagent in a Teflon Bag. The concentrations of PAN and PPN in the synthesized solutions were quantified by ion chromatography (IC). Further calibration of the GC-ECD for PAN was conducted by in situ photochemical formation of gaseous PAN which was quantified by a NO(x) analyzer. The two calibration methods agreed well with each other, and the overall uncertainties for measuring atmospheric PAN were estimated to be ± 13% and ± 15% based on the calibrations of IC and NO(x), respectively. The detection limits (three times the signal to noise ratio) for PAN, PPN, and CCl(4) were estimated to be 22, 36, and 5 pptv (parts per trillion by volume), respectively. The atmospheric concentrations of these compounds were measured for several days in August in Beijing, and the values obtained in this study were found to be in good agreement with the data reported in the literature for Beijing using other GC-ECD methods.

[Implementation of an electronic nose for rapid detection of volatile chloralkane and chloroalkene].

An electronic nose, core detector of which was composed of three metal-doped SnO2 gas sensors and a photo ionization detector (PID) as a sensor array, was developed for rapid detection of volatile chloralkane and chloroalkene. A gas recognition model was developed based on test and analysis with nine of pure gas and five of mixtures, and then the electronic nose was applied to several water samples and the validity was evaluated with a gas chromatography. The results revealed that the sensor array responded differently between the chloralkane and chloroalkene. PID was less sensitive to chloralkane, while linearly responded to chloroalkene (R2 > 0.997). Sensor TGS2602 performed sensitive to carbon tetrachloride (CT), trichloromethane (TCM) and 1,2-dichloroethane (1,2-DCA), with a linear response to the former two but a poor linear response to 1,2-DCA. Sensors TGS2600 and TGS2620 were by far more sensitive and linearly (R2 > 0.995) responded to dichloromethane (DCM) and 1,2-DCA. Therefore in the final gas recognition model, PID was used to determine the concentration of chloroalkene, sensor TGS2602 was used to determine CT and TCM, sensor TGS2600 or TGS2620 was used to determine DCM and 1,2-DCA. When applied to gas mixtures, sensor TGS2602 responded less sensitive than the sum of the response to each single component, while other sensors responded equally. The electronic nose showed a determined result linearly correlated to GC (R2 > 0.96) as applied to samples with a mixture of DCM and perchloroethylene.

[Determination of chloroform and carbon tetrachloride in residential air by capillary gas chromatography].

OBJECTIVE: To establish solvent desorption capillary gas chromatography method for determination of chloroform and carbon tetrachloride in residential air. METHODS: The sample was absorbed by active carbon glass tube, then desorbed by Acetone and determined by Capillary Gas Chromatography. RESULTS: Linear range of this method: 5.0 x 10(-4)-1.0 x 10(-1) mg/m3 for chloroform, 1.9 x 10(-4)-1.0 x 10(-2) mg/m3 for carbon tetrachloride. The sample could be stored in the active carbon glass tube for 7 days. The re-occurrence rate of this method is good. RSD is: 0.41%-1.54% for chloroform, 0.31%-1.03% for carbon tetrachloride. Detection limit of this method: 1.5 x 10(-3) ng for chloroform, and 5.8 x 10(-4) ng for carbon tetrachloride. Recovery rate for different concentrations: 88.5%-98.6% For chloroform, and 91.0%-99.0% for carbon tetrachloride. Sampling efficiency: 93.7%-99.2% for chloroform, and 90.6%-99.2% for carbon tetrachloride. Other Volatile halogenated hydrocarbons with similar structures and similar nature in the residential air do not interfere the measurement. CONCLUSION: The method was easy and quick, with high sensibility. It was applicable to monitor the chloroform and carbon tetrachloride in residential air.

Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron.

Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT.

Sonochemical degradation of perchloroethylene: the influence of ultrasonic variables, and the identification of products.

Sonochemistry is a technique that offers promise for pollutant degradation, but earlier studies on various chlorinated substrates do not give a definitive view of the effectiveness of this methodology. We now report a thorough study of ultrasonic operational variables upon perchloroethylene (PCE) degradation in water (variables include ultrasonic frequency, power and system geometry as well as substrate concentration) and we attempt to close the mass balance where feasible. We obtained fractional conversions of >97% showing very effective loss of pollutant starting material, and give mechanistic proposals for the reaction pathway based on cavitational phenomena inducing pyrolytic and free radical processes. We note major products of Cl(-) and CO(2)/CO, and also trichloroethylene (TCE) and dichloroethylene (DCE) at ppm concentrations as reported earlier. The formation at very low (ppb) concentration of small halocompounds (CHCl(3), CCl(4)) and also of higher-mass species, such as pentachloropropene, hexachloroethane, is noteworthy. But of particular importance in our work is the discovery of significant quantities of chloroacetate derivatives at ppm concentrations. Although these compounds have been described as by-products with other techniques such as radiolysis or photochemistry, this is the first time that these products have been identified in the sonochemical treatment of PCE; this allows a much more effective account of the mass balance and may explain earlier inconsistencies. This reaction system is now better identified, but a corollary is that, because these haloacetates are themselves species of some toxicity, the use of ultrasound here may not sufficiently diminish wastewater toxicity.

Degradation of carbon tetrachloride in the presence of zero-valent iron.

Efforts to achieve the decomposition of carbon tetrachloride through anaerobic and aerobic bioremediation and chemical transformation have met with limited success because of the conditions required and the formation of hazardous intermediates. Recently, particles of zero-valent iron (ZVI) have been used with limited success for in situ remediation of carbon tetrachloride. We studied a modified microparticulate product that combines controlled-release carbon with ZVI for stimulation of in situ chemical reduction of persistent organic compounds in groundwater. With this product, a number of physical, chemical, and microbiological processes were combined to create very strongly reducing conditions that stimulate rapid, complete dechlorination of organic solvents. In principle, the organic component of ZVI microparticles is nutrient rich and hydrophilic and has high surface area capable of supporting the growth of bacteria in the groundwater environment. In our experiments, we found that as the bacteria grew, oxygen was consumed, and the redox potential decreased to values reaching -600 mV. The small modified ZVI particles provide substantial reactive surface area that, in these conditions, directly stimulates chemical dechlorination and cleanup of the contaminated area without accumulation of undesirable breakdown products. The objective of this work was to evaluate the effectiveness of ZVI microparticles in reducing carbon tetrachloride under laboratory and field conditions. Changes in concentrations and in chemical and physical parameters were monitored to determine the role of the organic products in the reductive dechlorination reaction. Laboratory and field studies are presented.

Desorption behavior of carbon tetrachloride and chloroform in contaminated low organic carbon aquifer sediments.

Slow release behavior of carbon tetrachloride (CCl(4)) and chloroform (CHCl(3)) in low organic carbon (<0.1%) deep aquifer sediments was quantified by 1-D column desorption studies with intact cores. The compounds had been in contact with the sediments for 30years. Comparison of the CCl(4) distribution coefficient (K(d)) from this study with those from short contact time experiments suggested that CCl(4)K(d)'s calculated from site contaminated sediments of long contact time are likely a factor of 10 or more higher than those calculated from short contact-time lab experiments. A significant portion of the CHCl(3) mass (55% to more than 90%) was resistant to aqueous desorption in sediments with clay contents ranging from 2.0% to 36.7% and organic carbon content ranging from 0.017% to 0.088%. In contrast, CCl(4) showed greatest mass retention (31% or more) only in the highest clay and organic carbon content sediment. Relatively easy solvent extraction of the residual masses of CCl(4) and CHCl(3) from the sediments indicated the compounds were not permanently sequestered. Tracer breakthrough in columns was well behaved, indicating interparticle diffusion was not causing the slow release behavior. Diffusion out of intraparticle pores is suggested to be the main process governing the observed behavior although, diffusion out of natural organic matter cannot be ruled out as a potential contributing factor. The half-life for release of the slow fraction of CHCl(3) mass from sediments was estimated to be in the range of weeks (100h) to months (1100h). Neither CCl(4) or CHCl(3) were detected at measurable levels in the column effluent of one of the sediments even though a significant mass fraction of CHCl(3) was found present on the sediment following desorption suggesting that our estimate of hundreds to thousands of hours for complete release of CHCl(3) masses from such sediment is conservative.