Monitoring of artemisinin, dihydroartemisinin, and artemether in environmental matrices using high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS)

The area cultivated with Artemisia annua for the extraction of the antimalarial compound artemisinin is increasing, but the environmental impact of this cultivation has not yet been studied. A sensitive and robust method using liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for the determination of artemisinin in soil. Dihydroartemisinin and artemether were included in the method, and performance on analytical columns of both traditional C(18) phenyl-hexyl and porous shell particles-based Kinetex types was characterized. The versatility of the method was demonstrated on surface water and groundwater samples and plant extracts. The limit of detection was 55, 30 (25 ng/g soil), and 4 ng/mL for dihydroartemisinin, artemisinin, and artemether, respectively. Method performance was demonstrated using naturally contaminated soil samples from A. annua fields in Kenya. The highest observed concentrations were above EC(10) for lettuce growth. Monitoring of artemisinin in soil with A. annua crop production seems necessary to further understand the impact in the environment.     

Demonstrating formation of potentially persistent transformation products from the herbicides bromoxynil and ioxynil using liquid chromatography-tandem mass spectrometry (LC-MS/MS)

It is shown that potentially persistent transformation products can be formed from the herbicides bromoxynil (3,5-dibromo-4-hydroxybenzonitrile) and ioxynil (3,5-diiodo-4-hydroxybenzonitrile), and possible leaching to groundwater is discussed. A similar process to the formation of BAM (2,6-dichlorobenzamide) from the herbicide dichlobenil (2,6-dichlorobenzonitrile) can be anticipated as bromoxynil and ioxynil are analogues of dichlobenil and they are degraded by the enzymes nitrilase, nitrile hydratase and amidase. A biodegradation study using cultured Variovorax sp. DSM 11402, a species commonly found in soil, demonstrated that ioxynil and bromoxynil were fully transformed into their corresponding amides in 2-5 days. These amides were not further degraded within 18 days, and formation of other degradation products was not observed. These results are in agreement with biodegradation experiments with dichlobenil. In soil, dichlobenil is transformed into its only observed degradation product BAM, which is persistent and mobile, and has been found in 19% of 5000 samples of Danish groundwater. Variovorax sp. is known to degrade the non-halogenated analogue benzamide, suggesting that degradation of the three amides may be hindered by the halogenated substituents (meta-Br; meta-I; ortho-Cl). This hypothesis is supported by QSAR modelling of fundamental properties. Using a new optimised liquid chromatography-tandem mass spectrometry (LC-MS/MS) method, the sorption and desorption properties of bromoxynil and ioxynil were characterised in sandy topsoil at four concentration levels. The estimated sorption coefficient K(d) was 1.4 L kg(-1) for bromoxynil and 5.4 L kg(-1) for ioxynil, indicating weak to moderate sorption to topsoil. Desorption of the herbicides showed that they were strongly and irreversible bound to the soil (K(des) > K(d)). The amount of herbicide desorbed depended on the initial concentration level. At low levels, K(des) values were higher, indicating stronger binding than at higher levels. The isocratic LC-MS/MS method developed for simultaneous detection of bromoxynil, ioxynil and their main degradation products is described. Using negative electrospray ionisation (ESI-), the detection limits were 0.4-1.0 microg L(-1), with relative standard deviations of 4-10% (n = 10) using direct injection without clean-up steps. The standard curves showed linearity in the range 5-100 microg L(-1) with r(2) > 0.992.     

Bioavailability of triazine herbicides in a sandy soil profile

The bioavailability of atrazine was evaluated in a Danish soil profile (Drengsted) using a combination of soil sorption, transport and mineralisation methods as well as inoculation using Pseudomonas ADP. Sorption of atrazine decreased markedly with depth as indicated by K_d values of 5.2 l kg^-1 for the upper soil and 0.1 l kg^-1 for the subsoils. The transport of atrazine was evaluated using soil TLC plates and the resulting R_f values were 0.1 for the upper soil and 0.9 for the subsoil. Only a relatively small amount of atrazine leached through undisturbed soil columns taken from the upper 60 cm. Inoculating with Pseudomonas strain ADP (1᎒⁶ CFU g^-1 dry weight soil) revealed that the degradation of 0.01 ppm atrazine was fully completed (80% mineralisation) within 10 days in the subsoil, while it reached less than 15% in the upper soil. Over a period of 500 days, a total mineralisation of 37% of added atrazine in the upper soil was found (2 mg kg^-1 incubated at 20° C). However, in the subsurface soil where 0.02 mg kg^-1 of atrazine was incubated at 10°C, the degradation was slower, only reaching about 12%. Terbuthylazine mineralisation was found to be temperature-dependent and low (less than 5%) in the upper soil and very much lower in the subsoil. Desethylterbuthylazine was the most frequently found metabolite. Finally, Pseudomonas strain ADP inoculated into soils from different depths increased the mineralisation of terbuthylazine dramatically. Modelling using a "two-compartment model" indicated that desorption of terbuthylazine is the limiting step for its mineralisation.     

Quantification of ptaquiloside and pterosin B in soil and groundwater using liquid chromatography-tandem mass spectrometry (LC-MS/MS)

The carcinogenic compound ptaquiloside is produced by bracken fern (Pteridium aquilinum L.). Ptaquiloside can enter the soil matrix and potentially leach to the aquatic environment, and methods for characterizing ptaquiloside content and fate in soil and groundwater are needed. A sensitive detection method has been developed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) for analyzing ptaquiloside and its transformation product pterosin B. Detection limits are 0.19 microg/L (ptaquiloside) and 0.15 microg/L (pterosin B), which are 300-650 times better than previously published LC-UV methods. Sequential soil extractions are made using 5 mM ammonium acetate for extraction of ptaquiloside, followed by 80% methanol extraction for pterosin B. Groundwater samples are cleaned-up and preconcentrated by a factor of 20 using solid-phase extraction. The LC-MS/MS method enables quantification of ptaquiloside and pterosin B in soil and groundwater samples at environmentally relevant concentrations and delivers a reliable identification because of the structure-specific detection method.     

Monitoring Methyl Tertiary Butyl Ether (MTBE) and other Organic Micropollutants in Groundwater: Results from the Danish National Monitoring Program

The paper presents results of analyses of 7671 groundwater samples collected from 1115 screens in the period 1993 to 2001 for the Danish National Groundwater Monitoring Program. In Denmark groundwater is widely used for drinking water and the objectives of the monitoring program is to describe the present conditions, the development of, and the impacts on the groundwater. The design of the Danish National Groundwater Monitoring Program is described and data are provided. Data originate from monitoring areas and are supplemented with data from the waterworks' control of nearly 6000 water supply wells. In addition to pesticides there is a series of other organic compounds that must be considered in relation to possible groundwater contamination. Sources of these compounds and their importance in relation to groundwater contamination is discussed on the basis of the monitoring data. The organic micropollutants monitored are grouped according to chemical properties: aromatic hydrocarbons, chlorophenols, detergents, halogenated aliphatic hydrocarbons, ethers (MTBE), phenols, and phthalates. The most frequently found compounds were toluene (18.7% ), phenol (14.6%), xylene (10.9), trichloromethane (9.5%), and benzene (in 8.8% of the screens monitored). The five compounds most frequently found at a concentration above the maximum residue limits (MRL) for drinkingwater were: dibuthylphthalate (28%), phenol (14%), 2,4-dichlorophenol (10%), trichloromethane (10%), pentachlorophenol (7% of findings exceeding the MRL for drinkingwater). Overall, one or several compound was observed at least once in 57.8% of the 1115 screens monitored within the period 1993–2001. On a yearly basis the median finding frequency was 19%.