LINKING SEDIMENT EXPOSURE WITH EFFECTS: MODELING TECHNIQUES, ORGANIC AVAILABILITY AND UPTAKE

1 INTRODUCTION Sediments are the ultimate sink for many hydrophobic contaminants and represent biologically important environmental habitats. Exposure of the sediment-associated contaminants is not only influenced by the fate and transport of sediment but also is influenced by a variety of physical, chemical, and biological processes that involve no net movement of sediments. These processes include pore water transport processes such as advection and diffusion, and sediment mixing process…     

Sediment geochemistry of the urban Lake Paulo Gorski

The objective of this study was to evaluate the concentration and distribution of heavy metals in the sediments of Paulo Gorski Lake, as well as the metals’ bioavailability and potential ecological risk, and to define the anthropogenic and natural heavy metal contributions to the lake. The chemical elements calcium (Ca), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), nickel (Ni), lead (Pb), and zinc (Zn) were quantified by flame atomic absorption spectrophotometry with two extraction methods to quantify the bioavailable and non-bioavailable fractions. The data were evaluated using multivariate statistics and sediment quality indices. All sediment collection points (S1, S2, S3, S4 and S5) are different in terms of the concentration of heavy metals, except for S4 and S5, which were statistically equal. The bioavailable fraction of the elements in the sediment follows the sequence Pb>Cu>Mn>Zn>Ni>Cr>phosphorus (P) for all points. The elements Co, Cr, Pb, and Zn showed moderate to considerable contamination at all points. Only points S3 and S5 had moderate ecological risk. Urbanization has been affecting Paulo Gorski Lake via the input of chemical elements, especially Co and Pb. The points most affected by heavy metal contamination are S3 and S5 when the sedimentological sensitivity factor is considered. The lake has high hydrodynamics, causing some of the contaminants that enter the system to leave it, leading to potential negative impacts downstream.     

土壤中砷的形态分析和生物有效性研究进展

土壤砷污染是当今全球十分严重的环境与健康问题之一。土壤砷形态及生物有效性研究是开展污染诊断、评估环境健康风险及开展砷污染土壤修复的重要依据。目前土壤砷形态的研究方法包括化学选择性提取操作定义法、溶剂提取仪器测定或吸附材料选择性分离法和同步辐射X射线近边能谱（XANES）直接测定法,这些方法相互结合在土壤砷的形态转化研究中发挥着重要作用。目前关于生物有效性研究存在多种方法并存的局面,化学提取法相对经济、方便,但存在很大的局限性,往往不能真实反映土壤砷的有效态含量,只能作为环境危害程度识别的参考;植物指示法需选择敏感性植物方能有效地指示土壤砷对环境与健康的潜在危害;土壤动物与微生物指示法代表了未来开展砷污染早期预警的发展方向,具有广阔的应用前景。模拟肠胃液提取法(In Vitro Gastrointestinal Method)比较接近动物或人体对土壤砷污染的真实吸收状态,在环境健康风险评价中发挥着重要作用。目前国外已发展出采用兔、仔猪和猴的动物模型以研究经口摄入的生物有效性砷,但尚不清楚哪种动物模型更能准确反映砷对人体的生物有效性。     

Bioremediation of Chlorinated Pesticides in Field‐Contaminated Soils and Suitability of Tenax Solid‐Phase Extraction as a Predictor of Its Effectiveness

Bioremediation is intensively studied today as a treatment method for soil contaminated with chlorinated pesticides, chemicals counted among persistent organic pollutants. In the presented work, results of desorption kinetics study using consecutive Tenax TA solid phase extraction (SPE) were tested as predictors of 3‐wk anaerobic soil bioremediation effectiveness for chlorinated pesticides γ‐HCH, DDT, and methoxychlor. Field‐contaminated samples were used in these experiments, and conditions of bioremediation tests were based on previous research. Amounts of pesticides removed during bioremediation (43–98% of initial concentrations) were in most cases much larger (average ratio 1.37) than rapidly desorbing fractions estimated in SPE using two‐compartment model of desorption kinetics. The scatter of results was also considerable (standard deviation 0.45). However, there was a statistically significant correlation between amounts removed and rapidly desorbing fractions (R² = 0.64), indicating a relationship between degradability and desorbability. Nonetheless, determination of rapidly desorbing fractions was considered rather a poor indicator of soil bioremediation efficiency for chlorinated pesticides. The total amounts of pesticides desorbed by Tenax in 72 h performed better in this respect (R² = 0.73, fraction removed/desorbed = 1.10 ± 0.20, average ± standard deviation). Disappearance of DDT during bioremediation was accompanied by DDD formation but this was considerably lower than results expected from stoichiometry.     

Seasonal variations and bioavailability of inorganic phosphorus in soils of Yeyahu Wetland in Beijing, China

Phosphorus (P) in soils has an important influence on the development and productivity of wetland. The objective of this study was to investigate the distribution, bioavailability and seasonal variations of inorganic phosphorus (IP) in soils of Yeyahu Wetland. The results showed that the concentration of Ca-bound P (Ca-P) remained the main occurrence in all IP fractions despite the season, at the same time the Al-bound P (Al-P) was always the lowest IP fraction despite the season. Al-P and Fe-bound P (Fe-P) concentration were all reached the highest value in May and the lowest in November, which was opposite to the occluded P (Oc-P) fraction. The notable higher Oc-P concentration in November observed in this study was probably due to the decomposition of plants and the subsequently releasing of oxides to soils. Ca-P didn't change much with season variations. Exchangeable P (Ex-P) and Oc-P were all positively correlated with soil moisture content and organic matter content, but Al-P was negatively correlated with these two soil properties. As a stable form, Ca-P was not associated with soil properties. Al-P, Fe-P and Ca-P might contribute to the storage of P in studied wetland with the principle component analysis results. The concentration rank order of the bio-available P in soils was generally as follows: Olsen-P > Algal available P (AAP) > Water soluble P (WSP) > Readily desorbed P (RDP). Olsen-P was positively correlated with Ex-P and Oc-P, and it was thought to be a more suitable indicator for bio-available P in soils.     

Bioavailability and bacterial degradation rates of dissolved organic matter in a temperate coastal area during an annual cycle

The bioavailability and bacterial degradation rates of dissolved organic matter (DOM) were determined over a seasonal cycle in Loch Creran (Scotland) by measuring the decrease in dissolved organic carbon (DOC), nitrogen (DON) and phosphorous (DOP) concentrations during long-term laboratory incubations (150 days) at a constant temperature of 14 °C. The experiments showed that bioavailable DOC (BDOC) accounted for 29 ± 11% of DOC (average ± SD), bioavailable DON (BDON) for 52 ± 11% of DON and bioavailable DOP (BDOP) for 88 ± 8% of DOP. The seasonal variations in DOM concentrations were mainly due to the bioavailable fraction. BDOP was degraded at a rate of 12 ± 4% d^– 1 (average ± SD) while the degradation rates of BDOC and BDON were 7 ± 2% d^– 1 and 9 ± 2% d^– 1 respectively, indicating a preferential mineralization of DOP relative to DON and of DON relative to DOC. Positive correlations between concentration and degradation rate of DOM suggested that the higher the concentration the faster DOM would be degraded. On average, 77 ± 9% of BDOP, 62 ± 14% of BDON and 49 ± 19% of BDOC were mineralized during the residence time of water in Loch Creran, showing that this coastal area exported C-rich DOM to the adjacent Firth of Lorne. Four additional degradation experiments testing the effect of varying temperature on bioavailability and degradation rates of DOM were also conducted throughout the seasonal cycle (summer, autumn, winter and spring). Apart from the standard incubations at 14 °C, additional studies at 8 °C and 18 °C were also conducted. Bioavailability did not change with temperature, but degradation rates were stimulated by increased temperature, with a Q₁₀ of 2.6 ± 1.1 for DOC and 2.5 ± 0.7 for DON (average ± SD).     

Comparison of Extraction Procedures for Assessing Soil Metal Bioavailability of to Wheat Grains

Agricultural soils have been analyzed to elucidate whether the trace metal distribution changes in relation to agricultural activities and to predict environmental risk. In addition to the extractability of Cu, Mn, Ni, Pb, and Zn in soils was compared by single extraction (hydrochloric acid (HCl), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), calcium chloride (CaCl₂), water (H₂O)), and sequential extraction procedures. The modified Community Bureau of Reference (BCR) sequential extraction procedure (three‐step) used to extraction of metals in soil samples. The extraction capacity of the analyzed metals was found by using single extraction procedures in the order: HCl > EDTA > DTPA > CaCl₂ > H₂O. A single correlation analysis was used to investigate the relationship between extractable metal concentrations in soil solutions and metal accumulation in wheat grains. Simple correlation analyses indicated that the extractable Pb and Ni of soils by HCl, EDTA, and DTPA single extraction procedures were significantly correlated with the metal contents of wheat grains. For CaCl₂, H₂O, and BCR extraction procedures there was a relatively poor correlation between the extractable Cu, Mn, Ni, Pb, and Zn of soils and metal contents of wheat grains.     

The impact of groundwater discharges on mercury partitioning, speciation and bioavailability to mussels in a coastal zone

The Mussel Watch program conducted along the French coasts for the last 20 years indicates that the highest mercury concentrations in the soft tissue of the blue mussel (Mytilus edulis) occur in animals from the eastern part of Seine Bay on the south coast of the English Channel, the “Pays de Caux”. This region is characterized by the presence of intertidal and submarine groundwater discharges, and no particular mercury effluent has been reported in its vicinity. Two groundwater emergence systems in the karstic coastal zone of the Pays de Caux (Etretat and Yport with slow and fast water percolation pathways respectively) were seasonally sampled to study mercury distribution, partitioning and speciation in water. Samples were also collected in the freshwater–seawater mixing zones in order to compare mercury concentrations and speciation between these “subterranean” or “groundwater” estuaries and the adjacent macrotidal Seine estuary, characterized by a high turbidity zone (HTZ). The mercury concentrations in the soft tissue of mussels from the same areas were monitored at the same time.The means of the “dissolved” (< 0.45 μm) mercury concentrations (HgT_D) in the groundwater springs were 0.99 ± 0.15 ng l^− 1 (n = 18) and 0.44 ± 0.17 ng l^− 1 (n = 17) at Etretat and Yport respectively. High HgT_D concentrations were associated with strong runoff over short water pathways during storm periods, while low concentrations were associated with long groundwater pathways. Mean particulate mercury concentrations were 0.22 ± 0.05 ng mg^− 1 (n = 16) and 0.16 ± 0.10 ng mg^− 1 (n = 17) at Etretat and Yport respectively, and decreased with increasing particle concentration probably as a result of dilution by particles from soil erosion. Groundwater mercury speciation was characterized by high reactive-to-total mercury ratios in the dissolved phase (HgR_D/HgT_D: 44–95%), and very low total monomethylmercury concentrations (MMHg < 8 pg l^− 1). The HgT_D distributions in the Yport and Etretat mixing zones were similar (overall mean concentration of 0.73 ± 0.21 ng l^− 1, n = 43), but higher than those measured in the adjacent industrialized Seine estuary (mean: 0.31 ± 0.11 ng l^− 1, n = 67). In the coastal waters along the Pays de Caux dissolved monomethylmercury (MMHg_D) concentrations varied from 9.5 to 13.5 pg l^− 1 (2 to 8% of the HgT_D). Comparable levels were measured in the Seine estuary (range: 12.2– 21.1 pg l⁻¹; 6–12% of the HgT_D). These groundwater karstic estuaries seem to be mostly characterized by the higher HgT_D and HgR_D concentrations than in the adjacent HTZ Seine estuary. While the HTZ of the Seine estuary acts as a dissolved mercury removal system, the low turbid mixing zone of the Pays de Caux receives the dissolved mercury inputs from the groundwater seepage with an apparent Hg transfer from the particulate phase to the “dissolved” phase (< 0.45 μm). In parallel, the soft tissue of mussels collected near the groundwater discharges, at Etretat and Yport, exhibited significantly higher values than those found in the mussel from the mouth of the Seine estuary. We observe that this difference mimics the differences found in the mercury distribution in the water, and argue that the dissolved phase of the groundwater estuaries and coastal particles are significant sources of bioavailable mercury for mussels.