Arsenic concentration in porewater of an alkaline coal ash disposal site: Roles of siderite precipitation/dissolution and soil cover

The geochemical behavior of As in porewaters of an alkaline coal ash disposal site was investigated using multilevel samplers. The disposal site was in operation from 1983 until 1994 and was covered with 0.3–0.5 m thick soils in 2001 when this study was initiated. Sequential extraction analyses and batch leaching experiments were also performed using the coal ash samples collected from the disposal site. The results suggest the important roles of siderite (FeCO₃) precipitation/dissolution and soil cover, which have been ignored previously. Arsenic levels in the porewater were very low (average of 10 μg L⁻¹) when the site was covered with soil due to coprecipitation with siderite. The soil cover enabled the creation of anoxic conditions, which raised the Fe concentration by the reductive dissolution of Fe-(hydr)oxides. Because of the high alkalinity generated from the alkaline coal ash, even a small increase in the Fe concentration (0.66 mg L⁻¹ on average) could cause siderite precipitation. When the soil cover was removed, however, an oxidizing condition was created and triggered the precipitation of dissolved Fe as (hydr)oxides. As a result, the dissolution of previously precipitated As-rich siderite caused higher As concentration in the porewater (average of 345 μg L⁻¹).     

An integrated approach to the toxicity assessment of Irish marine sediments: validation of established marine bioassays for the monitoring of Irish marine sediments

This paper describes the ecotoxicological evaluation of marine sediments from three sites around Ireland representative of a range of contaminant burdens. A comprehensive assessment of potential sediment toxicity requires the consideration of multiple exposure phases. In addition to the evaluation of multi-exposure phases the use of a battery of multi-trophic test species has been advocated by a number of researchers as testing of single or few organisms may not detect toxicants with a specific mode of action. The Microtox(R) solid phase test (SPT) and the 10-d acute amphipod test with Corophium volutator were used to assess whole sediment toxicity. Porewater and elutriates were assessed with the Microtox(R) acute test, the marine prasinophyte Tetraselmis suecica, and the marine copepod Tisbe battagliai. Solvent extracts were assayed with the Microtox(R) and T. battagliai acute tests. Alexandra Basin was identified as the most toxic site according to all tests, except the Microtox(R) SPT which identified the Dunmore East site as being more toxic. However, it was not possible to correlate the observed ecotoxicological effects with a specific and/or class of contaminants based on sediment chemistry alone. Therefore porewaters found to elicit significant toxicity (Dunmore East and Alexandra Basin) with the test battery were selected for further TIE assessment with T. battalgiai and the Microtox(R) system. The results of this study have important implications for risk assessment in estuarine and coastal waters in Ireland, where, at present the monitoring of sediment and water quality is predominantly reliant on chemical analysis alone.     

潮滩沉积物-水界面营养盐N、P分布及交换特征

通过2月枯季和8月洪季样品的采集、室内分析和测试,对滨岸带潮滩沉积物孔隙水中营养盐含量的分布、迁移和扩散通量进行了初步研究。结果表明,NH_4~--N和N0_3~--N的平均含量8月洪季比2月枯季低,但是NO_2-N含量在8月份却达到最高,为0.04 mg/L;TP在季节分布上变化不大,8月洪季时含量较高。在空间分布上发现,排污口及大面积围垦对营养盐局部分布的影响较大。营养盐剖面分布总体趋势为NH_4~--N含量随深度增加而增加,NO_3~--N随深度增加而减少,但同时受到沉积速率和污水排放的影响。潮滩沉积物—水界面间无机氮磷的平均扩散通量分别为7.15、-0.53μg/(cm~2·d),因此沉积物是N的输入源,P的汇。同时还发现,污染物的排放能极大地改变该地区的N、P迁移量甚至迁移方向。     

Simultaneous measurement of aqueous redox-sensitive elements and their species across the soil-water interface

The redox-sensitive elements, such as iron, manganese, sulfur, phosphorus, and arsenic, shift their speciation every millimeter (mm) across the soil-water interface in the flooded soil environments. Monitoring of element speciation at this high-resolution (HR) within the SWI is still difficult. The key challenge lies in obtaining sufficient porewater samples at specific locations along the soil gradient for downstream analysis. Here with an optimized inductively coupled plasma mass spectrometry (ICP-MS) method and a HR porewater sampler, we demonstrate mm-scale element profiles mapping across the SWI in paddy soils. High-concentrations of iron and manganese (> 10 mg/L) were measured by ICP-MS in an extended dynamic range mode to avoid signal overflow. The iron profile along the SWI generated by the ICP-MS method showed no significant difference (p < 0.05) compared to that measured independently using a colorimetric method. Furthermore, four arsenic (arsenite, arsenate, monomethylarsonic and dimethylarsinic acid), two phosphorus (phosphite and phosphate) and two sulfur (sulfide and sulfate) species were separated in 10 min by ion chromatography -ICP-MS with the NH₄HCO₃ mobile phase. We verified the technique using paddy soils collected from the field, and present the mm-scale profiles of iron, manganese, and arsenic, phosphorus, sulfur species (relative standard deviation < 8%). The technique developed in this study will significantly promote the measurement throughput in limited samples (e.g. 100 μL) collected by HR samplers, which would greatly facilitate redox-sensitive elements biogeochemical cycling in saturated soils.     

In situ measurements of concentrations of Cd, Co, Fe and Mn in estuarine porewater using DGT

Vertical profiles of metals were measured by the in situ application of DGT (diffusive gradients in thin films). Well-defined laboratory systems ensured the good reproducibility and precision DGT accumulated metals on a chelex resin after diffusional transport through a layer of hydrogel. Three kinds of DGT probes (with three thicknesses of diffusive gel: 0.40 mm, 0.80 mm and 1.92 mm) measured interfacial concentration and induced flux from solid to solution phase which had intricate variations with depth. The DGT induced flux and interfacial concentration of four metals belonged to “partially sustained” state, indicating a labile equilibrium of metals between solid phase and porewater. The concentration profiles showed the good correlation between Mn and Co and peak concentrations of Mn and Fe between −2.00 cm and −5.25 cm with depth.     

Obtaining the porewater composition of a clay rock by modeling the in- and out-diffusion of anions and cations from an in-situ experiment

A borehole in the Callovo–Oxfordian clay rock in ANDRA's underground research facility was sampled during 1 year and chemically analyzed. Diffusion between porewater and the borehole solution resulted in concentration changes which were modeled with PHREEQC's multicomponent diffusion module. In the model, the clay rock's pore space is divided in free porewater (electrically neutral) and diffuse double layer water (devoid of anions). Diffusion is calculated separately for the two domains, and individually for all the solute species while a zero-charge flux is maintained. We explain how the finite difference formulas for radial diffusion can be translated into mixing factors for solutions. Operator splitting is used to calculate advective flow and chemical reactions such as ion exchange and calcite dissolution and precipitation. The ion exchange reaction is formulated in the form of surface complexation, which allows distributing charge over the fixed sites and the diffuse double layer. The charge distribution affects pH when calcite dissolves, and modeling of the experimental data shows that about 7% of the cation exchange capacity resides in the diffuse double layer. The model calculates the observed concentration changes very well and provides an estimate of the pristine porewater composition in the clay rock.     

A model compound study: the ecotoxicological evaluation of five organic contaminants employing a battery of marine bioassays

This paper describes the ecotoxicological evaluation of five organic contaminants frequently detected in marine sediments (tributyltin, triphenyltin, benzo[a]pyrene, fluoranthene, and PCB 153) using three marine species (Vibrio fischeri, Tetraselmis suecica, and Tisbe battagliai). The sensitivity of each species varied for all compounds. The triorganotins were consistently the most toxic to all species. The applicability of each test system to assess the acute toxicity of environmental contaminants and their use in Toxicity Identification Evaluation (TIE) is discussed. Suitability of the Microtox and T. battagliai tests for employment in TIE studies were further assessed through spiking experiments with tributyltin. Results demonstrated that the most effective treatment to remove organotin toxicity from the sample was the C18 resin. The results of this study have important implications for risk assessment in estuarine and coastal waters in Ireland, where, at present the monitoring of sediment and water quality is predominantly reliant on chemical analysis alone.