A near real-time system for continuously monitoring airborne subtilisin-type enzymes in the industrial atmosphere

We describe the development and validation of a portable system comprising an air sampler coupled to an automated flow injection analysis device. The system is able to monitor airborne concentrations of subtilisin-type enzymes in the workplace atmosphere on a continuous basis. Sampling is in two stages: using a sampling head that is designed to mimic human respiration at approx. 1 m s(-1) at a sampling rate of 600 l min(-1). In the second stage, the captured particles are deposited by impaction from the air stream onto the inner surface of a cyclone that is continuously washed with a jet of buffer solution. Deposited particles are then washed into a reservoir from which samples are taken every 5-6 min and injected automatically into a continuous flow injection analysis system. Proteolytic enzyme in the sample passes through a bioreactor maintained at about 40 degrees C. This contains a cellulose solid phase matrix on which is covalently immobilised Texas Red-labelled gelatin as substrate. The passing enzyme partially digests the substrate releasing fluorophore that is detected down stream in a flow cell coupled to a fluorimeter. The system is calibrated using enzyme standards and the intensity of the resulting peaks from the ex-air samples is converted to airborne concentrations using a mathematical model programmed into a PC. The system has a limit of detection of 4.8 ng m(-3) and a dynamic range of 5-60 ng m(-3). The within assay precision (RSD) is 6.3-9.6% over this range. The within batch precision is 20.3% at 20 ng m(-3) and the corresponding between batch value is 19.5%. The system has been run for periods up to 8 h in the laboratory and for up to 4 h at a factory site and the values obtained compared with time-averaged values obtained from a conventional Galley sampler and in-house analysis when reasonable agreement of the results was observed. The stability of the system over 21 days of continuous use with standards injected periodically was studied. Linearity was observed for all the standard plots throughout. At the end of 21 days, after a total exposure equivalent to 2395 ng ml(-1) of Savinase, the signal due to the 5.0 ng ml(-1) standard was still easily detectable.     

Preparation and evaluation of candidate certified reference materials (CRMs) for nutrients in seawater

Certified reference materials (CRMs) are an essential part of the quality assurance (QA) necessary for the reliable analytical measurement of nutrients in seawater. The CRMs currently available for these analyses are not matrix matched to marine samples. QUASIMEME routinely produces test materials for the nutrients in seawater and nutrients in estuarine water and low-salinity open water Laboratory Performance Studies (LPS) that are both homogeneous and stable. QUASIMEME, in conjunction with Eurofins Scientific, Denmark have produced two reference materials (RMs). The homogeneity testing and preliminary stability studies were carried out by QUASIMEME, and the results are presented in this article. Participants of the QUASIMEME LPS who demonstrated satisfactory long-term performance for the analysis of nutrients in seawater and nutrients in estuarine water and low-salinity open water were invited to take part in the certification exercise. Twenty laboratories returned data, a summary of which is also presented. The certification and long-term stability testing and additional data analysis were carried out by Eurofins Scientific, Denmark, and are outwith the scope of this article and not reported here. Eurofins Scientific, Denmark have marketed these RMs as part of their range of VKI Reference Materials (further information is available from eurofins@eurofins.dk).     

Analysing the sensitivity behaviour of two hydrology models

Recently, the New Morris Method has been presented as an effective sensitivity analysis tool for mathematical models. The New Morris Method estimates the sensitivity of an output parameter to a given set of input parameters (first-order effects) and the extent these parameters interact with each other (second-order effects). This method requires the specification of two parameters (runs and resolution) that control the sampling of the output parameter to determine its sensitivity to various inputs. The criteria for these parameters have been set on the analysis of a well-behaved analytical function (see Cropp and Braddock, Reliab. Eng. Syst. Saf. 78:77–83, 2002), which may not be applicable to other physical models that describe complex processes. This paper will investigate the appropriateness of the criteria from (Cropp and Braddock, 2002) and hence the effectiveness of the New Morris Method to determine the sensitivity behaviour of two hydrologic models: the Soil Erosion and Deposition System and Griffith University Representation of Urban Hydrology. In the first case, this paper will separately analyse the sensitivity of an output parameter on a set of input parameters (first- and second-order effects) for each model and discuss the physical meaning of these sensitivities. This will be followed by an investigation into the sampling criteria by exploring the convergence of the sensitivity behaviour for each model as the sampling of the parameter space is increased. By comparing these trends to the convergence behaviour from Cropp and Braddock (2002), we will determine how well the New Morris Method estimates the sensitivity for each model and whether the sampling criteria are appropriate for these models. It will be shown that the New Morris Method can provide additional insight into the functioning of these models, and that, under a different metric, the sensitivity behaviour of these models does converge confirming the sampling criteria set by Cropp and Braddock.     

Mathematical Modeling of Column and Field Dense Nonaqueous Phase Liquid Tracer Tests

Mathematical models for the simulation of dense nonaqueous phase liquid tracer tests (DTTs) in laboratory columns and in the field are developed and examined. The DTT technique is a means of estimating the quantity of dense nonaqueous phase liquid (DNAPL) in a domain of interest in an aquifer. The two-dimensional field DTT model uses the Method of Principal Directions and an asymmetrical upwind algorithm for describing advective transport. Both models include diffusion transport of tracer into and from low-permeability porous structures such as clay lenses, as well as the mass transport kinetics of partitioning tracer to and from the DNAPL droplets. The dependence of the effluent tracer concentration curves on the parameters of the models is explored, and conclusions are drawn regarding the applicability of, and several possible problems with, the DTT technique. Model results indicate that the DTT performs well at locating distributed droplets of DNAPL, but is unlikely to be useful in the assessment of pooled DNAPL.     

Assessing Landscape Condition Relative to Water Resources in the Western United States: A Strategic Approach

The Environmental Monitoring and Assessment Program (EMAP) is proposing an ambitious agenda to assess the status of streams and estuaries in a 12-State area of the western United States by the end of 2003. Additionally, EMAP is proposing to access landscape conditions as they relate to stream and estuary conditions across the west. The goal of this landscape project is to develop a landscape model that can be used to identify the relative risks of streams and estuaries to potential declines due to watershed-scale, landscape conditions across the west. To do so, requires an understanding of quantitative relationships between landscape composition and pattern metrics and parameters of stream and estuary conditions. This paper describes a strategic approach for evaluating the degree to which landscape composition and pattern influence stream and estuary condition, and the development and implementation of a spatially-distributed, landscape analysis approach.     

Monitoring Air Quality in Mountains: Designing an Effective Network

A quantitatively robust yet parsimonious air-quality monitoring network in mountainous regions requires special attention to relevant spatial and temporal scales of measurement and inference. The design of monitoring networks should focus on the objectives required by public agencies, namely: 1) determine if some threshold has been exceeded (e.g., for regulatory purposes), and 2) identify spatial patterns and temporal trends (e.g., to protect natural resources). A short-term, multi-scale assessment to quantify spatial variability in air quality is a valuable asset in designing a network, in conjunction with an evaluation of existing data and simulation-model output. A recent assessment in Washington state (USA) quantified spatial variability in tropospheric ozone distribution ranging from a single watershed to the western third of the state. Spatial and temporal coherence in ozone exposure modified by predictable elevational relationships ( 1.3 ppbv ozone per 100 m elevation gain) extends from urban areas to the crest of the Cascade Range. This suggests that a sparse network of permanent analyzers is sufficient at all spatial scales, with the option of periodic intensive measurements to validate network design. It is imperative that agencies cooperate in the design of monitoring networks in mountainous regions to optimize data collection and financial efficiencies.     

Closing the phosphorus loop in England: The spatio-temporal balance of phosphorus capture from manure versus crop demand for fertiliser

Every year 90 million tonnes of housed livestock manures are produced in the UK. This is a valuable reservoir of global phosphorus (P) and a point in the cycle where it is vulnerable to being lost from the terrestrial system. Improved manure management for the effective reuse of phosphorus is vital to simultaneously tackle a major source of water pollution and reduce our dependence on imported fertilisers. This paper quantifies, for the first time, the spatial and temporal challenges of recycling the required amount of manure P from areas of livestock production to areas of crop production in eight regions of England. The analysis shows that England has a P deficit and therefore the capacity to fully utilise the manure P on arable land, but that uneven spatial distribution of livestock poses a significant challenge to closing the P loop in agriculture. Two of the eight regions were shown to have surplus manure P, with the remaining six regions having P deficits, indicating that an annual export of 4.7 thousand tonnes P (2.8 million tonnes manure) must take place from the west to the east of the country each year to balance P supply and demand. Moreover, housed manure production peaks between October and February, requiring an excess of 23.0 thousand tonnes P (15 million tonnes manure) to be stored until it can be used for crop fertilisation from March onwards. The results demonstrate the scale of the challenge in managing manure P in an agricultural system that has separated livestock production from crop production, a pattern that is echoed throughout the developed world. To overcome the spatial and temporal challenges, a logistical system is recommended that will balance the nutrient potential (nitrogen and P content and availability) and pollution potential (eutrophication, greenhouse gas emissions, particulates and nitrous oxide from transport) for cost-effective and environmentally compatible redistribution of manure P from areas of surplus to areas of deficit, when required.     

Effects of Alien Plants on Ecosystem Structure and Functioning and Implications for Restoration: Insights from Three Degraded Sites in South African Fynbos

We investigated the type and extent of degradation at three sites on the Agulhas Plain, South Africa: an old field dominated by the alien grass Pennisetum clandestinum Pers. (kikuyu), an abandoned Eucalyptus plantation, and a natural fynbos community invaded by nitrogen fixing—Australian Acacia species. These forms of degradation are representative of many areas in the region. By identifying the nature and degree of ecosystem degradation we aimed to determine appropriate strategies for restoration in this biodiversity hotspot. Vegetation surveys were conducted at degraded sites and carefully selected reference sites. Soil-stored propagule seed banks and macro- and micro-soil nutrients were determined. Species richness, diversity and native cover under Eucalyptus were extremely low compared to the reference site and alterations of the soil nutrients were the most severe. The cover of indigenous species under Acacia did not differ significantly from that in reference sites, but species richness was lower under Acacia and soils were considerably enriched. Native species richness was much lower in the kikuyu site, but soil nutrient status was similar to the reference site. Removal of the alien species alone may be sufficient to re-initiate ecosystem recovery at the kikuyu site, whereas active restoration is required to restore functioning ecosystems dominated by native species in the Acacia thicket and the Eucalyptus plantation. To restore native plant communities we suggest burning, mulching with sawdust and sowing of native species.     

Phosphorus and nitrogen in runoff after phosphorus- or nitrogen-based manure applications

Application of beef cattle () manure based on nitrogen (N) requirements of crops has resulted in elevated concentrations of soil test phosphorus (P) in surface soils, and runoff from this cropland can contribute to eutrophication of surface waters. We conducted a 3-yr field study (2005-2007) on a Lethbridge loam soil cropped to dryland barley () in southern Alberta, Canada to evaluate the effect of annual and triennial P-based and annual N-based feedlot manure on P and N in runoff. The manure was spring applied and incorporated. There was one unamended control plot. A portable rainfall simulator was used to generate runoff in the spring of each year after recent manure incorporation, and the runoff was analyzed for total P, total dissolved P, total particulate P, dissolved reactive P, total N, total dissolved N, total particulate N, NO-N, and NH-N. Annual or triennial P-based application resulted in significantly ( ≤ 0.05) lower (by 50 to 94%) concentrations or loads of mainly dissolved P fractions in runoff for some years compared with annual N-based application, and this was related to lower rates of annual manure P applied. For example, mean dissolved reactive P concentrations in 2006 and 2007 were significantly lower for the annual P-based (0.12-0.20 mg L) than for the annual N-based application (0.24-0.48 mg L), and mean values were significantly lower for the triennial P-based (0.06-0.13 mg L) than for the annual N-based application. In contrast, other P fractions in runoff were unaffected by annual P-based application. Our findings suggested no environmental benefit of annual P-based application over triennial P-based application with respect to P and N in runoff. Similar concentrations and loads of N fractions in runoff for the P- and N-based applications indicated that shifting to a P-based application would not significantly influence N in runoff.