Sampling design for compliance monitoring of surface water quality: A case study in a Polder area

International agreements such as the EU Water Framework Directive (WFD) ask for efficient sampling methods for monitoring natural resources. In this paper a general methodology for designing efficient, statistically sound monitoring schemes is described. An important decision is the choice between a design-based and a model-based method, implying the choice between probability (random) sampling and purposive sampling. For mapping purposes, model-based methods are more appropriate, whereas to obtain valid results for the universe as a whole, such as in testing water quality standards against legal standards, we generally prefer a design-based method. Four basic sampling patterns in space-time universe are described: static, synchronous, static-synchronous, and rotational. A case study is carried out for monitoring the quality of surface water at two farms in western Netherlands, wherein a synchronous sampling design is applied, with stratified simple random sampling in both space and time. To reduce laboratory costs the aliquots taken at the locations of a given sampling round are bulked to form a composite. To test the spatiotemporal mean N-total concentration during the summer half-year against the MAR standard with a power of 80% at a concentration 15% below the MAR standard and with a confidence of 95%, six to nine sampling rounds are needed with 50 to 75 locations per sampling round. For P-total the required number of sampling rounds differs strongly between the two farms, but is for both farms much larger than for N-total

Opportunities and challenges for official statistics in a digital society

National systems of official statistics are expected to provide governments, businesses and the public with data about the economic, demographic, social and environmental situation. Digitisation of data collection for official statistics is mooted as having a major potential impact on society. Greater use of administrative data held in government is proceeding slowly. Evidence is limited, but access to big data − from satellites, point-of-sale systems and social media − is being explored and trialled. Initiatives are driven by new requirements for official statistics as well as pressures on traditional data collection from households and businesses. Effective government use of new data sources has the possibility of creating the ultimate evidence base for policies intended to improve lives, and anonymised data are also being made available to other researchers. The article uses the UK as a case study to outline how the big data evidence-to-policy process is intended to work in that context, and to assess the challenges faced in making it work as intended. We conclude that technical developments need to be accompanied throughout with attention to the marketing of official statistics and engagement with all users and potential users. The goal is to produce trusted as well as trustworthy statistics

Infrared spectroscopy of cataclysmic variables: III. Dwarf novae below the period gap and novalike variables

We present K-band spectra of the short-period dwarf novae YZ Cnc, LY Hya, BK Lyn, T Leo, SW UMa and WZ Sge, the novalike variables DW UMa, V1315 Aql, RW Tri, VY Scl, UU Aqr and GP Com, and a series of field dwarf stars with spectral types ranging from K2-M6. The spectra of the dwarf novae are dominated by emission lines of HI and HeI. The large velocity and equivalent widths of these lines, in conjunction with the fact that the lines are double-peaked in the highest inclination systems, indicate an accretion disc origin. In the case of YZ Cnc and T Leo, for which we obtained time-resolved data covering a complete orbital cycle, the emission lines show modulations in their equivalent widths which are most probably associated with the bright spot (the region where the gas stream collides with the accretion disc). There are no clear detections of the secondary star in any of the dwarf novae below the period gap, yielding upper limits of 10-30% for the contribution of the secondary star to the observed K-band flux. In conjunction with the K-band magnitudes of the dwarf novae, we use the derived secondary star contributions to calculate lower limits to the distances to these systems. The spectra of the novalike variables are dominated by broad, single-peaked emission lines of HI and HeI - even the eclipsing systems we observed do not show the double-peaked profiles predicted by standard accretion disc theory. With the exception of RW Tri, which exhibits NaI, CaI and 12CO absorption features consistent with a M0V secondary contributing 65% of the observed K-band flux, we find no evidence for the secondary star in any of the novalike variables. The implications of this result are discussed.Comment: 13 pages, 5 figures, to appear in MNRA

UBVRI photopolarimetry of the long period eclipsing AM Herculis binary V1309

We report simultaneous UBVRI photo-polarimetric observations of the long period (7.98 h) AM Her binary V1309 Ori. The length and shape of the eclipse ingress and egress varies from night to night. We suggest this is due to the variation in the brightness of the accretion stream. By comparing the phases of circular polarization zero-crossovers with previous observations, we confirm that V1309 Ori is well synchronized, and find an upper limit of 0.002 percent for the difference between the spin and orbital periods. We model the polarimetry data using a model consisting of two cyclotron emission regions at almost diametrically opposite locations, and centered at colatitude 35 (deg) and 145 (deg) on the surface of the white dwarf. We also present archive X-ray observations which show that the negatively polarised accretion region is X-ray bright.Comment: 11 pages, 12 figures (2 colour), Fig1 and Fig 4 are in lower resolution than in original paper, accepted for publication in Monthly Notices of the Royal Astronomical Societ

Kinetic Resolution in Asymmetric Epoxidation using Iminium Salt Catalysis

The first reported examples of kinetic resolution in epoxidation reactions using iminium salt catalysis are described, providing up to 99% ee in the epoxidation of racemic cis-chromenes

Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air

The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (εapp) for mid- and high-latitude stratospheric samples are (-2.4±0.5) ‰ and (-2.3±0.4) ‰ for CFC-11, (-12.2±1.6) ‰ and (-6.8±0.8) ‰ for CFC-12 and (-3.5±1.5) ‰ and (-3.3±1.2) ‰ for CFC-113, respectively. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere-troposphere exchange. We compare these projections to the long-term δ(37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978 – 2010) and tropospheric firn air samples from Greenland (NEEM site) and Antarctica (Fletcher Promontory site). From 1970 to the present-day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties a constant average emission isotope delta is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope delta has been affected by changes in CFC manufacturing processes, or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 ml), using a single-detector gas chromatography-mass spectrometry system

The Quiescent Spectrum of the AM CVn star CP Eri

We used the 6.5m MMT to obtain a spectrum of the AM CVn star CP Eri in quiescence. The spectrum is dominated by He I emission lines, which are clearly double peaked with a peak-to-peak separation of ~1900 km/s. The spectrum is similar to that of the longer period AM CVn systems GP Com and CE 315, linking the short and the long period AM CVn systems. In contrast with GP Com and CE 315, the spectrum of CP Eri does not show a central 'spike' in the line profiles, but it does show lines of SiII in emission. The presence of these lines indicates that the material being transferred is of higher metallicity than in GP Com and CE 315, which, combined with the low proper motion of the system, probably excludes a halo origin of the progenitor of CP Eri. We constrain the primary mass to M_1>0.27 M_sun and the orbital inclination to 33 degr < i < 80 degr. The presence of the He I lines in emission opens up the possibility for phase resolved spectroscopic studies which allows a determination of the system parameters and a detailed study of helium accretion disks under highly varying circumstances.Comment: 12 pages, 2 figures, accepted for publication in ApJ Letter

First asymmetric synthesis of the natural enantiomer of the indolizidino[8,7-b]indole alkaloid harmicine

We report a novel, facile and asymmetric approach for the synthesis of the indole alkaloid harmicine via a highly diastereoselective N-acyliminium cyclization reaction as a key synthetic step, and verify the relative stereochemistry of the key synthetic intermediate in this approach through X-ray crystallography