The determination of trace metal pollutants in environmental matrices using ion chromatography

A review is presented detailing the development of ion chromatography (IC) as a selective analytical tool for the determination of toxic metals and their organic species in many environmental sample matrices. A brief outline of ion chromatographic principles, together with an overview of the stationary phases used to separate metals, namely ion exchangers, modified ion pair sorbents and chelating ion exchangers, and the methods for detecting metal ions including hyphenation with spectroscopy and sample preparation schemes are also given, prior to a critical examination of developed methods for various metals including arsenic, chromium, cadmium, lead, mercury, beryllium, aluminium and uranium since 1990.     

Mitigating Greenhouse Gas Emissions from Tropical Agriculture: Scope and Research Priorities

The scope of mitigation options in tropical agriculture is discussed for three different activities (a) agroforestry, (b) rice-based production systems and (c) pasture/animal husbandry. The prevention of deforestation - and the re-forestation of degraded land - could become a key elements to national climate protection programs of some developing countries. Agroforestry may offer economically viable windows of opportunity for sustainable use of tropical forests whereas additional funds (e.g. through “Clean Development Mechanism”) will be required to make re-forestation programs profitable. Alternative management practices in rice-based systems may offer win-win options to reduce emissions and - at the same time - to obtain another improvement in the production system, namely through optimized timing of nitrogen fertilizer, temporary drainage in irrigated rice fields and integrated residue management. Introducing pasture in degraded land can sequester substantial amounts of carbon (similar to re-forestation). Future research has to include participation of stakeholders from all conceivable levels, i.e. farmers' cooperatives, non-governmental organizations, national agricultural research centers and extension services, to devise simple and financially interesting incentives for reducing emissions. The feasibility of environmentally friendly production techniques has to be disseminated to the public through ‘success stories’ (documented in public media) and demonstration farms.     

UVR-induced photoinhibition of summer marine phytoplankton communities from Patagonia

During austral summer 2006, experiments were carried out to evaluate the effects of ultraviolet radiation (UVR, 280–400 nm) on carbon fixation of natural phytoplankton assemblages from Patagonia (Argentina). Surface water samples were collected (ca. 100 m offshore) at mid morning using an acid-cleaned (1 N HCl) dark container. The short-term impact of UVR (measured as radiocarbon incorporation) was immediately assessed by exposing samples to three artificial illumination treatments: PAR (400–700 nm), PAR + UV-A (320–700 nm), and PAR + UV-A + UV-B (280–700 nm). Pico-nanoplankton characterized the assemblages, and taxon-specific pigment fingerprinting combined with CHEMTAX and supplemented with microscopic observations showed varied proportions of diatoms, chlorophytes, and cyanobacteria throughout January–February 2006. Photosynthetic efficiency, as assessed through assimilation numbers, was high [between 4.4 and 10.4 μg C (μg chl-a)⁻¹ h⁻¹], and it was probably favored by the supply of inorganic nutrients from the Chubut River. UVR-induced photoinhibition appeared to be related to the taxonomic composition: in general, higher photoinhibition was observed when diatoms dominated, whereas this was lower when samples were dominated by chlorophytes. Our data suggest that xanthophyll pigments might have provided only limited protection in these already highlighted acclimated assemblages.     

Perfluorinated acids as novel chemical tracers of global circulation of ocean waters

Perfluorinated acids (PFAs) such as perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are global environmental contaminants. The physicochemical properties of PFAs are unique in that they have high water solubilities despite the low reactivity of carbon-fluorine bond, which also imparts high stability in the environment. Because of the high water solubilities, the open-ocean water column is suggested to be the final sink for PFOS and PFOA. However, little is known on the distribution of PFAs in the oceans around the world. Here we describe the horizontal (spatial) and vertical distribution of PFAs in ocean waters worldwide. PFOS and PFOA concentrations in the North Atlantic Ocean ranged from 8.6 to 36pg l(-1) and from 52 to 338pg l(-1), respectively, whereas the corresponding concentrations in the Mid Atlantic Ocean were 13-73pg l(-1) and 67-439pg l(-1). These were completely different from the surface waters of the South Pacific Ocean and the Indian Ocean (overall range of <5-11pg l(-1) for PFOS and PFOA). Vertical profiles of PFAs in the marine water column were associated with the global ocean circulation theory. Vertical profiles of PFAs in water columns from the Labrador Sea reflected the influx of the North Atlantic Current in surface waters, the Labrador Current in subsurface waters, and the Denmark Strait Overflow Water in deep layers below 2000m. Striking differences in the vertical and spatial distribution of PFAs, depending on the oceans, suggest that these persistent acids can serve as useful chemical tracers to allow us to study oceanic transportation by major water currents. The results provide evidence that PFA concentrations and profiles in the oceans adhere to a pattern consistent with the global "Broecker's Conveyor Belt" theory of open ocean water circulation.     

Future agriculture with minimized phosphorus losses to waters: Research needs and direction

The series of papers in this issue of AMBIO represent technical presentations made at the 7th International Phosphorus Workshop (IPW7), held in September, 2013 in Uppsala, Sweden. At that meeting, the 150 delegates were involved in round table discussions on major, predetermined themes facing the management of agricultural phosphorus (P) for optimum production goals with minimal water quality impairment. The six themes were (1) P management in a changing world; (2) transport pathways of P from soil to water; (3) monitoring, modeling, and communication; (4) importance of manure and agricultural production systems for P management; (5) identification of appropriate mitigation measures for reduction of P loss; and (6) implementation of mitigation strategies to reduce P loss. This paper details the major challenges and research needs that were identified for each theme and identifies a future roadmap for catchment management that cost-effectively minimizes P loss from agricultural activities.     

Determination of fluoroquinolone antibiotics in wastewater effluents by liquid chromatography-mass spectrometry and fluorescence detection

The occurrence of quinolone antibiotics (QAs) was investigated in wastewater effluents and surface river/lake waters in the US and Canada by using solid-phase extraction with mixed phase cation exchange disk cartridge and liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography fluorescence detection (LC-FLD). Ofloxacin (OFL) was detected in secondary and final effluents of a wastewater treatment plant (WWTP) in East Lansing, Michigan, at concentrations of 204 and 100 ng/l, respectively. The mass flow calculation, estimated by multiplying the OFL concentration in the final effluent by the average influent volume of the WWTP, showed that the discharge of OFL to the river was 4.8 g/day. The OFL concentrations in wastewater effluents measured in this study are comparable to or less than those observed in several European countries. QAs were not detected in river and lake waters analyzed in this study, which may due to dilution effects and to the higher detection limits, relative to those reported previously. OFL concentrations were approximately 1-2 orders of magnitude lower than the EC50 concentrations for environmental bacterium. However, greater concentrations of other QAs in sewage sludge from WWTPs may result in cumulative effects. Considering that the sewage sludge is applied to the land as fertilizers, soil-dwelling organisms could experience greater exposures to such antibiotics. Monitoring studies of QAs in sewage from WWTPs and in sediment/soil near aquaculture facilities and livestock farms will be necessary for the evaluation of the environmental distribution and risk of these compounds.     

Total mercury determination in sand boxes from Montreal

Direct mercury analysis was successfully applied to determine trace levels of total mercury in samples from sand boxes in Montréal (Québec, Canada). Twenty sand boxes were sampled from across the city and divided into two size fractions, a fine fraction (<100 microm) and a whole fraction. The concentrations of mercury ranged from 1.6 to 35 microg Hg kg(-1) dry soil for the fine fraction and from 0.7 to 6 microg Hg kg(-1) dry soil for the whole fraction. The mercury concentrations correlated with the soil organic carbon content (R2= 0.67) in the sand. The ratio of the concentration of mercury in the fine over the whole fraction varied from 2.2 to 18. Using published soil ingestion rates for children, the calculated daily intake values varied from 0 to 0.5 ng Hg kg(-1) bw d(-1) with an estimated oral ingestion of 200 mg of sand and from 0.2 to 4.7 ng Hg kg(-1) bw d(-1) with an ingestion of 1750 mg of sand. None of the sand boxes contain sufficient amounts of mercury so as to exceed the currently accepted daily intake threshold of 0.105 microg Hg kg(-1) bw d(-1) established by Health Canada.     

Framework for improved confidence in modeled nitrous oxide estimates for biofuel regulatory standards

Biofuels vary greatly in their carbon intensity, depending on the specifics of how they are produced. Policy frameworks are needed to ensure that biofuels actually achieve intended reductions in greenhouse gas emissions. Current approaches do not account for important variables during cultivation that influence emissions. Estimating emissions based on biogeochemical models would allow accounting of farm-specific conditions, which in turn provides an incentive for producers to adopt low emissions practices. However, there are substantial uncertainties in the application of biogeochemical models. This paper proposes a policy framework that manages this uncertainty while retaining the ability of the models to account for (and hence incentivize) low emissions practices. The proposed framework is demonstrated on nitrous oxide (N₂O) emissions from the cultivation of winter barley. The framework aggregates uncertainties over time, which (1) avoids penalizing producers for uncertainty in weather, (2) allows for a high degree of confidence in the emissions reductions achieved, and (3) attenuates the uncertainty penalties borne by producers within a timescale of several years. Results indicate that with effective management, N₂O emissions from feedstock cultivation may be <?5% of the carbon intensity of gasoline, whereas the existing policy approach estimates emissions >?20% of the carbon intensity of gasoline. If these emissions reductions are monetized, the framework can provide up to $0.002 per liter credits (0.8 cents per gallon) to fuel producers, which could incentivize emissions mitigation practices by biofuel feedstock suppliers, such as avoiding fall N application on silty clay loam soils. The conservatism in the current approach fails to incentivize the adoption of biofuels, while the lack of specificity fails to incentivize site-level mitigation practices. Improved uncertainty accounting and consideration of farm-level practices will incentivize mitigation efforts at landscape to global scales.