Stijn Baken

Metal Complexation Properties of Freshwater Dissolved Organic Matter Are Explained by Its Aromaticity and by Anthropogenic Ligands

Dissolved organic matter (DOM) in surface waters affects the fate and environmental effects of trace metals. We measured variability in the Cd, Cu, Ni, and Zn affinity of 23 DOM samples isolated by reverse osmosis from freshwaters in natural, agricultural, and urban areas. Affinities at uniform pH and ionic composition were assayed at low, environmentally relevant free Cd, Cu, Ni, and Zn activities. The C-normalized metal binding of DOM varied 4-fold (Cu) or about 10-fold (Cd, Ni, Zn) among samples. The dissolved organic carbon concentration ranged only 9-fold in the waters, illustrating that DOM quality is an equally important parameter for metal complexation as DOM quantity. The UV-absorbance of DOM explained metal affinity only for waters receiving few urban inputs, indicating that in those waters, aromatic humic substances are the dominant metal chelators. Larger metal affinities were found for DOM from waters with urban inputs. Aminopolycarboxylate ligands (mainly EDTA) were detected at concentrations up to 0.14 μM and partly explained the larger metal affinity. Nickel concentrations in these surface waters are strongly related to EDTA concentrations (R2=0.96) and this is underpinned by speciation calculations. It is concluded that metal complexation in waters with anthropogenic discharges is larger than that estimated with models that only take into account binding on humic substances.

Oxidation of iron causes removal of phosphorus and arsenic from streamwater in groundwater-fed lowland catchments

The fate of iron (Fe) may affect that of phosphorus (P) and arsenic (As) in natural waters. This study addresses the removal of Fe, P, and As from streams in lowland catchments fed by reduced, Fe-rich groundwater (average: 20 mg Fe L(-1)). The concentrations of dissolved Fe (<0.45 μm) in streams gradually decrease with increasing hydraulic residence time (travel time) of the water in the catchment. The removal of Fe from streamwater is governed by chemical reactions and hydrological processes: the oxidation of ferrous iron (Fe(II)) and the subsequent formation of particulate Fe oxyhydroxides proceeds as the water flows through the catchment into increasingly larger streams. The Fe removal exhibits first-order kinetics with a mean half-life of 12 h, a value in line with predictions by a kinetic model for Fe(II) oxidation. The Fe concentrations in streams vary seasonally: they are higher in winter than in summer, due to shorter hydraulic residence time and lower temperature in winter. The removal of P and As is much faster than that of Fe. The average concentrations of P and As in streams (42 μg P L(-1) and 1.4 μg As L(-1)) are 1 order of magnitude below those in groundwater (393 μg P L(-1) and 17 μg As L(-1)). This removal is attributed to fast sequestration by oxidizing Fe when the water enters oxic environments, possibly by adsorption on Fe oxyhydroxides or by formation of ferric phosphates. The average P and As concentrations in groundwater largely exceed local environmental limits for freshwater (140 μg P L(-1) and 3 μg As L(-1)), but in streams, they are below these limits. Naturally occurring Fe in groundwater may alleviate the environmental risk associated with P and As in the receiving streams.

Vanadium bioavailability in soils amended with blast furnace slag

Blast furnace (BF) slags are commonly applied as soil amendments and in road fill material. In Sweden they are also naturally high in vanadium. The aim of this study was to assess the vanadium bioavailability in BF slags when applied to soil. Two soils were amended with up to 29% BF slag (containing 800 mg V kg(-1)) and equilibrated outdoors for 10 months before conducting a barley shoot growth assay. Additional soil samples were spiked with dissolved vanadate(V) for which assays were conducted two weeks (freshly spiked) and 10 months (aged) after spiking. The BF slag vanadium was dominated by vanadium(III) as shown by V K-edge XANES spectroscopy. In contrast, results obtained by HPLC-ICP-MS showed that vanadium(V), the most toxic vanadium species, was predominant in the soil solution. Barley shoot growth was not affected by the BF slag additions. This was likely due to limited dissolution of vanadium from the BF slag, preventing an increase of dissolved vanadium above toxic thresholds. The difference in vanadium bioavailability among treatments was explained by the vanadium concentration in the soil solution. It was concluded that the vanadium in BF slag is sparingly available. These findings should be of importance in environmental risk assessment.

Internal Loading and Redox Cycling of Sediment Iron Explain Reactive Phosphorus Concentrations in Lowland Rivers

The phosphate quality standards in the lowland rivers of Flanders (northern Belgium) are exceeded in over 80% of the sampling sites. The factors affecting the molybdate reactive P (MRP) in these waters were analyzed using the data of the past decade (>200 000 observations). The average MRP concentration in summer exceeds that winter by factor 3. This seasonal trend is opposite to that of the dissolved oxygen (DO) and nitrate concentrations. The negative correlations between MRP and DO is marked (r = -0.89). The MRP concentrations are geographically unrelated to erosion sensitive areas, to point-source P-emissions or to riverbed sediment P concentration. Instead, MRP concentrations significantly increase with increasing sediment P/Fe concentration ratio (p < 0.01). Laboratory static sediment-water incubations with different DO and temperature treatments confirmed suspected mechanisms: at low DO in water (<4 mg L-1), reductive dissolution of ferric Fe oxides was associated with mobilization of P to the water column from sediments with a molar P/Fe ratio >0.4. In contrast, no such release was found from sediments with lower P/Fe irrespective of temperature and DO treatments. This study suggests that internal loading of the legacy P in the sediments explains the MRP concentrations which are most pronounced at low DO concentrations and in regions where the P/Fe ratio in sediment is large.

Impact of dry-wet and freeze-thaw events on pesticide mineralizing populations and their activity in wetland ecosystems: A microcosm study.

Riparian wetlands are proposed to mitigate diffuse pollution of surface water by pesticides in agricultural landscapes. Wetland ecosystems though are highly dynamic environments and seasonal disturbances such as freezing and drying can affect microbial population sizes in the sediment and their functionality including pesticide biodegradation, which has hardly been studied. This study examined the effect of artificially induced dry-wet or freeze-thaw events on the mineralization of the pesticides isoproturon (IPU) and 2-methoxy-4-chlorophenoxy acetic acid (MCPA) in wetland microcosms, either without or with prior enrichment of IPU/MCPA degrading populations. Without prior enrichment, mineralization of IPU and MCPA was significantly reduced after exposure to especially freeze-thaw events, as evidenced by lower mineralization rates and longer lag times compared to non-exposed microcosms. However, herbicide mineralization kinetics correlated poorly with cell numbers of herbicide mineralizers as estimated by a most probable number (MPN) approach and the number of IPU and MCPA mineralizers was unexpectedly higher in freeze-thaw and dry-wet cycle exposed setups compared to the control setups. This suggested that the observed effects of season-bound disturbances were due to other mechanisms than decay of pesticide mineralizers. In addition, in systems in which the growth of pesticide mineralizing bacteria was stimulated by amendment of IPU and MCPA, exposure to a freeze-thaw or dry-wet event only marginally affected the herbicide mineralization kinetics. Our results show that season bound environmental disturbances can affect pesticide mineralization kinetics in wetlands but that this effect can depend on the history of pesticide applications.