An experimental ecotoxicological study and its application to the behavioural study of organic mercury (CH3HgCl) in the environment: influence of temperature and pH

Laboratory experiments were carried out to study the influence of temperature (24, 28 and 30 °C) and pH (1–10) on organic mercury (CH₃HgCl) transfer and accumulation in an experimental ecotoxicological model. We followed the evolution of CH₃HgCl in a basic model (water+air) by varying temperature and pH. In a second step, we completed the model by adding sediment and fish. We added CH₃HgCl to water at the beginning of each experiment which was repeated at least three times. Results demonstrated that mercury was released from methylmercury into the air regardless of water pH and its concentration in the air increased with increasing pH. By contrast, in presence of sediment, almost all the mercury was fixed onto the sediment and no mercury was traced in air or in water. Interestingly, in the presence of sediment, the life span of fish under methylmercury exposure lasted longer despite their higher mercury body level content at their death. These results indicate that water is a bad exposure indicator for aquatic pollution. In case of chronic pollution, sediments, fish and aquatic plants are more appropriate indicators.     

Dissolved organic matter in pore water of freshwater sediments: effects of separation procedure on quantity, quality and functionality

Pore water was separated either with or without water extraction prior to centrifugation (7600 or 20 000 × g) in order to investigate the effects of separation procedure on the amount and properties of dissolved organic matter (DOM i.e. the material passing through a 0.45-μm filter) in three freshwater sediments. On the basis of solubility in alkaline, organic matter was concluded to compose of humic substances in two (S1 and S3) and of humin (S2) in one of the sediments. DOM in the samples was quantified by total organic carbon measurement. Specific UV-absorption (SUVA) and high performance size exclusion chromatography (HPSEC) analyses were used to characterize DOM. Sorption of pyrene was used as a measure for functionality of DOM. Both water extraction and centrifugation speed were shown to affect the properties of DOM; however, the effects were sediment dependent. Water extraction increased the amount of DOM separated from the two sediments that had humic character (S1 and S3). In most cases water extraction increased SUVA and shifted the molecular size distribution of DOM towards larger sizes. The separation procedure had also an effect on the functionality of DOM. In water extracted samples of S2 and S3 the sorption of pyrene was higher than in the corresponding samples separated without water extraction, whereas in S1 similar effect was not found. Generally, centrifugation speed had smaller effects on the properties of DOM than water extraction. The fact that the effects of separation procedure on DOM depend on the sediment characteristics complicates the comparison between samples and evaluation of functionality in field conditions.     

Comparisons of coarse and fine versions of two carbons for reducing the bioavailabilities of sediment-bound hydrophobic organic contaminants

Coarse (whole) and finely ground Ambersorb 1500 and coarse and fine coconut charcoal were compared as to their efficiencies in scavenging organic contaminants desorbed from sediment. Aqueous slurries of a test sediment spiked (1 ppm) with p,p^′-DDE (DDE), 2,2^′,5,5^′-tetrachlorobiphenyl (TCB), naphthalene (NAP), or phenanthrene (PHEN), and containing 1% levels of the test carbons were treated by shaking at 35 °C while exposed to clusters of low-density polyethylene membrane (detox spiders). Controls consisted of spiked sediments and detox spiders but no added carbon of any kind and thus represented unimpeded bioavailabilities (to the spiders). After the treatments––agitation periods from 2.5 to 60 h, depending on contaminant hydrophobicity––the exposed detox spiders were analyzed. The fine carbon of either type was more effective than its coarser variant in obstructing contaminant bioavailabilities. The finer variants of both carbons obstructed the bioavailabilities of NAP and PHEN equally well as did the coarser variants of both. Whole Ambersorb 1500 and coarse coconut charcoal were similarly ineffective in intercepting TCB and DDE. Ground Ambersorb 1500 obstructed virtually all bioavailability of all four contaminants and was far more effective than fine coconut charcoal in intercepting DDE and TCB. An additional experiment compared the effectiveness of ground Ambersorb 1500 and fine coconut charcoal in obstructing the bioavailabilities from sediment of a broad array of spiked organochlorine pesticides. The performance of ground Ambersorb 1500 was again found to be superior; the bioavailable levels of each of the 27 pesticides were markedly lower in the presence of ground Ambersorb 1500 than in the presence of fine coconut charcoal.     

Subsurface sediment contamination during borehole drilling with an air-actuated down-hole hammer

Drilling methods can severely alter physical, chemical, and biological properties of aquifers, thereby influencing the reliability of water samples collected from groundwater monitoring wells. Because of their fast drilling rate, air-actuated hammers are increasingly used for the installation of groundwater monitoring wells in unconsolidated sediments. However, oil entrained in the air stream to lubricate the hammer-actuating device can contaminate subsurface sediments. Concentrations of total hydrocarbons, heavy metals (Cu, Ni, Cr, Zn, Pb, and Cd), and nutrients (particulate organic carbon, nitrogen, and phosphorus) were measured in continuous sediment cores recovered during the completion of a 26-m deep borehole drilled with a down-hole hammer in glaciofluvial deposits. Total hydrocarbons, Cu, Ni, Cr and particulate organic carbon (POC) were all measured at concentrations far exceeding background levels in most sediment cores. Hydrocarbon concentration averaged 124 +/- 118 mg kg(-1) dry sediment (n = 78 samples) with peaks at depths of 8, 14, and 20 m below the soil surface (maximum concentration: 606 mg kg(-1)). The concentrations of hydrocarbons, Cu, Ni, Cr, and POC were positively correlated and exhibited a highly irregular vertical pattern, that probably reflected variations in air loss within glaciofluvial deposits during drilling. Because the penetration of contaminated air into the formation is unpreventable, the representativeness of groundwater samples collected may be questioned. It is concluded that air percussion drilling has strong limitations for well installation in groundwater quality monitoring surveys.     

Testing sediment biological effects with the freshwater amphipod Hyalella azteca: the gap between laboratory and nature

The freshwater amphipod, Hyalella azteca, is widely used in laboratory sediment toxicity and bioaccumulation tests. However, its responses in the laboratory are probably very different from those in the field. A review of the literature indicates that in its natural habitat this species complex is primarily epibenthic, derives little nutrition from the sediments, and responds primarily to contaminants in the overlying water column (including water and food), not sediment or porewater. In laboratory sediment toxicity tests H. azteca is deprived of natural food sources such as algal communities on or above the sediments, and is subjected to constant light without any cover except that afforded by burial into the sediments. Under these constraining laboratory conditions, H. azteca has been reported to respond to sediment or porewater contamination. In nature, contamination of overlying water from sediment is less likely than in the laboratory because of the large, generally non-static sink of natural surface water. H. azteca does not appear to be the most appropriate test species for direct assessments of the bioavailability and toxicity of sediment contaminants, though it is probably appropriate for testing the toxicity of surface waters. Toxic and non-toxic responses will be highly conservative, though the latter are probably the most persuasive given the exposure constraints. Thus H. azteca is probably a suitable surrogate species for determining sediments that are likely not toxic to field populations; however, it is not suitable for determining sediments that are likely toxic to field populations.     

Effects of lipids on the sorption of hydrophobic organic compounds on geosorbents: a case study using phenanthrene

The impact of the lipid fraction of natural geosorbents on the sorption of a polycyclic aromatic hydrocarbon was assessed using several experiments. In the first set of experiments phenanthrene was sorbed on a coastal sediment as well as on its humin and humic acid fractions before and after lipid extraction. Before lipid extraction, sorption shows dominantly partitioning characteristics. However, the extraction of lipids from sediment and humin drastically increases, by up to one order of magnitude, their sorption affinity for phenanthrene at low sorbate concentrations, resulting in increased isotherm nonlinearity. This effect is less pronounced for humic acids. One mechanism proposed for the increasing sorption is that lipids, despite their very low relative abundance in the sediments, can compete with phenanthrene for specific high affinity sorption sites (e.g., matrix pores and adsorption sites). This competition is not surprising considering the similar hydrophobic nature of lipids and phenanthrene. Lipids, or any non-polar molecules, could also act like plasticizers by swelling rigid domains and disrupting high affinity sites. In both cases, the removal of lipids (and extraction solvents) makes those sites available for phenanthrene. These provide alternative explanations to the previously proposed “solvent conditioning effect” believed to occur when geosorbents are treated with non-polar solvents modifying the matrix structure, an effect yet to be proven at molecular scale. To further investigate the impact of lipids on sorption, other independent experiments were performed. In a second experiment, re-addition of lipids to the extracted sediment restored the sorption isotherm linearity observed in the native material supporting the absence of irreversible extraction artifacts. However, high addition of lipids (i.e., after saturation of high affinity sites) seems to also enlarge the low affinity partitioning domain. These results are consistent with dual-mode, hole-filling, sorption models involving diffusion. In the final set of experiments, solid-state ¹⁹F-NMR using F-labeled lipids sorbed onto the sediments confirmed that lipids may be in different domains (mobile or rigid) that interact or not with phenanthrene. The possible effects of lipid removal on sorption have been overlooked and should be considered when geosorbents are pretreated.     

In-situ observations of internal dissolved heavy metal release in relation to sediment suspension in lake Taihu, China

Despite laboratory experiments that have been performed to study internal heavy metal release, our understanding of how heavy metals release in shallow eutrophic lakes remains limited for lacking in-situ evidence. This study used automatic environmental sensors and a water sampling system to conduct high-frequency in-situ observations (1-hr intervals) of water environmental variables and to collect water samples (3-hr intervals), with which to examine the release of internal heavy metals in Lake Taihu, China. Under conditions of disturbance by strong northerly winds, sediment resuspension in both the estuary area and the lake center caused particulate heavy metal resuspension. However, the patterns of concentrations of dissolved heavy metals in these two areas were complex. The concentrations of dissolved Se and Mo increased in both areas, indicating that release of internal dissolved Se and Mo is triggered by sediment resuspension. The concentrations of dissolved Ni, Zn, As, Mn, Cu, V, and Co tended to increase in the estuary area but decrease in the lake center. The different trends between these two areas were controlled by pH and cyanobacteria, which are related to eutrophication. During the strong northerly winds, the decrease in concentrations of dissolved heavy metals in the lake center was attributable primarily to absorption by the increased suspended solids, and to growth-related assimilation or surface adsorption by the increased cyanobacteria. The findings of this study suggest that, short-term changes of environmental conditions are very important in relation to reliable monitoring and risk assessment of heavy metals in shallow eutrophic lakes.     

Historical trends of PCBs and PBDEs as reconstructed in a lake sediment from southern Tibetan Plateau

High-altitude lake sediment can be used as a natural archive to reconstruct the history of pollutants. In this work, the temporal distribution of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined using a high-resolution gas chromatography coupled with high-resolution mass spectrometer (HRGC/HRMS) in an alpine lake sediment core collected from the southern Tibetan Plateau (TP) to examine whether the expected decreasing trends due to the implementation of the international Conventions could be observed. The concentrations of PCBs and PBDEs in the sediment core were in the range of 11.8–142 pg/g dw and ND-457 pg/g dw, and their fluxes were in the range of 2.51–31.7 ng/(m²·yr) and ND-43.2 ng/(m²·yr), respectively. The prevalence of low-chlorinated (tri-CB) PCBs and low-brominated (tri- to tetra-) PBDEs in most sections of the sediment profiles was observed, suggesting that the light molecular weight PCBs and PBDEs have most likely reached lake sediments by long-range atmospheric transport from distant sources. Despite the restrictions on their applications, the sediment records for the concentrations and fluxes showed no corresponding decreasing trend with restrictions for PCBs, which suggested that these POPs (e.g., PCBs) were still emitted to the environment owing to the influence of primary or secondary emissions. To our knowledge, this is the first report on input history of atmospheric PCBs and PBDEs recorded in TP Lake sediment.     

Spatial and historical distribution of organic phosphorus driven by environment conditions in lake sediments

The chemistry of sedimentary organic phosphorus (OP) and its fraction distribution in sediments are greatly influenced by environmental conditions such as terrestrial inputs and runoffs. The linkage of OP with environmental conditions was analyzed on the basis of OP spatial and historical distributions in lake sediments. The redundancy analysis and OP spatial distribution results suggested that both NaOH-OP (OP extracted by NaOH) and Re-OP (residual OP) in surface sediments from the selected 13 lakes reflected the gradient effects of environmental conditions and the autochthonous and/or allochthonous inputs driven by latitude zonality in China. The lake level and salinity of Lake Hulun and the runoff and precipitation of its drainage basin were reconstructed on the basis of the geochemistry index. This work showed that a gradient in weather conditions presented by the latitude zonality in China impacts the OP accumulation through multiple drivers and in many ways. The drivers are mainly precipitation and temperature, governing organic matter (OM) production, degradation rate and transportation in the watershed. Over a long temporal dimension (4000 years), the vertical distributions of Re-OP and NaOH-OP based on a dated sediment profile from HLH were largely regulated by the autochthonous and/or allochthonous inputs, which depended on the environmental and climate conditions and anthropogenic activities in the drainage basin. This work provides useful environmental geochemistry information to understand the inherent linkage of OP fractionation with environmental conditions and lake evolution.     

Estimation of total sediment load concentration obtained by experimental study using artificial neural networks

Estimation of sediment concentration in rivers is very important for water resources projects planning and managements. The sediment concentration is generally determined from the direct measurement of sediment concentration of river or from sediment transport equations. Direct measurement is very expensive and cannot be conducted for all river gauge stations. However, sediment transport equations do not agree with each other and require many detailed data on the flow and sediment characteristics. The main purpose of the study is to establish an effective model which includes nonlinear relations between dependent (total sediment load concentration) and independent (bed slope, flow discharge, and sediment particle size) variables. In the present study, by performing 60 experiments for various independent data, dependent variables were obtained, because of the complexity of the phenomena, as a soft computing method artificial neural networks (ANNs) which is the powerful tool for input–output mapping is used. However, ANN model was compared with total sediment transport equations. The results show that ANN model is found to be significantly superior to total sediment transport equations.