Geology topics

D. Barcelo

Publications and source records attributed to D. Barcelo.

6 recordsLinked to original sources

USGS2001

Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides

An evaluation of over 75 pesticides by high-performance liquid chromatography/mass spectrometry (HPLC/MS) clearly shows that different classes of pesticides are more sensitive using either atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI). For example, neutral and basic pesticides (phenylureas, triazines) are more sensitive using APCI (especially positive ion). While cationic and anionic herbicides (bipyridylium ions, sulfonic acids) are more sensitive using ESI (especially negative ion). These data are expressed graphically in a figure called an ionization-continuum diagram, which shows that protonation in the gas phase (proton affinity) and polarity in solution, expressed as proton addition or subtraction (pKa), is useful in selecting APCI or ESI. Furthermore, sodium adduct formation commonly occurs using positive ion ESI but not using positive ion APCI, which reflects the different mechanisms of ionization and strengthens the usefulness of the ionization-continuum diagram. The data also show that the concept of "wrong-way around" ESI (the sensitivity of acidic pesticides in an acidic mobile phase) is a useful modification of simple pKa theory for mobile-phase selection. Finally, this finding is used to enhance the chromatographic separation of oxanilic and sulfonic acid herbicides while maintaining good sensitivity in LC/MS using ESI negative.

Analytical Chemistry↗

USGS2001

Identification of a new degradation product of the antifouling agent Irgarol 1051 in natural samples

A main degradation product of Irgarol [2-(methylthio)-4-(tert-butylamino)-6-(cyclopropylamino)-s-triazine], one of the most widely used compounds in antifouling paints, was detected at trace levels in seawater and sediment samples collected from several marinas on the Mediterranean coast. This degradation product was identified as 2-methylthio-4-tert-butylamino-s-triazine. The unequivocal identification of this compound in seawater samples was carried out by solid-phase extraction (SPE) coupled on-line with liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS). SPE was carried out by passing 150 ml of seawater sample through a cartridge containing a polymeric phase (PLRP-s), with recoveries ranging from 92 to 108% (n=5). Using LC-MS detection in positive ion mode, useful structural information was obtained by increasing the fragmentor voltage, thus permitting the unequivocal identification of this compound in natural samples. Method detection limits were in the range of 0.002 to 0.005 ??g/l. Overall, the combination of on-line SPE and LC-APCI-MS represents an important advance in environmental analysis of herbicide degradation products in seawater, since it demonstrates that trace amounts of new polar metabolites may be determined rapidly. This paper reports the LC-MS identification of the main degradation product of Irgarol in seawater and sediment samples. ?? 2001 Elsevier Science B.V. All rights reserved.

Conference Paper↗

USGS2001

Determination of drugs in surface water and wastewater samples by liquid chromatography-mass spectrometry: Methods and preliminary results including toxicity studies with Vibrio fischeri

In the present work a combined analytical method involving toxicity and liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) was developed for the determination of pharmaceutical compounds in water samples. The drugs investigated were the analgesics: ibuprofen, ketoprofen, naproxen, and diclofenac, the decomposition product of the acetyl salicylic acid: salicylic acid and one lipid lowering agent, gemfibrozil. The selected compounds are acidic substances, very polar and all of them are analgesic compounds that can be purchased without medical prescription. The developed protocol consisted, first of all, on the use Microtox?? and ToxAlert??100 toxicity tests with Vibrio fischeri for the different pharmaceutical drugs. The 50% effective concentration (EC50) values and the toxicity units (TU) were determined for every compound using both systems. Sample enrichment of water samples was achieved by solid-phase extraction procedure (SPE), using the Merck LiChrolut?? EN cartridges followed by LC-ESI-MS. Average recoveries loading 1 l of samples with pH=2 varied from 69 to 91% and the detection limits in the range of 15-56 ng/l. The developed method was applied to real samples from wastewater and surface-river waters of Catalonia (north-east of Spain). One batch of samples was analyzed in parallel also by High Resolution Gas Chromatography coupled with Mass Spectrometry (HRGC-MS) and the results have been compared with the LC-ESI-MS method developed in this work. ?? 2001 Elsevier Science B.V. All rights reserved.

Conference Paper↗

USGS2000

Selective trace enrichment of chlorotriazine pesticides from natural waters and sediment samples using terbuthylazine molecularly imprinted polymers

Two molecularly imprinted polymers were synthesized using either dichloromethane or toluene as the porogen and terbuthylazine as the template and were used as solid-phase extraction cartridges for the enrichment of six chlorotriazines (deisopropylatrazine, deethylatrazine, simazine, atrazine, propazine, and terbuthylazine) in natural water and sediment samples. The extracted samples were analyzed by liquid chromatography/diode array detection (LC/DAD). Several washing solvents, as well as different volumes, were tested for their ability to remove the matrix components nonspecifically adsorbed on the sorbents. This cleanup step was shown to be of prime importance to the successful extraction of the pesticides from the aqueous samples. The optimal analytical conditions were obtained when the MIP imprinted using dichloromethane was the sorbent, 2 mL of dichloromethane was used in the washing step, and the preconcentrated analytes were eluted with 8 mL of methanol. The recoveries were higher than 80% for all the chlorotriazines except for propazine (53%) when 50- or 100-mL groundwater samples, spiked at 1 ??g/L level, were analyzed. The limits of detection varied from 0.05 to 0.2 ??g/L when preconcentrating a 100-mL groundwater sample. Natural sediment samples from the Ebre Delta area (Tarragona, Spain) containing atrazine and deethylatrazine were Soxhlet extracted and analyzed by the methodology developed in this work. No significant interferences from the sample matrix were noticed, thus indicating good selectivity of the MIP sorbents used.

Analytical Chemistry↗

USGS2000

Multivariate correlation between concentrations of selected herbicides and derivatives in outflows from selected U.S. midwestern reservoirs

Multivariate correlations between the concentrations of selected herbicides and herbicide derivatives in outflows from selected reservoirs in the Midwestern United States for April 1992 through September 1993 were investigated using principal component analysis (PCA) and multivariate curve resolution (MCR). Two independent sources for alachlor ethanesulfonic acid, one major source related to spring flush and seasonal runoff and another minor source related to groundwater, were identified using PCA. Results of MCR provided a semiquantitative interpretation of the environmental sources of the observed herbicide concentrations in reservoir outflows and allowed the examination of their temporal and geographical distributions. Samples with higher herbicide concentrations were collected from reservoirs in Indiana and Ohio, especially during the late spring and summer.

Environmental Science & Technology↗

USGS1998

Degradation of chloroacetanilide herbicides: The prevalence of sulfonic and oxanilic acid metabolites in Iowa groundwaters and surface waters

Water samples were collected from 88 municipal wells throughout Iowa during the summer and were collected monthly at 12 stream sites in eastern Iowa from March to December 1996 to study the occurrence of the sulfonic and oxanilic metabolites of acetochlor, alachlor, and metolachlor. The sulfonic and oxanilic metabolites were present in almost 75% of the groundwater samples and were generally present from 3 to 45 times more frequently than their parent compounds. In groundwater, the median value of the summed concentrations of acetochlor, alachlor, and metolachlor was less than 0.05 μg/L, and the median value of the summed concentrations of the six metabolites was 1.2 μg/L. All surface water samples contained at least one detectable metabolite compound. Individual metabolites were detected from 2 to over 100 times more frequently than the parent compounds. In surface water, the median value of the summed concentrations of the three parent compounds was 0.13 μg/L, and the median value of the summed concentrations of the six metabolites was 6.4 μg/L. These data demonstrate the importance of analyzing both parent compounds and metabolites to more fully understand the environmental fate and transport of herbicides in the hydrologic system.

Iowa↗