Measurement of 13C/12C of chloroacetic acids by gas chromatography/combustion/isotope ratio mass spectrometry

This paper describes a novel analytical methodology using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) to measure the 13C/12C ratios of chloroacetic acids (CAAs). CAAs are a major class of environmental pollutants that are widely distributed throughout the world, often at relatively high concentrations, and are of concern due to their toxic effects, particularly on plants. The 13C/12C of CAA reagents was measured by IRMS subsequent to offline combustion. Aqueous solutions of these CAAs were derivatized to the corresponding methyl chloroacetates (MCAAs) with acidic methanol with a known isotopic composition, extracted into pentane, and analyzed by GC/C/IRMS. Measured 13C/12C ratios of derivatized MCAAs were in agreement with calculated values within 1 per thousand for monochloroacetic acid and trichloroacetic acid and within 2 per thousand for dichloroacetic acid, suggesting that methylation and other analytical methodology steps do not isotopically fractionate derivatized MCAAs. 13C/12C ratios of reagent CAAs from different sources had varying isotopic signatures suggesting differences in source carbon and/or production methods. Our results underscore the potential of stable isotopes to serve as tracers of environmental sources of CAAs.     

Treatment of atrazine by integrating photocatalytic and biological processes

This research examines the degradation of atrazine by photocatalytic oxidation (PCO) under different experimental conditions. Deisopropylatrazine, deethylatrazine and deethyldeisopropylatrazine were formed as major intermediates based on gas chromatography-mass spectrometry. The reaction mixture was found to be toxic towards two bioassays, i.e. the Microtox and amphipods survival tests even when atrazine was completely degraded by PCO within 2 h under optimized conditions. The results indicate that adding H2O2 could significantly enhance the degradation of atrazine by PCO. Ammeline, ammelide and cyanuric acid (CA) became the major intermediates/products as detected by high performance liquid chromatography from 6th to the 40th h of PCO treatment. After 72 h PCO treatment, only CA was detectable in the reaction mixture. Further degradation of CA was carried out by a newly isolated CA-degrading bacterium, Sphingomonas capsulata. The photochemical pretreatment integrated with microbial degradation lead to the complete degradation and detoxification of atrazine.     

Microbial activity during composting of anthracene-contaminated soil

Microbial activity of an anthracene-spiked soil mixed with kitchen waste during laboratory composting at 56-59 degrees C was studied using an in-vessel technology. The effect of old compost containing acclimated microorganisms on the composting efficiency was also investigated. Microbial succession, microbial enzyme activity, microbial diversity and anthracene removal rate were analyzed during 42 days of composting. The results demonstrated that inoculating with old compost increased the amounts of thermophilic microorganisms, but did not significantly increase anthracene removal. A microbial succession from mesophilic bacteria to thermophilic bacteria and thermophilic actinomycetes was observed during composting. Polyphenol oxidase activity decreased while catalase activity varied irregularly. Microbial diversity increased drastically when temperature elevated from 35 to 56 degrees C, but decreased when temperature maintained at 56-59 degrees C.     

Effects of leachate recirculation on biogas production from landfill co-disposal of municipal solid waste,sewage sludge and marine sediment

Leachate recirculation is an emerging technology associated with the management of landfill. The impact of leachate recirculation on the co-disposal of three major wastes (municipal solid waste, sewage sludge and sediment dredgings) was investigated using a laboratory column study. Chemical parameters (pH, COD, ammoniacal-N, total-P) and gas production (total gas volume, production rates and concentrations of CH4 and CO2) were monitored for 11 weeks. Leachate recirculation reduced waste-stabilization time and was effective in enhancing gas production and improving leachate quality, especially in terms of COD. The results also indicated that leachate recirculation could maximize the efficiency and waste volume reduction rate of landfill sites.     

Copper tolerance,uptake and accumulation by Phragmites australis

Copper (Cu) uptake and accumulation of five populations of Phragmites australis growing in two mine sites (Parys Mountain, Wales, UK and Plombières, Belgium) contaminated with Cu and three 'clean' sites (Felixstowe, UK; Wisbech, UK and Mai Po, Hong Kong) were studied under field and glasshouse conditions. Cu tolerances in these populations of seedlings raised from seeds collected from the above five sites were also studied under glasshouse conditions. Although concentrations of Cu in the plant tissues (leaves, stems, rhizomes and roots) of P. australis and the associated soils from the Cu-contaminated sites were significantly higher than those of the plant tissues and the soils collected in the clean sites, small differences were found between the two Cu-contaminated populations and the three clean populations when seedlings were grown in 0.1 and 0.5 microg ml(-1) Cu treatment solutions. In general, different populations of seedlings showed similar growth responses, metal uptake and indices of Cu tolerance when cultured in the same Cu treatment solution for 3 weeks. There was insufficient evidence to support the hypothesis that the Cu-contaminated populations have evolved to Cu-tolerant ecotypes.     

HPLC pigment analysis of marine phytoplankton during a red tide occurrence in Tolo Harbour,Hong Kong

A red tide was detected in the inner parts of Tolo Harbour, Hong Kong, in November 2000. Water samples were collected from a fixed station at the centre of the red tide patch for microscopic analysis of phytoplankton community composition and high performance liquid chromatography (HPLC) analysis of phytoplankton pigments. At the peak of the red tide on 24 November 2000, phytoplankton was dominated by the dinoflagellate Scrippsiella trochoidea. The red tide began to decline at the end of November and, by 1 December 2000, the phytoplankton was dominated by diatoms. Chlorophylls and carotenoids in water samples were analysed using HPLC pigment separation technique. Dinoflagellates were indicated by the signature pigment peridinin. Significant correlation (r=0.999) was found between the peridinin concentration and dinoflagellate density. A decrease in peridinin and an increase in fucoxanthin, a major carotenoid in diatoms, marked the shift in phytoplankton composition at the end of the red tide. HPLC analysis also revealed the occurrence of minor phytoplankton groups that are difficult to identify by light microscopy. Red tide monitoring and study of red tide dynamics in Hong Kong have been based on cell counting and spectrophotometric or fluorometric measurement of chlorophyll a. HPLC pigment analysis provides an effective alternative for investigating phytoplankton dynamics during red tide and other algal blooms.     

Activated sludge inhibition by chemical stressors--a comprehensive study.

The effects of shock loads of 1-chloro-2,4-dinitrobenzene (CDNB); cadmium; 1-octanol; 2,4-dinitrophenol (DNP); weakly complexed cyanide; pH 5, 9, and 11; and high ammonia levels on activated sludge biomass growth, respiration rate, flocculation, chemical oxygen demand removal, dewaterability, and settleability were studied. For all chemical shocks, except ammonia and pH, concentrations that caused 15, 25, and 50% respiration inhibition were used to provide a single pulse shock to sequencing batch reactor systems containing a nitrifying or non-nitrifying biomass. Cadmium and pH 11 shocks were most detrimental to all processes, followed by CDNB. The DNP and cyanide primarily affected respiration, while pH 5, pH 9, octanol, and ammonia did not affect the treatment process to a significant extent. A chemical source-process effect matrix is provided, which we believe will aid in the development of methods that prevent and/or attenuate the effects of toxic shock loads on activated sludge systems.     

Enhanced uptake of As, Zn, and Cu by Vetiveria zizanioides and Zea mays using chelating agents

Vetiveria zizaniodes (vetiver) is commonly known for its effectiveness in soil and sediment erosion control. It can tolerate to extreme soil conditions and produce a high biomass even growing in contaminated areas. Zea mays (maize) can also produce a very high biomass with a fast growth rate and possesses some degree of metal tolerance. A greenhouse study was conducted to investigate the feasibility of using vetiver and maize for remediation of arsenic (As)-, zinc (Zn-), and copper (Cu)-amended soils and evaluate the effects of chelating agents on metal uptake by these plants. Vetiver had a better growth (dry weight yield of root and shoot) than maize under different treatment conditions. The effects of different chelating agents on As, Zn, and Cu extraction from soil to soil solution were studied. Among the nine chelating agents used, it was noted that 20 mmol NTA could maximize As and Zn bioavailability, while 20 mmol HEIDA could maximize Cu bioavailability in the soil solution. The surge time in maximizing metal uptake ranged from 16 to 20 days which indicated that timing on plant harvest was an important factor in enhanced metal accumulation. In general, vetiver was a more suitable plant species than maize in terms of phytoextraction of metals from metal-contaminated soil. Application of NTA in As-amended soil and HEIDA in Cu-amended soil at the rate of 20 mmol kg(-1) increased 3-4-fold of As and Cu in shoot of both plants, whereas application of NTA (20 mmol kg(-1)) increased 37- and 1.5-fold of Zn accumulation in shoot of vetiver and maize, respectively. The potential environmental risk of metal mobility caused by chelating agents used for phytoextraction should not be overlooked.