Temporal variation in total phosphorus concentrations revealed from a multidecadal monitoring program on Big Platte Lake,Michigan

Effective water quality management depends on enactment of appropriately designed monitoring programs to reveal current and forecasted conditions. Because water quality conditions are influenced by numerous factors, commonly measured attributes such as total phosphorus (TP) can be highly temporally varying. For highly varying processes, monitoring programs should be long-term and periodic quantitative analyses are needed so that temporal trends can be distinguished from stochastic variation, which can yield insights into potential modifications to the program. Using generalized additive mixed modeling, we assessed temporal (yearly and monthly) trends and quantified other sources of variation (daily and subsampling) in TP concentrations from a multidecadal depth-specific monitoring program on Big Platte Lake, Michigan. Yearly TP concentrations decreased from the late 1980s to late 1990s before rebounding through the early 2000s. At depths of 2.29 to 13.72 m, TP concentrations have cycled around stationary points since the early 2000s, while at the surface and depths ≥?18.29 concentrations have continued declining. Summer and fall peaks in TP concentrations were observed at most depths, with the fall peak at deeper depths occurring 1 month earlier than shallower depths. Daily sampling variation (i.e., variation within a given month and year) was greatest at shallowest and deepest depths. Variation in subsamples collected from depth-specific water samples constituted a small fraction of total variation. Based on model results, cost-saving measures to consider for the monitoring program include reducing subsampling of depth-specific concentrations and reducing the number of sampling depths given observed consistencies across the program period.     

A mass transfer model of ammonia volatilisation from anaerobic digestate

Anaerobic digestion (AD) is becoming increasingly popular for treating organic waste. The methane produced can be burned to generate electricity and the digestate, which is high in mineral nitrogen, can be used as a fertiliser. In this paper we evaluate potential losses of ammonia via volatilisation from food waste anaerobic digestate using a closed chamber system equipped with a sulphuric acid trap. Ammonia losses represent a pollution source and, over long periods could reduce the agronomic value of the digestate. Observed ammonia losses from the experimental system were linear with time. A simple non-steady-state partitioning model was developed to represent the process. After calibration, the model was able to describe the behaviour of ammonia in the digestate and in the trap very well. The average rate of volatilisation was approximately 5.2 g N m^?2 week^?1. The model was used to extrapolate the findings of the laboratory study to a number of AD storage scenarios. The simulations highlight that open storage of digestate could result in significant losses of ammonia to the atmosphere. Losses are predicted to be relatively minor from covered facilities, particularly if depth to surface area ratio is high.     

Monitoring fluvial water chemistry for trend detection: hydrological variability masks trends in datasets covering fewer than 12 years

This paper sub-samples four 35 year water quality time series to consider the potential influence of short-term hydrological variability on process inference derived from short-term monitoring data. The data comprise two time series for nitrate (NO(3)-N) and two for DOC (using water colour as a surrogate). The four catchments were selected not only because of their long records, but also because the four catchments are very different: upland and lowland, agricultural and non-agricultural. Multiple linear regression is used to identify the trend and effects of rainfall and hydrological 'memory effects' over the full 35 years, and then a moving-window technique is used to subsample the series, using window widths of between 6 and 20 years. The results suggest that analyses of periods between six and eleven years are more influenced by local hydrological variability and therefore provide misleading results about long-term trends, whereas periods of longer than twelve years tend to be more representative of underlying system behaviour. This is significant: if such methods for analysing monitoring data were used to validate changes in catchment management, a monitoring period of less than 12 years might be insufficient to demonstrate change in the underlying system.     

A modelling assessment of the atmospheric fate of volatile methyl siloxanes and their reaction products

Volatile methyl siloxanes break down in the atmosphere by reacting with OH radicals to form OH-substituted silanols. As the silanols become increasingly OH substituted they are increasingly likely to be removed from the atmosphere by wet and dry deposition. A simple equilibrium partitioning model was constructed to explore the relative rates of removal by different mechanisms (reaction vs. deposition) for siloxanes and their resultant silanols. A mass balance is calculated for the parent siloxane molecule and for each silanol, characterised by the number of OH substitutions. The model includes the effect of incomplete equilibrium between the vapour, adsorbed and dissolved phases of silanols in the atmosphere using a non-equilibrium factor (epsilon) expressing relative departure from equilibrium. Model results show: (1) maximum vapour-phase concentrations for non-substituted siloxanes and single-OH-substituted silanols; (2) maximum dissolved-phase and adsorbed-phase concentrations for two-OH-substituted silanols; (3) >99% of the original material will be removed in wet deposition and <1% in dry deposition as silanols. For increasing OH-substitutions, the decreasing concentration of precursor molecules (as a consequence of combined removal processes) means that concentrations are negligible, in all phases, beyond three or four substitutions. Predictions were relatively insensitive to assumed departures from phase equilibrium. Predictions of silanol hydrolysis in liquid water droplets suggest that the mix of diol chain lengths in precipitation may not be in thermodynamic equilibrium and will depend on atmospheric residence time and pH.     

A Molecular Genetic Assessment of Mating-System Variation in a Naturally Bird-Pollinated Shrub: Contributions from Birds and Introduced Honeybees

Abstract: Introductions of European honeybees have occurred globally, potentially affecting the natural pollination ecology of many plants. Introduced honeybees are now the most frequent visitors to the inflorescences of the self-compatible, bird-pollinated Australian shrub Grevillea macleayana and may therefore be expected to have altered the mating system. To examine the degree to which birds continue to play a role in determining the mating system of G. macleayana in this disturbed system, we compared outcrossing rates in open-pollinated inflorescences with inflorescences from which birds had been selectively excluded. Outcrossing rates were estimated from the microsatellite genotypes of over 100 seeds per population in three populations. Outcrossing rates (  t ) in open-pollinated seeds were surprisingly low (0.062–0.225) and did not vary significantly among the three populations. Nevertheless, outcrossing was significantly lower when birds were excluded (data pooled from all populations). Two lines of evidence suggest that there are temporal fluctuations in outcrossing rate and hence that birds usually have a major effect on the mating system of G. macleayana . First, at one site, t was substantially lower than estimates from an earlier study (0.06 in 1995 cf. 0.85 in 1990). Second, fixation indices based on seeds were high in all populations (  >0.68), whereas values for the established plants ( parental generation) were much lower in two of the three populations (0.06–0.32). Our findings suggest that honeybee activity is so high that the contribution of birds to pollination in G. macleayana is sometimes relatively trivial.     

A comparison of river water quality sampling methodologies under highly variable load conditions

When river water quality fluctuates over relatively short periods of time with respect to the sampling frequency, the collection of grab samples may be inappropriate for characterising average water quality. This paper presents the results of a water quality monitoring study carried out on a stretch of the river Lambro (northern Italy) dominated by a periodically overloaded sewage treatment works (STW) located near its upstream end. Water quality was strongly influenced by a pronounced diurnal cycle in pollutant loads caused by the regular emission of untreated waste water during periods of high domestic flow (daytime). Two different sampling techniques were employed: grab sampling and 24-h composite sampling using automatic samplers. Samples were collected at the plant overflow and at several sites along the river and analysed for two common ingredients of household detergents, linear alkylbenzene sulphonate (LAS) and boron (B) and for routine water quality variables. The results obtained show that: (1) The diurnal variability of point-source-derived chemical concentrations in the river downstream of the undersized STW increased with increasing removal efficiency in sewage treatment. (2) The shape of the diurnal concentration signal remained relatively intact for a considerable distance downstream of the STW for several water quality variables, suggesting that hydrodynamic dispersion plays a relatively minor role in controlling concentration patterns in this river. (3) In-stream degradation of LAS was consistent with first order kinetics with a rate constant of 0.05-0.06 h(-1). (4) Grab sampling is a relatively inefficient methodology for capturing mean concentrations for rivers subjected to highly variable loads, especially when it is restricted to office hours. The inefficiency of grab sampling is more marked for substances (e.g. LAS) which are effectively removed during sewage treatment than for substances which are not. (5) For LAS, diurnal variability in the concentration signal decreases with distance downstream, making grab sampling an increasingly reliable methodology for estimating mean concentrations. (6) 24-h composite sampling is an efficient way of eliminating the effect of diurnal variations in load strength.     

A new generic approach for estimating the concentrations of down-the-drain chemicals at catchment and national scale

A new generic approach for estimating chemical concentrations in rivers at catchment and national scales is presented. Domestic chemical loads in waste water are estimated using gridded population data. River flows are estimated by combining predicted runoff with topographically derived flow direction. Regional scale exposure is characterised by two summary statistics: PEC(works), the average concentration immediately downstream of emission points, and, PEC(area), the catchment-average chemical concentration. The method was applied to boron at national (England and Wales) and catchment (Aire-Calder) scales. Predicted concentrations were within 50% of measured mean values in the Aire-Calder catchment and in agreement with results from the GREAT-ER model. The concentration grids generated provide a picture of the spatial distribution of expected chemical concentrations at various scales, and can be used to identify areas of potentially high risk.     

Mass balance modelling of contaminants in river basins: application of the flexible matrix approach

It is useful to have available a variety of catchment-scale water quality models that range in complexity, spatial resolution and data requirements. In a previous paper [Warren, C., Mackay, D., Whelan, M., Fox, K., 2005. Mass balance modelling of contaminants in river basins: a flexible matrix approach. Chemosphere 61, 1458-1467] a series of simple to intermediately complex mass balance models was presented which can be used for tiered exposure assessments in river basins. The connectivity of the segments is expressed using a matrix that permits flexibility in application, enabling the model to be re-segmented and applied to different catchments as required. In this paper, the intermediate models, QWASI matrix-rate constant (QMX-R) and QWASI matrix-fugacity (QMX-F) are used to estimate concentrations of linear alkylbenzene sulfonates (LAS) in the rivers Aire and Calder, UK, and of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in the Fraser River basin, Canada. The results compare satisfactorily with monitoring data, suggesting that these QWASI-based models for exposure and risk assessment may be applicable under data-limited conditions. The use of QWASI-based models for regulatory purposes in an evaluative river system is also discussed with reference to assessments of para-dichlorobenzene (pDCB), trichloroethylene (TCE), bis(2-ethylhexyl) phthalate (DEHP) and toluene. It is shown that multi-media QWASI model predictions can be usefully depicted graphically on chemical space diagrams and used to highlight regions in which advection, partitioning to sediments and volatilization may be important determinants of chemical fate in river systems.     

Insectivorous birds consume an estimated 400–500 million tons of prey annually

In this paper, we present an estimate of the predation impact of the global population of insectivorous birds based on 103 (for the most part) published studies of prey consumption (kg ha^?1 season^?1) of insectivorous birds in seven biome types. By extrapolation—taking into account the global land cover of the various biomes—an estimate of the annual prey consumption of the world’s insectivorous birds was obtained. We estimate the prey biomass consumed by the world’s insectivorous birds to be somewhere between 400 and 500 million metric tons year^?1, but most likely at the lower end of this range (corresponding to an energy consumption of ≈?2.7?×?10¹⁸ J year^?1 or ≈?0.15% of the global terrestrial net primary production). Birds in forests account for >?70% of the global annual prey consumption of insectivorous birds (≥?300 million tons year^?1), whereas birds in other biomes (savannas and grasslands, croplands, deserts, and Arctic tundra) are less significant contributors (≥?100 million tons year^?1). Especially during the breeding season, when adult birds feed their nestlings protein-rich prey, large numbers of herbivorous insects (i.e., primarily in the orders Coleoptera, Diptera, Hemiptera, Hymenoptera, Lepidoptera, and Orthoptera) supplemented by spiders are captured. The estimates presented in this paper emphasize the ecological and economic importance of insectivorous birds in suppressing potentially harmful insect pests on a global scale—especially in forested areas.