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PubMed2005

Mobilization of arsenic by dissolved organic matter from iron oxides, soils and sediments.

The arsenic contamination of aquifers has been linked to the input of dissolved organic matter (DOM). In light of this suggestion, the aim of this study was to quantify chemical effects of DOM on desorption and redox transformations of arsenic bound to synthetic iron oxide and natural samples from different geochemical environments (soils, shallow aquifer, lake sediment). In batch experiments, solutions containing 25-50 mg/L of two different types of DOM (purified peat humic acid and DOM from a peat drainage) were used as extractants in comparison to inorganic solutions. DOM solution was able to mobilize arsenic from all solid phases. Mobilization from iron oxides (maximum: 53.3%) was larger than from natural samples (maximum: 2.9%). The mobilization effect of extractants decreased in the order HCl>NaH2PO4>DOM>NaNO3. DOM solutions, therefore, mainly targeted weakly sorbed arsenic. Mobilization was complete within 24-36 h and DOM was sorbed during incubation indicating competition for sorption sites. The same patterns were observed for different DOM types and concentrations. Addition of DOM lead to (a) enhanced reduction (maximum 7.8%) and oxidation (6.4%) of arsenic in aqueous solution and (b) the appearance of arsenite in aqueous phase of soil samples (5.5%). As the primary mechanism for the arsenic release from solid phases we identified the competition between arsenic and organic anions for sorption sites, whereas redox reactions were probably of minor importance. The results of this study demonstrate that sorption of DOM has a strong potential to mobilize arsenic from soils and sediments.

Adsorption↗
PubMed2006

Metal speciation in sulphidic sediments: a new method based on oxidation kinetics modelling in the presence of EDTA.

The solid phase partitioning of metals (Zn, Cu and Pb) was determined in four anoxic, metal polluted sediments by investigating at pH 8 the 1 day oxidation kinetics of the metal sulphide phases present in the sediments in a background solution containing excess EDTA. A mathematical model consisting of a combination of two pseudo-first order reactions was used to fit the metal release data as a function of oxidation time. The model permitted to fractionate the trace metals in a 'quickly-oxidizable' and a 'slowly-oxidizable' fraction, which could be assigned to two different trace metal pools, respectively (1) FeS minerals (e.g. amorphous FeS, mackinawite) and (2) discrete trace metal sulphide phases. The sum of the fractions associated with these sulphide pools was taken as an approximation for the sulphide-associated fraction of the trace metals and coincided (for the case of Zn and Pb) with the sulphide-associated fraction derived from the analysis of acid volatile sulphide (AVS) and simultaneously extracted metals (SEM). Oxidation kinetics modelling allowed also determining the sulphide-associated fraction of a broad range of trace metals (as demonstrated for Cu) more accurately than the AVS/SEM method, which suffers from non-efficient extraction of a number of trace metal sulphides. A correction was made for the determination of the sulphide-associated fraction by subtracting the trace metal fraction dissolved after 1 day under anoxic conditions in the background EDTA solution. The combination of (1) one day oxidation kinetics modelling and (2) correction for the 1 day anoxic EDTA-soluble fraction is a suitable method to determine accurately the true sulphide speciation of trace metals in anoxic sediments.

Edetic Acid↗
PubMed2004

Sorption-desorption behavior of triazine and phenylurea herbicides in Kishon river sediments.

Sorption and desorption hysteresis of widely applied triazine and phenylurea herbicides were studied for river sediments. Organic carbon normalized sorption coefficient (K(OC)) values for all herbicides were significantly higher for the sediment from the downstream region of the river vs. the upstream sediment. On the basis of the measured K(OC) values, the triazine herbicides can be arranged in the following order: terbutryn > terbuthylazine > ametryn > atrazine. Among the phenylurea herbicides, chlorotoluron exhibited higher sorption than isoproturon (K(OC) values of 137 vs. 60 and 228 vs. 125 L/kg for the upstream and downstream sediments, respectively). Moreover, chlorotoluron exhibited lower desorption potential as compared with isoproturon (apparent hysteresis index values were 0.2-0.3 for chlorotoluron vs. 0.6-0.9 for isoproturon, measured with the upstream sediment). High sorption affinity of chlorotoluron to the sediments is probably due to stronger H-bonding interactions of the herbicide molecules with the sorbents. For both phenylurea herbicides, desorption hysteresis increased with decrease in sorbed amount. This behavior was opposite to the hysteresis trend observed for the triazines. The Cl-triazines (atrazine and terbuthylazine) exhibited higher desorption hysteresis than the S-triazines (ametryn and terbutryn). Therefore, the apparent hysteresis index values calculated for the Cl-triazines were lower than the values of S-triazines (about 0.4 and 0.7, respectively). Based on the relative strength of H-bonding interactions of Cl- and S-triazines with formate anion and on the desorption hysteresis data we suggest a gradient-derived hole-filling sorption mechanism for the triazine herbicides with the river sediments.

Adsorption↗
PubMed2001

Recovery of 4-nonylphenol and 4-nonylphenol ethoxylates from river sediments by pressurised liquid extraction.

The pressurised liquid extraction (PLE) of 4-nonylphenol (4-NP) with methanol (100 degrees C and 100 atm) from river sediments was compared with methanolic Soxhlet extraction, the standard method for the sediment analysis. The PLE method showed a precision (average RSD ranged from 6 to 33%) and an accuracy (average recovery 85 and 87% for 4-NP and 4-NPE, respectively) comparable to those of Soxhlet. The extraction was performed on river sediments and no organic carbon content influence was found. The comparative study presented in this paper demonstrates that PLE is an alternative suitable extraction method for 4-nonylphenol and 4-nonylphenol ethoxylate determination in sediments.

Chromatography, Liquid↗
PubMed2002

Transport and sedimentation of Cu in a microtidal estuary, SE Norway.

The transport and sedimentation of copper in the Glomma estuary, SE Norway during a period of 90% reduction in the industrial input of Cu, was studied from sediment trap material and compared to samples of the bottom sediments. Traps were deployed at four stations for several monthly periods during 1990, 1994 and 1995. Trapped material was analysed for suspended particulate matter (SPM), total organic carbon (TOC) and nitrogen (TN), Cu, and Al. Only about 10% of the Cu from the river is trapped in the estuary. Still there was a moderate but significant reduction in Cu concentration in the trap SPM from 1990 to 1994, reflecting the industrial reductions, but only if excluding summer samples apparently influenced by antifouling Cu from boat paint. Settling matter therefore seems appropriate and sensitive for monitoring changes in the Cu load. The results supported the view that TOC is the main carrier of Cu to the sediments.

Copper↗
PubMed2003

Evaluation of time-to-effects as a basis for quantifying the toxicity of contaminated sediments.

Due to uncertainties as to appropriate procedures and dilution materials, most sediment tests are conducted only with undiluted, whole samples. Hence, it is not possible to use conventional concentration-response approaches to quantify toxicity of samples that elicit a 100% effect (e.g., mortality) at a preset test interval (typically 10 d). An alternative approach to quantifying the relative toxicity of test sediments is to determine time-to-effects. The objective of this study was to assess the utility of a time-to-effects approach for quantifying toxicity of freshwater sediments to the invertebrates Hyalella azteca and Chironomus tentans. Survival of both species and growth of C. tentans was determined using five sediments (four test samples and a control sediment) by destructively sampling replicate test chambers over the course of a "standard" 10-d assay. Studies with the control sediment and a non-toxic test sample indicated excellent recovery of test animals, even early in the test (e.g., <24 h) when individuals of both species are relatively small. Reasonable, typically monotonic, time-to-death relationships were observed for both H. azteca and C. tentans exposed to three comparatively toxic test sediments, all of which caused significant mortality by 10 d. Use of the time-to-effects approach allowed expression of toxicity of the three samples relative to one another, as well as documentation of decreases in toxicity of one of the sediments with increased storage time. These studies demonstrate the feasibility of use of time-to-effects as a basis for quantifying the relative toxicity of contaminated sediments.

Animals↗
PubMed2002

Partitioning of metals in sediments from the Odiel River (Spain).

The Odiel River runs through an area known as the Iberian pyrite belt in the province of Huelva in the southwestern corner of the Iberian Peninsula. Its waters are acidic and contain large amounts of heavy metals from erosion and mining activity. In addition, the Odiel River estuary is one of the most industrialized areas in southern Spain and, consequently, receives the discharge of industrial and urban waste. Seventeen sediment samples from the Odiel and its main tributaries were analyzed for this study. The chemical partitioning of metals (Cu, Zn, Cd, Pb, Fe, Ni, Cr and Co) in each sample was determined in four fractions (acid-soluble, reducible, oxidizable and residual). The total content of each of the metals was also determined. The results showed high concentrations of Fe, Cu, Zn, Pb and Cd, undoubtedly as a result of contamination from the mining and industrial activity mentioned above. However, the concentrations of the other metals analyzed were low since there are no sources of pollution by them in the Odiel River. Based on the chemical distribution of metals, we found that Cd, Zn and Cu are the most mobile metals (i.e., metals that can pass easily into the water under changing environmental conditions). Cd is the metal that showed the highest percentages in the acid-soluble fraction (the most labile) and the lowest in the residual fraction. However, Pb, Fe, Cr and Ni are present in the greatest percentages in the residual fraction, which implies that these metals are strongly linked to the sediments.

Environmental Monitoring↗
PubMed2002

Quantitative assessment of the long term behaviour of 90Sr in Lake Uruskul, Southern Urals, Russia.

The present paper is aimed at assessing the long term behaviour of 90Sr migration from water to bottom sediments of Lake Uruskul, Southern Urals, Russia. The lake was contaminated following the nuclear accident at the Mayak nuclear complex in 1957 (the Kyshtym accident). Some transfer parameters relevant to the behaviour of 90Sr in the water-sediment system were evaluated: a) the radionuclide migration velocity from the water column to the bottom sediment, b) the radionuclide migration rate from bottom sediment to water, and c) the radionuclide migration rate from bottom sediment to deep sediment. The estimated values of the above parameters were 6.4 x 10(-1) m s(-1), 5.7 x 10(-10) s(-1) and 5.2 x 10(-10) s(-1), respectively. These values were compared with data obtained for some Italian lakes contaminated by 90Sr after the nuclear weapons tests fallout. The relatively low radionuclide migration from water to sediment of these lakes is reflected by the values of the ratio migration velocity/migration rate from sediment to water (4 m and 12 m) that are significantly lower than the corresponding value in the Russian lake (112 m). The peculiar hydrochemical conditions of Lake Uruskul (high pH, high mineralisation, etc.) are considered to be responsible for the high radionuclide migration from water to sediment.

Environmental Monitoring↗
PubMed2004

Influence of ripening on pHstat leaching behaviour of heavy metals from dredged sediments.

The influence of oxidation and ripening on the kinetics of heavy metal release from anoxic sediments was investigated by means of porewater analysis and pH(stat) leaching tests. During simulated land disposal of an anoxic river sediment, a considerable heavy metal (Cd, Zn and Ni) release into the porewater was observed after 25 days of exposure of the sediment to the air. The release kinetics of Cd and Zn during pH(stat) leaching indicated that their release was related to the oxidation of Cd- and Zn-sulfides. It was not completely clear whether the release of Ni was due to the oxidation of Ni-sulfides or to the introduction of H(+)(generated by the oxidation of sulfides or introduced by titration). The release of Cu seemed to be explained by the oxidation of both Fe-sulfides and Cu-sulfides. As such, pH(stat) experiments provided an indirect way to assess the mineralogy of the anoxic sediment. During ripening of the sediment, the release rate of Zn and Cd in pH(stat) leaching tests increased. For Ni, however, a similar release pattern was observed in the anoxic sediment and in the ripened sediments. Two weeks' drying at 100 degrees C resulted in an increase in the leachability of Cu. Nevertheless, at pH 4 and 6, the thermally treated sediment displayed a slower leaching of Cd and Zn than the ripened sediment. Although thermal treatment is often used to simulate ageing in soils, it cannot be used to simulate ripening of anoxic sediments.

Environmental Pollutants↗
PubMed2004

Dynamic processes in the Venice region outlined by environmental isotopes.

Research carried out in the last 40 years has shown the scientific importance of groundwater circulation both in the Northern Adriatic sea bed and within the uppermost sedimentary layers of the Venice lagoon and of the Venice plain. Hydrodynamic processes are strictly controlled by a well-cemented sedimentary horizon lying under and around Venice ('caranto'), which plays the role of regional aquitard. This layer was attributed to the subaerial cementation of the Flandrian (8-10 ka Before Present) sedimentary surface. The caranto is generalised as a continuum horizon, being an easy explanation for several environmental, hydrogeological and geotechnical problems, e.g., a base layer for landfills, a confining layer for deep aquifers and the best substratum for locating the oak wooden pile-dwelling needed to support the largest buildings. The preservation of the isotope signal within the deep aquifers and aquiclude system records the changes in surface and groundwater characteristics and suggests the present and past recharge regimes. In this region, the heavily perturbed hydrodynamic conditions do not allow for the use of isotopic signals to derive a correct reconstruction of the present recharge. The perturbations induced by the intensive anthropogenic activity force to follow climate evolution by considering deep groundwater and pore waters. In addition, the presence of carbonatic rocks inside terrigeneous sediments affects the reconstruction of the past. Results indicate that carbonatic rocks are created by seepage, through the sediments, of gaseous carbon compounds from decaying organic layers. The gas interactions with the intra-sedimentary saline and fresh waters produce CO2, inducing the cementation of the sediments.

Cities↗
PubMedDate not supplied

Geochemical effects on metals following permanganate oxidation of DNAPLs.

The application of in situ chemical oxidation for dense, nonaqueous phase liquid (DNAPL) remediation requires delivery of substantial levels of oxidant chemicals into the subsurface to degrade target DNAPLs and to satisfy natural oxidant demand. This practice can raise questions regarding changes in subsurface conditions, yet information regarding potential effects, especially at the field scale, has been lacking. This paper describes an evaluation of the effects on metals associated with in situ chemical oxidation using potassium permanganate at Launch Complex 34 (LC34), Cape Canaveral Air Station, Florida. At LC34, high concentrations of permanganate (1 to 2 wt%) were injected into the subsurface as part of a demonstration of DNAPL remediation technologies. In a companion experimental effort at the Colorado School of Mines, field samples were characterized and laboratory batch and mini-column studies were completed to assess effects of permanganate oxidation on metals in the subsurface one year after completion of the field demonstration. Results indicated there was potential for long-term immobilization of a portion of introduced manganese and no treatment-induced loss in subsurface permeability due to deposition of manganese oxides particles, which are a product of the oxidation reactions. Permanganate treatment did cause elevated manganese, chromium, and nickel concentrations in site ground water within the treated region. Some of these metals effects can be attenuated during downgradient flow through uncontaminated and untreated aquifer sediments.

Environmental Pollution↗
PubMed2006

Influences of infaunal burrows on the community structure and activity of ammonia-oxidizing bacteria in intertidal sediments.

Influences of infaunal burrows constructed by the polychaete (Tylorrhynchus heterochaetus) on O(2) concentrations and community structures and abundances of ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB) in intertidal sediments were analyzed by the combined use of a 16S rRNA gene-based molecular approach and microelectrodes. The microelectrode measurements performed in an experimental system developed in an aquarium showed direct evidence of O(2) transport down to a depth of 350 mm of the sediment through a burrow. The 16S rRNA gene-cloning analysis revealed that the betaproteobacterial AOB communities in the sediment surface and the burrow walls were dominated by Nitrosomonas sp. strain Nm143-like sequences, and most of the clones in Nitrospira-like NOB clone libraries of the sediment surface and the burrow walls were related to the Nitrospira marina lineage. Furthermore, we investigated vertical distributions of AOB and NOB in the infaunal burrow walls and the bulk sediments by real-time quantitative PCR (Q-PCR) assay. The AOB and Nitrospira-like NOB-specific 16S rRNA gene copy numbers in the burrow walls were comparable with those in the sediment surfaces. These numbers in the burrow wall at a depth of 50 to 55 mm from the surface were, however, higher than those in the bulk sediment at the same depth. The microelectrode measurements showed higher NH(4)(+) consumption activity at the burrow wall than those at the surrounding sediment. This result was consistent with the results of microcosm experiments showing that the consumption rates of NH(4)(+) and total inorganic nitrogen increased with increasing infaunal density in the sediment. These results clearly demonstrated that the infaunal burrows stimulated O(2) transport into the sediment in which otherwise reducing conditions prevailed, resulting in development of high NH(4)(+) consumption capacity. Consequently, the infaunal burrow became an important site for NH(4)(+) consumption in the intertidal sediment.

Ammonia↗
PubMed2005

A field-based microcosm method to assess the effects of polluted urban stream sediments on aquatic macroinvertebrates.

A method using field-based microcosms was developed to determine the effects of contaminated sediments on aquatic macroinvertebrates. Fine sediments from nonpolluted, moderately polluted, and severely polluted bodies of water were placed in microcosms positioned within the littoral zone of a nonpolluted wetland near Melbourne (Victoria, Australia). In three experiments, 47 taxa, including 18 Chironomidae, 6 taxa from other Diptera families, and 7 Hemiptera taxa, colonized the microcosms, mostly via eggs deposited by flying adults. The effects of sediment type on the presence and abundance of common taxa were considered statistically. Pollution levels in sediments (indexed either by a principal components analysis or by the concentration of zinc, the predominant metal) resulted in reduced occurrence and abundance of eight taxa but had no effect on another five taxa. These findings were validated with an extensive field database for the distribution of macroinvertebrates and associated concentrations of zinc in sediments from streams and wetlands in the Melbourne region. The occurrence of eight taxa and the abundance of two taxa varied at similar zinc concentrations in sediments from both the microcosms and the field. Patterns for another two species did not match the microcosm results, but these groups contained multiple species with potentially diverse responses. The present results suggest that contaminant levels in sediments probably have a direct effect on the occurrence and abundance of macroinvertebrates in bodies of water in urban areas. The microcosm method can be used to gather information regarding the effects of sediment quality on macroinvertebrates in lentic habitats, particularly for indigenous species that cannot be easily reared or tested in laboratory conditions. Because almost all macroinvertebrates in microcosms develop from eggs, the most sensitive life stages (i.e., first and second instars) are exposed to polluted sediments.

Animals↗
PubMed2005

Sorbate size-dependent maximum capacities for adsorption of organic compounds in the slowly and very slowly desorbing domains of a sediment.

Maximum capacities were determined for adsorption of six polycyclic aromatic hydrocarbons, seven polychlorinated biphenyls, and five chlorobenzenes in both the slowly desorbing domain and the very slowly desorbing domain of a sediment. For separate compound classes in the two desorption domains, log-transformed maximum adsorption capacities were linearly related to the relative magnitude of the shadow of the sorbate on an imaginary planar surface. For planar compounds, the ratio of maximum adsorption capacities for the slowly desorbing domain and the very slowly desorbing domain was approximately two. This ratio was eightfold higher for strongly nonplanar polychlorinated biphenyls, which suggests that adsorption depends on sorbate thickness in the very slow desorption domain but not in the slow desorption domain. The rates of decrease of the log-transformed sum of maximum capacities for adsorption in the slow desorption domain and the very slow desorption domain with increasing relative magnitude of the shadow of the sorbate on a planar surface were similar to those derived from literature data regarding maximum capacities for adsorption onto a soil and a sediment. It is proposed that the rates of decrease for both the slow desorption domain and the very slow desorption domain may have general applicability to soils and sediments.

Adsorption↗
PubMed2001

[Sediment-copper interaction and vertical distribution in hyper-concentrated turbulent system].

This paper presents a special problem on vertical distribution for sediment and copper in hyper-concentrated turbulent solid-liquid system that is essentially different from the ordinary low concentrated turbulent system. A resonance type turbulent simulation equipment is used for the experimental study in which a vertically uniform turbulent field of the mixture of loess and water is produced in a testing cylinder with a grille stirrer that moves up and down harmoniously with varying vibration frequencies. In order to compare the variations of the vertical profiles of sediment and copper in low- and hyper-concentrated solid-liquid system, different scenarios for input sediment content ranging from 5 to 800 kg/m3 was considered in the experimental studies. It was found that solids copper content increases with input sediment content, S, and reaches its peak as S goes to 10 kg/m3 and then decreases rapidly with increasing input sediment content. Such a behavior is possibly resulted from the joint effect of the specific adsorption of copper on loess, precipitation of carbonate and hydroxide of copper due to high carbonate content in the loess and the so-called "particulate concentration effect" due to the present of the sediment variation in water. The vertical sediment concentration distribution resulted from the uniform turbulence is generally uniform, but slight non-uniformity does occur as sediment concentration exceeds certain value. However, the vertical concentration distributions of soluble copper seem not affected much by the variation of sediment concentrations.

Copper↗