Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.     

Spatial variability of soil phosphorus in relation to the topographic index and critical source areas: sampling for assessing risk to water quality

A measure of soil P status in agricultural soils is generally required for assisting with prediction of potential P loss from agricultural catchments and assessing risk for water quality. The objectives of this paper are twofold: (i) investigating the soil P status, distribution, and variability, both spatially and with soil depth, of two different first-order catchments; and (ii) determining variation in soil P concentration in relation to catchment topography (quantified as the "topographic index") and critical source areas (CSAs). The soil P measurements showed large spatial variability, not only between fields and land uses, but also within individual fields and in part was thought to be strongly influenced by areas where cattle tended to congregate and areas where manure was most commonly spread. Topographic index alone was not related to the distribution of soil P, and does not seem to provide an adequate indicator for CSAs in the study catchments. However, CSAs may be used in conjunction with soil P data for help in determining a more "effective" catchment soil P status. The difficulties in defining CSAs a priori, particularly for modeling and prediction purposes, however, suggest that other more "integrated" measures of catchment soil P status, such as baseflow P concentrations or streambed sediment P concentrations, might be more useful. Since observed soil P distribution is variable and is also difficult to relate to nationally available soil P data, any assessment of soil P status for determining risk of P loss is uncertain and problematic, given other catchment physicochemical characteristics and the sampling strategy employed.     

Uncertainties in vegetated buffer strip function in controlling phosphorus export from agricultural land in the Canadian prairies

Environmental Science and Pollution Research - Vegetated buffer strips (VBSs) are widely encouraged as a cost-effective strategy to address phosphorus (P) pollution associated with agricultural...     

Inputs and losses by surface runoff and subsurface leaching for pastures managed by continuous or rotational stocking

Pasture management practices can affect forage quality and production, animal health and production, and surface and groundwater quality. In a 5-yr study conducted at the North Appalachian Experimental Watershed near Coshocton, Ohio, we compared the effects of two contrasting grazing methods on surface and subsurface water quantity and quality. Four pastures, each including a small, instrumented watershed (0.51-1.09 ha) for surface runoff measurements and a developed spring for subsurface flow collection, received 112 kg N ha(-1) yr(-1) and were grazed at similar stocking rates (1.8-1.9 cows ha(-1)). Two pastures were continuously stocked; two were subdivided so that they were grazed with frequent rotational stocking (5-6 times weekly). In the preceding 5 yr, these pastures received 112 kg N ha(-1) yr(-1) after several years of 0 N fertilizer and were grazed with weekly rotational stocking. Surface runoff losses of N were minimal. During these two periods, some years had precipitation up to 50% greater than the long-term average, which increased subsurface flow and NO(3)-N transport. Average annual NO(3)-N transported in subsurface flow from the four watersheds during the two 5-yr periods ranged from 11.3 to 22.7 kg N ha(-1), which was similar to or less than the mineral-N received in precipitation. Flow and transport variations were greater among seasons than among watersheds. Flow-weighted seasonal NO(3)-N concentrations in subsurface flow did not exceed 7 mg L(-1). Variations in NO(3)-N leached from pastures were primarily due to variable precipitation rather than the effects of continuous, weekly rotational, or frequent rotational stocking practices. This suggests that there was no difference among these grazing practices in terms of NO(3)-N leaching.     

VARIABILITY IN THERMAL STRATIFICATION IN A RESERVOIR1

ABSTRACT: The thermal stratification characteristics of a flow-augmentation reservoir, Round Valley Reservoir, New Jersey, and attendant driving conditions were documented and analyzed for portions of three years. Substantial differences in the thermal stratification regime of the reservoir occurred in response to the documented changes in meteorological, operating, and light penetration conditions. The features of stratification that were affected included: the depth of the upper mixed layer, the average temperature of the epilimnion, the temperature gradient in the metalimnion, and the average temperature in the hypolimnion.     

Respiration and physiological state in marine bacteria

The relationship between oxygen consumption (R) and respiratory electron-transport-system (ETS) activity was investigated in batch cultures of 5 species of marine bacteria, Vibrio adaptatus, V. anguillarum, a partially identified Vibrio sp. SA774, Serratia marinorubra, and Pseudomonas perfectomarinus. Although cellular levels of R and ETS varied widely among the species tested, the R:ETS ratios for growing or senescent populations were relatively constant among the species; these ratios were 5.02 in growth and 0.426 in senescence, with coefficients of variation of 29 and 20%, respectively. The lower senescent-phase R:ETS ratio was due to a depression of the respiration rates following growth termination. The regression log (R per cell) = 0.832 log (ETS per cell) + 0.727 for the growing populations was similar to that determined for marine zooplankton. The slight dependency of the R:ETS ratio on organism dry weight found for zooplankton was supported by our data. Planktonic respiration rates estimated from measured ETS-depth profiles in the eastern tropical North Pacific Ocean using the senescent-phase R:ETS ratio were similar to published oxygen consumption rates in the deep sea.Contribution No. M79-61 from the University of Washington's Department of Oceanography, and No. 79032 from the Bigelow Laboratory for Ocean Sciences.     

Patterns in swimming by a scyphomedusa: a novel approach to quantifying behavior in individuals

Behavior is commonly studied at the group level using several individuals, but there is increasing evidence that the behavior of a few individuals often has a disproportionate effect on the response of a population to its environment. The present study used a suite of statistical techniques, random series analysis, analysis of variance, spectral analysis, and goodness-of-fit tests of frequency histograms, to quantitatively describe the time-dependent changes in individual behavior. Each technique reveals a different facet of the behavior and, when simultaneously applied to the data, distinguishes significant differences among the behaviors of several individuals. The approach was developed and tested on the swimming behavior of four specimens of the scyphomedusa Aurelia aurita (Linnaeus, 1758), which were observed for 19 days, beginning 16 January 1998, and videotaped under identical environmental conditions during that period. The analyses showed that each medusa swam in a unique pattern, varying swimming at characteristic frequencies. Application of the approach to individual-based numerical modeling, to the role of endogenous stimuli in the behavioral repertoire, and to in situ studies of animal behavior is discussed.Communicated by J.P. Grassle, New Brunswick     

Rotary Kiln Incineration II. Laboratory-Scale Desorption and Kiln-Simulator Studies—Solids

With landfill costs increasing and regulations on landfilling becoming more stringent, alternatives to conventional hazardous waste treatment strategies are becoming more desirable. Incineration Is presently a permanent, proven solution for the disposal of most organic contaminants, but also a costly one, especially in the case of solids which require some auxiliary fuel. The goal of this research is to develop an understanding of the phenomena associated with the evolution of contaminants from solids In the primary combustor of an Incineration system. A four-fold approach is being used. First, a bench-scale particle characterization reactor was developed to study the transport phenomena on a particle basis, where the controlling processes are mainly intraparticle. Second, a bed-characterization reactor was built to examine the controlling transport phenomena within a bed of particles, where the processes are primarily interparticle. The results of these studies can be applied to any primary combustor. A pilot-scale rotary kiln was developed to study the evolution of contaminants from solids within a realistic temperature and rotation environment. Finally, in situ measurements are being obtained from a full-scale rotary-kiln.

This paper describes results obtained in a study using a commercial sorbent contaminated with toluene. The data are from the particle-characterization reactor and the rotary-kiln simulator. The results show that the method of contamination and charge size do not have a large effect on desorption, while temperature and contaminant concentration are important parameters In the evolution of contaminants in a rotary kiln.     

Transport of copper as affected by titania nanoparticles in soil columns

The effects of TiO₂ nanoparticles on the transport of Cu through four different soil columns were studied. For two soils (HB and DX), TiO₂ nanoparticles acted as a Cu carrier and facilitated the transport of Cu. For a third soil (BJ) TiO₂ nanoparticles also facilitated Cu transport but to a much lesser degree, but for a fourth soil (HLJ) TiO₂ nanoparticles retarded the transport of Cu. Linear correlation analysis indicated that soil properties rather than sorption capacities for Cu primary governed whether TiO₂ nanoparticles-facilitated Cu transport. The TiO₂-associated Cu of outflow in the Cu-contaminated soil columns was significantly positively correlated with soil pH and negatively correlated with CEC and DOC. During passage through the soil columns 46.6-99.9% of Cu initially adsorbed onto TiO₂ could be “stripped” from nanoparticles depending on soil, where Cu desorption from TiO₂ nanoparticles increased with decreasing flow velocity and soil pH.     

Field-scale rotary kiln incineration: Oxygen responses at the kiln,afterburner, and stack

There currently exists a need for better characterization and simulation of the processes that occur during the incineration of hazardous wastes in the environment of a rotary kiln. Addressing this need, a comprehensive research program was formed with the goal of developing a rudimentary predictive capability for rotary kiln incineration of hazardous wastes. This comprehensive program is headed by Louisiana State University and includes interaction with the University of Utah and also various industrial participants. Such cooperation allows use of laboratory, pilot, and field scale equipment. While laboratory scale experiments provide the necessary decoupling of complex phenomena and a high degree of experimental control, and pilot scale studies provide more realism at the expense of experimental control, the problems of scale-up make generalization of results to field scale units very tenuous. The unique aspect of the LSU program is the coupling of the laboratory and pilot scale units with afield scale unit in order to overcome these generalizations. In this study, plastic packs containing a mixture of toluene and sorbent were fed to a field-scale rotary kiln incinerator at a rate of one pack every 10 minutes. Selected continuous gas samples and temperatures were obtained from the exit of the rotary kiln, from the afterburner, and from the stack. These measurements were obtained during various operating conditions. These data provide, for the first time, an ability to compare conditions in the kiln to simultaneous conditions in the afterburner and stack. This paper outlines several new experimental features of our field-scale tests conducted in October 1990. Oxygen responses from the kiln, the afterburner, and the stack are compared during various operating conditions.