Study of the voltammetric behaviour of the ethalfluralin and methalpropalin and its determination in environmental matrices at hanging mercury drop electrode

An electroanalytical method has been developed for the determination of the herbicides ethalfluralin[N-ethyl-N-(2-methyl-2-propenyl)-2,6-dinitro-4-(trifluoromethyl) bezenamine] and methalpropalin [N-(2-methyl-2-propenyl)-2, 6-dinitro-N-propyl-4 (trifluoromethyl) benzenamine] by differential pulse adsorptive stripping voltammetry (DP-AdSV) on a hanging mercury drop electrode (HMDE) with universal buffer as supporting electrolyte. The optimum adsorption conditions were found to be pH 6.0, an accumulation potential of -0.6 V (HMDE vs SCE), an accumulation time of 80 s. and scan rate 45 mVs(-1). Calibration curve is linear in the range 1.30 x 10(-9) to 1.32 x 10(-5) M of ethalfluralin and 1.13 x 10(-5) to 2.0 x 10(-8) M of methalpropalin with detection limits of 1.08 x 10(-9) and 1.87 x 10(-8) M, respectively. The relative SD and correlation coefficients were found to be 1.24%, 0.998 and 1.34%, 0.995, respectively for ten replicates. The method is applied to the determination of the ethalfluralin and methalpropalin in formulations and environmental matrices.     

Use of denuder/filter apparatus to investigate terpene ozonolysis

A denuder/filter apparatus was used to collect the gaseous and particulate reaction products from ozonlysis of α-pinene, limonene and α-terpineol in an effort to develop sampling techniques for characterizing indoor environment chemistry. Carboxylic acids found in the particulate phase were derivatized to 2,2,2-trifuoroethylamides by reaction with 3-ethyl-1-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA). Carbonyl compounds collected in both gas phase and particulate phase were derivatized to their respective oximes by reaction with O-(2,3,4,5,6-pentafluoro-benzyl)hydroxylamine hydrochloride (PFBHA). The ozonolysis of α-pinene yielded the carboxylic acids: cis-pinonic acid and pinic acid and the proposed carboxylic acids methanetricarboxylic acid and terpenylic acid; the carbonyls: 4-oxopentanal, norpinonaldehyde, pinon aldehyde and the proposed carbonyl methylidenepropanedial. The ozonolysis of limonene yielded the carboxylic acids: limonic acid and pinic acid and the carbonyls: 1-(4-methylcyclohex-3-en-1-yl)ethanone (4AMCH), glyoxal, methyl glyoxal, 4-oxopentanal and 6-oxo-3-(prop-1-en-2-yl)heptanal (IPOH). The ozonolysis of α-terpineol yielded the proposed carboxylic acids: terpenylic acid and homoterpenylic acid and the carbonyls: (5E)-6-hydroxyhept-5-en-2-one, methyl glyoxal and 4-oxopentanal.     

Tradeoffs between soil, water, and carbon -- a national scale analysis from New Zealand

The tradeoffs between the regulation of soil erosion, provision of fresh water, and climate regulation associated with new Pinus radiata forests in New Zealand are explored using national models. These three ecosystem services for which there is strong demand are monetised as commodities (avoided soil erosion is NZ $1 per tonne; water is NZ $1 per cubic metre; and sequestered carbon is assumed to be NZ?$73 per tonne). This permits their summation on a spatial basis to produce a national map of the net benefit of these ecosystem services. Net benefit is spatially variable depending primarily on the relative mix of forest growth rates and demand for irrigation water. New P.?radiata forests (once mature) generally reduce mass-movement erosion by an order of magnitude. This provides significant benefits for erosion control where there are high natural rates of erosion. Benefits are especially large in catchments where high sedimentation is increasing flood risk and degrading aquatic ecosystems. The generally high growth rates of P.?radiata in New Zealand (8.5 tonnesCha(-1)yr(-1) on average for existing forest) add significant environmental benefits of carbon sinks to climate regulation. However, the reduction of water yield associated with new forests (between 30% and 50%) can neutralise these benefits in catchments where there is demand for irrigation water, such as the eastern foothills of the Southern Alps and the tussock grasslands in the South Island.     

Local social capital and the acceptance of Protected Area policies: an empirical study of two Ramsar river delta ecosystems in northern Greece

Managing Protected Areas (PAs) is a challenging task, and globally many instruments have been utilised for this purpose. Existing research demonstrates that the effectiveness of these instruments is highly dependent on their social acceptability among local communities resident within PAs. Consequently, investigating local attitudes and perceptions of Protected Area (PA) policies has been emphasised in recent studies. Drawing on empirical work conducted in two National Parks including river delta ecosystems designated as Ramsar wetlands in northern Greece, this paper examines local residents' perceptions of three hypothesized policy options (regulatory, market-based and participatory) for Park management. The influence of social capital elements (social trust, institutional trust and social networks) on residents' perceptions is explored. The findings reveal a high degree of importance attached by resident communities to Park designation in both PAs, though residents' perceptions of the proposed management options varied. The regulatory option was regarded as the least restrictive, while the most restrictive was perceived to be the market-based option. However, greater benefits were identified by residents from the market-based option, while the fewest benefits were considered to arise from the proposed regulatory option. Furthermore, local residents' perceptions were significantly shaped by the proposed management and decision-making structure offered under each policy option. The influence of different social capital elements on residents' perceptions also varied in the study sample, with social trust and institutional trust positively correlated with the benefits that were perceived to arise from the different policy options. Moreover, when social capital was measured as an aggregate indicator at the level of the individual, it was positively correlated with perceived environmental benefits.     

Estimation of daily intake of potentially toxic elements from urban street dust and the role of oral bioaccessibility testing

The pseudo-total and oral bioaccessible concentration of six potentially toxic elements (PTEs) in urban street dust was investigated. Typical pseudo-total concentrations across the sampling sites ranged from 4.4 to 8.6 mg kg⁻¹ for As, 0.2-3.6 mg kg⁻¹ for Cd, 25-217 mg kg⁻¹ for Cu, 14-46 mg kg⁻¹ for Ni, 70-4261 mg kg⁻¹ for Pb, and, 111-652 mg kg⁻¹ for Zn. This data compared favourably with other urban street dust samples collected and analysed in a variety of cities globally; the exception was the high level of Pb determined in a specific sample in this study. The oral bioaccessibility of PTEs in street dust is also assessed using in vitro gastrointestinal extraction (Unified Bioaccessibility Method, UBM). Based on a worst case scenario the oral bioaccessibility data estimated that Cd and Zn had the highest % bioaccessible fractions (median >45%) while the other PTEs i.e. As, Cu, Ni and Pb had lower % bioaccessible fractions (median <35%). The pseudo-total and bioaccessible concentrations of PTEs in the samples has been compared to estimated tolerable daily intake values based on unintentional soil/dust consumption. Cadmium, Cu and Ni are well within the oral tolerable daily intake rates. With respect to As and Pb, only the latter exceeds the TDI_oral if we model ingestion rate based on atmospheric ‘dustiness’ rather than the US EPA (2008) unintentional soil/dust consumption rate of 100 mg d⁻¹. We consider it unlikely that even a child with pica tendencies would ingest as much as 100 mg soil/dust during a daily visit to the city centre, and in particular to the sites with elevated Pb concentrations observed in this study.     

Breakthrough indicator for aromatic VOCs using needle trap samplers for activated carbon adsorbent

Internal circulation cabinets equipped with granular activated carbon (GAC) for adsorbing volatile organic compounds (VOCs) are widely used to store bottles containing organic solvents in universities, colleges, and hospital laboratories throughout Taiwan. This work evaluates the VOC adsorption capacities of GAC using various adsorption times for gas stream mixtures of 100 ppm toluene and 100 ppm o-xylene. Additionally, needle trap sampling (NTS) technology was used to indicate the time for renewing the GAC to avoid VOC breakthrough from adsorbents. Experimental results demonstrate that the proposed models can linearly express toluene and o-xylene adsorption capacities as the natural logarithm of adsorption time (ln(t)) and can accurately simulate the equilibrium adsorption capacities (Qe, g VOCs/g GAC) for gaseous toluene and o-xylene. The NTS, packed with 60-80 mesh divinylbenzene (DVB) particles, was compared in terms of extraction efficiency by simultaneously using the 75-microm Carboxen/polydimethylsiloxane-solid-phase microextraction (Carboxen/PDMS-SPME) fiber for time-weighted average (TWA) sampling, and experimental results indicated that the packed DVB-NTS achieved higher toluene extraction rates. Additionally, the NTS installed in the outlet air stream for adsorbing toluene and o-xylene exhausted through GAC accurately indicated toluene and o-xylene breakthrough times of 4700-5000 min. The GAC-NTS operational instructions to indicate the replacing time of adsorbent in the internal circulation cabinets are also included in this paper.     

Windsor, Ontario exposure assessment study: design and methods validation of personal, indoor, and outdoor air pollution monitoring

The Windsor, Ontario Exposure Assessment Study evaluated the contribution of ambient air pollutants to personal and indoor exposures of adults and asthmatic children living in Windsor, Ontario, Canada. In addition, the role of personal, indoor, and outdoor air pollution exposures upon asthmatic children's respiratory health was assessed. Several active and passive sampling methods were applied, or adapted, for personal, indoor, and outdoor residential monitoring of nitrogen dioxide, volatile organic compounds, particulate matter (PM; PM-2.5 pm [PM2.5] and < or =10 microm [PM10] in aerodynamic diameter), elemental carbon, ultrafine particles, ozone, air exchange rates, allergens in settled dust, and particulate-associated metals. Participants completed five consecutive days of monitoring during the winter and summer of 2005 and 2006. During 2006, in addition to undertaking the air pollution measurements, asthmatic children completed respiratory health measurements (including peak flow meter tests and exhaled breath condensate) and tracked respiratory symptoms in a diary. Extensive quality assurance and quality control steps were implemented, including the collocation of instruments at the National Air Pollution Surveillance site operated by Environment Canada and at the Michigan Department of Environmental Quality site in Allen Park, Detroit, MI. During field sampling, duplicate and blank samples were also completed and these data are reported. In total, 50 adults and 51 asthmatic children were recruited to participate, resulting in 922 participant days of data. When comparing the methods used in the study with standard reference methods, field blanks were low and bias was acceptable, with most methods being within 20% of reference methods. Duplicates were typically within less than 10% of each other, indicating that study results can be used with confidence. This paper covers study design, recruitment, methodology, time activity diary, surveys, and quality assurance and control results for the different methods used.     

Impact of silver nanoparticles on natural marine biofilm bacteria

There has been a recent increase in the use of silver nanoparticles (Ag NPs) in a wide range of consumer products due to their highly effective antimicrobial properties. However, Ag NPs give cause for concern since their wide use makes them likely to be released into aquatic ecosystems and potentially affect natural bacterial communities. In this study marine biofilms were grown in situ in a coastal site (Singapore Harbour) and exposed in the laboratory for a further 24 h to 0-2000 μg L⁻¹ of well characterised Ag NPs. Increasing concentrations of Ag NPs caused a significant decrease in biofilm volume and biomass, and Ag uptake by biofilms per unit of volume was also dependent on concentration. Terminal fragment length polymorphisms and subsequent cluster and phylogenetic analysis showed the presence of major bacterial groups in biofilms irrespective of treatment with Ag NPs. This implies that even at the highest concentrations studied these taxonomic groups were not displaced. Nevertheless, biofilm succession was impeded on Ag NP treated biofilms, affecting the relative abundance of major bacterial groups in the biofilm community, with potential longer term effects on biofilm development and function.     

(210)Pb and composition data of near-surface sediments and interstitial waters evidencing anthropogenic inputs in Amazon River mouth, Macapá, Brazil

Activity profiles of excess ²¹⁰Pb determined in three sediment cores from Amazon River mouth, Macapá city, Brazil, provided the evaluation of sedimentation rates, contributing to a better knowledge of the hydrological conditions in the site that is the capital of Amapá State and is drained by the waters of the huge Amazon River. Chemical data were also determined in the sediments, allowing identify signatures coupled to anthropogenic inputs held in the past in Amapá State. Significant direct relationships between LOI (loss on ignition) and organic matter were found for all sediments profiles. Silica was found to be inversely related to organic matter in the three profiles; its decrease accompanied an increase on the specific surface of the sediments. This relationship was confirmed by a great number of inverse significant correlations among silica and oxides Na₂O, K₂O, CaO, MgO, Al₂O₃, P₂O₅, Fe₂O₃ and MnO. It was possible to identify the role of organic matter on adsorption of several oxides in the core sediments profiles. Apparent sediment mass accumulation rates corresponding to values between 450 and 2510 mg cm⁻² yr⁻¹ were obtained, and are compatible with the results of others studies. The ²¹⁰Pb activities in one sampling point suggested the occurrence of anthropogenic inputs related to the initial period of the mining activities conducted in Serra do Navio, Amapá State, for the commercialization of Mn ores. This was reinforced by the abrupt fluctuations in chemical data obtained for the sediments and composition of the interstitial waters occurring there. The Atlantic hurricane activity also appeared to affect the sedimentation rates in the area, as two different values were recorded in each profile.     

Management Implications of the Response of Two Tilapiine Cichlids to Long-Term Changes in Lake Level,Allodiversity and Exploitation in an Equatorial Lake

The tilapiine cichlids Oreochromis leucostictus and Tilapia zillii were introduced into Lake Naivasha, Kenya, in 1956. Previous studies on data collected to 1987 revealed they were persistent following establishment, despite environmental variability and exploitation. Recent data, however, suggest this persistence is under threat as data indicate some significant declines in aspects of their abundance since 1999. The influence of changes in lake level, allodiversity and fishing effort on this decline was tested and showed that a decline in lake level was a significant causal factor. The recent change in allodiversity, with the establishment and dominance of Cyprinus carpio in the fishery, was not significant on the catch per unit effort of O. leucostictus but was on T. zillii. Since 1999, catches of tilapiines in the fishery have been independent of fishing effort, contrary to between 1975 and 1987, suggesting their management through application of fishery models may no longer be applicable. As it was anthropogenic-mediated lake level changes that were mainly responsible for their decline, then lake management should focus on sustainable water utilization that maximizes lake levels in accordance with the basin-wide water balance.