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The occurrence and significance of polychlorinated biphenyls in the environment

SUMMARY: Polychlorinated biphenyls constitute a group of chlorine-bearing compounds of industrial origin that have permeated the natural environment throughout the world. Their chemical structure resembles that of some of the organochlorine pesticides. They are troublesome interferences in gas chromatographic analysis of these pesticides. Although methods have been developed to overcome analytical problems, measurements of quantity still are only approximate. Special studies in the United States, Netherlands, and Great Britain have traced PCB's to industrial effluent, but other possible sources have not been followed. Their use in paints, cartons, and insulating fluids suggests that environmental pollution may be from many different sources. PCB's are present in fish and wildlife in many countries of the world. Quantities are higher in animals living near industrial areas. PCB's build up in biological food chains with increases of tens to thousands of times from lower to higher organisms. Experimental studies have shown that PCB's have a toxicity to mallards, pheasants, bobwhite quail, coturnix quail, red-winged blackbirds, starlings, cowbirds, and grackles that is of the same order as the toxicity of DDE to these species. Overt signs of poisoning also are similar to those caused by compounds of the DDT group. Toxic effects of DDE and Aroclor 1254 to coturnix chicks were additive, but not synergistic. PCB's containing higher percentages of chlorine are more toxic to birds than those containing lower percentages. PCB's of foreign manufacture contained contaminants to an extent that greatly increased their toxicity Aroclor 1242. Statistical evaluations of the role that different chemicals may play in thinning of eggshells of brown pelicans show that DDE residues correlate better with shell thinning than do residues of dieldrin or PCB's. Studies of the effects of PCB's in the environment are as yet insufficient for well-rounded conclusions. The evidence available indicates that they must be viewed as potential problems until fuller data can be assembled. Toxicity to insects of PCB's of different degrees of chlorination is the reverse of the pattern in birds: the lower chlorinations are more toxic to insects. PCB's enhanced the toxicity of dieldrin and DDT to insects. Shrimp are very sensitive to PCB's and most will die as a result of 20-day exposure to a concentration of 5 ppb. PCB's also inhibit shell growth of oysters. Fish and crabs are less sensitive; all accumulate residues to many times the concentrations in the water, and a test with crabs showed that they lost the residues very slowly. Residues of PCB's in the brains of birds killed by these compounds measure in the hundreds of parts per million. PCB's may have contributed to mortality of some birds in the field. PCB's induce microsomal enzyme activity in birds and mammals and the lower chlorinated mixtures have estrogenic activity in rats. Exposure to PCB's increased the susceptibility of mallard ducklings to duck hepatitis virus. Offspring of pheasants whose parents received high dosages of PCB's made poor choices in visual cliff tests. Egg production and hatching after pipping also were affected. Long-term studies of the reproductive effects of Aroclor 1254 on mallards and bobwhite quail and of Aroclor 1254 plus DDE on quail showed no significant differences from controls. In studies of chickens, however, egg production, hatchability, and shell thickness were impaired by high doses of Aroclor 1254 and by low doses of Aroclor 1242. Statistical evaluations of the role that different chemicals may play in thinning of eggshells of brown pelicans show that DDE residues correlate better with shell thinning than do residues of dieldrin or PCB's. Studies of the effects of PCB's in the environment are as yet insufficient for well-rounded conclusions. The evidence available indicates that they must be

Transactions of the North American Wildlife and Na

Geohydrologic and water-quality characterization of a fractured-bedrock test hole in an area of Marcellus shale gas development, Bradford County, Pennsylvania

Open-File Miscellaneous Investigation 13–01.1 presents the results of geohydrologic investigations on a 1,664-foot-deep core hole drilled in the Bradford County part of the Gleason 7.5-minute quadrangle in north-central Pennsylvania. In the text, the authors discuss their methods of investigation, summarize physical and analytical results, and place those results in context. Four appendices include (1) a full description of the core in an Excel worksheet; (2) water-quality and core-isotope analytical results in Excel workbooks; (3) geophysical logs in LAS and PDF files, and an Excel workbook containing attitudes of bedding and fractures calculated from televiewer logs; and (4) MP4 clips from the downhole video at selected horizons.

Pennsylvania

Sensitivity of fish density estimates to standard analytical procedures applied to Great Lakes hydroacoustic data

Standardized methods of data collection and analysis ensure quality and facilitate comparisons among systems. We evaluated the importance of three recommendations from the Standard Operating Procedure for hydroacoustics in the Laurentian Great Lakes (GLSOP) on density estimates of target species: noise subtraction; setting volume backscattering strength (S v ) thresholds from user-defined minimum target strength (TS) of interest (TS-based S v threshold); and calculations of an index for multiple targets (N v index) to identify and remove biased TS values. Eliminating noise had the predictable effect of decreasing density estimates in most lakes. Using the TS-based Sv threshold decreased fish densities in the middle and lower layers in the deepest lakes with abundant invertebrates (e.g., Mysis diluviana). Correcting for biased in situ TS increased measured density up to 86% in the shallower lakes, which had the highest fish densities. The current recommendations by the GLSOP significantly influence acoustic density estimates, but the degree of importance is lake dependent. Applying GLSOP recommendations, whether in the Laurentian Great Lakes or elsewhere, will improve our ability to compare results among lakes. We recommend further development of standards, including minimum TS and analytical cell size, for reducing the effect of biased in situ TS on density estimates.

Great Lakes

A new formula for the analytical solution of the radial dispersion problem

A new formula is presented for the analytical solution of the radial dispersion problem, which analyzes the dispersive transport of a tracer in radial flow from a recharge well. This formula is simpler than a solution presented by previous investigators, but the two solutions are shown to be equivalent. Because the analytical solution consists of an integral of an oscillatory function, it is evaluated as an alternating series, the terms of which are the integrals over successive half cycles of the integrand. An efficient algorithm is used to accelerate convergence of the series. The accuracies of previous solutions obtained by finite difference, numerical Laplace transform, and perturbation methods are examined by comparison with the analytical solution. Numerical values of the solution are tabulated for readers interested in checking the accuracies of solute transport codes.

Water Resources Research

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory-Evaluation of alkaline persulfate digestion as an alternative to Kjeldahl digestion for determination of total and dissolved nitrogen and phosphorus in water

Alkaline persulfate digestion was evaluated and validated as a more sensitive, accurate, and less toxic alternative to Kjeldahl digestion for routine determination of nitrogen and phosphorus in surface- and ground-water samples in a large-scale and geographically diverse study conducted by U.S. Geological Survey (USGS) between October 1, 2001, and September 30, 2002. Data for this study were obtained from about 2,100 surface- and ground-water samples that were analyzed for Kjeldahl nitrogen and Kjeldahl phosphorus in the course of routine operations at the USGS National Water Quality Laboratory (NWQL). These samples were analyzed independently for total nitrogen and total phosphorus using an alkaline persulfate digestion method developed by the NWQL Methods Research and Development Program. About half of these samples were collected during nominally high-flow (April-June) conditions and the other half were collected during nominally low-flow (August-September) conditions. The number of filtered and whole-water samples analyzed from each flow regime was about equal.By operational definition, Kjeldahl nitrogen (ammonium + organic nitrogen) and alkaline persulfate digestion total nitrogen (ammonium + nitrite + nitrate + organic nitrogen) are not equivalent. It was necessary, therefore, to reconcile this operational difference by subtracting nitrate + nitrite concentra-tions from alkaline persulfate dissolved and total nitrogen concentrations prior to graphical and statistical comparisons with dissolved and total Kjeldahl nitrogen concentrations. On the basis of two-population paired t-test statistics, the means of all nitrate-corrected alkaline persulfate nitrogen and Kjeldahl nitrogen concentrations (2,066 paired results) were significantly different from zero at the p = 0.05 level. Statistically, the means of Kjeldahl nitrogen concentrations were greater than those of nitrate-corrected alkaline persulfate nitrogen concentrations. Experimental evidence strongly suggests, however, that this apparent low bias resulted from nitrate interference in the Kjeldahl digestion method rather than low nitrogen recovery by the alkaline persulfate digestion method. Typically, differences between means of Kjeldahl nitrogen and nitrate-corrected alkaline persulfate nitrogen in low-nitrate concentration (< 0.1 milligram nitrate nitrogen per liter) subsets of filtered surface- and ground-water samples were statistically equivalent to zero at the p =level.Paired analytical results for dissolved and total phosphorus in Kjeldahl and alkaline persulfate digests were directly comparable because both digestion methods convert all forms of phosphorus in water samples to orthophosphate. On the basis of two-population paired t-test statistics, the means of all Kjeldahl phosphorus and alkaline persulfate phosphorus concentrations (2,093 paired results) were not significantly different from zero at the p = 0.05 level. For some subsets of these data, which were grouped according to water type and flow conditions at the time of sample collection, differences between means of Kjeldahl phosphorus and alkaline persulfate phosphorus concentrations were not equivalent to zero at the p = 0.05 level. Differences between means of these subsets, however, were less than the method detection limit for phosphorus (0.007 milligram phosphorus per liter) by the alkaline persulfate digestion method, and were therefore analytically insignificant.This report provides details of the alkaline persulfate digestion procedure, interference studies, recovery of various nitrogen- and phosphorus-containing compounds, and other analytical figures of merit. The automated air-segmented continuous flow methods developed to determine nitrate and orthophosphate in the alkaline persulfate digests also are described. About 125 microliters of digested sample are required to determine nitrogen and phosphorus in parallel at a rate of about 100 samples per hour with less than 1-percent sample in

Water-Resources Investigations Report

Performance evaluation and methods comparison of transcriptomic-based approaches for the characterization of wastewater treatment effluent

Wastewater treatment effluents (WWTE) present complex risks to aquatic ecosystems that are difficult to characterize using traditional methods. This study systematically evaluated the consistency and performance of transcriptomic-based approaches over time with repeated sampling and with differing experimental approaches (selection of reference condition, grab vs. composite sampling, deployed vs. laboratory exposed). RNA-seq was performed on larval fathead minnow (FHM) exposed in the laboratory to moderately hard reconstituted water (MRHW) or individual grab samples collected from an upstream site and a WWTE in the morning and afternoon over two successive days, as well as FHM deployed concurrently with grab sampling at the same sites. Composite transcriptional profiles were generated by pooling count data from grab sample exposures. The choice of comparator significantly affected results. The use of the upstream site as the reference consistently yielded fewer differentially expressed genes (DEGs) and minimal overlap compared to DEG sets from the other comparisons. Using MRHW as a comparator, DEG sets showed high consistency across grab samples, with morning samples demonstrating larger, highly consistent gene expression sets (96 % overlap) compared to afternoon samples, revealing clear and consistent within-day expression patterns. With the MHRW comparator, DEG sets from grab sample composites and deployments also overlapped substantially, indicating that transcriptional profiles accurately reflect WWTE composition regardless of exposure method. Comparisons with non-targeted (NTA) and targeted analytical datasets confirmed that gene expression interpretations aligned with effluent composition while highlighting limitations of relying solely on targeted analyte sets for connecting expression to specific chemicals. Though highly dependent on experimental design, these results demonstrate that transcriptomic-based methods provide significant utility for characterizing the bioactivity of complex environmental mixtures, and when paired with NTA datasets, have the potential to deliver a comprehensive assessment of their environmental risk.

Environmental Pollution

Fission-track and K-Ar ages of Tertiary ash-flow tuffs, north-central Nevada

Ages obtained from three Tertiary ash-flow tuffs in central Nevada by fission-track and K-Ar dating are concordant. Samples dated by these methods from the same localities give the same age within the limits of analytical uncertainty. Samples of three units from widely separated localities were dated further to confirm the concordance of the dating methods and to establish that ages can be used, in conjunction with normal geologic techniques, as a criteria for correlation. The minerals dated by K-Ar were biotite and sanidine; and sphene zircon and apatite were used to determine the fission track ages. The Bates Mountain Tuff was dated at 24.0 m.y. (F.T.) and 24.0 m.y. (K-Ar). The Fish Creek Mountains Tuff has a fission-track age of 24.4 m.y., and a K-Ar age of 23.9 m.y. The average fission-track age for the Caetano Tuff is 34.9 m.y., and it has an average K-Ar age of 32.3 m.y. The amount of analytical uncertainty is slightly greater in the fission track method. Sampling, preparation, and determination of the age by the fission-track method is competitive with the K-Ar method.

Nevada

A transient laboratory method for determining the hydraulic properties of 'tight' rocks-II. Application

In Part I a general analytical solution for the transient pulse test was presented. Part II presents a graphical method for analyzing data from a test to obtain the hydraulic properties of the sample. The general solution depends on both hydraulic conductivity and specific storage and, in theory, analysis of the data can provide values for both of these hydraulic properties. However, in practice, one of two limiting cases may apply in which case it is possible to calculate only hydraulic conductivity or the product of hydraulic conductivity times specific storage. In this paper we examine the conditions when both hydraulic parameters can be calculated. The analyses of data from two tests are presented. In Appendix I the general solution presented in Part I is compared with an earlier analysis, in which compressive storage in the sample is assumed negligible, and the error in calculated hydraulic conductivity due to this simplifying assumption is examined.

International Journal of Rock Mechanics and Mining

Comparison of passive and pumped sampling methods for analysis of groundwater quality, Kirtland Air Force Base, Albuquerque, New Mexico, 2019

A plume of ethylene dibromide (EDB) dissolved in groundwater extends northeast from the Bulk Fuels Facility on Kirtland Air Force Base, New Mexico. The leading edge of the EDB plume is upgradient from several water-supply wells. In 2013, the U.S. Geological Survey (USGS), in cooperation with the Albuquerque Bernalillo County Water Utility Authority and the U.S. Air Force, installed four sentinel well nests and two aquifer-test pumping wells between the EDB plume and the water-supply wells to serve as an early warning if the plume travels toward the water-supply wells. Since 2015, the USGS has used submersible pumps to sample the sentinel wells quarterly. In February 2017, the USGS began using dual-membrane passive diffusion bag samplers for quarterly sampling in the wells. To ensure that the passive samplers are obtaining representative samples of the groundwater contaminants, the USGS, in cooperation with the U.S. Air Force, initiated a study in 2019 to compare results from pump sampling and passive samplers and to use vertical profiling to determine the optimal depth for passive sampler placement in the screened interval to better inform long-term monitoring of the site. Vertical profiling included deploying passive samplers throughout the submerged screened interval of four shallow sentinel wells. After retrieval of the passive samplers, pump samples were collected. The results of analyses of both types of samples were compared. Volatile organic compound results for this study were all below the raised reporting levels, which is a level five times the maximum concentration detected in a blank and determined by an in-depth quality assessment; therefore, this study focused on inorganic constituent results, including major ions, trace elements, and stable isotopes of water, to calculate the relative percent difference (RPD) between the pump and passive sampling method results as a way to determine where passive samplers would be best placed in each of the wells. Several analytes had an RPD of more than plus or minus 50 percent, and several analytes were not within the estimated variability for each sampling method. Additionally, the variability within each sampling method was quantified and compared. Factors that likely contributed to the lack of comparison between each sampling method included temporal variability, flow regime, volume of sample integrated through different aquifer intervals, and reduction/oxidation processes. RPD and method variability were used to determine the intervals within each well with the greatest agreement between sampling methods. Optimal sampling depths for each well were then correlated to the intervals where quarterly sampling has been occurring.

New Mexico

Relationship and variation of qPCR and culturable enterococci estimates in ambient surface waters are predictable

The quantitative polymerase chain reaction (qPCR) method provides rapid estimates of fecal indicator bacteria densities that have been indicated to be useful in the assessment of water quality. Primarily because this method provides faster results than standard culture-based methods, the U.S. Environmental Protection Agency is currently considering its use as a basis for revised ambient water quality criteria. In anticipation of this possibility, we sought to examine the relationship between qPCR-based and culture-based estimates of enterococci in surface waters. Using data from several research groups, we compared enterococci estimates by the two methods in water samples collected from 37 sites across the United States. A consistent linear pattern in the relationship between cell equivalents (CCE), based on the qPCR method, and colony-forming units (CFU), based on the traditional culturable method, was significant (P < 0.05) at most sites. A linearly decreasing variance of CCE with increasing CFU levels was significant (P < 0.05) or evident for all sites. Both marine and freshwater sites under continuous influence of point-source contamination tended to reveal a relatively constant proportion of CCE to CFU. The consistency in the mean and variance patterns of CCE versus CFU indicates that the relationship of results based on these two methods is more predictable at high CFU levels (e.g., log 10 CFU > 2.0/100 mL) while uncertainty increases at lower CFU values. It was further noted that the relative error in replicated qPCR estimates was generally higher than that in replicated culture counts even at relatively high target levels, suggesting a greater need for replicated analyses in the qPCR method to reduce relative error. Further studies evaluating the relationship between culture and qPCR should take into account analytical uncertainty as well as potential differences in results of these methods that may arise from sample variability, different sources of pollution, and environmental factors.

Environmental Science & Technology

Quality-Assurance Data for Routine Water Analyses by the U.S. Geological Survey Laboratory in Troy, New York - July 2005 through June 2007

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2005 through June 2007. Results for the quality-control samples for 19 analytical procedures were evaluated for bias and precision. Control charts indicate that data for eight of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: total aluminum, calcium, magnesium, nitrate (colorimetric method), potassium, silicon, sodium, and sulfate. Eight of the analytical procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits; these procedures were: total aluminum, calcium, dissolved organic carbon, chloride, nitrate (ion chromatograph), potassium, silicon, and sulfate. The magnesium and pH procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The acid-neutralizing capacity, total monomeric aluminum, nitrite, and specific conductance procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicated that the procedures for 16 of 17 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 21 analytes. At least 93 percent of the samples met data-quality objectives for all analytes except acid-neutralizing capacity (85 percent of samples met objectives), total monomeric aluminum (83 percent of samples met objectives), total aluminum (85 percent of samples met objectives), and chloride (85 percent of samples met objectives). The ammonium and total dissolved nitrogen did not meet the data-quality objectives. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project met the Troy Laboratory data-quality objectives for 87 percent of the samples analyzed. The P-sample (low-ionic-strength constituents) analysis had two outliers each in two studies. The T-sample (trace constituents) analysis and the N-sample (nutrient constituents) analysis had one outlier each in two studies. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 85 percent of the samples met data-quality objectives for 11 of the 14 analytes; the exceptions were acid-neutralizing capacity, total aluminum and ammonium. Data-quality objectives were not met in 41 percent of samples analyzed for acid-neutralizing capacity, 50 percent of samples analyzed for total aluminum, and 44 percent of samples analyzed for ammonium. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 86 percent of the samples analyzed for calcium, magnesium, pH, potassium, and sodium. Data-quality objectives were met by 76 percent of the samples analyzed for chloride, 80 percent of the samples analyzed for specific conductance, and 77 percent of the samples analyzed for sulfate.

Open-File Report

Increasing accuracy of dispersal kernels in grid-based population models

Dispersal kernels in grid-based population models specify the proportion, distance and direction of movements within the model landscape. Spatial errors in dispersal kernels can have large compounding effects on model accuracy. Circular Gaussian and Laplacian dispersal kernels at a range of spatial resolutions were investigated, and methods for minimizing errors caused by the discretizing process were explored. Kernels of progressively smaller sizes relative to the landscape grid size were calculated using cell-integration and cell-center methods. These kernels were convolved repeatedly, and the final distribution was compared with a reference analytical solution. For large Gaussian kernels ( σ > 10 cells), the total kernel error was <10 −11 compared to analytical results. Using an invasion model that tracked the time a population took to reach a defined goal, the discrete model results were comparable to the analytical reference. With Gaussian kernels that had σ ≤ 0.12 using the cell integration method, or σ ≤ 0.22 using the cell center method, the kernel error was greater than 10%, which resulted in invasion times that were orders of magnitude different than theoretical results. A goal-seeking routine was developed to adjust the kernels to minimize overall error. With this, corrections for small kernels were found that decreased overall kernel error to <10 −11 and invasion time error to <5%.

Ecological Modelling

Comparison of two methods for estimating base flow in selected reaches of the South Platte River, Colorado

The U.S. Geological Survey, in cooperation with the Colorado Water Conservation Board, compared two methods for estimating base flow in three reaches of the South Platte River between Denver and Kersey, Colorado. The two methods compared in this study are the Mass Balance and the Pilot Point methods. Base-flow estimates made with the two methods were based upon a 54-year period of record (1950 to 2003). The Mass Balance method for estimating base flow is based on a mass balance of all known inflows to and outflows from a given stream reach, with the equation being solved for groundwater flow into or out of the reach. A positive mass balance indicates a gaining reach (base flow) and a negative balance indicates a losing reach. The mass balance was calculated using daily mean streamflow, wastewater treatment plant discharge, and stream diversion data. Monthly mean base flow was calculated as the average of all daily mean mass-balance results for a given month. The Pilot Point method is based on a daily mean mass balance of all inflows to and outflows from a stream reach. The Pilot Point differs from the Mass Balance method in that extreme daily mass-balance results are constrained utilizing two analytical solutions that represent the maximum possible streamflow gain or loss. Additionally, the Pilot Point method utilizes a smoothing function, based on a moving average of the daily constrained mass-balance results. The moving average for this study utilized a moving-average period, called the bin width, of 61 days. The maximum and minimum base-flow constraints and the smoothing function are utilized to provide base-flow estimates that exhibit reasonable maximum values and temporal variability consistent with the concept of groundwater flow being gradual and slow. Both the Mass Balance and Pilot Point results provided similar patterns in annual and monthly base flow. All three reaches were indicated to be gaining reaches, particularly after about 1970, with the magnitude of base flow increasing downstream. This degree of similarity between the two methods was expected because both methods are based on a streamflow mass balance. The magnitude of estimates provided by the two methods was measurably different. The stream gains and losses estimated using the Mass Balance method were consistently more variable and of greater magnitude than those estimated using the Pilot Point method. In the Denver to Henderson reach, the median estimated annual mean base flow was 34.0 cubic feet per second (ft 3 /s) using the Mass Balance method and was 39.1 ft 3 /s using the Pilot Point method. In the Henderson to Fort Lupton reach, the median estimated annual mean base flow was 50.0 ft 3 /s using the Mass Balance method and was 40.0 ft 3 /s using the Pilot Point method. In the Fort Lupton to Kersey reach, the median estimated annual mean base flow was 234 ft 3 /s using the Mass Balance method and was 214 ft 3 /s using the Pilot Point method. The Mass Balance results were quite variable over time such that they appeared suspect with respect to the concept of groundwater flow as being gradual and slow. The large degree of variability in the day-to-day and month-to-month Mass Balance results is likely the result of many factors. These factors could include ungaged stream inflows or outflows, short-term streamflow losses to and gains from temporary bank storage, and any lag in streamflow accounting owing to streamflow lag time of flow within a reach. The Pilot Point time series results were much less variable than the Mass Balance results and extreme values were effectively constrained. Less day-to-day variability, smaller magnitude extreme values, and smoother transitions in base-flow estimates provided by the Pilot Point method are more consistent with a conceptual model of groundwater flow being gradual and slow. The Pilot Point method provided a better fit to the conceptual model of groundwater flow and appeared to provide reasonable estimates of base flow.

Colorado

Long-range hazard assessment of volcanic ash dispersal for a Plinian eruptive scenario at Popocatépetl volcano (Mexico): implications for civil aviation safety

Popocatépetl is one of Mexico’s most active volcanoes threatening a densely populated area that includes Mexico City with more than 20 million inhabitants. The destructive potential of this volcano is demonstrated by its Late Pleistocene–Holocene eruptive activity, which has been characterized by recurrent Plinian eruptions of large magnitude, the last two of which destroyed human settlements in pre-Hispanic times. Popocatépetl’s reawakening in 1994 produced a crisis that culminated with the evacuation of two villages on the northeastern flank of the volcano. Shortly after, a monitoring system and a civil protection contingency plan based on a hazard zone map were implemented. The current volcanic hazards map considers the potential occurrence of different volcanic phenomena, including pyroclastic density currents and lahars. However, no quantitative assessment of the tephra hazard, especially related to atmospheric dispersal, has been performed. The presence of airborne volcanic ash at low and jet-cruise atmospheric levels compromises the safety of aircraft operations and forces re-routing of aircraft to prevent encounters with volcanic ash clouds. Given the high number of important airports in the surroundings of Popocatépetl volcano and considering the potential threat posed to civil aviation in Mexico and adjacent regions in case of a Plinian eruption, a hazard assessment for tephra dispersal is required. In this work, we present the first probabilistic tephra dispersal hazard assessment for Popocatépetl volcano. We compute probabilistic hazard maps for critical thresholds of airborne ash concentrations at different flight levels, corresponding to the situation defined in Europe during 2010, and still under discussion. Tephra dispersal mode is performed using the FALL3D numerical model. Probabilistic hazard maps are built for a Plinian eruptive scenario defined on the basis of geological field data for the “Ochre Pumice” Plinian eruption (4965 14 C yr BP). FALL3D model input eruptive parameters are constrained through an inversion method carried out with the semi-analytical HAZMAP model and are varied by sampling them using probability density functions. We analyze the influence of seasonal variations on ash dispersal and estimate the average persistence of critical ash concentrations at relevant locations and airports. This study assesses the impact that a Plinian eruption similar to the Ochre Pumice eruption would have on the main airports of Mexico and adjacent areas. The hazard maps presented here can support long-term planning that would help minimize the impacts of such an eruption on civil aviation.

Popocatépetl Volcano

Detecting temporal trends in species assemblages with bootstrapping procedures and hierarchical models

Quantifying patterns of temporal trends in species assemblages is an important analytical challenge in community ecology. We describe methods of analysis that can be applied to a matrix of counts of individuals that is organized by species (rows) and time-ordered sampling periods (columns). We first developed a bootstrapping procedure to test the null hypothesis of random sampling from a stationary species abundance distribution with temporally varying sampling probabilities. This procedure can be modified to account for undetected species. We next developed a hierarchical model to estimate species-specific trends in abundance while accounting for species-specific probabilities of detection. We analysed two long-term datasets on stream fishes and grassland insects to demonstrate these methods. For both assemblages, the bootstrap test indicated that temporal trends in abundance were more heterogeneous than expected under the null model. We used the hierarchical model to estimate trends in abundance and identified sets of species in each assemblage that were steadily increasing, decreasing or remaining constant in abundance over more than a decade of standardized annual surveys. Our methods of analysis are broadly applicable to other ecological datasets, and they represent an advance over most existing procedures, which do not incorporate effects of incomplete sampling and imperfect detection.

Philosophical Transactions of the Royal Society B:

Methods for simulating solute breakthrough curves in pumping groundwater wells

In modeling there is always a trade-off between execution time and accuracy. For gradient-based parameter estimation methods, where a simulation model is run repeatedly to populate a Jacobian (sensitivity) matrix, there exists a need for rapid simulation methods of known accuracy that can decrease execution time, and thus make the model more useful without sacrificing accuracy. Convolution-based methods can be executed rapidly for any desired input function once the residence-time distribution is known. The residence-time distribution can be calculated efficiently using particle tracking, but particle tracking can be ambiguous near a pumping well if the grid is too coarse. We present several embedded analytical expressions for improving particle tracking near a pumping well and compare them with a finely gridded finite-difference solution in terms of accuracy and CPU usage. Even though the embedded analytical approach can improve particle tracking near a well, particle methods reduce, but do not eliminate, reliance on a grid because velocity fields typically are calculated on a grid, and additional error is incurred using linear interpolation of velocity. A dilution rate can be calculated for a given grid and pumping well to determine if the grid is sufficiently refined. Embedded analytical expressions increase accuracy but add significantly to CPU usage. Structural error introduced by the numerical solution method may affect parameter estimates.

Computers & Geosciences

A novel method to characterise levels of pharmaceutical pollution in large scale aquatic monitoring campaigns

Much of the current understanding of pharmaceutical pollution in the aquatic environment is based on research conducted in Europe, North America and other select high-income nations. One reason for this geographic disparity of data globally is the high cost and analytical intensity of the research, limiting accessibility to necessary equipment. To reduce the impact of such disparities, we present a novel method to support large-scale monitoring campaigns of pharmaceuticals at different geographical scales. The approach employs the use of a miniaturised sampling and shipping approach with a high throughput and fully validated direct-injection High-Performance Liquid Chromatography-Tandem Mass Spectrometry method for the quantification of 61 active pharmaceutical ingredients (APIs) and their metabolites in tap, surface, wastewater treatment plant (WWTP) influent and WWTP effluent water collected globally. A 7-day simulated shipping and sample stability assessment was undertaken demonstrating no significant degradation over the 1–3 days which is typical for global express shipping. Linearity (r 2 ) was consistently ≥0.93 (median = 0.99 ± 0.02), relative standard deviation of intra- and inter-day repeatability and precision was <20% for 75% and 68% of the determinations made at three concentrations, respectively, and recovery from Liquid Chromatography Mass Spectrometry grade water, tap water, surface water and WWTP effluent were within an acceptable range of 60–130% for 87%, 76%, 77% and 63% of determination made at three concentrations respectively. Limits of detection and quantification were determined in all validated matrices and were consistently in the ng/L level needed for environmentally relevant API research. Independent validation of method results was obtained via an interlaboratory comparison of three surface-water samples and one WWTP effluent sample collected in North Liberty, Iowa (USA). Samples used for the interlaboratory validation were analysed at the University of York Centre of Excellence in Mass Spectrometry (York, UK) and the U.S. Geological Survey National Water Quality Laboratory in Denver (Colorado, USA). These results document the robustness of using this method on a global scale. Such application of this method would essentially eliminate the interlaboratory analytical variability typical of such large-scale datasets where multiple methods were used.

Applied Sciences

Mapping polar bear maternal denning habitat in the National Petroleum Reserve -- Alaska with an IfSAR digital terrain model

The National Petroleum Reserve–Alaska (NPR-A) in northeastern Alaska provides winter maternal denning habitat for polar bears ( Ursus maritimus ) and also has high potential for recoverable hydrocarbons. Denning polar bears exposed to human activities may abandon their dens before their young are able to survive the severity of Arctic winter weather. To ensure that wintertime petroleum activities do not threaten polar bears, managers need to know the distribution of landscape features in which maternal dens are likely to occur. Here, we present a map of potential denning habitat within the NPR-A. We used a fine-grain digital elevation model derived from Interferometric Synthetic Aperture Radar (IfSAR) to generate a map of putative denning habitat. We then tested the map’s ability to identify polar bear denning habitat on the landscape. Our final map correctly identified 82% of denning habitat estimated to be within the NPR-A. Mapped denning habitat comprised 19.7 km2 (0.1% of the study area) and was widely dispersed. Though mapping denning habitat with IfSAR data was as effective as mapping with the photogrammetric methods used for other regions of the Alaskan Arctic coastal plain, the use of GIS to analyze IfSAR data allowed greater objectivity and flexibility with less manual labor. Analytical advantages and performance equivalent to that of manual cartographic methods suggest that the use of IfSAR data to identify polar bear maternal denning habitat is a better management tool in the NPR-A and wherever such data may be available.

Alaska