Parts-per-trillion LC-MS(Q) analysis of herbicides and transformation products in surface water

The goal of this study was to develop a robust method of analyzing surface water samples for S-triazine herbicides, chloroacetanilide herbicides, and their transformation products (TPs) using solid-phase extraction (SPE) followed by liquid chromatograph-mass spectrometry (LC-MS) with electrospray ionization (ESI) by in-source collision-induced dissociation (ISCID) capability of an orthogonal electrospray ionization probe on a single quadrupole LC-MS system. The method developed here met the goals of the study and yielded estimated method detection limits (EMDLs) averaging 0.3 ± 0.1 ng L(-1) for S-triazines and their TPs and 0.7 ± 0.4 ng L(-1) for chloroacetanilides and TPs. Spiked filtered river water yielded SPE recoveries ranging from 94.2 % ± 4.8 % for S-triazines and TPs after eliminating three compounds with less that 65 % recovery from analysis and 95.9 % ± 19 % for chloroacetanilides and their TPs. The method was field-tested with filtered water samples collected from four sites over a four-month period. Detectible values of S-triazines and TPs ranged from 0.3 to 1540 ng L(-1) with a mean of 79.3 and a median of 19.4 ng L(-1). Detectible values for chloroacetanilides and TPs ranged from 0.31 to 3780 ng L(-1) with a mean of 252 and a median of 25.6 ng L(-1). An additional goal was to determine if the method was useful for microbial degradation studies using native bacterial communities. The bacteria transformed atrazine (2-chloro-4-ethylamino-6-isopropylamino-S-triazine) solely into 2-hydroxy atrazine (2-hydroxy-4-ethylamino-6-isopropylamino-S-triazine) with concentrations of 78.4, 63.3 and 32.5 ng L(-1) after 12 days of incubation compared with 6.3 and 7.1 ng L(-1) for control dark and control sunlight respectively.     

POTENTIAL EFFECTS OF CHANGED CLIMATES ON HEAVY RAINFALL FREQUENCIES IN TIlE MIDWEST1

ABSTRACT: An important question posed by potential future shifts in climate relates to possible shifts in heavy rainfall events (intensity and/or frequency) used to design hydraulic structures. Heavy rain events were defined as those producing amounts having average recurrence intervals of two years or longer for a specific storm period at a given location. Estimates of such heavy rainfall shifts in the humid continental climate of the midwest were derived by using spatial and temporal analogs. Comparisons in areas of relatively warm, wet conditions were made with those having measurably cooler, drier average conditions. The spatial-temporal analogs provided comparative differences in precipitation and temperature similar to the magnitude of changes obtained from GCM estimates. Spatial analogs/analyses indicated 10 to 15 percent increases in the frequency distribution of rain events having recurrence intervals of 5 to 50 years. Two periods of notably drier and warmer conditions during the past 90 years revealed 5 to 15 percent decreases in the number of 2- to 10-year heavy rain events. The suppression percentages showed a strong tendency to increase with increasing recurrence interval from 2 to 10 years.     

EFFECTS OF THE URBAN ENVIRONMENT ON HEAVY RAINFALL DISTRIBUTION1

ABSTRACT: A network of 225 recording raingages was operated over an area of 5200 km² in the St. Louis region during 1971-1975, in conjunction with an extensive investigation of urban effects on precipitation. Study of urban-induced effects on the frequency of heavy rainstorms has revealed a pronounced increase in the occurrence of storms producing 25 mm (1 inch) or more of rain. The increase is greatest in an area that is frequently in the path of storms passing across two urban-industrial regions. Analyses of raincells (rain intensity centers) within heavy convective storms shows a pronounced increase in water yield from cells exposed to potential urban effects, compared with those exposed only to the surrounding rural environment. Naturally-occurring heavy cells tend to undergo the greatest enhancement from urban exposure. Other analyses indicate an above-average frequency of excessive rain rates for periods of five minutes to two hours downwind of the urban-industrial complex. It is concluded that urban-induced intensification of short-duration rainstorms is sufficient to merit inclusion in the design and operation of urban-area hydrologic systems that control the flow of surplus storm water.     

A HYDROMETEOROLOGICAL RESEARCH PROGRAM1

ABSTRACT: An extensive research program in hydrometeorology was recently initiated in the Chicago region. Major objectives are to 1) develop a real-time, prediction-monitoring system for storm rainfall using a combination of weather radar and telemetered raingage data, 2) determine precipitation measurement requirements for hydrologic design, operation, and modeling purposes, 3) define the time-space characteristics of heavy rainstorms in the Chicago urban area, and 4) establish methods for applying the Chicago findings in other cities. Basic components of the field measurement program are a network of over 300 recording raingages in 4000 mi² in and around Chicago, plus two sophisticated weather radar systems for obtaining real-time information on storm parameters pertinent to optimizing operation of urban water resources systems. The raingage networks are to be used to compile information relevant to both design and operational aspects of urban hydrology. Radars are to be used primarily in developing the real-time operational techniques. Testing and evaluation of the real-time operational system will be done in cooperation with the Metropolitan Sanitary District of Chicago, operator of one of the most complex urban water control systems among major metropolitan areas.     

The empirical modeling of an ecosystem

The authors have endeavored to create a verified a-posteriori model of a planktonic ecosystem. Verification of an empirically derived set of first-order, quadratic differential equations proved elusive due to the sensitivity of the model system to changes in initial conditions. Efforts to verify a similarly derived set of linear differential equations were more encouraging, yielding reasonable behavior for half of the ten ecosystem compartments modeled. The well-behaved species models gave indications as to the rate-controlling process in the ecosystem.     

Grazing by adult estuarine calanoid copepods of the Chesapeake Bay

Grazing by adult female Eurytemora affinis, Acartia tonsa and A. clausi on natural distributions of particles from the Chesapeake Bay has been investigated. During the course of a year's sampling, a wide variety of particle size-biomass distributions were observed as seasonal shifts in detritus, and over 150 algal species occurred. These distributions were grouped into 5 basic types in the analyses of feeding. All three species demonstrated similar capabilities for feeding over a broad range of particle size with selection (higher filtering rates) on larger particles and on biomass peaks. Feeding on multiple-peak distributions resulted in strong selection or tracking of each biomass peak with reduced filtering rates between peaks. Evidence is presented which suggests that the copepods first feed on large particles and then successively switch to biomass peaks of the smaller size categories. Comparisons of the feeding behavior of Eurytemora affinis and the Acartia species showing that the Acartia species have greater capabilities for taking large particles may be associated with modifications of their mouth parts for raptorial feeding. The results suggest considerable flexibility in copepod feeding behavior which cannot be explained solely by the mechanism of a fixed sieve.     

Relationships between psychological climate perceptions and work outcomes: a meta‐analytic review

In this study, meta‐analytic procedures were used to examine the relationships between individual‐level (psychological) climate perceptions and work outcomes such as employee attitudes, psychological well‐being, motivation, and performance. Our review of the literature generated 121 independent samples in which climate perceptions were measured and analyzed at the individual level. These studies document considerable confusion regarding the constructs of psychological climate, organizational climate, and organizational culture and reveal a need for researchers to use terminology that is consistent with their level of measurement, theory, and analysis. Our meta‐analytic findings indicate that psychological climate, operationalized as individuals' perceptions of their work environment, does have significant relationships with individuals' work attitudes, motivation, and performance. Structural equation modeling analyses of the meta‐analytic correlation matrix indicated that the relationships of psychological climate with employee motivation and performance are fully mediated by employees' work attitudes. We also found that the James and James ( 1989 ) PC_g model could be extended to predict the impact of work environment perceptions on employee attitudes, motivation, and performance. Despite the number of published individual‐level climate studies that we found, there is a need for more research using standardized measures so as to enable analyses of the organizational and contextual factors that might moderate the effects of psychological climate perceptions. Finally, we argue for a molar theory of psychological climate that is rooted in the psychological processes by which individuals make meaning or their work experiences. Copyright © 2003 John Wiley & Sons, Ltd.     

Grazing in juvenile stages of some estuarine calanoid copepods

The grazing of juvenile Eurytemora affinis, Acartia tonsa and A. clausi from the Chesapeake Bay (USA) was investigated using natural particle distributions and freshly caught copepods, live-sorted into stages. Data were analyzed in 110 size channels using an electronic particle counter, and filtering rates (FR) were estimated based on total particle removal (mean FR), and that for each size channel (giving maximum FR). Mean and maximum filtering rates increased from NVI (Nauplius Stage VI) through CVI (Copepodid Stage VI). Both rates plotted against weight satisfied a log fit best for A. tonsa, and a linear fit best for E. affinis. Results for A. tonsa were quite variable, apparently due to differences in temperature between experiments. Particle selection was investigated from the shape of the filtering rate curve over particle size. We define selective feeding by a FR curve which is higher in some size categories, and non-selective feeding by a flat FR curve. The general pattern was one of selective feeding in all copepodid stages of the three calanoid copepods investigated. E. affinis tended to track biomass peaks while Acartia spp.'s feeding was more variable, including feeding in size ranges of greatest particle concentration, on larger particles, and in other size categories as well. Experiments with nauplii tended to yield flat FR curves, and it may be that selective grazing appears with, or is greatly accentuated by, metamorphosis from NVI to CI (Copepodid Stage I).University of Maryland, Center for Environmental and Estuarine Studies Contribution No. 762.