Cavity-enhanced optical frequency comb spectroscopy in the mid-infrared - application to trace detection of H2O2

We demonstrate the first cavity-enhanced optical frequency comb spectroscopy in the mid-infrared wavelength region and report the sensitive real-time trace detection of hydrogen peroxide in the presence of a large amount of water. The experimental apparatus is based on a mid-infrared optical parametric oscillator synchronously pumped by a high power Yb:fiber laser, a high finesse broadband cavity, and a fast-scanning Fourier transform spectrometer with autobalancing detection. The comb spectrum with a bandwidth of 200 nm centered around 3.75 {\mu}m is simultaneously coupled to the cavity and both degrees of freedom of the comb, i.e., the repetition rate and carrier envelope offset frequency, are locked to the cavity to ensure stable transmission. The autobalancing detection scheme reduces the intensity noise by a factor of 300, and a sensitivity of 5.4 {\times} 10^-9 cm^-1 Hz^-1/2 with a resolution of 800 MHz is achieved (corresponding to 6.9 {\times} 10^-11 cm^-1 Hz^-1/2 per spectral element for 6000 resolved elements). This yields a noise equivalent detection limit for hydrogen peroxide of 8 parts-per-billion (ppb); in the presence of 2.8% of water the detection limit is 130 ppb. Spectra of acetylene, methane and nitrous oxide at atmospheric pressure are also presented, and a line shape model is developed to simulate the experimental data.Comment: submitted to special FLAIR 2011 issue of Appl. Phys.

Mechanisms underlying the sperm quality advantage in sperm competition and cryptic female choice in Drosophila melanogaster

Contrary to early predictions of sperm competition theory, postcopulatory sexual selection favoring increased investment per sperm (e.g., sperm size, sperm quality) has been demonstrated in numerous organisms. Recent findings reveal that sperm production strategies are highly variable, with males of some species producing relatively few, giant sperm. We empirically demonstrate for Drosophila melanogaster that both sperm quality and sperm quantity independently contribute to competitive male fertilization success. The interaction between sperm quality and quantity suggests an internal positive reinforcement on selection for sperm quality, with selection predicted to intensify as investment per sperm increases and the number of sperm competing declines. The mechanism underlying the sperm quality advantage is elucidated through examination of the relationship between female sperm-storage organ morphology and the differential organization of different length sperm within the organ. Our results exemplify that primary sex cells can bear secondary sexual straits

Mid-Infrared Time-Resolved Frequency Comb Spectroscopy of Transient Free Radicals

We demonstrate time-resolved frequency comb spectroscopy (TRFCS), a new broadband absorption spectroscopy technique for the study of trace free radicals on the microsecond timescale. We apply TRFCS to study the time-resolved, mid-infrared absorption of the deuterated hydroxyformyl radical trans-DOCO, an important short-lived intermediate along the OD + CO reaction path. Directly after photolysis of the chemical precursor acrylic acid-d_1, we measure absolute trans-DOCO product concentrations with a sensitivity of 5 × 10^(10) cm^(–3) and observe its subsequent loss with a time resolution of 25 μs. The multiplexed nature of TRFCS allows us to detect simultaneously the time-dependent concentration of several other photoproducts and thus unravel primary and secondary chemical reaction pathways

Mid-infrared VIPA Spectrometer for Rapid and Broadband Trace Gas Detection

We present and characterize a 2-D imaging spectrometer based on a virtually-imaged phased array (VIPA) disperser for rapid, high-resolution molecular detection using mid-infrared (MIR) frequency combs at 3.1 and 3.8 \mu m. We demonstrate detection of CH4 at 3.1 \mu m with >3750 resolution elements spanning >80 nm with ~600 MHz resolution in a <10 \mu s acquisition time. In addition to broadband detection, rapid, time-resolved single-image detection is demonstrated by capturing dynamic concentration changes of CH4 at a rate of ~375 frames per second. Changes in absorption above the noise floor of 5\times 10-4 are readily detected on the millisecond time scale, leading to important future applications such as real time monitoring of trace gas concentrations and detection of reactive intermediates

Guiding principles for the development and application of solid-phase phosphorus adsorbents for freshwater ecosystems

While a diverse array of phosphorus (P)-adsorbent materials is currently available for application to freshwater aquatic systems, selection of the most appropriate P-adsorbents remains problematic. In particular, there has to be a close correspondence between attributes of the P-adsorbent, its field performance, and the management goals for treatment. These management goals may vary from a rapid reduction in dissolved P to address seasonal enrichments from internal loading, targeting external fluxes due to anthropogenic sources, or long term inactivation of internal P inventories contained within bottom sediments. It also remains a challenge to develop new methods and materials that are ecologically benign and cost-effective. We draw on evidence in the literature and the authors’ personal experiences in the field, to summarise the attributes of a range of P-adsorbent materials. We offer 'guiding principles' to support practical use of existing materials and outline key development needs for new materials

Postcopulatory sexual selection in Drosophila

The arena of sexual selection expands after copulation to include the female reproductive tract when promiscuous females house ejaculates from more than one male. Male-male competition continues in the form of sperm competition, and female choice continues in the form of cryptic female choice. This study aims to contribute (1) to the understanding of the mechanisms underlying postcopulatory sexual selection and (2) to the unification of postcopulatory sexual selection theory and traditional sexual selection theory. Strong offensive and defensive sperm competitors are favored by postcopulatory sexual selection. Offensive and defensive sperm competitive ability were only found to be significantly repeatable in D. melanogaster across multiple sperm competition bouts between the same two males within the same female. Additionally, experimental evolution techniques revealed that the heritabilities of sperm offense and defense are low in genetically variable populations. These experiments highlight the complex nature of sperm precedence and the maintenance of genetic variation in ejaculate characteristics. Postcopulatory sexual selection on males can lead to decreased sperm numbers by favoring larger sperm. However, a decline in sperm numbers is predicted to weaken selection on males and increase selection on females. Sexual selection for longer sperm, therefore, is expected to be self-limiting. Competitive mating experiments confirmed this big-sperm paradox in Drosophila . A resolution is provided by incorporating knowledge of postcopulatory processes into the interpretation of measures of sexual selection intensity. Males with little sperm competition risk or few mating opportunities should divert resources away from gamete production because sperm are no longer regarded as energetically cheap and effectively limitless in supply. This prediction was met in the giant-sperm producing D. bifurca . Solitary males with infrequent access to females were found to produce sperm at a rate much slower than males raised in constant association with females and other males. Understanding the adaptive significance of polyandry is a challenge. No direct fitness advantages of polyandry were found in D. melanogaster . If polyandry evolved to promote postcopulatory competition between males successful at precopulatory competition, then promiscuous females may benefit if these males disproportionately fertilize their eggs. However, no such indirect genetic benefits were revealed

Adaptive modulation of sperm production rate in Drosophila bifurca, a species with giant sperm

Sperm have traditionally been regarded as energetically cheap and effectively limitless in supply, although evidence conflicting with this view has become increasingly abundant. For instance, males from a variety of taxa have been shown to strategically partition sperm across ejaculates in response to perceived sperm competition risk. It follows that males might also be predicted to adaptively modulate the rate at which sperm are produced. Here we show that, in the giant sperm producing fruitfly Drosophila bifurca, solitary males with infrequent access to females produce sperm at a much lower rate than males raised in association with females and other males. Our results support the prediction that males with little risk of sperm competition risk or few mating opportunities should divert resources away from gamete production