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We synthesize, optically trap, and rotate individual nanovaterite crystals with a mean particle radius of 423 nm. Rotation rates of up to 4.9 kHz in heavy water are recorded [1]. Laser-induced heating due to residual absorption of the nanovaterite particle results in the superlinear behavior of the rotation rate as a function of trap power. A finite element method based on the Navier-Stokes model for the system allows us to determine the residual optical absorption coefficient for a trapped nanovaterite particle. This is further confirmed by the theoretical model. Our data reveal that the nanoparticle experiences a different Stokes drag torque or force depending on whether we consider rotational or translational motion, which is in a good agreement with the theoretical prediction of the rotational hot Brownian motion [2]. The data allow us to determine the correction factors for the local viscosity for both the rotational and translational motion of the nanoparticle. The use of nanovaterite particles opens up new studies for levitated optomechanics in vacuum [3–6] as well as microrheological properties of cells or biological media [7]. For these latter studies, nanovaterite offers prospects of microviscosity measurements in ultrasmall volumes and, due to its size, potentially simpler uptake by cellular media [8].

Rotational control over optically trapped particles has gained significant prominence in recent years. The marriage between light fields possessing optical angular momentum and the material properties of microparticles has been useful to controllably spin particles in liquid, air and vacuum. The rotational degree of freedom adds new functionality to optical traps: in addition to allowing fundamental tests of optical angular momentum, the transfer of spin angular momentum in particular can allow measurements of local viscosity and exert local stresses on cellular systems. We demonstrate optical trapping and controlled rotation of nanovaterite crystals. These particles represent the smallest birefringent crystals ever trapped and set into rotation. Rotation rates of up to 5kHz in water are recorded, representing the fastest rotation to date for dielectric particles in liquid. Laser-induced heating results in the superlinear behaviour of the rotation rate as a function of trap power. We study both the rotational and translational modes of trapped nanovaterite crystals. The particle temperatures derived from those two optomechanical modes are in good agreement, which is supported by a numerical model revealing that the observed heating is dominated by absorption of light by the particles rather than by the surrounding liquid. A comparison is performed with trapped silica particles of similar size. The use of nanovaterite particles open up new studies for levitated optomechanics in vacuum as well as microrheological properties of cells or biological media. Their size and low heating offers prospects of viscosity measurements in ultra-small volumes and potentially simpler uptake by cellular media.

Researchers experimentally investigate the superluminal kinematics of scattering light sources through ultrafast time-resolved imaging., The invariance of the speed of light is one of the foundational pillars of our current understanding of the universe. It implies a series of consequences related to our perception of simultaneity and, ultimately, of time itself. Whereas these consequences are experimentally well studied in the case of subluminal motion, the kinematics of superluminal motion lack direct evidence or even a clear experimental approach. We investigate kinematic effects associated with the superluminal motion of a light source. By using high-temporal-resolution imaging techniques, we directly demonstrate that if the source approaches an observer at superluminal speeds, the temporal ordering of events is inverted and its image appears to propagate backward. Moreover, for a source changing its speed and crossing the interface between subluminal and superluminal propagation regions, we observe image pair annihilation and creation, depending on the crossing direction. These results are very general and show that, regardless of the emitter speed, it is not possible to unambiguously determine the kinematics of an event from imaging and time-resolved measurements alone. This has implications not only for light, but also, for example, for sound and other wave phenomena.

Intense rains produced flooding during the spring and summer of 1993 over much of the midwestern USA including many agricultural areas of Missouri. Because of potential contamination from floodwater, an investigation was conducted to determine the changes in concentrations of agricultural chemicals in water samples from alluvial wells in Missouri after the flood. Water samples from 80 alluvial wells with historical data were collected in March, July, and November 1994, and analyzed for dissolved herbicides, herbicide metabolites, and nitrate (NO 3 ). There were no statistically significant differences in the distribution of alachlor ((2,chloro-2'-6'-diethyl-N-[methoxymethyl]-acetanilide), atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5 triazine), and nitrate concentrations between pre- and postflood samples (α = 0.05). The detection frequency of alachlor and atrazine in postflood samples was generally lower than the frequency in preflood samples. Analyses of agricultural chemicals in water samples from an intensely sampled well field indicate significant differences between the distribution of dissolved P concentrations in pre- and postflood samples (α = 0.05). However, no significant differences were detected between the pre- and postflood distributions of NO 3 or ammonia concentrations. Because of the numerous sources of temporal variability and the relatively short record of water-quality data for the study wells, a cause-and-effect relation between changes in agricultural chemical concentrations and a single factor of the 1993 flood is difficult to determine. Based on the results of this study, the 1993 flood did not cause widespread or long-term significant changes in concentrations of agricultural chemicals in water from alluvial aquifers in Missouri.

A study of the water resources of the Springfield, Missouri, area in the 1970s determined that a cone of depression, formed by groundwater pumping, had developed in the Ozark aquifer beneath the city (Emmett and others, 1978). Continued ground-water usage in the 1970s and 1980s caused concern that ground-water resources would not be sufficient to meet the future needs of Springfield, Missouri, during periods of drought. As a result, a ground-water flow model of the Springfield area was developed by the U. S. Geological Survey (USGS) to assess the future role of ground water as a water source for the area (Imes, 1989). Results of the USGS model led to a decision by the City Utilities of Springfield to primarily rely on surface water from Stockton Lake as a source of city drinking water. Municipal and industrial ground-water usage continues in Springfield, but at lower rates than previously experienced (Jim Vandike, Missouri Department of Natural Resources, written commun., 2007). Rapid growth in the area has caused commercial, industrial, and domestic water use to increase. Population growth has been especially rapid in Nixa, Ozark, and Republic, and water use in the vicinity of these cities has grown an estimated 39 percent since 1990 (Dintelmann and others, 2006). Unlike Springfield, ground water is the primary source of water for these cities. The increased stress on the Ozark aquifer (fig. 1), the primary aquifer in the study area, has

Pyrolysis mass spectrometry (Py-MS), time/temperature resolved Py-MS (TTR-Py-MS), and pyrolysis tandem mass spectrometry (Py-MS/MS) were used to determine the structure of an additive present in Biomer and Lycra Spandex. The additive was found to form a second phase in the polymer matrix which was insoulble in N,N′-dimethylacetamide. This insoluble portion (7% by weight) was separated by centrifugation. The structure of this additive is proposed to be poly(2-diisopropyl amino ethyl methacrylate)(DPA-EMA). The additive is present as a stabilizer for UV radiation and chloride and hypochlorite ion attack. A chloride containing compound of similar structure (2-diisopropyl amino ethyl chloride) (CAS No. 96-79-7) is also detected. This chloride-containing compound may be formed by reaction of the polymeric additive with chloride ions during storage or pyrolysis.

The chemistry and toxicity of base flow and urban stormwater were characterized to determine if urban stormwater was degrading the water quality of the Pearson Creek and Wilsons Creek Basins in and near the city of Springfield, Greene County, Missouri. Potentially toxic components of stormwater (nutrients, trace metals, and organic compounds) were identified to help resource managers identify and minimize the sources of toxicants. Nutrient loading to the James River from these two basins (especially the Wilsons Creek Basin) is of some concern because of the potential to degrade downstream water quality. Toxicity related to dissolved trace metal constituents in stormwater does not appear to be a great concern in these two basins. Increased heterotrophic activity, the result of large densities of fecal indicator bacteria introduced into the streams after storm events, could lead to associated dissolved oxygen stress of native biota. Analysis of stormwater samples detected a greater number of polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs) than were present in baseflow samples. The number and concentrations of pesticides detected in both the base-flow and stormwater samples were similar. Genotoxicity tests were performed to determine the bioavilability of chemical contaminants and determine the potential harmful effects on aquatic biota of Pearson Creek and Wilsons Creek. Genotoxicity was determined from dialysates from both long-term (approximately 30 days) and storm-event (3 to 5 days) semipermeable membrane device (SPMD) samples that were collected in each basin. Toxicity tests of SPMD samples indicated evidence of genotoxins in all SPMD samples. Hepatic activity assessment of one longterm SPMD sample indicated evidence of contaminant uptake in fish. Chemical analyses of the SPMD samples found that relatively few pesticides and pesticide metabolites had been sequestered in the lipid material of the SPMD; however, numerous PAHs and VOCs were detected in both the long-term and the storm-event exposures. It is suspected, based on the compounds detected in the SPMDs and the water samples, that the observed genotoxicity is largely the result of PAHs and VOCs that were probably derived from petroleum inputs or combustion sources. Therefore the water quality and thus the aquatic environments in the Pearson Creek and Wilsons Creek Basins are being degraded by urban derived contaminants.

In 1998, an 8-mile reach of the Jacks Fork was included on Missouri’s list of impaired waters as required by Section 303(d) of the Federal Clean Water Act. The identified pollutant on the Jacks Fork was fecal coliform bacteria. Potential sources of fecal contamination to the Jacks Fork include a wastewater treatment plant; campground pit-toilet or septic-system effluent; a large commercial, cross-country horseback trail riding facility; canoeists, boaters, and tubers; and cows. The U.S. Geological Survey, in cooperation with the National Park Service, conducted a study to better understand the extent and sources of microbiological contamination within the Jacks Fork from Alley Spring to the mouth, which includes the 8-mile 303(d) reach. Identification of the sources would provide the National Park Service and the State of Missouri with the information needed to craft a solution of abatement, regulation, prevention, and mitigation with the end result being the removal of the Jacks Fork from the 303(d) list. Fifteen sites were sampled from November 1999 through December 2000. An additional site was sampled one time. Samples were collected mostly during base-flow conditions during a variety of nonrecreational and recreational season river uses. Samples were analyzed for selected fecal indicator bacteria, physical properties, nutrients, and wastewater organic compounds. During the sampling period, the wholebody-contact recreation standard for fecal coliform (200 colonies per 100 milliliters of sample) was exceeded at three sites on August 10, 2000, and also at one site on May 11, June 7, and October 3, 2000. Fecal coliform densities and instantaneous loads generally increased from background concentrations at the Eminence site, peaked about 2 river miles downstream, and then decreased until the most downstream site sampled. Generally, the largest densities and loads at sites downstream from Eminence not related to wetweather flow were observed during a trail ride held August 6 to12, 2000. A 24-hour sample collection effort was conducted the weekend of July 15 and 16, 2000, to investigate the effect that large numbers of swimmers, canoeists, and tubers had on fecal coliform densities in the Jacks Fork. Five or six samples were collected at six sites between Saturday morning and the following Sunday afternoon. No fecal coliform density at any of the sites sampled exceeded the whole-body-contact recreation standard. Because bacteria survive longer in streambed sediments than in water, a source of bacteria in the water column could be from resuspension of accumulated bacteria from streambed sediments. Water and streambed-sediment samples were collected at three sites on August 3, 2000, 1 week before a trail ride and again at three sites on

The Ozark National Scenic Riverways (ONSR), the Nation's first scenic riverway, was created by an Act of Congress (Public Law 88-492) on August 24, 1964, for "the purpose of conserving and interpreting unique scenic and other natural values and objects of historic interest, including preservation of parts of the Current River and the Jacks Fork River in Missouri as free-flowing streams, preservation of springs and caves, management of wildlife, and provisions for use and enjoyment of the outdoor recreation resources thereof by the people of the United States" (National Park Service, 1981). The primary natural resources protected by the park are 134 miles of the Current and Jacks Fork Rivers (fig. 1). About 1.5 million people visit the ONSR annually to take advantage of excellent recreational opportunities, including canoeing, johnboating, swimming, fishing, tubing, camping, hiking, caving, horseback riding, and hunting.

Curie-point pyrolysis mass spectrometry (Py-MS) and direct probe pyrolysis high resolution mass spectrometry (Py-HRMS) were used to identify the components and additives used in the synthesis and compounding of Biomer, Lycra Spandex, Tecoflex, and Pellethane. Two types of Biomer were identified (P and Q, our notation) which are composed of poly(tetramethylene glycol) (PTMG) capped with 4,4′-methylenebis(phenylisocyanate) (MDI) and chain-extended with ethylenediamine (EDA). Both forms contain 4,4′-butylidene-bis-(6-t-butyl-m-cresol) antioxidant, and Biomer Q also contains an additive which appears to be a quaternary ammonium chloride salt. Lycra Spandex was found to be identical to Biomer Q, with the exception that a low molecular weight polydimethylsiloxane oil is also present. This silicone oil can be removed by solvent extraction. Tecoflex (type SG80A) is composed of PTMG capped with 4,4′-diisocyanatodicyclohexylmethane and extended with 1,4-butanediol (BD). An industrial grade and a medical grade of Pellethane were analyzed. Both were composed of PTMG capped with MDI and extended with 1,4-butanediol. the industrial grade also contains an antioxidant, possibly butylated diphenylamine.

Pyrolysis mass spectrometry in combination with computerized multivariate statistical analysis enables qualitative and quantitative analysis of nonvolatile organic materials containing molecular assemblies of a complexity and size far beyond the capabilities of direct mass spectrometry. The state of the art in pyrolysis mass spectrometry techniques is illustrated through specific applications, including structural determination and quality control of synthetic polymers, quantitative analysis of polymer mixtures, classification and structural characterization of fossil organic matter, and nonsupervised numerical extraction of component patterns from complex biological samples.

Identification des composants polymeres du Biomer (polyetherurethanneuree) utilise dans la fabrication des chambres de cœur artificiel

Multvariate analysis of time-resolved pyrolysis/mass spectrometric data is described. The approach is based on the variance diagram (VARDIA), a recently developed technique that quantifies the clustering of variables in two-dimensional factor analysis (sub)-spaces in a rotational scanning procedure. A maximum in the VARDIA plot indicates a correlated behavior of the mass variables, indicating a common origin. This common origin is generally caused by a change in the concentration of a chemical component. With this information the “factor spectrum” and the scores of the component can be retrieved. For time-resolved serial data, consideration of the clustering behavior of the variables as a function of time is more appropriate than a rotational scanning procedure. Adaptation of the VARDIA for serial data, such as time-resolved data, is described. This approach has the advantage that all the factors can be used. It will be shown that the resolution of the obtained curve than the total ion current curve as a function of time. Examples will be given for time-resolved data of coal, rubber and wood samples.

A set of twelve natural rubber vulcanizates was analyzed by Curie-point pyrolysis-mass spectrometry (Py-MS). Multivariate analysis successfully correlated the Py-MS data with either total or polysulfidic crosslink density measurements. (Polysulfidic means two or more sulfurs.) The principal correlation observed was an increase in the ratio of monomer to dimer pyrolyzate yield with an increase in crosslink density. The feasibility of using Py-MS for total crosslink density determination has thus been demonstrated. The Py-MS data, however, did not allow us to distinguish different types of crosslinks.

The potentialities of computerized pyrolysis mass spectrometry (m.s.) are discussed for applications in process monitoring and quality assurance involving nonvolatile materials such as polymers. The traditional obstacles to more widespread acceptance of pyrolysis m.s. for industrial applications are reviewed in the light of recent developments which provide a major reduction in the cost, size and complexity of the equipment. Rapid advances in computerized data reduction, evaluation and interpretation methods for complex mass-spectral patterns are also transforming the classical “fingerprinting” concept of pyrolysis m.s. into a much more detailed compositional and structural characterization approach. These new developments are illustrated by means of several practial examples ranging from quality control of clinically important polyurethanes to monitoring of wood pulping processes and of growth phenomena in microbial cultures.

Several analytical pyrolysis methods, namely pyrolysis mass spectrometry (Py-MS), time-resolved pyrolysis mass spectrometry (TRPy-MS), and pyrolysis short column gas chromatography mass spectrometry (Py-GC/MS) were used to analyze polymers of clinical interest both before and after implantation. A sample of Biomer, a poly(ether urethane urea) used in the Utah artificial heart, was analyzed using these methods. Two poly(ether urethanes) (Tecoflex and Pellethane) and a poly(dimethylsilicone) (Silastic) sample were analyzed using Py-GC/MS. The direct Py-MS of Biomer identified the components used in the manufacture of Biomer. Py-GC/MS of Biomer, Tecoflex, Pellethane, and Silastic also identified the components used in their manufacture. The analysis of explanted Biomer detected the presence of adsorbed cholestadiene, the reaction of chloride ions with a stabilizer, and the presence of a siloxane contaminant. The cholestadiene was detected on the outside housing of an artificial heart which had been implanted for 297 days. The cholestadiene was detected at low levels and was identified by library search on the MS data system. The siloxane contaminant was also identified by the MS data system. All of the methods demonstrated required only short instrumental analysis times (10 min or less). Data analysis required much more time, but much of the data analysis can be automated.