Evidence for a mutual effect of biofilms, suspended particles and sediments on DDT sorption

This report shows that biofilms and suspended particles double DDT sorption capacity on surface sediments. Sorption of pollutants by solid materials, such as biofilms, suspended particles and sediments, is a major process controlling the fate of hydrophobic pollutants in natural waters. Most previous studies focused on the sorption of hydrophobic pollutants by single-solid material, whereas few studies considered the mutual effect of different solids on the sorption. Various solid materials often interact with each other when they coexist in the same system. Therefore, pollutants sorption could be different from that in the single-solid sorption system. Here we studied the mutual effect of biofilms, suspended particles and surface sediments on the sorption of dichlorodiphenyltrichloroethane (DDT). Results showed that biofilms and suspended particles double DDT sorption capacity on surface sediments. The different effects were mainly determined by distinct components and structures of the three solid materials, particularly by organic components. Here we show the mutual effect of biofilms, suspended particles and sediments on DDT sorption.     

Sorption of DDTs on biofilms, suspended particles and river sediments: effects of heavy metals

The sorption by solid materials is one of the most important processes that affect the fate of hydrophobic organic pollutants in aquatic systems. Current studies focus on the sorption of hydrophobic pollutants by single natural solid material, whereas few studies compared the sorption behaviors of different solids. Furthermore, natural aquatic environment is a complex system where hydrophobic pollutants coexist with many other pollutants, but only limited studies reported the effects of coexisting components on the sorption. Here we studied the sorption of dichlorodiphenyltrichloroethanes (DDTs) by three common solids in natural water, i.e., biofilms, suspended particles and sediments. The effects of typical coexisting heavy metals on the sorption were also examined. The results show that the sorption is described by a dual-mode sorption model. Compared with sediments, more DDTs were sorbed by biofilms and suspended particles. Coexisting Pb, Cd and Cu increased the sorption of DDTs on sediments while decreasing the sorption on biofilms slightly, with little effect on the sorption on suspended particles. The different sorption behaviors of the solids were mainly determined by the composition of the solids: more organics were observed in biofilms and suspended particles.     

The role of soil humic and fulvic acid in the sorption of endosulfan (alpha and beta)

The sorption behaviour of alpha- and beta-endosulfan in soil organic matter was investigated using standard soil humic acid (HA) and soil fulvic acid (FA) with a modified solubility enhancement method and a dialysis bag technique. For HA, all the experiments were conducted at an ionic strength of 0.001 mol/L, in both the presence and absence of calcium and at an ionic strength of 0.01 mol/L. For FA, the experiments were conducted at two ionic strengths: 0.001 mol/L (with calcium) and 0.01 mol/L. This study is the first to describe the striking differences in the sorption behaviours of the two stereoisomers of endosulfan in HA and in FA. The sorption coefficients of alpha-endosulfan in HA and FA were significantly higher than those of beta-endosulfan. Beta-endosulfan has comparable sorption coefficients (1.5–5.4 L/g) in HA and in FA. Ionic strength and the presence of calcium have no significant effect on the sorption of beta-endosulfan in HA. However, calcium can significantly (p=0.01) enhance the solubility of alpha-endosulfan in HA. Changes in ionic strength by one order of magnitude also affect the solubility of alpha-endosulfan in HA. The sorption coefficients of alpha-endosulfan in HA (10–36 L/g) were greater than those in FA (9–14 L/g). The chirality of the alpha-isomer was hypothesised to be the primary reason behind its higher sorption in soil organic matter relative to the beta-isomer. In the presence of dissolved HA and FA found in natural soil environments, solubility of endosulfan can be increased by five times than the aqueous solubility of endosulfan without HA and FA.     

Dr Gwyneth Dorothy Howells (1925–2009), former Editor in Chief of Chemistry and Ecology

This paper presents the results of the examination of concentrations of chlorinated hydrocarbons in surface sediments from the middle of the Adriatic. the sampling area was chosen as part of the protection programme of the Adriatic Sea and is located at two transverse transects, each consisting of four stations. the sediments were collected during the summer cruise of 1990. Quantification of individual components was performed by Capillary Gas Chromatography (CGC) using reference standards. Areal distribution of the concentrations of HCB, lindane, DDT and its metabolites, dieldrin, endrin and PCBs are presented. the values obtained varied within a wide range of concentration from 20 pg/g dry weight for lindane to 700 pg/g dry weight for Σ DDT and the sum of PCBs as Aroclor 1254 from 0.3 to 6.6 ng/g.

The main source of these compounds is thought to be from suspended matter entering the Adriatic sea via the River Po and transported by currents to its middle part.     

Chlorinated Hydrocarbons in Surface Sediments From the Open Adriatic

This paper presents the results of the examination of concentrations of chlorinated hydrocarbons in surface sediments from the middle of the Adriatic. the sampling area was chosen as part of the protection programme of the Adriatic Sea and is located at two transverse transects, each consisting of four stations. the sediments were collected during the summer cruise of 1990. Quantification of individual components was performed by Capillary Gas Chromatography (CGC) using reference standards. Areal distribution of the concentrations of HCB, lindane, DDT and its metabolites, dieldrin, endrin and PCBs are presented. the values obtained varied within a wide range of concentration from 20 pg/g dry weight for lindane to 700 pg/g dry weight for Σ DDT and the sum of PCBs as Aroclor 1254 from 0.3 to 6.6 ng/g.

The main source of these compounds is thought to be from suspended matter entering the Adriatic sea via the River Po and transported by currents to its middle part.     

Influence of dissolved organic matter from corn straw on Zn andCusorption to Chinese loess

The interaction of Zn and Cu with dissolved organic matter (DOM) is a significant physicochemical process affecting their sorption as well as mobility in soil. The objective of this study was to examine the influence of DOM from corn straw on the sorption of Zn and Cu by loess through batch adsorption technique. The sorption isotherms of Zn and Cu could be well described by the Freundlich equation, and the partition distribution coefficient (k) in the presence of DOM was reduced by 86% for Zn and 58% for Cu, as compared to the control receiving no DOM, suggesting that DOM had a stronger inhibitory effect on Zn sorption than that of Cu. In addition, the sorption of metal increased with an increase in pH for loess, with maximum inhibition on metal sorption observed at pH > 7.6 for Zn and pH > 5.5 for Cu in the absence ofDOM but Cu sorption of DOM was suddenly decreased with an increase of pH at pH > 7.9 in the presence of DOM. At a DOM concentration of <200 mg L^?1, sorption of Zn and Cu was reduced by 46% for Zn and 32% for Cu with an increase in DOM concentration.     

Metal immobilization by sludge-derived biochar: roles of mineral oxides and carbonized organic compartment

Pyrolyzing sludge into biochar is a potentially promising recycling/disposal solution for municipal wastewater sludge, and the sludge-derived biochar (SDBC) presents an excellent sorbent for metal immobilization. As SDBC is composed of both mineral oxides and carbonized organic compartment, this study therefore compared the sorption behaviour of Pb and Zn on SDBC to those of individual and mixture of activated carbon (AC) and amorphous aluminium oxide (Al₂O₃). Batch experiments were conducted at 25 and 45 °C, and the metal-loaded sorbents were artificially aged in the atmosphere for 1–60 days followed by additional sorption experiments. The Pb sorption was generally higher than Zn sorption, and the co-presence of Pb reduced Zn sorption on each studied sorbent. Higher sorption capacities were observed at 45 °C than 25 °C for SDBC and AC, while the opposite was shown for Al₂O₃, indicating the significance of temperature-dependent diffusion processes in SDBC and AC. Nevertheless, metal sorption was more selective on Al₂O₃ that showed a greater affinity towards Pb over Zn under competition, correlating with the reducible fraction of sequential extraction. Furthermore, significant amounts of Pb and Zn were additionally sorbed on SDBC following 30-day ageing. The X-ray diffraction revealed the formation of metal-phosphate precipitates, while the X-ray photoelectron spectroscopy showed a larger quantity of metal–oxygen bonding after 30-day ageing of metal-loaded SDBC. The results may imply favourable long-term transformation and additional sorption capacity of SDBC. In conclusion, SDBC resembles the sorption characteristics of both organic and mineral sorbents in different aspects, presenting an appropriate material for metal immobilization during soil amendment.     

The sorption of selenite from aqueous solutions by pyrite

Selenium (Se) is an essential trace nutrient for mammals; however, the range between deficit and toxic levels is narrow. In this study, the potential sorption of selenite onto pyrite particles from an aqueous solution was investigated. An intraparticle diffusion model was used to describe kinetic data of sorption, yielding diffusivity values of 5 × 10^?7 cm²/s. The Langmuir isotherm equation could be used to describe the experimental data. The fitting results indicated that b and {Se(IV)}_max have values of 0.37 L/mg and 3.49 mg/g, respectively. The sorption of selenite onto the surface of pyrite particles was dependent on a pH range of 2–12, and the quantity of sorption onto pyrite was negatively correlated with pH; that is, the amount of sorption onto pyrite increased with a decrease in pH. In addition, organic matter did not exert a significant effect on removal of selenite. With a reaction time greater than 1 week, sorption of selenite onto pyrite particles was found to partially reduce the amount of elemental Se.     

Waste control by waste: efficient removal of bisphenol A with steel slag,a novel activator of peroxydisulfate

Activated persulfates are efficient reagents for oxidation of organic contaminants and water treatment. Various compounds are currently used to activate persulfates, but there is a need for cheap and efficient activators. Here, we report the first use of steel slag, an industrial solid waste, as a solid activator for peroxydisulfate activation. We tested this system for bisphenol A degradation. Results indicate that about 70% of bisphenol A can be removed within 1 h. Conditions were 50 μg/L of bisphenol A, 2 g/L of peroxydisulfate, 3 g/L of steel slag and temperature of 298 K. The components and surface morphology of unused and recycled steel slag were analyzed by X-ray diffraction and scanning electron microscopy, whereas the main reactive oxygen species were elucidated by using radical scavengers. Findings show that both base oxides and iron oxides are responsible for peroxydisulfate activation. A redox mechanism involving liquid and solid phases is proposed. Overall, this study reveals the successful recycling of steel slag to activate persulfates for water treatment, following the principle of ‘waste control by waste.’     

Phenanthrene sorption to environmental black carbon in sediments from the Song-Liao watershed (China)

Black carbon (BC) in ten contaminated sediments from the Song-Liao watershed, NE China, was isolated upon treatments using a combustion method at 375°C, and the isolates’ sorption isotherms for phenanthrene (Phen) were determined. All sorption isotherms were nonlinear and fitted well by the Freundlich model. A negative relation was found between Freundlich sorption nonlinearity parameter (n values) and BC/total organic carbon (TOC) content of the original sediments (r²=0.687, p<0.01), indicating the dominance of BC in Phen sorption nonlinearity. The BC isolates from this industrialized region had n values of 0.342 to 0.505 and logK_FOC values of 6.02 to 6.42(μg·kg⁻¹·OC⁻¹)/(μg·L⁻¹) ⁿ for Phen. At a given C_e, the BC had higher K_oc value than the original sediments, revealing a higher sorption capacity for BC. BC was responsible for 50.0% to 87.3% of the total sorption at C_e=0.05 S_w, clearly indicating the dominance of BC particles in overall sorption of Phen by sediments.     

Unwanted metals and hydrophobic contaminants in bioreactor effluents are associated with the presence of humic substances

Biological treatment of landfill leachate is challenging due to the presence of complex compounds. Here, we treated an old landfill leachate using a membrane bioreactor under the following conditions: 24 h for hydraulic retention, 65 days of sludge retention and an average organic load rate of 1.71 ± 0.16 g/L/day. We observed a high removal of ammonia, phosphorous and some metals. However, removal of organic carbon was incomplete. Despite a major removal of suspended solids, hydrophobic and volatile hydrophilic compounds, high concentration of fulvic acid and hydrophilic contaminants was found in the effluent. Overally, we demonstrate that the presence of humic substances in the effluent is associated with the detection of arsenic, copper and chromium and di(2-ethylhexyl) phthalate.     

Characterization of interaction between different adsorbents and copper by simulation experiments using sediment-extracted organic matter from Taihu Lake,China

The complex capacity of different types of organic matters （OMs） for Cu was quantitatively studied by simulation experiments using different adsorbents prepared from the sediment in Taihu Lake. The free Cu was measured with ion selective electrode （ISE） and complex capacity was calculated using a conditional formation constant model. The result indicated that the complex capacity was 0.048 mmol·g-1, 0.009 and 0.005 mmol.g-1for raw sediment, sediment without DOM, sediment without insoluble organic matters but with DOM and sediment without OM. Insoluble organic matter played a major role in the sorption of Cu in sediment and it can adsorb most Cu from water column. In the solution, Cu mainly existed as a complex with DOM and the DOM-Cu complexation capacity was 327.87 mg. g-1. The change of TOC and pH indicated ion-exchange in the interaction between free Cu and DOM. When the Cu concentration in the experiment reached the complex capacity of DOM, precipitation was the major mechanism to remove Cu from water phase, which was observed from UV absorbance change of DOM, that is, its aromaticity increased while molecular weight decreased. The desorption result indi- cated that DOM was more capable of desorbing Cu from adsorbents without OM than adsorbent with OM. The desorbed quantity with DOM was 1.65, 1.78 and 2.25 times higher than that with water for adsorbents without OM, raw adsorbents （sediment） and adsorbents without DOM.     

Optimisation of bisphenol A removal from water using chemically modified pine bark and almond shell

The ability of pine bark and almond shells to remove bisphenol A (BPA) from aqueous solutions was evaluated. Samples of these traditional agro-forestry by-products were milled, sieved into different particle size fractions (0.10–0.15 and 1.5–2.0 mm) and submitted to two different types of treatment. Sorption experiments were conducted in a batch system at room temperature and natural pH. Sorption equilibrium was attained after 48 h for all systems under study. Bisphenol A was adsorbed more effectively on the smaller particles of the sorbents. Pine bark and almond shell pretreated with formaldehyde presented higher sorption efficiency (95%), followed by almond shell (87%) and pine bark (82%) washed with hot water. All the sorption isotherms were found to fit a Freundlich equation, with correlation coefficients (R ²) between 0.823 and 0.989. The sorption coefficient (K _F) ranged from 0.06 to 0.74 (mg^1?1/n ·L ^1/n ·g ^?1). These results indicate that utilisation of both materials as an alternative sorbent for the removal of bisphenol A from contaminated waters is promising because they are available in large amounts and have an acceptable cost–efficiency ratio when compared with traditional adsorbents.     

Urban sediment contamination in a former Hg mining district,Idrija, Slovenia

Road sediments from gully pots of the drainage system and stream sediments from local streams were investigated for the first time in the urban area of Idrija town, the central part of the second largest and strongly contaminated Hg mining district in the world. Hg concentrations in road sediments were lower than in stream sediments. They ranged from 16 to 110 mg/kg (Md = 29 mg/kg) for <0.125 mm particles and from 7 to 125 mg/kg (Md = 35 mg/kg) for <0.04 mm particles, while Hg concentrations in stream sediments ranged from 10 to 610 mg/kg (Md = 95 mg/kg) for <0.125 particles and from 10 to 440 mg/kg (Md = 105 mg/kg) for <0.04 mm particles. High Hg loadings in stream sediments were successfully linked with identified mercury sources (rocks containing mercury ore, areas of former ore roasting sites, ore residue dumps), because they are located in the drainage areas of streams, from which the sediments were collected. Links between Hg loadings in road sediments and identified mercury sources were not recognized. Solid phases of Hg were determined by thermo-desorption technique and are similar for both types of sediments. Results show the occurrence of three different forms: elemental mercury, mercury bound to matrix components and cinnabar. Approximately 50 % of Hg in samples consist of non-cinnabar fractions. This is important, since they are potentially bioavailable. An interesting new discovery according to previous research of environmental media from Idrija area by solid-phase Hg thermo-desorption technique is that elemental mercury was determined in almost all investigated sediments in minor amounts (Md = 3 %).     

Chromium geochemistry in coastal environment of the Western Harbour,Egypt: water column,suspended matter and sediments

The distribution of Cr between water, total suspended matter (TSM) and sediments in the maine harbour in Egypt (Western Harbour), has been studied in two surveys. Dissolved Cr displayed a negative association with salinity, indicating land sources outlets as a major source of inputs for it. The Harbour presents higher Cr concentrations in dissolved form above the background (0.17 μg/L) concentration for total dissolved Cr. The most important factors controlling the distribution of particulate Cr in the Western Harbour are the depositional from several activities inside the Harbour, as well as different charges from several landbased sources along its southern edge. Chromium was associated in decreasing amount in the: residual >oxidizable-organic >acid reducible >exchangeable fractions of the analyzed sediments. Therefore, the results indicate that Cr in sediments from W.H is not available for exchange and/or release into the marine environment.     

Processes of distribution of pharmaceuticals in surface freshwaters: implications for risk assessment

The global consumption and production of pharmaceuticals is increasing concomitantly with concern regarding their environmental fate and effects. Active pharmaceutical ingredients are mainly released into the aquatic environment through wastewater effluent discharge. Once in the environment, pharmaceuticals can undergo processes of natural attenuation, i.e. dilution, sorption, transformation, depending on physico-chemical properties of the compound, such as water solubility, lipophilicity, vapour pressure, and environmental conditions, such as pH, temperature and ionic strength. A major natural attenuation process is the sorption on dissolved organic matter, colloids, suspended solids and sediments, which in turn control pharmaceuticals distribution, residence time and persistence in aquatic systems. Here we review studies of sorption capacity of natural sorbents to pharmaceuticals. These report on the importance of several environmental and sorbent-specific properties, such as the composition, quality, and amount of the sorbent, and the environmental pH, which determines the speciation of both the sorbent and compound. The importance of accounting for distribution processes on freshwater sorbents for any determination of environmental concentrations of pharmaceuticals is apparent, while the reliability of surrogate standards for measuring dissolved organic matter (DOM) distribution is evaluated in the context of the need for robust environmental risk assessment protocols.     

Effects of different sediment fractions on sorption of galaxolide

Sorption isotherms of galaxolide (HHCB) of different fractions from two sediments with different mineral and organic carbon contents were determined to compare HHCB sorption behavior and contribution to the total sorption. The HHCB sorption isotherms that used the batch equilibration method were studied on different sediments of different fractions. The sorption isotherms of 600°C heating fractions were detailed using the linear model, while the other fractions were nonlinear and fitted well with the Freundlich model. The dissolved organic carbon (DOC) removed, NaOH extracted, and 375°C heating fractions showed more nonlinear sorption than the original sediments, which suggested more heterogeneous sorption sites in these fractions. Compared to the original sediments, the 375°C heating fractions had higher carbonnormalized distribution coefficient (K _oc) values, indicating a higher sorption affinity for HHCB. Among the different sediment fractions, the contribution of the 600°C heating fractions to the overall sorption were the lowest (< 20%), while the 375°C heating fractions were the highest (up to 85%).     

Concentration of arsenic in water, sediments and fish species from naturally contaminated rivers

Arsenic (As) may occur in surface freshwater ecosystems as a consequence of both natural contamination and anthropogenic activities. In this paper, As concentrations in muscle samples of 10 fish species, sediments and surface water from three naturally contaminated rivers in a central region of Argentina are reported. The study area is one of the largest regions in the world with high As concentrations in groundwater. However, information of As in freshwater ecosystems and associated biota is scarce. An extensive spatial variability of As concentrations in water and sediments of sampled ecosystems was observed. Geochemical indices indicated that sediments ranged from mostly unpolluted to strongly polluted. The concentration of As in sediments averaged 6.58 μg/g ranging from 0.23 to 59.53 μg/g. Arsenic in sediments barely followed (r = 0.361; p = 0.118) the level of contamination of water. All rivers showed high concentrations of As in surface waters, ranging from 55 to 195 μg/L. The average concentration of As in fish was 1.76 μg/g. The level of contamination with As differed significantly between species. Moreover, the level of bioaccumulation of As in fish species related to the concentration of As in water and sediments also differed between species. Whilst some fish species seemed to be able to regulate the uptake of this metalloid, the concentration of As in the large catfish Rhamdia quelen mostly followed the concentration of As in abiotic compartments. The erratic pattern of As concentrations in fish and sediments regardless of the invariable high levels in surface waters suggests the existence of complex biogeochemical processes behind the distribution patterns of As in these naturally contaminated ecosystems.     

Aluminum fractionation in acidic soils and river sediments in the Upper Mero basin (Galicia,NW Spain)

This study aims to determine aluminum fractions in the fine earth of acidic soils under different land uses (forest, pasture and cultivation) and in the river bed sediments of the headwater of the Mero River in order to identify and quantify Al-bearing phases to assess Al mobility and potential bioavailability (environmental availability) in the monitoring area. Sequential extraction is used to evaluate the Al partitioning into six fractions operationally defined: soluble/exchangeable/specifically adsorbed, bound to manganese oxides, associated with amorphous compounds, aluminum bound to oxidizable organic matter, associated with crystalline iron oxides, and residual fraction (aluminum within the crystal lattices of minerals). The mean concentration of total aluminum (24.01 g kg^?1) was similar for the three considered uses. The mean percentage of the aluminum fractions, both in soils and sediments, showed the following order: residual fraction ? amorphous compounds ≈ crystalline iron oxides > water-soluble/exchangeable/specifically adsorbed > bound to oxidizable organic matter ≈ Mn oxides. However, in the soils, the amorphous compounds and water-soluble/exchangeable/specifically adsorbed fraction showed considerable differences between some types of uses, the percentage of aluminum linked to amorphous compounds being higher in forest soils (16% of total Al) compared to other uses (mean about 8% of total Al). The highest values of water-soluble/exchangeable/specifically adsorbed Al were also found in forest soils (mean 8.6% of the total Al versus about 4% of pasture and cultivation), which is consistent with the lower pH and higher organic matter content in forest soils. Nevertheless, the potentially bioavailable fraction (sum of the first three fractions) is low, suggesting very low geoavailability of this element in both soils and sediments; hence, the possibility to affect the crops and water quality is minimal.     

Spatio-temporal variations of fluorescence properties of dissolved organic matter along the River Têt (Pyrénées-Orientales,France)

Fluorescence excitation-emission matrices showed the spectral signature of dissolved organic matter (DOM) downstream in the River Têt at all seasons corresponding to humic substances with maximum fluorescence emission λem=420–460 nm for excitations of λex=340–360 nm and the occasional presence of tryptophan, tracer of anthropogenic pressure, spectroscopically identified by λex/λem=310/350 nm. A factorial discriminant analysis, performed using the parameters selected (λex/λem pairs of wavelength), succeeded in a better discrimination of seasons than stations, and clearly showed the presence of two fluorophores. Fluorophore 1, with two absorption bands: λex=260–320 nm and 330–390 nm for λem=440–500 nm, and Fluorophore 2, with one absorption band: λex=300–360 nm for λem=410 nm, which are attributed to humic acid (HA) and fulvic acid (FA), respectively. Variations of DOM relative contents downstream in the River Têt, according to seasons and stations, showed high amounts of DOM (pedogenic character) along the river in the humid period, with the highest value obtained in the mountain section. In contrast, in summer, the DOM contents were low (aquagenic character). Moreover, DOM presents a relatively constant composition with a percentage of FA ranging from 40% at the mountain station to 48% at the mouth river, whatever the season.