Ozonation kinetics of cork-processing water in a bubble column reactor

The oxidative degradation of organic pollutants present in cork-processing water at natural pH (6.45) was studied in a bubble column ozonation reactor. A steady reduction in both chemical oxygen demand (COD) and total organic carbon (TOC) was observed under the action of ozone alone and the feasibility of deep mineralisation (organic matter removal more than 90% in 120 min under the following experimental conditions: liquid volume 9L; superficial gas velocity 6.8x10(-3) m s(-1); ozone partial pressure 1.31 kPa; initial COD 328 mg L(-1); initial TOC 127 mg L(-1)) was demonstrated. The monitoring of pH, redox potential (ORP) and the mean oxidation number of carbon (MOC) was correlated with the oxidation and mineralisation of the organic species in the water. The ozonation of cork-processing water in the bubble column was analysed in terms of a mole balance coupled with ozonation kinetics modelled by the two-film theory of mass transfer and chemical reaction. Under the experimental conditions used, and in contrast with the literature, it was determined that the reaction follows a fast kinetic regime at the beginning of the oxidation process, shifting to the moderate and the slow kinetic regimes at later stages of the oxidation reaction. The dynamic change of the rate coefficient estimated by the model was correlated to changes in the water composition.     

Mercury speciation in the Valdeazogues River-La Serena Reservoir system: Influence of Almadén (Spain) historic mining activities

Mercury (Hg) speciation and partitioning have been investigated in a river-reservoir system impacted by the Almadén mining activities, the world's largest Hg district. This study is the first to simultaneously investigate Hg dynamics from above the mining district and into the La Serena Reservoir (3219 Hm³), being the third largest reservoir in Europe and the largest in Spain.Water, sediment and biota were sampled at different seasons during a 2-year study from the Valdeazogues River, which flows east-west from the mining District, to La Serena Reservoir. Simultaneously, a comprehensive study was undertaken to determine the influence of some major physico-chemical parameters that potentially influence the fate of Hg within the watershed.Concentrations of dissolved Hg in water were below 0.14 µg/L, whereas particulate Hg ranged from 0.1 to 87 µg/g, with significant seasonal variation. Total Hg concentrations varied from 7 to 74 µg/g in sediment from the Valdeazogues River, while in sediments from La Serena Reservoir were below 2 µg/g. On the other hand, methyl-Hg reached concentrations up to 0.3 ng/L in water and 6 ng/g in sediment from La Serena Reservoir, whereas maximum concentrations in Valdeazogues River were 5 ng/L and 880 ng/g in water and sediment, respectively. The distribution of Hg species in the Valdeazogues River-La Serena Reservoir system indicated a source of Hg from the mine waste distributed along the river. Total Hg in water was strongly correlated with total dissolved solids and chlorophyll a concentrations, whereas organic carbon and Fe concentrations seem to play a role in methylation of inorganic Hg in sediment. Total Hg concentrations were low in fish from Valdeazogues River (0.8-8.6 ng/g, wet weight) and bivalves from La Serena Reservoir (10-110 ng/g, wet weight), but most was present as methyl-Hg.     

Ozonation kinetics of winery wastewater in a pilot-scale bubble column reactor

The degradation of organic substances present in winery wastewater was studied in a pilot-scale, bubble column ozonation reactor. A steady reduction of chemical oxygen demand (COD) was observed under the action of ozone at the natural pH of the wastewater (pH 4). At alkaline and neutral pH the degradation rate was accelerated by the formation of radical species from the decomposition of ozone. Furthermore, the reaction of hydrogen peroxide (formed from natural organic matter in the wastewater) and ozone enhances the oxidation capacity of the ozonation process. The monitoring of pH, redox potential (ORP), UV absorbance (254 nm), polyphenol content and ozone consumption was correlated with the oxidation of the organic species in the water. The ozonation of winery wastewater in the bubble column was analysed in terms of a mole balance coupled with ozonation kinetics modeled by the two-film theory of mass transfer and chemical reaction. It was determined that the ozonation reaction can develop both in and across different kinetic regimes: fast, moderate and slow, depending on the experimental conditions. The dynamic change of the rate coefficient estimated by the model was correlated with changes in the water composition and oxidant species.     

Environmental modelling in the Gulf of Cadiz: Heavy metal distributions in water and sediments

The Gulf of Cadiz (GoC) connects the Atlantic Ocean and the Mediterranean Sea. An environmental study of the GoC is carried out through numerical modelling. First, a 3D baroclinic model is used to obtain the residual circulation and a 2D barotropic model is applied to calculate tides. The results of these models are used by a 3D sediment transport model which provides suspended matter concentrations and sedimentation rates in the GoC. Then heavy metal dispersion patterns are investigated using a 3D model which includes water-sediment metal interactions and uses the outputs of the hydrodynamic and sediment transport models. The metal transport model has been applied to simulate the dispersion of Zn, Cu and Ni introduced into the GoC from three rivers draining the Iberian Pyrite Belt, in the southern Iberian Peninsula. Results from the hydrodynamic, sediment and metal transport models have been compared with measurements in the GoC. In particular, the contamination of sediments collected along the southern coast of Spain is well reproduced by the model. Metal plumes reach the Strait of Gibraltar, thus the three rivers constitute a source of pollutants into the Mediterranean Sea.     

Kinetics of the chemical oxidation of polysulfide anions in aqueous solution

The kinetic properties of the chemical oxidation of aqueous polysulfide solutions have been studied in phosphate-buffered systems at pH 7-12, at temperatures between 20 and 40 degrees C, and ionic strength between 0.05 and 0.50 M. Polysulfide solutions were mixed with a buffer solution of known dissolved oxygen concentration, after which the decrease in the oxygen concentration of the solution was measured in time. The rate of oxygen consumption can be described by the empirical relation d[O2]/dt= -k[Sx(2-)][O2](0.59) . The reaction rate constant k is moderately dependent on pH and goes through a maximum at pH 10. The rate of oxygen consumption for polysulfide solutions is approximately four times higher than for sulfide solutions. At pH values below 9, reaction products were formed according to Sx(2-)+3/2O2-->S2O3(2-)+(x-2)S(0) . At pH values higher than 9, more thiosulfate and additional sulfide were formed, which is attributed to the low chemical stability of the sulfur of oxidation state zero, formed upon polysulfide oxidation. Our results strongly suggest that hydrolysis of this 'nascent' elemental sulfur to HS- and S2O3(2-) is faster than hydrolysis of crystalline inorganic sulfur or colloidal particles of biologically produced sulfur, and has a significant contribution already at 30 degrees C and pH 10.     

Examining the link between terrestrial and aquatic phosphorus speciation in a subtropical catchment: the role of selective erosion and transport of fine sediments during storm events

This study examined the link between terrestrial and aquatic phosphorus (P) speciation in the soils and sediments of a subtropical catchment. Specifically, the study aimed to identify the relative importance of P speciation in source soils, erosion and transport processes upstream, and aquatic transformation processes as determinants of P speciation in lake sediments (Lake Wivenhoe). Using a sequential extraction technique, NH₄Cl extractable P (NH₄Cl-P; exchangeable P), bicarbonate-dithionite extractable P (BD-P; reductant soluble P), NaOH extractable P (NaOH-rP; Al/Fe oxide P), HCl extractable P (HCl-P; apatite-P), and residual-P (Res-P; organic and residual inorganic P) fractions were compared in different soil/sediment compartments of the upper Brisbane River (UBR) catchment, Queensland, Australia. Multidimensional scaling identified two distinct groups of samples, one consisting of lake sediments and suspended sediments, and another consisting of riverbed sediments and soils. The riverbed sediments and soils had significantly higher HCl-P and lower NaOH-rP and Res-P relative to the lake and suspended sediments (P < 0.05). Analysis of the enrichment factors (EFs) of soils and riverbed sediments showed that fine grained particles (<63 μm) were enriched in all but the HCl-P fraction. This indicated that as finer particles are eroded from the soil surface and transported downstream there is a preferential export of non-apatite P (NaOH-rP, NaOH-nrP, BD-P and Res-P). Therefore, due to the preferential erosion and transport of fine sediments, the lake sediments contained a higher proportion of more labile forms of inorganic-P relative to the broader soil/sediment system. Our results suggest that a greater focus on the effect of selective erosion and transport on sediment P speciation in lakes and reservoirs is needed to better target management strategies aimed at reducing P availability, particularly in P-limited water bodies impacted by soil erosion.     

Geochemical stability of chromium in sediments from the lower Hackensack River, New Jersey

Elevated levels of chromium, partly attributable to historical disposal of chromite ore processing residue, are present in sediment along the eastern shore of the lower Hackensack River near the confluence with Newark Bay. Due to anaerobic conditions in the sediment, the chromium is in the form of Cr(III), which poses no unacceptable risks to human health or to the river ecology. However, as water quality conditions have improved since the 1970s, aerobic conditions have become increasingly prevalent in the overlying water column. If these conditions result in oxidation of Cr(III) to Cr(VI), either under quiescent conditions or during severe weather or anthropogenic scouring events, the potential for adverse ecological effects due to biological exposures to Cr(VI) is possible, though the reaction kinetics associated with oxidation of Cr(III) to Cr(VI) are unfavorable. To investigate the stability of Cr(III) in Hackensack River sediments exposed to oxic conditions, sediment suspension and oxidation experiments and intertidal sediment exposure experiments that exposed the sediments to oxic conditions were conducted. Results revealed no detectable concentrations of Cr(VI), and thus no measurable potential for total chromium oxidation to Cr(VI). Furthermore, total chromium released from sediment to elutriate water in the oxidation and suspension experiments ranged from below detection (<0.01 mg/L) to 0.18 mg/L, below the freshwater National Recommended Water Quality Criteria (NRWQC) of 0.57 mg/L for Cr(III). These results support conclusions of a stable, in situ geochemical environment in sediments in the lower Hackensack River with respect to chromium. Results showed that chemicals other than Cr(VI), including copper, lead, mercury, zinc, and PCBs, were released at levels that may pose a potential for adverse ecological effects.     

Effects of ferric hydroxide on the anaerobic biodegradation kinetics and toxicity of vegetable oil in freshwater sediments

Biodegradation of vegetable oil in freshwater sediments exhibits self-inhibitory characteristics when it occurs under methanogenic conditions but not under iron-reducing conditions. The basis of the protective effect of iron was investigated by comparing its effects on oil biodegradation rate and the toxicity of oil-amended sediments to those of clay and calcium, which reduce the toxicity of oil-derived long-chain fatty acids by adsorption and precipitation, respectively. Kinetic parameters for an integrated mixed-second-order model were estimated by nonlinear regression using cumulative methane production as the response variable and used to compare the effects of the three treatment factors on the rate of oil biodegradation. Ferric hydroxide was the only factor that significantly (P<0.05) increased the rate of methane production from canola oil, whereas calcium significantly reduced the oil biodegradation rate. Measurement of sediment toxicity using the Microtox Solid-Phase Test showed that inhibitory products formed within 5 days of oil addition, but the sediment toxicity decreased over time as the extent of oil mineralization increased. None of the other amendments significantly reduced the toxicity of oil-containing sediments. Since ferric hydroxide stimulated the rate of oil biodegradation without affecting the toxicity of oiled sediments, it must operate through a mechanism that is different from those previously described for clay and calcium.     

Enhanced recovery of arsenite sorbed onto synthetic oxides by L-ascorbic acid addition to phosphate solution: calibrating a sequential leaching method for the speciation analysis of arsenic in natural samples

Stripping voltammetry capable of detecting 0.3microg/L arsenate and arsenite was applied for speciation analysis of arsenic sorbed onto synthetic ferrihydrite, goethite at As/Fe ratio of approximately 1.5mg/g with or without birnessite after sequential extraction using 1M phosphate (24 and 16 h) and 1.2M HCl (1h). Precautions to avoid oxygen were undertaken by extracting under anaerobic conditions and by adding 0.1M l-ascorbic acid to 1M NaH(2)PO(4) (pH 5). Addition of l-ascorbic acid did not reduce As(V) to As(III). The recovery rate for As(III) using l-ascorbic acid for extraction (pH 5) but not for adsorption was 81% and 74% of total sorbed As, and was 99% and 97% of extracted As for ferrihydrite and goethite, respectively. Birnessite oxidized most As(III) during the adsorption procedure. l-ascorbic acid used both in adsorption and extraction procedures improved the recovery of As(III) to 79-94% for ferrihydrite-birnessite and 57-94% for goethite-birnessite systems with Fe/Mn ratios of 7, 70, 140 and 280g/g.     

Mobilization and speciation of chromium in compost: a methodological approach

An integral approach to study the mobility of chromium in compost is presented. The approach is based on batch pH dependence leaching tests and the analysis of the leachates for total chromium, chromium(VI) and complexes of chromium(III) with natural organic matter. As leachings are performed with no aggressive reagents (ultrapure water with added nitric acid or potassium hydroxide), the method can be considered a good approach to simulate natural scenarios. The analysis of leachates is complemented with the determination of total chromium and total Cr(VI) in the solid sample. Speciation analysis are done by high performance liquid chromatography with inductively coupled plasma mass spectrometry as detection technique; Cr(VI) is determined by ion chromatography, whereas Cr(III) complexes with natural organic matter by size exclusion chromatography. In the compost studied, Cr(VI) accounted for 6% of the total chromium in the solid, whereas no significant amounts of Cr(VI) were mobilized in the pH range studied (4-10). Chromium is mobilized as Cr(III) bound to organic matter, both to humic and fulvic acids, with an increasing contribution of humic acids at higher pHs.     

Numerical modelling of the deterioration of the Parisian metro infrastructures based on a new auscultation method

Many underground transport systems have aged and need heavy maintenance. Most of these tunnels have been affected by diverse weathering processes that have led to superficial or deep deterioration of the structure. To schedule maintenance operations, managers of these infrastructure networks need to assess the current state of tunnels. However, current diagnostic methods are mainly based on visual observations that cannot completely characterise the current state of these structures and predict the kinetics of degradation and its effect on the structural behaviour over time. In this context, we propose a methodology designed to obtain a state of deterioration of infrastructures and their evolution over time by integrating different parameters into the geometry of the tunnels and the value of the mechanical parameters of each zone (tunnel components and the ground). A numerical modelling procedure based on the parameters derived from a new methodology for auscultation is used to highlight the most damaged areas, which can disrupt the stability of the underground structures. The instantaneous decrease in the mechanical parameters of galleries is considered (from the initial state) to reproduce different states of alteration displayed on different surveys. Several scenarios are proposed to indicate the possible degradation observed on this underground.     

Influence of the sediment on lead speciation in the Tagus estuary

The aim of this work is to study the influence of the Tagus estuarine sediment on lead speciation in the overlying natural water. The water sample in the presence of the sediment was contaminated three times with Pb(II) in a laboratory experiment. In different periods of time, at 1-7 days after each contamination, small volumes of water were titrated with lead. The titration was followed by anodic stripping voltammetry in differential pulse mode. Before and after contamination systematic analysis of the voltammetric parameters (peak current, peak potential and peak width) were carried out to get a clear picture of Pb(II) complexation in the soluble fraction in contact with the sediment. Two main types of organic ligands, macromolecular ligands and small compounds, were detected before contamination. Both of them form labile complexes (degree of lability within the timescale of some milliseconds). The small compounds, with a diffusion coefficient similar to that of the free metal ion, present a homogeneous behaviour in terms of Pb complexation. On the other hand macromolecular ligands, with a diffusion coefficient of 1.2 x 10(-6) cm2s(-1), can be described by two different binding groups, which might be of phenolic and carboxylic type as presented by humic matter. The sediment eliminated lead contamination (10(-6) moldm(-3) was the maximum concentration added) from 12 dm3 of water (surface of 8 dm2) within 2 days. It was also found that the sediment released organic ligands responsible for both labile and inert Pb complexes "seen" by voltammetry. The release of organic ligands that decreases the bioavailability of Pb(II) was clearly detected 1 week after contamination. Therefore, the sediment acts as a buffer for lead through two mechanisms against lead contamination: removing lead ions from the solution and releasing organic ligands to the water column. In a short period of time the sediment responds as a self-cleaning system for Pb(II) contamination in the estuarine water, which may have a very important influence in environmental pollution.     

Electrochemical oxidation of organics in water: Role of operative parameters in the absence and in the presence of NaCl

The electrochemical oxidation of organics in water was investigated theoretically and experimentally to determine the role of several operative parameters on the performances of the process in the presence and in the absence of sodium chloride. Theoretical considerations were used to design the experimental investigation and were confirmed by the results of the electrochemical oxidation of oxalic acid (OA) at boron doped diamond (BDD) or IrO₂-Ta₂O₅ (DSA-O₂) anodes in a continuous batch recirculation reaction system equipped with a parallel plate undivided electrochemical cell. Polarization curves and chronoamperometric measurements indicated that, in the presence of chlorides, the anodic oxidation of OA is partially replaced by an indirect oxidation process. This result was confirmed by electrolyses experiments that show that, in the presence of suitable amount of chlorides, oxidation of OA takes place mainly by a homogeneous process. Interestingly, a very different influence of the nature of the anodic material, the flow rate and the current density on the performances of the process arises in the absence and in the presence of chlorides so that optimization of the two processes requires very different operative conditions. In the absence of chlorides, high current efficiency (CE) is obtained at BDD when most part of the process is under charge transfer controlled kinetics, i.e. when low current densities and high flow rates are imposed. On the other hand, in the presence of NaCl, higher CE are generally obtained at DSA anode when high current densities and low flow rates are imposed, i.e. when a high concentration of chemical oxidants is obtained as a result of the chloride oxidation. The effect of other operative parameters such as the OA concentration and the pH were further investigated.     

Biokinetics of Hg and Pb accumulation in the encapsulated egg of the common cuttlefish Sepia officinalis: Radiotracer experiments

Uptake and depuration kinetics of dissolved ²⁰³Hg and ²¹⁰Pb were determined during the entire embryonic development of the eggs of the cuttlefish, Sepia officinalis (50 d at 17 °C). ²⁰³Hg and ²¹⁰Pb were accumulated continuously by the eggs all along the development time reaching load/concentration ratio (LCR) of 467 ± 43 and 1301 ± 126 g, respectively. During the first month, most of the ²⁰³Hg and ²¹⁰Pb remained associated with the eggshell indicating that the latter acted as an efficient shield against metal penetration. From this time onwards, ²⁰³Hg accumulated in the embryo, indicating that it passed through the eggshell, whereas ²¹⁰Pb did not cross the chorion during the whole exposure time. It also demonstrated that translocation of Hg associated with the inner layers of the eggshell is a significant source of exposure for the embryo. This study highlighted that the maturing embryo could be subjected to the toxic effects of Hg in the coastal waters where the embryonic development is taking place.     

Effects of pH and competing anions on the speciation of arsenic in fixed ionic strength solutions by solid phase extraction cartridges

Anion exchange resins (AERs) separate As(V) and As(III) in solution by retaining As(V) and allowing As(III) to pass through. Anion exchange resins offer several advantages including cost, portability, and ease of use. The use of AERs for the instantaneous speciation of As minimizes the effects of preservatives on As species analysis. The aims of this study were to: (1) Examine the effects of pH and competing anions on the efficacy of solid phase extraction cartridges (SPECs) for speciation of As in a 0.01 molL(-1) NaNO(3) background electrolyte. (2) Identify optimal conditions (e.g. flow rates) for As speciation. (3) Calculate method detection limits (MDLs) from spiked background electrolyte and percent recoveries of As species from spiked extracts of mine wastes. The most effective SPEC retained As(V) through a range of environmentally relevant pH values (4-8). The mass loading capacity for As(V) was reduced in the background electrolyte (0.006 mg) compared with As(V) in deionized H(2)O (0.75 mg). Some retention (10-20%) of As(III) occurred on pre-wetted cartridges. Approximately 98% of spiked As(III) passed through dry cartridges. The recommended flow rate (0.5 mL min(-1)) was increased to 5 mL min(-1) without significant effect on As(V) retention. The presence of anions decreased the retention of As(V) with sulfate and phosphate having the greatest impact. MDLs were 0.004 mg L(-1) for both inorganic species. Spike recoveries in 0.01 M NaNO(3) mine waste extracts averaged 94% for As(III) and 107% for As(V).     

Experimental and modelling study on the uptake and desorption kinetics of 133Ba by suspended estuarine sediments from southern Spain

Dispersion of pollutants in aquatic environments depends on their uptake by suspended solids. This work deals with the uptake kinetics of 133Ba (gamma-emitter and a good analogue of 226Ra) by suspended estuarine sediments (which can be resuspended into the water column under certain conditions). This study presents a wide set of tracing experiments, including second tracing, decantation and desorption processes. The purpose is to characterize 133Ba uptake by sediments and to investigate the use and limitations of box models in order to describe the uptake kinetics. Water and sediment samples were collected in the Huelva estuary (Spain), where environmental 226Ra concentrations have been increased by two phosphate fertilizer industries. Samples were characterized by granulometric, organic carbon content, cation exchange capacity and XRF-EP analyses. Results revealed three-step kinetics, with characteristic times of minutes, hours and days. These results enabled the selection and calibration of a suitable box model and facilitated the testing of its use as a fully predictive tool.     

PAHs in sediments of the Black River and the Ashtabula River, Ohio: source apportionment by factor analysis

Sources of polycyclic aromatic hydrocarbons (PAHs) in the Black River and Ashtabula River sediments were apportioned using a factor analysis (FA) model with nonnegative constraints. Source profiles, contributions (microg/g) and percent contributions are determined with no prior knowledge of sources. The FA model includes scaling and backscaling of data with average PAH concentrations, without sample normalization. The present work is a follow-up to studies that used a chemical mass balance model to apportion sources to the same data sets. Literature source profiles, modified based on gas/particle partitioning of individual PAHs, from nine PAH sources were considered for comparison. FA results for a three-source solution indicate traffic (58%), coke oven (26%), and wood burning/coal tar (16%) are the primary PAH sources to Black River sediments. The primary PAH sources to the Ashtabula River sediments are traffic (51%), coke oven (44%), and wood burning (5%). This work supports the previous studies of Black River and Ashtabula River PAHs by CMB model. In addition, FA provides a more realistic fit to Ashtabula River model data by eliminating 100% contributions from one source.     

Point source influences on the carbon and nitrogen geochemistry of sediments in the Stockholm inner archipelago, Sweden

This study reports analyses of carbon and nitrogen content, and delta(15)N and delta(13)C in sediments of the H?ggarnsfj?rden Bay near Stockholm. Samples have been taken upstream, near, and downstream of a point source of processed leach water from a garbage dump. The surface sediment at the upstream and downstream sites has delta(15)N and delta(13)C close to the expected background of the area, even though a contribution from the leach water can be observed downstream of the point source. The sediment close to the outflow is strongly influenced by the carbon and nitrogen in the leach water.     

Study on a discrete-time dynamic control model to enhance nitrogen removal with fluctuation of influent in oxidation ditches

The aim of study was proposed a new control model feasible on-line implemented by Programmable Logic Controller (PLC) to enhance nitrogen removal against the fluctuation of influent in Carrousel oxidation ditch. The discrete-time control model was established by confirmation model of operational conditions based on a expert access, which was obtained by a simulation using Activated Sludge Model 2-D (ASM2-D) and Computation Fluid Dynamics (CFD), and discrete-time control model to switch between different operational stages. A full-scale example is provided to demonstrate the feasibility of the proposed operation and the procedure of the control design. The effluent quality was substantially improved, to the extent that it met the new wastewater discharge standards of NH₃-N < 5 mg/L and TN < 15 mg/L enacted in China throughout a one-day period with fluctuation of influent.