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Aquatic Geochemistry (v.6, #3)

Ammonium Photoproduction from Aquatic Humic and Colloidal Matter by Weiwei Wang; Matthew A. Tarr; Thomas S. Bianchi; Erika Engelhaupt (pp. 275-292).

It has recently been shown thatnitrogen contained in humic substances can be releasedas low molecular weight species through photochemicalprocesses or reactions. Nitrogen released in thismanner may then become available for biological useand chemical reactivity. This report providesadditional kinetic data for nitrogen photochemistry oforganic matter in natural waters from Louisiana andfor Suwannee River humic and fulvic acids. Naturalwater samples were fractionated into colloidal(>0.2 μm, <1000 Dalton) and dissolved (>1000Dalton) fractions and the kinetics of these fractionsas well as 0.2 μm filtered water samples weremeasured. For irradiations of less than 10 hours ofsimulated noon-time sun, samples showed linearproduction of ammonium and first-order fading at350 nm. Ammonium photoproduction was enhanced asmuch as three-fold by lowering pH, but linear kineticswere maintained. Light-dark cycling showed continuedrelease of ammonium immediately after irradiation,followed by uptake at longer post irradiation times.A two step mechanism was proposed to explain theobserved kinetics. Calculated net daytime release ofammonium from natural surface waters ranged from 0.33to 1.9 μM h^-1 in the samples studied,corresponding to a photic zone conversion rate of9–20% of the total organic nitrogen per day intoammonium.

Keywords: ammonium; colloids; dissolved organic nitrogen; humics; nitrogen cycling; photochemistry

The Differential Geochemical Behavior of Arsenic and Phosphorus in the Water Column and Sediments of the Saguenay Fjord Estuary, Canada by Alfonso Mucci; Louis-Filip Richard; Marc Lucotte; Constance Guignard (pp. 293-324).

The distribution and partitioning of dissolved andparticulate arsenic and phosphorus in the water columnand sediments of the Saguenay Fjord in Quebec, Canada,are compared. In addition, selective and/or sequentialextractions were carried out on the suspendedparticulate matter (SPM) and solid sediments tocontrast their geochemical behaviors in this naturalaquatic system.Results of our analyses show that both arsenic andsoluble reactive phosphate are actively scavenged fromthe water column by settling particles. Upon theiraccumulation at the sediment-water interface some Asand P may be released to porewaters following thedegradation of organic matter to which they areassociated. The porewater concentrations are, however,limited by their strong affinity for authigenic,amorphous iron oxyhydroxides which accumulate in theoxic sediments near the sediment-water interface.The geochemical behavior of arsenic and phosphorusdiverge most strikingly upon the development of anoxicconditions in the sediments. Following their burial inthe anoxic zone, amorphous iron oxyhydroxides arereduced and dissolved, releasing phosphate and arsenicto the porewaters. We observed, however, thatporewater arsenic concentrations increase at shallowerdepths than phosphate in the sediments. The reductionof arsenate, As(V), to arsenite, As(III), and itsdesorption prior to the reductive dissolution of thecarrier phase(s) may explain this observation.Driven by the strong concentration gradientestablished in the suboxic zone, phosphate diffuses uptowards the oxic layer where it is readsorbed byauthigenic iron oxyhydroxides. In the organic-rich andrapidly accumulating sediments at the head of theFjord, porewater sulfate depletion and the resultingabsence of a sulfide sink for Fe(II), may lead to theformation of vivianite in the fermentation zone, apotential sink for phosphate. Arsenite released to theporewaters in the suboxic and anoxic zones of thesediments diffuses either down, where it is adsorbedto or incorporated with authigenic iron sulfides, orup towards the oxic boundary. Arsenite appears tomigrate well into the oxic zone where it may beoxidized by authigenic manganese oxides before beingadsorbed by iron oxyhydroxides present at the samedepth. Whereas, in the absence of authigenic carbonatefluorapatite precipitation, the ability of oxicsediments to retain mineralized phosphate is afunction of their amorphous iron oxyhydroxide content,arsenic retention may depend on the availability ofmanganese oxides, the thickness of the oxic layer and,its co-precipitation with iron sulfides at depth.

Sedimentary Trace Elements as Proxies to Depositional Changes Induced by a Holocene Fresh-Brackish Water Transition by John Sternbeck; Gustav Sohlenius; Rolf O. Hallberg (pp. 325-345).

A halocline developed in the GotlandDeep, Baltic Sea, at c. 8.0 ¹⁴C ky BP, as theresult of a transition from fresh to brackish water.The sediment-water interface changed from oxic topredominantly anoxic, depositional conditions wereperiodically euxinic and pyrite formation wasextensive. This environmental change led topyritization of the upper part of earlier depositedsediments. This study discusses how the distributionof trace elements (As, Ba, Cd, Cu, Co, Mo, Mn, Ni, Pb,U, Zn and V) were affected by the changing redoxconditions, productivity and salinity. The reducingconditions led to pyritization of Cu, Co, Ni, Cd, Mo,Mn and As. Lead and Zn concentrations are very low inpyrite, in agreement with their coordination tosulfide being tetrahedral. Certain elements areenriched in those sediments deposited under euxinicconditions. This enrichment was caused by scavengingof elements dissolved in the water column and isrestricted to elements that have a comparably longresidence time in the Baltic Sea. Molybdenum appearsto be the most unambigious proxy for euxinicconditions, whereas enrichment of U also requiresbrackish water in the productive zone. In the brackishenvironment, enrichment of Ba and V are linked to thecycling of organic carbon. Manganese and As are theonly elements that have been significantly remobiliseddue to the downward moving pyritization front.

Keywords: Baltic Sea; euxinic; Holocene; pyrite; trace elements; redox conditions; sediments

Speciation of Trace Elements in Acidic PoreWaters from Waste Rock Dumps by Ultrafiltration andIon Exchange Combined with ICPMS and ICPOES by Alexander Pleßow; Hartmut Heinrichs (pp. 347-366).

A speciation procedure developed on reactive acidicpore water samples from mining areas is presented.Methods with low consumption of solution are requiredthat allow rapid sample preparation to avoid equilibriumchanges as far as possible. The entire procedure includesonly three parallel separation steps. One aliquot is filteredthrough an 1 kd ultrafiltration membrane to separate traceelements adsorbed or complexed by colloids. One cationand one anion exchange are performed with two additionalaliquots to determine simple hydrated ions and smallinorganic complex ions. Commonly used procedures ofion exchange seem to be problematic. This new techniqueis based on a novel ion exchanger. Subsequently the threefractions obtained from the separation procedures and theoriginal pore water sample are analysed by ICPMS, ICPOES,ET-AAS, Flame-AAS, FES and IC to determine the concentrationsof the major ions and additionally up to 50 trace elements. Theinfluence of pH-values and several dissolved compounds iscontrolled in experiment series with synthetically preparedsolutions to reveal potential artifacts.

Keywords: acidic mine drainage; adsorption; artifact; colloid; complex; element species; organic ligand; separation

Abundance, Sources and Speciation of Trace Elements in Humus-Rich Streams Affected by Acid Sulphate Soils by Mats Åström; Nina Corin (pp. 367-383).

The behaviour of trace elements (Al, As, Cd, Co, Cr,Cu, Fe, Mn, Ni, V, Zn) was studied in five humus-richstreams (dissolved organic carbon = 14–40 mg/L)impacted by acid sulphate soils developed in marinesulphide-bearing fine-grained sediments. During heavyrainfalls in autumn, on which the study focusses, themetals Al, Cd, Co, Cu, Mn, Ni and Zn are extensivelyleached from these acidic soils (pH = 2.5–4.5), whileAs, Cr, Fe and V are not leached more strongly fromthis soil type than from areas of till and peat. Aspeciation experiment, based on anion and cationexchange of the stream waters in the field, showedthat (1) the metals Al, Cd, Co, Mn, Ni and Zn aretransported in the streams mainly as inorganiccations, (2) Cu exists mainly in cationic form but isalso to a significant extent associated with dissolvedhumic substances, (3) Fe occurs mainly in the anionicfraction explained by organic coating on colloidal Feoxyhydoxides and (4) the hydrochemistry of As, Cr andV is complex as these elements may exist in severalunquantified anionic fractions and to a minor extentin cationic species/forms. Whereas the proportion ofacid sulphate soils in the catchments had a largeimpact on concentrations levels of several elements inthe stream waters, these soils did not have a largeaffect on the speciation of elements in water.

Keywords: acid soils; anions; cations; humus; metal; speciation; stream

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Aquatic Geochemistry (v.6, #3)

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Aquatic Geochemistry (v.6, #3)