Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 1-aliphatic hydrocarbons

The temporal variability and bioaccumulation dynamics of C_12–25 n-alkanes, isoprenoids and unresolved aliphatic hydrocarbons (UCM) were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the sewage impacted Buenos Aires coastal area. Fish muscles contain huge amounts of n-C_12–25 (165 ± 93, 70 ± 48 or 280 ± 134 μg g⁻¹, dry, fresh and lipid weight, respectively) and UCM (931 ± 560, 399 ± 288 and 1567 ± 802 μg g⁻¹) reflecting the chronic bioaccumulation of fossil fuels from sewage particulates. On a temporal basis, lipid normalized aliphatic concentrations peaked by the end of 2001–2002 during the rainiest period over the last four decades (1750 vs. 1083 ± 4.6 mm in 1999, 2004 and 2005), reflecting an enhanced exposition due to massive anthropogenic fluxes from Metropolitan Buenos Aires in wet years. The hydrocarbon composition in fish muscles is enriched in n-C_15–17 and isoprenoids relative to a fresh crude oil and settling particulates, with fresher signatures during the 2001–2002 maxima. Fish/settling material bioaccumulation factors (BAFs: 0.4–6.4 dry weight or 0.07–0.94 lipid-organic carbon) plotted against K_ow showed a parabolic pattern maximizing at n-C_14–18 and isoprenoids. The optimal bioaccumulation window corresponds to highly hydrophobic (log K_ow: 7.2–9.9), intermediate-size C_14–18 n-alkanes and C_15–20 isoprenoids (MW: 198–282; length: 17.9 to 25.4 Å) with melting points ranging from −19.8 to 28 °C. The uptake efficiency is inversely correlated to melting points and increased from 75% for n-C₂₅ to above 90% for n-C_14–15 and isoprenoids.     

Removal of added nitrate in the single, binary, and ternary systems of cotton burr compost, zerovalent iron, and sediment: Implications for groundwater nitrate remediation using permeable reactive barriers

Recent research has shown that carbonaceous solid materials and zerovalent iron (Fe(0)) may potentially be used as media in permeable reactive barriers (PRBs) to degrade groundwater nitrate via heterotrophic denitrification in the solid carbon system, and via abiotic reduction and autotrophic denitrification in the Fe(0) system. Questions arise as whether the more expensive Fe(0) is more effective than the less expensive carbonaceous solid materials for groundwater nitrate remediation, and whether there is any synergistic effect of mixing the two different types of materials. We carried out batch tests to study the nature and rates of removal of added nitrate in the suspensions of single, binary, and ternary systems of cotton burr compost, Peerless Fe(0), and a sediment low in organic carbon. Cotton burr compost acted as both organic carbon source and supporting material for the growth of indigenous denitrifiers. Batch tests showed that cotton burr compost alone removed added nitrate at a greater rate than did Peerless Fe(0) alone on an equal mass basis with a pseudo-first-order rate constant k=0.0830+/-0.0031 h(-1) for cotton burr compost and a k=0.00223+/-0.00022 h(-1) for Peerless Fe(0); cotton burr compost also removed added nitrate at a faster rate than did cotton burr compost mixed with Peerless Fe(0) and/or the sediment. Furthermore, there was no substantial accumulation of ammonium ions in the cotton burr compost system, in contrast to the systems containing Peerless Fe(0) in which ammonium ions persisted as major products of nitrate reduction. It is concluded that cotton burr compost alone may be used as an excellent denitrification medium in a PRB for groundwater nitrate removal. Further study is needed to evaluate performance of its field applications.     

Sorption of organic contaminants by biopolymers: role of polarity, structure and domain spatial arrangement

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.     

HPLC-MSn and GC-MS methods to study sunlight and UV-lamp degradations of 1-amino-5-naphthalene sulfonate

HPLC-DAD, HPLC-MS/MS, GC-MS and spectrophotometric methods are employed to investigate the degradation process of sodium 1-amino-5-naphthalene sulfonate (1A5NS) aqueous solutions, when exposed to sunlight and UV-lamp (254 nm) irradiations. Experimental results show that both sunlight and 254 nm UV-lamp irradiations destroy the chemical and give rise to major degradation products, characterised by the same m/z ratios. Degradation times are lower for sunlight irradiation, for which a t(1/2) value of 137.4 min has been evaluated, in comparison with the value of t(1/2) of 26.8 min, observed for UV-lamp irradiation. The degradation pathway and the structures of the degradation products are proposed.     

Advanced oxidation processes for the treatment of olive-oil mills wastewater

In this work, the treatment of an actual industrial waste with three advanced oxidation processes (AOP) has been studied: conductive-diamond electrooxidation (CDEO), ozonation and Fenton oxidation. The wastewater comes from olive-oil mills (OMW) and contains a COD of nearly 3000 mg dm(-3). CDEO allowed achieving the complete mineralization of the waste with high current efficiencies. Likewise, both ozonation and Fenton oxidation were able to treat the wastes, but they obtained very different results in terms of efficiency and mineralization. The accumulation of oxidation-refractory compounds as final products excludes the use of ozonation and Fenton oxidation as a sole treatment technology. This confirms that besides the hydroxyl-radical mediated oxidation, CDEO combines other important oxidation processes such as the direct electro-oxidation on the diamond surface and the oxidation mediated by other electrochemically formed compounds generated on this electrode.     

XAFS studies of cobalt(II) binding by solid peat and soil-derived humic acids and plant-derived humic acid-like substances

This work has examined cobalt(II) binding by a variety of solid humic acids (HAs) isolated from peat, plant and soil sources at temperatures down to 60K. The results confirm that X-ray absorption near-edge spectroscopy (XANES) measurements cannot distinguish between aquo and carboxylato ligands in the inner coordination sphere of Co(II). However, between 1 and 2 inner-sphere carboxylato ligands can be detected in all the peat, plant and soil-derived HA samples by extended X-ray absorption fine structure (EXAFS) measurements, indicating inner-sphere coordination of HA-bound Co(II). The precision of C(carboxylate) detection is limited by the extent and quality of the data and the contribution from inner-sphere O to the Fourier transformed peaks used to detect carbon. Putative chelate ring formation is consistent with a relatively negative entropy change in step A, the stronger Co(II) binding step by HA functional groups, and could relate to 'non-exchangeable' metal binding by HSs.     

Plant senescence: a mechanism for nutrient release in temperate agricultural wetlands

The beneficial uptake of nutrients by wetland plants is countered to some extent by nutrient release back into the aquatic environment due to vegetative die-back. This current study examined whether Leersia oryzoides, a common wetland plant, exhibits luxury uptake of nutrients from simulated farm runoff. The study also tested whether with subsequent decomposition, these nutrients are released back into the water column. When exposed to elevated (>2mg/L N and P) runoff, L. oryzoides assimilated significantly higher concentrations of nitrogen (p<0.001) and phosphorus (p<0.001) in above-ground biomass as compared to non-enriched treatments (<0.05 mg/L N and P). Subsequently, senescence of enriched above-ground biomass yielded significantly higher concentrations of phosphorus (2.19+/-0.84 mg P/L). Using L. oryzoides as our model, this study demonstrates nitrogen and phosphorus sequestration during the growing season and release of phosphorus in the winter.     

Essential and non-essential element concentrations in two sleeper shark species collected in arctic waters

A number of elements/metals have increased in arctic biota and are of concern due to their potential toxicity. Most studies on elements in the Arctic have focused on marine mammals and seabirds, but concentrations in the Greenland shark (Somniosus microcephalus) and Pacific sleeper shark (Somniosus pacificus), the only two shark species known to regularly inhabit arctic waters, have never been reported. To address this data gap, concentrations and patterns of 25 elements were analyzed in liver of Greenland sharks collected about Cumberland Sound (n=24) and Pacific sleeper sharks collected about Prince William Sound (n=14). Several non-essential elements differed between species/locations, which could suggest geographical exposure differences or ecological (e.g., diet) differences between the species. Certain essential elements also differed between the two sleeper sharks, which may indicate different physiological requirements between these closely related shark species, although information on such relationships are lacking for sharks and fish.     

Chemically catalyzed uptake of 2,4,6-trinitrotoluene by Vetiveria zizanioides

The efficiency of vetiver grass (Vetiveria zizanioides) in removing 2,4,6-trinitrotoluene (TNT) from aqueous media was explored in the presence of a common agrochemical, urea, used as a chaotropic agent. Chaotropic agents disrupt water structure, increasing solubilization of hydrophobic compounds (TNT), thus, enhancing plant TNT uptake. The primary objectives of this study were to: (i) characterize TNT absorption by vetiver in hydroponic media, and (ii) determine the effect of urea on chemically catalyzing TNT uptake by vetiver grass in hydroponic media. Results showed that vetiver exhibited a high TNT uptake capacity (1.026 mgg(-1)), but kinetics were slow. Uptake was considerably enhanced in the presence of urea, which significantly (p<0.001) increased the 2nd-order reaction rate constant over that of the untreated (no urea) control. Three major TNT metabolites were detected in the roots, but not in the shoot, namely 1,3,5-trinitrobenzene, 4-amino 2,6-dinitrotoluene, and 2-amino 4,6-dinitrotoluene, indicating TNT degradation by vetiver grass.     

Pentachlorophenol association with fulvic acids from recycled wastes

The apparent water solubility of pentachlorophenol was measured at pH=6 and at 25 degrees C in pure water, aqueous solutions of three salts (NaCl, KNO(3) and CaCl(2) at 0.010, 0.10 and 1.0M) and in aqueous solutions of three fulvic acids samples extracted from a natural soil (sFA), composted sewage sludge (csFA) and composted livestock's material (lsFA). A solubility enhancement method was developed for the measurement of partition coefficients (K(oc), L/kg organic carbon). Pentachlorophenol associates strongly with the fulvic acid samples and the calculated K(oc) were the following (averages and standard deviations): (sFA) (211+/-22) x 10(2), (csFA) (253+/-26) x 10(2), (lsFA) (235+/-10) x 10(2). For comparison purposes the K(oc) for pyrene were also calculated for the three FA samples and were the following: (sFA) (119+/-10) x 10(2), (csFA) (239+/-21) x 10(2), (lsFA) (92+/-10) x 10(2). The analysis of variance (one-way ANOVA) of the effect of the type of FA sample on the solubilization of pentachlorophenol and pyrene shows that this factor causes significant differences on the aqueous solubilization of these two organic substances.