Ionic liquid extraction unveils previously occluded humic-bound iron in peat soil pore water

Globally, peatland ecosystems store tremendous amounts of C relative to their extent on the landscape, largely owing to saturated soils which limit decomposition. While there is still considerable uncertainty regarding CO2 production potential below the water table in peatland ecosystems, extracellular Fe reduction has been suggested as a dominant pathway for anaerobic metabolism. However, colorimetric methods commonly used to quantitate Fe and partition between redox species are known to be unreliable in the presence of complex humic substances, which are common in peatland pore water. We evaluated both the standard o-phenanthroline (o-P) Method and an ionic liquid extraction (ILE) Method followed by quantitation with inductively coupled plasma optical emission spectrometry (ICP–OES) to compare total Fe recovery and Fe2+/Fe3+ ratios in four distinct peatland ecosystems, ranging from rich fen to bog. While total Fe concentrations measured with ILE and o-P were correlated, the ILE method proved to be superior in both total Fe quantitation and in separately quantifying ferric (Fe3+) and ferrous (Fe2+) iron. In peat pore water, the o-P Method underestimated Fe3+ by as much as 100%. A multivariate approach utilizing fluorescence- and ultraviolet (UV)–visable (Vis) spectroscopy identified indices of dissolved organic matter (DOM) humification and redox status that correlated with poor performance of the o-P Method in peat pore water. Where these interferences are present, we suggest that site-specific empirical correction factors for quantitation of total Fe by o-P can be created from ILE of Fe, but recommend ILE for accurate appraisals of iron speciation and redox processes

Summer CO2 evasion from streams and rivers in the Kolyma River basin, north-east Siberia

Inland water systems are generally supersaturated in carbon dioxide (CO2) and are increasingly recognized as playing an important role in the global carbon cycle. The Arctic may be particularly important in this respect, given the abundance of inland waters and carbon contained in Arctic soils; however, a lack of trace gas measurements from small streams in the Arctic currently limits this understanding.We investigated the spatial variability of CO2 evasion during the summer low-flow period from streams and rivers in the northern portion of the Kolyma River basin in north-eastern Siberia. To this end, partial pressure of carbon dioxide (pCO2) and gas exchange velocities (k) were measured at a diverse set of streams and rivers to calculate CO2 evasion fluxes. We combined these CO2 evasion estimates with satellite remote sensing and geographic information system techniques to calculate total areal CO2 emissions. Our results show that small streams are substantial sources of atmospheric CO2 owing to high pCO2 and k, despite being a small portion of total inland water surface area. In contrast, large rivers were generally near equilibrium with atmospheric CO2. Extrapolating our findings across the Panteleikha-Ambolikha sub-watersheds demonstrated that small streams play a major role in CO2 evasion, accounting for 86% of the total summer CO2 emissions from inland waters within these two sub-watersheds. Further expansion of these regional CO2 emission estimates across time and space will be critical to accurately quantify and understand the role of Arctic streams and rivers in the global carbon budget

Glyphosate, Other Herbicides, And Transformation Products In Midwestern Streams, 2002

The use of glyphosate has increased rapidly, and there is limited understanding of its environmental fate. The objective of this study was to document the occurrence of glyphosate and the transformation product aminomethylphosphonic acid (AMPA) in Midwestern streams and to compare their occurrence with that of more commonly measured herbicides such as acetochlor, atrazine, and metolachlor. Water samples were collected at sites on 51 streams in nine Midwestern states in 2002 during three runoff events: after the application of pre-emergence herbicides, after the application of post-emergence herbicides, and during harvest season. All samples were analyzed for glyphosate and 20 other herbicides using gas chromatography/mass spectrometry or high performance liquid chromatography/mass spectrometry. The frequency of glyphosate and AMPA detection, range of concentrations in runoff samples, and ratios of AMPA to glyphosate concentrations did not vary throughout the growing season as substantially as for other herbicides like atrazine, probably because of different seasonal use patterns. Glyphosate was detected at or above 0.1 μg/l in 35 percent of pre-emergence, 40 percent of post-emergence, and 31 percent of harvest season samples, with a maximum concentration of 8.7 μg/l. AMPA was detected at or above 0.1 μg/l in 53 percent of pre-emergence, 83 percent of post-emergence, and 73 percent of harvest season samples, with a maximum concentration of 3.6 μg/l. Glyphosate was not detected at a concentration at or above the U.S. Environmental Protection Agency’s maximum contamination level (MCL) of 700 μg/l in any sample. Atrazine was detected at or above 0.1 μg/l in 94 percent of pre-emergence, 96 percent of postemergence, and 57 percent of harvest season samples, with a maximum concentration of 55 μg/l. Atrazine was detected at or above its MCL (3 μg/l) in 57 percent of pre-emergence and 33 percent of postemergence samples

Validating epilepsy diagnoses in routinely collected data

Purpose: Anonymised, routinely-collected healthcare data is increasingly being used for epilepsy research. We validated algorithms using general practitioner (GP) primary healthcare records to identify people with epilepsy from anonymised healthcare data within the Secure Anonymised Information Linkage (SAIL) databank in Wales, UK. Method: A reference population of 150 people with definite epilepsy and 150 people without epilepsy was ascertained from hospital records and linked to records contained within SAIL (containing GP records for 2.4 million people). We used three different algorithms, using combinations of GP epilepsy diagnosis and anti-epileptic drug (AED) prescription codes, to identify the reference population. Results: Combining diagnosis and AED prescription codes had a sensitivity of 84% (95% ci 77–90) and specificity of 98% (95–100) in identifying people with epilepsy; diagnosis codes alone had a sensitivity of 86% (80–91) and a specificity of 97% (92–99); and AED prescription codes alone achieved a sensitivity of 92% (70–83) and a specificity of 73% (65–80). Using AED codes only was more accurate in children achieving a sensitivity of 88% (75–95) and specificity of 98% (88–100). Conclusion: GP epilepsy diagnosis and AED prescription codes can be confidently used to identify people with epilepsy using anonymised healthcare records in Wales, U