Interaction of phenanthrene and its primary metabolite (1-hydroxy-2-naphthoic acid) with estuarine sediments and humic fractions

Experiments were conducted to compare the sorption and desorption of phenanthrene and its primary degradation product, 1-hydroxy-2-naphthoic acid (HNA), in estuarine sediment, humic acid (HA) and humin. Ionic composition, ionic strength (0.4 M) and pH (7.6) were employed to mimic native estuarine pore water at the sediment-water interface. Sorption to whole sediment and organic matter (OM) fractions was significantly lower for HNA than for phenanthrene. Whereas HNA did not sorb to HA, uptake to sediment and humin was observed, suggesting that HNA does not bind directly to OM. Phenanthrene uptake was characterized by hysteretic behavior and exhibited slow desorption. In contrast, HNA initially was more readily desorbed from sediment and humic fractions, but a significant fraction was not recovered in repeated desorption runs. The lower sorption of HNA reflects its greater polarity and water solubility, but the consistent retention of a non-desorbing fraction suggests strong binding and/or chemical transformation reactions may be important. It was postulated that abiotic transformation of HNA may occur in estuarine sediments, in part due to the presence of redox active minerals (Fe(III) and Mn(IV) oxides). The presence of Fe and Mn solids in the estuarine sediment was verified by sequential extraction and studies were then conducted to investigate the transformation of HNA in the presence of synthetic goethite (alpha-FeOOH) and birnessite (delta-MnO2) as model solids. Reaction with birnessite led to transformation of all HNA in solution within 24 h and resulted in the formation of partial oxidation products (POPs). Following reaction with goethite, HNA was present in solution and POPs were observed in the weakly bound fraction. This study indicates that degradation products of polycyclic aromatic hydrocarbons (PAHs) may have distinctly different sorption affinities and reactivities toward environmental surfaces than their parent compounds.     

Ionic contribution to the self-potential signals associated with a redox front

In contaminant plumes or in the case of ore bodies, a source current density is produced at depth in response to the presence of a gradient of the redox potential. Two charge carriers can exist in such a medium: electrons and ions. Two contributions to the source current density are associated with these charge carriers (i) the gradient of the chemical potential of the ionic species and (ii) the gradient of the chemical potential of the electrons (i.e., the gradient of the redox potential). We ran a set of experiments in which a geobattery is generated using electrolysis reactions of a pore water solution containing iron. A DC power supply is used to impose a difference of electrical potential of 3 V between a working platinum electrode (anode) and an auxiliary platinum electrode (cathode). Both electrodes inserted into a tank filled with a well-calibrated sand infiltrated by a (0.01 mol L^− 1 KCl + 0.0035 mol L^− 1 FeSO₄) solution. After the direct current is turned off, we follow the pH, the redox potential, and the self-potential at several time intervals. The self-potential anomalies amount to a few tens of millivolts after the current is turned off and decreases over time. After several days, all the redox-active compounds produced initially by the electrolysis reactions are consumed through chemical reactions and the self-potential anomalies fall to zero. The resulting self-potential anomalies are shown to be much weaker than the self-potential anomalies observed in the presence of an electronic conductor in the laboratory or in the field. In the presence of a biotic or an abiotic electronic conductor, the self-potential anomalies can amount to a few hundred millivolts. These observations point out indirectly the potential role of bacteria forming biofilms in the transfer of electrons through sharp redox potential gradient in contaminant plumes that are rich in organic matter.     

230Th/232Th activity ratios as a chronological marker complementing 210Pb dating in an estuarine system affected by industrial releases

The main purpose of this research is to show the usefulness of the 230Th/232Th activity ratios as a chronological marker that can be helpful in the dating of sediment cores collected from an estuarine system located in the south west of Spain highly polluted by wastes from fertilizer plants. These wastes, being released for 30 years, and enriched in radionuclides from the uranium series including 210Pb, invalidate the application of the 210Pb dating technique in full extent to the sediment cores collected in this estuary. However, the evaluation and the interpretation of both 210Pb and 230Th/232Th profiles allows the determination of average sedimentation rates in different parts of the cores, contaminated and noncontaminated zone, that agree in the case analysed in this research. Through this approach, a confident chronology covering the last century, which is essential to analyse and reconstruct the historical evolution of other pollutants in this heavily contaminated system can be established.     

Validation of isotope signatures in sediments affected by anthropogenic inputs from uranium series radionuclides

This paper aims to show the usefulness of 226Ra/228Ra activity ratios and confirm the possibility of using 230Th/232Th activity ratios as chronological markers in sediment cores from an estuarine system strongly contaminated by discharges from non-nuclear industries (fertiliser plants). The validation was carried out using an independent, well-established dating technique based on the analysis of the 137Cs fallout profile, which comprises the same time interval as that covered by both isotope ratios. The advantage of using the 226Ra/228Ra activity ratio profile instead of the Th-isotope profile is that determination can be accomplished with a non-destructive, simpler and less time-consuming technique, because both Ra isotopes can be determined by gamma-ray spectrometry.     

Investigations into the differential reactivity of endogenous and exogenous mercury species in coastal sediments

Stable isotopic tracer methodologies now allow the evaluation of the reactivity of the endogenous (ambient) and exogenous (added) Hg to further predict the potential effect of Hg inputs in ecosystems. The differential reactivity of endogenous and exogenous Hg was compared in superficial sediments collected in a coastal lagoon (Arcachon Bay) and in an estuary (Adour River) from the Bay of Biscay (SW France). All Hg species (gaseous, aqueous, and solid fraction) and ancillary data were measured during time course slurry experiments under variable redox conditions. The average endogenous methylation yield was higher in the estuarine (1.2 %) than in the lagoonal sediment (0.5 %), although both methylation and demethylation rates were higher in the lagoonal sediment in relation with a higher sulfate-reducing activity. Demethylation was overall more consistent than methylation in both sediments. The endogenous and exogenous Hg behaviors were always correlated but the exogenous inorganic Hg (IHg) partitioning into water was 2.0–4.3 times higher than the endogenous one. Its methylation was just slightly higher (1.4) in the estuarine sediment while the difference in the lagoonal sediment was much larger (3.6). The relative endogenous and exogenous methylation yields were not correlated to IHg partitioning, demonstrating that the bioavailable species distributions were different for the two IHg pools. In both sediments, the exogenous IHg partitioning equaled the endogenous one within a week, while its higher methylation lasted for months. Such results provide an original assessment approach to compare coastal sediment response to Hg inputs.     

Oxidation-reduction potential changes in aeration tanks and microprofiles of activated sludge floc in medium- and low-strength wastewaters.

Real-time control of aeration tank operation is key to high-efficiency pollutant removal and energy savings. One of the aims of this study was to examine the potential for using redox potential (oxidation-reduction potential [ORP]) to indicate wastewater quality online in aeration tanks treating medium (chemical oxygen demand [COD] of 70 to 150 mg/L) and low (COD of 15 to 30 mg/L) pollutant-concentration wastewaters. The field-scale data provide a good relationship between ORP values and nutrient removal along the length of the aeration tanks. The ORP values increased dramatically as organic matter was removed along the aeration tanks, indicating the improvement of the bulk liquor redox status. Dissolved oxygen higher than 1.0 mg/L was necessary for good biodegradation and improvement of the liquid redox status. Nitrification occurred at higher ORP values (380 to 420 mV) than was the case for organic substrate oxidation (250 to 300 mV). The microprofiles obtained from microelectrode measurements substantiate the heterogeneity of the microbial processes inside activated sludge flocs. Because of microbial oxygen utilization, the aerobic region in the activated sludge floc was limited to the top layer (0.1 to 0.2 mm) of the activated sludge aggregate present in medium-strength wastewater, with an anoxic zone dominating inside the flocs. When dissolved oxygen in the bulk water was higher than 4.0 mg/L, the anoxic zone inside the floc disappeared. At low wastewater pollutant concentrations, the ORP and dissolved oxygen inside the activated sludge aggregates were higher than those from medium-strength wastewater. The prospect of using ORP as an online control approach for aeration tank operation and the potential reasons for activated sludge floc size varying with pollutant strengths are also discussed.     

Heavy metals from the River Adayar,India: infiltration into the adjacent groundwater aquifer

In the Adayar riverbed and its estuary 5 undisturbed sediment cores were drilled using a petrol-driven hammer. Cores of a depth of 4-5 m were sampled in 0.5 m steps. The distribution of heavy metals (Cr, Mn, Ni, Cu, Zn, Cd and Pb) in the top layers of fluvial and estuarine sediments indicates recent anthropogenic input: Revealing that the river acts as a sink for drainage from the residential and industrial zones. In this study, the mobilization of heavy metals into greater depths and their probable effects on the groundwater body are discussed. The high concentration of heavy metals and the influent character of the river Adayar allow the mobilization of metal ions and their transport into the deeper layers of the sediment. A changing environment due to effects such as saltwater intrusion and monsoon floods is the driving force for this phenomenon.     

Use of artificial sediments in a comparative toxicity study with larvae and postlarvae of the grass shrimp, Palaemonetes pugio

An artificial sediment was tested for use in evaluating the potential hazard of toxicants on benthic organisms. The seawater-sediment system was assessed by use of the pyrethroid insecticide, fenvalerate, as the model toxicant for testing with larvae of the grass shrimp, Palaemonetes pugio, an ecologically important estuarine species. The sediment was prepared from commercially available components, and mixed with the toxicant to provide concentrations of 1, 10 and 100 microg fenvalerate kg(-1) dry sediment in 20 ppt seawater. Sediment free of the insecticide served as the control. Throughout the study, fenvalerate was not detected in the water column, but was measured in sediment at the nominal concentration of 100 microg kg(-1). The P. pugio population was adversely affected by fenvalerate. The effect occurred at metamorphosis, when larvae changed from pelagic individuals to benthic organisms. At this period, larvae were in direct contact with sediment. A portion of the population was tolerant of the insecticide.     

Pt and Pd in sediments from the Pearl River Estuary,South China: background levels,distribution, and source

Purpose  

This study assessed the concentrations of platinum (Pt) and palladium (Pd) in surface sediments and sedimentary cores collected from the Pearl River Estuary with a view of evaluating the distribution, background levels, possible sources, and contamination level of anthropogenic Pt and Pd.     

Self-potential monitoring of a crude oil-contaminated site (Trecate,Italy)

We present a multidisciplinary approach for characterization of a crude oil-contaminated site (Trecate, Italy), integrating geophysical data, such as subsoil electrical potential (in millivolts) and electrical resistivity (in ohm meters) distribution, with hydrogeological and bio-chemical data. Self-potential measurements have been evaluated together with active geoelectrical measurements and hydrological information, to provide spatial and temporal information about the self-potential sources and their possible correlations with the contamination state of the subsoil. Three self-potential surveys (March 2010, October 2010, and March 2011) were conducted at the site, both in the contaminated and uncontaminated regions. The obtained self-potential maps show large time-lapse differences in correspondence of the contaminated area, with positive electrical potential values (up to 50 mV) in spring surveys and an electrical potential dipolar distribution in October (2010) survey (amplitude from ?15 to 25 mV). To understand the origin of the measured self-potential signals, a model using vertical dipolar electrical sources was built, taking into account the electrical resistivity distribution deduced from electrical resistivity tomography. The self-potential source identification allows the Trecate contamination state to be better delineated. In particular, two self-potential contributions are superimposed: the electrokinetic mechanism is predominant in spring, while the redox mechanism represents the most important contribution in autumn.     

In-situ partitioning of butyltin compounds in estuarine sediments

The in-situ solid/pore-water partitioning of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) was determined for an estuarine sediment profile collected from a commercial marina. Total butyltin levels exceeded sediment quality guideline values, and were 220-8750 microg/kg for TBT, 150-5450 microg/kg for DBT and 130-4250 microg/kg for MBT. Pore-water butyltin concentrations ranged from 0.05 to 2.35 microg/l for TBT, 0.07-3.25 microg/l for DBT, and 0.05-0.53 microg/l for MBT. The partitioning of butyltin compounds between the sediment solid-phase and pore-water was described by an organic carbon normalised distribution ratio (D(OC)). The observed D(OC) values were similar for TBT, DBT and MBT, and were 10(5)-10(6) l/kg. Values for the Butyltin Degradation Index (BDI) were larger than 1 at depths greater than 10 cm below the sediment/water-column interface. This indicates that substantial TBT degradation has occurred in the sediments, and suggests that natural attenuation may be a viable sediment remediation strategy.     

Electrochemical oxidation of benzene on boron-doped diamond electrodes

This work presents an electrochemical investigation of the benzene oxidation process in aqueous solution on boron-doped diamond (BDD) electrodes. Additionally, in order to determine the main products generated during the oxidation process, electrolysis and high performance liquid chromatography experiments were carried out. The complete degradation of this compound was performed aiming to a further application in waste water treatment. The cyclic voltammetry studies indicate that benzene is irreversibly oxidized in acid medium (H₂SO₄ 0.5 M) on the BDD electrode surface at 2.0 V versus Ag/AgCl in a diffusion controlled process. During the cycling, other products are generated, and a pair of peaks was observed that can be associated with the oxi-reduction of anyone of the following species: hydroquinone, benzoquinone, resorcinol or catechol. The electrolysis experiments were carried out at 2.4 and 2.5 V on the BDD electrode surface in a solution containing 1 × 10⁻² M of benzene (below the saturation concentration in aqueous solution), for 3 and 5 h, respectively. The main products measured were: hydroquinone, resorcinol, p-benzoquinone, catechol and phenol. The complete electrochemical benzene degradation was performed in the electrolysis experiments using a rotating BDD disc electrode (2.5 V for 5 h) and the main products detected were all measured at concentrations lower than 10⁻⁵ M in this condition. The boron-doped diamond electrode had proved to be a valuable tool for the electrochemical degradation of the benzene, a very stable chemical compound.     

The origin of speciation: trace metal kinetics over natural water/sediment interfaces and the consequences for bioaccumulation

The speciation of heavy metals was measured over a variety of natural and undisturbed water/sediment interfaces. Simultaneously, two benthic species (oligochaete Limnodrilus spp. and the midge Chironomus riparius) were exposed to these sediments. Under occurring redox conditions, free ion activities of trace metals Cd, Cu, Ni, Pb, and Zn were measured with a chelating exchange technique, while geochemical conditions (i.e., redox) remained in tact. Free ion activities were compared with total dissolved concentrations in pore waters and surface waters in order to relate speciation to bioaccumulation. Limnodrilus spp. and C. riparius have accumulation patterns that could be linked to time-dependent exposure concentrations, expressed as chemical speciation, in the surface water and the sediment's pore water. Concentrations of free metal ions in the overlying surface water, rather than in sediment pore water, proved to be the best predictor for uptake. For the first time, measurements are obtained from sediments without disturbing physical-chemical conditions and thus bioavailability, a major restriction of other studies so far.     

Large-scale fires and time trends of PCDDS/DFs in sediments

Drastic increases in PCDDs/DFs concentrations were identified in the uppermost layers of a sediment core sample taken from the coastal area of Kobe City. As large-scale fires caused by the Great Hanshin-Awaji earthquake were deemed to be a possible cause, we performed additional sampling of sediment cores and surface sediment samples, estimating the total amount of PCDDs/DFs released from fires and presuming the load to sediments by individual transport routes, such as air and water, using an air diffusion model to investigate the influence of fires. The total amount of PCDDs/DFs released from fires was estimated at 2000 g-total PCDDs/DFs, 22 g-TEQ. Increases in PCDDs/DFs generated in fires were principally transported through water rather than air. If 20% of the total PCDDs/DFs formed in fires had entered water, it would correspond to the entire increase of PCDDs/DFs concentration in sediment cores.     

Assessment of acid leachable trace metals in sediment cores from River Uppanar, Cuddalore, Southeast coast of India

An acid leachable technique is employed in core samples (C1, C2 and C3) to develop a baseline data on the sediment quality for trace metals of River Uppanar, Cuddalore, southeast coast of India. Acid leachable metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd) indicate peak values at the sulphidic phase and enrichment of metals in the surface layers are due to the anthropogenic activities. Association of trace metals with Fe, Mn indicates their adsorption onto Fe-Mn oxyhydroxides and their correlation with S indicate that they are precipitated as metal sulphides. Factor analysis identified three possible types of geochemical associations and the supremacy of trace metals along with Fe, Mn, S and mud supports their geochemical associations. Factor analysis also signifies that anthropogenic activities have affected both the estuarine and fresh water regions of River Uppanar.     

Transformation of N-, O-, and S- heterocycles (NOSHs) in estuarine sediments: Effects of redox potential and sediment particle size

The transformation of 19 N-, O-, and S- heterocycles (NOSHs) was examined in estuarine sediment-water microcosms. The effects of redox potential (Eh) and sediment particle size on compound transformation rates were evaluated, and stable products were identified. Results from stirred, controlled Eh/pH microcosms (CEPMs) showed that most of the NOSHs were significantly transformed under oxidized and reduced conditions over 15 week incubations, and the resulting product distributions were similar. In general, the rates and extent of transformation were greater in oxidized sediments of low surface area vs. those with high particle surface area and reduced redox conditions. Further experiments in sealed, unstirred microcosms also showed that NOSH transformation proceeded more slowly and on fewer compounds in fine vs. coarser grained sediments under oxidized conditions. Unlike the stirred systems, however, NOSH transformation rates were similar or greater under reduced vs. oxidized conditions. Thus, reduced, methanogenic clay of high surface area displayed some of the fastest rates of NOSH transformation. Data from liquid-liquid partitioning experiments suggested that this effect was related to the formation of NOSH complexes with iron and perhaps other redox-active metals in sediments.     

固定化氧化还原介体加速亚硝酸盐生物反硝化作用

考察了利用循环伏安法所制备的固定化氧化还原介体(AQS/PPy/ACF)加速亚硝酸盐生物反硝化的特性,及其降解过程中pH和氧化还原电位(ORP)的变化特征。结果表明,AQS/PPy/ACF可显著地加速亚硝酸盐的生物降解;在不考虑各因子间交互作用的条件下,AQS/PPy/ACF加速亚硝酸盐降解的最佳条件为温度35℃,pH=8和碳氮比为6;AQS/PPy/ACF加速亚硝酸盐生物反硝化过程中pH的变化趋势与传统的亚硝酸盐生物反硝化过程中pH的变化趋势相似;AQS/PPy/ACF的加入可使亚硝酸盐生物反硝化过程中的ORP降低约45 mV;AQS/PPy/ACF具有较好的催化稳定性。本研究可为亚硝酸盐的生物降解提供新的技术途径,并为该技术的实际应用提供理论基础。     

Vertical distributions of persistent organic pollutants (POPs) caused from organochlorine pesticides in a sediment core taken from Ariake bay, Japan

Persistent organic pollutants (POPs) of organochlorine pesticides such as dichlorodiphenyl trichloroethane (DDTs) and its metabolites, hexachlorobenzene (HCB), heptachlor, chlordane compounds (CHLs), aldrin, dieldrin, endrin, mirex and isomers of hexachlorocyclohexane (HCHs), were analyzed in sediment cores collected from Ariake Bay, Japan. Although Chikugo River has the largest flow in Ariake Bay, the total concentration of POPs in surface sediment was found in St.3, mouth of the Yabe River, where that level was two times higher than St.1, mouth of the Chikugo River. It could be assumed that the potential source of POPs contamination is relatively close to this study area. Relatively high residue levels of HCB, HCHs and DDTs in sediment core were found during the period from 1967 to 1970. In this layer, the HCB concentration investigated in sediment cores of Ariake Bay was maximum, 2.6 ng g(-1) dry weight and higher than that of Tokyo Bay and subsequently detected in deeper sediment cores. The ratio of (DDD+DDE)/SigmaDDTs was high in top sediments (0-2 cm). Although there was a concentration of DDTs in the top sediment, it was noticed that DDT emission did not cause direct input of DDT recently. The HCHs determined in upper sediment cores might be originated from long-range accumulation in environment after dispersing of technical-grade HCH. Moreover, the CHLs, dieldrin and heptachlor concentrations were detected and recently increased in sediment core. POPs in sediment cores of Ariake Bay based on the possibility of PCP contamination during the early 1960s were reflected.     

Alteration of sediment organic matter in sediment microbial fuel cells

The alteration of physico-chemical properties of sediment organic matter (SOM) incubated under current-harvesting conditions as well as no-current producing conditions over 120 days using sediment microbial fuel cell systems was examined. The SOM was microbially oxidized under anaerobic conditions with an electrode serving as a terminal electron acceptor. It was found that SOM around the electrochemically-active electrodes became more humified, aromatic, and polydispersed, and had a higher average molecular weight, along with its partial degradation and electricity generation compared to that for the original sediment. These changes in SOM properties were analogous to those commonly observed in the early stages of the SOM diagenetic process (i.e. humification). Such a humification-like process was evidently more stimulated when electrical current was produced than no-current condition. These new findings associated with microbially-catalyzed electricity generation may present a potential for the energy-efficient remediation, monitoring, and/or management of the geo-environment.