Xuwei Deng

Simultaneous determination of eight common odors in natural water body using automatic purge and trap coupled to gas chromatography with mass spectrometry.

Production and fate of taste and odor (T&O) compounds in natural waters are a pressing environmental issue. Simultaneous determination of these complex compounds (covering a wide range of boiling points) has been difficult. A simple and sensitive method for the determination of eight malodors products of cyanobacterial blooms was developed using automatic purge and trap (P&T) coupled with gas chromatography-mass spectrometry (GC-MS). This extraction and concentration technique is solvent-free. Dimethylsulfide (DMS), dimethyltrisulfide (DMTS), 2-isopropyl-3-methoxypyrazine (IPMP), 2-isobutyl-3-methoxypyrazine (IBMP), 2-methylisoborneol (MIB), β-cyclocitral, geosmin (GSM) and β-ionone were separated within 15.3 min. P&T uses trap #07 and high-purity nitrogen purge gas. The calibration curves of the eight odors show good linearity in the range of 1-500 ng/L with a correlation coefficient above 0.999 (levels=8) and with residuals ranging from approximately 83% to 124%. The limits of detection (LOD) (S/N=3) are all below 1.5 ng/L that of GSM is even lower at 0.08 ng/L. The relative standard deviations (RSD) are between 3.38% and 8.59% (n=5) and recoveries of the analytes from water samples of a eutrophic lake are between 80.54% and 114.91%. This method could be widely employed for monitoring these eight odors in natural waters.

A systematic study on spatial and seasonal patterns of eight taste and odor compounds with relation to various biotic and abiotic parameters in Gonghu Bay of Lake Taihu, China

A systematic study was conducted on seasonal and spatial patterns of taste and odor (T&O) compounds with relation to biotic and abiotic parameters at fifteen sites in Gonghu Bay of Lake Taihu in 2008. We developed a sensitive and automated method to simultaneously analyze eight T&O compounds (boiling points ranging from 38°C to 239°C) by using Purge-and-Trap (P&T) coupled with GC/MS. Maximum particulate dimethyl trisulfide (DMTS, 69.6 ng/L) exceeded its odor threshold concentrations (OTC, 10 ng/L) and maximum dissolved DMTS was 6.1 ng/L, but still far below concentration in the drinking water pollution incident of Wuxi City in 2007 when DMTS reached 1768-11,399 ng/L. Geosmin (GEO), 2-methylisoborneol (MIB), β-cyclocitral, β-ionone and 2-isobutyl-3-methoxypyrazine (IBMP) occasionally or frequently exceeded their OTCs, whereas 2-isopropyl-3-methoxypyrazine (IPMP) and dimethyl sulfide (DMS) did not. We found for the first time significant correlations between particulate β-cyclocitral and β-ionon concentrations and intracellular and extracellular microcystin concentrations. Spatially, Nanquan Waterworks faced more risk by T&O contamination than Xidong Waterworks. High concentrations of NO(3)-N, TDN and TN could be risky signs of taste and odor events by DMS, DMTS, IPMP, IBMP and GEO.

Microwave-assisted purge-and-trap extraction device coupled with gas chromatography and mass spectrometry for the determination of five predominant odors in sediment, fish tissues, and algal cells

Off-flavors are among the most troublesome compounds in the environment worldwide. The lack of a viable theory for studying the sources, distribution, and effect of odors has necessitated the accurate measurement of odors from environmental compartments. A rapid and flexible microwave-assisted purge-and-trap extraction device for simultaneously determining five predominant odors, namely, dimethyltrisulfide, 2-methylisoborneol, geosmin, β-cyclocitral and β-ionone, from the primary sources and sinks is demonstrated. This instrument facilitates the extraction and concentration of odors from quite different matrices simultaneously. This device is a solvent-free automated system that does not require cleaning and is timesaving. The calibration curves of the five odor compounds showed good linearity in the range of 1-500 ng/L, with correlation coefficients above 0.999 (levels=7) and with residuals ranging from approximately 77% to 104%. The limits of detection (S/N=3) were below 0.15 ng/L in algae sample and 0.07 ng/g in sediment and fish tissue samples. The relative standard deviations were between 2.65% and 7.29% (n=6). Thus the proposed design is ready for rapid translation into a standard analytical tool and is useful for multiple applications in the analysis of off-flavors.

Off-flavor compounds from decaying cyanobacterial blooms of Lake Taihu

The effect of cyanobacterial bloom decay on water quality and the complete degradation of cyanobacterial blooms in a short period were examined by an enclosure experiment in Gonghu Bay of Lake Taihu, China. Water quality parameters as well as taste and odor compounds during the breakdown of cyanobacterial blooms were measured. Results showed that the decay of cyanobacterial blooms caused anoxic water conditions, decreased pH, and increased nutrient loading to the lake water. The highest concentrations of dimethyl sulfide (DMS), dimethyl trisulfide (DMTS), and beta-cyclocitral were observed in the anoxic water, at 62331.8, 12413.3, and 1374.9 ng/L, respectively. 2-Methylisoborneol was dominant during the live growth phase of cyanobacterial blooms, whereas DMS and DMTS were dominant during the decomposition phase. Dissolved oxygen, pH, and chlorophyll a were negatively correlated with DMS, DMTS, and beta-cyclocitral, whereas total phosphorus, total nitrogen, and ammonium (NH(4+)-N) were positively correlated with DMS, DMTS, beta3-cyclocitral, and beta-ionone. The experimental results suggested that preventing the anaerobic decomposition of cyanobacterial blooms is an important strategy against the recurrence of a malodor crisis in Lake Taihu.

Development of Models for Predicting the Predominant Taste and Odor Compounds in Taihu Lake, China

Taste and odor (T&O) problems, which have adversely affected the quality of water supplied to millions of residents, have repeatedly occurred in Taihu Lake (e.g., a serious odor accident occurred in 2007). Because these accidents are difficult for water resource managers to forecast in a timely manner, there is an urgent need to develop optimum models to predict these T&O problems. For this purpose, various biotic and abiotic environmental parameters were monitored monthly for one year at 30 sites across Taihu Lake. This is the first investigation of this huge lake to sample T&O compounds at the whole-lake level. Certain phytoplankton taxa were important variables in the models; for instance, the concentrations of the particle-bound 2-methylisoborneol (p-MIB) were correlated with the presence of Oscillatoria, whereas those of the p-β-cyclocitral and p-β-ionone were correlated with Microcystis levels. Abiotic factors such as nitrogen (TN, TDN, NO3-N, and NO2-N), pH, DO, COND, COD and Chl-a also contributed significantly to the T&O predictive models. The dissolved (d) T&O compounds were related to both the algal biomass and to certain abiotic environmental factors, whereas the particle-bound (p) T&O compounds were more strongly related to the algal presence. We also tested the validity of these models using an independent data set that was previously collected from Taihu Lake in 2008. In comparing the concentrations of the T&O compounds observed in 2008 with those concentrations predicted from our models, we found that most of the predicted data points fell within the 90% confidence intervals of the observed values. This result supported the validity of these models in the studied system. These models, basing on easily collected environmental data, will be of practical value to the water resource managers of Taihu Lake for evaluating the probability of T&O accidents.

Simultaneous quantitative determination of microcystin-LR and its glutathione metabolites in rat liver by liquid chromatography-tandem mass spectrometry

The roles of glutathione (GSH) and cysteine (Cys) in the detoxification of Microcystin-LR (MC-LR) have recently become a popular area of research. However, lacking analysis methods for MC-LR-GSH and MC-LR-Cys (two main GSH pathway metabolites) in mammals, elucidation of the detoxification mechanism and metabolic pathway of MC-LR in mammals is difficult. In this study, a novel method for the simultaneous quantitative analysis of MC-LR, MC-LR-GSH and MC-LR-Cys in rat liver was developed and validated. The analytes were simultaneously extracted from rat liver using 3M sodium chloride solution containing 0.01M EDTA-Na2-5% acetic acid, followed by solid-phase extraction (SPE) on Oasis HLB and silica cartridges and determination by liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS/MS). Under the optimized pretreatment conditions and instrument parameters, good recoveries of MC-LR, MC-LR-GSH and MC-LR-Cys were obtained at three concentrations (0.2, 1.0 and 2.5 μg g(-1) dry weight (DW)) with values ranging from 97.7 ± 4.2 to 98.7 ± 5.1%, 70.1 ± 4.8 to 71.1 ± 4.1% and 79.8 ± 3.5 to 81.4 ± 4.0%, respectively. The relative standard deviations (RSDs) of these compounds at 0.2, 1.0 and 2.5 μg g(-1) DW were between 4.3% and 6.9%. The limits of detection (LODs) were 0.005, 0.007 and 0.006 μg g(-1) DW and the limits of quantification (LOQs) were 0.017, 0.023 and 0.020 μg g(-1) DW for MC-LR, MC-LR-GSH and MC-LR-Cys, respectively. Furthermore, this method was successfully applied to both time- and dosage-effect studies of MC-LR, MC-LR-GSH and MC-LR-Cys in vivo.

Risk assessment of microcystins in silver carp (Hypophthalmichthys molitrix) from eight eutrophic lakes in China

Bioaccumulation and risk assessment of microcystins (MCs) in muscle of silver carp (Hypophthalmichthys molitrix) from eight eutrophic lakes along the Yangtze River of China were examined by using liquid chromatography electrospray ionisation mass spectrometry. MCs contents in seston collected from these eutrophic lakes ranged from 0.02 to 21.7 μg/L. MCs concentrations in silver carp muscle samples varied from 0.014 to 0.036 μg/g DW with an average of 0.028 μg/g DW. The total length of silver carp showed a significant negative correlation with MCs concentrations in their muscle (r=-0.85, p<0.05), suggesting that MCs accumulation in silver carp muscle seems to be size dependent. EDI values of MCs in fish muscle from these eight eutrophic lakes varied from 0.0027 to 0.0071 μg/kg day, which was much lower than the TDI value of 0.04 μg/kg day previously established by WHO, indicating that it is safe to consume silver carp muscle from eutrophic lakes in China.

Microcystis aeruginosa/Pseudomonas pseudoalcaligenes interaction effects on off-flavors in algae/bacteria co-culture system under different temperatures

We conducted an experiment to study the interaction effects of Microcystis aeruginosa and Pseudomonas pseudoalcaligenes on off-flavors in an algae/bacteria co-culture system at three temperatures (24, 28 and 32°C). Gas chromatography-mass spectrometry was applied to measure off-flavor compounds dimethyl sulfide (DMS), dimethyl trisulfide (DMTS), 2-methylisoborneol, geosmin (GEO) and β-cyclocitral. During the lag phase of co-cultured M. aeruginosa (first 15days), P. pseudoalcaligenes significantly increased the production of DMS, DMTS and β-cyclocitral at all three temperatures. In the exponential phase of co-cultured M. aeruginosa (after 15days), M. aeruginosa became the main factor on off-flavors in the co-culture system, and β-cyclocitral turned to the highest off-flavor compound. These results also indicated that DMS, DMTS and β-cyclocitral were the main off-flavor compounds in our M. aeruginosa/P. pseudoalcaligenes co-culture system. Univariate analysis was applied to investigate the effects of M. aeruginosa and P. pseudoalcaligenes on the production of off-flavors. The results demonstrated that both M. aeruginosa and P. pseudoalcaligenes could increase the production of DMS and DMTS, while β-cyclocitral was mainly determined by M. aeruginosa. Our results also provide some insights into understanding the relationship between cyanobacteria and heterotrophic bacteria.