Determination of (40)ca(+) in the presence of (40)ar(+): an illustration of the utility of time-gated detection in pulsed glow discharge mass spectrometry.

The glow discharge ionization source operated in the pulsed, or modulated, power mode affords a number of distinct advantages over its steady-state counterpart. It is well-known that pulsed plasma operation permits the application of higher instantaneous powers by allowing time for the sample to cool. This minimizes sample overheating while effecting higher sputtering yields and lower limits of detection. The presence of discrete time regimes affords the added advantage of temporal selectivity. Such selectivity allows the observation of analyte ions during a time regime in which their signal is at a maximum while that of electron ionized background species is declining. Significantly, time regimes are found when no background argon ion signals are observable but analyte ion signals remain. This means that discrimination against isobaric interferences arising from the discharge gas is possible. A prime example of the utility of this advantage arises in the determination of calcium with an argon glow discharge. Both the major argon and calcium isotopes are found at a nominal m/z of 40. Time-gated mass spectrometeric detection during the afterpeak time regime enables the ready determination of (40)Ca(+) in samples at the ppm level. A linear calibration curve is obtained that also demonstrates the elimination of the (40)Ar(+) signal from mass spectra obtained with either a dc or rf glow discharge ion source.

Time-of-Flight Mass Spectrometry with a Pulsed Glow Discharge Ionization Source.

The pulsed glow discharge (GD) plasma source exhibits several characteristics that make it ideally suited for use with time-of-flight mass spectrometry (TOFMS). TOFMS uniquely affords the ability to monitor a narrow temporal window for a time-varying process such as ion formation in the pulsed glow discharge plasma. Pulsed GD-TOFMS exhibited distinct advantages for the direct determination of trace elements in solid state samples. Initially, the pulse-powered GD-TOFMS system used for these investigations exhibited poor resolution. In an effort to improve resolution, a slit was introduced to narrow the ion beam orthogonally entering the extraction region of the TOFMS. In an effort to determine optimal operating conditions, the influence of slit width on TOF performance was investigated. In the course of this study, the slit width was found to influence isotope ratio accuracy as well as resolution. A slit width of 1.0 mm was determined to provide the best compromise between resolution and isotope ratio accuracy. Pulsed GD-TOFMS affords improved sensitivity and selectivity because Penning ionization is enhanced during the time period immediately following the termination of the discharge power. Ions sampled by an extraction pulse applied after power termination also yield a mass spectrum that is free of contributions arising from electron-ionized interferences. This advantage arises because only ions generated via the Penning ionization mechanism persist after the termination of discharge power. Sampling in the "afterpeak" time regime eliminates the saturation of the detector arising from discharge support gas ion signal.

Ion formation processes in the afterpeak time regime of pulsed glow discharge plasmas.

The formation of ions following the termination of power in a pulsed glow discharge ion source is investigated. The populations of ionized species containing sputtered atoms M(+), M 2 (1) :, and MAr(+) are observed to maximize after the termination of discharge power. Collisions involving sputtered atoms and metastable argon atoms, Penning and associative ionization, are considered to be responsible for the formation of ions in the discharge afterpeak time regime. The domination of these ion formation processes during the afterpeak time regime is supported by the results from investigations of discharge operating parameters, metastable argon atom quenching, and ion kinetic energy distributions.

Surface-induced dissociation in tandem quadrupole mass spectrometers: A comparison of three designs.

Three different devices that-can be used for surface-induced dissociation (SID) m tandem quadrupole instruments are compared here. The designs were compared by examining the fragmentation of several compounds including benzene, W(CO)6, and (CH3)4N(+). These studies show that SID can be readily implemented on a variety of tandem quadrupoIe instruments and that the spectra obtained with the in-line and 90° instruments are similar. Evidence is presented that confirms that high average internal energies and narrow distributions of internal energy are available by this technique. Efficiencies for fragmentation of odd-electron ions are on the order of those previously reported by others. The overall SID efficiency for even-electron ions is higher than that for odd-electron ions of similar structure.

Maternal reproductive history and birth characteristics in childhood acute lymphoblastic leukemia.

Using birth-registration data, a case-control study was done to investigate the possible associations of childhood acute lymphoblastic leukemia (ALL) with birth characteristics and maternal reproductive history. The data included cases born and diagnosed in Minnesota since 1969. Matched analyses were conducted using 337 cases and 1336 birth year-matched controls. There was a statistically significant increased odds of ALL for birth to older (greater than 35 years) mothers (odds ratio (OR) = 2.14, 95% confidence interval (CI) = 1.28, 3.58), older fathers (OR = 1.62, 95% CI = 1.14, 2.30), mothers with at least a high school education (OR = 1.61, 95% CI = 1.05, 2.48), and larger intervals (greater than 5 years) between the birth of the proband and the preceding sibling (OR = 1.86, 95% CI = 1.12, 3.09). The increased odds of ALL for birth by Caesarean section approached significance (OR = 1.42, P = 0.06). No overall association was found for: gender, race, paternal education, fetal-loss history, birth order, prenatal care history, pregnancy complications, inducement of labor, multiple birth, gestational age, or birth weight. Age at diagnosis was an important effect modifier of some analyses. For cases diagnosed before age 2 years, there was a 2.7-fold increased odds of ALL if the last pregnancy had resulted in a fetal loss (P = 0.03). For cases diagnosed before age 4 years, birth weight greater than 3800 g was associated with a significant 2.05-fold increased odds of ALL. These data strengthen the hypothesis that prenatal events may play a causative role in childhood ALL, particularly in those cases diagnosed at a younger age.

Prenatal and perinatal risk factors for neuroblastoma. A case-control study.

Neuroblastoma is the most common neoplasm in children less than 1 year of age and has one of the earliest incidence peaks of all childhood cancers. Using birth registration data, a matched case-control study was undertaken to investigate potential prenatal and perinatal risk factors. Ninety-seven neuroblastoma patients who were born in Minnesota were matched with four controls each. No associations were identified for sex, race, parental age, parental education, complications of pregnancy, labor, or delivery, or the previously reported factors of birth weight greater than 4000 g or gestational duration of 36 weeks or less. In 6.6% of the cases and 0.8% of the controls, physical anomalies were noticed before discharge from the newborn nursery. Of the six anomalies reported in the cases, four were found to be the tumor itself or a complication of it. A significant protective effect (odds ratio (OR), 0.47) was noticed for a maternal history of previous fetal loss. Future studies, including biologic markers and stage stratification, may yield more insight into the cause of this disease.

Birth weight as a risk factor for childhood acute lymphoblastic leukemia.

Increased birth weight previously has been reported to be associated with childhood acute leukemia although the etiologic importance of this finding remains unclear. To further assess birth weight and associated parameters as a risk factor for childhood leukemia, a case/control study was performed using children with acute lymphoblastic leukemia (ALL) born in the state of Minnesota and diagnosed since 1969. Data obtained from birth registrations of 219 cases were compared with two control groups matched on date and county of birth (group I) or year of birth (group II). No significant differences were observed in mean birth weights of cases and controls. Statistically significant associations with birth weights greater than 3800 g were identified in cases diagnosed within the first 4 years of life. No associations were found between birth weight and ALL for case children diagnosed after 4 years of age. Factors that might be associated with increased birth weight, including maternal age, birth order, length of gestation, and socioeconomic status as measured by paternal education, were not found to be associated with an increased risk for ALL. The significance of the finding of high birth weight as a risk factor for childhood ALL remains unknown but suggests that pregnancy-related events may be of importance in the etiology of ALL in young children.

Assessment of body elimination attitude.

Constructed a 26-item Likert format Body Elimination Attitude Scale with good internal consistency and temporal stability (N = 60). Factor analysis yielded seven factors labeled Fecal Smell, Personal Hygiene, Sight, Dirty Hair, Animal Feces, Mucous-like Discharge, and Sound. Both the prominence of items that pertained to defecation and the positive association of the Scale with a measure of obsessive personality-anal character were viewed as consistent with psychoanalytic theory. Correlations with psychometric instruments revealed greater body elimination disgust to be associated with psychopathology. Youth, lesser education, having fewer children, being female, and lesser income also were associated with greater disgust.