Levels of persistent organic pollutants and residual pattern of DDTs in small cetaceans from the coast of São Paulo, Brazil

The State of São Paulo is the most developed area in Brazil and was impacted by persistent organic pollutants for several decades. This study investigated organochlorines in five species of small cetaceans (Pontoporia blainvillei, Stenella frontalis, Sotalia guianensis, Tursiops truncatus and Steno bredanensis) found dead along the coast of São Paulo between 1997 and 2003. DDTs (15.9 μg g⁻¹ lipid; mean for all pooled individuals) and PCBs (8.08 μg g⁻¹) exhibited the highest concentrations in the animals, reflecting large amounts formerly used in Brazil. Lower levels of mirex (0.149 μg g⁻¹), HCB (0.051 μg g⁻¹), CHLs (0.008 μg g⁻¹) and HCHs (0.007 μg g⁻¹) were detected in all species. Residual pattern of DDTs in dolphins suggests that o,p′-DDT is more recalcitrant than p,p′-DDT in the body of the animals and/or the environment. In contrast to p,p′-DDT, residues of o,p′-DDT seem to be preferentially converted into o,p′-DDD rather than o,p′-DDE.     

Removal of Congo Red from Aqueous Solution by Sorption on Organified Rectorite

Batch sorption technique was carried out for the removal of anionic dye Congo red (CR) from aqueous solution using raw rectorite (R‐REC) and organified rectorite (CTA⁺‐REC) modified by cetyltrimethylammonium bromide (CTAB) as adsorbents. The effects of organification degree of CTA⁺‐REC as well as the process parameters including the pH of dye solution, sorption time, and initial dye concentration on adsorption capacity for CR were investigated and the sorption kinetics was also evaluated. The results showed that the sorption behaviors of R‐REC and CTA⁺‐REC for CR followed pseudo‐second‐order kinetic model and the sorption equilibrium data perfectly obeyed the Langmuir isotherm. The thermodynamic parameters including entropy of sorption (ΔS⁰), enthalpy of sorption (ΔH⁰), and Gibbs free energy of sorption (ΔG⁰) were obtained and analyzed. Fourier transform infrared study revealed that a chemisorption process occurred between CR and CTA⁺‐REC. REC modified by cationic surfactants showed the higher adsorption capacities for CR compared to R‐REC and in theory would be used as an efficient and promising adsorbent for the removal of anionic dyes in wastewater treatment.     

Non-food-chain transfer of sediment-associated persistent organic pollutants to a marine benthic fish

We investigated the transfer of persistent organic pollutants (POPs) from unspiked bottom sediment to a benthic marine fish, marbled sole (Pleuronectes yokohamae), via non-food-chain pathways, i.e., via sediment particles and water column. One-year-old sole were held for 28 days in an exposure tank with bottom sediment or in a control tank. o,p′-DDE and tri- to penta-chlorobiphenyls were transferred from the sediment to the fish via non-food-chain pathways, as demonstrated by concentrations in the exposed fish at 2.5-30 times the control levels. A model analysis based on first-order kinetic equations indicated that the overall rate constant of transfer of these compounds from sediment to fish was generally lower than that from food (median of ratio, 0.48). It also suggested that relatively high concentrations of the other POPs in the food and the longer times necessary for them to reach a steady state masked any transfer of them from the sediment.     

DDT in endangered Galapagos sea lions (Zalophus wollebaeki)

We characterize for the first time the presence of DDT and its metabolites in tropical Galapagos sea lions (Zalophus wolleabeki). ∑DDT concentrations in Galapagos sea lion pups sampled in 2005 and 2008 ranged from 16 to 3070 μg/kg lipid. Concentrations of ∑DDT in pups in 2008 averaged 525 μg/kg lipid and were 1.9 times higher than that (281 μg/kg lipid) detected in pups in 2005. These concentrations are lower than those reported in many pinnipeds elsewhere, comparable to those in Hawaiian monk seals, and higher than those in southern elephant seals. The health risk characterization showed that 1% of the male pups exceeded the p,p′-DDE toxic effect concentration associated with anti-androgenic effects reported in rats. The findings provide preliminary guidance on the relationship between DDT use and ecological impacts, serving as a reference point against which possible future impact of tropical DDT use can be assessed.     

Sorption behavior of nonylphenol on marine sediments: effect of temperature, medium, sediment organic carbon and surfactant

The sorption behavior of nonylphenol (NP, a toxic endocrine disruptor) on marine sediments was studied in detail through a series of kinetic and thermodynamic sorption experiments. The results showed that the sorption reaction of NP on marine sediments reached equilibrium in 1.5 h and that it accorded well with the non-linear Ho-McKay pseudo-second-order model. The sorption isotherms of NP on H₂O-treated sediments could be well described by the Linear isotherm model, while the sorption isotherm on H₂O₂-treated sediments could be well fitted with the Freundlich isotherm model. A positive correlation was found between the distribution coefficient (K_d) and the sediment organic carbon contents. The medium salinity showed a positive relation with the K_d and a negative relation with the dissolved organic carbon (DOC). Hexadecyl trimethyl ammonium bromide (CTAB) enhanced the sorption amount of NP the most, while sodium dodecylbenzenesulfonate (SDBS) enhanced it the least. The sorption reaction of NP on marine sediments was a spontaneous, physical, exothermic and entropy-decreasing process.     

Occurrence of persistent organic pollutants in marine fish from the Natuna Island,South China Sea

Five marine fish species were collected from the Natuna Island, South China Sea to investigate the occurrence of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs). Concentrations of PBDEs, PCBs, and DDTs in marine fish ranged from 2.85 to 7.82, 14.3 to 48.1, and 7.99 to 40.3 ng/g lipid weight, respectively. Higher concentrations of PBDEs, PCBs, and DDTs were observed in Snakefish (Trachinocephalus myops), which might be attributed to their different feeding and living habits. PCBs were the predominant POPs in all marine fish, followed by DDTs and PBDEs. BDE 47 and PCB 153 were the predominant congener of PBDEs and PCBs, respectively. Compositional distribution of DDTs indicated the possible presence of fresh input sources around the Natuna Island. The ratios of o,p′-DDT/p,p′-DDT being less than 1 in fish samples suggested that DDT contributions from dicofol seemed considerably low. New input sources of DDT in South China Sea are worth further research.     

The temporal series of the New Guinea 29 April 1996 aftershock sequence

The aim of our search is the analysis of aftershock temporal series following a mainshock with magnitude M ≥ 7.0. Investigating aftershock behavior may find the key to explain better the mechanism of seismicity as a whole.In particular, the purpose of this work is to highlight some methodological aspects related to the observation of possible anomalies in the temporal decay. The data concerning the temporal series, checked according to completeness criteria, come from the NEIC-USGS data bank. Here we carefully analyze the New Guinea 29 April 1996 seismic sequence.The observed temporal series of the shocks per day can be considered as a sum of a deterministic contribution (the aftershock decay power law, n(t) = K·(t + c)^−p + K₁) and of a stochastic contribution (the random fluctuations around a mean value represented by the above mentioned power law). If the decay can be modeled as a non-stationary Poissonian process where the intensity function is equal to n(t) = K·(t + c)^−p + K₁, the number of aftershocks in a small time interval Δt is the mean value n(t)·Δt, with a standard deviation .     

Advances in separating effects of climate variability and human activity on stream discharge: An overview

Separating effects of climate change (ΔQ^c) and human activity (ΔQ^h) on stream discharge at the watershed scale is needed for developing adaptive measures to climate change. However, information is scarce in existing literature regarding whether such separating is feasible and whether reliable results can be produced. The objectives of this overview were to: (1) compare currently-used methods; (2) assess assumptions and issues of the methods; and (3) present a generic framework that overcomes possible issues. Based on the overview of fifteen recent representative studies, two methods can be used to estimate absolute magnitudes of ΔQ^c and ΔQ^h, while another method can be used to distinguish relative magnitudes of ΔQ^c versus ΔQ^h only. Because the methods’ fundamental assumptions about baseline versus altered period, water storage change and deep groundwater loss, precipitation-runoff relationship, hysteresis influence of human activity, and record of time series can seldom be satisfied for many watersheds, it is more realistic and practical to distinguish relative effects than to estimate absolute magnitudes of ΔQ^c and ΔQ^h. Moreover, a generic framework was presented for gauged watersheds with negligible groundwater loss, aiming to avoid misuse of the methods in practice.     

Adsorption of Two Taste and Odor Compounds IPMP and IBMP by Granular Activated Carbon in Water

Granular activated carbon (GAC) adsorption of two representative taste and odor (T & O) compounds, 2‐isopropyl‐3‐methoxy pyrazine (IPMP), and 2‐isobutyl‐3‐methoxy pyrazine (IBMP), in drinking water was investigated. Results show that the modified Freundlich equation best fit the experimental data during the adsorption isotherm tests, and the pseudo first‐order kinetics and intra‐particle diffusion kinetics well described the adsorption kinetics pattern. The calculated thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) indicated a spontaneous and endothermic adsorption process. Factors affecting the treatment efficiency were carefully evaluated. Acidic and alkaline conditions both favored GAC adsorption of IPMP and IBMP, especially the former. With the GAC dosage increasing, the first order adsorption rates increased, while the intra‐particle adsorption rates decreased. Within 12 h, 200 mg/L GAC could remove >90% of 150 µg/L IPMP and IBMP via adsorption at pH 3–11. Therefore, GAC is a promising treatment technology to control the T & O compounds associated water pollution.     

Residues,sources and tissue distributions of organochlorine pesticides in dog sharks (Mustelus griseus) from Zhoushan Fishing Ground,China

Ten dog sharks (Mustelus griseus) collected from Zhoushan Fishing Ground, China, were analysed for organochlorine pesticides in various tissues, including muscle, liver, skin, gill and fin, with the aim to study the residues, sources and tissue distributions of these chemicals in high trophic level marine fishes. The concentrations of DDTs, HCHs, and chlordanes varied from 7.27–26.62, 2.67–3.35, and 0.54–0.61 ng/g wet weight, respectively, with the estimated daily intake far below the acceptable daily intake and Chinese edible hygienic criteria. Data from the tissue distribution suggested a tendency of DDTs and chlordanes to accumulate in the liver, but for HCHs, direct gill penetration may be an important means of entrance. In addition, the compositional profiles indicated that the residues of HCHs and chlordanes mainly originated from the historical usage of these chemicals. However, the predominant maternal compounds and the o,p′-DDT/p,p′-DDT ratios reflected a recent use of dicofol.     

Lentil Straw: A Novel Adsorbent for Removing of Hazardous Dye – Sorption Behavior Studies

Sorption behavior of Lanaset Red (LR) G on lentil straw (LS) was studied as a function of particle size, adsorbent dose, initial pH value, initial dye concentration, and contact time. Sorption kinetics data was well described by logistic model. Modified logistic equation can be used to explain effects of initial dye concentrations and contact time on the sorption of LR G with high R² value. Freundlich model was found to be excellent in representing the equilibrium data. Thermodynamic parameters like free energy (ΔG⁰), enthalpy (ΔH⁰), and entropy (ΔS⁰) were calculated by the use of Langmuir constant. Thermodynamic data showed that the sorption processes were spontaneous and endothermic in nature. Desorption process suggested that strong binding and weak interactions could be formed between adsorbent surface and dye molecules. Results revealed that LS has a remarkable potential for the sorption of LR G.     

Sorption of heavy oil onto Jiaozhou Bay sediment

The sorption of heavy oil onto sediment collected from Jiaozhou Bay was studied in a series of kinetic and equilibrium experiments using NaCl solutions. The effects of temperature, salinity, and pH of the medium on sorption behavior were investigated.Sorption equilibrium of the heavy oil and sediment was established within 60 min. The process was shown to follow a pseudo-second-order kinetic rate model. The sorption rate decreased with increasing initial heavy oil concentration in the solution. Batch equilibrium experiments showed that the sorption isotherm could be described by the Freundlich model. The standard free energy change and enthalpy change at the temperatures studied (283, 288, 293, and 298 K) were negative. These findings indicated that the process was spontaneous and exothermic. Salinity, pH and temperature influenced sorption performance. Sorption was favored by higher concentrations of NaCl, by lower pH values and by lower temperatures.     

Tolerance of Brazilian brain coral Mussismilia braziliensis to sediment and organic matter inputs

In Brazil, where reefs occur in markedly turbid environments, the relationship between sedimentation/organic matter and corals is poorly known. Thus, the ex situ effects of sediment with and without organic matter over the ΔF/Fm and physical state of Mussismilia braziliensis were analyzed. The ΔF/Fm and coral physical state, evaluated through the susceptibility index to sedimentation (SI), were measured in seven colonies exposed to sedimentation (0–450 mg cm⁻² day⁻¹) free of organic matter after 45 days of exposure, and in 12 colonies exposed to sedimentation (0–500 mg cm⁻² day⁻¹) with organic matter content (10%), in which case ΔF/Fm was measured after 72 h and SI after 120 h. In both cases there were effects of increasing sedimentation on the SI with no effect on ΔF/Fm. Despite the tolerance to high sedimentation rates shown by this coral, we noted that the presence of organic matter might reduce its tolerance to sedimentation stress.     

Assessment of the distribution and risks of organochlorine pesticides in core sediments from areas of different human activity on Lake Baiyangdian,China

Burial characteristics and risks associated with 13 organochlorine pesticides (OCPs; α-HCH, β-HCH, γ-HCH, δ-HCH, p,p′-DDE, p,p′-DDD, p,p′-DDT, heptachlor, aldrin, dieldrin, endrin, α-endosulfan and β-endosulfan) in core sediments of Lake Baiyangdian were investigated. The core sediments were taken from areas of different anthropogenic activity along the lake. Concentrations of hexachlorocyclohexane (HCH), dichlorodiphenyltrichloroethane (DDT), heptachlor, aldrin, and endosulfan ranged from 0.64 to 2.72, nd (undetectable levels) to 2.79, 0.29 to 1.37, nd to 2.62, and nd to 1.76 ng g^?1, respectively. Concentrations of OCPs in the core sediments exhibited the following spatial trend: Dongtianzhuang > Shaochedian > Zaolinzhuang. Concentrations in the surficial layer were also found to be greater than those in the bottom layer. OCPs were dominated by HCH. β-HCH was found in the greatest concentrations, indicating that the majority of HCH came from older inputs to the area. The ratio of DDT and its metabolites (DDD and DDE) also suggested a lack of recent inputs to the lake environment. The residues of heptachlor, aldrin, and endosulfan in core sediments indicated that cyclodienes were historically applied in the area. The OCP risk assessment, which was based on effect range low and threshold effect level values, suggested that the top layer of sediment in Dongtianzhuang cores had a relatively high toxicity to human health and the environment.     

Effects of low tide rainfall on the erodibility of intertidal cohesive sediments

Low tide rainfall may represent an important but little studied process affecting sediment fluxes on intertidal mudflats. In this study, we simulated rainfall events on an intertidal mudflat (median grain size=18.4 μm) of low slope (1 in 300) then quantified effects on sediment erodibility. Treatments consisted of a high (4.1 mm min⁻¹ for 6 min) and low (0.36 mm min⁻¹ for 60 min) rain intensity, chosen to match naturally occurring events and experiments were conducted seasonally (May and August) to encompass variations in ambient sediment stability. Changes in bed elevation due to rainfall were estimated using marked rods and sediment erodibility parameters (mass of sediment eroded at a flow velocity of 0.3 m s⁻¹ (ME-30, g m⁻²) and critical erosion velocity (U_crit, m s⁻¹)) were determined in annular flumes (bed area=0.17 m²). Ambient/control sediment erodibility in May (ME-30=211 g m⁻², U_crit=0.18 m s⁻¹) was higher than in August (ME-30=30 g m⁻², U_crit=0.26 m s⁻¹) and was correlated with changes in biological activity. In May, surface sediment was influenced by high densities of the bioturbating snail Hydrobia ulvae (1736 ind. m⁻²) and low biomass of the sediment stabilising microphytobenthos (5.7 μg chlorophyll a cm⁻²). In contrast, in August H. ulvae densities were low (52 ind. m⁻²) and microphytobenthic biomass higher (9.2 μg chlorophyll a cm⁻²). The high rain treatment caused a decrease in bed elevation of between 1.5 mm (May) and 4.4 mm (August) and significantly reduced sediment organic content and microphytobenthic biomass. Rainfall increased sediment erodibility; compared to ambient sediments ME-30 increased by a factor of 1.4× in May and 8.8× in August and caused a 10–30% decline in U_crit. The seasonal difference in treatment effect was due to the change in ambient sediment stability. The low rain treatment in August had no effect on bed elevation, microphytobenthic biomass or sediment erodibility. In May, the same treatment caused a reduction in bed elevation (0.5 mm) and microphytobenthic biomass but counter-intuitively, a decrease in sediment erodibility (ME-30 was reduced by 40%, U_crit increased by 5%) compared to controls. We attribute this result to removal by rainfall of easily eroded surface flocs and biogenic roughness which resulted in an underlying sediment with a smoother surface and greater resistant to erosion. Results suggest that high intensity rain events may destabilise intertidal sediments making them more susceptible to erosion by returning tidal currents and that the sediment eroded during such events may represent a considerable fraction (up to 25%) of the seasonal variation in shore elevation. The impact of natural rain events are likely to vary considerably due to variations in droplet size, intensity and duration and the interaction with ambient sediment stability.     

Removal of Heavy Metals from Synthetic Mixture as well as Pharmaceutical Sample Via Cation Exchange Resin Modified with Rhodamine B: Its Thermodynamic and Kinetic Studies

A new sorbent was prepared by loading rhodamine B on Amberlite IR‐120. Various physico‐chemical parameters such as effects of adsorbate concentration, contact time, pH, and temperature on the sorption of the dye have been studied. Thermodynamic parameters (ΔH° and ΔS°) were also evaluated for the sorption of dye. Kinetic studies revealed that the sorption of the dye was best fit for pseudo‐second‐order kinetic. The metal ion uptake in different solvent systems has been explored through column studies. On the basis of distribution coefficient (K_d), some heavy metal ions of analytical interest from binary mixtures have been separated. The limit of detection (LOD) for the Ni²⁺ and Fe³⁺ metal ions was 0.81 and 0.60 µg L^?1, and the limit of quantification (LOQ) was found to be 2.72 and 2.0 µg L^?1. This sorbent has also been successfully applied in the analysis of multivitamin formulation. The applicability of the modified resin in the separation of heavy metals constituting real and synthetic samples has been explored.     

Implications of turbulent shear on clay floc break-up along the Atlantic estuary (Bouregreg), Morocco

Water depth,salinity,current,and suspended sediment concentration(SSC)were measured along with the grain size distribution of bed sediment along an estuarine longitudinal section.The floc size increased with increase in the percentage of clay and silt,while decreased with increase in the percentage of sand content of bed sediment.The turbulent shear,G,had a direct effect on floc size with its value increasing with increase in G up to a G value of 15 s^-1,while an inverse relation existed between floc size and G at higher G(G>15 s^-1).Further,higher turbulence enabled sand to get resuspended and cause additional shear leading to the break-up of flocs.An attempt was made to modify G to account for the combined effect of water turbulence(G)and shear imparted by sand(Ga)and the impact of the modification of G on the predictability of floc size was evaluated.A new model was developed which explains floc size in terms of sediment concentration(C),salinity gradient(S),and G for different scenarios based on the value of G.Sensitivity analysis was done for observed floc size(FS)and predicted floc size using four approaches:(I)FSαC^x;(II)FSαC^xS-y;(III)FSαC^xS^-yGz for G<15 s^-1and FSαC^xS^-yG-z for G>15 s^-1;and(IV)FSαC^xS^-yG_m^-zfor G>15 s^-1and G_m=G+Ga,where x,y,and z are determined by calibration.It was observed that the predictability of the floc size improved when the turbulence was modified to account for shear imparted by sand so that the coefficient of determination was increased from 0.78 for model III to 0.89 for model IV.Further,the settling velocity was expressed as a function of suspended sediment concentration,turbulent shear,and salinity gradient.The predictability of settling velocity was improved(R2 increased from 0.77 to 0.86)when the additional turbulence created by sand was incorporated in the non-dimensional empirical equation.The study highlights the influence of sand in causing the break-up of flocs and suggests that for turbulence shear values high enough to resuspend sand,and G has to be modified to account for the additional shear imparted by sand in mixed sediment estuarine environments.     

Synthesis and Characterization of Poly(2‐hydroxyethylmethacrylate‐hydroxyapatite) a Novel Composite for the Removal of Lead(II) from Aqueous Solutions

In the present study, a novel adsorbent, poly (2‐hydroxyethylmethacrylate‐hydroxyapatite) [P(HEMA‐Hap)], was prepared and characterized. The synthesis was achieved by means of free‐radical polymerization and a number of structural characterization methods, including FT‐IR, XRD, TGA, SEM, BET‐porosity, and swelling tests. Pb²⁺ adsorption was performed using a series of pH, time, and temperature ranges. The reusability of the composite was also tested. The results obtained indicated that the novel adsorbent is able to bind Pb²⁺ ions with strong chemical affinity. The adsorption results were fitted to the classic Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) sorption models. Thermodynamic parameters obtained demonstrated that the sorption process was spontaneous (ΔG < 0), endothermic (ΔH > 0), as expected. The process was also consistent with the pseudo‐second‐order model, and chemical adsorption was determined to be the rate‐controlling step. It was also shown that the composite could be used for five consecutive adsorption processes.     

S‐Doped Magnetic Mesoporous Carbon for Efficient Adsorption of Methyl Orange from Aqueous Solution

A simple and rapid soft‐templating coupled with one‐pot solvent thermal method is developed to synthesize S‐doped magnetic mesoporous carbon (S‐doped MMC). In this method, phenolic resin is used as a carbon precursor and Pluronic copolymer P123 is used as a template and 2,5‐dimercapto‐1,3,4‐thiadiazole is used as sulfur source. Prepared S‐doped MMC processes a high specific surface area, the Fe₃O₄ particles are well embedded in the mesoporous carbon walls that exhibit a strong magnetic response, and the hydrated iron nitrate loading amount of 0.808 g is the best. Batch adsorption experiments are carried out at different pH, initial concentration, temperature, and contact time on the adsorption of methyl orange (MO) by S‐doped MMC. The kinetic data of the adsorption process are better fitted with pseudo‐second‐order model than the pseudo‐first‐order model. Langmuir model is more suitable for the equilibrium data than Freundlich model. The thermodynamic parameters including ΔG⁰, ΔH⁰, and ΔS⁰ indicate that the adsorption is a feasible, spontaneous, and endothermic process. Finally, it is found that the coexistence of PO₄^3?, NO₃^?, SO₄^2?, Cl^?, and CO₃^2? does not influence the adsorption process. These results illustrate S‐doped MMC can be an efficient adsorbent for the removal of MO from wastewater.