Nikolaos P. Nikolaidis

Arsenic removal by zero-valent iron: field, laboratory and modeling studies.

Field and laboratory studies were conducted to elucidate the design factors and mechanisms of arsenic removal from contaminated ground water using zero-valent iron. Large scale, field pilot experiments demonstrated for more than 8 months that iron filing filters can efficiently remove arsenite from aqueous solutions to levels less than 10 micro g/L. The maximum arsenic accumulation measured was 4.4 mg As/g of media. The iron filing filters leached significant quantities of iron (73% of the iron was leached). A critical design parameter of the system was found to be the hydraulic detention time of the water in the filter. TCLP analyses of the spent media indicated that the arsenic concentration in the leachate was two orders of magnitude lower than the 5mg/L of TCLP for arsenic. Spectroscopic and laboratory arsenic leaching studies (alkaline extraction and TCLP) suggest that the arsenic surface precipitate is related to sulfur. The aging process (due to the longevity of the removal mechanism) makes the precipitation process virtually irreversible. A mathematical model was developed to simulate the removal process using a partitioning coefficient and a mass transfer process. Calibration of these parameters using the data for three columns revealed that the equilibrium-partitioning coefficient was the same for all three columns while the mass transfer coefficient was a function of the flow rate. The calibrated mass transfer coefficients are similar to those reported in the literature if they are normalized to the surface area of the media.

Arsenic accumulation in irrigated agricultural soils in Northern Greece.

The accumulation of arsenic in soils and food crops due to the use of arsenic contaminated groundwater for irrigation has created worldwide concern. In the Chalkidiki prefecture in Northern Greece, groundwater As reach levels above 1000μg/L within the Nea Triglia geothermal area. While this groundwater is no longer used for drinking, it represents the sole source for irrigation. This paper provides a first assessment of the spatial extent of As accumulation and of As mobility during rainfall and irrigation periods. Arsenic content in sampled soils ranged from 20 to 513mg/kg inside to 5-66mg/kg outside the geothermal area. Around irrigation sprinklers, high As concentrations extended horizontally to distances of at least 1.5m, and to 50cm in depth. During simulated rain events in soil columns (pH=5, 0μg As/L), accumulated As was quite mobile, resulting in porewater As concentrations of 500-1500μg/L and exposing plant roots to high As(V) concentrations. In experiments with irrigation water (pH=7.5, 1500μg As/L), As was strongly retained (50.5-99.5%) by the majority of the soils. Uncontaminated soils (<30mg As/kg) kept soil porewater As concentrations to below 50μg/L. An estimated retardation factor R(f)=434 for weakly contaminated soil (<100mg/kg) indicates good ability to reduce As mobility. Highly contaminated soils (>500mg/kg) could not retain any of the added As. Invoked mechanisms affecting As mobility in those soils were adsorption on solid phases such as Fe/Mn-phases and As co-precipitation with Ca. Low As accumulation was found in collected olives (0.3-25μg/kg in flesh and 0.3-5.6μg/kg in pits). However, soil arsenic concentrations are frequently elevated to far above recommended levels and arsenic uptake in faster growing plants has to be assessed.

Mitigation measures for chromium-VI contaminated groundwater - The role of endophytic bacteria in rhizofiltration.

A constructed wetland pilot with Juncus acutus L. plants was investigated for its rhizofiltration efficiency in treating Cr(VI)-contaminated groundwater. Measurements of Cr(VI) and total Cr were performed to estimate the rate of removal. In addition, Cr concentration in plant tissues was measured and the role of endophytic bacteria on plants tolerance to Cr(VI) toxicity was investigated. The results support that J. acutus is able to rhizofiltrate Cr(VI) from contaminated water with up to 140μg/L while Cr content analysis in plant tissues revealed that the majority of Cr was accumulated by the plants. Moreover, two leaf (Acidovorax sp. strain U3 and Ralstonia sp. strain U36) isolated endophytic bacteria were found to tolerated 100mg/L Cr(VI) while nine root isolates showed resistance to 500mg/L Cr(VI). The endophytic bacteria Pseudomonas sp. strain R16 and Ochrobactrum sp. strain R24 were chosen for Cr(VI) reduction assays. All four strains exhibited a strong potential to reduce Cr(VI) to Cr(III) aerobically. Among them Pseudomonas sp. strain R16 was found able to completely reduced 100mg/L Cr(VI) after 150h of incubation. These results suggest that J. acutus is an excellent choice for CWs whose function is the removal of Cr(VI) from contaminated groundwater for subsequent use in crop irrigation.

Water and sediment transport modeling of a large temporary river basin in Greece

The objective of this research was to study the spatial distribution of runoff and sediment transport in a large Mediterranean watershed (Evrotas River Basin) consisting of temporary flow tributaries and high mountain areas and springs by focusing on the collection and use of a variety of data to constrain the model parameters and characterize hydrologic and geophysical processes at various scales. Both monthly and daily discharge data (2004-2011) and monthly sediment concentration data (2010-2011) from an extended monitoring network of 8 sites were used to calibrate and validate the Soil and Water Assessment Tool (SWAT) model. In addition flow desiccation maps showing wet and dry aquatic states obtained during a dry year were used to calibrate the simulation of low flows. Annual measurements of sediment accumulation in two reaches were used to further calibrate the sediment simulation. Model simulation of hydrology and sediment transport was in good agreement with field observations as indicated by a variety of statistical measures used to evaluate the goodness of fit. A water balance was constructed using a 12 year long (2000-2011) simulation. The average precipitation of the basin for this period was estimated to be 903 mm yr(-1). The actual evapotranspiration was 46.9% (424 mm yr(-1)), and the total water yield was 13.4% (121 mm yr(-1)). The remaining 33.4% (302 mm yr(-1)) was the amount of water that was lost through the deep groundwater of Taygetos and Parnonas Mountains to areas outside the watershed and for drinking water demands (6.3%). The results suggest that the catchment has on average significant water surplus to cover drinking water and irrigation demands. However, the situation is different during the dry years, where the majority of the reaches (85% of the river network are perennial and temporary) completely dry up as a result of the limited rainfall and the substantial water abstraction for irrigation purposes. There is a large variability in the sediment yield within the catchment with the highest annual sediment yield (3.5 t ha(-1)yr(-1)) to be generated from the western part of the watershed. The developed methodology facilitated the simulation of hydrology and sediment transport of the catchment providing consistent results and suggesting its usefulness as a tool for temporary rivers management.

Simultaneous photocatalytic oxidation of As(III) and humic acid in aqueous TiO2 suspensions

The simultaneous photocatalytic oxidation of As(III) and humic acid (HA) in aqueous Degussa P25 TiO(2) suspensions was investigated. Preliminary photocatalytic studies of the binary As(III)/TiO(2) and HA/TiO(2) systems showed that As(III) was oxidized more rapidly than HA and the extent of photocatalytic oxidation of each individual component (i.e. As(III) or HA) increased with decreasing its initial concentration and/or increasing catalyst loading. The simultaneous photocatalytic oxidation of As(III) and HA in the ternary As(III)/HA/TiO(2) system showed that both As(III) and HA oxidation was reduced in the ternary system compared to the corresponding binary systems. The effect of operating conditions in the ternary system, such as initial As(III), HA and TiO(2) concentrations (in the range 3-20mg/L, 10-100mg/L and 50-250 mg/L respectively), initial solution pH (3.6-6.7) and reaction time (10-30 min), on photocatalytic As(III) and HA oxidation was assessed implementing a two-level factorial experimental design methodology. Seven and ten factors were found statistically important in the case of photocatalytic As(III) and HA oxidation respectively. Based on these statistically significant factors, a first order polynomial model describing As(III) and HA photocatalytic oxidation was constructed and a very good agreement was obtained between the experimental values and those predicted by the model, while the observed differences may be readily explained as random noise.

Effects of Municipal Solid Waste Compost on Soil Properties and Vegetables Growth

ABSTRACT This work investigates the impact of municipal solid waste compost (MSW-compost) application (0, 50, and 100 t/ha) on the growth, and on nutrient and trace elements content in lettuce and tomato plants grown in large, 40-L pots. Our findings showed inhibition of plants’ growth with increasing dose of MSW-compost, compared to plants receiving conventional fertilization. Growth inhibition was associated with a sharp decrease in soil NO3–N content. On the other hand, a slower decrease in soil NO3–N content occurred in non-planted pots amended with MSW-compost. These findings provide evidence that N immobilization and/or decreased N mineralization were responsible for inhibited growth by constraining N availability. With regard to the other macro-nutrients, K, P, Mg, Ca, and Fe, their contents in leaves of both crops were maintained at optimum levels. Higher zinc and copper content was measured in leaves of both crops but they did not exceed the optimum range for growth. No accumulation of trace elements was found in the fruits. The content of heavy metals in the tissues of plants grown in MSW-compost amended soil, remained at levels similar to those of the non-amended soil, suggesting that they do not pose a significant risk either for plant growth or public health. The findings of our study suggest that further emphasis should be given on the investigation of the factors regulating N mineralization and availability in order to avoid reductions in crop yield.

Arsenic mobility and stabilization in topsoils.

Agricultural topsoil can be polluted with arsenic due to irrigation with contaminated water from geothermal sources. This work evaluates the mobility of arsenic in topsoils and stabilization of arsenic with zero valent iron (ZVI), in short term experiments. The objective of this study was the development of a simplified empirical model that can predict the concentration of iron released from ZVI and the concentration of arsenic remaining in the solution during short term stabilization experiments. The empirical model correlates the release of arsenic from soil with dissolved iron concentration during stabilization experiments, in different pH and ZVI/solution ratios. Reaction time and the ratio of ZVI/soil affect the efficiency of arsenic stabilization in topsoils with ZVI. In addition, the release/desorption experiments and adsorption experiments, under different conditions, showed that the concentration of arsenate desorbed from soil depends on the temperature. Higher concentrations of arsenate were reported, as the temperature increased.

Characterization and mobility of geogenic chromium in soils and river bed sediments of Asopos basin

A field and laboratory study was conducted to assess the origin and mobility of CrVI in Asopos basin in Greece. Sampling was designed in such way as to capture the spatial variability of chromium occurring in sediments and soils in different lithological units in the area. Physicochemical and geochemical characterization of surface agricultural soils obtained from river terraces and river bed sediments was conducted in order to determine the natural background of chromium. Lithologies with strong calcareous, siliceous and ultramafic components were identified using principal component analysis. Laboratory mobility studies quantified the rates of chromium sorption and release from soils and their capacity to adsorb chromium. Heavy metal analysis and local geology study support the hypothesis that the main source of chromium is of geogenic origin. Chromium distribution in Asopos river bed was influenced from the eroded products derived from extensive areas with ultramafic rocks the last 5Ma. The mobility studies showed that leaching process was very fast and sorption capacity was significant and capable to retain chromium in case of waste release in the river. Finally the mobility of chromium release is limited due to existing attenuation capacity controlled by ferric oxides coatings on the soil and sediments.

Sediment provenance, soil development, and carbon content in fluvial and manmade terraces at Koiliaris River Critical Zone Observatory

PurposeThe purpose of this study was the investigation of sediment provenance and soil formation processes within a Mediterranean watershed (Koiliaris CZO in Greece) with particular emphasis on natural and manmade terraces.Material and methodsFive sites (K1–K5) were excavated and analyzed for their pedology (profile description), geochemistry [including rare earth elements (REEs) and other trace elements], texture, and mineralogy along with chronological analysis (optical luminescence dating). The selected sites have the common characteristic of being flat terraces while the sites differed with regard to bedrock lithology, elevation, and land use.Results and discussionThree characteristic processes of soil genesis were identified: (1) sediments transportation from outcrops of metamorphic rocks and sedimentation at the fluvial sites (K1–K2), (2) in situ soil development in manmade terraces (K3, K4), and (3) strong eolian input and/or material transported by gravity from upslope at the mountainous site (K5). REE patterns verified the soil genesis processes while they revealed also soil development processes such as (a) calcite deposition (K1), (b) clay illuviation and strong weathering (K4), and (c) possibly fast oxidation/precipitation processes (K3). Carbon sequestration throughout the soil profile was high at manmade terraces at higher elevation compared to fluvial environments due to both climatic effects and possibly intensive anthropogenic impact.ConclusionsSoils at Koiliaris CZO were rather young soils with limited evolution. The different soil age, land use, and climatic effect induced various soil genesis and soil development processes. The manmade terraces at higher elevation have much higher carbon sequestration compared to the anthropogenic impacted fluvial areas.

SoilTrEC: a global initiative on critical zone research and integration

Soil is a complex natural resource that is considered non-renewable in policy frameworks, and it plays a key role in maintaining a variety of ecosystem services (ES) and life-sustaining material cycles within the Earths Critical Zone (CZ). However, currently, the ability of soil to deliver these services is being drastically reduced in many locations, and global loss of soil ecosystem services is estimated to increase each year as a result of many different threats, such as erosion and soil carbon loss. The European Union Thematic Strategy for Soil Protection alerts policy makers of the need to protect soil and proposes measures to mitigate soil degradation. In this context, the European Commission-funded research project on Soil Transformations in European Catchments (SoilTrEC) aims to quantify the processes that deliver soil ecosystem services in the Earths Critical Zone and to quantify the impacts of environmental change on key soil functions. This is achieved by integrating the research results into decision-support tools and applying methods of economic valuation to soil ecosystem services. In this paper, we provide an overview of the SoilTrEC project, its organization, partnerships and implementation.