Empirical likelihood confidence intervals for adaptive cluster sampling

Adaptive cluster sampling (ACS) is an efficient sampling design for estimating parameters of rare and clustered populations. It is widely used in ecological research. The modified Hansen-Hurwitz (HH) and Horvitz-Thompson (HT) estimators based on small samples under ACS have often highly skewed distributions. In such situations, confidence intervals based on traditional normal approximation can lead to unsatisfactory results, with poor coverage properties. Christman and Pontius (Biometrics 56:503–510, 2000) showed that bootstrap percentile methods are appropriate for constructing confidence intervals from the HH estimator. But Perez and Pontius (J Stat Comput Simul 76:755–764, 2006) showed that bootstrap confidence intervals from the HT estimator are even worse than the normal approximation confidence intervals. In this article, we consider two pseudo empirical likelihood functions under the ACS design. One leads to the HH estimator and the other leads to a HT type estimator known as the Hájek estimator. Based on these two empirical likelihood functions, we derive confidence intervals for the population mean. Using a simulation study, we show that the confidence intervals obtained from the first EL function perform as good as the bootstrap confidence intervals from the HH estimator but the confidence intervals obtained from the second EL function perform much better than the bootstrap confidence intervals from the HT estimator, in terms of coverage rate.     

Beurteilung des Ozonrisikos für die Waldregionen Bayerns am Beispiel des Jahres 2002 und des Extremtrockenjahres 2003 auf der Basis der externen Ozonexposition und der internen Ozonaufnahme

Background, aim, and scope Increasing background concentrations of ground-level tropospheric ozone and more frequent and prolonged summer drought incidences due to climate change are supposed to increase the stress on Bavarian forests. For such scenarios growth reduction and yield losses are predicted. Sustainable forest management in Bavaria aims to significantly increase the proportion of beech (Fagus sylvatica L.) because of its broad ecological amplitude. In our regional study different approaches for calculating ozone impact were used to estimate the risks for Bavarian forests in the average climatic, rather moist year 2002 and the extremely dry year 2003.Materials and methods Measurements were conducted for eleven forest ecosystem sites and two forest research sites representing typical Bavarian forest stands under different climatic conditions and situated in different altitudes. For risk assessment currently used approaches were applied either based on the calculation of the cumulative ozone exposure (external dose; MPOC maximal permitted ozone concentration; critical level AOT40_phen? accumulated ozone exposure over a threshold of 40 nl [O₃] l^–1, for the effective phenolgy of beech) or based on the calculation of the phytomedically relevant ozone flux into the stomata (internal dose, critical level AF_st>1,6, accumulated stomatal flux above a flux threshold of 1.6 nmol O₃?m^–2 PLA; PLA = projected leaf area). For calculations continuously recorded ozone concentrations and meteorological and phenological data from nearby rural open field background measuring stations from the national air pollution control and from forested sites were used. Additionally ozone induced leaf symptoms were assessed.Results The exposure-based indices AOT40_phen and MPOC as well as the flux-based index AF_st>1.6suggest that Bavarian forests are at risk from O₃ during a rather moist average year concerning climate conditions (2002) as well as in an extreme dry year (2003). Thus, growth reductions of 5?% are predicted when thresholds are exceeded. Threshold exceedance occurred in both years at all plots, mostly already at the beginning of the growing season and often even many times over. Ozone induced leaf symptoms could be detected only on a few plots in a very slight occurrence.Discussion The results for the applied critical level indices differed depending on climatic conditions during the growing seasons: Regarding exposure-based indices, the highest degree of threshold exceedance occurred in the dry year of 2003 at all plots; the flux-based approach indicated the highest stomatal ozone uptake and thus an increased risk at moist sites or during humid years, whereas the risk was decreasing at dry sites with prolonged water limitation. Hence, soil and accordingly plant water availability was the decisive factor for the flux-modelled internal ozone uptake via stomata. Drought and increased ozone impact can generate synergistic, but also antagonistic effects for forest trees. At water limited rather dry forest sites restricted transpiration and thus production, but concurrently lower ozone uptake and reduced risk for damage can be expected.Conclusions, recommendations, and perspectives For realistic site-specific risk assessment in forest stands the determination of the internal ozone dose via modeling flux based internal stomatal ozone uptake is more appropriate than the calculation of the external ozone dose. The predicted 5?% growth reductions are in discrepancy with the frequently observed increment increase during the last decades in forest stands. Comprehensive and significant statistical verification for ozone induced forest growth reduction as well as the systematic validation of thresholds for ozone in the field is still lacking. However, a multiplicity of different specific new and retrospective growth analysis data should allow closing the gap. Moreover, the determination of canopy transpiration with sap flow measurements is a novel approach to provide cause-effect related, site specific results for the effective internal ozone dose as well as for canopy water supply and consecutively for regional risk estimation. A further future objective is the refinement of O₃ flux modelling by further consideration of soil/water budget characteristics and the above mentioned improved estimations of crown and canopy transpiration. Further, the introduction of threshold ranges for forest trees in view of their specific regional climatic conditions and their validation in real forest stands is necessary for developing meaningful ozone risk predictions for forests.     

Subjective theories of organizing and learning from events

The present paper outlines potential shortcomings of analyzing events in high hazard systems. We argue that the efficiency of organizational learning within high hazard systems is at least partially undermined by the subjective theories of organizing held by their members. These subjective theories basically reflect an “engineering” understanding of “how a system and its components perform”, and are assumed to involve (social-) psychological blind spots when applied to the analysis of events. More specifically, we argue that they neglect individual motives and goals that critically drive work performance and social interactions in high hazard systems. First, we focus on the process of identifying the causes of failed organizing within the course of an event analysis. Our analysis reveals a mismatch between the basic functional assumptions of the event analyst on the motives of social actors involved in an event and on the other hand, the perspective held by the social actors themselves. Second, we discuss the process of correcting failed social system performance after events. Thereby we draw on blind spots that emerge from the direct application of technical safety principles (i.e., standardization and redundancy) to the organization of social systems. Finally, we propose some future research strategies for developing event analysis methods which are aimed at improving an organization’s learning potential.     

Proposing an information criterion for individual-based models developed in a pattern-oriented modelling framework

Individual-based models (IBMs) have been improved in quality and reliability in recent years with an approach called pattern-oriented modelling (POM). POM proposes guidelines to develop models reproducing multiple patterns observed on the field and to test systematically how well the IBMs reproduce them. POM studies used generally traditional methods of goodness of fit such as the sum of squares evaluation or ad hoc comparisons of fitting errors and variations. Model selection, however, can be a rigorous statistical approach based on information theory and information criteria such as the Akaike's information criterion (AIC) or the deviance information criterion (DIC). So far, it has not been tried to link POM to these rigorous techniques. The main problems to achieve that are: (a) the difficulty to have likelihood functions for IBMs’ parameters and (b) the possibility to obtain posterior distributions of IBMs’ parameters given the patterns to reproduce. In a first part, this paper answers problem (a) by proposing and explaining how to calculate a deviance measure (POMDEV) for models developed in a context of POM. And while answering the second problem, a second part of the paper proposes an information criterion for model selection in a POM context (the pattern-oriented modelling information criterion: POMIC). This criterion does not yet have the same theoretical foundation as, e.g., AIC, but uses formal analogies to the DIC. In a third part POMIC is tested with a modelling exercise. This exercise shows the potential of POMIC to use multiple patterns for selecting among multiple potential submodels and eventually select the most parsimonious and well fitting model version. We conclude that POMIC, although being a heuristically derived approach, can greatly improve the POM framework.     

Determination of Oxides of Nitrogen in Combustion Effluents with a Nitrate Ion Selective Electrode

The nitrate ion selective electrode was investigated as an alternative approach to the present colorimetric determination of nitrate resulting from oxidative absorption of nitrogen oxides from combustion effluents. The electrode offers advantages of speed and relatively simple experimental procedure. Replicate measurements of 10^?4–10^?2M nitric acid solutions using bracketing standards show that the electrode approach is capable of good precision (coefficient of variation = ±4%). Comparison of a method utilizing the nitrate electrode with the more laborious phenol disulfonic acid method for the measurement of nitrogen oxides in both oil and gas fired combustion effluents showed agreement within 4% of the mean even in the presence of high levels of SO₂. The correlation coefficient found for PDS vs nitrate electrode is 0.987.     

Influence of temporally variable groundwater flow conditions on point measurements and contaminant mass flux estimations

Monitoring of contaminant concentrations, e.g., for the estimation of mass discharge or contaminant degradation rates, often is based on point measurements at observation wells. In addition to the problem, that point measurements may not be spatially representative, a further complication may arise due to the temporal dynamics of groundwater flow, which may cause a concentration measurement to be not temporally representative. This paper presents results from a numerical modeling study focusing on temporal variations of the groundwater flow direction. “Measurements” are obtained from point information representing observation wells installed along control planes using different well frequencies and configurations. Results of the scenario simulations show that temporally variable flow conditions can lead to significant temporal fluctuations of the concentration and thus are a substantial source of uncertainty for point measurements. Temporal variation of point concentration measurements may be as high as the average concentration determined, especially near the plume fringe, even when assuming a homogeneous distribution of the hydraulic conductivity. If a heterogeneous hydraulic conductivity field is present, the concentration variability due to a fluctuating groundwater flow direction varies significantly within the control plane and between the different realizations. Determination of contaminant mass fluxes is also influenced by the temporal variability of the concentration measurement, especially for large spacings of the observation wells. Passive dosimeter sampling is found to be appropriate for evaluating the stationarity of contaminant plumes as well as for estimating average concentrations over time when the plume has fully developed. Representative sampling has to be performed over several periods of groundwater flow fluctuation. For the determination of mass fluxes at heterogeneous sites, however, local fluxes, which may vary considerably along a control plane, have to be accounted for. Here, dosimeter sampling in combination with time integrated local water flux measurements can improve mass flux estimates under dynamic flow conditions.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

An evaluation of lead concentrations in imported hot sauces

In the last decade, the U.S. Food and Drug Administration (FDA) has issued several warnings and recalls for food products that exceed FDA standards for lead. Products containing chili peppers and salt were often suspected as sources of lead contamination, and included items such as candy that are routinely investigated. However, products such as hot sauces that contain similar ingredients have not been the focus of evaluations. This study quantified lead concentrations in imported hot sauces, evaluated product compliance to existing United States standards, and calculated potential dietary lead exposure for children using the Integrated Exposure Uptake Biokinetic Model. Finally, recommendations for reducing the risk of lead exposure from hot sauces are provided. Twenty-five (25) bottles of imported hot sauces manufactured in Mexico and South America were purchased in Clark County, Nevada. All hot sauces were analyzed for lead concentrations, pH, and leaded packaging. Hot sauces were analyzed by inductively coupled plasma mass spectrometry and packaging was analyzed using x-ray fluorescence technology. Four brands of hot sauces (16%) exceeded 0.1 ppm lead, the current FDA action level for lead in candy. Hot sauces with lead concentrations >0.1 ppm lead contained salt and were manufactured in Mexico. Subsequent analysis of additional lots of hot sauces exceeding 0.1 ppm lead revealed inconsistent lead concentrations between and within manufacturer lots. The lead concentrations of the plastic hot sauce lids ranged from below the limit of detection to 2,028 ppm lead. There was no association between lead concentrations in hot sauces and pepper type. These results indicate the need for more rigorous screening protocols for products imported from Mexico, the establishment of an applicable standard for hot sauce, and resources to allow for the enforcement of existing food safety policies. The data reported herein represent the first known investigation of lead concentrations in hot sauces.     

Polyfluoroalkyl phosphate esters and perfluoroalkyl carboxylic acids in target food samples and packaging—method development and screening

Polyfluoroalkyl phosphate mono-, di-, and tri-esters (mono-, di-, and triPAPs) are used to water- and grease-proof food packaging materials, and these chemicals are known precursors to perfluoroalkyl carboxylic acids (PFCAs). Existing analytical methods for PAPs lack sample clean-up steps in the sample preparation. In the present study, a method based on ultra performance liquid chromatography coupled to tandem mass spectrometry (UPLC/MS/MS) was developed and optimized for the analysis of mono-, di-, and triPAPs, including a clean-up step for the raw extracts. The method was applied to food samples and their PAP-containing packaging materials. The optimized UPLC/MS/MS method enabled the separation and identification of a total of 4 monoPAPs, 16 diPAPs, and 7 triPAPs in the technical mixture Zonyl®-RP. For sample clean-up, weak anion exchange solid phase extraction columns were tested. PAPs standard solutions spiked onto the columns were separated into a fraction containing neutral compounds (triPAPs) and a fraction with ionic compounds (mono- and diPAPs) with recoveries between 72–110 %. Method limits of quantification for food samples were in the sub to low picogram per gram range. For quantitative analysis of PAPs, compound-specific labeled internal standards showed to be essential as sorption and matrix effects were observed. Mono-, di-, and/or triPAPs were detected in all food packaging materials obtained from the Swedish market. Up to nine diPAPs were detected in the food samples, with the 6:2/6:2 and 6:2/8:2 diPAPs as the dominant compounds. DiPAP concentrations in the food samples ranged from 0.9 to 36 pg/g, which was comparable to individual PFCA concentrations in the same samples. Consumption of food packed in PAP-containing materials could be an indirect source of human exposure to PFCAs.     

Bioaccumulation of perfluoroalkyl acids in dairy cows in a naturally contaminated environment

Beef and dairy products may be important vectors of human exposure to perfluoroalkyl acids (PFAAs), but the understanding of how PFAAs are accumulated and transferred through agricultural food chains is very limited. Here, the bioaccumulation of PFAAs in dairy cows receiving naturally contaminated feed and drinking water was investigated by conducting a mass balance of PFAAs for a herd of dairy cows in a barn on a typical Swedish dairy farm. It was assumed that the cows were able to reach steady state with their dietary intake of PFAAs. Perfluorooctane sulfonic acid (PFOS) and perfluoroalkyl carboxylic acids (PFCAs) with 8 to 12 carbons were detected in cow tissue samples (liver, muscle, and blood) at concentrations up to 130 ng kg^?1. Mass balance calculations demonstrated an agreement between total intake and excretion within a factor of 1.5 and consumption of silage was identified as the dominant intake pathway for all PFAAs. Biomagnification factors (BMFs) were highly tissue and homologue specific. While BMFs of PFOS and PFCAs with 9 and 10 fluorinated carbons in liver ranged from 10 to 20, perfluorooctanoic acid (PFOA) was not biomagnified (BMF?<?1) in any of the investigated tissues. Biotransfer factors (BTFs; defined as the concentration in tissue divided by the total daily intake) were calculated for muscle and milk. Log BTFs ranged from ?1.95 to ?1.15 day kg^?1 with the highest BTF observed for PFOS in muscle. Overall, the results of this study suggest that long-chain PFAAs have a relatively high potential for transfer to milk and beef from the diet of dairy cows. However, a low input of PFAAs to terrestrial systems via atmospheric deposition and low bioavailability of PFAAs in soil limits the amount of PFAAs that enter terrestrial agricultural food chains in background contaminated environments and makes this pathway less important than aquatic exposure pathways. The BTFs estimated here provide a useful tool for predicting human exposure to PFAAs via milk and beef under different contamination scenarios.