Transient behavior of heavy metals in soils during electrokinetic remediation

This paper presents a systematic bench-scale laboratory study performed to assess the transient behavior of chromium, nickel, and cadmium in different soils during electrokinetic remediation. A series of laboratory electrokinetic experiments was conducted using two different clayey soils, kaolin and glacial till. For each type of soil, four electrokinetic experiments with 1, 2, 4, and 10 d of treatment time were performed. In all tests, the contaminants were Cr(VI), Ni(II), and Cd(II) combined in the soil. A geochemical assessment was performed using the geochemical model MINEQL(+) to determine the partitioning of the heavy metals in soils as precipitated, adsorbed, and aqueous forms. Results showed that in kaolin, the extent of Ni(II) and Cd(II) migration towards the cathode increased as the treatment time increased. Unlike kaolin, in glacial till treatment time had no effect on nickel and cadmium migration because of its high buffering capacity. In both kaolin and glacial till, the extent of Cr(VI) migration towards the anode increased as the treatment time increased. However, Cr(VI) migration was higher in glacial till as compared to kaolin because of the high pH conditions that existed in glacial till. In all tests, some Cr(VI) was reduced to Cr(III), and the Cr(VI) reduction rate to Cr(III) as well as the Cr(III) migration were significantly affected by the treatment time. Overall, this study showed that the electroosmotic flow as well as the direction and extent of contaminant migration and removal depend on the polarity of the contaminant, the type of soil, and the treatment duration.     

Environmental Monitoring of Benzene and Alkylated Benzene from Vehicular Emissions

The volatile organic pollutants from direct vehicular exhaust were trapped with activated charcoal, desorbed with carbon disulphide and analysed by GC/MS with tert-butyl benzene as an internal standard. A comparative study was made from the exhaust of 1000 cc, 1300 cc, 1600 cc cars, pickup, lorry(diesel), 125 cc and 70 cc motorbikes. The level of pollutants emitted were in the following order, motorbike(petrol) car(petrol) pickup(petrol) lorry(diesel). The range of highest emission (125 cc motorbike) to the lowest emission (lorry(diesel)) was of the order of 102 for benzene, 6×102 for ethyl benzene, 5×102 for toluene and 3×102 for xylenes. Among cars, those fitted with catalytic convertors emitted a lower level of benzene (2 to 3 times) when compared with those without catalytic convertors. Similar studies on the air in air-conditioned buses, non air-conditioned buses and three metres from the edge of the road shows that they have the same pollutant level. The level of these pollutant as compared to those from direct car exhaust are of the order of 102 times less for benzene, xylene and toluene and 103 times less for ethylbenzene. The levels of benzene, toluene, ethylbenzene and xylenes by the road side and in the buses were found to be lower than the exposure limits of ACGIH, OSHA and EH40.     

Laboratory and field evidence of the photonitration of 4-chlorophenol to 2-nitro-4-chlorophenol and of the associated bicarbonate effect

Background, aim and scope  

Photochemical processes can decontaminate the aqueous environment from xenobiotics, but they also produce secondary pollutants. This paper presents field and laboratory evidence of the transformation of 4-chlorophenol (4CP) into 2-nitro-4-chlorophenol (2N4CP).     

Petrosia testudinaria as a biomarker for metal contamination at Gulf of Mannar, southeast coast of India

Coastal marine ecosystems in many parts of the world are under unrelenting stress caused by urban development, pollutants and other ecological impacts such as building of infrastructure, land reclamation for port and industrial development, habitat modification, tourism and recreational activities. The present work is a first extensive field study using the marine sponge, Petrosia testudinaria as a biomarker to detect heavy metal pollution between near and off shore environment of 'Gulf of Mannar', India. Sponges were collected from near shore (0.5-1 km) and offshore (5-7 km), locations and their metal concentrations were determined by inductively coupled plasma-mass spectrometry (ICPMS). Our results show that the near shore sponge accumulated greater concentrations of heavy metals (Al, Fe, Mn, As, Ni, Co, Cu, Se) ranging from 0.13 to 64 times higher concentration than the sponges located away from the shore. The results indicate that the accumulated metals alter the macromolecule composition (sugars, proteins and lipids) in near shore sponges. Frequent monitoring is necessary to assess the eco-health of the marine environment by choosing bioindicator species like sponges, which provide accurate, reliable measurement of environmental quality.     

Emissions of polychlorinated biphenyls (PCBs) from sludge drying beds to the atmosphere in Chicago

Ambient air PCB concentrations in the Lake Calumet region in Southeast Chicago have been found to be significantly higher than in nearby non-urban areas. This area is highly industrialized and also contains municipal sludge drying facilities and landfills. In an effort to quantify the importance of the sludge drying facilities to the elevated concentrations, upwind/downwind air samples from the Calumet East sludge drying bed were obtained between April and October 2002. For these samples, the downwind minus upwind (downwind-upwind) concentration varied from 0.33 to 1.27ngm(-3) for non-northeast (NE) direction winds suggesting sludge drying is a source of PCBs to the atmosphere. However, the upwind concentrations were higher than the downwind for winds from the NE of the sampling site suggesting more significant source(s), possibly Lake Calumet or the so called "Cluster site" NE of the sludge drying beds. Flux chamber experiments carried out during the sampling period measured average PCB fluxes of 210ngm(-2)h(-1) (range 43-910ngm(-2)h(-1)) which resulted in an overall flux of 0.005kgday (d)(-1) ( approximately 2kgyr(-1)). A developed regression equation between moisture content and sludge concentration estimated higher PCB losses of 0.26kgd(-1) ( approximately 95kgyr(-1)). Although these two approaches yielded different values, they both indicate that the emission from the Calumet East sludge drying beds were of minimal importance when compared to the total estimated amount of 2-70kgd(-1) (700-2100kgyr(-1)) of PCBs entering the Chicago atmosphere.     

Total immobilization of soil heavy metals with nano-Fe/Ca/CaO dispersion mixtures

This report shows that soil heavy metals can be totally immobilized by grinding with nano-Fe/Ca/CaO. Remediation of soils contaminated by heavy metals is a critical issue in Japan. Indeed, contaminated soils are notoriously difficult to remediate using available technologies. Major setbacks in typical immobilization techniques for heavy metals are wet conditions, forming secondary effluents and further treatment for effluents. Solidification with nano-Fe/Ca/CaO dispersion mixture is a promising treatment for the total immobilization of soil heavy metals As, Cd, Cr, Pb, and separation in dry conditions. Here, we studied the heavy metal immobilization by simple grinding with the addition of three mixtures: nano-Fe/CaO, nano-Fe/Ca/CaO, and nano-Fe/Ca/CaO/PO₄. Samples were analyzed by inductively coupled plasma optical emission spectrometry (ICP-OES) and scanning electron microscopy combined with electron dispersive spectroscopy (SEM–EDS). Results show that the addition of nano-Fe/Ca/CaO immobilized 95–99 % of heavy metals, versus 65–80 % by simple grinding. After treatment, 36–45 wt% of magnetic and 64–55 wt% of nonmagnetic fractions of soil were separated. Their condensed heavy metal concentration was 85–95 % and 10–20 %, respectively. Nano-Fe/Ca/CaO treatment reduced the concentration of leachates heavy metals to values lower than the Japan soil elution standard regulatory threshold of 0.01 mg/l for As, Cd, and Pb; and 0.05 mg/l for Cr. This technology can therefore immobilize totally soil heavy metals and reduce heavy metal by separation.     

Modelling livelihoods and household resilience to droughts using Bayesian networks

Over the last four decades, the Indian government has been investing heavily in watershed development (WSD) programmes that are intended to improve the livelihoods of rural agrarian communities and maintain or improve natural resource condition. Given the massive investment in WSD in India, and the recent shift from micro-scale programmes (<500 ha) to meso-scale (~5000 ha) clusters, robust methodological frameworks are needed to measure and analyse impacts of interventions across landscapes as well as between and within communities. In this paper, the sustainable livelihoods framework is implemented using Bayesian networks (BNs) to develop models of drought resilience and household livelihoods. Analysis of the natural capital component model provides little evidence that watershed development has influenced household resilience to drought and indicators of natural capital, beyond an increased area of irrigation due to greater access to groundwater. BNs have proved a valuable tool for implementing the sustainable livelihoods framework in a retrospective evaluation of implemented WSD programmes. Many of the challenges of evaluating watershed interventions using BNs are the same as for other analytical approaches. These are reliance on retrospective studies, identification and measurement of relevant indicators and isolating intervention impacts from contemporaneous events. The establishment of core biophysical and socio-economic indicators measured through longitudinal household surveys and monitoring programmes will be critical to the success of BNs as an evaluation tool for meso-scale WSD.     

Stable chlorine intramolecular kinetic isotope effects from the abiotic dehydrochlorination of DDT

INTENTION, GOAL, SCOPE, BACKGROUND: Identifying different sources and following reaction pathways of chlorinated organic contaminants in the environment can be challenging, especially when only their concentrations are available. Compound-specific stable chlorine measurements of some contaminants have recently been shown to provide additional information and an increased understanding of their biogeochemistry. These studies, however, have been generally limited to volatile molecules. OBJECTIVE: Here, the stable chlorine isotope ratios of the semi-volatile pesticide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) were investigated. Specifically, the intramolecular stable chlorine isotopic compositions of DDT and the kinetic isotope effect (KIE) for the abiotic dehydrochlorination of DDT to 2,2-bis(p-chlorophenyl)-1,1-dichloroethene (DDE) were determined. METHODS: Selective chemical oxidation of DDT to dichlorobenzophenone (DCBP) and analysis of each compound was used to calculate the stable chlorine isotope ratios of the alkyl and aromatic chlorines in DDT. To determine the KIE for dehydrochlorination, DDT was reacted in a basic solution to yield DDE at 52 degrees C, 60 degrees C, and 72 degrees C for 3, 5, and 5 days, respectively. RESULTS AND DISCUSSION: Significant intramolecular stable chlorine isotopic differences were observed in one sample of DDT where the alkyl and aromatic delta 37Cl values were -5.76 +/- 0.45 and -2.21 +/- 0.24%@1000, respectively. Dehydrochlorination of DDT to DDE in basic solutions at 52, 60, and 70 degrees C resulted in a substantial intramolecular KIE where the alkyl chlorines of DDE shifted by approximately 3%@1000 relative to the alkyl chlorines in DDT. However, no temperature dependence was observed. The KIE, calculated by an iterative program, was 1.009. CONCLUSIONS: Intramolecular differences in the stable chlorine isotope ratios were observed in DDT and this is the first such finding. Dehydrochlorination of DDT yields a measurable and distinct intramolecular stable chlorine KIE. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate the existence of significant intramolecular differences in chlorinated organic compounds. Many other chlorinated semi-volatile and volatile organic contaminants are synthesized from multiple sources of chlorine, and we recommend that similar studies be performed on many such molecules in order to attain a clear understanding of their intramolecular chlorine isotopic differences. The existence of a measurable KIE for the dehydrochlorination of DDT to DDE shows the potential strength of using isotopic measurements to investigate the biogeochemistry of these important compounds. For example, the isotopically depleted aqueous chloride produced by dehydrochlorination of DDT to DDE may be a useful tracer of these reactions in freshwater environments.     

Approach for the use of MSW settlement predictions in the assessment of landfill capacity based on reliability analysis

In the analysis and design of municipal solid waste (MSW) landfills, there are many uncertainties associated with the properties of MSW during and after MSW placement. Several studies are performed involving different laboratory and field tests to understand the complex behavior and properties of MSW, and based on these studies, different models are proposed for the analysis of time dependent settlement response of MSW. For the analysis of MSW settlement, it is very important to account for the variability of model parameters that reflect different processes such as primary compression under loading, mechanical creep and biodegradation. In this paper, regression equations based on response surface method (RSM) are used to represent the complex behavior of MSW using a newly developed constitutive model. An approach to assess landfill capacities and develop landfill closure plans based on prediction of landfill settlements is proposed. The variability associated with model parameters relating to primary compression, mechanical creep and biodegradation are used to examine their influence on MSW settlement using reliability analysis framework and influence of various parameters on the settlement of MSW are estimated through sensitivity analysis.     

Differential pulse adsorptive stripping voltammetric determination of simeton in its formulations and vegetables

A sensitive adsorptive stripping voltammetric method for the determination of simeton with universal buffer solution has been described. The method was based on the adsorption accumulation of simeton at a hanging mercury drop electrode. The overall reduction process is under controlled diffusion. The adsorptive peak was observed at ?0.8 V vs SCE in acidic solution 2 < pH < 6. The peak response was characterized with respect to pH, accumulation potential, time, and scan rate. The calibration plot was found to be linear from 1.13 × 10^???5 to 3.5 × 10^???8 M with a limit of detection of 2.0 × 10^???8 M. Finally, the method has been applied for the determination of simeton in its formulations and vegetable samples.