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Analysis of low molecular mass organic acids in natural waters by ion exclusion chromatography tandem mass spectrometry
Mid Sweden University, Faculty of Science, Technology and Media, Department of Natural Sciences.ORCID iD: 0000-0002-3646-294X
Mid Sweden University, Faculty of Science, Technology and Media, Department of Natural Sciences.
Mid Sweden University, Faculty of Science, Technology and Media, Department of Natural Sciences.
Mid Sweden University, Faculty of Science, Technology and Media, Department of Natural Sciences.
Responsible organisation
2007 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1176, no 1-2, 89-93 p.Article in journal (Refereed) Published
Abstract [en]

A sensitive and selective method for the analysis of aliphatic low molecular mass organic acids (LMMOAs) in natural waters is presented. The method is based on separation with ion exclusion chromatography and detection with electrospray ionization tandem mass spectrometry (LC-MS/MS). The extra selectivity gained by applying MS/MS allows for a minimum of sample preparation and the use of a sub-optimal mobile phase regarding chromatographic resolution. Instead the mobile phase, comprising aqueous formic acid With methanol as organic modifier, was mainly optimized for maximum sensitivity and long term MS stability. Detection limits for malonic, fumaric, maleic, succinic, citraconic, glutaric, malic, alpha-ketoglutaric, tartaric, shikimic, trans-aconitic, cis-aconitic, isocitric and citric acid were in the range 1-50 nM, while the detection limits for pyruvic, oxalic and lactic acid were around 250 nM for an injection volume of 100 mu L. Due to their metal-chelating properties, these LMMOAs are all considered to affect the bioavailability of metals and to be involved in soil forming processes. It is thus of interest to be able to monitor their presence in natural waters, and the method developed within this work was successfully applied for the analysis of LMMOAs in soil solution and stream water samples.

Place, publisher, year, edition, pages
2007. Vol. 1176, no 1-2, 89-93 p.
Keyword [en]
chromatography, mass spectrometry, organic acids, soil solution, stream water
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:miun:diva-3639DOI: 10.1016/j.chroma.2007.10.064ISI: 000251848100011Scopus ID: 2-s2.0-36549056005Local ID: 5315OAI: oai:DiVA.org:miun-3639DiVA: diva2:28671
Available from: 2008-12-09 Created: 2008-12-09 Last updated: 2016-09-26Bibliographically approved
In thesis
1. Soil and stream water chemistry in a boreal catchment - interactions, influences of dissolved organic matter and effects of wood ash application
Open this publication in new window or tab >>Soil and stream water chemistry in a boreal catchment - interactions, influences of dissolved organic matter and effects of wood ash application
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Two small bordering catchments in Bispgården, Central Sweden, wereinvestigated in regard to soil solution and stream water chemistry during the frostfree seasons of 2003-2007. Both catchments were drained by first order streams,Fanbergsbäcken and Gråbergsbäcken, and in Fanbergsbäckens catchment anextensive investigation of the soil and soil solution chemistry was conducted bylysimeter and centrifugation sampling. The area of intensive soil solutioninvestigation was situated in a slope towards a stream incorporating a rechargearea, with podzolic soil, and a discharge area close to the stream with an arenosolsoil. Samples were continuously taken in both the recharge- and the discharge areaof the slope, and stream water was sampled in the streams of both catchments. Themain variables of interest of the study were the interactions, the influence ofdissolved organic carbon and the effects of wood ash application to soil solutionand stream water.The natural variations and the interactions between soil solution and streamwater were monitored during 2003-2004. In soil solution, most of the investigatedsubstances tended to increase during the growing season, due to weathering andmicrobial degradation of biota. Ca, Mg, Al and Fe were highly associated todissolved organic carbon (DOC) throughout the catchment. The low molecularfraction of DOC seemed to have a higher impact on the soil processes in therecharge area, while high molecular DOC was more important for transport ofcations in the discharge area and the stream water.The concentration of different substances in the two streams differedsignificantly, even though the catchments were similar in size, shape andforestation. The seasonal patterns of most of the substances measured weresignificantly correlated between the streams, however. Cations and pH correlatedwell with DOC and flow. The flow pattern driven by precipitation seems to be thedriver of the stream water chemistry.Wood ash was applied at a dosage of 3 ton/ha to one of the catchments in theautumn of 2004, to investigate the initial effects on the soil solution- and streamwater chemistry. WAA is recommended by the Swedish Forest Agency tocounteract acidification in soil and runoff that may be caused by an intensivebiomass harvesting. The impact of the WAA was studied during 2005-2006.Compared to the control temporarily higher concentrations of K, Ca and SO4 wereobserved in the soil solution of the ashed area. In the stream water the effects of theWAA were easier to distinguish due to higher sampling frequency. The strongesteffect was seen for K, but increases in the stream water were also noted for DOC,Ca, Mg, Si, Cl and malonate. No increase in pH could be statistically verifiedhowever, and overall the initial effects of the WAA seem mild.

Abstract [sv]

Två angränsande avrinningsområden i Bispgården i centrala Sverigeundersöktes under den snöfria säsongen 2003-2006. Båda avrinningsområdenadränerades av första ordningens bäckar och i det ena, Fanbergsbäckensavrinningsområde, gjordes en omfattande undersökning av mark och markvattenkemin.Markvatten provtogs genom centrifugering och med lysimetrar.Provtagningen gjordes i inströmningsområdet där jordmånen var en typiskpodzol samt närmare bäcken, i utströmningsområdet, där jordmånen var enarenosol. Bäckvatten provtogs i båda avrinningsområdena. Interaktioner mellanmark, markvatten och bäckvatten undersöktes med särskilt fokus på inverkan avorganiskt kol samt påverkan av askåterföring.De naturliga variationerna i markkemin samt interaktionerna mellan mark- ochbäck vatten undersöktes 2003-2004. I markvatten ökade merparten av de studeradeämnena under provtagningssäsongen beroende av ökad vittring och recirkulationav biota och fallförna. Ca, Al och Fe var i stor utsträckning associerade till löstorganiskt kol (DOC). Den lågmolekylära fraktionen av DOC hade en störreinverkan på markprocesserna i inströmningsområdet, medan den högmolekyläradelen var viktigare för transport av katjoner i utströmningsområdet samt ibäckvattnet.Koncentrationsnivåerna av olika substanser i bäckarna uppvisade skillnadertrots avrinningsområdenas yttre likheter med avseende på storlek, form ochbeskogning. Trots de kvantitativa skillnaderna erhölls emellertid liknandesäsongsvariationer i koncentrationerna, vilket indikerade att kemin i huvudsakstyrdes av mängden DOC som i sin tur berodde av avrinningen som drevs avnederbörden. Höga halter av Ca, Mg, Al och Fe återfanns associerade tillhögmolekylärt DOC i bäckvattnet i en utsträckning som inte rapporterats tidigare.På hösten 2004 spreds 3 ton aska/ha till Fanbergsbäckens avrinningsområde föratt undersöka de initiala effekterna på mark- och bäckvatten kemin. Askåterföringbör ske minst en gång per omloppstid vid helträdsavverkning, i enlighet medSkogsstyrelsens rekommendationer, främst för att motverka försurning i mark ochavrinnande vatten som antas uppstå vid intensivt uttag av biomassa. De initialaeffekterna av askåterföringen på mark- och bäckvattnets kemi studerades under2005-2006 och Gråbergsbäcken kunde användas som obehandlad kontroll vidundersökning av vattenkemin i Fanbergsbäcken. I undersökningen av markvattenviåterfanns stora säsongsvariationer, vilket gjorde det svårt att urskilja eventuellaeffekter av askåterföringen. Tillfälligt högre värden av K, Ca och SO4 återfannsdock i det askade området i jämförelse med kontrollområdet. På grund av högreprovtagningsfrekvens i bäckvattnet var det lättare att påvisa förändringar ibäckvatten kemin. Framförallt märktes en signifikant ökning av K jämfört medkontrollbäcken. Sådana ökningar, om än inte lika markanta återfanns också förDOC, Ca, Mg, Si, Cl och malonat. En tendens till ökat pH kunde observeras, mendenna kunde inte verifieras statistiskt. De initiala effekterna av askåterföringen varsåledes till synes milda, och den eftertraktade pH-effekten erhölls ej i dennaundersökning.

Place, publisher, year, edition, pages
Sundsvall: Mittuniversitetet, 2010
Series
Mid Sweden University doctoral thesis, ISSN 1652-893X ; 99
Keyword
Boreal forest, catchment studies, dissolved organic carbon, soil solution
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:miun:diva-12998 (URN)978-91-86694-04-3 (ISBN)
Public defence
2010-11-26, 13:00
Supervisors
Available from: 2011-01-14 Created: 2011-01-14 Last updated: 2011-01-20Bibliographically approved

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