The influence of sampling protocol on nonmethane hydrocarbon mixing ratios

The effect of sampling protocol on ambient air hydrocarbon mixing ratios was examined on eight sampling days in Los Angeles during 2007 and 2008. Four protocols, which were based on previously published multi-city urban hydrocarbon studies in the United States, were compared and differences were quantified. Whole air canister samples were collected and analyzed for nonmethane hydrocarbons (NMHCs). Differing sampling protocols resulted in large differences in mixing ratios, up to an order of magnitude, for certain NMHCs on the same sampling day. However, the magnitude of the variability between NMHC levels obtained by the four protocols was not consistent throughout the eight sampling days. It was found that sampling time, followed by sampling location, had the greatest influence on the magnitude of the mixing ratio. Ratios between hydrocarbons, often used in urban studies to gain information on emission sources, also varied depending on the protocol used. Comparison of absolute NMHC mixing ratios collected in urban environments using differing sampling protocols should be made with care.     

Packed in-tube solid phase microextraction with graphene oxide supported on aminopropyl silica: Determination of target triazines in water samples

On-line in-tube solid phase microextraction (in-tube SPME) coupled to high performance liquid chromatography and tandem mass spectrometry (HPLC-MS/MS) was successfully applied to the determination of selected triazines in water samples. The method based on the employment of a packed column containing graphene oxide (GO) supported on aminopropyl silica (Si) showed that the extraction phase has a high potential for triazines extraction aiming to its physical-chemical properties including ultrahigh specific surface area, good mechanical and thermal stability and high fracture strength. Injection volume and loading time were both investigated and optimized. The method validation using Si-GO to extract and concentrate the analytes showed satisfactory results, good sensitivity, good linearity (0.2–4.0 µg L^?1) and low detection limits (1.1–2.9 ng L^?1). The high extraction efficiency was determined with enrichment factors ranging from 1.2–2.9 for the lowest level, 1.3–4.9 intermediate level and 1.2–3.0 highest level (n = 3). Although the analytes were not detected in the real samples evaluated, the method has demonstrated to be efficient through its application in the analysis of spiked triazines in ground and mineral water samples.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO(4) plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO(4) plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg(-1), respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

The greening of brownfields in American cities

The redevelopment of brownfields has become a central component of government efforts to revitalize many US cities. While the focus of these efforts has concentrated on promoting industrial and commercial redevelopment, some cities have started to also consider converting brownfields into parks and open space as part of a more comprehensive renewal strategy. Based on a survey of 20 case studies, this paper identifies and discusses: (1) the primary issues involved in brownfield greening projects; (2) the benefits of such projects; and (3) the specific planning processes involved. The overall conclusion drawn from the survey is that numerous renewal‐oriented benefits can ensue from greening projects, if there is extensive stakeholder commitment devoted to deal with its financial and development‐oriented challenges.     

Tillage and field scale controls on greenhouse gas emissions

There is a lack of understanding of how associations among soil properties and management-induced changes control the variability of greenhouse gas (GHG) emissions from soil. We performed a laboratory investigation to quantify relationships between GHG emissions and soil indicators in an irrigated agricultural field under standard tillage (ST) and a field recently converted (2 yr) to no-tillage (NT). Soil cores (15-cm depth) were incubated at 25 degrees C at field moisture content and 75% water holding capacity. Principal component analysis (PCA) identified that most of the variation of the measured soil properties was related to differences in soil C and N and soil water conditions under ST, but soil texture and bulk density under NT. This trend became more apparent after irrigation. However, principal component regression (PCR) suggested that soil physical properties or total C and N were less important in controlling GHG emissions across tillage systems. The CO2 flux was more strongly determined by microbial biomass under ST and inorganic N content under NT than soil physical properties. Similarly, N2O and CH4 fluxes were predominantly controlled by NO3- content and labile C and N availability in both ST and NT soils at field moisture content, and NH4+ content after irrigation. Our study indicates that the field-scale variability of GHG emissions is controlled primarily by biochemical parameters rather than physical parameters. Differences in the availability and type of C and N sources for microbial activity as affected by tillage and irrigation develop different levels and combinations of field-scale controls on GHG emissions.     

Integrating Environmental and Socio-Economic Indicators of a Linked Catchment–Coastal System Using Variable Environmental Intensity

Can we develop land use policy that balances the conflicting views of stakeholders in a catchment while moving toward long term sustainability? Adaptive management provides a strategy for this whereby measures of catchment performance are compared against performance goals in order to progressively improve policy. However, the feedback loop of adaptive management is often slow and irreversible impacts may result before policy has been adapted. In contrast, integrated modelling of future land use policy provides rapid feedback and potentially improves the chance of avoiding unwanted collapse events. Replacing measures of catchment performance with modelled catchment performance has usually required the dynamic linking of many models, both biophysical and socio-economic—and this requires much effort in software development. As an alternative, we propose the use of variable environmental intensity (defined as the ratio of environmental impact over economic output) in a loose coupling of models to provide a sufficient level of integration while avoiding significant effort required for software development. This model construct was applied to the Motueka Catchment of New Zealand where several biophysical (riverine water quantity, sediment, E. coli faecal bacteria, trout numbers, nitrogen transport, marine productivity) models, a socio-economic (gross output, gross margin, job numbers) model, and an agent-based model were linked. An extreme set of land use scenarios (historic, present, and intensive) were applied to this modelling framework. Results suggest that the catchment is presently in a near optimal land use configuration that is unlikely to benefit from further intensification. This would quickly put stress on water quantity (at low flow) and water quality (E. coli). To date, this model evaluation is based on a theoretical test that explores the logical implications of intensification at an unlikely extreme in order to assess the implications of likely growth trajectories from present use. While this has largely been a desktop exercise, it would also be possible to use this framework to model and explore the biophysical and economic impacts of individual or collective catchment visions. We are currently investigating the use of the model in this type of application.     

Spatial and social connectivity of fish-eating “Resident” killer whales (Orcinus orca) in the northern North Pacific

The productive North Pacific waters of the Gulf of Alaska, Aleutian Islands and Bering Sea support a high density of fish-eating “Resident” type killer whales (Orcinus orca), which overlap in distribution with commercial fisheries, producing both direct and indirect interactions. To provide a spatial context for these interactions, we analyzed a 10-year dataset of 3,058 whale photo-identifications from 331 encounters within a large (linear ~4,000 km) coastal study area to investigate the ranging and social patterns of 532 individually identifiable whales photographed in more than one encounter. Although capable of large-scale movements (maximum 1,443 km), we documented ranges generally <200 km, with high site fidelity across summer sampling intervals and also re-sightings during a winter survey. Bayesian analysis of pair-wise associations identified four defined clusters, likely representing groupings of stable matrilines, with distinct ranging patterns, that combined to form a large network of associated whales that ranged across most of the study area. This provides evidence of structure within the Alaska stock of Resident killer whales, important for evaluating ecosystem and fisheries impacts. This network included whales known to depredate groundfish from longline fisheries, and we suggest that such large-scale connectivity has facilitated the spread of depredation.     

Characterizing spatial structure of sediment E. coli populations to inform sampling design

Escherichia coli can persist in streambed sediments and influence water quality monitoring programs through their resuspension into overlying waters. This study examined the spatial patterns in E. coli concentration and population structure within streambed morphological features during baseflow and following stormflow to inform sampling strategies for representative characterization of E. coli populations within a stream reach. E. coli concentrations in bed sediments were significantly different (p?=?0.002) among monitoring sites during baseflow, and significant interactive effects (p?=?0.002) occurred among monitoring sites and morphological features following stormflow. Least absolute shrinkage and selection operator (LASSO) regression revealed that water velocity and effective particle size (D ₁₀) explained E. coli concentration during baseflow, whereas sediment organic carbon, water velocity and median particle diameter (D ₅₀) were important explanatory variables following stormflow. Principle Coordinate Analysis illustrated the site-scale differences in sediment E. coli populations between disconnected stream segments. Also, E. coli populations were similar among depositional features within a reach, but differed in relation to high velocity features (e.g., riffles). Canonical correspondence analysis resolved that E. coli population structure was primarily explained by spatial (26.9–31.7 %) over environmental variables (9.2–13.1 %). Spatial autocorrelation existed among monitoring sites and morphological features for both sampling events, and gradients in mean particle diameter and water velocity influenced E. coli population structure for the baseflow and stormflow sampling events, respectively. Representative characterization of streambed E. coli requires sampling of depositional and high velocity environments to accommodate strain selectivity among these features owing to sediment and water velocity heterogeneity.